CA1229939A - Hardner for epoxide resin masses - Google Patents
Hardner for epoxide resin massesInfo
- Publication number
- CA1229939A CA1229939A CA000467065A CA467065A CA1229939A CA 1229939 A CA1229939 A CA 1229939A CA 000467065 A CA000467065 A CA 000467065A CA 467065 A CA467065 A CA 467065A CA 1229939 A CA1229939 A CA 1229939A
- Authority
- CA
- Canada
- Prior art keywords
- oxide
- dicyandiamide
- weight
- epoxide resin
- hardener
- 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.)
- Expired
Links
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
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/315—Compounds containing carbon-to-nitrogen triple bonds
- C08K5/3155—Dicyandiamide
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)
- Exhaust Gas After Treatment (AREA)
- Ceramic Products (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT
Hardner for epoxide resin masses The present invention provides a hardner for epoxide resin masses based on dicyandiamide, wherein it contains a) dicyandiamide with a particle size of ?90% ?10 µm.
and b) 0.1 to 30% by weight of silicon dioxide and/or of an oxide of a metal of Group IIA or IIB of the Periodic Table with a large specific surface area.
Hardner for epoxide resin masses The present invention provides a hardner for epoxide resin masses based on dicyandiamide, wherein it contains a) dicyandiamide with a particle size of ?90% ?10 µm.
and b) 0.1 to 30% by weight of silicon dioxide and/or of an oxide of a metal of Group IIA or IIB of the Periodic Table with a large specific surface area.
Description
YO-YO I
Toe prevent invention is concerned with a hardier for epoxide resin masse bayed on dicyandiamide~
It it Noel to use dicyandiam:ide for the harden-in of epoxide resins of US. Patent Specification owe. 2,637,715 and 3,391,113). The advantages of the dicyandiamide are, in particular, its toxicological harmlessness and the absence of smell, as well as its chemically inert behaviGur, so that the resin-hardner mixture ha a good storage-stability.
The disadvantages of dicyandiamide are its poor volubility and the non-optimal distributability of the hardier in the epoxide resin which, for example, can lead to an increased consumption of hardier. However, this increased amount used give rise, in turn, to the effect that the-haxdened resin-can contain regions with a high content-of non-consumed-hardner and thus -can have defects in end product Attempts have not been lacking to improve this problem of the poor di3~ributability in liquid epoxide resins or in epoxide resins melting at a higher-temp-erasure Depending upon the intended use, the follow-in ways have been employed thy use ox an appropriate solvent-or solvent mixture for the production of impregnation solutions from epoxide resin and hardier (cf. Federal Republic of Germany Patent Specification No. 30 26 706 and Gunman Democratic Republic Patent-Specification owe 133 955), .
~2~3~33~
I
the use of substituted dicyandiamides with improved distributability in epoxide resin masses (cf., for example, French Patent Specification No. 22 07 911), and the use of dicyandiamide dispersions in liquid epoxide resin mixtures.
Whereas, according to the firs way, only a few solvent mixtures could be found which display the necessary criteria, such a good volubility or good compatibility with the epoxide resin mixtures, in the case of the second way, the provision of substituted dicyandiamides is uneconomical because the production of these products gives rise to high operational and investment costs, In the cave of the last-mentioned way, the difficulty arise that dicyandiamide must be used which is as finely divided as pro sidle in order to achieve a good distribution in powdered epoxide resin-hardner mixture or to obtain dispersions in liquid epoxide resin mixtures and, on the other hand, finely-divided dicyandiamide has a marked tendency to cake so that finely-divided dicyandiamide forms agglomerates within a very short space of time which also can scarcely be broken up again by grinding. In the case of dicyandiamide suspensions, this agglomer-anion of finely-ground dicyandiamide leads to the formation of comparatively large flock, which give rise to considerable problems in the epoxide resin ,, mixtures.
I
Therefore, it is an object of the present invention to provide a hardier for epoxide Ryan masse based on dicyandiamide which does not display the above-mentioned known disadvantages, which is characterized by good application-technical properties and which can be produced economically.
Thus, according to the present invention, where is provided a hardier for epoxide resin masses based on dicyandiamide, wherein it contains a) dicyandiamide with a particle size off 90% 10 us and by 0.1 to OWE by weight of silicon dioxide and/or of an oxide of a metal of Group IDA or IT of the Periodic Table with a large specific surface area Surprisingly, we have found that the hardier according to the-present invention for epoxide resin masse has an improved distributability in the oxide resin, as well as an increased storage stability in the epoxide resin-hardner dispersions.--- Furthermore, the addition of silicon dioxide and/or of oxides of metal of Group IDA or JIB of the Periodic Table bring about a sometime considerable shortening of the gel times in comparison with normal dicyandiamide, which was also not foreseeable.
The epoxide resin hardier according to the present invention based on dicyandiamide consists of a dicyandiamide with a particle it I 90% I 10 em. J
~L~2~339 a well a silicon dioxide and/or an oxide of a metal of Group IDA or JIB of the Periodic Table with a large specific surface area the specific surface area preferably being at least 50 m2/gO according to BET, in order to achieve the action according o the present invention. Types of silicon dioxide which are commercially available under the trade awry Aerosol degas), a well a HDK (Weaker), have proved to be especially advantageous.
Especially preferred oxides of metals of Group IDA and JIB of the Periodic Table include magnesium oxide, as well as mixture thereof but, in principle, other oxides, for example those of barium or of strontium, can alto be used.
The amount of the silicon dioxide or of the oxide of a metal of Group IT or JIB of the Periodic able is 0.1 to 3~/0 by weight and preferably from 0.2 to owe by weight referred to the weight of the dicyandiamide.
The production of the epoxide resin hardier according to the present invention preferably takes place by continuously dosing the silicon dioxide and/or the oxide of a metal of Group IT or JIB of the Periodic Table to the dicyandiamide before grinding to the desired grain give so that the metal oxides have the same particle size distribution as the dicyandiamide.
This prevents the finely-ground dicyandiamide from clumping together immediately after the grinding procedure, which would result in the formation of undesired agglomerates. Thus, the mixing of the components can be completed in one step The grinding of the dicyandiamide and/or of the metal oxide can by carried out without problems in conventional technical devices, such as grader mills or the like, i.e. without separation of dicyandiamide and of the metal oxides during the grinding process The dicyandiamide-containing epoxide hardier according to the present invention, which has a bulk density of 300 to 500 gloater, can be optimally distributed in solid or liquid epoxide resins, it thereby being possible to reduce the amount of hardier in comparison with conventional hardness based on dicyandiamide. We have found that amounts I- of 3 to 6% by weight, referred to the epoxide equip -valet weight, are sufficient.
The hardening reaction with the hardier accord-in to the present invention can be additionally activated with conventional hardening accelerators, for example 2-methylimidazole, substituted urea ~monouron, Doreen), dimethylbenzylamine or substituted methylenedianilines. The hardened epoxide resin has a clearly improved chemical resistance and adhesion in comparison with products produced with conventional J
I
dicyandiamide-containing hardeners The following Examples are given for the purpose of illustrating the present invention. For comparison purpose, epoxide resin hardness Bud on dicyandiamide are produced by grinding dicyandiam:ide with the follow-in additives and compared with one another:
hardier a): dicyandiamide with 1.3% by weight silicon dioxide HDK 20 with a specific surface area of 200 mug (Weaker) hardier I): ~icyandiamide with owe by weight calcium oxide hardier c): dicyandiamide with 0.8% by weight magnesium oxide hardier d): dicyandiamide with I by weight zinc oxide hardier en dicyandiamide without addition Example 1.
of yo-yo air hardier a): 4 - 5 my little agglomeration) hardier boo 4 _ 5 em. (scarcely any agglomeration) hardier c): 4 - 5 em. (scarcely any agglomeration) hardier do: 4 - 5 em. (scarcely any agglomeration) ; hardier of: lo em. (agglomerates up to 40 my -I
' ' -i -8-For the wet sieving, there it produced a 15%
suspension of the qualities obtained in ethyl acetate saturated with dicyandiamide. Err homogeneous mixing the suspension is treated for 5 minutes in an ultra-sonic bath and then filtered through a vibrating previously weighed out filter with a mesh size of 10 em.
After the filter ha been rewashed Whitehall further 50 go ethyl acetate, it is dried and reweighed.
From this is given the percentage content of Dyson-doomed with a grain diameter of lest than 10 em.
hardier a: 99% 10 em.
hardier b): 98% 10 my hardier c): 98% 10 em.
hardier d): 98% 10 em.
hardier en: 45% C 10 em.
. . .--The gel times of various epoxide hardness accord-in to the present invention are determined with Epikote 1007 and compared with conventional Dyson-doomed with an average particle size of 80 em, ~2~3~
Jo hardier (owe by woo dicyandiamide gel time at 180C.
rev to Epikot~ 1007) in min.
dicyandiamide ~80 my 7.0 epoxide resin h~rdner a 6.0 5 epoxide resin hardier b) 5.0 epoxide resin hardier c) 6.0 epoxide resin hardier d) 5.0 dicyandiamide (80 m.) 3 0 0.25% 2-~ethylimidazole 10 epoxide resin hardier a) 2.5 0.25% 2-methyli~idazole . . ,, _ __ Dispersions are produced each of 4% of the hardier according to the present invention in Epikote 828 and compared with a dispersion of 4% dicyandiamide (80 em.) within a period of time of 4 weeks:
____ hardier dispersion after 4 weeks : storage _____ dicyandiamide (80 em) almost all the material deposited hardier a) stable dispersion hardier b) stable dispersion hardier c) stable dispersion 25 hardier d) stable dispersion hardier e) about 5~/0 deposited as flocks 2Z9~
Jo --10--.
The dispersions described in Example 4 are applied in the form of a lacquer layer to a cleaned steel sheet and hardened at 180C. for one hour, the S following observations thereby being made:
dicyandiamide (80 my): punctuate coating with unused hardier, not completely hardened hardier ago smooth, transparent coating 10 hardier b): smooth, white-pigmented coating hardier c): smooth, almost transparent coating hardier d): smooth, slightly pigmented coating 15 hardier e): uneven, slightly punctuate coating with unused h~rdner ,
Toe prevent invention is concerned with a hardier for epoxide resin masse bayed on dicyandiamide~
It it Noel to use dicyandiam:ide for the harden-in of epoxide resins of US. Patent Specification owe. 2,637,715 and 3,391,113). The advantages of the dicyandiamide are, in particular, its toxicological harmlessness and the absence of smell, as well as its chemically inert behaviGur, so that the resin-hardner mixture ha a good storage-stability.
The disadvantages of dicyandiamide are its poor volubility and the non-optimal distributability of the hardier in the epoxide resin which, for example, can lead to an increased consumption of hardier. However, this increased amount used give rise, in turn, to the effect that the-haxdened resin-can contain regions with a high content-of non-consumed-hardner and thus -can have defects in end product Attempts have not been lacking to improve this problem of the poor di3~ributability in liquid epoxide resins or in epoxide resins melting at a higher-temp-erasure Depending upon the intended use, the follow-in ways have been employed thy use ox an appropriate solvent-or solvent mixture for the production of impregnation solutions from epoxide resin and hardier (cf. Federal Republic of Germany Patent Specification No. 30 26 706 and Gunman Democratic Republic Patent-Specification owe 133 955), .
~2~3~33~
I
the use of substituted dicyandiamides with improved distributability in epoxide resin masses (cf., for example, French Patent Specification No. 22 07 911), and the use of dicyandiamide dispersions in liquid epoxide resin mixtures.
Whereas, according to the firs way, only a few solvent mixtures could be found which display the necessary criteria, such a good volubility or good compatibility with the epoxide resin mixtures, in the case of the second way, the provision of substituted dicyandiamides is uneconomical because the production of these products gives rise to high operational and investment costs, In the cave of the last-mentioned way, the difficulty arise that dicyandiamide must be used which is as finely divided as pro sidle in order to achieve a good distribution in powdered epoxide resin-hardner mixture or to obtain dispersions in liquid epoxide resin mixtures and, on the other hand, finely-divided dicyandiamide has a marked tendency to cake so that finely-divided dicyandiamide forms agglomerates within a very short space of time which also can scarcely be broken up again by grinding. In the case of dicyandiamide suspensions, this agglomer-anion of finely-ground dicyandiamide leads to the formation of comparatively large flock, which give rise to considerable problems in the epoxide resin ,, mixtures.
I
Therefore, it is an object of the present invention to provide a hardier for epoxide Ryan masse based on dicyandiamide which does not display the above-mentioned known disadvantages, which is characterized by good application-technical properties and which can be produced economically.
Thus, according to the present invention, where is provided a hardier for epoxide resin masses based on dicyandiamide, wherein it contains a) dicyandiamide with a particle size off 90% 10 us and by 0.1 to OWE by weight of silicon dioxide and/or of an oxide of a metal of Group IDA or IT of the Periodic Table with a large specific surface area Surprisingly, we have found that the hardier according to the-present invention for epoxide resin masse has an improved distributability in the oxide resin, as well as an increased storage stability in the epoxide resin-hardner dispersions.--- Furthermore, the addition of silicon dioxide and/or of oxides of metal of Group IDA or JIB of the Periodic Table bring about a sometime considerable shortening of the gel times in comparison with normal dicyandiamide, which was also not foreseeable.
The epoxide resin hardier according to the present invention based on dicyandiamide consists of a dicyandiamide with a particle it I 90% I 10 em. J
~L~2~339 a well a silicon dioxide and/or an oxide of a metal of Group IDA or JIB of the Periodic Table with a large specific surface area the specific surface area preferably being at least 50 m2/gO according to BET, in order to achieve the action according o the present invention. Types of silicon dioxide which are commercially available under the trade awry Aerosol degas), a well a HDK (Weaker), have proved to be especially advantageous.
Especially preferred oxides of metals of Group IDA and JIB of the Periodic Table include magnesium oxide, as well as mixture thereof but, in principle, other oxides, for example those of barium or of strontium, can alto be used.
The amount of the silicon dioxide or of the oxide of a metal of Group IT or JIB of the Periodic able is 0.1 to 3~/0 by weight and preferably from 0.2 to owe by weight referred to the weight of the dicyandiamide.
The production of the epoxide resin hardier according to the present invention preferably takes place by continuously dosing the silicon dioxide and/or the oxide of a metal of Group IT or JIB of the Periodic Table to the dicyandiamide before grinding to the desired grain give so that the metal oxides have the same particle size distribution as the dicyandiamide.
This prevents the finely-ground dicyandiamide from clumping together immediately after the grinding procedure, which would result in the formation of undesired agglomerates. Thus, the mixing of the components can be completed in one step The grinding of the dicyandiamide and/or of the metal oxide can by carried out without problems in conventional technical devices, such as grader mills or the like, i.e. without separation of dicyandiamide and of the metal oxides during the grinding process The dicyandiamide-containing epoxide hardier according to the present invention, which has a bulk density of 300 to 500 gloater, can be optimally distributed in solid or liquid epoxide resins, it thereby being possible to reduce the amount of hardier in comparison with conventional hardness based on dicyandiamide. We have found that amounts I- of 3 to 6% by weight, referred to the epoxide equip -valet weight, are sufficient.
The hardening reaction with the hardier accord-in to the present invention can be additionally activated with conventional hardening accelerators, for example 2-methylimidazole, substituted urea ~monouron, Doreen), dimethylbenzylamine or substituted methylenedianilines. The hardened epoxide resin has a clearly improved chemical resistance and adhesion in comparison with products produced with conventional J
I
dicyandiamide-containing hardeners The following Examples are given for the purpose of illustrating the present invention. For comparison purpose, epoxide resin hardness Bud on dicyandiamide are produced by grinding dicyandiam:ide with the follow-in additives and compared with one another:
hardier a): dicyandiamide with 1.3% by weight silicon dioxide HDK 20 with a specific surface area of 200 mug (Weaker) hardier I): ~icyandiamide with owe by weight calcium oxide hardier c): dicyandiamide with 0.8% by weight magnesium oxide hardier d): dicyandiamide with I by weight zinc oxide hardier en dicyandiamide without addition Example 1.
of yo-yo air hardier a): 4 - 5 my little agglomeration) hardier boo 4 _ 5 em. (scarcely any agglomeration) hardier c): 4 - 5 em. (scarcely any agglomeration) hardier do: 4 - 5 em. (scarcely any agglomeration) ; hardier of: lo em. (agglomerates up to 40 my -I
' ' -i -8-For the wet sieving, there it produced a 15%
suspension of the qualities obtained in ethyl acetate saturated with dicyandiamide. Err homogeneous mixing the suspension is treated for 5 minutes in an ultra-sonic bath and then filtered through a vibrating previously weighed out filter with a mesh size of 10 em.
After the filter ha been rewashed Whitehall further 50 go ethyl acetate, it is dried and reweighed.
From this is given the percentage content of Dyson-doomed with a grain diameter of lest than 10 em.
hardier a: 99% 10 em.
hardier b): 98% 10 my hardier c): 98% 10 em.
hardier d): 98% 10 em.
hardier en: 45% C 10 em.
. . .--The gel times of various epoxide hardness accord-in to the present invention are determined with Epikote 1007 and compared with conventional Dyson-doomed with an average particle size of 80 em, ~2~3~
Jo hardier (owe by woo dicyandiamide gel time at 180C.
rev to Epikot~ 1007) in min.
dicyandiamide ~80 my 7.0 epoxide resin h~rdner a 6.0 5 epoxide resin hardier b) 5.0 epoxide resin hardier c) 6.0 epoxide resin hardier d) 5.0 dicyandiamide (80 m.) 3 0 0.25% 2-~ethylimidazole 10 epoxide resin hardier a) 2.5 0.25% 2-methyli~idazole . . ,, _ __ Dispersions are produced each of 4% of the hardier according to the present invention in Epikote 828 and compared with a dispersion of 4% dicyandiamide (80 em.) within a period of time of 4 weeks:
____ hardier dispersion after 4 weeks : storage _____ dicyandiamide (80 em) almost all the material deposited hardier a) stable dispersion hardier b) stable dispersion hardier c) stable dispersion 25 hardier d) stable dispersion hardier e) about 5~/0 deposited as flocks 2Z9~
Jo --10--.
The dispersions described in Example 4 are applied in the form of a lacquer layer to a cleaned steel sheet and hardened at 180C. for one hour, the S following observations thereby being made:
dicyandiamide (80 my): punctuate coating with unused hardier, not completely hardened hardier ago smooth, transparent coating 10 hardier b): smooth, white-pigmented coating hardier c): smooth, almost transparent coating hardier d): smooth, slightly pigmented coating 15 hardier e): uneven, slightly punctuate coating with unused h~rdner ,
Claims (11)
1. A hardner for epoxide resin masses based on dicyan-diamide, comprising a) dicyandiamide with a particle size of ?90%
?10 µm, and b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area.
?10 µm, and b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area.
2. A hardner according to claim 1, comprising 0.2 to 20% by weight of said at least one oxide, referred to the weight of the dicyandiamide,
3. A hardner according to claim 2, wherein the at least one oxide has a specific surface area according to BET
of at least 50 m2/g.
of at least 50 m2/g.
4. A hardner according to claim 1 or 2, wherein the at least one oxide is silicon dioxide haying a specific surface area according to BET of at least 50 m2/g,
5. A hardner according to claim 1 or 2, wherein the at least one oxide is a metal oxide of a metal of Group IIA
or IIB of the Periodic Table, having a specific surface area according to BET of at least 50 m2/g.
or IIB of the Periodic Table, having a specific surface area according to BET of at least 50 m2/g.
6. The hardener according to claim 1 or 2, wherein the at least one oxide is selected from the group consisting of magnesium oxide, calcium oxide and zinc oxide.
7. A hardener for epoxide resin masses compris-ing:
(a) dicyandiamide of which at least 90% has a particle size not greater than 10µm, and (b) 0.1 to 30%, by weight, of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Groups IIA and IIB of the Periodic Table, said at least one oxide having a specific surface area according to BET of at least 50m2/g.
(a) dicyandiamide of which at least 90% has a particle size not greater than 10µm, and (b) 0.1 to 30%, by weight, of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Groups IIA and IIB of the Periodic Table, said at least one oxide having a specific surface area according to BET of at least 50m2/g.
8. A hardener according to claim 7, having a bulk density of 300 to 500 g/litre.
9. An epoxide composition comprising:
(a) an epoxide resin mass, and (b) a hardener as defined in claim 7 or 8, in an amount of 3 to 6%, by weight, referred to the equivalent weight of (a).
(a) an epoxide resin mass, and (b) a hardener as defined in claim 7 or 8, in an amount of 3 to 6%, by weight, referred to the equivalent weight of (a).
10. A process for the production of a hardener for epoxide resin masses comprising:
(a) dicycndiamide with a particle size of ? 90%
? 10µm, and (b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area, which process comprises:
measuring the at least one oxide into the dicyandiamide before grinding and grinding the dicyan-diamide and at least one oxide together to the desired particle size to form said hardener.
(a) dicycndiamide with a particle size of ? 90%
? 10µm, and (b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area, which process comprises:
measuring the at least one oxide into the dicyandiamide before grinding and grinding the dicyan-diamide and at least one oxide together to the desired particle size to form said hardener.
11. A hardener for epoxide resin masses compris-ing:
(a) dicyandiamide with a particle size of ? 90%
? 10µm, and (b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area, produced by a process comprising:
measuring the at least one oxide into the dicyandiamide before grinding and grinding the dicyan-diamide and at least one oxide together to the desired particle size to form said hardener.
(a) dicyandiamide with a particle size of ? 90%
? 10µm, and (b) 0.1 to 30% by weight of at least one oxide selected from the group consisting of silicon dioxide and oxides of metals of Group IIA and IIB of the Periodic Table, with a large specific surface area, produced by a process comprising:
measuring the at least one oxide into the dicyandiamide before grinding and grinding the dicyan-diamide and at least one oxide together to the desired particle size to form said hardener.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19833340788 DE3340788A1 (en) | 1983-11-11 | 1983-11-11 | HARDENER FOR EPOXY RESINS |
| DEP3340788.6 | 1983-11-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1229939A true CA1229939A (en) | 1987-12-01 |
Family
ID=6214045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000467065A Expired CA1229939A (en) | 1983-11-11 | 1984-11-05 | Hardner for epoxide resin masses |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0148365B2 (en) |
| JP (1) | JPS60124618A (en) |
| AT (1) | ATE28653T1 (en) |
| CA (1) | CA1229939A (en) |
| DE (2) | DE3340788A1 (en) |
| FI (1) | FI844415L (en) |
| NO (1) | NO160377C (en) |
| ZA (1) | ZA848542B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61223023A (en) * | 1985-03-28 | 1986-10-03 | Nitto Electric Ind Co Ltd | Curing agent composition for epoxy resin |
| JPH0668091B2 (en) * | 1987-10-27 | 1994-08-31 | 三菱電機株式会社 | Thermosetting insulating resin paste |
| JPH0660230B2 (en) * | 1989-09-30 | 1994-08-10 | 東燃株式会社 | Epoxy resin composition |
| JPH0662737B2 (en) * | 1989-10-31 | 1994-08-17 | 東燃株式会社 | Epoxy resin composition |
| DE102008022007A1 (en) * | 2008-05-02 | 2009-11-05 | Alzchem Trostberg Gmbh | Dicyandiamide granules with high dissolution rate and good flowability and process for its preparation |
| DE102009052061A1 (en) | 2009-11-05 | 2011-05-12 | Alzchem Trostberg Gmbh | Use of guanidine derivatives as curing accelerator for epoxy resins |
| DE102010020882A1 (en) | 2010-05-18 | 2011-11-24 | Alzchem Trostberg Gmbh | Semicarbazone for curing epoxy resins |
| JP2021147496A (en) * | 2020-03-19 | 2021-09-27 | 三菱ケミカル株式会社 | Epoxy resin composition, and prepreg and fiber-reinforced plastic using the same |
| JP2023035684A (en) * | 2021-09-01 | 2023-03-13 | 株式会社豊田中央研究所 | Heat-curable composition |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH565216A5 (en) * | 1970-06-12 | 1975-08-15 | Schering Ag | |
| DE2338430C3 (en) * | 1973-07-28 | 1978-10-12 | Schering Ag, 1000 Berlin Und 4619 Bergkamen | Heat-curable, thickened epoxy resin compounds |
| US3882064A (en) * | 1973-12-27 | 1975-05-06 | Du Pont | Epoxy resin powder coating composition |
| US4169187A (en) * | 1977-04-01 | 1979-09-25 | E. I. Du Pont De Nemours And Company | Powder coating composition of a mixture of epoxy resins |
| JPS585925B2 (en) * | 1978-07-23 | 1983-02-02 | 東邦ベスロン株式会社 | Epoxy resin composition for carbon fiber prepreg |
| US4311753A (en) * | 1979-07-17 | 1982-01-19 | General Electric Company | Curing agent for epoxy resin laminating compositions comprising a mixture of dicyandiamide and a tetra-alkylguanidine |
-
1983
- 1983-11-11 DE DE19833340788 patent/DE3340788A1/en not_active Withdrawn
-
1984
- 1984-11-01 ZA ZA848542A patent/ZA848542B/en unknown
- 1984-11-05 CA CA000467065A patent/CA1229939A/en not_active Expired
- 1984-11-07 JP JP59233424A patent/JPS60124618A/en active Granted
- 1984-11-09 AT AT84113531T patent/ATE28653T1/en not_active IP Right Cessation
- 1984-11-09 EP EP84113531A patent/EP0148365B2/en not_active Expired - Lifetime
- 1984-11-09 FI FI844415A patent/FI844415L/en not_active Application Discontinuation
- 1984-11-09 DE DE8484113531T patent/DE3465096D1/en not_active Expired
- 1984-11-09 NO NO844495A patent/NO160377C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0148365A1 (en) | 1985-07-17 |
| NO160377C (en) | 1989-04-12 |
| JPH0443086B2 (en) | 1992-07-15 |
| FI844415A0 (en) | 1984-11-09 |
| NO844495L (en) | 1985-05-13 |
| JPS60124618A (en) | 1985-07-03 |
| DE3465096D1 (en) | 1987-09-03 |
| DE3340788A1 (en) | 1985-05-23 |
| ATE28653T1 (en) | 1987-08-15 |
| NO160377B (en) | 1989-01-02 |
| ZA848542B (en) | 1985-06-26 |
| FI844415L (en) | 1985-05-12 |
| EP0148365B2 (en) | 1994-08-24 |
| EP0148365B1 (en) | 1987-07-29 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |