Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—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 curing agents used
• • 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
  • C08G59/40—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 curing agents used
  • C08G59/62—Alcohols or phenols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/15—Heterocyclic compounds having oxygen in the ring
  • C08K5/156—Heterocyclic compounds having oxygen in the ring having two oxygen atoms in the ring
  • C08K5/1575—Six-membered rings

Definitions

• the present invention relates to a delayed curable photocurable resin composition and a sealing material.
• An organic electroluminescence element (organic EL element) has a configuration in which an electron transport layer, a light emitting layer, and an electron injection layer are disposed between an anode and a cathode, and is injected from each electrode by applying a voltage. Light is emitted when the holes and electrons combine in the light emitting layer.
• Such an organic EL element does not require a backlight like a liquid crystal display, can emit light at a low driving voltage, and has various characteristics such as high contrast and flexibility. Collecting.
• dam-fill sealing that combines a dam material that firmly bonds the base material and the lid with a fill material that fills the space between the base material and the lid has attracted attention as a sealing method for organic EL elements.
• a curable resin is used for these dam materials and fill materials, UV light is irradiated to cure the curable resin.
• organic EL elements deteriorate due to moisture, UV light, gas generated during curing (outgas), etc., and therefore, when the organic EL element is irradiated with UV light, the deterioration of the organic EL element is promoted and the element life is shortened. Problem arises.
• Patent Document 1 describes a delayed curable photocurable resin composition in which a small amount of polyalkylene glycol is added as a delayed curing agent to a cationic photopolymerization initiator and a cationic photopolymerizable resin. Since the delayed curable photocurable resin composition requires a certain amount of time to complete curing after UV irradiation, the organic EL element is sealed after irradiating only the delayed curable photocurable resin composition with UV. can do.
• Patent Document 2 describes a photo-post-curable composition containing a photo-cationic polymerizable resin, a photocationic polymerization initiator, and dicyclohexano-18-crown-6-ether as a delayed curing agent.
• this post-photocurable composition it is possible to suppress outgassing during curing.
• dicyclohexano-18-crown-6-ether is composed of a crown ether having a high cation scavenging ability and a large number of alkyl groups. Therefore, it has a higher cation trapping power than crown ether.
• An object of the present invention is to provide a delayed curable photocurable resin composition and a sealing material that have moderate delayed curable properties and suppress the generation of outgas during curing.
• a delayed curable photocurable resin composition comprising a cationic photopolymerizable compound, a cationic photopolymerizable initiator, and a delayed curing agent,
• the delayed curing agent has the following general formula (1):
• R 1 and R 2 are the same or different and are a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, an epoxy group, and a thiol group
• At least one selected from the group consisting of R 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an unsaturated hydrocarbon group having 2 to 20 carbon atoms.
• At least one species is shown.
• x and y are integers of 2 or more. However, x and y are not 2 at the same time.
• a delayed curable photocurable resin composition which is a compound represented by: Item 2.
• Item 3. The delayed curable photocurable resin composition according to item 1 or 2, wherein the delayed curing agent is at least one selected from the group consisting of polytrimethylene ether glycol and polytetramethylene ether glycol.
• Item 4. Item 4. The delayed curable photocurable resin composition according to any one of Items 1 to 3, further comprising a filler.
• Item 5. Item 5.
• the delayed curable photocurable resin composition according to any one of Items 1 to 4 which has a viscosity of 50 mPa ⁇ s to 1,000,000 mPa ⁇ s measured at 25 ° C. and 1 rpm using an E-type viscometer.
• Item 6. 6 A sealing material produced using the delayed curable photocurable resin composition according to any one of items 1 to 5.
• the delayed curable photocurable resin composition of the present invention has a polyalkylene glycol compound having a specific structure as a delayed curing agent, the curing reaction proceeds by light irradiation, but it is possible after light irradiation. Since the working time can be adjusted appropriately, it has moderate delayed curability and little outgassing occurs during curing.
• the delayed curable photocurable resin composition of the present invention can be suitably used as a sealing material, particularly as a sealing material for organic EL elements.
• the delayed curable photocurable resin composition of the present invention is a delayed curable photocurable resin composition containing a photocationic polymerizable compound, a photocationic polymerizable initiator, and a delayed curing agent,
• the delayed curing agent has the following general formula (1):
• R 1 and R 2 are the same or different and are selected from a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, an epoxy group, and a thiol group. At least one selected from the group consisting of: R 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an unsaturated hydrocarbon group having 2 to 20 carbon atoms. At least one species is shown. x and y are integers of 2 or more. However, x and y are not 2 at the same time. z is an integer of 1 or more. ) It is a compound represented by these.
• the delayed curable photocurable resin composition of the present invention contains a photocationically polymerizable compound.
• the photocationically polymerizable compound is not particularly limited as long as it is a compound having at least one photocationically polymerizable functional group in the molecule.
• Examples of the compound having a photocationically polymerizable functional group include compounds having at least one epoxy group, oxetanyl group, hydroxyl group, vinyl ether group, episulfide group, ethyleneimine group and the like in the molecule.
• a compound having at least one epoxy group in the molecule (hereinafter also referred to as an epoxy compound), Alternatively, a compound having at least one oxetanyl group in the molecule (hereinafter also referred to as oxetanyl compound) is preferably used.
• the property (molecular weight) of the photocationically polymerizable compound is not particularly limited, and may be, for example, monomeric, oligomeric, or polymeric. Moreover, these photocationic polymerizable compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them.
• the epoxy compound is not particularly limited.
• bisphenol type epoxy resins such as bisphenol A type epoxy resin and bisphenol F type epoxy resin
• novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin
• Group epoxy resin alicyclic epoxy resin, heterocyclic epoxy resin, polyfunctional epoxy resin, biphenyl type epoxy resin, glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin
• hydrogenated bisphenol A Type epoxy resins alcohol type epoxy resins, brominated epoxy resins, halogenated epoxy resins, rubber-modified epoxy resins, urethane-modified epoxy resins, epoxidized polybutadiene, epoxidized styrene Tajien - styrene block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resins, epoxy group-containing acrylic resins.
• These epoxy compounds may be used individually by 1 type,
• epoxy compound Commercially available products can be used as the epoxy compound.
• epoxy compounds commercially available for example, “Epicoat” series such as trade names “Epicoat 806”, “Epicoat 828”, “Epicoat 1001”, “Epicoat 1002” manufactured by Mitsubishi Chemical Corporation; Examples thereof include “Celoxide” series such as “Celoxide 2021” manufactured by Chemical Industry Co., Ltd.
• the oxetanyl-based compound is not particularly limited.
• These oxetanyl compounds may be used alone
• Examples of other photocationically polymerizable compounds other than the above epoxy compounds and oxetanyl compounds include, for example, epoxide compounds, cyclic ether compounds, vinyl ether compounds, vinylamine compounds, unsaturated hydrocarbon compounds, lactone compounds and other cyclic ester compounds, At least one photocation such as a lactam compound, cyclic carbonate compound, cyclic acetal compound, aldehyde compound, cyclic amine compound, cyclic sulfide compound, cyclosiloxane compound, cyclotriphosphazene compound, and other photocationically polymerizable groups or monomers Examples thereof include a photocationically polymerizable compound having a polymerizable group. Of these, cyclic ether monomers such as epoxide monomers, vinyl organic monomers, and the like are preferably used. These other photocationically polymerizable compounds may be used singly or in combination of two or more.
• HEVE 2-hydroxyethyl vinyl ether
• DEGV diethylene glycol monovinyl ether
• HBVE 4-hydroxybutyl vinyl ether
• Maruzen Petrochemical Co., Ltd. Aron Oxetane
• Etanacor Ube Industries Co., Ltd.
• the delayed curable photocurable resin composition of the present invention contains a photocationic polymerization initiator.
• the cationic photopolymerization initiator is not particularly limited as long as it can generate cations by light irradiation and can initiate the curing reaction of the cationic photopolymerizable compound.
• Examples of the cationic photopolymerization initiator used in the cationic photopolymerizable composition of the present invention include onium salts and mixed ligand metal salts.
• Specific examples of the onium salt include aromatic diazonium salts, aromatic iodonium salts, aromatic sulfonium salts, aromatic phosphonium salts, and aromatic bismuthonium salts.
• the anion of the onium salt is not particularly limited, and may be any of PF 6 ⁇ , SbF 6 ⁇ , B (C 6 F 5 ) 4 ⁇ and the like.
• the mixed ligand metal salt examples include ( ⁇ 6-benzene) ( ⁇ 5-cyclopentadienyl) iron (II), silanol-aluminum complex, and the like. Of these, aromatic sulfonium salts are preferred. These photocationic polymerization initiators can be used alone or in combination of two or more.
• an arylsulfonium salt is preferable, and S, S, S ′, S′-tetraphenyl-S, S ′-(4,4′-thiodiphenyl) disulfonium bishexafluorophosphate, diphenyl- Examples thereof include 4-phenylthiophenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluorophosphate.
• the aromatic sulfonium salt a commercially available product can be used.
• aromatic sulfonium salts include, for example, manufactured by Dow Chemical Co., Ltd., trade name: UVI6992, manufactured by San Apro Co., Ltd., trade name: CPI-100P, manufactured by BASF, Inc., trade name: Irgacure 270 ⁇ Registered trademark of ASF Corporation).
• the cationic photopolymerization initiator is used in a proportion of, for example, about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the cationic photopolymerizable compound (total amount).
• a photocationic polymerization initiator in the above-mentioned range with respect to the photocationically polymerizable compound, the photocationic polymerization composition can be obtained without slowing the polymerization rate when the photocationic polymerizable composition is photocationically polymerized. Good physical properties.
• the delayed curable photocurable resin composition of the present invention has the following general formula (1) as a delayed curing agent:
• R 1 and R 2 are the same or different and each represents a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, an epoxy group, and 1 shows at least one selected from the group consisting of thiol groups.
• halogen atom examples include a fluorine atom, a chlorine atom, and a bromine atom, and a fluorine atom is preferable.
• saturated hydrocarbon group having 1 to 20 carbon atoms examples include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; branched alkyl groups such as isopropyl, isobutyl, and tert-butyl groups; Examples thereof include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Of these, methyl, ethyl and the like are preferable.
• Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, 1-propenyl group and 2-propenyl group (allyl group); alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group Groups and the like. Of these, vinyl groups are preferred.
• R 1 and R 2 are preferably a hydrogen atom, methyl, ethyl or the like.
• R 3 , R 4 , R 5 and R 6 are the same or different and are selected from the group consisting of a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an unsaturated hydrocarbon group having 2 to 20 carbon atoms. At least one.
• saturated hydrocarbon group having 1 to 20 carbon atoms examples include linear alkyl groups such as methyl, ethyl, n-propyl, and n-butyl; branched alkyl groups such as isopropyl, isobutyl, and tert-butyl groups; Examples thereof include cycloalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Of these, methyl, ethyl and the like are preferable.
• Examples of the unsaturated hydrocarbon group having 2 to 20 carbon atoms include alkenyl groups such as vinyl group, 1-propenyl group and 2-propenyl group (allyl group); alkynyl groups such as ethynyl group, 1-propynyl group and 2-propynyl group Groups and the like. Of these, vinyl groups are preferred.
• R 3 , R 4 , R 5 and R 6 are preferably a hydrogen atom, methyl, ethyl or the like.
• X and y are integers of 2 or more. However, x and y are not 2 at the same time. That is, when x is an integer of 2 or more, y is an integer of 3 or more, and when x is an integer of 3 or more, y is an integer of 2 or more.
• the upper limit of x is not particularly limited, and is preferably an integer of 10 or less, and more preferably an integer of 4 or less.
• the upper limit of y is not particularly limited, preferably an integer of 10 or less, and more preferably an integer of 4 or less.
• x is preferably an integer of 3 or more
• Z is an integer of 1 or more, preferably an integer of 3 or more, and more preferably an integer of 5 or more.
• the upper limit of z is not particularly limited, and is preferably an integer of 150 or less, and more preferably an integer of 40 or less.
• the compound represented by the general formula (1) is a polyalkylene glycol compound having a main chain structure in which a dihydric alcohol is dehydrated and condensed into a multimer, A hydrocarbon skeleton sandwiched between an ether bond and an ether bond is a compound in which two hydrocarbon portions having 2 carbon atoms are not continuously connected.
• a cation derived from a photocationic polymerization initiator produced by light irradiation at an ether bond site is cleaved as a catalyst, and the following formula:
• a dioxane derivative having a stable six-membered ring structure as described above is formed, resulting in outgassing.
• the derivative that is considered to be formed by the decomposition of the delayed curable agent is energetically unstable. It is unlikely to occur, and as a result, the generation amount of outgas is considered to be reduced.
• delayed curing agent of the present invention examples include polytrimethylene ether glycol and polytetramethylene ether glycol.
• the delayed curing agent of the present invention is used at a ratio of, for example, about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of the photocationically polymerizable compound (total amount).
• a delayed curing agent in the above range with respect to the cationic photopolymerizable compound a delayed effect can be sufficiently obtained in the delayed curing photocurable resin composition, and the delayed curing photocurable resin composition is cured. It is possible to reduce the amount of outgas generated during the generation.
• the delayed curable photocurable resin composition of the present invention can contain various additives as required.
• additives for example, a filler for further improving the strength of the cured product, an adhesion imparting agent for further improving the adhesiveness, a viscosity adjusting agent for adjusting the viscosity, and thixotropic properties (thixotropic properties) are imparted.
• Thixotropic agent (thixotropic agent) to improve, physical property modifier to improve tensile properties, bulking agent, reinforcing agent, softener (plasticizer), sagging inhibitor, antioxidant (anti-aging agent), Examples thereof include a heat stabilizer, a flame retardant, an antistatic agent, and an organic solvent.
• the filler is not particularly limited, and conventionally known fillers can be widely used.
• fillers include inorganic powders such as colloidal silica, talc, clay, mica, zeolite, aluminum oxide, titanium oxide, chromium oxide, zirconium oxide, calcium carbonate, magnesium oxide; glass balloons, alumina balloons, ceramics Inorganic hollow bodies such as balloons; Organic spherical bodies such as nylon beads, acrylic beads, silicone beads, Teflon (registered trademark) beads; Organic hollow bodies such as vinylidene chloride balloons and acrylic balloons; Glass, polyester, rayon, nylon, cellulose, etc. Monofilament and the like.
• clay, mica, and talc are preferably used because they are excellent in the baffle effect that prevents moisture from entering.
• the adhesiveness-imparting agent is not particularly limited, and conventionally known ones can be widely used.
• adhesion imparting agents include silane coupling agents such as glycidoxytrimethoxysilane, glycidoxypropylmethyldiethoxysilane, N- (aminoethyl) aminopropyltrimethoxysilane, and mercaptopropyltrimethoxysilane; titanium coupling Agents; aluminum coupling agents and the like. These adhesiveness imparting agents can be used alone or in combination of two or more.
• additives other than those described above conventionally known additives can be widely used.
• the delayed curable photocurable resin composition of the present invention preferably includes a filler among the above additives.
• each predetermined amount of various additives such as the photocationic polymerizable compound, photocationic polymerization initiator and curing retarder, and the filler to be added as necessary, Examples thereof include a method of uniformly kneading under normal temperature, under heating, under normal pressure, under reduced pressure, under pressure, or under an inert gas stream.
• the delayed curable photocurable resin composition of the present invention can ensure a sufficient pot life for the curing reaction after irradiation with light.
• the pot life is preferably 5 minutes or more.
• the substrates and the like can be bonded together before curing proceeds, and sufficient adhesive strength can be obtained.
• the amount of outgas after curing the delayed curable photocurable resin composition of the present invention is preferably 500 ppm or less, and more preferably 200 ppm or less.
• the viscosity of the delayed curable photocurable resin composition of the present invention is, for example, at 25 ° C. and 1 rpm when the photocurable composition of the present invention is used as a sealing material for sealing an organic EL element.
• a preferred lower limit is 50 mPa ⁇ s
• a preferred upper limit is 1 million mPa ⁇ s.
• the viscosity is a value obtained when measured under the above conditions using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., TV-22 type).
• the photocationic polymerization initiator is activated by irradiating light, and the curing reaction of the photocationically polymerizable compound proceeds.
• the light source of the light irradiated at this time is not particularly limited as long as it can irradiate light including near ultraviolet light or visible light, for example, low pressure mercury lamp, medium pressure mercury lamp, high pressure mercury lamp, ultra high pressure mercury lamp, excimer Examples include lasers, chemical lamps, black light lamps, microwave-excited mercury lamps, metal halide lamps, sodium lamps, halogen lamps, xenon lamps, fluorescent lamps, sunlight, and electron beam irradiation devices.
• the above various light sources may be used alone or in combination of two or more.
• examples of the irradiation procedure of the various light sources to the photo-curable composition of the present invention include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, and the like. Any irradiation procedure may be used.
• the use of the delayed curable photocurable resin composition of the present invention is not particularly limited. Applications include, for example, adhesives, sealing materials, single-sided tapes, double-sided tapes, sealing films, sealing agents, coating agents, lining agents, printing inks, electronic materials, and the like. Especially, it is preferable to use as an adhesive agent or a sealing material. Also, using these adhesives, sealing materials, single-sided tapes, double-sided tapes, sealing films, etc., display substrate bonding or flexible circuit tape connection, optical component bonding, electronic component mounting, etc. be able to.
• the delayed curable photocurable resin composition of the present invention is extremely suitable as a sealing material for top emission type organic EL devices.
• a sealing material produced using the delayed curable photocurable resin composition of the present invention is also one aspect of the present invention.
• Example 1-5 and Comparative Example 1-4 According to the composition shown in Table 1 below, each material was uniformly mixed with a three roll mill (manufactured by IMEX Co., Ltd., BR-150V), and the organic EL sealing materials of Example 1-5 and Comparative Example 1-4 were used. Produced.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Epoxy Resins (AREA)
• Electroluminescent Light Sources (AREA)
• Sealing Material Composition (AREA)
• Polyethers (AREA)

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• 2016
  • 2016-12-01 CN CN201680068589.6A patent/CN108368238A/zh active Pending
  • 2016-12-01 KR KR1020187017390A patent/KR20180088842A/ko not_active Application Discontinuation
  • 2016-12-01 JP JP2017554184A patent/JPWO2017094854A1/ja active Pending
  • 2016-12-01 WO PCT/JP2016/085778 patent/WO2017094854A1/ja active Application Filing
  • 2016-12-02 TW TW105139902A patent/TW201730238A/zh unknown

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