WO2014157642A1 - エネルギー線硬化型樹脂組成物及びその硬化物 - Google Patents
エネルギー線硬化型樹脂組成物及びその硬化物 Download PDFInfo
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- WO2014157642A1 WO2014157642A1 PCT/JP2014/059201 JP2014059201W WO2014157642A1 WO 2014157642 A1 WO2014157642 A1 WO 2014157642A1 JP 2014059201 W JP2014059201 W JP 2014059201W WO 2014157642 A1 WO2014157642 A1 WO 2014157642A1
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- acrylate
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- 0 CCC(*C1(*)*CC(*)(*[N+](C=C)[O-])C*1)=O Chemical compound CCC(*C1(*)*CC(*)(*[N+](C=C)[O-])C*1)=O 0.000 description 1
Classifications
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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
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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
- C08F220/26—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
Definitions
- Energy beam curable resin is generally excellent in workability because it can be processed without solvent. Further, since the curing speed is fast and the energy requirement is low, the energy beam curing technique is an important technique in various industries including display peripheral materials.
- thin displays called flat panel displays (FPD), in particular, plasma displays (PDP) and liquid crystal displays (LCD) have been put on the market and are widely used.
- organic EL displays OLEDs are expected as next-generation self-luminous thin film displays, and some products have already been put into practical use.
- An organic EL element of an organic EL display has a structure in which an element body composed of a thin film laminate including a light emitting layer sandwiched between a cathode and an anode is formed on a glass substrate on which a driving circuit such as a TFT is formed.
- a layer such as a light emitting layer or an electrode of the element portion is easily deteriorated by moisture or oxygen, and the deterioration of brightness, life, and discoloration occurs due to the deterioration. Therefore, the organic EL element is sealed so as to block moisture or impurities from entering from the outside.
- a higher-performance sealing material is desired, and various sealing techniques have been studied.
- Patent Document 1 As a typical sealing method of an organic EL element, a method of fixing a metal or glass sealing cap in which a desiccant is inserted in advance to a substrate of an organic EL element using a sealing adhesive has been studied.
- Patent Document 1 an adhesive is applied to the outer peripheral portion of the substrate of the organic EL element, a sealing cap is placed thereon, and then the adhesive is solidified to fix the substrate and the sealing cap. It is sealed.
- sealing with a glass sealing cap is the mainstream.
- a glass sealing cap is produced by processing a digging for inserting a desiccant into a flat glass substrate, and thus tends to be expensive.
- the sealing with the sealing cap cannot extract light from the sealing cap side.
- the light emitted from the light source is extracted from the substrate side of the element, and is limited to the bottom emission type element.
- a bottom emission type element there are problems of a decrease in aperture ratio due to the drive circuit portion formed on the substrate and a decrease in extraction efficiency due to light being partially blocked by the drive circuit portion. Therefore, development of a sealing method applicable to a top emission type element that extracts light from the opposite side of the substrate of the organic EL element is desired.
- the thin film sealing method is a method in which a thin film made of an inorganic or organic material is laminated on an organic EL element to form a passivation film (Patent Document 2).
- Patent Document 2 In order to impart sufficient moisture resistance to the device by this method, it is necessary to sequentially stack a number of thin films on the device. Therefore, in the thin film sealing method, the film forming process is long and expensive, and the initial investment tends to be high due to the introduction of a large vacuum system required for film formation.
- the solid sealing method is a method in which a passivation film is provided so as to cover the entire element portion of the organic EL element, and a transparent substrate for sealing is provided thereon via a sealing material (see Patent Document 3).
- a passivation film is formed by vapor deposition or sputtering of an inorganic material, and it is often an incomplete film having pinholes or a film having low mechanical strength. Therefore, in the solid sealing method, after providing a passivation film on the element, a sealing transparent substrate such as a glass substrate is provided through a sealing adhesive to improve sealing reliability.
- a sealing method is attracting attention as a method capable of sealing a top emission type element simply and at low cost.
- the sealing adhesive used for these has high transmittance in the visible light region, light resistance that can withstand light emission, stable moldability, low curing shrinkage for suppressing residual stress, and light emitting elements in moisture. For example, a low water vapor transmission rate for protecting from water is required.
- a solid sealing method using a known adhesive as an organic EL element sealing adhesive, satisfactory results are obtained with reliability, productivity, and water vapor transmission rate. It is difficult to do so, and it has been desired to develop a sealing adhesive that can be suitably used for the solid sealing method.
- Japanese Patent No. 3876630 Japanese Patent No. 2679586 Japanese Patent No. 4421938 Japanese Patent No. 4655172 Japanese Unexamined Patent Publication No. 2001-81182 Japanese Unexamined Patent Publication No. 2000-169552
- An object of the present invention is to provide a resin composition suitable for a sealing material for an organic EL device and a cured product having excellent curability, low visible light transmittance, curing shrinkage rate, and low water vapor permeability.
- an energy beam curable resin composition having a specific composition and a cured product thereof can solve the above problems, and have completed the present invention.
- the present invention relates to the following (1) to (13).
- a resin composition containing a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, a cyclic (meth) acrylate compound (B) and a polymerization initiator (C) The compound (B) is a (meth) acrylate compound having an aromatic hydrocarbon skeleton other than the compound (A), a (meth) acrylate compound having an alicyclic hydrocarbon skeleton, and a (meth) acrylate compound having a heterocyclic skeleton.
- the compound (B) is a (meth) acrylate compound having an alicyclic hydrocarbon skeleton, and is a (meth) acrylate compound having two or more alicyclic hydrocarbon skeletons in one molecule
- the resin composition according to (6), wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton includes a dicyclodecane structure, a tricyclodecane ring, or an adamantane ring as the alicyclic hydrocarbon skeleton.
- the resin composition according to (6), wherein the (meth) acrylate compound having an alicyclic hydrocarbon skeleton is a (meth) acrylate compound represented by the following formula (3).
- each R 3 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R 3 is represented by the following formula (4): is there.
- R 6 and R 7 each independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or a (poly) alkyleneoxy group.
- R 8 represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group.
- R 9 represents hydrogen or an alkylene group having 1 to 4 carbon atoms.
- Z represents a carbon atom or an oxygen atom. Or represents a nitrogen atom.
- X represents a direct bond or an alkylene group having 1 to 3 carbon atoms
- Y represents a hydrogen atom or a methyl group
- R 1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or (meta ) Represents an acryloyl group
- R 2 represents a direct bond or a (poly) alkyleneoxy group having 1 to 10 carbon atoms.
- each R 3 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R 3 is represented by the following formula (4): is there.
- R 2 represents a direct bond or a (poly) alkyleneoxy group having 1 to 10 carbon atoms
- Y represents a hydrogen atom or a methyl group
- * represents a bond to a cyclic skeleton.
- the resin composition of the present invention and its cured product are particularly suitable for an organic EL device sealing material because of its excellent visible light transmittance, low curing shrinkage, and low water vapor permeability.
- the resin composition of the present invention contains a (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton, a cyclic (meth) acrylate compound (B), and a polymerization initiator (C).
- A aromatic hydrocarbon skeleton
- B cyclic (meth) acrylate compound
- C polymerization initiator
- the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton contained in the resin composition of the present invention any known compound may be used as long as it has at least one aromatic ring in the molecule. be able to.
- the resin composition can have water repellency, and the water vapor transmission rate can be reduced.
- the said effect can fully be show
- the said effect will be more excellent by having two or more aromatic rings in a molecule
- Examples of such a skeleton having two or more aromatic rings in the molecule include a biphenyl skeleton and a bisphenol skeleton, and these skeletons can exhibit excellent water vapor permeability.
- These aromatic hydrocarbon skeletons may or may not have a substituent.
- the aromatic hydrocarbon skeleton has a substituent, the substituent is an alkyl group having 1 to 6 carbon atoms, carbon An alkoxy group having 1 to 6 carbon atoms and an alkenyl group having 1 to 6 carbon atoms are preferable.
- the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton include the following monofunctional (meth) acrylate compounds and bifunctional or higher (meth) acrylate compounds.
- monofunctional (meth) acrylate compounds include benzyl (meth) acrylate, ethoxy modified cresol (meth) acrylate, propoxy modified cresol (meth) acrylate, neopentyl glycol benzoate (meth) acrylate, o-phenylphenol (meth) Acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meth) acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (Meth) acrylate compounds having a single ring such as (meth) acrylate, o-phenylbenzyl
- Bifunctional or higher functional (meth) acrylate compounds include (poly) ethoxy modified bisphenol A di (meth) acrylate, (poly) propoxy modified bisphenol A di (meth) acrylate, and (poly) ethoxy modified bisphenol F di (meth) acrylate.
- Examples of the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton include epoxy (meth) acrylate compounds in addition to the above (meth) acrylate monomers.
- Epoxy (meth) acrylates include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, biphenyl type phenol aralkyl resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, fluorene epoxy resin, bisphenol S. And a reaction product of epoxy resin such as epoxy resin and (meth) acrylic acid.
- the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton specifically, for example, a (meth) acrylate compound having a partial skeleton represented by the following formula (1) can be preferably used.
- X represents a direct bond or an alkylene group having 1 to 3 carbon atoms.
- X represents a direct bond or an alkylene group having 1 to 3 carbon atoms.
- a (meth) acryloyl group is connected to the aromatic hydrocarbon skeleton directly or via a hydrocarbon group, and the hydrocarbon group in the case of being connected via a hydrocarbon group
- examples thereof include an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms having an ether bond.
- the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton used in the present invention is preferably a (meth) acrylate compound represented by the following formula (2).
- R 1 represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, or the following formula: (4) and R 2 represents a direct bond or a (poly) alkyleneoxy group having 1 to 10 carbon atoms.
- R 2 represents a direct bond or a (poly) alkyleneoxy group having 1 to 10 carbon atoms
- Y represents a hydrogen atom or a methyl group
- * represents a bond to the benzene skeleton.
- Specific examples of such (meth) acrylate compounds include o-phenylphenol (meth) acrylate, o-phenylphenol monoethoxy (meth) acrylate, o-phenylphenol polyethoxy (meth) acrylate, p-phenylphenol (meta ) Acrylate, p-phenylphenol monoethoxy (meth) acrylate, p-phenylphenol polyethoxy (meth) acrylate, o-phenylbenzyl acrylate, p-phenylbenzyl acrylate, (poly) propoxy-modified bisphenol A di (meth) acrylate, (Poly) ethoxy modified bisphenol F di (meth) acrylate, (poly)
- the content of the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton in the resin composition is usually preferably 5 to 95 parts by weight and preferably 10 to 80 parts by weight with respect to 100 parts by weight of the resin composition. More preferred is 20 to 70 parts by weight.
- the cyclic (meth) acrylate compound (B) used in the present invention has a (meth) acrylate having the above aromatic hydrocarbon skeleton, a (meth) acrylate having an alicyclic hydrocarbon skeleton, or a heterocyclic skeleton ( (Meth) acrylates can be used.
- a (meth) acrylate compound having an aromatic hydrocarbon skeleton is used as the cyclic (meth) acrylate compound (B)
- the resin composition has two types of “aromatic hydrocarbon skeletons having different structures.
- the (meth) acrylate having an aromatic hydrocarbon skeleton that can be used as a cyclic (meth) acrylate compound is the same as those listed above, but the same (meth) acrylate compound as the compound (A) is used. I can't.
- a (meth) acrylate compound having an aromatic hydrocarbon skeleton is used in a resin composition, there is an effect of preventing the permeation of water vapor as compared with other skeletons such as those having a chain structure.
- the (meth) acrylate compound having an alicyclic hydrocarbon skeleton that can be used in the present invention, known compounds can be used without any particular limitation, and the alicyclic hydrocarbon skeleton is a saturated hydrocarbon skeleton. It is preferable that Such a cyclic skeleton has an effect of preventing permeation of water vapor as compared with other skeletons such as those having a chain structure, and is combined with the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton. By disposing in the curing system, it becomes possible to remarkably prevent the permeation of water vapor by a synergistic effect.
- cyclic hydrocarbon skeleton examples include a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a dicyclodecane structure, a tricyclodecane ring, an adamantane ring, and an isobornyl ring.
- (meth) acrylate compounds having a bridged cyclic hydrocarbon skeleton such as a tricyclodecane ring and an adamantane ring are preferred.
- a (meth) acryloyl group is connected to the cyclic hydrocarbon skeleton directly or via a hydrocarbon group, and the hydrocarbon group in the case of being connected via a hydrocarbon group
- examples thereof include an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms having an ether bond.
- (meth) acrylate compounds having an alicyclic hydrocarbon skeleton include the following monofunctional (meth) acrylate compounds and bifunctional or higher (meth) acrylate compounds.
- Monofunctional (meth) acrylate compounds include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.
- Examples of the bifunctional or higher polyfunctional (meth) acrylate compound include alicyclic (meth) acrylates such as tricyclodecane dimethanol (meth) acrylate.
- a (meth) acrylate compound having a structure represented by the following formula (3) can be preferably used.
- each R 3 independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom or the following formula (4), and at least one of R 3 is represented by the following formula (4): is there.
- R 2 represents a direct bond or a (poly) alkyleneoxy group having 1 to 10 carbon atoms
- Y represents a hydrogen atom or a methyl group
- * represents a bond to a cyclic skeleton.
- Specific examples of the (meth) acrylate compound of the above formula (3) include alicyclic (meth) acrylates such as tricyclodecane dimethanol (meth) acrylate.
- the content of the (meth) acrylate compound having an alicyclic hydrocarbon skeleton in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the resin composition. 20 to 70 parts by weight is particularly preferable.
- the (meth) acrylate compound having a heterocyclic skeleton that can be used as a cyclic (meth) acrylate compound in the present invention will be described below.
- Such a heterocyclic skeleton has an effect of preventing permeation of water vapor as compared with other skeletons such as those having a chain structure, and is combined with the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton.
- the heterocyclic skeleton that can be used include a dioxane structure, a trioxane structure, and an isocyanurate structure.
- a (meth) acryloyl group is connected to the heterocyclic skeleton. Specifically, it is preferable that a (meth) acryloyl group is linked directly or via a hydrocarbon group to the heterocyclic skeleton, and as a hydrocarbon group when linked via a hydrocarbon group, And an alkylene group having 1 to 10 carbon atoms or an alkylene group having 1 to 10 carbon atoms having an ether bond.
- the (meth) acrylate compound having a heterocyclic skeleton include the following (meth) acrylate compounds. That is, tetrahydrofurfuryl (meth) acrylate, alkoxylated tetrahydrofurfuryl acrylate caprolactone modified tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, isocyanuric acid EEO modified diacrylate (M-215), ⁇ -caprolactone modified tris ( Acoxyethyl) isocyanurate (M-327), isocyanuric acid EO-modified di- and triacrylate (M-313 or M-315), hydroxypivalaldehyde-modified trimethylolpropane diacrylate (R-604), pentamethylpiperidi Nyl methacrylate (FA-711), tetramethylpiperidinyl methacrylate (FA-712HM), cyclic trimethylolpropane formal
- Examples of such (meth) acrylate compounds having a heterocyclic skeleton include, for example, morpholine skeleton, tetrahydrofuran skeleton, oxane skeleton, dioxane skeleton, triazine skeleton, carbazole skeleton, pyrrolidine skeleton, piperidine skeleton, and isocyanurate structure as examples of the heterocyclic ring.
- a (meth) acrylate compound having a structure represented by the following formula (7) can be used.
- R 8 is a direct bond, an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms
- R 9 is a hydrogen atom, an alkyl group or alkenyl group having 1 to 4 carbon atoms
- X is a nitrogen atom or oxygen atom
- Y represents a methylene group or a carbonyl group
- m represents an integer of 1 to 4, provided that X is not all a methylene group.
- a compound represented by the following formula (6) can be preferably used.
- R 8 represents a direct bond or an alkylene group or alkyleneoxy group having 1 to 6 carbon atoms.
- R 9 represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms.
- Z represents a carbon atom, oxygen Represents an atom or a nitrogen atom.
- the content of the (meth) acrylate compound having a heterocyclic skeleton in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the resin composition. 20 to 70 parts by weight is particularly preferable.
- a (meth) acrylate compound having a structure represented by the following partial structural formula (A) (hereinafter, polyEO-modified (meth) acrylate)
- the total weight of the compound (referred to as a compound) is preferably less than the total weight of the (meth) acrylate compound other than the polyEO-modified (meth) acrylate compound, and more preferably 1 ⁇ 2 or less.
- t represents an integer of 2 or more.
- the total weight of the polyEO-modified (meth) acrylate compound in the resin composition is preferably 10 parts by weight or less, more preferably 5 parts by weight or less with respect to 100 parts by weight of the resin composition. 2 parts by weight or less is particularly preferable.
- the cyclic polyEO-modified (meth) acrylate compound which is a cyclic (meth) acrylate compound and is a polyEO-modified (meth) acrylate compound, is a (meth) acrylate having the aromatic hydrocarbon skeleton of the present invention. Since it is preferable not to use the compound (A) or the cyclic (meth) acrylate compound (B), even if it is used, it is preferably 20 parts by weight or less, particularly preferably 10 parts by weight or less, based on 100 parts by weight of the resin composition.
- the ratio of the (meth) acrylate compound (A) having an aromatic hydrocarbon skeleton and the cyclic (meth) acrylate compound (B) contained in the resin composition is 1: 9 to 9: 1 by weight ratio.
- 7: 3 to 9: 1 is more preferable, and 5: 5 to 9: 1 is particularly preferable.
- polymerization initiator (C) used in the present invention various polymerization initiators such as a photopolymerization initiator and a thermal radical polymerization initiator can be used.
- the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-1- [ Acetophenones such as 4- (methylthio) phenyl] -2-morpholinopropan-1-one and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; 2-ethyl Anthraquinone Anthraquinones such as 2-tert-butylanthraquinone, 2-chloroanthraquino
- Benzophenones such as benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 4,4′-bismethylaminobenzophenone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6 -Phosphine oxides such as -trimethylbenzoyl) -phenylphosphine oxide and diphenyl- (2,4,6-trimethylbenzoyl) phosphine oxide It can be.
- Preferred are acetophenones, and more preferred are 2-hydroxy-2-methyl-phenylpropan-1-one and 1-hydroxycyclohexyl-phenyl ketone.
- a photoinitiator may be used independently and may be used in mixture of multiple types.
- the thermal radical polymerization initiator is not particularly limited as long as it is a compound that generates radicals by heating and initiates a chain polymerization reaction, but is not limited to organic peroxides, azo compounds, benzoin compounds, benzoin ether compounds, acetophenone compounds, benzoates. Examples thereof include pinacol, and benzopinacol is preferably used.
- organic peroxides include Kayamek (trademark) A, M, R, L, LH, SP-30C, Parkadox (trademark) CH-50L, BC-FF, Kadox (trademark) B-40ES, and Parkadox.
- thermal radical polymerization initiator preferred are benzopinacol-based thermal radical polymerization initiators (including those obtained by chemically modifying benzopinacol).
- benzopinacol 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy- 1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra (4-methylphenyl) ethane, 1,2-diphenoxy-1,1,2,2-tetra (4-methoxyphenyl) ethane, 1,2-bis (trimethylsiloxy) -1,1,2,2-tetraphenylethane, 1,2-bis (triethylsiloxy) -1,1,2,2-tetraphenyl Ethane, 1,2-bis (t-butyldimethylsiloxy) -1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1- And droxy-2-triethylsiloxy-1,1,2,2-tetraphenyle
- the benzopinacol is commercially available from Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd. Moreover, etherification of the hydroxy group of benzopinacol can be easily synthesized by a known method. Moreover, silyl etherification of the hydroxy group of benzopinacol can be obtained by synthesizing by a method in which the corresponding benzopinacol and various silylating agents are heated under a basic catalyst such as pyridine.
- silylating agents examples include trimethylchlorosilane (TMCS), hexamethyldisilazane (HMDS), N, O-bis (trimethylsilyl) trifluoroacetamide (BSTFA) and triethylsilylating agents, which are generally known trimethylsilylating agents.
- TMCS trimethylchlorosilane
- HMDS hexamethyldisilazane
- BSTFA O-bis (trimethylsilyl) trifluoroacetamide
- triethylsilylating agents which are generally known trimethylsilylating agents.
- the triethylchlorosilane (TECS) and t-butyldimethylsilylating agent examples include t-butylmethylsilane (TBMS). These reagents can be easily obtained from markets such as silicon derivative manufacturers.
- the reaction amount of the silylating agent is preferably 1.0 to 5.0 times mol for 1 mol of the hydroxy
- the amount is less than 1.0 times the mole, the reaction efficiency is poor and the reaction time is prolonged, which may promote thermal decomposition.
- the amount is more than 5.0 times, the separation may be deteriorated during the recovery or the purification may be difficult.
- the content of the polymerization initiator (C) of the present invention is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the total amount of the resin composition.
- a polymerization initiator (C) may be used independently and may be used in mixture of multiple types.
- the resin composition of the present invention uses a (meth) acrylate compound other than the compound (A) and the compound (B) in consideration of the viscosity, refractive index, adhesion and the like of the resin composition of the present invention to be obtained. You may do it. Specific examples include (meth) acrylate monomers, which include monofunctional (meth) acrylate, bifunctional (meth) acrylate, and three or more (meth) acryloyl groups in the molecule. Polyfunctional (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and the like can be used.
- Examples of the monofunctional (meth) acrylate include imide (meth) acrylate having an imide ring structure, butanediol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2- Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylate having a hydroxyl group such as dipropylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, butoxyethyl (meth) acrylate, caprolactone ( (Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, octafluoropentyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, Alkyl groups such as sode
- Examples include (meth) acrylates of polyhydric alcohols such as (meth) acrylates, ethoxydiethylene glycol (meth) acrylates, 2-ethylhexyl carbitol (meth) acrylates, polyethylene glycol (meth) acrylates, and polypropylene glycol (meth) acrylates. Can do.
- Examples of the (meth) acrylate monomer having two functional groups include acrylates such as diacrylated isocyanurate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, , 9-nonanediol di (meth) acrylate, (meth) acrylate having a linear methylene structure such as polytetramethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Examples thereof include di (meth) acrylates of polyhydric alcohols such as glycol di (meth) acrylate and polypropylene di (meth) acrylate.
- acrylates such as diacrylated isocyanurate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ,
- polyfunctional (meth) acrylate monomer examples include polyfunctional (meth) acrylate having an isocyanurate ring such as tris (acryloxyethyl) isocyanurate, (poly) caprolactone-modified tris (acryloxyethyl) isocyanurate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, (poly) ethoxy modified pentaerythritol tetra (meth) acrylate, (poly) propoxy modified pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, (poly) Caprolactone-modified dipentaerythritol penta (meth) acrylate, (poly) ethoxy-modified dipentaerythritol penta (meth) acryl
- the content of the (meth) acrylate monomer other than the compound (A) and the compound (B) in the resin composition is usually preferably 5 to 95 parts by weight with respect to 100 parts by weight of the resin composition. 80 parts by weight is more preferable, and 20 to 70 parts by weight is particularly preferable.
- urethane (meth) acrylate can be used to the extent that the characteristics are not impaired.
- examples of the urethane (meth) acrylate include diol compounds (for example, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, neopentyl glycol, 1,6- Hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentane Diol, 2-butyl-2-ethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, polyethylene glycol, polypropylene glycol, bisphenol A polyethoxydiol
- the content of the urethane (meth) acrylate compound in the resin composition is usually preferably 5 to 95 parts by weight, more preferably 10 to 80 parts by weight, and more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the resin composition. Particularly preferred.
- fine particles can be appropriately contained in the resin composition.
- the fine particles include organic fine particles and inorganic fine particles.
- the fine particles can be used singly or in combination of plural kinds in consideration of required light transmittance, hardness, scratch resistance, curing shrinkage rate, and refractive index. From the viewpoint of improving the transmittance (particularly, the transmittance at 380 nm to 780 nm), it is preferable not to contain fine particles.
- organic fine particles examples include polystyrene resin beads, acrylic resin beads, urethane resin beads, polycarbonate resin beads and other organic polymer beads, porous polystyrene resin beads, porous acrylic resin beads, and porous urethane resin beads.
- Porous organic polymer beads such as porous polycarbonate resin beads, benzoguanamine-formalin condensate resin powder, benzoguanamine-melamine-formalin condensate resin powder, urea-formalin condensate resin powder, aspartic acid ester derivative powder, Examples include zinc stearate powder, stearic acid amide powder, epoxy resin powder, polyethylene powder, cross-linked polymethyl methacrylate resin beads and cross-linked polymethyl methacrylate / styrene resin beads. Etc. are preferred. These organic fine particles can be easily obtained as a commercial product, and can also be prepared with reference to known literature.
- inorganic fine particles examples include conductive metal oxides, transparent metal oxides, and other inorganic fillers.
- Examples of the conductive metal oxide that can be used in the present invention include zinc antimonate, tin oxide-doped indium oxide (ITO), antimony-doped tin oxide (ATO), antimony pentoxide, tin oxide, aluminum-doped zinc oxide, and gallium-doped zinc oxide. And fluorine-doped tin oxide.
- transparent metal oxide examples include silica, titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / antimony pentoxide composite, and zirconium oxide / tin oxide. / Antimony pentoxide composite, titanium oxide / zirconium oxide / tin oxide composite, and the like.
- inorganic fillers that can be used in the present invention include calcium oxide, calcium chloride, zeolite, silica gel and the like.
- the fine particles that can be used in the present invention are preferably fine particles having excellent hardness and scratch resistance and a high refractive index. Titanium oxide, zirconium oxide, cerium oxide, zinc oxide, iron oxide, titanium oxide / zirconium oxide / tin oxide / pentoxide An antimony composite, a zirconium oxide / tin oxide / antimony pentoxide composite, and a titanium oxide / zirconium oxide / tin oxide composite are preferably used.
- the primary particle diameter of the fine particles is preferably 100 nm or less. The blending ratio of these is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total amount of compound (A) + compound (B).
- a fine particle dispersant a polycarboxylic acid dispersant, a silane coupling agent, a titanate coupling agent, a silicone dispersant such as a modified silicone oil, or an organic copolymer dispersant may be used in combination. Is possible.
- the blending ratio of these is about 0 to 30% by mass, preferably about 0.05 to 5% by mass with respect to the total mass of the resin composition of the present invention.
- the primary particle size means the smallest particle size of the particles when the aggregation is broken. That is, in the case of elliptical fine particles, the minor axis is the primary particle diameter.
- the primary particle size can be measured by a dynamic light scattering method, observation with an electron microscope, or the like. Specifically, using a JSM-7700F field emission scanning electron microscope manufactured by JEOL Ltd., the primary particle size can be measured under an acceleration voltage of 30 kV.
- the primary particle size is preferably 100 nm or less. Fine particles having a size of 5 to 100 nm can be preferably used. By being 100 nm or less, it becomes possible to provide a cured product having high transmittance while imparting scratch resistance.
- fine particles can be used by dispersing in a solvent.
- inorganic fine particles are readily available as commercial products in a form dispersed in water or an organic solvent.
- organic solvents used include aromatic hydrocarbon solvents such as toluene, xylene, ethylbenzene, and tetramethylbenzene, hexane, and octane.
- Aliphatic hydrocarbon solvents such as decane, and mixtures thereof such as petroleum ether, white gasoline, solvent naphtha, etc.
- ester solvents include alkyl acetates such as ethyl acetate, propyl acetate and butyl acetate, and ⁇ -butyrolactone Cyclic esters such as ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether monoacetate, diethylene glycol monoethyl ether monoacetate, triethylene glycol monoethyl ether monoacetate, diethylene glycol monoacetate (Mono or poly) alkylene glycol monoalkyl ether monoacetates such as tilether monoacetate, propylene glycol monomethyl ether monoacetate, butylene glycol monomethyl ether monoacetate, polycarboxylic acids such as dialkyl glutarate, dialkyl succinate, dialkyl adipate Alkyl esters, etc., ether solvents include alkyl ethers such as diethyl ether and ethyl butyl ether, ethylene glycol dimethyl ether, ethylene glycol diethy
- the content of fine particles is usually preferably 0.001 to 20 parts by weight, more preferably 0.001 to 10 parts by weight, and more preferably 0.001 to 100 parts by weight of the resin composition. ⁇ 5 parts by weight is particularly preferred.
- the resin composition of the present invention includes a mold release agent, an antifoaming agent, a leveling agent, a light stabilizer, an antioxidant, a polymerization inhibitor, and a plasticizer in order to improve convenience during handling. Further, an antistatic agent or the like can be used in combination depending on the situation.
- plasticizers are used to obtain durability and flexibility.
- the material used is selected depending on the desired viscosity, durability, transparency, flexibility and the like.
- olefinic polymers such as polyethylene and polypropylene, dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, dicyclohexyl phthalate, ethyl phthalyl ethyl glycolate Phthalates such as butyl phthalyl butyl glycolate, trimellitic esters such as tris (2-ethylhexyl) trimellitate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adip
- polymers such as acrylic polymer, polyester elastomer, urethane polymer and nitrile rubber can be added as necessary.
- the weight average molecular weight is preferably 10,000 g / mol or less, particularly preferably 5,000 g / mol or less, from the viewpoint of compatibility.
- the content of the organic compound having no reactive group in the resin composition is preferably 1.5% by weight or less, and 1.0% by weight or less, based on the resin composition. Is more preferable, and 0.5% by weight or less is particularly preferable.
- An organometallic compound such as alkylaluminum can also be added to reduce the water vapor permeability. Although a solvent can also be added, what does not add a solvent is preferable.
- the light transmittance at each wavelength in the wavelength range of 380 to 780 nm is preferably 90% or more.
- the light transmittance can be measured with a measuring instrument such as a spectrophotometer U-3900H manufactured by Hitachi High-Technologies Corporation.
- a glass transition temperature is 70 degreeC or more, and 100 degreeC or more is especially preferable.
- the resin composition of the present invention can be prepared by mixing and dissolving each component according to a conventional method.
- each component can be charged into a round bottom flask equipped with a stirrer and a thermometer and stirred at 20 to 80 ° C., preferably 40 to 80 ° C. for 0.5 to 6 hours.
- the viscosity of the resin composition of the present invention is a composition having a viscosity of 1000 mPa ⁇ s or less at 25 ° C. measured using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.) as a viscosity suitable for workability. Is preferable, and 500 mPa ⁇ s or less is particularly preferable.
- the resin composition of the present invention can be easily cured by energy rays.
- energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays and laser rays, particle rays such as alpha rays, beta rays and electron rays.
- ultraviolet rays, laser beams, visible rays, or electron beams are preferred in the present invention.
- the cured product of the present invention can be obtained by irradiating the resin composition of the present invention with the energy beam.
- the liquid refractive index of the resin composition of the present invention is usually 1.45 to 1.55, preferably 1.48 to 1.52.
- the refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.).
- the water vapor transmission rate at 60 ° C. with a thickness of 100 ⁇ m is preferably 200 g / m 2 ⁇ day or less, more preferably 100 g / m 2 ⁇ day or less, and 60 g / m. 2 ⁇ day or less is particularly preferable. By being in the said range, it becomes possible to prevent effectively that a device is damaged by permeation
- the organic EL element solid sealing method using the resin composition of the present invention includes a step of forming a passivation film on the organic EL element formed on the substrate, and applying a sealing adhesive on the passivation film. It is preferable to have a step of providing a sealing transparent substrate and a step of curing the sealing adhesive, and the curable resin composition according to the present invention described above can be used as the sealing adhesive. .
- the organic EL element to be sealed includes, for example, a substrate, a lower electrode, an organic EL layer including at least a light emitting layer, and an element unit body including an upper electrode.
- the substrate is a flat substrate made of an electrically insulating material such as a glass substrate, a transparent organic material made of cycloolefin, polycarbonate, polymethyl methacrylate, or the like, or an organic / inorganic hybrid transparent substrate made of the transparent organic material made of high-rigidity glass fiber or the like.
- a simple substrate can be used.
- the following are mentioned as a typical structure of an element part main body.
- a lower electrode (cathode) made of an Al—Li alloy or the like is deposited on one side of a substrate by resistance heating deposition.
- an electron transport layer made of an oxadiazole derivative or a triazole derivative, a light-emitting layer, a hole transport layer made of TPD or the like and an upper electrode (anode) are formed by resistance heating vapor deposition.
- the organic EL element can be manufactured by sequentially laminating by a thin film forming method such as an ion beam sputtering method.
- the layer structure or material of the organic EL element is not particularly limited as long as it functions as a display element.
- the resin composition of the present invention can be applied to any structure of organic EL elements.
- the passivation film is formed so as to cover the organic EL element.
- the passivation film can be formed by a method such as vapor deposition or sputtering of an inorganic material such as silicon nitride or silicon oxide.
- the passivation film is provided to prevent moisture, ionic impurities, and the like from entering the organic EL element.
- the thickness of the passivation film is preferably in the range of 10 nm to 100 ⁇ m, and more preferably in the range of 100 nm to 10 ⁇ m.
- the passivation film is generally an incomplete film with pinholes or a film with low mechanical strength, although it depends on the film forming method. Therefore, in the solid sealing method using the resin composition of the present invention, an adhesive is further applied onto the passivation film, the adhesive is pressure-bonded using a transparent substrate for sealing, and the adhesive is cured by curing. Reliability can be increased.
- the ultraviolet curable resin composition and cured product of the present invention were obtained with the compositions shown in the following examples.
- the evaluation method and evaluation criteria for the resin composition and the cured film were as follows.
- the Example containing an organic solvent it evaluated, after volatilizing an organic solvent fully with an evaporator.
- Moisture permeability The resin composition is sandwiched between 5 mm thick glass substrates, the film thickness is adjusted using a 100 ⁇ m spacer, and cured at 3000 mJ / cm 2 with a high pressure mercury lamp (120 W / cm, ozone-less). Produced. The moisture permeability of the obtained test piece was measured with a Lyssy water vapor permeability meter L80-5000 (manufactured by Systech Illinois), 60 ° C. ⁇ 90% RH. The results are shown in Table 1.
- Tg (glass transition point) The Tg point of the cured resin composition was measured with a viscoelasticity measurement system EXSTAR DMS-6000 (manufactured by SII Nanotechnology Co., Ltd.), tensile mode, and frequency 1 Hz. The results are shown in Table 1.
- Comparative Example 1 was not completely cured by 2000 mJ / cm 2 with a high-pressure mercury lamp (120 W / cm, ozone-less), only measurable items were described.
- R-604 hydroxypivalaldehyde-modified trimethylolpropane diacrylate, Nippon Kayaku Co., Ltd.
- R-684 tricyclodecane dimethylol acrylate, Nippon Kayaku Co., Ltd.
- OPP-1 orthophenylphenoxyethyl Acrylate, Nippon Kayaku Co., Ltd.
- PHE Phenoxyethyl acrylate, Shin-Nakamura Chemical Co., Ltd.
- FA-320A Ethylene oxide 2 mol modified bisphenol A diacrylate, Hitachi Chemical Co., Ltd.
- Nikanol Y -50 Reaction product of meta-xylene and formaldehyde (number average molecular weight 250), ADAMANTATE M-104: 1-adamantyl methacrylate manufactured by Fudou Co., Ltd., MH-002: 1,2-bis manufactured by Idemitsu Kosan Co., Ltd. (Trimethylsiloxy) -1,1,2,2-tetrapheny Luethan, Irgacure 184D: 1-hydroxycyclohexyl phenyl ketone, manufactured by Wako Pure Chemical Industries, Ltd., manufactured by BASF Corporation
- the resin composition of the present invention having a specific composition has a high Tg, a low curing shrinkage rate, and a low moisture permeability. Therefore, for example, it is suitable for various sealing materials, particularly for organic EL device sealing materials.
- the cure shrinkage ratios were all 2% or less, and no cracks were observed in the brittleness test. All the transmittances were 90% or more.
- the resin composition of the present invention and its cured product have excellent visible light transmittance, high Tg, low curing shrinkage rate, moisture permeability, and low brittleness. Therefore, it is suitable for various sealing materials, particularly for organic EL device sealing materials. It is suitable.
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Abstract
Description
(1)芳香族炭化水素骨格を有する(メタ)アクリレート化合物(A)、環状(メタ)アクリレート化合物(B)及び重合開始剤(C)を含有する樹脂組成物であって、
化合物(B)が、化合物(A)以外の芳香族炭化水素骨格を有する(メタ)アクリレート化合物、脂環式炭化水素骨格を有する(メタ)アクリレート化合物およびヘテロ環骨格を有する(メタ)アクリレート化合物からなる群から選択される少なくとも1種類の(メタ)アクリレート化合物である樹脂組成物。
(2)化合物(A)が、1分子中に芳香族炭化水素骨格を2つ以上有する(メタ)アクリレート化合物である(1)に記載の樹脂組成物。
(3)化合物(A)の芳香族炭化水素骨格が、下記式(1)で表される骨格を有する(1)または(2)に記載の樹脂組成物。
(4)化合物(A)が下記式(2)で表される化合物である(1)~(3)のいずれか一つに記載の樹脂組成物。
(5)1分子中に2つ以上の芳香族炭化水素骨格を有する(メタ)アクリレート化合物が、フルオレン骨格、ナフタレン骨格またはビフェニル骨格を有する(メタ)アクリレート化合物である(2)に記載の樹脂組成物。
(6)化合物(B)が、脂環式炭化水素骨格を有する(メタ)アクリレート化合物であり、1分子中に2つ以上の脂環式炭化水素骨格を有する(メタ)アクリレート化合物である(1)~(5)のいずれか一つに記載の樹脂組成物。
(7)脂環式炭化水素骨格を有する(メタ)アクリレート化合物が、脂環式炭化水素骨格としてジシクロデカン構造、トリシクロデカン環またはアダマンタン環を含む(6)に記載の樹脂組成物。
(8)脂環式炭化水素骨格を有する(メタ)アクリレート化合物が、下記式(3)で表される(メタ)アクリレート化合物である(6)に記載の樹脂組成物。
(9)脂環式炭化水素骨格が下記式(5)で表される(メタ)アクリレート化合物である(6)に記載の樹脂組成物。
(10)化合物(B)が、ヘテロ環骨格を有する(メタ)アクリレート化合物であり、下記式(6)で表される(メタ)アクリレート化合物である(1)~(5)のいずれか一つに記載の樹脂組成物。
(11)下記式(2)で表される化合物(A):下記式(3)で表される化合物(B)の重量比が9:1~1:9である(1)に記載の樹脂組成物。
(12)(1)~(11)のいずれか一つに記載の樹脂組成物を硬化させてなる低透湿バリアフィルム。
(13)OLED用途に用いられる(1)~(11)のいずれか一つに記載の樹脂組成物。
上記の構成により、2種類の異なる骨格の(メタ)アクリレート化合物が硬化時に相互に硬化系に導入されることとなり、低収縮率を実現しつつ、環状骨格を有する化合物を1種類含有させるだけでは達成できなかった極めて優れた低水蒸気透過率の効果を達成することが可能となる。
尚、これらの芳香族炭化水素骨格は、置換基を有していても、有していなくてもよく、置換基を有する場合には、当該置換基は炭素数1~6のアルキル基、炭素数1~6のアルコキシ基、炭素数1~6のアルケニル基であることが好ましい。
単官能(メタ)アクリレート化合物の例としては、ベンジル(メタ)アクリレート、エトキシ変性クレゾール(メタ)アクリート、プロポキシ変性クレゾール(メタ)アクリレート、ネオペンチルグリコールベンゾエート(メタ)アクリレート、o-フェニルフェノール(メタ)アクリレート、o-フェニルフェノールモノエトキシ(メタ)アクリレート、o-フェニルフェノールポリエトキシ(メタ)アクリレート、p-フェニルフェノール(メタ)アクリレート、p-フェニルフェノールモノエトキシ(メタ)アクリレート、p-フェニルフェノールポリエトキシ(メタ)アクリレート、o-フェニルベンジルアクリレート、p-フェニルベンジルアクリレート等の単環を有する(メタ)アクリレート化合物、カルバゾール(ポリ)エトキシ(メタ)アクリレート、カルバゾール(ポリ)プロポキシ(メタ)アクリレート、(ポリ)カプロラクトン変性カルバゾール(メタ)アクリレート等の複素環を有する(メタ)アクリレート化合物、ナフチル(メタ)アクリレート、ナフチル(ポリ)エトキシ(メタ)アクリレート、ナフチル(ポリ)プロポキシ(メタ)アクリレート、(ポリ)カプロラクトン変性ナフチル(メタ)アクリレート、ビナフトール(メタ)アクリレート、ビナフトール(ポリ)エトキシ(メタ)アクリレート、ビナフトール(ポリ)プロポキシ(メタ)アクリレート、(ポリ)カプロラクトン変性ビナフトール(メタ)アクリレート、ナフトール(メタ)アクリレート、ナフトール(ポリ)エトキシ(メタ)アクリレート、ナフトール(ポリ)プロポキシ(メタ)アクリレート、(ポリ)カプロラクトン変性ナフトール(メタ)アクリレート等の縮合環を有する(メタ)アクリレート化合物が挙げられる。
2官能以上の(メタ)アクリレート化合物としては、(ポリ)エトキシ変性ビスフェノールAジ(メタ)アクリレート、(ポリ)プロポキシ変性ビスフェノールAジ(メタ)アクリレート、(ポリ)エトキシ変性ビスフェノールFジ(メタ)アクリレート、(ポリ)プロポキシ変性ビスフェノールFジ(メタ)アクリレート、(ポリ)エトキシ変性ビスフェノールSジ(メタ)アクリレート、(ポリ)プロポキシ変性ビスフェノールSジ(メタ)アクリレート、ヘキサヒドロフタル酸ジ(メタ)アクリレート、ビスフェノキシ(ポリ)エトキシフルオレン等の単環を有する(メタ)アクリレート化合物、ビフェニルジメタノールジ(メタ)アクリレート等の複素環を有する(メタ)アクリレート化合物、ナフトールジ(メタ)アクリレート、ビナフトール(ポリ)エトキシジ(メタ)アクリレート、ビナフトール(ポリ)プロポキシジ(メタ)アクリレート、(ポリ)カプロラクトン変性ビナフトールジ(メタ)アクリレート等の縮合環を有する(メタ)アクリレート化合物、ビスフェノールフルオレンジ(メタ)アクリレート、ビスフェノキシメタノールフルオレンジ(メタ)アクリレート、ビスフェノキシエタノールフルオレンジ(メタ)アクリレート、ビスフェノキシカプロラクトンフルオレンジ(メタ)アクリレート等の多環芳香族を有する(メタ)アクリレート化合物等が挙げられる。
エポキシ(メタ)アクリレートとしては、ビスフェノールA型エポキシ樹脂、ビスフェノールF型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、ビフェニル型フェノールアラルキル樹脂、ビスフェノールAのプロピレンオキサイド付加物の末端グリシジルエーテル、フルオレンエポキシ樹脂、ビスフェノールS型エポキシ樹脂等のエポキシ樹脂類と(メタ)アクリル酸との反応物等を挙げることができる。
上記の部分骨格を有することにより、芳香環が付与できる撥水性をより効果的に発現することが可能となると考えられる。
具体的には、上記の(メタ)アクリレート化合物の中でも、ビスフェノールA骨格、ビスフェノールF骨格等のビスフェノール骨格や、ビフェニル骨格を有する(メタ)アクリレート化合物は上記(1)式に該当し、好適に使用できる。
さらに、芳香族炭化水素骨格には(メタ)アクリロイル基が連結していることが好ましい。具体的には、上記芳香族炭化水素骨格に、(メタ)アクリロイル基が直接または炭化水素基を介して連結していることが好ましく、炭化水素基を介して連結している場合の炭化水素基としては、炭素数1~10のアルキレン基または、エーテル結合を有する炭素数1~10のアルキレン基が挙げられる。
このような(メタ)アクリレート化合物の具体例は、o-フェニルフェノール(メタ)アクリレート、o-フェニルフェノールモノエトキシ(メタ)アクリレート、o-フェニルフェノールポリエトキシ(メタ)アクリレート、p-フェニルフェノール(メタ)アクリレート、p-フェニルフェノールモノエトキシ(メタ)アクリレート、p-フェニルフェノールポリエトキシ(メタ)アクリレート、o-フェニルベンジルアクリレート、p-フェニルベンジルアクリレート、(ポリ)プロポキシ変性ビスフェノールAジ(メタ)アクリレート、(ポリ)エトキシ変性ビスフェノールFジ(メタ)アクリレート、(ポリ)プロポキシ変性ビスフェノールFジ(メタ)アクリレート、等が挙げられる。
ここで、環状(メタ)アクリレート化合物(B)として、芳香族炭化水素骨格を有する(メタ)アクリレート化合物を使用した場合、樹脂組成物は、構造の異なる2種類の「芳香族炭化水素骨格を有する(メタ)アクリレート化合物」を含有することとなる。すなわち、環状(メタ)アクリレート化合物として使用できる芳香族炭化水素骨格を有する(メタ)アクリレートは、上に列挙したものと同じであるが、化合物(A)と同じ(メタ)アクリレート化合物を使用することはできない。
このように芳香族炭化水素骨格を有する(メタ)アクリレート化合物を樹脂組成物中に使用した場合においては、鎖状構造のもの等の他の骨格と比較して、水蒸気の透過を防ぐ効果があり、芳香族炭化水素骨格を有する(メタ)アクリレート化合物(A)と併せて硬化系に配置されることによって、相乗効果によって顕著に水蒸気の透過を防ぐことが可能となる。
環式炭化水素骨格としては、具体的に使用できる骨格としては、シクロペンタン骨格、シクロヘキサン骨格、シクロヘプタン骨格、ジシクロデカン構造、トリシクロデカン環、アダマンタン環、イソボルニル環等を挙げることができる。
中でも、トリシクロデカン環、アダマンタン環等といった橋かけ環式炭化水素骨格を有する(メタ)アクリレート化合物が好ましい。このような化合物においては、脂環式炭化水素骨格に橋かけがなされているため、立体的な構造をとって環状構造の空間に炭素原子が配置されているため、水蒸気の透過をより有効に防ぐことができる。そして、上記相乗効果は、このような橋かけ環式炭化水素骨格を有する(メタ)アクリレート化合物との混合によって、より高いものとなる。
さらに、環式炭化水素骨格には(メタ)アクリロイル基が連結していることが好ましい。具体的には、上記環式炭化水素骨格に、(メタ)アクリロイル基が直接または炭化水素基を介して連結していることが好ましく、炭化水素基を介して連結している場合の炭化水素基としては、炭素数1~10のアルキレン基または、エーテル結合を有する炭素数1~10のアルキレン基が挙げられる。
単官能(メタ)アクリレート化合物としては、イソボルニル(メタ)アクリレート、ジシクロペンタニル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、ジシクロペンテニロキシエチル(メタ)アクリレート、シクロヘキシル(メタ)アクリレート等の脂環式(メタ)アクリレート、1,3-アダマンタンジオールジ(メタ)アクリレート、1,3-アダマンタンジメタノールジ(メタ)アクリレート、2-メチル-2-アダマンチル(メタ)アクリレート、2-エチル-2-アダマンチル(メタ)アクリレート、3-ヒドロキシ-1-アダマンチル(メタ)アクリレート、1-アダマンチル(メタ)アクリレート等が挙げられる。
2官能以上の多官能(メタ)アクリレート化合物としては、トリシクロデカンジメタノール(メタ)アクリレート等の脂環式(メタ)アクリレート等が挙げられる。
上記式(3)の(メタ)アクリレート化合物の具体例としては、トリシクロデカンジメタノール(メタ)アクリレート等の脂環式(メタ)アクリレート等が挙げられる。
このようなヘテロ環骨格においては、鎖状構造のもの等の他の骨格と比較して、水蒸気の透過を防ぐ効果があり、芳香族炭化水素骨格を有する(メタ)アクリレート化合物(A)と併せて硬化系に配置されることによって、相乗効果によって顕著に水蒸気の透過を防ぐことが可能となる。
ヘテロ環骨格としては、具体的に使用できる骨格としては、ジオキサン構造、トリオキサン構造、イソシアヌレート構造等を挙げることができる。
さらに、ヘテロ環骨格には(メタ)アクリロイル基が連結していることが好ましい。具体的には、上記ヘテロ環骨格に、(メタ)アクリロイル基が直接または炭化水素基を介して連結していることが好ましく、炭化水素基を介して連結している場合の炭化水素基としては、炭素数1~10のアルキレン基または、エーテル結合を有する炭素数1~10のアルキレン基が挙げられる。
即ち、テトラヒドロフルフリル(メタ)アクリレート、アルコキシ化テトラヒドロフルフリルアクリレートカプロラクトン変性テトラヒドロフルフリル(メタ)アクリレート、モルホリン(メタ)アクリレート、イソシアヌル酸EEO変性ジアクリレート(M-215)、ε-カプロラクトン変性トリス(アクロキシエチル)イソシアヌレート(M-327)、イソシアヌル酸EO変性ジ及びトリアクリレート(M-313またはM-315)、ヒドロキシピバルアルデヒド変性トリメチロールプロパンジアクリレート(R-604)、ペンタメチルピペリジニルメタクリレート(FA-711)、テトラメチルピペリジニルメタクリレート(FA-712HM)、環状トリメチロールプロパンフォルマルアクリレート(SR531)が挙げられる。
ここで、好ましくは下記式(6)で表される化合物を使用することができる。
なぜならば、上記ポリEO変性(メタ)アクリレート化合物は水蒸気透過率が劣り、当該ポリEO変性(メタ)アクリレート化合物の含有量が多く、樹脂組成物中において支配的になると、水蒸気透過率が劣る恐れがあるためである。
そして、樹脂組成物中にポリEO変性(メタ)アクリレート化合物の総重量が、樹脂組成物100重量部に対して、10重量部以下であることが好ましく、5重量部以下であることがより好ましく、2重量部以下であることが特に好ましい。
上記好ましい範囲とすることで、水蒸気透過率に極めて優れた樹脂組成物を得ることが可能となる。
上記熱ラジカル重合開始剤として、好ましいのはベンゾピナコール系の熱ラジカル重合開始剤(ベンゾピナコールを化学的に修飾したものを含む)である。具体的には、ベンゾピナコール、1,2-ジメトキシ-1,1,2,2-テトラフェニルエタン、1,2-ジエトキシ-1,1,2,2-テトラフェニルエタン、1,2-ジフェノキシ-1,1,2,2-テトラフェニルエタン、1,2-ジメトキシ-1,1,2,2-テトラ(4-メチルフェニル)エタン、1,2-ジフェノキシ-1,1,2,2-テトラ(4-メトキシフェニル)エタン、1,2-ビス(トリメチルシロキシ)-1,1,2,2-テトラフェニルエタン、1,2-ビス(トリエチルシロキシ)-1,1,2,2-テトラフェニルエタン、1,2-ビス(t-ブチルジメチルシロキシ)-1,1,2,2-テトラフェニルエタン、1-ヒドロキシ-2-トリメチルシロキシ-1,1,2,2-テトラフェニルエタン、1-ヒドロキシ-2-トリエチルシロキシ-1,1,2,2-テトラフェニルエタン、1-ヒドロキシ-2-t-ブチルジメチルシロキシ-1,1,2,2-テトラフェニルエタン等、が挙げられ、好ましくは1-ヒドロキシ-2-トリメチルシロキシ-1,1,2,2-テトラフェニルエタン、1-ヒドロキシ-2-トリエチルシロキシ-1,1,2,2-テトラフェニルエタン、1-ヒドロキシ-2-t-ブチルジメチルシロキシ-1,1,2,2-テトラフェニルエタン、1,2-ビス(トリメチルシロキシ)-1,1,2,2-テトラフェニルエタンであり、さらに好ましくは1-ヒドロキシ-2-トリメチルシロキシ-1,1,2,2-テトラフェニルエタン、1,2-ビス(トリメチルシロキシ)-1,1,2,2-テトラフェニルエタンであり、特に好ましくは1,2-ビス(トリメチルシロキシ)-1,1,2,2-テトラフェニルエタンである。
上記ベンゾピナコールは東京化成工業株式会社、和光純薬工業株式会社等から市販されている。また、ベンゾピナコールのヒドロキシ基をエーテル化することは、周知の方法によって容易に合成可能である。また、ベンゾピナコールのヒドロキシ基をシリルエーテル化することは、対応するベンゾピナコールと各種シリル化剤をピリジンなどの塩基性触媒下で加熱させる方法により合成して得ることができる。シリル化剤としては、一般に知られているトリメチルシリル化剤であるトリメチルクロロシラン(TMCS)、ヘキサメチルジシラザン(HMDS)、N,O-ビス(トリメチルシリル)トリフルオロアセトアミド(BSTFA)やトリエチルシリル化剤としてトリエチルクロロシラン(TECS)、t-ブチルジメチルシリル化剤としてt-ブチルメチルシラン(TBMS)などが挙げれる。これらの試薬はシリコン誘導体メーカー等の市場から容易に入手することが出来る。シリル化剤の反応量としては対象化合物の水酸基1モルに対して1.0~5.0倍モルが好ましい。さらに好ましくは1.5~3.0倍モルである。1.0倍モルより少ないと反応効率が悪く、反応時間が長くなるため熱分解を促進する恐れがある。5.0倍モルより多いと回収の際に分離が悪くなったり、精製が困難になる恐れがある。
ウレタン(メタ)アクリレートとしては、例えば、ジオール化合物(例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリプロピレングリコール、1,4-ブタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、1,8-オクタンジオール、1,9-ノナンジオール、2-メチル-1,8-オクタンジオール、3-メチル-1,5-ペンタンジオール、2,4-ジエチル-1,5-ペンタンジオール、2-ブチル-2-エチル-1,3-プロパンジオール、シクロヘキサン-1,4-ジメタノール、ポリエチレングリコール、ポリプロピレングリコール、ビスフェノールAポリエトキシジオール、ビスフェノールAポリプロポキシジオール等)又はこれらジオール化合物と二塩基酸若しくはその無水物(例えば、コハク酸、アジピン酸、アゼライン酸、ダイマー酸、イソフタル酸、テレフタル酸、フタル酸若しくはこれらの無水物)との反応物であるポリエステルジオールと、有機ポリイソシアネート(例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、2,2,4-トリメチルヘキサメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート等の鎖状飽和炭化水素イソシアネート、イソホロンジイソシアネート、ノルボルナンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、メチレンビス(4-シクロヘキシルイソシアネート)、水添ジフェニルメタンジイソシアネート、水添キシレンジイソシアネート、水添トルエンジイソシアネート等の環状飽和炭化水素イソシアネート、2,4-トリレンジイソシアネート、1,3-キシリレンジイソシアネート、p-フェニレンジイソシアネート、3,3’-ジメチル-4,4’-ジイソシアネート、6-イソプロピル-1,3-フェニルジイソシアネート、1,5-ナフタレンジイソシアネート等の芳香族ポリイソシアネート)を反応させ、次いで水酸基含有(メタ)アクリレートを付加した反応物等が挙げられる。
ウレタン(メタ)アクリレート化合物の樹脂組成物中の含有量は、樹脂組成物100重量部に対して、通常5~95重量部が好ましく、10~80重量部がより好ましく、20~70重量部が特に好ましい。
尚、透過率(特に、380nm~780nmでの透過率)を向上させる観点からは、微粒子を含有させないことが好ましい。
本発明においては、1次粒径が100nm以下であることが好ましい。そして、5~100nmである微粒子が好適に使用できる。100nm以下であることにより、耐擦傷性を付与しつつ、透過率が高い硬化物を提供することが可能となる。
また、本発明の樹脂組成物においては、ガラス転移温度が70℃以上であることが好ましく、100℃以上が特に好ましい。
本発明の樹脂組成物においては、厚み100μmの60℃での水蒸気透過率が200g/m2・day以下であることが好ましく、100g/m2・day以下であることがより好ましく、60g/m2・day以下であることが特に好ましい。当該範囲にあることで、水分の透過により、素子にダメージを与えることを有効に防ぐことが可能となる。
(1)下部電極/発光層/上部電極
(2)下部電極/電子輸送層/発光層/上部電極
(3)下部電極/発光層/正孔輸送層/上部電極
(4)下部電極/電子輸送層/発光層/正孔輸送層/上部電極
例えば、上記(4)の層構造を有する有機EL素子は、基板の片面上に、Al-Li合金等からなる下部電極(陰極)を抵抗加熱蒸着法またはスパッタ法によって形成し、次いで有機EL層として、オキサジアゾール誘導体やトリアゾール誘導体等からなる電子輸送層、発光層、TPD等からなる正孔輸送層及び上部電極(陽極)を抵抗加熱蒸着法又はイオンビームスパッタ法等の薄膜形成方法によって順次積層することによって作製することが可能である。なお、有機EL素子の層構造、又は材料は表示素子として機能するものであれば特に限定されるものではない。また、本発明の樹脂組成物はいかなる構造の有機EL素子であっても適用可能である。
これを、JIS K7112 B法に準拠し、硬化物の比重(DS)を測定した。また、23±2℃で樹脂組成物の比重(DL)を測定し、次式により硬化収縮率を算出した。測定結果は4回の測定結果の平均値で示す。
硬化収縮率(%)=(DS-DL)/DS×100
R-684:トリシクロデカンジメチロールアクリレート、日本化薬(株)社製
OPP-1:オルソフェニルフェノキシエチルアクリレート、日本化薬(株)社製
PHE:フェノキシエチルアクリレート、新中村化学工業(株)社製
FA-320A:エチレンオキサイド2モル変性ビスフェノールA型ジアクリレート、日立化成工業(株)社製
ニカノールY-50:メタキシレンとホルムアルデヒドとの反応物(数平均分子量250)、フドー(株)社製
ADAMANTATE M-104:1-アダマンチルメタクリレート、出光興産(株)社製
MH-002:1,2-ビス(トリメチルシロキシ)-1,1,2,2-テトラフェニルエタン、和光純薬(株)社製
イルガキュア184D:1-ヒドロキシシクロヘキシルフェニルケトン、BASF(株)社製
なお、本願は、2013年3月29日付で出願された日本国特許出願(2013-071027)に基づいており、その全体が引用により援用される。また、ここに引用されるすべての参照は全体として取り込まれる。
Claims (13)
- 芳香族炭化水素骨格を有する(メタ)アクリレート化合物(A)、環状(メタ)アクリレート化合物(B)及び重合開始剤(C)を含有する樹脂組成物であって、
化合物(B)が、化合物(A)以外の芳香族炭化水素骨格を有する(メタ)アクリレート化合物、脂環式炭化水素骨格を有する(メタ)アクリレート化合物およびヘテロ環骨格を有する(メタ)アクリレート化合物からなる群から選択される少なくとも1種類の(メタ)アクリレート化合物である樹脂組成物。 - 化合物(A)が、1分子中に芳香族炭化水素骨格を2つ以上有する(メタ)アクリレート化合物である請求項1に記載の樹脂組成物。
- 1分子中に2つ以上の芳香族炭化水素骨格を有する(メタ)アクリレート化合物が、フルオレン骨格、ナフタレン骨格またはビフェニル骨格を有する(メタ)アクリレート化合物である請求項2に記載の樹脂組成物。
- 化合物(B)が、脂環式炭化水素骨格を有する(メタ)アクリレート化合物であり、1分子中に2つ以上の脂環式炭化水素骨格を有する(メタ)アクリレート化合物である請求項1~5のいずれか一項に記載の樹脂組成物。
- 脂環式炭化水素骨格を有する(メタ)アクリレート化合物が、脂環式炭化水素骨格としてジシクロデカン構造、トリシクロデカン環またはアダマンタン環を含む請求項6に記載の樹脂組成物。
- 下記式(2)で表される化合物(A):下記式(3)で表される化合物(B)の重量比が9:1~1:9である請求項1に記載の樹脂組成物。
(式中、Xは直接結合または炭素数1~3のアルキレン基を表し、Yは水素原子またはメチル基を表し、R1は水素原子、炭素数1~3のアルキル基、ハロゲン原子または(メタ)アクリロイル基を表し、R2は直接結合または炭素数1~10の(ポリ)アルキレンオキシ基を表す。)
(式中、R3はそれぞれ独立して、水素原子、炭素数1~3のアルキル基、ハロゲン原子または下記式(4)を表し、かつ、R3の少なくとも1つは下記式(4)である。)
(式中、R2は直接結合または炭素数1~10の(ポリ)アルキレンオキシ基を表し、Yは水素原子またはメチル基を表し、*は環状骨格へ結合する。) - 請求項1~11のいずれか一項に記載の樹脂組成物を硬化させてなる低透湿バリアフィルム。
- OLED用途に用いられる請求項1~11のいずれか一項に記載の樹脂組成物。
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WO2022230637A1 (ja) * | 2021-04-30 | 2022-11-03 | コニカミノルタ株式会社 | 電子デバイス封止用組成物、電子デバイス封止膜形成方法及び電子デバイス封止膜 |
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WO2021200668A1 (ja) | 2020-03-31 | 2021-10-07 | デンカ株式会社 | 感光性組成物、硬化物、有機エレクトロルミネッセンス表示装置および感光性組成物の製造方法 |
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Also Published As
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TWI654212B (zh) | 2019-03-21 |
CN105073800B (zh) | 2018-05-04 |
KR20150137049A (ko) | 2015-12-08 |
CN105073800A (zh) | 2015-11-18 |
KR102193400B1 (ko) | 2020-12-21 |
JP2014193970A (ja) | 2014-10-09 |
JP6099198B2 (ja) | 2017-03-22 |
TW201504265A (zh) | 2015-02-01 |
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