WO2023085387A1 - Composition de formation de résine d'uréthane et agent adhésif de type à deux parties - Google Patents

Composition de formation de résine d'uréthane et agent adhésif de type à deux parties Download PDF

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WO2023085387A1
WO2023085387A1 PCT/JP2022/042003 JP2022042003W WO2023085387A1 WO 2023085387 A1 WO2023085387 A1 WO 2023085387A1 JP 2022042003 W JP2022042003 W JP 2022042003W WO 2023085387 A1 WO2023085387 A1 WO 2023085387A1
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component
particles
urethane
composition according
composition
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PCT/JP2022/042003
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Japanese (ja)
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考宏 相澤
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東ソー株式会社
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    • 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
    • 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
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • C09J175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a urethane resin-forming composition and a two-component adhesive.
  • Various types of adhesives are known, such as epoxy adhesives and urethane adhesives.
  • Structural adhesives are required to have strength and durability, and especially for automotive applications, a high glass transition temperature (Tg) is required from the viewpoint of strength stability in the operating temperature range.
  • Epoxy-based adhesives generally have a higher Tg and higher strength than urethane-based adhesives, but are brittle.
  • urethane-based adhesives are attracting attention as structural adhesives that require toughness.
  • a reactive two-liquid type adhesive is sometimes used, and one example of such an adhesive is disclosed in Patent Document 1.
  • the storage stability of the first liquid is improved while maintaining the effect of obtaining good adhesion performance without applying a primer treatment or sanding treatment. is also considered to be superior.
  • the composition disclosed in Patent Document 1 consists of a first liquid containing a prepolymer obtained by reacting a polyisocyanate and a polyol, and a second liquid containing a polyol and a catalyst.
  • the second liquid is a high molecular weight polyol having a number average molecular weight of 1000 or more (II ) and a low-molecular-weight polyol having a number average molecular weight of less than 1000
  • the molar ratio of (I), (II) and the low-molecular-weight polyol is a predetermined amount.
  • an object of one embodiment of the present invention is to provide a urethane resin-forming composition that contributes to the production of adhesives having high toughness.
  • it is intended to provide a urethane resin-forming composition that can be used as an adhesive and that can give a cured product with high toughness even when a filler is contained. be.
  • Another object of the present invention is to provide a two-component adhesive with high toughness.
  • a composition according to one embodiment of the present invention and a two-component adhesive according to one embodiment include the following aspects (1) to (17).
  • a component (A) comprising an isocyanate-terminated polyisocyanate
  • a component (B) comprising a polyol
  • a component (C) containing urethane particles The component (B) is a cross-linking agent (b1) (a cross-linking agent (b1) having a functional group reactive with the isocyanate of the component (A) and having an average number of functional groups exceeding 2);
  • a urethane resin-forming composition comprising a carbonate group-containing polyol (b2).
  • the urethane particles are thermoplastic polyurethane particles;
  • the glass transition temperature of the urethane particles (the glass transition temperature defined by the peak temperature of tan ⁇ measured by dynamic viscoelasticity measurement under conditions of a heating rate of 2 mm/min and a measurement frequency of 10 Hz) is 20° C. or less.
  • (11) The composition according to (1) above, wherein the urethane particles are crosslinked polyurethane particles.
  • (16) The composition according to any one of (1) to (15) above, wherein the component (C) further contains an inorganic filler.
  • the liquid is a two-component adhesive containing the component (C) containing urethane particles.).
  • a urethane resin-forming composition that contributes to the production of an adhesive having high toughness, particularly a urethane resin-forming composition that can be used as an adhesive, contains a filler.
  • a urethane resin-forming composition capable of obtaining a cured product having high toughness even in such a case.
  • there is provided a two-component adhesive with high toughness there is provided.
  • Compositions comprise component (A) comprising an isocyanate-terminated polyisocyanate, component (B) comprising a polyol, and component (C) comprising urethane particles,
  • component (B) is a cross-linking agent (b1); and a carbonate group-containing polyol (b2).
  • Component (A) comprises an isocyanate-terminated polyisocyanate.
  • component (A) may contain fillers, polymer particles, antioxidants, stabilizers, and the like.
  • the isocyanate-terminated polyisocyanate is preferably the main component of component (A). % by weight, 95-100% by weight, or 100% by weight.
  • the isocyanate-terminated polyisocyanate preferably exhibits a liquid state at room temperature (23°C).
  • liquid means having fluidity at 23° C., and there are no restrictions on the viscosity as long as it can be mixed with the component (B). More specifically, the fluidity is contained in a flat-bottomed cylindrical glass test tube with an inner diameter of 30 mm and a height of 120 mm, the height of the material is 55 mm, the test tube is kept at 23 ° C., When the test tube is held horizontally, the liquid state is defined as the tip of the liquid surface passing through a portion 85 mm from the bottom of the test tube within 90 seconds.
  • liquid also applies to other components as described above.
  • the isocyanate group-terminated polyisocyanate may be an isocyanate compound containing two or more isocyanate groups in the molecule.
  • the isocyanate group-terminated polyisocyanate may be partially trimerized using a trimerization catalyst or partially allophanatized using an allophanatizing catalyst. It may be polymerized.
  • blocked polyisocyanates blocked polyisocyanates blocked with blocking agents such as phenols, alcohols, oximes, ⁇ -dicarbonyl compounds, and lactams are also included in the "isocyanate group-terminated polyisocyanates" in the present invention. .
  • isocyanate group-terminated polyisocyanates examples include aromatic isocyanates, aliphatic isocyanates, alicyclic isocyanates, and araliphatic isocyanates.
  • aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 2,4′-diphenylmethane diisocyanate, 4, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4, 4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropan
  • 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 diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diiso
  • alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4-isocyanate- n-butylidene)pentaerythritol, 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]-hept
  • araliphatic isocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof, ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene and the like.
  • Component (B) contains a polyol and includes a cross-linking agent (b1) and a carbonate group-containing polyol (b2).
  • the cross-linking agent is a compound that reacts with the isocyanate-terminated polyisocyanate of component (A) to introduce a cross-linked structure, and a cross-linking agent having an average number of functional groups of more than 2 or 3 or more is preferable.
  • the isocyanate-reactive functional groups include active hydrogen-containing groups such as hydroxyl groups, amino groups, and mercapto groups.
  • Component (B) may contain reaction inhibitors, antioxidants, antifoaming agents, etc., in addition to these. These may be added to component (A) instead of component (B), or may be added to both component (A) and component (B).
  • the total content of the crosslinking agent (b1) and the carbonate group-containing polyol (b2) relative to the total amount of component (B) is, for example, 80 to 100% by mass, 85 to 100% by mass, 90 to 100% by mass, 95 to 100% by mass. Or it can be 100% by mass.
  • cross-linking agent (b1) cross-linking agent (b1) having a functional group reactive with the isocyanate of component (A) and having an average number of functional groups exceeding 2) include polyols having an average number of functional groups of 3 or more.
  • carbonate group-containing polyol is a polyol having an average number of functional groups exceeding 2
  • the polyol is included in the carbonate group-containing polyol (b2) instead of the cross-linking agent (b1).
  • the carbonate group-containing polyol (b2) is used from the viewpoint of strength, heat resistance, weather resistance, and durability, and when considering its use as an adhesive, it is a liquid polycarbonate that can be handled as a liquid at room temperature (23 ° C.). Polyols are particularly preferred.
  • carbonate group-containing polyols 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, diethylene glycol, dipropylene glycol, neo pentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, glycerin, trimethylolpropane, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis( ⁇ -hydroxyethyl)benzene, one or
  • Component (C) contains urethane particles.
  • the urethane particles should just contain a urethane skeleton.
  • Preferred urethane particles are thermoplastic polyurethane particles or crosslinked polyurethane particles.
  • the volume average particle diameter of the urethane particles is 200 ⁇ m or less, preferably 100 ⁇ m or less, and particularly preferably 50 ⁇ m or less.
  • the volume average particle diameter can be measured using a laser diffraction/scattering particle size distribution analyzer such as Microtrac MT3300EXII (manufactured by Microtrac Bell Co., Ltd.).
  • the urethane particles may be blended with the isocyanate-terminated polyisocyanate (A), may be blended with the polyol (B), or may be blended with both the polyisocyanate (A) and the polyol (B).
  • the content of the urethane particles in the urethane resin composition is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. Further, it may be 7% by mass to 20% by mass.
  • the blending amount of urethane particles is 1% by mass or more, the fracture toughness value is further improved.
  • the amount of the urethane particles is 50% by mass or less, the viscosity becomes lower, so that the coating property is improved when used as an adhesive.
  • the tensile elastic modulus of the urethane particles at 23°C in accordance with JIS K7312: 1996 may be 500 MPa or less, preferably 300 MPa or less, particularly preferably 100 MPa or less, or 50 MPa or less, 30 MPa or less, or 20 MPa or less.
  • the fracture toughness value is further improved.
  • the tensile elastic modulus of the urethane particles at 23° C. in accordance with JIS K7312:1996 may be, for example, 1 MPa or higher, 2 MPa or higher, 3 MPa or higher, 5 MPa or higher, or 10 MPa or higher.
  • the tensile modulus of the urethane resin-forming composition (cured product of the urethane resin-forming composition) at 23° C. according to JIS K7312:1996 is higher than the tensile modulus of urethane particles measured under the same conditions. preferable.
  • the ratio (P/L) of the tensile elastic modulus (P) of the urethane particles to the tensile elastic modulus of the cured product of the urethane resin-forming composition (L) is preferably 1/5 or less, preferably 1/10. It may be less than or equal to 1/100 or more and 1/20 or less.
  • the melting point of the thermoplastic polyurethane particles is preferably 160° C. or lower, more preferably 70° C. or higher and 140° C. or lower, and particularly preferably 130° C. or lower. It is preferable that the urethane particles have a melting point of 160° C. or less because they are well compatible with the base material.
  • the melting point here means the outflow start temperature, and the outflow start temperature can be measured with a Koka-type flow tester.
  • the measurement conditions can be a load of 9.8 N, a die of ⁇ 1 ⁇ 1 mm, and a heating rate of 3° C./min.
  • the glass transition temperature of the thermoplastic polyurethane particles is 20°C or lower, preferably 0°C or lower, more preferably -20°C or lower, and even more preferably -30°C or lower.
  • the glass transition temperature can be defined by the peak temperature of tan ⁇ obtained by dynamic viscoelasticity measurement under conditions of a heating rate of 2 mm/min and a measurement frequency of 10 Hz.
  • the storage modulus of the thermoplastic polyurethane particles is preferably 10 8 Pa or less at room temperature (23° C.). More preferably, it is 10 7 Pa or more and 10 8 Pa or less.
  • the elastic modulus of the urethane particles at room temperature is 10 8 Pa or less, the particles have an optimum elastic modulus, and the effect of improving fracture toughness is further enhanced.
  • the storage elastic modulus can be determined as the storage elastic modulus at 23° C. by dynamic viscoelasticity measurement under conditions of a heating rate of 2 mm/min and a measurement frequency of 10 Hz.
  • inorganic fillers and the like may be included, for example, silica and the like may be included at the same time.
  • component (C) is not particularly limited, but it can be blended using, for example, a revolution-rotation stirrer or the like.
  • Component (C) may be blended in advance with both or one of components (A) and (B), or component (C) may be blended at the same time when components (A) and (B) are mixed. good.
  • the amount of component (C) blended with components (A) and (B) may or may not be equal. .
  • composition can take various forms.
  • the composition is a one-component composition containing all of component (A), component (B) and component (C) in one component, component (A) and component (B) are present separately, and component (C ) is contained in at least one of component (A) and component (B), and a three-component composition in which component (A), component (B) and component (C) are present separately (component (C) may be contained in at least one of component (A) and component (B)), components other than component (A), component (B) and component (C) are present separately (at least part of component (C) may be contained in at least one of component (A), component (B) and other components).
  • the isocyanate-terminated polyisocyanate in component (A) is preferably blocked polyisocyanate blocked with a blocking agent.
  • the composition cures (crosslinks) through the reaction of the isocyanate-terminated polyisocyanate in component (A) with the polyol in component (B).
  • a curing (crosslinking) reaction can be caused by heating or the like.
  • a curing (crosslinking) reaction can be caused by heating or the like as necessary.
  • the crosslinkable group concentration in the urethane resin-forming composition can be 0.3 mmol/g or more.
  • the crosslinkable group concentration may be 0.4 mmol/g or more, 0.5 mmol/g or more, 0.6 mmol/g or more, or 0.7 mmol/g or more.
  • the crosslinkable group concentration can be, for example, 10.0 mmol/g or less, 8.0 mmol/g or less, 6.0 mmol/g or less, or 5.0 mmol/g or less.
  • the crosslinkable group concentration can be obtained as a calculated value.
  • a crosslinkable group means a functional group that forms a crosslink.
  • a trifunctional polyol eg, glycerin
  • one hydroxyl group in one molecule forms a crosslink, and the remaining two hydroxyl groups do not contribute to the crosslink (these two contribution), so in this case there is one crosslinkable group. That is, in the case of a trifunctional polyol, since the trifunctional polyol has one crosslinkable group, the content of the crosslinkable group is synonymous with the content of the trifunctional polyol.
  • the crosslinkable group concentration and the crosslink density are synonymous.
  • the composition may contain a solvent. That is, at least one of component (A) and component (B) may contain a solvent.
  • the total solvent content is preferably 1% by mass or less, and a solvent-free type containing substantially no solvent is particularly preferred.
  • the solvent-free type which does not substantially contain a solvent, includes the case where the solvent component is contained as an impurity, and the case where the solvent component is contained in an amount that cannot be removed even by purification.
  • the solvent content in the composition is 1% by mass or less, it is possible to further suppress the occurrence of dripping due to excessively low viscosity.
  • a catalyst can also be used for the purpose of promoting the reaction between the isocyanate group-terminated polyisocyanate and the polyol. That is, at least one of component (A) and component (B) may contain a catalyst. It is particularly preferable from the viewpoint of reactivity control that the content of the catalyst is 0.05% by mass or less in the composition.
  • catalysts include isocyanurate-forming catalysts and urethanization-catalysts, and specific examples are shown below.
  • isocyanuration catalysts examples include triethylamine, N-ethylpiperidine, N,N'-dimethylpiperazine, N-ethylmorpholine, tertiary amines such as Mannich bases of phenol compounds, and potassium acetate. Moreover, these isocyanurate-forming catalysts can be used alone or in combination of two or more.
  • the urethanization catalyst can be appropriately selected from known catalysts and used, and examples thereof include amine-based catalysts, imidazole-based catalysts, metal catalysts, and the like.
  • amine catalysts 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'-pentamethyl
  • Examples include dipropylenetriamine, N,N,N',N'-tetramethylhexamethylenediamine, bis(2-dimethylaminoethyl)ether and the like.
  • imidazole-based catalysts examples include 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, and the like.
  • metal catalysts include organotin catalysts such as stannus diacetate, stannus dioctoate, stannus dioleate, stannus dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate. etc. can be mentioned.
  • compositions according to the above embodiments exhibit a high Tg (80° C. or higher) and an excellent adhesive strength (10 MPa or higher) at room temperature, and further obtain an excellent fracture toughness value (1 kJ/m 2 or higher).
  • Tg can be measured by DMA7100 (manufactured by Hitachi High-Tech Science Co., Ltd.) and can be evaluated by the tan ⁇ peak temperature when the measurement frequency is 10 Hz.
  • Normal temperature means 15° C. or more and 35° C. or less, and particularly means 20° C. or more and 30° C. or less.
  • the adhesive strength conforms to the tensile shear adhesive strength of adhesives of JIS K6850:1999. Fracture toughness values were evaluated by the double cantilever beam (DCB) test, which was performed according to ASTM D3433-99.
  • composition described above can also be used as an adhesive (especially a two-part type adhesive) for various purposes, and the application fields include, for example, the automobile field, the display field, the recording medium field, the electronic material field, and the battery field. , optical parts, construction, electronic equipment, aviation, etc.
  • 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 components (A) and (B) are used by mixing and reacting. After mixing, the mixture may be stored at room temperature (23° C.) for curing, or, for example, may be cured by heating at 80 to 180° C. for about 1 to 60 minutes.
  • the isocyanate group-terminated polyisocyanate and polyol were produced by the method described below.
  • the information and abbreviations of the raw materials used are as follows.
  • isocyanate group-terminated polyisocyanate 1000 g of Millionate NM, which is a mixture of 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, is added to a 2 L stirring vessel filled with nitrogen, and the liquid temperature is adjusted to 60°C. 0.05 g of dimethylaminomethylphenol was added to allow the nurate reaction to proceed, and 0.1 g of a terminator (benzoyl chloride) was added at an appropriate timing to deactivate the catalyst to obtain an isocyanate group-terminated polyisocyanate. The resulting isocyanate group-terminated polyisocyanate had a nurate content of 45% and an NCO content of 26%.
  • composition of urethane particles and other fillers Urethane particles, polyamide particles, talc, and zeolite were added to the isocyanate group-terminated prepolymer and polyol in advance so that the ratios described in "Additives” in Table 2 were obtained. (manufactured by Shashin Kagaku Co., Ltd.). Component (C) was evenly blended with the isocyanate group-terminated prepolymer and polyol.
  • composition was prepared by combining an isocyanate group-terminated prepolymer and a polyol, each of which was previously compounded with urethane particles and other fillers so as to achieve the ratio described in Table 2, "Composition”. Then, a cured product was prepared according to the following "Preparation of Test Piece and Evaluation Criteria", and the adhesive strength, fracture toughness value, and Tg were measured by the methods described below.
  • Table 2 shows the urethane group concentration, crosslink density, and nurate concentration. These values are those of the urethane resin composition (resin that is a cured product obtained by reacting component (A) and component (B)).
  • the urethane group concentration is a calculated value for the cured product, and can be calculated from the amount of isocyanate groups contained in component (A) and the amount of hydroxyl groups contained in component (B).
  • the crosslink density can be determined from the amount of polyol having 3 or more hydroxyl groups in the total amount of the cured product, and the nurate content is the content of the isocyanurate modified product in the isocyanate-terminated polyisocyanate (A). It was calculated from peak area % in Gel Permeation Chromatography (GPC) measurement used as a calibration curve. The crosslink density (synonymous with crosslinkable group concentration) was obtained as a calculated value.
  • Sheet molding A resin sheet having a thickness of about 2 mm was obtained by hot press molding both the urethane particles and the polyamide particles.
  • the urethane resin composition was prepared by mixing component (A) and component (B) according to the formulation shown in Table 2, storing the mixture at 23°C for 16 hours, baking it at 180°C for 20 minutes, and curing it at 23°C for 1 week. A resin sheet was obtained.
  • Table 1 shows the results.
  • (3) Viscoelasticity Evaluation Dynamic viscoelasticity of the obtained resin sheet was measured by temperature dispersion using a viscoelasticity measuring instrument (trade name: DMA7100, manufactured by Hitachi High-Tech Science). The measurement temperature range was ⁇ 100° C. to 250° C., the temperature increase rate was 2 mm/min, the measurement frequency was 10 Hz, and the peak temperature of tan ⁇ was defined as Tg. Table 1 shows the results.
  • Adhesive strength at room temperature [23°C x 16 hours curing ⁇ 180°C x 20 minutes (23°C environmental measurement)] Adhesive is applied to the surfaces of two aluminum plates (length 100 mm x width 25 mm x thickness 1 mm; A6061, T-Zr treated) so that the overlapping area of the aluminum plates is 12.5 mm length x 25 mm width.
  • An adhesion test piece was prepared by bonding, leaving this under conditions of 23° C. for 16 hours, and further curing at 180° C. for 20 minutes. At this time, glass beads were used to adjust the thickness of the adhesive layer to 0.25 mm to obtain an adhesive test piece.
  • the tensile shear strength of the adhesive portion was measured using a tensile tester (trade name: Autocom universal testing machine AC-10kN-C, manufactured by TSE Co., Ltd.) for the adhesive test piece prepared as described above. . This measurement was performed in accordance with JIS K6850:1999, Tensile Shear Bond Strength of Adhesives. The measurement conditions were a temperature of 23° C., a distance between chucks of 111.5 mm, and a test speed of 10 mm/min.
  • TB in Table 1 is tensile strength
  • EB is elongation at break
  • M50 is tensile stress at 50% elongation
  • M100 is tensile stress at 100% elongation
  • M200 is 200% elongation
  • M300 represents the tensile stress at 300% elongation.
  • Tg evaluation The composition was mixed, stored at 23°C for 16 hours, baked at 180°C for 20 minutes, and cured at 23°C for 1 week.
  • the viscoelasticity was measured by temperature dispersion using an elasticity measuring machine (trade name: DMA7100, manufactured by Hitachi High-Tech Science).
  • the measurement temperature range was ⁇ 100° C. to 250° C.
  • the temperature increase rate was 2 mm/min
  • the measurement frequency was 10 Hz
  • the peak temperature of tan ⁇ was defined as Tg.
  • Tg was 80°C or higher, the value was judged to be sufficiently high.
  • Resin thickness Adjusted with a spacer to be 0.35 mm
  • Spacer uses Teflon (registered trademark) tape
  • Test substrate S50C steel (electroless nickel plating) is used
  • Load (N) Young's modulus of E base material (MPa): 208000 B Base material width (mm): 25.49 m constant (from contoured type): 3.54
  • Examples 1 to 8 contain urethane particles, and when the same amount of inorganic filler is included as compared to Comparative Examples 1 and 3 to 6 in which polyamide particles are blended, the fracture toughness is always higher when urethane particles are included. was value. Further, according to Comparative Examples 2 to 6, the polyamide particles have the highest fracture toughness value in Comparative Example 2 in which polyamide particles are not blended, and Comparative Examples 3 to 6 in which polyamide particles are blended have higher fracture toughness values than Comparative Example 2. is low. On the other hand, according to Comparative Example 2 and Examples 2 to 5, Comparative Example 2, which does not contain urethane particles, has the lowest fracture toughness value, and Examples 2 to 5, which contain urethane particles, are all higher than Comparative Example 2. Fracture toughness value is high.
  • Comparative Example 14 contained silicone particles and Comparative Example 15 contained polyetherimide particles, but both had low fracture toughness values of less than 1.0.
  • the reference example did not contain all urethane particles, polyamide particles, and inorganic fillers, and the fracture toughness test resulted in interfacial fracture, making it impossible to accurately evaluate the toughness of the resin. In addition, traces of foaming were also observed in the resin.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

La présente invention comprend un composant (A) contenant un polyisocyanate à terminaison isocyanate, un composant (B) contenant un polyol, et un composant (C) contenant des particules d'uréthane. Le composant (B) contient un agent de réticulation (b1) et un polyol contenant un groupe carbonate (b2).
PCT/JP2022/042003 2021-11-12 2022-11-10 Composition de formation de résine d'uréthane et agent adhésif de type à deux parties WO2023085387A1 (fr)

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* Cited by examiner, † Cited by third party
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JPH07196758A (ja) * 1993-12-28 1995-08-01 Nippon Polyurethane Ind Co Ltd 強化ポリウレタン用フィラー含有ポリオールおよび該ポリオールを用いた強化ポリウレタンの製造方法
JP2002332402A (ja) * 2001-03-06 2002-11-22 Sanyo Chem Ind Ltd 水性分散体およびポリウレタン樹脂ペーストゾル
JP2007070591A (ja) * 2005-08-10 2007-03-22 Yokohama Rubber Co Ltd:The 硬化性樹脂／ポリウレタン混合物および硬化性樹脂組成物
JP2015514155A (ja) * 2012-04-16 2015-05-18 ドリッテ パテントポートフォーリオ ベタイリグングスゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトＤｒｉｔｔｅ Ｐａｔｅｎｔｐｏｒｔｆｏｌｉｏ Ｂｅｔｅｉｌｉｇｕｎｇｓｇｅｓｅｌｌｓｃｈａｆｔ ｍｂＨ ＆ Ｃｏ． ＫＧ 官能基化ポリウレタンナノ粒子およびラジカル硬化性モノマーのエマルション重合により製造することができる重合物、前記重合物の製造方法および前記重合物の使用。
JP2015525822A (ja) * 2012-08-09 2015-09-07 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 複合フォーム
JP2019065234A (ja) * 2017-10-05 2019-04-25 東ソー株式会社 熱可塑性ポリウレタン粒子含有塩化ビニル樹脂組成物及びその用途
JP2021091863A (ja) * 2019-12-06 2021-06-17 東ソー株式会社 ポリウレタン樹脂形成性組成物、接着剤用組成物、硬化物および接着物
JP2021143321A (ja) * 2019-07-10 2021-09-24 東ソー株式会社 組成物、接着剤用組成物および接着剤

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07196758A (ja) * 1993-12-28 1995-08-01 Nippon Polyurethane Ind Co Ltd 強化ポリウレタン用フィラー含有ポリオールおよび該ポリオールを用いた強化ポリウレタンの製造方法
JP2002332402A (ja) * 2001-03-06 2002-11-22 Sanyo Chem Ind Ltd 水性分散体およびポリウレタン樹脂ペーストゾル
JP2007070591A (ja) * 2005-08-10 2007-03-22 Yokohama Rubber Co Ltd:The 硬化性樹脂／ポリウレタン混合物および硬化性樹脂組成物
JP2015514155A (ja) * 2012-04-16 2015-05-18 ドリッテ パテントポートフォーリオ ベタイリグングスゲゼルシャフト ミット ベシュレンクテル ハフツング ウント コンパニー コマンディートゲゼルシャフトＤｒｉｔｔｅ Ｐａｔｅｎｔｐｏｒｔｆｏｌｉｏ Ｂｅｔｅｉｌｉｇｕｎｇｓｇｅｓｅｌｌｓｃｈａｆｔ ｍｂＨ ＆ Ｃｏ． ＫＧ 官能基化ポリウレタンナノ粒子およびラジカル硬化性モノマーのエマルション重合により製造することができる重合物、前記重合物の製造方法および前記重合物の使用。
JP2015525822A (ja) * 2012-08-09 2015-09-07 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 複合フォーム
JP2019065234A (ja) * 2017-10-05 2019-04-25 東ソー株式会社 熱可塑性ポリウレタン粒子含有塩化ビニル樹脂組成物及びその用途
JP2021143321A (ja) * 2019-07-10 2021-09-24 東ソー株式会社 組成物、接着剤用組成物および接着剤
JP2021091863A (ja) * 2019-12-06 2021-06-17 東ソー株式会社 ポリウレタン樹脂形成性組成物、接着剤用組成物、硬化物および接着物

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