KR20190118547A - Polarizing film with optical function layer and liquid crystal display device - Google Patents

Abstract

This invention is a polarizing film with an optical function layer which has the optical function layer (A) containing a pigment | dye, and polyvinyl alcohol-type polarizer (P), The said optical function layer (A) and the said polyvinyl alcohol-type polarizer (P) The distance x is characterized by being 45 µm or less. The polarizing film with an optical function layer of this invention is favorable with time stability, and has an optical function layer containing the pigment | dye which can maintain the wide gamut by a pigment | dye.

Description

Polarizing film with optical function layer and liquid crystal display device

The present invention relates to a polarizing film with an optical functional layer having an optical functional layer having a dye and a polarizing film having a polyvinyl alcohol polarizer. The said polarizing film with an optical function layer can form image display apparatuses, such as a liquid crystal display device (LCD) and an organic electroluminescence display, as this alone or as an optical film which laminated | stacked this.

It is indispensable for an image display apparatus etc. to arrange | position a polarizing element on both surfaces of a liquid crystal cell from the image formation system, and generally, a polarizing film is affixed. When sticking the said polarizing film to a liquid crystal cell, an adhesive is used normally. Moreover, in order for adhesion | attachment of a polarizing film and a liquid crystal cell, each material is closely adhered using an adhesive in order to reduce the loss of light. In this case, since the adhesive has a merit such as not requiring a drying step for fixing the polarizing film, a polarizing film with a pressure sensitive adhesive layer formed as an adhesive layer on one side of the polarizing film in advance is generally used.

Moreover, it is proposed to add an arbitrary color to a polarizing film by adding dye or a pigment to the said adhesive layer, and to obtain a high contrast liquid crystal display (patent document 1). Recently, brightness and clarity (i.e., wide color gamut) are required for an image display device, and an organic EL display device (OLED) has attracted attention, but wide color gamut is also required for a liquid crystal display device. For example, as a method of wide-color gamuting a liquid crystal display device, laminating a polarizing film on one side or both sides of the liquid crystal cell through an adhesive layer containing a dye having an absorption maximum wavelength in a range of a specific wavelength (560-610 nm). It is proposed (patent documents 2 and 3).

Japanese Utility Model Registration 3030512 Japanese Patent Laid-Open No. 2011-039093 Japanese Patent Publication No. 2014-092611

As mentioned above, a pigment | dye may be contained in the film layer applied to an optical member in addition to what may be contained in an adhesive layer. Thus, the optical function layer containing a pigment | dye can be formed by containing a pigment | dye in resin layers like a film layer or an adhesive layer. However, since the pigment | dye is contained in the said optical function layer, the pigment | dye in the said optical function layer deteriorates with time from a viewpoint of the moisture permeability of the resin layer used as the base of the said optical function layer, and the said optical function layer gradually fades. In particular, when the optical functional layer is a pressure-sensitive adhesive layer containing a dye, from the viewpoint of moisture permeability, the durability of the pressure-sensitive adhesive layer is not sufficient, and even the pressure-sensitive adhesive layer initially colored by the dye gradually fades. Thus, when the pigment | dye in an optical function layer (especially an adhesive layer) deteriorates with time, it was difficult to maintain the wide color gamut by a pigment | dye.

It is an object of the present invention to provide a polarizing film with an optical functional layer having good optical stability and having an optical functional layer containing a dye capable of maintaining photochromic gamut by a dye.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, the present inventors found the following polarizing film with an adhesive layer, and came to complete this invention.

That is, this invention is a polarizing film with an optical function layer which has an optical function layer containing a pigment in at least one side of the polarizing film which has a polyvinyl alcohol-type polarizer, The optical function layer containing the said polyvinyl alcohol-type polarizer and the said pigment | dye. The distance of 45 micrometers or less relates to the polarizing film with an optical function layer. It is preferable that distance with the said optical function layer with the said polyvinyl alcohol-type polarizer is 25 micrometers or less.

In the said polarizing film with an optical function layer, the thing in which the said adhesive layer with the said polyvinyl alcohol-type polarizer is laminated directly can be used.

In the said polarizing film with an optical function layer, it can have at least 1 layer which does not have a pigment | dye of thickness 45 micrometers or less between the said adhesive layer with the said polyvinyl alcohol-type polarizer.

In the said polarizing film with an optical function layer, it is preferable that the oxygen transmittance of the said polyvinyl alcohol-type polarizer is 1 [cm <3> / (m <2> * 24h * atm]] or less.

The said polarizing film with an optical function layer WHEREIN: The said pigment can use what has a maximum absorption wavelength in at least any one of wavelength range 470-510 nm and wavelength range 570-610 nm.

In the said polarizing film with an optical function layer, the said dye can use tetraaza porphyrin type pigment | dye.

In the said polarizing film with an optical function layer, it is preferable to contain the said pigment | dye 0.01-5 weight part with respect to 100 weight part of base polymers which form the resin layer of the said optical function layer.

In the said polarizing film with an optical function layer, it is preferable that the adhesive layer containing the said pigment is 25 micrometers or less in thickness.

Moreover, this invention relates to the image display apparatus which has the said polarizing film with an optical function layer.

(Effects of the Invention)

In the polarizing film with an optical function layer of this invention, it has an optical function layer containing a pigment | dye. The optical functional layer can adjust the color of the entire liquid crystal display by absorbing light of a portion of wavelengths by a dye, and can improve sharpness by wide color gamut. In particular, a dye having a maximum absorption wavelength in at least one of the wavelength range 470 to 510 nm and the wavelength range 570 to 610 nm is used for color expression in a wavelength range other than RGB (wavelength range 470 to 510 nm and / or wavelength range 570 to 610 nm). The unnecessary light emission can be absorbed to suppress the unnecessary light emission, which is effective for wide color gamut.

It was found that the discoloration of the dye in the optical functional layer containing the dye is caused by oxygen present in the air or in the resin penetrating into the optical functional layer, activated by heat, and attacking the dye. It is thought that oxygen penetrates from the upper, lower, left, and right sides of the pressure-sensitive adhesive layer.

In the polarizing film with an optical function layer of this invention, the optical function layer containing the said pigment is applied to the polarizing film using a polyvinyl alcohol-type polarizer. The polyvinyl alcohol polarizer has a low oxygen transmittance and can prevent the ingress of oxygen into the optical functional layer from the upper or lower surface of the optical functional layer containing the dye. In addition, the polarizing film with an optical function layer of this invention uses a separator etc. with low oxygen transmittance on the other surface of the said optical function layer, and the adherend with low oxygen transmittance | permeability, such as glass, at the time of specific use. The present invention can provide an optical functional layer which can prevent the intrusion of oxygen into the optical functional layer, suppress the discoloration (decomposition) of the dye, and stably maintain the color gamut over time.

Moreover, in the polarizing film with an optical function layer of this invention, the optical function layer and polyvinyl alcohol-type polarizer containing the said pigment are laminated so that these distance may be 45 micrometers or less. By the said distance being 45 micrometers or less, it can prevent also about oxygen invading from the edge part of the polarizing film with an optical function layer, and also discolors (decomposes) of a pigment | dye at the edge part of the polarizing film with an optical function layer, and is stable over time. It is possible to maintain wide gamut.

1: is sectional drawing which shows typically the outline of the polarizing film with an optical function layer of this invention.
It is sectional drawing which shows typically one Embodiment of the polarizing film with an optical function layer of this invention.
It is sectional drawing which shows typically one Embodiment of the polarizing film with an optical function layer of this invention.
It is sectional drawing which shows typically one Embodiment of the polarizing film with an optical function layer of this invention.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of the polarizing film with an optical function layer of this invention is described in detail using drawing. However, this invention is not limited to embodiment of drawing.

As shown in FIG. 1, the polarizing film with an optical function layer of this invention has an optical function layer (A) containing a polyvinyl alcohol-type polarizer P and a pigment | dye. The polyvinyl alcohol polarizer P and the optical function layer A are laminated so that their distance x is 45 μm or less. The shorter the distance x, the more the intrusion of oxygen from the end can be prevented. 25 micrometers or less are preferable, as for distance x, 10 micrometers or less are more preferable, Furthermore, 5 micrometers or less and 1 micrometer or less are more preferable.

FIG. 2 is a case where the polyvinyl alcohol polarizer P and the optical function layer A are directly stacked (x = 0 μm). In addition, in FIG. 2, the case of the polarizing film (one protective polarizing film) which has the transparent protective film F in the one side (side which does not form the optical function layer A) of polyvinyl alcohol-type polarizer P is illustrated. have. In addition, in FIG. 2, the case where the base material S is formed in the optical function layer A is illustrated, and as a base material S used for the period until the specific use of the polarizing film with an optical function layer, separator, a vapor deposition film, etc. Can be mentioned. In the specific use, glass, a vapor-deposited transparent substrate, etc. are mentioned.

In addition, in FIG. 3, in the aspect of FIG. 2, the case where the layer B with a thickness of 45 micrometers or less is provided between the said polyvinyl alcohol-type polarizer P and the said optical function layer A is illustrated. In FIG. 3, the case of the first layer B is illustrated, but the layer B may be a combination of a plurality of layers. As a layer (B), an adhesive layer, a film layer, etc. are mentioned, for example. In addition, the thickness of layer (B) can be designed according to the characteristic of each layer in the range of 45 micrometers or less.

In addition, in FIG. 4, in the aspect of FIG. 2, the said polyvinyl alcohol-type polarizer P and the said optical function layer A are laminated | stacked directly (the said x = 0 micrometer), and the said optical function layer A The case which has layer (C) in) is illustrated. Although the case of one layer is illustrated as said layer (C), layer (C) may combine multiple layers. As layer (C), an adhesive layer, a surface treatment layer (hard coat layer, anti-glare layer, antireflection layer, etc.) etc. are mentioned, for example. In addition, the thickness of layer (C) can be designed according to the characteristic of each layer in the range of 45 micrometers or less. Layer (C) may be applied in combination with layer (B).

The polarizing film with an optical function layer of this invention has the optical function layer containing the polarizing film which has a polyvinyl alcohol-type polarizer, and a pigment | dye. Hereinafter, each member is demonstrated.

<Optical functional layer>

The optical function layer of this invention will not be specifically limited if it is a resin layer containing a pigment | dye. A film layer, an adhesive layer, etc. are mentioned as said resin layer. The optical functional layer may be formed of a composition containing a base polymer and a dye.

<Color>

Various pigment | dyes can be used for the pigment | dye which the optical function layer of this invention contains. As a pigment | dye, various compounds, such as tetraaza porphyrin type, porphyrin type, cyanine type, azo type, pyrromethene type, squarylium type, xanthene type, oxonol type, squaraine type, are mentioned, for example. The dye is preferably a tetraaza porphyrin-based dye, a porphyrin-based dye, a cyanine-based dye, a squarylium-based dye, or a squaraine-based dye from the viewpoint of photochromic region, and particularly a tetraazaporphyrin-based dye. The said dye is specifically disclosed by Unexamined-Japanese-Patent No. 2011-116818. Only 1 type may be used for the said pigment and it may use 2 or more types together.

It is preferable that the said pigment has maximum absorption wavelength in at least one of wavelength range 470-510 nm and wavelength range 570-610 nm. The pigment | dye which has the maximum absorption wavelength in the said wavelength range can absorb the light emission which is unnecessary for color expression, and can suppress the light emission, and is effective for wide color gamut. As a pigment | dye which has the maximum absorption wavelength in the said wavelength range, a tetraaza porphyrin type pigment | dye can be used suitably. For example, as a pigment | dye which shows the maximum absorption wavelength in a wavelength range of 570-610 nm, it is Yamamoto Chemicals Inc. Tetraazaporphyrin compound (brand name: PD-320, PD311) of the production, YAMADA CHEMICAL CO., LTD. The produced tetraaza porphyrin type compound (brand name: FDG-007) etc. are mentioned. In addition, the measurement of the maximum absorption wavelength of a pigment | dye is performed with the spectrophotometer (V-570 by JASCO Corporation).

Although content of the pigment | dye in the optical function layer of this invention is adjusted by the absorption wavelength range of a pigment | dye, an extinction coefficient, and the kind of base polymer, it is preferable that it is usually 0.01-5 weight part with respect to 100 weight part of base polymers, and 0.05- 3 weight part is more preferable, and 0.1-1 weight part is more preferable. In particular, when using a tetraaza porphyrin type pigment | dye, the said range is preferable.

<Adhesive layer>

The optical function layer of this invention can be mentioned the adhesive layer containing a pigment | dye, The said adhesive layer can be formed from the adhesive composition containing an adhesive base polymer and a pigment | dye. Although there is no restriction | limiting in particular about the kind of adhesive base polymer, For example, a rubber type polymer, a (meth) acrylic type polymer, a silicone type polymer, a urethane type polymer, a vinyl alkyl ether type polymer, a polyvinyl alcohol type polymer, a polyvinylpyrrolidone type polymer, Various polymers, such as a polyacrylamide polymer and a cellulose polymer, are mentioned.

The adhesive composition of this invention contains an adhesive base polymer as a main component. A main component refers to the component with the most content rate among the total solid contained in an adhesive composition, for example, is a component which occupies more than 50 weight% of the total solid contained in an adhesive composition, and refers to the component which occupies more than 70 weight%.

Among these adhesive base polymers, those having excellent optical transparency, exhibiting moderate wettability and cohesiveness and adhesive adhesive properties, and excellent in weather resistance, heat resistance, and the like are preferably used. As showing such a characteristic, a (meth) acrylic-type polymer is used preferably. Hereinafter, the acrylic adhesive which uses the (meth) acrylic-type polymer which contains the alkyl (meth) acrylate of the formation material of an adhesive layer as a monomer unit as a base polymer is demonstrated.

<(Meth) acrylic polymer>

The said (meth) acrylic-type polymer normally contains alkyl (meth) acrylate as a main component as a monomer unit. In addition, (meth) acrylate refers to acrylate and / or methacrylate, and has the same meaning as (meth) of this invention.

As an alkyl (meth) acrylate which comprises the main skeleton of the said (meth) acrylic-type polymer, the C1-C18 thing of a linear or branched alkyl group can be illustrated. These may be used alone or in combination. It is preferable that the average carbon number of these alkyl groups is 3-9.

Moreover, alkyl (meth) acrylate containing aromatic rings, such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate, can be used from the point of adhesion characteristics, durability, adjustment of phase difference, adjustment of refractive index, etc. .

In the (meth) acrylic polymer, at least one copolymerizable monomer having a polymerizable functional group having an unsaturated double bond such as a (meth) acryloyl group or a vinyl group can be introduced by copolymerization for the purpose of improving adhesion or heat resistance. . As a specific example of such a copolymerization monomer, For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, Contains hydroxyl groups, such as (meth) acrylic acid 8-hydroxyoctyl, (meth) acrylic acid 10-hydroxydecyl, (meth) acrylic acid 12-hydroxylauryl, and (4-hydroxymethylcyclohexyl) -methylacrylate Monomers; Carboxyl group-containing monomers such as (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid and crotonic acid; Acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; Caprolactone adducts of acrylic acid; Sulfonic acid group containing styrene sulfonic acid, allyl sulfonic acid, 2- (meth) acrylamide-2-methylpropanesulfonic acid, (meth) acrylamide propanesulfonic acid, sulfopropyl (meth) acrylate, (meth) acryloyloxy naphthalene sulfonic acid, etc. Monomers; Phosphoric acid group containing monomers, such as 2-hydroxyethyl acryloyl phosphate, etc. are mentioned.

Furthermore, (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-butyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methylol propane (meth) acrylamide, etc. (N-substituted) amide monomers; (Meth) acrylic-acid alkylaminoalkyl-type monomers, such as amino ethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; Alkoxy alkyl (meth) acrylate monomers, such as (meth) acrylic-acid methoxyethyl and (meth) acrylate ethoxyethyl; N- (meth) acryloyloxymethylene succinimide, N- (meth) acryloyl-6-oxyhexamethylene succinimide, N- (meth) acryloyl-8-oxyoctamethylene succinimide, N Succinimide-based monomers such as acryloyl morpholine; Maleimide monomers such as N-cyclohexyl maleimide, N-isopropyl maleimide, N-lauryl maleimide and N-phenyl maleimide; N-methyl itaconimide, N-ethyl itaconimide, N-butyl itaconimide, N-octyl itaconimide, N-2-ethylhexyl itaconimide, N-cyclohexyl itacon Itaconic imide type monomers, such as mead and N-lauryl itaconimide, etc. are mentioned as a monomer example for the purpose of modification.

Further, as modified monomers, vinyl acetate, vinyl propionate, N-vinylpyrrolidone, methylvinylpyrrolidone, vinylpyridine, vinylpiperidone, vinylpyrimidine, vinylpiperazine, vinylpyrazine, vinylpyrrole, vinylimidazole, Vinyl monomers such as vinyl oxazole, vinyl morpholine, N-vinyl carboxylic acid amides, styrene, α-methyl styrene, and N-vinyl caprolactam; Cyanoacrylate monomers such as acrylonitrile and methacrylonitrile; Epoxy group-containing acrylic monomers such as glycidyl (meth) acrylate; Glycol-based acrylic ester monomers such as polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, and methoxypolypropylene glycol (meth) acrylate; Acrylic acid ester type monomers, such as (meth) acrylic acid tetrahydrofurfuryl, fluorine (meth) acrylate, silicone (meth) acrylate, and 2-methoxyethyl acrylate, can also be used. Moreover, isoprene, butadiene, isobutylene, vinyl ether, etc. are mentioned.

Moreover, the silane monomer etc. which contain a silicon atom as a copolymerizable monomer of that excepting the above are mentioned. Examples of the silane monomers include 3-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, and 8-. Vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloyloxydecyltrimethoxysilane, 10-acryloyloxydecyltrimethoxysilane, 10-methacryloyloxydecyltri Ethoxysilane, 10-acryloyl oxydecyl triethoxysilane, etc. are mentioned.

Moreover, as a copolymerization monomer, a tripropylene glycol di (meth) acrylate, the tetraethylene glycol di (meth) acrylate, a 1, 6- hexanediol di (meth) acrylate, and a bisphenol A diglycidyl ether di (meth) acryl Latene, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Unsaturated double bonds, such as (meth) acryloyl groups, such as esterified products of (meth) acrylic acid and polyhydric alcohols, such as dipentaerythritol hexa (meth) acrylate and caprolactone modified dipentaerythritol hexa (meth) acrylate As a functional group similar to a monomer component in the polyfunctional monomer which has two or more, and frame | skeletons, such as polyester, an epoxy, and a urethane, (meth) It may be used as a methacrylic group, a vinyl group and the like, such as unsaturated double bond, two or more additional polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate.

Although the said (meth) acrylic-type polymer has alkyl (meth) acrylate as a main component in the weight ratio of all the constituent monomers, although the ratio of the said copolymerization monomer in a (meth) acrylic-type polymer is not specifically limited, The ratio of the said copolymerization monomer is all It is preferable that it is about 0 to 20%, about 0.1 to 15%, and about 0.1 to 10% in the weight ratio of a constituent monomer.

Among these copolymerization monomers, hydroxyl group-containing monomers and carboxyl group-containing monomers are preferably used from the viewpoint of adhesion and durability. A hydroxyl group containing monomer and a carboxyl group containing monomer can be used together. These copolymerization monomers become a reaction point with a crosslinking agent, when an adhesive composition contains a crosslinking agent. Since hydroxyl group containing monomer, carboxyl group containing monomer, etc. are rich in reactivity with an intermolecular crosslinking agent, they are used suitably for the improvement of the cohesiveness and heat resistance of the adhesive layer obtained. A hydroxyl group containing monomer is preferable at the point of rework property, and a carboxyl group containing monomer is preferable at the point of making both durability and rework property compatible.

When a hydroxyl group containing monomer is contained as said copolymerization monomer, 0.01-15 weight% is preferable, as for the ratio, 0.03-10 weight% is more preferable, 0.05-7 weight% is still more preferable. When it contains a carboxyl group-containing monomer as said copolymerization monomer, 0.05-10 weight% is preferable, as for the ratio, 0.1-8 weight% is more preferable, 0.2-6 weight% is further more preferable.

As for the (meth) acrylic-type polymer of this invention, the thing of the range of 500,000-3 million in weight average molecular weight is used normally. In consideration of durability, especially heat resistance, it is preferable to use a weight average molecular weight of 700,000 to 270 million. It is more preferable that it is 800,000-2,500,000. If the weight average molecular weight is less than 500,000, it is not preferable in terms of heat resistance. Moreover, when a weight average molecular weight becomes larger than 3 million, a large amount of diluting solvent is needed in order to adjust to the viscosity for coating, and it is unpreferable in that cost increases. In addition, a weight average molecular weight is measured by GPC (gel permeation chromatography) and says the value computed by polystyrene conversion.

In the production of such a (meth) acrylic polymer, a known production method such as radiation polymerization such as solution polymerization or UV polymerization, bulk polymerization, emulsion polymerization or various radical polymerization can be appropriately selected. The obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer and a graft copolymer.

In solution polymerization, for example, ethyl acetate, toluene or the like is used as the polymerization solvent. As a specific solution polymerization example, reaction adds a polymerization initiator under inert gas streams, such as nitrogen, and it is normally performed on reaction conditions for about 5 to 30 hours at about 50-70 degreeC.

The polymerization initiator, chain transfer agent, emulsifier, etc. used for radical polymerization are not specifically limited, It can select suitably and can use. In addition, the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator, a chain transfer agent, and reaction conditions, and the appropriate usage-amount is adjusted according to these types.

As the radical polymerization initiator, for example, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) dihydrochloride, 2,2'-azobis [2- (5- Methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (2-methylpropionamidine) sulfate, 2,2'-azobis (N, N'-di Azo initiators such as methylene isobutyl amidine) and 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate (manufactured by Wako Pure Chemical Industries, VA-057); Persulfates such as potassium sulfate and ammonium persulfate, di (2-ethylhexyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy Neodecanoate, t-hexyl peroxy pivalate, t-butyl peroxy pivalate, dilauroyl peroxide, di-n-octanoyl peroxide, 1,1,3,3-tetramethylbutylperoxy 2-ethylhexanoate, di (4-meth Peroxide initiators, persulfates, such as benzoyl) peroxide, dibenzoyl peroxide, t-butyl peroxy isobutyrate, 1,1-di (t-hexyl peroxy) cyclohexane, t-butyl hydroperoxide, and hydrogen peroxide Although redox type initiator which combined peroxide and a reducing agent, such as the combination of a sodium hydrogen sulfite, the combination of a peroxide, and sodium ascorbate, etc. are mentioned, It is not limited to these.

Although the said radical polymerization initiator may be used independently and may mix and use 2 or more types, it is preferable that content as a whole is about 0.005-1 weight part with respect to 100 weight part of monomers, and is about 0.02-0.5 weight part It is more preferable.

As the chain transfer agent, for example, lauryl mercaptan, glycidyl mercaptan, mercapto acetic acid, 2-mercaptoethanol, thioglycolic acid, thioglucolic acid 2-ethylhexyl, 2,3-dimercapto-1- Propanol etc. are mentioned. Although a chain transfer agent may be used independently and may be used in mixture of 2 or more type, content as a whole is about 0.1 weight part or less with respect to 100 weight part of total amounts of a monomer component.

Moreover, as an emulsifier used at the time of emulsion polymerization, anionic emulsifiers, such as sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkyl phenyl ether sodium sulfate, for example And nonionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, and polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used independently and may use 2 or more types together.

Moreover, as an emulsifier into which radically polymerizable functional groups, such as a propenyl group and an allyl ether group, were introduce | transduced as a reactive emulsifier, For example, Acrolon HS-10, HS-20, KH-10, BC-05, BC-10 , BC-20 (all of which are manufactured by DKS Co., Ltd.), Adecarierthorpe SE 10N (manufactured by ADEKA Corporation), and the like. Reactive emulsifiers are preferred because they are absorbed into the polymer chain after polymerization and thus have good water resistance. As for the usage-amount of an emulsifier, 0.5-1 weight part is more preferable from 0.3-5 weight part, polymerization stability, and mechanical stability with respect to 100 weight part of total amounts of a monomer component.

<Bridge school>

Moreover, in this invention, a crosslinking agent can be contained in the adhesive composition which forms the adhesive layer which has a pigment | dye. As the crosslinking agent, an organic crosslinking agent or a polyfunctional metal chelate can be used. As an organic type crosslinking agent, an isocyanate type crosslinking agent, a peroxide type crosslinking agent, an epoxy type crosslinking agent, an imine type crosslinking agent, etc. are mentioned. Multifunctional metal chelates are those in which a polyvalent metal is covalently or coordinated with an organic compound. Examples of the 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. . As an atom in the organic compound covalently bonded or coordinated, an oxygen atom etc. are mentioned, As an organic compound, an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, a ketone compound, etc. are mentioned.

As a compound by an isocyanate type crosslinking agent, for example, isocyanate monomers such as tolylene diisocyanate, chlorphenylenediisocyanato, tetramethylenediisocyanato, xylylene diisocyanate, diphenylmethane diisocyanate and hydrogenated diphenylmethane diisocyanate And urethane prepolymers such as isocyanate compounds, isocyanurates, biuret compounds, polyether polyols, polyester polyols, acrylic polyols, polybutadiene polyols, and polyisoprene polyols, in which these isocyanate monomers are added with trimethylolpropane and the like. Isocyanate etc. are mentioned. Especially preferably, it is a polyisocyanate compound and is 1 type or polyisocyanate compound derived from it selected from the group which consists of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate. Here, the polyisocyanate compound selected from the group consisting of hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate, or a polyisocyanate compound derived therefrom includes hexamethylene diisocyanate, hydrogenated xylylene diisocyanate and isophorone diisocyanate. , Polyol-modified hexamethylene diisocyanate, polyol-modified hydrogenated xylylene diisocyanate, trimer-type hydrogenated xylylene diisocyanate, polyol-modified isophorone diisocyanate and the like. The exemplified polyisocyanate compound is preferable because the reaction with the hydroxyl group proceeds rapidly, particularly with the acid and base contained in the polymer as a catalyst, in particular contributing to the rapid crosslinking.

The peroxide can be suitably used as long as it generates radically active species by heating or light irradiation to advance the crosslinking of the base polymer of the pressure-sensitive adhesive composition, but in view of workability and stability, a peroxide having a half-life temperature of 80 ° C to 160 ° C for 1 minute It is preferable to use, and it is more preferable to use the peroxide which is 90 degreeC-140 degreeC.

As the peroxide, for example, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), di-sec-butylperoxydicarbonate (1 minute half-life temperature: 92.4 ° C), t- Butyl peroxy neodecanoate (1 minute half life temperature: 103.5 ° C.), t-hexyl peroxy pivalate (1 minute half life temperature: 109.1 ° C.), t-butyl peroxy pivalate (1 minute half life temperature: 110.3 ° C.) , Dilauroyl peroxide (half life temperature: 116.4 ° C.), di-n-octanoyl peroxide (half life temperature: 117.4 ° C.), 1,1,3,3-tetramethylbutylperoxy-2 Ethylhexanoate (1 minute half-life temperature: 124.3 ° C), di (4-methylbenzoyl) peroxide (1 minute half-life temperature: 128.2 ° C), dibenzoylperoxide (1 minute half-life temperature: 130.0 ° C), t- Butyl peroxy isobutyrate (1 minute half life temperature: 136.1 degreeC), 1,1-di (t-hexyl peroxy) cyclohexane (1 minute half life temperature: 149.2 degreeC) etc. are mentioned. Among them, di (4-t-butylcyclohexyl) peroxydicarbonate (1 minute half-life temperature: 92.1 ° C), dilauroyl peroxide (1 minute half-life temperature: 116.4 ° C), di Benzoyl peroxide (1 minute half-life temperature: 130.0 ° C) and the like are preferably used.

In addition, the half life of a peroxide is an index which shows the decomposition rate of a peroxide, and means the time until the residual amount of a peroxide becomes half. The decomposition temperature for obtaining the half life at any time and the half life time at any temperature are described in the manufacturer's catalog and the like, for example, in NOF Corporation's `` Organic Peroxide Catalog 9th Edition (May 2003) ''. It is described.

20 weight part or less is preferable with respect to 100 weight part of base polymers, such as a (meth) acrylic-type polymer, in an adhesive composition, More preferably, 0.01-20 weight part is more preferable, 0.03-10 weight part is more preferable. In addition, when the said crosslinking agent is more than 20 weight part, moisture resistance is not enough and peeling easily arises in a reliability test etc.

Moreover, a silane coupling agent can be contained in the adhesive composition which forms the adhesive layer which has the pigment | dye of this invention. By using a silane coupling agent, durability can be improved. Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4 Epoxy group-containing silane coupling agents such as -epoxycyclohexyl) ethyltrimethoxysilane, 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, and 3-triethoxy Amino group-containing silane coupling agents such as silyl-N- (1,3-dimethylbutylidene) propylamine and N-phenyl-γ-aminopropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-metha Isocyanate group containing silane coupling agents, such as (meth) acryl group containing silane coupling agents, such as a krilloxy propyl triethoxysilane, and 3-isocyanate propyl triethoxysilane, etc. are mentioned.

Although the said silane coupling agent may be used independently and may mix and use 2 or more types, as a whole content, 0.001-5 weight part of said silane coupling agents with respect to 100 weight part of base polymers, such as said (meth) acrylic-type polymer, It is preferable, 0.01-1 weight part is more preferable, Furthermore, 0.02-1 weight part is more preferable, 0.05-0.6 weight part is still more preferable. It is an amount which improves durability and maintains adhesive force to optical members, such as a liquid crystal cell, suitably.

Moreover, in this invention, polyether modified silicone can be mix | blended in the adhesive composition which forms the adhesive layer which has a pigment | dye. As polyether modified silicone, what is disclosed by Unexamined-Japanese-Patent No. 2010-275522 can be used, for example.

In addition, in the present invention, other well-known additives may be contained in the adhesive composition which forms the adhesive layer which has a pigment | dye, For example, powder, such as a coloring agent and a pigment, dye, surfactant, a plasticizer, a tackifier, Depending on the use of surface lubricants, leveling agents, softeners, anti-aging agents, antioxidants, light stabilizers, ultraviolet absorbers, polymerization inhibitors, inorganic or organic fillers, metal powders, particulates, foils, etc. Can be. Moreover, you may employ | adopt the redox system which added the reducing agent within the range which can be controlled.

Although the adhesive layer which has a pigment | dye is formed with the said adhesive composition, in formation of an adhesive layer, it is preferable to fully consider the influence of crosslinking process temperature and crosslinking treatment time, while adjusting the addition amount of a crosslinking agent.

The crosslinking treatment temperature and the crosslinking treatment time can be adjusted by the crosslinking agent to be used. It is preferable that crosslinking process temperature is 170 degrees C or less.

In addition, such crosslinking process may be performed at the temperature at the time of the drying process of an adhesive layer, and you may provide and perform a crosslinking process process separately after a drying process.

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

As a method of forming the adhesive layer which has a pigment | dye, the said adhesive composition is apply | coated to the separator etc. which carried out the peeling process, for example, after drying and removing a polymerization solvent etc. and forming an adhesive layer, it transfers to the polarizing film which has a polyvinyl alcohol-type polarizer. The adhesive composition is apply | coated to the polarizing film which has a polyvinyl alcohol-type polarizer, or the method of forming the adhesive layer in a polarizing film which has a polyvinyl alcohol-type polarizer, etc. by drying and removing a polymerization solvent etc. to a polarizing film which has a polyvinyl alcohol-type polarizer. In addition, in application | coating of an adhesive, you may add newly 1 or more types of solvents other than a polymerization solvent suitably.

As a separator which peeled, the silicone peeling liner is used preferably. As a method of drying an adhesive in the process of apply | coating and drying the adhesive composition of this invention on such a liner, and forming an adhesive layer, the method suitable suitably according to the objective can be employ | adopted. Preferably, the method of overheating and drying the said coating film is used. The heat drying temperature is preferably 40 ° C to 200 ° C, more preferably 50 ° C to 180 ° C, and particularly preferably 70 ° C to 170 ° C. By setting heating temperature in the said range, the adhesive which has the outstanding adhesive characteristic can be obtained.

As the drying time, a suitable time may be employed. The drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 10 minutes, and particularly preferably 10 seconds to 5 minutes.

Furthermore, an adhesive layer is formed on the surface of the polarizing film which has a polyvinyl alcohol-type polarizer, for example, about 0.5-2 micrometers in thickness, or after performing various easy-adhesion processes, such as a corona treatment and a plasma treatment. can do. In addition, you may perform an easily bonding process on the surface of an adhesive layer.

Various methods are used as a formation method of the said adhesive layer. Specifically, for example, 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, die coater, etc. The extrusion coating method etc. are mentioned.

The thickness of the said adhesive layer is not specifically limited, For example, it is about 1-100 micrometers. Preferably it is 2-50 micrometers, More preferably, it is 2-40 micrometers, More preferably, it is 5-35 micrometers. It is preferable that the adhesive layer containing the said pigment is 25 micrometers or less in thickness, in order to prevent the invasion of oxygen from the edge part of the said adhesive layer.

In the case where the pressure-sensitive adhesive layer is exposed, the pressure-sensitive adhesive layer may be protected by a sheet (separator) subjected to peeling treatment until it is provided for practical use.

<Film layer>

Moreover, as an optical function layer of this invention, the film layer containing a pigment is mentioned, The said film layer can be formed from the composition containing the base polymer for film formation, and a pigment | dye. As a material of the base polymer which forms a film layer, the same thing as the material which comprises the transparent protective film mentioned later can be illustrated. In particular, as the material, cellulose resins such as triacetyl cellulose, polyester resins, (meth) acrylic resins, cyclic polyolefin resins (norbornene-based resins) and the like are preferably used. The film layer can be suitably applied to a polyvinyl alcohol polarizer using an adhesive, an adhesive, or the like.

Various methods can be employ | adopted for the formation method of the film layer containing a pigment | dye. For example, when melt | dissolving the pellet of the said resin material in a solvent, a film layer can be manufactured by mixing a pigment | dye, preparing a composition, and casting or extruding the said composition. In that case, a film layer can be shape | molded to moderate thickness. At the time of preparation of the said composition, an additive can be mix | blended suitably.

The thickness of the said film layer is not specifically limited, It is the same as that of an adhesive layer, For example, it is about 1-100 micrometers. Preferably it is 2-50 micrometers, More preferably, it is 2-40 micrometers, More preferably, it is 5-35 micrometers. The separator can also be applied to a film layer containing a dye.

As the constituent material of the separator, for example, plastic film such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, porous material such as paper, cloth, nonwoven fabric, net, foam sheet, metal foil, laminate thereof and the like Although a suitable thin leaf of etc. is mentioned, a plastic film is used suitably from the point which is excellent in surface smoothness.

It will not specifically limit, if it is a film which can protect the said optical function layer (especially an adhesive layer) as this plastic film, For example, a polyvinyl alcohol film, a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, poly Methyl pentene film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, an ethylene-vinyl acetate copolymer film, etc. are mentioned.

The thickness of the separator is usually 5 to 200 µm, preferably about 5 to 100 µm. The separator may be subjected to release and antifouling treatments such as silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agents and silica powder, and antistatic treatments such as coating, kneading and vapor deposition. In particular, the peelability from the optical functional layer (particularly, the pressure-sensitive adhesive layer) can be further improved by appropriately performing a peeling treatment such as silicon treatment, long chain alkyl treatment, or fluorine treatment on the surface of the separator.

In addition, the sheet | seat which carried out the peeling process used in preparation of the said polarizing film with an adhesive layer can be used as a separator of the polarizing film with an optical function layer as it is, and the simplification in a process surface is possible.

As the separator, one having an oxygen permeability of 1 [cm 3 / (m 2 · 24h · atm)] or less is preferable. The oxygen permeability is preferably 0.8 [cm 3 / (m 2 · 24h · atm)] or less, more preferably 0.6 [cm 3 / (m 2 · 24h · atm)] or less, and 0.5 [cm 3 / (m 2 · 24h · atm) ] Are more preferable. The oxygen permeability is determined by the material, the thickness and the like. Oxygen transmittance of an optical member is specifically measured by description of an Example.

As a separator which can satisfy | fill the said low oxygen permeability, a polyvinyl alcohol film, a polyethylene terephthalate film, the film which carried out aluminum vapor deposition, polyacrylonitrile, ethylene vinyl alcohol, etc. are preferable, for example. Moreover, it is preferable that it is 10-100 micrometers, and, as for the thickness of the said film, it is more preferable that it is 25-75 micrometers.

<Polarizing film>

The polarizing film of this invention has the said polyvinyl alcohol-type polarizer. The polyvinyl alcohol polarizer may have low oxygen transmittance and an oxygen transmittance of 1 [cm 3 / (m 2 · 24 h · atm)] or less.

The polarizing film is generally used to have a transparent protective film on one side or both sides of the polyvinyl alcohol polarizer.

The said polyvinyl alcohol polarizer is not specifically limited, Various things can be used. As a polarizer, for example, a diaxial substance of iodine or a dichroic dye is adsorbed onto a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film. And polyene oriented films such as stretched and dehydrated products of polyvinyl alcohol and dehydrochloric acid treated products of polyvinyl chloride. Among these, the polarizer which consists of dichroic substances, such as a polyvinyl alcohol-type film and iodine, is preferable. Although the thickness in particular of these polarizers is not restrict | limited, Usually, it is about 80 micrometers or less.

The polarizer which dyed a polyvinyl alcohol-type film with iodine and uniaxially stretched can be created, for example, by dyeing a polyvinyl alcohol-type film by immersing it in the aqueous solution of iodine, and extending | stretching 3 to 7 times the original length. If necessary, it may be immersed in an aqueous solution such as potassium iodide, which may contain boric acid, zinc sulfate, zinc chloride, or the like. If necessary, the polyvinyl alcohol-based film may be dipped in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, the contamination of the polyvinyl alcohol-based film with the antiblocking agent can be washed, and the polyvinyl alcohol-based film is swelled to prevent unevenness such as dyeing. Stretching may be performed after dyeing with iodine, may be performed while dyeing, or may be dyed with iodine after stretching. It can extend | stretch also in aqueous solution, such as boric acid and potassium iodide, or a water bath.

Moreover, as a polarizer, the thin polarizer whose thickness is 10 micrometers or less can be used. It is preferable that the said thickness is 1-7 micrometers from the viewpoint of thickness reduction. It is preferable that such a thin polarizer is excellent in durability because it has little thickness unevenness, excellent visibility, and small dimensional change, and thickness can also be reduced as a polarizing film.

Typical thin polarizers include Japanese Patent Application Laid-Open No. 51-069644, Japanese Patent Application Laid-Open No. 2000-338329, WO2010 / 100917 Pamphlet, PCT / JP2010 / 001460, or Japanese Patent Application No. 2010-269002. The thin polarizing film described in Unexamined-Japanese-Patent No. 2010-263692 specification is mentioned. These thin polarizing films can be obtained by the manufacturing method including the process of extending | stretching and dyeing a polyvinyl alcohol-type resin (henceforth a PVA-type resin) layer, and the extending | stretching resin base material in the state of a laminated body. If it is this manufacturing method, even if a PVA-type resin layer is thin, it is supported by the resin base material for extending | stretching, and it becomes possible to extend | stretch without problems, such as the fracture by extending | stretching.

As said thin polarizing film, it can extend | stretch at high magnification among the manufacturing methods including the process of extending | stretching in the state of a laminated body, and the process of dyeing, and can improve polarization performance, The specification of WO2010 / 100917 pamphlet and PCT / JP2010 / 001460 is possible. Or obtained by a manufacturing method including a step of stretching in an aqueous boric acid solution as described in Japanese Patent Application No. 2010-269002 or Japanese Patent Application No. 2010-263692, in particular Japanese Patent Application No. 2010-269002 It is preferable that it is obtained by the manufacturing method including the process of carrying out auxiliary drawing air before extending | stretching in the boric-acid aqueous solution as described in Unexamined-Japanese-Patent No. 2010-263692 specification.

As a material which comprises a transparent protective film, the thermoplastic resin which is excellent in transparency, mechanical strength, thermal stability, moisture barrier property, isotropy, etc. is used, for example. Specific examples of such thermoplastic resins include cellulose resins such as triacetyl cellulose, polyester resins, polyether sulfone resins, polysulfone resins, polycarbonate resins, polyamide resins, polyimide resins, polyolefin resins, (meth) acrylic resins, and cyclic compounds. Polyolefin resin (norbornene-based resin), polyarylate resin, polystyrene resin, polyvinyl alcohol resin, and mixtures thereof. In addition, a transparent protective film is bonded to one side of the polarizer by an adhesive layer, but on the other side, a thermosetting resin such as (meth) acrylic, urethane, acrylic urethane, epoxy, silicone, or ultraviolet curable resin can be used as the transparent protective film. have. One or more types of arbitrary appropriate additives may be contained in the transparent protective film. As an additive, a ultraviolet absorber, antioxidant, a lubricating agent, a plasticizer, a mold release agent, a coloring inhibitor, a flame retardant, a nucleating agent, an antistatic agent, a pigment, a coloring agent, etc. are mentioned, for example. Content of the said thermoplastic resin in a transparent protective film becomes like this. Preferably it is 50-100 weight%, More preferably, it is 50-99 weight%, More preferably, it is 60-98 weight%, Especially preferably, it is 70-97 weight% . When content of the said thermoplastic resin in a transparent protective film is 50 weight% or less, there exists a possibility that the high transparency etc. which a thermoplastic resin originally has cannot fully be expressed.

The thickness of a transparent protective film is not specifically limited, For example, it is about 10-90 micrometers. Preferably it is 15-60 micrometers, More preferably, it is 20-50 micrometers. When a transparent protective film is arrange | positioned between the said polyvinyl alcohol-type polarizer and the adhesive layer containing the said pigment, the transparent protective film of the thickness adjusted so that the total thickness with an adhesive bond layer etc. may be 45 micrometers or less is used.

A functional layer (surface layer) such as a hard coat layer, an antireflection layer, an anti-sticking layer, a diffusion layer, or an antiglare layer may be formed on the surface of the transparent protective film that does not adhere to the polarizer.

The adhesive used for bonding the polarizer and the transparent protective film is not particularly limited as long as it is optically transparent, and various types of water-based, solvent-based, hot-melt, radical-curable, and cationic-curable types are used. Suitable. The thickness of an adhesive bond layer is about 0.01-3 micrometers normally, It is preferable that it is 0.3-2 micrometers, and 0.5-1.5 micrometers is more preferable.

As a layer which does not have a pigment | dye which can be formed between the said polyvinyl alcohol-type polarizer and the adhesive layer which has the said pigment (for example, layer (B in the aspect of FIG. 3)), for example, the said anchor layer, Transparent protective film applied to polarizer, adhesive layer (to bond the transparent protective film to polarizer), pressure-sensitive adhesive layer (without color), retardation layer (or retardation film), light scattering layer, light emitting layer, undercoat layer, liquid crystal A layer, a polarizing layer, etc. are mentioned. The said layer (B) can be used as a single | mono layer, and can also combine multiple layers. In addition, when using multiple layers (for example, layer (B1), layer (B2)), for example, polarizer (P) / layer (B1) / adhesive layer (it does not have a pigment) What laminated | stacked the some layer B through the adhesive layer which does not have a pigment | dye like / layer (B2) / adhesive layer (A) (having a pigment) can be used. The thickness of the layer (B) can be designed in accordance with the properties of each layer in the range of 45㎛ or less. The thing of low oxygen permeability is also preferable about the said layer (B).

<LCD panel>

The polarizing film with an optical function layer of the said invention can be used suitably when forming a liquid crystal panel. For example, in the case of the polarizing film with an adhesive layer whose optical functional layer of the polarizing film with optical function layer of this invention is an adhesive layer, the said polarizing film with an adhesive layer is polarized with said adhesive layer on at least one surface of a liquid crystal cell. It is bonded together through the adhesive layer of a film, and forms a liquid crystal panel. The polarizing film with an adhesive layer of this invention is used suitably for the visual recognition side of a liquid crystal cell.

Although the liquid crystal cell can use arbitrary types, such as TN type, STN type, (pi) type, VA type, and IPS type, for example, the liquid crystal cell of an IPS mode is used suitably for the liquid crystal panel of this invention.

In addition to the polarizing film, other optical layers may be applied to the formation of the liquid crystal panel. Although there is no limitation in particular about the optical layer, For example, of a liquid crystal panel, such as a reflecting plate, a semi-transmissive plate, a retardation plate (including wavelength plates, such as 1/2 or 1/4), a visual compensation film, a brightness enhancement film, etc. The optical layer which may be used for formation can use 1 layer or 2 or more layers in the visual recognition side and / or a back side of a liquid crystal cell.

<Liquid crystal display device>

The liquid crystal panel is used for a liquid crystal display device, and is formed by assembling appropriately a component such as an illumination system and mounting a drive circuit as necessary. In the formation of the liquid crystal display device, for example, a diffuser plate, an antiglare layer, an antireflection film, a protective plate, a prism array, a lens array sheet, a light diffuser plate, a backlight, or a suitable component may be placed at a suitable position. You can place more than that. Moreover, a suitable liquid crystal display device, such as using a backlight or a reflecting plate, can be formed for an illumination system.

EXAMPLE

Although an Example demonstrates this invention concretely below, this invention is not limited by these Examples. In addition, all the parts and% in each case are a basis of weight. The room temperature standing conditions which are not specifically defined below are all 23 degreeC 65% RH.

<Measurement of the weight average molecular weight of the (meth) acrylic polymer>

The weight average molecular weight (Mw) of the (meth) acrylic-type polymer was measured by GPC (gel permeation chromatography). Similar measurements were made for Mw / Mn.

Analysis device: manufactured by TOSOH Corporation, HLC-8120GPC

Column: made by TOSOH Corporation, G7000H _XL + GMH _XL + GMH _XL

Column size: each 7.8 mm diameter x 30 cm total 90 cm

Column temperature: 40 ℃

Flow rate: 0.8 mL / min

Injection volume: 100 μL

Eluent: tetrahydrofuran

Detector: Differential Refractometer (RI)

Standard sample: polystyrene

Measurement of Oxygen Permeability

It was calculated | required according to JISK 7126-2 on 23 degreeC and the conditions of 0% RH using the oxygen transmittance | permeability measuring apparatus OX-TRAN made from MOCON.

Example 1

<Production of Polarizing Film>

In order to produce a thin polarizing layer, first, a laminate in which a 9 μm-thick PVA layer was formed on an amorphous PET substrate was formed by air assisted stretching at a stretching temperature of 130 ° C., and then the stretched laminate was dyed by dyeing. An optical film laminate comprising a 4 μm-thick PVA layer integrally formed with an amorphous PET substrate such that a colored laminate was produced and the colored laminate was stretched in boric acid water at a stretching temperature of 65 ° C. to a total draw ratio of 5.94 times. Created a sieve. By this two-stage stretching, the PVA molecules of the PVA layer formed on the amorphous PET substrate are highly ordered, and the thickness 4 constituting the highly functional polarizing layer in which iodine adsorbed by dyeing is highly ordered in one direction as a polyiodine ion complex. An optical film laminate comprising a PVA layer of μm could be produced. Further, while applying a polyvinyl alcohol-based adhesive to the surface of the polarizing layer of the optical film laminate (1 μm in thickness of the formed adhesive layer), a saponified 40 μm thick first acrylic resin film (oxygen transmittance of 5 [cm 3 / (M 2 · 24 h · atm)]), and then the amorphous PET substrate was peeled off to prepare a single protective polarizing film using a thin polarizer (oxygen transmittance less than 0.02 [cm 3 / (m 2 · 24 h · atm)]). This is called a thin piece protective polarizing film.

<Preparation of (meth) acrylic polymer>

A monomer mixture containing 100 parts of butyl acrylate, 0.01 part of 2-hydroxyethyl acrylate, and 5 parts of acrylic acid was charged into a reaction vessel equipped with a cooling tube, a nitrogen introduction tube, a thermometer, and a stirring device. Further, 0.1 part of 2,2'-azobisisobutyronitrile was added together with 100 parts of ethyl acetate as a polymerization initiator with respect to 100 parts of the monomer mixture, nitrogen gas was introduced and nitrogen was substituted while gradually stirring, followed by liquid temperature in the flask. Was maintained at around 55 ° C to carry out polymerization for 8 hours to prepare a solution (solid content concentration of 30% by weight) of an acrylic polymer having a weight average molecular weight (Mw) of 1.8 million and Mw / Mn = 4.1.

(Preparation of Adhesive Composition)

With respect to 100 parts of solid content of the acrylic polymer solution prepared above,

0.3 parts of benzoyl peroxide (trade name NYPER BMT manufactured by NOF Corporation),

1 part of isocyanate crosslinking agent (trade name Coronate L manufactured by TOSOH Corporation),

0.25 parts of a tetraaza porphyrin-based dye (trade name PD-320 manufactured by Yamamoto Chemicals Inc. having a maximum absorption wavelength at a wavelength of 595 nm), and

Was blended to obtain an adhesive composition.

(Production of Polarizing Film with Adhesive Layer)

The pressure-sensitive adhesive composition was uniformly coated directly on the surface of the polarizer (PVA layer) of the thin piece protective polarizing film with an applicator, dried for 2 minutes in an air circulation oven at 155 ° C., and a pigment having a thickness of 20 μm on the surface of the polarizer. The pressure-sensitive adhesive layer having a pressure-sensitive adhesive layer was formed to prepare a single protective polarizing film with pressure-sensitive adhesive layer.

Example 2

In Example 1, except that the adhesive layer which does not have a pigment | dye of thickness 20 micrometers was laminated on the surface of the said polarizer, and the pressure-sensitive adhesive layer which has a pigment | dye of thickness 20 micrometers was formed, it carried out similarly to Example 1, and the single layer protection with an adhesive layer was carried out. The polarizing film was produced.

In addition, the same adhesive composition was used for formation of the adhesive layer which does not have a pigment | dye of 20 micrometers in thickness except having mix | blended the pigment | dye in the adhesive composition used for formation of the adhesive layer which has the said pigment | dye. The pressure-sensitive adhesive layer was formed by coating the pressure-sensitive adhesive composition uniformly with an applicator on the surface of the release substrate (MRF38CK manufactured by Mitsubishi Plastics, Inc.) of the polyethylene terephthalate film treated with a silicone-based release agent, It carried out by drying for minutes, and transferred the said adhesive layer to the said polarizer and laminated | stacked it.

Example 3

What formed the adhesive layer which has the pigment | dye of thickness 20micrometer after laminating | stacking two layers (total thickness 40micrometer) of the adhesive layer which does not have the pigment | dye of thickness 20micrometer used in Example 2 on the surface of the said polarizer in Example 1 A protective film polarizing film with an adhesive layer was produced in the same manner as in Example 1. In addition, formation of the adhesive layer which does not have a pigment | dye is the same as that of the description of Example 2.

Example 4

<Production of Polarizing Film>

A 40 micrometer-thick 2nd acrylic resin film (oxygen permeability 5 [cm <3> / (m <2> * 24h * atm]]) which saponified to the surface of the polarizer (PVA layer) of the thin piece protective polarizing film obtained in Example 1 is an adhesive agent It bonded together through (1 micrometer in thickness of an adhesive bond layer), and produced both protective polarizing films. This is called a thin double-protective polarizing film.

(Production of Polarizing Film with Adhesive Layer)

The pressure-sensitive adhesive composition used in Example 1 was uniformly applied directly to the back surface (opposite to the adhesive layer) of the second acrylic resin film of the positive protective polarizing film by an applicator, and dried in an air circulation type constant temperature oven at 155 ° C. for 2 minutes. The adhesive layer which has a pigment | dye of thickness 20micrometer was formed in the back surface of the said 2nd acrylic resin film, and the single protection polarizing film with an adhesive layer was produced.

Comparative Example 1

What formed the adhesive layer which has a pigment | dye of thickness 20micrometer after laminating | stacking three layers (total thickness 60micrometer) of the adhesive layer which does not have the pigment | dye of thickness 20micrometer used in Example 2 on the surface of the said polarizer in Example 1 A protective film polarizing film with an adhesive layer was produced in the same manner as in Example 1 except for the above. In addition, formation of the adhesive layer which does not have a pigment | dye is the same as that of the description of Example 2.

Comparative Example 2

Instead of forming the pressure-sensitive adhesive composition in the surface of the polarizer (PVA layer) of the thin piece protective polarizing film in Example 1, a 40 μm thick acrylic resin film (oxygen transmittance of 5 [cm 3 / (m 2 · 24h. The acrylic resin film with an adhesive layer was produced like Example 1 except having formed at atm)]).

The following evaluation was performed as a sample using the single-protective or double-protective polarizing film with an adhesive layer obtained by the said Example and a comparative example, or the acrylic resin film with an adhesive layer. The evaluation results are shown in Table 1.

(Evaluation of the fading)

After the sample was cut into a test piece of 50 mm in length x 25 mm in width, the state (initial stage) of the front and end portions was captured as a photograph using a scanner (specifically, PIXUS MX923 manufactured by Canon Corporation). Subsequently, after performing a durability test in which the sample was left in a thermostat at 85 ° C. for 24 hours, it was taken out and returned to room temperature (23 ° C.), and then again captured the state of the front and end of the sample (after 24 hours) as a photograph using the same scanner. did. The photographs before (initial) and after (24) hours before the test injection were binarized, and the presence or absence of color loss at the front and the amount of color loss at the end were measured by the following method.

<Front color missing>

Visually evaluated whether color was missing based on the image of the binarization photograph before putting a test piece into the durability test, and the binarization photograph after insertion. Table 1 also shows the transmittance before and after the test piece was put into the durability test. The measurement of the transmittance | permeability was performed in the state which a test piece is 23 degreeC using the spectrophotometer (Integrated sphere) spectrophotometer (Dot-3c of MURAKAMI COLOR RESEARCH LABORATORY CO., LTD.).

○ There is no difference in color than before.

× The color is clearly lighter than before.

<Color missing part>

The distance of the longest part of the part where the color of the peripheral edge was clearly missing from the peripheral edge of the test piece toward the center was measured with a ruler, and this was evaluated as color omission (fading progress distance: mm).

In the Example, there was no color omission at the front, and the amount of color omission at the end was small. 3 mm or less is preferable, as for color fall-out of an edge part (mm), 2 mm or less is more preferable, It is more preferable that it is 1 mm or less, It is preferable that it is 0 mm. On the other hand, in Comparative Example 1, since the polyvinyl alcohol-based polarizer was used, no color loss was observed from the front, but the distance between the polyvinyl alcohol-based polarizer and the optical functional layer (adhesive layer) may exceed 45 µm. Color deviation at the end (fading progression distance: mm) was confirmed. In the comparative example 2, since the said polyvinyl alcohol-type polarizer was not used, the color omission of the front side and the color omission of the edge part were confirmed together.

P polyvinyl alcohol polarizer
A optical function layer
F transparent protective film
S separator
B, C and other layers
x Pressure-sensitive adhesive layer and distance from polyvinyl alcohol polarizer

Claims (10)

A polarizing film with an optical functional layer having an optical functional layer containing a dye on at least one side of a polarizing film having a polyvinyl alcohol polarizer, wherein the distance between the polyvinyl alcohol polarizer and the optical functional layer containing the dye is 45 μm. The following is a polarizing film with an optical function layer characterized by the above-mentioned. The method of claim 1,
The distance of the said polyvinyl alcohol-type polarizer and the said adhesive layer is 25 micrometers or less, The optical function layer polarizing film characterized by the above-mentioned. The method according to claim 1 or 2,
The said adhesive layer with the said polyvinyl alcohol-type polarizer is laminated | stacked directly, The polarizing film with an optical function layer characterized by the above-mentioned. The method according to claim 1 or 2,
At least one layer which does not have a pigment | dye of thickness 45 micrometers or less is provided between the said optical function layer with the polyvinyl alcohol-type polarizer, The polarizing film with an optical function layer characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The said polyvinyl alcohol-type polarizer has oxygen transmittance of 1 [cm <3> / (m <2> * 24h * atm]] or less, The polarizing film with an optical function layer characterized by the above-mentioned. The method according to any one of claims 1 to 5,
Said pigment | dye has maximum absorption wavelength in at least one of wavelength range 470-510 nm and wavelength range 570-610 nm, The polarizing film with an optical function layer characterized by the above-mentioned. The method according to any one of claims 1 to 6,
The said dye is a tetraaza porphyrin type pigment | dye, The polarizing film with optical function layers characterized by the above-mentioned. The method according to any one of claims 1 to 7,
0.01-5 weight part of said pigment | dyes are contained with respect to 100 weight part of base polymers which form the resin layer of the said optical function layer, The polarizing film with an adhesive layer characterized by the above-mentioned. The method according to any one of claims 1 to 8,
The optical function layer containing the said pigment is 25 micrometers or less in thickness, The polarizing film with optical function layer characterized by the above-mentioned. The image display apparatus which has a polarizing film with an optical function layer as described in any one of Claims 1-9.

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