WO2015002100A1 - Organic el element - Google Patents

Organic el element Download PDF

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Publication number
WO2015002100A1
WO2015002100A1 PCT/JP2014/067245 JP2014067245W WO2015002100A1 WO 2015002100 A1 WO2015002100 A1 WO 2015002100A1 JP 2014067245 W JP2014067245 W JP 2014067245W WO 2015002100 A1 WO2015002100 A1 WO 2015002100A1
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group
organic
compound
moisture
formula
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PCT/JP2014/067245
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French (fr)
Japanese (ja)
Inventor
高橋　昌之
新井　隆之
奈美 鬼丸
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Jsr株式会社
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Priority claimed from JP2014105708A external-priority patent/JP6467785B2/en
Priority claimed from JP2014109420A external-priority patent/JP6357877B2/en
Priority claimed from JP2014110475A external-priority patent/JP6323171B2/en
Application filed by Jsr株式会社 filed Critical Jsr株式会社
Priority to KR1020157031460A priority Critical patent/KR20160030080A/en
Priority to CN201480031663.8A priority patent/CN105307753A/en
Publication of WO2015002100A1 publication Critical patent/WO2015002100A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/26—Drying gases or vapours
    • B01D53/28—Selection of materials for use as drying agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/871—Self-supporting sealing arrangements
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/874—Passivation; Containers; Encapsulations including getter material or desiccant

Definitions

  • the present invention relates to an organic EL element.
  • organic electroluminescence (EL) element is known as one of electronic devices that have been actively developed.
  • the organic EL element is a simple device having a basic structure of a laminated structure composed of an anode / organic light emitting layer / cathode, but has a problem that the organic light emitting layer is easily affected by moisture.
  • the organic EL element needs to be used in a state where moisture in the element is removed and sealed, but it is difficult to completely seal such an electronic device by sealing.
  • an organic EL element has been proposed in which a moisture trapping agent made of a specific organometallic compound is placed in the element in advance, and the moisture trapping agent traps moisture to keep the inside of the element in a low humidity environment (for example, (See Patent Document 1).
  • the organoaluminum compounds exemplified as the moisture scavenger in Patent Document 1 and the like are very reactive and may react with moisture in the air. Therefore, handling in air is difficult, and when using a conventional moisture scavenger, handling under air or nitrogen controlled to a sufficiently low humidity has been essential. And when manufacturing an organic EL element using the conventional moisture capture agent, the manufacturing process became complicated, for example, an operation in a low humidity atmosphere was required.
  • a moisture trapping member that can be handled under normal air and can be used in the manufacture of electronic devices such as organic EL elements.
  • an organic EL element that includes a moisture trap that can remove moisture in the element and reduce moisture intrusion into the element and handle it under air.
  • an object of the present invention is to provide a moisture trap that can be handled under air in an electronic device such as an organic EL element and a liquid crystal display element, which removes moisture in the element and reduces moisture intrusion into the element. And providing an organic EL device including the moisture trap.
  • the present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by an organic EL element having the following configuration, and have completed the present invention.
  • the present invention relates to the following [1] to [5].
  • An organic EL device comprising a moisture trap,
  • the moisture trap is (A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound; (B) at least one compound selected from the group consisting of an acid generator and a base generator; (C) An organic EL device comprising a curable compound.
  • the compound (A) is (A1) at least one compound selected from a compound represented by formula (A1-1), a compound represented by formula (A1-2), and a compound represented by formula (A1-3); (A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and (A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected, The organic EL device according to [1], wherein the compound (B) is an acid generator.
  • R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or a carbon number.
  • An organic group of 1 to 18, and R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure, and n is 0 or an integer of 1 to 18 * Represents a bonding position
  • R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 8 is independently an organic group having 3 to 30 carbon atoms. There; wherein (A1-3), wherein R 8 has the same meaning as in formula (A1-2).
  • X is a silicon atom, a titanium atom or a zirconium atom
  • R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms
  • R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent.
  • Group optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group; p is an integer from 0 to 6; r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
  • the compound (A) is (A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and (A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected,
  • X is a silicon atom, a titanium atom or a zirconium atom
  • R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms
  • R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent.
  • Group optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group; p is an integer from 0 to 6; r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
  • a moisture trap that removes moisture in the element and reduces moisture intrusion into the element and can be handled in the air is used. It is possible to provide an organic EL element such as an organic EL illumination or an organic EL display element that can suppress the generation of dark spots even when driven for a long time.
  • the organic EL device of the present invention includes the moisture trap of the present invention.
  • the moisture trap of the present invention is formed using the moisture trap forming composition of the present invention.
  • the moisture trap forming composition of the present invention for forming the moisture trap of the present invention will be described, the moisture trap of the present invention formed using the moisture trap forming composition, and this moisture trap.
  • the organic EL device of the present invention having the above will be described.
  • the moisture trap forming composition of the present invention has at least one compound selected from the group consisting of a compound having a hydrolyzable group, and at least one type selected from the group consisting of an acid generator and a base generator. Contains a compound and a curable compound.
  • At least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate, at least one compound selected from the group consisting of an acid generator and a base generator , And the curable compound are also referred to as a moisture trapping agent (A), an acid / base generator (B), and a curable compound (C), respectively.
  • the moisture trapping agent (A), the acid / base generator (B) ) And curable compound (C) are also referred to as component (A), component (B) and component (C), respectively.
  • component (A), component (B) and component (C) respectively.
  • the moisture trapping agent (A) is, for example, a compound having a hydrolyzable structure, that is, a hydrolyzable group in the presence of an acid or a base.
  • the moisture trapping agent (A) include at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), Carboxylic anhydride (A2), and at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) may be mentioned.
  • Each of these compounds (A1) to (A3) may be used alone or in combination of two or more.
  • the compounds (A1) to (A3) are also referred to as moisture trapping agents (A1) to (A3), respectively.
  • the moisture trapping agent (A1) is at least one compound selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2).
  • the moisture trapping agent (A1) is stable with low reactivity with water under neutral and basic conditions, but easily causes hydrolysis reaction in the presence of an acid.
  • R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or 1 carbon atom.
  • R 3 , R 4 and R 7 together with the carbon atoms to which they are directly bonded may form a cyclic structure
  • n is 0 or an integer from 1 to 18 Yes
  • * indicates a bond position.
  • R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • each R 8 is independently an organic group having 3 to 30 carbon atoms.
  • Examples of the “organic group having 1 to 18 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, decyl.
  • a linear or branched alkyl group having 1 to 18 carbon atoms such as dodecyl and octadecyl, preferably an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms such as cyclohexyl and methylcyclohexyl; C4-C18 cycloalkyl group-substituted alkyl groups such as cyclohexylmethyl and cyclohexylethyl; phenyl groups; phenyl-substituted alkyl groups such as benzyl and phenethyl groups; aralkyl groups having 7 to 18 carbon atoms; A group in which a part of the group is substituted with an oxygen atom (hereinafter also referred to as “oxygen atom substituent”); Group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group,
  • oxygen atom substituents examples include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl; alkanoyloxyalkyl groups such as acetoxymethyl and acetoxyethyl; aryloxy such as phenoxymethyl and phenoxyethyl An alkyl group; an alkoxy group such as methoxy; an aryloxy group such as phenoxy; and a hydroxyalkyl group such as hydroxymethyl.
  • the total number of carbon atoms of the groups represented by R 2 , R 3 , R 4 , R 5 , R 6 and R 7 (when n is 0, R 2 to R 5 are
  • the total number of carbon atoms of the groups represented is preferably 0 to 18, more preferably 0 to 12, from the viewpoint of water absorption ability and solubility.
  • R 3 , R 4 and R 7 in the above formula (A1-1) form a cyclic structure together with the carbon atoms to which they are directly bonded. You may do it.
  • the cyclic structure include a cyclohexane ring and a cyclopentane ring.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.
  • R 2 to R 5 are each independently a hydrogen atom, the aforementioned alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a group having 4 to 18 carbon atoms. It is preferably a cycloalkyl group-substituted alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, or an oxygen atom substituent, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, More preferably.
  • R 6 to R 7 are each independently a hydrogen atom, a hydroxyl group, the above-described alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 4 to 4 carbon atoms.
  • R 1 to R 7 in the above formula (A1-1) are preferably the above atoms or groups from the viewpoint of the water absorption ability of the moisture trapping agent (A) and compatibility with other components.
  • n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1.
  • R 6 and R 7 may be the same or different.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
  • R 8 is preferably independently a group represented by the above formulas g1 to g7. .
  • Examples of the compound having a structural moiety represented by the formula (A1-1) include a compound represented by the following formula. More specifically, as will be described later, a compound obtained by reacting an ortho ester (a1), a polyhydric alcohol (a2) and a hydroxyl group-containing compound (a3) can be mentioned, and specific examples thereof include: Examples thereof include compounds represented by the following formula (A1-i), formula (A1-ii), and formula (A1-iii).
  • A is a structural moiety represented by the formula (A1-1);
  • Y is a hydroxyl group-containing compound (a3) described later having p (p ⁇ 2) hydroxyl groups in one molecule.
  • a residue excluding m (2 ⁇ m ⁇ p) hydroxyl groups; m is an integer of 2 to p.
  • the compound having a structural moiety represented by the formula (A1-1) can be obtained, for example, by reacting an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) described below.
  • an ortho ester (a1) a polyhydric alcohol (a2)
  • a hydroxyl group-containing compound (a3) described below.
  • the ortho ester (a1) is a compound represented by the following formula (a1).
  • R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; each of three Rxs is independently an organic group having 1 to 18 carbon atoms.
  • the organic group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a substituted alkyl group having 4 to 18 carbon atoms.
  • a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
  • Examples of the orthoester (a1) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, orthobutyric acid. Ethyl is mentioned. Among these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate are preferable.
  • Ortho ester (a1) may be used alone or in combination of two or more.
  • Polyhydric alcohol (a2) examples include a compound having two or more hydroxyl groups in one molecule, and a compound represented by the formula (a2-1) is preferable. Specific examples include ⁇ -glycol having two hydroxyl groups in one molecule, and a compound having two or more hydroxyl groups in one molecule other than ⁇ -glycol.
  • R 2 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms.
  • R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms.
  • R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure.
  • R 2 to R 7 in formula (a2-1) are synonymous with the same symbols in formula (A1-1), and preferred examples are also the same as those described in formula (A1-1).
  • n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1.
  • R 6 and R 7 may be the same or different.
  • ⁇ -glycol in which n is 0 is preferable.
  • ⁇ -Glycol has two adjacent hydroxyl groups. Therefore, the reaction between the ortho ester and ⁇ -glycol proceeds efficiently, which is suitable for the production of a moisture scavenger.
  • Examples of ⁇ -glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dodecanediol, 1,2- Hydrolyzate of dihydroxycyclohexane, pinacol, long-chain alkyl monoepoxide; fatty acid monoglycerides ( ⁇ form) such as glycerin monoacetate ( ⁇ form), glycerin monostearate ( ⁇ form); 3-ethoxypropane-1,2-diol , 3-phenoxypropane-1,2-diol.
  • ethylene glycol, 1,2-propylene glycol, and 1,2-hexanediol are preferable.
  • a compound in which n is 1 is particularly preferable.
  • the compound has two or three or more hydroxyl groups in close proximity like the ⁇ -glycol described above. Therefore, the reaction between the ortho ester and the compound proceeds efficiently, which is suitable for the synthesis of the ortho ester compound (A1-1).
  • Examples of the compound in which n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2- Ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propane Diol, (2-allyloxymethyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, glycerin, 2-phenoxypropane-1,3-diol Diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylo
  • neopentyl glycol 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexane Diol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, (2-allyloxy Particularly preferred are methyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol and glycerin.
  • the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule.
  • the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, from the polyhydric alcohol (a2) such as a compound represented by the formula (a2-1)
  • a hydroxyl group-containing compound (a3) can also be selected and used.
  • the compound selected as the hydroxyl group-containing compound (a3) is selected from compounds other than the compound selected as the polyhydric alcohol (a2).
  • Examples of the hydroxyl group-containing compound (a3) include a compound having 2 hydroxyl groups in one molecule and a compound having 3 or more, preferably 3 to 40 hydroxyl groups in one molecule.
  • Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, and 3-methyl.
  • Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxy).
  • the hydroxyl group-containing compound (a3) is preferably a compound having a molecular weight in the range of 90 to 100,000, particularly 90 to 5,000.
  • the hydroxyl group-containing compound (a3) is preferably a compound having a hydroxyl value in the range of 20 mgKOH / g to 1850 mgKOH / g, particularly 40 mgKOH / g to 1650 mgKOH / g.
  • reaction ratio In the case of producing the ortho ester compound (A1-1) by reacting the ortho ester (a1), the polyhydric alcohol (a2) and the hydroxyl group-containing compound (a3), the ortho ester (a1) and the polyhydric alcohol are produced.
  • the blending ratio of (a2) and the hydroxyl group-containing compound (a3) is not particularly limited.
  • the amount of the orthoester (a1) is 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, more preferably 0.1 mol, relative to 1 mol equivalent of the hydroxyl group in the hydroxyl group-containing compound (a3).
  • the amount of the polyhydric alcohol (a2) is 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, more preferably 0.1 mol to 2 mol. Use in a proportion within the range is appropriate from the standpoint of ease of molecular weight control.
  • the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2)
  • the compound selected as the hydroxyl group-containing compound (a3) is a compound other than the compound selected as the polyhydric alcohol (a2). Selected.
  • the moisture trapping agent (A1) can be obtained by subjecting three components of an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) to a condensation reaction.
  • the above-mentioned three components are usually added in the presence of an organic solvent and an acid catalyst such as formic acid as necessary, usually at room temperature to 250 ° C., preferably 70 ° C. to 200 ° C. for 1 hour to 20 It can be preferably produced by heating for about an hour to cause a condensation reaction.
  • International Publication No. 01/021611 pamphlet can be referred to.
  • the water scavenger having a structure in which the hydroxyl group in the hydroxyl group-containing compound (a3) is blocked by a 5-membered ring or a 6-membered ring formed from the ortho ester (a1) and the polyhydric alcohol (a2). (A1) can be obtained.
  • Examples of the compound having a structural moiety represented by the formula (A1-1) include, for example, compounds represented by the formula (A1-i), the formula (A1-ii), and the formula (A1-iii). It is done.
  • the compound represented by the formula (A1-i) includes, for example, the orthoester of the above formula (a1), the polyhydric alcohol of the above formula (a2-1), and 2 to 6 hydroxyl groups in one molecule described above. It can synthesize
  • Y 2 is a divalent residue obtained by removing two hydroxyl groups from a compound having two hydroxyl groups in one molecule.
  • R 1 ⁇ R 7 and n have the same meanings as R 1 ⁇ R 7 and n in formula (A1-1).
  • the above compound is synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a hydroxyl group-containing compound (a3) having two hydroxyl groups in one molecule as raw materials. can do.
  • Y 3 is a tetravalent residue obtained by removing four hydroxyl groups from a compound having four hydroxyl groups in one molecule.
  • R 1 ⁇ R 7 and n have the same meanings as R 1 ⁇ R 7 and n in the formula (A1-1).
  • the compound include, as a raw material, an ortho ester of the above formula (a1), a polyhydric alcohol of the above formula (a2-1), and a hydroxyl group-containing compound (a3) compound having four hydroxyl groups in one molecule described above. By using it, it can be synthesized.
  • the moisture trapping agent (A2) is a carboxylic acid anhydride, and examples thereof include monocarboxylic acid anhydrides, dicarboxylic acid anhydrides, and tetracarboxylic dianhydrides.
  • the moisture scavenger (A2) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.
  • Examples of monocarboxylic acid anhydrides include trifluoroacetic anhydride, benzoic anhydride, isatoic anhydride, isopentanoic anhydride, isobutyric anhydride, n-valeric anhydride, crotonic anhydride, and the like.
  • the carbon number of the monocarboxylic acid anhydride is preferably 4 to 20, more preferably 4 to 14, from the viewpoint of the volatility of the carboxylic acid that can be generated by hydrolysis.
  • dicarboxylic anhydride examples include compounds represented by the following formula (A2-1).
  • Ra is a divalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and “an aromatic group is Non-condensed polycyclic aromatic groups connected to each other directly or by a bridging member (eg —O—, —CO—, —S—, —SO 2 —, an alkylene group, —C (CF 3 ) 2 —) Is a divalent group selected from The carbon number of Ra is usually 1-30, but is preferably 4-30, more preferably 6-18, from the viewpoint of the volatility of the dicarboxylic acid that can be produced by hydrolysis.
  • a bridging member eg —O—, —CO—, —S—, —SO 2 —, an alkylene group, —C (CF 3 ) 2 —
  • dicarboxylic acid anhydride examples include aliphatic dicarboxylic acid anhydrides, alicyclic dicarboxylic acid anhydrides, and aromatic dicarboxylic acid anhydrides.
  • aliphatic dicarboxylic acid anhydrides include, for example, anhydrides of aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; maleic acid, Examples thereof include anhydrides of aliphatic unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, mesaconic acid and citraconic acid.
  • alicyclic dicarboxylic acid anhydride examples include alicyclic dicarboxylic acid anhydrides such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and 4-methylcyclohexanedicarboxylic acid anhydride. .
  • aromatic dicarboxylic acid anhydride refers to a dicarboxylic acid anhydride of an organic compound in which at least two carboxyl groups are bonded to an aromatic ring.
  • aromatic dicarboxylic acid anhydride include phthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 2,3-dicarboxyphenyl phenyl ether, 3,4-dicarboxyphenyl phenyl ether, 2,3-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid, 2,3-dicarboxyphenylphenylsulfone, 3,4-dicarboxyphenylphenylsulfone, 2,3-dicarboxyphenylphenylsulfide, 3,4- Dicarboxyphenyl phenyl sulfide, 1,2-naphthalenedicarboxylic acid, 2,3-n
  • the dicarboxylic anhydride that is the moisture trapping agent (A2) may be used alone or in combination of two or more.
  • tetracarboxylic dianhydride examples include compounds represented by the following formula (A2-2).
  • Rb represents a tetravalent organic group such as an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an “aromatic group”.
  • Non-condensed polycyclic aromatics in which they are connected to each other directly or by a bridging member eg —O—, —CO—, —S—, —SO 2 —, an alkylene group, —C (CF 3 ) 2 —
  • Rb usually has 4 to 100 carbon atoms, but preferably 4 to 30 and more preferably 4 to 18 from the viewpoint of volatility of tetracarboxylic acid that can be generated by hydrolysis.
  • Examples of the tetracarboxylic dianhydride described above include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides.
  • Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5
  • R 11 and R 13 are divalent organic groups having an aromatic ring;
  • R 12 and R 14 are a hydrogen atom or an alkyl group A plurality of R 12 and R 14 may be the same or different.
  • An aromatic tetracarboxylic dianhydride means a tetracarboxylic anhydride of an organic compound in which at least four carboxyl groups are bonded to an aromatic ring.
  • Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfone.
  • Tetracarboxylic dianhydride 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′ , 4,4′-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) dipheny Sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′
  • the tetracarboxylic dianhydride that is the moisture trapping agent (A2) may be used alone or in combination of two or more.
  • the moisture trapping agent (A3) is at least one selected from a compound represented by the formula (A3-1) and a compound represented by the formula (A3-2).
  • the moisture trapping agent (A3) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.
  • X represents a silicon atom, a titanium atom, or a zirconium atom. Among these, a silicon atom is preferable.
  • R 21 is at least one selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, and an isocyanate group.
  • An organic group having the above group an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group.
  • R 22 is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number 3 -12 cycloalkyl group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group Or a mercapto group.
  • r is an integer of 0 to 2; p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3 preferable.
  • s is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
  • Examples of the organic group for R 21 in formulas (A3-1) and (A3-2) include groups represented by the following formulae.
  • * represents a bonding position
  • R 23 is a hydrogen atom or a methyl group
  • R 24 is an alkylene group having 1 to 3 carbon atoms
  • n is an integer of 1 to 3.
  • alkyl group for R 21 in the above formula (A3-1) and the above formula (A3-2) may be either linear or branched, and for example, methyl, ethyl, n-propyl, isopropyl, n Examples include -butyl, isobutyl, t-butyl, pentyl, and hexyl.
  • Examples of the cycloalkyl group include cyclohexyl.
  • the alkyl group in R 22 is any of linear, branched and cyclic Good.
  • the alkyl group in R 22 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.
  • examples of the aromatic hydrocarbon group for R 22 in the above formula (A3-1) and the above formula (A3-2) include monocyclic to tricyclic aromatic hydrocarbon groups. Include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferable, and a phenyl group is more preferable.
  • the alkyl group, cycloalkyl group and aromatic hydrocarbon group in R 22 in the above formula (A3-1) and the above formula (A3-2) may have a substituent.
  • substituents include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms.
  • the position and number of substituents are arbitrary, and when it has two or more substituents, the substituents may be the same or different.
  • the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among these, a fluorine atom is preferable.
  • the halogen atom can substitute a part or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aromatic hydrocarbon group, but preferably all are substituted.
  • Specific examples of the halogen-substituted alkyl group and the halogen-substituted cycloalkyl group include perfluoroalkyl groups such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorocyclopropyl group, and perfluoroalkyl groups.
  • a cycloalkyl group is mentioned.
  • Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group.
  • the (meth) acryloyloxy group in R 22 described above is a concept including an acryloyloxy group and a methacryloyloxy group.
  • R 22 is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth) acryloyloxy group, or a glycidoxy group.
  • R2 when two or more R2 exists in the same molecule, they may be the same or different.
  • More specific examples of the compound represented by the above formula (A3-1) and the compound represented by the above formula (A3-2) which are moisture trapping agents (A3) include silane compounds wherein X is a silicon atom Can be mentioned.
  • examples of the silane compound in which r is 0 and s is 1 include two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane.
  • Alkoxysilane compounds having two C6-C14 aromatic hydrocarbon groups such as diphenyldimethoxysilane; 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyl (Meth) acryloylo such as oxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane Alkoxysilane compounds having a silyl group and an alkyl group having 1 to 20 carbon atoms; 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldiethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-acryl
  • examples of the silane compound in which r is 1 and s is 1 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxy Alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-iso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane
  • An alkoxysilane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane
  • an aromatic hydrocarbon group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltrie
  • examples of the silane compound in which r is 2 and s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxy.
  • examples include silane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane.
  • Examples of the compound represented by the above formula (A3-1) further include compounds represented by the following formula (A3-i), formula (A3-ii) and formula (A3-ii-2).
  • the compounds of formula (A3-i), formula (A3-ii) and formula (A3-ii-2), as exemplified by the following formula have a hydroxyl group and a polymerizable group (oxiranyl group, It can be obtained by reacting a compound having both an oxetanyl group and a (meth) acryloyl group in the presence of an alkali.
  • Examples of the compound represented by the above formula (A3-1) further include compounds represented by the following formulas (A3-iii) and (A3-iv).
  • the compounds of formula (A3-iii) and formula (A3-iv), as shown by the following formula, can be converted to a silane compound having a methoxy group with a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group). Group) and the like, can be obtained by reacting in the presence of an alkali.
  • Examples of the compound represented by the above formula (A3-1) further include a compound represented by the following formula (A3-v).
  • One glycidoxy group such as 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and two alkyl groups having 1 to 20 carbon atoms Having an alkoxysilane compound;
  • Examples thereof include silane compounds having one glycidoxy group and two aromatic hydrocarbon groups having 6 to 14 carbon atoms, such as 3-glycidoxypropyldiphenylmethoxysilane and 3-glycidoxypropyldiphenylethoxysilane.
  • the water-capturing body-forming composition of the embodiment of the present invention contains an acid / base generator (B), and when subjected to at least one of heating and light irradiation, an acid or base is generated from the acid / base generator (B). It is formed.
  • the acid or base is present in the system by promoting the hydrolysis reaction of the water trapping agent (A) based on the water present in the system in which the composition for forming a moisture trap of the present embodiment is used. Water can be consumed with high efficiency. In the present specification, “moisture capture” is used in this sense.
  • the hydrolysis product of the moisture trapping agent (A) is less likely to degrade the performance of electronic devices such as organic EL elements and liquid crystal display elements as will be described later.
  • the moisture trap of the organic EL device when the moisture trap of the organic EL device is formed using the moisture trap forming composition, moisture in the device can be removed with high efficiency. Further, in the moisture trap such as the sealing material formed from the moisture trap forming composition of the embodiment of the present invention, the moisture trap agent (A) or a part of the structure derived therefrom remains partially without being decomposed. it seems to do. For this reason, moisture in the element can be absorbed over a long period of time after the formation, and deterioration of the characteristics of the organic EL element due to moisture can be suppressed.
  • the decomposition products are dispersed in the organic EL element by volatilization or the like, reach the organic EL layer that becomes the light emitting layer of the organic EL element, contaminate, and generate dark spots.
  • the hydrolysis product generated from the moisture trapping agent (A) has an appropriate molecular weight, so that volatilization and the like are suppressed and remain in the moisture trap such as a sealing material. Can do.
  • the hydrolyzed product has a larger molecular size, it tends to stay in the moisture trapping body. Therefore, a compound having a relatively large molecular weight is preferable as the moisture trapping agent (A).
  • the water scavenger (A) used in the embodiment of the present invention hardly generates a highly volatile hydrolysis product such as a low molecular weight alcohol even in a state where water is trapped. Even when it is used for an organic EL element in which a dark spot is likely to be generated due to adhesion of an object, generation of a dark spot due to adhesion of the decomposition product to the organic EL layer can be suppressed.
  • moisture trapping agent (A) moisture trapping agents (A1) to (A3)) is shown below.
  • the hydrolysis reaction of a water trapping agent having a structural site of the formula (i-1) and a water trapping agent having a structural site of the formula (i-2), which are examples of the water trapping agent (A1) is as follows.
  • a chemical reaction formula can be shown.
  • * represents a bonding position. It is considered that an alcohol compound is generated as a hydrolysis product. These alcohol compounds are less volatile and have an appropriate molecular weight.
  • examples of the moisture trapping agent (A2) are a monocarboxylic acid anhydride of the following formula (ii-1), a dicarboxylic acid anhydride of the following formula (ii-2), and a tetracarboxylic acid of the following formula (ii-3).
  • the following chemical reaction formula can be shown for the hydrolysis reaction of acid dianhydride. It is considered that carboxylic acid compounds such as carboxylic acid (ii-1-1), dicarboxylic acid (ii-2-1) and tetracarboxylic acid (ii-3-1) are formed as hydrolysis products. These carboxylic acid compounds are difficult to volatilize and have an appropriate molecular weight.
  • the following chemical reaction formula can be shown for the hydrolysis reaction of the compounds of formula (iii-1) and formula (iii-2), which are examples of the moisture scavenger (A3).
  • As hydrolysis products alcohol compound (iii-1-1) and metal hydroxide (iii-1-2), alcohol compound (iii-2-1) and metal hydroxide (iii-2-2) Generate. Unreacted R 1 O in the metal hydroxide (iii-1-2) can react with water to further generate an alcohol compound (iii-1-1). Alcohol compounds (iii-1-1) and (iii-2-1) can react at the R 21 group and remain in the moisture trap.
  • Metal hydroxides (iii-1-2) and (iii-2-2) can react at the R 22 group and remain in the moisture trap. Further, the metal hydroxides (iii-1-2) and (iii-2-2) are fixedly held in the moisture trap by the R 22 group and scattered in the moisture trap, and the water is recovered by the condensation reaction. Occurrence is prevented.
  • the component (B) is at least one compound (B) selected from the group consisting of an acid generator and a base generator (acid / base generator (B). )).
  • the acid generator and the base generator which are the components (B) of the moisture trap forming composition of the present embodiment, are also referred to as “acid generator (B1)” and “base generator (B2)”, respectively.
  • the water trap forming composition of the embodiment of the present invention contains the acid generator (B1), at least one selected from the water traps (A1) to (A3) is used as the water trap (A). It is done.
  • the water-capturing body forming composition of the embodiment of the present invention contains the base generator (B2), at least one selected from the water-capturing agents (A2) to (A3) is used as the water-capturing agent (A). It is done.
  • Examples of the acid generator (B1) include a radiation sensitive acid generator and a thermal acid generator, and a radiation sensitive acid generator is preferable.
  • Examples of the base generator (B2) include a radiation sensitive base generator and a thermal base generator, and a radiation sensitive base generator is preferred.
  • a radiation-sensitive acid generator and a radiation-sensitive base generator can be defined as compounds capable of releasing an acidic active substance and a basic active substance, respectively, by irradiating them with radiation.
  • the acidic active substance to be released acts as a catalyst when the above-described water trapping agent (A) is subjected to a hydrolysis reaction, for example.
  • the released basic active substance acts as a catalyst when, for example, the above-described moisture trapping agent (A2) and moisture trapping agent (A3) are subjected to a hydrolysis reaction.
  • Examples of the radiation irradiated to decompose the radiation-sensitive acid generator or the radiation-sensitive base generator and generate the cation of the acidic active substance or the anion of the basic active substance include, for example, visible light, ultraviolet light, far ultraviolet light, Examples include X-rays and charged particle beams.
  • ultraviolet rays it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.
  • the content when the component (B) is the acid generator (B1) is preferably 0.001 with respect to 100 parts by mass of the component (A).
  • the amount is from 20 to 20 parts by mass, more preferably from 0.01 to 10 parts by mass.
  • the content when the component (B) is the base generator (B2) is preferably 0.001 with respect to 100 parts by mass of the component (A).
  • the amount is from 20 to 20 parts by mass, more preferably from 0.01 to 10 parts by mass.
  • each of the acid generator (B1) and the base generator (B2) may be used alone or in combination of two or more.
  • Acid generator (B1) for example, light or thermal cation curing catalysts such as iodonium salts, sulfonium salts, phosphonium salts, and anion curing catalysts such as imidazoles and acid anhydrides can be used.
  • a cationic curing catalyst is preferable and a photocationic curing catalyst is more preferable. This is because the curing rate is high and the polymerization reaction does not start unless light is applied, so that the storage stability is good.
  • cation curing catalyst examples include cations such as iodonium, sulfonium and phosphonium substituted with an alkyl group or aryl group, SbF 6 ⁇ , BF 4 ⁇ , B (C 6 F 5 ) 4 ⁇ , and PF 6.
  • P (Rf) n F (6-n) - Rf is, for example, perfluoroalkyl group having 1-8 carbon atoms; n is an integer of 1 to 3), C n F 2n + 1 SO 3 - (n is
  • a salt composed of an anion such as N (SO 2 CF 3 ) 2 ⁇ , C (SO 2 CF 3 ) 3 ⁇ and the like is used.
  • CPI-100P, CPI101A, CPI-200K, CPI-210S and the like manufactured by Sun Apro
  • SunAid registered trademark
  • SI-150L SunAid (registered trademark) SI-110L
  • Sun Aid Registered Trademark
  • SI-80L Sun Aid (Registered Trademark) SI-80L
  • Sun Aid Registered Trademark
  • SI-100L etc.
  • CI series such as Rhodia PI-2074, Nippon Soda CI2920, etc.
  • Optomer (registered trademark) SP series such as registered trade mark SP-150
  • Opton CP series such as CP-66, WPA series and WPI series manufactured by Wako Pure Chemical Industries.
  • B (C 6 F 5 ) 4 ⁇ , P (Rf) n F (6-n) ⁇ , N (SO 2 CF 3 ) 2 — and C (SO 2 CF 3 ) 3 — are preferred, and the cation is preferably a sulfonium cation substituted with an alkyl group or an aryl group from the viewpoint of storage stability.
  • the base generator (B2) is preferably a radiation-sensitive base generator, and the radiation-sensitive base generator is not particularly limited as long as it is a compound that generates a base such as an amine upon irradiation with radiation.
  • the radiation sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, acyloxyiminos, ⁇ , ⁇ -dimethyl-3,5-dimethoxybenzyl carbamates.
  • Transition metal complexes include, for example, bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.
  • orthonitrobenzyl carbamates examples include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy].
  • Acyloxyiminos include, for example, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime may be mentioned.
  • radiation sensitive base generators include bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate and Ilbenzophenone oxime is particularly preferred.
  • the moisture capturing body forming composition of the embodiment of the present invention contains a curable compound (C) as the component (C).
  • the moisture capturing body forming composition of the embodiment of the present invention can increase the crosslinking reactivity by containing the curable compound (C).
  • substrate can be improved.
  • the curable compound (C) is a compound having a polymerizable group.
  • hardenable compound (C) can be used individually or in combination of 2 or more types.
  • Examples of the curable compound (C) include a compound having a cyclic ether group and a compound having a polymerizable double bond.
  • Examples of the compound having a cyclic ether group include a compound having an epoxy group and a compound having an oxetanyl group.
  • the compound having an epoxy group for example, As a monofunctional epoxy compound, Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p- Ethyl phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl, etc.
  • a monofunctional epoxy compound Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidy
  • Polyglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether; 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Glycidyl ethers; Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycer
  • oxetanyl group for example, As monofunctional oxetane compounds, 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dodecyloxymethyl) oxetane, 3 -Ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, etc.
  • monofunctional oxetane compounds 3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) ox
  • the compound having a cyclic ether group is preferably a compound having an epoxy group, more preferably a polyfunctional epoxy compound, and more preferably polyglycidyl ethers of polyhydric alcohols from the viewpoint of enhancing the crosslinking reactivity.
  • Polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are particularly preferable.
  • a compound having an oxygen atom is preferable, and a (meth) acrylate compound is more preferable.
  • Examples of the (meth) acrylate compound include monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds.
  • Examples of the monofunctional (meth) acrylate compound include (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate.
  • polyfunctional (meth) acrylate compound examples include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecanediyl.
  • polyfunctional (meth) acrylate compound for example, biscoat # 195, # 230, same # 260, same # 335HP, same # 540, same # 700 (above, manufactured by Osaka Organic Chemical Industry), TMPT, 9G, 9PG, 701, BPE-500, DCP, DOD-N, HD-N, NOD-N, NPG (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
  • the compound having a polymerizable double bond is preferably a polyfunctional (meth) acrylate compound, more preferably a polyfunctional methacrylate compound, polyethylene glycol dimethacrylate, polypropylene from the viewpoint of enhancing the crosslinking reactivity.
  • Glycol dimethacrylate is more preferred, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferred.
  • the content of the curable compound (C) is preferably 10 parts by mass to 3000 parts by mass, and more preferably 50 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the component (A).
  • the moisture trap forming composition of the embodiment of the present invention is at least one selected from a radical polymerization initiator (D), fine particles (E) and an additive as necessary, as long as the effects of the present invention are not impaired.
  • Other components of the seed may be included.
  • Other optional components may be used alone or in combination of two or more.
  • the radical polymerization initiator (D) and the fine particles (E) may be referred to as component (D) and component (E), respectively.
  • the moisture trap forming composition of the embodiment of the present invention can further contain a radical polymerization initiator (D).
  • the radical polymerization initiator (D) means a compound that generates radicals by actinic rays, heat, acid, or base, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator.
  • the radical polymerization initiator (D) for example, the alcohol compound and the metal alkoxide compound formed by the hydrolysis reaction shown in the above chemical reaction formula are efficiently contained in the moisture trap formed from the composition. It is well fixed and easy to stay.
  • the radical polymerization initiator (D) may be used alone or in combination of two or more.
  • thermal radical polymerization initiator examples include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl- 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′- Azobis [N- (2-propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide) Azo compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide); t-butylperoxybenzoate, 2,5-dimethyl-2,5 Di (t-butylperoxy) peroxides such as hexane and the like.
  • an azo compound is preferable, and dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (N-butyl-2-methylpropion) is preferred. Amide) and 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) are more preferred.
  • Examples of commercially available azo compounds include V-70, V-65, V-601, V-59, V-40, VF-096, V-30, VAm-110, and VAm-111 (above, Wako Pure Chemical Industries, Ltd.).
  • peroxides examples include perbutyl (registered trademark) Z, perhexa (registered trademark) 25B (manufactured by NOF Corporation) and the like.
  • Examples of the above-mentioned photo radical polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, ⁇ -Diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, imide sulfonate compounds, and the like.
  • the radical photopolymerization initiator is at least selected from the group consisting of acylphosphine oxide compounds, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds. It is preferable that 1 type is included.
  • acylphosphine oxide compounds for example, 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferable.
  • thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Examples include diethylthioxanthone and 2,4-diisopropylthioxanthone.
  • acetophenone compounds examples include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
  • biimidazole compounds examples include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2,4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole and the like.
  • the hydrogen donor means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
  • the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, etc.
  • an amine-based hydrogen donor can be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable in that the sensitivity can be further improved.
  • triazine compound described above examples include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tria
  • O-acyloxime compounds examples include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and ethanone-1- [9-ethyl-6.
  • radical photopolymerization initiator 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone-1 -[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.
  • Photo radical polymerization initiator examples include, for example, Irgacure (registered trademark) 184, 369, OX01, OX02, 819, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur (registered trademark) 1116, 1173, 4265, TPO, Lucyrin (registered trademark) TPO (above, manufactured by BASF), Ubekril P36 (manufactured by UCB), Ezacure ( Registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (above, manufactured by Fratelli Lamberti).
  • the content of the radical polymerization initiator (D) is preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). By making content of a radical polymerization initiator (D) into said range, the desired radical polymerization reaction can be advanced rapidly.
  • the moisture trap forming composition of the embodiment of the present invention may further contain fine particles (E).
  • the fine particles (E) are components for imparting light scattering properties to the moisture trap of the embodiment of the present invention formed using the moisture trap forming composition of the present embodiment. Therefore, the fine particles (E) are preferably light scattering particles.
  • the moisture trap forming composition of the present embodiment contains such fine particles, the heat resistance and the light extraction efficiency can be improved.
  • the fine particles (E) are not particularly limited as long as they have an effect of scattering and extracting light formed by an organic EL element, for example, and may be organic particles or inorganic particles.
  • organic particles polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine resin beads, polycarbonate beads, polystyrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde condensate beads, and the like are used.
  • inorganic particles SiO 2 , ZrO 2 , TiO 2 , Al 2 O 3 , In 2 O 3 , ZnO, SnO 2 , Sb 2 O 3 and the like are used. These may be used alone or in combination of two or more.
  • commercially available fine particles (E) include, for example, titania particles such as RTTCHN15WT% -E06 manufactured by CI Kasei, TS-149 manufactured by Teika, TIPA15WT% -X480 manufactured by CI Kasei, and N-SOL- manufactured by NanoGram. 101-20PM or the like can be used.
  • titania particles such as RTTCHN15WT% -E06 manufactured by CI Kasei, TS-149 manufactured by Teika, TIPA15WT% -X480 manufactured by CI Kasei, and N-SOL- manufactured by NanoGram. 101-20PM or the like
  • zirconia particles Optolake (registered trademark) 6320Z manufactured by JGC Catalysts & Chemicals Co., Ltd., Nanouse (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Co., Ltd., Zirconia SZR-K manufactured by Sakai Chemical Co., Ltd. Can be used.
  • the fine particles (E) have an average particle size of 50 nm to 500 nm in the moisture trap forming composition and a particle size of 600 nm or more with respect to the total amount of the fine particles (E).
  • the content of particles is 20% by volume or less.
  • the average particle diameter of the fine particles (E) is less than 50 nm, a sufficient scattering effect does not appear and the refractive index of the formed moisture trap is affected, which is not preferable.
  • it is larger than 500 nm, the scattering angle becomes narrow even if the scattering intensity (haze value) is high, so that effective scattering cannot be obtained, the light extraction efficiency is lowered, and the change of the light extraction efficiency due to the wavelength increases.
  • the color tone tends to change, which is not preferable. More preferably, it is 50 nm to 300 nm.
  • the content of particles having a particle diameter of 600 nm or more with respect to the total amount of the fine particles (E) is more than 20% by volume, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. Further, since the surface roughness of the formed moisture trap is increased, there is a possibility that the film thickness unevenness or protrusions of the moisture trap may occur.
  • the content of particles of 600 nm or more is more preferably 15% by volume or less.
  • the “average particle diameter” and “particle diameter” of the fine particles (E) are different from the average primary particle diameter described later, and the moisture trapping body in consideration of the particle diameter of the secondary particles due to aggregation. It is the dispersed particle size in the forming composition. These can be obtained by actual measurement with an optical microscope or by a dynamic light scattering method.
  • the reason for distinguishing from the average primary particle size is that even when scattering particles having the same average primary particle size are used, the average particle size depends on the dispersion state of the fine particles in the water trapping body forming composition. This is because the diameter and the particle size distribution may be different.
  • the “average particle size” is the value of the dispersed particle size at 50% by volume of the measurement sample, and the content of particles having a particle size of 600 nm or more is the particle size of 600 nm or more of the dispersed particle size of the measurement sample. % By volume. These can be measured by “Nanotrack (registered trademark) UPA” manufactured by Nikkiso Co., Ltd. in the dynamic light scattering method.
  • the coefficient of variation is preferably 30% or less.
  • the “variation coefficient” is expressed as a percentage of a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter, and is an index of the degree of variation with respect to the average particle diameter. If the coefficient of variation is greater than 30%, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. More preferably, the coefficient of variation is 20% or less.
  • the fine particles (E) are preferably used in the form of a dispersion previously dispersed in a solvent.
  • a method for dispersing the fine particles (E) As a method for dispersing the fine particles (E), a method using a dispersing agent in accordance with the surface state of the fine particles and using a disperser is preferable.
  • disperser examples include paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homo Mixer, homogenizer ("Clearmix (registered trademark)” manufactured by M Technique Co., Ltd.), wet jet mill ("Genus (registered trademark) PY” manufactured by Genus, “Nanomizer (registered trademark)” manufactured by Nanomizer), micro bead mill (“Super Apec Mill” and “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.) can be used.
  • disperser glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads, and the like are preferably used.
  • dispersion two or more types of dispersers or two or more types of media having different sizes may be used and may be implemented step by step.
  • the average particle size and particle size distribution of the fine particles (E) can be adjusted to a suitable range by appropriately adjusting the dispersion conditions, for example, the disperser, the dispersion medium, the dispersion time, and the dispersant. Is possible. In the case of organic particles, it can be adjusted by the synthesis conditions such as the polymerization temperature and the polymerization composition, or the dispersion conditions such as the disperser, dispersion medium, dispersion time, and dispersant.
  • the amount of the fine particles (E) used is preferably 1% by mass to 25% by mass and more preferably 1% by mass to 20% by mass in the moisture trap forming composition. If it is less than 1% by mass, a sufficient scattering effect may not appear, and if it exceeds 25% by mass, the particles tend to aggregate and the surface roughness of the moisture trap to be formed may increase.
  • the moisture trap forming composition of the embodiment of the present invention may contain an additive as necessary. Specifically, a sensitizer, a curing accelerator, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, Surfactant etc. are illustrated.
  • the moisture trap forming composition of the present invention is a mixture of the above-described component (A), component (B) and component (C), and the component (D), component (E), stabilizer and the like are determined as necessary. It can prepare by mixing in the ratio.
  • the moisture trap forming composition of the embodiment of the present invention is used for forming a moisture trap used for an electronic device in which moisture may deteriorate characteristics, particularly for forming a moisture trap constituting an organic EL element.
  • the water capturing ability of the water capturing body of this embodiment can be expressed.
  • the moisture trap of the embodiment of the present invention is formed using the moisture trap forming composition of the embodiment of the present invention.
  • the coating film is irradiated with radiation.
  • examples thereof include a method of irradiating, a method of heating, and a method of forming by curing by irradiation and heating.
  • the radiation is not particularly limited as long as it can cure the coating film of the moisture trap forming composition, but UV (ultraviolet) light is preferable.
  • the coating film of the moisture trap forming composition can be cured by ultraviolet irradiation (eg, 500 to 15000 mJ / cm 2 ) using a high-pressure mercury lamp.
  • the heating temperature is preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C.
  • the heating time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours.
  • the moisture trap of this embodiment is selected from the group consisting of (A) a compound having a hydrolyzable group and a hydrolyzate of the compound, which is formed from the above-described moisture trap forming composition of the embodiment of the present invention. And (B) at least one compound selected from the group consisting of an acid generator and a base generator, and (C) a curable compound.
  • (A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound is also referred to as (A) compound, and (B) an acid generator. And at least one compound selected from the group consisting of base generators is also referred to as (B) compound, and (C) curable compound is also referred to as (C) compound.
  • the compound (A) is a moisture trap (A) of the moisture trap forming composition.
  • Component (A) the compound which has a hydrolysable group among (A) compounds is contained in the water-trapping body formation composition as a water-trapping agent (A).
  • the (B) compound contained in the moisture trap of this embodiment is derived from the acid / base generator (B) (component (B)) of the moisture trap formation composition of the embodiment of the present invention.
  • the (C) compound contained in the moisture trap of the present embodiment is due to the curable compound (C) (component (C)) of the moisture trap forming composition of the embodiment of the present invention.
  • the example of the compound (A) having a hydrolyzable group is the same as the example of the water trapping agent (A) of the water trap forming composition, and the example of the compound (B) is a water trap. It is the same as the acid / base generator (B) of the forming composition, and examples of the (C) compound are the same as the curable compound (C) of the moisture trap forming composition.
  • the moisture trapping agents (A1) to (A3) are used as the moisture trapping agents (A).
  • the moisture trapping agent (A) is at least selected from the moisture trapping agents (A2) to (A3).
  • One type is used.
  • the compound is (A1) a compound represented by the formula (A1-1), a compound represented by the formula (A1-2), and At least one compound selected from compounds represented by formula (A1-3) (also referred to as (A1) compound), (A2) at least one compound selected from carboxylic acid anhydride and carboxylic acid compound (( A2) also referred to as a compound), and (A3) a compound represented by formula (A3-1), a compound represented by formula (A3-2), and a compound represented by formula (A3-3) (( A3) It is also referred to as a compound.) It is at least one selected from the group consisting of at least one compound selected from the above, and (B) the compound is preferably an acid generator.
  • the (A) compound is at least one selected from the group consisting of the above-mentioned (A2) compound and the above-mentioned (A3) compound, (B) It is preferable that a compound is a base generator.
  • R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or a carbon number.
  • An organic group of 1 to 18, and R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure, and n is 0 or an integer of 1 to 18 * Represents a bonding position
  • R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms
  • R 8 is independently an organic group having 3 to 30 carbon atoms. There; wherein (A1-3), wherein R 8 has the same meaning as in formula (A1-2).
  • X is a silicon atom, a titanium atom or a zirconium atom
  • R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms
  • R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent.
  • Group optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group; p is an integer from 0 to 6; r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
  • the compound represented by the formula (A1-3) has the formula (A) as described with reference to the action and effect of the moisture trapping body-forming composition of the embodiment of the present invention.
  • carboxylic acid anhydride which is the compound (A) is the carboxylic acid anhydride of the water trapping agent (A2) described above.
  • carboxylic acid compound of (A) compounds is the hydrolysis product of the carboxylic anhydride, as demonstrated about the effect of the moisture-capturing body formation composition of embodiment of this invention.
  • the compound represented by the formula (A3-3) is represented by the formula (A3-1) as described for the action and effect of the moisture trapping body forming composition of the embodiment of the present invention.
  • a hydrolysis product of the compound represented by formula (A3-2) is represented by the formula (A3-3) as described for the action and effect of the moisture trapping body forming composition of the embodiment of the present invention.
  • the moisture trap of the embodiment of the present invention is at least one selected from the group consisting of the moisture traps (A1) to (A3) of the moisture trap forming composition of the embodiment of the present invention and their hydrolysis products. Contains seed compounds.
  • the moisture trap of the present embodiment is formed from the above-described moisture trap forming composition of the embodiment of the present invention, and can contain (D) a radical polymerization initiator.
  • the (D) radical polymerization initiator is a radical polymerization initiator (D) (component (D) of the water trap formation composition of the embodiment of the present invention. )). Therefore, the example of the (D) radical polymerization initiator is the same as the component (D) of the moisture trap forming composition.
  • the moisture trap of the present embodiment is formed from the above-described moisture trap forming composition of the embodiment of the present invention, and can contain (E) fine particles.
  • the moisture trap of this embodiment includes (E) fine particles
  • the (E) fine particles are due to the fine particles (E) (component (E)) of the moisture trap forming composition of the embodiment of the present invention.
  • examples of the fine particles (E) are the same as the component (E) of the moisture trap forming composition.
  • the moisture trap of this embodiment can improve heat resistance by containing (E) fine particles, and can be applied to an organic EL element to improve light extraction efficiency.
  • the moisture trap of the embodiment of the present invention described above efficiently removes moisture in an electronic device such as an organic EL element to be applied at the time of formation, and also removes moisture in the element after formation. Can be consumed.
  • the moisture trap of this embodiment is the state which trapped the moisture, it is hard to produce decomposition products with high volatility like low molecular alcohol etc., for example, when used for an organic EL element etc.
  • the generation of dark spots due to the adhesion of the decomposition products to the organic EL layer can be suppressed. That is, the moisture trap of the embodiment of the present invention can be suitably used particularly for an organic EL element.
  • the moisture trap forming composition of the embodiment of the present invention is used in the configuration of the electronic device according to the embodiment of the present invention, which forms a moisture trap and there is a concern that the moisture may deteriorate the characteristics.
  • the electronic device according to the embodiment of the present invention may be any electronic device as long as moisture is an electronic device that may cause deterioration in characteristics. Examples of such electronic devices include organic EL elements and liquid crystal display elements. In the case of an organic EL element, for example, a highly reliable organic EL lighting device or organic EL display element can be configured.
  • the moisture trap is formed from the moisture trap forming composition of the embodiment of the present invention. Can be removed efficiently. And since the moisture trap of the embodiment of the present invention can absorb the moisture in the element for a long period after its formation, it is possible to suppress deterioration of the element due to moisture.
  • FIG. 1 is a cross-sectional view schematically showing a first example of an organic EL element according to an embodiment of the present invention.
  • An organic EL element 100 that is a first example of the organic EL element according to the embodiment of the present invention shown in FIG. 1 includes an organic EL layer 10 and a structure 20 that houses the organic EL layer 10 and blocks it from the outside air. And a moisture trap 30 formed in the structure 20.
  • the moisture trap 30 is formed using the moisture trap forming composition of the embodiment of the present invention described above.
  • the structure 20 includes a substrate 22, a sealing substrate 24, and a sealing material 26 that are substrates for elements that support the organic EL layer 10.
  • the organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other.
  • a known structure comprising an organic light emitting layer / cathode or the like can be employed. If necessary, a charge (hole) injection layer or a charge (hole) transport layer can be provided between the anode and the organic light emitting layer, and an electron can be provided between the cathode and the organic light emitting layer. An injection layer or an electron transport layer can be provided.
  • the organic EL layer 10 is disposed on the substrate 22 of the structure 20 as shown in FIG.
  • the organic EL element 100 can have a bottom emission structure or a top emission structure.
  • the organic EL layer 10 includes a back electrode serving as an anode, an organic light emitting layer, and a cathode.
  • the translucent or semi-transparent front electrode is arranged on the substrate 22 in this order.
  • the back electrode of the organic EL layer 10 preferably has light reflectivity.
  • the material for the back electrode metals, alloys, conductive metal oxides, other conductive compounds, and mixtures thereof can be used.
  • Alkali metals eg, Li, Na, and K, etc.
  • Alkaline earth metals eg, Mg, Ca, etc.
  • Lithium-aluminum alloys and mixed metals containing them LiF / Al alloys and mixed metals containing them
  • Magnesium-silver alloys and mixed metals containing them Magnesium-silver alloys and mixed metals containing them
  • rare earth metals such as indium and ytterbium.
  • a material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof are preferable.
  • the film thickness of the back electrode of the organic EL layer 10 can be appropriately selected depending on the material, but is preferably 100 nm to 1 ⁇ m.
  • methods such as an electron beam vapor deposition method, a sputtering method, a resistance heating vapor deposition method, and a coating method can be used.
  • the metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. It is also possible to form a metal electrode by simultaneously vapor-depositing a plurality of metals, or an alloy prepared in advance may be vapor-deposited.
  • the material of the organic light emitting layer of the organic EL layer 10 can inject holes from the anode and the like when an electric field is applied, and can also inject electrons from the cathode and the like, and moves the injected charges.
  • the material is not particularly limited as long as it is a material that can form a layer having a function and a function of emitting light by providing a recombination field of holes and electrons.
  • the materials of the organic light emitting layer of the organic EL layer 10 are, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, Perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidins Compounds, and various metal complexes represented by metal complexes or rare earth complexes of 8-quinolinol derivatives; and, And polymer compounds such
  • Blue light emission can be obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (TBP), 9,10-diphenylanthracene derivative, or the like as a guest material.
  • TBP 2,5,8,11-tetra-t-butylperylene
  • 9,10-diphenylanthracene derivative or the like as a guest material.
  • styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), 9,10-di-2-naphthylanthracene (DNA), and 9,10-bis (2-naphthyl) It can also be obtained from anthracene derivatives such as 2-tert-butylanthracene (t-BuDNA).
  • a polymer such as poly (9,9-dioctylfluorene) may also be used.
  • Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (FIrpic), and bis (2-phenylpyridinato) acetylacetonate. It can be obtained by using iridium (Ir (ppy) (acac)) or the like as a guest material. Also obtained from metal complexes such as tris (8-hydroxyquinoline) aluminum (Alq3), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) chlorogallium (Ga (mq) 2 Cl) Can do. Further, a polymer such as poly (p-phenylene vinylene) may be used.
  • coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (FIrpic), and bis (2-
  • the orange to red luminescence is rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (DCM1), 4- (dicyanomethylene) -2-methyl- 6- (9-Jurolidyl) ethynyl-4H-pyran (DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (BisDCM), bis [2- ( 2-thienyl) pyridinato] acetylacetonatoiridium (Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (Ir (pq) (acac)) and the like are used as guest materials Obtained by.
  • a metal complex such as bis (8-quinolinolato) zinc (Znq 2 ) or bis [2-cinnamoyl-8-quinolinolato] zinc (Znsq 2 ).
  • a polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may be used.
  • White light emission defines the energy level of each layer of the organic EL laminated structure and emits light using tunnel injection (European Patent No. 0390551).
  • a light emitting element is described (Japanese Patent Laid-Open No. 3-230484), a light emitting layer having a two-layer structure is described (Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. 2-216790), and a light emitting layer Are made of materials having different emission wavelengths (JP-A-4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm).
  • the blue light emitting layer contains a blue fluorescent dye
  • the green light emitting layer has a red phosphor. It has a region containing a dye, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.
  • the thickness of the organic light emitting layer of the organic EL layer 10 is not particularly limited, but is usually preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.
  • a method for forming the organic light emitting layer of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Blodgett) method.
  • the resistance heating vapor deposition method and the coating method are preferable.
  • the front electrode of the organic EL layer 10 preferably has a light-transmitting property or a semi-light-transmitting property when the organic EL element 100 has a top emission structure.
  • a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used as a material for such a translucent or semi-transparent front electrode of the organic EL layer 10.
  • Conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO); Metals such as gold, silver, chromium and nickel; Other inorganic conductive materials such as copper iodide and copper sulfide; Organic conductive materials such as polyaniline, polythiophene, PEDOT / PSS, and polypyrrole; And mixtures or laminates thereof.
  • a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, translucency, and the like.
  • the front electrode of the organic EL layer 10 can be made of a light-transmitting electrode by laminating metals and ITO in order to control the electron injection property to the organic light-emitting layer while maintaining the light-transmitting property. is there.
  • the thickness of the ultrathin metal is preferably from 0.1 nm to 20 nm from the viewpoint of maintaining translucency.
  • Alkali metals such as Li, Na, and K
  • Alkaline earth metals such as Mg and Ca
  • Lithium-aluminum alloys and mixed metals containing them LiF / Al alloys and mixed metals containing them
  • Magnesium-silver alloys and mixed metals containing them and rare earth metals such as indium and ytterbium.
  • the above metals are preferably aluminum, lithium-aluminum alloy and mixed metal thereof, magnesium-silver alloy and mixed metal thereof.
  • the film thickness of the front electrode can be appropriately selected depending on the material, but is usually preferably about 50 nm to 300 nm.
  • the front electrode As a method for forming the front electrode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a solution or dispersion coating method are used.
  • the formed front electrode is etched to form a pattern as desired.
  • the driving voltage of the organic EL element can be lowered or the luminous efficiency can be increased by washing or other processing. For example, when ITO is used for the front electrode, UV-ozone treatment or the like is effective.
  • the organic EL layer 10 has a hole injection layer or a hole transport layer between the anode and the organic light emitting layer, these materials have a function of injecting holes from the anode, and transport the injected holes. Any one having a function of blocking the electrons injected from the cathode may be used. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives.
  • Fluorenone derivatives Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds
  • Examples thereof include copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene.
  • the material of the electron injection layer and the electron transport layer transports electrons from the cathode.
  • Any function may be used as long as it has a function or a function of blocking holes injected from the anode.
  • Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl.
  • the film thickness of the hole injection layer, hole transport layer, electron injection layer, and electron transport layer of the organic EL layer 10 is not particularly limited, but is preferably 10 nm to 500 nm.
  • Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.
  • a method for forming these layers of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Blodgett) method.
  • the resistance heating vapor deposition method and the coating method are preferable.
  • the moisture trap 30 formed in the structure 20 is disposed separately from the organic EL layer 10 as shown in FIG. .
  • the structure 20 of the organic EL element 100 includes a substrate 22, a sealing material 26 formed on the periphery of the organic EL layer 10 in the substrate 22, and a sealing substrate 24 fixed to the substrate 22 by the sealing material 26. It has.
  • the organic EL layer 10 is sealed with a substrate 22, a sealing substrate 24 and a sealing material 26.
  • the inside of the organic EL element 100 has a hollow structure and may be filled with an inert gas so as not to deteriorate the organic EL layer 10.
  • the sealing material 26 is a sealing material formed from an adhesive composition.
  • Examples of the substrate 22 of the organic EL element 100 include a glass substrate, and examples of the sealing substrate 24 include a structure made of glass or the like.
  • the sealing material 26 fixes the sealing substrate 24 to the substrate 22 and seals the organic EL layer 10 between the sealing substrate 24 and the substrate 22.
  • the structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated and sealed using the sealing material 26.
  • the substrate 22 and the sealing substrate 24 are bonded to each other with a coating film made of an adhesive composition, and then the coating film is cured by irradiation and / or heating.
  • the sealing material 26 is formed, and the organic EL layer 10 can be sealed in the sealing space.
  • the moisture trap 30 formed in the structure 20 can capture and efficiently remove moisture in the sealed space in which the organic EL layer 10 is sealed.
  • the structure and arrangement of the moisture trap 30 are not particularly limited.
  • the moisture trap 30 is arranged on the sealing substrate 24 so as to be separated from the organic EL layer 10 like the organic EL element 100 of FIG.
  • the moisture trap 30 may be disposed on the side surface of the organic EL layer 10 or the sealing material 26 in the sealed space.
  • the moisture trap 30 may be laminated on the organic EL layer so as to be in close contact with the organic EL layer 10 and is disposed so as to fill the entire sealing space in the structure 20 without any gaps, as will be described later. May be.
  • the organic EL element 100 having the above structure is provided with the moisture trap 30 to remove moisture in the element. And the organic EL element 100 can suppress the fall of the light emission characteristics, such as a brightness
  • the organic EL element 100 can constitute, for example, a highly reliable organic EL lighting device.
  • the organic EL element 100 can also constitute an organic EL display device.
  • the organic EL element 100 uses, for example, a TFT substrate in which a thin film transistor (TFT) as a switching element is formed for each pixel arranged in a matrix as the substrate 22, and a plurality of organic ELs that emit a plurality of different colors.
  • TFT thin film transistor
  • FIG. 2 is a cross-sectional view schematically showing a second example of the organic EL element of the embodiment of the present invention.
  • an organic EL element 200 which is a second example of the organic EL element according to the embodiment of the present invention has a moisture trap 130 formed in the structure 20.
  • the moisture trap 130 is formed using the moisture trap forming composition of the embodiment of the present invention described above.
  • the organic EL element 200 is different from the organic EL element 100 of FIG. 1 in that the moisture trap 130 formed in the structure 20 is formed in close contact with the organic EL layer 10.
  • the same reference numerals are given to the same components as the organic EL element 100 of FIG.
  • the moisture trap 130 removes moisture at the time of formation, and can prevent moisture from entering the organic EL layer 10 due to its hygroscopicity after the formation. Furthermore, since the moisture trap 130 is formed so as to be in close contact with the organic EL layer 10, the organic EL layer 10 can also be protected.
  • the organic EL element 200 can constitute, for example, a highly reliable organic EL lighting device.
  • FIG. 3 is a cross-sectional view schematically showing a third example of the organic EL element of the embodiment of the present invention.
  • a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects.
  • the gas barrier film 40 is provided to prevent moisture and oxygen from coming into contact with the organic EL layer 10.
  • the gas barrier film 40 is not particularly limited and a conventionally known film can be used, and examples thereof include a film in which organic films and inorganic films are alternately laminated.
  • the organic EL element 300 includes the gas barrier film 40 together with the moisture capturing body 30, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10.
  • the organic EL element 300 can constitute, for example, a highly reliable organic EL lighting device.
  • FIG. 4 is a cross-sectional view schematically showing a fourth example of the organic EL element according to the embodiment of the present invention.
  • gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects.
  • the gas barrier film 40 is the same as that provided in the organic EL element 300 shown in FIG.
  • the organic EL element 400 includes the gas barrier film 40 together with the moisture trap 130, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10.
  • the organic EL element 400 can constitute, for example, a highly reliable organic EL lighting device.
  • FIG. 5 is a cross-sectional view schematically showing a fifth example of the organic EL element of the embodiment of the present invention.
  • the moisture trap 30 formed from the moisture trap formation composition of the embodiment of the present invention is formed on the organic EL layer 10 with respect to the organic EL element 400 shown in FIG. 4. Further, it is different in that it has a gas barrier film 40 that covers the entire surface of the moisture trap 30 and the side surface of the organic EL layer 10, and is the same in other respects.
  • the gas barrier film 40 is the same as that provided in the organic EL elements 300 and 400 shown in FIGS.
  • the organic EL element 500 includes the gas barrier film 40 together with the moisture traps 30 and 130, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10.
  • the organic EL element 500 can constitute, for example, a highly reliable organic EL lighting device.
  • the 1 H-NMR spectrum of the moisture scavenger (AO-1) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 0.76 to 0.96 (24H, m), ⁇ 1.20 to 1.40 (24H, m), ⁇ 1.10 to 1.60 (32H, m), ⁇ 3.. 34-4.10 (24H, m), ⁇ 5.24 (4H, s).
  • the 1 H-NMR of the moisture trapping agent (AO-2) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 0.88 (12H, s), ⁇ 1.25 to 1.35 (64H, m), ⁇ 1.35-1.45 (8H, m), ⁇ 3.90 (4H, m), ⁇ 3.95 to 4.05 (8H, m), ⁇ 5.80 (8H, s), ⁇ 6.30 (4H, s).
  • the 1 H-NMR spectrum of the moisture scavenger (AO-3) was measured and found to be as follows.
  • Synthesis Example 4 Synthesis of Water Capture Agent (AO-4) Similar to the water capture agent (AO-1), methyl orthoformate, 2-butyl-2-ethyl-1,3-propanediol, trimethylolpropane and The following water scavenger (AO-4) was obtained from a 90% aqueous formic acid solution.
  • the 1 H-NMR of the moisture trapping agent (AO-4) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 0.90 (6H, t), ⁇ 1.20 to 1.40 (6H, m), ⁇ 1.55 (2H, q), ⁇ 1.60 to 1.75 (8H, m), ⁇ 3.80 (4H, d), ⁇ 3.85 (8H, q), ⁇ 5.80 (2H, s), ⁇ 6.05 (3H, s).
  • the 1 H-NMR spectrum of the moisture scavenger (AO-5) was measured and found to be as follows.
  • the 1 H-NMR spectrum of the moisture scavenger (AO-7) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 0.83 (12H, m), ⁇ 1.24 to 1.56 (8 H, m), ⁇ 3.20 to 4.10 (40 H, d), ⁇ 5.10 to 5. 36 (12H, m), ⁇ 5.88 (4H, m).
  • the 1 H-NMR spectrum of the moisture scavenger (AO-8) was measured and found to be as follows.
  • the 1 H-NMR spectrum of the moisture scavenger (AO-9) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 3.20 to 4.20 (24H, m), ⁇ 4.20 to 4.70 (4H, m), ⁇ 5.60 to 6.10 (4H, m).
  • the 1 H-NMR of the moisture trapping agent (AO-11) was measured and found to be as follows. 1 H-NMR (CDCl 3 ); ⁇ 0.91 (9H, t), ⁇ 1.77 (6H, q), ⁇ 3.77 (6H, s), ⁇ 4.28 (6H, d), ⁇ 4.41 (6H) , D), ⁇ 5.42 (1H, s).
  • the production of the moisture scavenger (A3-i) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of ⁇ 4.5- ⁇ 3.5 derived from the group.
  • the production of the moisture scavenger (A3-ii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of ⁇ 4.5- ⁇ 3.5 derived from the group.
  • the generation of the moisture scavenger (A3-ii-2) is different from the peak of the starting material 3-ethyl-3-oxetane methanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of ⁇ 4.5- ⁇ 3.5 derived from the methyloxy group.
  • the generation of the moisture scavenger (A3-iii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6), which is 3-ethyl-3-oxetanemethyloxy. This was done by observing the peak of ⁇ 4.5- ⁇ 3.5 derived from the group.
  • the production of the moisture scavenger (A3-iv) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing a peak at ⁇ 4.5-3.5 derived from the group.
  • Component (A) moisture trapping agent (A1), moisture trapping agent (A2), moisture trapping agent (A3), and conventional moisture trapping agent) and components used for the preparation of each moisture trap forming composition of this example (B) (acid / base generator (B)), component (C) (curable compound (C)), component (D) (radical polymerization initiator (D)) and component (E) (fine particles (E) ) Is shown below.
  • component (A) moisture trapping agent (A1), moisture trapping agent (A2), moisture trapping agent (A3), and conventional moisture trapping agent
  • B acid / base generator
  • component (C) curable compound (C)
  • component (D) radical polymerization initiator (D)
  • component (E) fine particles (E) ) Is shown below.
  • AS-1 to AS-6 of the moisture trapping agent (A2) of the component (A) the melting points (° C.) are also shown.
  • AO-1 Moisture trap (AO-1)
  • AO-2 Moisture trap (AO-2)
  • AO-3 Moisture trap (AO-3)
  • AO-4 Moisture trap (AO-4)
  • AO-5-1 Moisture trap (AO-5-1)
  • AO-6 Moisture trap (AO-6)
  • AO-7 Moisture trap (AO-7)
  • AO-8 Moisture trap (AO-8)
  • AO-9 Moisture trap (AO-9)
  • AO-10 Moisture trap (AO-10)
  • AO-11 Moisture trap (AO-11)
  • AO-12 Moisture trap (AO-12)
  • AS-3 Glycerin bis anhydro trimellitate monoacetate (manufactured by Shin Nippon Rika Co., Ltd.) / 65 ° C-85 ° C
  • AS-4 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) / 172 ° C.
  • AS-5 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.) / 287 ° C.
  • AS-6 Tetrapropenyl succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) /-5 ° C
  • AX-1 Aluminum triisopropoxide (Al (i-PrO) 3 ) (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • AX-2 Calcium oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • B-1 CPI-200K (San Apro)
  • B-2 Sun-Aid (registered trademark) SI-80L (manufactured by Sanshin Chemical Industry)
  • B-3 2-Nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate
  • Component (C) C-1: Epicoat (registered trademark) 828 (manufactured by Mitsubishi Chemical) C-2: Denacol (registered trademark) EX-212 (manufactured by Nagase) C-3: NK ester 9PG (manufactured by Shin-Nakamura Chemical)
  • D-1 Lucillin (registered trademark) TPO (manufactured by BASF)
  • D-2 V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)
  • E-1 Nanouse (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Industries, Ltd. (primary particle size of zirconium oxide 20 nm, average particle size 80 nm by dynamic light scattering, solid content concentration 20% by mass)
  • E-2 RTTCHN 15WT% -E06 manufactured by CI Kasei Co., Ltd. (primary particle size of titanium oxide 25 nm, average particle size 100 nm by dynamic light scattering, solid content concentration 15% by mass)
  • Example 1 Preparation of moisture trap forming composition (JO-1)) Under atmospheric environment, 20 parts by mass of (AO-1) which is the moisture trapping agent (A1) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. Thereafter, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (JO-1).
  • AO-1 which is the moisture trapping agent (A1) of component (A)
  • C-1) component (C)
  • Examples 2 to 19 and Comparative Examples 1 to 4 Preparation of moisture trap forming composition (JO-2) to (JO-23)) Except having used each component of the kind and compounding quantity which are shown in following Table 1, it operated similarly to Example 1 and prepared each moisture capture body formation composition.
  • Example 17 to 19 the component (E) was used in an amount corresponding to the solid content shown in Table 1.
  • Example 20 (Preparation of moisture trap forming composition (JS-1)) Under atmospheric environment, 20 parts by mass of (AS-1) which is a moisture trapping agent (A2) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. Thereafter, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (JS-1).
  • AS-1 which is a moisture trapping agent (A2) of component (A)
  • C-1) which is component (C) to obtain a uniform solution.
  • component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (JS-1).
  • Each component and amount used are shown in Table 2 together with other examples described later.
  • Example 30 to 32 the component (E) was used in an amount corresponding to the solid content described in Table 2.
  • Example 33 (Preparation of moisture trap forming composition (J-1)) Under atmospheric environment, 20 parts by mass of (A-1) which is a moisture trapping agent (A3) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. After that, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (J-1).
  • A3 a moisture trapping agent
  • C-1 component (B-1)
  • Examples 34 to 44 and Comparative Example 6 Preparation of Moisture Capturing Body Forming Compositions (J-2) to (J-13) Except having used each component of the kind and compounding quantity which are shown in following Table 3, it operated similarly to Example 33 and prepared each moisture capture body formation composition.
  • Example 40 to 44 the component (E) was used in an amount corresponding to the solid content shown in Table 3.
  • ⁇ Manufacture of organic EL elements Poly (3,4) as a hole injection material on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having an ITO film having a thickness of 15 nm formed on a glass plate having a length and width of 25 mm and a thickness of 0.7 mm and a pattern of 2 mm in width.
  • a coating solution for forming a hole injection layer containing ethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS) is spin-coated at 3000 rpm for 50 seconds to form a hole injection layer having a thickness of 50 nm, and then high purity. Heating and drying were performed at 200 ° C. for 10 minutes in nitrogen.
  • the hole injection layer forming coating solution a solution in which PEDOT / PSS was dissolved in pure water at a solid content of 0.1% by mass was used.
  • a 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated at 2000 rpm for 50 seconds to form an organic light emitting layer having a thickness of 70 nm, and then baked at 60 ° C. for 10 minutes.
  • LiF was deposited to 10 nm at a deposition rate of 0.1 nm / sec under a pressure condition of 10 ⁇ 5 Pa, and 20 nm of Ca was deposited at a deposition rate of 0.1 nm / sec.
  • a cathode was formed by laminating 100 nm of Al at a deposition rate.
  • each of the above moisture trapping composition was applied on the organic EL layer formed on the glass substrate by spin coating, and a coating film having a thickness of 50 ⁇ m was formed by heating at 120 ° C. for 5 minutes.
  • the film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation).
  • a composition having the same composition as the moisture-trapping composition obtained in Comparative Example 1 was applied to the peripheral edge of the obtained glass substrate with a dispenser using a dispenser to form a coating film having a thickness of 100 ⁇ m. did.
  • a counter glass substrate having a length and width of 25 mm and a thickness of 0.7 mm is bonded to the film-formed glass substrate through the coating film, and an ultrahigh pressure mercury lamp ( After irradiation with ultraviolet light (UV) of 1 J / cm 2 using an intensity at 365 nm of 100 nm, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material. . Only in Example 3, Example 5, Example 22, Example 24, and Example 36, using the vacuum laminating apparatus, the coated glass substrate was coated with the opposite glass substrate having a length and width of 25 mm and a thickness of 0.7 mm on the film-formed glass substrate. After heating at 100 ° C. for 30 minutes, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material.
  • UV ultraviolet light
  • the organic EL element was manufactured as described above.
  • the present invention can provide a moisture trap forming composition capable of forming a moisture trap that can be handled in air and hardly generates a volatile decomposition product. Therefore, the present invention can provide a moisture trap formed from the moisture trap forming composition and an electronic device including the moisture trap with high productivity. And it can use suitably for electronic devices, such as an organic EL element which suppresses generation

Abstract

Provided are: a moisture capturing body which can be handled in the air; and an organic EL element which is provided with this moisture capturing body. A moisture capturing body-forming composition is prepared so as to contain, as components, at least one compound that is selected from the group consisting of compounds having a hydrolyzable group, at least one compound that is selected from the group consisting of acid generators and base generators, and a curable compound. A moisture capturing body (30) is formed using this moisture capturing body-forming composition. An organic EL element (100) is provided by hermetically sealing the moisture capturing body (30) together with an organic EL layer (10), which includes an organic light emitting layer, within a structure (20) so as to be blocked from the outside air.

Description

有機ＥＬ素子Organic EL device
　本発明は有機ＥＬ素子に関する。 The present invention relates to an organic EL element.
　近年、盛んに開発が進められている電子デバイスの一つとして、有機エレクトロルミネッセンス（ＥＬ）素子が知られている。有機ＥＬ素子は、陽極／有機発光層／陰極からなる積層構造を基本の構造とする簡素なデバイスであるが、有機発光層が水分の影響を受けやすいという課題を有している。 In recent years, an organic electroluminescence (EL) element is known as one of electronic devices that have been actively developed. The organic EL element is a simple device having a basic structure of a laminated structure composed of an anode / organic light emitting layer / cathode, but has a problem that the organic light emitting layer is easily affected by moisture.
　すなわち、有機ＥＬ素子は、駆動期間の長期化に伴って、素子に侵入した水分の影響により、所謂ダークスポットの形成が懸念されるほか、輝度や発光効率等の発光特性が徐々に低下する懸念を有している。そのため、有機ＥＬ素子は、素子内の水分を除去し、さらに密閉した状態で使用する必要があるが、このような電子デバイスを封止により完全に密閉することは困難である。 That is, in the organic EL element, as the driving period becomes longer, there is a concern that so-called dark spots may be formed due to the influence of moisture that has entered the element, and light emission characteristics such as luminance and light emission efficiency may be gradually decreased. have. Therefore, the organic EL element needs to be used in a state where moisture in the element is removed and sealed, but it is difficult to completely seal such an electronic device by sealing.
　そこで、あらかじめ素子内に特定の有機金属化合物からなる水分捕獲剤を配置し、この水分捕獲剤に水分を捕獲させることで素子内を低湿度環境に保つ有機ＥＬ素子が提案されている（例えば、特許文献１を参照。）。 Therefore, an organic EL element has been proposed in which a moisture trapping agent made of a specific organometallic compound is placed in the element in advance, and the moisture trapping agent traps moisture to keep the inside of the element in a low humidity environment (for example, (See Patent Document 1).
特許第３９３６１５１号公報Japanese Patent No. 3936151
　しかしながら、例えば、特許文献１等において水分捕獲剤として例示された有機アルミニウム化合物は、非常に反応性が高く、空気中の水分と反応する懸念がある。そのため、空気中での取り扱いが難しく、従来の水分捕獲剤を使用する場合には、十分に低い湿度に管理された空気や窒素下での取り扱いが必須とされていた。そして、従来の水分捕獲剤を用いて有機ＥＬ素子を製造する場合、低湿度雰囲気下での作業が必要とされる等、製造工程が煩雑なものになっていた。 However, for example, the organoaluminum compounds exemplified as the moisture scavenger in Patent Document 1 and the like are very reactive and may react with moisture in the air. Therefore, handling in air is difficult, and when using a conventional moisture scavenger, handling under air or nitrogen controlled to a sufficiently low humidity has been essential. And when manufacturing an organic EL element using the conventional moisture capture agent, the manufacturing process became complicated, for example, an operation in a low humidity atmosphere was required.
　したがって、通常の空気下での取り扱いが可能で、有機ＥＬ素子等の電子デバイスの製造に使用できる水分捕獲用部材が求められている。そして、素子内の水分を除去するとともに素子内への水分の侵入を低減し、空気下で取り扱うことができる水分捕獲体を備える有機ＥＬ素子が求められている。 Therefore, there is a need for a moisture trapping member that can be handled under normal air and can be used in the manufacture of electronic devices such as organic EL elements. There is a need for an organic EL element that includes a moisture trap that can remove moisture in the element and reduce moisture intrusion into the element and handle it under air.
　本発明は、以上のような問題に鑑みてなされたものである。すなわち、本発明の課題は、有機ＥＬ素子および液晶表示素子等の電子デバイスにおいて、素子内の水分を除去するとともに素子内への水分の侵入を低減し、空気下で取り扱うことができる水分捕獲体を提供することにあり、また、その水分捕獲体を備える有機ＥＬ素子を提供することにある。 The present invention has been made in view of the above problems. That is, an object of the present invention is to provide a moisture trap that can be handled under air in an electronic device such as an organic EL element and a liquid crystal display element, which removes moisture in the element and reduces moisture intrusion into the element. And providing an organic EL device including the moisture trap.
　本発明者らは上記課題を解決すべく鋭意検討を行った。その結果、以下の構成を有する有機ＥＬ素子により上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by an organic EL element having the following configuration, and have completed the present invention.
　例えば、本発明は、以下の［１］～［５］に関する。 For example, the present invention relates to the following [1] to [5].
　［１］水分捕獲体を備える有機ＥＬ素子であって、
　前記水分捕獲体が、
　（Ａ）加水分解性基を有する化合物および該化合物の加水分解物からなる群より選択される少なくとも１種の化合物と、
　（Ｂ）酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物と、
　（Ｃ）硬化性化合物と
を含む有機ＥＬ素子。 [1] An organic EL device comprising a moisture trap,
The moisture trap is
(A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound;
(B) at least one compound selected from the group consisting of an acid generator and a base generator;
(C) An organic EL device comprising a curable compound.
　［２］前記（Ａ）化合物が、
　（Ａ１）式（Ａ１－１）で表される化合物、式（Ａ１－２）で表される化合物および式（Ａ１－３）で表される化合物から選ばれる少なくとも１種の化合物、
　（Ａ２）カルボン酸無水物およびカルボン酸化合物から選ばれる少なくとも１種の化合物、並びに、
　（Ａ３）式（Ａ３－１）で表される化合物、式（Ａ３－２）で表される化合物および式（Ａ３－３）で表される化合物から選ばれる少なくとも１種の化合物
からなる群から選択される少なくとも１種の化合物であり、
　前記（Ｂ）化合物が、酸発生剤である前記［１］に記載の有機ＥＬ素子。 [2] The compound (A) is
(A1) at least one compound selected from a compound represented by formula (A1-1), a compound represented by formula (A1-2), and a compound represented by formula (A1-3);
(A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and
(A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected,
The organic EL device according to [1], wherein the compound (B) is an acid generator.
Figure JPOXMLDOC01-appb-C000004
 ［式（Ａ１－１）中、Ｒ１～Ｒ５は、それぞれ独立に水素原子または炭素数１～１８の有機基であり、Ｒ６およびＲ７は、それぞれ独立に水素原子、水酸基または炭素数１～１８の有機基であり、Ｒ３、Ｒ４およびＲ７は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよく、ｎは０または１～１８の整数であり、＊は結合位を示し；式（Ａ１－２）中、Ｒ１は水素原子または炭素数１～１８の有機基であり；Ｒ８はそれぞれ独立に炭素数３～３０の有機基であり；式（Ａ１－３）中、式Ｒ８は式（Ａ１－２）と同義である。］
Figure JPOXMLDOC01-appb-C000004
 [In the formula (A1-1), R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or a carbon number. An organic group of 1 to 18, and R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure, and n is 0 or an integer of 1 to 18 * Represents a bonding position; in formula (A1-2), R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; and R 8 is independently an organic group having 3 to 30 carbon atoms. There; wherein (A1-3), wherein R 8 has the same meaning as in formula (A1-2). ]
Figure JPOXMLDOC01-appb-C000005
 ［式（Ａ３－１）、式（Ａ３－２）および式（Ａ３－３）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基、カルボニル基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、またはメルカプト基であり；
ｐは０～６の整数であり；
ｒは０～２の整数であり、ｓは１～３０の整数である。］
Figure JPOXMLDOC01-appb-C000005
 [In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom; R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent. Group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group;
p is an integer from 0 to 6;
r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
　［３］前記（Ａ）化合物が、
　（Ａ２）カルボン酸無水物およびカルボン酸化合物から選ばれる少なくとも１種の化合物、並びに、
　（Ａ３）式（Ａ３－１）で表される化合物、式（Ａ３－２）で表される化合物および式（Ａ３－３）で表される化合物から選ばれる少なくとも１種の化合物
からなる群から選択される少なくとも１種の化合物であり、
　前記（Ｂ）化合物が、塩基発生剤である前記［１］に記載の有機ＥＬ素子。 [3] The compound (A) is
(A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and
(A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected,
The organic EL device according to [1], wherein the compound (B) is a base generator.
Figure JPOXMLDOC01-appb-C000006
 ［式（Ａ３－１）、式（Ａ３－２）および式（Ａ３－３）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基、カルボニル基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、またはメルカプト基であり；
ｐは０～６の整数であり；
ｒは０～２の整数であり、ｓは１～３０の整数である。］
Figure JPOXMLDOC01-appb-C000006
 [In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom; R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent. Group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group;
p is an integer from 0 to 6;
r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
　［４］前記水分捕獲体が、さらに、（Ｄ）ラジカル重合開始剤を含有する前記［１］～［３］のいずれか１項の有機ＥＬ素子。 [4] The organic EL device according to any one of [1] to [3], wherein the moisture trap further contains (D) a radical polymerization initiator.
　［５］前記水分捕獲体が、さらに、（Ｅ）微粒子を含有する前記［１］～［４］のいずれか１項の有機ＥＬ素子。 [5] The organic EL element according to any one of [1] to [4], wherein the moisture trap further contains (E) fine particles.
　本発明によれば、有機ＥＬ素子および液晶表示素子等の電子デバイスにおいて、素子内の水分を除去するとともに素子内への水分の侵入を低減し、空気下で取り扱うことができる水分捕獲体を用い、長時間駆動されてもダークスポットの発生を抑制できる有機ＥＬ照明や有機ＥＬ表示素子等の有機ＥＬ素子を提供することができる。 According to the present invention, in an electronic device such as an organic EL element and a liquid crystal display element, a moisture trap that removes moisture in the element and reduces moisture intrusion into the element and can be handled in the air is used. It is possible to provide an organic EL element such as an organic EL illumination or an organic EL display element that can suppress the generation of dark spots even when driven for a long time.
本発明の実施形態の有機ＥＬ素子の第一例を模式的に示す断面図である。It is sectional drawing which shows typically the 1st example of the organic EL element of embodiment of this invention. 本発明の実施形態の有機ＥＬ素子の第二例を模式的に示す断面図である。It is sectional drawing which shows typically the 2nd example of the organic EL element of embodiment of this invention. 本発明の実施形態の有機ＥＬ素子の第三例を模式的に示す断面図である。It is sectional drawing which shows typically the 3rd example of the organic EL element of embodiment of this invention. 本発明の実施形態の有機ＥＬ素子の第四例を模式的に示す断面図である。It is sectional drawing which shows typically the 4th example of the organic EL element of embodiment of this invention. 本発明の実施形態の有機ＥＬ素子の第五例を模式的に示す断面図である。It is sectional drawing which shows typically the 5th example of the organic EL element of embodiment of this invention.
　本発明の有機ＥＬ素子は、本発明の水分捕獲体を備える。本発明の水分捕獲体は、本発明の水分捕獲体形成組成物を用いて形成される。 The organic EL device of the present invention includes the moisture trap of the present invention. The moisture trap of the present invention is formed using the moisture trap forming composition of the present invention.
　以下、本発明の水分捕獲体を形成するための本発明の水分捕獲体形成組成物について説明し、その水分捕獲体形成組成物を用いて形成された本発明の水分捕獲体およびこの水分捕獲体を有する本発明の有機ＥＬ素子について説明する。 Hereinafter, the moisture trap forming composition of the present invention for forming the moisture trap of the present invention will be described, the moisture trap of the present invention formed using the moisture trap forming composition, and this moisture trap. The organic EL device of the present invention having the above will be described.
　〔水分捕獲体形成組成物〕
　本発明の水分捕獲体形成組成物は、加水分解性基を有する化合物からなる群より選択される少なくとも１種の化合物と、酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物と、硬化性化合物とを含有する。 [Moisture trap forming composition]
The moisture trap forming composition of the present invention has at least one compound selected from the group consisting of a compound having a hydrolyzable group, and at least one type selected from the group consisting of an acid generator and a base generator. Contains a compound and a curable compound.
　以下、各成分について詳述する。 Hereinafter, each component will be described in detail.
　尚、以下の説明において、加水分解性基を有する化合物および加水分解物からなる群より選択される少なくとも１種の化合物、酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物、並びに、硬化性化合物を、それぞれ水分捕獲剤（Ａ）、酸・塩基発生剤（Ｂ）および硬化性化合物（Ｃ）ともいい、また、水分捕獲剤（Ａ）、酸・塩基発生剤（Ｂ）および硬化性化合物（Ｃ）を、それぞれ成分（Ａ）、成分（Ｂ）および成分（Ｃ）ともいう。特に言及しない限り、その他の例においても同様である。 In the following description, at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate, at least one compound selected from the group consisting of an acid generator and a base generator , And the curable compound are also referred to as a moisture trapping agent (A), an acid / base generator (B), and a curable compound (C), respectively. Also, the moisture trapping agent (A), the acid / base generator (B) ) And curable compound (C) are also referred to as component (A), component (B) and component (C), respectively. The same applies to other examples unless otherwise specified.
　〔水分捕獲剤（Ａ）〕
　水分捕獲剤（Ａ）は、例えば、酸または塩基の存在下で加水分解しうる構造、すなわち、加水分解基を有する化合物である。水分捕獲剤（Ａ）としては、例えば、式（Ａ１－１）で表される構造部位を有する化合物および式（Ａ１－２）で表される化合物から選ばれる少なくとも１種の化合物（Ａ１）、カルボン酸無水物（Ａ２）、並びに式（Ａ３－１）で表される化合物および式（Ａ３－２）で表される化合物から選ばれる少なくとも１種の化合物（Ａ３）が挙げられる。これらの化合物（Ａ１）～（Ａ３）は各々１種単独で用いてもよく、２種以上を併用してもよい。以下の説明において、化合物（Ａ１）～（Ａ３）を、それぞれ水分捕獲剤（Ａ１）～（Ａ３）ともいう。 [Moisture capture agent (A)]
The moisture trapping agent (A) is, for example, a compound having a hydrolyzable structure, that is, a hydrolyzable group in the presence of an acid or a base. Examples of the moisture trapping agent (A) include at least one compound (A1) selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2), Carboxylic anhydride (A2), and at least one compound (A3) selected from the compound represented by formula (A3-1) and the compound represented by formula (A3-2) may be mentioned. Each of these compounds (A1) to (A3) may be used alone or in combination of two or more. In the following description, the compounds (A1) to (A3) are also referred to as moisture trapping agents (A1) to (A3), respectively.
　＜水分捕獲剤（Ａ１）＞
　水分捕獲剤（Ａ１）は、式（Ａ１－１）で表される構造部位を有する化合物、および式（Ａ１－２）で表される化合物から選ばれる少なくとも１種の化合物である。水分捕獲剤（Ａ１）は、中性および塩基性条件下においては水との反応性が低く安定であるが、酸の存在下では加水分解反応を容易に起こす。 <Moisture capture agent (A1)>
The moisture trapping agent (A1) is at least one compound selected from a compound having a structural moiety represented by the formula (A1-1) and a compound represented by the formula (A1-2). The moisture trapping agent (A1) is stable with low reactivity with water under neutral and basic conditions, but easily causes hydrolysis reaction in the presence of an acid.
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
　式（Ａ１－１）中、Ｒ１～Ｒ５は、それぞれ独立に水素原子または炭素数１～１８の有機基であり；Ｒ６およびＲ７は、それぞれ独立に水素原子、水酸基または炭素数１～１８の有機基であり；Ｒ３、Ｒ４およびＲ７は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよく；ｎは０または１～１８の整数であり；＊は結合位を示す。式（Ａ１－２）中、Ｒ１は水素原子または炭素数１～１８の有機基であり；Ｒ８はそれぞれ独立に炭素数３～３０の有機基である。 In formula (A1-1), R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms; R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or 1 carbon atom. R 3 , R 4 and R 7 together with the carbon atoms to which they are directly bonded may form a cyclic structure; n is 0 or an integer from 1 to 18 Yes; * indicates a bond position. In the formula (A1-2), R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; each R 8 is independently an organic group having 3 to 30 carbon atoms.
　尚、水分捕獲剤（Ａ１）に係る各式の説明において、特に言及しない限り、
　「炭素数１～１８の有機基」としては、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ヘキシル、ヘプチル、ｎ－オクチル、２－エチルヘキシル、デシル、ドデシル、オクタデシル等の直鎖状または分岐鎖状の炭素数１～１８のアルキル基、好ましくは炭素数１～６のアルキル基；シクロヘキシル、メチルシクロヘキシル等の炭素数３～１２のシクロアルキル基；シクロヘキシルメチル、シクロヘキシルエチル等の炭素数４～１８のシクロアルキル基置換アルキル基；フェニル基；フェニル置換されたアルキル基（例：ベンジル基、フェネチル基）等の炭素数７～１８のアラルキル基；これらの基の一部が酸素原子で置換されてなる基（以下「酸素原子置換基」ともいう）；ビニル基、アリル基、（メタ）アクリロイルオキシ基、オキシラニル基、オキセタニル基、グリシジル基；カルボキシル基が挙げられ、また、下記式ｇ１～ｇ７で表される基を挙げることもでき；
　「炭素数３～３０の有機基」としては、例えば、“アルキレン基、ヒドロキシアルキレン基、アルキル基、ビニル基、アリル基、（メタ）アクリロイルオキシ基、オキシラニル基、オキセタニル基およびグリシジル基”から選ばれる少なくとも１種の基を有する炭素数３～２０の有機基が挙げられ、また、下記式ｇ１～ｇ７で表される基を挙げることもできる。下記式ｇ１～ｇ７中、＊は結合位を示す。 In addition, in description of each formula which concerns on a moisture capture agent (A1), unless otherwise mentioned,
Examples of the “organic group having 1 to 18 carbon atoms” include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, 2-ethylhexyl, decyl. A linear or branched alkyl group having 1 to 18 carbon atoms such as dodecyl and octadecyl, preferably an alkyl group having 1 to 6 carbon atoms; a cycloalkyl group having 3 to 12 carbon atoms such as cyclohexyl and methylcyclohexyl; C4-C18 cycloalkyl group-substituted alkyl groups such as cyclohexylmethyl and cyclohexylethyl; phenyl groups; phenyl-substituted alkyl groups such as benzyl and phenethyl groups; aralkyl groups having 7 to 18 carbon atoms; A group in which a part of the group is substituted with an oxygen atom (hereinafter also referred to as “oxygen atom substituent”); Group, an allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, a glycidyl group; include carboxyl group, also can be a group represented by the following formulas g1 ~ g7;
Examples of the “organic group having 3 to 30 carbon atoms” include “alkylene group, hydroxyalkylene group, alkyl group, vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group and glycidyl group”. And an organic group having 3 to 20 carbon atoms having at least one kind of group, and groups represented by the following formulas g1 to g7. In the following formulas g1 to g7, * represents a bonding position.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　上述した、酸素原子置換基としては、例えば、メトキシメチル、エトキシメチル、プロポキシメチル、ブトキシメチル等のアルコキシアルキル基；アセトキシメチル、アセトキシエチル等のアルカノイルオキシアルキル基；フェノキシメチル、フェノキシエチル等のアリールオキシアルキル基；メトキシ等のアルコキシ基；フェノキシ等のアリールオキシ基；ヒドロキシメチル等のヒドロキシアルキル基が挙げられる。 Examples of the oxygen atom substituent described above include alkoxyalkyl groups such as methoxymethyl, ethoxymethyl, propoxymethyl, and butoxymethyl; alkanoyloxyalkyl groups such as acetoxymethyl and acetoxyethyl; aryloxy such as phenoxymethyl and phenoxyethyl An alkyl group; an alkoxy group such as methoxy; an aryloxy group such as phenoxy; and a hydroxyalkyl group such as hydroxymethyl.
　上記式（Ａ１－１）中、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６およびＲ７で表される基の炭素数の合計（ｎが０である場合、Ｒ２～Ｒ５で表される基の炭素数の合計）は、吸水能力と溶解性の観点から、好ましくは０～１８、より好ましくは０～１２である。 In the above formula (A1-1), the total number of carbon atoms of the groups represented by R 2 , R 3 , R 4 , R 5 , R 6 and R 7 (when n is 0, R 2 to R 5 are The total number of carbon atoms of the groups represented is preferably 0 to 18, more preferably 0 to 12, from the viewpoint of water absorption ability and solubility.
　また、上記式（Ａ１－１）のＲ３、Ｒ４およびＲ７（ｎ＝０の場合は、Ｒ３およびＲ４）は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよい。環状構造としては、例えば、シクロヘキサン環、シクロペンタン環が挙げられる。 In addition, R 3 , R 4 and R 7 in the above formula (A1-1) (when n = 0, R 3 and R 4 ) form a cyclic structure together with the carbon atoms to which they are directly bonded. You may do it. Examples of the cyclic structure include a cyclohexane ring and a cyclopentane ring.
　上記式（Ａ１－１）中、Ｒ１は、水素原子または炭素数１～６のアルキル基であることが好ましく、水素原子であることがより好ましい。 In the above formula (A1-1), R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and more preferably a hydrogen atom.
　上記式（Ａ１－１）中、Ｒ２～Ｒ５は、それぞれ独立に水素原子、上述した、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、炭素数４～１８のシクロアルキル基置換アルキル基、フェニル基、炭素数７～１８のアラルキル基、酸素原子置換基であることが好ましく、水素原子または炭素数１～６のアルキル基であることがより好ましく、水素原子であることがより好ましい。 In the above formula (A1-1), R 2 to R 5 are each independently a hydrogen atom, the aforementioned alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a group having 4 to 18 carbon atoms. It is preferably a cycloalkyl group-substituted alkyl group, a phenyl group, an aralkyl group having 7 to 18 carbon atoms, or an oxygen atom substituent, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, More preferably.
　上記式（Ａ１－１）中、Ｒ６～Ｒ７は、それぞれ独立に水素原子、水酸基、上述した、炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、炭素数４～１８のシクロアルキル基置換アルキル基、フェニル基、炭素数７～１８のアラルキル基、酸素原子置換基、ビニル基、アリル基、（メタ）アクリロイルオキシ基、オキシラニル基、オキセタニル基、グリシジル基、カルボキシル基、上記式ｇ１～ｇ７で表される基であることが好ましく、水素原子、水酸基、炭素数１～６のアルキル基または上記式ｇ１～ｇ２で表される基であることがより好ましい。 In the above formula (A1-1), R 6 to R 7 are each independently a hydrogen atom, a hydroxyl group, the above-described alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 4 to 4 carbon atoms. 18 cycloalkyl group-substituted alkyl group, phenyl group, aralkyl group having 7 to 18 carbon atoms, oxygen atom substituent, vinyl group, allyl group, (meth) acryloyloxy group, oxiranyl group, oxetanyl group, glycidyl group, carboxyl group The groups represented by the above formulas g1 to g7 are preferable, and a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, or a group represented by the above formulas g1 to g2 is more preferable.
　上記式（Ａ１－１）のＲ１～Ｒ７は、水分捕獲剤（Ａ）の吸水能力および他の成分との相溶性の観点から、上記原子または基が好ましい。 R 1 to R 7 in the above formula (A1-1) are preferably the above atoms or groups from the viewpoint of the water absorption ability of the moisture trapping agent (A) and compatibility with other components.
　上記式（Ａ１－１）中、ｎは０または１～１８の整数であり、好ましくは０または１であり、より好ましくは１である。ｎが２以上の整数である場合、Ｒ６およびＲ７はそれぞれ同一でも異なっていてもよい。 In the above formula (A1-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R 6 and R 7 may be the same or different.
　上記式（Ａ１－２）中、Ｒ１は水素原子または炭素数１～６のアルキル基であることが好ましく、Ｒ８はそれぞれ独立に上記式ｇ１～ｇ７で表される基であることが好ましい。 In the above formula (A1-2), R 1 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 8 is preferably independently a group represented by the above formulas g1 to g7. .
　［式（Ａ１－１）で表される構造部位を有する化合物］
　式（Ａ１－１）で表される構造部位を有する化合物は、例えば、下記式で表される化合物が挙げられる。より具体的には、後述するように、オルトエステル（ａ１）と多価アルコール（ａ２）と水酸基含有化合物（ａ３）とを反応させて得られる化合物を挙げることができ、その具体例としては、後述する式（Ａ１－ｉ）、式（Ａ１－ｉｉ）、式（Ａ１－ｉｉｉ）で表される化合物が挙げられる。 [Compound having a structural moiety represented by the formula (A1-1)]
Examples of the compound having a structural moiety represented by the formula (A1-1) include a compound represented by the following formula. More specifically, as will be described later, a compound obtained by reacting an ortho ester (a1), a polyhydric alcohol (a2) and a hydroxyl group-containing compound (a3) can be mentioned, and specific examples thereof include: Examples thereof include compounds represented by the following formula (A1-i), formula (A1-ii), and formula (A1-iii).
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　上記式中、Ａは、式（Ａ１－１）で表される構造部位であり；Ｙは、１分子中にｐ個（ｐ≧２）の水酸基を有する、後述する水酸基含有化合物（ａ３）から、ｍ個（２≦ｍ≦ｐ）の水酸基を除いた残基であり；ｍは２～ｐの整数である。 In the above formula, A is a structural moiety represented by the formula (A1-1); Y is a hydroxyl group-containing compound (a3) described later having p (p ≧ 2) hydroxyl groups in one molecule. , A residue excluding m (2 ≦ m ≦ p) hydroxyl groups; m is an integer of 2 to p.
　式（Ａ１－１）で表される構造部位を有する化合物としては、例えば、以下に説明するオルトエステル（ａ１）と多価アルコール（ａ２）と水酸基含有化合物（ａ３）とを反応させて得られる化合物が挙げられる。 The compound having a structural moiety represented by the formula (A1-1) can be obtained, for example, by reacting an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) described below. Compounds.
　（オルトエステル（ａ１））
　オルトエステル（ａ１）は、下記の式（ａ１）で表される化合物である。 (Orthoester (a1))
The ortho ester (a1) is a compound represented by the following formula (a1).
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式（ａ１）中、Ｒ１は水素原子または炭素数１～１８の有機基であり；３個のＲｘはそれぞれ独立に炭素数１～１８の有機基である。前記有機基としては、上述した、直鎖状または分岐鎖状の炭素数１～１８のアルキル基、炭素数３～１２のシクロアルキル基、炭素数４～１８のシクロアルキル基置換アルキル基が好ましく、直鎖状または分岐鎖状の炭素数１～６のアルキル基がより好ましい。 In the formula (a1), R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; each of three Rxs is independently an organic group having 1 to 18 carbon atoms. The organic group is preferably a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a substituted alkyl group having 4 to 18 carbon atoms. A linear or branched alkyl group having 1 to 6 carbon atoms is more preferable.
　オルトエステル（ａ１）としては、例えば、オルトギ酸メチル、オルトギ酸エチル、オルトギ酸プロピル、オルトギ酸ブチル、オルト酢酸メチル、オルト酢酸エチル、オルトプロピオン酸メチル、オルトプロピオン酸エチル、オルト酪酸メチル、オルト酪酸エチルが挙げられる。これらの中でも、オルトギ酸メチル、オルトギ酸エチル、オルト酢酸メチル、オルト酢酸エチルが好ましい。 Examples of the orthoester (a1) include methyl orthoformate, ethyl orthoformate, propyl orthoformate, butyl orthoformate, methyl orthoacetate, ethyl orthoacetate, methyl orthopropionate, ethyl orthopropionate, methyl orthobutyrate, orthobutyric acid. Ethyl is mentioned. Among these, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, and ethyl orthoacetate are preferable.
　オルトエステル（ａ１）は１種単独で用いてもよく、２種以上を併用してもよい。 Ortho ester (a1) may be used alone or in combination of two or more.
　（多価アルコール（ａ２））
　多価アルコール（ａ２）としては、例えば、１分子中に水酸基を２個以上有する化合物が挙げられ、式（ａ２－１）で表される化合物が好ましい。具体的には、１分子中に水酸基を２個有するα－グリコール、α－グリコール以外の１分子中に水酸基を２個以上有する化合物が挙げられる。 (Polyhydric alcohol (a2))
Examples of the polyhydric alcohol (a2) include a compound having two or more hydroxyl groups in one molecule, and a compound represented by the formula (a2-1) is preferable. Specific examples include α-glycol having two hydroxyl groups in one molecule, and a compound having two or more hydroxyl groups in one molecule other than α-glycol.
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式（ａ２－１）中、Ｒ２～Ｒ５は、それぞれ独立に水素原子または炭素数１～１８の有機基である。Ｒ６およびＲ７は、それぞれ独立に水素原子、水酸基または炭素数１～１８の有機基である。Ｒ３、Ｒ４およびＲ７は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよい。式（ａ２－１）中のＲ２～Ｒ７は、式（Ａ１－１）中の同一記号と同義であり、好適例も式（Ａ１－１）での説明と同様である。 In formula (a2-1), R 2 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms. R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms. R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure. R 2 to R 7 in formula (a2-1) are synonymous with the same symbols in formula (A1-1), and preferred examples are also the same as those described in formula (A1-1).
　式（ａ２－１）中、ｎは０または１～１８の整数であり、好ましくは０または１であり、より好ましくは１である。ｎが２以上の整数である場合、Ｒ６およびＲ７はそれぞれ同一でも異なっていてもよい。 In formula (a2-1), n is 0 or an integer of 1 to 18, preferably 0 or 1, and more preferably 1. When n is an integer of 2 or more, R 6 and R 7 may be the same or different.
　ｎが０であるα－グリコールが好ましい。α－グリコールは、隣接した２つの水酸基を有する。したがって、オルトエステルとα－グリコールとの反応が効率良く進行して、水分捕獲剤の製造に好適となる。 Α-glycol in which n is 0 is preferable. α-Glycol has two adjacent hydroxyl groups. Therefore, the reaction between the ortho ester and α-glycol proceeds efficiently, which is suitable for the production of a moisture scavenger.
　α－グリコールとしては、例えば、エチレングリコール、１，２－プロピレングリコール、１，２－ブチレングリコール、２，３－ブチレングリコール、１，２－ヘキサンジオール、１，２－ドデカンジオール、１，２－ジヒドロキシシクロヘキサン、ピナコール、長鎖アルキルモノエポキシドの加水分解物；グリセリンモノアセテート（α体）、グリセリンモノステアレート（α体）等の脂肪酸モノグリセリド（α体）；３－エトキシプロパン－１，２－ジオール、３－フェノキシプロパン－１，２－ジオールが挙げられる。これらの中でも、エチレングリコール、１，２－プロピレングリコール、１，２－ヘキサンジオールが好ましい。 Examples of α-glycol include ethylene glycol, 1,2-propylene glycol, 1,2-butylene glycol, 2,3-butylene glycol, 1,2-hexanediol, 1,2-dodecanediol, 1,2- Hydrolyzate of dihydroxycyclohexane, pinacol, long-chain alkyl monoepoxide; fatty acid monoglycerides (α form) such as glycerin monoacetate (α form), glycerin monostearate (α form); 3-ethoxypropane-1,2-diol , 3-phenoxypropane-1,2-diol. Among these, ethylene glycol, 1,2-propylene glycol, and 1,2-hexanediol are preferable.
　ｎが１である化合物が特に好ましい。前記化合物は、上述したα－グリコールと同様に近接した２つまたは３つ以上の水酸基を有する。したがって、オルトエステルと前記化合物との反応が効率良く進行して、オルトエステル化合物（Ａ１－１）の合成に好適となる。 A compound in which n is 1 is particularly preferable. The compound has two or three or more hydroxyl groups in close proximity like the α-glycol described above. Therefore, the reaction between the ortho ester and the compound proceeds efficiently, which is suitable for the synthesis of the ortho ester compound (A1-1).
　ｎが１である化合物としては、例えば、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，３－ブタンジオール、２－エチル－１，３－ヘキサンジオール、２，２－ジエチル－１，３－プロパンジオール、２，２，４－トリメチル－１，３－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、（２－アリルオキシメチル）－２－エチルプロパン－１，３－ジオール、２－（ヒドロキシメチル）－２－エチルプロパン－１，３－ジオール、グリセリン、２－フェノキシプロパン－１，３－ジオール、２－メチル－２－フェニルプロパン－１，３－ジオール、１，３－プロピレングリコール、１，３－ブチレングリコール、ジメチロールプロピオン酸、ジメチロールブタン酸、２－エチル－１，３－オクタンジオール、１，３－ジヒドロキシシクロヘキサン；グリセリンモノアセテート（β体）、グリセリンモノステアレート（β体）等の脂肪酸モノグリセリド（β体）が挙げられる。これらの中でも、ネオペンチルグリコール、２－メチル－１，３－プロパンジオール、２－メチル－２，４－ペンタンジオール、３－メチル－１，３－ブタンジオール、２－エチル－１，３－ヘキサンジオール、２，２－ジエチル－１，３－プロパンジオール、２，２，４－トリメチル－１，３－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、（２－アリルオキシメチル）－２－エチルプロパン－１，３－ジオール、２－（ヒドロキシメチル）－２－エチルプロパン－１，３－ジオール、グリセリンが特に好ましい。 Examples of the compound in which n is 1 include neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2- Ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propane Diol, (2-allyloxymethyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol, glycerin, 2-phenoxypropane-1,3-diol Diol, 2-methyl-2-phenylpropane-1,3-diol, 1,3-propylene glycol, 1,3-butylene glycol, dimethylol pro Fatty acid monoglycerides (β form) such as on acid, dimethylol butanoic acid, 2-ethyl-1,3-octanediol, 1,3-dihydroxycyclohexane; glycerin monoacetate (β form), glycerin monostearate (β form) Is mentioned. Among these, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 3-methyl-1,3-butanediol, 2-ethyl-1,3-hexane Diol, 2,2-diethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, (2-allyloxy Particularly preferred are methyl) -2-ethylpropane-1,3-diol, 2- (hydroxymethyl) -2-ethylpropane-1,3-diol and glycerin.
　（水酸基含有化合物（ａ３））
　水酸基含有化合物（ａ３）は、１分子中に２個以上の水酸基を有する化合物である。 (Hydroxyl-containing compound (a3))
The hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule.
　水酸基含有化合物（ａ３）が１分子中に２個以上の水酸基を有する化合物である場合、例えば、式（ａ２－１）で表される化合物等のように、多価アルコール（ａ２）の中から水酸基含有化合物（ａ３）を選択して使用することもできる。その場合、水酸基含有化合物（ａ３）として選択される化合物は、多価アルコール（ａ２）として選択された化合物以外の化合物が選択されることが好ましい。 When the hydroxyl group-containing compound (a3) is a compound having two or more hydroxyl groups in one molecule, for example, from the polyhydric alcohol (a2) such as a compound represented by the formula (a2-1) A hydroxyl group-containing compound (a3) can also be selected and used. In that case, it is preferable that the compound selected as the hydroxyl group-containing compound (a3) is selected from compounds other than the compound selected as the polyhydric alcohol (a2).
　水酸基含有化合物（ａ３）としては、例えば、１分子中に２個の水酸基を有する化合物、および１分子中に３個以上、好ましくは３個～４０個の水酸基を有する化合物が挙げられる。 Examples of the hydroxyl group-containing compound (a3) include a compound having 2 hydroxyl groups in one molecule and a compound having 3 or more, preferably 3 to 40 hydroxyl groups in one molecule.
　２個の水酸基を有する化合物としては、例えば、１，４－ブタンジオール、１，４－ジヒドロキシシクロヘキサン、１，５－ペンタンジオール、１，６－ヘキサンジオール、２，５－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、１，４－ジメチロールシクロヘキサン、トリシクロデカンジメタノール、２，２－ジメチル－３－ヒドロキシプロピル－２，２－ジメチル－３－ヒドロキシプロピオネート［このものはヒドロキシピバリン酸とネオペンチルグリコールとのエステルに相当する］、ビスフェノールＡ、ビスフェノールＦ、ビス（４－ヒドロキシヘキシル）－２，２－プロパン、ビス（４－ヒドロキシヘキシル）メタン、３，９－ビス（１，１－ジメチル－２－ヒドロキシエチル）－２，４，８，１０－テトラオキサスピロ［５，５］ウンデカン、ジエチレングリコール、トリエチレングリコール、テトラ以上のポリエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラ以上のポリプロピレングリコール、エチレンオキサイドとプロピレンオキサイドとを共重合してなる両末端に水酸基を有する共重合体、ポリカプロラクトンジオール等の両末端に水酸基を有する直鎖状ポリエステル、ポリカーボネートジオール、ジエポオキシドのカルボン酸付加物が挙げられる。 Examples of the compound having two hydroxyl groups include 1,4-butanediol, 1,4-dihydroxycyclohexane, 1,5-pentanediol, 1,6-hexanediol, 2,5-hexanediol, and 3-methyl. 1,5-pentanediol, 1,4-dimethylolcyclohexane, tricyclodecane dimethanol, 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate [this is hydroxy Corresponds to an ester of pivalic acid and neopentyl glycol], bisphenol A, bisphenol F, bis (4-hydroxyhexyl) -2,2-propane, bis (4-hydroxyhexyl) methane, 3,9-bis (1 , 1-Dimethyl-2-hydroxyethyl) -2,4,8,10-tetraoxy Spiro [5,5] undecane, diethylene glycol, triethylene glycol, tetra or higher polyethylene glycol, dipropylene glycol, tripropylene glycol, tetra or higher polypropylene glycol, hydroxyl groups at both ends formed by copolymerization of ethylene oxide and propylene oxide A linear polyester having hydroxyl groups at both ends, such as a polycaprolactone diol, polycarbonate diol, and a diepoxide carboxylic acid adduct.
　３個以上の水酸基を有する化合物としては、例えば、グリセリン、ジグリセリン、トリグリセリン、ペンタエリスリトール、ジペンタエリスリトール、ソルビトール、マンニット、トリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、トリス（２－ヒドロキシエチル）イソシアヌレート、グルコン酸、３個以上の水酸基を含有するポリマー（３個以上の水酸基を含有するポリエステル、ポリエーテル、アクリルポリマー、ケトン樹脂、フェノール樹脂、エポキシ樹脂、ウレタン樹脂、ポリ酢酸ビニルのケン化物であるポリビニルアルコール、グルコース等の天然糖類等）が挙げられる。 Examples of the compound having three or more hydroxyl groups include glycerin, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, sorbitol, mannitol, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxy). Ethyl) isocyanurate, gluconic acid, polymers containing 3 or more hydroxyl groups (polyesters containing 3 or more hydroxyl groups, polyethers, acrylic polymers, ketone resins, phenol resins, epoxy resins, urethane resins, polyvinyl acetates) Saponified polyvinyl alcohol, natural sugars such as glucose, etc.).
　水酸基含有化合物（ａ３）としては、分子量が９０～１０００００、特に９０～５０００の範囲内にある化合物が好ましい。また、水酸基含有化合物（ａ３）としては、水酸基価が２０ｍｇＫＯＨ／ｇ～１８５０ｍｇＫＯＨ／ｇ、特に４０ｍｇＫＯＨ／ｇ～１６５０ｍｇＫＯＨ／ｇの範囲内にある化合物が好ましい。 The hydroxyl group-containing compound (a3) is preferably a compound having a molecular weight in the range of 90 to 100,000, particularly 90 to 5,000. The hydroxyl group-containing compound (a3) is preferably a compound having a hydroxyl value in the range of 20 mgKOH / g to 1850 mgKOH / g, particularly 40 mgKOH / g to 1650 mgKOH / g.
　（反応比率）
　上述したオルトエステル（ａ１）と多価アルコール（ａ２）と水酸基含有化合物（ａ３）とを反応させて、オルトエステル化合物（Ａ１－１）を製造する場合において、オルトエステル（ａ１）と多価アルコール（ａ２）と水酸基含有化合物（ａ３）との配合比率は、特に限定されるものではない。 (Reaction ratio)
In the case of producing the ortho ester compound (A1-1) by reacting the ortho ester (a1), the polyhydric alcohol (a2) and the hydroxyl group-containing compound (a3), the ortho ester (a1) and the polyhydric alcohol are produced. The blending ratio of (a2) and the hydroxyl group-containing compound (a3) is not particularly limited.
　例えば、水酸基含有化合物（ａ３）中の水酸基１モル当量に対して、オルトエステル（ａ１）の量が０．０１モル～１０モル、好ましくは０．０５モル～５モル、より好ましくは０．１モル～２モルの範囲内にあり、かつ、多価アルコール（ａ２）の量が０．０１モル～１０モル、好ましくは０．０５モル～５モル、より好ましくは０．１モル～２モルの範囲内にある割合で用いることが、分子量制御のし易さなどの面から適当である。尚、多価アルコール（ａ２）の中から水酸基含有化合物（ａ３）を選択する場合、水酸基含有化合物（ａ３）として選択される化合物は、多価アルコール（ａ２）として選択された化合物以外の化合物が選択される。 For example, the amount of the orthoester (a1) is 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, more preferably 0.1 mol, relative to 1 mol equivalent of the hydroxyl group in the hydroxyl group-containing compound (a3). And the amount of the polyhydric alcohol (a2) is 0.01 mol to 10 mol, preferably 0.05 mol to 5 mol, more preferably 0.1 mol to 2 mol. Use in a proportion within the range is appropriate from the standpoint of ease of molecular weight control. When the hydroxyl group-containing compound (a3) is selected from the polyhydric alcohol (a2), the compound selected as the hydroxyl group-containing compound (a3) is a compound other than the compound selected as the polyhydric alcohol (a2). Selected.
　水分捕獲剤（Ａ１）は、オルトエステル（ａ１）、多価アルコール（ａ２）および水酸基含有化合物（ａ３）の３成分を縮合反応させることによって得ることができる。例えば、上述の３成分を、必要に応じて有機溶剤およびギ酸等の酸触媒の存在下で、通常は室温～２５０℃、好ましくは７０℃～２００℃の範囲内の温度で、１時間～２０時間程度、加熱して縮合反応させることによって好適に製造することができる。また、以上の方法で得られた化合物が有する基を、公知の方法により他の基に変換してもよい。合成方法については、例えば、国際公開第０１／０２１６１１号パンフレットを参考にすることができる。 The moisture trapping agent (A1) can be obtained by subjecting three components of an ortho ester (a1), a polyhydric alcohol (a2), and a hydroxyl group-containing compound (a3) to a condensation reaction. For example, the above-mentioned three components are usually added in the presence of an organic solvent and an acid catalyst such as formic acid as necessary, usually at room temperature to 250 ° C., preferably 70 ° C. to 200 ° C. for 1 hour to 20 It can be preferably produced by heating for about an hour to cause a condensation reaction. Moreover, you may convert the group which the compound obtained by the above method has into another group by a well-known method. For the synthesis method, for example, International Publication No. 01/021611 pamphlet can be referred to.
　このようにして、水酸基含有化合物（ａ３）中の水酸基が、オルトエステル（ａ１）と多価アルコール（ａ２）とから形成される５員環や６員環等によってブロックされた構造の水分捕獲剤（Ａ１）を得ることができる。 In this way, the water scavenger having a structure in which the hydroxyl group in the hydroxyl group-containing compound (a3) is blocked by a 5-membered ring or a 6-membered ring formed from the ortho ester (a1) and the polyhydric alcohol (a2). (A1) can be obtained.
　（式（Ａ１－１）で表される構造部位を有する化合物の例）
　式（Ａ１－１）で表される構造部位を有する化合物の具体例としては、例えば、式（Ａ１－ｉ）、式（Ａ１－ｉｉ）、式（Ａ１－ｉｉｉ）で表される化合物が挙げられる。 (Example of a compound having a structural moiety represented by the formula (A1-1))
Specific examples of the compound having a structural moiety represented by the formula (A1-1) include, for example, compounds represented by the formula (A1-i), the formula (A1-ii), and the formula (A1-iii). It is done.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式（Ａ１－ｉ）中、Ｙ１は、１分子中にｐ個（ｐ＝２～６）の水酸基を有する化合物からｍ個（２≦ｍ≦ｐ）の水酸基を除いたｍ価の残基である。Ｒ１～Ｒ７およびｎは、上記式（Ａ１－１）中のＲ１～Ｒ７およびｎと同義である。式（Ａ１－ｉ）で表される化合物は、例えば、上記式（ａ１）のオルトエステル、上記式（ａ２－１）の多価アルコール、および上述した１分子中に２個～６個の水酸基を有する化合物を原料として用いることで、合成することができる。 In formula (A1-i), Y 1 is an m-valent residue obtained by removing m (2 ≦ m ≦ p) hydroxyl groups from a compound having p (p = 2 to 6) hydroxyl groups in one molecule. It is. R 1 ~ R 7 and n have the same meanings as R 1 ~ R 7 and n in the formula (A1-1). The compound represented by the formula (A1-i) includes, for example, the orthoester of the above formula (a1), the polyhydric alcohol of the above formula (a2-1), and 2 to 6 hydroxyl groups in one molecule described above. It can synthesize | combine by using the compound which has this as a raw material.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式（Ａ１－ｉｉ）中、Ｙ２は、１分子中に２個の水酸基を有する化合物からその２個の水酸基を除いた２価の残基である。Ｒ１～Ｒ７およびｎは、式（Ａ１－１）中のＲ１～Ｒ７およびｎと同義である。上記化合物は、例えば、式（ａ１）のオルトエステル、式（ａ２－１）の多価アルコール、および１分子中に２個の水酸基を有する水酸基含有化合物（ａ３）を原料として用いることで、合成することができる。 In the formula (A1-ii), Y 2 is a divalent residue obtained by removing two hydroxyl groups from a compound having two hydroxyl groups in one molecule. R 1 ~ R 7 and n have the same meanings as R 1 ~ R 7 and n in formula (A1-1). The above compound is synthesized by using, for example, an ortho ester of the formula (a1), a polyhydric alcohol of the formula (a2-1), and a hydroxyl group-containing compound (a3) having two hydroxyl groups in one molecule as raw materials. can do.
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式（Ａ１－ｉｉｉ）中、Ｙ３は、１分子中に４個の水酸基を有する化合物からその４個の水酸基を除いた４価の残基である。Ｒ１～Ｒ７およびｎは、上記式（Ａ１－１）中のＲ１～Ｒ７およびｎと同義である。上記化合物は、例えば、上記式（ａ１）のオルトエステル、上記式（ａ２－１）の多価アルコール、および上述した１分子中に４個の水酸基を有する水酸基含有化合物（ａ３）化合物を原料として用いることで、合成することができる。 In the formula (A1-iii), Y 3 is a tetravalent residue obtained by removing four hydroxyl groups from a compound having four hydroxyl groups in one molecule. R 1 ~ R 7 and n have the same meanings as R 1 ~ R 7 and n in the formula (A1-1). Examples of the compound include, as a raw material, an ortho ester of the above formula (a1), a polyhydric alcohol of the above formula (a2-1), and a hydroxyl group-containing compound (a3) compound having four hydroxyl groups in one molecule described above. By using it, it can be synthesized.
　［式（Ａ１－２）で表される化合物］
　式（Ａ１－２）で表される構造部位を有する化合物は、その具体例として、例えば、下記式で表される化合物を挙げることができる。 [Compound represented by formula (A1-2)]
Specific examples of the compound having a structural moiety represented by the formula (A1-2) include compounds represented by the following formulas.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　＜水分捕獲剤（Ａ２）＞
　水分捕獲剤（Ａ２）は、カルボン酸無水物であり、例えば、モノカルボン酸の無水物、ジカルボン酸無水物およびテトラカルボン酸二無水物が挙げられる。水分捕獲剤（Ａ２）は、中性条件下においては水との反応性が低く安定であるが、酸または塩基の存在下では加水分解反応を容易に起こす。 <Moisture capture agent (A2)>
The moisture trapping agent (A2) is a carboxylic acid anhydride, and examples thereof include monocarboxylic acid anhydrides, dicarboxylic acid anhydrides, and tetracarboxylic dianhydrides. The moisture scavenger (A2) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.
　［モノカルボン酸の無水物］
　モノカルボン酸の無水物としては、トリフルオロ酢酸無水物、安息香酸無水物、イサトイン酸無水物、イソペンタン酸無水物、イソ酪酸無水物、ｎ－吉草酸無水物、クロトン酸無水物等が挙げられる。モノカルボン酸の無水物の炭素数は、加水分解により生成しうるカルボン酸の揮発性の観点から、好ましくは４～２０、より好ましくは４～１４である。 [Monocarboxylic acid anhydride]
Examples of monocarboxylic acid anhydrides include trifluoroacetic anhydride, benzoic anhydride, isatoic anhydride, isopentanoic anhydride, isobutyric anhydride, n-valeric anhydride, crotonic anhydride, and the like. . The carbon number of the monocarboxylic acid anhydride is preferably 4 to 20, more preferably 4 to 14, from the viewpoint of the volatility of the carboxylic acid that can be generated by hydrolysis.
　［ジカルボン酸無水物］
　ジカルボン酸無水物としては、下記式（Ａ２－１）で表される化合物が挙げられる。 [Dicarboxylic anhydride]
Examples of the dicarboxylic acid anhydride include compounds represented by the following formula (A2-1).
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
　上記式（Ａ２－１）中、Ｒａは、２価の有機基、例えば脂肪族基、環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、および“芳香族基が直接または架橋員（例：－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、アルキレン基、－Ｃ（ＣＦ３）２－）により相互に連結された非縮合多環式芳香族基”から選ばれる２価の基である。Ｒａの炭素数は、通常１～３０であるが、加水分解により生成しうるジカルボン酸の揮発性の観点から、好ましくは４～３０、より好ましくは６～１８である。 In the above formula (A2-1), Ra is a divalent organic group such as an aliphatic group, a cycloaliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and “an aromatic group is Non-condensed polycyclic aromatic groups connected to each other directly or by a bridging member (eg —O—, —CO—, —S—, —SO 2 —, an alkylene group, —C (CF 3 ) 2 —) Is a divalent group selected from The carbon number of Ra is usually 1-30, but is preferably 4-30, more preferably 6-18, from the viewpoint of the volatility of the dicarboxylic acid that can be produced by hydrolysis.
　上述のジカルボン酸無水物としては、例えば、脂肪族ジカルボン酸無水物、脂環式ジカルボン酸無水物、芳香族ジカルボン酸無水物が挙げられる。 Examples of the dicarboxylic acid anhydride include aliphatic dicarboxylic acid anhydrides, alicyclic dicarboxylic acid anhydrides, and aromatic dicarboxylic acid anhydrides.
　上述の脂肪族ジカルボン酸無水物としては、例えば、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の脂肪族飽和ジカルボン酸の無水物；マレイン酸、フマル酸、イタコン酸、メサコン酸、シトラコン酸等の脂肪族不飽和ジカルボン酸の無水物が挙げられる。 Examples of the above-mentioned aliphatic dicarboxylic acid anhydrides include, for example, anhydrides of aliphatic saturated dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; maleic acid, Examples thereof include anhydrides of aliphatic unsaturated dicarboxylic acids such as fumaric acid, itaconic acid, mesaconic acid and citraconic acid.
　上述の脂環式ジカルボン酸無水物としては、例えば、ヘキサヒドロフタル酸、ヘキサヒドロイソフタル酸、ヘキサヒドロテレフタル酸、４－メチルシクロヘキサンジカルボン酸無水物等の脂環式ジカルボン酸の無水物が挙げられる。 Examples of the alicyclic dicarboxylic acid anhydride include alicyclic dicarboxylic acid anhydrides such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and 4-methylcyclohexanedicarboxylic acid anhydride. .
　上述の芳香族ジカルボン酸無水物とは、少なくとも２つのカルボキシル基が、芳香族環に結合した有機化合物のジカルボン酸無水物のことを言う。芳香族ジカルボン酸無水物としては、例えば、フタル酸、２，３－ベンゾフェノンジカルボン酸、３，４－ベンゾフェノンジカルボン酸、２，３－ジカルボキシフェニルフェニルエーテル、３，４－ジカルボキシフェニルフェニルエーテル、２，３－ビフェニルジカルボン酸、３，４－ビフェニルジカルボン酸、２，３－ジカルボキシフェニルフェニルスルホン、３，４－ジカルボキシフェニルフェニルスルホン、２，３－ジカルボキシフェニルフェニルスルフィド、３，４－ジカルボキシフェニルフェニルスルフィド、１，２－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸、１，２－アントラセンジカルボン酸、２，３－アントラセンジカルボン酸、１，９－アントラセンジカルボン酸等の芳香族ジカルボン酸の無水物が挙げられる。 The above-mentioned aromatic dicarboxylic acid anhydride refers to a dicarboxylic acid anhydride of an organic compound in which at least two carboxyl groups are bonded to an aromatic ring. Examples of the aromatic dicarboxylic acid anhydride include phthalic acid, 2,3-benzophenone dicarboxylic acid, 3,4-benzophenone dicarboxylic acid, 2,3-dicarboxyphenyl phenyl ether, 3,4-dicarboxyphenyl phenyl ether, 2,3-biphenyldicarboxylic acid, 3,4-biphenyldicarboxylic acid, 2,3-dicarboxyphenylphenylsulfone, 3,4-dicarboxyphenylphenylsulfone, 2,3-dicarboxyphenylphenylsulfide, 3,4- Dicarboxyphenyl phenyl sulfide, 1,2-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,2-anthracenedicarboxylic acid, 2,3-anthracenedicarboxylic acid, 1,9- Anthracene dicarboxylic acid, etc. Anhydrides of aromatic dicarboxylic acids.
　水分捕獲剤（Ａ２）であるジカルボン酸無水物は、１種単独で用いてもよく、２種以上を併用してもよい。 The dicarboxylic anhydride that is the moisture trapping agent (A2) may be used alone or in combination of two or more.
　［テトラカルボン酸二無水物］
　テトラカルボン酸二無水物としては、下記式（Ａ２－２）で表される化合物が挙げられる。 [Tetracarboxylic dianhydride]
Examples of tetracarboxylic dianhydride include compounds represented by the following formula (A2-2).
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　上記式（Ａ２－２）中、Ｒｂは、４価の有機基、例えば脂肪族基、環式脂肪族基、単環式芳香族基、縮合多環式芳香族基、並びに、“芳香族基が直接または架橋員（例：－Ｏ－、－ＣＯ－、－Ｓ－、－ＳＯ２－、アルキレン基、－Ｃ（ＣＦ３）２－）により相互に連結された非縮合多環式芳香族基”から選ばれる４価の基である。Ｒｂの炭素数は、通常４～１００であるが、加水分解により生成しうるテトラカルボン酸の揮発性の観点から、好ましくは４～３０、より好ましくは４～１８である。 In the above formula (A2-2), Rb represents a tetravalent organic group such as an aliphatic group, a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group, and an “aromatic group”. Non-condensed polycyclic aromatics in which they are connected to each other directly or by a bridging member (eg —O—, —CO—, —S—, —SO 2 —, an alkylene group, —C (CF 3 ) 2 —) A tetravalent group selected from the group “. Rb usually has 4 to 100 carbon atoms, but preferably 4 to 30 and more preferably 4 to 18 from the viewpoint of volatility of tetracarboxylic acid that can be generated by hydrolysis.
　上述のテトラカルボン酸二無水物としては、例えば、脂肪族テトラカルボン酸二無水物、脂環式テトラカルボン酸二無水物、芳香族テトラカルボン酸二無水物が挙げられる。 Examples of the tetracarboxylic dianhydride described above include aliphatic tetracarboxylic dianhydrides, alicyclic tetracarboxylic dianhydrides, and aromatic tetracarboxylic dianhydrides.
　上述の脂肪族および脂環式テトラカルボン酸二無水物としては、例えば、ブタンテトラカルボン酸二無水物、１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，３－ジメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，３－ジクロロ－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－テトラメチル－１，２，３，４－シクロブタンテトラカルボン酸二無水物、１，２，３，４－シクロペンタンテトラカルボン酸二無水物、１，２，４，５－シクロヘキサンテトラカルボン酸二無水物、３，３’，４，４’－ジシクロヘキシルテトラカルボン酸二無水物、２，３，５－トリカルボキシシクロペンチル酢酸二無水物、３，５，６－トリカルボキシノルボルナン－２－酢酸二無水物、２，３，４，５－テトラヒドロフランテトラカルボン酸二無水物、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５－メチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５－エチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－７－メチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－７－エチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－８－メチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－８－エチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、１，３，３ａ，４，５，９ｂ－ヘキサヒドロ－５，８－ジメチル－５（テトラヒドロ－２，５－ジオキソ－３－フラニル）－ナフト［１，２－ｃ］－フラン－１，３－ジオン、５－（２，５－ジオキソテトラヒドロフラル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸二無水物、ビシクロ［２，２，２］－オクト－７－エン－２，３，５，６－テトラカルボン酸二無水物、式（Ｔ－１）および式（Ｔ－２）のそれぞれで表される化合物が挙げられる。 Examples of the aliphatic and alicyclic tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride Anhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopent Acetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b- Hexahydro-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 Methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5 Ethyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7- Methyl-5 (tetrahydro-2,5-dioxo 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-ethyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-ethyl-5 (tetrahydro-2,5-dioxo- 3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5,8-dimethyl-5 (tetrahydro-2,5- Dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3 -Dione, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo [2,2,2] -oct-7-ene-2 , 3,5,6-tetracarboxylic dianhydride, compounds represented by formula (T-1) and formula (T-2), respectively.
Figure JPOXMLDOC01-appb-C000018
Figure JPOXMLDOC01-appb-C000018
　上記の式（Ｔ－１）および式（Ｔ－２）中、Ｒ１１およびＲ１３は、芳香環を有する２価の有機基であり；Ｒ１２およびＲ１４は、水素原子またはアルキル基であり、複数存在するＲ１２およびＲ１４は、それぞれ同一でも異なっていてもよい。 In the above formulas (T-1) and (T-2), R 11 and R 13 are divalent organic groups having an aromatic ring; R 12 and R 14 are a hydrogen atom or an alkyl group A plurality of R 12 and R 14 may be the same or different.
　芳香族テトラカルボン酸二無水物とは、少なくとも４つのカルボキシル基が芳香族環に結合した有機化合物のテトラカルボン酸無水物のことを言う。芳香族テトラカルボン酸二無水物としては、例えば、ピロメリット酸二無水物、３，３’，４，４’－ベンゾフェノンテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルスルホンテトラカルボン酸二無水物、１，４，５，８－ナフタレンテトラカルボン酸二無水物、２，３，６，７－ナフタレンテトラカルボン酸二無水物、３，３’，４，４’－ビフェニルエーテルテトラカルボン酸二無水物、３，３’，４，４’－ジフェニルメタンテトラカルボン酸二無水物、３，３’，４，４’－ジメチルジフェニルシランテトラカルボン酸二無水物、３，３’，４，４’－テトラフェニルシランテトラカルボン酸二無水物、１，２，３，４－フランテトラカルボン酸二無水物、４，４’－ビス（３，４－ジカルボキシフェノキシ）ジフェニルスルフィド二無水物、４，４’－ビス（３，４－ジカルボキシフェノキシ）ジフェニルスルホン二無水物、４，４’－ビス（３，４－ジカルボキシフェノキシ）ジフェニルプロパン二無水物、３，３’，４，４’－パーフルオロイソプロピリデンジフタル酸二無水物、３，３’，４，４’－ビフェニルテトラカルボン酸二無水物、ビス（フタル酸）フェニルホスフィンオキサイド二無水物、ｐ－フェニレン－ビス（トリフェニルフタル酸）二無水物、ｍ－フェニレン－ビス（トリフェニルフタル酸）二無水物、ビス（トリフェニルフタル酸）－４，４’－ジフェニルエーテル二無水物、ビス（トリフェニルフタル酸）－４，４’－ジフェニルメタン二無水物、エチレングリコール－ビス（アンヒドロトリメリテート）、プロピレングリコール－ビス（アンヒドロトリメリテート）、１，４－ブタンジオール－ビス（アンヒドロトリメリテート）、１，６－ヘキサンジオール－ビス（アンヒドロトリメリテート）、１，８－オクタンジオール－ビス（アンヒドロトリメリテート）、２，２－ビス（４－ヒドロキシフェニル）プロパン－ビス（アンヒドロトリメリテート）、２，３，４，５－ピリジンテトラカルボン酸二無水物、２，６－ビス（３，４－ジカルボキシフェニル）ピリジン、下記式（Ｔ－３－１）～（Ｔ－３－４）のそれぞれで表される化合物が挙げられる。 An aromatic tetracarboxylic dianhydride means a tetracarboxylic anhydride of an organic compound in which at least four carboxyl groups are bonded to an aromatic ring. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenyl sulfone. Tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenyl Ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylmethane tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′ , 4,4′-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) dipheny Sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ', 4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p- Phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenyl) Phthalic acid) -4,4'-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol -Bis (anhydrotrimellitate), 1,4-butanediol-bis (anhydrotrimellitate), 1,6-hexanediol-bis (anhydrotrimellitate), 1,8-octanediol-bis (Anhydro trimellitate), 2,2-bis (4-hydroxyphenyl) propane-bis (anhydro trimellitate), 2,3,4,5-pyridinetetracarboxylic dianhydride, 2,6- Examples thereof include bis (3,4-dicarboxyphenyl) pyridine and compounds represented by the following formulas (T-3-1) to (T-3-4).
Figure JPOXMLDOC01-appb-C000019
Figure JPOXMLDOC01-appb-C000019
　水分捕獲剤（Ａ２）であるテトラカルボン酸二無水物は１種単独で用いてもよく、２種以上を併用してもよい。 The tetracarboxylic dianhydride that is the moisture trapping agent (A2) may be used alone or in combination of two or more.
　＜水分捕獲剤（Ａ３）＞
　水分捕獲剤（Ａ３）は、式（Ａ３－１）で表される化合物および式（Ａ３－２）で表される化合物から選ばれる少なくとも１種である。水分捕獲剤（Ａ３）は、中性条件下においては水との反応性が低く安定であるが、酸または塩基の存在下では加水分解反応を容易に起こす。 <Moisture capture agent (A3)>
The moisture trapping agent (A3) is at least one selected from a compound represented by the formula (A3-1) and a compound represented by the formula (A3-2). The moisture trapping agent (A3) is stable with low reactivity with water under neutral conditions, but easily causes a hydrolysis reaction in the presence of an acid or a base.
Figure JPOXMLDOC01-appb-C000020
Figure JPOXMLDOC01-appb-C000020
　上記式（Ａ３－１）および（Ａ３－２）中、Ｘは、ケイ素原子、チタン原子、または、ジルコニウム原子を示す。これらの中でも、ケイ素原子が好ましい。 In the above formulas (A3-1) and (A3-2), X represents a silicon atom, a titanium atom, or a zirconium atom. Among these, a silicon atom is preferable.
　上記式（Ａ３－１）および（Ａ３－２）中、Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、あるいは、ベンジル基を示す。 In the above formulas (A3-1) and (A3-2), R 21 is at least one selected from a (meth) acryloyl group, an oxiranyl group, an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, and an isocyanate group. An organic group having the above group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a phenyl group, or a benzyl group.
　上記式（Ａ３－１）および（Ａ３－２）中、Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、または、メルカプト基を示す。 In the above formulas (A3-1) and (A3-2), R 22 is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon number 3 -12 cycloalkyl group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4-epoxycyclohexyl group Or a mercapto group.
　式（Ａ３－１）および（Ａ３－２）中、ｒは０～２の整数であり；ｐは０～６の整数であり、０～３の整数が好ましく、０または３であることがより好ましい。ｓは１～３０の整数であり、１～２０の整数が好ましく、１～１０の整数がより好ましい。 In the formulas (A3-1) and (A3-2), r is an integer of 0 to 2; p is an integer of 0 to 6, preferably an integer of 0 to 3, more preferably 0 or 3 preferable. s is an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.
　－（ＣＨ２）ｐ－Ｒ２２で表される基が複数ある場合はそれぞれ同一であっても異なっていてもよい。－ＯＲ２１で表される基が複数ある場合はそれぞれ同一であっても異なっていてもよい。 When there are a plurality of groups represented by — (CH 2 ) p —R 22, they may be the same or different. When there are a plurality of groups represented by —OR 21, they may be the same or different.
　式（Ａ３－１）および（Ａ３－２）中のＲ２１における前記有機基としては、例えば、下記式で表される基が挙げられる。下記式中、＊は結合位を示し、Ｒ２３は水素原子またはメチル基であり、Ｒ２４は炭素数１～３のアルキレン基であり、ｎは１～３の整数である。 Examples of the organic group for R 21 in formulas (A3-1) and (A3-2) include groups represented by the following formulae. In the following formula, * represents a bonding position, R 23 is a hydrogen atom or a methyl group, R 24 is an alkylene group having 1 to 3 carbon atoms, and n is an integer of 1 to 3.
Figure JPOXMLDOC01-appb-C000021
Figure JPOXMLDOC01-appb-C000021
　また、上記式（Ａ３－１）および上記式（Ａ３－２）中のＲ２１におけるアルキル基は、直鎖状および分岐状のいずれでもよく、例えば、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔ－ブチル、ペンチル、ヘキシルが挙げられ、シクロアルキル基としては、例えば、シクロヘキシルが挙げられる。 In addition, the alkyl group for R 21 in the above formula (A3-1) and the above formula (A3-2) may be either linear or branched, and for example, methyl, ethyl, n-propyl, isopropyl, n Examples include -butyl, isobutyl, t-butyl, pentyl, and hexyl. Examples of the cycloalkyl group include cyclohexyl.
　成分（Ａ）の上記式（Ａ３－１）で表される化合物および上記式（Ａ３－２）で表される化合物において、Ｒ２２におけるアルキル基は、直鎖状、分岐状および環状のいずれでもよい。Ｒ２２におけるアルキル基の炭素数は１～２０であるが、炭素数は１～１０が好ましく、１～６がより好ましい。具体的には、Ｒ２１において例示したアルキル基の他、ｎ－ヘプチル基、ｎ－オクチル基、２－エチルへキシル基、ｎ－ノニル基、ｎ－デシル基、ｎ－ウンデシル基、ｎ－ドデシル基、ｎ－トリデシル基、ｎ－テトラデシル基、ｎ－ヘキサデシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。 In the compound represented by the above formula (A3-1) and the compound represented by the above formula (A3-2) in the component (A), the alkyl group in R 22 is any of linear, branched and cyclic Good. The alkyl group in R 22 has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms. Specifically, in addition to the alkyl group exemplified for R 21 , n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Group, n-tridecyl group, n-tetradecyl group, n-hexadecyl group, cycloheptyl group, cyclooctyl group and the like.
　また、上記式（Ａ３－１）および上記式（Ａ３－２）中のＲ２２における芳香族炭化水素基としては、例えば、単環から３環式の芳香族炭化水素基が挙げられ、具体的には、フェニル基、トリル基、ナフチル基、アントリル基、フェナントリル基が挙げられる。これらの中でも、フェニル基、トリル基、ナフチル基が好ましく、フェニル基がより好ましい。 In addition, examples of the aromatic hydrocarbon group for R 22 in the above formula (A3-1) and the above formula (A3-2) include monocyclic to tricyclic aromatic hydrocarbon groups. Include a phenyl group, a tolyl group, a naphthyl group, an anthryl group, and a phenanthryl group. Among these, a phenyl group, a tolyl group, and a naphthyl group are preferable, and a phenyl group is more preferable.
　さらに、上記式（Ａ３－１）および上記式（Ａ３－２）中のＲ２２におけるアルキル基、シクロアルキル基および芳香族炭化水素基は置換基を有していてもよく、置換基としては、例えば、ハロゲン原子、水酸基、ニトロ基、シアノ基、炭素数１～６のアルコキシ基等を挙げることができる。尚、置換基の位置および数は任意であり、置換基を２以上有する場合、その置換基は同一であっても異なっていてもよい。ハロゲン原子としては、フッ素原子、臭素原子、塩素原子およびヨウ素原子が挙げられ、それらの中でも、フッ素原子が好ましい。ハロゲン原子は、アルキル基、シクロアルキル基および芳香族炭化水素基の水素原子の一部または全部を置換することができるが、全て置換されているものが好ましい。ハロゲン置換アルキル基およびハロゲン置換シクロアルキル基の具体例としては、トリフルオロメチル基、パーフルオロエチル基、パーフルオロプロピル基、パーフルオロイソプロピル基、パーフルオロシクロプロピル基等のパーフルオロアルキル基およびパーフルオロシクロアルキル基が挙げられる。また、炭素数１～６のアルコキシ基としては、例えば、メトキシ基、エトキシ基、ｎ－プロポキシ基、ｉｓｏ－プロポキシ基が挙げられる。 Further, the alkyl group, cycloalkyl group and aromatic hydrocarbon group in R 22 in the above formula (A3-1) and the above formula (A3-2) may have a substituent. Examples thereof include a halogen atom, a hydroxyl group, a nitro group, a cyano group, and an alkoxy group having 1 to 6 carbon atoms. In addition, the position and number of substituents are arbitrary, and when it has two or more substituents, the substituents may be the same or different. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among these, a fluorine atom is preferable. The halogen atom can substitute a part or all of the hydrogen atoms of the alkyl group, cycloalkyl group and aromatic hydrocarbon group, but preferably all are substituted. Specific examples of the halogen-substituted alkyl group and the halogen-substituted cycloalkyl group include perfluoroalkyl groups such as trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorocyclopropyl group, and perfluoroalkyl groups. A cycloalkyl group is mentioned. Examples of the alkoxy group having 1 to 6 carbon atoms include a methoxy group, an ethoxy group, an n-propoxy group, and an iso-propoxy group.
　上述のＲ２２における（メタ）アクリロイルオキシ基とは、アクリロイルオキシ基およびメタクリロイルオキシ基を包含する概念である。 The (meth) acryloyloxy group in R 22 described above is a concept including an acryloyloxy group and a methacryloyloxy group.
　以上で例示された中でも、Ｒ２２としては、炭素数１～６のアルキル基、フェニル基、（メタ）アクリロイルオキシ基またはグリシドキシ基が好ましい。尚、同一分子内にＲ２が複数存在する場合、それらは同一であっても異なっていてもよい。 Among those exemplified above, R 22 is preferably an alkyl group having 1 to 6 carbon atoms, a phenyl group, a (meth) acryloyloxy group, or a glycidoxy group. In addition, when two or more R2 exists in the same molecule, they may be the same or different.
　水分捕獲剤（Ａ３）である上記式（Ａ３－１）で表される化合物および上記式（Ａ３－２）で表される化合物のより具体的な例としては、Ｘがケイ素原子であるシラン化合物を挙げることができる。 More specific examples of the compound represented by the above formula (A3-1) and the compound represented by the above formula (A3-2) which are moisture trapping agents (A3) include silane compounds wherein X is a silicon atom Can be mentioned.
　上記式（Ａ３－１）で表される化合物において、ｒが０かつｓが１であるシラン化合物としては、例えば、ジメチルジメトキシシラン、ジブチルジメトキシシラン等の炭素数１～２０のアルキル基を２つ有するアルコキシシラン化合物；ジフェニルジメトキシシラン等の炭素数６～１４の芳香族炭化水素基を２つ有するアルコキシシラン化合物；３－メタクリロイルオキシプロピルメチルジメトキシシラン、３－メタクリロイルオキシプロピルエチルジメトキシシラン、３－メタクリロイルオキシプロピルメチルジエトキシシラン、３－アクリロイルオキシプロピルメチルジメトキシシラン、３－アクリロイルオキシプロピルエチルジメトキシシラン、３－アクリロイルオキシプロピルメチルジエトキシシラン等の（メタ）アクリロイルオキシ基と炭素数１～２０のアルキル基とを有するアルコキシシラン化合物；３－メタクリロイルオキシプロピルフェニルジメトキシシラン、３－メタクリロイルオキシプロピルフェニルジエトキシシラン、３－アクリロイルオキシプロピルフェニルジメトキシシラン、３－アクリロイルオキシプロピルフェニルジエトキシシラン等の（メタ）アクリロイルオキシ基と炭素数６～１４の芳香族炭化水素基とを有するアルコキシシラン化合物；３，３’－ジメタクリロイルオキシプロピルジメトキシシラン、３，３’－ジアクリロイルオキシプロピルジメトキシシラン等の（メタ）アクリロイルオキシ基を２つ有するアルコキシシラン化合物；３－グリシドキシプロピルメチルジメトキシシラン、３－グリシドキシプロピルエチルジメトキシシラン、３－グリシドキシプロピルメチルジエトキシシラン、３－グリシドキシプロピルエチルジエトキシシラン等のグリシドキシ基と炭素数１～２０のアルキル基とを有するアルコキシシラン化合物；３－グリシドキシプロピルフェニルジメトキシシラン、３－グリシドキシプロピルフェニルジエトキシシラン等のグリシドキシ基と炭素数６～１４の芳香族炭化水素基とを有するアルコキシシラン化合物が挙げられる。 In the compound represented by the formula (A3-1), examples of the silane compound in which r is 0 and s is 1 include two alkyl groups having 1 to 20 carbon atoms such as dimethyldimethoxysilane and dibutyldimethoxysilane. Alkoxysilane compounds having two C6-C14 aromatic hydrocarbon groups such as diphenyldimethoxysilane; 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylethyldimethoxysilane, 3-methacryloyl (Meth) acryloylo such as oxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropylethyldimethoxysilane, 3-acryloyloxypropylmethyldiethoxysilane Alkoxysilane compounds having a silyl group and an alkyl group having 1 to 20 carbon atoms; 3-methacryloyloxypropylphenyldimethoxysilane, 3-methacryloyloxypropylphenyldiethoxysilane, 3-acryloyloxypropylphenyldimethoxysilane, 3-acryloyloxy Alkoxysilane compounds having a (meth) acryloyloxy group such as propylphenyldiethoxysilane and an aromatic hydrocarbon group having 6 to 14 carbon atoms; 3,3′-dimethacryloyloxypropyldimethoxysilane, 3,3′-di Alkoxysilane compounds having two (meth) acryloyloxy groups such as acryloyloxypropyldimethoxysilane; 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylethyldimethoxysila Alkoxysilane compounds having a glycidoxy group and an alkyl group having 1 to 20 carbon atoms, such as 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropylethyldiethoxysilane; 3-glycidoxypropylphenyldimethoxy Examples thereof include alkoxysilane compounds having a glycidoxy group such as silane and 3-glycidoxypropylphenyldiethoxysilane and an aromatic hydrocarbon group having 6 to 14 carbon atoms.
　上記式（Ａ３－１）で表される化合物において、ｒが１かつｓが１であるシラン化合物としては、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリ－ｉｓｏ－プロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリ－ｉｓｏ－プロポキシシラン、エチルトリブトキシシラン、ブチルトリメトキシシラン、デシルトリメトキシシラン等の炭素数１～２０のアルキル基を１つ有するアルコキシシラン化合物；トリフルオロプロピルトリメトキシシラン等の炭素数１～２０のハロゲン置換アルキル基を１つ有するアルコキシシラン化合物；フェニルトリメトキシシラン、フェニルトリエトキシシラン等の炭素数６～１４の芳香族炭化水素基を１つ有するアルコキシシラン化合物；３－メタクリロイルオキシプロピルトリメトキシシラン、３－メタクリロイルオキシプロピルトリエトキシシラン、３－メタクリロイルオキシプロピルトリプロポキシシラン、３－アクリロイルオキシプロピルトリメトキシシラン、３－アクリロイルオキシプロピルトリエトキシシラン、３－アクリロイルオキシプロピルトリプロポキシシラン等の（メタ）アクリロイルオキシ基を１つ有するアルコキシシラン化合物が挙げられる。 In the compound represented by the formula (A3-1), examples of the silane compound in which r is 1 and s is 1 include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-iso-propoxysilane, methyltributoxy Alkoxysilane compounds having one alkyl group having 1 to 20 carbon atoms such as silane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltri-iso-propoxysilane, ethyltributoxysilane, butyltrimethoxysilane, decyltrimethoxysilane An alkoxysilane compound having one halogen-substituted alkyl group having 1 to 20 carbon atoms such as trifluoropropyltrimethoxysilane; an aromatic hydrocarbon group having 6 to 14 carbon atoms such as phenyltrimethoxysilane and phenyltriethoxysilane; I have one Coxysilane compounds; 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-methacryloyloxypropyltripropoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acryloyloxypropyltriethoxysilane, 3- Examples include alkoxysilane compounds having one (meth) acryloyloxy group such as acryloyloxypropyltripropoxysilane.
　上記式（Ａ３－１）で表される化合物において、ｒが２かつｓが１であるシラン化合物としては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラ－ｎ－プロポキシシラン、テトラ－ｉｓｏ－プロポキシシラン、テトラブトキシシラン、テトラフェノキシシラン、テトラベンジロキシシランが挙げられる。 In the compound represented by the formula (A3-1), examples of the silane compound in which r is 2 and s is 1 include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetra-iso-propoxy. Examples include silane, tetrabutoxysilane, tetraphenoxysilane, and tetrabenzyloxysilane.
　上記式（Ａ３－１）で表される化合物としては、さらに、以下に示す式（Ａ３－ｉ）、式（Ａ３－ｉｉ）および式（Ａ３－ｉｉ－２）の化合物を挙げることができる。式（Ａ３－ｉ）、式（Ａ３－ｉｉ）および式（Ａ３－ｉｉ－２）の化合物等は、下記式で例示されるように、テトラエトキシシランに、水酸基と重合性基（オキシラニル基、オキセタニル基、（メタ）アクリロイル基等）とを併せ持つ化合物をアルカリ存在下で反応させることにより得ることができる。 Examples of the compound represented by the above formula (A3-1) further include compounds represented by the following formula (A3-i), formula (A3-ii) and formula (A3-ii-2). The compounds of formula (A3-i), formula (A3-ii) and formula (A3-ii-2), as exemplified by the following formula, have a hydroxyl group and a polymerizable group (oxiranyl group, It can be obtained by reacting a compound having both an oxetanyl group and a (meth) acryloyl group in the presence of an alkali.
Figure JPOXMLDOC01-appb-C000022
Figure JPOXMLDOC01-appb-C000022
　上記式（Ａ３－１）で表される化合物としては、さらに、以下で示す式（Ａ３－ｉｉｉ）および式（Ａ３－ｉｖ）の化合物を挙げることができる。式（Ａ３－ｉｉｉ）および式（Ａ３－ｉｖ）の化合物等は、下記式で示されるように、メトキシ基を有するシラン化合物に、水酸基と重合性基（オキシラニル基、オキセタニル基、（メタ）アクリロイル基等）とを併せ持つ化合物をアルカリ存在下で反応させることで得ることができる。 Examples of the compound represented by the above formula (A3-1) further include compounds represented by the following formulas (A3-iii) and (A3-iv). The compounds of formula (A3-iii) and formula (A3-iv), as shown by the following formula, can be converted to a silane compound having a methoxy group with a hydroxyl group and a polymerizable group (oxiranyl group, oxetanyl group, (meth) acryloyl group). Group) and the like, can be obtained by reacting in the presence of an alkali.
Figure JPOXMLDOC01-appb-C000023
Figure JPOXMLDOC01-appb-C000023
　上記式（Ａ３－１）で表される化合物としては、さらに、下記の式（Ａ３－ｖ）で表される化合物が挙げられる。 Examples of the compound represented by the above formula (A3-1) further include a compound represented by the following formula (A3-v).
Figure JPOXMLDOC01-appb-C000024
Figure JPOXMLDOC01-appb-C000024
　また、上記式（Ａ３－２）で表される化合物としては、
　３－メタクリロイルオキシプロピルジメチルメトキシシラン、３－メタクリロイルオキシプロピルジエチルエトキシシラン、３－メタクリロイルオキシプロピルジメチルエトキシシラン、３－アクリロイルオキシプロピルジメチルメトキシシラン、３－アクリロイルオキシプロピルジエチルメトキシシラン、３－アクリロイルオキシプロピルジメチルエトキシシラン等の（メタ）アクリロイルオキシ基を１つ有し、炭素数１～２０のアルキル基を２つ有するアルコキシシラン化合物；
　３－メタクリロイルオキシプロピルジフェニルメトキシシラン、３－メタクリロイルオキシプロピルジフェニルエトキシシラン、３－アクリロイルオキシプロピルジフェニルメトキシシラン、３－アクリロイルオキシプロピルジフェニルエトキシシラン等の（メタ）アクリロイルオキシ基を１つ有し、炭素数６～１４の芳香族炭化水素基を２つ有するアルコキシシラン化合物；
　３－グリシドキシプロピルジメチルメトキシシラン、３－グリシドキシプロピルジエチルメトキシシラン、３－グリシドキシプロピルジメチルエトキシシラン等のグリシドキシ基を１つ有し、炭素数１～２０のアルキル基を２つ有するアルコキシシラン化合物；
　３－グリシドキシプロピルジフェニルメトキシシラン、３－グリシドキシプロピルジフェニルエトキシシラン等のグリシドキシ基を１つ有し、炭素数６～１４の芳香族炭化水素基を２つ有するシラン化合物
が挙げられる。 In addition, as the compound represented by the above formula (A3-2),
3-methacryloyloxypropyldimethylmethoxysilane, 3-methacryloyloxypropyldiethylethoxysilane, 3-methacryloyloxypropyldimethylethoxysilane, 3-acryloyloxypropyldimethylmethoxysilane, 3-acryloyloxypropyldiethylmethoxysilane, 3-acryloyloxypropyl An alkoxysilane compound having one (meth) acryloyloxy group such as dimethylethoxysilane and two alkyl groups having 1 to 20 carbon atoms;
It has one (meth) acryloyloxy group such as 3-methacryloyloxypropyldiphenylmethoxysilane, 3-methacryloyloxypropyldiphenylethoxysilane, 3-acryloyloxypropyldiphenylmethoxysilane, 3-acryloyloxypropyldiphenylethoxysilane, and the like. An alkoxysilane compound having two aromatic hydrocarbon groups of formula 6 to 14;
One glycidoxy group such as 3-glycidoxypropyldimethylmethoxysilane, 3-glycidoxypropyldiethylmethoxysilane, 3-glycidoxypropyldimethylethoxysilane, and two alkyl groups having 1 to 20 carbon atoms Having an alkoxysilane compound;
Examples thereof include silane compounds having one glycidoxy group and two aromatic hydrocarbon groups having 6 to 14 carbon atoms, such as 3-glycidoxypropyldiphenylmethoxysilane and 3-glycidoxypropyldiphenylethoxysilane.
　水分捕獲剤（Ａ３）である上記式（Ａ３－１）で表される化合物および上記式（Ａ３－２）で表される化合物において、市販品で購入できるものとして、例えば、ＯＸＴ－１９１（東亞合成社製）およびＸ－２２－３０００Ｔ（信越化学工業社製）等が挙げられる。 In the compound represented by the above formula (A3-1) and the compound represented by the above formula (A3-2) which are the moisture trapping agent (A3), commercially available products such as OXT-191 (Toago) Synthetic Co., Ltd.) and X-22-3000T (manufactured by Shin-Etsu Chemical Co., Ltd.).
　＜作用効果の説明＞
　本発明の実施形態の水分捕獲体形成組成物の作用効果について、以下に説明する。 <Description of effects>
The effects of the moisture trap forming composition of the embodiment of the present invention will be described below.
　本発明の実施形態の水分捕獲体形成組成物は、酸・塩基発生剤（Ｂ）を含有し、加熱および光照射の少なくとも一方を受けると、酸・塩基発生剤（Ｂ）から酸または塩基が形成される。この酸または塩基により、本実施形態の水分捕獲体形成組成物が使用される系内に存在する水に基づき、水分捕獲剤（Ａ）の加水分解反応が促進されることで系内に存在する水を高効率に消費することができる。本明細書において、「水分の捕獲」とは、このような意味で用いられる。水分捕獲剤（Ａ）の加水分解生成物は、後述するように有機ＥＬ素子および液晶表示素子等の電子デバイスの性能を劣化させる懸念が少ない。 The water-capturing body-forming composition of the embodiment of the present invention contains an acid / base generator (B), and when subjected to at least one of heating and light irradiation, an acid or base is generated from the acid / base generator (B). It is formed. The acid or base is present in the system by promoting the hydrolysis reaction of the water trapping agent (A) based on the water present in the system in which the composition for forming a moisture trap of the present embodiment is used. Water can be consumed with high efficiency. In the present specification, “moisture capture” is used in this sense. The hydrolysis product of the moisture trapping agent (A) is less likely to degrade the performance of electronic devices such as organic EL elements and liquid crystal display elements as will be described later.
　このため、本発明では、上記水分捕獲体形成組成物を用いて上記有機ＥＬ素子の水分捕獲体を形成する時に、素子内の水分を高効率に除去することができる。また、本発明の実施形態の水分捕獲形成組成物から形成された封止材等の水分捕獲体には、水分捕獲剤（Ａ）またはこれに由来する構造部分が一部、分解されずに残留していると考えられる。このため、その形成の後も長期間に亘って素子内の水分を吸収することができ、水分に起因する有機ＥＬ素子の特性低下を抑制することができる。 For this reason, in the present invention, when the moisture trap of the organic EL device is formed using the moisture trap forming composition, moisture in the device can be removed with high efficiency. Further, in the moisture trap such as the sealing material formed from the moisture trap forming composition of the embodiment of the present invention, the moisture trap agent (A) or a part of the structure derived therefrom remains partially without being decomposed. it seems to do. For this reason, moisture in the element can be absorbed over a long period of time after the formation, and deterioration of the characteristics of the organic EL element due to moisture can be suppressed.
　尚、一般的に分解生成物は、例えば、揮発等をして有機ＥＬ素子内に分散し、有機ＥＬ素子の発光層となる有機ＥＬ層に達して汚染し、ダークスポットを発生させる等、有機ＥＬ素子の性能を劣化させる懸念がある。しかしながら、本発明では、水分捕獲剤（Ａ）から生成する加水分解生成物は、適度な分子量を備えていることから揮発等が抑制されており、封止材等の水分捕獲体中に留まることができる。加水分解生成物は分子サイズが大きいほど、水分捕獲体に留まりやすいため、水分捕獲剤（Ａ）としては、分子量が比較的大きい化合物が好ましい。 In general, the decomposition products are dispersed in the organic EL element by volatilization or the like, reach the organic EL layer that becomes the light emitting layer of the organic EL element, contaminate, and generate dark spots. There is a concern of degrading the performance of the EL element. However, in the present invention, the hydrolysis product generated from the moisture trapping agent (A) has an appropriate molecular weight, so that volatilization and the like are suppressed and remain in the moisture trap such as a sealing material. Can do. As the hydrolyzed product has a larger molecular size, it tends to stay in the moisture trapping body. Therefore, a compound having a relatively large molecular weight is preferable as the moisture trapping agent (A).
　本発明の実施形態で用いられる水分捕獲剤（Ａ）は、水分を捕獲した状態であっても、低分子アルコール等のような揮発性の高い加水分解生成物を生じ難く、例えば、加水分解生成物の付着によりダークスポットを生じ易い有機ＥＬ素子に用いられた場合でも、有機ＥＬ層への上記分解生成物の付着によるダークスポットの発生を抑制することができる。 The water scavenger (A) used in the embodiment of the present invention hardly generates a highly volatile hydrolysis product such as a low molecular weight alcohol even in a state where water is trapped. Even when it is used for an organic EL element in which a dark spot is likely to be generated due to adhesion of an object, generation of a dark spot due to adhesion of the decomposition product to the organic EL layer can be suppressed.
　水分捕獲剤（Ａ）（水分捕獲剤（Ａ１）～（Ａ３））の加水分解反応の例を以下に示す。 An example of the hydrolysis reaction of the moisture trapping agent (A) (moisture trapping agents (A1) to (A3)) is shown below.
　例えば、水分捕獲剤（Ａ１）の一例である、式（ｉ－１）の構造部位を有する水分捕獲剤および式（ｉ－２）の構造部位を有する水分捕獲剤の加水分解反応について、以下の化学反応式を示すことができる。尚、下記式において、＊は結合位を示す。加水分解生成物として、アルコール化合物が生成すると考えられる。これらのアルコール化合物は揮発しにくく、また適度な分子量を有する。 For example, the hydrolysis reaction of a water trapping agent having a structural site of the formula (i-1) and a water trapping agent having a structural site of the formula (i-2), which are examples of the water trapping agent (A1), is as follows. A chemical reaction formula can be shown. In the following formula, * represents a bonding position. It is considered that an alcohol compound is generated as a hydrolysis product. These alcohol compounds are less volatile and have an appropriate molecular weight.
Figure JPOXMLDOC01-appb-C000025
Figure JPOXMLDOC01-appb-C000025
　例えば、水分捕獲剤（Ａ２）の例である、下記式（ｉｉ－１）のモノカルボン酸無水物、下記式（ｉｉ－２）のジカルボン酸無水物および下記式（ｉｉ－３）のテトラカルボン酸二無水物の加水分解反応について、以下の化学反応式を示すことができる。加水分解生成物として、カルボン酸（ｉｉ－１－１）、ジカルボン酸（ｉｉ－２－１）およびテトラカルボン酸（ｉｉ－３－１）等のカルボン酸化合物が生成すると考えられる。これらのカルボン酸化合物は揮発しにくく、また適度な分子量を有する。 For example, examples of the moisture trapping agent (A2) are a monocarboxylic acid anhydride of the following formula (ii-1), a dicarboxylic acid anhydride of the following formula (ii-2), and a tetracarboxylic acid of the following formula (ii-3). The following chemical reaction formula can be shown for the hydrolysis reaction of acid dianhydride. It is considered that carboxylic acid compounds such as carboxylic acid (ii-1-1), dicarboxylic acid (ii-2-1) and tetracarboxylic acid (ii-3-1) are formed as hydrolysis products. These carboxylic acid compounds are difficult to volatilize and have an appropriate molecular weight.
Figure JPOXMLDOC01-appb-C000026
Figure JPOXMLDOC01-appb-C000026
　例えば、水分捕獲剤（Ａ３）の例である、式（ｉｉｉ－１）および式（ｉｉｉ－２）の化合物の加水分解反応について、以下の化学反応式を示すことができる。加水分解生成物として、アルコール化合物（ｉｉｉ－１－１）および金属水酸化物（ｉｉｉ－１－２）、アルコール化合物（ｉｉｉ－２－１）および金属水酸化物（ｉｉｉ－２－２）を生成する。金属水酸化物（ｉｉｉ－１－２）中の未反応のＲ１Ｏは水と反応し、さらにアルコール化合物（ｉｉｉ－１－１）を生成することができる。アルコール化合物（ｉｉｉ－１－１）および（ｉｉｉ－２－１）は、Ｒ２１基において反応し、水分捕獲体中に留まることができる。金属水酸化物（ｉｉｉ－１－２）および（ｉｉｉ－２－２）は、Ｒ２２基において反応し、水分捕獲体中に留まることができる。さらに、金属水酸化物（ｉｉｉ－１－２）および（ｉｉｉ－２－２）は、Ｒ２２基により水分捕獲体内で固定的に保持されて水分捕獲体内に散在し、縮合反応による水の再発生が防止される。 For example, the following chemical reaction formula can be shown for the hydrolysis reaction of the compounds of formula (iii-1) and formula (iii-2), which are examples of the moisture scavenger (A3). As hydrolysis products, alcohol compound (iii-1-1) and metal hydroxide (iii-1-2), alcohol compound (iii-2-1) and metal hydroxide (iii-2-2) Generate. Unreacted R 1 O in the metal hydroxide (iii-1-2) can react with water to further generate an alcohol compound (iii-1-1). Alcohol compounds (iii-1-1) and (iii-2-1) can react at the R 21 group and remain in the moisture trap. Metal hydroxides (iii-1-2) and (iii-2-2) can react at the R 22 group and remain in the moisture trap. Further, the metal hydroxides (iii-1-2) and (iii-2-2) are fixedly held in the moisture trap by the R 22 group and scattered in the moisture trap, and the water is recovered by the condensation reaction. Occurrence is prevented.
Figure JPOXMLDOC01-appb-C000027
Figure JPOXMLDOC01-appb-C000027
　＜酸・塩基発生剤（Ｂ）＞
　本発明の実施形態の水分捕獲体形成組成物は、成分（Ｂ）として、酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物（Ｂ）（酸・塩基発生剤（Ｂ））を含有する。以下、本実施形態の水分捕獲体形成組成物の成分（Ｂ）である酸発生剤および塩基発生剤をそれぞれ「酸発生剤（Ｂ１）」および「塩基発生剤（Ｂ２）」とも言う。 <Acid / base generator (B)>
In the composition for forming a moisture trap of the embodiment of the present invention, the component (B) is at least one compound (B) selected from the group consisting of an acid generator and a base generator (acid / base generator (B). )). Hereinafter, the acid generator and the base generator, which are the components (B) of the moisture trap forming composition of the present embodiment, are also referred to as “acid generator (B1)” and “base generator (B2)”, respectively.
　本発明の実施形態の水分捕獲体形成組成物が酸発生剤（Ｂ１）を含有する場合、水分捕獲剤（Ａ）として、水分捕獲剤（Ａ１）～（Ａ３）から選ばれる少なくとも１種が用いられる。本発明の実施形態の水分捕獲体形成組成物が塩基発生剤（Ｂ２）を含有する場合、水分捕獲剤（Ａ）として、水分捕獲剤（Ａ２）～（Ａ３）から選ばれる少なくとも１種が用いられる。 When the water trap forming composition of the embodiment of the present invention contains the acid generator (B1), at least one selected from the water traps (A1) to (A3) is used as the water trap (A). It is done. When the water-capturing body forming composition of the embodiment of the present invention contains the base generator (B2), at least one selected from the water-capturing agents (A2) to (A3) is used as the water-capturing agent (A). It is done.
　酸発生剤（Ｂ１）としては、感放射線性酸発生剤および熱酸発生剤が挙げられ、感放射線性酸発生剤が好ましい。塩基発生剤（Ｂ２）としては、感放射線性塩基発生剤および熱塩基発生剤が挙げられ、感放射線性塩基発生剤が好ましい。 Examples of the acid generator (B1) include a radiation sensitive acid generator and a thermal acid generator, and a radiation sensitive acid generator is preferable. Examples of the base generator (B2) include a radiation sensitive base generator and a thermal base generator, and a radiation sensitive base generator is preferred.
　感放射線性酸発生剤および感放射線塩基発生剤は、これらに放射線を照射することにより、それぞれ酸性活性物質および塩基性活性物質を放出することができる化合物と定義することができる。放出される酸性活性物質は、例えば、上述の水分捕獲剤（Ａ）を加水分解反応させる際の触媒として作用する。放出される塩基性活性物質は、例えば、上述の水分捕獲剤（Ａ２）および水分捕獲剤（Ａ３）を加水分解反応させる際の触媒として作用する。 A radiation-sensitive acid generator and a radiation-sensitive base generator can be defined as compounds capable of releasing an acidic active substance and a basic active substance, respectively, by irradiating them with radiation. The acidic active substance to be released acts as a catalyst when the above-described water trapping agent (A) is subjected to a hydrolysis reaction, for example. The released basic active substance acts as a catalyst when, for example, the above-described moisture trapping agent (A2) and moisture trapping agent (A3) are subjected to a hydrolysis reaction.
　感放射線性酸発生剤または感放射線性塩基発生剤を分解し、酸性活性物質のカチオンまたは塩基性活性物質のアニオンを発生するために照射する放射線としては、例えば、可視光線、紫外線、遠紫外線、Ｘ線および荷電粒子線が挙げられる。これらの放射線の中でも、一定のエネルギーレベルを有し、大きな硬化速度を達成可能であり、しかも照射装置が比較的安価かつ小型であることから、紫外線を使用することが好ましい。 Examples of the radiation irradiated to decompose the radiation-sensitive acid generator or the radiation-sensitive base generator and generate the cation of the acidic active substance or the anion of the basic active substance include, for example, visible light, ultraviolet light, far ultraviolet light, Examples include X-rays and charged particle beams. Among these radiations, it is preferable to use ultraviolet rays because they have a constant energy level, can achieve a high curing rate, and the irradiation device is relatively inexpensive and small.
　本発明の実施形態の水分捕獲体形成組成物において、成分（Ｂ）が酸発生剤（Ｂ１）である場合のその含有量は、成分（Ａ）１００質量部に対して、好ましくは０．００１質量部～２０質量部、より好ましくは０．０１質量部～１０質量部である。成分（Ｂ）の含有量を前記範囲とすることで、例えば、放射線感度の優れた水分捕獲体形成組成物を得ることができる。 In the moisture trap forming composition of the embodiment of the present invention, the content when the component (B) is the acid generator (B1) is preferably 0.001 with respect to 100 parts by mass of the component (A). The amount is from 20 to 20 parts by mass, more preferably from 0.01 to 10 parts by mass. By setting the content of the component (B) in the above range, for example, a moisture trap forming composition having excellent radiation sensitivity can be obtained.
　本発明の実施形態の水分捕獲体形成組成物において、成分（Ｂ）が塩基発生剤（Ｂ２）である場合のその含有量は、成分（Ａ）１００質量部に対して、好ましくは０．００１質量部～２０質量部、より好ましくは０．０１質量部～１０質量部である。成分（Ｂ）の含有量を前記範囲とすることで、例えば、放射線感度の優れた組成物を得ることができる。 In the moisture trap forming composition of the embodiment of the present invention, the content when the component (B) is the base generator (B2) is preferably 0.001 with respect to 100 parts by mass of the component (A). The amount is from 20 to 20 parts by mass, more preferably from 0.01 to 10 parts by mass. By setting the content of the component (B) in the above range, for example, a composition having excellent radiation sensitivity can be obtained.
　本発明の実施形態の水分捕獲体形成組成物において、酸発生剤（Ｂ１）、塩基発生剤（Ｂ２）は各々１種単独で用いてもよく、２種以上を併用してもよい。 In the moisture trap forming composition of the embodiment of the present invention, each of the acid generator (B1) and the base generator (B2) may be used alone or in combination of two or more.
　［酸発生剤（Ｂ１）］
　酸発生剤（Ｂ１）としては、例えば、ヨードニウム塩、スルホニウム塩、ホスホニウム塩等の光または熱カチオン硬化触媒、イミダゾール類、酸無水物等のアニオン硬化触媒を使用することができる。これらの中ではカチオン硬化触媒が好ましく、光カチオン硬化触媒がより好ましい。硬化速度が速いこと、また光を当てない限り重合反応が開始しないので、保存安定性が良好なためである。 [Acid generator (B1)]
As the acid generator (B1), for example, light or thermal cation curing catalysts such as iodonium salts, sulfonium salts, phosphonium salts, and anion curing catalysts such as imidazoles and acid anhydrides can be used. In these, a cationic curing catalyst is preferable and a photocationic curing catalyst is more preferable. This is because the curing rate is high and the polymerization reaction does not start unless light is applied, so that the storage stability is good.
　具体的なカチオン硬化触媒としては、例えば、アルキル基またはアリール基で置換されたヨードニウム、スルホニウム、ホスホニウム等のカチオンと、ＳｂＦ６ －、ＢＦ４ －、Ｂ（Ｃ６Ｆ５）４ －、ＰＦ６ －、Ｐ（Ｒｆ）ｎＦ（６－ｎ） －（Ｒｆは、例えば、炭素数１～８のパーフルオロアルキル基；ｎは１～３の整数）、ＣｎＦ２ｎ＋１ＳＯ３ －（ｎは、例えば、１～８の整数）、Ｎ（ＳＯ２ＣＦ３）２ －、Ｃ（ＳＯ２ＣＦ３）３ －等のアニオンとからなる塩が使用される。具体的には、ＣＰＩ－１００Ｐ、ＣＰＩ１０１Ａ、ＣＰＩ－２００Ｋ、ＣＰＩ－２１０Ｓ等（以上、サンアプロ製）、サンエイド（登録商標）ＳＩ－１５０Ｌ、サンエイド（登録商標）ＳＩ－１１０Ｌ、サンエイド（登録商標）ＳＩ－６０Ｌ、サンエイド（登録商標）ＳＩ－８０Ｌ、サンエイド（登録商標）ＳＩ－１００Ｌ等（以上、三新化学工業製）、ローディア製ＰＩ－２０７４、日本曹達製ＣＩ２９２０等のＣＩシリーズ、アデカ製オプトマー（登録商標）ＳＰ－１５０等のオプトマー（登録商標）ＳＰシリーズ、ＣＰ－６６等のオプトンＣＰシリーズ、和光純薬製ＷＰＡＧシリーズおよびＷＰＩシリーズ等が挙げられる。 Specific examples of the cation curing catalyst include cations such as iodonium, sulfonium and phosphonium substituted with an alkyl group or aryl group, SbF 6 − , BF 4 − , B (C 6 F 5 ) 4 − , and PF 6. -, P (Rf) n F (6-n) - (Rf is, for example, perfluoroalkyl group having 1-8 carbon atoms; n is an integer of 1 to 3), C n F 2n + 1 SO 3 - (n is For example, a salt composed of an anion such as N (SO 2 CF 3 ) 2 − , C (SO 2 CF 3 ) 3 − and the like is used. Specifically, CPI-100P, CPI101A, CPI-200K, CPI-210S and the like (manufactured by Sun Apro), SunAid (registered trademark) SI-150L, SunAid (registered trademark) SI-110L, SunAid (registered trademark) SI -60L, Sun Aid (Registered Trademark) SI-80L, Sun Aid (Registered Trademark) SI-100L, etc. (above, Sanshin Chemical Industries), CI series such as Rhodia PI-2074, Nippon Soda CI2920, etc. Optomer (registered trademark) SP series such as registered trade mark SP-150, Opton CP series such as CP-66, WPA series and WPI series manufactured by Wako Pure Chemical Industries.
　これらの酸発生剤（Ｂ１）の中でも、カチオン硬化触媒において、アニオンとしては反応性の点からＢ（Ｃ６Ｆ５）４ －、Ｐ（Ｒｆ）ｎＦ（６－ｎ） －、Ｎ（ＳＯ２ＣＦ３）２ －、Ｃ（ＳＯ２ＣＦ３）３ －が好ましく、カチオンとしては貯蔵安定性の点でアルキル基またはアリール基で置換されたスルホニウムカチオンが好ましい。 Among these acid generators (B1), in the cationic curing catalyst, as anion, B (C 6 F 5 ) 4 − , P (Rf) n F (6-n) − , N (SO 2 CF 3 ) 2 — and C (SO 2 CF 3 ) 3 — are preferred, and the cation is preferably a sulfonium cation substituted with an alkyl group or an aryl group from the viewpoint of storage stability.
　［塩基発生剤（Ｂ２）］
　塩基発生剤（Ｂ２）としては、感放射線性塩基発生剤が好ましく、感放射線性塩基発生剤としては、放射線の照射によりアミン等の塩基を発生する化合物である限り、特に限定されない。感放射線性塩基発生剤としては、例えば、コバルト等の遷移金属錯体、オルトニトロベンジルカルバメート類、アシルオキシイミノ類、α，α－ジメチル－３，５－ジメトキシベンジルカルバメート類が挙げられる。 [Base generator (B2)]
The base generator (B2) is preferably a radiation-sensitive base generator, and the radiation-sensitive base generator is not particularly limited as long as it is a compound that generates a base such as an amine upon irradiation with radiation. Examples of the radiation sensitive base generator include transition metal complexes such as cobalt, orthonitrobenzyl carbamates, acyloxyiminos, α, α-dimethyl-3,5-dimethoxybenzyl carbamates.
　遷移金属錯体としては、例えば、ブロモペンタアンモニアコバルト過塩素酸塩、ブロモペンタメチルアミンコバルト過塩素酸塩、ブロモペンタプロピルアミンコバルト過塩素酸塩、ヘキサアンモニアコバルト過塩素酸塩、ヘキサメチルアミンコバルト過塩素酸塩、ヘキサプロピルアミンコバルト過塩素酸塩が挙げられる。 Transition metal complexes include, for example, bromopentammonium cobalt perchlorate, bromopentamethylamine cobalt perchlorate, bromopentapropylamine cobalt perchlorate, hexaammonia cobalt perchlorate, hexamethylamine cobalt perchlorate. Examples include chlorate and hexapropylamine cobalt perchlorate.
　オルトニトロベンジルカルバメート類としては、例えば、［［（２－ニトロベンジル）オキシ］カルボニル］メチルアミン、［［（２－ニトロベンジル）オキシ］カルボニル］プロピルアミン、［［（２－ニトロベンジル）オキシ］カルボニル］ヘキシルアミン、［［（２－ニトロベンジル）オキシ］カルボニル］シクロヘキシルアミン、［［（２－ニトロベンジル）オキシ］カルボニル］アニリン、［［（２－ニトロベンジル）オキシ］カルボニル］ピペリジン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ヘキサメチレンジアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］フェニレンジアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］トルエンジアミン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ジアミノジフェニルメタン、ビス［［（２－ニトロベンジル）オキシ］カルボニル］ピペラジン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］メチルアミン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］プロピルアミン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］ヘキシルアミン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］シクロヘキシルアミン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］アニリン、［［（２，６－ジニトロベンジル）オキシ］カルボニル］ピペリジン、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］ヘキサメチレンジアミン、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］フェニレンジアミン、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］トルエンジアミン、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］ジアミノジフェニルメタン、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］ピペラジン、２－ニトロフェニルメチル－４－メタクリロイルオキシピぺリジン－１－カルボキシラートが挙げられる。 Examples of orthonitrobenzyl carbamates include [[(2-nitrobenzyl) oxy] carbonyl] methylamine, [[(2-nitrobenzyl) oxy] carbonyl] propylamine, [[(2-nitrobenzyl) oxy]. Carbonyl] hexylamine, [[(2-nitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2-nitrobenzyl) oxy] carbonyl] aniline, [[(2-nitrobenzyl) oxy] carbonyl] piperidine, bis [ [(2-Nitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] phenylenediamine, bis [[(2-nitrobenzyl) oxy] carbonyl] toluenediamine, bis [[ (2-Nitrobenzyl) Oki ] Carbonyl] diaminodiphenylmethane, bis [[(2-nitrobenzyl) oxy] carbonyl] piperazine, [[(2,6-dinitrobenzyl) oxy] carbonyl] methylamine, [[(2,6-dinitrobenzyl) oxy] Carbonyl] propylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] hexylamine, [[(2,6-dinitrobenzyl) oxy] carbonyl] cyclohexylamine, [[(2,6-dinitrobenzyl) oxy ] Carbonyl] aniline, [[(2,6-dinitrobenzyl) oxy] carbonyl] piperidine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] hexamethylenediamine, bis [[(2,6-dinitrobenzyl ) Oxy] carbonyl] phenylenediamine, bis [(2,6-dinitrobenzyl) oxy] carbonyl] toluenediamine, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] diaminodiphenylmethane, bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate.
　アシルオキシイミノ類としては、例えば、プロピオニルアセトフェノンオキシム、プロピオニルベンゾフェノンオキシム、プロピオニルアセトンオキシム、ブチリルアセトフェノンオキシム、ブチリルベンゾフェノンオキシム、ブチリルアセトンオキシム、アジポイルアセトフェノンオキシム、アジポイルベンゾフェノンオキシム、アジポイルアセトンオキシム、アクロイルアセトフェノンオキシム、アクロイルベンゾフェノンオキシム、アクロイルアセトンオキシムが挙げられる。 Acyloxyiminos include, for example, propionyl acetophenone oxime, propionyl benzophenone oxime, propionyl acetone oxime, butyryl acetophenone oxime, butyryl benzophenone oxime, butyryl acetone oxime, adipoyl acetophenone oxime, adipoyl benzophenone oxime, adipoyl Acetone oxime, acryloyl acetophenone oxime, acryloyl benzophenone oxime, acryloyl acetone oxime may be mentioned.
　感放射線性塩基発生剤のその他の例としては、ビス［［（２，６－ジニトロベンジル）オキシ］カルボニル］ピペラジン、２－ニトロフェニルメチル－４－メタクリロイルオキシピぺリジン－１－カルボキシラートおよびアクロイルベンゾフェノンオキシムが特に好ましい。 Other examples of radiation sensitive base generators include bis [[(2,6-dinitrobenzyl) oxy] carbonyl] piperazine, 2-nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate and Ilbenzophenone oxime is particularly preferred.
　＜硬化性化合物（Ｃ）＞
　本発明の実施形態の水分捕獲体形成組成物は、成分（Ｃ）として、硬化性化合物（Ｃ）を含有する。本発明の実施形態の水分捕獲体形成組成物は、硬化性化合物（Ｃ）を含有することで架橋反応性を高めることができる。そして、この水分捕獲体形成組成物から形成される本発明の実施形態の水分捕獲体の強度および基板との密着性を向上させることができる。 <Curable compound (C)>
The moisture capturing body forming composition of the embodiment of the present invention contains a curable compound (C) as the component (C). The moisture capturing body forming composition of the embodiment of the present invention can increase the crosslinking reactivity by containing the curable compound (C). And the intensity | strength of the moisture capture body of embodiment of this invention formed from this moisture capture body formation composition and adhesiveness with a board | substrate can be improved.
　硬化性化合物（Ｃ）は、重合性基を有する化合物である。 The curable compound (C) is a compound having a polymerizable group.
　尚、硬化性化合物（Ｃ）は、単独で、または２種以上組み合わせて用いることができる。 In addition, a sclerosing | hardenable compound (C) can be used individually or in combination of 2 or more types.
　硬化性化合物（Ｃ）としては、例えば、環状エーテル基を有する化合物および重合性二重結合を有する化合物等が挙げられる。 Examples of the curable compound (C) include a compound having a cyclic ether group and a compound having a polymerizable double bond.
　上述の環状エーテル基を有する化合物としては、例えば、エポキシ基を有する化合物、オキセタニル基を有する化合物等が挙げられる。 Examples of the compound having a cyclic ether group include a compound having an epoxy group and a compound having an oxetanyl group.
　上述のエポキシ基を有する化合物としては、例えば、
　単官能エポキシ化合物として、
　グリシジルエーテル、ブチルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、ステアリルグリシジルエーテル、ラウリルグリシジルエーテル、ブトキシポリエチレングリコールグリシジルエーテル、フェノールポリエチレングリコールグリシジルエーテル、アリルグリシジルエーテル、フェニルグリシジルエーテル、ｐ－メチルフェニルグリシジルエーテル、ｐ－エチルフェニルグリシジルエーテル、ｐ－ｓｅｃ－ブチルフェニルグリシジルエーテル、ｐ－ｔｅｒｔ－ブチルフェニルグリシジル等、
　多官能エポキシ化合物として、
　ビスフェノールＡジグリシジルエーテル、ビスフェノールＦジグリシジルエーテル、ビスフェノールＳジグリシジルエーテル、水添ビスフェノールＡジグリシジルエーテル、水添ビスフェノールＦジグリシジルエーテル、水添ビスフェノールＡＤジグリシジルエーテル等のビスフェノールのポリグリシジルエーテル類；
　１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル等の多価アルコールのポリグリシジルエーテル類；
　エチレングリコール、プロピレングリコール、グリセリン等の脂肪族多価アルコールに１種または２種以上のアルキレンオキサイドを付加することにより得られるポリエーテルポリオールの脂肪族ポリグリシジルエーテル類；
　３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート、２－（３，４－エポキシシクロヘキシル－５，５－スピロ－３，４－エポキシ）シクロヘキサン－メタ－ジオキサン、ビス（３，４－エポキシシクロヘキシルメチル）アジペート、ビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート、３，４－エポキシ－６－メチルシクロヘキシル－３’，４’－エポキシ－６’－メチルシクロヘキサンカルボキシレート、メチレンビス（３，４－エポキシシクロヘキサン）、ジシクロペンタジエンジエポキサイド、エチレングリコールのジ（３，４－エポキシシクロヘキシルメチル）エーテル、エチレンビス（３，４－エポキシシクロヘキサンカルボキシレート）、ラクトン変性３，４－エポキシシクロヘキシルメチル－３’，４’－エポキシシクロヘキサンカルボキシレート等の３，４－エポキシシクロヘキシル基を有する化合物等が挙げられる。 As the above-mentioned compound having an epoxy group, for example,
As a monofunctional epoxy compound,
Glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, stearyl glycidyl ether, lauryl glycidyl ether, butoxy polyethylene glycol glycidyl ether, phenol polyethylene glycol glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p- Ethyl phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, p-tert-butylphenyl glycidyl, etc.
As a multifunctional epoxy compound,
Polyglycidyl ethers of bisphenols such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol AD diglycidyl ether;
1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether Glycidyl ethers;
Aliphatic polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin;
3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3 , 4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxy Rate, methylene bis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylene bis (3,4-epoxycyclohexanecarboxylate), lactone modified 3, 4-D Carboxymethyl epoxycyclohexylmethyl-3 ', compounds having a 4'-epoxycyclohexane carboxylate of the 3,4-epoxycyclohexyl group.
　上述のオキセタニル基を有する化合物としては、例えば、
　単官能オキセタン化合物として、
　３－エチル－３－ヒドロキシメチルオキセタン（オキセタンアルコール）、２－エチルヘキシルオキセタン、３－エチル－３－（２－エチルヘキシロキシメチル）オキセタン、３－エチル－３－（ドデシロキシメチル）オキセタン、３－エチル－３－（オクタデシロキシメチル）オキセタン、３－エチル－３－（フェノキシメチル）オキセタン、３－エチル－３－ヒドロキシメチルオキセタン等、
　多官能オキセタン化合物として、
　キシリレンビスオキセタン、１－ブトキシ－２，２－ビス〔（３－エチルオキセタン－３－イル）メトキシメチル〕ブタン、３－エチル－３｛［（３－エチルオキセタン－３－イル）メトキシ］メチル｝オキセタン、１，１，１－トリス〔（３－エチルオキセタン－３－イル）メトキシメチル〕プロパン等が挙げられる。 As a compound having the above oxetanyl group, for example,
As monofunctional oxetane compounds,
3-ethyl-3-hydroxymethyloxetane (oxetane alcohol), 2-ethylhexyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (dodecyloxymethyl) oxetane, 3 -Ethyl-3- (octadecyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3-hydroxymethyloxetane, etc.
As a polyfunctional oxetane compound,
Xylylenebisoxetane, 1-butoxy-2,2-bis [(3-ethyloxetane-3-yl) methoxymethyl] butane, 3-ethyl-3 {[((3-ethyloxetane-3-yl) methoxy] methyl } Oxetane, 1,1,1-tris [(3-ethyloxetane-3-yl) methoxymethyl] propane and the like.
　上述の環状エーテル基を有する化合物としては、架橋反応性を高める観点から、これらの中で、エポキシ基を有する化合物が好ましく、多官能エポキシ化合物がより好ましく、多価アルコールのポリグリシジルエーテル類がさらに好ましく、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテルが特に好ましい。 Among these, the compound having a cyclic ether group is preferably a compound having an epoxy group, more preferably a polyfunctional epoxy compound, and more preferably polyglycidyl ethers of polyhydric alcohols from the viewpoint of enhancing the crosslinking reactivity. Polyethylene glycol diglycidyl ether and polypropylene glycol diglycidyl ether are particularly preferable.
　上述の重合性二重結合を有する化合物としては、酸素原子を有する化合物が好ましく、（メタ）アクリレート化合物がより好ましい。 As the compound having a polymerizable double bond, a compound having an oxygen atom is preferable, and a (meth) acrylate compound is more preferable.
　上記（メタ）アクリレート化合物としては、例えば、単官能（メタ）アクリレート化合物、多官能（メタ）アクリレート化合物等が挙げられる。 Examples of the (meth) acrylate compound include monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds.
　上述の単官能（メタ）アクリレート化合物としては、例えば、（メタ）アクリロイルモルホリン、７－アミノ－３，７－ジメチルオクチル（メタ）アクリレート、イソボルニルオキシエチル（メタ）アクリレート、イソボルニル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、エチルジエチレングリコール（メタ）アクリレート、ジメチルアミノエチル（メタ）アクリレート、ジエチルアミノエチル（メタ）アクリレート、ラウリル（メタ）アクリレート、ジシクロペンタジエン（メタ）アクリレート、ジシクロペンテニルオキシエチル（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、Ｎ，Ｎ－ジメチル（メタ）アクリルアミドテトラクロロフェニル（メタ）アクリレート、テトラヒドロフルフリル（メタ）アクリレート、テトラブロモフェニル（メタ）アクリレート、トリブロモフェニル（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、ブトキシエチル（メタ）アクリレート、ペンタクロロフェニル（メタ）アクリレート、ペンタブロモフェニル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、ポリプロピレングリコールモノ（メタ）アクリレート、イソボルニル（メタ）アクリレート、メチルトリエチレンジグリコール（メタ）アクリレート、フェノキシエチル（メタ）アクリレート、フェノキシ－２－メチルエチル（メタ）アクリレート、フェノキシエトキシエチル（メタ）アクリレート、３－フェノキシ－２－ヒドロキシプロピル（メタ）アクリレート、２－フェニルフェノキシエチル（メタ）アクリレート、４－フェニルフェノキシエチル（メタ）アクリレート、３－（２－フェニルフェニル）－２－ヒドロキシプロピル（メタ）アクリレート、エチレンオキシドを反応させたｐ－クミルフェノールの（メタ）アクリレート、２－ブロモフェノキシエチル（メタ）アクリレート、４－ブロモフェノキシエチル（メタ）アクリレート、２，４－ジブロモフェノキシエチル（メタ）アクリレート、２，６－ジブロモフェノキシエチル（メタ）アクリレート、２，４，６－トリブロモフェニル（メタ）アクリレート、２，４，６－トリブロモフェノキシエチル（メタ）アクリレート等が挙げられる。 Examples of the monofunctional (meth) acrylate compound include (meth) acryloylmorpholine, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobornyloxyethyl (meth) acrylate, and isobornyl (meth) acrylate. 2-ethylhexyl (meth) acrylate, ethyldiethylene glycol (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentadiene (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (meth) acrylamide tetrachlorophenyl (meth) acrylate, tetrahydrofurfuryl (Meth) acrylate, tetrabromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) Acrylate, pentabromophenyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, isobornyl (meth) acrylate, methyltriethylenediglycol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxy -2-Methylethyl (meth) acrylate, phenoxyethoxyethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl Meth) acrylate, 2-phenylphenoxyethyl (meth) acrylate, 4-phenylphenoxyethyl (meth) acrylate, 3- (2-phenylphenyl) -2-hydroxypropyl (meth) acrylate, and p-polymer reacted with ethylene oxide Milphenol (meth) acrylate, 2-bromophenoxyethyl (meth) acrylate, 4-bromophenoxyethyl (meth) acrylate, 2,4-dibromophenoxyethyl (meth) acrylate, 2,6-dibromophenoxyethyl (meth) Examples include acrylate, 2,4,6-tribromophenyl (meth) acrylate, 2,4,6-tribromophenoxyethyl (meth) acrylate, and the like.
　上述の多官能（メタ）アクリレート化合物としては、例えば、エチレングリコールジ（メタ）アクリレート、ジシクロペンテニルジ（メタ）アクリレート、トリエチレングリコールジアクリレート、テトラエチレングリコールジ（メタ）アクリレート、トリシクロデカンジイルジメチレンジ（メタ）アクリレート、トリシクロデカンジメタノールジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートジ（メタ）アクリレート、トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、カプロラクトン変性トリス（２－ヒドロキシエチル）イソシアヌレートトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ＥＯ変性トリメチロールプロパントリ（メタ）アクリレート、ＰＯ変性トリメチロールプロパントリ（メタ）アクリレート、トリプロピレングリコールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、１，６－ヘキサンジオールジ（メタ）アクリレート、１，９－ノナンジオールジ（メタ）アクリレート、１，１０－デカンジオールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ポリエステルジ（メタ）アクリレート、ポリエチレングリコールジ（メタ）アクリレート、ポリプロピレングリコールジ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールテトラ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールヘキサ（メタ）アクリレート、カプロラクトン変性ジペンタエリスリトールペンタ（メタ）アクリレート、エトキシ化ビスフェノールＡジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート、フェノールノボラックポリグリシジルエーテルの（メタ）アクリレート、１，３－ビス（（メタ）アクリロイルオキシ）－２－プロパノール、９，９－ビス［４－［２－（アクリロイルオキシ）エトキシ］フェニル］－９Ｈ－フルオレン等が挙げられる。多官能（メタ）アクリレート化合物としては、これらの中で、ポリプロピレングリコールジ（メタ）アクリレートが好ましい。 Examples of the polyfunctional (meth) acrylate compound include ethylene glycol di (meth) acrylate, dicyclopentenyl di (meth) acrylate, triethylene glycol diacrylate, tetraethylene glycol di (meth) acrylate, and tricyclodecanediyl. Dimethylene di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified Tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, EO-modified trimethylolpropane tri (meth) acrylate , PO-modified trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyester di (meth) Acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate Dipentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate, ethoxylated bisphenol A di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Ditrimethylolpropane tetra (meth) acrylate, (meth) acrylate of phenol novolac polyglycidyl ether, 1,3-bis ((meth) acryloyloxy) -2-propanol, 9,9-bis [4- [2- (acryloyl) Oxy) ethoxy] phenyl] -9H-fluorene and the like. Among these, as the polyfunctional (meth) acrylate compound, polypropylene glycol di (meth) acrylate is preferable.
　上述の多官能（メタ）アクリレート化合物の市販品としては、例えば、ビスコート＃１９５、同＃２３０、同＃２６０、同＃３３５ＨＰ、同＃５４０、同＃７００（以上、大阪有機化学工業製）、ＴＭＰＴ、９Ｇ、９ＰＧ、７０１、ＢＰＥ－５００、ＤＣＰ、ＤＯＤ－Ｎ、ＨＤ－Ｎ、ＮＯＤ－Ｎ、ＮＰＧ（以上、新中村化学工業製）等が挙げられる。 As a commercial item of the above-mentioned polyfunctional (meth) acrylate compound, for example, biscoat # 195, # 230, same # 260, same # 335HP, same # 540, same # 700 (above, manufactured by Osaka Organic Chemical Industry), TMPT, 9G, 9PG, 701, BPE-500, DCP, DOD-N, HD-N, NOD-N, NPG (above, manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.
　上述の重合性二重結合を有する化合物としては、架橋反応性を高める観点から、これらの中で、多官能（メタ）アクリレート化合物が好ましく、多官能メタクリレート化合物がより好ましく、ポリエチレングリコールジメタクリレート、ポリプロピレングリコールジメタクリレートがさらに好ましく、ポリエチレングリコール＃４００ジメタクリレート、ポリプロピレングリコール＃４００ジメタクリレートが特に好ましい。 Among these, the compound having a polymerizable double bond is preferably a polyfunctional (meth) acrylate compound, more preferably a polyfunctional methacrylate compound, polyethylene glycol dimethacrylate, polypropylene from the viewpoint of enhancing the crosslinking reactivity. Glycol dimethacrylate is more preferred, and polyethylene glycol # 400 dimethacrylate and polypropylene glycol # 400 dimethacrylate are particularly preferred.
　硬化性化合物（Ｃ）の含有量としては、成分（Ａ）１００質量部に対して、１０質量部～３０００質量部が好ましく、５０質量部～２０００質量部がより好ましい。硬化性化合物（Ｃ）の含有量を上記範囲とすることで、本実施形態の水分捕獲体形成組成物から形成される、本発明の実施形態の水分捕獲体の基板への密着性を効果的に高めることができる。 The content of the curable compound (C) is preferably 10 parts by mass to 3000 parts by mass, and more preferably 50 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the component (A). By making content of a sclerosing | hardenable compound (C) into the said range, the adhesiveness to the board | substrate of the moisture trap body of embodiment of this invention formed from the moisture trap body formation composition of this embodiment is effective. Can be increased.
＜その他の任意成分＞
　本発明の実施形態の水分捕獲体形成組成物は、本発明の効果を損なわない範囲で、必要に応じて、ラジカル重合開始剤（Ｄ）、微粒子（Ｅ）および添加剤から選択される少なくとも１種の他の成分を含有してもよい。その他の任意成分は、１種単独で使用してもよく、２種以上を併用してもよい。尚、ラジカル重合開始剤（Ｄ）および微粒子（Ｅ）をそれぞれ、成分（Ｄ）および成分（Ｅ）ということがある。 <Other optional components>
The moisture trap forming composition of the embodiment of the present invention is at least one selected from a radical polymerization initiator (D), fine particles (E) and an additive as necessary, as long as the effects of the present invention are not impaired. Other components of the seed may be included. Other optional components may be used alone or in combination of two or more. The radical polymerization initiator (D) and the fine particles (E) may be referred to as component (D) and component (E), respectively.
［ラジカル重合開始剤（Ｄ）］
　本発明の実施形態の水分捕獲体形成組成物は、さらにラジカル重合開始剤（Ｄ）を含有することができる。ラジカル重合開始剤（Ｄ）としては、活性光線、熱、酸または塩基によりラジカルを発生する化合物を意味し、例えば、熱ラジカル重合開始剤および光ラジカル重合開始剤等が挙げられる。ラジカル重合開始剤（Ｄ）を含有することで、例えば、上述の化学反応式に示す加水分解反応によって形成されたアルコール化合物および金属アルコキシド化合物が、前記組成物から形成される水分捕獲体中に効率良く固定化され、留まることが容易となる。 [Radical polymerization initiator (D)]
The moisture trap forming composition of the embodiment of the present invention can further contain a radical polymerization initiator (D). The radical polymerization initiator (D) means a compound that generates radicals by actinic rays, heat, acid, or base, and examples thereof include a thermal radical polymerization initiator and a photo radical polymerization initiator. By containing the radical polymerization initiator (D), for example, the alcohol compound and the metal alkoxide compound formed by the hydrolysis reaction shown in the above chemical reaction formula are efficiently contained in the moisture trap formed from the composition. It is well fixed and easy to stay.
　本発明の実施形態の水分捕獲体形成組成物において、ラジカル重合開始剤（Ｄ）は１種単独で用いてもよく、２種以上を併用してもよい。 In the moisture trap forming composition of the embodiment of the present invention, the radical polymerization initiator (D) may be used alone or in combination of two or more.
　上述の熱ラジカル重合開始剤としては、例えば、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２－メチルブチロニトリル）、１，１’－アゾビス（シクロヘキサン－１－カルボニトリル）、２，２’－アゾビス［Ｎ－（２－プロペニル）２－メチルプロピオンアミド］、１－［（１－シアノ－１－メチルエチル）アゾ］ホルムアミド、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）等のアゾ化合物；ｔ－ブチルパーオキシベンゾエート、２，５－ジメチル－２，５－ジ（ｔ－ブチルペルオキシ）ヘキサン等の過酸化物等が挙げられる。これらの中で、熱ラジカル重合開始剤としては、アゾ化合物が好ましく、ジメチル－２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（Ｎ－ブチル－２－メチルプロピオンアミド）、２，２’－アゾビス（Ｎ－シクロヘキシル－２－メチルプロピオンアミド）がより好ましい。 Examples of the thermal radical polymerization initiator include 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl- 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′- Azobis [N- (2-propenyl) 2-methylpropionamide], 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide) Azo compounds such as 2,2′-azobis (N-cyclohexyl-2-methylpropionamide); t-butylperoxybenzoate, 2,5-dimethyl-2,5 Di (t-butylperoxy) peroxides such as hexane and the like. Among these, as the thermal radical polymerization initiator, an azo compound is preferable, and dimethyl-2,2′-azobis (2-methylpropionate), 2,2′-azobis (N-butyl-2-methylpropion) is preferred. Amide) and 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) are more preferred.
　上述のアゾ化合物の市販品としては、例えば、Ｖ－７０、Ｖ－６５、Ｖ－６０１、Ｖ－５９、Ｖ－４０、ＶＦ－０９６、Ｖ－３０、ＶＡｍ－１１０、ＶＡｍ－１１１（以上、和光純薬工業製）等が挙げられる。 Examples of commercially available azo compounds include V-70, V-65, V-601, V-59, V-40, VF-096, V-30, VAm-110, and VAm-111 (above, Wako Pure Chemical Industries, Ltd.).
　上述の過酸化物の市販品としては、例えば、パーブチル（登録商標）Ｚ、パーヘキサ（登録商標）２５Ｂ（以上、日油製）等が挙げられる。 Examples of the above-mentioned commercially available peroxides include perbutyl (registered trademark) Z, perhexa (registered trademark) 25B (manufactured by NOF Corporation) and the like.
　上述の光ラジカル重合開始剤としては、例えば、チオキサントン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物、Ｏ－アシルオキシム系化合物、オニウム塩系化合物、ベンゾイン系化合物、ベンゾフェノン系化合物、α－ジケトン系化合物、多核キノン系化合物、アシルホスフィンオキサイド系化合物、イミドスルホナート系化合物等が挙げられる。これらの中で、光ラジカル重合開始剤としては、アシルホスフィンオキサイド系化合物、チオキサントン系化合物、アセトフェノン系化合物、ビイミダゾール系化合物、トリアジン系化合物およびＯ－アシルオキシム系化合物からなる群より選択される少なくとも１種を含んでいることが好ましい。 Examples of the above-mentioned photo radical polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -Diketone compounds, polynuclear quinone compounds, acylphosphine oxide compounds, imide sulfonate compounds, and the like. Among these, the radical photopolymerization initiator is at least selected from the group consisting of acylphosphine oxide compounds, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds. It is preferable that 1 type is included.
　上述のアシルホスフィンオキサイド系化合物としては、例えば、２，４，６－トリメトキシベンゾイル－ジフェニル－ホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド等が好ましい。 As the above-mentioned acylphosphine oxide compounds, for example, 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like are preferable.
　上述のチオキサントン系化合物としては、例えば、チオキサントン、２－クロロチオキサントン、２－メチルチオキサントン、２－イソプロピルチオキサントン、４－イソプロピルチオキサントン、２，４－ジクロロチオキサントン、２，４－ジメチルチオキサントン、２，４－ジエチルチオキサントン、２，４－ジイソプロピルチオキサントン等が挙げられる。 Examples of the thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4- Examples include diethylthioxanthone and 2,4-diisopropylthioxanthone.
　上述のアセトフェノン系化合物としては、例えば、２－メチル－１－［４－（メチルチオ）フェニル］－２－モルフォリノプロパン－１－オン、２－ベンジル－２－ジメチルアミノ－１－（４－モルフォリノフェニル）ブタン－１－オン、２－（４－メチルベンジル）－２－（ジメチルアミノ）－１－（４－モルフォリノフェニル）ブタン－１－オン等が挙げられる。 Examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho And linophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
　上述のビイミダゾール系化合物としては、例えば、２，２’－ビス（２－クロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、２，２’－ビス（２，４－ジクロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール、２，２’－ビス（２，４，６－トリクロロフェニル）－４，４’，５，５’－テトラフェニル－１，２’－ビイミダゾール等が挙げられる。尚、光重合開始剤としてビイミダゾール系化合物を用いる場合、水素供与体を併用することが、感度を改良することができる点で好ましい。水素供与体とは、露光によりビイミダゾール系化合物から発生したラジカルに対して、水素原子を供与することができる化合物を意味する。水素供与体としては、例えば、２－メルカプトベンゾチアゾール、２－メルカプトベンゾオキサゾール等のメルカプタン系水素供与体；４，４’－ビス（ジメチルアミノ）ベンゾフェノン、４，４’－ビス（ジエチルアミノ）ベンゾフェノン等のアミン系水素供与体が挙げられる。本実施形態において、水素供与体は、単独でまたは２種以上を組み合わせて用いることができるが、１種以上のメルカプタン系水素供与体と１種以上のアミン系水素供与体とを組み合わせて使用することが、より感度を改良することができる点で好ましい。 Examples of the above-mentioned biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis. (2,4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′ , 5,5′-tetraphenyl-1,2′-biimidazole and the like. In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The hydrogen donor means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, etc. And an amine-based hydrogen donor. In this embodiment, the hydrogen donor can be used alone or in combination of two or more, but one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable in that the sensitivity can be further improved.
　上述のトリアジン系化合物としては、例えば、２，４，６－トリス（トリクロロメチル）－ｓ－トリアジン、２－メチル－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（５－メチルフラン－２－イル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（フラン－２－イル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（４－ジエチルアミノ－２－メチルフェニル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－〔２－（３，４－ジメトキシフェニル）エテニル〕－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－メトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－エトキシスチリル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン、２－（４－ｎ－ブトキシフェニル）－４，６－ビス（トリクロロメチル）－ｓ－トリアジン等が挙げられる。 Examples of the triazine compound described above include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-eth Shisuchiriru) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n- butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine.
　上述のＯ－アシルオキシム系化合物としては、例えば、１，２－オクタンジオン、１－［４－（フェニルチオ）フェニル］－２－（Ｏ－ベンゾイルオキシム）、エタノン－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、エタノン－１－［９－エチル－６－（２－メチル－４－テトラヒドロフラニルメトキシベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）、エタノン－１－［９－エチル－６－｛２－メチル－４－（２，２－ジメチル－１，３－ジオキソラニル）メトキシベンゾイル｝－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）等が挙げられる。 Examples of the O-acyloxime compounds include 1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and ethanone-1- [9-ethyl-6. -(2-Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl)- 9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like.
　以上、例示した中で、光ラジカル重合開始剤としては、２，４，６－トリメトキシベンゾイル－ジフェニル－ホスフィンオキシド、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキサイド、エタノン－１－［９－エチル－６－（２－メチルベンゾイル）－９Ｈ－カルバゾール－３－イル］－１－（Ｏ－アセチルオキシム）が好ましい。 In the above examples, as the radical photopolymerization initiator, 2,4,6-trimethoxybenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, ethanone-1 -[9-Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) is preferred.
　上述の光ラジカル重合開始剤の市販品としては、例えば、イルガキュア（登録商標）１８４、同３６９、同ＯＸ０１，同ＯＸ０２，同８１９、同６５１、同５００、同８１９、同９０７、同７８４、同２９５９、ＣＧＩ１７００、ＣＧＩ１７５０、ＣＧＩ１８５０、ＣＧ２４－６１、ダロキュア（登録商標）１１１６、同１１７３、同４２６５、同ＴＰＯ、ルシリン（登録商標）ＴＰＯ（以上、ＢＡＳＦ製）、ユベクリルＰ３６（ＵＣＢ製）、エザキュアー（登録商標）ＫＩＰ１５０、同ＫＩＰ６５ＬＴ、同ＫＩＰ１００Ｆ、同ＫＴ３７、同ＫＴ５５、同ＫＴＯ４６、同ＫＩＰ７５／Ｂ（以上、フラテツリ・ランベルティ製）等が挙げられる。  Commercially available products of the above-mentioned photo radical polymerization initiator include, for example, Irgacure (registered trademark) 184, 369, OX01, OX02, 819, 651, 500, 819, 907, 784, 2959, CGI 1700, CGI 1750, CGI 1850, CG 24-61, Darocur (registered trademark) 1116, 1173, 4265, TPO, Lucyrin (registered trademark) TPO (above, manufactured by BASF), Ubekril P36 (manufactured by UCB), Ezacure ( Registered trademark) KIP150, KIP65LT, KIP100F, KT37, KT55, KTO46, KIP75 / B (above, manufactured by Fratelli Lamberti).
　ラジカル重合開始剤（Ｄ）の含有量としては、成分（Ａ）１００質量部に対して、０．０５質量部～１５質量部が好ましく、０．１質量部～１０質量部がより好ましい。ラジカル重合開始剤（Ｄ）の含有量を上記の範囲とすることで、所望とするラジカル重合反応を速やかに進行させることができる。 The content of the radical polymerization initiator (D) is preferably 0.05 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). By making content of a radical polymerization initiator (D) into said range, the desired radical polymerization reaction can be advanced rapidly.
［微粒子（Ｅ）］
　本発明の実施形態の水分捕獲体形成組成物は、さらに微粒子（Ｅ）を含有することができる。微粒子（Ｅ）は、本実施形態の水分捕獲体形成組成物を用いて形成される本発明の実施形態の水分捕獲体に光散乱性を付与するための成分である。したがって、微粒子（Ｅ）は、光散乱粒子であることが好ましい。本実施形態の水分捕獲体形成組成物がこのような微粒子を含有することで、耐熱性向上および光取出し効率を向上させることができる。 [Fine particle (E)]
The moisture trap forming composition of the embodiment of the present invention may further contain fine particles (E). The fine particles (E) are components for imparting light scattering properties to the moisture trap of the embodiment of the present invention formed using the moisture trap forming composition of the present embodiment. Therefore, the fine particles (E) are preferably light scattering particles. When the moisture trap forming composition of the present embodiment contains such fine particles, the heat resistance and the light extraction efficiency can be improved.
　微粒子（Ｅ）は、例えば、有機ＥＬ素子により形成される光を散乱し、取り出す効果を有するものであれば特に限定されず、有機粒子であっても、無機粒子であってもよい。 The fine particles (E) are not particularly limited as long as they have an effect of scattering and extracting light formed by an organic EL element, for example, and may be organic particles or inorganic particles.
　有機粒子としては、ポリメチルメタクリレートビーズ、アクリル－スチレン共重合体ビーズ、メラミン樹脂ビーズ、ポリカーボネートビーズ、ポリスチレンビーズ、架橋ポリスチレンビーズ、ポリ塩化ビニルビーズ、およびベンゾグアナミン－メラミンホルムアルデヒド縮合物ビーズ等が用いられる。無機粒子としては、ＳｉＯ２、ＺｒＯ２、ＴｉＯ２、Ａｌ２Ｏ３、Ｉｎ２Ｏ３、ＺｎＯ、ＳｎＯ２、およびＳｂ２Ｏ３等が用いられる。これらは、単独で用いても２種類以上を併用してもよい。 As the organic particles, polymethyl methacrylate beads, acrylic-styrene copolymer beads, melamine resin beads, polycarbonate beads, polystyrene beads, cross-linked polystyrene beads, polyvinyl chloride beads, benzoguanamine-melamine formaldehyde condensate beads, and the like are used. As the inorganic particles, SiO 2 , ZrO 2 , TiO 2 , Al 2 O 3 , In 2 O 3 , ZnO, SnO 2 , Sb 2 O 3 and the like are used. These may be used alone or in combination of two or more.
　また、微粒子（Ｅ）の市販品としては、例えば、チタニア粒子として、シーアイ化成社製ＲＴＴＣＨＮ１５ＷＴ％－Ｅ０６、テイカ社製ＴＳ－１４９、シーアイ化成社製ＴＩＰＡ１５ＷＴ％－Ｘ４８０、ＮａｎｏＧｒａｍ社製Ｎ－ＳＯＬ－１０１－２０ＰＭ等を用いることができる。ジルコニア粒子として、日揮触媒化成社製オプトレイク（登録商標）６３２０Ｚ、日産化学社製ナノユース（登録商標）ＯＺ－Ｓ３０Ｋ－ＡＣ、堺化学社製ジルコニアＳＺＲ－Ｋ、ソーラー社製ｎａｎｏｎ５　ＺＲ－０１０等を用いることができる。 Further, commercially available fine particles (E) include, for example, titania particles such as RTTCHN15WT% -E06 manufactured by CI Kasei, TS-149 manufactured by Teika, TIPA15WT% -X480 manufactured by CI Kasei, and N-SOL- manufactured by NanoGram. 101-20PM or the like can be used. As zirconia particles, Optolake (registered trademark) 6320Z manufactured by JGC Catalysts & Chemicals Co., Ltd., Nanouse (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Co., Ltd., Zirconia SZR-K manufactured by Sakai Chemical Co., Ltd. Can be used.
　本実施形態の水分捕獲体形成組成物において、微粒子（Ｅ）は、水分捕獲体形成組成物中の平均粒子径が５０ｎｍ～５００ｎｍであり、かつ、微粒子（Ｅ）の全量に対する粒子径６００ｎｍ以上の粒子の含有量が２０体積％以下である。 In the moisture trap forming composition of the present embodiment, the fine particles (E) have an average particle size of 50 nm to 500 nm in the moisture trap forming composition and a particle size of 600 nm or more with respect to the total amount of the fine particles (E). The content of particles is 20% by volume or less.
　微粒子（Ｅ）の平均粒子径が５０ｎｍ未満であると、充分な散乱効果が現れない上に、形成される水分捕獲体の屈折率に影響を与えてしまうため、好ましくない場合がある。また、５００ｎｍより大きいと、散乱強度（ヘイズ値）が高くても散乱角度が狭くなるため、有効な散乱が得られず、光取出し効率が低くなったり、光取出し効率の波長による変化が大きくなり色調が変化しやすく、好ましくない場合がある。より好ましくは、５０ｎｍ～３００ｎｍである。 If the average particle diameter of the fine particles (E) is less than 50 nm, a sufficient scattering effect does not appear and the refractive index of the formed moisture trap is affected, which is not preferable. On the other hand, if it is larger than 500 nm, the scattering angle becomes narrow even if the scattering intensity (haze value) is high, so that effective scattering cannot be obtained, the light extraction efficiency is lowered, and the change of the light extraction efficiency due to the wavelength increases. The color tone tends to change, which is not preferable. More preferably, it is 50 nm to 300 nm.
　微粒子（Ｅ）の全量に対する粒子径６００ｎｍ以上の粒子の含有量が２０体積％より多いと、光取出し効率の波長による変化が大きくなり、色調が変化しやすいため、好ましくない場合がある。また、形成される水分捕獲体の表面粗さが大きくなるため、水分捕獲体の膜厚ムラあるいは突起等が生じるおそれがある。６００ｎｍ以上の粒子の含有量は、より好ましくは１５体積％以下である。 If the content of particles having a particle diameter of 600 nm or more with respect to the total amount of the fine particles (E) is more than 20% by volume, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. Further, since the surface roughness of the formed moisture trap is increased, there is a possibility that the film thickness unevenness or protrusions of the moisture trap may occur. The content of particles of 600 nm or more is more preferably 15% by volume or less.
　尚、本発明において、微粒子（Ｅ）の「平均粒子径」および「粒子径」とは、後述の平均１次粒子径とは異なり、凝集による２次粒子の粒子径を加味した、水分捕獲体形成組成物中での分散粒径のことである。これらは光学顕微鏡にて実測あるいは動的光散乱法によって求めることができる。ここで、平均１次粒子径と区別する理由は、同じ平均１次粒子径の散乱粒子を用いた場合であっても、水分捕獲体形成組成物中での上記微粒子の分散状態により、平均粒子径および粒度分布は異なる場合があるためである。また、「平均粒子径」は測定サンプルの５０体積％における分散粒径の値であり、粒子径が６００ｎｍ以上の粒子の含有量は、測定サンプルの分散粒径のうち、６００ｎｍ以上の粒子径の体積％である。これらは動的光散乱法では日機装（株）社製「ナノトラック（登録商標）ＵＰＡ」で測定することができる。 In the present invention, the “average particle diameter” and “particle diameter” of the fine particles (E) are different from the average primary particle diameter described later, and the moisture trapping body in consideration of the particle diameter of the secondary particles due to aggregation. It is the dispersed particle size in the forming composition. These can be obtained by actual measurement with an optical microscope or by a dynamic light scattering method. Here, the reason for distinguishing from the average primary particle size is that even when scattering particles having the same average primary particle size are used, the average particle size depends on the dispersion state of the fine particles in the water trapping body forming composition. This is because the diameter and the particle size distribution may be different. The “average particle size” is the value of the dispersed particle size at 50% by volume of the measurement sample, and the content of particles having a particle size of 600 nm or more is the particle size of 600 nm or more of the dispersed particle size of the measurement sample. % By volume. These can be measured by “Nanotrack (registered trademark) UPA” manufactured by Nikkiso Co., Ltd. in the dynamic light scattering method.
　微粒子（Ｅ）の粒度分布としては、変動係数が３０％以下であることが好ましい。「変動係数」とは、粒子径の標準偏差を平均粒子径で除した値の百分率で表されるものであり、平均粒子径に対するばらつきの大きさの指標となる。変動係数が３０％より大きいと、光取出し効率の波長による変化が大きくなり、色調が変化しやすいため、好ましくない場合がある。より好ましくは変動係数が２０％以下である。 As the particle size distribution of the fine particles (E), the coefficient of variation is preferably 30% or less. The “variation coefficient” is expressed as a percentage of a value obtained by dividing the standard deviation of the particle diameter by the average particle diameter, and is an index of the degree of variation with respect to the average particle diameter. If the coefficient of variation is greater than 30%, the change in the light extraction efficiency depending on the wavelength increases and the color tone tends to change, which may not be preferable. More preferably, the coefficient of variation is 20% or less.
　微粒子（Ｅ）は、その使用方法として、あらかじめ溶剤に分散した分散液を用いることが好ましい。 The fine particles (E) are preferably used in the form of a dispersion previously dispersed in a solvent.
　微粒子（Ｅ）の分散方法としては、上記微粒子の表面状態に合わせた分散剤を用い、分散機を用いる方法が好ましい。 As a method for dispersing the fine particles (E), a method using a dispersing agent in accordance with the surface state of the fine particles and using a disperser is preferable.
　上述の分散機としては、ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノーミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、コボールミル、ホモミキサー、ホモジナイザー（エム・テクニック社製「クレアミックス（登録商標）」等）、湿式ジェットミル（ジーナス社製「ジーナス（登録商標）ＰＹ」、ナノマイザー社製「ナノマイザー（登録商標）」）、微小ビーズミル（寿工業（株）社製「スーパーアペックミル」および「ウルトラアペックミル」）等が使用できる。 Examples of the disperser include paint conditioner (manufactured by Red Devil), ball mill, sand mill (such as “Dyno mill” manufactured by Shinmaru Enterprises), attritor, pearl mill (such as “DCP mill” manufactured by Eirich), coball mill, homo Mixer, homogenizer ("Clearmix (registered trademark)" manufactured by M Technique Co., Ltd.), wet jet mill ("Genus (registered trademark) PY" manufactured by Genus, "Nanomizer (registered trademark)" manufactured by Nanomizer), micro bead mill (“Super Apec Mill” and “Ultra Apec Mill” manufactured by Kotobuki Industries Co., Ltd.) can be used.
　ここで、上述の分散機にメディアを使う場合には、ガラスビーズ、ジルコニアビーズ、アルミナビーズ、磁性ビーズ、およびポリスチレンビーズ等を用いることが好ましい。分散に関しては、２種類以上の分散機、または大きさの異なる２種類以上のメディアをそれぞれ用い、段階的に実施しても差し支えない。 Here, when media are used in the above-described disperser, glass beads, zirconia beads, alumina beads, magnetic beads, polystyrene beads, and the like are preferably used. Regarding dispersion, two or more types of dispersers or two or more types of media having different sizes may be used and may be implemented step by step.
　微粒子（Ｅ）の平均粒子径および粒度分布は、無機粒子の場合は分散条件、例えば、分散機、分散媒、分散時間、および分散剤等を適宜調整することによって好適な範囲に調整することが可能である。また、有機粒子の場合は、重合温度、および重合組成等の合成条件、あるいは、分散機、分散媒、分散時間、および分散剤等の分散条件によって調整できる。 In the case of inorganic particles, the average particle size and particle size distribution of the fine particles (E) can be adjusted to a suitable range by appropriately adjusting the dispersion conditions, for example, the disperser, the dispersion medium, the dispersion time, and the dispersant. Is possible. In the case of organic particles, it can be adjusted by the synthesis conditions such as the polymerization temperature and the polymerization composition, or the dispersion conditions such as the disperser, dispersion medium, dispersion time, and dispersant.
　微粒子（Ｅ）の使用量は、水分捕獲体形成組成物中、１質量％～２５質量％が好ましく、１質量％～２０質量％がより好ましい。１質量％未満では充分な散乱効果が現れないおそれがあり、２５質量％を超えると粒子同士が凝集しやすく、形成される水分捕獲体の表面粗さが大きくなるおそれがある。 The amount of the fine particles (E) used is preferably 1% by mass to 25% by mass and more preferably 1% by mass to 20% by mass in the moisture trap forming composition. If it is less than 1% by mass, a sufficient scattering effect may not appear, and if it exceeds 25% by mass, the particles tend to aggregate and the surface roughness of the moisture trap to be formed may increase.
［添加剤］
　本発明の実施形態の水分捕獲体形成組成物は、必要に応じて添加剤を含有してもよい。具体的には、増感剤、硬化促進剤、光増感剤、分散助剤、充填剤、密着促進剤、酸化防止剤、紫外線吸収剤、凝集防止剤、熱重合禁止剤、消泡剤、界面活性剤等が例示される。 [Additive]
The moisture trap forming composition of the embodiment of the present invention may contain an additive as necessary. Specifically, a sensitizer, a curing accelerator, a photosensitizer, a dispersion aid, a filler, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, a thermal polymerization inhibitor, an antifoaming agent, Surfactant etc. are illustrated.
　＜水分捕獲体形成組成物の調製方法＞
　本発明の水分捕獲体形成組成物は、上述した成分（Ａ）、成分（Ｂ）および成分（Ｃ）を混合し、必要に応じて成分（Ｄ）、成分（Ｅ）および安定剤等を所定の割合で混合することにより調製することができる。 <Preparation method of moisture trap forming composition>
The moisture trap forming composition of the present invention is a mixture of the above-described component (A), component (B) and component (C), and the component (D), component (E), stabilizer and the like are determined as necessary. It can prepare by mixing in the ratio.
　本発明の実施形態の水分捕獲体形成組成物は、水分が特性を低下させる懸念のある電子デバイスに用いられる水分捕獲体の形成用として、特に有機ＥＬ素子を構成する水分捕獲体の形成用として、好適に用いることができる。例えば、本実施形態の水分捕獲体形成組成物を用いて水分捕獲体を形成し、それを含む有機ＥＬ素子を作成（例えば、封止）した後、放射線照射および加熱の少なくとも一方を行うことで、本実施形態の水分捕獲体の水分捕獲能力を発現させることができる。 The moisture trap forming composition of the embodiment of the present invention is used for forming a moisture trap used for an electronic device in which moisture may deteriorate characteristics, particularly for forming a moisture trap constituting an organic EL element. Can be preferably used. For example, by forming a moisture trap using the moisture trap formation composition of the present embodiment and creating (for example, sealing) an organic EL element including the moisture trap, performing at least one of radiation irradiation and heating. The water capturing ability of the water capturing body of this embodiment can be expressed.
　〔水分捕獲体〕
　本発明の実施形態の水分捕獲体は、上述したように、本発明の実施形態の水分捕獲体形成組成物を用いて形成される。 [Moisture trap]
As described above, the moisture trap of the embodiment of the present invention is formed using the moisture trap forming composition of the embodiment of the present invention.
　本実施形態の水分捕獲体の形成方法としては、上述した本発明の実施形態の水分捕獲体形成組成物を用い、例えば、ガラス等の基板上に塗膜を形成した後、この塗膜を放射線照射する方法、または、加熱する方法、または、放射線照射および加熱をする方法により硬化させて形成する形成方法等が挙げられる。 As a method for forming a moisture trap according to the present embodiment, for example, after forming a coating film on a substrate such as glass using the moisture trap forming composition of the embodiment of the present invention described above, the coating film is irradiated with radiation. Examples thereof include a method of irradiating, a method of heating, and a method of forming by curing by irradiation and heating.
　上述の放射線としては、水分捕獲体形成組成物の塗膜を硬化できれば特に限定されないが、ＵＶ（紫外）光が好ましい。例えば、高圧水銀ランプを用い、紫外線照射（例：５００～１５０００ｍＪ／ｃｍ２）によって水分捕獲体形成組成物の塗膜の硬化を行うことができる。 The radiation is not particularly limited as long as it can cure the coating film of the moisture trap forming composition, but UV (ultraviolet) light is preferable. For example, the coating film of the moisture trap forming composition can be cured by ultraviolet irradiation (eg, 500 to 15000 mJ / cm 2 ) using a high-pressure mercury lamp.
　また、上述した加熱する方法の、加熱温度としては、３０℃～２００℃が好ましく、５０℃～１５０℃がより好ましい。加熱時間としては、１分間～２４時間が好ましく、１０分間～５時間がより好ましい。 In the heating method described above, the heating temperature is preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C. The heating time is preferably 1 minute to 24 hours, more preferably 10 minutes to 5 hours.
　本実施形態の水分捕獲体は、上述した本発明の実施形態の水分捕獲体形成組成物から形成されて、（Ａ）加水分解性基を有する化合物および該化合物の加水分解物からなる群より選択される少なくとも１種の化合物と、（Ｂ）酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物と、（Ｃ）硬化性化合物とを含む。 The moisture trap of this embodiment is selected from the group consisting of (A) a compound having a hydrolyzable group and a hydrolyzate of the compound, which is formed from the above-described moisture trap forming composition of the embodiment of the present invention. And (B) at least one compound selected from the group consisting of an acid generator and a base generator, and (C) a curable compound.
　尚、以下の説明において、（Ａ）加水分解性基を有する化合物および該化合物の加水分解物からなる群より選択される少なくとも１種の化合物を（Ａ）化合物ともいい、（Ｂ）酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物を（Ｂ）化合物ともいい、（Ｃ）硬化性化合物を（Ｃ）化合物ともいう。 In the following description, (A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound is also referred to as (A) compound, and (B) an acid generator. And at least one compound selected from the group consisting of base generators is also referred to as (B) compound, and (C) curable compound is also referred to as (C) compound.
　本実施形態の水分捕獲体は、上述したように、本発明の実施形態の水分捕獲体形成組成物から形成されるため、（Ａ）化合物は、水分捕獲体形成組成物の水分捕獲剤（Ａ）（成分（Ａ））によるものである。すなわち、（Ａ）化合物のうちの加水分解性基を有する化合物は、水分捕獲剤（Ａ）として水分捕獲体形成組成物に含有されたものである。同様に、本実施形態の水分捕獲体の含む（Ｂ）化合物は、本発明の実施形態の水分捕獲体形成組成物の酸・塩基発生剤（Ｂ）（成分（Ｂ））によるものである。また、本実施形態の水分捕獲体の含む（Ｃ）化合物は、本発明の実施形態の水分捕獲体形成組成物の硬化性化合物（Ｃ）（成分（Ｃ））によるものである。 As described above, since the moisture trap of the present embodiment is formed from the moisture trap forming composition of the embodiment of the present invention, the compound (A) is a moisture trap (A) of the moisture trap forming composition. ) (Component (A)). That is, the compound which has a hydrolysable group among (A) compounds is contained in the water-trapping body formation composition as a water-trapping agent (A). Similarly, the (B) compound contained in the moisture trap of this embodiment is derived from the acid / base generator (B) (component (B)) of the moisture trap formation composition of the embodiment of the present invention. In addition, the (C) compound contained in the moisture trap of the present embodiment is due to the curable compound (C) (component (C)) of the moisture trap forming composition of the embodiment of the present invention.
　したがって、（Ａ）化合物である加水分解性基を有する化合物の例は、水分捕獲体形成組成物の水分捕獲剤（Ａ）の例と同様であり、（Ｂ）化合物の例は、水分捕獲体形成組成物の酸・塩基発生剤（Ｂ）と同様であり、（Ｃ）化合物の例は、水分捕獲体形成組成物の硬化性化合物（Ｃ）と同様である。 Therefore, the example of the compound (A) having a hydrolyzable group is the same as the example of the water trapping agent (A) of the water trap forming composition, and the example of the compound (B) is a water trap. It is the same as the acid / base generator (B) of the forming composition, and examples of the (C) compound are the same as the curable compound (C) of the moisture trap forming composition.
　また、上述したように、本発明の実施形態の水分捕獲体形成組成物においては、酸発生剤（Ｂ１）を含有する場合、水分捕獲剤（Ａ）として、水分捕獲剤（Ａ１）～（Ａ３）から選ばれる少なくとも１種が用いられる。一方、本発明の実施形態の水分捕獲体形成組成物においては、塩基発生剤（Ｂ２）を含有する場合、水分捕獲剤（Ａ）として、水分捕獲剤（Ａ２）～（Ａ３）から選ばれる少なくとも１種が用いられる。 Further, as described above, in the moisture trap forming composition of the embodiment of the present invention, when the acid generator (B1) is contained, the moisture trapping agents (A1) to (A3) are used as the moisture trapping agents (A). ) Is used. On the other hand, in the moisture trap forming composition of the embodiment of the present invention, when the base generator (B2) is contained, the moisture trapping agent (A) is at least selected from the moisture trapping agents (A2) to (A3). One type is used.
　そのため、本実施形態の水分捕獲体においては、より具体的に、（Ａ）化合物が、（Ａ１）式（Ａ１－１）で表される化合物、式（Ａ１－２）で表される化合物および式（Ａ１－３）で表される化合物から選ばれる少なくとも１種の化合物（（Ａ１）化合物ともいう。）、（Ａ２）カルボン酸無水物およびカルボン酸化合物から選ばれる少なくとも１種の化合物（（Ａ２）化合物ともいう。）、並びに、（Ａ３）式（Ａ３－１）で表される化合物、式（Ａ３－２）で表される化合物および式（Ａ３－３）で表される化合物（（Ａ３）化合物ともいう。）から選ばれる少なくとも１種の化合物からなる群から選択される少なくとも１種であり、（Ｂ）化合物が、酸発生剤であることが好ましい。 Therefore, in the moisture trap of the present embodiment, more specifically, (A) the compound is (A1) a compound represented by the formula (A1-1), a compound represented by the formula (A1-2), and At least one compound selected from compounds represented by formula (A1-3) (also referred to as (A1) compound), (A2) at least one compound selected from carboxylic acid anhydride and carboxylic acid compound (( A2) also referred to as a compound), and (A3) a compound represented by formula (A3-1), a compound represented by formula (A3-2), and a compound represented by formula (A3-3) (( A3) It is also referred to as a compound.) It is at least one selected from the group consisting of at least one compound selected from the above, and (B) the compound is preferably an acid generator.
　また別の例として、本実施形態の水分捕獲体においては、（Ａ）化合物が、上述の（Ａ２）化合物、および、上述の（Ａ３）化合物からなる群から選択される少なくとも１種であり、（Ｂ）化合物が、塩基発生剤であることが好ましい。 As another example, in the moisture trap of the present embodiment, the (A) compound is at least one selected from the group consisting of the above-mentioned (A2) compound and the above-mentioned (A3) compound, (B) It is preferable that a compound is a base generator.
Figure JPOXMLDOC01-appb-C000028
 ［式（Ａ１－１）中、Ｒ１～Ｒ５は、それぞれ独立に水素原子または炭素数１～１８の有機基であり、Ｒ６およびＲ７は、それぞれ独立に水素原子、水酸基または炭素数１～１８の有機基であり、Ｒ３、Ｒ４およびＲ７は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよく、ｎは０または１～１８の整数であり、＊は結合位を示し；式（Ａ１－２）中、Ｒ１は水素原子または炭素数１～１８の有機基であり；Ｒ８はそれぞれ独立に炭素数３～３０の有機基であり；式（Ａ１－３）中、式Ｒ８は式（Ａ１－２）と同義である。］
Figure JPOXMLDOC01-appb-C000028
 [In the formula (A1-1), R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or a carbon number. An organic group of 1 to 18, and R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure, and n is 0 or an integer of 1 to 18 * Represents a bonding position; in formula (A1-2), R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; and R 8 is independently an organic group having 3 to 30 carbon atoms. There; wherein (A1-3), wherein R 8 has the same meaning as in formula (A1-2). ]
Figure JPOXMLDOC01-appb-C000029
 ［式（Ａ３－１）、式（Ａ３－２）および式（Ａ３－３）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基、カルボニル基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、またはメルカプト基であり；
ｐは０～６の整数であり；
ｒは０～２の整数であり、ｓは１～３０の整数である。］
Figure JPOXMLDOC01-appb-C000029
 [In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom; R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent. Group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group;
p is an integer from 0 to 6;
r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
　このとき、（Ａ）化合物のうちの式（Ａ１－３）で表される化合物は、本発明の実施形態の水分捕獲体形成組成物の作用効果について例を挙げて説明したように、式（Ａ１－１）で表される化合物および式（Ａ１－２）で表される化合物の加水分解生成物である。 At this time, among the compounds (A), the compound represented by the formula (A1-3) has the formula (A) as described with reference to the action and effect of the moisture trapping body-forming composition of the embodiment of the present invention. A hydrolysis product of the compound represented by A1-1) and the compound represented by Formula (A1-2).
　また、（Ａ）化合物であるカルボン酸無水物は、上述した水分捕獲剤（Ａ２）のカルボン酸無水物である。そして、（Ａ）化合物のうちのカルボン酸化合物は、本発明の実施形態の水分捕獲体形成組成物の作用効果について説明したように、そのカルボン酸無水物の加水分解生成物である。 Further, the carboxylic acid anhydride which is the compound (A) is the carboxylic acid anhydride of the water trapping agent (A2) described above. And the carboxylic acid compound of (A) compounds is the hydrolysis product of the carboxylic anhydride, as demonstrated about the effect of the moisture-capturing body formation composition of embodiment of this invention.
　また、（Ａ）化合物のうちの式（Ａ３－３）で表される化合物は、本発明の実施形態の水分捕獲体形成組成物の作用効果について説明したように、式（Ａ３－１）で表される化合物および式（Ａ３－２）で表される化合物の加水分解生成物である。 Further, among the compounds (A), the compound represented by the formula (A3-3) is represented by the formula (A3-1) as described for the action and effect of the moisture trapping body forming composition of the embodiment of the present invention. And a hydrolysis product of the compound represented by formula (A3-2).
　本発明の実施形態の水分捕獲体は、本発明の実施形態の水分捕獲体形成組成物の水分捕獲剤（Ａ１）～（Ａ３）およびそれらの加水分解生成物からなる群より選択される少なくとも１種の化合物を含む。 The moisture trap of the embodiment of the present invention is at least one selected from the group consisting of the moisture traps (A1) to (A3) of the moisture trap forming composition of the embodiment of the present invention and their hydrolysis products. Contains seed compounds.
　さらに、本実施形態の水分捕獲体は、上述した本発明の実施形態の水分捕獲体形成組成物から形成されて、（Ｄ）ラジカル重合開始剤を含有することができる。本実施形態の水分捕獲体が（Ｅ）微粒子を含む場合、その（Ｄ）ラジカル重合開始剤は、本発明の実施形態の水分捕獲体形成組成物のラジカル重合開始剤（Ｄ）（成分（Ｄ））によるものである。したがって、（Ｄ）ラジカル重合開始剤の例は、水分捕獲体形成組成物の成分（Ｄ）と同様である。本実施形態の水分捕獲体は（Ｄ）ラジカル重合開始剤を含有することで、アルコール化合物等の上記加水分解反応の生成物が水分捕獲体中に効率良く固定化され、留まることが容易となる。 Furthermore, the moisture trap of the present embodiment is formed from the above-described moisture trap forming composition of the embodiment of the present invention, and can contain (D) a radical polymerization initiator. When the water trap of this embodiment contains (E) fine particles, the (D) radical polymerization initiator is a radical polymerization initiator (D) (component (D) of the water trap formation composition of the embodiment of the present invention. )). Therefore, the example of the (D) radical polymerization initiator is the same as the component (D) of the moisture trap forming composition. By containing the (D) radical polymerization initiator in the moisture trap of this embodiment, the product of the hydrolysis reaction such as an alcohol compound is efficiently immobilized and easily retained in the moisture trap. .
　さらに、本実施形態の水分捕獲体は、上述した本発明の実施形態の水分捕獲体形成組成物から形成されて、（Ｅ）微粒子を含有することができる。本実施形態の水分捕獲体が（Ｅ）微粒子を含む場合、その（Ｅ）微粒子は、本発明の実施形態の水分捕獲体形成組成物の微粒子（Ｅ）（成分（Ｅ））によるものである。したがって、（Ｅ）微粒子の例は、水分捕獲体形成組成物の成分（Ｅ）と同様である。本実施形態の水分捕獲体は（Ｅ）微粒子を含有することで、耐熱性を向上させることができ、また、有機ＥＬ素子に適用されて光取出し効率を向上させることができる。 Furthermore, the moisture trap of the present embodiment is formed from the above-described moisture trap forming composition of the embodiment of the present invention, and can contain (E) fine particles. When the moisture trap of this embodiment includes (E) fine particles, the (E) fine particles are due to the fine particles (E) (component (E)) of the moisture trap forming composition of the embodiment of the present invention. . Accordingly, examples of the fine particles (E) are the same as the component (E) of the moisture trap forming composition. The moisture trap of this embodiment can improve heat resistance by containing (E) fine particles, and can be applied to an organic EL element to improve light extraction efficiency.
　以上で説明した本発明の実施形態の水分捕獲体は、その形成時において、適用される有機ＥＬ素子等の電子デバイス内の水分を効率良く除去するとともに、形成の後も、素子内の水分を消費することができる。 The moisture trap of the embodiment of the present invention described above efficiently removes moisture in an electronic device such as an organic EL element to be applied at the time of formation, and also removes moisture in the element after formation. Can be consumed.
　そして、本実施形態の水分捕獲体は、水分を捕獲した状態であっても、低分子アルコール等のような揮発性の高い分解生成物を生じ難く、例えば、有機ＥＬ素子等に用いられた場合、有機ＥＬ層への上記分解生成物の付着によるダークスポットの発生を抑制することができる。すなわち、本発明の実施形態の水分捕獲体は、特に有機ＥＬ素子用として、好適に用いることができる。 And even if the moisture trap of this embodiment is the state which trapped the moisture, it is hard to produce decomposition products with high volatility like low molecular alcohol etc., for example, when used for an organic EL element etc. The generation of dark spots due to the adhesion of the decomposition products to the organic EL layer can be suppressed. That is, the moisture trap of the embodiment of the present invention can be suitably used particularly for an organic EL element.
　〔電子デバイス〕
　本発明の実施形態の水分捕獲体形成組成物は、水分捕獲体を形成し、水分が特性を低下させる懸念のある本発明の実施形態の電子デバイスの構成に用いられる。本発明の実施形態の電子デバイスとしては、水分が特性を低下させる懸念のある電子デバイスであれば、いかなる電子デバイスであってもよい。そのような電子デバイスとしては、例えば、有機ＥＬ素子および液晶表示素子が挙げられる。有機ＥＬ素子である場合、例えば、高信頼の有機ＥＬ照明装置や有機ＥＬ表示素子を構成することができる。 [Electronic device]
The moisture trap forming composition of the embodiment of the present invention is used in the configuration of the electronic device according to the embodiment of the present invention, which forms a moisture trap and there is a concern that the moisture may deteriorate the characteristics. The electronic device according to the embodiment of the present invention may be any electronic device as long as moisture is an electronic device that may cause deterioration in characteristics. Examples of such electronic devices include organic EL elements and liquid crystal display elements. In the case of an organic EL element, for example, a highly reliable organic EL lighting device or organic EL display element can be configured.
　本発明の実施形態の有機ＥＬ素子が、本発明の実施形態の水分捕獲体を備えることで、本発明の実施形態の水分捕獲体形成組成物からその水分捕獲体が形成される時に、素子内の水分を効率良く除去することができる。そして、本発明の実施形態の水分捕獲体は、その形成の後も長期間に亘って素子内の水分を吸収することができるため、水分に起因する素子の劣化を抑制することができる。 When the organic EL element of the embodiment of the present invention includes the moisture trap of the embodiment of the present invention, the moisture trap is formed from the moisture trap forming composition of the embodiment of the present invention. Can be removed efficiently. And since the moisture trap of the embodiment of the present invention can absorb the moisture in the element for a long period after its formation, it is possible to suppress deterioration of the element due to moisture.
　＜有機ＥＬ素子＞
　次に、本発明の実施形態の有機ＥＬ素子について図面を参照しながら説明する。 <Organic EL device>
Next, the organic EL element of the embodiment of the present invention will be described with reference to the drawings.
　図１は、本発明の実施形態の有機ＥＬ素子の第一例を模式的に示す断面図である。 FIG. 1 is a cross-sectional view schematically showing a first example of an organic EL element according to an embodiment of the present invention.
　図１に示す、本発明の実施形態の有機ＥＬ素子の第一例である有機ＥＬ素子１００は、有機ＥＬ層１０と、有機ＥＬ層１０を収納して外気から遮断するための構造体２０と、構造体２０内に形成された水分捕獲体３０とを備えている。水分捕獲体３０は、上述した本発明の実施形態の水分捕獲体形成組成物を用いて形成されたものである。また、構造体２０は、有機ＥＬ層１０を支持する素子用の基板である基板２２や封止用基板２４やシール材２６を含んで構成される。 An organic EL element 100 that is a first example of the organic EL element according to the embodiment of the present invention shown in FIG. 1 includes an organic EL layer 10 and a structure 20 that houses the organic EL layer 10 and blocks it from the outside air. And a moisture trap 30 formed in the structure 20. The moisture trap 30 is formed using the moisture trap forming composition of the embodiment of the present invention described above. The structure 20 includes a substrate 22, a sealing substrate 24, and a sealing material 26 that are substrates for elements that support the organic EL layer 10.
　有機ＥＬ素子１００の有機ＥＬ層１０は、構造の詳細を省略するが、有機材料からなる有機発光層が互いに対向する一対の電極の間に挟持されてなる構造であればよく、例えば、陽極／有機発光層／陰極等からなる公知の構造をとることができる。そして、必要に応じ、陽極と有機発光層との間には、電荷（正孔）注入層や電荷（正孔）輸送層を設けることができ、陰極と有機発光層との間には、電子注入層や電子輸送層を設けることができる。有機ＥＬ層１０は、図１に示すように、構造体２０の基板２２上に配置される。 Although the details of the structure of the organic EL layer 10 of the organic EL element 100 are omitted, it is sufficient that the organic light emitting layer made of an organic material is sandwiched between a pair of electrodes facing each other. A known structure comprising an organic light emitting layer / cathode or the like can be employed. If necessary, a charge (hole) injection layer or a charge (hole) transport layer can be provided between the anode and the organic light emitting layer, and an electron can be provided between the cathode and the organic light emitting layer. An injection layer or an electron transport layer can be provided. The organic EL layer 10 is disposed on the substrate 22 of the structure 20 as shown in FIG.
　有機ＥＬ素子１００は、ボトムエミッション構造またはトップエミッション構造とすることができるが、有機ＥＬ素子１００がトップエミッション構造の場合、有機ＥＬ層１０は、陽極となる背面電極と、有機発光層と、陰極となる透光性または半透光性の前面電極とが、基板２２上でこの順となるように配置されて構成される。 The organic EL element 100 can have a bottom emission structure or a top emission structure. When the organic EL element 100 has a top emission structure, the organic EL layer 10 includes a back electrode serving as an anode, an organic light emitting layer, and a cathode. The translucent or semi-transparent front electrode is arranged on the substrate 22 in this order.
　その場合、有機ＥＬ層１０の背面電極は光反射性を有することが好ましい。この背面電極の材料としては、金属、合金、導電性金属酸化物、他の導電性化合物、およびこれらの混合物を用いることができる。 In that case, the back electrode of the organic EL layer 10 preferably has light reflectivity. As the material for the back electrode, metals, alloys, conductive metal oxides, other conductive compounds, and mixtures thereof can be used.
　有機ＥＬ層１０の背面電極の材料の具体例としては、
アルカリ金属（例えば、Ｌｉ、Ｎａ、およびＫ等）およびそのフッ化物；
アルカリ土類金属（例えば、Ｍｇ、およびＣａ等）およびそのフッ化物；
金、銀、鉛、アルミニウム、ナトリウム－カリウム合金、およびこれらを含む混合金属；
リチウム－アルミニウム合金およびこれを含む混合金属；
ＬｉＦ／Ａｌ合金およびこれを含む混合金属；
マグネシウム－銀合金およびこれを含む混合金属；
インジウム、およびイッテリビウム等の希土類金属等が挙げられる。
好ましくは仕事関数が４ｅＶ以下の材料であり、より好ましくはアルミニウム、リチウム－アルミニウム合金およびそれらの混合金属、マグネシウム－銀合金およびその混合金属等を挙げることができる。 As a specific example of the material of the back electrode of the organic EL layer 10,
Alkali metals (eg, Li, Na, and K, etc.) and fluorides thereof;
Alkaline earth metals (eg, Mg, Ca, etc.) and fluorides thereof;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals containing them;
Lithium-aluminum alloys and mixed metals containing them;
LiF / Al alloys and mixed metals containing them;
Magnesium-silver alloys and mixed metals containing them;
And rare earth metals such as indium and ytterbium.
A material having a work function of 4 eV or less is preferable, and aluminum, a lithium-aluminum alloy and a mixed metal thereof, a magnesium-silver alloy and a mixed metal thereof are preferable.
　有機ＥＬ層１０の背面電極の膜厚は材料により適宜選択可能であるが、１００ｎｍ～１μｍが好ましい。背面電極の作製には、電子ビーム蒸着法、スパッタリング法、抵抗加熱蒸着法、およびコーティング法等の方法を用いることができる。このとき、金属を単体で蒸着することも、二成分以上を同時に蒸着することもできる。また、複数の金属を同時に蒸着して合金電極を形成することも可能であり、またあらかじめ調整した合金を蒸着させてもよい。 The film thickness of the back electrode of the organic EL layer 10 can be appropriately selected depending on the material, but is preferably 100 nm to 1 μm. For the production of the back electrode, methods such as an electron beam vapor deposition method, a sputtering method, a resistance heating vapor deposition method, and a coating method can be used. At this time, the metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. It is also possible to form a metal electrode by simultaneously vapor-depositing a plurality of metals, or an alloy prepared in advance may be vapor-deposited.
　また、有機ＥＬ層１０の有機発光層の材料は、電界印加時に、陽極等から正孔を注入することができるとともに、陰極等から電子を注入することができる機能、注入された電荷を移動させる機能、および、正孔と電子の再結合の場を提供して発光させる機能を有する層を形成することができる材料であれば特に限定されない。 Moreover, the material of the organic light emitting layer of the organic EL layer 10 can inject holes from the anode and the like when an electric field is applied, and can also inject electrons from the cathode and the like, and moves the injected charges. The material is not particularly limited as long as it is a material that can form a layer having a function and a function of emitting light by providing a recombination field of holes and electrons.
　有機ＥＬ層１０の有機発光層の材料は、例えば、ベンゾオキサゾール誘導体、ベンゾイミダゾール誘導体、ベンゾチアゾール誘導体、スチリルベンゼン誘導体、ポリフェニル誘導体、ジフェニルブタジエン誘導体、テトラフェニルブタジエン誘導体、ナフタルイミド誘導体、クマリン誘導体、ペリレン誘導体、ペリノン誘導体、オキサジアゾール誘導体、アルダジン誘導体、ピラリジン誘導体、シクロペンタジエン誘導体、ビススチリルアントラセン誘導体、キナクリドン誘導体、ピロロピリジン誘導体、チアジアゾロピリジン誘導体、シクロペンタジエン誘導体、スチリルアミン誘導体、芳香族ジメチリディン化合物、および８－キノリノール誘導体の金属錯体または希土類錯体に代表される各種金属錯体；
および、
ポリチオフェン、ポリフェニレン、およびポリフェニレンビニレン等のポリマー化合物等が挙げられる。 The materials of the organic light emitting layer of the organic EL layer 10 are, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, Perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidins Compounds, and various metal complexes represented by metal complexes or rare earth complexes of 8-quinolinol derivatives;
and,
And polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene.
　有機ＥＬ層１０の有機発光層となる発光材料の具体例を下記に挙げるが、以下の具体的に例示したものに限定されるわけではない。 Specific examples of the light emitting material to be the organic light emitting layer of the organic EL layer 10 are listed below, but are not limited to those specifically exemplified below.
　青色の発光は、例えば、ペリレン、２，５，８，１１－テトラ－ｔ－ブチルペリレン（ＴＢＰ）、および９，１０－ジフェニルアントラセン誘導体等をゲスト材料として用いることによって得られる。また、４，４’－ビス（２，２－ジフェニルビニル）ビフェニル（ＤＰＶＢｉ）等のスチリルアリーレン誘導体、９，１０－ジ－２－ナフチルアントラセン（ＤＮＡ）、および９，１０－ビス（２－ナフチル）－２－ｔｅｒｔ－ブチルアントラセン（ｔ－ＢｕＤＮＡ）等のアントラセン誘導体から得ることもできる。また、ポリ（９，９－ジオクチルフルオレン）等のポリマーを用いてもよい。 Blue light emission can be obtained by using, for example, perylene, 2,5,8,11-tetra-t-butylperylene (TBP), 9,10-diphenylanthracene derivative, or the like as a guest material. In addition, styrylarylene derivatives such as 4,4′-bis (2,2-diphenylvinyl) biphenyl (DPVBi), 9,10-di-2-naphthylanthracene (DNA), and 9,10-bis (2-naphthyl) It can also be obtained from anthracene derivatives such as 2-tert-butylanthracene (t-BuDNA). A polymer such as poly (9,9-dioctylfluorene) may also be used.
　緑色の発光は、クマリン３０、クマリン６等のクマリン系色素、ビス［２－（２，４－ジフルオロフェニル）ピリジナト］ピコリナトイリジウム（ＦＩｒｐｉｃ）、およびビス（２－フェニルピリジナト）アセチルアセトナトイリジウム（Ｉｒ（ｐｐｙ）（ａｃａｃ））等をゲスト材料として用いることによって得られる。また、トリス（８－ヒドロキシキノリン）アルミニウム（Ａｌｑ３）、ＢＡｌｑ、Ｚｎ（ＢＴＺ）、およびビス（２－メチル－８－キノリノラト）クロロガリウム（Ｇａ（ｍｑ）２Ｃｌ）等の金属錯体からも得ることができる。また、ポリ（ｐ－フェニレンビニレン）等のポリマーを用いてもよい。 Green light is emitted from coumarin dyes such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (FIrpic), and bis (2-phenylpyridinato) acetylacetonate. It can be obtained by using iridium (Ir (ppy) (acac)) or the like as a guest material. Also obtained from metal complexes such as tris (8-hydroxyquinoline) aluminum (Alq3), BAlq, Zn (BTZ), and bis (2-methyl-8-quinolinolato) chlorogallium (Ga (mq) 2 Cl) Can do. Further, a polymer such as poly (p-phenylene vinylene) may be used.
　橙色から赤色の発光は、ルブレン、４－（ジシアノメチレン）－２－［ｐ－（ジメチルアミノ）スチリル］－６－メチル－４Ｈ－ピラン（ＤＣＭ１）、４－（ジシアノメチレン）－２－メチル－６－（９－ジュロリジル）エチニル－４Ｈ－ピラン（ＤＣＭ２）、４－（ジシアノメチレン）－２，６－ビス［ｐ－（ジメチルアミノ）スチリル］－４Ｈ－ピラン（ＢｉｓＤＣＭ）、ビス［２－（２－チエニル）ピリジナト］アセチルアセトナトイリジウム（Ｉｒ（ｔｈｐ）２（ａｃａｃ））、およびビス（２－フェニルキノリナト）アセチルアセトナトイリジウム（Ｉｒ（ｐｑ）（ａｃａｃ））等をゲスト材料として用いることによって得られる。ビス（８－キノキリノラト）亜鉛（Ｚｎｑ２）、ビス［２－シンナモイル－８－キノリノラト］亜鉛（Ｚｎｓｑ２）等の金属錯体からも得ることができる。また、ポリ（２，５－ジアルコキシ－１，４－フェニレンビニレン）等のポリマーを用いてもよい。 The orange to red luminescence is rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (DCM1), 4- (dicyanomethylene) -2-methyl- 6- (9-Jurolidyl) ethynyl-4H-pyran (DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl] -4H-pyran (BisDCM), bis [2- ( 2-thienyl) pyridinato] acetylacetonatoiridium (Ir (thp) 2 (acac)), bis (2-phenylquinolinato) acetylacetonatoiridium (Ir (pq) (acac)) and the like are used as guest materials Obtained by. It can also be obtained from a metal complex such as bis (8-quinolinolato) zinc (Znq 2 ) or bis [2-cinnamoyl-8-quinolinolato] zinc (Znsq 2 ). Further, a polymer such as poly (2,5-dialkoxy-1,4-phenylene vinylene) may be used.
　白色の発光は、有機ＥＬ積層構造体の各層のエネルギー準位を規定し、トンネル注入を利用して発光させるもの（欧州特許第０３９０５５１号公報）、同じくトンネル注入を利用する素子で実施例として白色発光素子が記載されているもの（特開平３－２３０５８４号公報）、二層構造の発光層が記載されているもの（特開平２－２２０３９０号公報および特開平２－２１６７９０号公報）、発光層を複数に分割してそれぞれ発光波長の異なる材料で構成されたもの（特開平４－５１４９１号公報）、青色発光体（蛍光ピ－ク３８０～４８０ｎｍ）と緑色発光体（４８０～５８０ｎｍ）とを積層させ、さらに赤色蛍光体を含有させた構成のもの（特開平６－２０７１７０号公報）、青色発光層が青色蛍光色素を含有し、緑色発光層が赤色蛍光色素を含有した領域を有し、さらに緑色蛍光体を含有する構成のもの（特開平７－１４２１６９号公報）等が挙げられる。 White light emission defines the energy level of each layer of the organic EL laminated structure and emits light using tunnel injection (European Patent No. 0390551). A light emitting element is described (Japanese Patent Laid-Open No. 3-230484), a light emitting layer having a two-layer structure is described (Japanese Patent Laid-Open No. 2-220390 and Japanese Patent Laid-Open No. 2-216790), and a light emitting layer Are made of materials having different emission wavelengths (JP-A-4-51491), a blue light emitter (fluorescent peak 380 to 480 nm) and a green light emitter (480 to 580 nm). A structure in which a red phosphor is further contained (Japanese Patent Laid-Open No. 6-207170), the blue light emitting layer contains a blue fluorescent dye, and the green light emitting layer has a red phosphor. It has a region containing a dye, such as construction of those (JP-A-7-142169) and the like further containing a green phosphor.
　有機ＥＬ層１０の有機発光層の膜厚は特に限定されるものではないが、通常１０ｎｍ～５００ｎｍが好ましい。各層は単層構造であってもよいし、同一組成または異種組成の複層構造であってもよい。 The thickness of the organic light emitting layer of the organic EL layer 10 is not particularly limited, but is usually preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.
　有機ＥＬ層１０の有機発光層の形成方法は特に限定されるものではないが、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、分子積層法、コーティング法（スピンコート法、キャスト法、およびディップコート法等）、およびＬＢ（Ｌａｎｇｍｕｉｒ　Ｂｌｏｄｇｅｔｔ）法などの方法が用いられる。好ましくは抵抗加熱蒸着法、およびコーティング法である。 A method for forming the organic light emitting layer of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Blodgett) method. The resistance heating vapor deposition method and the coating method are preferable.
　また、有機ＥＬ層１０の前面電極は、上述したように、有機ＥＬ素子１００がトップエミッション構造である場合、透光性または半透光性を有することが好ましい。 Further, as described above, the front electrode of the organic EL layer 10 preferably has a light-transmitting property or a semi-light-transmitting property when the organic EL element 100 has a top emission structure.
　そのような有機ＥＬ層１０の透光性または半透光性の前面電極の材料としては、金属、合金、金属酸化物、電気伝導性化合物、またはこれらの混合物等を用いることができる。 As a material for such a translucent or semi-transparent front electrode of the organic EL layer 10, a metal, an alloy, a metal oxide, an electrically conductive compound, a mixture thereof, or the like can be used.
　有機ＥＬ層１０の透光性または半透光性の前面電極の材料の具体例としては、
酸化スズ、酸化亜鉛、酸化インジウム、および酸化インジウムスズ（ＩＴＯ）等の導電性金属酸化物；
金、銀、クロム、およびニッケル等の金属；
ヨウ化銅および硫化銅などの他の無機導電性物質；
ポリアニリン、ポリチオフェン、ＰＥＤＯＴ／ＰＳＳ、およびポリピロール等の有機導電性物質；
およびこれらの混合物または積層物等が挙げられる。 As a specific example of the translucent or semi-transparent front electrode material of the organic EL layer 10,
Conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO);
Metals such as gold, silver, chromium and nickel;
Other inorganic conductive materials such as copper iodide and copper sulfide;
Organic conductive materials such as polyaniline, polythiophene, PEDOT / PSS, and polypyrrole;
And mixtures or laminates thereof.
　上述した有機ＥＬ層１０の前面電極の中で、好ましくは導電性金属酸化物であり、特に、生産性、高導電性、および透光性等の点からＩＴＯが好ましい。 Among the front electrodes of the organic EL layer 10 described above, a conductive metal oxide is preferable, and ITO is particularly preferable in terms of productivity, high conductivity, translucency, and the like.
　また、有機ＥＬ層１０の前面電極は、透光性を保ちながら有機発光層への電子の注入性を制御するために、金属類とＩＴＯを積層して透光性電極とすることも可能である。ここで、極薄の金属の厚さとしては０．１ｎｍ～２０ｎｍが透光性を保つ観点で好ましい。また、ここでいう金属類としては、
アルカリ金属（例えばＬｉ、Ｎａ、およびＫ等）およびそのフッ化物；
アルカリ土類金属（例えばＭｇ、およびＣａ等）およびそのフッ化物；
金、銀、鉛、アルミニウム、ナトリウム－カリウム合金、およびこれらを含む混合金属；
リチウム－アルミニウム合金およびこれを含む混合金属；
ＬｉＦ／Ａｌ合金およびこれを含む混合金属；
マグネシウム－銀合金およびこれを含む混合金属；
インジウム、およびイッテリビウム等の希土類金属等が挙げられる。 In addition, the front electrode of the organic EL layer 10 can be made of a light-transmitting electrode by laminating metals and ITO in order to control the electron injection property to the organic light-emitting layer while maintaining the light-transmitting property. is there. Here, the thickness of the ultrathin metal is preferably from 0.1 nm to 20 nm from the viewpoint of maintaining translucency. In addition, as metals here,
Alkali metals (such as Li, Na, and K) and fluorides thereof;
Alkaline earth metals (such as Mg and Ca) and their fluorides;
Gold, silver, lead, aluminum, sodium-potassium alloys, and mixed metals containing them;
Lithium-aluminum alloys and mixed metals containing them;
LiF / Al alloys and mixed metals containing them;
Magnesium-silver alloys and mixed metals containing them;
And rare earth metals such as indium and ytterbium.
　以上の例示の中で、上述の金属類として、好ましくはアルミニウム、リチウム－アルミニウム合金およびそれらの混合金属、マグネシウム－銀合金およびその混合金属等である。 Among the above examples, the above metals are preferably aluminum, lithium-aluminum alloy and mixed metal thereof, magnesium-silver alloy and mixed metal thereof.
　前面電極の膜厚は材料により適宜選択可能であるが、通常５０ｎｍ ～３００ｎｍ程度が好ましい。 The film thickness of the front electrode can be appropriately selected depending on the material, but is usually preferably about 50 nm to 300 nm.
　前面電極の形成方法としては、電子ビーム法、スパッタリング法、抵抗加熱蒸着法、化学反応法（ゾル－ゲル法など）、および溶解物や分散物の塗布などの方法が用いられる。形成した前面電極は、所望に応じて、エッチング処理を行い、パターンを形成する。さらに、洗浄その他の処理により、有機ＥＬ素子の駆動電圧を下げたり、発光効率を高めることも可能である。例えば、前面電極にＩＴＯを用いた場合、ＵＶ－オゾン処理等が効果的である。 As a method for forming the front electrode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), and a solution or dispersion coating method are used. The formed front electrode is etched to form a pattern as desired. Furthermore, the driving voltage of the organic EL element can be lowered or the luminous efficiency can be increased by washing or other processing. For example, when ITO is used for the front electrode, UV-ozone treatment or the like is effective.
　さらに、有機ＥＬ層１０が陽極と有機発光層との間に正孔注入層や正孔輸送層を有する場合、それらの材料は、陽極から正孔を注入する機能、注入された正孔を輸送する機能、陰極から注入された電子を障壁する機能のいずれかを有しているものであればよい。その具体例としては、カルバゾール誘導体、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体、ピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、芳香族第三級アミン化合物、スチリルアミン化合物、芳香族ジメチリディン系化合物、ポルフィリン系化合物、ポリシラン系化合物、ポリ（ Ｎ－ビニルカルバゾール）誘導体、アニリン系共重合体、チオフェンオリゴマー、およびポリチオフェン等の導電性高分子オリゴマー等が挙げられる。 Further, when the organic EL layer 10 has a hole injection layer or a hole transport layer between the anode and the organic light emitting layer, these materials have a function of injecting holes from the anode, and transport the injected holes. Any one having a function of blocking the electrons injected from the cathode may be used. Specific examples include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styrylanthracene derivatives. , Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, aniline compounds Examples thereof include copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene.
　また、有機ＥＬ層１０が陰極と有機発光層との間に電子注入層や電子輸送層を有する場合、電子注入層および電子輸送層の材料は、陰極から電子を注入する機能、電子を輸送する機能、または陽極から注入された正孔を障壁する機能を有しているものであればよい。その具体例としては、トリアゾール誘導体、オキサゾール誘導体、オキサジアゾール誘導体、フルオレノン誘導体、アントラキノジメタン誘導体、アントロン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、カルボジイミド誘導体、フルオレニリデンメタン誘導体、ジスチリルピラジン誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物、シロール誘導体、フタロシアニン誘導体、および８－キノリノール誘導体の金属錯体；メタルフタロシアニン、ベンゾオキサゾール、およびベンゾチアゾールを配位子とする金属錯体に代表される各種金属錯体等が挙げられる。 Further, when the organic EL layer 10 has an electron injection layer or an electron transport layer between the cathode and the organic light emitting layer, the material of the electron injection layer and the electron transport layer transports electrons from the cathode. Any function may be used as long as it has a function or a function of blocking holes injected from the anode. Specific examples include triazole derivatives, oxazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyryl. Metal complexes of pyrazine derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, silole derivatives, phthalocyanine derivatives, and 8-quinolinol derivatives; represented by metal complexes with metal phthalocyanine, benzoxazole, and benzothiazole as ligands And various metal complexes.
　有機ＥＬ層１０の正孔注入層、正孔輸送層、電子注入層および電子輸送層の膜厚は特に限定されるものではないが、通常１０ｎｍ～５００ｎｍが好ましい。各層は単層構造であってもよいし、同一組成または異種組成の複層構造であってもよい。 The film thickness of the hole injection layer, hole transport layer, electron injection layer, and electron transport layer of the organic EL layer 10 is not particularly limited, but is preferably 10 nm to 500 nm. Each layer may have a single layer structure, or a multilayer structure having the same composition or different compositions.
　有機ＥＬ層１０のこれらの層の形成方法は特に限定されるものではないが、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、分子積層法、コーティング法（スピンコート法、キャスト法、およびディップコート法等）、およびＬＢ（Ｌａｎｇｍｕｉｒ　Ｂｌｏｄｇｅｔｔ）法等の方法が用いられる。好ましくは抵抗加熱蒸着法、およびコーティング法である。 A method for forming these layers of the organic EL layer 10 is not particularly limited, but a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a molecular lamination method, a coating method (spin coating method, casting method, and dip method). And a method such as a LB (Langmuir Blodgett) method. The resistance heating vapor deposition method and the coating method are preferable.
　以上の構造の有機ＥＬ層１０を備えた有機ＥＬ素子１００では、構造体２０内に形成された水分捕獲体３０が、図１に示すように、有機ＥＬ層１０と離間して配置されている。 In the organic EL element 100 including the organic EL layer 10 having the above structure, the moisture trap 30 formed in the structure 20 is disposed separately from the organic EL layer 10 as shown in FIG. .
　有機ＥＬ素子１００の構造体２０は、基板２２と、基板２２において有機ＥＬ層１０の周辺部上に形成されたシール材２６と、シール材２６により基板２２に固定された封止用基板２４とを備えている。有機ＥＬ層１０は、基板２２、封止用基板２４およびシール材２６によって封止されている。有機ＥＬ素子１００内部は中空構造であり、有機ＥＬ層１０を劣化させないために不活性ガスで満たされていてもよい。 The structure 20 of the organic EL element 100 includes a substrate 22, a sealing material 26 formed on the periphery of the organic EL layer 10 in the substrate 22, and a sealing substrate 24 fixed to the substrate 22 by the sealing material 26. It has. The organic EL layer 10 is sealed with a substrate 22, a sealing substrate 24 and a sealing material 26. The inside of the organic EL element 100 has a hollow structure and may be filled with an inert gas so as not to deteriorate the organic EL layer 10.
　シール材２６は、接着剤組成物から形成されるシール材である。有機ＥＬ素子１００の基板２２としてはガラス基板等が挙げられ、封止用基板２４としてはガラス等からなる構造体が挙げられる。シール材２６は、封止用基板２４を基板２２に固定するとともに、封止用基板２４と基板２２との間で、有機ＥＬ層１０を密封する。尚、構造体２０の構造は、有機ＥＬ層１０を収納するとともにシール材２６を用いてそれを密封できればよく、特に限定されない。 The sealing material 26 is a sealing material formed from an adhesive composition. Examples of the substrate 22 of the organic EL element 100 include a glass substrate, and examples of the sealing substrate 24 include a structure made of glass or the like. The sealing material 26 fixes the sealing substrate 24 to the substrate 22 and seals the organic EL layer 10 between the sealing substrate 24 and the substrate 22. The structure of the structure 20 is not particularly limited as long as the organic EL layer 10 can be accommodated and sealed using the sealing material 26.
　例えば、有機ＥＬ素子１００を作成する際、接着剤組成物からなる塗膜により基板２２と封止用基板２４とを接着させた後、放射線照射および／または加熱することで、その塗膜を硬化させてシール材２６を形成し、封止空間内に有機ＥＬ層１０を密封することができる。 For example, when the organic EL element 100 is formed, the substrate 22 and the sealing substrate 24 are bonded to each other with a coating film made of an adhesive composition, and then the coating film is cured by irradiation and / or heating. Thus, the sealing material 26 is formed, and the organic EL layer 10 can be sealed in the sealing space.
　構造体２０内に形成された水分捕獲体３０は、有機ＥＬ層１０が密封された封止空間内の水分を捕獲して、効率良く除去することができる。水分捕獲体３０の構造および配置は特に限定されるものではないが、例えば、図１の有機ＥＬ素子１００のように、有機ＥＬ層１０と離間するように、封止用基板２４上に配置される。また、水分捕獲体３０は、封止空間内において、有機ＥＬ層１０またはシール材２６の側面に配置されてもよい。また、水分捕獲体３０は、有機ＥＬ層１０に密着するように有機ＥＬ層上に積層されていてもよく、後述するように、構造体２０内の封止空間全体を隙間なく埋めるように配置されていてもよい。 The moisture trap 30 formed in the structure 20 can capture and efficiently remove moisture in the sealed space in which the organic EL layer 10 is sealed. The structure and arrangement of the moisture trap 30 are not particularly limited. For example, the moisture trap 30 is arranged on the sealing substrate 24 so as to be separated from the organic EL layer 10 like the organic EL element 100 of FIG. The Further, the moisture trap 30 may be disposed on the side surface of the organic EL layer 10 or the sealing material 26 in the sealed space. In addition, the moisture trap 30 may be laminated on the organic EL layer so as to be in close contact with the organic EL layer 10 and is disposed so as to fill the entire sealing space in the structure 20 without any gaps, as will be described later. May be.
　以上の構造の有機ＥＬ素子１００は、水分捕獲体３０を備えることで、素子内の水分が除去される。そして、有機ＥＬ素子１００は、水分に起因する、輝度や発光効率等の発光特性の低下を抑制することができる。有機ＥＬ素子１００は、例えば、高信頼の有機ＥＬ照明装置を構成することができる。 The organic EL element 100 having the above structure is provided with the moisture trap 30 to remove moisture in the element. And the organic EL element 100 can suppress the fall of the light emission characteristics, such as a brightness | luminance and light emission efficiency resulting from a water | moisture content. The organic EL element 100 can constitute, for example, a highly reliable organic EL lighting device.
　また、有機ＥＬ素子１００は、有機ＥＬ表示装置を構成することも可能である。有機ＥＬ素子１００は、例えば、基板２２として、マトリクス状に配列された画素毎にスイッチング素子である薄膜トランジスタ（ＴＦＴ）が形成されたＴＦＴ基板を使用し、異なる複数の色を発光する複数の有機ＥＬ層１０を、画素に対応してマトリクス状に設けることにより、アクティブマトリクス型の有機ＥＬ表示装置を構成することができる。 Further, the organic EL element 100 can also constitute an organic EL display device. The organic EL element 100 uses, for example, a TFT substrate in which a thin film transistor (TFT) as a switching element is formed for each pixel arranged in a matrix as the substrate 22, and a plurality of organic ELs that emit a plurality of different colors. By providing the layers 10 in a matrix corresponding to the pixels, an active matrix organic EL display device can be configured.
　以下で、本発明の実施形態の有機ＥＬ素子の別の例について説明する。 Hereinafter, another example of the organic EL element of the embodiment of the present invention will be described.
　図２は、本発明の実施形態の有機ＥＬ素子の第二例を模式的に示す断面図である。 FIG. 2 is a cross-sectional view schematically showing a second example of the organic EL element of the embodiment of the present invention.
　図２に示す、本発明の実施形態の有機ＥＬ素子の第二例である有機ＥＬ素子２００は、構造体２０内に水分捕獲体１３０を形成して有する。水分捕獲体１３０は、上述した本発明の実施形態の水分捕獲体形成組成物を用いて形成されたものである。 2, an organic EL element 200 which is a second example of the organic EL element according to the embodiment of the present invention has a moisture trap 130 formed in the structure 20. The moisture trap 130 is formed using the moisture trap forming composition of the embodiment of the present invention described above.
　有機ＥＬ素子２００は、構造体２０内に形成された水分捕獲体１３０が有機ＥＬ層１０に密着させるように形成されている点で、図１の有機ＥＬ素子１００とは異なる。図２に示す有機ＥＬ素子２００において、有機ＥＬ層１０等、上述した図１の有機ＥＬ素子１００と共通する構成要素については同一の符号を付し、重複する説明は省略する。 The organic EL element 200 is different from the organic EL element 100 of FIG. 1 in that the moisture trap 130 formed in the structure 20 is formed in close contact with the organic EL layer 10. In the organic EL element 200 shown in FIG. 2, the same reference numerals are given to the same components as the organic EL element 100 of FIG.
　有機ＥＬ素子２００において、水分捕獲体１３０は、形成時に水分の除去を行うとともに、形成の後もその吸湿性により有機ＥＬ層１０へ水分が侵入することを防止することができる。そしてさらに、水分捕獲体１３０は有機ＥＬ層１０に密着させるように形成されていることから、有機ＥＬ層１０を保護することもできる。有機ＥＬ素子２００は、例えば、高信頼の有機ＥＬ照明装置を構成することができる。 In the organic EL element 200, the moisture trap 130 removes moisture at the time of formation, and can prevent moisture from entering the organic EL layer 10 due to its hygroscopicity after the formation. Furthermore, since the moisture trap 130 is formed so as to be in close contact with the organic EL layer 10, the organic EL layer 10 can also be protected. The organic EL element 200 can constitute, for example, a highly reliable organic EL lighting device.
　図３は、本発明の実施形態の有機ＥＬ素子の第三例を模式的に示す断面図である。 FIG. 3 is a cross-sectional view schematically showing a third example of the organic EL element of the embodiment of the present invention.
　図３に示す有機ＥＬ素子３００では、図１に示す有機ＥＬ素子１００に対して、有機ＥＬ層１０の全面を覆うガスバリヤフィルム４０が設けられている点で異なり、その他の点で同一である。 3 differs from the organic EL element 100 shown in FIG. 1 in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects.
　ガスバリヤフィルム４０は、水分および酸素が有機ＥＬ層１０と接触することを防止するために設けられている。ガスバリヤフィルム４０としては、特に限定されず従来公知のものを使用することができ、例えば、有機膜と無機膜とが交互に積層されてなるフィルムが挙げられる。 The gas barrier film 40 is provided to prevent moisture and oxygen from coming into contact with the organic EL layer 10. The gas barrier film 40 is not particularly limited and a conventionally known film can be used, and examples thereof include a film in which organic films and inorganic films are alternately laminated.
　また、ガスバリヤフィルム４０としては、米国特許出願公開第２００５／２０２６４６号明細書、米国特許出願公開第２００５／１７６１８１号明細書、米国特許出願公開第２００３／２０３２１０号明細書、米国特許出願公開第２００９／２０８７５４号明細書、国際公開第２００３／０２８９０３号パンフレット、国際公開第２００８／０９４３５２号パンフレット、国際公開第２００９／００９３０６号パンフレット、国際公開第２０１０／０７７５４４号パンフレットなどに記載されたフィルムを挙げることもできる。 Further, as the gas barrier film 40, US Patent Application Publication No. 2005/202646, US Patent Application Publication No. 2005/176181, US Patent Application Publication No. 2003/203210, US Patent Application Publication No. 2009. / 208754 specification, International Publication No. 2003/028903 pamphlet, International Publication No. 2008/094352 pamphlet, International Publication No. 2009/009306 pamphlet, International Publication No. 2010/077754 pamphlet, etc. You can also.
　有機ＥＬ素子３００は、水分捕獲体３０とともにガスバリヤフィルム４０を備えることで、素子内の水分が除去されるとともに、有機ＥＬ層１０に水分が接触することをより低減することができる。有機ＥＬ素子３００は、例えば、高信頼の有機ＥＬ照明装置を構成することができる。 The organic EL element 300 includes the gas barrier film 40 together with the moisture capturing body 30, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10. The organic EL element 300 can constitute, for example, a highly reliable organic EL lighting device.
　図４は、本発明の実施形態の有機ＥＬ素子の第四例を模式的に示す断面図である。 FIG. 4 is a cross-sectional view schematically showing a fourth example of the organic EL element according to the embodiment of the present invention.
　図４に示す有機ＥＬ素子４００では、図２に示す有機ＥＬ素子２００に対して、有機ＥＬ層１０の全面を覆うガスバリヤフィルム４０が設けられている点で異なり、その他の点で同一である。ガスバリヤフィルム４０は、図３に示す有機ＥＬ素子３００が備えるのと同様のものである。 4 differs from the organic EL element 200 shown in FIG. 2 in that a gas barrier film 40 that covers the entire surface of the organic EL layer 10 is provided, and is the same in other respects. The gas barrier film 40 is the same as that provided in the organic EL element 300 shown in FIG.
　有機ＥＬ素子４００は、水分捕獲体１３０とともにガスバリヤフィルム４０を備えることで、素子内の水分が除去されるとともに、有機ＥＬ層１０に水分が接触することをより低減することができる。有機ＥＬ素子４００は、例えば、高信頼の有機ＥＬ照明装置を構成することができる。 The organic EL element 400 includes the gas barrier film 40 together with the moisture trap 130, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10. The organic EL element 400 can constitute, for example, a highly reliable organic EL lighting device.
　図５は、本発明の実施形態の有機ＥＬ素子の第五例を模式的に示す断面図である。 FIG. 5 is a cross-sectional view schematically showing a fifth example of the organic EL element of the embodiment of the present invention.
　図５に示す有機ＥＬ素子５００では、図４に示す有機ＥＬ素子４００に対して、有機ＥＬ層１０上に、本発明の実施形態の水分捕獲体形成組成物から形成された水分捕獲体３０をさらに設けて有しており、水分捕獲体３０の全面および有機ＥＬ層１０の側面を覆うガスバリヤフィルム４０が設けられている点で異なり、その他の点で同一である。 In the organic EL element 500 shown in FIG. 5, the moisture trap 30 formed from the moisture trap formation composition of the embodiment of the present invention is formed on the organic EL layer 10 with respect to the organic EL element 400 shown in FIG. 4. Further, it is different in that it has a gas barrier film 40 that covers the entire surface of the moisture trap 30 and the side surface of the organic EL layer 10, and is the same in other respects.
ガスバリヤフィルム４０は、図３および図４に示す有機ＥＬ素子３００，４００が備えるのと同様のものである。 The gas barrier film 40 is the same as that provided in the organic EL elements 300 and 400 shown in FIGS.
　有機ＥＬ素子５００は、水分捕獲体３０，１３０とともにガスバリヤフィルム４０を備えることで、素子内の水分が除去されるとともに、有機ＥＬ層１０に水分が接触することをより低減することができる。有機ＥＬ素子５００は、例えば、高信頼の有機ＥＬ照明装置を構成することができる。 The organic EL element 500 includes the gas barrier film 40 together with the moisture traps 30 and 130, thereby removing moisture in the element and further reducing contact of moisture with the organic EL layer 10. The organic EL element 500 can constitute, for example, a highly reliable organic EL lighting device.
　以下、実施例に基づき本発明の実施形態を詳述するが、この実施例によって本発明が限定的に解釈されるものではない。 Hereinafter, although embodiments of the present invention will be described in detail based on examples, the present invention is not construed to be limited to these examples.
＜１Ｈ－ＮＭＲの測定＞
　１Ｈ－ＮＭＲは、核磁気共鳴装置（日本電子社の「ＪＮＭ－ＥＣＳ４００」（４００ＭＨｚ））を用いて２５℃で測定した。 <Measurement of 1 H-NMR>
1 H-NMR was measured at 25 ° C. using a nuclear magnetic resonance apparatus (“JNM-ECS400” (400 MHz) manufactured by JEOL Ltd.).
＜水分捕獲剤（Ａ１）の合成＞
　本発明の実施形態の水分捕獲体形成組成物に含有される水分捕獲剤（Ａ１）として、上記式（Ａ１－１）で表される構造部位を有する化合物または上記式（Ａ１－２）で表される化合物の例である（ＡＯ－１）化合物～（ＡＯ－１２）化合物についてその合成方法を説明する。それら合成方法については、特許文献である国際公開（ＷＯ）０１／０２１６１１号パンフレットを参考にすることができる。尚、以下においては、（ＡＯ－１）化合物～（ＡＯ－１２）化合物をそれぞれ、水分捕獲剤（ＡＯ－１）～水分捕獲剤（ＡＯ－１２）という。 <Synthesis of moisture capturing agent (A1)>
As the water-capturing agent (A1) contained in the water-capturing body-forming composition of the embodiment of the present invention, a compound having a structural moiety represented by the above formula (A1-1) or the above formula (A1-2) The synthesis method of compounds (AO-1) to (AO-12), which are examples of the compounds to be synthesized, will be described. Regarding these synthesis methods, it is possible to refer to a patent document, International Publication (WO) 01/021611. Hereinafter, the (AO-1) compound to the (AO-12) compound are referred to as a moisture trapping agent (AO-1) to a moisture trapping agent (AO-12), respectively.
　［合成例１］水分捕獲剤（ＡＯ－１）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル５３．０部、２－ブチル－２－エチル－１，３－プロパンジオール８０．０部、ペンタエリスリトール１７．０部および９０ｗｔ％ギ酸水溶液０．５部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃に１時間保持した。その後、２時間かけて１７５℃まで昇温して４６．５部のメタノールを回収し、無色透明で粘調のポリオルトエステルとして水分捕獲剤（ＡＯ－１）を得た。 [Synthesis Example 1] Synthesis of moisture scavenger (AO-1) In a reaction apparatus equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device, 53.0 parts of methyl orthoformate, 2-butyl-2-ethyl -1,3-propanediol 80.0 parts, pentaerythritol 17.0 parts and 90 wt% formic acid aqueous solution 0.5 parts were charged and maintained at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. . Thereafter, the temperature was raised to 175 ° C. over 2 hours, and 46.5 parts of methanol was recovered to obtain a water scavenger (AO-1) as a colorless, transparent and viscous polyorthoester.
Figure JPOXMLDOC01-appb-C000030
Figure JPOXMLDOC01-appb-C000030
　水分捕獲剤（ＡＯ－１）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．７６～０．９６（２４Ｈ，ｍ），δ１．２０～１．４０（２４Ｈ，ｍ），δ１．１０－１．６０（３２Ｈ，ｍ），δ３．３４～４．１０（２４Ｈ，ｍ），δ５．２４（４Ｈ，ｓ）． The 1 H-NMR spectrum of the moisture scavenger (AO-1) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.76 to 0.96 (24H, m), δ 1.20 to 1.40 (24H, m), δ 1.10 to 1.60 (32H, m), δ 3.. 34-4.10 (24H, m), δ 5.24 (4H, s).
　［合成例２］水分捕獲剤（ＡＯ－２）の合成
　上述の水分捕獲剤（ＡＯ－１）と同様に、オルトギ酸メチル、１，２－ドデカンジオール、ペンタエリスリトールおよび９０％ギ酸水溶液から、下記の水分捕獲剤（ＡＯ－２）を得た。 [Synthesis Example 2] Synthesis of water trapping agent (AO-2) In the same manner as the water trapping agent (AO-1) described above, methyl orthoformate, 1,2-dodecanediol, pentaerythritol and 90% formic acid aqueous solution were used as follows. Water trapping agent (AO-2) was obtained.
Figure JPOXMLDOC01-appb-C000031
Figure JPOXMLDOC01-appb-C000031
　水分捕獲剤（ＡＯ－２）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；　δ０．８８（１２Ｈ，ｓ），δ１．２５～１．３５（６４Ｈ，ｍ），δ１．３５－１．４５（８Ｈ，ｍ），δ３．９０（４Ｈ，ｍ），δ３．９５～４．０５（８Ｈ，ｍ），δ５．８０（８Ｈ，ｓ），δ６．３０（４Ｈ，ｓ）． The 1 H-NMR of the moisture trapping agent (AO-2) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ0.88 (12H, s), δ1.25 to 1.35 (64H, m), δ1.35-1.45 (8H, m), δ3.90 (4H, m), δ 3.95 to 4.05 (8H, m), δ 5.80 (8H, s), δ 6.30 (4H, s).
　［合成例３］水分捕獲剤（ＡＯ－３）の合成
　水分捕獲剤（ＡＯ－１）と同様に、オルトギ酸メチル、バチルアルコール、ペンタエリスリトールおよび９０％ギ酸水溶液から、下記の水分捕獲剤（ＡＯ－３）を得た。 Synthesis Example 3 Synthesis of Water Capture Agent (AO-3) Similar to the water capture agent (AO-1), the following water capture agent (AO) was obtained from methyl orthoformate, batyl alcohol, pentaerythritol and 90% formic acid aqueous solution. -3) was obtained.
Figure JPOXMLDOC01-appb-C000032
Figure JPOXMLDOC01-appb-C000032
　水分捕獲剤（ＡＯ－３）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；　δ０．８８（１２Ｈ，ｓ），δ１．２５～１．３０（１０４Ｈ，ｍ），δ１．３０－１．４５（２４Ｈ，ｍ），δ３．４０（１２Ｈ，ｍ），δ３．６０～３．８０（８Ｈ，ｍ），δ３．９５～４．００（８Ｈ，ｍ），δ４．２０～４．３０（４Ｈ，ｍ），δ５．８０（８Ｈ，ｓ），δ６．２５（４Ｈ，ｓ）． The 1 H-NMR spectrum of the moisture scavenger (AO-3) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ0.88 (12H, s), δ1.25 to 1.30 (104H, m), δ1.30-1.45 (24H, m), δ3.40 (12H, m), δ 3.60 to 3.80 (8H, m), δ 3.95 to 4.00 (8H, m), δ 4.20 to 4.30 (4H, m), δ 5.80 (8H, s) , Δ6.25 (4H, s).
　［合成例４］水分捕獲剤（ＡＯ－４）の合成
　水分捕獲剤（ＡＯ－１）と同様に、オルトギ酸メチル、２－ブチル－２－エチル－１，３－プロパンジオール、トリメチロールプロパンおよび９０％ギ酸水溶液から、下記の水分捕獲剤（ＡＯ－４）を得た。 Synthesis Example 4 Synthesis of Water Capture Agent (AO-4) Similar to the water capture agent (AO-1), methyl orthoformate, 2-butyl-2-ethyl-1,3-propanediol, trimethylolpropane and The following water scavenger (AO-4) was obtained from a 90% aqueous formic acid solution.
Figure JPOXMLDOC01-appb-C000033
Figure JPOXMLDOC01-appb-C000033
　水分捕獲剤（ＡＯ－４）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．９０（６Ｈ，ｔ），δ１．２０～１．４０（６Ｈ，ｍ），δ１．５５（２Ｈ，ｑ），δ１．６０～１．７５（８Ｈ，ｍ），δ３．８０（４Ｈ，ｄ），δ３．８５（８Ｈ，ｑ），δ５．８０（２Ｈ，ｓ），δ６．０５（３Ｈ，ｓ）． The 1 H-NMR of the moisture trapping agent (AO-4) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.90 (6H, t), δ 1.20 to 1.40 (6H, m), δ 1.55 (2H, q), δ 1.60 to 1.75 (8H, m), δ 3.80 (4H, d), δ 3.85 (8H, q), δ 5.80 (2H, s), δ 6.05 (3H, s).
　［合成例５］水分捕獲剤（ＡＯ－５）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル５３．０部、２－ブチル－２－エチル－１，３－プロパンジオール８０．０部、メタクリル酸ヒドロキシエステル６５．０部および９０％ギ酸水溶液０．５部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃ に１時間保持した。その後、２時間かけて１７５℃まで昇温してメタノールを除去し、粘調なメタクリル基を有する水分捕獲剤（ＡＯ－５）を得た。 [Synthesis Example 5] Synthesis of moisture scavenger (AO-5) In a reaction apparatus equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device, 53.0 parts of methyl orthoformate, 2-butyl-2-ethyl -1,3-propanediol 80.0 parts, methacrylic acid hydroxy ester 65.0 parts and 90% formic acid aqueous solution 0.5 part were charged, and the methanol produced by the alcohol exchange reaction was distilled off at about 85 ° C. for 1 hour. Retained. Thereafter, the temperature was raised to 175 ° C. over 2 hours to remove methanol, and a water scavenger (AO-5) having a viscous methacryl group was obtained.
Figure JPOXMLDOC01-appb-C000034
Figure JPOXMLDOC01-appb-C000034
　水分捕獲剤（ＡＯ－５）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．９０（２Ｈ，ｔ），δ１．２０～１．４０（６Ｈ，ｍ），δ１．７０（２Ｈ，ｑ），δ２．０５（３Ｈ，ｓ），δ３．６５（２Ｈ，ｑ），δ３．８５（４Ｈ，ｄ），δ４．２５（２Ｈ，ｄ），δ６．０５（１Ｈ，ｓ），δ６．４０（１Ｈ，ｓ），δ６．５０（１Ｈ，ｓ）． The 1 H-NMR spectrum of the moisture scavenger (AO-5) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.90 (2H, t), δ 1.20 to 1.40 (6H, m), δ 1.70 (2H, q), δ 2.05 (3H, s), δ3 .65 (2H, q), δ 3.85 (4H, d), δ 4.25 (2H, d), δ 6.05 (1H, s), δ 6.40 (1H, s), δ 6.50 (1H, s).
　次いで、冷却管および攪拌機を備えたフラスコに、２，２’－アゾビス（２，４－ジメチルバレロニトリル）７質量部、プロピレングリコールモノメチルエーテルアセテート２００質量部を仕込んだ。引き続きメタクリル基を有する水分捕獲剤（ＡＯ－５）７０質量部、スチレン３０質量部を仕込み窒素置換した後、ゆるやかに撹拌を始めた。溶液の温度を７０℃に上昇させ、この温度を５時間保持して重合体を形成し、重合体である水分捕獲剤（ＡＯ－５－１）を含む溶液を得た。重合体である水分捕獲剤（ＡＯ－５－１）のポリスチレン換算重量平均分子量（Ｍｗ）は８０００であった。得られた溶液の固形分濃度は３４．１質量％であった。 Subsequently, 7 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of propylene glycol monomethyl ether acetate were charged into a flask equipped with a condenser and a stirrer. Subsequently, 70 parts by mass of a water scavenger having a methacrylic group (AO-5) and 30 parts by mass of styrene were charged and purged with nitrogen, and then gently stirring was started. The temperature of the solution was raised to 70 ° C., and this temperature was maintained for 5 hours to form a polymer. Thus, a solution containing a moisture trapping agent (AO-5-1) as a polymer was obtained. The polystyrene equivalent weight average molecular weight (Mw) of the water trapping agent (AO-5-1) as a polymer was 8,000. The solid content concentration of the obtained solution was 34.1% by mass.
Figure JPOXMLDOC01-appb-C000035
Figure JPOXMLDOC01-appb-C000035
　水分捕獲剤（ＡＯ－５－１）の１Ｈ－ＮＭＲを測定したところ、水分捕獲剤（ＡＯ－５）の２重結合によるδ６．４０付近のピークが消失したことを確認した。 When 1 H-NMR of the moisture trapping agent (AO-5-1) was measured, it was confirmed that the peak around δ 6.40 due to the double bond of the moisture trapping agent (AO-5) disappeared.
　［合成例６］水分捕獲剤（ＡＯ－６）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル５３．０部、２－ブチル－２－エチル－１，３－プロパンジオール８０．０部、ノボラック樹脂（群栄化学株式会社製　ＨＡＩＨＹＡＫＵ）１００．０部および９０％ギ酸水溶液０．５部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃に２時間保持した。その後、２時間かけて１７５℃まで昇温してメタノールを除去し、粘調なオルトエステルを有するノボラック樹脂として水分捕獲剤（ＡＯ－６）を得た。 [Synthesis Example 6] Synthesis of moisture scavenger (AO-6) In a reactor equipped with a stirrer, a cooler, a temperature controller and a solvent recovery device, 53.0 parts of methyl orthoformate, 2-butyl-2-ethyl -1,3-propanediol 80.0 parts, novolak resin (HAIHYAKU made by Gunei Chemical Co., Ltd.) 100.0 parts and 90% formic acid aqueous solution 0.5 parts were charged, and methanol produced by the alcohol exchange reaction was distilled off. However, it was kept at about 85 ° C. for 2 hours. Thereafter, the temperature was raised to 175 ° C. over 2 hours to remove methanol, and a water scavenger (AO-6) was obtained as a novolak resin having a viscous orthoester.
Figure JPOXMLDOC01-appb-C000036
Figure JPOXMLDOC01-appb-C000036
　水分捕獲剤（ＡＯ－６）の１Ｈ－ＮＭＲを測定したところ、原料であるノボラック樹脂の水酸基のδ５．３０付近のピークが消失したことを確認した。 When 1 H-NMR of the moisture trapping agent (AO-6) was measured, it was confirmed that the peak near δ 5.30 of the hydroxyl group of the novolak resin as a raw material disappeared.
　［合成例７］水分捕獲剤（ＡＯ－７）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル５３．０部、トリメチロールプロパンモノアリルエーテル８０．０部、ペンタエリスリトール１７．０部および９０ｗｔ％ギ酸水溶液０．５部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃に１時間保持した。その後、２時間かけて１７５℃まで昇温して４６．５部のメタノールを回収し、無色透明で粘調のポリオルトエステルとして水分捕獲剤（ＡＯ－７）を得た。 [Synthesis Example 7] Synthesis of moisture scavenger (AO-7) In a reactor equipped with a stirrer, a cooler, a temperature controller and a solvent recovery device, 53.0 parts of methyl orthoformate, trimethylolpropane monoallyl ether 80 0.0 parts, 17.0 parts of pentaerythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off the methanol produced by the alcohol exchange reaction. Thereafter, the temperature was raised to 175 ° C. over 2 hours, and 46.5 parts of methanol was recovered to obtain a water scavenger (AO-7) as a colorless, transparent, viscous polyorthoester.
Figure JPOXMLDOC01-appb-C000037
Figure JPOXMLDOC01-appb-C000037
　水分捕獲剤（ＡＯ－７）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．８３（１２Ｈ，ｍ），δ１．２４～１．５６（８Ｈ，ｍ），δ３．２０～４．１０（４０Ｈ，ｄ），δ５．１０～５．３６（１２Ｈ，ｍ），δ５．８８（４Ｈ，ｍ）． The 1 H-NMR spectrum of the moisture scavenger (AO-7) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.83 (12H, m), δ 1.24 to 1.56 (8 H, m), δ 3.20 to 4.10 (40 H, d), δ 5.10 to 5. 36 (12H, m), δ 5.88 (4H, m).
　［合成例８］水分捕獲剤（ＡＯ－８）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、水分捕獲剤（ＡＯ－１）５０．０部、ｔ－ブトキシカリウム３．０部を仕込み、窒素雰囲気下１６０℃で６時間撹拌した。その後、アルカリ吸着材としてキョーワード（登録商標）６００Ｓ（協和化学工業製）を０．６部加え１２０℃で１時間処理後、反応液を室温まで冷却し、吸着材をろ別して、無色透明で粘調のポリオルトエステルとして水分捕獲剤（ＡＯ－８）を得た。 [Synthesis Example 8] Synthesis of Moisture Capture Agent (AO-8) In a reactor equipped with a stirrer, a cooler, a temperature control device, and a solvent recovery device, 50.0 parts of moisture capture agent (AO-1), t- 3.0 parts of butoxypotassium was charged and stirred at 160 ° C. for 6 hours under a nitrogen atmosphere. After that, 0.6 parts of KYOWARD (registered trademark) 600S (manufactured by Kyowa Chemical Industry Co., Ltd.) was added as an alkali adsorbent, treated at 120 ° C. for 1 hour, the reaction liquid was cooled to room temperature, the adsorbent was filtered off, A water scavenger (AO-8) was obtained as a viscous polyorthoester.
Figure JPOXMLDOC01-appb-C000038
Figure JPOXMLDOC01-appb-C000038
　水分捕獲剤（ＡＯ－８）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．８７（１２Ｈ，ｍ），δ１．４０（８Ｈ，ｍ），δ１．５５（１２Ｈ，ｄ），δ３．２０～４．２０（２４Ｈ，ｄ），δ３．２５～４．１０（３２Ｈ，ｍ），δ４．２５～４．４５（４Ｈ，ｍ），δ５．１０～５．４０（４Ｈ，ｍ），δ５．８０～６．１５（４Ｈ，ｍ）． The 1 H-NMR spectrum of the moisture scavenger (AO-8) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ0.87 (12H, m), δ1.40 (8H, m), δ1.55 (12H, d), δ3.20 to 4.20 (24H, d), δ3 .25 to 4.10 (32H, m), δ 4.25 to 4.45 (4H, m), δ 5.10 to 5.40 (4H, m), δ 5.80 to 6.15 (4H, m) .
　［合成例９］水分捕獲剤（ＡＯ－９）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル６３．０部、グリセリン５５．０部、ペンタエリスリトール２０．０部および９０ｗｔ％ギ酸水溶液０．５部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃に１時間保持した。その後、２時間かけて１７５℃まで昇温して５７．０部のメタノールを回収し、さらに１７５℃、３００Ｐａの条件で濃縮し、揮発成分を除去した。無色透明粘調のポリオルトエステルとして水分捕獲剤（ＡＯ－９）を得た。 [Synthesis Example 9] Synthesis of moisture scavenger (AO-9) In a reactor equipped with a stirrer, a cooler, a temperature controller and a solvent recovery device, 63.0 parts of methyl orthoformate, 55.0 parts of glycerin, penta 20.0 parts of erythritol and 0.5 parts of a 90 wt% formic acid aqueous solution were charged, and the mixture was kept at about 85 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. Then, it heated up to 175 degreeC over 2 hours, 57.0 parts methanol was collect | recovered, and also it concentrated on 175 degreeC and 300 Pa conditions, and removed the volatile component. A water scavenger (AO-9) was obtained as a polyorthoester having a colorless and transparent viscosity.
Figure JPOXMLDOC01-appb-C000039
Figure JPOXMLDOC01-appb-C000039
　水分捕獲剤（ＡＯ－９）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ３．２０～４．２０（２４Ｈ，ｍ），δ４．２０～４．７０（４Ｈ，ｍ），δ５．６０～６．１０（４Ｈ，ｍ）． The 1 H-NMR spectrum of the moisture scavenger (AO-9) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 3.20 to 4.20 (24H, m), δ 4.20 to 4.70 (4H, m), δ 5.60 to 6.10 (4H, m).
　［合成例１０］水分捕獲剤（ＡＯ－１０）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル４２．５部、グリセリン５５．３部および９０ｗｔ％ギ酸水溶液０．４部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約８５℃に２時間保持した。その後、４時間かけて１５０℃まで昇温し、３００Ｐａの条件で濃縮し、揮発成分を除去した。無色透明粘調のポリオルトエステルとして水分捕獲剤（ＡＯ－１０）を得た。 [Synthesis Example 10] Synthesis of moisture scavenger (AO-10) In a reactor equipped with a stirrer, a cooler, a temperature controller and a solvent recovery device, 42.5 parts of methyl orthoformate, 55.3 parts of glycerin and 90 wt. A 0.4% aqueous formic acid solution was charged, and the mixture was kept at about 85 ° C. for 2 hours while distilling off methanol produced by the alcohol exchange reaction. Then, it heated up to 150 degreeC over 4 hours, concentrated on 300 Pa conditions, and removed the volatile component. A water scavenger (AO-10) was obtained as a polyorthoester having a colorless and transparent viscosity.
Figure JPOXMLDOC01-appb-C000040
Figure JPOXMLDOC01-appb-C000040
　水分捕獲剤（ＡＯ－１０）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ３．４６～４．５４（１８Ｈ，ｍ），δ５．８２～６．０６（２Ｈ，ｍ）． The 1 H-NMR spectrum of the moisture scavenger (AO-10) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 3.46 to 4.54 (18H, m), δ 5.82 to 6.06 (2H, m).
　［合成例１１］水分捕獲剤（ＡＯ－１１）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル１２．７部、ＯＸＴ－１０１, ５０．２部および９０ｗｔ％ギ酸水溶液０．６部を仕込み、アルコール交換反応により生成するメタノールを留去しながら約９５℃に１６時間保持した。その後、１４０℃まで昇温し、３００Ｐａの条件で濃縮し、揮発成分を除去した。白色固体のポリオルトエステルとして水分捕獲剤（ＡＯ－１１）を得た。 [Synthesis Example 11] Synthesis of moisture scavenger (AO-11) In a reaction apparatus equipped with a stirrer, a cooler, a temperature control device and a solvent recovery device, 12.7 parts of methyl orthoformate, OXT-101, 50.2 And 0.6 part of a 90 wt% formic acid aqueous solution were added, and the mixture was kept at about 95 ° C. for 16 hours while distilling off methanol produced by the alcohol exchange reaction. Then, it heated up to 140 degreeC and concentrated on 300 Pa conditions, and removed the volatile component. A moisture scavenger (AO-11) was obtained as a white solid polyorthoester.
Figure JPOXMLDOC01-appb-C000041
Figure JPOXMLDOC01-appb-C000041
　水分捕獲剤（ＡＯ－１１）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．９１（９Ｈ，ｔ），δ１．７７（６Ｈ，ｑ），δ３．７７（６Ｈ，ｓ），δ４．２８（６Ｈ，ｄ），δ４．４１（６Ｈ，ｄ），δ５．４２（１Ｈ，ｓ）． The 1 H-NMR of the moisture trapping agent (AO-11) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.91 (9H, t), δ 1.77 (6H, q), δ 3.77 (6H, s), δ 4.28 (6H, d), δ 4.41 (6H) , D), δ 5.42 (1H, s).
　［合成例１２］水分捕獲剤（ＡＯ－１２）の合成
　撹拌機、冷却器、温度制御装置および溶剤回収装置を備えた反応装置に、オルトギ酸メチル２１．２部、グリセリン１８．４部、および９０ｗｔ％ギ酸水溶液１部を仕込み、アルコール交換反応により生成するメタノールを留去しながら８５℃で１．５時間、９０℃で１時間反応した。その後、ＯＸＴ－１０１, ２５．６部を加え、約１４０℃まで６時間かけて昇温しながら生成するメタノールを留去後、１４０℃、３００Ｐａの条件で濃縮し、揮発成分を除去した。無色透明油状物のポリオルトエステルとして水分捕獲剤（ＡＯ－１２）を得た。 [Synthesis Example 12] Synthesis of moisture scavenger (AO-12) In a reactor equipped with a stirrer, a cooler, a temperature controller and a solvent recovery device, 21.2 parts of methyl orthoformate, 18.4 parts of glycerin, and 1 part of a 90 wt% formic acid aqueous solution was charged, and the reaction was carried out at 85 ° C. for 1.5 hours and at 90 ° C. for 1 hour while distilling off methanol produced by the alcohol exchange reaction. Thereafter, 25.6 parts of OXT-101 was added, and methanol formed while distilling the temperature up to about 140 ° C. over 6 hours was distilled off, followed by concentration under conditions of 140 ° C. and 300 Pa to remove volatile components. A water scavenger (AO-12) was obtained as a polyorthoester as a colorless transparent oil.
Figure JPOXMLDOC01-appb-C000042
Figure JPOXMLDOC01-appb-C000042
　水分捕獲剤（ＡＯ－１２）の１Ｈ－ＮＭＲを測定したところ、以下の通りであった。
　１Ｈ－ＮＭＲ　（ＣＤＣｌ３）；δ０．８８（３Ｈ，ｔ），δ１．７２（２Ｈ，ｑ），δ３．４４～４．４２（１２Ｈ，ｍ），δ５．８７（１Ｈ，ｓ） The 1 H-NMR spectrum of the moisture scavenger (AO-12) was measured and found to be as follows.
1 H-NMR (CDCl 3 ); δ 0.88 (3H, t), δ 1.72 (2H, q), δ 3.44 to 4.42 (12H, m), δ 5.87 (1H, s)
＜水分捕獲剤（Ａ３）の合成＞
　本発明の実施形態の水分捕獲体形成組成物に含有される水分捕獲剤（Ａ３）の例である（Ａ３－ｉ）化合物、（Ａ３－ｉｉ）化合物、（Ａ３－ｉｉ－２）化合物、（Ａ３－ｉｉｉ）化合物および（Ａ３－ｉｖ）化合物それぞれの合成について説明する。尚、以下においては、それら化合物をそれぞれ、水分捕獲剤（Ａ３－ｉ）、水分捕獲剤（Ａ３－ｉｉ）、水分捕獲剤（Ａ３－ｉｉ－２）、水分捕獲剤（Ａ３－ｉｉｉ）および水分捕獲剤（Ａ３－ｉｖ）という。 <Synthesis of moisture capture agent (A3)>
(A3-i) compound, (A3-ii) compound, (A3-ii-2) compound, which is an example of the water trapping agent (A3) contained in the water trap forming composition of the embodiment of the present invention, ( The synthesis of each of the A3-iii) compound and the (A3-iv) compound will be described. In the following, these compounds are respectively referred to as a moisture trapping agent (A3-i), a moisture trapping agent (A3-ii), a moisture trapping agent (A3-ii-2), a moisture trapping agent (A3-iii), and moisture. It is called capture agent (A3-iv).
［合成例１３］水分捕獲剤（Ａ３－ｉ）の合成
　乾燥窒素雰囲気下、冷却管および撹拌機を備えた２００ｍＬの三口フラスコにテトラエトキシシラン４．１６ｇ（０．０２０モル）、および３－エチル－３－オキセタンメタノール９．６２８ｇ（０．０８３モル）、触媒量の水酸化カリウム水溶液、溶媒としてのテトラヒドロフラン５０ｇを仕込み、攪拌した。６０℃で３時間撹拌した。この温度を保ちながら、少しずつ減圧して生成したエタノールおよびテトラヒドロフランを留去し、水分捕獲剤（Ａ３－ｉ）を得た。 Synthesis Example 13 Synthesis of Moisture Capture Agent (A3-i) Under a dry nitrogen atmosphere, tetraethoxysilane (4.16 g, 0.020 mol) and 3-ethyl were added to a 200 mL three-necked flask equipped with a condenser and a stirrer. -3-Oxetanemethanol 9.628 g (0.083 mol), a catalytic amount of an aqueous potassium hydroxide solution, and 50 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the pressure was gradually reduced to distill off the ethanol and tetrahydrofuran produced to obtain a water scavenger (A3-i).
　水分捕獲剤（Ａ３－ｉ）の生成は、１Ｈ－ＮＭＲ（４００ＭＨｚ、ａｃｅｔｏｎｅ－ｄ６）にて原料の３－エチル－３－オキセタンメタノールのピークとは異なる、３－エチル－３－オキセタンメチルオキシ基に由来するδ４．５－δ３．５のピークを観測することにて行った。 The production of the moisture scavenger (A3-i) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of δ4.5-δ3.5 derived from the group.
Figure JPOXMLDOC01-appb-C000043
Figure JPOXMLDOC01-appb-C000043
［合成例１４］水分捕獲剤（Ａ３－ｉｉ）の合成
　乾燥窒素雰囲気下、冷却管および撹拌機を備えた２００ｍＬの三口フラスコにテトラエトキシシラン４．１６ｇ（０．０２０モル）、およびメタクリル酸２－ヒドロキシエチル１０．８０ｇ（０．０８３モル）、触媒量の水酸化カリウム水溶液、溶媒としてのテトラヒドロフラン５０ｇを仕込み、攪拌した。６０℃で３時間撹拌した。この温度を保ちながら、少しずつ減圧して生成したエタノールおよびテトラヒドロフランを留去し、水分捕獲剤（Ａ３－ｉｉ）を得た。 Synthesis Example 14 Synthesis of Moisture Capture Agent (A3-ii) Under a dry nitrogen atmosphere, tetraethoxysilane (4.16 g, 0.020 mol) and methacrylic acid 2 were added to a 200 mL three-necked flask equipped with a condenser and a stirrer. -10.80 g (0.083 mol) of hydroxyethyl, a catalytic amount of an aqueous potassium hydroxide solution, and 50 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the pressure was gradually reduced to distill off the ethanol and tetrahydrofuran produced to obtain a water scavenger (A3-ii).
　水分捕獲剤（Ａ３－ｉｉ）の生成は、１Ｈ－ＮＭＲ（４００ＭＨｚ、ａｃｅｔｏｎｅ－ｄ６）にて原料の３－エチル－３－オキセタンメタノールのピークとは異なる、３－エチル－３－オキセタンメチルオキシ基に由来するδ４．５－δ３．５のピークを観測することにて行った。 The production of the moisture scavenger (A3-ii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of δ4.5-δ3.5 derived from the group.
Figure JPOXMLDOC01-appb-C000044
Figure JPOXMLDOC01-appb-C000044
［合成例１５］水分捕獲剤（Ａ３－ｉｉ－２）の合成
　乾燥窒素雰囲気下、冷却管および撹拌機を備えた２００ｍＬの三口フラスコにテトラエトキシシラン４．１６ｇ（０．０２０モル）、およびブレンマーＰＰ－５００（ｎ＝９、日油製）５５ｇ（０．０８３モル）、触媒量の水酸化カリウム水溶液、溶媒としてのテトラヒドロフラン１００ｇを仕込み、攪拌した。６０℃で３時間撹拌した。この温度を保ちながら、少しずつ減圧して生成したエタノールおよびテトラヒドロフランを留去し、水分捕獲剤（Ａ３－ｉｉ―２）を得た。 [Synthesis Example 15] Synthesis of Moisture Capture Agent (A3-ii-2) Under a dry nitrogen atmosphere, tetraethoxysilane (4.16 g, 0.020 mol) and blemmer were added to a 200 mL three-necked flask equipped with a condenser and a stirrer. PP-500 (n = 9, manufactured by NOF Corporation) 55 g (0.083 mol), a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were charged and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the pressure was gradually reduced to distill off the ethanol and tetrahydrofuran produced to obtain a water scavenger (A3-ii-2).
　水分捕獲剤（Ａ３－ｉｉ―２）の生成は、１Ｈ－ＮＭＲ（４００ＭＨｚ、ａｃｅｔｏｎｅ－ｄ６）にて原料の３－エチル－３－オキセタンメタノールのピークとは異なる、３－エチル－３－オキセタンメチルオキシ基に由来するδ４．５－δ３．５のピークを観測することにて行った。 The generation of the moisture scavenger (A3-ii-2) is different from the peak of the starting material 3-ethyl-3-oxetane methanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing the peak of δ4.5-δ3.5 derived from the methyloxy group.
Figure JPOXMLDOC01-appb-C000045
Figure JPOXMLDOC01-appb-C000045
［合成例１６］水分捕獲剤（Ａ３－ｉｉｉ）の合成
　乾燥窒素雰囲気下、冷却管および撹拌機を備えた２００ｍＬの三口フラスコに３－メタクリロイルオキシプロピルメチルジメトキシシラン４．６４ｇ（０．０２０モル）、および、３－エチル－３－オキセタンメタノール９．６２８ｇ（０．０８３モル）、触媒量の水酸化カリウム水溶液、溶媒としてのテトラヒドロフラン１００ｇを仕込み、攪拌した。６０℃で３時間撹拌した。この温度を保ちながら、少しずつ減圧して生成したメタノールおよびテトラヒドロフランを留去し、水分捕獲剤（Ａ３－ｉｉｉ）を得た。 [Synthesis Example 16] Synthesis of moisture scavenger (A3-iii) 4.64 g (0.020 mol) of 3-methacryloyloxypropylmethyldimethoxysilane in a 200 mL three-necked flask equipped with a condenser and a stirrer in a dry nitrogen atmosphere In addition, 9.628 g (0.083 mol) of 3-ethyl-3-oxetanemethanol, a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were added and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the methanol and tetrahydrofuran produced by depressurizing gradually were distilled off to obtain a water scavenger (A3-iii).
　水分捕獲剤（Ａ３－ｉｉｉ）の生成は、１Ｈ－ＮＭＲ（４００ＭＨｚ、ａｃｅｔｏｎｅ－ｄ６）にて原料の３－エチル－３－オキセタンメタノールのピークとは異なる、３－エチル－３－オキセタンメチルオキシ基に由来するδ４．５－δ３．５のピークを観測することにて行った。 The generation of the moisture scavenger (A3-iii) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6), which is 3-ethyl-3-oxetanemethyloxy. This was done by observing the peak of δ4.5-δ3.5 derived from the group.
Figure JPOXMLDOC01-appb-C000046
Figure JPOXMLDOC01-appb-C000046
［合成例１７］水分捕獲剤（Ａ３－ｉｖ）の合成
　乾燥窒素雰囲気下、冷却管および撹拌機を備えた２００ｍＬの三口フラスコに３－アクリロイルオキシプロピルジメチルメトキシシラン４．０４ｇ（０．０２０モル）、および、３－エチル－３－オキセタンメタノール９．６２８ｇ（０．０８３モル）、触媒量の水酸化カリウム水溶液、溶媒としてのテトラヒドロフラン１００ｇを仕込み、攪拌した。６０℃で３時間撹拌した。この温度を保ちながら、少しずつ減圧して生成したメタノールおよびテトラヒドロフランを留去し、水分捕獲剤（Ａ３－ｉｖ）を得た。 Synthesis Example 17 Synthesis of Moisture Capture Agent (A3-iv) 4.04 g (0.020 mol) of 3-acryloyloxypropyldimethylmethoxysilane in a 200 mL three-necked flask equipped with a condenser and a stirrer in a dry nitrogen atmosphere In addition, 9.628 g (0.083 mol) of 3-ethyl-3-oxetanemethanol, a catalytic amount of an aqueous potassium hydroxide solution, and 100 g of tetrahydrofuran as a solvent were added and stirred. Stir at 60 ° C. for 3 hours. While maintaining this temperature, the pressure was gradually reduced and methanol and tetrahydrofuran produced were distilled off to obtain a water scavenger (A3-iv).
　水分捕獲剤（Ａ３－ｉｖ）の生成は、１Ｈ－ＮＭＲ（４００ＭＨｚ、ａｃｅｔｏｎｅ－ｄ６）にて原料の３－エチル－３－オキセタンメタノールのピークとは異なる、３－エチル－３－オキセタンメチルオキシ基に由来するδ４．５－３．５のピークを観測することにて行った。 The production of the moisture scavenger (A3-iv) is different from the peak of the starting material 3-ethyl-3-oxetanemethanol in 1 H-NMR (400 MHz, acetone-d6). This was done by observing a peak at δ4.5-3.5 derived from the group.
Figure JPOXMLDOC01-appb-C000047
Figure JPOXMLDOC01-appb-C000047
＜水分捕獲体形成組成物の調製＞
　本実施例の各水分捕獲体形成組成物の調製に用いた成分（Ａ）（水分捕獲剤（Ａ１）、水分捕獲剤（Ａ２）、水分捕獲剤（Ａ３）および従来の水分捕獲剤）、成分（Ｂ）（酸・塩基発生剤（Ｂ））、成分（Ｃ）（硬化性化合物（Ｃ））、成分（Ｄ）（ラジカル重合開始剤（Ｄ））および成分（Ｅ）（微粒子（Ｅ））を以下に示す。尚、成分（Ａ）の水分捕獲剤（Ａ２）のＡＳ－１～ＡＳ－６については、それぞれの融点（℃）も併せて示す。 <Preparation of moisture trap forming composition>
Component (A) (moisture trapping agent (A1), moisture trapping agent (A2), moisture trapping agent (A3), and conventional moisture trapping agent) and components used for the preparation of each moisture trap forming composition of this example (B) (acid / base generator (B)), component (C) (curable compound (C)), component (D) (radical polymerization initiator (D)) and component (E) (fine particles (E) ) Is shown below. As for AS-1 to AS-6 of the moisture trapping agent (A2) of the component (A), the melting points (° C.) are also shown.
　［成分（Ａ）］
　（水分捕獲剤（Ａ１））
　ＡＯ－１：水分捕獲剤（ＡＯ－１）
　ＡＯ－２：水分捕獲剤（ＡＯ－２）
　ＡＯ－３：水分捕獲剤（ＡＯ－３）
　ＡＯ－４：水分捕獲剤（ＡＯ－４）
　ＡＯ－５－１：水分捕獲剤（ＡＯ－５－１）
　ＡＯ－６：水分捕獲剤（ＡＯ－６）
　ＡＯ－７：水分捕獲剤（ＡＯ－７）
　ＡＯ－８：水分捕獲剤（ＡＯ－８）
　ＡＯ－９：水分捕獲剤（ＡＯ－９）
　ＡＯ－１０：水分捕獲剤（ＡＯ－１０）
　ＡＯ－１１：水分捕獲剤（ＡＯ－１１）
　ＡＯ－１２：水分捕獲剤（ＡＯ－１２） [Component (A)]
(Moisture capture agent (A1))
AO-1: Moisture trap (AO-1)
AO-2: Moisture trap (AO-2)
AO-3: Moisture trap (AO-3)
AO-4: Moisture trap (AO-4)
AO-5-1: Moisture trap (AO-5-1)
AO-6: Moisture trap (AO-6)
AO-7: Moisture trap (AO-7)
AO-8: Moisture trap (AO-8)
AO-9: Moisture trap (AO-9)
AO-10: Moisture trap (AO-10)
AO-11: Moisture trap (AO-11)
AO-12: Moisture trap (AO-12)
　（水分捕獲剤（Ａ２））
　ＡＳ－１：４－メチルヘキサヒドロフタル酸無水物（新日本理化（株）製）／－１５℃
　ＡＳ－２：４，４’－（ヘキサフルオロイソプロピリデン）ジフタル酸無水物（和光純薬工業（株）製）／２４４℃
　ＡＳ－３：グリセリンビス　アンヒドロトリメリテート　モノアセテート（新日本理化（株）製）／６５℃－８５℃
　ＡＳ－４：５－（２，５－ジオキソテトラヒドロフリル）－３－メチル－３－シクロヘキセン－１，２－ジカルボン酸無水物（東京化成工業（株）製）／１７２℃
　ＡＳ－５：３，３’，４，４’－ジフェニルスルホンテトラカルボン酸２無水物（新日本理化（株）製）／２８７℃
　ＡＳ－６：テトラプロぺニル無水コハク酸（新日本理化（株）製）／－５℃ (Moisture capture agent (A2))
AS-1: 4-Methylhexahydrophthalic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) /-15 ° C
AS-2: 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) / 244 ° C.
AS-3: Glycerin bis anhydro trimellitate monoacetate (manufactured by Shin Nippon Rika Co., Ltd.) / 65 ° C-85 ° C
AS-4: 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) / 172 ° C.
AS-5: 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.) / 287 ° C.
AS-6: Tetrapropenyl succinic anhydride (manufactured by Shin Nippon Rika Co., Ltd.) /-5 ° C
　（水分捕獲剤（Ａ３））
　Ａ－１：水分捕獲剤（Ａ３－ｉ）
　Ａ－２：水分捕獲剤（Ａ３－ｉｉ）
　Ａ－３：水分捕獲剤（Ａ３－ｉｉ－２）
　Ａ－４：水分捕獲剤（Ａ３－ｉｉｉ）
　Ａ－５：水分捕獲剤（Ａ３－ｉｖ） (Moisture capture agent (A3))
A-1: Moisture trap (A3-i)
A-2: Moisture trap (A3-ii)
A-3: Moisture trap (A3-ii-2)
A-4: Moisture trap (A3-iii)
A-5: Moisture trap (A3-iv)
　（従来の水分捕獲剤）
　ＡＸ－１：アルミニウムトリイソプロポキシド（Ａｌ（ｉ－ＰｒＯ）３）（東京化成工業（株）製）
　ＡＸ－２：酸化カルシウム（東京化成工業（株）製） (Conventional moisture trap)
AX-1: Aluminum triisopropoxide (Al (i-PrO) 3 ) (manufactured by Tokyo Chemical Industry Co., Ltd.)
AX-2: Calcium oxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
　［成分（Ｂ）］
　Ｂ－１：ＣＰＩ－２００Ｋ（サンアプロ製）
　Ｂ－２：サンエイド（登録商標）ＳＩ－８０Ｌ（三新化学工業製）
　Ｂ－３：２－ニトロフェニルメチル－４－メタクリロイルオキシピぺリジン－１－カルボキシラート [Component (B)]
B-1: CPI-200K (San Apro)
B-2: Sun-Aid (registered trademark) SI-80L (manufactured by Sanshin Chemical Industry)
B-3: 2-Nitrophenylmethyl-4-methacryloyloxypiperidine-1-carboxylate
　［成分（Ｃ）］
　Ｃ－１：エピコート（登録商標）８２８（三菱化学製）
　Ｃ－２：デナコール（登録商標）ＥＸ－２１２（ナガセ製）
　Ｃ－３：ＮＫエステル９ＰＧ（新中村化学製） [Component (C)]
C-1: Epicoat (registered trademark) 828 (manufactured by Mitsubishi Chemical)
C-2: Denacol (registered trademark) EX-212 (manufactured by Nagase)
C-3: NK ester 9PG (manufactured by Shin-Nakamura Chemical)
　［成分（Ｄ）］
　Ｄ－１：ルシリン（登録商標）ＴＰＯ（ＢＡＳＦ社製）
　Ｄ－２：Ｖ－６０１（和光純薬社製） [Component (D)]
D-1: Lucillin (registered trademark) TPO (manufactured by BASF)
D-2: V-601 (manufactured by Wako Pure Chemical Industries, Ltd.)
［成分（Ｅ）］
　Ｅ－１：日産化学社製ナノユース（登録商標）ＯＺ－Ｓ３０Ｋ－ＡＣ（酸化ジルコニウムの一次粒径２０ｎｍ、動的光散乱による平均粒径８０ｎｍ、固形分濃度２０質量％）
　Ｅ－２：シーアイ化成社製ＲＴＴＣＨＮ１５ＷＴ％－Ｅ０６（酸化チタニウムの一次粒径２５ｎｍ、動的光散乱による平均粒径１００ｎｍ、固形分濃度１５質量％） [Component (E)]
E-1: Nanouse (registered trademark) OZ-S30K-AC manufactured by Nissan Chemical Industries, Ltd. (primary particle size of zirconium oxide 20 nm, average particle size 80 nm by dynamic light scattering, solid content concentration 20% by mass)
E-2: RTTCHN 15WT% -E06 manufactured by CI Kasei Co., Ltd. (primary particle size of titanium oxide 25 nm, average particle size 100 nm by dynamic light scattering, solid content concentration 15% by mass)
［実施例１］（水分捕獲体形成組成物（ＪＯ－１）の調製）
　大気環境下で、成分（Ｃ）である（Ｃ－１）８０質量部に、成分（Ａ）の水分捕獲剤（Ａ１）である（ＡＯ－１）２０質量部を添加して均一な溶液とした後、この溶液に成分（Ｂ）である（Ｂ－１）１質量部を加えて水分捕獲体形成組成物（ＪＯ－１）を調製した。使用した各成分および配合量は、後述する他の実施例とともに、表１にまとめて示す。 [Example 1] (Preparation of moisture trap forming composition (JO-1))
Under atmospheric environment, 20 parts by mass of (AO-1) which is the moisture trapping agent (A1) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. Thereafter, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (JO-1). Each component and the amount used are shown in Table 1 together with other examples described later.
［実施例２～１９および比較例１～４］
（水分捕獲体形成組成物（ＪＯ－２）～（ＪＯ－２３）の調製）
　下記表１に示す種類および配合量の各成分を用いた以外は、実施例１と同様に操作し、各水分捕獲体形成組成物を調製した。 [Examples 2 to 19 and Comparative Examples 1 to 4]
(Preparation of moisture trap forming composition (JO-2) to (JO-23))
Except having used each component of the kind and compounding quantity which are shown in following Table 1, it operated similarly to Example 1 and prepared each moisture capture body formation composition.
　尚、実施例１７～実施例１９では、成分（Ｅ）を表１に記載の固形分に相当する量を用いた。 In Examples 17 to 19, the component (E) was used in an amount corresponding to the solid content shown in Table 1.
［実施例２０］（水分捕獲体形成組成物（ＪＳ－１）の調製）
　大気環境下で、成分（Ｃ）である（Ｃ－１）８０質量部に、成分（Ａ）の水分捕獲剤（Ａ２）である（ＡＳ－１）２０質量部を添加して均一な溶液とした後、この溶液に成分（Ｂ）である（Ｂ－１）１質量部を加えて水分捕獲体形成組成物（ＪＳ－１）を調製した。使用した各成分および配合量は、後述する他の実施例とともに、表２にまとめて示す。 [Example 20] (Preparation of moisture trap forming composition (JS-1))
Under atmospheric environment, 20 parts by mass of (AS-1) which is a moisture trapping agent (A2) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. Thereafter, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (JS-1). Each component and amount used are shown in Table 2 together with other examples described later.
［実施例２１～３２および比較例５］
（水分捕獲体形成組成物（ＪＳ－２）～（ＪＳ－１４）の調製）
　下記表２に示す種類および配合量の各成分を用いた以外は、実施例２０と同様に操作し、各水分捕獲体形成組成物を調製した。 [Examples 21 to 32 and Comparative Example 5]
(Preparation of Moisture Capturing Body Forming Composition (JS-2) to (JS-14))
Except having used each component of the kind and compounding quantity which are shown in following Table 2, it operated similarly to Example 20 and prepared each moisture capture body formation composition.
　尚、実施例３０～実施例３２では、成分（Ｅ）を表２に記載の固形分に相当する量を用いた。 In Examples 30 to 32, the component (E) was used in an amount corresponding to the solid content described in Table 2.
［実施例３３］（水分捕獲体形成組成物（Ｊ－１）の調製）
　大気環境下で、成分（Ｃ）である（Ｃ－１）８０質量部に、成分（Ａ）の水分捕獲剤（Ａ３）である（Ａ－１）２０質量部を添加して均一な溶液とした後、この溶液に成分（Ｂ）である（Ｂ－１）１質量部を加えて水分捕獲体形成組成物（Ｊ－１）を調製した。使用した各成分および配合量は、後述する他の実施例とともに、表３にまとめて示す。 [Example 33] (Preparation of moisture trap forming composition (J-1))
Under atmospheric environment, 20 parts by mass of (A-1) which is a moisture trapping agent (A3) of component (A) is added to 80 parts by mass of (C-1) which is component (C) to obtain a uniform solution. After that, 1 part by mass of component (B) (B-1) was added to this solution to prepare a moisture trap forming composition (J-1). Each component and the amount used are shown in Table 3 together with other examples described later.
［実施例３４～４４および比較例６］（水分捕獲体形成組成物（Ｊ－２）～（Ｊ－１３）の調製）
　下記表３に示す種類および配合量の各成分を用いた以外は、実施例３３と同様に操作し、各水分捕獲体形成組成物を調製した。 [Examples 34 to 44 and Comparative Example 6] (Preparation of Moisture Capturing Body Forming Compositions (J-2) to (J-13))
Except having used each component of the kind and compounding quantity which are shown in following Table 3, it operated similarly to Example 33 and prepared each moisture capture body formation composition.
　尚、実施例４０～４４では、成分（Ｅ）を表３に記載の固形分に相当する量を用いた。 In Examples 40 to 44, the component (E) was used in an amount corresponding to the solid content shown in Table 3.
　＜有機ＥＬ素子の製造＞
　縦横２５ｍｍ、厚さ０．７ｍｍのガラス板に膜厚１５ｎｍのＩＴＯ膜が幅２ｍｍのパターンで形成されたガラス基板（旭硝子（株）製）上に、正孔注入材料としてポリ（３，４）エチレンジオキシチオフェン／ポリスチレンサルフォネイト（ＰＥＤＯＴ／ＰＳＳ）を含有する正孔注入層形成用塗液を３０００ｒｐｍで５０秒間スピンコートを行い、膜厚５０ｎｍの正孔注入層を形成した後、高純度窒素中、２００℃で１０分間加熱・乾燥を行った。ここで、正孔注入層形成用塗液としては、ＰＥＤＯＴ／ＰＳＳを純水に固形分０．１質量％で溶解したものを用いた。正孔注入層上に、発光材料ポリフルオレン誘導体の１．０質量％溶液を２０００ｒｐｍで５０秒間スピンコートを行い、膜厚７０ｎｍの有機発光層を形成した後、６０℃で１０分間焼成した。有機発光層上に、１０－５Ｐａの圧力条件下、０．１ｎｍ／ｓｅｃの蒸着速度でＬｉＦを１０ｎｍ、０．１ｎｍ／ｓｅｃの蒸着速度でＣａを２０ｎｍ積層し、その上に２０ｎｍ／ｓｅｃの蒸着速度でＡｌを１００ｎｍ積層して陰極を形成した。 <Manufacture of organic EL elements>
Poly (3,4) as a hole injection material on a glass substrate (manufactured by Asahi Glass Co., Ltd.) having an ITO film having a thickness of 15 nm formed on a glass plate having a length and width of 25 mm and a thickness of 0.7 mm and a pattern of 2 mm in width. A coating solution for forming a hole injection layer containing ethylenedioxythiophene / polystyrene sulfonate (PEDOT / PSS) is spin-coated at 3000 rpm for 50 seconds to form a hole injection layer having a thickness of 50 nm, and then high purity. Heating and drying were performed at 200 ° C. for 10 minutes in nitrogen. Here, as the hole injection layer forming coating solution, a solution in which PEDOT / PSS was dissolved in pure water at a solid content of 0.1% by mass was used. On the hole injection layer, a 1.0 mass% solution of the light emitting material polyfluorene derivative was spin-coated at 2000 rpm for 50 seconds to form an organic light emitting layer having a thickness of 70 nm, and then baked at 60 ° C. for 10 minutes. On the organic light emitting layer, LiF was deposited to 10 nm at a deposition rate of 0.1 nm / sec under a pressure condition of 10 −5 Pa, and 20 nm of Ca was deposited at a deposition rate of 0.1 nm / sec. A cathode was formed by laminating 100 nm of Al at a deposition rate.
　次いで、ガラス基板上に形成された有機ＥＬ層上に、上記各水分捕獲形成組成物を、スピンコートにて塗布し、１２０℃、５分間の加熱により、膜厚５０μｍの塗膜を形成した。塗膜の膜厚は、デプスゲージ５４７－２５１（（株）ミツトヨ製）で測定した。次いで、得られた成膜済みガラス基板の周縁部に、比較例１で得られた水分捕獲形成組成物と同組成の組成物を、ディスペンサーを用いて塗布し、厚さ１００μｍの塗膜を形成した。 Next, each of the above moisture trapping composition was applied on the organic EL layer formed on the glass substrate by spin coating, and a coating film having a thickness of 50 μm was formed by heating at 120 ° C. for 5 minutes. The film thickness of the coating film was measured with a depth gauge 547-251 (manufactured by Mitutoyo Corporation). Next, a composition having the same composition as the moisture-trapping composition obtained in Comparative Example 1 was applied to the peripheral edge of the obtained glass substrate with a dispenser using a dispenser to form a coating film having a thickness of 100 μm. did.
　次いで、真空張り合わせ装置を用いて、成膜済みガラス基板へ縦横２５ｍｍ、厚さ０．７ｍｍの対向ガラス基板を前記塗膜を介して貼り合わせ、水分捕獲体（硬化）条件として、超高圧水銀灯（３６５ｎｍにおける強度が１００ｍＷ）を用いて１Ｊ／ｃｍ２の紫外光（ＵＶ）を照射した後、８０℃で３０分間加熱することにより、前記塗膜を硬化させ、水分捕獲体およびシール材を形成した。実施例３、実施例５、実施２２、実施例２４および実施例３６のみ、真空張り合わせ装置を用いて、成膜済みガラス基板へ縦横２５ｍｍ、厚さ０．７ｍｍの対向ガラス基板を前記塗膜を介して貼り合わせ、１００℃で３０分間加熱した後、８０℃で３０分間加熱することにより、前記塗膜を硬化させ、水分捕獲体およびシール材を形成した。 Next, using a vacuum laminating apparatus, a counter glass substrate having a length and width of 25 mm and a thickness of 0.7 mm is bonded to the film-formed glass substrate through the coating film, and an ultrahigh pressure mercury lamp ( After irradiation with ultraviolet light (UV) of 1 J / cm 2 using an intensity at 365 nm of 100 nm, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material. . Only in Example 3, Example 5, Example 22, Example 24, and Example 36, using the vacuum laminating apparatus, the coated glass substrate was coated with the opposite glass substrate having a length and width of 25 mm and a thickness of 0.7 mm on the film-formed glass substrate. After heating at 100 ° C. for 30 minutes, the coating film was cured by heating at 80 ° C. for 30 minutes to form a moisture trap and a sealing material.
　以上のようにして、有機ＥＬ素子を製造した。 The organic EL element was manufactured as described above.
　＜評価＞
　上記調製した実施例１～実施例４４および比較例１～６の各水分捕獲体形成組成物の製膜性、各水分捕獲体の耐熱性、ガラス密着性、発光外観および光取出し効率を下記方法に従い評価した。その評価結果を表１、表２および表３に合わせて示す。 <Evaluation>
The film forming properties, heat resistance, glass adhesion, light emission appearance, and light extraction efficiency of each of the water trapping body-forming compositions of Examples 1 to 44 and Comparative Examples 1 to 6 prepared above are as follows. It evaluated according to. The evaluation results are shown in Table 1, Table 2, and Table 3.
［製膜性］
　上記調製した各水分捕獲体形成組成物を用い、長辺６６ｍｍ、短辺２４ｍｍ、厚さ１．１ｍｍのガラス基板に、長辺５８ｍｍ、短辺１３ｍｍ、深さ０．３ｍｍの掘込みを設け、この堀込みに水分捕獲体形成組成物２００μＬを塗布した後、高圧水銀ランプを用いてＵＶ照射（照射エネルギー：１Ｊ／ｃｍ２）により硬化させて水分捕獲体を形成し、目視により外観観察を行った。このとき、クラックおよび凹凸が認められない場合、製膜性は良好「○」と、クラックまたは凹凸の少なくともいずれかが認められた場合、不良「×」と評価した。 [Film forming properties]
Using each of the prepared moisture trap forming compositions, a glass substrate having a long side of 66 mm, a short side of 24 mm, and a thickness of 1.1 mm is provided with a long side of 58 mm, a short side of 13 mm, and a depth of 0.3 mm. After applying 200 μL of the moisture trap forming composition to this trench, it is cured by UV irradiation (irradiation energy: 1 J / cm 2 ) using a high pressure mercury lamp to form a moisture trap, and the appearance is visually observed. It was. At this time, when no cracks and unevenness were observed, the film-forming property was evaluated as “good”, and when at least one of cracks or unevenness was observed, the film was evaluated as defective “x”.
［耐熱性］
　サンプル管中に、上記調製した各水分捕獲体形成組成物を適量入れ、上述の［製膜性］の硬化条件と同じ条件で、膜厚２ｍｍの水分捕獲体をサンプル管底部に形成した。次いで、形成した水分捕獲体を大気に暴露して十分吸湿させた後、サンプル管の蓋を閉めてシールし、サンプル管の底部が上（製膜面が上）となるように固定した状態で８５℃の環境下に静置した。その後、３３６時間経過した時点の水分捕獲体の状態を観察した。このとき、水分捕獲体に全く変化が認められなかった場合、耐熱性は極良好「○」と評価し、極軽微な変化のみが認められた場合、良好「△」と評価し、水分捕獲体が下方へ垂れて変形が認められた場合、不良「×」と評価した。 [Heat-resistant]
An appropriate amount of each of the prepared water trap forming compositions was put in a sample tube, and a water trap with a thickness of 2 mm was formed on the bottom of the sample tube under the same conditions as the above [Film-forming property] curing conditions. Next, after exposing the formed moisture trap to the atmosphere to absorb moisture sufficiently, the lid of the sample tube is closed and sealed, and the sample tube is fixed so that the bottom of the sample tube is on top (the film-forming surface is on top). It left still in 85 degreeC environment. Thereafter, the state of the moisture trap when 336 hours passed was observed. At this time, if no change was observed in the moisture trap, the heat resistance was evaluated as “good”, and if only a slight change was observed, it was evaluated as “good”. Was evaluated as a defective “x” when deformation was observed.
［ガラス密着性］
　上記調製した各水分捕獲体形成組成物を用い、長辺６６ｍｍ、短辺２４ｍｍ、厚さ１．１ｍｍのガラス基板に、上述の［製膜性］の硬化条件と同じ条件で、膜厚２ｍｍの水分捕獲体を形成した。大気中における、上記ガラス基板からの各水分捕獲体の剥離の有無を観察した。このとき、剥離が認められない場合、密着性は良好「○」と、剥離した場合、不良「×」と評価した。 [Glass adhesion]
Using each of the prepared moisture trap forming compositions, a glass substrate having a long side of 66 mm, a short side of 24 mm, and a thickness of 1.1 mm is formed on a glass substrate having a thickness of 2 mm under the same conditions as the above [Film-forming properties] curing conditions. A moisture trap was formed. The presence or absence of peeling of each moisture trap from the glass substrate in the air was observed. At this time, when peeling was not recognized, the adhesiveness was evaluated as “good”, and when peeled, it was evaluated as defective “x”.
　［有機ＥＬ素子の評価］（発光外観（ダークスポット、ムラ）、光取出し効率の評価）
　上記［有機ＥＬ素子の製造］で得られたそれぞれの有機ＥＬ素子について、室温において順方向電流を１０ｍＡ／ｃｍ２通電し、発光外観（ダークスポット、ムラ）を観察した。また、コニカミノルタセンシング（株）社製分光放射輝度計「ＣＳ－２０００」により正面輝度を測定し、光散乱層を形成していない基板で作製した有機ＥＬ素子の正面輝度を基準とし、白色発光素子の正面輝度の向上率を算出した。 [Evaluation of organic EL elements] (Evaluation of light emission appearance (dark spots, unevenness), light extraction efficiency)
About each organic EL element obtained by the above [Manufacture of organic EL elements], a forward current of 10 mA / cm 2 was applied at room temperature, and the appearance of light emission (dark spots, unevenness) was observed. In addition, the front luminance was measured with a spectral radiance meter “CS-2000” manufactured by Konica Minolta Sensing Co., Ltd., and white light was emitted based on the front luminance of the organic EL device produced on the substrate on which the light scattering layer was not formed. The improvement rate of the front luminance of the element was calculated.
　評価は、下記基準に基づき行った。
・発光外観（ダークスポット、ムラ）
　ダークスポット、ムラが観察されない：良（○）、
　ダークスポット、ムラが観察される：不可（×）
・光取出し効率
　正面輝度向上率１．２倍以上：優（◎）、
　正面輝度向上率１．０倍以上～１．２倍未満：良（○）、
　正面輝度向上率１．０倍未満：不良（×） Evaluation was performed based on the following criteria.
・ Luminescent appearance (dark spots, unevenness)
Dark spots and unevenness are not observed: Good (○),
Dark spots and unevenness are observed: Impossible (×)
-Light extraction efficiency Front brightness improvement rate 1.2 times or more: Excellent (◎),
Front brightness improvement rate of 1.0 times or more to less than 1.2 times: Good (○),
Front luminance improvement rate less than 1.0 times: defective (×)
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000048
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000049
Figure JPOXMLDOC01-appb-T000050
Figure JPOXMLDOC01-appb-T000050
　表１～表３の評価結果から明らかなように、本実施例の水分捕獲体形成組成物および本実施例の水分捕獲体形成組成物から形成された水分捕獲体では、製膜性、耐熱性および密着性のいずれにおいても良好または極良好であった。それに対し、比較例の水分捕獲体形成組成物から形成された水分捕獲体では、耐熱性が不良であった。 As is apparent from the evaluation results in Tables 1 to 3, in the moisture trap forming composition of this example and the moisture trap formed from the moisture trap forming composition of this example, the film forming property and heat resistance are In addition, both the adhesion and the adhesion were good or extremely good. On the other hand, in the moisture trap formed from the moisture trap forming composition of the comparative example, the heat resistance was poor.
　本発明は、空気下での取り扱いが可能で、かつ揮発性の分解生成物を生じ難い水分捕獲体を形成可能な水分捕獲体形成組成物を提供することができる。そのため、本発明は、この水分捕獲体形成組成物から形成される水分捕獲体、および、その水分捕獲体を備える電子デバイスを高い生産性で提供することができる。そして、特に、ダークスポットの発生を抑制する有機ＥＬ素子や、水分の影響を抑制する液晶表示素子等の電子デバイスに好適に使用することができる。 The present invention can provide a moisture trap forming composition capable of forming a moisture trap that can be handled in air and hardly generates a volatile decomposition product. Therefore, the present invention can provide a moisture trap formed from the moisture trap forming composition and an electronic device including the moisture trap with high productivity. And it can use suitably for electronic devices, such as an organic EL element which suppresses generation | occurrence | production of a dark spot especially, and a liquid crystal display element which suppresses the influence of moisture.
　１０　　有機ＥＬ層
　２０　　構造体
　２２　　基板
　２４　　封止用基板
　２６　　シール材
　３０，１３０　　水分捕獲体
　４０　　ガスバリヤフィルム
　１００，２００，３００，４００，５００　　有機ＥＬ素子 DESCRIPTION OF SYMBOLS 10 Organic EL layer 20 Structure 22 Substrate 24 Sealing substrate 26 Sealing material 30,130 Moisture trap 40 Gas barrier film 100, 200, 300, 400, 500 Organic EL element

Claims (5)

  1. 　水分捕獲体を備える有機ＥＬ素子であって、
    　前記水分捕獲体が、
    　（Ａ）加水分解性基を有する化合物および該化合物の加水分解物からなる群より選択される少なくとも１種の化合物と、
    　（Ｂ）酸発生剤および塩基発生剤からなる群より選択される少なくとも１種の化合物と、
    　（Ｃ）硬化性化合物と
    を含むことを特徴とする有機ＥＬ素子。     An organic EL device comprising a moisture trap,
    The moisture trap is
    (A) at least one compound selected from the group consisting of a compound having a hydrolyzable group and a hydrolyzate of the compound;
    (B) at least one compound selected from the group consisting of an acid generator and a base generator;
    (C) An organic EL device comprising a curable compound.
  2. 　前記（Ａ）化合物が、
    　（Ａ１）式（Ａ１－１）で表される化合物、式（Ａ１－２）で表される化合物および式（Ａ１－３）で表される化合物から選ばれる少なくとも１種の化合物、
    　（Ａ２）カルボン酸無水物およびカルボン酸化合物から選ばれる少なくとも１種の化合物、並びに、
    　（Ａ３）式（Ａ３－１）で表される化合物、式（Ａ３－２）で表される化合物および式（Ａ３－３）で表される化合物から選ばれる少なくとも１種の化合物
    からなる群から選択される少なくとも１種の化合物であり、
    　前記（Ｂ）化合物が、酸発生剤であることを特徴とする請求項１に記載の有機ＥＬ素子。
    Figure JPOXMLDOC01-appb-C000001
     ［式（Ａ１－１）中、Ｒ１～Ｒ５は、それぞれ独立に水素原子または炭素数１～１８の有機基であり、Ｒ６およびＲ７は、それぞれ独立に水素原子、水酸基または炭素数１～１８の有機基であり、Ｒ３、Ｒ４およびＲ７は、これらが直接結合する炭素原子と一緒になって環状構造を形成していてもよく、ｎは０または１～１８の整数であり、＊は結合位を示し；式（Ａ１－２）中、Ｒ１は水素原子または炭素数１～１８の有機基であり；Ｒ８はそれぞれ独立に炭素数３～３０の有機基であり；式（Ａ１－３）中、式Ｒ８は式（Ａ１－２）と同義である。］
    Figure JPOXMLDOC01-appb-C000002
     ［式（Ａ３－１）、式（Ａ３－２）および式（Ａ３－３）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基、カルボニル基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、またはメルカプト基であり；
    ｐは０～６の整数であり；
    ｒは０～２の整数であり、ｓは１～３０の整数である。］     The compound (A) is
    (A1) at least one compound selected from a compound represented by formula (A1-1), a compound represented by formula (A1-2), and a compound represented by formula (A1-3);
    (A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and
    (A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected,
    The organic EL device according to claim 1, wherein the compound (B) is an acid generator.
    Figure JPOXMLDOC01-appb-C000001
     [In the formula (A1-1), R 1 to R 5 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 6 and R 7 are each independently a hydrogen atom, a hydroxyl group or a carbon number. An organic group of 1 to 18, and R 3 , R 4 and R 7 may be combined with the carbon atom to which they are directly bonded to form a cyclic structure, and n is 0 or an integer of 1 to 18 * Represents a bonding position; in formula (A1-2), R 1 is a hydrogen atom or an organic group having 1 to 18 carbon atoms; and R 8 is independently an organic group having 3 to 30 carbon atoms. There; wherein (A1-3), wherein R 8 has the same meaning as in formula (A1-2). ]
    Figure JPOXMLDOC01-appb-C000002
     [In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom; R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent. Group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group;
    p is an integer from 0 to 6;
    r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
  3. 　前記（Ａ）化合物が、
    　（Ａ２）カルボン酸無水物およびカルボン酸化合物から選ばれる少なくとも１種の化合物、並びに、
    　（Ａ３）式（Ａ３－１）で表される化合物、式（Ａ３－２）で表される化合物および式（Ａ３－３）で表される化合物から選ばれる少なくとも１種の化合物
    からなる群から選択される少なくとも１種の化合物であり、
    　前記（Ｂ）化合物が、塩基発生剤であることを特徴とする請求項１に記載の有機ＥＬ素子。
    Figure JPOXMLDOC01-appb-C000003
     ［式（Ａ３－１）、式（Ａ３－２）および式（Ａ３－３）中、Ｘは、ケイ素原子、チタン原子またはジルコニウム原子であり；Ｒ２１は、（メタ）アクリロイル基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、メルカプト基、カルボニル基およびイソシアネート基から選ばれる少なくとも１種の基を有する有機基、炭素数１～６のアルキル基、炭素数３～１２のシクロアルキル基、フェニル基、またはベンジル基であり；Ｒ２２は、水素原子、置換基を有してもよい炭素数１～２０のアルキル基、置換基を有してもよい炭素数３～１２のシクロアルキル基、置換基を有してもよい炭素数６～１４の芳香族炭化水素基、（メタ）アクリロイルオキシ基、グリシドキシ基、オキシラニル基、オキセタニル基、３，４－エポキシシクロヘキシル基、またはメルカプト基であり；
    ｐは０～６の整数であり；
    ｒは０～２の整数であり、ｓは１～３０の整数である。］     The compound (A) is
    (A2) at least one compound selected from carboxylic acid anhydrides and carboxylic acid compounds, and
    (A3) From the group consisting of at least one compound selected from the compound represented by formula (A3-1), the compound represented by formula (A3-2), and the compound represented by formula (A3-3) At least one compound selected,
    The organic EL device according to claim 1, wherein the compound (B) is a base generator.
    Figure JPOXMLDOC01-appb-C000003
     [In the formulas (A3-1), (A3-2) and (A3-3), X is a silicon atom, a titanium atom or a zirconium atom; R 21 is a (meth) acryloyl group, an oxiranyl group, An organic group having at least one group selected from an oxetanyl group, a 3,4-epoxycyclohexyl group, a mercapto group, a carbonyl group and an isocyanate group, an alkyl group having 1 to 6 carbon atoms, and a cycloalkyl group having 3 to 12 carbon atoms R 22 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a cycloalkyl having 3 to 12 carbon atoms which may have a substituent. Group, optionally substituted aromatic hydrocarbon group having 6 to 14 carbon atoms, (meth) acryloyloxy group, glycidoxy group, oxiranyl group, oxetanyl group, 3,4 It is an epoxycyclohexyl group or a mercapto group;
    p is an integer from 0 to 6;
    r is an integer from 0 to 2, and s is an integer from 1 to 30. ]
  4. 　前記水分捕獲体が、さらに、（Ｄ）ラジカル重合開始剤を含有することを特徴とする請求項１～３のいずれかに１項に記載の有機ＥＬ素子。 4. The organic EL element according to claim 1, wherein the moisture trap further contains (D) a radical polymerization initiator.
  5. 　前記水分捕獲体が、さらに、（Ｅ）微粒子を含有することを特徴とする請求項１～５のいずれかに１項に記載の有機ＥＬ素子。 The organic EL element according to any one of claims 1 to 5, wherein the moisture trap further contains (E) fine particles.
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