CN106062121B

CN106062121B - Sealing material and its solidfied material

Info

Publication number: CN106062121B
Application number: CN201580011222.6A
Authority: CN
Inventors: 冈部润; 山本佑五; 富田裕介
Original assignee: Mitsui Chemical Industry Co Ltd
Current assignee: Mitsui Chemical Industry Co Ltd
Priority date: 2014-05-02
Filing date: 2015-04-27
Publication date: 2018-03-13
Anticipated expiration: 2035-04-27
Also published as: JPWO2015166657A1; WO2015166657A1; KR101864976B1; TW201546160A; KR20160111434A; JP5872129B1; TWI651358B; CN106062121A

Abstract

The problem of the present invention, which is to provide one kind, can form that moisture permeability is low, and the sealing material of the sealant of the moderately low sealant of modulus of elasticity, thickness of thin.In order to solve above-mentioned problem, the present application provides a kind of sealing material, and it is included：Polymerizable monomer (B), it has the functional group of at least one free redical polymerization in each molecule, and molecular weight is more than 50 and less than 1000, is liquid at 23 DEG C；Anhydride ester derivs (C), it includes at least one composition five-membered ring or the anhydride group of hexatomic ring and the functional group of free redical polymerization in each molecule；And radical polymerization initiator (D), it includes at least one party of hot radical polymerization initiator and optical free radical polymerization initiator.

Description

Sealing material and its solidfied material

Technical field

The present invention relates to a kind of sealing material and its solidfied material.

Background technology

Organic EL (Electro-Luminescence, electroluminescent) elements are used for always because consumption electric power is few In display or lighting device etc..Organic EL element because of the moisture in air, oxygen due to easily deteriorating, therefore with various close Envelope component is sealed and used.

Organic el device for example can be comprising substrate, the organic EL element being configured on the substrate and paired with substrate Hermetic sealing substrate structure.As an example of the method for sealing the organic EL element of such structure, can enumerate： Sealing material is coated between hermetic sealing substrate and substrate and between organic EL element and hermetic sealing substrate, and the method (face for solidifying it Sealing Method).

Also, in order that the moisture permeability of the sealant of the solidfied material comprising sealing material reduces, it have studied and add in sealing material Add hygroscopic fillers.Specifically, it is proposed that the sealing material (1~patent document of patent document 3) comprising calcium oxide particle；Or bag Sealing material (patent document 4) of the particle containing porous silica etc..

In addition, as moisture agent for capturing, it is also known that organo-metallic compound, it is also proposed that comprising its hyaline membrane etc. (specially Sharp 5~patent document of document 7).And, it is also proposed that organo-metallic compound and powdered inorganic oxide are caught as moisture Catch agent and be added in hot-melt type member etc. (patent document 8).

On the other hand, as two functional monomers with acrylic resin and epoxy resin reaction, it is known in intramolecular The compound (non-patent literature 1) of functional group and anhydride group comprising free redical polymerization.In addition, in the past it is also known that solidifying Property resin manufacture composition in addition in an intramolecular there is the compound of anhydride group and acidic group (patent document 9).

Prior art literature

Patent document

Patent document 1：No. 2010/084939 publication of International Publication No.

Patent document 2：Japanese Unexamined Patent Publication 2005-122910 publications

Patent document 3：Japanese Unexamined Patent Publication 2007-184279 publications

Patent document 4：Japanese Unexamined Patent Publication 2007-284472 publications

Patent document 5：Japanese Unexamined Patent Publication 2005-298598 publications

Patent document 6：Japanese Unexamined Patent Publication 2011-026521 publications

Patent document 7：Japanese Unexamined Patent Publication 2012-006991 publications

Patent document 8：No. 2007/123039 publication of International Publication No.

Patent document 9：Japanese Unexamined Patent Application Publication 2010-523787 publications

Non-patent literature

Non-patent literature 1：A Reworkable Photothermal Dual-curing System (Chem.Lett.2013,42,1056-1058) (can reprocess the double cure systems of photo-thermal (Chemistry Letters, 2013,42,1056- 1058))

The content of the invention

Problems to be solved by the invention

As 1~patent document of patent document 8, in order that the moisture permeability of sealant reduces, add and inhale in sealant Moist filler, organo-metallic compound etc. are at first sight regarded as effective.However, it with the addition of hygroscopic fillers, You Jijin When belonging to compound, the transparency of the solidfied material of sealing material is damaged sometimes, or the viscosity of sealing material uprises, moistening diffusion during coating Property reduce etc., the application as encapsulant is restricted.In addition, according to the purposes of various equipment, sealing is sometimes required that The filming of layer, but conventional sealing material is difficult to thinly be coated with, it is also difficult to and reply is such to be required.

In addition, being investigated the crosslink density for improving resin, the moisture permeability of sealant is reduced.But if improve resin Crosslink density, then contraction of the sealing material in solidification become big.There are the following problems for its result：Include the solidification containing the sealing material Substrate, the hermetic sealing substrate of the device of the sealant of thing, easily produce strain.In addition, there is a problem in that：Due to sealant Modulus of elasticity improve, therefore sealant can not absorb from outside ess-strain, can not fully protect by sealer (such as Organic EL element).

The present invention is in view of situation as described above forms.That is, the present invention, which provides one kind, can form that moisture permeability is low, can also tackle The formation of thin sealant and the sealing material of the moderately low sealant of modulus of elasticity.

For solving the method for problem

That is, the first invention of the invention is on sealing material as shown below, flap seal material as obtained by it.

[1] a kind of sealing material, it is included：Polymerizable monomer (B), it has at least one free redical in each molecule The functional group of polymerization, and molecular weight is more than 50 and less than 1000, is liquid at 23 DEG C；Anhydride ester derivs (C), it is each At least one composition five-membered ring or the anhydride group of hexatomic ring and the functional group of free redical polymerization are included in molecule；And from By base polymerization initiator (D), at least one party comprising hot radical polymerization initiator and optical free radical polymerization initiator.

[2] sealing material as described in [1], it is further included：Olefin polymer (A) containing polymerizable functional group, It has the functional group of at least one free redical polymerization in each molecule, and number-average molecular weight is more than 5000 and 70000 Below.

[3] sealing material as described in [1] or [2], its viscosity determined by E types viscosimeter under 25 DEG C, 1.0rpm are More than 5mPas and below 20000mPas.

[4] sealing material as any one of [1] to [3], wherein, the polymerizable monomer (B) and the acid anhydrides spread out The functional group of the free redical polymerization possessed by biological (C), separately for selected from by (methyl) acryloyl group, ethene The functional group of one or more of the group that base, pi-allyl, vinyl ether group are formed.

[5] sealing material as any one of [2] to [4], wherein, the olefin-based containing polymerizable functional group is gathered The functional group of the free redical polymerization possessed by compound (A), for selected from by (methyl) acryloyl group, vinyl, pi-allyl, The functional group of one or more of the group that vinyl ether group is formed.

[6] sealing material as any one of [1] to [5], wherein, the anhydride ester derivs (C) are in each molecule In have at least one free redical polymerization functional group hexahydrophthalic anhydride derivative (C').

[7] a kind of flap seal material, it is obtained as the sealing material any one of [1] to [6] as described above.

The second invention of the present invention is the solidfied material on sealing material as shown below.

[8] a kind of solidfied material of sealing material, the sealing material are the sealing material any one of [1] to [6] as described above.

[9] a kind of solidfied material of sealing material, the sealing material are sealing material as any one of [2] to [6], its bullet Property modulus is more than 0.1MPa and below 100MPa.

[10] a kind of solidfied material of sealing material, the sealing material are the sealing material as described in [8], and it is 400nm in wavelength When directional light light transmittance be more than 90%.

[11] a kind of solidfied material of sealing material, the sealing material are the sealing material as described in [9], and it is 400nm in wavelength When directional light light transmittance be more than 90%.

[12] a kind of sealing material, it is included：Olefin polymer (A) containing polymerizable functional group, it is in each molecule In have at least one free redical polymerization functional group, and number-average molecular weight be more than 5000 and less than 70000；Hexahydro neighbour's benzene Dicarboxylic acid anhydride derivative (C'), it has the functional group of at least one free redical polymerization in each molecule；And free radical Polymerization initiator (D), it includes at least one party of hot radical polymerization initiator and optical free radical polymerization initiator.

Invention effect

According to the sealing material of the present invention, the solidfied material that moisture permeability is low and modulus of elasticity is moderately low can be obtained.Further, since The viscosity of sealing material can be reduced, therefore also the solidfied material (sealant) of sealing material can be subjected to filming.

Brief description of the drawings

Figure 1A~Fig. 1 C are the schematic diagrames of the production order for the test sample for representing the solidfied material moisture permeability based on Ca methods.

Fig. 2A is the summary section for a form for representing organic el device, and Fig. 2 B are other that represent organic el device The summary section of form.

Fig. 3 A~Fig. 3 C are the schematic diagrames of one of the manufacturing step for the organic el device for representing Fig. 2A.

Fig. 4 A are the summary sections for other forms for representing organic el device, and Fig. 4 B are by Fig. 4 A organic el device The top view for the situation that hermetic sealing substrate removes.

Embodiment

1. on sealing material.

The sealing material of the present invention is the composition for forming the sealant of the various equipment such as organic el device.Sealing material Composition suitably selects according to its purpose.Such as formed thickness of thin sealant when etc., be set to comprising polymerizable monomer (B), The sealing material of anhydride ester derivs (C) and radical polymerization initiator (D).Now, sealing material can be included containing polymerization as needed The olefin polymer (A) of property functional group.On the other hand, in the low sealant of formation modulus of elasticity etc., it is set to contain The sealing material of the olefin polymer (A) of polymerizable functional group, anhydride ester derivs (C) and radical polymerization initiator (D).This When, polymerizable monomer (B) can be included as needed.

In the past, in order to improve the hygroscopicity of sealant, it have studied and hygroscopic fillers etc. are added in sealing material.If however, Sealing material includes hygroscopic fillers etc., then the transparency of the solidfied material of sealing material is damaged, or the screening characteristics step-down of sealing material and it is difficult Fully to cover by sealer.In addition, if sealing material includes filler etc., there is a problem in that：The viscosity of sealing material uprises And it is difficult to sealant carrying out filming.In addition, also it is difficult to only fully reduce the saturating of solidfied material by adding hygroscopic fillers Humidity.On the other hand, in order to reduce the moisture permeability of the solidfied material of sealing material, it is investigated the crosslink density for improving resin, but In this method, the cure shrinkage of sealing material becomes big, and the substrate being laminated with the solidfied material of sealing material produces strain sometimes.But also There are the following problems：Because the modulus of elasticity of solidfied material improves, therefore the solidfied material can not fully absorb the stress from outside Strain, can not adequately protect by sealer etc..

In contrast, in the solidfied material of the sealing material of the present invention, pass through the anhydride ester derivs with polymerizable functional group (C) anhydride group catches moisture.Think herein, even the common acid anhydrides such as hexahydrophthalic anhydride, can also catch The water that intrusion is come in, it is effective to add in sealing material.However, common acid anhydrides is not carried out with the other compositions in sealing material Polymerisation.Therefore, easily oozed out after the solidification of sealing material, it is difficult to give full play of moisture and catch performance.If in addition, these Compound is oozed out, then also has pollution by the worry of sealer.

In contrast, the anhydride ester derivs (C) that the sealing material of the present invention is included have the official of free redical polymerization reaction Can group, carry out polymerisation with the olefin polymer (A) containing polymerizable functional group, polymerizable monomer (B) etc..Therefore, exist The structure (anhydride group) from anhydride ester derivs (C) in solidfied material equably be present.That is, in the solidification of sealing material of the invention In thing, the composition (anhydride ester derivs (C)) for catching moisture does not ooze out, and can effectively catch moisture.

In addition, in the sealing material of the present invention, spread out by the olefin polymer (A) containing polymerizable functional group with acid anhydrides Biological (C) polymerization, is difficult to excessively improve so as to the crosslink density of solidfied material.As a result, sealing material is difficult to shrink in solidification, Substrate being laminated with the solidfied material of sealing material etc. is difficult to produce warpage etc..In addition and then, due to solidfied material modulus of elasticity appropriateness It is low, load from outside etc. is can absorb, therefore can adequately protect by sealer not by the shadow of the ess-strain from outside etc. Ring.

In addition, the sealing material in the present invention is filled without the alkene polymer (A) containing polymerizable functional group or its content When dividing few, the viscosity of sealing material.As a result, sealing material can be coated with by ink-jet method etc., the solidfied material of gained can be made (close Sealing) thickness it is thinning.

Hereinafter, olefin polymer (A), the polymerism containing polymerizable functional group that can be included to the sealing material of the present invention Monomer (B), anhydride ester derivs (C) and radical polymerization initiator (D) and other compositions illustrate.

1-1. contains the olefin polymer (A) of polymerizable functional group

Olefin polymer (A) containing polymerizable functional group is that in each molecule there is at least one free redical to gather The functional group of conjunction, and number-average molecular weight is more than 5000 and less than 70000 olefin polymer.

The number-average molecular weight of olefin polymer (A) containing polymerizable functional group is more than 5000 and less than 70000, excellent Elect 10000~40000 as.If the number-average molecular weight of the olefin polymer (A) containing polymerizable functional group is less than 70000, Then the mobility of sealing material fully improves, and seals various components easily by sealing material.On the other hand, if containing polymerism official The number-average molecular weight for the olefin polymer (A) that can be rolled into a ball is more than 5000, then the modulus of elasticity of the solidfied material of sealing material easily becomes It is low.

Herein, free redical polymerization contained in the olefin polymer containing polymerizable functional group (A) each molecule The quantity of functional group is more than 1, is appropriately configured according to modulus of elasticity of the solidfied material of desired sealing material etc..If The quantity of the functional group of free redical polymerization contained by olefin polymer (A) containing polymerizable functional group becomes more, then seals The modulus of elasticity of the solidfied material of material easily improves.

The functional group of free redical polymerization contained by olefin polymer (A) containing polymerizable functional group, can be with The functional group of ethene unsaturated bond.Specially (methyl) acryloyl group, vinyl, pi-allyl, vinyl ether group etc., just react Property etc. for viewpoint, be preferably (methyl) acryloyl group etc..Included in the olefin polymer (A) containing polymerizable functional group During the functional group of multiple free redical polymerizations, the functional group of these free redical polymerizations can be the functional group of identical type, also may be used For different types of functional group.

Olefin polymer (A) containing polymerizable functional group can be will " polyolefin polymer " with " with can be free The compound that the compound of the functional group of base polymerization " combined polymerization forms, or can be by " there is the function of free redical polymerization Group compound " will " polyolefin polymer " modification obtained by compound.The functional group of free redical polymerization can be directly with gathering Olefin polymer combines, and can also roll into a ball via bivalence linking base and be combined with polyolefin polymer.By the official of free redical polymerization There is no particular restriction for the species for the link group that energy group links, and can enumerate：Can have substituent carbon number be 4~12 straight chain or Branched alkylidene；The carbon number can with substituent is 4~12 cycloalkylidene etc..In addition, linking a part for group can wrap Include-COO- ,-O- etc..

In addition, as the substituent linked contained by group, such as can enumerate：Alkyl, hydroxyl, alkoxy, carboxyl, alkoxy Alkoxy, aralkoxy, aryl, aryloxy group, aryloxy group alkyl epoxide, alkylthio group, alkylthioalkylthio, aromatic alkylthio, arylthio, Arylthio alkylthio group, halogen atom etc..

As the example on olefin polymer " via the functional group of free redical polymerization for linking group and combining ", Such as it can enumerate：Group shown in following formulas (Y2).

[changing 1]

In above-mentioned formula (Y2), R₁₃Represent hydrogen atom or methyl.In above-mentioned formula, R₁₄Expression carbon number is 2~12, preferably The alkylidene for being 2~6 for carbon number.Alkylene basis representation straight-chain alkyl-sub, branched alkylidene or cycloalkylidene it is any.In addition, In formula (Y2), q represents more than 1 and less than 23 number.One molecule of the olefin polymer (A) containing polymerizable functional group It is interior can also to be included two or more only comprising the group shown in a kind of above-mentioned formula (Y2).

On the other hand, the polyolefin as the main framing of the olefin polymer (A) containing polymerizable functional group polymerize Thing, can be the polymer at least one of the alkene alkene for being 2~20 selected from carbon number.The polyolefin polymer can be A kind of homopolymer of alkene, or the random copolymer of two or more alkene, block copolymer.

Include to obtain the example for the alkene that the carbon number of polyolefin polymer is 2~20：Ethene, propylene, 1- Butylene, 1- amylenes, 3-methyl-1-butene, 1- hexenes, 4-methyl-1-pentene, 3- Methyl-1-pentenes, 1- octenes, 1- decene, 1- The carbon numbers such as dodecylene, tetradecene, cetene, 1- vaccenic acids, 1- eicosylenes are 2~20 straight-chain Or branched alpha-olefin；Cyclopentene, cycloheptene, ENB, 5- methyl -2- ENBs, tetracyclododecane, 2- methyl - The carbon numbers such as 1,4,5,8- dimethanos -1,2,3,4,4a, 5,8,8a- octahydro naphthalene are 3~20 cyclic olefin.

In addition, also include to obtain the alkene that the carbon number of polyolefin polymer is 2~20：Vinyl cyclohexyl Alkane, diene, polyenoid etc..The example of diene or polyenoid includes：Carbon number be 4~20 and with two or more double bond ring-type or The compound of chain.Specifically include：Butadiene, isoprene, 4- methyl-1,3-pentylenes, 1,3- pentadienes, 1,4- penta 2 Alkene, 1,5- hexadienes, 1,4- hexadienes, 1,3- hexadienes, 1,3- octadienes, 1,4- octadienes, 1,5- octadienes, 1,6- pungent two Alkene, 1,7- octadienes, ethylidene norbornene, vinyl norbornene, bicyclopentadiene, 7- methyl isophthalic acids, 6- octadienes, 4- are sub- Ethyl -8- methyl isophthalic acids, 7- nonadienes, 5,9- dimethyl -1,4,8- last of the ten Heavenly stems triolefins etc..

The concrete example of polyolefin polymer includes：The polyethylene such as high density polyethylene (HDPE), medium density polyethylene；Polypropylene； Poly-1-butylene；Poly- methyl butene；Ethylene/alpha-olefin copolymer；Ethene based elastomers, propylene-based elastomers, isoprene rubber Etc. olefin-based elastomer etc..Polyolefin polymer is preferably olefin-based elastomer, especially preferably isoprene rubber.

In addition, one with " compound with the functional group of free redical polymerization " of the reaction of said polyolefins based polymer Individual example includes：Polymerizable monomer (B) described later, its derivative etc..This is set " to there is free redical by using known method The compound of the functional group of polymerization " and polyolefin polymer reaction, so as to obtain the olefin-based containing polymerizable functional group Polymer (A).

1-2. polymerizable monomers (B)

Polymerizable monomer (B) is the functional group for having in each molecule at least one free redical polymerization, and molecular weight It is the compound of liquid at 23 DEG C for more than 50 and less than 1000.If sealing material includes polymerizable monomer (B), sealing material The easy step-down of viscosity, and the solidfied material of sealing material crosslink density improve.In addition, polymerizable monomer (B) is set to not include Equivalent to anhydride ester derivs described later (C) material.

The quantity of the functional group of contained free redical polymerization is more than 1 in each molecule of polymerizable monomer (B), Preferably 1~16, more preferably 1~4, more preferably 1~3.The official of free redical polymerization contained by polymerizable monomer (B) It can be vinyl, (methyl) acryloyl group, pi-allyl, vinyl ether group etc. that can roll into a ball, and be preferably (methyl) acryloyl group.It is polymerizeing Property monomer (B) in when including the functional group of multiple free redical polymerizations, can be the functional group of identical type, or not of the same race The functional group of class.

On the other hand, the molecular weight of polymerizable monomer (B) is 50~1000, preferably 50~500.If polymerizable monomer (B) molecular weight is the scope, then easily fully adjusts the viscosity of sealing material.

The example of polymerizable monomer (B) includes：There is the list (methyl) third of (methyl) acryloyl group in an intramolecular Olefin(e) acid system monomer and there are two (methyl) acrylic monomers of two (methyl) acryloyl groups in an intramolecular.

There is list (methyl) acrylic monomer of (methyl) acryloyl group as in an intramolecular, such as can arrange Lift：Monomer shown in following formulas (1B).

[changing 2]

R in formula (1B)₇Represent hydrogen atom or methyl.In addition, the R in formula (1B)₈Represent that hydrogen atom or carbon number are 4 ~18 alkyl.The alkyl that carbon number is 4~18 represents straight chained alkyl, branched alkyl or alicyclic type hydrocarbon.

The concrete example of list (methyl) acrylic monomer shown in the formula (1B) includes：(methyl) acrylic acid, (first Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, The different stearyl ester of (methyl) acrylic acid, (methyl) isoamyl acrylate, (methyl) isodecyl acrylate, (methyl) acrylic acid are different pungent Ester, the different myristin of (methyl) acrylic acid, (methyl) tridecyl acrylate, (methyl) cyclohexyl acrylate, acrylic acid two Cyclopentene epoxide ethyl ester etc..These a kind of single (methyl) acrylic monomers can be only included in the sealing material of the present invention, in addition It can include two or more.

There are two (methyl) acrylic monomers of two (methyl) acryloyl groups in an intramolecular, can be following formulas Monomer shown in (2B).

[changing 3]

R in formula (2B)₉And R₁₀Separately represent hydrogen atom or methyl.In addition, in formula (2B), R₁₁Represent carbon Number is 4~12 alkyl.The alkyl that carbon number is 4~12 represents straight-chain alkyl-sub, branched alkylidene or cycloalkylidene.

The concrete example of two (methyl) acrylic monomers shown in the formula (2B) includes：1,3 butylene glycol two (methyl) Acrylate, 1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, (first of neopentyl glycol two Base) acrylate, 1,9- nonanediols two (methyl) acrylate etc..Can be only comprising these a kind of two (methyl) propylene in sealing material Acid system monomer, it can also include two or more.

When single (methyl) acrylic monomer and two (methyl) acrylic monomers are included in sealing material, they contain Ratio is any, if but two (methyl) acrylic monomers containing ratio become it is more, under hot and humid environment it is closely sealed reliably Property improve.

In addition, the example of polymerizable monomer (B) also includes：An intramolecular have more than one vinyl monomer, Monomer of one intramolecular with more than one pi-allyl, in monomer of the intramolecular with more than one vinyl ether group, one Intramolecular has the vinyl ether compound of (methyl) acryloyl group.

The example in an intramolecular with the monomer of more than one vinyl includes：Styrene, 4-Vinyl phenol, to chlorine Styrene, to bromstyrol, p-methylstyrene, to methoxy styrene, to t-butoxystyrene, to tert-butoxy carbonyl oxygen The fragrant family vinyl compounds such as base styrene, 1- vinyl naphthalenes, 2- vinyl naphthalenes；1- heptene, 3,3- dimethyl -1- penta Alkene, 4,4- dimethyl -1- amylenes, 2,4- diphenyl -4-methyl-1-pentene, 3- methyl isophthalic acids-hexene, 4- methyl isophthalic acids-hexene, 5- Methyl isophthalic acid-hexene, 1- octenes, 2,2- dimethyl -1- hexenes, 3,4- dimethyl -1- hexenes, 4,4- dimethyl -1- hexenes, 1- nonyls Alkene, 3,5,5- trimethyl -1- hexenes, 1- decene, 1- endecatylenes, 1- dodecylenes, 1- tridecylenes, tetradecene, 1- 15 carbenes, cetene, 1- heptadecenes, 1- vaccenic acids, the carbenes of 1- 19,1- eicosylenes, the dodecylenes of 1- bis- Etc. fatty family vinyl compound；Vinyl acetate, monochloro acetic acid vinyl acetate, vinyl benzoate, pivalic acid vinyl acetate, fourth Vinyl acetate, vinyl laurate, hexanedioic acid vinyl ester, vinyl methacrylate, vinyl crotonate, 2 ethyl hexanoic acid second The generating vinyl carboxylate ester compounds such as alkene ester；The vinyl chemical combination containing nitrogen-atoms such as N- vinyl carbazoles, NVP Thing.

The example in an intramolecular with the monomer of more than one pi-allyl includes：Diallyl phthalate, isophthalic Diformazan diallyl phthalate, diallyl p phthalate, trimethylolpropane allyl ether, isocyanuric acid ester triallyl, The methallyl of isocyanuric acid ester three, cyanurate triallyl etc..

The example in an intramolecular with the monomer of more than one vinyl ether group includes：Ethyl vinyl ether, isobutyl group Vinyl ethers, butanediol divinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, hydroxyethyl vinyl ether, ring Hexane dimethanol divinyl ether, cyclohexane dimethanol monovinyl ether, diethylene glycol divinyl ether, glycol divinyl Base ether, triethylene glycol mono vinyl ether etc..

The example in an intramolecular with the vinyl ether compound of (methyl) acryloyl group includes：Acrylic acid 2- (2- second Alkenyloxy group ethyoxyl) ethyl ester, methacrylic acid 2- (2- vinyloxyethoxies) ethyl ester etc..

1-3. anhydride ester derivs (C)

Anhydride ester derivs (C) are that have the functional group of at least one free redical polymerization and composition five in each molecule The compound of the anhydride group of yuan of rings or hexatomic ring, such as can be the functional group that free redical polymerization is combined with various acid anhydrides Compound.The quantity of the functional group of free redical polymerization contained by each molecule of anhydride ester derivs (C) is more than 1, Preferably 1.It is described poly- in the solidification of sealing material if including the functional group of free redical polymerization in anhydride ester derivs (C) Conjunction property monomer (B), the olefin polymer (A) containing polymerizable functional group polymerize with anhydride ester derivs (C), and suppress acid anhydrides and spread out Biological (C's) oozes out.

The functional group of free redical polymerization contained by anhydride ester derivs (C) can be the function with ethene unsaturated bond Group.Specially (methyl) acryloyl group, vinyl, pi-allyl, vinyl ether group etc., for the viewpoint of reactivity etc., preferably For (methyl) acryloyl group etc..The functional group of free redical polymerization can be directly combined on the main framing comprising anhydride group, It can be combined via group is linked.Link group can with the olefin polymer (A) containing polymerizable functional group can The functional group of radical polymerization is identical with the link group that polyolefin polymer links.Comprising more in anhydride ester derivs (C) Can be the functional group of identical type, or different types of functional group during the functional group of individual free redical polymerization.

Anhydride ester derivs (C) for example can be the compound shown in following formulas (1C).

[changing 4]

In the formula (1C), X represents organic group that carbon number is 2~14 (wherein, anhydride group contained carbon to each other Number is 2 or 3), R₁The functional group of free redical polymerization is represented, Y represents singly-bound or links group.In addition, n represents more than 1 and 12 Following number.

X in the formula (1C) for example can be：Fatty group；Monocyclic fatty group；Condensation polycyclic formula fatty group； Monocyclic aromatic base；Condensation polycyclic formula aromatic series base；Ring type fatty group it is interconnected directly or by cross-linked structure and Into non-condensation polycyclic formula fatty group；Aromatic series base interconnected non-condensation polycyclic formed directly or by cross-linked structure Formula aromatic series base.

Above-mentioned X is more specifically the structure from various acid anhydrides, such as can be from aromatic dicarboxylic acid acid anhydride, alicyclic dicarboxyl The group of acid anhydrides.The example of aromatic dicarboxylic acid acid anhydride includes：Phthalic anhydride, naphthalic anhydride, anthracene dicarboxylic acid anhydride etc..It is another Aspect, the example of alicyclic dicarboxylic acid's acid anhydride include：Succinic anhydride, maleic anhydride, tetrabydrophthalic anhydride, hexahydro O-phthalic Acid anhydrides, 5- ENB -2,3- dicarboxylic acid anhydrides, (1 α, 4 α)-norbornane -2 α, 3 alpha, alpha-dimethyl acid anhydrides etc..

In addition, X can have substituent.Substituent can be carbon number be 1~6 alkyl, carbon number be 1~6 alkoxy, benzene oxygen Base, halogen etc..

On the other hand, the R in above-mentioned formula (1C)₁Concretely (methyl) acryloyl group, vinyl, pi-allyl, ethene Base ether.

In addition, when Y in above-mentioned formula (1C) is links group, alkylidene that it is 1~10 selected from carbon number that Y, which can be, bag The alkenylene or the bivalence linking base group of phenylene that carbon number containing 1~3 unsaturated group is 2~10.The one of the link group Part hydrogen can be optionally substituted by halogen.

Anhydride ester derivs shown in above-mentioned formula (1C) are preferably hexahydrophthalic anhydride derivative (C') or adjacent benzene two Formic anhydride derivative (C "), especially preferably hexahydrophthalic anhydride derivative (C').

As the concrete example of hexahydrophthalic anhydride derivative, can enumerate：Compound shown in following formulas (2C).Should The molecular weight of compound is preferably 296~5000.

[changing 5]

In above-mentioned formula (2C), n represents more than 1 and less than 4 numerical value.In addition, in above-mentioned formula (2C), R₁₁Independently Ground represents the group of the functional group comprising more than one free redical polymerization.R₁₁Group shown in preferably following formulas (X1), Group comprising vinyl, the group comprising pi-allyl or the group comprising vinyl ether group.

[changing 6]

In above-mentioned formula (X1), R₃For hydrogen atom or methyl.In above-mentioned formula, R₄Represent that carbon number is 2~12, is preferably carbon Number is 2~6 straight-chain alkyl-sub, branched alkylidene or cycloalkylidene.In addition, in formula (X1), p represent more than 1 and 23 with Under numerical value.

In addition, equivalent to R in above-mentioned formula (2C)₁₁The example of " group for including vinyl " include：1,3- dioxies For octahydro isobenzofuran -5- formic acid 3- butene-1s-base ester base, 1,3- dioxo octahydro isobenzofuran -5- formic acid 5- hexyls - 1- base esters base, 1,3- dioxo octahydro isobenzofuran -5- formic acid 7- octene-1s-base ester base.

And then in above-mentioned formula (2C), equivalent to R₁₁The example of " group for including pi-allyl " include：1,3- dioxies For octahydro isobenzofuran -5- allyl formates base, 1,3- dioxo octahydro isobenzofuran -5- formic acid 2- (allyloxy) second Ester group.

In above-mentioned formula (2C), equivalent to R₁₁The example of " group for including vinyl ether group " include：1,3- dioxies For octahydro isobenzofuran -5- formic acid 2- (vinyl epoxide) ethoxycarbonyl, 1,3- dioxo octahydro isobenzofuran -5- formic acid 2- (2- (vinyl epoxide) ethyoxyl) ethoxycarbonyl, 1,3- dioxos octahydro isobenzofuran -5- formic acid 4- (vinyl epoxide) fourth Ester group.

Compound shown in above-mentioned formula (2C) can have substituent.As long as substituent does not damage effect of the invention then simultaneously It is not particularly limited, such as can is straight-chain or branched-chain alkyl that carbon number is 1~5 etc..

The especially preferred example of anhydride ester derivs (C) is the compound shown in following formulas (3C).

[changing 7]

In above-mentioned formula (3C), R₅Represent hydrogen atom or methyl.

1-4. radical polymerization initiators (D)

Radical polymerization initiator (D) is to make the above-mentioned alkene containing polymerizable functional group by heating or light irradiation Hydrocarbon system polymer (A), anhydride ester derivs (C) or polymerizable monomer (B) carry out the compound of radical polymerization.Radical polymerization is drawn Hair agent (D) can be optical free radical polymerization initiator, or hot radical polymerization initiator.Radical polymerization contained by sealing material The species of initiator (D) is suitably selected according to the curing of sealing material, can only be included in sealing material any in them One side, it can also include both sides.

There is no particular restriction for optical free radical polymerization initiator, can be known optical free radical polymerization initiator.Optical free radical The example of polymerization initiator includes：Alkyl phenones based compound, acylphosphine oxide based compound, titanocenes based compound, oxime ester Based compound, styrax based compound, acetophenone based compound, benzophenone based compound, thioxanthones based compound, α-acyl oxime Ester based compound, benzoyl formiate based compound, benzil based compound, Azo, diphenyl sulfide based compound, Organic pigment based compound, iron-phthalocyanine based compound, benzoin ether based compound, anthraquinone based compound etc..Can be only in sealing material Comprising one kind in these optical free radical polymerization initiators, can also include two or more.

For the viewpoint of reactivity etc., optical free radical polymerization initiator is especially preferably alkyl phenones based compound, acyl Base phosphine oxide based compound.

On the other hand, also it is not particularly limited for hot radical polymerization initiator, can is that known hot radical polymerization is drawn Send out agent.Hot radical polymerization initiator for example can be known organic peroxide.The example bag of hot radical polymerization initiator Include：Peroxidating 2,4 dichloro benzene formyl, the peroxidating pivalic acid tert-butyl ester, peroxidating 3,5,5- trimethyl acetyls, caprylyl peroxide, Decanoyl peroxide, lauroyl peroxide, succinic acid peroxide, acetyl peroxide, peroxidating (the 2 ethyl hexanoic acid tert-butyl ester), peroxide Change toluyl, benzoyl peroxide, peroxidating Malaysia tert-butyl acrylate, peroxide between (2 ethyl hexanoic acid tert-pentyl ester), peroxidating Change bay tert-butyl acrylate, the peroxidating -3,5,5 Trimethylhexanoic acid tert-butyl ester, cyclohexanone peroxide, isopropyl peroxide carbonic acid uncle Butyl ester, 2,5- dimethyl -2,5- two (benzoylperoxy) hexane, 2,2- bis(t-butylperoxy)s octane, peroxidating second Tert-butyl acrylate, 2,2- bis(t-butylperoxy)s butane, peroxidized t-butyl perbenzoate, 4,4- bis(t-butylperoxy) valeric acids N-butyl, diperoxy M-phthalic acid di tert butyl carbonate, cumyl peroxide, methyl ethyl ketone peroxide etc..In sealing material A kind of hot radical polymerization initiator can be only included, can also be included two or more.

In addition, free radical chain transfer agent can be included in sealing material together with radical polymerization initiator.If include free radical Chain-transferring agent, then the curability of sealing material further improve.The example of free radical chain transfer agent includes：α-methylstyrene dimerization The disulfides such as species, the thio-alcohol containing sulfydryl, diphenyl disulfide, terminal unsaturation methacrylate n polymers Class, cobalt complexes of porphyrin class etc..A kind of free radical chain transfer agent can be only included in sealing material, can also be included two or more.

Relative to the mass parts of total amount 100 of the compound with free-radical polymerised functional group, free radical chain transfer agent Content is preferably the mass parts of 0.1 mass parts~10, the mass parts of more preferably 0.5 mass parts~5.

1-5. other compositions

In the range of the effect of the present invention is not damaged significantly, other resins can be included in sealing material.Other resins are for example It can be thermosetting resin etc..The example of thermosetting resin includes：Epoxy resin, phenol resin, diallyl phthalate resin, Carbamide resin, polyester resin etc..A kind of thermosetting resin can be only included in sealing material, can also be included two or more.

Filling material can be included in sealing material.The example of contained filling material includes in sealing material：Bead, polystyrene gather Polymer particle, methacrylate based polymer particle, ethylene-based polymer particle, acrylic polymer particle etc..Sealing material In be able to can also be included two or more only comprising a kind of filling material.

Modifying agent, stabilizer can be included in sealing material.The concrete example of modifying agent includes：Age resister, levelling agent, wetability Modifying agent, surfactant, plasticizer etc..These modifying agent can be used alone a kind of or combine two or more and use.It is another Aspect, the concrete example of stabilizer include：Ultra-violet absorber, preservative, antiseptic etc..These modifying agent, stabilizer are sealing It is able to can also be included two or more only comprising one kind respectively in material.

Antioxidant can be included in sealing material.Antioxidant be instigate irradiated by plasma, solar radiation is and caused Free radical inactivation material (hindered amine as light stabilizer (Hindered Amine Light Stabilizer, HALS)) or incited somebody to action Material of peroxide breaks down etc..Antioxidant has the function of preventing that the solidfied material of sealing material from changing colour.Antioxidant can be to be obstructed Amine, phenol antioxidant, phosphorous antioxidant etc..

The example of hindered amine includes：Double (2,2,6,6- tetramethyl piperidine -4- bases) sebacates, bis- chloro- 6- of 2,4- are tertiary pungent Base amido-s-triazine and polycondensation product, double [1- (the 2- hydroxyls of 4,4'- hexamethylene bis (amido -2,2,6,6- tetramethyl piperidines) Base -2- methyl propoxyl group) -2,2,6,6- tetramethyl piperidine -4- bases] sebacate.

The example of phenol antioxidant includes：Single phenols such as 2,6- di-t-butyls-paracresol, 2,2' methylene bis (4- first Base -6- tert-butyl phenols) etc. the polymer electrolyte phenol such as bisphenols, 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyls) butane Class.

Phosphorous antioxidant preferably uses：Antioxidant selected from phosphorous acid esters and oxide-based selected from oxa- phospho hetero phenanthrene Stainblocker.

Particularly in terms of assigning to the patience of ultraviolet, steady (Tinuvin) 123 (double (pungent oxygen of 1- preferably over day Base -2,2,6,6- tetramethyl -4- piperidyls) sebacate), steady (Tinuvin) 765 over day (it is double (1,2,2,6,6- pentamethyls - 4- piperidyls) sebacate and 1,2,2,6,6- pentamethyl -4- piperidyl decanedioic acid methyl esters mixture), Hostavin PR25 Steady (Tinuvin) 312 or Hostavin vsu (ethane diamides N- (2- second over (4- methoxy-benzyls dimethyl malenate), day Phenyl)-N'- (2- ethylphenyls)), (double (3- aminocarbonyl propyls) ethylenediamines -2,4- of N, N'- are double by CHIMASSORB 119FL [N- butyl-N- (1,2,2,6,6- pentamethyl -4- piperidyls) amido] chloro- 1,3,5- triazines condensation products of -6-.

Solvent can be included as needed in the sealing material of the present invention.Solvent, which has, makes each composition be uniformly dispersed or dissolve Function.The example of solvent includes：The aromatic solvents such as toluene, dimethylbenzene；The ketone such as acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK) Series solvent；Ether, butyl oxide, tetrahydrofuran, twoThe ethers such as alkane, ethylene glycol monoalkyl ether；1-METHYLPYRROLIDONE etc. is non-proton Property polar solvent；Esters such as ethyl acetate, butyl acetate etc..

The composition of 1-6. sealing material

As described above, the composition of the sealing material of the present invention is suitably selected according to the purposes of sealing material.Such as in blowing Black head spray sealing material and in use, the viscosity of preferably sealing material is low.It is therefore preferable that it is set to comprise at least the polymerism list The composition of body (B), anhydride ester derivs (C) and radical polymerization initiator (D).

Now, relative to the total amount of sealing material, preferably comprising 60 mass %~96 mass % polymerizable monomer (B), The mass % of more preferably 70 mass %~89.If the amount of polymerizable monomer (B) is more than 60 mass %, the solidfied material of sealing material With sufficient intensity.On the other hand, if the amount of polymerizable monomer (B) is below 90 mass %, relatively sufficiently comprising acid Acid anhydride derivative (C), the moisture permeability step-down of the solidfied material of sealing material.

In addition, relative to the total amount of sealing material, preferably comprising 3 mass %~39 mass % anhydride ester derivs (C), more The mass % of preferably 10 mass %~29.If the amount of anhydride ester derivs is more than 3 mass %, the moisture-inhibiting of the solidfied material of sealing material Spend abundant step-down.

Moreover, relative to the mass parts of total quality 100 of polymerizable monomer (B) and anhydride ester derivs (C), 1 is preferably comprised The radical polymerization initiator (D) of the mass parts of mass parts~25, the mass parts of more preferably 1 mass parts~20.If radical polymerization The amount of initiator (D) is above range, then polymerizable monomer (D), anhydride ester derivs (C) fully solidify, the solidfied material of sealing material Modulus of elasticity easily fall within desired scope.

In addition, in the sealing material, as needed, relative to the total amount of sealing material, it can include the mass %'s of 1 mass %~10 Alkene polymer (A) containing polymerizable functional group.

On the other hand, sealing material viscosity can it is high in the case of, reduce sealing material solidfied material modulus of elasticity In the case of, it can be set to include the alkene polymer (A) containing polymerizable functional group, anhydride ester derivs (C) and radical polymerization The composition of initiator (D).Now, as needed, polymerizable monomer (B) can be included.

Now, relative to the total amount (quality) of sealing material, preferably comprising 30 mass %~90 mass % contain polymerization The olefin polymer (A) of property functional group, the mass % of more preferably 30 mass %~60.If the alkene containing polymerizable functional group The amount of based polymer (A) is more than 30 mass %, then the modulus of elasticity of the solidfied material of sealing material easily falls within desired model In enclosing.On the other hand, it is relative to fill if the amount of the olefin polymer (A) containing polymerizable functional group is below 90 mass % Ground is divided to include anhydride ester derivs (C), the moisture permeability step-down of the solidfied material of sealing material.

In addition, relative to the olefin polymer (A) containing polymerizable functional group, anhydride ester derivs (C) and polymerism list Total quality of body (B), the amount of polymerizable monomer (B) be preferably below 65 mass %, the matter of more preferably 5 mass %~50 Measure %.If the amount of polymerizable monomer (B) is above range, the modulus of elasticity of sealing material can be made become relatively low.

And then relative to the total amount (quality) of sealing material, preferably comprising 3 mass %~40 mass % anhydride ester derivs (C).If the amount of anhydride ester derivs (C) is more than 3 mass %, the abundant step-down of moisture permeability of the solidfied material of sealing material.The opposing party Face, if the amount of the anhydride ester derivs (C) in sealing material is below 40 mass %, relatively sufficiently contain polymerism function The olefin polymer (A) of group, the modulus of elasticity step-down of sealing material.

In addition, relative to the total amount of the compound with free-radical polymerised functional group, i.e. containing polymerizable functional group The mass parts of total amount 100 of olefin polymer (A), anhydride ester derivs (C) and polymerizable monomer (B), the radical polymerization Initiator (D) is preferably the mass parts of 2 mass parts~15, the mass parts of more preferably 5 mass parts~10.

The physical property of 1-7. sealing material

The viscosity determined by E types viscosimeter under 25 DEG C, 1.0rpm of the sealing material of the present invention, preferably 5mPas ~20000mPas.If the viscosity of sealing material is above range, the screening characteristics of sealing material (such as screen printability or ink-jet Printing) improve, coating becomes easy.The viscosity of sealing material is such as the RC-500 manufactured with eastern machine industry E type viscosimeters It is measured.

When carrying out the coating of sealing material with silk-screen printing, distributor coating, sealing material of the invention passes through E type viscosity The viscosity that meter determines under 25 DEG C, 1.0rpm, preferably 10mPas~20000mPas, more preferably 10mPas~ 5000mPa·s。

On the other hand, when carrying out the coating of sealing material by ink jet printing, sealing material of the invention passes through E type viscosity The viscosity that meter determines under 25 DEG C, 1.0rpm, preferably 5mPas~1000mPas, more preferably 5mPas~ 100mPa·s。

In addition, the moisture content of sealing material is preferably below 0.5 mass %, it is further excellent more preferably below 0.1 mass % Elect as below 0.06 mass %.The circuit of organic EL element is configured with due to easily being deteriorated because of moisture, therefore is preferably to the greatest extent may be used The moisture content of sealing material can be reduced.

The moisture content of sealing material can be obtained in the following manner：About 0.1g specimen sample is measured, uses karl Fischer (Karl Fisher) moisture meter is heated to 150 DEG C, determines now caused amount of moisture (solids gasification method).

The sealing material of the present invention is preferably to be used as to form the sealing material of photosemiconductor sealant.So-called light is partly led Body, e.g. convert the electricity into light and luminous element.Photosemiconductor specifically includes：Inorganic light-emitting diode (Light Emitting Diode, LED) element, organic EL element etc., preferably organic EL element.Photosemiconductor is due to easily because of moisture Deng and deteriorate, it is therefore necessary to by face seal.

In addition, according to the sealing material of the present invention, the composition (such as pigment etc.) easily deteriorated by moisture etc. can be also protected. The moisture permeability of the solidfied material of the sealing material of the present invention is low.Therefore, if added in sealing material easily deteriorated by moisture etc. into Point, then the composition is difficult to and contact with moisture, can suppress its deterioration.

The sealing material of the present invention can be with the state of liquid by cover sealer, and it is solidified and sealant is made. During with the state of liquid by cover sealer, as long as such as being coated on by silk-screen printing, distributor coating, ink-jet application etc. On the photosemiconductors such as machine EL element, and coating layer is solidified and the photosemiconductors such as organic EL element are subjected to face sealing.Separately Outside, by the present invention sealing material be configured to it is membranaceous after, will can be sealed by the film by sealer.Be configured to it is membranaceous after, will When being sealed by sealer, by the photosemiconductor upper laminate film shape sealing material such as organic EL element, and make its solidification, so as to have The photosemiconductors such as machine EL element carry out face sealing.

The curing of sealing material is suitably selected according to species of radical polymerization initiator etc..For heat cure During type sealing material, solidify sealing material by heating.As long as heating-up temperature is the temperature higher than 23 DEG C, consider by sealer Heat resisting temperature, efficiency etc. and suitably set.

On the other hand, for light-cured type sealing material when, solidify sealing material by light irradiation.The wavelength of the light irradiated Species according to optical free radical polymerization initiator etc. and suitably selected, such as can be ultraviolet light or visible ray etc..Irradiated The accumulative light quantity of light be usually 100mJ/cm²~10000mJ/cm²Degree.Can further it be heated after light irradiation.

The manufacture method of 1-8. sealing material

As long as the sealing material of the present invention does not damage the effect of the present invention, can be manufactured with arbitrary method.Such as by following Step manufactures：1) olefin polymer (A) containing polymerizable functional group, polymerizable monomer (B), anhydride ester derivs (C) are prepared And the step of polymerization initiator (D) etc.；And 2) under non-reactive gas ambient, the step of each composition is mixed below 30 DEG C Deng.Mixing includes：With ball mill by method that these compositions disperse, be fitted into the method being stirred into flask, entered with three rollers The method that row is kneaded.

By the present invention sealing material be configured to membranaceous when, as long as such as by liquid airproof material be coated on peel off substrate on, Peeled off dried coating film.As long as the methods of coating of sealing material is coated with using silk-screen printing, distributor is carried out.

Solidfied materials of the 1-9. on sealing material

The moisture permeability of the solidfied material of the sealing material of the present invention is preferably as low as possible.That is, it is determining using the following method, 60 DEG C, the Ca reaction time starteds under 90%RH, preferably more than 24 hours.The Ca reaction time starteds are longer, represent solidfied material Moisture permeability is lower.

The moisture permeability (Ca reacts the time started) of solidfied material based on Ca methods can pass through following sequential determination.Fig. 1 is to represent The schematic diagram of the production order of the test sample of solidfied material moisture permeability based on Ca methods.

1) making of sample

As shown in Figure 1A, prepare to be impregnated in acetone and carry out the (size of glass substrate 2 that 10 minutes ultrasonic waves clean：25mm × 25mm, thickness：0.7mm).On the glass substrate 2, evaporator (ALS science and technology (ALS Technology) company systems are used Make), evaporation film 4 of the thickness for 170nm calcium metal is formed under the following conditions.It is adjusted using evaporation with mask, so that From the end of the evaporation film 4 of calcium metal, the length L untill the end of glass substrate 2 turns into 4mm.

(evaporation condition)

Vacuum during evaporation：3.0×10^-5Pa

Film speed：/ second

Calcium metal raw material：High-purity chemical manufacture, particle

The glass substrate of the evaporation film with calcium metal of gained is transferred to N in the case where being not exposed in air₂ In the glove box of atmosphere.Then, as shown in Figure 1B, prepare in addition the glass substrate 6 after acetone cleans (25mm × 55mm, thickness：On 2mm), by the thickness after solidification turn into 100 μm in a manner of be added dropwise the present invention sealing material after, make its dry and Form film 8.

Then, as shown in Figure 1 C, make the glass substrate of the film with sealing material, pasted with the glass substrate with evaporation film Close and sandwich is made, and fixed with fixture.The thickness of the sandwich of gained can pass through the glass in the film with sealing material Clamping thickness is 100 μm Teflon (Teflon) (registrar between substrate and the glass substrate of evaporation film with calcium metal Mark) piece is adjusted as sept etc..From length L' of the end of the evaporation film 4 of calcium metal untill the end of film 8 It is set to 4mm.

Then, for thermohardening type sealing material when, being heated sandwich at 100 DEG C by baking oven consolidates sealing material in 30 minutes Change and sample is made.For light-cured type sealing material when, by mercury vapor lamp to sandwich irradiate 3000mJ ultraviolet after, 80 DEG C heating makes sealing material solidify and sample is made for 30 minutes.

2) Ca reacts the measure of time started

Sample in constant temperature and humidity cabinet under 60 DEG C, 90%RH obtained by preservation.Then, the evaporation film of calcium metal is determined End be changed into transparent from metallic luster untill time (Ca react to time started).That is, if calcium metal (metallic luster) and water are anti- Should, then it is changed into transparent calcium hydroxide Ca (OH)₂.The Ca reaction time starteds are longer, represent more to be difficult to calcium metal and water occurs Reaction, moisture permeability are lower.

As described later, in organic el device, moisture, oxygen in air are easily from the gap of substrate and hermetic sealing substrate Intrusion.Accordingly, with respect to the moisture permeability of the sealant in organic el device, compared with agar diffusion method, device structure of the Ca methods closer to reality Into, and can be measured by evaluation unit, therefore can precision evaluated well.The moisture-inhibiting determined by common agar diffusion method Degree, (aftermentioned Fig. 2A self sealss substrate 26 is towards the side of substrate 22 from the direction that the interarea of organic el device invades for primary evaluation To) moisture permeability, in contrast, the moisture permeability determined by Ca methods, side that primary evaluation invades from the side of organic el device To the moisture permeability in (direction of Fig. 2A described later self sealss substrate 26 with the gap of substrate 22 towards the side of organic EL element). In this way, the direction invaded from the side of organic el device in the evaluable direction invaded as the moisture in air, oxygen of Ca methods Moisture permeability, therefore can precision evaluate well organic el device sealant moisture permeability.

Herein, the modulus of elasticity of the solidfied material of sealing material of the invention is suitably selected according to the purposes of sealing material, composition Select.For example, when sealing material includes olefin polymer (A) containing polymerizable functional group, preferably more than 0.1MPa And below 100MPa, more preferably 0.1MPa~20MPa.If the modulus of elasticity of the solidfied material of sealing material is below 100MPa, By the layer of the solidfied material comprising sealing material, protect is not influenceed by sealer by ess-strain of outside etc..The solidification of sealing material The modulus of elasticity of thing is obtained in such a way.In cupping machine, distance installs sample as 30mm between chuck, is originating Load is 10N, draw speed is that strain is determined under 30mm/ minutes.Also, stress, transverse axis is taken to take the stress of strain should by the longitudinal axis The slope of the line part of varied curve, calculates modulus of elasticity.On the other hand, polymerizable functional group is contained without described in sealing material During olefin polymer (A), modulus of elasticity can be set to 10MPa~10GPa.

The present invention sealing material solidfied material wavelength be 400nm directional light light transmittance, preferably more than 90%, more Preferably more than 95%.If the light transmittance of the directional light of solidfied material is more than 90%, sealing material can be applied to various light half The sealing component of conductor.The light transmittance of directional light is the light transmittance of the directional light of the solidfied material of 100 μm of sealing material, passes through purple Outer visible spectrophotometer etc. is measured.

2. organic el device

Generally, organic el device includes：The organic EL element that is configured on substrate, the hermetic sealing substrate paired with substrate, match somebody with somebody It is placed between substrate and hermetic sealing substrate and covers the sealant of (face sealing) organic EL element.Can be by a part for sealant or complete Portion is set to the solidfied material of the sealing material.In addition, the solidfied material moisture permeability as described above of the sealing material of the present invention is low, therefore not When organic EL element is completely covered, when other components be present between the solidfied material of the sealing material of the present invention and organic EL element, Also organic EL element can be protected not influenceed by moisture.Even if moreover, in the organic el device of structure of hermetic sealing substrate is not provided with, The solidfied material of the sealing material of the present invention also is used as the sealing material for protecting organic EL element not influenceed by moisture.By the present invention's When the solidfied material of sealing material is used as protecting sealing material that organic EL element is not influenceed by moisture, the structure of organic el device is simultaneously unlimited It is fixed.Organic el device can be organic el display panel or organic EL illuminating etc..

Fig. 2A is the summary section for a form for representing organic el device.This form is to be set to entire surface sealant The example of the solidfied material of the sealing material.As shown in Figure 2 A, organic el device 20 is sequentially laminated with：Substrate 22, organic EL element 24 and hermetic sealing substrate 26.Face sealant 28 is configured between substrate 22 and hermetic sealing substrate 26, face sealant 28 covers organic EL Around element 24.In this way, organic EL element 24 is carried out face sealing by face sealant 28.

Substrate 22 and hermetic sealing substrate 26 are usually glass substrate or resin film etc., substrate 22 and at least the one of hermetic sealing substrate 26 Side is transparent glass substrate or transparent resin film.The example of such transparent resin film includes：Poly terephthalic acid second Aromatic polyester resins such as diester etc..

When organic EL element 24 is top emission type, organic EL element 24 from the side of substrate 22 including：Reflective pixel electricity Pole layer 30 (including aluminium, silver etc.), organic EL layer 32, transparent counter electrode layer 34 (include ITO (Indium Tin Oxide：Oxidation Indium tin), IZO (indium-zinc oxide) etc.).Reflective pixel electrode layer 30, organic EL layer 32 and transparent counter electrode layer 34 can pass through Vacuum evaporation and sputter etc. and film forming.

Face sealant 28 can be set to the sealant of the solidfied material of the sealing material comprising the present invention.Include the sealing material of the present invention Solidfied material face sealant 28 directional light light transmittance as described above, it is preferred to for more than 90%.Reason is, if directional light printing opacity Rate is too low, then from element takes out the efficiency of light, light absorbing efficiency is easily reduced on element.The light transmittance of face sealant 28 The upper limit can for example be set to 99% or so.

As described above, the sealing material of the present invention, due to viscosity is adjusted into relatively low scope, therefore screening characteristics is good, can shape Into the face sealant 28 of uniform thickness.In addition, the moisture permeability that the solidfied material of the sealing material of the present invention is based particularly on Ca methods is filled Ground is divided to reduce.Therefore, comprising the present invention sealing material solidfied material face sealant 28, can particularly be captured from substrate 22 with The gap of hermetic sealing substrate 26 is moisture, oxygen etc. in the air that the side surface direction of organic EL element enters, can suppress they with Organic EL element 24 contacts.

In addition, from the interarea laterally inner side direction of organic el device 20, (in Fig. 2A, self sealss substrate 26 is towards substrate 22 Direction) intrusion moisture transmission, can be by the way that substrate 22 or hermetic sealing substrate 26 be set into the low material of moisture permeability to suppress.

As other forms of organic el device, the form for including such as lower member can be enumerated：1) it is configured at having on substrate Machine EL element；2) contacted with organic EL element and cover the resin cured matter layer of (face sealing) organic EL element；3) with the tree Fat solidified material layer contacts, and covers the passivation layer of the resin cured matter layer；4) hermetic sealing substrate (reference picture of passivation layer is covered 2B).Resin cured matter layer can be set to the solidfied material of the sealing material.

Fig. 2 B are the summary sections for other forms for representing organic el device.As shown in Figure 2 B, organic el device 20' Face sealant 28 includes the resin cured matter layer 28-1 of the solidfied material of the sealing material comprising the present invention, covering resin solidified material layer 28-1 passivation layer 28-2 and then the second resin cured matter layer 28-3 for covering passivation layer 28-2, in addition, with Fig. 2A substantially Form in the same manner.Other member of formation of organic el device 20' shown in Fig. 2 B and the structure of the organic el device 20 shown in Fig. 2A It is identical into component.

Resin cured matter layer 28-1 contained by face sealant 28 is preferably to be contacted with organic EL element.Resin cured matter layer 28-1 thickness is preferably 0.1 μm~20 μm.

Passivation layer 28-2 contained by face sealant 28 is preferably the inorganic compound layer of the film forming under plasma ambient.It is so-called The film forming under plasma ambient, for example, refer to by plasma chemical vapor deposition (Chemical Vapor Deposition, CVD) method film forming, but be not particularly limited, it can also pass through sputtering method, vapour deposition method film forming.Passivation layer 28-2 material is preferably saturating Bright inorganic compound, it can illustrate：Silicon nitride, silica, SiONF, SiON etc., are not particularly limited.Passivation layer 28-2 thickness Degree is preferably 0.1 μm~5 μm.

Passivation layer 28-2 can be contacted and film forming with resin cured matter layer 28-1.Reason is to include sealing material of the invention Even if the resin cured matter layer 28-1 of solidfied material is exposed under plasma ambient, its transparency can be also maintained.

Passivation layer 28-2 is preferably not contacted directly with organic EL element 24, and is directly contacted with resin cured matter layer 28-1 And film forming.If passivation layer 28-2 to be made directly is contacted and film forming with organic EL element 24, due to the end of organic EL element 24 For acute angle, therefore cover and reduce caused by passivation layer 28-2 sometimes.If in contrast, by being used as sealing material of the invention After the resin cured matter layer 28-1 of solidfied material seals the face of organic EL element 24, by passivation layer on resin cured matter layer 28-1 28-2 film forming, then can make passivation layer 28-2 film formation surface become gentle, and covering improves.

The second resin cured matter layer 28-3 contained by face sealant 28 can be and resin cured matter layer 28-1 identical materials (layer of the solidfied material of the sealing material comprising the present invention), or different materials.Such as the second resin cured matter layer 28-3 Moisture can be higher than resin cured matter layer 28-1 moisture sometimes.Reason is, the second resin cured matter layer 28-3 not with Organic EL element directly contacts.In addition, (taken out for top emission type organic el device via the second resin cured matter layer 28-3 The luminous organic el device of organic EL element) when, the second resin cured matter layer 28-3 light transmittance must and resin cured matter Layer 28-1 is similarly high.

Organic el device can be manufactured by arbitrary method, be may travel to lower step and manufactured：1) preparation is configured with organic The step of substrate of EL element；2) organic EL element is covered by sealing material, sealing material is solidified and the step of face sealant is made Suddenly；3) the step of being sealed by hermetic sealing substrate.

Fig. 3 is the schematic diagram of one of the fabrication schedule for the organic el device for representing Fig. 2A.First, preparation has been laminated organic The substrate 22 (reference picture 3A) of EL element 24.Organic EL element 24 includes：Reflective pixel electrode layer 30, organic EL layer 32 and transparent Counter electrode layer 34, and then can have other functional layers.Then, the liquid airproof material 28-1' of the present invention is coated on organic EL On element 24, or flap seal material 28-1' is laminated in organic EL element 24 (reference picture 3B).Then, it is superimposed hermetic sealing substrate 26, sealing material is solidified and resin cured matter layer 28-1 is made in this condition, and gluing, sealing substrate 26 (reference picture 3C).Such as This obtains organic el device 20.

Organic el device is as needed, can be manufactured further across the step that face sealant is exposed in plasma.

The example for the step that face sealant is exposed in plasma includes：Pass through plasma CVD method on the sealant of face By passivating film film forming the step of, opposite sealant irradiation plasma and the step of change surface characteristic etc..By changing surface spy Property (such as improving wetability), can improve the adaptation with other components.

As described above, a part for the containment member of organic el device can be only set to the solidfied material of the sealing material.Example Such as, other further forms as organic el device, can enumerate the form (reference picture 4A) including such as lower member：1) configure In the organic EL element on substrate；2) contacted with organic EL element and cover at least the one of the side of (sealing) organic EL element The first partial resin cured matter layer；3) contacted with organic EL element and cover the upper surface of (face sealing) organic EL element At least one of second resin cured matter layer；4) the sealing base of the first resin cured matter layer and the second resin cured matter layer is covered Plate.First resin cured matter layer can be set to the solidfied material of the sealing material.

Fig. 4 A are the summary sections for other forms for representing organic el device；Fig. 4 B are by Fig. 4 A organic el device The top view for the situation that 20 " hermetic sealing substrate 26 removes.As shown in Figure 4 A, organic el device 20 " has face sealant 28 and covered Cover the stop material (dam material) 36 of its periphery；Face sealant 28 further by covering organic EL element 24 side Second sealant 28B of the upper surface of one sealant 28A and covering organic EL element 24 is formed, in addition, with Fig. 2A substantially Form in the same manner.Other member of formation of organic el device 20 " shown in Fig. 4 A and Fig. 4 B, with the organic el device shown in Fig. 2A 20 member of formation is identical.

Stop that there is no particular restriction for material 36, can be made up of epoxy resin etc..Such stop material 36 can be by distributor side Formula is coated or is added dropwise and is formed.

Second sealant 28B is preferably without water imbibition filler, filler etc..Reason is, as described later, due to organic The upper surface of EL element does not contact with water imbibition filler, filler etc., therefore can suppress the damage (scratch) of organic EL element.Separately Outside, due also to the second sealant 28B without water imbibition filler, filler etc. easily improves total light transmittance, the transparency is excellent.

Second sealant 28B wavelength is that 400nm directional light light transmittance is preferably more than 90%.Reason is, if parallel Light light transmittance is too low, then from element takes out the efficiency of light, light absorbing efficiency is easily reduced on element.Solidified material layer 28 it is saturating The upper limit of light rate can for example be set to 99% or so.One of method for improving directional light light transmittance is free from filler or sets filler For below 10 mass %.

Such face sealant 28 for example in a manner of the side for covering organic EL element, can be coated with the sealing by 1) Material and the step of make it be solidified to form the first sealant 28A；Then, 2) in a manner of the upper surface for covering organic EL element, The step of being coated with other sealing material and making it be solidified to form the second sealant 28B and formed.Form the close of the first sealant 28A The coating of material is sealed, such as can be carried out by distributor mode, ink-jetting style；The coating of the second sealant 28B sealing material is formed, It can be carried out by screen printing mode, ink-jetting style.

In the organic el device so formed, because the side of organic EL element is covered by the solidfied material of the sealing material Lid, therefore can highly suppress the moisture in air, the transmission of oxygen.Further, since the upper surface of organic EL element by without The solidfied material covering of other sealing material of water imbibition filler, filler etc., therefore can suppress because water imbibition filler, filler etc. draw The damage (scratch) of the organic EL element risen, and also ensure that the transparency.That is, low moisture permeability and the transparency or scratch resistance can be taken into account Trace.

Embodiment

Hereinafter, with reference to embodiment, the present invention will be described.The scope of the present invention is not by embodiment limited interpretation.

[embodiment 1]

Using the compound shown in as the following formula (A1) of the polyolefin polymer (A) containing polymerizable functional group (in Kuraprene (registration mark) UC-102, the manufacture of Kuraray (Kuraray) company, number-average molecular weight 17000, a molecule Free redical polymerization average functional group number=2) 54 mass parts；As shown in polymerizable monomer (B) following formula (B1) Acrylic acid dicyclopentenyl epoxide ethyl ester (FA-512AS, the manufacture of chemical conversion industry company of Hitachi) 46 mass parts；As anhydride ester derivs (C) the hexahydrophthalic anhydride derivative (C') (4-META-H, Japan's chemical conversion company system are made) 10 shown in following formula (C1) Mass parts；As the peroxidating shown in the following formula (D1) of radical polymerization initiator -2 ethyl hexanoic acid tert-pentyl ester (Luperox 575th, Ah Ke Majifu (ARKEMA Yoshitomi) company manufactures) mixing of 5 mass parts, prepare sealing material.

[changing 8]

[changing 9]

[changing 10]

[changing 11]

[comparative example 1]

Without hexahydrophthalic anhydride derivative (C'), and be set to the ratio of components shown in table 1, in addition, with reality Apply the identical mode of example 1 and prepare sealing material.

[comparative example 2]

Manufactured using new Japan Chemical, RIKACID MH700 (4- methylhexahydrophthalic anhydrides/hexahydro O-phthalic The mixture of acid anhydrides (mass ratio=70/30)) hexahydrophthalic anhydride derivative (C') is replaced, and it is set to the group shown in table 1 Into than in addition, preparing sealing material in the same manner as example 1.

[evaluation]

Determine the viscosity of sealing material prepared in each embodiment and comparative example.Moreover, by the following method, measure sealing Light transmittance, moisture permeability, the modulus of elasticity of the solidfied material of material.Show the result in table 1.

Viscosity

It is (rich to strangle the Digital Rheometer model DII-III for flying (BROOKFIELD) company and manufacturing by E types viscosimeter ULTRA), 25 DEG C, the viscosity of sealing material under 1.0rpm are determined.

Directional light light transmittance

As background data, using ultra-violet and visible spectrophotometer (Shimadzu Seisakusho Ltd. UV-2550), alkali-free glass is determined The directional light light transmittance of 190nm~800nm of plate wavelength region (visible ray, ultraviolet light).

With 2 alkali-free glass plate grip seal materials same as described above, Teflon piece is clamped in the end of alkali-free glass plate (thickness is 100 μm), so as to which 100 μm will be set to by the thickness of the sealing material clamped by 2 alkali-free glass plates.By it at 100 DEG C Heating makes its solidification for 30 minutes, obtains the solidfied material for the sealing material that thickness is 100 μm.

By ultra-violet and visible spectrophotometer (Shimadzu Seisakusho Ltd. UV-2550), measure is clamped with 2 alkali-free glass plates The directional light light transmittance of 190nm~800nm of the solidfied material of sealing material wavelength region.Further, since Teflon piece is configured at The end of glass plate, therefore measurement result will not be impacted.

Also, the determination of light transmittance result of the solidfied material by sealing material, subtract alkali-free glass plate as background data Light transmittance, and calculate the directional light light transmittance of the solidfied material of sealing material.

Evaluation is carried out by the directional light light transmittance that wavelength is 400nm.

Moisture permeability (Ca methods)

1) making of sample

Prepare to be impregnated in acetone and carried out the glass substrate (size that 10 minutes ultrasonic waves clean：25mm × 25mm, thickness Degree：0.7mm).On the glass substrate, using evaporator (manufacture of ALS scientific ＆ technical corporation), forming thickness under the following conditions is The evaporation film (reference picture 1A) of 170nm calcium metal.Mask is used during evaporation, from the end of the evaporation film of calcium metal to glass base Length L untill the end of plate is set to 4mm.

(evaporation condition)

Vacuum during evaporation：3.0×10^-5Pa

Film speed：/ second

Calcium metal raw material：High-purity chemical manufacture, particle

The glass substrate of the evaporation film with calcium metal of gained is transferred to N in the case where being not exposed in air₂ In the glove box of atmosphere.Then, in the glass substrate (25mm × 55mm, the thickness that are cleaned through acetone prepared in addition：On 2mm), After made sealing material is added dropwise in embodiment and comparative example in a manner of the thickness after solidification turns into 100 μm, make its dry and Form film (reference picture 1B).

Then, by the glass substrate of the film with sealing material with calcium metal evaporation film glass substrate be bonded and Sandwich is made, and is fixed by fixture.The thickness of the sandwich of gained passes through the glass substrate in the film with sealing material Teflon (registration mark) piece that clamping thickness is 100 μm between the glass substrate of the evaporation film with calcium metal is as interval Thing and be adjusted.In addition, the length L' from the end of the evaporation film of calcium metal untill the end of the film of sealing material is also set For 4mm (reference picture 1C).

Then, being heated the sandwich 30 minutes at 100 DEG C with baking oven solidifies sealing material, and sample is made.Any In the case of kind, the sealing material after solidification turns into membranaceous.

2) Ca reacts the measure of time started

Sample in constant temperature and humidity cabinet under 60 DEG C, 90%RH obtained by preservation.Then, the evaporation film of calcium metal is determined End be changed into transparent from metallic luster untill time (Ca reaction the time started, unit：Hour).In Ca methods, evaluation comes from The moisture permeability of the side surface direction of the solidfied material of membranaceous sealing material.Also, the situation for being more than 24 hours by the Ca reaction time starteds Zero is set to, the situation less than 24 hours is set to ×.

Modulus of elasticity

Sealing material is made into its solidification for 30 minutes in 100 DEG C of heating, obtains the solidfied material that thickness is 100 μm.By the piece of gained The solidfied material of material cuts out 10mm × 30mm as sample.On the universal tensile testing machine of Intesco companies manufacture, between chuck Distance installs sample for 30mm, initial load be 10N, draw speed be to be tested under 30mm/ minutes.Being taken according to the longitudinal axis should Power, transverse axis take the slope of the line part of the stress-strain diagram of strain, calculate modulus of elasticity.

[table 1]

As shown in table 1, the olefin polymer (A) containing polymerizable functional group, polymerizable monomer (B), hexahydro are being included In the sealing material of the embodiment 1 of phthalic anhydride derivative (C') and radical polymerization initiator (D), the Ca reaction time starteds It is very long.Because hexahydrophthalic anhydride derivative (C') has the functional group of free redical polymerization, therefore in sealing material During solidification, with polymerizable monomer (B), the olefin polymer (A) containing polymerizable functional group etc. polymerize.As a result, due to The structure (anhydride group) from hexahydrophthalic anhydride derivative (C') is equably included in the solidfied material of sealing material, therefore Speculate the moisture for the solidfied material side intrusion for effectively capturing self sealss material.

In addition, in the sealing material of embodiment 1, modulus of elasticity is sufficiently low to 17MPa.This is due to hexahydrophthalic acid Acid anhydride derivative (C') has the functional group of free redical polymerization, in the solidification of sealing material, with polymerizable monomer (B), containing poly- Olefin polymer (A) of He Xing functional groups etc. polymerize, therefore speculates that the crosslink density of the solidfied material of sealing material does not improve excessively, And modulus of elasticity appropriateness step-down.

In contrast, in the sealing material of comparative example 2, although including 4- methylhexahydrophthalic anhydrides, hexahydro neighbour's benzene Dicarboxylic acid anhydride, but the Ca reaction time starteds are short.It is presumably due to 4- methylhexahydrophthalic anhydrides, hexahydrophthalic anhydride The solidfied material of self sealss material oozes out, therefore could not fully catch moisture.

In addition, the modulus of elasticity of the solidfied material of the sealing material of comparative example 1 and comparative example 2 is more than 38MPa.Speculate containing poly- The olefin polymer (A) of He Xing functional groups, the crosslink density of polymerizable monomer (B) improve.

[embodiment 2]

Will be as compound (FA-124AS, the Hitachi's chemical conversion company system shown in polymerizable monomer (B) following formula (B2) Make, average functional group number=2 of number-average molecular weight 198, free redical polymerization in a molecule) 80 mass parts；As acid anhydrides Hexahydrophthalic anhydride derivative (C') (4-META-H, Japan's chemical conversion company system shown in the formula (C1) of derivative (C) Make) 20 mass parts；As the peroxidating shown in the formula (D1) of radical polymerization initiator -2 ethyl hexanoic acid tert-pentyl ester (Luperox 575, the manufacture of Ah Ke Majifu companies) 5 mass parts mixing, prepares sealing material.

[changing 12]

[embodiment 3]

Peroxidating -2 ethyl hexanoic acid uncle penta is replaced using the double -2- methylbutyronitriles of 2,2'- azos shown in following formula (D2) Ester, in addition, sealing material is prepared in the same way as in example 2.

[changing 13]

[embodiment 4]

Peroxidating -2- ethyl hexyls are replaced using the 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone shown in following formula (D3) Sour tert-pentyl ester, in addition, sealing material is prepared in the same way as in example 2.

[changing 14]

[comparative example 3]

RIKACID MH700 (the 4- methylhexahydrophthalic anhydrides/hexahydro O-phthalic manufactured using new Japan Chemical The mixture of acid anhydrides (mass ratio=70/30)) replace hexahydrophthalic anhydride derivative (C'), in addition, with implementation The identical mode of example 2 prepares sealing material.

[comparative example 4]

Peroxidating -2 ethyl hexanoic acid tert-pentyl ester is replaced using the double -2- methylbutyronitriles of 2,2'- azos shown in formula (D2), is removed Beyond this, sealing material is prepared in a manner of with the identical of comparative example 3.

[comparative example 5]

Peroxidating -2 ethyl hexanoic acid uncle is replaced using the 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone shown in formula (D3) Pentyl ester, in addition, sealing material is prepared in a manner of with the identical of comparative example 3.

[comparative example 6]

By epoxy resin (cresol novolak type EPICLON (registration mark) N-680, epoxide equivalent be 200 (g/eq)- 220 (g/eq), the manufacture of DIC companies) 50 mass parts；(bisphenol-f type, YL983U0, epoxide equivalent are high-purity liquid-state epoxy resin 165 (g/eq) -175 (g/eq), Mitsubishi Chemical Ind's manufacture) 50 mass parts；Silica filler is (Admafine SO-C6, refined All agate (ADMATECHS) company manufactures) 100 mass parts；Light cationic initiator R2074 (Luo Na-Planck (Rhone- Poulenc) company manufactures) mixing of 3 mass parts, prepare sealing material.

[evaluation]

Directional light light transmittance

In heat cure, its solidification will be made within 30 minutes in 80 DEG C of heating with the sealing material that 2 alkali-free glass plates clamp, in purple When outside line (Ultraviolet, UV) solidifies, 3000mJ/cm is irradiated to the sealing material clamped with 2 alkali-free glass plates²Wavelength Make its solidification for 365nm light, obtain the solidfied material for the sealing material that thickness is 100 μm, in addition, with foregoing (embodiment 1 Deng) the assay method identical mode of directional light light transmittance be measured.

Moisture permeability (Ca methods)

Moisture permeability (Ca) is determined in a manner of with the method identical of foregoing (embodiment 1 etc.).Then by determination sample 100 DEG C carry out 30 minutes heat, evaluate moisture permeability in the same manner as described above.

[table 2]

As shown in table 2, polymerizable monomer (B), hexahydrophthalic anhydride derivative (C') and radical polymerization are being included In the sealing material of 2~embodiment of embodiment 4 of initiator (D), the Ca reaction time starteds are very long.Due to hexahydrophthalic acid Acid anhydride derivative (C') has the functional group of free redical polymerization, therefore in the solidification of sealing material, it is poly- with polymerizable monomer (B) Close, and the structure (anhydride group from hexahydrophthalic anhydride derivative (C') is equably included in the solidfied material of sealing material Group), therefore speculate the moisture for the solidfied material side intrusion for effectively capturing self sealss material.Even if in addition, it is heat-treated, Ca It is also unchanged to react the time started.Because hexahydrophthalic anhydride derivative (C') polymerize with polymerizable monomer (B), therefore push away Survey is not oozed out.

On the other hand, in the sealing material of 3~comparative example of comparative example 5, although comprising 4- methylhexahydrophthalic anhydrides, Hexahydrophthalic anhydride, but the Ca reaction time starteds are short.It is presumably due to 4- methylhexahydrophthalic anhydrides, hexahydro neighbour's benzene The solidfied material of dicarboxylic acid anhydride self sealss material oozes out, therefore could not fully catch moisture.

In addition, the Ca reaction time started length of the sealing material comprising epoxy resin of comparative example 6, i.e. moisture permeability are very It is low, but viscosity is very high, and directional light light transmittance is low.In contrast, to confirm viscosity low for the sealing material of 2~embodiment of embodiment 4, Also the coating for example, by ink-jet method can be carried out.In addition, directional light light transmittance also up to 98%.

The application advocates the priority based on Japanese Patent Application filed in 2 days Mays in 2014 2014-094957.This application Content described in specification and accompanying drawing is all referenced in present specification.

[industry utilizability]

The moisture permeability of the solidfied material of the sealing material of the present invention is low, and modulus of elasticity is moderately low.Therefore, can be applied to various The sealant of Optical devices.

Symbol description

20、20'、20”：Organic el device

22：Substrate

24：Organic EL element

26：Hermetic sealing substrate

28：Face sealant

28-1：Solidified material layer

28-2：Passivation layer

28-3：Second resin cured matter layer

28A：First sealant

28B：Second sealant

Claims

1. a kind of sealing material, it is included：Polymerizable monomer B, it has at least one free redical polymerization in each molecule Functional group, and molecular weight is more than 50 and less than 1000, is liquid at 23 DEG C；

Anhydride ester derivs C, it includes the anhydride group of at least one composition five-membered ring or hexatomic ring in each molecule and can be certainly The functional group being polymerize by base；And

Radical polymerization initiator D, it includes at least one party of hot radical polymerization initiator and optical free radical polymerization initiator.

2. sealing material as claimed in claim 1, it is further included：Olefin polymer A containing polymerizable functional group, its In each molecule have at least one free redical polymerization functional group, and number-average molecular weight be more than 5000 and 70000 with Under.

3. sealing material as claimed in claim 1, its viscosity determined by E types viscosimeter under 25 DEG C, 1.0rpm are More than 5mPas and below 20000mPas.

4. sealing material as claimed in claim 1, wherein, institute possessed by the polymerizable monomer B and the anhydride ester derivs C The functional group of free redical polymerization is stated, separately for selected from by (methyl) acryloyl group, vinyl, pi-allyl, vinyl The functional group of one or more of the group that ether is formed.

5. sealing material as claimed in claim 2, wherein, the olefin polymer A containing polymerizable functional group is had The free redical polymerization functional group, for selected from by (methyl) acryloyl group, vinyl, pi-allyl, vinyl ether group institute The functional group of one or more of the group of composition.

6. sealing material as claimed in claim 2, wherein, the anhydride ester derivs C is with least one in each molecule The hexahydrophthalic anhydride derivative C' of the functional group of free redical polymerization.

7. a kind of flap seal material, it is obtained as the sealing material described in claim 1.

8. a kind of solidfied material of sealing material, the sealing material is the sealing material described in claim 1.

9. a kind of solidfied material of sealing material, the sealing material is the sealing material described in claim 2, and its modulus of elasticity is 0.1MPa Above and below 100MPa.

10. a kind of solidfied material of sealing material, the sealing material is the sealing material described in claim 8, and it is when wavelength is 400nm Directional light light transmittance be more than 90%.

11. a kind of solidfied material of sealing material, the sealing material is the sealing material described in claim 9, and it is when wavelength is 400nm Directional light light transmittance be more than 90%.

12. a kind of sealing material, it is included：

Olefin polymer A containing polymerizable functional group, it has at least one free redical polymerization in each molecule Functional group, and number-average molecular weight is more than 5000 and less than 70000；

Hexahydrophthalic anhydride derivative C', it has the functional group of at least one free redical polymerization in each molecule； And