Composition, adhesive composition and adhesive

Abstract

To provide a composition, an adhesive composition, and an adhesive which are capable of exhibiting excellent adhesive strength at room temperature and high temperature.SOLUTION: The composition contains a curing agent (A), an isocyanate group-terminated polyisocyanate (B), and a filler (C). The curing agent (A) contains a polyol (a1) and a diamine (a2). The content of the diamine (a2) is 0.05 mmol / g or more and 1.00 mmol / g or less based on resin components in the composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to a composition, an adhesive composition, and an adhesive. [Background technology]

[0002] There are various types of adhesives known, including epoxy adhesives, urethane adhesives, etc. Epoxy adhesives lack fracture toughness compared to urethane adhesives, and although they are strong, they are brittle. For this reason, urethane-based adhesives have been attracting attention as structural adhesives that require fracture toughness. For example, Patent Document 1 discloses a urethane-based two-component adhesive that includes an isocyanate component, an isocyanate-terminated prepolymer and / or prepolymer mixture having a specific isocyanate functionality, an amine, and a trimerization catalyst, and has a stoichiometric ratio of the amine to the isocyanate group in a specific range. According to Patent Document 1, this urethane-based two-component adhesive is easier to handle, more widely applicable, and is strong after curing, yet not very brittle at the same time. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Special Publication No. 2017-502103 Summary of the Invention [Problem to be solved by the invention]

[0004] The urethane-based two-component adhesive disclosed in Patent Document 1 has an aluminum-aluminum tensile shear strength of 5.58 MPa at 150° C., and can exhibit good adhesive strength at high temperatures. However, the urethane-based two-component adhesive disclosed in Patent Document 1 has an aluminum-aluminum tensile shear strength of 9.13 MPa at 20° C. This tensile shear strength does not satisfy the adhesive strength required at about room temperature, and further improvement is required. Therefore, one embodiment of the present disclosure is directed to providing a composition, an adhesive composition, and an adhesive that can exhibit excellent adhesive strength at room temperature and high temperatures. [Means for solving the problem]

[0005] In one embodiment of the present disclosure, the composition comprises: A hardener (A); An isocyanate-terminated polyisocyanate (B); A composition comprising: The curing agent (A) contains a polyol (a1) and a diamine (a2), The content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less.

[0006] In another embodiment of the present disclosure, the composition comprises: A hardener (A); and an isocyanate group-terminated polyisocyanate (B), The curing agent (A) contains a polyol (a1) and a diamine (a2), the content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less; The diamine (a2) includes an aromatic diamine.

[0007] An adhesive composition according to another embodiment of the present disclosure includes the above-mentioned composition. An adhesive according to another embodiment of the present disclosure includes the adhesive composition described above. Effect of the Invention

[0008] According to one embodiment of the present disclosure, it is possible to provide a composition, an adhesive composition, and an adhesive that can exhibit excellent adhesive strength at room temperature and high temperatures. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Exemplary embodiments for implementing the present disclosure are described in detail below. <First embodiment (composition)> In one embodiment of the present disclosure, the composition comprises: A hardener (A); An isocyanate-terminated polyisocyanate (B); A composition comprising: The curing agent (A) contains a polyol (a1) and a diamine (a2), The content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less.

[0010] [Hardening agent (A)] The curing agent (A) contains a polyol (a1) and a diamine (a2). The curing agent (A) may contain a curing agent other than the polyol (a1) and the diamine (a2).

[0011] [[Polyol (a1)]] Examples of the polyol (a1) include polyols having an average functionality of 3 or more and polyols having an average functionality of 2 or less. Examples of polyols having an average functionality of 3 or more include glycerin, trimethylolpropane, pentaerythritol, N,N-bishydroxypropyl-N-hydroxyethylamine, triethanolamine, triisopropanolamine, monomer polyols of ethylenediamine propylene oxide modified products, monomer polyols of trimethylolpropane propylene oxide modified products, pentaerythritol propylene oxide modified products, and polycaprolactone polyols obtained by ring-opening addition of cyclic esters such as ε-caprolactone, β-butyrolactone, γ-butyrolactone, γ-valerolactone, and δ-valerolactone to polyols such as glycerin, trimethylolpropane, and pentaerythritol as initiators. These may be used alone or in combination of two or more.

[0012] Examples of polyols having an average functionality of 2 or less include polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as 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, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and tetrahydrofuran.

[0013] Other examples include polyols having two or less carbonate bonds, ester bonds, ether bonds, etc., such as polymer polyols, polycarbonate polyols, polyester polyols, polyether polyols, etc. Among these, polycarbonate polyols are preferred from the viewpoints of strength, heat resistance, weather resistance, and durability, and liquid polycarbonate polyols that can be handled in a liquid state at room temperature are particularly preferred. Although the details of why polycarbonate polyol has excellent strength, heat resistance, weather resistance, and durability are not clear, the present inventors speculate that it is superior to the use of polyether polyol or polyester polyol due to the high cohesive strength of the carbonate bond.

[0014] Examples of polycarbonate polyols 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, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, dimer Examples of such polyols include those obtained by a dealcoholization reaction or a dephenolization reaction between one or more polyols, such as an acid diol, an ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, or xylylene glycol, and one or more dialkyl carbonates, such as dimethyl carbonate or diethyl carbonate, alkylene carbonates, such as ethylene carbonate or propylene carbonate, or carbonates, such as diphenyl carbonate, dinaphthyl carbonate, dianthryl carbonate, diphenanthryl carbonate, or diindanyl carbonate. These may be contained alone or in combination of two or more.

[0015] Examples of polyester polyols include dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, and fumaric acid, and anhydrides thereof; and polyester polyols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and the like. Examples of the polyamide polyol include those obtained by condensation polymerization of one or more of hexanediol, 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, glycerin, trimethylolpropane, diol dimer acid, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, etc. Also, polyester-amide polyols obtained by replacing a part of them with low molecular weight polyamines or low molecular weight amino alcohols such as hexamethylenediamine, isophoronediamine, and monoethanolamine can be used. These may be contained alone or in combination of two or more.

[0016] Examples of polyether polyols include low molecular weight polyols such as 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, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, diol dimer acid, bisphenol A, bis(β-hydroxyethyl)benzene, and xylylene glycol. Examples of the polyether polyols include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, etc., using as an initiator a compound having two active hydrogen groups such as diamines, low molecular weight polyamines such as ethylene diamine, propylene diamine, toluene diamine, metaphenylenediamine, diphenylmethane diamine, xylylene diamine, etc., and polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as alkyl glycidyl ethers such as methyl glycidyl ether, aryl glycidyl ethers such as phenyl glycidyl ether, and tetrahydrofuran. These may be contained alone or in combination of two or more.

[0017] [[Diamine (a2)]] The diamine (a2) is not particularly limited, but preferably contains a diamine having electron-withdrawing properties, and more preferably contains two primary amino groups.

[0018] More specifically, the diamine (a2) may be, for example, an aromatic diamine, an aliphatic diamine, an alicyclic diamine, etc. Among these, an aromatic diamine is preferred.

[0019] [[[Aromatic diamines]]] The aromatic diamine may, for example, be a diamine represented by formula (1):

[0020] [ka]

[0021] In formula (1), Each R is independently any one selected from the group consisting of an amino group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxycarbonyl group, and an alkylthio group; n is an integer less than or equal to 4; When n is 1, R is an amino group; If n is an integer between 2 and 4, Any one of R is an amino group; The other R is any one other than an amino group.

[0022] Here, the halogen atom is preferably a chlorine atom. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having 5 to 7 carbon atoms which may have a substituent. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms. The alkylthio group is preferably an alkylthio group having 1 to 3 carbon atoms.

[0023] Examples of aromatic diamines include diamines represented by formula (2):

[0024] [ka]

[0025] In formula (2), R 1 and R 2 each independently represents one selected from the group consisting of a halogen atom, an alkyl group, an alkoxycarbonyl group, and an alkylthio group; R 3is a divalent group composed of one or more atoms selected from the group consisting of carbon atoms, sulfur atoms, hydrogen atoms, and oxygen atoms; p and q each independently represent an integer of 3 or less.

[0026] Here, the halogen atom is preferably a chlorine atom. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 7 carbon atoms. The alkylthio group is preferably an alkylthio group having 1 to 3 carbon atoms.

[0027] R 3 -R 4 -, -SO2-, -SR 4 -S-, -COO-R 4 -OOC- or -COO-R 5 -OC- is preferred, where R 4 is an alkyl group having 1 to 5 carbon atoms, R 5 is an oxyalkylene group having 1 to 5 carbon atoms. 4 is more preferably an alkyl group having 1 to 3 carbon atoms, and R 5 is more preferably an oxyalkylene group having 1 to 3 carbon atoms.

[0028] Examples of aromatic diamines include phenylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 4-chloro-3,5-diaminobenzoic acid isobutyl, 4,4'-methylenebis(phenylamine), 4,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl sulfone.

[0029] [[[Aliphatic diamines]]] Examples of the aliphatic diamine include ethylenediamine, trimethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, and octamethylenediamine.

[0030] [[[Alicyclic diamines]]] Examples of the alicyclic diamine include alicyclic diamine compounds such as cyclopentanediamine, cyclohexyldiamine, 4,4-diaminodicyclohexylmethane, 1,4-diaminocyclohexane, and isophoronediamine.

[0031] [[Diamine (a2) content]] The content of diamine (a2) is 0.05 mmol / g or more and 1.00 mmol / g or less based on the resin component in the composition. If the content of diamine (a2) is less than 0.05 mmol / g, the adhesive strength is insufficient. If the content of diamine (a2) is more than 1.00 mmol / g, the curing speed is too fast, and the handling property is deteriorated. The content of diamine (a2) relative to the resin component in the composition is preferably 0.90 mmol / g or less, more preferably 0.80 mmol / g or less, even more preferably 0.70 mmol / g or less, and preferably 0.10 mmol / g or more. In one embodiment, for example, the content of diamine (a2) in adhesive applications may be 0.20 mmol / g or more, 0.35 mmol / g or more, or 0.45 mmol / g or more, and may be 0.90 mmol / g or less, 0.80 mmol / g or less, or 0.75 mmol / g or less. Furthermore, in other embodiments, for example, in applications for large rolls such as papermaking rolls and ironmaking rolls, the content of diamine (a2) may be 0.50 mmol / g or less, 0.40 mmol / g or less, or may be 0.10 mmol / g or more. Here, the resin component does not include the filler (C) described in detail below, but includes the curing agent (A) and the isocyanate-terminated polyisocyanate (B), and may include other resin components. Even if the filler (C) is a filler made of a resin, it is not included in the resin component.

[0032] [Isocyanate-terminated polyisocyanate (B)] There is no limitation on the isocyanate-terminated polyisocyanate (B) as long as it is an isocyanate-terminated urethane prepolymer obtained by modifying an unmodified isocyanate (b1) such as an aliphatic isocyanate, alicyclic isocyanate, aromatic isocyanate, or araliphatic isocyanate with a polyol. If necessary, additives such as a reaction regulator or an antioxidant may be added. Among them, from the viewpoint of reactivity and viscosity, an isocyanate-terminated polyisocyanate (B) obtained by reacting an aromatic isocyanate with a polyol (b2) having an average functionality of 2 is preferred. Since the isocyanate-terminated polyisocyanate (B) used in the adhesive is liquid at room temperature, it is particularly preferred that the unmodified isocyanate (b1) used for modification is liquid at room temperature.

[0033] There is no particular limitation on the method for producing the isocyanate-terminated polyisocyanate (B), and any known method can be used. For example, after a mixture of 4,4'-diphenylmethane diisocyanate / 2,4'-diphenylmethane diisocyanate is added to a stirring vessel, a bifunctional or trifunctional polyol not containing an amino group is added and stirred while keeping the temperature in the vessel at 40 to 70°C. Then, a urethane reaction is carried out for about 2 to 5 hours while keeping the temperature in the stirring vessel at 70 to 90°C, and the isocyanate-terminated polyisocyanate (B) can be obtained.

[0034] [[Aliphatic isocyanates]] Examples of aliphatic isocyanates include hexamethylene diisocyanate, tetramethylene 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 Examples of the isocyanate include diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanate methyl octane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyl octane, bis(isocyanate ethyl) carbonate, bis(isocyanate ethyl) ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanate methyl ester, 2-isocyanate ethyl-2,6-diisocyanate hexanoate, and 2-isocyanate propyl-2,6-diisocyanate hexanoate.

[0035] [[Alicyclic isocyanate]] Examples of alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanate methyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate-n-butylidene)pentaerythritol, hydrogenated dimer acid diisocyanate, 2-isopropyl ether ... 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-5-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-6-isocyanatemethyl-bicyclo[2.2.1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-5-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanatemethyl-3-(3-isocyanatepropyl)-6-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-5-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane, 2-isocyanatemethyl-2-(3-isocyanatepropyl)-5-(2-isocyanateethyl)-bicyclo-[2.2.1]-heptane, Examples of such isocyanate include isocyanate methyl-2-(3-isocyanate propyl)-6-(2-isocyanate ethyl)-bicyclo-[2.2.1]-heptane, 2,5-bis(isocyanate methyl)-bicyclo[2.2.1]-heptane, hydrogenated diphenylmethane diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated tetramethylxylene diisocyanate.

[0036] [[Aromatic isocyanates]] Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate, 2,4'-diphenylmethane diisocyanate, a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrophenyl ... Examples of the diisocyanate include 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, and 3,3'-dimethoxydiphenyl-4,4'-diisocyanate.

[0037] [[Aromatic Aliphatic Isocyanates]] Examples of the aromatic aliphatic isocyanate include 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or a mixture thereof, ω,ω'-diisocyanato-1,4-diethylbenzene, and the like.

[0038] From the viewpoint of ease of handling after prepolymerization, the isocyanate-terminated polyisocyanate (B) is preferably one obtained from a polyol having an average functionality of 2.

[0039] Examples of polyols having an average functionality of 2 include polyols having two or more ether bonds, ester bonds, carbonate bonds, etc., such as polyether polyols, polycarbonate polyols, and polyester polyols.

[0040] Examples of the polyether polyol, polycarbonate polyol, and polyester polyol include the same polyether polyol, polycarbonate polyol, and polyester polyol as those exemplified as the curing agent (A).

[0041] Among these, polyether polyol (polytetramethylene glycol) obtained by ring-opening polymerization of a cyclic ether monomer such as tetrahydrofuran is preferred from the viewpoint of exhibiting excellent physical properties.

[0042] Filler Examples of the filler (C) include known fillers, such as inorganic fillers and organic fillers. The filler (C) preferably contains an inorganic filler.

[0043] Examples of inorganic fillers include, but are not limited to, talc, zeolite, silica, microballoons, clay, glass balloons, carbon black, etc. These can be used alone or in combination of two or more. Among them, a combination of zeolite and talc is preferred. Zeolite has the effect of suppressing foaming, and talc has the effect of preventing dripping.

[0044] Examples of organic fillers include polyamide particles, acrylic particles, carbon nanotubes, starch, natural organic fibers, and synthetic fibers.

[0045] The content of the filler (C) in the composition is preferably 70% by mass or less, and more preferably from 10% by mass to 50% by mass. When the content of the filler (C) is 70% by mass or less, the filler (C) is mixed more uniformly with the other components, and better adhesive strength and coatability are obtained.

[0046] The filler (C) and other composition components can be easily mixed by a three-roll mill, a planetary mixer, a revolving agitator, etc. In this case, it is preferable to carry out the kneading under a nitrogen atmosphere in order to prevent the mixing of moisture from the outside air.

[0047] [solvent] The composition may contain a solvent, but the content of the solvent is preferably 1% by mass or less, and it is particularly preferable that the composition is a solvent-free type that does not substantially contain a solvent. The solvent-free type that does not substantially contain a solvent includes the case where a solvent component is contained as an impurity, and the case where a solvent component is contained in an amount that cannot be removed even by purification. If the content of the solvent in the composition is 1% by mass or less, the viscosity is too low, and dripping can be further suppressed.

[0048] [catalyst] A catalyst can be used to promote the reaction between the curing agent (A) and the isocyanate-terminated polyisocyanate (B). It is particularly preferred that the catalyst content in the composition is 0.05% by mass or less, since this further suppresses the decrease in the elastic modulus of the resin at high temperatures (150 to 200°C) and provides better high-temperature adhesion. The catalyst includes an isocyanurate catalyst, a urethanization catalyst, etc., specific examples of which are shown below.

[0049] [[Isocyanurate catalyst]] Examples of the isocyanurate catalyst include tertiary amines such as triethylamine, N-ethylpiperidine, N,N'-dimethylpiperazine, N-ethylmorpholine, Mannich bases of phenol compounds, potassium acetate, etc. These isocyanurate catalysts can be used alone or in combination of two or more.

[0050] [[Urethane catalyst]] The urethanization catalyst can be appropriately selected from known catalysts, and examples thereof include amine-based catalysts, imidazole-based catalysts, and metal catalysts.

[0051] [[[Amine catalyst]]] Examples of the amine catalyst include triethylenediamine, 2-methyltriethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N",N"-pentamethyldiethylenetriamine, N,N,N',N",N"-pentamethyl-(3-aminopropyl)ethylenediamine, N,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N",N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether, and the like.

[0052] [[[Imidazole-based catalysts]]] Examples of the imidazole catalyst include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, and 1-dimethylaminopropylimidazole.

[0053] [[[Metal-based catalysts]]] Examples of the metal catalyst include organotin catalysts such as stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate.

[0054] [Cross-linking component having cross-linkable group] The composition may further contain a crosslinking component having a crosslinkable group. In this case, the content of the crosslinkable group relative to the resin component in the composition is preferably 0.05 mmol / g or more and 1.00 mmol / g or less.

[0055] [Other additives] The composition may further contain, as necessary, additives such as a reaction inhibitor, an antioxidant, and an antifoaming agent.

[0056] The composition according to the first embodiment can exhibit excellent adhesive strength at room temperature and at high temperatures. Here, room temperature means 15° C. or higher and 35° C. or lower, particularly 20° C. or higher and 30° C. or lower, and in the examples described below, the room temperature is set to 25° C.

[0057] <Second embodiment (composition)> In one embodiment of the present disclosure, the composition comprises: A hardener (A); and an isocyanate group-terminated polyisocyanate (B), The curing agent (A) contains a polyol (a1) and a diamine (a2), the content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less; The diamine (a2) includes an aromatic diamine.

[0058] The composition according to this embodiment is the same as the composition according to the first embodiment except that the composition according to this embodiment does not need to contain the filler (C) that is essential in the first embodiment and that the diamine (a2) is an aromatic diamine. Therefore, the composition according to this embodiment is the same as the composition according to the first embodiment except that the composition according to this embodiment does not need to contain the filler (C) that is essential in the first embodiment and that the diamine (a2) is an aromatic diamine. Therefore, the description of the composition according to this embodiment that is common to the first embodiment will be omitted.

[0059] [Aromatic diamines] The aromatic diamine may be the same as that in the first embodiment. Also, a diamine other than the aromatic diamine may be used in combination.

[0060] The composition according to the second embodiment described above can exhibit excellent adhesive strength at room temperature and at high temperatures.

[0061] <Third embodiment (adhesive composition, adhesive)> The adhesive composition according to one embodiment of the present disclosure contains the above-mentioned composition (first embodiment, second embodiment). The adhesive composition may be the above-mentioned composition itself, or may further contain other components. Moreover, an adhesive according to one embodiment of the present disclosure contains the above-mentioned adhesive composition. The adhesive may be the above-mentioned adhesive composition itself, or may further contain other components.

[0062] The adhesive according to one embodiment of the present disclosure can be used as an adhesive for various applications, such as in the automotive field, display field, recording medium field, electronic materials field, battery field, optical component field, construction field, electronic device field, and aviation field. In the automotive field, examples include structural parts, switches, headlamps, internal engine parts, electrical parts, drive engines, brake oil tanks, etc. of automobiles. In the display field, liquid crystal displays, organic electroluminescence, light emitting diode display devices and the like can be mentioned. Examples of recording media include video discs, CDs, DVDs, MDs, pickup lenses, VCM magnets, spindle motors, hard disk peripherals, and Blu-ray discs. Examples of the electronic materials field include electronic components, electric circuits, electric contacts, and semiconductor elements, etc. More specific examples of these applications include sealing materials, die bonding agents, conductive adhesives, anisotropic conductive adhesives, and interlayer adhesives for multilayer substrates including build-up substrates. In the battery field, examples include lithium ion batteries, manganese batteries, alkaline batteries, nickel-based batteries, fuel cells, silicon-based solar cells, dye-sensitized solar cells, and organic solar cells. The optical component field includes optical switch peripherals in optical communication systems, optical fiber materials for optical connector peripherals, optical passive components, optical circuit components, and optoelectronic integrated circuit peripherals. Examples of the electronic device field include camera modules. EXAMPLES

[0063] The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these in any way.

[0064] In a 5 L stirring vessel filled with nitrogen, polyol (a1) and a crosslinking component were added in the proportions shown in Tables 1 and 2 and stirred. While maintaining the temperature inside the stirring vessel at 40 to 70°C, the mixture was mixed and stirred for about 1 to 3 hours, and then diamine (a2) melted at or above its melting point was mixed in to obtain various curing agents (A).

[0065] In addition, each material was added to a nitrogen-filled 5 L stirring vessel according to the blending ratios shown in Tables 1 and 2 and stirred. Thereafter, the temperature inside the stirring vessel was kept at 70 to 90°C and the urethane reaction was allowed to proceed for about 2 to 5 hours to obtain various isocyanate-terminated polyisocyanates (B) that were prepolymers.

[0066] Furthermore, in Examples 1 to 10 and Comparative Examples 11 to 12, a filler (C) was added to an isocyanate group-terminated polyisocyanate (B) according to the formulations shown in Tables 1 and 2, and mixed using a revolutionary agitator (product name: Kakuhunter, manufactured by Shashin Kagaku Co., Ltd.).

[0067] Next, the adhesive was prepared by mixing the curing agent (A) with a stainless steel spatula until it was uniform according to the recipe shown in Tables 1 and 2. The obtained adhesive was evenly applied to an aluminum plate (100 mm long x 25 mm wide x 1 mm thick; A6061, T-Zr treated) to prepare an adhesion test piece conforming to JIS K 6850:1999.

[0068] The abbreviations of the raw materials shown in Tables 1 and 2 are as follows. [Raw materials] (1) Hardener (A) "MOCA"; 3,3'-dichloro-4,4'-diaminodiphenylmethane (Kumiai Chemical Industry Co., Ltd.), Hydroxyl value (amino group) = 420KOHmg / g, f = 2 "CDAB": 4-chloro-3,5-diaminobenzoic acid isobutyl (YSK Co., Ltd.), Hydroxyl value (amino group) = 462KOHmg / g, f = 2 "TMP": Trimethylolpropane (manufactured by Mitsubishi Gas Chemical Co., Ltd.) Trimethylolpropane, hydroxyl value = 1255KOHmg / g, f = 3 "MA-170": Leocon MA-170 (manufactured by Lion Specialty Chemicals), N,N-bishydroxypropyl-N-hydroxyethylamine, Hydroxyl value = 950 KOH mg g, f = 3 "PCD-500": KurarayPolyol C-590 (manufactured by Kuraray Co., Ltd.), Polycarbonate polyol, hydroxyl value = 224KOHmg / g, f = 2 "PCD-1000": Kuraray Polyol C-1090 (manufactured by Kuraray) Polycarbonate polyol, hydroxyl value = 112KOHmg / g, f = 2 "PCD-2000": Kuraray Polyol C-2090 (manufactured by Kuraray Co., Ltd.), Polycarbonate polyol, hydroxyl value = 56KOHmg / g, f = 2 "PES-1000": Kuraray Polyol P-1010 (manufactured by Kuraray Co., Ltd.), Polyester polyol, hydroxyl value = 112KOHmg / g, f = 2

[0069] (2) Isocyanate-terminated polyisocyanate (B) "NM": Millionate NM (manufactured by Tosoh Corporation) 4,4'-Diphenylmethane diisocyanate / 2,4'-diphenylmethane diisocyanate mixture, NCO content=33.5%, f=2 "T-100"; Coronate T-100 (manufactured by Tosoh Corporation) 2,4-tolylene diisocyanate, NCO content=48.2%, f=2 "PTMG-850"; PTMG850 (manufactured by Mitsubishi Chemical Corporation), Polytetramethylene glycol, hydroxyl value 132KOHmg / g, f=2

[0070] (3) Filler (C) "Zeolite": Zeolum A-3 (manufactured by Tosoh Corporation) "Talc": Crown Talc R (manufactured by Matsumura Sangyo Co., Ltd.)

[0071] [Table 1]

[0072] [Table 2]

[0073] <Test piece preparation and evaluation criteria> (1) Adhesive strength at room temperature [25°C x 16 hours curing (measured in a 25°C environment)] An adhesive was applied to the surface of two aluminum plates (100 mm long x 25 mm wide x 1 mm thick; A6061, T-Zr treated), and the aluminum plates were bonded together so that the overlapping area was 12.5 mm long x 25 mm wide, and this was left to harden for 16 hours at 25°C to prepare an adhesion test specimen. At this time, glass beads were used to adjust the thickness of the adhesive layer to 0.25 mm, and an adhesion test specimen was obtained. The tensile shear strength of the adhesive joint of the adhesive test piece prepared as described above was measured using a tensile tester (product name: Autocom Universal Tester AC-10kN-C, manufactured by TSE Co., Ltd.). This measurement was performed in accordance with JIS K6850:1999, Tensile Shear Adhesive Strength of Adhesives. The measurement conditions were a temperature of 25°C, a chuck distance of 111.5 mm, and a test speed of 10 mm / min. The fractured interface after the adhesion test was observed and recorded in Tables 1 and 2 as CF = cohesive failure and AF = interfacial failure.

[0074] (2) Adhesive strength at high temperatures [180°C x 20 minutes (measured in a 180°C environment)] In order to confirm the heat resistance of the test pieces (adhesive resin) after the adhesive had been cured at 25°C for 16 hours, they were left at 180°C for 20 minutes, and then the tensile shear strength of the adhesive joint was measured in the same manner as in (1) above, except that the measurement conditions were changed to a temperature of 180°C.

[0075] <Evaluation Results> Examples 1 to 2, 4 to 10, and Examples 1' and 2' all exhibited good adhesive strength at room temperature and at high temperatures. On the other hand, in Comparative Examples 3, 11 to 12, and 3', which did not contain diamine, the adhesive strength at high temperatures was low and not at a satisfactory level.

Claims

1. A curing agent (A); A composition comprising an isocyanate group-terminated polyisocyanate (B), The curing agent (A) contains a polyol (a1) and a diamine (a2), the content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less, The polyol (a1) comprises a polycarbonate polyol, The adhesive composition, wherein the diamine (a2) comprises a diamine represented by formula (1): 【Chemistry 1】 In formula (1), Each R is independently any one selected from the group consisting of an amino group, a halogen atom, an alkyl group, a cycloalkyl group, and an alkoxycarbonyl group; n is an integer less than or equal to 4; When n is 1, R is an amino group; When n is an integer between 2 and 4, Any one of R is an amino group; The other R is any one other than an amino group.

2. A curing agent (A); A composition comprising an isocyanate group-terminated polyisocyanate (B), The curing agent (A) contains a polyol (a1) and a diamine (a2), the content of the diamine (a2) relative to the resin component in the composition is 0.05 mmol / g or more and 1.00 mmol / g or less, The polyol (a1) comprises a polycarbonate polyol, The adhesive composition, wherein the diamine (a2) comprises a diamine represented by formula (2): 【Chemistry 2】 In formula (2), R １ and R ２ each independently represents one selected from the group consisting of a halogen atom, an alkyl group, and an alkoxycarbonyl group; R ３ is a divalent group composed of one or more atoms selected from the group consisting of carbon atoms, sulfur atoms, hydrogen atoms, and oxygen atoms; p and q each independently represent an integer of 3 or less.

3. The adhesive composition according to claim 1 or 2, further comprising a filler (C).

4. The adhesive composition according to claim 3 , wherein a content of the filler (C) is 70 mass % or less.

5. The adhesive composition according to claim 4 , wherein the content of the filler (C) is 10% by mass or more and 50% by mass or less.

6. The adhesive composition according to any one of claims 3 to 5, wherein the filler (C) comprises an inorganic filler.

7. The adhesive composition according to any one of claims 1 to 6, which is a solvent-free adhesive composition.

8. An adhesive comprising the adhesive composition according to any one of claims 1 to 7.

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