KR20140073673A

KR20140073673A - Polarising plate and preparation method thereof

Info

Publication number: KR20140073673A
Application number: KR1020120140845A
Authority: KR
Inventors: 유민근; 조천희
Original assignee: 동우 화인켐 주식회사
Priority date: 2012-12-06
Filing date: 2012-12-06
Publication date: 2014-06-17

Abstract

The present invention relates to a polarizing plate and a manufacturing method thereof. More specifically, the manufacturing method for the polarizing plate includes the steps of: giving a plasma discharge treatment on one or more surfaces of a polarizer protection film by using a reaction gas including a maleic acid or succinic anhydride based compound; and bonding the surface of the polarizer protection film processed during the plasma discharge treatment with a polarizer by using an adhesive composite including a polyallylamine-based resin with a specific repeating unit, an amine resin which has pH of 7-11 and is water-soluble and cationic, and a cross-linking agent. Accordingly, the polarizing plate can enable excellent adhesion with a non-adhesive protection film and maintain the adhesion strength for an extended period of time even in a high temperature and high humidity environment ny being bonded with the polarizer while maintaining optical properties at least equivalent to a conventional product.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizing plate,

The present invention relates to a polarizing plate excellent in adhesive strength and durability reliability to an anti-adhesion protective film and a method for producing the same.

2. Description of the Related Art Liquid crystal display devices (LCDs) are used in various applications such as computers, televisions, mobile phones, car navigation systems, and portable information terminals.

Such a liquid crystal display device has a liquid crystal cell composed of a liquid crystal layer, a transparent glass plate including a transparent electrode layer, or a plastic-based plate-like material arranged in a uniform manner in terms of the image forming method; It is indispensable that the polarizing plate is disposed on both surfaces of the liquid crystal cell.

Generally, the polarizer has a structure in which a polarizer in which a dichroic substance is adsorbed and oriented on a polyvinyl alcohol (PVA) resin film and a transparent polarizer protective film for protecting the polarizer on at least one side of the polarizer are stacked. The polarizer protective film may be a cellulose-based protective film such as triacetylcellulose (TAC), a cycloolefin-based protective film, or an acrylic protective film.

Such a polarizer protective film is adhered to a polarizer by an adhesive, and has a disadvantage that it is required to perform a surface treatment process suitable for the kind of the protective film or to apply the adhesive selectively.

Alkali treatment, corona treatment, plasma treatment and the like are used for the surface treatment. However, in the alkali treatment, the optical characteristics of the polarizing plate due to the unevenness or remaining alkali component may be changed, and the corona treatment and the plasma treatment have a disadvantage in that the surface treatment effect is low and the effect maintenance period is short.

The present invention can be applied regardless of the kind of the protective film, and it is possible to maintain the adhesive force even under the high adhesive force and the high temperature and high humidity condition when the anti-adhesion protective film (the uncured cellulose film, the acrylic film or the propylene film) And a method for producing the polarizing plate.

In order to attain the above object, the present invention provides a method for producing a polarizer, comprising the steps of: applying a plasma discharge treatment to at least one surface of a polarizer protective film using a reaction gas containing a maleic anhydride-based or succinic anhydride- Amine-based resin; an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic; And a step of bonding a polarizer to the plasma discharge treated surface of the polarizer protective film by using an adhesive composition comprising a crosslinking agent and a crosslinking agent.

The maleic anhydride-based or succinic anhydride-based compound may be at least one member selected from the group consisting of maleic anhydride, 2-dodecene-1-ayl succinic anhydride, citraconic anhydride and itaconic anhydride.

The reaction gas may be formed by vaporizing a maleic anhydride-based or a succinic anhydride-based compound into an inert gas.

The maleic anhydride-based or succinic anhydride-based compound may be contained in the reaction gas in an amount of 1 to 5% by volume.

The polyallylamine-based resin may have a weight average molecular weight of 1,000 to 70,000.

The polyallylamine-based resin may be a homopolymer.

The main chain of the amine-based resin may be N, N'-bis (2-aminoethyl) -1,2-ethanediamine.

The amine resin may be one obtained by further copolymerizing one or more compounds selected from the group consisting of epoxy, amino and isobenzofuran dione.

3 to 50 parts by weight of an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic, based on 100 parts by weight of a polyallylamine-based resin having a repeating unit represented by the formula (1); And 1 to 20 parts by weight of the crosslinking agent.

Further, the present invention provides a polarizing element comprising: a polarizer; An adhesive layer which is laminated on one surface or both surfaces of the polarizer and comprises a polyallylamine resin having a repeating unit represented by the formula 1, an amine resin having a pH of 7 to 11 and a water-soluble and cationic amine, and a crosslinking agent; And a polarizer protective film laminated on the adhesive layer, the polarizer protective film being plasma-treated with a reaction gas containing a maleic anhydride-based or a succinic anhydride-based compound.

The method for producing a polarizing plate according to the present invention can be easily used in the application of an anti-adhesion protective film (an uncured cellulosic film, an acrylic film, a propylene-based film, or the like), which is difficult to be bonded with an aqueous adhesive for a polarizing plate.

In addition, the method for producing a polarizing plate according to the present invention has an excellent adhesive strength while maintaining optical properties equal to or more than conventional ones, and is excellent in adhesion with a polarizer and a polarizer protective film under high temperature and high humidity conditions, .

The method for producing a polarizing plate according to the present invention comprises the steps of: performing plasma discharge processing on at least one surface of a polarizer protective film using a reaction gas containing a maleic anhydride-based or a succinic anhydride-based compound; A polyallylamine-based resin having a repeating unit represented by the following formula (1); an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic; And a step of bonding a polarizer to the plasma discharge treated surface of the polarizer protective film by using an adhesive composition comprising a crosslinking agent.

[Chemical Formula 1]

Hereinafter, the present invention will be described in detail as follows.

First, a plasma discharge treatment is performed on at least one surface of a polarizer protective film using a reaction gas containing a maleic anhydride-based or succinic anhydride-based compound.

When the plasma discharge treatment is performed by the above method, a maleic anhydride-based or succinic anhydride-based compound is introduced onto the surface of the polarizer-protective film. A polar group such as a hydroxyl group (-OH) formed by hydration and a hydrophilic group of a maleic anhydride-based or succinic anhydride-based compound on the surface of the polarizer protective film forms a bond with polyvinyl alcohol constituting the polarizer, The adhesive force can be maintained for a long time and the durability of the polarizing plate is improved. However, since the hydrophilic group of the maleic anhydride-based or succinic anhydride-based compound introduced into the surface of the protective film is weak due to moisture, there is a problem that the durability is lowered compared to the conventional process. Therefore, a polyallylamine-based resin excellent in endurance reliability, an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic; And an adhesive composition comprising a crosslinking agent is used to improve durability.

The maleic anhydride-based or succinic anhydride-based compound may be at least one selected from the group consisting of maleic anhydride, 2-dodecene-1-ayl succinic anhydride, citraconic anhydride and itaconic anhydride.

The maleic anhydride-based or succinic anhydride-based compound may be contained in the reaction gas in an amount of 1% by volume to 5% by volume. If the content is less than 1 vol%, the amount of the maleic anhydride-based or succinic anhydride-based compound to be incorporated into the protective film is insufficient to improve the adhesion. If the content is more than 5 vol%, the maleic anhydride- The adhesiveness may be lowered by the system compound.

The maleic anhydride-based or succinic anhydride-based compound is vaporized in a heatable vaporizer and used in a plasma discharge treatment apparatus together with an inert gas. The plasma discharge apparatus is generally used in the art, and its configuration is not particularly limited.

As the inert gas, a gas used for transferring the maleic anhydride-based or succinic anhydride-based compound may be used. Specifically, nitrogen, argon, helium, or the like can be used.

The vaporizer temperature is preferably 110 ° C or less, preferably 50 to 100 ° C, in consideration of the flash point of the maleic anhydride-based or succinic anhydride-based compound.

The flow rate of the reaction gas introduced into the plasma discharge treatment is controlled by the temperature of the vaporizer and the flow rate of the inert gas.

In addition, the voltage to be applied for generating the plasma is not particularly limited, and may be in the range of usually 1 to 10 kV.

Also, the operating frequency of the power supply is not particularly limited, and may be in the range of 1 kHz to 150 MHz, or more, and may be in the stronger GHz range. However, considering the influence of heat of the plasma-treated protective film, it is preferably 1 to 500 kHz.

Further, the inter-electrode distance of the plasma apparatus is determined in consideration of the pressure and concentration of the base gas, the thickness of the solid dielectric, the magnitude of the applied voltage, and the like. When the distance between the electrodes is short, a stable discharge plasma tends to be obtained, but it is generally preferably 0.5 to 50 mm. When the distance between the electrodes is less than 0.5 mm, the concentration of the reaction gas in the base gas varies greatly between the electrodes, the activation treatment tends to be uneven, and the thickness of the object to be provided between the electrodes becomes limited. In addition, when the interelectrode distance exceeds 50 mm, it is difficult to generate a uniform discharge plasma.

Polarizer protective films are those generally used in the art, and specifically include polyester films such as polyethylene terephthalate, polyethylene isophthalate, polyethylene naphthalate and polybutylene terephthalate; Cellulose-based films such as diacetylcellulose and triacetylcellulose; A polyolefin-based film having a norbornene structure; Polycarbonate film; Acrylic films such as polymethyl (meth) acrylate and polyethyl (meth) acrylate; Styrene-based films such as polystyrene and acrylonitrile-styrene copolymer; Polycarbonate-based films; Vinyl chloride film; Amide type films such as nylon and aromatic polyamide; Imidazole film; Polyethersulfone-based films; Sulfone based films; Polyether ether ketone-based films; A sulfided polyphenylene-based film; Vinyl alcohol film; Vinylidene chloride films; Polyoxymethylene-based films; Epoxy-based films, and the like.

The protective film may contain one or more suitable additives. Examples of the additives include ultraviolet absorbers, antioxidants, lubricants, plasticizers, mold release agents, coloring inhibitors, flame retardants, nucleating agents, antistatic agents, pigments and colorants.

The thickness of the protective film is usually 20 to 200 mu m.

The surface of the polarizer protective film subjected to the plasma discharge treatment in the above manner has a water contact angle in the range of 10 to 50 degrees.

Next, the step of bonding the polarizer with the plasma discharge treated surface of the polarizer protective film using an adhesive composition.

The adhesive composition of the present invention comprises a polyallylamine-based resin having a repeating unit represented by the above formula (1); an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic; And a cross-linking agent.

The polyallylamine-based resin has a repeating unit represented by the formula (1), and a homopolymer or a copolymer can be used, but a homopolymer is preferable considering physical properties such as adhesive strength and durability.

The polyallylamine resin preferably has a weight average molecular weight of 1,000 to 70,000 in order to improve the adhesiveness. When the weight average molecular weight is less than 1,000, it is difficult to obtain the desired adhesive force. When the weight average molecular weight is more than 70,000, bubbles may be incorporated during the bonding process of the polarizer and the protective film.

The amine-based resin serves to improve the adhesion (adhesion) between the polyallylamine-based resin and the polarizer and the polarizer protective film. The amine-based resin is cationic and has a pH of 7 to 11. Further, it is water-soluble in consideration of miscibility with the polyvinyl alcohol-based resin.

When an anionic resin is used, the adhesion (adhesion) between the polarizer and the polarizer protective film may be lowered. If the pH is less than 7, water resistance may be deteriorated. If the pH is more than 11, adhesion (adhesion) may be deteriorated.

The amine-based resin may be a resin containing N, N'-bis (2-aminoethyl) -1,2-ethanediamine as a main chain, and may be selected from epoxy resins, amino resins, and isobenzofuran dione resins. It is possible to more advantageously use the above-mentioned copolymer in which more than one kind of compound is copolymerized to achieve the effect of the present invention.

Commercially available products may be Sumirez Resin SPI-203 (50) H manufactured by Taoka Chemical Co., and Sumirez Resin SPI-106N manufactured by Taoka Chemical.

Such an amine resin is contained in an amount of 3 to 50 parts by weight, preferably 5 to 25 parts by weight, based on 100 parts by weight of the polyallylamine resin (based on the solid content). When the content is less than 3 parts by weight, the adhesive strength may be lowered. When the content is more than 50 parts by weight, the viscosity may be high and the processability may be deteriorated.

The crosslinking agent serves to improve the adhesion and durability of the polyallylamine-based resin, the polarizer and the polarizer protective film, the reliability at high temperature, and the shape of the pressure-sensitive adhesive.

The cross-linking agent may be an isocyanate-based, epoxy-based, peroxide-based, metal chelating-based, oxazoline-based, melamine-based, glyoxylate-based or aziridine-based one or a mixture of two or more thereof.

A glyoxylate which is advantageous in terms of double stickiness and durability is preferable.

The present invention specifically describes the glyoxylate crosslinking agent, which is a preferable crosslinking agent component in the following, but is not limited thereto.

The glyoxylate may be an alkali metal salt or an alkaline earth metal salt of glyoxylic acid. The alkali metal salt and the alkaline earth metal salt of the above-mentioned glyoxylic acid can obtain substantially the same effect, and there is no particular limitation on their use. This is presumably because both the alkali metal and the alkaline earth metal are low in electronegativity and the carboxylic acid salt of the metal or the earth metal is similar in chemical properties. In addition, since the portion acting as a crosslinking agent is an aldehyde group of the glyoxylate, it is predicted that the metal or the metal will exhibit the same effect.

Examples of the glyoxylate include alkali metal salts such as lithium glyoxylate, sodium glyoxylate and potassium glyoxylate, alkaline earth metal salts such as magnesium glyoxylate, calcium glyoxylate, strontium glyoxylate and barium glyoxylate, Can be used. In consideration of the solubility in water, an alkali metal salt is preferable, and sodium glyoxylate is particularly preferable.

Such a crosslinking agent is contained in an amount of 1 to 20 parts by weight, preferably 5 to 10 parts by weight based on 100 parts by weight of the polyallylamine resin (based on the solid content). If the content is less than 1 part by weight, the water resistance of the polarizing plate may not be sufficiently exhibited. If the content is more than 20 parts by weight, the optical characteristics (transmittance, polarization degree) of the polarizing plate may be lowered.

The adhesive composition may be used in an amount of at least one selected from the group consisting of a plasticizer, a silane coupling agent, an antistatic agent, a fine particle, an alcohol, and a leveling agent, which are generally used in the art within the range not hindering the desired effect have. In particular, in order to improve the spreadability of the composition for forming an adhesive layer, it is preferable to use an alcohol, a leveling agent or the like.

It is preferable that the adhesive composition is in a liquid form in order to form a uniform adhesive layer on the surface of the polarizer or the protective film as the adhesive. A solution type or a dispersed liquid type of various solvents can be used for such a liquid type adhesive, and a solution type is preferable in view of the coated surface of the substrate, and a solution type or a dispersed liquid type in which water is used as a solvent is suitable from the viewpoint of stability.

For the purpose of shortening the drying process, a water / alcohol mixed solvent in which an alcoholic solvent having a boiling point lower than that of water is easily mixed with water in an adhesive solution may be used. The boiling point of the alcoholic solvent is preferably 100 占 폚 or lower, particularly 80 占 폚 or lower, or 70 占 폚 or lower.

A polarizer is one in which a dichroic dye is adsorbed and oriented on a stretched polyvinyl alcohol-based film.

The polyvinyl alcohol-based resin constituting the polarizer can be obtained by saponifying a polyvinyl acetate-based 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. Other monomers copolymerizable with vinyl acetate include acrylamide monomers having an unsaturated carboxylic acid type, an unsaturated sulfonic acid type, an olefin type, a vinyl ether type, and an ammonium group. The polyvinyl alcohol resin may also be modified. For example, polyvinyl formal or polyvinyl acetal modified with aldehydes may be used. The saponification degree of the polyvinyl alcohol-based resin is usually 85 to 100 mol%, preferably 98 mol% or more. The degree of polymerization of the polyvinyl alcohol-based resin is usually 1,000 to 10,000, preferably 1,500 to 5,000.

Such a polyvinyl alcohol-based resin film is used as the original film of the polarizer. The method of forming the film of the polyvinyl alcohol-based resin is not particularly limited, and a known method can be used. The thickness of the original film is not particularly limited, and may be, for example, 10 to 150 mu m.

The polarizer of the present invention is produced by continuously uniaxially stretching a polyvinyl alcohol-based film in an aqueous solution, staining with a dichroic dye and adsorbing, treating with an aqueous solution of boric acid, and washing and drying. The thickness of the polarizer produced as described above is 5 to 40 탆.

The method of bonding the polarizer and the protective film may be a conventional method in the art. For example, a polarizer or a protective film may be formed by a flexible method, a Meyer bar coating method, a gravure coating method, a die coating method, a dip coating method, A method in which an adhesive composition is applied to the bonding surfaces of the films and then these are bonded. The flexographic method is a method in which the polarizer or the protective film is moved in the vertical direction, the horizontal direction, or the inclined direction between the two, while applying the adhesive composition to the joint surface. After applying the adhesive composition, a polarizer or a protective film is put on a nip roll or the like and bonded.

After bonding the polarizer and the protective film, a drying treatment can be carried out. The drying treatment is carried out, for example, by spraying hot air. The drying temperature is suitably selected in the range of 40 to 100 占 폚, preferably 60 to 100 占 폚. The drying time may be about 20 to 1,200 seconds. After drying, it is preferable to cure at a room temperature or a slightly higher temperature, for example, at a temperature of 20 to 50 DEG C for about 12 to 600 hours. The thickness of the adhesive layer after drying is usually 0.001 to 5 mu m, preferably 0.01 to 2 mu m, more preferably 0.01 to 1 mu m or less. If the thickness of the adhesive layer exceeds 5 탆, the problem of appearance defects of the polarizing plate tends to occur.

A surface treatment layer such as a hard coating layer, an antireflection layer, an antiglare layer, and an antistatic layer may be further laminated on the other side of the polarizer to which the polarizer protective film is bonded on one side. Further, an optical functional film may be further laminated by a pressure-sensitive adhesive layer. Examples of the optically functional film include an optical compensation film in which a liquid crystal compound or a polymer compound thereof is oriented on the surface of a base material, an optical compensation film that transmits polarized light of any kind and reflects polarized light of a property opposite to that, A retardation film including a cyclic polyolefin resin, an antireflection functional film having a concavo-convex shape on its surface, an additional film having a surface antireflection treatment, a reflection film having a reflective function on the surface, And a transflective film having both a reflecting function and a transmitting function.

According to the above-described manufacturing method, the present invention provides a polarizer comprising: a polarizer; An adhesive layer which is laminated on one surface or both surfaces of the polarizer and comprises a polyallylamine resin having a repeating unit represented by the formula 1, an amine resin having a pH of 7 to 11 and a water-soluble and cationic amine, and a crosslinking agent; And a polarizer protective film laminated on the adhesive layer and plasma-treated with a reaction gas containing a maleic anhydride-based or succinic anhydride-based compound.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.

Example One

1) plasma process

One surface of a triacetyl cellulose-based polarizer protective film having a width of 250 mm × length of 700 mm × thickness of 80 μm was activated on the surface of the film by using a plasma discharge treatment apparatus (PN-APP300TT, Emaye).

During the discharge treatment, the reaction gas was supplied to the plasma electrode portion at a flow rate of 10 L / min by mixing 1 vol% maleic anhydride and 99 vol% nitrogen. An AC power source having a frequency of 20 kHz was used as the power source of the plasma generator, and a voltage of 8.5 kV was applied. The distance between the plasma electrodes was 2 mm and the discharge processing speed was 300 mm / sec.

2) Preparation of adhesive composition

(Sumirez Resin SPI-203 (50) H product, pH 5) was added to 100 parts by weight (solids content) of an aqueous solution of a polyallylamine resin having a weight average molecular weight of 1,000 (product of Nitto Bosa Co., 10 parts by weight) and 5 parts by weight of sodium glyoxalate (10% by weight aqueous solution) crosslinking agent were mixed to prepare an adhesive composition. At this time, the respective components were mixed based on the solid content.

3) Polarizer production

The adhesive composition of the above (2) was coated on both sides of the polarizer on which iodine was adsorbed and oriented so that the dry film thickness became 0.1 탆, and the protective film of (1) was bonded using niprol. The bonding was performed so that the plasma-treated side of the protective film and the polarizer were bonded. And then dried in a hot-air dryer at 80 ° C for 5 minutes to prepare a polarizing plate.

Example 2 and Comparative Example 1-3: Types and contents of reaction gas

The surface of the protective film was subjected to plasma treatment using the reaction gas shown in Table 1 below, and a polarizing plate was prepared using the same.

Classification (% by volume) Acid anhydride Inert gas Example 2-1 Anhydrous 2-dodecen-1-ylsuccinic acid (1) Nitrogen (99) Example 2-2 Anhydrous citraconic acid (1) Nitrogen (99) Example 2-3 Itaconic anhydride (1) Nitrogen (99) Examples 2-4 Maleic anhydride (3) Nitrogen (97) Example 2-5 Maleic anhydride (5) Nitrogen (95) Comparative Example 1 Oxygen (1) Nitrogen (99) Comparative Example 2 Hydroxyethyl acrylate (1) Nitrogen (99)

Example 3: Variation of protective film type

The same procedure as in Example 1 was carried out except that the kinds of protective films were changed to plasma treatments as shown in Table 2 below, and a polarizing plate was prepared using the same.

division Types of protective film Example 3-1 Cycloolefin Polarizer Protective Film
(Noboren, Japan Zeon Corporation, Zeonoa) Example 3-2 Acrylic Polarizer Protective Film (I-Film, Zeon Company, Japan)

Example 4 and Comparative Example 4-7

The adhesive composition was prepared in the same manner as in Example 1 except that the composition shown in Table 3 below was used, and a polarizing plate was prepared using the adhesive composition.

division
(Parts by weight) Polyallylamine resin Amine-based resin Cross-linking agent additive Kinds
(Weight average molecular weight) content Kinds content Example 4-1 PAA-01 products
(1,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Example 4-2 PAA-05 products
(5,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Example 4-3 PAA-08 products
(8,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Example 4-4 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Example 4-5 PAA-25C Products
(25,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Examples 4-6 Products PAA-H-10C
(60,000) 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Examples 4-7 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-106N 10 Sodium glyoxylate (5) - Examples 4-8 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 10 Aziridine resin (5) - Examples 4-9 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 10 Epoxy resin (5) - Examples 4-10 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 10 Melamine resin (5) - Examples 4-11 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 10 Aziridine resin (5) Na ₂ CO ₃
(5) Examples 4-12 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 25 Sodium glyoxylate (5) - Examples 4-13 PAA-15C Products
(15,000) 100 Sumirez Resin SPI-203 (50) H 50 Sodium glyoxylate (5) - Comparative Example 3 PAA-15C Products
(15,000) 100 - - Sodium glyoxylate (5) - Comparative Example 4 - - Sumirez Resin SPI-203 (50) H 100 Sodium glyoxylate (5) - Comparative Example 5 Epichlorohydrin-modified methyldiallylamine resin 100 Sumirez Resin SPI-203 (50) H 10 Sodium glyoxylate (5) - Comparative Example 6 PAA-15C Products
(15,000) 100 PAS-J-81 10 Sodium glyoxylate (5) - PAA-01 products, PAA-05 products, PAA-08 products, PAA-15 products, PAA-25 products, PAA-H-10C products:
Sumirez Resin SPI-203 (50) H: pH8, cationic, Taoka Chemical
Sumirez Resin SPI-106N: pH9, cationic, Taoka Chemical
PAS-J-81: pH7, cationic, Nittobo
Melamine resin: MW-30HM product, oxidized chemical company
Epoxy resin: Sumirez resin 650 product, Taoka Chemical Industries
Aziridine resin: CX-100 product, DSM company
Epichlorohydrin-modified methyldiallylamine resin: KCA101L product, Senka Co., Ltd.,

Experimental Example

The physical properties of the polarizing plate prepared in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 4 below.

1. Adhesion

The polarizer of the prepared polarizer and the polarizer protective film treated by plasma discharge were peeled off by hand, and the degree of peeling and the degree of breakage between them were observed, and evaluated based on the following criteria. At this time, the polarizer and the protective film are not peeled off from each other, and the more excellent the adhesion is.

○: Not peeled and damaged.

△: Almost peeled and not partially damaged.

X: peeled and hardly broken.

2. Water Contact angle

The water contact angle of the treated surface after the plasma treatment was measured using a contact angle meter (CAM200, manufactured by KSV Instruments). At this time, the water contact angle is preferably less than 50 degrees.

3. Optical properties (polarization degree, transmittance)

The prepared polarizer was cut into a size of 2.5 cm x 2.5 cm, and then the transmittance was measured using an ultraviolet ray spectrophotometer (V-7100, manufactured by JASCO). At this time, the polarization degree is defined by the following equation (1).

(Wherein T ₁ is the parallel transmittance obtained when the pair of polarizers are arranged in parallel with the absorption axis, and T ₂ is the orthogonal transmittance obtained when the pair of polarizers are arranged so that the absorption axes are perpendicular to each other) .

4. Endurance reliability

The durability reliability (long-term adhesive strength maintenance) was predicted by observing the state of peeling in hot water.

The prepared polarizing plate was cut into a size of 2.5 cm x 5 cm and then immersed in water at 60 ° C for 30 minutes to observe the peeling state. In this case, the smaller the amount of peeling, the better the durability reliability. If the peeling amount is 1000 탆 or more, the durability reliability is predicted to be poor.

division Adhesion Water contact angle
(°) Optical characteristic Endurance reliability
(탆) Polarization degree (%) Transmittance (%) Example 1 ○ 25 ° 99.995 42.0 100 μm or less Example 2-1 ○ 25 ° 99.996 42.1 100 μm or less Example 2-2 ○ 26 ° 99.995 42.0 100 μm or less Example 2-3 ○ 24 ° 99.994 42.2 100 μm or less Examples 2-4 ○ 20 ° 99.995 42.0 100 μm or less Example 2-5 ○ 18 ° 99.996 41.9 100 μm or less Example 3-1 ○ 25 ° 99.995 42.0 100 μm or less Example 3-2 ○ 25 ° 99.996 42.0 100 μm or less Example 4-1 ○ 25 ° 99.995 42.0 100 μm or less Example 4-2 ○ 25 ° 99.995 42.0 100 μm or less Example 4-3 ○ 25 ° 99.995 42.0 100 μm or less Example 4-4 ○ 25 ° 99.995 42.0 100 μm or less Example 4-5 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-6 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-7 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-8 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-9 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-10 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-11 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-12 ○ 25 ° 99.995 42.0 100 μm or less Examples 4-13 ○ 25 ° 99.995 42.0 100 μm or less Comparative Example 1 × 55 ° 99.995 42.0 1500 탆 Comparative Example 2 △ 55 ° 99.995 42.0 2000 탆 Comparative Example 3 △ 55 ° 99.995 42.0 1800 탆 Comparative Example 4 × 55 ° 99.995 42.0 2500 탆 Comparative Example 5 × 55 ° 99.995 42.0 2000 탆 Comparative Example 6 △ 55 ° 99.995 42.0 2500 탆

As shown in Table 4, the polarizing plates of Examples 1 to 4 according to the present invention had optical characteristics such as the degree of polarization and transmittance, which were equal to or higher than those of the conventional polarizing plate, as compared with Comparative Examples 1 to 6, Was superior.

Claims

Applying a plasma discharge treatment to at least one surface of the polarizer protective film using a reaction gas containing a maleic anhydride-based or a succinic anhydride-based compound; and
A polyallylamine-based resin having a repeating unit represented by the following formula (1); an amine-based resin having a pH of 7 to 11 and being water-soluble and cationic; And bonding the polarizer to the plasma discharge treated surface of the polarizer protective film by using an adhesive composition comprising a crosslinking agent and a crosslinking agent,
[Chemical Formula 1]

The polarizing plate according to claim 1, wherein the maleic anhydride-based or succinic anhydride-based compound is at least one selected from the group consisting of maleic anhydride, 2-dodecene-1-ylsuic anhydride, citraconic anhydride and itaconic anhydride. Gt;

The method of manufacturing a polarizing plate according to claim 1, wherein the reaction gas is formed by vaporizing a maleic anhydride-based or a succinic anhydride-based compound in an inert gas.

[4] The method of producing a polarizing plate according to claim 3, wherein the maleic anhydride-based or succinic anhydride-based compound is contained in the reaction gas in an amount of 1 to 5% by volume.

The method of manufacturing a polarizing plate according to claim 1, wherein the polyallylamine resin has a weight average molecular weight of 1,000 to 70,000.

The method of producing a polarizing plate according to claim 5, wherein the polyallylamine-based resin is a homopolymer.

The method for producing a polarizing plate according to claim 1, wherein the main chain of the amine resin is N, N'-bis (2-aminoethyl) -1,2-ethanediamine.

[Claim 7] The method according to claim 7, wherein the amine resin is further copolymerized with at least one compound selected from the group consisting of epoxy, amino and isobenzofuran dione.

[3] The method according to claim 1, wherein 3 to 50 parts by weight of the amine-based resin having a pH of 7 to 11 and being water-soluble and cationic, based on 100 parts by weight of the polyallylamine- And 1 to 20 parts by weight of the cross-linking agent.

A polarizer;
An adhesive layer which is laminated on one surface or both surfaces of the polarizer and comprises a polyallylamine resin having a repeating unit represented by the following formula 1, an amine resin having a pH of 7 to 11 and a water-soluble and cationic amine, and a crosslinking agent; And
A polarizer protective film laminated on the adhesive layer and plasma-treated with a reaction gas containing a maleic anhydride-based or succinic anhydride-based compound:
[Chemical Formula 1]