DE20019104U1 - Temperature-independent composite safety plate - Google Patents

Description

Description

The present invention relates to a breakthrough-resistant and/or bullet-resistant and/or blast-resistant and/or sound-insulating composite safety panel with the features specified in the preamble of claim 1.

From the prior art, a bulletproof glass pane is known which comprises several glass panels which are connected to one another in a sandwich-like manner by means of polyvinyl butyral films arranged between them.

Such armored glass panes are disadvantageous in many ways:

A particularly serious disadvantage in the case of bulletproof glass panes constructed in this way is that their bullet-resistant and break-in-resistant effect is essentially completely lost at low temperatures as well as high temperatures.

At low temperatures, the loss of the penetration-resistant and bullet-resistant effect is explained by the fact that the glass transition temperature of the polyvinyl butyral adhesive films falls below this temperature, and these films become very brittle when their glass transition temperature is exceeded.

At high temperatures, however, the thermoplastic, linearly linked polyvinyl butyral adhesive films soften, and this softening can even lead to a slow change in shape (creep) of the polyvinyl butyral adhesive films.

Both at low temperatures and at higher temperatures, firing at such armored glass panes will therefore result in an unwanted bullet penetration.

Due to the large number of glass layers and plastic films that have to be bonded together, the production of such armored glass panes requires a particularly high level of manufacturing effort.

For example, many layers and films must first be produced and then bonded together using complex processes. In particular, the temperature and pressure-controlled bonding process of the individual layers and films is time-consuming and costly.

In particular, numerous interface transitions ultimately result in extremely poor transmission properties, which can even lead to the formation of interference patterns in the form of Newton rings.

Another disadvantage of these well-known bulletproof glass panes is their poor color neutrality when viewed through. When looking at colored objects through this well-known bulletproof glass pane, you always notice color distortions, for example in the form of a green or brown tint.

The high glass content, i.e. the numerous glass panes of this well-known bulletproof glass pane, also leads to a very high surface weight.

The high surface weight also requires a great deal of structural effort with regard to the window frame and glazing, which may even require a motor-driven drive for the window or door sash.

The high surface weight also results in very limited design options with regard to architectural uses.
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Also known from the prior art are bulletproof glass panes which have polycarbonate plates between glass panels.

On the one hand, a polyurethane-based hot melt film can be used to bond the glass panels and polycarbonate sheets together during an autoclave process. On the other hand, a special casting resin, also based on polyurethane, can be used for this bonding purpose. These adhesive layers each have a small thickness in the range of just 0.5 mm to 2 mm.

The thermal expansion coefficients of glass and polycarbonate are very different. A particular disadvantage of these well-known polycarbonate/glass structures with thin adhesive layers is the occurrence of strong tensions in the composite if these armored glass panes are exposed to frequent temperature changes during use.
The high tensions in the composite regularly lead to significantly disruptive interference patterns, which have a very negative effect on the transmission behavior. Due to the high tensions in the composite, delamination often occurs, especially with larger panes.

With regard to the penetration-, bullet- and explosion-resistant properties, these polycarbonate/glass structures with thin adhesive layers are just as disadvantageous as the glass/glass structures held together by polyvinyl butyral adhesive films due to their lack of temperature independence.

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The object of the present invention is therefore to provide a composite safety panel which is bullet-resistant and/or break-in-resistant and/or blast-resistant and/or sound-insulating even at different temperatures, which requires only a small amount of manufacturing effort for its production, whose surface weight is extremely low and which consequently requires only a small amount of structural glazing effort, possibly without the use of a motor drive, and offers wide architectural uses and which, in the case of its transparent design, has excellent transmission properties, essentially does not have the problem of the formation of interference patterns and has excellent color neutrality.

According to the invention, this object is achieved in a generic composite safety panel by the features specified in the characterizing part of claim 1.

Particularly preferred embodiments are the subject of the subclaims.

Embodiments of the invention are described in more detail with reference to the drawings.

Figure 1 shows a schematic cross-section of a composite safety panel according to the invention with a carrier on one side of which two plastic layers are applied, each of these two plastic layers developing its maximum dissipative effect at a different temperature;

Figure 2 shows a schematic cross section through a composite safety panel according to the invention with two external supports, between which two plastic layers

are provided, with each plastic layer developing its maximum dissipative effect at a different temperature;

Figure 3 shows a schematic cross section through a composite safety panel according to the invention with two external supports, between which three plastic layers are provided, each plastic layer developing its maximum dissipative effect at a different temperature and these temperatures being different in each case;

Figure 4 shows a schematic cross section through a composite safety panel according to the invention with two carriers, wherein two plastic layers are provided between the two carriers and a further plastic layer is applied to the outside of a carrier, wherein each plastic layer develops its maximum dissipative effect at a different temperature;

Figure 5 shows a schematic cross section through a composite safety panel according to the invention with two carriers, wherein two plastic layers are provided between the two carriers and a further plastic layer is applied to the outside of each carrier, wherein each plastic layer develops its maximum dissipative effect at a different temperature;

Figure 6 shows a schematic cross section through a composite safety plate according to the invention with two carriers, wherein only one plastic layer is formed between the two carriers and only one further plastic layer is provided on the outside of one carrier, while a package of two plastic layers is attached to the outside of the other carrier, wherein

each plastic layer develops its maximum dissipative effect at a different temperature;

Figure 7 shows a schematic cross section through a composite safety panel according to the invention with three supports, wherein a single plastic layer is formed between the one outer support and the middle support, while two plastic layers are provided between the other outer support and the middle support, wherein each plastic layer develops its maximum dissipative effect at a different temperature;

Figure 8 shows a schematic cross section through a composite safety panel according to the invention with three supports, wherein two plastic layers are provided between one outer support and the inner support and between the other outer support and the inner support, wherein each plastic layer develops its maximum dissipative effect at a different temperature;

Figure 9 shows a schematic cross section through a composite safety panel according to the invention with two external supports, with two plastic layers being attached to the inside of one support and a gap filled with air or a protective gas being formed between the inner plastic layer and the other support, with each of the plastic layers developing its maximum dissipative effect at a different temperature;

Figure 10 shows a schematic cross-section through a composite safety panel according to the invention with three supports, wherein two plastic layers are provided between the one outer support and the middle support,

while between the other outer carrier and the middle carrier there is a gap filled with air or a protective gas, whereby each of the plastic layers develops its maximum dissipative effect at a different temperature.

A particular advantage of the composite safety plate according to the invention is that, despite a particularly simple structure according to the German industrial

IG enorm DIN 52290 Part 3 (06/1984) a breakthrough-resistant and/or according to the European industrial standard DIN EN 10 63 (07/1993) and/or the German industrial standard DIN 52290 Part 2 (11/1988) a bullet-resistant and/or according to the German industrial standard DIN 52290 Part 5 (12/1987) an explosion-resistant and/or according to the European industrial standards DIN EN ISO 717/1 and 717/2 (01/1997) and/or according to the German industrial standard DIN 52210 (08/1984) a sound-insulating effect.

The composite safety panel according to the invention can comprise one, two, three, four, five, six, seven, eight, nine, ten or more supports (1). As a rule, however, the composite safety panel according to the invention has only one, two or three supports (1).

Two, three, four, five, six, seven, eight, ten or more functionally energy-absorbing and energy-dissipating plastic layers (2) can be applied to these carriers (1).

In particularly preferred embodiments, each plastic layer (2) and/or each carrier (1) develops the maximum of its energy-absorbing, dissipatory effect at a different temperature or a different temperature range.

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This has the consequence that the composite safety panel according to the invention is penetration-resistant and/or bullet-resistant and/or blast-resistant and/or sound-insulating not only at a single temperature value, but in a temperature range of at least Δ4O ⁰ C in accordance with the above standard provisions.

Of particular importance are the bullet-resistant and penetration-resistant effects in a wide temperature range of at least &Dgr; 4O ⁰ C, especially since these effects are completely unexpected in the construction of the sound-absorbing composite safety panel according to the invention.

When selecting and assembling appropriate plastic layers (2) and/or supports (1), it is possible to design the composite safety panel according to the invention in such a way that it is penetration-resistant 0 and/or bullet-resistant and/or blast-resistant and/or sound-insulating in a temperature range of at least &Dgr; 50 ⁰ C, &Dgr; 60 ⁰ C, &Dgr; 70 ⁰ C, &Dgr; ^{80 0 C} , &Dgr; 90 0 C, &Dgr; 100 ⁰ C, &Dgr; HO ⁰ C or in a broader temperature range within the meaning of the above standard regulations.

Which materials are particularly suitable for forming the plastic layers (2) and/or the carriers (1), for example, is specified below.

The composite safety plate according to the invention can, for example, comprise a first plastic layer (2) which has a maximum energy-absorbing dissipation effect, for example, in the range from about -30 ⁰ C to 0 ⁰ C. In preferred embodiments, the composite safety plate according to the invention also contains a second plastic layer (2) which develops its maximum dissipation effect, for example, in the range from about 0 ⁰ C to +30 ⁰ C. If necessary, in the composite safety plate according to the invention

A third plastic layer (2) is provided on the composite safety panel, which exhibits its maximum dissipation effect, for example, in the range from + 30 ⁰ C to + 60 ⁰ C. Finally, with the composite safety panel according to the invention, it is possible to apply a fourth plastic layer (2) which develops its maximum dissipation effect, for example, in the range from + 60 ⁰ C to + 90 ⁰ C.

As a rule, each plastic layer (2) and/or each carrier (1) converts a large proportion of the acting kinetic energy into deformation and/or heat, particularly at its predetermined operating temperature. This at least largely prevents the acting object (projectile, axe) from completely or at least partially penetrating the composite safety plate.

The plastic layers (2) may be the same or different from one another with regard to their chemical composition and/or their degree of cross-linking.

The same applies to the carriers (1).

Each plastic layer (2) can therefore have a different chemical composition and/or different degrees of cross-linking compared to the other plastic layers (2) and/or compared to the at least one carrier (1).

The term "cross-linking" here means a spatial linking of polymer chains to form a network polymer. The degree of cross-linking is a measure of the frequency of linking of polymer chains to one another. The more frequent this cross-linking is, the harder the polymers generally become. If the degree of cross-linking is relatively low and the polymers are soft or elastic, they are called elastomers; if the degree of cross-linking is higher, the polymers are relatively hard and are called duromers. These two classes of polymer differ from

Thermoplastics are characterized by the fact that the polymers do not melt or liquefy when the temperature is increased. In the case of elastomers and thermosets, the mechanical properties - particularly in the temperature range above 50 ⁰ C - are not nearly as dependent on temperature as is the case with thermoplastics.

As a rule, each plastic layer (2) does not only act as an adhesive layer. Preferably, each carrier (1)

and/or each plastic layer (2) rather has a functional significance with regard to the bullet-resistant and/or breakthrough-resistant and/or explosion-resistant and/or sound-insulating effect. 15

Each plastic layer (2) and/or each carrier (1) can be designed as a single layer or multiple layers. In the case of a multiple layer design, the individual layers are preferably directly connected to one another. Of course, these multiple layers can be separated from one another, for example by intermediate layers of a different chemical composition and/or a different degree of cross-linking.

As a rule, the Shore A hardness of each individual plastic layer (2) measured in accordance with the German industrial standard DIN 53505 (06/1987) is greater than 70 at the temperature or in the temperature range at which it develops its maximum dissipative effect. The Shore D hardness is preferably greater than 25 there.

Each individual plastic layer (2) can, for example, have a thickness in the range from 3 mm to 120 mm, preferably in the range from 3.1 mm to 100 mm, in particular in the range from 5 to 30 mm.

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Each carrier (1) can, for example, have a thickness in the range from about 1 mm to 40 mm, preferably from about 1.5 mm to 35 mm, in particular from about 1.6 mm to 20 mm.

If the composite safety panel according to the invention is transparent, it can have a transparency according to the German industrial standard DIN 67507 (06/1980), for example in the range from 80% to 96%, preferably 85% to 95%, in particular from 89 % to 94%, with a thickness of the composite safety panel of 30 mm (see graphic figure 1), due to the structure according to the invention and the selection of the plastic layers (2) and the carriers (I) according to the invention.

However, the composite safety panel according to the invention can also comprise one or more plastic layers (2) and/or carriers (1) which are uniformly or unevenly colored transparent and/or opaque.

0 In preferred embodiments of the composite safety panel according to the invention, the plastic layers (2) are provided directly on top of one another without intermediate adhesive layers or adhesive films.

The package(s) of plastic layers (2) or each individual plastic layer (2) can also be provided directly on the carrier(s) (1) without an intermediate adhesive layer.

In particular, Figures 2 and 3 show that the composite safety panel according to the invention can comprise, for example, two external supports (1), between which one, two, three, four, five, six, seven, eight, nine or ten plastic layers (2) are provided, each in direct contact with one another.

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Figures 4, 5 and 6 show exemplary embodiments of the composite safety panel according to the invention, which comprise two supports (1) between which one, two, three, four, five, six, seven or more plastic layers (2) are provided, wherein one, two, three, four, five or more plastic layers (2) are applied to the outside of one or both supports (1).

From Figures 7 and 8 it can be seen that in preferred embodiments of the composite safety panel according to the invention, for example, three supports (1) can be provided, wherein between the adjacent supports (1) one, two, three, four, five or more plastic layers (2) can be provided in direct contact with one another.

Figure 9 shows a further embodiment of the composite safety panel according to the invention, which comprises two external supports (1). One, two, three, four, five or more plastic layers (2) can be attached to the inside of one support (1), preferably in direct contact with one another. An air gap (3) is optionally formed between the last internal plastic layer (2) and the other external support (1).

Finally, Figure 10 shows a further possible embodiment of the composite safety plate according to the invention, which comprises three supports (1), whereby one, two, three, four, five or more plastic layers (2) are formed between the one outer support (1) and the middle support (1). Between the other 35

An intermediate space (3) filled with air or protective gas can be provided between the outer support (1) and the central support (1).

The composite safety panel according to the invention can preferably be used as a breakthrough-resistant and/or bullet-resistant and/or blast-resistant and/or sound-absorbing and/or UV-protection panel for civil and/or military purposes in a vehicle on land, in the air or on water or in the field of construction.

The at least one carrier (1) can be made essentially from amorphous, non-crystalline materials, glass, alkali-lime glass such as soda-lime glass and/or borosilicate glass, window glass, float glass, lead crystal glass, mirror glass, tempered glass, wire glass, ornamental glass, coated glasses, frosted glass, quartz glass, glass ceramics, crystal glass, optical glasses, technical glasses, radiation protection glasses, foam glass, Dall glass, safety glass, colored glasses, opal glass, opaque glass, cloudy glass, appliance glass, silica glass, high-lead crystal glass, cerium-doped glass, flint glasses, crown glasses, sealing glasses, metallic and/or metal oxide coated glasses, printed glasses or painted glasses, whereby all of these types of glass are flat, even, curved or spherically curved and/or from ceramic materials, glass ceramics, oxide ceramics, powder metallurgy, coarse clay ceramic materials, fine clay ceramic materials, coarse special ceramic materials, fine special ceramic materials, clay, pottery, earthenware, stoneware, porcelain and/or wood and/or metal and/or plastic and/or mixtures thereof.

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Preferably, the one or more plastic layers (2) and/or the at least one carrier (1), optionally made of plastic, comprises a chemically and/or thermally and/or physically hardened mass of a hardenable plastic.

This plastic can, for example, be selected from the group of casting resins or reaction resins based on polyurethanes, cross-linked polyurethanes, partially cross-linked polyurethanes, polyureas, epoxies, unsaturated or saturated polyesters, polyethylene terephthalates (PET), polybutylene terephthalates (PBT), poly-(meth)acrylates, silicones, silicone resin polymers, MS polymers (mixed silicone polymers) or from the group of hot melt adhesives, coatings and sealants, for example based on polyethylene or its copolymers or polyvinyl acetate or mixtures thereof.

As already stated, the curable plastic forming the single-layer or multi-layer plastic layer (2) can be a polyurethane.

In this case, the plastic comprises a first component A, which can be selected from the group of polyether polyols, polyester polyols, polyether polyester polyols, phosphoric acid polyol esters, sulfonic acid polyol esters, (meth-)acrylic acid polyol esters, lactone polyols, polycarbonate polyols, saturated or unsaturated aliphatic, cyclic, alicyclic or aromatic polyols and/or mixtures thereof.

Its second component B can, for example, be selected from the group of aliphatic or aromatic polyisocyanates, which can be present as monomeric, prepolymerized and/or blocked polyisocyanates, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, trime-

Ethylhaxamethylene diisocyanate (TMDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI or MCH), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (Hi ₂ MDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), their allophanates, biurets, uretdiones, isocyanurates, their blocked compounds or adducts with caprolactam, malonic acid esters, alkyl acetoacetates, as ketoximes, Schiff bases or mixtures thereof.

Its optionally present third component C, a catalyst, can be selected, for example, from the group of tertiary amines and their salts, in particular their chlorides, sulfates, nitrates, phosphates, phosphonates, phosphites, carboxylates with mono- or polyvalent carboxylic acids, organometallic compounds, in particular alkyl compounds of lead, zinc, tin, zirconium, titanium, their metal soaps or complex compounds with mono- or polyvalent aliphatic or aromatic carboxylic acids or anhydrous salts of polyvalent metals, in particular the halides or the carboxylates of lead, tin, zinc, manganese, titanium, zirconium, magnesium, calcium, or mixtures thereof.

In addition, the curable plastic from the group of polyurethanes can comprise a component D which is selected from the group of sterically hindered amine light stabilizers, in particular the derivatives of 1,2, 2, 6, 6-pentamethylpiperidinol or 2,2,6,6-tetramethylpiperidine, where the substituents on the piperidine N atom are a hydrogen or an oxygen atom or represent a hydroxy, alkoxy, alkyl or acetoxy group and where the substituents on the C-1 carbon atom are a hydrogen or an oxygen atom or represent a hydroxy, alkoxy, alkyl, acetoxy group or an imide or benzylidene.

Alternatively or additionally, the curable plastic from the group of polyurethanes can comprise a component E which is selected from the group of UV absorbers, oxalanilides, hydroxybenzophenones, benzotriazoles, benzotriazines or mixtures thereof.

As already mentioned, the curable plastic can be a polyurea.

As a rule, this comprises a first component A, which is selected from the group of aliphatic, cycloaliphatic or aromatic amines with primary, secondary or tertiary amino groups, primary or secondary polyamines, bifunctional amines, adducts of the aforementioned amines or ammonia with oxiranes, ethylene oxide, ethoxylates, epoxides, (meth)acrylic acids or (meth)acrylic acid esters or mixtures thereof.

Its second component B can be selected from the group of aliphatic or aromatic polyisocyanates, which can be present as monomeric, prepolymerized and/or blocked polyisocyanates, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI or MCH), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), their allophanates, biurets, uretdiones, isocyanurates, their blocked compounds or adducts with caprolactam, malonic acid esters, alkyl acetoacetates, as ketoximes, Schiff bases or mixtures thereof.

Its third component C can be selected from the group of tertiary amines and their salts, in particular their chlorides, sulfates, nitrates, phosphates, phosphonates, phosphites, carboxylates with mono- or polyvalent carboxylic acids, organometallic compounds, in particular alkyl compounds of lead, zinc, tin, zirconium, titanium, their metal soaps or complex compounds with mono- or polyvalent aliphatic or aromatic carboxylic acids or anhydrous salts of polyvalent metals, in particular the halides or the carboxylates of lead, tin, zinc, manganese, titanium, zirconium, magnesium, calcium, or mixtures thereof.

If the curable plastic is an epoxy, it can comprise a first component A which is selected from the group of oxiranes, the diglycidyl ethers of bisphenol A, bisphenol F or their partially hydrogenated derivatives, unmixed or mixed with a reactive diluent for epoxy resins such as C12-C14 alkyl glycidyl ether, butanediol diclycidyl ether, hexanediol diglycidyl ether, ethylhexyl glycidyl ether, ethylhexanediol diglycidyl ether, cyclohexanedimethyldiol diglycidyl ether, polyoxypropylene diglycidyl ether, polyoxypropylene triglycidyl ether

Its second component can, for example, be selected from the group of aliphatic, cycloaliphatic or araliphatic amines, polyamines or their adducts with oxiranes, diglycidyl ethers of bisphenol A, bisphenol F or their partially hydrogenated derivatives, polyoxyethylene amines, polyoxypropylene amines or mixtures thereof.

If the curable plastic is an unsaturated polyester, it can comprise a first component A, which is selected, for example, from the group of esters, optionally of maleic acid, fumaric acid, adipic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, mesaconic acid, citraconic acid or itaconic acid with bi-, tri- or tetrafunctional aliphatic alcohols such as ethanediol, propanediol, butanediol, hexanediol, ethylhexanediol, propanetriol, trimethylolethane, erythritol, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, hydrogenated bisphenol-A, and monomers such as a-methylstyrene, methyl acrylate, vinyl acetate, divinylbenzene, diallyl phthalate, triallyl cyanurate or triallyl phosphate,

As an accelerator/initiator, it can comprise a second component B, which is selected, for example, from the group of tertiary amines or amino alcohols such as N,N'-dimethylaniline or N,N'-dimethylaminoethanol or from the group of hydroperoxides in combination with heavy metal salt accelerators or peroxides in combination with tertiary aromatic amines or photoinitiators.

As a Cc-3 accelerator, it can comprise a third component C, which is selected, for example, from the group of salts of polyvalent metals of carboxylic acids (metal soaps) such as cobalt octoate, manganese octoate, manganese stearate, calcium octoate.

As an initiator, it can comprise a fourth component D, which is selected, for example, from the group of peroxides or azo compounds such as cumene hydroperoxide or azobisisobutyronitrile (AIBN).

If the curable plastic is selected from the group of (meth)acrylates, it generally comprises a first component A, which is selected, for example, from the group of (cyclo)aliphatic esters of (meth)acrylic acid, their prepolymers, methyl methacrylate, butyl methacrylate, hexyl methacrylate, hexanediol methacrylate, ethylhexyl diol dimethacrylate, polyoxypropylene dimethacrylate, trimethylolethane trimethacrylate or mixtures thereof.

As an accelerator, it can comprise a second component B, which is selected, for example, from the group of tertiary amines or amino alcohols such as N, ^NS -dimethylaniline, N,N'-dimethylaminoethanol or mixtures thereof.

As a co-accelerator, it can comprise a third component C, which is selected, for example, from the group of salts of polyvalent metals of carboxylic acids (metal soaps) such as cobalt octoate, manganese octoate, manganese stearate, calcium octoate or mixtures thereof.

As an initiator, it can further comprise a fourth component D, which is selected, for example, from the group of peroxide compounds, triphenylphosphine oxides or azo compounds, such as cumene hydroperoxide or azobisisobutyronitrile (AIBN).

If the curable plastic is a silicone resin polymer, it can comprise a first component A, which is selected, for example, from the group of dialkylpolysiloxanes with dimethylvinylsiloxy end groups.

In addition, it may comprise a second component B, which may be selected from the group of alkylhydrosiloxanes
is selected.

As a catalyst, it may comprise a third component C, which is selected, for example, from the group of
Platinum compounds such as hexachloroplatinic acid.

Regardless of its type, the curable plastic can comprise an adhesion promoter which is selected, for example, from the group of silanes and their hydrolysates, polysiloxanes and their hydrolysates, silicones,
gaseous silanes, epoxysilanes and silanes that are gaseous at room temperature. In principle, however, any of
state-of-the-art adhesion promoters are used
come.

The possible integration of an adhesion promoter into the plastic layer (2) can make it possible to dispense with

on the adhesive film known from the state of the art
Polyurethane support enables this. In this way
The translucent light is spared the passage through the light-refracting transition surfaces of the adhesive films.

Regardless of its type, the curable
Plastic may additionally comprise a UV stabilizer which is selected, for example, from the group of oxalanilides, hydroxybenzophenones, benzotriazoles, benzotriatines and/or mixtures thereof.

Regardless of its type, the curable
Plastics may also contain an antioxidant,
which is selected, for example, from the group of

sterically hindered phenols such as tetrakis(methylene(3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate))methane, tris(2,4-di-tertiary-butylphenyl)phosphite, octadecyl-3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate, tetrakis(2,4-di-tertiary-butylphenyl)-4,4'-biphenylenediphosphonite or mixtures thereof.

Irrespective of its respective type, the curable plastic can comprise a temperature or heat stabilizer which is selected, for example, from the group of sterically hindered phenols such as tetrakis (methylene(3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate)!methane, tris(2,4-di-tertiary-butylphenyl)phosphite, octadecyl-3,5-di-tertiary-butyl-4-hydroxyhydrocinnamate, tetrakis(2,4-di-tertiary-butylphenyl)-4,4'-biphenylenediphosphonite or mixtures thereof.

In summary, it can be stated that the composite safety panel according to the invention in particular fully retains its bullet-resistant and penetration-resistant effect both at low temperatures and at high temperatures.
The feared loss of the penetration-resistant and bullet-resistant effect of the armored glass panes of the state of the art when the glass transition temperature of the adhesive films falls below or when the thermoplastic adhesive films soften, does not occur with the composite safety panel according to the invention.

As the examples show, the composite safety plate according to the invention prevents bullet penetration extremely effectively both at low temperatures and at higher temperatures.

In the composite safety plate according to the invention, the individual layers can preferably be produced and connected to one another by simply and inexpensively pouring them onto one another. The manufacturing effort for a composite safety plate according to the invention is therefore particularly low and leads to particularly low manufacturing costs.

The time-consuming and costly temperature- and pressure-controlled bonding processes of numerous layers and films known from the prior art are generally eliminated in the case of the composite safety plate according to the invention.

The manufacturing effort for the composite safety panel according to the invention is therefore particularly low, since the production of separate layers and films, which have to be bonded together in a technically very demanding, temperature and pressure-controlled bonding process, is no longer necessary. In the case of the composite safety panel according to the invention, it may only be necessary to fill a plastic mass into the space between two panes.

Finally, the composite safety panel according to the invention essentially does not have the problem of the formation of interference patterns, even when viewed at an angle. This is because the composite safety panel according to the invention has a significantly reduced number of thin adhesive layers that give rise to interference patterns compared to the bulletproof glass panels known from the prior art.

The small number of interfaces/glass panels in the case of the composite safety panel according to the invention also leads to excellent transmission properties (see Figure 1).
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Furthermore, the composite safety panel according to the invention has excellent color neutrality because only two materials are used, namely glass and plastic, instead of the large number of materials known from the prior art (e.g. glass, polyvinyl butyral film and polyacrylate resin). The better color neutrality of the composite safety panel according to the invention compared to the color neutrality of the bulletproof glass pane known from the prior art is also due to the fact that the glass layers in the composite safety panel according to the invention may be significantly thinner.

Furthermore, the possibility according to the invention of using fewer and possibly thinner glass panels considerably reduces the green component of the composite safety panel according to the invention, which is caused in particular by the iron content.

Finally, the use of thick-walled plastic layers (2) which not only have an adhesive effect but also function, with a thickness possibly in the range of 2 mm to 120 mm, leads to a saving of the numerous glass layers known from the prior art.

In the case of the composite safety panel according to the invention, a large part of the glass can be replaced by plastic while maintaining the same resistance class - while reducing the surface weight.

The strikingly low surface weight allows for a particularly low structural glazing effort. The engine

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Operation of window and door leaves is usually not necessary in the case of the composite safety panel according to the invention.

Examples 1 to 3 describe the production of exemplary components for exemplary casting resins according to the invention for producing an exemplary composite safety plate according to the invention which develops its maximum dissipative effect at different temperatures.

Subsequently, the advantages of a composite safety panel according to the invention compared to composite safety panels known from the prior art are demonstrated using comparative examples.

Example 1 : Preparation of an exemplary polyol component (α-component) for the preparation of an exemplary polyurethane for an application temperature of 20 ⁰ C

3115 g (89.0%) of a polyether polyol with an average of 3 OH groups (trifunctional) per molecule (based on polypropylene oxide started with trimethylolpropane), an average molecular weight of approx. 450 g/mol and an OH number of approx. 380 mg KOH/g were placed in a closed stirring apparatus consisting of a 5000 mL round-bottom flask with a paddle stirrer, a thermometer, a vacuum connection and a water bath. 297.5 g (8.5%) of a difunctional polyether polyol (based on polypropylene oxide started with diethylene glycol) with an average molecular weight of approx. 2000 g/mol and an OH number of approx. 56 mg KOH/g and 87.5 g (2.5%) butylbenzyl phthalate as a plasticizer were then added to this mixture.

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ized and mixed homogeneously at approx. 50 revolutions per minute (50 l/min) within 5 minutes. Then 1.05 g (0.03%) dibutyltin dilaurate was added as an accelerator and mixed homogeneously for a further 5 minutes at approx. 50 revolutions per minute. The speed of the stirrer was then reduced to 30 l/min and a vacuum was applied over the next 20 minutes, which was 5 mbar at the end of the specified time. The speed was then carefully and slowly increased to 50 l/min. The rate at which the pressure is reduced and the increase in the stirrer speed depend on the foaming of the mixture, which is more or less pronounced depending on the water content and amount of dissolved gases. The mixture was then stirred at a vacuum of 5 mbar for a period of 70 minutes at a temperature of 23 ⁰ C at 50 l/min. After the stirrer motor was switched off, the mixture was ventilated with dried nitrogen. The result is a clear, colorless mixture, which must be protected from moisture.

Example 2 : Preparation of an exemplary polyol component (A component) for the preparation of an exemplary polyurethane for an application temperature of 0 ⁰ C

In the same stirring apparatus as in Example 1, 1428 g (40.8%) of a trifunctional polyether polyol (based on propylene oxide started with trimethylolpropane) with an average molecular weight of approx. 486 g/mol and an OH number of approx. 385 mg KOH/g were mixed with 1428 g (40.8%) of a trifunctional polyether polyol of the same base and an average molecular weight of approx. 660 g/mol and an OH number of approx. 255 mg KOH/g as well as 234.5 g (6.7%) of a difunctional polyether polyol based on propylene oxide started with diethylene glycol with a

average molecular weight of 2000 g/mol and an OH number of 56 mg KOH/g and 234.5 g (6.7%) of a difunctional polyether polyol based on propylene oxide started with diethylene glycol and capped at the ends with ethylene oxide with an average molecular weight of approx. 2000 g/mol and an OH number of 57 mg KOH/g as well as 175 g (5.0%) of trimethylolpropane and 2.1 g (0.06%) of dibutyltin dilaurate as accelerator were mixed homogeneously with one another at a stirrer speed of 50 l/min and a temperature of 23 ⁰ C within 10 minutes. The speed was then reduced to 30 l/min and a vacuum was applied for the next 20 minutes, which was increased to 5 mbar over the specified time. The speed of the stirrer was then slowly and carefully increased to 50 l/min. The speed of the pressure reduction and the increase in the stirrer speed depends on the foaming of the mixture, which can vary depending on the water content and the amount of dissolved gases. The mixture was then stirred at a vacuum of 5 mbar for a period of 70 minutes at a temperature of 23 ⁰ C at 50 l/min. After the stirrer motor was switched off, it was ventilated with dried nitrogen. A clear, colorless mixture was obtained, which must be protected from moisture.

Example 3 : Preparation of an exemplary polyol component (A component) for the preparation of an exemplary polyurethane for an application temperature of 50 ⁰ C

In the same stirring apparatus as in Examples 1 and 2, 3150 g (90.0%) of a trifunctional polyether polyol based on propylene oxide were started with trimethylolpropane with an average molecular weight of approx.

g/mol and an OH number of approx. 380 mg KOH/g and 350 g

(10.0%) of a difunctional polyether polyol based on propylene oxide, capped at the ends with ethylene oxide and with an average molecular weight of approx. 2000 g/mol and an OH number of approx. 57 mg KOH/g, were mixed homogeneously within 5 minutes at a stirrer speed of 50 l/min. 1.75 g (0.05%) of dibutyltin dilaurate were then mixed in homogeneously as an accelerator within 5 minutes at 50 l/min. The speed was then reduced to 30 l/min and a vacuum was applied over the next 20 minutes, which was increased to 5 mbar over the course of the specified time. The stirrer speed was then slowly and carefully increased again to 50 l/min. The rate at which the pressure is reduced and the stirrer speed increases depends on the foaming of the mixture, which can vary depending on the water content and the amount of dissolved gases. The mixture was then stirred at a vacuum of 5 mbar for 70 minutes at a temperature of 23 ⁰ C at 50 l/min. After the stirring motor was switched off, it was ventilated with dried nitrogen. A clear, colorless mixture was obtained, which must be protected from moisture.

Example 4 : Preparation of an exemplary isocyanate component (B component) for the production of exemplary polyurethanes for use temperatures of 0, 20 and 50 ⁰ C

In the same stirring apparatus as in Examples 1 to 3, 2780 g (69.5%) of isophorone diisocyanate as isocyanate monomer, 1200 g (30.0%) of a difunctional isocyanate prepolymer (based on isophorone diisocyanate reacted with polyether polyol based on propylene oxide) with an average molecular weight of approx. 2200 g/mol and an NCO content of approx. 3.8% and 20 g (0.5%) of isocyanate

·

28

topropyltriethoxysilane as adhesion promoter at a stirrer speed of 50 l/min, and slowly and carefully applying a vacuum at a temperature of 23 ⁰ C. After 20 minutes, the maximum vacuum of 5 mbar was reached. Stirring was then continued under these conditions for a period of 60 minutes. After switching off the stirrer motor, the mixture was ventilated with dried nitrogen. A clear, colorless mixture was obtained which must be protected from moisture.

Example 5 : Preparation of an exemplary polyurethane resin according to the invention from an exemplary component A (polyol component) according to Examples 1, 2 and 3 and an exemplary component B (isocyanate component component) according to Example 4 and preparation of the test specimens for the Shore hardness determination

To determine the mixing ratio of the two components A and B, the OH numbers of the polyol components from Examples 1 to 3 and the NCO content of the isocyanate component from Example 4 had to be determined. The OH number of the α components from Example 1 was determined by the acylation method to be 343 mg KOH/g, from Example 2 to be 331 mg KOH/g and from Example 3 to be 348 mg KOH/g. The NCO content of the B component from Example 4 was determined to be 27.5% by quantitative reaction with di-n-butylamine and back titration of the amine.

The calculation of the amount of component B used for a given amount of component α at a molar ratio of OH:NCO = 1:1.1 was carried out using the following formula:

Amount of B component in g for 100g A component = (OH number) *42*10/(56*mass fraction NCO in %)

This resulted in the following mixing ratios:

100 g component A from example 1 : 102.9 g component B from example 4

100 g component A from example 2 : 99.4 g component B from example 4

100 g component A from example 3 : 104.3 g component B from example 4

The components were mixed in a beaker by weighing appropriate amounts of components A and B into a 250 mL beaker. The two components were then mixed homogeneously in an open beaker at 100 l/min within 5 minutes using a paddle stirrer. The beaker containing this mixture was then immediately placed in a desiccator which was on a magnetic stirrer and stirred for a further 5 minutes at a speed of 30 l/min using a 6 cm long magnetic stirring bar. A vacuum of 10 mbar was applied and the casting resin was degassed at a temperature of 23 ⁰ C.

To determine the Shore hardness according to DIN 53505 (06/87), 9.5 g of the freshly mixed casting resin were filled into a polyethylene lid with a diameter of 40 mm so that the filling height was 6 mm. After 12 hours of curing at approx. 23°C, the lid and its contents were stored in a heating cabinet at 60 ⁰ C for 4 hours. After cooling to room temperature and conditioning for 4 hours at 23 ⁰ C and 53% relative humidity, the samples were removed from the lids, coated with talcum powder and the Shore α and Shore Dr hardnesses were measured. The following values were obtained:

ti

30

Table 1:

Polyurethane casting resin
by mixing Shore A
hardness
[1] Shore D
hardness
[1] Example 1 with 4 (Example 1/4)
(Operating temperature 20 ⁰ C) 84 72 Example 2 with 4
(Operating temperature O ⁰ C) 75 52 Example 3 with 4
(Operating temperature 50 ⁰ C) 94 78

In order to see what the Shore hardness of the mixtures looks like for the individual optimized operating temperatures, the hardnesses were measured at different temperatures. The values obtained are summarized in Tables 2 and 3.

Table 2:

Shore A
0 ⁰ C Shore A
23°C Shore A
5O ⁰ C Example 1/4
(20°C) 94 84 68 Example 2/4
(0 ⁰ C) 85 75 64 Example 3/4
(50 ⁰ C) 99 94 87

·

Table 3:

Shore D
0 ⁰ C Shore D
23°C Shore D
50 ⁰ C Example 1/4
(2O ⁰ C) 76 72 27 Example 2/4
(O ⁰ C) 68 52 25 Example 3/4
(50 ⁰ C) 83 78 50

The 3 polyurethane casting resins compared are optimized in terms of their bombardment properties for a very specific application temperature specified in the examples. This means that they have their maximum energy-absorbing, dissipative effect at the specified application temperature. As can be seen from Tables 2 and 3, the optimal Shore-α hardness of the casting resin at the corresponding application temperature is approximately 80 to 90 and the Shore-D hardness approximately 50 to 70.

Example 6 : Comparison example of the Shore hardness of different polymeric interlayers for the production of laminated safety glass

For the production of state-of-the-art laminated safety glass (VSG), a film made of polyvinyl butyral (PVB) is used. For comparison, in this example, a PVB film from HT-Troplast with the trade name Trosifol MB was used. Casting resins can also be used to produce VSG, which are preferably based on the

it c* ·

Based on polyacrylate. For comparison, a product from Chemetall with the trade name Naftolan UV 33 was used in this example. In this example, the hardness was measured at different temperatures. The results are summarized in Tables 4 and 5.

Table 4:

Shore A
0 ⁰ C Shore A
23 ⁰ C Shore A
50 ⁰ C Example 2/4 85 75 64 (O ⁰ C) 94 49 35 80 25 21 Trosifol PVB-
foil Naftolan UV 33

Table 5:

Shore D
0 ⁰ C Shore D
23°C Shore D
5O ⁰ C Example 2/4 68 52 25 (O ⁰ C) 53 25 <10 28 10 <10 Trosifol PVB-
FoI ie Naftolan UV 33

These results show that the influence of temperature on the hardness of PVB and polyacrylates is significantly more pronounced than that of the polyurethanes according to the invention. It is therefore obvious that the energy-absorbing, dissipative effect of materials based on PVB or polyacrylates

·

·

laten is dependent on the temperature to a much greater extent than is the case with the polyurethane casting resins according to the invention. To confirm this, a comparison of the bullet-resistant properties is carried out in a later example.

Example 7 : Production of exemplary composite safety panels according to a process according to the invention

To produce a laminated safety glass pane, a steel U-profile with a web width of 19 mm and a side width of 5 mm (spacer) was bent into a square measuring 490*490 mm. The length of the U-profile of 1960 mm was measured so that both ends of the profile touched. A 1 mm thick round bead of a polyisobutylene-based sealant from Chemetall with the trade name Naftotherm BU-S was then applied to both sides of the U-profile. This frame was placed on a horizontal, cleaned and pre-treated glass panel measuring 500*500 mm, which was 6 mm thick, so that a uniform edge of approx. 5 mm was created all around. A second cleaned and pre-treated glass panel measuring 500*500 mm and 4 mm thick was placed on the frame so that it was flush with the first glass panel. Then a gentle pressure was applied to the glass panel composite by hand, which pressed it together in such a way that a uniform gap of 20 mm was created between the glass panels, which was sealed to the outside. The remaining edge with a recess depth of approx. 8 mm was then filled with a sealant based on polysulfide polymer from Chemetall with the trade name Naftotherm M82. After the sealant had hardened at room temperature overnight, the

·

·

For edge sealing, two holes with a diameter of 6 mm were drilled so that they were arranged one above the other. These holes were used to fill the casting resin.

For filling, the glass panel composite was placed horizontally on the mm thick glass panel. Then 2400 mL of mixed polyurethane casting resin were produced by mixing the polyol component from example 1 and the isocyanate component from example 4 in the calculated weight ratio from example 5, with the mixing being carried out using a commercially available mixing and dosing system. This partially filled glass panel composite was then cured horizontally for 12 hours at room temperature of around 23 ⁰ C and then the remaining space was filled with a polyurethane casting resin which was produced by mixing the polyol component from example 2 and the isocyanate component from example 4 in the calculated weight ratio from example 5. 2400 mL of casting resin were poured in through the second drilled filling opening. Curing also took place within 12 hours at room temperature. This glass panel composite was tempered at 50 ^° C in a circulating air cabinet for 5 hours before further testing to ensure that the hardening reaction was completely finished. The panel was then stored at room temperature for at least another 24 hours before testing. This manufacturing method produced a transparent, colorless-looking glass panel composite, which did not visually reveal that the plastic layer consists of two individual, directly bonded cast resin layers.

A second glass panel composite was produced by using a thermoplastically applicable material based on polyisobutylene from Chemetall as a spacer with the hand-

i I · &diams;

&bull; · &iacgr;

&diams; ·

35

Naftotherm BU-TPS was used. For this purpose, a strand of approximately 7 mm thickness and 22 mm width was applied vertically to the first cleaned and pretreated, 6 mm thick float glass panel. A second 4 mm thick glass panel, which had also been cleaned and prepared, was then placed congruently. All further steps were carried out in the same way as the pane production in the previous section, so that a gap of 20 mm was created between the panes. This variant of the laminated glass structure has the advantage that the edge bond (^spacer = edge seal) is permanently plastic and can therefore compensate for expansion differences in the thickness of the glass panel structure.

Example 8 : Shot test of a composite safety plate according to the invention at two different temperatures

The test of the bullet-resistant properties was carried out in accordance with DIN 52290 Part 2 (11/1988) according to resistance class C3-SA with a caliber of .44 Magnum at a firing distance of 3 m. For this purpose, the laminated safety glass was fixed in a clamping device so that the 6 mm thick glass panel was facing the attack. A total of 3 shots were fired at the laminated safety glass, with the hits marking the corners of an equilateral triangle with sides measuring 125 mm. For the test, the first glass panel laminate from Example 7 was heated to a temperature of 3O ⁰ C, while the second glass panel laminate was cooled to -10 ⁰ C. The firing took place at the specified temperature in each case. None of the 3 shots per glass panel laminate penetrated the laminated safety glass, which meant that the bullet test was passed.

·

Example 9: Comparative example of a bullet test of a laminated safety glass pane with only one thick polymeric interlayer at three different temperatures

It is known from DE 19824996 Al that a laminated safety glass in the form of bulletproof glass consisting of two glass panels and a thick polymer intermediate layer has bullet-resistant properties. The bullet-resistant test was carried out in the same way as in Example 8. In this example, it was investigated to what extent a laminated safety glass constructed in this way can withstand bullet-resistant temperatures of -10, 30 and ^{50 °} C. The panes were manufactured by Rosenheimer Spezialglas and had a structure consisting of the following components: 6 mm float glass panel / 20 mm polymer intermediate layer / 4 mm float glass panel. To test the bullet-resistant properties, the 6 mm glass panel was turned towards the bullet.

At 30 ⁰ C the laminated glass pane withstood the attack without any problems, whereas at -10 ⁰ C the pane was penetrated after the second shot and at 50 ⁰ C after the third shot. This test therefore shows that a structure consisting of only one thick polymer intermediate layer of the same composition can only withstand a relatively narrow temperature range.

Example 10 : Comparative example of a bullet test with state-of-the-art laminated safety glass panes at two different temperatures

A structure was tested which consisted of: an 8 mm glass panel / 2 mm casting resin (Naftolan UV 33 from Chemetall) / 12 mm glass panel / 2 mm casting resin (UV 33) / 10 mm

Glass panel / 2 ram cast resin (UV 33) / 4 mm glass panel (=glass/glass structure). The 8 mm glass panel was facing the shot during the test. A polycarbonate/glass structure was also tested which had the following structure: 4 mm glass panel / 1.14 mm PVB film / 6 mm glass panel / 1.52 mm PVB film / 6 mm glass panel / 1.5 mm polyurethane film / 6 mm polycarbonate panel (=PC/glass structure). The polycarbonate panel was facing away from the shot. The shot test was carried out at -10 and 20 ⁰ C as in Example 8. The results are summarized in Table 6.

Table 6:

Bombard with
.4 4 Magnum at
0 ⁰ C Bombard with
. 4 4 Magnum at
20 ⁰ C Glass/Glass On
building Failed Passed PC/glass construction Failed Passed Construction
Example 9 Failed Passed Construction
Example 3 Passed Passed

From the table it can be seen that only the structure according to the invention can withstand bombardment at cold temperatures.

Example 11 : Comparative example of transmission measurements

The transmission measurements were carried out with a dual-beam UV/VIS spectrophotometer type Lambda 12 from Perkin

ϕ i
&bgr; ·

Elmer in the range of 300 to 800 nm at 480 nm/min. scanning speed with measuring intervals of 5 nm. There was no sample in the reference beam during the measurement, ie
the measurement was carried out against air. In Figure 1, the transmission was plotted against the wavelength. The individual laminated safety glasses from the examples were measured. These are in detail the PC/glass structure and
the glass/glass structure from Example 10, the structure from Example 9 and the structure according to the invention from Example 7. The transmission spectra are shown in Figure 1.

Graphic Figure 1:

100

280

Transmission comparison

PC/glass structure Example 10 - - ■ Structure Example 9 Structure according to the invention Example 7

Glass/glass construction example 10

380

480 580

Wavelength [nm]

680

780

· · a

The spectra show that the structure from Example 9 and the structure according to the invention from Example 7 have the highest transmission in the visible wavelength range. It is surprising that although the polymeric intermediate layer of the structure according to the invention consists of two differently composed casting resins, i.e. of two different layers, the transmission behavior can be considered to be identical to the transmission behavior of the structure from Example 9 with a single thick polymer layer based on the transmission curves. The multilayer structures of the prior art can be classified as significantly worse in terms of their transmission behavior. This is impressively shown by the fact that their transmission curves over the entire visible wavelength range are significantly below the transmission curve of an inventive structure according to Example 7.

0 Example 12 : Comparison example of light transmission rates

The light transmission was evaluated according to DIN 67507 (06/1980) in the wavelength range between 380 and 780 niti. The values obtained are shown in Table 7:

Table 7:

Light transmission
&tgr; [%] PC/glass construction example 10 79 Glass/glass structure example 10 79 Structure Example 9 88 Inventive structure Example 7 88

As can be seen from Table 7, the light transmission of the two prior art structures from Example 10 is 9%, which is significantly worse than the light transmission of the structures from Comparative Example 9 and Example 7 according to the invention. It is surprising that although the polymeric intermediate layer of the structure according to the invention from Example 7 consists of two layers, no reflection loss occurs at the interface between the polymeric layers and therefore the light transmission there is identical to the light transmission of the structure according to Comparative Example 9 with a single thick polymeric intermediate layer.

Example 13 : Comparative example of colour impression evaluation

To evaluate the color impression, the transmission curve was evaluated using the three-range method based on DIN 5033 Part 6 (08/1976) and the colorimetric values according to DIN 5033 Part 3 (1992) and DlN 6174 (01/1979) were compared according to CIELAB. This was done using the PECOL software version 3.0 from Perkin Elmer from 1994. The parameters for the evaluation were 2° standard observer at standard light D65. The result was the brightness coefficient L*, the red-green shift a* and the blue-yellow shift b* according to CIELAB. The individual values are compiled in Table 8.

&bull;t

Table 8:

Example 10 L 01 -2 a* b* PC/glass construction Example 10 91, 32 -8th ,57 -0.93 Glass/glass construction 9 90, 92 -2 ,21 0.47 Structure example Construction 94, 79 -2 ,49 1.14 According to the invention.
Example 7 ' 94, ,59 0.84

In this compilation, the L* value is the most important. The higher this value, the clearer the color behind it is assessed by an observer. The values show that this value is highest for the two structures with a thick polymer intermediate layer. The a* and b* values only say something about the color of the structures. The closer these values are to zero, the more colorless the structures are. In the glass/glass structure, the green coloring can be seen due to the high glass content.

In practice, these values mean that when the structure according to the invention is used in a facade, an observer cannot see that bulletproof glass is used.

However, this is usually the case when using state-of-the-art bulletproof glass.

»

42

Example 14 : Comparative example concerning the surface weights with laminated safety glass panes of the state of the art

The weight per unit area is the weight of a panel per square meter. For comparison, bulletproof glass panels were used that withstand a shot according to DIN 52290 Part 2 (11/1988) according to resistance class C3 with a .44 Magnum caliber at a shooting distance of 3 m at room temperature.

The structures used in the prior art are those from Example 10. These are a glass/glass structure made with a casting resin and a glass/polycarbonate structure.

In Table 9 the basis weights are compared.

Table 9:

Construction: Basis weight [kg/m ² ] Glass/glass construction Example 10 91 PC/glass construction example 10 52 Inventive structure
Example 7 45

It is noteworthy that the glass/glass structure of the prior art is twice as heavy as the structure according to the invention. Even the PC/glass structure is about 16% heavier than the structure according to the invention.

In practice, this means that the new design significantly reduces the required construction effort. As a rule, in the case of the bullet-resistant window constructions according to the invention, a motor

drive to open the sashes can be saved. A reduction in the frame portion is also usually possible with the glazing according to the invention due to the reduced surface weight, which significantly improves the overall impression of a facade.

Claims (27)

1. Composite safety panel which is break-in-resistant in accordance with the German industrial standard DIN 52290 Part 3 (06/1984) and/or bullet-resistant in accordance with the European industrial standard DIN EN 1063 (07/1993) and/or the German industrial standard DIN 52290 Part 2 (11/1988) and/or blast-resistant in accordance with the German industrial standard DIN 52290 Part 5 (12/1987) and/or sound-insulating in accordance with the European industrial standards DIN EN ISO 717-1 and 717-2 (01/1997) and/or the German industrial standard DIN 52210 (08/1984), characterized in that it comprises one, two, three, four, five, six, seven, eight, nine, ten or more supports (1) which are of the same or different composition and on which two, three, four, five, six, seven, eight, ten or more functionally energy-absorbing and energy-dissipating plastic layers (2) are applied, which are of the same or different composition, each plastic layer (2) and/or each carrier (1) developing the maximum of its energy-absorbing, dissipatory effect at a different temperature or a different temperature range, so that the composite safety panel is penetration-resistant and/or bullet-resistant and/or blast-resistant and/or sound-insulating in a wide temperature range of at least Δ 40°C within the meaning of the above standard regulations. 2. Composite safety panel according to claim 1, characterized in that a first plastic layer (2) has a maximum energy-absorbing dissipation effect in the range from approximately -30°C to 0°C, a second plastic layer (2) develops a maximum dissipation effect in the range from approximately 0°C to +30°C and a third plastic layer (2) shows a maximum dissipation effect in the range from approximately +30°C to +60°C and optionally a fourth plastic layer (2) develops a maximum dissipation effect in the range from +60° to +90°C. 3. Composite safety plate according to one or more of the preceding claims, characterized in that each plastic layer (2) and/or each carrier (1) converts a large proportion of the acting kinetic energy into deformation and/or heat at least at a predetermined operating temperature and thereby also prevents the acting object (projectile, axe) from completely or partially penetrating the composite safety plate. 4. Composite safety panel according to one or more of the preceding claims, characterized in that each carrier (1) and/or each plastic layer (2) is essentially functional with regard to the bullet-resistant and/or breakthrough-resistant and/or blast-resistant and/or sound-insulating effect. 5. Composite safety panel according to one or more of the preceding claims, characterized in that each plastic layer (2) and/or each carrier (1) is designed as a single layer or multiple layers, wherein in the case of a multiple layer design the individual layers are directly connected to one another or are separated from one another by intermediate layers of a different chemical composition and/or a different degree of cross-linking. 6. Composite safety panel according to one or more of the preceding claims, characterized in that the Shore A hardness of each individual plastic layer (2) measured in accordance with the German industrial standard DIN 53505 (06/1987) is greater than 70 at the temperature or in the temperature range at which it develops its maximum dissipative effect, and that the Shore D hardness measured in accordance with the German industrial standard DIN 53505 (06/1987) is greater than 25 there. 7. Composite safety panel according to one or more of the preceding claims, characterized in that each individual plastic layer (2) has a thickness in the range of 3 mm to 120 mm. 8. Composite safety panel according to one or more of the preceding claims, characterized in that each carrier (1) has a thickness in the range of about 1 mm to 40 mm. 9. Composite safety panel according to one or more of the preceding claims, characterized in that it has a light transmission according to the German industrial standard DTN 67507 (06/1980) in the range of 80% to 96% with a thickness of the composite safety panel of 30 mm. 10. Composite safety panel according to one or more of the preceding claims, characterized in that one or more of the plastic layers (2) and/or the carrier (1) are uniformly or unevenly colored transparent and/or opaque. 11. Composite safety panel according to one or more of the preceding claims, characterized in that at least one carrier (1) is essentially made of amorphous, non-crystalline materials, glass, alkali-lime glasses such as soda-lime glass and/or borosilicate glass, window glass, float glass, lead crystal glass, mirror glass, tempered glass, wire glass, ornamental glass, coated glasses, frosted glass, quartz glass, glass ceramics, crystal glass, optical glasses, technical glasses, radiation protection glasses, foam glass, Dall glass, safety glass, colored glasses, opal glass, opaque glass, cloudy glass, appliance glass, silica glass, high-lead crystal glass, cerium-doped glass, flint glasses, crown glasses, sealing glasses, metallic and/or metal oxide coated glasses, printed glasses or painted glasses, all of these types of glass being flat, even, curved or spherically curved and/or made of ceramic materials, glass ceramics, oxide ceramics, powder metallurgy, coarse clay ceramic materials, fine clay ceramic materials, coarse special ceramic materials, fine special ceramic materials, clay, pottery, earthenware, stoneware, porcelain and/or wood and/or metal and/or plastic and/or mixtures thereof. 12. Composite safety panel according to one or more of the preceding claims, characterized in that each plastic layer (2) has a different chemical composition and/or a different degree of cross-linking compared to the other plastic layers (2) and/or compared to the at least one carrier (1). 13. Composite safety panel according to one or more of the preceding claims, characterized in that the plastic layers (2) are provided directly on top of one another without an adhesive layer in between. 14. Composite safety panel according to one or more of the preceding claims, characterized in that the package of plastic layers (2) or each individual plastic layer (2) is provided directly on the carrier or carriers (1) without an intermediate adhesive layer. 15. Composite safety panel according to one or more of the preceding claims, characterized in that the one or more plastic layers (2) and/or the at least one carrier (1) optionally made of plastic comprises a chemically and/or thermally and/or physically hardened mass of a hardenable plastic which is selected from the group of casting resins or reaction resins based on polyurethanes, cross-linked polyurethanes, partially cross-linked polyurethanes, polyureas, epoxies, unsaturated or saturated polyesters, polyethylene terephthalates (PET), polybutylene terephthalates (PBT), poly-(meth)acrylates, silicones, silicone resin polymers, MS polymers (mixed silicone polymers), hot-melt adhesives, coatings and sealing compounds optionally based on polyethylene or its copolymers, polyvinyl acetate or mixtures thereof. 16. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of polyurethanes comprises a first component A, which is selected from the group of polyether polyols, polyester polyols, polyether polyester polyols, phosphoric acid polyol esters, sulfonic acid polyol esters, (meth-) acrylic acid polyol esters, lactone polyols, polycarbonate polyols, saturated or unsaturated aliphatic, cyclic, alicyclic or aromatic polyols and/or mixtures thereof
a second component B, which is selected from the group of aliphatic or aromatic polyisocyanates, which can be present as monomeric, prepolymerized and/or blocked polyisocyanates, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI or MCH), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), their allophanates, butylates, uretdiones, isocyanurates, their blocked compounds or adducts with caprolactam, malonic acid esters, alkyl acetoacetates, as ketoximes, Schiff bases or mixtures thereof,
and a third component C as a catalyst, which is selected from the group of tertiary amines and their salts, in particular their chlorides, sulfates, nitrates, phosphates, phosphonates, phosphites, carboxylates with mono- or polyvalent carboxylic acids, organometallic compounds, in particular alkyl compounds of lead, zinc, tin, zirconium, titanium, their metal soaps or complex compounds with mono- or polyvalent aliphatic or aromatic carboxylic acids or anhydrous salts of polyvalent metals, in particular the halides or the carboxylates of lead, tin, zinc, manganese, titanium, zirconium, magnesium, calcium, or mixtures thereof. 17. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of polyureas contains a first component A, which is selected from the group of aliphatic, cycloaliphatic or aromatic amines with primary, secondary or tertiary amino groups, primary or secondary polyamines, bifunctional amines, adducts of the aforementioned amines or ammonia with oxiranes, ethylene oxide, ethoxylates, epoxides, (meth)-acrylic acids or (meth)-acrylic acid esters or mixtures thereof,
and a second component B, which is selected from the group of aliphatic or aromatic polyisocyanates, which can be present as monomeric, prepolymerized and/or blocked polyisocyanates, hexamethylene diisocyanate (HDI), tetramethylene diisocyanate, trimethylhexamethylene diisocyanate (TMDI), xylylene diisocyanate (XDI), methylcyclohexyl diisocyanate (HTDI or MCH), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI), diphenylmethane diisocyanate (MDI), toluene diisocyanate (TDI), their allophanates, biurets, uretdiones, isocyanurates, their blocked compounds or adducts with caprolactam, malonic acid esters, alkyl acetoacetates, as ketoximes, Schiff bases or mixtures thereof,
and a third component C, which is selected from the group of tertiary amines and their salts, in particular their chlorides, sulfates, nitrates, phosphates, phosphonates, phosphites, carboxylates with mono- or polyvalent carboxylic acids, organometallic compounds, in particular alkyl compounds of lead, zinc, tin, zirconium, titanium, their metal soaps or complex compounds with mono- or polyvalent aliphatic or aromatic carboxylic acids or anhydrous salts of polyvalent metals, in particular the halides or the carboxylates of lead, tin, zinc, manganese, titanium, zirconium, magnesium, calcium, or mixtures thereof. 18. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of epoxides comprises a first component A, which is selected from the group of oxiranes, diglycidyl ethers of bisphenol A, bisphenol F or their partially hydrogenated derivatives, unmixed or mixed with a reactive diluent for epoxy resins such as C12-C14 alkyl glycidyl ethers, butanediol diclycidyl ethers, hexanediol diglycidyl ethers, ethylhexyl glycidyl ethers, ethylhexanediol diglycidyl ethers, cyclohexanedimethyldiol diglycidyl ethers, polyoxypropylene diglycidyl ethers, polyoxypropylene triglycidyl ethers and a second component B, which is selected from the group of aliphatic, cycloaliphatic or araliphatic amines, polyamines or their adducts with oxiranes, diglycidyl ethers of bisphenol A, bisphenol F or their partially hydrogenated derivatives, polyoxyethyleneamines, polyoxypropyleneamines or mixtures thereof. 19. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of unsaturated polyesters comprises a first component A which is selected from the group of esters, optionally of maleic acid, fumaric acid, adipic acid, phthalic acid, phthalic anhydride, tetrahydrophthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, mesaconic acid, citraconic acid or itaconic acid with bi-, tri- or tetrafunctional aliphatic alcohols such as ethanediol, propanediol, butanediol, hexanediol, ethylhexanediol, propanetriol, trimethylolethane, erythritol, pentaerythritol, ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, hydrogenated bisphenol-A, and monomers such as α-methylstyrene, methyl acrylate, vinyl acetate, divinylbenzene, diallyl phthalate, triallyl cyanurate or Triallyl phosphate,
as accelerator/initiator a second component B which is selected from the group of tertiary amines or amino alcohols such as N,N'-dimethylaniline or N,N'-dimethylaminoethanol or from the group of hydroperoxides in combination with heavy metal salt accelerators or peroxides in combination with tertiary aromatic amines or photoinitiators,
as a co-accelerator, a third component C which is selected from the group of salts of polyvalent metals of carboxylic acids (metal soaps) such as cobalt octoate, manganese octoate, manganese stearate, calcium octoate and as an initiator, a fourth component D which is selected from the group of peroxides or azo compounds such as cumene hydroperoxide or azobisisobutyronitrile (AIBN). 20. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of (meth)acrylates comprises a first component A which is selected from the group of (cyclo)aliphatic esters of (meth)acrylic acid, their prepolymers, methyl methacrylate, butyl methacrylate, hexyl methacrylate, hexanediol methacrylate, ethylhexanediol dimethacrylate, polyoxypropylene dimethacrylate, trimethylolethane trimethacrylate or mixtures thereof,
as an accelerator, a second component B which is selected from the group of tertiary amines or amino alcohols such as N,N'-dimethylaniline, N,N'-dimethylaminoethanol or mixtures thereof,
as a co-accelerator, a third component C, which is selected from the group of salts of polyvalent metals of carboxylic acids (metal soaps) such as cobalt octoate, manganese octoate, manganese stearate, calcium octoate or mixtures thereof,
and as initiator a fourth component D which is selected from the group of peroxide compounds, triphenylphosphine oxides or azo compounds such as cumene hydroperoxide or azobisisobutyronitrile (AIBN). 21. Composite safety plate according to claim 15, characterized in that the curable plastic from the group of silicone resin polymers comprises a first component A which is selected from the group of dialkylpolysiloxanes with dimethylvinylsiloxy end groups,
a second component B, which is selected from the group of alkylhydrosiloxanes
and as a catalyst a third component C which is selected from the group of platinum compounds such as hexachloroplatinic acid. 22. Composite safety plate according to one or more of claims 15 to 23, characterized in that the curable plastic comprises an adhesion promoter which is selected from the group of silanes and their hydrolysates, polysiloxanes and their hydrolysates, silicones, gaseous silanes, epoxysilanes and silanes which are gaseous at room temperature. 23. Composite safety panel according to one or more of the preceding claims, characterized in that it comprises two external supports (1), between which one, two, three, four, five, six, seven, eight, nine or ten plastic layers (2) are provided, each in direct contact with one another. 24. Composite safety panel according to one or more of claims 1 to 22, characterized in that it comprises two supports (1), between which one, two, three, four, five, six, seven or more plastic layers (2) are provided, one, two, three, four, five or more plastic layers (2) being applied to the outside of one or both supports (1). 25. Composite safety panel according to one or more of claims 1 to 22, characterized in that it comprises three supports (1), one, two, three, four, five or more plastic layers (2) being provided in direct contact with one another between the adjacent supports (1). 26. Composite safety panel according to one or more of claims 1 to 22, characterized in that it comprises two external supports (1), one, two, three, four, five or more plastic layers (2) being attached to the inside of one support (1) in direct contact with one another and an air gap (3) being formed between the last internal plastic layer (2) and the other external support (1). 27. Composite safety panel according to one or more of claims 1 to 22, characterized in that it comprises three supports (1), one, two, three, four, five or more plastic layers (2) being formed between the one outer support (1) and the middle support (1), and an intermediate space (3) filled with air or protective gas being provided between the other outer support (1) and the middle support (1).