Classifications

• • 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
  • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/223—Di-epoxy compounds together with monoepoxy compounds
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/226—Mixtures of di-epoxy compounds
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
• • 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
  • C08G59/20—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 epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
• • 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
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
• • G—PHYSICS
  • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
  • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
  • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
  • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
  • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
  • H10H20/80—Constructional details
  • H10H20/85—Packages
  • H10H20/852—Encapsulations
  • H10H20/854—Encapsulations characterised by their material, e.g. epoxy or silicone resins
• • 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
  • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
• • 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
• • 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
  • H10K59/30—Devices specially adapted for multicolour light emission
  • H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
  • H10K71/50—Forming devices by joining two substrates together, e.g. lamination techniques
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
  • H10K85/10—Organic polymers or oligomers

Definitions

• the present invention relates to a composition, a cured body, a display device, and a method for manufacturing a display device.
• organic electroluminescence (organic EL) display elements and organic thin-film solar cell elements.
• organic thin film elements are easy to fabricate by vacuum deposition, solution coating, and the like, and therefore have excellent productivity.
• An organic electroluminescent display element has a thin film structure in which an organic light-emitting material layer is sandwiched between a pair of electrodes facing each other. Electrons are injected into this organic light-emitting material layer from one electrode and holes are injected from the other electrode, whereby the electrons and holes combine in the organic light-emitting material layer to emit light by themselves.
• Organic electroluminescent display elements have the advantages of having better visibility than liquid crystal display elements and the like that require a backlight, being able to be made thinner, and being able to be driven by a low DC voltage.
• organic electroluminescence display elements have a problem in that when the organic light-emitting material layer or electrodes are exposed to the outside air, their light-emitting characteristics deteriorate rapidly and their lifespan is shortened. Therefore, in order to improve the stability and durability of organic electroluminescence display elements, a sealing technique that isolates the organic light-emitting material layer and electrodes from moisture and oxygen in the air is essential for organic electroluminescence display elements.
• Patent Document 1 describes a sealant for organic electroluminescence display elements that contains a cationic polymerizable compound that contains an epoxy compound having a hydrogenated bisphenol skeleton and a thermal cationic polymerization initiator having a cationic moiety represented by a specific chemical formula, and that is characterized in that the content of the thermal cationic polymerization initiator having a cationic moiety represented by the specific chemical formula is less than 0.1 parts by weight per 100 parts by weight of the cationic polymerizable compound, and that the sealant has excellent low-temperature curing properties, storage stability, and flatness of the cured film.
• Patent Document 2 describes a composition that contains (A) a cationic polymerizable compound, (B) a photocationic polymerization initiator, and (C) one or more phosphoric acid compounds selected from the group consisting of phosphoric esters and phosphorous esters, in which the cationic polymerizable compound (A) contains (A-1) an alicyclic compound having an epoxy group and (A-2) an aromatic compound having an epoxy group, the aromatic compound having an epoxy group (A-2) contains (A-2-1) a bisphenol A type epoxy resin and (A-2-2) a bisphenol F type epoxy resin, and the ratio A1/A2 (mass ratio) of the content A1 of the bisphenol A type epoxy resin (A-2-1) to the content A2 of the bisphenol F type epoxy resin (A-2-2) is 0.2 to 5, and that shows little increase in viscosity after light irradiation, can be suitably used as a sealant for organic electroluminescence elements, and is unlikely to deteriorate the organic electroluminescence elements.
• JP 2016-051602 A International Publication No. 2020/171186
• the present invention provides a composition with an improved balance of application and curing properties, as well as a cured product, a display device, and a method for manufacturing a display device using the composition.
• the inventors conducted extensive research to achieve the above object. As a result, they discovered that the balance between the application property and curing property of the composition can be improved by setting the parameter of the viscosity increase starting temperature of the composition within a specific range, and thus completed the present invention.
• the present invention provides the following composition, cured body, display device, and method for manufacturing a display device.
• a composition comprising a cationic polymerizable compound (A), a cationic polymerization initiator (B), and a curing retarder (X), A composition, wherein when viscosity measurement is performed under the following ⁇ Measurement Condition 1>, the viscosity increase starting temperature at which the viscosity change per unit time becomes 100 mPa ⁇ s/sec is 45°C or higher and 95°C or lower.
• ⁇ Measurement condition 2> Apparatus: Differential scanning calorimeter Temperature: From 0°C to 150°C at a rate of 2°C per minute Sample amount: 5 mg Atmosphere: Nitrogen flow [6] The composition according to any one of the above [1] to [5], wherein the cationically polymerizable compound (A) contains an epoxy group. [7] The composition according to the above-mentioned [6], wherein the cationically polymerizable compound (A) comprises one or more compounds selected from the group consisting of an alicyclic compound (A1) having an epoxy group, an aromatic compound (A2) having an epoxy group, and a glycidyl ether compound (A3).
• the cationic polymerization initiator (B) includes a thermal cationic polymerization initiator.
• the content of the cationic polymerization initiator (B) is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cationic polymerizable compound (A).
• the hardening retarder (X) comprises an amino acid derivative (X1), The composition according to any one of the above-mentioned [1] to [12], wherein the amino acid derivative (X1) has an amide group and an ester group.
• the composition according to the above-mentioned [13], wherein the molecular weight of the amino acid derivative (X1) is 130 or more and 1000 or less.
• the content of the curing retarder (X) is 0.01 parts by mass or more and 10 parts by mass or less per 100 parts by mass of the cationically polymerizable compound (A).
• the composition according to [16] above, wherein the light-emitting diode element comprises an organic electroluminescence display element or a micro LED.
• a display device comprising: a light-emitting diode element; a substrate; and a cured sealing layer formed from the cured body according to the above item [18] and located between the light-emitting diode element and the substrate.
• the light-emitting diode element comprises an organic electroluminescence display element or a micro LED.
• the substrate includes a color filter.
• [22] A step of applying the composition according to any one of the above [1] to [17] to at least one of a first substrate and a second substrate; and bonding the first substrate and the second substrate together via the applied composition to obtain a laminate,
• the first substrate includes a light emitting diode element.
• the present invention provides the following method for manufacturing a display device.
• ⁇ 1> applying a composition to at least one of a first substrate and a second substrate; a step of bonding the first substrate and the second substrate together via the applied composition to obtain a laminate; and curing the composition by heating the laminate,
• the first substrate includes a light emitting diode element
• the composition comprises a cationically polymerizable compound (A), a thermal cationic polymerization initiator (B), and a curing retarder (X).
• A cationically polymerizable compound
• B thermal cationic polymerization initiator
• X curing retarder
• ⁇ 3> The method for manufacturing a display device according to the above item ⁇ 1> or ⁇ 2>, wherein the light-emitting diode element includes an organic electroluminescence display element or a micro LED.
• the light-emitting diode element includes an organic electroluminescence display element or a micro LED.
• the second base material includes a color filter.
• ⁇ 5> The method for manufacturing a display device according to any one of ⁇ 1> to ⁇ 4> above, wherein when a viscosity measurement is performed under the following ⁇ Measurement Condition 1>, the composition has a viscosity increase starting temperature of 45° C.
• ⁇ 7> The method for manufacturing a display device according to the above item ⁇ 6>, wherein V 0 is 0.01 mPa ⁇ s or more and 1000 mPa ⁇ s or less.
• V8> The method for manufacturing a display device according to the above item ⁇ 6> or ⁇ 7>, wherein V1 is 0.01 mPa ⁇ s or more and 500 mPa ⁇ s or less.
• ⁇ 9> The method for producing a display device according to any one of ⁇ 1> to ⁇ 8> above, wherein the composition has a heat generation starting temperature of 50° C. or higher in differential scanning calorimetry under the following ⁇ Measurement Condition 2>.
• ⁇ Measurement condition 2> Apparatus: Differential scanning calorimeter Temperature: From 0°C to 150°C at a rate of 2°C per minute Sample amount: 5 mg Atmosphere: Nitrogen flow ⁇ 10> The method for producing a display device according to any one of the above items ⁇ 1> to ⁇ 9>, wherein the cationically polymerizable compound (A) contains an epoxy group. ⁇ 11> The method for producing a display device according to any one of ⁇ 1> to ⁇ 10> above, wherein the thermal cationic polymerization initiator (B) contains an onium salt compound.
• the hardening retarder (X) comprises an amino acid derivative (X1), The method for producing a display device according to any one of the above items ⁇ 1> to ⁇ 12>, wherein the amino acid derivative (X1) has an amide group and an ester group.
• ⁇ 14> The method for producing a display device according to the above item ⁇ 13>, wherein the amino acid derivative (X1) has a molecular weight of 130 or more and 1,000 or less.
• the content of the curing retarder (X) is 0.01 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cationic polymerizable compound (A).
• the present invention provides a composition with an improved balance of application and curing properties, as well as a cured product, a display device, and a method for manufacturing a display device using the composition.
• composition of the present embodiment is a composition containing a cationic polymerizable compound (A), a cationic polymerization initiator (B), and a cure retarder (X), and when viscosity measurement is performed under the following ⁇ Measurement Condition 1>, the viscosity increase starting temperature at which the viscosity change per unit time becomes 100 mPa ⁇ s/sec is 45° C. or higher and 95° C. or lower.
• the viscosity increase starting temperature defined as above is controlled to be 45° C. or more and 95° C. or less. This allows the composition of this embodiment to have an improved balance between the coatability and curability. The reason for this is not clear, but the following reasons are thought to be the cause. Since the composition of the present embodiment has a viscosity increase starting temperature of a certain level or higher, there is a certain amount of time between the start of heating and the start of viscosity increase. In other words, a certain amount of time is ensured for the composition to maintain a viscosity that allows it to wet and spread. This is thought to result in the composition being able to wet and spread appropriately (i.e., the applicability is improved).
• the composition of the present embodiment has a viscosity increase starting temperature that is equal to or lower than a certain level, the curing speed of the composition falls within an appropriate range, which is believed to maintain the curability. It is believed that this improves the balance between coatability and curability.
• the present inventors have studied compositions to be applied to uneven substrates such as color filters and substrates with light-emitting diode elements (TFT substrates), and have found that uneven coating is an issue with such uneven substrates.
• TFT substrates light-emitting diode elements
• improving the coatability to eliminate the uneven coating results in a loss of curability of the composition.
• there is a trade-off between coatability and curability The present inventors have therefore conducted research to resolve this trade-off relationship, and as a result have found that the trade-off relationship between coatability and curability can be resolved and the performance balance between coatability and curability can be improved by setting the viscosity increase starting temperature of the composition within a certain range.
• the composition of this embodiment has a viscosity rise start temperature above a certain level, which ensures that the composition maintains a viscosity that allows it to wet and spread for a certain amount of time, allowing the composition to flow appropriately into recesses. In other words, the composition is prevented from curing before it flows into the recesses. This makes it possible to apply the composition evenly to uneven substrates.
• the viscosity rise start temperature is below a certain level, the curing speed is within an appropriate range, which also maintains curability.
• cationic polymerizable compound (A), cationic polymerization initiator (B), and cure retarder (X) that constitute the composition of this embodiment, and to appropriately adjust the content ratio of each component.
• the viscosity rise start temperature defined as above is preferably 50°C or higher, more preferably 55°C or higher, even more preferably 60°C or higher, even more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, and even more preferably 80°C or higher, from the viewpoint of further improving the curing properties of the composition, it is preferably 90°C or lower, more preferably 85°C or lower, even more preferably 80°C or lower, and even more preferably 75°C or lower, from the viewpoint of improving the balance of performance between the applicability and the curing properties, it is preferably 50°C or higher but 90°C or lower, more preferably 55°C or higher but 90°C or lower, even more preferably 60°C or higher but 90°C or lower, even more preferably 65°C or higher but 90°C or lower, even more preferably 70°C or higher but 85°C or lower, and even more preferably 75°C or higher but 80°C or lower.
• V1 / V0 is preferably 3 or less, more preferably 2 or less, even more preferably 1 or less, even more preferably 0.9 or less, even more preferably 0.8 or less, and even more preferably 0.7 or less; from the viewpoint of further improving the curability, it is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and even more preferably 0.5 or more; and from the viewpoint of improving the performance balance of the coatability and the curability, it is preferably 0.1 or more and 3 or less, more preferably 0.1 or more and 2 or less, even more preferably 0.1 or more and 1 or less, even more preferably 0.3 or more and 0.9 or less, even more preferably 0.4 or more and 0.8 or less, and even more
• the V0 is preferably 0.01 mPa ⁇ s or more, more preferably 0.1 mPa ⁇ s or more, even more preferably 1 mPa ⁇ s or more, even more preferably 10 mPa ⁇ s or more, even more preferably 100 mPa ⁇ s or more, even more preferably 150 mPa ⁇ s or more, even more preferably 200 mPa ⁇ s or more, even more preferably 250 mPa ⁇ s or more, even more preferably 280 mPa ⁇ s or more, and from the viewpoint of further improving the coatability, it is preferably 1000 mPa ⁇ s or less, more preferably 900 mPa ⁇ s or less, even more preferably 800 mPa ⁇ s or less, even more preferably 700 mPa ⁇ s or less, even more preferably 600 mPa ⁇ s or less, and From the viewpoint of further improving the coatability, the viscosity is preferably 0.01 mPa ⁇ s or more and 1000 mP
• the viscosity V1 is preferably 0.01 mPa ⁇ s or more, more preferably 0.1 mPa ⁇ s or more, even more preferably 1 mPa ⁇ s or more, even more preferably 10 mPa ⁇ s or more, even more preferably 100 mPa ⁇ s or more, and even more preferably 150 mPa ⁇ s or more.
• the viscosity V1 is preferably 500 mPa ⁇ s or less, more preferably 480 mPa ⁇ s or less, even more preferably 460 mPa ⁇ s or less, and even more preferably From the viewpoint of further improving the coatability, the viscosity is preferably from 0.01 mPa ⁇ s to 500 mPa ⁇ s, more preferably from 0.1 mPa ⁇ s to 500 mPa ⁇ s, even more preferably from 1 mPa ⁇ s to 500 mPa ⁇ s, even more preferably from 10 mPa ⁇ s to 480 mPa ⁇ s, even more preferably from 100 mPa ⁇ s to 460 mPa ⁇ s, and even more preferably from 150 mPa ⁇ s to 440 mPa ⁇ s.
• the heat generation start temperature of the composition of this embodiment in differential scanning calorimetry under the ⁇ Measurement Condition 2> below is preferably 50°C or higher, more preferably 55°C or higher, and even more preferably 58°C or higher, from the viewpoint of further improving the coatability, and is, for example, 150°C or lower, preferably 120°C or lower, more preferably 110°C or lower, even more preferably 100°C or lower, even more preferably 95°C or lower, and even more preferably 90°C or lower, from the viewpoint of improving the balance of coatability and curability, and is preferably 50°C or higher and 150°C or lower, more preferably 50°C or higher and 120°C or lower, even more preferably 50°C or higher and 110°C or lower, even more preferably 50°C or higher and 100°C or lower, even more preferably 55°C or higher and 95°C or lower, and even more preferably 58°C or higher and 90°C or lower.
• the heat generation onset temperature can be determined from the DSC curve obtained under the above-mentioned ⁇ Measurement Condition 2>. Specifically, the heat generation onset temperature can be determined as the intersection point between the baseline of the DSC curve before the onset of heat generation and the tangent to the point where the change in the amount of heat generation is maximum after the onset of heat generation.
• the liquid density of the composition of this embodiment in an atmosphere of 25°C is preferably 1.10 or more, more preferably 1.12 or more, even more preferably 1.15 or more, even more preferably 1.20 or more, and is preferably 4 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.5 or less.
• the liquid density of the composition of this embodiment is a value measured using a 5 mL Gay-Lussac type pycnometer in accordance with 8.2.2 of JIS-K-0061. The type and content of each component of the composition of this embodiment may be appropriately adjusted so that the liquid density falls within the above range.
• the static surface tension of the composition of this embodiment is preferably 50 mN/m or less, more preferably 40 mN/m or less, and even more preferably 35 mN/m or less, from the viewpoint of further improving the applicability.
• the lower limit of the static surface tension is not particularly limited, but may be, for example, 10 mN/m or more, 20 mN/m or more, or 25 mN/m or more.
• the pendant drop method is a method in which a liquid is pushed out from the tip of a tube and the surface tension is calculated from the shape of the pendant drop that hangs down.
• Component (A) is a compound having cationic polymerizability, and can also be called a compound having a cationic polymerizable group.
• the cationic polymerizable group include cyclic ether groups such as an epoxy group (oxirane ring) and an oxetane group (oxetane ring); and cationic polymerizable vinyl groups.
• Component (A) preferably contains an epoxy group. That is, the component (A) preferably contains one or more compounds selected from the group consisting of an epoxy compound, an oxetane compound, and a cationically polymerizable vinyl compound, and more preferably contains an epoxy compound.
• the epoxy compound include an alicyclic compound (A1) having an epoxy group (alicyclic epoxy compound), an aromatic compound (A2) having an epoxy group (aromatic epoxy compound), and a glycidyl ether compound (A3).
• Component (A) may be a compound having one cationic polymerizable group, or may be a compound having two or more cationic polymerizable groups.
• Component (A) preferably has two or more cationic polymerizable groups, and more preferably has two cationic polymerizable groups.
• component (A) preferably contains a bromine atom.
• component (A) containing a bromine atom means that it contains a bromine atom-containing compound.
• the component (A1) may be, for example, a compound obtained by epoxidizing a compound having a cycloalkene ring or a derivative thereof.
• the cycloalkene ring include a cyclohexene ring, a cyclopentene ring, and a pinene ring.
• the epoxidation can be carried out, for example, using an oxidizing agent.
• the oxidizing agent include hydrogen peroxide and peracid.
• Such component (A1) include one or more selected from the group consisting of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl(meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl(meth)acrylate), and (3,3',4,4'-diepoxy)bicyclohexyl.
• the (A1) component may be, for example, a compound obtained by hydrogenating a compound having an epoxy group and an aromatic ring, or a derivative thereof.
• compounds having an epoxy group and an aromatic ring include bisphenol A type epoxy resins and bisphenol F type epoxy resins.
• Examples of such (A1) components include hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins.
• component (A1) a compound having a 1,2-epoxycyclohexane structure is preferred.
• a compound having a 1,2-epoxycyclohexane structure for example, a compound represented by formula (A1-1) is preferred.
• X represents a single bond or a linking group (a divalent group having one or more atoms).
• the compound represented by formula (A1-1) is (3,3',4,4'-diepoxy)bicyclohexyl.
• the linking group may be, for example, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked together.
• X is preferably a linking group.
• the linking group is preferably a group having an ester bond, and more preferably a group in which an ester bond and a divalent hydrocarbon group are linked together.
• An example of a compound having a group having an ester bond as a linking group is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (molecular weight 252).
• the divalent hydrocarbon group is preferably an alkanediyl group, more preferably an alkanediyl group having 1 to 3 carbon atoms.
• the compound represented by formula (A1-1) is preferably 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
• the molecular weight of the (A1) component is preferably 450 or less, more preferably 400 or less, even more preferably 300 or less, and even more preferably 280 or less.
• the molecular weight of the (A1) component may be, for example, 100 or more, 150 or more, or 200 or more.
• the number average molecular weight of the component (A1) is preferably in the above-mentioned range.
• the number average molecular weight refers to a value calculated in terms of polystyrene measured by gel permeation chromatography (GPC) under the following measurement conditions.
• the content of the (A1) component in the composition of this embodiment when the total amount of the (A) component in the composition of this embodiment is taken as 100 parts by mass, is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 18 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, and is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less, even more preferably 60 parts by mass or less.
• Component (A2) Aromatic Compound Having an Epoxy Group
• Component (A2) is a compound having an epoxy group and an aromatic ring.
• Component (A2) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups.
• Component (A2) preferably has two or more epoxy groups, and more preferably has two epoxy groups.
• Component (A2) may be a compound having no alicyclic group.
• Component (A2) may be used alone or in combination of two or more.
• any of a monomer, oligomer, or polymer can be used, and examples thereof include one or more selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, novolac phenol type epoxy resins, cresol novolac type epoxy resins, and modified products thereof.
• halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether
• bromine atom-containing epoxy resins such as brominated bisphenol A type epoxy resins, brominated bisphenol F type novolac type epoxy resins, and brominated phenol novolac type epoxy resins
• other bromine atom-containing aromatic epoxy compounds As the bromine atom-containing aromatic epoxy compound, halophenyl glycidyl ether is preferred.
• dibromophenyl glycidyl ether is preferred.
• the (A2) component preferably contains one or more compounds selected from the group consisting of compounds having a bisphenol structure (e.g., bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.) and bromine atom-containing aromatic epoxy compounds, more preferably contains one or more compounds selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and halophenyl glycidyl ethers, even more preferably contains one or more compounds selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and dibromophenyl glycidyl ethers, and even more preferably contains at least one compound selected from the group consisting of bisphenol F type epoxy resins and dibromophenyl glycidyl ethers.
• a bisphenol structure e.g., bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.
• bromine atom-containing aromatic epoxy compounds more preferably contains one or more compounds selected from the group
• the molecular weight of the (A2) component is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more, and is preferably 5000 or less, more preferably 1000 or less, even more preferably 700 or less, and even more preferably 450 or less.
• the number average molecular weight of component (A2) is within the above range.
• the number average molecular weight refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the measurement conditions described above.
• the content of component (A2) in the composition of this embodiment when the total amount of component (A) in the composition of this embodiment is taken as 100 parts by mass, is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, and is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 82 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less.
• Component (A3) Glycidyl Ether Compound Component (A3) is a compound having a glycidyl ether group. Component (A3) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups. Component (A3) preferably has two or more epoxy groups, and more preferably has two epoxy groups. Component (A3) may be a compound having no alicyclic group or aromatic ring. Component (A3) may be used alone or in combination of two or more. Component (A3) is preferably excluding components (A1) and (A2).
• the component (A3) is preferably a diglycidyl ether compound.
• the diglycidyl ether compound preferably includes one or more selected from the group consisting of diglycidyl ethers of alkylene glycols, such as diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,6-hexanediol, and diglycidyl ether of neopentyl glycol; polyglycidyl ethers of polyhydric alcohols, such as di- or triglycidyl ethers of glycerin or an alkylene oxide adduct thereof; and diglycidyl ethers of polyalkylene glycols, such as diglycidyl ethers of polyethylene glycol or an alkylene oxide adduct thereof, and diglycidyl ethers of polypropylene glycol or an alkylene oxide adduct
• the diglycidyl ether of alkylene glycol preferably includes one or more selected from the group consisting of diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,6-hexanediol, and diglycidyl ether of neopentyl glycol, and more preferably includes one or two selected from the group consisting of diglycidyl ether of 1,6-hexanediol and diglycidyl ether of neopentyl glycol.
• the alkylene glycol include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, etc.
• the polyalkylene glycol include polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or its alkylene oxide adduct, etc.
• the alkylene oxide include ethylene oxide, propylene oxide, etc.
• the content of component (A3) in the composition of this embodiment when the total amount of component (A) in the composition of this embodiment is taken as 100 parts by mass, is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less.
• the total content of the (A1), (A2) and (A3) components in the composition of this embodiment when the total amount of the (A) component in the composition of this embodiment is taken as 100 parts by mass, is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, and is, for example, 100 parts by mass or less.
• the component (B) contains one or more members selected from the group consisting of a photocationic polymerization initiator that can be activated by light to initiate cationic polymerization of the component (A) and a thermal cationic polymerization initiator that can be activated by heat to initiate cationic polymerization of the component (A).
• the component (B) preferably contains a thermal cationic polymerization initiator.
• thermal cationic polymerization initiators include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by ADEKA CORPORATION), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the CI series (manufactured by Nippon Soda Co., Ltd.).
• the (B) component preferably contains an onium salt compound, more preferably contains one or more selected from the group consisting of sulfonium salt compounds, phosphonium salt compounds, iodonium salt compounds, and ammonium salts, even more preferably contains an ammonium salt compound, even more preferably contains a quaternary ammonium salt compound, and even more preferably contains one or more selected from the group consisting of quaternary ammonium salts of boric acid, quaternary ammonium salts of hexafluoroantimony acid, and quaternary ammonium salts of trifluoromethanesulfonic acid.
• Component (B) may be dissolved in a solvent in advance to facilitate mixing with other components such as component (A).
• the solvent is not particularly limited, but examples include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.
• the content of the (B) component in the composition of this embodiment is, relative to 100 parts by mass of the (A) component, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, from the viewpoint of further improving the curability, from the viewpoint of suppressing deterioration of the object to which the composition is applied, and from the viewpoint of improving the durability of the cured body obtained from the composition, it is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3.0 parts by mass or less, and even more preferably 2.5 parts by mass or less, and from the viewpoint of further improving the curability, from the viewpoint of suppressing deterioration of the object to which the composition is applied, and from the viewpoint of improving the durability of the cured body obtained from the composition, it is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts
• Component (X) Cure Retarder
• Component (X) is an agent that can retard the curing of the composition of this embodiment.
• the (X) component preferably contains one or more compounds selected from the group consisting of amino acid derivatives (X1), ether compounds (X2), thioether compounds (X3), metal complex compounds (X4) and nitroxy radical compounds (X5), more preferably contains one or more compounds selected from the group consisting of amino acid derivatives (X1) and ether compounds (X2), and even more preferably contains an amino acid derivative (X1).
• the content of the (X) component in the composition of this embodiment is, relative to 100 parts by mass of the (A) component, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, from the viewpoint of further improving the performance balance between the application property and the curing property, and from the viewpoint of improving the storage stability, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 2.0 parts by mass or less, and even more preferably 1.5 parts by mass or less, and from the viewpoint of further improving the performance balance between the application property and the curing property, and from the viewpoint of improving the storage stability, preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, even more preferably 0.2 parts by mass or more and 5 parts by mass or less, even more preferably 0.5 parts by mass or more and
• Component (X1) Amino Acid Derivative
• the component (X1) is a compound having an amide group and an ester group in the molecule.
• the (X1) component preferably contains an aspartic acid derivative, and more preferably contains a compound represented by the following general formula (1).
• the compound represented by the following general formula (1) can be synthesized, for example, by referring to the method described in Japanese Patent No. 3379997.
• R1 and R2 each independently represent one or more selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, a substituted alkyl group having from 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, and are preferably an alkyl group having from 1 to 20 carbon atoms, more preferably an alkyl group having from 1 to 10 carbon atoms, even more preferably an alkyl group having from 1 to 6 carbon atoms, even more preferably an alkyl group having from 2 to 4 carbon atoms, and even more preferably an isobutyl group.
• R1 and R2 are preferably one or two groups selected from the group consisting of alkyl groups having a branched structure and substituted alkyl groups having a branched structure, and more preferably an alkyl group having a branched structure.
• R3 is independently one or more selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 2 to 16 carbon atoms, even more preferably an alkyl group having 4 to 14 carbon atoms, even more preferably an alkyl group having 6 to 12 carbon atoms, even more preferably an alkyl group having 8 to 10 carbon atoms, and even more preferably an alkyl group having 10 carbon atoms.
• R 4 is independently one or more selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group,
• m is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 16 or less, more preferably an integer of 1 or more and 12 or less, even more preferably an integer of 1 or more and 10 or less, even more preferably an integer of 1 or more and 8 or less, even more preferably an integer of 1 or more and 6 or less, even more preferably an integer of 1 or more and 4 or less, even more preferably an integer of 1 or more and 3 or less, even more preferably 3.
• n is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 16 or less, more preferably an integer of 1 or more and 12 or less, even more preferably an integer of 1 or more and 10 or less, even more preferably an integer of 1 or more and 8 or less, even more preferably an integer of 1 or more and 6 or less, even more preferably an integer of 1 or more and 4 or less, even more preferably an integer of 1 or more and 2 or less, even more preferably 2.
• the molecular weight of the (X1) component is preferably 130 or more, more preferably 150 or more, even more preferably 200 or more, even more preferably 250 or more, even more preferably 300 or more, even more preferably 350 or more, even more preferably 400 or more, even more preferably 450 or more, and from the viewpoint of further improving the performance balance between application property and curing property, it is preferably 1000 or less, more preferably 900 or less, even more preferably 850 or less, even more preferably 800 or less, It is preferably 750 or less, more preferably 700 or less, even more preferably 650 or less, and even more preferably 600 or less.
• it is preferably 130 to 1000, more preferably 150 to 900, even more preferably 200 to 850, even more preferably 250 to 800, even more preferably 300 to 750, even more preferably 350 to 700, even more preferably 400 to 650, and even more preferably 450 to 600.
• the content of the (X1) component in the composition of this embodiment is, from the viewpoint of further improving the performance balance between the application property and the curing property and from the viewpoint of improving the storage stability, preferably 0.01 parts by mass or more, more preferably 0.02 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, and even more preferably 0.15 parts by mass or more, relative to 100 parts by mass of the (A) component, and from the viewpoint of further improving the performance balance between the application property and the curing property, preferably 5 parts by mass or less, more preferably 2 parts by mass or less, even more preferably 1.0 parts by mass or less, even more preferably 0.8 parts by mass or less, even more preferably 0.5 parts by mass or less, and even more preferably 0.3 parts by mass or less.
• the component (X2) is a compound having an ether bond.
• the component (X2) may be a chain ether or a cyclic ether.
• the chain ether include polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol.
• the polyalkylene oxide include polyoxyethylene-dimethyl ether.
• the cyclic ether include crown ethers. Examples of the crown ether include 18-crown-6-ether and 15-crown-5-ether.
• the (X2) component is preferably a cyclic ether, more preferably a crown ether, and even more preferably 18-crown-6-ether.
• the content of the (X2) component in the composition of this embodiment is, from the viewpoint of further improving the performance balance between the application property and the curing property and from the viewpoint of further improving the storage stability, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, relative to 100 parts by mass of the (A) component, from the viewpoint of further improving the performance balance between the application property and the curing property, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 2.0 parts by mass or less, even more preferably 1.5 parts by mass or less, and even more preferably 1.2 parts by mass or less.
• the component (X3) is a compound having a thioether bond.
• the (X3) component may be a chain thioether or a cyclic thioether.
• Examples of the chain thioether include diethyl thioether, isobutyl sulfide, and dithiaoctanediol.
• Examples of the cyclic thioether include 1,3-dithiane, 1,3,5-trithiane, 1,4,7-trithiacyclononane, and 1,4,8,11-tetrathiacyclotetradecane.
• Component (X4) Metal Complex Compound
• the component (X4) is a metal complex that functions as a cure retarder.
• Examples of the component (X4) include metal acetylacetonates.
• metal acetylacetonates include acetylacetonates of aluminum, titanium, zinc, zirconium, and copper. Among these, acetylacetonates of aluminum and zinc are preferred, and aluminum acetylacetonate is more preferred.
• Component (X5) Nitroxy Radical Compound
• the component (X5) is a compound having a nitroxide group.
• Examples of the (X5) component include 2,2,6,6-tetramethyl-1-piperidinyloxy (hereinafter referred to as TEMPO) or its derivatives such as 4-benzooxyloxy-TEMPO, 4-methoxy-TEMPO, 4-carboxyl-4-amino-TEMPO, 4-chloro-TEMPO, 4-hydroxylimine-TEMPO, 4-hydroxy-TEMPO, and 4-oxo-TEMPO; 4-amino-TEMPO, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (hereinafter referred to as PROXYL) or its derivatives such as 3-carboxyl-PROXYL, 3-carbamoyl-PROXYL, 2,2-dimethyl-4,5-cyclohexyl-PROXYL, 3-oxo-PROXYL, and 3-hydroxylimine-PROXYL.
• PROXYL 3-aminomethyl-PROXYL, 3-methoxy-PROXYL, 3-t-butyl-PROXYL, 3-maleimide-PROXYL, 3,4-di-t-butyl-PROXYL, 3-carboxylic-2,2,5,5-tetramethyl-1-PROXYL, and the like; dialkyl nitroxide radicals or derivatives thereof such as di-t-butyl nitroxide and t-butyl-t-amyl nitroxide; diaryl nitroxide radicals or derivatives thereof such as diphenyl nitroxide; 4,4-dimethyl-1-oxazolidinyloxy (hereinafter referred to as DOXYL) or derivatives thereof such as 2-di-t-butyl-DOXYL, 5-decane-DOXYL, 2-cyclohexane-DOXYL, and the like.
• DOXYL 4,4-dimethyl-1-oxazolidiny
• the total content of the (A), (B) and (X) components in the composition of this embodiment when the total amount of the composition of this embodiment is taken as 100 parts by mass, is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, and is, for example, 100 parts by mass or less, from the viewpoint of further improving the performance balance of application property and curing property.
• composition of this embodiment may further contain other components in addition to the components (A), (B) and (X).
• Other components include, for example, photosensitizers, silane coupling agents, antioxidants, inorganic fillers, resin particles, metal deactivators, bulking agents, stabilizers, neutralizing agents, lubricants, and antibacterial agents.
• the method for producing the composition of this embodiment is not particularly limited as long as the above components can be mixed sufficiently.
• the method for mixing the components is not particularly limited, but examples include a mixing method that uses the mixing force associated with the rotation of a propeller, and a method that uses a normal dispersing machine such as a planetary mixer that rotates and revolves around its axis. These mixing methods are preferred because they are low cost and allow stable mixing.
• composition of this embodiment can be cured using a curing method that suits the composition.
• thermosetting composition it may be cured by heating.
• the heating temperature of the composition is preferably 45°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, even more preferably 60°C or higher, even more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, from the viewpoint of further improving the curing property, and is, for example, 200°C or lower, preferably 150°C or lower, more preferably 120°C or lower, even more preferably 110°C or lower, even more preferably 105°C, even more preferably 100°C or lower, even more preferably 95°C or lower, from the viewpoint of preventing deterioration.
• the composition may be cured by irradiation with light.
• the light source for the irradiation light is not particularly limited, and examples thereof include a halogen lamp, a metal halide lamp, a high-power metal halide lamp (containing indium or the like), a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a xenon excimer lamp, a xenon flash lamp, and an LED.
• the above light sources have different emission wavelengths and energy distributions. Therefore, the light source can be appropriately selected depending on the reaction wavelength of the photocationic polymerization initiator.
• Natural light can also be a reaction initiation light source.
• the irradiation method may be direct irradiation, focused irradiation using a reflecting mirror or the like, or focused irradiation using a fiber or the like. Irradiation may also be performed using a low wavelength cut filter, a heat ray cut filter, a cold mirror, or the like.
• the amount of light irradiation is not particularly limited and may be appropriately adjusted depending on the thickness of the coating film of the composition, etc.
• the amount of light irradiation may be, for example, 50 mJ/cm 2 or more and 20,000 mJ/cm 2 or less, and preferably 100 mJ/cm 2 or more and 10,000 mJ/cm 2 or less.
• composition of this embodiment is not particularly limited, but since the composition of this embodiment has a good balance of application properties and curing properties, it is preferable to use it to encapsulate a light-emitting diode element.
• the light-emitting diode element preferably includes an organic electroluminescence display element or a micro LED.
• composition of this embodiment may also be cured into a predetermined shape (e.g., a film, a sheet, etc.) to form a cured encapsulating layer having a predetermined shape.
• a predetermined shape e.g., a film, a sheet, etc.
• the cured encapsulating layer can be placed on a light-emitting diode element to encapsulate the light-emitting diode element.
• the cured product of the present embodiment is obtained by curing the composition of the present embodiment.
• the composition of this embodiment has a good balance of application properties and curing properties, so the cured product of this embodiment obtained by curing the composition of this embodiment can be suitably used as a cured encapsulating layer (particularly a cured encapsulating layer for a light-emitting diode element).
• the conditions for obtaining the cured product of this embodiment are not particularly limited, and the above-mentioned conditions can be applied as the conditions for curing the composition of this embodiment.
• the display device of the present embodiment includes a light-emitting diode element, a substrate, and a cured sealing layer formed of the above-described cured body and positioned between the light-emitting diode element and the substrate.
• the substrate provided in the display device of this embodiment includes, for example, one or more types selected from the group consisting of a color filter, a glass substrate, a silicon substrate, a plastic substrate, etc., and preferably includes a color filter.
• a manufacturing method of a display device includes the steps of: applying the composition to at least one of a first substrate and a second substrate; and bonding the first substrate and the second substrate together via the applied composition to obtain a laminate, wherein the first substrate includes a light-emitting diode element.
• the manufacturing method of the display device of this embodiment preferably further includes a step of curing the composition by heating the laminate.
• the heating temperature in this step is preferably 45°C or higher, more preferably 50°C or higher, more preferably 55°C or higher, more preferably 60°C or higher, more preferably 65°C or higher, more preferably 70°C or higher, more preferably 75°C or higher, more preferably 80°C or higher, and more preferably 85°C or higher from the viewpoint of further improving curing properties, and is, for example, 200°C or lower, preferably 150°C or lower, more preferably 120°C or lower, more preferably 110°C or lower, more preferably 105°C or lower, more preferably 100°C or lower, and more preferably 95°C or lower from the viewpoint of preventing deterioration.
• the manufacturing method of the display device of this embodiment preferably does not include a step of irradiating the composition applied to the substrate with ultraviolet light in order to cure the composition, from the viewpoint of further improving the balance of application and curing performance.
• the light-emitting diode element of this embodiment preferably includes an organic electroluminescent display element or a micro LED, and more preferably includes a micro LED.
• the substrate of this embodiment includes, for example, one or more substrates selected from the group consisting of a color filter, a glass substrate, a silicon substrate, a plastic substrate, and the like, and preferably includes a color filter.
• examples of the method for applying the composition of the present embodiment to a substrate include coating film formation methods such as a solution coating method and a spray coating method, a flash deposition method, an inkjet method, etc.
• the inkjet method is preferred from the viewpoint of further improving productivity.
• the film thickness of the composition applied on the substrate is, for example, 1 ⁇ m to 15 ⁇ m, preferably 3 ⁇ m to 10 ⁇ m. By forming a film of 1 ⁇ m or more and curing it, it is easy to obtain sufficient sealing ability as a cured sealing layer. In addition, a film thickness of 15 ⁇ m or less leads to miniaturization of display devices and reduction in manufacturing costs.
• a manufacturing method of a display device of the present embodiment includes a step of applying a composition to at least one of a first substrate and a second substrate, a step of bonding the first substrate and the second substrate with the applied composition therebetween to obtain a laminate, and a step of curing the composition by heating the laminate, wherein the first substrate includes a light-emitting diode element, and the composition includes a cationically polymerizable compound (A), a thermal cationic polymerization initiator (B), and a curing retarder (X).
• A cationically polymerizable compound
• B thermal cationic polymerization initiator
• X curing retarder
• the method for producing a display device of the present embodiment it is possible to improve the balance between the performance of the coating property of the composition on the substrate and the curing property on the substrate.
• the reason for this is not clear, the following reasons are considered to be the cause. Since the composition used in the manufacturing method of the display device of this embodiment contains a curing retarder (X), there is a time lag between the start of heating the laminate and the start of the viscosity of the composition increasing. That is, a certain amount of time is ensured for the composition to maintain a viscosity that allows it to wet and spread. Therefore, it is believed that the composition will wet and spread appropriately and then cure appropriately.
• X curing retarder
• the present inventors have studied compositions to be applied to uneven substrates such as color filters and substrates with light-emitting diode elements (TFT substrates), and have found that uneven coating is an issue with such uneven substrates.
• TFT substrates light-emitting diode elements
• improving the coatability to eliminate the uneven coating results in a loss of curability of the composition.
• there is a trade-off between coatability and curability Therefore, the present inventors have conducted research to resolve this trade-off relationship, and have found that the trade-off relationship between coatability and curability can be resolved and the performance balance between coatability and curability can be improved by providing a step of curing the composition by heating the laminate and further blending a curing retarder (X) in the composition.
• X curing retarder
• the composition used in the manufacturing method of the display device of this embodiment contains a curing retarder (X), so a certain amount of time is ensured for the composition to maintain a viscosity that allows it to wet and spread. This allows the composition to flow appropriately into the recesses and then harden. In other words, the composition is prevented from hardening before it flows into the recesses, and the composition hardens after it flows into the recesses. This makes it possible to apply the composition evenly even to uneven substrates.
• X curing retarder
• the heating temperature in the step of heating the laminate is, from the viewpoint of further improving the curing property, preferably 45°C or higher, more preferably 50°C or higher, even more preferably 55°C or higher, even more preferably 60°C or higher, even more preferably 65°C or higher, even more preferably 70°C or higher, even more preferably 75°C or higher, even more preferably 80°C or higher, even more preferably 85°C or higher, and, from the viewpoint of preventing deterioration, is, for example, 200°C or lower, preferably 150°C or lower, more preferably 120°C or lower, even more preferably 110°C or lower, even more preferably 105°C or lower, even more preferably 100°C or lower, even more preferably 95°C or lower.
• the manufacturing method of the display device of this embodiment preferably does not include a step of irradiating the composition applied to the substrate with ultraviolet light to cure the composition. Furthermore, the manufacturing method of the display device of this embodiment can simplify the manufacturing process because it can omit the ultraviolet curing step.
• the light-emitting diode element of this embodiment preferably includes an organic electroluminescent display element or a micro LED, and more preferably includes a micro LED.
• the substrate of this embodiment includes, for example, one or more substrates selected from the group consisting of a color filter, a glass substrate, a silicon substrate, a plastic substrate, and the like, and preferably includes a color filter.
• examples of the method for applying the composition of the present embodiment to a substrate include coating film formation methods such as a solution coating method and a spray coating method, a flash deposition method, an inkjet method, etc.
• the inkjet method is preferred from the viewpoint of further improving productivity.
• the film thickness of the composition applied on the substrate is, for example, 1 ⁇ m to 15 ⁇ m, preferably 3 ⁇ m to 10 ⁇ m. By forming a film of 1 ⁇ m or more and curing it, it is easy to obtain sufficient sealing ability as a cured sealing layer. In addition, a film thickness of 15 ⁇ m or less leads to miniaturization of display devices and reduction in manufacturing costs.
• the viscosity increase starting temperature at which the amount of viscosity change per unit time of the composition of the present embodiment becomes 100 mPa ⁇ s/sec is, from the viewpoint of further improving the coatability, preferably 45° C. or higher, more preferably 50° C. or higher, even more preferably 55° C. or higher, even more preferably 60° C. or higher, even more preferably 65° C. or higher, even more preferably 70° C. or higher, even more preferably 75° C. or higher, and even more preferably 80° C. or higher, and from the viewpoint of further improving the curability of the composition, it is preferably 95° C. or lower, and even more preferably 95° C.
• the temperature is preferably 45° C. or more and 95° C. or less, more preferably 50° C. or more and 95° C. or less, even more preferably 55° C. or more and 95° C. or less, even more preferably 60° C. or more and 95° C. or less, even more preferably 65° C. or more and 90° C. or less, even more preferably 70° C. or more and 85° C. or less, even more preferably 75° C. or more and 80° C. or less, and even more preferably 80° C. or more and 75° C. or less.
• V1 / V0 is preferably 3 or less, more preferably 2 or less, even more preferably 1.0 or less, even more preferably 0.9 or less, even more preferably 0.8 or less, and even more preferably 0.7 or less; from the viewpoint of further improving the curability, it is preferably 0.1 or more, more preferably 0.3 or more, even more preferably 0.4 or more, and even more preferably 0.5 or more; and from the viewpoint of improving the performance balance of the coatability and the curability, it is preferably 0.1 or more and 3 or less, more preferably 0.1 or more and 2 or less, even more preferably 0.1 or more and 1.0 or less, even more preferably 0.3 or more and 0.9 or less, even more preferably 0.4 or more and 0.8 or less, and even
• the V0 is preferably 0.01 mPa ⁇ s or more, more preferably 0.1 mPa ⁇ s or more, even more preferably 1 mPa ⁇ s or more, even more preferably 10 mPa ⁇ s or more, even more preferably 100 mPa ⁇ s or more, even more preferably 150 mPa ⁇ s or more, even more preferably 200 mPa ⁇ s or more, even more preferably 250 mPa ⁇ s or more, even more preferably 280 mPa ⁇ s or more, and from the viewpoint of further improving the coatability, it is preferably 1000 mPa ⁇ s or less, more preferably 900 mPa ⁇ s or less, even more preferably 800 mPa ⁇ s or less, even more preferably 700 mPa ⁇ s or less, even more preferably 600 mPa ⁇ s or less, and From the viewpoint of further improving the coatability, the viscosity is preferably 0.01 mPa ⁇ s or more and 1000 mP
• the viscosity V1 is preferably 0.01 mPa ⁇ s or more, more preferably 0.1 mPa ⁇ s or more, even more preferably 1 mPa ⁇ s or more, even more preferably 10 mPa ⁇ s or more, even more preferably 100 mPa ⁇ s or more, and even more preferably 150 mPa ⁇ s or more.
• the viscosity V1 is preferably 500 mPa ⁇ s or less, more preferably 480 mPa ⁇ s or less, even more preferably 460 mPa ⁇ s or less, and even more preferably From the viewpoint of further improving the coatability, the viscosity is preferably from 0.01 mPa ⁇ s to 500 mPa ⁇ s, more preferably from 0.1 mPa ⁇ s to 500 mPa ⁇ s, even more preferably from 1 mPa ⁇ s to 500 mPa ⁇ s, even more preferably from 10 mPa ⁇ s to 480 mPa ⁇ s, even more preferably from 100 mPa ⁇ s to 460 mPa ⁇ s, and even more preferably from 150 mPa ⁇ s to 440 mPa ⁇ s.
• the heat generation start temperature of the composition of this embodiment in differential scanning calorimetry under the ⁇ Measurement Condition 2> below is preferably 50°C or higher, more preferably 55°C or higher, and even more preferably 58°C or higher, from the viewpoint of further improving the coatability, and is, for example, 150°C or lower, preferably 120°C or lower, more preferably 110°C or lower, even more preferably 100°C or lower, even more preferably 95°C or lower, and even more preferably 90°C or lower, from the viewpoint of improving the balance of coatability and curability, and is preferably 50°C or higher and 150°C or lower, more preferably 50°C or higher and 120°C or lower, even more preferably 50°C or higher and 110°C or lower, even more preferably 50°C or higher and 100°C or lower, even more preferably 55°C or higher and 95°C or lower, and even more preferably 58°C or higher and 90°C or lower.
• the heat generation onset temperature can be determined from the DSC curve obtained under the above-mentioned ⁇ Measurement Condition 2>. Specifically, the heat generation onset temperature can be determined as the intersection point between the baseline of the DSC curve before the onset of heat generation and the tangent to the point where the change in the amount of heat generation is maximum after the onset of heat generation.
• the liquid density of the composition of this embodiment in an atmosphere of 25°C is preferably 1.10 or more, more preferably 1.12 or more, even more preferably 1.15 or more, even more preferably 1.20 or more, and is preferably 4 or less, more preferably 3.0 or less, even more preferably 2.5 or less, even more preferably 2.0 or less, even more preferably 1.5 or less.
• the liquid density of the composition of this embodiment is a value measured using a 5 mL Gay-Lussac type pycnometer in accordance with 8.2.2 of JIS-K-0061. The type and content of each component of the composition of this embodiment may be appropriately adjusted so that the liquid density falls within the above range.
• the static surface tension of the composition of this embodiment is preferably 50 mN/m or less, more preferably 40 mN/m or less, and even more preferably 35 mN/m or less, from the viewpoint of further improving the applicability.
• the lower limit of the static surface tension is not particularly limited, but may be, for example, 10 mN/m or more, 20 mN/m or more, or 25 mN/m or more.
• the pendant drop method is a method in which a liquid is pushed out from the tip of a tube and the surface tension is calculated from the shape of the pendant drop that hangs down.
• Component (A) is a compound having cationic polymerizability, and can also be called a compound having a cationic polymerizable group.
• the cationic polymerizable group include cyclic ether groups such as an epoxy group (oxirane ring) and an oxetane group (oxetane ring); and cationic polymerizable vinyl groups.
• Component (A) preferably contains an epoxy group. That is, the component (A) preferably contains one or more compounds selected from the group consisting of an epoxy compound, an oxetane compound, and a cationically polymerizable vinyl compound, and more preferably contains an epoxy compound.
• the epoxy compound include an alicyclic compound (A1) having an epoxy group (alicyclic epoxy compound), an aromatic compound (A2) having an epoxy group (aromatic epoxy compound), and a glycidyl ether compound (A3).
• Component (A) may be a compound having one cationic polymerizable group, or may be a compound having two or more cationic polymerizable groups.
• Component (A) preferably has two or more cationic polymerizable groups, and more preferably has two cationic polymerizable groups.
• the (A) component preferably contains one or more compounds selected from the group consisting of an alicyclic compound having an epoxy group (A1), an aromatic compound having an epoxy group (A2), and a glycidyl ether compound (A3), and more preferably contains an alicyclic compound having an epoxy group (A1), an aromatic compound having an epoxy group (A2), and a glycidyl ether compound (A3).
• a preferred (A) component contains an alicyclic compound having an epoxy group (A1) and an aromatic compound having an epoxy group (A2).
• component (A) preferably contains a bromine atom.
• component (A) containing a bromine atom means that it contains a bromine atom-containing compound.
• component (A) is thermally polymerizable.
• Component (A1) Alicyclic Compound Having Epoxy Group
• Component (A1) is a compound having an epoxy group and an alicyclic group.
• Component (A1) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups.
• Component (A1) preferably has two or more epoxy groups, more preferably has two epoxy groups.
• Component (A1) may be a compound having no aromatic ring.
• Component (A1) may be used alone or in combination of two or more.
• the component (A1) may be, for example, a compound obtained by epoxidizing a compound having a cycloalkene ring or a derivative thereof.
• the cycloalkene ring include a cyclohexene ring, a cyclopentene ring, and a pinene ring.
• the epoxidation can be carried out, for example, using an oxidizing agent.
• the oxidizing agent include hydrogen peroxide and peracid.
• Such component (A1) include one or more selected from the group consisting of 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexylalkyl(meth)acrylate (e.g., 3,4-epoxycyclohexylmethyl(meth)acrylate), and (3,3',4,4'-diepoxy)bicyclohexyl.
• the (A1) component may be, for example, a compound obtained by hydrogenating a compound having an epoxy group and an aromatic ring, or a derivative thereof.
• compounds having an epoxy group and an aromatic ring include bisphenol A type epoxy resins and bisphenol F type epoxy resins.
• Examples of such (A1) components include hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins.
• a compound having a 1,2-epoxycyclohexane structure is preferred.
• a compound having a 1,2-epoxycyclohexane structure for example, a compound represented by formula (A1-1) is preferred.
• X represents a single bond or a linking group (a divalent group having one or more atoms).
• the compound represented by formula (A1-1) is (3,3',4,4'-diepoxy)bicyclohexyl.
• the linking group may be, for example, a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide bond, or a group in which a plurality of these are linked together.
• X is preferably a linking group.
• the linking group is preferably a group having an ester bond, and more preferably a group in which an ester bond and a divalent hydrocarbon group are linked together.
• An example of a compound having a group having an ester bond as a linking group is 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (molecular weight 252).
• the divalent hydrocarbon group is preferably an alkanediyl group, more preferably an alkanediyl group having 1 to 3 carbon atoms.
• the compound represented by formula (A1-1) is preferably 3',4'-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate.
• the molecular weight of the (A1) component is preferably 450 or less, more preferably 400 or less, even more preferably 300 or less, and even more preferably 280 or less.
• the molecular weight of the (A1) component may be, for example, 100 or more, 150 or more, or 200 or more.
• the number average molecular weight of the component (A1) is preferably in the above-mentioned range.
• the number average molecular weight refers to a value calculated in terms of polystyrene measured by gel permeation chromatography (GPC) under the following measurement conditions.
• the content of the (A1) component in the composition of this embodiment when the total amount of the (A) component in the composition of this embodiment is taken as 100 parts by mass, is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 18 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, and is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 80 parts by mass or less, even more preferably 75 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less, even more preferably 60 parts by mass or less.
• Component (A2) Aromatic Compound Having an Epoxy Group
• Component (A2) is a compound having an epoxy group and an aromatic ring.
• Component (A2) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups.
• Component (A2) preferably has two or more epoxy groups, and more preferably has two epoxy groups.
• Component (A2) may be a compound having no alicyclic group.
• Component (A2) may be used alone or in combination of two or more.
• any of a monomer, oligomer, or polymer can be used, and examples thereof include one or more selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, fluorene type epoxy resins, novolac phenol type epoxy resins, cresol novolac type epoxy resins, and modified products thereof.
• halophenyl glycidyl ethers such as bromophenyl glycidyl ether and dibromophenyl glycidyl ether
• bromine atom-containing epoxy resins such as brominated bisphenol A type epoxy resins, brominated bisphenol F type novolac type epoxy resins, and brominated phenol novolac type epoxy resins
• other bromine atom-containing aromatic epoxy compounds As the bromine atom-containing aromatic epoxy compound, halophenyl glycidyl ether is preferred.
• dibromophenyl glycidyl ether is preferred.
• the (A2) component preferably contains one or more compounds selected from the group consisting of compounds having a bisphenol structure (e.g., bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.) and bromine atom-containing aromatic epoxy compounds, more preferably contains one or more compounds selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and halophenyl glycidyl ethers, even more preferably contains one or more compounds selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and dibromophenyl glycidyl ethers, and even more preferably contains at least one compound selected from the group consisting of bisphenol F type epoxy resins and dibromophenyl glycidyl ethers.
• a bisphenol structure e.g., bisphenol A structure, bisphenol F structure, bisphenol S structure, etc.
• bromine atom-containing aromatic epoxy compounds more preferably contains one or more compounds selected from the group
• the molecular weight of the (A2) component is preferably 100 or more, more preferably 150 or more, and even more preferably 200 or more, and is preferably 5000 or less, more preferably 1000 or less, even more preferably 700 or less, and even more preferably 450 or less.
• the number average molecular weight of component (A2) is within the above range.
• the number average molecular weight refers to a polystyrene-equivalent value measured by gel permeation chromatography (GPC) under the above-mentioned measurement conditions.
• the content of component (A2) in the composition of this embodiment when the total amount of component (A) in the composition of this embodiment is taken as 100 parts by mass, is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, even more preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, even more preferably 30 parts by mass or more, even more preferably 35 parts by mass or more, even more preferably 40 parts by mass or more, and is preferably 90 parts by mass or less, more preferably 85 parts by mass or less, even more preferably 82 parts by mass or less, even more preferably 70 parts by mass or less, even more preferably 65 parts by mass or less.
• Component (A3) Glycidyl ether compound
• Component (A3) is a compound having a glycidyl ether group.
• Component (A3) may be a compound having one epoxy group, or may be a compound having two or more epoxy groups.
• Component (A3) preferably has two or more epoxy groups, more preferably has two epoxy groups.
• Component (A3) may be a compound having no alicyclic group or aromatic ring.
• Component (A3) may be used alone or in combination of two or more.
• Component (A3) is preferably excluding components (A1) and (A2).
• the component (A3) is preferably a diglycidyl ether compound.
• the diglycidyl ether compound preferably includes one or more selected from the group consisting of diglycidyl ethers of alkylene glycols, such as diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,6-hexanediol, and diglycidyl ether of neopentyl glycol; polyglycidyl ethers of polyhydric alcohols, such as di- or triglycidyl ethers of glycerin or an alkylene oxide adduct thereof; and diglycidyl ethers of polyalkylene glycols, such as diglycidyl ethers of polyethylene glycol or an alkylene oxide adduct thereof, and diglycidyl ethers of polypropylene glycol or an alkylene oxide adduct
• the diglycidyl ether of alkylene glycol preferably includes one or more selected from the group consisting of diglycidyl ether of ethylene glycol, diglycidyl ether of propylene glycol, diglycidyl ether of 1,6-hexanediol, and diglycidyl ether of neopentyl glycol, and more preferably includes one or two selected from the group consisting of diglycidyl ether of 1,6-hexanediol and diglycidyl ether of neopentyl glycol.
• the alkylene glycol include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, etc.
• the polyalkylene glycol include polyethylene glycol or its alkylene oxide adduct, polypropylene glycol or its alkylene oxide adduct, etc.
• the alkylene oxide include ethylene oxide, propylene oxide, etc.
• the content of component (A3) in the composition of this embodiment when the total amount of component (A) in the composition of this embodiment is taken as 100 parts by mass, is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, even more preferably 1.0 parts by mass or more, even more preferably 1.5 parts by mass or more, and is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less.
• the total content of the (A1), (A2) and (A3) components in the composition of this embodiment when the total amount of the (A) component in the composition of this embodiment is taken as 100 parts by mass, is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, and is, for example, 100 parts by mass or less.
• the component (B) can be activated by heat to initiate the cationic polymerization of the component (A).
• component (B) Commercially available products of component (B) include, for example, Adeka Opton CP-66, Adeka Opton CP-77 (manufactured by ADEKA CORPORATION), San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.), and the CI series (manufactured by Nippon Soda Co., Ltd.).
• Adeka Opton CP-66 Adeka Opton CP-77
• San-Aid SI-60L San-Aid SI-80L
• San-Aid SI-100L manufactured by Sanshin Chemical Industry Co., Ltd.
• CI series manufactured by Nippon Soda Co., Ltd.
• the (B) component preferably contains an onium salt compound, more preferably contains one or more selected from the group consisting of sulfonium salt compounds, phosphonium salt compounds, iodonium salt compounds, and ammonium salts, even more preferably contains one or more selected from the group consisting of phosphonium salt compounds, iodonium salt compounds, and ammonium salts, even more preferably contains an ammonium salt compound, even more preferably contains a quaternary ammonium salt compound, and even more preferably contains one or more selected from the group consisting of a quaternary ammonium salt of boric acid, a quaternary ammonium salt of hexafluoroantimony acid, and a quaternary ammonium salt of trifluoromethanesulfonic acid.
• an onium salt compound more preferably contains one or more selected from the group consisting of sulfonium salt compounds, phosphonium salt compounds, iodonium salt compounds, and ammonium salts,
• Component (B) may be dissolved in a solvent in advance to facilitate mixing with other components such as component (A).
• the solvent is not particularly limited, but examples include carbonates such as propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, and diethyl carbonate.
• the content of component (B) in the composition of this embodiment is, from the viewpoint of further improving the curability, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.10 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 0.8 parts by mass or more, per 100 parts by mass of component (A); and from the viewpoints of further improving the curability, further suppressing deterioration of the object to which the composition is applied, improving the durability of the cured body obtained from the composition, and improving storage stability, it is preferably 10 parts by mass or less, More preferably, it is 5 parts by mass or less, even more preferably 3 parts by mass or less, and even more preferably 2.5 parts by mass or less.
• it is preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 10 parts by mass or less, even more preferably 0.10 parts by mass or more and 5 parts by mass or less, even more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and even more preferably 0.8 parts by mass or more and 2.5 parts by mass or less.
• Cure Retarder is an agent that can retard the curing of the composition of this embodiment.
• the (X) component preferably contains one or more compounds selected from the group consisting of amino acid derivatives (X1), ether compounds (X2), thioether compounds (X3), metal complex compounds (X4) and nitroxy radical compounds (X5), more preferably contains one or more compounds selected from the group consisting of amino acid derivatives (X1) and ether compounds (X2), and even more preferably contains an amino acid derivative (X1).
• the content of the (X) component in the composition of this embodiment is, from the viewpoint of further improving the performance balance between application property and curing property and improving storage stability, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.2 parts by mass or more, even more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, from the viewpoint of further improving the performance balance between application property and curing property, preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 2 parts by mass or less, and even more preferably 1.5 parts by mass or less, and from the viewpoint of further improving the performance balance between application property and curing property and improving storage stability, preferably 0.01 parts by mass or more and 10 parts by mass or less, more preferably 0.1 parts by mass or more and 10 parts by mass or less, even more preferably 0.2 parts by mass or more and 5 parts by mass or less, even more preferably 0.5 parts by mass or more and 2.0 parts by mass or less, and even more preferably
• Component (X1) Amino Acid Derivative
• the component (X1) is a compound having an amide group and an ester group in the molecule.
• the (X1) component preferably contains an aspartic acid derivative, and more preferably contains a compound represented by the following general formula (1).
• the compound represented by the following general formula (1) can be synthesized, for example, by referring to the method described in Japanese Patent No. 3379997.
• R1 and R2 each independently represent one or more selected from the group consisting of a hydrogen atom, an alkyl group having from 1 to 20 carbon atoms, a substituted alkyl group having from 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, and are preferably an alkyl group having from 1 to 20 carbon atoms, more preferably an alkyl group having from 1 to 10 carbon atoms, even more preferably an alkyl group having from 1 to 6 carbon atoms, even more preferably an alkyl group having from 2 to 4 carbon atoms, and even more preferably an isobutyl group.
• R1 and R2 are preferably one or two groups selected from the group consisting of alkyl groups having a branched structure and substituted alkyl groups having a branched structure, and more preferably an alkyl group having a branched structure.
• R3 is independently one or more selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 2 to 16 carbon atoms, even more preferably an alkyl group having 4 to 14 carbon atoms, even more preferably an alkyl group having 6 to 12 carbon atoms, even more preferably an alkyl group having 8 to 10 carbon atoms, and even more preferably an alkyl group having 10 carbon atoms.
• R 4 is independently one or more selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a substituted alkyl group having 1 to 20 carbon atoms, an aryl group, and a substituted aryl group, preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms, more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, even more preferably one or more selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 2 carbon atoms, even more preferably a hydrogen atom or a methyl group,
• m is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 16 or less, more preferably an integer of 1 or more and 12 or less, even more preferably an integer of 1 or more and 10 or less, even more preferably an integer of 1 or more and 8 or less, even more preferably an integer of 1 or more and 6 or less, even more preferably an integer of 1 or more and 4 or less, even more preferably an integer of 1 or more and 3 or less, even more preferably 3.
• n is an integer of 1 or more and 20 or less, preferably an integer of 1 or more and 16 or less, more preferably an integer of 1 or more and 12 or less, even more preferably an integer of 1 or more and 10 or less, even more preferably an integer of 1 or more and 8 or less, even more preferably an integer of 1 or more and 6 or less, even more preferably an integer of 1 or more and 4 or less, even more preferably an integer of 1 or more and 2 or less, even more preferably 2.
• the molecular weight of the (X1) component is preferably 130 or more, more preferably 150 or more, even more preferably 200 or more, even more preferably 250 or more, even more preferably 300 or more, even more preferably 350 or more, even more preferably 400 or more, even more preferably 450 or more, and from the viewpoint of further improving the performance balance between application property and curing property and from the viewpoint of improving storage stability, it is preferably 1000 or less, more preferably 900 or less, even more preferably 850 or less, More preferably, it is 800 or less, more preferably 750 or less, more preferably 700 or less, more preferably 650 or less, and even more preferably 600 or less.
• it is preferably 130 to 1000, more preferably 150 to 900, more preferably 200 to 850, more preferably 250 to 800, more preferably 300 to 750, more preferably 350 to 700, more preferably 400 to 650, and even more preferably 450 to 600.
• Component (X2) Ether Compound
• the component (X2) is a compound having an ether bond.
• the component (X2) may be a chain ether or a cyclic ether.
• the chain ether include polyalkylene oxides such as polyethylene glycol, polypropylene glycol, and polyoxytetramethylene glycol.
• the polyalkylene oxide include polyoxyethylene-dimethyl ether.
• the cyclic ether include crown ethers. Examples of the crown ether include 18-crown-6-ether and 15-crown-5-ether.
• the (X2) component is preferably a cyclic ether, more preferably a crown ether, and even more preferably 18-crown-6-ether.
• Component (X3) Thioether Compound
• the component (X3) is a compound having a thioether bond.
• the (X3) component may be a chain thioether or a cyclic thioether.
• Examples of the chain thioether include diethyl thioether, isobutyl sulfide, and dithiaoctanediol.
• Examples of the cyclic thioether include 1,3-dithiane, 1,3,5-trithiane, 1,4,7-trithiacyclononane, and 1,4,8,11-tetrathiacyclotetradecane.
• Component (X4) Metal Complex Compound
• the component (X4) is a metal complex that functions as a cure retarder.
• Examples of the component (X4) include metal acetylacetonates.
• metal acetylacetonates include acetylacetonates of aluminum, titanium, zinc, zirconium, and copper. Among these, acetylacetonates of aluminum and zinc are preferred, and aluminum acetylacetonate is more preferred.
• Component (X5) Nitroxy Radical Compound
• the component (X5) is a compound having a nitroxide group.
• Examples of the (X5) component include 2,2,6,6-tetramethyl-1-piperidinyloxy (hereinafter referred to as TEMPO) or its derivatives such as 4-benzooxyloxy-TEMPO, 4-methoxy-TEMPO, 4-carboxyl-4-amino-TEMPO, 4-chloro-TEMPO, 4-hydroxylimine-TEMPO, 4-hydroxy-TEMPO, and 4-oxo-TEMPO; 4-amino-TEMPO, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy (hereinafter referred to as PROXYL) or its derivatives such as 3-carboxyl-PROXYL, 3-carbamoyl-PROXYL, 2,2-dimethyl-4,5-cyclohexyl-PROXYL, 3-oxo-PROXYL, and 3-hydroxylimine-PROXYL.
• the total content of the (A), (B) and (X) components in the composition of this embodiment when the total amount of the composition of this embodiment is taken as 100 parts by mass, is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, even more preferably 80 parts by mass or more, even more preferably 90 parts by mass or more, even more preferably 95 parts by mass or more, even more preferably 98 parts by mass or more, and is, for example, 100 parts by mass or less, from the viewpoint of further improving the performance balance of application property and curing property.
• composition of this embodiment may further contain other components in addition to the components (A), (B) and (X).
• Other components include, for example, photosensitizers, silane coupling agents, antioxidants, inorganic fillers, resin particles, metal deactivators, bulking agents, stabilizers, neutralizing agents, lubricants, and antibacterial agents.
• the method for producing the composition of this embodiment is not particularly limited as long as the above components can be mixed sufficiently.
• the method for mixing the components is not particularly limited, but examples include a mixing method that uses the mixing force associated with the rotation of a propeller, and a method that uses a normal dispersing machine such as a planetary mixer that rotates and revolves around its axis. These mixing methods are preferred because they are low cost and allow stable mixing.
• the aspartic acid derivative (x1-1) was synthesized with reference to the method described in Japanese Patent No. 3379997. Specifically, 115 parts by mass of 3-decyloxypropylamine were added dropwise to 120 parts by mass of di-i-butyl maleate over a period of 2.5 hours in a reaction vessel at 75° C. The resulting mixture was stirred at 125° C.
• Component (X2) Ether compound (X2-1) 18-crown-6-ether ("Crown Ether O-18" manufactured by Tokyo Chemical Industry Co., Ltd.)
• V0 and V1 The viscosity of the compositions of the examples and comparative examples was measured under the following ⁇ Measurement Condition 1>, and the temperature at which the viscosity change per unit time reached 100 mPa ⁇ s/sec was defined as the viscosity increase starting temperature. The results are shown in Table 1. The viscosity 20 seconds after the start of the measurement was designated as V0 , and the viscosity at ((the viscosity increase starting temperature)-10)° C. was designated as V1 . These results are also shown in Table 1.
• ⁇ Exothermic start temperature> For the compositions of the Examples and Comparative Examples, the heat generation onset temperatures were measured in differential scanning calorimetry under the following ⁇ Measurement Condition 2>. The results are shown in Table 1.
• ⁇ Measurement condition 2> Apparatus: Differential scanning calorimeter ("DSC6220" manufactured by Hitachi High-Tech Science Corporation) Temperature: 0°C to 150°C at a rate of 2°C per minute Sample amount: 5 mg Atmosphere: Nitrogen flow
• Example 1 As shown in Table 1, firstly, in Examples 1 to 4, the composition had a larger wet-spread area and was superior in applicability compared to Comparative Example 2. Also, all of the Examples cured within a certain time, unlike Comparative Example 1, which cured very slowly and the curing time could not be measured. From these facts, it can be seen that the composition of this embodiment has an excellent balance of applicability and curing performance.
• Examples 1 to 3 which contained the hardening retarder (x1-1), had a larger wet spread area than Example 4, which did not contain the hardening retarder (x1-1). In other words, the coating properties were improved. Furthermore, Examples 1 to 3 had a smaller viscosity increase rate than Example 4. In other words, the storage stability was improved.

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