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
  • C08G59/66—Mercaptans
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16

Definitions

• the present disclosure relates to a composition set, an adhesive composition, and an adhesive.
• Patent Document 1 discloses an epoxy resin composition (adhesive composition) containing an epoxy resin, a polythiol resin, and a latent curing agent.
• compositions containing conventional epoxy resins do not have sufficient curing speed at room temperature (25°C), and there is still room for improvement.
• the main objective of this disclosure is to provide a composition set that can be used to prepare an adhesive composition that has a sufficient curing speed at room temperature (25°C).
• composition set comprising a base agent containing an epoxy resin and a (meth)acryloyl compound, and a curing agent containing an amine compound and a thiol compound, makes it possible to prepare an adhesive composition with a sufficient curing speed.
• the inventors also discovered that the use of an ester-free thiol compound as the thiol compound results in excellent storage stability of the composition set (particularly the curing agent).
• composition set comprising: a base agent containing an epoxy resin having an epoxy group and a (meth)acryloyl compound having a (meth)acryloyl group; and a curing agent containing an amine compound and a thiol compound having a thiol group.
• amine compound is a primary amine compound.
• primary amine compound is an aliphatic primary amine compound.
• ester-free thiol compound is a thiol compound having two or more thiol groups.
• An adhesive composition comprising an epoxy resin having an epoxy group, a (meth)acryloyl compound having a (meth)acryloyl group, an amine compound, and a thiol compound having a thiol group.
• An adhesive comprising a first adherend, a second adherend, and an adhesive part that adheres the first adherend and the second adherend to each other, wherein the adhesive part comprises a cured product of an adhesive composition containing the base agent and the curing agent in the composition set described in any one of [1] to [5], or a cured product of the adhesive composition described in [6].
• composition set according to any one of [1] to [3] and an adhesive body according to [4].
• a composition set comprising: a base agent containing an epoxy resin having an epoxy group and a (meth)acryloyl compound having a (meth)acryloyl group; and a curing agent containing an amine compound and a thiol compound having a thiol group.
• the amine compound is a primary amine compound.
• the primary amine compound is an aliphatic primary amine compound.
• An adhesive comprising a first adherend, a second adherend, and an adhesive part that adheres the first adherend and the second adherend to each other, the adhesive part comprising a cured product of an adhesive composition containing the base agent and the curing agent in the composition set according to any one of [1] to [3].
• a composition set comprising: a base agent containing an epoxy resin having an epoxy group and a (meth)acryloyl compound having a (meth)acryloyl group; and a curing agent containing an amine compound and a thiol compound having a thiol group, wherein the thiol compound includes an ester-free thiol compound.
• a base agent containing an epoxy resin having an epoxy group and a (meth)acryloyl compound having a (meth)acryloyl group
• a curing agent containing an amine compound and a thiol compound having a thiol group, wherein the thiol compound includes an ester-free thiol compound.
• the composition set according to [1] wherein the amine compound is a primary amine compound.
• the primary amine compound is an aliphatic primary amine compound.
• An adhesive comprising a first adherend, a second adherend, and an adhesive part that adheres the first adherend and the second adherend to each other, the adhesive part comprising a cured product of an adhesive composition containing the base agent and the curing agent in the composition set according to any one of [1] to [4].
• a composition set that can prepare an adhesive composition that has a sufficient curing speed at room temperature (25°C). Some forms of the composition set also have excellent storage stability.
• an adhesive body using such a composition set is provided.
• a numerical range indicated using " ⁇ " indicates a range that includes the numerical values before and after " ⁇ " as the minimum and maximum values, respectively.
• the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages.
• the upper or lower limit value of the numerical range may be replaced with a value shown in an example.
• (meth)acrylate means acrylate or the corresponding methacrylate.
• the materials exemplified below may be used alone or in combination of two or more.
• the content of each component in the composition means the total amount of the multiple substances present in the composition, unless otherwise specified.
• composition set The composition set of one embodiment includes a base agent containing an epoxy resin having an epoxy group and a (meth)acryloyl compound having a (meth)acryloyl group, and a curing agent containing an amine compound and a thiol compound having a thiol group.
• the "composition set” can also be called an "adhesive set” or an "adhesive composition set”.
• the composition set of this embodiment can obtain an adhesive composition containing a base agent and a curing agent by mixing the base agent and the curing agent.
• the base material contains an epoxy resin having an epoxy group.
• the number of epoxy groups in the epoxy resin may be 2 or more, or may be 2 to 4.
• the number of epoxy groups in the epoxy resin may be 2.
• epoxy resins examples include glycidyl ether type epoxy resins which are reaction products of bisphenol A, bisphenol F, bisphenol AD, bisphenol S, naphthalenediol, hydrogenated bisphenol A, etc. with epichlorohydrin; novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resins and biphenyl aralkyl type epoxy resins; glycidyl ester type epoxy resins which are reaction products of polybasic acids (e.g., phthalic acid, dimer acid) with epichlorohydrin; glycidyl amine type epoxy resins which are reaction products of amine compounds (e.g., p-aminophenol, diaminodiphenylmethane, isocyanuric acid, etc.) with epichlorohydrin; and aliphatic epoxy resins.
• novolac type epoxy resins such as
• the epoxy equivalent of the epoxy resin is not particularly limited, but may be 90 to 300 g/eq or 110 to 290 g/eq.
• the epoxy resin content may be 50 mass% or more, 55 mass% or more, 60 mass% or more, or 65 mass% or more based on the total amount of the epoxy resin and the (meth)acryloyl compound, from the viewpoints of adhesive strength and heat resistance.
• the epoxy resin content may be 90 mass% or less, 85 mass% or less, 80 mass% or less, or 75 mass% or less based on the total amount of the epoxy resin and the (meth)acryloyl compound, from the viewpoints of viscosity and wettability to the adherend.
• the base agent contains a (meth)acryloyl compound having a (meth)acryloyl group.
• (meth)acryloyl compound includes compounds having a (meth)acryloyl group and an epoxy group.
• the number of (meth)acryloyl groups in the (meth)acryloyl compound may be 1 or 2 or more.
• the number of (meth)acryloyl groups in the (meth)acryloyl compound may be 2 to 4, or may be 2.
• the (meth)acryloyl compound having a (meth)acryloyl group may be an acryloyl compound having an acryloyl group from the viewpoint of reaction rate.
• the molecular weight of the (meth)acryloyl compound may be 150 to 1000, 180 to 800, or 200 to 600, from the viewpoints of viscosity, compatibility with the epoxy resin, and odor.
• the (meth)acryloyl compound may include, for example, a bifunctional (meth)acryloyl compound having two (meth)acryloyl groups.
• the bifunctional (meth)acryloyl compound may be, for example, a di(meth)acrylate of an aliphatic polyol.
• di(meth)acrylate of an aliphatic polyol examples include diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene polypropylene glycol di(meth)acrylate, and bisphenol A type epoxy (meth)acrylate.
• the (meth)acryloyl compound may contain a polyfunctional (meth)acryloyl compound having three or more (meth)acryloyl groups in addition to a difunctional (meth)acryloyl compound.
• polyfunctional (meth)acryloyl compounds include trifunctional (meth)acryloyl compounds such as trimethylolpropane tri(meth)acrylate and pentaerythritol tri(meth)acrylate; and tetrafunctional (meth)acryloyl compounds such as ditrimethylolpropane tetra(meth)acrylate.
• the content of the (meth)acryloyl compound may be 10 mass% or more, 15 mass% or more, 20 mass% or more, or 25 mass% or more based on the total amount of the epoxy resin and the (meth)acryloyl compound, from the viewpoints of viscosity and wettability to the adherend.
• the content of the (meth)acryloyl compound may be 50 mass% or less, 45 mass% or less, 40 mass% or less, or 35 mass% or less based on the total amount of the epoxy resin and the (meth)acryloyl compound, from the viewpoints of adhesive strength and heat resistance.
• the epoxy resin and (meth)acryloyl compound may be the main components of the base material.
• the total content of the epoxy resin and (meth)acryloyl compound may be, for example, 60 mass% or more, 70 mass% or more, 80 mass% or more, or 90 mass% or more based on the total amount of the base material, and may be 100 mass% or less, 99 mass% or less, or 97 mass% or less.
• the curing agent contains an amine compound.
• the amine compound is a compound having an amino group.
• the number of amino groups in the amine compound may be one or more, and may be 2 to 4.
• the number of amino groups in the amine compound may be two.
• the amine compound may be a primary amine compound (a compound having an -NH2 group).
• the amine compound may be a compound having an amino group and not having a thiol group, and is preferably not a compound having both an amino group and a thiol group.
• the molecular weight or number average molecular weight of the amine compound may be 100 to 15,000, 120 to 5,000, or 140 to 2,000.
• the number average molecular weight is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.
• primary amine compounds include aliphatic primary amine compounds having one amino group, such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, and n-decylamine; aliphatic primary amine compounds having two or more amino groups, such as ethylenediamine, 1,6-hexanediamine, 1,3-bisaminomethylcyclohexane, and polyoxypropylenediamine; aromatic primary amine compounds having one amino group, such as aniline and 1-naphthylamine; and aromatic primary amine compounds having two or more amino groups, such as 1,2-phenylenediamine and 1,4-phenylenediamine.
• the primary amine compound may be, for example, an aliphatic primary amine compound or may be an aliphatic primary amine compound having two or more amino groups.
• the content of the amine compound may be 10% by mass or more, 15% by mass or more, 20% by mass or more, or 25% by mass or more based on the total amount of the amine compound and the thiol compound from the viewpoint of reactivity.
• the content of the amine compound may be 50% by mass or less, 45% by mass or less, 40% by mass or less, or 35% by mass or less based on the total amount of the amine compound and the thiol compound from the viewpoint of moist heat resistance.
• the curing agent contains a thiol compound having a thiol group.
• the number of thiol groups possessed by the thiol compound may be 1 or 2 or more, and may be 2 to 6.
• the number of thiol groups possessed by the thiol compound may be 2 or 3.
• the thiol compound may be a compound having a thiol group and not having an amino group, and is preferably not a compound having both an amino group and a thiol group.
• the molecular weight or number average molecular weight of the thiol compound may be 100 to 1000, 120 to 800, or 150 to 600.
• thiol compounds include trimethylolpropane tris(3-mercaptopropionate) (TMTP), pentaerythritol tetrakis(3-mercaptopropionate) (PEMP), dipentaerythritol hexakis(3-mercaptopropionate) (DPMP), tris-[(3-mercaptopropionyloxy)-ethyl]-isocyanurate (TEMPIC), tris(3-mercaptopropyl)isocyanurate (TMPIC), ethylene glycol bisthioglycolate (EGTG), trimethylolpropane tristhioglycolate (TM TG), pentaerythritol tetrakis thioglycolate (PETG), pentaerythritol tetrakis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercap
• thiol compounds include thiol compounds that do not have an ester bond (-C(O)-O-) in the molecule (ester-free thiol compounds).
• ester-free thiol compounds When the thiol compound contains an ester-free thiol compound, the curing agent in the composition set tends to have excellent storage stability.
• the ester-free thiol compound is not particularly limited as long as it is a thiol compound that does not have an ester bond in the molecule, but may be, for example, a thiol compound that has a linking group that links two or more thiol groups, and the linking group is an alkylene chain (alkylene group) in which a part of the carbon atoms may be substituted with at least one atom selected from the group consisting of oxygen atoms and sulfur atoms.
• the number of carbon atoms in the alkylene chain (alkylene group) may be, for example, 1 to 1,000.
• ester-free thiol compounds examples include 1,4-butanedithiol, 1,6-hexaneedithiol, and 1,10-decanedithiol.
• ester-free thiol compounds include thiol compounds having a polyether chain.
• the thiol compounds having a polyether chain may further have a hydroxyl group, for example.
• thiol compounds having a polyether chain include, for example, Polythiol QE340M (trithiol having a polyether chain, manufactured by Toray Fine Chemicals Co., Ltd.); Thiokol LP series (dithiol having a polyether chain, manufactured by Toray Fine Chemicals Co., Ltd.); etc.
• the content of the ester-free thiol compound may be 50-100 mass%, 70-100 mass%, or 90-100 mass%, or may be 100 mass%, based on the total amount of thiol compounds.
• the content of the thiol compound having an ester bond in the molecule may be 0-50 mass%, 0-30 mass%, or 0-10 mass%, or may be 0 mass%, based on the total amount of thiol compounds.
• the thiol compound may include an ester-free thiol compound, but may not include a thiol compound having an ester bond in the molecule.
• the content of the thiol compound may be 50% by mass or more, 55% by mass or more, 60% by mass or more, or 65% by mass or more, based on the total amount of the amine compound and the thiol compound, from the viewpoint of reactivity.
• the content of the thiol compound may be 90% by mass or less, 85% by mass or less, 80% by mass or less, or 75% by mass or less, based on the total amount of the amine compound and the thiol compound, from the viewpoint of pot life.
• the amine compound and the thiol compound may be the main components of the curing agent.
• the total content of the amine compound and the thiol compound may be, for example, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more, and may be 100% by mass or less, 99% by mass or less, or 97% by mass or less, based on the total amount of the curing agent.
• the base agent, the curing agent, or both of them may contain other components in addition to the epoxy resin, the (meth)acryloyl compound, the amine compound, and the thiol compound.
• the other components include inorganic fillers, organic fillers, silane coupling agents, pigments, and the like.
• the content of the other components may be 0 to 40% by mass, 30% by mass or less, 20% by mass or less, or 10% by mass or less, or 1% by mass or more, or 3% by mass or more, based on the total amount of the base agent.
• the content of the other components may be 0 to 40% by mass, 30% by mass or less, 20% by mass or less, or 10% by mass or less, or 1% by mass or more, or 3% by mass or more, based on the total amount of the curing agent.
• inorganic fillers include inorganic particles such as silica, alumina, silica-alumina, titania, zirconia, magnesia, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotlite, and whiskers.
• inorganic particles such as silica, alumina, silica-alumina, titania, zirconia, magnesia, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotlite, and whiskers.
• organic fillers examples include organic particles such as silicone, acrylic silicone, MBS (methacrylate butadiene styrene), polyamide, and polyimide.
• the organic filler may have a uniform structure or a core-shell structure.
• the silane coupling agent may be, for example, a compound having a hydrolyzable silyl group and a functional group that reacts with at least one selected from the group consisting of an epoxy resin, a (meth)acryloyl compound, an amine compound, and a thiol compound.
• the hydrolyzable silyl group is, for example, a group having a silicon atom and 1 to 3 alkoxy groups bonded to the silicon atom.
• the number of carbon atoms in the alkoxy group bonded to the silicon atom may be, for example, 1 to 4.
• the functional group include an amino group, an epoxy group, a thiol group, and a (meth)acryloyl group.
• compounds having a hydrolyzable silyl group and a functional group are classified as silane coupling agents.
• silane coupling agents include, for example, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-5803, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103P, KBM-573, KBM-575, KBM-802, and KBM-803 (all product names manufactured by Shin-Etsu Chemical Co., Ltd.).
• pigments examples include carbon black and titanium oxide particles.
• the storage conditions for the base agent and the curing agent are not particularly limited, but may be in an air atmosphere or in an inert gas atmosphere such as a nitrogen atmosphere.
• the storage conditions for the curing agent may be in an inert gas atmosphere such as a nitrogen atmosphere, from the viewpoint of suppressing oxidation of the thiol group of the thiol compound.
• the composition set of this embodiment can obtain an adhesive composition containing a base agent and a curing agent by mixing the base agent and the curing agent.
• the composition set of this embodiment is used, for example, to obtain an adhesive having a first adherend, a second adherend, and an adhesive part that bonds the first adherend and the second adherend to each other.
• An adhesive article includes a first adherend, a second adherend, and an adhesive part that bonds the first adherend and the second adherend to each other.
• the adhesive part includes a cured product of an adhesive composition that contains a base agent and a curing agent in the composition set.
• first and second adherends examples include plastic substrates such as polyvinyl chloride, acrylonitrile/butadiene/styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), poly(methyl methacrylate) (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene/propylene copolymer (EPM), ethylene/propylene/diene polymer (EPDM), and carbon fiber reinforced plastic (CFRP), as well as metal substrates such as aluminum, steel, copper, and stainless steel.
• the first and second adherends may be the same or different from each other.
• adhesives examples include plastic laminate substrates, metal laminate substrates, electronic components, semiconductor components, display components, and vehicle components.
• the adhesive can be manufactured, for example, by a method including the steps of arranging a first adherend and a second adherend with a gap therebetween, injecting a base agent and a curing agent into the gap between the first adherend and the second adherend, and curing the adhesive composition containing the base agent and the curing agent.
• the base agent and the curing agent may be mixed at approximately the same time as they are injected into the gap between the first adherend and the second adherend, or may be mixed and then injected into the gap between the first adherend and the second adherend. Injection into the gap can be performed, for example, using a mixing nozzle.
• the adhesive can also be produced by a method including, for example, the steps of applying an adhesive composition containing a base agent and a curing agent onto a first adherend, bonding the first adherend and a second adherend together with the applied adhesive composition sandwiched between them, and curing the adhesive composition containing a base agent and a curing agent.
• the mixing ratio of the base agent and the curing agent is adjusted so that the adhesive cures appropriately, taking into consideration the stoichiometric ratio of the reaction between the epoxy resin and (meth)acryloyl compound contained in the base agent and the amine compound and thiol compound contained in the curing agent.
• the volume ratio of the base agent to the curing agent and the mass ratio of the base agent to the curing agent may be the same as above.
• the curing conditions are adjusted so that the adhesive composition is appropriately cured.
• the curing conditions may be, for example, an environment of 10 to 40°C.
• the adhesive composition may be cured by heating, and the heating temperature in this case may be, for example, 40 to 120°C.
• the curing time may be, for example, 30 minutes or less.
• composition sets of Examples 1 to 3 which include a base agent containing an epoxy resin and a (meth)acryloyl compound and a curing agent containing an amine compound and a thiol compound, had a shorter curing time in an adhesive composition containing a base agent and a curing agent than the composition sets of Comparative Examples 1 and 2, which do not satisfy these conditions.
• composition sets of Examples 1 and 2 which contain an ester-free thiol compound as the thiol compound of the curing agent, did not observe gelation of the curing agent and were found to have better storage stability than the composition sets of Example 3 and Comparative Example 2, which contain a thiol compound with an ester bond in the molecule as the thiol compound of the curing agent.
• the composition set of Example 1 which was stored under a nitrogen atmosphere, did not generate a coating on the surface layer and was found to have better storage stability than the composition set of Example 2, which was stored under an air atmosphere. From these results, it was confirmed that the composition set of the present disclosure is capable of preparing an adhesive composition having a sufficient curing speed at room temperature (25°C).

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• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Adhesives Or Adhesive Processes (AREA)
• Epoxy Resins (AREA)

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Citations (6)

• 2024
  • 2024-03-27 JP JP2025511070A patent/JPWO2024204435A1/ja active Pending
  • 2024-03-27 WO PCT/JP2024/012446 patent/WO2024204435A1/ja not_active Ceased
  • 2024-03-28 TW TW113111799A patent/TW202442742A/zh unknown

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