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CN105073799A - Energy ray-curable resin composition and cured product of same - Google Patents

Energy ray-curable resin composition and cured product of same Download PDF

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Publication number
CN105073799A
CN105073799A CN201480019185.9A CN201480019185A CN105073799A CN 105073799 A CN105073799 A CN 105073799A CN 201480019185 A CN201480019185 A CN 201480019185A CN 105073799 A CN105073799 A CN 105073799A
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CN
China
Prior art keywords
methyl
acrylic compound
acrylate
skeleton
resin combination
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CN201480019185.9A
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Chinese (zh)
Inventor
木户场润
松尾雄一朗
内藤伸彦
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Publication of CN105073799A publication Critical patent/CN105073799A/en
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    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/844—Encapsulations

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Electroluminescent Light Sources (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)

Abstract

The invention discloses an energy ray-curable resin composition and cured product of same. According to the invention, a resin composition contains a (meth)acrylate compound (A) having an alicyclic hydrocarbon skeleton, a cyclic (meth)acrylate compound (B), and a polymerization initiator (C), wherein the cyclic (meth) acrylate compound (B) is a (meth)acrylate compound different from the above compound (A) and is at least one (meth)acrylate compound selected from the group consisting of (meth)acrylate compounds having an alicyclic hydrocarbon skeleton and (meth)acrylate compounds having a heterocyclic skeleton.

Description

Energy ray curable resin composition and cured article thereof
Background technology
Energy ray curable resin generally can be processed in the absence of a solvent, and therefore workability is excellent.In addition, because curing speed is fast, energy requirement is low, therefore energy ray curing technology is important technology in the various industries being representative with indicating meter periphery material.In recent years, in indicating meter, 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, expect that organic electroluminescent (EL) indicating meter (OLED) is as follow-on emissive type thin-film display, and a part of goods are practical.The organic EL of OLED display has the structure of the element portion main body being formed with the thin-film laminate comprised containing the luminescent layer clamped by negative electrode and anode on the substrates such as the glass being formed with the driving circuits such as TFT.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 is sealed to block from the moisture of outside or the intrusion of impurity.In order to realize high-quality and the organic EL of high reliability, expect more high performance sealing material, all the time in the various packing technique of research.
As the representational sealing method of organic EL, have studied and to be used by the sealing cover being inserted with the metal of siccative or glass in advance sealing to stick with glue agent to be fixed on method (patent documentation 1) on the substrate of organic EL.In the method, at the substrate peripheral part coating binder of organic EL, sealing cover is set thereon, then makes adhesive solidification, thus substrate and sealing cover are fixed, thus sealing organic el element.In such method, what utilize the sealing cover of glass to carry out is sealed to main flow.But the sealing cover of glass is made by the borehole processing carried out for siccative being inserted smooth glass substrate, therefore has the tendency that cost uprises.In addition, the sealing utilizing sealing cover to carry out, owing to inserting siccative in the inner side of sealing cover, thus cannot extract light from sealing 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 driving circuit portion be formed on substrate, and the reduction of the extraction efficiency caused because driving circuit portion covers a part of light.Therefore, expect to develop the sealing method that can be applicable to extract the top emission type element of light from the opposition side of the substrate of organic EL.
As the representational sealing method that can be applicable to top emission type element, there are diaphragm seal method and sealed solid method.Diaphragm seal method is that laminated multi-layer comprises the method (patent documentation 2) that film that is inorganic or organic materials forms passive film on organic EL.In order to give sufficient moisture resistance by the method to element, need the film stacking gradually several layers on element.Therefore, for diaphragm seal method, film formation process is long and cost is high, and in addition, the introducing of the large-scale vacuum system device required for film forming, thus has the tendency that initial investment uprises.
On the other hand, sealed solid method is that the mode of the element portion covering whole organic EL arranges passive film, and arranges the method (see patent documentation 3) of sealing transparency carrier via sealing material thereon.Usually, passive film is by evaporation or sputtering inorganic materials and being formed, but in most cases it is have the defective film of pin hole or the weak film of physical strength.Therefore, in sealed solid method, after element arranges passive film, stick with glue agent via sealing and the sealing transparency carriers such as glass substrate are set, improve the reliability of sealing thus.Such sealed solid method receives publicity as the method can implementing simply and at low cost the sealing of top emission type element.
In the sealing utilizing sealed solid method to carry out of organic EL, heat or light-cured resin can be used to stick with glue agent as sealing, but their characteristic is owing to likely making a significant impact the performance of element and the productivity of sealing operation, therefore extremely important.Such as, when sealing sticks with glue the water vapour permeability deficiency of agent, likely invade element portion from the pin hole of passive film, cause the deterioration of element.In addition, if the curing reaction of sealing material is slow, then curing process expends time in, and the productivity of sealing operation likely reduces.
Agent is sticked with glue for the sealing used in these; except requiring except the high-transmission rate in visible region, also require can tolerate luminescence photostabilization, stable plasticity, for suppress unrelieved stress low cure shrinkage, for the protection of the low water vapour permeability etc. of luminous element from moisture.Known tackiness agent can be used to stick with glue agent as the sealing of organic EL and implement sealing by sealed solid method, but be difficult to obtain to meet the result of reliability and productivity, water vapour permeability 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. 3876630th, Japanese Patent
Patent documentation 2: No. 2679586th, Japanese Patent
Patent documentation 3: No. 4421938th, Japanese Patent
Patent documentation 4: No. 4655172nd, Japanese Patent
Patent documentation 5: Japanese Unexamined Patent Publication 2001-81182 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2000-169552 publication
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide the resin combination of the sealing material being suitable for organic EL and the cured article of transmission of visible light is excellent, cure shrinkage, Water Vapour Permeability and fragility are low this resin combination.
For the means of dealing with problems
The present inventor has carried out research extensively and profoundly to solve above-mentioned problem, found that, energy ray-curable resin combination and the cured article thereof with specific composition can solve above-mentioned problem, thus complete the present invention.
That is, the present invention relates to following (1) ~ (9).
(1) a kind of resin combination, it contains (methyl) acrylic compound (A), ring-type (methyl) acrylic compound (B) and the polymerization starter (C) with alicyclic hydrocarbon skeleton, wherein
Ring-type (methyl) acrylic compound (B) is (methyl) acrylic compound different from described compound (A), and for being selected from least one (methyl) acrylic compound in the group that is made up of (methyl) acrylic compound with alicyclic hydrocarbon skeleton and (methyl) acrylic compound with heterocyclic skeleton.
(2) resin combination as described in (1), wherein, there is (methyl) acrylic compound (A) of alicyclic hydrocarbon skeleton for having (methyl) acrylic compound of two or more alicyclic hydrocarbon skeleton in a part.
(3) resin combination as described in (1) or (2), wherein, the alicyclic hydrocarbon skeleton respectively had in (methyl) acrylic compound of alicyclic hydrocarbon skeleton is dicyclo decane skeleton, tricyclodecane skeleton or adamantane framework separately.
(4) resin combination as described in (1) or (2), wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (1)
In formula, R 1represent the alkyl of hydrogen atom, carbonatoms 1 ~ 3, halogen atom or following formula (2) independently of one another, and at least one R 1for following formula (2),
In formula, R 2represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10, Y represents hydrogen atom or methyl, * and cyclic skeleton bonding.
(5) resin combination as described in (1) or (2), wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (3)
In formula, R 3and R 4represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6.
(6) resin combination according to any one of (1) ~ (5), wherein, ring-type (methyl) acrylic compound (B) is for having (methyl) acrylic compound of heterocyclic skeleton, (methyl) acrylic compound with heterocyclic skeleton is (methyl) acrylic compound represented by following formula (4)
In formula, R 5represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6 independently of one another, R 6represent the alkyl of hydrogen or carbonatoms 1 ~ 4 independently of one another, Z represents methylene radical, Sauerstoffatom or nitrogen-atoms independently of one another, but Z is not all methylene radical.
(7) resin combination as described in (6), wherein, (methyl) acrylic compound (A) represented by above formula (1): the weight ratio of ring-type (methyl) acrylate (B) represented by above formula (4) is 9:1 ~ 1:9.
(8) a low moisture-inhibiting barrier film, it obtains by making the resin composition according to any one of (1) ~ (7).
(9) resin combination according to any one of (1) ~ (7), it is for OLED purposes.
Invention effect
The transmission of visible light of resin combination of the present invention and cured article thereof is excellent, and cure shrinkage, Water Vapour Permeability and fragility are low, is therefore particularly suitable for the sealing material of organic EL.
Embodiment
Resin combination of the present invention contains (methyl) acrylic compound (A), ring-type (methyl) acrylic compound (B) and the polymerization starter (C) with alicyclic hydrocarbon skeleton.
By above-mentioned formation, different (methyl) acrylic compound of two kinds of skeletons is incorporated in curing system mutually when solidifying, and can realize only by containing a kind of effect with the irrealizable extremely excellent low water vapour permeability of compound of cyclic skeleton while realizing low-shrinkage.
In addition, the skeleton recorded in the present invention can have substituting group, also can not have substituting group, and when having substituting group, this substituting group is preferably the thiazolinyl of the alkyl of carbonatoms 1 ~ 6, the alkoxyl group of carbonatoms 1 ~ 6 or carbonatoms 1 ~ 6.
As operable in the present invention, that there is alicyclic hydrocarbon skeleton (methyl) acrylic compound (A), can use known (methyl) acrylic compound with alicyclic hydrocarbon skeleton without particular limitation, alicyclic hydrocarbon skeleton is preferably stable hydrocarbon skeleton.Compared with other skeletons such as the skeleton of such ring type skeleton and chain-like structure, have prevent water vapor through effect, by being configured in curing system together with ring-type (methyl) acrylic compound, utilize synergy can prevent significantly water vapor through.
As alicyclic hydrocarbon skeleton, as operable skeleton particularly, cyclopentane framework, hexanaphthene skeleton, suberane skeleton, dicyclo decane skeleton, tricyclodecane skeleton, adamantane framework, isobornyl skeleton etc. can be enumerated.
Wherein, preferably there is (methyl) acrylic compound of the endocyclic such as tricyclodecane skeleton, adamantane framework hydrocarbon skeleton.In such compound, alicyclic hydrocarbon skeleton forms bridge joint, therefore forms three-dimensional arrangement and be configured in the space of ring texture by carbon atom, therefore can more effectively prevent water vapor through.And above-mentioned synergy is by mixing with such (methyl) acrylic compound with endocyclic hydrocarbon skeleton and become higher.
In addition, preferably (methyl) acryl is connected on ring type hydrocarbon skeleton.Particularly; preferably (methyl) acryl directly or be connected on above-mentioned ring type hydrocarbon skeleton via alkyl; as alkyl when connecting via alkyl, the alkylidene group of the alkylidene group can enumerating carbonatoms 1 ~ 10 or the carbonatoms 1 ~ 10 with ehter bond.
As such concrete example with (methyl) acrylic compound of alicyclic hydrocarbon skeleton, (methyl) acrylic compound of more than following simple function (methyl) acrylic compound or difunctionality can be enumerated.
As simple function (methyl) acrylic compound, (methyl) isobornyl acrylate can be enumerated, (methyl) vinylformic acid tetrahydrochysene dicyclopentadiene base ester, (methyl) vinylformic acid dihydro dicyclopentadiene base ester, (methyl) vinylformic acid dihydro dicyclopentadiene base oxygen base ethyl ester, (methyl) cyclohexyl acrylate, 1, 3-diamantane glycol two (methyl) acrylate, 1, 3-diamantane dimethanol two (methyl) acrylate, (methyl) vinylformic acid 2-methyl-2-adamantane esters, (methyl) vinylformic acid 2-ethyl-2-adamantane esters, (methyl) vinylformic acid 3-hydroxyl-1-adamantane esters, ester ring type (methyl) acrylate such as (methyl) vinylformic acid 1-adamantane esters.As multifunctional (methyl) acrylic compound more than difunctionality, ester ring type (methyl) acrylate etc. such as Tricyclodecane Dimethanol (methyl) acrylate can be enumerated.
As such (methyl) acrylic compound with ring type hydrocarbon skeleton, (methyl) acrylic compound with the structure represented by following formula (1) preferably can be used.
In formula, R 1represent the alkyl of hydrogen atom, carbonatoms 1 ~ 3, halogen atom or following formula (2) independently of one another, and at least one R 1for following formula (2),
In formula, R 2represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10, Y represents hydrogen atom or methyl, * and cyclic skeleton bonding.
In addition, (methyl) acrylic compound represented by following formula (3) can preferably be used.
In formula, R 3and R 4represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6.At this, as the concrete example of such (methyl) acrylic compound, ester ring type (methyl) acrylate etc. such as Tricyclodecane Dimethanol (methyl) acrylate can be enumerated.
The content of (methyl) acrylic compound in resin combination with alicyclic hydrocarbon skeleton is preferably 5 ~ 95 weight parts usually relative to resin combination 100 weight part, is more preferably 10 ~ 80 weight parts, is particularly preferably 20 ~ 70 weight parts.
As the ring-type used in the present invention (methyl) acrylate (B), (methyl) acrylate with alicyclic hydrocarbon skeleton, (methyl) acrylate with heterocyclic skeleton can be used.
At this, use there is alicyclic hydrocarbon skeleton (methyl) acrylic compound as ring-type (methyl) acrylic compound time, resin combination becomes the resin combination with (methyl) acrylic compound of alicyclic hydrocarbon skeleton containing having two kinds of different structures.And (methyl) acrylate with alicyclic hydrocarbon skeleton that can use as ring-type (methyl) acrylate, can use (methyl) acrylic compound same as described above.
When using two kinds to have (methyl) acrylic compound of alicyclic hydrocarbon skeleton like this, compared with other skeletons such as the skeleton of chain-like structure, have prevent water vapor through effect, by being configured in curing system together with (methyl) acrylic compound with alicyclic hydrocarbon skeleton, utilize synergy can prevent significantly water vapor through.
Below (methyl) acrylic compound with heterocyclic skeleton that can use as ring-type (methyl) acrylic compound in the present invention is described.
Compared with other skeletons such as the skeleton of such heterocyclic skeleton and chain-like structure, have prevent water vapor through effect, by being configured in curing system together with (methyl) acrylic compound with alicyclic hydrocarbon skeleton, utilize synergy can prevent significantly water vapor through.
As heterocyclic skeleton, as operable skeleton particularly, dioxane skeleton, trioxane skeleton, isocyanuric acid ester skeleton etc. can be enumerated.
In addition, preferably (methyl) acryl is connected on heterocyclic skeleton.Particularly, preferably (methyl) acryl is directly or be connected on above-mentioned heterocyclic skeleton via alkyl, as alkyl when connecting via alkyl, and the alkyl of the alkyl can enumerating carbonatoms 1 ~ 10 or the carbonatoms 1 ~ 10 with ehter bond.
As such concrete example with (methyl) acrylic compound of heterocyclic skeleton, following (methyl) acrylic compound can be enumerated.
Namely, can enumerate: (methyl) tetrahydrofurfuryl acrylate, alkoxylate tetrahydrofurfuryl acrylate, caprolactone modification (methyl) tetrahydrofurfuryl acrylate, morpholine (methyl) acrylate, isocyanuric acid EO modified diacrylate (M-215), 6-caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester (M-327), isocyanuric acid EO modified diacrylate and triacrylate (M-313 or M-315), hydroxy pivalin aldehyde modification trimethylolpropane diacrylate (R-604), methacrylic acid pentamethvl ester (FA-711), methacrylic acid tetramethyl piperidine ester (FA-712HM), cyclic trimethylolpropane formal acrylate (SR531).
As such (methyl) acrylic compound with heterocyclic skeleton, such as the example of heterocycle, can enumerate: morpholine skeleton, tetrahydrofuran (THF) skeleton, amylene oxide skeleton, dioxane skeleton, triazine skeleton, carbazole skelton, tetramethyleneimine skeleton, piperidine scaffolds, preferably can use (methyl) acrylic compound with the structure represented by following formula (5).
In formula, R 5represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6 independently of one another, R 6represent the alkyl or alkenyl of hydrogen atom or carbonatoms 1 ~ 4, X represents nitrogen-atoms, Sauerstoffatom or methylene radical independently of one another, and Y represents methylene radical or carbonyl independently of one another, and m represents the integer of 1 ~ 4, but X is not all methylene radical.
At this, the compound represented by following formula (4) preferably can be used.
In formula, R 5represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6 independently of one another, R 6represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another, Z represents methylene radical, Sauerstoffatom or nitrogen-atoms independently of one another.But Z is not all methylene radical.
The content of (methyl) acrylic compound in resin combination with heterocyclic skeleton is preferably 5 ~ 95 weight parts usually relative to resin combination 100 weight part, is more preferably 10 ~ 80 weight parts, is particularly preferably 20 ~ 70 weight parts.
About resin combination of the present invention, in (methyl) acrylic compound composition in resin combination, the gross weight preferably with (methyl) acrylic compound (hereinafter referred to as poly-EO modification (methyl) acrylic compound) of the structure represented by following part structural formula (A) is less than the gross weight of (methyl) acrylic compound except poly-EO modification (methyl) acrylic compound, is more preferably less than 1/2.This is because, the water vapour permeability of above-mentioned poly-EO modification (methyl) acrylic compound is poor, when the content of this poly-EO modification (methyl) acrylic compound is many, when preponderating in resin combination, likely water vapour permeability is poor.
In formula, t represents the integer of more than 2.
And in resin combination, the gross weight of poly-EO modification (methyl) acrylic compound is preferably below 10 weight parts relative to resin combination 100 weight part, is more preferably below 5 weight parts, is particularly preferably below 2 weight parts.
In the present invention, as ring-type (methyl) acrylic compound and as poly-EO modification (methyl) acrylic compound, ring-type gathers EO modification (methyl) acrylic compound, preferably not as (methyl) acrylic compound or the use of ring-type (methyl) acrylic compound with aromatic hydrocarbon skeleton of the present invention, even if therefore use, also be preferably below 20 weight parts relative to resin combination 100 weight part, be particularly preferably below 10 weight parts.
In the present invention, the ratio of (methyl) acrylate (A) and ring-type (methyl) acrylic compound (B) with alicyclic hydrocarbon skeleton of containing in resin combination is preferably 1:9 ~ 9:1 with mass ratio range, be more preferably 7:3 ~ 9:1, be particularly preferably 5:5 ~ 9:1.
By being set as above-mentioned preferred scope, the resin combination that water vapour permeability is extremely excellent can be obtained.
As the polymerization starter used in the present invention (C), the various polymerization starter such as Photoepolymerizationinitiater initiater, hot radical polymerization starter can be used.
In addition, as Photoepolymerizationinitiater initiater, can enumerate particularly: the bitter almond oil camphor classes such as bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether, benzoin isobutyl ether; Methyl phenyl ketone, 2,2-dimethoxy-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-hydroxycyclohexyl phenyl ketone, 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholinopropane-1-ketone, oligomeric [2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] acetone]; The Anthraquinones such as 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthene ketones such as 2,4-diethyl thioxanthone, ITX, CTX; The ketal classes such as methyl phenyl ketone dimethyl ketal, dibenzoyl dimethyl ketal; Benzophenone, 4-benzoyl-4 '-methyldiphenyl thioether, 4, the benzophenones such as 4 '-dimethylamino benzopheone; The phosphinoxidess such as TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, phenylbenzene-(2,4,6-trimethylbenzoyl) phosphine oxide; Deng.Be preferably acetophenones, more preferably can enumerate 2-hydroxy-2-methyl phenyl-propane-1-ketone, 1-hydroxycyclohexyl phenyl ketone.It should be noted that, in resin combination of the present invention, Photoepolymerizationinitiater initiater can be used alone or multiple used in combination.
In addition, as hot radical polymerization starter, as long as by adding thermogenesis free radical and the compound causing chain polymerization is then not particularly limited, organo-peroxide, azo-compound, bitter almond oil camphor compound, benzoin ether compound, acetophenone compound, benzpinacol etc. can be enumerated, preferably use benzpinacol.Such as, as Kayamek (trade mark) A of organo-peroxide, M, R, L, LH, SP-30C, Perkadox (trade mark) CH-50L, BC-FF, Cadox (trade mark) B-40ES, Perkadox (trade mark) 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 (trade mark) H, C, ND, L, Percumyl (trade mark) H, D, Peroyl (trade mark) IB, IPP, Perocta (trade mark) ND (Japan Oil Co's manufacture) etc. can obtain as commercially available product.In addition, VA-044, V-070, VPE-0201, VSP-1001 etc. (Wako Pure Chemical Industries, Ltd.'s manufacture) etc. as azo-compound can obtain as commercially available product.
As above-mentioned hot radical polymerization starter, preferred benzpinacol class hot radical polymerization starter (comprise and the material after chemically modified is carried out to benzpinacol).Can enumerate particularly: benzpinacol, 1,2-dimethoxy-1,1,2,2-tetraphenyl ethane, 1,2-diethoxy-1,1,2,2-tetraphenyl ethane, 1,2-hexichol Oxy-1,1,2,2-tetraphenyl ethane, 1,2-dimethoxy-1,1,2,2-tetra-(4-aminomethyl phenyl) ethane, 1,2-hexichol Oxy-1,1,2,2-tetra-(4-p-methoxy-phenyl) ethane, 1,2-two (trimethylsiloxy)-1,1,2,2-tetraphenyl ethane, two (silicoheptane alcoxyl base)-1,1,2, the 2-tetraphenyl ethane of 1,2-, 1,2-two (t-butyldimethylsilyloxy base)-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl-silicane Oxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-t-butyldimethylsilyloxy base-1,1,2,2-tetraphenyl ethane etc., preferred 1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-triethyl-silicane Oxy-1,1,2,2-tetraphenyl ethane, 1-hydroxyl-2-t-butyldimethylsilyloxy base-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy)-1,1,2,2-tetraphenyl ethane, further preferred 1-hydroxyl-2-trimethylsiloxy-1,1,2,2-tetraphenyl ethane, 1,2-two (trimethylsiloxy)-1,1,2,2-tetraphenyl ethane, particularly preferably 1,2-two (trimethylsiloxy)-1,1,2,2-tetraphenyl ethane.
Above-mentioned benzpinacol is by the sale such as Tokyo HuaCheng Industry Co., Ltd, Wako Pure Chemical Industries, Ltd..In addition, the etherification of hydroxyl groups of benzpinacol easily can be synthesized by known method.In addition, the hydroxyl silyl etherificate of benzpinacol can be undertaken being synthesized into by the method heating corresponding benzpinacol and various silylating agent under the basic catalysts such as pyridine.As silylating agent, the known trimethylchlorosilane as trimethylsilylation agent (TMCS), hexamethyldisilazane (HMDS), N, O-two (trimethyl silyl) trifluoroacetamide (BSTFA), the chlorotriethyl silane (TECS) as triethylsilyl agent, the t-butyldimethylsilyl (TBMS) etc. as t-butyldimethylsilyl agent can be enumerated usually.These reagent easily can obtain from the markets such as silicon derivative manufacturers.As the reacting weight of silylating agent, be preferably 1.0 ~ 5.0 times moles relative to the hydroxyl 1 mole of subject compound.More preferably 1.5 ~ 3.0 times moles.When being less than 1.0 times moles, reaction efficiency is poor, and therefore long reaction time likely promotes thermolysis.During more than 5.0 times moles, be separated when likely reclaiming and be deteriorated or be difficult to purifying.
The content of composition of the present invention (C) is preferably 0.1 ~ 10 mass parts relative to total amount 100 mass parts of resin combination, is more preferably 0.5 ~ 5 mass parts.It should be noted that, in resin combination of the present invention, polymerization starter (C) can be used alone or multiple used in combination.
As (methyl) acrylic compound (D) with aromatic hydrocarbon skeleton that can optionally contain in resin combination of the present invention, as long as have (methyl) acrylic compound of at least one aromatic nucleus in molecule, then can use arbitrarily known compound.Have in the compound of aromatic nucleus at such, owing to having aromatic nucleus, resin combination therefore can be made to have water repellency, can water vapour permeability be reduced.And if (methyl) acrylic compound for having more than one aromatic nucleus in molecule, then this effect can realize fully.In addition, by having two or more aromatic nucleus in molecule, this effect is more excellent, therefore preferably.As the skeleton in such molecule with two or more aromatic nucleus, can enumerate biphenyl backbone or bisphenol backbone, these skeletons can realize showing excellent water vapour permeability.
As such concrete example with (methyl) acrylic compound of aromatic hydrocarbon skeleton, (methyl) acrylic compound of more than following simple function (methyl) acrylic compound or difunctionality can be enumerated.
As the example of simple function (methyl) acrylic compound, can enumerate: (methyl) benzyl acrylate, oxyethyl group modification cresols (methyl) acrylate, propoxy-modification cresols (methyl) acrylate, neopentyl glycol benzoic ether (methyl) acrylate, orthoxenol (methyl) acrylate, orthoxenol monosubstituted ethoxy (methyl) acrylate, orthoxenol polyethoxye (methyl) acrylate, p-phenyl phenol (methyl) acrylate, p-phenyl phenol monosubstituted ethoxy (methyl) acrylate, p-phenyl phenol polyethoxye (methyl) acrylate, the adjacent phenylbenzyl ester of vinylformic acid, vinylformic acid has (methyl) acrylic compound of monocycle to phenylbenzyl ester etc., carbazole (gathering) oxyethyl group (methyl) acrylate, carbazole (gathering) propoxy-(methyl) acrylate, (gathering) caprolactone modification carbazole (methyl) acrylate etc. have (methyl) acrylic compound of heterocycle, (methyl) vinylformic acid naphthalene ester, (gathering) oxyethyl group (methyl) vinylformic acid naphthalene ester, (gathering) propoxy-(methyl) vinylformic acid naphthalene ester, (gathering) caprolactone modification (methyl) vinylformic acid naphthalene ester, dinaphthol (methyl) acrylate, dinaphthol (gathering) oxyethyl group (methyl) acrylate, dinaphthol (gathering) propoxy-(methyl) acrylate, (gathering) caprolactone modification dinaphthol (methyl) acrylate, naphthols (methyl) acrylate, naphthols (gathering) oxyethyl group (methyl) acrylate, naphthols (gathering) propoxy-(methyl) acrylate, (gathering) caprolactone modification naphthols (methyl) acrylate etc. has (methyl) acrylic compound of condensed ring.
As (methyl) acrylic compound more than difunctionality, can enumerate: (gathering) oxyethyl group modified bisphenol A two (methyl) acrylate, (gathering) propoxy-modified bisphenol A two (methyl) acrylate, (gathering) oxyethyl group modified bisphenol F bis-(methyl) acrylate, (gathering) propoxy-modified bisphenol F bis-(methyl) acrylate, (gathering) oxyethyl group modified bisphenol S bis-(methyl) acrylate, (gathering) propoxy-modified bisphenol S bis-(methyl) acrylate, hexahydrophthalic acid two (methyl) acrylate, two phenoxy group (gathering) oxyethyl group fluorenes etc. has (methyl) acrylic compound of monocycle, biphenyl dimethanol two (methyl) acrylate etc. has (methyl) acrylic compound of heterocycle, dinaphthol two (methyl) acrylate, dinaphthol (gathering) oxyethyl group two (methyl) acrylate, dinaphthol (gathering) propoxy-two (methyl) acrylate, (gathering) caprolactone modification dinaphthol two (methyl) acrylate etc. have (methyl) acrylic compound of condensed ring, bisphenol fluorene two (methyl) acrylate, two phenoxy group methyl alcohol fluorenes two (methyl) acrylate, two phenoxyethyl alcohol fluorenes two (methyl) acrylate, two phenoxy group caprolactone fluorenes two (methyl) acrylate etc. have (methyl) acrylic compound etc. of Ppolynuclear aromatic.
As (methyl) acrylic compound with aromatic hydrocarbon skeleton, except above-mentioned (methyl) acrylate monomer, epoxy (methyl) acrylic compound can also be enumerated.
As epoxy (methyl) acrylate, can enumerate: the epoxy resin such as terminal glycidyl group ether, fluorenes epoxy resin, bisphenol-s epoxy resin and (methyl) acrylic acid reaction product etc. of the propylene oxide adduct of bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, biphenyl type phenol aralkyl resin, dihydroxyphenyl propane.
Wherein, as (methyl) acrylic compound with aromatic hydrocarbon skeleton, (methyl) acrylic compound such as with following part skeleton preferably can be used particularly.
In formula, X represents the alkylidene group of Direct Bonding or carbonatoms 1 ~ 3.
Thinking by having above-mentioned part skeleton, more effectively can show the water repellency that aromatic nucleus can be given.
Particularly, in above-mentioned (methyl) acrylic compound, (methyl) acrylic compound with bisphenol backbone or biphenyl backbone corresponds to above-mentioned formula (B), can preferably use.
In addition, preferably (methyl) acryl is connected on aromatic hydrocarbon skeleton.Particularly; preferably (methyl) acryl directly or be connected on above-mentioned aromatic hydrocarbon skeleton via alkyl; as alkyl when connecting via alkyl, the alkylidene group of the alkylidene group can enumerating carbonatoms 1 ~ 10 or the carbonatoms 1 ~ 10 with ehter bond.
In addition, as (methyl) acrylic compound with aromatic hydrocarbon skeleton used in the present invention, (methyl) acrylic compound preferably represented by following formula (7).
In formula, X represents the alkylidene group of Direct Bonding or carbonatoms 1 ~ 3, and Y represents hydrogen atom or methyl, R 7represent the alkyl of hydrogen atom, carbonatoms 1 ~ 3, halogen atom or following formula (2), R 2represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10;
In formula, R 2represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10, Y represents hydrogen atom or methyl, * and benzene skeleton bonding.
The concrete example of (methyl) acrylic compound like this, orthoxenol (methyl) acrylate can be enumerated, orthoxenol monosubstituted ethoxy (methyl) acrylate, orthoxenol polyethoxye (methyl) acrylate, p-phenyl phenol (methyl) acrylate, p-phenyl phenol monosubstituted ethoxy (methyl) acrylate, p-phenyl phenol polyethoxye (methyl) acrylate, the adjacent phenylbenzyl ester of vinylformic acid, vinylformic acid is to phenylbenzyl ester, (gathering) propoxy-modified bisphenol A two (methyl) acrylate, (gathering) oxyethyl group modified bisphenol F bis-(methyl) acrylate, (gathering) propoxy-modified bisphenol F bis-(methyl) acrylate etc.
The content of (methyl) acrylic compound in resin combination with aromatic hydrocarbon skeleton is preferably 5 ~ 95 weight parts usually relative to resin combination 100 weight part, is more preferably 10 ~ 80 weight parts, is particularly preferably 20 ~ 70 weight parts.
In addition, in resin combination of the present invention, consider the viscosity, specific refractory power, adhesivity etc. of resin combination of the present invention that obtain, can use except (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton, ring-type (methyl) acrylic compound (B), there is aromatic hydrocarbon skeleton (methyl) acrylic compound (D) except (methyl) acrylic compound.Particularly; (methyl) acrylate monomer can be enumerated; as this (methyl) acrylate monomer, multifunctional (methyl) acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate etc. in simple function (methyl) acrylate, difunctionality (methyl) acrylate, molecule with more than three (methyl) acryls can be used.
As simple function (methyl) acrylate, can enumerate such as: imide (methyl) acrylate with imide ring structure, butyleneglycol list (methyl) acrylate, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 2-hydroxybutyl, (methyl) vinylformic acid 4-hydroxybutyl, 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) vinylformic acid octafluoro pentyl ester, (methyl) Octyl acrylate, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid, the different myristin of (methyl) vinylformic acid, (methyl) lauryl acrylate etc. has (methyl) acrylate of alkyl, (methyl) acrylate etc. of the polyvalent alcohols such as ethoxydiglycol (methyl) acrylate, 2-ethylhexyl Trivalin SF (methyl) acrylate, polyoxyethylene glycol (methyl) acrylate, polypropylene glycol (methyl) acrylate.
As (methyl) acrylate monomer with Liang Ge functional group, can enumerate: the acrylate of the isocyanic ester such as diacrylated isocyanuric acid ester; 1,4-butyleneglycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, polytetramethylene glycol two (methyl) acrylate etc. have (methyl) acrylate of straight chain methylene radical structure; Two (methyl) acrylate etc. of the polyvalent alcohols such as ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate.
As multifunctional (methyl) acrylate monomer, can enumerate: isocyanuric acid three (acryloyl-oxyethyl) ester, (gathering) caprolactone modification isocyanuric acid three (acryloyl-oxyethyl) ester etc. have multifunctional (methyl) acrylate of isocyanurate ring, tetramethylolmethane three (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, (gathering) oxyethyl group modification tetramethylolmethane four (methyl) acrylate, (gathering) propoxy-modification tetramethylolmethane four (methyl) acrylate, Dipentaerythritol five (methyl) acrylate, (gathering) caprolactone modification Dipentaerythritol five (methyl) acrylate, (gathering) oxyethyl group modification Dipentaerythritol five (methyl) acrylate, (gathering) propoxy-modification Dipentaerythritol five (methyl) acrylate, Dipentaerythritol six (methyl) acrylate, (gathering) caprolactone modification Dipentaerythritol six (methyl) acrylate, (gathering) oxyethyl group modification Dipentaerythritol six (methyl) acrylate, (gathering) propoxy-modification Dipentaerythritol six (methyl) acrylate, polypentaerythritol many (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, (gathering) oxyethyl group modification trimethylolpropane tris (methyl) acrylate, (gathering) propoxy-modification trimethylolpropane tris (methyl) acrylate, two (TriMethylolPropane(TMP)) four (methyl) acrylate, multifunctional (methyl) acrylate of the polyvalent alcohols such as glycerine three (methyl) acrylate, phosphorous multifunctional (methyl) acrylate such as tricresyl phosphate (methyl) acrylate, TriMethylolPropane(TMP) benzoic ether (methyl) acrylate etc. has multifunctional (methyl) acrylate of aromatic group, multifunctional (methyl) acrylate of the sour modifications such as 2,2,2-tri-acryloyloxymethyl succsinic acid, multifunctional (methyl) acrylate etc. with silicone matrix of polysiloxane six (methyl) acrylate etc.
The content of (methyl) acrylate monomer in resin combination except (methyl) acrylic compound (A), (methyl) acrylic compound (B), (methyl) acrylic compound (D) is like this preferably 5 ~ 95 weight parts usually relative to resin combination 100 weight part, be more preferably 10 ~ 80 weight parts, be particularly preferably 20 ~ 70 weight parts.
In the present invention, not damaging in the degree of characteristic, carbamate (methyl) acrylate can be used.
As carbamate (methyl) acrylate, can enumerate such as: diatomic alcohol compounds (such as, ethylene glycol, Diethylene Glycol, triethylene glycol, propylene glycol, dipropylene glycol, 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, hexanaphthene-Isosorbide-5-Nitrae-dimethanol, polyoxyethylene glycol, polypropylene glycol, polymer with bis phenol A oxyethyl group glycol, polymer with bis phenol A propoxy-glycol etc.) or as these diatomic alcohol compounds and diprotic acid or its acid anhydrides (such as, succsinic acid, hexanodioic acid, nonane diacid, dimeracid, m-phthalic acid, terephthalic acid, phthalic acid or their acid anhydrides) the polyester diol of reaction product, with organic multiple isocyanate (such as, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate, the chain stable hydrocarbon isocyanic ester such as 2,4,4-trimethyl hexamethylene diisocyanate, the cyclic saturated hydrocarbon isocyanic ester such as isophorone diisocyanate, norbornene alkyl diisocyanate, dicyclohexyl methane diisocyanate, methylene-bis (4-cyclohexyl isocyanate), hydrogenated diphenyl methane diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tolylene diisocyanate, 2,4-tolylene diisocyanate, 1,3-xylylene diisocyanate, to phenylene vulcabond, 3,3 '-dimethyl-4,4 '-vulcabond, 6-sec.-propyl-1, the aromatic polyisocyanates such as 3-phenyl diisocyanate, 1,5-naphthalene diisocyanate) reaction, then addition contains (methyl) acrylate of hydroxyl and the reaction product etc. that obtains.
The content of carbamate (methyl) acrylic compound in resin combination is preferably 5 ~ 95 weight parts usually relative to resin combination 100 weight part, is more preferably 10 ~ 80 weight parts, is particularly preferably 20 ~ 70 weight parts.
In the present invention, in resin combination, suitably can contain particulate.As particulate, organic fine particles, inorganic particles can be enumerated.In addition, particulate (E) can consider required transmittance, hardness, scuff resistance, cure shrinkage, specific refractory power and to be used alone or multiple used in combination.
In addition, from the viewpoint of raising transmissivity (transmissivity particularly under 380nm ~ 780nm), preferably not containing particulate.
In addition, the second-order transition temperature of resin combination of the present invention is preferably more than 70 DEG C, is particularly preferably more than 100 DEG C.
As organic fine particles operable in the present invention, can enumerate: the organic polymer pellets such as polystyrene resin bead, acrylic resin bead, urethane resin bead, polycarbonate resin bead; The porous organic polymer bead of expanded polystyrene resin beads, porous propylene acid resin bead, cellular polyurethane resin beads, porous polycarbonate resin beads etc.; The toner of phenyl guanamines-formaldehyde condensation products, the toner of phenyl guanamines-carbamide condenses, the toner of melocol condenses, the powder, zinc stearate powder, stearylamide powder, epoxy powder, polyethylene powders etc. of aspartate derivatives, preferred crosslinked polymethylmethacrylaparticles resin beads, crosslinked polymethylmethacrylaparticles styrene resin bead etc.These organic fine particles easily can obtain as commercially available product, also can be prepared with reference to known document in addition.
As inorganic particles operable in the present invention, can enumerate: conductive metal oxide, transparent metal oxide, other mineral filler etc.
As conductive metal oxide operable in the present invention, can enumerate: zinc antimonates, doped sno_2 Indium sesquioxide (ITO), antimony-doped tin oxide (ATO), antimony peroxide, stannic oxide, aluminium-doped zinc oxide, Ga-doped zinc oxide, fluorine-doped tin oxide etc.
As transparent metal oxide operable in the present invention, can enumerate: silicon-dioxide, titanium oxide, zirconium white, cerium oxide, zinc oxide, ferric oxide, titanium oxide/zirconium white/stannic oxide/antimony peroxide mixture, zirconium white/stannic oxide/antimony peroxide mixture, titanium oxide/zirconium white/stannic oxide mixture etc.
As other mineral filler operable in the present invention, can enumerate: calcium oxide, calcium chloride, zeolite, silica gel etc.
As particulate operable in the present invention, preferred hardness and excellent abrasion, the particulate that specific refractory power is high, preferably can use titanium oxide, zirconium white, cerium oxide, zinc oxide, ferric oxide, titanium oxide/zirconium white/stannic oxide/antimony peroxide mixture, zirconium white/stannic oxide/antimony peroxide mixture, titanium oxide/zirconium white/stannic oxide mixture.In addition, because the optical sheet used in the display requires high transmission rate, therefore the primary particle size of particulate is preferably below 100nm.Their mixing ratio is preferably 1 ~ 30 mass parts relative to total amount 100 mass parts of composition (A)+composition (B), is more preferably 5 ~ 20 mass parts.
In addition, also can be used together the dispersion agent as particulate such as polycarboxylic acid class dispersion agent, silane coupling agent, titante coupling agent, the polysiloxane-based dispersion agent of modified silicon wet goods, organic copolymer class dispersion agent.Their mixing ratio is about 0 ~ about 30 quality % relative to the total mass of resin combination of the present invention, is 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, this 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 electronic microscope can be used under the condition of acceleration voltage 30kV to measure primary particle size.
In the present invention, primary particle size is preferably below 100nm.And, preferably can use the particulate that primary particle size is 5nm ~ 100nm.Be below 100nm by primary particle size, can scuff resistance be given and the cured article providing transmissivity high.
These particulates can disperse to use in a solvent.Particularly inorganic particles easily obtains commercially available product with the form be dispersed in water or organic solvent, as used organic solvent, can enumerate: varsol, esters solvent, ether solvent and ketones solvent.As varsol, can enumerate: the aromatic hydrocarbon solvents such as toluene, dimethylbenzene, ethylbenzene, durene; The aliphatic solventss such as hexane, octane, decane; And as the sherwood oil, white gasoline, solvent naphtha etc. of their mixture.As esters solvent, can enumerate: the alkyl acetate classes such as ethyl acetate, propyl acetate, butylacetate; The cyclic ester classes such as gamma-butyrolactone; 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, butyleneglycol monomethyl ether monoacetate etc. (single or poly-) alkylene glycol monoalkyl ethers monoacetate class; The polycarboxylic acid alkyl esters etc. such as dialkyl glutarate, dialkyl succinate, hexanedioic acid dialkyl ester.As ether solvent, can enumerate: the alkyl ethers such as ether, ethyl-butyl ether; The glycol ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, dimethyl ether, dipropylene glycol diethyl ether, TRIGLYME, triethylene glycol diethyl ether; The ring-type ethers etc. such as tetrahydrofuran (THF).As ketones solvent, can enumerate: acetone, methyl ethyl ketone, pimelinketone, isophorone etc.
When using particulate in the present invention, the content of particulate is preferably 0.001 ~ 20 weight part usually relative to resin combination 100 weight part, is more preferably 0.001 ~ 10 weight part, is particularly preferably 0.001 ~ 5 weight part.
In resin combination of the present invention, except mentioned component, in order to improve the convenience etc. during process, can according to circumstances also with containing releasing agent, defoamer, flow agent, photostabilizer, antioxidant, stopper, softening agent, antistatic agent etc.
In addition, have many in order to obtain weather resistance, flexibility and use the example of softening agent.The material used is selected according to desired viscosity, weather resistance, the transparency, flexibility etc.Specifically can enumerate such as: the olefin polymer such as polyethylene, polypropylene; The phthalic esters such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, phthalic acid two (2-ethylhexyl) ester, Di Iso Decyl Phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, oxyacetic acid ethylphthalyl ethyl glycolate ethyl ester, oxyacetic acid butyl phthaloyl butyl ester; The trimellitates such as tri trimellitate (2-ethylhexyl) ester; Polycizer W 260, diisobutyl adipate, hexanodioic acid two (2-ethylhexyl) ester, diisononyl adipate, diisodecyl adipate, hexanodioic acid two (2-(2-Butoxyethoxy) ethyl) ester, nonane diacid two (2-ethylhexyl) ester, Uniflex DBS, sebacic acid two (2-ethylhexyl) fatty group dibasic acid such as ester, ethyl succinate; The ortho-phosphoric acid esters such as trimethyl phosphite 99, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenylphosphate, Tritolyl Phosphate, tricresyl phosphate (xylyl) ester, cresyl phosphate diphenyl ester, phosphoric acid 2-ethylhexyl diphenyl ester; The ricinoleate esters such as ethanoyl methyl ricinolcic acid; Polyester such as poly-(hexanodioic acid 1,3 butylene glycol esters); The acetic ester such as vanay; The sulphonamide such as N-butylbenzenesulfonamide; Polyalkylene oxide (two) benzoic ethers such as polyoxyethylene glycol benzoic ether, polyethylene glycol dibenzoate, polypropylene glycol benzoic ether, dibenzonate, polytetramethylene glycol benzoic ether, polytetramethylene glycol dibenzoate; The polyethers such as polypropylene glycol, polyoxyethylene glycol, polytetramethylene glycol; The poly-alkoxy-modified dihydroxyphenyl propane such as polyethoxye modified bisphenol A, poly-propoxy-modified bisphenol A; The poly-alkoxy-modified Bisphenol F such as polyethoxye modified bisphenol F, poly-propoxy-modified bisphenol F; The polycyclc aromatic compounds such as naphthalene, phenanthrene, anthracene; The naphthol derivatives such as (connection) naphthols, (gathering) oxyethyl group modification (connection) naphthols, (gathering) propoxy-modification (connection) naphthols, (gathering) tetramethylene glycol modification (connection) naphthols, (gathering) caprolactone modification (connection) naphthols; The sulfocompounds such as diphenyl sulfide, diphenyl polysulfide, benzothiazole based bisulfide, diphenyl thiourea, morpholinodithio benzothiazole, cyclohexylbenzothiazole-2-sulphenamide, tetramethyl-thiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, curing four (2-ethylhexyl) thiuram, tetramethylthiuram monosulfide, bis-pentamethylenethiuram tetrasulfide.Preferably can enumerate (gathering) ethylene glycol bisthioglycolate benzoic ether, (gathering) propylene glycol dibenzoate, dinaphthol, (gathering) oxyethyl group modification dinaphthol, (gathering) propoxy-modification dinaphthol, diphenyl sulfide.
In addition, the polymer class such as acrylic polymers, polyester elastomer, urethane polymer and nitrile rubber can also be added as required.
About the organic compound ingredient without reactive group, from the viewpoint of consistency, its weight-average molecular weight is preferably below 10000g/mol, is particularly preferably below 5000g/mol.In the present invention, the content of organic compound in resin combination without reactive group is preferably less than 1.5 % by weight relative to resin combination, is more preferably less than 1.0 % by weight, is particularly preferably less than 0.5 % by weight.By being set as less than 1.5 % by weight, the composition that can prevent from not having reactive group is incompatible and with the residual situation of the form of the insoluble composition such as solid state or gel, therefore the transparency, the thermotolerance variation as solidification physical property can be prevented, therefore preferably.In addition, in order to reduce water vapour permeability, also the organometallic compounds such as aluminum alkyls can be added.Also can add solvent, but preferably not add solvent.
For resin combination of the present invention, preferably have excellent characteristic about transmissivity, particularly, in wavelength 380nm ~ 780nm scope, the transmittance of each wavelength is preferably more than 90%.The determining instruments such as the spectrophotometer U-3900H that transmittance can be manufactured by Co., Ltd. Hitachi's high-tech measure.
Resin combination of the present invention can by preparing each composition mixed dissolution according to conventional methods.Such as, each composition can be dropped in the round-bottomed flask with whipping appts, thermometer, and stir 0.5 hour ~ 6 hours at 20 ~ 80 DEG C, preferably 40 ~ 80 DEG C and obtain.
About the viscosity of resin combination of the present invention, as the viscosity of applicable workability, the viscosity that preferred use E type viscometer (TV-200: Toki Sangyo Co., Ltd.'s system) measures is the composition of below 1000mPas at 25 DEG C, is particularly preferably below 500mPas.
Resin combination of the present invention easily can make it solidify by energy-ray.At this, as the concrete example of energy-ray, can enumerate: the hertzian wave such as ultraviolet, visible ray, infrared rays, X-ray, gamma-radiation, laser beam; The particle ray etc. such as alpha-ray, β ray, electron rays.In the present invention, among these energy-rays, preferred ultraviolet, laser beam, visible ray or electron rays.
By irradiating above-mentioned energy-ray to resin combination of the present invention according to conventional methods, cured article of the present invention can be obtained.The liquid refractivity of resin combination of the present invention is generally 1.45 ~ 1.55, is preferably 1.48 ~ 1.52.Specific refractory power can pass through the mensuration such as Abbe refractomecer (model: DR-M2, Atagi Corp.'s (ア タ go) system).
Water vapour permeability at 60 DEG C of the thickness 100 μm of resin combination of the present invention is preferably 200g/m 2below it, be more preferably 100g/m 2below it, be particularly preferably 60g/m 2below it.By being adjusted to this scope, can effectively prevent due to moisture through and to element produce infringement.
The sealed solid method of the organic EL of resin combination of the present invention is used to preferably include following operation: being formed at the operation organic EL on substrate being formed passive film; Above-mentioned passive film is coated with sealing and sticks with glue agent, and the operation of sealing transparency carrier is set; With the operation making above-mentioned sealing stick with glue agent solidification.The curable resin composition of the invention described above can be used to stick with glue agent as sealing.
The organic EL sealed such as 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 polycarbonate, polymethylmethacrylate etc., this transparent organic material glass fibre etc. carried out high rigidization and the organic/inorganic mixed transparent substrate 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 enumerate following formation.
(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
The organic EL such as with the Rotating fields of above-mentioned (4) by forming by resistive heating evaporation or sputtering method the lower electrode (negative electrode) comprising Al-Li alloy etc. on the one side of substrate, then can be stacked gradually by the film forming method such as resistive heating evaporation or ion beam sputtering and comprising the 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 of organic EL or material play as display element function, be not particularly limited.In addition, resin combination of the present invention all can be applied in the organic EL of any structure.
Passive film is formed in the mode covering organic EL.Passive film can use the inorganic materials such as silicon nitride, silicon oxide to be formed by the method such as evaporation or sputtering.Passive film is arranged to prevent moisture, ionic impurity etc. from invading organic EL.The thickness of passive film is preferably the scope of 10nm ~ 100 μm, is more preferably the scope of 100nm ~ 10 μm.
For passive film, although depend on film, being generally the defective film that there is pin hole, is in most cases the weak film of physical strength.Therefore, in the sealed solid method using resin combination of the present invention, further coating binder on passive film, uses sealing transparency carrier to crimp, and makes adhesive solidification, improve the reliability of sealing thus.
Embodiment
Next, the present invention is illustrated in greater detail by embodiment.The present invention is not limited in any way the following examples.It should be noted that, the unit " part " of numerical value represents mass parts.
The resin combination of the present invention that composition (numerical value is " part ") according to the embodiment 1 ~ 5 of table 1, comparative example 1 ~ 2 obtains ultraviolet hardening and the ultraviolet-curing resin composition compared and their cured article.In addition, carry out as described below about the evaluation method of resin combination and cured article and judgement criteria.It should be noted that, about the embodiment containing organic solvent, evaluate after utilizing vaporizer to make organic solvent fully volatilize.
(1) Water Vapour Permeability: ultraviolet curing resin clamped by the glass substrate thick with 5mm, uses the spacer of 100 μm to regulate thickness, and with high voltage mercury lamp (120W/cm, ozone free) with 3000mJ/cm 2be cured, thus make test film.For the test film obtained, use Lyssy water vapor permeance meter L80-5000 (SystechIllinois Inc.), measure the Water Vapour Permeability under 60 DEG C × 90%RH condition.Result is as shown in table 1.
(2) Tg (second-order transition temperature): for the Tg point of the ultraviolet curing resin layer after solidification, measure with determination of viscoelasticity system EXSTARDMS-6000 (SIINanoTechnology Co., Ltd. system), stretch mode, frequency 1Hz.Result is as shown in table 1.
(3) fragility: on easy gluing PET (A4300100 μm thick: Toyo Boseki K.K manufactures), use Meyer metering bar coater (メ イ ヤ ー バ ー コ ー タ ー) to be coated with the thickness of 20 μm, and use high voltage mercury lamp (80W/cm, ozone free) to carry out 3000mJ/cm 2irradiation make it solidify and obtain test film.Then, by this test film bending 180 ° is evaluated.
(4) transmissivity: clamp ultraviolet curing resin with glass substrate, uses the spacer of 60 μm to regulate thickness, and with high voltage mercury lamp (120W/cm, ozone free) with 3000mJ/cm 2be cured, thus make test film.For the test film obtained, use spectrophotometer U-3900 (Co., Ltd. Hitachi's high-tech system), measure with measurement range 780 ~ 380nm, light source C, 2 °, visual angle, and the transmissivity under recording 400nm.
(5) cure shrinkage: by the film proportion at the liquid specific gravity before the solidification at 25 DEG C and obtain by solidifying 25 DEG C, uses following mathematical expression (1) to calculate cure shrinkage.It should be noted that, the test film of cure shrinkage uses the test film after being solidified by the method identical with the test film of Water Vapour Permeability.
Cure shrinkage=(film proportion-liquid specific gravity)/film proportion × 100 (1)
Table 1
ADAMANTATEM-104: adamantylmethacrylate, Idemitsu Kosen Co., Ltd. manufactures
R-684: Tricyclodecane Dimethanol acrylate, Nippon Kayaku K. K manufactures
R-604: hydroxy pivalin aldehyde modification trimethylolpropane diacrylate, Nippon Kayaku K. K manufactures
UR203: liquid polyisoprene, Kuraray company manufactures
NIKANOLY-50: the reaction product (number-average molecular weight 250) of m-xylene and formaldehyde, Fudow Co., Ltd. manufactures
Irgacure184D:1-hydroxycyclohexyl phenyl ketone, BASF Co., Ltd. manufactures
The results verification measured, embodiment 1 ~ 5 does not all crack in friability test, and transmissivity is all more than 90%, and cure shrinkage is the lower shrinkage of 3 ~ 4%.
As can be seen from the evaluation result of embodiment 1 ~ 5 and comparative example 1 ~ 2, the Tg with the resin combination of the present invention of specific composition is high, and Water Vapour Permeability, cure shrinkage are low.Therefore, the sealing material of such as various sealing material, particularly organic EL is suitable for.
Invention has been detailed description with reference to specific mode, but it is obvious to the skilled person that and can make various changes and modifications when without departing from the spirit and scope of the present invention.
In addition, the Japanese patent application (2013-072059) that the application submitted to based on March 29th, 2013, this application entirety is quoted by reference.In addition, whole references of quoting at this are incorporated in this specification sheets as a whole.
Industrial applicability
The transmission of visible light of resin combination of the present invention and cured article thereof is excellent, and Tg is high, and Water Vapour Permeability, fragility and cure shrinkage are low, is therefore suitable for the sealing material of various sealing material, particularly organic EL.

Claims (9)

1. a resin combination, it contains (methyl) acrylic compound (A), ring-type (methyl) acrylic compound (B) and the polymerization starter (C) with alicyclic hydrocarbon skeleton, wherein,
Ring-type (methyl) acrylic compound (B) is (methyl) acrylic compound different from described compound (A), and for being selected from least one (methyl) acrylic compound in the group that is made up of (methyl) acrylic compound with alicyclic hydrocarbon skeleton and (methyl) acrylic compound with heterocyclic skeleton.
2. resin combination as claimed in claim 1, wherein, has (methyl) acrylic compound (A) of alicyclic hydrocarbon skeleton for having (methyl) acrylic compound of two or more alicyclic hydrocarbon skeleton in a part.
3. resin combination as claimed in claim 1 or 2, wherein, the alicyclic hydrocarbon skeleton respectively had in (methyl) acrylic compound of alicyclic hydrocarbon skeleton is dicyclo decane skeleton, tricyclodecane skeleton or adamantane framework separately.
4. resin combination as claimed in claim 1 or 2, wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (1),
In formula, R 1represent the alkyl of hydrogen atom, carbonatoms 1 ~ 3, halogen atom or following formula (2) independently of one another, and at least one R 1for following formula (2),
In formula, R 2represent (gathering) alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 10, Y represents hydrogen atom or methyl, * and cyclic skeleton bonding.
5. resin combination as claimed in claim 1 or 2, wherein, (methyl) acrylic compound (A) with alicyclic hydrocarbon skeleton is (methyl) acrylic compound represented by following formula (3),
In formula, R 3and R 4represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6.
6. the resin combination according to any one of Claims 1 to 5, wherein, ring-type (methyl) acrylic compound (B) is for having (methyl) acrylic compound of heterocyclic skeleton, (methyl) acrylic compound with heterocyclic skeleton is (methyl) acrylic compound represented by following formula (4)
In formula, R 5represent alkylidene group or the alkylene oxide group of Direct Bonding or carbonatoms 1 ~ 6 independently of one another, R 6represent the alkyl of hydrogen atom or carbonatoms 1 ~ 4 independently of one another, Z represents methylene radical, Sauerstoffatom or nitrogen-atoms independently of one another, but Z is not all methylene radical.
7. resin combination as claimed in claim 6, wherein, (methyl) acrylic compound (A) represented by above formula (1): the weight ratio of ring-type (methyl) acrylate (B) represented by above formula (4) is 9:1 ~ 1:9.
8. a low moisture-inhibiting barrier film, it obtains by making the resin composition according to any one of claim 1 ~ 7.
9. the resin combination according to any one of claim 1 ~ 7, it is for OLED purposes.
CN201480019185.9A 2013-03-29 2014-03-28 Energy ray-curable resin composition and cured product of same Pending CN105073799A (en)

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JP2013072059A JP6284217B2 (en) 2013-03-29 2013-03-29 Energy ray curable resin composition and cured product thereof
PCT/JP2014/059292 WO2014157668A1 (en) 2013-03-29 2014-03-28 Energy ray-curable resin composition and cured product of same

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN113248653A (en) * 2020-02-13 2021-08-13 三星Sdi株式会社 Composition for encapsulating organic light emitting device and organic light emitting device display apparatus

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160053750A (en) * 2014-10-29 2016-05-13 삼성에스디아이 주식회사 Sealant composition for display, organic protective layer comprising the same, and display apparatus comprising the same
KR102475431B1 (en) 2016-10-14 2022-12-08 덴카 주식회사 composition
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CN111972047A (en) 2018-04-16 2020-11-20 电化株式会社 Sealing agent for organic electroluminescent display element
JP6573089B1 (en) * 2018-05-31 2019-09-11 パナソニックＩｐマネジメント株式会社 Ultraviolet curable resin composition, method for manufacturing light emitting device, and light emitting device
CN112236497B (en) 2018-09-11 2023-08-18 株式会社Lg化学 Encapsulation composition
JP7191219B2 (en) * 2018-11-12 2022-12-16 エルジー・ケム・リミテッド sealant composition
US20240317914A1 (en) * 2020-12-31 2024-09-26 Lg Chem, Ltd. Encapsulating composition and organic electronic device comprising same
WO2023032372A1 (en) 2021-08-30 2023-03-09 コニカミノルタ株式会社 Electronic device sealing composition, electronic device sealing film forming method, and electronic device sealing film
KR20240071097A (en) * 2022-11-15 2024-05-22 솔루스첨단소재 주식회사 Compound for encapsulating organic light emitting diode and organic light emitting display device comprising the same
KR20240071098A (en) * 2022-11-15 2024-05-22 솔루스첨단소재 주식회사 Compound for encapsulating organic light emitting diode and organic light emitting display device comprising the same
KR20240071095A (en) * 2022-11-15 2024-05-22 솔루스첨단소재 주식회사 Compound for encapsulating organic light emitting diode and organic light emitting display device comprising the same

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0459385A (en) * 1990-06-29 1992-02-26 Ricoh Co Ltd Optical information recording medium
JP2007002144A (en) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd Ultraviolet-curing type resin composition and its cured product
JP2007197544A (en) * 2006-01-26 2007-08-09 Nippon Kayaku Co Ltd Active energy ray-curable resin composition for inkjet recording system and its cured product
EP2103646A1 (en) * 2008-03-21 2009-09-23 Fujifilm Corporation Barrier laminate and method for producing same, barrier film substrate, device and optical component
JP2011023072A (en) * 2009-07-16 2011-02-03 Nippon Kayaku Co Ltd Uv curing resin composition for optical disk, and cured material thereof

Family Cites Families (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2679586B2 (en) 1993-08-17 1997-11-19 東亞合成株式会社 Active energy ray-curable composition
JP2000169552A (en) 1998-12-08 2000-06-20 Toagosei Co Ltd Cationically curable resin composition
JP2001081182A (en) 1999-09-09 2001-03-27 Nippon Shokubai Co Ltd Polymerizable resin and polymerizable resin composition
JP4655172B2 (en) 2000-04-27 2011-03-23 日立化成工業株式会社 Hydroxyl-containing oxetane compounds
JP3876630B2 (en) 2001-03-01 2007-02-07 東亞合成株式会社 Curable composition
JP4104383B2 (en) * 2002-06-05 2008-06-18 住友ベークライト株式会社 Transparent water vapor barrier film and method for producing the same
JP4421938B2 (en) 2004-05-10 2010-02-24 日東電工株式会社 UV curable resin composition
JP4609051B2 (en) * 2004-11-29 2011-01-12 Ｊｓｒ株式会社 Shock absorbing laminated structure, LCD, plasma display, organic EL display, field emission display or shock absorbing laminated structure for electronic paper, and display device
JP2007045951A (en) * 2005-08-10 2007-02-22 Sumitomo Bakelite Co Ltd Method for producing transparent substrate plate, transparent substrate plate and electronic device equipped with the same
JP5636196B2 (en) * 2010-02-26 2014-12-03 大阪有機化学工業株式会社 Adamantane derivative and resin composition containing the same
JP4944277B2 (en) * 2010-08-11 2012-05-30 積水化学工業株式会社 Cured product and transparent composite sheet
JP2013028776A (en) * 2011-03-10 2013-02-07 Sekisui Chem Co Ltd Transparent composite sheet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0459385A (en) * 1990-06-29 1992-02-26 Ricoh Co Ltd Optical information recording medium
JP2007002144A (en) * 2005-06-27 2007-01-11 Nippon Kayaku Co Ltd Ultraviolet-curing type resin composition and its cured product
JP2007197544A (en) * 2006-01-26 2007-08-09 Nippon Kayaku Co Ltd Active energy ray-curable resin composition for inkjet recording system and its cured product
EP2103646A1 (en) * 2008-03-21 2009-09-23 Fujifilm Corporation Barrier laminate and method for producing same, barrier film substrate, device and optical component
JP2011023072A (en) * 2009-07-16 2011-02-03 Nippon Kayaku Co Ltd Uv curing resin composition for optical disk, and cured material thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113248653A (en) * 2020-02-13 2021-08-13 三星Sdi株式会社 Composition for encapsulating organic light emitting device and organic light emitting device display apparatus
CN113248653B (en) * 2020-02-13 2023-05-19 三星Sdi株式会社 Composition encapsulating organic light emitting device and organic light emitting device display apparatus

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JP2014196387A (en) 2014-10-16
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Application publication date: 20151118