JP2014162827A - Adhesive encapsulating film, production method of adhesive encapsulating film, and coating liquid for adhesive encapsulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive encapsulating film having both a low moisture vapor transmission rate, namely a high moisture barrier property, and high adhesiveness.SOLUTION: The adhesive encapsulating film comprises polyisobutylene having a number average molecular weight of 10,000 or more and a carbon double bond content of 1.6 to 50.0%. By preparing an adhesive encapsulating film by using polyisobutylene as an elastomer in order to realize a high moisture barrier property and by using a tackifier resin whose carbon double bond content is within a specific range in order to realize a high adhesiveness, an adhesive encapsulating film having high durability, which can satisfy both of a high moisture barrier property and high adhesiveness, can be obtained. Further, when the film is used as an adhesive encapsulating film for an organic electroluminescence element, occurrence of dark spots can be suppressed.

Description

  The present invention relates to an adhesive sealing film, and more particularly to an adhesive sealing film using polyisobutylene. The present invention also relates to a method for producing the adhesive sealing film and a coating liquid for the adhesive sealing film.

  The organic electroluminescent device has a light emitting part that is unstable with respect to moisture and oxygen. Therefore, in order to extend the lifetime of the device, the organic electroluminescence device is intended to protect the device from moisture and oxygen entering from the outside. The use of a stop film has been studied. Among these, in particular, a rubber-based adhesive sealing film containing an elastomer and a tackifying resin has an advantage that it can be used by being attached to a desired place of the organic electroluminescence element without using an adhesive. Therefore, various rubber-based adhesive sealing films have been studied so far.

  Patent Documents 1 and 2 report that an adhesive sealing film was prepared by mixing a tackifying resin with a polyisoprene resin used as an elastomer.

  On the other hand, among the elastomers, polyisobutylene has high weather resistance and is excellent in moisture and oxygen barrier properties. So far, as an adhesive sealing film using polyisobutylene as an elastomer, Patent Document 3 reports an adhesive sealing film using polyisobutylene and a hydrogenated cyclic olefin polymer.

Japanese Unexamined Patent Publication No. 2005-129520 Japanese Unexamined Patent Publication No. 2008-115383 Japan Special Table 2009-524705

  However, an adhesive sealing film using polyisobutylene and a hydrogenated cyclic olefin-based polymer has a high moisture barrier property but does not have sufficient adhesiveness. Therefore, when using such an adhesive sealing film as an adhesive sealing film of an organic electroluminescence element, there is a concern about moisture intrusion from an adhesive interface.

  Then, the subject of this invention is providing the adhesive sealing film which has low moisture permeability, ie, a high moisture barrier property, and high adhesiveness.

  In order to solve the above problems, the present inventors use polyisobutylene as an elastomer in order to realize a high moisture barrier property, and a carbon double bond content of 1.6 to 1.6 in order to realize high adhesiveness. By producing an adhesive sealing film using a 50% tackifying resin, an adhesive sealing film having both high moisture barrier properties and high adhesiveness can be produced, and the present invention is satisfied. As a result, it was found that an adhesive sealing film having high durability can be produced, and the present invention has been achieved.

That is, the gist of the present invention is as follows.
[1] An adhesive sealing film containing polyisobutylene having a number average molecular weight of 10,000 or more and a tackifying resin having a carbon double bond content of 1.6% or more and 50.0% or less. And
An adhesive sealing film in which the concentration of toluene remaining in the film is 3000 ppm or less.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the 1H-NMR measurement of the tackifying resin is performed, It is expressed by the following formula.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the 1H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and protons bonded to double-bonded carbon The amount is the sum of the proton spectral areas observed at 4.6-8.0 ppm. )
[2] The adhesive sealing film according to [1], wherein the tackifying resin has a number average molecular weight of 800 or more and 1600 or less.
[3] In the above [1] or [2], the tackifying resin is one or two selected from the group consisting of a rosin resin, a terpene resin, an alicyclic petroleum resin, and an aromatic petroleum resin. Adhesive sealing film that is more than seeds.
[4] The adhesive sealing film according to any one of [1] to [3], wherein the polyisobutylene has a number average molecular weight of 10,000 or more and 1,000,000 or less.
[5] The adhesive sealing film according to any one of [1] to [4], wherein a moisture content remaining in the film is 500 ppm or less.
[6] The adhesive sealing film according to any one of [1] to [5], wherein a carbon double bond content in the adhesive sealing film is 1.8% or more and 50.0% or less.
(Here, the carbon double bond content in the adhesive sealing film is the amount of protons bonded to the double-bonded carbon with respect to all protons when the adhesive sealing film is measured by 1H-NMR. It is a ratio and is represented by the following formula.
Carbon double bond content in adhesive sealing film = (Amount of protons bound to double-bonded carbon contained in adhesive sealing film
/ All protons contained in the adhesive sealing film) × 100
In the 1H-NMR measurement, the total amount of protons contained in the adhesive sealing film is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and is bonded to the double-bonded carbon. The proton content is the sum of the proton spectral areas observed at 4.6 to 8.0 ppm. )
[7] The adhesive sealing film according to any one of [1] to [6], wherein the minimum value of the storage elastic modulus at −20 to 50 ° C. is 1 × 10 9 Pa or less.
[8] The adhesive sealing film according to any one of [1] to [7], which is an adhesive sealing film for organic electroluminescence.
[9] A method for producing the adhesive sealing film according to any one of [1] to [8], wherein the polyisobutylene having a number average molecular weight of 10,000 or more and a carbon double bond content are 1. The manufacturing method of the adhesive sealing film which dries after apply | coating the coating liquid for adhesive sealing films containing 6% or more and 50.0% or less tackifying resin on a base material.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the 1H-NMR measurement of the tackifying resin is performed, It is expressed by the following formula.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the 1H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and protons bonded to double-bonded carbon The amount is the sum of the proton spectral areas observed at 4.6-8.0 ppm. )
[10] A coating solution for an adhesive sealing film comprising polyisobutylene having a number average molecular weight of 10,000 or more and a tackifying resin having a carbon double bond content of 1.6% or more and 50.0% or less. Then, a coating liquid for an adhesive sealing film for producing the adhesive sealing film according to any one of the above [1] to [8] by drying on the substrate.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the 1H-NMR measurement of the tackifying resin is performed, It is expressed by the following formula.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the 1H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and protons bonded to double-bonded carbon The amount is the sum of the proton spectral areas observed at 4.6-8.0 ppm. )
[11] The adhesive encapsulating film coating solution according to [10], further containing toluene.
[12] The adhesive sealing film application according to [10] or [11], wherein the content of carbon double bonds in the solid content of the adhesive sealing film coating solution is 1.8 to 50.0%. liquid.
(Here, the solid content of the coating solution for the adhesive sealing film is obtained by removing the solvent from the coating solution for the adhesive sealing film. The carbon double in the solid content of the coating solution for the adhesive sealing film) The bond content is the ratio of the amount of protons bonded to double-bonded carbon to the total amount of protons when the solid content is measured by 1H-NMR, and is represented by the following formula.
Carbon double bond content in solid content of coating solution for adhesive sealing film = (contained in coating solution for adhesive sealing film,
The amount of protons bonded to double-bonded carbon / the total amount of protons contained in the solid content of the coating solution for adhesive sealing film) × 100
In the 1H-NMR measurement, the amount of all protons contained in the solid content is the sum of the proton spectrum areas observed at 0.1 to 8.0 ppm, and the amount of protons bonded to the double-bonded carbon. Is the sum of the spectral areas of protons observed at 4.6 to 8.0 ppm. )

ADVANTAGE OF THE INVENTION According to this invention, high moisture barrier property and high adhesiveness are made compatible, and also the highly durable adhesive sealing film and its coating liquid are provided.
The adhesive sealing film of the present invention can be applied to adhesive sealing films for various electric devices such as organic or inorganic electroluminescence, solar cells, and displays.

FIG. 1 is a cross-sectional view showing an example of an organic EL light emitting device according to the present invention. FIG. 2 is a cross-sectional view showing an example of the manufacturing process of the organic EL light emitting device according to the present invention. FIG. 2 (a) shows a state in which the first electrode 2 is formed on the surface of the translucent substrate 1, FIG. FIG. 2B is a diagram showing a state in which an organic functional layer 3 serving as a light emitting layer is formed on the first electrode 2, and FIG. 2C is a diagram showing a state in which the second electrode 4 is formed on the organic functional layer 3. . FIG. 3 is a plan view showing an example of the manufacturing process of the organic EL light emitting device according to the present invention. FIG. 3 (a) shows a flexible sheet serving as the protective layer 7, and FIG. 3 (b) shows the protective layer 7. FIG. 3C shows a state in which the hygroscopic layer 6 is formed in a matrix on the surface of FIG. 3. FIG. 3C shows a state in which the protective layer 7 is cut piece by piece. FIG. It is a figure which shows the state in which the sealing layer 5 was formed.

  Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. The content of is not specified.

[Coating liquid for adhesive sealing film]
The coating solution for an adhesive sealing film of the present invention is a coating solution for producing the adhesive sealing film of the present invention, and usually contains a solvent, a polyisobutylene, a tackifying resin, and other components. .

<Polyisobutylene>
The number average molecular weight of the polyisobutylene used in the present invention is usually 10,000 or more, preferably 50,000 or more, more preferably 70,000 or more, particularly preferably 100,000 or more, and usually 1,000,000 or less, preferably 500,000 or less, more preferably Is 250,000 or less, particularly preferably 200,000 or less.
When the number average molecular weight of the polyisobutylene is not less than the above lower limit, creep resistance is improved, which is preferable in terms of application to a device to be used for a long time. On the other hand, when the number average molecular weight of the polyisobutylene is not more than the above upper limit, the adhesiveness is improved, which is preferable. Here, the number average molecular weight of polyisobutylene can be determined by polystyrene conversion using a gel permeation chromatography (GPC) method.

  In the present invention, the polyisobutylene is preferably a homopolymer of isobutylene, but may be a copolymer of isobutylene as a main component and isobutylene and other monomers such as isoprene.

<Tackifying resin>
The tackifying resin refers to a resin that improves the adhesive strength and adhesive strength of polyisobutylene in the sealing film of the present invention.

Examples of the tackifier resin include rosin resins, terpene resins, aliphatic petroleum resins, aromatic petroleum resins, aliphatic / aromatic hybrid petroleum resins, and alicyclic petroleum resins.
Examples of rosin resins include gum rosin, wood rosin, tall oil rosin, rosin-modified maleic resin, polymerized rosin, rosin phenol, rosin ester, and hydrogenated rosin.
Specific examples of the terpene resin include terpene resins, terpene phenol resins, aromatic modified terpene resins, and hydrogenated terpene resins. The terpene resin is obtained by polymerizing any one of α-pinene, β-pinene and dipentene (limonene), or copolymerizing a mixture. The terpene phenol resin is a copolymer of terpene and phenol, and examples thereof include α-pinenephenol resin, dipentenephenol resin, and terpene bisgenol resin. The aromatic modified terpene resin is obtained by copolymerizing a terpene monomer and an aromatic monomer. The hydrogenated terpene resin is obtained by hydrogenating a terpene resin, a terpene phenol resin, or an aromatic modified terpene resin.
Examples of the aliphatic petroleum resin include those obtained by polymerizing a C5 petroleum resin such as piperylene, isoprene, 2-methylbutene-2, dicyclopentadiene alone, or copolymerizing a mixture.
Examples of the aromatic petroleum resins include coumarone resins, inden resins, hydrogenated coumarone resins, hydrogenated inden resins, phenol resins, styrene resins, hydrogenated styrene resins, and xylene resins. The coumarone resin is obtained by copolymerizing coumarone and any one of styrene, vinyltoluene, and α-methylstyrene, or by copolymerizing a mixture. The indene resin is obtained by copolymerizing indene and any of styrene, vinyltoluene, and α-methylstyrene, or by copolymerizing a mixture. Hydrogenated coumarone resin is a hydrogenated coumarone resin. Hydrogenated indene resin is a hydrogenated indene resin. The phenol resin is a copolymer of phenols and aldehydes. Examples of the styrene resin include acrylonitrile butadiene styrene copolymer, acrylonitrile styrene copolymer, and styrene thermoplastic elastomer. The styrenic thermoplastic elastomer has a polystyrene block and a rubber intermediate block, and examples of the intermediate rubber block include polybutadiene, a polyethylene / butylene copolymer, an ethylene / propylene copolymer, and a vinyl / polyisoprene copolymer. Hydrogenated styrene resin is a hydrogenated styrene resin. The xylene-based resin is a copolymer of m-xylene and formaldehyde.
Examples of the aliphatic / aromatic hybrid petroleum resin include an aliphatic / aromatic hybrid petroleum resin and a hydrogenated aliphatic / aromatic hybrid petroleum resin. The mixed aliphatic / aromatic petroleum resin is a copolymer of isoprene, piperylene, 2-methylbutene, -1 and 2, styrene, vinyltoluene, α-methylstyrene, indene, dicyclopentadiene or a mixture thereof. Hydrogenated aliphatic / aromatic hybrid petroleum resin is a hydrogenated aliphatic / aromatic hybrid petroleum resin.
Examples of the alicyclic petroleum resin include dicyclopentadiene resin and hydrogenated dicyclopentadiene resin. The dicyclopentadiene resin is obtained by copolymerizing dicyclopentadiene and any one of styrene, butadiene, pentadiene, vinyl acetate, maleic anhydride, and phenol, or a mixture thereof. Hydrogenated dicyclopentadiene resin is obtained by hydrogenating dicyclopentadiene resin.
The tackifying resin may be hydrogenated.
These tackifier resins may be used alone or in combination of two or more.

  From the viewpoint of adhesiveness, among the tackifying resins, rosin resins, terpene resins, alicyclic petroleum resins, and aromatic petroleum resins are preferable, among which terpene resins and alicyclic petroleum resins are preferable, Among these, alicyclic petroleum resins are particularly preferable, and dicyclopentadiene resins containing dicyclopentadiene as a monomer component are particularly preferable. From the viewpoint of transparency, terpene resins are preferred, and among these, aromatic modified terpene resins are particularly preferred.

The carbon double bond content of the tackifying resin is usually 1.6% or more, preferably 2.0% or more, more preferably 5.0% or more, still more preferably 8.0% or more, usually 50.0%. Hereinafter, it is preferably 40.0% or less, more preferably 30.0% or less, further preferably 25.0% or less, and particularly preferably 15.0% or less. When the carbon double bond content is not less than the above lower limit, the adhesiveness is improved, which is preferable.
It is preferable that the carbon double bond content is not more than the above upper limit because weather resistance is improved.

Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the carbon having double bonds to the total amount of protons when the tackifying resin is measured by ¹ H-NMR, It is expressed by the following formula.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the tackifier resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and is bonded to the double-bonded carbon. The proton amount is the sum of the proton spectral areas observed at 4.6 to 8.0 ppm.

  The softening point of the tackifying resin is usually 50 ° C. or higher, preferably 80 ° C. or higher, more preferably 100 ° C. or higher, further preferably 120 ° C. or higher, particularly preferably 140 ° C. or higher, 300 ° C. or lower, preferably 200 ° C. Below, more preferably 150 ° C. or less. When a softening point is more than the following lower limit, it is preferable from a viewpoint of the long-term durability of the device using this adhesive sealing film. It is preferable that the softening point is not more than the above upper limit because the adhesiveness is improved. Here, the softening point of the tackifier resin can be measured by a known method, and examples thereof include a ring and ball method, a thermomechanical analysis (TMA) method, and the like.

  The number average molecular weight of the tackifying resin is usually 400 or more, preferably 600 or more, more preferably 800 or more, and usually 2000 or less, preferably 1800 or less, more preferably 1600 or less. When the number average molecular weight is not less than the above lower limit, it is preferable from the viewpoint of long-term durability of a device using such an adhesive sealing film. When the number average molecular weight is not more than the above upper limit, it is preferable from the viewpoint of adhesiveness. Here, the number average molecular weight of the tackifier resin can be determined by polystyrene conversion using a gel permeation chromatography (GPC) method.

<Solvent>
As the solvent of the coating solution for the adhesive sealing film, any known one can be used as long as it dissolves the polyisobutylene and tackifying resin contained in the adhesive sealing film. Water, an organic solvent, or a mixture thereof It may be a solvent. Examples of organic solvents include alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, butyl alcohol, methyl cellosolve, butyl cellosolve, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Esters such as monoethyl ether acetate, ethers such as diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, amides such as dimethylformamide and N-methylpyrrolidone, acetone, methyl ethyl ketone, acetylacetone , Ketones such as cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene, heptane, Hexane, pentane, it can be used decane, known organic solvents such as aliphatic hydrocarbons such as cyclohexane. These may be used alone or in combination of two or more.

  Of the above solvents, an organic solvent is preferable, and toluene is more preferable from the viewpoint of improving solubility.

  In addition, the coating liquid for adhesive sealing films can select the presence or absence of a solvent suitably according to a use. From the viewpoint of dissolving the high molecular weight polyisobutylene, it is preferable to use a solvent. Moreover, when there is no solvent, it is preferable to use a solvent from a viewpoint that the base material which apply | coats the coating liquid for adhesive sealing films is restrict | limited to a thing with high heat resistance. On the other hand, no solvent is preferable from the viewpoint of influence on the environment and the human body.

<Other ingredients>
Softener (plasticizer), corrosion inhibitor, heat stabilizer, ultraviolet absorber, infrared absorber, colorant, antioxidant, antifungal agent, pH adjuster, difficult Flame retardants, crystal nucleating agents, conductive particles, inorganic particles, organic particles, viscosity modifiers, lubricants, surface treatment agents, leveling agents, crosslinking agents, antifoaming agents, polymerizable monomers, photopolymerizable initiators, etc. Various components may be included for the purpose of providing a function.

  Known softeners may be used as the softener, and are not particularly limited. For example, aromatic hydrocarbon, paraffinic, naphthenic petroleum hydrocarbon, low molecular weight polybutene, low molecular weight polyisobutylene, low molecular weight polyisoprene, Examples include various depolymerized rubbers (liquid rubbers), mineral oils (process oils), liquid rubbers such as hydrogenated liquid polyisoprene and derivatives thereof, petrolactam, petroleum asphalts, and the like. These softeners may be used alone or in combination of two or more. Here, the low molecular weight polyisobutylene refers to those having a number average molecular weight less than that of the polyisobutylene according to the present invention, that is, a number average molecular weight of less than 126000.

  From the viewpoint of improving adhesiveness, workability, and high barrier properties, it is preferable to add low molecular weight polybutene or low molecular weight polyisobutylene.

  Since the carbon double bond contained in the tackifying resin tends to oxidatively deteriorate due to its chemical structure, it is effective to add an antioxidant to the coating film coating solution. The antioxidant is not particularly limited as long as it is usually used in the field of adhesives, resin materials or rubber materials. Specifically, phenolic antioxidants, phosphite antioxidants and amine-based antioxidants are used. An antioxidant is mentioned. From the viewpoint of the influence on the organic electroluminescence element, a phenol-based antioxidant and an amine-based antioxidant are preferable, and a phenol-based antioxidant is particularly preferable.

  As a polymerizable monomer, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) Acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxy Monofunctional monomers such as butyl (meth) acrylate, glycidyl (meth) acrylate, N- (meth) acryloylmorpholine, vinylpyrrolidone, styrene, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethylene glycol di (meth) acrylate, tricyclodecane di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexamethylene di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripropylene di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate Polyfunctional monomers such as bets and the like (herein "(meth) acrylate" refers to either or both of the "acrylate", "methacrylate".). These polymerizable monomers can be used individually by 1 type or in mixture of multiple types.

  In addition, since heteroatoms such as oxygen atoms and nitrogen atoms contained in the polymerizable monomer tend to adsorb moisture, from the viewpoint of high barrier properties, the coating liquid for sealing film is a polymerizable monomer. It is preferable not to contain a body.

  In addition, natural rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer, etc., elastomers other than polyisobutylene, phenol resin, urea resin, melamine resin, epoxy resin as long as the adhesive function is not impaired Various polymers such as thermosetting resins such as unsaturated polyester resin, polyimide, polyurethane, and silicon resin, and thermoplastic resins such as polystyrene, polyacrylate, polyester, polyether, polyamide, and polyvinyl alcohol may be used. These components may be used alone or in combination of two or more.

<Coating solution composition>
The solid content concentration of the coating solution for adhesive sealing film is usually 1% by weight or more, preferably 10% by weight or more, more preferably 20% by weight, still more preferably 30% by weight or more, and usually 99.99% by weight or less. , Preferably 80% by weight or less, more preferably 50% by weight or less. When solid content concentration is more than the said minimum, since the adhesive sealing film of a desired film thickness is obtained, it is preferable from a viewpoint of sealing performance. When solid content concentration is below the said upper limit, it is preferable from a viewpoint which can use high molecular weight polyisobutylene as an elastomer and can manufacture an adhesive sealing film, without being restrict | limited to a highly heat-resistant base material.

  The polyisobutylene content in the solid content of the coating solution for adhesive sealing film is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more, and usually 90% by weight. % Or less, preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 60% by weight or less. When the polyisobutylene content in the solid content is not less than the above lower limit, it is preferable from the viewpoint of improving adhesiveness and moisture barrier properties. Moreover, when the polyisobutylene content in solid content is below the said upper limit, it is preferable from a viewpoint of an adhesive improvement.

  Here, the solid content of the coating liquid for adhesive sealing film is obtained by removing the solvent from the coating liquid for adhesive sealing film.

  The tackifying resin content in the solid content of the coating solution for adhesive sealing film is usually 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, further preferably 40% by weight or more, 90% by weight. % Or less, preferably 80% by weight or less, more preferably 70% by weight or less, and still more preferably 60% by weight or less. When the content of tackifying resin in the solid content is not more than the above upper limit, it is preferable from the viewpoint of improving adhesiveness and moisture barrier properties. Moreover, when tackifying resin content in solid content is more than the said minimum, it is preferable from a viewpoint of adhesive improvement.

  The mixing weight ratio (polyisobutylene / tackifying resin) of polyisobutylene and tackifying resin contained in the coating solution for adhesive sealing film is usually 10/90 or more, preferably 20/80 or more, more preferably 30/70. More preferably, it is 40/60 or more, usually 90/10 or less, preferably 80/20 or less, more preferably 70/30 or less, and further preferably 60/40 or less. When the mixing weight ratio of polyisobutylene and tackifying resin is not less than the above lower limit, it is preferable from the viewpoint of improving the adhesiveness and moisture barrier properties. Moreover, when the mixing weight ratio of polyisobutylene and tackifying resin is below the said upper limit, it is preferable from a viewpoint of an adhesive improvement.

  The total content of polyisobutylene and tackifying resin in the solid content of the coating solution for adhesive sealing film is usually 70% by weight or more, preferably 80% by weight or more, more preferably 90% by weight or more, and further preferably 95% by weight. % Or more. When the total content of polyisobutylene and tackifying resin in the solid content is not less than the above lower limit, it is preferable from the viewpoint of improving adhesiveness and moisture barrier properties.

  When the softening agent is contained in the coating liquid for adhesive sealing film, the content of the softening agent in the solid content of the coating liquid for adhesive sealing film is usually 0.01% by weight or more, preferably 1% by weight or more, More preferably, it is 5% by weight or more, usually 30% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. When content of the softening agent in solid content is more than the said minimum, it is preferable from a viewpoint of the adhesive improvement by initial stage adhesion (tack). When it is below the above upper limit, creep resistance is improved, which is preferable in terms of application to a device used for a long time.

<Carbon double bond content>
The content of carbon double bonds in the solid content of the coating solution for adhesive sealing film is usually 1.8% or more, preferably 2.0% or more, more preferably 3.0% or more, and further preferably 4.0. % Or more, usually 50.0% or less, preferably 40.0% or less, more preferably 30.0% or less, still more preferably 20.0% or less, and particularly preferably 10.0% or less. When the content of the carbon double bond in the solid content of the coating liquid for adhesive sealing film is not less than the above lower limit, it is preferable because the adhesiveness is improved. When the content of the carbon double bond in the solid content of the coating solution for adhesive sealing film is not more than the above upper limit, it is preferable because durability is improved.

Here, the content of the carbon double bond in the solid content of the coating liquid for adhesive sealing film is the carbon having double bonds with respect to all the proton amounts when the solid content is measured by ¹ H-NMR. It is the ratio of the amount of protons bound, and is represented by the following formula.
Carbon double bond content in solid content of coating solution for adhesive sealing film = (contained in coating solution for adhesive sealing film,
The amount of protons bonded to double-bonded carbon / the total amount of protons contained in the solid content of the coating solution for adhesive sealing film) × 100
In the above ¹ H-NMR measurement, the amount of all protons contained in the solid content is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and protons bonded to double-bonded carbon The amount is the sum of the proton spectral areas observed at 4.6-8.0 ppm.

[Adhesive sealing film]
The adhesive sealing film in the present invention is characterized by containing a polyisobutylene having a number average molecular weight of 10,000 or more and a tackifying resin containing 1.6 to 50.0% of a carbon double bond. It is a sealing film having adhesiveness. In particular, the adhesive sealing film in the present invention can be used by being attached to a desired location of the organic electroluminescence element without using an adhesive, and can be filled in the desired location. .

<Carbon double bond content>
The carbon double bond content in the adhesive sealing film is usually 1.8% or more, preferably 2.0% or more, more preferably 3.0% or more, still more preferably 4.0% or more, and usually 50. It is 0% or less, preferably 40.0% or less, more preferably 30.0% or less, further preferably 20.0% or less, and particularly preferably 10.0% or less. When the carbon double bond content in the adhesive sealing film is not less than the above lower limit, it is preferable because the adhesiveness is improved. When the carbon double bond content in the adhesive sealing film is not more than the above upper limit, it is preferable because durability is improved.

Here, the carbon double bond content in the adhesive sealing film is the amount of protons bound to the double-bonded carbon with respect to all protons when the adhesive sealing film is measured by ¹ H-NMR. It is a ratio and is represented by the following formula.
Carbon double bond content in adhesive sealing film = (Amount of protons contained in adhesive sealing film bound to double-bonded carbon / Amount of all protons contained in adhesive sealing film ) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the adhesive sealing film is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, The amount of protons bound is the sum of the spectral areas of protons observed at 4.6 to 8.0 ppm.

<Composition>
The adhesive sealing film of the present invention can be produced using the aforementioned coating liquid for adhesive sealing film of the present invention, and the components other than the solvent in the coating liquid for adhesive sealing film of the present invention, That is, it is composed of a polyisobutylene having a number average molecular weight of 10,000 or more, a tackifier resin containing a carbon double bond, and, if necessary, the above-mentioned components contained in a coating solution for an adhesive sealing film, and a suitable number average Polyisobutylene having a molecular weight of 10,000 or more, a tackifier resin containing a carbon double bond, and other components are the same as those described as those contained in the adhesive sealing film coating solution. In addition, the composition of the polyisobutylene having a number average molecular weight of 10,000 or more contained in the adhesive sealing film, a tackifier resin containing a carbon double bond, and components used as necessary is the adhesive property of the present invention described above. It is the same as that of composition of solid content other than the solvent of the coating liquid for sealing films.

<Film thickness>
The film thickness of the adhesive sealing film is usually 1 μm or more, preferably 10 μm or more, more preferably 20 μm or more, and usually 1 mm or less, preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less. When the film thickness is at least the above lower limit, the moisture barrier property is improved, which is preferable. When a film thickness is below the said upper limit, it is preferable from a viewpoint which the device applied is not restrict | limited.

<Glass transition temperature>
The glass transition temperature of the adhesive sealing film is usually −50 ° C. or higher, preferably −30 ° C. or higher, more preferably −20 ° C. or higher, further preferably −10 ° C. or higher, particularly preferably 0 ° C. or higher, and usually 200 ° C. The temperature is preferably 150 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 80 ° C. or lower, and particularly preferably 50 ° C. or lower. When the glass transition temperature is equal to or higher than the lower limit, the adhesiveness can be improved in both cases where the glass transition temperature is equal to or lower than the upper limit.

  The glass transition temperature of the adhesive sealing film is measured by a differential scanning calorimeter (DSC), a dynamic viscoelasticity measuring device (DMA), or a thermomechanical analyzer (TMA).

<Storage modulus>
The minimum value of the storage elastic modulus at −20 to 50 ° C. of the adhesive sealing film is usually 1 × 10 ⁹ Pa or less, preferably 8 × 10 ⁸ Pa or less, and usually 1 × 10 ³ Pa or more, preferably 1 × 10. ⁴ Pa or more. When the minimum value of the storage elastic modulus at −20 to 50 ° C. of the adhesive sealing film is equal to or more than the above lower limit, the adhesive sealing film can be applied to a device for long-term use, which is preferable. Moreover, since adhesiveness can be improved, it is preferable. When the minimum value of the storage elastic modulus at −20 to 50 ° C. of the adhesive sealing film is not more than the above upper limit, the adhesiveness can be improved, which is preferable.

  The storage elastic modulus of the adhesive sealing film is measured by a dynamic viscoelasticity measuring device (DMA) in a shear mode or a film shear mode at a frequency of 1 Hz in a nitrogen gas atmosphere.

<Tensile shear adhesive strength>
Tensile shear adhesive strength of the adhesive encapsulating film typically 50 N / 100 mm ² or more, preferably 100 N / 100 mm ² or more, more preferably 200 N / 100 mm ² or more and usually 10000 N / 100 mm ² or less. When the tensile shear adhesive strength is not less than the above lower limit, it is preferable because the adhesiveness is high. When the tensile shear adhesive strength is not more than the above upper limit, it is preferable from the viewpoint of recycling.

The tensile shear adhesive force of the adhesive sealing film is measured by the following method.
The test plate is an aluminum plate (10 cm × 3 cm × 1 mm), the test plate sandwiched with an adhesive sealing film (15 mm × 15 mm × 50 μm) is sandwiched between clips, and heated at 100 ° C. for 20 minutes to form an adhesive sealing film Is crimped to the test plate. The tensile shear adhesive force at a tensile speed of 50 mm / min is measured on the test plate after pressure-bonding the adhesive sealing film using a tensile tester in a test environment of 23 ° C., 50% RH, and a distance between chucks of 10 cm.

<Moisture permeability>
About the adhesive sealing film, the water vapor permeability measured by the following method is usually 100 g · m ⁻² · 24 h ⁻¹ or less, preferably 80 g · m ⁻² · 24 h ⁻¹ or less, more preferably 60 g · m ^{−. 2} · 24h ⁻¹ or less. When the moisture permeability is not more than the above upper limit, the moisture barrier property can be improved, which is preferable. When the moisture permeability is at least the above lower limit, the carbon double bond content in the adhesive sealing film can be increased, which is preferable from the viewpoint of improving the adhesiveness.

The moisture permeability is measured by the following method.
Two peeled PET (polyethylene terephthalate) films (MRV38, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) obtained by cutting a circular adhesive sealing film (film thickness 25 μm) having a diameter of 1.2 cm into a circle having a diameter of 1.2 cm. The laminated body A is produced by sandwiching. This layered product A is set on the lid (hole cap) of a syringe vial (syringe vial, Model CV-5, manufactured by Maruemu Co., Ltd.), and anhydrous calcium chloride particles (particle size: 3-5 mm, domestic chemical stock) are contained in the syringe vial. 2 g of company) is put in and a sample for measuring moisture permeability is prepared. A sample for measuring moisture permeability is placed in an atmosphere of 60 ° C. and 95% RH, and the weight after 24 hours and 72 hours is measured. After 24 to 72 hours, the weight increase per 24 hours is adhesively sealed. Divide by the film area to obtain the moisture permeability of the laminate A.

[Method for producing adhesive sealing film]
The adhesive sealing film of the present invention can be produced by a melt extrusion method. Preferably, the adhesive sealing film coating liquid of the present invention is applied according to the method for producing an adhesive sealing film of the present invention. It is manufactured by coating and drying on a substrate.

<Application method>
Examples of the method for applying the coating liquid for adhesive sealing film of the present invention to the substrate include spray coating, dip coating, doctor blade coating, curtain roll coating, gravure roll coating, reverse roll coating, Examples include the air knife coating method, rod coating method, die coating method, offset printing method, comma coating method, and lip coating method.

<Application environment>
The relative humidity during application of the coating solution for adhesive sealing film is usually 20% or more, preferably 25% or more, more preferably 30% or more, still more preferably 50% or more, and usually 85% or less, preferably 80. % Or less, more preferably 75% or less. When the relative humidity is within the above-mentioned range, the uniformity of the adhesive sealing film is improved, which may suppress a decrease in adhesion and moisture barrier properties due to a decrease in film uniformity.
There is no restriction | limiting in the atmosphere at the time of application | coating of the coating liquid for adhesive sealing films. For example, the coating solution for the adhesive sealing film may be applied in an air atmosphere, and may be applied in an inert gas atmosphere such as argon.

<Filtration>
Since the light emitting part of the organic electroluminescence element is unstable with respect to foreign matter, filtration is performed to remove the foreign matter. As a filtration method, a known method can be used. For example, a known method such as a filter paper, a nonwoven fabric, a metal mesh, a sintered metal, a porous plate, a porous ceramic, or a filter can be used. Although there is no limitation in particular as a mesh of a filter medium, Usually, the thing of about 5-20 micrometers is used suitably. Filtration is usually performed at room temperature under normal pressure, reduced pressure, or increased pressure.

  Although there is no restriction | limiting in the temperature of the coating liquid for adhesive sealing films, Usually, 0 degreeC or more, Preferably it is 10 degreeC or more, More preferably, it is 20 degreeC or more, Usually, 200 degrees C or less, Preferably it is 150 degrees C or less, More preferably, it is 100. ° C or lower, more preferably 80 ° C or lower. When the temperature at the time of application is within the above range, the film thickness unevenness of the adhesive sealing film due to the volatilization of the solvent can be suppressed, and the deterioration of the adhesiveness and moisture barrier property due to the deterioration of the uniformity of the film can be suppressed. There is property and is preferable.

<Dry>
When the coating liquid for adhesive sealing film is solvent-free, since the adhesive sealing film is obtained by cooling the coating liquid after coating, drying after coating is not required, but for adhesive sealing film When the coating solution contains a solvent, drying for removing the solvent is performed after coating.

  As the drying method, a known method can be used, and examples thereof include a natural drying method, a heat drying method (hot air drying method, infrared drying method, far infrared drying method, etc.). You may implement and may implement in combination of 2 or more type.

  In the case of the heat drying method, the heating temperature is usually 40 ° C. or higher, preferably 60 ° C. or higher, more preferably 80 ° C. or higher, more preferably 100 ° C. or higher, usually 300 ° C. or lower, preferably 200 ° C. or lower, more preferably 150. It is below ℃. When heating temperature is more than the said minimum, the residual solvent in an adhesive sealing film can be reduced and it is preferable. When heating temperature is below the said upper limit, deterioration by the heating of an adhesive sealing film can be suppressed, and it is preferable. Moreover, since the base material which can be used is not restrict | limited to a heat resistant base material, it is preferable.

  The heating time during drying is usually 1 second or longer, preferably 10 seconds or longer, more preferably 30 seconds or longer, more preferably 1 minute or longer, particularly preferably 5 minutes or longer, most preferably 3 hours or longer, and usually 24 hours or shorter. , Preferably 12 hours or less, more preferably 6 hours or less, and even more preferably 4 hours or less. When heating time is more than the said minimum, the residual solvent in an adhesive sealing film can be reduced and it is preferable. When the drying time is not more than the above upper limit, it is possible to prevent thermal deterioration of the substrate and the substrate, and it is also preferable from the viewpoint of productivity.

Since the residual solvent tends to lower the adhesive force and moisture barrier property, the content of the residual solvent is usually 10,000 ppm or less, more preferably 3000 ppm or less, still more preferably 1000 ppm or less, and particularly preferably 300 ppm or less. Here, residual toluene can be calculated | required by conversion of the chloroform solution of a sheet | seat using a gas chromatography (GC) method. When the residual solvent is within the above range, it is preferable because the influence of the solvent volatilization on the device is suppressed and the growth of the non-light emitting portion is suppressed.
Further, since residual moisture tends to lower the adhesive strength and moisture barrier property, the content of residual moisture is usually 500 ppm or less, more preferably 100 ppm or less, further preferably 50 ppm or less, and particularly preferably 30 ppm or less. Here, the residual moisture can be determined using Karl Fischer or TPD-MS. When the residual moisture is within the above range, it is preferable because the influence of water on the element is suppressed and the growth of the non-light emitting portion is suppressed.

  A known heating device can be used for heating, and examples thereof include an oven, a hot plate, an IR heater, and an electromagnetic wave heating device.

  The atmosphere during drying includes an air atmosphere, a nitrogen gas atmosphere, an Ar gas atmosphere, a He gas atmosphere, a carbon dioxide atmosphere, and the like.

  The coating film after heat drying may be cooled or cooled.

<Base material>
As a base material to which the coating liquid for adhesive sealing film is applied, paper, glass plates and the like can be used in addition to various resin films. As the resin material of the resin film, a thermoplastic resin or a thermosetting resin can be used, and there is no particular limitation. Examples of the thermoplastic resin include polyolefin resins, polystyrene resins, vinyl chloride resins, acrylic resins, polyester resins, fluorine resins, polycarbonate resins, nylon resins, and cellulose acetate. Examples of the thermosetting resin include polyester resin, acrylic resin, epoxy resin, phenol resin, unsaturated alkyd resin, melamine resin, and urethane resin. The resin film used in the present invention can be produced by a known method, and examples thereof include extrusion, calendering, injection, hollow, and compression molding.

  When the substrate is a resin film, the thickness is usually 10 μm or more and is usually 1 cm or less, preferably 5 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less. When thickness is below the said upper limit, after apply | coating an adhesive sealing film on a base material, it can roll and preserve | save and it is preferable from the surface of productivity. When thickness is more than the said minimum, when peeling an adhesive sealing film from a base material, the intensity | strength of a base material can be raised and it is preferable. When the substrate is paper or glass plate, the thickness is usually 10 μm or more, and usually 1 cm or less, preferably 5 mm or less, more preferably 1 mm or less. When the thickness is less than or equal to the above upper limit, the weight does not become too heavy, which is preferable from the viewpoint of ease of handling. When the thickness is equal to or greater than the above lower limit, the strength of the base material is sufficient when the adhesive sealing film is peeled from the base material, which is preferable.

  A release agent may be applied to the application surface of the substrate. As the release agent, a known one such as a silicone resin can be used.

  The adhesive sealing film formed by applying a coating solution for adhesive sealing film on a substrate and drying it as necessary is covered with another substrate and sandwiched between two substrates It is good. At this time, the materials of the two substrates may be the same or different. Moreover, the thickness of two base materials may be the same and may differ. From the viewpoint of peeling the adhesive sealing film from the substrate, it is preferable that the two substrates have different thicknesses.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

[Evaluation of adhesive sealing film]
The adhesive sealing film was evaluated by the following method.

<Evaluation of tensile shear adhesive strength>
The test plate was an aluminum plate (10 cm × 3 cm × 1 mm), the test plate sandwiched with the test piece (adhesive sealing film) was sandwiched between clips, and the test plate was heated in an oven at 100 ° C. for 20 minutes. Except for being crimped to JIS Z1541, the test environment is 23 ° C., 50% RH, test piece (adhesive sealing film) 15 mm × 15 mm × 50 μm, test plate size 10 cm × 3 cm, and distance between chucks 10 cm. The tensile shear adhesive force at a tensile speed of 50 mm / min was measured using a tensile tester (Tensilon UTC-5T, manufactured by Orientec Co., Ltd.). The test plate was ultrasonically cleaned with a solvent in which equal amounts of toluene and isopropyl alcohol were mixed before attaching the test piece.

<Evaluation of moisture permeability>
A 1.2 cm diameter circular adhesive sealing film (film thickness 25 μm) is sandwiched between two peeled PET films (MRV 38, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) cut into a circular shape with a diameter of 1.2 cm and laminated. Body A was prepared. This layered product A is set on the lid (hole cap) of a syringe vial (syringe vial, Model CV-5, manufactured by Maruemu Co., Ltd.), and anhydrous calcium chloride particles (particle size: 3-5 mm, domestic chemical stock) are contained in the syringe vial. 2 g of company manufactured) was put into a sample for measuring moisture permeability.
A sample for measuring moisture permeability was placed in an atmosphere of 60 ° C. and 95% RH, and the weight after 24 hours and 72 hours was measured. The weight increase per 24 hours was measured from 24 hours to 72 hours. Dividing by area, the moisture permeability of laminate A was determined.

<Evaluation of storage elastic modulus and glass transition temperature>
Using a viscoelastic spectrometer (DMS6100, manufactured by SII NanoTechnology Co., Ltd.), in the film shear mode, the storage elastic modulus and glass transition temperature of the adhesive sealing film (3.5 cm × 1.0 cm × 2 mm) It was measured. The measurement conditions at this time were a nitrogen gas atmosphere, a heating rate of 2 ° C./min, and a frequency of 1 Hz.

<High temperature and high humidity test>
A test piece (15 mm × 15 mm × 50 μm adhesive sealing film) is sandwiched between aluminum plates (10 cm × 3 cm × 1 mm) and heated at 100 ° C. for 20 minutes, and then the sample is subjected to an environmental tester (Silvery). Emperor, SE-23CRA, manufactured by Kato Corporation) and left in an atmosphere of 60 ° C. and 95% RH for 72 hours.

<Evaluation of carbon double bond content>
The carbon double bond content in the tackifying resin, the carbon double bond content in the adhesive sealing film, and the carbon double bond content in the solid content of the coating liquid for adhesive sealing film are ¹ H-NMR (proton Nuclear magnetic resonance) apparatus (AVANCE400, AV400, manufactured by Bruker Biospin) was used for measurement. At this time, it melt | dissolved in deuterated chloroform so that the solid content concentration of a sample might be 1 weight%, and measured on condition of the following.
Resonance frequency: 400 MHz
Probe: 5mmφ probe Measurement temperature: 27 ° C
Sample rotation speed: 20Hz
Measurement method: Single pulse method Flip angle: 90 ° Repeat time: 1 s
Measurement time: 2.73 s
Integration count: 16 times Observation width: 6 kHz
Broadening factor: 0.1 Hz

Such carbon double bond content is represented by the following formula.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
Carbon double bond content in adhesive sealing film = (Amount of protons bound to double-bonded carbon contained in adhesive sealing film
/ All protons contained in the adhesive sealing film) × 100
Carbon double bond content in the solid content of the coating solution for adhesive sealing film = (the amount of protons bound to the carbon having double bonds contained in the solid content)
/ Amount of all protons contained in the solid content) × 100
Here, the solid content of the coating liquid for adhesive sealing film is obtained by removing the solvent from the coating liquid for adhesive sealing film.
The total amount of protons contained in the entire tackifying resin, the total amount of protons contained in the entire adhesive sealing film, and the total amount of protons contained in the solid content of the coating solution for adhesive sealing film are 0. Is the sum of the proton spectral areas (integrated values) at 1 to 8.0 ppm, and the amount of protons bound to the double-bonded carbon is the proton spectral area (integrated values) at 4.6 to 8.0 ppm. Is the sum of

<Number average molecular weight>
The number average molecular weight of polyisobutylene and tackifying resin is measured under the following conditions by gel permeation chromatography, and a calibration curve (created using the peak molecular weight of standard polystyrene) obtained from measurement of commercially available standard polystyrene is used. And calculated as a polystyrene equivalent value.
Apparatus: 2695-2410 (manufactured by Waters)
Column: KF602.5-KF603-KF604 (manufactured by Showa Denko)
Eluent: THF
Flow rate: 0.7 mL / min
Sample concentration: 1.0% by weight
Injection volume: 20 μL,
Column temperature: 40 ° C

[Example 1]
<Preparation of adhesive sealing film>
2.5 g of polyisobutylene (number average molecular weight 120,000, homopolymer of isobutylene, manufactured by BASF), alicyclic petroleum resin (cyclopentadiene-dicyclopentadiene copolymer, Quintone TD-401, Nippon Zeon Co., Ltd.) 6.3 g) was dissolved in 12.7 g of toluene (manufactured by Kanto Chemical Co., Ltd.) at room temperature (20-30 ° C.) with stirring using a mix rotor (VMR-3, manufactured by ASONE Co., Ltd.) A coating solution A for a stop film was prepared.
The coating solution A for adhesive sealing film was applied onto a peeled PET film (MRV38, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) using an applicator, and dried by heating on a hot plate at 100 ° C. for 20 minutes. Then, it vacuum-dried at 100 degreeC for 3 hours, and produced the adhesive sealing film A.
Table 1 shows the composition of the adhesive sealing film A (same as the solid content composition of the coating liquid for adhesive sealing film) and the solid content concentration of the coating liquid A for adhesive sealing film. Table 2 shows the tackifying resin. The carbon double bond content in the used alicyclic petroleum resin, adhesive sealing film A, and coating liquid A for adhesive sealing film is shown.

<Evaluation of adhesive sealing film>
When the adhesive sealing film A was evaluated by the above-described methods, the tensile shear adhesive strength was 400 N / 100 cm 2, the minimum storage elastic modulus at −20 to 50 ° C. was 3.7 × 10 ⁸ Pa, glass The transition temperature was 34 ° C., and the moisture permeability of the laminate A was 45 g · m ⁻² · 24 h ⁻¹ . Further, the tensile shear adhesive strength after the high temperature and high humidity test was 397 N / 100 cm ² .
The evaluation results of the adhesive sealing film A are shown in Table 3.

[Example 2]
2.5 g of polyisobutylene (number average molecular weight 200,000, homopolymer of isobutylene, manufactured by BASF), 6.3 g of aromatic modified terpene resin (YS Resin TR105, manufactured by Yasuhara Chemical Co., Ltd.), polybutene (HV-100, number average molecular weight) 980, JX Nippon Mining & Energy Co., Ltd.) 1.0 g was dissolved in toluene (Kanto Chemical Co., Ltd.) 31.5 g. Liquid B was prepared. The same operation as Example 1 was performed using the coating liquid B for adhesive sealing films, the adhesive sealing film B was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film B and the solid content concentration of the coating liquid B for adhesive sealing film, and Table 2 shows the modified terpene resin, adhesive sealing film B, and adhesive seal used as tackifying resins. Carbon double bond content in the coating liquid B for stop films is shown. The evaluation results of the adhesive sealing film B are shown in Table 3.

[Example 3]
The same operation as in Example 2 was performed except that an aromatic modified terpene resin (YS resin TO125, manufactured by Yasuhara Chemical Co., Ltd.) was used instead of the aromatic modified terpene resin (YS resin TR105, manufactured by Yasuhara Chemical Co., Ltd.). The coating liquid C for adhesive sealing films was prepared. The same operation as Example 1 was performed using the coating liquid C for adhesive sealing films, and the adhesive sealing film C was produced and evaluated.
Table 1 shows the composition of the adhesive sealing film C and the solid content concentration of the coating liquid C for adhesive sealing film, and Table 2 shows the modified terpene resin, adhesive sealing film C, and adhesive seal used as tackifying resins. The carbon double bond content in the coating liquid C for a stop film is shown. Table 3 shows the evaluation results of the adhesive sealing film C.

[Example 4]
Instead of polyisobutylene (number average molecular weight 200,000, manufactured by BASF), polyisobutylene (number average molecular weight 126,000, homopolymer of isobutylene, manufactured by BASF) is used, and alicyclic petroleum resin is used instead of modified terpene resin (Quintone TD-401, manufactured by Nippon Zeon Co., Ltd.) was used, and the same operation as in Example 3 was performed except that the composition shown in Table 1 was used, to prepare a coating solution D for adhesive sealing film. The same operation as Example 1 was performed using the coating liquid D for adhesive sealing films, the adhesive sealing film D was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film D and the solid content concentration of the coating liquid D for adhesive sealing film. Table 2 shows the alicyclic petroleum resin, adhesive sealing film D used as a tackifying resin. Carbon double bond content in the coating liquid D for adhesive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film D.

[Example 5]
An adhesive sealing film E was produced in the same manner as in Example 1 except that 4.4 g of polyisobutylene and alicyclic petroleum resin were dissolved. Table 1 shows the composition of the adhesive sealing film E and the solid content concentration of the coating liquid E for adhesive sealing film. Table 2 shows the alicyclic petroleum resin, adhesive sealing film E used as the tackifying resin. Carbon double bond content in the coating liquid E for adhesive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film E.

[Example 6]
An adhesive sealing film F was produced in the same manner as in Example 1 except that 5.3 g of polyisobutylene and 3.5 g of alicyclic petroleum resin were dissolved. Table 1 shows the composition of the adhesive sealing film F and the solid content concentration of the coating liquid F for adhesive sealing film. Table 2 shows the alicyclic petroleum resin, adhesive sealing film F used as a tackifier resin, Carbon double bond content in the coating liquid E for adhesive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film F.

[Example 7]
A terpene resin (YS Resin PX1250, manufactured by Yasuhara Chemical Co., Ltd.) is used instead of the aromatic modified terpene resin (YS Resin TR105, manufactured by Yasuhara Chemical Co., Ltd.), and a terpene resin having a number average molecular weight of 126000 is used as polyisobutylene. An adhesive sealing film coating solution H was prepared in the same manner as in Example 2 except that 4.4 g of each was added and no polybutene was added. The same operation as Example 1 was performed using the coating liquid H for adhesive sealing films, the adhesive sealing film H was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film H and the solid content concentration of the coating liquid H for adhesive sealing film, and Table 2 shows the terpene resin, adhesive sealing film H, and adhesive sealing used as tackifying resins. Carbon double bond content in the coating liquid H for films is shown. Table 3 shows the evaluation results of the adhesive sealing film H.

[Comparative Example 1]
Polyisobutylene (number average molecular weight 200,000, homopolymer of isobutylene, manufactured by BASF) is used instead of polyisobutylene (number average molecular weight 120,000, manufactured by BASF), and hydrogenated aliphatic is used instead of aliphatic petroleum resin / A coating liquid I for adhesive sealing film was prepared in the same manner as in Example 1 except that an aromatic hybrid petroleum resin (Imabe P-100, manufactured by Idemitsu Kosan Co., Ltd.) was used. The same operation as Example 1 was performed using the coating liquid I for adhesive sealing films, the adhesive sealing film I was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film I and the solid content concentration of the coating liquid I for adhesive sealing film, and Table 2 shows the hydrogenated alicyclic petroleum resin and adhesive sealing film I used as tackifying resins. The carbon double bond content in the coating liquid I for adhesive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film I.

[Comparative Example 2]
A coating liquid J for an adhesive sealing film was prepared in the same manner as in Example 5 except that an aliphatic petroleum resin (Quinton A100) was used instead of the alicyclic petroleum resin. The same operation as Example 5 was performed using the coating liquid J for adhesive sealing films, the adhesive sealing film J was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film J and the solid content concentration of the coating liquid J for adhesive sealing film. Table 2 shows the aliphatic petroleum resin, adhesive sealing film J, and adhesive used as tackifying resins. Carbon double bond content in coating liquid J for adhesive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film J.

[Comparative Example 3]
A coating solution K for adhesive sealing film was prepared in the same manner as in Example 5 except that a hydrogenated indene resin (Alcon P100) was used instead of the alicyclic petroleum resin. The same operation as Example 5 was performed using the coating liquid K for adhesive sealing films, the adhesive sealing film K was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film K and the solid content concentration of the coating liquid K for adhesive sealing film, and Table 2 shows the aliphatic petroleum resin, adhesive sealing film K, and adhesive used as tackifying resins. Carbon double bond content in the coating liquid K for conductive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film K.

[Comparative Example 4]
A coating liquid L for adhesive sealing film was prepared in the same manner as in Example 5 except that an isobutylene-isoprene copolymer (number average molecular weight 1260, Butyl 268, manufactured by JSR Corporation) was used instead of polyisobutylene. Was prepared. The same operation as Example 5 was performed using the coating liquid L for adhesive sealing films, the adhesive sealing film L was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film L and the solid content concentration of the coating liquid L for adhesive sealing film, and Table 2 shows the aliphatic petroleum resin, adhesive sealing film L, and adhesive used as tackifying resins. Carbon double bond content in the coating liquid K for conductive sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film L.

[Comparative Example 5]
Adhesive sealing was carried out in the same manner as in Example 5 except that 0.4 g of epoxy resin (HP7200H, manufactured by DIC Corporation), 4.2 g of polyisobutylene, and 4.2 g of alicyclic petroleum resin were dissolved in the additive. A coating solution M for a stop film was prepared. The same operation as Example 5 was performed using the coating liquid M for adhesive sealing films, the adhesive sealing film M was produced, and the evaluation was performed.
Table 1 shows the composition of the adhesive sealing film M and the solid content concentration of the coating liquid M for adhesive sealing film, and Table 2 shows the aliphatic petroleum resin, adhesive sealing film M, and adhesive used as tackifying resins. Carbon double bond content in the coating liquid M for porous sealing films is shown. Table 3 shows the evaluation results of the adhesive sealing film M.

The following can be seen from the above results.
As in Examples 1 to 7 and Comparative Example 1, the moisture permeability of the adhesive sealing film using polyisobutylene was low, indicating a high moisture barrier property. Furthermore, as in Examples 1 to 7, when the carbon double bond content of the tackifier resin is 1.6% or more, and the carbon double bond content in the adhesive sealing film is 1.8% or more, The tensile shear adhesive strength was 143 N / 100 mm ² or more, and high adhesiveness was exhibited. On the other hand, when the carbon double bond content of the tackifying resin is less than 1.6% and the carbon double bond content in the adhesive sealing film is less than 1.7% as in Comparative Example 1, tensile shear bonding The force was as low as 42 N / 100 mm ² and did not show high adhesion.
Further, as shown in Example 1, it was revealed that the adhesive sealing film of the present invention had a small change in tensile shear adhesive strength before and after the high temperature and high humidity test, and high weather resistance.
From the above, it can be seen that by using a polyisobutylene and a tackifier resin having a high carbon double bond content, an adhesive sealing film having both high moisture barrier properties and high adhesiveness can be produced.

[Example 8-10, Comparative Example 6]
In the following Examples and Comparative Examples, examples in which the tackifier resin of the present invention is applied to an organic electroluminescence element are shown. However, the organic electroluminescence element is not limited to the illustrated embodiment and is not interpreted.
The organic EL light emitting device shown in FIG. 1 is manufactured by the following method.
First, an organic electroluminescence device having a 2 mm square light emitting region is manufactured by the procedure shown in FIG.

<Formation of hole injection layer on ITO substrate>
As an ITO substrate 1, an indium tin oxide (ITO) transparent conductive film (anode 2) having a thickness of 70 nm is formed on a glass substrate 1 having a length of 3.75 cm, a width of 2.5 cm, and a thickness of 0.7 mm. Is used.
Subsequently, a polymer compound (PB-1, weight average molecular weight: 52000, number average molecular weight: 32500) having a repeating structure represented by the following formula (6), and 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) ) Prepare a composition in which borate is mixed at a mass ratio of 100: 20 and dissolved in ethyl benzoate so that the concentration of the mixture is 2.0% by weight. This composition is spin-coated on the ITO substrate 1 in the air atmosphere in two steps of spinner rotation speed of 500 rpm for 2 seconds and further 1500 rpm for 30 seconds. Then, a 30-nm-thick hole injection layer is formed by heating at 230 ° C. for 15 minutes.

<Formation of hole transport layer>
Next, 4,4′-bis [N- (9-phenanthryl) -N-phenyl-amino] biphenyl (PPD) represented by the above formula (2) is vacuum-deposited as the hole transport layer so as to have a film thickness of 40 nm. Film is formed by the method.

<Formation of light emitting layer>
Next, tris (8-hydroxyquinolinate) aluminum (Alq3) is formed as a light emitting layer by a vacuum deposition method so as to have a film thickness of 60 nm.

<Electron injection layer>
Next, lithium fluoride (LiF) is deposited on the light emitting layer by a vacuum deposition method so as to have a film thickness of 0.5 nm to form an electron injection layer. The organic functional layer 3 is defined from the hole injection layer to the electron injection layer.

<Formation of cathode>
Subsequently, aluminum is vapor-deposited by a vacuum vapor deposition method so that it may become a film thickness of 80 nm, and the cathode 4 is formed.

Next, a back member is manufactured according to the procedure shown in FIG.
<Formation of moisture absorption layer>
A 40 μm-thick aluminum foil (manufactured by Tokai Aluminum Foil Co., Ltd.) is cut into a 100 mm square. Using Dry Paste-S1 (manufactured by SaesGetters) mainly composed of calcium oxide as a desiccant, on a cut aluminum foil, in an air atmosphere, using a screen printer (HP-300, manufactured by Neurong Seimitsu Kogyo Co., Ltd.) A hollow rectangular hygroscopic layer having a thickness of 60 μm, a width of 3 mm, and a side of 16 mm is formed. Immediately after printing, move to a nitrogen atmosphere and bake on a hot plate at 200 ° C. for 30 minutes. The aluminum foil is cut into a 23 mm square so that the hollow square moisture absorption layer is in the center.

<Formation of sealing layer>
4.0 g of polyisobutylene (number average molecular weight 120,000, homopolymer of isobutylene, manufactured by BASF), alicyclic petroleum resin (cyclopentadiene-dicyclopentadiene copolymer, Quintone TD-401, Nippon Zeon Co., Ltd.) 4.0 g, 0.08 g of antioxidant (phenolic antioxidant, Irganox 1010, manufactured by BASF) and 16.0 g of toluene (manufactured by Kanto Chemical Co., Ltd.) at room temperature (20 to 30 ° C.) at a mixed rotor (VMR- 3. It is made to melt | dissolve by stirring using ASONE Co., Ltd., and the coating liquid A for adhesive sealing films is prepared.
The adhesive sealing film coating solution A is applied onto a peeled PET film (MRV38, thickness 38 μm, manufactured by Mitsubishi Plastics Co., Ltd.) using an applicator, and heated and dried on an 80 ° C. hot plate for 5 minutes. Then, it vacuum-drys at 100 degreeC for 4 hours, and produces the adhesive sealing film A. In addition, about the adhesive sealing film, the solution which melt | dissolved the said film 0.1g in chloroform is made into a sample, and toluene in a film is quantified by comparing with the chloroform solution containing toluene.
The prepared adhesive sealing film A is attached to an aluminum foil so as to cover the entire surface of the hygroscopic layer, thereby forming a sealing layer. In order to make it adhere so that air may not enter between aluminum foil and adhesive sealing film A, and a sealing layer, a sheet-like adhesive is roller-pressed on a PET film on a 100 degreeC hotplate. .

<Lamination of organic electroluminescence element and back member>
Affixed by hand so that the adhesive surface of the sealing layer prepared as described above covers the light emitting layer of the organic electroluminescence element, and the edge of the moisture absorbing layer protrudes 4 mm from the edge of the light emitting area of the light emitting layer along the horizontal direction. wear. Place the glass side of the organic electroluminescence element on a hot plate at 100 ° C., press the aluminum foil of the back member with a roller, and then, outside the light emitting region of the back member, the region where the moisture absorption layer is not formed, Pressure is applied with a roller to obtain the organic EL light emitting device shown in FIG. This organic EL light-emitting device is surrounded by a hollow rectangular moisture-absorbing layer while maintaining a constant interval along the outer periphery of the light-emitting region of the light-emitting layer.
Using the organic electroluminescence device prepared as described above, the presence or absence of dark spots was evaluated. The results are shown in the table below.

  From the above results, it can be seen that the initial dark spot generation is suppressed when the residual toluene amount is 3000 ppm or less.

DESCRIPTION OF SYMBOLS 1 Translucent board | substrate 2 1st electrode 2a Extraction electrode 3 of 2nd electrode Organic functional layer 3a Light emission area | region edge part 4 of the light emitting layer which comprises the organic functional layer 3 2nd electrode 5 Sealing layer 5a Sealing layer 5 end 6 hygroscopic layer 6a hygroscopic layer 6 end 7 protective layer 9
10 Organic EL light emitting device

Claims (12)

An adhesive sealing film containing polyisobutylene having a number average molecular weight of 10,000 or more and a tackifying resin having a carbon double bond content of 1.6% or more and 50.0% or less,
An adhesive sealing film in which the concentration of toluene remaining in the film is 3000 ppm or less.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the tackifying resin is measured by ¹ H-NMR. Is represented by the following equation.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and is bonded to the double-bonded carbon. The proton amount is the sum of the proton spectral areas observed at 4.6 to 8.0 ppm. )   The adhesive sealing film according to claim 1, wherein the tackifying resin has a number average molecular weight of 800 or more and 1600 or less.   The adhesiveness according to claim 1 or 2, wherein the tackifying resin is one or more selected from the group consisting of a rosin resin, a terpene resin, an alicyclic petroleum resin, and an aromatic petroleum resin. Sealing film.   The adhesive sealing film according to any one of claims 1 to 3, wherein the polyisobutylene has a number average molecular weight of 10,000 or more and 1,000,000 or less.   The adhesive sealing film according to any one of claims 1 to 4, wherein the amount of water remaining in the film is 500 ppm or less. The adhesive sealing film according to any one of claims 1 to 5, wherein a carbon double bond content in the adhesive sealing film is 1.8% or more and 50.0% or less.
(Here, the carbon double bond content in the adhesive sealing film is the amount of protons bound to the double-bonded carbon with respect to all the protons when the adhesive sealing film is measured by ¹ H-NMR. The ratio is expressed by the following formula.
Carbon double bond content in adhesive sealing film = (Amount of protons bound to double-bonded carbon contained in adhesive sealing film
/ All protons contained in the adhesive sealing film) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the adhesive sealing film is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and the double bonded carbon The amount of protons bound is the sum of the spectral areas of protons observed at 4.6 to 8.0 ppm. ) The adhesive sealing film according to any one of claims 1 to 6, wherein the minimum value of the storage elastic modulus at -20 to 50 ° C is 1 x 10 ⁹ Pa or less.   The adhesive sealing film which is an adhesive sealing film for organic electroluminescence in any one of Claim 1 thru | or 7. A method for producing the adhesive sealing film according to any one of claims 1 to 8, wherein the polyisobutylene having a number average molecular weight of 10,000 or more and a carbon double bond content of 1.6% or more 50 The manufacturing method of the adhesive sealing film which dries after apply | coating the coating liquid for adhesive sealing films containing tackifying resin which is 0.0% or less on a base material.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the tackifying resin is measured by ¹ H-NMR. Is represented by the following equation.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and is bonded to the double-bonded carbon. The proton amount is the sum of the proton spectral areas observed at 4.6 to 8.0 ppm. ) A coating solution for an adhesive sealing film comprising a polyisobutylene having a number average molecular weight of 10,000 or more and a tackifying resin having a carbon double bond content of 1.6% or more and 50.0% or less, The coating liquid for adhesive sealing films for manufacturing the adhesive sealing film of any one of Claim 1 thru | or 8 by making it dry after apply | coating on a material.
(Here, the carbon double bond content in the tackifying resin is the ratio of the amount of protons bonded to the double bonded carbon to the total amount of protons when the tackifying resin is measured by ¹ H-NMR. Is represented by the following equation.
Carbon double bond content in tackifier resin = (the amount of protons bound to double-bonded carbon contained in the tackifier resin)
/ Amount of all protons contained in the tackifying resin) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the tackifying resin is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and is bonded to the double-bonded carbon. The proton amount is the sum of the proton spectral areas observed at 4.6 to 8.0 ppm. )   The coating solution for an adhesive sealing film according to claim 10, further containing toluene. The coating solution for adhesive sealing films according to claim 10 or 11, wherein the content of carbon double bonds in the solid content of the coating solution for adhesive sealing films is 1.8 to 50.0%.
(Here, the solid content of the coating solution for the adhesive sealing film is obtained by removing the solvent from the coating solution for the adhesive sealing film. The carbon double in the solid content of the coating solution for the adhesive sealing film) The bond content is the ratio of the amount of protons bonded to double-bonded carbon to the total amount of protons when the solid content is measured by ¹ H-NMR, and is represented by the following formula.
Carbon double bond content in solid content of coating solution for adhesive sealing film = (contained in coating solution for adhesive sealing film,
The amount of protons bonded to double-bonded carbon / the total amount of protons contained in the solid content of the coating solution for adhesive sealing film) × 100
In the ¹ H-NMR measurement, the amount of all protons contained in the solid content is the sum of the proton spectral areas observed at 0.1 to 8.0 ppm, and protons bonded to double-bonded carbon The amount is the sum of the proton spectral areas observed at 4.6-8.0 ppm. )

Images