WO2013069787A1 - Epoxy curing agent - Google Patents

Epoxy curing agent 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
Prior art date
Application number
PCT/JP2012/079174
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French (fr)
Japanese (ja)
Inventor
晴康 北口
木曾　浩之
Original Assignee
東ソー株式会社
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Publication date
Priority claimed from JP2011245698A external-priority patent/JP5866986B2/en
Priority claimed from JP2011245697A external-priority patent/JP5776500B2/en
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/en

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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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Abstract

The present invention provides an amine composition that has low reactivity with epoxy resins and with which the workable time can be extended. The present invention uses, as an epoxy curing agent, an alkylated polyalkylene polyamine (c) including, in the molecule thereof: one or two types of substituents selected from the group consisting of C1-6 N-alkylated amino groups (R-NH-; wherein R represents a C1-6 alkyl group), an amino group (H2N-), and an imino group (-NH-); and two active amine hydrogen atoms.

Description

エポキシ硬化剤Epoxy curing agent
　本発明は、エポキシ硬化剤、それを含有するエポキシ樹脂組成物、及びそれから得られるエポキシ樹脂硬化物に関する。 The present invention relates to an epoxy curing agent, an epoxy resin composition containing the same, and an epoxy resin cured product obtained therefrom.
　エポキシ樹脂をエポキシ硬化剤によって硬化、固化又は架橋して得られるエポキシ樹脂硬化物は、金属、木材、コンクリート等の表面コーティングの他、塗料、接着剤、床材、コンクリート用建造物や風車ブレード等の土木・建築材料用途等の幅広い用途で使用されている。
　構造物表面に均一な皮膜を形成する際、低反応性のエポキシ硬化剤が一般的に使用されている。例えば、入り組んだ構造を有する構造物表面や大型の構造物表面に皮膜を形成する場合には、作業時間を十分に確保するという観点から低反応性のエポキシ硬化剤が求められている。
　低反応性のエポキシ硬化剤として、ポリエーテルポリアミンが一般的に使用されている。しかしながらポリエーテルポリアミンを使用した場合でも、作業時間が十分に確保されない場合がある。 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.
In forming a uniform film on the structure surface, a low-reactivity epoxy curing agent is generally used. For example, in the case where a film is formed on the surface of a structure having an intricate structure or a large structure, 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.
　一方、床材やコンクリート用建造物、風車ブレード等の用途では、アミンとエポキシ組成物から製品を製造する際の作業時間が長いアミン系硬化剤が好まれ、かつ得られるエポキシ樹脂の機械強度も必要とされる。 On the other hand, for applications such as flooring, concrete structures and windmill blades, amine-based curing agents with a long working time when manufacturing products from amines and epoxy compositions are preferred, and the mechanical strength of the resulting epoxy resin is also high. Needed.
　このようなエポキシ硬化剤としては、例えば、エチレンジアミンやジエチレントリアミン等のポリアルキレンポリアミンが使用されるが、この場合、アミンとエポキシ化合物との硬化速度が非常に速いため、十分な作業時間が確保されない。また、低反応性のエポキシ硬化剤として、上記したポリエーテルポリアミンを使用した場合でも、作業時間が十分に確保されない場合がある。
　そのため、ポリアルキレンポリアミンの反応性をさらに低減したジアルキルジエチレントリアミン類（例えば、特許文献１、特許文献２参照）が提案されている。
　しかしながら、これらのジアルキルジエチレントリアミン類では依然として反応性は高く、入り組んだ構造を有する構造物表面や大型の構造物表面のコーティング材料として使用する場合には十分でなかった。
　また、得られるエポキシ樹脂硬化物の機械強度が低下するという問題もあった。 As such an epoxy curing agent, for example, polyalkylene polyamines such as ethylenediamine and diethylenetriamine are used. In this case, the curing speed of the amine and the epoxy compound is very fast, so that a sufficient working time cannot be ensured. Further, even when the above-described polyether polyamine is used as the low-reactivity epoxy curing agent, 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.
However, these 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.
米国特許第３，２８０，０４３号明細書US Pat. No. 3,280,043 欧州特許出願公開第２１５７１１２号明細書European Patent Application No. 2157112
　本発明は上記の背景技術に鑑みてなされたものであり、その目的は、（１）エポキシ樹脂との反応性が低く、作業可能時間の長時間化が可能なエポキシ樹脂硬化剤を提供すること、及び（２）エポキシ樹脂との反応性が低く、かつ機械強度に優れるエポキシ樹脂硬化物を与えることが可能なエポキシ硬化剤を提供することである。 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.
　本発明者らは、エポキシ硬化剤について、鋭意検討を重ねた結果、本発明を完成するに至った。すなわち、本発明は以下に示すとおりのエポキシ硬化剤、それを含有するエポキシ樹脂組成物、及びそれから得られるエポキシ樹脂硬化物である。 As a result of intensive studies on the epoxy curing agent, the present inventors have completed the present invention. That is, 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.
　［１］炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種の置換基を分子内に有し、かつ分子内に活性アミン水素原子を２個有するアルキル化ポリアルキレンポリアミン（ｃ）を含有するエポキシ硬化剤。
　［２］炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を４個有するアルキル化ポリアルキレンポリアミン（ａ）と、
炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を３個有するアルキル化ポリアルキレンポリアミン（ｂ）と、
上記［１］アルキル化ポリアルキレンポリアミン（ｃ）とを含有し、（ａ）＋（ｂ）＋（ｃ）に対して、（ａ）が０．０１～５重量％、（ｃ）が０．５～４０重量％、（ｂ）が残部であることを特徴とするエポキシ硬化剤。
　［３］アルキル化ポリアルキレンポリアミン（ｃ）が、下記式（３） [1] 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 ( Epoxy containing an alkylated polyalkylene polyamine (c) having one or two substituents selected from the group consisting of —NH— in the molecule and having two active amine hydrogen atoms in the molecule Curing agent.
[2] 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— An alkylated polyalkylene polyamine (b) having one or two or more substituents selected from the group consisting of) in the molecule and three active amine hydrogen atoms in the molecule;
[1] containing an alkylated polyalkylene polyamine (c), wherein (a) is 0.01 to 5% by weight and (c) is 0.1% relative to (a) + (b) + (c). An epoxy curing agent characterized in that 5 to 40% by weight and (b) is the balance.
[3] The alkylated polyalkylene polyamine (c) is represented by the following formula (3):
Figure JPOXMLDOC01-appb-C000005
 （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは０～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）
で示されるアルキル化ポリアルキレンポリアミンであることを特徴とする上記［１］又は［２］に記載のエポキシ硬化剤。
　［４］アルキル化ポリアルキレンポリアミン（ａ）が下記式（１）
Figure JPOXMLDOC01-appb-C000005
 (Wherein 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 epoxy curing agent according to the above [1] or [2], which is an alkylated polyalkylene polyamine represented by the formula:
[4] The alkylated polyalkylene polyamine (a) is represented by the following formula (1):
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）
で示されるアルキル化ポリアルキレンポリアミンであり、アルキル化ポリアルキレンポリアミン（ｂ）が下記式（２）
Figure JPOXMLDOC01-appb-C000006
(Wherein 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.)
Wherein the alkylated polyalkylene polyamine (b) is represented by the following formula (2):
Figure JPOXMLDOC01-appb-C000007
 （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）
で示されるアルキル化ポリアルキレンポリアミンであり、かつアルキル化ポリアルキレンポリアミン（ｃ）が下記式（３）
Figure JPOXMLDOC01-appb-C000007
 (Wherein 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.)
And the alkylated polyalkylene polyamine (c) is represented by the following formula (3):
Figure JPOXMLDOC01-appb-C000008
 （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）
で示されるアルキル化ポリアルキレンポリアミンであることを特徴とする上記［２］に記載のエポキシ硬化剤。
　［５］アルキル化ポリアルキレンポリアミン（ｃ）が、Ｎ，Ｎ’－ジイソプロピルエチレンジアミン、Ｎ，Ｎ’－ジｓｅｃ－ブチル－エチレンジアミン、Ｎ，Ｎ’，Ｎ’’－トリイソプロピルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’’－トリｓｅｃ－ブチル－ジエチレントリアミン、Ｎ，Ｎ’－ジイソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも一種であることを特徴とする上記［１］乃至［４］のいずれかに記載のエポキシ硬化剤。
　［６］アルキル化ポリアルキレンポリアミン（ａ）が、Ｎ－イソプロピルジエチレントリアミン、Ｎ－ｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであり、
アルキル化ポリアルキレンポリアミン（ｂ）が、Ｎ－イソプロピルエチレンジアミン、Ｎ－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’－ジイソプロピルジエチレントリアミン、Ｎ，Ｎ’－ジｓｅｃブチル－ジエチレントリアミン、Ｎ－イソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであり、かつ
アルキル化ポリアルキレンポリアミン（ｃ）が、Ｎ，Ｎ’－ジイソプロピルエチレンジアミン、Ｎ，Ｎ’－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’，Ｎ’’－トリイソプロピルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’’－トリｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ジイソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであることを特徴とする上記［２］乃至［５］のいずれかに記載のエポキシ硬化剤。
　［７］上記［１］乃至［６］のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを含有することを特徴とするエポキシ樹脂組成物。
　［８］上記［１］乃至［６］のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを反応させて得られるエポキシ樹脂硬化物。
　［９］上記［１］乃至［６］のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを反応させることを特徴とするエポキシ樹脂硬化物の製造方法。
Figure JPOXMLDOC01-appb-C000008
 (Wherein 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.)
The epoxy curing agent according to the above [2], which is an alkylated polyalkylene polyamine represented by the formula:
[5] 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] above, which is at least one selected from the group consisting of butyl-N, N′-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine The epoxy hardener in any one.
[6] 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′-. From bis [2- (isopropylamino) ethyl] -1,2-ethanediamine and N-sec-butyl-N, N′-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine And at least one 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 | or the epoxy hardener in any one of [5].
[7] An epoxy resin composition comprising the epoxy curing agent according to any one of [1] to [6] and an epoxy resin.
[8] An epoxy resin cured product obtained by reacting the epoxy curing agent according to any one of [1] to [6] with an epoxy resin.
[9] 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.
　本発明のエポキシ硬化剤によれば、一般に使用されるエポキシ硬化剤用アミンより反応性が低く、作業可能時間の長時間化が可能なエポキシ硬化剤用アミン組成物を提供することが出来る。 According to the epoxy curing agent of the present invention, it is possible to provide 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.
　以下、本発明を詳細に説明する。
　本発明のエポキシ硬化剤は、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種の置換基を分子内に有し、かつ分子内に活性アミン水素原子を２個有するアルキル化ポリアルキレンポリアミン（ｃ）を含有することをその特徴とする。 Hereinafter, the present invention will be described in detail.
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 ).
　本発明で用いられるアルキル化ポリアルキレンポリアミン（ｃ）は、活性アミン水素原子を２個有するため、エポキシ樹脂との反応性が非常に遅い。したがって、エポキシ樹脂との反応速度を抑制し、作業可能時間の長時間化することができる。 Since 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.
　また、本発明のエポキシ硬化剤は、
　炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を４個有するアルキル化ポリアルキレンポリアミン（ａ）と、
　炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を３個有するアルキル化ポリアルキレンポリアミン（ｂ）と、
　炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種の置換基を分子内に有し、かつ分子内に活性アミン水素原子を２個有するアルキル化ポリアルキレンポリアミン（ｃ）とを含有し、
　アルキル化ポリアルキレンポリアミン（ａ）～（ｃ）の合計量［（ａ）＋（ｂ）＋（ｃ）］に対して、アルキル化ポリアルキレンポリアミン（ａ）が０．０１～５重量％の範囲であり、アルキル化ポリアルキレンポリアミン（ｃ）が０．５～４０重量％の範囲であり、アルキル化ポリアルキレンポリアミン（ｂ）が残部であること、
をその特徴とする。
　なお、本発明において、「活性アミン水素原子」とは、エポキシ基と反応可能な、窒素原子に付加した水素原子を意味する。 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— 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— An alkylated polyalkylene polyamine (b) having one or two or more substituents selected from the group consisting of) in the molecule and three 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— An alkylated polyalkylene polyamine (c) having one or two substituents selected from the group consisting of) and two active amine hydrogen atoms in the molecule;
The alkylated polyalkylene polyamine (a) is in the range of 0.01 to 5% by weight with respect to the total amount [(a) + (b) + (c)] of the alkylated polyalkylene polyamine (a) to (c). 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.
In the present invention, the “active amine hydrogen atom” means a hydrogen atom added to a nitrogen atom that can react with an epoxy group.
　本発明のエポキシ硬化剤は、アルキル化ポリアルキレンポリアミン（ａ）と、アルキル化ポリアルキレンポリアミン（ｂ）と、アルキル化ポリアルキレンポリアミン（ｃ）とを含有する場合、（ａ）＋（ｂ）＋（ｃ）に対して（ａ）が０．０１～５重量％、（ｃ）が０．５～４０重量％、（ｂ）が残部とすることで、エポキシ樹脂との反応性が低く、かつ強度特性に優れるエポキシ樹脂硬化物を与えるエポキシ硬化剤となる。好ましくは、（ａ）＋（ｂ）＋（ｃ）に対して（ａ）が０．０５～３重量％、（ｃ）が５～２０重量％、（ｂ）が残部である。 When 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. Preferably, (a) is 0.05 to 3% by weight, (c) is 5 to 20% by weight, and (b) is the balance with respect to (a) + (b) + (c).
　アルキル化ポリアルキレンポリアミン（ａ）が、（ａ）＋（ｂ）＋（ｃ）に対して５重量％よりも多い場合、強度特性が改善するものの、エポキシ樹脂との反応性が増大するために、十分な作業時間を確保することができない。（ａ）が、（ａ）＋（ｂ）＋（ｃ）に対して０．０１重量％よりも少ない場合、強度特性の改善に十分な効果が得られない。
　また、アルキル化ポリアルキレンポリアミン（ｃ）が、（ａ）＋（ｂ）＋（ｃ）に対して４０重量％よりも多い場合、エポキシ樹脂との反応性が低減するものの、強度特性の改善に十分な効果が得られない。（ｃ）が、（ａ）＋（ｂ）＋（ｃ）に対して０．５重量％よりも少ない場合、エポキシ樹脂との反応性の低減に十分な効果が得られない。
　本発明のエポキシ硬化剤は、アルキル化ポリアルキレンポリアミン（ｃ）及びアルキル化ポリアルキレンポリアミン（ａ）からなるのが好ましい。
　また、本発明のエポキシ硬化剤は、アルキル化ポリアルキレンポリアミン（ｃ）、アルキル化ポリアルキレンポリアミン（ｂ）及びアルキル化ポリアルキレンポリアミン（ａ）からなるのが特に好ましい。 When 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. When (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.
Further, when 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. When (c) is less than 0.5% by weight with respect to (a) + (b) + (c), a sufficient effect for reducing the reactivity with the epoxy resin 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).
　本発明において、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）中のアルキル基（Ｒ）としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、シクロヘキシル基等が挙げられる。 In the present invention, the alkyl group (R) in the N-alkylated amino group having 1 to 6 carbon atoms (R—NH—, where R represents an alkyl 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.
　本発明において、アルキル化ポリアルキレンポリアミン（ａ）～（ｃ）は、ポリアルキレンポリアミン鎖の末端に１級アミノ基を有する場合、エポキシ樹脂との反応性が高くなり作業時間が短くなる。よって、アルキル化ポリアルキレンポリアミン（ａ）～（ｃ）としては、末端にアミノ基を有さない化合物がより好ましい。
　上記したアルキル化ポリアルキレンポリアミン（ａ）としては、具体的には、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を４個有する、上記式（１）で示されるアルキル化ポリアルキレンポリアミンが例示される。
　また、上記したアルキル化ポリアルキレンポリアミン（ｂ）としては、具体的には、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を３個有する、上記式（２）で示されるアルキル化ポリアルキレンポリアミンが例示される。 In the present invention, 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. ), One or more 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 atom in the molecule And an alkylated polyalkylene polyamine represented by the above formula (1).
The 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. ), One or more 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 in the molecule The alkylated polyalkylene polyamine represented by the above formula (2) having 3 hydrogen atoms is exemplified.
　さらに、上記したアルキル化ポリアルキレンポリアミン（ｃ）としては、具体的には、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種の置換基を分子内に有し、かつ分子内に活性アミン水素原子を２個有する、上記式（３）で示されるアルキル化ポリアルキレンポリアミンが例示される。 Further, the 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.
　上記式（１）、（２）において、Ｒ１～Ｒ５は各々独立して、水素原子又は炭素数１～６のアルキル基を表し、アルキル基は直鎖、分岐、環状のいずれでもよい。好ましくはＲ１及びＲ３が水素原子である。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、シクロヘキシル基等が挙げられる。また、ｎは１～６の整数であり、１～３の整数であることが好ましい。
　また、上記式（３）において、Ｒ１～Ｒ５は各々独立して、水素原子又は炭素数１～６のアルキル基を表し、アルキル基は直鎖、分岐、環状のいずれでもよい。好ましくはＲ１及びＲ３が水素原子である。炭素数１～６のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、ｔｅｒｔ－ブチル基、ｓｅｃ－ブチル基、ペンチル基、イソペンチル基、ヘキシル基、シクロヘキシル基等が挙げられる。また、ｎは０～６の整数であり、１～６の整数であることが好ましく、１～３の整数であることがさらに好ましい。 In the above formulas (1) and (2), 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. Preferably R 1 and R 3 are hydrogen atoms. Examples of 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.
In the above formula (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. Preferably R 1 and R 3 are hydrogen atoms. Examples of 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 0 to 6, preferably an integer of 1 to 6, and more preferably an integer of 1 to 3.
　本発明において、アルキル化ポリアルキレンポリアミン（ａ）の好適な例としては、Ｎ－イソプロピルジエチレントリアミン、Ｎ－ｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミン等が挙げられる。 In the present invention, preferred examples of the alkylated polyalkylene polyamine (a) 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.
　本発明において、アルキル化ポリアルキレンポリアミン（ｂ）の好適な例としては、例えば、Ｎ－イソプロピルエチレンジアミン、Ｎ－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’－ジイソプロピルジエチレントリアミン、Ｎ，Ｎ’－ジｓｅｃブチル－ジエチレントリアミン、Ｎ－イソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、Ｎ－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミン等が挙げられる。
　本発明において、アルキル化ポリアルキレンポリアミン（ｃ）の好適な例としては、例えば、Ｎ，Ｎ’－ジイソプロピルエチレンジアミン、Ｎ，Ｎ’－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’，Ｎ’’－トリイソプロピルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’’－トリｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ジイソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、Ｎ，Ｎ’－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミン等が挙げられる。 In the present invention, 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.
In the present invention, 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.
　本発明のエポキシ硬化剤において、上記したアルキル化ポリアルキレンポリアミン（ｃ）の含有量は、エポキシ硬化剤全体に対して、通常１重量％以上、好ましくは３重量％以上である。含有量が多いほど、エポキシ樹脂との反応性が低下し、作業可能時間が長くなる。 In the epoxy curing agent of the present invention, 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.
　また、本発明のエポキシ硬化剤は、上記したアルキル化ポリアルキレンポリアミン（ｃ）を含有するか、又は上記したアルキル化ポリアルキレンポリアミン（ａ）と、アルキル化ポリアルキレンポリアミン（ｂ）と、アルキル化ポリアルキレンポリアミン（ｃ）とを含有するものである。よって、それ以外の成分を必ずしも必要とするものではないが、本発明の趣旨を逸脱しない範囲で、その他のアミンを含有していてもよい。このようなアミンとしては、例えば、３個以上の活性アミン水素原子を有する多官能性アミンが挙げられる。ただし、このような多官能性アミンであっても、エポキシ樹脂との反応性が著しく向上させる成分については、全く使用しないか、又はエポキシ樹脂との低反応性を維持できる範囲で使用することが望ましい。 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.
　３個以上の活性アミン水素原子を有する多官能性アミンとしては、例えば、脂肪族アミン、脂環式アミン、芳香族アミンの他、脂肪族アミン、芳香族アミン若しくは脂環式アミンのマンニッヒ塩基誘導体、脂肪族アミン、芳香族アミン若しくは脂環式アミンのポリアミド誘導体、脂肪族アミン、芳香族アミン若しくは脂環式アミンのアミン付加誘導体等が知られている。 Examples of the polyfunctional amine having 3 or more active amine hydrogen atoms 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.
　脂肪族アミンとしては、例えば、ポリエチレンアミン（ＥＤＡ、ＤＥＴＡ、ＴＥＴＡ、ＴＥＰＡ、ＰＥＨＡ等）、ポリプロピレンアミン、アミノプロピル化エチレンジアミン（Ａｍ３、Ａｍ４、Ａｍ５等）、アミノプロピル化プロピレンジアミン、１，６－ヘキサンジアミン、３，３，５－トリメチル－１，６－ヘキサンジアミン、３，５，５－トリメチル－１，６－ヘキサンジアミン、２－メチル－１，５－ペンタンジアミン［Ｄｙｔｅｋ（登録商標）－Ａとして市販されている］等、又はそれらの組み合わせが挙げられる。
　また、ハンツマン（Ｈｕｎｔｓｍａｎ）社からジェファーミン（Ｊｅｆｆａｍｉｎｅ）の商品名で入手できるポリ（アルキレンオキシド）ジアミンやトリアミンも、このような脂肪族アミンとして例示される。ジェファーミンとしては、特に限定するものではないが、例えば、ジェファーミンＤ－２３０、ジェファーミンＤ－４００、ジェファーミンＤ－２０００、ジェファーミン）Ｄ－４０００、ジェファーミンＴ－４０３、ジェファーミンＥＤＲ－１４８、ジェファーミンＥＤＲ－１９２、ジェファーミンＣ－３４６、ジェファーミンＥＤ－６００、ジェファーミンＥＤ－９００、ジェファーミンＥＤ－２００１等、又はそれらの組み合わせが挙げられる。 Examples of the aliphatic amine 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. For example, Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine) D-4000, Jeffamine T-403, Jeffamine EDR- 148, Jeffermin EDR-192, Jeffermin C-346, Jeffermin ED-600, Jeffermin ED-900, Jeffermin ED-2001, or combinations thereof.
　また、脂環式アミン又は芳香族アミンとしては、特に限定するものではないが、例えば、１，２－ジアミノシクロヘキサン、１，３－ジアミノシクロヘキサン、１，４－ジアミノシクロヘキサン、水素化オルトトルエンジアミン、水素化メタトルエンジアミン、メタキシリレンジアミン、水素化メタキシリレンジアミン（１，３－ＢＡＣとして市販されている）、イソホロンジアミン、各種の異性体又はノルボルナンジアミン、３，３’－ジメチル－４，４’－ジアミノジシクロヘキシルメタン、４，４’－ジアミノジシクロヘキシルメタン、２，４’－ジアミノジシクロヘキシルメタン、メチレン架橋ポリ（シクロヘキシル－芳香族）アミンの混合物等、又はそれらの組み合わせが挙げられる。 In addition, 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.
　マンニッヒ塩基誘導体は、例えば、上記した脂肪族アミン、脂環式アミン又は芳香族アミンとフェノール若しくは置換フェノール及びホルムアルデヒドとの反応により作られ得る。ポリアミド誘導体は、例えば、上記した脂肪族アミン、脂環式アミン又は芳香族アミンと、二量体脂肪酸、又は二量体脂肪酸及び脂肪酸の混合物との反応により調製され得る。アミドアミン誘導体は、例えば、脂肪族アミン、脂環式アミン又は芳香族アミンと脂肪酸との反応により調製され得る。アミン付加物は、例えば、脂肪族アミン、脂環式アミン又は芳香族アミンと、エポキシ樹脂（例えば、ビスフェノール－Ａのジグリシジルエーテル、ビスフェノール－Ｆのジグリシジルエーテル、エポキシノボラック樹脂等）との反応により調製され得る。なお、脂肪族アミン、脂環式アミン又は芳香族アミンに、単官能エポキシ樹脂（例えば、フェニルグリシジルエーテル、クレシルグリシジルエーテル、ブチルグリシジルエーテル、他のアルキルグリシジルエーテル等）を付加してもよい。 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.). Can be prepared. A monofunctional epoxy resin (for example, phenyl glycidyl ether, cresyl glycidyl ether, butyl glycidyl ether, or other alkyl glycidyl ether) may be added to the aliphatic amine, alicyclic amine, or aromatic amine.
　本発明において、上記したアルキル化ポリアルキレンポリアミン（ａ）、アルキル化ポリアルキレンポリアミン（ｂ）、アルキル化ポリアルキレンポリアミン（ｃ）の製造方法は特に限定するものではないが、対応するポリアルキレンポリアミンを部分的にＮ－アルキル化することで得られる。例えば、少なくとも２個の窒素原子を有する少なくとも１種のポリアルキレンポリアルキレンポリアミン、少なくとも１種のアルキル化剤、及び水素を触媒の存在下で反応することで得られる。 In the present invention, 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.
　ここで用いられるポリアルキレンポリアミンとしては、特に限定するものではないが、例えば、ポリエチレンポリアミン、ポリプロピレンポリアミン及びそれらの組合せが挙げられる。ポリエチレンポリアミンとしては、例えば、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン（ＴＥＴＡ）、テトラエチレンペンタミン（ＴＥＰＡ）、ペンタエチレンヘキサミン（ＰＥＨＡ）、及び他の高次ポリエチレンポリアミンが挙げられる。また、例えば、ＴＥＴＡは線状ＴＥＴＡだけでなく、トリス－アミノエチレンアミンも含んでいてもよい。
　ここで用いられるアルキル化剤としては、特に限定するものではないが、例えば、シクロペンタノン、シクロヘキサノン、炭素数１～６のアルデヒド、炭素数２～６のケトン等が挙げられる。 Although it does not specifically limit as a polyalkylene polyamine used here, For example, a polyethylene polyamine, a polypropylene polyamine, and those combination are mentioned. Examples of polyethylene polyamines include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and other higher order polyethylene polyamines. Also, for example, 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.
　ここで用いられる触媒としては、例えば、ニッケル、ラネーニッケル、ラネーコバルト白金黒、酸化白金、パラジウム、パラジウム／活性炭（Ｐｄ／Ｃ）、等、一般に用いられる水素化触媒が挙げられ、これらのいずれを用いてもよい。触媒の添加量はポリアルキレンポリアミンに対して０．１～１０重量％の範囲が好ましい。 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.
　アルキル化剤とポリアルキレンポリアミンとのモル反応比（アルキル化剤／ポリアルキレンポリアミン）は、特に限定するものではないが、好ましくは２以上、さらに好ましくは２．１以上である。これは、モル反応比が２．１以上の場合、アルキル化されずに残存する未反応のポリアルキレンポリアミンが１重量％以下となるためである。 The molar reaction ratio between the alkylating agent and the polyalkylene polyamine (alkylating agent / 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.
　次に本発明のエポキシ樹脂組成物について説明する。
　本発明のエポキシ樹脂組成物は、上記した本発明のエポキシ硬化剤とエポキシ樹脂とを含有することをその特徴とする。
　本発明において、エポキシ樹脂としては、エポキシ樹脂硬化物の製造に一般に用いられる未硬化のエポキシ樹脂でよく、特に限定するものではないが、例えば、１分子当たり２以上の１，２－エポキシ基を含有する未硬化のエポキシ樹脂が挙げられる。具体的には、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、エポキシノボラック樹脂、脂環式エポキシ樹脂、多官能性エポキシ樹脂、臭素化エポキシ樹脂等が例示される。これらのエポキシ樹脂は無溶媒のものでも、溶媒で希釈したものでも使用することができる。
　上記した本発明のエポキシ硬化剤用アミン組成物中のエポキシ硬化剤とエポキシ樹脂とを反応させることで、エポキシ樹脂硬化物が得られる。 Next, the epoxy resin composition of the present invention will be described.
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.
In the present invention, 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.
　本発明のエポキシ樹脂組成物を用い、又は上記した本発明のエポキシ硬化剤とエポキシ樹脂とを反応させることによって、エポキシ樹脂硬化物を形成する際には、従来公知の可塑剤を使用することができる。このような可塑剤としては、特に限定するものではないが、ベンジルアルコール、ノニルフェノール、種々のフタル酸エステル等が好適なものとして挙げられる。
　また、本発明のエポキシ樹脂組成物を用い、又は上記した本発明のエポキシ硬化剤とエポキシ樹脂とを反応させることによって、エポキシ樹脂硬化物を形成する際には、溶媒、充填剤、顔料、顔料分散剤、レオロジー修飾剤、チキソトロピー剤、流動化及び平滑化補助剤、消泡剤等を用いてもよい。好適な溶媒としては、例えば、芳香族炭化水素化合物、脂肪族炭化水素化合物、エステル、ケトン、エーテル、アルコール等が挙げられる。 When forming an epoxy resin cured product by using the epoxy resin composition of the present invention or reacting the above-described epoxy curing agent of the present invention with an epoxy resin, a conventionally known plasticizer may be used. it can. Such a plasticizer is not particularly limited, and examples thereof include benzyl alcohol, nonylphenol, various phthalates, and the like.
When forming an epoxy resin cured product by using the epoxy resin composition of the present invention or reacting the epoxy curing agent of the present invention with an epoxy resin, 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.
　以下、本発明を実施例に基づきさらに詳細に説明するが、本発明はこれらに限定されるこのではない。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereto.
　＜反応性の測定＞
　エポキシ硬化剤及びエポキシ樹脂（エピコート８２８、三菱化学社製）を２０ｍｌのサンプル瓶に秤量し、スパチュラで均一になるまで混合した後、２５℃の一定条件において硬化し、振動式粘度計（商品名：ＶＭ－１Ｇ－ＭＪ、山一電機社製）、データ収集システム（商品名：ＮＲ－１０００、Ｋｅｙｅｎｃｅ社製）を用いて粘度の経時変化を測定した。混合後、粘度値が１０００ｃＰに到達するまでの時間により反応性を評価した。１０００ｃＰ到達時間が長いほど、反応性が低く、作業可能時間が長いことを意味する。 <Measurement of reactivity>
An epoxy curing agent and an epoxy resin (Epicoat 828, manufactured by Mitsubishi Chemical Corporation) are weighed into a 20 ml sample bottle, mixed with a spatula until uniform, and then cured at a constant condition of 25 ° C., and a vibration viscometer (trade name) : VM-1G-MJ (manufactured by Yamaichi Electronics Co., Ltd.), and a data collection system (trade name: NR-1000, manufactured by Keyence Co.) were used to measure changes with time in viscosity. After mixing, the reactivity was evaluated by the time until the viscosity value reached 1000 cP. The longer the 1000 cP arrival time, the lower the reactivity and the longer the workable time.
　＜塗膜の引張強度及び可撓性の評価＞
　エポキシ硬化剤用アミン及びエポキシ樹脂（エピコート１００１、油化シェルエポキシ社製）をトルエンで７０重量％に希釈したエポキシ樹脂溶液を５００ｍｌのサンプル瓶に秤量し、スパチュラで均一になるまで混合した後、隙間を２００マイクロメーターに調整したドクターブレードを用いてポリプロピレンフィルム（２０ｃｍ×４０ｃｍ×０．２ｍｍ）上に均一塗布し、低温恒温恒湿機（商品名：ＰＬ－３Ｋ、エスペック社製）を用いて、２５℃、相対湿度５０％の一定条件で４８時間乾燥、硬化させた。
　その後、引張試験用ダンベル型打ち抜き器（ＪＩＳ　Ｋ　６２５９　２号型ダンベル状）を用いてテストピースを作成した。平行締付錠を用いてテストピースをテンシロン万能試験機（商品名：ＲＴＭ５００、オリエンテック社製）に取り付け、３０ｍｍ／ｍｉｎの速度で引張り、サンプルピースの最大引張り強度（ＭＰａ）を測定した。 <Evaluation of tensile strength and flexibility of coating film>
An epoxy resin solution in which an amine for epoxy curing agent and an epoxy resin (Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) are diluted to 70% by weight with toluene are weighed into a 500 ml sample bottle and mixed until uniform with a spatula. Using a doctor blade with the gap adjusted to 200 micrometers, uniformly apply it onto a polypropylene film (20 cm x 40 cm x 0.2 mm), and then use a low-temperature thermo-hygrostat (trade name: PL-3K, manufactured by Espec). The film was dried and cured for 48 hours under constant conditions of 25 ° C. and 50% relative humidity.
Then, the 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.
　合成例１．
　１０Ｌオートクレーブ中に、ジエチレントリアミン（ＤＥＴＡ）１５００ｇ（１４．５ｍｏｌ）、アセトン１６８９ｇ（２９．１ｍｏｌ）、メタノール３１８９ｇ、及びＰｄ／Ｃ触媒１２８ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、アセトン、及び生成水を除去し、イソプロピル化ジエチレントリアミン混合物を得た。
　得られたイソプロピル化ジエチレントリアミン混合物から、トリイソプロピル化ジエチレントリアミン（Ａ）２９０ｇ、ジイソプロピル化ジエチレントリアミン（Ｂ）１６３０ｇ、をそれぞれ蒸留分離した。 Synthesis Example 1
In a 10 L autoclave, 1500 g (14.5 mol) of diethylenetriamine (DETA), 1689 g (29.1 mol) of acetone, 3189 g of methanol, and 128 g of Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, acetone, and produced water were removed with an evaporator to obtain an isopropylated diethylenetriamine mixture.
From the resulting isopropylated diethylenetriamine mixture, 290 g of triisopropylated diethylenetriamine (A) and 1630 g of diisopropylated diethylenetriamine (B) were separated by distillation.
　合成例２．
　１０Ｌオートクレーブ中に、エチレンジアミン（ＥＤＡ）１０００ｇ（１６．６ｍｏｌ）、アセトン２２５１ｇ（３８．８ｍｏｌ）、メタノール３２５１ｇ、及びＰｄ／Ｃ触媒１３０．１ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、アセトン、及び生成水を除去し、イソプロピル化エチレンジアミン混合物を得た。
　得られたイソプロピル化エチレンジアミン混合物から、ジイソプロピル化エチレンジアミン２１００ｇを蒸留分離した。 Synthesis Example 2
In a 10 L autoclave, 1000 g (16.6 mol) of ethylenediamine (EDA), 2251 g (38.8 mol) of acetone, 3251 g of methanol, and 130.1 g of Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, acetone, and generated water were removed with an evaporator to obtain an isopropylated ethylenediamine mixture.
From the resulting isopropylated ethylenediamine mixture, 2100 g of diisopropylated ethylenediamine was separated by distillation.
　合成例３．
　１０Ｌオートクレーブ中に、トリエチレンテトラミン（ＴＥＴＡ）１１００ｇ（７．５ｍｏｌ）、メチルエチルケトン２１７２．９ｇ（３０．１ｍｏｌ）、メタノール３２７２．９ｇ、及びＰｄ／Ｃ触媒１３０ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、メチルエチルケトン、及び生成水を除去し、ｓｅｃ－ブチル化トリエチレンテトラミン混合物を得た。
　得られたｓｅｃ－ブチル化トリエチレンテトラミン混合物から、テトラｓｅｃ－ブチル化トリエチレンテトラミン８２０ｇを蒸留分離した。 Synthesis Example 3
In a 10 L autoclave, 1100 g (7.5 mol) of triethylenetetramine (TETA), 2172.9 g (30.1 mol) of methyl ethyl ketone, 3272.9 g of methanol, and 130 g of a Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, methyl ethyl ketone, and produced water were removed by an evaporator to obtain a sec-butylated triethylenetetramine mixture.
From the obtained sec-butylated triethylenetetramine mixture, 820 g of tetrasec-butylated triethylenetetramine was separated by distillation.
　実施例１．
　合成例１で得たトリイソプロピル化ジエチレントリアミン０．０３ｇ、及びジイソプロピル化ジエチレントリアミン３．３５ｇ、並びにエポキシ樹脂（エピコート８２８、三菱化学社製）１０ｇを２０ｍｌのサンプル瓶に秤量し、スパチュラで均一になるまで混合した後、２５℃の一定条件において硬化、振動式粘度計（商品名：ＶＭ－１Ｇ－ＭＪ、山一電機社製）、データ収集システム（商品名：ＮＲ－１０００、Ｋｅｙｅｎｃｅ社製）を用いて粘度の経時変化を測定した。混合後、粘度値が１０００ｃＰに到達するまでの時間を測定したところ、８．６時間であった。 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.
　実施例２～実施例１０、参考例１及び比較例１～比較例３．
　表１、表２に示す種類と量のアミンを用いた以外は、実施例１と同様に実施した。その結果を表１、表２に併せて示す。 Examples 2 to 10, Reference Example 1 and Comparative Examples 1 to 3
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.
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
　この表から、本発明のアルキル化ポリアルキレンポリアミン（ｃ）を含むエポキシ硬化剤を用いた実施例１～実施例９の場合の方が、当該エポキシ硬化剤を用いない比較例１～比較例３の場合よりも、長い作業時間を達成できることが分かる。
Figure JPOXMLDOC01-appb-T000010
From this table, in the case of Examples 1 to 9 using the epoxy curing agent containing the alkylated polyalkylene polyamine (c) of the present invention, Comparative Examples 1 to 3 in which the epoxy curing agent is not used. It can be seen that a longer working time can be achieved than in the case of.
　また、アルキル化ポリアルキレンポリアミン（ｃ）以外に、３個以上の活性アミン水素原子を有する多官能性アミンを併用する場合、エポキシ樹脂との反応性に影響を与えない多官能性アミンについては好適に使用できるが（実施例１０参照）、エポキシ樹脂との反応性を著しく向上させる成分を多用すると、本発明の効果が発揮されないことが理解される（参考例１参照）。 In addition to the alkylated polyalkylene polyamine (c), when a polyfunctional amine having 3 or more active amine hydrogen atoms is used in combination, 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).
　合成例４．
　１０Ｌオートクレーブ中に、ジエチレントリアミン（ＤＥＴＡ）１５００ｇ（１４．５ｍｏｌ）、アセトン１６８９ｇ（２９．１ｍｏｌ）、メタノール３１８９ｇ、及びＰｄ／Ｃ触媒１２８ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、アセトン、及び生成水を除去し、イソプロピル化ジエチレントリアミン混合物を得た。
　得られたイソプロピル化ジエチレントリアミン混合物から、モノイソプロピル化ジエチレントリアミン（Ａ）４８０ｇ、ジイソプロピル化ジエチレントリアミン（Ｂ）１６３０ｇ、及びトリイソプロピル化ジエチレントリアミン（Ｃ）２９０ｇをそれぞれ蒸留分離した。 Synthesis Example 4
In a 10 L autoclave, 1500 g (14.5 mol) of diethylenetriamine (DETA), 1689 g (29.1 mol) of acetone, 3189 g of methanol, and 128 g of Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, acetone, and produced water were removed with an evaporator to obtain an isopropylated diethylenetriamine mixture.
From the resulting isopropylated diethylenetriamine mixture, 480 g of monoisopropylated diethylenetriamine (A), 1630 g of diisopropylated diethylenetriamine (B), and 290 g of triisopropylated diethylenetriamine (C) were each separated by distillation.
　合成例５．
　１０Ｌオートクレーブ中に、エチレンジアミン（ＥＤＡ）１０００ｇ（１６．６ｍｏｌ）、アセトン２２５１ｇ（３８．８ｍｏｌ）、メタノール３２５１ｇ、及びＰｄ／Ｃ触媒１３０．１ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、アセトン、及び生成水を除去し、イソプロピル化エチレンジアミン混合物を得た。
　得られたイソプロピル化エチレンジアミン混合物から、ジイソプロピル化エチレンジアミン（Ｄ）２１００ｇを蒸留分離した。 Synthesis Example 5
In a 10 L autoclave, 1000 g (16.6 mol) of ethylenediamine (EDA), 2251 g (38.8 mol) of acetone, 3251 g of methanol, and 130.1 g of Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, acetone, and generated water were removed with an evaporator to obtain an isopropylated ethylenediamine mixture.
From the resulting isopropylated ethylenediamine mixture, 2100 g of diisopropylated ethylenediamine (D) was distilled and separated.
　合成例６．
　１０Ｌオートクレーブ中に、トリエチレンテトラミン（ＴＥＴＡ）１１００ｇ（７．５ｍｏｌ）、メチルエチルケトン２１７２．９ｇ（３０．１ｍｏｌ）、メタノール３２７２．９ｇ、及びＰｄ／Ｃ触媒１３０ｇを仕込んだ。オートクレーブを窒素、その次に水素でパージし、オートクレーブ中の空気を除去した。オートクレーブを水素で３ＭＰａに加圧して、１２０℃まで０．５時間で昇温した。オートクレーブ内圧を水素で３ＭＰａに保ち、さらに６時間反応を行った。反応終了後、オートクレーブを冷却、減圧し、反応生成物をろ過して触媒を除去した。エバポレーターでメタノール、メチルエチルケトン、及び生成水を除去し、ｓｅｃ－ブチル化トリエチレンテトラミン混合物を得た。
　得られたｓｅｃ－ブチル化トリエチレンテトラミン混合物から、ジｓｅｃ－ブチル化トリエチレンテトラミン（Ｅ）２５０ｇ蒸留分離した。 Synthesis Example 6
In a 10 L autoclave, 1100 g (7.5 mol) of triethylenetetramine (TETA), 2172.9 g (30.1 mol) of methyl ethyl ketone, 3272.9 g of methanol, and 130 g of a Pd / C catalyst were charged. The autoclave was purged with nitrogen and then with hydrogen to remove the air in the autoclave. The autoclave was pressurized to 3 MPa with hydrogen and heated to 120 ° C. in 0.5 hours. The internal pressure of the autoclave was kept at 3 MPa with hydrogen, and the reaction was further performed for 6 hours. After completion of the reaction, the autoclave was cooled and decompressed, and the reaction product was filtered to remove the catalyst. Methanol, methyl ethyl ketone, and produced water were removed by an evaporator to obtain a sec-butylated triethylenetetramine mixture.
From the obtained sec-butylated triethylenetetramine mixture, 250 g of disec-butylated triethylenetetramine (E) was distilled and separated.
　実施例１１．
　合成例４で得たモノイソプロピル化ジエチレントリアミン０．００３ｇ（０．０１重量％）、ジイソプロピル化ジエチレントリアミン２６．８９３ｇ（９９．４９重量％）、及びトリイソプロピル化ジエチレントリアミン０．１３５ｇ（０．５重量％）、並びにエポキシ樹脂（エピコート８２８、三菱化学社製）８０ｇを１００ｍｌのサンプル瓶に秤量し、スパチュラで均一になるまで混合した後、２５℃の一定条件において硬化、振動式粘度計（商品名：ＶＭ－１Ｇ－ＭＪ、山一電機社製）、データ収集システム（商品名：ＮＲ－１０００、Ｋｅｙｅｎｃｅ社製）を用いて粘度の経時変化を測定した。混合後、粘度値が１０００ｃＰに到達するまでの時間を測定したところ、８．６時間であった。
　合成例４で得たモノイソプロピル化ジエチレントリアミン０．００３ｇ（０．０１重量％）、ジイソプロピル化ジエチレントリアミン２７．５５９ｇ（９９．４９重量％）、及びトリイソプロピル化ジエチレントリアミン０．１３８ｇ（０．５重量％）、並びにエポキシ樹脂（エピコート１００１、油化シェルエポキシ社製）をトルエンで７０重量％に希釈したエポキシ樹脂溶液３００ｇを５００ｍｌのサンプル瓶に秤量し、スパチュラで均一になるまで混合した後、隙間を２００マイクロメーターに調整したドクターブレードを用いてポリプロピレンフィルム（２０ｃｍ×４０ｃｍ×０．２ｍｍ）上に均一塗布し、低温恒温恒湿機（商品名：ＰＬ－３Ｋ、エスペック社製）を用いて、２５℃、相対湿度５０％の一定条件で４８時間乾燥、硬化させた。
　その後、引張試験用ダンベル型打ち抜き器（ＪＩＳ　Ｋ　６２５９　２号型ダンベル状）を用いてテストピースを作成した。平行締付錠を用いてテストピースをテンシロン万能試験機（商品名：ＲＴＭ５００、オリエンテック社製）に取り付け、３０ｍｍ／ｍｉｎの速度で引張り、サンプルピースの最大引張り強度（ＭＰａ）を測定したところ、５．９ＭＰａであった。 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 In addition, 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.) and a data collection system (trade name: NR-1000, manufactured by Keyence Co.) were used to measure the change in viscosity over time. After mixing, the time until the viscosity value reached 1000 cP was measured and found to be 8.6 hours.
0.003 g (0.01 wt%) of monoisopropylated diethylenetriamine obtained in Synthesis Example 4, 27.559 g (99.49 wt%) of diisopropylated diethylenetriamine, and 0.138 g (0.5 wt%) of triisopropylated diethylenetriamine In addition, 300 g of an epoxy resin solution obtained by diluting an epoxy resin (Epicoat 1001, manufactured by Yuka Shell Epoxy Co., Ltd.) to 70% by weight with toluene is weighed into a 500 ml sample bottle and mixed until uniform with a spatula, and then the gap is 200. Apply uniformly onto a polypropylene film (20 cm x 40 cm x 0.2 mm) using a doctor blade adjusted to a micrometer, and use a low-temperature thermo-hygrostat (trade name: PL-3K, manufactured by Espec) at 25 ° C. , Dried and cured for 48 hours under constant conditions of 50% relative humidity I let you.
Then, the test piece was created using the dumbbell type punch for tensile tests (JIS K 6259 No. 2 type dumbbell shape). When a test piece was attached to a Tensilon universal testing machine (trade name: RTM500, manufactured by Orientec Co., Ltd.) using a parallel fastening lock, the sample piece was pulled at a speed of 30 mm / min, and the maximum tensile strength (MPa) of the sample piece was measured. It was 5.9 MPa.
　実施例１１～実施例２９、比較例４～比較例８、参考例２～１１．
　表３～表５に示す種類と量のアミンを用いた以外は、実施例１と同様に実施した。その結果を表３～表５に併せて示す。 Examples 11 to 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.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
　これらの表から、本発明のアルキル化ポリアルキレンポリアミン（ａ）～（ｃ）を含むエポキシ硬化剤を用いた実施例１１～２９では、作業可能時間が長く（１０００ｃＰ到達時間が８時間以上）、かつエポキシ樹脂の強度が優れる（引張強度が５．８ＭＰａ以上）ことが分かる。一方、比較例４、５、７、８は、エポキシ樹脂の引張強度が優れるものの（引張強度が５．８ＭＰａ以上）、作業可能時間が短い（１０００ｃＰ到達時間が８時間以下）、また、比較例６は、作業可能時間が長い（１０００ｃＰ到達時間が８時間以上）ものの、エポキシ樹脂の強度に劣る（引張強度が５．８ＭＰａ以下）ことが分かる。
Figure JPOXMLDOC01-appb-T000013
From these tables, in Examples 11 to 29 using the epoxy curing agent containing the alkylated polyalkylene polyamines (a) to (c) of the present invention, the workable time is long (1000 cP arrival time is 8 hours or more), And it turns out that the intensity | strength of an epoxy resin is excellent (tensile strength is 5.8 Mpa or more). On the other hand, Comparative Examples 4, 5, 7, and 8 have excellent tensile strength of the epoxy resin (tensile strength is 5.8 MPa or more), but the workable time is short (time to reach 1000 cP is 8 hours or less). 6 shows that although the workable time is long (time to reach 1000 cP is 8 hours or more), the strength of the epoxy resin is inferior (tensile strength is 5.8 MPa or less).
　なお、参考例５、７、９では、エポキシ樹脂の引張強度が優れるものの（引張強度が５．８ＭＰａ以上）、作業可能時間が短くなり（１０００ｃＰ到達時間が８時間以下）、また、参考例４、６、８、１０、１１では、作業可能時間が長い（１０００ｃＰ到達時間が８時間以上）ものの、エポキシ樹脂の強度に劣る（引張強度が５．８ＭＰａ以下）ことが分かる。 In Reference Examples 5, 7, and 9, although the tensile strength of the epoxy resin is excellent (tensile strength is 5.8 MPa or more), the workable time is shortened (time to reach 1000 cP is 8 hours or less). 6, 8, 10, and 11, it can be seen that the workable time is long (1000 cP arrival time is 8 hours or more), but the epoxy resin is inferior in strength (tensile strength is 5.8 MPa or less).
　このように、本発明のアルキル化ポリアルキレンポリアミン（ａ）～（ｃ）を含むエポキシ硬化剤を用いて、エポキシ樹脂との反応性が低く、かつ機械強度に優れるエポキシ樹脂硬化物を与えるためには、アルキル化ポリアルキレンポリアミン（ａ）～（ｃ）の組成が極めて重要であることが分かる。 Thus, in order to provide an epoxy resin cured product having low reactivity with an epoxy resin and excellent mechanical strength, using the epoxy curing agent containing the alkylated polyalkylene polyamines (a) to (c) of the present invention. It can be seen that the composition of the alkylated polyalkylene polyamines (a) to (c) is extremely important.
　本発明のアルキル化ポリアルキレンポリアミン（ｃ）を含むエポキシ樹脂硬化剤は、硬化剤として反応性が低く、エポキシ樹脂と混合して使用する際に、十分な作業時間を達成することができるため、入り組んだ構造を有する構造物表面や大型構造物表面のコーティングなど、長い作業時間を必要とする用途で、好適に使用される。 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.
　また、本発明のアルキル化ポリアルキレンポリアミン（ａ）～（ｃ）を含むエポキシ硬化剤は、硬化剤として反応性が低く、かつ機械強度に優れるエポキシ樹脂を与えることが可能なため、床材やコンクリート用建造物、風車ブレード等、長い作業時間を必要とし、かつ十分な強度を必要とする用途で、好適に使用される。 In addition, 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.
　なお、２０１１年１１月９日に出願された日本特許出願２０１１－２４５６９７号及び２０１１年１１月９日に出願された日本特許出願２０１１－２４５６９８号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 It should be noted that the description, claims, and abstract of Japanese Patent Application No. 2011-245597 filed on November 9, 2011 and Japanese Patent Application No. 2011-245698 filed on November 9, 2011 The entire contents are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims (9)

  1. 　炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種の置換基を分子内に有し、かつ分子内に活性アミン水素原子を２個有するアルキル化ポリアルキレンポリアミン（ｃ）を含有するエポキシ硬化剤。 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— An epoxy curing agent containing an alkylated polyalkylene polyamine (c) having one or two substituents selected from the group consisting of 2) in the molecule and two active amine hydrogen atoms in the molecule.
  2. 　炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を４個有するアルキル化ポリアルキレンポリアミン（ａ）と、炭素数１～６のＮ－アルキル化アミノ基（Ｒ－ＮＨ－：ここでＲは炭素数１～６のアルキル基を表す。）、アミノ基（Ｈ２Ｎ－）及びイミノ基（－ＮＨ－）からなる群より選択される１種又は２種以上の置換基を分子内に有し、かつ分子内に活性アミン水素原子を３個有するアルキル化ポリアルキレンポリアミン（ｂ）と、請求項１に記載のアルキル化ポリアルキレンポリアミン（ｃ）とを含有し、（ａ）＋（ｂ）＋（ｃ）に対して、（ａ）が０．０１～５重量％、（ｃ）が０．５～４０重量％、（ｂ）が残部であることを特徴とするエポキシ硬化剤。 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— An alkylated polyalkylene polyamine (a) having one or two or more substituents selected from the group consisting of 4) and 4 active amine hydrogen atoms in the molecule; 6 N-alkylated amino groups (R—NH—, where R represents an alkyl group having 1 to 6 carbon atoms), amino groups (H 2 N—) and imino groups (—NH—) The alkylated polyalkylene polyamine (b) having one or more selected substituents in the molecule and three active amine hydrogen atoms in the molecule, and the alkylation according to claim 1 Polyalkylene polyamine (c), and (a) + (b) + An epoxy curing agent, wherein (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).
  3. 　アルキル化ポリアルキレンポリアミン（ｃ）が、下記式（３）
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは０～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）で示されるアルキル化ポリアルキレンポリアミンであることを特徴とする請求項１又は請求項２に記載のエポキシ硬化剤。     The alkylated polyalkylene polyamine (c) is represented by the following formula (3):
    Figure JPOXMLDOC01-appb-C000001
     (Wherein 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 The epoxy curing agent according to claim 1 or 2, wherein the epoxy curing agent is an alkylated polyalkylene polyamine represented by the following formula:
  4. 　アルキル化ポリアルキレンポリアミン（ａ）が下記式（１）
    Figure JPOXMLDOC01-appb-C000002
    （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）で示されるアルキル化ポリアルキレンポリアミンであり、アルキル化ポリアルキレンポリアミン（ｂ）が下記式（２）
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）で示されるアルキル化ポリアルキレンポリアミンであり、かつアルキル化ポリアルキレンポリアミン（ｃ）が下記式（３）
    Figure JPOXMLDOC01-appb-C000004
     （式中、Ｒ１～Ｒ５は各々独立して水素原子又は炭素数１～６のアルキル基を表し、ｎは１～６の範囲である。ただし、Ｒ１～Ｒ５は全て水素原子又は全てアルキル基になることはない。）で示されるアルキル化ポリアルキレンポリアミンであることを特徴とする請求項２に記載のエポキシ硬化剤。     The alkylated polyalkylene polyamine (a) is represented by the following formula (1):
    Figure JPOXMLDOC01-appb-C000002
    (Wherein 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 Are not all alkyl groups.), And the alkylated polyalkylene polyamine (b) is represented by the following formula (2):
    Figure JPOXMLDOC01-appb-C000003
     (Wherein 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 Are not all alkyl groups.) And the alkylated polyalkylene polyamine (c) is represented by the following formula (3):
    Figure JPOXMLDOC01-appb-C000004
     (Wherein 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 The epoxy curing agent according to claim 2, wherein the epoxy curing agent is an alkylated polyalkylene polyamine represented by the following formula:
  5. 　アルキル化ポリアルキレンポリアミン（ｃ）が、Ｎ，Ｎ’－ジイソプロピルエチレンジアミン、Ｎ，Ｎ’－ジｓｅｃ－ブチル－エチレンジアミン、Ｎ，Ｎ’，Ｎ’’－トリイソプロピルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’’－トリｓｅｃ－ブチル－ジエチレントリアミン、Ｎ，Ｎ’－ジイソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも一種であることを特徴とする請求項１乃至請求項４のいずれかに記載のエポキシ硬化剤。 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-butyl-N The at least one selected from the group consisting of N, -bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine, Epoxy curing agent.
  6. 　アルキル化ポリアルキレンポリアミン（ａ）が、Ｎ－イソプロピルジエチレントリアミン、Ｎ－ｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであり、アルキル化ポリアルキレンポリアミン（ｂ）が、Ｎ－イソプロピルエチレンジアミン、Ｎ－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’－ジイソプロピルジエチレントリアミン、Ｎ，Ｎ’－ジｓｅｃブチル－ジエチレントリアミン、Ｎ－イソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであり、かつアルキル化ポリアルキレンポリアミン（ｃ）が、Ｎ，Ｎ’－ジイソプロピルエチレンジアミン、Ｎ，Ｎ’－ｓｅｃブチル－エチレンジアミン、Ｎ，Ｎ’，Ｎ’’－トリイソプロピルジエチレントリアミン、Ｎ，Ｎ’，Ｎ’’－トリｓｅｃブチル－ジエチレントリアミン、Ｎ，Ｎ’－ジイソプロピル－Ｎ，Ｎ’－ビス［２－（イソプロピルアミノ）エチル］－１，２－エタンジアミン、及びＮ，Ｎ’－ｓｅｃ－ブチル－Ｎ，Ｎ’－ビス［２－（ｓｅｃ－ブチルアミノ）エチル］－１，２－エタンジアミンからなる群より選ばれる少なくとも１種のアルキル化ポリアルキレンポリアミンであることを特徴とする請求項２乃至請求項５のいずれかに記載のエポキシ硬化剤。 The alkylated polyalkylene polyamine (a) is N-isopropyldiethylenetriamine, N-secbutyl-diethylenetriamine, N, N′-bis [2- (isopropylamino) ethyl] -1,2-ethanediamine, and N, N ′; -At least one alkylated polyalkylene polyamine selected from the group consisting of bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine, wherein the alkylated polyalkylene polyamine (b) is N- Isopropylethylenediamine, N-secbutyl-ethylenediamine, N, N′-diisopropyldiethylenetriamine, N, N′-disecbutyl-diethylenetriamine, N-isopropyl-N, N′-bis [2- (isopropylamino) ethyl] -1 , 2-ethanediamine, and At least one alkylated polyalkylene polyamine selected from the group consisting of —sec-butyl-N, N′-bis [2- (sec-butylamino) ethyl] -1,2-ethanediamine, and alkylated Polyalkylene polyamine (c) is N, N′-diisopropylethylenediamine, N, N′-secbutyl-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-butyl-N, N′-bis At least one selected from the group consisting of [2- (sec-butylamino) ethyl] -1,2-ethanediamine Epoxy curing agent according to any one of claims 2 to 5, characterized in that an alkylated polyalkylenepolyamine.
  7. 　請求項１乃至請求項６のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを含有することを特徴とするエポキシ樹脂組成物。 An epoxy resin composition comprising the epoxy curing agent according to any one of claims 1 to 6 and an epoxy resin.
  8. 　請求項１乃至請求項６のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを反応させて得られるエポキシ樹脂硬化物。 A cured epoxy resin obtained by reacting the epoxy curing agent according to any one of claims 1 to 6 with an epoxy resin.
  9. 　請求項１乃至請求項６のいずれかに記載のエポキシ硬化剤とエポキシ樹脂とを反応させることを特徴とするエポキシ樹脂硬化物の製造方法。 A method for producing a cured epoxy resin, comprising reacting the epoxy curing agent according to any one of claims 1 to 6 with an epoxy resin.
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JP2002284861A (en) * 2001-03-22 2002-10-03 Ajinomoto Co Inc Latent curing agent composition for use in one liquid epoxy resin composition and one liquid epoxy resin composition
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