JP2015114386A - Liquid crystal panel and image display device - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal panel that does not become clouded by humidification, and an image display device using the liquid crystal panel. One surface of a liquid crystal cell is a high contact angle surface having a contact angle with water of 40 to 110 ?, and the liquid crystal cell has a high contact angle surface of 60 ° C. and 90% R.D. H. Pressure-sensitive adhesive layer having a saturated moisture content of 0.3 to 6% by weight, and 40 ° C., 90% R.D. H. Has a first polarizing film having a water permeability of 0.5 to 30 g / (m 2 · day), and the other surface of the liquid crystal cell is 40 ° C., 90% R.D. H. A liquid crystal panel comprising a second polarizing film having a moisture permeability of 8 g / (m 2 · day) or more. [Selection] Figure 1

Description

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

  In a liquid crystal panel used for a liquid crystal display device or the like, a polarizing film is usually laminated on both sides of a liquid crystal cell formed from a liquid crystal layer disposed between a pair of transparent substrates via an adhesive layer. Such a pressure-sensitive adhesive layer for optical applications such as liquid crystal panels is required to have high transparency, but if it is returned to room temperature after exposure to high temperature and high humidity conditions, the pressure-sensitive adhesive layer may become clouded (whitened). Was known. This white turbidity phenomenon is considered to be caused by the moisture absorbed in the pressure-sensitive adhesive layer under moist heat being agglomerated when the temperature is returned to room temperature. Consideration has been made.

  Examples of the pressure-sensitive adhesive composition that can suppress the clouding of the pressure-sensitive adhesive layer include, for example, an alkyl ester monomer having 1 to 18 carbon atoms of (meth) acrylic acid, a copolymerizable monomer containing a hydroxyl group, and a dialkyl. An optical pressure-sensitive adhesive composition containing an acrylic resin, which is a copolymer having a weight average molecular weight of 300,000 to 2,000,000, comprising a substituted acrylamide monomer and a crosslinking agent, or a nitrogen-containing vinyl that does not contain a hydroxyl group A pressure-sensitive adhesive composition comprising at least one monomer or an alkoxy group-containing alkyl (meth) acrylate monomer and at least one copolymerizable vinyl monomer containing a hydroxyl group without containing a carboxyl group in a functional group is known. (For example, refer to Patent Documents 1 and 2).

JP 2011-195651 A JP 2013-64079 A

  In Patent Documents 1 and 2, the specific pressure-sensitive adhesive composition is intended to suppress the whitening of the pressure-sensitive adhesive layer, but is defined in relation to the adherend such as a liquid crystal cell. In addition, the water permeability of the polarizing film has not been studied at all, and is not sufficient from the viewpoint of suppressing white turbidity as the whole liquid crystal panel.

  In recent years, there has been a demand for improvement in viewing angle characteristics and reduction in thickness and weight. In order to satisfy these requirements, low moisture-permeable films are often used as retardation films and protective films. However, the low moisture-permeable film is difficult to pass moisture, so when the moisture contained in the pressure-sensitive adhesive layer returns to room temperature under humidification, it is difficult for it to come out of the pressure-sensitive adhesive, and the pressure-sensitive adhesive layer turns cloudy. It was.

  In addition, on one transparent substrate of the liquid crystal cell constituting the liquid crystal panel, there is one in which a transparent conductive film such as an indium tin oxide (ITO) thin film is formed, and the adhesive layer in contact with the transparent conductive film is It turned out that white turbidity tends to be suppressed compared with the adhesive layer which contacts transparent substrates, such as a glass substrate. That is, since the properties of both surfaces of the liquid crystal cell are usually different, it has been found that it is necessary to appropriately suppress white turbidity on both surfaces of the liquid crystal cell to suppress white turbidity as a whole liquid crystal panel.

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

  As a result of intensive studies to solve the above problems, the present inventors control the moisture content of the adhesive layer on 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 on the other surface. Thus, the inventors have found that the object can be achieved and have completed the present invention.

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

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

  60 ° C., 90% R.D. of the pressure-sensitive adhesive layer. H. The saturated moisture content in is preferably 0.5 to 6% by weight.

  The high contact angle surface of the liquid crystal cell is preferably formed of 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 water of 3 ° or more and less than 40 °.

  The second polarizing film has a temperature of 60 ° C. and 90% R.D. H. It is preferable to be laminated on the liquid crystal cell through an adhesive layer having a saturated moisture content of 0.5 to 6% by weight.

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

  In the present invention, a pressure-sensitive adhesive layer having a specific saturated moisture content and a first polarizing film having a specific moisture permeability are arranged on the high contact angle surface of the liquid crystal cell, and the specific moisture permeability is provided on the other surface of the liquid crystal cell. By disposing the second polarizing film having, white turbidity due to humidification as the entire liquid crystal panel can be suppressed. This is because the value of the water contact angle is large at the high contact angle surface of the liquid crystal cell, so that the amount of moisture entering from the interface between the high contact angle surface of the liquid crystal cell and the pressure-sensitive adhesive layer is reduced during humidification. When taking out from the bottom to room temperature, the amount of water that aggregates decreases, and therefore, a first polarizing film having a specific moisture permeability is laminated on the surface through an adhesive layer having a specific saturated moisture content. Thus, the cloudiness of the pressure-sensitive adhesive layer can be suppressed. On the other hand, the other surface of the liquid crystal cell usually uses a base material with a small contact angle of water such as a glass substrate, and the amount of moisture entering from the interface between the base material and the pressure-sensitive adhesive layer is large. When taking out from humidification to room temperature, the amount of water that aggregates increases, but since the surface has the second polarizing film having a specific moisture permeability, the moisture contained in the pressure-sensitive adhesive layer is efficiently exposed to the outside. It is released and can suppress white turbidity.

  Further, as one method for suppressing white turbidity, a method for increasing the moisture content of the pressure-sensitive adhesive layer is known. In such a method of simply increasing the moisture content of the pressure-sensitive adhesive layer, the composition of the pressure-sensitive adhesive layer is limited and the durability (foaming / peeling) of the pressure-sensitive adhesive layer tends to deteriorate. As described above, in the liquid crystal panel, by making the configuration of the upper and lower sides of the liquid crystal cell specific, white turbidity of the entire liquid crystal panel can be suppressed, and the durability is good. The degree of freedom in designing the pressure-sensitive adhesive layer is wider than the method for increasing the moisture content of the pressure-sensitive adhesive layer.

It is sectional drawing which shows typically one Embodiment of the liquid crystal panel of this invention. It is sectional drawing which shows typically one Embodiment of the liquid crystal panel of this invention. It is sectional drawing which shows typically one Embodiment of the liquid crystal panel of this invention.

1. Liquid crystal panel The liquid crystal panel of the present invention has polarizing films on both sides of a liquid crystal cell,
One surface of the liquid crystal cell is a high contact angle surface having a contact angle with water of 40 to 110 °,
On the high contact angle surface, 60 ° C., 90% R.D. H. Pressure-sensitive adhesive layer having a saturated moisture content of 0.3 to 6% by weight, and 40 ° C., 90% R.D. H. Having a first polarizing film having a moisture permeability of 0.5 to 30 g / (m ² · day),
On the other surface of the liquid crystal cell, 40 ° C., 90% R.D. H. It has the 2nd polarizing film whose water vapor transmission rate is 8 g / (m < ² > * day) or more. Hereinafter, the liquid crystal panel of the present invention will be described in detail.

(1) Liquid crystal cell The liquid crystal cell used in the liquid crystal panel of the present invention is not particularly limited as long as the contact angle with respect to water on one side is 40 to 110 °. A first substrate (viewing side) disposed on one side of the liquid crystal layer, and a second substrate (light source side) disposed on the other side of the liquid crystal layer. And the second substrate may include a pixel electrode and a counter electrode for applying a voltage to the liquid crystal layer.

  The liquid crystal cell substrate 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 base materials having transparency can be mentioned, and the materials thereof include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, and polycarbonate resins. Resin, polyamide resin, polyimide resin, polyolefin resin, (meth) acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide Examples thereof include resins.

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

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

  Although the contact angle with respect to the water of the said high contact angle surface is 40-110 degrees, 45-100 degrees may be sufficient and 45-90 degrees may be sufficient. The contact angle of the high contact angle surface on which the transparent conductive film or the like as described above is formed is usually 40 ° or more. Moreover, when a contact angle exceeds 110 degrees, adhesiveness with an adhesive layer falls and there exists a tendency for durability to deteriorate.

  The transparent substrate is preliminarily subjected to etching treatment or undercoating treatment such as sputtering, corona discharge, plasma treatment, flame, ultraviolet irradiation, electron beam irradiation, chemical conversion, oxidation on the surface, and a transparent conductive film provided thereon You may make it improve the adhesiveness with respect to the said base material of an acrylic resin coating film. In addition, before providing the transparent conductive film or the acrylic resin coating film, dust may be removed and cleaned by solvent cleaning or ultrasonic cleaning as necessary.

  The constituent material of the transparent conductive film is not particularly limited, and is selected from the group consisting of indium, tin, zinc, gallium, antimony, titanium, silicon, zirconium, magnesium, aluminum, gold, silver, copper, palladium, and tungsten. A metal oxide of at least one metal is used. The metal oxide may further contain a metal atom shown in the above group, if necessary. For example, indium oxide (ITO) containing tin oxide and tin oxide containing antimony are preferably used, and ITO is particularly preferably used. As ITO, it is preferable to contain 80 to 99 weight% of indium oxide and 1 to 20 weight% of tin oxide.

  The ITO may be crystalline ITO or non-crystalline (amorphous) ITO. Crystalline ITO can be obtained by applying a high temperature during sputtering or by further heating 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 transparent conductive film is not uniformly applied in the surface, and the resistance value in the panel surface is not stable or a predetermined resistance value tends to be not obtained. On the other hand, when it exceeds 200 nm, the productivity of the transparent conductive film is lowered, the cost is increased, and the optical characteristics are also lowered.

  It does not specifically limit as a formation method of the said transparent conductive film, A conventionally well-known method is employable. Specifically, for example, a vacuum deposition method, a sputtering method, and an ion plating method can be exemplified. In addition, an appropriate method can be adopted depending on the required film thickness.

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

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

  In addition, the liquid crystal cell may be provided with a color filter, a black matrix, or the like on any substrate as necessary. In the present invention, the liquid crystal cell is mounted on a commercially available liquid crystal display device. You can also use what you have.

(2) Adhesive layer A first polarizing film is bonded to the high contact angle surface of the liquid crystal cell via an adhesive layer.

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

  The pressure-sensitive adhesive layer in the present invention is preferably formed from a pressure-sensitive adhesive composition containing a base polymer and a crosslinking agent. The pressure-sensitive adhesive composition can be an acrylic, synthetic rubber-based, rubber-based, or silicone-based pressure-sensitive adhesive, but from the viewpoint of transparency, heat resistance, etc., a (meth) acrylic polymer is a base polymer. An acrylic pressure-sensitive adhesive is preferred.

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

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

  The monomer component may contain other polymerizable monomer other than the (meth) acrylic acid ester having an alkyl group having 2 to 14 carbon atoms. The other polymerizable monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. For example, a hydroxyl group-containing monomer, carboxyl And group-containing monomers.

  As the hydroxyl group-containing monomer, a monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group and having a hydroxyl group can be used without particular limitation. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl (meth) acrylate, etc. can be mentioned, and these can be used alone or in combination. Two or more kinds can be mixed and used. A hydroxyl group-containing monomer is preferable because it has an effect of increasing adhesion to a transparent conductive film (particularly ITO). Among these, a hydroxyl group-containing acrylic monomer having 2 to 14 carbon atoms in the side chain is preferable because it has a high effect of increasing the adhesion to the transparent conductive film and has a stronger hydrophilic property.

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

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

  The content of the carboxyl group-containing monomer is preferably 10% by weight or less in the monomer component. When the carboxyl group-containing monomer exceeds 10% by weight in the monomer component, it is not preferable because the transparent conductive film such as an ITO film tends to deteriorate significantly under humidified conditions.

  The other copolymerization monomer is not particularly limited as long as it has a polymerizable functional group related to an unsaturated double bond such as a (meth) acryloyl group or a vinyl group. For example, cyclohexyl (meth) acrylate, (Meth) acrylic acid alicyclic hydrocarbon esters such as bornyl (meth) acrylate and isobornyl (meth) acrylate; for example, (meth) acrylic acid aryl esters such as phenyl (meth) acrylate; for example, vinyl acetate, Vinyl esters such as vinyl propionate; styrenic monomers such as styrene; epoxy group-containing monomers such as glycidyl (meth) acrylate and methyl glycidyl (meth) acrylate; for example, acrylamide, diethylacrylamide, acryloylmorpholine (ACMO), N-vinyl pi Amide group-containing monomers such as lidone (NVP); for example, amino group-containing monomers such as N, N-dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate; for example, N-vinylpyrrolidone, Cyclic nitrogen-containing monomers such as N-vinyl-ε-caprolactam and methylvinylpyrrolidone; for example, alkoxy group-containing monomers such as methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate; for example, acrylonitrile, methacrylonitrile, etc. A cyano group-containing monomer; a functional monomer such as 2-methacryloyloxyethyl isocyanate; an olefin-based monomer such as ethylene, propylene, isoprene, butadiene, and isobutylene; Vinyl ether monomers; for example, halogen atom-containing monomers such as vinyl chloride; N-vinylcarboxylic acid amides and the like.

  Examples of copolymerizable monomers include maleimide monomers such as N-cyclohexylmaleimide, N-isopropylmaleimide, N-laurylmaleimide, and N-phenylmaleimide; for example, N-methylitaconimide, N-ethylitaconimide, N -Itacone imide monomers such as butyl itaconimide, N-octyl itacon imide, N-2-ethylhexyl itacon imide, N- cyclohexyl itacon imide, N- lauryl itacon imide; for example, N- (meth) acryloyloxymethylene succinimide, N- Succinimide monomers such as (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide; for example, styrene sulfonic acid, Examples include sulfonic acid group-containing monomers such as aryl sulfonic acid, 2- (meth) acrylamide-2-methylpropane sulfonic acid, (meth) acrylamide propane sulfonic acid, sulfopropyl (meth) acrylate, and (meth) acryloyloxynaphthalene sulfonic acid. .

  In addition, as the copolymerizable monomer, for example, glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate Other examples include, for example, tetrahydrofurfuryl (meth) acrylate, a heterocyclic ring such as fluorine (meth) acrylate, and an acrylate monomer containing a halogen atom.

  Furthermore, a polyfunctional monomer can be used as the copolymerizable monomer. Examples of the polyfunctional monomer include compounds having two or more unsaturated double bonds such as a (meth) acryloyl group and a vinyl group. For example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetraethylene glycol di (meth) acrylate, etc. (mono or poly) In addition to (mono or poly) alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and (mono or poly) propylene glycol di (meth) acrylate such as propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pen Esterified product of (meth) acrylic acid and polyhydric alcohol such as erythritol tri (meth) acrylate and dipentaerythritol hexa (meth) acrylate; polyfunctional vinyl compound such as divinylbenzene; allyl (meth) acrylate, (meth) Examples thereof include compounds having a reactive unsaturated double bond such as vinyl acrylate. In addition, as a polyfunctional monomer, polyester (meta) having two or more unsaturated double bonds such as (meth) acryloyl group and vinyl group as functional groups similar to the monomer component is added to a skeleton such as polyester, epoxy, and urethane. ) Acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, and the like can also be used.

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

  The weight average molecular weight of the (meth) acrylic polymer used in the present invention is preferably in the range of 1,200,000 to 3,000,000, more preferably 1,200,000 to 2,700,000, and even more preferably 1,200,000 to 2,500,000. If the weight average molecular weight is less than 1,200,000, it may not be preferable in terms of heat resistance. Moreover, when the weight average molecular weight is less than 1,200,000, the low molecular weight component increases in the pressure-sensitive adhesive composition, and the low molecular weight component bleeds out from the pressure-sensitive adhesive layer, which may impair transparency. Moreover, the pressure-sensitive adhesive layer obtained using a (meth) acrylic polymer having a weight average molecular weight of less than 1,200,000 may have poor solvent resistance and mechanical properties. On the other hand, if the weight average molecular weight is larger than 3 million, a large amount of dilution solvent is required to adjust the viscosity for coating, which is not preferable from the viewpoint of cost. Moreover, it is preferable from a viewpoint of corrosion resistance and durability because a weight average molecular weight exists in the said range. The weight average molecular weight is a value calculated by polystyrene conversion measured by GPC (gel permeation chromatography).

  Production of such a (meth) acrylic polymer can be appropriately selected from known production methods such as solution polymerization, bulk polymerization, emulsion polymerization, and various radical polymerizations, and is not particularly limited. From the viewpoint of the moisture content of the pressure-sensitive adhesive layer, solution polymerization is preferred. Further, the (meth) acrylic polymer obtained may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.

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

  The polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.

  Examples of the polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (5-methyl-2). -Imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) disulfate, 2,2'-azobis (N, N'-dimethyleneisobutylamidine), 2,2 Azo initiators such as' -azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (trade name: VA-057, manufactured by Wako Pure Chemical Industries, Ltd.), potassium persulfate, Persulfates such as ammonium sulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di sec-butyl peroxydicarbonate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1, 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoyl peroxide, t-butylperoxyisobutyrate, 1,1-di (t- Hexylperoxy) peroxide initiators such as cyclohexane, t-butyl hydroperoxide, hydrogen peroxide, peroxides such as a combination of persulfate and sodium bisulfite, a combination of peroxide and sodium ascorbate, And redox initiators combined with reducing agents. But it is not limited thereto.

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

  Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto-1-propanol. The chain transfer agent may be used alone or in combination of two or more, but the total content is 0.1 parts by weight with respect to 100 parts by weight of the total amount of monomer components. Less than or equal to

  Various silane coupling agents can be added to the pressure-sensitive adhesive composition used in the present invention in order to improve adhesion under high-temperature and high-humidity conditions. As the silane coupling agent, one having any appropriate functional group can be used. Examples of the functional group include vinyl group, epoxy group, amino group, mercapto group, (meth) acryloxy group, acetoacetyl group, isocyanate group, styryl group, polysulfide group and the like. Specifically, for example, vinyl group-containing silane coupling agents such as vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycol Epoxy group-containing silane coupling agents such as sidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane; γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, γ-triethoxysilyl-N- (1,3-dimethylbutylidene) Propylamine, N-phenyl-γ Amino group-containing silane coupling agents such as aminopropyltrimethoxysilane; γ-mercaptopropylmethyldimethoxysilane and other mercapto group-containing silane coupling agents; p-styryltrimethoxysilane and other styryl group-containing silane coupling agents; (Meth) acrylic group-containing silane coupling agents such as acryloxypropyltrimethoxysilane and γ-methacryloxypropyltriethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane; bis (triethoxysilyl) And polysulfide group-containing silane coupling agents such as propyl) tetrasulfide.

  The silane coupling agent may be used alone or in combination of two or more, but the total content is based on 100 parts by weight of the base polymer (solid content), The amount is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, and further preferably 0.02 to 0.8 part by weight. When the amount of the silane coupling agent exceeds 1 part by weight, an unreacted coupling agent component is generated, which is not preferable from the viewpoint of durability.

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

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

  As the cross-linking agent, a polyfunctional compound is used, and an organic cross-linking agent and a polyfunctional metal chelate are exemplified. 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, an aziridine crosslinking agent, and a peroxide crosslinking agent. A polyfunctional metal chelate is one in which a polyvalent metal atom is covalently or coordinately bonded to an organic compound. Examples of polyvalent metal atoms include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti, and the like. Can be mentioned. Examples of the atom in the organic compound that is covalently bonded or coordinated include an oxygen atom, and examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound. These crosslinking agents can be used alone or in combination of two or more. Among these, a peroxide type crosslinking agent and an isocyanate type crosslinking agent are preferable, and it is more preferable to use these in combination.

  The isocyanate-based crosslinking agent refers to a compound having two or more isocyanate groups in a molecule (including isocyanate-regenerating functional groups in which isocyanate groups are temporarily protected by a blocking agent or quantification).

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

  More specifically, for example, lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate, alicyclic isocyanates such as cyclopentylene diisocyanate, cyclohexylene diisocyanate and isophorone diisocyanate, 2,4-tolylene diisocyanate, Aromatic diisocyanates such as 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate, trimethylolpropane / tolylene diisocyanate trimer adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd. ), Trimethylolpropane / hexamethylene diisocyanate trimer adduct (trade name: Coronate HL, manufactured by Nippon Polyurethane Industry Co., Ltd.), hexame Isocyanurate of diisocyanate (trade name: Coronate HX, manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like, trimethylolpropane adduct of xylylene diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals, Inc.), Trimethylolpropane adduct of hexamethylene diisocyanate (trade name: D160N, manufactured by Mitsui Chemicals); polyether polyisocyanate, polyester polyisocyanate, and adducts of these with various polyols, isocyanurate bond, burette bond And polyisocyanate polyfunctionalized with an allophanate bond. Among these, it is preferable to use an aliphatic isocyanate because the reaction rate is high.

  Various peroxides are used as the peroxide-based crosslinking agent. Examples of peroxides include di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, and t-butylperoxyneodecanoate. , T-hexylperoxypivalate, t-butylperoxypivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxyisobutyrate, 1 1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, di (4-methylbenzoyl) peroxide, dibenzoylperoxide, t-butylperoxyisobutyrate, and the like. Among these, di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and dibenzoyl peroxide, which are particularly excellent in crosslinking reaction efficiency, are preferably used.

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

  Furthermore, the pressure-sensitive adhesive composition used in the present invention includes a viscosity modifier, a release modifier, a tackifier, a plasticizer, a softener, glass fiber, glass beads, metal powder, and other inorganic materials as necessary. Various additives such as powder fillers, pigments, colorants (pigments, dyes, etc.), pH adjusters (acids or bases), antioxidants, UV absorbers, etc. Agents can also be used as appropriate.

  The method for forming the pressure-sensitive adhesive layer is not particularly limited, but the pressure-sensitive adhesive composition is applied on various substrates, dried by a dryer such as a heat oven, and the pressure-sensitive adhesive layer is formed by evaporating the solvent and the like. The pressure-sensitive adhesive layer may be transferred onto a polarizing film or a liquid crystal cell substrate, which will be described later, and the pressure-sensitive adhesive layer is coated directly on the polarizing film or the liquid crystal cell. It may be formed. In this invention, the method of producing the polarizing film with an adhesive layer which formed the adhesive layer on the polarizing film previously, and sticking the said polarizing film with an adhesive layer to a liquid crystal cell is preferable.

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

  Various methods are used as a method of applying the pressure-sensitive adhesive composition to the substrate or polarizing film. Specifically, for example, fountain coater, roll coat, kiss roll coat, gravure coat, reverse coat, roll brush, spray coat, dip roll coat, bar coat, knife coat, air knife coat, curtain coat, lip coat, Daiko Examples of the method include an extrusion coating method using a catalyst.

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

  The thickness (after drying) of the pressure-sensitive adhesive layer is, for example, preferably 5 to 100 μm, more preferably 7 to 70 μm, and further preferably 10 to 50 μm. When the thickness of the pressure-sensitive adhesive layer is less than 5 μm, the adhesion to the adherend becomes poor, and the durability under high temperature and high temperature and humidity tends to be insufficient. On the other hand, when the thickness of the pressure-sensitive adhesive layer exceeds 100 μm, the pressure-sensitive adhesive composition is not sufficiently dried during the application and drying of the pressure-sensitive adhesive layer, and bubbles remain or the surface of the pressure-sensitive adhesive layer. There is a tendency that unevenness in thickness occurs and problems in appearance tend to become apparent.

  Examples of the constituent material of the release film include resin films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and nonwoven fabric, nets, foam sheets, metal foils, and laminates thereof. An appropriate thin leaf body can be used, but a resin film is preferably used from the viewpoint of excellent surface smoothness.

  Examples of the resin film include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene- Examples thereof include a vinyl acetate copolymer film.

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

  The transparent resin film substrate is not particularly limited, and various resin films having transparency are used. The resin film is formed of a single layer film. For example, the materials include polyester resins such as polyethylene terephthalate and polyethylene naphthalate, acetate resins, polyethersulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins. , Polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide resin, and the like. Of these, polyester resins, polyimide resins and polyethersulfone resins are particularly preferable.

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

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

  Examples of the polymers include polyurethane resins, polyester resins, acrylic resins, polyether resins, cellulose resins, polyvinyl alcohol resins, polyvinyl pyrrolidone, polystyrene resins, and the like. Among these, polyurethane resins, polyester resins, and acrylic resins are particularly preferable. These resins can be appropriately mixed with a crosslinking agent. These other binder components can be used singly or in combination of two or more as appropriate. The thickness of the anchor layer is not particularly limited, but is preferably 5 to 300 nm.

  The method for forming the anchor layer is not particularly limited and can be performed by a generally known method. In forming the anchor layer, the iodine polarizing film can be activated. Various methods can be employed for the activation treatment, such as corona treatment, low-pressure UV treatment, plasma treatment, and the like.

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

  Moreover, when the adhesive layer of the polarizing film with an adhesive layer for transparent conductive films and the adhesive layer on the liquid crystal cell are exposed, the adhesive layer is protected with a release film (separator) until it is put to practical use. May be. The above-mentioned thing can be mentioned as a release film. When a release film is used as a base material in the production of the above-mentioned pressure-sensitive adhesive layer, the release film is made of a transparent conductive material by laminating the pressure-sensitive adhesive layer on the release film and a polarizing film or a liquid crystal cell. It can be used as a release film for a pressure-sensitive adhesive layer of a pressure-sensitive adhesive layer for a film or a liquid crystal cell with a pressure-sensitive adhesive layer, and the process can be simplified.

(3) 1st polarizing film As a 1st polarizing film bonded together to the high contact angle surface of the said liquid crystal cell through the above-mentioned adhesive layer, 40 degreeC, 90% R. H. The moisture permeability is not particularly limited as long as it has a moisture permeability of 0.5 to 30 g / (m ² · day). As the moisture permeability of the first polarizing film is preferably ^{3.0~30g / (m 2 · day)} , more preferably ^{6.0~30g / (m 2 · day)} , 9 even more preferably from ^{.0~30g / (m 2 · day)} , and most preferably ^{21.0~30g / (m 2 · day)} . When the moisture permeability of the first polarizing film is less than 0.5 g / (m ² · day), it becomes difficult for moisture in the pressure-sensitive adhesive layer to escape to the outside through the first polarizing film. As a result, white turbidity of the pressure-sensitive adhesive layer is deteriorated, foaming is generated, and durability is deteriorated. The adjustment of the moisture permeability of the first polarizing film can be performed by appropriately adjusting the moisture permeability, thickness, etc. of the transparent protective film described later.

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

  The polarizer is not particularly limited, and various types can be used. Examples of polarizers include dichroic iodine and dichroic dyes on hydrophilic polymer films such as polyvinyl alcohol films, partially formalized polyvinyl alcohol films, and ethylene / vinyl acetate copolymer partially saponified films. Examples thereof include polyene-based oriented films such as those obtained by adsorbing substances and uniaxially stretched, polyvinyl alcohol dehydrated products and polyvinyl chloride dehydrochlorinated products. Among these, a polarizer composed of a polyvinyl alcohol film and a dichroic substance such as iodine is preferable, and an iodine polarizer containing iodine and / or iodine ions is more preferable. The thickness of these polarizers is not particularly limited, but is generally about 5 to 80 μm.

  A polarizer obtained by dyeing a polyvinyl alcohol film with iodine and uniaxially stretching it can be produced, for example, by dyeing polyvinyl alcohol in an aqueous solution of iodine and stretching it 3 to 7 times the original length. If necessary, it can be immersed in an aqueous solution such as potassium iodide which may contain boric acid, zinc sulfate, zinc chloride or the like. Further, if necessary, the polyvinyl alcohol film may be immersed in water and washed before dyeing. In addition to washing the polyvinyl alcohol film surface with dirt and anti-blocking agents by washing the polyvinyl alcohol film with water, it also has the effect of preventing unevenness such as uneven coloring by swelling the polyvinyl alcohol film. is there. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. The film can be stretched even in an aqueous solution such as boric acid or potassium iodide or in a water bath.

  In the present invention, a thin polarizer having a thickness of 10 μm or less can also be used. From the viewpoint of thinning, the thickness is preferably 1 to 7 μm. Such a thin polarizer is preferable in that the thickness unevenness is small, the visibility is excellent, the dimensional change is small, the durability is excellent, and the thickness of the polarizing film can be reduced.

  As the thin polarizer, typically, Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or a patent. The thin polarizing film described in the specification of 4751481 and Unexamined-Japanese-Patent No. 2012-0753563 can be mentioned. These thin polarizing films can be obtained by a production method including a step of stretching and dyeing a polyvinyl alcohol-based resin (hereinafter also referred to as PVA-based resin) layer and a stretching resin substrate in the state of a laminate. With this manufacturing method, even if the PVA-based resin layer is thin, it can be stretched without problems such as breakage due to stretching by being supported by the stretching resin substrate.

  As the thin polarizing film, International Publication No. 2010/100917 pamphlet in that it can be stretched at a high magnification and the polarization performance can be improved among the production methods including the step of stretching in the state of a laminate and the step of dyeing. , WO 2010/100917 pamphlet, or Patent 4751481 specification or JP 2012-073563 A, which is obtained by a production method including a step of stretching in a boric acid aqueous solution is preferable. What is obtained by the manufacturing method including the process of extending | stretching in the air auxiliary before extending | stretching in the boric-acid aqueous solution which is described in the specification of 4751481 or Unexamined-Japanese-Patent No. 2012-073563 is preferable.

As a material for forming the transparent protective film provided on one side or both sides of the polarizer, 40 ° C., 90% R.D. H. What is necessary is just to select so that the water vapor transmission rate may be 0.5-30 g / (m < ² > * day), and it does not specifically limit. Examples of the material for forming the transparent protective film include polyester polymers such as polyethylene terephthalate and polyethylene naphthalate, cellulose polymers such as diacetyl cellulose and triacetyl cellulose, acrylic polymers such as polymethyl methacrylate, polystyrene, acrylonitrile and styrene. Examples thereof include styrene polymers such as copolymers (AS resin), polycarbonate polymers, and the like. In addition, polyethylene, polypropylene, polyolefins having a cyclo or norbornene structure, polyolefin polymers such as ethylene / propylene copolymers, vinyl chloride polymers, amide polymers such as nylon and aromatic polyamide, imide polymers, sulfone polymers , Polyether sulfone polymer, polyether ether ketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, vinyl butyral polymer, arylate polymer, polyoxymethylene polymer, epoxy polymer, or Examples of the polymer that forms the transparent protective film include blends of the polymer. The transparent protective film can also be formed as a cured layer of thermosetting or ultraviolet curable resin such as acrylic, urethane, acrylurethane, epoxy, and silicone.

The transparent protective film is 40 ° C., 90% R.D. H. There is no particular limitation on the water vapor transmission rate, but it is preferably 0.5 to 2500 g / (m ² · day). Among the transparent protective films, the protective film on the liquid crystal cell side is 40 ° C., 90% R.D. H. The moisture permeability in is preferably 0.5 to 300 g / (m ² · day). 40 ° C., 90% R.D. of the transparent protective film on the liquid crystal cell side. H. By making the water vapor transmission rate in the above range, the effect of suppressing white turbidity tends to be obtained, which is preferable.

  Although the thickness of a protective film can be determined suitably, generally it is about 1-500 micrometers from points, such as workability | operativity, such as intensity | strength and handleability, and thin film property.

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

  Moreover, in this invention, the water vapor transmission rate of a 1st polarizing film should just become the said range, for example, a phase difference film etc. can be formed on a polarizer instead of a transparent protective film. Further, another transparent protective film or a retardation film can be provided on the transparent protective film.

  The surface of the transparent protective film that does not adhere to the opposite side (viewing side) of the liquid crystal cell may be subjected to a hard coat layer, antireflection treatment, anti-sticking treatment, or treatment for diffusion or anti-glare. good.

(4) Second Polarizing Film The liquid crystal cell constituting the liquid crystal panel of the present invention has a surface opposite to the surface having a water contact angle of 40 to 110 °, 40 ° C., 90% R.D. H. The second polarizing film has a moisture permeability of 8 g / (m ² · day) or more.

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

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. Moreover, the difference between the moisture permeability of the second polarizing film and the moisture permeability of the first polarizing film is not particularly limited, but is preferably greater than, for example, 10 g / (m ² · day). The moisture permeability of the second polarizing film and the first polarizing film is preferably in the above relationship, from the viewpoint of suppressing white turbidity of the entire liquid crystal panel.

As a polarizer and a protective film which comprise the said 2nd polarizing film, the thing similar to the said 1st polarizing film can be mentioned. However, the transparent protective film used for the second polarizing film is 40 ° C. and 90% R.D. H. The moisture permeability is not particularly limited, but is preferably 5 to 3000 g / (m ² · day). Moreover, among the transparent protective films which comprise a 2nd polarizing film, 40 degreeC and 90% R. H. The moisture permeability in is preferably 10 to 2000 g / (m ² · day). 40 ° C., 90% R.D. of the transparent protective film on the liquid crystal cell side. H. By making the water vapor transmission rate in the above range, the effect of suppressing white turbidity tends to be obtained, which is preferable.

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

  In addition, the second polarizing film can be attached to the liquid crystal cell via the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer can be the same as that used in the first polarizing film. 60 ° C., 90% R.D. of the pressure-sensitive adhesive layer for attaching the second polarizing film to the liquid crystal cell. H. The saturated moisture content in is preferably 0.5 to 6% by weight from the viewpoint of suppressing clouding.

(5) Configuration of Liquid Crystal Panel The configuration of the liquid crystal panel of the present invention is a liquid crystal cell having a high contact angle surface, an adhesive layer having a specific saturated moisture content, and a specific moisture permeability on the high contact angle surface. What is necessary is just to have the 1st polarizing film which has and to have the 2nd polarizing film which has a specific moisture permeability in the other surface of a liquid crystal cell, and is not specifically limited about another structure. Although the specific structure of the liquid crystal panel of this invention is demonstrated based on FIGS. 1-3, this invention is not limited to this.

The mode of the liquid crystal panel 12 of the present invention shown in FIG. 1 is as follows.
The liquid crystal cell 10 includes a liquid crystal layer 8, a first transparent substrate 7 (viewing side) disposed on one side of the liquid crystal layer 8, and a second transparent substrate disposed on the other side of the liquid crystal layer. 9 (light source side), and the transparent conductive layer 6 is formed on the first transparent substrate 7. A first polarizing film 4a is laminated on the high contact angle surface A of the liquid crystal cell 10 via an adhesive layer 5a. The 1st polarizing film 4a has the polarizer 2a between the visual recognition side transparent protective film 1a and the liquid crystal cell side transparent protective film 3a.

  Further, the liquid crystal panel 12 of the present invention shown in FIG. 2 has a retardation layer 11 formed instead of the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG. 1, and the liquid crystal panel of the present invention shown in FIG. The panel 12 is obtained by forming a retardation layer 11 on the liquid crystal cell side transparent protective film 3a of the liquid crystal panel of FIG. 1 via an adhesive layer 5c.

  Moreover, the liquid crystal panel of this invention can contain suitably what formed the transparent film or the brightness improvement film etc. via the adhesive layer on the visual recognition side transparent protective film 1a other than the above.

  The lower the moisture permeability of the polarizing film, the more likely it is that white turbidity and durability (foaming) tend to deteriorate, and the lower the water contact angle of the surface of the liquid crystal cell to which the adhesive layer is attached, Since water easily enters from between the pressure-sensitive adhesive layers, the cloudiness and durability tend to deteriorate. Furthermore, the pressure-sensitive adhesive layer has a trade-off relationship between white turbidity and durability (foaming). When the saturated moisture content of the pressure-sensitive adhesive layer is high, the white turbidity is good, but the durability (foaming) deteriorates. Conversely, when the saturated moisture content of the pressure-sensitive adhesive layer is low, white turbidity deteriorates and durability (foaming) becomes good. That is, in the present invention, the white turbidity of the entire liquid crystal panel can be suppressed by setting the moisture permeability of the polarizing film and the moisture content of the pressure-sensitive adhesive layer to an appropriate range in relation to the water contact angle of the liquid crystal cell surface. Is.

2. Image Display Device The image display device of the present invention includes the liquid crystal panel of the present invention. Hereinafter, a liquid crystal display device will be described as an example, but the present invention can be applied to any display device that requires a liquid crystal panel.

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

  The image display device of the present invention may be any as long as it includes the liquid crystal panel of the present invention, and other configurations are the same as those of the conventional image display device.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail using an Example, this invention is not limited to a following example, unless the summary is exceeded. In each example, parts and% are based on weight, and all room temperature standing conditions not specifically defined below are 23 ° C. and 65% R.D. H. It is.

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

<Measurement of weight average molecular weight (Mw) of acrylic polymer>
The weight average molecular weight of the prepared acrylic polymer was measured by GPC (gel permeation chromatography).
Device: HLC-8220GPC, manufactured by Tosoh Corporation
column:
Sample column: manufactured by Tosoh Corporation, TSK guard column Super HZ-H (1) + TSK gel Super HZM-H (2)
Reference column; manufactured by Tosoh Corporation, TSKgel Super H-RC (1)
Flow rate: 0.6mL / min
Injection volume: 10 μL
Column temperature: 40 ° C
Eluent: THF
Injection sample concentration: 0.2% by weight
Detector: differential refractometer 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 stretched up to 3 times while being dyed in an iodine solution of 0.3% concentration at 30 ° C. between rolls having different speed ratios. Thereafter, the total draw ratio was stretched to 6 times while being immersed in an aqueous solution containing 60% at 4% concentration of boric acid and 10% concentration of potassium iodide for 0.5 minutes. Next, after washing by immersing in an aqueous solution containing potassium iodide at 30 ° C. and 1.5% concentration for 10 seconds, it was dried at 50 ° C. for 4 minutes to obtain a polarizer having a thickness of 25 μm. A PVA-based resin aqueous solution is applied to both sides of the polarizer, an acrylic film having a thickness of 40 μm (moisture permeability: 50 g / (m ² · day)) on one side, and a TAC film having a thickness of 60 μm on the other side ( Moisture permeability: 1000 g / (m ² · day)) was bonded to produce 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 40 μm thick acrylic film used in Production Example 1 was replaced with a 30 μm thick acrylic film (moisture permeability: 68 g / (m ² · day)), a 60 μm thick TAC film, and a 40 μm thick film. A polarizing film (2) was obtained in the same manner as in Production Example 1 except that the film was changed to a TAC film (moisture permeability: 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, the acrylic film having a thickness of 20 μm (moisture permeability: 110 g / (m ² · day)), the TAC film having a thickness of 60 μm, and a thickness of 25 μm. It is changed to a TAC film (moisture permeability: 2000 g / (m ² · day)), and on the side of the acrylic film having a thickness of 20 μm, a COP having a thickness of 20 μm is further interposed via an adhesive having a thickness of 10 μm. A polarizing film (3) was obtained in the same manner as in Production Example 1 except that a base film (moisture permeability: 6.5 g / (m ² · day)) was bonded. The moisture permeability of the obtained polarizing film (3) was 6.1 g / (m ² · day).

Production Example 4 (Production of Polarizing Film (4))
In Production Example 3, the same as in Production Example 3 except that a 20 μm thick COP film (moisture permeability: 6.5 g / (m ² · day)) was not bonded via a 10 μm thick adhesive. Thus, a polarizing film (4) was obtained. The obtained polarizing film (4) had a moisture permeability of 35 g / (m ² · day).

Production Example 5 (Production of Polarizing Film (5))
A 25 μm thick PET film (moisture permeability: 21 g / (m ² · day)) is further passed through a 10 μm adhesive on the 25 μm thick TAC film side of the polarizing film (4) of Production Example 4. Were bonded together 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))
On the side of the TAC film having a thickness of 25 μm of the polarizing film (4) of Production Example 4, a PET film having a thickness of 20 μm (moisture permeability: 28 g / (m ² · day)) is further passed through a 10 μm adhesive. Were bonded together to obtain a polarizing film (6). The obtained polarizing film (6) had a moisture permeability of 9.7 g / (m ² · day).

Production Example 7 (Production of Polarizing Film (7))
The polarizing film (4) of Production Example 4 is coated with a 30 μm thick COP film (moisture permeability: 3.4 g / (m ² · day) through a 10 μm thick adhesive on the 20 μm thick acrylic film side. )) Was bonded to obtain a polarizing film (7). The water vapor permeability of the obtained polarizing film (7) was 2.9 g / (m ² · day).

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

Example 1
(Preparation of acrylic pressure-sensitive adhesive composition)
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer and a stirrer, 99 parts of butyl acrylate, 1 part of 4-hydroxybutyl acrylate, and 100 parts of AIBN as a initiator (solid content) 0.1 part with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Then, ethyl acetate was added to the reaction solution to prepare a solution containing an acrylic polymer having a weight average molecular weight of 1.6 million. Obtained (solid content concentration 30% by weight). As a cross-linking agent, 0.1 part of trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemicals) per 100 parts of the solid content of the acrylic polymer solution, and 0.1 part of dibenzoyl peroxide. 3 parts, 0.075 part of γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent is blended, and an acrylic pressure-sensitive adhesive composition (1 )

(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) is uniformly coated with a fountain coater on the surface of a polyethylene terephthalate film (base material) that has been treated with a silicone-based release agent. It was dried for a minute, and an adhesive layer having a thickness of 20 μm was formed on the surface of the substrate. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

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

Example 2
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) which is a transparent conductive layer, the polarizing film with the adhesive layer (2) is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 3
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 4
(Preparation of acrylic pressure-sensitive adhesive composition)
In a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, and a stirring device, 99.5 parts of butyl acrylate, 0.5 part of 4-hydroxybutyl acrylate, and AIBN as a monomer (solid content) After adding 0.1 part with ethyl acetate to 100 parts and reacting at 60 ° C. under a nitrogen gas stream for 7 hours, ethyl acetate was added to the reaction solution to obtain an acrylic polymer having a weight average molecular weight of 1.6 million. A solution containing it was obtained (solid content concentration 30% by weight). As a cross-linking agent, 0.1 part of trimethylolpropane xylylene diisocyanate (trade name: Takenate D110N, manufactured by Mitsui Chemicals) per 100 parts of the solid content of the acrylic polymer solution, and 0.1 part of dibenzoyl peroxide. 3 parts, 0.075 part of γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent is blended to prepare an acrylic pressure-sensitive adhesive composition (2 )

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

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 5
(Preparation of acrylic pressure-sensitive adhesive composition)
In a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer and a stirrer, 99.9 parts of 2-ethylhexyl acrylate, 0.1 part of 6-hydroxyhexyl acrylate, and AIBN as a monomer (solid Min) 0.1 part per 100 parts was added with ethyl acetate and reacted at 60 ° C. for 7 hours under a nitrogen gas stream. Ethyl acetate was then added to the reaction solution to give an acrylic polymer having a weight average molecular weight of 1.8 million. A solution containing the polymer was obtained (solid content concentration 30% by weight). As a cross-linking agent, 0.1 part of trimethylolpropane / tolylene diisocyanate adduct (trade name: Coronate L, manufactured by Nippon Polyurethane Industry Co., Ltd.) per 100 parts of the solid content of the acrylic polymer solution, dioctyltin 0.03 part of dilaurate-based crosslinking accelerator (trade name: ENVILIZER OL-1, manufactured by Tokyo Fine Chemical Co., Ltd.), and γ-glycidoxypropyltrimethoxysilane (trade name: KBM-403) as a silane coupling agent 0.01 parts of Shin-Etsu Chemical Co., Ltd.) was blended to obtain an acrylic pressure-sensitive adhesive composition (3).

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

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 6
(Preparation of monomer components used for UV polymerization)
61 parts by weight of 2-ethylhexyl acrylate, 14 parts by weight of N-vinyl-2-pyrrolidone, 2 parts of photopolymerization initiator (trade name: Irgacure 184, manufactured by BASF) and a photopolymerization initiator (trade name) : Irgacure 651, manufactured by BASF) 0.05 parts by weight was charged into a four-necked flask to prepare a monomer mixture. Next, the monomer mixture was partially photopolymerized by exposing it to ultraviolet rays under a nitrogen atmosphere to obtain a partially polymerized product (acrylic polymer syrup) having a polymerization rate of about 10% by weight.
The total amount (75.1 parts by weight) of the resulting acrylic polymer syrup was added to 3 parts by weight of 2-hydroxyethyl acrylate (2HEA), 22 parts by weight of 4-hydroxybutyl acrylate (HBA), dipentaerythritol pentaacrylate (trade name: After adding 0.12 parts by weight of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.), these were uniformly mixed to prepare monomer component (4).

(Preparation of adhesive layer by UV polymerization)
Next, the final thickness of the monomer component (4) prepared above on the release-treated surface of a 38 μm-thick polyester film (trade name: Diafoil MRF, manufactured by Mitsubishi Resin Co., Ltd.) whose one side is peel-treated with silicone. Was applied to form a coating layer. Next, a 38 μm thick polyester film (trade name: Diafoil MRE, manufactured by Mitsubishi Resin Co., Ltd.) having one surface peeled with silicone on the surface of the applied monomer component, the peel-treated surface of the film is on the coating layer side It coat | covered so that it might become. Thereby, the coating layer of the monomer component was shielded from oxygen. Using a chemical light lamp (manufactured by Toshiba Corporation) on the sheet having the coating layer thus obtained, ultraviolet rays having an illuminance of 5 mW / cm ² (measured with Topcon UVR-T1 having a maximum sensitivity of about 350 nm) are used. Irradiated for 360 seconds to cure the coating layer to form a pressure-sensitive adhesive layer, thereby preparing a pressure-sensitive adhesive sheet. The polyester film coated on both surfaces of the pressure-sensitive adhesive layer functions as a release liner (separator).

(Preparation of polarizing film with adhesive layer)
The separator of the pressure-sensitive adhesive layer was peeled only on one side, and the separator formed with the pressure-sensitive adhesive layer was transferred to the acrylic film surface of the polarizing film (3) obtained in Production Example 3 to obtain a polarizing film with a pressure-sensitive adhesive layer ( 3) was produced. The moisture content of the pressure-sensitive adhesive layer formed on the polarizing film (3) was 3.1% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer produced by the same method as in Example 1 was bonded to form a liquid crystal panel.

Example 7
(Preparation of emulsion-type acrylic pressure-sensitive adhesive composition)
To the container, 780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added and mixed to obtain a monomer mixture. Next, to 1000 parts of the monomer mixture prepared in the above ratio, 30 parts of Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.), which is a reactive surfactant, and 635 parts of ion-exchanged water are added. Using a special machine chemical industry), the mixture was stirred at 6000 (rpm) for 5 minutes to prepare a monomer emulsion.
Next, 200 parts of the monomer emulsion prepared above and 515.9 parts of ion-exchanged water were charged into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel, and a stirring blade, After sufficiently purging the reaction vessel with nitrogen, 0.6 part of ammonium persulfate was added, and polymerization was performed at 60 ° C. for 1 hour with stirring. Subsequently, the remaining monomer emulsion was dropped into the reaction vessel at 60 ° C. over 3 hours and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Next, after cooling the polymer emulsion to room temperature, an emulsion-type acrylic pressure-sensitive adhesive having a pH of 8 added thereto and adjusted to a solid content of 45.6% by adding ammonia water having a concentration of 10% is obtained. It was.

(Preparation of polarizing film with adhesive layer)
A die coater on the release film (trade name: Diafoil MRF-38, polyethylene terephthalate base material, manufactured by Mitsubishi Chemical Polyester Co., Ltd.) so that the emulsion-type acrylic pressure-sensitive adhesive has a thickness of 20 μm after drying. Then, it was dried at 120 ° C. for 5 minutes to form an adhesive layer. Subsequently, the separator which formed the said adhesive layer was transferred to the acrylic film surface of the polarizing film (3) obtained by manufacture example 3, and the polarizing film (3) with an adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 5.0% by weight.

(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Subsequently, the separator which formed the adhesive layer which consists of an acrylic adhesive composition (1) on the acrylic film surface of the polarizing film (4) obtained by manufacture example 4 was transferred, and a polarizing film with an adhesive layer Was made. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 8
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

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

Example 9
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) which is a transparent conductive layer, a polarizing film (7) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Example 10
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to the acrylic film surface of the polarizing film (6) obtained in Production Example 6 and the acrylic film surface of the polarizing film (4) obtained in Production Example 4. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

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

Example 11
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, two polarizing films (1) obtained in Production Example 1 were prepared, and a separator on which an adhesive layer was formed was transferred to each acrylic film surface of the polarizing film (1). An attached polarizing film was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
A polarizing film (1) with an adhesive layer is provided on the transparent conductive layer side of a liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm), which is a transparent conductive layer, and on the opposite side of the liquid crystal cell. The liquid crystal panel was formed by bonding.

Example 12
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

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

Examples 13 and 14
A liquid crystal cell having an amorphous ITO layer (contact angle with respect to water: 73 °, thickness: 20 nm) used in Example 1 (production of liquid crystal panel) was converted into a crystallized ITO layer (contact angle with respect to water: 58 °, thickness). A liquid crystal panel was produced in the same manner as in Example 1 except that the liquid crystal cell was changed to a liquid crystal cell having a thickness of 20 nm) and a liquid crystal cell having an acrylic resin layer (contact angle with water: 72 °, thickness: 5 μm).

Comparative Example 1
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (4) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (3) with an adhesive layer was bonded together to form a liquid crystal panel.

Comparative Example 2
(Preparation of acrylic pressure-sensitive adhesive composition)
A 2 L three-necked flask was fitted with a three-way cock and the inside was replaced with nitrogen. At room temperature, 868 g of toluene, 43.4 g of 1,2-dimethoxyethane, isobutylbis (2,6-di-t-butyl-4-methylphenoxy) ) 60.0 g of a toluene solution containing 40.2 mmol of aluminum was added, and 3.68 g of a mixed solution of cyclohexane and n-hexane containing 6.37 mmol of sec-butyllithium was further added. Subsequently, 51.5 g of methyl methacrylate (MMA) was added thereto, and the mixture was stirred at room temperature for 60 minutes. Subsequently, the internal temperature of the polymerization solution was cooled to −30 ° C., and 240 g of n-butyl acrylate (nBA) was added dropwise over 2 hours. Next, 51.5 g of methyl methacrylate was added, and after stirring at room temperature overnight, 3.50 g of methanol was added to stop the polymerization reaction. The obtained reaction solution was poured into methanol, and the precipitate was collected by filtration. By drying this, 340 g of block copolymer 1 was obtained.

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

(Preparation of polarizing film with adhesive layer)
The block copolymer 1 is dissolved in toluene to prepare a pressure-sensitive adhesive solution having a solid content of 30%, and the pressure-sensitive adhesive layer after drying is formed on a separator made of a polyester film (thickness 38 μm) subjected to a release treatment. The adhesive was applied by reverse coating so that the thickness was 25 μm, and the solvent was volatilized by heating at 90 ° C. for 3 minutes to obtain an adhesive layer. Subsequently, the separator which formed the said adhesive layer was transferred to the acrylic film surface of the polarizing film (3) obtained by manufacture example 3, and the polarizing film (3) with an adhesive layer was produced. The moisture content of the obtained pressure-sensitive adhesive layer was 0.1% by weight.

(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Subsequently, the separator which formed the adhesive layer which consists of an acrylic adhesive composition (1) on the acrylic film surface of the polarizing film (4) obtained by manufacture example 4 was transferred, and a polarizing film with an adhesive layer Was made. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Comparative Example 3
(Preparation of emulsion-type acrylic pressure-sensitive adhesive composition)
To the container, 780 parts of butyl acrylate, 200 parts of methyl methacrylate, and 20 parts of acrylic acid were added and mixed to obtain a monomer mixture. Next, to 1000 parts of the monomer mixture prepared in the above ratio, 60 parts of Aqualon HS-10 (Daiichi Kogyo Seiyaku Co., Ltd.), which is a reactive surfactant, and 635 parts of ion-exchanged water are added. Using a special machine chemical industry), the mixture was stirred at 6000 (rpm) for 5 minutes to prepare a monomer emulsion.
Next, 200 parts of the monomer emulsion prepared above and 515.9 parts of ion-exchanged water were charged into a reaction vessel equipped with a cooling pipe, a nitrogen introduction pipe, a thermometer, a dropping funnel, and a stirring blade, After sufficiently purging the reaction vessel with nitrogen, 0.6 part of ammonium persulfate was added, and polymerization was performed at 60 ° C. for 1 hour with stirring. Subsequently, the remaining monomer emulsion was dropped into the reaction vessel at 60 ° C. over 3 hours and then polymerized for 3 hours to obtain a polymer emulsion having a solid content concentration of 46.2%. Next, after cooling the polymer emulsion to room temperature, an aqueous acrylic pressure-sensitive adhesive (4) was added to which ammonia water having a concentration of 10% was added to adjust the pH to 8 and the solid content was adjusted to 45.6%. )

(Preparation of polarizing film with adhesive layer)
A release film (trade name: Diafoil) was prepared so that the acrylic adhesive composition (1) prepared in Example 1 and the emulsion acrylic adhesive (4) had a thickness of 20 μm after drying. After coating with a die coater on MRF-38, polyethylene terephthalate base material, manufactured by Mitsubishi Chemical Polyester Co., Ltd., it was dried at 120 ° C. for 5 minutes to form an adhesive layer. Subsequently, the separator which formed the adhesive layer which consists of said emulsion type acrylic adhesive (4) was transferred to the acrylic film surface of the polarizing film (3) obtained by manufacture example 3, and polarized light with an adhesive layer A film was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 6.2% by weight. Moreover, the separator which formed the adhesive layer which consists of an acrylic adhesive composition (1) on the acrylic film surface of the polarizing film (4) obtained by manufacture example 4 was transferred, and a polarizing film with an adhesive layer Was made. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

(Manufacture of liquid crystal panels)
On the transparent conductive layer side of the liquid crystal cell having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) as a transparent conductive layer, a polarizing film (3) with an adhesive layer is placed on the opposite side of the liquid crystal cell. The polarizing film (4) with an adhesive layer was bonded together to form a liquid crystal panel.

Comparative Example 4
(Preparation of polarizing film with adhesive layer)
The acrylic pressure-sensitive adhesive composition (1) produced in Example 1 was uniformly applied to the surface of a polyethylene terephthalate film (base material) treated with a silicone-based release agent with a fountain coater, and air circulation at 155 ° C. It dried for 2 minutes in the type | mold constant temperature oven, and formed the 20-micrometer-thick adhesive layer on the surface of a base material. Further, another sheet of the same pressure-sensitive adhesive layer was produced. Next, the separator on which the pressure-sensitive adhesive layer was formed was transferred to 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. A polarizing film with a pressure-sensitive adhesive layer was prepared. The moisture content of the obtained pressure-sensitive adhesive layer was 0.7% by weight.

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

  The following evaluation was performed about the adhesive layer obtained by the Example and the comparative example, and the liquid crystal panel.

<Measurement method of saturated moisture content of pressure-sensitive adhesive layer>
About 50 mg of a sample was collected from the pressure-sensitive adhesive layer of the polarizing film with the pressure-sensitive adhesive layer produced in Examples and Comparative Examples. The sample was measured for the weight (W1) in a state where moisture was completely removed at 100 ° C. for 1 hour using a moisture adsorption / desorption measuring device (IGA-Sorp, manufactured by Hiden), and then 23 ° C, 0% R.V. H. For 2 hours at 23 ° C. and 55% R.I. H. For 5 hours at 60 ° C. and 90% R.V. H. For 5 hours at 23 ° C. and 55% R.P. H. For 5 hours, and the change in weight was observed. When there was no change in the weight of the sample (saturated state), its weight (W2) was measured. The saturated moisture content was measured from the following formula.

<White turbidity test>
(Preparation of test samples)
An adherend 1 having an amorphous ITO layer (contact angle with water: 73 °, thickness: 20 nm) formed on one surface of an alkali-free glass substrate (contact angle with water: 38 °) by a sputtering method, alkali-free glass An adherend 2 having a crystallized ITO layer (water contact angle: 58 °, thickness: 20 nm) formed on one surface of a substrate (water contact angle: 38 °) was produced. The Sn ratio of the crystalline ITO thin film was 10% by weight. The Sn ratio of the amorphous ITO thin film was 3% by weight. Further, an 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 surface of the adherend 1 according to the following procedure was prepared. In Examples 1-12 and Comparative Examples 1-4, a polarizing film (polarizing film in Table 1) using the adherend 1 and laminated on the transparent conductive layer side (viewing side) of the liquid crystal cell in the liquid crystal panel of each Example. 1) is adhered to the amorphous ITO layer side of the adherend 1, and the polarizing film (polarizing film 2 in Table 1) laminated on the opposite side (light source side) of the liquid crystal cell is attached to the non-alkali glass side of the adherend 1 A sample was prepared for the cloudiness test. Moreover, in Example 13, the polarizing film (1) with an adhesive layer used in Example 13 was used for the crystallization ITO layer of the adherend 2 and the adhesive layer used in Example 13 was used on the alkali-free glass side. A polarizing film (4) was affixed, and in Example 14, the polarizing film with adhesive layer (1) used in Example 14 was used on the acrylic resin layer side of the adherend 3 and Example 14 was used on the alkali-free glass side. The polarizing film with a pressure-sensitive adhesive layer (4) used in 1 was affixed and used as a sample for the cloudiness test. The adherends 1 to 3 reproduce the surface states of the liquid crystal cells used in Examples and Comparative Examples.

(Method for forming acrylic resin layer)
5 parts of photopolymerization initiator (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) is blended with 100 parts of polyfunctional urethane acrylate (solid content: 100%), and diluted solvent (methyl isobutyl ketone (MIBK)). ) To prepare a coating solution having a solid content of 45%. After applying to the surface of the amorphous ITO layer of the adherend 1 so that the film thickness after drying is 5 μm, it is dried at 80 ° C. and cured by UV irradiation (integrated light amount: 300 mJ), and the acrylic resin layer is formed. Thus, the adherend 3 was formed.

(Measurement of cloudiness)
The test sample was autoclaved at 50 ° C. and 5 atm for 15 minutes, and then subjected to 60 ° C. and 90% R.D. H. Was placed in a constant temperature and humidity machine. The sample after 120 hours was observed and evaluated according to the following evaluation criteria.
1: Confirmed with a microscope, no water drops 2: Confirmed with a microscope, a small amount of water droplets could be confirmed, but there was no white turbidity by visual inspection 3: Partially white turbidity by visual inspection 4: Visual opacity on the entire surface 5: Full opacity

<Durability test>
The test sample prepared in <white turbidity test> was subjected to an autoclave treatment at 50 ° C. and 5 atm for 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 according to the following evaluation criteria.
1: There is no foaming 2: There is foaming that cannot be visually confirmed in a small part 3: There is foaming that can be visually confirmed in a very small part 4: There is foaming that can be visually confirmed in part 5: There is foaming that can be visually confirmed over the entire surface

1a Viewing side transparent protective film 1b Liquid crystal cell side transparent protective film 2a Polarizer 2b Polarizer 3a Liquid crystal cell side transparent protective film 3b Viewing side transparent protective film 4a First polarizing film 4b Second polarizing film 5a Adhesive layer 1
5b Adhesive layer 2
6 transparent conductive layer 7 first transparent substrate 8 liquid crystal layer 9 second transparent substrate 10 liquid crystal cell 11 retardation layer 12 liquid crystal panel A high contact angle surface

Claims (7)

One surface of the liquid crystal cell is a high contact angle surface having a contact angle with water of 40 to 110 °,
On the high contact angle surface of the liquid crystal cell,
60 ° C., 90% R.D. H. A pressure-sensitive adhesive layer having a saturated moisture content of 0.3 to 6% by weight, and
40 ° C., 90% R.D. H. Having a first polarizing film having a moisture permeability of 0.5 to 30 g / (m ² · day),
On the other side of the liquid crystal cell,
40 ° C., 90% R.D. H. A liquid crystal panel comprising a second polarizing film having a moisture permeability of 8 g / (m ² · day) or more. The liquid crystal panel according to claim 1, wherein the moisture permeability of the second polarizing film is larger than the moisture permeability of the first polarizing film. 60 ° C., 90% R.D. of the pressure-sensitive adhesive layer. H. 3. The liquid crystal panel according to claim 1, wherein a saturated moisture content in is from 0.5 to 6% by weight. The liquid crystal panel according to claim 1, wherein a high contact angle surface of the liquid crystal cell is formed of a transparent conductive layer. The other surface of the high contact angle surface of the liquid crystal cell is a low contact angle surface having a contact angle with water of 3 ° or more and less than 40 °, according to any one of claims 1 to 4. LCD panel. The second polarizing film has a temperature of 60 ° C. and 90% R.D. H. The liquid crystal panel according to claim 1, wherein the liquid crystal panel is laminated on a liquid crystal cell via an adhesive layer having a saturated moisture content of 0.5 to 6% by weight. An image display device comprising the liquid crystal panel according to claim 1.

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