WO2013100875A2

WO2013100875A2 - Elastic material for protection against ionised radiation

Info

Publication number: WO2013100875A2
Application number: PCT/TR2012/000230
Authority: WO
Inventors: Mevlut ERTAN; Ercument Ekrem OZCAN
Original assignee: Ertan Mevlut; Ozcan Ercument Ekrem
Priority date: 2011-12-28
Filing date: 2012-12-26
Publication date: 2013-07-04
Also published as: WO2013100875A3

Abstract

The present invention relates to protective material comprising organic materials (wool, fiber etc) and Sn SnO, BaO, BaSO₄, W, W₂O₃, WI₃, WC, Bi, Bi₂O₃, BiIO, BiI₃, Bismuthsubnitrate, Bismuthsubcarbonate and different low density metal mixtures or compositions thereof, not comprising lead (Pb), used in order to protect both the patient and the operator from the x-rays emanating out of the devices used during the diagnosis and treatment process of diseases. In order to ensure this, first of all a carrier that carries protective material such as an elastic matrix has been developed, followed by the addition of filler elements and compositions that decrease radiation, and said process has been completed by comparing the lead reference prepared with the same matrix characteristics that provide 90kV ionized ray protection.

Description

DESCRIPTION

ELASTIC MATERIAL FOR PROTECTION AGAINST IONISED RADIATION

Technical Field

The present invention, is related to protective material that does not contain lead

(Pb), used in order to protect both the patient and the operator from ionised X-rays emanating out of the devices used during the diagnosis and treatment process of patients.

Prior Art

X-rays are high frequency and thus are formed of ionised photons comprising high energy electromagnetic waves. While passing through any kind of material, said photons lead to ionisation by interacting with the atoms or molecules that form said material. If the medium from which the photons are passing through is a live cell or a tissue and if they are subjected continuously to this ray the metabolism of the cell will be effected negatively. However X-rays play a crucial role in the diagnosis and treatment of patients due to its characteristics that can enable imaging through radiation and due to the fact that said radiation can eliminate cells or tumours in radiation applications in the medical field. Aside from using x-rays for diagnosis, its usage for treatment such as radiotherapy treatment of cancer patients, in angiogram and orthopaedic radiation applications is common wherein the patient and medical staff are subjected to a long time of ionised rays during such applications. However X-rays have direct or indirect negative effects on living organisms proportional to the ray amounts given. In protection from radiation accepted worldwide which is ALARA (as low as possible), the basis of protection from radiation comprises the principle of providing the lowest possible dose of ray by taking into consideration economical and social factors. In this case the protection either of the body part aside from the organ to which X-ray is being applied to during treating a patient or the medical staff from direct or scattered ionised rays must be the primary health precaution that needs to be taken. For this reason, the protective materials that protect from radiation such as x-rays, are not only used in medical technology to protect the medical staff related to such an application but also to protect the parts of the patient which are not desired to be subjected to such radiation. In order to protect from such rays in medical applications protective clothes, gloves, hats or l thyroid protectors, protection for the genital area, pads, curtains and screens are used to protect medical staff and patients. These radiation protective products need to have special features that absorb and/or refract the beam arriving at voltage values established between 60-125 keV exiting out of the X-ray tube.

The radiation impermeability feature of protective products mentioned above is calculated according to the formula given below;

/ = /„ i₀→ ke¥fcm?s (the intensity dose exiting out of the X-ray tube)

l→ ke¥ /ctn^zs (the intensity dose exiting out of the X-ray tube)

(μ/ρ) mass attenuation coefficient unit (cm2)

x— > samplethickness, unit(cm)

The higher the mass attenuation coefficient (μ/ρ) of the product the lower the intensity (I) of the beam emanating out of the sample.

Table- 1 shows the mass attenuation coefficients (μ/ ?) of some materials in different x-ray intensities.

Table-1. The mass attenuation coefficient of some elements and compositions according to different X-ray strengths

Table-2. The attenuation characteristics of elements.

Material N_re) 0.1 kg/m² (rel PB) 60-80 kV de

and 0.1 Group kg/m² PbGW

increase

60 - 90 kV 60 - 125 kV 100-125 kV 125- *150 kV

Sn 1.64 1.30 0.96 0.80 -0.005 A

Bi 1.41 1.27 1.13 1.17 -0.005 A

W 0.91 1.07 1.25 1.07 +-0.000 A

Gd 1.85 2.05 2.27 1.56 +0.007 B

Er 1.20 1.45 1.70 1.36 +0.009 B

As it can be seen in this table elements or their compounds can be classified according to below grouping as mentioned in the patent document numbered WO 2005/023116.

Group-A:Relativerley less effective materials Nrel < 1.2 - 1-6 mm PbGW. 0.1 kg/m² and elements that show negative increase at 60*80 kV. These are Sn, Bi, W and their compounds

Group-B: those showing significant increase in N rel > 1.3 mm PbGW pro 0.1 kg/m2 60-80 kV.

By taking this feature into account, in the absorption and/or diffraction feature of the protective equipment providing protection against radiation; the attenuation value, is defined as the attenuation factor and is determined according to the EN 61331-1 standard (Devices providing protection against X-rays used for diagnosis in Medicine, Section 1: Determination of the attenuation characteristics of Materials) as lead equivalence or as lead attenuation value.

Generally lead and lead compounds are used in x-ray protective materials as they are easy to obtain and they are fully protective. However as products with lead contents are so heavy that they can be uncomfortable to the human anatomy (lead density (d)= 11.00 g/cm³), and as they are difficult to recycle, and damaging to the environment and human health when mixed into water, they are (deemed the most important toxic waste which is the hardest to recycle among environmental pollutants according to both the united nations and the world health organisation) disadvantageous. Due to such disadvantages studies are carried out to produce alternative materials that provide protection from ionised rays.

In the studies carried out, instead of lead, it has been determined that materials such as bismuth (Bi), aluminium (Al), antimony (Sb), barium (Ba), iodine (I), copper (Cu), cadmium (Cd), mercury (Hg), nickel (Ni), tantalum (Ta), tellerium (Te), uranium (U), zirconium (Zr), tin (Sn), tungsten (W), Zinc (Zn), Iron (Fe), cerium (Ce), caesium (Cs), indium (In), gadolinium (Gd) and magnesium (Mg) which carry similar characteristics but whose toxicity are much lower than lead could be used. The suitable radiation attenuation materials can be the elements mentioned above or the salts and especially the oxides of these compounds or a mixture thereof. However their usage as elastic pads or textile products that have been laminated, and that are at a certain thickness (in products that have been produced using lead as 0.1-0.6 mm/area in comparison with test reference samples) or are a unit area in practical applications have been put forward (US 4,938,233; US 5,278,219; US 6,310,355 Bl; WO 2005/023116 Al).

As binding matrix materials that provide elasticity characteristics and that enable for the filling materials to be combined, polymeric structures comprising viscoelastic vinyl polymers, vinyl acetate copolymers, silicon and urethanes (polyester, polyether, polybutadiene), polychloroprene, rubber (natural and synthetic), polystyrene-butadiene block copolymers, poly(n-butyl metachrilate), PS diluted with tricresyl phosphate(polystyrene), polymethylacrilate, poly (alfa-methylstyrene), cellulase trinitrate, polyacrylonitrile, PVC (polyvinylchloride), cellulose tributyrin, cellulose nitrate, gelatine and various PS and polyisoprenes or cross linked poly(beta-hydroxyethylmetacrilate) gels, polyethylenes [LDPE, LLDPE, VLDPE, MDPE, HDPE, MPE (metallocene polyethylene), EVA, EMA (ethyl metacrylate), EEA (ethylene ethylacrilate), EBA (ethylene butyl acrilate)], acid copolymers, [ethylene metacrylic acid, ethylene acrylic acid, ionomer sold under the commercial name of Surlyn comprising zinc and sodium, adhesive polymers that can be extruded and sold under the commercial name of Bynel, thermoplastic elastomers [styrenic block copolymers, thermoplastic polyurethane, polyolefin blends, elastomeric alloys, thermoplastic copolyesters and metallocene plastomers], thermoplastic polyamide (nylon), polypropylenes can be used. Especially rubbers such as IR (polyisoprene rubber), BR (polybutadiene rubber), SBR (styrene-butadiene copolymer rubber) can also be used. In this patent, these polymers are also used as a matrix for ray protective elements and their compounds. Plasticizers are added in order to increase the elasticity, processability, tensibility, to decrease the melting viscosity, to decrease the secondary transition temperature (glass transition temperature) and in order to be able to add further filling materials into the structure of the polymer to be used inside the protective material. Di-alkyl phthalate, di- undecylenic phthalate (DUP), dioctyl phthalate (DOP), di-isononyl phthlalate (DINP), dioctyltherephthalate (DOTP), tributyl phosphate, and dioctyl maleate, DHA (di-n-hexyle adipate) and dicarboxylic/tricarboxylic esthers such as BBP (butyl benzyle phthalate), disononyl cyclo hexane (DINCH-Hexamoll®), benzoates, epoxy vegetable oils, sulphonamides, organophosfates and adipates, can be used as plasticizers.

Regarding the initial studies in material formulation, in the patent document numbered GB 954,594 published in 1964, the product has been described in which lead powder is used instead of lead plates, silicon rubber is used in the matrix formulation as a binder and sheep's wool is used in a little amount as supporting material.

In the patent document numbered US 4,938,233 products that can be manufactured using dispersant filling materials, loaded on elastic polymeric matrix, and protecting against dispersed rays are described. In this document the plasticizer/polymer rate is between 5: 1 to 32:1; thus the amount of the ray attenuating filler material can be loaded up to 80%. In the application, it is known that the 6mm sample in the rate of 97% x- ray dispersion attenuation factor comprises 75% barium sulphate (BaS0₄).

In the patent document numbered US 2002/0148980 Al the attenuation filler obtained by mixing bismuth oxide and barium sulphate in the amount of (22:78 w/w), in order to attenuate the dispersed rays have been formed in a manner to comprise LDPE 1031 coded low density polyethylene in different amounts. This product has the characteristics to attenuate at least 10-50% of primary X-rays of 100 keV. Moreover in this patent document, it has been defined that the amount of radiation attenuation material can change both the attenuation amount, and the elasticity provided by the polymer and according to various sources; it has been stated that the weight of the attenuation material must be higher than the weight of the polymeric material.

In the patent document numbered US 2009/0272921 Al the material is a material which provides protection in the lead equivalence of 0.25 mm, 0.35 mm, 0.50 mm, 1.00 mm, and comprises low and high atom numbered protective materials in layers.

In the patent document numbered WO 2004/055833 Al the mixture obtained from at least 26% gadolinium and barium, indium, tin, lanthanum, molybdenum, niobium, tantalum, zirconium and tungsten alloys/compounds and rubber and polyurethane polymers as matrices are used in order to provide protection from radiation.

In the patent document numbered US 3,961,123 novolac resins (phenolic polymer) comprising sulphonic acid, and metallic atom lead whose radiation attenuation capacity is high and compounds of cadmium or barium elements are bound to polymers ionically by an ionic transformation process. The thread manufactured is then used in manufacturing textiles that can prevent the passage of radiation.

In the patent document numbered US 5,278,219 the polymeric material that can submit, disperse and absorb energies such as x-rays, γ ray, sound and electricity, and that contains at least 90% metallic filler material, has been put under protection such that it has a thickness that can attenuate x-rays as much as at least a 0.1mm lead can attenuate an x- ray higher than lOkeV.

In the patent document numbered US 6,310,355 Bl the material that is protected is lighter than other materials in comparison due to its porous surface. Inside the pores materials such as gas (helium etc.), and materials such as foam are present. These pores or cavities do not have any kind of negative effect in attenuating the passage of x-rays. This material is a protective material that can decrease a lOOkeV primary X-ray at least by 50%, that has a shore (00) rigidity of less than 100, and whose friction coefficient is less than 0.15.

In the patent document numbered US 2004/0041107 Al a material is described wherein it can decrease by at least 50% a 100 keV primary X-ray, that can be obtained by extrusion, which has at least one layer, and a part of its attenuation filler is obtained by dispersing in a polymeric structure.

The patent document numbered US 2005/0121631 Al describes the thin, light and elastic product developed to be used in radiation attenuation. Said product is obtained by moulding high molecule weighted metal particles and low viscosity viscous latex and casting said materials. Said material can comprise metal parts up to 89% in their structures.

In the method described in the patent document numbered DE 19955192 Al a polymer matrix in the production of protective material and a metal numbered with a high atom close to lead is used. In the high elasticity structure described in patent numbered DE 20100267 Ul, a light and soft rubber type radio protective material is defined. Tin element with atom numbered 50 and oxide has been added inside this matrix material as filler.

In the patent document numbered US 5,548,125 tungsten dispersion is provided inside natural rubber. In the patent document numbered US 2004/0262546 a dispersion inside natural rubber either as Bi₂0₃ on its own or a mixture of W₂0₃ and SnO, SnSb0₂ have been proposed. It has been seen that the radio protective effects of providing radiation protective fillers comprising bismuth, tungsten, tin and oxides thereof are lower in comparison to metallic lead and thus gloves to be produced as such do not provide protection adequate enough in terms of radio protect! vity; however said product is still deemed to be more useful practically due to it being softer, and having plastic and elastic characteristics. A study similar to the study of the radiation protection effect of filler material's particle size, that is to be described under the comprehensive definition of this invention which has characteristics equivalent to lead or higher protective characteristics and practicality has been described in the patent document FP 2,911,991. This patent has targeted to solve the problem in the matrix by encapsulating as a liquid the radio opaque material bismuth oxide. This study which was carried out, aims to eliminate the hardening effect of bismuth oxide in the elastomers by forming an interface structure between bismuth oxide filler particles and elastomer plastic.

In the patent documents DE 11 2009 002 123 T5 and patent documents RU 2054439 and RU 2028331 it has been seen that the non lead radiation decreasing material produced via a carrier system and with a latex binder of an organic rare metal oxides was not durable against high energy rays and it has been seen that the matrix showed degradation and that elements such as bismuth metals could be directly added to the polymer matrix.

Hence it has been thought to support the elastic polymers and plasticizers of this invention as mentioned above with natural polymers such as cotton, silk, sheep's wool, Ankara Angora goats wool and Toros black goat's wool, and in application when the protein sourced gelatine, bovine, albumin, human albumin and other keratinized proteins from animal sources were added at the rate of 1-15%, large numbers of products that are resistant against radiation applications and products that attenuate against partially low energy rays have been planned to be prepared by ourselves. Ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), O Acid glycoprotein and silk β- keratinize mostly carried 27-43% glycine, 23-30% alanine, 12-16% leucine or serine and 12- 17 other aminoacids. β-keratin type is a sample for regular proteins. Protein fibers such as sheep, goat, and black goat fibers are seen to be proteins with a structure (a-helix structure) formed of basic keratin proteins carrying 4-16% cistern. Especially when sheep's wool, Angora goats wool, Toros black goat's wool is compaired, it has been observed that the cistern rate is respectively sheep's wookAngora goats wookToros black goat's wool, and when these wools have been added at a rate of 10-25% to the main matrix polymer, it has been determined that against 90 keV intensity X-ray, between 2-15% wool had the least, and black goat's wool had highest rate of attenuation; and in the matrix as it is specific to Turkey Toros goat's fibre and Ankara Angora fiber has been added to the formulation as strengtheners (E. Buddecke, Grundriss Der Biochemie, FiirStudierende der Medizin Zahnmedizin und Naturwissenschaften, 8. Auflage, Walter de Gruyter, Berlin, New York 1989, syf 146-147.)

To the explanations in the below mentioned table, some natural polymers ionized x- ray attenuation characteristics have been compared as samples. When it is taken into consideration that PVC/NBR (40/60) matrix is evaluated and the attenuation characteristic of the same ray of the matrix is between 1-4% the findings in the table are remarkable.

Table 3: some of the natural polymer's comparative x-ray attenuation characteristics

(Radiation strength 90kvP, distance: 60cm, sample thickness: 1.4mm)

As it is known, the medical research methods carried out to measure by using x-rays between the dose of 60-150 keV is as follows; ,

• 60-90 keV X-ray Dose

In single or panoramic radio techniques, in the radiological inspections in dentistry.

• 60-125 keV X-ray Dose

Angiogram, computerized tomography (CT), heart-catheter, classic radiology, thorax- heart radiation techniques.

• 100-125 keV X- ray Dose

Computerized Tomographies (CT) • 125 - 150 keV X-ray Dose

Special computerized tomographies, bone density measurement, Special thorax-heart ray measurement technique, Nuclear medical diagnostic techniques, radiology and special applications in nuclear medicine

· 60-125 keV X-ray Dose

General radiation field

• 100-140 keV X-ray Dose

CT measurements

Brief Description of the Invention

The aim of the invention is related to the preparation of a material formulation that provides protection from low intensity X-rays which does not comprise lead. The formulation has been planned to comprise 3 steps. 1) Matrix formulation 2) The determination of the structure and characteristics of a filler material 3) The effect of the particle size of the filler material to the ray attenuation.

1) Matrix Formulation

The basic formula for the matrix formulation shall be carried out within the framework of the rates given in Table 4.

Table-4. General Matrix Formulation

Basic composition polymers of the matrix materials carrying the filler agent can be polymers such as;

Viscoelastic vinyl polymers, vinyl acetate copolymers, silicon and urethanes (polyester, polyether, polybutadiene), polychloroprene, rubber (natural and synthetic), polystyrene-butadiene block copolymers, poly(n-butyl metacrylate), PS diluted with tricresol phosphate (polystyrene), polymethylacrilate, poly (alfa-methylstyrene), cellulase trinitrate, polyacrylonitrile, PVC (polyvinylchloride), cellulose tributyrin, cellulose nitrate, gelatine and various PS and polyisoprenes or cross linked poly(beta-hydroxyethylmetacrilate) gels, polyethylenes [LDPE, LLDPE, VLDPE, MDPE, HDPE, MPE (metallocene polyethylene), EVA, EMA (ethyl metacrylate), EEA (ethylene ethylacrilate), EBA (ethylene butyl acrilate)], acid copolymers, [ethylene metacrylic acid, ethylene acrylic acid] ionomer sold under the commercial name of Surlyn comprising zinc and sodium, (adhesive) polymers that can be extruded and sold under the commercial name of Bynel, thermoplastic elastomers [styrenic block copolymers, thermoplastic polyurethane, polyolefin blends, elastomeric alloys, thermoplastic copolyesters and metallocene plastomers], thermoplastic polyamide (nylon), polypropylenes can be used. Especially rubbers such as IR (polyisoprene rubber), BR (polybutadiene rubber), NBR (Nitrile butadiene rubber), SBR (styrene-butadiene copolymer rubber) and various mixtures thereof can also be used.

Plasticizers inside the matrix material basic composition carrying the filler agent;

Plasticizers are added in order to increase the elasticity, processability, tensibility, to decrease the melting viscosity, to decrease the secondary transition temperature (glass transition temperature) and in order to be able to add further filling materials into the structure of the polymer to be used inside the protective material. As plasticizers di-alkyl phthalate, di-undecylenic phthalate (DUP), dioctyl phthalate (DOP), di-isononyl phthlalate (DINP), di-hexyle phthalate (DHP), tributyl phosphate, and dioctyl maleate, di-n-hexyle adipate (DHA), and butyl benzyle phthalate (BBP), di-hexyle therephthalate (DHTP), dibutyl therephthalate (DBTP), dioctyl therephthalate (DOTP), disononyl cyclo hexane (DINCH- Hexamoll®), benzoates, epoxy vegetable oils (black opium poppy, canola oil and raw cotton oil etc), various sulphonamides and organophosphates are used.

Catalysts inside the matrix material composition carrying the filler agent;

These type of catalysts used today, are separated into two groups as alkaline and acidic groups. Various catalysts add commencement of scorching and scorching characters to rubber mixtures and different physical and aging characteristics to vulcanised parts.

The classification of certain catalysts according to their vulcanization velocity is as follows:

•Slow catalysts: Aldehyde-amine, thiocarbanalide.

«Mid velocity catalysts: Guanidine

•Semi ultra catalysts: Thiazole-sulphenamides

•Ultra catalysts: Thiurams (dimorpholine thiuram disulphate, dipyyrrolidine thiuram disulphate, dipiperidine thiuram disulphate, tetraethyl thiuram disulphate, tetraisopropyle thiuram disulphate, tetramethyl thiuram disulphate), dithiocarbamates (zinc diethyl dithiocarbamate, manganese diethyl dithiocarbamate), xanthates (barium-, calcium, zinc- xanthate)

Activator inside the matrix material main composition carrying the filler agent;

In this invention BaO, ZnO, TiO inorganics were used as activators.

Antioxidants inside the matrix material's basic composition carrying the filler agent;

The polymer and conditioners in the matrix which are basic materials mostly are oxidized with air oxidisation and their life span decreases. The antioxidants released into the medium for this reason can be some inorganic antioxidants aside from organic antioxidants such as Gallic acid, benzoic acid, resorcinol, pyrogallon, hydroquinone, ascorbic acid, Polymerized 2,2,4-trimethyl-l,2-dihydroquinoline(TMQ), N-isopropyl-N'-phenyl-p- Phenylenediamine(IPPD), N-(l,3-dimethyl-butyl)-N'-phenyl-P Phenylenediamin.

Strengthened inside the matrix material basic composition carrying the filler material;

Various types of supporting polymers regarded as pre filler agents in order to provide durability and polymer stabilization in the matrix can be used. Although from the carbohydrate polymers, known polymers such as cotton, cellulase etc are not suitable, proteins and polypeptides rich in sulphur and which are not soluble in water can be used. Ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), en-Acid glycoprotein, silk, sheep's wool, wool from different types of goat such as Toros black goat, Ankara Angora goats wool and other animal type wool and carbon black, or one or more thereof can be used as strengtheners.

2) The determination of the structure and characteristics of the filler agent

When the above patents are examined, elements and compositions with the atom number between 49-55 and elements and compositions with the atom number between 56-83 from the basic element groups, have tried to be tested. As it has been defined, in the first group Sn, Sb, I and sometimes Se, in the second group Ba, W, Ir, Pb and Bi is used. In the recent years, some elements and compositions from the lanthanum and actinium series can be benefited from. When the price advantage and risk advantage relationship from these elements and compositions are taken into consideration, in this present invention Sn, Sb, I, Ba, W, Pb an Bi and compositions thereof are examined. When the basic non lead radioprotective aim of the invention is taken into consideration, it has to be noted that the production carried out with lead has only been used as reference material. The first group Sn, Sb, I, Se and compositions thereof from the elements we have listed, have been noted to have 45keV X-ray intensity attenuation; while Ba, I, W, Bi and compositions thereof have been noted to absorb ionized rays and have been used in order to attenuate ray intensity higher than 60keV. In the present invention although Sn and SnO, BaO are not used as they are characterised to be intensively basic, BaS0₄, W, W₂0₃, WI₃, WC, Bi, Bi₂0₃, BilO, Bil₃, Bismuthsubnitrate, Bismuth subcarbonate have been taken into consideration and have been added to the matrix as filler agents. In the present invention all of these elements and compositions have been each examined and also they have been examined as multiple mixtures.

3) The effect of the particle size of the filler agent to the ray attenuation rate

The mixture of the matrix and the filler agent is not constituted with a chemical reaction but is constituted more with a physical and mechanical mixture. In this physical mixture the effective structural characteristic has been observed in two ways as shown below;

a. The effect of particle size to the filler agent,

b. Carrying out a liquid crystal mixture in the form of microcapsulation.

a) The morphological structure of the particle size of the filler agent which is the first characteristic and its effects have been examined and finalized by us (Figure 1).

b) As the liquid crystal mixture in the form of microcapsulation which is the second characteristic is only valid for manufactures (gloves etc) carried out with liquid formulation and from the manufacturing carried out based on said formulations a special study has not been conducted by us.

Another aim of the invention is to carry our basic formulations in order to be able to produce non lead, protective gear, providing protection from low intensity x-rays suitable to prepare protective chambers for dentistry, such as protective garments, gloves, hats, thyroid protectors, genital region protectors, pads, curtains, screens, comprising Sn and SnO, BaO, BaS0_4/ W, W₂0₃, WI₃, WC, Bi, Bi₂0₃, BilO, Bil₃, Bismuthsubnitrate, Bismuth subcarbonate and organic materials such as "ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), Oi-Acid glycoprotein, silk, sheep's wool, different types of goat's wool (Toros black goat, Ankara Angora goat) and other animal type wool" which can be converted into a layer in a dough machine by a homogenously mixing procedure conducted via a mixer/Banbury/kneader.

Description of the Drawings

Figure la. Shows the images of W(2-5 pm) filler agents in the scanning electron microscopes

Figure lb. Shows the images of Bi (10-13 pm) filler agents in a scanning electron microscope Figure lc. Shows the images of BilO (11-16 pm) filler agents in a scanning electron microscope

Figure Id. Shows the images of Sn (2-5 pm) filler agents in a scanning electron microscope Figure le. Shows the images of Bi203 filler agents in a scanning electron microscope

Figure 2. Show the ionised x-ray intensity attenuation characteristic of the material prepared.

1. X-rav tube

2. X ray

3. Tanned sample

4. Electrometer

5. Iyonised chamber (at a 60 cm lateral 60 cm vertical distance)

Detailed description of the Invention

The non lead protective material comprises one or more inorganic active fillers such as Sn and SnO, BaO, BaS0₄, W, W₂0₃, WI₃, WC, Bi, Bi₂0_3/ BilO, Bil₃, Bismuthsubnitrate, Bismuth subcarbonate. Bismuthsubcarbonate; has been used to prepare BilO aside from Bi₂0₃ and Bismuthsubnitrate filler agent, but BaO was only used at the rate of 0-1.0% as a catalyst in order to achieve an attenuation filler agent.

Moreover the particle size of the attenuation material is important in terms of the distribution inside the polymer matrix. It is recorded in the literature that the attenuation per unit mass with the combination of the elements which are compatible to each other in the structure that has been established is higher than those elements that are used on its own.

In the present invention 6-12% difference in the favour of the small particled protective element and compositions has been determined between the protective elements and compositions whose particle size is smaller than 60 pm and higher than 60 pm in terms of the ion attenuation rate. Hence the attenuation size of the BilO which has a particle size smaller than 16pm established in this invention is 11% higher when compared with the crystal shaped BilO mentioned in the patent numbered WO 2004/099078. In order to attain durability, resistance, protection for ray attenuation in the matrix prepared aside from the non lead protective material subject to the invention one or more of the organic materials such as ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), or Acid glycoprotein, silk, sheep's wool, different goat type wools (Toros black goat, Ankara Angora goat) and other wools with animal origin are used.

The matrix in the non lead protective material subject to the invention, comprises one or more polymeric binders defined under the title "Basic composition polymers of the matrix materials carrying the filler agent" as a binder.

The matrix in the non lead protective material subject to the invention comprises one or more plasticizers defined under the title "Plasticizers inside the matrix material basic composition, carrying the filler agent" as plasticizers.

1. The preparation methods of various chemicals;

1.1 BilO Synthesis:

Sample-1

The Bilo synthesis in the patent document numbered WO 2004/099078 has been given in detail in the figure below;

20.0 g Bi(N0₃)₃, is mixed into 5H₂0 70 ml 50% acetic acid solution and is dissolved (Solution I). 10.0 g sodium acetate, 6.0 g Nal and 3.5 g sodium benzoate is dissolved in 350 ml water (Solution II). Solution I is slowly mixed and added to solution II during one minute, and an intense yellow coloured precipitation is obtained. The mixture is mixed in room temperature for 24 hours in order to obtain recrystalization and at the end of this period an orange coloured mixture is obtained. After the produce is drained water is added and re^¬ mixed. At the end of the process the mixture is drained and is washed with 200ml water three times. The mixture is dried at 80 °C/10³ Pa and BilO is obtained.

Sample-2

As the obtained BilO is a crystallized structure the BilO synthesis having a particle size smaller than 16 pm using a different synthesis process; is dissolved in 120.0 g (6.0 part/weight) KI or (5.4 part/weight Nal) 300.0 ml de-ionised water, 700.0 ml de-ionized water is added to 200.0 g (10 part/weight) Bismuthsubnitrate, and the mixture is mixed in a mechanical mixture (1200 cycle/minute), and the mixture is heated at 85 °C temperature. KI (or Nal) solution is slowly (2-10 minutes) added on top. The mixture is mixed for a further 30 minutes and left to cool. After the mixture is washed three times each time with 300ml de-ionized water, the mixture is drained and is dried at 80 °C/10³ Pa ; thus BilO is obtained. The mass obtained has a particle size larger than 16pm. (Yield 96%).

* part weight: weight/weight (wt/wt)

1.2 SnO synthesis

225.63 g (lmol) SnCI₂ is mixed with 500.0 ml de-ionized water up to 80 °C temperature and is mixed and dissolved. 80.0 g NaOH is dissolved in 500.0 ml de-ionized water and SnCI₂ precipitation is added to NaOH solvent and mixed (1250 cycle/minute) slowly (in 5-15 minutes). The mixture is mixed for 45 minutes and is left to cool. It is washed with 300 ml de-ionized water each time and after it has been drained it is dried at 90 °C/10³ Pa and grey SnO with a particle size smaller than 16pm is obtained (Yield %89).

1.3 Bil¾ Synthesis

70 g (0.33 mol) Bismuth and 128 g (lmol) Iodine is mixed in a fume cupboard and following this it is kept inside a container in a drying oven at 110 °C for an hour. The mass is dissolved in 250 ml ethanol, it is poured into a lit de-ionized water via a mechanic mixer and a micro particle Bil₃ is obtained (Yield 75%). 2. Preparation of Matrixes:

Sample 2.1.

10-80 part/weight latex

20-90 part/weight plasticizer 0.5-1 part/weight catalyst

0-1 part/weight activator

0-1 part weight antioxidant 2-6 part/weight strengtheners

Sample 2,2,

15-60 part/weight PVC

40-85 part/weight plasticizer 0-0.5 part/weight catalyst

0-1 part/weight activator

0-1 part/weight antioxidant 2-10 part/weight strengtheners

Sample 2.3.

10-60 part/weight PVAc-Acrilate 40-90 part/weight plasticizer 0-0.5 part/weight catalyst

0-1 part/weight activator

0-1 pait weight antioxidant 2-10 part/weight strengtheners

Sample 2.4. 0-100 part weight natural rubber 0 part/weight plasticizer 0-0.5 part/weight catalyst 0-1 part/ weight activator 0-1 part/weight antioxidant 2-10 part/weight strengtheners

Sample 2.5.

20-70 part/weight PVC/NB 30-80 part/weight plasticizer 0-0.5 part/weight catalyst 0-1 part/ weight activator 0-1 part/weight antioxidant 2-10 part/weight strengtheners

Sample 2.6.

10-40 part/weight PVC

60-90 part/weight natural rubber 0-40 part/weight plasticizer 0-0.5 part/weight catalyst 0-1 part/weight activator 0-1 part/weight antioxidant 2-10 part/weight strengtheners

Sample 2.7.

10-40 part/weight PVC/NBR 60-90 part/weight natural rubber

0-40 part weight plasticizer

0-0.5 part/weight catalyst

0-1 part weight activator

0-1 part weight antioxidant

2-10 part/weight strengtheners

Sample 2.8.

10-60 part/weight PVC/NBR

60-90 part/weight PVC

0-40 part/weight plasticizer

0-0.5 part/weight catalyst

0-1 part/weight activator

0-1 part/weight antioxidant

2-10 part/weight strengtheners

Sample 2.9.

10-40 part/weight EPDM

0-40 part/weight plasticizer

0-0.5 part weight catalyst

0-1 part/weight activator

0-1 part/weight antioxidant

2-10 part/weight strengtheners

3. Lamination with Matrix of the ionized ray decreasing material

Sample 3.1. The sample which comprises 60 part/weight DOP is taken from sample- 2.1, 40 part/weight BaS0₄ (d=2.61g/cm³) is added and mixed, lamination is carried out in a lamination machine.

Sample 3.2.

The sample which comprises 70 part/weight DHA is taken from sample- 2.1, 30 part/weight BaS0₄ (d=2.61g/cm³) is added and mixed, lamination is carried out in a lamination machine

Sample 3.3.

The sample which comprises 60 part/weight (comprising DOP and Ankara Angora goats wool) is taken from sample- 2.1, 40 part weight BaS0₄ (d=2.61g/cm³) is added and mixed, lamination is carried out in a lamination machine

Sample 3.4.

The sample which comprises 60 part/weight (90 part weight DOP and 10 Part/weight PVC) is taken from sample- 2.2, 40 part/weight BaS0₄ (d=2.61g/cm³) is added and mixed, lamination is carried out in a lamination machine

Sample 3.5.

The sample which comprises 50 part weight (70 part/weight DOP and 30 part/weight latex) is taken from sample- 2.1, 50part weight Bismuthsubnitrate is added and mixed, lamination is carried out in a lamination machine

Sample 3.6.

The sample which comprises 50 part/weight (70 part/weight DOP and 30 part/weight latex) is taken from sample- 2.1, 50 part/weight BaC0₃ is added and mixed, lamination is carried out in a lamination machine (However BaC0₃ was not suitable for mass lamination due to its base)

Sample 3.7.

The sample which comprises 42 part/weight (90 part/weight DHA and 10 part/weight PVAc-Acrilate) is taken from sample- 2.3, 58 part/weight BaS0₄ (d=2.61g/cm³) is added and mixed, lamination is carried out in a lamination machine. (However PVAc-Acrilate copolymer does not allow for lamination with this technique) Sample 3.8.

The sample which comprises 50 part/weight (70 part/weight Hexamoll (DINCH) and 30 part/weight latex) is taken from sample- 2.1, 50 part/weight Bismuthsubnitrate is mixed, lamination is carried out in a lamination machine.

Sample 3.9.

The sample which comprises 39 part/weight is taken from Sample -2.4, and is mixed with 61 part/weight BaS0₄ (d=2.61g/cm³). The mixture is laminated in a lamination machine.

Sample 3.10.

The sample which comprises 40 part/weight is taken from Sample -2.4, and is mixed with 60 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.11.

45.7 part/weight is taken from sample 2.4 (79 part/weight natural rubber and 21 part/weight Ankara Angora goats wool), and is mixed with 54.3 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.12.

36 part/weight is taken from sample 2.4 (79 part/weight natural rubber and 21 part weight Ankara Angora goats wool), and is mixed with 56.8 part weight Bismuthsubnitrate and 7.2 part/weight Tungsten. The mixture is laminated in a lamination machine.

Sample 3.13.

38.6 part/weight is taken from sample 2.4 (79 part/weight natural rubber and 21 part/weight Ankara Angora goats wool), and is mixed with 52.8 part/weight Bismuthsubnitrate and 8.6 part/weight Tungsten carbide. The mixture is laminated in a lamination machine.

Sample 3.14.

39.8 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part/weight Ankara Angora goats wool), and is mixed with 17.2 part weight BaS0_4/ 39.2 part/weight Bismuthsubnitrate and 3.8 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.15.

36.2 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part/weight Ankara Angora goats wool), and is mixed with 15.6 part/weight BaS0₄, 35.6 part weight Bismuthsubnitrate and 9.2 part weight Tungsten and 3.4 part weight BilO. The mixture is laminated in a lamination machine.

Sample 3.16.

36.3 part/weight is taken from sample 2.4 (83.4 part/weight natural rubber and 16.6 part weight Ankara Angora goats wool), and is mixed with 15.6 par weight BaS0₄, 35.7 part/weight Bismuthsubnitrate and 8.9 part/weight Tungsten carbide and 3.4 part weight BilO. The mixture is laminated in a lamination machine.

Sample 3.17.

44.8^' part/weight is taken from Sample-2.5, and is mixed with 55.2 part weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.18.

45.6 part/weight is taken from Sample-2.5, (96.5 part weight PVC/NBR and 3.5 part/weight silk) and is mixed with 54.4 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.19.

40.6 part/weight is taken from Sample-2.5, (96.5 part weight PVC/NBR and 3.5 part weight silk) and is mixed with 48.3 part/weight Bismuthsubnitrate and 11.1 part/weight Bil₃. The mixture is laminated in a lamination machine.

Sample 3.20.

45.6 part/weight is taken from Sample-2.5, (96.5 part/weight PVC/NBR and 3.5 part/weight Ankara Angora goats' wool) and is mixed with 54.4 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.21. 52.6 part/weight is taken from Sample-2.5, (72.5 part/weight PVC/NBR and 2.5 part/weight Ankara Angora goats wool and 25 part/weight gelatine) and is mixed with 47.4 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.22.

55.6 part/weight is taken from Sample-2.6, (65.3 part/weight natural rubber and 18.5 part/weight Ankara Angora goats wool and 16.2 part/weight PVC) and is mixed with 32.5 part/weight Bismuthsubnitrate. The mixture is laminated in a lamination machine.

Sample 3.23.

56.8 part/weight is taken from Sample-2.4, and is mixed with 29.4 part weight Bismuthsubnitrate and 13.8 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.24.

46.4 part weight is taken from Sample-2.4, and is mixed with 24.1 part/weight Bismuthsubnitrate and 18.2 part/weight Bismuthsubcarbonate and 11.3 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.25.

50.7 part/weight is taken from Sample-2.6, (85 part/weight natural rubber and 15 part/weight PVC) and is mixed with 22.3 part/weight Bismuthsubnitrate, 10 part/weight BilO and 22.3 part/weight Bismuthsubcarbonate. The mixture is laminated in a lamination machine.

Sample 3.26.

44.5 part/weight is taken from Sample-2.6, (85 part/weight natural rubber and 15 part/weight PVC) and is mixed with 19.8 part/weight Bismuthsubnitrate, 9.1 partyweight BilO and 14.7 part weight Bismuthsubcarbonate and 11.9 part weight Tungsten. The mixture is laminated in a lamination machine.

Sample 3.27.

44.3 part/weight is taken from Sample-2.6, (85 part/weight natural rubber and 15 part/weight PVC) and is mixed with 19.5 part/weight Bismuthsubnitrate, 9.1 part weight BilO and 14.8 part weight Bismuthsubcarbonate and 12.3 part/weight Tungsten carbide. The mixture is laminated in a lamination machine. Sample 3.28. (Reference Sample-l)

54.4 part/weight is taken from Sample-2.6, (76 part/weight natural rubber and 24 part/weight PVC) and is mixed with 45.6 part/weight PbO. The mixture is laminated in a lamination machine.

Sample 3.29.

43.3 part/weight is taken from Sample-2.6, (76 part/weight natural rubber and 24 part/weight PVC) and is mixed with 56.7 part weight BilO. The mixture is laminated in a lamination machine.

Sample 3.30.

29.4 part/weight is taken from Sample-2.5, and is mixed with 70.6 part/weight

Bismuth. The mixture is laminated in a lamination machine.

Sample 3.31.

29.4 part/weight is taken from Sample-2.5, and is mixed with 70.6 part/weight Tungsten. The mixture is laminated in a lamination machine.

Sample 3.32.

30.8 part/weight is taken from Sample-2.5, and is mixed with 69.2 part/weight Bi₂0₃. The mixture is laminated in a lamination machine.

Sample 3.33.

56 part/weight is taken from Sample-2.5, and is mixed with 44 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.34.

34.6 part weight is taken from Sample-2.7, (78.6 part/weight natural rubber and 21.4 part/weight PVC/NBR), and is mixed with 65.4 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3,35. (Reference Sample-2)

29.4 part weight is taken from Sample-2.5, and is mixed with 70.6 part/weight PbO. The mixture is laminated in a lamination machine.

Sample 3.36.

47 part/weight is taken from Sample-2.7, (46.8 part/weight natural rubber and 40.4 part/weight Ankara Angora goats wool and 12.8 part weight PVC/NBR), and is mixed with 53 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.37.

20 part/weight is taken from Sample-2.6, (76 part/weight natural rubber and 24 part weight PVC), and is mixed with 80 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.38.

15 part/weight is taken from Sample-2.5, and is mixed with 80 part/weight Bismuth. The mixture is laminated in a lamination machine.

Sample 3.39.

20 part/weight is taken from Sample-2.5, and is mixed with 80 part/weight Tungsten. The mixture is laminated in a lamination machine.

Sample 3.40.

15 part/weight is taken from Sample-2.5, and is mixed with 80 part weight Bi₂0₃. The mixture is laminated in a lamination machine.

Sample 3.41.

15 part/weight is taken from Sample-2.5, and is mixed with 85 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.42.

20 part/weight is taken from Sample-2.7, (78.6 part/weight natural rubber and 21.4 part/weight PVC/NBR) and is mixed with 80 part/weight BilO. The mixture is laminated in a lamination machine. Thickness =0.80-0.90 mm d=1.87 g/cm³

Sample 3.43. (Reference Sample-3)

20 part/weight is taken from Sample-2.5, and is mixed with 80 part/weight PbO. The mixture is laminated in a lamination machine.

Sample 3.44.

15 part/weight is taken from Sample-2.7, (46.8 part/weight natural rubber and 40.4 part/weight Ankara Angora goats wool and 12.8 part/weight PVC/NBR) and is mixed with 85 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.45.

20 part/weight is taken from Sample-2.8, (60 part/weight PVC/NBR and 1 part/weight Ankara Angora goats' wool) and is mixed with 80 part/weight Bismuth. The mixture is laminated in a lamination machine.

Sample 3.46. (Reference Sample-4)

25 part/weight is taken from Sample-2.8, (44 part/weight PVC/NBR and 26 part/weight Ankara Angora goats' wool) and is mixed with 75 part weight PbO. The mixture is laminated in a lamination machine.

Sample 3.47.

20 part/weight is taken from Sample-2.8, and is mixed with 60 part/weight Bismuth, 20 part/weight Tungsten. The mixture is laminated in a lamination machine.

Sample 3.48.

55.5 part/weight is taken from Sample-2.9, and is mixed with 44.5 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.49.

64.6 part/weight is taken from Sample-2.5, (85.6 part/weight PVC/NBR and 14.4 part/weight Toros black goat's wool) and is mixed with 35.4 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.50.

20 part/weight is taken from Sample-2.8, and is mixed with 18 part weight Bil₃ 62 part/weight Bismuth. The mixture is laminated in a lamination machine.

Sample 3.51.

33,34 part/weight is taken from Sample-2.8, and is mixed with 33,33 part/weight tin oxide, 33,33 part/weight tin. The mixture is laminated in a lamination machine.

Sample 3.52.

31,5 part/weight is taken from Sample-2.8, and is mixed with 27,2 part/weight BaS0₄, 29,1 part/weight BilO, 12,2 part/weight Tungsten carbide. The mixture is laminated in a lamination machine. Sample 3.53.

50 part/weight is taken from Sample-2.8, and is mixed with 25 part/weight Bismuth, 25 part/weight BilO. The mixture is laminated in a lamination machine.

Sample 3.54.

50 part/weight is taken from Sample-2.8, and is mixed with 25 part/weight Bismuth,

25 part/weight Bi₂0₃. The mixture is laminated in a lamination machine.

Sample 3.55.

50 part/weight is taken from Sample-2.8, and is mixed with 56 part weight Bismuth, 24 part/weight tin. The mixture is laminated in a lamination machine.

Sample 3.56.

20 part weight is taken from Sample-2.8, and is mixed with 80 part/weight Tin. The mixture is laminated in a lamination machine. Within the scope if these basic concepts, it is possible to develop many various applications regarding the "Protective material with polymer and binders providing protection against radiation" subject to the invention, and said invention cannot be limited to the examples given herein; above all the invention is as described in the Claims.

4. Measurement of the attenuation rates

The attenuation characteristics of the ionised rays have been explained in detail above and said samples showing attenuation characteristics have been obtained according to the system given below schematically (Figure 2). The sample material range which will be measured with a x-ray source has been taken as 60cm as a standard. The ray intensity (a) distributed and refracted with an electrometer emanating from a 60 to lOOkeV source has been measured with an b) electrometer. The a) ray intensity passing through the electrometer following the submission of the rays to the material at the same ray intensities have been b) measured with the reflection of the rays to an electrometer; and

1. while the ray attenuation characteristic and the attenuation coefficient is found together (the ray intensity absorbed by the attenuating material) 2. the ray reflection rates are determined by finding the ray intensity that is reflected with an b) electrometer. All of the values have been shown in Table 5.

Table 5: The lamination thickness of the samples and the ionized x-ray at a 60cm distance and the % decrease values of the rays arriving at a 90kvP X-ray dose.

22 2.31 43.31

23 4.44 49.65

24 5.05 59.79

25 5.74 49.83

26 5.89 57.76

27 5.47 55.90

24 5.05 59.79

Bismuthsubcarbonate 25 5.74 49.83

26 5.89 57.76

27 5.47 55.90

15 5.47 44.10

26 5.89 57.76

29 5.54 49.31

33 7.79 55.61

34 7.59 69.97

36 6.78 81.52

BilO 37 9.13 87.50

41 9.57 93.00

42 9.06 88.33

44 9.89 94.14

48 7.10 60.44

49 3.07 35.30

52 7.72 70.21

53 8.86 84.23

Bil₃ 50 6.49 86.17

32 11.97 73.92

Bi₂0₃ 40 9.25 89.27

54 8.64 82.36

30 9.45 65.99

38 9.67 88.37

Bi 45 9.31 82.75

47 6.16 88.79

50 6.49 86.17 55 9.17 81.79

31 9.95 72.35

Tungsten 39 5.86 83.00

47 6.16 88.79

26 5.89 57.76

Tungsten Carbide 27 5.47 55.90

52 7.72 70.21

28 4.99 45.34

35 8.79 80.87

43 9.87 95.18

PbO

46 8.17 80.60

Sn 51 4.73 72.39

56 9.34 82.98

SnO 51 4.73 72.39

Claims

1. A filler agent carrier material preventing ionized x-rays characterized in that; it comprises between 25 to 85 part/weight polymer, 15 to 75 part/weight plasticizer, 0 to 1.0 part/weight catalyst, 0 to 1.0 part/weight activator, 0 to 1.0 part/weight antioxidant and 2 to 20 part weight strengthener.

2. A filler agent carrier material preventing ionized x-rays according to Claim 1, characterized in that; the strengthener is formed of wool, sheep's wool, Ankara Angora goats wool, Toros black goat's wool, ovomucoid, gelatine, human serum albumin (HSA), bovine serum albumin (BSA), di-Acid glycoprotein, natural protein group comprising silk or of carbon black or one or more thereof.

3. A filler agent carrier material preventing ionized x-rays according to Claim 2, characterized in that; said strengthener comprises sheep, goat, or black goat's protein fibers varying between 4-16% which are especially high in cytokine.

4. A filler agent carrier material preventing ionized x-rays according to Claim 2, characterized in that; said strengthener comprises especially Ankara Angora goat and Toros black goat's wool.

5. A filler agent carrier material preventing ionized x-rays according to Claim 2, characterized in that; it comprises between 10-60 part/weight of a filler agent.

6. A filler agent carrier material preventing ionized x-rays, characterized in that; it comprises between 10 to 80 part/weight polymer, 0 to 80 part/weight plasticizer, 0 to 1.0 part/weight catalyst, 0 to 1.0 part/weight activator, 0 to 1.0 part/weight antioxidant and 2 to 20 part/weight strengthener.

7. A filler agent carrier material preventing ionized x-rays according to Claim 6, characterized in that; it comprises between 40 to 90 part weight filler agent.

8. A filler agent according to claim 5 or 7; wherein said filler agent is selected from Sn, Sb, I, Ba, W, Pb and Bi and compositions thereof, SnO, BaO, BaS0₄, W, W₂0₃, WI₃ Tungsten carbide, Bi₂0_3/ BilO, Bil₃, Bismuthsubnitrate, Bismuthsubcarbonate or from a group comprising a mixture thereof.

9. A material that prevents ionized X-rays comprising a filler agent according to claim 5 or

7, characterized in that; it comprises 0.1-5mm thick layered products.

10. A material preventing ionized x-rays according to claim 9 characterized in that; it comprises one of more layers.

11. A filler agent carrier material preventing ionized x-rays according to claim 1 or 6, characterized in that; said polymer is made of natural rubber and synthetic rubber, NBR, EPDM, PVC and a mixture of one or more thereof.

12. A filler agent carrier material preventing ionized x-rays according to claim 1 or 6, characterized in that; said plasticizers, are selected from the group of dicarboxylic/thcarboxylic esthers such as dialkyi phthalate, dioctylphthalate (DOP), dihexyl phthalate (DHP), dihexyl therephthalate (DHTP), dioctyl (DOTP), di-isononyl cyclohexane (DINCH-Hexamolla).

13. A filler agent carrier material preventing ionized x-rays according to claim 1 or 6, characterized in that; said antioxidants are chosen from the group of resorcin, pyrogallon, hydroquinone, ascorbic acid, Polymerized 2,2,4-trimethyl-l,2- dihydroquinoline(TMQ) and metal-thiosulphate.

14. A filler agent carrier material preventing ionized x-rays according to claim 1 or 6, characterized in that; said catalysts, are chosen from the group of Thiurams (dimorpholine thiuram disulphate, dipyrrolidine thiuram disulphate, dipiperidine thiuram disulphate, tetraethyl thiuram disulphate, tetraisopropyle thiuram disulphate, tetramethyl thiuram disulphate), dithiocarbamides (zincdiethyl dithiocarbamide, manganese diethyl dithiocarbamide).