WO2013069787A1 - Agent de durcissement époxy - Google Patents

Agent de durcissement époxy Download PDF

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Publication number
WO2013069787A1
WO2013069787A1 PCT/JP2012/079174 JP2012079174W WO2013069787A1 WO 2013069787 A1 WO2013069787 A1 WO 2013069787A1 JP 2012079174 W JP2012079174 W JP 2012079174W WO 2013069787 A1 WO2013069787 A1 WO 2013069787A1
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WO
WIPO (PCT)
Prior art keywords
polyalkylene polyamine
group
alkylated
curing agent
epoxy resin
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PCT/JP2012/079174
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English (en)
Japanese (ja)
Inventor
晴康 北口
木曾　浩之
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東ソー株式会社
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Priority claimed from JP2011245698A external-priority patent/JP5866986B2/ja
Priority claimed from JP2011245697A external-priority patent/JP5776500B2/ja
Application filed by 東ソー株式会社 filed Critical 東ソー株式会社
Publication of WO2013069787A1 publication Critical patent/WO2013069787A1/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
    • C08G59/50—Amines
    • C08G59/5006—Amines aliphatic
    • C08G59/502—Polyalkylene polyamines
    • 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

Definitions

  • the present invention relates to an epoxy curing agent, an epoxy resin composition containing the same, and an epoxy resin cured product obtained therefrom.
  • Epoxy resin cured products obtained by curing, solidifying, or cross-linking epoxy resins with epoxy curing agents include coatings, adhesives, flooring, concrete structures, windmill blades, etc., as well as surface coatings for metals, wood, concrete, etc. It is used in a wide range of applications such as civil engineering and building materials.
  • a low-reactivity epoxy curing agent is generally used.
  • a low-reactivity epoxy curing agent is required from the viewpoint of ensuring sufficient working time.
  • Polyether polyamines are commonly used as low-reactivity epoxy curing agents. However, even when a polyether polyamine is used, the working time may not be sufficiently secured.
  • an epoxy curing agent for example, polyalkylene polyamines such as ethylenediamine and diethylenetriamine are used.
  • the curing speed of the amine and the epoxy compound is very fast, so that a sufficient working time cannot be ensured.
  • the working time may not be sufficiently ensured. Therefore, dialkyldiethylenetriamines (see, for example, Patent Document 1 and Patent Document 2) in which the reactivity of polyalkylenepolyamine is further reduced have been proposed.
  • dialkyldiethylenetriamines are still highly reactive and are not sufficient when used as a coating material for the surface of a structure having an intricate structure or the surface of a large structure. Moreover, there also existed a problem that the mechanical strength of the epoxy resin hardened material obtained fell.
  • the present invention has been made in view of the above-mentioned background art, and an object thereof is to provide (1) an epoxy resin curing agent having low reactivity with an epoxy resin and capable of extending the workable time. And (2) To provide an epoxy curing agent capable of providing an epoxy resin cured product having low reactivity with an epoxy resin and excellent in mechanical strength.
  • the present invention is an epoxy curing agent as shown below, an epoxy resin composition containing the same, and an epoxy resin cured product obtained therefrom.
  • N-alkylated amino group having 1 to 6 carbon atoms R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino group (H 2 N—) and imino group
  • N-alkylated amino group having 1 to 6 carbon atoms R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino group (H 2 N—) and imino group
  • An alkylated polyalkylene polyamine (a) having one or more substituents selected from the group consisting of -NH-) in the molecule and having four active amine hydrogen atoms in the molecule; N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino group (H 2 N—) and imino group (—NH—
  • R 1 to R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in the range of 0 to 6. However, R 1 to R 5 are all hydrogen atoms or Not all alkyl groups.
  • the alkylated polyalkylene polyamine (a) is represented by the following formula (1):
  • R 1 to R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in the range of 1 to 6. However, R 1 to R 5 are all hydrogen atoms or Not all alkyl groups.
  • alkylated polyalkylene polyamine (b) is represented by the following formula (2):
  • R 1 to R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and n is in the range of 1 to 6. However, R 1 to R 5 are all hydrogen atoms or Not all alkyl groups.
  • alkylated polyalkylene polyamine (c) is represented by the following formula (3):
  • the alkylated polyalkylene polyamine (c) is N, N′-diisopropylethylenediamine, N, N′-disec-butyl-ethylenediamine, N, N ′, N ′′ -triisopropyldiethylenetriamine, N, N ′ , N ′′ -trisec-butyl-diethylenetriamine, N, N′-diisopropyl-N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, and N, N′-sec- [1] to [4]
  • the alkylated polyalkylene polyamine (a) is N-isopropyldiethylenetriamine, N-secbutyl-diethylenetriamine, N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, and N , N′-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine, at least one alkylated polyalkylene polyamine selected from the group consisting of
  • the alkylated polyalkylene polyamine (b) is N-isopropylethylenediamine, N-secbutyl-ethylenediamine, N, N′-diisopropyldiethylenetriamine, N, N′-disecbutyl-diethylenetriamine, N-isopropyl-N, N′-.
  • alkylated polyalkylene polyamine selected from the group consisting of N, N′-diisopropylethylenediamine, N, N′-secbutyl-ethylenediamine, and N, N ′.
  • N ′′ -triisopropyldiethylenetriamine N, N ′, N ′′ -trisecbutyl-diethylenetriamine, N, N′-diisopropyl-N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, and N, N′-sec-butyl-
  • the above [2] which is at least one alkylated polyalkylene polyamine selected from the group consisting of N, N′-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine Thru
  • An epoxy resin composition comprising the epoxy curing agent according to any one of [1] to [6] and an epoxy resin.
  • An epoxy resin cured product obtained by reacting the epoxy curing agent according to any one of [1] to [6] with an epoxy resin.
  • a method for producing a cured epoxy resin comprising reacting the epoxy curing agent according to any one of [1] to [6] with an epoxy resin.
  • an amine composition for an epoxy curing agent that is less reactive than a generally used amine for an epoxy curing agent and can increase the workable time.
  • the epoxy curing agent of the present invention comprises an N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), an amino group (H 2 N— ) And an imino group (—NH—), an alkylated polyalkylene polyamine having one or two substituents in the molecule and two active amine hydrogen atoms in the molecule (c ).
  • the alkylated polyalkylene polyamine (c) used in the present invention has two active amine hydrogen atoms, the reactivity with the epoxy resin is very slow. Therefore, the reaction rate with the epoxy resin can be suppressed, and the workable time can be prolonged.
  • the epoxy curing agent of the present invention is N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino group (H 2 N—) and imino group (—NH—
  • R—NH— An alkylated polyalkylene polyamine (a) having one or more substituents selected from the group consisting of) in the molecule and having four active amine hydrogen atoms in the molecule; N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino group (H 2 N—) and imino group (—NH—
  • the alkylated polyalkylene polyamine (c) is in the range of 0.5 to 40% by weight and the alkylated polyalkylene polyamine (b) is the balance, Is the feature.
  • the “active amine hydrogen atom” means a hydrogen atom added to a nitrogen atom that can react with an epoxy group.
  • the epoxy curing agent of the present invention contains an alkylated polyalkylene polyamine (a), an alkylated polyalkylene polyamine (b), and an alkylated polyalkylene polyamine (c), (a) + (b) + Reactivity with the epoxy resin is low because (a) is 0.01 to 5% by weight, (c) is 0.5 to 40% by weight and (b) is the balance with respect to (c). It becomes an epoxy curing agent that gives a cured epoxy resin having excellent strength characteristics.
  • (a) is 0.05 to 3% by weight
  • (c) is 5 to 20% by weight
  • (b) is the balance with respect to (a) + (b) + (c).
  • the alkylated polyalkylene polyamine (a) is more than 5% by weight with respect to (a) + (b) + (c), the strength characteristics are improved, but the reactivity with the epoxy resin is increased. Unable to ensure sufficient working time.
  • (a) is less than 0.01% by weight with respect to (a) + (b) + (c)
  • a sufficient effect for improving the strength characteristics cannot be obtained.
  • the alkylated polyalkylene polyamine (c) is more than 40% by weight based on (a) + (b) + (c)
  • the reactivity with the epoxy resin is reduced, but the strength characteristics are improved. A sufficient effect cannot be obtained.
  • the epoxy curing agent of the present invention preferably comprises an alkylated polyalkylene polyamine (c) and an alkylated polyalkylene polyamine (a).
  • the epoxy curing agent of the present invention is particularly preferably composed of an alkylated polyalkylene polyamine (c), an alkylated polyalkylene polyamine (b) and an alkylated polyalkylene polyamine (a).
  • the alkyl group (R) in the N-alkylated amino group having 1 to 6 carbon atoms is, for example, Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group, and a cyclohexyl group.
  • alkylated polyalkylene polyamines (a) to (c) when the alkylated polyalkylene polyamines (a) to (c) have a primary amino group at the terminal of the polyalkylene polyamine chain, the reactivity with the epoxy resin is increased and the working time is shortened. Therefore, as the alkylated polyalkylene polyamines (a) to (c), compounds having no amino group at the terminal are more preferable.
  • the alkylated polyalkylene polyamine (a) is specifically an N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms.
  • alkylated polyalkylene polyamine (b) is specifically an N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R is an alkyl group having 1 to 6 carbon atoms.
  • alkylated polyalkylene polyamine (c) is specifically an N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R is an alkyl group having 1 to 6 carbon atoms. And 1 or 2 substituents selected from the group consisting of an amino group (H 2 N—) and an imino group (—NH—) in the molecule, and an active amine hydrogen in the molecule Examples thereof include an alkylated polyalkylene polyamine represented by the above formula (3) having 2 atoms.
  • R 1 to R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic.
  • R 1 and R 3 are hydrogen atoms.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group, and a cyclohexyl group. Is mentioned.
  • N is an integer of 1 to 6, and preferably an integer of 1 to 3.
  • R 1 to R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group may be linear, branched or cyclic.
  • R 1 and R 3 are hydrogen atoms.
  • the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a sec-butyl group, a pentyl group, an isopentyl group, a hexyl group, and a cyclohexyl group.
  • N is an integer of 0 to 6, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
  • alkylated polyalkylene polyamine (a) examples include N-isopropyldiethylenetriamine, N-secbutyl-diethylenetriamine, N, N′-bis [2- (isopropylamino) ethyl] -1,2, -Ethanediamine, N, N'-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine and the like.
  • suitable examples of the alkylated polyalkylene polyamine (b) include, for example, N-isopropylethylenediamine, N-secbutyl-ethylenediamine, N, N′-diisopropyldiethylenetriamine, N, N′-disecbutyl- Diethylenetriamine, N-isopropyl-N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, N-sec-butyl-N, N′-bis [2- (sec-butylamino) And ethyl] -1,2-ethanediamine.
  • suitable examples of the alkylated polyalkylene polyamine (c) include, for example, N, N′-diisopropylethylenediamine, N, N′-secbutyl-ethylenediamine, N, N ′, N ′′ -triisopropyl Diethylenetriamine, N, N ′, N ′′ -trisecbutyl-diethylenetriamine, N, N′-diisopropyl-N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, N, N Examples include '-sec-butyl-N, N'-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine.
  • the content of the above-mentioned alkylated polyalkylene polyamine (c) is usually 1% by weight or more, preferably 3% by weight or more based on the whole epoxy curing agent. The greater the content, the lower the reactivity with the epoxy resin and the longer the workable time.
  • the epoxy curing agent of the present invention contains the above-mentioned alkylated polyalkylene polyamine (c) or the above-mentioned alkylated polyalkylene polyamine (a), alkylated polyalkylene polyamine (b), and alkylated. It contains polyalkylene polyamine (c). Therefore, other components are not necessarily required, but other amines may be contained without departing from the gist of the present invention. Examples of such amines include polyfunctional amines having 3 or more active amine hydrogen atoms. However, even for such a polyfunctional amine, a component that significantly improves the reactivity with the epoxy resin may not be used at all, or may be used within a range that can maintain a low reactivity with the epoxy resin. desirable.
  • polyfunctional amine having 3 or more active amine hydrogen atoms examples include aliphatic amines, alicyclic amines, aromatic amines, and aliphatic amines, aromatic amines, or Mannich base derivatives of alicyclic amines. Also known are polyamide derivatives of aliphatic amines, aromatic amines or alicyclic amines, amine addition derivatives of aliphatic amines, aromatic amines or alicyclic amines, and the like.
  • aliphatic amine examples include polyethyleneamine (EDA, DETA, TETA, TEPA, PEHA, etc.), polypropyleneamine, aminopropylated ethylenediamine (Am3, Am4, Am5, etc.), aminopropylated propylenediamine, 1,6-hexane.
  • Diamine 3,3,5-trimethyl-1,6-hexanediamine, 3,5,5-trimethyl-1,6-hexanediamine, 2-methyl-1,5-pentanediamine [Dytek®-A And the like, or a combination thereof.
  • Poly (alkylene oxide) diamines and triamines available under the trade name Jeffamine from Huntsman are also exemplified as such aliphatic amines.
  • the Jeffamine is not particularly limited.
  • the alicyclic amine or aromatic amine is not particularly limited, and examples thereof include 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, hydrogenated orthotoluenediamine, Hydrogenated metatoluenediamine, metaxylylenediamine, hydrogenated metaxylylenediamine (commercially available as 1,3-BAC), isophoronediamine, various isomers or norbornanediamine, 3,3′-dimethyl-4, Examples include 4′-diaminodicyclohexylmethane, 4,4′-diaminodicyclohexylmethane, 2,4′-diaminodicyclohexylmethane, a mixture of methylene-bridged poly (cyclohexyl-aromatic) amine, and the like, or combinations thereof.
  • the Mannich base derivative can be produced, for example, by reacting the above-described aliphatic amine, alicyclic amine, or aromatic amine with phenol or substituted phenol and formaldehyde.
  • the polyamide derivative can be prepared, for example, by reacting the above-mentioned aliphatic amine, alicyclic amine or aromatic amine with a dimer fatty acid or a mixture of a dimer fatty acid and a fatty acid.
  • Amidoamine derivatives can be prepared, for example, by reaction of aliphatic amines, alicyclic amines or aromatic amines with fatty acids.
  • the amine adduct is, for example, a reaction between an aliphatic amine, an alicyclic amine or an aromatic amine and an epoxy resin (for example, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, epoxy novolac resin, etc.).
  • an epoxy resin for example, bisphenol-A diglycidyl ether, bisphenol-F diglycidyl ether, epoxy novolac resin, etc.
  • a monofunctional epoxy resin for example, phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, or other alkyl glycidyl ether
  • the production method of the above-mentioned alkylated polyalkylene polyamine (a), alkylated polyalkylene polyamine (b) and alkylated polyalkylene polyamine (c) is not particularly limited. Obtained by partial N-alkylation. For example, it can be obtained by reacting at least one polyalkylene polyalkylene polyamine having at least two nitrogen atoms, at least one alkylating agent, and hydrogen in the presence of a catalyst.
  • polyalkylene polyamine used here, for example, a polyethylene polyamine, a polypropylene polyamine, and those combination are mentioned.
  • polyethylene polyamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and other higher order polyethylene polyamines.
  • DETA diethylenetriamine
  • TETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • PEHA pentaethylenehexamine
  • TETA may contain not only linear TETA but also tris-aminoethyleneamine.
  • the alkylating agent used here is not particularly limited, and examples thereof include cyclopentanone, cyclohexanone, aldehydes having 1 to 6 carbon atoms, and ketones having 2 to 6 carbon atoms.
  • Examples of the catalyst used here include commonly used hydrogenation catalysts such as nickel, Raney nickel, Raney cobalt platinum black, platinum oxide, palladium, palladium / activated carbon (Pd / C), and any of these. May be.
  • the addition amount of the catalyst is preferably in the range of 0.1 to 10% by weight based on the polyalkylene polyamine.
  • the molar reaction ratio between the alkylating agent and the polyalkylene polyamine is not particularly limited, but is preferably 2 or more, more preferably 2.1 or more. This is because when the molar reaction ratio is 2.1 or more, the unreacted polyalkylene polyamine remaining without being alkylated is 1% by weight or less.
  • the epoxy resin composition of the present invention is characterized by containing the above-described epoxy curing agent of the present invention and an epoxy resin.
  • the epoxy resin may be an uncured epoxy resin generally used in the production of a cured epoxy resin, and is not particularly limited. For example, two or more 1,2-epoxy groups per molecule are included. Examples thereof include an uncured epoxy resin. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy novolac resin, alicyclic epoxy resin, polyfunctional epoxy resin, brominated epoxy resin and the like are exemplified. These epoxy resins can be used either without solvent or diluted with a solvent. An epoxy resin hardened material is obtained by making the epoxy hardener and epoxy resin in the amine composition for epoxy hardeners of this invention mentioned above react.
  • a conventionally known plasticizer may be used. It can.
  • a plasticizer is not particularly limited, and examples thereof include benzyl alcohol, nonylphenol, various phthalates, and the like.
  • a solvent, a filler, a pigment, and a pigment are used.
  • Dispersants, rheology modifiers, thixotropic agents, fluidizing and smoothing aids, antifoaming agents and the like may be used.
  • Suitable solvents include, for example, aromatic hydrocarbon compounds, aliphatic hydrocarbon compounds, esters, ketones, ethers, alcohols and the like.
  • test piece was created using the dumbbell type punch for tensile tests (JIS K 6259 No. 2 type dumbbell shape).
  • the test piece was attached to a Tensilon universal testing machine (trade name: RTM500, manufactured by Orientec Co., Ltd.) using a parallel fastening lock, pulled at a speed of 30 mm / min, and the maximum tensile strength (MPa) of the sample piece was measured.
  • MPa maximum tensile strength
  • Example 1 0.03 g of triisopropylated diethylenetriamine obtained in Synthesis Example 1, 3.35 g of diisopropylated diethylenetriamine, and 10 g of an epoxy resin (Epicoat 828, manufactured by Mitsubishi Chemical Corporation) are weighed in a 20 ml sample bottle until uniform with a spatula. After mixing, curing at a constant temperature of 25 ° C., using a vibration type viscometer (trade name: VM-1G-MJ, manufactured by Yamaichi Electronics Co., Ltd.) and a data collection system (trade name: NR-1000, manufactured by Keyence) The change in viscosity over time was measured. After mixing, the time until the viscosity value reached 1000 cP was measured and found to be 8.6 hours.
  • a vibration type viscometer trade name: VM-1G-MJ, manufactured by Yamaichi Electronics Co., Ltd.
  • NR-1000 data collection system
  • Example 2 Reference Example 1 and Comparative Examples 1 to 3
  • Example 2 Reference Example 1 and Comparative Examples 1 to 3
  • Tables 1 and 2 The same procedure as in Example 1 was performed except that the types and amounts of amines shown in Tables 1 and 2 were used. The results are also shown in Tables 1 and 2.
  • the polyfunctional amine that does not affect the reactivity with the epoxy resin is suitable. Although it can be used (see Example 10), it is understood that the effects of the present invention are not exhibited when a component that significantly improves the reactivity with the epoxy resin is used (see Reference Example 1).
  • Example 11 0.003 g (0.01 wt%) of monoisopropylated diethylenetriamine obtained in Synthesis Example 4, 26.893 g (99.49 wt%) of diisopropylated diethylenetriamine, and 0.135 g (0.5 wt%) of triisopropylated diethylenetriamine
  • 80 g of epoxy resin (Epicoat 828, manufactured by Mitsubishi Chemical Corporation) was weighed into a 100 ml sample bottle, mixed with a spatula until uniform, and then cured under constant conditions at 25 ° C.
  • vibration viscometer (trade name: VM) -1G-MJ (manufactured by Yamaichi Electronics Co., Ltd.)
  • a data collection system (trade name: NR-1000, manufactured by Keyence Co.) were used to measure the change in viscosity over time.
  • Example 11 29, Comparative Examples 4 to 8, Reference Examples 2 to 11.
  • the same procedure as in Example 1 was performed except that the types and amounts of amines shown in Tables 3 to 5 were used. The results are also shown in Tables 3 to 5.
  • the epoxy resin curing agent containing the alkylated polyalkylene polyamine (c) of the present invention has low reactivity as a curing agent, and can achieve a sufficient working time when used in combination with an epoxy resin. It is preferably used in applications that require a long working time, such as coating on the surface of a structure having an intricate structure or the surface of a large structure.
  • the epoxy curing agent containing the alkylated polyalkylene polyamines (a) to (c) of the present invention can provide an epoxy resin having low reactivity and excellent mechanical strength as a curing agent. It is suitably used in applications that require a long working time and sufficient strength, such as concrete structures and windmill blades.

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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)
  • Epoxy Resins (AREA)

Abstract

La présente invention concerne une composition d'amine qui a une faible réactivité avec des résines époxy et avec laquelle le temps ouvrable peut être prolongé. La présente invention utilise, comme agent de durcissement époxy, une polyalkylène polyamine alkylée (c) comprenant, dans sa molécule : un ou deux types de substituants choisis dans le groupe consistant en les groupes amino N-alkylés en C1-6 (R-NH- ; où R représente un groupe alkyle en C1-6), un groupe amino (H2N-) et un groupe imino (-NH-) ; et deux atomes d'hydrogène d'amine actifs.
PCT/JP2012/079174 2011-11-09 2012-11-09 Agent de durcissement époxy WO2013069787A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2011-245698 2011-11-09
JP2011-245697 2011-11-09
JP2011245698A JP5866986B2 (ja) 2011-11-09 2011-11-09 エポキシ硬化剤
JP2011245697A JP5776500B2 (ja) 2011-11-09 2011-11-09 エポキシ硬化剤用アミン組成物

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017145714A (ja) * 2016-02-16 2017-08-24 クリーンエナジーファクトリー株式会社 風力発電機

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258388A (ja) * 1994-03-16 1995-10-09 Air Prod And Chem Inc ポリ−ｎ−メチル化第２級アミンを含む可撓化されたポリエポキシド樹脂
JPH08325360A (ja) * 1995-04-11 1996-12-10 Air Prod And Chem Inc エポキシ硬化剤としての部分的にメチル化されたポリアミン
JP2002284861A (ja) * 2001-03-22 2002-10-03 Ajinomoto Co Inc 一液型エポキシ樹脂組成物用の潜在性硬化剤組成物および一液型エポキシ樹脂組成物
JP2003201337A (ja) * 2001-09-28 2003-07-18 Nippon Oil Corp 常温硬化型エポキシ樹脂組成物の硬化時間を調整する方法及びコンクリート構造物の補強方法
JP2007022955A (ja) * 2005-07-15 2007-02-01 Tosoh Corp アルキル化ポリアルキレンポリアミン組成物、及びその製造方法
JP2010037560A (ja) * 2008-08-06 2010-02-18 Air Products & Chemicals Inc ベンジル化ポリアルキレンポリアミン及びその使用
JP2011057675A (ja) * 2009-09-11 2011-03-24 Air Products & Chemicals Inc 尿素硬化剤を含有する低温硬化性のエポキシ組成物
JP2011068814A (ja) * 2009-09-28 2011-04-07 Dic Corp エポキシ樹脂組成物及びその硬化物
JP2012052113A (ja) * 2010-09-01 2012-03-15 Air Products & Chemicals Inc 低温硬化性エポキシ組成物

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07258388A (ja) * 1994-03-16 1995-10-09 Air Prod And Chem Inc ポリ−ｎ−メチル化第２級アミンを含む可撓化されたポリエポキシド樹脂
JPH08325360A (ja) * 1995-04-11 1996-12-10 Air Prod And Chem Inc エポキシ硬化剤としての部分的にメチル化されたポリアミン
JP2002284861A (ja) * 2001-03-22 2002-10-03 Ajinomoto Co Inc 一液型エポキシ樹脂組成物用の潜在性硬化剤組成物および一液型エポキシ樹脂組成物
JP2003201337A (ja) * 2001-09-28 2003-07-18 Nippon Oil Corp 常温硬化型エポキシ樹脂組成物の硬化時間を調整する方法及びコンクリート構造物の補強方法
JP2007022955A (ja) * 2005-07-15 2007-02-01 Tosoh Corp アルキル化ポリアルキレンポリアミン組成物、及びその製造方法
JP2010037560A (ja) * 2008-08-06 2010-02-18 Air Products & Chemicals Inc ベンジル化ポリアルキレンポリアミン及びその使用
JP2011057675A (ja) * 2009-09-11 2011-03-24 Air Products & Chemicals Inc 尿素硬化剤を含有する低温硬化性のエポキシ組成物
JP2011068814A (ja) * 2009-09-28 2011-04-07 Dic Corp エポキシ樹脂組成物及びその硬化物
JP2012052113A (ja) * 2010-09-01 2012-03-15 Air Products & Chemicals Inc 低温硬化性エポキシ組成物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017145714A (ja) * 2016-02-16 2017-08-24 クリーンエナジーファクトリー株式会社 風力発電機

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