JP6492410B2 - Organic device - Google Patents

Description

The present invention relates to an organic device.

In recent years, organic devices such as organic electroluminescence (EL) elements have attracted attention. The organic EL element has organic layers such as an organic light emitting layer, an electron transport layer, and a hole transport layer, and these organic layers may be deteriorated by reacting with water vapor or oxygen in the atmosphere. In order to protect organic devices such as EL elements, a thin film sealing technique for forming a gas barrier layer with a thin film is required.

For example, Patent Document 1 discloses that a CVD method using a plasma generated under a pressure of 600 to 1520 Torr using, as a raw material, an organic silicon compound that is liquid in a temperature range of 20 to 150 ° C. on a polymer film. _A method for producing a gas barrier film characterized by forming a thin film mainly composed of silicon oxide represented by _x (x = 1.0 to 2.0) is described. Patent Document 2 describes a gas barrier film having a gas barrier layer of any one of a SiCNFH layer, a SiOCNH layer, and a SiCNH layer deposited by Cat-CVD. Patent Document 3 discloses a barrier film made of silicon nitride, wherein a ratio N / (Si + N) representing an atomic ratio of nitrogen N and silicon Si is between 0.60 and 0.65. A membrane is described.

Also proposed is a method of protecting the element body from moisture and oxygen by forming an inorganic thin film such as silicon nitride on the element body and applying a resin thereon by spin coating or dipping. ing. In such a method, it is necessary to form a dense inorganic thin film in order to provide a sufficient barrier property to the inorganic thin film. However, since the organic material of the element main body is sealed, the film forming temperature of the inorganic thin film Can not be raised. For this reason, defects occur in the inorganic thin film or a dense thin film cannot be formed. Therefore, in order to provide sufficient barrier properties, it is necessary to form the inorganic thin film thickly.
On the other hand, when the inorganic thin film is thickened, cracks are likely to occur due to an increase in stress, and there is a problem that the barrier property is lowered.
Therefore, it has been proposed to relieve stress generated in an inorganic thin film by alternately laminating organic materials and inorganic materials.

For example, Patent Document 4 describes an organic electroluminescence device including a barrier layer having a structure in which organic layers and inorganic layers are alternately formed and laminated.

Patent Document 5 includes a passivation layer including a plurality of alternately stacked barrier layers and a plurality of buffer layers, and the barrier layer is selected from a metal or semiconductor active oxide, active nitride, or active oxynitride. The organic EL element is characterized in that the buffer layer contains one or more substances and the buffer layer contains an organic polymer or an organic low molecule.

Patent Document 6 discloses a gas barrier laminate film having, on a base film, at least one inorganic layer and at least one layer of an organic layer mainly composed of a polymer of an acrylic monomer, A gas barrier laminate film characterized by containing a polymerization product of a bifunctional or higher polymerizable monomer having at least one sulfonyl group is described.

U.S. Patent No. 6,057,059 describes an encapsulated organic light emitting device that includes a first barrier stack that includes at least one first barrier layer and at least one first polymer layer.

JP 11-256338 A JP 2010-235979 A JP 2011-231357 A JP 2003-17244 A JP 2007-317646 A JP 2008-87163 A JP 2002-532850 A

The barrier layers of the organic EL elements described in Patent Documents 4 to 7 are obtained by alternately laminating inorganic layers and organic layers, and these organic layers are adhered to the inorganic layer and bonded to the inorganic layer. Used to relieve the stress generated.
Since the organic layer needs to have good adhesion to the inorganic layer, an organic material is selected with an emphasis on adhesion to the inorganic material. At present, organic materials with high properties are used.

This invention is made | formed in view of the said present condition, and is excellent in adhesiveness with an inorganic sealing layer, Furthermore, it aims at providing the organic device which has the organic sealing layer which has the outstanding low water vapor permeability. And

The inventors of the present invention have made extensive studies on an organic sealing layer having excellent adhesion to the inorganic sealing layer and having excellent low water vapor permeability.
Fluoropolymers are generally difficult to adhere to other materials and are difficult to apply to applications that require adhesion. However, as a result of studies by the present inventors, the organic sealing layer containing a fluoropolymer having a specific structure has good adhesion to the inorganic sealing layer and also has excellent low water vapor permeability. As a result, the present invention has been completed.

That is, the present invention is an organic device having a laminated structure in which an inorganic sealing layer and an organic sealing layer are laminated, and the organic sealing layer includes a fluorine-containing copolymer having a fluorine-containing olefin unit and a vinyl alcohol unit. It is an organic device characterized by including coalescence.

The fluorine-containing olefin is preferably tetrafluoroethylene.

It is preferable that the content rate of the fluorine-containing olefin unit in the said fluorine-containing copolymer is 40 mol% or more.

It is preferable that the alternating rate of the fluorine-containing olefin unit and the vinyl alcohol unit in the fluorine-containing copolymer is 94% or less.

The fluorine-containing copolymer preferably has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit.

The fluorine-containing copolymer is preferably a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit.

The organic device of the present invention is preferably an organic electroluminescence element.

ADVANTAGE OF THE INVENTION According to this invention, the organic device which has an organic sealing layer excellent in adhesiveness with an inorganic sealing layer and low water vapor permeability can be provided.

It is a cross-sectional schematic diagram which shows an example of the organic device (organic EL element) of this invention. It is a cross-sectional schematic diagram which shows an example of the organic device (organic EL element) of this invention.

Hereinafter, the present invention will be specifically described.

The organic device of the present invention is an organic device having a laminated structure in which an inorganic sealing layer and an organic sealing layer are stacked, and the organic sealing layer includes a fluorine-containing olefin unit and a vinyl alcohol unit. Including copolymers.

The organic device of the present invention has an organic sealing layer. Since the said organic sealing layer is formed from the said specific fluorine-containing copolymer, it is excellent in low water vapor permeability. Therefore, in the organic device of the present invention, the organic element part such as the organic light emitting layer is not easily deteriorated.
Moreover, since the said organic sealing layer is formed from the said specific fluorine-containing copolymer, it is excellent in adhesiveness with an inorganic sealing layer. Therefore, the organic device of the present invention is excellent in durability. The organic sealing layer is also excellent in adhesion with an electrode or the like formed from an inorganic material.
In the organic device of the present invention, when the barrier layer is formed by alternately laminating inorganic sealing layers and organic sealing layers formed of an inorganic material, the organic sealing layer is in close contact with the inorganic sealing layer. In addition to contributing to relaxation of the stress between the inorganic sealing layers, excellent low water vapor permeability can be imparted to the barrier layer.
For example, a barrier layer of an organic EL element is required to have a low water vapor permeability of the order of 10 ⁻⁵ , but even if the number of inorganic sealing layers is reduced as compared with the conventional technique, an excellent low water vapor permeability is obtained. The device can be granted and the above requirements can be achieved. In addition, since the number of stacked layers can be reduced, the manufacturing process can be simplified.
Furthermore, the organic sealing layer is particularly suitable as a sealing layer used in organic devices because it is excellent in light transmittance and plasma resistance.

The thickness of the organic sealing layer is not particularly limited, and may be set as appropriate depending on the type, structure, required characteristics, and the like of the organic device. For example, from the viewpoint of device protection, the thickness is preferably 10 nm or more, and more preferably 50 nm or more. From the viewpoint of productivity, it is preferably 150 μm or less, more preferably 100 μm or less, and further preferably 50 μm or less.

The fluorine-containing copolymer has a fluorine-containing olefin unit and a vinyl alcohol unit (—CH ₂ —CH (OH) —).

The said fluorine-containing olefin unit represents the polymerization unit based on a fluorine-containing olefin. The fluorine-containing olefin is a monomer having a fluorine atom.

Examples of the fluorine-containing olefin include tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], vinyl fluoride, hexafluoropropylene [HFP], hexafluoroisobutene, CH ₂ = CZ. ¹ (CF ₂ ) _n1 Z ² (wherein Z ¹ is H, F or Cl, Z ² is H, F or Cl, and n1 is an integer of 1 to 10), CF ₂ = CF-ORf ¹ (wherein Rf ¹ represents a perfluoroalkyl group having 1 to 8 carbon atoms) and CF ₂ = CF-OCH ₂ -rf ² (wherein, Rf ² is a perfluoroalkyl group having 1 to 5 carbon atoms) selected from the group consisting of alkyl perfluorovinyl ether derivative represented by the It is preferably be at least one kind of fluorine-containing olefin.

Examples of the monomer represented by CH ₂ = CZ ¹ (CF ₂ ) _n1 Z ² include CH ₂ = CFCF ₃ , CH ₂ = CHCF ₃ , CH ₂ = CFCHF ₂ and CH ₂ = CClCF ₃ .

Examples of the PAVE include perfluoro (methyl vinyl ether) [PMVE], perfluoro (ethyl vinyl ether) [PEVE], perfluoro (propyl vinyl ether) [PPVE], perfluoro (butyl vinyl ether), etc. Among them, PMVE PEVE or PPVE is more preferable.

As the alkyl perfluorovinyl ether derivative, those in which Rf ² is a perfluoroalkyl group having 1 to 3 carbon atoms are preferable, and CF ₂ = CF—OCH ₂ —CF ₂ CF ₃ is more preferable.

As said fluorine-containing olefin, at least 1 sort (s) selected from the group which consists of TFE, CTFE, and HFP is more preferable, and TFE is still more preferable.

The fluorine-containing copolymer preferably has a fluorine-containing olefin unit content of 40 mol% or more in the fluorine-containing copolymer, the fluorine-containing olefin unit is from 40 mol% to 80 mol%, and vinyl alcohol. More preferably, the unit is 20 mol% or more and 60 mol% or less. When the content of each monomer unit in the fluorine-containing copolymer is in such a range, an organic encapsulating layer having low water vapor permeability and excellent adhesion with the inorganic encapsulating layer can be obtained. As the content of each monomer unit, the fluorine-containing olefin unit is 45 mol% or more and 75 mol% or less, the vinyl alcohol unit is more preferably 25 mol% or more and 55 mol% or less, and the fluorine-containing olefin unit is 50 mol% or less. It is particularly preferred that the content is from mol% to 70 mol%, and the vinyl alcohol unit is from 30 mol% to 50 mol%.

The fluorine-containing copolymer preferably has an alternating ratio of fluorine-containing olefin units and vinyl alcohol units of 94% or less. When the alternating rate is in such a range, an effect of high solvent solubility can be obtained. More preferably, it is 90% or less, and particularly preferably 80% or less. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. If the alternating rate is low, the heat resistance may decrease, which is not preferable.

The alternating rate of the fluorinated olefin unit and the vinyl alcohol unit was determined by performing ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone is dissolved, and calculating from the following formula: It can be calculated as the alternating rate of chain.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of V bonded to two T like T- (T: fluorine-containing olefin unit, V: vinyl alcohol unit)
The number of V units of A, B, and C is calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of the vinyl alcohol unit (—CH ₂ —CH (OH) —) of ¹ H-NMR measurement. The estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

The fluorine-containing copolymer is further represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). It may have a vinyl ester monomer unit. Thus, it is also preferable that the said fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit. Furthermore, it is also preferable that the copolymer is a fluorine-containing olefin / vinyl alcohol / vinyl ester monomer copolymer substantially consisting of a fluorine-containing olefin unit, a vinyl alcohol unit and a vinyl ester monomer unit.

The vinyl ester monomer unit is a monomer represented by —CH ₂ —CH (O (C═O) R) — (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 17 carbon atoms). Although it is a unit, as R in the said formula, a C1-C11 alkyl group is preferable and a C1-C5 alkyl group is more preferable. Particularly preferred is an alkyl group having 1 to 3 carbon atoms.

Examples of the vinyl ester monomer unit include monomer units derived from the following vinyl esters.
Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valelate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, vinyl pelargonate, vinyl caprate, Vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova-10 (Showa Shell Sekiyu KK) )), Vinyl benzoate, vinyl versatate.
Among these, monomer units derived from vinyl acetate, vinyl propionate, and vinyl versatate are preferable. More preferred are vinyl acetate monomer units and vinyl propionate monomer units, and even more preferred are vinyl acetate monomer units.

When the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit, the content of each monomer unit is 40 mol% or more and 80 mol% or less of the fluorine-containing olefin unit. The vinyl alcohol unit is preferably more than 0 mol% and less than 60 mol%, and the vinyl ester monomer unit is preferably more than 0 mol% and less than 60 mol%. When the content of each monomer unit is in such a range, the organic water-sealing layer has low water vapor permeability and excellent adhesion with an inorganic material. As the content of each monomer unit, the fluorine-containing olefin unit is from 45 mol% to 75 mol%, the vinyl alcohol unit is from 5 mol% to 50 mol%, and the vinyl ester monomer unit is from 5 mol% to 50 mol%. More preferably, the fluorine-containing olefin unit is 50 mol% or more and 70 mol% or less, the vinyl alcohol unit is 10 mol% or more and 40 mol% or less, and the vinyl ester monomer unit is 10 mol% or more. More preferably, it is 40 mol% or less.

When the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit, the alternating rate of the fluorine-containing olefin unit, the vinyl alcohol unit, and the vinyl ester monomer unit is 94% or less. Is preferred. When the alternating rate is in such a range, an effect of high solvent solubility can be obtained. More preferably, it is 90% or less, and particularly preferably 80% or less. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40% or more. If the alternating rate is low, the heat resistance may decrease, which is not preferable.

The alternating rate of the fluorinated olefin unit, the vinyl alcohol unit, and the vinyl ester monomer unit is determined by performing ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone is dissolved, It can be calculated as an alternating rate of three chains from the following formula.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of Vs bonded to two Ts such as T- (T: fluorinated olefin unit, V: vinyl alcohol unit or vinyl ester monomer unit)
The number of V units of A, B, and C is the vinyl alcohol unit (—CH ₂ —CH (OH) —) and vinyl ester monomer unit (—CH ₂ —CH (O (C═O)) of ¹ H-NMR measurement. Calculated from the intensity ratio of H of the main chain bonded to the tertiary carbon of R)-). The estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

The said fluorine-containing copolymer may have other monomer units other than a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit in the range which does not impair the effect of this invention.

As said other monomer, as a monomer which does not contain a fluorine atom (however, except vinyl alcohol and a vinyl ester monomer), for example, ethylene, propylene, 1-butene, 2-butene, vinyl chloride, Preference is given to at least one fluorine-free ethylenic monomer selected from the group consisting of vinylidene chloride, vinyl ether monomers and unsaturated carboxylic acids.

The total content of the other monomer units is preferably 0 to 50 mol%, more preferably 0 to 40 mol%, based on all monomer units of the fluorine-containing copolymer, More preferably, it is 30 mol%.

In the present specification, the content of each monomer unit constituting the fluorine-containing copolymer can be calculated by appropriately combining NMR, FT-IR, and elemental analysis depending on the type of monomer.

The weight average molecular weight of the fluorine-containing copolymer is not particularly limited, but is preferably 9,000 or more, and more preferably 10,000 or more. More preferably, it is 20,000-2,000,000, Most preferably, it is 30,000-1,000,000.
The weight average molecular weight can be determined by gel permeation chromatography (GPC).

As described later, the fluorine-containing copolymer can be produced by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. That is, the fluorine-containing copolymer is preferably a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit.

Below, the manufacturing method of the said fluorine-containing copolymer is demonstrated.
Usually, the fluorine-containing copolymer is produced by copolymerizing a fluorine-containing olefin such as tetrafluoroethylene and a vinyl ester monomer such as vinyl acetate and then hydroxylating the obtained copolymer. Can do. When the alternation ratio of the fluorine-containing copolymer is 94% or less, it is preferable to carry out the polymerization under the condition that the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept almost constant. That is, the above-mentioned fluorine-containing copolymer is polymerized under a condition in which the composition ratio of the fluorine-containing olefin and the vinyl ester monomer is kept almost constant to obtain a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. It is preferably obtained by a production method comprising a step and a step of obtaining a copolymer having a fluorine-containing olefin unit and a vinyl alcohol unit by hydroxylating the obtained copolymer.

Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl isovalerate, vinyl caproate, vinyl heptylate, vinyl caprylate, vinyl pivalate, pelargon. Vinyl acetate, vinyl caprate, vinyl laurate, vinyl myristate, vinyl pentadecylate, vinyl palmitate, vinyl margarate, vinyl stearate, vinyl octylate, Veova-9 (manufactured by Showa Shell Sekiyu KK), Veova 10 (manufactured by Showa Shell Sekiyu KK), vinyl benzoate, vinyl versatate, and the like. Of these, vinyl acetate, vinyl propionate, and vinyl versatate are preferably used because they are easily available and inexpensive.
As said vinyl ester monomer, 1 type of these may be used and 2 or more types may be mixed and used.

Examples of the method of copolymerizing the fluorinated olefin and the vinyl ester monomer include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like, and emulsion polymerization is easy because it is industrially easy to implement. However, it is preferable to produce by solution polymerization or suspension polymerization, but not limited thereto.

In emulsion polymerization, solution polymerization, or suspension polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant, a dispersant, and the like can be used, and those usually used can be used.

The solvent used in the solution polymerization is preferably a solvent capable of dissolving the fluorine-containing olefin, the vinyl ester monomer, and the fluorine-containing copolymer to be synthesized. For example, n-butyl acetate, t-butyl acetate, ethyl acetate Esters such as methyl acetate and propyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Methanol and ethanol Alcohols such as tert-butanol and isopropanol; cyclic ethers such as tetrahydrofuran and dioxane; fluorine-containing solvents such as HCFC-225; dimethyl sulfoxide, dimethylformamide, and mixtures thereof.
Examples of the solvent used in the emulsion polymerization include water, a mixed solvent of water and alcohol, and the like.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

As the surfactant, a commonly used surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used. Moreover, you may use a fluorine-containing surfactant.

In the suspension polymerization, a dispersant may be used. Dispersants include water-soluble cellulose ethers such as partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose used in ordinary suspension polymerization, water-soluble polymers such as acrylic acid polymers, and gelatin. Can be illustrated. Suspension polymerization is carried out under the condition that the ratio of water / monomer is usually 1.5 / 1 to 3/1 in terms of weight ratio, and the dispersant is 0.01 to 0. 1 part by weight is used. If necessary, a pH buffer such as polyphosphate can be used.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
The amount of the chain transfer agent added may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.001 to 10% by mass relative to the polymerization solvent.

The polymerization temperature may be in a range where the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 100 ° C.

The polymerization pressure may be in a range in which the composition ratio during the reaction of the fluorinated olefin and the vinyl ester monomer is substantially constant, and may be 0 to 10 MPaG.

Hydroxylation of an acetate group derived from vinyl acetate is well known in the art, and can be performed by a conventionally known method such as alcoholysis or hydrolysis using an acid or base. Of these, hydrolysis using a base is generally called saponification. In this specification, however, hydroxylation of a vinyl ester monomer is hereinafter called saponification regardless of the method. By this saponification, the acetate group (—OCOCH ₃ ) is converted into a hydroxyl group (—OH). Similarly, other vinyl ester monomers can be saponified by a conventionally known method to obtain a hydroxyl group.

The degree of saponification in the case of obtaining the above-mentioned fluorine-containing copolymer by saponifying a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit is the content of each monomer unit of the fluorine-containing copolymer described above. The range may be within the range, specifically 50% or more is preferable, 60% or more is more preferable, and 70% or more is more preferable.

The saponification degree is calculated from the following equation by IR measurement or ¹ H-NMR measurement of the fluorine-containing copolymer.
Saponification degree (%) = D / (D + E) × 100
D: number of vinyl alcohol units in the fluorinated copolymer E: number of vinyl ester monomer units in the fluorinated copolymer

The fluorine-containing copolymer is a vinyl ether monomer (CH ₂ = CH-OR) (hereinafter simply referred to as a vinyl ether monomer) in which a fluorine-containing olefin and a protecting group (R) that can be converted to vinyl alcohol by a deprotection reaction are bonded. To obtain a fluorinated olefin / vinyl ether copolymer, and deprotecting the fluorinated olefin / vinyl ether copolymer to obtain a fluorinated olefin / vinyl alcohol copolymer. It can also be obtained by a production method comprising steps.

A method for copolymerizing the fluorinated olefin and the vinyl ether monomer and a method for deprotecting the fluorinated olefin / vinyl ether copolymer are well known in the art. It can be carried out. By deprotecting the fluorinated olefin / vinyl ether copolymer, the protecting group alkoxy group is converted to a hydroxyl group, and a fluorinated olefin / vinyl alcohol copolymer is obtained.

The fluorine-containing olefin / vinyl ether copolymer obtained by copolymerizing the fluorine-containing olefin and the vinyl ether monomer is a molar ratio of the fluorine-containing olefin and the vinyl ether monomer (fluorine-containing olefin) / (vinyl ether unit The (mer) is preferably (40-60) / (60-40), and more preferably (45-55) / (55-45). When the molar ratio is in the above range and the deprotection is in the range described later, a fluorinated copolymer in which the molar ratio of each polymer unit is in the above range can be produced.

The deprotection of the fluorinated olefin / vinyl ether copolymer is preferably performed so that the degree of deprotection is 1 to 100%, and more preferably 30 to 100%.

The degree of deprotection is determined by ¹ H-NMR, the integrated value of protons derived from an acetyl group (CH ₃ C (═O) O—) near 2.1 ppm before and after deprotection, and 0.8 to 1.8 ppm. It can be measured by quantifying the integral value of protons derived from the main chain methylene group (—CH ₂ —CH—).
¹ H-NMR: GEMINI-300 manufactured by Varian

The vinyl ether monomer preferably does not contain a fluorine atom. The vinyl ether monomer is not particularly limited as long as it is deprotected, but tertiary butyl vinyl ether is preferable from the viewpoint of availability.

When the said fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ether unit, it is preferable that the alternating rate of a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ether unit is 94% or less. When the alternating rate is in such a range, an effect of high solvent solubility can be obtained. Further, it is preferably 30% or more, more preferably 35% or more, and further preferably 40%. If the alternating rate is low, the heat resistance is lowered, which is not preferable.

The alternating rate of the fluorinated olefin unit, the vinyl alcohol unit and the vinyl ether unit was measured by ¹ H-NMR measurement of the fluorinated copolymer using a solvent in which the fluorinated copolymer such as heavy acetone was dissolved. It can be calculated as an alternating rate of three chains from the equation.
Alternating rate (%) = C / (A + B + C) × 100
A: The number of V combined with two Vs such as -VVVV- B: The number of V combined with V and T as -VVT- C: -TV- Number of Vs bonded to two Ts such as T- (T: fluorine-containing olefin unit, V: vinyl alcohol unit or vinyl ether unit)
The number of V units of A, B, and C is the tertiary carbon of vinyl alcohol unit (—CH ₂ —CH (OH) —) and vinyl ether unit (—CH ₂ —CH (OR)) measured by ¹ H-NMR. It calculates from the intensity ratio of H of the main chain to couple | bond. The estimation of the strength ratio of H in the main chain by ¹ H-NMR measurement is carried out with the fluorine-containing copolymer before hydroxylation.

Examples of the method for copolymerizing the fluorine-containing olefin and the vinyl ether monomer include solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, and the like, which are industrially easy to implement. Although it is preferable to manufacture by emulsion polymerization, solution polymerization, or suspension polymerization, it is not this limitation.

In the above emulsion polymerization, solution polymerization or suspension polymerization, a polymerization initiator, a solvent, a chain transfer agent, a surfactant, a dispersant and the like can be used, and those usually used can be used.

The solvent used in the solution polymerization is preferably a solvent capable of dissolving the fluorine-containing olefin, the vinyl ether monomer, and the fluorine-containing copolymer to be synthesized. For example, n-butyl acetate, t-butyl acetate, Esters such as ethyl acetate, methyl acetate and propyl acetate; Ketones such as acetone, methyl ethyl ketone and cyclohexanone; Aliphatic hydrocarbons such as hexane, cyclohexane and octane; Aromatic hydrocarbons such as benzene, toluene and xylene; Methanol Alcohols such as ethanol, tert-butanol and isopropanol; cyclic ethers such as tetrahydrofuran and dioxane; fluorine-containing solvents such as HCFC-225; dimethyl sulfoxide, dimethylformamide, and mixtures thereof.
Examples of the solvent used in the emulsion polymerization include water, a mixed solvent of water and alcohol, and the like.

Examples of the polymerization initiator include oil-soluble radical polymerization initiators typified by peroxycarbonates such as diisopropyl peroxydicarbonate (IPP) and di-n-propyl peroxydicarbonate (NPP). Water-soluble radical polymerization initiators such as persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, ammonium percarbonate, potassium salt and sodium salt can be used. Particularly in emulsion polymerization, ammonium persulfate and potassium persulfate are preferred.

As the surfactant, a commonly used surfactant can be used. For example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used. Moreover, you may use a fluorine-containing surfactant.

In the suspension polymerization, a dispersant may be used. Dispersants include water-soluble cellulose ethers such as partially saponified polyvinyl acetate, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose used in ordinary suspension polymerization, water-soluble polymers such as acrylic acid polymers, and gelatin. Can be illustrated. Suspension polymerization is carried out under the condition that the ratio of water / monomer is usually 1.5 / 1 to 3/1 in terms of weight ratio, and the dispersant is 0.01 to 0.00 per 100 parts by weight of monomer. 1 part by weight is used. If necessary, a pH buffer such as polyphosphate can be used.

Examples of the chain transfer agent include hydrocarbons such as ethane, isopentane, n-hexane, and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; and acetates such as ethyl acetate and butyl acetate; Examples include alcohols such as methanol and ethanol; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride.
The amount of the chain transfer agent added may vary depending on the size of the chain transfer constant of the compound used, but is usually used in the range of 0.001 to 10% by mass relative to the polymerization solvent.

The polymerization temperature may be in a range in which the composition ratio during the reaction of the fluorinated olefin and the vinyl ether monomer is substantially constant, and may be 0 to 100 ° C.

The polymerization pressure may be in a range where the composition ratio during the reaction of the fluorinated olefin and the vinyl ether monomer is substantially constant, and may be 0 to 10 MPaG.

The deprotection of the vinyl ether monomer can be performed by a conventionally known method such as acid, heat or light. By this deprotection, the leaving group (for example, —C (CH ₃ ) ₃ ) can be replaced with hydrogen to obtain a hydroxyl group.

The degree of deprotection in the case of obtaining the above-mentioned fluorine-containing copolymer by deprotecting the copolymer having the above-mentioned fluorine-containing olefin unit and vinyl ether monomer unit is the content of each monomer unit of the above-mentioned fluorine-containing copolymer. Is within the range described above, specifically 50% or more is preferable, 60% or more is more preferable, and 70% or more is more preferable.

The degree of deprotection is calculated from the following formula by IR measurement of the fluorine-containing copolymer or the above-mentioned ¹ H-NMR measurement.
Deprotection degree (%) = D / (D + E) × 100
D: Number of vinyl alcohol units in the fluorinated copolymer E: Number of vinyl ether monomer units in the fluorinated copolymer

The organic sealing layer can be formed from an organic device sealing agent containing a fluorine-containing copolymer having a fluorine-containing olefin unit and a vinyl alcohol unit.
The organic device sealant can be prepared in a conventional manner in the form of a solvent-type paint, a water-type paint, a powder paint, or the like. Among these, the form of a solvent-type paint is preferable from the viewpoint of easy film formation and good drying properties.
That is, it is preferable that the organic device sealing agent further contains a solvent. By including a solvent, thin film coating becomes easier and the resulting coating film can be made thinner.

The solvent is preferably an organic solvent, esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; tetrahydrofuran Cyclic ethers such as dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; glycols such as propylene glycol methyl ether and ethyl cellosolve Ethers; diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-undecane n- dodecane, aliphatic hydrocarbons such as mineral spirit; a mixed solvent, and the like.
Of these, esters are preferable, and butyl acetate is particularly preferable.

When the organic device sealant is a solvent-type paint, the concentration of the fluorinated copolymer with respect to the total amount of the organic device sealant of 100% by mass is preferably 0.1 to 95% by mass, and 10 to 70% by mass. % Is more preferable.

In the organic device sealing agent, various additives can be further blended in addition to the fluorinated polymer in accordance with the required properties within a range not impairing the effects of the present invention. Examples of the additive include a silane coupling agent, an inorganic filler, a curing agent, and a curing catalyst. Examples of the curing agent include isocyanate curing agents and amino resin curing agents.

Examples of the method for forming the organic sealing layer from the organic device sealing agent include a coating method and a vacuum film forming method.
When the organic sealing layer is formed by coating, various conventionally used coating methods such as spin coating, roll coating, gravure coating, knife coating, dip coating, curtain flow coating, spray coating, and bar coating are used. be able to.
As the vacuum film formation method, for example, film formation methods such as vacuum evaporation, molecular beam evaporation (MBE), ion plating, ion beam evaporation, conventional sputtering, magnetron sputtering, ion beam sputtering, and ECR sputtering are preferable. A resistance heating vapor deposition method that allows easy control of the deposition rate is more preferred.
As a method of forming the organic sealing layer, a method by coating is preferable from the viewpoint of simplicity of the process, and a spin coating method is more preferable.

The organic device of the present invention has a stacked structure in which an organic sealing layer and an inorganic sealing layer are stacked. Since the said organic sealing layer is excellent in adhesiveness with an inorganic sealing layer, it can provide especially excellent low water vapor permeability to an organic device by using together with an inorganic sealing layer.
The organic device of the present invention may be a laminate of one organic sealing layer and one inorganic sealing layer, or two or more organic sealing layers and two or more inorganic sealing layers. The layers may be alternately stacked.
The number of stacked organic sealing layers may be appropriately set according to the required low water vapor permeability and the thickness of the organic sealing layer and the inorganic sealing layer, and is preferably 1 to 10, for example.
Similarly, the number of laminated inorganic sealing layers is preferably 1 to 10.

The inorganic sealing layer is a layer made of an inorganic material. The inorganic sealing layer is preferably a layer made of an oxide, nitride, or oxynitride of a metal such as silicon, aluminum, titanium, zirconium, tin, etc., and may be formed of a composite thereof. Good.
In view of the excellent low water vapor permeability of the inorganic sealing layer and the excellent adhesion between the inorganic sealing layer and the organic sealing layer, the material forming the inorganic sealing layer is an oxide of silicon, aluminum or zirconium, Nitride or oxynitride is preferable, and silicon oxide, nitride, or oxynitride is more preferable.
What is necessary is just to set the thickness of an inorganic sealing layer suitably with the barrier property requested | required, the material which comprises an inorganic sealing layer, etc. For example, when the inorganic sealing layer is too thick, cracks due to stress may occur, so that it is preferably 200 nm or less, and more preferably 150 nm or less.
Moreover, since it is excellent in low water vapor permeability, it is preferably 10 nm or more, and more preferably 30 nm or more.

As the method for forming the inorganic sealing layer, physical vapor deposition (PVD) such as vapor deposition, sputtering or ion plating, various chemical vapor deposition (CVD), plating, sol-gel, etc. There is a liquid phase growth method. Of these, chemical vapor deposition (CVD) and physical properties are avoided in that the effect of heat on the element part and the substrate during the formation of the inorganic sealing layer is avoided, the production rate is high, and a uniform thin film layer is easily obtained. Vapor phase epitaxy (PVD) is preferred. Moreover, since a thick film is easy to obtain, an inorganic sealing layer can also be formed by a sol-gel method. Here, the thick film refers to a film in the range of 100 nm to 1 μm.

As an organic device of this invention, the organic EL element which consists of an electrode and a light emitting layer; Organic thin film solar cell, an organic transistor, an organic field effect transistor etc. are mentioned, for example.
The organic device of the present invention includes an organic EL element main body composed of an electrode and a light emitting layer; an organic transistor element composed of an electrode, an insulating film and an organic semiconductor; a junction such as a pn junction or a pin junction It is preferable to have an organic element main body part such as an organic thin film solar cell element part made up of and an electrode.

One suitable form of the organic device of the present invention is an organic electroluminescence (organic EL) element.
The organic EL element includes two opposing electrodes formed on a substrate, a light emitting layer disposed between the two opposing electrodes, an organic sealing layer formed from the organic device sealing agent, and an inorganic It is preferable to have a sealing layer.
The organic sealing layer is usually provided on the opposite side of the light emitting layer from the substrate. The organic sealing layer may be formed on the electrode formed on the light emitting layer, or may be formed on the inorganic sealing layer formed on the electrode.
Each of the organic sealing layer and the inorganic sealing layer may be a single layer, or two or more layers may be laminated. The number of layers of the organic sealing layer and the inorganic sealing layer may be determined as appropriate, and is, for example, 1 to 10, respectively.

As an electrode used for the organic EL element, a metal electrode made of a metal and a transparent electrode made of an oxide or the like are usually used.

Examples of the material for forming the metal electrode include metals such as aluminum, indium, magnesium, silver, calcium, barium, and lithium. As a material for the metal electrode, these metals may be used alone, or two or more of these metals, or an alloy of these metals and other metals may be used.
Since the adhesiveness with the organic sealing layer is excellent, the metal is preferably aluminum, indium or magnesium.

As a material for forming the transparent electrode, a material generally known as a material for the transparent electrode can be used. For example, indium tin oxide (ITO) is preferably used, but tin oxide (SnO ₂ ), zinc oxide (ZnO), and the like can also be used.

A well-known thing can be employ | adopted as a board | substrate and an organic light emitting layer which are used for an organic EL element. For example, a glass substrate can be used as the substrate, or a flexible plastic substrate can be used, and is not particularly limited. The organic light emitting layer may include a hole injection transport layer, an electron injection transport layer, and the like.

FIG. 1 is a schematic cross-sectional view showing an example of an organic EL element.
The organic EL element 100 includes an organic element body 10 made of a transparent electrode layer 2, an organic light emitting layer 3, and a metal electrode layer 4, a barrier layer 20 formed on the organic element body 10, and a barrier. And a protective layer 30 formed on the layer 20.
The barrier layer 20 has a structure in which an organic sealing layer F and an inorganic sealing layer M formed from the organic device sealing agent are laminated.
The barrier layer 20 in which the organic sealing layer F and the inorganic sealing layer M are laminated is excellent in low water vapor permeability that the inorganic sealing layer M has and low water vapor permeability that the organic sealing layer F has. It has water vapor permeability. In addition, by providing the organic sealing layer F, the thickness of the inorganic sealing layer M can be reduced.

In the organic EL element 100, the thickness of the organic sealing layer F is preferably 0.1 to 20 μm, and more preferably 0.5 to 15 μm.
The thickness of the inorganic sealing layer M is preferably 10 to 200 nm, and more preferably 30 to 150 nm.

In the organic EL element 100, for example, after forming the transparent electrode layer 2, the organic light emitting layer 3, and the metal electrode layer 4 on the substrate 1 by a general method, the organic sealing layer F is formed by a sputtering method or a casting method. Then, the inorganic sealing layer M can be formed by the plasma CVD method, and then the protective layer 30 can be formed by a general method.

In addition, although the said organic EL element 100 is laminated | stacked in order of the metal electrode layer 4, the organic sealing layer F, and the inorganic sealing layer M, the organic device which is the organic EL element of this invention is inorganic sealing. The order of the layer and the organic sealing layer may be reversed.

FIG. 2 is a schematic cross-sectional view showing another example of the organic EL element.
The organic EL element 200 includes an organic element body 10 made of a transparent electrode layer 2, an organic light emitting layer 3, and a metal electrode layer 4, a barrier layer 20 formed on the organic element body 10, and a barrier. And a protective layer 30 formed on the layer 20.
The barrier layer 20 has a structure in which organic sealing layers F1 to Fn and inorganic sealing layers M1 to Mn formed from the organic device sealing agent are alternately stacked.
The number of layers may be set as appropriate depending on the required low water vapor transmission rate, the thickness of the organic sealing layer and the inorganic sealing layer, etc., for example, the number of layers of the organic sealing layer and the inorganic sealing layer is: It is preferable that it is 1-10, respectively.

In the organic EL element 200, the thickness of the organic sealing layer is preferably 0.1 to 20 μm, and more preferably 0.2 to 10 μm.
The thickness of the inorganic sealing layer is preferably 10 to 200 nm, and more preferably 30 to 150 nm.

In the organic EL element 200, for example, after forming the transparent electrode layer 2, the organic light emitting layer 3, and the metal electrode layer 4 on the substrate 1 by a general method, the organic sealing layer F1 is formed by a sputtering method or a casting method. Then, the inorganic sealing layer M1 is formed by the plasma CVD method, the barrier layer 20 is formed by repeating this process n times, and then the protective layer 30 is formed by a general method. .

In addition, although the barrier layer 20 shown by FIG. 2 is the thing by which the organic sealing layer and inorganic sealing layer which are formed from the said organic device sealing agent were laminated | stacked alternately, it is the organic EL element of this invention. In an organic device, at least one organic sealing layer formed from an organic device sealing agent may be included. For example, the organic device which is the organic EL element of the present invention may be one in which a part of the organic sealing layer in the organic EL element 200 is replaced with a layer made of another organic material.

Next, the present invention will be described with reference to examples. However, the present invention is not limited to such examples.

Each numerical value of the examples was measured by the following method.

[Measurement of composition and alternating rate of fluoropolymer by NMR (nuclear magnetic resonance method)]
^{For the 1} H-NMR (nuclear magnetic resonance method) measurement, JNM-EX270 (manufactured by JEOL: 270 MHz) was used. Heavy acetone was used as the solvent.

[Molecular weight and molecular weight distribution]
By gel permeation chromatography (GPC), using Tosoh's GPC HLC-8020, Shodex columns (one GPC KF-801, one GPC KF-802, GPC KF-806M) The average molecular weight was calculated from data measured by flowing tetrahydrofuran (THF) as a solvent at a flow rate of 1 ml / min.
When the sample did not dissolve in THF, the average molecular weight was calculated by the following method. A high-performance liquid chromatograph manufactured by JASCO Corporation was used, and the analysis column set was one guard column (Shodex GPC KD-G [4.6 mm ID × 10 mm L]) and an analysis column (KD-806M [8. 0 mm ID × 300 mm L]) 3 were used. The measurement was performed using N-methyl-2-pyrrolidone containing 10 mM LiBr as a mobile solvent, RI as a detector, and a polystyrene standard sample as a calibration curve sample, with a flow rate of 1 ml / min and a sample implantation amount of 200 μL. A data station (ChromNAV) was used for data analysis.

[Glass transition temperature (Tg)]
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO), the temperature range from −50 ° C. to 200 ° C. was raised at a rate of 10 ° C./min (first run) -temperature fall-temperature rise (second run) The intermediate point of the endothermic curve in the second run was defined as Tg (° C.).

[Melting point (Tm)]
Using DSC (Differential Scanning Calorimeter: RTG220, manufactured by SEIKO Co., Ltd.), melting when the temperature is increased (first run) -temperature decrease-temperature increase (second run) at 10 ° C./min, and the temperature is increased in the second run. The temperature corresponding to the maximum value in the heat curve was defined as Tm (° C.).

[IR analysis]
The measurement was performed at room temperature using a Perkin Elmer Fourier transform infrared spectrophotometer 1760X.

[Fluorine content]
By burning 10 mg of sample by the oxygen flask combustion method, absorbing the decomposition gas in 20 ml of deionized water, and measuring the fluorine ion concentration in the absorption liquid by the fluorine selective electrode method (fluorine ion meter, model 901 manufactured by Orion) Determined (mass%).

Synthesis example 1
In a 2.5 L stainless steel autoclave, 980 g of butyl acetate as a solvent and 17 g of vinyl acetate as a vinyl ester monomer are added, 6.2 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, and a flange is formed. The autoclave was replaced with vacuum and the bath temperature was raised to 60 ° C. With stirring, 93 g of tetrafluoroethylene was sealed as a fluorine olefin gas to start the reaction. At this time, the pressure in the tank was 0.740 MPa, and the stirring speed was 200 rpm.
Addition of vinyl acetate was started at the start of the reaction, and 93 g of vinyl acetate was added over 4 hours. During the reaction, tetrafluoroethylene was continuously supplied using a solenoid valve so that the ratio of vinyl acetate / tetrafluoroethylene was constant. The stirring speed was 200 rpm.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.720 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.740 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.

Four hours after the start of the reaction, the supply of tetrafluoroethylene and vinyl acetate was stopped. Thereafter, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and 1110 g of a butyl acetate solution of vinyl acetate / tetrafluoroethylene copolymer (solid content concentration 21.0% by mass) was obtained.
After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer A1.

The composition of the polymer A1 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from ¹ H-NMR, and the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.

Synthesis example 2
A 3 L stainless steel autoclave was charged with 1000 g of pure water, 23.2 g of vinyl acetate, Neocor P (76.4 mass% isopropyl alcohol solution of sodium dioctylsulfosuccinate: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), nitrogen-substituted, and tetrafluoro Ethylene 37g was added and the inside of a tank was heated up to 80 degreeC. Thereafter, 30 g of tetrafluoroethylene was added. At this time, the pressure in the tank was 0.809 MPa. Under stirring, 22 g of a 1% by mass aqueous solution of ammonium persulfate (APS) was added to initiate the reaction. The addition of vinyl acetate was started at the start of the reaction, and 283 g of vinyl acetate was added over 6 hours. During the reaction, tetrafluoroethylene was continuously supplied using a solenoid valve so that the ratio of vinyl acetate / tetrafluoroethylene was constant. The stirring speed was 500 rpm.

Specifically, when tetrafluoroethylene is consumed and the inside of the tank reaches 0.775 MPa, the solenoid valve is automatically opened to supply tetrafluoroethylene, and when 0.800 MPa is reached, the solenoid valve is automatically closed and tetrafluoroethylene is closed. While controlling the supply and pressure of tetrafluoroethylene in a cycle in which the supply of ethylene was stopped, vinyl acetate was added in accordance with the consumption of tetrafluoroethylene.

Six hours after the start of the reaction, the supply of tetrafluoroethylene and vinyl acetate was stopped. Then, after reacting for 1 hour, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, thereby obtaining 1661 g of a vinyl acetate / tetrafluoroethylene copolymer emulsion (solid content concentration 38.5% by mass).

The resulting vinyl acetate / tetrafluoroethylene copolymer (Polymer A2) had a glass transition temperature of 40 ° C. and a particle size of 116 nm.
The particle size was measured using a laser light scattering particle size measuring device (manufactured by Otsuka Electronics Co., Ltd., trade name ELS-3000).

Synthesis example 3
Into a 3 L stainless steel autoclave, 1200 g of butyl acetate as a solvent and 140 g of vinyl acetate as a vinyl ester monomer were added, 7.2 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was replaced with vacuum, and the bath temperature was raised to 60 ° C. Under stirring, tetrafluoroethylene was sealed as a fluorine olefin gas to initiate the reaction. At this time, the pressure in the tank was 1.00 MPa, and the stirring speed was 500 rpm. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed. In 6 hours, the inside of the tank was returned to room temperature and normal pressure to stop the polymerization, and the remaining gas was blown to complete the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer A3.

The composition of polymer A3 was determined from elemental analysis of fluorine, the alternating ratio of fluorine olefin and vinyl ester was calculated from ¹ H-NMR, and the weight average molecular weight and molecular weight distribution (Mw / Mn) were determined from GPC. The glass transition temperature was measured from DSC. The results are shown in Table 2.

Synthesis example 4
A 300 mL stainless steel autoclave is charged with 50 g of butyl acetate solvent and 10 g of vinyl stearate monomer, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) is added as a polymerization initiator, the flange is tightened, and the autoclave is vacuum-substituted. Then, 8.0 g of tetrafluoroethylene was encapsulated as a fluorine olefin gas, and 2.6 g of hexafluoropropylene was subsequently encapsulated, and the mixture was placed in a shaking thermostat at 60 ° C. to initiate the reaction. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 15 hours, and the remaining gas was blown to complete the reaction.

After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain polymer B1.

The same analysis as in Synthesis Example 1 was performed except that the melting point was measured instead of the glass transition temperature. The results are shown in Table 2.

Synthesis example 5
In a 300 mL stainless steel autoclave, 50 g of butyl acetate as a solvent and 10 g of vinyl acetate as a vinyl ester monomer were added, 0.4 g of perbutyl PV (product name, manufactured by NOF Corporation) was added as a polymerization initiator, and the flange was tightened. The autoclave was vacuum-replaced, 17 g of chlorotrifluoroethylene was sealed as a fluorine olefin gas, and the reaction was started by placing it in a shaking thermostat at 60 ° C. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 4 hours, the remaining gas was blown to terminate the reaction, and polymer B2 was obtained. The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis Example 6
(Synthesis of t-butyl vinyl ether / tetrafluoroethylene copolymer)
A 300 ml stainless steel autoclave is charged with 150 g of t-butanol, 26.7 g of t-butyl vinyl ether and 0.48 g of potassium carbonate, 0.46 g of a 70% isooctane solution of perbutyl PV as a catalyst is added, the flange is tightened, and the autoclave is vacuum-substituted. Then, 26.7 g of tetrafluoroethylene was sealed, and the reaction was started by placing it in a 60 ° C. shaking thermostat. Since the polymerization pressure was lowered, the consumption of the gas monomer was confirmed, the shaking was stopped in 3 hours, and the remaining gas was blown to complete the reaction.
After completion of the reaction, the polymer solution was reprecipitated in a large amount of methanol solution, and the polymer was purified to obtain a t-butyl vinyl ether / tetrafluoroethylene copolymer (polymer C1). The composition of the t-butyl vinyl ether / tetrafluoroethylene copolymer determined by elemental analysis of fluorine was 52/48 (molar ratio). The reaction conditions are summarized in Table 1, and the physical properties of the obtained polymer are summarized in Table 2.

Synthesis example 7 (saponification homogeneous system)
The TFE / vinyl acetate polymer A3 obtained in Synthesis Example 3 was uniformly dissolved in a 50 g THF solvent so as to have a concentration of 10% by mass. Thereafter, a 0.6N NaOH solution was added to give an equivalent amount of vinyl acetate in the polymer, and after 30 minutes the polymer was reprecipitated in a large amount of water. After washing with 1N HCl, it was thoroughly washed with ion-exchanged water, and the reprecipitated polymer was suction filtered and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate from the relative intensity of the carbonyl peak by IR, TFE / vinyl alcohol / vinyl acetate polymer A3-34 having a hydrolysis rate of 34% was obtained. The results are summarized in Table 3.

Synthesis examples 8 to 10 (saponification homogeneous system)
By changing the saponification time of Synthesis Example 7, AFE-vinyl alcohol / vinyl acetate polymers A3-45, A3-86, and A3-96 were obtained. The results are summarized in Table 3.

Synthesis Examples 11 to 13 (saponification uniform system)
A saponification polymer, A1-98, B1-97 and Synthesis Example 7 were used in the same manner as in Synthesis Example 7, except that the saponification time of Synthesis Example 7 was 1 day and the polymers obtained in Synthesis Example 1 and Synthesis Examples 4-5 were used. B2-96 was obtained. The results are summarized in Table 3.

Synthesis Example 14
The emulsion of vinyl acetate / tetrafluoroethylene copolymer obtained in Synthesis Example 2 was freeze-coagulated, rinsed with pure water, and then dried. The TFE / vinyl acetate polymer (Polymer A2) had a concentration of 10 in 50 g THF solvent. It was uniformly dissolved so as to be mass%. After that, 0.6N NaOH solution was added so as to be equivalent to vinyl acetate in the polymer. After stirring for 24 hours, neutralized with 1N HCl, re-precipitated in a large amount of pure water, and washed well with ion-exchanged water. The re-precipitated polymer was filtered by suction and dried at 80 ° C. for 2 hours with a dryer. As a result of calculating the hydrolysis rate from the relative intensity of the carbonyl peak by IR, a TFE / vinyl alcohol / vinyl acetate polymer (A2-96) having a hydrolysis rate of 96% was obtained. The results are summarized in Table 3.

Synthesis Example 15 (deprotection step):
(Hydrolysis: Synthesis of vinyl alcohol / tetrafluoroethylene copolymer)
In a 100 ml eggplant flask, 5.26 g of t-butyl vinyl ether / tetrafluoroethylene copolymer obtained in Synthesis Example 6 (t-butyl vinyl ether / tetrafluoroethylene = 52/48 (molar ratio)), 1,4-dioxane 2 4 ml, 4N HCl aqueous solution 100 ml was added and heated and stirred at 80 ° C. After 2 hours, heating was stopped and the mixture was allowed to cool, and the precipitated polymer was washed 3 times with pure water. The polymer was dissolved in tetrahydrofuran (THF), reprecipitated in a solution of ethanol / water (50/50% by volume), and dried in vacuo to obtain a purified vinyl alcohol / tetrafluoroethylene copolymer (C1-95). ). The degree of deprotection was 95%. The results are summarized in Table 3.

Example 1
Polymer A1-98 obtained in Synthesis Example 11 was dissolved in a butyl acetate solvent so as to be 55% by mass. Thereafter, 12 parts by mass of Sumidur N3300 (manufactured by Sumika Bayer Urethane Co., Ltd.), which is an isocyanate curing agent, was added as a crosslinking agent to 100 parts by mass of the solution to obtain a curable composition. This composition was applied using a bar coat (# 24) onto a PET substrate having a SiO _x N _y film of about 80 nm formed on the surface. After the application, it was preliminarily dried at room temperature for 60 minutes and then cured at 100 ° C. in a blower dryer for 60 minutes. Each sample was aged at 50 ° C. for an additional 2 days. The film thickness after curing was measured with a micrometer. The film thickness was 102 μm.
Moreover, the obtained sample was subjected to a cross-cut adhesion test to evaluate the adhesion. Moreover, the haze value and the total light transmittance were measured. The results are shown in Table 4.

(Cross-cut adhesion test)
Evaluation was performed by a cross-celling cellophane tape peeling test of JIS K5600. The coating film is cut with a grid knife at intervals of 1 mm with a cutter knife, peeled after attaching a cellophane tape, 10 points with no peeled part, 8 points with more than 0% and less than 5%, 5 points % And less than 15% were evaluated as 6 points, 15% and less than 35% as 4 points, 35% and less than 65% as 2 points, and 65% or more as 0 points.

(Measurement of haze value and total light transmittance)
The haze value and total light transmittance were measured according to ASTM D1003 using a haze meter (Hazeguard II manufactured by Toyo Seiki Co., Ltd.).

Examples 2-9
In the same manner as in Example 1, for the polymers A3-45, A3-86, A3-96, A1-98, B1-97, B2-96, A2-96, C1-95, a SiO _x N _y film was formed on the surface. Various physical properties were measured after coating on the formed PET film. The results are shown in Table 5.

Example 10
Polymer A2-96 obtained in Synthesis Example 14 was dissolved in a butyl acetate solution so as to be 40% by mass. Then, a self-supporting film having a thickness of 400 μm was obtained by casting.
The haze value and total light transmittance of the obtained film were measured in the same manner as in Example 1.
Further, the ultraviolet transmittance was also measured. The results are shown in Table 6.

Example 11 (plasma resistance)
Using the ICP high-density plasma apparatus (model RIE-101iPH, manufactured by Samco International Laboratories), the self-supporting film obtained in Example 10 was subjected to Ar amount: 50 sccm, O ₂ amount: 40 sccm, 1 Pa, 100 W (250 mW / As a result of performing a plasma treatment for 3 minutes under the condition of cm ² ) and visually evaluating the appearance, it was not damaged at all.
It is considered that there is no problem in the process of forming the inorganic sealing layer.

Examples 12-14
1 g of the polymer obtained in Synthesis Example 7, 9 or 10 was dissolved in a butyl acetate solvent to make 5 g as a whole. Then, after filtering using a 0.45 μm PTFE filter, it was applied onto a 104 μm thick PET film (Lumirror manufactured by Toray Industries, Inc.) using a bar coat (# 24). After preliminary drying at room temperature for 1 hour, the film was dried for 1 day in a blower dryer at 60 ° C. to obtain a laminated film.

The film thickness of the entire laminated film after curing was measured at 10 points with a micrometer, the average value was obtained, and the thickness of the laminated polymer was determined from the difference from the PET film of the substrate. The results are summarized in Table 7.

Each of the produced laminated films was cut to a size of 100 mm × 100 mm, and Dr. based on JIS K7129 (A method). The water vapor permeability of the laminated film was measured using a water vapor permeability meter L80-5000 manufactured by Lyssy. Note that the surface side in direct contact with water vapor is PET, and the dry air side is a film formed from the polymer obtained in Synthesis Example 7, 9 or 10.
Further, a value obtained by dividing the obtained water vapor permeability value by the total thickness of the laminated film was defined as a water vapor transmission coefficient. The results are summarized in Table 7.

Comparative Example 1
The water vapor permeability of only the PET film of the substrate was measured. The results are summarized in Table 7.
Clearly, the laminated film showed a lower water vapor transmission coefficient than the PET single film.

Example 15
A SiO _x N _y film was formed on the free-standing film obtained in Example 10 by a low temperature plasma CVD method. In accordance with JIS K7129 B method, the water vapor permeability was measured using a water vapor permeability tester (PERMATRAN W3 / 33 (manufactured by MOCON)) under the conditions of a temperature of 40 ° C. and a humidity of 90% RH. .
The thickness was measured using a spectroscopic ellipsometer M-2000D manufactured by J-Woollam Japan, Inc., and WVASE32 as analysis software.

1: Substrate 2: Transparent electrode layer 3: Organic light emitting layer 4: Metal electrode layers F, F1, F2-Fn: Organic sealing layers M, M1, M2-Mn formed from organic device sealing agent: Inorganic sealing Layer 10: Organic element body 20: Barrier layer 30: Protective layer 100, 200: Organic EL element

Claims (7)

An organic device having a laminated structure in which an inorganic sealing layer and an organic sealing layer are laminated,
The organic encapsulating layer may look containing a fluorine-containing copolymer having a fluorine-containing olefin units and vinyl alcohol units,
The organic device according to claim 1, wherein the inorganic sealing layer has a thickness of 200 nm or less . The organic device according to claim 1, wherein the fluorine-containing olefin is tetrafluoroethylene. The organic device according to claim 1 or 2, wherein the fluorine-containing olefin unit content in the fluorine-containing copolymer is 40 mol% or more. The organic device according to claim 1, 2, or 3, wherein an alternating rate of the fluorine-containing olefin unit and the vinyl alcohol unit in the fluorine-containing copolymer is 94% or less. The organic device according to claim 1, 2, 3, or 4, wherein the fluorine-containing copolymer has a fluorine-containing olefin unit, a vinyl alcohol unit, and a vinyl ester monomer unit. 6. The organic device according to claim 1, wherein the fluorine-containing copolymer is a copolymer obtained by hydroxylating a copolymer having a fluorine-containing olefin unit and a vinyl ester monomer unit. The organic device according to claim 1, which is an organic electroluminescence element.

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