CN104813741A - Resin composition, and cured product (1) thereof - Google Patents

Resin composition, and cured product (1) thereof Download PDF

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Publication number
CN104813741A
CN104813741A CN201380062164.0A CN201380062164A CN104813741A CN 104813741 A CN104813741 A CN 104813741A CN 201380062164 A CN201380062164 A CN 201380062164A CN 104813741 A CN104813741 A CN 104813741A
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compound
skeleton
cyclic compound
methyl
group
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CN104813741B (en
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内藤伸彦
木户场润
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

Abstract

The present invention relates to a resin composition which has a low viscosity (at 25 DEG C) of not more than 1300mPas and a relatively high liquid refractive index of at least 1.50, which is used to seal a surface of an organic electroluminescent (EL) element, and with which a cured product exhibiting excellent visible light transmission, excellent light resistance, a high Tg, and a low water vapour transmission rate can be obtained. The resin composition has a viscosity measured at 25 DEG C of not more than 1300mPas, and includes an aromatic compound (A) and a cyclic compound (B). Aromatic compound (A) has an oxetanyl group or an epoxy group, and has at least one skeleton selected from the group consisting of: a skeleton of biphenyl, bisphenol A, bisphenol F, bisphenol S, or the like represented by formula (A-A) [...]; a phenylene skeleton which may be substituted with a C1-4 alkyl group, and which is represented by formula (A-B) [...]; an anthracene skeleton; and a phenanthrene skeleton. Cyclic compound (B) has an oxetanyl group or an epoxy group, and satisfies the following conditions (conditions for cyclic compound (B): that the ring in cyclic compound (B) be an aromatic ring, an aliphatic ring, or a heterocycle; in cases when the ring is (a) an aromatic ring, that the cyclic compound have an oxetanyl group or an epoxy group, and an aromatic ring having a structure different to that of the compound used as aromatic compound (A); and, in cases when the ring is (b) an aliphatic ring, that the cyclic compound be either an alicyclic epoxy resin, or, a cyclic compound having an oxetanyl group or an epoxy group, and a cycloalkylene skeleton or an alicyclic hydrocarbon skeleton having a cross-linking structure).

Description

Resin combination and solidfied material (1) thereof
Background technology
Recently, low-moisture permeability material is important material in various industry.Particularly in electric and electronic, display periphery industry, in order to keep quality, it is requisite material, and expects more high performance low-moisture permeability material.
In recent years, in display, be called as the thin display of flat-panel monitor (FPD), particularly plasma display (PDP), liquid crystal display (LCD) has been put into the market and has extensively popularized.In addition, organic electroluminescent (EL) display (OLED) is expected to as follow-on emissive type thin-film display, and is practical in a part of commodity.The organic EL element of OLED display has to be formed on the substrate such as glass of the drive circuit being formed with TFT etc. and comprises containing by the structure of the element portion main body of the thin-film laminate of the luminescent layer of negative electrode and anode clamping.The layers such as the luminescent layer of element portion or electrode are easily deteriorated because of moisture or oxygen, produce reduction, the variable color in brightness or life-span because of deterioration.Therefore, organic EL element is sealed to block from the moisture of outside or the intrusion of impurity.In order to realize high-quality and the organic EL element of high reliability, expect more high performance encapsulant, all the time in the various Sealing Technology of research.
As the representational encapsulating method of organic EL element, have studied and to be used by the seal cover being inserted with the metal of drier or glass in advance sealing to stick with glue agent to be fixed on method (patent documentation 1) on the substrate of organic EL element.In the method, at the substrate peripheral part coating binder of organic EL element, seal cover being set thereon, then by making adhesive solidification, substrate and seal cover being fixed, thus sealing organic el element.In such method, the seal cover of glass is utilized to carry out being sealed to main flow.But the seal cover of glass is made by the borehole processing carried out for drier being inserted smooth glass substrate, therefore has the tendency that cost uprises.In addition, utilize seal cover to seal, owing to inserting drier in the inner side of seal cover, thus cannot extract light from seal cover side.That is, extract from the substrate-side of element the light sent from light source, be restricted to bottom emission type element.When bottom emission type element, Problems existing is, the reduction of the aperture opening ratio caused by the drive circuit portion be formed on substrate, and the reduction of the extraction efficiency caused because drive circuit portion covers a part of light.Therefore, expect to develop the encapsulating method that can be applicable to extract the top emission type element of light from the opposition side of the substrate of organic EL element.
As the representational encapsulating method that can be applicable to top emission type element, there are elastic membrane sealing method and sealed solid method.Elastic membrane sealing method is that laminated multi-layer comprises the method (patent documentation 2) that film that is inorganic or organic material forms passivating film in organic EL element.In order to give sufficient moisture resistance by the method to element, to need on element the film of sequentially stacked several layers.Therefore, in elastic membrane sealing method, film formation process is long and cost is high, and in addition, the introducing of the large-scale vacuum system equipment required for film forming, thus initial investment has the tendency uprised.
On the other hand, sealed solid method arranges passivating film to cover the element portion of whole organic EL element, and arrange the method for sealing transparency carrier via encapsulant thereon.Usually, passivating film is by evaporation or sputtering inorganic material and being formed, but it is in most cases film that the faulty film or mechanical strength with pin hole are weak.Therefore, in sealed solid method, after element arranges passivating film, stick with glue via sealing the sealing transparency carrier that agent arranges glass substrate etc., improve the reliability of sealing thus.In addition, also studied by heat or photocurable resin are filled in air gap, improve the method for the reliability of sealing.Such sealed solid method receives publicity as the method simply and at low cost can implementing the sealing of the element of top emission type.
When organic EL element utilizes sealed solid method to seal, can use that heat or light-cured resin stick with glue agent as sealing, face sealing sticks with glue agent, but it is because their characteristic may have a significant effect to the productivity ratio of the performance of element and sealing operation, therefore extremely important.Such as, sealing stick with glue the moisture-vapor transmission of agent enough not low time, element portion can be invaded from the pin hole of passivating film, likely cause the deterioration of element.In addition, if the curing reaction of encapsulant is slow, then curing process expends time in, and the productivity ratio of sealing operation likely can reduce.
The sealing used in these sticks with glue agent; except requiring except the high permeability of visible region, also require tolerate the light resistance of luminescence, stable formability, for suppressing the low cure shrinkage of residual stress, protecting light-emitting component from the low moisture-vapor transmission etc. of moisture.Known adhesive can be used to stick with glue agent by sealed solid method enforcement sealing as the sealing of organic EL element, but be difficult to the result obtaining meeting both reliability and productivity ratio at present, expect that developing the sealing that can be suitable for sealed solid method sticks with glue agent.
Prior art document
Patent documentation
Patent documentation 1: No. 4876609th, Japan Patent
Patent documentation 2: Japanese Unexamined Patent Publication 2012-059553
Patent documentation 3: No. 4655172nd, Japan Patent
Patent documentation 4: Japanese Unexamined Patent Publication 2001-81182 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2011-225773 publication
Patent documentation 6: No. 4850231st, Japan Patent
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of encapsulant of organic EL element, the resin combination being particularly suitable for face sealing and visible light transmissivity, light resistance, curability is excellent, Tg is high, cure shrinkage, moisture-vapor transmission are low solidfied material.
For the means of dealing with problems
The present inventor etc. conduct in-depth research to solve the problem, and found that, have specific composition and viscosity is the resin combination of below certain value and solidfied material thereof can solve the problem, thus complete the present invention.
That is, the present invention relates to the invention described in following (1) ~ (25).
(1) for the resin combination that the face of organic EL element seals, it contains: have at least one skeleton of group and the aromatic compound (A) of oxetanyl or epoxy radicals that are selected from and are made up of skeleton, anthracene skeleton and the luxuriant and rich with fragrance skeleton shown in the formula (A-B) of the skeleton shown in the formula of following (i) (A-A), following (ii); With there is oxetanyl or epoxy radicals and meet the cyclic compound (B) of the condition of following (iii); And
The viscosity that this resin combination measures at 25 DEG C is below 1300mPas;
Skeleton shown in (i) formula (A-A):
In above-mentioned formula, X represents Direct Bonding, sulphur atom or dimethylated methylene base, R 1represent the alkyl of hydrogen atom or carbon number 1 ~ 4, m represents the integer of 1 ~ 4;
(ii) skeleton shown in formula (A-B):
In above-mentioned formula, R 2represent the alkyl of hydrogen atom or carbon number 1 ~ 4, n represents the integer of 1 ~ 4;
(iii) condition of this cyclic compound (B):
Ring in this cyclic compound (B) is aromatic ring, aliphat ring or heterocycle, wherein, when ring is (a) aromatic ring, this cyclic compound is the compound of the different structure of the compound had from use as described aromatic compound (A); In addition, when ring is (b) aliphat ring, this cyclic compound is have the ester ring type hydrocarbon skeleton of bridged linkage or the cyclic compound of cycloalkylidene skeleton and oxetanyl or epoxy radicals or alicyclic epoxy resin.
(2) resin combination as described in above-mentioned (1), wherein, aromatic compound (A) has the skeleton in the group be selected from described in following (A-1),
A-1: phenyl, biphenyl, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
(3) resin combination as described in above-mentioned (1) or (2), wherein, aromatic compound (A) for have select free phenyl, biphenyl and bisphenol-A to form group in skeleton as the compound of aromatic backbone.
(4) resin combination according to any one of above-mentioned (1) ~ (3), wherein, cyclic compound (B) has the ring in the group be selected from described in following (B-1),
B-1: aromatic ring, above-mentioned aliphat ring and heterocycle.
(5) resin combination as described in above-mentioned (1), wherein, cycloalkylidene skeleton forms the skeleton shown in following formula (B-A):
In above-mentioned formula, Y represents Direct Bonding, sulphur atom or methylene, R 3represent the alkyl of hydrogen atom or carbon number 1 ~ 4, t represents the integer of 1 ~ 4.
(6) resin combination as described in above-mentioned (1), wherein, cyclic compound (B) is alicyclic epoxy resin.
(7) resin combination according to any one of above-mentioned (1) ~ (4), wherein, the ring of cyclic compound (B) is aromatic ring.
(8) resin combination as described in above-mentioned (7), wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-2),
B-2: phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
(9) resin combination as described in above-mentioned (8), wherein, cyclic compound (B) for have select free phenyl, biphenyl, naphthalene, dinaphthalene and bisphenol-A to form group in the oxetane compound of skeleton or epoxy compounds.
(10) resin combination according to any one of above-mentioned (1) ~ (4), wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-3),
B-3: isobornyl, adamantane, pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
(11) resin combination as described in above-mentioned (4) or (10), wherein, cyclic compound (B) is for having oxetane compound or the epoxy compounds of the skeleton in the group that is selected from and is made up of adamantane, cyclohexane and hydrogenated bisphenol A.
(12) resin combination according to any one of above-mentioned (1) ~ (4), wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-4),
B-4: morpholine, oxolane, oxinane, dioxane, triazine, carbazole, pyrrolidines and piperidines.
(13) resin combination as described in above-mentioned (4) or (12), wherein, cyclic compound (B) is for having oxetane compound or the epoxy compounds of the skeleton in the group that is selected from and is made up of oxinane, dioxane and triazine.
(14) resin combination according to any one of above-mentioned (1) ~ (13), it is also containing curing agent (C).
(15) resin combination as described in above-mentioned (14), wherein, curing agent (C) is light cationic polymerization initiators.
(16) resin combination as described in above-mentioned (15), wherein, described smooth cationic polymerization initiators for being selected from least one in the group described in following (C-1),
C-1: sulfonium salt, iodine salt, salt, ammonium salt and stibate.
(17) resin combination as described in above-mentioned (14), wherein, curing agent (C) is thermal curing agents.
(18) resin combination as described in above-mentioned (17), wherein, described thermal curing agents is selected from the group described in following (C-2),
C-2: aminated compounds, anhydrides compound, amides compound, phenolic compound, carboxylic acid compound, glyoxaline compound, isocyanuric acid adduct, metallic compound, sulfonium salt, ammonium salt, stibate, salt, microcapsule-type curing agent.
(19) resin combination according to any one of above-mentioned (1) ~ (18), wherein, relative to total amount 100 mass parts of aromatic compound (A) with cyclic compound (B), the aromatic compound (A) containing 20 ~ 80 mass parts.
(20) resin combination according to any one of above-mentioned (1) ~ (19), wherein, relative to total amount 100 mass parts of aromatic compound (A) with cyclic compound (B), the cyclic compound (B) containing 20 ~ 80 mass parts.
(21) resin combination according to any one of above-mentioned (1) ~ (20), wherein, when aromatic compound (A) is set to 100 mass parts with the total amount of cyclic compound (B), the curing agent (C) containing 0.1 ~ 5 mass parts.
(22) resin combination according to any one of above-mentioned (1) ~ (21), wherein, when forming the solidfied material of thickness 100 μm, 60 DEG C, the moisture-vapor transmission of this solidfied material that measures under the condition of relative humidity 90% is 35g/m 2less than 24 hours.
(23) OLED display, wherein, the solidfied material that utilization makes the resin composition according to any one of above-mentioned (1) ~ (22) and obtains has carried out face sealing.
(24) for the film that the face of OLED display seals, it by be coated on by the resin combination according to any one of above-mentioned (1) ~ (22) on base material and to make it solidify and obtain, and has barrier property.
(25) application of the resin combination according to any one of above-mentioned (1) ~ (22) in the sealing of the face of organic EL element.
Invention effect
Low and its solidfied material of the viscosity of resin combination of the present invention is visible light transmissivity, light resistance is excellent, Tg is high, cure shrinkage, moisture-vapor transmission are low, is therefore particularly suitable for the encapsulant of organic EL element, is particularly suitable for face sealing.
Embodiment
As the above-mentioned aromatic compound (A) contained by resin combination of the present invention, following illustrated oxetane compound or epoxy compounds can be enumerated.
Aromatic compound (A) contained by resin combination of the present invention is as long as the aromatic compound (A) of at least one skeleton that has in the group being selected from and being made up of skeleton, anthracene skeleton and the luxuriant and rich with fragrance skeleton shown in the skeleton shown in above-mentioned formula (A-A), above-mentioned formula (A-B) and oxetanyl or epoxy radicals.
It should be noted that, in the present invention, anthracene skeleton or luxuriant and rich with fragrance skeleton can have substituting group, also can unsubstituted.Have in substituent situation, alternatively base can be enumerated: alkyl, alkoxyl or thiazolinyl, and these substituting groups are all preferably carbon number 1 ~ 4.
In the present invention, as aromatic compound (A), use the aromatic compound of skeleton and oxetanyl or the epoxy radicals had in the group being selected from and being made up of skeleton, anthracene skeleton and the luxuriant and rich with fragrance skeleton shown in the skeleton shown in following formula (A-A) or following formula (A-B).
(in above-mentioned formula, X represents Direct Bonding, sulphur atom or dimethylated methylene base, R 1represent the alkyl of hydrogen atom or carbon number 1 ~ 4, m represents the integer of 1 ~ 4.)
(in above-mentioned formula, R 2represent the alkyl of hydrogen atom or carbon number 1 ~ 4, n represents the integer of 1 ~ 4.Wherein, the skeleton that above-mentioned formula (A-A) comprises or not)
By combining this aromatic compound (A) (hereinafter also referred to composition (A)) and above-mentioned cyclic compound (B) (hereinafter also referred to composition (B)), extremely excellent moisture-proof effect can be obtained.Above-mentioned skeleton becomes and intercepts fully moisture, thus prevents moisture-inhibiting.
In above-mentioned formula (A-A) skeleton, preferably, X is Direct Bonding or has dimethylated methylene base, particularly preferably Direct Bonding (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 connected or connected by alkyl.
In above-mentioned skeleton, when oxetanyl or epoxy radicals are connected by alkyl, can enumerate as this alkyl: the alkylidene of carbon number 1 ~ 10 or there is the alkylidene of carbon number 1 ~ 10 of ehter bond.Ehter bond can in this alkylidene, also can at arbitrary end of this alkylidene.Be preferably the alkylidene (being more preferably the alkylidene of carbon number 1 ~ 3) of carbon number 1 ~ 4, the alkylidene (being more preferably the alkylidene of the alkylidene-oxygen atom-carbon number 1 ~ 3 of carbon number 1 ~ 3) etc. of the alkylidene-oxygen atom-carbon number 1 ~ 4 of carbon number 1 ~ 4 comprises the alkylidene (being more preferably the alkylidene of carbon number 2 ~ 6) of the carbon number 2 ~ 10 of ehter bond between carbon atom, or-oxygen methyl etc. has the alkylidene (alkyl of-oxygen base-carbon number 1 ~ 4 of the carbon number 1 ~ 4 of ehter bond at alkylidene end, be more preferably-the alkyl of oxygen base-carbon number 1 ~ 4).When end has ehter bond, usual ether and aromatic rings bonding, alkyl and oxetanes ring or epoxide ring bonding.
As the aromatic compound (A) containing oxetanyl, such as following illustrative oxetane compound can be enumerated.
Can enumerate such as: 1, two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene of 4-, 3-ethyl-3-phenoxymethyloxetane, xylylene dioxygen azetidine, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 3-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 2-, 4, 4 '-bis-[(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, 2 '-bis-[(3-ethyl-3-oxetanyl) methoxyl group] biphenyl, 3, 3 ', 5, 5 '-tetramethyl [4, 4 '-bis-(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, two [(3-Ethyloxetane-3-base) methoxyl group] naphthalene of 7-, 4, the oxetane compounds such as 4 '-bis-[(1-ethyl-3-oxetanyl) methyl] sulfenyl diphenyl sulfide ether acid.
As the aromatic compound (A) with epoxy radicals, can enumerate: styrene oxide, phenyl glycidyl ethers etc. have the epoxy compounds of phenyl skeleton, biphenylyl glycidyl ether, xenyl diglycidyl ether, to tert-butyl-phenyl glycidol ether, 3, 3 ', 5, 5 '-tetramethyl-4, 4 '-bis-(glycidyl oxygen base)-1, 1 '-biphenyl, phenyl aralkyl type epoxy compound, biphenyl aralkyl type epoxy compound etc. has the epoxy compounds of biphenyl backbone, phenol novolak-type epoxy compound, the novolak type epoxy compounds such as cresol novolak type epoxy compound, the bisphenol A type epoxy compound such as bisphenol A diglycidyl ether or brominated bisphenol A diglycidyl ether, the bisphenol S type epoxy compounds such as bisphenol-S diglycidyl ether or brominated bisphenol S diglycidyl ether, two phenyl fluorenes diglycidyl ether or two phenyl fluorenes ethanol glycidol ethers etc. have the epoxy compounds etc. of fluorene skeleton (being preferably two phenyl fluorene skeleton).
At this, as the example of xenyl aralkyl epoxy compounds, the compound of following formula (A-Aa) can be enumerated.
(in above-mentioned formula, G represents glycidyl, and p represents the integer of 1 ~ 50.)
As the compound of above-mentioned formula (A-Aa), can enumerate: commercially available o-phenyl phenol glycidol ether (Sanko Co., Ltd.'s system) etc.
As the concrete skeleton of composition (A), the skeleton in the group be selected from described in following (A-1) can be enumerated, A-1: phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
In resin combination of the present invention, in the above-mentioned skeleton of mentioned component (A), preferred phenyl skeleton (not comprising the skeleton of formula (A-A), lower same), biphenyl backbone, bisphenol A skeleton or bisphenol S skeleton.Be more preferably viscosity, moisture permeability is low, light penetration is excellent biphenyl backbone, bisphenol A skeleton.Among above-mentioned, be more preferably biphenyl backbone.
In addition, as mentioned component (A), preferably there is the composition (A) of 1 oxetanyl or epoxy radicals, be more preferably the aromatic compound (A) that skeleton also has above-mentioned preferred skeleton or preferred skeleton.Mono-epoxy compound more preferably containing biphenyl backbone or single oxetanes based compound.
As mentioned component (A), as long as have any one in oxetanyl or epoxy radicals, be more preferably epoxy radicals.
As the preferred aromatic compound (A) with epoxy radicals, can enumerate: the mono-epoxy compound containing biphenyl backbone, mono-epoxy compound containing phenyl skeleton, such as: phenylphenol glycidol ether (being more preferably o-phenyl phenol glycidol ether) or limonene oxide.
Relative to total amount 100 mass parts of composition (the A)+composition (B) as reactive compounds, the content of composition of the present invention (A) is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.In addition, in order to realize low moisture permeability, the functional equivalent of composition (A) is preferably 10 ~ 500g/ equivalent, is more preferably 50 ~ 250g/ equivalent.
As the cyclic compound (B) contained by resin combination of the present invention, can enumerate: oxetane compound or epoxy compounds, the oxetane compound with the aliphat ring of specific skeleton or epoxy compounds, the oxetane compound with heterocycle or the epoxy compounds with the aromatic rings of specific skeleton.
As the ring in cyclic compound (B), the ring in the group be selected from described in following (B-1) can be enumerated,
B-1: aromatic rings, aliphat ring and heterocycle.
At this, when selecting to have the oxetane compound of aromatic rings or epoxy compounds as cyclic compound (B), use the compound having and select as the different structure of the structure of the compound of aromatic compound (A).
In addition, as cyclic compound (B), preferably there is the cyclic compound (B) of multiple (at least 2) oxetanyl or epoxy radicals usually.
As the oxetane compound with aromatic rings or the epoxy compounds that can be used as cyclic compound (B), can enumerate with as above-mentioned aromatic compound (A) illustrative Compound Phase with compound, in the present invention, with this aromatic compound (A) and the used time, as mentioned above, importantly use the compound that structure is different from the compound used as this aromatic compound (A) as cyclic compound (B).
As the concrete aromatic rings skeleton of cyclic compound (B) with aromatic rings, the skeleton in the group be selected from described in following (B-2) can be enumerated, B-2: phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.Among those, as preferred skeleton, the skeleton in the group formed for selecting free phenyl, biphenyl, naphthalene, dinaphthalene and bisphenol-A.
Below enumerate concrete compound.
As the oxetane compound with aromatic rings that can be used as cyclic compound (B), the compound same with the Compound Phase cited by the part at mentioned component (A) can be enumerated, following compound can be illustrated particularly.
Can enumerate such as: 1, two { [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene of 4-, 3-ethyl-3-phenoxymethyloxetane, xylylene dioxygen azetidine, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 4-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 3-, 1, two [(3-Ethyloxetane-3-base) methoxyl group] benzene of 2-, 4, 4 '-bis-[(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, 2 '-bis-[(3-ethyl-3-oxetanyl) methoxyl group] biphenyl, 3, 3 ', 5, 5 '-tetramethyl [4, 4 '-bis-(3-Ethyloxetane-3-base) methoxyl group] biphenyl, 2, two [(3-Ethyloxetane-3-base) methoxyl group] naphthalene of 7-, 4, 4 '-bis-[(1-ethyl-3-oxetanyl) methyl] sulfenyl diphenyl sulfide ether acid etc.
As the epoxy compounds with aromatic rings that can be used as cyclic compound (B), following compound can be illustrated.
Can enumerate such as: styrene oxide, phenyl glycidyl ethers etc. have the epoxy compounds of phenyl skeleton, biphenylyl glycidyl ether, xenyl diglycidyl ether, to tert-butyl-phenyl glycidol ether, 3,3 ', 5,5 '-tetramethyl-4,4 '-bis-(glycidyl oxygen base)-1,1 '-biphenyl, xenyl aralkyl type epoxy compound etc. has the epoxy compounds of biphenyl backbone, phenol novolak-type epoxy compound, the novolak type epoxy compounds such as cresol novolak type epoxy compound, bisphenol A diglycidyl ether, the bisphenol A type epoxy compound such as brominated bisphenol A diglycidyl ether, bisphenol-S diglycidyl ether, the bisphenol S type epoxy compounds such as brominated bisphenol S diglycidyl ether, two phenyl fluorenes diglycidyl ether, two phenyl fluorenes ethanol glycidol ethers etc. have the epoxy compounds of fluorene skeleton, glycidyl oxygen base naphthalene, two (2, the 3-epoxy radicals propane-1-base oxygen base) naphthalene of 1,6-, dinaphthalene glycidol ether, dinaphthalene diglycidyl ether, dinaphthol ethanol diglycidyl ether etc. has the epoxy compounds etc. of naphthalene skeleton.
In the present invention, when selecting to have the oxetane compound of aromatic rings or epoxy compounds as cyclic compound (B), in above-claimed cpd, use have from select as the different structure of the compound of composition (A), the compound with aromatic ring and oxetanyl or epoxy radicals.Now, in resin combination of the present invention, containing 2 kinds of different oxetane compounds with aromatic rings or epoxy compounds.
When the compound selecting to have an aromatic rings is as cyclic compound (B), as the preferred skeleton containing this aromatic rings, can enumerate: phenyl skeleton, biphenyl backbone, bisphenol A skeleton, Bisphenol F skeleton, bisphenol S skeleton or naphthalene skeleton etc.Be more preferably viscosity, moisture permeability is low, light transmittance is excellent biphenyl backbone, bisphenol A skeleton or naphthalene skeleton.Be more preferably biphenyl backbone or bisphenol A skeleton, most preferably be bisphenol A skeleton.The viscosity of these compounds is preferably below 1500mPas.
As the preferred cyclic compound (B) with aromatic rings, the cyclic compound (B) with above-mentioned preferred skeleton can be enumerated, have that preferred skeleton, the further cyclic compound (B) of preferred skeleton, most preferred skeleton are respectively preferred, preferred, most preferred cyclic compound (B) further.In this cyclic compound (B), can be any one in oxetanyl and epoxy radicals, usually be preferably epoxy radicals.Particularly as cyclic compound (B), preferably there is the epoxy compounds of biphenyl backbone or bisphenol A skeleton, particularly preferably there is the compound of multiple epoxy radicals.
Relative to total amount 100 mass parts of composition (the A)+composition (B) as reactive compounds, the content of composition of the present invention (B) is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.In order to realize low moisture permeability, the functional equivalent of composition (B) is 10 ~ 1000g/ equivalent, is preferably 50 ~ 500g/ equivalent.
In addition, from the viewpoint of low-moisture permeability, composition (A) uses different compounds from composition (B).This is because, in order to make moisture permeability reduce, think that electron-dense compound is effective, but not only electron density but also and compound between the balance of crosslink density be also important.Therefore, reduce to make moisture permeability, such as, as composition (A), use and contain phenyl skeleton, biphenyl backbone or bisphenol A skeleton and the compound with a polymerizable groups (oxetanyl or epoxy radicals), as composition (B), use containing phenyl skeleton, biphenyl backbone, bisphenol A skeleton or naphthalene skeleton with above-mentioned preferred content respectively and there is the mode of the compound of multiple (2 ~ more than 3) polymerizable groups (oxetanyl or epoxy radicals).As an example of preferred combination, can enumerate using under type: as composition (A), use and there is biphenyl backbone or bisphenol A skeleton and the compound (preferably there is the compound of an epoxy radicals) with an oxetanyl or epoxy radicals, as composition (B), use has phenyl skeleton, biphenyl backbone or bisphenol A skeleton and there is the compound of multiple (at least 2) oxetanyl or epoxy radicals (being preferably epoxy radicals) or epoxy compounds (the such as limonene oxide containing cyclohexane skeleton, 3, 4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters and A Hydrogenated Bisphenol A 2-glycidyl ether compound etc.).It should be noted that, 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 ether.The viscosity of these compounds used as composition (A) and composition (B) is all preferably below 1300mPas, is more preferably below 800mPas, more preferably below 500mPas.
Then, for the cyclic compound (B) with aliphat ring in cyclic compound (B), be described in detail following.
In the present invention, as the cyclic compound (B) with aliphat ring, use and there is the ester ring type hydrocarbon skeleton of bridged linkage or the cyclic compound of cycloalkylidene skeleton and oxetanyl or epoxy radicals or alicyclic epoxy resin.
The above-mentioned ester ring type hydrocarbon skeleton with bridged linkage or cycloalkylidene skeleton (not having the cycloalkylidene skeleton of bridged linkage) can have substituting group, also can not have substituting group.Under having substituent situation, alternatively base can be enumerated: alkyl, thiazolinyl or alkoxyl, and these groups are preferably carbon number 1 ~ 4, is more preferably carbon number 1 ~ 3.
As the above-mentioned aliphat ring skeleton with the cyclic compound (B) of aliphat ring, can enumerate: there is the ester ring type hydrocarbon skeleton (being preferably the ester ring type hydrocarbon skeleton with bridged linkage of carbon number 7 ~ 10) of bridged linkage and (be not preferably the cycloalkylidene skeleton of carbon number 4 ~ 7 containing the cycloalkylidene skeleton of bridged linkage, be more preferably the cycloalkylidene skeleton of carbon number 5 or 6, more preferably cyclohexyl skeleton).It should be noted that, in cycloalkylidene skeleton, cyclohexylidene skeleton can be 2 cycloalkylidene skeleton Direct Bonding or via linking group bonding, can be the skeleton shown in following formula (B-A).
(in above-mentioned formula, Y represents Direct Bonding, sulphur atom or methylene, R 3represent the alkyl of hydrogen atom or carbon number 1 ~ 4, t represents the integer of 1 ~ 4.)
As the aliphat ring skeleton of this cyclic compound (B), according to circumstances, preferably not there is the cycloalkylidene skeleton of the carbon number 4 ~ 7 of bridged linkage, be more preferably the cycloalkylidene skeleton of carbon number 5 or 6, most preferably be the cyclohexylidene skeleton of divalent.It should be noted that, cyclohexylidene skeleton can form the skeleton shown in above-mentioned formula (B-A).
If illustrate the preferred aliphat ring skeleton of this cyclic compound (B), then can enumerate: be selected from the skeleton in the group described in following formula B-3, B-3: isobornyl, adamantane, pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S, more preferably can enumerate: pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
Not containing in the cycloalkylidene skeleton of bridged linkage, most preferably be cyclohexylidene skeleton.When cyclohexylidene skeleton, the cyclohexane skeleton sometimes not forming the skeleton shown in formula (B-A) is the situation preferably, sometimes defining the skeleton shown in formula (B-A) is preferred, therefore can suitable choice for use.
As the cyclic compound (B) with aliphat ring used in the present invention, can enumerate: cyclic compound or the alicyclic epoxy resin with above-mentioned aliphat ring skeleton and oxetanyl or epoxy radicals.
By combining above-mentioned cyclic compound (B) and above-mentioned aromatic compound (A), extremely excellent moisture-proof effect can be obtained.This is because above-mentioned skeleton becomes and intercepts fully moisture, thus prevents moisture-inhibiting.
In above-mentioned formula (B-A) skeleton preferably, Y is Direct Bonding or the skeleton with methylene, is particularly preferably Direct Bonding.
In addition, as the ester ring type hydrocarbon skeleton with bridged linkage, specifically can enumerate: adamantane framework, dicyclopentadiene skeleton or isobornyl skeleton as preferred skeleton, according to circumstances, preferred adamantane framework or isobornyl skeleton.
In addition, as the concrete example of cycloalkylidene skeleton (not there is the cycloalkylidene skeleton of bridged linkage), can enumerate: cyclopentane framework, cyclohexane skeleton, cycloheptane skeleton etc. are as preferred skeleton, as mentioned above, 2 in these can Direct Bonding or form above-mentioned formula (B-A) skeleton via linking group bonding.
Above-mentioned there is bridged linkage ester ring type hydrocarbon skeleton, cycloalkylidene skeleton (comprising above-mentioned formula (B-A) skeleton) and oxetanyl or epoxy radicals, preferably directly connect or connected by alkyl (can ehter bond be comprised).
And as concrete connected mode, oxetanyl or epoxy radicals and alkyl bonding, this alkyl directly or be connected with aliphat ring via ehter bond.When being connected by alkyl, as alkyl, can enumerate: the alkyl of carbon number 1 ~ 10 or there is the alkyl of carbon number 1 ~ 10 of ehter bond.As preferred linking group, alkyl containing ehter bond, can enumerate: the alkylidene (being preferably the alkylidene of carbon number 2 ~ 6) comprising the carbon number 2 ~ 10 of ehter bond between the carbon atoms such as the alkylidene (being preferably the alkylidene of the alkylidene-oxygen atom-carbon number 1 ~ 3 of carbon number 1 ~ 3) of the alkylidene-oxygen atom-carbon number 1 ~ 4 of carbon number 1 ~ 4, or-oxygen methyl etc. is at alkylidene end alkylidene (alkyl of-oxygen base-carbon number 1 ~ 4) alkyl of oxygen base-carbon number 1 ~ 3 (be more preferably-) with the carbon number 1 ~ 4 of ehter bond etc.This alkylidene is when end has ehter bond, and usual ether and aliphat ring key close, alkyl and oxetanes ring or epoxide ring bonding.In addition, as alicyclic epoxy resin, epoxy radicals can be formed directly on aliphat ring.
As such oxetane compound with aliphat ring, can enumerate: 3 (4), 8 (9)-bis-[(1-ethyl-3-oxetanyl) methoxy]-three rings [5.2.1.2.6] decane etc.
As such epoxy compounds with aliphat ring, can enumerate: limonene oxide, formula described later (b-1a), formula (b-1b) and the alicyclic epoxy resin described in formula (b-1c), hydrogenated bisphenol A epoxy compound, A Hydrogenated Bisphenol A F diglycidyl ether, the bisphenol F type epoxy compounds such as bromination hydrogenation Bisphenol F diglycidyl ether, A Hydrogenated Bisphenol A S diglycidyl ether, the bisphenol S type epoxy compounds such as bromination hydrogenation bisphenol-S diglycidyl ether, diepoxy tristane, tristane diglycidyl ether etc. has the epoxy compounds of tricyclodecane skeleton, adamantane glycidol ether etc. has the epoxy compounds etc. of adamantane framework.
Formula (b-1a):
Formula (b-1b):
Formula (b-1c):
(n is mean value and represents the positive number of 1 ~ 5.)
As the compound with aliphat ring in cyclic compound (B), the cyclic compound (B) of preferred alicyclic epoxy resin or the skeleton during there is the group that is selected from and is made up of isobornyl skeleton, adamantane framework and bisphenol A skeleton.From colourless and reactive excellent, aspect that glass transition temperature is high, particularly preferably can enumerate: alicyclic epoxy resin or there is the cyclic compound (B) of adamantane framework.
Relative to total amount 100 mass parts of composition (the A)+composition (B) as reactive compounds, the content with the cyclic compound (B) of aliphat ring of the present invention is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.In order to realize low moisture permeability, the preferred functional equivalent of this cyclic compound (B) is 10 ~ 1000g/ equivalent, is more preferably 50 ~ 500g/ equivalent.
As the example of heterocycle, can enumerate: morpholine skeleton, oxolane skeleton, oxinane skeleton, dioxane skeleton, triazine skeleton, carbazole skelton, pyrrolidines skeleton and piperidine scaffolds.They can have substituting group, also can not have substituting group, have in substituent situation, can enumerate: alkyl, alkoxyl or thiazolinyl as this substituting group, it typically is carbon number about 1 ~ about 4.
Above-mentioned heterocyclic skeleton and oxetanyl or epoxy radicals can Direct Bonding, also can be connected by divalent alkyl, but usually be connected by divalent alkyl.When being connected by alkyl, as alkyl, can enumerate: the alkylidene of carbon number 1 ~ 10 or there is the alkylidene of carbon number 1 ~ 10 of ehter bond.
As the oxetane compound with heterocycle, can enumerate: the product etc. of isocyanuric acid (CIC acid) and oxa-cyclobutanol.
As the epoxy compounds with heterocycle, can enumerate: isocyanuric acid 1, compound, dioxane glycol diglycidyl ether etc. that 3,5-three-glycidyl ester etc. has isocyanuric acid ester skeleton have the epoxy compoundss such as the compound of dioxane glycol skeleton.
As the composition (B) with heterocycle, preferably there is the compound of isocyanuric acid ester skeleton, particularly preferably product, isocyanuric acid 1,3, the 5-three-glycidyl ester of CIC acid and oxa-cyclobutanol.
Relative to total amount 100 mass parts of composition (the A)+composition (B) as reactive compounds, the content with the composition (B) of heterocycle is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.In order to improve moisture permeability, preferably the functional equivalent of this composition (B) is 10 ~ 500g/ equivalent, is more preferably 50 ~ 250g/ equivalent.
The present invention relates to the hardening resin composition containing mentioned component (A), mentioned component (B), the preferred combination below for the combination as these compositions is described.
As preferred combination, preferably use the weight average molecular weight of any one in mentioned component (A) or mentioned component (B) to be less than 2000, be more preferably less than 1000, be particularly preferably the composition of less than 500 and form hardening resin composition.This is because, by so low-molecular-weight composition being used as any one in composition (A), composition (B), can agent of low hygroscopicity be guaranteed, and low viscosity and easily launching after coating, therefore can obtain at the excellent composition of the manufacture view of OLED.
In addition, particularly in the case of thermal curing, any one of going back in preferred component (A) and composition (B) is oxetane compound.This is because, be oxetane compound by any one, can agent of low hygroscopicity be guaranteed, and the resin combination that the curability that can obtain the short time is excellent.
In addition, as the preferred usage rate of composition (A) with composition (B), (A)/(B) is 8/2 ~ 2/8, is more preferably 7/3 ~ 3/7.
When wanting to improve Tg (glass transition temperature), if be aromatic compound, then can introduce bisphenol A skeleton, if be ester ring type compound, then can introduce dicyclopentadiene skeleton, isobornyl skeleton, adamantane framework.
Particularly in the present invention, the viscosity (viscosity when measuring at 25 DEG C: lower same) of resin combination is generally below 1500mPas, be preferably below 1300mPas, be more preferably below 1200mPas, preferably make to reach below above-mentioned viscosity with time composition (B) in blending constituent (A).
In the present invention, preferably, as composition (A), use and contain biphenyl backbone and monofunctional, aromatic's compound with 1 oxetanyl or epoxy radicals, preferably there is the epoxy compounds (being preferably the monoglycidyl ether containing biphenyl backbone) containing biphenyl backbone of 1 epoxy radicals, be more preferably o-phenyl phenol glycidol ether, as composition (B), use the multifunctional cyclic compound (B) with at least 2 oxetanyls or epoxy radicals.As this multifunctional cyclic compound (B), consider the high Tg etc. of the low moisture-vapor transmission of the viscosity of resin combination, solidfied material, low cure shrinkage, solidfied material, preferably there is the cyclic compound (B) of the aliphat ring of aromatic ring or non-bridging.As this multifunctional cyclic compound (B), preferably, viscosity is below 1400mPas, is preferably below 1350mPas, and has the cyclic compound (B) etc. of cycloalkane skeleton as aromatic ring skeleton of the carbon number 5 ~ 7 of the skeleton shown in above-mentioned formula (A-A) or non-bridging.More preferably, viscosity is below 1400mPas, is preferably below 1350mPas, and there is the skeleton shown in above-mentioned formula (A-A) as aromatic ring skeleton, and there is the epoxy compounds of at least 2 epoxy radicals or/and have the alicyclic epoxy resin of at least 2 epoxy radicals, further preferably, viscosity is below 1350mPas, and there is the polyglycidyl ether compound and/or 3 of biphenyl backbone or bisphenol A skeleton, 4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters.
In addition, according to circumstances, as cyclic compound (B), also the oxetane compound with the condensed cyclic structure such as fluorenes or carbazole or epoxy compounds can be used.
As the alicyclic epoxy resin of composition (B), low from viscosity, that processability good, curing rate is excellent aspect is preferred.In cycloaliphatic epoxy, be preferably the cycloaliphatic epoxy of 2 officials' energy, particularly preferably 3,4-epoxy hexane ylmethyls-3 ', 4 '-epoxy hexane formic acid esters.
In addition, also can use the oxetane compound with the condensed cyclic structure such as fluorenes or carbazole beyond composition (A) and composition (B) or epoxy compounds as required, painting membrane rigidity can be given.These oxetane compounds or epoxy compounds can be used alone, and also can use two or more.
Curing agent (C) contained by resin combination of the present invention has reactivity with mentioned component (A) and/or (B).Can use and cause the compound of curing reaction as curing agent by the energy-ray of light etc. or heat.Can be used any one in the present invention, but usually cause the curing agent (C) of curing reaction preferably by energy-ray.
As the curing agent (C) being caused curing reaction by light homenergic ray, as long as produce cationic compound by standing ultraviolet (wavelength about 200 ~ about 400nm), just can use ad lib, can enumerate such as: cationic polymerization initiators, particularly light cationic polymerization initiators, can illustrate: sulfonium salt, iodine salt, salt, ammonium salt, stibate.
As sulfonium salt, can enumerate: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoro antimonate, triphenylsulfonium four (pentafluorophenyl group) borate, 4,4 '-bis-[diphenyl sulfonium] diphenyl sulfide-bis-hexafluorophosphate, 4,4 '-bis-[two (beta-hydroxy ethyoxyl) phenyl sulfonium] diphenyl sulfide-bis-hexafluoro antimonate, 7-[two (p-methylphenyl) sulfonium]-ITX hexafluorophosphate, 7-[two (p-methylphenyl) sulfonium]-ITX hexafluoro antimonate, 7-[two (p-methylphenyl) sulfonium]-2-isopropyl four (pentafluorophenyl group) borate, phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide-hexafluorophosphate, phenylcarbonyl group-4 '-diphenyl sulfonium-diphenyl sulfide-hexafluoro antimonate, 4-tert-butyl-phenyl carbonyl-4 '-diphenyl sulfonium-diphenyl sulfide-hexafluorophosphate, 4-tert-butyl-phenyl carbonyl-4 '-diphenyl sulfonium-diphenyl sulfide-hexafluoro antimonate, 4-tert-butyl-phenyl carbonyl-4 '-diphenyl sulfonium-diphenyl sulfide-four (pentafluorophenyl group) borate, sulfur phenenyl diphenyl sulfonium hexafluoro antimonate, sulfur phenenyl diphenyl sulfonium hexafluorophosphate, 4-{4-[2-chlorobenzene formacyl] thiophenyl } two (4-fluorophenyl) the sulfonium hexafluoro antimonate of phenyl, the halide of sulfur phenenyl diphenyl sulfonium hexafluoro antimonate, 4,4 ', 4 "-three (beta-hydroxy ethoxyl phenenyl) sulfonium hexafluoro antimonate, 4,4 '-bis-[diphenyl sulfonium] diphenyl sulfide-bis-hexafluoro antimonate, diphenyl [4-(thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate, three [4-(4-acetylbenzene sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides etc.
As iodine salt, can enumerate: diphenyl iodine four (pentafluorophenyl group) borate, diphenyl iodine hexafluorophosphate, diphenyl iodine hexafluoro antimonate, two (4-nonyl phenyl) iodine hexafluorophosphate, (tri-isopropyl benzene base) iodine four (pentafluorophenyl group) borate etc.
As salt, can enumerate: bromination three normal-butyl (2,5-dihydroxy phenyl) hexadecyl tributyl deng.
As ammonium salt, can enumerate: benzyltrimethylammonium chloride, phenyl tributyl ammonium chloride, benzyltrimethylammonium bromide etc.
As stibate, can enumerate: triphenylsulfonium hexafluoro antimonate, to (thiophenyl) phenyl diphenyl sulfonium hexafluoro antimonate, 4-chlorphenyl diphenyl sulfonium hexafluoro antimonate, the two hexafluoro antimonate of two [4-(diphenyl sulfonium) phenyl] thioether and diallyl iodine hexafluoro antimonate etc.
The curing agent (C) (light cationic polymerization initiators) of curing reaction is caused as the energy-ray by light etc. used in the present invention, preferred salt compounded of iodine and sulfonium salt, wherein, preferred high sensitive and (tri-isopropyl benzene base) iodine four (pentafluorophenyl group) borate easily obtained from market, sulfur phenenyl diphenyl sulfonium hexafluoro antimonate, 4-{4-[2-chlorobenzene formacyl] thiophenyl } two (4-fluorophenyl) the sulfonium hexafluoro antimonate of phenyl, diphenyl [4-(thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate, three [4-(4-acetylbenzene sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides etc.
In addition; in view of to the harmfulness of environment and human body and the regulation of various countries, most preferably use not containing (tri-isopropyl benzene base) iodine four (pentafluorophenyl group) borate, diphenyl [4-(thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate, three [4-(4-acetylbenzene sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides of antimony element.
Relative to total amount 100 mass parts of composition (A)+composition (B), the content of smooth cationic polymerization initiators of the present invention is 0.05 ~ 5 mass parts, is preferably 0.1 ~ 3 mass parts.It should be noted that, in resin combination of the present invention, light cationic polymerization initiators can be used alone, and also can mix multiple use.
As thermal curing agents, can enumerate such as: aminated compounds, anhydrides compound, amides compound, phenolic compound, carboxylic acid compound etc.As the concrete example of operable curing agent, can enumerate: diaminodiphenyl-methane, diethylenetriamines, trien, diamino diphenyl sulfone, IPD, dicyanodiamide, the polyamide synthesized by linolenic dimer and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrabydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride, 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, resorcinol, naphthalenediol, three (4-hydroxy phenyl) methane, 1,1,2,2-tetra-(4-hydroxy phenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthols, alkyl-substituted naphthaline phenol, dihydroxy benzenes, dihydroxy naphthlene etc.) and formaldehyde, acetaldehyde, benzaldehyde, parahydroxyben-zaldehyde, salicylaldhyde, parahydroxyacet-ophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4 '-bis-(chloromethyl)-1,1 '-biphenyl, 4,4 '-bis-(methoxy)-1,1 '-biphenyl, Isosorbide-5-Nitrae '-bis-(chloromethyl) benzene, Isosorbide-5-Nitrae ' condensation polymer of-bis-(methoxy) benzene etc. and their modifier, the halogenated bisphenol classes such as tetrabromobisphenol A, imidazoles, trifluoroboranes-amine complex, guanidine derivatives, the condensation product etc. of terpenes and phenols, but be not limited to these.They can be used alone, and also can use two or more.
In addition, in the sealing of the face of encapsulant, particularly organic EL, in most cases preferably use the acid anhydrides of the rear excellent transparency of solidification, preferable methyl tetrabydrophthalic anhydride, methylnadic anhydride, carbic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, ethylene-dimalonic acid acid anhydride, dicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, methyl bicycle [2.2.1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride etc. has the acid anhydrides of alicyclic ring skeleton.These acid anhydrides with alicyclic skeleton can use commercially available product, such as, can obtain as the solid-state product of H-TMA series or liquid product (although be liquid product, being at room temperature semisolid, the non-constant of operability) from gas chemical company of Mitsubishi etc.
In addition, when using cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride, when being used alone, owing to being solid-state or that viscosity is high semisolid, therefore operability extreme difference sometimes.Therefore, preferably with other curing agent, the acid anhydrides preferably with alicyclic skeleton using.Now, as the curing agent that can be used together, as long as be aqueous and that viscosity is low curing agent, just be not particularly limited, such as commercially available curing agent, can enumerate: the curing agent such as the HNA-100 (new Japan Chemical (strain) system) containing methylnadic anhydride, carbic anhydride or the RIKACID MH700 (new Japan Chemical (strain) system) containing hexahydrophthalic anhydride, methylhexahydrophthalic anhydride.And the used time, can in advance by solid or semi-solid cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride and low viscous curing agent (as heating condition, in order to prevent curing agent from volatilizing, are preferably less than 150 DEG C in room temperature or heating, be more preferably less than 120 DEG C) be mixed under condition evenly, become the state that operability is good thus.In addition, the depression of encapsulant after process operability and solidification, the usage rate of cyclohexane-1,3,4-tricarboxylic acid-3,4-acid anhydride in whole curing agent is 20 ~ 90 quality %, is preferably the scope of below 30 ~ 80 quality %.When mixed proportion is more than 90 quality %, the operability extreme difference of curing agent.In addition, when being less than 20 quality %, the improvement effect likely in the depression of encapsulant diminishes.
Use the mix proportion of the system of thermal curing agents of the present invention, the equivalent according to the carboxyl of the functional equivalent contained by epoxy compounds or oxetane compound and carboxylic acids curing agent decides.Preferably relative to functional group 1 equivalent, carboxyl is 0.2 ~ 5 equivalent, is more preferably 0.5 ~ 2 equivalent.When exceeding this scope, curing reaction cannot fully carry out, and produce excessive functional group, carboxyl residual, therefore the toughness of solidfied material, thermal endurance cannot give full play to.
In resin combination of the present invention, by curing catalysts together with curing agent and use, or curing catalysts can be used alone and not use curing agent.As the concrete example of operable curing accelerator, can enumerate: glyoxal ethyline, 2-phenylimidazole, 2-lauryl imidazoles, 2-heptadecyl imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1 benzyl 2 methyl imidazole, 1-cyano ethyl-glyoxal ethyline, 1-cyano ethyl-2-phenylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2,4-diaminourea-6-(2 '-methylimidazole (1 ')) ethyl s-triazine, 2,4-diaminourea-6-(2 '-undecyl 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 2:3 addition product of glyoxal ethyline isocyanuric acid, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-3,5-bishydroxymethyl imidazoles, 2-phenyl-4-hydroxymethyl-5-methylimidazole, the various imidazoles of 1-cyano ethyl-2-phenyl-3,5-dicyano ethoxyl methyl imidazoles and those imidazoles and phthalic acid, M-phthalic acid, terephthalic acid (TPA), trimellitic acid, Pyromellitic Acid, naphthalenedicarboxylic acid, maleic acid, the salt of the polybasic carboxylic acids such as oxalic acid, the amide-types such as dicyanodiamide, 1,8-diazabicyclo (5.4.0) laurylene-7 diaza compound such as grade and their tetraphenyl borate salts, the salt of phenol novolacs etc., the salt of above-mentioned polybasic carboxylic acid class or phosphonic acid based, TBAB, softex kw, the hot cationic initiators of ammonium salt class such as tricaprylmethyl ammonium bromide, triphenylphosphine, three (tolyl) phosphine, tetraphenylphosphonibromide bromide the phosphine classes such as tetraphenylphosphoniphenolate tetraphenyl borate salts, the hot cationic initiator of compounds, 1-naphthyl methyl methyl-p-hydroxybenzene sulfonium hexafluoro antimonate, benzyl methyl-p-hydroxybenzene sulfonium hexafluoro antimonate, dimethyl-to the hot cationic initiators of metaantimmonic acid salt such as acetoxyl group phenyl sulfonium hexafluoro antimonate, 1-naphthyl methyl methyl-p-hydroxybenzene sulfonium hexafluorophosphate, benzyl methyl-p-hydroxybenzene sulfonium hexafluorophosphate, dimethyl-to acetoxyl group phenyl sulfonium hexafluorophosphate etc. the metallic compounds such as phenols, amine additives, tin octoate such as the hot cationic initiator of salt, 2,4,6-triamido methylphenols etc. and the microcapsule-type curing accelerator etc. that these curing accelerator microencapsulations are obtained.Use any of those curing accelerators, the characteristic required by transparent resin composition that can obtain according to the such as transparency, curing rate, operating condition etc. and suitably selecting.Be preferably hot cationic initiator, be particularly preferably the hot cationic initiator of salt.Relative to total amount 100 mass parts of composition (A)+composition (B), curing accelerator uses usually in the scope of 0.001 ~ 15 mass parts, is preferably 0.01 ~ 5 mass parts.
In the present invention, and be also effective by the redox reaction of the cracking type Photoepolymerizationinitiater initiater used in radical polymerization system.When paralled system, the generation easiness of single Electron Transfer Reactions determines reactive, the iodine that the energy level of LUMO (lowest unoccupied molecular orbital: the index as the generation easiness of electron transfer reaction) is low the reactivity of salt is good.As long as cracking type Photoepolymerizationinitiater initiater, arbitrary Photoepolymerizationinitiater initiater, can enumerate such as: 2-hydroxy-2-methyl-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone.
As the curing agent used in the present invention, consider the thermal history to member of formation, if for hot curing, to be then preferably cured below 100 DEG C, preferably to use hot cationic polymerization initiators.In addition, the light cationic polymerization initiators without the need to heat energy is also preferably used.
Can as required and use particulate in resin combination of the present invention.
As this particulate, can enumerate: organic fine particles, inorganic particles.In addition, for particulate, required light transmittance, hardness, marresistance, cure shrinkage, refractive index can be considered, separately or mix multiple use.
As may be used for organic fine particles of the present invention, can enumerate: polystyrene resin bead, acrylic resin bead, polyurethane resin bead, the organic polymer pellets such as polycarbonate resin bead, expanded polystyrene resin beads, porous propylene acid resin bead, cellular polyurethane resin beads, the porous organic polymer beads such as porous polycarbonate resin beads, the toner of phenyl guanamines-formaldehyde condensation products, the toner of phenyl guanamines-carbamide condensation product, the toner of melocol condensation product, the powder of aspartate derivatives, zinc stearate powder, stearic amide powder, epoxy powder, polyethylene powders etc., preferred crosslinked polymethylmethacrylaparticles resin beads, crosslinked polymethylmethacrylaparticles styrene resin bead etc.These organic fine particles can easily obtain as commercially available product, in addition, also can be prepared with reference to known document.
As may be used for inorganic particles of the present invention, can enumerate: conductive metal oxide, transparent metal oxide, other inorganic filler etc.
As may be used for conductive metal oxide of 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, fluorine-doped tin oxide etc.
As may be used for transparent metal oxide of the present invention, can enumerate: silicon dioxide, titanium oxide, zirconia, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/antimony pentaoxide compound, zirconia/tin oxide/antimony pentaoxide compound, titanium oxide/zirconia/tin oxide compound etc.
As may be used for other inorganic filler of the present invention, can enumerate: calcium oxide, calcium chloride, zeolite, silica gel etc.
As may be used for particulate of the present invention, preferred hardness and excellent abrasion, the particulate that refractive index is high, preferably can use titanium oxide, zirconia, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconia/tin oxide/antimony pentaoxide compound, zirconia/tin oxide/antimony pentaoxide compound, titanium oxide/zirconia/tin oxide compound.In addition, the optical sheet for display requires high light transmittance, therefore preferred below the 100nm of the primary particle size of particulate.As their mixing ratio, be 1 ~ 30 mass parts relative to total amount 100 mass parts of composition (A)+composition (B), be preferably 5 ~ 20 mass parts.
In addition, also can be used together the dispersant as particulate such as polybasic carboxylic acid class dispersant, silane coupler, titanate esters system coupling agent, the polysiloxane-based dispersant of modified silicon wet goods, organic copolymer class dispersant.As mixing ratio during these materials of cooperation, be about 0.001 ~ about 30 quality % relative to the gross mass of resin combination of the present invention, be preferably about 0.05 ~ about 5 quality %.
It should be noted that, the minimum particle diameter that when primary particle size refers to and breaks up gathering, its particle has.That is, when the particulate of ellipse, using minor axis as primary particle size.Primary particle size can be measured by dynamic light scattering method, electron microscope observation etc.Particularly, Jeol Ltd. JSM-7700F electric field emission type scanning electron microscopy can be used, under accelerating voltage 30kV condition, measure primary particle size.
These particulates can disperse to use in a solvent.Particularly inorganic particles easily obtains commercially available product with the form being dispersed in water or organic solvent.As used organic solvent, can enumerate: the aliphatic hydrocarbon solvents such as the aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ethylbenzene, durol, hexane, octane, decane and benzinum, unleaded gas, solvent naphtha etc. as their mixture, as esters solvent, can enumerate: ethyl acetate, propyl acetate, the alkyl acetate classes such as butyl acetate, the cyclic ester classes such as gamma-butyrolacton, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, Triethylene glycol ethyl ether monoacetate, diethylene glycol monobutyl ether monoacetate, propylene glycol monomethyl ether monoacetate, butanediol monomethyl ether monoacetate etc. (single or poly-) alkylene glycol monoalkyl ethers monoacetate class, dialkyl glutarate, dialkyl succinate, the polybasic carboxylic acid alkyl esters etc. such as hexanedioic acid dialkyl ester, as ether solvent, can enumerate: the ring-type such as glycol ethers, the oxolane ethers such as the alkyl ether such as ether, methyl butyl ether, glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether, as ketones solvent, can enumerate: acetone, methyl ethyl ketone, cyclohexanone, isophorone etc.
In addition, in resin combination of the present invention, consider the viscosity, refractive index, adhesiveness etc. of the resin combination of the present invention obtained, except composition (A), composition (B), also can use reactive compounds.Particularly; can enumerate: (methyl) acrylate; as this (methyl) acrylate, multifunctional (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate etc. in simple function (methyl) acrylate, 2 officials' energy (methyl) acrylate, molecule with more than 3 (methyl) acryloyl groups can be used.
As simple function (methyl) acrylate, such as, can enumerate: (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, (methyl) acrylic acid dihydro dicyclopentadiene base ester, (methyl) acrylic acid dihydro dicyclopentadiene base oxygen base ethyl ester, ester ring type (methyl) acrylate such as (methyl) cyclohexyl acrylate, (methyl) tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, morpholine (methyl) acrylate etc. has (methyl) acrylate of heterocycle, (methyl) benzyl acrylate, ethyoxyl modification cresols (methyl) acrylate, propoxyl group modification cresols (methyl) acrylate, 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, p-phenyl phenol monosubstituted ethoxy (methyl) acrylate, p-phenyl phenol polyethoxy (methyl) acrylate, acrylic acid-adjacent phenyl benzyl ester, (methyl) acrylate of aromatic rings such as acrylic acid-have phenyl benzyl ester etc., carbazole (gathering) ethyoxyl (methyl) acrylate, carbazole (gathering) propoxyl group (methyl) acrylate, (gathering) caprolactone modification carbazole (methyl) acrylate etc. has (methyl) acrylate of heterocycle, (methyl) acrylic acid naphthalene ester, (gathering) ethyoxyl (methyl) acrylic acid naphthalene ester, (gathering) propoxyl group (methyl) acrylic acid naphthalene ester, (gathering) caprolactone modification (methyl) acrylic acid naphthalene ester, dinaphthol (methyl) acrylate, dinaphthol (gathering) ethyoxyl (methyl) acrylate, dinaphthol (gathering) propoxyl group (methyl) acrylate, (gathering) caprolactone modification dinaphthol (methyl) acrylate, naphthols (methyl) acrylate, naphthols (gathering) ethyoxyl (methyl) acrylate, naphthols (gathering) propoxyl group (methyl) acrylate, (gathering) caprolactone modification naphthols (methyl) acrylate etc. has (methyl) acrylate of condensed ring, there is acid imide (methyl) acrylate of imide ring structure, butanediol list (methyl) acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, (methyl) acrylic acid 2-hydroxybutyl, (methyl) acrylic acid 4-hydroxybutyl, DPG (methyl) acrylate etc. has (methyl) acrylate of hydroxyl, (methyl) acrylate, (methyl) acrylate, butoxy ethyl, 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) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) acrylic acid, the different myristin of (methyl) acrylic acid, (methyl) lauryl acrylate etc. has (methyl) acrylate of alkyl, ethoxydiglycol (methyl) acrylate, 2-ethylhexyl carbitol (methyl) acrylate, polyethylene glycol (methyl) acrylate, (methyl) acrylate etc. of the polyalcohols such as polypropylene glycol (methyl) acrylate.
As (methyl) acrylate monomer with 2 functional groups, can enumerate: hydrogenation neovaleraldehyde modification trimethylolpropane two (methyl) acrylate etc. has (methyl) acrylate of heterocycle, (gathering) ethyoxyl modified bisphenol A two (methyl) acrylate, (gathering) propoxyl group modified bisphenol A two (methyl) acrylate, (gathering) ethyoxyl modified bisphenol F bis-(methyl) acrylate, (gathering) propoxyl group modified bisphenol F bis-(methyl) acrylate, (gathering) ethyoxyl modified bisphenol S bis-(methyl) acrylate, (gathering) propoxyl group modified bisphenol S bis-(methyl) acrylate, hexahydrophthalic acid two (methyl) acrylate, two phenoxy group (gathering) ethyoxyl fluorenes etc. has (methyl) acrylate of aromatic rings, biphenyl dimethanol two (methyl) acrylate etc. has (methyl) acrylate of heterocycle, dinaphthol two (methyl) acrylate, dinaphthol (gathering) ethyoxyl two (methyl) acrylate, dinaphthol (gathering) propoxyl group two (methyl) acrylate, (gathering) caprolactone modification dinaphthol two (methyl) acrylate etc. has (methyl) acrylate of condensed ring, bisphenol fluorene two (methyl) acrylate, two phenoxy group methyl alcohol fluorenes two (methyl) acrylate, two phenoxetol fluorenes two (methyl) acrylate, two phenoxy group caprolactone fluorenes two (methyl) acrylate etc. have (methyl) acrylate of Ppolynuclear aromatic, the acrylate of the isocyanates such as diacrylated isocyanuric acid ester, BDO two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, poly-BDO two (methyl) acrylate etc. has (methyl) acrylate of straight chain methylene structure, ester ring type (methyl) acrylate such as Tricyclodecane Dimethanol (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, two (methyl) acrylate etc. of the polyalcohols such as polypropylene glycol two (methyl) acrylate.
As multifunctional (methyl) acrylate monomer, can enumerate: three (acryloyl-oxyethyl) isocyanuric acid ester, (gathering) caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester etc. has multifunctional (methyl) acrylate of isocyanurate ring, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (gathering) ethyoxyl modification pentaerythrite four (methyl) acrylate, (gathering) propoxyl group modification pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, (gathering) caprolactone modification dipentaerythritol five (methyl) acrylate, (gathering) ethyoxyl modification dipentaerythritol five (methyl) acrylate, (gathering) propoxyl group modification dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate, (gathering) caprolactone modification dipentaerythritol six (methyl) acrylate, (gathering) ethyoxyl modification dipentaerythritol six (methyl) acrylate, (gathering) propoxyl group modification dipentaerythritol six (methyl) acrylate, polypentaerythritol many (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (gathering) ethyoxyl modification trimethylolpropane tris (methyl) acrylate, (gathering) propoxyl group modification trimethylolpropane tris (methyl) acrylate, two trimethylolpropane four (methyl) acrylate, multifunctional (methyl) acrylate of the polyalcohols such as glycerine three (methyl) acrylate, tricresyl phosphate (methyl) acrylate etc. phosphorous multifunctional (methyl) acrylate etc., trimethylolpropane benzoic ether (methyl) acrylate etc. has aromatic multifunctional (methyl) acrylate, sour modification multifunctional (methyl) acrylate such as 2,2,2-tri-acryloyloxymethyl butanedioic acid, polysiloxanes six (methyl) acrylate etc. has multifunctional (methyl) acrylate etc. of silicone matrix.
As carbamate (methyl) acrylate, can enumerate: make diatomic alcohol compounds (such as: ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, DPG, tripropylene glycol, BDO, neopentyl glycol, 1,6-hexylene glycol, 1,8-ethohexadiol, 1,9-nonanediol, 2-methyl isophthalic acid, 8-ethohexadiol, 3-methyl isophthalic acid, 5-pentanediol, 2,4-diethyl-1,5-PD, 2-butyl-2-ethyl-1,3-PD, cyclohexane-Isosorbide-5-Nitrae-dimethanol, polyethylene glycol, polypropylene glycol, polymer with bis phenol A ethyoxyl 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, adipic acid, azelaic acid, dimeric dibasic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid or their acid anhydrides) the polyester diol of product, with organic multiple isocyanate (such as: tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, the chain saturated hydrocarbons isocyanates such as 2,4,4-trimethyl hexamethylene diisocyanate, IPDI, norbornene alkyl diisocyanate, dicyclohexyl methyl hydride diisocyanate, di-2-ethylhexylphosphine oxide (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, the cyclic saturated hydrocarbon isocyanates such as HTDI, 2,4-toluene di-isocyanate(TDI), 1,3-eylylene diisocyanate, to phenylene vulcabond, 3,3 '-dimethyl-4,4 '-vulcabond, 6-isopropyl-1,3-phenyl diisocyanate, the aromatic poly-isocyanates such as 1,5-naphthalene diisocyanate) reaction, then addition contains (methyl) acrylate of hydroxyl and the product etc. that obtains.
As polyester (methyl) acrylate, can enumerate: as polyester diol and (methyl) acrylic acid product etc. of the product of diatomic alcohol compounds and binary acid or its acid anhydrides.
Wherein, as (methyl) acrylate that may be used for resin combination of the present invention, preferably use the material that cure shrinkage is low.Particularly, preferably there is (methyl) acrylate of ring structure, can enumerate: (methyl) isobornyl acrylate, (methyl) acrylic acid tetrahydrochysene dicyclopentadiene base ester, (methyl) acrylic acid dihydro dicyclopentadiene base ester, (methyl) acrylic acid dihydro dicyclopentadiene base oxygen base ethyl ester, (methyl) cyclohexyl acrylate, p-Cumenylphenol (gathering) ethyoxyl (methyl) acrylate, naphthols (gathering) ethyoxyl (methyl) acrylate, naphthols (gathering) propoxyl group (methyl) acrylate, phenylphenol (gathering) ethyoxyl (methyl) acrylate, phenylphenol (gathering) propoxyl group (methyl) acrylate, (methyl) benzyl acrylate, Tricyclodecane Dimethanol (methyl) acrylate, hydrogenation neovaleraldehyde modification trimethylolpropane two (methyl) acrylate, biphenyl dimethanol two (methyl) acrylate etc.Be particularly preferably phenylphenol (gathering) ethyoxyl (methyl) acrylate that Tg is high, cure shrinkage is low of solidfied material, Tricyclodecane Dimethanol (methyl) acrylate, hydrogenation neovaleraldehyde modification trimethylolpropane two (methyl) acrylate, biphenyl dimethanol two (methyl) acrylate.It should be noted that, in resin combination of the present invention, (methyl) acrylate as other composition can be used alone, and also can mix multiple use.Use level in the present invention during cooperation (methyl) acrylate is 100 mass parts relative to composition (A)+composition (B) is 10 ~ 200 mass parts, is preferably 50 ~ 150 mass parts.
In addition, when using (methyl) acrylate, preferably use the Photoepolymerizationinitiater initiater beyond above-mentioned smooth cationic polymerization initiators.Particularly, can enumerate: the benzoin classes such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether; Acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 2, the acetophenones such as 2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropane-1-ketone, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone]; The Anthraquinones such as 2-EAQ, 2-tert-butyl group anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, ITX, CTX; The ketal classes such as acetophenone dimethyl ketal, benzyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 4, the benzophenones such as 4 '-bis-methylamino benzophenone; The phosphinoxides etc. such as TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, diphenyl-(2,4,6-trimethylbenzoyl) phosphine oxide.Be preferably acetophenones, more preferably can enumerate: 2-hydroxy-2-methyl-phenyl-propane-1-ketone, 1-hydroxycyclohexylphenylketone.When using this radical polymerization initiator, relative to (methyl) acrylate component 100 mass parts, be preferably 0.1 ~ 10 mass parts.Be more preferably 1 ~ 5 mass parts.It should be noted that, in resin combination of the present invention, Photoepolymerizationinitiater initiater can be used alone, and also can mix multiple use.
The usage ratio of each composition of resin combination of the present invention can be considered desired refractive index, durability, viscosity, adhesiveness etc. and determine.
Usually, when composition (A)+composition (B) is set to 100 mass parts, the content of composition (A) is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.The content of composition (B) is 20 ~ 80 mass parts, is preferably 30 ~ 70 mass parts.If be hot cationic initiator, then the content of composition (C) is 0.05 ~ 5 mass parts, is preferably 0.1 ~ 3 mass parts.
Relative to the total amount of resin combination of the present invention, the total amount of usual composition (A)+composition (B) is preferably about 50 ~ about 99 quality %, be more preferably 70 ~ 99 quality %, more preferably 80 ~ 99 quality %, can be according to circumstances 90 ~ 99 quality %, can also be 95 ~ 99 quality %.Remainder is mentioned component (C) and optional adding ingredient.
In resin combination of the present invention, except mentioned component, in order to improve the convenience etc. during process, according to circumstances, can be used together containing release agent, defoamer, levelling agent, light stabilizer, antioxidant, polymerization inhibitor, plasticizer, antistatic agent etc.
In addition, in order to obtain durability, flexibility, use the example of plasticizer also a lot.As used material, select according to desired viscosity, durability, the transparency, flexibility etc.Particularly, can enumerate: polyethylene, the olefin polymers such as polypropylene, repefral, diethyl phthalate, dibutyl phthalate, phthalic acid two (2-ethylhexyl) ester, diisooctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, glycolic ethylphthalyl ethyl glycolate ethyl ester, the phthalic acid esters such as glycolic butyl phthalyl butyl ester, the trimellitates such as tri trimellitate (2-ethylhexyl) ester, dibutyl adipate, diisobutyl adipate, adipic acid two (2-ethylhexyl) ester, diisononyl adipate, diisodecyl adipate (DIDA), adipic acid two (2-(2-Butoxyethoxy) ethyl) ester, azelaic acid two (2-ethylhexyl) ester, dibutyl sebacate, decanedioic acid two (2-ethylhexyl) ester, the fatty group dibasic acids such as diethyl succinate, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tricresyl phosphate (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tricresyl phosphate (dimethylbenzene) ester, cresyl phosphate diphenyl ester, the orthophosphates such as phosphoric acid 2-Octyl Nitrite diphenyl ester, the ricinoleate esters such as acetyl group methyl ricinolcic acid, polyester such as poly-(1,3-BDO adipate esters), the acetic acid esters such as glyceryl triacetate, the sulfonamide such as N-butylbenzenesulfonamide, polyethylene glycol benzoic ether, polyethylene glycol dibenzoate, polypropylene glycol benzoic ether, dibenzonate, poly-BDO benzoic ether, polyalkylene oxide (two) benzoic ethers such as poly-BDO benzoic ether, polypropylene glycol, polyethylene glycol, the polyethers such as poly-BDO, polyethoxy modified bisphenol A, the poly-alkoxy-modified bisphenol-A such as poly-propoxyl group modified bisphenol A, polyethoxy modified bisphenol F, the poly-alkoxy-modified Bisphenol F such as poly-propoxyl group modified bisphenol F, naphthalene, luxuriant and rich with fragrance, the Ppolynuclear aromatics such as anthracene, (connection) naphthols, (gathering) ethyoxyl modification (connection) naphthols, (gathering) propoxyl group modification (connection) naphthols, (gathering) BDO modification (connection) naphthols, the naphthol derivatives such as (gathering) caprolactone modification (connection) naphthols, diphenyl sulfide, diphenyl polysulfide, benzothiazolyl disulfide, rhenocure CA, morpholinodithio benzothiazole, cyclohexylbenzothiazole-2-sulfenamide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, curing four (2-ethylhexyl) thiuram, tetramethylthiuram monosulfide, the sulfur-containing compounds such as bis-pentamethylenethiuram tetrasulfide.Be preferably (gathering) ethylene glycol phenyl formic acid esters, (gathering) propylene glycol phenyl formic acid esters, dinaphthol, (gathering) ethyoxyl modification (connection) naphthols, (gathering) propoxyl group modification (connection) naphthols, diphenyl sulfide.
In order to improve adhesive tension, coupling agent can be added.For used coupling agent, be not particularly limited, but preferably containing silane coupler.As silane coupler, can enumerate such as: 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(2-amino-ethyl) 3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl) 3-TSL 8330, APTES, 3-mercaptopropyi trimethoxy silane, vinyltrimethoxy silane, N-(2-(vinyl-benzylamino) ethyl) 3-TSL 8330 hydrochloride, 3-methacryloxypropyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, the silane couplers such as 3-r-chloropropyl trimethoxyl silane, isopropyl (N-ethylaminoethyl is amino) titanate esters, isopropyl three isostearoyl base titanate esters, two (dioctylphyrophosphoric acid) fluoroacetic acid titanium, tetra isopropyl two (dioctyl phosphito ester) titanate esters, the titanium class coupling agents such as new alkoxyl three (p-N-(beta-aminoethyl) aminophenyl) titanate esters, acetylacetone,2,4-pentanedione zirconium, methacrylic acid zirconium, propionic acid zirconium, new alkoxy zirconium ester, the new trineodecanoyl zirconate of new alkoxyl three, new alkoxyl three (dodecanoyl) benzenesulfonyl zirconate, new alkoxyl three (ethylene amino-ethyl) zirconate, new alkoxyl three (m-aminophenyl base) zirconate, zirconium carbonate ammonium, aluminium acetylacetonate, aluminium methacrylate, zirconium or the aluminium class coupling agents such as propionic acid aluminium, they can be used alone, and also can mix two or more and use.In these coupling agents, be preferably silane coupling agent, be more preferably amino silicone alkanes coupling agent or epoxy radicals silicone hydride class coupling agent.By using coupling agent, can obtain that moisture-proof reliability is excellent, encapsulant that the reduction of adhesive strength after moisture absorption is few.The content of this coupling agent is about 0.05 ~ about 3 mass parts relative to reactive resin compositions 100 mass parts.
In addition, as required, also the polymer class such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be added.For the composition without reactive group, from the viewpoint of compatibility, weight average molecular weight is preferably 10,000g/mol.In addition, in order to reduce moisture-vapor transmission, also the organo-metallic compounds such as alkyl aluminum can be added.Also can add solvent, but preferably not add solvent.
In resin combination of the present invention, the weight average molecular weight of each composition is preferably 10, below 000g/mol, is more preferably 5, below 000g/mol.The composition large due to weight average molecular weight does not dissolve, and the resin combination thus prepared becomes muddy liquid.Owing to must be even and transparent for the resin combination of display, be therefore unaccommodated.In addition, also require excellent characteristic for transmitance, specifically, the light transmittance of each wavelength within the scope of optimal wavelength 380 ~ 780nm is more than 90%.Light transmittance can be measured by sensing equipments such as Co., Ltd. Hitachi high-tech spectrophotometer U-3900H.
Resin combination of the present invention can according to conventional methods by preparing each composition mixed dissolution.Such as by each composition is dropped in the round-bottomed flask with agitating device, thermometer, and can stir 0.5 ~ 6 hour at 40 ~ 80 DEG C and obtain.
The viscosity of the operability of the processability when viscosity of resin combination of the present invention needs for being suitable for manufacturing display etc., is particularly suitable for the viscosity of the face sealing of organic EL element.Organic EL element forms following structure usually: by the region that bank material surrounds, the substrates such as glass stack gradually metal electrode, organic carrier transport layer, organic EL luminescent layer, ITO electrode, passivating film from this substrate-side, this passivating film is filled with packing material (face resin composition for encapsulating), thereon further with hermetic sealing substrate sealings such as glass.This packing material is filled into the space between the substrate of above-mentioned metal electrode side and the hermetic sealing substrate of its opposition side; play the effect of the moisture protecting organic luminous layer from outside etc.; usual use hardening resin composition; after filling this resin combination; the hermetic sealing substrates such as usual mounting glass; then resin composition is made, thus sealing organic luminous layer.Therefore, in order to seal the gap between aforesaid substrate completely, this resin combination is preferably low viscosity.
This viscosity be preferably use E type viscosimeter (TV-200: the Dong Ji industry companies's system) viscosity that measures at 25 DEG C be 1.5Pas (1500mPas) below, be more preferably below 1300mPas, more preferably below 700mPas, is particularly preferably below 400mPas.Lower limit is not particularly limited, and is generally about 50mPas.
In the present invention, the resin combination containing the curing agent being caused curing reaction by energy-ray easily can make it solidify by energy-ray.At this, as the concrete example of energy-ray, can enumerate: the particle ray etc. such as the electromagnetic waves such as ultraviolet, visible ray, infrared ray, X ray, gamma-radiation, laser, α-ray, beta rays, electron ray.In the present invention, among those, ultraviolet, laser, visible ray or electron ray is preferably.
According to conventional methods, by irradiating above-mentioned energy-ray to resin combination of the present invention, solidfied material of the present invention can be obtained.The liquid refractivity of resin combination of the present invention is generally 1.45 ~ 1.70, is preferably 1.50 ~ 1.65.Refractive index can use the mensuration such as Abbe refractomecer (model: DR-M2, Co., Ltd. ア タ go system).
In addition, the shrinkage (cure shrinkage) during the solidification of resin combination of the present invention is the smaller the better, is preferably less than 5%, is more preferably less than 4%, and more preferably less than 3.5%.
In addition, in order to protect organic luminous layer from the moisture etc. of outside, the moisture-vapor transmission of the solidfied material of resin combination of the present invention is 50g/m 224 hours (60 DEG C, measure under the condition of humidity 90%, lower with) below, be preferably 35g/m 2less than 24 hours, be more preferably 30g/m 2less than 24 hours, be preferably less than 30g/m further 224 hours.
In addition, the glass transition temperature of solidfied material is preferably up to a certain degree, and in the present invention, this Tg is preferably more than 40 DEG C, is more preferably more than 45 DEG C, most preferably is more than 50 DEG C.
Below record the optimal way of resin combination of the present invention.
I. the resin combination that seals of the face for OLED display, it contains following aromatic compound (A), cyclic compound (B) (wherein, when being selected from the skeleton in the group described in B-2, the compound for different from the compound used as aromatic compound (A)) and curing agent (C);
Aromatic compound (A) is for having the aromatic compound (A) of at least one skeleton in the group that is selected from and is made up of skeleton, anthracene skeleton and the luxuriant and rich with fragrance skeleton shown in the skeleton shown in above-mentioned formula (A-A), above-mentioned formula (A-B) and oxetanyl or epoxy radicals;
Cyclic compound (B) is for having the cyclic compound or alicyclic epoxy resin that are selected from least one skeleton in the group described in following B-2 or the group described in following B-3 and oxetanyl or epoxy radicals; B-2: phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S; B-3: isobornyl, adamantane, pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
Ii. the resin combination described in above-mentioned i, wherein, any one of aromatic compound (A) and cyclic compound (B) comprises 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) for have select free phenyl, biphenyl and bisphenol-A to form group in skeleton as the aromatic compound (A) of aromatic backbone.
Iv. the resin combination according to any one of above-mentioned i ~ iii, wherein, aromatic compound (A) comprises the aromatic compound (A) with an oxetanyl or epoxy radicals.
V. the resin combination according to any one of above-mentioned i ~ iv, wherein, aromatic compound (A) comprises the aromatic compound (A) with an epoxy radicals.
Vi. the resin combination according to any one of above-mentioned i ~ v, wherein, aromatic compound (A) is o-phenyl phenol glycidol ether.
Vii. the resin combination according to any one of above-mentioned i ~ vi, wherein, cyclic compound (B) is selected from the cyclic compound (B) of the skeleton in the group described in following (B-3) for the skeleton in the group that has (a) and select free phenyl, biphenyl, naphthalene, dinaphthalene and bisphenol-A to form or (b)
B-3: isobornyl, adamantane, pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
Viii. the resin combination according to any one of above-mentioned i ~ vii, wherein, cyclic compound (B) for have select free phenyl, biphenyl, bisphenol-A, pentamethylene, cyclohexane and hydrogenated bisphenol A to form group in the cyclic compound (B) of skeleton.
Ix. the resin combination described in above-mentioned viii, wherein, cyclic compound (B) is for having the cyclic compound (B) of the skeleton in the group that is selected from and is made up of biphenyl, bisphenol-A and cyclohexane.
X. the resin combination according to any one of above-mentioned i ~ ix, wherein, cyclic compound (B) is cyclic compound (B) or the limonene oxide at least with at least 2 oxetanyls or epoxy radicals.
Xi. the resin combination according to 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) comprises the bisphenol A diglycidyl ether that viscosity is below 1500mPas.
Xiii. the resin combination according to any one of above-mentioned i ~ xii, wherein, cyclic compound (B) comprises alicyclic epoxy resin.
Xiv. the resin combination according to 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 below 1300mPas.
Xvi. the resin combination according to any one of above-mentioned i ~ xv, wherein, when forming the solidfied material of thickness 100 μm, 60 DEG C, the moisture-vapor transmission of this solidfied material that measures under the condition of relative humidity 90% is 35g/m 2less than 24 hours.
Xvii. the resin combination described in above-mentioned xvi, wherein, the moisture-vapor transmission of above-mentioned solidfied material is 30g/m 2less than 24 hours.
Xviii. the resin combination according to any one of above-mentioned i ~ xvii, its cure shrinkage is less than 4%.
Xix. the resin combination according to any one of above-mentioned i ~ xvii, wherein, the liquid refractivity of resin combination is 1.54 ~ 1.7.
Xx. the resin combination according to any one of above-mentioned i ~ xix, wherein, the glass transition temperature (Tg) of the solidfied material of resin combination 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 according to any one of above-mentioned i ~ xxi, wherein, aromatic compound (A): the ratio of cyclic compound (B) is 3:7 ~ 7:3.
Xxiii. the resin combination according to any one of above-mentioned i ~ xxi, wherein, aromatic compound (A): the ratio of cyclic compound (B) is 3.5:6.5 ~ 6.5:3.5.
Xxiv. the resin combination according to any one of above-mentioned i ~ xxi, wherein, curing agent is light cationic polymerization initiators.
Xxv. the resin combination described in above-mentioned xxiv, wherein, light cationic polymerization initiators is for being selected from by (tri-isopropyl benzene base) iodine compound in the group of four (pentafluorophenyl group) borate, diphenyl [4-(thiophenyl) phenyl] sulfonium trifluoro three (pentafluoroethyl group) phosphate and three [4-(4-acetylbenzene sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides composition.
Xxvi. the resin combination according to any one of above-mentioned i ~ xxv, wherein, aromatic compound (A) is o-phenyl phenol glycidol ether, what cyclic compound (B) was below viscosity 1500mPas is selected from by bisphenol A diglycidyl ether, xylylene dioxygen azetidine, 3, 3 ', 5, 5 '-tetramethyl-4, 4 '-bis-(glycidoxy)-1, 1 '-biphenyl, biphenyl aralkyl-type polyglycidyl ether, 3, 4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters, compound in the group of hydrogenated bisphenol A diglycidyl ether and limonene oxide composition.
Xxvii. the resin combination described in above-mentioned xxvi, wherein, what cyclic compound (B) was below viscosity 1500mPas is selected from by bisphenol A diglycidyl ether, 3,4-epoxy hexane ylmethyl-3 ', the compound in the group of 4 '-epoxy hexane formic acid esters and hydrogenated bisphenol A diglycidyl ether composition.
Xxviii. the resin combination according to any one of above-mentioned i ~ xxv, wherein, the aliphat ring of the alicyclic epoxy resin of cyclic compound (B) is carbon number 6 or 7, is more preferably cyclohexane ring.
The sealed solid method of organic EL element of the present invention comprises following operation: be formed at the operation organic EL element on substrate being formed passivating film; Coated face resin composition for encapsulating on above-mentioned passivating film, and the operation of sealing transparency carrier is set; With the operation making above-mentioned resin composition for encapsulating solidification; It is characterized in that, use the hardening resin composition of the invention described above as sealing resin combination.
The organic EL element sealed is made up of substrate and the element portion main body that comprises lower electrode, the organic EL layer at least comprising luminescent layer and upper electrode.Use glass substrate, comprise the transparent organic material of cycloolefin or Merlon, polymethyl methacrylate etc., this transparent organic material glass fibre etc. carried out high rigidization and the hybrid transparency carrier etc. that obtains comprises the flat substrate of electrical insulating property material as substrate.In addition, the representativeness as element portion main body is formed, and 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
Such as, the organic EL element with the Rotating fields of above-mentioned (4) can make as follows: on the one side of substrate, form by resistive heating evaporation or sputtering method the lower electrode (negative electrode) comprising Al-Li alloy etc., then stacked gradually by the film forming method such as resistive heating evaporation or ion beam sputtering and comprise electron transfer layer, the luminescent layer of oxadiazole derivative, triazole derivative etc., comprise TPD (N, N '-diphenyl-N, N '-bis-(3-aminomethyl phenyl)-1,1-xenyl-4,4 '-diamines) etc. hole transmission layer and upper electrode (anode) as organic EL layer.It should be noted that, as long as the Rotating fields of organic EL element or material play the function as display element, be just not particularly limited.In addition, sealed solid method of the present invention can both be applied for the organic EL element of any structure.
Passivating film is formed in the mode covering organic EL element.Passivating film can use the inorganic material such as silicon nitride, silica to be formed by the method such as evaporation or sputtering.Passivating film is arranged to prevent moisture, ionic impurity etc. from invading organic EL element.The thickness of passivating film is preferably the scope of 10nm ~ 100 μm, more preferably the scope of 100nm ~ 10 μm.In order to improve reliability, also can stacked passivating film.
For passivating film, although depend on membrane formation process, being generally the faulty film that there is pin hole, is in most cases the weak film of mechanical strength.Therefore, in sealed solid method, further coating binder on passivating film, uses sealing transparency carrier to crimp, and makes adhesive solidification, thus improve the reliability of sealing.
Embodiment
Next, the present invention is illustrated in greater detail by embodiment.The invention is not restricted to following embodiment.It should be noted that, the unit " part " of numerical value represents mass parts.
With the composition shown in following embodiment and comparative example, obtain embodiment and comparative example ultraviolet-curing resin composition separately and respective solidfied material.In addition, the evaluation method of resin combination and cured film and evaluation criterion are carried out as follows.
(1) viscosity: use E type viscosimeter (TV-200: Toki Sangyo Co., Ltd.'s system) to measure at 25 DEG C.
(2) liquid refractivity: with Abbe refractomecer (DR-M2; Co., Ltd. ア タ go system) measure joined together by the refractive index (25 DEG C) of resin combination.
(3) moisture-vapor transmission: clamp energy-ray or thermohardening type resin with glass substrate, uses the sept of 100 μm to regulate thickness, with high-pressure mercury lamp (80W/cm, ozone free) at 3000mJ/cm 2condition under or heat 1 hour and make it solidify at 100 DEG C, thus make test pieces.The test pieces Lyssy moisture-vapor transmission meter L80-5000 (SystechIllinois Inc.) of gained, the condition mensuration moisture permeability at 60 DEG C × 90%RH.
(4) Tg (glass transition temperature): for the energy-ray after solidification or the Tg point of thermohardening type resin bed, measure with determination of viscoelasticity system EXSTAR DMS-6000 (SII nanosecond science and technology Co., Ltd. system), stretch mode, frequency 1Hz.
(5) cure shrinkage: be coated with energy-ray or thermohardening type resin bed on base material, by high-pressure mercury lamp (80W/cm, ozone free) 3000mJ/cm 2irradiation or 100 DEG C, drier heating 1 hour, make resin composition, thus make the solidfied material of film gravity test.
According to JIS K7112B method, measure the proportion (DS) of solidfied material.In addition, at 23 ± 2 DEG C, measure the proportion (DL) of resin combination, calculate cure shrinkage by following formula.The measurement result mean value of the measurement result of 4 times represents.
Cure shrinkage (%)=(DS-DL)/DS × 100
(6) processability: on clean glass substrate, by KAYATORON Z-5536, with thickness 5 μm, uses point gum machine (SHOTMASTER: Musashi エ Application ジ ニ ア リ Application グ Co., Ltd. system), carries out the coating of seal pattern.
Then, point gum machine is used to drip droplet in the same manner as seal pattern in seal pattern frame the resin combination of embodiment and comparative example.
Then, by glass substrate clean for another sheet, use laminating apparatus, in a vacuum, with the baseplate-laminating after above-mentioned dropping resin combination.Then, be communicated with air, form gap, irradiate UV (accumulative light quantity: 3000mJ/cm 2) and make it solidify, drop into the baking oven of 120 DEG C, be heating and curing 1 hour, thus make sample for evaluation.
Evaluation criterion
Zero ... dropping liquid is sprawled rapidly in sample room, resin combination gapless and being full of equably in sample room
△ ... dropping liquid is slightly slow to sprawling in sample room, but resin combination gapless and being full of equably in sample room
× ... dropping liquid is not fully sprawled in sample room, in sample room, produce gap, and resin combination is not full of in sample room equably
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-(glycidoxy)-1,1 '-biphenyl
KAYARAD NC-3000H: Nippon Kayaku K. K's biphenyl aralkyl-type polyglycidyl ether
SEJ-01R: Nippon Kayaku K. K's system 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane formic acid esters
GSID 26-1:, BASF Amada Co., Ltd. system (three [4-(4-acetylbenzene sulfenyl) phenyl] sulfonium three [(trifluoromethyl) sulfonyl] methanides
EPOLIGHT 4000: Kyoeisha Chemical Co., Ltd.'s hydrogen manufacturing bisphenol A diglycidyl ether
Limonene oxide: RENESSENZ Inc. limonene oxide
EPOLIGHT 80MF: Kyoeisha Chemical Co., Ltd.'s glycerin diglycidyl ether
EPOLIGHT 100MF: Kyoeisha Chemical Co., Ltd.'s trihydroxymethylpropanyltri diglycidyl ether
From the evaluation result of embodiment 1 ~ 5 and comparative example 1 ~ 3, the Tg with the resin combination of the present invention of specific composition is high, cure shrinkage, moisture-vapor transmission are low.Therefore, the face encapsulant of the smears of such as Obstruct membrane, various encapsulant, particularly organic EL element is suitable for.
Industrial applicability
Visible light transmissivity, the light resistance of resin combination of the present invention and solidfied material thereof are excellent, Tg is high, cure shrinkage, moisture-vapor transmission are low, are therefore suitable for various encapsulant, are particularly suitable for the face encapsulant of organic EL element.

Claims (25)

1. for the resin combination that the face of organic electroluminescent device seals, it contains: the aromatic compound (A) with at least one skeleton in the group being selected from and being made up of skeleton, anthracene skeleton and the luxuriant and rich with fragrance skeleton shown in the formula (A-B) of the skeleton shown in the formula of following (i) (A-A), following (ii) and oxetanyl or epoxy radicals; With there is oxetanyl or epoxy radicals and meet the cyclic compound (B) of the condition of following (iii); And
The viscosity that this resin combination measures at 25 DEG C is below 1300mPas;
Skeleton shown in (i) formula (A-A):
In above-mentioned formula, X represents Direct Bonding, sulphur atom or dimethylated methylene base, R 1represent the alkyl of hydrogen atom or carbon number 1 ~ 4, m represents the integer of 1 ~ 4;
(ii) skeleton shown in formula (A-B):
In above-mentioned formula, R 2represent the alkyl of hydrogen atom or carbon number 1 ~ 4, n represents the integer of 1 ~ 4;
(iii) condition of this cyclic compound (B):
Ring in this cyclic compound (B) is aromatic ring, aliphat ring or heterocycle, wherein, when ring is (a) aromatic ring, this cyclic compound is the compound of the different structure of the compound had from use as described aromatic compound (A); In addition, when ring is (b) aliphat ring, this cyclic compound is have the ester ring type hydrocarbon skeleton of bridged linkage or the cyclic compound of cycloalkylidene skeleton and oxetanyl or epoxy radicals or alicyclic epoxy resin.
2. resin combination as claimed in claim 1, wherein, aromatic compound (A) has the skeleton in the group be selected from described in following (A-1),
A-1: phenyl, biphenyl, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
3. resin combination as claimed in claim 1 or 2, wherein, aromatic compound (A) for have select free phenyl, biphenyl and bisphenol-A to form group in skeleton as the compound of aromatic backbone.
4. the resin combination according to any one of claims 1 to 3, wherein, cyclic compound (B) has the ring in the group be selected from described in following (B-1),
B-1: aromatic ring, above-mentioned aliphat ring and heterocycle.
5. resin combination as claimed in claim 1, wherein, cycloalkylidene skeleton forms the skeleton shown in following formula (B-A):
In above-mentioned formula, Y represents Direct Bonding, sulphur atom or methylene, R 3represent the alkyl of hydrogen atom or carbon number 1 ~ 4, t represents the integer of 1 ~ 4.
6. resin combination as claimed in claim 1, wherein, cyclic compound (B) is alicyclic epoxy resin.
7. the resin combination according to any one of Claims 1 to 4, wherein, the ring of cyclic compound (B) is aromatic ring.
8. resin combination as claimed in claim 7, wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-2),
B-2: phenyl, biphenyl, naphthalene, dinaphthalene, anthracene, phenanthrene, bisphenol-A, Bisphenol F and bisphenol S.
9. resin combination as claimed in claim 8, wherein, cyclic compound (B) for have select free phenyl, biphenyl, naphthalene, dinaphthalene and bisphenol-A to form group in the oxetane compound of skeleton or epoxy compounds.
10. the resin combination according to any one of Claims 1 to 4, wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-3),
B-3: isobornyl, adamantane, pentamethylene, cyclohexane, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F and A Hydrogenated Bisphenol A S.
11. resin combinations as described in claim 4 or 10, wherein, cyclic compound (B) is for having oxetane compound or the epoxy compounds of the skeleton in the group that is selected from and is made up of adamantane, cyclohexane and hydrogenated bisphenol A.
12. resin combinations according to any one of Claims 1 to 4, wherein, cyclic compound (B) has the skeleton in the group be selected from described in following (B-4),
B-4: morpholine, oxolane, oxinane, dioxane, triazine, carbazole, pyrrolidines and piperidines.
13. resin combinations as described in claim 4 or 12, wherein, cyclic compound (B) is for having oxetane compound or the epoxy compounds of the skeleton in the group that is selected from and is made up of oxinane, dioxane and triazine.
14. resin combinations according to any one of claim 1 ~ 13, it is also containing curing agent (C).
15. resin combinations as claimed in claim 14, wherein, curing agent (C) is light cationic polymerization initiators.
16. resin combinations as claimed in claim 15, wherein, described smooth cationic polymerization initiators for being selected from least one in the group described in following (C-1),
C-1: sulfonium salt, iodine salt, salt, ammonium salt and stibate.
17. resin combinations as claimed in claim 14, wherein, curing agent (C) is thermal curing agents.
18. resin combinations as claimed in claim 17, wherein, described thermal curing agents is selected from the group described in following (C-2),
C-2: aminated compounds, anhydrides compound, amides compound, phenolic compound, carboxylic acid compound, glyoxaline compound, isocyanuric acid adduct, metallic compound, sulfonium salt, ammonium salt, stibate, salt, microcapsule-type curing agent.
19. resin combinations according to any one of claim 1 ~ 18, wherein, relative to total amount 100 mass parts of aromatic compound (A) with cyclic compound (B), the aromatic compound (A) containing 20 ~ 80 mass parts.
20. resin combinations according to any one of claim 1 ~ 19, wherein, relative to total amount 100 mass parts of aromatic compound (A) with cyclic compound (B), the cyclic compound (B) containing 20 ~ 80 mass parts.
21. resin combinations according to any one of claim 1 ~ 20, wherein, when aromatic compound (A) is set to 100 mass parts with the total amount of cyclic compound (B), the curing agent (C) containing 0.1 ~ 5 mass parts.
22. resin combinations according to any one of claim 1 ~ 21, wherein, when forming the solidfied material of thickness 100 μm, 60 DEG C, the moisture-vapor transmission of this solidfied material that measures under the condition of relative humidity 90% is 35g/m 2less than 24 hours.
23. 1 kinds of display of organic electroluminescence, wherein, the solidfied material that utilization makes the resin composition according to any one of claim 1 ~ 22 and obtains has carried out face sealing.
The film that 24. 1 kinds of faces for display of organic electroluminescence seal, it by be coated on by the resin combination according to any one of claim 1 ~ 22 on base material and to make it solidify and obtain, and has barrier property.
The application of resin combination according to any one of 25. claims 1 ~ 22 in the sealing of the face of organic electroluminescent device.
CN201380062164.0A 2012-11-28 2013-11-27 Resin combination and its solidfied material (1) Expired - Fee Related CN104813741B (en)

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Granted publication date: 20180105