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KR101935080B1 - Method for manufacturing polarizer - Google Patents

Method for manufacturing polarizer Download PDF

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Publication number
KR101935080B1
KR101935080B1 KR1020147011642A KR20147011642A KR101935080B1 KR 101935080 B1 KR101935080 B1 KR 101935080B1 KR 1020147011642 A KR1020147011642 A KR 1020147011642A KR 20147011642 A KR20147011642 A KR 20147011642A KR 101935080 B1 KR101935080 B1 KR 101935080B1
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KR
South Korea
Prior art keywords
film
roll
adhesive
active energy
energy ray
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KR1020147011642A
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Korean (ko)
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KR20140088539A (en
Inventor
준 후루카와
아즈사 히로이와
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스미또모 가가꾸 가부시키가이샤
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Publication of KR20140088539A publication Critical patent/KR20140088539A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
    • B29D11/00—Producing optical elements, e.g. lenses or prisms
    • B29D11/00634—Production of filters
    • B29D11/00644—Production of filters polarizing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C65/1429—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface
    • B29C65/1435—Joining or sealing of preformed parts, e.g. welding of plastics materials; Apparatus therefor by heating, with or without pressure using wave energy, i.e. electromagnetic radiation, or particle radiation characterised by the way of heating the interface at least passing through one of the parts to be joined, i.e. transmission welding
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C66/73—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/739—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset
    • B29C66/7392—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic
    • B29C66/73921—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the intensive physical properties of the material of the parts to be joined, by the optical properties of the material of the parts to be joined, by the extensive physical properties of the parts to be joined, by the state of the material of the parts to be joined or by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of the parts to be joined being a thermoplastic or a thermoset characterised by the material of at least one of the parts being a thermoplastic characterised by the materials of both parts being thermoplastics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2011/00—Optical elements, e.g. lenses, prisms
    • B29L2011/0066—Optical filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/412—Transparent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/42—Polarizing, birefringent, filtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2310/00—Treatment by energy or chemical effects
    • B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
    • B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B32B37/1284—Application of adhesive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/16—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating
    • B32B37/20—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with all layers existing as coherent layers before laminating involving the assembly of continuous webs only
    • B32B37/203—One or more of the layers being plastic
    • B32B37/206—Laminating a continuous layer between two continuous plastic layers
    • 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
    • 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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  • Ophthalmology & Optometry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The present invention relates to a process for producing a polarizing film, comprising the steps of applying an adhesive of an active energy ray curable type to one side of a transparent film or one side or both sides of a polarizing film, and a lamination step of laminating a transparent film on one side or both sides of the polarizing film through an adhesive A joining step of joining the transparent film and the polarizing film by applying pressure to the laminate by sandwiching the laminate between a pair of joining rolls rotating in the conveying direction; A first active energy ray irradiation step of irradiating the laminate with an active energy ray to cure the adhesive, in this order, at least one of the pair of bonding rolls is a rubber Roll, and the rotation speed of the rotation roll is faster than the rotation speed of the rubber roll.

Figure R1020147011642

Description

METHOD FOR MANUFACTURING POLARIZER [0002]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a polarizing plate useful as one of optical components constituting a liquid crystal display or the like.

The polarizing film is widely used as a polyvinyl alcohol-based resin film in which a dichromatic dye is adsorbed and oriented, and an iodine-based polarizing film using iodine as a dichromatic dye or a dye-based polarizing film using a dichromatic direct dye as a dichromatic dye Film and the like are known. These polarizing films are usually polarized by bonding a transparent film such as a triacetylcellulose film to one or both sides thereof with an adhesive.

As a method of laminating a transparent film on one side or both sides of a polarizing film, an active energy ray-curable resin is applied to the surface of the transparent film in advance, and then the polarizing film and the transparent film are sandwiched between a pair of nip rolls (Japanese Patent Application Laid-Open No. 2004-245925, Patent Document 2: Japanese Patent Application Laid-Open No. 2009-134190, Patent Document 3: Japanese Patent Application Laid- Japanese Patent Application Laid-Open No. 11-95560).

Patent Document 3 discloses that when the active energy ray-curable resin is cured by irradiating an active energy ray, the laminate is cured while adhering to the outer surface of the roll, thereby suppressing occurrence of wave curling and the like. However, (Hereinafter referred to as " corrugated wrinkles ") is generated in the corrugated plate in the polarizing plate produced when the balance of the rotation speed of the roll for adhering the laminate to the active energy ray irradiation is inadequate .

Japanese Patent Application Laid-Open No. 2004-245925 Japanese Patent Application Laid-Open No. 2009-134190 Japanese Patent Laid-Open No. 11-95560

An object of the present invention is to suppress generation of corrugated wrinkles in a method comprising the step of curing the active energy ray-curable resin while bringing the laminate into contact with the outer peripheral surface of the roll as described above.

The present invention relates to a method for producing a polarizing plate in which a transparent film is bonded to one side or both sides of a polarizing film, wherein an active energy ray-curable adhesive is applied to one side of the transparent film or one side or both sides of the polarizing film An adhesive applying step and a lamination body in which the transparent film is laminated on one side or both sides of the polarizing film through the adhesive are sandwiched between a pair of bonding rolls rotating in the carrying direction and pressure is applied to the laminate, A bonding step of bonding the transparent film and the polarizing film to each other; and a step of irradiating the laminate with an active energy ray to cure the adhesive, while the laminate is transported in a state of being in tight contact with the rotating roll rotating in the carrying direction And an energy beam irradiation step in this order, wherein at least one of the pair of bonding rolls And the rubber roll has a surface that is driven to rotate, the rotational speed of the rotating rolls is faster than the rotation speed of the rubber roll. The rotary roll is preferably a cooling roll.

In the present invention, the rotating speed of the rotating roll is preferably 100.1 to 102.0 when the rotating speed of the rubber roll is 100.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a polarizing plate having favorable appearance with suppressed generation of corrugated wrinkles. Therefore, by using the polarizing plate obtained by the manufacturing method of the present invention, it is possible to provide a liquid crystal display device of high quality.

1 is a schematic side view showing an embodiment of an apparatus for producing a polarizing plate according to the present invention.

The present invention relates to a method for producing a polarizing plate in which a transparent film is bonded to one side or both sides of a polarizing film, comprising the steps of applying an adhesive of an active energy ray curing type to one side of a transparent film or one side or both sides of a polarizing film And a laminated body in which a transparent film is laminated on one side or both sides of a polarizing film through the adhesive is sandwiched between a pair of bonding rolls which are rotated in a carrying direction and a pressure is applied to the laminated body to form a transparent film and a polarizing film And a first active energy ray irradiation step in which the laminate is irradiated with an active energy ray to cure the adhesive while the laminate is transported in a state of being closely contacted with the rotating roll rotating in the carrying direction do. At least one of the pair of bonding rolls is a rubber roll which is rotationally driven with a surface including rubber, and the rotational speed of the rotational roll is faster than the rotational speed of the rubber roll.

First, each element used in the manufacturing method of the present invention will be described in detail.

(Polarizing film)

Specifically, the polarizing film used in the method for producing a polarizing plate of the present invention is one obtained by orienting a dichromatic dye on a uniaxially stretched polyvinyl alcohol resin film. The polyvinyl alcohol-based resin is obtained by saponifying a polyvinyl acetic acid-based resin. Examples of the polyvinyl acetate-based resin include polyvinyl acetate, which is a homopolymer of vinyl acetate, as well as copolymers of vinyl acetate and other monomers copolymerizable therewith (for example, ethylene-vinyl acetate copolymer). Other monomers copolymerizable with vinyl acetate include unsaturated carboxylic acids, olefins, vinyl ethers, unsaturated sulfonic acids, and acrylamides having an ammonium group. The degree of saponification of the polyvinyl alcohol-based resin is 85 mol% or more, preferably 90 mol% or more, and more preferably 98 to 100 mol%. The average degree of polymerization of the polyvinyl alcohol-based resin is usually 1000 to 10000, preferably 1500 to 5000. These polyvinyl alcohol-based resins may be modified, and for example, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, or the like modified with aldehydes may be used.

Such a film of a polyvinyl alcohol-based resin is used as a original film of a polarizing film. The method of forming the polyvinyl alcohol-based resin is not particularly limited, and can be formed by a conventionally known appropriate method. The thickness of the original film containing the polyvinyl alcohol-based resin is not particularly limited, but is, for example, about 10 to 150 mu m. Usually, it is supplied in a roll form and has a thickness in the range of 20 to 100 mu m, preferably 30 to 80 mu m, and an industrially practical width in the range of 1500 to 6000 mm.

(Vinylon VF-PS # 7500, manufactured by Kuraray Co., Ltd. / OPL film M-7500, manufactured by Nippon Gosei Co., Ltd.) Vinylon VF-PE # 6000, Kuraray Co., Ltd.) has a thickness of 60 mu m.

The polarizing film is usually formed by a process of dyeing a polyvinyl alcohol resin film with a dichroic dye to adsorb the dichroic dye (dyeing process), a process of treating a polyvinyl alcohol resin film adsorbed with a dichroic dye with an aqueous solution of boric acid (A boric acid treatment step), and a step of washing with water after the treatment with the aqueous solution of boric acid (a water washing step).

In producing the polarizing film, the polyvinyl alcohol-based resin film is usually uniaxially stretched. This uniaxial stretching may be performed before the dyeing process, during the dyeing process, or after the dyeing process . In the case of performing uniaxial stretching after the dyeing treatment step, the uniaxial stretching may be performed before the boric acid treatment step or during the boric acid treatment step. Of course, it is also possible to perform uniaxial stretching in these plural steps.

The uniaxial stretching may be uniaxially stretched between different rolls of the main yarn, or uniaxially stretched by using a heat roll. In addition, it may be dry stretching in which stretching is performed in the atmosphere, or wet stretching in which stretching is performed in a state of being swollen with a solvent. The stretching magnification is usually about 3 to 8 times.

The dyeing by the dichroic dye of the polyvinyl alcohol-based resin film in the dyeing treatment step is carried out, for example, by immersing a polyvinyl alcohol-based resin film in an aqueous solution containing a dichroic dye. As the dichroic dye, for example, iodine, a dichroic dye and the like are used. The dichroic dyes include, for example, Si. children. Dichroic direct dyes including disazo compounds such as C. I. DIRECT RED 39, dichromatic direct dyes including compounds such as trisazo, tetrakisazo, and the like. The polyvinyl alcohol-based resin film is preferably subjected to immersion treatment with water before the dyeing treatment.

When iodine is used as the dichroism dye, a method in which a polyvinyl alcohol resin film is dipped in an aqueous solution containing iodine and potassium iodide is generally employed. The content of iodine in this aqueous solution is usually 0.01 to 1 part by weight per 100 parts by weight of water, and the content of potassium iodide is usually 0.5 to 20 parts by weight per 100 parts by weight of water. When iodine is used as the dichroism dye, the temperature of the aqueous solution used for dyeing is usually 20 to 40 占 폚, and the immersion time (dyeing time) for this aqueous solution is usually 20 to 1800 seconds.

On the other hand, when a dichroic dye is used as the dichroic dye, a method in which a polyvinyl alcohol resin film is dipped in an aqueous solution containing a dichroic dye is generally employed. The content of the dichroic dye in this aqueous solution is usually water, and 100 parts by weight of 1 × 10 -4 to 10 parts by weight, preferably 1 × 10 -3 to 1 part by weight, particularly preferably 1 × 10 -3 to 1 × 10 - 2 are parts by weight. This aqueous solution may contain an inorganic salt such as sodium sulfate as a dyeing aid. When a dichroic dye is used as the dichroism dye, the dye aqueous solution used for dyeing usually has a temperature of 20 to 80 캜, and the dipping time (dyeing time) for the aqueous solution is usually 10 to 1,800 seconds.

The boric acid treatment step is carried out by immersing a polyvinyl alcohol-based resin film stained with a dichroic dye in an aqueous solution containing boric acid. The amount of boric acid in the boric acid-containing aqueous solution is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. When iodine is used as the dichroic dye in the above-described dyeing process, it is preferable that the boric acid-containing aqueous solution used in the boric acid treatment step contains potassium iodide. In this case, the amount of potassium iodide in the boric acid-containing aqueous solution is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, per 100 parts by weight of water. The immersing time in the boric acid-containing aqueous solution is usually 60 to 1200 seconds, preferably 150 to 600 seconds, more preferably 200 to 400 seconds. The temperature of the boric acid-containing aqueous solution is usually 40 占 폚 or higher, preferably 50 to 85 占 폚, and more preferably 55 to 75 占 폚.

In the subsequent water washing treatment step, the polyvinyl alcohol resin film after the boric acid treatment is subjected to water washing treatment, for example, by immersion in water. The temperature of water in the water washing treatment is usually 4 to 40 占 폚, and the immersion time is usually 1 to 120 seconds. After the washing treatment, the drying treatment is usually carried out to obtain a polarizing film. The drying treatment is preferably carried out using a hot-air dryer, a far-infrared heater, or the like. The temperature of the drying treatment is usually 30 to 100 占 폚, preferably 50 to 80 占 폚. The drying treatment time is usually 60 to 600 seconds, preferably 120 to 600 seconds.

Thus, the polyvinyl alcohol-based resin film is subjected to uniaxial stretching, dyeing with a dichroic dye, boric acid treatment and washing treatment to obtain a polarizing film. The thickness of the polarizing film is usually in the range of 5 to 50 mu m.

(Transparent film)

In the present invention, a transparent film is bonded to one side or both sides of the above-mentioned polarizing film. Examples of the material constituting the transparent film include a cycloolefin resin, a cellulose acetate resin, a polyester resin such as polyethylene terephthalate, polyethylene naphthalate and polybutylene terephthalate, a polycarbonate resin, an acrylic resin, Polypropylene, and the like, which are conventionally widely used in the field. When a transparent film is bonded to both sides of a polarizing film, each transparent film may be the same or may be a different kind of film.

The cycloolefin-based resin is a thermoplastic resin (also referred to as a thermoplastic cycloolefin-based resin) having a unit of a monomer containing a cyclic olefin (cycloolefin), such as norbornene or a polycyclic norbornene monomer. The cycloolefin resin may be a hydrogenated product of a ring-opening polymer of the cycloolefin or a ring-opening copolymer using two or more cycloolefins, or an addition polymer with a cycloolefin, a chain olefin, or an aromatic compound having a vinyl group. It is also effective that a polar group is introduced.

When a copolymer of a cycloolefin and an aromatic compound having a chain or olefin and / or a vinyl group is used, examples of the chain olefin include ethylene and propylene. Examples of the aromatic compound having a vinyl group include styrene, Substituted styrene, and the like. In such a copolymer, the unit of the monomer containing the cycloolefin may be 50 mol% or less (preferably 15 to 50 mol%). Especially when a terpolymer of a cycloolefin, a chain olefin and an aromatic compound having a vinyl group is used, the unit of the monomer containing the cycloolefin can be a relatively small amount as described above. In such a terpolymer, the unit of the monomer containing a chain olefin is usually 5 to 80 mol%, and the unit of the monomer containing an aromatic compound having a vinyl group is usually 5 to 80 mol%.

Examples of the cycloolefin resin include commercially available products such as Topas (manufactured by Ticona), Aton (manufactured by JSR Corporation), Zeonor (manufactured by Nippon Zeon Co., Ltd.) ZEONEX (manufactured by Nippon Zeon Co., Ltd.), APEL (manufactured by Mitsui Chemicals, Inc.), and OXIS (manufactured by Okura Corporation) can be preferably used. When the cycloolefin resin is formed into a film, known methods such as a solvent casting method and a melt extrusion method are suitably used. Further, a preformed cycloolefin such as, for example, Essen (manufactured by Sekisui Chemical Co., Ltd.), SCA40 (manufactured by Sekisui Chemical Co., Ltd.), Zeonor film (manufactured by Optesis) A commercially available product of a film made of a resin can also be used.

The cycloolefin-based resin film may be uniaxially stretched or biaxially stretched. By stretching, an arbitrary retardation value can be imparted to the cycloolefin-based resin film. The stretching is usually carried out while unwinding the film roll, and is stretched by a heating furnace in the direction of advancement of the roll (longitudinal direction of the film), in the direction perpendicular to the progressing direction (width direction of the film), or both. The temperature of the heating furnace is usually in the range of the glass transition temperature + 100 deg. C in the vicinity of the glass transition temperature of the cycloolefin-based resin. The magnification of the stretching is usually 1.1 to 6 times, preferably 1.1 to 3.5 times.

When the cycloolefin-based resin film is in the roll-wound state, since the films tends to adhere to each other and blockiness tends to occur, roll-winding is usually carried out after the protective film is bonded. Since the cycloolefin-based resin film generally has a low surface activity, the surface to be bonded to the polarizing film is subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet ray irradiation treatment, frame (flame) treatment and saponification treatment . Among them, a plasma treatment, particularly an atmospheric pressure plasma treatment and a corona treatment, which can be carried out relatively easily, is preferable.

As the cellulose acetate based resin, a cellulose ester partially or completely esterified product includes, for example, cellulose acetate ester, propionic ester, butyric acid ester, mixed ester thereof and the like. More specifically, a triacetylcellulose film, a diacetylcellulose film, a cellulose acetate propionate film, a cellulose acetate butyrate film and the like can be given. Examples of such a cellulose ester based resin film include commercially available products such as Fuji Tack TD80 (manufactured by Fuji Film), Fuji Tack TD80UF (manufactured by Fuji Film), Fuji Tack TD80UZ (manufactured by Fuji Film Co., Ltd.) , KC8UYW (manufactured by Konica Minolta Opto Co., Ltd.), KC8UY (manufactured by Konica Minolta Opto Co., Ltd.), Fujitac TD60UL (manufactured by Fuji Film Co., Ltd.), KC2UAW KC6UAW (manufactured by Konica Minolta Opto Co., Ltd.), and the like can be preferably used.

Also, as the transparent film, a cellulose acetate resin film imparted with a retardation property is also preferably used. Examples of commercial products of the cellulose acetate based resin film to which such retardation properties are imparted include WV BZ 438 (manufactured by Fuji Film), KC4FR-1 (manufactured by Konica Minolta Opto Co., Ltd.), KC4CR-1 (Konica Minolta Opto Co., , KC4AR-1 (manufactured by Konica Minolta Opto), and the like. Acetate cellulose is also referred to as acetylcellulose or cellulose acetate.

These cellulose acetate resin films are easily absorbed, and the water content of the polarizer sometimes affects the end sagging of the polarizer. The moisture content at the time of production of the polarizing plate is preferably as close as possible to the storage environment of the polarizing plate, for example, the equilibrium moisture content in a production line of a clean room or a storage room of a winding roll, and depends on the composition of the laminated film. , And more preferably from 2.5% to 3.0%. The numerical value of the moisture content of the polarizing plate was measured by a dry weight method, and the change in weight after 105 ° C / 120 minutes.

The thickness of the transparent film used in the polarizing plate manufacturing method of the present invention is preferably small, but if it is too thin, the strength is lowered and the workability is lowered. On the other hand, if the thickness is too large, the transparency may deteriorate or the curing time required after the lamination may be prolonged. Therefore, the suitable thickness of the transparent film is, for example, 5 to 200 占 퐉, preferably 10 to 150 占 퐉, and more preferably 10 to 100 占 퐉.

A surface treatment such as a corona treatment, a flame treatment, a plasma treatment, an ultraviolet treatment, a primer coating treatment or a saponification treatment is applied to the polarizing film and / or the transparent film in order to improve the adhesion between the adhesive and the polarizing film and / .

The transparent film may be subjected to surface treatment such as antiglare treatment, anti-reflection treatment, hard coating treatment, antistatic treatment and antifouling treatment, either singly or in combination of two or more kinds. The transparent protective film and / or the transparent film surface protective layer may contain an ultraviolet absorber such as a benzophenone-based compound or a benzotriazole-based compound or a plasticizer such as a phenylphosphate-based compound or a phthalic acid ester compound.

Further, the transparent film can have optical functions such as a function as a retardation film, a function as a luminance enhancement film, a function as a reflection film, a function as a transflective film, a function as a diffusion film, and a function as an optical compensation film. In this case, for example, it is possible to have such a function by laminating an optical functional film such as a retardation film, a luminance enhancement film, a reflection film, a transflective film, a diffusion film, or an optical compensation film on the surface of a transparent film In addition to this, the transparent film itself may be provided with such a function. In addition, a plurality of functions such as a diffusion film having the function of a brightness enhancement film may be provided in the transparent film.

For example, the stretching process described in Japanese Patent No. 2841377, Japanese Patent No. 3094113, and the like are performed on the above-mentioned transparent film, or the process described in Japanese Patent No. 3168850 is performed to give a function as a retardation film can do. The retardation property in the retardation film can be appropriately selected, for example, in the range of the front retardation value of 5 to 100 nm and the thickness retardation value of 40 to 300 nm. Further, by forming fine holes in the above-mentioned transparent film by the method described in Japanese Patent Application Laid-Open Nos. 2002-169025 and 2003-29030, or by forming fine holes having different center wavelengths of selective reflection 2 By superimposing the cholesteric liquid crystal layer above the layer, a function as a brightness enhancement film can be given.

When a metal thin film is formed on the above-mentioned transparent film by vapor deposition, sputtering or the like, a function as a reflective film or a transflective film can be given. By coating the above-mentioned transparent film with a resin solution containing fine particles, a function as a diffusion film can be imparted. Further, by coating a liquid crystal compound such as a discotic liquid crystal compound and orienting the above-mentioned transparent film, a function as an optical compensation film can be imparted. Further, the transparent film may contain a compound exhibiting a retardation. Further, various optical functional films may be directly bonded to the polarizing film by using a suitable adhesive. Examples of the commercially available optical functional film include a luminance enhancement film such as DBEF (available from 3M Company, Japan, available from Sumitomo 3M Ltd.), a WV film (manufactured by Fuji Film Co., Ltd.) (Manufactured by Shin-Etsu Chemical Co., Ltd.), VA-TAC (manufactured by Konica Minolta Opto Co., Ltd.) ), And Sumikarite (manufactured by Sumitomo Chemical Co., Ltd.).

(Active energy ray curable adhesive)

The polarizing film and the transparent film are bonded together through an adhesive of an active energy ray curing type. As an active energy ray curable adhesive, an adhesive containing an epoxy resin composition containing an epoxy resin which is cured by irradiation of an active energy ray from the viewpoints of weatherability, refractive index, cationic polymerizability and the like can be mentioned. However, the present invention is not limited thereto. Various types of active energy ray-curable adhesives (organic solvent adhesives, hot melt adhesives, solventless adhesives, etc.) conventionally used in the production of polarizers, such as acrylamide, An adhesive containing an acrylic resin composition such as acrylate, epoxy acrylate and the like can be employed.

The epoxy resin means a compound having two or more epoxy groups in the molecule. From the standpoint of weatherability, refractive index, cationic polymerizability and the like, the epoxy resin contained in the curable epoxy resin composition as the adhesive is preferably an epoxy resin containing no aromatic ring in the molecule (for example, see Patent Document 1). As such epoxy resins, hydrogenated epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins and the like can be exemplified.

The hydrogenated epoxy resin can be obtained by a method of glycidyl etherification of a nuclear hydrogenated polyhydroxy compound obtained by selectively subjecting a polyhydroxy compound as a raw material of an aromatic epoxy resin to a nuclear hydrogenation reaction under pressure in the presence of a catalyst . Examples of the aromatic epoxy resin include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; Novolak type epoxy resins such as phenol novolak epoxy resin, cresol novolak epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; Glycidyl ethers of tetrahydroxyphenylmethane, glycidyl ethers of tetrahydroxybenzophenone, and epoxy polyvinylphenols. The epoxy resin may be used alone or in combination of two or more. Of hydrogenated epoxy resins, hydrogenated glycidyl ethers of bisphenol A are preferred.

The alicyclic epoxy resin means an epoxy resin having at least one epoxy group bonded to an alicyclic ring in the molecule. The "epoxy group bonded to the alicyclic ring" means a bridging oxygen atom -O- in the structure represented by the following formula. In the following formulas, m is an integer of 2 to 5.

Figure 112014041062899-pct00001

The compound in which one or more hydrogen atoms of the (CH 2 ) m in the above formula are removed from other groups in the chemical structure may be an alicyclic epoxy resin. (CH 2 ) m may be suitably substituted with a straight chain alkyl group such as methyl group or ethyl group. Among the alicyclic epoxy resins, an epoxy resin having an oxabicyclohexane ring (wherein m = 3 in the above formula) or an oxabicycloheptane ring (in which m = 4 in the above formula) exhibits excellent adhesiveness, . Hereinafter, the alicyclic epoxy resin which is preferably used is specifically exemplified, but the present invention is not limited thereto.

(a) epoxycyclohexylmethyl epoxycyclohexanecarboxylates represented by the following formula (I):

Figure 112014041062899-pct00002

(Wherein R 1 and R 2 represent, independently of each other, a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms).

(b) Epoxycyclohexanecarboxylates of alkanediol represented by the following formula (II):

Figure 112014041062899-pct00003

(Wherein R 3 and R 4 represent, independently of each other, a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms, and n represents an integer of 2 to 20).

(c) epoxycyclohexylmethyl esters of dicarboxylic acids represented by the following formula (III):

Figure 112014041062899-pct00004

(Wherein R 5 and R 6 are each independently of the other a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms, and p represents an integer of 2 to 20).

(d) epoxycyclohexyl methyl ethers of polyethylene glycol represented by the following formula (IV):

Figure 112014041062899-pct00005

(Wherein R 7 and R 8 are, independently of each other, a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms, and q represents an integer of 2 to 10).

(e) epoxycyclohexyl methyl ethers of alkane diols represented by the following formula (V):

Figure 112014041062899-pct00006

(Wherein R 9 and R 10 are independently of each other a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms, and r represents an integer of 2 to 20).

(f) a diepoxy trispyro compound represented by the following formula (VI):

Figure 112014041062899-pct00007

(Wherein R < 11 > and R < 12 > independently represent a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms).

(g) a diepoxy monospiro compound represented by the following formula (VII):

Figure 112014041062899-pct00008

(Wherein R 13 and R 14 represent, independently of each other, a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms).

(h) vinylcyclohexene epoxides represented by the following formula (VIII):

Figure 112014041062899-pct00009

(Wherein R 15 represents a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms).

(i) epoxycyclopentyl ethers represented by the following formula (IX):

Figure 112014041062899-pct00010

(Wherein R 16 and R 17 represent, independently of each other, a hydrogen atom or a straight chain alkyl group having 1 to 5 carbon atoms).

(j) diepoxytricyclodecane compounds represented by the following formula (X):

Figure 112014041062899-pct00011

(Wherein R 18 represents a hydrogen atom or a straight chain alkyl group of 1 to 5 carbon atoms).

Among the above-exemplified alicyclic epoxy resins, the following alicyclic epoxy resins are more preferably used because they are commercially available, or as analogues thereof, and are relatively easy to obtain.

(A) an ester of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (7-oxa-bicyclo [4.1.0] hept- 1 = compound of R < 2 > = H]

(B) An esterified product of 4-methyl-7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and (4-methyl- [In the formula (I), a compound of R 1 = 4-CH 3 and R 2 = 4-CH 3 ]

(C) an esterified product of 7-oxabicyclo [4.1.0] heptane-3-carboxylic acid and 1,2-ethanediol [compound of formula (II) wherein R 3 = R 4 = H, n = 2] ,

Compounds of formula (III) wherein R 5 = R 6 = H, p = 4], (D) (7-oxabicyclo [4.1.0] hept-3-yl) methanol and adipic acid [

(E) (R 4 = CH 3 , R 6 = CH 3 ) in the formula (III) with an esterified product of (4-methyl- 4-CH 3 , p = 4]

(F) (7- oxabicyclo [4.1.0] hept-3-yl) ether in the cargo [formula (V) of methanol and 1,2-ethanediol, R 9 = R 10 = a H, r = 2 compound].

Examples of the aliphatic epoxy resin include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof. More specifically, diglycidyl ether of 1,4-butanediol; Diglycidyl ether of 1,6-hexanediol; Triglycidyl ether of glycerin; Triglycidyl ether of trimethylolpropane; Diglycidyl ether of polyethylene glycol; Diglycidyl ether of propylene glycol; And polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide or propylene oxide) to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin.

The epoxy resin constituting the adhesive containing the epoxy resin composition may be used alone or in combination of two or more. The epoxy equivalent of the epoxy resin used in this composition is usually in the range of 30 to 3,000 g / equivalent, preferably 50 to 1,500 g / equivalent. If the epoxy equivalent is less than 30 g / equivalent, the flexibility of the composite polarizer after curing may be lowered or the adhesive strength may be lowered. On the other hand, if it exceeds 3,000 g / equivalent, compatibility with other components contained in the adhesive may be lowered.

In this adhesive, cationic polymerization is preferably used as a curing reaction of the epoxy resin from the viewpoint of reactivity. Therefore, it is preferable to incorporate a cationic polymerization initiator into the curable epoxy resin composition which is an active energy ray curable adhesive. The cationic polymerization initiator generates a cationic species or a Lewis acid by irradiation of an active energy ray such as visible light, ultraviolet ray, X-ray or electron ray to initiate the polymerization reaction of the epoxy group. Hereinafter, the cationic polymerization initiator for generating a cationic species or Lewis acid by irradiation of an active energy ray to initiate the polymerization reaction of the epoxy group is referred to as " photo cationic polymerization initiator ".

The method of curing the adhesive by irradiation of an active energy ray using a photo cationic polymerization initiator enables curing at room temperature and reduces the need to take into account distortion due to heat resistance or expansion of the polarizing film, It is advantageous in that it can be bonded. Further, since the photo cationic polymerization initiator acts catalytically with light, it is excellent in storage stability and workability even when mixed with an epoxy resin.

Examples of the photo cationic polymerization initiator include aromatic diazonium salts; Onium salts such as aromatic iodonium salts and aromatic sulfonium salts; Iron-arene complexes and the like.

Examples of the aromatic diazonium salt include benzene diazonium hexafluoroantimonate, benzene diazonium hexafluorophosphate, benzene diazonium hexafluoroborate, and the like. Examples of the aromatic iodonium salt include diphenyl iodonium tetrakis (pentafluorophenyl) borate, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.

The aromatic sulfonium salts include, for example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4'-bis ( Diphenylsulfone bis (hexafluorophosphate), 4,4'-bis [di (? - hydroxyethoxy) phenylsulfonio] diphenylsulfide bis (hexafluoroantimonate) (P-toluyl) sulfonyl] diphenylsulfide bis (hexafluorophosphate), 4,4'-bis [di (? - hydroxyethoxy) phenylsulfonio] (P-toluyl) sulfonium] -2-isopropylthioxanthone tetrakis (pentafluorophenyl) borate, 4-phenyl Diphenylsulfide hexafluorophosphate, 4- (p-tert-butylphenylcarbonyl) -4'-diphenylsulfone-diphenylsulfide hexafluorophosphate, And the like can be mentioned diphenyl sulfide tetrakis (pentafluorophenyl) borate-antimonate, 4- (p-tert- butylphenyl-carbonyl) -4'-di (p- toluyl) Pony O.

Examples of the iron-arene complexes include xylene-cyclopentadienyl iron (II) hexafluoroantimonate, cumene-cyclopentadienyl iron (II) hexafluorophosphate, xylene-cyclopentadienyl iron ) -Tris (trifluoromethylsulfonyl) methanide, and the like.

Commercially available products of these cationic photopolymerization initiators can be easily obtained. For example, "Kayarad PCI-220" and "Kayarad PCI-620" (trade names, manufactured by Nippon Kayaku Co., , "Adeka Optomer SP-150" and "Adeka Optomer SP-170" (manufactured by Adeka Corporation), "CI-6990" (manufactured by Union Carbide Corporation) DPI-101 "," CIP-2082S "and" CIP-2064S "(manufactured by Nippon Soda Co., Ltd.)," CIT- DPI-103, DPI-105, MPI-103, MPI-105, BBI-101, BBI-102, BBI- 105, TPS-101, TPS-102, TPS-103, TPS-105, MDS-103, MDS-105, DTS- (Manufactured by Midori Kagaku Co., Ltd.) and " PI-2074 " (manufactured by Rhodia).

The cationic photopolymerization initiator may be used singly or as a mixture of two or more thereof. Among them, an aromatic sulfonium salt is preferably used because it has an ultraviolet ray absorbing property even in a wavelength range of 300 nm or more and is therefore excellent in curability and can provide a cured product having good mechanical strength and adhesive strength.

The compounding amount of the photo cationic polymerization initiator is usually 0.5 to 20 parts by weight, preferably 1 part by weight or more, and more preferably 15 parts by weight or less, based on 100 parts by weight of the epoxy resin. If the blending amount of the photo cationic polymerization initiator is less than 0.5 part by weight based on 100 parts by weight of the epoxy resin, the curing becomes insufficient and the mechanical strength and the adhesive strength tend to be lowered. If the compounding amount of the photo cationic polymerization initiator is more than 20 parts by weight based on 100 parts by weight of the epoxy resin, the amount of the ionic substance in the cured product increases to increase the hygroscopicity of the cured product.

When a photo cationic polymerization initiator is used, the curable epoxy resin composition may further contain a photosensitizer, if necessary. By using a photosensitizer, the reactivity of the cationic polymerization is improved, and the mechanical strength and adhesive strength of the cured product can be improved. Examples of the photosensitizer include a carbonyl compound, an organic sulfur compound, a persulfate compound, a redox compound, an azo compound and a diazo compound, a halogen compound, a light reducing pigment and the like.

More specific examples of the photosensitizer include benzoin derivatives such as benzoin methyl ether, benzoin isopropyl ether, and?,? -Dimethoxy-? -Phenylacetophenone; Benzophenone derivatives such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (diethylamino) benzophenone; Thioxanthone derivatives such as 2-chlorothioxanthone, and 2-isopropylthioxanthone; Anthraquinone derivatives such as 2-chloro anthraquinone, and 2-methyl anthraquinone; Acridone derivatives such as N-methyl acridone, and N-butyl acridone; Other examples include?,? - diethoxyacetophenone, benzyl, fluorenone, xanthone, uranyl compound, and halogen compound. The photosensitizer may be used alone or in combination of two or more. It is preferable that the photosensitizer is contained in the range of 0.1 to 20 parts by weight in 100 parts by weight of the curable epoxy resin composition.

The epoxy resin contained in the adhesive is cured from photo cation polymerization, but may also be cured by both photo cation polymerization and thermal cation polymerization. In the latter case, a photo cationic polymerization initiator and a thermal cationic polymerization initiator are preferably used in combination.

Examples of the thermal cationic polymerization initiator include a benzylsulfonium salt, a thiophenium salt, a thioronium salt, a benzylammonium salt, a pyridinium salt, a hydrazinium salt, a carboxylic acid ester, a sulfonic acid ester, and an amine imide. These thermal cationic polymerization initiators can be easily obtained as commercial products, and examples thereof include "ADEKA OPTON CP77" and "ADEKA OPTON CP66" (trade names, manufactured by Adeka Kagaku Co., Ltd.) CI-2639 "and" CI-2624 "(manufactured by Nippon Soda Co., Ltd.)," Sun Aid SI-60L "," Sun Aid SI-80L "and" Sun Aid SI- Manufactured by Kabushiki Kaisha).

The active energy ray curable adhesive may further contain a compound that promotes cationic polymerization such as oxetanes and polyols.

The oxetanes are compounds having a 4-membered ring ether in the molecule, and examples thereof include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanyl) methoxy (3-ethyl-3-oxetanyl) methyl] ether, 3-ethyl-3- (2-ethylhexyloxymethyl) ox Cetane, phenol novolac oxetane, and the like. These oxetanes are commercially available as commercially available products, and examples thereof include "AARON oxetane OXT-101", "AARON oxetane OXT-121", "AARON oxethane OXT-211" , "Aronoxetan OXT-221" and "Aronoxetan OXT-212" (all manufactured by Toagosei Co., Ltd.). These oxetanes are contained in the curable epoxy resin composition in an amount of usually 5 to 95% by weight, preferably 30 to 70% by weight.

As the polyol, it is preferable that an acid group other than the phenolic hydroxyl group is not present. For example, a polyol compound having no functional group other than the hydroxyl group, a polyester polyol compound, a polycaprolactone polyol compound, a polyol compound having a phenolic hydroxyl group , Polycarbonate polyol, and the like. The molecular weight of these polyols is usually 48 or more, preferably 62 or more, more preferably 100 or more, and further preferably 1,000 or less. These polyols are usually contained in a proportion of not more than 50% by weight, preferably not more than 30% by weight, in the curable epoxy resin composition.

Additives such as an ion trapping agent, an antioxidant, a chain transfer agent, a tackifier, a thermoplastic resin, a filler, a flow regulator, a leveling agent, a plasticizer, and an antifoaming agent may be further added to the active energy ray curable adhesive. Examples of the ion trap agent include inorganic compounds such as powdery bismuth, antimony, magnesium, aluminum, calcium, titanium and mixtures thereof. Examples of the antioxidant include hindered phenol antioxidants have.

The active energy ray-curable adhesive can be used as a solvent-free adhesive agent substantially not containing a solvent component. However, since each coating method has an optimum viscosity range, a solvent may be added for viscosity adjustment. As the solvent, it is preferable to use a solvent which dissolves an epoxy resin composition or the like well without lowering the optical performance of the polarizing film. For example, organic solvents such as hydrocarbons typified by toluene and esters typified by ethyl acetate . The viscosity of the active energy ray-curable adhesive used in the present invention is, for example, in the range of about 5 to 1000 mPa · s, preferably 10 to 200 mPa · s, and more preferably 20 to 100 mPa · s.

≪ Polarizing plate production method >

Next, a manufacturing apparatus and a manufacturing method of a polarizing plate of the present invention will be described with reference to the drawings. BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a schematic view showing an embodiment of a production apparatus used in a production method of a polarizing plate of the present invention. FIG.

The apparatus for producing a polarizing plate shown in Fig. 1 comprises adhesive applicators 11 and 12 for applying an adhesive to one surface of a transparent film 2 and 3, transparent films 2 and 3 and a polarizing film 1 (Nip rolls) 51 and 52 for joining the rolls to obtain the laminate 4 and a rotary roll 13 in which the laminate 4 is brought into close contact with each other, The first active energy ray irradiating devices 31 and 32 provided on the upstream side in the conveying direction and the second active energy ray irradiating devices 16 to 18 provided on the downstream side in the conveying direction and the conveying nip rolls 19, I have installed.

First, an adhesive of an active energy ray curing type is applied (adhesive applying step) to one side of the transparent films 2 and 3 which are continuously unwound from the roll-shaped state by means of the adhesive applicators 11 and 12.

A laminate in which transparent films 2 and 3 coated with an adhesive are laminated on both sides of a polarizing film 1 which has been continuously unwound from a roll-like wound state through an adhesive agent At least one of the bonding rolls is pressed in the direction of the other bonding roll so as to apply pressure to the laminated body to sandwich the polarizing film 1 and the transparent films 2 and 3 ) Are bonded to form a laminate 4 (bonding step).

Next, from the first active energy ray irradiating device (31, 32) toward the outer circumferential surface of the rotary roll (13) in the process of transporting the laminate (4) while closely contacting the outer surface of the rotary roll (13) , And the adhesive is polymerized and cured (first active energy ray irradiation step).

Further, the second active energy ray irradiating devices 16 to 18 disposed on the downstream side in the carrying direction are devices for completely polymerizing and curing the adhesive (second active energy ray irradiating step), and can be added or omitted have. Finally, the layered product 4 passes through the transporting nip roll 19 and is wound on the winding roll 20 as a polarizing plate. Hereinafter, each process will be described in detail.

(Adhesive application step)

The method of coating the adhesive on the transparent films 2, 3 is not particularly limited, but various coating methods such as doctor blade, wire bar, die coater, comma coater, and gravure coater can be used. Among them, a gravure roll is preferable as the adhesive applicators 11 and 12 in consideration of the thin film coating, the degree of freedom of the pass line, and the correspondence to the wide width.

When the adhesive is applied using a gravure roll as the adhesive applicators 11 and 12, the thickness (coating thickness) of the applied adhesive is preferably about 0.1 to 10 mu m, more preferably 0.2 to 4 mu m to be. The coating thickness of the adhesive is adjusted in accordance with the draw ratio, which is the velocity ratio of the gravure roll to the line speed of the transparent film. In general, by adjusting the draw ratio (speed / line speed of the gravure roll) to 0.5 to 10, the coating thickness of the adhesive can be adjusted to about 0.1 to 10 mu m. More specifically, the gravure roll is rotated in the direction opposite to the conveying direction of the transparent film (2, 3) with the line speed of the transparent film (2, 3) set at 10 to 100 m / 1000 m / min, the coating thickness of the adhesive can be adjusted to about 0.1 to 10 탆.

After the adhesive is produced, it is preferable that the adhesive is heated to a predetermined temperature within a range of usually 15 to 40 ° C ± 5 ° C (for example, 30 ° C ± 5 ° C when the predetermined temperature is 30 ° C) Is applied under an environment adjusted to ± 1 ° C.

(Bonding step)

In this step, the transparent films 2, 3 coated with the adhesive by the above-described process are laminated on both sides of the polarizing film 1 which has been continuously unwound from the roll-like wound state through the adhesive. The lamination body is pressed in the direction of the bonding roll 52 in the state in which the lamination body is sandwiched between the pair of bonding rolls 51 and 52 which are rotated in the carrying direction, And the transparent films 2 and 3 are bonded to each other to form the layered product 4. At this time, it is preferable to form an angle within a range of ± 3 ° with respect to a surface perpendicular to the pressing direction of the bonding roll, preferably an angle within a range of ± 1 °, It is preferable to transport the polarizing film between the joining rolls. By doing so, the polarizing film and the transparent film do not come into contact with each other immediately before the bonding roll, and bubbles are not generated.

1, an adhesive is uniformly applied to one surface of the transparent films 2 and 3, and the polarizing film 1 is laminated on the surface of the transparent films 2 and 3 coated with the adhesive, The adhesive is uniformly applied to both surfaces of the polarizing film 1 and the transparent films 2 and 3 are laminated on the surface of the polarizing film 1 coated with the adhesive to form a bonding roll 51, and 52, respectively.

As the material of the bonding rolls 51 and 52, a metal roll or a rubber roll whose surface is rubber can be mentioned. At least one of the pair of bonding rolls 51 and 52 is a rubber roll which is rotationally driven with a surface containing rubber. In the production apparatus shown in Fig. 1, for example, the lower roll 52 can be a rubber roll. Usually, the rotation speed of the rubber roll to be rotationally driven coincides with the line speed of the laminate passing between the pair of bonding rolls. As the joining roll on the other side, a metal roll is preferably used, which may be driven in line with the movement of the line of the laminate or rotationally driven. The rotation speed of the rubber roll is, for example, 10 to 50 m / min.

As the base material of the metal roll, various known materials can be used, preferably SUS304, and the surface is more preferably subjected to chromium plating treatment. The material of the rubber roll is not particularly limited, and examples thereof include EPDM, NBR, urethane, titanium, silicon and the like. The hardness of the rubber roll is not particularly limited, but is usually 60 to 100 °, preferably 85 to 95 °. The hardness of the rubber roll can be measured by a hardness meter according to JIS K6253. As a commercially available hardness meter, for example, a rubber hardness meter "Type-A" manufactured by Asuka Co., Ltd. is used. Specifically, the resistance of the surface of the rubber roll when the surface is pressed by a rod or the like is measured with a hardness meter.

The pressure applied to the laminate by the pressing of the metal roll and the rubber roll is preferably 0.5 to 3.0 MPa, more preferably 0.7 to 2.3 MPa in the instantaneous pressure in the sheet type Freescale (for ultra low pressure) MPa. The diameter of the bonding rolls 51 and 52 is not particularly limited, but is usually 50 to 400 mm. The diameters of the two (pair of) bonding rolls 51 and 52 may be the same or different.

(First active energy ray irradiation step)

The rotating roll 13 constitutes a convex curved surface whose outer circumferential surface is mirror-finished, and the laminated body 4 is conveyed while closely contacting the surface thereof, and in the process, the adhesive is polymerized by the active energy ray irradiating devices 31 and 32 Cure. The diameter of the rotary roll 13 is not particularly limited when the adhesive is polymerized and cured to sufficiently adhere the layered product 4. [ The rotary roll 13 is driven at a rotational speed higher than the rotational speed of the rubber roll which is driven to rotate among the pair of the bonding rolls 51 and 52. When the rotational speed of the rubber roll to be rotationally driven is 100, the rotational speed of the rotary roll 13 is preferably 100.1 to 102.0, more preferably 100.1 to 101.5 . If it is less than 100.1, wave curling tends to occur in the laminate. On the other hand, if it is more than 102.0, there is a possibility that friction between the film and the roll becomes slippery and scratches may occur.

The rotation speed of the rotary roll 13 is, for example, 10 to 50 m / min. The rotation speed of the rotary roll 13 need not be controlled constantly. For example, it may be appropriately controlled while confirming the occurrence of corrugated wrinkles in accordance with the type of film, slipperiness of the roll surface, and the like.

The rotary roll 13 may also serve as a cooling roll for dissipating heat generated in the layered product 4 during polymerization curing by irradiation of active energy rays. In this case, the surface temperature of the cooling roll is preferably set to 4 to 30 占 폚.

The light source used for polymerizing and curing the adhesive by irradiation of an active energy ray is not particularly limited, but is preferably a light source having a light emission distribution at a wavelength of 400 nm or less. Examples of such light sources include low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, ultra high pressure mercury lamps, chemical lamps, black light lamps, microwave excited mercury lamps, and metal halide lamps. It is preferable that the irradiation of the active energy ray in the first active energy ray irradiation step is performed in plural steps. Fig. 1 shows a case in which irradiation of active energy rays is performed in two steps, that is, two light sources (active energy ray irradiation devices 31 and 32) are arranged along the conveying direction of the laminate.

The light irradiation intensity for each active ray ray-curable adhesive is determined depending on the composition of the adhesive and is not particularly limited, but is preferably 10 to 5000 mW / cm 2 . When the light irradiation intensity to the resin composition is less than 10 mW / cm 2 , the reaction time becomes excessively long. When the light irradiation intensity exceeds 5000 mW / cm 2 , heat radiated from the light source and heat generated during polymerization of the composition, There is a possibility that yellowing of the epoxy resin composition or the like or deterioration of the polarizing film may occur. The irradiation intensity is preferably the intensity in the wavelength range effective for activation of the photo cationic polymerization initiator, more preferably the intensity in the wavelength range of 400 nm or less, more preferably the wavelength range of 280 to 320 nm (UVB).

When the active energy ray is ultraviolet ray, in the step of irradiating the layered product 4 with the active energy ray, a tensile force of 100 to 800 N / m is applied to the layered product 4 in the longitudinal direction (conveying direction) It is preferable that the layered product 4 is transported at a line speed of 0.1 second or more.

(Second active energy ray irradiation step)

When the accumulated energy of the active energy rays by the active energy ray irradiators 31 and 32 is insufficient, the second and subsequent active energy ray irradiators 16 to 18 are further provided, the active energy ray is further irradiated, It is preferable to accelerate the curing of the adhesive of the layered product 4. [ It is preferable that one active energy ray irradiation process and the sum of the integrated quantity of light of the whole process, 10mJ / cm 2 or more, particularly from 10 to 5,000mJ / cm 2 are to be set. If the integrated amount of light for the adhesive is less than 10 mJ / cm 2 , the generation of the active species derived from the initiator is not sufficient and the curing of the adhesive becomes insufficient. On the other hand, if the accumulated light quantity exceeds 5,000 mJ / cm 2 , the irradiation time becomes extremely long, which leads to an improvement in productivity. At this time, depending on the combination of the film to be used and the kind of the adhesive agent, it depends on what wavelength range (UVA (320 to 390 nm), UVB (280 to 320 nm), etc.)

In order to surely cure the adhesive at the end of the polarizing plate (laminate), for example, a "Light Hammer 10" manufactured by Fusion, which is an electrodeless D valve lamp, is arranged to be transverse to the running of the film And the like.

The rate at which the active energy ray-curable resin is cured, that is, the reaction rate is preferably 90% or more, and more preferably 95% or more.

(Polarizing plate winding step)

The tension for winding the laminate (polarizing plate) 4 is 30 N / cm 2 to 150 N / cm 2 . Preferably 30N / cm 2 to 120N / cm 2. If it is less than 30 N / cm 2 , it is not preferable because a winding deviation occurs when a long winding roll is fed. When it is larger than 150 N / cm 2 , the winding is likely to be tightened and sagging easily occurs.

Further, the longer the winding length becomes, the more easily the winding tension (the phenomenon in which it becomes difficult to return to the flat state when unwinding) becomes the same with the same tension, so that the tension can be continuously or stepwise lowered while the polarizing plate is wound around the core . Even in the method of lowering the tension by placing such a taper, the tension at that time is set to 150 N / cm 2 or less.

The length of the polarizing plate wound around the core is not particularly limited, but is preferably 100 m or more and 4000 m or less.

The diameter of the cylindrical core is preferably 6 inches to 12 inches. The larger diameter of the core is preferable, and 11 inches or 12 inches is more preferable, but if it is too large, transport or storage becomes difficult.

The material of the cylindrical core is not particularly limited so long as it can be used for a clean room and can secure adequate strength so that it can not oscillate and can wind a wide polarizing plate. ) Can be selected.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[Example 1]

(Production of polarizing film)

As the original film of polyvinyl alcohol, a long polyvinyl alcohol film "OPL film M-7500 (manufactured by Nippon Gosei)" having a degree of polymerization of 2400, a degree of saponification of 99.9 mol%, a thickness of 75 μm and a width of 3000 mm was used. The stretching was carried out with the peripheral speed difference between the driving nip rolls before and after the treatment tank.

First, the original film was immersed in a swelling tank containing pure water at 30 DEG C for 80 seconds while keeping the tension of the film so that the original film was not loosened, thereby sufficiently swelling the film. The ratio of the roll speed at the inlet to the exit due to swelling in the swelling bath was 1.2. After dewatering in a nip roll, it was immersed in a water immersion tank containing pure water at 30 DEG C for 160 seconds. The draw ratio in the machine direction in this tank was 1.09 times.

Next, uniaxial stretching was performed at a draw ratio of about 1.5 times while immersing in a dyeing bath containing an aqueous solution of iodine / potassium iodide / water in a weight ratio of 0.02 / 2.0 / 100. Thereafter, uniaxial stretching was carried out by soaking in a boric acid bath containing an aqueous solution of 12 / 3.7 / 100 by weight of potassium iodide / boric acid / water at 55.5 DEG C for 130 seconds, until the cumulative stretching magnification from the disk reached 5.7. Thereafter, it was immersed in a boric acid bath containing an aqueous solution of potassium iodide / boric acid / water in a weight ratio of 9 / 2.4 / 100 at 40 ° C for 60 seconds.

Then, the substrate was rinsed with pure water at 8 DEG C for about 16 seconds in a water bath, and then dried at about 60 DEG C and then at about 85 DEG C successively, and the retention time in the drying furnace was set to 160 seconds Drying was carried out. Thus, a polarizing film having a thickness of 28 mu m in which iodine was adsorbed and oriented was obtained.

(Production of polarizing plate)

As the transparent film, a cellulose acetate based resin film "KC4CR-1 (manufactured by Konica Minolta Opto)" having a thickness of 40 μm and a thickness of 80 μm and a triacetyl cellulose film "KC8UX2MW" (manufactured by Konica Minolta Co., ) Were prepared.

Using the polarizing film and the transparent film prepared as described above, a polarizing plate was produced by the apparatus shown in Fig. First, an epoxy resin composition " KR series " (manufactured by Adeka), which is an ultraviolet curable adhesive, was adhered to one side of an acetic acid cellulose resin film " KC4CR-1 " Ltd.) was used. An epoxy resin composition " KR series " (manufactured by Adeka), an ultraviolet curing type adhesive, was applied to one side of the triacetyl cellulose film " KC8UX2MW " At this time, the thickness of the adhesive layer on the cellulose acetate resin film " KC4CR-1 " was set to about 4.0 mu m, and the triacetyl cellulose film " KC8UX2MW " (The total thickness of the adhesive layer is about 7.3 mu m).

Next, on both sides of the polarizing film, the acrylic resin-based resin film " KC4CR-1 " and the triacetyl cellulose film " KC8UX2MW " (A bonding step) by means of a resin composition (ultraviolet curable adhesive).

The polarizing film to which the above two kinds of transparent films were bonded was fed at a line speed of 25 m / min while a tension of 600 N / m was applied in the longitudinal direction to the cooling roll, and a metal halide lamp 2 (GS-YUASA (Manufactured by Fusion Corporation, manufactured by Fusion Co., Ltd., electric power 130 W / cm, manufactured by Fuji Photo Film Co., Ltd.), and then the first active energy ray irradiation step was performed. 1, etc., 216 mW / cm), and the second active energy ray irradiation step was performed to produce a polarizing plate.

The above-mentioned electrodeless D-valve lamp 3 etc. were arranged in three rows in the longitudinal direction of the film, in which six electrodeless D-valve lamps were arrayed in the film width direction.

At the time of passing through the metal halide lamp, the triacetyl cellulose film "KC8UX2MW" bonded to the polarizing film was brought into contact with the outer circumferential surface of a cooling roll set at 23 ° C and irradiated with ultraviolet rays from the cellulose acetate resin film "KC4CR-1" side . The rotation speed of the rubber roll driven and rotated in the bonding step was 25.00 m / min, and the rotation speed of the cooling roll was 25.23 m / min. That is, when the rotation speed of the rubber roll was 100, the rotation speed of the cooling roll was 100.9.

The integrated light amount of the first active energy ray irradiation step and the second active energy ray irradiation step in this example was 468 mJ / cm 2 . The accumulated light quantity here is based on a measurement value by a light irradiating intensity measuring device (UV Power Fuck II manufactured by Fusion UV) at a wavelength range (UVB) of 280 to 320 nm.

(Appearance evaluation)

The appearance of the polarizing plate of Example 1 prepared as described above was observed by reflection inspection of a fluorescent lamp, and as a result, generation of corrugated wrinkles was not observed.

[Example 2]

Except that a 60 mu m-thick cycloolefin resin film " ZEONOR " (manufactured by Nippon Zeon Co., Ltd.) was used in place of the acetic acid cellulose based resin film " KC4CR- A polarizing plate of Example 2 was prepared.

(Appearance evaluation)

The appearance of the polarizing plate of Example 2 prepared as described above was observed in the same manner as in Example 1. As a result, generation of corrugated wrinkles was not observed.

[Example 3]

As a transparent film, a cycloolefin resin film "ZEONOR" (manufactured by Nippon Zeon Co., Ltd.) having a thickness of 25 μm was used in place of the acetic acid cellulose-based resin film "KC4CR-1" in place of the triacetylcellulose film "KC8UX2MW" A 25 占 퐉 thick triacetyl cellulose film " K2UAW " (manufactured by Konica Minolta Co., Ltd.) was used, and the rotation speed of the rubber roll driven and rotated in the bonding step was 25.00 m / min and the rotation speed of the cooling roll was 25.08 m / Respectively. That is, when the rotation speed of the rubber roll was 100, the rotation speed of the cooling roll was 100.3. A polarizing plate of Example 3 was produced in the same manner as in Example 1, except for this point.

(Appearance evaluation)

The appearance of the polarizing plate of Example 3 prepared as described above was observed in the same manner as in Example 1. As a result, generation of corrugated wrinkles was not observed.

[Example 4]

As a transparent film, a cycloolefin resin film "ZEONOR" (manufactured by Nippon Zeon Co., Ltd.) having a thickness of 50 μm was used in place of the acetic acid cellulose type resin film "KC4CR-1" in place of the triacetyl cellulose film "KC8UX2MW" A triacetyl cellulose film " TD60UL " (manufactured by Fuji Film Co., Ltd.) having a thickness of 60 mu m was used. The rotation speed of the rubber roll driven and rotated in the bonding step was 25.00 m / Min. That is, when the rotation speed of the rubber roll was 100, the rotation speed of the cooling roll was 101.1. A polarizing plate of Example 4 was produced in the same manner as in Example 1, except for this point.

(Appearance evaluation)

The appearance of the polarizing plate of Example 4 prepared as described above was observed in the same manner as in Example 1. As a result, generation of corrugated wrinkles was not observed.

[Example 5]

A polarizing plate was prepared in the same manner as in Example 1 except that the rotation speed of the cooling roll was 102.2 relative to the rotation speed 100 of the rubber roll driven and rotated in the joining step.

(Appearance evaluation)

The appearance of the polarizing plate of Example 5 prepared as described above was observed, and it was confirmed that the occurrence of corrugated wrinkles was not observed, but the occurrence of friction scratches was confirmed.

[Comparative Example 1]

The polarizing plate of Comparative Example 1 was produced in the same manner as in Example 1 except that the rotation speed of the cooling roll was 100, that is, the same rotation speed as the rotation speed 100 of the rubber roll driven and rotated in the joining step.

(Appearance evaluation)

The appearance of the polarizing plate of Comparative Example 1 produced as described above was observed, and the occurrence of corrugated wrinkles was confirmed.

The polarizing plate of the present invention can be effectively applied to various display devices including a liquid crystal display device.

1: polarizing film
2, 3: Transparent film
4: laminate (polarizer)
11, 12: Adhesive coating device
13: rotating roll (cooling roll)
16, 17, 18, 31, 32: an active energy ray irradiation device
19: Return nip roll
20: winding roll

Claims (4)

A method for producing a polarizing plate comprising a polarizing film and a transparent film bonded to one or both sides of the polarizing film,
An adhesive applying step of applying an active energy ray-curable adhesive to one surface of the transparent film or one surface or both surfaces of the polarizing film;
A laminated body in which the transparent film is laminated on one or both sides of the polarizing film through the adhesive is sandwiched between a pair of bonding rolls which are rotated in the carrying direction to apply pressure to the laminated body, A joining step of joining the polarizing film,
A first active energy ray irradiation step of irradiating an active energy ray to the laminate to cure the adhesive while conveying the laminate in a state of being closely contacted with a rotating roll rotationally driven in the carrying direction, ,
At least one of the pair of bonding rolls is a rubber roll which is rotationally driven with a surface including rubber,
Wherein the rotating speed of the rotating roll is faster than the rotating speed of the rubber roll. The method of manufacturing a polarizing plate according to claim 1, wherein the surface of the laminated body in contact with the rubber roll in the joining step is in contact with the rotating roll in the first active energy ray irradiation step. The method of manufacturing a polarizing plate according to claim 1 or 2, wherein the rotating roll is a cooling roll. The method of manufacturing a polarizing plate according to claim 1 or 2, wherein the rotating speed of the rotating roll is 100.1 or more and 102.0 or less when the rotating speed of the rubber roll is 100.
KR1020147011642A 2011-10-07 2012-10-02 Method for manufacturing polarizer KR101935080B1 (en)

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