WO1999058591A1

WO1999058591A1 - Products for repairing, filling, glueing, protecting, organic or anorganic materials by mixing curable reactive compositions

Info

Publication number: WO1999058591A1
Application number: PCT/NL1999/000286
Authority: WO
Inventors: Jacob Woudsma; Vincent Alfred Joseph Woudsma
Original assignee: Jacob Woudsma; Vincent Alfred Joseph Woudsma
Priority date: 1998-05-12
Filing date: 1999-05-10
Publication date: 1999-11-18
Also published as: NL1009134A1; NL1009134C2

Abstract

This invention provides in a workshop on the spot new flexible epoxy resin compositions made from epoxy functional materials using solidifying agents or hardeners. These compositions, which are useful as fillers, primes, mortars, adhesives and coatings for wood, metal, etc., are made by mixing epoxy resins or epoxy group containing compounds with hardener systems and other polymer resin based compositions, which cause a faster or slower and better controlled curing technology with a better quality. These products are novel materials in the epoxy and paint technology. Addition of other components in the workshop on the spot before solidifying or curing the mixed composition produces a range of new other products reducing the costs for the application and logistics. The production of no or less chemical waste is an extra advantage and a positive contribution to the environment.

Description

- 1 -

PRODUCTS FOR REPAIRING, FILLING, GLUEING, PROTECTING, ORGANIC R ANORGANIC MATERIALS BY MIXING CURABLE REACTIVE COMPOSITIONS

During the last ten years the application of cured products like epoxy containing products has increased enormously in the Netherlands, due to the increase of woodrot and the attempt to decrease the maintenance costs of wooden window frames of houses. Moreover the application of epoxy composition based products increased due to the tendency of using a higher quality of applied products as requested by the house owners.

Ten years ago all epoxy based products were not enough flexible to repair wood exposed to outdoor conditions, giving a minimum performance and high application costs. A first step to the solution was the introduction of new flexible cured epoxy compositions as described and explained in Dutch patent nr 193253.

These products, however, all have the disadvantage of not curing at temperatures below about 10-15 degrees centigrade or they are bad in their processing properties. For instance in case the products needed to be painted a smooth topfinish was difficult to achieve.

In practice there are a small number of other flexible cured epoxy resin based compositions. However these products are curing too fast or too slowly and are only suitable for specific repairing operations. The curing time of the epoxy resin compositions becomes uncontrollable at temperatures below about 10-15 degrees centigrade as will normally occur in the Netherlands during the autumn, winter or spring. This normally results in high maintenance costs since the application is mainly outside. The application of accelators or retarders has not solved these problems. All these products are changing the properties of the cured epoxy resins negatively and make them unsuitable or less suitable for repairing , filling, protecting or glueing organic or anorganic materials exposed to outdoor conditions. Surprisingly, we have found that a mixture of an epoxy resin and a combination of a solidifying or a harderner system based on a polymercaptane and a polyethera ine mixed on the spot -not in the factory- will solve the problems as explained. And it will also result into one or more of the following advantages:

a) improved flexibility b) adjustment of the performance c)a controllable curing time/application time d)more economic in use e) adjustment for a number of different products for a different application f ) an improved price performance ratio g) lower logistic costs h)no chemical waste anymore i)less harmful to the environment j ) less harmful to the worker k) easier processing properties 1) fewer mixing failures m) easier, better and more economic in finish n) fewer products in use o) cheaper application

The present invention provides a composition as Claim I and includes the products from it partly or entirely being cured such as polymer resin compositions.

For example, the composition of this invention consists of the following ingredient classes:

(A) epoxy resins or epoxy group containing compounds.

(B) a solidifying system or a hardener system of at least one hardener which will react with (A) to give a solid, but which is not present in sufficient quantities to allow or cause complete curing of (A) under the reaction -3- conditions chosen for (A) and (B) .

(C) a solidifying or a hardener system for (A) which consists of at least two hardeners of which one remains separately unreacted under the conditons of reaction chosen for, but will be initiated by the speed of reaction of the other hardener and will partly cure the epoxy compositon (A)

(D) addition of components already being present in (A) , (B) or (C) .

(E) addition of other additives that may be required to modify the physical properties of the cured or partly cured compositions or converting it into other products.

The solid or liquid epoxy resin composition is made by mixing (A) , (B) , (C) , (D) and (E) together or separately by any convenient method, but in such a way that (A) , (B) , (C) , (D) or (E) or combinations derived from them will cause the desired type of a product after becoming homogeneous .

The epoxy resins or epoxy group containing compounds, (A) , employed in this invention maybe liquid or mixed liquid and solid mixed liquid resins. Epoxy resins based on diglycidylether of bisphenol A or bisphenol F < 700 Mol are preferred.

The preferred solidifying systems, (B) , used to convert the liquid resins to a solid, are compounds or mixtures of compounds whose most reactive groups relative to the epoxy materials employed are amines, generally primary, secondary or tertiary amines. Acids and anhydrides are also solidifying agents, but they restrict the type of hardener system.

The solidifying system we prefer are systems whose result in flexible cured or a partly cured mass and do not restrict -4 - to the type of hardener system by using the same solidifying system as hardener system.

The ratio between the different hardeners determines the chemical physical properties and curing time and must be variable in (B) and (C) in case one will achieve a different performance or a different curing time of the mixed product

(A) and (B) , depending on the type of the application.

The solidifying or useful hardener systems, (B) and (C) , for an epoxy compound (A) are combinations of dicyaandiamide, aromatic amines such as diaminodiphenyl sulphones, borontrifluoride amine complexes, imidazoles, carboxylic acids, hydrazides, substituted ureas, polyether amines and polymercaptanes . However, combinations of polyether amines and polymercaptanes are preferred. As already explained a key requirement of these two hardeners is to mix them in the desired quantity right before use depending on the conditions of the application and performance of the product one wishes to achieve.

The same components (D) , as already present in (A), (B)or (C) are added to modify the physical properties of the composition if necessary or converting it into different products. Example 1 :

While the same thinner is used as in the epoxy resin composition (A) , phenylpropyleneglycol will change a filler or primes into an adhesive or a filled impregnation product with a much lower viscosity and is then eminently suitable for filling up tears in wood or concrete or as a sealer against moisture penetration or as an adhesive for wood, metal, plastic etc. Example 2 : Using the same and more hardener, for instance Euredur 76, the chemical resistance of the cured end products applied on a metal substrate as mentioned in examples 3, 4, and 5 -5- will improve the chemical resistance.

Other additives (E) , which can be used or mixed with (A) , (B) , (C)and (D) to modify the other physical properties of the cured and/or partly cured compositions include, but are not limited to epoxies, thinners used in the epoxies, thixotropes, toughening agents, wetting agents, surfactants, smoke suppressants, expanding agents, hollow microspheres, flow assisting materials, fusible glasses, stabilisers, lubricants molybdenum disulphide or polytetrafluoroethylene and abrasives such as silicon carbide, diamond, alumina, sand, silicates, ceramic vacuum balls, reactive polymers or copolymers like acrylate, alkyds, polyesters, nylon, biopolymers like vinylacetate and starch derivates of potatoes or rice etc, or polyurethanes etc. present in most standard paints.

For example, to modify the flexible, reactive or undercured or partly cured epoxy group containing composition with another modified, also reactive polymersystem to form a new range of better quality paints. They last longer than the present standards or become partly biodegradable in combination with new biodegradable polymers like biopolymers such as polyvinylacetate produced by bacteria. The ratio between this two types of polymers make it possible to adjust the desired performance, resulting in new possibilities for a new epoxy technology.

Examples of this invention are as follows:

A composition of a mixture (A) , which is packed in a tube and contains 72 weight % of a liquid epoxy (A) , fillers, pigments, thinners etc based on a modified epoxy resin A/F for example Riitapox BS 500 produced by Bakelite AG Duisburg or similar IRS analysis as indicated on appendix/enclosure 3) , and a composition of a solidifying or harderner system packed in two tubes. The first tube contains a harderner based on a polymercaptane, fillers, pigments, thinners, etc. with a geltime of about 5 minutes at room temperature. (standard 2) . - 6-

The second tube contains a composition of another solidifying and harder system, which contains a harder based on a polyetheramine, fillers, thinners, pigments etc. with a geltime of about 45 minutes at room temperature . (standard 1) .

Surprisingly we found that a mixing ratio of 1:1 by volume or by weight (epoxy/harderner or epoxy/two harderners) as well for the single products as for the mixed products will not give problems in curing or reaction problems with the standard paints such as alkyd or acrylates . The advantage is that the two products can also be used independently, for example tube 1 and tube 2 or tube 1 and 3. The flexibility of the mixed end product are higher and the improved processing properties also resulted into a cheaper finish due to the reduction of the application time. This invention makes it possible to use one system for all the applications of epoxy products for repairing, filling, priming, equalizing or as a coating for the protection of organic or anorganic materials. Application of fewer products since for instance preserving wood against woodrot is not necessary due to the increased quality of these products . (See also example 1).

By mixing a different flexible product with a partly cured epoxy composition with a polylyacrylate-, or a polyvinylacetate resin the physical properties of the products for instance against the uv light resistance using another toplayer can considerably be improved. Generally we can conclude that the flexibility of the partly cured epoxy composition compared with the completely cured epoxy is also surprisingly better.

Preferable is a combination of a harder based on a polymercaptane like Euredur 90 supplied by Witco GmbH Bergkamen Germany, which result in R-CH2-CH20H-CH2-S-R'

(see also infrared spectrum analysis, appendix/enclosure

1 of the R-S-H composition) and a second harder which -7- contains at least polyetheramine like Euredur 76 also supplied by Witco GmbH Bergkamen Germany. (see also infrared spectrum analysis, appendix/enclosure 2 the composition of the Euredur 76) .

This invention can be applied in two ways or applying the already mixed two endproducts based on the two harderners and epoxy composition, whether mixing the two harderners first and then adding the epoxy composition. In case the harderners are exposed to each other or thoroughly mixed together under normal conditions, there will be a strong negative influence on the flexibility, curing time and paintability of the product. Mixing in a workshop on the spot will prevent this problem as the following tests have showed.

Examples 3, 4 and 5:

A partly cured epoxy composition was prepared by mixing together 101, 95 and 103 grammes of an epoxy composition containing 72 % by weight of an epoxy resin packed in a tube 1, 32, 48 and 79 grammes of a harderner composition based on a polymercaptane like Euredur 90 packed in tube 2, and 70,47 and 24 grammes of a second harderner composition based on a polyetheramine like Euredur 76 packed in tube 3 until a homogeneous composition. In order to determine the flexibility of the partly cured end product the products were applied into a layer thickness of 2 mm on a polyethylene foil and cured at a temperature of 20 degrees centigrade and 40% humidity. After a period of 8 weeks the flexibility is determined of which the highest figure indicates the highest flexibility (1 to 4). Example 6 :

Using fillers as described above and by pressing them in a machine with static mixing tubes the thixotropic properties of the product will make the product suitable for spraying layers of 0,25-2 mm thickness in one turn. Only the the pressure of compressor have to be changed or another static mixing tube with a different length has to be used. This technology gives enormous advantages and is much cheaper in application costs in case more than one layer has be applied.

Quantity in example example example standard standard grammes 3 4 5 1 2

1) Epoxy resin 101 95 103 100 98

2) Harder or solidifying agent: Euredur 90 32 48 79 99

3) Hardener or solidifying agent : Euredur 76 70 47 24 101

Geltime in minutes 35 25 15 45 Temperature degr . centigr , 20 20 20 20 20

Drying time 16 hrs 3 hrs 12 hrs 24 hrs 1 hrs

Flexibility 1-2 1-2 advised advised suppliers suppliers ratio ratio epoxy/ epoxy/ hardener hardener d 167/250 167/200

Processing allows allows allows properties better better better compared with control control control the two cured 5 hardener compositions - 9-

Remarks :

All three examples show a better flexibility , easier mixingprocessing properties both by manual- as machinery equipment and a controllable and better adjustable curing system.

Also the tenability of the products used to repair or fill of wood, concrete or metal is limited and in practice a maximum a one year. They become chemical waste, hich can easily be prevented by converting or adjusting these two products into other valuable products like adhesives, coatings , mortars etc. in a workshop on the spot. (as already mentioned in example 1) . These examples give only an indication of the application of this invention and what it can do. It will be clear to people working with resins and hardeners of these types that many variations exist, both in the chemistry and the additives which can be used to influence the properties of the compositions in a workshop on the spot, which can be used in the industry for a range of new products.

The opportunity to use better products and to reduce the chemical waste will be an enormous advance and a challenge for the polymer technology such as epoxy, silicones, urethane, acrylate, alkyd, polyesterresins and especially the latest developments such as nylon based resins and the biomerpolymers like vinylacetate (latex) produced by bacteria and starch deratives which both are biodegradable in the environment. The products, without limiting, can be applied in the form of fillers, primes, adhesives, mortars and coatings for the timber, stone, concrete, plastic, metal such as the ship building and car industry, paper and textile industry.

Claims

-10- CLAIMS

1) A epoxy resin composition which is a functional reaction product by mixing together:

(A) epoxy resins or epoxy group containing compounds

(B) a partly cured system by using a hardener system of at least one harderner which will react with (A) to give a solid or solidified composition, but which is not present in sufficient quantities to allow or cause complete curing of (A) under the reaction conditions chosen (A) and (B) .

(C) a solidifying or an hardener system for (A) which consists of at least two hardeners of which one of the hardener remains separately unreacted under the conditons of reaction chosen for, but will be initiated by the speed of reaction of the other hardener and will partly cure the epoxy composition (A) .

(D) addition of the same components as already being present in (A), (B) or (C) to modify the physical properties of the composition.

(E) addition of other additives that may be required to modify the physical properties of the cured or partly cured epoxy resin compositions (A) or reacting them with other polymers which are cured or contain functional groups to react with the partly cured epoxy compositions.

2) A composition according to claim 1 where the epoxy composition is containing a liquid epoxy resin (A) .

3) A composition according to claim 1 and 2 where the majority of the epoxy groups are present as glycidylether, glycidyl amine glycidyl ester cycloaliphatic, a bisphenol A or bisphenol F diglycidylether, an epoxinovolak or other epoxy resins

4) A composition according to claim 1 to 3 where the hardener systems are present as polyetheramines and/or polymercaptanes.

5) A composition according to claim 1 to 4 where the hardener systems include amines, dicyandiamide, aromatic amines such -lias diaminodifhenyl sulphones, borontrifluride amine complexes, imidazoles, carboxylic acids, anhydrides, hydrazides and substituted ureas.

6) A composition according to claim 1 to 5 where (A) and the 5 application of (B) and/or (C) in a weight or volume ratio of 1:1 is used.

7) A composition according to claim 1 to 6 which is mixed, cast, pressed or formed to shape , cured or partly cured.

8) A composition according to claim 1 to 7 which is partly 10 cured and in contact with liquids, paints, primes, and/or other UV light resistance improving additives.

9) A composition according to claim 1 to 8 where to the composition of (A) , (B) , (C) an extra component (D) is added to the composition as already present in (A) , (B) and (C) .

1510) A composition according to claim 1 to 9 also contains (E) other polymer or copolymer resins and/or combinations or modifications of an alkyd, an acrylate, an urethane, a silicone, a nylon-based deratives, a polyester resin in or a biopolymer such as a vinylacetate or a resin derived from

20 starch.

11) A composition according to claim 1 to 10 where the cured material is contacted with or incorporated into another curable system to modify properties and the two systems are cured together.

2512) A composition according to claim 1 to 11 where the solidifying product is cured at room temperature

13) Mixing of at least two cured products with a different geltime according claim 1 to 12 in the form of fillers, primes, adhesives, mortars and coatings, without limiting,

30 for the timber, stone, concrete, plastic, metal such as shipbuilding and car industry, paper, textile industry etc.

14) Products according to claim 1 to 13 which are applied in or near the workshop on the spot.

15) Mixing of products with a different geltime and mixed in or 35 near the workshop making flexible cured or partly cured fillers, paints or other solidifying layers for the protectioning of material and/or reflection of light.