DE2700608A1 - NON-FLAMMABLE COMPOSITE INSULATION - Google Patents

Description

Non-combustible composite insulation

The invention relates to non-combustible composite insulation materials, consisting consisting of a core layer A with low density and outer layers B with high density and high mechanical strength applied to both sides Strength. The Wärmedämmeηde core layer contains inorganic Light particles that are connected to one another by high-temperature-resistant organic binders.

There is a need in the construction industry for insulating materials which should not be flammable according to DIN Ί102. Besides, they should good mechanical strengths, especially high compressive and flexural strengths, but also good edge stability and abrasion resistance exhibit.

Insulation materials made of inorganic light particles such as perlite and vermiculite are known. Both inorganic binders, such as cement, clay or talc, and organic binders, such as bitumen, starch or acrylic polymers, are used to glue the particles together. Temperature-resistant, high-polymer binders with a long-term use temperature according to DIN 53 M of more than 100 ^° C., as described, for example, in German patent application P 26 30 83 * i, are particularly suitable.

Insulation materials with inorganic binders stand out favorable fire properties; However, their densities are generally so high that they are due to their high coefficient of thermal conductivity as thermal insulation materials do not show a great effect. If the amount of binder is reduced, lower densities are obtained, however, the mechanical strength then decreases very sharply. When using organic binders, the lower Have permanent use temperature than 100 ° C, there is the disadvantage that a test in the fire shaft according to DIN 4102, sheet

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(3rd Pass from February 1970), Paragraphs 3.2 and 4.1, an undestroyed residual length of significantly less than 35 cm remains. When using organic binders, which have a Daucrgebrauchstemperatur of about 10O ⁰ C, one obtains namely a building material class A2 according to DIN 4102, the desired mechanical strengths are not achieved.

It has now been found that both goals, namely good thermal insulation and non-combustibility on the one hand and high mechanical strength on the other hand can be achieved if one has a core layer according to the German patent application P 26 30 834, which for the good Thermal insulation and is responsible for the non-combustibility, combined on both sides with cover layers that give the insulation material the give the necessary mechanical level.

The invention relates to a composite insulation material made of a core layer A and two top layers B, the layers having the following composition:

A) core layer:

99 to 60 wt. inorganic light _{particles A 1} with an average particle diameter between 0.05 and 3 mm and a bulk density between 30 and 150 g / l,

0 to 40% by weight of fibrous or granular inorganic additives A ₂ ,

wherein the particles are interconnected by

1 to 30 wt.% Of a heat resistant organic high molecular weight binder A, with a continuous use temperature according to DIN 53 146 of greater than 100 ° C,

B) top layers:

30 to 90 wt. a flat carrier material B ₁ from one another

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connected inorganic or organic fibers or wires.

0 to 60 wt.?) Of a fine-grain, water-insoluble mineral filler B ₉ with a grain size of 1 to 200 μm and a

3
Bulk density greater than 1 g / cm, and

3 to 30 wt.% Of a heat resistant organic high molecular binder B ,, with a continuous use temperature according to DIN 53 ΊΊ6 of more than 100 ° C

The finished composite insulation material preferably has a thickness of 10 mm to 100 mm, in particular from 10 to 60 mm, the cover layers 0.5 to 5, in particular 0.5 to 2 mm thick. The core preferably has a density of 70 to 300 g / l, the cover layers from 600 to 2000 g / l.

The inorganic light _{particles A 1} have an average particle diameter between 0.05 and 3 mm, preferably between 0.2 and 2 mm. Their bulk density is between 30 and 150, preferably between 10 and 100 g / l. Silicate materials are preferably used, such as water-insoluble alkali metal silicates with a SiOp: Me ₂ O ratio of greater than 4.5: 1 or silicates of main groups 2 and 3 of the periodic table. Expanded perlite or vermiculite are particularly preferred; however, expanded foam glass, fly ash or expanded plaster of paris are also suitable.

The core layer can optionally contain up to 40% by weight of fibrous or granular inorganic additives A ₂ . Fibrous additives improve the modulus of elasticity of the building materials. The fibers should have a length of 2 mm to 3 cm. Glass fibers, which are used in amounts of 2 to 10% by weight, and rock or mineral wool, which are used in amounts of 5 to 30% by weight, in each case based on the total mixture, are preferred. Granular additives improve the strength of the building materials. The grains should have a diameter of 1 to 100 μm. Talc or gypsum, which are used in amounts of 15 to 30% by weight, based on the total mixture, are preferred.

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In the core layers, the particles A ₁ and A ^ are connected to one another by 1 to 30, preferably 1 to 20 and in particular 2 to 10% by weight of an organic, high-polymer binder A. In the case of non-flammable insulation materials, the upper limit of the binding agent concentration is determined by the additional requirement of DIN Ί102, according to which the calorific value must be below 1000 kcal / kg. It depends on the type of binder and can easily be measured experimentally using the test specified in DIN-Morm. The lower limit of the binder concentration is given by the desired level of mechanical properties. The binders are preferably polycondensates with a continuous use temperature according to DIN 53 ')') 6 of more than 100 °. The permanent use temperature is defined as the temperature at which the substance in question can be stored in the air for 25,000 hours without any noticeable change in its properties.

In the production of the core layers, preference is given to using 1 to 50, preferably 2 to 10% by weight, preferably aqueous dispersions or solutions of precondensates A-, ^{1 which} can be hardened to form the high-polymer binder A-, which optionally contain conventional dispersion stabilizers, crosslinking agents, May contain catalysts, leveling agents or other additives in small amounts. In principle, the binders can also be used as a dispersion or solution in organic solvents; then, however, a separate solvent work-up is necessary, which leads to energy and environmental problems. The precondensates A-, ¹ cure at elevated temperatures, optionally in the presence of crosslinking agents or crosslinking catalysts, with further condensation or crosslinking to form the high-polymer binder A-. In principle, however, it is also possible to use dispersions or solutions of those binders A, which are already in high molecular weight form.

Examples of suitable binders A are: polyesterimides, Polyamide imides, polyimides, polyesters, polyamides, polybenzimidazoles, polyoxazoles, melamine / formaldehyde resins, urea / formaldehyde resins and phenol / formaldehyde resins and mixtures of these.

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Polycondensates containing anabolic inide rings are particularly preferred, i.e. polyesterimides, polyamideimides and polyimides.

Aqueous dispersions of Polycsterimideri are described, for example, in German Offenlegungsschrift 22 10 i \ 8> \ and 23 51 077. Hs are polycondensation products of aromatic polycarboxylic acids, polyhydric alcohols and polyhydric amines. They generally contain, ^r '.' - to 7, preferably 1 to 5 Hcw.'i imide nitrogen iriForm of fünfrliedrigeri Iniidringcri which are arieliiert having aromatic nuclei. The following raw materials can be used for their production:

10 equivalents of aromatic tri- or tetracarboric acids, their Anhydrides or esters, e.g. trimellitic acid, pyromellitic acid or their anhydrides, optionally together with aromatic dicarboxylic acids or their esters, e.g. terephthalic acid, isophthalic acid or iaphthalenedicarboxylic acid, as well as their lower alkyl esters;

5 to 20 equivalents of lower aliphatic diols, optionally together with 3- or 'J-valigori alcohols, for example ethylene glycol, Propylene glycol, butanediol, together with glycerin, trimethylolpropane or trishydroxyethyl isocyanurate;

1 to 5 equivalent di- or tri-primary amines, for example Ethylenediamine, hexamethylenediamine, benzidine, piaminodiphenylmcthan, diaminodiphenyl ketone, diamiriodiphenyl ether or diaminodiphenyl sulfone, Phenylenediamine, tolylenediamine, xylylenediamine or Mg1amiη.

The starting materials can - preferably in the presence of solvents - Either condensed together, or precondensates can be used, e.g. diimide dicarboxylic acids from 2 moles of trimellitic anhydride and 1 mole of a diprimary aromatic amine.

The production of polyesterimidone is described, for example, in the German Auslegeschriften 1 '»' (5 263, l't 95 100, 1 * 4 95 152 and 16 45> 05, as well as in DT-OS 2'I 12 HJl.

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In the aqueous dispersions, the polyesterimides are in particle form with average Tcilcheridurchmcssern below 50, preferably below 5 µm. They generally contain from 0.01 to 5, preferably 0.1 to 3 wt.% Dispersant, wherein, before all the polar group-containing high polymeric organic substances come into question, such as polyvinyl alcohol, cellulose ether, polyvinyl pyrrolidone, polyacrylic acid, partially hydrolyzed copolymers of Acrylestern and Acrylonitrile; copolymers of vinyl pyrrolidone and vinyl propionate are preferred. In addition, they contain crosslinking catalysts in amounts of 0.5 to 5 wt. ", Eg Oxotitanate, triethanolamine titanate, titanium lactate or titanium oxalate. Moreover, they may contain flow-control agents, thickeners, Antithixotropiermittel and neutralizing agents. When curing at temperatures above 200 to 220 ⁰ C occurs a further condensation and crosslinking the polyesterimides.

Polyamide-imides are condensation products of a tricarboxylic acid anhydride and an aromatic diamine (DT-OS 15 20 968, 15 95 and 17 20 909). Aqueous dispersions of polyamide-imide precondensates are described, for example, in DT-OS 25 28 251. They are prepared by reacting 2 moles of tricarboxylic anhydride, preferably trimellitic anhydride, with 1 mole of an aromatic diamine in an aliphatic diol as solvent, esterification of the diimide dicarboxylic acids formed ir. it dom diol and subsequent displacement of the diol by an aromatic diamine with formation of anide. The pre-condensate obtained has a degree of condensation between 1 and 10, preferably between 2 and 5. It can be ground and dispersed in water. This aqueous dispersion can also contain the usual additives, such as dispersion stabilizers and esterification catalysts. Upon curing at temperatures above 200 to 22O ⁰ C further condensation occurs with chain extension.

Polyimides are condensation products of aromatic tetracarboxylic acids or their derivatives and aromatic diaminone (DT-AS 12 02 98I, 1 '»20 706). Aqueous solutions of polyimide precursors, the polyamic acids, can by reacting Tctracar-

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Acids (preferably pyromellitic acid) can be prepared with aromatic diamines in aqueous solution in the presence of ammonia and amines (DT-OS 17 20 836, GB-PS 1 176 853). Upon curing at temperatures above ¹ I IO to l60 ° C Weiterkondcnsation occurs to the polyimide.

Crosslinked polyesters, preferably those based on aromatic dicarboxylic acids, are also suitable. Here you can buy waftrigo dispersions or to produce solutions that or only the uncritical contain slightly crosslinked polyester together with polyols as crosslinking agents. When curing at temperatures above about 130 to 150 ° C further condensation occurs with crosslinking.

Strongly crosslinked melamine / formaldehyde and phenol / formaldehyde resins are also suitable. Pre-condensates made from melamine, phenol, cresol or higher alkyl phenols with formaldehyde, which have weights of between about 200 and 1200, are used here. For further crosslinking, formaldehyde can be added as formalin or hexamethylenetetramine. Reim curing at temperatures above about 120 ° C occurs IUO ⁰ V / pus condensation among crosslinking. Substituting conventional hardener to, it may also be crosslinked below 120 ⁰ C.

Component B _{1 of} the outer layers is a flat carrier material made of interconnected inorganic or organic fibers or wires, which preferably do not soften or expand at temperatures below 150 ° C. Glass fiber fleeces and glass fiber logs are particularly suitable; however, loosely laid glass fibers or grids made of glass fibers or metal wires can also be used. Cellulose masses, for example paper, are also suitable. The glass fibers can be provided with the usual layers.

Fine-grained, water-insoluble mineral fillers with a grain size between 1 and 200 μm, preferably between 1 and 50 μm, may be used as component B _{2 of the outer layers}

3
A bulk density of greater than 1 g / cm is used. Here come m

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Question: plaster of paris, cement, pumice powder, quartz powder or metal oxides; preferred are silicates such as talc, kaolin or mica.

As component B ₇ . The same temperature-resistant organic high-molecular binders can be used as for component A-, the core layer. Component B is preferably used in amounts of from 5 to 20 wt.%.

The composite insulation boards according to the invention can be according to various Process are produced.

In a preferred embodiment, the starting materials are mixed of the individual layers, preforms them without compacting them, places the preformed layers on top of one another and presses them together then with the application of heat. In principle, however, it is also possible prefabricate the individual layers and glue them together, preferably non-flammable adhesives, e.g. based on water glass, are used.

The core layer A can basically be preformed in two ways will:

1. In a preferred embodiment, the lightweight articles A ₁ are sprayed with an approximately 1 bin BO, preferably 2 to 20 days by weight, aqueous dispersion or solution of the binder A- or a binder precondensate A-, the particles in usual mixing machines are kept in motion. It is a particular advantage of the use of aqueous binder systems that a particularly fine and uniform distribution of light particles and binder is obtained. The product is then mechanically freed from some of the water and, in the moist state, is pre-pressed together with the outer layers and, if necessary, cured in the process. If the core layer is to _{contain fibers A 0} , the fibers are first slurried with stirring in water which contains surface-active substances as customary disintegrating agents. This will be done then

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the binder dispersions or solutions, as well as the light particles given and mixed vigorously. Most of the water is on a sheet former common in the paper industry sucked off.

2. In another embodiment, the aqueous dispersion or solution of a binder precondensate A-, 'on the inorganic Conductive particles A., if necessary in a mixture with additives Ap sprayed on, and then dried at temperatures below the curing temperature of the binder. Preferably this happens at 100 to 180 ° C, in particular at 110 to 160 ° C in a fluidized bed or in other conventional mixing units. The dry mixture obtained is then pressed together with the outer layers, with the binder precondensates Harden.

The outer layers B can be produced by analogous processes. The carrier material aqueous dispersion of the binder B, or one to the binder B, curable precondensate B, ^1, and optionally the filler B ₂ B is preferably ₁ wt with a 1 to 80, preferably Ί0 to 75 ^. Impregnated, the mass is predried and the cover layers thus preformed are pressed moist with the preformed core layer A and optionally cured.

The compression of the core layer A and surface layers B takes place at temperatures above the curing temperature of the binder precondensates A, ¹ and B ', preferably at temperatures above 150 ⁰ C, in particular between 200 and 300 ° C at a pressure of 1-30 bar, preferably between 1 and 10 bar. The curing temperature differs from binder to binder. It is also not a precisely defined temperature, but a temperature range: at the lower limit, curing takes a very long time; at the upper limit, curing takes place momentarily. The temperature selected in this process step is accordingly based on the residence time specified by the press equipment. The pressing process is carried out in heated press units,

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e.g. in belt presses. It generally lasts for about 2 to 20 minutes.

The insulation materials according to the invention can be used for decorative purposes or be laminated with foils, e.g. on aluminum, to increase fire resistance.

The parts and percentages given in the examples refer to each other on weight.

example 1

A. Making the core layer

A polyesterimide made from terephthalic acid, glycol, trishydroxyethyl isocyariurate, trimellitic anhydride and diaminodiphenylmethane is used as a 6-strength aqueous suspension as the binder precondensate A _1. The suspension contains, based on solids, 3 % of a copolymer of vinyl propionate and vinyl pyrrolidone, and 1 % triethanolamine titanate. 95 parts of expanded perlite with an average particle diameter of 0.7 and a bulk density of 70 g / l are sprayed with this dispersion (5 parts of solids), mixed intimately in a gravity mixer and dried at 130.degree.

B. Manufacture of the top layers

ρ paper with a basis weight of about 150 g / m 2 is

Minium foil with a thickness of 15 μm (surface weight 40 g / m) bonded by 30 % (based on solids) of a 70% aqueous phenolic resin of the resol type made from 1 kmol phenol and 1.6 kmol formaldehyde.

C. Manufacture of the composite insulation material

On both sides of the core layer A, the prefabricated cover layers B are placed with the paper side. By pressing

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a tabular insulating plate produced which is thermally heated to about 25O ⁰ C, the binder being crosslinked.

The insulating plate has the following properties:

Density: 220 g / l

Thermal conductivity: 0.05 kcal / mh ⁰ C

2
Compressive strength: 0.75 N / mm

Flexural strength: 1.0 N / mm ²
Water absorption: 25 vol.
h under water)

Example 2

A. Making the core layer

9k parts of a 70% strength aqueous phenolic resin of the resol type, which is obtained from 1 kMol phenol and 1.6 kMol formaldehyde, mixed with 6 parts of an alkylated phenolic resin precondensate based on nonylphenol / formaldehyde are used as the binder precondensate. 17 parts of the binder mixture are intimately mixed with 83 parts of perlite with a bulk density of 75 g / l in a gravity mixer.

B. Manufacture of the top layers

35 parts of a glass fleece are impregnated with a pasty mass of 35 parts of kaolin and 30 parts (solids) of the binder mixture described under A and MO % water.

C. Manufacture of the composite insulation material

The insulation plate is produced essentially analogously to Example 1. Here, however, it is compressed to approx. 200 g / l and ^{heated to approx. 100 °} C. by means of high frequency, the binder hardening.

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Characteristics:

Thermal conductivity: 0.05 kcal / m.h. ° C

Compressive strength: 0.8 N / mm

Flexural strength: 0.9 N / mm

Water absorption: approx. 1 Vol.X

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Claims (10)

O.Z. 32 Claims Ö Non-combustible composite insulation material consisting of a core layer A and two outer layers B, characterized in that the layers have the following composition: A. Core layer: 99 to 60 wt. inorganic light _{particles A 1} with an average particle diameter between 0.05 and 3 mm and a bulk density between 30 and 150 g / l, 0 to ^ O weight! " fibrous or granular inorganic additives A ₂ , wherein the particles are interconnected by 1 to 30% by weight of a temperature-resistant organic high molecular weight Binder A, with a continuous use temperature according to DIN 53 M 6 of more than 100 ° C. B. Top layers: 30 to 90% by weight of a flat carrier material B ₁ made of interconnected inorganic or organic fibers or wires, 0 to 60% wt. Of a fine, water-insoluble mineral filler B ₉ having a grain size of 1 to 200 um 3 and a bulk density of greater than 1 g / cm, and 3 to 30% wt. Of a temperature resistant organic high molecular binder B, with a continuous use temperature door according to DIN 53 M6 of more than 100 C. 2. Non-combustible composite insulating material according to claim 1, characterized in that the inorganic light particles A _{1 are} expanded perlite or vermiculite. 809829/0052 - m - ORIGINAL INSPECTED -} A - o.z. 32 369 3. Non-combustible composite insulating material according to claim 1, characterized in that the additives A _{2 are} glass fibers of a length between 2 mm and 5 cm. 4. Non-combustible composite insulating material according to claim 1, characterized in that the binders A are polycondensates. 5. Non-combustible composite insulating material according to claim 1, characterized in that the binders A ^ are polyester imides or polyamide imides. 6. Non-combustible composite insulation material according to claim 1, characterized in that the binders A are highly crosslinked melamine / formaldehyde or phenol / formaldehyde resins. 7. Non-combustible composite insulation material according to claim 1, characterized in that the flat carrier material is glass fiber fleece or glass fiber scrim. 8. Non-combustible composite insulating material according to claim 1, characterized in that the mineral fillers B _{1 are} silicates, preferably talc, kaolin or mica. 9. Non-combustible composite insulation according to claim. 1, characterized in that the binders B are polycondensates. 10. A method for producing the insulating materials according to claim 1, characterized by the following steps: The starting components A ₁ and optionally A ₃ or B ₁ and optionally B ₂ are mixed with 1 to 80% strength by weight aqueous dispersions or solutions of the binders A or B or of to the binders A or B -. curable precondensates A, ¹ or B 'mixed or soaked; the layers A and B are preformed and optionally dried; 809829/0052 - 15 - O. Z. 32 the pre-formed layers are in the layer sequence c B-A-B together Finally, the preformed layers are pressed together at temperatures above 100 ° C. and pressures between 1 and 30 bar, the precondensates />, 'and B ₇ . ¹ cure. BASF Akticncescllschaft 809829/0052
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