WO2022249282A1 - Composition durcissable et procédé de production de composition durcissable - Google Patents

Composition durcissable et procédé de production de composition durcissable Download PDF

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Publication number
WO2022249282A1
WO2022249282A1 PCT/JP2021/019812 JP2021019812W WO2022249282A1 WO 2022249282 A1 WO2022249282 A1 WO 2022249282A1 JP 2021019812 W JP2021019812 W JP 2021019812W WO 2022249282 A1 WO2022249282 A1 WO 2022249282A1
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WIPO (PCT)
Prior art keywords
curable composition
elastomer
latent curing
curing agent
composition according
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PCT/JP2021/019812
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English (en)
Japanese (ja)
Inventor
敏雄 小林
敬章 井上
Original Assignee
サンスター技研株式会社
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Application filed by サンスター技研株式会社 filed Critical サンスター技研株式会社
Priority to PCT/JP2021/019812 priority Critical patent/WO2022249282A1/fr
Priority to JP2021194779A priority patent/JP7228664B2/ja
Priority to JP2021196265A priority patent/JP7122449B1/ja
Priority to CN202210564498.9A priority patent/CN115386321A/zh
Priority to US17/751,337 priority patent/US11920028B2/en
Priority to EP22174835.3A priority patent/EP4095196A3/fr
Publication of WO2022249282A1 publication Critical patent/WO2022249282A1/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
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

  • the present invention relates to a curable composition, and more particularly to a curable composition containing an elastomer, an epoxy resin and a latent curing agent.
  • the curable composition can be suitably used, for example, in automotive adhesives, more specifically in automotive bodywork adhesives (eg, structural adhesives, mastic adhesives, etc.).
  • Automobile bodies are manufactured in white through a body process that includes press molding steel plates and welding and assembling.
  • the white body is painted in a painting process including electrodeposition painting, electrodeposition baking, painting, and painting baking.
  • the bodywork adhesive is an adhesive used when manufacturing a body-in-white that is manufactured in a bodywork process.
  • the adhesive is generally required to have oil surface adhesion and rust resistance.
  • the adhesive is a one-liquid thermosetting type. hardens with
  • Patent Document 1 discloses a curability obtained by blending a composition containing a synthetic rubber, a plasticizer, a filler, and a core-shell type acrylic resin with a diluent and an adhesion imparting agent that is a combination of an epoxy resin and a latent curing agent.
  • a composition is disclosed (see [Claim 1] to [Claim 3], [0043] [Table 1]).
  • Patent Document 1 discloses that the curable composition does not require vinyl chloride resin, is less harmful to the environment, and exhibits excellent adhesiveness to alloyed aluminum materials. It will be stated that the range of application of the aluminum oxide material is widened, and that there is a great effect of further reducing the weight of the vehicle body (see [0008]).
  • Patent document 2 discloses a mastic adhesive for adhering to body panels, which is composed of synthetic rubber, polyvinyl chloride, a plasticizer and a filler, and contains a titanium oxide pigment at a rate of 0.2 to 10% by weight (claimed range, see Table 1 on page 4). Patent Document 2 states that there is no problem of foaming or carbonization even when near-infrared heating is performed at a temperature of 140 to 270° C. for 3 minutes or less (see page 2, right column, lines 11 to 16).
  • Patent Document 3 discloses that a curable resin composition comprising a urethane-rubber-modified epoxy resin and a latent curing agent has improved adhesion from low temperature to room temperature, and furthermore, a urethane-rubber-modified epoxy resin, blocked urethane and It is disclosed that a curable composition comprising a latent curing agent is particularly excellent in tensile elongation at low temperature as well as adhesion from low temperature to room temperature (see [0065] [Table 1] to [0067]).
  • Patent Document 1 a test piece is cured by holding it at 170° C. for 20 minutes (see [0038] to [0039]).
  • Patent Document 2 does not disclose a specific curing temperature.
  • Patent Document 3 holds the test piece at 180° C. for 30 minutes for curing (see [0063] to [0064]).
  • Patent Documents 1 to 3 all disclose curable compositions that cure at 170°C or higher, and it is difficult to meet the recent demand for lower temperatures.
  • an elastomer (A), an epoxy resin (B) and a latent curing agent (C) are contained, and the latent curing agent (C) is two or more latent curing agents.
  • the present inventors have completed the present invention by finding that a curable composition comprising a combination of agents is suitable for use as an adhesive for automobiles, more specifically for automotive bodywork.
  • a curable composition comprising an elastomer (A), an epoxy resin (B) and a latent curing agent (C), A curable composition wherein the latent hardener (C) comprises a combination of two or more latent hardeners.
  • the elastomer (A) contains at least one selected from styrene-butadiene copolymers, nitrile-butadiene copolymers, butadiene polymers, isoprene polymers, ethylene-propylene-diene rubbers, acrylics, and urethanes. thing. 3. 2.
  • the curable composition according to 1 above wherein part of the elastomer (A) contains a compound pre-reacted with the epoxy resin (B). 4. 4. The curable composition according to any one of 1 to 3 above, further comprising a thermoplastic resin (E). 5. 5. The curable composition according to 4 above, wherein the thermoplastic resin (E) contains at least one selected from acrylic resins, PVC resins, vinyl acetate resins, and copolymers thereof. 6. 6. The curable composition according to any one of 1 to 5 above, which comprises an elastomeric cross-linking agent (F). 7. 7. The curable composition according to 6 above, wherein the elastomer cross-linking agent (F) contains at least one selected from sulfur and peroxides. 8. 8.
  • n 10 to 23
  • D filler
  • a method for producing a curable composition comprising mixing an elastomer (A), an epoxy resin (B) and a latent curing agent (C), At least part of the latent curing agent (C) is pulverized in advance to an average particle size of 25 ⁇ m or less, and/or at least part of the latent curing agent (C) is dispersed in the epoxy resin (B). , a method for producing a curable composition. 16. At least part of the elastomer (A) is solid, and the partly solid elastomer (A) and at least part of the plasticizer (G) or the epoxy resin (B) are mixed and dissolved to obtain the elastomer (A).
  • Step 1 of obtaining a mixture 1 comprising step 2 of mixing at least a portion of the latent hardener (accelerator) (C) and at least a portion of the plasticizer (G) to obtain a mixture 2 comprising the latent hardener (accelerator) (C); Step 3: mixing said Mixture 1, said Mixture 2 and the components of the curable composition other than Mixtures 1 and 2 to obtain a mixture in which all components are mixed; 16.
  • a method for producing a curable composition according to 15 above comprising: 17. 17.
  • the manufacturing method according to 16 above, wherein the mixing of the elastomer (A) and the plasticizer (G) includes adding the plasticizer (G) in portions to the elastomer (A) passed through mixing rolls. 18. 18.
  • the production method according to any one of 15 to 17 above which comprises stirring the mixture under reduced pressure at 10 mmHg or more and 150 mmHg or less for 20 minutes or more after mixing all the components. 19. 18. The process according to any one of 15 to 17 above, which comprises, after mixing all the ingredients, vacuuming and stirring the mixture at less than 10 mmHg for 10 minutes or less. 20. 20. The production method according to any one of 15 to 19 above, wherein the stirring includes using a twin-screw mixer, a planetary mixer or a sigma mixer.
  • the curable composition of embodiments of the present invention comprises an elastomer (A), an epoxy resin (B) and a latent curing agent (C), wherein the latent curing agent (C) comprises two or more latent curing agents
  • the curable composition can be suitably used for automotive adhesives, more specifically for automotive bodywork adhesive applications
  • the present invention provides a novel curable composition, which comprises comprising an elastomer (A), an epoxy resin (B) and a latent curing agent (C), Latent hardener (C) comprises a combination of two or more latent hardeners.
  • Curable compositions of embodiments of the present invention comprise an elastomer (A), an epoxy resin (B) and a latent curing agent (C).
  • the elastomer (A) means a polymer having rubber elasticity, and is a polymer generally called an elastomer, including thermosetting elastomers and thermoplastic elastomers. There are no particular restrictions as long as a curable composition can be obtained.
  • Examples of the elastomer (A) include styrene-butadiene copolymers, nitrile-butadiene copolymers, butadiene polymers, isoprene polymers, ethylene-propylene-diene polymers, acrylic polymers, and polymers containing urethane bonds. can be done.
  • Elastomer (A) includes styrene-butadiene copolymer (styrene-butadiene rubber), nitrile-butadiene copolymer, butadiene polymer (butadiene rubber), isoprene polymer, ethylene-propylene-diene polymer, acrylic polymer, and urethane bond It preferably contains at least one selected from polymers, more preferably at least one selected from styrene-butadiene copolymers (styrene-butadiene rubber) and butadiene polymers (butadiene rubber).
  • part of the elastomer (A) may contain a compound pre-reacted with the epoxy resin (B).
  • the familiarity (or compatibility) between the elastomer and the epoxy resin can be further improved, and the overall physical properties of the curable composition can be further improved.
  • a commercial item can be used as an elastomer (A).
  • SBR1009 (trade name) manufactured by ISP Japan
  • SB-1009 (trade name) manufactured by Nitriflex
  • SBR1009 (trade name) manufactured by Lion Elastomers
  • Nipol DN214 (trade name) manufactured by Nippon Zeon
  • BR1220 (trade name) manufactured by JSR Corporation
  • N230S (trade name) manufactured by JSR Corporation
  • Elastomers (A) can be used alone or in combination.
  • Curable compositions of embodiments of the present invention may comprise, for example, from 2 to 20 parts by weight of elastomer (A) per 100 parts by weight of curable composition, and from 3 to 15 parts by weight of elastomer (A). It preferably contains 4 to 10 parts by mass of elastomer (A), more preferably 5 to 9 parts by mass of elastomer (A).
  • the curable composition of the embodiment of the present invention contains 2 to 20 parts by mass of the elastomer (A) per 100 parts by mass of the curable composition, more appropriate curability can be obtained. Better workability due to viscosity can be obtained, and the hardness of the cured product can be adjusted more appropriately.
  • the curable composition of embodiments of the present invention can further comprise a thermoplastic resin (E).
  • the thermoplastic resin (E) is a powdery or particulate polymer that is solid at room temperature, and is dispersed in a liquid component such as an epoxy resin and a plasticizer (if used), that is, in a sol state. When heated (e.g., 80° C. or higher), the thermoplastic resin is swollen by the epoxy resin and plasticizer, which are liquid components, and solidifies when cooled.
  • the curable composition of the embodiment of the present invention further contains a thermoplastic resin (E)
  • the curability can be further improved, and the physical properties can be improved by changing the amount of the thermosetting resin (E) added. can be adjusted more easily.
  • thermoplastic resins (E) examples include acrylic resins, vinyl chloride (PVC) resins, vinyl acetate (vinyl acetate) resins, and copolymers thereof.
  • thermoplastic resin (E) a thermoplastic resin having a polarizable structure having a polar group and a non-polar group is preferable, and examples thereof include acrylic resins, polyvinyl chloride (PVC) resins, and vinyl acetate (vinyl acetate) resins. and copolymers thereof are preferred.
  • acrylic resins, polyvinyl chloride (PVC) resins, vinyl acetate (vinyl acetate) resins, and combinations of their copolymers can be exemplified.
  • thermoplastic resin (E) may have a core-shell structure, is in a dispersed state at room temperature, and preferably contains a resin (for example, an acrylic resin) that is soluble when heated.
  • the thermoplastic resin (E) is preferably particulate.
  • the average particle size of the thermoplastic resin (E) is preferably 0.01 to 100 ⁇ m, more preferably 0.05 to 10 ⁇ m, even more preferably 0.1 to 5 ⁇ m, and 0.2 Even more preferably ⁇ 2 ⁇ m.
  • the thermoplastic resin (E) is in the form of particles, it can be more easily plasticized by heating and more uniformly mixed with the elastomer (A), the epoxy resin (B), and the like.
  • the average particle size of the thermoplastic resin can be measured by a laser particle size distribution measurement method using SALD-200VER (trade name) manufactured by Shimadzu Corporation.
  • thermoplastic resin (E).
  • Mitsubishi Rayon LP-3106 (trade name), Mitsubishi Rayon LP-3102 (trade name), Mitsubishi Rayon LP-3108 (trade name), Mitsubishi Rayon LP-3109 (trade name) ) etc.
  • ZEFIAC F351 (trade name) manufactured by AICA Kogyo Co., Ltd., ZEFIAC F351 (trade name) manufactured by Aika Kogyo Co., Ltd.
  • PSH-10 trade name
  • Kaneka Corporation PCH-72 (trade name) manufactured by Kaneka Corporation
  • PSH-24 (trade name) manufactured by Kaneka Corporation
  • PBM-6 (trade name) manufactured by Kaneka Corporation, and the like.
  • Thermoplastic resins (E) can be used alone or in combination.
  • the curable composition of embodiments of the present invention may contain, for example, 0.2 to 20 parts by weight of thermoplastic resin (E) per 100 parts by weight of curable composition, and 0.4 to 15 parts by weight. of the thermoplastic resin (E), more preferably 1 to 10 parts by mass of the thermoplastic resin (E), more preferably 2 to 9 parts by mass of the thermoplastic resin (E). .
  • the curable composition of the embodiment of the present invention per 100 parts by weight of the curable composition, when containing 0.2 to 20 parts by weight of the thermoplastic resin (E), more appropriate physical properties and curability and storage stability can be advantageous.
  • the curable compositions of embodiments of the present invention may include an elastomeric crosslinker (F).
  • the elastomer cross-linking agent (F) refers to a substance capable of cross-linking the elastomer (A) to adjust the rubbery properties of the elastomer (A) (for example, making it harder). No, as long as the desired curable composition of the present invention can be obtained, there is no particular limitation.
  • the curable composition of the embodiment of the present invention contains the elastomer cross-linking agent (F)
  • the curability can be improved and the hardness can be increased, and the hardness can be adjusted by adjusting the amount. can play
  • elastomer cross-linking agents (F) include sulfur, peroxides, quinone compounds, and the like.
  • the elastomer cross-linking agent (F) preferably contains at least one selected from sulfur, peroxides and quinone compounds, more preferably at least one selected from peroxides and quinone compounds.
  • a commercially available product can be used as the cross-linking agent (F) for the elastomer.
  • NOF Chemical Co., Ltd. Perhexa V (trade name) (n-butyl 4,4-di(t-butylperoxy) valerate), NOF Chemical Co., Ltd. Perhexa C (1,1-di(t-butylperoxy)) Cyclohexane) (trade name) and other peroxides; (p-quinonedioxime) Barnok GM-P (trade name) and O,O'-dibenzoyl-p-quinonedioxime) Barnok manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd. Examples include quinone compounds such as DGM (trade name).
  • the elastomeric crosslinkers (F) can be used alone or in combination.
  • Curable compositions of embodiments of the present invention may comprise, for example, from 0.03 to 5 parts by weight of elastomeric crosslinker (F) per 100 parts by weight of curable composition, and from 0.08 to 4 parts by weight. parts by mass of the elastomeric cross-linking agent (F), more preferably 0.1 to 3 parts by mass of the elastomeric cross-linking agent (F).
  • the curable composition of the embodiment of the present invention has more suitable physical properties (e.g., hardness) when it contains 0.3 to 5 parts by weight of the elastomer cross-linking agent (F) per 100 parts by weight of the curable composition. can be obtained more easily.
  • a curable composition according to embodiments of the present invention comprises an epoxy resin (B).
  • epoxy resin refers to a compound containing two or more epoxy groups in the molecule and generally referred to as an epoxy resin.
  • epoxy resins include glycidyl ether type epoxy resins, glycidyl amine type epoxy resins, glycidyl ester type epoxy resins, and the like.
  • epoxy resin contained in the curable composition of the embodiment of the present invention further, for example, Bisphenol type epoxy resins such as bisphenol A, bisphenol F, brominated bisphenol A, diglycidyl ether of bisphenol AD, diglycidyl ether of alkylene oxide adduct of bisphenol A, and aromatic rings contained in these epoxy resins are hydrogenated.
  • Bisphenol type epoxy resins such as bisphenol A, bisphenol F, brominated bisphenol A, diglycidyl ether of bisphenol AD, diglycidyl ether of alkylene oxide adduct of bisphenol A, and aromatic rings contained in these epoxy resins are hydrogenated.
  • an acrylonitrile-butadiene copolymer-modified epoxy resin prepared by Polyhydroxy compounds [e.g., polyalkylene glycols (polyethylene glycol, polypropylene glycol, polyethylene propylene glycol, etc.); hexylene glycol, butylene glycol, propylene glycol, ethylene glycol, neopentyl glycol, triethylene glycol, pentanediol, hexanetriol, glycerol Alkylene oxide-modified glycidyl ether type epoxy resin obtained by reacting epihalohydrin with an aliphatic polyhydric hydroxy compound such as Urethane-modified epoxy resin (mixing ratio is 10:90 to 50:50) obtained by reacting a polyurethane prepolymer in which polyisocyanate is added to the end of polyalkylene glycol with hydroxyl groups of epoxy resin, or carboxyl groups on the surface of acrylic rubber particles. and epoxy resin (mixing ratio is 10:90 to
  • a commercial item can be used as said epoxy resin.
  • Examples of commercially available products thereof include “jER (registered trademark) 828” manufactured by Mitsubishi Chemical Corporation, “ADEKA RESIN EPR-4023” manufactured by ADEKA CORPORATION, “ADEKA GLYCIROL ED-506", “ADEKA RESIN EPU- 73B”, “ADEKA RESIN EPU-78-11”, “Kaneace MX-257” manufactured by Kaneka Corporation, ⁇ HBE-100” manufactured by Shin Nippon Rika Co., Ltd., and the like.
  • Epoxy resins can be used alone or in combination.
  • the curable composition of embodiments of the present invention may contain, for example, 0.1 to 50 parts by weight of the epoxy resin (B) per 100 parts by weight of the curable composition, and 0.5 to 10 parts by weight of It preferably contains the epoxy resin (B), more preferably contains 1 to 8 parts by mass of the epoxy resin (B), and more preferably contains 1.5 to 5 parts by mass of the epoxy resin (B).
  • the adhesion to the substrate e.g., to aluminum
  • the curable compositions of embodiments of the present invention comprise a latent hardener (C), and the latent hardener (C) comprises a combination of two or more latent hardeners.
  • latent curing agent refers to a curing agent for epoxy resins that does not substantially function as a curing agent at room temperature, but can be heated (e.g., to 165°C, preferably to 150°C). is a compound that functions as a curing agent, and is not particularly limited as long as the desired curable composition of the present invention can be obtained.
  • latent curing agents include dicyandiamide; adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, dodecanediohydrazide, 1,3-bis(hydrazinocarboethyl)-5-isopropylhydantoin, eicosane dihydrazide, Dihydrazide compounds such as acid dihydrazide, hydroquinone diglycolic acid dihydrazide, resorcinol diglycolic acid dihydrazide, 4,4′-ethylidenebisphenoldiglycolic acid dihydrazide; 4,4′-diaminodiphenyl sulfone; imidazole, 2-n-heptadecyl imidazole, Imidazole compounds such as 2-undecylimidazole; melamine; triazine compounds such as 2,4-diamino-6-(2'-methyl)
  • CG-NA (trade name) manufactured by Air Products
  • EH-4030s (trade name) manufactured by ADEKA
  • ADH (trade name) manufactured by Otsuka Chemical
  • EH3731s (trade name) manufactured by ADEKA
  • AlzChem AlzChem.
  • Dyhard UR200 (trade name) manufactured by Otsuka Chemical Co., Ltd.
  • DDH (trade name) manufactured by Otsuka Chemical Co., Ltd.
  • the melting points of at least two latent curing (accelerator) agents contained in the latent curing agent (C) preferably differ by 10 to 80°C, more preferably by 13 to 50°C. , differ by 15-25°C.
  • the melting points of at least two latent curing (accelerator) agents contained in the latent curing agent (C) differ by 10 to 80 ° C.
  • At least one contained in the latent curing agent (C) is preferably at least one selected from dicyandiamide; dihydrazide compounds; imidazole compounds; triazine compounds; and dialkylurea compounds.
  • at least one contained in the latent curing agent (C) contains at least one selected from dicyandiamide; dihydrazide compound; imidazole compound; triazine compound; and dialkylurea compound, storage stability and adhesion are excellent.
  • At least one contained in the latent curing agent (C) preferably has a C10 to C23 aliphatic alkane structure (or an aliphatic alkyl group), and a C10 to C18 aliphatic alkane structure, more preferably a C12 to C17 aliphatic alkane structure.
  • the latent curing agent (C) has a C10 to C23 aliphatic alkane structure, the low-temperature adhesion is more excellent.
  • At least one contained in the latent curing agent (C) preferably has a C10 to C23 aliphatic alkylene structure (or aliphatic alkylene group), and a C10 to C18 aliphatic alkylene Having a structure is more preferable.
  • at least one contained in the latent curing agent (C) preferably contains a dihydrazide compound, preferably an aliphatic dihydrazide compound, more preferably an aliphatic dicarboxylic acid dihydrazide. preferable.
  • the aliphatic dicarboxylic acid dihydrazide preferably contains an aliphatic alkylene structure having 10 to 23 carbon atoms, more preferably contains an aliphatic alkylene structure having 10 to 18 carbon atoms, and even more preferably contains dodecanediohydrazide. .
  • the latent curing agents (C) contains a dihydrazide compound, the low-temperature adhesion is more excellent.
  • At least one of the latent curing agents (C) preferably contains a latent curing (accelerating) agent represented by formula (1).
  • the latent curing agents (C) contains the latent curing (accelerating) agent represented by the formula (1), an advantageous effect of better low-temperature curability can be obtained.
  • the curable composition of embodiments of the present invention may contain, for example, 0.05 to 2.5 parts by weight of the latent curing agent (C) per 100 parts by weight of the curable composition, and 0.07 to It preferably contains 2.0 parts by mass of the latent curing agent (C), more preferably 0.1 to 1.6 parts by mass of the latent curing agent (C), and 0.2 to 1.0 parts by mass. It is more preferable to contain the latent curing agent (C) in parts by mass.
  • the curable composition of the embodiment of the present invention contains 0.05 to 2.5 parts by mass of the latent curing agent (C) per 100 parts by mass of the curable composition, the curability and storage stability are improved. Well balanced.
  • the curable composition of embodiments of the present invention may further comprise filler (D).
  • fillers are compounds that can extend the weight of the curable compositions of the present embodiments as well as impart some strength to films formed from the curable compositions. It is not particularly limited as long as it can contribute to viscosity adjustment or weight reduction and the desired curable composition of the present invention can be obtained.
  • fillers examples include calcium carbonate (heavy calcium carbonate, precipitated calcium carbonate, surface-treated calcium carbonate, etc.), magnesium carbonate, alkaline earth metal carbonates and sulfates such as barium sulfate, mica (mica), and graphite.
  • talc clay, glass flakes (glass beads), vermiculite, kaolinite, wollastonite (acicular calcium metasilicate), silica, diatomaceous earth, gypsum, cement, converter slag, whitebait, zeolite, cellulose powder , powdered rubber, xonolite, potassium titanate, bentonite, aluminum nitride, silicon nitride, zinc white, titanium oxide, alumina, zinc oxide, iron oxide, magnesium oxide, titanium oxide, magnesium hydroxide, aluminum hydroxide, calcium silicate, etc.
  • calcium carbonate whiskers acicular calcium carbonate
  • ceramic staple fibers or their whiskers rock wool staple fibers, glass fiber staple fibers, potassium titanate staple fibers, calcium silicate staple fibers, aluminum silicate, carbon fiber staple fibers, aramid Fiber short fibers, mineral fibers such as sepiolite, fibrous fillers such as various whiskers, hollow fillers such as glass balloons, silica balloons, resin balloons, carbon inorganic hollow spheres, and organic synthetic resins such as vinylidene chloride and acrylonitrile Examples include organic hollow fillers such as plastic balloons, metallic fillers such as aluminum fillers, and the like.
  • Curable compositions of embodiments of the present invention may comprise, for example, from 20 to 80 parts by weight of filler (D) per 100 parts by weight of curable composition, and from 25 to 70 parts by weight of filler (D ), more preferably 30 to 60 parts by mass of the filler (D), and more preferably 35 to 55 parts by mass of the filler (D).
  • the curable composition of the embodiment of the present invention can further improve workability when it contains 20 to 80 parts by mass of the filler (D) per 100 parts by mass of the curable composition.
  • the curable composition in embodiments of the present invention may further comprise a plasticizer (G).
  • the plasticizer (G) is not particularly limited as long as it can increase plasticity and soften, and the desired curable composition of the present invention can be obtained.
  • plasticizers for example, alkylbenzyl phthalates such as butyl benzyl phthalate (butyl benzyl phthalate: BBP), octyl benzyl phthalate (octyl benzyl phthalate: OBP), and isononyl benzyl phthalate (isononyl benzyl phthalate); phthalic acid Dimethylcyclohexyl (dimethylcyclohexyl phthalate: DMCHP); polyester phthalate; benzoic acid ester; diisononyl phthalate (diisononyl phthalate: DINP), dioctyl phthalate (dioctyl phthalate: DOP), dimethyl phthalate (dimethyl phthalate: DMP), phthalic acid Diethyl (diethyl phthalate: DEP), dibutyl phthalate (dibutyl phthalate: DBP), diheptyl phthalate (
  • the plasticizer preferably comprises a phthalate diester, and more preferably the phthalate diester comprises alkylbenzyl phthalate and/or dialkyl phthalate.
  • the plasticizer contains diester phthalate, it is preferable because it has moderate curability and is excellent in storage stability.
  • the curable composition of the embodiment of the present invention can contain a plasticizer, for example, 5 to 60 parts by weight, preferably 10 to 55 parts by weight, based on 100 parts by weight of the total curable composition. It is more preferable to contain up to 50 parts by mass, and even more preferably 20 to 40 parts by mass.
  • a plasticizer for example, 5 to 60 parts by weight, preferably 10 to 55 parts by weight, based on 100 parts by weight of the total curable composition. It is more preferable to contain up to 50 parts by mass, and even more preferably 20 to 40 parts by mass.
  • the curable composition of the embodiment of the present invention can contain other components as appropriate.
  • other components include ordinary curing agents (excluding the latent curing agents described above), diluents, surfactants, and other additives.
  • the curing agent is a compound that does not have a curing effect at room temperature but exhibits a curing effect at a certain temperature, and is the object of the present invention, except for the latent curing agent described above. It is not particularly limited as long as the curable composition can be obtained.
  • the diluent is particularly limited as long as it can impart fluidity to the curable composition of the present invention and the desired curable composition of the present invention can be obtained. never.
  • diluents include hydrocarbon solvents such as paraffin solvents, isoparaffin solvents, naphthene solvents, and aromatic solvents.
  • additives include, for example, hygroscopic agents (calcium oxide, molecular sieves, etc.), thixotropic agents (organic bentonite, fumed silica, aluminum stearate, metallic soaps, castor oil derivatives, etc.). ), stabilizer [2,6-di-t-butyl-4-methylphenol, 2,2-methylene-bis(4-methyl-6-t-butylphenol), nickel dibutyldithiocarbamate, etc.], curing accelerator ( dibutyltin dilaurate, lead octylate, bismuth octylate, etc.), coupling agents such as silane or titanium, and the like.
  • Other additives can be appropriately used without particular limitation as long as the intended curable composition of the present invention can be obtained.
  • the present invention is a method for producing a curable composition comprising mixing an elastomer (A), an epoxy resin (B) and a latent curing agent (C), comprising: At least part of the latent curing agent (C) is pulverized in advance to an average particle size of 25 ⁇ m or less, and/or at least part of the latent curing agent (C) is dispersed in the epoxy resin (B). provides a method of making a curable composition.
  • the apparatus and method for mixing the elastomer (A), epoxy resin (B) and latent curing agent (C) are not particularly limited as long as the desired curable composition of the present invention can be produced.
  • a mixing device specifically, for example, a twin-screw mixer, planetary mixer, sigma mixer, kneader, attritor, grain mill, roll, dissolver, or the like can be used. Mixing is more preferably performed using a twin-screw mixer, planetary mixer or sigma mixer. A twin screw mixer, planetary mixer or sigma mixer can be used to disperse highly viscous materials more efficiently. Further, the mixing can be done using a container that allows mixing, for example, in a tank, vessel, or the like.
  • the latent curing agent (C) is pulverized in advance to an average particle size of 25 ⁇ m or less, and/or the latent curing agent (C) is Dispersing at least a portion in the epoxy resin (B). Since the manufacturing method of the embodiment of the present invention includes such a step, the latent curing agent (C) can be dispersed more uniformly in the curable composition, and the curing property having better properties Compositions can be manufactured.
  • the apparatus and method for pulverizing the latent curing agent (C) to an average particle size of 25 ⁇ m or less are not particularly limited as long as the curable composition aimed at by the present invention can be produced.
  • a crushing apparatus and method various crushing apparatuses and methods can be used. Specifically, for example, KJ400 (trade name) manufactured by Kurimoto Iron Works Co., Ltd. can be used.
  • the average particle size of the latent curing agent (C) can be measured by a laser particle size distribution measurement method. Specifically, for example, it is measured using SALD-200VER (trade name) manufactured by Shimadzu Corporation. can do.
  • the average particle size is preferably 50 ⁇ m or less, more preferably 30 ⁇ m or less, and even more preferably 25 ⁇ m or less.
  • the latent curing agent (C) is pre-pulverized to an average particle size of 25 ⁇ m or less, the adhesive strength can be more stable.
  • the latent curing agent (C) may be at least partially dispersed in the epoxy resin (B).
  • 25% of the latent curing agent (C) is dispersed in the epoxy resin (B)
  • more preferably 50% is dispersed in the epoxy resin (B)
  • all of it is dispersed in the epoxy resin (B). is more preferred.
  • the adhesive strength can be more stable.
  • a method of making a curable composition according to embodiments of the present invention includes the following steps: At least a part of the elastomer (A) is solid, and a part of the solid elastomer (A) is mixed and dissolved with at least a part of the plasticizer (G) or the liquid component epoxy resin (B), Step 1 of obtaining a mixture 1 comprising elastomer (A); step 2 of mixing at least a portion of the latent hardener (accelerator) (C) and at least a portion of the plasticizer (G) to obtain a mixture 2 comprising the latent hardener (accelerator) (C); Step 3 of mixing Mixture 1 obtained in Step 1, Mixture 2 obtained in Step 2, and other components of the curable composition other than Mixtures 1 and 2;
  • step 1 it is preferable to employ a method of promoting dissolution of the elastomer (A) by further adding a portion of the filler (D) to reduce the cohesive force of the elastomer (A).
  • the input order in step 3 may be changed as appropriate.
  • the stirring device and method and the mixing device and method used in steps 1 to 3 are not particularly limited as long as the curable composition aimed at by the present invention can be produced.
  • the manufacturing method of the embodiment of the present invention can have advantageous effects such as improved dispersibility, shortened process time, and improved adhesive strength.
  • the manufacturing method of the embodiment of the present invention may include adding the plasticizer (G) in portions to the elastomer (A) passed through mixing rolls in the mixing of the elastomer (A) and the plasticizer (G). can.
  • the apparatus and method for passing the elastomer through the mixing rolls, and the apparatus and method for adding the plasticizer (G) in portions are the curable composition aimed at by the present invention. is not particularly limited as long as it can be manufactured.
  • the manufacturing method of embodiments of the present invention may allow for a more homogeneous dispersion of elastomer (A) when it includes adding the plasticizer (G) in portions to elastomer (A) passed through mixing rolls.
  • the solid elastomer (A) is preferably formed (or sheeted) into a thin sheet by passing it through mixing rolls. It is preferable to apply a plasticizer (G) to the sheeted elastomer (A) through mixing rolls. The softening of the elastomer (A) can be facilitated by the plasticizer (G). There are usually multiple passes through the mixing rolls.
  • the elastomer (A) already exemplified is suitable for sheeting through mixing rolls.
  • the manufacturing method of embodiments of the present invention can include depressurizing and stirring the mixture after all components are mixed.
  • the apparatus and method for reducing the pressure and stirring the mixture are not particularly limited as long as the curable composition aimed at by the present invention can be produced.
  • the mixture may be stirred under reduced pressure, for example, at a reduced pressure of 150 mmHg or less, preferably 120 mmHg or less, preferably 100 mmHg or less, and more preferably 80 mmHg or less.
  • the time for stirring under reduced pressure is not particularly limited as long as air bubbles in the adhesive are removed and physical properties are not deteriorated due to excessive foaming during heat curing. you can go When the mixture is stirred under reduced pressure, an advantageous effect can be obtained in that extremely strong foaming can be prevented when the curable composition is heat-cured.
  • the lower limit of the degree of reduced pressure is, for example, 1 mmHg or more, preferably 6 mmHg or more, more preferably 10 mmHg or more. If the degree of pressure reduction is less than 10 mmHg, the time is preferably 10 minutes or less, more preferably 5 minutes or less under those conditions. When the pressure of the mixture is reduced to less than 10 mmHg, more air bubbles are removed from the composition, so that the strength of the cured product of the curable composition can be further improved. It may break. It is believed that the minute air bubbles remaining in the cured product can stop the growth of cracks when cracks occur inside the cured product.
  • the curable composition of the embodiment of the present invention has aluminum plate adhesion (curing at 150 ° C.) (shear strength), aluminum plate adhesion (curing at 165 ° C.) (shear strength), and aluminum plate adhesion after storage at 50 ° C. for 5 days. (150°C curing) (shear strength), elongation of cured product (165°C curing), adhesion to steel plate (165°C curing) (shear strength) and (peel strength), impact strength of cured product, curable composition It is preferable that the storage stability and the dripping property of the curable composition are excellent. Detailed evaluation methods are described in Examples.
  • the curable composition of the present embodiment can be applied to a desired location with any desired thickness and application form using a known coating method such as bead coating, slit coating, spray coating, swirl coating, shot coating, or the like. For example, it can be cured by heating to a predetermined temperature using a hot air circulation drying oven or the like.
  • a method of manufacturing an automobile comprising using the curable compositions of embodiments of the present invention.
  • the curable compositions of embodiments of the present invention can be used in bodywork processes for manufacturing automobiles. More specifically, it can be suitably used for adhesives for vehicle body processes (eg, structural adhesives, mastic adhesives, etc.).
  • the present invention in another aspect, provides a method of lowering the curing temperature of a curable composition, comprising using the curable composition described above.
  • Elastomer (a1) Styrene-butadiene rubber (SBR1009 (trade name) manufactured by ISP Japan) (a2) Butadiene rubber (BR1220 (trade name) manufactured by Zeon Corporation)
  • B) Epoxy resin (b1) Bisphenol A type epoxy resin (JER828 (trade name) manufactured by Mitsubishi Chemical Corporation) (b2) Urethane-modified epoxy resin (EPU-78-11 (trade name) manufactured by ADEKA) (A part of the epoxy resin is previously modified with a urethane elastomer, including (A).)
  • HBE-100 Hydrogenated bisphenol A type epoxy resin manufactured by Shin Nippon Rika Co., Ltd.
  • Polypropylene glycol diglycidyl ether (adeka glycyrrol ED-506 (trade name) manufactured by ADEKA)
  • (C) latent curing (accelerator) agent (c1) dicyandiamide (CG-NA (trade name) manufactured by Air Products), melting point 207-210°C, average particle size 30 ⁇ m or more (c2) 2-heptadecyl imidazole, melting point 88°C, average particle size 30 ⁇ m or more (c3) 2-undecylimidazole, melting point 72°C, average particle size 30 ⁇ m or more (c4) 2,4-diamino-6-(2'-methylimidazolyl (1'))- Ethyl-o-triazine (2MZA (trade name) manufactured by Shikoku Kasei Co., Ltd.), melting point 248-258° C., average particle size 25 ⁇ m or less (c5) N,N-dimethyl-N′-(3,4-dichlorophenyl)urea ( Diuron) (Dyhard UR200 (trade name) manufactured by AlzChem), melting point 172 to 182° C
  • the latent curing agent (C) was pulverized using KJ400 (trade name) manufactured by Kurimoto Corporation. Their average particle size was measured by a laser particle size distribution measurement method using SALD-200VER (trade name) manufactured by Shimadzu Corporation. The average particle size obtained is described above.
  • curable compositions of Examples 1-14 and Comparative Examples 1-3 were produced as follows.
  • the elastomer (A) was sheeted with a mixing roll, and the sheeted elastomer (A) was put into a pressure kneader.
  • Epoxy resin (B) or plasticizer (G) and calcium carbonate were added little by little, stirred and kneaded to dissolve elastomer (A).
  • a mixture containing the elastomer (A) was mixed and stirred together with other components such as the epoxy resin (B) and the latent curing agent (C) using a planetary mixer or the like to produce a curable composition.
  • the following were performed in the production methods of the curable compositions of Examples 1 to 12 and Comparative Examples 1 and 2.
  • the latent hardener (C) was used premixed (in a 1:1 weight ratio) with part of the plasticizer (G). That is, the latent curing agent (C) was dispersed in the plasticizer (G) and used.
  • the mixture obtained by mixing all the components was stirred under a reduced pressure of 10 mmHg to 100 mmHg for 20 minutes to 60 minutes. to obtain the intended curable composition.
  • the curable compositions of Examples 13-14 and Comparative Example 3 were prepared as follows. Since (b2) containing elastomer (A) component is used and elastomer (A) component is not used alone, epoxy resin (including (b2) containing elastomer), latent curing agent (C) and other components were mixed and stirred using a planetary mixer or the like to produce a curable composition. Furthermore, in the method for producing the curable compositions of Examples 13 and 14 and Comparative Example 3, the following was performed as necessary.
  • the latent curing agent (C) is mixed with a portion of the filler (D) (the same amount as the latent curing agent (C)), and a pulverizer is used so that the average particle size is 10 ⁇ m or less. It was pulverized and used. That is, the latent curing agent (C) was used, which was mixed with a part of the filler (D) and pulverized to have an average particle size of 10 ⁇ m or less.
  • the mixture obtained by mixing all the components was stirred under a vacuum of 60 mmHg or less for 30 minutes (while stirring under a vacuum of less than 10 mmHg for 12 minutes, The degree of pressure reduction was 4 mmHg) to obtain the intended curable composition.
  • the mixture obtained by mixing all the components was stirred under a reduced pressure of 60 mmHg or less for 30 minutes (during which the reduced pressure of less than 10 mmHg was reduced to 0 minutes). and the maximum pressure reduction was 15 mmHg), thus obtaining the intended curable composition.
  • Adhesion to aluminum plate (curing at 150°C (low temperature))
  • the surface of an aluminum plate (1.0 ⁇ 25 ⁇ 100 mm) according to JISA5182 was degreased with white gasoline.
  • a curable composition was applied to the surface of the aluminum plate.
  • a steel plate according to JIS G3141 whose surface was similarly degreased was overlaid, and a spacer was used to adjust the thickness of the curable composition to 3 mm.
  • a sample was obtained by curing the curable composition under conditions of 150° C. for 30 minutes.
  • Shear strength test method of JASO M 323-77 using an autograph (Shimadzu Corporation, DSC-5000), at a tensile speed of 50 mm / min, aluminum plate adhesion (curing at 150 ° C. (low temperature)) Shear strength (kPa) was measured. Furthermore, the broken state of the cured product of the curable composition was visually observed.
  • the evaluation criteria for the state of destruction are as follows. Tables 1 and 2 show the shear strength (kPa) and breaking state.
  • Adhesion to aluminum plate (cured at 165°C (standard))
  • the surface of an aluminum plate (1.0 ⁇ 25 ⁇ 100 mm) according to JISA5182 was degreased with white gasoline.
  • a curable composition was applied to the surface of the aluminum plate.
  • a steel plate according to JIS G3141 whose surface was similarly degreased was overlaid, and a spacer was used to adjust the thickness of the curable composition to 3 mm.
  • the curable composition was cured at 165° C. for 30 minutes to obtain a sample.
  • Elongation of cured product (cured at 165°C) The elongation was measured according to JIS K 6251 "Tensile test". The curable composition produced as described above was applied to a sheet of 3 mm in thickness, baked under predetermined conditions (165° C., 30 minutes), and then punched into a dumbbell-shaped No. 2 shape to obtain a test sample. Obtained. The elongation at break measured at a pull speed of 50 mm/min was recorded as elongation. Hardness was measured as follows. The above cured products were stacked so as to have a thickness of about 12 mm, and the hardness of the cured product was measured according to JIS K 6253 using a TYPE-A hardness tester.
  • Adhesion to steel plate (hardened at 165°C (standard)) (shear strength)
  • the surface of a steel plate (1.6 ⁇ 25 ⁇ 100 mm) according to JIS G3141 was degreased with white gasoline.
  • a curable composition was applied to the surface of the steel plate.
  • a steel plate according to JIS G3141 whose surface was similarly degreased was overlapped and pressed, and the curable composition was cured at 165° C. for 30 minutes to obtain a sample.
  • the peel strength test method of JASO M 353 using an autograph (Shimadzu Corporation, DSC-5000), at a tensile speed of 50 mm / min, the shear strength ( MPa) was measured.
  • Adhesion to steel plate (cured at 165°C (standard)) (peel strength)
  • the surface of a steel plate (0.8 ⁇ 25 ⁇ 150 mm) according to JIS G3141 is degreased with toluene, and a curable composition is applied to the surface. , and cured for 30 minutes to obtain a sample.
  • the 180° peel strength (N/25 mm) of the sample was measured at a tensile speed of 200 mm/min using an autograph (Shimadzu Corporation, DSC-5000) according to the JASO M353 peel strength test method. Furthermore, the broken state of the cured product was visually observed and evaluated. Evaluation criteria are as follows. Tables 1 and 2 show the 180° peel strength (N/25mm) and breaking state. ⁇ : Less than 10% interfacial failure, 90% or more cohesive failure ⁇ : 10% or more and less than 70% interfacial failure / 30% or more and less than 90% cohesive failure ⁇ : 90% or more interfacial failure
  • Impact strength of cured product (cured at 165°C (standard)) Using a steel plate described in JIS G3141, the curable composition was cured at 165° C. for 30 minutes according to the wedge impact test described in JIS K6865 to prepare a test piece. Impact testing was performed using a high speed tensile tester. The test speed was 2 m/s. The impact strength (N/mm) was obtained by dividing the average strength in the range of 25 to 90% of the total displacement during the test by the width of the test piece.
  • the storage stability of the curable composition was evaluated by storing it at 40° C. for 14 days and measuring the change in viscosity during that time. Specifically, it was evaluated as follows. A 250 cc bottle with a depth of 13 cm was filled with the curable composition, and the viscosity was measured by a rotational viscometer according to JISK6833. A No. 7 rotor was used for viscosity measurement, and measurements were made with two rotations. The material temperature at the time of measurement was 20°C. The viscosity of the curable composition one day after production and the viscosity increase rate measured after standing at 40° C. for 14 days were used as the following evaluation criteria. ⁇ : Less than 30% thickening rate ⁇ -: 30% to less than 40% thickening rate ⁇ : 40% to less than 60% thickening rate ⁇ : 60% or more thickening rate
  • the curable compositions of Examples 1 to 14 had aluminum plate adhesion (curing at 150°C, curing at 165°C, curing at 150°C after storage at 50°C for 5 days), elongation at break (curing at 165°C), hardness, adhesion to steel plate ( Curing at 165° C.) (shear strength and peel strength), impact strength, storage stability and sagging were all excellent.
  • the curable composition of embodiments of the present invention comprises an elastomer (A), an epoxy resin (B) and a latent curing agent (C), wherein the latent curing agent (C) comprises two or more latent curing agents
  • the curable composition can be suitably used for automotive adhesives, more specifically for automotive bodywork adhesive applications.
  • the curable composition can be suitably used, for example, in automotive adhesives, more specifically in automotive bodywork adhesives (eg, structural adhesives, mastic adhesives, etc.).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition durcissable contenant un élastomère (A), une résine époxy (B) et un agent de durcissement latent (C), l'agent de durcissement latent (C) comprenant une combinaison de deux types ou plus d'agents de durcissement latents.
PCT/JP2021/019812 2021-05-25 2021-05-25 Composition durcissable et procédé de production de composition durcissable WO2022249282A1 (fr)

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PCT/JP2021/019812 WO2022249282A1 (fr) 2021-05-25 2021-05-25 Composition durcissable et procédé de production de composition durcissable
JP2021194779A JP7228664B2 (ja) 2021-05-25 2021-11-30 硬化性組成物及び硬化性組成物の製造方法
JP2021196265A JP7122449B1 (ja) 2021-05-25 2021-12-02 硬化性組成物及び硬化性組成物の製造方法
CN202210564498.9A CN115386321A (zh) 2021-05-25 2022-05-23 固化性组合物及固化性组合物的制造方法
US17/751,337 US11920028B2 (en) 2021-05-25 2022-05-23 Curable composition and method for producing curable composition
EP22174835.3A EP4095196A3 (fr) 2021-05-25 2022-05-23 Composition durcissable et procédé de production d'une composition durcissable

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145185A (ja) * 1990-10-05 1992-05-19 Sunstar Eng Inc 構造用接着剤
JP2000345010A (ja) * 1999-04-01 2000-12-12 Mitsui Chemicals Inc 異方導電性ペースト
WO2004108807A1 (fr) * 2003-06-04 2004-12-16 Sunstar Giken Kabushiki Kaisha Composition de matiere de remplissage pateuse a expansion thermique, et procede d'isolation acoustique consistant a remplir une section fermee d'un element de carrosserie d'un vehicule automobile
WO2008016122A1 (fr) * 2006-08-04 2008-02-07 Mitsui Chemicals, Inc. Matière d'étanchéité pour cristaux liquides, procédé pour la production d'écrans à cristaux liquides avec celle-ci et écrans à cristaux liquides
JP2016145440A (ja) * 2015-01-30 2016-08-12 三ツ星ベルト株式会社 アラミド心線の製造方法及び処理剤並びに伝動ベルトの製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04145185A (ja) * 1990-10-05 1992-05-19 Sunstar Eng Inc 構造用接着剤
JP2000345010A (ja) * 1999-04-01 2000-12-12 Mitsui Chemicals Inc 異方導電性ペースト
WO2004108807A1 (fr) * 2003-06-04 2004-12-16 Sunstar Giken Kabushiki Kaisha Composition de matiere de remplissage pateuse a expansion thermique, et procede d'isolation acoustique consistant a remplir une section fermee d'un element de carrosserie d'un vehicule automobile
WO2008016122A1 (fr) * 2006-08-04 2008-02-07 Mitsui Chemicals, Inc. Matière d'étanchéité pour cristaux liquides, procédé pour la production d'écrans à cristaux liquides avec celle-ci et écrans à cristaux liquides
JP2016145440A (ja) * 2015-01-30 2016-08-12 三ツ星ベルト株式会社 アラミド心線の製造方法及び処理剤並びに伝動ベルトの製造方法

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