DE2426919C3 - Photoluminescent building material and a method for its manufacture - Google Patents

Description

The invention relates to a voluminescent building material according to the preamble of Claim I and a method for its production.

Such a building material is described in FR PS 21 68 685. Since this material luminesces in the entire volume, it retains its luminescent properties even if the surface wears out due to abrasion. In addition to a phosphor of the ZnS type, the known building material contains a transparent filler, so that both The light required for excitation of the phosphor as well as the light emitted again by the phosphor can traverse the volume of the material.

However, such a building material does not yet have a sufficiently strong luminescence for some applications.

The present invention is therefore intended to develop a building material luminescent in volume according to the preamble of claim 1 in such a way that it luminesces even more brightly. This object is achieved according to the invention by a building material according to claim 1.

In the case of the building material according to the invention, the UV components of the ambient light are also used Excitation of luminescence. This is done by using a filler not only in the visible, but also also used in UV-permeable filler and that

ίο one in addition to raising awareness one more Provides substance in the building material which absorbs in the UV and is within the absorption spectrum of the Phosphorus emits and so for an indirect absorption of the UV light quanta by the phosphorus ensures (cascade luminescence).

There are three cases in which to choose the filler differentiate:

1. The material includes a synthetic resin permeable to ultraviolet rays and beyond various fillers permeable to these rays; overall you get a very intensely photoluminescent material

2. The material has one for ultraviolet rays permeable synthetic resin, while the fillers are only permeable to visible light.

3. The material has a synthetic resin that is only permeable to visible radiation, but the fillers are transparent to ultraviolet rays in this case.

Advantageous further developments of the invention are given in the subclaims.

The invention is described in more detail below on the basis of exemplary embodiments.

example 1

The UV-transparent components of the material contain silicon dioxide in a suitable form, e.g .: ground quartz glass, ground quartz, silica gel, silica anhydride, silica gel. Some of them can this body is in the form of a colloid into which the ultraviolet radiation can penetrate.

Such a photoluminescent building material with hydraulic binder can thus be as follows Composition "A" have.

»Λ« components

Weight share

10

1 to 2

I to 2

Hydraulic binder (White cement or Portland cement or super cement)

Pholuminescent crystals

ZnS or

CdS or

(ZnS - CdS) Cu - Rb UV-permeable colloid

(Silica gel vein

Silica anhydride (kieselguhr) or Silica gel)

Water 30 to 50

mineral fillers with high Transmission in the UV and in the visible range of the spectrum (quartz or silica anhydride or Calcium carbonate or quartz glass)

In this case a photoluminescent concrete According to the composition, the mineral fillers can optionally be used on their own up to indicated height can be used, or they can be used proportionally, provided that their Granulation allows the production of a material with the desired strength, using, for example, the granulation curve of Fuller or de Bolomey.

The photoluminescent crystals, the binder and the water can advantageously be taken together in the form of an aqueous dispersion, suspension or Emulsion conditioned. In particular, the silica gel is suitable for preparing a suspension of the silica and zinc sulfide in which the Zinc sulfide is distributed uniformly and stably

Such an aqueous dispersion, suspension or emulsion with photoluminescent properties can serve not only to moisten a cement concrete, but also to moisten Cement mortar, from gypsum concrete, stucco (plaster plus glue) and from staff.

»Β« components

Parts by weight

Example II Aqueous auxiliaries with crystalline Bs- 1 to 2

constituents or constituents, soft

high permeability in UV and

in the visible part of the spectrum

exhibit,

z. B. silicic acid compounds, carbonates (e.g. an emulsion of acrylic resin or of butadiene-styrene or of latex or a yinyl resin)

Colloids 1 to 2 transparent to UV

(from silica gel or from silica anhydride or made of silica gel)

Water 2 to 3

40 to 70 permeable to UV and visible Fillers

(Quartz or silicic acid or water-containing silicates or calcite or Quartz glass or borosilicate glass or a Mixture of corundum / quartz)

According to this example, which by the way can be combined with the first, the transparent components which form part of the photoluminescent building material are replaced by one or more suitably selected synthetic resins are (or have) those which, in particular in the case of of concrete the Fulfill the function of a binding agent, which completely absorbs the hydraulic binding agent of the cement of the concrete or can partially replace and the mass the two properties of permeability to ultraviolet rays to excite the photoluminescent Crystals and the transparency for the visible radiation emitted in the mass during photoluminescence. In the same way as that at the first embodiment is provided with the silica gel, the synthetic resin can also be used as Carriers are used to introduce the photoluminescent crystals into the mass.

The photoluminescent crystals enclosed in a synthetic resin involved in the manufacture of the concrete have an enlarged specific surface and consequently an increased sensitivity on.

Such a photoluminescent material with hydraulic binder and this supporting, photoluminescent synthetic resin has z. B. the following Overall composition »B«:

As in Example I, the mineral fillers can also be used individually here in a similar manner or used together, paying attention to suitable granulation, as before Has been carried out Advantageously, the luminescent fillers, the binder, the Water and the synthetic resin-containing auxiliary together in a single phase (aqueous dispersion, Suspension or emulsion) can be conditioned with the same success as described above.

"B" components

Oewichl parts

Hydraulic binder (White cement)

Photoluminescentc crystals (ZnS (Rb, Mn, Cu.Ag) or S (Zn: Cu) or Ca ₂ S or Zn ₂ SiO ₄ Mn (0.3)

10

1 to 2

Example HI

According to this example, photoluminescent materials do not contain conventional, hydraulic binder but a synthetic binder, i.e. a synthetic resin that hardens when exposed to heat or a thermoplastic such as polyurethane, a polyester, an epoxy resin, an acrylic resin or a vinyl resin.

In this case, the composition is a mortar

or concrete essentially as follows:

"C" components Parts by weight Resin that cures when exposed to heat. 100 of the crystalline type Aromatic plasticizer 50 Aromatic hardener 50 Mineral filler with high 800 to 1200 Permeability in UV and in Visible Photoluminescent substances 20th (Sulfides or oxides) Colloids (silica gel) 5

The photoluminescent crystals aren't either necessarily always crystals of zinc sulfide or ZnS: Cu (0.003%) [Cl] in cubic or hexagonal Form, or crystals of Zn: CdS; Ag (0.01) NaCl, you can also use photoluminescent crystals be of the oxidic type, e.g. B. zinc tungstate or a Complex like aluminum oxide with chromium as an activator.

In the case of the last-described composition "C", it is particularly advantageous as a synthetic resin to use an epoxy synthetic resin as a liquid mass of 100 parts by weight and to use a polyamide as a plasticizer as a liquid mass (amide number GY 250) to 52 parts by weight. In addition, the mineral fillers can contain water-containing silicate (talc, 0.15 μm) to 50 parts by weight, calcite (z. B. Durcal 40) to 100 parts by weight and calcite (0 135 μm) to 50 parts by weight.

A synthetic binder material for making synthetic concrete has the following Composition »D« on:

"F" components

"D" components

Parts by weight

Synthetic binder consisting of

a synthetic resin: epoxy resin an aromatic hardener with a Polyamine amide number 550 a plasticizer

Photoiuminescent crystals

(e.g. ZnS, CaS, CdS, Zn ₂ -SiO ₄₁ SrS) Colloid permeable in the UV

(e.g. silica gel or silica gel) Mineral fillers

aluminous silicates

Quartz (0 0.6 to 1.5 mm) Quartz powder

74
37

37
20th

10
350
510

Another synthetic concrete with a synthetic binder has the following composition "E":

"E" components Weight share Synthetic binder Polyurethane resin UO aromatic plasticizer 20th Component with dispersion in the UV 5 (Silica gel) photoluminescent crystals 20th Permeable in UV and visible Fillers Quartz sand (pure, washed, 1350 0 0.2 to 1 mm) Quartz powder (0 0.25 mm) 150 Calcite (0 43 a) 100

The following is the composition of a similar material for making a self smooth synthetic soil, which is marked with »F« i »':,:

Parts by weight

Synthetic resin 290 1. Polyester (amide number 1150) 70 2. Polyester (amide number 550) 260 3. Polyurethane Photoluminescent components 56 1. ZnS crystals 4th 2. UV suspending agents Fillers 195 1. Calcite 130 2. Quartz flour W6 615 3. Quartz flour W 2 Plasticizers 40 1. Thinner 100 2. Zeolite L paste

With this composition, the three fillers listed above can be replaced by a quartz / Konind aggregate (e.g. Minarthit).

It is also possible to produce a material for a floor covering based on polyrinychloride (PVC), which has the following composition, denoted by an "H":

"H" components

Weight partc

PVC (made by emulsion) 100 U.V. substance in colloidal form 2 (Silica gel) Photoluminescent crystals 20th Fillers in powder and granulate form: Borosilicate glass 200 Quartz powder 100 Aluminum silicate (kaolin) 100 Tricresyl phosphate 40 42% chlorinated paraffins 20th

If the resin is not itself for ultraviolet

Rays permeable, it can turn into an aromatic Solvent to be dissolved, which energy in

absorb a UV frequency band and in one can send out other, higher ones again.

In the example above It (choice of synthetic resins as "Transparent components") became the basic compositions for photoluminescent materials specified:

a) conventional materials with hydraulic binders and additives based on synthetic resins, b) Materials with synthetic binders, where in particular the crystalline synthetic resins as a carrier of the photoluminescent components can be used.

In addition, great care has been taken to to give the materials additional permeability for ultraviolet rays of high frequency, in which the following choice was made:

a) Crystalline synthetic resins.

b) fillers such as silicon compounds. Silicates. Mica,

c) weak pigment fillers such as calcite,

d) aromatic thinners or solvents, e.g. B. from the benzene series.

This leads to the idea of cascade photoluminescence, which a more extensive use of the energies absorbed at high energies (hr) permitted.

With this, the energy supplied to the sulfide-type phosphorescent centers is increased and thus likewise the energy of the delayed luminescence of the materials.

In addition, the specific surface of each photoluminescent center is of the order of magnitude iümai is enlarged by associating it with supports formed by crystalline synthetic resins the capture cross-section for the incident rays is also increased in the same way.

The following is an example of a cascade luminescence given. In a synthetic material with a polyurethane binder, they absorb Quartz fillers and an aromatic thinner such as anthracene or the like. Energy in the range of 3600 to 3800 A. to send them out again in the range from 3800 to 4000 Å, which is the lower threshold of the sensitivity range of the hexagonal SZn: Cu (0.003) crystal, which has a green, delayed luminescence between 3800 and 5400 Å.

The energy transmitted by the quartz components and the aromatic components comes from this to the energy absorbed by the zinc sulfide type photoluminescent centers, so that the stored light energy is increased.

In such systems one always observes a delayed luminescence which is greater. as the delayed luminescence from the photoluminescent centers alone.

In addition, to increase the permeability of the material in the ultraviolet and to improve the permeability for light, substances called porophores or porogens can be incorporated into the material, the pores of which represent collection points for the light and which permit. Manufacture materials with cell structures. This increase in permeability results in an improvement in the mechanical properties of the material as a result of the fillers, which rrv ¹ . the synthetic resin combined with the photoluminescent pigment.

Below are the following with "I". "J". "K" denoted compositions for photoluminescent Materials specified:

"J" components Weight share Crystalline resin that is not sown 100 tster has Photoluminescent crystals of the type 10 ZnS. CaS. SrS Borosilicate powder or microspheres IO glass or quartz U V.-Kollf) id. e.g. silica gel 2 catalyst 0.6 Emulsifier I. water 4th modifier 0.5 •> K «components Weight share

Fpo.xy resin 100

Photoluminescent Crystals 15

Powder or microspheres made from borosihkat 10
glass or quartz

U.V. colloid. /.B. Silica gel 2

Hardener 73

Porophore 7

Accelerator 2J

Starting from a more or less flexible reinforcement, which is formed by fabrics or the like , luminescent materials can be made in sheet form, which can be obtained by a sequence interconnected layers are formed. These layers are preferably: a Embedding resin, a fabric made of glass or quartz Synthetic resin, a mat made of glass or quartz, a synthetic resin for the production of a final surface layer (also called »gel coat«). The synthetic resins listed here can be made from polyester. Polyurethane or Be epoxy type and are made photoluminescent in the manner already described.

The entire layer that hardens when exposed to heat is exposed to heat or catalysis takes place in the cold state, and so a deposit is obtained or a thin material which photoluminesces in its volume and can be used as a building material i.

In the following possible compositions are "L". "M". "N" for such synthetic materials specified for the "synthetic resins for embedding" and the "synthetic resins for making a last surface layer ":

-I- components Weight
share "L" (synthetic resin for embedding: a + b). Weight
share Crystalline polyester resin 96 Components Photoluminescent crystals 10 of the ZnS type 180 U.V. silica gel in colloidal form 2 (a) - 1. Resin
(e.g. polyester type) 20th Diphenylmethane diisocyanate 100 J monomer Borosilicate glass or quartz in powder form 10 (e.g. styrene) 3 water 3 3. Catalyst Wetting agents 1 (7. B. peroxide)

F-'orlsel / iing Components (weight

partc

(b) - Photoluminescent Crystals:

1. of the type ZnS 20

2. Suspending agent (silica 2 acidic I)

> M «(Kumthur / / um embedding: a + b)

Components (weight

share

(a) - Resin:

1. of the Hpoxy type KX)

2. Hardener 8

(b) - Photoluminescent Ingredients:

IZnS 12

2. Suspending agent (e.g. silica I

sä u lively I)

»N« (synthetic resin for the production of a surface; a + b)

Components by weight

share

(a) - Resin:

1. Polyester 180

2. Styrene 20-type monomer

3. Fillers: aluminum-based 12 silicates

(b) - Photoluminescent Ingredients:

1. Zinc sulfide in crystalline form 20

2. suspending agent (silica gel)

3. Microspheres made of quartz glass 18 or borosilicate glass

Claims (10)

Patent claims: 1. In volume photoluminescent building material with a binder, a translucent Filler and a phosphorus-containing matrix, characterized in that it is a Contains another substance that absorbs in the ultraviolet and is within the absorption spectrum of the phosphor, and that the filler is emitted both for ultraviolet light and for visible light Light is permeable. Z building material according to claim 1, characterized in that the binder is a synthetic resin 3. Building material according to claim 1 and 2, characterized in that the further substance is a is an aromatic compound which is soluble in the synthetic resin 4. Building material according to claim 1 to 3, wherein the phosphorus is a zinc sulfide, characterized in that that the binder is a polyurethane, that the filler is a quartz filler and that the aromatic compound is anthracene 5. Building material according to one of claims 1 to 4, characterized in that the filler is one or contains a plurality of SiOr compounds 6. Building material according to claim 5, characterized in that the filler is selected from the following Group is selected: ground quartz glass, ground quartz, silica anhydride 7. Building material according to claim 5, characterized in that at least one of the silicon dioxide compounds is in colloid form 8. Building material according to claim 7, characterized in that the present in colloidal form SiOr compound is silica gel and zinc sulfide is suspended in it 9. Building material according to one of claims 1 to 8, characterized in that there is also one Contains porophoric aggregate 10. Process for the production of a building material according to claims 1 to 9, characterized in that the phosphorus, the colloidal silicon dioxide compound and the water are added an emulsion, suspension or dispersion to which the resin is added.