WO2024095701A1 - Composition durcissable à composant unique - Google Patents

Composition durcissable à composant unique Download PDF

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Publication number
WO2024095701A1
WO2024095701A1 PCT/JP2023/036591 JP2023036591W WO2024095701A1 WO 2024095701 A1 WO2024095701 A1 WO 2024095701A1 JP 2023036591 W JP2023036591 W JP 2023036591W WO 2024095701 A1 WO2024095701 A1 WO 2024095701A1
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Prior art keywords
curable composition
epoxy resin
composition according
mass
component curable
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PCT/JP2023/036591
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English (en)
Japanese (ja)
Inventor
剛宏 村田
淳之 宇野
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サンスター技研株式会社
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Priority to JP2023567893A priority Critical patent/JP7489556B1/ja
Publication of WO2024095701A1 publication Critical patent/WO2024095701A1/fr

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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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/23—Azo-compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
    • C08K5/24—Derivatives of hydrazine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D109/00—Coating compositions based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09D109/02—Copolymers with acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
    • C09D125/02—Homopolymers or copolymers of hydrocarbons
    • C09D125/04—Homopolymers or copolymers of styrene
    • C09D125/08—Copolymers of styrene
    • C09D125/10—Copolymers of styrene with conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic

Definitions

  • the present invention relates to a one-component curable composition, and more specifically, to a coating-type one-component curable composition that contains (A) an epoxy resin, (B) a solid rubber, (C) a latent curing agent, (D) a filler, and (E) a foaming agent.
  • Thinned sheet metal is used to reduce the weight of automobile bodies.
  • Sheet metal reinforcement materials are used to ensure the tension rigidity and dent resistance of the sheet metal.
  • sheet metal reinforcement materials have a three-layer structure of glass cloth, adhesive, and release paper, and are sold commercially as standard products with a certain plate shape.
  • Such standard sheet metal reinforcement materials are used after being adjusted to the desired shape.
  • the adjusted shape of the sheet metal reinforcement material is attached to the sheet metal, but due to the influence of the usage environment, the adhesiveness decreases and the attachment position becomes misaligned, so corrections must be made by a person (worker). Therefore, it is difficult to fully automate sheet metal reinforcement using standard sheet metal reinforcement materials, and this inevitably leads to a decrease in productivity.
  • Patent Document 1 discloses a spreadable sheet metal reinforcement composition made by blending an inorganic filler with a specific aspect ratio (L/D) with a liquid composition of a thermosetting epoxy resin to form a highly viscous, viscous material.
  • Patent Document 1 discloses that the spreadable sheet metal reinforcement composition can be applied under heating, and by allowing it to cool and solidify after application, it does not scatter, dissolve, or fall off during the process up to curing and baking, particularly in terms of shower resistance, chemical conversion treatment solutions, and electrolytes, and also improves the bending strength and rigidity of the sheet metal in terms of reinforcing effect, and does not cause distortion in the sheet metal even after curing (see Patent Document 1 [0005]).
  • Patent Document 1 has excellent properties, but there is a demand for improved reinforcement while suppressing distortion, and for improved shower resistance while maintaining pump discharge performance.
  • Patent Document 1 obtains a coated sheet metal reinforcing material by making it a high-viscosity viscous material, and does not teach anything about improving bending strength, improving shower resistance, or maintaining low viscosity and pump discharge performance.
  • the present invention therefore aims to provide a one-component curable composition that can be applied by heating while maintaining a low viscosity, but does not scatter, dissolve, or fall off during the process from application to curing and baking, particularly in the case of showers, chemical conversion coating solutions, and electrodeposition solutions, and that, after curing, improves the bending strength and rigidity of sheet metal without causing distortion in the sheet metal.
  • a one-component curable composition comprising (A) an epoxy resin, (B) a solid rubber, (C) a latent curing agent, (D) a filler, and (E) a foaming agent, (A) the epoxy resin contains (A1) an unmodified bisphenol-type epoxy resin, The one-component curable composition contains 10 to 100 parts by mass of a solid rubber (B) per 100 parts by mass of an epoxy resin (A), (B) The solid rubber is a one-component curable composition containing (B1) a styrene-butadiene-divinylbenzene copolymer. 2.
  • the one-component curable composition according to 1 above having a viscosity of 50 to 300 Pa ⁇ s at 40° C. and a shear rate of 430 sec ⁇ 1 . 3.
  • the filler (D) contains an inorganic filler having an aspect ratio (L/D) of 5 or more.
  • the one-part curable composition according to an embodiment of the present invention is capable of improving reinforcement while suppressing distortion, and improving shower resistance while maintaining pump dischargeability. Furthermore, the one-part curable composition can be suitably applied to sheet metal, and can be suitably used as a paint-type sheet metal reinforcement material.
  • a one-part curable composition includes (A) an epoxy resin, (B) a solid rubber, (C) a latent curing agent, (D) a filler, and (E) a foaming agent.
  • the epoxy resin contains (A1) an unmodified bisphenol-type epoxy resin
  • the one-component curable composition contains 10 to 100 parts by mass of a solid rubber (B) per 100 parts by mass of an epoxy resin (A);
  • the solid rubber (B) includes a styrene-butadiene-divinylbenzene copolymer (B1).
  • the epoxy resin (A) refers to a thermosetting resin that can be cured by generating a crosslinked network through the epoxy groups present therein, and is generally called an epoxy resin.
  • the (A) epoxy resin may be, for example, a glycidyl ether type epoxy resin, a glycidyl amine type epoxy resin, a glycidyl ester type epoxy resin, or the like.
  • the (A) epoxy resin preferably contains (A1) an unmodified bisphenol-type epoxy resin.
  • the unmodified bisphenol epoxy resin (A1) is an epoxy resin having a bisphenol skeleton, which is not particularly modified, and is not particularly limited as long as it can provide the epoxy resin composition of the present invention.
  • Examples of the unmodified bisphenol type epoxy resin (A1) include diglycidyl ethers of bisphenol A, bisphenol F, brominated bisphenol A, and bisphenol AD.
  • the viscosity of the unmodified bisphenol epoxy resin (A1) at 25°C is preferably 1500 mPa ⁇ s or more, more preferably 2000 to 25000 mPa ⁇ s, even more preferably 2500 to 20000 mPa ⁇ s, and even more preferably 3000 to 15000 mPa ⁇ s.
  • the (A1) unmodified bisphenol type epoxy resin preferably has an epoxy equivalent of 150 to 800 g/eq, more preferably an epoxy equivalent of 160 to 500 g/eq, even more preferably an epoxy equivalent of 165 to 250 g/eq, and even more preferably an epoxy equivalent of 170 to 200 g/eq.
  • the workability is superior.
  • the unmodified bisphenol epoxy resin (A1) a commercially available product can be used. Examples of the commercially available product include "jER (registered trademark) 828", “jER (registered trademark) 1001" and “jER (registered trademark) 807” manufactured by Mitsubishi Chemical Corporation.
  • the epoxy resin (A) preferably contains 25 to 90 mass% of the unmodified bisphenol epoxy resin (A1), based on 100 mass% of the epoxy resin, alternatively may contain 25 to 60 mass%, more preferably contain 29 to 80 mass%, may contain 29 to 56 mass%, further preferably contain 33 to 65 mass%, even more preferably contain 33 to 52 mass%, and further more preferably contain 35 to 49 mass%.
  • the curable composition according to an embodiment of the present invention can have a more balanced improvement in Tg, elastic modulus, and flexural strength.
  • the epoxy resin (A) may include a low-viscosity epoxy resin (A2).
  • the low-viscosity epoxy resin (A2) refers to an epoxy resin having a viscosity of less than 5000 mPa ⁇ s at 25° C., preferably having a viscosity of 40 to 5000 mPa ⁇ s, more preferably having a viscosity of 45 to 4000 mPa ⁇ s, even more preferably having a viscosity of 50 to 3000 mPa ⁇ s, and even more preferably having a viscosity of 60 to 2500 mPa ⁇ s.
  • the curable composition according to an embodiment of the present invention can ensure pumpability at relatively low temperatures (40-50° C.).
  • the low-viscosity epoxy resin (A2) preferably has an epoxy equivalent of 250 to 700, more preferably 280 to 680, and even more preferably 300 to 650.
  • the curable composition of the embodiment of the present invention has flexibility and exhibits a large displacement amount at maximum strength in a bending test.
  • the curable composition of the present embodiment can achieve both of the above effects.
  • the low-viscosity epoxy resin (A2) may contain a dibasic acid ester-based epoxy resin (A2-1).
  • Dibasic acid ester epoxy resins include epoxy resins based on esters of dibasic acids (for example, long-chain dibasic acids such as dimer acid, phthalic acid, and hydrogenated phthalic acid).
  • the dibasic acid ester-based epoxy resin (A2-1) corresponds to the above-mentioned (A2) low-viscosity epoxy resin, and is not particularly limited as long as the epoxy resin composition targeted by the present invention can be obtained.
  • the dibasic acid ester epoxy resin (A2-1) commercially available products can be used. Examples of such commercially available products include "jER (registered trademark) 871" (dimer acid glycidyl ester) manufactured by Mitsubishi Chemical Corporation.
  • Low-viscosity epoxy resins can also include diglycidyl ethers of alkylene oxide adducts of bisphenol A, bisphenol F, bisphenol AD, etc., bifunctional epoxy resins used as reactive diluents, and monofunctional epoxy resins that form part of the epoxy resin.
  • the epoxy resin (A) preferably contains 20 to 80 mass% of the low-viscosity epoxy resin (A2) relative to 100 mass% of the epoxy resin (A), more preferably 30 to 75 mass%, even more preferably 40 to 70 mass%, and even more preferably 50 to 65 mass%.
  • the curable composition according to an embodiment of the present invention can ensure pump dischargeability at a relatively low temperature (40 to 50° C.).
  • the low-viscosity epoxy resin (A2) does not include the unmodified bisphenol-type epoxy resin (A1).
  • the (A) epoxy resin may include (A1) an unmodified bisphenol-type epoxy resin and (A2) other epoxy resins that do not fall under the category of low-viscosity epoxy resins.
  • the (A3) other epoxy resin is an epoxy resin that does not fall under the category of (A1) unmodified bisphenol-type epoxy resin and (A2) low-viscosity epoxy resin, and is not particularly limited as long as the intended curable composition of the present invention can be obtained.
  • the (A) epoxy resin may contain (A3) other epoxy resin in an amount of 40 mass% or less, 30 mass% or less, or 20 mass% or less, based on 100 mass% of the epoxy resin.
  • Examples of such (A3) other epoxy resins include rubber-modified epoxy resins [such as a reaction product obtained by blending a bisphenol-type epoxy resin (diglycidyl ether of bisphenol A, bisphenol F, bisphenol AD, diglycidyl ether of an alkylene oxide adduct of bisphenol A, etc.) with a butadiene-acrylonitrile-(meth)acrylic acid copolymer in a mass ratio of 1:5 to 4:1, preferably 1:3 to 3:2, and reacting them at a temperature of 80 to 180° C.], urethane-modified epoxy resins [such as a reaction product obtained by reacting a polyurethane prepolymer having a polyisocyanate added to the end of a polyalkylene glycol with a hydroxyl group of an epoxy resin (mixing ratio of 10:90 to 50:50); for example, a reaction product obtained by reacting an excess amount of a diisocyanate (tolylene diisocyanate, diphen
  • the content of aromatic rings in the epoxy resin (A) is preferably 15 to 40 mass%, more preferably 18 to 35 mass%, even more preferably 20 to 32 mass%, and even more preferably 25 to 30 mass%, based on 100 mass% of the epoxy resin (A).
  • the curable composition according to an embodiment of the present invention can achieve better balanced improvements in Tg, elastic modulus, and flexural strength.
  • the curable composition according to an embodiment of the present invention may contain, for example, 25 to 80 parts by mass of the epoxy resin (A) per 100 parts by mass of the curable composition, preferably contains 30 to 70 parts by mass of the epoxy resin (A), more preferably contains 35 to 65 parts by mass of the epoxy resin (A), and more preferably contains 40 to 60 parts by mass of the epoxy resin (A).
  • the curable composition of the embodiment of the present invention contains 25 to 80 parts by mass of the epoxy resin (A) per 100 parts by mass of the curable composition, the curability and bending strength of the curable composition of the embodiment of the present invention can be further improved.
  • the solid rubber (B) is a solid rubber-like substance, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.
  • the "solid” in “solid rubber” means that the rubber is solid at room temperature (23°C). When rubber and a liquid component coexist, this means that the portion of the rubber excluding the liquid component is solid at room temperature (23°C). Therefore, even if rubber coexists with a liquid component at room temperature and may dissolve and/or swell, if the rubber is solid at room temperature (23°C) when the liquid component is removed, this corresponds to solid rubber.
  • the solid rubber (B) contains a styrene-butadiene-divinylbenzene copolymer (B1), and the curable composition according to an embodiment of the present invention can exhibit the advantageous effects of suppressing a decrease in Tg and a decrease in strength due to foaming (displacement at maximum strength in a bending test) while further improving shower resistance.
  • the solid rubber (B) preferably contains 20 to 80 mass % of the styrene-butadiene-divinylbenzene copolymer (B1), more preferably 25 to 75 mass %, even more preferably 30 to 70 mass %, and even more preferably 35 to 65 mass %, based on 100 mass % of the solid rubber (B).
  • the solid rubber (B) further contains at least one selected from a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer, an ethylene-propylene-diene copolymer, an isoprene polymer, and a butadiene polymer.
  • the solid rubber (B) may include a styrene-butadiene copolymer (B2) and an acrylonitrile-butadiene copolymer (B3).
  • the solid rubber (B) contains the styrene-butadiene copolymer (B2), it is possible to suppress a decrease in Tg of the cured product (reinforcing material) of the curable composition according to an embodiment of the present invention, ensure reinforcing properties, and suppress a decrease in strength due to foaming (displacement at maximum strength in a bending test).
  • the solid rubber (B) contains an acrylonitrile-butadiene copolymer (B3), the amount of displacement at maximum strength in a bending test of the curable composition according to an embodiment of the present invention can be further increased.
  • the solid rubber (B1) and/or the solid rubber (B2) preferably has an acid content of 0.2 to 8 mass%, more preferably 0.3 to 6 mass%, and even more preferably 0.5 to 4 mass%.
  • the storage stability of the curable composition according to the embodiment of the present invention can be further improved.
  • the curable composition according to an embodiment of the present invention may contain, for example, 10 to 100 parts by mass of the solid rubber (B) per 100 parts by mass of the epoxy resin (A), preferably contains 20 to 90 parts by mass of the solid rubber (B), more preferably contains 30 to 80 parts by mass of the solid rubber (B), and even more preferably contains 40 to 70 parts by mass of the solid rubber (B).
  • the curable composition of the embodiment of the present invention contains 10 to 100 parts by mass of the solid rubber (B) per 100 parts by mass of the epoxy resin (A)
  • the strain resistance of the curable composition of the embodiment of the present invention can be further improved while the displacement amount at maximum strength in a bending test can be further increased.
  • (C) latent curing agent refers to a compound that is a curing agent for (A) epoxy resin, does not substantially function as a curing agent at room temperature, but functions as a curing agent when heated (for example, to 165°C, preferably 150°C), and is not particularly limited as long as the curable composition targeted by the present invention can be obtained.
  • latent hardeners include dicyandiamide; dihydrazide compounds such as adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, dodecanediohydrazide, 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, eicosanedioic acid dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, and 4,4'-ethylidenebisphenol diglycolic acid dihydrazide; 4,4'-diaminodiphenyl sulfone; imidazole compounds such as imidazole, 2-n-heptadecylimidazole, and 2-undecylimidazole; melamine; 2,4-diamino-6- Examples of such compounds include triazine compounds such as
  • latent hardeners can be used. Examples include CG-NA (product name) manufactured by Air Products, EH-4030s (product name) manufactured by ADEKA, ADH (product name) manufactured by Otsuka Chemical, EH3731s (product name) manufactured by ADEKA, Dyhard UR200 (product name) manufactured by AlzChem, and DDH (product name) manufactured by Otsuka Chemical.
  • the curable composition according to an embodiment of the present invention may contain, for example, 1 to 30 parts by mass of the latent curing agent (C) per 100 parts by mass of the epoxy resin, preferably contains 2 to 25 parts by mass of the latent curing agent (C), more preferably contains 3 to 20 parts by mass of the latent curing agent (C), and more preferably contains 4 to 15 parts by mass of the latent curing agent (C).
  • the curable composition according to an embodiment of the present invention has an excellent balance between curability and storage stability when it contains 1 to 30 parts by mass of the latent curing agent (C) per 100 parts by mass of the epoxy resin.
  • the (D) filler is a compound that increases the amount of the curable composition of the embodiment of the present invention and can impart a certain degree of strength to the cured product formed from the curable composition, and in some cases can contribute to viscosity adjustment or weight reduction, and is not particularly limited as long as the curable composition intended by the present invention can be obtained.
  • Fillers include, for example, calcium carbonate (heavy calcium carbonate, precipitated calcium carbonate, surface-treated calcium carbonate, etc.), magnesium carbonate, carbonates and sulfates of alkaline earth metals such as barium sulfate, mica, graphite, talc, clay, glass flakes, vermiculite, kaolinite, wollastonite (acicular calcium metasilicate), silica, diatomaceous earth, gypsum, cement, converter slag, shirasu, zeolite, cellulose powder, powdered rubber, zonolite, potassium titanate, bentonite, aluminum nitride, silicon nitride, zinc oxide, titanium oxide, alumina, zinc oxide, iron oxide, magnesium oxide, titanium oxide, magnesium hydroxide, water.
  • alkaline earth metals such as barium sulfate, mica, graphite, talc, clay, glass flakes, vermiculite, kaolinite, wollastonite (aci
  • fillers examples include aluminum oxide, calcium silicate, calcium carbonate whiskers (needle-shaped calcium carbonate), ceramic short fibers or whiskers, rock wool short fibers, glass fiber short fibers, potassium titanate short fibers, calcium silicate short fibers, aluminum silicate, carbon fiber short fibers, aramid fiber short fibers, mineral fibers such as sepiolite, various whiskers, and other fibrous fillers, hollow fillers such as glass balloons, silica balloons, resin balloons, and carbon inorganic hollow spheres, organic hollow fillers such as plastic balloons made of organic synthetic resins such as vinylidene chloride and acrylonitrile, and metallic fillers such as aluminum fillers.
  • the filler preferably includes needle-shaped fillers having a length of 0.4 mm or more, more preferably includes needle-shaped fillers having a length of 0.4 mm or more and 40 mm or less, even more preferably includes needle-shaped fillers having a length of 5 mm or more and 30 mm or less, and even more preferably includes needle-shaped fillers having a length of 6 mm or more and 20 mm or less.
  • the strain resistance of the curable composition according to an embodiment of the present invention can be further improved.
  • the (D) filler preferably contains an inorganic filler having an aspect ratio (L/D) of 4 or more, more preferably contains an inorganic filler having an aspect ratio (L/D) of 4.5 or more and 20 or less, and even more preferably contains an inorganic filler having an aspect ratio (L/D) of 5 or more and 15 or less.
  • the distortion resistance of the curable composition according to the embodiment of the present invention can be further improved.
  • the inorganic filler may be any of the above-mentioned examples of fillers, excluding organic fillers (e.g., hollow fillers such as short rock wool fibers, short aramid fibers, resin balloons, and organic hollow fillers such as plastic balloons made of organic synthetic resins such as vinylidene chloride and acrylonitrile),
  • organic fillers e.g., hollow fillers such as short rock wool fibers, short aramid fibers, resin balloons, and organic hollow fillers such as plastic balloons made of organic synthetic resins such as vinylidene chloride and acrylonitrile
  • the curable composition of the embodiment of the present invention may contain, for example, 20 to 70 parts by mass of the (D) filler per 100 parts by mass of the curable composition, preferably contains 35 to 65 parts by mass of the (D) filler, more preferably contains 30 to 60 parts by mass of the (D) filler, and more preferably contains 35 to 55 parts by mass of the filler (D).
  • the curable composition of the embodiment of the present invention can have improved distortion resistance when it contains 20 to 70 parts by mass of the filler (D) per 100 parts by mass of the curable composition.
  • the foaming agent (E) refers to a substance added to increase the volume of the material, for example, a substance added to generate bubbles, and is, for example, a substance that generates a gas by decomposition or a substance that itself becomes a gas, and is not particularly limited as long as the curable composition targeted by the present invention can be obtained. Since the curable composition according to the embodiment of the present invention contains a foaming agent, the thickness after curing can be increased more efficiently, and the reinforcing property can be improved. Furthermore, by foaming, the elastic modulus of the cured product (i.e., the reinforcing material) obtained by curing the curable composition can be reduced, and the distortion can be reduced.
  • the (E) foaming agent for example, a foaming agent which foams upon heating is preferable, and examples thereof include inorganic foaming agents and organic foaming agents.
  • inorganic foaming agents include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and azides.
  • organic blowing agents include n-nitroso compounds, azo compounds (e.g., azodicarbonamide; ADCA), fluorinated alkanes, hydrazine compounds (e.g., 4,4'-oxybis(benzenesulfonylhydrazide): OBSH), semicarbazide compounds, and triazole compounds.
  • an example can be a heat-expandable particle (unexpanded balloon) in which a heat-expandable substance (e.g., isobutane, butane, etc.) is contained in a microcapsule made of a thermoplastic resin (e.g., polyvinylidene chloride, polyacrylonitrile, poly(meth)acrylic acid ester, etc.).
  • a heat-expandable substance e.g., isobutane, butane, etc.
  • a microcapsule made of a thermoplastic resin (e.g., polyvinylidene chloride, polyacrylonitrile, poly(meth)acrylic acid ester, etc.).
  • the foaming agent (E) preferably includes at least one selected from the group consisting of an azo-based compound (e.g., an ADCA-based chemical foaming agent), a hydrazine-based compound (e.g., an OBSH-based chemical foaming agent), and an unexpanded balloon.
  • an azo-based compound e.g., an ADCA-based chemical foaming agent
  • a hydrazine-based compound e.g., an OBSH-based chemical foaming agent
  • the curable composition according to the embodiment of the present invention can further improve the bending strength and further reduce the distortion while obtaining a desired foaming ratio.
  • the curable composition of the embodiment of the present invention may contain, for example, 0.1 to 10 parts by mass of the (E) foaming material per 100 parts by mass of the curable composition, preferably contains 0.2 to 5 parts by mass of the (E) foaming material, more preferably contains 0.3 to 3 parts by mass of the (E) foaming material, and even more preferably contains 0.4 to 2 parts by mass of the (E) foaming material.
  • the curable composition according to the embodiment of the present invention contains 0.1 to 10 parts by mass of the foaming material (E) per 100 parts by mass of the curable composition, the curable composition can be foamed more appropriately, and the curable composition can ensure better reinforcement while further suppressing distortion.
  • the curable composition according to the embodiment of the present invention may contain other components as appropriate.
  • other components include ordinary curing agents (excluding the latent curing agents described above), diluents, surfactants, and other additives.
  • a curing agent is a compound that does not have a curing effect at room temperature, but exhibits a curing effect when heated to a certain temperature, and is not particularly limited as long as the curable composition intended by the present invention can be obtained, except for the latent curing agents described above.
  • the diluent is not particularly limited as long as it can impart fluidity to the curable composition of an embodiment of the present invention and can provide the curable composition targeted by the present invention.
  • the diluent include hydrocarbon solvents such as paraffinic solvents, isoparaffinic solvents, naphthenic solvents, and aromatic solvents.
  • examples of other additives include moisture absorbents (calcium oxide, molecular sieves, etc.), thixotropic agents (organic bentonite, fumed silica, aluminum stearate, metal soaps, castor oil derivatives, etc.), stabilizers [2,6-di-t-butyl-4-methylphenol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), nickel dibutyldithiocarbamate, etc.], curing accelerators (dibutyltin dilaurate, lead octylate, bisnath octylate, etc.), coupling agents such as silane or titanium, plasticizers, etc.
  • Other additives can be used as appropriate without any particular restrictions as long as the curable composition intended by the present invention can be obtained.
  • the curable compositions of the present embodiments can be prepared by mixing the components described above.
  • the mixing device and method are not particularly limited as long as they are capable of producing the curable composition of the present invention.
  • Specific examples of such mixing devices that can be used include a twin-shaft mixer, a planetary mixer, a sigma mixer, a kneader, an attritor, a grain mill, a roll, and a dissolver.
  • the mixing can be performed using a container capable of mixing, for example, in a tank, vessel, or the like.
  • the curable composition according to the embodiment of the present invention may be a one-part type or a two-part type, and can generally be used as a one-part curable composition.
  • the curable composition according to an embodiment of the present invention can be applied to a required location in any thickness and coating form using a known coating method, such as bead coating, slit coating, spray coating, swirl coating, shot coating, or the like, and can be cured by heating to a predetermined temperature using, for example, a hot air circulating drying oven.
  • the curable composition according to the embodiment of the present invention can be used as a coating-type, one-part curable composition.
  • coating can be performed by a computer-controlled automatic coater or a robot coater.
  • a method for manufacturing an automobile can be provided that includes using a curable composition of an embodiment of the present invention.
  • the curable composition of the embodiment of the present invention can be used in a production line for manufacturing automobiles to provide a reinforcing layer on the sheet metal of an automobile body. That is, a reinforcing layer can be provided by applying the curable composition of the embodiment of the present invention to the sheet metal of an automobile body and curing it by heating.
  • a reinforced sheet metal structure and a manufacturing method thereof can be provided in which a reinforcing layer is provided by applying the curable composition of the embodiment of the present invention to the sheet metal of an automobile body and curing it by heating. It is then possible to provide a pumpable, curable composition for sheet metal reinforcement.
  • the viscosity of the curable composition according to the embodiment of the present invention at 40° C. and a shear rate of 430 sec ⁇ 1 is preferably 50 to 300 Pa ⁇ s, more preferably 65 to 250 Pa ⁇ s, even more preferably 80 to 200 Pa ⁇ s, and even more preferably 90 to 180 Pa ⁇ s.
  • the viscosity of the curable composition of the embodiment of the present invention is 50 to 300 Pa ⁇ s at 40° C. and a shear rate of 430 sec ⁇ 1
  • the curable composition of the embodiment of the present invention can further improve the pump dischargeability.
  • the expansion ratio of the curable composition according to the embodiment of the present invention is preferably from 10 to 200%, and more preferably from 30 to 150%.
  • the expansion ratio of the curable composition of the embodiment of the present invention is 10 to 200%, the curable composition of the embodiment of the present invention can further improve the reinforcement property and the strain resistance.
  • the flexural strength of the cured product of the curable composition according to an embodiment of the present invention is preferably 18 N or more, more preferably 20 to 60 N, even more preferably 22 to 50 N, and even more preferably 24 to 40 N.
  • the curable composition according to an embodiment of the present invention can further improve the reinforcing property.
  • the displacement (bending) of the cured product of the curable composition according to an embodiment of the present invention is preferably 4.5 mm or more, more preferably 4.8 to 20 mm, even more preferably 5 to 17 mm, and even more preferably 5.5 to 15 mm.
  • the curable composition according to an embodiment of the present invention does not crack even when subjected to impact, and can further ensure reinforcing properties.
  • the cured product of the curable composition according to an embodiment of the present invention preferably has a warpage of 5 mm or less, more preferably from ⁇ 1 to 4 mm, even more preferably from ⁇ 0.5 to 3.5 mm, and even more preferably from 0 to 3 mm.
  • the curable composition according to an embodiment of the present invention can further suppress distortion of the reinforcing panel.
  • the elastic modulus of the cured product of the curable composition according to an embodiment of the present invention is preferably 1000 to 3000 MPa, more preferably 1100 to 2500 MPa, even more preferably 1200 to 2000 MPa, and even more preferably 1300 to 1800 MPa.
  • the elastic modulus of the cured product of the curable composition of the embodiment of the present invention is 1000 to 3000 MPa, the reinforcing property of the curable composition of the embodiment of the present invention can be further improved.
  • the Tg of the cured product of the curable composition according to an embodiment of the present invention is preferably 40 to 140°C, more preferably 50 to 120°C, even more preferably 60 to 100°C, and even more preferably 70 to 95°C.
  • the reinforcement property of the curable composition of the embodiment of the present invention can be further improved.
  • Foaming agent (e1) Foaming agent (Vinihol AC#R (product name) manufactured by Eiwa Kasei Co., Ltd.) (e2) Foaming agent (Neo Celbon #1000M (product name) manufactured by Eiwa Kasei Co., Ltd.) (e3) Foaming agent (Expancel 920-80 (product name) manufactured by Japan Ferrite Co., Ltd.)
  • Viscosity Measurement The viscosity of the curable composition was measured using a pressure type apparent viscometer in accordance with JASO323-77. The cylinder of the viscometer was filled with the curable composition, and the temperature was adjusted to 40°C using a jacket or the like. It was confirmed that the temperature was 40°C. A capillary No. 3 (length: 74.1 mm, capillary diameter: 1.85 mm) was used. The shear rate was measured at 430 s -1 . The viscosity range in which the curable composition can be applied is considered to be 300 Pa.s or less, and the viscosity of the curable composition is preferably 50 Pa.s or more and 300 Pa.s or less.
  • a test specimen was prepared by applying the curable composition to a 200 ⁇ 300 ⁇ 0.8 mm SPCC-SD steel plate so as to have a size of 150 ⁇ 200 ⁇ 1.8 mm.
  • a shower of water at a temperature of 50° C., at an angle of 45 degrees, and at a water pressure of 490 kPa was applied to the surface of the test specimen on which the curable composition was applied.
  • the distance from the shower nozzle to the test specimen was 700 mm, and the shower was applied for 1 minute. After the shower, the applied surface was visually observed to confirm the presence or absence of peeling or displacement of the curable composition.
  • the evaluation criteria for shower resistance are as follows. ⁇ : The curable composition is completely free from peeling or displacement. ⁇ : The curable composition is not peeled off or displaced.
  • the curable composition has very slight peeling or displacement, but is not problematic.
  • the curable composition is slightly peeled off or displaced, but this does not pose a problem in practical use.
  • the curable composition is slightly peeled off or displaced, which is problematic in practical use.
  • the curable composition was applied in a bead shape to an aluminum plate of 3 x 7 cm to prepare a test specimen.
  • the test specimen was measured based on the underwater displacement method (see JASO323-77 Specific Gravity Test Method A) and the expansion ratio was calculated from the density (specific gravity) of the curable composition before and after curing.
  • Expansion ratio (%) (reciprocal of density after curing - reciprocal of density before curing) ⁇ reciprocal of density before curing ⁇ 100
  • the test specimen of the curable composition was placed in a forced circulation oven and cured for 25 minutes at 180° C. From the viewpoints of the reinforcement property and curing distortion of the cured product of the curable composition, the expansion ratio is preferably 10 to 200%, and more preferably 30 to 150%.
  • Bending strength and displacement (bending) The curable composition was applied to a 25 ⁇ 200 ⁇ 0.8 mm SPCC-SD steel plate to a thickness of 1.8 mm, and the applied steel plate was placed in a forced circulation oven to cure the curable composition at 180° C. for 25 minutes to obtain a test specimen.
  • a three-point bending test of this test specimen was performed using a bending strength tester specified in JIS K6911 under conditions of a support distance of 100 mm and a load rate of 1 mm/min, and the load (N/25 mm) at 1 mm displacement and the displacement at maximum load were obtained to measure the bending strength and bending.
  • the load (bending strength) at 1 mm displacement is preferably 18 N or more
  • the displacement (bending) at maximum load is preferably 4.5 mm or more.
  • Amount of warpage The curable composition was applied to a 25 x 200 x 0.8 mm SPCC-SD steel plate to a thickness of 1.8 mm, and the applied steel plate was placed in a forced circulation oven to cure the curable composition at 180°C for 25 minutes to obtain a test specimen. A weight of 1 kgf was placed on one side of this test specimen, and the warpage height (mm) on the opposite side was determined. Considering the amount of warpage that does not cause poor appearance in an actual vehicle, it is preferable that the amount of warpage is 5 mm or less.
  • the curable composition was applied to a 0.8 mm aluminum plate that had been subjected to a release treatment such as Teflon (registered trademark) processing so that the thickness after curing was 1 to 2 mm, and the coated test piece was placed in a forced circulation oven, and the curable composition was cured at 180°C for 25 minutes to obtain a cured product.
  • the size of the cured product was processed to a width of 5 mm and a length of 50 mm, and the elastic modulus and tan ⁇ were measured using a dynamic mechanical analysis (DMA) device at a heating rate of 2°C/min in the range of -50 to 150°C.
  • DMA dynamic mechanical analysis
  • the elastic modulus at 23°C and the temperature showing the peak position of tan ⁇ were recorded as Tg. From the perspective of dent resistance in an actual vehicle and the temperature environment in use, it is preferable to satisfy both an elastic modulus of 1000 to 3000 MPa and a Tg of 40°C to 140°C.
  • the curable compositions and their cured products of Examples 1 to 12 can be used as pumpable one-part curable compositions for sheet metal reinforcement, which can improve reinforcement while suppressing distortion and improve shower resistance while maintaining pumpability.
  • the curable compositions and their cured products of Comparative Examples 1 to 5 are unable to improve reinforcement while suppressing distortion, or improve shower resistance while maintaining pump dischargeability, and are therefore not sufficient as one-part curable compositions for application.
  • the one-part curable composition according to an embodiment of the present invention is capable of improving reinforcement while suppressing distortion, and improving shower resistance while maintaining pump dischargeability. Furthermore, the one-part curable composition can be suitably applied to sheet metal, and can be suitably used as a paint-type sheet metal reinforcement material.

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Abstract

L'invention concerne une composition durcissable à composant unique contenant (A) une résine époxy, (B) un caoutchouc solide, (C) un agent de durcissement latent, (D) une charge, et (E) un agent moussant, (A) contenant (A1) une résine époxy bisphénol non modifiée, la composition à composant unique contenant 10 à 100 parties en masse de (B) pour 100 parties en masse de (A), et (B) contenant (B1) un copolymère styrène-butadiène-divinylbenzène.
PCT/JP2023/036591 2022-11-01 2023-10-06 Composition durcissable à composant unique WO2024095701A1 (fr)

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JP2006176668A (ja) * 2004-12-22 2006-07-06 Daicel Chem Ind Ltd 発泡性充填材組成物
JP2009299028A (ja) * 2008-05-16 2009-12-24 Asahi Rubber Kk 塗布型板金補強材用エポキシ樹脂組成物
JP2011132507A (ja) * 2009-11-26 2011-07-07 Ajinomoto Co Inc エポキシ樹脂組成物
JP2011148091A (ja) * 2009-02-05 2011-08-04 Nitto Denko Corp 外板用補強材および外板の補強方法
US20130245161A1 (en) * 2012-03-13 2013-09-19 Elite Material Co., Ltd. Resin composition for insulation film
JP2018024872A (ja) * 2016-08-08 2018-02-15 シーカ テクノロジー アクチェンゲゼルシャフト ポンプ移送可能な熱発泡性充填組成物
JP2019038926A (ja) * 2017-08-24 2019-03-14 サンスター技研株式会社 一液型熱硬化性接着剤組成物及び該接着剤組成物が塗布されてなる車両の車体構造

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ES2388526T3 (es) 2003-06-04 2012-10-16 Sunstar Giken Kabushiki Kaisha Composición de carga termo-expansible y pastosa y método de aislamiento sonoro por medio de un relleno de sección cerrada de miembro de carrocería de coche
EP3978557A1 (fr) 2020-09-30 2022-04-06 Sika Technology Ag Compositions de remplissage pompables et thermiquement expansibles à temps ouvert prolongé

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Publication number Priority date Publication date Assignee Title
JP2002226995A (ja) * 2001-02-01 2002-08-14 Sunstar Eng Inc 塗布型板金補強材組成物
JP2005022339A (ja) * 2003-07-04 2005-01-27 Nitto Denko Corp 鋼板補強シート
JP2006176668A (ja) * 2004-12-22 2006-07-06 Daicel Chem Ind Ltd 発泡性充填材組成物
JP2009299028A (ja) * 2008-05-16 2009-12-24 Asahi Rubber Kk 塗布型板金補強材用エポキシ樹脂組成物
JP2011148091A (ja) * 2009-02-05 2011-08-04 Nitto Denko Corp 外板用補強材および外板の補強方法
JP2011132507A (ja) * 2009-11-26 2011-07-07 Ajinomoto Co Inc エポキシ樹脂組成物
US20130245161A1 (en) * 2012-03-13 2013-09-19 Elite Material Co., Ltd. Resin composition for insulation film
JP2018024872A (ja) * 2016-08-08 2018-02-15 シーカ テクノロジー アクチェンゲゼルシャフト ポンプ移送可能な熱発泡性充填組成物
JP2019038926A (ja) * 2017-08-24 2019-03-14 サンスター技研株式会社 一液型熱硬化性接着剤組成物及び該接着剤組成物が塗布されてなる車両の車体構造

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