Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
  • C08K5/3432—Six-membered rings
  • C08K5/3435—Piperidines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere
  • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/02—Details
  • H05B33/04—Sealing arrangements, e.g. against humidity
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
  • H10K50/80—Constructional details
  • H10K50/84—Passivation; Containers; Encapsulations
  • H10K50/844—Encapsulations
• • 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
  • H10K59/10—OLED displays

Definitions

• the present invention relates to a curable composition, a sealant, a frame sealant, a display panel, and a method for manufacturing the same.
• organic EL elements organic electroluminescence elements
• display elements are generally susceptible to deterioration due to moisture and oxygen in the air. For this reason, in various display devices, the display elements are generally sealed with a sealing layer.
• an organic EL display panel has an element substrate having an organic EL element, an opposing substrate, and a sealing layer disposed between them to seal the organic EL element.
• Such organic EL display panels are manufactured by various methods.
• the dam-fill method is known as one such manufacturing method.
• an organic EL display panel is manufactured through, for example, the steps of 1) applying a first sealant in a frame shape onto an opposing substrate, 2) filling the area surrounded by the first sealant with a second sealant to form a sealant layer, 3) irradiating the sealant layer with light, 4) bonding a substrate on which an organic EL element is disposed to the opposing substrate having the sealant layer after light irradiation, and 5) heating and curing the sealant layer (see, for example, Patent Document 1).
• a frame sealant used in the above-mentioned method for example, a sealant containing a polyolefin, an epoxy compound (curable resin A), a heat curing agent, and a water-absorbent filler is known (see, for example, Patent Document 2).
• a thermal cationic initiator is used as the heat curing agent.
• sealant for organic EL elements is a sealant that contains a photocurable compound containing a (meth)acrylic-modified epoxy resin and a photocationic polymerization initiator (see, for example, Patent Document 3).
• the sealant shown in Patent Document 2 is cured by heating at 100°C, which has the drawback that the element is easily damaged by heat. To prevent such damage, the sealant is required to have low-temperature curing properties.
• the above-mentioned sealant is required to have a predetermined pot life or more after light irradiation, that is, to be able to maintain a moderately low viscosity after light irradiation.
• the sealant applied to one substrate is irradiated with light to cause provisional curing, and then the other substrate is bonded to the substrate and heated to cause full curing.
• the sealant shown in Patent Documents 2 and 3 is prone to excessive viscosity increase because the curing reaction proceeds too much after light irradiation and before the other substrate is bonded.
• the curable composition after light irradiation can maintain its shape well when cured by heating. In this way, it is desirable to be able to achieve both lamination suitability and shape retention while maintaining handling during application.
• the present invention was made in consideration of the above circumstances, and provides a curable composition, a sealant, a frame sealant, a display panel, and a method for manufacturing the same that have low-temperature curing properties and can achieve both lamination suitability and shape retention.
• a curable composition comprising a curable compound, a photocationic polymerization initiator, and a tertiary amine, the content of the tertiary amine being 20 parts by mass or more relative to 100 parts by mass of the photocationic polymerization initiator, and having a complex viscosity at 25°C of 1.0 x 103 Pa ⁇ s or more and 5.0 x 104 Pa ⁇ s or less after 600 seconds of irradiation with light having a wavelength of 365 nm at an illuminance of 100 mW/ cm2 and an accumulated light quantity of 3000 mJ/cm2.
• a sealant comprising the curable composition according to any one of [1] to [6].
• a frame sealant comprising the curable composition according to any one of [1] to [6].
• a display panel comprising: an element substrate on which elements are arranged; a counter substrate arranged opposite the element substrate with the elements interposed therebetween; and a sealing portion arranged between the element substrate and the counter substrate for sealing the elements, the sealing portion including a cured product of the sealant according to [7].
• a method for manufacturing a display panel comprising: a step of applying a first sealant in a frame shape along an outer periphery of a display area on one surface of an element substrate or an opposing substrate; a step of filling a second sealant into the area surrounded by the first sealant to form a sealant layer; a step of irradiating the sealant layer with light; a step of bonding one substrate and the other substrate together via the sealant layer irradiated with light; and a step of heating and curing the sealant layer, wherein at least one of the first sealant and the second sealant is the sealant described in [7].
• the present invention was made in consideration of the above circumstances, and provides a curable composition, a sealant, a frame sealant, a display panel, and a method for manufacturing the same that have low-temperature curing properties and can achieve both lamination suitability and shape retention.
• the curable composition of the present invention contains a curable compound, a photocationic polymerization initiator, and a tertiary amine, and has a complex viscosity adjusted to a range of 1.0 ⁇ 10 3 Pa ⁇ s to 5.0 ⁇ 10 4 Pa ⁇ s at 25° C. 600 seconds after irradiation with light of 365 nm wavelength at an illuminance of 100 mW/cm 2 and an integrated light quantity of 3000 mJ/cm 2. This allows the applied shape to be well maintained while maintaining the fluidity and tackiness during lamination.
• the complex viscosity after light irradiation when the complex viscosity after light irradiation is 1.0 ⁇ 10 3 Pa ⁇ s or more, the applied shape is easily maintained even when heated thereafter. This can improve the sealing property of the cured product.
• the complex viscosity after light irradiation is 5.0 ⁇ 10 4 Pa ⁇ s or less, the fluidity and tackiness during lamination are not easily impaired, and lamination suitability can be maintained well.
• the complex viscosity of the curable composition can be adjusted by the amount of tertiary amine, the composition of the curable compound, etc.
• the curable composition of the present invention contains a predetermined amount or more of a tertiary amine relative to the photocationic polymerization initiator.
• a curable composition is irradiated with light, an acid is first generated from the photocationic polymerization initiator. This acid is captured by a sufficient amount of the tertiary amine, so that after light irradiation, the curable compound is less likely to be cured by the acid, and the increase in viscosity can be reduced.
• the curable composition is then heated, the acid captured by the tertiary amine is released, and the curable compound polymerizes (cures).
• the curable compound preferably contains an epoxy compound and at least one of a (meth)acrylic-modified epoxy compound and a (meth)acrylic compound.
• the photocationic polymerization initiator When the photocationic polymerization initiator generates an acid by light irradiation, it may also generate radicals instantaneously. The radicals cause the (meth)acrylic-modified epoxy compound or the (meth)acrylic compound to cure. As a result, the viscosity of the curable composition is appropriately increased by light irradiation, making it easier to maintain its shape.
• the curable composition according to one embodiment of the present invention will be specifically described below.
• Curable Composition contains a curable compound, a cationic photopolymerization initiator, and a tertiary amine.
• the curable compound includes a curable compound that reacts with a cationic photopolymerization initiator.
• the curable compound that reacts with a cationic photopolymerization initiator is a compound that polymerizes and hardens using, as a medium, active species of acids or radicals generated by the cationic photopolymerization initiator upon receiving light or heat energy.
• Such a curable compound preferably includes a compound that includes a cationic polymerizable group, and from the viewpoint of enhancing thermosetting properties, preferably includes an epoxy compound.
• the curable compound contains an epoxy compound. Furthermore, from the viewpoint of making it easier to adjust the viscosity after light irradiation to a predetermined level or higher, it is preferable that the curable compound further contains at least one of a (meth)acrylic compound and a (meth)acrylic-modified epoxy compound in addition to the epoxy compound.
• Epoxy Compound The curable compound may contain only one type of epoxy compound, or may contain two or more types of epoxy compounds.
• an epoxy compound refers to a compound having one or more epoxy groups in the molecule.
• epoxy compounds do not include compounds having both an epoxy group and a (meth)acryloyl group.
• the number of epoxy groups contained in one molecule of an epoxy compound may be one or may be two or more. From the viewpoint of increasing the curing reactivity, it is preferable that the number of epoxy groups contained in one molecule of an epoxy compound is two or more.
• epoxy compounds include known epoxy compounds, such as aromatic epoxy compounds, aliphatic epoxy compounds, and alicyclic epoxy compounds. Among these, from the viewpoint of further reducing the moisture permeability of the cured product, it is preferable that at least one of the epoxy compounds contains an aromatic epoxy compound.
• aromatic epoxy compound examples include glycidyl ethers of alcohols (including polyhydric alcohols) containing an aromatic ring.
• bisphenol-type glycidyl ether compounds obtained by reacting epichlorohydrin with bisphenols such as bisphenol A, bisphenol S, bisphenol F, bisphenol AD, etc., or diols obtained by modifying these aromatic diols with ethylene glycol, propylene glycol, alkylene glycol, etc.
• trisphenol type glycidyl ether compounds obtained by reacting a trisphenol compound (e.g., 1,1,1-tris(hydroxyphenyl)methane, 1-[ ⁇ -methyl- ⁇ -(4-hydroxyphenyl)ethyl]-3-[ ⁇ , ⁇ -bis(4-hydroxyphenyl)ethyl]benzene (or 4-[4-[1,1-bis(4-hydroxyphenyl)ethyl]- ⁇ , ⁇ -dimethylbenzyl]phenol) with epichlorohydrin
• bisphenol type epoxy compounds such as bisphenol A type epoxy compounds and bisphenol F type epoxy compounds, cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, triphenol methane type epoxy compounds, triphenol ethane type epoxy compounds, trisphenol type epoxy compounds, dicyclopentadiene type epoxy compounds, diphenyl ether type epoxy compounds, and biphenyl type epoxy compounds are preferred.
• the epoxy compound may be liquid or solid. From the viewpoint of improving the coatability of the curable composition, a liquid epoxy compound is preferred. From the viewpoint of reducing the moisture permeability of the cured product, a solid epoxy compound is preferred.
• the softening point of the solid epoxy compound is preferably 40°C or higher and 150°C or lower. The softening point can be measured by the ring and ball method specified in JIS K7234.
• the weight average molecular weight of the epoxy compound is preferably 200 or more and 10,000 or less, and more preferably 300 or more and 5,000 or less.
• the weight average molecular weight of the epoxy compound is measured in terms of polystyrene by gel permeation chromatography (GPC).
• the curable compound may contain only one type of epoxy compound, or may contain two or more types.
• a liquid epoxy compound may be combined with a solid epoxy compound.
• a bifunctional aromatic epoxy compound may be combined with a trifunctional or higher aromatic epoxy compound.
• the trifunctional or higher aromatic epoxy compound when a difunctional aromatic epoxy compound is combined with a trifunctional or higher aromatic epoxy compound, the trifunctional or higher aromatic epoxy compound can be, for example, 10% by mass or more, preferably 30% by mass or more and 70% by mass or less, based on the total amount of epoxy compounds.
• the content of the trifunctional or higher aromatic epoxy compound is 10% by mass or more, the moisture permeability of the cured product can be further increased.
• the viscosity of the curable composition after light irradiation is likely to increase, the acid generated from the photocationic polymerization initiator is trapped by the tertiary amine, so that excessive viscosity increase can be suppressed.
• the total amount of epoxy compounds is preferably 50% by mass or more, more preferably 50% by mass or more and 95% by mass or less, and even more preferably 70% by mass or more and 95% by mass or less, based on the curable compounds.
• amount of epoxy compounds is 50% by mass or more, it is easier to increase the curing reactivity by heating.
• viscosity of the curable composition after light irradiation can be reduced, so that the fluidity and tackiness during lamination can be improved.
• the amount of epoxy compounds is 95% by mass or less, for example, the amount of (meth)acrylic-modified epoxy compounds or (meth)acrylic compounds becomes relatively large, so that it is easier to moderately increase the viscosity of the curable composition after light irradiation, and shape retention is more likely to be improved.
• the (meth)acrylic modified epoxy compound refers to a compound having one or more epoxy groups and one or more (meth)acryloyl groups in the molecule.
• the curable compound may contain only one type of (meth)acrylic modified epoxy compound, or may contain two or more types.
• the number of epoxy groups and (meth)acryloyl groups in the (meth)acrylic-modified epoxy compound is not particularly limited, and each may be only one, or may be two or more.
• the (meth)acrylic-modified epoxy compound has good compatibility with epoxy compounds.
• the (meth)acrylic modified epoxy compound is obtained by modifying at least one of the epoxy groups of a bifunctional or higher functional epoxy compound with a (meth)acryloyl group.
• the (meth)acrylic modified epoxy compound is obtained, for example, by reacting a bifunctional or higher functional epoxy compound with (meth)acrylic acid in the presence of a basic catalyst.
• the epoxy compound modified with a (meth)acryloyl group may be a polyfunctional epoxy compound having two or more epoxy groups in the molecule, and from the viewpoint of improving the applicability and suppressing the decrease in adhesive strength due to too high crosslinking density, a bifunctional epoxy compound is preferred.
• bifunctional epoxy compounds include bisphenol type epoxy compounds (bisphenol A type, bisphenol F type, 2,2'-diallyl bisphenol A type, bisphenol AD type, hydrogenated bisphenol type, etc.), biphenyl type epoxy compounds, and naphthalene type epoxy compounds.
• bisphenol type epoxy compounds of bisphenol A type and bisphenol F type are preferred from the viewpoint of easily improving the applicability.
• a (meth)acrylic modified epoxy compound derived from a bisphenol type epoxy compound has an advantage of being superior in applicability compared to a (meth)acrylic modified epoxy compound derived from a biphenyl ether type epoxy compound.
• the ratio of the number of moles of (meth)acryloyl groups to the number of moles of epoxy groups is preferably 1 or more, and more preferably 2 or more.
• the weight average molecular weight of the (meth)acrylic modified epoxy compound measured by gel permeation chromatography (GPC) is preferably 300 to 500.
• a (meth)acrylic compound is a compound having one or more (meth)acryloyl groups in the molecule. However, a (meth)acrylic compound does not include a compound having both a (meth)acryloyl group and an epoxy group.
• a curable compound may contain only one type of (meth)acrylic compound, or may contain two or more types.
• the number of (meth)acryloyl groups contained in one molecule of a (meth)acrylic compound may be one or more.
• Examples of (meth)acrylic compounds containing one (meth)acryloyl group in one molecule include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate.
• Examples of (meth)acrylic compounds having two or more (meth)acryloyl groups in one molecule include di(meth)acrylates derived from polyethylene glycol, propylene glycol, polypropylene glycol, etc.; di(meth)acrylates derived from tris(2-hydroxyethyl)isocyanurate; di(meth)acrylates derived from a diol obtained by adding 4 or more moles of ethylene oxide or propylene oxide to 1 mole of neopentyl glycol; di(meth)acrylates (bisphenol A or F type epoxy (meth)acrylates) derived from a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A or bisphenol F; di- or tri(meth)acrylates derived from a polyol obtained by adding 2 or 3 moles of ethylene oxide or propylene oxide to 1 mole of trimethylolpropane; di(meth)acrylates derived from a diol obtained by
• di(meth)acrylate derived from a diol obtained by adding 2 moles of ethylene oxide or propylene oxide to 1 mole of bisphenol A or bisphenol F (bisphenol A or F type epoxy (meth)acrylate) is preferred.
• the weight average molecular weight of the (meth)acrylic compound measured by gel permeation chromatography is preferably 200 to 10,000, and more preferably 200 to 5,000.
• the weight average molecular weight of the (meth)acrylic compound is preferably about 310 to 1000.
• the weight average molecular weight is a value measured, for example, by gel permeation chromatography (GPC) in terms of polystyrene.
• the total amount of the (meth)acrylic modified epoxy compound and the (meth)acrylic compound may be 50% by mass or less, preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 30% by mass or less, based on the total amount of the curable compounds.
• the total amount is 5% by mass or more, it is easy to appropriately increase the viscosity of the curable composition after light irradiation, and it is easy to further increase the shape retention.
• the total amount is 50% by mass or less, the relative amount of the epoxy compound increases, so that it is easy to keep the viscosity of the curable composition after light irradiation low, and the fluidity and tackiness are not easily impaired.
• the total amount of the curable compounds may be the same as the total amount of the epoxy compound, the (meth)acrylic modified epoxy compound, and the (meth)acrylic compound.
• the curable compound may further contain an oxetane compound and the like in addition to the above.
• the total amount of the curable compounds is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 70% by mass or less, relative to the total amount of the curable composition.
• the curability of the curable composition tends to be higher.
• the total amount is 90% by mass or less, for example, when an inorganic filler is included, the relative amount of the inorganic filler is large, so that the shape retention and low moisture permeability are more likely to be improved.
• the photocationic polymerization initiator has a function of curing the curable compound.
• the photocationic polymerization initiator is, for example, a photoacid generator that generates an acid upon light irradiation. Note that the photocationic polymerization initiator may also instantaneously generate radicals when generating an acid upon light irradiation.
• the absorption wavelength of the photocationic polymerization initiator is not particularly limited, but it is preferable that the photocationic polymerization initiator absorbs light having a wavelength of 360 nm or more, and it is more preferable that the photocationic polymerization initiator absorbs light having a wavelength of 360 nm or more and 430 nm or less. If the absorption wavelength of the photocationic polymerization initiator is within the above range, it is possible to reduce the effect on optical elements, for example.
• the photocationic polymerization initiator is not particularly limited, and any known photocationic polymerization initiator can be used.
• photocationic polymerization initiator examples include aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, and the like, whose anion portion is BF 4 ⁇ , (Rf) n PF 6 -n ⁇ (Rf is an organic group, n is an integer of 1 to 5), PF 6 ⁇ , SbF 6 ⁇ , or BX 4 ⁇ (X is a phenyl group substituted with at least two or more fluorine or trifluoromethyl groups).
• aromatic sulfonium salts include bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluorophosphate, bis[4-(diphenylsulfonio)phenyl]sulfide bishexafluoroantimonate, bis[4-(diphenylsulfonio)phenyl]sulfide bistetrafluoroborate, bis[4-(diphenylsulfonio)phenyl]sulfide tetrakis(pentafluorophenyl)borate, diphenyl-4-(phenylthio)phenylsulfonium hexafluorophosphate, diphenyl-4-(phenylthio)phenylsulfonium hexafluoroantimonate, diphenyl-4-(phenylthio)phenylsulfonium tetrafluoroborate, etc.
• aromatic iodonium salts include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis(pentafluorophenyl)borate, bis(dodecylphenyl)iodonium hexafluorophosphate, bis(dodecylphenyl)iodonium hexafluoroantimonate, bis(dodecylphenyl)iodonium tetrafluoroborate, bis(dodecylphenyl)iodonium tetrakis(pentafluorophenyl)borate, etc.
• aromatic diazonium salts include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis(pentafluorophenyl)borate, etc.
• aromatic ammonium salts examples include 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, etc.
• photocationic polymerization initiators examples include Irgacure 250, Irgacure 270, Irgacure 290 (manufactured by BASF), CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-400PG (manufactured by San-Apro), SP-150, SP-170, SP-171, SP-056, SP-066, SP-130, SP-140, SP-601, SP-606, SP-701 (manufactured by ADEKA).
• sulfonium salts such as Irgacure 270, Irgacure 290, CPI-100P, CPI-101A, CPI-200K, CPI-210S, CPI-310B, CPI-400PG, SP-150, SP-170, SP-171, SP-056, SP-066, SP-601, SP-606, and SP-701 are preferred.
• the cationic photopolymerization initiator may be of one type or of two or more types in combination.
• the content of the photocationic polymerization initiator is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass or less, and even more preferably 0.8 parts by mass or more and 8 parts by mass or less, relative to 100 parts by mass of the curable compound. If the content of the photocationic polymerization initiator is 0.1 parts by mass or more, more acid is likely to be generated by light irradiation, so that the curing reaction when curing by heating can be more likely to occur. In addition, when the curable composition contains a (meth)acrylic-modified epoxy compound or the like, more radicals are instantaneously generated when acid is generated, so that curing by light irradiation can also occur appropriately. If the content of the photocationic polymerization initiator is 20 parts by mass or less, bleed-out can be reduced, so that contamination of optical elements and the like can be reduced.
• Tertiary amines capture the acid generated from the photocationic polymerization initiator upon light irradiation, thereby making it difficult for the curing reaction of the curable compound to occur upon light irradiation, and can suppress an excessive increase in the viscosity of the curable composition after light irradiation.
• Tertiary amines include monofunctional tertiary amines having one amino group in the molecule, bifunctional tertiary amines having two amino groups, and trifunctional or higher tertiary amines having three or more amino groups.
• bifunctional tertiary amines and trifunctional or higher tertiary amines are preferred from the viewpoint of further increasing the acid trapping efficiency, and bifunctional tertiary amines are more preferred from the viewpoint of easier maintenance of compatibility with epoxy compounds.
• the tertiary amine preferably has an N-O bond, from the viewpoint of making it easier to release the trapped acid when heated and further improving low-temperature curing properties.
• a bifunctional tertiary amine having an N-O bond is preferred.
• the tertiary amine has a hindered structure, from the viewpoint of making it easier to release the trapped acid when heated and further improving low-temperature curing properties.
• hindered structures include structures with steric hindrance, such as 2,2,6,6-tetramethylpiperidine.
• the tertiary amine is preferably a bifunctional tertiary amine having an N-O bond, more preferably a bifunctional tertiary amine having an N-O bond and a hindered structure, and even more preferably a tertiary amine having an N-O bond and two 2,2,6,6-tetramethylpiperidine structures in the molecule.
• Such tertiary amines include compounds represented by formula (1) or (2).
• R 3 represents an alkyl group having 1 to 20 carbon atoms.
• Examples of linear or branched alkyl groups having 1 to 20 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and an eicosyl group.
• Two R 3s may be the same or different from each other.
• R 4 represents a linear or branched alkyl group having 1 to 20 carbon atoms.
• linear or branched alkyl groups having 4 to 20 carbon atoms include a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and an eicosyl group.
• Two R 4s may be the same or different from each other.
• R5 represents an alkylene group having 1 to 8 carbon atoms.
• alkylene group having 1 to 8 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, and an octylene group.
• Examples of the compound represented by formula (1) include a compound represented by formula (1-1); examples of the compound represented by formula (2) include a compound represented by formula (2-1).
• tertiary amines can also be used.
• examples of commercially available tertiary amines include Adeka STAB LA-81 (manufactured by ADEKA CORPORATION) and Tinuvin 123 (manufactured by BASF Japan).
• the tertiary amine may contain only one type, or may contain two or more types.
• the content of the tertiary amine is preferably 20 parts by mass or more per 100 parts by mass of the photocationic polymerization initiator from the viewpoint of capturing the acid generated from the photocationic polymerization initiator. If the content of the tertiary amine is 20 parts by mass or more, a larger amount of acid can be trapped, making it easier to suppress the increase in viscosity after light irradiation and increasing tackiness. From the same viewpoint, the content of the tertiary amine is preferably 60 parts by mass or more, and more preferably 65 parts by mass or more, per 100 parts by mass of the photocationic polymerization initiator.
• the upper limit of the content of the tertiary amine is not particularly limited, but it may be, for example, 100 parts by mass or less from the viewpoint of further reducing the amount of tertiary amine remaining as an unreacted component after curing, further reducing the decrease in adhesion and moisture permeability of the cured product, and improving the physical properties of the cured product.
• the content of the tertiary amine is preferably, for example, 0.5 parts by mass or more and 20 parts by mass or less, and more preferably 1 part by mass or more and 5 parts by mass or less, relative to 100 parts by mass of the curable compound. If the content of the tertiary amine is 0.5 parts by mass or more, a larger amount of acid can be trapped, making it easier to suppress an increase in viscosity after light irradiation and further increasing tack. If the content of the tertiary amine is 20 parts by mass or less, the amount of tertiary amine remaining unreacted after heat curing can be reduced, making it possible to further suppress a decrease in the physical properties of the cured product.
• the curable composition may further contain other components in addition to the above-mentioned components.
• the other components include inorganic fillers, photosensitizers, silane coupling agents, curing agents other than photocationic polymerization initiators, tackifiers, organic fine particles, plasticizers, antioxidants, and defoamers.
• the inorganic filler can have the function of improving the shape retention of the cured product and reducing the moisture permeability of the cured product.
• inorganic fillers include calcium carbonate, magnesium carbonate, barium sulfate, magnesium sulfate, aluminum silicate, zirconium silicate, iron oxide, titanium oxide, titanium nitride, alumina other than the above, zinc oxide, silicon dioxide (silica), potassium titanate, kaolin, talc, glass beads, sericite activated clay, bentonite, aluminum nitride, and silicon nitride. Of these, silicon dioxide and talc are preferred.
• the inorganic filler may have a regular shape such as a sphere, plate, or needle, or may have an irregular shape.
• the average primary particle diameter of the inorganic filler is preferably 0.1 ⁇ m or more and 5 ⁇ m or less, and more preferably 0.5 ⁇ m or more and 3 ⁇ m or less, from the viewpoint of, for example, the shape retention and thickness adjustment of the cured product after lamination. If the average primary particle diameter of the inorganic filler is 5 ⁇ m or less, it is easier to reduce unevenness in the thickness of the cured product after lamination, and if it is 0.1 ⁇ m or more, it is possible to further suppress the increase in viscosity.
• the average primary particle diameter of the inorganic filler is in a range smaller than 0.1 ⁇ m, for example, 7 nm or more and less than 100 nm.
• the average primary particle diameter of the inorganic filler can be measured by the laser diffraction method described in JIS Z8825 (2013).
• the specific surface area of the inorganic filler is preferably 0.5 m 2 /g or more and 20 m 2 /g or less.
• the specific surface area of the inorganic filler is measured by the BET method described in JIS Z8830 (2013).
• the curable composition may contain only one type of inorganic filler, or may contain two or more types. From the viewpoint of adjusting the viscosity (thixotropy) and the shape retention and thickness of the cured product, for example, the curable composition may contain an inorganic filler having a relatively small average primary particle diameter (e.g., less than 0.1 ⁇ m) and an inorganic filler having a relatively large average primary particle diameter (e.g., 0.1 ⁇ m or more). It is preferable that the content of the inorganic filler having a relatively small average particle diameter is less than the content of the inorganic filler having a relatively large average particle diameter.
• the content of the inorganic filler is preferably 10 parts by mass or more and 350 parts by mass or less, relative to 100 parts by mass of the curable compound.
• the content of the inorganic filler is 10 parts by mass or more, it is easier to improve the shape retention of the cured product and to reduce moisture permeability.
• the content of the inorganic filler is 350 parts by mass or less, not only is the applicability of the curable composition less likely to be impaired, but also a decrease in adhesive strength due to a decrease in the relative amount of the curable compound or a loss in flexibility of the cured product can be more suppressed. From the same viewpoint, it is more preferable that the content of the inorganic filler is 150 parts by mass or more and 300 parts by mass or less.
• Photosensitizer has the function of further improving the polymerization initiation efficiency of the above-mentioned cationic photopolymerization initiator and further accelerating the curing reaction of the curable compound.
• photosensitizers include thioxanthone compounds such as 2,4-diethylthioxanthone, 2,2-dimethoxy-1,2-diphenylethan-1-one, benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, 4,4'-bis(dimethylamino)benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 9,10-dibutoxyanthracene, etc.
• the curable composition may contain only one type of photosensitizer, or may contain two or more types.
• the content of the photosensitizer is, for example, preferably 0.1 parts by mass or more and 5 parts by mass or less, and more preferably 0.5 parts by mass or more and 2 parts by mass or less, relative to 100 parts by mass of the curable compound.
• the curable composition may contain only one type of photosensitizer, or may contain two or more types.
• Silane Coupling Agent examples include vinyltrimethoxysilane, ⁇ -(meth)acryloxypropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane.
• the content of the silane coupling agent is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 1.0 parts by mass or more and 5.0 parts by mass or less, relative to 100 parts by mass of the curable compound. If the content of the silane coupling agent is 0.1 parts by mass or more, it is easier to increase the adhesive strength of the cured product, and if it is 10 parts by mass or less, it is possible to further reduce the decrease in moisture permeability resistance of the cured product.
• the curable composition may further contain a curing agent other than the photocationic polymerization initiator, as long as the object and effect of the present invention are not impaired.
• a curing agent include a photoradical polymerization initiator.
• the total amount of the other components is preferably 0.1% by mass or more and 50% by mass or less based on the total amount of the curable composition. When the total amount is 50% by mass or less, the viscosity of the curable composition is unlikely to increase excessively, and the coatability is unlikely to be impaired.
• the viscosity of the curable composition measured using an E-type viscometer at 25°C and 2.5 revolutions per minute is, for example, preferably 20 Pa ⁇ s or more and 500 Pa ⁇ s or less, more preferably 30 Pa ⁇ s or more and 300 Pa ⁇ s or less.
• the viscosity of the curable composition is 20 Pa ⁇ s or more, the composition has a moderately high viscosity, and therefore the shape retention during application is more likely to be improved.
• the viscosity of the curable composition is 500 Pa ⁇ s or less, the application property during application by, for example, a dispenser, screen printing, or the like is less likely to be impaired.
• the complex viscosity at 25° C. after 600 seconds is preferably 1.0 ⁇ 10 3 Pa ⁇ s or more and 5.0 ⁇ 10 4 Pa ⁇ s or less, more preferably 2.0 ⁇ 10 3 Pa ⁇ s or more and 3.0 ⁇ 10 4 Pa ⁇ s or less.
• the complex viscosity of the curable composition is 5.0 ⁇ 10 4 Pa ⁇ s or less, it has tack even after light irradiation, and the fluidity at the time of lamination is not easily impaired, and the lamination suitability is not easily impaired.
• the complex viscosity of the curable composition is 1.0 ⁇ 10 3 Pa ⁇ s or more, the applied shape can be well maintained, so that the shape retention of the cured product is high and the leak resistance is easily improved.
• the complex viscosity can be measured by irradiating the curable composition with a metal halide lamp at a UV illuminance of 100 mW/cm2 with an integrated light quantity of 3000 mJ/ cm2 while measuring the curable composition using a dynamic viscoelasticity measuring device (e.g., a MARSIII rheometer manufactured by Haake Corporation) at a measurement frequency of 1 Hz, a cell gap of 30 ⁇ m, and a temperature of 25° C. , and then measuring the complex viscosity after 600 seconds have elapsed.
• a dynamic viscoelasticity measuring device e.g., a MARSIII rheometer manufactured by Haake Corporation
• the viscosity of the curable composition after light irradiation can be adjusted by the content of the tertiary amine and the composition of the curable compound. For example, if the amount of tertiary amine is large relative to the amount of cationic photopolymerization initiator, more acid generated from the cationic photopolymerization initiator upon light irradiation can be trapped, making it easier to suppress an increase in the viscosity of the curable composition after light irradiation. On the other hand, if the amount of (meth)acrylic-modified epoxy compound or (meth)acrylic compound is large, the viscosity after light irradiation is likely to be high.
• the curable composition according to the present embodiment can be used as a sealant since the viscosity of the curable composition according to the present embodiment can be adjusted to a suitable level for bonding after irradiation with light. That is, the sealant contains the curable composition.
• the sealant can be used as a sealant or adhesive for various elements such as organic EL elements, LED elements, liquid crystal elements, semiconductor elements, solar cell elements, etc.
• the sealant may be a sealant for sealing light-emitting elements such as organic EL elements and micro LED elements.
• the sealant may be a surface sealant or a frame sealant. Frame sealants are required to have a high degree of shape retention when cured, and therefore the curable composition is particularly suitable as a frame sealant.
• a display panel according to one embodiment of the present invention has an element substrate, a counter substrate, and a sealing portion disposed between them for sealing the elements.
• the element substrate has a substrate and an element.
• the substrate is a transparent substrate.
• the material of the transparent substrate may be an inorganic material such as glass, or may be a plastic such as polycarbonate, polyethylene terephthalate, polyethersulfone, and PMMA.
• the element may be various elements such as an organic EL element, an LED element (including micro LED), a liquid crystal element, a semiconductor element, and a solar cell element.
• the organic EL element is disposed on the substrate and has a laminated structure of an anode/light-emitting layer/negative electrode.
• the opposing substrate is disposed so as to face the element substrate via the element.
• the opposing substrate may be a transparent substrate similar to that described above.
• the opposing substrate may have, for example, a color filter layer.
• the sealing portion includes a frame-shaped first sealing portion arranged to surround the outer periphery of the element, and a second sealing portion filled in the area surrounded by the first sealing portion.
• the first sealing portion is a hardened product of the first sealant (dam material).
• the second sealing portion is a hardened product of the second sealant (fill material).
• At least one of the first sealant and the second sealant, preferably the first sealant, is the above-mentioned curable composition.
• the display panel can be manufactured by any method.
• the display panel can be manufactured by 1) applying a first sealant in a frame shape on one of the opposing substrate and the element substrate so as to surround a display region; 2) filling a region surrounded by the first sealant applied in a frame shape with a second sealant to form a sealant layer; 3) irradiating the sealant layer with light; 4) bonding one substrate to another substrate via the sealant layer irradiated with light; 5) a step of heating and curing the sealant layer.
• step 1) the first sealant is applied in a frame shape surrounding the display area on one of the opposing substrate and the element substrate, for example, on the opposing substrate.
• application method can be done, for example, with a dispenser or the like.
• step 2 the area surrounded by the frame-shaped application of the first sealant is filled with the second sealant to form a sealant layer.
• the sealant layer is irradiated with light.
• the type of light to be irradiated is appropriately selected depending on the type of cationic photopolymerization initiator in the curable composition, which is the first sealant, but light in the visible light region is preferred, for example light with a wavelength of 370 nm or more and 450 nm or less. This is because light in this range of wavelengths causes relatively little damage to the drive electrode.
• a known light source that emits ultraviolet or visible light can be used, for example a metal halide lamp.
• the amount of light irradiation is preferably such that a suitable amount of tack remains in the curable composition after irradiation.
• the amount of light irradiation may be from 1000 mJ/ cm2 to 10,000 mJ/ cm2 with an intensity of from 10 mW/ cm2 to 1,000 mW/ cm2 .
• the light irradiation starts the hardening of the first sealant and the second sealant. After the light irradiation is finished, the temperature of the substrate may rise to about 35°C, and the substrate may wait in this state. In this way, by waiting for a predetermined time after the light irradiation, rather than bonding the substrates immediately, the hardening of the first sealant and the second sealant progresses appropriately, and the viscosity of the substrate increases.
• step 4 when the viscosity of the first sealant and the second sealant has increased to an appropriate level, the opposing substrate and the element substrate are bonded together via the sealant layer.
• the bonding is performed by pressing the element substrate and the opposing substrate with a press or the like in a vacuum chamber so as to crush the sealant layer.
• the first sealant which has a relatively high viscosity, is present in a frame shape around the second sealant, preventing the second sealant from leaking out.
• step 5 the laminate is heated to heat and harden the first and second sealants.
• the heating temperature may be any temperature at which the sealant layer hardens, and from the viewpoint of minimizing damage to the element due to heat, a low temperature is preferable, for example, a temperature lower than 100°C, preferably 40°C or higher and 90°C or lower, and more preferably 60°C or higher and 85°C or lower.
• the heating time depends on the heating temperature, but is, for example, 60 minutes or longer and 120 minutes or shorter.
• step 3 the viscosity of the curable composition when irradiated with light is adjusted to a predetermined range.
• the curable compound contains an epoxy compound and a (meth)acrylic modified epoxy compound, most of the acid generated by light irradiation is captured by a tertiary amine. Therefore, even when light is irradiated, the epoxy compound is hardly cured, so that the viscosity after light irradiation can be kept low.
• the (meth)acrylic-modified epoxy compound can be cured by a small amount of radicals instantaneously generated by light irradiation, which increases the viscosity of the curable composition appropriately and makes it easier to maintain the applied shape.
• the curable composition irradiated with light can maintain the applied shape while maintaining the fluidity and tackiness during lamination, which allows the sealing property of the cured product to be improved while maintaining the lamination suitability in the step 4).
• step 5 the acid captured by the tertiary amine is released by heating, and the epoxy groups of the epoxy compound or (meth)acrylic modified epoxy compound react and harden. As a result, sufficient adhesive strength is obtained.
• the curable composition is mainly used as a sealant for organic EL elements, but it can also be used as a sealant or adhesive for various elements such as LED elements (including micro LEDs), liquid crystal elements, semiconductor elements, solar cell elements, and as an interlayer filler for touch panels.
• the curable composition can also be used as a sealant or adhesive applied to substrates that do not have optical transparency, such as printed circuit boards used in smart antennas for electric vehicles and substrates having a light-shielding portion under wiring used in dye-sensitized solar cells.
• Epoxy compound (A) (1) Epoxy compound (A1) Epoxy compound (A1-1): Aromatic trifunctional epoxy compound (VG3101L, 2-(glycidyloxyphenyl)propylphenyl)-1,1-di(glycidyloxyphenyl)ethane, solid, manufactured by Printec Co., Ltd.
• Epoxy compound (A1-2) bisphenol F type epoxy resin (YL983U, bifunctional, liquid, manufactured by Mitsubishi Chemical Corporation)
• Tertiary amine (C) A compound represented by the following formula (Tinuvin 123 manufactured by BASF Japan Ltd.)
• Inorganic filler (D) Inorganic filler (D-1): spherical silica (Tokuyama Corporation, Sign Seal SP07M, average particle size 0.7 ⁇ m)
• Inorganic filler (D-2) fine silica powder (Tokuyama Corporation, HM-30S, average particle size 7 nm)
• Inorganic filler (D-3) spherical silica (manufactured by Admatechs Co., Ltd., YA-010C, average particle size 10 nm)
• Silane coupling agent (F) ⁇ KBM403 manufactured by Shin-Etsu Chemical Co., Ltd.
• Curable Composition 170 parts by mass of epoxy compound (A1-1), 170 parts by mass of epoxy compound (A1-2), 60 parts by mass of (meth)acrylic-modified epoxy compound (A2), 15 parts by mass of photocationic polymerization initiator (B), 5 parts by mass of tertiary amine (C), 500 parts by mass of inorganic filler (D-1), 20 parts by mass of inorganic filler (D-2), 15 parts by mass of inorganic filler (D-3), 5 parts by mass of photosensitizer (E), and 30 parts by mass of silane coupling agent (F) were mixed in a roll kneader to obtain a curable composition.
• Viscosity (before light irradiation)
• the viscosity of the obtained curable composition was measured using an E-type viscometer (TVE-35L type viscometer, manufactured by Toki Sangyo Co., Ltd., rotor name: 3° ⁇ R9.7) according to JIS K5600-2-3 ( The measurement was performed at 25° C. in accordance with the cone and plate viscometer method of the 2014 Japanese Patent Application Laid-Open (2014). The rotation speed of the cone and plate during the measurement was 2.5 rotations per minute.
• a coating film having a thickness of 10 ⁇ m was prepared on a 0.7 mm thick non-alkali glass using a bar coater No. 6. The coating film was left for 3 minutes at room temperature (25° C.) while purging with nitrogen. Then, the coating film was irradiated with ultraviolet light (a metal halide lamp with a wavelength of 395 nm, a UV illuminance of 100 mW/cm 2, and an accumulated light quantity of 3000 mJ/cm 2 ). Next, the coating film was touched with a hand wearing a protective gear to confirm the tackiness.
• ultraviolet light a metal halide lamp with a wavelength of 395 nm, a UV illuminance of 100 mW/cm 2, and an accumulated light quantity of 3000 mJ/cm 2 .
• tackiness after light irradiation was evaluated based on the following criteria. 4: Sufficient tack remains. 3: Some tack remains. 2: A little less tack remains, but some tack remains. 1: No tack. A rating of 2 or above was rated as good.
• the above-prepared curable composition was mixed with 2% by mass of 5 ⁇ m spherical silica spacers. This was applied to a 0.7 mm thick non-alkali glass sheet in a shape of 40 mm x 40 mm using a dispenser. The cross-sectional area of the applied curable composition was 5000 ⁇ m3 .
• a second sealant fill material was dropped into the area surrounded by the first sealant in an amount equivalent to the volume of the area, and the two were bonded together under vacuum. Note that a thermosetting epoxy fill material was used as the fill material. The laminate was taken out and heated at 80° C. for 60 minutes to obtain a simple panel.
• the lamination suitability of the obtained simple panel was evaluated based on the following criteria.
• the obtained curable composition was applied in a circular shape on a non-alkali glass of 25 mm x 45 mm x 0.7 mm using a screen plate.
• the seal pattern was a circle with a diameter of 1 mm.
• the coating film of the curable composition was irradiated with light having a wavelength of 365 nm at an irradiation intensity of 100 mW/ cm2 for 30 seconds from one side of the non-alkali glass, and then a pair of non-alkali glass of 0.7 mm thickness was bonded to the coating film, and heated in an oven at 80°C for 60 minutes to obtain a laminate sample.
• the obtained sample was then aged in a thermostatic chamber at 23° C. for 24 hours, and then pulled in a tensile testing machine (Intesco Model 210 tensile testing machine) in a direction parallel to the surface at a speed of 2 mm/min, and the stress at this time was measured.
• a tensile testing machine Intesco
• Shape Retention Property For the simplified panel prepared for the evaluation of the lamination suitability in (3) above, the shape of the first sealing portion (dam) was observed by an electron microscope. Then, the shape retention property was evaluated according to the following criteria. ⁇ : The shape of the dam is maintained. ⁇ : The shape of the dam is deformed. ⁇ : The dam breaks and the fill material flows out. If it was ⁇ , it was rated as good.
• the curable compositions of Examples 1 to 3 have a lower complex viscosity after light irradiation than the curable compositions of Comparative Examples 1 and 2, and are found to retain tack. This shows that they have high lamination suitability and good adhesive strength.
• the curable compositions of Examples 1 to 3 have a moderately higher complex viscosity after light irradiation than the curable compositions of Comparative Examples 3 and 4, and are found to have high shape retention when cured by heating.
• the curable compositions of Examples 4 to 9 have a complex viscosity after light irradiation that is appropriately lower than the curable compositions of Comparative Examples 6 and 7, and it is understood that sufficient tack remains. This shows that the lamination suitability is high and the adhesive strength is also good. Furthermore, the curable compositions of Examples 4 to 9 have a complex viscosity after light irradiation that is appropriately higher than the curable composition of Comparative Example 5, and it is understood that the shape retention during heat curing is better.
• the curable compositions of Examples 2 to 6 which not only contain a predetermined amount or more of tertiary amine but also have a complex viscosity after light irradiation adjusted to a range of 1.0 ⁇ 10 3 Pa ⁇ s or more and 5.0 ⁇ 10 4 Pa ⁇ s or less, moderately increase in viscosity while maintaining a predetermined tack even after light irradiation, and are excellent in both suitability for lamination and shape retention.
• curable composition that has low-temperature curing properties and is capable of achieving both lamination suitability and shape retention.

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