TW201530222A - Liquid crystal panel and image display apparatus - Google Patents

Abstract

The object of the present invention is to provide a liquid crystal panel without opacification due to humidifying and an image display apparatus using the liquid crystal panel. The aforementioned liquid crystal panel is characterized in that one surface of a liquid crystal unit is a high contact angle surface whose contact angle as opposed to water is 40-110 degree. The high contact angle surface of the liquid crystal unit is provided with an adhesive layer whose saturation moisture content under 60 degree Celsius and 90 percent R.H. is 0.3-6 weight percent and a first polarization film whose moisture permeability under 40 degree Celsius and 90 percent R.H. is 0.5-30g/m2/day. The other surface of the liquid crystal unit is provided with a second polarization film whose moisture permeability under 40 degree Celsius and 90 percent R.H. is 8g/m2/day.

Description

Liquid crystal panel and image display device

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

In the liquid crystal panel used in a liquid crystal display device or the like, a polarizing film is usually laminated on both sides of a liquid crystal cell formed by a liquid crystal layer disposed between a pair of transparent substrates via an adhesive layer. The adhesive layer for optical use such as a liquid crystal panel requires high transparency. However, it is known that when it is exposed to room temperature after exposure to high temperature and high humidity, the adhesive layer may be white turbid (whitening). It is considered that this white turbidity is caused by aggregation of moisture which is absorbed in the adhesive layer under moist heat to return to room temperature, and various studies have been conducted to suppress whitening of the adhesive layer due to humidification.

As an adhesive composition capable of suppressing clouding of the adhesive layer, for example, an optical adhesive composition or an adhesive composition comprising, for example, a carbon containing (meth)acrylic acid, is known. a monomer having a weight average molecular weight of from 1 to 18 alkyl ester monomers, a hydroxyl group-containing copolymerizable monomer, and a dialkyl substituted acrylamide monomer having a weight average molecular weight of from 300,000 to 2,000,000 as a copolymer, And a crosslinking agent; the adhesive composition comprising: at least one of a hydroxyl group-free nitrogen-containing vinyl monomer or an alkoxy-containing alkyl (meth) acrylate monomer, and a carboxyl group in the functional group At least one of the hydroxyl group-containing copolymerizable vinyl monomers (for example, refer to Patent Documents 1 and 2).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2011-195651

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-64079

In the above-mentioned Patent Documents 1 and 2, it is intended to suppress the whitening of the adhesive layer by using a specific adhesive composition, but there is no provision for the relationship with the adherend such as a liquid crystal cell, and the polarizing film is also provided. The moisture permeability has not been studied, and it is not sufficient from the viewpoint of suppressing clouding of the entire liquid crystal panel.

In recent years, it has been desired to increase the viewing angle characteristics or to reduce the thickness and weight, and to meet these requirements, a low moisture permeable film is often used as a retardation film or a protective film. However, it is understood that the low moisture permeable film is less likely to permeate moisture, and therefore, the moisture contained in the pressure-sensitive adhesive layer under humidification is less likely to be discharged to the outside of the adhesive when it is returned to room temperature, and the adhesive layer is clouded.

In addition, it is understood that a transparent conductive film such as an indium tin oxide (ITO) film is formed on one transparent substrate of a liquid crystal cell constituting the liquid crystal panel, and the transparent conductive film is compared with an adhesive layer in contact with a transparent substrate such as a glass substrate. The adhesive layer that is in contact has a tendency to inhibit clouding. In other words, it is understood that the properties of both surfaces of the liquid crystal cell are different. Therefore, it is necessary to suppress appropriate white cloudation on both surfaces of the liquid crystal cell, thereby suppressing clouding of the entire liquid crystal panel.

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

The present inventors have made an effort to solve the above problems, and as a result, it has been found that by controlling the moisture content of the adhesive layer of the high contact angle surface of the liquid crystal cell, the moisture permeability of the polarizing film, and the moisture permeability of the polarizing film of the other surface, The above object is achieved to complete the present invention.

That is, the present invention relates to a liquid crystal panel characterized in that a contact angle of a liquid crystal cell with respect to water is a contact angle of 40 to 110°, and a high contact angle of the liquid crystal cell has a: 60° C. The first polarizing film having a saturated water content of 0.3 to 6% by weight at 90% RH and a first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ‧day) at 40 ° C and 90% RH The other surface of the unit has a second polarizing film having a moisture permeability of 8 g/(m ² ‧day) or more at 40 ° C and 90% RH.

The moisture permeability of the second polarizing film is preferably larger than the moisture permeability of the first polarizing film.

The saturated moisture content of the above adhesive layer at 60 ° C and 90% R.H. is preferably 0.5 to 6% by weight.

The high contact angle of the liquid crystal cell is preferably formed by a transparent conductive layer.

The other surface of the high contact angle surface of the liquid crystal cell is preferably a low contact angle surface having a contact angle with respect to water of 3 or more and less than 40.

The second polarizing film is preferably laminated on the liquid crystal cell via an adhesive layer having a saturated water content of 0.5 to 6% by weight at 60 ° C and 90% R.H.

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

In the present invention, the adhesive layer having a specific saturated moisture content and the first polarizing film having a specific moisture permeability are disposed on the high contact angle surface of the liquid crystal cell, and are disposed on the other surface of the liquid crystal cell. The second polarizing film having a moisture permeability can suppress whitening due to humidification of the entire liquid crystal panel. The reason for this is that the value of the water contact angle is large at the high contact angle of the liquid crystal cell, so that the amount of water infiltrated from the interface between the high contact angle surface of the liquid crystal cell and the adhesive layer in humidification is small, and as a result, When it is taken out at room temperature under humidification, the amount of water to be agglomerated is reduced. Therefore, by depositing a first polarizing film having a specific moisture permeability through an adhesive layer having a specific saturated moisture content, whitening of the adhesive layer can be suppressed. On the other hand, for the other surface of the liquid crystal cell, a substrate having a small contact angle with water such as a glass substrate is usually used, and a large amount of water permeates from the interface between the substrate and the adhesive layer. When the temperature is removed at room temperature from humidification, the amount of water to be agglomerated increases, but the second polarizing film having a specific moisture permeability is provided on the surface, so that the moisture contained in the adhesive layer is effectively released to the outside. It can inhibit white clouding.

Further, as one of methods for suppressing clouding, a method of increasing the moisture content of the adhesive layer is known. Such a method of simply increasing the moisture content of the adhesive layer not only has a limited composition of the adhesive layer but also has a tendency to deteriorate the durability (foaming, peeling) of the adhesive layer, but in the present invention, as described above By setting the configuration of the upper side and the lower side of the liquid crystal cell in the liquid crystal panel to be specific, it is possible to suppress clouding of the entire liquid crystal panel, and also to improve durability, and further improve the moisture content of the adhesive layer. Compared to the method, the adhesive layer can be designed with greater freedom.

1a‧‧‧Visual side transparent protective film

1b‧‧‧ Liquid crystal side transparent protective film

2a‧‧‧Polarized elements

2b‧‧‧Polarized elements

3a‧‧‧ Liquid crystal side transparent protective film

3b‧‧‧visible side transparent protective film

4a‧‧‧1st polarizing film

4b‧‧‧2nd polarizing film

5a‧‧‧Adhesive layer 1

5b‧‧‧Adhesive layer 2

6‧‧‧Transparent conductive layer

7‧‧‧1st transparent substrate

8‧‧‧Liquid layer

9‧‧‧2nd transparent substrate

10‧‧‧Liquid Crystal Unit

11‧‧‧ phase difference layer

12‧‧‧ LCD panel

A‧‧‧High contact angle

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

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

Fig. 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 is characterized in that the liquid crystal cell has a polarizing film on both sides thereof, and one surface of the liquid crystal cell has a contact angle of 40 to 110° with respect to water, and the high contact angle surface has An adhesive layer having a saturated water content of 0.3 to 6% by weight at 60 ° C and 90% RH and a first polarizing film having a moisture permeability of 0.5 to 30 g / (m ² ‧day) at 40 ° C and 90% RH, The other surface of the liquid crystal cell has 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 of the present invention will be described in detail below.

(1) Liquid crystal cell

The liquid crystal cell used in the liquid crystal panel of the present invention is not particularly limited as long as the contact angle of one surface with respect to water is 40 to 110°, and includes, for example, a liquid crystal layer and one side of the liquid crystal layer. a first substrate (visible side) and a second substrate (light source side) disposed on the other side of the liquid crystal layer, wherein an image electrode for applying a voltage to the liquid crystal layer is formed on the first substrate or the second substrate Counter electrode.

The substrate for a liquid crystal cell is not particularly limited as long as it is a transparent substrate, and examples thereof include a glass substrate and a plastic substrate. Examples of the glass substrate include an alkali glass substrate and an alkali-free glass substrate. In addition, as the plastic substrate, various plastic substrates having transparency are exemplified, and examples of the material thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, and acetate resins. Resin, polyether oxime resin, polycarbonate resin, polyamine resin, polyamidene resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride A vinyl resin, a polystyrene resin, a polyvinyl alcohol resin, a polyarylate resin, a polyphenylene sulfide resin, or the like.

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

Usually, a transparent conductive film such as an indium tin oxide (ITO) film is formed on one transparent substrate of a liquid crystal cell constituting a liquid crystal panel, and a surface on which the transparent conductive film is formed can be a high contact angle surface. Further, for example, in an On-Cell type or an In-Cell type touch panel, metal wiring such as copper or silver is provided on the outermost layer, or an acrylic resin or the like may be applied to the metal wiring depending on the case. In this case, the surface can also be a high contact angle.

The contact angle of the high contact angle surface with respect to water is 40 to 110 degrees, and may be 45 to 100 degrees or 45 to 90 degrees. The contact angle of the high contact angle surface of the transparent conductive film or the like as described above is usually 40 or more. Further, when the contact angle exceeds 110°, the adhesion to the adhesive layer is lowered and the durability tends to be deteriorated.

The transparent substrate may be previously subjected to sputtering, corona discharge, plasma treatment, flame, ultraviolet irradiation, electron beam irradiation, chemical treatment, oxidation, or the like, or a primer treatment to improve the setting. The adhesion of the transparent conductive film or the acrylic resin coating film thereon to the substrate. In addition, before the transparent conductive film or the acrylic resin coating film is provided, dust removal and cleaning can be performed by solvent cleaning or ultrasonic cleaning as needed.

The constituent material of the transparent conductive film is not particularly limited, and may be selected from the group consisting of indium, tin, zinc, gallium, germanium, titanium, lanthanum, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal in the group. In the metal oxide, a metal atom shown in the above group may be further contained as needed. For example, indium oxide (ITO) containing tin oxide, tin oxide containing antimony or the like can be preferably used, and ITO is particularly preferably used. As ITO. Preferably, it contains 80 to 99% by weight of indium oxide and 1 to 20% by weight of tin oxide.

Further, the ITO may be either crystalline ITO or amorphous (amorphous) ITO. The crystalline ITO can be obtained by applying a high temperature during sputtering or by heating the amorphous ITO.

The thickness of the transparent conductive film is not particularly limited, but is preferably 7 nm or more, more preferably 12 to 200 nm, still more 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, the in-plane uniformity of the transparent conductive film cannot be achieved, and the resistance value in the panel surface is unstable or a specific resistance value cannot be obtained. On the other hand, in the case of more than 200 nm, the productivity of the transparent conductive film is lowered, the cost is also increased, and the optical characteristics are also lowered.

The method for forming the transparent conductive film is not particularly limited, and a conventionally known method can be employed. Specifically, for example, a vacuum deposition method, a sputtering method, or an ion plating method can be exemplified. Alternatively, an appropriate method can be employed depending on the desired film thickness.

Further, the contact angle of the other surface of the high contact angle surface of the liquid crystal cell with respect to water is not particularly limited, and usually, the contact angle with respect to water is often small for the glass substrate or the like. Face. The other surface of the high contact angle of the liquid crystal cell is preferably a low contact angle surface of, for example, a contact angle with respect to water of 3 or more and less than 40.

The driving mode of the liquid crystal cell is not particularly limited, and any known method may be used, and examples thereof include a twisted nematic (TN) mode, a super twisted nematic (STN) mode, a horizontal alignment (ECB) mode, and a vertical alignment. (VA) mode, plane conversion (IPS) mode, fringe field conversion (FFS) mode, curved nematic (OCB) mode, hybrid alignment (HAN) mode, ferroelectric liquid crystal (SSFLC) mode, antiferroelectric liquid crystal (AFLC) Mode liquid crystal unit.

Further, in the liquid crystal cell, a color filter, a black matrix, or the like may be provided on any of the substrates as needed, and in the present invention, a liquid crystal cell may be directly used as a liquid crystal display device mounted on a commercially available liquid crystal display device.

(2) Adhesive layer

The first polarizing film is bonded to the high contact angle surface of the liquid crystal cell via an adhesive layer.

The adhesive layer is not particularly limited as long as it has a saturated water content of from 0.3 to 6% by weight at 60 ° C and 90% R.H. The saturated moisture content of the adhesive layer is preferably from 0.5 to 5% by weight, further preferably from 0.5 to 3.5% by weight, particularly preferably from 0.7 to 3.5% by weight. When the saturated moisture content of the adhesive layer exceeds 6% by weight, the amount of moisture that can enter the adhesive layer increases, and foaming may occur at a high temperature, which tends to deteriorate durability. In addition, when the saturated water content is less than 0.3% by weight, the water content contained in the pressure-sensitive adhesive layer is low, and the white turbidity of the pressure-sensitive adhesive layer is deteriorated, and the white opacity of the liquid crystal panel as a whole cannot be sufficiently suppressed.

The adhesive layer of the present invention is preferably formed of an adhesive composition comprising a base polymer and a crosslinking agent. The adhesive composition can be made into an adhesive such as an acrylic, a synthetic rubber, a rubber or an anthrone, and it is preferably a (meth)acrylic polymer from the viewpoints of transparency, heat resistance and the like. Acrylic adhesive for base polymers.

As the (meth)acrylic polymer of the base polymer of the acrylic adhesive, it is preferred to polymerize a monomer component containing a (meth) acrylate having an alkyl group having 2 to 14 carbon atoms. Further, it is preferably obtained by polymerizing a monomer component containing a (meth) acrylate having an alkyl group having 2 to 14 carbon atoms as a main monomer. Here, the main single system means that it is preferably 60% by weight or more, and more preferably 70% by weight or more based on the total monomer component of the constituent (meth)acrylic polymer. Further, (meth) acrylate means acrylate and/or methacrylate, and has the same meaning as (meth) of the present invention.

Examples of the (meth) acrylate having an alkyl group having 2 to 14 carbon atoms include, for example, ethyl (meth)acrylate, n-butyl (meth)acrylate, and tert-butyl (meth)acrylate. , isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, (a) N-decyl acrylate, isodecyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, (methyl) The n-tridecyl acrylate or n-tetradecyl (meth) acrylate may be used singly or in combination of two or more kinds. Among these, the (meth) acrylate having an alkyl group having 2 to 12 carbon atoms is more hydrophilic and therefore more preferable.

The monomer component other than the (meth)acrylic acid ester having an alkyl group having 2 to 14 carbon atoms may be contained in the monomer component. The other polymerizable monomer is not particularly limited as long as it is a polymerizable functional group having an unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group, and examples thereof include a single group containing a hydroxyl group. A monomer, a monomer having a carboxyl group, and the like.

As the monomer having a hydroxyl group, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth)acrylinyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and (meth)acrylic acid. 6-hydroxyhexyl ester, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxydodecyl (meth)acrylate, (meth)acrylic acid (4- The hydroxymethylcyclohexyl)methyl ester may be used singly or in combination of two or more kinds. Hydroxyl The monomer has an effect of improving the adhesion to a transparent conductive film (particularly ITO), and therefore is preferable. Among these, the acrylic monomer having a hydroxyl group of 2 to 14 in the side chain has a higher effect of improving the adhesion to the transparent conductive film, and is more hydrophilic, so that it is preferable.

The content of the hydroxyl group-containing monomer is preferably 10% by weight or less, more preferably 0 to 5% by weight, still more preferably 0.1 to 4% by weight based on the monomer component. Further, in the present invention, in particular, the hydroxyl group-containing acrylic monomer having a carbon number of 12 or less in the side chain can be used to adjust the hydrophilicity of the adhesive composition, and as a result, it can be adjusted. The saturated moisture content of the adhesive layer formed by the adhesive composition is therefore preferred.

As the monomer having a carboxyl group, a monomer having a carboxyl group having an unsaturated double bond such as a (meth)acryl fluorenyl 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, and fumaric acid. Crotonic acid, etc., these may be used singly or in combination.

The content of the monomer having a carboxyl group is preferably 10% by weight or less based on the monomer component. When the monomer having a carboxyl group exceeds 10% by weight of the monomer component, the transparent conductive film such as an ITO film tends to be significantly deteriorated under humidification conditions, which is not preferable.

The other comonomer is not particularly limited as long as it is a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and examples thereof include a (meth)acrylic acid ring. An alicyclic (meth) acrylate such as hexyl ester, borneol (meth)acrylate or isobornyl (meth)acrylate; for example, an aryl (meth)acrylate such as phenyl (meth)acrylate; For example, a vinyl ester such as vinyl acetate or vinyl propionate; for example, a styrene monomer such as styrene; for example, a glycidyl (meth)acrylate or a methyl glycidyl (meth)acrylate; a monomer having an oxy group; for example, a monomer containing a guanamine group such as acrylamide, diethyl acrylamide, propylene morpholine (ACMO), N-vinylpyrrolidone (NVP); for example, (methyl) N,N-dimethylaminoethyl acrylate, (meth)acrylic acid An amine group-containing monomer such as N,N-dimethylaminopropyl ester; for example, a cyclic nitrogen-containing compound such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam, or methylvinylpyrrolidone a monomer; for example, an alkoxy group-containing monomer such as methoxyethyl (meth)acrylate or ethoxyethyl (meth)acrylate; for example, a cyano group such as acrylonitrile or methacrylonitrile; a functional monomer such as 2-methylpropenyloxyethyl isocyanate; for example, an olefin monomer such as ethylene, propylene, isoprene, butadiene or isobutylene; for example, vinyl ether A vinyl ether monomer; for example, a monomer containing a halogen atom such as vinyl chloride; or a N-vinyl carboxamide.

Further, examples of the copolymerizable monomer include N-cyclohexylmaleimide, N-isopropylmaleimide, N-dodecylmaleimide, and N-phenyl group. Maleic imine monomers such as maleic imine; for example, N-methyl itaconimine, N-ethyl itaconimine, N-butyl itaconide, N-xin Phytosamine, N-2-ethylhexyl ketimine, N-cyclohexyl ketimine, N-dodecyl ketimine, etc. For example, N-(meth) propylene oxime methylene succinimide, N-(methyl) propylene fluorenyl-6-oxyhexamethylene succinimide, N-(methyl) An amber quinone imine monomer such as acrylonitrile-8-oxy octamethylene succinimide; for example, styrene sulfonic acid, allyl sulfonic acid, 2-(methyl) acrylamide oxime-2- A sulfonic acid group-containing monomer such as methyl propanesulfonic acid, (meth) acrylamide propyl sulfonic acid, sulfopropyl (meth) acrylate, or (meth) propylene phthaloxy naphthalene sulfonic acid.

Further, examples of the copolymerizable monomer include polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxy ethylene glycol (meth) acrylate, and methoxy polymerization. a diol-based acrylate monomer such as propylene glycol (meth) acrylate; and, for example, an acrylate series containing a hetero ring or a halogen atom such as tetrahydrofurfuryl (meth) acrylate or fluorine (meth) acrylate Body and so on.

Further, as the copolymerizable monomer, a polyfunctional monomer can be used. The polyfunctional monomer may, for example, be a compound having two or more (meth)acrylonyl groups or an unsaturated double bond such as a vinyl group. For example, ethylene glycol di(meth)acrylate, diethylene glycol di(a) Acrylate, triethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetraethylene glycol di(meth)acrylate, etc. (mono or poly)ethylene glycol (mono or poly) propylene glycol di(meth) acrylate (mono or poly) alkyl diol di(meth) acrylate, such as di(meth) acrylate or propylene glycol di(meth) acrylate; Further, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate , an esterified product of (meth)acrylic acid and a polyhydric alcohol such as pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, or a polyfunctional vinyl compound such as divinylbenzene; (meth)acrylic acid allyl A compound having a reactive unsaturated double bond such as a base ester or a vinyl (meth)acrylate. In addition, as the polyfunctional monomer, it is also possible to use two or more kinds of a carboxyl group such as a polyester, an epoxy or a urethane to form a (meth) acrylonitrile group or a vinyl group having the same functional group as the monomer component. A polyester (meth) acrylate, an epoxy (meth) acrylate, a urethane (meth) acrylate or the like having an unsaturated double bond.

The ratio of the monomer other than the hydroxyl group-containing monomer or the carboxyl group-containing monomer is preferably 40% by weight or less, more preferably 0 to 30% by weight, still more preferably 0 to 20% by weight based on the monomer component. However, a monomer containing a guanamine group or a monomer containing an amine group may improve the hydrophilicity of the adhesive composition and deteriorate durability (foaming), and therefore, preferably 15 weights of the monomer components, respectively. % or less, 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 3,000,000, more preferably 1.2 million to 2.7 million, and still more preferably 1.2 million to 2.5 million. When the weight average molecular weight is less than 1.2 million, it may be inferior in terms of heat resistance. Further, when the weight average molecular weight is less than 1.2 million, the amount of the low molecular weight component in the adhesive composition increases, and the low molecular weight component sometimes bleeds out from the adhesive layer to impair transparency. Further, an 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 or mechanical properties. In addition, if the weight average molecular weight is more than 3 million, in order to adjust to the viscosity for coating, a large amount of thinner is required. Solvent release is not good in terms of cost. Further, the weight average molecular weight is in the above range, and is also preferable from the viewpoint of corrosion resistance and durability. The weight average molecular weight is a value calculated by GPC (gel permeation chromatography) and calculated in terms of polystyrene.

A known production method such as solution polymerization, bulk polymerization, emulsion polymerization, or various radical polymerization can be appropriately selected for the production of such a (meth)acrylic polymer, and is not particularly limited, and the viewpoint of the moisture content of the adhesive layer is considered. In terms of the present invention, solution polymerization is preferred. Further, the obtained (meth)acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer and the like.

In the solution polymerization, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. As a specific solution polymerization example, the reaction is carried out under the following reaction conditions: a polymerization initiator is added under an inert gas flow such as nitrogen, and it is usually carried out at about 50 to 70 ° C for about 5 to 30 hours.

The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth)acrylic polymer can be controlled according to the polymerization initiator, the amount of the chain transfer agent used, and the reaction conditions, and the amount of use can be appropriately adjusted depending on the types thereof.

As the polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-amidinopropane) dihydrochloride, 2,2'-azo Bis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-methylpropionamidine) disulfate, 2,2' -Azobis(N,N'-dimethylene isobutylphosphonium), 2,2'-azobis[N-(2-carboxyethyl)-2-methylpropionamidine hydrate (commodity Name: azo-based initiator such as VA-057, manufactured by Wako Pure Chemical Industries Co., Ltd.; persulfate such as potassium persulfate or ammonium persulfate, di(2-ethylhexyl)peroxydicarbonate, (4-tert-butylcyclohexyl)peroxydicarbonate, dibutyl phthalate dihydrate, tert-butyl peroxy neodecanoate, third hexyl peroxypivalate, peroxidized neopentyl Tert-butyl acid ester, dilaurin peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, bis(4-methylbenzene) Methionine) peroxide, benzammonium peroxide, isobutyl peroxide a peroxide-based initiator such as tert-butyl acid ester, 1,1-di(trihexylperoxy)cyclohexane, tert-butyl hydroperoxide or hydrogen peroxide; persulfate and sodium hydrogen sulfite The combination is a combination of a peroxide and a sodium ascorbate, and the redox initiator is a combination of a peroxide and a reducing agent, but is not limited thereto.

The polymerization initiator may be used singly or in combination of two or more kinds, and the content as a whole is preferably 0.005 to 1 by weight based on 100 parts by weight of the monomer component forming the (meth)acrylic polymer. About.

As the chain transfer agent, for example, dodecyl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, mercaptoacetic acid, 2-ethylhexyl thioglycolate, 2,3-dimercapto-1 -propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the content as a whole is preferably about 0.1 part by weight or less based on 100 parts by weight of the total of the monomer components.

In order to improve the adhesion under high temperature and high humidity conditions, various decane coupling agents may be added to the adhesive composition used in the present invention. As the decane coupling agent, any decane coupling agent having an appropriate functional group can be used. Examples of the functional group include a vinyl group, an epoxy group, an amine group, a mercapto group, a (meth)acryloxy group, an ethyl oxime group, an isocyanate group, a styryl group, a polysulfide group, and the like. Specific examples thereof include vinyl-containing decane coupling agents such as vinyl triethoxy decane, vinyl tripropoxy decane, vinyl triisopropoxy decane, and vinyl tributoxy decane; Γ-glycidoxypropyltrimethoxydecane, γ-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 2-(3 , an epoxy group-containing decane coupling agent such as 4-epoxycyclohexyl)ethyltrimethoxydecane; γ-aminopropyltrimethoxydecane, N-β-(aminoethyl)-γ-amino group Propylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, γ-triethoxycarbamido-N-(1, An amine group-containing decane coupling agent such as 3-dimethylbutylidene) propylamine or N-phenyl-γ-aminopropyltrimethoxydecane; and fluorenyl group containing γ-mercaptopropylmethyldimethoxydecane a decane coupling agent; a styryl group containing a styryl group a decane coupling agent; a methacrylic acid-based decane coupling agent such as γ-acryloxypropyltrimethoxy decane or γ-methacryloxypropyltriethoxy decane; 3-isocyanate propyl group; a decane coupling agent containing an isocyanate group such as triethoxysilane or a decane coupling agent containing a polysulfide group such as bis(triethoxymethane alkylpropyl)tetrasulfide.

The decane coupling agent may be used singly or in combination of two or more kinds, and the content of the decane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight based on 100 parts by weight of the base polymer (solid content component). The parts by weight are further preferably 0.02 to 0.8 parts by weight. When the compounding amount of the decane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is produced, which is not preferable in terms of durability.

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

Further, in the adhesive composition used in the present invention, the cohesive force associated with the durability of the adhesive can be imparted by adding a crosslinking agent.

As the crosslinking agent, a polyfunctional compound can be used, and examples thereof include an organic crosslinking agent or a polyfunctional metal chelate compound. Examples of the organic crosslinking agent include an epoxy crosslinking agent, an isocyanate crosslinking agent, a carbodiimide crosslinking agent, an imine crosslinking agent, an oxazoline crosslinking agent, and a nitrogen-based crosslinking agent. A pyridine-based crosslinking agent, a peroxide-based crosslinking agent, and the like. The polyfunctional metal chelate is a covalent bond or a coordination bond of an organic compound with a polyvalent metal atom. Examples of the polyvalent metal atom include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, and Ti. Wait. Examples of the atom in the organic compound which is a covalent bond or a coordinate bond include an oxygen atom and the like. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents may be used alone or in combination of two or more. Among these, a peroxide-based crosslinking agent and an isocyanate-based crosslinking agent are preferred, and more preferably These combinations are used.

The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups in one molecule (including an isocyanate-regenerating functional group in which an isocyanate group is temporarily protected by a block agent or a number of monomers).

Examples of the isocyanate crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, examples thereof include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, and fats such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate. Aromatic diisocyanates such as cycloisocyanates, 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzene dimethylene diisocyanate, polymethylene polyphenyl isocyanate, trihydroxyl Methylpropane/toluene diisocyanate 3-polymer adduct (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.), trimethylolpropane/hexamethylene diisocyanate 3-polymer adduct (trade name) : CORONATE HL, manufactured by Japan Polyurethane Industry Co., Ltd., isocyanate ester of hexamethylene diisocyanate (trade name: CORONATE HX, manufactured by Japan Polyurethane Industry Co., Ltd.), etc., benzodiazepine Trimethylolpropane adduct of methyl diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, Mitsui Chemicals) (share) system Polyether polyisocyanate, polyester polyisocyanate, and these adducts with various polyols, polyfunctionalized by isocyanurate bond, biuret bond, allophanate bond, etc. Polyisocyanate, etc. Among these, it is preferred to use an aliphatic isocyanate when the reaction rate is fast.

As the peroxide-based crosslinking agent, various peroxides can be used. Examples of the peroxide include di(2-ethylhexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, and di-tert-butylperoxydicarbonate. Peroxidic neodecanoic acid tert-butyl ester, peroxypivalic acid third hexyl ester, peroxypivalic acid tert-butyl ester, peroxide two Laurel, di-n-octyl peroxide, 1,1,3,3-tetramethylbutylperoxy isobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethyl Hexanoate, bis(4-methylbenzhydryl) peroxide, dibenzoyl peroxide, tert-butyl peroxyisobutyrate, and the like. Among these, bis(4-t-butylcyclohexyl)peroxydicarbonate which is excellent in crosslinking reaction efficiency, dilaurin peroxide, and dibenzoic acid peroxide are particularly preferably used.

The ratio of the crosslinking agent in the adhesive composition is not particularly limited, and is usually a ratio of about 10 parts by weight or less based on 100 parts by weight of the base polymer (solid content) to the crosslinking agent (solid content). To deploy. The compounding ratio of the above crosslinking agent is preferably from about 0.01 to 10 parts by weight, more preferably from about 0.01 to about 5 parts by weight. Further, particularly in the case of using a peroxide-based crosslinking agent, it is preferably about 0.05 to 1 part by weight, more preferably about 0.06 to 0.5 part by weight, per 100 parts by weight of the base polymer (solid content). .

Further, a viscosity adjusting agent, a peeling adjuster, a tackifier, a plasticizer, a softener, a glass fiber, a glass bead, a metal powder, and other inorganic powders may be used in the adhesive composition used in the present invention as needed. a filler, a pigment, a coloring agent (pigment, dye, etc.), a pH adjuster (acid or alkali), an antioxidant, an ultraviolet absorber, etc., and various types may be appropriately used without departing from the object of the present invention. additive.

The method for forming the pressure-sensitive adhesive layer is not particularly limited, and the pressure-sensitive adhesive composition may be applied to various substrates, dried by a dryer such as a heating oven, and a solvent or the like may be volatilized to form an adhesive layer, and the adhesive layer may be adhered thereto. The adhesive layer may be applied to the polarizing film or the liquid crystal cell substrate described below, or the adhesive composition may be directly applied onto the polarizing film or the liquid crystal cell to form an adhesive layer. In the present invention, a polarizing film in which an adhesive layer of an adhesive layer is formed on a polarizing film in advance, and a polarizing film of the adhesive layer is attached to a liquid crystal cell is preferred.

The substrate is not particularly limited, and examples thereof include various substrates such as a release film and a transparent resin film substrate.

As a method of applying the adhesive composition to the above substrate or a polarizing film, each of the coating methods can be used. Ways. Specific examples include, for example, a spray coater, roll coating, contact roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roller coating, bar coating, blade coating, Air knife coating, curtain coating, lip coating, extrusion coating method using a die coater or the like.

The drying conditions (temperature, time) are not particularly limited, and may be appropriately set depending on the composition and concentration of the adhesive composition, for example, drying at about 80 to 170 ° C, preferably at 90 to 200 ° C for 1 to 60 minutes. Good for 2~30 minutes.

The thickness of the adhesive layer (after drying) is, for example, preferably from 5 to 100 μm, more preferably from 7 to 70 μm, still more preferably from 10 to 50 μm. When the thickness of the adhesive layer is less than 5 μm, the adhesion to the adherend is insufficient, and the durability at high temperature, high temperature and high humidity tends to be insufficient. On the other hand, when the thickness of the adhesive layer exceeds 100 μm, the adhesive layer cannot be sufficiently dried when the adhesive composition is applied and dried, and the thickness of the surface of the remaining bubbles or the adhesive layer is uneven. A tendency to show a problem in appearance.

The constituent material of the release film may, for example, be a resin film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film, or a porous material such as paper, cloth or non-woven fabric, or a foamed sheet. A resin film is preferably used in terms of excellent surface smoothness, such as a material, a metal foil, and a suitable sheet such as a laminate.

Examples of the resin film include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, and a polyparaphenylene. A formic acid ethylene glycol film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, or the like.

The thickness of the release film is usually 5 to 200 μm, preferably about 5 to 100 μm. The mold release film may be subjected to mold release and antifouling treatment using an anthrone-based, fluorine-based, long-chain alkyl-based or fatty amide-based release agent, cerium oxide powder or the like, or a coating type. Antistatic treatment of kneading type, vapor deposition type, etc. In particular, by appropriately performing a release treatment such as an anthrone treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the release film, it is possible to further The peelability from the above adhesive layer is improved.

The transparent resin film substrate is not particularly limited, and various resin films having transparency can be used. This resin film is formed of a single film. For example, examples of the material thereof include a polyester resin such as polyethylene terephthalate or polyethylene naphthalate, an acetate resin, a polyether oxime resin, a polycarbonate resin, and a poly Amidoxime resin, polyimide resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin A polyarylate resin or a polyphenylene sulfide resin. Among these, a polyester resin, a polyimide resin, and a polyether oxime resin are particularly preferable.

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

In addition, a tackifying layer may be provided between the polarizing film and the adhesive layer. The material for forming the adhesion-promoting layer is not particularly limited, and examples thereof include various polymers, sols of metal oxides, cerium oxide sols, and the like. Among these, polymers are particularly preferably used. The use form of the above polymer may be any of a solvent-soluble type, a water-dispersible type, and a water-soluble type.

Examples of the polymer include a polyurethane resin, a polyester resin, an acrylic resin, a polyether resin, a cellulose resin, a polyvinyl alcohol resin, and a polyvinylpyrrolidone. Polystyrene resin or the like. Among these, a polyurethane resin, a polyester resin, and an acrylic resin are particularly preferable. A crosslinking agent can be suitably formulated among the above resins. These other binder components may be used singly or in combination of two or more kinds depending on the use. The thickness of the adhesion-promoting layer is not particularly limited, but is preferably 5 to 300 nm.

The method for forming the above-mentioned adhesion-promoting layer is not particularly limited, and it can be carried out by a generally known method. Further, when the adhesion promoting layer is formed, the iodine-based polarizing film can be subjected to an activation treatment. The activation treatment can be carried out by various methods such as corona treatment, low pressure UV treatment, plasma treatment, and the like.

The method of forming an adhesive layer on the adhesion-promoting layer on the polarizing film is as described above.

In addition, an adhesive layer and a liquid crystal of a polarizing film with an adhesive layer for a transparent conductive film When the adhesive layer on the unit is exposed, the adhesive layer may be protected by a release film (separator) before being supplied to the actual use. The above-mentioned substance is mentioned as a release film. When a release film is used as the substrate in the production of the above adhesive layer, the release film can be used as a transparent conductive film by laminating the adhesive layer on the release film with a polarizing film or a liquid crystal cell. The release film with the adhesive layer of the adhesive layer or the adhesive layer of the liquid crystal cell with the adhesive layer can be simplified in terms of steps.

(3) First polarizing film

The first polarizing film bonded to the high contact angle surface of the liquid crystal cell via the adhesive layer may have a moisture permeability of 40 to 30 g/(m ² ‧day) at 40° C. and 90% RH. There is no special limit. Further, 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), still more preferably 9.0 to 30 g/(m ² ‧day), the best is 21.0~30g/(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 adhesive layer is not easily discharged to the outside through the first polarizing film. As a result, white clouding of the adhesive layer is deteriorated, foaming occurs, and durability is deteriorated. The adjustment of the moisture permeability of the first polarizing film can be carried out by appropriately adjusting the moisture permeability, the thickness, and the like of the transparent protective film described below.

As the polarizing film, a polarizing film having a transparent protective film on one side or both sides of a polarizing element is generally used.

The polarizing element is not particularly limited, and various polarizing elements can be used. Examples of the polarizing element include adsorption of iodine or a dichroic dye of a dichroic dye to a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and an ethylene-vinyl acetate copolymer-based partial saponification. A hydrophilic polymer film such as a film is subjected to uniaxial stretching, a dehydration treatment of polyvinyl alcohol, or a polyene alignment film such as a dechlorination treatment of polyvinyl chloride. Among these, a polarizing element comprising a polyvinyl alcohol-based film and a dichroic substance such as iodine is preferable, and an iodine-based polarizing element containing iodine and/or iodide ion is more preferable. Further, the thickness of the polarizing element is not particularly limited, but is usually about 5 to 80 μm.

A polarizing element obtained by dyeing and uniaxially stretching a polyvinyl alcohol-based film with iodine can be produced, for example, by immersing polyvinyl alcohol in an aqueous iodine solution, and extending it to the original length of 3 ~7 times. It may be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like as needed. Further, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing as needed. By washing the polyvinyl alcohol-based film with water, the surface of the polyvinyl alcohol-based film can be washed with dirt or an anti-adhesion agent, and the polyvinyl alcohol-based film can be swollen to prevent unevenness in dyeing unevenness. Effect. The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. The extension can be carried out in an aqueous solution such as boric acid or potassium iodide or in a water bath.

Further, in the present invention, a thin polarizing element having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably from 1 to 7 μm. Such a thin polarizing element is preferable because it has a small thickness unevenness, is excellent in visibility, and has a small dimensional change. Therefore, it is excellent in durability and can also be made thinner as the thickness of the polarizing film.

As a thin type of polarizing element, a representative of the Japanese Patent Laid-Open No. 51-069644, or Japanese Patent Laid-Open No. 2000-338329, or International Publication No. 2010/100917, International Publication No. 2010/100917 The thin type polarizing film described in the Japanese Patent No. 4751481 or the Japanese Patent Laid-Open Publication No. 2012-073563. The thin polarizing film can be obtained by a method of stretching a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a state of a laminate; and a dyeing step . According to this method, even if the PVA-based resin layer is thin, it can be supported by the resin substrate for stretching, whereby stretching can be performed without causing problems such as breakage due to stretching.

In the method of the step of extending the state of the laminated body and the dyeing step, the high-magnification stretching and the improvement of the polarizing performance can be achieved, and the thin polarizing film is preferably disclosed by the international publication. Manual No. 2010/100917, International Publication No. 2010/100917, or Japanese Patent No. 4751481, or Japanese Patent Special The polarizing film obtained by the method of the step of performing the stretching in the aqueous solution of boric acid described in Japanese Patent Publication No. 2012-073563 is particularly preferably described in the specification of Japanese Patent No. 4751481, or the Japanese Patent Publication No. 2012-073563. A polarizing film obtained by a method of performing an auxiliary air extension step before stretching in an aqueous solution of boric acid is included.

The material for forming the transparent protective film provided on one surface or both surfaces of the polarizing element is such that the moisture permeability at 40° C. and 90% RH of the first polarizing film is 0.5 to 30 g/(m ² ‧day) The selection is not particularly limited. Examples of the material for forming the transparent protective film include polyester-based polymers such as polyethylene terephthalate or polyethylene naphthalate, diethyl fluorenyl cellulose, or triethylene sulfhydryl. A cellulose polymer such as cellulose, an acrylic polymer such as polymethyl methacrylate, a styrene polymer such as polystyrene or an acrylonitrile-styrene copolymer (AS resin), or a polycarbonate polymer. Wait. Further, examples thereof include polyethylene, polypropylene, polyolefin having a ring- or norbornene structure, a polyolefin-based polymer such as an ethylene-propylene copolymer, a vinyl chloride polymer, nylon, or an aromatic polyamine. Isoamine polymer, quinone imine polymer, fluorene polymer, polyether fluorene polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, partial A vinyl chloride polymer, a vinyl butyral polymer, an aryl ester polymer, a polyoxymethylene polymer, an epoxy polymer, or a mixture of the above polymers is used as a polymer forming the transparent protective film. example. The transparent protective film can also be formed as a hardened layer of a thermosetting type or an ultraviolet curable resin such as an acrylic type, an urethane type, an acrylamide type, an epoxy type or an anthrone type.

The moisture permeability of the transparent protective film at 40 ° C and 90% RH is not particularly limited, but is preferably 0.5 to 2500 g / (m ² ‧ day). Further, among the transparent protective films, the moisture permeability at 40 ° C and 90% RH of the protective film on the liquid crystal cell side is preferably 0.5 to 300 g / (m ² ‧ day). It is preferable to set the moisture permeability of the transparent protective film on the liquid crystal cell side at 40 ° C and 90% RH in the above range, and it is preferable to obtain an effect of further suppressing clouding.

The thickness of the protective film can be appropriately determined, and the workability and film are evaluated in terms of strength and operability. In terms of sex, etc., it is usually about 1 to 500 μm.

The polarizing element and the protective film are usually adhered via a water-based adhesive or the like. Examples of the water-based adhesive include an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, an ethylene-based emulsion, an aqueous polyurethane, and an aqueous polyester. Examples of the adhesive agent for the polarizing element and the transparent protective film include an ultraviolet curable adhesive, an electron beam curable adhesive, and the like. The adhesive for an electron beam curing type polarizing film exhibits good adhesion to the above various transparent protective films. Further, the binder used in the present invention may contain a metal compound filler.

In the present invention, the moisture permeability of the first polarizing film may be within the above range. For example, a retardation film or the like may be formed on the polarizing element instead of the transparent protective film. Further, another transparent protective film or a retardation film may be further provided on the transparent protective film.

Regarding the surface of the transparent protective film that is not on the opposite side (visible side) of the liquid crystal cell, a hard coat layer or an anti-reflection treatment may be applied to prevent adhesion, diffusion, or anti-glare.

(4) Second polarizing film

The surface of the liquid crystal cell constituting the liquid crystal panel of the present invention having a water contact angle of 40 to 110° on the opposite side of the surface has a moisture permeability at 40° C. and 90% RH of 8 g/(m ² ‧day) or more. The second polarizing film.

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, further preferably 25 g/(m ² ‧day) or more, particularly Good for more than 25g / (m ² ‧ days). When the moisture permeability is less than 8 g/(m ² ‧day), the moisture in the adhesive layer is not easily discharged to the outside through the second polarizing film. As a result, the adhesive layer of the liquid crystal cell having a water contact angle of 40 to 110° on the opposite side of the contact surface has a tendency to become cloudy, which is not preferable.

Further, the moisture permeability of the second polarizing film is preferably larger than the moisture permeability of the first polarizing film. That is, it is preferable that the first polarizing film is a low moisture permeability film, and the second polarizing film is a high moisture permeability film. Further, the difference between the moisture permeability of the second polarizing film and the moisture permeability of the first polarizing film is not particularly limited, and for example, it is preferably 10 g/(m ² ‧day) or more. The above-described relationship between the moisture permeability of the second polarizing film and the first polarizing film is preferable, and it is preferable from the viewpoint of suppressing clouding of the entire liquid crystal panel.

The polarizing element and the protective film constituting the second polarizing film are the same as those of the first polarizing film. The moisture permeability of the transparent protective film used in the second polarizing film at 40° C. and 90% RH is not particularly limited, but is preferably 5 to 3000 g/(m ² ‧day). Further, among the transparent protective films constituting the second polarizing film, the moisture permeability at 40 ° C and 90% RH of the protective film on the liquid crystal cell side is preferably 10 to 2000 g / (m ² ‧ day). When the transparent protective film on the liquid crystal cell side has a moisture permeability at 40 ° C and 90% RH in the above range, it is preferable to obtain an effect of further suppressing clouding.

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

Further, the second polarizing film may be attached to the liquid crystal cell via an adhesive layer, and the adhesive layer may be the same as the user of the first polarizing film, for example, for attaching the second polarizing film to the liquid crystal. The adhesive layer of the unit has a saturated water content of 0.5 to 6% by weight at 60 ° C and 90% RH, and is preferable from the viewpoint of suppressing clouding.

(5) Composition of liquid crystal panel

The liquid crystal panel of the present invention has a liquid crystal cell having a high contact angle surface, and has an adhesive layer having a specific saturated moisture content and a first polarizing film having a specific moisture permeability on the high contact angle surface. Further, the second polarizing film having a specific moisture permeability may be provided on the other surface of the liquid crystal cell, and the other configuration is not particularly limited. The specific configuration of the liquid crystal panel of the present invention can be described based on FIGS. 1 to 3, but the present invention is not limited thereto.

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

2, the liquid crystal panel 12 of the present invention is formed with a retardation layer 11 instead of the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG. 1, and FIG. 3 shows the liquid crystal panel 12 of the present invention via the adhesive layer 5c. The phase difference layer 11 is further formed on the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG.

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

The lower the moisture permeability of the polarizing film, the white turbidity, the more likely the durability (foaming) is deteriorated, and the lower the water contact angle of the surface of the liquid crystal cell to which the adhesive layer is attached, the more the water is humidified under humidification. Since it is easy to infiltrate between the liquid crystal cell and the adhesive layer, it has a tendency to become cloudy and deteriorate in durability. Further, when the white turbidity and the durability (foaming) of the adhesive layer are in a trade-off relationship, when the saturated moisture content of the adhesive layer is high, white turbidity is good, but durability (foaming) is deteriorated, and conversely, When the saturated moisture content of the adhesive layer is low, the white turbidity is deteriorated, but the durability (foaming) is good. In other words, in the present invention, by setting the moisture permeability of the polarizing film and the moisture content of the pressure-sensitive adhesive layer in an appropriate range in the relationship with the water contact angle of the surface of the liquid crystal cell, whitening of the entire liquid crystal panel can be suppressed.

2. Image display device

The image display device of the present invention comprises the liquid crystal panel of the present invention. Hereinafter, a liquid crystal display device will be described by way of an example, and the present invention is applicable 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 is applicable include a liquid crystal display device, an electroluminescence (EL) display, a plasma display (PD), and field emission. Display (FED: Field Emission Display), etc.

The image display device of the present invention is only required to include the liquid crystal panel of the present invention, and the other configuration is the same as that of the conventional image display device.

Example

Hereinafter, the present invention will be described in detail by way of examples, and the present invention is not limited to the following examples as long as it does not exceed the gist of the invention. In addition, in each of the examples, the parts and % are based on the weight, and unless otherwise specified, the room temperature conditions are 23 ° C and 65% R.H.

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

The water vapor transmission rate (moisture permeability) of the transparent protective film and the polarizing film was measured by using a water vapor transmission rate measuring device (PERMATRAN-W, manufactured by MOCON Corporation) under the conditions of 40 ° C and 90% R.H. atmosphere for 24 hours. The measurement was carried out in accordance with 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 permeation chromatography).

Device: manufactured by Tosoh Corporation, HLC-8220GPC

Column:

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

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

Flow rate: 0.6mL/min

Injection volume: 10μL

Column temperature: 40 ° C

Dissolution: THF

Injection sample concentration: 0.2% by weight

Detector: Differential Refractometer

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

Production Example 1 (Production of Polarizing Film (1))

A PVA film having a thickness of 80 μm was dyed at 30 ° C in a 0.3% iodine solution for 1 minute between rolls having different speed ratios, and was extended to 3 times. Then, while immersing it in an aqueous solution containing 4% of boric acid and 10% of potassium iodide at 60 ° C for 0.5 minutes, the film was stretched to a total stretch ratio of 6 times. Then, it was washed by immersing in an aqueous solution containing potassium iodide at a concentration of 1.5% at 30 ° C for 10 seconds, and then dried at 50 ° C for 4 minutes to obtain a polarizing element having a thickness of 25 μm. A PVA-based resin aqueous solution was applied to both surfaces of the polarizing element, and an acrylic film (water permeability: 50 g/(m ² ‧ day)) having a thickness of 40 μm was bonded to one surface, and a TAC system having a thickness of 60 μm was bonded to the other surface. A film (water permeability: 1000 g/(m ² ‧day)) was used to prepare a polarizing film (1). The obtained polarizing film (1) had a moisture permeability of 20 g/(m ² ‧day).

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

The acrylic film having a thickness of 40 μm used in Production Example 1 was changed to an acrylic film having a thickness of 30 μm (water permeability: 68 g/(m ² ‧ day)), and a TAC film having a thickness of 60 μm was changed to a TAC film having a thickness of 40 μm. A polarizing film (2) was obtained in the same manner as in Production Example 1 except that the moisture permeability was 1400 g/(m ² ‧day). The obtained polarizing film (2) had a moisture permeability of 25 g/(m ² ‧day).

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

The acrylic film having a thickness of 40 μm used in Production Example 1 was changed to an acrylic film having a thickness of 20 μm (water permeability: 110 g/(m ² ‧day)), and a TAC film having a thickness of 60 μm was changed to a TAC film having a thickness of 25 μm. (water vapor transmission rate: 2000 g/(m ² ‧ day)), and a pressure-sensitive adhesive having a thickness of 10 μm was applied to the acrylic film side having a thickness of 20 μm to further bond a COP film having a thickness of 20 μm (water permeability: 6.5 g/(m ² ‧ A polarizing film (3) was obtained in the same manner as in Production Example 1 except for the above. The moisture permeability of the obtained polarizing film (3) was 6.1 g/(m ² ‧day).

Production Example 4 (Production of Polarizing Film (4))

A polarizing film was obtained in the same manner as in Production Example 3 except that a COP film having a thickness of 20 μm (moisture permeability: 6.5 g/(m ² ‧day)) was not bonded to the adhesive of 10 μm in the production example 3 4). The obtained polarizing film (4) had a moisture permeability of 35 g/(m ² ‧day).

Production Example 5 (Production of Polarizing Film (5))

Further, a PET film (water permeability: 21 g/(m ² ‧day)) having a thickness of 25 μm was bonded to the TAC film side having a thickness of 25 μm on the polarizing film (4) of Production Example 4 via an adhesive of 10 μm to obtain a polarizing film. (5). The moisture permeability of the obtained polarizing film (5) was 7.2 g/(m ² ‧day).

Production Example 6 (Production of Polarizing Film (6))

Further, a PET film (water permeability: 28 g/(m ² ‧day)) having a thickness of 20 μm was bonded to the TAC film side having a thickness of 25 μm on the polarizing film (4) of Production Example 4 via an adhesive of 10 μm to obtain a polarizing film. (6). 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 (water permeability: 3.4 g/(m ² ‧day)) having a thickness of 30 μm was bonded to the acrylic film side having a thickness of 20 μm on the polarizing film (4) of Production Example 4 via an adhesive having a thickness of 10 μm to obtain polarized light. Membrane (7). 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 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 by weight of 100 parts of the monomer (solid content) are added. The AIBN as a starter was added with ethyl acetate, and after reacting at 60 ° C for 7 hours under a nitrogen gas stream, ethyl acetate was added to the reaction liquid to obtain an acrylic polymer having a weight average molecular weight of 1.6 million. Solution (solid content concentration: 30% by weight). 0.1 parts of trimethylolpropane benzenedimethylene diisocyanate (trade name: TAKENATE D110N, manufactured by Mitsui Chemicals Co., Ltd.) and 0.3 parts of peroxide per 100 parts of the solid content of the acrylic polymer solution Benzoic acid was used as a crosslinking agent to prepare 0.075 parts of γ-glycidoxypropyltrimethoxydecane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a decane coupling agent to obtain an acrylic adhesive. Composition (1).

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) was uniformly applied to the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater, and air circulation at 155 ° C was performed. The coating was dried in a constant temperature oven for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (1) obtained in Production Example 1 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4 were transferred and adhered to each other to form an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

A polarizing film with an adhesive layer attached to a transparent conductive layer side (visible side) of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer (1) A polarizing film (4) with an adhesive layer is attached to the opposite side (light source side) of the liquid crystal cell to form a liquid crystal panel.

Example 2

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (2) obtained in Production Example 2 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4 were transferred and adhered to each other to form an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (2) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 3

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (3) obtained in Production Example 3 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4 were transferred and formed with a spacer of an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 4

(Preparation of acrylic adhesive composition)

To a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 99.5 parts of butyl acrylate, 0.5 part of 4-hydroxybutyl acrylate, and 0.1 part by weight of 100 parts of the monomer (solid content) were added. EIBN, which was added as a starter with ethyl acetate, was reacted at 60 ° C for 7 hours under a nitrogen stream, and then ethyl acetate was added to the reaction mixture to obtain an acrylic polymer having a weight average molecular weight of 1.6 million. Solution (solid content concentration: 30% by weight). 0.1 parts of trimethylolpropane benzenedimethylene diisocyanate (trade name: TAKENATE D110N, manufactured by Mitsui Chemicals Co., Ltd.) and 0.3 parts of peroxide per 100 parts of the solid content of the acrylic polymer solution Benzoic acid was used as a crosslinking agent to prepare 0.075 parts of γ-glycidoxypropyltrimethoxydecane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a decane coupling agent to obtain an acrylic adhesive. Composition (2).

In the third embodiment (manufacture of a polarizing film with an adhesive layer), the adhesive layer formed on the polarizing film (3) using the acrylic adhesive composition (2) is used, and In the same manner as in Example 3, a liquid crystal panel was produced. The moisture content of the adhesive layer formed on the polarizing film (3) was 0.5% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 5

(Preparation of acrylic adhesive composition)

To a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device, 99.9 parts of 2-ethylhexyl acrylate, 0.1 part of 6-hydroxyhexyl acrylate, and 100 parts of the monomer (solid content) were added. 0.1 part of AIBN as a starter added with ethyl acetate was reacted at 60 ° C for 7 hours under a nitrogen stream, and then ethyl acetate was added to the reaction mixture to obtain a weight average molecular weight of 1.8 million. A solution of an acrylic polymer (solid content concentration: 30% by weight). 0.1 parts of trimethylolpropane/toluene diisocyanate adduct (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.) and 0.03 parts of lauric acid per 100 parts of the solid content of the acrylic polymer solution Acid dioctyltin-based crosslinking accelerator (trade name: Enbilizer OL-1, manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking agent, and formulated 0.01 parts of γ-glycidoxypropyltrimethoxydecane (commercial product) Name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) As a decane coupling agent, an acrylic pressure-sensitive adhesive composition (3) was obtained.

(Production of polarizing film with adhesive layer)

In the third embodiment (preparation of a polarizing film with an adhesive layer), the adhesive layer formed on the polarizing film (3) using the acrylic adhesive composition (3) is used, and In the same manner as in Example 3, a liquid crystal panel was produced. The moisture content of the adhesive layer formed on the polarizing film (3) was 0.3% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 6

(Preparation of monomer components used in UV polymerization)

61 parts by weight of 2-ethylhexyl acrylate and 14 parts by weight of N-vinyl-2-pyrrolidone, and two kinds of photopolymerization initiators (trade name: Irgacure 184, manufactured by BASF Corporation) of 0.05 parts by weight were placed in a four-necked flask. And a photopolymerization initiator (trade name: Irgacure 651, manufactured by BASF Corporation) in an amount of 0.05 parts by weight to prepare a monomer mixture. Then, the above monomer mixture was exposed to ultraviolet rays under a nitrogen atmosphere to partially photopolymerize, thereby obtaining a partial polymer (acrylic polymer slurry) having a polymerization rate of about 10% by weight.

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

(Production of adhesive layer using UV polymerization)

Then, the monomer component (4) prepared above was applied to a polyester film having a thickness of 38 μm which was subjected to a release treatment on one side with an anthrone (product name: DIAFOIL MRF, Mitsubishi resin (at a final thickness of 20 μm). The release treated surface of the product) is formed into a coating layer. Then, the surface of the monomer component to be coated was coated with a polyester film (trade name: DIAFOIL MRF, manufactured by Mitsubishi Resin Co., Ltd.) having a thickness of 38 μm which was subjected to a release treatment on one side with an anthrone, and the film was peeled off. The treated surface is the coating layer side. Thereby, the coating layer of the monomer component is isolated from oxygen. Using a chemical lamp (manufactured by Toshiba Co., Ltd.), the sheet having the coating layer thus obtained was irradiated with ultraviolet light of 5 mW/cm ² (measured using TOPCON UVR-T1 having a maximum sensitivity of about 350 nm). In seconds, the coating layer was hardened to form an adhesive layer, and an adhesive sheet was produced. The polyester film coated on both sides of the adhesive layer functions as a release liner (separator).

(Production of polarizing film with adhesive layer)

The separator of the above-mentioned adhesive layer was peeled off only one surface, and the separator having the adhesive layer formed thereon was transferred and adhered to the surface of the acrylic film of the polarizing film (3) obtained in Production Example 3, and a polarizing film with an adhesive layer was prepared. (3). The moisture content of the adhesive layer formed on the polarizing film (3) is 3.1. weight%.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer prepared in the same manner as in Example 1 was bonded to form a liquid crystal panel.

Example 7

(Preparation of Emulsion-type Acrylic Adhesive Composition)

780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added to the container, and they were mixed to obtain a monomer mixture. Then, 30 parts of Aqualon HS-10 (manufactured by Daiichi Kogyo Co., Ltd.) and 635 parts of ion-exchanged water as a reactive surfactant were added to 1000 parts of the monomer mixture prepared in the above ratio, and a homogenizer was used. (manufactured by Special Machine Industry Co., Ltd.) was stirred at 6000 (rpm) for 5 minutes to prepare a monomer emulsion.

Then, 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 tube, a nitrogen introduction tube, a thermometer, a dropping funnel, and a stirring blade, and then the reaction vessel was sufficiently nitrogen-substituted. After adding 0.6 parts of ammonium persulfate, it was polymerized at 60 ° C for 1 hour while stirring. Then, the reaction vessel was kept at 60 ° C, and the remaining monomer emulsion was added dropwise thereto over 3 hours, and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Then, after cooling the above polymer emulsion to room temperature, ammonia water having a concentration of 10% was added thereto to obtain an emulsion type acrylic pressure-sensitive adhesive having a pH of 8 and a solid content adjusted to 45.6%.

(Production of polarizing film with adhesive layer)

The film was coated on a release film (trade name: DIAFOIL MRF-38, polyethylene terephthalate substrate, manufactured by Mitsubishi Chemical Co., Ltd.) using a die coater in a thickness of 20 μm after drying. The above emulsion type acrylic adhesive was applied, and then dried at 120 ° C for 5 minutes to form an adhesive layer. Then, the spacer formed with the above adhesive layer is transferred and adhered The acrylic film surface of the polarizing film (3) obtained in Production Example 3 was used to produce a polarizing film (3) with an adhesive layer. The obtained adhesive layer had a water content of 5.0% by weight.

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) prepared in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. Then, a separator containing the adhesive layer of the acrylic pressure-sensitive adhesive composition (1) was formed by transferring the acrylic film surface of the polarizing film (4) obtained in Production Example 4 to form a polarizing film with an adhesive layer. The obtained adhesive layer had a water content of 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 8

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (5) obtained in Production Example 5 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4 were transferred and formed with a spacer of an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (5) having an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 9

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (7) obtained in Production Example 7 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4 were transferred and adhered to each other to form an adhesive layer. A polarizing film with an adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (7) adhered to an adhesive layer on a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 10

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (6) obtained in Production Example 6 and Production Example 4 The acrylic film surface obtained by the polarizing film (4) is transferred and formed with a spacer of an adhesive layer to form a polarizing film with an adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (6) having an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Example 11

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, two polarizing films (1) obtained in Production Example 1 were prepared, and a spacer having an adhesive layer was transferred and adhered to the respective acrylic film faces of the polarizing film (1) to prepare a polarizing film with an adhesive layer. . The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film with an adhesive layer attached to the transparent conductive layer side of the liquid crystal cell having a transparent ITO layer (contact angle with respect to water: 73°, thickness: 20 nm) and the opposite side of the liquid crystal cell ( 1) Forming a liquid crystal panel.

Example 12

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. Drying in an air circulating constant temperature oven at 155 ° C for 2 minutes on the surface of the substrate An adhesive layer having a thickness of 20 μm. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (1) obtained in Production Example 1 and the acrylic film surface of the polarizing film (6) obtained in Production Example 6 were transferred and adhered to form a separator of an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (1) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (6) with an adhesive layer is attached to form a liquid crystal panel.

Example 13, 14

The liquid crystal cell having an amorphous ITO layer (contact angle with respect to water: 73°, thickness: 20 nm) used in Example 1 (manufacture of a liquid crystal panel) was changed to have a crystallized ITO layer (contact with water) The liquid crystal cell having an angle of 58° and a thickness of 20 nm was changed to a liquid crystal cell having an acrylic resin layer (contact angle with respect to water: 72°, thickness: 5 μm), and the same as in the first embodiment. Method of making a liquid crystal panel.

Comparative example 1

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) produced in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. In addition, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (4) obtained in Production Example 4 and the acrylic film surface of the polarizing film (3) obtained in Production Example 3 were transferred and adhered to each other to form an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (4) having an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (3) with an adhesive layer is attached to form a liquid crystal panel.

Comparative example 2

(Preparation of acrylic adhesive composition)

After installing a three-way switch in a 2 L three-necked flask and replacing it with nitrogen, 868 g of toluene and 43.4 g of 1,2-dimethoxyethane were added thereto at room temperature, and 40.2 mmol of bis (2,6-) was added thereto. 60.0 g of a toluene solution of di-tert-butyl-4-methylphenoxy)isobutylaluminum was further added, and 3.68 g of a mixed solution of cyclohexane and n-hexane containing 6.37 mmol of a second butyllithium was further added. Then, 51.5 g of methyl methacrylate (MMA) was added thereto, and the mixture was stirred at room temperature for 60 minutes. Then, the internal temperature of the polymerization liquid was cooled to -30 ° C, and 240 g of n-butyl acrylate (nBA) was added dropwise over 2 hours. Then, 51.5 g of methyl methacrylate was added, and the mixture was stirred at room temperature for one night, and then 3.50 g of methanol was added to terminate the polymerization. The obtained reaction liquid was poured into methanol, and the precipitate was recovered by filtration. 340 g of the block copolymer 1 was obtained by drying it.

^{As a result of 1} H-NMR measurement and GPC measurement, the above block copolymer 1 was a triblock copolymer of PMMA-PnBA-PMMA, and had a weight average molecular weight (Mw) of 7.9 × 10 ⁴ and a number average molecular weight (Mn) of 6.2. ×10 ⁴ , molecular weight distribution (Mw/Mn) was 1.27. Further, PMMA-PnBA-PMMA represents polymethyl methacrylate-polybutyl n-butyl acrylate-polymethyl methacrylate. The weight ratio of the monomer units of the block copolymer 1 was nBA/MMA = 70/30.

(Production of polarizing film with adhesive layer)

The block copolymer 1 was dissolved in toluene to prepare an adhesive solution having a solid content concentration of 30%, and the thickness of the adhesive layer after drying was 25 μm using a reverse coating method. The coating was applied to a separator containing a polyester film (thickness: 38 μm) subjected to mold release treatment, and heat-treated at 90 ° C for 3 minutes to volatilize the solvent to obtain an adhesive layer. Then, the separator of the above-mentioned adhesive layer was formed by transferring the acrylic film surface of the polarizing film (3) obtained in Production Example 3, and a polarizing film (3) with an adhesive layer was produced. The obtained adhesive layer had a water content of 0.1% by weight.

(Production of polarizing film with adhesive layer)

The acrylic adhesive composition (1) prepared in Example 1 was uniformly coated on the surface of a polyethylene terephthalate film (substrate) treated with an anthrone-based release agent using a spray coater. The adhesive was dried in an air circulating oven at 155 ° C for 2 minutes to form an adhesive layer having a thickness of 20 μm on the surface of the substrate. Then, a separator containing the adhesive layer of the acrylic pressure-sensitive adhesive composition (1) was formed by transferring the acrylic film surface of the polarizing film (4) obtained in Production Example 4 to form a polarizing film with an adhesive layer. The obtained adhesive layer had a water content of 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Comparative example 3

(Preparation of Emulsion-type Acrylic Adhesive Composition)

780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added to the container, and they were mixed to obtain a monomer mixture. Then, 60 parts of Aqualon HS-10 (manufactured by Daiichi Kogyo Co., Ltd.) and 635 parts of ion-exchanged water as a reactive surfactant were added to 1000 parts of the monomer mixture prepared in the above ratio, and a homogenizer was used. (manufactured by Special Machine Industry Co., Ltd.) was stirred at 6000 (rpm) for 5 minutes to prepare a monomer emulsion.

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

(Production of polarizing film with adhesive layer)

The film was coated on a release film (trade name: DIAFOIL MRF-38, polyethylene terephthalate substrate, manufactured by Mitsubishi Chemical Co., Ltd.) using a die coater in a thickness of 20 μm after drying. The acrylic pressure-sensitive adhesive composition (1) prepared in Example 1 and the emulsion-type acrylic pressure-sensitive adhesive (4) were applied, and then dried at 120 ° C for 5 minutes to form an adhesive layer. Then, the separator having the adhesive layer containing the emulsion type acrylic pressure-sensitive adhesive (4) was transferred and transferred to the acrylic film surface of the polarizing film (3) obtained in Production Example 3, and the polarizing layer of the adhesive layer was prepared. membrane. The obtained adhesive layer had a water content of 6.2% by weight. Further, the separator having the adhesive layer containing the acrylic pressure-sensitive adhesive composition (1) was transferred and transferred to the acrylic film surface of the polarizing film (4) obtained in Production Example 4, and a polarizing film with an adhesive layer was prepared. . The obtained adhesive layer had a water content of 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (3) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (4) with an adhesive layer is attached to form a liquid crystal panel.

Comparative example 4

(Production of polarizing film with adhesive layer)

Polyethylene terephthalate treated with an anthrone-based stripper using a spray coater The surface of the ester film (substrate) was uniformly coated with the acrylic adhesive composition (1) produced in Example 1, and dried in an air circulating oven at 155 ° C for 2 minutes to form a thickness of 20 μm on the surface of the substrate. Agent layer. Further, another piece of the same adhesive layer was produced. Then, the acrylic film surface of the polarizing film (1) obtained in Production Example 1 and the acrylic film surface of the polarizing film (7) obtained in Production Example 7 were transferred to each other to form a separator having an adhesive layer. A polarizing film of the adhesive layer. The moisture content of the obtained adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panel)

a polarizing film (1) with an adhesive layer attached to a transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (a contact angle with respect to water: 73°, thickness: 20 nm) as a transparent conductive layer, in a liquid crystal cell On the opposite side, a polarizing film (7) with an adhesive layer is attached to form a liquid crystal panel.

The following evaluations were performed on the adhesive layer and the liquid crystal panel obtained in the examples and the comparative examples.

<Method for Measuring Saturated Water Content of Adhesive Layer>

Approximately 50 mg of the sample was collected from the adhesive layer of the polarizing film with the adhesive layer prepared in the examples and the comparative examples. The weight (W1) of the state in which the sample was completely removed by water at 100 ° C for 1 hour was measured using a moisture adsorption-desorption measuring apparatus (IGA-Sorp, manufactured by Hiden Co., Ltd.), and then placed at 23 ° C, 0% RH. After 2 hours, it was allowed to stand at 23 ° C, 55% RH for 5 hours, at 60 ° C, 90% RH for 5 hours, and at 23 ° C, 55% RH for 5 hours, and the change in weight was observed. The weight (W2) was measured at the time point (saturated state) at which the weight of the sample did not change. The saturated water content was determined by the following formula.

<White turbidity test>

(production of test samples)

An adherend 1 having an amorphous ITO layer (contact angle with respect to water: 73°, thickness: 20 nm) formed on one surface of an alkali-free glass substrate (contact angle with respect to water: 38°) by sputtering The adherend 2 in which a crystallized ITO layer (contact angle with respect to water: 58°, thickness: 20 nm) was formed on one surface of an alkali-free glass substrate (contact angle with respect to water: 38°) was prepared. The Sn ratio of the crystalline ITO film was 10% by weight. The Sn ratio of the amorphous ITO film was 3% by weight. In addition, the adherend 3 in which an acrylic resin layer (contact angle with respect to water: 72°, thickness: 5 μm) was formed on the amorphous ITO layer of the adherend 1 in the following order. In the examples 1 to 12 and the comparative examples 1 to 4, a polarizing film (the polarizing film of Table 1) laminated on the transparent conductive layer side (visible side) of the liquid crystal cell of the liquid crystal panel of each example was used. 1) attached to the amorphous ITO layer side of the adherend 1, and a polarizing film (polarizing film 2 of Table 1) laminated on the opposite side (light source side) of the liquid crystal cell is attached to the alkali-free glass of the adherend 1 Side, as a sample for white turbidity test. Further, in Example 13, the polarizing film (1) with the adhesive layer used in Example 13 was attached to the crystallized ITO layer of the adherend 2, and the use in Example 13 was attached to the alkali-free glass side. a polarizing film (4) with an adhesive layer; in Example 14, the polarizing film (1) of the adhesive layer used in Example 14 was attached to the side of the acrylic resin layer of the adherend 3, and the alkali-free film was used. The polarizing film (4) with the adhesive layer used in Example 14 was attached to the glass side, and each of the samples for the white turbidity test was prepared. The adherends 1 to 3 reproduced the surface states of the liquid crystal cells used in the examples and the comparative examples.

(Method of Forming Acrylic Resin Layer)

5 parts of a photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) was mixed with 100 parts of polyfunctional urethane acrylate (solid content: 100%), and a diluent solvent (methyl isobutyl) was used. Ketone (MIBK)) A coating liquid having a solid content of 45% was prepared. Amorphous in the above-mentioned adherend 1 in such a manner that the film thickness after drying is 5 μm After coating on the ITO layer, it was dried at 80 ° C, and cured by UV irradiation (accumulated light amount: 300 mJ) to form an acrylic resin layer, which was used as the adherend 3 .

(white turbidity measurement)

The sample for the above sample was subjected to autoclave heat treatment at 50 ° C, 5 atm, and 15 minutes, and then placed in a constant temperature and humidity machine at 60 ° C and 90% R.H. The sample was observed after 120 hours, and evaluated according to the following evaluation criteria.

1: Confirm with a microscope, no water droplets

2: Confirmed by a microscope, a small amount of water droplets can be confirmed, but no white turbidity is observed.

3: Some of the eyes are cloudy

4: The overall appearance is slightly cloudy

5: Overall white turbid

<Endurance test>

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

1: no foaming

2: No foaming was observed in very few parts of the visual inspection

3: Only a small part of the visual confirmation of foaming

4: Visual inspection confirmed foaming

5: Visual confirmation of foaming as a whole

1a‧‧‧Visual side transparent protective film

1b‧‧‧ Liquid crystal side transparent protective film

2a‧‧‧Polarized elements

2b‧‧‧Polarized elements

3a‧‧‧ Liquid crystal side transparent protective film

3b‧‧‧visible side transparent protective film

4a‧‧‧1st polarizing film

4b‧‧‧2nd polarizing film

5a‧‧‧Adhesive layer 1

5b‧‧‧Adhesive layer 2

6‧‧‧Transparent conductive layer

7‧‧‧1st transparent substrate

8‧‧‧Liquid layer

9‧‧‧2nd transparent substrate

10‧‧‧Liquid Crystal Unit

12‧‧‧ LCD panel

A‧‧‧High contact angle

Claims (7)

A liquid crystal panel characterized in that one surface of the liquid crystal cell has a contact angle of 40 to 110° with respect to water, and has a high contact angle on the liquid crystal cell: 60° C. and 90% RH. The adhesive layer having a saturated water content of 0.3 to 6% by weight and the first polarizing film having a moisture permeability of 0.5 to 30 g/(m ² ‧day) at 40 ° C and 90% RH are on the other side of the liquid crystal cell It has 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 of claim 1, wherein the moisture permeability of the second polarizing film is greater than the moisture permeability of the first polarizing film. The liquid crystal panel of claim 1 or 2, wherein the adhesive layer has a saturated water content of 0.5 to 6% by weight at 60 ° C and 90% R.H. The liquid crystal panel according to any one of claims 1 to 3, wherein the high contact angle of the liquid crystal cell is formed by a transparent conductive layer. The liquid crystal panel according to any one of claims 1 to 4, wherein the other surface of the high contact angle surface of the liquid crystal cell has a contact angle with respect to water of 3° or more and less than 40°. The liquid crystal panel according to any one of claims 1 to 5, wherein the second polarizing film is laminated on the liquid crystal cell via an adhesive layer having a saturated water content of 0.5 to 6% by weight at 60 ° C and 90% R.H. An image display device comprising the liquid crystal panel of any one of claims 1 to 6.