Classifications

• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/088—Removal of water or carbon dioxide from the reaction mixture or reaction components
  • C08G18/0885—Removal of water or carbon dioxide from the reaction mixture or reaction components using additives, e.g. absorbing agents
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3212—Polyhydroxy compounds containing cycloaliphatic groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3271—Hydroxyamines
  • C08G18/329—Hydroxyamines containing aromatic groups
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/44—Polycarbonates
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• • 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
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
  • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
  • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
• • 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
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/06—Polyurethanes from polyesters
• • 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
  • C08G2170/00—Compositions for adhesives

Definitions

• the present disclosure relates to a urethane resin-forming composition, an adhesive, a cured product, and a method for producing the cured product.
• Fracture toughness is one of the physical properties that has received the most attention.
• the fracture toughness value is considered as a composite index of flexibility and stiffness, and is indicated as a unit of energy. The higher the fracture toughness value, the better the resistance when energy is applied to the adhesive (such as impact), so the higher the fracture toughness value, the better.
• Patent Document 1 describes a first liquid containing a prepolymer obtained by reacting a polyisocyanate with a polyol having a specific molecular weight and a specific blending amount of a filler, and a second liquid containing a polyol having a specific molecular weight and a catalyst. and wherein the number of moles of hydroxyl groups derived from the polyol in the first liquid and the number of moles of hydroxyl groups derived from the polyol in the second liquid have a specific relationship. According to Patent Document 1, such a urethane-based adhesive composition can obtain good adhesive performance and is also excellent in storage stability.
• Patent Document 1 the tensile shear strength is measured as adhesive performance, but the fracture toughness value is not sufficient. Therefore, there is a demand for an adhesive that has a high fracture toughness value and a high degree of compatibility between flexibility and rigidity.
• one aspect of the present disclosure is directed to providing a urethane resin-forming composition and an adhesive capable of forming a cured product having a high fracture toughness value. Moreover, one aspect of the present disclosure is directed to providing a cured product having a high fracture toughness value and a method for producing the same.
• the main component (A) is an isocyanate group-terminated prepolymer (A -1), including
• the curing agent (B) comprises at least one diol (B-1) selected from the group consisting of aliphatic diols and alicyclic diols, and a diol (B-2) represented by the following formula (1). and including A urethane resin-forming composition, wherein at least one of the component (a) and the curing agent (B) contains a polyfunctional component.
• L is a trivalent group consisting of one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms
• R is a group having at least one ring structure selected from the group consisting of an alicyclic structure, an aromatic ring and a heterocyclic ring.
• a two-component adhesive comprising the urethane resin-forming composition according to any one of (1) to (10).
• An automotive structural adhesive comprising the urethane resin-forming composition according to any one of (1) to (10).
• the main component (A) is an isocyanate group-terminated prepolymer (A -1), including
• the curing agent (B) comprises at least one diol (B-1) selected from the group consisting of aliphatic diols and alicyclic diols, and a diol (B-2) represented by the following formula (1). and including A method for producing a cured product, wherein at least one of the component (a) and the curing agent (B) contains a polyfunctional component.
• L is a trivalent group consisting of one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms
• R is a group having at least one ring structure selected from the group consisting of an alicyclic structure, an aromatic ring and a heterocyclic ring.
• a urethane resin-forming composition and an adhesive capable of forming a cured product having a high fracture toughness value.
• an adhesive capable of forming a cured product having a high fracture toughness value.
• a cured product having a high fracture toughness value and a method for producing the same.
• a urethane resin-forming composition includes a main agent (A) and a curing agent (B).
• the urethane resin-forming composition may be a two-component type in which the main agent (A) and the curing agent (B) are present separately, or a one-component composition in which the main agent (A) and the curing agent (B) are combined. It may be of a three-component type or a multi-component type of three or more components. If the one-liquid type requires long-term storage, it is preferable to take known measures such as blocking the isocyanate group-terminated prepolymer (A-1) so that the functional groups do not react in the one-liquid state.
• the urethane resin-forming composition comprises, for example, a first agent containing the main agent (A) and a second agent containing the curing agent (B). , may be included.
• each agent may be in a liquid form at the time of use, and may be solid at room temperature, for example.
• the main component (A) is an isocyanate group-terminated prepolymer (A- 1).
• the curing agent (B) comprises at least one diol (B-1) selected from the group consisting of aliphatic diols and alicyclic diols, and a diol (B-2) represented by the following formula (1). ,including.
• L is a trivalent group consisting of one or more atoms selected from the group consisting of a carbon atom, a hydrogen atom, a nitrogen atom and an oxygen atom; It is a group having at least one ring structure selected from the group consisting of rings. ]
• At least one of component (a) and curing agent (B) contains a polyfunctional component.
• the urethane resin-forming composition may be, for example, a composition that forms a urethane resin having a urethane group concentration of 2000 mmol/kg or more and 4500 mmol/kg or less (more preferably 2500 mmol/kg or more and 4000 mmol/kg or less).
• the main component (A) and curing agent (B) may be a selected composition.
• the main agent (A) contains an isocyanate group-terminated prepolymer (A-1).
• the isocyanate group-terminated prepolymer (A-1) is a reaction product of component (a) containing polyol (a-1) having a number average molecular weight of 2500 or more and polyisocyanate (a-2).
• polyols (a-1) examples include polyols having one or more bonds selected from the group consisting of ester bonds, ether bonds and carbonate bonds.
• Such polyols (a-1) include polyester polyols, polyether polyols, polycarbonate polyols and the like.
• Polyol (a-1) can be used alone or in combination of two or more.
• polyester polyols include condensation polymers of polyols and dicarboxylic acids or their anhydrides.
• Polyols may be one or more, and examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol Heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, dimer acid diol, ethylene oxide a
• Dicarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, and sebacic acid. , 1,4-cyclohexyldicarboxylic acid, ⁇ -hydromuconic acid, ⁇ -hydromuconic acid, ⁇ -butyl- ⁇ -ethylglutaric acid, ⁇ , ⁇ -diethylsuccinic acid, maleic acid, fumaric acid and the like.
• polyether polyols examples include polyether polyols that are addition polymers of alkylene oxides using a compound having two active hydrogen groups as an initiator, polyether polyols that are ring-opening polymers of cyclic ethers, and the like. be done.
• the compound having two active hydrogen groups may be one or two or more.
• diol 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1, 5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis( ⁇ -hydroxyethyl)benzene, xylylene glycol, etc.), polyamines (eg, ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc.), and the like.
• alkylene oxides may be used, and may be, for example, ethylene oxide, propylene oxide, butylene oxide, and the like.
• One or more cyclic ethers may be used, and examples thereof include alkyl glycidyl ethers (eg, methyl glycidyl ether), aryl glycidyl ethers (eg, phenyl glycidyl ether, etc.), tetrahydrofuran, and the like. .
• polycarbonate polyols examples include polyols, carbonates and condensation polymers.
• Polyols may be one or more, and examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylol Heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, dimer acid diol, ethylene oxide adduct of
• Carbonates may be one or more, and examples include dialkyl carbonates (eg, dimethyl carbonate, diethyl carbonate, etc.), alkylene carbonates (eg, ethylene carbonate, propylene carbonate, etc.), diphenyl carbonate, dinaphthyl It may be a carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and the like.
• dialkyl carbonates eg, dimethyl carbonate, diethyl carbonate, etc.
• alkylene carbonates eg, ethylene carbonate, propylene carbonate, etc.
• diphenyl carbonate dinaphthyl It may be a carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and the like.
• the number average molecular weight of the polyol (a-1) is 2500 or more, preferably 2500 or more and 10000 or less, more preferably 2500 or more and 7000 or less.
• the number average molecular weight of polyol (a-1) indicates a value measured by a method (titration method) based on JIS K 0070-1992.
• the content of polyol (a-1) may be, for example, 5% by mass or more, 10% by mass or more, 12% by mass or more, or 15% by mass or more based on the total amount of component (a).
• the content of polyol (a-1) may be, for example, 61% by mass or less, 59% by mass or less, 57% by mass or less, or 55% by mass or less based on the total amount of component (a).
• the content of polyol (a-1) is small, the change in elastic modulus of the cured product tends to be more suppressed.
• the content of the structural unit derived from the polyol (a-1) is, for example, 10 mmol/kg or more, 20 mmol/kg or more, 30 mmol/kg or more, 40 mmol/kg or more, 50 mmol/kg or more, etc., 200 mmol/kg or less, 180 mmol/kg or less, 160 mmol/kg or less, 140 mmol/kg or less, 130 mmol/kg or less, 120 mmol/kg or less, 110 mmol/kg or less, 100 mmol/kg or less, etc.
• the content of the structural unit derived from the polyol (a-1) is preferably 10 mmol/kg or more and 300 mmol/kg or less, and more preferably 50 mmol/kg or more and 250 mmol/kg. /kg or less is more preferable.
• the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from the polyol (a-1) in the above range is formed. may be a composition.
• the polyol (a-1) may also be blended with the curing agent (B). That is, the above "content of structural units derived from polyol (a-1)” includes structural units derived from polyol (a-1) in component (a), and polyol (a -1) may be the total amount of structural units derived from.
• Polyisocyanates (a-2) include polyisocyanates having two or more isocyanate groups in the molecule.
• Polyisocyanate (a-2) is preferably a polyisocyanate (diisocyanate) having two isocyanate groups in the molecule.
• polyisocyanates examples include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. These can be used individually by 1 type or in combination of 2 or more types. Among these, aromatic polyisocyanates are preferably used from the viewpoint of reactivity, viscosity and the like.
• aromatic polyisocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 2,2′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,2′-diphenylmethane diisocyanate/4,4′-diphenylmethane diisocyanate mixture, 2,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate/4,4′-diphenylmethane diisocyanate mixture, 2,2′-diphenylmethane diisocyanate/2,4′-diphenylmethane diisocyanate/4,4′-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyan
• araliphatic polyisocyanates include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate/1,4-xylylene diisocyanate mixture, 1,3-bis(1 -isocyanato-1-methylethyl)benzene, 1,4-bis(1-isocyanato-1-methylethyl)benzene, 1,3-bis(1-isocyanato-1-methylethyl)benzene/1,4-bis( 1-isocyanato-1-methylethyl)benzene mixture, ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene and the like.
• aliphatic polyisocyanates examples include tetramethylene diisocyanate, hexamethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4-diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyl
• alicyclic polyisocyanates include isophorone diisocyanate, cyclohexane diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4- isocyanato-n-butylidene)pentaerythritol, hydrogenated hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2 -isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane, 2-isophor
• the content of the polyisocyanate (a-2) may be, for example, 40% by mass or more, 42% by mass or more, 44% by mass or more, or 46% by mass or more based on the total amount of component (a).
• the content of the polyisocyanate (a-2) may be, for example, 95% by mass or less, 90% by mass or less, 88% by mass or less, or 85% by mass or less based on the total amount of component (a).
• the content of polyisocyanate (a-2) is small, the fracture toughness value tends to be further improved.
• the content of the structural unit derived from the polyisocyanate (a-2) is preferably 500 mmol/kg or more and 3000 mmol/kg or less, and more preferably 750 mmol/kg or more and 2500 mmol/kg. kg or less is more preferable.
• the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from the polyisocyanate (a-2) in the above range is formed.
• composition made by It can also be said that the content of structural units derived from the polyisocyanate (a-2) in the isocyanate group-terminated prepolymer (A-1) in the urethane resin-forming composition may be within the above range.
• the component (a) may contain polyfunctional components.
• a polyfunctional component is a compound having three or more reactive groups.
• the reactive group may be any group that can react with an isocyanate group or a hydroxy group to form a bond.
• Reactive groups may be, for example, isocyanate groups or active hydrogen groups (eg, hydroxy groups, amino groups, etc.).
• a polyfunctional component can be used individually by 1 type or in combination of 2 or more types.
• the polyfunctional component may be a polyol (a-1), may be a polyisocyanate (a-2), and may be a compound (a- 3).
• Compound (a-3) may be a compound having 3 or more active hydrogen groups, may be a compound having 3 or more hydroxy groups, or may be a compound having 3 hydroxy groups.
• Examples of the compound (a-3) include glycerin, trimethylolpropane, pentaerythritol, N,N-bishydroxypropyl-N-hydroxyethylamine, triethanolamine, triisopropanolamine, monomer polyols modified from ethylenediamine propylene oxide, Monomer polyol of trimethylolpropane propylene oxide modified and pentaerythritol propylene oxide modified can be mentioned.
• polyols having three or more hydroxy groups eg, glycerin, trimethylolpropane, pentaerythritol, etc.
• cyclic esters eg, ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, etc.
• polycaprolactone polyols which are ring-opening addition polymers.
• the content of the polyfunctional component may be, for example, 10% by mass or less, 7% by mass or less, 5% by mass or less, or 3% by mass or less based on the total amount of component (a).
• Component (a) may not contain polyfunctional components, and the content of polyfunctional components may be 0% by mass or more based on the total amount of component (a).
• the content of the structural unit derived from the polyfunctional component is preferably 25 mmol/kg or more and 1000 mmol/kg or less, and is 40 mmol/kg or more and 600 mmol/kg or less. is more preferable.
• the content of the structural unit derived from the polyfunctional component is within the above range, there is a tendency to obtain a cured product having a higher fracture toughness value (G 1c ) and superior toughness.
• the urethane resin-forming composition is a composition in which the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from a multifunctional component in the above range is formed.
• the polyfunctional component may also be blended in the curing agent (B). That is, the above-mentioned "content of structural units derived from multifunctional components” refers to structural units derived from the multifunctional component in component (a) and structural units derived from the multifunctional component in the curing agent (B). It can be the total amount.
• the content of structural units derived from the crosslinkable groups possessed by the multifunctional component is preferably 25 mmol/kg or more and 1000 mmol/kg or less, and 40 mmol/kg or more. It is more preferably 600 mmol/kg or less.
• the content of the structural unit derived from the crosslinkable group is within the above range, there is a tendency to obtain a cured product having a high fracture toughness value (G 1c ) and excellent toughness.
• the urethane resin-forming composition is a composition in which the main agent (A) and the curing agent (B) are selected so that the content of the structural unit derived from the crosslinkable group is within the above range.
• the polyfunctional component may also be blended in the curing agent (B). That is, the above-mentioned "content of structural units derived from crosslinkable groups” means that the structural units derived from the crosslinkable groups possessed by the polyfunctional component in component (a) and the polyfunctional component in curing agent (B) are It may be the total amount of structural units derived from the crosslinkable groups possessed.
• the crosslinkable group is a functional group that forms a crosslink.
• a trifunctional polyol eg, glycerin
• one hydroxy group in one molecule forms crosslinks, and the remaining two hydroxy groups do not contribute to crosslinks.
• Component (a) is a group consisting of diol (B-1), diol (B-2) and diol (B-4) described later as components other than polyol (a-1) and polyisocyanate (a-2). It may further contain one or more selected diols (a-4).
• the content of diol (a-4) may be, for example, 5% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less based on the total amount of component (a).
• Component (a) may not contain diol (a-4), and the content of diol (a-4) may be 0% by mass or more based on the total amount of component (a).
• At least one of the polyol (a-1) and the polyisocyanate (a-2) in the component (a) is preferably liquid at 25°C and 1 atm.
• the ratio of the total number of hydroxy groups to the total number of isocyanate groups may be, for example, 0.02 or more, 0.03 or more, 0.04 or more, or 0.05 or more. Also, the ratio (OH/NCO) in component (a) may be, for example, 0.5 or less, 0.4 or less, 0.3 or less, or 0.2 or less.
• the isocyanate group-terminated prepolymer (A-1) is a reaction product of component (a).
• the isocyanate group-terminated prepolymer (A-1) may be a reaction product obtained by reacting all of component (a) or may be a reaction product obtained by reacting a part of component (a).
• the reaction conditions for component (a) are not particularly limited as long as the isocyanate groups and hydroxy groups in component (a) can react to form urethane bonds.
• the reaction temperature for component (a) may be, for example, 70-80°C.
• the reaction time for component (a) may be, for example, 2 to 6 hours.
• the isocyanate group-terminated prepolymer (A-1) is preferably liquid at 25°C and 1 atm.
• the main agent (A) may contain components other than the isocyanate group-terminated prepolymer (A-1). As other components, those that do not react with the functional groups of the isocyanate group-terminated prepolymer (A-1) and the curing agent (B) described later (eg, colorants, antistatic agents, preservatives, etc.) are preferred.
• the main agent (A) is preferably liquid at 25°C and 1 atm.
• the curing agent (B) comprises at least one diol (B-1) selected from the group consisting of aliphatic diols and alicyclic diols, and a diol (B-2) represented by formula (1).
• Diol (B-1) can be used alone or in combination of two or more.
• Diol (B-2) can be used alone or in combination of two or more.
• aliphatic diols examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, neopentyl glycol, diethylene glycol, di propylene glycol, and the like.
• Alicyclic diols include, for example, 1,4-cyclohexanediol, cycloheptanediol, cyclooctanediol, 1,4-cyclohexanedimethanol, hydroxypropylcyclohexanol, isohexide, tricyclo[5.2.1.02 , 6 ] decane-4,8-dimethanol and alkylene oxide adducts thereof.
• the number average molecular weight of diol (B-1) is preferably 500 g/mol or less, more preferably 250 g/mol or less.
• the number average molecular weight indicates a value measured by a method (titration method) based on JIS K 0070-1992.
• the content of the structural unit derived from the diol (B-1) is preferably 150 mmol/kg or more and 2000 mmol/kg or more, and more preferably 200 mmol/kg or more and 1500 mmol/kg.
• the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from the diol (B-1) in the above range is formed.
• the diol (B-1) may also be blended in the component (a) described above in the urethane resin-forming composition. That is, the above "content of structural units derived from diol (B-1)" includes structural units derived from diol (B-1) in component (a) and diol (B -1) may be the total amount of structural units derived from.
• the diol (B-2) is a compound represented by formula (1).
• the diol (B-2) may have a straight chain portion and a side chain portion having a ring structure.
• L is a trivalent group consisting of one or more atoms selected from the group consisting of carbon atoms, hydrogen atoms, nitrogen atoms and oxygen atoms.
• R is a group having at least one ring structure selected from the group consisting of an alicyclic structure, an aromatic ring and a heterocyclic ring.
• L may be, for example, a group having a straight chain portion with 10 or less carbon atoms connecting two hydroxy groups.
• Diol (B-2) may be, for example, a compound represented by formula (1-1).
• R has the same definition as above.
• L 1 and L 2 each independently represent a hydrocarbon group which may have a substituent.
• a 1 represents CR 1 (R 1 represents a hydrogen atom or an optionally substituted hydrocarbon group) or N;
• the hydrocarbon groups in L 1 and L 2 may be, for example, alkanediyl groups.
• the number of carbon atoms in the hydrocarbon group in L 1 and L 2 may be, for example, 1 to 10, or may be 1 to 5, not including the number of carbon atoms in the substituent.
• substituents that the hydrocarbon group in L 1 and L 2 may have include an alkyl group (eg, an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group, an alkoxy group (eg, a 10 alkoxy group), aryl group (eg, phenyl group) and the like, and these groups may further have a substituent (eg, the above substituent).
• a hydrocarbon group in R 1 may be, for example, an alkyl group, a cycloalkyl group or an aryl group.
• the number of carbon atoms in the hydrocarbon group in R 1 may be, for example, 1 to 8, or may be 1 to 5, not including the number of carbon atoms in the substituent.
• Examples of the substituent that the hydrocarbon group in R 1 may have include an alkyl group (eg, an alkyl group having 1 to 8 carbon atoms), a cycloalkyl group, an alkoxy group (eg, an alkoxy group having 1 to 8 carbon atoms). group), aryl group (eg, phenyl group), and the like, and these groups may further have a substituent (eg, the above substituent).
• R 1 is preferably a hydrogen atom.
• R is a group having at least one ring structure selected from the group consisting of an alicyclic structure, an aromatic ring and a heterocyclic ring, preferably at least one selected from the group consisting of an alicyclic structure and an aromatic ring It is a group having a ring structure, more preferably a group having an aromatic ring.
• the number of carbon atoms constituting the ring structure of R is preferably 10 or less.
• R may be, for example, an optionally substituted phenyl group or an optionally substituted cyclohexyl group.
• substituents that the phenyl group and cyclohexyl group in R may have include an alkyl group (eg, an alkyl group having 1 to 5 carbon atoms), a cycloalkyl group, an alkoxy group (eg, a alkoxy group), aryl group (eg, phenyl group), and the like, and these groups may further have a substituent (eg, the above substituent).
• Examples of the diol (B-2) include 3-phenyl-1,5-pentanediol, 2-(phenylmethyl)-1,4-butanediol, 2,4-dimethyl-3-phenyl-1,5- Pentanediol, 3-phenyl-1,4-pentanediol, 2-(2-phenylethyl)-1,3-propanediol, 3-methyl-3-phenyl-1,5-pentanediol, 3-(4-methyl Phenyl)-1,5-pentanediol, 3-methyl-3-(4-methylphenyl)-1,5-pentanediol, 2-[2-(4-ethylphenyl)ethyl]-1,3-propanediol , 2-[4-(1-methylethyl)phenyl]-1,4-butanediol, 2,2′-(p-tolylimino)di
• the content of the structural unit derived from the diol (B-2) is preferably 40 mmol/kg or more and 600 mmol/kg or more, and more preferably 60 mmol/kg or more and 500 mmol/kg.
• the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from the diol (B-2) in the above range is formed.
• the diol (B-2) may also be added to the component (a) described above in the urethane resin-forming composition. That is, the above "content of structural units derived from diol (B-2)" includes structural units derived from diol (B-2) in component (a) and diol (B -2) may be the total amount of structural units derived from.
• the curing agent (B) may further contain a polyfunctional component.
• a polyfunctional component is a compound having three or more reactive groups.
• a polyfunctional component can be used individually by 1 type or in combination of 2 or more types.
• the polyfunctional component the same as the polyfunctional component in component (a) can be exemplified.
• the polyfunctional component contained in the curing agent (B) is preferably a compound (B-3) having 3 or more hydroxy groups.
• Examples of the compound (B-3) include glycerin, trimethylolpropane, pentaerythritol, N,N-bishydroxypropyl-N-hydroxyethylamine, triethanolamine, triisopropanolamine, monomer polyols modified from ethylenediamine propylene oxide, Monomer polyol of trimethylolpropane propylene oxide modified and pentaerythritol propylene oxide modified can be mentioned.
• polyols having three or more hydroxy groups eg, glycerin, trimethylolpropane, pentaerythritol, etc.
• cyclic esters eg, ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, etc.
• polycaprolactone polyols which are ring-opening addition polymers.
• the content of the polyfunctional component is, for example, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, based on the total amount of the curing agent (B). It may be mass % or less.
• Curing agent (B) may not contain a polyfunctional component, and the content of the polyfunctional component may be 0% by mass or more based on the total amount of curing agent (B).
• the content of the structural unit derived from the polyfunctional component in the urethane resin formed from the urethane resin-forming composition is as described above.
• the curing agent (B) may further contain the compounds exemplified as the polyol (a-1) above.
• the curing agent (B) may further contain a diol (B-4) having a number average molecular weight of less than 1000 as a component other than the diol (B-1) and diol (B-2) described above.
• Diol (B-4) more preferably has a number average molecular weight of less than 500.
• diol (B-4) examples include diols having at least one bond selected from the group consisting of an ether bond, an ester bond and a carbonate bond.
• diols examples include polyether polyols, polycarbonate polyols, polyester polyols, and the like.
• polyether polyols, polycarbonate polyols and polyester polyols are the same as the above polyol (a-1) (however, the number average molecular weight is different).
• the content of structural units derived from diol (B-4) may be, for example, 100 mmol/kg or less, 80 mmol/kg or less, or 60 mmol/kg or less. Further, in the urethane resin formed from the urethane resin-forming composition, the content of the structural unit derived from the diol (B-4) may be, for example, 0 mmol/kg or more, 5 mmol/kg or more, or 10 mmol/kg or more.
• the main agent (A) and the curing agent (B) are selected so that a urethane resin having a content of structural units derived from the diol (B-4) in the above range is formed.
• the diol (B-4) may also be blended in the component (a) described above in the urethane resin-forming composition. That is, the above "content of structural units derived from diol (B-4)" includes structural units derived from diol (B-4) in component (a) and diol (B -4) may be the total amount of structural units derived from.
• the curing agent (B) may further contain an active hydrogen-containing compound as a component other than the above.
• active hydrogen-containing compounds include compounds having functional groups such as amino groups, thiol groups, and carboxyl groups. These active hydrogen-containing compounds can be used singly or in combination of two or more.
• the curing agent (B) may contain other components than those mentioned above. As other components, those that do not react with the functional groups of the isocyanate group-terminated prepolymer (A-1) and curing agent (B) (eg, colorants, antistatic agents, preservatives, etc.) are preferred.
• At least one of the diol (B-1) and the diol (B-2) in the curing agent (B) is preferably liquid at 25° C. and 1 atmosphere, and both are liquid at 25° C. and 1 atmosphere. is more preferable.
• the ratio (B/A) of the total number of hydroxy groups in the curing agent (B) to the total number of isocyanate groups in the main agent (A) is, for example, 0.6 or more, 0.7 or more, 0.8 or more, or 0.9. or more. Also, the ratio (B/A) may be, for example, 1.2 or less, 1.15 or less, 1.10 or less, or 1.05 or less. When the ratio (B/A) is within the above range, the resin strength tends to be further improved. When the urethane resin-forming composition is of a two-component type, the two components are mixed so that the main component (A) and the curing agent (B) satisfy the above ratio (B/A). can be anything.
• the curing agent (B) is preferably liquid at 25°C and 1 atm.
• At least one of the main agent (A) and the curing agent (B) is preferably liquid at 25°C and 1 atm. and more preferably liquid at 1 atm.
• the urethane resin-forming composition may further contain a filler (C).
• the filler (C) may be contained in the first agent together with the main agent (A), and may be contained in the second agent together with the curing agent (B). It may be contained in both the first agent and the second agent. That is, the urethane resin-forming composition may contain, for example, a first agent containing the main agent (A) and the filler (C) and a second agent containing the curing agent (B).
• the filler (C) includes known fillers.
• the filler (C) may be, for example, an inorganic filler or an organic filler, preferably an inorganic filler.
• a filler (C) can be used individually by 1 type or in combination of 2 or more types.
• inorganic fillers examples include talc, zeolite, silica, microballoons, clay, glass balloons, carbon black, and calcium carbonate. Inorganic fillers are not limited to these. These can be used alone or in combination of two or more.
• organic fillers examples include polyamide particles, acrylic particles, carbon nanotubes, starch, natural organic fibers, and synthetic fibers.
• the content of the filler (C) is, for example, preferably 10% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 50% by mass or less, relative to the total mass of the urethane resin-forming composition. preferable.
• the content of the filler (C) is 10% by mass or more, dripping can be suppressed more satisfactorily.
• the content of the filler (C) is 70% by mass or less, the filler (C) and other components are more uniformly mixed with each other, resulting in better adhesive strength and coatability.
• the urethane resin-forming composition is of a two-component type, the total mass of the urethane resin-forming composition is the total amount of the first agent and the second agent mixed to form a cured product. you can
• the urethane resin-forming composition may be of a two-component type in which a first agent containing the main agent (A) and a second agent containing the curing agent (B) are separately present. It may be a one-liquid type mixed with the curing agent (B).
• the temperature and time for mixing the first agent and the second agent may be, for example, 10 to 35°C and 1 to 60 minutes.
• the mixing method for mixing the first agent and the second agent is not particularly limited. For example, they may be mixed manually with a spatula, or mixed using a mechanical rotary mixer, static mixer, or the like.
• the urethane resin-forming composition preferably has a solvent content of 1.0% by mass or less. Further, the urethane resin-forming composition may be substantially solvent-free, that is, solvent-free. However, when a solvent is included as an impurity, it belongs to the category of substantially no solvent.
• the solvent content in the first agent is preferably 1.0% by mass or less
• the solvent content in the second agent is 1.0% by mass or less. It is preferably 0% by mass or less.
• the content of the solvent in the first and second agents to be mixed is 1.0% by mass or less with respect to the total amount of the first and second agents to be mixed to form the cured product. is preferably
• the urethane resin-forming composition can be suitably used as an adhesive (especially a two-component adhesive) for various uses.
• Application fields include, for example, the automobile field, the display field, the recording medium field, the electronic material field, the battery field, the optical component field, the construction field, the electronic equipment field, and the aviation field.
• the automotive field for example, it can be used for automobile structural parts, switch parts, headlamps, internal engine parts, electrical parts, drive engines, and brake oil tanks.
• the display field for example, it can be used in liquid crystal displays, organic electroluminescence, and light-emitting diode displays.
• recording media for example, it can be used for video discs, CDs, DVDs, MDs, pickup lenses, VCM magnets, spindle motors, hard disk peripheral members, and Blu-ray discs.
• the field of electronic materials for example, it can be used for electronic components, electric circuits, electrical contacts, or semiconductor elements. Conductive adhesives, interlayer adhesives for multilayer substrates including build-up substrates, and the like.
• the battery field for example, it can be used in lithium ion batteries, manganese batteries, alkaline batteries, nickel batteries, fuel cells, silicon solar cells, dye-sensitized solar cells, and organic solar cells.
• optical parts for example, it can be used around optical switches in optical communication systems, optical fiber materials around optical connectors, optical passive parts, optical circuit parts, and around optoelectronic integrated circuits.
• the field of electronic equipment for example, it can be used for camera modules.
• the urethane resin-forming composition has a high fracture toughness value, so it can be particularly suitably used as an adhesive for automobile structures.
• a cured product according to one aspect of the present disclosure is a cured product of the urethane resin-forming composition described above.
• the cured product contains a urethane resin that is a reaction product of the main agent (A) and the curing agent (B).
• the urethane group concentration of the urethane resin in the cured product may be, for example, 2000 mmol/kg or more and 4500 mmol/kg or less, preferably 2500 mmol/kg or more and 4000 mmol/kg or less. With such a urethane group concentration, the fracture toughness value (G 1c ) of the cured product tends to be higher, and the cured product tends to have more excellent toughness.
• the urethane resin-forming composition is cured by reacting the main agent (A) and the curing agent (B).
• the composition for forming a urethane resin may be cured by, for example, mixing the first agent and the second agent and allowing the main agent (A) and the curing agent (B) to react.
• the reaction conditions for reacting the main agent (A) and the curing agent (B) are not particularly limited.
• the heating temperature may be 100 to 200°C, and the heating time may be 20 minutes to 10 hours.
• the reaction between the main agent (A) and the curing agent (B) may be carried out in one stage of heating, or may be carried out in multiple stages of heating of two or more stages.
• the fracture toughness value of the cured product may be, for example, 0.3 or more, 0.5 or more, 0.7 or more, or 0.8 or more.
• the upper limit of the fracture toughness value of the cured product is not particularly limited.
• the fracture toughness value of the cured product may be, for example, 6.0 or less, 4.0 or less, or 3.0 or less.
• each raw material of the main agent was charged according to the recipes shown in Tables 1 to 5 and stirred. Thereafter, while maintaining the temperature in the stirring vessel at 70 to 80° C., the urethanization reaction was allowed to proceed for about 2 to 5 hours to obtain the main component (A).
• the filler (C) (50% by mass of talc/50% by mass of zeolite) is added to the main agent (A) so that the amount of filler in the system is 1/3 (mass ratio), and mixed and degassed. got the drug.
• each raw material of the curing agent was put into a 2 L stirring container filled with nitrogen according to the recipes shown in Tables 1 to 5 and stirred. After that, while maintaining the temperature in the stirring container at 70 to 80° C., the mixture was stirred for about 1 to 3 hours to obtain a curing agent (B).
• This curing agent (B) was used as the second agent.
• the first agent and the second agent were mixed according to the compositions shown in Tables 1 to 5, stirred for 30 seconds, and then applied onto the first substrate.
• a 0.35 mm thick Teflon (registered trademark) seal was attached to the first substrate in a range of 4.9 cm from one end in order to give a preliminary crack to the test piece.
• a 0.35 mm thick Teflon (registered trademark) seal was pasted on the first substrate in a range of 2 cm from the other end side in order to make the coating thickness of the adhesive uniform.
• a second base material was placed on the coated surface and fixed with a clamp.

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