CN105073800B - Energy ray curable resin composition and its solidfied material - Google Patents

Energy ray curable resin composition and its solidfied material Download PDF

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Publication number
CN105073800B
CN105073800B CN201480019186.3A CN201480019186A CN105073800B CN 105073800 B CN105073800 B CN 105073800B CN 201480019186 A CN201480019186 A CN 201480019186A CN 105073800 B CN105073800 B CN 105073800B
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methyl
acrylate
poly
resin combination
skeleton
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CN105073800A (en
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木户场润
松尾雄朗
松尾雄一朗
内藤伸彦
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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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1811—C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety

Abstract

A kind of resin combination, it contains (methyl) acrylate compounds (A), ring-type (methyl) acrylate compounds (B) and polymerization initiator (C) with fragrant hydrocarbon skeleton, wherein, compound (B) is selected from least one of the group being made of (methyl) acrylate compounds, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton and (methyl) acrylate compounds with heterocyclic skeleton with fragrant hydrocarbon skeleton in addition to compound (A) (methyl) acrylate compounds.

Description

Energy ray curable resin composition and its solidfied material
Background technology
Energy ray curable resin can generally be processed in the absence of a solvent, therefore workability is excellent.Further, since Curing rate is fast, energy requirement is low, therefore energy ray curing technology is in the various productions using display periphery material as representative It is important technology in industry.In recent years, in display, be referred to as the thin display of flat-panel monitor (FPD), particularly wait from Daughter display (PDP), liquid crystal display (LCD) have been put into the market and widely available.In addition, expect organic electroluminescent (EL) display (OLED) is used as follow-on emissive type thin-film display, and a part of product is practical.It is organic The organic EL element of EL display has on the substrates such as the glass formed with drive circuits such as TFT formed with comprising containing cloudy The structure of the components Department main body of the thin-film laminate of the luminescent layer of pole and anode clamping.The layers such as the luminescent layer or electrode of components Department hold Easily deteriorated because of moisture or oxygen, brightness or the reduction in service life, discoloration are produced because of deterioration.Therefore, organic EL element is sealed To block the intrusion from exterior moisture or impurity.In order to realize the organic EL element of high-quality and high reliability, it is expected more High performance sealing material, is studying various sealing techniques all the time.
As the representational encapsulating method of organic EL element, have studied will be previously inserted the made of metal or glass of drier The sealing cover of glass is fixed on the method (patent document 1) on the substrate of organic EL element using sealing with adhesive.This method In, in the substrate peripheral part coating binder of organic EL element, sealing cover is set on it, then cures adhesive, thus Substrate and sealing cover are fixed, so that sealing organic el element.In such method, carried out using the sealing cover of glass system It is sealed to mainstream.But the sealing cover of glass system is by carrying out the borehole for drier to be inserted into flat glass substrate Process and make, therefore the tendency become higher with cost.In addition, the sealing carried out using sealing cover is due in the inner side of sealing cover Drier is inserted into, thus light can not be extracted from sealing cover side.That is, the light sent from the substrate-side extraction of element from light source, is limited It is formed on bottom emission type element.In the case of bottom emission type element, there are the problem of be：By the driving being formed on substrate The reduction of aperture opening ratio caused by circuit portion, and due to drive circuit portion cover a part of light and caused by extraction efficiency drop It is low.It can be applied to therefore, it is desirable to develop from the top emission type element of the opposite side of the substrate of organic EL element extraction light Encapsulating method.
As the representational encapsulating method that can be applied to top emission type element, there are diaphragm seal method and sealed solid Method.Diaphragm seal method in organic EL element laminated multi-layer include inorganic or organic material film and form the side of passivating film Method (patent document 2).In order to assign sufficient moisture resistance, it is necessary to stack gradually several layers on element to element by this method Film.Therefore, for diaphragm seal method, film formation process is long and of high cost, further, since the required large-scale vacuum that forms a film The introducing of system equipment, thus the tendency become higher with initial investment.
On the other hand, sealed solid method is that passivating film is set in a manner of covering the components Department of whole organic EL element, and The method (referring to patent document 3) of sealing transparent substrate is set over which sealing material.In general, passivating film passes through evaporation Or sputtering inorganic material and formed, but it is the defective film with pin hole or the weak film of mechanical strength in most cases.Cause This, in sealed solid method, after setting passivating film on element, the sealings such as glass substrate are set with thoroughly via sealing adhesive Bright substrate, thus improves the reliability of sealing.Such sealed solid method is sent out as that can implement top simply and at low cost The method of the sealing of light type element attracts attention.
In the sealing carried out using sealed solid method of organic EL element, heat or light-cured resin conduct can be used Sealing adhesive, but their characteristic produces notable shadow due to being possible to the performance of element and the productivity of sealing operation Ring, thus it is extremely important.For example, when the water vapour permeability of sealing adhesive is insufficient, it is possible to invaded from the pin hole of passivating film Enter components Department, cause the deterioration of element.In addition, if the curing reaction of sealing material is slow, then curing process expends the time, sealing The productivity of operation is likely to decrease.
For the sealing adhesive used in these, in addition to requiring the high-transmission rate in visible region, Also require be resistant to luminous light resistance, the formability of stabilization, the low cure shrinkage for suppressing residual stress, for protecting Light-emitting component is from low water vapour permeability of moisture etc..Known adhesive can be used to be used as the sealing of organic EL element Adhesive and implement to seal by sealed solid method, but be difficult to obtain and disclosure satisfy that reliability and productivity, water vapour at present Transmitance as a result, it is expected to develop the sealing adhesive that can be suitable for sealed solid method.
Prior art literature
Patent document
Patent document 1：Japanese Patent No. 3876630
Patent document 2：Japanese Patent No. 2679586
Patent document 3：Japanese Patent No. 4421938
Patent document 4：Japanese Patent No. 4655172
Patent document 5：Japanese Unexamined Patent Publication 2001-81182 publications
Patent document 6：Japanese Unexamined Patent Publication 2000-169552 publications
The content of the invention
Problem to be solved by the invention
Resin combination and curing it is an object of the invention to provide the sealing material for being suitable for organic EL element The low solidfied material of the excellent, transmission of visible light of property, cure shrinkage, water vapour permeability.
The means used to solve the problem
The present inventor has carried out research extensively and profoundly in order to solve the above problems, it turns out that, there is specific composition Energy ray-curable resin combination and its solidfied material can solve the above subject, so as to complete the present invention.
That is, the present invention relates to following (1)~(13).
(1) a kind of resin combination, it contains (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton, ring-type (methyl) acrylate compounds (B) and polymerization initiator (C), wherein,
Compound (B) is selected from by (methyl) acrylate chemical combination with fragrant hydrocarbon skeleton in addition to compound (A) Thing, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton and (methyl) acrylate compounds group with heterocyclic skeleton Into at least one of group (methyl) acrylate compounds.
(2) resin combination as described in (1), wherein, compound (A) is to have two or more aromatic hydrocarbon bone in a molecule (methyl) acrylate compounds of frame.
(3) resin combination as described in (1) or (2), wherein, the fragrant hydrocarbon skeleton of compound (A) has by following formula (1) The skeleton of expression,
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3.
(4) resin combination as any one of (1)~(3), wherein, compound (A) is to be represented by following formula (2) Compound,
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3, and Y represents hydrogen atom or methyl, R1Represent that hydrogen is former Son, the alkyl of carbon number 1~3, halogen atom or (methyl) acryloyl group, R2Represent Direct Bonding or carbon number 1~10 (poly-) alkylene oxide group.
(5) resin combination as described in (2), wherein, in a molecule (methyl) with two or more fragrance hydrocarbon skeleton Acrylate compounds are (methyl) acrylate compounds with fluorene skeleton, naphthalene skeleton or biphenyl backbone.
(6) resin combination as any one of (1)~(5), wherein, compound (B) is with alicyclic hydrocarbon skeleton (methyl) acrylate compounds, be a molecule in have two or more alicyclic hydrocarbon skeleton (methyl) acrylate chemical combination Thing.
(7) resin combination as described in (6), wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton contain There are bicyclic decane structure, tristane ring or adamantane ring as alicyclic hydrocarbon skeleton.
(8) resin combination as described in (6), wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton are (methyl) acrylate compounds represented by following formula (3),
In formula, R3Hydrogen atom, the alkyl of carbon number 1~3, halogen atom or following formula (4) are represented independently of one another, and And at least one R3For following formula (4),
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * It is bonded with cyclic skeleton.
(9) resin combination as described in (6), wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton are (methyl) acrylate compounds represented by following formula (5),
In formula, R6And R7The alkylidene or (poly-) alkylene oxide group of Direct Bonding or carbon number 1~6 are represented independently of one another.
(10) resin combination as any one of (1)~(5), wherein, compound (B) is with heterocyclic skeleton (methyl) acrylate compounds, are (methyl) acrylate compounds represented by following formula (6),
In formula (6), R8Represent Direct Bonding, the alkylidene or alkylene oxide group of carbon number 1~6, R9Represent hydrogen or carbon atom The alkyl of number 1~4, Z represent carbon atom, oxygen atom or nitrogen-atoms.
(11) resin combination as described in (1), wherein, the compound (A) represented by following formula (2)：Represented by following formula (3) Compound (B) weight ratio be 9：1~1：9,
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3, and Y represents hydrogen atom or methyl, R1Represent that hydrogen is former Son, the alkyl of carbon number 1~3, halogen atom or (methyl) acryloyl group, R2Represent Direct Bonding or carbon number 1~10 (poly-) alkylene oxide group；
In formula, R3Hydrogen atom, the alkyl of carbon number 1~3, halogen atom or following formula (4) are represented independently of one another, and And at least one R3For following formula (4)；
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * It is bonded with cyclic skeleton.
(12) a kind of low moisture-inhibiting barrier film, its by make the resin composition any one of (1)~(11) and Obtain.
(13) resin combination as any one of (1)~(11), it is used for OLED purposes.
Invention effect
The resin combination of the present invention and its transmission of visible light of solidfied material are excellent, and cure shrinkage, water vapour pass through Rate is low, therefore particularly suitable for the sealing material of organic EL element.
Embodiment
The resin combination of the present invention contains (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton, ring-type (first Base) acrylate compounds (B) and polymerization initiator (C).
By above-mentioned composition, different (methyl) acrylate compounds of two kinds of skeletons are mutually incorporated into when curing In curing system, can be realized while low-shrinkage is realized only by containing a kind of compound with cyclic skeleton not The effect for the extremely excellent low water vapour permeability that can be realized.
What is contained in resin combination as the present invention has (methyl) acrylate compounds of fragrant hydrocarbon skeleton (A), then can be arbitrarily using known as long as intramolecular has (methyl) acrylate compounds of at least one aromatic rings Compound.With aromatic rings in such compound with aromatic rings, it is possible thereby to make resin combination that there is water repellency, Water vapour permeability can be reduced.Moreover, there is (methyl) acrylate chemical combination of more than one aromatic rings if intramolecular Thing, then the effect can fully realize.In addition, having two or more aromatic rings by intramolecular, the effect is more excellent, because This is preferred.As the skeleton in such molecule with two or more aromatic rings, biphenyl backbone or bisphenol backbone can be enumerated, this A little skeletons, which can be realized, shows excellent water vapour permeability.
In addition, these fragrant hydrocarbon skeletons there can be substituent, there can not also be substituent, in the feelings with substituent Under condition, which is preferably the alkyl of carbon number 1~6, the alkoxy of carbon number 1~6, the alkene of carbon number 1~6 Base.
As the concrete example of such (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton, can enumerate down (methyl) acrylate compounds more than simple function (methyl) acrylate compounds or difunctionality stated.
As the example of simple function (methyl) acrylate compounds, can enumerate：(methyl) benzyl acrylate, ethyoxyl Modified cresols (methyl) acrylate, propoxyl group are modified cresols (methyl) acrylate, neopentyl glycol benzoic ether (methyl) third Olefin(e) acid ester, o-phenyl phenol (methyl) acrylate, o-phenyl phenol monosubstituted ethoxy (methyl) acrylate, o-phenyl phenol gather Ethyoxyl (methyl) acrylate, p-phenyl phenol (methyl) acrylate, p-phenyl phenol monosubstituted ethoxy (methyl) acrylic acid Ester, p-phenyl phenol polyethoxy (methyl) acrylate, acrylic acid neighbour's phenylbenzyl ester, acrylic acid have phenylbenzyl ester etc. There are monocyclic (methyl) acrylate compounds；Carbazole (poly-) ethyoxyl (methyl) acrylate, carbazole (poly-) propoxyl group (first Base) acrylate, (poly-) caprolactone modification carbazole (methyl) acrylate etc. have (methyl) acrylate compounds of heterocycle； (methyl) acrylic acid naphthalene ester, (poly-) ethyoxyl (methyl) acrylic acid naphthalene ester, (poly-) propoxyl group (methyl) acrylic acid naphthalene ester, (poly-) oneself Lactone-modified (methyl) acrylic acid naphthalene ester, dinaphthol (methyl) acrylate, dinaphthol (poly-) ethyoxyl (methyl) acrylate, Dinaphthol (poly-) propoxyl group (methyl) acrylate, (poly-) caprolactone modification dinaphthol (methyl) acrylate, naphthols (methyl) Acrylate, naphthols (poly-) ethyoxyl (methyl) acrylate, naphthols (poly-) propoxyl group (methyl) acrylate, (poly-) caprolactone Modified naphthols (methyl) acrylate etc. has (methyl) acrylate compounds of condensed ring.
As (methyl) acrylate compounds more than difunctionality, can enumerate：(poly-) ethyoxyl modified bisphenol A two (methyl) acrylate, (poly-) propoxyl group modified bisphenol A two (methyl) acrylate, bis- (first of (poly-) ethyoxyl modified bisphenol F Base) acrylate, bis- (methyl) acrylate of (poly-) propoxyl group modified bisphenol F, bis- (methyl) third of (poly-) ethyoxyl modified bisphenol S It is olefin(e) acid ester, bis- (methyl) acrylate of (poly-) propoxyl group modified bisphenol S, hexahydrophthalic acid two (methyl) acrylate, double Phenoxy group (poly-) ethyoxyl fluorenes etc. has monocyclic (methyl) acrylate compounds；Biphenyl dimethanol two (methyl) acrylate Deng (methyl) acrylate compounds with heterocycle；Dinaphthol two (methyl) acrylate, two (first of dinaphthol (poly-) ethyoxyl Base) acrylate, two (methyl) acrylate of dinaphthol (poly-) propoxyl group, (poly-) caprolactone modification dinaphthol two (methyl) propylene Acid esters etc. has (methyl) acrylate compounds of condensed ring；Bisphenol fluorene two (methyl) acrylate, double phenoxy group methanol fluorenes two (methyl) acrylate, double phenoxetol fluorenes two (methyl) acrylate, two (methyl) acrylic acid of double phenoxy group caprolactone fluorenes Ester etc. has (methyl) acrylate compounds of Ppolynuclear aromatic etc..
As (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton, except above-mentioned (methyl) acrylate Beyond monomer, epoxy (methyl) acrylate compounds can also be enumerated.
As epoxy (methyl) acrylate, can enumerate：Bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol Phenolic resin varnish type epoxy resin, biphenyl type phenol aralkyl resin, bisphenol-A propylene oxide adduct terminal glycidyl group Reaction product of the epoxy resins such as ether, fluorenes epoxy resin, bisphenol-s epoxy resin and (methyl) acrylic acid etc..
Wherein, specifically can be preferably using example as (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton Such as (methyl) acrylate compounds of the part skeleton with following formula (1).
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3.
Think by with above-mentioned part skeleton, can more effectively show the water repellency that aromatic rings can assign.
Specifically, in above-mentioned (methyl) acrylate compounds, there is the bis-phenol bones such as bisphenol A skeleton, Bisphenol F skeleton Frame or (methyl) acrylate compounds of biphenyl backbone correspond to above-mentioned formula (1) it is preferable to use.
Additionally, it is preferred that (methyl) acryloyl group is connected on fragrant hydrocarbon skeleton.And specifically, it is preferable to (methyl) acryloyl group is straight Connect or be connected to via alkyl on above-mentioned fragrant hydrocarbon skeleton, as alkyl when being connected via alkyl, carbon atom can be enumerated The alkylidene of number 1~10 or with ehter bond carbon number 1~10 alkylidene.
In addition, as (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton used in the present invention, preferably by (methyl) acrylate compounds that following formula (2) represents.
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3, and Y represents hydrogen atom or methyl, R1Represent that hydrogen is former Son, the alkyl of carbon number 1~3, halogen atom or following formula (4), R2Represent (poly-) Asia of Direct Bonding or carbon number 1~10 Alkoxy；
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * It is bonded with benzene skeleton.
The concrete example of such (methyl) acrylate compounds, can enumerate 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) propylene Acid esters, acrylic acid neighbour's phenylbenzyl ester, acrylic acid are to phenylbenzyl ester, (poly-) propoxyl group modified bisphenol A two (methyl) acrylic acid Ester, bis- (methyl) acrylate of (poly-) ethyoxyl modified bisphenol F, bis- (methyl) acrylate of (poly-) propoxyl group modified bisphenol F etc..
Content of (methyl) acrylate compounds (A) in resin combination with fragrant hydrocarbon skeleton is relative to resin 100 parts by weight of composition are preferably generally 5~95 parts by weight, more preferably 10~80 parts by weight, particularly preferably 20~70 weights Measure part.
As ring-type (methyl) acrylate compounds (B) used in the present invention, there can be aromatic hydrocarbon using above-mentioned (methyl) acrylate of skeleton, (methyl) acrylate with alicyclic hydrocarbon skeleton, (methyl) propylene with heterocyclic skeleton Acid esters.
Here, (methyl) acrylate compounds with fragrant hydrocarbon skeleton are used as ring-type (methyl) acroleic acid esterification During compound (B), resin combination contains two kinds different " (methyl) acrylate compounds with fragrant hydrocarbon skeleton " of structure. I.e., it is possible to as ring-type (methyl) acrylate compounds use have (methyl) acrylate of fragrant hydrocarbon skeleton with it is above-mentioned That enumerates is identical, but cannot use (methyl) acrylate compounds identical with compound (A).
When (methyl) acrylate compounds with fragrant hydrocarbon skeleton are used in resin combination, with chain Other skeletons such as the skeleton of structure are compared, have prevent water vapour pass through effect, by with (the first with fragrant hydrocarbon skeleton Base) acrylate compounds (A) are configured in curing system together, it can significantly prevent the saturating of water vapour using synergy Cross.
, can be without spy as (methyl) acrylate compounds with alicyclic hydrocarbon skeleton that can be used in the present invention Not Xian Zhi ground using known (methyl) acrylate compounds with alicyclic hydrocarbon skeleton, alicyclic hydrocarbon skeleton is preferably saturated hydrocarbons Skeleton.Such ring type skeleton has the effect for preventing that water vapour from passing through compared with other skeletons such as the skeleton of chain structure, leads to Cross together with (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton and configure in curing system, utilize synergy It can significantly prevent the transmission of water vapour.
As ring type hydrocarbon skeleton, as the skeleton that can specifically use, cyclopentane framework, hexamethylene bone can be enumerated Frame, cycloheptane skeleton, bicyclic decane structure, tristane ring, adamantane ring, isoborneol basic ring etc..
Wherein, preferred (methyl) acrylate compounds with the endocyclic hydrocarbon skeleton such as tristane ring, adamantane ring. In such compound, bridge joint is formed on alicyclic hydrocarbon skeleton, therefore obtains stereochemical structure and configures carbon atom in cyclic structure Space in, therefore can more efficiently prevent from water vapour transmission.Moreover, by with such with endocyclic hydrocarbon skeleton (methyl) acrylate compounds mix, and above-mentioned synergy becomes higher.
Additionally, it is preferred that (methyl) acryloyl group is connected on ring type hydrocarbon skeleton.And specifically, it is preferable to (methyl) acryloyl group is straight Connect or be connected to via alkyl on above-mentioned ring type hydrocarbon skeleton, as alkyl when being connected via alkyl, carbon atom can be enumerated The alkylidene of number 1~10 or with ehter bond carbon number 1~10 alkylidene.
As the concrete example of such (methyl) acrylate compounds with alicyclic hydrocarbon skeleton, there is following simple functions (methyl) acrylate compounds more than (methyl) acrylate compounds or difunctionality.
As simple function (methyl) acrylate compounds, (methyl) isobornyl acrylate, (methyl) third can be enumerated Olefin(e) acid tetrahydrochysene dicyclopentadiene base ester, (methyl) propylene acid dihydride dicyclopentadiene base ester, (methyl) propylene acid dihydride two Polycyclopentadithio.henes alkenyl epoxide ethyl ester, (methyl) cyclohexyl acrylate etc. ester ring type (methyl) acrylate, 1,3- adamantane glycol Two (methyl) acrylate, 1,3- adamantane dimethanol two (methyl) acrylate, (methyl) acrylic acid 2- methyl -2- adamantane Base ester, (methyl) acrylic acid 2- ethyl -2- adamantane esters, (methyl) acrylic acid 3- hydroxyl -1- adamantane esters, (methyl) third Olefin(e) acid 1- adamantane esters etc..
As multifunctional (methyl) acrylate compounds more than difunctionality, Tricyclodecane Dimethanol (first can be enumerated Base) ester ring type (methyl) acrylate such as acrylate etc..
As such (methyl) acrylate compounds with ring type hydrocarbon skeleton, can preferably use has under (methyl) acrylate compounds for the structure that formula (3) represents.
In formula, R3Hydrogen atom, the alkyl of carbon number 1~3, halogen atom or following formula (4) are represented independently of one another, and And at least one R3For following formula (4).
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * It is bonded with cyclic skeleton.
As the concrete example of (methyl) acrylate compounds of above formula (3), Tricyclodecane Dimethanol (first can be enumerated Base) ester ring type (methyl) acrylate such as acrylate etc..
Content of (methyl) acrylate compounds in resin combination with alicyclic hydrocarbon skeleton is relative to resin group 100 parts by weight of compound are preferably generally 5~95 parts by weight, more preferably 10~80 parts by weight, particularly preferably 20~70 weight Part.
Below to can be as (the first with heterocyclic skeleton that ring-type (methyl) acrylate compounds use in the present invention Base) acrylate compounds illustrate.
Such heterocyclic skeleton has the effect for preventing that water vapour from passing through compared with other skeletons such as the skeleton of chain structure Fruit, by being configured together with (methyl) acrylate compounds (A) with fragrant hydrocarbon skeleton in curing system, utilizes collaboration Effect can significantly prevent the transmission of water vapour.
As heterocyclic skeleton, as the skeleton that can specifically use, dioxane structure, trioxa can be enumerated Cyclohexane structure, isocyanurate structure etc..
Additionally, it is preferred that (methyl) acryloyl group is connected on heterocyclic skeleton.And specifically, it is preferable to (methyl) acryloyl group is direct Or be connected to via alkyl on above-mentioned heterocyclic skeleton, as alkyl when being connected via alkyl, can enumerate carbon number 1~ 10 alkylidene or with ehter bond carbon number 1~10 alkylidene.
As the concrete example of such (methyl) acrylate compounds with heterocyclic skeleton, there is following (methyl) third Enoic acid ester compounds.
I.e., it is possible to enumerate：(methyl) tetrahydrofurfuryl acrylate, alkoxylate tetrahydrofurfuryl acrylate, caprolactone modification (first Base) tetrahydrofurfuryl acrylate, morpholine (methyl) acrylate, isocyanuric acid EO modified diacrylates (M-215), 6-caprolactone Modified three (acryloyl-oxyethyl) isocyanuric acid esters (M-327), isocyanuric acid EO modified diacrylates and triacrylate (M-313 or M-315), hydroxy pivalin aldehyde are modified trimethylolpropane diacrylate (R-604), methacrylic acid pentamethyl piperazine Pyridine ester (FA-711), methacrylic acid tetramethyl piperidine ester (FA-712HM), cyclic trimethylolpropane formal acrylate (SR531)。
, can be with as such (methyl) acrylate compounds with heterocyclic skeleton, such as the example as heterocycle Enumerate：Morpholine skeleton, tetrahydrofuran skeleton, oxinane skeleton, dioxane skeleton, triazine skeleton, carbazole skelton, Pyrrolidines skeleton, piperidine scaffolds, isocyanurate structure, can preferably use the (first with the structure represented by following formula (7) Base) acrylate compounds.
In formula, R8Represent Direct Bonding, the alkylidene or alkylene oxide group of carbon number 1~6, R9Represent hydrogen atom, carbon atom The alkyl or alkenyl of number 1~4, X represent nitrogen-atoms, oxygen atom or methylene, and Y represents methylene or carbonyl, m represent 1~4 it is whole Number, still, the not all methylene of X.
Here, it is preferred that the compound represented by following formula (6) can be used.
In formula, R8Represent Direct Bonding, the alkylidene or alkylene oxide group of carbon number 1~6, R9Represent hydrogen atom, carbon atom The alkyl of number 1~4, Z represent carbon atom, oxygen atom or nitrogen-atoms.
Content of (methyl) acrylate compounds in resin combination with heterocyclic skeleton is relative to resin combination 100 parts by weight of thing are preferably generally 5~95 parts by weight, more preferably 10~80 parts by weight, particularly preferably 20~70 parts by weight.
On the resin combination of the present invention, in (methyl) acrylate compounds component in resin combination, preferably (hereinafter referred to as poly- EO is modified (first to (methyl) acrylate compounds with the structure represented by following part structural formula (A) Base) acrylate compounds) gross weight be less than except poly- EO modification (methyl) acrylate compounds in addition to (methyl) propylene The gross weight of ester compound, more preferably less than 1/2.
In formula, t represents more than 2 integer.
This is because the water vapour permeability that above-mentioned poly- EO is modified (methyl) acrylate compounds is poor, when the poly- EO changes Property (methyl) acrylate compounds content it is more, dominant in resin combination when, it is possible to water vapour permeability is poor.
Moreover, poly- EO is modified the gross weight of (methyl) acrylate compounds relative to resin combination in resin combination 100 parts by weight are preferably below 10 parts by weight, more preferably below 5 parts by weight, particularly preferably below 2 parts by weight.
In the present invention, (methyl) acrylate chemical combination is modified as ring-type (methyl) acrylate compounds and as poly- EO Thing, preferably poly- EO modifications (methyl) acrylate compounds of the ring-type, (first with fragrant hydrocarbon skeleton not as the present invention Base) acrylate compounds (A) or ring-type (methyl) acrylate compounds (B) use, therefore even if use, relative to resin 100 parts by weight of composition are preferably also below 20 parts by weight, particularly preferably below 10 parts by weight.
In the present invention, what is contained in resin combination has (methyl) acrylate (A) and ring-type (first of fragrant hydrocarbon skeleton Base) ratios of acrylate compounds (B) with weight ratio meter is preferably 1：9~9：1, more preferably 7：3~9：1, particularly preferably For 5：5~9：1.
By being set as above-mentioned preferable scope, the extremely excellent resin combination of water vapour permeability can be obtained.
As the polymerization initiator (C) used in the present invention, Photoepolymerizationinitiater initiater, hot radical polymerization can be used to trigger The various polymerization initiators such as agent.
In addition, as Photoepolymerizationinitiater initiater, can specifically enumerate：Benzoin, benzoin methylether, benzoin ethyl ether, benzene The benzoin class such as anisoin isopropyl ether, benzoin isobutyl ether；Acetophenone, 2,2- dimethoxy -2- phenyl acetophenones, 2,2- diethoxies Base -2- phenyl acetophenones, 1,1- dichloroacetophenones, 2- hydroxy-2-methyls-phenyl-propane -1- ketone, diethoxy acetophenone, 1- Hydroxycyclohexyl phenyl ketone, 2- methyl isophthalic acids-[4- (methyl mercapto) phenyl] -2- morpholinopropane -1- ketone, oligomeric [2- hydroxyls -2- Methyl isophthalic acid-[4- (1- methyl ethylenes) phenyl] acetone] etc. acetophenones；2- ethyl hydrazine, 2- tert-butyl groups anthraquinone, 2- chrloroanthracenes The Anthraquinones such as quinone, 2- amyl anthraquinones；The thioxanthene ketone class such as 2,4- diethyl thioxanthones, 2-isopropylthioxanthone, 2-chlorothioxanthone；Benzene The ketal classes such as acetophenone dimethyl base ketal, dibenzoyl dimethyl ketal；Benzophenone, 4- benzoyls -4 '-methyldiphenyl thioether, The benzophenones such as 4,4 '-dimethylamino benzopheone；2,4,6- trimethyl benzoyl diphenyl bases phosphine oxide, double (2,4,6- Trimethylbenzoyl) phosphinoxides such as-phenyl phosphine oxide, diphenyl-(2,4,6- trimethylbenzoyls) phosphine oxide；Deng. Preferably acetophenones, can more preferably enumerate 2- hydroxy-2-methyl phenyl-propane -1- ketone, 1- hydroxycyclohexyl phenyl ketones. It should be noted that in the resin combination of the present invention, Photoepolymerizationinitiater initiater can be used alone or a variety of be used in mixed way.
In addition, as hot radical polymerization initiator, as long as generated free radicals by heating and trigger chain polymerization The compound of reaction is then not particularly limited, and it is even can to enumerate organic peroxide, azo-compound, benzoin compound, benzene Relation by marriage ether compound, acetophenone compound, benzpinacol etc., preferably using benzpinacol.For example, as organic peroxide Kayamek (trade mark) A, M, R, L, LH, SP-30C, Perkadox (trade mark) CH-50L, BC-FF, Cadox (trade mark) B-40ES, Perkadox 14, Trigonox (trade mark) 22-70E, 23-C70,121,121-50E, 121-LS50E, 21-LS50E, 42, 42LS, Kayaester (trade mark) P-70, TMPO-70, CND-C70, OO-50E, AN, Kayabutyl (trade mark) B, Perkadox16, Kayacarbon (trade mark) BIC-75, AIC-75 (manufacture of chemical drug ア Network ゾ Co., Ltd.), Permek (trade mark) N, H, S, F, D, G, Perhexa (trade mark) H, HC, TMH, C, V, 22, MC, Percure (trade mark) AH, AL, HB, Perbutyl (business Mark) H, C, ND, L, Percumyl (trade mark) H, D, Peroyl (trade mark) IB, IPP, Perocta (trade mark) ND (Japan Oil Co Manufacture) etc. can be obtained as commercially available product.In addition, VA-044, V-070, VPE-0201, VSP-1001 as azo-compound (Wako Pure Chemical Industries, Ltd.'s manufacture) etc. can be obtained as commercially available product.
It is preferably that benzpinacol class hot radical polymerization initiator is (including right as above-mentioned hot radical polymerization initiator Benzpinacol be chemically modified after material).It can specifically enumerate：Benzpinacol, 1,2- dimethoxys -1,1,2,2- four Diphenylphosphino ethane, 1,2- diethoxy -1,1,2,2- tetraphenyls ethane, 1,2- hexichol Oxy-1s, 1,2,2- tetraphenyls ethane, 1,2- Dimethoxy -1,1,2,2- four (4- aminomethyl phenyls) ethane, 1,2- hexichol Oxy-1s, 1,2,2- tetra- (4- aminomethyl phenyls) ethane, Double (the trimethylsiloxy) -1,1,2,2- tetraphenyls ethane of 1,2-, double (silicohetane the alkoxy) -1,1,2,2- of 1,2- Double (t-butyldimethylsilyloxy the base) -1,1,2,2- tetraphenyls ethane of tetraphenyl ethane, 1,2-, 1- hydroxyl -2- trimethyls Siloxy -1,1,2,2- tetraphenyls ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1s, 1,2,2- tetraphenyls ethane, 1- Hydroxyl -2- t-butyldimethylsilyloxy bases -1,1,2,2- tetraphenyl ethane etc., are preferably 1- hydroxyl -2- trimethyl first silicon Alkoxy -1,1,2,2- tetraphenyls ethane, 1- hydroxyl -2- triethyl-silicane Oxy-1s, 1,2,2- tetraphenyls ethane, 1- hydroxyls Double (trimethylsiloxy) -1,1 of base -2- t-butyldimethylsilyloxy base -1,1,2,2- tetraphenyls ethane, 1,2-, 2,2- tetraphenyl ethane, more preferably 1- hydroxyl -2- trimethylsiloxies -1,1,2,2- tetraphenyl ethane, 1,2- Double (trimethylsiloxy) -1, double (trimethylsiloxy) -1 of 1,2,2- tetraphenyl ethane, particularly preferably 1,2-, 1,2,2- tetraphenyl ethane.
Above-mentioned benzpinacol is sold by Tokyo HuaCheng Industry Co., Ltd, Wako Pure Chemical Industries, Ltd. etc..In addition, will The etherification of hydroxyl groups of benzpinacol can easily be synthesized by known method.In addition, the hydroxyl first silicon by benzpinacol It is alkyl etherified can be by heating the side of corresponding benzpinacol and various silylating agents under the basic catalysts such as pyridine Method is synthesized into.As silylating agent, can enumerate commonly known as trimethylsilylation agent Trim,ethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), double (trimethyl silyl) trifluoroacetamides of N, O- (BSTFA), the chlorotriethyl silane (TECS) as triethylsilyl agent, as t-butyldimethylsilyl T-butyldimethylsilyl (TBMS) of agent etc..These reagents can be readily available from the markets such as silicon derivative manufacturers.Make It it is preferably 1.0~5.0 times moles relative to 1 mole of the hydroxyl of subject compound for the reacting dose of silylating agent.Further Preferably 1.5~3.0 times moles.During less than 1.0 times moles, reaction efficiency is poor, and reaction time length, it is therefore possible to promote heat point Solution.During more than 5.0 times moles, it is possible to which separation is deteriorated or is difficult to purify when recycling.
The content of the polymerization initiator (C) of the present invention relative to 100 mass parts of total amount of resin combination be preferably 0.1~ 10 mass parts, more preferably 0.5~5 mass parts.It should be noted that in the resin combination of the present invention, polymerization initiator (C) It can be used alone or a variety of be used in mixed way.
In addition, in the resin combination of the present invention, viscosity, the refraction of obtained resin combination of the invention are considered Rate, adhesiveness etc., can use (methyl) acrylate compounds in addition to compound (A), compound (B).Specifically, may be used To enumerate (methyl) acrylate monomer, as (methyl) acrylate monomer, simple function (methyl) acrylic acid can be used Ester, difunctionality (methyl) acrylate, intramolecular have multifunctional (methyl) acrylic acid of more than three (methyl) acryloyl groups Ester, polyester (methyl) acrylate, epoxy (methyl) acrylate etc..
As simple function (methyl) acrylate, can enumerate for example：Acid imide (methyl) with imide ring structure Acrylate；Butanediol list (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- hydroxyls third Ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, dipropylene glycol (methyl) acrylate etc. have (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, (first Base) 2-ethyl hexyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) third Olefin(e) acid 2- ethylhexyls, (methyl) stearyl acrylate, (methyl) isostearyl acrylate, the different nutmeg of (methyl) acrylic acid Ester, (methyl) lauryl acrylate etc. have (methyl) acrylate of alkyl；Ethoxydiglycol (methyl) acrylate, 2- ethylhexyls carbitol (methyl) acrylate, polyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate (methyl) acrylate Deng polyalcohol etc..
As (methyl) acrylate monomer with Liang Ge functional groups, can enumerate：Diacrylated isocyanuric acid ester Deng the acrylate of isocyanates；1,4- butanediols two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate etc. have straight chain methylene structure (methyl) acrylate；Ethylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, two (first of propane diols Base) polyalcohol such as acrylate and polypropylene glycol two (methyl) acrylate two (methyl) acrylate etc..
As multifunctional (methyl) acrylate monomer, can enumerate：Isocyanuric acid three (acryloyl-oxyethyl) ester, (poly-) caprolactone modification isocyanuric acid three (acryloyl-oxyethyl) ester etc. has multifunctional (methyl) third of isocyanurate ring Olefin(e) acid ester；Pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylate, (poly-) ethyoxyl are modified Ji Wusi Alcohol four (methyl) acrylate, (poly-) propoxyl group are modified pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) Acrylate, (poly-) caprolactone modification dipentaerythritol five (methyl) acrylate, (poly-) ethyoxyl are modified dipentaerythritol five (methyl) acrylate, (poly-) propoxyl group are modified dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) third Olefin(e) acid ester, (poly-) caprolactone modification dipentaerythritol six (methyl) acrylate, (poly-) ethyoxyl are modified six (first of dipentaerythritol Base) acrylate, (poly-) propoxyl group be modified dipentaerythritol six (methyl) acrylate, more (methyl) acrylic acid of polypentaerythritol Ester, trimethylolpropane tris (methyl) acrylate, (poly-) ethyoxyl be modified trimethylolpropane tris (methyl) acrylate, (poly-) propoxyl group be modified 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. is phosphorous Multifunctional (methyl) acrylate；Trimethylolpropane benzoic ether (methyl) acrylate etc. has more officials of aromatic group Can (methyl) acrylate；Multifunctional (methyl) acrylic acid that the acid of tri- acryloyloxymethyl butanedioic acids of 2,2,2- etc. is modified Ester；Multifunctional (methyl) acrylate with silicone matrix of polysiloxanes six (methyl) acrylate etc. etc..
Such (methyl) acrylate monomer containing in resin combination in addition to compound (A), compound (B) Amount is preferably generally 5~95 parts by weight relative to 100 parts by weight of resin combination, more preferably 10~80 parts by weight, especially excellent Elect 20~70 parts by weight as.
In the present invention, in the degree for not damaging characteristic, carbamate (methyl) acrylate can be used.
As carbamate (methyl) acrylate, can enumerate for example：Diatomic alcohol compounds are (for example, ethylene glycol, two Ethylene glycol, triethylene glycol, propane diols, dipropylene glycol, tripropylene glycol, 1,4- butanediols, neopentyl glycol, 1,6-HD, 1,8- Ethohexadiol, 1,9- nonanediols, 2- methyl isophthalic acids, 8- ethohexadiols, 3- methyl isophthalic acids, 5- pentanediols, 2,4- diethyl -1,5- pentanediols, 2-butyl-2-ethyl-1,3-propanediol, hexamethylene -1,4- dimethanols, polyethylene glycol, polypropylene glycol, bisphenol-A polyethoxy two Alcohol, polymer with bis phenol A propoxyl group glycol etc.) or as these diatomic alcohol compounds and binary acid or its acid anhydrides (for example, butanedioic acid, oneself The binary acid such as diacid, azelaic acid, dimeric dibasic acid, M-phthalic acid, terephthalic acid (TPA), phthalic acid or their acid anhydrides) it is anti- Answer product polyester diol, with organic multiple isocyanate (for example, tetramethylene diisocyanate, hexa-methylene diisocyanate The chain saturated hydrocarbons such as ester, 2,2,4- trimethyl hexamethylene diisocyanates, 2,4,4- trimethyl hexamethylene diisocyanates Isocyanates；Isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methyl hydride diisocyanate, methylene Double (4- cyclohexyl isocyanates), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene two The cyclic saturated hydrocarbon isocyanates such as isocyanates；2,4 toluene diisocyanate, 1,3- benzene dimethylene diisocyanate, to Asia Phenyl diisocyanate, 3,3 '-dimethyl -4,4 '-diisocyanate, 6- isopropyl -1,3- phenyl diisocyanates, 1,5- naphthalenes The aromatic polyisocyanates such as diisocyanate) reaction, then addition contains anti-obtained from (methyl) acrylate of hydroxyl Answer product etc..
Content of carbamate (methyl) acrylate compounds in resin combination is relative to resin combination 100 Parts by weight are preferably generally 5~95 parts by weight, more preferably 10~80 parts by weight, particularly preferably 20~70 parts by weight.
In the present invention, particulate can be suitably contained in resin combination.As particulate, organic fine particles, inorganic can be enumerated Particulate.In addition, particulate can be contemplated required light transmittance, hardness, marresistance, cure shrinkage, refractive index be used alone or Person is a variety of to be used in mixed way.
In addition, from the viewpoint of transmissivity (transmissivity under particularly 380nm~780nm) is improved, preferably do not contain Particulate.
As the organic fine particles that can be used in the present invention, can enumerate：Polystyrene resin bead, acrylic resin The organic polymer pellets such as bead, polyurethane resin bead, polycarbonate resin bead；It is expanded polystyrene resin beads, more The porous organic polymer of hole acrylic resin bead, cellular polyurethane resin beads, porous polycarbonate resin beads etc. Bead；The toner of phenyl guanamine-formaldehyde condensation product, the toner of phenyl guanamines-carbamide condensation product, urea- The toner of formaldehyde condensation products, the powder of aspartate derivatives, zinc stearate powder, stearmide powder, asphalt mixtures modified by epoxy resin Cosmetics end, polyethylene powders etc., preferably crosslinked polymethylmethacrylaparticles resin beads, crosslinked polymethylmethacrylaparticles benzene Vinyl bead etc..These organic fine particles can be readily available as commercially available product, in addition can also refer to known document into It is prepared by row.
As the inorganic particles that can be used in the present invention, can enumerate：Conductive metal oxide, transparent metal oxide Thing, other inorganic fillers etc..
As the conductive metal oxide that can be used in the present invention, can enumerate：Zinc antimonates, doped sno_2 oxidation Indium (ITO), antimony-doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminium-doped zinc oxide, Ga-doped zinc oxide, Fluorin doped Tin oxide etc..
As the transparent metal oxide that can be used in the present invention, can enumerate：Silica, titanium oxide, zirconium oxide, The oxygen of cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconium oxide/tin oxide/antimony pentoxide compound, zirconium oxide/tin oxide/five Change two antimony compounds, titanium oxide/zirconium oxide/oxidation tin composite etc..
As the other inorganic fillers that can be used in the present invention, can enumerate：Calcium oxide, calcium chloride, zeolite, silica gel Deng.
As the particulate that can be used in the present invention, preferred hardness and excellent abrasion, the particulate of high refractive index can be with It is multiple preferably using titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide/zirconium oxide/tin oxide/antimony pentoxide Compound, zirconium oxide/tin oxide/antimony pentoxide compound, titanium oxide/zirconium oxide/oxidation tin composite.Further, since aobvious Show the optical sheet requirement high transparency used in device, therefore the primary particle size of particulate is preferably below 100nm.Their match ratio Example is preferably 1~30 mass parts relative to 100 mass parts of total amount of compound (A)+compound (B), more preferably 5~20 mass Part.
Alternatively, it is also possible to and with polybasic carboxylic acid class dispersant, silane coupling agent, titante coupling agent, modified silicon oil etc. Dispersant as particulate of polysiloxane-based dispersant, organic copolymer species dispersant etc..Their mixing ratio relative to The gross mass of the resin combination of the present invention is about 0~about 30 mass %, is preferably from about 0.05~about 5 mass %.
It should be noted that the minimum particle diameter that the particle has when primary particle size refers to break up aggregation.That is, in ellipse Particulate in the case of, using minor axis as primary particle size.Primary particle size can pass through dynamic light scattering method, electron microscope observation Etc. being measured.Specifically, Jeol Ltd. JSM-7700F electric field emission type scanning electron microscope can be used Primary particle size is measured under the conditions of accelerating potential 30kV.
In the present invention, primary particle size is preferably below 100nm.Furthermore, it is possible to preferably using primary particle size for 5nm~ The particulate of 100nm.It is below 100nm by primary particle size, marresistance can be assigned and provide transmissivity high solidfied material.
These particulates can disperse to use in a solvent.Particularly inorganic particles are easily to be dispersed in water or organic solvent Form obtain commercially available product, as used organic solvent, can enumerate：Varsol, esters solvent, ether solvent and ketone Class solvent.As varsol, can enumerate：The aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ethylbenzene, durene；Hexane, octane, the last of the ten Heavenly stems The aliphatic hydrocarbon solvents such as alkane；And petroleum ether, unleaded gas, solvent naphtha as their mixture etc..As esters Solvent, can enumerate：The alkyl acetate class such as ethyl acetate, propyl acetate, butyl acetate；The ring-type esters such as gamma-butyrolacton；Second Glycol monomethylether 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, adipic acid dioxane Polybasic carboxylic acid alkyl esters such as base ester etc..As ether solvent, can enumerate：The alkyl ethers such as ether, ethyl-butyl ether；Second two Diethylene glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol two The glycol ethers such as ether；Ring-type ethers such as tetrahydrofuran etc..As ketones solvent, can enumerate：Acetone, methyl ethyl ketone, ring Hexanone, isophorone etc..
When particulate is used in the present invention, the content of particulate is preferably generally 0.001 relative to 100 parts by weight of resin combination ~20 parts by weight, more preferably 0.001~10 parts by weight, particularly preferably 0.001~5 parts by weight.
In the resin combination of the present invention, in addition to mentioned component, convenience during in order to improve processing etc., Ke Yigen According to situation and with containing releasing agent, defoamer, levelling agent, light stabilizer, antioxidant, polymerization inhibitor, plasticizer, antistatic agent Deng.
In addition, durability, flexibility in order to obtain, there is many examples using plasticizer.Used material is according to institute's phase The viscosity of prestige, durability, the transparency, flexibility etc. select.It can specifically enumerate：The olefin polymers such as polyethylene, polypropylene； Repefral, diethyl phthalate, dibutyl phthalate, phthalic acid two (2- ethylhexyls) Ester, diisooctyl phthalate, butyl benzyl phthalate, diisononyl phthalate, phthalic acid two The phthalic acids such as cyclohexyl, glycolic ethylphthalyl ethyl glycolate ethyl ester, ethanol acid butyl phthalyl butyl ester Ester；The trimellitates such as tri trimellitate (2- ethylhexyls) ester；Dibutyl adipate, diisobutyl adipate, adipic acid two (2- ethylhexyls) ester, diisononyl adipate, diisodecyl adipate (DIDA), adipic acid two (2- (2- Butoxyethoxies) ethyl) Ester, azelaic acid two (2- ethylhexyls) ester, dibutyl sebacate, decanedioic acid two (2- ethylhexyls) ester, diethyl succinate etc. Fatty group dibasic acid；Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, phosphoric acid triphen Ester, tricresyl phosphate, tricresyl phosphate (xylyl) ester, cresyl phosphate diphenyl ester, phosphoric acid 2- ethylhexyl diphenyl esters etc. are just Phosphate；The ricinoleate esters such as acetyl group methyl ricinolcic acid；Polyester such as poly- (adipic acid 1,3 butylene glycol esters)；Triacetic acid glycerine The acetic acid esters such as ester；The sulfonamide such as N-butylbenzenesulfonamide；Polyethylene glycol benzoic ether, polyethylene glycol dibenzoate, poly- the third two Alcohol benzoic ether, dibenzonate, polytetramethylene glycol benzoic ether, polytetramethylene glycol dibenzoate Deng polyalkylene oxide (two) benzoic ether；The polyethers such as polypropylene glycol, polyethylene glycol, polytetramethylene glycol；Polyethoxy is modified double The poly-alkoxyl modified bisphenol As such as phenol A, poly- propoxyl group modified bisphenol A；Polyethoxy modified bisphenol F, poly- propoxyl group modified bisphenol F Etc. poly-alkoxyl modified bisphenol F；The polycyclc aromatic compounds such as naphthalene, phenanthrene, anthracene；(connection) naphthols, (poly-) ethyoxyl are modified (connection) naphthalene Phenol, (poly-) propoxyl group are modified (connection) naphthols, (poly-) tetramethylene glycol is modified (connection) naphthols, (poly-) caprolactone modification (connection) naphthols Deng naphthol derivative；Diphenyl sulfide, diphenyl polysulfide, benzothiazole based bisulfide, rhenocure CA, two sulphur of morpholinyl For benzothiazole, cyclohexylbenzothiazole -2- sulfenamides, tetramethylthiuram disulfide, tetraethylthiuram disulfide, two Vulcanize tetrabutyl thiuram, curing four (2- ethylhexyls) thiuram, tetramethylthiuram monosulfide, five methylene of tetra-sulfurized pair The sulfur-containing compounds such as base thiuram.Preferably (poly-) ethylene glycol dibenzoate, (poly-) propylene glycol dibenzoate, dinaphthol, (poly-) ethyoxyl is modified dinaphthol, (poly-) propoxyl group is modified dinaphthol, diphenyl sulfide.
In addition, acrylic polymer, polyester elastomer, urethane polymer and nitrile can also be added as needed Rubber etc. polymerize species.
On the organic compound ingredient without reactive group, from the viewpoint of compatibility, its weight average molecular weight Preferably below 10000g/mol, particularly preferably below 5000g/mol.In the present invention, without the organic of reactive group Content of the compound in resin combination is preferably more preferably 1.0 weights below 1.5 weight % relative to resin combination Measure below %, particularly preferably below 0.5 weight %.By being set as below 1.5 weight %, can prevent without reactivity The component of group is incompatible and is remained in the form of the insoluble component such as solid-like or gelatinous, therefore can prevent as solidfied material Property the transparency, heat resistance be deteriorated, therefore preferably.In addition, in order to reduce water vapour permeability, it is organic that alkyl aluminum etc. can be added Metallic compound.Solvent can also be added, it is preferred that not adding solvent.
For the resin combination of the present invention, preferably there is excellent characteristic, specifically, wavelength on transmissivity The light transmittance of each wavelength is preferably more than 90% in 380nm~780nm scopes.Light transmittance can pass through Co., Ltd. Hitachi's high-tech The determining instruments such as the spectrophotometer U-3900H of system measure.
In addition, for the resin combination of the present invention, glass transition temperature is preferably more than 70 DEG C, particularly preferably For more than 100 DEG C.
The resin combination of the present invention can be by according to conventional methods preparing each component mixed dissolution.For example, can Each component input is carried in the round-bottomed flask of agitating device, thermometer, and stirred at 20~80 DEG C, preferably 40~80 DEG C 0.5 it is small when~6 it is small when and obtain.
On the viscosity of the resin combination of the present invention, viscosity as suitable workability, preferably using E type viscosimeters (TV-200：Dong Ji industry companies system) measure viscosity at 25 DEG C below 1000mPas composition, particularly preferably Below 500mPas.
The resin combination of the present invention can easily make its curing by energy-ray.Here, as energy-ray Concrete example, can enumerate：The electromagnetic waves such as ultraviolet, visible ray, infrared ray, X-ray, gamma-rays, laser beam；Alpha ray, β are penetrated Particle rays such as line, electron ray etc..In the present invention, among these energy-rays, preferred ultraviolet, laser beam, visible Light or electron ray.
By irradiating above-mentioned energy-ray to the resin combination of the present invention according to conventional methods, it can obtain the present invention's Solidfied material.The liquid refractivity of the resin combination of the present invention is usually 1.45~1.55, is preferably 1.48~1.52.Refractive index Abbe refractomecer (model can be passed through：DR-M2, Atagi Corp.'s (ア タ go) system) etc. measure.
Water vapour permeability at 60 DEG C of 100 μm of the thickness of the resin combination of the present invention is preferably 200g/m2My god Hereinafter, it is more preferably 100g/m2It is following, particularly preferably 60g/m2It is following., can be effective by within the range Ground prevents the transmission due to moisture and produces infringement to element.
Following process is preferably included using the sealed solid method of the organic EL element of the resin combination of the present invention：In shape Into in the process that passivating film is formed in the organic EL element on substrate；Sealing adhesive is coated with above-mentioned passivating film, and is set The process for putting sealing transparent substrate；With make the above-mentioned cured process of sealing adhesive.Consolidating for the invention described above can be used The property changed resin combination is as sealing adhesive.
The organic EL element to be sealed for example by substrate and comprising lower electrode, including at least organic EL of luminescent layer The components Department main body of layer and upper electrode is formed.Using glass substrate, include cycloolefin or makrolon, poly-methyl methacrylate The transparent organic material of ester etc., the transparent organic material is subjected to high rigidity with glass fibre etc. obtained from organic/inorganic Mixed transparent substrate etc. includes the flat substrate of electrical insulating property material as substrate.In addition, the representativeness as components Department main body Form, following composition can be enumerated.
(1) lower electrode/luminescent layer/upper electrode
(2) lower electrode/electron transfer layer/luminescent layer/upper electrode
(3) lower electrode/luminescent layer/hole transmission layer/upper electrode
(4) lower electrode/electron transfer layer/luminescent layer/hole transmission layer/upper electrode
For example, the organic EL element of the Rotating fields with above-mentioned (4) can be by being added on the single side of substrate by resistance Thermal evaporation deposition or sputtering method form the lower electrode (cathode) for including Al-Li alloys etc., then by resistive heating evaporation or The film forming methods such as ion beam sputtering, which stack gradually, to be includedThe electron transfer layer of oxadiazole derivative, triazole derivative etc., Luminescent layer, the hole transmission layer comprising TPD etc. and upper electrode (anode) make as organic EL layer.It should be noted that As long as the Rotating fields or material of organic EL element are played as display element function, it is not particularly limited.In addition, the present invention Resin combination can be applied in the organic EL element of any structure.
Passivating film is formed in a manner of covering organic EL element.Passivating film can use the inorganic materials such as silicon nitride, silica The methods of material is by being deposited or sputtering is formed.Moisture, ionic impurity etc. invade organic EL element and set passivating film in order to prevent. The thickness of passivating film is preferably the scope of 10nm~100 μm, more preferably the scope of 100nm~10 μm.
For passivating film, although depending on film build method, the defective film generally there are pin hole is most In the case of for the weak film of mechanical strength.Therefore, in the sealed solid method using the resin combination of the present invention, in passivating film Upper further coating binder, is crimped using sealing with transparent substrate, and cures adhesive, and what thus raising sealed can By property.
Embodiment
Next, the present invention is described in more detail by embodiment.The present invention is not limited to the following examples.Need It is noted that the unit " part " of numerical value represents mass parts.
With the resin combination and solidfied material of the invention for forming to obtain ultraviolet hardening shown in following embodiments.Separately Outside, the evaluation method and evaluation criterion on resin combination and cured film are performed as follows.It should be noted that on Embodiment containing organic solvent, is evaluated after organic solvent is fully volatilized using evaporator.
(1) moisture permeability：Resin combination is clamped with the glass substrate of 5mm thickness, thickness is adjusted using 100 μm of septs, And with high-pressure sodium lamp (120W/cm, ozone free) with 3000mJ/cm2Cured, so as to make test film.For obtained examination Piece is tested, using Lyssy water vapour permeability meters L80-5000 (Systech Illinois company systems), measures 60 DEG C × 90%RH Under the conditions of moisture permeability.The results are shown in Table 1.
(2) Tg (glass transition temperature)：For the Tg points of the resin combination after curing, with determination of viscoelasticity system EXSTAR DMS-6000 (SII NanoTechnology Co. Ltd. systems), stretch mode, frequency 1Hz are measured.As a result such as Shown in table 1.
(3) cure shrinkage：The coating resin composition on base material, and carried out with high-pressure sodium lamp (120W/cm, ozone free) 3000mJ/cm2Irradiation make its curing, so as to make the solidfied material of film gravity test.
For the solidfied material, according to JIS K7112 B methods, the proportion (DS) of solidfied material is measured.In addition, at 23 ± 2 DEG C The proportion (DL) of resin combination is measured, and is calculated as follows cure shrinkage.Measurement result is averaged with four measurement results Value represents.
Cure shrinkage (%)=(DS-DL)/DS × 100
(4) brittleness：In easy gluing PET (100 μ m-thicks of A4300：Toyo Boseki K.K manufactures) on, scraped using Meyer Rod coater (メ イ ヤ ー バ ー コ ー タ ー) uses high-pressure sodium lamp (120W/ with 20 μm of thickness coating resin composition Cm, ozone free) carry out 3000mJ/cm2Irradiation make its curing, so as to obtain test film.Then, by by the test film bending 180 ° and evaluated.
(5) transmissivity：Resin combination is clamped with glass substrate, adjusts thickness using 60 μm of septs, and use high pressure Mercury lamp (120W/cm, ozone free) is with 3000mJ/cm2Cured, so as to make test film.For obtained test film, use Spectrophotometer U-3900 (Co., Ltd. Hitachi's high-tech system), with measurement range：780~380nm, light source：C, visual angle：2 ° of progress Measure, and record the transmissivity under 400nm.
Table 1
In comparative example 1, using high-pressure sodium lamp (120W/cm, ozone free) with 2000mJ/cm2It is not fully cured, therefore only remembers The project that can be measured is carried.
R-604：Hydroxy pivalin aldehyde is modified trimethylolpropane diacrylate, Nippon Kayaku K. K's manufacture
R-684：Tricyclodecane Dimethanol acrylate, Nippon Kayaku K. K's manufacture
OPP-1：Acrylic acid neighbour's phenylphenoxy ethyl ester, Nippon Kayaku K. K's manufacture
PHE：Acrylate, the manufacture of chemical industry Co., Ltd. of Xin Zhong villages
FA-320A：The bisphenol A-type diacrylate of 2 mole of ethylene oxide, Hitachi Chemical Co., Ltd.'s manufacture
NIKANOL Y-50：The reaction product of meta-xylene and formaldehyde (number-average molecular weight 250), Fudow Co. Ltd. systems Make
ADAMANTATE M-104：Methacrylic acid 1- adamantane esters, Idemitsu Kosen Co., Ltd.'s manufacture
MH-002：1,2- double (trimethylsiloxy) -1,1,2,2- tetraphenyl ethane, Wako Pure Chemicals Co., Ltd. system Make
Irgacure 184D：1- hydroxycyclohexyl phenyl ketones, the manufacture of BASF Co., Ltd.
The evaluation result of embodiment 1~8 and comparative example 1 from table 1 can be seen that the tree of the invention with specific composition The Tg high of oil/fat composition, cure shrinkage, moisture permeability are low.Therefore, for example various sealing materials can be suitable for, particularly had The sealing material of machine EL element.In addition, in embodiment, cure shrinkage all less than 2%, does not also see in brittleness test Observe the generation of crackle.Transmissivity all more than 90%.
The present invention is described in detail with reference to specific mode, but it is aobvious and easy to those skilled in the art What is seen is to make various changes and modifications without departing from the spirit and scope of the present invention.
In addition, the Japanese patent application (2013-071027) that the application was submitted based on March 29th, 2013, this application is whole Body is quoted by quoting.It is in addition, cited herein all referring to being incorporated to as a whole in this specification.
Industrial applicability
The resin combination of the present invention and its transmission of visible light of solidfied material are excellent, Tg high, and cure shrinkage, moisture-inhibiting Degree, brittleness are low, therefore are suitable for various sealing materials, particularly the sealing material of organic EL element.

Claims (13)

1. a kind of carry out cured resin combination merely with energy-ray, it contains (methyl) propylene with fragrant hydrocarbon skeleton Ester compound (A), ring-type (methyl) acrylate compounds (B) and polymerization initiator (C), wherein,
Compound (A) is more than simple function or difunctionality has monocyclic (methyl) acrylate compounds, simple function or double More than function (methyl) acrylate compounds with heterocycle or selected from following groups (methyl) propylene with naphthyl Ester compound,
(methyl) acrylic acid naphthalene ester, (poly-) ethyoxyl (methyl) acrylic acid naphthalene ester, (poly-) propoxyl group (methyl) acrylic acid naphthalene ester, (poly-) caprolactone modification (methyl) acrylic acid naphthalene ester, dinaphthol (methyl) acrylate, dinaphthol (poly-) ethyoxyl (methyl) third Olefin(e) acid ester, dinaphthol (poly-) propoxyl group (methyl) acrylate, (poly-) caprolactone modification dinaphthol (methyl) acrylate, naphthols (methyl) acrylate, naphthols (poly-) ethyoxyl (methyl) acrylate, naphthols (poly-) propoxyl group (methyl) acrylate, (poly-) Caprolactone modification naphthols (methyl) acrylate, dinaphthol two (methyl) acrylate, dinaphthol (poly-) ethyoxyl two (methyl) Acrylate, two (methyl) acrylate of dinaphthol (poly-) propoxyl group and (poly-) caprolactone modification dinaphthol two (methyl) acrylic acid Ester；
Relative to 100 parts by weight of resin combination, content of the compound (A) in resin combination is 20~70 parts by weight；
Compound (B) is selected from by being that 20~70 parts by weight have an alicyclic hydrocarbon skeleton relative to 100 parts by weight of resin combination (methyl) acrylate compounds and there is heterocyclic skeleton for 20~70 parts by weight relative to 100 parts by weight of resin combination (methyl) acrylate compounds composition at least one of group (methyl) acrylate compounds；
Water vapour permeability at 60 DEG C of the resin combination is 47g/m2It is following, and the transmissivity under 400nm is 90% More than.
2. resin combination as claimed in claim 1, wherein, compound (A) is to have two or more aromatic hydrocarbon in a molecule (methyl) acrylate compounds of skeleton.
3. resin combination as claimed in claim 1 or 2, wherein, the fragrant hydrocarbon skeleton of compound (A) has by following formula (1) The skeleton of expression,
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3.
4. resin combination as claimed in claim 1 or 2, wherein, compound (A) is the compound represented by following formula (2),
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3, and Y represents hydrogen atom or methyl, R1Represent hydrogen atom, carbon Alkyl, halogen atom or (methyl) acryloyl group of atomicity 1~3, R2Represent (poly-) of Direct Bonding or carbon number 1~10 Alkylene oxide group.
5. resin combination as claimed in claim 2, wherein, in a molecule (methyl) with two or more fragrance hydrocarbon skeleton Acrylate compounds are (methyl) acrylate compounds with fluorene skeleton, naphthalene skeleton or biphenyl backbone.
6. resin combination as claimed in claim 1 or 2, wherein, compound (B) is (methyl) third with alicyclic hydrocarbon skeleton Enoic acid ester compounds, are (methyl) acrylate compounds in a molecule with two or more alicyclic hydrocarbon skeleton.
7. resin combination as claimed in claim 6, wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton contain There are bicyclic decane structure, tristane ring or adamantane ring as alicyclic hydrocarbon skeleton.
8. resin combination as claimed in claim 6, wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton are (methyl) acrylate compounds represented by following formula (3),
In formula, R3Hydrogen atom, the alkyl of carbon number 1~3, halogen atom or following formula (4) are represented independently of one another, and extremely A few R3For following formula (4),
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * and ring-type Skeleton is bonded.
9. resin combination as claimed in claim 6, wherein, (methyl) acrylate compounds with alicyclic hydrocarbon skeleton are (methyl) acrylate compounds represented by following formula (5),
In formula, R6And R7The alkylidene or (poly-) alkylene oxide group of Direct Bonding or carbon number 1~6 are represented independently of one another.
10. resin combination as claimed in claim 1 or 2, wherein, compound (B) is (methyl) third with heterocyclic skeleton Enoic acid ester compounds, are (methyl) acrylate compounds represented by following formula (6),
In formula, R8Represent Direct Bonding, the alkylidene or alkylene oxide group of carbon number 1~6, R9Represent hydrogen or carbon number 1~4 Alkyl, Z represents carbon atom, oxygen atom or nitrogen-atoms.
11. resin combination as claimed in claim 1, wherein, the compound (A) represented by following formula (2)：By following formula (3) table The weight ratio for the compound (B) shown is 9：1~1：9,
In formula, X represents the alkylidene of Direct Bonding or carbon number 1~3, and Y represents hydrogen atom or methyl, R1Represent hydrogen atom, carbon Alkyl, halogen atom or (methyl) acryloyl group of atomicity 1~3, R2Represent (poly-) of Direct Bonding or carbon number 1~10 Alkylene oxide group；
In formula, R3Hydrogen atom, the alkyl of carbon number 1~3, halogen atom or following formula (4) are represented independently of one another, and extremely A few R3For following formula (4)；
In formula, R2Represent Direct Bonding or (poly-) alkylene oxide group of carbon number 1~10, Y represents hydrogen atom or methyl, * and ring-type Skeleton is bonded.
12. resin combination as claimed in claim 1 or 2, it is used for OLED purposes.
13. a kind of low moisture-inhibiting barrier film, it is obtained by making the resin composition any one of claim 1~11 Arrive.
CN201480019186.3A 2013-03-29 2014-03-28 Energy ray curable resin composition and its solidfied material Expired - Fee Related CN105073800B (en)

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