WO2014058042A1 - 光硬化性接着剤組成物、偏光板とその製造法、光学部材及び液晶表示装置 - Google Patents
光硬化性接着剤組成物、偏光板とその製造法、光学部材及び液晶表示装置 Download PDFInfo
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- WO2014058042A1 WO2014058042A1 PCT/JP2013/077718 JP2013077718W WO2014058042A1 WO 2014058042 A1 WO2014058042 A1 WO 2014058042A1 JP 2013077718 W JP2013077718 W JP 2013077718W WO 2014058042 A1 WO2014058042 A1 WO 2014058042A1
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- acrylate
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- resin
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
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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
-
- 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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- 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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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133528—Polarisers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- G02B5/3083—Birefringent or phase retarding elements
Definitions
- the present invention relates to a photocurable adhesive composition used for bonding a polarizer and a protective film in a polarizing plate, a polarizing plate in which a protective film is bonded to a polarizer using the adhesive composition, and the polarizing plate. It is related with the manufacturing method.
- the present invention also relates to an optical member and a liquid crystal display device using the polarizing plate.
- the polarizing plate is useful as one of the optical components constituting the liquid crystal display device.
- the polarizing plate is usually used by being incorporated in a liquid crystal display device in a state where protective films are laminated on both sides of the polarizer. It is also known that a protective film is provided only on one side of the polarizer, but in many cases, the other side is not merely a protective film, but a layer having another optical function also serves as the protective film. It will be pasted.
- a method for producing a polarizer a method in which a uniaxially stretched polyvinyl alcohol resin film dyed with a dichroic dye is treated with boric acid, washed with water and dried is widely known.
- a protective film is bonded to the polarizer immediately after washing and drying as described above. This is because the dried polarizer has a low physical strength, and once it is wound, problems such as tearing in the processing direction occur. Therefore, the polarizer after drying is usually applied immediately after applying an aqueous adhesive, and then a protective film is simultaneously bonded on both sides via this adhesive. Usually, a triacetyl cellulose film having a thickness of 30 to 120 ⁇ m is used as the protective film.
- a polyvinyl alcohol-based adhesive is often used for adhesion between a polarizer and a protective film, particularly a protective film made of a triacetyl cellulose film, but there are also attempts to use a urethane-based adhesive instead.
- a urethane prepolymer is used as an adhesive, and a polarizer having a high water content is bonded to a cellulose acetate-based protective film such as a triacetylcellulose film.
- JP 2000-32432 A proposes that a polyvinyl alcohol polarizer and a protective film made of a thermoplastic saturated norbornene resin are bonded with a polyurethane adhesive. Yes.
- the polyurethane adhesive has a problem that it takes a long time to cure, and the adhesive strength is not always sufficient.
- JP 2002-174729 A discloses a polarizer made of a polyvinyl alcohol-based resin film.
- a protective film made of an amorphous polyolefin resin is bonded to one surface of the resin, and a protective film made of a resin different from the amorphous polyolefin resin, for example, triacetylcellulose, is bonded to the other surface.
- a water-based first adhesive containing a specific urethane resin is interposed on one surface of a polarizing film made of a polyvinyl alcohol-based resin.
- a water-based second adhesive different from the first adhesive for example, a water-soluble polyvinyl alcohol-based resin
- an amorphous polyolefin-based resin in Patent Document 4 and also called a cycloolefin-based resin in Patent Document 5 is a polycyclic compound such as norbornene, derivatives thereof, and dimethanooctahydronaphthalene.
- a thermoplastic resin hydrogenated therewith is preferably used.
- Patent Document 6 discloses an adhesive mainly composed of an epoxy resin not containing an aromatic ring.
- the adhesive is irradiated with active energy rays to perform cationic polymerization.
- active energy rays to perform cationic polymerization.
- the epoxy adhesive disclosed herein is particularly effective for bonding various transparent resin films including amorphous polyolefin resin and cellulose resin to a polarizer.
- a protective film it has become clear that the adhesive force is not always sufficient.
- the present inventors can achieve good adhesion in a short time when a low moisture-permeable resin film selected from an acrylic resin, a polyester resin, a polycarbonate resin, and an amorphous polyolefin resin is used as a protective film for a polarizer.
- a low-viscosity photo-curing adhesive that develops strength.
- a composition containing a glycidyl ether type epoxy resin having an aromatic ring and an oxetane compound gives good adhesion, particularly when it contains 5 to 25% by weight of a (meth) acrylate monomer having an alicyclic skeleton. It discovered that high adhesive force and durability were expressed (patent document 7).
- this adhesive has a problem that although the production process itself requires only a short process of light irradiation, sufficient adhesive force cannot be exhibited until a while after the film is wound. For this reason, there existed a problem that the film handling after light irradiation in a production process was difficult.
- a photocurable adhesive composition containing an alicyclic epoxy compound, a specific poly (meth) acrylate, a photocationic polymerization initiator, and an oxetane alcohol. was found to be effective (Patent Document 8).
- the adhesive composition was a photocurable adhesive for polarizing plates that was excellent not only in adhesive strength and durability but also in productivity.
- the problem to be solved by the present invention is a case where a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin is used as a protective film, immediately after light irradiation.
- a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin is used as a protective film, immediately after light irradiation.
- adhesive strength has good final adhesive strength after a certain period of time, does not cause problems such as poor appearance after durability tests, has good adhesive strength immediately after the end of the moist heat test, and has low viscosity before curing
- Another object of the present invention is to provide an optical member capable of forming a liquid crystal display
- the photocurable adhesive composition of the present invention is a uniaxially stretched polarizer made of a polyvinyl alcohol resin film in which a dichroic dye is adsorbed and oriented, a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin.
- composition of the present invention is preferably an epoxy compound represented by the following formula (4) as the component (A).
- di (meth) acrylate of diol having 5 to 10 carbon atoms is more preferable.
- acrylate is more preferable.
- the preferable content ratio of the component (A) and the component (B) is 10 to 50% by weight and 20 to 45% by weight in the composition, respectively.
- the component (E) includes a polymer having an alkyl (meth) acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit and having a weight average molecular weight of 1,000 to 500,000. preferable.
- a polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit and having a weight average molecular weight of 1,000 to 200,000 [hereinafter also referred to as “component (E1)”]
- component (E2) A polymer containing 60 wt% or more of an alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms as a monomer unit and having a weight average molecular weight of 1,000 to 200,000 [hereinafter also referred to as “component (E2)” ] Is preferable.
- the component (E2) is a polymer obtained by high-temperature polymerization, further comprising 60% by weight or more of an alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and having a weight average molecular weight. Polymers having 1,000 to 20,000 are preferred.
- composition of the present invention preferably contains 1 to 30% by weight of an oxetane compound represented by the following formula (3) as the component (F) in the composition.
- the radically polymerizable components such as the component (B) contained in these photocurable adhesive compositions can be cured with radicals generated when the component (C) is decomposed by light.
- the radical photopolymerization initiator (G) in a proportion of 10% by weight or less.
- an acyl phosphine oxide compound is preferable in terms of excellent adhesive strength.
- these photocurable adhesive compositions contain 0.01 to 0.5% by weight of a leveling agent as component (H) in order to obtain a coated surface with excellent smoothness. It is preferable.
- the polarizing plate of the present invention is a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous material through an adhesive to a polarizer made of a polyvinyl alcohol resin film that is uniaxially stretched and adsorbed and oriented with a dichroic dye. It is a polarizing plate formed by laminating a protective film made of a transparent resin film selected from polyolefin resins, and the adhesive is a polarizing plate formed from any one of the above photocurable adhesive compositions.
- This polarizing plate is polarized through an adhesive application step of applying any one of the photocurable adhesive compositions to at least one of the bonding surfaces of the polarizer and the protective film, and an adhesive layer obtained. Including a bonding step of bonding the child and the protective film, and a curing step of curing the photocurable adhesive composition in a state where the polarizer and the protective film are bonded via the adhesive layer. It can be manufactured by a method. Specifically, after applying the uncured photocurable adhesive composition to the polarizer, a protective film is bonded to the coated surface of the adhesive composition, and then the adhesive composition is cured.
- a method of forming an adhesive layer by curing the adhesive composition while uniformly spreading the adhesive composition and then curing the adhesive composition can be employed.
- the liquid crystal display device of the present invention provides an optical member in which the above polarizing plate and an optical layer exhibiting another optical function are laminated.
- the other optical layer preferably includes a retardation plate.
- the photocurable adhesive composition of the present invention uses a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin as a protective film, after light irradiation
- a resin film having a low moisture permeability selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin
- This adhesive composition is particularly useful when the protective film is made of an acrylic resin.
- the viscosity of the adhesive composition of the present invention is very low, it can be easily applied thinly and bonded without defects.
- a polarizing plate obtained by laminating a polarizer and a protective film via this adhesive composition is not only cured in a short process of light irradiation but also immediately after light irradiation. Since a certain strength of adhesive strength can be obtained, it can be manufactured with high productivity. Furthermore, an optical member in which this polarizing plate is combined with another optical layer can form a liquid crystal display device with excellent reliability.
- a photocurable adhesive composition having a specific composition is used to adhere a protective film made of a transparent resin film to a polarizer made of a polyvinyl alcohol-based resin film that is uniaxially stretched and adsorbed and oriented with a dichroic dye.
- a polarizing plate is obtained by bonding a polarizer and a protective film through a photocurable adhesive composition.
- This polarizing plate can be laminated with an optical layer having other optical functions to form an optical member.
- the optical member can be disposed on at least one side of the liquid crystal cell to form a liquid crystal display device.
- description is advanced in order of a photocurable adhesive composition, a polarizing plate, the manufacturing method of a polarizing plate, an optical member, and a liquid crystal display device.
- photocurable adhesive composition in this invention, in order to bond a polarizer and a protective film, the photocurable adhesive composition of a specific composition is used.
- this photocurable adhesive composition may be simply referred to as “photocurable adhesive” or “composition”.
- the photocurable adhesive of the present invention essentially contains the following five components (A), (B), (C), (D) and (E).
- A Epoxy compound having an alicyclic epoxy group represented by the following formula (1) in the molecule
- B Poly (meth) acrylate
- C photocationic polymerization of a polyol having 2 to 15 carbon atoms Initiator
- D Polymer having oxetane compound
- E alkyl (meth) acrylate represented by formula (2) below as an essential constituent monomer unit
- the epoxy compound (A) is also referred to as “component (A)” or “epoxy compound (A)”
- the poly (meth) acrylate (B) is referred to as “component (B)” or “ Also called “poly (meth) acrylate (B)”
- the photocationic polymerization initiator of (C) is also called “(C) component” or “photocationic polymerization initiator (C)”
- the oxetane compound of (D) above Is also referred to as “component (D)” or “oxetane compound (D)”
- a polymer having the above-mentioned (E) alkyl (meth) acrylate as an essential constituent monomer unit is also referred to as “component (E)”.
- the content ratio of the components (A) to (E) in the composition is 10 to 65% by weight of the component (A), 10 to 55% by weight of the component (B), and (C) component based on the whole composition. Is 0.5 to 10% by weight, the component (D) is 1 to 25% by weight, and the component (E) is 0.1 to 25% by weight.
- the photo-curable adhesive can optionally contain an oxetane compound represented by the following formula (3) as the component (F), and the content is preferably 1 to 30% by weight.
- a radical photopolymerization initiator can be contained as the component (G), and a leveling agent can be contained as the component (H).
- the oxetane compound of (F) is also referred to as “(F) component” or “oxetane compound (F)”
- the radical photopolymerization initiator of (G) is referred to as “(G) component” or “ It is also referred to as “photo radical polymerization initiator (G)”
- the leveling agent (H) is also referred to as “(H) component” or “leveling agent (H)”.
- the epoxy compound as the component (A) is an epoxy compound having at least two alicyclic epoxy groups represented by the following formula (1) in the molecule, and is generally known.
- Various curable epoxy compounds can be used.
- the wavy line portion represents the coupling position with another structure.
- the component (A) examples include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxycyclohexylmethyl-3,4. -Epoxycyclohexanecarboxylate-modified caprolactone, esterified product of polyvalent carboxylic acid and 3,4-epoxycyclohexylmethyl alcohol or caprolactone-modified product, silicone compound having an alicyclic epoxy group represented by the above formula (1) at the terminal Etc.
- the number of alicyclic epoxy groups represented by the formula (1) in the component (A) is preferably 2 to 10 in view of excellent low viscosity, curability, adhesive strength and durability. 6 is more preferable, and 2 is more preferable.
- an epoxy compound represented by the following formula (4) is preferable because it is excellent in low viscosity, curability, adhesive strength and durability.
- the (A) component epoxy compound can be used alone or in combination of two or more.
- the content ratio of the epoxy compound as the component (A) is in the range of 10 to 65% by weight based on the entire composition. By setting it as this range, the adhesive force immediately after light irradiation, the final adhesive force, and durability can be made favorable. Further, when the content ratio of the component (A) is in the range of 10 to 50% by weight, the adhesive strength can be improved.
- the poly (meth) acrylate as the component (B) is a polyol poly (meth) acrylate having 2 to 15 carbon atoms.
- the adhesiveness to the polarizer and durability are excellent while lowering the viscosity of the composition.
- di (meth) acrylate of a diol having 5 to 10 carbon atoms is more preferable in terms of low viscosity, adhesive strength, and durability.
- the (meth) acrylate acrylate is preferable from the viewpoint of curability.
- component (B) examples include neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, and cyclohexanedimethylol.
- the component (B) may have an ester skeleton or an isocyanurate skeleton.
- Specific examples of the compound having an ester skeleton include an esterification reaction product of neopentyl glycol, hydroxypivalic acid, and (meth) acrylic acid.
- Examples of the compound having an isocyanurate skeleton include isocyanuric acid alkylene oxide. Examples include adduct di- or tri (meth) acrylate.
- esterification reaction products of 1,6-hexanediol di (meth) acrylate and neopentyl glycol, hydroxypivalic acid and (meth) acrylic acid are excellent in low viscosity, adhesion and durability, and low It is particularly preferable in terms of odor.
- the content ratio of the component (B) is in the range of 10 to 55% by weight based on the whole composition. By setting it as this ratio, the adhesive force immediately after light irradiation, the final adhesive force, and durability can be made favorable. Further, when the content ratio of the component (B) is in the range of 20 to 45% by weight, the adhesive force can be further improved.
- the photocurable adhesive of the present invention contains the epoxy compound (A), the oxetane compound (D) described above as a curing component, and an oxetane compound described later as necessary, and these are all cured by cationic polymerization. Therefore, a photocationic polymerization initiator is blended as the component (C).
- This cationic photopolymerization initiator generates a cationic species or a Lewis acid by irradiation with active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams, and starts a polymerization reaction of an epoxy group or an oxetanyl group.
- a cationic photopolymerization initiator as component (C), curing at room temperature becomes possible, reducing the need to consider the heat resistance of the polarizer and distortion due to expansion or contraction, and adhere the protective film well. be able to.
- the cationic photopolymerization initiator acts catalytically upon irradiation with active energy rays, it is excellent in storage stability and workability even when mixed with the epoxy compound (A) and the oxetane compound (D).
- Examples of compounds that generate cationic species and Lewis acids upon irradiation with active energy rays include aromatic diazonium salts, onium salts such as aromatic iodonium salts and aromatic sulfonium salts, and iron-allene complexes.
- aromatic diazonium salt examples include the following compounds. Benzenediazonium hexafluoroantimonate, Benzenediazonium hexafluorophosphate, Benzenediazonium hexafluoroborate, etc.
- aromatic iodonium salt examples include the following compounds. Diphenyliodonium tetrakis (pentafluorophenyl) borate, Diphenyliodonium hexafluorophosphate, Diphenyliodonium hexafluoroantimonate, Di (4-nonylphenyl) iodonium hexafluorophosphate, etc.
- aromatic sulfonium salt examples include the following compounds. Triphenylsulfonium hexafluorophosphate, Triphenylsulfonium hexafluoroantimonate, Triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis (diphenylsulfonio) diphenyl sulfide bishexafluorophosphate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluoroantimonate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenyl sulfide bishexafluorophosphate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluor
- iron-allene complex examples include the following compounds. Xylene-cyclopentadienyl iron (II) hexafluoroantimonate, Cumene-cyclopentadienyl iron (II) hexafluorophosphate, Xylene-cyclopentadienyliron (II) -tris (trifluoromethylsulfonyl) methanide and the like.
- photocationic polymerization initiators may be used alone or in combination of two or more.
- aromatic sulfonium salts are particularly preferably used because they have ultraviolet absorption characteristics even in a wavelength region of 300 nm or more, and thus can provide a cured product having excellent curability and good mechanical strength and adhesive strength. .
- the component (C) commercially available products can be easily obtained.
- “Kayarad PCI-220” and “Kayarad PCI-620” (above, manufactured by Nippon Kayaku Co., Ltd.) under the trade names, respectively.
- the content ratio of the component (C) is in the range of 0.5 to 10% by weight based on the entire composition. When the proportion is less than 0.5% by weight, the adhesive is not sufficiently cured, and the mechanical strength and the adhesive strength are lowered. On the other hand, when the proportion exceeds 10% by weight, the ionic substance in the cured product Since the hygroscopic property of the cured product increases and the durability performance may decrease due to an increase in the amount of the curable resin, it is not preferable.
- the content ratio of the component (C) is preferably 1 to 5% by weight. By setting the content within this range, optical properties such as transparency and durability can be improved.
- ⁇ Oxetane compound (D)> In the photocurable adhesive of the present invention, an oxetane compound represented by the following formula (2) is blended as the component (D). (D) By including a component, the adhesive force expression speed after light irradiation can be improved. Moreover, the final adhesive force when the relative humidity of the coating environment is about 45% can be improved. Furthermore, by including the component (D) in the relative humidity of the coating environment that can vary, the adhesive force can be expressed even if the relative humidity of the coating environment varies somewhat.
- the content ratio of the component (D) needs to be 1 to 25% by weight, preferably 1 to 18% by weight, based on the whole composition.
- the content ratio of the component (D) needs to be 1 to 25% by weight, preferably 1 to 18% by weight, based on the whole composition.
- the adhesive strength development rate after light irradiation and the final adhesive strength when the relative humidity of the coating environment is about 45% are improved.
- the relative humidity of the coating environment is about 45% without deteriorating the final adhesive force even when the relative humidity of the coating environment becomes about 65%.
- the final adhesive force and the adhesive force expression rate under both humidity conditions can be improved.
- the content of component (D) is more preferably 1 to 12% by weight.
- finish of a moist heat test can be made favorable by including (E) component.
- a polymer “having an alkyl (meth) acrylate as an essential constituent monomer unit” has the same meaning as a polymer “having at least a constituent monomer unit derived from an alkyl (meth) acrylate”. .
- the component (E) various polymers can be used as long as the polymer has an alkyl (meth) acrylate as an essential constituent monomer unit.
- the polymer which contains 50 mol% or more of alkyl (meth) acrylate as a structural monomer unit is preferable, More preferably, it is a polymer containing 80 mol% or more.
- alkyl (meth) acrylate examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, Hexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate N-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate,
- alkyl (meth) acrylates containing an alkyl group having 1 to 10 carbon atoms are preferred, and alkyl (meth) acrylates having a lower alkyl group having 1 to 4 carbon atoms are more preferred.
- Component (E) may be a copolymer of an ethylenically unsaturated monomer (hereinafter referred to as “other monomer”) copolymerizable with (meth) acrylate in addition to alkyl (meth) acrylate. good.
- other monomer ethylenically unsaturated monomer
- monomers include carboxyl group-containing monomers such as (meth) acrylic acid; sulfonic acid group-containing monomers such as acrylamide 2-methylpropanesulfonic acid and styrenesulfonic acid; Monomer; cyano group-containing monomer such as (meth) acrylonitrile, vinyl ester; aromatic vinyl compound such as styrene and ⁇ -methylstyrene; acid anhydride group-containing monomer; hydroxyethyl (meth) acrylate, hydroxyethyl Hydroxyl group-containing monomers such as hydroxyalkyl (meth) acrylates such as (meth) acrylate and hydroxybutyl (meth) acrylate; Amide group-containing monomers such as acrylamide, dimethylacrylamide and diethylacrylamide; Amino group-containing monomers Imide group-containing monomer glycidyl (meth) acryl Epoxy group-containing monomers over preparative like; (meth) acryl
- various polymers can be used from the aforementioned polymers.
- a copolymer of an alkyl (meth) acrylate and an acidic group-containing monomer is preferable.
- the acidic group-containing monomer include a carboxyl group-containing monomer, a sulfone group-containing monomer, an acid anhydride group-containing monomer, and a phosphate group-containing monomer. Is preferred.
- the copolymer is preferably a copolymer having an acid value of 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, for the purpose of improving the storage stability of the composition.
- the molecular weight of component (E) is preferably 1,000 to 500,000, more preferably 1,000 to 200,000 in terms of weight average molecular weight (hereinafter referred to as “Mw”).
- Mw means a molecular weight measured by gel permeation chromatography (hereinafter also referred to as “GPC”) in terms of polystyrene.
- component (E) various polymers can be used from the above-mentioned polymers, including an alkyl (meth) acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and having a weight average.
- a polymer having a molecular weight of 1,000 to 500,000 is preferred. More preferable examples of the polymer include the following two types of polymers.
- Component (E1) a polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit and having an Mw of 1,000 to 200,000.
- Component (E2) a carbon number of one to one as a constituent monomer unit. Polymer containing 60 wt% or more of alkyl acrylate containing 10 alkyl groups and having Mw of 1,000 to 200,000
- the component (E1) is a polymer containing methyl methacrylate as a constituent monomer unit in an amount of 60% by weight or more and having an Mw of 1,000 to 200,000, which is preferable because of excellent adhesion to acrylic resins.
- the component (E1) may be a copolymer with an acidic group-containing monomer. Examples of the acidic group-containing monomer include the same monomers as described above, and a carboxyl group-containing monomer is preferable.
- the copolymer is preferably a copolymer having an acid value of 20 mgKOH / g or less, more preferably 15 mgKOH / g or less, for the same reason as described above.
- the component (E1) is commercially available, for example, Diamar BR-80 manufactured by Mitsubishi Rayon Co., Ltd. (PMMA having a methyl monomer content of 60% by weight or more as a constituent monomer unit, Mw 95,000, acid value 0 mgKOH / g) Polymer), BR-83 (containing PMMA polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 40,000, acid value 2 mgKOH / g) and BR-87 (methyl as constituent monomer unit) PMMA polymer having a methacrylate content of 60% by weight or more, Mw 25,000, acid value 10.5 mgKOH / g) and the like.
- Diamar BR-80 manufactured by Mitsubishi Rayon Co., Ltd.
- BR-83 containing PMMA polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 40,000, acid value 2 mgKOH / g
- BR-87 methyl as constituent monomer
- the component (E1) may be one produced by high temperature polymerization, preferably high temperature continuous polymerization described later.
- the component (E2) contains 60% by weight or more of an alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit, and has an Mw of 1,000 to 200,000, such as a polarizer or an acrylic resin. It is preferable because it is excellent in adhesion to the protective film.
- Examples of the alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms include the same compounds as described above.
- the component (E2) may be an alkyl methacrylate or a copolymer with other monomers as long as it contains 60% by weight or more of an alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit. .
- the component (E2) may be a block copolymer [hereinafter referred to as “component (E2-1)”] of an alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms and an alkyl methacrylate or other monomer. good.
- component (E2-1) a block copolymer having a polyacrylate block unit and a polymethacrylate block unit, a block polymer having a block unit of a polymer block of a polyacrylate block unit and other monomers, etc.
- a block polymer having a polyacrylate block unit and a polymethacrylate block unit, and a block polymer containing polybutyl acrylate and polymethyl methacrylate as block units are preferable.
- component (E2-1) those prepared according to conventional polymerization using the above monomers can be used, and examples thereof include radical polymerization, living anion polymerization, and living radical polymerization. It is done.
- polymerization forms include solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization.
- the component (E2-1) is commercially available, and examples include Clarity (LA1114, LA2140e, LA2330, LA2250) manufactured by Kuraray Co., Ltd.
- the component (E2) has a Mw of 1,000 to 200,000, preferably a polymer having an Mw of 1,000 to 100,000, more preferably 1,000 to 20,000.
- the polymer having Mw has a low viscosity, and the composition obtained can be low in viscosity, so that the coating can be easily performed, and the number of blended parts can be increased even if there is a restriction that the composition has a low viscosity. As a result, it is preferable because the adhesive force can be improved.
- a polymer using a large amount of chain transfer agent If a polymer using a large amount of chain transfer agent is used, the cation curability and adhesive strength of the composition are liable to decrease, and if a polymer using a large amount of polymerization initiator is used, the composition is stable when stored. The property tends to decrease. Therefore, it is a polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator, and 60% by weight of alkyl acrylate containing an alkyl group having 1 to 10 carbon atoms as a constituent monomer unit.
- a polymer having Mw of 1,000 to 20,000 [hereinafter referred to as “component (E2-2)”] is preferred.
- component (E2-2) means what converted the molecular weight measured by GPC into polystyrene.
- the temperature of the high temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.
- high-temperature continuous polymerization not only has excellent productivity, but also has advantages such as excellent compatibility because it is difficult to achieve a composition distribution in the copolymer product.
- the high-temperature continuous polymerization can be carried out by a known method (for example, JP-T-57-502171, JP-A-59-6207, JP-A-60-215007, etc.).
- the glass transition temperature of the component (E2-2) is preferably 20 ° C. or lower, more preferably ⁇ 90 to 0 ° C.
- the glass transition temperature means a value measured at a rate of temperature increase of 2 ° C./min using a differential scanning calorimeter (DSC).
- the component (E) in the present invention may be a polymer in which a radical polymerizable functional group such as a (meth) acryloyl group or a cationic polymerizable functional group such as an epoxy group or an oxetanyl group is introduced.
- a radical polymerizable functional group such as a (meth) acryloyl group or a cationic polymerizable functional group such as an epoxy group or an oxetanyl group
- methods for introducing these functional groups include a method of introducing at the end of living anion polymerization or living radical polymerization, a method of adding a compound having a polymerizable functional group to a functional group in the polymer, and the like.
- (meth) acrylates having these functional groups can be copolymerized.
- the component (E) only one of the aforementioned compounds may be used, or two or more may be used in combination.
- a combination of the component (E) it is preferable to use a combination of the component (E1) and the component (E2), more preferably in terms of excellent adhesion to different types of substrates. It is preferable to use a combination of the component (E1) and the component (E2-2).
- the combined ratio of the component (E1) and the component (E2) is preferably 1/9 to 7/3.
- the content ratio of the component (E) needs to be 0.1 to 25% by weight, preferably 1 to 20% by weight, based on the whole composition.
- the adhesive strength immediately after the end of the moist heat resistance test can be improved.
- an oxetane compound represented by the following formula (3) can be blended as the component (F).
- the adhesive force expression speed after light irradiation and the final adhesive force can further be improved.
- the content ratio of the component (F) is preferably 1 to 30% by weight. By setting it as this range, the adhesive force expression speed after light irradiation and the final adhesive force can further be improved.
- the content ratio of component (F) is more preferably 1 to 20% by weight.
- the radical curable component such as the component (B) contained in the photo-curable adhesive of the present invention can be cured with radicals generated when the component (C) is decomposed by light, but the irradiation dose is small.
- a radical photopolymerization initiator as the component (G).
- the blending ratio of component (G) is preferably 10% by weight or less, more preferably 0.1 to 3% by weight, based on the entire composition. If the blending amount is 10% by weight or more, the durability may be lowered, which is not preferable.
- component (G) include the following compounds.
- the component (G) one type can be used alone, or two or more types can be blended and used according to desired performance.
- the content is preferably 10% by weight or less, more preferably 0.1 to 3% by weight, based on the entire composition.
- the content ratio of the radical photopolymerization initiator (G) is in the above range, sufficient strength is obtained and the curability is excellent.
- an acyl phosphine oxide compound is preferable in terms of excellent adhesive strength.
- the photocurable adhesive of the present invention preferably contains a leveling agent as the component (H) for the purpose of obtaining a coated surface having excellent smoothness.
- a leveling agent as the component (H) for the purpose of obtaining a coated surface having excellent smoothness.
- the component (H) include silicone leveling agents and fluorine leveling agents, and various commercially available leveling agents can be used.
- a silicone leveling agent having a (meth) acryloyl group is particularly preferable in that the adhesive strength immediately after the end of the wet heat resistance test is excellent.
- a preferable content ratio of the component (H) is 0.01 to 0.5% by weight based on the whole composition.
- the addition ratio is in the above range, the effect of adding the leveling agent is sufficiently obtained, and the adhesiveness is excellent.
- the photocurable adhesive of the present invention may contain other cationic curable components and radical curable components in addition to the components (A) to (H) described above.
- Examples of the cationic curable component other than the (A) component, the (D) component, and the (F) component include various epoxy compounds, oxetane compounds, and vinyl ether compounds.
- epoxy compound other than the component (A) examples include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of brominated bisphenol A, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl Type epoxy resin, hydroquinone diglycidyl ether, resorcin diglycidyl ether, terephthalic acid diglycidyl ester, phthalic acid diglycidyl ester, addition reaction product of terminal carboxylic acid polybutadiene and bisphenol A type epoxy resin, dicyclopentadiene dioxide, limonene dioxide 4-vinylcyclohexene dioxide, 1,6-hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, Taerythritol tetraglycidyl ether, polytetramethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidy
- oxetane compound other than the component (D) and the component (F) include an alkoxyalkyl group-containing monofunctional oxetane such as 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3 -Aromatic group-containing monofunctional oxetanes such as phenoxymethyl oxetane, 1,4-bis [(3-ethyloxetane-3-yl) methoxymethyl] benzene, 1,4-bis [(3-ethyloxetane-3- Yl) methoxy] benzene, 1,3-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 1,2-bis [(3-ethyloxetane-3-yl) methoxy] benzene, 4,4 ′ -Bis [(3-ethyloxetane-3-
- vinyl ether compound examples include cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, triethylene glycol divinyl ether, cyclohexane dimethanol divinyl ether, and the like.
- the content ratio of the cationic curable component other than the component (A), the component (D) and the component (F) is preferably less than 20% by weight, more preferably less than 10% by weight, based on the whole composition. Particularly preferably, it is less than 5% by weight.
- radical curable component other than the component (B) examples include various compounds such as (meth) acrylates, (meth) acrylamides, maleimides, (meth) acrylic acid, maleic acid, itaconic acid, (meta ) Acrylic aldehyde, (meth) acryloylmorpholine, N-vinyl-2-pyrrolidone, triallyl isocyanurate, divinyl adipate, vinyltrimethoxysilane and the like.
- (meth) acrylates having one (meth) acryloyl group in the molecule include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl ( (Meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate -Hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1,4-cyclohexanedimethylol (
- polyfunctional (meth) acrylate examples include polyethylene glycol di ( (Meth) acrylate (excluding polyols having 15 or less carbon atoms), polypropylene glycol di (meth) acrylate (excluding polyols having 15 or less carbon atoms), di (meth) acrylate of bisphenol A alkylene oxide adduct, urethane (meth) acrylate And (meth) acrylates and epoxy (meth) acrylates of polyester polyols having 16 or more carbon atoms.
- polyester (meth) acrylate having three or more (meth) acryloyl groups examples include dendrimer type (meth) acrylates.
- the blending ratio of the polyfunctional (meth) acrylate is preferably 2 to 20% by weight in the composition.
- (meth) acrylamides include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (meth) acrylamide, N- (3-N , N-dimethylaminopropyl) (meth) acrylamide, methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, N, N-diallyl (meth) acrylamide and the like.
- maleimides include N-methylmaleimide, N-hydroxyethylmaleimide, N-hydroxyethylcitraconimide, urethanized reaction product of N-hydroxyethylcitraconimide and isophorone diisocyanate, and the like.
- the content ratio of the radical curable component other than the component (B) is preferably less than 20% by weight based on the entire composition.
- the photosensitizer include benzophenone, methyl o-benzoylbenzoate, 2-isopropylthioxanthone, and 9,10-dibutoxyanthracene.
- the photosensitizer here functions as a sensitizer for the photocationic polymerization initiator of the component (C). To do.
- These may be used alone or in combination of two or more.
- the content ratio of the photosensitizer is preferably less than 3% by weight based on the whole composition.
- thermal cationic polymerization initiator examples include benzylsulfonium salt, thiophenium salt, thiolanium salt, benzylammonium salt, pyridinium salt, hydrazinium salt, carboxylic acid ester, sulfonic acid ester, and amine imide. These initiators can be easily obtained as commercial products.
- the content ratio of the thermal cationic polymerization initiator is preferably less than 3% by weight based on the whole composition.
- polyol compound examples include ethylene glycol, propylene glycol, polyether polyol compound, polyester polyol compound, polycaprolactone polyol compound, and polycarbonate polyol compound.
- the blending ratio of the polyol compound is preferably less than 10% by weight based on the whole composition.
- the viscosity of the photo-curable adhesive of the present invention is 150 mPa ⁇ s or less at 25 ° C. in order to obtain a coating surface that can be used in the production process of a polarizing plate, that is, a thin coated film with excellent smoothness. It is preferably 100 mPa ⁇ s or less. More preferably, it is 50 mPa ⁇ s or less.
- a small amount of water may be added to the photocurable adhesive of the present invention in order to improve the adhesive force to a highly dry polarizer.
- the amount of water added is preferably less than 3% by weight, more preferably less than 1% by weight, based on the entire composition.
- an ion trap agent an antioxidant, a light stabilizer, a chain transfer agent, a tackifier, a thermoplastic resin, metal oxide fine particles, an antifoaming agent, a dye, An organic solvent can also be blended.
- the photocurable adhesive described above is used for adhering a protective film to a polarizer made of a polyvinyl alcohol-based resin film that is uniaxially stretched and adsorbed and oriented with a dichroic dye, and thus the protective film is provided on the polarizer. Bonded to become a polarizing plate. That is, the polarizing plate according to the present invention is obtained by bonding a protective film to a polarizer made of a polyvinyl alcohol-based resin film that is uniaxially stretched and adsorbed and oriented with a dichroic dye.
- the protective film may be bonded only to one side of the polarizer, or may be bonded to both sides of the polarizer. When a protective film is bonded to both surfaces of the polarizer, each protective film may be made of the same type of resin, or may be made of a different type of resin.
- the polyvinyl alcohol resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate resin.
- the polyvinyl acetate resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, and copolymers of vinyl acetate and other monomers copolymerizable therewith.
- examples of other monomers copolymerized with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, and unsaturated sulfonic acids.
- the degree of saponification of the polyvinyl alcohol resin is preferably in the range of 85 to 100 mol%, more preferably 98 to 100 mol%.
- This polyvinyl alcohol-based resin may be further modified, and for example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used.
- the degree of polymerization of the polyvinyl alcohol-based resin is preferably in the range of 1,000 to 10,000, more preferably 1,500 to 10,000.
- the polarizing plate is a step of uniaxially stretching such a polyvinyl alcohol resin film, a step of dyeing the polyvinyl alcohol resin film with a dichroic dye, and adsorbing the dichroic dye, and the dichroic dye is adsorbed.
- the uniaxial stretching may be performed before dyeing with a dichroic dye, may be performed simultaneously with dyeing with a dichroic dye, or may be performed after dyeing with a dichroic dye.
- this uniaxial stretching may be performed before boric acid treatment or during boric acid treatment.
- rolls having different peripheral speeds may be uniaxially stretched or uniaxially stretched using a hot roll.
- atmosphere may be sufficient
- stretches in the state swollen with the solvent may be sufficient.
- the draw ratio is preferably about 4 to 8 times.
- the polyvinyl alcohol resin film may be immersed in an aqueous solution containing the dichroic dye.
- iodine or a dichroic dye is used as the dichroic dye.
- iodine When iodine is used as the dichroic dye, a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing iodine and potassium iodide is suitably employed.
- the iodine content in this aqueous solution is preferably about 0.01 to 0.5 parts by weight per 100 parts by weight of water, and the potassium iodide content is preferably 0.5 to 10 parts by weight per 100 parts by weight of water. About a part.
- the temperature of this aqueous solution is preferably about 20 to 40 ° C., and the immersion time in this aqueous solution is preferably about 30 to 300 seconds.
- a method of immersing and dyeing a polyvinyl alcohol-based resin film in an aqueous solution containing a water-soluble dichroic dye is suitably employed.
- the content of the dichroic dye in this aqueous solution is preferably about 1 ⁇ 10 ⁇ 3 to 1 ⁇ 10 ⁇ 2 parts by weight per 100 parts by weight of water.
- This aqueous solution may contain an inorganic salt such as sodium sulfate.
- the temperature of this aqueous solution is preferably about 20 to 80 ° C., and the immersion time in this aqueous solution is preferably about 30 to 300 seconds.
- the boric acid treatment after dyeing with a dichroic dye is performed by immersing the dyed polyvinyl alcohol resin film in an aqueous boric acid solution.
- the boric acid content in the boric acid aqueous solution is preferably about 2 to 15 parts by weight, more preferably about 5 to 12 parts by weight per 100 parts by weight of water.
- this aqueous boric acid solution preferably contains potassium iodide.
- the content of potassium iodide in the boric acid aqueous solution is preferably about 2 to 20 parts by weight, more preferably 5 to 15 parts by weight per 100 parts by weight of water.
- the immersion time in the boric acid aqueous solution is preferably about 100 to 1,200 seconds, more preferably about 150 to 600 seconds, and further preferably about 200 to 400 seconds.
- the temperature of the boric acid aqueous solution is preferably 50 ° C. or higher, more preferably 50 to 85 ° C.
- the polyvinyl alcohol resin film after the boric acid treatment is washed with water.
- the water washing treatment is suitably performed, for example, by immersing a boric acid-treated polyvinyl alcohol resin film in water.
- a drying process is performed to obtain a polarizer.
- the water temperature in the water washing treatment is preferably about 5 to 40 ° C., and the immersion time is preferably about 2 to 120 seconds.
- the drying process performed thereafter is preferably performed using a hot air dryer or a far infrared heater.
- the drying temperature is preferably 40 to 100 ° C.
- the treatment time in the drying treatment is preferably about 120 to 600 seconds.
- a polarizer comprising a polyvinyl alcohol-based resin film on which iodine or dichroic dye as a dichroic dye is adsorbed and oriented is obtained.
- a protective film is bonded to one side or both sides of the polarizer using the photocurable adhesive described above.
- Triacetyl cellulose film is widely employed conventionally as a protective film of the polarizer has a generally moisture permeability of approximately 400g / m 2 / 24hr, the present invention is stuck on at least one surface of the polarizer
- a resin having a moisture permeability lower than that of triacetyl cellulose, and a polyester resin, a polycarbonate resin, an acrylic resin, or an amorphous polyolefin-based resin is employed.
- polyester resin used for the protective film is not particularly limited, but polyethylene terephthalate is particularly preferable in terms of mechanical properties, solvent resistance, scratch resistance, cost, and the like.
- Polyethylene terephthalate means a resin in which 80 mol% or more of repeating units are composed of ethylene terephthalate, and may contain structural units derived from other copolymerization components.
- copolymer components include isophthalic acid, p- ⁇ -hydroxyethoxybenzoic acid, 4,4′-dicarboxydiphenyl, 4,4′-dicarboxybenzophenone, bis (4-carboxyphenyl) ethane, adipic acid, Dicarboxylic acid components such as sebacic acid, 5-sodium sulfoisophthalic acid, and 1,4-dicarboxycyclohexane; propylene glycol, butanediol, neopentyl glycol, diethylene glycol, cyclohexanediol, bisphenol A ethylene oxide adduct, polyethylene glycol And diol components such as polypropylene glycol and polytetramethylene glycol.
- dicarboxylic acid components and diol components can also be used in combination of two or more as required. It is also possible to use a hydroxycarboxylic acid such as p-hydroxybenzoic acid in combination with the dicarboxylic acid component or diol component.
- a hydroxycarboxylic acid such as p-hydroxybenzoic acid
- a small amount of a dicarboxylic acid component and / or a diol component having an amide bond, a urethane bond, an ether bond, a carbonate bond, or the like may be used.
- the polyester resin can be produced by directly reacting terephthalic acid and ethylene glycol (and other dicarboxylic acids and / or other diols if necessary), so-called direct polymerization method, dimethyl ester of terephthalic acid and ethylene glycol ( Furthermore, an arbitrary method such as a so-called transesterification method in which a dimethyl ester of another dicarboxylic acid and / or another diol) is transesterified as necessary can be employed.
- the polyester resin may contain a well-known additive as needed. Examples of additives that can be included include a lubricant, an antiblocking agent, a heat stabilizer, an antioxidant, an antistatic agent, a light resistance agent, and an impact resistance improver. However, since transparency is required as a protective film laminated on the polarizing film, it is preferable to keep the amount of these additives to a minimum.
- a protective film made of a stretched polyester resin can be produced by forming the raw material resin into a film and subjecting it to uniaxial stretching or biaxial stretching. By performing the stretching treatment, a film having high mechanical strength can be obtained.
- the method for producing the stretched polyester resin film is arbitrary and is not particularly limited. However, the non-oriented film obtained by melting the raw material resin and extruding it into a sheet is formed at a temperature above the glass transition temperature. And a method of performing heat setting after transverse stretching.
- the polycarbonate resin used for the protective film is a polyester formed from carbonic acid and glycol or bisphenol.
- an aromatic polycarbonate having a diphenylalkane in the molecular chain is preferably used because it is excellent in heat resistance, weather resistance and acid resistance.
- examples of such polycarbonates include 2,2-bis (4-hydroxyphenyl) propane (also known as bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane,
- Illustrative are polycarbonates derived from bisphenols, such as 1,1-bis (4-hydroxyphenyl) isobutane or 1,1-bis (4-hydroxyphenyl) ethane.
- any method such as a casting film forming method or a melt extrusion method may be used.
- a polycarbonate resin is dissolved in an appropriate organic solvent to form a polycarbonate resin solution, which is cast on a metal support to form a web, and the web is peeled off from the metal support.
- a method of obtaining a film by drying the peeled web with hot air after taking off can be mentioned.
- the acrylic resin used for the protective film is not particularly limited, but is generally a polymer having a methacrylic acid ester as a main monomer, and is preferably a copolymer in which a small amount of other comonomer components are copolymerized. .
- the methacrylic acid ester as the main component of the acrylic resin is preferably alkyl methacrylate, and methyl methacrylate is particularly preferably used.
- the comonomer component methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl-hexyl acrylate, etc. are generally used.
- an aromatic vinyl compound such as styrene, a vinyl cyanide compound such as acrylonitrile, or the like may be used as a comonomer component.
- any method such as ordinary bulk polymerization, suspension polymerization, emulsion polymerization, etc. can be adopted.
- bulk polymerization in which no water-soluble component is present in the polymerization system is particularly preferably employed.
- a chain transfer agent In order to obtain a suitable glass transition temperature or to obtain a viscosity exhibiting a formability to a suitable film, it is preferable to use a chain transfer agent during polymerization. What is necessary is just to determine the quantity of a chain transfer agent suitably according to the kind and composition of a monomer.
- the acrylic resin may contain a well-known additive as needed.
- additives include, for example, lubricants, anti-blocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance improvers, surfactants and the like.
- lubricants for example, lubricants, anti-blocking agents, heat stabilizers, antioxidants, antistatic agents, light resistance agents, impact resistance improvers, surfactants and the like.
- transparency is required as a protective film laminated on the polarizing film, it is preferable to keep the amount of these additives to a minimum.
- any method such as a melt casting method, a melt extrusion method such as a T-die method or an inflation method, or a calendar method may be used.
- the method of melt-extruding raw material resin, for example from a T die, and making a film by making at least one side of the film-form thing contact a roll or a belt is preferable at the point from which a surface property favorable film
- the acrylic resin may contain acrylic rubber particles, which are impact modifiers, from the viewpoints of film-formability on the film and impact resistance of the film.
- the acrylic rubber particles here are particles having an elastic polymer mainly composed of an acrylate ester as an essential component, and those having a single layer structure consisting essentially of this elastic polymer, or this elastic polymer. Can be a multi-layer structure having a single layer.
- An example of such an elastic polymer is a cross-linked elastic copolymer obtained by copolymerizing an alkyl acrylate as a main component with another vinyl monomer and a cross-linkable monomer copolymerizable therewith.
- alkyl acrylate as the main component of the elastic polymer include those having an alkyl group with about 1 to 8 carbon atoms, such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and the like.
- An acrylate having an alkyl group of several 4 or more is preferably used.
- examples of other vinyl monomers copolymerizable with the alkyl acrylate include compounds having one polymerizable carbon-carbon double bond in the molecule, and more specifically, methacrylic acid such as methyl methacrylate.
- aromatic vinyl compounds such as esters and styrene and vinylcyan compounds such as acrylonitrile.
- crosslinkable monomer examples include a crosslinkable compound having at least two polymerizable carbon-carbon double bonds in the molecule, and more specifically, ethylene glycol di (meth) acrylate and butanediol.
- examples include (meth) acrylates of polyhydric alcohols such as di (meth) acrylate, alkenyl esters of (meth) acrylic acid such as allyl (meth) acrylate, and divinylbenzene.
- a laminate of a film made of an acrylic resin not containing rubber particles and a film made of an acrylic resin containing rubber particles can be used as a protective film.
- an acrylic resin is used as a protective film, it is possible to obtain good adhesion without corona treatment when the composition of the present invention is used.
- corona treatment may be performed before applying the adhesive.
- the amorphous polyolefin resin used for the protective film is usually a polymer having a polymer unit derived from a polycyclic cyclic olefin such as norbornene, a derivative thereof, or dimethanooctahydronaphthalene. When a double bond remains as in the above, it is preferably a thermoplastic resin hydrogenated there.
- the amorphous polyolefin-based resin may be a copolymer of a cyclic olefin and a chain olefin, or a polar group may be introduced. Among them, a thermoplastic saturated norbornene resin is representative.
- amorphous polyolefin resins examples include “Arton” from JSR Corporation, “ZEONEX” and “ZEONOR” from Nippon Zeon Corporation, “APO” and “APO” from Mitsui Chemicals, Inc. Appel ”.
- a known method such as a solvent casting method or a melt extrusion method is appropriately used for forming the film.
- amorphous polyolefin-based resin When an amorphous polyolefin-based resin is used as the protective film, it is preferable to perform a corona treatment before applying the adhesive in order to obtain good adhesion.
- anti-glare property can be imparted to the protective film disposed on the viewing side, that is, on the side opposite to the liquid crystal cell.
- an antiglare layer having surface irregularities on the surface on the viewing side of the protective film that is, the surface opposite to the surface to be bonded to the polarizer.
- the antiglare layer imparts irregularities to the active energy ray-curable resin by an embossing method, or imparts irregularities by blending and curing the active energy ray-curable resin with fine particles having a refractive index different from that. It is formed by the method.
- the protective film is made of an acrylic resin, a light diffusing layer in which fine particles having a refractive index different from that in the acrylic resin as a binder are blended, and a transparent layer made of an acrylic resin in which such fine particles are not blended, It is also effective to form a protective film with the laminated film.
- a laminated film composed of two layers, the light diffusion layer and the transparent layer is bonded to the polarizer on the light diffusion layer side, and both surfaces of the light diffusion layer are the transparent layers.
- interposed by can be employ
- the surface on the viewing side that is, the surface to be bonded to the polarizer is It is also effective to further improve the antiglare performance by providing the antiglare layer as described above on the opposite surface.
- the epoxy resin alone which does not contain an aromatic ring, described in Patent Document 6 (Japanese Patent Application Laid-Open No. 2004-245925), does not necessarily have sufficient adhesiveness.
- the composition of the present invention gives good adhesion even when such an acrylic resin film is used as a protective film. Therefore, the present invention is particularly useful when an acrylic resin film is used as a protective film.
- the protective film made of the transparent resin film selected from the polyester resin, polycarbonate resin, acrylic resin and amorphous polyolefin-based resin described above is provided on at least one surface of the polarizer. Bonded via an adhesive.
- a protective film only to one side of a polarizer for example, it may take a form such as directly providing an adhesive layer for bonding to another member such as a liquid crystal cell on the other side of the polarizer. it can.
- the respective protective films may be of the same type or different types.
- a form in which a polyester resin film is bonded as a protective film on both sides of a polarizer a form in which a polycarbonate resin is bonded as a protective film on both sides of a polarizer, and an acrylic resin as a protective film on both sides of the polarizer
- the transparent resin film is bonded as a protective film
- the other surface of the polarizer is any one selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin-based resin, and the one-side protective film
- a transparent resin film selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin is bonded to one side of the polarizer as a protective film, and the polyester resin is attached to the other side of the polarizer. It is also possible to adopt a form in which a transparent resin film different from any of polycarbonate resin, acrylic resin and amorphous polyolefin resin is bonded as a protective film.
- two protective films may be bonded one step at a time, or both surfaces may be bonded in one step.
- the protective film When a protective film is pasted on both sides of a polarizer, and one of them is a resin film different from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin, the other A preferred example of the resin is a cellulose resin.
- the protective film made of polyester resin, polycarbonate resin, acrylic resin and amorphous polyolefin-based resin bonded to one surface of the polarizer can be passed through the photocurable adhesive described above according to the present invention. Although it adhere
- a polyvinyl alcohol-based adhesive is attached to the bonding surface of the resin film having a high moisture permeability.
- Adhesives other than the epoxy type such as an agent may be used.
- the photocurable adhesive according to the present invention gives a high adhesive force to the cellulose-based resin film exemplified here, it is advantageous to use the same adhesive on both sides of the polarizer because the operation becomes simple. It is.
- the cellulose-based resin that can be used as one protective film is a cellulose partial or completely esterified product, and examples thereof include cellulose acetate, propionate, butyrate, and mixed esters thereof. Specific examples include triacetyl cellulose, diacetyl cellulose, cellulose acetate propionate, and cellulose acetate butyrate. Examples of commercially available films made of such cellulose ester resins include “Fujitac TD80”, “Fujitac TD80UF” and “Fujitac TD80UZ” manufactured by Fujifilm Co., Ltd., “Konica Minolta Opt Co., Ltd.” KC8UX2M "and" KC8UY ".
- a cellulose resin film provided with an optical compensation function can also be used.
- an optical compensation film for example, a film in which a compound having a retardation adjusting function is contained in a cellulose resin, a film in which a compound having a retardation adjusting function is applied to the surface of the cellulose resin film, and a cellulose resin film are uniaxially Or the film obtained by extending
- Examples of commercially available cellulose-based optical compensation films include “Wide View Film ⁇ ⁇ ⁇ WV BZ 438” and “Wide View Film WV EA” manufactured by Fuji Film Co., Ltd., “Konica Minolta Opto Co., Ltd.” KC4FR-1 "and” KC4HR-1 ".
- Polysulfone resin, cycloaliphatic polyimide are examples of other resins that are different from polyester resin, polycarbonate resin, acrylic resin, and amorphous polyolefin resin, and can be used as one protective film. Resin etc. are mentioned.
- the protective film may be subjected to easy adhesion treatment such as saponification treatment, corona treatment, primer treatment, anchor coating treatment on the bonding surface prior to bonding to the polarizer. Moreover, you may have various process layers, such as a hard-coat layer, an antireflection layer, and a glare-proof layer, on the surface on the opposite side to the bonding surface to the polarizer of a protective film.
- the thickness of the protective film is preferably in the range of about 5 to 200 ⁇ m, more preferably 10 to 120 ⁇ m, and still more preferably 10 to 85 ⁇ m.
- the polarizing plate of the present invention is provided on at least one of the bonding surfaces of the polarizer described above and a protective film made of a transparent resin film selected from a polyester resin, a polycarbonate resin, an acrylic resin, and an amorphous polyolefin resin.
- the adhesive application step of applying the photocurable adhesive described above, the bonding step of bonding the polarizer and the protective film through the resulting adhesive layer, and the polarization through this adhesive layer It can manufacture by the method of including the hardening process which hardens a photocurable adhesive agent in the state in which the child
- the above-described photocurable adhesive is applied to at least one of the bonding surfaces of the polarizer and the protective film.
- the application method is not particularly limited. For example, various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- various coating methods such as a doctor blade, a wire bar, a die coater, a comma coater, and a gravure coater can be used.
- the method of pressing with a roll etc. and spreading uniformly can also be utilized.
- the atmospheric temperature in the adhesive application step is preferably 15 to 30 ° C., and particularly preferably 20 to 25 ° C.
- the relative humidity in the coating atmosphere is preferably 80% or less, more preferably 70% or less, still more preferably 30 to 70%, and particularly preferably 40 to 60%.
- the temperature of the adhesive at the time of application may be heated or heated for the purpose of improving the coating property by lowering the viscosity or improving the adhesive force described later.
- the heating or heating temperature at this time is preferably 80 ° C. or less, and more preferably in the range of 20 to 60 ° C.
- the adhesive coating film may be exposed to an atmosphere of 15 to 30 ° C. and a humidity of 80% or less after it is applied to the film until it enters the bonding step. It is preferable at the point which makes adhesive force favorable.
- ⁇ Bonding process> After apply
- this bonding step for example, when a photocurable adhesive is applied to the surface of the polarizer in the previous application step, a protective film is superimposed thereon, and in the previous application step, the surface of the protective film is photocurable.
- a polarizer is superimposed thereon.
- a photocurable adhesive is cast between the polarizer and the protective film, the polarizer and the protective film are superposed in that state.
- both sides are protected in this state (when a protective film is placed on one side of the polarizer, the polarizer side and the protective film side, and when a protective film is placed on both sides of the polarizer, both sides are protected.
- the pressure is sandwiched between rolls from the membrane side).
- metal, rubber, or the like can be used as the material of the roll.
- the rolls arranged on both sides may be the same material or different materials.
- the one in which the polarizer and the protective film are bonded through the uncured photocurable adhesive is then subjected to a curing step.
- the photocurable adhesive is irradiated with active energy rays to cure the adhesive layer containing the epoxy compound, (meth) acrylate, oxetane compound, and the like, thereby bonding the polarizer and the protective film.
- the active energy ray may be irradiated from either the polarizer side or the protective film side.
- active energy rays are applied from either side of the protective film in a state where the protective film is bonded to both sides of the polarizer via a photocurable adhesive. It is advantageous to simultaneously cure the photocurable adhesive on both sides.
- either one of the protective films contains an ultraviolet absorber (for example, when a cellulose-based resin film containing an ultraviolet absorber is used as one protective film)
- the active energy rays are ultraviolet rays. In this case, the ultraviolet ray is usually irradiated from the side of the protective film not containing the other ultraviolet absorbent.
- the active energy ray visible light, ultraviolet ray, X-ray, electron beam and the like can be used, but ultraviolet ray is generally preferably used because it is easy to handle and has a sufficient curing rate.
- the light source of the active energy ray is not particularly limited, but has a light emission distribution at a wavelength of 400 nm or less, for example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a chemical lamp, a black light lamp, a microwave excitation mercury lamp, a metal halide lamp.
- An LED lamp or the like can be used.
- the light irradiation intensity to the photocurable adhesive is determined for each target composition and is not particularly limited, but the irradiation intensity in the wavelength region effective for activating the polymerization initiator is UV. It is preferable to set it to 1 to 3,000 mW / cm 2 as ⁇ B (ultraviolet light of 280 to 320 nm).
- ⁇ B ultraviolet light
- the light irradiation time to the photocurable adhesive is controlled for each composition to be cured, and is not particularly limited.
- the integrated light amount represented by the product of the irradiation intensity and the irradiation time is UV-B. It is preferably set to be 10 to 5,000 mJ / cm 2 .
- the photocurable adhesive When curing the photocurable adhesive by irradiating with active energy rays, it should be cured under conditions that do not deteriorate the functions of the polarizing plate, such as the degree of polarization of the polarizer, the transmittance and hue, and the transparency of the protective film. Is preferred.
- the thickness of the adhesive layer is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, still more preferably 10 ⁇ m or less, and particularly preferably 5 ⁇ m or less.
- the polarizer A heating step may be added as long as the optical properties are not impaired.
- the heating conditions at this time are preferably within a range in which the polarizer does not shrink and the optical characteristics are not deteriorated. Suitable heating conditions vary depending on the molecular weight of the acrylic resin and the like, and examples thereof include 1 to 10 seconds at 60 ° C. and 5 to 30 seconds at 40 ° C. Even if the temperature of the adhesive is cooled to 40 ° C.
- the effect of improving the adhesive strength is not impaired.
- the active energy ray is bonded after the polarizer and the protective film are bonded even without heating, that is, at 20 to 25 ° C.
- the length of the production line until irradiation is increased, and the time after the adhesive and acrylic resin are in contact with each other is increased to about 60 seconds.
- optical member When using a polarizing plate, it can also be set as the optical member which laminated
- the optical layer laminated on the polarizing plate for the purpose of forming an optical member, for example, formation of a liquid crystal display device such as a reflective layer, a transflective reflective layer, a light diffusing layer, a retardation plate, a light collecting plate, a brightness enhancement film, etc.
- a liquid crystal display device such as a reflective layer, a transflective reflective layer, a light diffusing layer, a retardation plate, a light collecting plate, a brightness enhancement film, etc.
- the reflective layer, transflective reflective layer, and light diffusing layer are used when forming an optical member comprising a reflective or transflective type, diffusive type, or a polarizing plate of both types.
- the reflection-type polarizing plate is used in a liquid crystal display device of a type that reflects incident light from the viewing side and displays the light source such as a backlight, so that the liquid crystal display device can be easily thinned.
- the transflective polarizing plate is used in a liquid crystal display device that displays as a reflection type in a bright place and displays using a light source such as a backlight in a dark place.
- An optical member as a reflective polarizing plate can form a reflective layer by attaching a foil or a vapor deposition film made of a metal such as aluminum to a protective film on a polarizer, for example.
- the optical member as a transflective polarizing plate can be formed by using the reflective layer as a half mirror, or by adhering a reflective plate exhibiting light transmittance by containing a pearl pigment or the like to the polarizing plate.
- an optical member as a diffusion type polarizing plate can be obtained by various methods such as a method of performing a mat treatment on a protective film on a polarizing plate, a method of applying a resin containing fine particles, and a method of adhering a film containing fine particles. Use to form a fine relief structure on the surface.
- the optical member as a polarizing plate for both reflection and diffusion can be formed by, for example, a method of providing a reflective layer reflecting the concavo-convex structure on the fine concavo-convex structure surface of the diffusive polarizing plate.
- the reflective layer having a fine concavo-convex structure has advantages such that incident light is diffused by irregular reflection, directivity and glare can be prevented, and unevenness in brightness and darkness can be suppressed.
- the resin layer or film containing fine particles has an advantage that incident light and its reflected light are diffused when passing through the fine particle-containing layer, and uneven brightness can be further suppressed.
- the reflective layer reflecting the surface fine concavo-convex structure can be formed by, for example, attaching a metal directly to the surface of the fine concavo-convex structure by a method such as vacuum deposition, ion plating, sputtering or other vapor deposition or plating.
- a method such as vacuum deposition, ion plating, sputtering or other vapor deposition or plating.
- the fine particles to be blended to form the fine surface uneven structure include inorganic fine particles composed of silica, aluminum oxide, titanium oxide, zirconia, tin oxide, indium oxide, and the like having an average particle diameter of 0.1 to 30 ⁇ m, crosslinked or Organic fine particles made of an uncrosslinked polymer or the like can be used.
- the above-mentioned retardation plate as an optical layer is used for the purpose of compensation of retardation by a liquid crystal cell.
- a liquid crystal cell examples thereof include a birefringent film made of a stretched film of various plastics, a film in which a discotic liquid crystal or a nematic liquid crystal is oriented and fixed, and a film substrate on which the above liquid crystal layer is formed.
- a cellulose-based film such as triacetyl cellulose is preferably used as the film substrate that supports the oriented liquid crystal layer.
- plastics forming the birefringent film include polyolefins such as polycarbonate, polyvinyl alcohol, polystyrene, polymethyl methacrylate, and polypropylene, polyarylate, polyamide, and amorphous polyolefin resin.
- the stretched film may be processed by an appropriate method such as uniaxial or biaxial.
- attachment with a heat-shrinkable film may be sufficient.
- two or more retardation plates may be used in combination for the purpose of controlling optical characteristics such as broadening the bandwidth.
- the condensing plate is used for the purpose of optical path control and can be formed as a prism array sheet, a lens array sheet, or a dot-attached sheet.
- the brightness enhancement film is used for the purpose of improving the brightness in a liquid crystal display device or the like.
- a plurality of thin film films having different refractive index anisotropies are laminated to make the reflectance anisotropy.
- Examples thereof include a reflection-type linearly polarized light separating sheet designed so as to occur, an oriented film of cholesteric liquid crystal polymer, and a circularly polarized light separating sheet in which the oriented liquid crystal layer is supported on a film substrate.
- the optical member is selected from the polarizing plate, the reflective layer or the semi-transmissive reflective layer, the light diffusion layer, the retardation plate, the light collector, the brightness enhancement film, etc.
- These optical layers can be combined to form a laminate of two layers or three or more layers.
- two or more optical layers such as a light diffusion layer, a phase difference plate, a light collecting plate, and a brightness enhancement film may be arranged. There is no particular limitation on the arrangement of each optical layer.
- the various optical layers forming the optical member are integrated with the polarizing plate using an adhesive, but the adhesive used for this purpose is not particularly limited as long as the adhesive layer is satisfactorily formed. It is preferable to use a pressure-sensitive adhesive (also referred to as a pressure-sensitive adhesive) from the viewpoint of easy bonding work and prevention of optical distortion.
- a pressure-sensitive adhesive also referred to as a pressure-sensitive adhesive
- an acrylic polymer, a silicone polymer, polyester, polyurethane, polyether or the like as a base polymer can be used. Above all, like acrylic adhesives, it has excellent optical transparency, retains appropriate wettability and cohesion, has excellent adhesion to substrates, and has weather resistance and heat resistance.
- alkyl esters of (meth) acrylic acid having an alkyl group having 20 or less carbon atoms such as methyl group, ethyl group and butyl group, (meth) acrylic acid, hydroxyethyl (meth) acrylate, etc.
- the coalescence is useful as a base polymer.
- the pressure-sensitive adhesive layer is formed on the polarizing plate by, for example, dissolving or dispersing the pressure-sensitive adhesive composition in an organic solvent such as toluene or ethyl acetate to prepare a liquid having a solid content concentration of 10 to 40% by weight.
- an organic solvent such as toluene or ethyl acetate
- the thickness of the pressure-sensitive adhesive layer is determined according to the adhesive force and the like, but a range of about 1 to 50 ⁇ m is appropriate.
- the adhesive layer is blended with fillers made of glass fibers, glass beads, resin beads, metal powders and other inorganic powders, pigments, colorants, antioxidants, UV absorbers, etc., as necessary. May be.
- ultraviolet absorbers include salicylic acid ester compounds, benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, and nickel complex compounds.
- the above optical members can be arranged on one side or both sides of the liquid crystal cell to form a liquid crystal display device.
- the liquid crystal cell to be used is arbitrary.
- a liquid crystal display device using various liquid crystal cells such as an active matrix drive type typified by a thin film transistor type and a simple matrix drive type typified by a super twisted nematic type. Can be formed.
- the optical members provided on both sides of the liquid crystal cell may be the same or different.
- each component used for the preparation of the photocurable adhesive composition is as follows.
- the compound name or each symbol (trade name itself or a part thereof) is displayed.
- Epoxy compound CEL-2021 An alicyclic epoxy compound represented by the above formula (4), “Celoxide 2021P” manufactured by Daicel Chemical Industries, Ltd.
- Component (B) ′ (meth) acrylate compound M-7100 other than component (B) : An acrylate mixture mainly composed of tri- or higher functional polyester acrylate, “Aronix M-7100” manufactured by Toagosei Co., Ltd. V # 1000: Dendrimer type polyester acrylate, “Biscoat # 1000” manufactured by Osaka Organic Chemical Industry Co., Ltd.
- CPI-100P Propylene carbonate solution containing 50% active ingredient mainly composed of triarylsulfonium hexafluorophosphate, “CPI-100P” manufactured by San Apro Co., Ltd. In the table, the number of parts of active ingredient is described.
- CPI-110P Triarylsulfonium hexafluorophosphate (active ingredient 100%), “CPI-110P” manufactured by San Apro Co., Ltd. Corresponds to the active ingredient in CPI-100P.
- BR-83 PMMA polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 40,000, acid value 2 mgKOH / g, “Dianal BR-83” manufactured by Mitsubishi Rayon Co., Ltd.
- BR-87 PMMA polymer containing 60% by weight or more of methyl methacrylate as a constituent monomer unit, Mw 25,000, acid value 10.5 mgKOH / g, “Dianal BR-87” manufactured by Mitsubishi Rayon Co., Ltd. LA2140: Mw 80,000, acid value 0 mgKOH / g.
- OXT-212 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, “Aron oxetane OXT-212” manufactured by Toagosei Co., Ltd.
- PC Propylene carbonate (solvent brought in from the CPI-100P)
- reaction liquid corresponding to the amount of the monomer mixture supplied was continuously withdrawn from the outlet.
- the reaction temperature decreased, a temperature increase due to the heat of polymerization was observed, but the internal temperature of the reactor was maintained at 183 to 185 ° C. by controlling the oil jacket temperature.
- the time point after 36 minutes from the stabilization of the reactor internal temperature was taken as the starting point for collecting the reaction liquid, and the reaction was continued for 25 minutes.
- 1.2 kg of the monomer mixture was supplied, The reaction solution was collected. Thereafter, the reaction solution was introduced into a thin film evaporator to separate volatile components such as unreacted monomers, and volatile components such as unreacted monomers were removed to obtain a polymer “polymer A”.
- the polystyrene-equivalent number average molecular weight (Mn) was 2,500
- the weight average molecular weight (Mw) was 7,500
- the viscosity at 25 ° C. was 20,000 mPa ⁇ s.
- Stretched norbornene-based resin film thickness 70 ⁇ m, trade name “ZEONOR film”, manufactured by Nippon Zeon Co., Ltd.
- the film was subjected to corona discharge treatment and then subjected to bonding with a polarizer.
- Acrylic resin film thickness 80 ⁇ m, trade name “Technoloy S001”, manufactured by Sumitomo Chemical Co., Ltd. This film was also subjected to corona discharge treatment and then subjected to bonding with a polarizer.
- the composition prepared above was applied to the corona discharge treated surface of the stretched norbornene-based resin film and the corona discharge treated surface of the acrylic resin film to a thickness of 3 ⁇ m with a bar coater. Next, between these two films, a polarizer in which iodine was adsorbed and oriented in polyvinyl alcohol was sandwiched, and the three films were simultaneously bonded with a roller. In this way, the polarizer with the protective film bonded on both sides is subjected to an ultraviolet irradiation device with a belt conveyor (the lamp uses a high-pressure mercury lamp manufactured by iGraphics Co., Ltd.), and the integrated light quantity is 250 mJ / cm from the surface of the stretched norbornene resin film. 2 (UV-B) was irradiated with ultraviolet rays to cure the adhesive composition. This experiment was performed under conditions of 23 ° C. and 50% relative humidity.
- the adhesive strength was determined according to the following four levels from the appearance and force when peeled by hand.
- ⁇ Not strong enough to break the material, but not weak enough to peel off with a little force.
- X Very weak enough to peel off with a little force.
- ⁇ Cooling cycle test> A thermal shock cycle test was repeated 300 times for a polarizing plate that had passed two days or more after irradiation with ultraviolet rays and placed at ⁇ 35 ° C. for 60 minutes and then at + 70 ° C. for 60 minutes. The polarizing plate after the cooling and heating cycle test was visually observed and judged according to the following three levels. ⁇ : No appearance defect was observed. ⁇ : Slightly poor appearance was observed. X: Appearance defect was recognized.
- ⁇ Moisture and heat resistance test> A polarizing plate that had passed two days or more after UV irradiation was cut into a width of 1 cm and a length of 6 cm, and placed in a high-temperature and high-humidity environment at 60 ° C. and a relative humidity of 90% for 500 hours. About the polarizing plate after a wet heat test, peeling and discoloration were observed visually and it determined by the following three levels. ⁇ : No peeling or discoloration was observed. ⁇ : Slight peeling or discoloration was observed. X: Peeling or discoloration was observed.
- Examples 1 to 9 will be described.
- the compositions of Examples 1 to 9, which are the adhesive compositions of the present invention, were used for the adhesion after 15 hours after the completion of the viscosity, the adhesion development rate, the final adhesion, the cold cycle test, the moist heat test and the moist heat test. Not only was it excellent in strength, but it also had good adhesion after 5 minutes after removal from the heat and humidity test. For this reason, not only the basic performance as an adhesive for polarizing plates was excellent, but also the reliability immediately after being transported in a high-temperature and high-humidity environment was improved.
- Comparative Example 1 When the acrylic resin was bent and peeled after the end of the moist heat test, the compositions of Examples 7 to 9 were broken immediately and could not be peeled off. That is, the adhesive force immediately after the end of the wet heat resistance test was further improved. Furthermore, the composition of Example 9 using the polymer A had a viscosity at 25 ° C. of 50 mPa ⁇ s or less, and was excellent in coatability.
- Comparative Example 1 will be described.
- the composition of Comparative Example 1 containing no component (E) is excellent in viscosity, adhesive force expression rate, final adhesive force, cooling / heating cycle test, and moist heat test, and the adhesive force 15 hours after the end of the moist heat test. However, the adhesive strength after 5 minutes after the end of the moist heat test was greatly reduced.
- the photocurable adhesive composition of the present invention has a low viscosity and is easy to be applied in a thin film, is excellent in the adhesive force expression speed and final adhesive force between the polarizer and the protective film after light irradiation, and immediately after the end of the wet heat resistance test. Since it is excellent also in adhesive force and it is excellent also in the durability of the polarizing plate obtained, it can be used conveniently for manufacture of a polarizing plate.
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Abstract
Description
当該接着剤組成物は、接着力と耐久性のみならず、生産性にも優れた偏光板用光硬化性接着剤であった。
この接着力低下は、通常環境で15時間放置すると、保護フィルムが材料破壊するほど剥離接着力が回復する。又、耐湿熱試験終了直後であっても、偏光板をガラスに貼り付けた製品形態で加わる力(せん断方向又は垂直方向の力)によっては、保護フィルムの剥離は起こらない。しかし、偏光板輸送中に高温高湿環境に曝された後、すぐに加工工程に入るという最悪のケースを想定すると、耐湿熱試験終了直後の剥離強度も向上させることが望まれる。
(A)分子内に少なくとも2個の下記式(1)に示す脂環式エポキシ基を有するエポキシ化合物、
(C)光カチオン重合開始剤、
(D)下記式(2)に示すオキセタン化合物及び
前記(A)~(E)成分の含有割合が、組成物中に、
(A)成分:10~65重量%
(B)成分:10~55重量%
(C)成分:0.5~10重量%
(D)成分:1~25重量%
(E)成分:0.1~25重量%
であることを特徴とする。
本発明の組成物は、(A)成分として、下記式(4)に示すエポキシ化合物が好ましい。
当該重合体としては、構成単量体単位としてメチルメタクリレートを60重量%以上含み、重量平均分子量が1,000~200,000である重合体〔以下、「(E1)成分」ともいう〕、構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、重量平均分子量が1,000~200,000である重合体〔以下、「(E2)成分」ともいう〕が好ましい。
(E2)成分としては、さらに、高温重合で得られた重合体であって、構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、重量平均分子量が1,000~20,000である重合体が好ましい。
(G)成分としては、アシルフォスフィンオキサイド化合物が、接着力に優れる点で好ましい。
本発明では、偏光子と保護膜とを貼合するのに、特定組成の光硬化性接着剤組成物を用いる。以下、この光硬化性接着剤組成物を、単に「光硬化性接着剤」又は「組成物」と呼ぶこともある。本発明の光硬化性接着剤は、以下の(A)、(B)、(C)、(D)及び(E)の5成分を必須に含有するものである。
(B)炭素数2~15個を有するポリオールのポリ(メタ)アクリレート
(C)光カチオン重合開始剤
(D)後記式(2)に示すオキセタン化合物
(E)アルキル(メタ)アクリレートを必須構成単量体単位とする重合体
本発明の光硬化性接着剤において、(A)成分となるエポキシ化合物は、分子内に少なくとも2個の下記式(1)に示す脂環式エポキシ基を有するエポキシ化合物であり、一般に知られている各種の硬化性エポキシ化合物を用いることができる。尚、式(1)において、波線部分は他の構造との結合位置を表す。
又、(A)成分における式(1)に示す脂環式エポキシ基の数は、低粘度、硬化性、接着力及び耐久性に優れる点で、2~10個であることが好ましく、2~6個であることがより好ましく、2個であることがさらに好ましい。
本発明の光硬化性接着剤において、(B)成分となるポリ(メタ)アクリレートは、炭素数2~15個を有するポリオールのポリ(メタ)アクリレートである。
(B)成分はエステル骨格やイソシアヌレート骨格を有しても良い。エステル骨格を有する化合物の具体例としては、ネオペンチルグリコールとヒドロキシピバリン酸と(メタ)アクリル酸のエステル化反応生成物などが挙げられ、イソシアヌレート骨格を有する化合物の例としては、イソシアヌル酸アルキレンオキサイド付加物のジ又はトリ(メタ)アクリレートなどが挙げられる。
本発明の光硬化性接着剤は、硬化成分として以上説明したエポキシ化合物(A)、オキセタン化合物(D)及び必要に応じて後記するオキセタン化合物を含有し、これらはいずれもカチオン重合により硬化するものであることから、(C)成分として光カチオン重合開始剤が配合される。この光カチオン重合開始剤は、可視光線、紫外線、X線、電子線等の活性エネルギー線の照射によって、カチオン種又はルイス酸を発生し、エポキシ基やオキセタニル基の重合反応を開始する。
ベンゼンジアゾニウム ヘキサフルオロアンチモネート、
ベンゼンジアゾニウム ヘキサフルオロホスフェート、
ベンゼンジアゾニウム ヘキサフルオロボレートなど。
ジフェニルヨードニウム テトラキス(ペンタフルオロフェニル)ボレート、
ジフェニルヨードニウム ヘキサフルオロホスフェート、
ジフェニルヨードニウム ヘキサフルオロアンチモネート、
ジ(4-ノニルフェニル)ヨードニウム ヘキサフルオロホスフェートなど。
トリフェニルスルホニウム ヘキサフルオロホスフェート、
トリフェニルスルホニウム ヘキサフルオロアンチモネート、
トリフェニルスルホニウム テトラキス(ペンタフルオロフェニル)ボレート、
4,4’-ビス(ジフェニルスルホニオ)ジフェニルスルフィド ビスヘキサフルオロホスフェート、
4,4’-ビス〔ジ(β-ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロアンチモネート、
4,4’-ビス〔ジ(β-ヒドロキシエトキシ)フェニルスルホニオ〕ジフェニルスルフィド ビスヘキサフルオロホスフェート、
7-〔ジ(p-トルイル)スルホニオ〕-2-イソプロピルチオキサントン ヘキサフルオロアンチモネート、
7-〔ジ(p-トルイル)スルホニオ〕-2-イソプロピルチオキサントン テトラキス(ペンタフルオロフェニル)ボレート、
4-フェニルカルボニル-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロホスフェート、
4-(p-tert-ブチルフェニルカルボニル)-4’-ジフェニルスルホニオ-ジフェニルスルフィド ヘキサフルオロアンチモネート、
4-(p-tert-ブチルフェニルカルボニル)-4’-ジ(p-トルイル)スルホニオ-ジフェニルスルフィド テトラキス(ペンタフルオロフェニル)ボレートなど。
キシレン-シクロペンタジエニル鉄(II)ヘキサフルオロアンチモネート、
クメン-シクロペンタジエニル鉄(II)ヘキサフルオロホスフェート、
キシレン-シクロペンタジエニル鉄(II)-トリス(トリフルオロメチルスルホニル)メタナイドなど。
本発明の光硬化性接着剤において、(D)成分として下記式(2)に示すオキセタン化合物を配合する。(D)成分を含むことにより、光照射後の接着力発現速度を向上させることができる。又、塗工環境の相対湿度が約45%のときの最終的な接着力を向上させることができる。さらに、変動しうる塗工環境の相対湿度において、(D)成分を含むことにより、塗工環境の相対湿度が多少変動しても接着力を発現させることができる。
本発明の光硬化性接着剤において、(E)成分を含むことにより、耐湿熱試験終了直後の接着力を良好にすることができる。尚、本発明において、「アルキル(メタ)アクリレートを必須構成単量体単位とする」重合体とは、「アルキル(メタ)アクリレート由来の構成単量体単位を少なくとも有する」重合体と同義である。
これら化合物の中でも、炭素数1~10のアルキル基を含むアルキル(メタ)アクリレートが好ましく、炭素数1~4の低級アルキル基を有するアルキル(メタ)アクリレートがより好ましい。
その他単量体の具体例としては、(メタ)アクリル酸等のカルボキシル基含有単量体;アクリルアミド2-メチルプロパンスルホン酸及びスチレンスルホン酸等のスルホン酸基含有単量体;リン酸基含有単量体;(メタ)アクリロニトリル等のシアノ基含有単量体、ビニルエステル;スチレン及びα-メチルスチレン等の芳香族ビニル化合物;酸無水物基含有単量体;ヒドロキシエチル(メタ)アクリレート、ヒドロキシエチル(メタ)アクリレート及びヒドロキシブチル(メタ)アクリレート等のヒドロキシアルキル(メタ)アクリレート等のヒドロキシル基含有単量体;アクリルアミド、ジメチルアクリルアミド、ジエチルアクリルアミド等のアミド基含有単量体;アミノ基含有単量体;イミド基含有単量体;グリシジル(メタ)アクリレート等のエポキシ基含有単量体;(メタ)アクリロイルモルホリン;並びにビニルエーテル等が挙げられる。
接着性に加え、組成物との溶解性を改善する目的では、アルキル(メタ)アクリレートと酸性基含有単量体の共重合体が好ましい。
酸性基含有単量体としては、カルボキシル基含有単量体、スルホン基含有単量体、酸無水物基含有単量体及びリン酸基含有単量体等が挙げられ、カルボキシル基含有単量体が好ましい。
当該共重合体としては、組成物の保存安定性を良好にするという理由で酸価が20mgKOH/g以下の共重合体が好ましく、より好ましくは15mgKOH/g以下である。
尚、本発明において、Mwとは、ゲルパーミエーションクロマトグラフィー(以下、「GPC」ともいう)により測定した分子量をポリスチレン換算したものを意味する。
当該重合体のより好ましい例としては、例えば、下記2種の重合体を挙げることができる。
・(E1)成分:構成単量体単位としてメチルメタクリレートを60重量%以上含み、Mwが1,000~200,000である重合体
・(E2)成分:構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、Mwが1,000~200,000である重合体
(E1)成分は、酸性基含有単量体との共重合体でも良く、酸性基含有単量体としては、前記と同様の単量体が挙げられ、カルボキシル基含有単量体が好ましい。
当該共重合体としては、前記と同様の理由で、酸価が20mgKOH/g以下の共重合体が好ましく、より好ましくは15mgKOH/g以下である。
(E1)成分は市販されており、例えば、三菱レイヨン(株)製のダイヤナールBR-80(構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw95,000、酸価0mgKOH/gのPMMA系ポリマー)、同BR-83(構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw40,000、酸価2mgKOH/gのPMMA系ポリマー)及び同BR-87(構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw25,000、酸価10.5mgKOH/gのPMMA系ポリマー)等が挙げられる。
炭素数1~10のアルキル基を含むアルキルアクリレートとしては、前記と同様の化合物が挙げられる。
(E2)成分としては、炭素数1~10のアルキル基を含むアルキルアクリレートを構成単量体単位として60重量%以上含めば、アルキルメタクリレートやその他単量体との共重合体であっても良い。
(E2-1)成分における単量体の好ましい組み合わせとしては、ポリアクリレートブロック単位とポリメタクリレートブロック単位を有するブロックポリマー、及びポリアクリレートブロック単位とその他単量体のポリマーのブロック単位を有するブロックポリマー等を挙げることができる。
これらの中でも、ポリアクリレート系ブロック単位とポリメタクリレート系ブロック単位を有するブロックポリマー、さらに、ポリブチルアクリレートとポリメチルメタクリレートをブロック単位として含むブロックポリマーが好ましい。
当該低分子量重合体を通常の重合方法で製造しようとすると、通常、連鎖移動剤や重合開始剤を多くする必要がある。連鎖移動剤を多量に使用した重合体を使用すると、組成物のカチオン硬化性や接着力が低下し易くなり、又、重合開始剤を多量に使用した重合体を使用すると、組成物の保存安定性が低下し易くなる。
このため、多量の連鎖移動剤や重合開始剤を必要としない高温重合により製造された重合体であって、構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、Mwが1,000~20,000である重合体〔以下、「(E2-2)成分」という〕が好ましい。
尚、本発明において、Mwとは、GPCにより測定した分子量をポリスチレン換算したものを意味する。
高温重合の中でも、高温連続重合は、生産性優れるだけでなく、共重合体製品中の組成分布が出来難いため、相溶性に優れる等の長所を有する。
高温連続重合は、公知の方法で実施することができる(例えば、特表昭57-502171号公報、特開昭59-6207号公報及び特開昭60-215007号公報等)。
具体的には、加圧可能な反応器を溶媒で満たし、加圧下で所定温度に設定した後、単量体、又は必要に応じて重合溶媒、重合開始剤とからなる単量体混合物を一定の供給速度で反応器へ供給し、単量体混合物の供給量に見合う量の反応液を抜き出す方法が挙げられる。
(E2-2)成分のガラス転移温度としては、20℃以下が好ましく、より好ましくは-90~0℃である。
尚、本発明において、ガラス転移温度とは、示差走査熱量計(DSC)を用いて、2℃/分の昇温速度で測定した値を意味する。
(E)成分の好ましい組み合わせとしては、異なる種類の基材との接着性に優れたものとなる点で、(E1)成分と(E2)成分を組み合わせて使用することが好ましく、より好ましくは、(E1)成分と(E2-2)成分を組み合わせて使用することが好ましい。
(E1)成分と(E2)成分の併用割合としては、1/9~7/3が好ましい。
本発明の光硬化性接着剤において、(F)成分として下記式(3)に示すオキセタン化合物を配合することができる。(F)成分を含むことにより、光照射後の接着力発現速度や最終的な接着力をさらに向上させることができる。
本発明の光硬化性接着剤に含まれる(B)成分等のラジカル硬化性成分は、(C)成分が光で分解する際に発生するラジカルで硬化させることが可能であるが、少ない照射量で十分な反応率を得るために、(G)成分として光ラジカル重合開始剤を配合することが好ましい。(G)成分の配合割合は、組成物全体を基準として10重量%以下であることが好ましく、より好ましくは0.1~3重量%である。配合量が10重量%以上であると、耐久性の低下を引き起こすことがあるため好ましくない。
ベンゾイン、ベンゾインメチルエーテル、ベンゾインエチルエーテル、ベンゾインイソプロピルエーテル、及びベンゾインイソブチルエーテルの如き、ベンゾインエーテル系光重合開始剤;
ベンゾフェノン、o-ベンゾイル安息香酸メチル、4-フェニルベンゾフェノン、4-ベンゾイル-4’-メチルジフェニルサルファイド、及び2,4,6-トリメチルベンゾフェノンの如き、ベンゾフェノン系光重合開始剤;
2-イソプロピルチオキサントン、2,4-ジエチルチオキサントン、2,4-ジクロロチオキサントン、及び1-クロロ-4-プロポキシチオキサントンの如き、チオキサントン系光重合開始剤;
2,4,6-トリメチルベンゾイルジフェニルフォスフィンオキサイド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルフォスフィンオキサイド、及びビス(2,4,6-トリメチルベンゾイル)フェニルフォスフィンオキサイドの如き、アシルフォスフィンオキサイド系光重合開始剤;
1,2-オクタンジオン,1-〔4-(フェニルチオフェニル)〕-,2-(O-ベンゾイルオキシム)の如き、オキシム・エステル系光重合開始剤;
カンファーキノンなど。
(G)成分の光ラジカル重合開始剤を配合する場合、その含有割合は、組成物全体を基準として、好ましくは10重量%以下、より好ましくは0.1~3重量%である。光ラジカル重合開始剤(G)の含有割合が上記範囲であると、十分な強度が得られ、又、硬化性に優れる。
(G)成分としては、アシルフォスフィンオキサイド系化合物が、接着力に優れる点で好ましい。
本発明の光硬化性接着剤において、平滑性に優れた塗布面を得る目的で、(H)成分のレベリング剤を含有することが好ましい。
(H)成分としては、シリコーン系レベリング剤及び、フッ素系レベリング剤等が挙げられ、市販されている各種レベリング剤を使用することができる。これらのうち、(メタ)アクリロイル基を有するシリコーン系レベリング剤は、耐湿熱試験終了直後の接着力が優れる点で、特に好ましい。
本発明の光硬化性接着剤は、上述した(A)~(H)成分の他に、その他のカチオン硬化性成分やラジカル硬化性成分を含有していてもよい。
多官能(メタ)アクリレートの配合割合としては、組成物中に2~20重量%が好ましい。
さらに、本発明の光硬化性接着剤には、本発明の効果を損なわない範囲で、硬化性を有さないその他の成分を任意に配合することができ、具体的には、光増感剤、熱カチオン重合開始剤、ポリオール化合物、水などが挙げられる。
以上説明した光硬化性接着剤は、一軸延伸され、二色性色素が吸着配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に保護膜を接着するために用いられ、こうして偏光子に保護膜が貼合されて偏光板となる。すなわち本発明に係る偏光板は、一軸延伸され、二色性色素が吸着配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に、保護膜を貼合したものである。保護膜は、偏光子の片面にだけ貼合してもよいし、偏光子の両面に貼合してもよい。偏光子の両面に保護膜を貼合する場合、それぞれの保護膜は、同じ種類の樹脂からなるものであってもよいし、異なる種類の樹脂からなるものであってもよい。
偏光子を構成するポリビニルアルコール系樹脂は、ポリ酢酸ビニル系樹脂をケン化することにより得られる。ポリ酢酸ビニル系樹脂として、酢酸ビニルの単独重合体であるポリ酢酸ビニルの他、酢酸ビニル及びこれと共重合可能な他のモノマーの共重合体などが例示される。酢酸ビニルに共重合される他のモノマーとしては、例えば、不飽和カルボン酸類、オレフィン類、ビニルエーテル類、不飽和スルホン酸類などが挙げられる。ポリビニルアルコール系樹脂のケン化度は、好ましくは85~100モル%、より好ましくは98~100モル%の範囲である。このポリビニルアルコール系樹脂は、さらに変性されていてもよく、例えば、アルデヒド類で変性されたポリビニルホルマールやポリビニルアセタールなども使用しうる。ポリビニルアルコール系樹脂の重合度は、好ましくは1,000~10,000、より好ましくは1,500~10,000の範囲である。
次いで、この偏光子は、先に説明した光硬化性接着剤を用いて、その片面又は両面に保護膜が貼合される。偏光子の保護膜として従来から広く採用されているトリアセチルセルロースフィルムは、概ね400g/m2/24hr程度の透湿度を有するが、本発明では、偏光子の少なくとも一方の面に貼合される保護膜として、かかるトリアセチルセルロースよりも低い透湿度を示す樹脂であって、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂又は非晶性ポリオレフィン系樹脂が採用される。
本発明の偏光板は、先に説明した偏光子と、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂及び非晶性ポリオレフィン系樹脂から選ばれる透明樹脂フィルムからなる保護膜との貼合面のうち少なくとも一方に、先に説明した光硬化性接着剤を塗布する接着剤塗布工程と、得られる接着剤層を介して偏光子と保護膜とを貼合する貼合工程と、この接着剤層を介して偏光子と保護膜とが貼合された状態で光硬化性接着剤を硬化させる硬化工程とを包含する方法によって製造することができる。
接着剤塗布工程では、偏光子と保護膜との貼合面のうち少なくとも一方に、先に説明した光硬化性接着剤が塗布される。偏光子又は保護膜の表面に直接光硬化性接着剤を塗布する場合、その塗布方法に特別な限定はない。例えば、ドクターブレード、ワイヤーバー、ダイコーター、カンマコーター、グラビアコーターなど、種々の塗工方式が利用できる。又、偏光子と保護膜の間に先に説明した光硬化性接着剤を流延させたのち、ロール等で加圧して均一に押し広げる方法も利用できる。
接着剤塗布工程の雰囲気温度は、15~30℃であることが好ましく、20~25℃であることが特に好ましい。又、塗布雰囲気の相対湿度は、80%以下であることが好ましく、より好ましくは70%以下、さらに好ましくは30~70%、特に好ましくは40~60%である。接着剤塗布工程の雰囲気温度と湿度を上記範囲に調節することにより、接着力発現速度や最終的な接着力を安定的に良好にすることができる。
尚、雰囲気温度とは別に、塗布する際の接着剤の温度は、低粘度化による塗工性改善や後記する接着力向上の目的で、加温又は加熱しておいても良い。この際の加温又は加熱温度は、80℃以下が好ましく、20~60℃の範囲がより好ましい。但し、フィルムに塗布されてから貼合工程に入るまでの間に、接着剤塗膜が、15~30℃、湿度80%以下の雰囲気に曝されることが、接着力発現速度や最終的な接着力を良好にする点で好ましい。
こうして光硬化性接着剤を塗布した後は、貼合工程に供される。この貼合工程では、例えば、先の塗布工程で偏光子の表面に光硬化性接着剤を塗布した場合は、そこに保護膜が重ね合わされ、先の塗布工程で保護膜の表面に光硬化性接着剤を塗布した場合は、そこに偏光子が重ね合わされる。又、偏光子と保護膜の間に光硬化性接着剤を流延させた場合は、その状態で偏光子と保護膜が重ね合わされる。偏光子の両面に保護膜を貼合する場合であって、両面とも本発明の光硬化性接着剤を用いる場合は、偏光子の両面にそれぞれ、光硬化性接着剤を介して保護膜が重ね合わされる。そして通常は、この状態で両面(偏光子の片面に保護膜を重ね合わせた場合は、偏光子側と保護膜側、又偏光子の両面に保護膜を重ね合わせた場合は、その両面の保護膜側)からロール等で挟んで加圧することになる。ここでロールの材質は、金属やゴム等を用いることが可能である。両面に配置されるロールは、同じ材質であってもよいし、異なる材質であってもよい。
以上のように、未硬化の光硬化性接着剤を介して偏光子と保護膜が貼合された状態のものは、次いで硬化工程に供される。この硬化工程では、光硬化性接着剤に活性エネルギー線を照射して、エポキシ化合物、(メタ)アクリレート及びオキセタン化合物等を含む接着剤層を硬化させ、偏光子と保護膜とを接着させる。偏光子の片面に保護膜を貼合した場合、活性エネルギー線は、偏光子側、保護膜側のどちらから照射してもよい。又、偏光子の両面に保護膜を貼合する場合は、偏光子の両面にそれぞれ光硬化性接着剤を介して保護膜を貼合した状態で、どちらか一方の保護膜側から活性エネルギー線を照射し、両面の光硬化性接着剤を同時に硬化させるのが有利である。ただし、どちらか一方の保護膜に紫外線吸収剤が配合されている場合(例えば、紫外線吸収剤が配合されたセルロース系樹脂フィルムを一方の保護膜とする場合)であって、活性エネルギー線が紫外線である場合は、通常、他方の紫外線吸収剤が配合されていない保護膜側から紫外線が照射される。
又、本発明の接着剤と保護フィルムの接着力を向上させる他の好ましい方法としては、加熱せずとも、すなわち20~25℃においても、偏光子と保護フィルムを貼合してから活性エネルギー線照射されるまでの製造ラインの長さを長くして、接着剤とアクリル樹脂が接してからの時間を60秒程度と長くする方法も挙げられる。
偏光板の使用に際しては、その一方の側に、偏光機能以外の光学機能を示す光学層を積層した光学部材とすることもできる。光学部材の形成を目的に偏光板に積層する光学層には、例えば、反射層、半透過型反射層、光拡散層、位相差板、集光板、輝度向上フィルムなど、液晶表示装置等の形成に用いられる各種のものがある。前記の反射層、半透過型反射層及び光拡散層は、反射型ないし半透過型や拡散型、それらの両用型の偏光板からなる光学部材を形成する場合に用いられるものである。
以上のような光学部材は、液晶セルの片側又は両側に配置して、液晶表示装置とすることができる。用いる液晶セルは任意であり、例えば、薄膜トランジスタ型に代表されるアクティブマトリクス駆動型のもの、スーパーツイステッドネマチック型に代表される単純マトリクス駆動型のものなど、種々の液晶セルを使用して液晶表示装置を形成することができる。液晶セルの両側に設ける光学部材は、同じものであってもよいし、異なるものであってもよい。
CEL-2021:前記式(4)に示す脂環式エポキシ化合物、ダイセル化学工業(株)製の“セロキサイド2021P”。
HDDA:1,6-ヘキサンジオールジアクリレート、共栄社化学(株)製の“ライトアクリレート1,6HX-A”。
M-7100:3官能以上のポリエステルアクリレートを主成分とするアクリレート混合物、東亞合成(株)製の“アロニックスM-7100”。
V#1000:デンドリマー型ポリエステルアクリレート、大阪有機化学工業(株)製の“ビスコート#1000”。
CPI-100P:トリアリールスルホニウムヘキサフルオロホスフェートを主成分とする有効成分50%のプロピレンカーボネート溶液、サンアプロ(株)製の“CPI-100P”。表中には有効成分の部数を記載。
CPI-110P:トリアリールスルホニウムヘキサフルオロホスフェート(有効成分100%)、サンアプロ(株)製の“CPI-110P”。CPI-100P中の有効成分に相当。
OXT-101:3-エチル-3-ヒドロキシメチルオキセタン、東亞合成(株)製の“アロンオキセタンOXT-101”。
BR-80:構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw95,000、酸価0mgKOH/gのPMMA系ポリマー、三菱レイヨン(株)製の“ダイヤナールBR-80”。
BR-83:構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw40,000、酸価2mgKOH/gのPMMA系ポリマー、三菱レイヨン(株)製の“ダイヤナールBR-83”。
BR-87:構成単量体単位としてメチルメタクリレート60重量%以上含有、Mw25,000、酸価10.5mgKOH/gのPMMA系ポリマー、三菱レイヨン(株)製の“ダイヤナールBR-87”。
LA2140:Mw80,000、酸価0mgKOH/g。メチルメタクリレートとブチルアクリレートのブロック共重合体、構成単量体単位としてブチルアクリレート60重量%以上含有、両末端PMMA。(株)クラレ製の“クラリティLA2140e”。
LA1114:Mw80,000、酸価0mgKOH/g。メチルメタクリレートとブチルアクリレートのブロック共重合体、構成単量体単位としてブチルアクリレート60重量%以上含有、片末端PMMA。(株)クラレ製の“クラリティLA1114”。
ポリマーA:後述する製造例1で得られるポリマー。
OXT-221:3-エチル-3-〔(3-エチルオキセタン-3-イル)メトキシメチル〕オキセタン、東亞合成(株)製の“アロンオキセタンOXT-221”。
Irg-184:1-ヒドロキシ-シクロヘキシル-フェニル-ケトン、BASF社製の“イルガキュア184”。
Irg-819:ビス(2,4,6-トリメチルベンゾイル)-フェニルフォスフィンオキサイド、BASF社製の“イルガキュア819”。
BYK-UV3500:ビックケミー(株)製の分子内にアクリロイル基を有するシリコーン系レベリング剤“BYK-UV3500”。
SH-28:東レ・ダウコーニング(株)製の分子内にアクリロイル基を有さないシリコーン系レベリング剤“DOW CORNING TORAY SH 28 PAINT ADDITIVE”。
OXT-212:3-エチル-3-(2-エチルヘキシルオキシメチル)オキセタン、東亞合成(株)製の“アロンオキセタンOXT-212”。
PC:プロピレンカーボネート(上記CPI-100Pから持ち込まれる溶剤)
オイルジャケットを備えた容量1,000mLの加圧式攪拌槽型反応器のジャケット温度を181℃に保った。次いで、反応器の圧力を一定に保ちながら、ブチルアクリレート(45部)、2-エチルヘキシルアクリレート(45部)、メチルメタクリレート(10部)、重合溶媒として、イソプロピルアルコール(9部)、メチルエチルケトン(9部)、重合開始剤としてジt-ブチルパーオキサイド(0.25部)からなる単量体混合物を、一定の供給速度(48g/分、滞留時間:12分)で原料タンクから反応器に連続供給を開始し、単量体混合物の供給量に相当する反応液を出口から連続的に抜き出した。反応開始直後に、一旦反応温度が低下した後、重合熱による温度上昇が認められたが、オイルジャケット温度を制御することにより、反応器の内温を183~185℃に保持した。反応器内温が安定してから36分後の時点を、反応液の採取開始点とし、これから25分間反応を継続した結果、1.2kgの単量体混合液を供給し、1.2kgの反応液を回収した。その後反応液を薄膜蒸発器に導入して、未反応モノマー等の揮発成分を分離して、未反応モノマー等の揮発成分を除去し、重合体「ポリマーA」を得た。GPCを測定した結果、ポリスチレン換算の数平均分子量(Mn)が2,500、重量平均分子量(Mw)が7,500であり、25℃における粘度が、20,000mPa・sであった。
表1及び表2に示す各成分をそれぞれの割合で配合し、常法に従って攪拌混合して、光硬化性接着剤組成物を調製した。尚、前記したとおり、(C)成分として用いた“CPI-100P”は有効成分を50%含有するプロピレンカーボネート溶液であるため、表中では、(C)成分とプロピレンカーボネートを分けて表示した。すなわち、表中の“CPI-100P”の配合量は、有効成分の割合を意味し、“CPI-100P”それ自体の配合量は、(C)成分の欄に示す量とプロピレンカーボネートの欄に示す量を合わせた量である。
得られた組成物の25℃における粘度は、東機産業(株)製のE型粘度計により測定した。
ここでは、保護膜として次の2種類のフィルムを用いた。
延伸ノルボルネン系樹脂フィルム:厚さ70μm、商品名“ZEONORフィルム”、日本ゼオン(株)製。このフィルムにコロナ放電処理を施してから、偏光子との貼合に供した。
アクリル樹脂フィルム:厚さ80μm、商品名“テクノロイS001”、住友化学(株)製。このフィルムも、コロナ放電処理を施してから、偏光子との貼合に供した。
この実験を、23℃、相対湿度50%の条件下で実施した。
紫外線照射後の偏光板について、以下の方法で、接着力発現速度、最終接着力、冷熱サイクル試験、耐湿熱試験、及び耐湿熱試験後の接着力を評価し、結果を表1及び表2にまとめた。
紫外線照射してから3分後に、アクリル樹脂フィルムと偏光子の間を手で剥離し、その時の接着力が強いものほど、接着力発現速度に優れると評価した。接着力は、手で剥離した際の様子及び力から、以下の4水準で判定した。
◎:アクリル樹脂フィルムが材料破壊。
○:ゆっくりと注意して剥離すれば材料破壊しないが強い接着力。
△:材料破壊する強度はないが、少しの力で剥離してしまうほどの弱さでもない。
×:少しの力で剥離してしまうほど非常に弱い。
紫外線照射してから1日後に、カッターナイフの刃を、アクリル樹脂フィルムの上から斜めに挿入し、その時の様子及び力から、以下の4水準で判定した。
◎:刃が入らないか、入った場合でも強度があり、アクリル樹脂フィルムが破れた。
○:刃が入ったが抵抗力があり、アクリル樹脂フィルムが界面でスライスされた。
△:刃が入るが、界面において刃が少しの力で進行するほどの弱さでもない。
×:刃が入り、界面において刃が少しの力で進行するほど弱い。
紫外線照射してから2日以上経過した偏光板に対して、-35℃に60分置き、次に+70℃に60分置くサイクルを300回繰り返す冷熱衝撃サイクル試験を実施した。冷熱サイクル試験後の偏光板を目視で観察し、以下の3水準で判定した。
○:外観不良が認められなかった。
△:外観不良が僅かに認められた。
×:外観不良が認められた。
紫外線照射してから2日以上経過した偏光板を、幅1cm、長さ6cmに切り出し、60℃、相対湿度90%の高温高湿環境下に500時間置いた。耐湿熱試験後の偏光板について、剥離や変色を目視で観察し、以下の3水準で判定した。
○:剥離や変色が見られなかった。
△:剥離や変色が僅かに認められた。
×:剥離や変色が認められた。
耐湿熱試験終了後、速やかに、23℃、相対湿度50%の環境に移し、高温高湿環境から取出して5分後の接着性を、偏光板の角を弾くことにより評価した。このとき、アクリル樹脂を内側にして角5mmを手で90°曲げた後、手を瞬間的に離し、剥離するか否かを10回以上評価し、以下の3水準で判定した。
○:10回以上で剥離が見られなかった。
△:平均して3回~9回の間に剥離が見られた。
×:2回以下で剥離が見られた。
耐湿熱試験終了後、速やかに、23℃、相対湿度50%の環境に移し、アクリル樹脂を上にして偏光板をガラス板に貼り付け、高温高湿環境から取り出して5分後及び15時間後に、引張速度60mm/分でアクリル樹脂を180°剥離して接着力を測定した。その時の強度及びアクリル樹脂材料破壊の様子から、下記の4水準で判定した。
◎:6N/cm以上又は剥離不能
○:3N/cm以上又は剥離途中でアクリル樹脂が材料破壊
△:0.1N/cm以上3N/cm未満
×:0.1N/cm未満
まず、実施例1~実施例9について説明する。
本発明の接着剤組成物である実施例1~実施例9の組成物は、粘度、接着力発現速度、最終接着力、冷熱サイクル試験、耐湿熱試験及び耐湿熱試験終了後15時間後の接着力に優れるだけでなく、耐湿熱試験終了後、取出し5分後の接着力も良好であった。このため、偏光板用接着剤としての基本的な性能に優れるだけでなく、高温高湿環境下で輸送された直後の信頼性も向上していた。
これらのうち、実施例7~実施例9の組成物は、耐湿熱試験終了後にアクリル樹脂を曲げて剥離しようとすると、アクリル樹脂がすぐに破壊し、剥離不能であった。すなわち、耐湿熱試験終了直後の接着力がより一層向上していた。
さらに、ポリマーAを使用した実施例9の組成物は、25℃における粘度が50mPa・s以下であり、塗工性にも優れていた。
次に、比較例1について説明する。
(E)成分を含まない比較例1の組成物は、粘度、接着力発現速度、最終接着力、冷熱サイクル試験及び耐湿熱試験に優れるものであり、耐湿熱試験終了後15時間後の接着力にも優れるものであったが、耐湿熱試験終了後5分後の接着力が大きく低下してしまった。
Claims (17)
- 一軸延伸され、二色性色素が吸着配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂及び非晶性ポリオレフィン系樹脂からなる群より選ばれる透明樹脂フィルムからなる保護膜を接着するための接着剤組成物であって、
(A)分子内に少なくとも2個の下記式(1)に示す脂環式エポキシ基を有するエポキシ化合物、
(C)光カチオン重合開始剤、
(D)下記式(2)に示すオキセタン化合物及び
を含有し、
前記(A)~(E)成分の含有割合が、組成物中に、
(A)成分:10~65重量%
(B)成分:10~55重量%
(C)成分:0.5~10重量%
(D)成分:1~25重量%
(E)成分:0.1~25重量%
であることを特徴とする光硬化性接着剤組成物。 - (B)成分が、炭素数5~10個を有するジオール(但し、アルキレンオキサイド単位の繰返し数3以上のポリエーテルジオールを除く)のジ(メタ)アクリレートである請求項1又は請求項2に記載の光硬化性接着剤組成物。
- (A)成分及び(B)成分の含有割合が、組成物中にそれぞれ10~50重量%及び20~45重量%である請求項1~請求項3のいずれかに記載の光硬化性接着剤組成物。
- (E)成分が、構成単量体単位として炭素数1~10のアルキル基を含むアルキル(メタ)アクリレートを含み、重量平均分子量が1,000~500,000である重合体を含む請求項1~請求項4のいずれかに記載の光硬化性接着剤組成物。
- (E)成分が、構成単量体単位としてメチルメタクリレートを60重量%以上含み、重量平均分子量が1,000~200,000である重合体を含む請求項5に記載の光硬化性接着剤組成物。
- (E)成分が、構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、重量平均分子量が1,000~200,000である重合体を含む請求項5に記載の光硬化性接着剤組成物。
- (E)成分が、高温重合で得られた重合体であって、構成単量体単位として炭素数1~10のアルキル基を含むアルキルアクリレートを60重量%以上含み、重量平均分子量が1,000~20,000である重合体を含む請求項7に記載の光硬化性接着剤組成物。
- さらに、(G)光ラジカル重合開始剤を組成物中に10重量%以下の割合で含有する請求項1~請求項9のいずれかに記載の光硬化性接着剤組成物。
- (G)成分がアシルフォスフィンオキサイド化合物を含む請求項10に記載の光硬化性接着剤組成物。
- さらに、(H)レベリング剤を組成物中に0.01~0.5重量%含有する請求項1~請求11のいずれかに記載の光硬化性接着剤組成物。
- 一軸延伸され、二色性色素が吸着配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に、接着剤を介して、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂及び非晶性ポリオレフィン系樹脂からなる群より選ばれる透明樹脂フィルムからなる保護膜が貼合されてなる偏光板であって、前記接着剤は、請求項1~請求項12のいずれかに記載の光硬化性接着剤組成物から形成されていることを特徴とする偏光板。
- 一軸延伸され、二色性色素が吸着配向されたポリビニルアルコール系樹脂フィルムからなる偏光子に、接着剤を介して、ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂及び非晶性ポリオレフィン系樹脂からなる群より選ばれる透明樹脂フィルムからなる保護膜を貼合し、偏光板を製造する方法であって、
前記偏光子と前記保護膜との貼合面のうち少なくとも一方に、請求項1~請求項12のいずれかに記載の光硬化性接着剤組成物を塗布する接着剤塗布工程と、
得られる接着剤層を介して前記偏光子と前記保護膜とを貼合する貼合工程と、
前記接着剤層を介して偏光子と保護膜とが貼合された状態で前記光硬化性接着剤組成物を硬化させる硬化工程と
を包含することを特徴とする偏光板の製造方法。 - 請求項13に記載の偏光板に他の光学層が積層されていることを特徴とする光学部材。
- 他の光学層は、位相差板を含む請求項15に記載の光学部材。
- 請求項15又は請求項16に記載の光学部材が、液晶セルの片側又は両側に配置されてなることを特徴とする液晶表示装置。
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JP7063684B2 (ja) | 2018-03-30 | 2022-05-09 | 三井化学株式会社 | 光学結像装置用接着剤およびその硬化物 |
JP2019178208A (ja) * | 2018-03-30 | 2019-10-17 | 三井化学株式会社 | 光学結像装置用接着剤およびその硬化物 |
JP2022504598A (ja) * | 2019-02-19 | 2022-01-13 | エルジー・ケム・リミテッド | 偏光板の製造方法 |
JP7391338B2 (ja) | 2019-02-19 | 2023-12-05 | エルジー・ケム・リミテッド | 偏光板の製造方法 |
US11975500B2 (en) | 2019-02-19 | 2024-05-07 | Lg Chem, Ltd. | Method for manufacturing polarizing plate |
JP7452266B2 (ja) | 2020-06-05 | 2024-03-19 | 株式会社レゾナック | 接着剤、及び接着体 |
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KR20150071019A (ko) | 2015-06-25 |
CN104823087B (zh) | 2018-01-12 |
KR102215376B1 (ko) | 2021-02-10 |
TW201422749A (zh) | 2014-06-16 |
TWI607074B (zh) | 2017-12-01 |
JPWO2014058042A1 (ja) | 2016-09-05 |
JP6223349B2 (ja) | 2017-11-01 |
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