TW202124659A - Composition, hardened body, sealing material for organic electroluminescent display element, and organic electroluminescence display device - Google Patents

Abstract

A composition containing a monomer component which contains a fluorine-containing monomer having a fluorine atom and a carbon-carbon unsaturated double bond, and a photopolymerization initiator, wherein at least a portion of the monomer component is a high-viscosity monomer with a viscosity measured by an E-type viscometer at 25°C of 50 mPa·s or higher, and the viscosity of the composition measured by an E-type viscometer at 25°C is at least 3 mPa·s but not more than 50 mPa·s.

Description

Composition, hardened body, sealing material for organic electroluminescence display element, and organic electroluminescence display device

The present invention relates to a composition and its hardened body. In addition, the present invention relates to a sealing material for an organic electroluminescence (EL) display element and an organic EL display device containing the sealing material.

Organic electroluminescence display elements (also referred to as organic EL display elements, organic EL elements, or OLED elements) are attracting attention as an element body capable of emitting light with high brightness. However, the organic EL display element has a problem of deterioration due to moisture, resulting in a decrease in luminescence characteristics.

In order to solve such a problem, a technique for sealing an organic EL display element using a sealing material formed by laminating an organic film and an inorganic film to prevent deterioration due to moisture has been studied (for example, Patent Documents 1 and 2). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2001-307873 A [Patent Document 2] JP 2009-37812 A

[The problem to be solved by the invention]

In recent years, the required characteristics of organic EL display elements have increased, and sealing materials that can achieve higher reliability and durability have been demanded.

As for the forming method of the sealing material, a method of forming an organic film by coating and curing a resin composition and laminating an inorganic film on the organic film is known. This method has a problem in that when unevenness occurs on the surface of the organic film, the adhesion to the inorganic film is reduced. In addition, when the resin composition is applied by the inkjet method, the coating liquid ejected from the inkjet nozzle snakes and deviates from a predetermined range, and it is difficult to form a correct organic film.

Therefore, the object of the present invention is to provide a composition capable of accurately forming an organic film with few surface irregularities in a predetermined range. In addition, the object of the present invention is to provide a cured body of the above composition, which is effective as a sealing material for organic EL display elements. In addition, an object of the present invention is to provide a sealing material for an organic EL display element containing the above-mentioned hardened body, and to provide an organic EL display device containing the sealing material. [Means to solve the problem]

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 above-mentioned monomer components are high-viscosity monomers with a viscosity of 50 mPa･s or more as measured by an E-type viscometer at 25°C. In addition, the viscosity of the above composition measured with an E-type viscometer at 25°C is 3 mPa･s or more and 50 mPa･s or less.

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

In the composition requested in one aspect, 5-65% by mass of the above-mentioned monomer components may also be the above-mentioned high-viscosity monomer.

In one aspect, at least a part of the above-mentioned monomer components may be a multifunctional monomer having two or more carbon-carbon unsaturated double bonds.

In the composition requested in one aspect, 70-98% by mass of the above-mentioned monomer components may also be the above-mentioned multifunctional monomer.

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

In the composition requested in one aspect, 10-60% by mass of the above-mentioned high-viscosity monomer may also be the above-mentioned monofunctional monomer.

The above composition can be preferably used as a sealing agent for an organic electroluminescence display element.

Another aspect of the present invention relates to a hardened body formed by hardening the above-mentioned composition.

Yet another aspect of the present invention relates to a sealing material for an organic electroluminescence display device, which contains the above-mentioned hardened body.

Yet another aspect of the present invention relates to a sealing material for an organic electroluminescence display element, which contains a laminate formed by laminating an inorganic film and an organic film, and the organic film contains the cured body as described in Claim 8.

Yet another aspect of the present invention relates to an organic electroluminescence display device including an organic electroluminescence display element and the above-mentioned sealing material for the organic electroluminescence display element. [Effects of Invention]

According to the present invention, there is provided a composition capable of accurately forming an organic film with few surface irregularities in a predetermined range. Furthermore, according to the present invention, a cured body of the above-mentioned composition is provided, and the cured body is effective as a sealing material for an organic EL display element. In addition, according to the present invention, a sealing material for an organic EL display element containing the above-mentioned hardened body is provided, and an organic EL display device containing the sealing material is provided.

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

＜Compositions＞ The composition of this embodiment contains a monomer component containing a fluorine-containing monomer, and a photopolymerization initiator. In this embodiment, at least a part of the monomer component is a high-viscosity monomer with a viscosity of 50 mPa･s or more measured with an E-type viscometer at 25°C. In addition, the viscosity of the composition of this embodiment measured with an E-type viscometer at 25°C is 3 mPa･s or more and 50 mPa･s or less.

Since the viscosity of the composition of this embodiment falls within the above range, the inkjet method can be ideally used. Since the surface is excellent in flatness and straightness, an organic film with less surface irregularities can be accurately formed in a predetermined range.

It is considered that the reason for achieving the above-mentioned effect is as follows, but it is not limited to this. First, it is considered that the composition of the present embodiment contains a fluorine-containing monomer, so the surface free energy becomes low, and after coating, the surface of the coating film is easily flattened, and an organic film with less surface irregularities can be formed. In addition, the composition of the present embodiment contains a high-viscosity monomer, and it is not easy to snake when ejected from an inkjet nozzle (that is, the straightness is improved), and a correct organic film can be formed in a predetermined range.

At least a part of the monomer component of this embodiment is a high-viscosity monomer with a viscosity of 50 mPa･s or more measured with an E-type viscometer at 25°C. The viscosity of the high-viscosity monomer should be 100mPa･s or more, more preferably 150mPa･s or more. In addition, the viscosity of the high-viscosity monomer is preferably 1000 mPa･s or less, more preferably 500 mPa･s or less, and even more preferably 300 mPa･s or less. That is, the viscosity of a high-viscosity monomer, as measured by an E-type viscometer at 25°C, can be, for example, 50-1000mPa･s, 50-500mPa･s, 50-300mPa･s, 100-1000mPa･ s, 100～500mPa･s, 100～300mPa･s, 150～1000mPa･s, 150～500mPa･s or 150～300mPa･s.

The viscosity of the composition of this embodiment (viscosity measured with an E-type viscometer at 25°C) is 3mPa･s or more, preferably 5mPa･s or more, and more preferably 10mPa･s or more. In addition, the viscosity of the composition of this embodiment (viscosity measured with an E-type viscometer at 25°C) is 50 mPa･s or less, preferably 45 mPa･s or less, and more preferably 40 mPa･s or less. If it is in such a viscosity range, there will be a tendency to improve the surface flatness. That is, the viscosity of the composition of the present embodiment, as measured with an E-type viscometer at 25°C, can be, for example, 3-50mPa･s, 3～45mPa･s, 3-40mPa･s, 5～ 50mPa･s, 5～45mPa･s, 5～40mPa･s, 10～50mPa･s, 10～45mPa･s or 10～40mPa･s.

The composition of this embodiment may contain high-viscosity monomers and low-viscosity monomers (monomers with a viscosity less than 50 mPa･s as measured by an E-type viscometer at 25°C) as monomer components. The ratio of the high-viscosity monomer to the low-viscosity monomer can be appropriately changed when the viscosity of the composition falls within the above-mentioned numerical range.

The ratio of the high-viscosity monomer in the monomer component may be, for example, 5% by mass or more, preferably 7% by mass or more, and more preferably 9% by mass or more. By increasing the ratio of high-viscosity monomers, there is a tendency to improve straightness. In addition, the ratio of the high-viscosity monomer in the monomer component may be, for example, 65% by mass or less, preferably 60% by mass or less, more preferably 55% by mass or less, or 50% by mass or less, or 45% by mass or less, 40% by mass or less, or 35% by mass or less. By reducing the ratio of high-viscosity monomers, there will be a tendency to reduce the viscosity of the composition and improve the ejectability. That is, the ratio of the high-viscosity monomer in the monomer component may be, for example, 5 to 65% by mass, 5 to 60% by mass, 5 to 55% by mass, 5 to 50% by mass, and 5 to 45% by mass. , 5-40% by mass, 5-35% by mass, 7-65% by mass, 7-60% by mass, 7-55% by mass, 7-50% by mass, 7-45% by mass, 7-40% by mass, 7 -35 mass%, 9-65% by mass, 9-60% by mass, 9-55% by mass, 9-50% by mass, 9-45% by mass, 9-40% by mass, or 9-35% by mass.

The composition of this embodiment may contain a monofunctional monomer having one carbon-carbon unsaturated double bond and a multifunctional monomer having two or more carbon-carbon unsaturated double bonds as monomer components.

The ratio of the polyfunctional monomer in the monomer component may be, for example, 70% by mass or more, preferably 75% by mass or more, and more preferably 80% by mass or more. By increasing the ratio of multifunctional monomers, there is a tendency to improve the moisture permeability of the hardened body and to improve the straightness. In addition, the ratio of the polyfunctional monomer in the monomer component may be, for example, 98% by mass or less, preferably 97% by mass or less, and more preferably 96% by mass or less. By reducing the proportion of multifunctional monomers, there is a tendency to improve the surface flatness. That is, the ratio of the multifunctional monomer in the monomer component may be, for example, 70 to 98% by mass, 70 to 97% by mass, 70 to 96% by mass, 75 to 98% by mass, and 75 to 97% by mass. , 75 to 96% by mass, 80 to 98% by mass, 80 to 97% by mass, or 80 to 96% by mass.

The polyfunctional monomer is preferably a monomer with 2-6 carbon-carbon unsaturated double bonds, preferably a monomer with 2 or 3 carbon-carbon unsaturated double bonds, and has 2 carbon-carbon unsaturated double bonds. The double-bonded bifunctional monomer is even better.

The composition of this embodiment can contain multifunctional monomers in the form of high-viscosity monomers, can also contain multi-functional monomers in the form of low-viscosity monomers, and can also contain multifunctional monomers that are high-viscosity monomers and those belonging to Both of low-viscosity monomers and multifunctional monomers.

The composition of this embodiment can contain monofunctional monomers in the form of high-viscosity monomers, can also contain monofunctional monomers in the form of low-viscosity monomers, and can also contain monofunctional monomers that are high-viscosity monomers and those belonging to Both of low-viscosity monomers and monofunctional monomers.

In this embodiment, at least a part of the high-viscosity monomer is preferably a monofunctional monomer.

The ratio of the monofunctional monomer in the high-viscosity monomer may be, for example, 9% by mass or more, preferably 10% by mass or more, more preferably 11% by mass or more, and even more preferably 12% by mass or more. In addition, the ratio of the monofunctional monomer in the high-viscosity monomer may be, for example, 60% by mass or less, preferably 55% by mass or less, and more preferably 50% by mass or less. By using a large amount of monofunctional monomers in the form of high-viscosity monomers, there is a tendency to further improve the moisture permeability, flexibility, and flexibility of the hardened body. That is, the ratio of the monofunctional monomer in the high-viscosity monomer can be, for example, 9-60% by mass, 9-55% by mass, 9-50% by mass, 10-60% by mass, and 10-55% by mass. %, 10-50% by mass, 11-60% by mass, 11-55% by mass, 11-50% by mass, 12-60% by mass, 12-55% by mass, or 12-50% by mass.

＜Fluorinated monomers＞ The fluorine-containing monomer is a monomer having a fluorine atom and a carbon-carbon unsaturated double bond. One type of fluorine-containing monomer may be used alone, or two or more types may be used in combination.

The fluorine-containing monomer can also be included in the monomer component in the form of a low-viscosity monomer. The viscosity of the fluorine-containing monomer (the viscosity measured with an E-type viscometer at 25°C), for example, may not reach 50mPa･s, preferably below 45mPa･s, preferably below 40mPa･s, and even more preferably below 35mPa･s . In addition, the viscosity of the fluorine-containing monomer (viscosity measured with an E-type viscometer at 25°C) may be, for example, 1 mPa･s or more, 2 mPa･s or more, or 3 mPa･s or more. That is, the viscosity of the fluorine-containing monomer, as measured by the E-type viscometer at 25°C, can be, for example, 1mPa･s or more and less than 50mPa･s, 1～45mPa･s, 1～40mPa･s , 1～35mPa･s, 2mPa･s or more and less than 50mPa･s, 2～45mPa･s, 2～40mPa･s, 2～35mPa･s, 3mPa･s or more and less than 50mPa･s, 3～45mPa ･S, 3～40mPa･s or 3～35mPa･s.

The number of fluorine atoms contained in the fluorine-containing monomer may be one or more, for example, it may be two or more, and preferably three or more. In addition, the upper limit of the number of fluorine atoms contained in the fluorine-containing monomer is not particularly limited. The number of fluorine atoms contained in the fluorine-containing monomer can be, for example, 40 or less, preferably 35 or less, more preferably 30 or less, and even more preferably 25 or less. That is, the number of fluorine atoms contained in the fluorine-containing monomer may be, for example, 1-40, 1-35, 1-30, 1-25, 2-40, 2-30, 2 ～30, 2-25, 3-40, 3-30, 3-30 or 3-25.

The content of the fluorine atom relative to the total amount of the fluorine-containing monomer may be, for example, 1% by mass or more, preferably 2% by mass or more, and more preferably 5% by mass or more. In addition, the content of fluorine atoms is based on the total amount of the fluorine-containing monomer. For example, it may be 90% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or less. . That is, the content of fluorine atoms based on the total amount of fluorine-containing monomers can be: 1 to 90% by mass, 1 to 75% by mass, 1 to 70% by mass, 1 to 65% by mass, and 2 to 90% by mass , 2 to 75% by mass, 2 to 70% by mass, 2 to 65% by mass, 5 to 90% by mass, 5 to 75% by mass, 5 to 70% by mass, or 5 to 65% by mass.

The number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer may be one or more. In addition, the number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer can be, for example, 4 or less. Considering that a hardened body with excellent flexibility can be easily obtained, it is preferably 3 or less, and more preferably 2 or less. good. That is, the number of carbon-carbon unsaturated double bonds possessed by the fluorine-containing monomer may be, for example, 1 to 4, 1 to 3, or 1 to 2.

The fluorine-containing monomer preferably has a (meth)acryloyl group as the group having a carbon-carbon double bond. That is, the fluorine-containing monomer is preferably a monomer having a fluorine atom and a (meth)acryloyl group. In addition, the (meth)acryloyl group means an acrylic group or a methacryloyl group.

One of the specific examples of the fluorine-containing monomer includes a compound represented by the following formula (A-1).

[化1]

In the 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 the carbon-carbon bond and the carbon-hydrogen bond in the fluorinated alkyl group.

The fluorinated alkyl group may be referred to as a group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. The number of carbon atoms of the fluorinated alkyl group is not particularly limited. For example, it may be 1 or more, preferably 2 or more, and more preferably 3 or more. In addition, the number of carbon atoms of the fluorinated alkyl group may be 25 or less, or 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 a difluoromethylene group (-CF ₂ -) can be ideally used.

Specific examples of fluorinated alkyl groups include: difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 1,1,1-trifluoroethyl, 2 ,2,2-Trifluoroethyl, perfluoroethyl, 1,1,2,2-tetrafluoropropyl, 1,1,1,2,2-pentafluoropropyl, 1,1,2,2 ,3,3-hexafluoropropyl, perfluoropropyl, perfluoroethylmethyl, 1-(trifluoromethyl)-1,2,2,2-tetrafluoroethyl, 2,2,3, 3-tetrafluoropropyl, perfluoropropyl, 1,1,2,2-tetrafluorobutyl, 1,1,2,2,3,3-hexafluorobutyl, 1,1,1,2, 2,3,3-Heptafluorobutyl, 1,1,2,2,3,3,4,4-octafluorobutyl, perfluorobutyl, 1,1-bis(trifluoro)methyl-2 ,2,2-Trifluoroethyl, 2-(perfluoropropyl)ethyl, 1,1,2,2,3,3,4,4-octafluoropentyl, 2,2,3,3, 4,4,5,5-octafluoropentyl, perfluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl, 1,1-bis(tri (Fluoromethyl)-2,2,3,3,3-pentafluoropropyl, 2-(perfluorobutyl)ethyl, 1,1,1,2,2,3,3,4,4-Nine Fluoropentyl, 1,1,2,2,3,3,4,4,5,5-decafluorohexyl, 1,1,2,2,3,3,4,4,5,5,6, 6-Dodecafluorohexyl, perfluorohexyl, perfluoropentylmethyl and perfluorohexyl, etc.

A part of the carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkyl group is inserted into a group with an oxygen atom (hereinafter also referred ^{to as the oxygen-containing group of R 2} ), which may be a group formed by inserting an oxygen atom at a single position, or It is a base formed by inserting more than two positions.

In addition, if an oxygen atom is inserted into the carbon-carbon bond, an ether bond is formed. In addition, if an oxygen atom is inserted into the carbon-hydrogen bond, a hydroxyl group is formed. That is, ^{the oxygen-containing group of R 2} can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group of R ^{2 include groups represented by the following formulae.}

[化2]

The content of fluorine atoms in the compound represented by the formula (A-1) may be, for example, 2% by mass or more, preferably 5% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more. In addition, the fluorine atom content in the compound represented by the formula (A-1) may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less. That is, the content of fluorine atoms in the compound represented by the formula (A-1) can be, for example, 2 to 75% by mass, 2 to 70% by mass, 2 to 65% by mass, 5 to 75% by mass, and 5 to 70% by mass. %, 5 to 65% by mass, 15 to 75% by mass, 15 to 70% by mass, 15 to 65% by mass, 30 to 75% by mass, 30 to 70% by mass, or 30 to 65% by mass.

One of the specific examples of the compound represented by the formula (A-1) includes, for example, the compound represented by the formula (A-1-1).

[化3]

In the 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. There are a plurality of R ²¹ which may be the same or different from each other. However, ^{at least one of R 21} is a fluorine atom.

If n is 1 or more, it is preferably 2 or more. In addition, the upper limit of n is not particularly limited. n may be 25 or less, or 20 or less, for example. That is, n may be, for example, 1-25, 1-20, 2-25, or 2-20.

There are a plurality of R ²¹ in formula (A-1-1), but at least one of them is a fluorine atom. In addition, ^{among R 21} , it is preferable that two or more are fluorine atoms, and it is more preferable that three or more are fluorine atoms. R ²¹ may all 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} may be, for example, 4-100%, 4-80%, 4-75%, 8-100%, 8-80%, 8-75% , 12～100%, 12～80% or 12～75%.

In the compound represented by the formula (A-1-1), at least one of the ^{divalent groups (-C(R 21} ) _{2 -) in parentheses marked with n is preferably difluoromethylene (-CF 2} -) ).

Another example of the specific example of the fluorine-containing monomer includes a compound represented by formula (A-2).

[化4]

In the formula (A-2), R ³ represents a hydrogen atom or a methyl group. In addition, 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. A plurality of R ³ may be the same or different from each other.

The fluorinated alkanediyl group may be referred to as a group in which part 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. For example, it may be 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. In addition, the number of carbon atoms of the fluorinated alkanediyl group may be, for example, 20 or less, preferably 17 or less, more preferably 15 or less, more preferably 12 or less, and more preferably 10 or less. That is, the number of carbon atoms of the fluorinated alkanediyl group can be, for example, 1-20, 1-17, 1-15, 1-12, 1-10, 2-20, 2-17, 2-15, 2. -12, 2-10, 3-20, 3-17, 3-15, 3-12, 3-10, 4-20, 4-17, 4-15, 4-12 or 4-10.

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

Specific examples of fluorinated alkanediyl groups include linear or branched fluorinated alkanediyl groups having 1 to 17 carbon atoms (e.g., 2,2,3,3,4,4,5,5,6, 6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediyl), fluorinated cycloalkanediyl with 1 to 17 carbon atoms, etc.

A part of the carbon-carbon bond and carbon-hydrogen bond in the fluorinated alkanediyl group has an oxygen atom inserted (hereinafter also referred ^{to as the oxygen-containing group of R 4} ), which may be a group formed by inserting an oxygen atom at a single position, or It can be a base formed by inserting more than two positions.

In addition, if an oxygen atom is inserted into the carbon-carbon bond, an ether bond is formed. In addition, if an oxygen atom is inserted into the carbon-hydrogen bond, a hydroxyl group is formed. That is, ^{the oxygen-containing group of R 4} can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group of R ^{4 include groups represented by the following formulae.}

[化5]

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

One of the specific examples of the compound represented by the formula (A-2) includes, for example, the compound represented by the formula (A-2-1).

[化6]

In the 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. A plurality of R ³ may be the same or different from each other. There are a plurality of R ⁴¹ which may be the same or different from each other. However, ^{at least one of R 41} is a fluorine atom.

It is sufficient if m is 1 or more, preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more. In addition, the upper limit of m is not particularly limited. For example, m may be 20 or less, preferably 17 or less, more preferably 15 or less, more preferably 12 or less, and more preferably 10 or less. That is, m may be, for example, 1-20, 1-17, 1-15, 1-12, 1-10, 2-20, 2-17, 2-15, 2-12, 2-10, 3～ 20, 3-17, 3-15, 3-12, 3-10, 4-20, 4-17, 4-15, 4-12 or 4-10.

There are a plurality of R ⁴¹ in formula (A-2-1), but at least one of them is a fluorine atom. In addition, ^{among R 41} , it is preferable that two or more are fluorine atoms, and it is more preferable that four or more are fluorine atoms. R ⁴¹ may all 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 ratio 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} can be, for example, 1-100%, 1-95%, 1-90%, 5-100%, 5-95%, 5-90% , 10～100%, 10～95% or 10～90%.

In the compound represented by formula (A-2-1), at least one of the ^{divalent groups (-C(R 41} ) _{2 -) in parentheses marked with m is preferably difluoromethylene (-CF 2} -) ).

Another example of the specific example of the fluorine-containing monomer includes a compound represented by formula (A-3).

[化7]

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

In addition, "R ⁶ represents a single bond" means that Ar ¹ is directly bonded to an oxygen atom.

The fluorinated aryl group of Ar ¹ is preferably a fluorinated phenyl group. The fluorinated phenyl group may 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, or may have five.

The ^{number of carbon atoms of the alkanediyl group of R 6} is not particularly limited, and may be, for example, 1 or more. In addition, the ^{number of carbon atoms of the alkanediyl group of R 6} may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, the ^{number of carbon atoms of the alkanediyl group of R 6} may be, for example, 1-17, 1-15, or 1-12.

Specific examples of alkanediyl groups include linear or branched alkanediyl groups having 1 to 17 carbon atoms (for example, methylene, ethylene, etc.), and cycloalkanediyl groups having 1 to 17 carbon atoms.

The fluorinated alkanediyl group of R ⁶ may be a group in which part 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 of R 6} is not particularly limited, and may be, for example, 1 or more. In addition, the ^{number of carbon atoms of the fluorinated alkanediyl group of R 6} may be, for example, 17 or less, preferably 15 or less, and more preferably 12 or less. That is, the ^{number of carbon atoms of the fluorinated alkanediyl group of R 6} may be, for example, 1-17, 1-15, or 1-12.

The fluorinated alkanediyl group of R ⁶ can desirably use a group containing a difluoromethylene group (-CF ₂ -).

A part of the carbon-carbon bond and carbon-hydrogen bond in an alkanediyl group or a fluorinated alkanediyl group is inserted into a group ^{containing an oxygen atom (hereinafter also referred to as the oxygen-containing group of R 6} ), which can be formed by inserting an oxygen atom into a single position The base of may also be a base formed by inserting two or more positions.

In addition, if an oxygen atom is inserted into the carbon-carbon bond, an ether bond is formed. In addition, if an oxygen atom is inserted into the carbon-hydrogen bond, a hydroxyl group is formed. That is, ^{the oxygen-containing group of R 6} can also be said to contain at least one group selected from the group consisting of an ether bond and a hydroxyl group.

Specific examples of the oxygen-containing group of R ⁶ include, for example, groups _{containing -CH 2} CH _{2 O-.}

The content of fluorine atoms 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. In addition, the fluorine atom content in the compound represented by the formula (A-3) may be, for example, 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less. That is, the content of fluorine atoms in the compound represented by formula (A-3) can be, for example, 3 to 90% by mass, 3 to 80% by mass, 3 to 70% by mass, 7 to 90% by mass, and 7 to 80% by mass. %, 7 to 70% by mass, 15 to 90% by mass, 15 to 80% by mass, or 15 to 70% by mass.

One of the specific examples of the compound represented by the formula (A-3) includes, for example, the compound represented by the formula (A-3-1).

[化8]

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, there are a plurality of R ⁶¹ which may be the same or different from each other. In addition, there are a plurality of R ⁶² which may be the same or different from each other. However, ^{at least one of R 62} is a fluorine atom.

p represents an integer of 0 or more. Here, p being 0 means that the benzene ring is directly bonded to the oxygen atom. p may also be an integer of 1 or more. In addition, the upper limit of p is not particularly limited. For example, p may be 17 or less, preferably 15 or less, and more preferably 12 or less. That is, p may be, for example, 1-17, 1-15, or 1-12.

^{When R 61} is present in the formula (A-3-1) (that is, when p is an integer of 1 or more), R ⁶¹ may be all hydrogen atoms, all fluorine atoms, or part of hydrogen atoms and other parts (Hereinafter, it may also be referred to as another part) is a fluorine atom.

There are a plurality of R ⁶² in formula (A-3-1), and at least one of them is a fluorine atom. In addition, ^{two or more of R 62} may be fluorine atoms, and three or more of R 62 may be fluorine atoms. In addition, all (5) of ^{R 62 may be fluorine atoms.}

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 ratio 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 can be, for example, 5-100%, 5-95%, 5-80%, 10-100%, 10-95%, 10 ～80%, 20～100%, 20～95% or 20～80%.

In an ideal aspect, the fluorine-containing monomer should preferably be 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) At least one of them.

Ideally, in another aspect, the fluorine-containing monomer should be selected from (meth)acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8- Tridecafluorooctyl ester, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol One of the group consisting of (meth)acrylate, (meth)acrylate-1H,1H,5H-octafluoropentyl ester, and (meth)acrylate-1H,1H,2H,2H-tridecafluorooctyl ester At least one.

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

In this embodiment, the monomer component may further contain other monomers (that is, monomers without fluorine atoms) other than the fluorine-containing monomer (hereinafter also referred to as monomer (B)). The monomer (B) can be said to have a carbon-carbon unsaturated double bond and no fluorine atom. The monomer (B) is preferably a monomer having a vinyl group as a carbon-carbon unsaturated double bond, and more preferably a monomer having a (meth)acryloyl group as a carbon-carbon unsaturated double bond.

The ratio of the fluorine-containing monomer in the monomer component is not particularly limited. For example, it may be 0.001% by mass or more, preferably 0.005% by mass or more, and more preferably 0.008% by mass or more. In addition, the ratio of the fluorine-containing monomer in the monomer component may be, for example, 97% by mass or less, preferably 95% by mass or less, and more preferably 93% by mass or less. That is, the ratio of the fluorine-containing monomer in the monomer component may be, for example, 0.001 to 97% by mass, 0.001 to 95% by mass, 0.001 to 93% by mass, 0.005 to 97% by mass, and 0.005 to 95% by mass. , 0.005 to 93% by mass, 0.008 to 97% by mass, 0.008 to 95% by mass, or 0.008 to 93% by mass.

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

The content of fluorine atoms relative to the total amount of monomer components can be, for example, 0.005% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 2% by mass or more, and more preferably 5 mass% or more Better yet. In addition, the content of fluorine atoms based on the total amount of monomer components may be, for example, 75% by mass or less, preferably 70% by mass or less, and more preferably 65% by mass or less. That is, the content of fluorine atoms relative to the total amount of monomer components can be, for example, 0.005 to 75% by mass, 0.005 to 70% by mass, 0.005 to 65% by mass, 0.5 to 75% by mass, 0.5 to 70% by mass, 0.5 to 65% by 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% by mass.

The monomer (B) may be a high-viscosity monomer or a low-viscosity monomer, but at least a part of the monomer (B) is preferably a high-viscosity monomer. The monomer component may contain two or more types of monomers (B). In this case, it may be two or more types of monomers (B), all of which are high-viscosity monomers, or it may be one of two or more types of monomers (B). One part is a high-viscosity monomer and the other part is a low-viscosity monomer.

Among the monomers (B), those that are high-viscosity monomers include, for example, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, and 2,4,5 (meth)acrylic acid. -Tetramethylphenyl ester, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate -3-phenoxypropyl ester (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl o- Phthalic 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 epoxy di(meth)acrylate, ethoxylated o-benzene Base phenol (meth)acrylate, m-phenoxybenzyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentyloxyethyl (meth)acrylate, dicyclopentyl(meth)acrylate Cyclopentenyl ester, dicyclopentenyloxyethyl (meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylation Trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate Base) acrylate, neopentyl erythritol tetra (meth) acrylate, neopentyl erythritol ethoxy tetra (meth) acrylate, dineopentaerythritol penta (meth) acrylate, dineopentaerythritol Hexa(meth)acrylate etc.

Among the monomers (B), those belonging to low-viscosity monomers include, for example, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 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 Esters, isooctyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, etc.

The monomer (B) can be a monofunctional monomer or a multifunctional monomer, but at least a part of the monomer (B) is preferably a monofunctional monomer, if one part is a monofunctional monomer and the other part is a multifunctional mono Better body. That is, the monomer component may contain two or more types of monomers (B), and it is preferable that among the two or more types of monomers (B), one part is a monofunctional monomer and the other part is a multifunctional monomer.

Among the monomers (B), those that are monofunctional monomers include, for example, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, and 2,4,5 (meth)acrylic acid. -Tetramethylphenyl ester, 4-chlorophenyl (meth)acrylate, phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-hydroxy (meth)acrylate -3-phenoxypropyl ester (2-HPA), 2-(meth)acryloyloxyhexahydrophthalic acid, 2-(meth)acryloyloxyethyl-2-hydroxypropyl o- Phthalic 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, dicyclopentyl (meth)acrylate, dicyclopentyl (meth)acrylate Ethyl oxyacetate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, (meth) ) Benzyl 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, and the like.

Among the monomers (B), those belonging to multifunctional monomers include, for example, ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, acrylic Oxylated ethoxylated bisphenol A di(meth)acrylate, bisphenol A epoxy di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane Tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentaerythritol tris(methyl) ) Acrylate, dimethylolpropane tetra (meth) acrylate, neopentyl erythritol tetra (meth) acrylate, neopentyl erythritol ethoxy tetra (meth) acrylate, dineopentaerythritol five (Meth) acrylate, dineopentaerythritol 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.

The photopolymerization initiator may be a compound that can be activated by active light such as visible light and ultraviolet light, and start or promote the polymerization of the monomer components. The photopolymerization initiator may be used alone or in combination of two or more kinds. The photopolymerization initiator is preferably a photoradical polymerization initiator.

及其衍生物； 樟腦醌、7,7-二甲基-2,3-二側氧基雙環[2.2.1]庚烷-1-甲酸、7,7-二甲基-2,3-二側氧基雙環[2.2.1]庚烷-1-羧基-2-溴乙基酯、7,7-二甲基-2,3-二側氧基雙環[2.2.1]庚烷-1-羧基-2-甲基酯、7,7-二甲基-2,3-二側氧基雙環[2.2.1]庚烷-1-甲醯氯等樟腦醌型光聚合起始劑； 2-甲基-1-[4-(甲基硫代)苯基]-2-𠰌啉基丙烷-1-酮、2-苄基-2-二甲基胺基-1-(4-𠰌啉基苯基)-丁酮-1等α-胺基烷基苯基酮型光聚合起始劑； 苯甲醯基二苯基氧化膦、二苯基-2,4,6-三甲基苯甲醯基氧化膦、苯甲醯基二乙氧基氧化膦、2,4,6-三甲基苯甲醯基二甲氧基苯基氧化膦、2,4,6-三甲基苯甲醯基二乙氧基苯基氧化膦、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦等醯基氧化膦型光聚合起始劑； 苯基乙醛酸甲酯； 氧基苯基乙酸-2-[2-側氧基-2-苯基-乙醯氧基-乙氧基]-乙酯； 氧基苯基乙酸-2-[2-羥基-乙氧基]-乙酯；等。The photo-radical polymerization initiator can include: benzophenone and its derivatives; benzil and its derivatives; anthraquinone and its derivatives; benzoin, benzoin methyl ether, benzoin ethyl ether, benzene Azoin propyl ether, benzoin isobutyl ether, benzil dimethyl ketal and other benzoin-type photopolymerization initiators; diethoxyacetophenone, 4-tertiary butyl trichloroacetophenone Acetophenone type photopolymerization initiator; ethyl 2-dimethylaminobenzoate; ethyl p-dimethylaminobenzoate; diphenyl disulfide; 9-oxothio𠮿

And its derivatives; camphorquinone, 7,7-dimethyl-2,3-dioxobicyclo[2.2.1]heptane-1-carboxylic acid, 7,7-dimethyl-2,3-di Pendant oxybicyclo[2.2.1]heptane-1-carboxy-2-bromoethyl ester, 7,7-dimethyl-2,3-dilateral oxybicyclo[2.2.1]heptane-1- Carboxy-2-methyl ester, 7,7-dimethyl-2,3-di-side oxybicyclo[2.2.1]heptane-1-methylchloride and other camphorquinone-type photopolymerization initiators; 2- Methyl-1-[4-(methylthio)phenyl]-2-𠰌line propan-1-one, 2-benzyl-2-dimethylamino-1-(4-𠰌line group) (Phenyl)-butanone-1 and other α-aminoalkyl phenyl ketone type photopolymerization initiators; benzyl diphenyl phosphine oxide, diphenyl-2,4,6-trimethylbenzyl Phosphine oxide, benzyl diethoxy phosphine oxide, 2,4,6-trimethylbenzyl dimethoxyphenyl phosphine oxide, 2,4,6-trimethylbenzyl Phosphine oxide type photopolymerization initiators such as phenyldiethoxyphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenyl phosphine oxide; methyl phenylglyoxylate ; Oxyphenylacetic acid-2-[2-oxo-2-phenyl-acetoxy-ethoxy]-ethyl; oxyphenylacetic acid-2-[2-hydroxy-ethoxy ]-Ethyl; etc.

Regarding the photopolymerization initiator, considering that it can be cured using only visible light of 390 nm or more, it is preferably an oxyphosphine oxide type photopolymerization initiator. In addition, the acylphosphine oxide type photopolymerization initiator may also be said to have an acylphosphine oxide group (-(C=O)-(P=O)<). In addition, considering that it can be cured with light of 395 nm or more and it is easy to obtain a cured body with higher visible light transmittance, diphenyl-2,4,6-trimethylbenzylphosphine oxide is particularly preferred. Examples of diphenyl-2,4,6-trimethylbenzylphosphine oxide include "Irgacure TPO" manufactured by BASF JAPAN.

The content of the photopolymerization initiator is preferably 0.05 parts by mass or more relative to 100 parts by mass of the total amount of monomer components, more preferably 0.5 parts by mass or more, more preferably 2 parts by mass or more, and more preferably 2.5 parts by mass or more. Better. By increasing the content of the photopolymerization initiator, the curing properties of the composition tend to be more improved. The content of the photopolymerization initiator is preferably 12 parts by mass or less with respect to 100 parts by mass of the total amount of monomer components, more preferably 8 parts by mass or less, and even more preferably 6 parts by mass or less. By reducing the content of the photopolymerization initiator, it becomes easier to obtain a hardened body with higher visible light transmittance. That is, the content of the photopolymerization initiator can be, for example, 0.05-12 parts by mass, 0.05-8 parts by mass, 0.05-6 parts by mass, 0.5-12 parts by mass relative to 100 parts by mass of the total amount of monomer components. , 0.5-8 parts by mass, 0.5-6 parts by mass, 2-12 parts by mass, 2-8 parts by mass, 2-6 parts by mass, 2.5-12 parts by mass, 2.5-8 parts by mass, or 2.5-6 parts by mass.

The composition of this embodiment may further contain other components other than the monomer component and the photopolymerization initiator. The composition of this embodiment may further contain, for example, a well-known additive that can be used in the field of sealants for organic EL display elements. Examples of additives include antioxidants, metal deactivators, fillers, stabilizers, neutralizers, lubricants, and antibacterial agents.

The composition of this embodiment can be cured by irradiating at least one of visible light or ultraviolet light. In addition, in this specification, the "curing" of the composition is not limited to hard curing, as long as the monomer components are polymerized to form a polymer. For example, the hardened body of the composition may be a rigid solid (for example, glass-like) or rubber-like.

The energy sources used to irradiate visible light or ultraviolet light include: deuterium lamp, high pressure mercury lamp, ultra-high pressure mercury lamp, low pressure mercury lamp, xenon lamp, xenon mercury mixed lamp, halogen lamp, excimer lamp, indium lamp, thallium lamp, LED lamp , Energy source such as electrodeless discharge lamp.

For the composition of this embodiment, considering that it is not easy to damage the organic EL display element, it is better to use light with a wavelength of 380nm or more to harden, and it is better to use light with a wavelength of 395nm or more to harden, and to use light with a wavelength of 395nm. It is best to harden. The wavelength of the irradiated light should be less than 500nm in consideration of avoiding the temperature rise of the irradiated part caused by infrared light and the possibility of damage to the organic EL display element. The energy source should preferably be a single-wavelength LED lamp.

So that when the composition of the irradiation dose should be hardened to 100 ~ 8000mJ / cm ^2, to 300 ~ 2000mJ / cm ² more preferably. By controlling the irradiation dose to 100mJ/cm ² or more, the composition can be sufficiently hardened and high bonding strength can be easily obtained. In addition, by controlling the irradiation amount to 8000 mJ/cm ² or less, the composition can be cured without damaging the organic EL display device. That is, the irradiation amount when the composition is cured can be, for example, 100 to 8000 mJ/cm ² , 300 to 8000 mJ/cm ² , 100 to 2000 mJ/cm ² , and 300 to 2000 mJ/cm ² .

The cured body of the composition of this embodiment is preferably excellent in transparency. Specifically, the spectral transmittance of the cured body in the ultraviolet-visible light region of 360nm or more and 800nm or less, per unit thickness of 10μm, preferably 95% or more, more preferably 97% or more, and even more preferably 99% or more . If the spectral transmittance is 95% or more, it is easy to obtain an organic EL display device excellent in brightness and contrast.

The cured body of the composition of this embodiment is based on JIS Z 0208:1976, exposed to an environment of 85°C and 85%RH for 24 hours and measured the value of the moisture permeability of 100μm thick, preferably 500g/m ² or less, which is It is more preferably 400 g/m ² or less, and even more preferably 350 g/m ^{2 or less.} If the moisture permeability is low, the occurrence of black spots caused by moisture reaching the organic light-emitting material layer can be suppressed more significantly.

The method of using the composition of this embodiment is not particularly limited. The composition of this embodiment can be preferably used as a sealing agent for organic EL display elements. Specifically, for example, by applying the composition to an object (for example, an organic EL display device) and hardening the composition on the object, a sealing material composed of a hardened body of the composition can be formed.

In addition, the composition may be cured into a predetermined shape (for example, a film shape, a sheet shape, etc.) to form a sealing material having a predetermined shape. At this time, for example, by disposing the sealing material on the organic EL display element, the organic EL display element can be sealed.

Since the composition of this embodiment has excellent surface flatness and straightness, even when it is applied to the inkjet method, an organic film with less surface irregularities can be accurately formed in a predetermined range. Therefore, the composition of this embodiment can be ideally used as a coating liquid for forming an organic film (preferably an organic film as a sealing material for an organic EL display element) by an inkjet method.

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

The top emission type organic EL display device includes an organic EL display element, a sealing layer sealing the organic EL display element, and a sealing substrate provided on the sealing layer.

The organic EL display element 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.

Examples of substrates of organic EL display elements include glass substrates, silicon substrates, and plastic substrates. Among them, a glass substrate and a plastic substrate are preferable, and a glass substrate is more preferable.

The plastic used for the plastic substrate can include: polyimide, polyetherimide, polyethylene terephthalate, polyethylene naphthalate, polyoxadiazole, aromatic polyamide, polyphenylene Bisimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, poly(p-styrene, polymethyl methacrylate, polystyrene, polycarbonate, polycyclic olefin, polyacrylic acid, etc.). Among them, considering low water permeability, low oxygen permeability, and excellent heat resistance, it is preferable to use polyimide, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate. One or more of the group consisting of ester, polyoxadiazole, aromatic polyamide, polybenzimidazole, polybenzobisthiazole, polybenzoxazole, polythiazole, and poly(p-styrene), considering ultraviolet light or The viewpoint of high permeability of energy rays such as visible light is one or more of the group consisting of polyimide, polyetherimide, polyethylene terephthalate, and polyethylene naphthalate Better.

Generally speaking, the anode uses a conductive metal oxide film, a semi-transparent metal film, etc. with a relatively large work function (a work function greater than 4.0 eV is ideal). Examples of anode materials include metal oxides such as indium tin oxide (ITO) and tin oxide; metals such as gold (Au), platinum (Pt), silver (Ag), and copper (Cu) Or an alloy containing at least one of them; organic transparent conductive films such as polyaniline or its derivatives, polythiophene or its derivatives, etc. If necessary, the anode can be formed with two or more layers. 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 is also considered). The film thickness of the anode is preferably 10 nm to 10 μm, more preferably 20 nm to 1 μm, and most preferably 50 nm to 500 nm. That is, the film thickness of the anode may be, 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 to 500 nm. 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 substance. The light-emitting layer contains a light-emitting material. Examples of luminescent materials include organic substances (low-molecular compounds or high-molecular compounds) that emit fluorescence or phosphorescence. The light-emitting layer may further contain dopant materials. Examples of the organic matter include dye-based materials, metal complex-based materials, and polymer materials. The dopant material is doped in the organic substance in order to improve the luminous efficiency of the organic substance, change the luminous wavelength, and so on. The thickness of the light-emitting layer composed of these organic substances and dopants doped as needed is usually 2 to 200 nm.

Examples of pigment-based materials include: methylcyclopentamine derivatives, tetraphenylbutadiene derivative compounds, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, and two Styrene benzene derivatives, stilbene arylene derivatives, pyrrole derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumaridine (trifumanyl amine) derivatives, diazole dimer, pyrazoline dimer, etc.

Metal complex-based materials include: iridium complexes, platinum complexes, and other metal complexes having luminescence derived from triplet excited states; aluminum quinolinol complexes, benzoquinolyl beryllium complexes Metal complexes such as benzoxazole zinc complexes, benzothiazole zinc complexes, azomethylzinc complexes, porphyrin zinc complexes, europium complexes, etc. Examples of metal complexes include rare earth metals such as turbidium (Tb), europium (Eu), and dysprosium (Dy) in the center metal; aluminum (Al), zinc (Zn), beryllium (Be), etc., in the ligand Metal complexes of oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, etc. Among them, a metal complex having aluminum (Al) in the center metal and a quinoline structure in the ligand is preferable. Among the metal complexes in which the central metal has aluminum (Al), and the ligand has a quinoline structure, etc., ginseng (8-hydroxyquinoline) aluminum is preferable.

Examples of polymer materials include: poly(p-styrene derivatives), polythiophene derivatives, poly(p-phenylene) derivatives, polysilane derivatives, polyacetylene derivatives, polypyridine derivatives, polyvinyl carbazole derivatives, and the above-mentioned pigments. Bulk or metal complex-based light-emitting materials are formed by polymerizing, etc.

Among the above-mentioned luminescent materials, materials that emit blue light include: stilbene arylene derivatives, oxadiazole derivatives, polyvinylcarbazole derivatives, poly(p-phenylene) derivatives, polypyridine derivatives, and these的polymers, etc. Among them, polymer materials are suitable. Among the polymer materials, one or more of the group consisting of polyvinylcarbazole derivatives, polyparaphenylene derivatives, and polypyridine derivatives are preferable.

Examples of materials that emit green light include quinacridone derivatives, coumarin derivatives, poly-p-styrene derivatives, polysulfonate derivatives, and polymers thereof. Among them, polymer materials are suitable. Among the polymer materials, preferably one or more of the group consisting of poly(p-styrene derivatives) and poly(phenylene derivatives).

Examples of materials that emit red light include coumarin derivatives, thiophene ring compounds, polyp-styrene derivatives, polythiophene derivatives, polysulfide derivatives, and polymers thereof. Among them, polymer materials are suitable. Among the polymer materials, one or more of the group consisting of poly(p-styrene derivatives, polythiophene derivatives, and polythiophene derivatives) is preferable.

Examples of doping materials include: perylene derivatives, coumarin derivatives, rubrene derivatives, quinacridone derivatives, squarylium derivatives, porphyrin derivatives, and styrene-based pigments , Tetracene derivatives, pyrazolone derivatives, decacyclene, phenoxazone, etc.

In addition to providing the light-emitting layer, the organic EL layer may also be appropriately provided: a layer provided between the light-emitting layer and the anode, and a layer provided between the light-emitting layer and the cathode. First, the layers provided between the light-emitting layer and the anode include: a hole injection layer that improves the efficiency of hole injection from the anode, and a hole transport layer that transfers holes injected from the anode or the hole injection layer to the light-emitting layer. Wait. The layer provided between the light-emitting layer and the cathode includes an electron injection layer that improves the efficiency of electron injection from the cathode, and an electron transport layer that transmits electrons injected from the cathode or the electron injection layer to the light-emitting layer.

Examples of materials for forming the hole injection layer include: phenylamine series such as 4',4''-ginseng(2-naphthyl(phenyl)amino)triphenylamine; starburst type amine series; phthalein Cyanine series; oxides such as vanadium oxide, molybdenum oxide, ruthenium oxide, and aluminum oxide; amorphous carbon, polyaniline, polythiophene derivatives, etc.

The material constituting the hole transport layer can include: polyvinylcarbazole or its derivatives, polysilane or its derivatives, polysiloxane derivatives with aromatic amines in the side chain 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 Derivatives, poly(p-styrene) or its derivatives, poly(2,5-thiopheneethylene) or its derivatives, etc.

When these hole injection layers or hole transport layers have the function of preventing the transmission of electrons, they are sometimes called electron blocking layers.

The materials constituting the electron transport layer include: oxadiazole derivatives, anthraquinone dimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyananthraquinone Methane or its derivatives, quinone derivatives, diphenyl dicyanoethylene or its derivatives, diphenoquinone derivatives, 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoline Or its derivatives, polychosene or its derivatives, etc. Examples of derivatives include metal complexes and the like. Among them, 8-hydroxyquinoline or a derivative thereof is preferable. Among 8-quinolinols or derivatives thereof, considering that they can also be used as a fluorescent or phosphorescent organic substance contained in the light-emitting layer, ginseng (8-quinolinol) aluminum is preferable.

According to the type of light-emitting layer, the electron injection layer may include: an electron injection layer composed of a single-layer structure of calcium (Ca) layer, or a metal from the IA and IIA groups of the periodic table, and the work function is 1.5～3.0eV The metal and the metal oxides, halides and carbonates of the group formed by one or more layers of a single layer structure, or composed of periodic table IA and IIA metals, and the work function It is an electron injection layer or the like composed of a layer formed by a layer formed of a metal of 1.5 to 3.0 eV and one or more of the group consisting of oxides, halides, and carbonates of the metal and a Ca layer. The metals of Group IA of the Periodic Table of Elements with a work function of 1.5 to 3.0 eV or their oxides, halides, and carbonates include lithium (Li), lithium fluoride, sodium oxide, lithium oxide, lithium carbonate, and the like. Metals of Group IIA of the Periodic Table of Elements with a work function of 1.5 to 3.0 eV or their oxides, halides, and carbonates include: strontium (Sr), magnesium oxide, magnesium fluoride, strontium fluoride, barium fluoride, strontium oxide , Magnesium carbonate, etc.

When these electron transport layers or electron injection layers have the function of preventing the transmission of holes, these electron transport layers and electron injection layers are sometimes referred to as hole blocking layers.

The cathode is preferably a transparent or semi-transparent material that has a small work function (a work function of less than 4.0 eV is ideal) and is easy to inject electrons into the light-emitting layer. Cathode materials include: 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) , Tb, Ytterbium (Yb) and other metals; or alloys composed of two or more of the above metals, or one or more of them and gold (Au), silver (Ag), platinum (Pt), An alloy composed of one or more of copper (Cu), chromium (Cr), manganese (Mn), titanium (Ti), cobalt (Co), nickel (Ni), tungsten (W), and tin (Sn); or graphite Or graphite intercalation compound; or ITO, tin oxide and other metal oxides.

The cathode can also be arranged in a stacked structure of two or more layers. The laminated structure of two or more layers includes the laminated structure of the above-mentioned metals, metal oxides, fluorides, their alloys, and metals such as Al, Ag, and Cr. The film thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability. The film thickness of the cathode is preferably 10 nm to 10 μm, more preferably 15 nm to 1 μm, and most preferably 20 nm to 500 nm. That is, the film thickness of the cathode may be, 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. The manufacturing method of the cathode can include: vacuum evaporation method, sputtering method, laminating method in which metal thin films are thermally compressed, and the like.

These layers provided between the light-emitting layer and the anode and between the light-emitting layer and the cathode can be appropriately selected in accordance with the performance required of the organic EL display device to be manufactured. For example, the structure of the organic EL display element used in this embodiment may have any of the following layer structures (i) to (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, "/" means that each layer is adjacent and stacked. The following is the same.)

The sealing layer is used to prevent gas such as water vapor and oxygen from contacting the organic EL display element, and is provided to seal the organic EL display element with a layer having high barrier properties to the gas. The sealing layer is formed alternately from the bottom of an inorganic film and an organic film. The inorganic/organic laminate can also be formed by repeating 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 gases such as water vapor and oxygen in the environment where 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 films, SiO films, SiON films, Al ₂ O ₃ films, and AlN films, or 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 narrower area than the area where the inorganic film is formed. This is because if the organic film is formed to be the same as or wider than the formation area of the inorganic film, the exposed area of the organic film will deteriorate. However, the uppermost organic film formed on the uppermost layer of the entire sealing layer is formed in an area substantially the same as the formation area of the inorganic film. Moreover, the top surface of the sealing layer is formed in a flattened manner. The organic film may be a film formed using the composition of the present embodiment described above (that is, a film containing a cured body of the composition).

As described above, the composition of this embodiment is suitable for inkjet coating, and has excellent ejection properties by inkjet and flatness after inkjet coating. If the coating method, which is the inkjet method, is used, the organic film can be formed uniformly at a high speed.

If the sealing layer is counted as one group of inorganic/organic laminates, it is preferably 1 to 5 groups. This is because when the inorganic/organic laminate has 6 groups or more, the sealing effect on the organic EL display element is approximately the same as that of the 5 groups. The thickness of the inorganic film of the inorganic/organic laminate is preferably 50 nm to 1 μm. The thickness of the organic film of the inorganic/organic laminate is preferably 1-15 μm, more preferably 3-10 μm. If the thickness of the organic film is 1 μm or more, it can completely cover the particles generated during element formation and can be coated on the inorganic film with good flatness. If the thickness of the organic film is 15 μm or less, moisture will not penetrate from the side of the organic film, and the reliability of the organic EL display element will be improved. The thickness of the organic film of the inorganic/organic laminate can be, for example, 1 to 15 μm, 1 to 10 μm, 3 to 15 μm, or 3 to 10 μm.

The sealing substrate is formed in close contact to cover the entire top surface of the uppermost organic film of the sealing layer. Examples of the sealing substrate include the aforementioned substrates. Among them, a substrate that is transparent to visible light is suitable. Among the substrates that are transparent to visible light (transparent sealing substrates), preferably one or more of the group consisting of a glass substrate and a plastic substrate, and a glass substrate is more preferable.

The thickness of the transparent sealing 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 arranging the transparent sealing substrate on the upper layer of the sealing layer, the degradation that occurs when the surface of the uppermost organic film is exposed to gas can be suppressed, and the barrier properties of the organic EL display device can be improved. The thickness of the transparent sealing substrate may be, 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.

Next, a method of manufacturing an organic EL display device having such a configuration will be described. First, a conventional method is used to form an anode that has been patterned into a predetermined shape, an organic EL layer including a light-emitting layer, and a cathode on the first substrate in order, and an organic EL display element is formed. For example, when an organic EL display device is used as a dot matrix display device, a bank is formed in order to partition the light-emitting area into a matrix, and an organic EL layer including a light-emitting layer is formed in the area surrounded by the bank.

Then, on the substrate on which the organic EL display element is formed, a film forming method such as PVD (Physical Vapor Deposition) method such as sputtering method, CVD method such as plasma CVD (Chemical Vapor Deposition) method, etc. is used to form a first film having a predetermined thickness. Inorganic membrane. Thereafter, a coating film forming method such as a solution coating method and a spray coating method, or a flash deposition method, an inkjet method, or the like is used to adhere the composition (sealant) of this embodiment to the first inorganic film. Among them, the inkjet method is preferable from the viewpoint of productivity. Thereafter, by irradiating energy rays such as ultraviolet rays and visible rays, the sealant is hardened and the first organic film is formed. Through the above steps, a set of inorganic/organic laminates are formed. The curing rate of the sealant is not particularly limited as long as the effect of the present embodiment can be exhibited. For example, it can be set to 90% or more, preferably 95% or more, as a value obtained in accordance with the measurement method described later.

The steps of forming the inorganic/organic laminate as shown above are repeated only a predetermined number of times. However, regarding the last group, that is, the uppermost inorganic/organic laminate, the top surface can be flattened, and the sealant can be adhered to by the coating method, flash evaporation method, inkjet method, etc. The top surface of the inorganic membrane.

Then, the transparent sealing substrate is bonded to the surface of the substrate to which the sealant is adhered. Position alignment during lamination. Thereafter, by irradiating energy rays from the side of the transparent sealing substrate, the sealant of the present embodiment, which is most present between the upper inorganic film and the transparent sealing substrate, is cured. Thereby, the sealant is hardened and the uppermost organic film is formed, and at the same time, the uppermost organic film and the transparent sealing substrate are bonded. As above, the manufacturing method of the organic EL display device ends.

After the sealant is attached to the inorganic film, it may be partially irradiated with energy rays to polymerize it. By doing so, when the transparent sealing substrate is loaded, the shape of the uppermost organic film can be prevented from collapsing. Regarding the thickness of the inorganic film and the organic film, each inorganic/organic laminate may be the same, and each inorganic/organic laminate may be different.

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

The above has described the ideal embodiment of the present invention, but the present invention is not limited to the above-mentioned embodiment. [Example]

Hereinafter, the present invention will be explained in more detail using examples, but the present invention is not limited to the examples.

The details of the components used in Examples and Comparative Examples are as follows. In addition, the viscosity of the monomer component shows a value measured with an E-type viscometer at 25°C. ＜Fluorinated monomers＞ ･「13F」 Produced by Osaka Organic Chemical Industry Co., Ltd., brand name "Viscoat 13F" Compound name: Acrylic acid-3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester Viscosity: 4mPa･s ･「LINC-162A」 Produced by Kyoeisha Chemical Co., Ltd., trade name "LINC-162A" Compound name: 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decane diacrylate Viscosity: 32mPa･s

＜Monomer (B)＞ ･「A-LEN-10」 Produced by Shinnakamura Chemical Industry Co., Ltd., trade name "NK ESTER A-LEN-10" Compound name: ethoxylated o-phenylphenol acrylate Viscosity: 150mPa･s ･「DCPA」 Produced by Shinnakamura Chemical Industry Co., Ltd., brand name "NK ESTER A-DCP" Compound name: Tricyclodecane dimethanol diacrylate Viscosity: 120mPa･s ･「BPE200」 Produced by Shinnakamura Chemical Industry Co., Ltd., brand name "NK ESTER BPE-200" Compound name: ethoxylated bisphenol A dimethacrylate Viscosity: 600mPa･s ･「SR262」 Manufactured by ARKEMA, product name "SR262" Compound name: 1,12-dodecanediol dimethacrylate Viscosity: 12mPa･s

＜Photopolymerization initiator＞ ･「TPO」 Manufactured by iGM Resins, trade name "Omnirad TPO" Compound name: Diphenyl-2,4,6-trimethylbenzyl phosphine oxide

(Example 1) Mix 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 5 parts by mass of "DCPA", 89 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Prepare the composition. That is, in the monomer components, the proportion of fluorine-containing monomers is set to 1% by mass, the proportion of high-viscosity monomers is set to 10% by mass, and the proportion of bifunctional monomers is set to 95% by mass. The viscosity (value measured with an E-type viscometer at 25°C) of the obtained composition was 13 mPa·s.

(Example 2) Mix 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Prepare the composition. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 1% by mass, the ratio of the high-viscosity monomer is set to 23% by mass, and the ratio of the bifunctional monomer is set to 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) Mix 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 50 parts by mass of "DCPA", 44 parts by mass of "SR262", and 3.5 parts by mass of "TPO". Prepare the composition. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 1% by mass, the ratio of the high-viscosity monomer is set to 55% by mass, and the ratio of the bifunctional monomer is set 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) Mix 0.01 parts by mass of "LINC-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". Prepare the composition. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 0.01% by mass, the ratio of the high-viscosity monomer is set to 23% by mass, and the ratio of the bifunctional monomer is set to 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 parts by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 5 parts by mass of "DCPA", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, in the monomer components, the proportion of fluorine-containing monomers is set to 90% by mass, the proportion of high-viscosity monomers is set to 10% by mass, and the proportion of bifunctional monomers is set to 95% by mass. The viscosity of the obtained composition (value measured with an E-type viscometer at 25°C) was 35 mPa·s.

(Example 6) Combine 1 part by mass of "LINC-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 Parts of "TPO" are mixed to prepare a composition. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 1% by mass, the ratio of the high-viscosity monomer is set to 23% by mass, and the ratio of the bifunctional monomer is set to 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) Mix 1 part by mass of "13F", 5 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 76 parts by mass of "SR262", and 3.5 parts by mass of "TPO" to prepare the composition Things. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 1% by mass, the ratio of the high-viscosity monomer is set to 23% by mass, and the ratio of the bifunctional monomer is set to 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 part by mass of "LINC-162A", 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 components, the proportion of the fluorine-containing monomer is set to 1% by mass, the proportion of the high-viscosity monomer is set to 0% by mass, and the proportion of the bifunctional monomer is set to 100% by mass. The viscosity of the obtained composition (value measured with an E-type viscometer at 25°C) was 12 mPa·s.

(Comparative example 2) 1 part by mass of "LINC-162A", 5 parts by mass of "A-LEN-10", 94 parts by mass of "DCPA", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, in the monomer components, the ratio of the fluorine-containing monomer is set to 1% by mass, the ratio of the high-viscosity monomer is set to 99% by mass, and the ratio of the bifunctional monomer is set to 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 parts by mass of "A-LEN-10", 18 parts by mass of "DCPA", 77 parts by mass of "SR262", and 3.5 parts by mass of "TPO" were mixed to prepare a composition. That is, in the monomer components, the proportion of the fluorine-containing monomer is set to 0% by mass, the proportion of the high-viscosity monomer is set to 23% by mass, and the proportion of the bifunctional monomer is set to 95% by 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 methods. The results are 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 24mm) at a temperature of 25°C and a rotation speed of 100rpm. ＜Surface tension＞ The surface tension of the composition was measured by a pendant drop method using a contact angle meter (DM500 manufactured by Kyowa Interface Science Co., Ltd.) under an environment of 23°C.

<Evaluation of surface flatness> On a 70mm×70mm×0.7mmt base material (alkali-free glass (Eagle XG manufactured by Corning)), a space of 10μm between the front, back, left and right is separated, and a size of 25μm×25μm×3μmt is prepared by etching. Groove. Then, on the substrate provided with the groove, a 200nm SiN film is formed by the plasma CVD method. Then, using an inkjet ejection device (MID500B manufactured by Musashi Engineering Co., Ltd., solvent-based head "MID HEAD"), the composition was pattern-coated so as to be 15 mm×15 mm×8 μmt. In addition, the substrate was cleaned with acetone and isopropanol before the pattern coating, and then cleaned with a UV ozone cleaning device UV-208 manufactured by Technovision for 5 minutes. After pattern coating, place it in a nitrogen environment at a temperature of 23°C and a relative humidity of 50% for 4 minutes. Under the nitrogen environment, use an LED lamp (UV-LED LIGHT SOURCE H- manufactured by HOYA) that emits light with a wavelength of 395 nm. 4MLH200-V1), under the condition that the cumulative light intensity of light with a wavelength of 395nm becomes 1,500mJ/cm ² , the composition is photocured. Then, the thickness of the cured film was measured in a direction perpendicular to the direction of movement of the nozzle using a stylus type shape measuring device (DektakXT manufactured by BRUKER). The difference between the maximum thickness and the minimum thickness in the plane after removing 0.2 mm from the end of the cured film is the evaluation result of the surface flatness.

<Evaluation of straightness> On a 70 mm×70 mm×0.7 mmt substrate (alkali-free glass (Eagle XG manufactured by Corning)), a 200 nm SiN film was formed by a plasma CVD method. Then, using an inkjet ejection device (MID500B manufactured by Musashi Engineering Co., Ltd., solvent-based head "MID HEAD"), the composition was pattern-coated on a predetermined area so as to be 15 mm×15 mm×8 μmt. After pattern coating, place it in a nitrogen environment at a temperature of 23°C and a relative humidity of 50% for 4 minutes. Under the nitrogen environment, use an LED lamp (UV-LED LIGHT SOURCE H- manufactured by HOYA) that emits light with a wavelength of 395 nm. 4MLH200-V1), under the condition that the cumulative light intensity of light with a wavelength of 395nm becomes 1,500mJ/cm ² , the composition is photocured. Then, with respect to the length of the hardened body that exceeds the specified area, a total of 60 places are measured with an optical microscope at 15 places on each side, and the maximum value is the value of straightness.

＜Evaluation of moisture permeability＞ A sheet-shaped hardened body with a thickness of 0.1 mm was prepared using the above-mentioned light hardening conditions. According to JIS Z0208:1976 "Test Method for Moisture Permeability of Moisture-proof Packaging Materials (Cup Method)", calcium chloride (anhydrous) is used as a moisture absorbent and exposed to conditions of 85°C and 85% relative humidity for 24 hours. The moisture permeability of a hardened body with a thickness of 100μm.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Surface flatness (nm) 140 110 380 300 45 80 115 Straightness (μm) 195 140 50 135 240 100 150 Water permeability (g/m ² ) 295 260 220 260 200 265 275

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Surface flatness (nm) 100 - 500 Straightness (μm) 450 - 145 Water permeability (g/m ² ) 305 210 260

As shown in Table 1, the composition of the examples can achieve both excellent surface flatness and straightness. In addition, the moisture permeability of the cured body formed from the composition of the example was sufficiently low, and it was confirmed that it is effective as a sealing material for an organic EL display element.

In addition, as shown in Table 2, in Comparative Example 1, the coating liquid tends to snake around during inkjet coating, which is a result of poor straightness. In addition, Comparative Example 3 was a result of poor surface flatness. In addition, the composition of Comparative Example 2 had a high viscosity and was difficult to eject from an inkjet nozzle, and the surface flatness and straightness could not be evaluated.

Claims (11)

A composition comprising: Monomer components, containing fluorine-containing monomers with fluorine atoms and carbon-carbon unsaturated double bonds, and Photopolymerization initiator; At least a part of the monomer component is a high-viscosity monomer with a viscosity of 50 mPa･s or more measured by an E-type viscometer at 25°C, The viscosity of the composition measured with an E-type viscometer at 25°C is 3mPa･s or more and 50mPa･s or less. The composition of claim 1, wherein 5-65% by mass of the monomer component is the high-viscosity monomer. The composition of claim 1 or 2, wherein at least a part of the monomer component is a multifunctional 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 multifunctional 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 1 carbon-carbon unsaturated double bond. The composition of claim 5, wherein 10-60% by mass of the high-viscosity monomer is the monofunctional monomer. The composition of any one of claims 1 to 6 is a sealant for organic electroluminescence display elements. A hardened body formed by hardening the composition according to any one of claims 1 to 7. A sealing material for an organic electroluminescence display element, which contains the hardened body as claimed in claim 8. A sealing material for an organic electroluminescence display element, comprising a laminate formed by laminating an inorganic film and an organic film, The organic film contains the hardened body as in Claim 8. An organic electroluminescence display device, comprising: Organic electroluminescence display element, and Such as claim 9 or 10 of the sealing material for organic electroluminescence display elements.