TW201736550A - Adhesive composition and adhesive layer for organic electroluminescent display device, polarizing film equipped with adhesive layer for organic electroluminescent display device, and organic electroluminescent display device - Google Patents

Abstract

This adhesive composition for an organic electroluminescent display device contains a base polymer, a UV absorber, and a dye compound in which the maximum absorption wavelength of the absorption spectrum is within the 380-430 nm wavelength range. The use of this adhesive composition for an organic electroluminescent display device in an organic electroluminescent display device makes it possible to suppress the deterioration of an organic electroluminescent element and to form an adhesive layer for an organic electroluminescent display device having high transparency. The present invention also makes it possible to provide an adhesive layer for an organic electroluminescent display device formed from the adhesive composition, an adhesive layer-equipped polarizing film comprising a polarizing film and the adhesive layer for an organic electroluminescent display device, and an organic electroluminescent display device comprising the adhesive layer and/or the adhesive layer-equipped polarizing film.

Description

Adhesive composition for organic EL display device, adhesive layer for organic EL display device, polarizing film with adhesive layer for organic EL display device, and organic EL display device

FIELD OF THE INVENTION The present invention relates to an adhesive composition for an organic EL (electroluminescence) display device (OLED). Moreover, the present invention relates to an adhesive layer for an organic EL display device formed of the above-described adhesive composition for an organic EL display device, and a polarizing film having an adhesive layer having the adhesive layer. Furthermore, the present invention relates to an organic EL display device using the above-described adhesive layer and/or the above polarizing film.

Background Art In recent years, organic EL display devices equipped with organic EL panels have been widely used in various applications such as mobile phones, car navigation devices, personal computer monitors, and televisions. In general, in order to suppress the natural light from being reflected by the metal electrode (cathode) so as to look like a mirror surface, the organic EL display device is provided with a circular polarizing plate (a laminate of a polarizing plate and a quarter-wave plate) on the viewing side surface of the organic EL panel. Wait). Further, a circular polarizing plate laminated on the viewing side surface of the organic EL panel may have a decorative panel or the like laminated. The constituent members of the organic EL display device such as the circular polarizing plate or the decorative panel are usually laminated by a bonding material such as an adhesive layer or an adhesive layer.

In an image display device such as an organic EL display device, constituent members and the like in the image display device may be deteriorated by incident ultraviolet light, and in order to suppress deterioration due to the ultraviolet light, it is known to provide an ultraviolet absorber. Layer body. Specifically, for example, a transparent double-sided adhesive sheet for an image display device having at least one ultraviolet absorbing layer and having a light transmittance of 30% or less at a wavelength of 380 nm and a long wavelength near a wavelength of 430 nm is known. The visible light transmittance of the side is 80% or more (for example, refer to Patent Document 1); or an adhesive sheet having an adhesive layer containing an acrylic polymer and a trivalent ultraviolet absorber (for example, refer to the patent document) 2).

For example, Japanese Laid-Open Patent Publication No. 2012-211305.

SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The adhesive sheets described in Patent Documents 1 and 2 can control the light transmittance at a wavelength of 380 nm. However, when the adhesive sheet is used in an organic EL display device, the organic EL device may be used. Deterioration due to prolonged use, insufficient. This is because the adhesive sheet described in Patent Documents 1 and 2 can absorb light having a wavelength of 380 nm, but cannot sufficiently absorb the wavelength of the short-wavelength side of the light-emitting region (close to the long wavelength side of 430 nm) of the organic EL element. The light in the region (380 nm to 430 nm) is deteriorated by the transmitted light.

Therefore, in order to suppress the deterioration of the organic EL device, it is necessary to use a layer in which the wavelength of the short-wavelength side (380 nm to 430 nm) of the light-emitting region (close to the long wavelength side of 430 nm) of the organic EL element is suppressed. The light is transmitted, and the visible light transmittance in the light-emitting region of the aforementioned organic EL element can be sufficiently ensured, and the transparency is high.

Therefore, an object of the present invention is to provide an adhesive composition for an organic EL display device which can form an adhesive layer for an organic EL display device, which has high transparency and is adhered by the adhesive. The agent layer is used in an organic EL display device, and deterioration of the organic EL element can be suppressed. Moreover, an object of the present invention is to provide an adhesive layer for an organic EL display device comprising the above-mentioned adhesive composition, a polarizing film having an adhesive layer of a polarizing film and an adhesive layer for an organic EL display device, and a polarizing film comprising An organic EL display device of the above-mentioned adhesive layer and/or the polarizing film with the above-mentioned adhesive layer.

Means for Solving the Problem In order to solve the above problems, the inventors have found the following adhesive composition for an organic EL display device, and have completed the present invention.

That is, the present invention relates to an adhesive composition for an organic EL display device, comprising: a base polymer; an ultraviolet absorber; and a pigment compound, wherein a maximum absorption wavelength of the absorption spectrum exists at a wavelength of 380 to 430 nm. Area.

The aforementioned base polymer is preferably a (meth)acrylic polymer.

The absorption wavelength of the ultraviolet absorber is preferably in the wavelength range of 300 to 400 nm.

Moreover, the present invention relates to an adhesive layer for an organic EL display device, which is characterized in that it is formed of an adhesive composition for an organic EL display device.

In the adhesive layer for an organic EL display device, it is preferable that an average transmittance of a wavelength of 300 to 400 nm is 5% or less, an average transmittance of a wavelength of 450 to 500 nm is 70% or more, and an average transmittance of a wavelength of 500 to 780 nm. More than 80%.

Further, the average transmittance may be such that the average transmittance of the wavelength of 300 to 400 nm is 5% or less, the average transmittance of the wavelength of 400 nm to 430 nm is 30% or less, and the average transmittance of the wavelength of 450 to 500 nm is 70%. As described above, the average transmittance of the wavelength of 500 to 780 nm is 80% or more.

Furthermore, the average transmittance may be as follows: an average transmittance of 5% or less at a wavelength of 300 to 400 nm, an average transmittance of a wavelength of 400 nm to 430 nm of more than 30% and less than 75%, and an average transmission of a wavelength of 450 to 500 nm. The rate is 80% or more, and the average transmittance of the wavelength of 500 to 780 nm is 80% or more.

Moreover, the present invention relates to a polarizing film comprising an adhesive layer for an organic EL display device, comprising: a polarizing film; and the above-mentioned adhesive layer for an organic EL display device.

Preferably, the polarizing film is provided with a transparent protective film on one side of the polarizing member and a retardation film on the other side, and the adhesive layer for the organic EL display device is preferably disposed on the opposite side of the contact surface of the retardation film. The side surface and/or the opposite side of the transparent protective film facing the contact surface of the polarizer.

The polarizing film with the adhesive layer for an organic EL display device preferably has a first adhesive layer, a transparent protective film, a polarizer, a second adhesive layer, a retardation film, and a third adhesive layer, and the first Among the adhesive layer, the second adhesive layer, and the third adhesive layer, at least one of the adhesive layers is the above-mentioned adhesive layer for an organic EL display device.

The retardation film is preferably a quarter-wave plate, and the polarizing film is preferably a circularly polarizing film.

Furthermore, the present invention relates to an organic EL display device using at least one of an adhesive layer for an organic EL display device and a polarizing film for an adhesive layer for an organic EL display device.

Advantageous Effects of Invention The adhesive composition for an organic EL display device of the present invention can form an adhesive layer for an organic EL display device having high transparency, and can suppress organic EL by using the adhesive layer in an organic EL display device. Deterioration of components. Therefore, when the organic EL display device uses the adhesive layer of the organic EL display device of the present invention and/or the polarizing film containing the adhesive layer of the adhesive layer for the organic EL display device, it can have excellent weather resistance. And long service life.

In the embodiment of the present invention, the adhesive composition for an organic EL display device of the present invention comprises: a base polymer; an ultraviolet absorber; and a pigment compound, which has the largest absorption spectrum. The absorption wavelength exists in the wavelength region of 380 to 430 nm. Here, the maximum absorption wavelength means that in the spectral absorption spectrum of the wavelength region of 300 to 460 nm, when there are a plurality of absorption maximum values, the maximum absorption wavelength of the maximum absorbance is displayed therein.

The base polymer used in the present invention is not particularly limited, and examples of the type of the adhesive composition include a rubber-based adhesive, an acrylic adhesive, a polyoxygen-based adhesive, and a urethane-based adhesive. A vinyl alkyl ether-based adhesive, a polyvinyl alcohol-based adhesive, a polyvinylpyrrolidone-based adhesive, a polypropylene amide-based adhesive, or a cellulose-based adhesive. Among these adhesives, an acrylic adhesive is preferably used because it has excellent optical transparency and exhibits adhesive properties such as appropriate adhesion, cohesiveness, and adhesion, and has excellent weather resistance, heat resistance, and the like. In the present invention, an acrylic adhesive composition containing a (meth)acrylic polymer as a base polymer is preferred.

For example, the acrylic adhesive composition preferably contains a partial polymer of a monomer component containing an alkyl (meth) acrylate and/or a (meth)acrylic polymerization obtained from the above monomer component. Matter; ultraviolet absorber; and pigment compound.

(1) Local polymer of monomer component and (meth)acrylic polymer The acrylic adhesive composition contains a partial polymer of a monomer component containing an alkyl (meth) acrylate and/or A (meth)acrylic polymer obtained from the above monomer component was obtained.

The alkyl (meth) acrylate may, for example, be an alkyl (meth) acrylate having a linear or branched alkyl group having 1 to 24 carbon atoms at the ester terminal. The alkyl (meth) acrylate may be used alone or in combination of two or more. Further, "alkyl (meth) acrylate" means an alkyl acrylate and/or an alkyl methacrylate, and (meth) of the present invention has the same meaning.

The alkyl (meth) acrylate may, for example, be a linear or branched alkyl (meth) acrylate having 1 to 24 carbon atoms. Among these, an alkyl (meth) acrylate having 1 to 9 carbon atoms is preferable, and an alkyl (meth) acrylate having 4 to 9 carbon atoms is more preferable, and carbon is most preferable. A number of 4 to 9 and having a branched alkyl (meth) acrylate. The alkyl (meth) acrylate is preferable in that it is easy to obtain a balance of adhesive properties. For example, alkyl (meth) acrylate having a carbon number of 4 to 9 may specifically be exemplified by n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl ( Methyl) acrylate, isobutyl (meth) acrylate, n-pentyl (meth) acrylate, isoamyl (meth) acrylate, isohexyl (meth) acrylate, isoheptyl ( Methyl) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, etc., which may be used alone or in combination of two or more. use.

In the present invention, the alkyl (meth) acrylate having an alkyl group having 1 to 24 carbon atoms at the ester terminal is preferably a total amount of the monofunctional monomer component relative to the (meth)acrylic polymer. 40% by weight or more, more preferably 50% by weight or more, and most preferably 60% by weight or more.

A comonomer other than the above alkyl (meth) acrylate may be contained as the monofunctional monomer component in the monomer component. The comonomer can be used as the remainder of the aforementioned alkyl (meth) acrylate in the monomer component.

The comonomer may, for example, comprise a cyclic nitrogen-containing monomer. The cyclic nitrogen-containing monomer can be used without any particular limitation, and has a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and has a cyclic group. Nitrogen structure. The cyclic nitrogen structure is preferably a cyclic nitrogen structure having a nitrogen atom in the cyclic structure. Examples of the cyclic nitrogen-containing monomer include an intrinsic amine-based vinyl monomer such as N-vinylpyrrolidone, N-vinyl-ε-caprolactam or methylvinylpyrrolidone; and vinylpyridine , vinyl piperidone, vinyl pyridinium, vinyl piperazine, vinyl pyridinium, vinyl pyrrole, vinyl imidazole, vinyl oxazole, vinyl phenylephrine, etc. Body and so on. Further, examples thereof include a (meth)acrylic monomer containing a heterocyclic ring such as a toughin ring, a piperidine ring, a pyrrolidine ring or a piperazine ring. Specific examples thereof include N-propylene hydrazinoline, N-propylene hydrazinopiperidine, N-methyl propylene hydrazine piperidine, and N-propylene decyl pyrrolidine. Among the above cyclic nitrogen-containing monomers, a decylamine-based vinyl monomer is preferred.

In the present invention, the cyclic nitrogen-containing monomer is preferably from 0.5 to 50% by weight, more preferably from 0.5 to 40% by weight, based on the total amount of the monofunctional monomer component forming the (meth)acrylic polymer. The most ideal is 0.5 to 30% by weight.

The monomer component used in the present invention may contain a hydroxyl group-containing monomer as a monofunctional monomer component. The hydroxyl group-containing monomer can be used without particular limitation, and has a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and has a hydroxyl group. Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 3-hydroxypropyl ( Methyl) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (methyl) Hydroxyalkyl (meth) acrylate such as acrylate or 12-hydroxylauryl (meth) acrylate; hydroxyalkylcycloalkane such as (4-hydroxymethylcyclohexyl)methyl (meth) acrylate (A) Base) acrylate. Further, examples thereof include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. These may be used singly or in combination. Among these, a hydroxyalkyl (meth) acrylate is suitable.

In the present invention, the hydroxyl group-containing monomer is preferably 1% by weight based on the total amount of the monofunctional monomer component forming the (meth)acrylic polymer, from the viewpoint of improving the adhesion and the cohesive force. The above is more preferably 2% by weight or more, and most preferably 3% by weight or more. On the other hand, when the amount of the hydroxyl group-containing monomer is too large, the adhesive layer becomes hard, and the adhesive force may be lowered. Further, the viscosity of the adhesive may become too high or gelatinized. The total amount of the monofunctional monomer component forming the (meth)acrylic polymer is preferably 30% by weight or less, more preferably 27% by weight or less, and most preferably 25% by weight or less.

Further, among the monomer components forming the (meth)acrylic polymer, other functional group-containing monomers may be contained as a monofunctional monomer, and examples thereof include a carboxyl group-containing monomer and a cyclic ether. Base monomer.

The carboxyl group-containing monomer can be used without particular limitation, and has a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and has a carboxyl group. Examples of the carboxyl group-containing monomer include (meth)acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, and isocrotonic acid. Etc. These may be used singly or in combination. These anhydrides can be used for itaconic acid and maleic acid. Among these, acrylic acid and methacrylic acid are preferable, and acrylic acid is particularly preferable. Further, among the monomer components used in the production of the (meth)acrylic polymer of the present invention, a carboxyl group-containing monomer may be optionally used, and a carboxyl group-containing monomer may not be used.

The monomer having a cyclic ether group can be used without any particular limitation, and has a polymerizable functional group having an unsaturated double bond such as a (meth) acrylonitrile group or a vinyl group, and A cyclic ether group such as an epoxy group or an oxycyclobutane group. Examples of the epoxy group-containing monomer include epoxypropyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate ring. Oxypropyl propyl ether and the like. Examples of the oxygen-containing cyclobutylalkyl monomer include 3-oxocyclobutanylmethyl (meth) acrylate, 3-methyl-oxycyclobutanemethyl (meth) acrylate, and 3-ethyl b. Base-oxycyclobutanemethyl (meth) acrylate, 3-butyl-oxocyclobutanylmethyl (meth) acrylate, 3-hexyl-oxocyclobutanylmethyl (methyl) Acrylate and the like. These may be used singly or in combination.

In the present invention, the carboxyl group-containing monomer and the monomer having a cyclic ether group are preferably 30% by weight or less based on the total amount of the monofunctional monomer component forming the (meth)acrylic polymer. It is 27% by weight or less, and most preferably 25% by weight or less.

In the monomer component forming the (meth)acrylic polymer of the present invention, the comonomer may, for example, be CH ₂ =C(R ¹ )COOR ² (the above R ¹ represents hydrogen or methyl, R ² An alkyl (meth) acrylate represented by a substituted alkyl group or a cyclic cycloalkyl group having 1 to 3 carbon atoms.

Here, the substituent of the alkyl group having 1 to 3 carbon atoms and substituted with R ² is preferably an aryl group having 3 to 8 carbon atoms or an aryloxy group having 3 to 8 carbon atoms. The aryl group is not limited, but a phenyl group is preferred.

Examples of such a monomer represented by CH ₂ =C(R ¹ )COOR ² include phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, and cyclohexyl (methyl). Acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, isodecyl (meth) acrylate, and the like. These may be used singly or in combination.

In the present invention, the above (meth) acrylate represented by CH ₂ =C(R ¹ )COOR ² may be used in an amount of 50 relative to the total amount of the monofunctional monomer component forming the (meth)acrylic polymer. The weight% or less is preferably 45% by weight or less, more preferably 40% by weight or less, and most preferably 35% by weight or less.

Other comonomers can also be used: vinyl acetate, vinyl propionate, styrene, α-methylstyrene; polyethylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate, (meth)acrylic acid a diol-based acrylate monomer such as methoxyethylene glycol or (meth)acrylic acid methoxypolypropylene glycol; tetrahydrofurfuryl (meth) acrylate, fluorinated (meth) acrylate, polyfluorene ( Acrylate-based monomer such as methyl acrylate or 2-methoxyethyl acrylate; amide-containing monomer, amine-containing monomer, imine-containing monomer, N-propylene hydrazino , vinyl ether monomer and the like. Further, as the comonomer, a monomer having a cyclic structure such as terpene (meth) acrylate or dicyclopentanyl (meth) acrylate can be used.

Further, examples thereof include a decane-based monomer containing a ruthenium atom. Examples of the decane-based monomer include 3-propenyloxypropyltriethoxydecane, vinyltrimethoxydecane, vinyltriethoxydecane, 4-vinylbutyltrimethoxydecane, and 4- Vinyl butyl triethoxy decane, 8-vinyl octyl trimethoxy decane, 8-vinyl octyl triethoxy decane, 10-methyl propylene decyl decyl trimethoxy decane, 10- Propylene methoxy decyl trimethoxy decane, 10-methyl propylene decyl decyl triethoxy decane, 10-propylene decyl decyl triethoxy decane, and the like.

In addition to the monofunctional monomer exemplified above, the monomer component forming the (meth)acrylic polymer of the present invention may contain a polyfunctional monomer as needed in order to adjust the cohesive force of the adhesive.

The polyfunctional monomer is a monomer having at least two polymerizable functional groups, and the polymerizable functional group has an unsaturated double bond such as a (meth)acryl fluorenyl group or a vinyl group, and examples thereof include, for example: Poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, new Pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2-ethanediol di(meth)acrylate, 1,6-hexanediol di(methyl) Polyols such as acrylate, 1,12-dodecanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethanetri(meth)acrylate, and the like Esterified (meth)acrylic acid; allyl (meth) acrylate, vinyl (meth) acrylate, divinyl benzene, epoxy acrylate, polyester acrylate, urethane acrylate , butyl di(meth) acrylate, hexyl di (meth) acrylate, and the like. Among these, trimethylolpropane tri(meth)acrylate, hexanediol di(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be suitably used. The polyfunctional monomer may be used alone or in combination of two or more.

The amount of the polyfunctional monomer to be used varies depending on the molecular weight, the number of functional groups, and the like, but it is preferably used in an amount of 3 parts by weight or less, more preferably 2 parts by weight, based on 100 parts by total of the monofunctional monomer. Hereinafter, it is most preferably 1 part by weight or less. Further, the lower limit is not particularly limited, but is preferably 0 parts by weight or more, more preferably 0.001 parts by weight or more. By using the amount of the polyfunctional monomer within the above range, the adhesion can be improved.

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

Further, in the present invention, a partial polymer of the above monomer component may be suitably used.

When the (meth)acrylic polymer is produced by radical polymerization, a polymerization initiator, a chain transfer agent, an emulsifier or the like used in the radical polymerization may be appropriately added to the monomer component to carry out polymerization. The polymerization initiator, the chain transfer agent, the emulsifier, and the like used in the radical polymerization are not particularly limited, and can be appropriately selected and used. Further, the weight average molecular weight of the (meth)acrylic polymer can be controlled by the amount of the polymerization initiator, the chain transfer agent used, and the reaction conditions, and the amount of use thereof can be appropriately adjusted depending on the types thereof.

For example, in solution polymerization or the like, for example, ethyl acetate, toluene or the like can be used as the polymerization solvent. As a specific solution polymerization example, the reaction is carried out by adding a polymerization initiator under an inert gas stream such as nitrogen, usually by a reaction condition of 50 to 70 ° C for 5 to 30 hours.

Examples of the thermal polymerization initiator used in the solution polymerization and the like include 2,2'-azobisisobutyronitrile, 2,2'-azobis-2-methylbutyronitrile, and 2,2'-azo. Di(2-methylpropionic acid) dimethyl ester, 4,4'-azobis-4-cyanovaleric acid, azobisisoprene, 2,2'-azobis(2-amidinopropane) Dihydrochloride, 2,2'-azobis[2-(5-methyl-2-imidazolin-2-yl)propane] dihydrochloride, 2,2'-azobis(2-A Diethyl sulfonate, 2,2'-azobis(N,N'-dimethyleneisobutylphosphonium), 2,2'-azobis[N-(2-carboxyethyl) An azo initiator such as -2-methylpropionamidine hydrate (VA-057, manufactured by Wako Pure Chemical Industries, Ltd.); persulfate such as potassium persulfate or ammonium persulfate, and di(2-ethyl) Hexyl)peroxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, di-sec-butylperoxydicarbonate, t-butylperoxy neodecanoate, t- Hexylperoxytrimethylacetate, t-butylperoxytrimethylacetate, dilauroyl peroxide, di-n-octyl peroxide, 1,1,3,3-tetra Butyl peroxy-2-ethylhexanoate, bis(4-methylbenzylidene) peroxide, benzhydryl peroxide, t- a peroxide-based initiator such as butylperoxy isobutyrate, 1,1-di(t-hexylperoxy)cyclohexane, t-butyl hydroperoxide or hydrogen peroxide; persulfate and The combination of a sodium hydrogen sulfite, a combination of a peroxide and sodium ascorbate, and the like, a combination of a peroxide and a redox initiator of a reducing agent, etc., is not limited thereto.

The polymerization initiator may be used singly or in combination of two or more kinds, but it is preferably 1 part by weight or less, more preferably 0.005 to 1 part by weight, per 100 parts by weight based on the total amount of the monomer components. The most desirable is 0.02 to 0.5 parts by weight.

Further, when 2,2'-azobisisobutyronitrile is used as the polymerization initiator, the polymerization initiator is preferably used in an amount of 0.2 part by weight or less based on 100 parts by weight of the total of the monomer components, more preferably It is made into 0.06~0.2 parts by weight.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, indole acetic acid, 2-indole ethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-diindole-1- Propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds, and the total content is 0.3 parts by weight or less based on 100 parts by weight of the total of the monomer components.

Further, examples of the emulsifier used in the emulsion polymerization include sodium lauryl sulfate, ammonium lauryl sulfate, sodium dodecylbenzenesulfonate, ammonium polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkylphenyl ether sulfate. An anionic emulsifier such as sodium; a nonionic emulsifier such as a polyoxyethylene alkyl ether, a polyoxyethylene alkylphenyl ether, a polyoxyethylene fatty acid ester, or a polyoxyethylene-polyoxypropylene block polymer. These emulsifiers may be used singly or in combination of two or more.

Further, as the reactive emulsifier, an emulsifier which has introduced a radical polymerizable functional group such as a propenyl group or an allyl ether group includes, for example, AQUALON HS-10, HS-20, KH-10, BC-05. BC-10, BC-20 (all of which are manufactured by First Industrial Pharmaceutical Co., Ltd.), ADEKA REASOAP SE10N (made by ADEKA), and the like. The amount of the emulsifier used is preferably 5 parts by weight or less based on 100 parts by weight of the total of the monomer components.

In addition, when the (meth)acrylic polymer is produced by radiation polymerization, it can be produced by irradiating the monomer component with radiation such as an electron beam or ultraviolet rays (UV). Among these, ultraviolet polymerization is preferred. Hereinafter, ultraviolet polymerization which is an ideal aspect in radiation polymerization will be described.

When ultraviolet polymerization is carried out, it is preferred to contain a photopolymerization initiator in the monomer component because the polymerization time can be shortened. Therefore, when ultraviolet polymerization is carried out, for example, it is preferable to form the ultraviolet curable acrylic pressure-sensitive adhesive composition by ultraviolet polymerization, and the ultraviolet-curable acrylic pressure-sensitive adhesive composition contains the aforementioned alkyl group ( a monomer component of a methyl acrylate and/or a partial polymer of the monomer component, a UV absorber, a dye compound, and a photopolymerization initiator. The adhesive layer formed by ultraviolet-polymerizing the ultraviolet curable acrylic pressure-sensitive adhesive composition can also form a thick-walled adhesive layer of 150 μm or more and can form a thick adhesive layer.

The photopolymerization initiator is not particularly limited, but it is preferred to include a photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more. When an ultraviolet absorber or a dye compound is contained in the adhesive composition, when ultraviolet polymerization is carried out, ultraviolet rays are absorbed by the ultraviolet absorber or the dye compound, and polymerization cannot be sufficiently performed. However, the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is preferable because it can sufficiently polymerize even if it contains an ultraviolet absorber or a dye compound.

The photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may, for example, be bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (Irgacure 819, manufactured by BASF), 2 4,6-trimethylbenzimidyl-diphenyl-phosphine oxide (LUCIRIN TPO, manufactured by BASF).

The photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more may be used singly or in combination of two or more.

Further, the amount of the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is not particularly limited, but it is preferably less than the amount of the ultraviolet absorber or the dye compound to be described later, preferably with respect to formation. The monofunctional monomer component of the (meth)acrylic polymer is used in an amount of 0.005 to 1 part by weight, more preferably 0.02 to 0.8 part by weight. By adding the amount of the photopolymerization initiator (A) to the above range, ultraviolet polymerization can be sufficiently carried out, which is preferable.

Further, the photopolymerization initiator may contain a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm. The photopolymerization initiator (B) generates radicals by ultraviolet rays and starts photopolymerization. If it is a photopolymerization initiator having an absorption band at a wavelength of less than 400 nm, there is no particular limitation, and a general use can be suitably used. Any of the photopolymerization initiators used. For example, a benzoin ether photopolymerization initiator, an acetophenone photopolymerization initiator, an α-keto alcohol photopolymerization initiator, a photoactive oxime photopolymerization initiator, and a benzoin light can be used. Photopolymerization initiator, diphenylethylenedione photopolymerization initiator, diphenyl ketone photopolymerization initiator, ketal photopolymerization initiator, thioxanthone photopolymerization A starting agent, a mercaptophosphine oxide photopolymerization initiator, and the like.

Specific examples of the benzoin ether photopolymerization initiator include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2- Diphenylethane-1-one, anisole methyl ether, and the like.

Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, and 1-hydroxycyclohexyl phenyl ketone. , 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, and the like.

The α-keto alcohol-based photopolymerization initiator may, for example, be 2-methyl-2-hydroxyethyl phenyl ketone or 1-[4-(2-hydroxyethyl)phenyl]-2-hydroxy-2- Methylpropan-1-one and the like.

The photoactive oxime-based photopolymerization initiator may, for example, be 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)-ruthenium or the like.

Examples of the benzoin-based photopolymerization initiator include benzoin and the like.

Examples of the diphenylethylenedione-based photopolymerization initiator include diphenylethylenedione and the like.

The diphenyl ketone photopolymerization initiator includes, for example, diphenyl ketone, benzamidine benzoic acid, 3,3'-dimethyl-4-methoxydiphenyl ketone, polyethylene diphenyl Ketone, α-hydroxycyclohexyl phenyl ketone, and the like.

The ketal-based photopolymerization initiator includes diphenylethylenedione dimethyl ketal and the like.

The 9-oxosulfuric-based photopolymerization initiator includes, for example, 9-oxosulfuron, 2-chloro-9-oxosulfanium, 2-methyl-9-oxosulfanium, 2,4- Dimethyl-9-oxosulfide, isopropyl-9-oxosulfide, 2,4-dichloro-9-oxosulfanium, 2,4-diethyl-9-oxosulfide , 2,4-diisopropyl-9-oxosulfuronium, dodecyl-9-oxosulfuronium, and the like.

The mercaptophosphine oxide photopolymerization initiator includes, for example, 2,4,6-trimethylbenzylidene-diphenyl-phosphine oxide, bis(2,4,6-trimethylbenzene) Mercapto)-phenylphosphine oxide and the like.

The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm may be used singly or in combination of two or more. The photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm can be added within the range which does not impair the effects of the present invention, but is preferably added in an amount relative to the monofunctional monomer component forming the (meth)acrylic polymer. 100 parts by weight is 0.005 to 0.5 parts by weight, more preferably 0.02 to 0.2 parts by weight.

In the present invention, when the monomer component is subjected to ultraviolet polymerization, it is preferred to add a photopolymerization initiator (B) having an absorption band at a wavelength of less than 400 nm to the monomer component, and to partially polymerize upon irradiation with ultraviolet rays. The photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more, the ultraviolet absorber, and the dye compound are added to the local polymer (prepolymer composition) of the monomer component, and ultraviolet polymerization is carried out. When the photopolymerization initiator (A) having an absorption band at a wavelength of 400 nm or more is added to the local polymer (prepolymer composition) of the monomer component which is partially polymerized by ultraviolet irradiation, the photopolymerization is preferably carried out. The initiator is added after being dissolved in the monomer.

(2) Ultraviolet Absorber The ultraviolet absorber is not particularly limited, and examples thereof include a trivalent ultraviolet absorber, a benzotriazole ultraviolet absorber, a diphenylketone ultraviolet absorber, and oxygen. A bisdiphenyl ketone-based ultraviolet absorber, a salicylate-based ultraviolet absorber, a cyanoacrylate-based ultraviolet absorber, and the like. These may be used alone or in combination of two or more. Among these, a three-dimensional ultraviolet absorber and a benzotriazole-based ultraviolet absorber are preferable, and it is preferably selected from a three-dimensional ultraviolet absorber having two or less hydroxyl groups in one molecule and one At least one ultraviolet absorber in the group consisting of a benzotriazole-based ultraviolet absorber having a benzotriazole skeleton in the molecule has good solubility in a monomer for forming an acrylic adhesive composition, Moreover, the ultraviolet absorbing ability at a wavelength of around 380 nm is high.

Specific examples of the trivalent ultraviolet absorber having two or less hydroxyl groups in one molecule include, for example, 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6 -(4-methoxyphenyl)-1,3,5-tris(Tinosorb S, manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2 , 4-dibutoxyphenyl)-1,3,5-trivalent (TINUVIN 460, manufactured by BASF), 2-(4,6-bis(2,4-dimethylphenyl)-1,3, a reaction product of 5-(3-methyl-2-yl)-5-hydroxyphenyl group and [(C10-C16 (mainly C12-C13) alkoxy)methyl]oxirane (TINUVIN400, manufactured by BASF), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-trimethyl-2-yl]-5-[3-(dodecyloxy)-2-hydroxyl Propyl]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-trivalent and (2-B Reaction product of hexyl)-dehydroglycerate (TINUVIN405, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-tri-2-yl)-5[(hexyl) Oxy]-phenol (TINUVIN 1577, manufactured by BASF), 2-(4,6-diphenyl-1,3,5-trimethyl-2-yl)-5-[2-(2-ethylhexyloxy) Ethyl]-phenol (ADK STAB LA46, manufactured by Adeco (ADEKA)), 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6- Bis(4-phenylphenyl)-1,3,5-three (TINUVIN479, BASF Corporation) and the like.

Further, a benzotriazole-based ultraviolet absorber having a benzotriazole skeleton in one molecule may, for example, be 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1- Phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN928, manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl)-2H- Benzotriazole (TINUVIN PS, manufactured by BASF), phenylpropionic acid and 3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-hydroxyl (C7) Esterified product of -9 side chain and linear alkyl group (TINUVIN 384-2, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-) Phenylethyl)phenol (TINUVIN900, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1 ,3,3-tetramethylbutyl)phenol (TINUVIN928, manufactured by BASF), methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyl Reaction product of phenyl)propionate/polyethylene glycol 300 (TINUVIN1130, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P, manufactured by BASF), 2(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN234, manufactured by BASF), 2-[5-chloro(2H)- Benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN326, manufactured by BASF), 2-(2H-benzotriene) -2-yl)-4,6-di-tert-pentylphenol (TINUVIN328, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3- Tetramethylbutyl)phenol (TINUVIN329, manufactured by BASF), methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate Reaction product with polyethylene glycol 300 (TINUVIN213, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (TINUVIN571, manufactured by BASF) , 2-[2-hydroxy-3-(3,4,5,6-tetrahydroindenylene-methyl)-5-methylphenyl]benzotriazole (Sumisorb 250, Sumitomo Chemical Industries Co., Ltd.) System) and so on.

In addition, examples of the diphenylketone-based ultraviolet absorber (diphenylketone-based compound) and the oxydiphenylketone-based ultraviolet absorber (oxydiphenylketone-based compound) include a 2,4-dihydroxy group. Diphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone, 2-hydroxy-4-methoxydiphenyl ketone-5-sulfonic acid (anhydride and trihydrate), 2-hydroxy-4 - Octyloxydiphenyl ketone, 4-dodecyloxy-2-hydroxydiphenyl ketone, 4-benzyloxy-2-hydroxydiphenyl ketone, 2,2',4,4'-four Hydroxydiphenyl ketone, 2,2'-dihydroxy-4,4-dimethoxydiphenyl ketone, and the like.

In addition, examples of the salicylate-based ultraviolet absorber (salicylate-based compound) include phenyl-2-propenyloxybenzoate and phenyl-2-propenyloxy-3-methyl. Benzobenzoate, phenyl-2-propenyloxy-4-methylbenzoate, phenyl-2-propenyloxy-5-methylbenzoate, phenyl-2-propene醯oxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4 Benzobenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl 2-hydroxy-3-methoxybenzoate, 2,4-di-tert-butylphenyl -3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN 120, manufactured by BASF).

Examples of the cyanoacrylate ultraviolet absorber (cyanoacrylate compound) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, and alkoxyalkyl-2- Cyanoacrylate, alkenyl-2-cyanoacrylate, alkynyl-2-cyanoacrylate, and the like.

The maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is preferably in the wavelength region of 300 to 400 nm, and more preferably in the wavelength region of 320 to 380 nm. The method for measuring the maximum absorption wavelength is the same as the method for measuring the dye-based compound described later.

The ultraviolet absorber may be used singly or in combination of two or more kinds, and the entire content is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth)acrylic polymer. More preferably, it is 0.5 to 3 parts by weight. By setting the amount of the ultraviolet absorber to be in the above range, the ultraviolet absorbing function of the pressure-sensitive adhesive layer can be sufficiently exhibited, and it is preferable that the polymerization is not inhibited during the ultraviolet ray polymerization.

(3) Pigment Compound The dye compound to be used in the present invention is not particularly limited as long as it is a compound having a maximum absorption wavelength of the absorption spectrum in the wavelength region of 380 to 430 nm. The maximum absorption wavelength of the absorption spectrum of the pigment compound is preferably present in the wavelength region of 380 to 420 nm. In the present invention, by using such a dye compound in combination with the ultraviolet absorber, light in a region (380 nm to 430 nm) which does not affect the light emission of the organic EL element can be sufficiently absorbed, and the light-emitting region of the organic EL element ( It is sufficiently transmitted through the side closer to the long wavelength than 430 nm, and as a result, deterioration of the organic EL element due to natural light can be suppressed. Further, the dye compound is not particularly limited as long as it has the above-mentioned wavelength characteristics, and is preferably a material which does not have fluorescence and phosphorescence (photoluminescence) which does not inhibit the display property of the organic EL element.

Further, the half value width of the dye compound is not particularly limited, but is preferably 80 nm or less, more preferably 5 to 70 nm, and most preferably 10 to 60 nm. When the half value of the dye compound is in the above range, it is possible to sufficiently absorb light that does not affect the region where the organic EL element emits light, and it is possible to control the light which is closer to the longer wavelength side than 430 nm to be sufficiently transmitted. . In addition, the method of measuring the half value width uses the method described below. <Method for Measuring Half Value Width> The half value width of the dye compound is obtained by using an ultraviolet-visible spectrophotometer (U-4100, manufactured by High-Tech Science Co., Ltd.), and the pigment compound is obtained by the following conditions. The transmission absorption spectrum of the solution was measured. The concentration is adjusted so that the absorbance at the maximum absorption wavelength constitutes a fractional spectrum measured by 1.0, and the wavelength interval (full width at half maximum) between two points constituting 50% of the peak is made the half value width of the dye compound. (Measurement conditions) Solvent: Toluene or chloroform Groove: Quartz tank Optical path length: 10 mm

The dye compound is not particularly limited as long as it is a compound having a maximum absorption wavelength of the absorption spectrum in the wavelength region of 380 to 430 nm. The above-mentioned coloring matter compound is, for example, an organic dye compound or an inorganic dye compound, and it is preferably an organic system from the viewpoint of maintaining dispersibility and transparency in a resin component such as a base polymer. Pigment compound.

Examples of the organic dye compound include a methylimine compound, an anthraquinone compound, a cinnamic acid compound, a pyrimidine compound, and a porphyrin compound.

A commercially available product can be suitably used as the organic dye compound. Specifically, the above-mentioned oxime compound can be, for example, BONASORB UA3911 (trade name, maximum absorption wavelength of absorption spectrum: 398 nm, half value width: 48 nm, Oriental (ORIENT) Chemical industry (stock) system, BONASORB UA3912 (trade name, absorption spectrum maximum absorption wavelength: 386nm, half-value width: 53nm, Oriental (ORIENT) chemical industry (stock)), cinnamic acid compounds can be listed, for example: SOM -5-0106 (trade name, maximum absorption wavelength of absorption spectrum: 416 nm, half-value width: 50 nm, manufactured by ORIENT Chemical Industry Co., Ltd.), and porphyrin-based compound may be, for example, FDB-001 (trade name, The maximum absorption wavelength of the absorption spectrum: 420 nm, half value width: 14 nm, manufactured by Yamada Chemical Industry Co., Ltd., and the like.

The above-mentioned dye compounds may be used singly or in combination of two or more kinds, and the total content thereof is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the monofunctional monomer component forming the (meth)acrylic polymer. More preferably, it is 0.02 to 5 parts by weight. By setting the amount of the dye compound to be in the above range, light which does not affect the light-emitting region of the organic EL element can be sufficiently absorbed, and the organic layer can be suppressed by using the adhesive layer formed of the adhesive composition. The deterioration of the EL element is therefore preferable.

(4) Decane coupling agent Further, a decane coupling agent may be contained in the adhesive composition of the present invention. The blending amount of the decane coupling agent is preferably 1 part by weight or less, more preferably 0.01 to 1 part by weight, per 100 parts by weight of the monofunctional monomer component forming the (meth)acrylic polymer, and most preferably 0.02 to 0.6 parts by weight.

The aforementioned decane coupling agent may, for example, be 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropyltriethoxydecane, 3-glycidoxypropylmethyldiethyl Epoxy decane-containing coupling agent such as oxydecane, 2-(3,4 epoxycyclohexyl)ethyltrimethoxydecane; 3-aminopropyltrimethoxydecane, N-2-(aminoethyl)- 3-Aminopropylmethyldimethoxydecane, 3-triethoxyindolyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-γ-aminopropyltrimethoxy An amino group-containing decane coupling agent such as decane; a (meth) acrylonitrile-based decane coupling agent such as 3-propenyloxypropyltrimethoxydecane or 3-methylpropenyloxypropyltriethoxydecane; An isocyanate-based decane coupling agent such as 3-isocyanate propyl triethoxy decane.

(5) Crosslinking agent The adhesive composition of the present invention may contain a crosslinking agent. The crosslinking agent includes an isocyanate crosslinking agent, an epoxy crosslinking agent, a polyfluorene crosslinking agent, an oxazoline crosslinking agent, an aziridine crosslinking agent, and a decane crosslinking agent. A crosslinking agent such as an alkyl etherified melamine crosslinking agent, a metal chelate crosslinking agent, or a peroxide. The crosslinking agents may be used alone or in combination of two or more. Among these, an isocyanate crosslinking agent is preferably used.

The above-mentioned crosslinking agent may be used singly or in combination of two or more kinds, and the total content thereof is preferably 5 parts by weight or less based on 100 parts by weight of the monofunctional monomer component forming the (meth)acrylic polymer. More preferably, it is 0.01 to 5 parts by weight, more preferably 0.01 to 4 parts by weight, particularly preferably 0.02 to 3 parts by weight.

The isocyanate-based crosslinking agent is a compound having two or more isocyanate groups (including an isocyanate-regenerating functional group for temporarily protecting an isocyanate group by a blocking agent or a polymerization) in one molecule. Examples of the isocyanate crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

More specifically, examples thereof include lower aliphatic polyisocyanates such as butyl diisocyanate and hexamethylene diisocyanate; and alicyclic rings such as cyclopentyl diisocyanate, cyclohexyl diisocyanate, and isophorone diisocyanate; Group of isocyanates; aromatic diisocyanates such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, decyl diisocyanate, polymethylene polyphenyl isocyanate; trimethylolpropane / Toluene diisocyanate trimer adduct (trade name: CORONATE L, manufactured by Japan Polyurethane Industry Co., Ltd.), trimethylolpropane / hexamethylene diisocyanate trimer adduct (commodity) Name: CORONATE HL, manufactured by Japan Polyurethane Industry Co., Ltd.), isocyanurate body of hexamethylene diisocyanate (trade name: CORONATE HX, Japan Polyurethane Industry Co., Ltd.) Isocyanate adduct, trimethylolpropane adduct of mercapto diisocyanate (trade name: D110N, manufactured by Mitsui Chemicals Co., Ltd.), trimethylolpropane addition of hexamethylene diisocyanate (product name: D160N, Mitsui Chemicals Co., Ltd.) Polyether polyisocyanate, polyester polyisocyanate, and these adducts with various polyols; polyisocyanates which have been polyfunctionalized by isocyanurate bonds, biuret bonds, ureacarboxylate bonds, etc. .

(6) Other Additives In the adhesive composition of the present invention, in addition to the above-mentioned components, appropriate additives may be contained depending on the use. For example, a tackifier (for example, a solid, semi-solid or liquid adhesive at room temperature composed of rosin derivative resin, polyterpene resin, petroleum resin, oil-soluble phenol resin, etc.) may be mentioned. Fillers such as hollow glass balloons; plasticizers; anti-aging agents; light stabilizers (HALS); antioxidants, etc.

In the present invention, the adhesive composition is preferably adjusted to have a viscosity suitable for application to a substrate or the like. For example, the viscosity adjustment of the adhesive composition is carried out by adding various polymers such as a tackifier or a polyfunctional monomer, or by partially polymerizing a monomer component in the adhesive composition. Further, the partial polymerization may be carried out before adding various polymers such as a tackifier or a polyfunctional monomer, or may be carried out later. The viscosity of the above-mentioned adhesive composition varies depending on the amount of the additive or the like. Therefore, the polymerization rate when the monomer component in the adhesive composition is partially polymerized cannot be determined singly, but the target is preferably 20% or less, which is more desirable. It is 3~20%, and the most ideal is 5~15%. If it is more than 20%, the viscosity becomes too high, and therefore, it is difficult to apply it to a substrate.

2. Adhesive layer for organic EL display device The adhesive layer for an organic EL display device of the present invention is formed of the above-described adhesive composition for an organic EL display device.

The method of forming the adhesive layer is not particularly limited and can be formed by a method generally used in the art. Specifically, the adhesive composition may be applied to at least one surface of the substrate, and the coating film formed of the adhesive composition may be dried or formed by irradiating an active energy ray such as ultraviolet rays.

The substrate is not particularly limited. For example, various substrates such as a release film and a transparent resin film substrate, or a polarizing film to be described later, may be suitably used as the substrate.

The constituent material of the release film may, for example, be a resin film such as polyethylene, polypropylene, polyethylene terephthalate or polyester film; or a porous material such as paper, cloth or nonwoven fabric; net, foamed sheet or metal; A resin film is suitably used from the viewpoint of excellent surface smoothness, such as a foil and a suitable sheet such as a laminate.

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

The thickness of the release film is usually 5 to 200 μm, preferably 5 to 100 μm. If necessary, the release film may be subjected to mold release and antifouling treatment using a polyfluorene-based, fluorine-based, long-chain alkyl or fatty acid amide-based release agent, bismuth powder, or the like. Antistatic treatment such as kneading type, vapor deposition type, etc. In particular, since the surface of the release film is appropriately subjected to a release treatment such as polyoxymethylene treatment, long-chain alkyl treatment, or fluorine treatment, the peeling property from the pressure-sensitive adhesive layer can be further improved.

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

The thickness of the film substrate is preferably 15 to 200 μm, more preferably 25 to 188 μm.

The method of applying the above adhesive composition to the above substrate may be: roll coating, contact roll coating, gravure coating, reverse coating, rolling brush coating, spray coating, immersion roller coating, bar coating, A well-known method such as blade coating, pneumatic blade coating, curtain coating, lip coating, and die coating machine is not particularly limited.

When the coating film formed of the above-mentioned adhesive composition is dried, the drying conditions (temperature, time) are not particularly limited, and can be appropriately set in accordance with the composition, concentration, and the like of the adhesive composition. For example, 60 to 170 ° C, preferably 60 to 150 ° C, and 1 to 60 minutes, preferably 2 to 30 minutes.

When the adhesive composition is an ultraviolet curable adhesive composition and the coating film formed of the ultraviolet curable adhesive composition is irradiated with ultraviolet rays, the ultraviolet illuminance to be irradiated is preferably 5 mW/cm ² or more. . When the ultraviolet illuminance is less than 5 mW/cm ² , the polymerization reaction time is prolonged, and productivity is sometimes poor. Further, the ultraviolet illuminance is preferably 200 mW/cm ² or less. When the ultraviolet illuminance is more than 200 mW/cm ² , since the photopolymerization initiator is consumed violently, the molecular weight of the polymer may be lowered, and in particular, the holding power at a high temperature may be lowered. Further, the cumulative amount of ultraviolet light is preferably from 100 mJ/cm ² to 5000 mJ/cm ² .

The ultraviolet lamp used in the present invention is not particularly limited, but an LED lamp is preferable. Compared with other ultraviolet lamps, LED lamps are low-heating lamps, and therefore, the temperature during polymerization of the adhesive layer can be suppressed. Therefore, the low molecular weight of the polymer can be prevented, and the cohesive force of the adhesive layer can be prevented from being lowered, and the holding force at a high temperature at the time of forming the adhesive sheet can be improved. Further, a plurality of ultraviolet lamps may be combined. Further, ultraviolet rays may be intermittently irradiated, and a light-emitting time for irradiating ultraviolet rays and a light-out time for not irradiating ultraviolet rays may be provided.

In the present invention, the final polymerization rate of the monomer component in the ultraviolet curable adhesive composition is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

In the present invention, the peak wavelength of the ultraviolet ray irradiated to the ultraviolet curable adhesive composition is preferably in the range of 200 to 500 nm, and more preferably in the range of 300 to 450 nm. When the peak wavelength of the ultraviolet light is more than 500 nm, the photopolymerization initiator cannot be decomposed, and the polymerization reaction may not start. Further, when the peak wavelength of the ultraviolet light is less than 200 nm, the polymer chain is cut, and the subsequent properties may be lowered.

The reaction is inhibited by oxygen in the air. Therefore, in order to isolate oxygen, it is preferable to form a release film or the like on a coating film formed of an ultraviolet curable acrylic adhesive composition, or to carry out photopolymerization under a nitrogen atmosphere. . The release film may, for example, be a release film as described above. Further, when a release film is used, the release film can be directly used as a separator of a polarizing film with an adhesive layer.

Further, when the ultraviolet curable adhesive composition used in the present invention contains a photopolymerization initiator (B), it is preferred to include the photopolymerization initiator (B) (sometimes referred to as "pre-addition polymerization" The composition of the initiator () and the monomer component containing the alkyl (meth) acrylate is irradiated with ultraviolet rays to form a local polymer of the monomer component, and ultraviolet absorbing is added to the local polymer of the monomer component. A photopolymerization initiator (A) (sometimes referred to as "post-addition polymerization initiator") having an absorption band at a wavelength of 400 nm or more, and an ultraviolet curable adhesive composition. The polymerization rate of the local polymer is preferably 20% or less, more preferably 3 to 20%, and most preferably 5 to 15%. The irradiation conditions of ultraviolet rays are as described above.

As described above, when the adhesive layer is formed of the ultraviolet curable adhesive composition containing the photopolymerization initiator (B), the polymerization rate of the monomer component can be improved by using the polymerization in the two-stage as described above, and the polymerization rate can be improved. The UV absorbing function of the final adhesive layer.

The thickness of the adhesive layer is preferably 12 μm or more, more preferably 50 μm or more, more preferably 100 μm or more, and particularly preferably 150 μm or more, from the viewpoint of ensuring absorption of light having a wavelength of less than 430 nm. The upper limit of the thickness of the adhesive layer is not particularly limited, but it is preferably 1 mm or less. When the thickness of the adhesive layer is more than 1 mm, the transmission of ultraviolet rays is difficult, and the polymerization of the monomer component is time-consuming. In addition, the processability or the winding and transportability in the step may cause problems, and the productivity may be poor. ideal.

The gel fraction of the adhesive layer of the present invention is not particularly limited, but is preferably 35% or more, more preferably 50% or more, still more preferably 75% or more, and particularly preferably 85% or more. When the gel fraction of the adhesive layer is small, the coagulation force is poor, and sometimes workability or handleability may cause problems.

The haze value of the adhesive layer measured at a thickness of 25 μm is preferably 2% or less, more preferably 0 to 1.5%, and most preferably 0 to 1%. By setting the haze to the above range, the adhesive layer has high transparency, which is preferable.

The average transmittance of the adhesive layer at a wavelength of 300 to 400 nm is preferably 5% or less, more preferably 2% or less. When the transmittance of the pressure-sensitive adhesive layer is in the above range, light that does not affect the light-emitting region of the organic EL element can be sufficiently absorbed, and deterioration of the organic EL element can be suppressed.

The average transmittance of the adhesive layer having a wavelength of 450 to 500 nm is preferably 70% or more, more preferably 75% or more, and the average transmittance of the wavelength of 500 to 780 nm is preferably 80% or more, and more preferably 85% or more. . When the transmittance of the adhesive layer is in the above range, light can be sufficiently transmitted in the light-emitting region (close to the long wavelength side of 430 nm) of the organic EL element, and the organic EL display device using the adhesive layer can sufficiently emit light.

Further, the average transmittance of the adhesive layer having a wavelength of 400 to 430 nm or less can be designed in accordance with characteristics required for an organic EL display device. For example, when the light of the region which does not affect the light emission of the organic EL element is sufficiently absorbed and the deterioration of the organic EL element is suppressed and protected, the wavelength of the adhesive layer is 400 to 430 nm or less. The transmittance is preferably 30% or less, more preferably 20% or less. On the other hand, when the organic EL element is protected from ultraviolet light and the coloring of the organic EL element is suppressed, the average transmittance of the adhesive layer having a wavelength of 400 to 430 nm or less is preferably more than 30% and 75% or less. It is desirable to be greater than 30% and less than 65%.

Here, the "average transmittance of a wavelength of 300 to 400 nm" means an average value of the measured transmittance after measuring the transmittance at a pitch of 1 nm in a region of a wavelength of 300 to 400 nm. The average transmittance in the other wavelength regions is also the same.

The adhesive layer of the present invention has the above-described transmittance, whereby light in a region that does not affect the light emission of the organic EL element can be sufficiently absorbed, and the light-emitting region of the organic EL element (close to the long wavelength side from 430 nm) can be sufficiently obtained. The ground is transmitted, and deterioration of the organic EL element due to natural light can be suppressed.

When the adhesive layer is exposed, the adhesive layer can be protected by the release film until it is practical.

3. Polarizing film with an adhesive layer for an organic EL display device The polarizing film for an adhesive layer for an organic EL display device of the present invention comprises: a polarizing film; and the above-mentioned adhesive layer for an organic EL display device.

The above adhesive layer can be suitably used for the adhesive layer for an organic EL display device. Further, when the adhesive layer is formed on a substrate other than the polarizing film, the adhesive layer can be bonded and transferred to the polarizing film. Further, the release film can be directly used as a separator of a polarizing film with an adhesive layer, which can be simplified on the step surface.

The polarizing film is not particularly limited, and examples thereof include a polarizing member and a transparent protective film on at least one side of the polarizing member.

(1) Polarizer The polarizer is not particularly limited, and various polarizers can be used. Examples of the polarizer include a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, and ethylene. The vinyl acetate copolymer is a hydrophilic polymer film such as a partially saponified film, which adsorbs a dichroic substance of iodine or a dichroic dye and is uniaxially stretched; a dehydrated material of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride A polyene oriented film or the like. Among these, a polarizing member composed of a polyvinyl alcohol-based film and a dichroic material such as iodine is suitable. The thickness of the polarizers is not particularly limited, but is generally 5 to 80 μm.

A polarizing member which dyes a polyvinyl alcohol-based film with iodine and uniaxially stretches can be produced, for example, by immersing polyvinyl alcohol in an aqueous solution of iodine for dyeing and extending it to 3 to 7 times the original length. . If necessary, it may be immersed in an aqueous solution containing potassium iodide such as boric acid, zinc sulfate or zinc chloride. Further, if necessary, the polyvinyl alcohol-based film may be immersed in water and washed with water before dyeing. By washing the polyvinyl alcohol-based film with water, it is possible to prevent unevenness in dyeing unevenness by swelling the polyvinyl alcohol-based film in addition to the stain or anti-caking agent on the surface of the polyvinyl alcohol-based film. . The extension may be carried out after dyeing with iodine, or may be extended while dyeing, or may be dyed with iodine after stretching. The extension can also be carried out in an aqueous solution or a water bath such as boric acid or potassium iodide.

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

Examples of the thin polarizing member include, for example, Japanese Laid-Open Patent Publication No. 51-069644 or JP-A-2000-338329, International Publication No. 2010/100917, International Publication No. 2010/100917, or Japanese Patent No. 4,751,481. The thin polarizing film described in Japanese Laid-Open Patent Publication No. 2012-073563. The thin polarizing film can be obtained by a method comprising the steps of: extending a layer of a polyvinyl alcohol-based resin (hereinafter also referred to as a PVA-based resin) and a resin substrate for stretching in a layered state; and a dyeing step . According to this production method, even if the PVA-based resin layer is thin, it can be stretched by supporting the resin substrate for stretching without causing problems such as cracking due to stretching.

In the method of forming the thin polarizing film including the step of stretching in the state of the laminated body and the dyeing step, it is preferable that the polarizing film can be extended to a high magnification to improve the polarizing performance. The method disclosed in the specification of the publication No. 2010/100917, the specification of the International Publication No. 2010/100917, or the specification of Japanese Patent No. 4,751, 481, or JP-A-2012-073563, which is produced by a method comprising the step of stretching in an aqueous solution of boric acid A thin polarizing film is obtained, and is particularly preferably produced by a method of assisting in the air extension in an aqueous solution of boric acid before being extended, as described in Japanese Patent No. 4,751, 481, or JP-A-2012-073563. The resulting thin polarizing film.

(2) Transparent protective film As the transparent protective film, a transparent protective film used hitherto can be suitably used. Specifically, it is preferably a transparent protective film formed of a material excellent in transparency, mechanical strength, thermal stability, moisture barrier properties, and the like, and examples thereof include, for example, polyethylene terephthalate. a polyester-based polymer such as an ester or polyethylene naphthalate, a cellulose-based polymer such as cellulose diacetate or cellulose triacetate, an acrylic polymer such as polymethyl methacrylate, or polystyrene or propylene. Nitrile. A styrene-based polymer such as a styrene copolymer (AS resin) or a polycarbonate-based polymer. Also, polyethylene, polypropylene, ring system or polyolefin with a norbornene structure, ethylene. a polyolefin-based polymer such as a propylene copolymer, a vinyl chloride-based polymer, a guanamine-based polymer such as nylon or an aromatic polyamine, a quinone-based polymer, a fluorene-based polymer, or a polyether fluorene-based polymer. Polyetheretherketone polymer, polyphenylene sulfide polymer, vinyl alcohol polymer, vinylidene chloride polymer, ethylene butyral polymer, aryl ester polymer, polyoxymethylene polymer, epoxy A polymer or a blend of the above polymers may be exemplified as a polymer which forms the transparent protective film. The transparent protective film can also be formed into a cured layer of a thermosetting type or an ultraviolet curable resin such as an acrylic, a urethane type, an urethane type, an epoxy type or a polyoxymethylene type.

The thickness of the transparent protective film can be appropriately determined, and is generally 1 to 500 μm from the viewpoints of workability such as strength and handleability, and film properties.

The polarizer and the transparent protective film are preferably adhered to each other through a water-based adhesive or the like. The water-based adhesive can be exemplified by an isocyanate-based adhesive, a polyvinyl alcohol-based adhesive, a gelatin-based adhesive, a vinyl-based latex, an aqueous polyurethane, and an aqueous polyester. In addition to the above, examples of the adhesive for the polarizer and the transparent protective film include an ultraviolet curable adhesive, an electron beam hardening adhesive, and the like. The adhesive for an electron beam hardening type polarizing film exhibits appropriate adhesion to the above various side discrimination transparent protective films. Further, the adhesive used in the present invention may contain a metal compound filler.

The surface of the transparent protective film which is not attached to the polarizing member may be subjected to a hard coat layer, a reflection preventing treatment, or a treatment for the purpose of preventing sticking or diffusion or preventing glare.

Further, as the transparent protective film, any of transparent protective films having a phase difference and exhibiting a function as an optical compensation layer can be used. When a transparent protective film having a phase difference is used, the phase difference characteristic can be appropriately adjusted to a value necessary for optical compensation. Such a retardation film can suitably use an extended film. When the refractive index in the slow axis direction is nx, the refractive index in the fast axis direction in the plane is ny, and the refractive index in the thickness direction is nz, the retardation film can be selected and used according to various uses. A retardation film in which nx=ny>nz, nx>ny>nz, nx>ny=nz, nx>nz>ny, nz=nx>ny, nz>nx>ny, nz>nx=ny. In addition, nx=ny includes not only the case where nx and ny are identical, but also the case where nx and ny are substantially the same. Further, ny=nz includes not only the case where ny and nz are completely the same, but also the case where ny and nz are substantially the same.

When the polarizing film used in the present invention is used as the antireflection circular polarizing plate of the organic EL display device, the retardation film is preferably delayed by 1⁄4 wavelength (about 100 to 170 nm) of the front surface of the transparent protective film. 4 wavelength plate.

When a retardation film is used as the transparent protective film, it is suitable for use in a case where a transparent protective film is provided on one side of the polarizing member and a retardation film is formed on the other side. Moreover, at this time, the setting of the adhesive layer is not particularly limited, and may be disposed on the opposite side of the transparent protective film from the contact surface of the polarizer, or may be disposed on the opposite side of the contact surface of the retardation film from the polarizer. The side surface is preferably provided on at least one of the faces or both of them from the viewpoint of suppressing deterioration of the organic EL element.

1(a) to 1(c) show an example of a specific structure of a polarizing film of an adhesive layer for an organic EL display device of the present invention. The polarizing film 1 with an adhesive layer for an organic EL display device in which the layers are laminated in the following order is as follows: as shown in Fig. 1 (a), the adhesive layer 2 / the transparent protective film 3 / the polarizing member 4 / phase difference The film 5; as shown in FIG. 1(b), is a transparent protective film 3/polarizer 4/phase difference film 5/adhesive layer 2; as shown in FIG. 1(c), an adhesive layer 2/transparent protective film 3/ Polarizer 4 / retardation film 5 / adhesive layer 2. In the above-mentioned FIGS. 1(a) and 1(b), the adhesive layer 2 is an adhesive layer for an organic EL display device of the present invention, and in FIG. 1(c), at least one of the two adhesive layers 2 is at least one of The adhesive layer for an organic EL display device of the present invention may be used, or both of them may be an adhesive layer for an organic EL display device of the present invention. In addition, in FIG. 1, the polarizing film 6 is a single-layer protective polarizing film composed of the polarizing member 4 and the transparent protective film 3, but is not limited thereto, and may be more transparent between the polarizing member 4 and the retardation film 5. A two-layer protective polarizing film for the protective film. Further, as described above, various functional layers such as a hard coat layer can be formed on the surface of the transparent protective film 3 that is not in contact with the polarizer 4.

Further, when the retardation film is laminated on the polarizing material through the adhesive, the adhesive layer may be an adhesive layer for the organic EL display device of the present invention. In other words, the polarizing film with the adhesive layer for the organic EL display device may have the first adhesive layer, the transparent protective film, the polarizer, the second adhesive layer, the retardation film, and the third adhesive layer in this order, and the first In the adhesive layer, the second adhesive layer, and the third adhesive layer, at least one of the adhesive layers is the adhesive layer for the organic EL display device.

4. Organic EL display device The organic EL display device of the present invention uses at least one of an adhesive layer for an organic EL display device of the present invention and/or a polarizing film for an adhesive layer for an organic EL display device of the present invention.

As an example of a specific structure of the organic EL display device, for example, an organic EL display device in which layers are laminated in the following order as shown in FIGS. 2 to 4 can be cited: a glass cover sheet or a plastic cover sheet 7 / an adhesive layer. 2/transparent protective film 3/polarizer 4/phase difference film 5/adhesive layer 2/organic EL display panel (OLED element panel) 8 (Fig. 2); cover glass or plastic cover sheet 7/adhesive layer 9/ Transparent protective film 3 / polarizing member 4 / retardation film 5 / adhesive layer 2 / organic EL display panel 8 (Fig. 3); cover glass or plastic cover sheet 7 / adhesive layer 2 / sensing layer 10 / adhesive Layer 2/transparent protective film 3/polarizer 4/phase difference film 5/adhesive layer 2/organic EL display panel 8 (Fig. 4). In the adhesive layer 2 in each of the above configurations, at least one of them may be the adhesive layer of the present invention, and all of the adhesive layers 2 may be the adhesive layer of the present invention. In addition to the above, the organic EL display device of the present invention may contain various functional layers such as a protective film and a hard coat layer. Further, an adhesive layer and/or an adhesive layer can be suitably used in the laminate of each layer. The adhesive layer other than the adhesive layer of the present invention can be suitably used as a general adhesive layer used in the art.

EXAMPLES Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to the examples. In addition, the parts and % in each case are on a weight basis.

Production Example 1 (Production of Acrylic Adhesive Composition (a)) 78 parts by weight of 2-ethylhexyl acrylate (2EHA), 18 parts by weight of N-vinyl-2-pyrrolidone (NVP), and acrylic acid A monomer mixture composed of 15 parts by weight of 2-hydroxyethyl (HEA) was blended with 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure 184, having an absorption band at a wavelength of 200 to 370 nm, manufactured by BASF Corporation) of 0.035 by weight. And 2,2-dimethoxy-1,2-diphenylethane-1-one (trade name: Irgacure 651, having an absorption band at a wavelength of 200 to 380 nm, manufactured by BASF Corporation) 0.035 parts by weight as a photopolymerization start After the agent, until the viscosity (measurement conditions: BH viscosity agent No. 5 rotor, 10 rpm, measured temperature 30 ° C) constitutes about 20 Pa. Up to s, ultraviolet rays were irradiated, and a prepolymer composition in which a part of the above monomer components was polymerized (polymerization ratio: 8%) was obtained. Next, 0.15 parts by weight of hexanediol diacrylate (HDDA) and 0.3 parts by weight of a decane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and mixed in the prepolymer composition. An acrylic adhesive composition (a) was obtained.

Production Example 2 (Production of Acrylic Adhesive Composition (b)) In a separable flask equipped with a thermometer, a stirrer, a reflux cooling tube, and a nitrogen introduction tube, 95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid were charged. After 0.2 part by weight of azobisisobutyronitrile and 233 parts by weight of ethyl acetate as a polymerization initiator, nitrogen gas was allowed to flow, and nitrogen substitution was performed for about 1 hour while stirring. Then, the flask was heated to 60 ° C and reacted for 7 hours to obtain an acrylic polymer having a weight average molecular weight (Mw) of 1.1 million. To the above acrylic polymer solution (100 parts by weight of the solid component), trimethylolpropane toluene diisocyanate as an isocyanate crosslinking agent (trade name: CORONATE L, Japan Polyurethane Industry ( 0.8 parts by weight of a decane coupling agent (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.) was added in an amount of 0.1 part by weight, and a solution of the adhesive composition (b) was prepared.

Production Example 3 (Manufacture of Adhesive Layer (B1-1)) The adhesive obtained in Production Example 2 was adhered to a separator having a thickness of 38 μm (a polyethylene terephthalate film having a surface-treated release). The solution of the agent composition (b) was applied to a thickness of 12 μm after drying, and a dry layer was formed at 100 ° C for 3 minutes to remove the solvent, and an adhesive layer was obtained. Then, the mixture was heated at 50 ° C for 48 hours to carry out a crosslinking treatment. Hereinafter, this adhesive layer is referred to as "organic EL display panel side adhesive layer (B1-1)".

Production Example 4 (Manufacture of Adhesive Layer (B1-2)) The separator (thickness-treated polyethylene terephthalate film having a surface of 38 μm) was prepared in Production Example 2. The adhesive composition (b) solution was applied to a thickness of 23 μm after drying, and a dry layer was formed at 100 ° C for 3 minutes to remove the solvent, and an adhesive layer was obtained. Then, the mixture was heated at 50 ° C for 48 hours to carry out a crosslinking treatment. Hereinafter, this adhesive layer is referred to as "organic EL display panel side adhesive layer (B1-2)".

Example 1 (Production of Adhesive Composition (A)) The acrylic pressure-sensitive adhesive composition (a) obtained in Production Example 1 (100 parts by weight of a monomer component forming an acrylic polymer) was added. 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxy) which has been dissolved in butyl acrylate to 15% solids Phenylphenyl)-1,3,5-trivalent (trade name: Tinosorb S, "ultraviolet absorber (b1)" in Tables 1 and 2, maximum absorption wavelength of absorption spectrum: 346 nm, manufactured by BASF, Japan) 0.7 Parts by weight (solid component weight), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (trade name: Irgacure 819, having an absorption band at a wavelength of 200 to 450 nm, manufactured by BASF Corporation, Japan) 0.3 parts by weight and BONASORB UA3911 (trade name, lanthanide compound, "Pigment Compound (c1) in Table 1, 2) which has been dissolved in N-vinyl-2-pyrrolidone (NVP) to form a solid content of 5%. ), the maximum absorption wavelength of the absorption spectrum: 398 nm, half-value width: 48 nm, manufactured by Orient Chemical Co., Ltd., 0.5 parts by weight (solid component weight), and stirred, thereby preparing an adhesive composition (A).

On the release-treated film of the release film, the adhesive composition (A) was applied to form a thickness of 150 μm after the formation of the adhesive layer, and then the release film was bonded to the surface of the adhesive composition layer. Then, ultraviolet irradiation was carried out under the conditions of illuminance: 6.5 mW/cm ² , light amount: 1500 mJ/cm ² , and peak wavelength: 350 nm, and the adhesive composition layer was photocured to form an adhesive layer (A-1).

Example 2 In addition to the pigment compound (c), BONASORB UA3912 (trade name, lanthanide compound, Tables 1, 2) which had been dissolved in N-vinyl-2-pyrrolidone (NVP) to a solid content of 10% was prepared. "Pigment compound (c2)", the absorption wavelength of the maximum absorption wavelength: 386 nm, half-value width: 53 nm, Oriental (ORIENT) Chemical Industry Co., Ltd.) 2.5 parts by weight (solid component weight), and coated as an adhesive The thickness of the layer after the formation of the layer was 100 μm, and the adhesive layer (A-2) was formed in the same manner as in Example 1.

Example 3 The type of the ultraviolet absorber of Example 1 was changed to 2-(2H-benzotriazol-2-yl)-6-(1-methyl) which had been dissolved in butyl acrylate to a solid content of 15%. 1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (trade name: Tinuvin 928, "ultraviolet absorber (b2)" in Tables 1, 2, absorption The maximum absorption wavelength of the spectrum: 349 nm, manufactured by BASF Corporation, Japan, and the addition amount was made into 1.5 parts by weight (solid component weight). In addition, the type of the dye compound was changed to a cinnamic acid-based compound (sample name: SOM-5-0103, "Pigment Compound (c3)" in Tables 1 and 2, and the maximum absorption wavelength of the absorption spectrum was 416 nm, half. The value is the same as that of the first embodiment except that the thickness is 50 nm, which is manufactured by ORIENT Chemical Co., Ltd., and is directly added in an amount of 0.2 part by weight (solid component weight) and coated to a thickness of 100 μm after the formation of the adhesive layer. The adhesive layer (A-3) is formed.

Example 4 The amount of the dye compound was changed to N-vinyl-2-pyrrolidone (NVP), except that the amount of the ultraviolet absorber (b1) of Example 1 was changed to 3.0 parts by weight (solid component weight). A porphyrin compound dissolved in a solid content of 1% (sample name: FDB-001, "Pigment Compound (c4)" in Tables 1 and 2, maximum absorption wavelength of absorption spectrum: 420 nm, half value width: 14 nm, The adhesive layer (A-4) was formed in the same manner as in Example 1 except that 0.1 part by weight (solid component weight) was prepared and applied to a thickness of 100 μm after the formation of the pressure-sensitive adhesive layer.

Example 5 (Production of Adhesive Composition (B)) The adhesive composition (b) solution obtained in Production Example 2 (100 parts by weight of a monomer component forming an acrylic polymer) was directly added. 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-trivalent ( Product name: Tinosorb S, "ultraviolet absorber (b1)" in Tables 1 and 2, maximum absorption wavelength of absorption spectrum: 346 nm, manufactured by BASF, Japan, 3 parts by weight (solid component weight), and BONASORB UA3912 (trade name) , lanthanide compound, "pigment compound (c2)" in Tables 1, 2, maximum absorption wavelength of absorption spectrum: 386 nm, half value width: 53 nm, 0.8 parts by weight (manufactured by ORIENT Chemical Industry Co., Ltd.) The solid component was weighed and stirred, whereby a solution of the adhesive composition (B) was obtained.

On the separator having a thickness of 38 μm (the surface of the polyethylene terephthalate film which has been subjected to release treatment), the obtained adhesive composition (B) solution was applied to a thickness of 25 μm after drying, and The solvent was removed by making a dry layer at 120 ° C for 3 minutes, and an adhesive layer was obtained. Then, the mixture was heated at 50 ° C for 48 hours to carry out a crosslinking treatment. An adhesive layer (B) is formed.

Comparative Example 1 An adhesive layer (A1) was formed in the same manner as in Example 1 except that the acrylic adhesive composition (a) containing the ultraviolet absorber (b1) and the dye compound (c1) of Example 1 was not prepared. -1).

Comparative Example 2 The organic EL display panel side adhesive layer (B1-2) of Production Example 3 was used.

Comparative Example 3 An adhesive layer (A1-2) was formed in the same manner as in Example 1 except that the pigment compound (c1) of Example 1 was not contained and the thickness of the adhesive layer formed was 100 μm.

Comparative Example 4 An adhesive layer (A1-3) was formed in the same manner as in Example 3 except that the pigment compound (c3) was not contained and the thickness of the adhesive layer was 150 μm.

Comparative Example 5 A thickness of 100 μm after the formation of the adhesive layer was carried out, except that the ultraviolet absorber (b1) of Example 1 was not contained, and the amount of the dye compound (c1) was 0.3 parts by weight (solid component weight). Further, an adhesive layer (A1-4) was formed in the same manner as in Example 1.

Comparative Example 6 An adhesive layer was formed in the same manner as in Example 2 except that the ultraviolet absorber (b1) of Example 2 was not contained, and the amount of the dye compound (c2) was 0.5 parts by weight (solid component weight). A1-5).

Comparative Example 7 An adhesive layer (A1-6) was formed in the same manner as in Example 3 except that the ultraviolet absorber (b2) of Example 3 was not contained.

Comparative Example 8 An adhesive layer (A1-7) was formed in the same manner as in Example 4 except that the ultraviolet absorber (b1) of Example 4 was not contained.

Example 6 (Production of Adhesive Layer (A-5)) The addition amount of the pigment compound (c1) of Example 1 was made into 0.7 part by weight (solid component weight), and applied to a thickness after formation of the adhesive layer. An adhesive layer (A-5) was formed in the same manner as in Example 1 except that the composition was 100 μm.

(Production of Polarizing Film (P)) Using a polyvinyl alcohol-based adhesive, a cycloolefin polymer having a thickness of 25 μm was bonded to the side of the polarizing member made of a stretched polyvinyl alcohol film impregnated with iodine and having a thickness of 5 μm. COP) film, and a polyvinyl alcohol-based adhesive, an acrylic film having a thickness of 20 μm on the side surface of the organic EL display panel of the polarizing member, and a polarizing film (P). The polarizing film has a degree of polarization of 99.995.

(Production of Polarizing Film with Adhesive Layer) The adhesive layer (A) prepared by laminating the surface of the polarizing film (P) (i.e., the surface of a cycloolefin polymer (COP) film having a thickness of 25 μm) -5). On the side surface of the organic EL display panel of the polarizing film (P) (that is, the surface of the acrylic film having a thickness of 20 μm), the image display portion side adhesive layer (B1-1) was laminated, and a retardation film (thickness: 56 μm, material) was laminated. : polycarbonate) and the image display portion side adhesive layer (B1-2), and form a polarizing film with an adhesive layer. The polarizing film with the adhesive layer obtained has an adhesive layer (A-5)/polarized film (P)/organic EL display panel side adhesive layer (B1-1)/phase difference film/organic EL display panel The construction of the side adhesive layer (B1-2).

Example 7 An adhesive layer (A-6) was formed in the same manner as in Example 2 except that the amount of the pigment compound (c2) of Example 2 was 0.5 parts by weight (solid component weight). Further, a polarizing film with an adhesive layer was formed in the same manner as in Example 6 except that the above-mentioned adhesive layer (A-6) was used.

Comparative Example 9 An adhesive layer (A1-8) was formed in the same manner as in Example 6 except that the adhesive layer (A-5) of Example 6 did not contain the dye compound (c1). Further, a polarizing film with an adhesive layer was formed in the same manner as in Example 6 except that the above-mentioned adhesive layer (A1-8) was used.

The following evaluation was performed about the obtained adhesive layer and the polarizing film with an adhesive layer.

<Measurement of Transmittance of Adhesive Layer> The release film of the adhesive layer obtained in the examples and the comparative examples was peeled off, and the adhesive layer was attached to a measuring jig by a spectrophotometer (product name) : U4100, manufactured by Hitachi Advanced Technology (High-Technologies). The transmittance is a transmittance in the range of 300 nm to 780 nm.

<Measurement of Transmittance of Polarizing Film Attached to Adhesive Layer> The release film of the polarizing film with an adhesive layer prepared in the examples and the comparative examples was peeled off and separated by a spectrophotometer (product name: U4100, The measurement was performed by Hitachi High-Technologies Co., Ltd. The transmittance is a transmittance in the range of 350 nm to 780 nm.

<Adhesion> A sheet having a length of 100 mm and a width of 20 mm was cut out from the adhesive layers obtained in the examples and the comparative examples. Next, the release film on the side of the adhesive layer was peeled off, and a PET film (trade name: Lumirror S-10, thickness: 25 μm, manufactured by Toray Co., Ltd.) was adhered. Next, the release film on the other side was peeled off, and on a glass plate (trade name: soda lime glass #0050, manufactured by Songlang Glass Industry Co., Ltd.) which was a test plate, a 2 kg rotor was used, and a reciprocating crimping was performed. The conditions were crimped, and a sample composed of the test plate/adhesive layer (A)/PET film was prepared. The prepared sample was subjected to autoclave treatment (50 ° C, 0.5 MPa, 15 minutes), and then allowed to cool under an ambient gas of 23 ° C and 50% R.H. for 30 minutes. After cooling, a tensile tester (device name: Autograph AG-IS, manufactured by Shimadzu Corporation) was used, and according to JIS Z0237, at a tensile rate of 300 mm/at an ambient gas of 23 ° C and 50% RH. The adhesive sheet (adhesive layer/PET film) was peeled off from the test plate under the conditions of a peeling angle of 180°, and a 180° peeling force (N/20 mm) was measured.

<Total Light Transmittance, Haze> The release film on the side from which the adhesive layer obtained in the examples and the comparative examples was peeled off, and bonded to a glass slide (trade name: white polishing No. 1, thickness: 0.8) ~1.0mm, total light transmittance: 92%, haze: 0.2%, Songlang Glass Industry Co., Ltd.). Further, the release film on the other side was peeled off, and a test piece having a layer structure of an adhesive layer/slide was prepared. The total light transmittance and the haze value in the visible light region of the test piece were measured using a haze meter (device name: HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.).

[Table 1]

[Table 2]

1‧‧‧Polarized film with adhesive layer for organic EL display device
2‧‧‧Adhesive layer
3‧‧‧Transparent protective film
4‧‧‧ polarizer
5‧‧‧ phase difference film
6‧‧‧ polarizing film
7‧‧‧glass cover or plastic cover
8‧‧‧Organic EL display panel
9‧‧‧ adhesive layer
10‧‧‧Sensor layer

1 (a) to (c) are cross-sectional views schematically showing an embodiment of a polarizing film of an adhesive layer for an organic EL display device of the present invention. Fig. 2 is a cross-sectional view schematically showing an embodiment of an organic EL display device of the present invention. Fig. 3 is a cross-sectional view schematically showing an embodiment of an organic EL display device of the present invention. Fig. 4 is a cross-sectional view schematically showing an embodiment of an organic EL display device of the present invention.

1‧‧‧Polarized film with adhesive layer for organic EL display device

2‧‧‧Adhesive layer

3‧‧‧Transparent protective film

4‧‧‧ polarizer

5‧‧‧ phase difference film

6‧‧‧ polarizing film

Claims (12)

An adhesive composition for an organic EL display device, comprising: a base polymer; an ultraviolet absorber; and a pigment compound, wherein a maximum absorption wavelength of the absorption spectrum exists in a wavelength region of 380 to 430 nm. The adhesive composition for an organic EL display device according to claim 1, wherein the base polymer is a (meth)acrylic polymer. The adhesive composition for an organic EL display device according to claim 1 or 2, wherein a maximum absorption wavelength of the absorption spectrum of the ultraviolet absorber is present in a wavelength region of 300 to 400 nm. An adhesive layer for an organic EL display device, which is characterized in that the organic EL display device according to any one of claims 1 to 3 is formed of an adhesive composition. An adhesive layer for an organic EL display device according to claim 4, wherein an average transmittance of a wavelength of 300 to 400 nm is 5% or less, an average transmittance of a wavelength of 450 to 500 nm is 70% or more, and an average transmittance of a wavelength of 500 to 780 nm is obtained. More than 80%. The adhesive layer for an organic EL display device according to claim 5, wherein an average transmittance of a wavelength of 300 to 400 nm is 5% or less, an average transmittance of a wavelength of 400 nm to 430 nm is 30% or less, and an average transmittance of a wavelength of 450 to 500 nm is obtained. 70% or more, the average transmittance of the wavelength of 500 to 780 nm is 80% or more. The adhesive layer for an organic EL display device according to claim 5, wherein an average transmittance of a wavelength of 300 to 400 nm is 5% or less, an average transmittance of a wavelength of 400 nm to 430 nm is more than 30% and less than 75%, and a wavelength of 450 to 500 nm is used. The average transmittance is 80% or more, and the average transmittance at a wavelength of 500 to 780 nm is 80% or more. A polarizing film comprising an adhesive layer for an organic EL display device, comprising: a polarizing film; and the adhesive layer for an organic EL display device according to any one of claims 4 to 7. The polarizing film of the adhesive layer of the organic EL display device according to claim 8, wherein the polarizing film is provided with a transparent protective film on one side of the polarizer and a retardation film on the other side, and the organic EL display device is used. The adhesive layer is disposed on the opposite side of the retardation film from the contact surface of the polarizer and/or on the opposite side of the transparent protective film from the contact surface of the polarizer. A polarizing film for an adhesive layer of an organic EL display device according to claim 8, which has a first adhesive layer, a transparent protective film, a polarizing member, a second adhesive layer, a retardation film, and a third adhesive layer. In the first adhesive layer, the second adhesive layer, and the third adhesive layer, at least one of the adhesive layers is the adhesive layer for the organic EL display device. The polarizing film of the adhesive layer for an organic EL display device according to claim 9 or 10, wherein the retardation film is a quarter-wave plate, and the polarizing film is a circularly polarizing film. An organic EL display device using an adhesive layer for an organic EL display device according to any one of claims 4 to 7 and an adhesive for an organic EL display device according to any one of claims 8 to 11. At least one of the layer of polarizing films.