CZ20002749A3 - Composition of mineral wool - Google Patents

Abstract

In the present invention, there is disclosed a mineral wool capable of dissolving in physiological medium and containing the following components: 35 to 60 percent by weight of SiOi2, preferably 40 to 55 percent by weight, 5 to 18 percent by weight of Ali2Oi3, preferably 6 to 16 percent by weight, 50 to 75 percent by weight of SiOi2 + Ali2Oi3 + Pi2Oi5, preferably 55 to 65 percent by weight, 20 to 40 percent by weight of RO (CaO + MgO), preferably 22 to 35 percent by weight, 2.8 to 10 percent by weight of Ri2O (Nai2O + Ki2O), preferably 3.5 to 8 percent by weight, 2.6 to 8 percent by weight of Pi2Oi5, preferably 3 to 6 percent by weight, 1 to 15 percent by weight of Fei2Oi3, preferably 3 to 10 percent by weight, 0 to 3 percent by weight of Bi2Oi3, 0 to 3 percent by weight of Ti{OMICRON}i2, preferably 0.05 to 3 percent by weight whereby the wool meets a criterion based on the ratio of R1 such that R1 = (SiOi2 + Ali2Oi3)/Pi2Oi5, wherein R1 is in the range of from 12 to 20.

Description

Composition (for mineral wool)

Field of the invention

The invention relates to the field of artificial mineral wool. In particular, it relates to mineral wool intended for the production of thermally insulating and / or acoustically insulating materials or substrates of alien cultures.

In particular, the invention is concerned with rock wool-like mineral wool, i.e. wool whose chemical composition results in high liquidus temperature and high fluidity at the spinning temperature associated with the high glass transition temperature.

BACKGROUND OF THE INVENTION

This type of mineral wool is usually spun by external centrifugation processes, for example, using a centrifugal drum set to which molten mass is fed by a static distribution device, as described in particular in European patents EP-0 465 310 or EP-0 439 385.

The mineral wool biodegradability criterion has been added to the already known criteria of industrial and economic feasibility and quality level for several years, ie its ability to dissolve rapidly in physiological environment in order to avoid any potential pathogenic risks associated with possible accumulation of the finest fibers in organism .

* · · · ·

An initial solution to the problem of selecting a rock-type mineral wool composition with a bio-insoluble character is to use a very high alumina content.

It is an object of the present invention to improve the chemical composition of the rock-type mineral wool, particularly in order to increase their biodegradability and / or link their biodegradability to the spinning capability in particular, particularly advantageously, by external centrifugation without excluding other spinning methods.

SUMMARY OF THE INVENTION

The object of the invention is a mineral wool capable of dissolving in a physiological environment, which contains the following components in the following weight content:

SÍO ₂ 35-60 % with advantages ou 40-55 % ^A1 ° 2 5-18 % 6-16 % S i 0 ₂ + Α12θ3 ^{+ Ρ} 2θ5 50-75 % 55-65 % RO (CaO + MgO) 20-40 % 22-35 % R ₂ 0 (Na ₂ 0 + K ₂ 0) 2,8-10 % 3,5-8 % ^P 2 ° 5 2,6-8 % 3-6 % ^Fe 2 ° 3 1-15 % 3-10 % ^B 3 ° 3 0-3 % tío ₂ 0-3 % 0,05-3 %

and which satisfies the criterion based on the ratio R1, such that R1 = (SiC > 2 + A.I2O3) / P2O5, wherein R1 is in the range of 12 to 20.

Iron content, Fe ₂ 0 ₂ means the sum of the various iron oxides contained in the composition (ferrous, ferric, etc.) expressed as Fe ₂ O3

The silica content, S1O2, in the selected compositions is in the range of 35 to 60% by weight, preferably higher than 38% by weight, in particular higher than 40% by weight and / or preferably lower than 58% by weight, particularly lower than 55% by weight . For selected compositions containing 5 to 12% by weight of Al2O3, this content is preferably greater than 45% by weight, in particular greater than 48% by weight, and for selected compositions containing 12 to 18% by weight of Al2O3, it is preferably less than 50% by weight, especially less than 45% by weight.

The content of alumina, Al 2 O 3, in the selected compositions is in the range of 5 to 18% by weight, preferably higher than 6% by weight and / or preferably lower than 17% by weight, in particular lower than 16% by weight.

The content of alkaline earth metals, RO, corresponds to the sum of calcium oxide CaO and magnesium oxide MgO. The selected compositions have an RO in the range of 20 to 40% by weight, in particular greater than 22% by weight and / or preferably less than 35% by weight.

RO can be predominantly CaO or MgO.

The content of calcium oxide, CaO, in the selected compositions ranges from 0.1 to 35% by weight. According to a first variant of the invention, the CaO content is small, in the range of 0.1 to 2% by weight. According to a second variant of the invention, the CaO content is reduced, greater than 2% by weight and less than 10% by weight. According to a third variant of the invention, the CaO content is high, preferably higher than 10% by weight, in particular higher than 15% by weight

And / or preferably less than 30% by weight, in particular less than 25% by weight.

The content of magnesium oxide, MgO, in the selected compositions ranges from 0.1 to 35% by weight. According to a first variant of the invention, the MgO content is small, in the range of 0.1 to 2% by weight. According to a second variant of the invention, the MgO content is reduced, in the range of 2 to 10% by weight, preferably higher than 5% by weight, in particular higher than 6% by weight. According to a third variant of the invention, the MgO content is high, in particular higher than 10% by weight, preferably lower than 20% by weight, in particular lower than 15% by weight.

The alkali metal content, R ₂₀ = Na ₂ O + K ₂ O, in the selected compositions is in the range of 2.8 to 10% by weight, preferably greater than 3% by weight and / or preferably less than 8% by weight, in particular less than 6% by weight. For selected compositions containing 5 to 12% by weight Al ₂ O ₂ , this content is preferably higher than 3.5% by weight, in particular higher than 4% by weight.

r ₂ ° may consist mostly of Na ₂ 0 or K ₂ 0.

Low Na ₂ O compositions contain, in particular, 0.1 to 1% by weight of Na ₂ O.

Low K ₂ O compositions contain, in particular, 0.1 to 1% K ₂ O by weight.

The phosphorus content, P ₂ O 4, ^{in the} selected compositions is in the range 2.6 to 8% by weight, preferably higher than 3% by weight, in particular higher than or equal to 3.2% by weight and / or preferably lower than 8% by weight in particular less than 6% by weight and optionally less than 5% by weight.

The iron content, Fe ₂ O ₂ , in the selected compositions ranges from 1 to 15% by weight, preferably higher than 3% by weight, in particular higher than 5% by weight, and / or preferably lower than 10% by weight, particularly lower % by weight.

In the following, all percentages of the components of the composition will be expressed as percent by weight and the compositions of the invention may contain up to 2 or 3% of compounds evaluated as non-analytical impurities, as is known in the art of such compositions. Possible TiO ₂ contents are considered to be impurities often occurring in the group of these compositions.

The choice of this composition has made it possible to cumulate a number of advantages, particularly in terms of the multifaceted and complex functions given by a number of its specific components.

In this way, therefore, a composition based on mineral wool of the rock type: the content of alkali metal oxides (R ₂ 0) primarily in the form of Na ₂ 0 and / or K ₂ 0 is decreased, generally less than 10%, preferably less than 6 %. At the same time, its content of alkaline earth metal oxides (RO), in particular in the form of CaO and / or MgO, is high, generally at least 20% and even more preferably at least 22%.

The spinning viscosity of this composition is suitable for external centrifugation.

• ·· · ·· «· ··

As far as biodegradability is concerned, it is known that certain components, for example? 2θ5, make it possible to significantly improve it, especially in rock type compositions, while other oxides tend to reduce it, at least at neutral pH. In this regard, reference may be made, for example, to European patent EP-0 459 897 and published international patent application WO 93/22251. However, a significant addition ^{is not} considered the most sensible way ^{in the} context of the present invention. In fact, other reasons may come to the forefront, for example economic (θ2θ5 comes from expensive raw materials) and also technical: changes in the amount of 52θ5 ^{and, for} example, alumina, may change other properties in the composition in an undesirable or unknown sense. ? 2θ5 ^M, and also affect the viscosity of the composition, just like alumina. The viscosimetric behavior of the composition is an important criterion for rock type compositions which are spun by external centrifugation to which the invention relates most.

In addition, some compounds may be of interest for certain properties, yet unfavorable due to the high biodegradability, which is an example of iron, advantageous, for example, for obtaining a good fire-resistance of mineral wool but reducing the rock wool biodegradability.

In addition, it is preferable to limit the alumina content to lower values, particularly below 18%. Solutions with a very high alumina content, of the order of 20%, generally lead to high raw material prices, especially because of the use of bauxite.

The term area of medium alumina compositions refers to a region of rock type compositions where 5% with an A 0 O 18 of 18%.

Ί · · · ·

The invention thus provided a reasonable compromise between all of these relevant data in the following manner: the composition comprises? 2θ5 ^{'and e} ^ ^sn Controlling ^the range 2.6 to 8%, and especially greater than 3% and / or less than 6%. It also contains at least a low iron oxide content which may appear to be advantageous (or unavoidable in trace amounts) but for reasons other than biodegradability. However, the composition achieves a high level of biodegradability without much addition of? 2θ5 by another means, in particular the relative ratio of the sum of the SiO2 and Al2O3 components relative to the P2O3 content.

Generally, rock type compositions having a significant alkali metal content contain a relative amount of S1O2 and Al2O3 based on the amount of P2O3 of either relatively high, about 20, especially greater than 50, or relatively reduced, about 10.

The invention relates to the field of compositions having an average alumina content in the range of 5 to 18% Al2O3, where P2O3 plays a particularly effective role in solubility in a living organism when the ratio R1 = (S1O2 + ^ 2θ3 ^ / ^ 2θ5 is in the range 12-12 20, and in particular greater than 13 and / or less than 18.

This selection has been shown to allow satisfactory fulfillment of the organism's solubility criteria, which can be measured by in vitro neutral pH tests or in vitro acid pH tests. In fact, it has not yet been decided which pH is most representative in the physiological environment in vivo, particularly in the lung area.

The invention makes it possible to obtain a high level of solubility in the body, at least measured in vitro, in that it

the mean alumina content and the reduced phosphorus content, adapting in particular the phosphorus content in relation to the S1O2 + Al2O3 content so as to obtain a beneficial effect at acidic or neutral pH.

It should be noted that the sum of SiC> 2 + Al 2 O 3 + Ρ ₂ θ5 makes it possible to largely regulate the viscosimetric behavior of the compositions and that it is preferably in the range of 50 to 75%, especially more than 55% and / or less than 65%.

Composition based on mineral wool according to the invention preferably comprises a plurality Ρ ₂ θ5 ^vs. T ^and drives the content of alkali metal such that the ratio R 2 = P ₂ C> 5 / R ₂ O is in the range 0.5 to 2, particularly more than 0.6 and / or less than 1.5. This criterion makes it possible to obtain a number of compositions in which the viscosity is particularly adapted to spinning by external centrifugation and which have sufficient solubility in the body.

Likewise, the amount of iron Fe ₂ O ₂ which satisfies a ratio R 3 = Ρ ₂ θ5 / Ρ ^ε 2θ3 in the range of 0.2 to 1.5, in particular higher than 0.5 and / or lower than 1, allows simultaneous satisfactory viscosity values to be obtained and good solubility in the body.

For compositions in the middle alumina region, particularly located in the lower part of the region, particularly with an Al 2 O 3 content in the range of 5 to 12%, it has been stated that these compositions having a silicon to phosphorus ratio representing R4, R4 = SiC 4 / Pgg, in the range of 11 to 20, and in particular greater than 12 and / or less than 16, provide very good solubility results in the living organism.

φ φ φ φφ φ 4

Φ Φ • φ Φ Φ • Φ • •

Of these series of compositions, those that additionally satisfy the criterion defined by the ratio R 5 where

R 5 = Al 2 O 3 / R 2 O, in the range of 0.5 to 4, especially less than 3.

Similarly, the compositions of the medium alumina region located particularly in the upper part of the region, in particular with an Al 2 O 3 content of 12 to 18%, were found to have an aluminum to phosphorus ratio forming a ratio R 6 where R 6 = Al 2 O 3 P2O5, in the range of up to 6, and in particular greater than 3 and / or less than 5, provide very good solubility results in the living organism.

Among these series of compositions, those which additionally satisfy the criterion defined by the ratio defined by the ratio R 7, where R 7 = SiO 2 / R 20, in the range of 8 to 20, especially higher than 10 and / or lower than 15, are particularly preferred.

Boron oxide may not be present in the composition or may be present in trace amounts, particularly in the range of 0.05 to 1%.

The addition of boron oxide, which is optional, in particular in an amount of 1 to 3%, may make it possible to improve the thermal insulating properties of the mineral wool, in particular by reducing the thermal conductivity coefficient in its radiation component.

The composition may also optionally contain TiO 2 as an impurity or specifically added, for example in an amount of up to 1 to 2

%.

99 99 99 99 99

The difference TqQgi-Tj2 is at least 10 ° C, preferably at least 50 ° C, in particular at least 100 ° C: this difference defines the working range of the compositions according to the invention, i.e. the temperature range over which they can be fiberized, especially by external centrifugation . Does the Tq -? Temperature (in ° C) corresponding to a viscosity of 7? (in poisons), where log Tf = 1, and the liquidus temperature (in ° C).

Mineral waves such as the above have a satisfactory level of solubility in the body, as measured by a method assuming either a neutral or slightly basic or acidic pH.

The mineral wool of the invention generally has a dissolution rate of at least 30, preferably at least 40 and even at least 50 ng / cm per hour (especially measured for silica), measured at pH 4.5 and / or at pH 6.9 and / or at pH 7.5.

In particular, the mineral wool of the invention has a composition specially adapted for spinning glass by external centrifugation.

These mineral wool are used primarily for the production of heat and / or acoustically insulating products or substrates of alien cultures. It is also an object of the present invention to include all products containing at least partially defined mineral wool.

φ · φ φ · · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ · · ·

DETAILED DESCRIPTION OF THE INVENTION

Further details and characteristics will emerge from the following description of preferred embodiments of the present invention, which are to be taken as examples only and are not intended to limit the scope of the invention in any way.

The following Table 1 summarizes the chemical composition in% by weight for the four examples of the invention (Ex. 1-4) and for the three Comparative Examples (Ex. 5, 6 and 7).

If the sum of the contents of all components is slightly less than 100%, it is understood that the residual content corresponds to non-analytical impurities / minor components, with values of not more than 0.5 to 1% being due to an approximation acceptable in this field of the analytical methods used.

The compositions of the examples were spun by external centrifugation, especially according to the recommendations of the previously cited patents.

Their workplaces defined by the difference T ^ _O g - ^ - T- £ j; were highly preferred and preferably greater than 250 ° C for Examples Pr 1 and Pr 2.

All of these compositions had a ratio (SiO2 + -2-3) /? 2θ5 in the range of 12 to 20. The first four examples had an alkaline content in the range of 3 to 10, while an Ex5 had an alkaline content of 1.2 and is therefore a comparative example.

A comparative example, Ex. 6, corresponds to a rock-type mineral wool composition, soluble in a living organism, with a very high concentration.

A A A A A A A

A «99 ·· 99 99 99 high alumina content.

Comparative example, Pr 7 corresponds to a medium alumina composition (at the top of this region) containing a small amount of? 2θ5 ·

Oxide dissolution rate measurement results

The silica, KSiCl 2, expressed in ng / cm per hour is shown in Table 1.

The exponent (P) data represent the powder measurement results.

The data indicated by the exponent (F) represent the results of the fiber measurements.

Powder measurements were performed according to the method proposed by the German Glass Society described in L. Springer, Laboratoriumbuch fur die Glassindustrie,

3rd Edition, 1950, Halle / S: W. Knapp Verlag.

The KS102 values measured on the powder were generally considered satisfactory if they were greater than 500, preferably greater than 1000 ng / cm per hour.

The dissolution rates of silica, K 2 O 2, were measured by an in vitro assay in a liquid buffered to a pH of about 7.4 to 7.5 labeled neutral liquid or an in vitro assay in a liquid buffered to a pH of about 4.5 labeled acidic liquid.

Based on these results, a surprising and positive effect of θ2θ5 ^on solubility in living organisms was found • 9 9 99

9

99 • 99,999 99,999 99 9

9999 9999 9999 • 9 99 99 99 9 9 99 for compositions with a moderate Al 2 O 3 content.

The important role of alkaline substances in compositions with moderate Al 2 O 3 content was also noted. The solubility values of S1O2 pH neutral at Pr 5 are very inadequate (particularly below the values of KS1O2 at Pr6 at pH neutral, which is used to present insufficient dissolution values at pH neutral, while KS1O2 at acidic pH at Pr 6 are considered satisfactory ).

Accordingly, these results indicate that the mean alkaline content makes it possible to obtain high K 2 O 2 values measured in a neutral and / or acidic liquid, for compositions with an average alumina content.

44 4 4 4 44 4 4 4 4 4

44

Table 1

4 4 4

4 4 • 44

4 4

4 4

44

AT PŘ2 PŘ3 PŘ4 | From “PR5 PŘ6 PŘ7 SiO ₂ 50.3 53.2 40.1 40.3 53.4 39.8 54.6 ΑΙΑ 7.1 6.2 14.0 16 5.8 22.4 17.2 CaO 21.5 18 21.8 20.1 24.2 14.6 7.4 MgO 6.45 6.6 12.3 11.8 4,5 9.8 4.8 R ₂ O 4.7 5.7 3.0 3.1 1,2 2.8 5.7 Fe ₂ O ₃ 5.8 6 5.8 5.6 6 7.5 8.6 Ρ 2θ5 4.2 4.3 3.3 3.2 4.1 0.6 0.25 no ₂ 0.02 0.02 0.02 0.02 0.35 1.9 1.1 ZrO ₂ 0.3 TOTAL 100 ALIGN! 100 ALIGN! 100.1 100.1 99.9 99.4 99.7 R1 - (C10 ₂ ♦ AljOjJ / FjOj 13.7 13.8 18.4 17.6 14.4 100 ALIGN! 290 R2 → P10 / R10 0.9 0.75 1.1 1 3.4 0.2 0.04 R3-P10O / FeaOa 0.7 0.7 0.6 0.6 0.7 0.1 0.03 R4 = SiO / P ₂ O ₃ (for 5 <AI ₂ O ₃ <12) 12 12.4 13 R5 = AA ^{/ R} a ° (for 5 i AI ₂ O ₃ S 12) 1.5 1.1 4.8 R6 = AIAIPiO, I for 2 a AI ₂ O ₃ a18) 4.2 5 37 70 R7 = S (0YR, 0 (for 2 AI ₂ 0, £ 18)) 13.4 13 14 9.8 (-C) 1500 1580 t '' ( ^D C) 1230 1230 KSIO ₃ neutral liquid 970 ^<η 1990 ^ 20 ^ 40 ⁽ⁿ 50 ^ 240 <p> KSiO ₃ acidic liquid 3800 ^(P) 6600 ^ 30 ^{, fi} 100 < ^p 1800 ^(P!

Claims (10)

PATENT CLAIMS 1. Mineral wool capable of dissolving in a physiological environment, characterized in that it contains the following components, the content by weight of which is given by weight: Si ° ₂ 35-60 % preferably 40-55 % ^A1 ° 2 5-18 % 6-16 % SiO ₂ + Al ₂ O ₂ + P 2θ5 50-75 % 55-65 % RO (CaO + MgO) 20-40 % 22-35 % R ₂ 0 (Na ₂ O + K ₂ O) 2,8-10 % 3,5-8 % ^P 2 ° 5 2,6-8 % 3-6 % ^Fe 2 ° 3 1-15 % 3-10 % ^B 3 ° 3 0-3 % tío ₂ 0-3 % 0,05-3 % wherein further the ratio R1 corresponding to R 1 = (SiO 2 + Al 2 O 3) / Ρ ₂ θ5> is in the range of 12 to 20. Mineral wool according to claim 1, characterized in that the ratio R1 is in the range of 13 to 18. Mineral wool according to any one of the preceding claims, characterized in that the ratio R2 corresponding to: R 2 = P ₂ O ₅ / R ₂ O is in the range 0.5 to 2, preferably 0.6 to 1.5. Mineral wool according to one of the preceding claims, characterized in that the ratio R 3, corresponding to the pic pik & σ-ρ 16 of the relation: R3 = Ρ2θ5 / ^ ^{ε 2θ3} is in the range from 0.2 to 1.5, preferably 0.5 and 1. Mineral wool according to any one of the preceding claims, characterized in that it contains an amount of alumina A AC ^ which corresponds to 5% - A1 ₂ O ₃ 12% with ratio R4 corresponding to: R 4 = SiO ₂ / P ₂ O ₅ is in the range of 11 to 20, preferably 12 to 16. Mineral wool according to claim 5, characterized in that the ratio R5, corresponding to: R 5 = Al ₂ O ₃ / R ₂ O is in the range of 0.5 to 4, in particular less than 3. 7. Mineral wool according to one of claims 1 to 4, characterized in that it contains an amount of aluminum oxide Al 2 O _3, which satisfies the relationship: 12% <Al ₂ 0 ₃ <18% with R6 ratio corresponding to: R6 - Αΐ2θ ₂ / Ρ ₂ θ ^ • aa * * · '^ · · ♦ a · aa · aa · a · a ···· a a ·· · · · t · · · · · and a and 9 and is in the range of 2 to 6, preferably 3 to 5. Mineral wool according to claim 7, characterized in that the ratio R 7, corresponding to: R 7 = SiO ₂ / R ₂ O is in the range of 8 to 20, preferably 10 to 15. Mineral wool according to any one of the preceding claims, characterized in that it is fiberized by external centrifugation. A product intended for thermal and / or acoustic insulation or an extraterrestrial culture substrate and consisting at least in part of mineral wool, characterized in that the wool has a chemical composition as defined in any of the preceding claims.