KR20220104681A - Composition, curing body, encapsulant for organic electroluminescent display device and organic electroluminescent display device - Google Patents

Abstract

A monomer component containing a fluorine atom and a fluorine-containing monomer having a carbon-carbon unsaturated double bond, and a photopolymerization initiator, wherein at least a part of the monomer component has a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C It is a high-viscosity monomer, The composition whose viscosity measured by the E-type viscometer at 25 degreeC is 3 mPa*s or more and 50 mPa*s or less.

Description

Composition, curing body, encapsulant for organic electroluminescent display device and organic electroluminescent display device

The present invention relates to a composition and a cured product thereof. Further, the present invention relates to an encapsulant for an organic electroluminescence (EL) display device and an organic EL display device including the same.

An organic electroluminescence display device (also referred to as an organic EL display device, an organic EL device, or an OLED device) is attracting attention as a device body capable of emitting light with high luminance. However, there existed a subject that an organic electroluminescent display element will deteriorate by water|moisture content and the light emitting characteristic will fall.

In order to solve such a subject, the technique of sealing an organic electroluminescent display element with the sealing material which laminated|stacked the organic film and an inorganic film, and preventing deterioration by water|moisture content is examined (for example, patent documents 1-2).

[Patent Document 1] Japanese Patent Laid-Open No. 2001-307873 [Patent Document 2] Japanese Patent Laid-Open No. 2009-37812

In recent years, the characteristics required for an organic EL display device are increasing, and an encapsulant capable of realizing higher reliability and durability is required.

As a method of forming a sealing material, an organic film is formed by application and curing of a resin composition, and a method of laminating an inorganic film on the organic film is known. In this method, when unevenness|corrugation arises on the surface of an organic film, there exists a subject that adhesiveness with an inorganic film falls. In addition, when the resin composition is applied by the inkjet method, the coating liquid discharged from the inkjet nozzle meanders, deviating from a predetermined range, and it is difficult to accurately form an organic film.

Accordingly, an object of the present invention is to provide a composition capable of accurately forming an organic film having few irregularities on a surface within a predetermined range. Moreover, this invention is a hardening body of the said composition, and an object of this invention is to provide the hardening body useful as a sealing material for organic electroluminescent display elements. Another object of the present invention is to provide an encapsulant for an organic EL display element including the cured body, and an organic EL display device including the encapsulant.

One aspect of the present invention relates to a composition comprising a monomer component containing a fluorine-containing monomer having a fluorine atom and a carbon-carbon unsaturated double bond, and a photopolymerization initiator. At least a part of the monomer component is a high-viscosity monomer having a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C. Moreover, the viscosity measured by the E-type viscometer at 25 degreeC of the said composition is 3 mPa*s or more and 50 mPa*s or less.

Since the composition has excellent surface flatness and straightness, it is possible to accurately form an organic film with few irregularities on the surface within a predetermined range.

In the composition according to one aspect, 5 to 65% by mass of the monomer component may be the high-viscosity monomer.

In one aspect, at least a part of the monomer component may be a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds.

In the composition according to one aspect, 70 to 98% by mass of the monomer component may be the polyfunctional monomer.

In one aspect, at least a portion of the high-viscosity monomer component may be a monofunctional monomer having one carbon-carbon unsaturated double bond.

In the composition according to an aspect, 10 to 60% by mass of the high-viscosity monomer component may be the monofunctional monomer.

The composition can be suitably used as an encapsulant for an organic electroluminescent display device.

Another aspect of the present invention relates to a cured product formed by curing the composition.

Another aspect of the present invention relates to an encapsulant for an organic electroluminescent display device including the cured body.

Another aspect of the present invention relates to an encapsulant for an organic electroluminescent display device comprising a laminate in which an inorganic film and an organic film are laminated, and wherein the organic film includes the cured body according to claim 8 .

Another aspect of the present invention relates to an organic electroluminescent display device including an organic electroluminescent display device and an encapsulant for the organic electroluminescent display device.

According to the present invention, there is provided a composition capable of accurately forming an organic film having few irregularities on the surface within a predetermined range. Moreover, according to this invention, it is a hardening body of the said composition, and the hardening body useful as a sealing material for organic electroluminescent display elements is provided. In addition, according to the present invention, there are provided an organic EL display device encapsulant including the cured body and an organic EL display device including the encapsulant.

Hereinafter, preferred embodiments of the present invention will be described in detail.

<Composition>

The composition of this embodiment contains the monomer component containing a fluorine-containing monomer, and a photoinitiator. In this embodiment, at least a part of the monomer component is a high-viscosity monomer whose viscosity measured by an E-type viscometer at 25°C is 50 mPa·s or more, and the composition of this embodiment has a viscosity measured by an E-type viscometer at 25°C of 3 mPa ·s or more and 50 mPa·s or less.

Since the composition of the present embodiment has a viscosity within the above range, it can be suitably used for the inkjet method, and since it is excellent in surface flatness and straightness, an organic film with few irregularities can be accurately formed on the surface within a predetermined range.

Although the reason why the said effect arises is not necessarily limited, It is thought as follows. First, since the composition of this embodiment contains a fluorine-containing monomer, the surface free energy becomes low, the surface of a coating film becomes easy to planarize after application|coating, and it is thought that the organic film with few unevenness|corrugations can be formed on the surface. Moreover, since the composition of this embodiment contains a high-viscosity monomer, it becomes difficult to meander at the time of discharge from an inkjet nozzle (that is, straightness improves), and formation of an organic film accurately in a predetermined range becomes possible.

At least a part of the monomer component of the present embodiment is a high-viscosity monomer having a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C. The viscosity of the high-viscosity monomer is preferably 100 mPa·s or more, and more preferably 150 mPa·s or more. The viscosity of the high-viscosity monomer is preferably 1000 mPa·s or less, more preferably 500 mPa·s or less, and still more preferably 300 mPa·s or less. That is, the viscosity of the high-viscosity monomer is a viscosity measured by an E-type viscometer at 25° C., for example, 50 to 1000 mPa·s, 50 to 500 mPa·s, 50 to 300 mPa·s, 100 to 1000 mPa·s, 100 to 500 mPa. ·s, 100 to 300 mPa·s, 150 to 1000 mPa·s, 150 to 500 mPa·s, or 150 to 300 mPa·s may be sufficient.

The viscosity (viscosity measured with an E-type viscometer at 25 degreeC) of the composition of this embodiment is 3 mPa*s or more, Preferably it is 5 mPa*s or more, More preferably, it is 10 mPa*s or more. Moreover, the viscosity (viscosity measured with the E-type viscometer at 25 degreeC) of the composition of this embodiment is 50 mPa*s or less, Preferably it is 45 mPa*s or less, More preferably, it is 40 mPa*s or less. In such a viscosity range, the surface flatness tends to be further improved. That is, the viscosity of the composition of the present embodiment is a viscosity measured by an E-type viscometer at 25°C, for example, 3 to 50 mPa·s, 3 to 45 mPa·s, 3 to 40 mPa·s, 5 to 50 mPa·s, 5 to 45 mPa·s, 5 to 40 mPa·s, 10 to 50 mPa·s, 10 to 45 mPa·s, or 10 to 40 mPa·s may be sufficient.

The composition of the present embodiment may contain, as a monomer component, a high-viscosity monomer and a low-viscosity monomer (a monomer having a viscosity of less than 50 mPa·s as measured by an E-type viscometer at 25°C). The ratio of the high-viscosity monomer and the low-viscosity monomer can be appropriately changed within the range in which the viscosity of the composition is within the above numerical range.

The ratio of the high-viscosity monomer to a monomer component may be 5 mass % or more, for example, Preferably it is 7 mass % or more, More preferably, it is 9 mass % or more. There exists a tendency for straightness to improve more by increasing the ratio of a high-viscosity monomer. In addition, the ratio of the high-viscosity monomer to a monomer component may be, for example, 65 mass % or less, Preferably it is 60 mass % or less, More preferably, it is 55 mass % or less, 50 mass % or less may be sufficient, and 45 mass % or less. % or less may be sufficient, 40 mass % or less may be sufficient, and 35 mass % or less may be sufficient. By decreasing the ratio of the high-viscosity monomer, the viscosity of the composition can be lowered and the ejection property tends to be further improved. That is, the ratio of the high-viscosity monomer to the monomer component is, for example, 5 to 65 mass%, 5 to 60 mass%, 5 to 55 mass%, 5 to 50 mass%, 5 to 45 mass%, 5 to 40 mass% , 5 to 35% by mass, 7 to 65% by mass, 7 to 60% by mass, 7 to 55% by mass, 7 to 50% by mass, 7 to 45% by mass, 7 to 40% by mass, 7 to 35% by mass, 9 -65 mass %, 9-60 mass %, 9-55 mass %, 9-50 mass %, 9-45 mass %, 9-40 mass %, or 9-35 mass % may be sufficient.

The composition of the present embodiment may contain, as a monomer component, a monofunctional monomer having one carbon-carbon unsaturated double bond and a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds.

The ratio of the polyfunctional monomer to a monomer component may be 70 mass % or more, for example, Preferably it is 75 mass % or more, More preferably, it is 80 mass % or more. By increasing the ratio of the polyfunctional monomer, the moisture permeability of the cured product tends to improve and the straightness tends to improve. Moreover, the ratio of the polyfunctional monomer to a monomer component may be 98 mass % or less, for example, Preferably it is 97 mass % or less, More preferably, it is 96 mass % or less. There exists a tendency for surface flatness to improve more by making the ratio of a polyfunctional monomer small. That is, the ratio of the polyfunctional monomer to the monomer component is, for example, 70 to 98 mass%, 70 to 97 mass%, 70 to 96 mass%, 75 to 98 mass%, 75 to 97 mass%, 75 to 96 mass%. %, 80-98 mass %, 80-97 mass %, or 80-96 mass % may be sufficient.

The polyfunctional monomer is preferably a monomer having 2 to 6 carbon-carbon unsaturated double bonds, more preferably a monomer having 2 or 3 carbon-carbon unsaturated double bonds, and has two or more carbon-carbon unsaturated double bonds A bifunctional monomer is more preferable.

The composition of this embodiment may contain a polyfunctional monomer as a high-viscosity monomer, may contain a polyfunctional monomer as a low-viscosity monomer, The polyfunctional monomer corresponding to a high-viscosity monomer, and a polyfunctional monomer corresponding to a low-viscosity monomer You may contain both.

The composition of the present embodiment may contain a monofunctional monomer as a high-viscosity monomer, may contain a monofunctional monomer as a low-viscosity monomer, and a monofunctional monomer corresponding to a high-viscosity monomer and a monofunctional monomer corresponding to a low-viscosity monomer. You may contain all of them.

In this embodiment, it is preferable that at least one part of a high-viscosity monomer is a monofunctional monomer.

The ratio of the monofunctional monomer to the high-viscosity monomer may be, for example, 9 mass % or more, preferably 10 mass % or more, more preferably 11 mass % or more, and still more preferably 12 mass % or more. . Moreover, the ratio of the monofunctional monomer to a high-viscosity monomer may be, for example, 60 mass % or less, Preferably it is 55 mass % or less, More preferably, it is 50 mass % or less. By using many monofunctional monomers as a high-viscosity monomer, there exists a tendency for the moisture permeability, flexibility, and flexibility of a hardening body to improve more. That is, the ratio of the monofunctional monomer to the high-viscosity monomer is, for example, 9 to 60% by mass, 9 to 55% by mass, 9 to 50% by mass, 10 to 60% by mass, 10 to 55% by mass, 10 to 50% by mass. %, 11-60 mass %, 11-55 mass %, 11-50 mass %, 12-60 mass %, 12-55 mass %, or 12-50 mass % may be sufficient.

<Fluorine-containing monomer>

A fluorine-containing monomer is a monomer having a fluorine atom and a carbon-carbon unsaturated double bond. A fluorine-containing monomer may be used individually by 1 type, and may be used in combination of 2 or more type.

The fluorine-containing monomer may be contained in the monomer component as a low-viscosity monomer. The viscosity of the fluorine-containing monomer (viscosity measured by an E-type viscometer at 25°C) may be, for example, less than 50 mPa·s, preferably 45 mPa·s or less, more preferably 40 mPa·s or less, still more preferably 35 mPa·s or less. In addition, the viscosity (viscosity measured by the E-type viscometer at 25 degreeC) of a fluorine-containing monomer may be 1 mPa*s or more, 2 mPa*s or more, and 3 mPa*s or more may be sufficient, for example. That is, the viscosity of the fluorine-containing monomer is a viscosity measured by an E-type viscometer at 25° C., for example, 1 mPa·s or more and less than 50 mPa·s, 1 to 45 mPa·s, 1 to 40 mPa·s, 1 to 35 mPa·s. , 2 mPa s or more and less than 50 mPa s, 2 to 45 mPa s, 2 to 40 mPa s, 2 to 35 mPa s, 3 mPa s or more and less than 50 mPa s, 3 to 45 mPa s, 3 to 40 mPa s or 3 ~35 mPa·s may be sufficient.

The number of fluorine atoms that the fluorine-containing monomer has may be one or more, for example, two or more, and preferably three or more. In addition, the upper limit of the number of the fluorine atoms which a fluorine-containing monomer has is not specifically limited. The number of fluorine atoms in the fluorine-containing monomer may be, for example, 40 or less, preferably 35 or less, more preferably 30 or less, and still more preferably 25 or less. That is, the number of fluorine atoms that the fluorine-containing monomer has is, for example, 1 to 40, 1 to 35, 1 to 30, 1 to 25, 2 to 40, 2 to 35, 2 to 30. , 2 to 25, 3 to 40, 3 to 35, 3 to 30, or 3 to 25 may be sufficient.

Content of the fluorine atom with respect to the whole quantity of a fluorine-containing monomer may be 1 mass % or more, for example, Preferably it is 2 mass % or more, More preferably, it is 5 mass % or more. In addition, the content of the fluorine atom may be, for example, 90 mass% or less, preferably 75 mass% or less, more preferably 70 mass% or less, still more preferably 65 mass%, based on the total amount of the fluorine-containing monomer. % or less. That is, the content of fluorine atoms is 1-90% by mass, 1-75% by mass, 1-70% by mass, 1-65% by mass, 2-90% by mass, 2-75% by mass, based on the total amount of the fluorine-containing monomer; 2-70 mass %, 2-65 mass %, 5-90 mass %, 5-75 mass %, 5-70 mass %, or 5-65 mass % may be sufficient.

The number of carbon-carbon unsaturated double bonds which a fluorine-containing monomer has may just be 1 or more. Further, the number of carbon-carbon unsaturated double bonds in the fluorine-containing monomer may be, for example, 4 or less, and from the viewpoint of easily obtaining a cured product excellent in flexibility, preferably 3 or less, preferably 2 or less to be. That is, the number of carbon-carbon unsaturated double bonds in the fluorine-containing monomer may be, for example, 1-4, 1-3, or 1-2.

The fluorine-containing monomer preferably has a (meth)acryloyl group as a group having a carbon-carbon double bond. That is, it is preferable that a fluorine-containing monomer is a monomer which has a fluorine atom and a (meth)acryloyl group. In addition, a (meth)acryloyl group represents an acryloyl group or a methacryloyl group.

As one specific example of a fluorine-containing monomer, the compound represented by a following formula (A-1) is mentioned.

In formula (A-1), R< ¹ > represents a hydrogen atom or a methyl group. In addition, R ² represents a fluorinated alkyl group or a group in which an oxygen atom is inserted into a part of a carbon-carbon bond and a carbon-hydrogen bond in a fluorinated alkyl group.

The fluorinated alkyl group can be said to be a group in which some or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The number of carbon atoms in the fluorinated alkyl group is not particularly limited, and may be, for example, one or more, preferably two or more, and more preferably three or more. Moreover, the carbon atom number of a fluorinated alkyl group may be 25 or less, and may be 20 or less, for example. That is, the number of carbon atoms of the fluorinated alkyl group may be, for example, 1 to 25, 1 to 20, 2 to 25, 2 to 20, 3 to 25, or 3 to 20.

As the fluorinated alkyl group, a group containing difluoromethylene (-CF ₂ -) can be suitably used.

Specific examples of the fluorinated alkyl group include difluoromethyl group, trifluoromethyl group, 1,1-difluoroethyl group, 2,2-difluoroethyl group, 1,1,1-trifluoroethyl group, 2,2,2- Trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoropropyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1,2,2,3, 3-hexafluoropropyl group, perfluoropropyl group, perfluoroethylmethyl group, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl group, 2,2,3,3- Tetrafluoropropyl group, perfluoropropyl group, 1,1,2,2-tetrafluorobutyl group, 1,1,2,2,3,3-hexafluorobutyl group, 1,1,1, 2,2,3,3-Peptafluorobutyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, perfluorobutyl group, 1,1-bis(trifluoro Rho) methyl-2,2,2-trifluoroethyl group, 2-(perfluoropropyl)ethyl group, 1,1,2,2,3,3,4,4-octafluoropentyl group, 2,2 ,3,3,4,4,5,5-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl group , 1,1-bis(trifluoromethyl)-2,2,3,3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 1,1,1,2,2,3 ,3,4,4-nonafluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3 ,4,4,5,5,6,6-dodecafluorohexyl group, perfluorohexyl group, perfluoropentylmethyl group, perfluorohexyl group, etc. are mentioned.

A group in which an oxygen atom is inserted into a part of a carbon-carbon bond and a carbon-hydrogen bond in a fluorinated alkyl group (hereinafter, also referred to as an oxygen-containing group of R ² ) may be a contribution in which an oxygen atom is inserted in one place, or is inserted in two or more places also contribute.

Also, when an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, when an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of R ² can also be referred to as a group containing at least one selected from the group consisting of an ether bond and a hydroxyl group.

As a specific example of the oxygen-containing group of R< ² >, group represented by a following formula is mentioned, for example.

The fluorine atom content in the compound represented by the formula (A-1) may be, for example, 2 mass % or more, preferably 5 mass % or more, more preferably 15 mass % or more, still more preferably 30 mass % or more. Moreover, the fluorine atom content in the compound represented by Formula (A-1) may be 75 mass % or less, for example, Preferably it is 70 mass % or less, More preferably, it is 65 mass % or less. That is, the fluorine atom content in the compound represented by formula (A-1) is, for example, 2-75 mass%, 2-70 mass%, 2-65 mass%, 5-75 mass%, 5-70 mass%. Mass %, 5-65 mass %, 15-75 mass %, 15-70 mass %, 15-65 mass %, 30-75 mass %, 30-70 mass %, or 30-65 mass % may be sufficient.

As one of the specific examples of the compound represented by Formula (A-1), the compound represented by Formula (A-1-1) is mentioned, for example.

In formula (A-1-1), R ¹ represents a hydrogen atom or a methyl group, R ²¹ represents a hydrogen atom or a fluorine atom, and n represents an integer of 1 or more. Two or more R ²¹ may be the same as or different from each other. However, at least one of R ²¹ is a fluorine atom.

n should just be 1 or more, Preferably it is 2 or more. In addition, the upper limit of n is not specifically limited. n may be 25 or less, for example, and 20 or less may be sufficient as it. That is, n may be 1-25, 1-20, 2-25, or 2-20, for example.

Although a plurality of R ²¹ is present in formula (A-1-1), at least one of them is a fluorine atom. Moreover, it is preferable that 2 or more of R ²¹ are fluorine atoms, and it is more preferable that 3 or more are fluorine atoms. All of R ²¹ may be fluorine atoms.

The ratio of the number of fluorine atoms to the total number of R ²¹ may be, for example, 4% or more, preferably 8% or more, and more preferably 12% or more. The ratio may be, for example, 100% or less, preferably 80% or less, and more preferably 75% or less. That is, the ratio of the number of fluorine atoms to the total number of R ²¹ is, for example, 4 to 100%, 4 to 80%, 4 to 75%, 8 to 100%, 8 to 80%, 8 to 75%, 12 to 100%, 12 to 80%, or 12 to 75% may be sufficient.

In the compound represented by the formula (A-1-1), at least one of the divalent groups (-C(R ²¹ ) ₂ -) in parentheses to which n is attached is preferably difluoromethylene (-CF ₂ -) do.

As another specific example of a fluorine-containing monomer, the compound represented by Formula (A-2) is mentioned.

In formula (A-2), R ³ represents a hydrogen atom or a methyl group. Further, R ⁴ represents a fluorinated alkanediyl group or a group in which an oxygen atom is inserted into a part of the carbon-carbon bond and the carbon-hydrogen bond in the fluorinated alkanediyl group. Two or more R ³ may be the same as or different from each other.

The fluorinated alkanediyl group can be said to be a group in which some or all of the hydrogen atoms of the alkanediyl group are substituted with fluorine atoms. The number of carbon atoms of the fluorinated alkanediyl group is not particularly limited, and may be, for example, 1 or more, preferably 2 or more, more preferably 3 or more, still more preferably 4 or more. The number of carbon atoms in the fluorinated alkanediyl group may be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, still more preferably 12 or less, still more preferably 10 or less. That is, the number of carbon atoms in the fluorinated alkanediyl group is, for example, 1 to 20, 1 to 17, 1 to 15, 1 to 12, 1 to 10, 2 to 20, 2 to 17, 2 to 15, 2 to 12. , 2 to 10, 3 to 20, 3 to 17, 3 to 15, 3 to 12, 3 to 10, 4 to 20, 4 to 17, 4 to 15, 4 to 12, or 4 to 10 may be sufficient.

As the fluorinated alkanediyl group, a group containing difluoromethylene (-CF ₂ -) can be suitably used.

Specific examples of the fluorinated alkanediyl group include a linear or branched fluorinated alkanediyl group having 1 to 17 carbon atoms (eg, 2,2,3,3,4,4,5,5,6,6,7,7). ,8,8,9,9-hexadecafluoro-1,10-decanediyl group), a C1-C17 fluorinated cycloalkanediyl group, etc. are mentioned.

A group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkanediyl group (hereinafter, also referred to as an oxygen-containing group of R ⁴ ) may be a contribution in which an oxygen atom is inserted at one place, or at two or more places It is also an embedded contribution.

Also, when an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, when an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of R ⁴ can also be referred to as a group including at least one selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group for R ⁴ include groups represented by the following formula.

The fluorine atom content in the compound represented by the formula (A-2) may be, for example, 4 mass % or more, preferably 8 mass % or more, and more preferably 12 mass % or more. In addition, the fluorine atom content in the compound represented by Formula (A-2) may be 90 mass % or less, for example, Preferably it is 75 mass % or less, More preferably, it is 65 mass % or less. That is, the fluorine atom content in the compound represented by the formula (A-2) is, for example, 4 to 90% by mass, 4 to 75% by mass, 4 to 65% by mass, 8 to 90% by mass, or 8 to 75% by mass. %, 8-65 mass %, 12-90 mass %, 12-75 mass %, or 12-65 mass % may be sufficient.

As one of the specific examples of the compound represented by Formula (A-2), the compound represented by Formula (A-2-1) is mentioned, for example.

In formula (A-2-1), R ³ represents a hydrogen atom or a methyl group, R ⁴¹ represents a hydrogen atom or a fluorine atom, and m represents an integer of 1 or more. Two or more R ³ may be the same as or different from each other. Two or more R ⁴¹ may be the same as or different from each other. However, at least one of R ⁴¹ is a fluorine atom.

m should just be 1 or more, Preferably it is 2 or more, More preferably, it is 3 or more, More preferably, it is 4 or more. In addition, the upper limit of m is not specifically limited. m may be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, still more preferably 12 or less, still more preferably 10 or less. That is, m is, for example, 1 to 20, 1 to 17, 1 to 15, 1 to 12, 1 to 10, 2 to 20, 2 to 17, 2 to 15, 2 to 12, 2 to 10, 3 to 20, 3-17, 3-15, 3-12, 3-10, 4-20, 4-17, 4-15, 4-12, or 4-10 may be sufficient.

A plurality of R ⁴¹ is present in the formula (A-2-1), and at least one of them is a fluorine atom. Moreover, it is preferable that 2 or more of R ⁴¹ are fluorine atoms, and it is more preferable that 4 or more are fluorine atoms. All of R ⁴¹ may be fluorine atoms.

The ratio of the number of fluorine atoms to the total number of R ⁴¹ may be, for example, 1% or more, preferably 5% or more, and more preferably 10% or more. The proportion may be, for example, 100% or less, preferably 95% or less, and more preferably 90% or less. That is, the ratio of the number of fluorine atoms to the total number of R ⁴¹ is, for example, 1 to 100%, 1 to 95%, 1 to 90%, 5 to 100%, 5 to 95%, 5 to 90%, 10 to 100%, 10 to 95%, or 10 to 90% may be sufficient.

In the compound represented by the formula (A-2-1), at least one of the divalent groups (-C(R ⁴¹ ) ₂ -) in the parentheses to which m is attached is preferably difluoromethylene (-CF ₂ -). do.

As another specific example of a fluorine-containing monomer, the compound represented by Formula (A-3) is mentioned.

In formula (A-3), R ⁵ represents a hydrogen atom or a methyl group. In addition, R ⁶ represents a single bond, an alkanediyl group, a fluorinated alkanediyl group, or a group in which an oxygen atom is inserted into a part of the carbon-carbon bond and the carbon-hydrogen bond in the alkanediyl group or the fluorinated alkanediyl group. In addition, Ar ¹ represents a fluorinated aryl group.

In addition, "R< ⁶ > represents a single bond" means that Ar< ¹ > and an oxygen atom are directly couple|bonding.

The fluorinated aryl group of Ar ¹ is preferably a fluorinated phenyl group. The fluorinated phenyl group can also be referred to as a group in which 1 to 5 of the hydrogen atoms in the phenyl group are substituted with fluorine atoms. The fluorinated phenyl group may have one or more fluorine atoms, and may have five.

The number of carbon atoms in the alkanediyl group of R ⁶ is not particularly limited, and may be, for example, one or more. Moreover, the carbon atom number of the alkanediyl group of R< ⁶ > may be 17 or less, for example, Preferably it is 15 or less, More preferably, it is 12 or less. That is, the carbon atom number of the alkanediyl group of R< ⁶ > may be 1-17, 1-15, or 1-12, for example.

Specific examples of the alkanediyl group include a linear or branched alkanediyl group having 1 to 17 carbon atoms (eg, a methylene group, ethylene group, etc.) and a cycloalkanediyl group having 1 to 17 carbon atoms.

The fluorinated alkanediyl group of R ⁶ can be said to be a group in which some or all of the hydrogen atoms of the aforementioned alkanediyl group are substituted with fluorine atoms. The number of carbon atoms in the fluorinated alkanediyl group for R ⁶ is not particularly limited, and may be, for example, one or more. Moreover, the carbon atom number of the fluorinated alkanediyl group of R< ⁶ > may be 17 or less, for example, Preferably it is 15 or less, More preferably, it is 12 or less. That is, the number of carbon atoms of the fluorinated alkanediyl group of R ⁶ may be, for example, 1 to 17, 1 to 15, or 1 to 12.

As the fluorinated alkanediyl group for R ⁶ , a group containing difluoromethylene (-CF ₂ —) can be suitably used.

In an alkanediyl group or a fluorinated alkanediyl group, a group in which an oxygen atom is inserted into a part of the carbon-carbon bond and carbon-hydrogen bond (hereinafter, also referred to as an oxygen-containing group of R ⁶ ) may be a contribution in which an oxygen atom is inserted at one place, Contributions inserted in two or more places may also be included.

Also, when an oxygen atom is inserted into a carbon-carbon bond, an ether bond is formed. Also, when an oxygen atom is inserted into a carbon-hydrogen bond, a hydroxyl group is formed. That is, the oxygen-containing group of R ⁶ can also be referred to as a group including at least one selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group for R ⁶ include groups containing —CH ₂ CH ₂ O—.

The fluorine atom content in the compound represented by the formula (A-3) may be, for example, 3% by mass or more, preferably 7% by mass or more, and more preferably 15% by mass or more. Moreover, 90 mass % or less may be sufficient as the fluorine atom content in the compound represented by Formula (A-3), Preferably it is 80 mass % or less, More preferably, it is 70 mass % or less. That is, the fluorine atom content in the compound represented by the formula (A-3) is, for example, 3 to 90% by mass, 3 to 80% by mass, 3 to 70% by mass, 7 to 90% by mass, 7 to 80% by mass. %, 7-70 mass %, 15-90 mass %, 15-80 mass %, or 15-70 mass % may be sufficient.

As one of the specific examples of the compound represented by Formula (A-3), the compound represented by Formula (A-3-1) is mentioned, for example.

In the formula (A-3-1), R ⁵ represents a hydrogen atom or a methyl group, R ⁶¹ represents a hydrogen atom or a fluorine atom, R ⁶² represents a hydrogen atom or a fluorine atom, and p represents an integer of 0 or more. When p is 1 or more, two or more R ⁶¹ may be the same as or different from each other. In addition, two or more R ⁶² may mutually be same or different. However, at least one of R ⁶² is a fluorine atom.

p represents an integer of 0 or more. Here, p is 0 indicates that the benzene ring and the oxygen atom are directly bonded. p may be an integer of 1 or more. In addition, the upper limit of p is not specifically limited. p may be 17 or less, for example, Preferably it is 15 or less, More preferably, it is 12 or less. That is, p may be 1-17, 1-15, or 1-12, for example.

When R ⁶¹ is present in the formula (A-3-1) (that is, when p is an integer greater than or equal to 1), all of R ⁶¹ may be a hydrogen atom, all of them may be a fluorine atom, some are hydrogen atoms, and other moieties (hereinafter, Tabu) may be a fluorine atom.

A plurality of R ⁶² is present in the formula (A-3-1), and at least one of them is a fluorine atom. Moreover, two or more of R ⁶² may be a fluorine atom, and 3 or more may be a fluorine atom or more. Moreover, all (5 pieces) of R ⁶² may be a fluorine atom.

The ratio of the number of fluorine atoms to the total number of R ⁶¹ and R ⁶² may be, for example, 5% or more, preferably 10% or more, and more preferably 20% or more. The proportion may be, for example, 100% or less, preferably 95% or less, and more preferably 80% or less. That is, the ratio of the number of fluorine atoms to the total number of R ⁶¹ and R ⁶² is, for example, 5 to 100%, 5 to 95%, 5 to 80%, 10 to 100%, 10 to 95%, 10 to 80%, 20-100%, 20-95%, or 20-80% may be sufficient.

In a preferred aspect, the fluorine-containing monomer is at least one selected from the group consisting of a compound represented by Formula (A-1), a compound represented by Formula (A-2), and a compound represented by Formula (A-3). It is preferable to include

In another preferred embodiment, the fluorine-containing monomer is 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl (meth)acrylate, 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol di(meth)acrylate, 1H, It is preferable to include at least one selected from the group consisting of 1H, 5H-octafluoropentyl (meth)acrylate, and 1H, 1H, 2H, and 2H-tridecafluorooctyl (meth)acrylate.

The fluorine-containing monomer is not limited to the above compound.

In the present embodiment, the monomer component may further have a monomer other than the fluorine-containing monomer (that is, a monomer having no fluorine atom) (hereinafter also referred to as a monomer (B)). The monomer (B) can be said to be a monomer having a carbon-carbon unsaturated double bond and not having a fluorine atom. It is preferable that it is a monomer which has a vinyl group as a carbon-carbon unsaturated double bond, and, as for a monomer (B), it is more preferable that it is a monomer which has a (meth)acryloyl group as a carbon-carbon unsaturated double bond.

The ratio of the fluorine-containing monomer to a monomer component is not specifically limited, For example, 0.001 mass % or more may be sufficient, Preferably it is 0.005 mass % or more, More preferably, it is 0.008 mass % or more. Moreover, the ratio of the fluorine-containing monomer to a monomer component may be 97 mass % or less, for example, Preferably it is 95 mass % or less, More preferably, it is 93 mass % or less. That is, the ratio of the fluorine-containing monomer to the monomer component is, for example, 0.001 to 97 mass%, 0.001 to 95 mass%, 0.001 to 93 mass%, 0.005 to 97 mass%, 0.005 to 95 mass%, 0.005 to 93 mass%. %, 0.008 to 97 mass%, 0.008 to 95 mass%, or 0.008 to 93 mass% may be sufficient.

The proportion of the fluorine-containing monomer in the monomer component is preferably 0.01% by mass or more, more preferably 0.1 to 10% by mass, still more preferably 0.3 to 7% by mass, from the viewpoint of further improving surface flatness and straightness, It is still more preferable that it is 0.5-5 mass %. That is, the ratio of the fluorine-containing monomer to the monomer component is, for example, 0.01 to 10 mass%, 0.01 to 7 mass%, 0.01 to 5 mass%, 0.1 to 10 mass%, 0.1 to 7 mass%, 0.1 to 5 mass%. %, 0.3-10 mass %, 0.3-7 mass %, 0.3-5 mass %, 0.5-10 mass %, 0.5-7 mass %, or 0.5-5 mass % may be sufficient.

The fluorine atom content with respect to the total amount of the monomer component may be, for example, 0.005 mass % or more, preferably 0.5 mass % or more, more preferably 1 mass % or more, still more preferably 2 mass % or more, further Preferably it is 5 mass % or more. Moreover, content of a fluorine atom may be 75 mass % or less on the basis of the whole quantity of a monomer component, Preferably it is 70 mass % or less, More preferably, it is 65 mass % or less. That is, the fluorine atom content with respect to the total amount of the monomer component is, for example, 0.005 to 75 mass%, 0.005 to 70 mass%, 0.005 to 65 mass%, 0.5 to 75 mass%, 0.5 to 70 mass%, 0.5 to 65 mass%. %, 1 to 75% by mass, 1 to 70% by mass, 1 to 65% by mass, 2 to 75% by mass, 2 to 70% by mass, 2 to 65% by mass, 5 to 75% by mass, 5 to 70% by mass or 5-65 mass % may be sufficient.

Although the monomer (B) may be a high-viscosity monomer or a low-viscosity monomer, it is preferable that at least a part of the monomer (B) is a high-viscosity monomer. The monomer component may contain two or more types of monomers (B), in this case, all of the two or more types of monomers (B) may be high-viscosity monomers, and some of the two or more types of monomers (B) are high-viscosity monomers, and the other part Silver may be a low-viscosity monomer.

Among the monomers (B), those corresponding to the high-viscosity monomers include, for example, 4-butylphenyl (meth) acrylate, phenyl (meth) acrylate, 2,4,5-tetramethylphenyl (meth) acrylate, and 4-chloro Phenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (2-HPA), 2- (meth) ) Acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalic acid, EO modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol ( meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, propoxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxydi(meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m -Phenoxybenzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acryl rate, tricyclodecanedimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, penta Erythritol tri (meth) acrylate, dimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol ethoxy tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaerythritol hexa(meth)acrylate etc. are mentioned.

Among the monomers (B), examples of the low-viscosity monomer include 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol. Di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, methyl (meth) acrylate , ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. are mentioned.

Although the monomer (B) may be a monofunctional monomer or a polyfunctional monomer, it is preferable that at least a part of the monomer (B) is a monofunctional monomer, It is more preferable that a part is a monofunctional monomer and the other part is a polyfunctional monomer. That is, it is preferable that the monomer component may contain 2 or more types of monomers (B), and it is preferable that one part of 2 or more types of monomers (B) is a monofunctional monomer, and the other part is a polyfunctional monomer.

Among the monomers (B), examples of the monofunctional monomer include 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4- Chlorophenyl (meth) acrylate, phenoxymethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate (2-HPA), 2- ( Meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropylphthalic acid, EO modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, PO-modified nonylphenol (meth)acrylate, ethoxylated-o-phenylphenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, dicyclofentanyl (meth)acrylate, dicyclopentanyl (meth)acrylate Clofentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylic a rate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc. are mentioned.

Among the monomers (B), examples of the polyfunctional monomer include ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, and propoxylated ethoxylated bisphenol A di(meth). ) acrylate, bisphenol A epoxydi(meth)acrylate, tricyclodecanedimethanoldi(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxy Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol ethoxytetra(meth)acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythol hexa (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1, 10-decanediol di(meth)acrylate, 1,12- dodecanediol di(meth)acrylate, etc. are mentioned.

A photoinitiator may be activated by actinic rays, such as visible light and an ultraviolet-ray, and may just be a compound which can initiate or accelerate|stimulate the polymerization of a monomer component. A photoinitiator may be used individually by 1 type, and may be used in combination of 2 or more type. As a photoinitiator, a photoradical polymerization initiator is preferable.

As a radical photopolymerization initiator

benzophenone and its derivatives;

benzyl and its derivatives;

anthraquinone and its derivatives;

benzoin type photoinitiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal;

acetophenone-type photoinitiators such as diethoxyacetophenone and 4-tert-butyltrichloroacetophenone;

2-dimethylaminoethyl benzoate;

p-dimethylaminoethylbenzoate;

diphenyldisulfide;

thioxanthone and its derivatives;

Camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1 -Carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxy-2-methylester, 7,7-dimethyl-2,3-diox campaquinone-type photoinitiators such as sobicyclo[2.2.1]heptane-1-carboxylic acid chloride;

2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone- α-aminoalkylphenone type photopolymerization initiators such as 1;

Benzoyldiphenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide, benzoyldiethoxyphosphine oxide, 2,4,6-trimethylbenzoyldimethoxyphenylphosphine oxide, 2,4,6- acylphosphine oxide-type photoinitiators such as trimethylbenzoyl diethoxyphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide;

phenyl-glyoxylic acid-methyl ester;

Oxy-phenyl-acetic acid 2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl ester;

oxy-phenyl-acetic acid 2-[2-hydroxy-ethoxy]-ethyl ester; and the like.

As a photoinitiator, an acylphosphine oxide type photoinitiator is preferable from a viewpoint which can be hardened|cured using only visible light of 390 nm or more. Further, the acylphosphine oxide type photopolymerization initiator can be referred to as a photopolymerization initiator having an acylphosphine oxide group (-(C=O)-(P=O)<). Moreover, diphenyl-2,4,6- trimethylbenzoyl phosphine oxide is especially preferable from a viewpoint from which it can harden|cure by light of 395 nm or more and a hardened|cured material with a higher visible light transmittance becomes easy to be obtained. As diphenyl-2,4,6- trimethylbenzoyl phosphine oxide, the BASF Japan company "Irgacure TPO" etc. are mentioned, for example.

0.05 mass part or more is preferable with respect to 100 mass parts of total amounts of a monomer component, as for content of a photoinitiator, 0.5 mass part or more is more preferable, 2 mass part or more is still more preferable, 2.5 mass part or more is still more preferable. There exists a tendency for the hardening performance of a composition to improve more by increasing content of a photoinitiator. 12 mass parts or less are preferable with respect to 100 mass parts of total amounts of a monomer component, as for content of a photoinitiator, 8 mass parts or less are more preferable, and its 6 mass parts or less are still more preferable. By reducing the content of the photoinitiator, a cured product having a higher visible light transmittance can be easily obtained. That is, the content of the photoinitiator is, for example, 0.05 to 12 parts by mass, 0.05 to 8 parts by mass relative to 100 parts by mass of the total amount of the monomer components. , 0.05 to 6 parts by mass, 0.5 to 12 parts by mass, 0.5 to 8 parts by mass, 0.5 to 6 parts by mass, 2 to 12 parts by mass, 2 to 8 parts by mass, 2 to 6 parts by mass, 2.5 to 12 parts by mass , 2. 5-8 mass parts or 2.5-6 mass parts may be sufficient.

The composition of this embodiment may contain other components other than a monomer component and a photoinitiator further. The composition of this embodiment may further contain the well-known additive used in the field of the sealing agent for organic electroluminescent display elements, for example. As an additive, antioxidant, a metal deactivator, a filler, a stabilizer, a neutralizing agent, a lubricant, an antibacterial agent etc. are mentioned, for example.

The composition of the present embodiment can be cured by irradiating at least one of visible light or ultraviolet light. In addition, in this specification, "curing" of a composition is not necessarily limited to rigidly solidifying, What is necessary is just to superpose|polymerize a monomer component and to form a polymer. For example, the cured body of the composition may be a rigid solid (eg, in the form of a glass) or may be in the form of a rubber.

Examples of energy irradiation sources for irradiating visible or ultraviolet light include deuterium lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, low-pressure mercury lamps, xenon lamps, xenon-mercury hybrid lamps, halogen lamps, excimer lamps, indium lamps, thallium lamps, and LED lamps. and energy irradiation sources such as electrodeless discharge lamps.

The composition of the present embodiment is preferably cured with light having a wavelength of 380 nm or more, more preferably cured with light having a wavelength of 395 nm or more, from the viewpoint of hardly causing damage to the organic EL display element, and cured with light having a wavelength of 395 nm or more. Most preferred. The wavelength of the irradiated light is preferably 500 nm or less because the temperature rise of the irradiated portion due to infrared light can be avoided and the possibility of damaging the organic EL display element is small. As an energy irradiation source, the LED lamp whose light emission wavelength is a short wavelength is preferable.

It is preferable that it is 100-8000 mJ/cm<2>, and, as for the irradiation amount at the time of hardening a composition, it is more preferable that it is 300-2000 mJ/cm<2>. By making an irradiation amount 100 mJ/cm<2> or more, a composition fully hardens|cures and it becomes easy to obtain high adhesive strength. Moreover, the composition can be hardened without damaging an organic electroluminescent display element by making an irradiation amount into 8000 mJ/cm<2> or less. That is, the irradiation amount at the time of hardening a composition may be 100-8000 mJ/cm<2>, 300-8000 mJ/cm<2>, 100-2000 mJ/cm<2>, 300-2000 mJ/cm<2>, for example.

It is preferable that the hardening body of the composition of this embodiment is excellent in transparency. Specifically, the cured body preferably has a spectral transmittance in the ultraviolet-visible light region of 360 nm or more and 800 nm or less per 10 μm in thickness of 95% or more, more preferably 97% or more, and still more preferably 99% or more. If the spectral transmittance is 95% or more, an organic EL display device excellent in luminance and contrast can be easily obtained.

According to JIS Z 0208: 1976, the cured product of the composition of this embodiment has a value of moisture permeability at 100 μm thickness measured by exposing it to an environment of 85° C. and 85% RH for 24 hours is 500 g/m ² or less, It is more preferable that it is 400 g/m< ² > or less, and it is still more preferable that it is 350 g/m< ² > or less. When water vapor transmission rate is low, generation|occurrence|production of the dark spot by the arrival of the water|moisture content to the organic light emitting material layer can be suppressed more remarkably.

The usage method of the composition of this embodiment is not specifically limited. The composition of this embodiment can be used suitably as a sealing agent for organic electroluminescent display elements. Specifically, for example, a composition can be applied to an object (eg, an organic EL display device), and the encapsulant composed of a cured product of the composition can be formed by curing the composition on the object.

Further, the composition may be cured into a predetermined shape (eg, film-like, sheet-like, etc.) to form a sealing material having a predetermined shape. In this case, for example, the organic EL display element can be sealed by disposing the encapsulant on the organic EL display element.

Since the composition of this embodiment is excellent in surface flatness and straightness, even when applied to an inkjet method, an organic film with few irregularities can be accurately formed in a predetermined range on the surface.

For this reason, the composition of this embodiment can be used suitably as a coating liquid for forming an organic film (preferably an organic film as a sealing material for organic electroluminescent display elements) by the inkjet method.

Hereinafter, a top emission organic EL display device will be described as an example for an aspect of an organic EL display device formed by using the composition of the present embodiment as an encapsulant. Further, the organic EL display device to which the composition of the present embodiment is applied is not limited to the top emission type organic EL display device of the bottom emission type in which light generated from the organic EL layer is irradiated from the substrate side. may be

A top emission type organic EL display device includes an organic EL display element, an encapsulation layer for encapsulating the organic EL display element, and an encapsulation substrate provided on the encapsulation layer.

The organic EL display device has, for example, a structure in which an anode, an organic EL layer including a light emitting layer, and a cathode are sequentially stacked on a substrate.

As a board|substrate of an organic electroluminescent display element, a glass substrate, a silicon substrate, a plastic substrate, etc. are mentioned, for example. Among these, a glass substrate and a plastic substrate are preferable, and a glass substrate is more preferable.

Examples of plastics used for plastic substrates include polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzoimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, polyparaphenylene vinylene, polymethyl methacrylate, polystyrene, polycarbonate, polycycloolefin, polyacryl, etc. are mentioned. Among these, polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polybenzoimidazole, polybenzobisthiazole, poly At least one of the group consisting of benzoxazole, polythiazole, and polyparaphenylenevinylene is preferable, and from the viewpoint of high transmittance of energy rays such as ultraviolet or visible light, polyimide, polyetherimide, polyethylene terephthalate, polyethylene At least one of the group consisting of naphthalates is more preferred.

As the anode, a conductive metal oxide film or translucent metal thin film having a relatively large work function (suitably having a work function greater than 4.0 eV) is generally used. As the material of the anode, for example, indium tin oxide (Indium Tin Oxide (hereinafter referred to as ITO), metal oxides such as tin oxide, metals such as gold (Au), platinum (Pt), silver (Ag), copper (Cu), or alloys containing at least one of these; Organic transparent conductive films, such as polyaniline or its derivative(s), polythiophene or its derivative(s), etc. are mentioned. The anode can be formed in a layer configuration of two or more layers, if necessary. The film thickness of the anode can be appropriately selected in consideration of electrical conductivity (in the case of a bottom emission type, light transmittance). 10 nm - 10 micrometers are preferable, as for the film thickness of an anode, 20 nm - 1 micrometer are more preferable, 50 nm - 500 nm are the most preferable. That is, the film thickness of the anode is, for example, 10 nm to 10 µm, 10 nm to 1 µm, 10 nm to 500 nm, 20 nm to 10 µm, 20 nm to 1 µm, 20 nm to 500 nm, 50 nm to 10 µm, 50 nm to 1 µm, or 50 nm ~500 nm may be sufficient. Examples of the method for producing the anode include a vacuum vapor deposition method, a sputtering method, an ion plating method, and a plating method. In the case of the top emission type, a reflective film for reflecting the light irradiated to the substrate side may be provided under the anode.

The organic EL layer includes at least a light emitting layer made of an organic material. This light emitting layer contains a light emitting material. Examples of the luminescent material include organic substances (low molecular weight compounds or high molecular weight compounds) that emit fluorescence or phosphorescence. The light emitting layer may further contain a dopant material. Examples of the organic substance include dye-based materials, metal complex-based materials, and polymeric materials. The dopant material is doped into the organic material for the purpose of improving the luminous efficiency of the organic material or changing the emission wavelength. The thickness of the light emitting layer made of these organic materials and a dopant doped as needed is usually 2 to 200 nm.

As the dye-based material, cyclophendamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine A ring compound, a perinone derivative, a perylene derivative, an oligothiophene derivative, a tripumanylamine derivative, an oxadiazole dimer, a pyrazoline dimer, etc. are mentioned.

Examples of the metal complex material include a metal complex having light emission from a triplet excited state such as an iridium complex and a platinum complex, an aluminum quinolinol complex, a benzoquinolinol beryllium complex, a benzoxazolyl zinc complex, a benzothiazole zinc complex, and azo Metal complexes, such as a methyl zinc complex, a porphyrin zinc complex, and a europium complex, etc. are mentioned. The metal complex includes rare earth metals such as terbium (Tb), europium (Eu) and dysprosium (Dy) as the central metal, aluminum (Al), zinc (Zn), beryllium (Be), etc., and oxadiazole and thia as ligands and metal complexes having a diazole, phenylpyridine, phenylbenzoimidazole, quinoline structure, and the like. Among these, a metal complex having aluminum (Al) as a central metal and a quinoline structure as a ligand is preferable. Tris(8-hydroxyquinolinate)aluminum is preferable among the metal complexes which have aluminum (Al) as a central metal and a quinoline structure etc. as a ligand.

Examples of the polymer material include polyparaphenylenevinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and the above dyes and metal complex light emitting materials. polymerized ones, and the like.

Among the luminescent materials, examples of the material emitting blue light include distyrylarylene derivatives, oxadiazole derivatives, polyvinylcarbazole derivatives, polyparaphenylene derivatives, polyfluorene derivatives, and polymers thereof. Among these, a polymer material is preferable. Among the polymer materials, at least one of the group consisting of polyvinylcarbazole derivatives, polyparaphenylene derivatives and polyfluorene derivatives is preferable.

Examples of the green light-emitting material include quinacridone derivatives, coumarin derivatives, polyparaphenylenevinylene derivatives, polyfluorene derivatives, and polymers thereof. Among these, a polymer material is preferable. Among the polymer materials, at least one selected from the group consisting of polyparaphenylenevinylene derivatives and polyfluorene derivatives is preferable.

Examples of the red light-emitting material include coumarin derivatives, thiophene ring compounds, polyparaphenylenevinylene derivatives, polythiophene derivatives, polyfluorene derivatives, and polymers thereof. Among these, a polymer material is preferable. Among the polymer materials, at least one of the group consisting of polyparaphenylenevinylene derivatives, polythiophene derivatives and polyfluorene derivatives is preferable.

Examples of the dopant material include perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squarium derivatives, porphyrin derivatives, styryl dyes, tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, and the like. have.

In the organic EL layer, a layer provided between the light emitting layer and the anode and a layer provided between the light emitting layer and the cathode other than the light emitting layer can be provided as appropriate. First, as a layer provided between the light emitting layer and the anode, a hole injection layer for improving the hole injection efficiency from the anode, a hole transport layer for transporting holes injected from the anode or the hole injection layer to the light emitting layer, and the like. Examples of the layer provided between the light emitting layer and the cathode include an electron injection layer for improving electron injection efficiency from the cathode, and an electron transport layer for transporting electrons injected from the cathode or the electron injection layer to the light emitting layer.

Examples of the material for forming the hole injection layer include phenylamines such as 4',4"-tris{2-naphthyl(phenyl)amino}triphenylamine, starburst amines, phthalocyanines, vanadium oxide, molybdenum oxide, oxide Oxides, such as ruthenium and aluminum oxide, amorphous carbon, polyaniline, polythiophene derivative, etc. are mentioned.

Examples of the material constituting the hole transport layer include polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, benzidine Derivatives, polyaniline or its derivatives, polythiophene or its derivatives, polyarylamine or its derivatives, polypyrrole or its derivatives, poly(p-phenylenevinylene) or its derivatives, poly(2,5-thienylenevinylene) or derivatives thereof.

When these hole injection layers or hole transport layers have a function of stopping the transport of electrons, they are sometimes referred to as electron blocking layers.

Examples of the material constituting the electron transport layer include oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinodimethane or its derivatives, fluorenone derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives, etc. have. A metal complex etc. are mentioned as a derivative|guide_body. Among these, 8-hydroxyquinoline or a derivative thereof is preferable. Among the 8-hydroxyquinoline or its derivatives, tris(8-hydroxyquinolinato)aluminum is preferable in that it can be used as an organic material that emits fluorescence or phosphorescence contained in the light emitting layer.

As the electron injection layer, depending on the type of the light emitting layer, an electron injection layer having a single layer structure of a calcium (Ca) layer, or a metal belonging to Groups IA and IIA of the periodic table and having a work function of 1.5 to 3.0 eV, and an oxide or halogen of the metal A single-layer structure of one or more layers formed of at least one of the group consisting of cargoes and carbonates, or metals of Groups IA and IIA of the periodic table, and metals having a work function of 1.5 to 3.0 eV, and oxides, halides and carbonates of those metals The electron injection layer which consists of a laminated structure of the layer formed of 1 or more types from the group which consists of, and a Ca layer, etc. are mentioned. Examples of metals of Group IA of the periodic table having a work function of 1.5 to 3.0 eV or oxides, halides and carbonates thereof include lithium (Li), lithium fluoride, sodium oxide, lithium oxide, and lithium carbonate. Examples of the metal of Group IIA of the periodic table having a work function of 1.5 to 3.0 eV or oxides, halides and carbonates thereof include strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium oxide, and magnesium carbonate. .

When these electron transport layers or electron injection layers have a function of stopping transport of holes, these electron transport layers or electron injection layers are sometimes referred to as hole blocking layers.

For the cathode, a transparent or translucent material having a relatively small work function (suitably having a work function of less than 4.0 eV) and easy electron injection into the light emitting layer is preferable. As the material of the cathode, lithium (Li), sodium (Na ), potassium (K), rubidium (Rb), cesium (Cs), beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), aluminum (Al), scandium (Sc) ), vanadium (V), zinc (Zn), yttrium (Y), indium (In), cerium (Ce), samarium (Sm), europium (Eu), terbium (Tb), metals such as ytterbium (Yb), Or an alloy consisting of two or more of the above metals, or one or more of these and gold (Au), silver (Ag), platinum (Pt), copper (Cu), chromium (Cr), manganese (Mn), titanium ( Ti), cobalt (Co), nickel (Ni), tungsten (W), an alloy consisting of one or more of tin (Sn), graphite or a graphite interlayer compound, or a metal oxide such as ITO or tin oxide. have.

The cathode may have a laminated structure of two or more layers. As a laminated structure of two or more layers, the laminated structure of the above-mentioned metal, a metal oxide, a fluoride, these alloys, and metals, such as Al, Ag, Cr, etc. are mentioned. The thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability. 10 nm - 10 micrometers are preferable, as for the film thickness of a cathode, 15 nm - 1 micrometer are more preferable, 20 nm - 500 nm are the most preferable. That is, the film thickness of the cathode is, for example, 10 nm to 10 µm, 10 nm to 1 µm, 10 nm to 500 nm, 15 nm to 10 µm, 15 nm to 1 µm, 15 nm to 500 nm, 20 nm to 10 µm, 20 nm to 1 µm, or 20 nm to 500 nm may be sufficient. As a manufacturing method of a cathode, a vacuum evaporation method, sputtering method, the lamination method of thermocompression bonding a metal thin film, etc. are mentioned.

The layer provided between the light emitting layer and the anode and between the light emitting layer and the cathode can be appropriately selected according to the performance required for the organic EL display device to be manufactured. For example, as a structure of the organic electroluminescent display element used in this embodiment, it can have any one of the layer structures of following (i)-(xv).

(i) anode/hole transport layer/light emitting layer/cathode

(ii) anode/light emitting layer/electron transport layer/cathode

(iii) anode/hole transport layer/light emitting layer/electron transport layer/cathode

(iv) anode/hole injection layer/light emitting layer/cathode

(v) anode/light emitting layer/electron injection layer/cathode

(vi) anode/hole injection layer/light emitting layer/electron injection layer/cathode

(vii) anode/hole injection layer/hole transport layer/light emitting layer/cathode

(viii) anode/hole transport layer/light emitting layer/electron injection layer/cathode

(ix) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode

(x) anode/hole injection layer/light emitting layer/electron transport layer/cathode

(xi) anode/light emitting layer/electron transport layer/electron injection layer/cathode

(xii) anode/hole injection layer/light emitting layer/electron transport layer/electron injection layer/cathode

(xiii) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode

(xiv) anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode

(xv) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

(Here, "/" indicates that each layer is stacked adjacent to each other. The same applies hereinafter.)

The encapsulation layer is a layer having a high barrier property to the gas in order to prevent a gas such as water vapor or oxygen from contacting the organic EL display element, and is provided to encapsulate the organic EL display element. In this encapsulation layer, an inorganic film and an organic film are alternately formed from below. The inorganic/organic laminate may be formed repeatedly two or more times.

The inorganic film of the inorganic/organic laminate is a film provided to prevent the organic EL display element from being exposed to a gas such as water vapor or oxygen present in an environment in which the organic EL display device is placed. The inorganic film of the inorganic/organic laminate is preferably a continuous dense film with few defects such as pinholes. Examples of the inorganic film include single films such as SiN film, SiO film, SiON film, Al ₂ O ₃ film, and AlN film, and laminated films thereof.

The organic film of the inorganic/organic laminate is provided to cover defects such as pinholes formed on the inorganic film and to impart flatness to the surface. The organic film is formed in a region narrower than the region where the inorganic film is formed. This is because, when the organic film is formed to be wider than or equal to the area where the inorganic film is formed, the organic film is deteriorated in the exposed region. However, the uppermost organic film formed on the uppermost layer of the entire encapsulation layer is formed in substantially the same region as the formation region of the inorganic film. Then, the upper surface of the encapsulation layer is formed to be planarized. The organic film may be a film formed using the composition of the present embodiment described above (that is, a film containing a cured product of the composition).

The composition of this embodiment is suitable for inkjet application|coating as mentioned above, and it is excellent in the discharge property by inkjet and the flatness after inkjet application|coating. When the coating method by the inkjet method is used, an organic film can be formed quickly and uniformly.

The encapsulation layer is preferably 1 to 5 sets if the inorganic/organic laminate is counted as one set. This is because, when the inorganic/organic laminate is six or more sets, the encapsulation effect for the organic EL display element is almost the same as that in the case of five sets. As for the thickness of the inorganic film of an inorganic/organic laminated body, 50 nm - 1 micrometer are preferable. 1-15 micrometers is preferable and, as for the thickness of the organic film of an inorganic/organic laminated body, 3-10 micrometers is more preferable. When the thickness of the organic film is 1 µm or more, it is possible to completely cover the particles generated during element formation, and it is possible to coat the inorganic film with good flatness. When the thickness of the organic film is 15 µm or less, moisture does not penetrate from the side surface of the organic film, and the reliability of the organic EL display device is improved. The thickness of the organic film of the inorganic/organic laminate may be, for example, 1 to 15 µm, 1 to 10 µm, 3 to 15 µm, or 3 to 10 µm.

The encapsulation substrate is formed in close contact so as to cover the entire upper surface of the uppermost organic layer of the encapsulation layer. The above-mentioned board|substrate is mentioned as this sealing board|substrate. Among these, a substrate transparent to visible light is preferable. Among the substrates transparent to visible light (transparent sealing substrate), at least one of the group consisting of a glass substrate and a plastic substrate is preferable, and a glass substrate is more preferable.

The thickness of the transparent encapsulation substrate is preferably 1 µm or more and 1 mm or less, more preferably 10 µm or more and 800 µm or less, and most preferably 50 µm or more and 300 µm or less. By providing the transparent encapsulation substrate in the upper layer of the encapsulation layer, deterioration which proceeds when the surface of the uppermost organic film touches the substrate can be suppressed, and the barrier property of the organic EL display device can be improved. The thickness of the plate is, for example, 1 μm to 1 mm, 1 μm to 800 μm, 1 μm to 300 μm, 10 μm to 1 mm, 10 μm to 800 μm, 10 μm to 300 μm, 50 μm to 1 mm, 50 μm to 800 µm or 50 µm to 300 µm may be sufficient.

Next, the manufacturing method of the organic electroluminescent display which has such a structure is demonstrated. First, an organic EL display device is formed by sequentially forming an anode, an organic EL layer including a light emitting layer, and a cathode patterned in a predetermined shape by a conventionally known method on a first substrate. For example, when an organic EL display device is used as a dot matrix display device, a bank is formed to divide the light emitting region in a matrix form, and an organic EL layer including the light emitting layer is formed in a region surrounded by the bank.

Next, a first inorganic film is formed on the substrate on which the organic EL display element is formed by a film formation method such as a PVD (Physical Vapor Deposition) method such as a sputtering method or a CVD method such as a plasma CVD (Chemical Vapor Deposition) method. Then, the composition (sealing agent) of this embodiment is made to adhere on the 1st inorganic film using coating film formation methods, such as a solution coating method and a spray coating method, a flash vapor deposition method, an inkjet method, etc. Among these, the inkjet method is preferable from the point of productivity. Thereafter, the encapsulant is cured by irradiation with energy rays such as ultraviolet rays or visible rays to form a first organic film. One set of inorganic/organic laminates is formed by the above process. Although the curing rate of the sealing agent is not particularly limited as long as the effect of the present embodiment is exhibited, for example, it is a value obtained according to the measurement method described later, and may be 90% or more, preferably 95% or more.

The formation process of the inorganic/organic laminated body shown above is repeated a predetermined number of times. However, regarding the last set, that is, the inorganic/organic laminate of the uppermost layer, the encapsulant may be attached to the upper surface of the inorganic film by a coating method, flash deposition method, inkjet method, or the like so that the upper surface is flattened.

Then, the transparent encapsulation substrate is bonded to the surface to which the encapsulant is attached on the substrate. Alignment is performed at the time of bonding. Then, the sealing agent of this embodiment which exists between the inorganic film of an uppermost layer and the transparent sealing substrate is hardened by irradiating an energy ray from the transparent sealing board|substrate side. As a result, the encapsulant is cured to form an uppermost organic film, and the uppermost organic film is adhered to the transparent encapsulation substrate. The manufacturing method of an organic electroluminescent display apparatus is complete|finished by the above.

After adhering a sealing agent on an inorganic membrane, you may irradiate an energy ray partially and superpose|polymerize. By doing in this way, when a transparent sealing board|substrate is mounted, the collapse of the shape of an uppermost organic film can be prevented. The thickness of the inorganic film and the organic film may be the same in each inorganic/organic laminate, or may be different in each inorganic/organic laminate.

In the present embodiment, the organic EL display device can be used as a planar light source, a segment display device, and a dot matrix display device.

As mentioned above, although preferred embodiment of this invention was described, this invention is not limited to the said embodiment.

Example

Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to an Example.

The detail of the component used by the Example and the comparative example is as follows. The viscosity of the monomer component represents a value measured with an E-type viscometer at 25°C.

<Fluorine-containing monomer>

・「13F」

Osaka Organic Chemical Co., Ltd., brand name "Viscoat 13F"

Compound name: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate

Viscosity: 4 mPa s

・「LINK-162A」

manufactured by Kyoeisha Chemical, trade name "LINK-162A"

Compound name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediacrylate

Viscosity: 32 mPa s

<Monomer (B)>

・「A-LEN-10」

Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name "NK Ester A-LEN-10"

Compound name: ethoxylated o-phenylphenol acrylate

Viscosity: 150 mPa s

・「DCPA」

Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name "NK Ester A-DCP"

Compound name: tricyclodecanedimethanol diacrylate

Viscosity: 120 mPa s

・「BPE200」

Manufactured by Shin-Nakamura Chemical Industry Co., Ltd., brand name "NK Ester BPE-200"

Compound Name: Ethoxylated Bisphenol A Dimethacrylate

Viscosity: 600 mPa s

・「SR262」

Manufactured by Alkema, brand name "SR262"

Compound name: 1,12-dodecanediol dimethacrylate

Viscosity: 12 mPa s

<Photoinitiator>

・「TPO」

Product made by iGM Resins, brand name "Omnirad TPO"

Compound name: diphenyl-2,4,6-trimethylbenzoylphosphine oxide

(Example 1)

1 mass part "LINK-162A", 5 mass parts "A-LEN-10", 5 mass parts "DCPA", 89 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1 mass%, the ratio of the high-viscosity monomer was 10 mass%, and the ratio of the bifunctional monomer was 95 mass%. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 13 mPa·s.

(Example 2)

1 mass part "LINK-162A", 5 mass parts "A-LEN-10", 18 mass parts "DCPA", 76 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1% by mass, the ratio of the high-viscosity monomer was 23% by mass, and the ratio of the bifunctional monomer was 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 16 mPa·s.

(Example 3)

1 mass part "LINK-162A", 5 mass parts "A-LEN-10", 50 mass parts "DCPA", 44 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was set to 1% by mass, the ratio of the high-viscosity monomer to 55% by mass, and the ratio of the bifunctional monomer to 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 36 mPa·s.

(Example 4)

0.01 parts by mass of "LINK-162A", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76.99 parts by mass of "SR262", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, in the monomer component, the ratio of the fluorine-containing monomer was 0.01% by mass, the ratio of the high-viscosity monomer was 23% by mass, and the ratio of the bifunctional monomer was 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 16 mPa·s.

(Example 5)

90 mass parts "LINK-162A", 5 mass parts "A-LEN-10", 5 mass parts "DCPA", and 3.5 mass parts "TPO" were mixed, and the composition was prepared. That is, in the monomer component, the ratio of the fluorine-containing monomer was 90% by mass, the ratio of the high-viscosity monomer was 10% by mass, and the ratio of the bifunctional monomer was 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 35 mPa·s.

(Example 6)

1 part by mass of "LINK-162A", 5 parts by mass of "A-LEN-10", 15 parts by mass of "DCPA", 3 parts by mass of "BPE200", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO" are mixed. to prepare a composition. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1% by mass, the ratio of the high-viscosity monomer was 23% by mass, and the ratio of the bifunctional monomer was 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 17 mPa·s.

(Example 7)

1 mass part "13F", 5 mass parts "A-LEN-10", 18 mass parts "DCPA", 76 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1% by mass, the ratio of the high-viscosity monomer was 23% by mass, and the ratio of the bifunctional monomer was 94% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 16 mPa·s.

(Comparative Example 1)

1 mass part "LINK-162A", 99 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1% by mass, the ratio of the high-viscosity monomer was 0% by mass, and the ratio of the bifunctional monomer was 100% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 12 mPa·s.

(Comparative Example 2)

1 mass part "LINK-162A", 5 mass parts "A-LEN-10", 94 mass parts "DCPA", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 1% by mass, the ratio of the high-viscosity monomer was 99% by mass, and the ratio of the bifunctional monomer was 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 120 mPa·s.

(Comparative Example 3)

5 mass parts "A-LEN-10", 18 mass parts "DCPA", 77 mass parts "SR262", and 3.5 mass parts "TPO" were mixed, and the composition was manufactured. That is, in the monomer component, the ratio of the fluorine-containing monomer was 0 mass %, the ratio of the high-viscosity monomer was 23 mass %, and the ratio of the bifunctional monomer was 95 mass %. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 16 mPa·s.

The compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated by the following method. A result is shown in Table 1 and Table 2.

<E-type viscosity>

The viscosity of the composition was measured using an E-type viscometer (cone plate type: cone angle 1° 34', cone rotor radius 24 mm) at a temperature of 25° C. and a rotation speed of 100 rpm.

<Surface tension>

The surface tension of the composition was measured by the pendant drop method using a contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.) under an atmosphere of 23°C.

<Evaluation of surface flatness>

On a substrate of 70 mm × 70 mm × 0.7 mmt (alkali-free glass (Eagle XG, available from Corning)), recesses of 25 μm×25 μm×3 μm were prepared by etching by opening a gap of 10 μm on the front and back sides. A 200 nm SiN film was formed on the substrate on which was provided by plasma CVD. Then, the composition was pattern-coated so that it might become 15 mm x 15 mm x 8 micrometers using the inkjet discharge apparatus (MID500B by Musashi Engineering, Inc., solvent type head "MID head"). In addition, the base material was washed with each of acetone and isopropanol before pattern application, and then washed for 5 minutes using a UV ozone cleaning device UV-208 manufactured by Technovision Corporation. After pattern application, it was left for 4 minutes in a nitrogen atmosphere at a temperature of 23°C and a relative humidity of 50%, and an LED lamp emitting a wavelength of 395 nm under a nitrogen atmosphere (UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA) The composition was photocured under the condition that the accumulated light amount of light having a wavelength of 395 nm was 1,500 mJ/cm 2 .

Next, the thickness of the cured film was measured in a direction perpendicular to the direction in which the head moved with a stylus-type shape measuring device (DektakXT manufactured by BRUKER). The difference between the maximum thickness and the minimum thickness in the surface in which 0.2 mm was subtracted from the edge part of the cured film was made into the evaluation result of surface flatness.

<Evaluation of straightness>

A 200 nm SiN film was formed by plasma CVD on a 70 mm x 70 mm x 0.7 mmt substrate (alkali-free glass (Eagle XG, manufactured by Corning)). Next, the composition was pattern-coated to the prescribed area|region so that it might become 15 mm x 15 mm x 8 micrometers using the inkjet discharge apparatus (MID500B by Musashi Engineering, Inc., solvent type head "MID head"). After pattern application, it was left for 4 minutes in a nitrogen atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and an LED lamp emitting a wavelength of 395 nm in a nitrogen atmosphere (UV-LED LIGHT SOURCE H-4MLH200-V1 manufactured by HOYA) The composition was photocured under the condition that the accumulated light amount of light having a wavelength of 395 nm was 1,500 mJ/cm 2 .

Next, about the protrusion length from the prescribed|regulated area|region of the hardening body, 15 places per side, a total of 60 places, were measured with the optical microscope, and the maximum value was made into the value of straightness.

<Evaluation of moisture permeability>

A sheet-like cured product having a thickness of 0.1 mm was produced under the above photocuring conditions. Calcium chloride (anhydrous) is used as a desiccant according to JIS Z0208: 1976 "Testing method for moisture permeability of moisture-proof packaging materials (cup method)", and exposed to conditions of temperature of 85 ° C. and relative humidity of 85% for 24 hours, and cured product with a thickness of 100 μm of the moisture permeability was measured.

As shown in Table 1, the composition of the Example was able to make the outstanding surface flatness and straightness compatible. Moreover, it was confirmed that the composition of an Example has sufficiently low moisture permeability of the cured body to be formed, and is useful as a sealing material for organic electroluminescent display elements.

Moreover, as shown in Table 2, in Comparative Example 1, the coating liquid was easy to meander at the time of inkjet application|coating, and the result was inferior to linearity. Moreover, in Comparative Example 3, the result was inferior to surface flatness. Moreover, in Comparative Example 2, the viscosity of the composition was high, discharge from the inkjet nozzle was difficult, and surface flatness and straightness could not be evaluated.

Claims (11)

A monomer component comprising a fluorine atom and a fluorine-containing monomer having a carbon-carbon unsaturated double bond;
a photopolymerization initiator;
At least a part of the monomer component is a high-viscosity monomer having a viscosity of 50 mPa·s or more as measured by an E-type viscometer at 25°C,
A composition having a viscosity of 3 mPa·s or more and 50 mPa·s or less as measured by an E-type viscometer at 25°C. The composition according to claim 1, wherein 5 to 65% by mass of the monomer component is the high viscosity monomer. The composition according to claim 1 or 2, wherein at least a part of the monomer component is a polyfunctional monomer having two or more carbon-carbon unsaturated double bonds. The composition of claim 3, wherein 70 to 98% by mass of the monomer component is the polyfunctional monomer. The composition according to any one of claims 1 to 4, wherein at least a part of the high-viscosity monomer is a monofunctional monomer having one carbon-carbon unsaturated double bond. The composition of claim 5, wherein 10 to 60% by mass of the high-viscosity monomer is the monofunctional monomer. The composition according to any one of claims 1 to 6, which is an encapsulant for an organic electroluminescent display device. The hardening body formed by hardening|curing the composition in any one of Claims 1-7. An encapsulant for an organic electroluminescent display device comprising the curing body according to claim 8 . Including a laminate in which an inorganic film and an organic film are laminated,
The organic film encapsulant for an organic electroluminescent display device comprising the cured body according to claim 8. an organic electroluminescent display device;
An organic electroluminescent display device comprising the encapsulant for an organic electroluminescent display device according to claim 9 or 10.