KR102204750B1 - Liquid crystal panel and image display apparatus - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal panel that does not become cloudy due to humidification and an image display device using the liquid crystal panel.
One side of the liquid crystal cell is a high contact angle surface with a contact angle of 40 to 110° with water, and a saturated moisture content of 0.3 to 6% by weight at 60°C and 90% RH on the high contact angle side of the liquid crystal cell A layer and a first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ·day) at 40°C and 90% RH, and on the other side of the liquid crystal cell, the moisture permeability at 40°C and 90% RH It is a liquid crystal panel characterized by having a 2nd polarizing film of 8 g/(m ² ·day) or more.

Description

Liquid crystal panel and image display device {LIQUID CRYSTAL PANEL AND IMAGE DISPLAY APPARATUS}

The present invention relates to a liquid crystal panel and an image display device including the liquid crystal panel.

In a liquid crystal panel used in a liquid crystal display device or the like, a polarizing film is laminated on both sides of a liquid crystal cell formed of a liquid crystal layer disposed between a pair of transparent substrates through an adhesive layer. Although such a pressure-sensitive adhesive layer for optical applications such as a liquid crystal panel is required to have high transparency, it has been known that the pressure-sensitive adhesive layer may become cloudy (whitening) when it is returned to room temperature after exposure to high temperature and high humidity conditions. This clouding phenomenon is thought to be caused by aggregation when moisture absorbed in the pressure-sensitive adhesive layer under moist heat is returned to room temperature, and various studies have been conducted on suppression of whitening of the pressure-sensitive adhesive layer by humidification.

As the pressure-sensitive adhesive composition capable of suppressing the turbidity of the pressure-sensitive adhesive layer, for example, a monomer containing an alkyl ester monomer having 1 to 18 carbon atoms of (meth)acrylic acid, a copolymerizable monomer containing a hydroxyl group, and a dialkyl substituted acrylamide monomer. At least one of an optical pressure-sensitive adhesive composition comprising an acrylic resin and a crosslinking agent, which is a copolymer having a weight average molecular weight of 300,000 to 2 million, or a nitrogen-containing vinyl monomer without a hydroxyl group or an alkoxy group-containing alkyl (meth)acrylate monomer A pressure-sensitive adhesive composition containing at least one of copolymerizable vinyl monomers containing no carboxyl group and containing a hydroxyl group is known (see, for example, Patent Documents 1 and 2).

Japanese Patent Publication No. 2011-195651 Japanese Patent Publication No. 2013-64079

In the above Patent Documents 1 and 2, it is intended to suppress the clouding of the pressure-sensitive adhesive layer by setting it as a specific pressure-sensitive adhesive composition, but it is not regulated at all in relation to an adherend such as a liquid crystal cell, and the moisture permeability of the polarizing film is examined at all. It was not made, and was not sufficient from the viewpoint of suppressing whitening of the liquid crystal panel as a whole.

In recent years, while improvement of viewing angle characteristics and reduction in thickness and weight are desired, low moisture permeability films are frequently used as retardation films or protective films in order to satisfy them. However, since the moisture permeable film is difficult to pass through, it was found that when the moisture contained in the pressure-sensitive adhesive layer was returned to room temperature under humidification, it was difficult to fall out of the pressure-sensitive adhesive and the pressure-sensitive adhesive layer became cloudy.

In addition, a transparent conductive film such as an indium tin oxide (ITO) thin film is formed on one transparent substrate of a liquid crystal cell constituting a liquid crystal panel, and the pressure-sensitive adhesive layer in contact with the transparent conductive film is in contact with a transparent substrate such as a glass substrate. Compared with the pressure-sensitive adhesive layer, it was found that there is a tendency to suppress whitening. That is, since the properties of both surfaces of a liquid crystal cell are usually different, it was found that it is necessary to suppress clouding appropriately on both surfaces of the liquid crystal cell to suppress the clouding of the liquid crystal panel as a whole.

Accordingly, an object of the present invention is to provide a liquid crystal panel that does not become cloudy due to humidification and an image display device including the liquid crystal panel.

In order to solve the above problems, the inventors of the present invention found that the above object can be achieved by controlling the moisture content of the pressure-sensitive adhesive layer on the high-contact angle side of the liquid crystal cell, the moisture permeability of the polarizing film, and the moisture permeability of the polarizing film on the other side. We found out and came to complete the present invention.

That is, in the present invention, one surface of the liquid crystal cell is a high contact angle surface having a contact angle of 40 to 110° with water, and the high contact angle surface of the liquid crystal cell has a saturated moisture content at 60°C and 90% RH of 0.3 to A pressure-sensitive adhesive layer of 6% by weight, and a first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ·day) at 40°C and 90% RH, and on the other side of the liquid crystal cell, 40°C, 90% It relates to a liquid crystal panel comprising a second polarizing film having a moisture permeability of 8 g/(m ² ·day) or more in RH.

It is preferable that the moisture permeability of the second polarizing film is greater than that of the first polarizing film.

It is preferable that the saturated moisture content of the pressure-sensitive adhesive layer at 60°C and 90% R.H. is 0.5 to 6% by weight.

It is preferable that the high contact angle surface of the liquid crystal cell is formed of a transparent conductive layer.

It is preferable that the other side of the high contact angle surface of the liquid crystal cell is a low contact angle surface having a contact angle with respect to water of 3° or more and less than 40°.

It is preferable that the said 2nd polarizing film is laminated|stacked on a liquid crystal cell via the pressure-sensitive adhesive layer whose saturated moisture content in 60 degreeC and 90% R.H. is 0.5-6 weight%.

Further, the present invention relates to an image display device comprising the liquid crystal panel.

In the present invention, by disposing a pressure-sensitive adhesive layer having a specific saturated moisture content and a first polarizing film having a specific moisture permeability on the high contact angle surface of the liquid crystal cell, and disposing a second polarizing film having a specific moisture permeability on the other side of the liquid crystal cell, Cloudiness due to humidification as a whole of the liquid crystal panel can be suppressed. This is because the value of the water contact angle is large in the high contact angle surface of the liquid crystal cell, so the amount of moisture that penetrates from the interface between the high contact angle surface of the liquid crystal cell and the pressure-sensitive adhesive layer during humidification decreases, and as a result, the amount of moisture that aggregates when taken out from humidification to room temperature Since there is less, it is possible to suppress the turbidity of the pressure-sensitive adhesive layer by laminating the first polarizing film having a specific moisture permeability through the pressure-sensitive adhesive layer having a specific saturated moisture content on the surface. On the other hand, on the other side of the liquid crystal cell, a substrate with a small contact angle of water, such as a glass substrate, is usually used, and the amount of moisture that penetrates from the interface between the substrate and the pressure-sensitive adhesive layer is large, and as a result, the amount of moisture that aggregates when taken out from humidification to room temperature. Although this increases, since the said surface has a 2nd polarizing film which has a specific moisture permeability, moisture contained in an adhesive layer is efficiently discharged to the outside, and it can suppress whitening.

In addition, a method of increasing the moisture content of the pressure-sensitive adhesive layer is known as one of the methods of suppressing clouding. In such a simple method of increasing the moisture content of the pressure-sensitive adhesive layer, the composition of the pressure-sensitive adhesive layer is limited, and the durability (foaming and peeling) of the pressure-sensitive adhesive layer tends to deteriorate. However, in the present invention, as described above, the liquid crystal cell in the liquid crystal panel By specifying the upper and lower configurations, it is possible to suppress whitening of the entire liquid crystal panel, and the durability is also good, and the degree of freedom in designing the pressure-sensitive adhesive layer is wider than that of the conventional method of increasing the moisture content of the pressure-sensitive adhesive layer.

1 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel of the present invention.
2 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel of the present invention.
3 is a cross-sectional view schematically showing an embodiment of a liquid crystal panel of the present invention.

1. LCD panel

The liquid crystal panel of the present invention has a polarizing film on both sides of a liquid crystal cell, and one side of the liquid crystal cell is a high contact angle surface having a contact angle of 40 to 110° with water, and 60°C and 90% RH on the high contact angle surface A pressure-sensitive adhesive layer having a saturated moisture content of 0.3 to 6% by weight and a first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ·day) at 40°C and 90% RH, and the other side of the liquid crystal cell It is characterized by having a second polarizing film having a moisture permeability of 8 g/(m ² ·day) or more at 40°C and 90% RH. Hereinafter, the liquid crystal panel of the present invention will be described in detail.

(1) liquid crystal cell

The liquid crystal cell used in the liquid crystal panel of the present invention may have a contact angle of 40 to 110° with respect to water on one side, and is not particularly limited. For example, a liquid crystal layer and an agent disposed on one side of the liquid crystal layer A pixel electrode for applying a voltage to the liquid crystal layer to the first substrate or the second substrate, including a substrate (viewer side) and a second substrate (light source side) disposed on the other side of the liquid crystal layer And a counter electrode formed thereon.

The substrate for a liquid crystal cell may be a transparent substrate and is not particularly limited, and examples thereof include a glass substrate and a plastic substrate. As a glass substrate, an alkali glass substrate, an alkali-free glass substrate, etc. are mentioned. In addition, various plastic substrates having transparency are exemplified as plastic substrates, and as materials thereof, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, Polyamide resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenyl Rensulfide-based resins, etc. are mentioned.

A surface (high contact angle surface) of the liquid crystal cell with a water contact angle of 40 to 110° may be formed on either the first substrate or the second substrate.

Usually, a transparent conductive film such as an indium tin oxide (ITO) thin film is formed on one transparent substrate of a liquid crystal cell constituting a liquid crystal panel, and the surface on which the transparent conductive film is formed can be a high contact angle surface. In addition, for example, in an on-cell type or in-cell type touch panel, metal wiring such as copper or silver is provided on the outermost layer, or in some cases, acrylic resin or the like is coated on the metal wiring. The surface can be a high contact angle surface.

The contact angle of the high contact angle surface with respect to water is 40 to 110°, but may be 45 to 100° or 45 to 90°. The contact angle of the high contact angle surface on which the above-described transparent conductive film or the like is formed is usually 40° or more. In addition, when the contact angle exceeds 110°, the adhesiveness with the pressure-sensitive adhesive layer decreases, and durability tends to deteriorate.

The transparent substrate has a transparent conductive film or acrylic resin coating film formed thereon by pre-sputtering, corona discharge, plasma treatment, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation, etc. You may try to improve the adhesion to. Further, before forming the transparent conductive film or the acrylic resin coating film, it may be subjected to vibration damping and cleaning by solvent cleaning or ultrasonic cleaning, if necessary.

The material for constituting the transparent conductive film is not particularly limited, and at least one selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten Metal oxides of the metals of are used. The metal oxide may further contain metal atoms shown in the group as necessary. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony, and the like are preferably used, and ITO is particularly preferably used. It is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide as ITO.

Moreover, as said ITO, any of crystalline ITO and amorphous (amorphous) ITO may be sufficient. Crystalline ITO can be obtained by applying a high temperature during sputtering or further heating amorphous ITO.

The thickness of the transparent conductive film is not particularly limited, but it is preferably 7 nm or more, more preferably 12 to 200 nm, further preferably 12 to 100 nm, and particularly preferably 18 to 70 nm. When the thickness of the transparent conductive film is less than 7 nm, there is a tendency that the transparent conductive film does not adhere uniformly in the plane, the resistance value in the panel surface is not stable, or a predetermined resistance value is not obtained. On the other hand, when it exceeds 200 nm, the productivity of the transparent conductive film decreases, the cost increases, and the optical properties tend to decrease.

The method for forming the transparent conductive film is not particularly limited, and a conventionally known method may be adopted. Specifically, a vacuum vapor deposition method, a sputtering method, and an ion plating method can be illustrated, for example. Further, a suitable method may be adopted according to the required film thickness.

In addition, the contact angle of the other side of the high contact angle surface of the liquid crystal cell with respect to water is not particularly limited, but it is usually a surface such as a glass substrate having a small contact angle with water. The other side of the high contact angle surface of the liquid crystal cell is preferably a low contact angle surface having a contact angle of 3° or more and less than 40°, for example.

The driving mode of the liquid crystal cell is not particularly limited, and any known one may be used. For example, a twisted nematic (TN) mode, a super twisted nematic (STN) mode, a horizontal alignment (ECB) mode, and a vertical alignment ( VA) mode, in-plane switching (IPS) mode, fringe field switching (FFS) mode, bend nematic (OCB) mode, hybrid alignment (HAN) mode, ferroelectric liquid crystal (SSFLC) mode, and antiferroelectric liquid crystal (AFLC) mode. A liquid crystal cell is mentioned.

In addition, in the liquid crystal cell, a color filter, a black matrix, etc. may be provided on either of the substrates as necessary, and in the present invention, a liquid crystal cell may be used as it is mounted on a commercially available liquid crystal display device.

(2) adhesive layer

A first polarizing film is bonded to the high-contact angle surface of the liquid crystal cell through an adhesive layer.

The pressure-sensitive adhesive layer may have a saturated moisture content of 0.3 to 6% by weight at 60°C and 90% R.H., and its composition is not particularly limited. The saturated moisture content of the pressure-sensitive adhesive layer is preferably 0.5 to 5% by weight, more preferably 0.5 to 3.5% by weight, and particularly preferably 0.7 to 3.5% by weight. When the saturated moisture content of the pressure-sensitive adhesive layer exceeds 6% by weight, the amount of moisture that can be introduced into the pressure-sensitive adhesive layer increases, and foaming may occur under high temperature, and durability tends to deteriorate. In addition, when the saturated moisture content is less than 0.3% by weight, the amount of water contained in the pressure-sensitive adhesive layer is low, the turbidity of the pressure-sensitive adhesive layer is deteriorated, and there is a tendency that whitening of the entire liquid crystal panel cannot be sufficiently suppressed.

It is preferable that the pressure-sensitive adhesive layer in the present invention is formed of a pressure-sensitive adhesive composition containing a base polymer and a crosslinking agent. The pressure-sensitive adhesive composition may be an acrylic, synthetic rubber, rubber, or silicone pressure sensitive adhesive, but from the viewpoint of transparency and heat resistance, an acrylic pressure sensitive adhesive having a (meth)acrylic polymer as a base polymer is preferable.

The (meth)acrylic polymer, which is the base polymer of the acrylic pressure-sensitive adhesive, is preferably obtained by polymerizing a monomer component containing a (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms, and (meth) having an alkyl group having 2 to 14 carbon atoms. It is more preferable that it is obtained by polymerizing a monomer component containing an acrylic acid ester as a main monomer. Here, the main monomer is preferably 60% by weight or more, and more preferably 70% by weight or more with respect to all monomer components constituting the (meth)acrylic polymer. In addition, (meth)acrylic acid ester refers to an acrylic acid ester and/or a methacrylic acid ester, and has the same meaning as the (meth) of the present invention.

As the (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms, for example, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate , Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylic Rate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc. These may be mentioned, and these may be used alone or in combination of two or more. Among these, a (meth)acrylic acid ester having an alkyl group having 2 to 12 carbon atoms is more preferable because its hydrophilic property is stronger.

The monomer component may contain other polymerizable monomers other than the (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms. The above other polymerizable monomers are not particularly limited as long as they have a polymerizable functional group relating to an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, but examples thereof include a hydroxyl group-containing monomer and a carboxyl group-containing monomer. have.

As the hydroxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and having a hydroxyl group can be used without particular limitation. As a hydroxyl group-containing monomer, for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth) Acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethylcyclohexyl)methyl (meth) Acrylate, etc. are mentioned, and these can be used individually by 1 type or in mixture of 2 or more types. The hydroxyl group-containing monomer is preferable because it has an effect of enhancing the adhesion to the transparent conductive film (especially ITO). Among these, a hydroxyl group-containing acrylic monomer having 2 to 14 carbon atoms in the side chain is preferable because it has a high effect of enhancing the adhesion to the transparent conductive film and has a stronger hydrophilic property.

The content of the hydroxyl group-containing monomer is preferably 10% by weight or less in the monomer component, more preferably 0 to 5% by weight, and still more preferably 0.1 to 4% by weight. In addition, in the present invention, in particular, by using the content of a hydroxyl group-containing acrylic monomer having a side chain of 12 or less in the above range, the hydrophilicity of the pressure-sensitive adhesive composition can be adjusted, and as a result, the saturated moisture content of the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition can be adjusted. It is preferable because there is.

As the carboxyl group-containing monomer, those having a polymerizable functional group having an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and having a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and the like, and these may be used alone or in combination. Can be used.

It is preferable that the content of the carboxyl group-containing monomer is 10% by weight or less in the monomer component. When the carboxyl group-containing monomer exceeds 10% by weight of the monomer component, it is not preferable because there is a tendency to significantly deteriorate transparent conductive films such as ITO films under humidification conditions.

Other copolymerization monomers are not particularly limited as long as they have a polymerizable functional group relating to an unsaturated double bond such as a (meth)acryloyl group or a vinyl group, and examples include cyclohexyl (meth)acrylate, bornyl (meth)acrylate, and ( (Meth)acrylic acid alicyclic hydrocarbon esters such as isobornyl meth)acrylate; (Meth) acrylate aryl esters, such as phenyl (meth) acrylate; Vinyl esters such as vinyl acetate and vinyl propionate; Styrene-based monomers such as styrene; Epoxy group-containing monomers, such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; Amide group-containing monomers such as acrylamide, diethylacrylamide, acryloylmorpholine (ACMO), and N-vinylpyrrolidone (NVP); Amino group-containing monomers such as N,N-dimethylaminoethyl (meth)acrylate and N,N-dimethylaminopropyl (meth)acrylate; Cyclic nitrogen-containing monomers such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, and methylvinylpyrrolidone; Alkoxy group-containing monomers such as methoxyethyl (meth)acrylate and ethoxyethyl (meth)acrylate; Cyano group-containing monomers such as acrylonitrile and methacrylonitrile; Functional monomers such as 2-methacryloyloxyethyl isocyanate; Olefinic monomers such as ethylene, propylene, isoprene, butadiene and isobutylene; Vinyl ether monomers such as vinyl ether; Halogen atom-containing monomers such as vinyl chloride; N-vinylcarboxylic acid amides, etc. are mentioned.

Further, examples of the copolymerizable monomer include maleimide-based monomers such as N-cyclohexylmaleimide, N-isopropyl maleimide, N-laurylmaleimide, and N-phenylmaleimide; For example, N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl Itaconimide-based monomers such as itaconimide and N-lauryl itaconimide; For example, N-(meth)acryloyloxymethylenesuccinimide, N-(meth)acryloyl-6-oxyhexamethylenesuccinimide, N-(meth)acryloyl-8-oxyoctamethylenesuccinimide Succinimide-based monomers such as imide; For example, styrenesulfonic acid, allylsulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidopropanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloyloxynaphthalenesulfonic acid, etc. And sulfonic acid group-containing monomers.

Further, examples of the copolymerizable monomer include glycol-based acrylic ester monomers such as polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, methoxyethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate; Other examples thereof include heterocycles such as tetrahydrofurfuryl (meth)acrylate and fluorine (meth)acrylate, and acrylic acid ester-based monomers containing halogen atoms.

In addition, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth)acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylic (Mono or poly) (mono or poly) alkylene such as (mono or poly) ethylene glycol di (meth) acrylate such as acrylate or (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate In addition to glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropanetri(meth)acrylic Esters of (meth)acrylic acid and polyhydric alcohols such as acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Polyfunctional vinyl compounds such as divinylbenzene; And compounds having a reactive unsaturated double bond such as allyl (meth)acrylate and vinyl (meth)acrylate. In addition, as a polyfunctional monomer, a polyester (meth)acrylate obtained by adding two or more unsaturated double bonds such as (meth)acryloyl group and vinyl group as a functional group similar to that of the monomer component to the skeleton of polyester, epoxy, urethane, etc. , Epoxy (meth) acrylate, urethane (meth) acrylate, etc. may be used.

The ratio of the copolymerization monomer other than the hydroxyl group-containing monomer and the carboxyl group-containing monomer is preferably 40% by weight or less, more preferably 0 to 30% by weight, and still more preferably 0 to 20% by weight in the monomer component. However, since the amide group-containing monomer and the amino group-containing monomer may increase the hydrophilicity of the pressure-sensitive adhesive composition and deteriorate durability (foaming), each of the monomer components is preferably 15% by weight or less, and more preferably 8% by weight or less. .

The weight average molecular weight of the (meth)acrylic polymer used in the present invention is preferably in the range of 1.2 million to 3 million, more preferably 1.2 million to 2.7 million, and even more preferably 1.2 million to 2.5 million. When the weight average molecular weight was less than 1.2 million, there were cases where it was not preferable from the viewpoint of heat resistance. In addition, when the weight average molecular weight is less than 1.2 million, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer to impair transparency. In addition, the pressure-sensitive adhesive layer obtained using a (meth)acrylic polymer having a weight average molecular weight of less than 1.2 million may have poor solvent resistance and mechanical properties. In addition, when the weight average molecular weight is greater than 3 million, a large amount of diluting solvent is required to adjust the viscosity to be applied, which is not preferable from the viewpoint of cost. Moreover, since the weight average molecular weight is in the said range, it is preferable also from a viewpoint of corrosion resistance and durability. The weight average molecular weight is measured by GPC (gel permeation chromatography) and refers to a value calculated in terms of polystyrene.

For the production of such (meth)acrylic polymers, known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations can be appropriately selected, and are not particularly limited, but in the present invention, from the viewpoint of the moisture content of the pressure-sensitive adhesive layer It is preferably solution polymerization. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

In solution polymerization, ethyl acetate, toluene, etc. are used as a polymerization solvent. As a specific example of solution polymerization, a polymerization initiator is added under a stream of an inert gas such as nitrogen, and the reaction is usually carried out under reaction conditions of about 5 to 30 hours at about 50 to 70°C.

The polymerization initiator, chain transfer agent, emulsifier, and the like used in radical polymerization are not particularly limited and may be appropriately selected and used. In addition, the weight average molecular weight of the (meth)acrylic polymer can be controlled by the amount of the polymerization initiator and the chain transfer agent used, and the reaction conditions, and the appropriate amount of the (meth)acrylic polymer is adjusted according to the kind.

As a polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane)dihydrochloride, 2,2'-azobis[2-(5-methyl) -2-imidazolin-2-yl)propane]dihydrochloride, 2,2'-azobis(2-methylpropionamidine)disulfate, 2,2'-azobis(N,N'-dimethylene Isobutylamidine), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine]hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.) A crude initiator, potassium persulfate, persulfates such as ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylper Oxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1 ,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, 1,1-di(t-hex) Peroxide-based initiators such as silperoxy)cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, etc., a combination of persulfate and sodium hydrogen sulfite, and a combination of peroxide and reducing agents such as a combination of peroxide and sodium ascorbate, etc. Although it can be mentioned, it is not limited to these.

The polymerization initiator may be used alone, or two or more may be used in combination, but the total content is about 0.005 to 1 part by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. desirable.

As a chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, thioglycolic acid 2-ethylhexyl, 2,3-dimercapto-1-propanol, etc. Can be lifted. The chain transfer agent may be used alone or in combination of two or more, but the total content is about 0.1 part by weight or less based on 100 parts by weight of the total amount of the monomer component.

Various silane coupling agents can be added to the pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high temperature and high humidity conditions. As the silane coupling agent, any suitable functional group can be used. As a functional group, a vinyl group, an epoxy group, an amino group, a mercapto group, a (meth)acryloxy group, an acetoacetyl group, an isocyanate group, a styryl group, a polysulfide group, etc. are mentioned, for example. Specifically, vinyl group-containing silane coupling agents such as vinyl triethoxysilane, vinyl tripropoxysilane, vinyl triisopropoxysilane, and vinyl tributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc. Epoxy group-containing silane coupling agent; γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl Amino group-containing silane coupling agents such as -N-(1,3-dimethylbutylidene)propylamine and N-phenyl-γ-aminopropyltrimethoxysilane; mercapto group-containing silane coupling agents such as γ-mercaptopropylmethyldimethoxysilane; styryl group-containing silane coupling agents such as p-styryl trimethoxysilane; (meth)acrylic group-containing silane coupling agents such as γ-acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; An isocyanate group-containing silane coupling agent such as 3-isocyanate propyl triethoxysilane; Polysulfide group-containing silane coupling agents, such as bis(triethoxysilylpropyl) tetrasulfide, etc. are mentioned.

The silane coupling agent may be used alone or in combination of two or more, but the overall content is preferably 1 part by weight or less, and 0.01 to 1 part by weight based on 100 parts by weight of the base polymer (solid content). It is more preferable that it is negative, and it is still more preferable that it is 0.02 to 0.8 weight part. When the blending amount of the silane coupling agent exceeds 1 part by weight, unreacted coupling agent components are generated, which is not preferable from the viewpoint of durability.

Further, when the silane coupling agent can be copolymerized with the monomer component by radical polymerization, the silane coupling agent can be used as the monomer component. The ratio is preferably 0.005 to 0.7 parts by weight based on 100 parts by weight of the base polymer (solid content).

Furthermore, it is preferable to add a crosslinking agent to the pressure-sensitive adhesive composition used in the present invention, since cohesive force related to the durability of the pressure-sensitive adhesive can be imparted.

As a crosslinking agent, a polyfunctional compound is used, and an organic type crosslinking agent and a polyfunctional metal chelate are mentioned. Examples of the organic crosslinking agent include epoxy crosslinking agents, isocyanate crosslinking agents, carbodiimide crosslinking agents, imine crosslinking agents, oxazoline crosslinking agents, aziridine crosslinking agents, and peroxide crosslinking agents. The polyfunctional metal chelate is one in which a polyvalent metal atom is covalently bonded or coordinated with an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, etc. . An oxygen atom etc. are mentioned as an atom in the organic compound which is covalently bonded or coordinated, and an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. are mentioned as an organic compound. These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferable, and a combination of them is more preferable.

An isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups (including an isocyanate regenerated functional group temporarily protected by a blocking agent or quantification of an isocyanate group) per molecule.

Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as tolylene diisocyanate and xylene diisocyanate, alicyclic isocyanates such as isophorone diisocyanate, and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and alicyclic isocyanates such as isophorone diisocyanate, and 2,4-tolyl Aromatic diisocyanates such as rendiisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, and polymethylene polyphenyl isocyanate, trimethylolpropane/tolylenediisocyanate trimer adducts (trade names: Coronate L, Nippon Polyurethane High School Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, Nippon Polyurethane Co., Ltd. product), isocyanurate body of hexamethylene diisocyanate (brand name : Isocyanate adducts such as coronate HX and Nippon Polyurethane High School Co., Ltd.), trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemical Co., Ltd.), trimethyl of hexamethylene diisocyanate Allpropane adduct (trade name: D160N, manufactured by Mitsui Chemical Co., Ltd.); Polyether polyisocyanate, polyester polyisocyanate, and adducts of these and various polyols, isocyanurate bonds, biuret bonds, polyisocyanates obtained by polyfunctionalization by allophanate bonds, and the like. Among these, the use of an aliphatic isocyanate is preferable because the reaction speed is high.

Various peroxides are used as the peroxide crosslinking agent. As peroxide, di(2-ethylhexyl)peroxydicarbonate, di(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxyneodecano 8, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di(4-methylbenzoyl)peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, etc. are mentioned. Among these, di(4-t-butylcyclohexyl)peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

The blending ratio of the crosslinking agent in the pressure-sensitive adhesive composition is not particularly limited, but is usually blended in a ratio of about 10 parts by weight or less of the crosslinking agent (solid content) to 100 parts by weight of the base polymer (solid content). The blending ratio of the crosslinking agent is preferably about 0.01 to 10 parts by weight, more preferably about 0.01 to 5 parts by weight. Further, in particular, when using a peroxide-based crosslinking agent, about 0.05 to 1 part by weight is preferable, and about 0.06 to 0.5 part by weight is more preferable based on 100 parts by weight of the base polymer (solid content).

Further, the pressure-sensitive adhesive composition used in the present invention includes a viscosity modifier, a peel modifier, a tackifier, a plasticizer, a softener, a glass fiber, glass beads, metal powder, and other inorganic powders, if necessary, as a filler, pigment, colorant (pigment , Dyes, etc.), pH adjusters (acids or bases), antioxidants, ultraviolet absorbers, and the like may be further appropriately used in various additives within a range not departing from the object of the present invention.

Although the method of forming the pressure-sensitive adhesive layer is not particularly limited, the pressure-sensitive adhesive composition is applied on various substrates, dried with a dryer such as a heat oven, and evaporated to form a pressure-sensitive adhesive layer, and a polarizing film or liquid crystal cell described later The method of transferring the pressure-sensitive adhesive layer onto the substrate of may be used, or the pressure-sensitive adhesive composition may be applied directly onto the polarizing film or liquid crystal cell to form a pressure-sensitive adhesive layer. In the present invention, a method of preparing a polarizing film with an adhesive layer in which an adhesive layer is formed on a polarizing film in advance is prepared, and a method of attaching the polarizing film with an adhesive layer to a liquid crystal cell is preferable.

It does not specifically limit as said base material, For example, various base materials, such as a release film and a transparent resin film base material, are mentioned.

Various methods are used as a method of applying the pressure-sensitive adhesive composition to the substrate or polarizing film. Specifically, for example fountain coater, roll coating, kiss roll coating, gravure coating, reverse coating, roll brush, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, die coater Methods, such as an extrusion coating method by etc., are mentioned.

Drying conditions (temperature, time) are not particularly limited and may be appropriately set depending on the composition and concentration of the pressure-sensitive adhesive composition, but for example, about 80 to 170°C, preferably 90 to 200°C for 1 to 60 minutes, preferably Is 2 to 30 minutes.

The thickness (after drying) of the pressure-sensitive adhesive layer is preferably 5 to 100 µm, more preferably 7 to 70 µm, and still more preferably 10 to 50 µm, for example. When the thickness of the pressure-sensitive adhesive layer is less than 5 µm, the adhesion to the adherend becomes insufficient, and durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, if the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the pressure-sensitive adhesive composition cannot be sufficiently dried when the pressure-sensitive adhesive composition is applied or dried when forming the pressure-sensitive adhesive layer, bubbles remain, or thickness irregularity occurs on the surface of the pressure-sensitive adhesive layer. As a result, the appearance problem tends to be easy to present.

As a constituent material of the release film, for example, resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabric, nets, foam sheets, metal foils, and laminates thereof, etc. Although a suitable thin leaf body etc. are mentioned, a resin film is used suitably from the point which is excellent in surface smoothness.

As a resin film, for example, polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, poly Urethane films, ethylene-vinyl acetate copolymer films, and the like.

The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The release film may be subjected to a release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based releasing agent, silica powder, or the like, or an antistatic treatment such as coating type, paste type, and vapor deposition type. In particular, by appropriately performing a release treatment such as a silicone treatment, a long chain alkyl treatment, or a fluorine treatment on the surface of the release film, the release property from the pressure-sensitive adhesive layer can be further improved.

Although it does not specifically limit as said transparent resin film base material, Various resin films which have transparency are used. The resin film is formed of a single layer of film. For example, as the material, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins , (Meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Among these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferred.

The thickness of the film substrate is preferably 15 to 200㎛.

Moreover, you may have an anchor layer between a polarizing film and an adhesive layer. The material for forming the anchor layer is not particularly limited, and examples thereof include various polymers, metal oxide sols, and silica sols. Among these, polymers are particularly preferably used. The use mode of the polymers may be any of a solvent-soluble type, an aqueous dispersion type, and an aqueous solution type.

Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinylpyrrolidone, and polystyrene resins. Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferred. A crosslinking agent can be appropriately blended into these resins. One or two or more of these other binder components can be suitably used according to the purpose. The thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.

The method of forming the anchor layer is not particularly limited, and it can be performed by a generally known method. Further, when the anchor layer is formed, the iodine-based polarizing film may be subjected to an activation treatment. The activation treatment can adopt various methods, for example, corona treatment, low pressure UV treatment, plasma treatment, and the like.

The method of forming the pressure-sensitive adhesive layer on the anchor layer on the polarizing film is as described above.

In addition, when the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer for transparent conductive films and the pressure-sensitive adhesive layer on the liquid crystal cell are exposed, the pressure-sensitive adhesive layer may be protected with a release film (separator) until practical use. As a release film, the thing mentioned above is mentioned. When a release film is used as a base material in the production of the pressure-sensitive adhesive layer, by bonding the pressure-sensitive adhesive layer on the release film and a polarizing film or liquid crystal cell, the release film is an adhesive of a polarizing film with a pressure-sensitive adhesive layer for a transparent conductive film or a liquid crystal cell with a pressure-sensitive adhesive layer. It can be used as a layer release film, and simplification in the process surface is possible.

(3) first polarizing film

As the first polarizing film to be bonded to the high contact angle surface of the liquid crystal cell via the pressure-sensitive adhesive layer described above, the moisture permeability at 40°C and 90% RH may be 0.5 to 30 g/(m ² ·day), and is particularly limited. It does not become. In addition, the moisture permeability of the first polarizing film is preferably 3.0 to 30 g/(m ² ·day), more preferably 6.0 to 30 g/(m ² ·day), and 9.0 to 30 g/(m ² ·day) It is more preferable that it is, and it is most preferable that it is 21.0 to 30 g/(m ² ·day). When the moisture permeability of the first polarizing film is less than 0.5 g/(m ² ·day), the moisture in the pressure-sensitive adhesive layer becomes difficult to fall out through the first polarizing film. As a result, while the whitening of the pressure-sensitive adhesive layer deteriorates, foaming occurs and durability deteriorates. Adjustment of the moisture permeability of the first polarizing film can be performed by appropriately adjusting the moisture permeability and thickness of the transparent protective film described later.

As a polarizing film, what has a transparent protective film on one side or both sides of a polarizer is generally used.

The polarizer is not particularly limited, and various types of polarizers can be used. As a polarizer, for example, uniaxial stretching by adsorbing dichroic substances such as iodine or dichroic dye to a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene/vinyl acetate copolymer-based partial saponification film. And polyene-based oriented films, such as dehydration treatment products of polyvinyl alcohol and dehydrochloric acid treatment products of polyvinyl chloride. Among these, a polarizer containing a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable, and an iodine polarizer containing iodine and/or iodine ions is more preferable. Further, the thickness of these polarizers is not particularly limited, but is generally about 5 to 80 µm.

A polarizer obtained by uniaxially stretching a polyvinyl alcohol-based film by dyeing it with iodine can be produced by, for example, dyeing by immersing polyvinyl alcohol in an aqueous solution of iodine and stretching it to 3 to 7 times its original length. If necessary, it may be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, or zinc chloride. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, not only can the surface of the polyvinyl alcohol-based film be cleaned of contamination or blocking agents, but also the polyvinyl alcohol-based film is swelled to prevent unevenness such as staining of dyeing. Stretching may be performed after dyeing with iodine, stretching may be performed while dyeing, or may be dyed with iodine after stretching. It can also be stretched in an aqueous solution such as boric acid or potassium iodide or in a water bath.

Further, in the present invention, a thin polarizer having a thickness of 10 µm or less can also be used. Speaking from the viewpoint of thinning, the thickness is preferably 1 to 7 µm. It is preferable that such a thin polarizer has little thickness unevenness, has excellent visibility, and has little dimensional change, so that it is excellent in durability, and further, the thickness as a polarizing film is also reduced in thickness.

Typical examples of the thin polarizer include Japanese Patent Laid-Open No. 51-069644, Japanese Patent Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or Japanese Patent No. 4751481 B. The thin polarizing film described in Japanese Patent Application Laid-Open No. 2012-073563 is mentioned. These thin polarizing films can be obtained by a manufacturing method including a step of stretching a polyvinyl alcohol-based resin (hereinafter, also referred to as a PVA-based resin) layer and a resin substrate for stretching in a laminated state and a step of dyeing. In this manufacturing method, even if the PVA-based resin layer is thin, it is supported by the resin substrate for stretching, so that it is possible to stretch without problems such as fracture due to stretching.

The thin polarizing film can be stretched at a high magnification among manufacturing methods including a step of stretching and dyeing in the state of a layered body, so that the polarization performance can be improved.International Publication No. 2010/100917 pamphlet, International Publication No. It is preferably obtained by a manufacturing method including a step of stretching in an aqueous boric acid solution as described in a pamphlet of 2010/100917 or Japanese Patent No. 4751481 or Japanese Patent Laid-Open No. 2012-073563, and in particular, Japanese Patent No. 4751481 or Japanese Patent It is preferable to obtain by a manufacturing method including a step of auxiliary air stretching before stretching in an aqueous boric acid solution described in Unexamined Publication No. 2012-073563.

As the material for forming the transparent protective film provided on one or both sides of the polarizer, the first polarizing film may have a moisture permeability of 0.5 to 30 g/(m ² ·day) at 40°C and 90% RH, It is not particularly limited. Examples of the material for forming the transparent protective film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, and polystyrene. Styrene polymers, such as acrylonitrile-styrene copolymer (AS resin), and polycarbonate polymers, etc. are mentioned. In addition, polyethylene, polypropylene, polyolefin having a cyclo- or norbornene structure, polyolefin-based polymers such as ethylene-propylene copolymers, vinyl chloride-based polymers, amide-based polymers such as nylon or aromatic polyamide, imide-based polymers, alcohol Pone polymer, polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, Epoxy polymers, blends of the polymers, etc. are also exemplified as examples of polymers forming the transparent protective film. The transparent protective film can also be formed as a resin cured layer of an acrylic, urethane, acrylic urethane, epoxy, silicone, or other thermosetting or ultraviolet curing type.

Although it does not specifically limit about the moisture permeability in 40 degreeC and 90% RH of a transparent protective film, it is preferable that it is 0.5-2500 g/(m ² ·day). Moreover, it is preferable that the moisture permeability in 40 degreeC and 90% RH of the protective film on the liquid crystal cell side is 0.5-300 g/(m ² ·day) among the transparent protective films. By setting the moisture permeability in 40°C and 90% RH of the transparent protective film on the liquid crystal cell side to the above range, the effect of suppressing clouding tends to be obtained, which is preferable.

Although the thickness of the protective film can be appropriately determined, it is generally about 1 to 500 µm in terms of workability such as strength and handling properties, and thin film properties.

The polarizer and the protective film are usually in close contact with each other through a water-based adhesive or the like. Examples of the water-based adhesive include isocyanate-based adhesives, polyvinyl alcohol-based adhesives, gelatin-based adhesives, vinyl-based latex-based, water-based polyurethane, and water-based polyesters. In addition to the above, examples of the adhesive between the polarizer and the transparent protective film include an ultraviolet curable adhesive and an electron beam curable adhesive. The adhesive for electron beam-curable polarizing films exhibits suitable adhesion to the above various transparent protective films. In addition, the adhesive used in the present invention can contain a metal compound filler.

Further, in the present invention, the moisture permeability of the first polarizing film may be within the above range, and for example, a retardation film or the like may be formed on the polarizer instead of the transparent protective film. In addition, a separate transparent protective film or a retardation film may be additionally installed on the transparent protective film.

The surface of the transparent protective film on which the opposite side (viewing side) of the transparent protective film is not adhered may be subjected to a hard coating layer, antireflection treatment, anti-sticking, or treatment for the purpose of diffusion or anti-glare.

(4) second polarizing film

A second polarizing film having a water vapor transmission rate of 8 g/(m ² ·day) or more at 40° C. and 90% RH is provided on the opposite side of the side of the liquid crystal cell constituting the liquid crystal panel of the present invention with a water contact angle of 40 to 110°. .

The moisture permeability of the second polarizing film is preferably 8 g/(m ² ·day) or more, more preferably 15 g/(m ² ·day) or more, more preferably 25 g/(m ² ·day) or more, and 25 g/ It is particularly preferable to exceed (m ² ·day). When the moisture permeability is less than 8 g/(m ² ·day), the moisture in the pressure-sensitive adhesive layer becomes difficult to fall out through the second polarizing film. As a result, white turbidity tends to occur in the pressure-sensitive adhesive layer on the side opposite to the high contact angle surface in which the water contact angle of the liquid crystal cell is 40 to 110°, which is not preferable.

In addition, it is preferable that the moisture permeability of the second polarizing film is greater than that of the first polarizing film. That is, it is preferable that the 1st polarizing film is a low moisture permeability film, and the 2nd polarizing film is a high moisture permeability film. In addition, the difference between the moisture permeability of the second polarizing film and the moisture permeability of the first polarizing film is not particularly limited, but is preferably larger than 10 g/(m ² ·day), for example. Since the water vapor transmission rate of the 2nd polarizing film and the 1st polarizing film exists in the said relationship, it is preferable from a viewpoint of whitening suppression of the whole liquid crystal panel.

As a polarizer constituting the second polarizing film and a protective film, the same thing as the first polarizing film can be mentioned. However, although the moisture permeability in 40 degreeC and 90% RH of the transparent protective film used for a 2nd polarizing film is not specifically limited, It is preferable that it is 5 to 3000 g/(m ² ·day). In addition, among the transparent protective films constituting the second polarizing film, the moisture permeability of the protective film on the liquid crystal cell side in 40°C and 90% RH is preferably 10 to 2000 g/(m ² ·day). By setting the moisture permeability in 40°C and 90% RH of the transparent protective film on the liquid crystal cell side to the above range, the effect of suppressing clouding tends to be obtained, which is preferable.

The thickness of the protective film used for the second polarizing film can be appropriately determined, but is generally about 1 to 500 µm in terms of workability such as strength and handling properties, and thin film properties.

In addition, the second polarizing film can be attached to the liquid crystal cell through the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is the same as those used in the first polarizing film, but, for example, a second polarizing film is attached to the liquid crystal cell. It is preferable from the viewpoint of whitening suppression that the saturated moisture content in 60 degreeC and 90% RH of the following adhesive layer is 0.5-6 weight%.

(5) Structure of liquid crystal panel

The configuration of the liquid crystal panel of the present invention includes a liquid crystal cell having a high contact angle surface, a pressure-sensitive adhesive layer having a specific saturated moisture content on the high contact angle surface, and a first polarizing film having a specific moisture permeability, and is also specific to the other side of the liquid crystal cell. It is sufficient to have a second polarizing film having moisture permeability, and other configurations are not particularly limited. A specific configuration of the liquid crystal panel of the present invention will be described based on FIGS. 1 to 3, but the present invention is not limited thereto.

The form of the liquid crystal panel 12 of the present invention shown in Fig. 1 is as follows.

The liquid crystal cell 10 includes a liquid crystal layer 8, a first transparent substrate 7 (viewing side) disposed on one side of the liquid crystal layer 8, and a first transparent substrate 7 disposed on the other side of the liquid crystal layer. 2 A transparent conductive layer 6 is formed on the first transparent substrate 7 including the transparent substrate 9 (the light source side). A first polarizing film 4a is laminated on the high-contact angle surface A of the liquid crystal cell 10 via an adhesive layer 5a. The first polarizing film 4a has a polarizer 2a between the visible side transparent protective film 1a and the liquid crystal cell side transparent protective film 3a.

In addition, the liquid crystal panel 12 of the present invention shown in FIG. 2 has a phase difference layer 11 formed in place of the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG. The liquid crystal panel 12 is formed on the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG. 1 with an adhesive layer 5c further interposed therebetween to form the retardation layer 11.

In addition, in addition to the above, the liquid crystal panel of the present invention may appropriately include a transparent film or a brightness enhancing film formed on the visible side transparent protective film 1a via an adhesive layer.

The lower the moisture permeability of the polarizing film, the more likely to deteriorate cloudiness and durability (foaming), and the lower the water contact angle of the surface of the liquid crystal cell to which the adhesive layer is attached, the more water enters between the liquid crystal cell and the adhesive layer under humidification. Since it becomes easy to do, there exists a tendency for the cloudiness and durability to deteriorate. In addition, the relationship between the white turbidity and durability (foaming) of the pressure-sensitive adhesive layer is a trade-off, and if the saturated moisture content of the pressure-sensitive adhesive layer is high, the white turbidity is good, but the durability (foaming) is deteriorated. Conversely, when the saturated moisture content of the pressure-sensitive adhesive layer is low Cloudiness deteriorates, and durability (foaming) becomes good. That is, in the present invention, the water permeability of the polarizing film and the moisture content of the pressure-sensitive adhesive layer are set in an appropriate range in relation to the water contact angle on the surface of the liquid crystal cell, whereby clouding as a whole liquid crystal panel can be suppressed.

2. Image display device

The image display device of the present invention includes the liquid crystal panel of the present invention. Hereinafter, a liquid crystal display device will be described as an example, but the present invention can be applied to all display devices requiring a liquid crystal panel.

Specific examples of the image display device to which the liquid crystal panel of the present invention can be applied include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), a field emission display (FED), and the like.

The image display device of the present invention should just include the liquid crystal panel of the present invention, and other configurations are the same as those of the conventional image display device.

[Example]

Hereinafter, the present invention will be described in detail using examples, but the present invention is not limited to the following examples unless departing from the gist of the present invention. In addition, in each example, all of the parts and% are based on weight, and the room temperature standing conditions which are not specifically specified below are all 23°C and 65% R.H.

<Measurement of moisture permeability of transparent protective film and polarizing film>

Using a water vapor transmission rate measuring device (PERMATRAN-W, manufactured by MOCON), 40°C, 90% R.H. It measured in an atmosphere for 24 hours, and the water vapor transmittance (moisture permeability) of a transparent protective film and a polarizing film was measured. Measurement was performed according to JIS K7129B.

<Measurement of weight average molecular weight (Mw) of acrylic polymer>

The weight average molecular weight of the produced acrylic polymer was measured by GPC (gel transmission chromatography).

Device: HLC-8220GPC manufactured by Tosoh Corporation

column:

Sample column; TSKguardcolumn Super HZ-H (1EA) + TSKgel Super HZM-H (2EA) manufactured by Tosoh Corporation

Reference column; TSKgel Super H-RC (1ea) manufactured by Tosoh Corporation

Flow: 0.6 mL/min

Injection volume: 10 μL

Column temperature: 40°C

Eluent: THF

Injection sample concentration: 0.2% by weight

Detector: differential refractometer

In addition, the weight average molecular weight was calculated in terms of polystyrene.

Production Example 1 (Preparation of polarizing film (1))

A PVA film having a thickness of 80 μm was stretched up to 3 times while dyeing for 1 minute in an iodine solution at 30° C. and 0.3% concentration between rolls having different speed ratios. Thereafter, it was immersed for 0.5 minutes in an aqueous solution containing 60° C., boric acid at 4% concentration and potassium iodide at 10% concentration, and the total draw ratio was extended to 6 times. Subsequently, after washing by immersing for 10 seconds in an aqueous solution containing potassium iodide at 30°C and 1.5% concentration, it was dried at 50°C for 4 minutes to obtain a polarizer having a thickness of 25 μm. A PVA-based resin aqueous solution was applied to both sides of the polarizer, and an acrylic film having a thickness of 40 µm (moisture permeability: 50 g/(m ² ·day)) was applied to one side, and a TAC-based film having a thickness of 60 µm (moisture permeability: 1000 g/) on the other side. (m ² ·day)) was bonded to produce a polarizing film (1). The moisture permeability of the obtained polarizing film (1) was 20 g/(m ² ·day).

Production Example 2 (Preparation of Polarizing Film (2))

The 40 µm-thick acrylic film used in Preparation Example 1 was used as a 30 µm-thick acrylic film (moisture permeability: 68 g/(m ² ·day)), and a 60 µm-thick TAC-based film was used as a 40 µm-thick TAC-based film (moisture permeability: 1400 g/(m ² ·day)), except having changed it, it carried out similarly to manufacture example 1, and obtained the polarizing film (2). The moisture permeability of the obtained polarizing film (2) was 25 g/(m ² ·day).

Production Example 3 (Preparation of Polarizing Film (3))

The 40 μm-thick acrylic film used in Preparation Example 1 was used as a 20 μm-thick acrylic film (moisture permeability: 110 g/(m ² ·day)), and a 60 μm-thick TAC-based film was used as a 25 μm-thick TAC-based film (moisture permeability: 2000 g/(m ² ·day)), and a 20 μm thick COP-based film (moisture permeability: 6.5 g/(m ² ·day) with a 10 μm-thick adhesive further interposed on the 20 μm-thick acrylic film side )), it carried out similarly to manufacture example 1, and obtained the polarizing film (3). The moisture permeability of the obtained polarizing film 3 was 6.1 g/(m ² ·day).

Production Example 4 (Preparation of polarizing film 4)

Polarizing film (4) in the same manner as in Production Example 3, except that a COP-based film having a thickness of 20 μm (moisture permeability: 6.5 g/(m ² ·day)) was not bonded through a 10 μm-thick adhesive in Production Example 3 Got it. The moisture permeability of the obtained polarizing film 4 was 35 g/(m ² ·day).

Production Example 5 (Production of polarizing film 5)

A PET-based film with a thickness of 25 µm (moisture permeability: 21 g/(m ² ·day)) was bonded to the side of the TAC-based film having a thickness of 25 µm of the polarizing film 4 of Production Example 4 through an additional 10 µm pressure-sensitive adhesive, The polarizing film (5) was obtained. The moisture permeability of the obtained polarizing film 5 was 7.2 g/(m ² ·day).

Production Example 6 (Preparation of polarizing film 6)

A PET-based film having a thickness of 20 µm (moisture permeability: 28 g/(m ² ·day)) was bonded to the side of the TAC-based film having a thickness of 25 µm of the polarizing film 4 of Production Example 4 through a 10 µm pressure-sensitive adhesive further interposed therebetween, The polarizing film (6) was obtained. The moisture permeability of the obtained polarizing film 6 was 9.7 g/(m ² ·day).

Production Example 7 (Production of polarizing film 7)

A COP-based film (moisture permeability: 3.4 g/(m ² ·day)) having a thickness of 30 μm was bonded to the polarizing film 4 of Production Example 4 through a pressure-sensitive adhesive having a thickness of 10 μm on the side of an acrylic film having a thickness of 20 μm, The polarizing film (7) was obtained. The moisture permeability of the obtained polarizing film (7) was 2.9 g/(m ² ·day).

The polarizing films (1) to (7) obtained in Production Examples 1 to 7 are as follows.

Example 1

(Preparation of acrylic pressure-sensitive adhesive composition)

In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 0.1 part of AIBN as an initiator were added with ethyl acetate per 100 parts of the monomer (solid content). After addition and reaction at 60°C for 7 hours under a nitrogen gas stream, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer having a weight average molecular weight of 1.6 million (solid content concentration 30% by weight). As a crosslinking agent, 0.1 parts of trimethylolpropane xylylenediisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemical Co., Ltd.) per 100 parts of the solid content of the acrylic polymer solution, 0.3 parts of dibenzoyl peroxide, and γ as a silane coupling agent -0.075 parts of glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive composition (1).

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) was uniformly applied to the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, dried in an air circulation constant temperature oven at 155° C. for 2 minutes, and then applied to the surface of the substrate. A pressure-sensitive adhesive layer having a thickness of 20 μm was formed. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 1 obtained in Production Example 1 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 were attached to each other to prepare a polarizing film with a pressure-sensitive adhesive layer. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 1 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side (viewing side) of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, on the opposite side of the liquid crystal cell (light source side) ) To the polarizing film 4 with an adhesive layer to form a liquid crystal panel.

Example 2

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was uniformly applied on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent in a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 2 obtained in Production Example 2 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film with a pressure-sensitive adhesive layer (2) on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 3

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 3 obtained in Production Example 3 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 4

(Preparation of acrylic pressure-sensitive adhesive composition)

99.5 parts of butyl acrylate, 0.5 parts of 4-hydroxybutyl acrylate, and 0.1 part of AIBN as an initiator in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirring device with ethyl acetate per 100 parts of the monomer (solid content) After addition and reaction at 60°C for 7 hours under a nitrogen gas stream, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer having a weight average molecular weight of 1.6 million (solid content concentration 30% by weight). As a crosslinking agent, 0.1 parts of trimethylolpropane xylylenediisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemical Co., Ltd.) per 100 parts of the solid content of the acrylic polymer solution, 0.3 parts of dibenzoyl peroxide, and γ as a silane coupling agent -0.075 parts of glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive composition (2).

In Example 3 (Preparation of a polarizing film with an adhesive layer), in the same manner as in Example 3, except that the adhesive layer formed on the polarizing film 3 was formed using the acrylic adhesive composition (2). A liquid crystal panel was produced. The moisture content of the pressure-sensitive adhesive layer formed on the polarizing film 3 was 0.5% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 5

(Preparation of acrylic pressure-sensitive adhesive composition)

99.9 parts of 2-ethylhexyl acrylate, 0.1 part of 6-hydroxyhexyl acrylate, and 0.1 part of AIBN as an initiator per 100 parts of monomer (solid content) acetic acid in a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirring device. After addition with ethyl and reacting at 60° C. for 7 hours under a stream of nitrogen gas, ethyl acetate was added to the reaction solution to obtain a solution containing an acrylic polymer having a weight average molecular weight of 1.8 million (solid content concentration 30% by weight). As a crosslinking agent, 0.1 part of an adduct body of trimethylolpropane/tolylene diisocyanate (trade name: Coronate L, manufactured by Nippon Polyurethane Co., Ltd.) per 100 parts of the solid content of the acrylic polymer solution and dioctyl tin dilaurate-based crosslinking accelerator (Brand name: Enviizer OL-1, manufactured by Tokyo Fine Chemicals Co., Ltd.) 0.03 parts, γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent ) Was blended to obtain an acrylic pressure-sensitive adhesive composition (3).

(Preparation of polarizing film with adhesive layer)

In Example 3 (Preparation of a polarizing film with an adhesive layer), in the same manner as in Example 3, except that the adhesive layer formed on the polarizing film 3 was formed using the acrylic adhesive composition (3). A liquid crystal panel was produced. The moisture content of the pressure-sensitive adhesive layer formed on the polarizing film 3 was 0.3% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 6

(Preparation of monomer component used for UV polymerization)

2-ethylhexyl acrylate 61 parts by weight, N-vinyl-2-pyrrolidone 14 parts by weight, two kinds of photopolymerization initiators (brand name: Irgacure 184, manufactured by BASF) 0.05 parts by weight and photopolymerization initiator (brand name: Ir Gacure 651, manufactured by BASF) 0.05 parts by weight of a 4-neck flask was added to prepare a monomer mixture. Subsequently, the monomer mixture was partially photopolymerized by exposure to ultraviolet rays in a nitrogen atmosphere to obtain a partial polymer (acrylic polymer syrup) having a polymerization rate of about 10% by weight.

To the total amount of the acrylic polymer syrup obtained (75.1 parts by weight), 2-hydroxyethyl acrylate (2HEA) 3 parts by weight, 4-hydroxybutyl acrylate (HBA) 22 parts by weight, dipentaerythritol pentaacrylate (brand name: KAYARAD After adding 0.12 parts by weight of DPHA, manufactured by Nippon Kayaku Co., Ltd., these were uniformly mixed to prepare a monomer component (4).

(Preparation of adhesive layer by UV polymerization)

Subsequently, the monomer component (4) adjusted above was peeled off one side with silicone, and the final thickness on the peeling-treated side of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi City Corporation) The coating layer was formed by coating so that the thickness was 20 μm. Subsequently, a 38 μm-thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi City Co., Ltd.) obtained by peeling off one side with silicone on the surface of the applied monomer component was prepared so that the peeling surface of the film was on the side of the coating layer. And coated. Thereby, the coating layer of the monomer component was blocked from oxygen. The sheet having the coating layer thus obtained was irradiated with ultraviolet rays of an illuminance of 5 mW/cm ² (measured by Topcon UVR-T1 with maximum sensitivity at about 350 nm) using a chemical light lamp (manufactured by Toshiba) for 360 seconds. Then, the coating layer was cured to form an adhesive layer, and an adhesive sheet was prepared. The polyester film coated on both sides of the pressure-sensitive adhesive layer functions as a release liner (separator).

(Preparation of polarizing film with adhesive layer)

Only one side of the separator of the pressure-sensitive adhesive layer was peeled off, and the separator in which the pressure-sensitive adhesive layer was formed on the acrylic film surface of the polarizing film 3 obtained in Production Example 3 was bonded to each other, thereby producing a polarizing film 3 with a pressure-sensitive adhesive layer. The moisture content of the pressure-sensitive adhesive layer formed on the polarizing film 3 was 3.1% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and the same as in Example 1 on the opposite side of the liquid crystal cell. A liquid crystal panel was formed by bonding the polarizing film 4 with an adhesive layer produced by the method.

Example 7

(Preparation of emulsion type acrylic pressure-sensitive adhesive composition)

To the container, 780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added and mixed to obtain a monomer mixture. Subsequently, 30 parts of Aqualon HS-10 (manufactured by Dai-Ichigo Kyoseyaku Co., Ltd.) and 635 parts of ion-exchanged water were added to 1000 parts of the monomer mixture prepared in the above ratio, and a homomixer (Tokushu Kika Kogyo Co., Ltd.) was used, and the mixture was stirred at 6000 rpm for 5 minutes to prepare a monomer emulsion.

Subsequently, 200 parts of the monomer emulsion prepared above and 515.9 parts of ion-exchanged water were added to a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel, and a stirring blade, and then the reaction vessel was sufficiently substituted with nitrogen. And 0.6 parts of ammonium persulfate were added, followed by polymerization at 60°C for 1 hour while stirring. Subsequently, the remaining monomer emulsion was added dropwise thereto over 3 hours while maintaining the reaction vessel at 60°C, and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Subsequently, after cooling the polymer emulsion to room temperature, 10% aqueous ammonia was added thereto to obtain an emulsion-type acrylic pressure-sensitive adhesive having a pH of 8 and further adjusted to a solid content of 45.6%.

(Preparation of polarizing film with adhesive layer)

After applying the emulsion-type acrylic pressure-sensitive adhesive on a release film (brand name: Diafoil MRF-38, polyethylene terephthalate base material, manufactured by Mitsubishi Chemical Co., Ltd.) so that the thickness after drying becomes 20 μm, by a die coater, It dried for 5 minutes at 120 ℃ to form a pressure-sensitive adhesive layer. Subsequently, the separator in which the pressure-sensitive adhesive layer was formed was attached to the acrylic film surface of the polarizing film 3 obtained in Production Example 3, and the polarizing film 3 with the pressure-sensitive adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 5.0% by weight.

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator in which the pressure-sensitive adhesive layer containing the acrylic pressure-sensitive adhesive composition (1) was formed on the acrylic film surface of the polarizing film 4 obtained in Production Example 4 was attached to each other, and a polarizing film with a pressure-sensitive adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 8

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having an adhesive layer formed on the acrylic film side of the polarizing film 5 obtained in Production Example 5 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 were attached to each other, thereby preparing a polarizing film with an adhesive layer. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 5 with a pressure-sensitive adhesive layer on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 9

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 7 obtained in Production Example 7 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 7 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 10

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 6 obtained in Production Example 6 and the acrylic film side of the polarizing film 4 obtained in Production Example 4 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 6 with a pressure-sensitive adhesive layer on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Example 11

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, two polarizing films (1) obtained in Production Example 1 were prepared, and a separator having a pressure-sensitive adhesive layer formed on each acrylic film surface of the polarizing film (1) was attached to each other, and a polarizing film with a pressure-sensitive adhesive layer was produced. . The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A liquid crystal panel was formed by bonding a polarizing film 1 with a pressure-sensitive adhesive layer on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer and the opposite side of the liquid crystal cell. .

Example 12

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 1 obtained in Production Example 1 and the acrylic film side of the polarizing film 6 obtained in Production Example 6 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film (1) with a pressure-sensitive adhesive layer on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 6) was bonded to form a liquid crystal panel.

Examples 13, 14

A liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) used in (Production of a liquid crystal panel) of Example 1 was crystallized ITO layer (contact angle to water: 58°, thickness: 20 nm) A liquid crystal panel was produced in the same manner as in Example 1, except that a liquid crystal cell having a and a liquid crystal cell having an acrylic resin layer (contact angle to water: 72°, thickness: 5 μm) was changed.

Comparative Example 1

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 4 obtained in Production Example 4 and the acrylic film side of the polarizing film 3 obtained in Production Example 3 was attached, and a polarizing film with a pressure-sensitive adhesive layer was produced. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 4 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 3) was bonded to form a liquid crystal panel.

Comparative Example 2

(Preparation of acrylic pressure-sensitive adhesive composition)

After attaching a three-way cock to a 2L three-necked flask and replacing the inside with nitrogen, toluene 868g, 1,2-dimethoxyethane 43.4g, isobutylbis(2,6-di-t-butyl-4- 60.0 g of a toluene solution containing 40.2 mmol of methylphenoxy)aluminum was added, and 3.68 g of a mixed solution of cyclohexane and n-hexane containing 6.37 mmol of sec-butyllithium was added. Then, 51.5 g of methyl methacrylate (MMA) was added to this, and it stirred at room temperature for 60 minutes. Subsequently, the internal temperature of the polymerization solution was cooled to -30°C, and 240 g of n-butyl acrylate (nBA) was added dropwise over 2 hours. Subsequently, 51.5 g of methyl methacrylate was added, and after stirring at room temperature overnight, 3.50 g of methanol was added to stop the polymerization reaction. The obtained reaction solution was poured into methanol, and the precipitate was recovered by filtration. By drying this, 340 g of block copolymer 1 was obtained.

As a result of 1H-NMR measurement and GPC measurement, the block copolymer 1 is a triblock copolymer of PMMA-PnBA-PMMA, the weight average molecular weight (Mw) is 7.9×10 ⁴ , and the number average molecular weight (Mn) is 6.2× It was 10 ⁴ and molecular weight distribution (Mw/Mn) was 1.27. In addition, PMMA-PnBA-PMMA represents polymethyl methacrylate-n-butyl polyacrylate-polymethyl methacrylate. The weight ratio of the monomer units of the block copolymer 1 was nBA/MMA=70/30.

(Preparation of polarizing film with adhesive layer)

The block copolymer 1 was dissolved in toluene to prepare a pressure-sensitive adhesive solution having a solid content concentration of 30%, and reverse the pressure so that the thickness of the pressure-sensitive adhesive layer after drying is 25 μm on a separator including a release-treated polyester film (38 μm in thickness). It applied by the coating method and heat-treated at 90 degreeC for 3 minutes, and the solvent was volatilized, and the adhesive layer was obtained. Subsequently, the separator in which the pressure-sensitive adhesive layer was formed was attached to the acrylic film surface of the polarizing film 3 obtained in Production Example 3, and the polarizing film 3 with the pressure-sensitive adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.1% by weight.

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Subsequently, the separator in which the pressure-sensitive adhesive layer containing the acrylic pressure-sensitive adhesive composition (1) was formed on the acrylic film surface of the polarizing film 4 obtained in Production Example 4 was attached to each other, and a polarizing film with a pressure-sensitive adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Comparative Example 3

(Preparation of emulsion type acrylic pressure-sensitive adhesive composition)

To the container, 780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added and mixed to obtain a monomer mixture. Subsequently, 60 parts of Aqualon HS-10 (manufactured by Dai-Ichigo Kyoseyaku Co., Ltd.) and 635 parts of ion-exchanged water were added to 1000 parts of the monomer mixture prepared in the above ratio, and a homomixer (Tokushu Kika Kogyo Co., Ltd.) was used, followed by stirring at 6000 (rpm) for 5 minutes to prepare a monomer emulsion.

Subsequently, 200 parts of the monomer emulsion prepared above and 515.9 parts of ion-exchanged water were added to a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel, and a stirring blade, and then the reaction vessel was sufficiently substituted with nitrogen. And 0.6 parts of ammonium persulfate were added, followed by polymerization at 60°C for 1 hour while stirring. Subsequently, the remaining monomer emulsion was added dropwise thereto over 3 hours while maintaining the reaction vessel at 60°C, and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Subsequently, after the polymer emulsion was cooled to room temperature, 10% aqueous ammonia was added thereto to obtain an emulsion-type acrylic pressure-sensitive adhesive (4) having a pH of 8 and further adjusted to a solid content of 45.6%.

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 and the emulsion-type acrylic pressure-sensitive adhesive (4) were dried so that the thickness after drying was 20 μm (trade name: Diafoil MRF-38, polyethylene terephthalate substrate, Mitsubishi Chemical After coating by a die coater on Ester Co., Ltd.), it was dried at 120°C for 5 minutes to form a pressure-sensitive adhesive layer. Subsequently, the separator in which the pressure-sensitive adhesive layer containing the emulsion-type acrylic pressure-sensitive adhesive 4 was formed was attached to the acrylic film surface of the polarizing film 3 obtained in Production Example 3 to prepare a polarizing film with a pressure-sensitive adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 6.2% by weight. Moreover, the separator in which the pressure-sensitive adhesive layer containing the acrylic pressure-sensitive adhesive composition (1) was formed on the acrylic film surface of the polarizing film (4) obtained in Production Example 4 was attached thereto to prepare a polarizing film with a pressure-sensitive adhesive layer. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film 3 with a pressure-sensitive adhesive layer was placed on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 4) was bonded to form a liquid crystal panel.

Comparative Example 4

(Preparation of polarizing film with adhesive layer)

The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 was evenly coated on the surface of a polyethylene terephthalate film (substrate) treated with a silicone-based release agent with a fountain coater, and dried in an air circulation constant temperature oven at 155°C for 2 minutes. , A pressure-sensitive adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. In addition, one more sheet of the same pressure-sensitive adhesive layer was produced. Subsequently, a separator having a pressure-sensitive adhesive layer formed on the acrylic film side of the polarizing film 1 obtained in Production Example 1 and the acrylic film side of the polarizing film 7 obtained in Production Example 7 was attached to each other to prepare a polarizing film with a pressure-sensitive adhesive layer. I did. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film (1) with a pressure-sensitive adhesive layer on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle to water: 73°, thickness: 20 nm) as a transparent conductive layer, and a polarizing film with a pressure-sensitive adhesive layer on the opposite side of the liquid crystal cell ( 7) was bonded to form a liquid crystal panel.

The following evaluation was performed about the pressure-sensitive adhesive layer and liquid crystal panel obtained in Examples and Comparative Examples.

<Measurement method of saturated moisture content of the adhesive layer>

Samples of about 50 mg were taken from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer prepared in Examples and Comparative Examples. The sample was subjected to a moisture adsorption and desorption measuring device (IGA-Sorp, manufactured by Hiden) to measure the weight (W1) in a state of completely removing moisture at 100°C for 1 hour, and then 23°C, 0% RH. At 2 hours, 23°C, 55% RH for 5 hours, 60°C, 90% RH for 5 hours, 23°C, 55% RH for 5 hours, and weight change was observed. The weight (W2) was measured when the sample had no change in weight (saturated state). The saturated moisture content was measured from the following equation.

<White Cloud Test>

(Preparation of test sample)

An adherend 1 in which an amorphous ITO layer (contact angle with water: 73°, thickness: 20 nm) was formed on one side of an alkali-free glass substrate (contact angle with water: 38°) by sputtering, and an alkali-free glass substrate (water The adherend 2 was prepared in which a crystallized ITO layer (contact angle to water: 58°, thickness: 20 nm) was formed on one side of the contact angle to: 38°. The Sn ratio of the crystalline ITO thin film was 10% by weight. The Sn ratio of the amorphous ITO thin film was 3% by weight. In addition, adherend 3 was prepared in which an acrylic resin layer (contact angle with water: 72°, thickness: 5 μm) was formed on the amorphous ITO layer surface of the adherend 1 according to the following procedure. In Examples 1 to 12 and Comparative Examples 1 to 4, a polarizing film (polarizing film 1 in Table 1) laminated on the transparent conductive layer side (viewer side) of the liquid crystal cell in the liquid crystal panel of each example using the adherend 1 ) Was attached to the amorphous ITO layer side of the adherend 1, and the polarizing film (polarizing film 2 in Table 1) laminated on the opposite side (light source side) of the liquid crystal cell was adhered to the alkali-free glass side of the adherend 1, and It was taken as a sample. In addition, in Example 13, the polarizing film 1 with an adhesive layer used in Example 13 was attached to the crystallized ITO layer of the adherend 2, and the polarizing film 4 with an adhesive layer used in Example 13 was attached to the alkali-free glass side. And, in Example 14, the polarizing film (1) with an adhesive layer used in Example 14 was used on the acrylic resin layer side of the adherend 3, and the polarizing film (4) with an adhesive layer used in Example 14 was formed on the alkali-free glass side. It adhered, and it was set as the sample for the cloudiness test, respectively. The adherends 1 to 3 reproduced the surface conditions of the liquid crystal cells used in Examples and Comparative Examples.

(Method of forming an acrylic resin layer)

5 parts of a photopolymerization initiator (trade name: Irgacure 907, Chiba Specialty Chemical) was blended with respect to 100 parts of polyfunctional urethane acrylate (solid content 100%), and the solid content was 45 with a diluent solvent (methylisobutyl ketone (MIBK)). The coating solution which is% was adjusted. After coating on the amorphous ITO layer surface of the adherend 1 so that the film thickness after drying becomes 5 μm, it was dried at 80° C., cured by UV irradiation (accumulated light amount: 300 mJ), and an acrylic resin layer was formed, and adherend 3 I did it.

(White turbidity measurement)

The test sample was subjected to an autoclave treatment at 50° C., 5 atm and 15 minutes, and then introduced into a thermo-hygrostat of 60° C. and 90% R.H. The sample after 120 hours was observed and evaluated according to the following evaluation criteria.

1: Check under a microscope, no water droplets

2: Check under a microscope, and although a small amount of water droplets can be confirmed, there is no cloudiness with the naked eye

3: There is some cloudiness with the naked eye

4: The whole surface is hazy with the naked eye

5: full surface cloudy

<Durability test>

The test sample prepared in <White Cloud Test> was subjected to an autoclave treatment at 50°C, 5 atm, and 15 minutes, and then put into a heating oven at 85°C. Foaming of the polarizing film after 500 hours was observed, and it evaluated by the following evaluation criteria.

1: no foaming

2: There is foam that cannot be seen with the naked eye in a small part

3: There is foam that can be seen with the naked eye in a small part

4: There is foam that can be seen with the naked eye in part

5: There is foam that can be checked with the naked eye on the entire surface

1a: View-side transparent protective film
1b: liquid crystal cell side transparent protective film
2a: polarizer
2b: polarizer
3a: liquid crystal cell side transparent protective film
3b: View-side transparent protective film
4a: first polarizing film
4b: second polarizing film
5a: adhesive layer 1
5b: pressure-sensitive adhesive layer 2
6: transparent conductive layer
7: first transparent substrate
8: liquid crystal layer
9: second transparent substrate
10: liquid crystal cell
11: retardation layer
12: liquid crystal panel
A: High contact angle

Claims (7)

One side of the liquid crystal cell is a high contact angle surface with a contact angle of 40 to 110° with respect to water,
On the high contact angle surface of the liquid crystal cell,
A pressure-sensitive adhesive layer having a saturated moisture content of 0.3 to 6% by weight at 60°C and 90% RH, and
Having a first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ·day) at 40°C and 90% RH,
On the other side of the liquid crystal cell,
A liquid crystal panel comprising a second polarizing film having a moisture permeability of 8 g/(m ² ·day) or more at 40°C and 90% RH. The liquid crystal panel according to claim 1, wherein a moisture permeability of the second polarizing film is greater than that of the first polarizing film. The liquid crystal panel according to claim 1, wherein the pressure-sensitive adhesive layer has a saturated moisture content of 0.5 to 6% by weight at 60°C and 90% R.H. The liquid crystal panel according to claim 1, wherein the high contact angle surface of the liquid crystal cell is formed by a transparent conductive layer. The liquid crystal panel according to claim 1, wherein the other side of the high contact angle surface of the liquid crystal cell is a low contact angle surface having a contact angle of 3° or more and less than 40° to water. The liquid crystal panel according to claim 1, wherein the second polarizing film is laminated on a liquid crystal cell via an adhesive layer having a saturated moisture content of 0.5 to 6% by weight at 60°C and 90% R.H. An image display device comprising the liquid crystal panel according to any one of claims 1 to 6.

Images