CN104813741B - Resin combination and its solidfied material (1) - Google Patents

Resin combination and its solidfied material (1) Download PDF

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Publication number
CN104813741B
CN104813741B CN201380062164.0A CN201380062164A CN104813741B CN 104813741 B CN104813741 B CN 104813741B CN 201380062164 A CN201380062164 A CN 201380062164A CN 104813741 B CN104813741 B CN 104813741B
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compound
resin combination
skeleton
methyl
ring
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CN104813741A (en
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内藤伸彦
木户场润
松尾雄朗
松尾雄一朗
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/04—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers only
    • C08G65/06—Cyclic ethers having no atoms other than carbon and hydrogen outside the ring
    • C08G65/16—Cyclic ethers having four or more ring atoms
    • C08G65/18—Oxetanes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H10K59/8722—Peripheral sealing arrangements, e.g. adhesives, sealants

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Epoxy Resins (AREA)
  • Polyethers (AREA)
  • Devices For Indicating Variable Information By Combining Individual Elements (AREA)

Abstract

The present invention relates to the resin combination of the sealing of the face for organic EL element, the visible light transmissivity of its solidfied material, light resistance are excellent, Tg is high, moisture-vapor transmission is low, viscosity (25 DEG C) as low as below 1300mPas, the liquid refractivity of resin combination are larger to more than 1.50, the resin combination contains following aromatic compounds (A) and following cyclic compounds (B), and the viscosity determined at 25 DEG C is below 1300mPas；Aromatic compound (A)：Aromatic compound (A) with least one of the group that can be formed by the alkyl-substituted phenylene skeleton, anthracene skeleton and luxuriant and rich with fragrance skeleton of carbon number 1~4 shown in the skeletons such as biphenyl, bisphenol-A, Bisphenol F and the bisphenol S selected shown in free style (A A) (omission), formula (A B) (omission) skeleton and oxetanyl or epoxy radicals；Cyclic compound (B)：With oxetanyl or epoxy radicals and meet the cyclic compound (B) of following conditions；The condition of the cyclic compound (B)：Ring in the cyclic compound (B) is aromatic ring, aliphatic ring or heterocycle, wherein, in the case where ring is (a) aromatic ring, the cyclic compound is the compound with the different structure of the compound from being used as above-mentioned aromatic compound (A) and with aromatic ring and oxetanyl or epoxy radicals；In addition, in the case where ring is (b) aliphatic ring, the cyclic compound is ester ring type hydrocarbon skeleton or cycloalkylidene skeleton and oxetanyl or the cyclic compound or alicyclic epoxy resin of epoxy radicals with bridged linkage.

Description

Resin combination and its solidfied material (1)
Background technology
Recently, low-moisture permeability material is important material in various industries.Particularly on electric and electronic, display periphery In industry, in order to keep quality, it is essential material, and it is expected the low-moisture permeability material of higher performance.
In recent years, in display, it is referred to as flat-panel monitor (FPD) thin display, particularly plasma display (PDP), liquid crystal display (LCD) has been put into the market and widely available.In addition, organic electroluminescent (EL) display (OLED) It is expected to as follow-on emissive type thin-film display, and has been practical in a part of commodity.Organic el display Organic EL element have on the substrates such as the glass of the drive circuit formed with TFT etc. formed with comprising containing by negative electrode and sun The structure of the element portion main body of the thin-film laminate of the luminescent layer of pole clamping.The layers such as the luminescent layer or electrode in element portion are easily because of water Point or oxygen and deteriorate, brightness or the reduction in life-span, discoloration are produced because of deterioration.Therefore, organic EL element is sealed to block The intrusion of moisture or impurity from outside.In order to realize the organic EL element of high-quality and high reliability, higher performance it is expected Encapsulant, studying various Sealing Technologies all the time.
As the representational encapsulating method of organic EL element, have studied will be previously inserted the metal system or glass of drier The closure of glass is fixed on the method (patent document 1) on the substrate of organic EL element using sealing with adhesive.This method In, in the substrate peripheral part coating binder of organic EL element, closure is set thereon, then by solidifying adhesive, Substrate and closure are fixed, so as to sealing organic el element.In such method, carried out using the closure of glass system close Envelope turns into main flow.But the closure of glass system is added by carrying out for drier to be inserted to the borehole of flat glass substrate Work and make, therefore have the tendency of cost and uprise.In addition, sealed using closure, due to being inserted in the inner side of closure Drier, thus light can not be extracted from closure side.That is, the light sent from the substrate-side extraction of element from light source, is restricted to Bottom emission type element.In the case of bottom emission type element, the problem of existing, is, by forming the drive circuit portion on substrate Caused by aperture opening ratio reduction, and due to drive circuit portion cover a part light and caused by extraction efficiency reduction.Cause This, it is expected to develop the sealing side for the top emission type element that can be applied to extract light from the opposite side of the substrate of organic EL element Method.
As the representational encapsulating method that can be applied to top emission type element, there are diaphragm seal method and sealed solid Method.Diaphragm seal method in organic EL element laminated multi-layer include inorganic or organic material film and form the side of passivating film Method (patent document 2).In order to by this method assign sufficient moisture resistance to element, it is necessary on element sequentially stacking number layer Film.Therefore, in diaphragm seal method, film formation process is long and cost is high, further, since the large-scale vacuum system required for film forming The introducing of equipment, thus initial investment uprises.
On the other hand, sealed solid method is to set passivating film to cover the element portion of whole organic EL element, and thereon The method that sealing transparency carrier is set via encapsulant.Generally, passivating film is formed by being deposited or sputtering inorganic material, But it is in most cases the faulty film with pin hole or the weak film of mechanical strength.Therefore, in sealed solid method, in member After passivating film is set on part, the sealing transparency carrier of glass substrate etc. is set via sealing with adhesive, thus improves sealing Reliability.In addition, also studied by the way that heat or photocurable resin are filled in air gap, the side of the reliability of sealing is improved Method.Such sealed solid method as the sealing for the element that can implement top emission type simply and at low cost method by Concern.
In the case where organic EL element is sealed using sealed solid method, heat or light-cured resin can be used to make For sealing adhesive, face sealing adhesive, but because their characteristic may be to the performance of element and sealing operation Productivity ratio has a significant effect, therefore extremely important., can be from for example, when sealing is insufficient to low with the moisture-vapor transmission of adhesive The pin hole intrusion element portion of passivating film, it is possible to cause the deterioration of element.In addition, if the curing reaction of encapsulant is slow, then Curing process expends the time, and the productivity ratio of sealing operation is possible to reduce.
The sealing adhesive used in these, in addition to requiring the high transmittance in visible region, is also required Luminous light resistance, stable formability, the low cure shrinkage for suppressing residual stress, protection light-emitting component is resistant to exempt from Low moisture-vapor transmission by moisture etc..Known adhesive can be used to be passed through as the sealing of organic EL element with adhesive Sealed solid method implements sealing, but is difficult to obtain at present and disclosure satisfy that reliability and the result both productivity ratio, it is expected to develop Go out to be suitable for the sealing adhesive of sealed solid method.
Prior art literature
Patent document
Patent document 1：Japanese Patent No. 4876609
Patent document 2：Japanese Unexamined Patent Publication 2012-059553
Patent document 3：Japanese Patent No. 4655172
Patent document 4：Japanese Unexamined Patent Publication 2001-81182 publications
Patent document 5：Japanese Unexamined Patent Publication 2011-225773 publications
Patent document 6：Japanese Patent No. 4850231
The content of the invention
Invent problem to be solved
It is an object of the invention to provide a kind of encapsulant of organic EL element, be especially suitable for face sealing resin Composition and visible light transmissivity, light resistance, curability are excellent, Tg is high, cure shrinkage, moisture-vapor transmission is low consolidates Compound.
The means used to solve the problem
The present inventor etc. have made intensive studies to solve the above problems, and as a result find, have specific composition and Viscosity can solve the above problems for the resin combination below certain value and its solidfied material, so as to complete the present invention.
That is, the invention described in the present invention relates to following (1)~(25).
(1) resin combination that a kind of face for organic EL element seals, it contains：With selected from by following (i) At least the one of the group that skeleton shown in formula (A-A), the skeleton shown in the formula (A-B) of following (ii), anthracene skeleton and luxuriant and rich with fragrance skeleton form Kind skeleton and oxetanyl or the aromatic compound of epoxy radicals (A)；With with oxetanyl or epoxy radicals and Meet the cyclic compound (B) of the condition of following (iii)；And
The viscosity that the resin combination determines at 25 DEG C is below 1300mPas；
(i) skeleton shown in formula (A-A)：
In above-mentioned formula, X represents Direct Bonding, sulphur atom or dimethylated methylene base, R1Represent hydrogen atom or carbon number 1~ 4 alkyl, m represent 1~4 integer；
(ii) skeleton shown in formula (A-B)：
In above-mentioned formula, R2The alkyl of hydrogen atom or carbon number 1~4 is represented, n represents 1~4 integer；
(iii) condition of the cyclic compound (B)：
Ring in the cyclic compound (B) is aromatic ring, aliphatic ring or heterocycle, wherein, it is (a) aromatic ring in ring In the case of, the cyclic compound is with the different structure of the compound from being used as the aromatic compound (A) Compound；In addition, in the case where ring is (b) aliphatic ring, the cyclic compound is with the ester ring type with bridged linkage Hydrocarbon skeleton or cycloalkylidene skeleton and oxetanyl or the cyclic compound or alicyclic epoxy resin of epoxy radicals.
(2) resin combination described in (1) as described above, wherein, aromatic compound (A), which has, is selected from following (A-1) institutes Skeleton in the group of record,
A-1：Phenyl, biphenyl, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
(3) resin combination described in (1) or (2) as described above, wherein, aromatic compound (A) is with selected from by benzene Compound of the skeleton as aromatic backbone in the group of base, biphenyl and bisphenol-A composition.
(4) resin combination any one of (1)~(3) as described above, wherein, cyclic compound (B), which has, to be selected from The ring in group described in following (B-1),
B-1：Aromatic ring, above-mentioned aliphatic ring and heterocycle.
(5) resin combination described in (1) as described above, wherein, cycloalkylidene skeleton forms the bone shown in following formula (B-A) Frame：
In above-mentioned formula, Y represents Direct Bonding, sulphur atom or methylene, R3Represent the alkane of hydrogen atom or carbon number 1~4 Base, t represent 1~4 integer.
(6) resin combination described in (1) as described above, wherein, cyclic compound (B) is alicyclic epoxy resin.
(7) resin combination any one of (1)~(4) as described above, wherein, the ring of cyclic compound (B) is virtue Fragrant race's ring.
(8) resin combination described in (7) as described above, wherein, cyclic compound (B) has to be remembered selected from following (B-2) Skeleton in the group of load,
B-2：Phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
(9) resin combination described in (8) as described above, wherein, cyclic compound (B) be with select free phenyl, biphenyl, The oxetane compound or epoxide of skeleton in the group of naphthalene, dinaphthalene and bisphenol-A composition.
(10) resin combination any one of (1)~(4) as described above, wherein, cyclic compound (B), which has, to be selected from The skeleton in group described in following (B-3),
B-3：Isobornyl, adamantane, pentamethylene, hexamethylene, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
(11) resin combination described in (4) or (10) as described above, wherein, cyclic compound (B) is with selected from by gold The oxetane compound or epoxide of skeleton in the group of firm alkane, hexamethylene and hydrogenated bisphenol A composition.
(12) resin combination any one of (1)~(4) as described above, wherein, cyclic compound (B), which has, to be selected from The skeleton in group described in following (B-4),
B-4：Morpholine, tetrahydrofuran, oxinane, dioxane, triazine, carbazole, pyrrolidines and piperidines.
(13) resin combination described in (4) or (12) as described above, wherein, cyclic compound (B) is with selected from by oxygen The oxetane compound or epoxide of skeleton in the group of azacyclohexane, dioxane and triazine composition.
(14) resin combination any one of (1)~(13) as described above, it also contains curing agent (C).
(15) resin combination described in (14) as described above, wherein, curing agent (C) is light cationic polymerization initiator.
(16) resin combination described in (15) as described above, wherein, the light cationic polymerization initiator is selected from following (C-1) at least one of group described in,
C-1：Sulfonium salt, iodineSalt,Salt, ammonium salt and stibate.
(17) resin combination described in (14) as described above, wherein, curing agent (C) is thermal curing agents.
(18) resin combination described in (17) as described above, wherein, the thermal curing agents are selected from described in following (C-2) Group,
C-2：Aminated compounds, anhydrides compound, amides compound, phenolic compound, carboxylic acid compound, imidazoles Class compound, isocyanuric acid adduct, metallic compound, sulfonium salt, ammonium salt, stibate,Salt, microcapsule-type curing agent.
(19) resin combination any one of (1)~(18) as described above, wherein, relative to aromatic compound (A) with the mass parts of total amount 100 of cyclic compound (B), the aromatic compound (A) containing 20~80 mass parts.
(20) resin combination any one of (1)~(19) as described above, wherein, relative to aromatic compound (A) with the mass parts of total amount 100 of cyclic compound (B), the cyclic compound (B) containing 20~80 mass parts.
(21) resin combination any one of (1)~(20) as described above, wherein, by aromatic compound (A) with When the total amount of cyclic compound (B) is set to 100 mass parts, the curing agent (C) containing 0.1~5 mass parts.
(22) resin combination any one of (1)~(21) as described above, wherein, form the solidification of 100 μm of thickness During thing, the moisture-vapor transmission of the solidfied material determined under conditions of 60 DEG C, relative humidity 90% is 35g/m224 hours Below.
(23) a kind of organic el display, wherein, utilize the resin combination made any one of above-mentioned (1)~(22) Solidfied material obtained from solidification has carried out face sealing.
(24) film that a kind of face for organic el display seals, it is by by any one of above-mentioned (1)~(22) institute The resin combination stated is coated on base material and it is solidified and is obtained, and has barrier property.
(25) resin combination the answering in the sealing of the face of organic EL element any one of above-mentioned (1)~(22) With.
Invention effect
The viscosity of the resin combination of the present invention is low and its solidfied material is visible light transmissivity, light resistance is excellent, Tg is high, solid It is low to change shrinkage factor, moisture-vapor transmission, is therefore particularly suited for the encapsulant of organic EL element, is particularly suitable for face sealing.
Embodiment
As the above-mentioned aromatic compound (A) contained by the resin combination of the present invention, can enumerate following illustrated Oxetane compound or epoxide.
Aromatic compound (A) contained by the resin combination of the present invention is selected from by above-mentioned formula (A-A) as long as having At least one of the group of skeleton, anthracene skeleton and luxuriant and rich with fragrance skeleton composition shown in shown skeleton, above-mentioned formula (A-B) skeleton and Oxetanyl or the aromatic compound of epoxy radicals (A).
It should be noted that in the present invention, anthracene skeleton or luxuriant and rich with fragrance skeleton can have substituent, can also unsubstituted. In the case of with substituent, it can be enumerated as substituent：Alkyl, alkoxy or alkenyl, these substituents are both preferably Carbon number 1~4.
In the present invention, as aromatic compound (A), using with selected from as the skeleton shown in following formula (A-A) or Skeleton, anthracene skeleton shown in following formula (A-B) and skeleton and oxetanyl or epoxy radicals in the group of luxuriant and rich with fragrance skeleton composition Aromatic compound.
(in above-mentioned formula, X represents Direct Bonding, sulphur atom or dimethylated methylene base, R1Represent hydrogen atom or carbon number 1 ~4 alkyl, m represent 1~4 integer.)
(in above-mentioned formula, R2The alkyl of hydrogen atom or carbon number 1~4 is represented, n represents 1~4 integer.Wherein, do not wrap The skeleton that (A-A) containing above-mentioned formula is included)
It is (following with above-mentioned cyclic compound (B) by combining the aromatic compound (A) (hereinafter also referred to composition (A)) Also referred to as composition (B)), extremely excellent moisture-proof effect can be obtained.Above-mentioned skeleton turns into the sufficient barrier of moisture, so as to Prevent moisture-inhibiting.
In above-mentioned formula (A-A) skeleton, it is preferable that X is Direct Bonding or has dimethylated methylene base, particularly preferred direct key Close (biphenyl backbone).
Above-mentioned (A-A) skeleton, (A-B) skeleton, anthracene skeleton or luxuriant and rich with fragrance skeleton and oxetanyl or epoxy radicals, preferably directly Connection is connected by alkyl.
In above-mentioned skeleton, when oxetanyl or epoxy radicals are connected by alkyl, it can be enumerated as the alkyl：Carbon The alkylidene of atomicity 1~10 or with ehter bond carbon number 1~10 alkylidene.Ehter bond can in the alkylidene, Can be in the either end of the alkylidene.Preferably alkylidene (the more preferably Asia of carbon number 1~3 of carbon number 1~4 Alkyl), the alkylidene of alkylidene-oxygen atom-carbon number 1~4 of carbon number 1~4 (more preferably carbon number 1~3 The alkylidene of alkylidene-oxygen atom-carbon number 1~3) etc. between carbon atom comprising ehter bond carbon number 2~10 alkylene The base alkylidene of carbon number 2~6 (more preferably) or-oxygen methyl etc. have in alkylidene end the carbon number 1 of ehter bond~ 4 alkylidene (alkyl of-epoxide-carbon number 1~4, the alkyl of more preferably-epoxide-carbon number 1~4).Have in end When having ehter bond, usual ether is bonded with aromatic rings, and alkyl is bonded with oxetanes ring or epoxide ring.
As the aromatic compound (A) containing oxetanyl, the oxa- ring fourth of for example following illustrations can be enumerated Hydride compounds.
It can enumerate for example：1,4- double { [(3- ethyl -3- oxetanyls) methoxyl group] methyl } benzene, 3- ethyls -3- Double [(3- Ethyloxetane -3- bases) first of phenoxymethyloxetane, xylylene dioxygen azetidine, 1,4- Epoxide] benzene, double [(3- Ethyloxetane -3- bases) methoxyl group] benzene of 1,3-, the double [(3- Ethyloxetanes -3- of 1,2- Base) methoxyl group] benzene, 4,4 '-bis- [(3- Ethyloxetane -3- bases) methoxyl group] biphenyl, 2,2 '-bis- [(3- ethyl -3- oxygen Azetidinyl) methoxyl group] biphenyl, 3,3 ', 5,5 '-tetramethyl [4,4 '-bis- (3- Ethyloxetane -3- bases) methoxyl groups] Biphenyl, 2,7- double [(3- Ethyloxetane -3- bases) methoxyl group] naphthalene, 4,4 '-bis- [(1- ethyl -3- oxetanyls) Methyl] oxetane compound such as sulfenyl diphenyl sulfide ether acid.
As the aromatic compound (A) with epoxy radicals, can enumerate：Styrene oxide, phenyl glycidyl ether etc. Epoxide with phenyl skeleton, biphenylyl glycidyl ether, xenyl diglycidyl ether, to tert-butyl-phenyl shrink Glycerin ether, 3,3 ', 5,5 '-tetramethyl -4,4 '-bis- (glycidyl epoxide) -1,1 '-biphenyl, phenyl aralkyl type epoxy Compound, biphenyl aralkyl type epoxy compound etc. have epoxide, the phenol novolak-type epoxy chemical combination of biphenyl backbone Novolak type epoxy compounds, bisphenol A diglycidyl ether or the brominated bisphenols such as thing, cresol novolak type epoxy compound The bisphenol A type epoxy compounds such as A diglycidyl ethers, bisphenol-S diglycidyl ether or brominated bisphenol S diglycidyl ethers etc. are double Phenol S type rings oxygen compound, double phenyl fluorenes diglycidyl ethers or double phenyl fluorenes ethanol glycidol ethers etc. have fluorene skeleton (preferably For double phenyl fluorene skeletons) epoxide etc..
Here, the example as xenyl aralkyl epoxy compound, following formula (A-Aa) compound can be enumerated.
(in above-mentioned formula, G represents glycidyl, and p represents 1~50 integer.)
As above-mentioned formula (A-Aa) compound, can enumerate：Commercially available o-phenyl phenol glycidol ether (three light strain formulas Commercial firm's system) etc..
As the specific skeleton of composition (A), the skeleton that can be enumerated in the group described in following (A-1), A-1： Phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
In the resin combination of the present invention, in the above-mentioned skeleton of mentioned component (A), preferably phenyl skeleton is not (including formula (A-A) skeleton, similarly hereinafter), biphenyl backbone, bisphenol A skeleton or bisphenol S skeleton.More preferably viscosity, moisture permeability are low, light is saturating Cross the excellent biphenyl backbone of rate, bisphenol A skeleton.Among above-mentioned, more preferably biphenyl backbone.
In addition, as mentioned component (A), the composition (A) preferably with 1 oxetanyl or epoxy radicals, more preferably Also there is the aromatic compound (A) of above-mentioned preferable skeleton or preferred skeleton for skeleton.More preferably containing connection The mono-epoxy compound of benzene skeleton or single oxetanes based compound.
As mentioned component (A), as long as there is any one in oxetanyl or epoxy radicals, more preferably ring Epoxide.
As the preferred aromatic compound (A) with epoxy radicals, can enumerate：Monocyclic oxygen containing biphenyl backbone Based compound, the mono-epoxy compound containing phenyl skeleton, such as：Phenylphenol glycidol ether (more preferably adjacent phenyl Phenol glycidyl ethers) or limonene oxide.
Relative to the mass parts of total amount 100 of the composition (A) as reactive compounds+composition (B), composition of the invention (A) content is 20~80 mass parts, preferably 30~70 mass parts.In addition, in order to realize low moisture permeability, the official of composition (A) It is preferably 10~500g/ equivalents that equivalent, which can be rolled into a ball, more preferably 50~250g/ equivalents.
As the cyclic compound (B) contained by the resin combination of the present invention, can enumerate：With with specific skeleton Aromatic rings oxetane compound or epoxide, the oxetanes with the aliphatic ring with specific skeleton Compound or epoxide, the oxetane compound or epoxide with heterocycle.
As the ring in cyclic compound (B), the ring that can be enumerated in the group described in following (B-1),
B-1：Aromatic rings, aliphatic ring and heterocycle.
Here, when oxetane compound or epoxide of the selection with aromatic rings are as cyclic compound (B), Use the compound of the different structure of the structure with the compound from being selected as aromatic compound (A).
In addition, as cyclic compound (B), it is usually preferred to have multiple (at least two) oxetanyls or epoxy radicals Cyclic compound (B).
As the oxetane compound or epoxide with aromatic rings that may be used as cyclic compound (B), Can enumerate with as above-mentioned aromatic compound (A) illustration compound identical compound, in the present invention, with the virtue Fragrant compounds of group (A) and used time, as described above, it is important that the change used using structure and as the aromatic compound (A) The different compound of compound is as cyclic compound (B).
As the specific fragrant ring skeleton of the cyclic compound (B) with aromatic rings, can enumerate selected from following (B-2) Skeleton in described group, B-2：Phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.Among those, As preferable skeleton, to select the skeleton in free phenyl, biphenyl, naphthalene, dinaphthalene and the group of bisphenol-A composition.
It is exemplified below specific compound.
As the oxetane compound with aromatic rings that may be used as cyclic compound (B), can enumerate with Compound identical compound cited by the part of mentioned component (A), can specifically illustrate following compounds.
It can enumerate for example：1,4- double { [(3- ethyl -3- oxetanyls) methoxyl group] methyl } benzene, 3- ethyls -3- Double [(3- Ethyloxetane -3- bases) first of phenoxymethyloxetane, xylylene dioxygen azetidine, 1,4- Epoxide] benzene, double [(3- Ethyloxetane -3- bases) methoxyl group] benzene of 1,3-, the double [(3- Ethyloxetanes -3- of 1,2- Base) methoxyl group] benzene, 4,4 '-bis- [(3- Ethyloxetane -3- bases) methoxyl group] biphenyl, 2,2 '-bis- [(3- ethyl -3- oxygen Azetidinyl) methoxyl group] biphenyl, 3,3 ', 5,5 '-tetramethyl [4,4 '-bis- (3- Ethyloxetane -3- bases) methoxyl groups] Biphenyl, 2,7- double [(3- Ethyloxetane -3- bases) methoxyl group] naphthalene, 4,4 '-bis- [(1- ethyl -3- oxetanyls) Methyl] sulfenyl diphenyl sulfide ether acid etc..
As the epoxide with aromatic rings that may be used as cyclic compound (B), following chemical combination can be illustrated Thing.
It can enumerate for example：Styrene oxide, phenyl glycidyl ether etc. have epoxide, the biphenyl of phenyl skeleton Base glycidol ether, xenyl diglycidyl ether, to tert-butyl-phenyl glycidol ether, 3,3 ', 5,5 '-tetramethyl -4,4 ' - Double (glycidyl epoxides) -1,1 '-biphenyl, xenyl aralkyl type epoxy compound etc. have the epoxy compound of biphenyl backbone It is the novolak type epoxy compounds such as thing, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, double Bisphenol A type epoxy compound, bisphenol-S diglycidyl ether, the bromines such as phenol A diglycidyl ethers, brominated bisphenol A diglycidyl ethers Change the bisphenol S type epoxy compounds such as bisphenol-S diglycidyl ether, double phenyl fluorenes diglycidyl ethers, double phenyl fluorenes ethanol to shrink Glycerin ether etc. has double (the 2,3- epoxy radicals propane -1- base oxygen of the epoxide, glycidyl epoxide naphthalene, 1,6- of fluorene skeleton Base) naphthalene, dinaphthalene glycidol ether, dinaphthalene diglycidyl ether, dinaphthol ethanol diglycidyl ether etc. have the ring of naphthalene skeleton Oxygen compound etc..
In the present invention, oxetane compound or epoxide of the selection with aromatic rings are as cyclic compound (B) when, in above-claimed cpd, using with the compound from being selected as composition (A) it is different it is structure, with aromatic ring And the compound of oxetanyl or epoxy radicals.Now, in resin combination of the invention, different have containing 2 kinds The oxetane compound or epoxide of aromatic rings.
When compound of the selection with aromatic rings is as cyclic compound (B), as containing the preferable of the aromatic rings Skeleton, it can enumerate：Phenyl skeleton, biphenyl backbone, bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton or naphthalene skeleton etc..It is more excellent Elect the biphenyl backbone, bisphenol A skeleton or naphthalene skeleton that viscosity, moisture permeability are low, light transmittance is excellent as.More preferably biphenyl backbone or double Phenol A skeletons, most preferably bisphenol A skeleton.The viscosity of these compounds is preferably below 1500mPas.
As the preferable cyclic compound (B) with aromatic rings, the ring-type with above-mentioned preferable skeleton can be enumerated Compound (B), the cyclic compound (B) with preferred skeleton, further preferred skeleton, most preferred skeleton are respectively More preferably, further preferred, most preferred cyclic compound (B).Can be oxa- ring in the cyclic compound (B) Butane group and any one in epoxy radicals, it is often preferred that epoxy radicals.Especially as cyclic compound (B), preferably there is connection The epoxide of benzene skeleton or bisphenol A skeleton, the particularly preferably compound with multiple epoxy radicals.
Relative to the mass parts of total amount 100 of the composition (A) as reactive compounds+composition (B), composition of the invention (B) content is 20~80 mass parts, preferably 30~70 mass parts.In order to realize low moisture permeability, the functional group of composition (B) works as Measure as 10~1000g/ equivalents, preferably 50~500g/ equivalents.
In addition, from the aspect of low-moisture permeability, composition (A) uses different compounds from composition (B).Because In order that moisture permeability reduces, it is believed that electron-dense compound is effective, but not only electron density but also and compound Between crosslink density balance and it is important.Therefore, in order that moisture permeability reduces, for example, as composition (A), using containing Phenyl skeleton, biphenyl backbone or bisphenol A skeleton and the chemical combination with a polymerizable groups (oxetanyl or epoxy radicals) Thing, as composition (B), used with above-mentioned preferable content contain phenyl skeleton, biphenyl backbone, bisphenol A skeleton or naphthalene bone respectively Frame and the mode with the compound of multiple (2~more than 3) polymerizable groups (oxetanyl or epoxy radicals).As The example more preferably combined, can enumerate in the following manner：As composition (A), using with biphenyl backbone or bisphenol-A bone Frame and the compound (compound preferably with an epoxy radicals) with an oxetanyl or epoxy radicals, as into Divide (B), using with phenyl skeleton, biphenyl backbone or bisphenol A skeleton and with multiple (at least two) oxetanyls or ring The compound of epoxide (be preferably epoxy radicals) or epoxide (such as limonene oxide, 3,4- rings containing hexamethylene skeleton Oxygen cyclohexenyl methyl -3 ', 4 '-epoxy hexane formic acid esters and A Hydrogenated Bisphenol A 2-glycidyl ether compound etc.).Need to illustrate , as A Hydrogenated Bisphenol A 2-glycidyl ether compound, can enumerate：Hydrogenated bisphenol A diglycidyl ether, A Hydrogenated Bisphenol A F Diglycidyl ether or A Hydrogenated Bisphenol A S diglycidyl ethers.These compounds used as composition (A) and composition (B) are glued Degree is both preferably below 1300mPas, more preferably more preferably below 800mPas, below 500mPas.
Then, for the cyclic compound (B) with aliphatic ring in cyclic compound (B), carried out in detail following Explanation.
In the present invention, as the cyclic compound (B) with aliphatic ring, using with the alicyclic ring with bridged linkage The cyclic compound or ester ring type asphalt mixtures modified by epoxy resin of formula hydrocarbon skeleton or cycloalkylidene skeleton and oxetanyl or epoxy radicals Fat.
The above-mentioned ester ring type hydrocarbon skeleton or cycloalkylidene skeleton (the sub- cycloalkanes without bridged linkage with bridged linkage Base skeleton) there can be substituent, can also not have substituent.In the case of with substituent, it can be arranged as substituent Lift：Alkyl, alkenyl or alkoxy, these groups are preferably carbon number 1~4, more preferably carbon number 1~3.
As the aliphatic ring skeleton of the above-mentioned cyclic compound (B) with aliphatic ring, can enumerate：With bridging knot The ester ring type hydrocarbon skeleton ester ring type hydrocarbon skeleton with bridged linkage of carbon number 7~10 (be preferably) of structure and without bridging knot The cycloalkylidene skeleton of structure (is preferably the sub- ring of the cycloalkylidene skeleton, more preferably carbon number 5 or 6 of carbon number 4~7 Alkyl skeleton, more preferably cyclohexyl skeleton).It should be noted that in cycloalkylidene skeleton, cyclohexylidene skeleton can Think 2 cycloalkylidene skeleton Direct Bondings or be bonded via linking group, can be the skeleton shown in following formula (B-A).
(in above-mentioned formula, Y represents Direct Bonding, sulphur atom or methylene, R3Represent the alkane of hydrogen atom or carbon number 1~4 Base, t represent 1~4 integer.)
As the aliphatic ring skeleton of the cyclic compound (B), according to circumstances, the carbon preferably without bridged linkage is former The sub- hexamethylene of the cycloalkylidene skeleton of the cycloalkylidene skeleton of subnumber 4~7, more preferably carbon number 5 or 6, most preferably divalent Base skeleton.It should be noted that cyclohexylidene skeleton can form the skeleton shown in above-mentioned formula (B-A).
If illustrating the preferable aliphatic ring skeleton of the cyclic compound (B), can enumerate：Selected from following formula B-3 Skeleton in described group, B-3：Isobornyl, adamantane, pentamethylene, hexamethylene, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and hydrogen Change bisphenol S, can more preferably enumerate：Pentamethylene, hexamethylene, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
In the cycloalkylidene skeleton without bridged linkage, most preferably cyclohexylidene skeleton.In cyclohexylidene skeleton In the case of, the hexamethylene skeleton for not forming the skeleton shown in formula (B-A) sometimes is preferable, formd sometimes shown in formula (B-A) The situation of skeleton be preferable, therefore can suitably select to use.
As the cyclic compound (B) with aliphatic ring used in the present invention, can enumerate：With above-mentioned aliphatic The cyclic compound or alicyclic epoxy resin of ring skeleton and oxetanyl or epoxy radicals.
By combining above-mentioned cyclic compound (B) and above-mentioned aromatic compound (A), extremely excellent moisture-proof can be obtained Property effect.Because above-mentioned skeleton turns into the sufficient barrier of moisture, so as to prevent moisture-inhibiting.
In above-mentioned formula (B-A) skeleton preferably, Y is Direct Bonding or the skeleton with methylene, is particularly preferably straight Connect bonding.
In addition, as the ester ring type hydrocarbon skeleton with bridged linkage, can specifically enumerate：Adamantane framework, two polycyclics penta Diene skeleton or isobornyl skeleton are as preferable skeleton, according to circumstances, preferably adamantane framework or isobornyl skeleton.
In addition, the concrete example as cycloalkylidene skeleton (the cycloalkylidene skeleton for not having bridged linkage), can be enumerated： Cyclopentane framework, hexamethylene skeleton, cycloheptane skeleton etc. are used as preferable skeleton, as described above, 2 in these can be direct Bonding is bonded via linking group and forms above-mentioned formula (B-A) skeleton.
The above-mentioned ester ring type hydrocarbon skeleton with bridged linkage, cycloalkylidene skeleton (including above-mentioned formula (B-A) skeleton) and oxygen Azetidinyl or epoxy radicals, preferably it is directly connected to or is connected by alkyl (ehter bond can be included).
Moreover, as specific connected mode, oxetanyl or epoxy radicals are bonded with alkyl, and the alkyl is direct or passes through It is connected by ehter bond with aliphatic ring.When being connected by alkyl, as alkyl, it can enumerate：The alkyl or tool of carbon number 1~10 There is the alkyl of the carbon number 1~10 of ehter bond.Alkyl as preferable linking group, containing ehter bond, can be enumerated：Carbon is former The alkylidene of alkylidene-oxygen atom-carbon number 1~4 of subnumber 1~4 (is preferably alkylidene-oxygen original of carbon number 1~3 The alkylidene of son-carbon number 1~3) etc. between carbon atom the alkylidene of the carbon number 2~10 comprising ehter bond (be preferably that carbon is former The alkylidene of subnumber 2~6) or-oxygen methyl etc. there is the alkylidene (- oxygen of the carbon number 1~4 of ehter bond in alkylidene end The alkyl of base-carbon number 1~4) (alkyl of more preferably-epoxide-carbon number 1~3) etc..The alkylidene has in end In the case of ehter bond, usual ether is bonded with aliphatic ring, and alkyl is bonded with oxetanes ring or epoxide ring.In addition, as fat Ring type epoxy resin is the same, and epoxy radicals can be formed directly on aliphatic ring.
As such oxetane compound with aliphatic ring, can enumerate：3 (4), 8 (9)-bis- [(1- second Base -3- oxetanyls) methoxy]-three rings [5.2.1.2.6] decane etc..
As such epoxide with aliphatic ring, can enumerate：Limonene oxide, formula (b- described later 1a), formula (b-1b) and alicyclic epoxy resin, hydrogenated bisphenol A epoxy compound, A Hydrogenated Bisphenol A F bis- described in formula (b-1c) Bisphenol F type epoxy compound, the A Hydrogenated Bisphenol A S 2-glycidyls such as glycidol ether, bromination hydrogenation Bisphenol F diglycidyl ether Bisphenol S type epoxy compound, diepoxy tristane, the tristanes two such as ether, bromination hydrogenation bisphenol-S diglycidyl ether shrink The epoxidations with adamantane framework such as the epoxide with tricyclodecane skeleton such as glycerin ether, adamantane glycidol ether Compound etc..
Formula (b-1a)：
Formula (b-1b)：
Formula (b-1c)：
(n is average value and represents 1~5 positive number.)
As the compound with aliphatic ring in cyclic compound (B), preferred alicyclic epoxy resin or with choosing The cyclic compound (B) of skeleton in the group of free isobornyl skeleton, adamantane framework and bisphenol A skeleton composition.From it is colourless, And the aspect excellent, that glass transition temperature is high of reactivity is set out, and can particularly preferably be enumerated：Alicyclic epoxy resin has The cyclic compound (B) of adamantane framework.
Relative to the mass parts of total amount 100 of the composition (A) as reactive compounds+composition (B), of the invention has fat The content of the cyclic compound (B) of fat race ring is 20~80 mass parts, preferably 30~70 mass parts.In order to realize low moisture-inhibiting Degree, the preferable functional equivalent of the cyclic compound (B) are 10~1000g/ equivalents, more preferably 50~500g/ equivalents.
As the example of heterocycle, can enumerate：Morpholine skeleton, tetrahydrofuran skeleton, oxinane skeleton, dioxane Hexane skeleton, triazine skeleton, carbazole skelton, pyrrolidines skeleton and piperidine scaffolds.They can have substituent, can not also have Substituted base, in the case of with substituent, it can be enumerated as the substituent：Alkyl, alkoxy or alkenyl, it typically is Carbon number about 1~about 4.
Above-mentioned heterocyclic skeleton can also can be connected with oxetanyl or epoxy radicals with Direct Bonding by divalent alkyl, But generally connected by divalent alkyl.In the case of being connected by alkyl, as alkyl, it can enumerate：Carbon number 1~10 Alkylidene or with ehter bond carbon number 1~10 alkylidene.
As the oxetane compound with heterocycle, can enumerate：Isocyanuric acid (CIC acid) and oxa- cyclobutanol Reaction product etc..
As the epoxide with heterocycle, can enumerate：Isocyanuric acid 1,3,5- three-glycidyl esters etc. have different The compound of cyanurate skeleton, dioxane glycol diglycidyl ether etc. have dioxane glycol skeleton The epoxides such as compound.
As the composition (B) with heterocycle, it is however preferred to have the compound of isocyanuric acid ester skeleton, particularly preferred CIC acid Reaction product, isocyanuric acid 1,3,5- three-glycidyl esters with oxa- cyclobutanol.
Relative to the mass parts of total amount 100 of the composition (A) as reactive compounds+composition (B), the composition with heterocycle (B) content is 20~80 mass parts, preferably 30~70 mass parts.In order to improve moisture permeability, the official of the preferable composition (B) It is 10~500g/ equivalents that equivalent, which can be rolled into a ball, more preferably 50~250g/ equivalents.
The present invention relates to the hardening resin composition containing mentioned component (A), mentioned component (B), below for conduct The preferable combination of the combination of these compositions illustrates.
As preferable combination, preferably using the weight average molecular weight of any one in mentioned component (A) or mentioned component (B) Composition for less than 2000, more preferably less than 1000, particularly preferably less than 500 forms hardening resin composition.This It is because of by the way that the composition of such low molecule amount to be used as to any one in composition (A), composition (B), it can be ensured that low moisture absorption Property, and be readily expanded after low viscosity and coating, therefore can obtain in the excellent composition of OLED manufacture view.
In addition, particularly in the case of thermal curing, any one further preferably in composition (A) and composition (B) is oxa- ring Butane compound.Because it is oxetane compound by any one, it can be ensured that agent of low hygroscopicity, and can obtain The resin combination excellent to the curability of short time.
In addition, as composition (A) and the preferable usage rate of composition (B), (A)/(B) is 8/2~2/8, more preferably 7/3~3/7.
When wanting to improve Tg (glass transition temperature), if aromatic compound, then bisphenol-A bone can be introduced Frame, if ester ring type compound, then it can introduce dicyclopentadiene skeleton, isobornyl skeleton, adamantane framework.
Particularly in the present invention, viscosity (viscosity when being determined at 25 DEG C of resin combination：It is usually similarly hereinafter) Below 1500mPas, preferably below 1300mPas, more preferably below 1200mPas, preferably at blending constituent (A) With to reach below above-mentioned viscosity when composition (B).
In the present invention, it is preferred to mode be, as composition (A), using containing biphenyl backbone and there is 1 oxa- ring fourth Monofunctional, aromatic's compound of alkyl or epoxy radicals, it is however preferred to have the epoxy compound containing biphenyl backbone of 1 epoxy radicals Thing (being preferably the monoglycidyl ether containing biphenyl backbone), more preferably o-phenyl phenol glycidol ether, as composition (B), using the multifunctional cyclic compound (B) with least two oxetanyl or epoxy radicals.As the multifunctional cyclic Compound (B), it is contemplated that the viscosity of resin combination, the low moisture-vapor transmission of solidfied material, low cure shrinkage, solidfied material High Tg etc., the cyclic compound (B) of the aliphatic ring preferably with aromatic ring or non-bridging.As the multifunctional cyclic chemical combination Thing (B), it is preferred that viscosity is below 1400mPas, is preferably below 1350mPas, and has above-mentioned formula (A-A) institute The cyclic compound (B) of the skeleton or the cycloalkanes hydrocarbon skeleton of the carbon number 5~7 of non-bridging shown as aromatic ring skeleton etc.. It is further preferred that viscosity is below 1400mPas, is preferably below 1350mPas, and with shown in above-mentioned formula (A-A) Skeleton is as aromatic ring skeleton, and epoxide with least two epoxy radicals or/and with least two epoxy radicals Alicyclic epoxy resin, it is further preferred that, viscosity is below 1350mPas, and has biphenyl backbone or bisphenol A skeleton Polyglycidyl ether compound and/or 3,4- epoxy hexane ylmethyls -3 ', 4 '-epoxy hexane formic acid esters.
In addition, according to circumstances, as cyclic compound (B), the oxygen with condensed cyclic structures such as fluorenes or carbazoles can also be used Oxetane compounds or epoxide.
As composition (B) alicyclic epoxy resin, from the aspect that viscosity is low, processability is good, curing rate is excellent It is preferable.In cycloaliphatic epoxy, the preferably cycloaliphatic epoxy of 2 functions, particularly preferred 3,4- epoxide rings Hexene ylmethyl -3 ', 4 '-epoxy hexane formic acid esters.
In addition, as needed can also use beyond composition (A) and composition (B) with condensed cyclic structures such as fluorenes or carbazoles Oxetane compound or epoxide, painting membrane rigidity can be assigned.These oxetane compounds or epoxy compound Thing can be used alone, and can also use two or more.
The curing agent (C) contained by resin combination in the present invention has reactivity with mentioned component (A) and/or (B). It can use and curing agent is used as by the energy-ray of light etc. or the compound of thermal initiation curing reaction.It can make in the present invention With curing agent (C) that is any, but generally preferably triggering curing reaction by energy-ray.
As the curing agent (C) for triggering curing reaction by energy-rays such as light, as long as by being subjected to ultraviolet (wavelength About 200~about 400nm) and produce the compound of cation, it is possible to use, can be enumerated for example without limitation：Cation Polymerization initiator, particularly light cationic polymerization initiator, it can illustrate：Sulfonium salt, iodineSalt,Salt, ammonium salt, stibate.
As sulfonium salt, can enumerate：Triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (five Fluorophenyl) borate, 4,4 '-bis- [diphenyl sulfonium] diphenyl sulfide-bis- hexafluorophosphates, 4,4 '-bis- [two (beta-hydroxy ethyoxyls) Phenyl sulfonium] diphenyl sulfide-bis- hexafluoro antimonates, 7- [two (p-methylphenyl) sulfoniums]-ITX hexafluorophosphate, 7- [two (p-methylphenyl) sulfoniums]-ITX hexafluoro antimonate, 7- [two (p-methylphenyl) sulfoniums] (five fluorine of -2- isopropyls four Phenyl) borate, phenylcarbonyl group -4 '-diphenyl sulfonium-diphenyl sulfide-hexafluorophosphate, phenylcarbonyl group -4 '-diphenyl sulfonium-two Diphenyl sulfide-hexafluoro antimonate, 4- tert-butyl-phenyls carbonyl -4 '-diphenyl sulfonium-diphenyl sulfide-hexafluorophosphate, 4- tert-butyl benzenes Base carbonyl -4 '-diphenyl sulfonium-diphenyl sulfide-hexafluoro antimonate, 4- tert-butyl-phenyls carbonyl -4 '-diphenyl sulfonium-diphenyl sulfide - Four (pentafluorophenyl group) borates, sulfur phenenyl diphenyl sulfonium hexafluoro antimonate, sulfur phenenyl diphenyl sulfonium hexafluorophosphate, 4- { 4- [2- Chlorobenzene formacyl] thiophenyl phenyl double (4- fluorophenyls) sulfonium hexafluoro antimonates, sulfur phenenyl diphenyl sulfonium hexafluoro antimonate halogenation Thing, 4,4 ', 4 "-three (beta-hydroxy ethoxyl phenenyl) sulfonium hexafluoro antimonates, 4,4 '-bis- [diphenyl sulfonium] diphenyl sulfide-bis- hexafluoros Stibate, diphenyl [4- (thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate, three [4- (4- acetylbenzenes sulfenyl) benzene Base] sulfonium three [(trifluoromethyl) sulfonyl] methanides etc..
As iodineSalt, it can enumerate：Diphenyl iodineFour (pentafluorophenyl group) borates, diphenyl iodineHexafluorophosphoric acid Salt, diphenyl iodineHexafluoro antimonate, two (4- nonyls phenyl) iodineHexafluorophosphate, (tri-isopropyl benzene base) iodineFour (five Fluorophenyl) borate etc..
AsSalt, it can enumerate：The normal-butyl of bromination three (2,5- dihydroxy phenyls)Hexadecyl tributylDeng.
As ammonium salt, can enumerate：Benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride, benzyltrimethylammonium bromide Deng.
As stibate, can enumerate：Triphenylsulfonium hexafluoro antimonate, to (thiophenyl) phenyl diphenyl sulfonium hexafluoro-antimonic acid The double hexafluoro antimonates of salt, 4- chlorphenyl diphenyl sulfoniums hexafluoro antimonate, double [4- (diphenyl sulfonium) phenyl] thioethers and diallyl IodineHexafluoro antimonate etc..
Trigger curing agent (C) (light cation of curing reaction as the energy-ray by light etc. used in the present invention Polymerization initiator), preferably salt compounded of iodine and sulfonium salt, wherein, preferably high sensitive and (the tri-isopropyl benzene base) that is easily obtained from market Iodine four (pentafluorophenyl group) borate, sulfur phenenyl diphenyl sulfonium hexafluoro antimonate, 4- { 4- [2- chlorobenzene formacyls] thiophenyl } benzene Base double (4- fluorophenyls) sulfonium hexafluoro antimonate, diphenyl [4- (thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate, three [4- (4- acetylbenzenes sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides etc..
In addition, in view of the regulation of the harmfulness and various countries to environment and human body, most preferably with (three without antimony element Cumenyl) iodine four (pentafluorophenyl group) borate, diphenyl [4- (thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphoric acid Salt, three [4- (4- acetylbenzenes sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides.
Relative to the mass parts of total amount 100 of composition (A)+composition (B), the content of light cationic polymerization initiator of the invention For 0.05~5 mass parts, preferably 0.1~3 mass parts.It should be noted that the present invention resin combination in, light sun from Sub- polymerization initiator can be used alone, and can also mix a variety of uses.
As thermal curing agents, can enumerate for example：Aminated compounds, anhydrides compound, amides compound, phenol generalization Compound, carboxylic acid compound etc..As the concrete example for the curing agent that can be used, can enumerate：Diaminodiphenyl-methane, two Ethylenetriamine, trien, diamino diphenyl sulfone, IPD, dicyanodiamide, by linolenic two Polyamide that polymers synthesizes with ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, Tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydro O-phthalic Acid anhydrides, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, bicyclic [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, hexamethylene -1,3,4- tricarboxylic acid -3,4- acid anhydrides, bisphenol-A, Bisphenol F, bisphenol S, bisphenol fluorene, Terpene diphenol, 4,4 '-xenol, 2,2 '-xenol, 3,3 ', 5,5 '-tetramethyl-[1,1 '-biphenyl] -4,4 '-glycol, quinhydrones, Benzenediol, naphthalenediol, three (4- hydroxy phenyls) methane, 1,1,2,2- tetra- (4- hydroxy phenyls) ethane, (phenol, alkyl take phenols Substituting phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) with formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, Salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 '-bis- (chloromethyl) -1, 1 '-biphenyl, 4,4 '-bis- (methoxies) -1,1 '-biphenyl, 1,4 '-bis- (chloromethyl) benzene, 1,4 '-bis- (methoxy) benzene Deng condensation polymer and halogenated bisphenol class, imidazoles, trifluoroboranes-amine complex, the guanidine such as their modifier, tetrabromobisphenol A spread out Condensation product of biology, terpenes and phenols etc., but it is not limited to these.They can be used alone, and can also use two or more.
In addition, in encapsulant, particularly organic EL face sealing, in most cases preferably using the transparency after solidification Excellent acid anhydrides, preferably methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic acid Acid anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, bicyclic [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, methyl bicycle [2.2.1] heptane -2,3- dicarboxylic acid anhydrides, hexamethylene -1,3,4- tricarboxylic acid -3,4- acid anhydrides etc. have the acid anhydrides of alicyclic ring skeleton.These Acid anhydrides with alicyclic skeleton can use commercially available product, such as can be obtained from gas chemical company of Mitsubishi etc. as H-TMA The solid-state product or liquid product (being semisolid at room temperature although being liquid product, operability is excessively poor) of series.
In addition, using hexamethylene -1,3, in the case of 4- tricarboxylic acid -3,4- acid anhydrides, when being used alone, due to for solid-state Or the semisolid that viscosity is high, therefore operational extreme difference sometimes.It is therefore preferable that with other curing agent, be preferably there is ester ring type bone The acid anhydrides of frame is used in combination.Now, as the curing agent that can be used together, as long as being liquid and the low curing agent of viscosity, just without special Limitation, such as commercially available curing agent, can enumerate：HNA-100 containing methylnadic anhydride, carbic anhydride is (new Japan Chemical (strain) is made) or RIKACID MH700 containing hexahydrophthalic anhydride, methylhexahydrophthalic anhydride it is (new Japan Chemical (strain) make) etc. curing agent.And the used time, can in advance by solid or hexamethylene -1,3 of semisolid, 4- tricarboxylic acids - 3,4- acid anhydrides and the curing agent of low viscosity in room temperature or are heated (as heating condition, in order to prevent curing agent from volatilizing, preferably 150 Below DEG C, more preferably less than 120 DEG C) under the conditions of mix to uniform, thus turn into the good state of operability.In addition, from After reason operability and solidification from the viewpoint of the depression of encapsulant, hexamethylene -1,3,4- tricarboxylic acids -3,4- acid anhydride is in whole solidifications Usage rate in agent is 20~90 mass %, the preferably scope below 30~80 mass %.Mixed proportion is more than 90 matter When measuring %, the operational extreme difference of curing agent.In addition, when being less than 20 mass %, it is possible to changing in terms of the depression of encapsulant Kind effect diminishes.
Using the match ratio of the system of the thermal curing agents of the present invention, according in epoxide or oxetane compound The equivalent of contained functional equivalent and the carboxyl of carboxylic acids curing agent determines.Preferably with respect to the equivalent of functional group 1, carboxyl For 0.2~5 equivalent, more preferably 0.5~2 equivalent.During more than the scope, curing reaction can not be carried out fully, and be produced The functional group of amount, the residual of carboxyl, therefore the toughness of solidfied material, heat resistance can not give full play to.
In the resin combination of the present invention, curing catalysts can be used in combination together with curing agent, or be used alone Curing catalysts and without using curing agent.As the concrete example for the curing accelerator that can be used, can enumerate：2- methyl miaows Azoles, 2- phenylimidazoles, 2- lauryls imidazoles, 2- heptadecyl imidazoles, 2- phenyl -4-methylimidazole, 1- benzyl -2- phenyl miaows Azoles, 1 benzyl 2 methyl imidazole, 1- cyano ethyls -2-methylimidazole, 1- cyano ethyl -2- phenylimidazoles, 1- cyano ethyls - 2- undecyl imidazoles, 2,4- diaminourea -6- (2 '-methylimidazole (1 ')) ethyl s-triazine, 2,4- diaminourea -6- (2 '-ten one Alkyl imidazole (1 ')) ethyl s-triazine, 2,4- diaminourea -6- (2 '-ethyl, 4-methylimidazole (1 ')) ethyl s-triazine, 2,4- Diaminourea -6- (2 '-methylimidazole (1 ')) ethyl s-triazine isocyanuric acid adduct, the 2 of 2-methylimidazole isocyanuric acid：3 Addition product, 2- phenylimidazoles isocyanuric acid adduct, 2- phenyl -3,5- bishydroxymethyls imidazoles, 2- phenyl -4- hydroxymethyls - The various imidazoles and those imidazoles of 5- methylimidazoles, 1- cyano ethyl -2- phenyl -3,5- dicyano ethoxyl methyl imidazoles Class and phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, Pyromellitic Acid, naphthalenedicarboxylic acid, maleic acid, grass Amide-type, 1,8- diazabicyclos (5.4.0) the grade diazas of laurylene -7 such as the salts of the polybasic carboxylic acids such as acid, dicyanodiamide The salt of the salts of compound and their tetraphenyl borate salts, phenol novolacs etc., above-mentioned polybasic carboxylic acid class or phosphonic acid The hot cationic initiator of the ammonium salt class such as class, TBAB, cetyl trimethylammonium bromide, tricaprylmethyl ammonium bromide, Triphenylphosphine, three (tolyl) phosphines, tetraphenylphosphonibromide bromideThe phosphines such as tetraphenylphosphoniphenolate tetraphenyl borate salts,Compounds heat sun Ionic initiator, 1- naphthyl methyls methyl-p-hydroxybenzene sulfonium hexafluoro antimonate, benzyl methyl-p-hydroxybenzene sulfonium hexafluoro antimony Hydrochlorate, dimethyl-to the hot cationic initiators of metaantimmonic acid salt such as acetoxyl group phenyl sulfonium hexafluoro antimonate, 1- naphthyl methyl first Base-p-hydroxybenzene sulfonium hexafluorophosphate, benzyl methyl-p-hydroxybenzene sulfonium hexafluorophosphate, dimethyl-to acetyloxy phenyl Base sulfonium hexafluorophosphate etc.It is the phenols such as the hot cationic initiator of salt, 2,4,6- triamido methylphenols, amine additives, pungent Metallic compounds such as sour tin etc. and by microcapsule-type curing accelerator etc. obtained from these curing accelerator microencapsulations.Make It is any with those curing accelerators, can be according to the transparent resin obtained such as the transparency, curing rate, operating condition Characteristic required by composition and suitably select.Preferably hot cationic initiator, particularly preferablyThe hot cation of salt draws Send out agent.Relative to the mass parts of total amount 100 of composition (A)+composition (B), curing accelerator is generally in the model of 0.001~15 mass parts Enclose interior use, preferably 0.01~5 mass parts.
In the present invention, and with the redox reaction of the cracking type Photoepolymerizationinitiater initiater used in radical polymerization system It is and effective.In the case of paralled system, the generation easiness decision of single Electron Transfer Reactions is reactive, and LUMO is (minimum Unoccupied orbital：Index as the generation easiness of electron transfer reaction) the low iodine of energy levelThe reactivity of salt is good.As long as It is cracking type Photoepolymerizationinitiater initiater, arbitrary Photoepolymerizationinitiater initiater, can enumerates for example：2- hydroxy-2-methyls-phenyl third Alkane -1- ketone, 1- hydroxycyclohexylphenylketones.
As the curing agent used in the present invention, the thermal history to member of formation is considered, if heat cure, then preferably exist Less than 100 DEG C are solidified, preferably using hot cationic polymerization.In addition, it is also preferred that using the light sun without heat energy from Sub- polymerization initiator.
As needed and particulate can be used in the resin combination of the present invention.
As the particulate, can enumerate：Organic fine particles, inorganic particles.In addition, for particulate, it may be considered that required The light transmittance wanted, hardness, marresistance, cure shrinkage, refractive index, individually or a variety of uses of mixing.
As the organic fine particles that can be used for the present invention, can enumerate：Polystyrene resin bead, acrylic resin are small It is the organic polymer pellets such as ball, polyurethane resin bead, polycarbonate resin bead, expanded polystyrene resin beads, porous The porous organic polymer beads such as acrylic resin bead, cellular polyurethane resin beads, porous polycarbonate resin beads, Toner, toner, the melocol of phenyl guanamines-carbamide condensation product of phenyl guanamine-formaldehyde condensation product The toner of condensation product, the powder of aspartate derivatives, zinc stearate powder, stearic amide powder, epoxy resin Powder, polyethylene powders etc., preferably crosslinked polymethylmethacrylaparticles resin beads, crosslinked polymethylmethacrylaparticles benzene second Olefine resin bead etc..These organic fine particles can be obtained easily as commercially available product, in addition, also referring to known document system It is standby.
As the inorganic particles that can be used for the present invention, can enumerate：Conductive metal oxide, transparent metal oxide Thing, other inorganic fillers etc..
As the conductive metal oxide that can be used for the present invention, can enumerate：Zinc antimonates, doped sno_2 indium oxide (ITO), antimony-doped tin oxide (ATO), antimony pentaoxide, tin oxide, aluminium-doped zinc oxide, Ga-doped zinc oxide, Fluorin doped oxidation Tin etc..
As the transparent metal oxide that can be used for the present invention, can enumerate：Silica, titanium oxide, zirconium oxide, oxygen Change cerium, zinc oxide, iron oxide, titanium oxide/zirconium oxide/tin oxide/antimony pentaoxide compound, zirconium oxide/tin oxide/antimony pentaoxide Compound, titanium oxide/zirconium oxide/oxidation tin composite etc..
As the other inorganic fillers that can be used for the present invention, can enumerate：Calcium oxide, calcium chloride, zeolite, silica gel etc..
As the particulate that can be used for the present invention, preferred hardness and the high particulate of excellent abrasion, refractive index can be with excellent Choosing using titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconium oxide/tin oxide/antimony pentaoxide compound, Zirconium oxide/tin oxide/antimony pentaoxide compound, titanium oxide/zirconium oxide/oxidation tin composite.In addition, the optics for display Piece requires high light transmittance, therefore preferred below the 100nm of primary particle size of particulate.As their mixing ratio, relative into The mass parts of total amount 100 for dividing (A)+composition (B) are 1~30 mass parts, preferably 5~20 mass parts.
In addition it is also possible to and with polybasic carboxylic acid class dispersant, silane coupler, titanate esters system coupling agent, modified silicon oil etc. The dispersant as particulate such as polysiloxane-based dispersant, organic copolymer species dispersant.Matching somebody with somebody during as these materials of cooperation Composition and division in a proportion example, the gross mass relative to the resin combination of the present invention is about 0.001~about 30 mass %, preferably from about 0.05~about 5 mass %.
It should be noted that the minimum particle diameter that its particle has when primary particle size refers to break up aggregation.That is, in ellipse Particulate in the case of, using minor axis as primary particle size.Primary particle size can pass through dynamic light scattering method, electron microscope observation Etc. being measured.Specifically, Jeol Ltd. JSM-7700F electric field emission type scanning electron microscopies can be used Mirror, primary particle size is determined under the conditions of accelerating potential 30kV.
These particulates can disperse to use in a solvent.Particularly inorganic particles are easily to be dispersed in water or organic solvent Form obtains commercially available product.As used organic solvent, can enumerate：The fragrance such as toluene, dimethylbenzene, ethylbenzene, durol It is the aliphatic hydrocarbon solvents such as race's hydrocarbon solvent, hexane, octane, decane and the petroleum ether as their mixture, unleaded gas, molten Agent naphtha etc.；As esters solvent, can enumerate：The alkyl acetate such as ethyl acetate, propyl acetate, butyl acetate class, γ- The ring-type such as butyrolactone esters, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether list second Acid esters, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, fourth two (single or poly-) the alkylene glycol monoalkyl ethers monoacetate such as alcohol monomethyl ether monoacetate class, dialkyl glutarate, butanedioic acid Polybasic carboxylic acid alkyl esters such as dialkyl ester, hexanedioic acid dialkyl ester etc.；As ether solvent, can enumerate：Ether, methyl fourth The alkyl ethers such as base ether, glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, three second two The ring-type ethers such as glycol ethers, the tetrahydrofurans such as diethylene glycol dimethyl ether, triethylene glycol diethyl ether；As ketones solvent, can enumerate：Third Ketone, methyl ethyl ketone, cyclohexanone, isophorone etc..
In addition, in the resin combination of the present invention, it is contemplated that the viscosity of obtained resin combination of the invention, refraction Rate, adhesiveness etc., in addition to composition (A), composition (B), reactive compounds can also be used.Specifically, can enumerate： (methyl) acrylate, as (methyl) acrylate, simple function (methyl) acrylate, 2 functions (methyl) can be used Acrylate, intramolecular have multifunctional (methyl) acrylate, polyester (methyl) propylene of more than 3 (methyl) acryloyl groups Acid esters, epoxy (methyl) acrylate etc..
As simple function (methyl) acrylate, such as can enumerate：(methyl) isobornyl acrylate, (methyl) propylene Sour tetrahydrochysene dicyclopentadiene base ester, (methyl) propylene acid dihydride dicyclopentadiene base ester, (methyl) propylene acid dihydride dimerization Cyclopentadienyl group epoxide ethyl ester, (methyl) cyclohexyl acrylate etc. ester ring type (methyl) acrylate, (methyl) acrylic acid tetrahydrochysene Chaff ester, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, morpholine (methyl) acrylate etc. have (methyl) propylene of heterocycle Acid esters, (methyl) benzyl acrylate, ethyoxyl are modified cresols (methyl) acrylate, propoxyl group is modified cresols (methyl) acrylic acid Ester, neopentyl glycol benzoic ether (methyl) acrylate, o-phenyl phenol (methyl) acrylate, o-phenyl phenol monosubstituted ethoxy (methyl) acrylate, o-phenyl phenol polyethoxy (methyl) acrylate, p-phenyl phenol (methyl) acrylate, to benzene Base phenol monosubstituted ethoxy (methyl) acrylate, p-phenyl phenol polyethoxy (methyl) acrylate, acrylic acid-adjacent phenyl benzyl Ester, acrylic acid-to (methyl) acrylate, carbazole (poly-) ethyoxyl (methyl) acrylic acid with aromatic rings such as phenyl benzyl ester Ester, carbazole (poly-) propoxyl group (methyl) acrylate, (poly-) caprolactone modification carbazole (methyl) acrylate etc. have heterocycle (methyl) acrylate, (methyl) acrylic acid naphthalene ester, (poly-) ethyoxyl (methyl) acrylic acid naphthalene ester, (poly-) propoxyl group (methyl) third Olefin(e) acid naphthalene ester, (poly-) caprolactone modification (methyl) acrylic acid naphthalene ester, dinaphthol (methyl) acrylate, dinaphthol (poly-) ethyoxyl (methyl) acrylate, dinaphthol (poly-) propoxyl group (methyl) acrylate, (poly-) caprolactone modification dinaphthol (methyl) propylene Acid esters, naphthols (methyl) acrylate, naphthols (poly-) ethyoxyl (methyl) acrylate, naphthols (poly-) propoxyl group (methyl) propylene (methyl) acrylate with condensed ring such as acid esters, (poly-) caprolactone modification naphthols (methyl) acrylate, with imide ring Acid imide (methyl) acrylate of structure, butanediol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (first Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, DPG (first Base) acrylate etc. has (methyl) acrylate, (methyl) acrylate, (methyl) acrylic acid of hydroxyl Butoxyethyl, caprolactone (methyl) acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Acrylic acid octafluoro pentyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) third The different monooctyl ester of olefin(e) acid, (methyl) 2-EHA, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, (first Base) the different myristin of acrylic acid, (methyl) lauryl acrylate etc. have (methyl) acrylate, the ethyoxyl diethyl two of alkyl Alcohol (methyl) acrylate, 2- ethylhexyls carbitol (methyl) acrylate, polyethylene glycol (methyl) acrylate, poly- the third two (methyl) acrylate of polyalcohol such as alcohol (methyl) acrylate etc..
As (methyl) acrylate monomer with 2 functional groups, can enumerate：Hydrogenate neovaleraldehyde and be modified trihydroxy methyl Propane two (methyl) acrylate etc. has (methyl) acrylate, (methyl) third of (poly-) ethyoxyl modified bisphenol A two of heterocycle Olefin(e) acid ester, (poly-) propoxyl group modified bisphenol A two (methyl) acrylate, (methyl) acrylic acid of (poly-) ethyoxyl modified bisphenol F bis- Ester, (methyl) acrylate of (poly-) propoxyl group modified bisphenol F bis-, (methyl) acrylate of (poly-) ethyoxyl modified bisphenol S bis-, (methyl) acrylate of (poly-) propoxyl group modified bisphenol S bis-, hexahydrophthalic acid two (methyl) acrylate, double phenoxy groups (methyl) acrylate with aromatic rings such as (poly-) ethyoxyl fluorenes, biphenyl dimethanol two (methyl) acrylate etc. are with heterocycle (methyl) acrylate, dinaphthol two (methyl) acrylate, (methyl) acrylate of dinaphthol (poly-) ethyoxyl two, dinaphthalene (methyl) acrylate of phenol (poly-) propoxyl group two, (poly-) caprolactone modification dinaphthol two (methyl) acrylate etc. have condensed ring (methyl) acrylate, bisphenol fluorene two (methyl) acrylate, (methyl) acrylate of double phenoxy group methanol fluorenes two, double phenoxy groups Ethanol fluorenes two (methyl) acrylate, (methyl) acrylate of double phenoxy group caprolactone fluorenes two etc. have (the first of Ppolynuclear aromatic Base) isocyanates such as acrylate, diacrylated isocyanuric acid ester acrylate, 1,4- butanediols two (methyl) propylene Acid esters, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, the poly- (first of 1,4- butanediols two Base) acrylate etc. has (methyl) acrylate, Tricyclodecane Dimethanol (methyl) acrylate of straight chain methylene structure Deng ester ring type (methyl) acrylate, ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propane diols Two (methyl) acrylate of polyalcohol such as two (methyl) acrylate, polypropylene glycol two (methyl) acrylate etc..
As multifunctional (methyl) acrylate monomer, can enumerate：Three (acryloyl-oxyethyl) isocyanuric acid esters, (poly-) caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester etc. has multifunctional (methyl) third of isocyanurate ring Olefin(e) acid ester, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (poly-) ethyoxyl are modified Ji Wusi Alcohol four (methyl) acrylate, (poly-) propoxyl group are modified pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Acrylate, (poly-) caprolactone modification dipentaerythritol five (methyl) acrylate, (poly-) ethyoxyl are modified dipentaerythritol five (methyl) acrylate, (poly-) propoxyl group are modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, (poly-) caprolactone modification dipentaerythritol six (methyl) acrylate, (poly-) ethyoxyl are modified the (first of dipentaerythritol six Base) acrylate, (poly-) propoxyl group be modified dipentaerythritol six (methyl) acrylate, more (methyl) acrylic acid of polypentaerythritol Ester, trimethylolpropane tris (methyl) acrylate, (poly-) ethyoxyl be modified trimethylolpropane tris (methyl) acrylate, (poly-) propoxyl group is modified trimethylolpropane tris (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, sweet Multifunctional (methyl) acrylate of the polyalcohols such as oily three (methyl) acrylate, tricresyl phosphate (methyl) acrylate etc. are phosphorous more Function (methyl) acrylate etc., trimethylolpropane benzoic ether (methyl) acrylate etc. have aromatic multifunctional Modified multifunctional (methyl) acrylate of the acid such as (methyl) acrylate, the acryloyloxymethyl butanedioic acids of 2,2,2- tri-, poly- silicon Oxygen alkane six (methyl) acrylate etc. has multifunctional (methyl) acrylate of silicone matrix etc..
As carbamate (methyl) acrylate, can enumerate：Make diatomic alcohol compounds (such as：Ethylene glycol, diethyl Glycol, triethylene glycol, propane diols, DPG, tripropylene glycol, 1,4- butanediols, neopentyl glycol, 1,6-HD, 1,8- are pungent Glycol, 1,9- nonanediols, 2- methyl isophthalic acids, 8- ethohexadiols, 3- methyl isophthalic acids, 5- pentanediols, 2,4- diethyl -1,5- pentanediols, 2- Butyl -2- ethyl -1,3- propane diols, hexamethylene -1,4- dimethanols, polyethylene glycol, polypropylene glycol, bisphenol-A polyethoxy glycol, Polymer with bis phenol A propoxyl group glycol etc.) or as these diatomic alcohol compounds and binary acid or its acid anhydrides (such as：Butanedioic acid, oneself two Acid, azelaic acid, dimeric dibasic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid or their acid anhydrides) reaction product it is poly- Ester dihydric alcohol, with organic multiple isocyanate (such as：Tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4- tri- It is the chain saturated hydrocarbons such as methyl hexamethylene diisocyanate, 2,4,4- trimethyl hexamethylene diisocyanates isocyanates, different Isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methyl hydride diisocyanate, di-2-ethylhexylphosphine oxide (4- cyclohexyl Isocyanates), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate etc. Cyclic saturated hydrocarbon isocyanates, 2,4 toluene diisocyanate, 1,3- eylylene diisocyanates, to the isocyanide of phenylene two Acid esters, 3,3 '-dimethyl -4,4 '-diisocyanate, 6- isopropyl -1,3- phenyl diisocyanates, 1,5- naphthalene diisocyanates Deng aromatic poly-isocyanate) reaction, reaction product etc. obtained from then addition contains (methyl) acrylate of hydroxyl.
As polyester (methyl) acrylate, can enumerate：As the anti-of diatomic alcohol compounds and binary acid or its acid anhydrides Answer the polyester diol of product and the reaction product of (methyl) acrylic acid etc..
Wherein, (methyl) acrylate as the resin combination that can be used for the present invention, preferably using cure shrinkage The low material of rate.And specifically, it is preferable to (methyl) acrylate with ring structure, can be enumerated：(methyl) isobomyl acrylate Ester, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, (methyl) propylene acid dihydride dicyclopentadiene base ester, (methyl) third Olefin(e) acid dihydro dicyclopentadiene base epoxide ethyl ester, (methyl) cyclohexyl acrylate, p-Cumenylphenol (poly-) ethyoxyl (first Base) acrylate, naphthols (poly-) ethyoxyl (methyl) acrylate, naphthols (poly-) propoxyl group (methyl) acrylate, phenyl benzene Phenol (poly-) ethyoxyl (methyl) acrylate, phenylphenol (poly-) propoxyl group (methyl) acrylate, (methyl) benzyl acrylate, Tricyclodecane Dimethanol (methyl) acrylate, hydrogenation neovaleraldehyde are modified trimethylolpropane two (methyl) acrylate, biphenyl Dimethanol two (methyl) acrylate etc..Phenylphenol (poly-) second that the Tg of particularly preferably solidfied material is high, cure shrinkage is low Epoxide (methyl) acrylate, Tricyclodecane Dimethanol (methyl) acrylate, hydrogenation neovaleraldehyde are modified trimethylolpropane two (methyl) acrylate, biphenyl dimethanol two (methyl) acrylate.It should be noted that in the resin combination of the present invention In, (methyl) acrylate as other compositions can be used alone, and can also mix a variety of uses.Coordinate in the present invention Use level during (methyl) acrylate, it is that 100 mass parts are 10~200 mass parts relative to composition (A)+composition (B), preferably For 50~150 mass parts.
In addition, when using (methyl) acrylate, preferably gathered using the light beyond above-mentioned light cationic polymerization initiator Close initiator.Specifically, can enumerate：Benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether Etc. benzoin class；Acetophenone, 2,2- diethoxy -2- phenyl acetophenones, 2,2- diethoxy -2- phenyl acetophenones, 1,1- bis- Chloro-acetophenone, 2- hydroxy-2-methyls-phenyl-propane -1- ketone, diethoxy acetophenone, 1- hydroxycyclohexylphenylketones, 2- first Base -1- [4- (methyl mercapto) phenyl] -2- morpholinopropane -1- ketone, oligomeric [2- hydroxy-2-methyls -1- [4- (1- ethylene methacrylics Base) phenyl] acetone] and etc. acetophenones；The Anthraquinones such as 2- EAQs, 2- tert-butyl groups anthraquinone, 2- chloroanthraquinones, 2- amyl anthraquinones； The thioxanthene ketone class such as 2,4- diethyl thioxanthones, ITX, CTX；Acetophenone dimethyl ketal, benzyl two The ketal class such as methyl ketal；Benzophenone, 4- benzoyls -4 '-methyldiphenyl thioether, 4,4 '-bis- methylamino benzophenone Deng benzophenone；2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, double (2,4,6- trimethylbenzoyls)-phenyl oxygen Change phosphinoxides such as phosphine, diphenyl-(2,4,6- trimethylbenzoyls) phosphine oxide etc..Preferably acetophenones, more preferably may be used To enumerate：2- hydroxy-2-methyls-phenyl-propane -1- ketone, 1- hydroxycyclohexylphenylketones.Trigger using the radical polymerization In the case of agent, relative to the mass parts of (methyl) acrylate component 100, preferably 0.1~10 mass parts.More preferably 1~5 Mass parts.It should be noted that in the resin combination of the present invention, Photoepolymerizationinitiater initiater can be used alone, and can also mix Close a variety of uses.
The use ratio of each composition of the resin combination of the present invention can contemplate desired refractive index, durability, glue Degree, adhesiveness etc. and determine.
Generally, when composition (A)+composition (B) is set into 100 mass parts, the content of composition (A) is 20~80 mass parts, Preferably 30~70 mass parts.The content of composition (B) is 20~80 mass parts, preferably 30~70 mass parts.If hot sun Ionic initiator, then the content of composition (C) is 0.05~5 mass parts, preferably 0.1~3 mass parts.
Relative to the total amount of the resin combination of the present invention, the total amount of usual composition (A)+composition (B) is preferably from about 50 ~about 99 mass %, more preferably 70~99 mass %, more preferably 80~99 mass %, according to circumstances can be 90~ 99 mass %, can also be 95~99 mass %.Remainder is mentioned component (C) and optional adding ingredient.
In the resin combination of the present invention, in addition to mentioned component, convenience during in order to improve processing etc., according to Situation, it can be used together containing releasing agent, defoamer, levelling agent, light stabilizer, antioxidant, polymerization inhibitor, plasticizer, antistatic Agent etc..
In addition, in order to obtain durability, flexibility, it is also many using the example of plasticizer.As used material, according to Desired viscosity, durability, the transparency, flexibility etc. are selected.Specifically, can enumerate：The alkene such as polyethylene, polypropylene Birds of the same feather flock together compound, repefral, diethyl phthalate, dibutyl phthalate, (the 2- second of phthalic acid two Base hexyl) ester, diisooctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, adjacent benzene two The adjacent benzene such as formic acid dicyclohexyl maleate, glycolic ethylphthalyl ethyl glycolate ethyl ester, ethanol acid butyl phthalyl butyl ester The trimellitates such as dicarboxylic acid esters, tri trimellitate (2- ethylhexyls) ester, dibutyl adipate, diisobutyl adipate, oneself Diacid two (2- ethylhexyls) ester, diisononyl adipate, diisodecyl adipate (DIDA), (2- (the 2- butoxy ethoxies of adipic acid two Base) ethyl) ester, azelaic acid two (2- ethylhexyls) ester, dibutyl sebacate, decanedioic acid two (2- ethylhexyls) ester, butanedioic acid The fatty group dibasic acids such as diethylester, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2- ethylhexyls) phosphorus Acid esters, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, cresyl phosphate diphenyl ester, phosphoric acid 2- ethylhexyls The polyester such as the ricinoleate esters such as the orthophosphates such as diphenyl ester, acetyl group methyl ricinolcic acid, poly- (1,3 butylene glycol adipate ester), The sulfonamide such as the acetic acid esters such as glyceryl triacetate, N-butylbenzenesulfonamide, polyethylene glycol benzoic ether, polyethylene glycol dibenzoic acid Ester, polypropylene glycol benzoic ether, dibenzonate, poly- 1,4- butanediols benzoic ether, poly- 1,4- butanediols benzene first The polyethers such as the polyalkylene oxides such as acid esters (two) benzoic ether, polypropylene glycol, polyethylene glycol, poly- 1,4- butanediols, polyethoxy are modified The poly-alkoxyl modified bisphenol As such as bisphenol-A, poly- propoxyl group modified bisphenol A, polyethoxy modified bisphenol F, poly- propoxyl group modified bisphenol The Ppolynuclear aromatics such as the poly-alkoxyl modified bisphenol such as F F, naphthalene, phenanthrene, anthracene, (connection) naphthols, (poly-) ethyoxyl be modified (connection) naphthols, (poly-) propoxyl group is modified (connection) naphthols, (poly-) 1,4- butanediols are modified the naphthalenes such as (connection) naphthols, (poly-) caprolactone modification (connection) naphthols Amphyl, diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, rhenocure CA, morpholinodithio benzo Thiazole, cyclohexylbenzothiazole -2- sulfenamides, tetramethylthiuram disulfide, tetraethylthiuram disulfide, curing four Butyl thiuram, curing four (2- ethylhexyls) thiuram, tetramethylthiuram monosulfide, tetra-sulfurized pair pentamethylene autumn are blue The sulfur-containing compounds such as nurse.Preferably (poly-) ethylene glycol phenyl formic acid esters, (poly-) propylene glycol phenyl formic acid esters, dinaphthol, (poly-) ethyoxyl Modified (connection) naphthols, (poly-) propoxyl group are modified (connection) naphthols, diphenyl sulfide.
In order to improve adhesive tension, coupling agent can be added.For used coupling agent, it is not particularly limited, but preferably Contain silane coupler.As silane coupler, can enumerate for example：3- glycidoxypropyltrime,hoxysilanes, 3- rings Oxygen propoxypropyl methyl dimethoxysilane, 3- glycidoxypropyls dimethoxysilane, 2- (3,4- epoxy hexamethylenes Base) ethyl trimethoxy silane, N- phenyl-gamma-amino propyl trimethoxy silicane, N- (2- amino-ethyls) 3- aminopropyl first Base dimethoxysilane, N- (2- amino-ethyls) 3- TSL 8330s, APTES, 3- Mercaptopropyi trimethoxy silane, vinyltrimethoxy silane, N- (2- (vinyl-benzylamino) ethyl) 3- aminopropyls Trimethoxy silane hydrochloride, 3- methacryloxypropyl trimethoxy silanes, 3- chloropropylmethyldimethoxysilanes, The silane couplers such as 3- r-chloropropyl trimethoxyl silanes, isopropyl (N- ethylaminoethyls amino) titanate esters, isopropyl three are different Stearyl titanate esters, two (dioctylphyrophosphoric acid) fluoroacetic acid titaniums, tetra isopropyl two (dioctyl phosphito ester) titanate esters, new alkane The titanium class coupling agents such as epoxide three (p- N- (beta-aminoethyl) aminophenyl) titanate esters, acetylacetone,2,4-pentanedione zirconium, methacrylic acid zirconium, Propionic acid zirconium, new alkoxy zirconium ester, three new trineodecanoyl zirconate of new alkoxy, new alkoxy three (dodecanoyl) benzenesulfonyl zirconium Acid esters, new alkoxy three (ethylene amino-ethyl) zirconate, new alkoxy three (m-aminophenyl base) zirconate, zirconium carbonate The zirconiums such as ammonium, aluminium acetylacetonate, aluminium methacrylate, propionic acid aluminium or aluminium class coupling agent, they can be used alone, and can also mix Two or more is used.In these coupling agents, preferably silane coupling agent, more preferably amino silicone alkanes coupling agent or epoxy radicals Silane coupling agent.By using coupling agent, it can obtain that moisture-proof reliability is excellent, the reduction of adhesive strength after moisture absorption is few Encapsulant.The content of the coupling agent is about 0.05~about 3 mass parts relative to the mass parts of reactive resin compositions 100.
In addition, as needed, can also add acrylic polymer, polyester elastomer, urethane polymer and Nitrile rubber etc. polymerize species.For the composition without reactive group, from the aspect of compatibility, weight average molecular weight is preferred For 10,000g/mol.In addition, in order to reduce moisture-vapor transmission, the organo-metallic compounds such as alkyl aluminum can also be added.Also may be used To add solvent, but preferably do not add solvent.
In the resin combination of the present invention, the weight average molecular weight of each composition is preferably 10, below 000g/mol, more preferably For below 5,000g/mol.Because the big composition of weight average molecular weight does not dissolve, thus the resin combination prepared becomes muddiness Liquid.Because the resin combination for display must be uniform and transparent, therefore it is unsuitable.In addition, for saturating The characteristic that rate also requires excellent is crossed, specifically, the light transmittance of each wavelength in the range of 380~780nm of optimal wavelength is 90% More than.Light transmittance can be determined by sensing equipments such as Co., Ltd. Hitachi high-tech spectrophotometer U-3900H.
The resin combination of the present invention can be according to conventional methods by prepared by each composition mixed dissolution.Such as can be with By the way that each composition input is carried in the round-bottomed flask of agitating device, thermometer, and stirred 0.5~6 hour at 40~80 DEG C And obtain.
The viscosity of the resin combination of the present invention needs the operational of processability during to be suitable for manufacturing display etc. Viscosity, it is especially suitable for the viscosity of the face sealing of organic EL element.Organic EL element is usually formed following structure：By cofferdam material Expect in the region that surrounds, stacked gradually on the substrates such as glass since the substrate-side metal electrode, organic carrier transport layer, Organic EL luminescent layers, ITO electrode, passivating film, filled on the passivating film with packing material (face resin composition for encapsulating), Further sealed thereon with hermetic sealing substrates such as glass.The packing material is filled into the opposite to that side of substrate of above-mentioned metal electrode side Hermetic sealing substrate between space, play a part of protecting organic luminous layer from moisture of outside etc., usually using curability Resin combination, after filling the resin combination, the hermetic sealing substrates such as glass are generally loaded, then make resin composition, from And seal organic luminous layer.Therefore, in order to which the gap between aforesaid substrate is fully sealed, the resin combination is preferably low viscous Degree.
The viscosity is preferably to use E type viscosimeters (TV-200：Dong Ji industry companies system) viscosity that is determined at 25 DEG C is Below, more preferably below 1300mPas, more preferably below 700mPas are special by 1.5Pas (1500mPas) You Xuanwei not below 400mPas.Lower limit is not particularly limited, typically about 50mPas.
In the present invention, the resin combination containing the curing agent for triggering curing reaction by energy-ray can pass through energy Amount ray easily makes its solidification.Here, the concrete example as energy-ray, can be enumerated：Ultraviolet, visible ray, infrared ray, Particle rays such as the electromagnetic waves such as X ray, gamma-radiation, laser, α-ray, beta rays, electron ray etc..In the present invention, at this Among a little, preferably ultraviolet, laser, visible ray or electron ray.
According to conventional methods, by irradiating above-mentioned energy-ray to the resin combination of the present invention, the present invention can be obtained Solidfied material.The liquid refractivity of the resin combination of the present invention is usually 1.45~1.70, and preferably 1.50~1.65.Refraction Rate can use Abbe refractomecer (model：DR-M2, Co., Ltd.'s ア タ go systems) etc. measure.
In addition, the shrinkage factor (cure shrinkage) during the solidification of the resin combination of the present invention is the smaller the better, preferably 5% Hereinafter, more preferably less than 4%, more preferably less than 3.5%.
In addition, in order to protect organic luminous layer from moisture etc. of outside, the solidfied material of resin combination of the invention Moisture-vapor transmission is 50g/m224 hours (under conditions of 60 DEG C, humidity 90% measure, similarly hereinafter) below, preferably 35g/ m2Less than 24 hours, more preferably 30g/m2Less than 24 hours, it is further preferably no larger than 30g/m224 hours.
In addition, the glass transition temperature of solidfied material is preferably up to a certain degree, in the present invention, the Tg is preferably 40 DEG C More than, more preferably more than 45 DEG C, most preferably more than 50 DEG C.
The preferred embodiment of the resin combination of the present invention is recorded below.
I. the resin combination that a kind of face for organic el display seals, its contain following aromatic compounds (A), Cyclic compound (B) (wherein, in the case of the skeleton in the group described in B-2, be with as aromatic compound (A) the different compound of the compound that uses) and curing agent (C)；
Aromatic compound (A) is with selected from as the skeleton shown in above-mentioned formula (A-A), the bone shown in above-mentioned formula (A-B) The aromatic series of at least one of the group of frame, anthracene skeleton and luxuriant and rich with fragrance skeleton composition skeleton and oxetanyl or epoxy radicals Compound (A)；
Cyclic compound (B) is with least one in the group described in following B-2 or the group described in following B-3 Kind skeleton and oxetanyl or the cyclic compound or alicyclic epoxy resin of epoxy radicals；B-2：Phenyl, biphenyl, Naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S；B-3：Isobornyl, adamantane, pentamethylene, hexamethylene, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
Ii. the resin combination described in above-mentioned i, wherein, aromatic compound (A) and cyclic compound (B) any one Include the compound at least with an oxetanyl or epoxy radicals.
Iii. the resin combination described in above-mentioned i or ii, wherein, aromatic compound (A) be with select free phenyl, connection Aromatic compound (A) of the skeleton as aromatic backbone in the group of benzene and bisphenol-A composition.
Iv. the resin combination any one of above-mentioned i~iii, wherein, aromatic compound (A), which includes, has one Individual oxetanyl or the aromatic compound of epoxy radicals (A).
V. the resin combination any one of above-mentioned i~iv, wherein, aromatic compound (A), which includes, has one The aromatic compound (A) of epoxy radicals.
Vi. the resin combination any one of above-mentioned i~v, wherein, aromatic compound (A) is o-phenyl phenol Glycidol ether.
Vii. the resin combination any one of above-mentioned i~vi, wherein, cyclic compound (B) is to be selected from (a) Skeleton or (b) in the group be made up of phenyl, biphenyl, naphthalene, dinaphthalene and bisphenol-A are selected from the bone in the group described in following (B-3) The cyclic compound (B) of frame,
B-3：Isobornyl, adamantane, pentamethylene, hexamethylene, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
Viii. the resin combination any one of above-mentioned i~vii, wherein, cyclic compound (B) be with selected from The cyclic compound (B) of skeleton in the group be made up of phenyl, biphenyl, bisphenol-A, pentamethylene, hexamethylene and hydrogenated bisphenol A.
Ix. the resin combination described in above-mentioned viii, wherein, cyclic compound (B) is with selected from by biphenyl, bisphenol-A With the cyclic compound (B) of the skeleton in the group of hexamethylene composition.
X. the resin combination any one of above-mentioned i~ix, wherein, cyclic compound (B) is at least to have at least 2 Individual oxetanyl or the cyclic compound of epoxy radicals (B) or limonene oxide.
Xi. the resin combination any one of above-mentioned i~x, wherein, the viscosity of cyclic compound (B) is Below 1500mPas.
Xii. the resin combination described in above-mentioned xi, wherein, cyclic compound (B) is below 1500mPas comprising viscosity Bisphenol A diglycidyl ether.
Xiii. the resin combination any one of above-mentioned i~xii, wherein, cyclic compound (B) includes ester ring type Epoxy resin.
Xiv. the resin combination any one of above-mentioned i~xiii, wherein, the viscosity of above-mentioned resin combination is Below 1500mPas.
Xv. the resin combination described in above-mentioned xiv, wherein, the viscosity of above-mentioned resin combination is preferably 1300mPas Below.
Xvi. the resin combination any one of above-mentioned i~xv, wherein, when forming the solidfied material of 100 μm of thickness, 60 DEG C, the moisture-vapor transmission of the solidfied material determined under conditions of relative humidity 90% be 35g/m2Less than 24 hours.
Xvii. the resin combination described in above-mentioned xvi, wherein, the moisture-vapor transmission of above-mentioned solidfied material is 30g/m2· Less than 24 hours.
Xviii. the resin combination any one of above-mentioned i~xvii, its cure shrinkage are less than 4%.
Xix. the resin combination any one of above-mentioned i~xvii, wherein, the liquid refractivity of resin combination is 1.54~1.7.
Xx. the resin combination any one of above-mentioned i~xix, wherein, the vitrifying of the solidfied material of resin combination Transition temperature (Tg) is more than 45 DEG C.
Xxi. the resin combination described in above-mentioned xx, wherein, above-mentioned glass transition temperature (Tg) is more than 50 DEG C.
Xxii. the resin combination any one of above-mentioned i~xxi, wherein, aromatic compound (A)：Ring-type chemical combination The ratio of thing (B) is 3：7~7：3.
Xxiii. the resin combination any one of above-mentioned i~xxi, wherein, aromatic compound (A)：Ring-type The ratio of compound (B) is 3.5：6.5~6.5：3.5.
Xxiv. the resin combination any one of above-mentioned i~xxi, wherein, curing agent triggers for light cationic polymerization Agent.
Xxv. the resin combination described in above-mentioned xxiv, wherein, light cationic polymerization initiator is selected from by (tri-isopropyl benzene Base) iodineFour (pentafluorophenyl group) borates, diphenyl [4- (thiophenyl) phenyl] (pentafluoroethyl group) phosphate of sulfonium trifluoro three and three Compound in the group of [4- (4- acetylbenzenes sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides composition.
Xxvi. the resin combination any one of above-mentioned i~xxv, wherein, aromatic compound (A) is adjacent phenyl Phenol glycidyl ethers, cyclic compound (B) are below viscosity 1500mPas selected from by bisphenol A diglycidyl ether, Asia Xylyl dioxygen azetidine, 3,3 ', 5,5 '-tetramethyl -4,4 '-bis- (glycidoxy) -1,1 '-biphenyl, biphenyl aralkyl Fundamental mode polyglycidyl ether, 3,4- epoxy hexane ylmethyls -3 ', 4 '-epoxy hexane formic acid esters, hydrogenated bisphenol A two shrink Compound in the group of glycerin ether and limonene oxide composition.
Xxvii. the resin combination described in above-mentioned xxvi, wherein, cyclic compound (B) is below viscosity 1500mPas Be selected from by bisphenol A diglycidyl ether, 3,4- epoxy hexane ylmethyls -3 ', 4 '-epoxy hexane formic acid esters and hydrogenation are double Compound in the group of phenol A diglycidyl ethers composition.
Xxviii. the resin combination any one of above-mentioned i~xxv, wherein, the ester ring type of cyclic compound (B) The aliphatic ring of epoxy resin is carbon number 6 or 7, more preferably cyclohexane ring.
The sealed solid method of the organic EL element of the present invention includes following process：Organic EL members on substrate is formed at The process that passivating film is formed on part；The coated face resin composition for encapsulating on above-mentioned passivating film, and the transparent base of sealing is set The process of plate；With the process for making above-mentioned face resin composition for encapsulating solidification；Characterized in that, the solidification using the invention described above Property resin combination is as the resin composition for encapsulating.
The organic EL element to be sealed by substrate and comprising lower electrode, including at least luminescent layer organic EL layer and The element portion main body of upper electrode is formed.Using glass substrate, include cycloolefin or makrolon, polymethyl methacrylate etc. Transparent organic material, the transparent organic material is subjected to high rigidity with glass fibre etc. obtained from hybrid Transparency carrier etc. includes the flat substrate of electrical insulating property material as substrate.In addition, the representativeness as element portion main body is formed, It can be listed below.
(1) lower electrode/luminescent layer/upper electrode
(2) lower electrode/electron transfer layer/luminescent layer/upper electrode
(3) lower electrode/luminescent layer/hole transmission layer/upper electrode
(4) lower electrode/electron transfer layer/luminescent layer/hole transmission layer/upper electrode
For example, the organic EL element of the Rotating fields with above-mentioned (4) can make as follows：On the one side of substrate, pass through Resistive heating evaporation or sputtering method form the lower electrode (negative electrode) for including Al-Li alloys etc., are then steamed by resistance heating The film forming method such as plating method or ion beam sputtering, which stacks gradually, to be includedThe electronics of oxadiazole derivative, triazole derivative etc. passes Defeated layer, luminescent layer, include TPD's (N, N '-diphenyl-N, N '-bis- (3- aminomethyl phenyls) -1,1- xenyls -4,4 '-diamines) etc. Hole transmission layer and upper electrode (anode) are used as organic EL layer.It should be noted that the Rotating fields or material of organic EL element As long as playing the function as display element, just it is not particularly limited.In addition, the sealed solid method of the present invention is for any knot The organic EL element of structure can be applied.
Passivating film is formed in a manner of covering organic EL element.Passivating film can use the inorganic materials such as silicon nitride, silica The methods of material is by being deposited or sputtering is formed.Passivating film is set to prevent the intrusion organic EL element such as moisture, ionic impurity. The thickness of passivating film is preferably the scope of the scope of 10nm~100 μm, more preferably 100nm~10 μm.In order to improve reliability, Passivating film can be laminated.
For passivating film, although depending on membrane formation process, the faulty film of pin hole, most feelings generally be present It is the weak film of mechanical strength under condition.Therefore, in sealed solid method, further coating binder, use are close on passivating film Envelope is crimped with transparency carrier, and solidifies adhesive, so as to improve the reliability of sealing.
Embodiment
Next, the present invention is described in more detail by embodiment.The invention is not restricted to following embodiment.Need to illustrate , unit " part " the expression mass parts of numerical value.
With forming shown in examples below and comparative example, embodiment and the respective ultraviolet hardening of comparative example are obtained Resin combination and respective solidfied material.In addition, for resin combination and cured film evaluation method and evaluation criterion with Following manner is carried out.
(1) viscosity：Use E type viscosimeters (TV-200：Toki Sangyo Co., Ltd.'s system) determined at 25 DEG C.
(2) liquid refractivity：With Abbe refractomecer (DR-M2；Co., Ltd.'s ア タ go systems) measure resin joined together The refractive index (25 DEG C) of composition.
(3) moisture-vapor transmission：Energy-ray or thermohardening type resin are clamped with glass substrate, uses 100 μm of interval Thing adjusts thickness, with high-pressure sodium lamp (80W/cm, ozone free) in 3000mJ/cm2Under conditions of or at 100 DEG C heating it is 1 small When and make its solidification, so as to make test piece.The test piece of gained Lyssy moisture-vapor transmission meter L80-5000 (Systech Illinois company systems), 60 DEG C × 90%RH condition determine moisture permeability.
(4) Tg (glass transition temperature)：For the Tg of the energy-ray after solidification or thermohardening type resin bed points, with viscous Elasticity measurement system EXSTAR DMS-6000 (SII nanosecond science and technology Co. Ltd. system), stretch mode, frequency 1Hz are measured.
(5) cure shrinkage：Energy-ray or thermohardening type resin bed are coated with base material, passes through high-pressure sodium lamp (80W/ Cm, ozone free) 3000mJ/cm2Irradiation or 100 DEG C of drier heat 1 hour, make resin composition, so as to make film The solidfied material of gravity test.
According to JIS K7112B methods, the proportion (DS) of solidfied material is determined.In addition, determine resin combination at 23 ± 2 DEG C Proportion (DL), cure shrinkage is calculated by following formula.Measurement result is represented with the average value of the measurement result of 4 times.
Cure shrinkage (%)=(DS-DL)/DS × 100
(6) processability：On clean glass substrate, by KAYATORON Z-5536, with 5 μm of thickness, point gum machine is used (SHOTMASTER：Musashi エ Application ジ ニ ア リ Application グ Co. Ltd. systems), carry out the coating of seal pattern.
Then, the resin combination of embodiment and comparative example is used into point gum machine in seal pattern in the same manner as seal pattern Droplet is added dropwise in inframe.
Then, by another clean glass substrate, using laminating apparatus, in a vacuum, with above-mentioned dropwise addition resin combination Substrate fitting after thing.Then, with atmosphere, gap, irradiation UV (accumulative light quantities are formed：3000mJ/cm2) and make it solid Change, the baking oven of 120 DEG C of input, be heating and curing 1 hour, so as to make sample for evaluation.
Evaluation criterion
Zero ... dropping liquid is sprawled rapidly in sample room, resin combination gapless and equably full of in sample room
△ ... dropping liquids sprawling into sample room is slightly slow, but resin combination gapless and equably full of in sample room
× ... dropping liquid is not sprawled fully in sample room, produces gap in sample room, and resin combination is not equably Full of in sample room
Table 1
OPP-G：Sanko Co., Ltd.'s o-phenyl phenol glycidol ether
OXT-121：Toagosei Co., Ltd's xylylene dioxygen azetidine
jER-828：Mitsubishi chemical Co., Ltd's bisphenol A diglycidyl ether
EP-4088S：Asahi Denka Co., Ltd.'s dicyclopentadiene dimethanol diglycidyl ether
YX-4000H：Mitsubishi chemical Co., Ltd's system 3,3 ', 5,5 '-tetramethyl -4,4 '-bis- (glycidoxies) -1,1 ' - Biphenyl
KAYARAD NC-3000H：Nippon Kayaku K. K's biphenyl aralkyl-type polyglycidyl ether
SEJ-01R：Nippon Kayaku K. K 3,4- epoxy hexane ylmethyls -3 ', 4 '-epoxy hexane formic acid esters
GSID 26-1：, BASF the Amada Co., Ltd.s system ([(fluoroform of three [4- (4- acetylbenzenes sulfenyl) phenyl] sulfonium three Base) sulfonyl] methanides
EPOLIGHT 4000：Kyoeisha Chemical Co., Ltd.'s hydrogen manufacturing bisphenol A diglycidyl ether
Limonene oxide：RENESSENZ company system limonene oxides
EPOLIGHT 80MF：Kyoeisha Chemical Co., Ltd.'s glycerin diglycidyl ether
EPOLIGHT 100MF：Kyoeisha Chemical Co., Ltd.'s trihydroxymethylpropanyltri diglycidyl ether
From embodiment 1~5 and the evaluation result of comparative example 1~3, the resin combination of the invention with specific composition Tg height, cure shrinkage, the moisture-vapor transmission of thing are low.Therefore, it is suitable for the smears of such as Obstruct membrane, various sealing material The face encapsulant of material, particularly organic EL element.
Industrial applicability
The resin combination of the present invention and its visible light transmissivity of solidfied material, light resistance is excellent, Tg is high, cure shrinkage Rate, moisture-vapor transmission are low, therefore are suitable for various encapsulants, the face encapsulant particularly suitable for organic EL element.

Claims (16)

1. the resin combination that a kind of face for organic electroluminescent device seals, it contains：With selected from by biphenyl, naphthalene, At least one of the group that dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S form skeleton and oxetanyl or epoxy The aromatic compound (A) of base；With with oxetanyl or epoxy radicals and meet the ring-type chemical combination of the condition of following (iii) Thing (B)；And
The viscosity that the resin combination determines at 25 DEG C is below 1300mPas；
(iii) condition of the cyclic compound (B)：
Ring in the cyclic compound (B) is aromatic ring or aliphatic ring, wherein, in the case where ring is (a) aromatic ring, The cyclic compound is with the different structure of the compound from being used as the aromatic compound (A) and with being selected from By the compound of the skeleton in biphenyl, naphthalene, dinaphthalene, anthracene and the luxuriant and rich with fragrance group formed；In addition, in the case where ring is (b) aliphatic ring, The cyclic compound is alicyclic epoxy resin, and the alicyclic epoxy resin is selected from by following formula (b-1a), (b-1b) and (b- 1c) the group formed,
Formula (b-1a)：
Formula (b-1b)：
Formula (b-1c)：
N is average value and represents 1~5 positive number,
The moisture-vapor transmission determined under conditions of 60 DEG C, humidity 90% of the solidfied material of the resin combination is 35g/m2· Less than 24 hours,
Relative to the mass parts of total amount 100 of aromatic compound (A) and cyclic compound (B), the resin combination contains 20 The aromatic compound (A) of~80 mass parts.
2. resin combination as claimed in claim 1, wherein, aromatic compound (A) has described selected from following (A-1) Group in skeleton,
A-1：Biphenyl, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
3. resin combination as claimed in claim 1 or 2, wherein, aromatic compound (A) is with selected from by biphenyl and double Compound of the skeleton as aromatic backbone in the group of phenol A compositions.
4. resin combination as claimed in claim 1, wherein, cyclic compound (B) is alicyclic epoxy resin.
5. resin combination as claimed in claim 1 or 2, wherein, the ring of cyclic compound (B) is aromatic ring.
6. resin combination as claimed in claim 5, wherein, cyclic compound (B) is with selected from by biphenyl, naphthalene and dinaphthalene The oxetane compound or epoxide of skeleton in the group of composition.
7. resin combination as claimed in claim 1 or 2, it also contains curing agent (C).
8. resin combination as claimed in claim 7, wherein, curing agent (C) is light cationic polymerization initiator.
9. resin combination as claimed in claim 8, wherein, the light cationic polymerization initiator is selected from following (C-1) At least one of described group,
C-1：Sulfonium salt, iodineSalt,Salt, ammonium salt and stibate.
10. resin combination as claimed in claim 7, wherein, curing agent (C) is thermal curing agents.
11. resin combination as claimed in claim 10, wherein, the thermal curing agents are selected from the group described in following (C-2),
C-2：Aminated compounds, anhydrides compound, amides compound, phenolic compound, carboxylic acid compound, imidazoles Compound, isocyanuric acid adduct, metallic compound, sulfonium salt, ammonium salt, stibate,Salt, microcapsule-type curing agent.
12. resin combination as claimed in claim 1 or 2, wherein, relative to aromatic compound (A) and cyclic compound (B) the mass parts of total amount 100, the cyclic compound (B) containing 20~80 mass parts.
13. resin combination as claimed in claim 1 or 2, wherein, by aromatic compound (A) and cyclic compound (B) When total amount is set to 100 mass parts, the curing agent (C) containing 0.1~5 mass parts.
14. a kind of display of organic electroluminescence, wherein, utilize the resin combination made any one of claim 1~13 Solidfied material obtained from thing solidification has carried out face sealing.
15. the film that a kind of face for display of organic electroluminescence seals, it is by by any one of claim 1~13 institute The resin combination stated is coated on base material and it is solidified and is obtained, and has barrier property.
16. resin combination the answering in the sealing of the face of organic electroluminescent device any one of claim 1~13 With.
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WO2014083850A1 (en) 2014-06-05
KR101999614B1 (en) 2019-07-12
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TWI658062B (en) 2019-05-01
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