KR101934940B1 - Polarizing film with adhesive layer, production process therefor and image display device - Google Patents

Abstract

A polarizer, an anchor coating layer containing a polyvinyl alcohol-based resin, and a pressure-sensitive adhesive layer in this order, even if the pressure-sensitive adhesive layer does not contain an isocyanate-based crosslinking agent, the anchoring force of the anchor coating layer and the pressure- A polarizing film with a pressure-sensitive adhesive layer is provided.
A polarizer, an anchor coat layer and a pressure-sensitive adhesive layer in this order, wherein the anchor coat layer comprises a water-based resin and a compound (a) having at least one primary alcohol capable of reacting with a hydroxyl group at the molecular end, And the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a mercapto group-containing silane coupling agent.

Description

TECHNICAL FIELD [0001] The present invention relates to a polarizing film with a pressure-sensitive adhesive layer,

The present invention relates to a polarizing film with a pressure-sensitive adhesive layer and a manufacturing method thereof. The polarizing film with a pressure-sensitive adhesive layer can be used alone or as an optical film laminated thereon to form an image display apparatus such as a liquid crystal display (LCD) or an organic EL display.

It is indispensable to arrange polarizing elements on both sides of the liquid crystal cell from the image forming system of the liquid crystal display apparatus and the like, and a polarizing film is generally adhered. When the polarizing film is adhered to the liquid crystal cell, an adhesive is usually used. In addition, adhesion between the polarizing film and the liquid crystal cell usually reduces the loss of light, and therefore, each material is closely adhered using a pressure-sensitive adhesive. In this case, a polarizing film with a pressure-sensitive adhesive layer formed in advance as a pressure-sensitive adhesive layer on one side of the polarizing film is generally used since the polarizing film has advantages such as no need of a drying step for fixing the polarizing film. A release film is usually adhered to the pressure-sensitive adhesive layer of the polarizing film with a pressure-sensitive adhesive layer.

In order to form the pressure-sensitive adhesive layer, a pressure-sensitive adhesive containing a base polymer and a crosslinking agent is usually used. As the base polymer, an acrylic polymer is commonly used, and as the cross-linking agent, an isocyanate-based cross-linking agent is commonly used.

Further, from the viewpoint of thinning, a polarizing film with a pressure-sensitive adhesive layer using a polarizing polarizing film in which a protective film is formed only on one side of the polarizing element has been proposed. However, in a severe environment such as a thermal shock (for example, a test for 250 hours at 95 캜), the polarizing film with a pressure-sensitive adhesive layer using a polarizing protective polarizing film has a shrinkage stress of the polarizer on the side where the protective film is formed, There is a problem that various cracks are likely to occur from a fine crack of several hundreds of micrometers in the absorption axis direction of the polarizer to a penetration crack penetrating the entire surface of the polarizer. That is, the pressure-sensitive adhesive film with a pressure-sensitive adhesive layer-attached polarizing film did not have sufficient durability under the harsh environment.

It has been proposed to form a protective layer composed of a water-soluble film-forming composition (polyvinyl alcohol resin composition) on at least one surface of a polarizer from the viewpoints of suppressing the occurrence of penetrating cracks and thinning and lightening Document 1).

Patent Document 1: Japanese Patent Application Laid-Open No. 2005-043858

As described above, when a protective layer (anchor coating layer) formed of a polyvinyl alcohol-based resin composition is formed and a pressure-sensitive adhesive layer containing an isocyanate-based crosslinking agent is formed on the protective layer, the polyvinyl alcohol- The protective layer and the pressure-sensitive adhesive layer have a good anchoring effect due to the reaction between the resulting hydroxyl group and an isocyanate group derived from an isocyanate-based crosslinking agent in the pressure-sensitive adhesive layer.

However, the pressure-sensitive adhesive layer containing an isocyanate-based crosslinking agent is required to have a pressure-sensitive adhesive layer for securing an anchoring force so as to have hardness corresponding to anti-dent property and workability Later, it required a certain aging time until shipment. In addition, since the pressure-sensitive adhesive composition containing an isocyanate-based crosslinking agent undergoes a self-crosslinking reaction, there is a pot life as a pressure-sensitive adhesive composition, which is difficult to handle. On the other hand, in the pressure-sensitive adhesive composition containing no isocyanate-based crosslinking agent, the anchoring property with the anchor coating layer formed from the polyvinyl alcohol-based resin composition was not sufficiently satisfactory.

The present invention relates to a polarizing film with a pressure-sensitive adhesive layer having a polarizer, an anchor coating layer containing an aqueous resin and a pressure-sensitive adhesive layer in this order, wherein the pressure-sensitive adhesive layer contains no isocyanate-based crosslinking agent and the anchor coating layer and the pressure- And an object of the present invention is to provide a polarizing film with a pressure-sensitive adhesive layer.

It is another object of the present invention to provide a method for producing a polarizing film with a pressure-sensitive adhesive layer. The present invention also relates to an image display apparatus having the polarizing film with a pressure-sensitive adhesive layer.

The present inventors have intensively studied and found that the above problems can be solved by the following polarizing film with a pressure-sensitive adhesive layer, etc., and have reached the present invention.

That is, the present invention is a polarizing film with a pressure-sensitive adhesive layer having a polarizer, an anchor coat layer and a pressure-

The anchor coating layer is formed from a water-based resin composition containing a water-based resin and a compound (a) having at least one primary alcohol capable of reacting with a hydroxyl group at the molecular end,

Wherein the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a silane coupling agent containing a mercapto group.

In the polarizing film with a pressure-sensitive adhesive layer, at least one selected from a polyvinyl alcohol-based resin, a polyurethane-based resin and an oxazoline group-containing polymer may be used as the water-based resin. The aqueous resin is preferably a polyvinyl alcohol-based resin. The polyvinyl alcohol-based resin preferably has a saponification degree of 96 mol% or more and an average degree of polymerization of 2000 or more.

In the polarizing film with a pressure-sensitive adhesive layer, it is preferable that the water-based resin composition contains 0.2 to 20 parts by weight of the compound (a) relative to 100 parts by weight of the water-based resin.

In the polarizing film with a pressure-sensitive adhesive layer, methylol melamine is preferably used as the compound (a).

In the polarizing film with a pressure-sensitive adhesive layer, it is preferable that the thickness of the anchor coating layer is 0.05 탆 or more and 6 탆 or less.

In the polarizing film with a pressure-sensitive adhesive layer, a (meth) acryl-based polymer having a hydroxyl group can be used as the base polymer having a hydroxyl group.

In the polarizing film with a pressure-sensitive adhesive layer, it is preferable that the pressure-sensitive adhesive composition contains 0.01 to 5 parts by weight of the mercapto group-containing silane coupling agent per 100 parts by weight of the base polymer having a hydroxyl group.

In the polarizing film with a pressure-sensitive adhesive layer, the pressure-sensitive adhesive composition may contain a crosslinking agent. As the crosslinking agent, it is preferable to contain a crosslinking agent (b) which does not react with a hydroxyl group. As the crosslinking agent (b) which does not react with the hydroxyl group, a peroxide is preferable.

In the polarizing film with a pressure-sensitive adhesive layer, it is preferable that the pressure-sensitive adhesive composition contains 0.01 to 2 parts by weight of a crosslinking agent (b) which does not react with the hydroxyl group, relative to 100 parts by weight of the base polymer having a hydroxyl group.

In the polarizing film with a pressure-sensitive adhesive layer, it is preferable that the polarizer has a thickness of 15 탆 or less.

In the polarizing film with a pressure-sensitive adhesive layer, the polarizer preferably has an optical characteristic represented by a single transmittance (T) and a polarization degree (P)

P > - (10 ^0.929 T ^-42.4 -1) x 100 (with T <42.3) and

P? 99.9 (where T? 42.3).

In the polarizing film with a pressure-sensitive adhesive layer, a protective film may be provided on at least one side of the polarizer.

In the polarizing film with a pressure-sensitive adhesive layer, a separator may be laminated on the pressure-sensitive adhesive layer.

Further, the present invention is a method for producing a polarizing film with a pressure-sensitive adhesive layer,

A step of coating an aqueous resin composition containing a water-based resin and a compound (a) having at least one primary alcohol at the molecular end thereof capable of reacting with a hydroxyl group on a polarizer, and then drying to form an anchor coating layer;

A step of forming a pressure-sensitive adhesive layer from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a mercapto group-containing silane coupling agent on the anchor coat layer,

And a method of producing a polarizing film with a pressure-sensitive adhesive layer.

The present invention also relates to an image display apparatus having the polarizing film with a pressure-sensitive adhesive layer.

The polarizing film with a pressure-sensitive adhesive layer of the present invention has a polarizer, an anchor coating layer containing an aqueous resin, and a pressure-sensitive adhesive layer in this order. The anchor coating layer contains a compound (a) having at least one first-class alcohol capable of reacting with a hydroxyl group at the molecular end, for example, methylol melamine, and the pressure-sensitive adhesive layer contains a mercapto group-containing silane coupling agent. The terminal first-stage alcohol such as methylol melamine in the anchor coating layer reacts with an aqueous resin (for example, a polyvinyl alcohol resin) of the anchor coat layer, and on the one hand, the silanol group and the silanol group of the mercapto group- It can be thought that it reacts. When the anchor coating layer is directly formed on the polarizer, it is considered that the first-stage alcohol at the end such as methylol melamine in the anchor coating layer reacts with the hydroxyl group derived from the polyvinyl alcohol-based resin in the polarizer. It is also conceivable that the silanol group of the mercapto group-containing silane coupling agent reacts with the hydroxyl group derived from the base polymer in the pressure-sensitive adhesive layer. The mercapto group-containing silane coupling agent can be considered to form a sulfide bond by self-condensation through reaction of mercapto groups (-SH, thiol groups) in the pressure-sensitive adhesive layer, thereby increasing the crosslinking of the pressure-sensitive adhesive layer. As described above, since the anchor coat layer and the pressure-sensitive adhesive layer are bonded to each other by reaction, even if the pressure-sensitive adhesive layer does not contain an isocyanate-based cross-linking agent, it can be considered that the anchor coat layer and the pressure- have.

1 is an example of a schematic cross-sectional view of a polarizing film with a pressure-sensitive adhesive layer of the present invention.
2 is an example of a schematic sectional view of a polarizing film with a pressure-sensitive adhesive layer of the present invention.
3 is an example of a schematic sectional view of a polarizing film with a pressure-sensitive adhesive layer of the present invention.

Hereinafter, the polarizing films (10, 11, 12) with a pressure-sensitive adhesive layer of the present invention will be described with reference to Figs. The polarizing films 10, 11, and 12 with the pressure-sensitive adhesive layer have the polarizer 1, the anchor coating layer 2 containing an aqueous resin, and the pressure-sensitive adhesive layer 3 in this order. In the polarizing films (10, 11) with a pressure-sensitive adhesive layer of the present invention, an anchor coating layer (2) formed from an aqueous resin composition containing an aqueous resin in the polarizer (1) . 2 and 3, the protective films 5 and 5 'can be formed on one side or both sides of the polarizer 1. 2 shows a case where the polarizer 1 has the protective film 5 on the side opposite to the side where the anchor coating layer 2 is formed in the polarizing film 10 with a pressure-sensitive adhesive layer. 3 shows protective films 5 and 5 'on both sides of the polarizer 1 in the polarizing film with a pressure-sensitive adhesive layer 10 and an anchor coating layer 2 on the protective film 5' Are formed on the substrate. 2 and 3, the polarizer 1 and the protective film 5 are laminated via an internal layer such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer). Although not shown, the adhesive layer and the adhesive layer can be laminated by forming an adhesive layer on the protective films 5 and 5 'or performing an activation treatment.

1 to 3, the separator 4 can be formed on the pressure-sensitive adhesive layer 3 in the polarizing films 10 and 11 with a pressure-sensitive adhesive layer of the present invention. When the polarizing film 11 with a pressure-sensitive adhesive layer has a protective film 5 as shown in Figs. 2 and 3, a surface protective film may be formed on the protective film 5. Fig.

<Polarizer>

The polarizer is not particularly limited, and various kinds of polarizers can be used. As the polarizer, for example, a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or an ethylene / vinyl acetate copolymerization system partial saponification film is adsorbed with a dichroic substance of iodine or a dichroic dye to uniaxially stretch , A polyene-based oriented film such as a dehydrated product of polyvinyl alcohol, a dehydrochlorinated product of polyvinyl chloride, and the like. Among them, a polyvinyl alcohol film and a polarizer made of a dichroic material such as iodine are suitable. The thickness of these polarizers is not particularly limited, but is generally 2 to 25 占 퐉.

A polarizer obtained by dying a polyvinyl alcohol film with iodine and uniaxially stretching can be produced by, for example, dying a polyvinyl alcohol-based film in an aqueous solution of iodine and stretching it to 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution of potassium iodide or the like which may contain boric acid, zinc sulfate, zinc chloride or the like. If necessary, the polyvinyl alcohol film may be dipped in water and washed with water before dyeing. The polyvinyl alcohol film is washed with water to clean the surface of the polyvinyl alcohol film and the polyvinyl alcohol film is swollen to prevent unevenness such as uneven dyeing. The stretching may be carried out after the dyeing with iodine, the stretching while dyeing, or the stretching followed by the dyeing with iodine. It can be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

As the polarizer, a thin polarizer having a thickness of 15 mu m or less can be used. The thickness of the polarizer is preferably 12 占 퐉, more preferably 10 占 퐉 or less, further preferably 8 占 퐉 or less, further preferably 7 占 퐉 or less, further preferably 6 占 퐉 or less in view of thinning and crack resistance due to thermal shock. On the other hand, the thickness of the polarizer is preferably 2 탆 or more, more preferably 3 탆 or more. Such a thin polarizer is excellent in durability against thermal shock because of its small thickness unevenness, excellent visibility, and small dimensional change.

As a thin polarizer having a thickness of 15 占 퐉 or less, a typical example of the polarizer is disclosed in Japanese Patent No. 4751486, Japanese Patent No. 4751481, Japanese Patent No. 4815544, Japanese Patent No. 5048120, Japanese Patent No. 5587517, (Polarizers) described in, for example, pamphlet of International Publication No. 2014/077599, International Publication No. 2014/077636, or the like, or a thin polarizing film (polarizer) obtainable from the production methods described therein.

The polarizer is characterized in that the optical characteristics represented by the simple transmittance (T) and the polarization degree (P) ^{satisfy the} following expressions P> - (10 ^0.929T-42.4 -1) x 100 (where T <42.3) , T? 42.3). The polarizing film configured to satisfy the above condition uniquely has the performance required as a display for a liquid crystal television using a large display element. Specifically, it has a contrast ratio of 1000: 1 or more and a maximum luminance of 500 cd / m 2 or more. For another application, for example, it is bonded to the visible side of the organic EL display device.

As the thin polarizing film, in view of being able to improve the polarization performance by being stretched at a high magnification in the manufacturing method including the step of stretching in the state of the laminate and the step of dyeing, the specifications of Japanese Patent No. 4751486, Japanese Patent No. 4751481, It is preferably obtained by a production method including a step of stretching in an aqueous boric acid solution described in the specification of Japanese Patent No. 4815544. In particular, the stretching in an aqueous boric acid solution described in the specification of Japanese Patent No. 4751481 or the Japanese Patent No. 4815544 It is preferable to be obtained by a manufacturing method including a step of auxiliary pneumatic drawing. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a lead resin base material in the form of a laminate, and a step of dyeing. According to this manufacturing method, even if the PVA resin layer is thin, it can be stretched without any trouble such as breakage due to stretching because it is supported on the resin substrate for connection.

<Protection film>

The material constituting the protective film is preferably excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy and the like. Examples thereof include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetylcellulose and triacetylcellulose, acrylic polymers such as polymethylmethacrylate, polystyrene and acrylonitrile-styrene copolymer (AS Resin), and polycarbonate-based polymers. Examples of the polymer include polyolefin polymers such as polyethylene, polypropylene, cycloolefin or norbornene structure, polyolefin polymers such as ethylene / propylene copolymer, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, Based polymers, polyvinyl butyral-based polymers, arylate-based polymers, polyoxymethylene-based polymers, polyether sulfone-based polymers, An epoxy-based polymer or a mixture of the above-described polymers may be mentioned as an example of the polymer forming the protective film. These protective films are usually bonded to the polarizer by an adhesive layer. The protective film can be formed by applying a thermosetting resin such as a (meth) acrylic, urethane, acrylic urethane, epoxy, or silicone resin or an ultraviolet curing resin to a polarizer and curing it.

As the protective film, a retardation film can be used. Examples of the retardation film include retardation films having a front retardation of 40 nm or more and / or a thickness retardation of 80 nm or more. The front retardation is usually in the range of 40 to 200 nm, and the retardation in the thickness direction is usually controlled in the range of 80 to 300 nm. When a retardation film is used as the protective film, since the retardation film also functions as a polarizer protective film, it can be thinned.

Examples of the retardation film include a birefringent film obtained by uniaxially or biaxially stretching a thermoplastic resin film. The stretching temperature, stretching ratio and the like are appropriately set according to the retardation value, the material of the film, and the thickness.

The thickness of the protective film can be suitably determined, but it is generally preferably 3 to 200 占 퐉, more preferably 3 to 100 占 퐉, from the viewpoints of workability such as strength and handling properties and thin layer properties. In particular, the thickness of the protective film (when a film is formed in advance) is preferably 10 to 60 占 퐉, more preferably 10 to 45 占 퐉, from the viewpoint of transportability. On the other hand, the thickness of the protective film (when formed by coating or curing) is preferably 3 to 25 占 퐉, more preferably 3 to 20 占 퐉, from the viewpoint of transportability. The protective film may be used in plural or plural layers.

A functional layer such as a hard coating layer, an antireflection layer, an anti-sticking layer, a diffusion layer, or an anti-glare layer may be formed on the surface of the protective film on which the polarizer is not adhered. In addition, the functional layer such as the hard coating layer, the antireflection layer, the anti-sticking layer, the diffusion layer, and the anti-glare layer may be formed on the protective film itself or may be formed separately from the protective film.

<Intervening layer>

The protective film and the polarizer are laminated via an intervening layer such as an adhesive layer, a pressure-sensitive adhesive layer, and an undercoat layer (primer layer). At this time, it is preferable to stack the both without air gap by the interposition layer.

The adhesive layer is formed by an adhesive. The kind of the adhesive is not particularly limited, and various kinds of adhesives can be used. The adhesive layer is not particularly limited provided that it is optically transparent. As the adhesive, any of various types such as an aqueous base, a solvent base, a hot melt base, and an active energy ray curable base can be used.

Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex system, and a water-based polyester. The water-based adhesive is usually used as an adhesive composed of an aqueous solution, and usually contains 0.5 to 60% by weight of solids.

The active energy ray curable adhesive is an adhesive which is cured by an active energy ray such as electron beam, ultraviolet ray (radical curing type, positive curing type), and can be used, for example, as an electron beam curable type or an ultraviolet curable type. As the active energy ray curable adhesive, for example, a photo-radical curable adhesive may be used. When the photo-radical curing type active energy ray curable adhesive is used as an ultraviolet curing type adhesive, the adhesive contains a radical polymerizing compound and a photo polymerization initiator.

When an aqueous adhesive or the like is used for coating the adhesive, it is preferable that the thickness of the finally formed adhesive layer is 30 to 300 nm. The thickness of the adhesive layer is more preferably 60 to 250 nm. On the other hand, when an active energy ray-curable adhesive is used, it is preferable that the thickness of the adhesive layer is 0.1 to 200 mu m. More preferably 0.5 to 50 占 퐉, and still more preferably 0.5 to 10 占 퐉.

Further, in the lamination of the polarizer and the protective film, this adhesive layer can be formed between the protective film and the adhesive layer.

<Anchor coating layer>

The anchor coating layer contains an aqueous resin. The anchor coating layer can be formed, for example, by applying a water-based resin composition containing an aqueous resin to a polarizing plate. As the aqueous resin, for example, at least one selected from a polyvinyl alcohol-based resin, a polyurethane-based resin and an oxazoline group-containing polymer can be used. Among them, when an anchor coating layer is directly formed on the polarizer as shown in Figs. 1 and 2, a polyvinyl alcohol-based resin is preferable as the water-based resin from the viewpoint of suppressing the occurrence of penetration cracks. On the other hand, when an anchor coating layer is formed on the protective film as shown in Fig. 3, a polyurethane resin or an oxazoline group-containing polymer is preferable as the water-base resin from the viewpoint of film formability and wettability to the protective film.

Examples of the polyvinyl alcohol-based resin include polyvinyl alcohol. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. As the polyvinyl alcohol-based resin, a saponification product of a copolymer of vinyl acetate and a monomer having copolymerization may be mentioned. When the monomer having the copolymerization is ethylene, an ethylene-vinyl alcohol copolymer can be obtained. Examples of the monomer having the above-mentioned copolymerization include unsaturated carboxylic acids such as maleic anhydride, maleic acid, fumaric acid, crotonic acid, itaconic acid and (meth) acrylic acid and esters thereof; (Meth) allyl sulfonic acid (soda), sulfone oxygen da (monoalkyl maleate), disulfone oxygen dialkyl maleate, N-methylol acrylamide, acrylamide alkylsulfonic acid alkali Salts, N-vinylpyrrolidone, N-vinylpyrrolidone derivatives, and the like. These polyvinyl alcohol resins may be used singly or in combination of two or more. Polyvinyl alcohol obtained by saponifying polyvinyl acetate from the viewpoint of satisfying the heat resistance and water resistance by controlling the crystal melting heat of the anchor coating layer to 30 mj / mg or more is preferable.

The degree of saponification of the polyvinyl alcohol-based resin may be 95 mol% or more, for example. From the viewpoint of satisfying the moisture resistance and water resistance, the degree of saponification is preferably 96 mol% or more, more preferably 99 mol% Is preferably 99.5 mol% or more. The degree of saponification represents the ratio of units that are actually saponified into vinyl alcohol units among the units that can be converted into vinyl alcohol units by saponification, and the residues are vinyl ester units. The saponification degree can be obtained according to JIS K 6726-1994.

The average degree of polymerization of the polyvinyl alcohol resin may be 500 or more, for example. However, from the viewpoint of satisfying the wet heat resistance and water resistance of the anchor coating layer, the average degree of polymerization is preferably 1,000 or more, more preferably 1,500 or more, Is preferably 2000 or more. The average polymerization degree of the polyvinyl alcohol-based resin is measured according to JIS-K6726.

As the polyvinyl alcohol-based resin, a modified polyvinyl alcohol-based resin having a hydrophilic functional group in the side chain of the polyvinyl alcohol or the copolymer thereof can be used. Examples of the hydrophilic functional group include an acetoacetyl group and a carbonyl group. In addition, a modified polyvinyl alcohol prepared by acetalizing, urethane, etherifying, grafting, phosphoric esterification, or the like of a polyvinyl alcohol resin can be used.

As the polyurethane-based resin, an emulsion of a polyurethane-based resin can be used. As the resin emulsion of polyurethane, a resin obtained by self-emulsification without using an emulsifier can be used.

As the polyurethane resin, for example, a one-component type obtained by a mid-portion reaction between a high molecular polyol and an isocyanate compound can be used. As the one-pack type polyurethane resin, for example, polyether-based polyurethane resin, polyester-based polyurethane resin and the like can be used. As the polyurethane resin, it is preferable that a hydroxyl group remains. Specifically, for example, a lacquer type polyurethane resin can be mentioned. The polyurethane resin can be formed by simply drying and removing a solvent or water.

The polyether-based polyurethane resin is generally obtained by a reaction between a polyether polyol and an isocyanate compound. The polyether polyol can be obtained by adding an alkylene oxide to one or more polyhydric alcohols by ring-opening polymerization. The polyester-based polyurethane resin is generally obtained by a reaction between a polyester polyol and an isocyanate compound. The polyester polyol is obtained by polycondensation of a polyhydric alcohol with a polybasic acid. The number average molecular weight of the high molecular weight polyol such as polyether polyol or polyether polyol is preferably 400 to 3000, more preferably 500 to 2000. The high molecular polyols such as polyether polyol and polyester polyol may be used singly or in a copolymer using two or more kinds thereof.

As the isocyanate compound, an isocyanate such as an aromatic, aromatic aliphatic, aliphatic or alicyclic group used in polyurethane can be suitably used. As the isocyanate compound, an adduct, dimer, trimer, or polymer thereof of the above isocyanate compound may be used. As the isocyanate compound, a modified isocyanate obtained by subjecting a part of the above isocyanate to urethanation, uretdione formation, carbodiimidation or the like can also be used.

When the polyurethane resin is dispersed in water, there is known a method of forcibly emulsifying and dispersing the resin using an emulsifier. In addition, a water-dispersible hydrophilic group anion, a cationic group or a nonionic group may be introduced into the resin to form a self-emulsifying agent. An ionic polymer complex may also be used.

Examples of the resin emulsion of the polyurethane include an adecarbon tie-dye HUX series manufactured by Asahi Denka Kogyo Kabushiki Kaisha, which is self-emulsified without using an emulsifier. Specific examples of the water-based urethane resin include Superflex series manufactured by Daiichi Kogyo Co., Ltd. and Takeraku W-6020 manufactured by Mitsui Kagaku Polyurethane Co., Ltd.

As the epoxy resin, an emulsion of an epoxy resin can be used. When the epoxy resin is dispersed in water, a method is known in which the resin is emulsified and dispersed by forcible emulsification using an emulsifier. Examples of the epoxy resin include Adeka Resin EM series manufactured by ADEKA Co., Ltd., and Verticalxide 2021P manufactured by Daicel Co., Ltd.

Examples of the oxazoline group-containing polymer include polymers having an acrylic skeleton or a styrene skeleton and having an oxazoline group in the side chain of the main chain. Among them, an oxazoline group-containing acrylic polymer having a main chain composed of an acrylic skeleton and having an oxazoline group in the side chain of the main chain is preferable.

Examples of the oxazoline group include a 2-oxazoline group, a 3-oxazoline group and a 4-oxazoline group, and among them, a 2-oxazoline group is preferable. The 2-oxazoline group is generally represented by the following formula (1).

(Wherein R ¹ to R ⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, a phenyl group or a substituted phenyl group.)

The oxazoline group-containing polymer may have a polyoxyalkylene group in addition to the oxazoline group.

The oxazoline group-containing polymer preferably has a number average molecular weight of 5,000 or more, more preferably 10,000 or more, and usually 1,000,000 or less. If the number average molecular weight is lower than 5,000, the strength of the anchor coat layer is insufficient, causing cohesive failure, and the anchoring power may not be improved. If the number average molecular weight is higher than 1,000,000, workability may be deteriorated. Further, the oxazoline group-containing polymer may have an oxazoline value of, for example, 1,500 g solid / eq. And preferably 1,200 g solid / eq. Or less. Oxazoline is 1,500 g solid / eq. , The amount of the oxazoline group contained in the molecule is decreased, and the anchoring power may not be improved in some cases.

Since the oxazoline group-containing polymer reacts with the hydroxyl group contained in the pressure-sensitive adhesive composition at a relatively low temperature, if the oxazoline group-containing polymer is included in the anchor coating layer, the oxazoline group-containing polymer can be firmly adhered to the functional group in the pressure- .

Specific examples of the oxazoline group-containing polymer include oxazoline group-containing acrylic polymers such as Epocross WS-300, Epocross WS-500 and Epocross WS-700 manufactured by Nippon Shokubai Co., And an oxazoline group-containing acrylic / styrenic polymer such as Epocross K-1000 series manufactured by Shokuba Corp. and Epocross K-2000 series manufactured by Shokubai, and they may be used singly or in combination of two or more.

The anchor coating layer of the present invention is formed from a water-based resin composition containing the water-based resin as a main component, but the water-based resin composition contains the compound (a) having at least one primary alcohol at the molecular end capable of reacting with a hydroxyl group do. By introducing the compound (a) into the anchor coating layer, the reaction between the mercapto group-containing silane coupling agent and the base polymer having a hydroxyl group in the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer as described above proceeds, The anchoring force can be improved.

It is preferable that the aqueous resin does not have a functional group having reactivity with the first-class alcohol capable of reacting with the hydroxyl group of the compound (a). Of the water-based resins exemplified above, polyvinyl alcohol- In particular, unmodified polyvinyl alcohol resin is preferably used. Or the unmodified polyvinyl alcohol resin is used, the hydrophilic functional group relating to the modification is preferably a mercapto group in the pressure-sensitive adhesive composition in the relationship with the first-class alcohol capable of reacting with the hydroxyl group of the compound (a) Containing silane coupling agent is preferably lower in reactivity than the functional group (silanol group) contained in the silane coupling agent.

The compound (a) is preferably blended at a ratio of, for example, 0.2 parts by weight to 20 parts by weight with respect to 100 parts by weight of the aqueous resin. It is preferable that the ratio of the compound (a) is 0.2 parts by weight or more to improve the anchoring power. The proportion of the compound (a) is preferably 1 part by weight or more, more preferably 3 parts by weight or more. On the other hand, when the proportion of the compound (a) is increased, the water resistance and appearance (appearance recognized as unevenness in the polarizing film) deteriorate, so that the proportion of the compound (a) is preferably 20 parts by weight or less, Is preferably 10 parts by weight or less, more preferably 7 parts by weight or less. The proportion of the compound (a) is determined by the kind of the base polymer having a hydroxyl group and the mercapto group-containing silane coupling agent used in the pressure-sensitive adhesive composition.

The proportion of the aqueous resin in the anchor coating layer or the water-based resin composition (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more.

As the compound (a), a compound having at least one first-class alcohol at the molecular end can be preferably used. Examples of the compound include amino-formaldehyde resins such as methylol urea, methylol melamine, condensates of alkylated methylol urea and formaldehyde, ethylene glycol, glycerin, 1,6-hexanediol, 1,8-octanediol , Aliphatic alcohols, and polyethylene glycols. Of these, amino-formaldehyde resins having a methylol group, among them methylolmelamine, are very suitable.

Further, a compound having a functional group reactive with a hydroxyl group other than the compound (a) may be used. For example, a compound having an amino group at the molecular end. Examples of the compound include alkylenediamines having two alkylene groups and amino groups such as ethylenediamine, triethylenediamine, hexamethylenediamine and the like; Hydrazine; But are not limited to, adipic acid dihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic dihydrazide, glutaric acid dihydrazide, isophthalic acid dihydrazide, sebacic acid dihydrazide, maleic acid dihydrazide, Dicarboxylic acid dihydrazide such as zid and itaconic acid dihydrazide; And water-soluble dihydrazines such as ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine and butylene-1,4-dihydrazine. Among these, hydrazine is most suitable. The compound having an amino group at the molecular end is, for example, very suitable for the case where the base polymer of the pressure-sensitive adhesive composition has a hydroxyl group (when the base polymer is a (meth) acrylic polymer, it contains a monomer containing a hydroxyl group as a monomer unit) Do.

Examples of the compound having a functional group reactive with a hydroxyl group other than the compound (a) include tolylene diisocyanate, hydrogenated tolylene diisocyanate, trimethylolpropane tolylene diisocyanate adduct, triphenylmethane triisocyanate, methylene bis 4-phenylmethane triisocyanate, isophorone diisocyanate, and their ketooxime blockers or phenol blockers; ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin di or triglycidyl ether , Epoxies such as 1,6-hexane diol diglycidyl ether, trimethylol propane triglycidyl ether, diglycidyl aniline and diglycidyl amine; aldehydes such as formaldehyde, acetaldehyde, propionaldehyde and butylaldehyde; Monoaldehydes such as glyoxal, malondialdehyde, succinodialdehyde , Dialdehydes such as glutaraldehyde, maleindialdehyde and phthalaldehyde, amino-formaldehyde resins such as condensation products of alkylated methylol melamine, acetoguanamine, benzoguanamine and formaldehyde, and furthermore, sodium, potassium , Divalent metals such as magnesium, calcium, aluminum, iron and nickel, salts of trivalent metals and oxides thereof. Among these, amino-formaldehyde resin and water-soluble dihydrazine are preferable.

The compound having a functional group reactive with a hydroxyl group other than the compound (a) can be used from the viewpoints of improving the water resistance and controlling the elastic modulus, but the ratio is preferably 20 parts by weight or less and 10 parts by weight or less , Further preferably 5 parts by weight or less.

The aqueous resin composition is prepared as a solution in which the aqueous resin is dissolved in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide and dimethylacetamide N-methylpyrrolidone. These may be used alone or in combination of two or more. Among them, it is preferable to use it as an aqueous solution using water as a solvent. The concentration of the aqueous resin in the aqueous resin composition (for example, an aqueous solution) is not particularly limited, but is preferably 0.1 to 15% by weight, and more preferably 0.5 to 10% by weight, in view of coatability,

Further, other than the compound (a) may be added to the aqueous resin composition (for example, an aqueous solution). Examples thereof include surfactants and the like. Examples of the surfactant include nonionic surfactants. In addition, various tackifiers, ultraviolet absorbers, antioxidants, heat stabilizers, stabilizers such as moisture stabilizers, and the like may be blended.

The thickness of the anchor coating layer is preferably 0.05 占 퐉, more preferably 0.2 占 퐉 or more, and the thickness of the anchor coating layer is preferably 0.5 占 퐉 or more, and more preferably 0.7 占 퐉 or more. Particularly, when a polyvinyl alcohol-based resin is used as the water-based resin, the thickness of the anchor coat layer is preferably 0.2 mu m or more, and cracking due to thermal shock can be suppressed by the anchor coat layer of the thickness. On the other hand, if the anchor coating layer is too thick, the optical reliability and water resistance are lowered. Therefore, the thickness of the anchor coating layer is preferably 6 탆 or less, more preferably 5 탆 or less, further preferably 3 탆 or less and further preferably 2 탆 or less.

The anchor coating layer can be formed by applying the water-based resin composition to the other side of the polarizer (the side having no protective film) and drying the same. The application of the water-based resin composition is carried out so as to be a thickness after drying (preferably 0.2 탆 to 6 탆). The application operation is not particularly limited, and any appropriate method can be employed. Various means such as a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method and a knife coating method (a comma coating method)

<Pressure-sensitive adhesive layer>

The pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a mercapto group-containing silane coupling agent. For forming the pressure-sensitive adhesive layer, a suitable adhesive having a hydroxyl group can be used, and there is no particular limitation on the kind thereof. Examples of the pressure-sensitive adhesive include rubber-based pressure-sensitive adhesives, acrylic pressure-sensitive adhesives, silicone pressure-sensitive adhesives, urethane pressure-sensitive adhesives, vinyl alkyl ether pressure-sensitive adhesives, polyvinyl alcohol pressure-sensitive adhesives, polyvinylpyrrolidone pressure-sensitive adhesives, polyacrylamide pressure-sensitive adhesives and cellulosic pressure-sensitive adhesives. Various base polymers may be used depending on the pressure-sensitive adhesive.

The proportion of the base polymer having a hydroxyl group in the pressure-sensitive adhesive layer or the pressure-sensitive adhesive composition (solid content) is preferably 80% by weight or more, more preferably 90% by weight or more, further preferably 95% by weight or more.

Among these pressure-sensitive adhesives, those having excellent optical transparency and exhibiting appropriate wettability, cohesiveness, and adhesive properties such as weatherability and heat resistance are preferably used. An acrylic pressure-sensitive adhesive is preferably used as this feature. As the base polymer of the acrylic pressure-sensitive adhesive, a (meth) acryl-based polymer is used. The (meth) acryl-based polymer usually contains alkyl (meth) acrylate as a main component as a monomer unit. Further, (meth) acrylate refers to acrylate and / or methacrylate and has the same meaning as (meth) acrylate of the present invention.

As the alkyl (meth) acrylate constituting the main skeleton of the (meth) acrylic polymer, those having 1 to 18 carbon atoms in the straight chain or branched chain alkyl group can be exemplified. Examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, amyl group, hexyl group, cyclohexyl group, heptyl group, 2-ethylhexyl group, isooctyl group, , An isodecyl group, a dodecyl group, an isomylstearyl group, a lauryl group, a tridecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group. These can be used alone or in combination. The average carbon number of such alkyl groups is preferably from 3 to 9.

The (meth) acryl-based polymer used in the present invention preferably contains a monomer containing a hydroxyl group as a monomer unit. The hydroxyl group-containing monomer has a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group, and also has a hydroxyl group. Specific examples of the hydroxyl group-containing monomer include, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (Meth) acrylic acid hydroxyalkyl such as (meth) acrylic acid 8-hydroxyoctyl, (meth) acrylic acid 10-hydroxydecyl and (meth) -Methyl acrylate, and the like.

(Meth) acryl-based polymer has an alkyl (meth) acrylate as a main component and a proportion of the hydroxyl group-containing monomer in the (meth) acryl-based polymer in the weight ratio of the total constituent monomers, , It is preferably 0.01 to 15%, more preferably 0.03 to 10%, further preferably 0.05 to 7%.

Further, one or more copolymerizable monomers having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be introduced into the (meth) acryl-based polymer by copolymerization for the purpose of improving the adhesive force and heat resistance have.

Examples of the copolymerizable monomer include carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Monomers containing acid anhydride groups such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; (Meth) acrylamido-2-methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxynaphthalenesulfonic acid Containing sulfonic acid group-containing monomers; And a phosphoric acid group-containing monomer such as 2-hydroxyethyl acryloyl phosphate.

Examples of the (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide and N-methylolpropane (N-substituted) amide-based monomers; (Meth) acrylic acid alkylaminoalkyl monomers such as aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate and t-butylaminoethyl (meth) acrylate; (Meth) acrylic acid alkoxyalkyl monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; (Meth) acryloyloxymethylenesuccinimide, N- (meth) acryloyl-6-oxyhexamethylenesuccinimide, N- (meth) acryloyl-8- - succinimide-based monomers such as acryloylmorpholine; Maleimide-based monomers such as N-cyclohexylmaleimide and N-isopropylmaleimide, N-laurylmaleimide and N-phenylmaleimide; N-diisopropylethylenediamine, N-methylethylenediamine, N-methylethylenediamine, N-methylethylenediamine, N-methylethylenediamine, N-methylethylenediamine, And itaconimide-based monomers such as N, N-lauryl itaconimide and the like can be mentioned as an example of a monomer for modification.

In addition, as the modifying monomer, there may be mentioned vinyl acetate, vinyl propionate, N-vinyl pyrrolidone, methyl vinyl pyrrolidone, vinyl pyridine, vinyl piperidone, vinyl pyrimidine, vinylpiperazine, vinyl pyrazine, vinyl pyrrole, Vinyl monomers such as vinyl oxazole, vinyl morpholine, N-vinylcarboxylic acid amides, styrene,? -Methylstyrene, and N-vinylcaprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; An epoxy group-containing acrylic monomer such as glycidyl (meth) acrylate; Glycol type acrylic ester monomers such as (meth) acrylic acid polyethylene glycol, (meth) acrylic acid polypropylene glycol, (meth) acrylic acid methoxyethylene glycol and (meth) acrylic acid methoxypolypropylene glycol; (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, fluorine (meth) acrylate, and acrylic ester monomers such as silicone (meth) acrylate and 2-methoxyethyl acrylate. Further, isoprene, butadiene, isobutylene, vinyl ether and the like can be mentioned.

Examples of the copolymerizable monomer other than the above include silane-based monomers containing a silicon atom. Examples of the silane-based monomer include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyl Octyltrimethoxysilane, octyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltri Ethoxysilane, 10-acryloyloxydecyltriethoxysilane, and the like.

Examples of the copolymerizable monomer include tripropylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (Meth) acryloyl group such as ester of (meth) acrylic acid and polyhydric alcohol such as dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) (Meth) acrylate as a functional group which is the same as the monomer component in the skeleton of a polyfunctional monomer, polyester, epoxy or urethane having two or more unsaturated double bonds, (Meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate and the like having two or more unsaturated double bonds such as an acryloyl group and a vinyl group may be used.

The proportion of the above-mentioned copolymerizable monomer (other than the hydroxyl group-containing monomer) in the (meth) acrylic polymer is not particularly limited, but is preferably about 0 to 20%, more preferably about 0.1 to 15% .

Of these copolymerizable monomers (other than hydroxyl group-containing monomers), carboxyl group-containing monomers are preferably used in view of adhesiveness and durability. When the monomer containing a carboxyl group is contained as the copolymerizable monomer, the proportion thereof is preferably from 0.05 to 10% by weight, more preferably from 0.1 to 8% by weight, further preferably from 0.2 to 6% by weight.

The (meth) acrylic polymer of the present invention usually has a weight average molecular weight in the range of 500,000 to 3,000,000. In consideration of durability, particularly heat resistance, it is preferable to use those having a weight average molecular weight of 700,000 to 27,000,000. And more preferably from 800,000 to 250,000. When the weight-average molecular weight is less than 500,000, it is not preferable from the viewpoint of heat resistance. If the weight average molecular weight is more than 3,000,000, a large amount of diluting solvent is required to adjust the viscosity for coating, which is not preferable because the cost is increased. The weight average molecular weight refers to a value measured by GPC (Gel Permeation Chromatography) and calculated by polystyrene conversion.

Such (meth) acryl-based polymers can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerization. The (meth) acryl-based polymer to be obtained may be any of random copolymers, block copolymers, graft copolymers and the like.

The polymerization initiator, chain transfer agent and emulsifier used in the radical polymerization are not particularly limited and can be appropriately selected and used. The weight average molecular weight of the (meth) acryl-based polymer can be controlled by the amount of the polymerization initiator, the amount of the chain transfer agent, and the reaction conditions.

Further, the pressure-sensitive adhesive composition of the present invention contains a mercapto group-containing silane coupling agent in addition to the base polymer having a hydroxyl group (for example, a (meth) acryl-based polymer). Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldiethoxysilane, And mercapto groups such as mercaptomethylphenylethyltrimethoxysilane, mercaptomethyltrimethoxysilane, 6-mercaptohexyltrimethoxysilane, and 10-mercaptodecyltrimethoxysilane, and the like.

As the mercapto group-containing silane coupling agent, an oligomer type mercapto group-containing silane coupling agent having at least two alkoxysilyl groups in the molecule is preferred. Specific examples thereof include X-41-1805, X-41-1818, and X-41-1810 manufactured by Shin-Etsu Chemical Co., These mercapto group-containing silane coupling agents are difficult to volatilize and have a plurality of alkoxysilyl groups, which is effective for improving durability and is preferable. Here, the oligomer type refers to a polymer having a molecular weight of less than or equal to the dimer of the monomer and less than 100 moles, and the weight average molecular weight of the oligomer type silane coupling agent is preferably approximately 300 to 30000.

The number of the alkoxysilyl groups of the oligomer type mercapto group-containing silane coupling agent may be two or more in the molecule, and the number thereof is not limited. The amount of the alkoxy group of the oligomer type mercapto group-containing silane coupling agent is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and even more preferably 20 to 40% by weight in the silane coupling agent .

Examples of the alkoxy group include, but are not limited to, alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, pentyloxy and hexyloxy. Of these, methoxy and ethoxy are preferable, and methoxy is more preferable. It is also preferable that both of methoxy and ethoxy are contained in one molecule.

The content of the mercapto group of the mercapto group-containing silane coupling agent is preferably 1,000 g / mol or less, more preferably 800 g / mol or less, more preferably 500 g / mol or less in the case of the mercapto group (-SH) desirable. The lower limit of the mercapto equivalent is not particularly limited, but is preferably 200 g / mol or more, for example.

The mercapto group-containing silane coupling agent may be used alone or in admixture of two or more kinds. The total content of the mercapto group-containing silane coupling agent may be 100 weight% (for example, (meth) acrylic polymer) More preferably 0.01 to 3 parts by weight, still more preferably 0.02 to 2 parts by weight, still more preferably 0.05 to 1 part by weight.

Further, a silane coupling system other than the mercapto group-containing silane coupling agent may be added to the pressure-sensitive adhesive composition of the present invention. Other coupling agents include 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylidene (Meth) acrylate such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, and the like; amino group-containing silane coupling agents such as propylamine and N-phenyl-gamma -aminopropyltrimethoxysilane; Group-containing silane coupling agents, and isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane.

The silane coupling agent other than the mercapto group-containing silane coupling agent can be added within a range that does not lose the effect of the present invention. The amount of the silane coupling agent to be used is not particularly limited. For example, from the viewpoint of adhesion to an adherend, 3 parts by weight or less, more preferably 2 parts by weight or less, and further preferably 1 part by weight or less, based on 100 parts by weight of the composition. By using a silane coupling agent other than a mercapto group, adhesion can be improved. However, since silane coupling agents other than the mercapto group can impart reworkability, the adhesion amount tends to deteriorate when the added amount is large.

In addition, the pressure-sensitive adhesive composition of the present invention may contain a crosslinking agent. These crosslinking agents may be used singly or in combination of two or more kinds. The crosslinking agent is preferably 2 parts by weight or less, more preferably 1.5 parts by weight or less, and further preferably 1 part by weight or less, based on 100 parts by weight of the base polymer having a hydroxyl group.

The pressure-sensitive adhesive composition of the present invention preferably contains a crosslinking agent (b) which does not react with a hydroxyl group as the crosslinking agent. The crosslinking agent (b) which does not react with the hydroxyl group may be used in combination with an isocyanate crosslinking agent, but is preferred in the case of not containing an isocyanate crosslinking agent. When the pressure-sensitive adhesive composition of the present invention does not contain an isocyanate-based cross-linking agent, there is no problem in terms of the handling of the port life. The crosslinking agent (b) which does not react with the hydroxyl group is not particularly required to be aged until reaching a predetermined gel fraction after the formation of the pressure-sensitive adhesive layer, and a hard material having a gel fraction of 80% or more from the initial stage of forming the pressure- Can be produced. Further, in the pressure-sensitive adhesive layer, since the crosslinking by the crosslinking agent (b) which does not react with the hydroxyl group is proceeding, the hydroxyl group of the base polymer can efficiently react with the silanol group of the mercapto group-containing silane coupling agent , It can be considered that the gel fraction of the pressure-sensitive adhesive layer can be made harder than 80% from the initial stage.

The crosslinking agent (b) may be used singly or as a mixture of two or more kinds. The total content of the crosslinking agent (b) may vary depending on the amount of the crosslinking agent b) is preferably 0.01 to 2 parts by weight, more preferably 0.04 to 1.5 parts by weight, further preferably 0.05 to 1 part by weight, further preferably 0.4 to 0.6 part by weight. Is appropriately selected within this range for the purpose of adjusting workability, reworkability, crosslinking stability, releasability and the like.

As the crosslinking agent (b), a peroxide can be preferably used.

The method of measuring the amount of decomposed peroxide remaining after the reaction treatment can be measured by, for example, HPLC (high performance liquid chromatography).

More specifically, for example, about 0.2 g of the pressure-sensitive adhesive composition after the reaction treatment was taken out, immersed in 10 ml of ethyl acetate, shaken out at 25 캜 for 3 hours at 120 rpm in a shaker, and then left standing at room temperature for 3 days. do. Subsequently, 10 ml of acetonitrile was added, and about 10 추출 of the extract obtained by shaking at 25 캜 for 30 minutes at 120 rpm and filtering with a membrane filter (0.45 탆) was injected into HPLC and analyzed to obtain the amount of peroxide after the reaction treatment .

The peroxide is not particularly limited as long as it is capable of generating radical active species by heating or light irradiation to progress the crosslinking of the base polymer of the pressure-sensitive adhesive composition. However, in view of workability and stability, peroxides having a half-life temperature for one minute of 80 ° C to 160 ° C , And it is more preferable to use a peroxide having a temperature of 90 ° C to 140 ° C.

Examples of peroxides that can be used include di (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 占 폚), di (4-t-butylcyclohexyl) peroxydicarbonate Butyl peroxyneodecanoate (1 minute half-life temperature: 103.5 占 폚), t-hexyl peroxy pivalate (1 minute half-life temperature: (1 minute half-life temperature: 110.1 占 폚), di-lauroyl peroxide (1 minute half-life temperature: 116.4 占 폚), di-n-octanoyl peroxide 117.4 占 폚), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half life temperature: 124.3 占 폚), di (4-methylbenzoyl) peroxide (1 minute half life temperature: 128.2 (Half-life temperature for one minute: 130.0 占 폚), t-butyl peroxyisobutyrate (one minute half life temperature: 136.1 占 폚), 1,1-di Silperoxy) cyclohexane (1 minute half-life temperature: 149.2 ° C). Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 占 폚), di rauroyl peroxide (1 minute half life temperature: 116.4 占 폚) Benzoyl peroxide (1 minute half-life temperature: 130.0 占 폚) and the like are preferably used.

The half-life period of peroxide is an index indicating the rate of decomposition of peroxide, and refers to the time until the amount of residual peroxide becomes half. The decomposition temperature for obtaining a half-life at an arbitrary time and the half-life time at an arbitrary temperature are described in a manufacturer's catalog. For example, the &quot; Organic Peroxide Catalog Ninth Edition (May 2003) &quot; And the like.

As the crosslinking agent other than the crosslinking agent (b), an organic crosslinking agent or a polyfunctional metal chelate can be used. Examples of the organic cross-linking agent include an isocyanate cross-linking agent, an epoxy cross-linking agent, and an imine cross-linking agent. A polyfunctional metal chelate is one in which a polyvalent metal is covalently bonded or coordinated with an organic compound. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, have. Examples of the atom in the covalent bond or coordinate bond organic compound include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

The amount of the cross-linking agent other than the cross-linking agent (b) is preferably controlled so that a solid content of the gel fraction of 80% or more from the initial stage of forming the pressure-sensitive adhesive layer can be controlled. For example, the crosslinking agent other than the crosslinking agent (b) may be used in an amount of 2 parts by weight or less based on 100 parts by weight of the pressure-sensitive adhesive composition, more preferably 1 part by weight or less, further preferably 0.5 part by weight or less. Particularly, in the case of using an isocyanate-based crosslinking agent as a crosslinking agent other than the crosslinking agent (b), the amount of the isocyanate-based crosslinking agent is controlled within a range that does not require aging. The isocyanate-based crosslinking agent is preferable in terms of securing an anchoring force to an adherend such as a film, and is also preferable in that the pressure-sensitive adhesive layer becomes hard and the dimensional change of the polarizing film is suppressed. Furthermore, it is particularly preferable to use the isocyanate crosslinking agent and the crosslinking agent (b) which does not react with the hydroxyl group, because a stronger anchoring force can be obtained.

The pressure-sensitive adhesive composition of the present invention may contain an alkali metal salt, a polyether-modified silicone compound and other known additives, for example, a polyether compound of polyalkylene glycol such as polypropylene glycol, a powder such as a colorant, A surfactant, a plasticizer, a tackifier, a surface lubricant, a leveling agent, a softener, an antioxidant, an antioxidant, a light stabilizer, an ultraviolet absorber, a polymerization inhibitor, an inorganic or organic filler, And the like can be appropriately added depending on the use. Also, a redox system to which a reducing agent is added may be employed within a controllable range.

In forming the pressure-sensitive adhesive layer by the pressure-sensitive adhesive composition, it is preferable that the amount of the entire crosslinking agent is adjusted and the influence of the crosslinking treatment temperature and the crosslinking treatment time is sufficiently taken into consideration.

The crosslinking treatment temperature and the crosslinking treatment time can be adjusted by the crosslinking agent to be used. The crosslinking treatment temperature is preferably 170 占 폚 or less.

The crosslinking treatment may be carried out at a temperature in the drying step of the pressure-sensitive adhesive layer, or may be carried out by forming a separate crosslinking step after the drying step.

The crosslinking treatment time can be set in consideration of productivity and workability, but is usually about 0.2 to 20 minutes, preferably about 0.5 to 10 minutes.

As a method for forming the pressure-sensitive adhesive layer, for example, a method of transferring the pressure-sensitive adhesive layer onto an anchor coating layer in the embodiment of Figs. 1 and 2 after the pressure-sensitive adhesive composition is applied to a separator or the like, In the embodiments 1 and 2, the pressure-sensitive adhesive composition is applied to the anchor coating layer, and the polymerization solvent or the like is dried and removed to form a pressure-sensitive adhesive layer on the polarizing film. Further, at the time of applying the pressure-sensitive adhesive, at least one solvent other than the polymerization solvent may be newly added.

A silicone release liner is preferably used as the separator treated as the release treatment. In the step of applying and drying the pressure-sensitive adhesive composition of the present invention on the liner to form the pressure-sensitive adhesive layer, a suitable method may be employed as the method of drying the pressure-sensitive adhesive composition, depending on the purpose. Preferably, a method of over-drying the coating film can be used. The heat drying temperature is preferably 40 to 200 占 폚, more preferably 50 to 180 占 폚, and particularly preferably 70 to 170 占 폚. By setting the heating temperature within the above range, a pressure-sensitive adhesive layer having excellent adhesive properties can be obtained.

The drying time can be appropriately set to an appropriate time. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, particularly preferably 10 seconds to 5 minutes.

As the method for forming the pressure-sensitive adhesive layer, various methods can be used. Specifically, extrusion coating such as roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, And the like.

The thickness of the pressure-sensitive adhesive layer is not particularly limited and is, for example, about 1 to 100 mu m. Preferably 2 to 50 占 퐉, more preferably 2 to 40 占 퐉, and still more preferably 5 to 35 占 퐉.

When the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected with a sheet (separator) which has been peeled off until it is provided for practical use.

Examples of the constituent material of the separator include plastic films such as polyethylene, polypropylene, polyethylene terephthalate and polyester film, porous materials such as paper, cloth and nonwoven fabric, and suitable thin sheets such as net, foam sheet, metal foil and laminate thereof Thin leaf), and the like, but a plastic film can be preferably used because of its excellent surface smoothness.

The plastic film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer, and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, A co-extruded film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.

The thickness of the separator is usually 5 to 200 占 퐉, preferably 5 to 100 占 퐉. If necessary, the separator may also be subjected to antistatic treatment such as releasing treatment by a releasing agent of a silicone type, fluorine type, long chain alkyl type or fatty acid amide type, silica powder, antistatic treatment, coating type, kneading type, . Particularly, the peeling property from the pressure-sensitive adhesive layer can be further improved by appropriately carrying out the surface treatment of the separator such as the silicone treatment, the long-chain alkyl treatment, the fluorine treatment and the like.

In addition, the peeled sheet used in the production of the polarizing film with a pressure-sensitive adhesive layer can be used as a separator of a polarizing film with a pressure-sensitive adhesive layer as it is, and simplification on the processing surface is possible.

<Surface Protective Film>

A surface protective film can be formed on the polarizing film with a pressure-sensitive adhesive layer. The surface protective film usually has a base film and a pressure-sensitive adhesive layer, and protects the polarizer through the pressure-sensitive adhesive layer.

As the base film of the surface protective film, a film material having isotropic (isotropic) or near isotropic property is selected from the viewpoint of inspection property and manageability. Examples of the film material include a polyester resin such as a polyethylene terephthalate film, a cellulose resin, an acetate resin, a polyether sulfone resin, a polycarbonate resin, a polyamide resin, a polyimide resin, And a transparent polymer such as an acrylic resin. Among these, a polyester resin is preferable. The base film may be used as a laminate of one kind or two or more kinds of film materials, or a stretched product of the film may be used. The thickness of the base film is generally 500 탆 or less, preferably 10 to 200 탆.

As the pressure-sensitive adhesive for forming the pressure-sensitive adhesive layer of the surface protective film, a pressure-sensitive adhesive containing a polymer such as a (meth) acryl-based polymer, a silicone-based polymer, a polyester, a polyurethane, a polyamide, a polyether, . From the viewpoints of transparency, weather resistance, heat resistance and the like, an acrylic pressure sensitive adhesive using an acrylic polymer as a base polymer is preferable. The thickness (dry film thickness) of the pressure-sensitive adhesive layer is determined according to the adhesive force required. And is usually about 1 to 100 mu m, preferably 5 to 50 mu m.

Further, on the surface protective film, a release treatment layer can be formed on the opposite surface of the base film on which the pressure-sensitive adhesive layer is formed by a low-adhesion material such as silicone treatment, long-chain alkyl treatment or fluorine treatment.

<Other optical layers>

The polarizing film with a pressure-sensitive adhesive layer of the present invention can be used as an optical film laminated with another optical layer in practical use. The optical layer is not particularly limited, but can be used for forming a liquid crystal display device such as a reflection plate, a semitransmissive plate, a phase difference plate (including a wave plate of 1/2 or 1/4) One or two or more optical layers can be used. Particularly, a reflection type polarizing film or a semi-transmission type polarizing film in which a reflection plate or a transflective plate is further laminated on the polarizing film with a pressure-sensitive adhesive layer of the present invention, an elliptically polarizing film or a circularly polarizing film in which a retardation film is further laminated on the polarizing film, Or a polarizing film in which a brightness enhancement film is further laminated on a polarizing film is preferable.

The optical film obtained by laminating the above optical layers on the polarizing film with a pressure-sensitive adhesive layer can be formed by sequentially laminating them separately in the course of production of a liquid crystal display or the like. However, And the like are advantageous in that the manufacturing process of the liquid crystal display device and the like can be improved. Appropriate adhesion means such as a pressure-sensitive adhesive layer can be used for the lamination. In the above-mentioned adhesion of the polarizing film with a pressure-sensitive adhesive layer and other optical films, the optical axis thereof can be set at an appropriate arrangement angle in accordance with a desired retardation property and the like.

The polarizing film or optical film with a pressure-sensitive adhesive layer of the present invention can be suitably used for the formation of various devices such as a liquid crystal display device. Formation of a liquid crystal display device can be carried out in accordance with a conventional method. That is, the liquid crystal display device is generally formed by appropriately assembling components such as a liquid crystal cell, a polarizing film with a pressure-sensitive adhesive layer or an optical film, and an illumination system as required, and inserting a driving circuit. In the present invention, Except that a polarizing film or an optical film with a pressure-sensitive adhesive layer according to the present invention is used. As for the liquid crystal cell, any kind of IPS type or VA type can be used, for example.

A suitable liquid crystal display device such as a liquid crystal display in which a polarizing film or optical film with a pressure-sensitive adhesive layer is disposed on one side or both sides of the liquid crystal cell, or a backlight or a reflector is used for the illumination system can be formed. In this case, the polarizing film or optical film with a pressure-sensitive adhesive layer according to the present invention can be provided on one side or both sides of the liquid crystal cell. When a polarizing film or an optical film with a pressure-sensitive adhesive layer is formed on both sides, they may be the same or different. In forming the liquid crystal display device, appropriate parts such as a diffusion plate, an anti-glare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffusion plate and a backlight are disposed at appropriate positions can do.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to the following examples. In the examples, all parts and% are based on weight. The room temperature leaving conditions without any special rules are 23 ° C and 65% RH.

<Measurement of weight average molecular weight of (meth) acryl-based polymer>

The weight average molecular weight of the (meth) acryl-based polymer was measured by GPC (gel permeation chromatography).

Analytical Apparatus: HLC-8120GPC manufactured by Tosoh Corporation

Column: manufactured by Tosoh Corporation, G7000H _XL + GMH _XL + GMH _XL

· Column size: Each 7.8mmφ × 30cm system 90cm

Column temperature: 40 ° C

· Flow rate: 0.8 ml / min

Injection amount: 100 μl

Eluent: tetrahydrofuran

Detector: Differential refractometer (RI)

· Standard sample: Polystyrene

<Production of Polarizer>

(IPA copolymerized PET) film (thickness: 100 mu m) having an absorption rate of 0.75% and a Tg of 75 DEG C was subjected to corona treatment on one side of the substrate, and polyvinyl alcohol (polymerization degree: 4200, (Saponification degree: 99.2 mol%) and acetoacetyl modified PVA (polymerization degree: 1200, acetoacetyl modification degree: 4.6%, degree of saponification: 99.0 mol% or more, trade name: Was applied at 25 캜 and dried to form a PVA resin layer having a thickness of 11 탆, thereby preparing a laminate.

The obtained laminate was free-end uniaxially stretched in an oven at 120 캜 in the longitudinal direction (lengthwise direction) between free rolls different in the main speed (air assisted stretching process).

Subsequently, the laminate was immersed (insolubilization treatment) for 30 seconds in an insolubilizing bath having a liquid temperature of 30 DEG C (an aqueous boric acid solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water).

Subsequently, the polarizing plate was immersed in a dyeing bath at a liquid temperature of 30 캜 while adjusting the iodine concentration and the immersion time so that the polarizing plate had a predetermined transmittance. In this embodiment, 0.2 part by weight of iodine was added to 100 parts by weight of water, and 1.0 part by weight of potassium iodide was blended to obtain an iodine aqueous solution for 60 seconds (dyeing treatment).

Subsequently, the resultant was immersed in a crosslinking bath (aqueous solution of boric acid obtained by mixing 3 parts by weight of potassium iodide and 3 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 30 占 폚 for 30 seconds (crosslinking treatment).

Thereafter, the laminate was immersed in a boric acid aqueous solution having a liquid temperature of 70 캜 (an aqueous solution obtained by blending 4 parts by weight of boric acid and 5 parts by weight of potassium iodide with respect to 100 parts by weight of water) Lengthwise direction) so that the total draw ratio was 5.5 times (in-water elongation treatment).

Thereafter, the laminate was immersed in a cleansing bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 30 DEG C (washing treatment).

Thus, an optical film laminate including a polarizer having a thickness of 5 占 퐉 was obtained.

(Preparation of protective film)

Protective film: The easily adhered surface of a (meth) acrylic resin film having a lactone ring structure with a thickness of 40 탆 was subjected to corona treatment.

(Preparation of adhesive applied to protective film)

40 parts by weight of N-hydroxyethyl acrylamide (HEAA), 60 parts by weight of acryloylmorpholine (ACMO) and 3 parts by weight of a photoinitiator "IRGACURE 819" (manufactured by BASF) were mixed to prepare an ultraviolet curable adhesive.

&Lt; Preparation of protective polarizing film >

The protective film was applied to the surface of the polarizing film of the optical film laminate while applying the ultraviolet curable adhesive so that the thickness of the cured adhesive layer became 0.5 mu m, and ultraviolet rays were irradiated as an active energy ray to cure the adhesive. UV light irradiation was performed using a gallium-containing metal halide lamp, irradiation apparatus: Light HAMMER 10 manufactured by Fusion UV Systems, Inc., valve: V valve, peak illuminance: 1600 mW / cm ² , A cumulative irradiation amount of 1000 / mJ / cm ² (wavelength: 380 to 440 nm) was used, and the illuminance of the ultraviolet ray was measured using Solatell's Sola-Check system. Subsequently, the amorphous PET substrate was peeled off to produce a protective polarizing film A using a thin polarizing film. The obtained polarizing protective polarizing film had an optical characteristic of a transmittance of 42.8% and a polarization degree of 99.99%.

<Formation of anchor coat layer: polyvinyl alcohol-based resin composition>

100 parts of a polyvinyl alcohol resin having a degree of polymerization of 2500 and a degree of saponification of 99.7 mol% and 5 parts of methylol melamine (trade name &quot; Watersol: S-695 &quot;, trade name, manufactured by DIC Corporation) were dissolved in pure water to prepare an aqueous solution having a solid concentration of 4% .

&Lt; Preparation of acrylic polymer &

A four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas introducing tube and a condenser was charged with a monomer mixture containing 99 parts of butyl acrylate and 1 part of 2-hydroxyethyl acrylate. Further, 0.1 part of 2,2'-azobisisobutyronitrile as a polymerization initiator was added to 100 parts of the monomer mixture (solid content) together with ethyl acetate, and nitrogen gas was introduced with gentle stirring to replace with nitrogen. Then, The polymerization reaction was carried out for 7 hours while maintaining the liquid temperature in the vicinity of 60 占 폚. Thereafter, ethyl acetate was added to the obtained reaction solution to prepare a solution of an acrylic polymer having a weight average molecular weight of 1,400, adjusted to a solid concentration of 30%.

(Preparation of pressure-sensitive adhesive composition)

An oligomer-type mercapto group-containing silane coupling agent (amount of alkoxy group: 30% by weight, mercapto equivalent: 450 g / mol, X-41-1810, manufactured by Shin-Etsu Chemical Co., Ltd.) was added to 100 parts of the solid content of the acryl- And 0.42 part of dibenzoyl peroxide were mixed to prepare an acrylic pressure-sensitive adhesive solution.

(Formation of pressure-sensitive adhesive layer)

Subsequently, the acrylic pressure-sensitive adhesive solution was uniformly coated on the surface of a polyethylene terephthalate film (separator film) treated with a silicone-based releasing agent and dried in an air circulating thermostatic oven at 155 ° C for 2 minutes to form a 20 μm thick Thereby forming a pressure-sensitive adhesive layer.

Example 1

&Lt; Anchor coating layer-adhered protective polarizing film >

The polyvinyl alcohol-based resin composition adjusted to 25 DEG C on the surface of the polarizing film (polarizer) of the polarizing protective polarizing film (the polarizing surface on which the protective film was not formed) was coated with a wire bar coater so as to have a thickness of 1 mu m , And then dried by hot air at 90 캜 for 20 seconds to prepare an anchor coating layer-attached protective polarizing film.

&Lt; Preparation of polarizing film with pressure-sensitive adhesive layer >

Subsequently, a pressure-sensitive adhesive layer formed on the release treatment surface of the release sheet (separator) was stuck to an anchor coating layer formed on the protective polarizing film to prepare a polarizing film with a pressure-sensitive adhesive layer.

Examples 2 to 11 and Comparative Examples 1 to 6

The kind of the aqueous resin to be blended in the anchor coat layer in Example 1, the blending amount of methylolmelamine (the blended amount was 100 parts of the aqueous resin), the silane coupling agent in the pressure-sensitive adhesive composition, the type and amount of the crosslinking agent 100 parts) was changed as shown in Table 1, an anchor coating layer-attached polarizing protective film and an adhesive layer-adhered polarizing film were prepared in the same manner as in Example 1.

The polarizing film with a pressure-sensitive adhesive layer obtained in the above Examples and Comparative Examples was evaluated as follows. The results are shown in Table 1.

&Lt; Measurement of initial gel fraction >

And about 0.1 g of the pressure-sensitive adhesive layer formed on the peeled surface of the separator film within one minute was scratched to obtain Sample 1. The sample 1 was wrapped in a Teflon (registered trademark) film (trade name: "NTF1122", manufactured by Nitto Denko Kabushiki Kaisha) having a diameter of 0.2 μm, The weight of Sample 2 before being provided in the following test was measured and was referred to as weight A. Further, the weight A is the total weight of the sample 1 (pressure-sensitive adhesive layer), the Teflon (registered trademark) film and the smoke chamber. Further, the total weight of the Teflon (registered trademark) film and the smoke chamber was referred to as "weight B". Then, the sample 2 was placed in a 50 ml container filled with ethyl acetate and allowed to stand at 23 占 폚 for 1 week. Thereafter, Sample 2 was taken out of the vessel and dried in a drier at 130 캜 for 2 hours to remove ethyl acetate, and then the weight of Sample 2 was measured. The weight of Sample 2 after being provided in the above test was measured, and it was referred to as "weight C". The gel fraction was calculated from the following equation.

Gel fraction (% by weight) = (C-B) / (A-B) 100

The initial gel fraction of the pressure-sensitive adhesive layer is preferably 80% or more. A low gel fraction leads to troubles such as dents.

<Tillage strength>

The polarizing film with a pressure-sensitive adhesive layer obtained in Examples and Comparative Examples was cut into a size of 25 mm x 150 mm and the vapor-deposited side of the pressure-sensitive adhesive layer side and the vapor-deposited side of the evaporated film deposited with indium-tin oxide on the surface of the polyethylene terephthalate film . Thereafter, the end of the polyethylene terephthalate film was peeled off by hand, and after confirming that the pressure-sensitive adhesive layer adhered to the polyethylene terephthalate film side, a tensile tester AG-1 manufactured by Shimadzu Seisakusho was used to measure 300 mm (N / 25 mm) was measured (25 캜) at the time of peeling at a rate of 1 / min.

The anchoring force of 15 N / 25 mm or more is preferable because the adhesive remained at the time of reworking and there was no lack of adhesive or dropout at the time of processing. The fracture state at the time of peeling is referred to as &quot; cohesive failure (fracture of anchor coat layer or pressure-sensitive adhesive layer) &quot; or &quot; interface peeling (peeling at interface between anchor coat layer and pressure-sensitive adhesive layer) &quot;. In Comparative Example 7, only an isocyanate-based crosslinking agent was used as a crosslinking agent in the pressure-sensitive adhesive layer. The examples and other comparative examples are values measured within 24 hours (without aging) of the polarizing film with a pressure-sensitive adhesive layer.

In Table 1, the peroxide is a trade name: NIPER BMT 40SV, benzoyl peroxide, manufactured by Nippon Oil Co., Ltd.;

The isocyanate system is commercially available under the tradename: Takenate D110N, trimethylol propane adduct of xylylene diisocyanate, manufactured by Mitsui Chemicals, Inc.;

X-41-1810: oligomer type mercapto group-containing silane coupling agent, amount of alkoxy group: 30% by weight, mercapto equivalent: 450 g / mol, manufactured by Shin-Etsu Chemical Co.,

KBM-802: monomer-type mercapto group-containing silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.;

KBM-803: a monomer-type mercapto group-containing silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.;

X-41-1056: Oligomer-type epoxy group-containing silane coupling agent, amount of alkoxy group: 17% by weight, epoxy equivalent: 280 g / mol, manufactured by Shin-Etsu Chemical Co.,

.

The crosslinking agent of Example 10 is a combination system of an isocyanate crosslinking agent and a peroxide crosslinking agent.

Oxazoline group-containing polymer: Epochros WS-700 (manufactured by Nippon Shokubai Co., Ltd.);

Polyurethane resin: Takerak W-6020 (manufactured by Mitsui Kagaku Polyurethane Co., Ltd.);

Epoxy resin: Celloxide 2021P (manufactured by Daicel Co., Ltd.).

1: Polarizer
2: Anchor coating layer (main component of polyvinyl alcohol resin)
3: Pressure-sensitive adhesive layer
4: Separator
5,5 ': Protective film
10: Polarizing film with pressure-sensitive adhesive layer
11: Polarizing film with pressure-sensitive adhesive layer

Claims (19)

As a polarizing film with a pressure-sensitive adhesive layer having a polarizer, an anchor coating layer and a pressure-sensitive adhesive layer in this order,
The anchor coating layer is formed from a water-based resin composition containing an aqueous resin and methylol melamine,
Wherein the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a silane coupling agent containing a mercapto group. The method according to claim 1,
Wherein the water-based resin is at least one selected from a polyvinyl alcohol-based resin, a polyurethane-based resin, an epoxy-based resin and an oxazoline group-containing polymer. 3. The method of claim 2,
The polarizing film with a pressure-sensitive adhesive layer, wherein the water-based resin is a polyvinyl alcohol-based resin. The method of claim 3,
Wherein the polyvinyl alcohol-based resin has a saponification degree of 96 mol% or more and an average degree of polymerization of 2000 or more. The method according to claim 1,
Wherein the water-based resin composition contains 0.2 to 20 parts by weight of methylolmelamine based on 100 parts by weight of the water-based resin. delete The method according to claim 1,
Wherein the anchor coating layer has a thickness of 0.05 占 퐉 or more and 6 占 퐉 or less. The method according to claim 1,
The polarizing film with a pressure-sensitive adhesive layer, wherein the base polymer having a hydroxyl group is a (meth) acryl-based polymer having a hydroxyl group. The method according to claim 1,
Wherein the pressure-sensitive adhesive composition comprises 0.01 to 5 parts by weight of the mercapto group-containing silane coupling agent per 100 parts by weight of the base polymer having the hydroxyl group. The method according to claim 1,
A polarizing film with a pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive composition contains a crosslinking agent. 11. The method of claim 10,
Wherein the cross-linking agent contains a cross-linking agent (b) that does not react with the hydroxyl group. 12. The method of claim 11,
Wherein the crosslinking agent (b) which does not react with the hydroxyl group is a peroxide. 12. The method of claim 11,
Wherein the crosslinking agent (b) which does not react with the hydroxyl group is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the base polymer having the hydroxyl group. The method according to claim 1,
Wherein the polarizer has a thickness of 15 占 퐉 or less. The method according to claim 1,
Wherein the polarizer has an optical characteristic represented by a simple transmittance (T) and a polarization degree (P)
P > - (10 ^0.929 T ^-42.4 -1) x 100 (with T <42.3) and
P? 99.9 (provided that T? 42.3). The method according to claim 1,
A polarizing film with a pressure-sensitive adhesive layer, which has a protective film on at least one side of the polarizer. The method according to claim 1,
A polarizing film with a pressure-sensitive adhesive layer, wherein a separator is laminated on the pressure-sensitive adhesive layer. A method for producing a polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 5 and 7 to 17,
A step of coating an aqueous resin composition containing a water-based resin and methylol melamine on a polarizer and then drying to form an anchor coat layer;
A step of forming a pressure-sensitive adhesive layer from a pressure-sensitive adhesive composition containing a base polymer having a hydroxyl group and a mercapto group-containing silane coupling agent on the anchor coat layer,
Wherein the pressure-sensitive adhesive layer has a pressure-sensitive adhesive layer. An image display apparatus having the polarizing film with a pressure-sensitive adhesive layer according to any one of claims 1 to 5 and 7 to 17.

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