WO2003014181A1 - Accelerateur de durcissement destine a un agent de durcissement a base d'amine pour resines epoxy et procede d'acceleration du durcissement d'une resine epoxy - Google Patents

Accelerateur de durcissement destine a un agent de durcissement a base d'amine pour resines epoxy et procede d'acceleration du durcissement d'une resine epoxy Download PDF

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Publication number
WO2003014181A1
WO2003014181A1 PCT/JP2002/008162 JP0208162W WO03014181A1 WO 2003014181 A1 WO2003014181 A1 WO 2003014181A1 JP 0208162 W JP0208162 W JP 0208162W WO 03014181 A1 WO03014181 A1 WO 03014181A1
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WO
WIPO (PCT)
Prior art keywords
epoxy resin
curing
amine
curing agent
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/008162
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English (en)
Japanese (ja)
Inventor
Tsunehiko Masatomi
Shoji Hiketa
Takashi Kitajima
Akihiro Nabeshima
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Otsuka Chemical Co Ltd
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Otsuka Chemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Otsuka Chemical Co Ltd filed Critical Otsuka Chemical Co Ltd
Publication of WO2003014181A1 publication Critical patent/WO2003014181A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G59/68—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 catalysts used
    • C08G59/687—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 catalysts used containing sulfur

Definitions

  • the present invention relates to a curing accelerator for an amine-based epoxy resin curing agent and a method for promoting curing of an epoxy resin.
  • the present invention relates to a curing accelerator for an amine epoxy resin curing agent and a method for promoting curing of an epoxy resin.
  • Epoxy resins have excellent electrical insulation, moisture resistance, heat resistance, solder resistance, chemical resistance, durability, adhesion, mechanical strength, etc. It is widely used as a sealing material, paint, adhesive, etc. in various fields such as construction.
  • epoxy resin is cured by adding a curing agent to the epoxy resin and heating.
  • Typical curing agents include, for example, diethylenetriamine, triethylenetetramine, isophoronediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamides, dicyandiamide, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acids, methylnadic anhydride, nopolak phenolic resin, tertiary amines, imidazoles, and amine complexes of boron trifluoride.
  • those which cure epoxy resins at room temperature include amine curing agents such as ethylenetriamine, triethylenetetramine, polyamides and tertiary amines.
  • amine curing agents such as ethylenetriamine, triethylenetetramine, polyamides and tertiary amines.
  • diethylenetriamine and triethylenetetramine require 4 days for curing, and polyamides and tertiary amines require 7 days. It is.
  • epoxy resin adhesives for outdoor construction are widely used in the field of civil engineering and construction, but as described above, it is very difficult to cure epoxy resin without heating with a conventional curing agent. However, it can take a very long time of 4-7 days to cure. In particular, in winter construction where the outdoor temperature often drops to 10 ° C or less, it is essential to start the curing reaction by heating.
  • An object of the present invention is to provide a curing accelerator capable of remarkably improving the curing speed of these amine-based epoxy resin curing agents, and a method of accelerating the curing. Disclosure of the invention
  • the present invention relates to a curing accelerator for an amine-based epoxy resin curing agent comprising a thiocyanate of a compound represented by the formula (1) as an active ingredient, and a curing acceleration method using the curing accelerator. Related.
  • alkyl having 1 to 8 carbon atoms examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isoptyl, t-butyl, s-butyl, n-pentyl, isopentyl, t-pentyl, neopentyl, and n-pentyl. Hexyl, isohexyl, heptyl, octyl and the like can be mentioned. Examples of the alkylene having 2 to 11 carbon atoms include ethylene, propylene, butylene, hexylene, octylene, Tylene, pendecamethylene and the like can be mentioned. Examples of the alkylene having 1 to 8 carbon atoms include methylene, ethylene, propylene, butylene, hexylene, and octylene.
  • the thiocyanate of the compound represented by the formula (1) used as an active ingredient of the fat curing accelerator of the amine-based epoxy resin curing agent of the present invention is represented by, for example, an aqueous solution of ammonium thiocyanate represented by the formula (1) Compound is added in an approximately equimolar amount, and the reaction is carried out for about 30 minutes to 5 hours while gradually heating to about 80 ° C while distilling off the produced ammonia and water. . It is preferably used in powder form.
  • the compound represented by the formula (1) include 1-aminopyrrolidine (1 AP), 1-aminopiperidine, 1-aminohomopiridine (AHP), 1-aminopiperazine, and 1-amino- N'-methylbiperazine (AMPI), N-aminomorpholine (AMP), N-aminothiomorpholine, 1,1-dimethylhydrazine (UD MH), 1,1-getylhydrazine, 1,1-dipropylhydrazine , 1,1-dibutylhydrazine, monomethylhydrazine, monoethylhydrazine, monopropylhydrazine, monoisopropylhydrazine, monobutylhydrazine, mono tert-butylhydrazine, 1-ethyl-11-methylhydrazine, 1-methylethyl-11 Propylhydrazine, 1-butyl-1-methylhydrazine, 1-methyl1-1-phenylhydrazine, 1-
  • the thiocyanate of the compound represented by the formula (1) can harden an epoxy resin by being used in combination with an amine-based curing agent as described in WO01 / 291109. Yes, but it cannot cure epoxy resin alone. However, this time, it was found that it has an effect of remarkably improving the curing speed of the amine-based epoxy resin curing agent, and it is confirmed that it is useful as a curing accelerator for the amine-based curing agent. Was called.
  • the amine-based curing agent includes diethylenetriamine, triethylenetetramine, isophoronediamine, metaxylylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polyamides, dicyandiamide, hexahydrophthalic anhydride, methyl Examples thereof include tetrahydrophthalic anhydride, methylnadic anhydride, nopolak phenolic resin, tertiary amines, imidazoles, amine complexes of boron trifluoride, and modified products thereof.
  • the mixing ratio of the amine-based curing agent to the epoxy resin is not particularly limited.
  • the type of the epoxy resin, the type and the amount of the other additives, the use of the obtained epoxy resin cured product, and the curing conditions (designed curing) It may be appropriately selected from a wide range according to various conditions such as time, curing temperature, curing place, etc., but usually 0.1 to 1 equivalent, preferably 0.6 to 1 equivalent to 1 equivalent of epoxy resin. It is preferable to use it to the extent.
  • the thiocyanate of the compound represented by the formula (1) is used as a curing accelerator in an amount of 1 to 150 parts by weight based on 100 parts by weight of the amine-based curing agent. Parts, preferably 5 to 50 parts by weight, the curing rate can be improved without substantially changing the physical properties of the cured product. Further, it is preferable to use 0.5 to 1 mol of the thiocyanate of the compound represented by the formula (1) with respect to 10 mol of the amine-based curing agent.
  • the epoxy resin to which the curing agent for epoxy resin of the present invention can be applied is not particularly limited, and may be a conventionally known epoxy resin. Examples thereof include glycidyl ether type epoxy resins, glycidylamine type epoxy resins, cycloaliphatic epoxy resins, glycidyl ester resins, heterocyclic epoxy resins, and urethane-modified epoxy resins.
  • Glycidyl ether type epoxy resins include bisphenol A type, bisphenol F type, brominated bisphenol A type, hydrogenated bisphenol A type, bisphenol S type, bisphenol AF type, biphenyl type, naphthalene type, Examples thereof include a fluorene type, a phenol nopolak type, a cresol nopolak type, a DPP nopolak type, a trifunctional type, a tris-hydroxyphenylmethane type, and a tetraphenylolethane type.
  • Examples of glycidylamine type epoxy resins include tetraglycidyldiaminodiphenylmethane, triglycidylisocyanurate, hydantoin type, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, aminophenol type, Examples include ananiline type and toluidine type.
  • the epoxy resin to which the epoxy resin curing accelerator of the present invention is applied may contain an inorganic filler, a reinforcing material, and the like, which are conventionally added to the epoxy resin.
  • inorganic fillers can be used, for example, silica, fused quartz, calcium carbonate, barium carbonate, barium sulfate, hydrated alumina, alumina, hydrated magnesia, zircon, cordierite, silicon nitride, boron nitride, nitrided Aluminum and the like.
  • Known reinforcing materials can be used.
  • examples include inorganic materials such as glass chops, asbestos, talc, and my strength, glass fibers, potassium titanate fibers, titanium dioxide fibers, wollastonite, zonotolite, and zinc silicate fibers. And organic fibers.
  • the thermal conductivity, crack resistance, electrical properties, tracking resistance, and the like of the obtained cured product can be adjusted by appropriately changing the type, purity, and amount of the filler and the reinforcing material.
  • the filler and the reinforcing material are added in a total amount of about 20 to 160 parts by weight, preferably about 50 to 120 parts by weight, based on 100 parts by weight of the epoxy resin. Good to do.
  • the filler and the reinforcing material may be used alone or in combination of two or more.
  • the epoxy resin to which the curing agent for epoxy resin of the present invention is applied may contain, if necessary, additives conventionally used as additives for epoxy resins.
  • additives include, for example, inorganic pigments (particulate titanium dioxide, power—pump racks, red iron oxide, yellow iron oxide, etc.), organic pigments, viscosity modifiers, leveling agents, defoamers, cups Examples include a ring agent, a plasticizer, a diluent, a flame retardant, and an organic solvent.
  • Epoxy resins cured using the epoxy resin curing accelerator of the present invention include, for example, various shapes composed of at least one of various materials such as metals, synthetic resins, cement, ceramics, fibers, and paper. Applicable to articles.
  • articles of various shapes are immersed in an epoxy resin to which an amine curing agent and the epoxy resin curing accelerator of the present invention are added, or an amine curing agent and the epoxy resin curing of the present invention are applied to the surface of the article.
  • the resin After applying or coating the epoxy resin to which the accelerator has been added, the resin may be left as it is and cured.
  • the conditions such as the temperature and the like are determined by the type of epoxy resin, the type and amount of the epoxy resin curing accelerator of the present invention, and the type and amount of epoxy resin to be obtained when other additives are added. It may be appropriately selected according to various conditions such as the use of the cured product, but it is usually about 40 to 80 ° C.
  • an epoxy resin to which an amine-based curing agent and the epoxy resin curing accelerator of the present invention are added is formed into a molded article having an arbitrary shape in accordance with a usual molding method such as casting, and this is formed with at least one of various materials. It can be attached to the various shaped articles according to the usual method such as bonding and fitting.
  • the curing conditions at the time of molding may be the same as in the case of application or impregnation.
  • the commercially available amine epoxy resin curing agents used in the examples and comparative examples are as follows.
  • Adeiki Hardener EH220 (made by Asahi Denka Kogyo Co., denatured aliphatic polyamine), Adeki Hardener EH227 (made by Asahi Denka Kogyo Co., Ltd., denatured aliphatic polyamine), Epomate RX3 (Japan Epoxy Resin Co., Ltd., heterocyclic ring) Epomate RX32 (Japan Epoxy Resin Co., Ltd., heterocyclic diamine modification), Epomate B 002 (Japan Epoxy Resin Co., Ltd., heterocyclic diamine modification), Epomate RX221 (Japan Epoxy) Resin Corporation, modified aliphatic polyamine), Epicure-1 3560 (Japan Epoxy Resin Co., modified aliphatic polyamine),
  • Example 1 Bisphenol A type epoxy resin [trade name: Epikote 828, epoxy equivalent: 190, manufactured by Japan Epoxy Resin Co., Ltd.] 1 Og, amine-based epoxy resin curing agent and 1-a in the proportions shown in Tables 1-4 Minopyrrolidine thiocyanate (NR-S) is added and mixed, coated on a glass substrate to a thickness of 0.3 mm and cured at room temperature, and the time to dry to the touch or the time until the Shore D hardness reaches 50. was measured. The results are shown in Tables 1-4.
  • the PHR in the table indicates the mixing ratio (parts by weight) with respect to 100 parts by weight of the epoxy resin.
  • EDA, DETA, and AEP were used, the time to dry the touch was not measured due to amine brushing, so the time at Shore D50 is shown.
  • Bisphenol A type epoxy resin [Product name: Epoxy 806, epoxy equivalent: 165, manufactured by Japan Epoxy Resin Co., Ltd.] Amines epoxy resin cured to 10 g at the ratio shown in Table 5 The agent and 1-aminopyrrolidine thiocyanate were added and mixed, applied to a glass substrate at a thickness of 0.3 mm, cured at 5 ° C., and the touch dry time was measured. Table 5 shows the results.
  • Touch dry time was measured in the same manner as in Example 1 except that dimethylhydrazine thiocyanate (UDMH-S) was used instead of 1-aminopyrrolidine thiocyanate. Table 6 shows the results.
  • UDMH-S dimethylhydrazine thiocyanate
  • the thiocyanate of the compound represented by the formula (1) cannot cure an epoxy resin by itself, but has a function of significantly improving the curing speed of an amine epoxy resin curing agent. Very useful as a curing accelerator for

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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

L'invention concerne un accélérateur de durcissement destiné à un agent de durcissement à base d'amine pour résines époxy, caractérisé en ce qu'il renferme un sel d'acide thiocyanique d'un composé représenté par la formule générale (I) comme ingrédient actif ; et un procédé permettant d'accélérer le durcissement d'une résine époxy faisant intervenir ledit accélérateur de durcissement. [Dans cette formule (I), R1 et R2 sont identiques ou différents et représentent chacun un groupe alkyle en C¿1-8?, un groupe phényle ou un groupe pyridyle, ou R?1 et R2¿ sont liés l'un à l'autre pour former un groupe alkylène en C¿2-11? ou un groupe représenté par R?3-R4-R5- (R3 et R5¿ étant identiques ou différents et représentant chacun un groupe alkylène en C¿1-8? et R4 représentant de l'oxygène, du soufre, un groupe représenté par =NR?6¿ ou =NNH¿2?, à condition que R?6¿ représente un groupe alkyle en C¿1-8?).]
PCT/JP2002/008162 2001-08-10 2002-08-09 Accelerateur de durcissement destine a un agent de durcissement a base d'amine pour resines epoxy et procede d'acceleration du durcissement d'une resine epoxy Ceased WO2003014181A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-243153 2001-08-10
JP2001243153A JP2003055440A (ja) 2001-08-10 2001-08-10 アミン系エポキシ樹脂硬化剤の硬化促進剤及びエポキシ樹脂の硬化促進方法

Publications (1)

Publication Number Publication Date
WO2003014181A1 true WO2003014181A1 (fr) 2003-02-20

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PCT/JP2002/008162 Ceased WO2003014181A1 (fr) 2001-08-10 2002-08-09 Accelerateur de durcissement destine a un agent de durcissement a base d'amine pour resines epoxy et procede d'acceleration du durcissement d'une resine epoxy

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JP (1) JP2003055440A (fr)
WO (1) WO2003014181A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001029109A1 (fr) * 1999-10-19 2001-04-26 Otsuka Kagaku Kabushiki Kaisha Agent de durcissement pour resine epoxy et composition de resine epoxy
JP2002226554A (ja) * 2001-01-31 2002-08-14 Otsuka Chem Co Ltd エポキシ樹脂用硬化促進剤及びエポキシ樹脂用硬化剤組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001029109A1 (fr) * 1999-10-19 2001-04-26 Otsuka Kagaku Kabushiki Kaisha Agent de durcissement pour resine epoxy et composition de resine epoxy
JP2002226554A (ja) * 2001-01-31 2002-08-14 Otsuka Chem Co Ltd エポキシ樹脂用硬化促進剤及びエポキシ樹脂用硬化剤組成物

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