CN107703577B - Polarizing plate and method for manufacturing same - Google Patents
Polarizing plate and method for manufacturing same Download PDFInfo
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- CN107703577B CN107703577B CN201710668721.3A CN201710668721A CN107703577B CN 107703577 B CN107703577 B CN 107703577B CN 201710668721 A CN201710668721 A CN 201710668721A CN 107703577 B CN107703577 B CN 107703577B
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- polarizing plate
- polyvinyl alcohol
- alcohol resin
- acetoacetyl
- modified polyvinyl
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
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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
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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
- C09J11/04—Non-macromolecular additives inorganic
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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
- C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
- C09J129/02—Homopolymers or copolymers of unsaturated alcohols
- C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- 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
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Polarising Elements (AREA)
Abstract
The present invention relates to a polarizing plate and a method for producing the same, and more particularly, to a polarizing plate and a method for producing the same, wherein the polarizing plate has a water content of 2.8 to 4.8%, and the thickness of an adhesive layer formed of an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions is 30 to 200 nm.
Description
Technical Field
The present invention relates to a polarizing plate exhibiting excellent water resistance and capable of preventing deterioration of optical characteristics, and a method for manufacturing the same.
Background
The polarizing plate can be used as one of optical members constituting a liquid crystal display device. The polarizing plate generally has a structure in which protective films are laminated on both surfaces of a polarizer, and is inserted into a liquid crystal display device. It is also known to provide a protective film only on one side of the polarizer, but in many cases, a layer having another function, for example, an optical function is joined to the other side not simply as a protective film but as a protective film.
A polarizing plate having the following structure is generally used: a polarizer is formed by using an iodine-based film in which iodine is adsorbed and oriented to polyvinyl alcohol and a dye-based film in which a dichroic dye is adsorbed and oriented to polyvinyl alcohol, and a protective film such as triacetyl cellulose (TAC) is bonded to at least one surface of the film via an adhesive layer formed using an aqueous solution of a polyvinyl alcohol-based resin (polyvinyl alcohol-based adhesive).
Thus, the following polarizing plate is proposed: the moist heat resistance is improved by joining a polarizer (polarizing film) and a protective film with a polyvinyl alcohol adhesive and then heating and drying the resultant film at a temperature of 80 to 100 ℃, but the problem that the protective film is easily peeled from the end face of the polarizer when the film is used under moist heat for a long time has not been solved.
In order to solve such a problem, patent document 1 discloses an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a polyvinyl alcohol resin (crosslinking modifier), a glyoxal (crosslinking agent), and zinc chloride (crosslinking catalyst). However, in the case of the above composition, there are problems as follows: since the crosslinking modifier is contained, the curing speed is slow, resulting in a decrease in the degree of polarization caused by deterioration due to moist heat.
Therefore, in order to prevent the protective film from separating from the short side of the polarizer even under moist heat conditions, development of an adhesive composition having excellent water resistance and capable of preventing a decrease in optical characteristics due to the excellent water resistance is currently required.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 1995-134212
Disclosure of Invention
Problems to be solved by the invention
In order to solve the above problems, an object of the present invention is to provide a polarizing plate exhibiting excellent water resistance and capable of preventing a decrease in optical characteristics, and a method for manufacturing the same.
Means for solving the problems
In order to achieve the above object, the polarizing plate of the present invention is characterized in that the water content is 2.8 to 4.8%, and the thickness of the adhesive layer formed of an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions is 30 to 200 nm.
In order to achieve the above object, a method for manufacturing a polarizing plate according to the present invention includes: (a) a step of applying an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions to both surfaces of a polarizer to form an adhesive layer; (b) a step of manufacturing a polarizing plate by bonding at least one protective film on the adhesive layer by a nip roll; and (c) drying the polarizing plate through at least 2 drying passages.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the polarizing plate of the present invention, the water content and the thickness of the adhesive layer are adjusted, thereby improving the water resistance without degrading the optical characteristics.
In addition, the polarizing plate manufactured by the method for manufacturing a polarizing plate according to the present invention also has the above-described effects.
Drawings
FIG. 1 is a view schematically showing a test method for evaluating water resistance according to an experimental example.
Detailed Description
In the present invention, when a certain component is "included" in a certain portion, unless otherwise specified to the contrary, it does not exclude other components, and means that other components can be further included.
Preferred embodiments of the present invention will be described in detail below.
< polarizing plate >
According to the polarizing plate of one embodiment of the present invention, the moisture content is 2.8 to 4.8%, and the thickness of the adhesive layer formed of the adhesive composition containing the acetoacetyl-modified polyvinyl alcohol resin, the glyoxal crosslinking agent, and the water-soluble salt of 2 or more polyvalent metal ions is 30 to 200nm, whereby the following effects are obtained: the protective film is prevented from separating from the short side of the polarizer even under wet heat conditions without accompanying a decrease in optical characteristics, and therefore, the water resistance can be improved.
The moisture content of the polarizing plate means a moisture content measured by the following weight moisture content measurement method: the weight change of the polarizing plate completed after completion of all the drying steps was observed before/after the heat treatment at 105 ℃ for 2 hours.
The polarizing plate in the present invention may mean a polarizing plate used in the art, and may be, for example, a polarizing plate obtained by bonding at least one protective film to at least one surface of a polarizer.
Adhesive layer
The polarizing plate of the present invention has an effect of improving water resistance by including an adhesive layer having a thickness of 30 to 200nm and formed of an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more kinds of polyvalent metal ions, and preventing separation of a protective film from a short side of a polarizer even under a moist heat condition without accompanying a decrease in optical characteristics, and when the thickness of the adhesive layer is less than 30nm, a problem in appearance may occur, and when the thickness exceeds 200nm, deterioration in moist heat may occur, and a problem of a decrease in optical characteristics may occur.
The adhesive composition includes: the liquid a containing the acetoacetyl group-modified polyvinyl alcohol resin and the glyoxal crosslinking agent and the liquid B containing the acetoacetyl group-modified polyvinyl alcohol resin and the water-soluble salt of 2 or more polyvalent metal ions can be produced by mixing the liquid a and the liquid B.
The acetoacetyl group-modified polyvinyl alcohol resin contained in each of the solutions a and B may be mixed with water (distilled water) in the form of an aqueous solution, and the content of the solid content of the acetoacetyl group-modified polyvinyl alcohol resin contained in each of the solutions a and B is 2.5 to 4.5 wt% based on 100 wt% of the acetoacetyl group-modified polyvinyl alcohol resin aqueous solution, whereby the following effects are exhibited: the protective film is prevented from separating from the short side of the polarizer even under a moist heat condition without causing a decrease in optical characteristics, and thus the water resistance can be improved. Specifically, when the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in each of the solutions a and B is less than 2.5%, the water resistance effect may be deteriorated, and when it exceeds 4.5%, the optical characteristics may be deteriorated.
Acetoacetyl-modified polyvinyl alcohol resin
The adhesive composition contained in the adhesive layer of the present invention can improve the adhesion between the protective film and the polarizer by containing the acetoacetyl-modified polyvinyl alcohol resin.
The acetoacetyl group-modified polyvinyl alcohol resin contains a functional group having a higher reactivity than a modified polyvinyl alcohol resin such as a carboxyl group-modified polyvinyl alcohol resin, a hydroxymethyl group-modified polyvinyl alcohol resin, or an amino group-modified polyvinyl alcohol resin, and is excellent in improvement of durability.
The acetoacetyl-modified polyvinyl alcohol resin is obtained by reacting a polyvinyl alcohol resin with a dienone (diketene) by a known method. Specifically, a method of adding a dienone to a polyvinyl alcohol resin after dispersing the resin in a solvent such as acetic acid; a method in which a polyvinyl alcohol resin is dissolved in advance in a solvent such as dimethylformamide or dioxane, and then a dienone is added thereto; or a method in which a polyvinyl alcohol resin is directly contacted with a dienone gas or liquid dienone.
The acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited as long as the acetoacetyl group modification degree is 0.1 mol% or more, but is preferably 0.1 to 40 mol%, more preferably 1 to 20 mol%, and most preferably 2 to 7 mol%. When the modification degree of the acetoacetyl group is less than 0.1 mol%, the water resistance of the adhesive layer is insufficient, and thus the effect of improving the water resistance is not high, and when the modification degree of the acetoacetyl group exceeds 40 mol%.
The saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is not particularly limited, but is preferably 80 mol% or more, and more preferably 85 mol% or more. When the saponification degree of the acetoacetyl group-modified polyvinyl alcohol resin is less than the above range, it is difficult to obtain sufficient water solubility, and thus the problem of lowering the adhesiveness may occur.
The polymerization degree of the acetoacetyl-modified polyvinyl alcohol resin is preferably within a range of 100 to 1500. When the polymerization degree of the acetoacetyl-modified polyvinyl alcohol resin is within the above range, the adhesive strength between the polarizer and the protective film in the polarizing plate is improved.
Specific examples of the acetoacetyl-modified polyvinyl alcohol resin include, but are not limited to, Z-100, Z-200H, Z-210, Z-220, and Z-320 (Gohsefimer, Japan synthetic chemical Co., Ltd.).
Glyoxal crosslinking agent
The adhesive composition contained in the adhesive layer of the present invention contains a glyoxal crosslinking agent.
When the glyoxal crosslinking agent is contained, the aldehyde group in the glyoxal crosslinking agent is subjected to condensation reaction with not only the acetoacetyl-modified polyvinyl alcohol resin but also the hydroxyl group contained in the polarizer and the protective film, whereby the crosslinking degree of the adhesive composition is improved, and the adhesive strength and water resistance between the polarizer and the protective film joined by the adhesive composition are improved.
The content of the glyoxal crosslinking agent may be 30 to 70 parts by weight based on 100 parts by weight of the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in the solution a. When the content of the glyoxal crosslinking agent is less than the above range, the problem of lowering the water resistance of the adhesive layer formed from the adhesive composition containing the glyoxal crosslinking agent may occur, and when the content exceeds the above range, the problem of lowering the liquid preparation stability may occur.
Water-soluble salts of polyvalent metal ions
The adhesive composition contained in the adhesive layer of the present invention contains the water-soluble salt of 2 or more kinds of polyvalent metal ions, and therefore, not only the effect of the glyoxal crosslinking agent is promoted and the crosslinking degree of the adhesive composition containing the glyoxal crosslinking agent is improved, but also the crosslinking degree between the polarizer and the protective film to be bonded by the glyoxal crosslinking agent is improved. This has the following effect: the adhesive strength and water resistance of the adhesive layer can be improved, and the reduction of optical durability associated therewith can be prevented.
The water-soluble salt of the polyvalent metal ion is specifically selected from zinc chloride, cobalt chloride, magnesium acetate, aluminum nitrate, zinc nitrate and zinc sulfate, and more preferably selected from zinc chloride, zinc nitrate and aluminum nitrate which are excellent in the action of the crosslinking catalyst.
When the water-soluble salt of a polyvalent metal ion contains zinc chloride, the content thereof may be 2 to 10 parts by weight based on 100 parts by weight of the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in the liquid B. When the content of zinc chloride is less than the above range, a problem of insufficient water resistance of the adhesive layer formed from the adhesive composition containing zinc chloride may occur, and when the content exceeds the above range, a problem of lowering the liquid preparation stability may occur.
When the water-soluble salt of a polyvalent metal ion contains zinc nitrate or aluminum nitrate, the content thereof may be 30 to 90 parts by weight based on 100 parts by weight of the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in the solution B. When the content of zinc nitrate or aluminum nitrate is less than the above range, the water resistance of the adhesive layer formed from the adhesive composition containing zinc nitrate or aluminum nitrate may be insufficient, and when the content exceeds the above range, the liquid mixing stability may be lowered.
The viscosity of the adhesive composition contained in the adhesive layer of the present invention at 20 ℃ is preferably in the range of 3 to 25 mPasec. When the viscosity of the adhesive composition is less than 3mPa · sec, the water resistance of the adhesive layer formed from the adhesive composition cannot be sufficiently exhibited, and when the viscosity exceeds 25mPa · sec, there is a problem that the optical characteristics of the polarizing plate including the adhesive layer are degraded.
The adhesive composition may further contain additives such as a plasticizer, a silane coupling agent, an antistatic agent, fine particles, an alcohol for improving the spreadability, and a leveling agent, in a range not to impair the effects of the present invention.
The form of the adhesive composition is not particularly limited, and a liquid type is preferable in order to form a uniform adhesive layer on the surface of the polarizer and the protective film as the adherend. As such a liquid type adhesive, a solution type or a dispersion type using various solvents can be used, and a solution type is preferable in view of the coatability of the substrate, and a solution type or a dispersion type using water as a solvent is preferable in view of the stability.
Polarizer (polarizing film)
The polyvinyl alcohol resin used for forming the polarizer is obtained by saponifying a polyvinyl acetate resin. Examples of 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 the other monomer copolymerizable with vinyl acetate include unsaturated carboxylic acids, unsaturated sulfonic acids, olefins, vinyl ethers, and acrylamides having an ammonium group. The saponification degree of the polyvinyl alcohol resin is usually 85 to 100 mol%, preferably 98 mol% or more. The polyvinyl alcohol resin may be further modified, and for example, a polyvinyl alcohol polymer modified with an aldehyde, polyvinyl acetal, or the like can be used. The polyvinyl alcohol resin constituting the polarizer has an average polymerization degree of usually 1000 to 10000, preferably 1500 to 5000.
The product (polyvinyl alcohol resin film) obtained by forming such a polyvinyl alcohol resin on a film is used for a master film of a polarizer. The method for forming the film from the polyvinyl alcohol resin is not particularly limited, and a known film forming method can be used. The thickness of the polyvinyl alcohol resin film to be a master is not particularly limited, and may be, for example, 10 to 150 μm.
Polarizers can generally be manufactured by a process comprising: the method for producing a master printing plate comprises the steps of uniaxially stretching the polyvinyl alcohol resin film to be a master printing plate, dyeing the polyvinyl alcohol resin film with a dichroic dye and adsorbing the dichroic dye, treating the polyvinyl alcohol resin film adsorbed with the dichroic dye with an aqueous boric acid solution, and washing with water after the treatment with the aqueous boric acid solution.
The uniaxial stretching may be carried out before dyeing, simultaneously with dyeing, or after dyeing. In the case of uniaxial stretching after dyeing, the uniaxial stretching may be performed before the boric acid treatment, may be performed during the boric acid treatment, or may be performed after the boric acid treatment. Of course, uniaxial stretching can also be performed by their multiple steps. In the uniaxial stretching, the original film may be uniaxially stretched between different rolls, or may be uniaxially stretched by a heat roll. Further, dry stretching such as stretching in the air may be used, or wet stretching may be used in which stretching is performed in a state of being swollen with a solvent. The draw ratio is usually 3 to 8 times.
In order to dye the polyvinyl alcohol resin film with the dichroic dye, for example, the polyvinyl alcohol resin film may be immersed in an aqueous solution containing the dichroic dye. As the dichroic dye, specifically, iodine or a dichroic dye may be used. The polyvinyl alcohol resin film is preferably subjected to an immersion treatment in water before the dyeing treatment.
When iodine is used as the dichroic dye, a method of immersing the polyvinyl alcohol resin film in an aqueous solution containing iodine and potassium iodide to dye the film is generally used. The aqueous solution generally contains 0.01 to 1 part by weight of iodine per 100 parts by weight of water, and the aqueous solution generally contains 0.5 to 20 parts by weight of potassium iodide per 100 parts by weight of water. The temperature of the aqueous solution used for dyeing is usually 20 to 40 ℃, and the immersion time in the aqueous solution is usually 20 to 1800 seconds.
When a dichroic dye is used as the dichroic dye, a method of immersing a polyvinyl alcohol resin film in an aqueous solution containing a water-soluble dichroic dye to dye the film is generally used. The content of the dichroic dye in the aqueous solution is usually 1 × 10 with respect to 100 parts by weight of water-4About 10 parts by weight, preferably about 1X 10-3About 1 part by weight. The aqueous solution may also contain an inorganic salt such as sodium sulfate as a dyeing auxiliary. The temperature of the aqueous dye solution used for dyeing is usually 20 to 80 ℃, and the immersion time of the aqueous dye solution is usually 10 to 1800 seconds.
The boric acid treatment after dyeing with the dichroic dye is performed by immersing the dyed polyvinyl alcohol-based resin film in an aqueous solution containing boric acid. The amount of boric acid in the aqueous solution containing boric acid is usually 2 to 15 parts by weight, preferably 5 to 12 parts by weight, relative to 100 parts by weight of water. When iodine is used as the dichroic dye, the aqueous solution containing boric acid preferably contains potassium iodide. The amount of potassium iodide in the aqueous solution containing boric acid is usually 0.1 to 15 parts by weight, preferably 5 to 12 parts by weight, based on 100 parts by weight of water. The immersion time in the aqueous solution containing boric acid is usually 60 to 1200 seconds, preferably 150 to 600 seconds, and more preferably 200 to 400 seconds. The temperature of the aqueous solution containing boric acid is usually 50 ℃ or higher, preferably 50 to 85 ℃, and more preferably 60 to 80 ℃.
The polyvinyl alcohol resin film after the boric acid treatment is usually subjected to a water washing treatment. The water washing treatment is performed by, for example, immersing the boric acid-treated polyvinyl alcohol resin film in water. The temperature of water in the water washing treatment is usually 5-40 ℃, and the dipping time is usually 1-120 seconds. After washing with water, drying treatment was performed to obtain a polarizer. The drying treatment is usually carried out by a hot air dryer or a far infrared heater. The temperature of the drying treatment is usually 30 to 100 ℃, preferably 50 to 80 ℃. The drying time is usually 60 to 600 seconds, preferably 120 to 600 seconds.
The polyvinyl alcohol resin film was uniaxially stretched, dyed with a dichroic dye, and subjected to boric acid treatment in this manner, to obtain a polarizer. The thickness of the polarizer is usually in the range of 5 to 40 μm, preferably in the range of 10 to 35 μm.
Protective film
As the protective film, various transparent resin films such as a cellulose resin film, a cycloolefin resin film, an acrylic resin film, and a polyester resin film can be specifically used.
When a cellulose resin film is used as the protective film, a cellulose acetate resin in which at least a part of cellulose is esterified is preferable. Examples thereof include triacetyl cellulose, diacetyl cellulose, and cellulose acetate propionate.
The cycloolefin resin is, for example, a thermoplastic resin having a monomer unit of a cycloolefin such as norbornene or polycyclic norbornene monomers, and may be a hydrogenated product of a ring-opened polymer of the cycloolefin or a ring-opened copolymer using 2 or more kinds of the cycloolefin, or an addition copolymer of the cycloolefin and a chain olefin or an aromatic compound having a vinyl group. In addition, a polar group may be introduced into the cycloolefin resin.
The method of bonding the polarizer and the protective film using the adhesive composition is not particularly limited, and examples thereof include the following methods: the adhesive composition is applied to the adhesive surface of the polarizer and/or the protective film by a casting method, a bar coating method, a gravure coating method, a die coating method, a dip coating method, a spraying method, or the like, and the two are superimposed. The above-mentioned casting method is a method of applying an adhesive composition to the surface of a polarizer or a protective film as an object to be applied while moving the polarizer or the protective film in a substantially vertical direction, a substantially horizontal direction, or an oblique direction therebetween.
After the adhesive composition was applied, the polarizer and the protective film were sandwiched between nip rolls (nip rolls) to bond them.
In addition, in order to improve the adhesiveness, the surface of the polarizer and/or the protective film may be appropriately subjected to surface treatment such as plasma treatment, corona treatment, ultraviolet irradiation treatment, flame treatment, and saponification treatment. The saponification treatment may be carried out by immersing the resin in an aqueous alkaline solution such as sodium hydroxide or potassium hydroxide.
After laminating the polarizer and the protective film, drying treatment is performed. The drying treatment is performed by spraying hot air, for example, and the temperature at this time is appropriately selected from the range of 50 to 100 ℃. The drying time is usually 30 to 1000 seconds.
< method for producing polarizing plate >
Another embodiment of the present invention is a method of manufacturing the polarizing plate, including: (a) a step of applying an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions to both surfaces of a polarizer to form an adhesive layer; (b) a step of bonding at least one protective film to the adhesive layer by a nip roll to produce a polarizing plate; (c) the polarizing plate passes through at least 2 drying passages to be dried. The method can make the water content of the polarizing plate to be 2.8-4.8%, and the thickness of the adhesive layer contained in the polarizing plate to be 30-200 nm. Therefore, a polarizing plate having the following effects can be manufactured: the protective film is prevented from being separated from the short side of the polarizer even under a wet heat condition without causing a decrease in optical characteristics, and thus the water resistance can be improved
In the method for manufacturing a polarizing plate of the present invention, the above-described constituent elements of the polarizing plate can be used as the constituent elements of the polarizing plate unless otherwise described below.
In the step (b), the nip rolls are a machine for bonding the protective film to at least one surface of the polarizer, at least 1 or more nip rolls are provided in the upper and lower surfaces of the polarizer and the protective film, respectively, and the nip rolls positioned on the upper and lower surfaces of the polarizer and the protective film can bond the protective film to the polarizer by applying pressure to the polarizer and the protective film passing therebetween.
The nip pressure, which is the pressure of the nip roll applied for bonding the polarizer and the protective film, may be 0.3 to 0.9MPa, and when the nip pressure is less than the above range, the adhesive layer between the polarizer and the protective film exceeds 200nm, which is the configuration of the present invention, and the moisture and heat deterioration occurs, and the optical characteristics are degraded, and when the nip pressure exceeds the above range, the adhesive layer does not reach 30nm, which is the configuration of the present invention, and the appearance may be deteriorated.
The nip gap (nipgap), which is the distance between the partial surface of the nip roll that contacts the upper surface of the protective film and the partial surface of the nip roll that contacts the lower surface of the protective film and the polarizer, can be-1500 to 500 μm. When the nip gap is less than the above range, the adhesive layer has a thickness of less than 30nm, which is the configuration of the present invention, and thus appearance defects may occur, and when the nip gap exceeds the above range, the adhesive layer has a thickness of more than 200nm, which is the configuration of the present invention, and thus deterioration of the wet heat and deterioration of the optical characteristics may occur. In this case, the nip rolls positioned above and below the polarizer and the protective film used for measuring the nip gap are the closest nip rolls to each other.
In the present invention, for convenience, the plurality of drying paths are named as a 1 st drying path, a 2 nd drying path, a 3 rd drying path, and the like in order of passing the polarizing plate. The drying passage may use hot air, and when the polarizing plate passes through at least 2 drying passages, the temperature of the hot air in the drying passage in the subsequent stage is preferably higher than the temperature of the hot air in the drying passage in the previous stage. For example, the temperature of the hot air in the 2 nd drying passage is higher than the temperature of the hot air in the 1 st drying passage. More specifically, the temperature of the hot air in the 1 st drying passage is preferably 50 ℃ or lower, and the temperature of the hot air in the last drying passage among the plurality of drying passages is preferably 80 ℃ or higher. When the temperature in the first drying passage 1 exceeds 50 ℃, the moisture-heat deterioration occurs due to rapid moisture evaporation, and the optical characteristics are degraded, and when the temperature of the hot air in the last drying passage is less than 80 ℃, the moisture percentage of the polarizing plate increases, and the optical characteristics are degraded with time.
< image display apparatus >
Another aspect of the present invention is an image display device including the polarizing plate.
The image display device of the present invention includes the polarizing plate, and specific examples thereof include, but are not limited to, a liquid crystal display, an OLED, a flexible display, and the like.
It is apparent to those skilled in the art that the preferred embodiments are set forth below to help understand the present invention, and the following embodiments are merely illustrative of the present invention, and various changes and modifications can be made within the scope and technical idea of the present invention, and such changes and modifications belong to the appended patent claims, as well as are of course apparent. In the following examples and comparative examples, "%" and "part(s)" representing the content are based on weight unless otherwise specified.
Production example
Production example 1 production of polarizer
A75 μm-thick polyvinyl alcohol film having an average polymerization degree of 2400 and a saponification degree of 99.9 mol% or more was uniaxially stretched in a dry state by about 5 times, immersed in water (distilled water) at 60 ℃ for 1 minute while maintaining the stretched state, and then immersed in an aqueous solution at 28 ℃ for 60 seconds, wherein the weight ratio of iodine/potassium iodide/distilled water was 0.05/5/100. Then, the substrate was immersed in an aqueous solution of potassium iodide/boric acid/distilled water at 72 ℃ in a weight ratio of 8.5/8.5/100 for 300 seconds, washed with distilled water at 26 ℃ for 20 seconds, and dried at 65 ℃ to prepare a polarizer in which iodine was adsorbed and oriented to a PVA-based film.
Production example 2 production of protective film
KC8UX (Konika, T) as a triacetylcellulose film was used by saponification.
Production example 3 production of adhesive composition
Preparation of liquid a composition: an acetoacetyl group-modified polyvinyl alcohol resin (ゴ - セノ - ル Z200, Nippon synthetic chemical industries, Ltd.) having a saponification degree of 99.2 mol% was dissolved in water (distilled water) to prepare an aqueous solution having a solid content shown in Table 1. A 40% aqueous solution (dahlia gold) of a glyoxal crosslinking agent was added to the aqueous solution at the content shown in table 1, and then mixed to prepare an adhesive a liquid composition.
Preparation of liquid B composition: an acetoacetyl group-modified polyvinyl alcohol resin (ゴ - セノ - ル Z200, manufactured by japan synthetic chemical industries, ltd.) having a saponification degree of 99.2 mol% was dissolved in water (distilled water) to prepare an aqueous solution having a solid content shown in table 1. Zinc chloride (dahlia gold) and zinc nitrate (dahlia gold) as water-soluble salts of polyvalent metal ions were added to the aqueous solution in the amounts shown in table 1 and mixed to prepare an adhesive B liquid composition.
The above-prepared liquid a composition and liquid B composition were mixed at room temperature and stirred for about 30 minutes to prepare an adhesive composition.
Examples 1 to 8 and comparative examples 1 to 7: manufacture of polarizing plate
The adhesive composition produced by the method of production example 3 was applied to both surfaces of the polarizer produced in production example 1 at the content shown in table 1, and then the protective films of production example 2 were bonded by nip rolls. In this case, the polarizing plates joined by the nip rolls were dried by the hot air dryer in the drying passage under the process conditions (nip pressure and nip gap) as shown in table 1. The drying process was performed in a total of 5 stages, and the temperature of the hot air in the 1 st drying passage and the temperature of the hot air in the 5 th drying passage were as shown in table 1, and the temperature of the hot air in the 2 nd drying passage was 50 ℃, the temperature of the hot air in the 3 rd drying passage was 70 ℃, the temperature of the hot air in the 4 th drying passage was 75 ℃, and the polarizing plate was finally manufactured by drying in each drying passage for 5 minutes. The moisture content of the polarizing plate thus produced and the thickness of the adhesive layer contained in the polarizing plate were measured and are shown in table 1.
In this case, the moisture content of the polarizing plate was measured by a gravimetric moisture content measuring method in which the change in weight before/after the heat treatment at 105 ℃ for 2 hours was observed.
[ TABLE 1 ]
Examples of the experiments
EXAMPLE 1 evaluation of adhesion (evaluation of cutting tool)
The polarizing plate manufactured as described above was left to stand at room temperature for 1 hour, and then the blade of the cutting tool was inserted between the films of the polarizing plate (between the polarizer and the polarizer protective film), and the manner of blade penetration when the blade was pushed forward was evaluated according to the following criteria, and the results are shown in table 2.
Very good: the edge of the cutting tool does not enter between all of the membranes.
O: when the blade is pushed forward, the blade stops when entering 1-2 mm between at least any one of the films.
And (delta): when the blade is pushed forward, the blade stops when entering 3-5 mm between at least any one of the films.
X: when the blade is pushed forward, the blade easily enters between at least any one of the films.
Experimental example 2 evaluation of Water resistance
The water resistance of each polarizing plate left alone for 24 hours in an environment of 23 ℃ and 55% relative humidity was evaluated by a hot water resistance test in the following manner.
The polarizing plate was cut into a size of 5 × 2cm with the absorption axis of the polarizing plate as the long side to prepare a sample, and the dimension in the long side direction was accurately measured. At this time, the sample uniformly showed a unique color over the entire surface due to iodine adsorbed to the polarizing film. Fig. 1 is a diagram schematically showing a method for evaluating water resistance, wherein (a) shows sample 1 before immersion in warm water, and (B) shows sample 1 after immersion in warm water. As shown in FIG. 1(A), one short side of the sample was held by a holder 5, and about 80% of the sample in the longitudinal direction was immersed in a water bath at 60 ℃ for 8 hours. Then, the sample 1 was taken out from the water tank, and water was wiped off.
By the immersion in warm water, the polarizer 4 of the polarizing plate contracts. The degree of shrinkage of the polarizer 4 was evaluated by measuring the distance from the terminal portion 1a (terminal end of the protective film) at the center of the short side of the sample 1 to the end of the polarizer 4 to be shrunk, and the length was set as the shrinkage length. As shown in fig. 1(B), by immersing in warm water, the polarizer 4 located at the center of the polarizer is contracted, so that iodine is eluted from the peripheral edge of the polarizer 4 between the protective films, and a discolored portion 3 is generated at the peripheral edge of the sample 1. Such a degree of discoloration was evaluated by measuring the distance from the terminal portion of the polarizer 4, which has shrunk at the center of the short side of the sample 1, to the region where the color unique to the polarizing plate remains, and the length of iodine discoloration was set. The sum of the shrinkage length and the iodine decolorization length was defined as a total etching length x. The total etched length x is the distance from the end 1a of the sample 1 at the center of the short side of the sample 1 to the region where the color peculiar to the polarizing plate remains. The smaller the shrinkage length, the iodine decolorization length, and the total etching length x, the higher the adhesiveness in the presence of water can be judged. The results of evaluation on the basis of the total etched length x by the following 4-degree scale are shown in Table 2.
Very good: the total etched length x is less than 0.1mm
O: the total etching length x is more than 0.1mm and less than 0.5mm
And (delta): the total etching length x is more than 0.5mm and less than 2mm
X: the total etching length x is more than 2mm
EXAMPLE 3 transmittance, degree of polarization (%)
The polarizing plate thus produced was cut into a size of 4cm × 4cm to prepare a test piece, the test piece was attached to a measurement holder, and the measurement was performed by an ultraviolet-visible spectrometer (V-7100, manufactured by JASCO Corporation), and the results are shown in table 2.
[ TABLE 2 ]
| Adhesion Property | Water resistance | Transmittance of light | Degree of polarization | |
| Example 1 | ◎ | ◎ | 43.1 | 99.996 |
| Example 2 | ◎ | ◎ | 42.9 | 99.997 |
| Example 3 | ◎ | ◎ | 42.8 | 99.997 |
| Example 4 | ◎ | ◎ | 42.8 | 99.997 |
| Example 5 | ◎ | ◎ | 42.9 | 99.997 |
| Example 6 | ◎ | ◎ | 43 | 99.995 |
| Example 7 | ◎ | ◎ | 43 | 99.993 |
| Example 8 | ◎ | ◎ | 42.9 | 99.996 |
| Comparative example 1 | ◎ | ○ | 43 | 99.997 |
| Comparative example 2 | ◎ | ◎ | 43 | 99.992 |
| Comparative example 3 | ◎ | ○ | 42.8 | 99.995 |
| Comparative example 4 | ◎ | ◎ | 42.9 | 99.996 |
| Comparative example 5 | ◎ | ○ | 42.9 | 99.992 |
| Comparative example 6 | ◎ | △ | 43 | 99.995 |
| Comparative example 7 | ◎ | △ | 42.9 | 99.995 |
Referring to table 2, it was confirmed that when the content of the solid content in the aqueous solution of the acetoacetyl-modified polyvinyl alcohol resin is less than the preferable range (2.5 to 4.5 wt%) of the present invention (comparative example 1), the moisture content of the polarizing plate is insufficient and the water resistance is poor as compared with the case where the preferable range of the present invention is satisfied (examples 1 to 8), and when the content exceeds the above range (comparative example 2), the moisture content of the polarizing plate increases, the thickness of the adhesive layer contained in the polarizing plate increases, and the optical characteristics deteriorate. In addition, when the process conditions (pressing pressure and pressing gap) of the polarizing plate of the present invention were out of the range of the present invention (comparative examples 3 to 4), it was confirmed that the water resistance and optical characteristics were degraded by producing a polarizing plate out of the ranges of the moisture percentage of the polarizing plate and the thickness of the adhesive layer contained in the polarizing plate required in the present invention. In the case where the temperature of the hot air in the 1 st drying passage during the drying of the polarizing plate exceeds the temperature range (50 ℃ or less) of the present invention (example 7), the moisture percentage of the polarizing plate and the thickness range of the adhesive layer contained in the polarizing plate required in the present invention can be satisfied, but the problem that the optical characteristics are slightly lowered as compared with the case where the temperature range is satisfied (examples 1 to 6 and 8), and in the case where the temperature range of the hot air in the 5 th drying passage deviates from the temperature range (80 ℃ or more) of the present invention (comparative example 5), it is confirmed that the moisture percentage of the polarizing plate required in the present invention is exceeded and the water resistance and the optical characteristics are lowered. In addition, when only 1 water-soluble salt of polyvalent metal ion was used (comparative examples 6 and 7), it was confirmed that the water resistance was lowered.
Claims (13)
1. A polarizing plate, comprising: a protective film bonded to at least one surface of a polarizer via an adhesive layer, wherein the water content of the polarizer is 2.8 to 4.8%, the adhesive layer is formed from an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions, the thickness of the adhesive layer is 30 to 200nm, and the adhesive composition contains: the liquid A containing an acetoacetyl-modified polyvinyl alcohol resin aqueous solution and a glyoxal crosslinking agent and the liquid B containing an acetoacetyl-modified polyvinyl alcohol resin aqueous solution and 2 or more kinds of water-soluble salts of polyvalent metal ions are contained in an amount of 2.5 to 4.5% by weight in terms of the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in each of the liquid A and the liquid B, based on 100% by weight of the acetoacetyl-modified polyvinyl alcohol resin aqueous solution.
2. The polarizing plate of claim 1, wherein the water-soluble salt of the polyvalent metal ion is 2 or more selected from zinc chloride, zinc nitrate, and aluminum nitrate.
3. The polarizing plate according to claim 1, wherein the acetoacetyl-modified polyvinyl alcohol resin has an average degree of polymerization of 100 to 1500.
4. The polarizing plate according to claim 1, wherein the content of the glyoxal crosslinking agent in liquid A is 30 to 70 parts by weight based on 100 parts by weight of the total solid content of the acetoacetyl-modified polyvinyl alcohol resin in liquid A.
5. The polarizing plate according to claim 1, wherein the water-soluble salt of a polyvalent metal ion contains 2 or more selected from zinc chloride, zinc nitrate and aluminum nitrate, and the content of the zinc chloride is 2 to 10 parts by weight based on 100 parts by weight of the total solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in the solution B.
6. The polarizing plate according to claim 1, wherein the water-soluble salt of a polyvalent metal ion contains 2 or more selected from zinc chloride, zinc nitrate and aluminum nitrate, and the content of the zinc nitrate or the aluminum nitrate is 30 to 90 parts by weight based on 100 parts by weight of the total solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in the solution B.
7. An image display device comprising the polarizing plate according to any one of claims 1 to 6.
8. A method for manufacturing a polarizing plate having a water content of 2.8 to 4.8% and a thickness of an adhesive layer contained in the polarizing plate of 30 to 200nm, the method comprising:
(a) applying an adhesive composition containing an acetoacetyl-modified polyvinyl alcohol resin, a glyoxal crosslinking agent, and a water-soluble salt of 2 or more polyvalent metal ions to both surfaces of a polarizer to form an adhesive layer, the adhesive composition comprising: a liquid A containing an acetoacetyl-modified polyvinyl alcohol resin aqueous solution and a glyoxal crosslinking agent, and a liquid B containing an acetoacetyl-modified polyvinyl alcohol resin aqueous solution and at least 2 kinds of water-soluble salts of polyvalent metal ions, wherein the solid content of the acetoacetyl-modified polyvinyl alcohol resin contained in each of the liquid A and the liquid B is 2.5 to 4.5% by weight relative to 100% by weight of the acetoacetyl-modified polyvinyl alcohol resin aqueous solution;
(b) a step of manufacturing a polarizing plate by bonding at least one protective film on the adhesive layer by a nip roll; and
(c) the stage of drying the polarizing plate by at least more than 2 drying channels.
9. The method for manufacturing a polarizing plate according to claim 8, wherein a nip pressure of the nip roll applied to the polarizing plate in the stage (b) is 0.3 to 0.9 MPa.
10. The method for manufacturing a polarizing plate according to claim 8, wherein the pressing gap in the stage (b) is from-1500 μm to-500 μm.
11. The method of manufacturing a polarizing plate according to claim 8, wherein when the polarizing plate passes through at least 2 or more drying passages in the stage (c), the temperature of the hot air in the drying passage in the subsequent stage is higher than the temperature of the hot air in the drying passage in the previous stage.
12. The method of manufacturing a polarizing plate according to claim 11, wherein a temperature of the hot air in the 1 st drying passage initially existing in the at least 2 or more drying passages is 50 ℃ or lower.
13. The method of manufacturing a polarizing plate according to claim 11, wherein a temperature of hot air in a drying passage finally existing in the at least 2 or more drying passages is 80 ℃ or higher.
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| CN101363933A (en) * | 2007-08-07 | 2009-02-11 | 住友化学株式会社 | Polarizing plate and production method thereof |
| CN101813799A (en) * | 2009-02-20 | 2010-08-25 | 住友化学株式会社 | Polarization plates and manufacture method thereof |
| KR20160004187A (en) * | 2014-07-02 | 2016-01-12 | 수미토모 케미칼 컴퍼니 리미티드 | Adhesive composition and polarizing plate comprising the same |
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| JP2002221619A (en) * | 2001-01-25 | 2002-08-09 | Gunze Ltd | Polarizing plate |
| JP2005326531A (en) * | 2004-05-13 | 2005-11-24 | Nitto Denko Corp | Polarizing plate equipped with protecting film, manufacturing method therefor, and image display device using polarizing plate |
| JP2008129258A (en) * | 2006-11-20 | 2008-06-05 | Nitto Denko Corp | Method for producing polarizing plate, polarizing plate, optical film and image display device |
| JP2008180765A (en) * | 2007-01-23 | 2008-08-07 | Sumitomo Chemical Co Ltd | Manufacturing method of polarizing film |
| JP5051696B2 (en) * | 2007-04-06 | 2012-10-17 | 住友化学株式会社 | Polarizer |
| JP5147014B2 (en) * | 2008-10-08 | 2013-02-20 | 住友化学株式会社 | High contrast polarizing plate and liquid crystal display device |
| KR101211745B1 (en) * | 2009-06-24 | 2012-12-12 | 주식회사 엘지화학 | Retardation film, fabrication method thereof, and liquid crystal display comprising the same |
| JP2012047799A (en) * | 2010-08-24 | 2012-03-08 | Nitto Denko Corp | Manufacturing method of polarizer |
| KR101459126B1 (en) * | 2011-12-21 | 2014-11-07 | 제일모직주식회사 | Polarizer plate and liquid crystal display comprising the same |
| KR101397705B1 (en) * | 2011-12-30 | 2014-05-23 | 제일모직주식회사 | Adhesive composition for polarizing plate |
| WO2016002808A1 (en) * | 2014-07-02 | 2016-01-07 | 住友化学株式会社 | Adhesive composition and polarizing plate containing same |
| KR20160028316A (en) * | 2014-09-03 | 2016-03-11 | 스미또모 가가꾸 가부시키가이샤 | Adhesive composition and polarizing plate using the same |
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| CN101363933A (en) * | 2007-08-07 | 2009-02-11 | 住友化学株式会社 | Polarizing plate and production method thereof |
| CN101813799A (en) * | 2009-02-20 | 2010-08-25 | 住友化学株式会社 | Polarization plates and manufacture method thereof |
| KR20160004187A (en) * | 2014-07-02 | 2016-01-12 | 수미토모 케미칼 컴퍼니 리미티드 | Adhesive composition and polarizing plate comprising the same |
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