AU2019200549B2 - Radiopaque glass and use thereof - Google Patents

Abstract

Abstract The invention relates to a radiopaque glass having a refractive index nd of 1.480 to 1.561, this glass, apart from impurities at most, being free from SrO and PbO. The glass is based on the SiO 2 , A1 20 3 and B203 system. The radiopacity is adjusted using CS20 in particular in combination with BaO and/or SnO2 optionally in conjunction with fluorine. The glass may be used in particular as dental glass or as optical glass. (Fig. 1)

Description

Radiopaque glass and use thereof

Description

The invention relates to a lead-free radiopaque glass and to the use thereof.

In the dental sector, polymer-based dental compositions are increasingly being used for dental restoration. These polymer-based dental compositions consist customarily of a matrix of organic resins and various inorganic fillers. The inorganic fillers consist predominantly of powders of glasses, (glass-)ceramics, quartz or other crystalline substances (e.g. YbFs), sol-gel materials and/or Aerosils, and are added as filler to the polymer-based composition.

The aim of using polymer-based dental compositions is to prevent possible harmful side-effects of amalgam and also to enhance aesthetics. Depending on the polymer-based dental compositions selected, they may be used for a variety of dental restoration measures, as for example for dental fillings or inlays, onlays, etc., and also for crowns and bridges.

The filler as such is intended on curing to minimize the shrinkage resulting from the polymerization of the resin matrix, and at the same time to increase the abrasion resistance. Where, for example, there is strong adhesion between tooth wall and filling, excessive polymerization shrinkage may result in fracture of the tooth wall. If the adhesion is not sufficient for this purpose, excessive polymerization shrinkage may bring about the formation of marginal gaps between tooth wall and filling, which may promote secondary caries.

Furthermore, certain physical and chemical requirements are imposed on the fillers:

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It must be possible for the filler to be processed to give very fine powders. The finer the powder, the more homogeneous is the appearance of the filling. At the same time there is an improvement in the polishability of the filling, leading to improved abrasion resistance, via the reduction in the surface area open to attack, and so to a filling which retains its durability for longer. So that the powders are easy to process, moreover, it is desirable if the powders do not suffer agglomeration.

It is advanageous, furthermore, if the filler is coated with a functionalized silane, since this facilitates the formulation of the dental composition and improves the mechanical properties. The surfaces of the filler particles are customarily covered at least partly with the functionalized silane.

In terms of its transparency and, where appropriate, index of refraction, the dental glass filler should conform as close as possible to the resin matrix. Furthermore, in its entirety, which thus also includes the filler, the polymer-based dental composition is adapted aesthetically to the natural tooth material, to make it as indistinguishable as possible from the surrounding, healthy tooth material. A very small particle size of the powdered filler likewise plays a part with regard to this aesthetic criterion.

Effective chemical resistance of the fillers, especially with regard to water, may make a contribution, furthermore, to a long lifetime of the dental restoration measures.

It is absolutely vital for the treatment of patients, furthermore, that dental restoration measures are visible in an X-ray image. Since the resin matrix is generally invisible in the X-ray image, the fillers have to ensure the necessary Xray absorption. A filler of this kind which provides adequate absorption of X-rays is referred to as being radiopaque. Responsible in general for the radiopacity are

-32019200549 29 Jan 2019 constituents of the filler, examples being certain components of a glass, or additives. Such additives are also called radiopacifiers. A customary radiopacifier, besides dental glass fillers, is YbFs, which may be added in crystalline, ground form.

According to DIN ISO 4049, the radiopacity of dental glasses or dental materials is reported, relative to the X-ray absorption of aluminium, as the aluminium equivalent thickness (ALET). A relative ALET is based on a sample thickness of 2 mm. The relative ALET of 200%, therefore, means that a glass plate having plane-parallel surfaces with a thickness of 2 mm produces the same attenuation of X-rays as an aluminium plate with a thickness of 4 mm. Analogously, a relative ALET of 500% means that a glass plate having plane-parallel surfaces of 2 mm in thickness produces the same attenuation of X-rays as an aluminium plate 10 mm thick. Below, the radiopacity of the glasses is reported by statements of the relative ALET (in %).

Because the polymer-based dental composition in the application is customarily introduced from cartridges into cavities, where it is modelled, it is intended frequently to be thixotropic in the uncured state. This means that its viscosity decreases when pressure is exerted, whereas without exposure to pressure it is dimensionally stable.

With regard to the filling materials, the inert compositions are distinguished from the reactive dental compositions. The reactive dental compositions include the dental cements. In the case of dental cements, examples being glass ionomer cements, the chemical reaction of the fillers with the organic acid leads to the curing of the dental composition, meaning that the curing properties of the dental composition and thus its workability are influenced by the reactivity of the fillers. The process involved here is often one of setting, which may be preceded by a superficial radical curing, under the action of UV light, for example. The glass here may serve as a filler, which triggers or participates in the chemical reaction,

-42019200549 29 Jan 2019 or else as an inert additive which is not involved in the reaction. In that case the chemical reaction is determined by further fillers likewise present in the glass ionomer cement.

Aside from the pure inert fillers and the pure reactive fillers, there are various intermediate stages, which cannot be listed here in detail. As examples of the intermediate stages, mention may be made of compomers and resin modified glass ionomer cement (RMGIC).

Composites, also called filling composites, in contrast, contain further fillers which in chemical terms are largely inert, since their curing characteristics are determined by constituents of the resin matrix, being therefore determined initially, and a chemical reaction of the fillers and/or additives is often undesired here.

Since on the basis of their different compositions glasses represent a class of material having diverse properties, they are frequently employed as fillers for polymer-based dental compositions. Applications other than as dental material, either in pure form or as a component of a materials mixture, are also possible, as for example for inlays, onlays, facing material for crowns and bridges, material for artificial teeth or other material for prosthetic, preservative and/or preventive tooth treatment. In their application as dental material, such glasses are referred to generally as dental glasses.

Another desirable property of the dental glass, in addition to those described above, is freedom from lead oxide (PbO), which is toxic.

Dental glasses therefore represent particularly high-grade glasses. Such glasses may likewise be employed in optical applications, especially where the application profits from the radiopacity of the glass. Because the radiopacity means that the glass absorbs electromagnetic radiation in the region of the X-ray

-52019200549 29 Jan 2019 spectrum, such glasses are at the same time filters for X-radiation. Sensitive electronic components may be damaged by X-radiation. In the case of electronic image sensors, for example, the passage of an X-ray quantum may damage the corresponding region of the sensor or may lead to an unwanted sensor signal which can be perceived, for example, as image interference and/or noisy pixels. For certain applications therefore it is necessary, or at least advantageous, for the electronic components to be protected from X-radiation, by filtering out such radiation from the spectrum of the incident radiation, using corresponding glasses.

Numerous dental glasses and other optical glasses having similar optical position or comparable chemical composition are described in the prior art, but these glasses exhibit considerable disadvantages in production and/or in use. In particular, many of the glasses contain sizeable proportions of fluorides and/or Li₂O, which evaporate very readily during melting and fusing, thereby complicating the precise establishment of the glass's composition.

Chemically inert, barium-free dental glasses for use as a filler in composites are subject matter of DE 198 49 388 A1. In the case of the low-index glasses, the glasses proposed therein necessarily include proportions of ZnO and F. The latter proportions may lead to reactions with the resin matrix, which may in turn have consequences for its polymerization behaviour. Moreover, the S1O2 proportion, at 20 - 45 wt%, is limited to allow the glass described to include sufficient radiopacifier and F. In particular, in the case of low ZnO and ZrO2 contents, the addition of up to 27 wt% of SrO is recommended.

W02005/060921 A1 describes a glass filler which is to be suitable particularly for dental composites. It contains 9 to 20 mol% of alkali metal oxides. The objective in that specification is to provide glass particles whose concentration of alkali metal ions is lower at the edge of the particles than in their centre. This means that the glasses described have a deliberate chemical instability, since otherwise

-62019200549 29 Jan 2019 it would not be possible to attain this concentration behaviour. It can be assumed that the necessarily low chemical stability is achieved by the stated proportions of the alkali metals in the original glass.

An alkali metal silicate glass serving as a filler for dental material is described in EP 0885606 B1. In the glass, which is of high S1O2 content, the AI2O3 proportion of at least 5 wt% raises the viscosity and so leads to very high melting temperatures. Sodium oxides and potassium oxides are included as mandatory components. Moreover, the glass contains no components giving it radiopacity.

DE 4443173 A1 comprises a barium-free glass of high zirconium content, having a ZrC>2 content of more than 12 wt%, and other oxides. Such fillers are too reactive, especially for modern dental compositions based, for example, on acrylate, with which excessively rapid, uncontrolled curing can occur. Zirconium oxide in this quantity has a tendency towards devitrification. It produces phase separation, possibly with nucleation and subsequent crystallization. Moreover, such glasses can only be produced with high alkali metal contents, in order to ensure not too high a melting temperature, which would overstrain the melting assemblies. In turn, however, such high contents of alkali metal are deleterious to the chemical stability of the glasses.

DE 199 45 517 A1 likewise describes a glass of high zirconium content which, in applications in the dental sector, displays the same problems as the glasses in the aforementioned specification.

DE 10 2005 051 387 B3 describes as dental glass a magnesium aluminosilicate glass which in order to achieve radiopacity and an index of refraction of 1.50 to 1.549, has high contents of La2Os and/or Y2O3 and also WO3 and ZrCX This glass is free from barium, strontium and alkali metal oxides. In view of the high magnesium oxide content of such glasses, they tend towards phase separation. Another disadvantage is the high crystallization susceptibility, owing to the

-72019200549 29 Jan 2019 contents of WO3 and ZrCX These contents additionally raise the melting temperatures. La2Os is a very costly raw material and ought therefore to be avoided.

DE 10 2009 008 951 A1 discloses a radiopaque, barium-free glass and the use thereof as dental glass, mandatorily containing zirconium oxide. In order to achieve a narrow index of refraction range of 1.518 to 1.533, ZrC>2 is used with CS2O and/or La2Os. In order that such glasses can be melted, furthermore, a high K2O proportion is required. Here again, a problem with such glasses is the crystallization tendency in combination with the relatively high melting temperatures and the raw materials costs occasioned by the La2Os used. Glasses with low indices of refraction are not described by this prior art.

DE 10 2011 084 501 B3 discloses a barium-free, radiopaque glass having an index of refraction of 1.50 to 1.58. The glass is based on a combination of SrO and La2C>3 and ZrC>2 as radiopacifier. Furthermore, CS2O may be added to increase the radiopacity. Disadvantages of these glasses are the high melting temperatures and the crystallization tendency. La2Os, as described above, is very expensive.

JP 2004-002062 A discloses a glass substrate for flat screens. Besides SrO, the glasses disclosed contain primarily BaO and also high proportions of AI2O3 and MgO. The AI2O3, SrO, BaO and MgO components are needed as network transformers in order to ensure the meltability of the glass. These glasses as well are not contemplated for use as dental glasses, since they lack by far the requisite radiopacity. Apart from that, the content of AI2O3 raises the viscosity of the high-Si02-content glass and therefore necessitates high melting temperatures for the purpose of production. High contents of MgO are a disadvantage in glasses for dental applications, which are intended to have low indices of refraction in conjunction with high radiopacity. MgO does not raise the radiopacity to the same extent as the other alkaline earth metal oxides CaO, SrO and BaO, instead being manifested primarily in an increase in the index of refraction n<j, and it may therefore complicate the desired balance between low index of refraction and high radiopacity.

Features shared by all of the glasses identified in the prior art are that they either have low hydrolytic resistance or are too reactive and/or are not radiopaque, or they include components harmful to health and/or the environment. Many known dental glasses, moreover, contain SrO, which greatly increases the melting temperature. In addition to this economic disadvantage, a high SrO proportion makes for difficult-to-control crystallization operations during the production process of numerous glasses. It has emerged, moreover, that with the known radiopacifiers, employed alone or in the known combinations (usually in combination with LajOs), the radiopacity achievable cannot be increased arbitrarily and satisfactorily without too great an increase in the refractive index. Glasses having a refractive index of greater than 1.65 can currently not be used satisfactorily in practice (as described in WO 2007/034258 Al, for example) as dental glasses, fillers for polymer-based dental compositions, etc. A disadvantage of lanthanum oxide, moreover, is that it is highly priced, so reducing the economics of the glasses produced using it.

Any discussion of documents, acts, materials, devices, articles or the like which has been included in the present specification is not to be taken as an admission that any or all of these matters form part of the prior art base or were common general knowledge in the field relevant to the present disclosure as it existed before the priority date of each of the appended claims.

Throughout this specification the word comprise, or variations such as comprises or comprising, will be understood to imply the inclusion of a stated element, integer or step, or group of elements, integers or steps, but not the exclusion of any other element, integer or step, or group of elements, integers or steps.

In one aspect of the invention there is provided radiopaque glass having a refractive index n<j of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO₂ 35 -75

B2O3

2-16

AI2O3	0.8-7.5
K2O	0-14
BaO	0.6 - 24
Cs2O	1-30
SnO2	0-15
F	0-8
BaO + CS2O + SnO2 + F	>10

The invention relates to a lead-free, radiopaque glass of relatively low refractive index, having an improved radiopacity.

In particular, it is an aspect of the invention, for improved ease of production, to provide a glass system with which it is possible, within a given refractive index range, to produce glasses having a precisely defined index of refraction and, with regard to the index of refraction, improved radiopacity more easily. The glass is to be suitable preferably for use in the medical sector, especially in the dental sector as dental glass, and as optical glass. It is to be rationally producible and nevertheless of high-grade and biocompatible, and also to be suitable for passive and active dental protection, and is to have excellent properties in terms of processability, the setting behaviour of surrounding polymer matrices, and also the long-term stability and the strength. In order to meet the requirements in modern dental treatment and dental technology, moreover, the glass according to the invention must have at least good hydrolytic stability.

The glass according to the invention in its basic matrix, furthermore, is to be free from colouring components such as FezCh, CoO, NiO, CuO etc., for example, apart from impurities at most or importations and/or residual constituents that are difficult to avoid in industrial production, in order so to enable an optimum starting colour location for possible adaptations to the tooth colour and/or, in the case of optical applications, to enable the adaptation of the spectrum of the electromagnetic radiation that passes through. Moreover, the glass is to be free from a second glass phase and/or from colouring particles which lead to scattering and likewise modify the perceived colour. One or more further glass phases would lower the resistance of the glass.

2019200549 29 Nov 2019

9A

The glass of the invention is defined according to the independent claims. Preferred embodiments and applications are apparent from the dependent claims.

Provided in particular is a radiopaque glass having a refractive index n<j of 1.480 to 1.561, 5 being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO₂ 35 -75

B₂O₃2 -16

AI2O3 0.8-7.5

K₂O0 -14

BaO 0 - 24

Cs₂O 1 - 30

SnO₂0-15

F0-8

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BaO + CS2O + SnC>2 + F >10.

CS2O is always present in the glass acting as radiopacifier. In advantageous embodiments, it ensures in combination with at least one further radiopacifier the high radiopacity of the glass. Particularly advantageous variants contain CS2O and at least BaO or SnO2 as radiopacifiers, wherein La20s can also be comprised optionally. The advantageous Sn02-containing radiopaque glasses comprise SnO2 besides CS2O and BaO, optionally together with La20s. A further advantageous embodiment comprises the combination of CS2O and La20s serving as radiopaque components, wherein an advantageous variant of this embodiment can be free from BaO.

Some advantageous variants of the mentioned radiopaque glasses can contain fluorine (fluorine-containing variants). The component fluorine can be comprised in order to better adjust the refractive index depending on the used radiopacifiers. If fluorine is contained, the content will advantageously be > 0.3 wt, preferably > 0.5 wt.%. A preferred upper limit can be 6 wt.%, advantageously 5.5 wt.%, preferably 2.5 wt.%. Other advantageous variants have a significantly reduced fluorine content with a range of 0 to < 0.3 wt%, i.e. such variants can be poor in fluorine (fluorine-poor variants) or are even free of fluorine (fluorine-free variants).

An advantageous fluorine-containing embodiment of the invention is a radiopaque glass having a refractive index nd of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

Sio2	35-75
B2O3	4 - 15, in particular 5-15
AI2O3	0.8-7.5
K2O	0 - 10
BaO	0.6 - 24

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CS2O

SnO2

F

BaO + CS2O + SnC>2 + F

- 30

- 15, in particular 1-15 > 0.3, in particular > 0.5 > 10

In the purpose of the invention, advantageous sub-variants of the fluorinecontaining variant are possible, i.e. a SnC>2-containing advantageous sub-variant and a SnCMree advantageous sub-variant. The advantageous SnCUcontaining sub-variant comprises SnC>2, advantageously with a content of > 0 - 15 wt%, preferably 0.3-15 wt% or 0.5-15 wt%, further advantageously 1-15 wt%. Another advantageous SnC>2 content is > 4 - 15 wt%. Alternatively, the fluorinecontaining radiopaque glasses can advantageously be SnCMree (SnC>2 free subvariant).

An advantageous fluorine-reduced embodiment (fluorine-poor or fluorine-free variant) of the invention is a radiopaque glass having a refractive index nd of

1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	35-75
B2O3	4 - 15, in particular 5-15
AI2O3	0.8-7.5
K2O	0 - 10
BaO	0 - 24, in particular 0.6 - 24
CS2O	1 - 30
SnO2	0-15
F	0 < 0.3
BaO + CS2O + SnO2 + F	> 10

In the purpose of the invention, advantageous sub-variants of the fluorinereduced variants are possible, i.e. a SnCUcontaining advantageous sub-variant and a SnCMree advantageous sub-variant. The advantageous SnCUcontaining

- 12 2019200549 29 Jan 2019 sub-variant comprises SnC>2, advantageously with a content of > 0 - 15 wt%, preferably 0.3-15 wt% or 0.5-15 wt%, further advantageously 1-15 wt%. Another advantageous SnC>2 content is > 4 - 15 wt%. Alternatively, the fluorinepoor and/or fluorine-free radiopaque glasses can advantageously be SnCk-free (SnC>2 free sub-variant).

The glass according to the invention has a refractive index nd (also called index of refraction) of 1.480 to 1.561. It is therefore very well adapted to the available dental polymers and/or acrylate-based resins in this refractive index range, thereby satisfying the aesthetic requirements imposed on a polymer-based dental composition, especially on a dental glass/polymer composite, for appearance to be natural.

The glass according to the invention achieves the properties of lead-containing dental glasses in relation to the requisite X-ray absorption without using lead or other substances objectionable on health grounds. The glass according to the invention is lead-free. The term free from in this context denotes an absence of these substances apart from unavoidable contamination at most, that may be caused, for example, by air contamination and/or impurity in raw materials employed. However, even contamination of the glass with the unwanted substances is in general not to exceed 300 ppm for Fe2Os, preferably not more than 100 ppm, 30 ppm for PbO, 20 ppm for AS2O3, 20 ppm for Sb20s, and 100 ppm for other impurities, especially in dental glasses. SrO is always closely associated with the BaO in the raw material. Depending on the purity of the BaO raw material, there may be up to 0.7 wt% of SrO in the glass according to the invention. These limits are embraced by the wording apart from impurities at most, free from. Particularly preferred, of course, is the complete absence of the stated unwanted substances from the glass according to the invention. No SrO component is actively added, preferably, to the glass according to the invention.

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The X-ray absorption and therefore the radiopacity is advantageously achieved through a combination of radiopacifiers.

According to an advantageous variant of the invention, radiopacity is achieved by the combination of CS2O, BaO and/or SnC>2, i.e. through the presence of at least two of these components, advantageously through the presence of these three components. Unlike earlier dental glasses, which attempted to achieve radiopacity usually through the high content of, as far as possible, one high absorbing component, or through a combination with La2Os, the radiopacity in accordance with these variants of the invention is achieved by the appropriate combination of at least two of these BaO, SnO2 and/or CS2O components, which are effective for the radiopacity. In this way it is possible to attain the particularly stringent requirements for the optical properties of the glass, and also to achieve the very good hydrolytic and/or chemical resistance. Preferred for the content of BaO, SnO2 and CS2O are in total at least 8 wt%, more preferably at least 10 wt%, very preferably at least 12 wt%. Too little of these components leads to insufficient X-ray absorption. The higher the sum of these radiopacifiers in the glass, the higher is the radiopacity as well. An advantageous upper limit for the sum of BaO, SnO2 and CS2O may be 51 wt%, preferably 49 wt%, more preferably 47 wt%, also preferably 45 wt%, further preferably 43 wt%.

Furthermore regarding especially the fluorine-containing advantageous variants, the radiopaque glass comprises a defined amount of fluorine, serving to specifically adjust the refractive index of the glass depending on the particular amount of radiopacifiers. This counteracts the effect whereby, as a result of using a larger quantity of radiopacifier in the glass, the radiopacity is indeed increased, but at the same time the refractive index of the resulting glasses goes up. Through the addition of fluorine it is possible to maintain within limits the increase in the refractive index, or even to prevent the increase in the refractive index.

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The combination of the radiopacifying components BaO, CS2O, and/or SnC>2 optionally with F has proved, surprisingly, to be particularly suitable for creating glasses which have a high radiopacity in the relatively wide refractive index range from 1.480 to 1.561. In the context of the invention, provision is made for this purpose for the sum of BaO, CS2O, SnO2 and F in wt% based on oxide to be at least 8 wt.% or at least 9 wt%, preferably at least 10 wt%. Advantageously the sum can be at least 11 wt% or at least 12 wt%, some advantageous variants can have at least 13 wt% or at least 14 wt% for the sum, other advantageous variants can have at least 15 wt% or at least 16 wt.% or at least 17 wt% for the sum. An advantageous upper limit for the sum of BaO, CS2O, SnO2 and F may be 56 wt%, preferably 54 wt%, more preferably 52 wt%, also preferably 50 wt%, further preferably 48 wt%. Some advantageous variants can have an upper limit of 42 wt% or 36 wt% or 35 wt% for the sum. It is common knowledge that glasses having a lower index of refraction tend to be able to achieve a lower radiopacity and correspondingly lower values of aluminium equivalent thickness than glasses having a higher index of refraction. The reason for this is that for low-index glasses only relatively low amounts of radiopacifiers can be used. If the proportion of the radiopacifiers were increased, the refractive index would shift to higher values. Through the advantageous combination of BaO, CS2O, and SnO2 in particular with F it is possible to shift the radiopacity of the glasses and, correspondingly, the aluminium equivalent thickness to higher values over the whole refractive index range according to the invention. This means that for a given index of refraction, it is possible to achieve substantially higher X-ray visibility values than was hitherto possible. It is possible, moreover, to specifically adjust the index of refraction in a radiopaque glass.

A particularly advantageous embodiment of a radiopaque glass having fluorine and an advantageous combination of three radiopacifiers comprises:

SiO₂

B2O3

38-70

6- 15

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AI2O3	1 - 7
K2O	0 - 7
BaO	0.8 - 20
CS2O	1 - 28
SnO2	1-15, preferably >4-15
F	0.75-2.5
BaO + CS2O + SnO2 + F	> 10

All in all, success has been achieved with the invention in providing a glass system which allows the refractive index of the glass to be precisely adjusted to the particular requirements by varying the proportions of the components within the stated system, wherein the glass has an improved radiopacity for a given refractive index. This simplifies the production of differently refracting glasses with high radiopacity.

Below the glass components are described for all glasses according to the invention and advantageous variants:

As a basis, the glass according to the invention comprises S1O2 with a proportion of 35 to 75 wt% as glass-forming component. The upper limit in accordance with the invention is 75 wt%. Higher contents of S1O2 may lead to disadvantageous^ high melting temperatures, whereas, moreover, the requisite radiopacity cannot be achieved. In the case of advantageous embodiments, 73 wt%, preferably 70 wt%, more preferably 68.5 wt% or 65 wt% may be selected as an S1O2 upper limit. Some advantageous variants have an S1O2 upper limit of 64 wt%, advantageously 61 wt% or 59 wt% or 56 wt% or 53 wt%. In accordance with the invention, the lower limit is 35 wt%. Lower contents may have adverse consequences for the chemical resistance and the devitrification tendency. The S1O2 lower limit in the case of an advantageous glass composition may be 36 wt%, preferably 37 wt%, more preferably 38 wt%, further preferably 39 wt%. Some advantageous variants can comprise at least 40 wt%, preferably at least

-162019200549 29 Jan 2019 wt% or at least 45 wt% or at least 47 wt% or at least 50 wt% of SiCX One preferred embodiment of the glass according to the invention envisages a S1O2 content of 38 to 70 wt% and more preferably of 39 to 70 wt%.

B2O3 is provided in the glass according to the invention with a content of 2 to 16 wt%, advantageously of 4 to 15 wt%, preferably of 5 to 15 wt%. It may be present advantageously in the range from 6 to 15 wt% or 7 to 15 wt%. Some advantageous variants comprise 3 to 14 wt% of this component. B2O3 has a positive influence on glass formation and on melting behaviour. It also acts as a flux. Apart from the lowering effect on the melting temperature, the use of B2O3 leads at the same time to an improvement in the crystallization stability of the glass according to the invention. In accordance with the invention, therefore, the lower limit is 2 wt%. For certain glasses, 3 wt% or 4 wt%, advantageously 5 wt%, preferably 6 wt%, preferably 7 wt%, may also be selected as an advantageous lower limit for boron oxide. The upper limit for boron oxide in accordance with the invention is 16 wt%, preferably 15 wt%. Higher proportions are not recommended in this system, so as not to jeopardise the chemical resistance. A maximum of 14.5 wt%, preferably a maximum of 14 wt%, of boron oxide may also advantageously be included. If contents of B2O3 are too high, there may be instances of separation in the glass, which in turn represent an unwanted inhomogeneity of refractive index and, moreover, have adverse effects on the chemical resistance.

The glass according to the invention necessarily includes AI2O3 in the range from 0.8 to 7.5 wt%. It may be present advantageously in the range from 0.8 to 6 wt% or 1 to 7 wt%. AI2O3 improves the chemical resistance of the glass. In accordance with the invention, therefore, it is present at not less than 0.8 wt% in the glass. At least 1 wt%, preferably at least 1.2 wt% of aluminium oxide may also advantageously be used. However, an AI2O3 content of around 7.5 wt% ought not to be exceeded, so as not to increase the viscosity of the glass especially in the hot processing area - to such an extent that the glass is difficult

- 172019200549 29 Jan 2019 to melt. Moreover, excessively large amounts of aluminium oxide impair the devitrification tendency and also the resistance of the glass towards acids. The upper limit of AI2O3 is preferably 7 wt%, more preferably indeed just 6.5 wt% or 6 wt%.

Alkali metal oxides from the group of U2O, Na2O and K2O may be needed in order for the glass to be able to be melted at all. K2O serves for adjustment of the melting temperatures and at the same time strengthens the glass network. In accordance with the invention, therefore, it is present with a proportion of 0 to 14 wt%, advantageously of 0 to 12 wt%, preferably of 0 to 10 wt% in the glass composition. For K2O the range from 0 to 7 wt% can be preferred, from 0 to 5 wt% can be particularly preferred for some advantageous variants. The upper limit of 14 wt% for K2O in accordance with the invention ought not to be exceeded, since the content of alkali metal oxides lowers the chemical resistance. Advantageously, also 12 wt% or 11 wt%, preferably 10 wt%, preferably 7 wt% preferably 6 wt% may be selected as an upper limit. Particularly advantageous variants comprise at most 5 wt%, more preferably at most 4 wt% of K2O. For some advantageous variants an advantageous lower limit for K2O can be 0.5 wt%, 1 wt%, 1,5 wt% or 2 wt%. Embodiments that are free of K2O are also possible in the purpose of the invention.

Sodium ions and lithium ions have a small size which renders them more readily leached out of the glass matrix, thereby diminishing the chemical resistance, especially the hydrolytic resistance. In one advantageous embodiment of the invention, the radiopaque glass is free from Na2O and/or U2O apart from impurities at most.

Impurities may be introduced into the glass by contamination of the raw materials used for glass production, and/or by contamination and/or corrosion of the melting assemblies employed. Such impurities generally do not exceed a proportion of 0.2 wt%, especially 0.1 wt%. This also, of course, includes the

-182019200549 29 Jan 2019 complete absence of the component in question. Free from a component therefore means that the glass essentially does not contain this component, i.e. that any such component is present as an impurity at most in the glass, but is not added as an individual component to the glass composition.

The content of barium oxide is 0 to 24 wt%, preferably 0.6 to 24 wt%. A preferred range is that from 0.8 to 20 wt%, more preferably for some variants from 1 to 18.5 wt%. Too high an amount of BaO leads to the deterioration of the chemical resistance. The upper limit of 24 wt% ought therefore not to be exceeded. As an upper limit it is also possible to select for some variants, advantageously, 22 wt% or 21 wt%, more advantageously 20 wt%, preferably 18.5 wt% or 18 wt%. Further advantageous upper limits can be 17 wt%, 15 wt%, 14 wt%, 12wt % or 10 wt%. In advantageous variants at least there ought to be 0.6 wt% of BaO present in the glass, in order to acquire, together with the other substances, the X-ray absorption. BaO may be present in the glass advantageously at not less than 0.8 wt%, preferably not less than 1 wt%, more preferably not less than 1.1 wt%. Some advantageous variants can have a lower limit of BaO of 2 wt%, 4 wt% or 6 wt%. However, BaO-free radiopaque glass variants are also possible in the context of the invention which are described now.

Advantageous embodiments of radiopaque glasses can be free of BaO. In such glasses radiopacity can be based on CS2O only. For producing a higher X-ray absorption, La2Os and/or SnO2 can advantageously be used in the glass as radiopacifier(s) in addition to the contained CS2O. Advantageous variants of a radiopaque glass having a refractive index nd of 1.480 to 1.561, being free from PbO and BaO apart from impurities at most, comprise (in wt% based on oxide)

S1O2 35 - 75, in particular 38 - 70

B2O3 2 - 16, in particular 5-15, preferably 6-15

AI2O3 0.8 - 7.5, in particular 0.8 - 6

K2O 0 - 14, in particular 0-10, preferably 0 - 7

- 19 2019200549 29 Jan 2019

CS2O

SnO2

F

La20s

BaO + CS2O + SnC>2 + F

- 30, in particular 6 - 28, preferably 7 -24

- 15, in particular 0-6, preferably 0 - 3

- 8, in particular 0-6, preferably 0-3

- 19, in particular 0-16 > 10.

Regarding the BaO-free variants the component CS2O or a combination of CS2O and La2C>3 and/or SnC>2 acting as radiopacifiers can be sufficient in order to produce the radiopacity wanted in the desired refractive index range. For glasses in medical applications, especially in the dental area BaO-free variants are an advantageous alternative to the known BaO-containing and/or SrO-containing radiopaque glasses. Advantagously BaO-free variants also have a low fluorine content, especially of less than 2 wt%, preferably of less than 1 wt% or less than 0.5 wt% or less than 0.3 wt.%. Advantageous BaO-free embodiments can also be free of fluorine.

CS2O in accordance with the invention is likewise used to establish the X-ray visibility, but at the same time also contributes to improving the meltability. In accordance with the invention, CS2O is present in the glass composition at 1 to 30 wt%, preferably 1 to 28 wt%, more preferably 1.5 to 26 wt%, and very preferably 2 to 25 wt%. The alkali metal Cs is more immobile in a glass matrix by comparison with the alkali metals Li, Na, K and Rb. It is therefore leached less severely and so detracts less from the chemical resistance than do the aforementioned alkali metals. Since too small an amount of CS2O results in poorer X-ray visibility and increased melting temperatures, the lower limit according to the invention is 1 wt%. In the case of an advantageous glass composition, the lower limit may also be 1.5 wt%, more advantageously 2 wt%, preferably 2.5 wt%, very preferably 3 wt%. Some advantageous variants can contain at least 5 wt% or at least 6 wt% or at least 7 wt% CS2O. Other advantageous variants can have a lower limit for CS2O of 9 wt% or 10 wt%. In accordance with the invention there ought to be not more than 30 wt% of CS2O

-20 2019200549 29 Jan 2019 present, since otherwise the chemical resistance is impaired. An advantageous glass composition contains not more than 28 wt% of CS2O, preferably not more than 26 wt% of CS2O, more preferably not more than 25 wt% or not more than 24 wt% of CS2O. Some advantageous variants can contain at most 22 wt%, preferably at most 20 wt% or at most 19 wt% of CS2O.

SnC>2 can advantageouly serve likewise for adjusting the X-ray visibility. It contributes to a high radiopacity, with the index of refraction being increased less strongly than in the case of other radiopacifiers. This component is present in the glass composition with a proportion of 0 to 15 wt%. Some advantageous variants of the glasses according to the invention are SnCMree.

In SnC>2-containing variants SnC>2 is present in the glass composition with an advantageous proportion of 0.5 to 15 wt%, advantageously of 1 to 15 wt%, advantageously 3 to 15 wt%, preferably 4 to 15 wt%, more preferably > 4 to 15 wt%, very preferably 4 to 12 wt%, especially preferably 4-10 wt%. Too small an amount of SnC>2 may lead to poor X-ray visibility, and so this component ought to be present at not less than 0.1 wt% or 0.3 wt%, advantageously not less than 0.5 wt% or not less than 1 wt% referring to the SnCUcontaining advantageous variants. Moreover, SnC>2 improves and secures the chemical resistance of the Cs20-containing glass. As an SnC>2 lower limit, 3 wt%, preferably 4 wt%, more preferably > 4 wt% may advantageously also be provided. Too high an amount of SnC>2 results in severe devitrification and/or crystallization tendency. The upper limit of 15 wt% ought therefore not to be exceeded. Selected as an upper limit there may also be, advantageously, 13 wt%, preferably 12 wt%, more preferably 10 wt%, very preferably also 9 wt% of SnCX Variants having less SnC>2 may have an advantageous upper limit of 6 wt% or 3 wt%.

In the context of the advantageous fluorine-containing variants of the invention, the radiopaque glass contains fluorine with a proportion of at least 0.3 wt%,

-21 2019200549 29 Jan 2019 preferably at least 0.5 wt%. Present advantageously are at most 8 wt%, preferably at most 5.5 wt%, preferably at most 5 wt.% or - for some variants - at most 2.5 wt% of fluorine. Some variants have an upper limit for F of 6 wt% or 3 wt%. Advantageous ranges for F in advantageous embodiments may also be 0.75 to 2.5 wt%, particularly advantageously from 0.75 to 2.25 wt%, preferably 1 to 2 wt%. Fluorine here is reported in atomic form, referred to the mass, in the composition. It serves for adjusting the refractive index in interaction with the above-described combination of radiopacifiers, and improves the melting characteristics of the glass batch by lowering the melting temperatures. It may therefore be included at not less than 0.3 wt%, preferably at not less than 0.5 wt% in the composition. 0.75 wt% as well, preferably 1 wt%, may be selected as an advantageous lower limit. The upper limit of 8 wt%, advantageously 6 wt%, preferably 5.5 wt%, preferably 5 wt% ought not to be exceeded, since otherwise the component may evaporate during the melting operation and there may be an inhomogeneous distribution of index of refraction in the glass. Fluorine may also advantageously be present with a proportion of at most 2.5 wt%, preferably at most 2.25 wt%, more preferably at most 2 wt% in some variants.

In the fluorine-poor variants of the invention less than 0.3 wt% of F is present. The fluorine-free variants are free of F.

At this point it may be noted that, in a manner evident to the skilled person and embraced by the present description, any of the stated upper and/or lower limits of one component may be combined arbitrarily with every stated upper and/or lower limit of another component.

In one advantageous embodiment of the glass of a corresponding variant comprising SnC>2 and F, provision is made for the molar ratio of SnC>2 to F to be at least 0.4, preferably at least 0.45, more preferably at least 0.49, very preferably at least 0.5. The molar ratio of SnC>2 to F in the advantageous embodiment is at most 0.85, preferably at most 0.79, more preferably at most

-22 2019200549 29 Jan 2019

0.77, with further preference at most 0.75, also preferably at most 0.72, very preferably at most 0.7. Through this measure it is possible to set the index of refraction of the glass precisely in conjunction with a relatively high X-ray absorption. A further advantage is that the precise ratio ensures the meltability of the glass. Too high a value results in inhomogeneous melts.

In order to improve further the adjustment of index of refraction and radiopacity, i.e. high aluminium equivalent thickness, in the radiopaque glass, it is advantageous if the molar ratio of CS2O to the sum of the above-stated opacifiers CS2O, BaO and SnO2 is at least 0.05, preferably at least 0.07, more preferably at least 0.1. It is advantageous not to exceed an upper limit of 0.48, preferably of 0.45, more preferably of 0.41. Too small a ratio leads to too low X-ray absorption. Too high a ratio reduces the chemical resistance.

The radiopaque glass may optionally contain ZrC>2 with a proportion of 0 to 2 wt%, preferably 0 to 1 wt%. This zirconium content improves the mechanical properties, and particularly the tensile strength and compressive strength, and also lowers the brittleness of the glass. Contents which are too high, however, may result in the glass becoming highly reactive, particularly in the environment of dental polymers. The glass, in contrast, is to be at least very largely inert towards dental polymers, especially composites, and is for example not to interfere with their polymerization behaviour. In one advantageous variant, the glass is free from zirconium oxide (ZrCX-free).

One advantageous embodiment of a radiopaque glass may comprise a limited proportion of alkaline earths from the CaO and MgO group. The proportion of CaO may be 0 to 2 wt%. MgO is likewise optional and may be present at from 0 to 2 wt%. In one especially preferred embodiment, the glass according to the invention is free from MgO, apart from impurities at most. MgO may be disadvantageous in glasses for dental applications, which are to combine low refractive indices with high radiopacity. MgO does not raise the radiopacity to the

-23 2019200549 29 Jan 2019 same extent as the other alkaline earth metal oxides CaO, SrO and BaO, because the X-ray absorption edge of MgO is well below theirs, and exhibits only a little influence in the area of the tungsten X-ray tubes used in the medical sector. MgO would merely increase the index of refraction and thereby complicate the balance between low index of refraction and high radiopacity.

The glass according to the invention is envisaged to be free from CeO2 and T1O2, optionally, apart from impurities at most. On account of their absorption in the UV region, CeO2 and T1O2 shift the UV edge of the glass, which may consequently acquire an unwanted yellowish colouration. In one preferred embodiment, the glass according to the invention is TiO2-free.

One particularly preferred embodiment of the glass is free from T1O2 and ZrO2.

ZnO and/or WO3 and/or Nb20s and/or HfO2 and/or Ta2Os and/or Gd2Os and/or SC2O3 and/or Y2O3 and/or Yb20s may be additionally present preferably and optionally individually or in any combinations at 0 to 2 wt% in each case.

In the context of the invention, La2Os can advantageously be used with a proportion of 0 to 19 wt%, preferably 0 to 16 wt.% or 0 to 15 wt% in order to adjust the desired radiopacity of the glasses. If La2Os is comprised, it will advantageously be present in the glass with at least 0.1 wt%, preferably at least 0.2 wt%, preferred at least 0.5 wt% or at least 1 wt% in general. Preferably, La203-containing glasses comprise more than 2 wt% of this component. Some advantageous variants have a suitable lower limit of 4 wt%. An advantageous upper limit of La2Os may be 19 wt% or 18 wt%, preferably 17 wt% or 16 wt% or 15 wt%. Other advantageous variants can have a suitable upper limit for La2Os of 13 wt% or 11 wt% or 10 wt% or 9 wt% or 8 wt% or 7.5 wt% or 6 wt% or 5 wt%.

As an alternative for La203-containing variants, the invention comprises advantageous variants having a significantly reduced content of La2Os. These

-242019200549 29 Jan 2019 variants contain not more than 2 wt%, preferably not more than 1.5 wt% or not more than 1 wt% of La2Os (La20s-poor variants). If La2Os shall be present in these variants, 0.1 wt% can be an advantageous lower limit for it. The restriction of the La2C>3 content has the advantageous effect that the refractive index of the glass is not increased too much. One preferred embodiment of the glass is free from La2Os (La20s-free variant). This offers cost advantages and allows the production of low-index glasses with high radiopacity.

It is possible for the radiopaque glass, for technical or optical applications, to comprise at least one refining agent, selected for example from the group of chlorides or sulphates, with a proportion of 0 to 2 wt%, advantageously of 0 to 1 wt%. SnC>2 as well can be used as a refining agent, with the advantage over refining agents that are likewise possible, such as AS2O3 and Sb2Os, and also the stated chlorides and sulphates, that no contamination by other refining agents is carried into the melting assemblies. This is advantageous if, subsequent to technical glasses, dental glasses are produced again.

The linear coefficient of thermal expansion a₍₂o-₃oo), measured in the temperature interval from 20°C to 300°C, of the glass according to the invention is preferably less than 7x10⁶ K¹. As a result of the low coefficient of thermal expansion, the glasses according to the invention, especially when used as filling material in polymers, are capable of compensating the natural, high thermal expansion of the polymers, thus giving the polymer-based dental composition a thermal expansion which is better adapted to the natural tooth material.

As already described, the glasses according to the invention are resistant to chemical attack - that is, they are chemically stable. They preferably have a water resistance HGB in accordance with DIN ISO 719 of Class 2 or better.

-252019200549 29 Jan 2019

The glasses according to the invention are therefore notable for good chemical resistance, resulting in a high degree of inertness in combination with the resin matrix, and thus with a very long lifetime of the dental composition as a whole.

According to a further preferred embodiment of the present invention, the glass according to the invention is also preferably free from other components not stated in the claims and/or in the present description. This means that according to one such embodiment, the glass substantially consists of the stated components. The expression substantially consist here means that other components are present as impurities at the most, but are not deliberately added as an individual component to the glass composition.

Nevertheless, the invention also envisages the use of the glass according to the invention as a basis for further glasses, in which up to 5 wt% of further components may be added to the glass according to the invention described. In such a case the glass consists, in accordance with the invention, of the glass described to an extent of at least 95 wt%.

It is, of course, also possible to adapt the coloured appearance of the glass for optical or other technical applications through the addition of oxides customary for the purpose. Oxides suitable for colouring glasses are known to the skilled person, examples including CuO and CoO, which for these purposes may be added preferably at from 0 to 0.5 wt%. Moreover, the glass may be given an antiseptic function through additions, for example, of Ag2O at 0 to 3 wt%.

The invention further encompasses glass powders composed of the glasses according to the invention, and the use of a radiopaque glass according to the invention as glass powder. The glass powders are produced by known methods, as described for example in DE 41 00 604 C1. The glass powder according to the invention and/or the powder particles preferably have an average particle size of up to 50 pm, more preferably up to 20 pm. An average particle size of 0.1 μιη may be reached as a lower limit, wherein of course smaller particle sizes are also encompassed by the invention. The aforementioned glass powder may serve as starting material for the use of the glasses according to the invention as fillers and/or dental glasses in general. An advantageous use of a radiopaque glass according to the invention is in a dental glass/polymer dental composition comprising dental polymer. A dental composition of this kind finds use, for example, as dental filling material, material for inlays, onlays, dental cement, facing material for crowns and bridges, material for artificial teeth, and/or other material for prosthetic, preservative and/or preventive dental treatment.

In one preferred embodiment, the surface of the glass powder, i.e. the surface of the glass powder particles, is silanized by the customary techniques. Silanization makes it possible to improve the binding of the inorganic fillers to the polymer matrix of the polymer-based dental composition.

A radiopaque glass according to the invention for use in the medical sector, more particularly in the dental medical sector as dental glass, and/or for diagnostic purposes is provided . Diagnostic purposes include medical applications, an example being use in a contrast medium.

Furthermore, a radiopaque glass according to the invention for use as dental glass for treating cavities in human and/or animal teeth and/or for dental restoration is also provided. The treatment generally comprises complete or partial filling of a cavity, a hollow, a gap, etc., in a tooth.

The glass according to the invention may be used as described preferably as dental glass. In that case it is advantageous if the dental glass is in the form of powder particles. It is further advantageous if it is a constituent of a polymer-based dental composition comprising dental polymer, more particularly forming a filler in powder form. The surfaces of the powder particles are preferably

-272019200549 29 Jan 2019 silanized. In one advantageous embodiment, further components may be admixed to the dental composition in addition to the glass powder, examples being a barium and/or strontium and/or lithium aluminate glass-ceramic powder, an addition for further increasing the radiopacity (e.g. ytterbium trifluoride and/or yttrium fluoride), or a filler for adjusting the viscosity (more particularly fumed and/or wet-precipitated silica).

The dental glass preferably finds application as a filler in composites (also called filling composites) for the treatment, more particularly the filling, of dental cavities and/or for dental restoration, more preferably for acrylate-based polymers, which require largely chemically inert fillers. Likewise within the context of the invention is the use of the glass according to the invention as a radiopacifier in dental compositions, especially polymer-based dental compositions. The glass according to the invention is a suitable replacement for expensive crystalline radiopacifiers such as YbFs, for example. The glass according to the invention is also suitable and intended for use as a filler in dental cements, e.g. glass ionomer cements. It is likewise possible for the glass according to the invention to be used as an inert additive in glass ionomer cements. Particularly preferred is the use as an inert additive in polymer-reinforced glass ionomer cements. The polymer-reinforced glass ionomer cements comprise a class of materials available for the past few years, exhibiting per se the curing reaction of a cement, which may take a very long time, but also including a resin matrix like the composite described above, so as to be curable initially.

Correspondingly, the radiopaque glass according to the invention is used preferably for producing a dental glass/polymer composite comprising a dental polymer. The dental polymer preferably comprises a UV-curable resin based on acrylate, methacrylate, 2,2-bis[4-(3-methacryloyloxy-2hydroxypropoxy)phenyl]propane (bis-GMA), triethylene glycol dimethacrylate (TEGDMA or TEGMA, depending on what is meant here), urethane dimethacrylate (UDMA), alkanediol dimethacrylate or cyanoacrylate.

-282019200549 29 Jan 2019

Likewise encompassed by the invention is the use of the glass according to the invention as an optical element which comprises the glass according to the invention. Optical elements are understood to be all articles, and especially components, which may be employed for optical applications. These may be components through which light passes. Examples of such components are cover glasses and/or lens elements, but also supports of other components, such as mirrors and glass fibres, for example.

Cover glasses are used preferably for protecting electronic components. These, of course, likewise include optoelectronic components. The cover glasses are present customarily in the form of glass plates having plane-parallel surfaces and are preferably mounted above the electronic component, thereby protecting it from environmental effects, but allowing electromagnetic radiation such as light and X-radiation, for example, to pass through the cover glass and interact with the electronic component. For certain optoelectronic components, however, Xradiation may also be harmful. A cover glass produced from the radiopaque glass according to the invention may therefore be used for instances such as Xray protective glass, for example, in medical apparatus.

A further possible application is the use of the radiopaque glass according to the invention as cover glass and/or substrate glass in display technology for cathode ray tubes (CRT).

On the basis of its optical properties, the glass according to the invention may likewise be used for optical applications. Being largely chemically inert, it is suitable for applications as substrate glass and/or cover glass in photovoltaics, as for example for the covering of silicon-based photovoltaic cells, of organic photovoltaic cells and/or as support material for thin-film photovoltaic modules. The X-ray absorption of the glass according to the invention has particular advantages, among others, in the use of photovoltaic modules in aerospace

-292019200549 29 Jan 2019 applications, since these modules may be exposed to particularly intense Xradiation outside the Earth's atmosphere. The property of the high X-ray absorption, moreover, allows the glass to be used, very generally, as X-ray protective glass.

By virtue of its high temperature stability, the glass according to the invention is also suitable as lamp glass, particularly for use in halogen lamps and/or fluorescent tubes and related constructions. If the mechanisms of light generation in the lamp give rise to X-radiation, a particular advantage of the glass according to the invention is that this radiation can be kept away from the surroundings. Furthermore, the glass according to the invention can be used in X-ray tubes.

Additionally encompassed by the invention is the vaporization of the glass according to the invention by physical methods and the deposition of the vaporized glass on components. Such physical vapour deposition processes, also called PVD processes for short, are familiar to the skilled person and described for example in DE 102 22 964 B4. In such processes, the glass according to the invention serves as the target to be vaporized. The components vapour-coated with the glass according to the invention may benefit both from the chemical resistance of the glass and from its X-ray absorption.

Furthermore, on account of their high stability, the glasses according to the invention are likewise suitable as matrix material for the secure temporary and/or permanent storage of radioactive waste, and also for the embedding of radioactive materials.

This glass also exhibits advantages in application as container glass or packaging for pharmaceutical products. In view of the high stability with respect to ambient media, interactions with ingredients can be almost ruled out.

-30 2019200549 29 Jan 2019

Examples

The invention is illustrated below with examples which elucidate the teaching of the invention but are not intended to restrict it.

Table 1: Working examples (AB) in wt%

2019200549 29 Jan 2019

CO CO <C

CT>

CM <7>

4.9

rd

co o>

12,9

co <£>

>

co ^r

CO co

100.0

1.504

40 CM

40

-m- CD <C

CD CM IO

<O <X>

LO

3.3

CO

13.5

CO cd

co Q

CM v—

co o> CM

100.0

co CM ip

O> CM

CO co

AB13

CM IO

O>

°o rd

0.8

CO o>

15.6

cd

CM T-

CO CO

100.0

1.527

CO CO cm'

co CO

AB12

CO CO

CO

CM CO

CD CM

o IO CM

co CM

co co'

1^“

CO

o o t—

o UT> ip τ

rd

co cn co T

AB11

•kJ CO <£>

Μζ CM

co

CM

CO

cd

r

ip T—

t—

s

MT CM

M·

m <C

co θ

co rd

O CO

CM

CM CM i—

co

l

’Mt;

CO id

100.0

CO IO p

rd

v—

cn cd C

CO <O

O>

m·'

2.4

CO id * 1

15.8

1

ip T““·

CO o' ’M

100.0

1.543

g cd

<

co CD

CO CO

CO CO

CF> m-

3.4

CO

ir> id

CO cd

1

CO T~~

CM id co

100.0

1,533

CM

O MT

AB7

CO to

IO σ>

IO

CM co

co o>

CO rd

IO cd

1

<p —

o co

100.0

1.525

f2 CM

s

HGB1

<y> id

AB6

o

cr> co

5.9

3.6

Mb id

co w—

cd

»

1.7

ip CM

100.0

1.522

CM

s? co

lO CO <C

co CO io

Μα»

CM LO

3.6

CO cr>

8.8

co

T—

o CM

100.0

1.515

CO CM

670

HGB1

id

MCD <C

io S

IO <o

CO td

3.9

co IO

rd

CM

1

CO T-

CT>

100.0

1.495

CO M; CM

o Μ

rO CD <C

CM CO CO

o> T““

MT

CM

o cd

CM cm

IO

1

O> v~

<p

100.0

1.488

co cd CM

O CO

AB2

co cd co

co co τ'—

co

co cm'

IO co

-a-

CM ^r

*·—

ip co T“—

100.0

1.497

O> M* OJ

o CM MT

CO

AB1

CM m*

co cd

co cd

co T-

CM cd —

o> co

1

co

id

100.0

1.548

<0 rd

CD M· CM τ—

σ> id

Example No.

CVi o <Λ

o CQJ

o’

o

o (fl’ o

BaO

_CM o c co

e IX)

δ CO 03 LL θ dr CO c O co

Total

C1

co o y ΓΊ Ξ?

Rel.ALET (%)

Hydrolytic class to DIN ISO 719

E3 “ro ° U .—. CZ GO ο TE c o y <D CO / _cz cl o cj 1— x 3, as —

-32 2019200549 29 Jan 2019

Table 1 encompasses working examples of the radiopaque glass in the preferred compositional range. All data pertaining to the composition is listed in wt%. The glasses contain the advantageous radiopacifier combination of CS2O, BaO and SnO2, and additionally a defined amount of fluorine. The stated combination and fluorine together form an advantageous radiopacifier system, with which the index of refraction in the range from 1.480 to 1.561 and the relative aluminium equivalent thickness in the range from approximately 120% up to more than approximately 1400% can be established.

All values for the relative aluminium equivalent thickness (ALET in %) that are listed in Table 1, corresponding to X-ray absorption (XRO in %), were determined in a method based on DIN ISO 4049. The grey values determined in the image were measured using image processing software and used for determination of the X-ray absorption. Table 1 additionally lists the refractive indices nd and densities of the working examples.

The glasses described in the examples were produced as follows:

The raw materials for the oxides are weighed out and then thoroughly mixed. The glass batch is melted at about 1580°C in a discontinuous melting assembly, then refined and homogenized. At a casting temperature of about 1600°C, the glass can be cast and processed as ribbons or in other desired dimensions. In a high-volume, continuous assembly, the temperatures can be reduced by at least about 100 K.

For further processing, the cooled glass ribbons were milled by means of the method known from DE 41 00 604 C1 to form a glass powder having an average particle size of not more than 10 pm. The glass properties were determined on glass bulks which had not been milled into powders. The glasses have good chemical resistance with respect to water.

-33 2019200549 29 Jan 2019

Additionally listed in Table 1 is the chemical resistance of variants of the glass according to the invention. Given by way of example for two examples is the hydrolytic resistance class (HGB) according to DIN ISO 719. The glasses according to the invention, however, also attain good values for acid resistance according to DIN 12116 and for alkali resistance according to DIN ISO 695.

The following table G1500 shows glasses having a refractive index in the range of 1.50. The values are given in wt%.

	Table G 1500, example-no.
	500-1	500-2	500-3	500-4	500-5	500-6	500-7	500-8	500-9
SiO2	54.2	61.2	57.0	54.8	61.6	61.4	60.3	61.5	60.2
B2O3	9.5	13.4	9.2	9.4	13.5	13.4	8.9	13.5	8.9
AI2O3	5.1	1.3	4.9	5.0	1.3	1.3	4.7	1.3	4.7
K2O	3.2	4.2	3.1	3.9	4.2	4.2	3.0	4.2	3.0
CS2O	9.6	15.9	9.3	9.5	19.4	17.8	9.0	18.3	9.0
SrO
BaO	13.4		12.9	13.2			12.5		12.3
S11O2
ZrO2
F	5.0		3.4	4.3			1.6		1.6
La2O3		4.0				1.9		1.2
Cs2O+BaO+SnO2+F	28.0	15.9	25.7	27.0	19.4	17.8	23.0	18.3	22.9
Total	100	100	100	100	100	100	100	100	100
nd	1.486	1.505	1.492	1.490	1.496	1.502	1.504	1.501	1.504
Density (g/cm3)	2.63	2.58	2.63	2.64	2.52	2.57	2.65	2.57	2.65
Rel. ALET [%]	543	478	531	577	462	474	517	473	517
Hydrolytic Class to DIN ISO 719						HGB2	HGB1		HGB1
Thermal Expansion a (20-300°C) (106 K’1)	6.1	5.4	5.7	6.1	5.3	5.5	5.2	5.5	5.2

-342019200549 29 Jan 2019

The following table G 1515 shows glasses having a refractive index in the range of 1.515. The values are given in wt%.

	Table G 1515, example-no.
	515-10	515-11	515-12	515-13	515-14	515-15	515-16	515-17
SiO2	50.9	61.9	62.0	51.4	59.3	49.7	58.4	50.4
B2O3	9.8	13.6	13.8	9.8	13.2	9.6	13.1	9.7
AI2O3	4.9	1.3	1.3	4.9	1.3	4.8	1.3	4.8
K2O	3.5	4.3	4.3	3.4	4.1	3.3	4.1	3.3
CS2O	21.0	8.4	8.5	21.0	11.9	23.3	13.1	22.3
BaO	8.3	4.2	4.2	8.3	4.1	8.1	4.0	8.2
SnO2
ZrO2			1.7
F	1.6			1.3		1.3		1.3
La2O3		6.3	4.1		6.1		6.0
Cs2O+BaO+SnO2+F	30.9	12.6	12.7	30.6	16.0	32.7	17.1	31.8
Total	100	100	100	100	100	100	100	100
nd	1.514	1.510	1.508	1.512	1.514	1.517	1.517	1.515
Density (g/cm3)	2.81	2.58	2.55	2.77	2.64	2.85	2.67	2.83
Rel. ALET (%)	938	446	437	725	530	792	560	766
Hydrolytic Class to DIN ISO 719
Thermal Expans, a (20-300°C) (10’6K-1)	6.5	4.9	4.6	6.1	5.2	6.6	5.5	6.5

-352019200549 29 Jan 2019

Table G 1515 continuation, example-no.

	515-18	515-19	515-20	515-21	515-22	515-23	515-24	515-25
Sio2	58.9	55.4	56.2	57.6	52.1	52.0	57.9	58.2
B2O3	13.2	10.5	10.6	8.8	8.0	9.7	12.9	10.8
AI2O3	1.3	3.1	3.1	3.1	4.9	4.9	1.2	3.2
K2O	4.1	3.7	3.8	3.8	3.2	3.5	4.0	3.8
CS2O	12.3	17.4	17.7	17.7	23.0	28.4	17.1	19.8
BaO	4.1	6.2	7.4	7.8	8.3
S11O2
ZrO2							0.8
F		0.7	0.7	0.7	0.8	1.6		0.7
La20s	6.1	3.0	0.5	0.5			6.0	3.5
Cs2O+BaO+SnO2+F	16.4	24.3	25.8	26.2	32.1	30.0	17.1	19.8
Total	100	100	100	100	100	100	100	100
nd	1.516	1.517	1.515	1.516	1.519	1.510	1.515	1.511
Density (g/cm3)	2.66	2.76	2.75	2.76	2.87	2.85	2.68	2.69
Rel. ALET (%)	542	663	639	653	795	729	571	576
Hydrolytic Class to DIN ISO 719	HGB2	HGB2		HGB2
Thermal Expans, a (20-300°C) (10'6K-1)	5.4	6.0	6.0	6.0	6.8	6.0	5.3	5.6

-362019200549 29 Jan 2019

The following table G 1525 shows glasses having a refractive index in the range of 1.525. The values are given in wt%.

	Table G 1525, example-no.
	525-13	525-15	525-16	525-18	525-19	525-20	525-21
SiO2	53.5	52.2	52.3	47.9	58.9	57.7	57.0
B2O3	9.9	9.7	9.8	9.7	13.4	13.3	13.1
AI2O3	5.1	5.0	5.0	4.6	1.3	1.3	1.3
K2O	3.2	3.1	3.2	11.5	4.2	4.2	4.1
CS2O	9.7	9.5	9.5	10.7	8.3	8.2	10.0
BaO	13.1	12.9	12.9		8.2	9.7	10.6
S11O2
ZrO2					1.7	1.7
F	1.2	1.2	1.2
La2O3	4.3	6.3	6.0	15.6	4.0	4.0	3.9
Cs2O+BaO+SnO2+F	24.0	23.6	23.6	10.7	16.5	17.9	20.6
Total	100	100	100	100	100	100	100
nd	1.521	1.526	1.525	1.539	1.521	1.525	1.526
Density (g/cm3)	2.79	2.82	2.82	2.82	2.67	2.71	2.74
Rel. ALET (%)	667	710	706	670	539	575	603
Hydrolytic Class to DIN ISO 719			HGB1- 2
Thermal Expans, a (20-300°C) (10 6 K’1)	5.9	6.0	6.0	8.0	5.3	5.4	5.8

-372019200549 29 Jan 2019

	Table G 1525 continuation, example-no.
	525-22	525-23	525-24	525-26	525-28	525-27	525-29
SiO2	55.9	51.6	51.8	52.4	53.4	50.2	57.1
B2O3	13.0	9.6	9.6	9.5	9.4	7.8	5.4
AI2O3	1.3	5.0	4.9	4.9	4.8	4.5	1.4
K2O	4.1	3.1	3.1	3.1	3.0	2.2	0.2
CS2O	15.6	11.2	11.9	15.4	15.3	19.6	14.7
BaO	9.7	12.5	12.5	12.4	12.2	11.9	19.9
S11O2	0.5
ZrO2
F		1.1	1.0	0.5		0.8	1.1
La2O3		5.8	5.2	1.9	1.9	3.0	0.2
Cs2O+BaO+SnO2+F	25.8	24.8	25.4	28.2	27.5	32.3	35.7
Total	100	100	100	100	100	100	100
nd	1.522	1.526	1.526	1.525	1.525	1.528	1.528
Density (g/cm3)	2.74	2.84	2.84	2.84	2.85	2.94	2.95
Rel. ALET (%)	647	738	740	747	744	906	888
Hydrolytic Class to DIN ISO 719				HGB2		HGB1
Thermal Expans, a (20-300°C) (10 6 K’1)	5.9	6.1	6.1	6.2	6.2	6.6	6.0

-382019200549 29 Jan 2019

	Table G 1525 continuation example-no.
	525-30	525-31	525-32
SiO2	57.4	57.4	55.0
B2O3	12.9	13.0	8.5
AI2O3	1.2	1.3	4.9
K2O	4.0	4.1	2.4
CS2O	16.7	22.2	21.4
MgO			1.9
CaO			1.9
BaO
S11O2		0.5
ZrO2	1.8	1.9
F			0.9
La2O3	6.0		3.3
Cs2O+BaO+SnO2+F	16.7	22.7	22.3
Total	100	100	100
nd	1.520	1.521	1.525
Density (g/cm3)	2.68	2.74	2.93
Rel. ALET (%)	590	630	700
Hydrolytic Class to DIN ISO719
Thermal Expans, a (20-300°C) (10 6 K’1)	5.5	5.8	6.5

-392019200549 29 Jan 2019

The following table G 1550 shows glasses having a refractive index in the range of 1.550. The values are given in wt%.

	Table G 1550, example-no.
	550-29	550-30	550-31	550-32	550-33	550-34	550-35	550-36
SiO2	44.1	42.8	48.1	45.9	45.1	46.4	47.0	50.0
B2O3	8.1	9.3	11.6	7.8	8.1	7.9	8.1	4.9
AI2O3	3.6	4.4	1.1	3.4	3.5	3.5	3.5	3.6
K2O		11.0	3.6	0.5
CS2O	16.5	13.4	13.7	15.7	16.3	16.1	16.3	16.4
BaO	17.9	7.0	7.1	17.1	17.7	17.5	19.0	19.1
SnC>2		0.9		1.5
F	1.6				1.1	0.5	0.5	0.5
La2O3	8.3	11.2	14.8	7.9	8.2	8.1	5.6	5.6
Cs2O+BaO+SnO2+F	35.9	21.3	20.8	34.4	35.1	34.1	35.8	36.0
Total	100	100	100	100	100	100	100	100
nd	1.546	1.550	1.553	1.557	1.551	1.553	1.549	1.547
Density (g/cm3)	3.16	2.97	3.00	3.14	3.15	3.13	3.11	3.10
Rel. ALET (%)	1138	885	921	1169	1124	1105	1081	1085
Hydrolytic Class to DIN ISO 719								HGB1
Thermal Expansion a (20-300°C) (10 6 K’1)	6.6	8.4	6.5	6.4	6.4	6.3	6.4	6.3

-40 2019200549 29 Jan 2019

	Table G 1550 continuation, example-no.
	550-37	550-38	550-39
SiO2	45.8	50.5	51.9
B2O3	7.7	12.2	8.7
AI2O3	3.4	1.2	3.8
K2O	0.5	3.8
CS2O	15.7	14.4	21.9
MgO		1.0	1.8
CaO		1.4	1.8
BaO	17.1
SnO2	1.5
F	0.3		0.8
La2O3	7.9	15.5	9.3
Cs2O+BaO+SnO2+F	34.6	14.4	22.7
Total	100	100	100
nd	1.552	1.553	1.541
Density (g/cm3)	3.18	2.96	3.06
Rel. ALET (%)	1180	783	850
Hydrolytic Class to DIN ISO719
Thermal Expansion a (20-300°C) (10 6 K’1)	6.6	6.6	6.2

The glasses shown in the tables G 1500, G 1515, G 1525 and G 1550 have been experimentally melted and are thus completely or at least partially subject matter of the invention. Accordingly, the corresponding examples are also working examples.

2019200549 29 Jan 2019

Table 2: Comparative examples (VB) in wt%

US 5,641,347

VB15

70.0

40 CM

to

100.0

1.513

125

VB14

<z> c£>

<Ζ> θ CM

16.0

A θ o •^»

1.548

190

04 o S8 CO 'T co os LU Q

VB13

CO 041

1--

CM T~

o

CO

TF

CO

o

1O RT—

θ <z>

1.535

365

VB12

CO CO

CM

CM

co

co

CO

CM

s

1.514

315

co CD B 8 o· θ Q LU £2l

VB11

g CO U>

10.00

θ θ τ—

6.10

1.50

θ ’TF θ

10.00

100.00

1.512

263

VB10

63.00

0.10

12.40

10.40

8.20

o σ> co

o θ CM

100.00

1.548

276

en cn

58.00

s CM

14.00

s CM

7.93

o cn CM

En

2.00

10.00

100.00

1.534

352

m <J> co s €E> <Z> O Od cs uu o

VB8

52.09

10.30

θ θ <η

m co ο

12.98

T oO

co co rr

CM co

CO co

100.00

1.526

472

VB7

52.69

10.42

<ο <ο ιο

co in CM

13.13

CO LO

8,59

CM

100.00

1.530

m cn c-n

VB6

56.26

c*> M“·

θ ιο

2.70

14.02

g ΤΓ

CM CO

OO’OOL

1.522

276

co CD § ^r co θ § LU Q

iun CO

64.00

CO σ> CM

co CM CM

1.26

CM CM

o> cc^

CO CM

co oq co

CM M; M*

σ> i co

100.00

1.530

co

VB4

CO CM CO CO

CT> CM

CO ΙΟ τ—

CO CM v”

CM

11.43

CO CO csi

W“ CO ¢0

4,40

co CM CO

100.00

1.532

CD co co

co m ->

o> ο» to

Ο> co θ

Μ <Ο

CO 'T CM

IO CO CO

CO in

θ

12.26

4.35

co co

100.00

1.538

3 co

VB2

61.14

co co θ

2.47

CM

7.48

12.19

4,33

co

100,00

m LO Ά t—

679

VB1

CO co σ> co

co co

CM

CO CO CM

to <S

11.89

4.22

co I

100,00

1,548

763

Example No.

ί

Cm O iz>

-rj o •CM CO

Ο

ο CM _ι

O

o

o CM CA o

o ro O

o

SrO

o 1“ NJ

o ra ______1

CM o FM

oJ 5

CM o c <O

M*5 o CM Q

Total

t?

relative ALET (%)

-42 2019200549 29 Jan 2019

Table 3: Comparative examples (VB) in mol%

Example No.	EP 1 547 572 A1
mol%	VB16	VB17	VB18	VB19
SiO2	75	74	80	85
Li2O
Na2O	11	16	12	12
K2O			4
AI2Os
B2Os	4
MgO
SrO
La2Os
Y2O3	10
ZrO2		10	4	3
TiO2
Total	100	100	100	100
nd	1.52	1.54	1.50	1.49
relative ALET [%]	200	120	190	80

Tables 2 and 3 list, for comparison, the compositions, refractive indices and the relative aluminium equivalent thicknesses in % (i.e. the X-ray absorption, XRO, in %) of comparative examples. The glasses are known dental glasses and radiopaque glasses and/or fillers for use in dental compositions, in which the radiopacity derives in each case from various radiopacifier systems (use of individual radiopacifiers and/or a combination of different radiopacifiers).

Figures

The figures show:

-43 2019200549 29 Jan 2019

Fig. 1 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table 1,

Fig. 2 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table 1 with advantageous upper and lower limits,

Fig. 3 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table G 1500 with advantageous upper and lower limits,

Fig. 4 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table G 1515 with advantageous upper and lower limits,

Fig. 5 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table G 1525 with advantageous upper and lower limits and

Fig. 6 the correlation between refractive index and relative aluminium equivalent thickness for the working examples of table G 1550 with advantageous upper and lower limits.

Figure 1 shows in graph form the advantageous correlation between refractive index and relative aluminium equivalent thickness for the working examples AB1 to AB12:

It is advantageous if, within the claimed refractive index range from 1.480 to

1.561, the refractive index is assigned a relative aluminium equivalent thickness ALET (in %), as may be described by the following function:

-442019200549 29 Jan 2019

Relative ALET (%) = (15480 to 15900) * n_d - (23015 to 22695).

According to a first advantageous variant of the invention, it is advantageous if the radiopaque glass with a refractive index n_d in the refractive index range between 1.480 and 1.561 has a relative aluminium equivalent thickness ALET (%) which is greater than or equal to a minimum relative aluminium equivalent thickness (min. relative ALET) which is defined by the following equation:

min. relative ALET (%) = C * n_d - D, where C = 11000 and D = 16160.

It is further advantageous if the radiopaque glass with a refractive index n_d in the refractive index range between 1.480 and 1.561 has a relative aluminium equivalent thickness ALET (%) which is less than or equal to a maximum relative aluminium equivalent thickness (max. relative ALET) which is determined by the equation:

max. relative ALET (%) = A * n_d - B, where A = 11430 and B = 16230.

For the radiopaque glasses, therefore, advantageously, every refractive index in the n_d range 1.480 to 1.561 may be assigned an interval of the relative ALET which is bounded by a maximum relative ALET and a minimum relative ALET. A preferred radiopaque glass having a defined refractive index n_d has a relative ALET which lies advantageously in the interval of the relative ALET, the interval being calculable by the equations stated above.

According to this first advantageous variant, the assignment (n_d; relative ALET) is made by the establishing of two linear equations which define the advantageous upper and lower limits of the relative ALET in the n_d range from 1.480 to 1.561 for preferred variants of glasses. Figure 2 shows the graphs of the linear equations for AB1 to AB15. The graphs form what are called enveloping lines. In the region between the upper enveloping line (maximum) and the lower

-452019200549 29 Jan 2019 enveloping line (minimum), the advantageous range of the relative ALET, which is assigned to the nd range from 1.480 to 1.561, is located for preferred variants of the glasses. As can be seen, the working examples are located between the enveloping lines.

According to a second advantageous variant of the invention, in the refractive index range between 1.480 and 1.561, the assignment between the refractive index nd of the glass and the relative aluminium equivalent thickness ALET (%) is made via the statement of the following intervals:

nd	ALET min.	and preferably	ALET max.
1.480 to <1.490	120%	and preferably	700%
1.490 to <1.510	260%	and preferably	1000%
1.510 to <1.530	520%	and preferably	1200%
1.530 to <1.550	780%	and preferably	1500%
1.550 to 1.561	850%, preferably 910%	and preferably	1600%

What this means, to give an example, is as follows: a radiopaque glass having a given composition in accordance with the invention and a refractive index which is within the nd range between 1.490 to < 1.510 (e.g. nd = 1.50) advantageously has a relative ALET which is at least 260% (corresponding to ALET min.). At maximum, the ALET of this glass may be preferably 1000% (corresponding to ALET max.). For radiopaque glasses which fall within other nd ranges, the other values indicated in each case for ALET min. and ALET max. are valid. ALET min. therefore defines a lower limit, and ALET max. an upper limit, for the relative ALET, referred to a defined nd range.

According to an alternative advantageous variant, in the refractive index range between 1.480 and 1.561, the assignment between the refractive index nd of the

-462019200549 29 Jan 2019 glass and the relative aluminium equivalent thickness ALET (%) is made via the statement of the following intervals:

nd	ALET min.	and preferably	ALET max.
1.480 to <1.490	120%	and preferably	760%
1.490 to <1.500	240%	and preferably	875%
1.500 to <1.510	360%	and preferably	990%
1.510 to <1.520	475%	and preferably	1105%
1.520 to <1.530	590%	and preferably	1220%
1.530 to <1.540	705%	and preferably	1335%
1.540 to <1.550	820%	and preferably	1450%
1.550 to 1.561	935%	and preferably	1565%

What this means, to give an example, is as follows: a radiopaque glass having a given composition in accordance with the invention and a refractive index which is within the nd range between 1.480 to < 1.490 (e.g. nd = 1.485) advantageously has a relative ALET which is at least 120% (corresponding to ALET min.). At maximum, the ALET of this glass may be preferably 760% (corresponding to ALET max.). For radiopaque glasses which fall within other nd ranges, the other values indicated in each case for ALET min. and ALET max. are valid. ALET min. therefore defines a lower limit, and ALET max. an upper limit, for the relative ALET, referred to a defined nd range.

For gathering the data, glass bulks were produced from the glass compositions of the working examples, and the associated parameters were ascertained: the relative aluminium equivalent thickness (in %) was determined by the technique described above. The refractive index nd was determined in a known way. The number of samples per working example was 2. Each parameter was measured multiply, and the average values were calculated for the refractive index and the X-ray absorption. Linear regression allows the correlation between index of refraction and radiopacity to be represented for the radiopaque glasses

-472019200549 29 Jan 2019 according to the invention, e.g. for those glasses having the advantageous radiopacifier system of SnCfy BaO, CS2O and F, as shown in Figure 1.

For comparison, index of refraction and relative aluminium equivalent thickness are likewise plotted in Figure 1 for the stated comparative examples, which are based on different radiopacifier systems. It can be seen that the working examples in the claimed refractive index range have a much higher X-ray absorption than the comparative examples (based on the respective refractive index). For the same index of refraction, X-ray absorption values achieved in the preferred glasses are substantially higher - for example, at nd = 1.548, working example AB1 has a relative ALET of 1240%, while comparative example VB1 has only 763%, comparative example VB10 only 276%, and comparative example VB14 only 190%. In the low index of refraction range as well, at around 1.49, working example AB3 exhibits a relative ALET of 310%, whereas that of comparative example VB19 is only 80%. Accordingly, the X-ray visibility of the glasses preferred in the context of the invention, and of a polymer-based dental composition produced using them, is significantly increased. Accordingly, for the same thickness, optical elements (e.g. glass protective elements, etc.), comprising the preferred glass absorb more X-radiation as known optical elements or else, for the same X-ray absorption, can be made thinner, thereby allowing a weight saving to be made.

Especially in the case of glasses with low indices of refraction, it was hitherto difficult to raise the radiopacity, and possible only to raise it insufficiently, because increasing the proportion of radiopacifiers would have increased the index of refraction at the same time. With the advantageous radiopacifier system, comprising SnC>2, BaO, CS2O and F, a significant rise in the radiopacity is achieved even at low indices of refraction, and, in the higher index of refraction range, the aluminium equivalent thickness is improved very greatly relative to the known glasses.

-482019200549 29 Jan 2019 ln Fig. 2, working example AB15, in relation to the radiopacifier components CS2O, BaO and SnO2, exhibits a similar composition and a similarly high relative ALET as working example AB7, but with a refractive index of 1.504 has a much lower refractive index than working example AB7 (nd=1.525). This is attributable to the advantageous influence of the fluorine component, allowing the refractive index to be adjusted specifically - and in this particular case, to be lowered. As a result it is possible specifically to produce a glass having a high relative ALET and a comparatively low refractive index.

A comparison of working examples AB13 and AB14, which are likewise shown in Fig. 2, makes it clear that through appropriate choice of the radiopacifiers in the preferred radiopacifier system, comprising SnC>2, BaO, CS2O and F, it is possible to produce glasses having approximately the same refractive index but having different relative ALETs.

The advantageous equations, graphs and intervals described above for correlating the refractive index of a glass and the relative aluminium equivalent thickness are correspondingly valid for the working examples of the invention which are mentioned in the tables G 1500, G 1515, G 1525 and G 1550 (see Fig. 3 to 6). In these figures the advantageous upper and lower limits (“enveloping lines”) are indicated as well as comparative examples for comparison.

The invention may be additionally described by the following declarations as well:

1. Dental composition or dental material, comprising a radiopaque glass according to the invention as filler, for the treatment, more particularly for the filling, of cavities in human and/or animal teeth and/or for dental restoration.

2. Glass powder comprising powder particles composed of the radiopaque glass according to the invention.

-49 2019200549 29 Jan 2019

3. Glass powder according to declaration 2, wherein the surfaces of the powder particles present are silanized.

4. Filler for polymer-based dental compositions for the treatment, more particularly filling, of cavities in human and/or animal teeth and/or for dental restoration, comprising the glass according to the invention.

5. Polymer-based dental composition comprising the radiopaque glass according to the invention or a glass powder composed of the glass according to the invention.

6. Dental glass/polymer composite comprising the radiopaque glass according to the invention or a glass powder composed of the glass according to the invention.

7. Dental glass/polymer composite according to declaration 6, wherein the dental polymer is preferably a UV-curable resin based on acrylate, methacrylate, 2,2-bis[4-(3-methacryloyloxy-2hydroxypropoxy)phenyl]propane (bis-GMA), triethylene glycol dimethacrylate (TEGDMA or TEGMA, depending on what is meant here), urethane dimethacrylate (UDMA), alkanediol dimethacrylate or cyanoacrylate.

8. Dental glass/polymer glass ionomer cement comprising the radiopaque glass according to the invention or a glass powder composed of the glass according to the invention.

9. Use of a radiopaque glass according to the invention as dental glass for producing a dental glass/polymer dental composition comprising dental polymer for the treatment, more particularly filling, of cavities in human and/or animal teeth and/or for dental restoration.

-502019200549 29 Jan 2019

10. Use of a radiopaque glass according to the invention as glass powder.

11. Use according to declaration 10, wherein the surfaces of the powder particles present are silanized.

12. Use according to declaration 10 or 11 in a dental glass/polymer dental composition comprising dental polymer.

13. Use of a radiopaque glass according to the invention as

- radiopacifier in a polymer-based dental composition and/or as

- element for optical applications and/or as

- cover glass and/or substrate glass in display technology for cathode ray tubes (CRT) and/or as

- cover glass and/or substrate glass in photovoltaics and/or as

- lamp glass in X-ray tubes and/or as

- material for the embedding of radioactive materials.

14. Radiopaque glass having a refractive index nd of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	35-75
B2O3	2 - 16
AI2O3	0.8-7.5
K2O	0 - 14
BaO	0 - 24
CS2O	1 - 30
SnO2	0 - 15
F	0 - 8
BaO + CS2O + SnO2 + F	> 10,

and preferably comprising La2Os with a content of 0 - 19.

-51 2019200549 29 Jan 2019

15. Radiopaque glass having a refractive index nd of 1.480 to 1.510, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	40 - 70, in particular 50 - 65
B2O3	5 - 15, in particular 6-15
AI2O3	0.8 - 7.5, in particular 0.8 - 6
K2O	0 - 10, in particular 2 - 6
BaO	0 - 24, in particular 0-17
CS2O	1 - 30, in particular 7 - 24
SnO2	0 - 15, in particular 0 - 3
F	0 - 8, in particular 0-6
La2O3	0 - 8, in particular 0 - 5
BaO + CS2O + SnO2 + F	> 10, in particular 13-35

16. Radiopaque glass having a refractive index nd of 1.505 to 1.520, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	42 - 65, in particular 47 - 64
B2O3	5 - 15, in particular 6-15
AI2O3	0.8 - 7.5, in particular 0.8 - 6
K2O	0 - 10, in particular 2 - 6
BaO	0 - 15, in particular 2-10
CS2O	5 - 30, in particular 6 - 26
SnO2	0 - 10, in particular 0 - 3
F	0 - 5, in particular 0-3
La2O3	0 - 9, in particular 0 - 7,5
BaO + CS2O + SnO2 + F	> 9, in particular 11-35

-522019200549 29 Jan 2019

17. Radiopaque glass having a refractive index nd of 1.519 to 1.542, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	42 - 65, in particular 45 - 61
B2O3	5 - 15, in particular 7-15
AI2O3	0.8 - 7.5, in particular 0.8 - 6
K2O	0 - 14, in particular 1.5-7
BaO	0 - 18, in particular 6-14
CS2O	5 - 25, in particular 6-19
SnO2	0 - 6, in particular 0 - 3
F	0 - 5, in particular 0-3
La2O3	0 - 19, in particular 0-17
BaO + CS2O + SnO2 + F	> 8, in particular 10-35

18. Radiopaque glass having a refractive index nd of 1.542 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO2	37 - 56, in particular 40 - 53
B2O3	2 - 16, in particular 3-14
AI2O3	0.8 - 7.5, in particular 0.8 - 6
K2O	0 - 14, in particular 0-12
BaO	0 - 24, in particular 4 - 24, preferably 4 - 21
CS2O	9 - 25, in particular 10-19
SnO2	0 - 6, in particular 0 - 3
F	0 - 5, in particular 0-3
La2O3	1 - 19, in particular 4-17
BaO + CS2O + SnO2 + F	> 10, in particular 15-42

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19. Radiopaque glass having a refractive index nd of 1.480 to 1.561, being free from PbO and BaO apart from impurities at most, comprising (in wt% based on oxide)

SiO₂

B2O3

AI2O3

K2O

CS2O

SnO₂

F

La₂O3

- 75, in particular 38 - 70

- 16, in particular 5-15, preferred 6-15

0.8 - 7.5, in particular 0.8 - 6

- 14, in particular 0-10, preferred 0 - 7

- 30, in particular 6 - 28, preferred 7 -24

- 15, in particular 0-6, preferred 0 - 3

- 8, in particular 0-6, preferred 0-3

- 19, in particular 0-16

BaO + CS2O + SnO₂ + F >10.

With the described radiopacifier combination (SnO₂, BaO, CS2O) and advantageously with the defined addition of fluorine it is possible to formulate a glass having on the one hand a desired index of refraction and on the other hand an extremely high X-ray absorption. In accordance with the invention, in the refractive index range from 1.480 to 1.561, it is possible to realize a range of the relative aluminium equivalent thickness from about 120% up to more than 1400%, e.g. up to 1600%.

The examples also demonstrate that the refractive indices nd of the glass system according to the invention, particularly in a range from 1.480 to 1.561, can be adapted to the intended application without detriment to the necessary ALETs. As a result, the system can be used advantageously in particular as a filler in dental compositions, but also for other applications which impose high requirements on factors including the purity and/or the chemical resistance and temperature stability. The glass system can be produced at favourable cost on an industrial scale.

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The glass according to the invention, furthermore, is relatively easy to melt and therefore efficient to produce. Found in particular has been a glass system in which, through changes in the individual constituents within the stated limits, it is possible to adjust the refractive index in line with the requirements of the application - for example, requirements asked of a dental filling material - with the resulting glass having an improved ALET. The variation of the possible refractive indices encompassed by the invention is relatively wide. This glass system permits especially rational industrial production of glasses within the glass system, especially since only a defined selection of raw materials need be held in stock, within which the proportions are varied in the stated amounts. Accordingly, the procedural regimes when melting the glasses within the glass system are also very similar.

Claims (21)

1. Radiopaque glass having a refractive index nd of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO₂ 35 - 75

B₂O₃2-16

AI2O3 0.8 - 7.5

K2O0-14

BaO 0.6 - 24

Cs₂O 1 - 30

SnO₂0-15

F0-8

BaO + CS2O + SnO₂ + F>10 wherein the glass with a refractive index nd in the refractive index range between 1.480 and 1.561 has a relative aluminium equivalent thickness ALET (%) which is greater than or equal to a minimum relative aluminium equivalent thickness (min. relative ALET) which is determined by the following equation:

min. relative ALET (%) = C * nd - D, where C = 11000 and D = 16160.

2. Radiopaque glass according to claim 1 having a refractive index nd of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

SiO₂ 35 - 75

B2O3 4-15

AI2O3 0.8 - 7.5

K2O 0-10

BaO 0.6 - 24

Cs₂O 1 - 30

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SnO2

F

BaO + CS2O + SnO2 + F

0 - 15 >0.3 > 10

3. Radiopaque glass according to claim 1 having a refractive index n_d of 1.480 to 1.561, being free from PbO apart from impurities at most, comprising (in wt% based on oxide)

Sio₂ 35-75 B2O3 4-15 AI2O3 0.8-7.5 K2O 0 - 10 BaO 0.6 - 24 CS2O 1 - 30 SnO2 0 - 15 F 0 - < 0.3 BaO + CS2O + SnO2 + F > 10

4. Radiopaque glass according to at least one of the preceding claims, comprising F with a proportion of not more than 5,5 wt% and/or La2Os with a content of 0 - 19 wt and/or B2O3 with a content of 5 - 15 wt%.

5. Radiopaque glass according to at least one of the preceding claims, comprising F with a proportion of not more than 2.5 wt% and/or La2Os with a content of 0 - 16 wt%.

6. Radiopaque glass according to Claim 1 or Claim 2, comprising (in wt% based on oxide)

SiO₂ 38 - 70

B2O36-15

AI2O31 - 7

K2O0-7

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BaO 0.8 - 20 CS2O 1 - 28 SnO2 1 - 15 F 0.75-2.5 BaO + CS2O + SnO2 + F > 10

7. Radiopaque glass according to at least one of the preceding claims, wherein the sum of the proporions of BaO and CS2O and SnO2 and F (in wt% based on oxide) is >12%.

8. Radiopaque glass according to at least one of the preceding claims, wherein the molar ratio of SnO2 to F is at least 0.4 and/or at most 0.85.

9. Radiopaque glass according to at least one of the preceding claims, wherein the molar ratio of CS2O to the sum of CS2O + BaO + SnO2 is at least 0.05 and/or at most 0.48,.

10. Radiopaque glass according to at least one of the preceding claims, further comprising (in wt% based on oxide) at least one of the following components

ZrO₂ 0 - 2 ZnO 0 - 2 MgO 0 - 2 CaO 0 - 2 WO₃ 0 - 2 Nb₂O₅ 0 - 2 HfO₂ 0 - 2 Ta2Os 0 - 2 Gd2Os 0 - 2 SC2O3 0 - 2 Y2O3 0 - 2 Yb₂O₃ 0 - 2 La2Os 0 - 2

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11. Radiopaque glass according to at least one of the preceding claims, wherein the glass, apart from impurities at most, is free from Na2O and/or U2O and/or MgO and/or CeO2 and/or T1O2 and/or La20s and/or ZrO2.

12. Radiopaque glass according to Claim 1, wherein the glass with a refractive index nd in the refractive index range between 1.480 and 1.561 has a relative aluminium equivalent thickness ALET (%) which is less than or equal to a maximum relative aluminium equivalent thickness (max. relative ALET) which is determined by the equation:

max. relative ALET (%) = A * nd - B, where A = 11430 and B = 16230.

13. Radiopaque glass according to at least one of the preceding Claims 1 to 10, wherein in the refractive index range between 1.480 and 1.561, assignment between the refractive index nd of the glass and the relative aluminium equivalent thickness ALET (%) is as follows:

nd ALET min. ALET max. 1.480 to <1.490 120% 700% 1.490 to <1.510 260% 1000% 1.510 to <1.530 520% 1200% 1.530 to <1.550 780% 1500% 1.550 to 1.561 850% 1600%

14. Radiopaque glass according to at least one of the preceding Claims 1 to 10, wherein in the refractive index range between 1.480 and 1.561, assignment between the refractive index nd of the glass and the relative aluminium equivalent thickness ALET (%) is as follows:

nd ALET min. ALET max. 1.480 to <1.490 120% 760%

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1.490 to <1.500 240% 875% 1.500 to <1.510 360% 990% 1.510 to <1.520 475% 1105% 1.520 to <1.530 590% 1220% 1.530 to <1.540 705% 1335% 1.540 to <1.550 820% 1450% 1.550 to 1.561 935% 1565%

15. Radiopaque glass consisting to an extent of at least 95% (in wt% based on oxide) of the glass according to at least one of the preceding claims.

16. Use of radiopaque glass according to at least one of the preceding claims in the medical sector, including the dental medical sector as dental glass and/or for diagnostic purposes.

17. Use of radiopaque glass according to at least one of preceding Claims 1 to 15 as dental glass for treating, including filling, cavities in human and/or animal teeth and/or for dental restoration.

18. Use of radiopaque glass according to Claim 16 or Claim 17, wherein the dental glass is in the form of powder particles and is part of a polymer-based dental composition comprising dental polymer.

19. Use of radiopaque glass according to Claim 18, wherein the dental glass is part of the polymer-based dental composition in the form of a filler of a filling composite or in the form of a filler or an inert additive in a dental cement, including a polymer-reinforced glass ionomer cement.

20. Use of radiopaque glass according to Claim 18 or Claim 19, wherein the surfaces of the powder particles are silanized.

21. Use of a radiopaque glass according to at least one of Claims 1 to 15 as

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- radiopacifier in a polymer-based dental composition and/or as

- element for optical applications and/or as

- cover glass and/or substrate glass in display technology in the case of cathode ray tubes (CRT) and/or as

- cover glass and/or substrate glass in photovoltaics and/or as

- glass in X-ray tubes and/or as

- material for embedding radioactive materials.