DE3814267A1 - EPOXY RESIN COMPOSITION - Google Patents

Abstract

The problem of the sedimentation and solidification of the inorganic filler in epoxy resins when transported or when stored at elevated temperature is solved by means of epoxy resin compositions which contain an inorganic filler, an anionic surfactant and a silane coupler.

Description

The present invention relates to an epoxy resin composition containing an inorganic filler, an anionic surfactant and a silane coupling agent.

Epoxy resin compositions in which one or more inorganic Fillers such as B. quartz powder, aluminum oxide, talc, calcium carbonate or the like, are incorporated, especially in the fields the casting and molding compounds and the synthetic resin impregnation as well as modified epoxy resin compositions, such as. B. as an adhesive, or Covering material and as such for use in construction engineering and used in the construction sector. These inorganic fillers containing epoxy resin compositions have a disadvantage that the inorganic filler during transport or during storage at elevated temperature tends to deposit or ver consolidate.

As a measure against this phenomenon, the combined use of Thixotropic agents such as B. very finely ground quartz powder (commer currently available under the trade names Aerosil), bentonite and the like chen, known.

However, this addition of fine quartz powder and the like is so far disadvantageous as this addition is the viscosity of the epoxy resin composition increases and thus the processability and labor productivity decrease puts.

Accordingly, in terms of containing inorganic fillers Epoxy resin compositions sought a way to solidify them  the inorganic filler without adding viscosity-increasing material, such as B. quartz powder, bentonite and the like to prevent.

One possibility is the addition of a surfactant that unites the epoxy resin Gives surface-active effect that the wettability of the inorganic filler due to the epoxy resin and thereby the dispersibility improved the inorganic filler and thus its solidification prevented. However, adding the surfactant will destroy the foam and foam-preventing properties of the composition clearly worsened. A product hardened from such a molding compound has therefore has an increased foam content and becomes fragile. Therefore, this method is not used in practice.

The object of the present invention is a Find epoxy resin composition, wherein the solidification of the inorganic filler is prevented by adding a surfactant without, however reduce the foam-destroying properties of the resin.

DE-A 26 52 045 describes the use of cationic surfactants as well Silane couplers for solidifying loose underground sand forma tions in boreholes known by curable organic resins. Further EP-A 57 595 describes a method for scratch and abrasion resistant Coating of glass containers with resin mixtures which u. a. Surfactants and Silane coupling agent included. In EP-A 83 053 nonionic Surfactants and silane coupling agents as components for aqueous primers compositions for glass fibers described. The same procedure only using cationic surfactants is from JP-A Sho 51-35 799 known. Furthermore, US-A 45 22 966 does not tarnish wear-resistant Descriptions for transparent polycarbonate fittings described, u. a. an epoxy-containing silane coupling agent and a non-ionic surfactant contained in an acrylate polymer composition.

It has now surprisingly been found that the foam-destroying and anti-foam properties can be improved and in addition solidification of the inorganic filler can be prevented, when combined in addition to an epoxy resin containing a surfactant a silane coupling agent is added.  

The present invention relates to an epoxy resin composition containing an inorganic filler and an anionic surfactant and a silane coupling agent.

The epoxy resin according to the invention expediently contains together setting 5-700 parts by weight of the inorganic filler 0.01-5.0 parts by weight Parts, especially 0.05-1.0 parts by weight, of the anionic surfactant and 0.001-10.0 parts by weight, especially 0.01-1.0 parts by weight of the silane adhesive mediator based on 100 parts by weight of the epoxy resin.

The amount of the anionic surfactant can also depend on the amount of the inorganic depending on the filler. However, the amount of anionic is Surfactants less than 0.01 parts by weight based on 100 parts by weight of epoxy resin, so this has no effect. If the amount of anionic Surfactant is greater than 5.0 parts by weight, so is the foam-destroying Property of the composition largely reduced, so that the silane coupling agent does not show its preventive effect. Therefore the appropriate amount of the anionic surfactant is 0.01-5.0% by weight Parts. If the amount of the anionic surfactant is less than 0.05% by weight Parts, this shows no practical effect, although the solidification of the inorganic filler is prevented to a small degree. If the amount of the anionic surfactant is 1.0-5.0 parts by weight, that is foam-destroying and foam-preventing properties so strong reduced that the silane coupling agent does not show its effect or the silane coupling agent must be used in a large amount, to show an effect what the glass transition temperature of the hardened Product lowers and the cost of the resin composition to one impractical height. Therefore, the preferred amount used is anionic surfactant 0.05-1.0 parts by weight.

The amount of silane coupling agent used can vary from the amount of depend on anionic surfactant. However, the amount of silane sticking is mediator less than 0.001 parts by weight based on 100 parts by weight of Epoxy resin, this has no effect. If the amount used Exceeding 10.0 parts by weight causes this large amount of silane sticking mediator a lowering of the glass transition temperature (Tg value).  Therefore, the silane coupling agent should be used in an amount of 0.001-10.0 parts by weight can be used. Is the amount of Silane coupling agent less than 0.01 parts by weight, so requires Foam-destroying process takes too much time and processability reduced, although some improvement in foam-destroying and foam-preventing properties is achieved. Amount of the silane coupling agent 1.0-10.0 parts by weight causes this large amount a lowering of the glass transition temperature and the heat resistance of the hardened product and also increases the cost of the composition, so the use of such a large amount of silane coupling agent is no longer of practical importance. Therefore, the preferred one is Amount of use of the silane coupling agent 0.01-1.0 parts by weight.

As epoxy resins according to the present invention are all polyepoxides suitable, the average of two or more 1,2-epoxy groups in own a molecule. It can be saturated, unsaturated, aliphatic, alicyclic, aromatic or heterocyclic epoxides act. These can also be a non-interfering substituent such. B. a halogen atom, a hydroxyl group, an ether group, an ester group or the like. Examples of such polyepoxides are Novolaks, polyglycidyl ethers of dihydric phenols such as. B. 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, bis- (4- hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone, resorcinol or Hydroquinone, polyglycidyl ether of trihydric alcohols such. B. Glycerol, polyglycidyl esters such as e.g. B. diglycidyl phthalate or diglycidyl isophthalate, epoxidized esters of polyethylenically unsaturated fat acids such as B. epoxidized linseed oil, epoxidized esters of unsaturated Alcohols with unsaturated carboxylic acids such as. B. 3,4-epoxycyclohexyl methyl 3,4-epoxicyclohexyl carboxylate; further epoxidized polyethylene unsaturated hydrocarbons such as B. epoxidized 2,2-bis (2-cyclo hexenyl) propane, epoxidized vinylcyclohexane, epoxidized cyclopenta diendimer and the like.

Polyglycidyl ethers of polyvalent are preferred as epoxy resins Phenols and epoxy esters of unsaturated alcohols with unsaturated Carboxylic acids.  

Surfactants include cationic, nonionic and anionic surfactants, as well those of the block copolymer type. Regarding the foam-forming property cationic non-ionic or block copolymer type surfactants these can not be improved in the direction of foam-destroying properties not even by adding a silane coupling agent, but only those of anionic surfactants are adhered by adding a silane Improved intermediary towards foam destruction. Therefore concerns the present invention the use of anionic surfactants.

Anionic surfactants include carboxylates, sulfonates, such as. B. alkylbenzene sulfonates, alkylnaphthalenesulfonates, alkali sulfonates, α- olefin sulfonates, α- sulfofatty acid esters, sulfosuccinic acid esters; Alkoxy, acyloxy or acylaminoalkane sulfonates, sulfates such as. B. alkyl sulfates or ether sulfates, phosphonates or phosphates.

Anionic surfactants particularly suitable for use in accordance with the invention are ether sulfates, such as. B. sodium polyoxyethylene lauryl ether sulfate, Triethanolamine polyoxyethylene lauryl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium alkyl sulfate, triethanolamine alkyl sulfate, which are particularly preferred.

Silane coupling agents include epoxy organosilanes, aminoorganosilanes, Carboxyorganosilanes, mercaptoorganosilanes, methacryloxyorganosilanes, Chlororganosilanes, vinylorganosilanes and cyanoorganosilanes.

Particularly suitable silane coupling agents are the epoxyorganosilanes such as e.g. B.

Glycidoxymethyltrimethoxysilane
Glycidoxymethyltriethoxysilane
β- glycidoxyethyltrimethoxysilane
β- glycidoxyethyltriethoxysilane
γ- glycidoxypropyltrimethoxysilane
γ- glycidoxypropyltriethoxysilane
γ- glycidoxypropyltri (methoxyethoxy) silane
γ- glycidoxypropyltriacetoxysilane
δ- glycidoxybutyltrimethoxysilane
δ- glycidoxybutyltriethoxysilane
Glycidoxymethyldimethoxysilane
Glycidoxymethyl (methyl) dimethoxysilane
Glycidoxymethyl (ethyl) dimethoxysilane
Glycidoxymethyl (phenyl) dimethoxysilane
Glycidoxymethyl (vinyl) dimethoxysilane
Glycidoxymethyl (dimethyl) methoxysilane
β- glycidoxyethyl (methyl) dimethoxysilane
β- glycidoxymethyl (ethyl) dimethoxysilane
β- glycidoxymethyl (dimethyl) methoxysilane
γ- glycidoxypropyl (methyl) dimethoxysilane
γ- glycidoxypropyl (ethyl) dimethoxysilane
γ- glycidoxypropyl (dimethyl) methoxysilane
δ- glycidoxybutyl (methyl) dimethoxysilane
δ- glycidoxybutyl (ethyl) dimethoxysilane
δ- glycidoxybutyl (dimethyl) methoxysilane
Bis (glycidoxymethyl) dimethoxysilane
Bis (glycidoxymethyl) diethoxysilane
Bis (glycidoxyethyl) dimethoxysilane
Bis (glycidoxyethyl) diethoxysilane
Bis (glycidoxypropyl) dimethoxysilane
Bis (glycidoxypropyl) diethoxysilane
Tris (glycidoxymethyl) methoxysilane
Tris (glycidoxymethyl) ethoxysilane
Tris (glycidoxyethyl) methoxysilane
Tris (glycidoxyethyl) ethoxysilane
Tris (glycidoxypropyl) methoxysilane
Tris (glycidoxypropyl) ethoxysilane
Glycidylmethyltrimethoxysilane
Glycidylmethyltriethoxysilane
b -Glycidylethyltrimethoxysilane
β- glycidylethyltriethoxysilane
β- glycidylpropyltrimethoxysilane
γ- glycidylpropyltriethoxysilane
γ- glycidylpropyltri (methoxyethoxy) silane
γ- glycidylpropyltriacetoxysilane
3,4-epoxycyclohexylmethyltrimethoxysilane
3,4-epoxycyclohexylmethyltriethoxysilane
3,4-epoxycyclohexylethyltrimethoxysilane
3,4-epoxycyclohexylpropyltrimethoxysilane
3,4-epoxycyclohexylbutyltrimethoxysilane.

Γ- Glycidoxypropyltrimethoxysilane and β - (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferred.

Since the epoxy resin composition according to the invention contains a surfactant, this causes an improved dispersibility of the inorganic Filler and prevents its solidification and sedimentation. Since the Composition further contains a silane coupling agent, the Deterioration of the foam-destroying properties from the surfactant salary overcome.

Thus, no solidification occurs in the composition according to the invention sedimentation of the inorganic filler, and this has excellent foam-destroying properties, so that at Use of such epoxy resin compositions as a casting or molding compound high quality hardened products can be obtained.

In addition, the epoxy resin compositions can also additional Components which are not important for the effect according to the invention, included, such as B. dyes or stabilizers.

Example 1:

A resin composition is prepared by mixing 100 parts by weight of a liquid bisphenol A-based epoxy resin with an epoxide equivalent of 189 (Araldit® GY 260, Ciba-Geigy) with 0.1 part by weight of triethanolamine polyoxyethylene lauryl ether sulfate, 0.02 part by weight. Parts γ- glycidoxypropyltrimethoxysilane and 50 parts by weight of crystalline quartz powder (available under the trade name 3H, Nagase & Co., Japan).

Example 2:

A resin composition is prepared by mixing 100 parts by weight of a liquid bisphenol F-based epoxy resin (Epiclon® 830-S, DIC Co., Japan) with 0.1 part by weight of triethanolsamine poly oxyethylene lauryl ether sulfate, 0.02 part by weight. Parts γ- glycidyloxypropyltri methoxysilane and 50 parts by weight of crystalline quartz powder (as in Example 1).

Comparative Example 1

A resin composition is prepared by mixing 100 parts by weight of one liquid epoxy resin based on bisphenol A (Araldit® GY 260, Ciba-Geigy) with 50 parts by weight of quartz powder (as in Example 1) poses.

Comparative Example 2

A resin composition is prepared by mixing 100 parts by weight of one liquid bisphenol G-based epoxy resin (Epiclon® 830-S, DIC Co., Japan) with 50 parts by weight of quartz powder (as in Example 1).

Application example 1

300 g each of the epoxy resin compositions from Examples 1, 2, Comparative examples 1 and 2 are filled into a 300 ml bottle. These are stored in a truck for 12 days (approx. 6000 km) Road transport test subjected. Then the degree of solidification checked. The results are shown in Table 1.

Table 1

In Table 1 and the following tables, the characters ○, ∆ and × mean the following degrees of solidification.

○ If a stick is pressed into the samples, it reaches the finger push the bottom of the samples with ease. ∆If a rod is pressed into the sample, it will reach the bottom of the Test only under strong pressure. × The rod cannot be pressed into the sample at all.  

In the epoxy resin compositions of Examples 1 and 2, according to the In the present invention, the quartz powder does not solidify and can can be easily stirred even if sedimentation takes place.

The epoxy resin compositions of Comparative Examples 1 and 2 are absent the anionic surfactant and the silane coupling agent, resulting in a compound leads to the quartz powder.

Example of use 2

One sample bottle each (30 cm Ø × 200 mm) is filled with epoxy resin compositions from Examples 1 and 2 and Comparative Examples 1 and 2 up to a height of 180 mm and in a vertical position in a hot air circulation oven at 80 ° C for 24 hours. resp. subjected to a heat aging test at 120 ° C for 8 hours. In this test, the contents of the sample bottle are separated into a clear layer A, a filler dispersion layer B and a layer C which contains excess filler. The heights of the layers are measured (layer A: a mm; layer B: b mm; layer C: c mm) and the degree of sedimentation is calculated according to the following equation. A larger degree of sedimentation means that the filler is more uniformly dispersed in the resin and the degree of solidification is smaller.

In addition, the degree of solidification according to application example 1 certainly.

The results are shown in Table 2.  

Table 2

The results of Table 2 show that the epoxy resin compositions of Examples 1 and 2 no solidification of the quartz powder in the heat show aging test; even if some sedimentation takes place finds, this sedimented quartz powder layer can be easily stirred will. On the other hand, the epoxy resin compositions of Ver same examples 1 and 2 clear sedimentation and clear hardening supply of the inorganic filler.

Example of use 3

Epoxy resin compositions, according to Example 1, but without silane adhesion mediator and with changing content of anionic surfactant manufactured and the heat aging test at 80 ° C / 24 hours as in use subjected to example 2.

The amounts of anionic surfactant used and the results are shown in Table 3.

Table 3

The results in Table 3 show that without using a silane coupling mediator the addition of an anionic surfactant the foam-destroying Properties of the composition deteriorate. The foam disruptive properties deteriorate with increasing amount anionic surfactant and if the amount of surfactant increases by more than 0.5 part by weight no foam destruction is achieved at all.

Regarding the degree of sedimentation, all compositions show good results Results.

Example of use 4

Epoxy resin compositions, according to Example 1, but with changing Silane coupling agent content is produced and the Heat aging test at 80 ° C / 24 hours analogous to application example 2 subject.

The amounts of silane coupling agent used and the results are shown in Table 4.  

Table 4

The results in Table 4 show that the effect of the silane adhesive is used in an amount of 0.015 parts by weight.

All compositions show regardless of the silane coupling agent lots of good results regarding the degree of sedimentation. Only that Composition without surfactant but with silane coupling agent shows one low level of sedimentation, which means that they are in a solid Condition is.

Application example 5

Epoxy resin compositions are prepared according to Example 1, wherein the anionic surfactant by cationic nonionic or block copoly mer surfactants is replaced and the amount of silane coupling agents varies will. The foam-destroying properties, the degree of sedimentation and the degree of solidification of these compositions are according to the in the Application examples 1-3 described method, the Degree of sedimentation determined only after heat aging at 80 ° C / 24 hours becomes. The results are shown in Table 5.  

Table 5

The results of this application example show that when using cationic or non-ionic surfactants are the foam-destroying properties and the degree of solidification cannot be improved.

If a block copolymer surfactant is used, it will destroy the foam the properties not improved, not even by adding one Silane coupling agent. The degree of solidification and the degree of sedimentation however will be improved.

In the epoxy resin compositions according to the invention Hardly any deposits or transport during storage at elevated temperatures and solidification of the inorganic filler. Even if this is deposits or solidifies, just stirring to dissolve. Continue  there is no increase in the viscosity of the epoxy resin composition still an increase in the tendency to foam, which results from it makes hardened products brittle.

Therefore, the epoxy resin compositions of the invention have a good one Workability and good labor productivity on and result as Casting and molding compounds hardened products of high quality.

Claims (11)

1. epoxy resin composition containing an inorganic filler, an anionic surfactant and a silane coupling agent. 2. The composition of claim 1, wherein the amount of the inorganic Filler 5-700 parts by weight based on 100 parts by weight of the epoxy resin is. 3. The composition of claim 1, wherein the amount of the anionic Surfactants 0.01-5.0 parts by weight based on 100 parts by weight of the epoxy resin is. 4. The composition of claim 3, wherein the amount of the anionic Surfactant is 0.05-1.0 parts by weight. 5. The composition of claim 1, wherein the amount of silane adhesion promoter mean 0.001-10.0 parts by weight based on 100 parts by weight of the epoxy resin amounts. 6. A composition according to claim 5, wherein the amount of silane coupling agent is 0.01-1.0 parts by weight. 7. The composition of claim 1, wherein the epoxy resin is a polyepoxide with an average of two or more 1,2-epoxy groups in the molecule poses. 8. The composition of claim 1, wherein the anionic surfactant is a Carboxylate, a sulfonate, a sulfate, a phosphonate or a phosphate means. 9. The composition of claim 8, wherein the anionic surfactant Means ether sulfate.   10. The composition of claim 1, wherein the silane coupling agent is a Epoxy, amino, carboxy, mercapto, methacryloxy, chlorine, vinyl or Cyanoorganosila represents. 11. The composition of claim 1, wherein the silane coupling agent is a Epoxyorganosilan represents.