Building composition marker

Abstract

The invention relates to the use of a building composition marker comprising at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof in a building composition. The invention also relates to a building composition comprising such a building composition marker, and to a process for producing the building composition. The invention further relates to a building composition marker comprising at least one alpha-amino acid, alpha-amino acid salt or mixture thereof, and one or more components selected from:vinyl ester homopolymers, vinyl ester copolymers comprising one or more vinyl ester units and one or more monomer units from the group selected from olefins, vinylaromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; (meth)acrylic ester homopolymers, (meth)acrylic ester copolymers comprising one or more (meth)acrylic ester units and one or more monomer units from the group of vinylaromatics, vinyl halides, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; homopolymers or copolymers of dienes and also of olefins, diene copolymers comprising one or more diene units and one or more monomer units from the group selected from vinyl halides, (meth)acrylic esters, esters of fumaric or maleic acid, and vinylaromatics; homopolymers of vinylaromatics; homopolymers of vinyl halides; andpolysaccharides, polysaccharide ethers, and mixtures thereof.

Claims

1. A method for determining the origin of a building composition, the method comprising: including a building composition marker in the building composition, wherein the building composition marker comprises at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof as a marker for determining the origin of a building composition; and adding a test composition to the building composition and reacting the test composition with the building composition marker to cause a visibly detectable color change.

2. The method according to claim 1, wherein the building composition is a composite material comprising: at least one binder, at least one particulate material, and/or at least one reinforcement material.

3. The method according to claim 1, wherein the building composition is selected from construction adhesives, mortars, plasters, renders, filling compounds, flooring compounds, leveling compounds, grouts, jointing mortars, or concrete modifiers, paints, gypsum based materials, thermal insulation composite system adhesives or tile adhesives.

4. The method according to claim 1, wherein the building composition marker further comprises: (i) one or more polymers selected from vinyl ester homopolymers, vinyl ester copolymers comprising one or more vinyl ester units and one or more monomer units from the group selected from olefins, vinylaromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; (meth)acrylic ester homopolymers, (meth)acrylic ester copolymers comprising one or more (meth)acrylic ester units and one or more monomer units from the group of vinylaromatics, vinyl halides, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; homopolymers or copolymers of dienes and also of olefins, diene copolymers comprising one or more diene units and one or more monomer units from the group selected from vinyl halides, (meth)acrylic esters, esters of fumaric or maleic acid, and vinylaromatics; homopolymers of vinylaromatics; or homopolymers of vinyl halides; and/or (ii) one or more polysaccharides, polysaccharide ethers, and mixtures thereof.

5. The method according to claim 1 further comprising: drying or curing the building composition to form a structure; and obtaining a sample from the structure; wherein adding the test composition to the building composition comprises adding the test composition to the sample.

6. The method according to claim 1, wherein including a building composition marker in the building composition comprises adding the building composition marker a dry building composition, a building composition slurry, a building composition solution, a building composition dispersion, or a building composition emulsion.

7. A method for determining the presence of a building composition marker in a building composition, comprising the steps of: a) taking a sample of the building composition; and b) mixing the sample with ninhydrin.

8. The method of claim 7 wherein the building composition marker comprises at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof.

9. The method of claim 8 wherein the building composition is selected from composite materials comprising at least one binder, at least one particulate material, and/or at least one reinforcement material.

10. The method of claim 8 wherein the building composition is selected from construction adhesives, mortars, plasters, renders, filling compounds, flooring compounds, leveling compounds, grouts, jointing mortars, or concrete modifiers, paints, gypsum based materials, thermal insulation composite system adhesives or tile adhesives.

11. The method of claim 7, wherein the building composition marker comprises: at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof as a marker for determining the origin of a building composition; (i) one or more polymers selected from vinyl ester homopolymers, vinyl ester copolymers comprising one or more vinyl ester units and one or more monomer units from the group selected from olefins, vinylaromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; (meth)acrylic ester homopolymers, (meth)acrylic ester copolymers comprising one or more (meth)acrylic ester units and one or more monomer units from the group of vinylaromatics, vinyl halides, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; homopolymers or copolymers of dienes and also of olefins, diene copolymers comprising one or more diene units and one or more monomer units from the group selected from vinyl halides, (meth)acrylic esters, esters of fumaric or maleic acid, and vinylaromatics; homopolymers of vinylaromatics; or homopolymers of vinyl halides; and/or (ii) one or more polysaccharides, polysaccharide ethers, and mixtures thereof.

12. The method of claim 7, further comprising after mixing the sample with ninhydrin visually inspecting the sample for the formation of Ruhemann's purple.

13. The method of claim 7, further comprisingbefore taking the sample of the building compositioncuring, drying or hardening the building composition.

14. The method of claim 7, wherein the building composition marker comprises at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof as a marker for determining the origin of a building composition.

15. The method of claim 1 wherein the building composition marker comprises at least one alpha-amino acid salt.

16. The method of claim 1 wherein the test composition comprises ninhydrin and wherein the visibly detectable color change is a color change to purple.

17. A building composition origin determination kit comprising: a building composition; a building composition marker included in the building composition, wherein the building composition marker comprises at least one alpha-amino acid, alpha-amino acid salt or a mixture thereof as a marker for determining the origin of the building composition; and a test composition selected for reaction with the building composition marker to cause a visibly detectable color change in the building composition, wherein the test composition comprises ninhydrin.

18. The building composition origin determination kit of claim 17 wherein the building composition is a composite material comprising: at least one binder, at least one particulate material, and/or at least one reinforcement material.

19. The building composition origin determination kit of claim 17 wherein the building composition marker further comprises: (i) one or more polymers selected from vinyl ester homopolymers, vinyl ester copolymers comprising one or more vinyl ester units and one or more monomer units from the group selected from olefins, vinylaromatics, vinyl halides, acrylic esters, methacrylic esters, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; (meth)acrylic ester homopolymers, (meth)acrylic ester copolymers comprising one or more (meth)acrylic ester units and one or more monomer units from the group of vinylaromatics, vinyl halides, monoesters or diesters of fumaric and/or maleic acid, or silicon-functional monomers; homopolymers or copolymers of dienes and also of olefins, diene copolymers comprising one or more diene units and one or more monomer units from the group selected from vinyl halides, (meth)acrylic esters, esters of fumaric or maleic acid, and vinylaromatics; homopolymers of vinylaromatics; or homopolymers of vinyl halides; and/or (ii) one or more polysaccharides, polysaccharide ethers, and mixtures thereof.

Description

EXAMPLES

Ninhydrin Test

(1) 1. Ninhydrin Solution Preparation

(2) For the Ninhydrin test using the Ninhydrin solution, Ninhydrin puriss. from Riedel-de Haen was used. A 1 wt % aqueous solution of Ninhydrin was prepared for the tests by dissolving 1 wt % Ninhydrin puriss. in deionized water based on the total weight of the Ninhydrin solution.

(3) 1.1. Ninhydrin Reaction

(4) Positive ninhydrin reaction results (referred to as ninhydrin test result) are listed as purple, negative ninhydrin reaction results as uncolored or as no color change in the Tables below.

(5) 1.2. Dry Cementitious Building Composition Base Mix

(6) TABLE-US-00001 TABLE 1 Dry cementitious building composition base mix for testing CEM I 20 wt % based on the total weight of the cementitious building composition base mix Calcium Carbonate 79.6% based on the total weight of the (Durcal 65) cementitious building composition base mix Cellulose ether 0.4% based on the total weight of the Bermocoll M 70 cementitious building composition base mix

(7) 1.3. Preparation of the Cementitious Building Composition for Testing

(8) Cementitious building compositions comprising varying amounts of glycine were prepared by mixing 100 g of the dry cementitious building composition base mix with varying amounts of glycine. In addition, varying amounts of varying polymers were added. The amounts and the polymers tested are listed below in the text and in Table 3. Comparative examples may contain polymer but do not contain glycine (blank sample).

(9) 1.4. Ninhydrin Test for Alpha-Amino Acids in Cementitious Building Compositions

(10) 1.4.1. Sample Preparation for Ninhydrin Test Using the Ninhydrin Solution

(11) 30 g of the dry cementitious building composition base mix were mixed with 30 g deionized water and left standing for 30 minutes. A 5 ml sample was taken of the clear supernatant. The pH of the sample was adjusted to pH 7 using 0.1 mol/l HCl (from Merck (Titrisol)). 1 ml of the pH 7 supernatant was added to 1 ml ninhydrin solution and heated in a 90 C. water bath for 2-3 minutes. The sample was inspected visually for the formation of Ruhemann's purple indicating the presence of glycine in the sample.

(12) 1.4.2. Comparison of Cementitious Building Compositions Containing 0 wt % Glycine and Various Amounts of Glycine

(13) 1.4.2.1. EVA Polymer Tg (Midpoint 5 C. (DSC)

(14) The cementitious building composition contained 2 wt % of an EVA redispersible polymer powder, Tg (Midpoint 5 C. (DSC, Perkin Elmer, Type: Pyris 6 DSC, heating rate: 10 K/min. The Tg (Midpoint) of the polymer was determined according to ASTM D3418-82(1988)e1)).

(15) The amount of glycine is based on the total weight of the cementitious building composition. The amounts are listed in Table 2. The glycine was not visible to the eye in the cementitious building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the cementitious building composition.

(16) The ninhydrin test results show that low amounts of glycine can be determined by visual inspection.

(17) TABLE-US-00002 TABLE 2 Amount of glycine in wt % Ninhydrin test result 0 (Blank sample) Uncolored 0.05 Purple 0.03 Purple 0.02 Purple 0.01 Purple

(18) 1.4.3. Ninhydrin Test of a Dry Cementitious Building Composition and of Said Cementitious Building Composition After Curing

(19) The cementitious building composition contained 2 wt % of an EVA polymer powder, Tg (Midpoint) 5 C. (DSC).

(20) The dry cementitious building composition was tested as described above under 1.4.1 (Sample preparation for ninhydrin test using the ninhydrin solution).

(21) Various amounts of glycine were added to the cementitious building composition as listed in Table 3 below. Further, various amounts of an EVA polymer powder, Tg (Midpoint 5 C. (DSC)) were added as listed in Table 3 below. The glycine was not visible to the eye in the cementitious building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the cementitious building composition.

(22) 1.4.4. The cured cementitious building composition was prepared as follows:

(23) Samples of the resulting dry cementitious building compositions were mixed with 20 wt % of water based on the total weight of the dry cementitious building composition. The resulting cementitious building composition slurry was applied on a PE sheet and allowed to cure and dry for 7 days at 23 C., 50% relative humidity. Thereafter, the samples were ground and tested as described above under 1.4.1 Sample preparation for ninhydrin test using the ninhydrin solution.

(24) TABLE-US-00003 TABLE 3 Ninhydrin test Ninhydrin test Amount of Amount of result of Dry result of Cured glycine and EVA Cementitious Cementitious amount of polymer in building building casein in wt % wt % composition composition 0 (Blank sample) 0 Uncolored Uncolored 0.05 Glycine 0 Purple Purple 0.03 Glycine 2 Purple Purple 0.05 Glycine 3 Purple Purple 0.1 Glycine 0 Purple Purple 0.5 Casein 0 Uncolored Uncolored (comparative sample)

(25) The ninhydrin test results show the presence of the glycine both in the dry cementitious building composition and in the cured cementitious building composition. The presence of the glycine can be tested before and after the cementitious building composition had changed to produce its final cured structure.

(26) In addition, a cementitious building composition containing 0.5 wt % casein instead of glycine was tested. The ninhydrin test was negative.

(27) 1.4.5. Ninhydrin Test of Cementitious Building Compositions Including the Optional Concentration Step

(28) The cementitious building composition contained 2 wt % EVA polymer powder Tg (Midpoint) 5 C. (DSC) based on the total weight of the cementitious building composition.

(29) Various amounts of glycine, based on the total weight of the cementitious building composition were added as listed below in Table 4. The glycine was not visible to the eye in the cementitious building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the cementitious building composition.

(30) For the ninhydrin test including the optional concentration step, 100 g of the dry cementitious building composition were mixed with 100 g deionised water and left standing for 30 minutes. A 20 ml sample was taken of the clear supernatant. The pH of the sample was adjusted to pH 7 using 0.1 mol/l HCl.

(31) The pH 7 supernatant was concentrated using a rotary evaporator (Buchi Rotavapor R-124 equipped with Buchi waterbath B-480) to 10% of the original volume.

(32) 1 ml of the concentrated pH 7 supernatant was added to 1 ml ninhydrin solution and heated in a 90 C. water bath for 2-3 minutes. The samples were inspected visually for the formation of Ruhemann's purple indicating the presence of glycine in the sample.

(33) TABLE-US-00004 TABLE 4 Amount of glycine in wt % Ninhydrin test result 0.01 Purple 0.005 Purple

(34) The ninhydrin test results show that low amounts of glycine can be determined by visual inspection.

(35) 1.4.6. Cementitious Building Composition Containing a VA/VeoVa Polymer

(36) The cementitious building composition was prepared by adding 2 wt %, based on the total weight of the cementitious building composition, of VA/VeoVa polymer powder Tg (Midpoint) of +18 C. to the cementitious building composition base mix.

(37) Various amounts of glycine were added, the amounts in wt % based on the total weight of the cementitious building composition are listed in Table 5. The glycine was not visible to the eye in the cementitious building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the cementitious building composition.

(38) TABLE-US-00005 TABLE 5 Amount of glycine in wt % Ninhydrin test result 0.009 Purple 0.017 Purple 0.03 Purple 0.085 Purple

(39) 1.4.7. Cementitious Building Composition Containing a VA/E/VC Polymer

(40) The cementitious building composition was prepared by adding 2 wt %, based on the total weight of the cementitious building composition, of a VA/E/VC polymer powder Tg (Midpoint) of +15 C. (DSC) to the cementitious building composition base mix.

(41) Various amounts of glycine were added, the amounts in wt % based on the total weight of the cementitious building composition are listed in Table 6. The glycine was not visible to the eye in the cementitious building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the cementitious building composition.

(42) The ninhydrin test result show that low amounts of glycine can be determined by visual inspection.

(43) TABLE-US-00006 TABLE 6 Amount of glycine in wt % Ninhydrin test result 0 Uncolored 0.05 Purple 0.5 Purple

(44) 1.5. Comparison of Polymer Plaster Building Compositions Containing 0 wt % Glycine and Various Amounts of Glycine

(45) TABLE-US-00007 TABLE 7 Dry polymer plaster composition base mix Calcium Carbonate 99.6 wt % based on the total weight of dry (Durcal 65) polymer plaster composition base mix Cellulose ether 0.4 wt % based on the total weight of dry Bermocoll M 70 polymer plaster composition base mix

(46) 1.5.1. Preparation of the Polymer Plaster Building Compositions for Testing

(47) The polymer plaster building composition was prepared by adding 2 wt %, based on the total weight of the polymer plaster building composition, to the polymer plaster building composition base mix. Various amounts of glycine were added, the amounts in wt % based on the total weight of the polymer plaster building composition are listed in Table 8. The glycine was not visible to the eye in the polymer plaster building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the polymer plaster building composition.

(48) 1.5.2. Sample Preparation for Ninhydrin Test Using the Ninhydrin Solution

(49) 30 g of the dry polymer plaster composition were mixed with 30 g deionized water and left standing for 30 minutes. A 5 ml sample was taken of the clear supernatant. 1 ml of the supernatant was added to 1 ml ninhydrin solution and heated in a 90 C. water bath for 2-3 minutes. The sample was inspected visually for the formation of Ruhemann's purple indicating the presence of glycine in the sample.

(50) 1.5.3. Ninhydrin Test of a Dry Polymer Plaster Building Composition Base Mix

(51) The polymer plaster building composition contained 2 wt % of various polymer powders as listed in Table 8 below.

(52) TABLE-US-00008 TABLE 8 Ninhydrin test result of polymer Amount of Glycine Type of Tg, mid in C. plaster in wt % polymer of polymer composition 0 (Blank sample) VA 40 Uncolored 0 (Blank sample) EVA 20 Uncolored 0.1 VA 40 Purple 0.05 EVA 20 Purple 0.03 VA/VeoVa 18 Purple

(53) The ninhydrin test results show that low amounts of glycine can be determined by visual inspection.

(54) 2. Comparison of Paint Building Compositions Containing 0 wt % Glycine and Various Amounts of Glycine

(55) 2.1. Dispersion PaintWhite

(56) 2.1.1. Preparation of a Paint Building Composition for Testing

(57) The white paint building composition for the testing was AkzoNobel Herbol Zenit Power (white) (aqueous wall paint according to DIN EN 13300). The white paint building composition main constituent materials are polyvinyl acetate (binder), TiO.sub.2 (pigment), Dolomit (filler), CaCO.sub.3 (filler), water, additives, and preservatives.

(58) 0.1 g glycine (dry) was mixed with 100 g of the white paint building composition. The glycine was not visible to the eye in the white paint building composition by visible inspection prior to adding the ninhydrin. The addition of the glycine thus did not lead to visible changes in the color of the white paint building composition.

(59) The comparative example was prepared accordingly, however, no glycine was added to the comparative example (blank sample).

(60) 2.1.2. Ninhydrin Test Using the Ninhydrin Solution

(61) 1 g of the paint sample containing the glycine was mixed with 1 ml of the 1% ninhydrin solution. The sample was heated in a 90 C. water bath for 2-3 minutes. 1 g of the blank sample was treated accordingly.

(62) TABLE-US-00009 TABLE 9 Amount of glycine in wt % Ninhydrin test result 0 (blank sample) No color change, the paint remained white 0.01 Purple

(63) The ninhydrin test results show that low amounts of glycine can be determined by visual inspection.

(64) 2.1.3. Ninihydrin in Dry Form

(65) 1 g of the paint sample containing the glycine was mixed with 0.01 g ninhydrin (dry) (Ninhydrin puriss. from Riedel-de Haen). The sample was heated in a 90 C. water bath for 2-3 minutes. The comparative example of 1 g of the white paint building composition without the addition of the glycine was treated accordingly (blank sample).

(66) TABLE-US-00010 TABLE 10 Amount of glycine in wt % Ninhydrin test result 0 (blank sample) No color change, the paint remained white 0.01 Purple

(67) The ninhydrin test results show that low amounts of glycine could be determined by visual inspection.

(68) 2.2. Dispersion PaintDark Grey

(69) 2.2.1. Preparation of a Paint Building Composition for Testing

(70) The paint building composition for the testing was AkzoNobel Herbol Zenit Power (white) (aqueous wall paint according to DIN EN 13300). 95 wt % Herbol Zenit Power white paint building composition was modified with 5 wt % Pintasol E-WL8 (Mixol, 73230 Kirchheim), resulting in a dark grey paint building composition. The constituent materials of the composition Pintasol E-WL8 are pigment black 7, CaCO.sub.3 (filler), in aqueous polyglycol- and 1,2-propanediol dispersion (binder)

(71) 0.1 g glycine (dry) was mixed with 100 g of the dark grey paint building composition. The glycine was not visible to the eye in the dark grey paint building composition by visible inspection prior to adding the ninhydrin solution. The addition of the glycine thus did not lead to visible changes in the color of the dark grey paint building composition.

(72) The glycine containing sample was diluted 1:10 with water and was left standing for 30 minutes. A supernatant of 1 ml was separated.

(73) The comparative example was prepared accordingly; however, no glycine was added to the comparative example (blank sample).

(74) 2.2.2. Ninhydrin Test Using the Ninhydrin Solution

(75) 1 g of the paint sample containing the glycine was mixed with 1 ml of the 1% ninhydrin solution. The sample was heated in a 90 C. water bath for 2-3 minutes. 1 g of the blank sample was treated accordingly.

(76) 2.2.3. Ninhydrin Test Using the Ninhydrin Solution

(77) 1 g of the paint sample containing the glycine was mixed with 1 ml of the 1% ninhydrin solution. The sample was heated in a 90 C. water bath for 2-3 minutes. The comparative example of 1 g of the paint without the addition of the glycine was treated accordingly (blank sample).

(78) TABLE-US-00011 TABLE 11 Amount of glycine in wt % Ninhydrin test result 0 (blank sample) No color change of the supernatant 0.01 Purple

(79) The ninhydrin test results show that low amounts of glycine can be determined by visual inspection.

(80) As can be seen from the ninhydrin tests, the addition of glycine can be used to determine the origin of the building composition by distinguishing between a marked and an unmarked building composition. It has further been shown that the glycine is a simple means to determine whether the intended building composition has been used by distinguishing between a marked and an unmarked building composition.