WO2014189124A1 - 有機ｅｌ素子封止用の樹脂組成物及びその硬化物 - Google Patents

有機ｅｌ素子封止用の樹脂組成物及びその硬化物 Download PDF

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Publication number
WO2014189124A1
WO2014189124A1 PCT/JP2014/063640 JP2014063640W WO2014189124A1 WO 2014189124 A1 WO2014189124 A1 WO 2014189124A1 JP 2014063640 W JP2014063640 W JP 2014063640W WO 2014189124 A1 WO2014189124 A1 WO 2014189124A1
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Prior art keywords
meth
acrylate
group
resin composition
acrylate compound
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PCT/JP2014/063640
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English (en)
French (fr)
Japanese (ja)
Inventor
伸彦 内藤
雄一朗 松尾
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日本化薬株式会社
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Priority to CN201480029746.3A priority Critical patent/CN105432142B/zh
Priority to KR1020157030739A priority patent/KR101846960B1/ko
Publication of WO2014189124A1 publication Critical patent/WO2014189124A1/ja

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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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C08F220/302—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and two or more oxygen atoms in the alcohol moiety
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols
    • 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
    • H10K50/8445—Encapsulations multilayered coatings having a repetitive structure, e.g. having multiple organic-inorganic bilayers

Definitions

  • the present invention relates to a curable resin composition that can be suitably used as various barrier materials, particularly as a film sealing material for organic EL elements, and a cured product thereof.
  • 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 method and sealing material are desired, and various 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).
  • silicon nitride is used as an inorganic material, and is often used by being laminated with an organic material such as a (meth) acrylate resin or an epoxy resin.
  • This film is usually formed by forming a laminated film by plasma CVD (chemical vapor deposition), which has a relatively high formation speed.
  • a film formed by plasma CVD of silicon nitride generally peels off when it is formed to a thickness of about several hundreds nm.
  • Japanese Patent No. 4876609 Japanese Unexamined Patent Application Publication No. 2012-059553 Japanese Unexamined Patent Publication No. 2009-270134 Japanese Patent No. 4759971
  • An object of the present invention relates to a resin composition suitable for a process for forming a resin layer on a single wafer or a continuously running substrate.
  • a resin composition suitable for an organic film for protecting an organic EL element is a resin composition suitable for an organic film for protecting an organic EL element, and provides a cured product having excellent curability and processability and high plasma damage resistance.
  • the present inventors have found that an ultraviolet curable resin composition having a specific composition and a cured product thereof can solve the above problems, and have completed the present invention. That is, the present invention relates to the following (1) to (19).
  • the monofunctional cyclic (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton represented by the following formula (2): The resin composition as described in any one.
  • the resin composition according to (10), wherein the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton includes any of a dicyclodecane ring, a tricyclodecane ring, an isobornyl ring, and an adamantane ring.
  • the monofunctional cyclic (meth) acrylate compound (A) is a monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton represented by any of the following formulas (3) to (6): (1) The resin composition according to any one of (7).
  • R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxyl group, hydroxy group or the following formula (7), either in R 3 is of the formula (7).
  • R 2 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxy group or a hydroxy group, and * is bonded to a cyclic skeleton.
  • R 2 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxy group or a hydroxy group, and * is bonded to a cyclic skeleton.
  • R 6 and R 7 each independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms, or an alkyleneoxy group.
  • the (meth) acrylate compound (B) having two or more functional groups is a (meth) acrylate compound having two or more functional groups having a heterocyclic skeleton represented by the following formula (9). (1) The resin composition according to any one of (12).
  • each R 8 independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group.
  • Each R 9 independently represents hydrogen, an alkylene group having 1 to 4 carbon atoms or a hydroxy group.
  • Z represents each independently carbon, oxygen, or nitrogen.
  • the resin composition of the present invention and its cured product are excellent in curability, processability, and visible light transmittance, and have little plasma damage. Therefore, it is useful as a resin composition for vapor deposition and is particularly suitable as a film sealing material for organic EL elements.
  • the resin composition of the present invention comprises a monofunctional cyclic (meth) acrylate compound (A), a cyclic (meth) acrylate compound (B) having two or more functional groups, and a polymerization initiator (C).
  • A monofunctional cyclic (meth) acrylate compound
  • B cyclic (meth) acrylate compound
  • C polymerization initiator
  • any known compounds can be used as long as they have an aromatic ring, an alicyclic ring or a heterocyclic ring.
  • plasma damage in a subsequent process can be suppressed to a low level by providing the ring structure.
  • This has a strong relationship with a compound having a cyclic structure, particularly an aromatic ring or an alicyclic ring, having high dry etching resistance. And the said effect can fully be show
  • the said effect will become more excellent by selecting the (meth) acrylate which has one or more aromatic rings or alicyclic rings in a molecule
  • the skeleton having one or more aromatic rings or alicyclic rings in the molecule include a phenyl skeleton, a biphenyl skeleton, a bisphenol skeleton, a cumyl skeleton, a naphthalene skeleton, a binaphthalene skeleton, a cyclohexane skeleton, a cyclopentane skeleton, a cyclobutane skeleton, Examples include a cyclopropane skeleton, a norbornene skeleton, an isobornyl skeleton, a dicyclodecane skeleton, a tricyclodecane skeleton, and an adamantane skeleton.
  • skeletons can exhibit excellent low plasma damage.
  • the skeleton described in the present invention may or may not have a substituent.
  • the substituent is an alkyl group having 1 to 6 carbon atoms or The alkoxy group has 1 to 6 carbon atoms.
  • a (meth) acrylate compound having a partial skeleton represented by the following formula (1) can be preferably used as the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton.
  • X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms.
  • the dotted line may or may not be present, and * represents a (meth) acryloyl group.
  • a (meth) acrylate compound having a phenyl skeleton, a biphenyl skeleton, a bisphenol skeleton, a naphthalene skeleton, or a binaphthalene skeleton corresponds to the above formula (1) and can be suitably used.
  • the alkyleneoxy group means an alkylene group having an ether bond, for example, a (poly) oxyethylene group, a (poly) oxypropylene group, —O— (CH 2 ) 2 —O. -Groups and the like, and so on.
  • the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton used in the present invention is preferably a (meth) acrylate compound represented by the following formula (2).
  • X represents an oxygen atom, an alkylene group having 1 to 3 carbon atoms or an alkyleneoxy group having 1 to 3 carbon atoms
  • R 1 represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, or 1 to 3 carbon atoms
  • Y represents a hydrogen atom, a directly bonded phenyl group or an alkyl group having 1 to 4 carbon atoms.
  • Specific examples of such (meth) acrylate compounds include benzyl (meth) acrylate, phenol monoethoxy (meth) acrylate, phenol polyethoxy (meth) acrylate, phenol monopropoxy (meth) acrylate, and phenol polypropoxy (meth) acrylate.
  • benzyl acrylate phenol monoethoxy acrylate, o-phenylphenol (poly) ethoxy acrylate, and o-phenyl benzyl acrylate are preferable, and benzyl acrylate is particularly preferable.
  • the content of the monofunctional (meth) acrylate compound having an aromatic hydrocarbon skeleton in the resin composition is usually preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the resin composition. 30 to 70 parts by mass are preferable.
  • the monofunctional (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 saturated carbonization. A hydrogen skeleton is preferred.
  • a cyclic skeleton compared with other skeletons such as those having a chain structure, there is an effect of preventing the permeation of water vapor, and the curing system is combined with a (meth) acrylate compound having an aromatic hydrocarbon skeleton. It becomes possible to prevent permeation
  • An organic EL element is easily deteriorated by an attack of an organic gas or water vapor, so that the water vapor transmission rate is low, that is, low moisture permeability is an important physical property.
  • the skeleton that can be specifically used as the cyclic hydrocarbon skeleton include a cyclopropane skeleton, a cyclobutane skeleton, a cyclopentane skeleton, a cyclohexane skeleton, a cycloheptane skeleton, a dicyclodecane ring, a tricyclodecane ring, an adamantane ring, an isobornyl ring, and a norbornene ring. Can be mentioned.
  • (meth) acrylate compounds having a bridged-ring hydrocarbon skeleton such as a tricyclodecane ring, isobornyl ring, adamantane ring and the like are preferable.
  • Such a compound is considered to be excellent in dry etching resistance and exhibiting an effect of suppressing plasma damage.
  • Such a compound has a high Tg (glass transition point) as compared with other skeletons such as a chain structure, but tends to have a low curing shrinkage. For this reason, the hardness under the use environment can be maintained, and the residual stress at the interface is small when curing on the substrate. For this reason, it is also a material with excellent substrate adhesion.
  • Such monofunctional (meth) acrylate compounds having an alicyclic hydrocarbon skeleton include isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo Pentenyloxyethyl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate, 1,3-adamantanediol (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl Examples include -2-adamantyl (meth) acrylate, 3-hydroxy-1-adamantyl (meth) acrylate, and 1-adamantyl (meth) acrylate. Of these, cyclohexyl acrylate is preferable.
  • a (meth) acrylate compound having a structure represented by the following formulas (3) to (6) is preferably used. it can.
  • R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxyl group, hydroxy group or the following formula (7), either in R 3 is of the formula (7).
  • R 2 is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogen atom, a carboxy group or a hydroxy group, and * is bonded to a cyclic skeleton.
  • the content of the monofunctional (meth) acrylate compound having an alicyclic hydrocarbon skeleton in the resin composition is usually preferably 10 to 90 parts by mass, and 20 to 80 parts by mass with respect to 100 parts by mass of the resin composition. More preferred is 30 to 70 parts by mass.
  • the (meth) acrylate compound having a heterocyclic skeleton that can be used as a monofunctional cyclic (meth) acrylate compound in the present invention will be described below.
  • a heterocyclic skeleton has an effect of preventing plasma damage as compared with other skeletons such as a chain structure, and has a (meth) acrylate compound having an aromatic hydrocarbon skeleton or an alicyclic hydrocarbon skeleton. By arranging them together in the curing system, plasma damage can be remarkably prevented by a synergistic effect.
  • Examples of the skeleton that can be specifically used as the heterocyclic skeleton include a dioxane skeleton, a trioxane skeleton, a tetrahydrofuran skeleton, a pyrrolidine skeleton, a piperidine skeleton, a spiroglycol skeleton, a morpholine skeleton, a triazine skeleton, an isocyanurate skeleton, a carbazole skeleton, and an imide ring skeleton.
  • a dioxane skeleton a trioxane skeleton, a tetrahydrofuran skeleton, a pyrrolidine skeleton, a piperidine skeleton, a spiroglycol skeleton, a morpholine skeleton, a triazine skeleton, an isocyanurate skeleton, a carbazole skeleton, and an imide ring skeleton.
  • the (meth) acrylate compound having a heterocyclic skeleton include the following (meth) acrylate compounds. That is, tetrahydrofurfuryl (meth) acrylate, alkoxylated tetrahydrofurfuryl (meth) acrylate, caprolactone modified tetrahydrofurfuryl (meth) acrylate, morpholine (meth) acrylate, isocyanuric acid EO modified (meth) acrylate, ⁇ -caprolactone modified ( (Meth) acryloxyethyl) isocyanurate, hydroxypivalaldehyde-modified trimethylolpropane (meth) acrylate, pentamethylpiperidinyl (meth) acrylate, tetramethylpiperidinyl (meth) acrylate, cyclic trimethylolpropane formal ( Examples include meth) acrylate, spiroglycol (meth) acrylate, and im
  • the content of the monofunctional (meth) acrylate compound having a heterocyclic skeleton in the resin composition is usually preferably 10 to 90 parts by mass, more preferably 20 to 80 parts by mass with respect to 100 parts by mass of the resin composition. 30 to 70 parts by mass is particularly preferable.
  • a (meth) acrylate compound having a structure represented by the following partial structural formula (PE) (hereinafter referred to as polyEO modified (meth) acrylate)
  • PE partial structural formula
  • the total mass of (referred to as a compound) is preferably less than the total mass of (meth) acrylate compounds other than the polyEO-modified (meth) acrylate compound, and more preferably 1 ⁇ 2 or less.
  • t represents an integer of 2 or more.
  • the polyEO-modified (meth) acrylate compound is susceptible to plasma damage, and if the content of the polyEO-modified (meth) acrylate compound is large and becomes dominant in the resin composition, the plasma damage property may be inferior. Because there is. And it is preferable that the total mass of the polyEO modified
  • 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 it as a compound or a cyclic (meth) acrylate compound, even if it is used, it is preferably 50 parts by mass or less, particularly preferably 20 parts by mass or less, relative to 100 parts by mass of the resin composition.
  • cyclic (meth) acrylate compound (B) having two or more functional groups used in the present invention any known compound can be used as long as it has an aromatic ring, an alicyclic ring or a heterocyclic ring. .
  • the skeleton suitable as an aromatic hydrocarbon skeleton is as described above.
  • (meth) acrylate biphenyl (Meth) acrylate having a heterocyclic ring such as dimethanol di (meth) acrylate, biphenol (poly) ethoxydi (meth) acrylate, biphenol (poly) propoxy di (meth) acrylate, phthalic acid-modified pentaerythritol tri (meth) acrylate, dihydroxy Naphthalene di (meth) acrylate, dihydroxynaphthalene (poly) ethoxydi (meth) acrylate, dihydroxynaphthalene (poly) propoxy di (meth) acrylate, binaphthol di (meth) acrylate Rate, binaphthol (poly) ethoxydi (meth) acrylate, binaphthol (poly) propoxy di (meth) acrylate, (poly) caprolactone modified binaphthol di (meth) acrylate and other (meth)
  • a compound having a naphthalene skeleton is preferable, and binaphthol (poly) ethoxydi (meth) acrylate is particularly preferable.
  • (meth) acrylate having a partial structure represented by the following formula (A) is preferable.
  • X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom.
  • the dotted line may or may not be present, and * represents a (meth) acryloyl group. Bonds with the organic group possessed.
  • (meth) acrylate represented by the following formula (B) is particularly preferable.
  • X represents a direct bond, a methylene group, a dimethylmethylene group, a sulfonyl group, a sulfur atom or an oxygen atom, and m and n are repeating numbers and represent an integer of 1 to 50.
  • m + n is preferably 2 to 30, particularly preferably m + n is 4 to 10.
  • acrylic acid and polybasic acid anhydride specifically, maleic anhydride, succinic anhydride, itaconic anhydride, Dibasic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetra Carboxylic anhydride, biphenyltetracarboxylic anhydride, etc.
  • Dibasic anhydrides such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone
  • maleic anhydride succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, and hexahydrophthalic anhydride are preferred because of excellent heat resistance and hydrolysis resistance.
  • Examples of the formula (meth) acrylate compound (B) having two or more functional groups having an alicyclic hydrocarbon skeleton include tricyclodecane dimethanol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, 1, 3-adamantane dimethanol di (meth) acrylate, hydrogenated bisphenol A (poly) ethoxydi (meth) acrylate, hydrogenated bisphenol A (poly) propoxy di (meth) acrylate, hydrogenated bisphenol F (poly) ethoxydi (meth) acrylate, Examples include alicyclic (meth) acrylates such as hydrogenated bisphenol F (poly) propoxy di (meth) acrylate, hydrogenated bisphenol S (poly) ethoxydi (meth) acrylate, and hydrogenated bisphenol S (poly) propoxy di (meth) acrylate. It is done.
  • a (meth) acrylate compound having two or more functional groups having an alicyclic hydrocarbon skeleton a (meth) acrylate compound having a structure represented by the following formula (3) is preferably used. be able to.
  • R 3 represents the following formula (7).
  • R 2 is the same as above, and * is bonded to the cyclic skeleton.
  • Specific examples of the (meth) acrylate compound of the above formula (3) include alicyclic (meth) acrylates such as tricyclodecane dimethanol di (meth) acrylate.
  • the content of the (meth) acrylate compound having two or more functional groups having an alicyclic hydrocarbon skeleton in the resin composition is usually preferably 10 to 90 parts by mass with respect to 100 parts by mass of the resin composition. 20 to 80 parts by mass is more preferable, and 30 to 70 parts by mass is particularly preferable.
  • Examples of the (meth) acrylate compound (B) having two or more functional groups having a heterocyclic skeleton include isocyanuric acid EO-modified di (meth) acrylate, ⁇ -caprolactone-modified tris ((meth) acryloxyethyl) isocyanurate, Isocyanuric acid EO-modified di and triacrylate, hydroxypivalaldehyde-modified trimethylolpropane di (meth) acrylate, spiroglycol di (meth) acrylate and the like.
  • 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, spiroglycol skeleton as examples of the heterocyclic ring.
  • a (meth) acrylate compound having a structure represented by the following formula (10) can be used.
  • each R 10 independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group
  • R 11 represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms
  • X represents A nitrogen atom, an oxygen atom or a methylene group
  • Y represents a methylene group or a carbonyl group
  • m represents an integer of 1 to 4, provided that X does not all become a methylene group.
  • a compound represented by the following formula (9) can be preferably used.
  • each R 8 independently represents a direct bond, an alkylene group having 1 to 6 carbon atoms or an alkyleneoxy group.
  • Each R 9 independently represents a hydrogen atom or an alkylene group having 1 to 4 carbon atoms.
  • Z represents a methylene group, an oxygen atom or a nitrogen atom.
  • the content of the (meth) acrylate compound having two or more functional groups having a heterocyclic skeleton in the resin composition is usually preferably 10 to 90 parts by mass, preferably 20 to 80 parts per 100 parts by mass of the resin composition. Part by mass is more preferable, and 30 to 70 parts by mass is particularly preferable.
  • the molecular weight of the (meth) acrylate monomer that can be used for film formation is preferably 100 to 1,000. More preferred is 120 to 700, and 150 to 400 is particularly preferred. This is because it is difficult to vaporize a monomer having a large molecular weight. If the evaporating easiness between the constituent resins is greatly different, the resin composition ratio in the evaporator may change. In addition, if the material is difficult to vaporize, the productivity is deteriorated, and as a result, the tact time is increased, which may increase the cost.
  • polymerization initiator (C) used in the present invention the following polymerization initiators can be used.
  • polymerization initiator examples 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- [4- ( Acetophenones such as methylthio) phenyl] -2-morpholinopropan-1-one and oligo [2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone]; 2-ethylanthraquinone, 2 -T Anthraquinones such as rt-butylanthraquinone, 2-chloro
  • an LED lamp may be used as a light source for photocuring for the purpose of minimizing damage to other materials.
  • LED lamps are considered to have lower irradiation energy than high-pressure mercury lamps and metal halide lamps.
  • the emission wavelength is 365 nm, 385 nm, 390 nm, 395 nm, 405 nm, etc., but each lamp has an absorption band on a relatively long wavelength side because it is close to visible light. It is necessary to select a photopolymerization initiator.
  • a photopolymerization initiator of phosphine oxides is preferable, and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide is particularly preferable.
  • An acylphosphine oxide photopolymerization initiator is particularly preferred.
  • the content of the component (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 component (A) and the component (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.
  • the (meth) acrylate monomer monofunctional (meth) acrylate, bifunctional (meth) acrylate, polyfunctional (meth) acrylate having 3 or more (meth) acryloyl groups in the molecule, urethane (meth) acrylate, Epoxy (meth) acrylate, polyester (meth) acrylate, and the like can be used.
  • Examples of monofunctional (meth) acrylates include butanediol (meth) acrylate, hexanediol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth).
  • (Meth) acrylate having hydroxyl group such as acrylate, 4-hydroxybutyl (meth) acrylate, 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, isodecyl (meth) ) Acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, isomyristyl (meth) acrylate, lauryl (meth
  • Examples of the (meth) acrylate monomer having two functional groups include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, (Meth) acrylate having a linear methylene structure such as 1,10-decanediol di (meth) acrylate and polytetramethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) acrylate, (poly) propylene glycol Examples include di (meth) acrylates of polyhydric alcohols such as di (meth) acrylate.
  • Polyfunctional (meth) acrylate monomers include pentaerythritol tri (meth) acrylate, pentaerythritol (poly) ethoxytri (meth) acrylate, pentaerythritol (poly) propoxytri (meth) acrylate, pentaerythritol tetra (meth) acrylate, penta Erythritol (poly) ethoxytetra (meth) acrylate, pentaerythritol (poly) propoxytetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol (poly) caprolactone penta (meth) acrylate, dipentaerythritol (poly) ) Ethoxypenta (meth) acrylate, dipentaerythritol (poly) propoxypenta (meth
  • urethane (meth) acrylate examples 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, bisphenol A polypropoxydiol Etc.) or polyesters that are the reaction product of these diol compounds
  • Epoxy (meth) acrylates include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, terminal glycidyl ether of bisphenol A propylene oxide adduct, fluorene epoxy resin, bisphenol S type epoxy resin, etc.
  • the reaction material of resin and (meth) acrylic acid etc. can be mentioned.
  • polyester (meth) acrylate examples include a polyester diol which is a reaction product of a diol compound and a dibasic acid or an anhydride thereof, and a reaction product of (meth) acrylic acid.
  • the content of the (meth) acrylate monomer other than the components (A) and (B) in the resin composition is usually preferably 5 to 95 parts by mass with respect to 100 parts by mass of the resin composition. 80 parts by mass is more preferable, and 20 to 70 parts by mass is particularly preferable.
  • the resin composition of the present invention may contain a compound having an oxetane ring.
  • a compound having an oxetane ring known compounds can be used without particular limitation.
  • the content of the oxetane compound in the resin composition is usually preferably 5 to 95 parts by mass, more preferably 10 to 80 parts by mass, and particularly preferably 20 to 70 parts by mass with respect to 100 parts by mass of the resin composition.
  • the resin composition of the present invention can appropriately contain a compound having an epoxy group.
  • the compound having an epoxy group include a monofunctional epoxy compound, a polyfunctional epoxy compound, and an alicyclic epoxy.
  • Examples of the monofunctional epoxy compound include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, and 1,3-butadiene monooxide.
  • 1,2-epoxydodecane epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, 3-vinylcyclohexene oxide, etc. It is done.
  • polyfunctional epoxy compounds include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S di Glycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-methane-dioxane, bis (3,4-epoxycyclo Xylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexan
  • Examples of the alicyclic epoxy include a compound containing cyclohexene oxide or cyclopentene oxide. Specific examples of the alicyclic epoxy include compounds having the following structure.
  • n is an average value and represents a positive number of 1 to 5.
  • the content of the component (B) of the present invention is preferably 0 to 70 parts by mass, more preferably 20 to 70 parts by mass with respect to 100 parts by mass of the total amount of the component (A) + component (B) as the reactive compound. Particularly preferred is 25 to 50 parts by mass.
  • the epoxy equivalent is preferably 50 to 500 g / eq, more preferably 100 to 300 g / eq.
  • a polymerization initiator such as a photocationic polymerization initiator.
  • the photocationic initiator include aromatic iodonium complex salts and aromatic sulfonium complex salts.
  • aromatic iodonium complex salt examples include diphenyliodonium tetrakis (pentafluorophenyl) borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di (4-nonylphenyl) iodonium hexafluorophosphate, and the like.
  • aromatic phonium complex salt examples include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, 4,4′-bis [diphenylsulfonio] diphenyl sulfide- Bishexafluorophosphate, 4,4′-bis [di ( ⁇ -hydroxyethoxy) phenylsulfonio] diphenylsulfide-bishexafluoroantimonate, 7- [di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoro Phosphate, 7- [Di (p-toluyl) sulfonio] -2-isopropylthioxanthone hexafluoro Phos
  • aromatic sulfonium salts thiophenyldiphenylsulfonium hexafluoroantimonate, 4- ⁇ 4- (2-chlorobenzoyl) phenylthio ⁇ phenylbis (4-fluorophenyl) sulfonium hexafluoro, which is highly sensitive and easily available from the market Antimonate, diphenyl [4- (phenylthio) phenyl] sulfonium trifluorotrispentafluoroethyl phosphate, tris [4- (4-acetylphenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide and the like are preferable.
  • phenylsulfanyl) phenyl] sulfonium tris [(trifluoromethyl) sulfonyl] methanide is used.
  • the content of the cationic photopolymerization initiator is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the total amount of the oxetane resin and the epoxy resin component.
  • a photocationic polymerization initiator may be used independently and may be used in mixture of multiple types.
  • 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
  • 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 mass or less, and 1.0% by mass or less with respect to the resin composition. Is more preferable, and 0.5% by mass or less is particularly preferable.
  • An organometallic compound such as alkylaluminum can also be added to reduce the water vapor permeability.
  • a solvent can be added, it is preferable to add no solvent in order to bring about a decrease in the degree of vacuum.
  • the substrate on which the resin layer is formed is not particularly limited, and PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PEN (polyethylene naphthalate), TAC (triacetyl cellulose), PC (polycarbonate) ), PI (polyimide), various resin films such as PMMA (polymethyl methacrylate), various metal sheets such as aluminum sheets, glass substrates, etc., as long as the monomer layer can be formed, gas barrier film, optical Various base films used for various functional films such as films and protective films can be used.
  • a glass substrate is often used for organic EL display applications. In order to produce a flexible organic EL display, the base material must also be flexible, and since high dimensional stability and heat resistance are required, thin film glass base materials, PEN, PI, or those Often composite materials are used.
  • Examples of the method for depositing the resin composition of the present invention on a substrate include an ink jet method, a roll coat method, a spin coat method, a die coat method, and a vapor deposition method.
  • the vapor deposition method is preferable.
  • the vapor deposition apparatus used in the vapor deposition method includes at least a step of supplying a liquid resin composition to an evaporator, a step of vaporizing the resin composition with the evaporator, and a step of discharging the vaporized resin composition. It is preferable to include means for supplying and depositing a resin composition on a substrate and curing the deposited resin composition.
  • the means for performing the supply step may be any system that can supply a certain amount of the resin composition to the evaporator, but it is preferable to control the supply amount with a dispenser or an inkjet. Particularly preferred is an ink jet supply.
  • An inkjet head includes a thermal type including an actuator that generates heat, and a piezoelectric type that vibrates by applying a voltage. In the present invention, the piezoelectric type is preferable. This is because the durability of the head and the controllability of the supplied resin are excellent.
  • the means for performing the vaporizing step is preferably such that the evaporator can adjust the internal pressure, and the internal pressure is preferably 0.01 Torr to 10 Torr. More preferably, it is 0.1 Torr to 1 Torr. Further, the evaporator is preferably capable of adjusting the internal temperature, and the internal temperature is preferably 100 to 300 ° C. More preferably, it is 200 to 250 ° C.
  • a means for performing the discharging step and the depositing step can discharge a certain amount of the vaporized resin composition from the evaporator and deposit it on a single wafer or a continuously running substrate to obtain a uniform resin layer.
  • the resin layer is usually preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 1 to 5 ⁇ m. By setting it as preferable thickness, the intensity
  • the light source to be cured is energy rays
  • the energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X-rays, gamma rays, laser rays, alpha rays, Examples thereof include particle beams such as beta rays and electron beams.
  • ultraviolet rays, laser beams, visible rays, or electron beams are preferred in the present invention.
  • Particularly preferred is ultraviolet light or visible light
  • examples of the light source include a high-pressure mercury lamp, a metal halide lamp, and an LED lamp. When it is necessary to consider power saving and damage to organic materials, an LED lamp with less heat generation 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.
  • 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 not particularly limited, but a low viscosity may be required because a nozzle using a piezo element may be used when supplying the resin into the vacuum chamber.
  • a composition having a viscosity of 200 mPa ⁇ s or less at 25 ° C. measured using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.) is preferable. More preferably, it is 50 mPa * s or less, Especially preferably, it is 20 mPa * s.
  • 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 preferably from 1.45 to 1.55, more preferably from 1.47 to 1.54.
  • the refractive index can be measured with an Abbe refractometer (model number: DR-M2, manufactured by Atago Co., Ltd.).
  • the ultraviolet curable resin composition and cured product of the present invention were obtained with the compositions shown in Table 1 below.
  • the evaluation methods and evaluation criteria for the physical properties of the resin composition and cured film shown in Table 1 are as follows.
  • Synthesis Example 1 and Synthesis Example 2 in Table 1 were synthesized by the following method.
  • the physical property values in the synthesis examples were measured by the following methods. [Epoxy equivalent] Measured by the method described in JIS K7236: 2001.
  • Synthesis Example 2 Synthesis of binaphthol polyethoxydiacrylate
  • 286.3 g (1.0 mol) of 1,1′-bi-2-naphthol and 264 of ethylene carbonate were added.
  • 41.5 g (0.3 mol) of potassium carbonate, and 2000 ml of toluene were charged and reacted at 110 ° C. for 12 hours.
  • the resulting reaction solution was washed with water and 1% NaOH aqueous solution, and then washed with water until the washing water became neutral.
  • Viscosity Viscosity was measured at 25 ° C. using an E-type viscometer (TV-200: manufactured by Toki Sangyo Co., Ltd.).
  • Liquid refractive index (25 ° C.) The refractive index (25 ° C.) of the prepared energy ray curable resin was measured with an Abbe refractometer (DR-M2: manufactured by Atago Co., Ltd.).
  • Tg glass transition point
  • Plasma damage An ultraviolet curable resin composition was applied to a glass substrate with a film thickness of 3 ⁇ m, a sample was cut into 1 cm square, and TDS (temperature programmed desorption gas analyzer) measurement before and after UV treatment was performed.
  • the UV treatment conditions were a wavelength of 170 nm, an illuminance of 2.3 mW / cm 2 , and an irradiation time of 5 minutes.
  • TDS measurement conditions WA1000S manufactured by Electronic Science Co., Ltd. was used, the heating rate was 10 ° C./min, 60 ° C. to 300 ° C., and heating was performed by IR.
  • FANCLIL (trade name) FA-BZA: benzyl acrylate, Hitachi Chemical Co., Ltd. New Frontier (trade name) PHE: Phenol monoethoxy acrylate, Daiichi Kogyo Seiyaku Co., Ltd. Aronix (trade name) M117: Nonylphenol polypropoxy Acrylate, Toagosei Co., Ltd. Biscoat (trade name) # 150: Tetrahydrofurfuryl acrylate, Osaka Organic Chemical Industry Co., Ltd. Biscoat (trade name) # 155: Cyclohexyl acrylate, Osaka Organic Chemical Industry Co., Ltd.
  • KAYARAD Product name
  • OPP-1 o-phenylphenol monoethoxy acrylate
  • KAYARAD R-604 manufactured by Nippon Kayaku Co., Ltd .
  • KAYARAD R-684 hydroxypivalaldehyde-modified trimethylolpropane diacrylate
  • Tricyclodecane dimethylol diacrylate Nippon Kayaku Co., Ltd.
  • New Frontier BPE-4A Bisphenol A tetraethoxydiacrylate, Daigaku Kogyo Seiyaku
  • Irgacure (trade name) 819 Bis (2, 4, 6 -Trimethylbenzoyl) -phenylphosphine oxide, Irgacure TPO manufactured by BASF Japan K.K .: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, Irgacure 369 manufactured by BASF Japan K.K .: 2-benzyl-2-dimethyl Amino-1- (4-morpholinophenyl) -butanone-1, Irgacure 184: 1-hydroxycyclohexyl-phenylketone manufactured by BASF Japan, HDDA manufactured by BASF Japan: 1,6-hexanedio Rudiacrylate, Bremer (trade name) AE-400 manufactured by Daicel-Cytec Co., Ltd .: Polyethylene glycol acrylate, KAYARAD DPHA
  • the resin composition of the present invention having a specific composition is excellent in processability, has a low curing shrinkage rate, and has low plasma damage. Therefore, it is suitable for, for example, an organic film for various barrier substrates, particularly a resin composition for film sealing of an organic EL element.
  • the resin composition of the present invention and its cured product are excellent in visible light transmittance and processability, have a low curing shrinkage rate and good substrate adhesion.
  • the plasma damage is small, it is suitable for various barrier materials, in particular, film sealing materials for organic EL elements.

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CN105432142B (zh) 2018-03-13
KR20160030077A (ko) 2016-03-16
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