AU2015203853A1 - Plaster-based Material Including An Agent Capable of Trapping Formaldehyde - Google Patents

Abstract

The present invention relates to a plaster-based material which includes an agent capable of trapping formaldehyde, in particular a plasterboard intended for the interior fittings of residential buildings. The agent capable of trapping formaldehyde is chosen from ethylene urea and its derivatives, compounds comprising active methylene(s), sulphites, tannins and their mixtures. Another subject matter of the invention is the use of the said plaster based material for reducing the amount of formaldehyde in the air inside buildings.

Description

I PLASTER-BASED MATERIAL INCLUDING AN AGENT CAPABLE OF TRAPPING FORMALDEHYDE The present application is a divisional application from Australian Patent Application No. 2010317906, the entire disclosure of which is incorporated into the present specification by this cross-reference, The invention relates to a plaster-based material which includes an agent capable of trapping formaldehyde, in particular a plasterboard intended for the interior fittings of residential buildings. Highly diverse composite materials are used in the field of the construction and equipping of buildings in general, in particular residential buildings or offices and public buildings (museums, cinemas, concert halls, and the like). Some of these materials, such as acoustic and/or thermal insulators, wood panels, furniture units or decorative items, use adhesives, paints and varnishes which comprise formaldehyde0based resins. These resins are highly advantageous as they are inexpensive and have excellent performances. Their major disadvantage lies in the fact that they comprise free formaldehyde and consequently that they are capable of emitting formaldehyde over time. In recent years, the proportion of formaldehyde in resins has greatly decreased due to the application of stricter regulations with regard to protection from undesirable emissions of volatile organic products which may exhibit a risk to the health of individulas. However, the attempts which have consisted in replacing the abovementioned resins with other formaldehyde-free resins have not been successful due to the very much higher cost and the poorer quality of the products obtained. Nevertheless, it is still desirable for the content of formaldehyde in the ambient air of buildings for residential use to be as low as possible. Means are known for achieving this aim. The proposal has been made to include particules of photocatalytic titanium oxide in a paint or a plaster material (US-A-2005/0226761) or in paper or a textile, plastic or wooden material (EP-A-1 437 397). JP-A-11128329 describes the use of an ammonium salt in an interior WO 2011/058172 PCT/EP2010/067475 building material, such as a plasterboard. JP-A-2002145655 provides for the inclusion of urea and/or melamine in a plasterboard. JP-A-I 0337803 describes the incorporation of a hydrazine derivative in 5 a plasterboard. The proposal is also made to include at least one hydrazide in combination a) with an inorganic absorbent in a plasterboard or in a decorative layer on wood (JP-A-2000103002), b) with silica gel in a plasterboard (JP~A-2004115340) or c) with an organic carbide (US-A-20040101695) in an interior building material. 0 The aim of the present invention is to reduce the content of formaldehyde inside buildings, in particular residential or public buildings, in order to improve the quality of the ambient air. To achieve this aim, the present invention provides a plaster-based material, in particular a plasterboard, which comprises an agent capable of 15 trapping formaldehyde chosen from ethylene urea and its derivatives, compounds comprising active methylene(s), sulphites, tannins and their mixtures. Another subject-matter of the invention is the use of the said plaster based material for reducing the amount of formaldehyde in the air inside 20 buildings. The ethylene urea derivatives according to the invention are preferably chosen from N-hydroxyethylene urea, N-aminoethylethylene urea, N-[(3-ailyloxy-2-hydroxypropyl)aminoethyl]ethylene urea, N-acryloyloxyethyl ethylene urea, N-methacryloyloxyethylethylene urea, N-acryloylaminoethyl 25 ethylene urea, N-methacryloylaminoethylethylene urea, N-methacryloyloxy acetoxyethyiene urea, N-methacryloyloxyacetaminoethylethylene urea and N-di(3-allyloxy-2-hydroxypropyl)aminoethylethylene urea, Ethylene urea is preferred. The compounds comprising active methylene(s) according to the 30 invention preferably correspond to the following formula (1): WO 2011/058172 PCT/EP2010/(67475 R, ... (O)a !(O) ..-.. R2 R3 n (i) in which: - R, and R2, which are identical or different, represent a hydrogen atom, a CrC2(, preferably C-C6, alkyl radical, an amino radical or a radical of formula (CH2)r0 O -C-R 4 in which R4 represents a radical CH2- C H 3 0 or

C.CH

2 10 Rs where Rs = H or -CH 3 and p is an integer varying from I to 6 - Rd represents a hydrogen atom, a CCi12 alkyl radical, a phenyl radical or a halogen atom 15 ~ a is equal to 0 or I - b is equal to 0 or 1 - n is equal to 1 or 2 The compound of formula (1) which is particularly preferred is acetoacetamide

(R

1 = -CH 3 ; R 2 = -NH 2 ; R 3 = H ; a 0; b 0 ; n = 1). 20 The sulphides according to the invention are, for example, ammonium bisulphite, potassium bisulphite, sodium bisulphite and alkali metal, in particular sodium, or alkaline earth metal metabisulphites. Sodium bisulphite is preferred. The tannins according to the invention can be non-condensed or condensed tannins, such as acacia (catechu), mimosa, quebracho, pine, pecan 25 nut, hemlock wood and sumac tannins. Acacia tannins are preferred.

WO 2061L/058172 PCT/EP2M 0/067475 4 The agent capable of reacting with formaldehyde is a compound which covalently bonds to formaldehyde. For this reason, the formaldehyde is trapped in a lasting fashion in the plaster-based material and is not re-emitted into the ambient air. 5 The amount of agent capable of trapping formaldehyde to be used can vary to a large extent, for example from 0.001 to 5 parts by weight per 100 parts by weight of gypsum, preferably from 0.01 to 1 and advantageously from 0.02 to 0.2 part. The plaster-based material can additionally comprise additives which 10 improve the physicochemical properties of the final product and which make it possible to have good conditions of use. The said material can thus comprise the following additives in the following proportions by weight, expressed per 100 parts by weight of gypsum: - 0.1 - 15 parts of an adhesion agent, the role of which is to increase the 15 adhesion of the paper coating with the plaster, for example a starch, in particular pretreated with an acid, or a dextrin, - 0.001 - 5 parts of a setting accelerator, for example calcium sulphate hydrate or potassium sulphate, - 0.0001 to 1 part of a foaming agent, the role of which is to create pores 20 in order to reduce the density of the final product, in particular of plasterboards. Mention may be made, by way of example, of sodium lauryl sulphate. The manufacture of plaster panels, in particular a plasterboard, is known per se. Although the invention is more particularly described with regard to 25 plaster panels, it is not limited to this type of material and comprises plaster based materials no matter the form thereof (powder, mortar, mastic). The plasterboard is formed according to a continuous process which consists in mixing powdered calcined gypsum (calcium sulphate hemihydrate) with water to form a paste, which is continuously deposited between two sheets 30 of paper. The product formed is formed or shaped, in order to obtain the desired thickness, and then it is continuously transported on a conveyor over a distance which allows the paste to achieve a level of hardening sufficient to be able to be cut into boards of predetermined length. Tihe boards are subsequently dried in WO 2011/058172 PCT/EP2010/067475 an oven in order to remove the excess water. Conventionally, the powdered components of the paste comprise calcium sulphate hemihydrate (CaSO 4 .0.5H 2 0; calcined gypsum) and the optional additives described above, The calcined gypsum undergoes a hydration 5 reaction in the presence of water and is converted to calcium sulphate dihydrate (CaSO 4 2H 2 0; gypsum). The amount of calcined gypsum employed to form the paste varies according to the nature of the panel to be manufactured, generally from 30 to 100 parts by weight per 100 parts by weight of water, preferably from 60 to 80 10 parts. The thickness of the panel can vary to a large extent, for example from 6 to 25 mm. The agent capable of trapping formaldehyde can be introduced into the plasterboard in various ways. 15 According to a first embodiment, the agent capable of trapping formaldehyde is added to the calcined gypsum paste before the latter is deposited between the sheets of paper. The addition of the agent capable of trapping formaldehyde can take place during the manufacture of the paste, for example by simultaneously or 20 successively introducing the calcined gypsum and the said agent into the water, or after the paste has been obtained. The simultaneous addition of the abovementioned constituents is preferred as it is easier to carry out. This embodiment makes it possible to have a homogeneous distribution of the agent capable of trapping formaldehyde in the plaster body and thus a 25 uniform content throughout the thickness of the board. According to a second embodiment, the agent capable of trapping formaldehyde is added to the paper sheet or sheets used as covering. The addition can take place during the manufacture of the paper, for example to the suspension of cellulose fibres or after the obtaining of the sheet. 30 The plaster-based material in accordance with the present invention can be provided in the forrn of a powder (plaster, mortar), of a paste (mastic, pointing material) or of a plaster panel. As regards more particularly the plaster panel, the latter can be a bare board or a board covered over at least one of its WO 2011/058 172 PCT/EP2010067475 faces with a paper sheet, an acoustic panel comprising perforations, a panel of plaster and of mineral or wood wool, or a board reinforced with fibres or a fabric. The plaster-based material in accordance with the invention can be used on walls, ceilings and floors, in particular for covering or pointing plaster or 5 cement panels, or, as regards panels, to form facings, partitions and false ceilings. The use of the plaster-based material inside a building makes it possible to reduce the amount of formaldehyde present in the atmosphere, which, for this reason, is thus decontaminated. 10 The examples which follow make it possible to illustrate the invention without, however, limiting it. EXAMPLES I TO 4 a) manufacture of the plaster-based material 600 g of calcium sulphate hemihydrate, the agent capable of trapping 15 formaldehyde, 3 g of starch, 1.8 g of ground gypsum (accelerator) and 630 g of water are introduced into a mixer. The agent capable of trapping formaldehyde is as follows: ~ ethylene urea (14 mg): Example I - acetoacetamide (15 mg): Example 2 20- sodium bisulphite (16 mg): Example 3 - acacia tannin (115 mg): Example 4 The mixture is stirred for 30 seconds in order to obtain a paste, The paste is poured into a brass mould (150 mm x 100 mm) covered internally on its bottom face with a paper sheet and then a second paper sheet, 25 cut to the dimensions of the mould, is applied to the paste, The two paper sheets were conditioned beforehand for 24 hours in a chamber having an atmosphere maintained at a relative humidity of 90%. After solidification, the plasterboard is removed from the mould It is dried in an oven under the following conditions: at 180'C until 80% of the water has 30 been removed, at 60*C for 12 hour and at 40*C for 24 hours. A plasterboard not comprising agent capable of trapping formaldehyde (Reference) is prepared under the same conditions. b) Ability to trap formaldehyde WO 2011/O5172 PCT/EP2010/067475 The ability to trap formaldehyde is measured in a gastight test chamber. A sample of the plasterboard (2.5 g) is placed in the test chamber and then the chamber is hermeticaly closed. 2.4 pl of a 37% by weight aqueous formaldehyde solution are subsequently deposited in a container placed inside 5 the chamber. After 3 hours, the air present in the test chamber is extracted using a pump connected to a device for measuring formaldehyde (reactive tube sold by Gastec under the reference RAE 10-121-05; measurement range: 0.1 to 5 ppmv). t0 The results given in the following table correspond to a mean value based on a series of three samples of the same plasterboard.

a Formaldehyde I Reduction in the (ppmv) formaidehyde E xample 1 0100 Example 2 0 100 Example 3 0O4 66.6 E xample 4 U 75.0 anyrnc ar11fret~ It is to be understood that, if any prior art publication is referred to herein such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country. In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention,

Claims (14)

1. Plaster-based material, characterized in that it includes an agent capable of trapping formaldehyde chosen from ethylene urea and its 5 derivatives, compounds comprising active methylene(s), sulphites, tannins and their mixtures.

2. Material according to Claim 1, characterized in that the ethylene urea derivatives are chosen from N-hydroxyethylene urea, N-aminoethylethylene urea, N-[(3-allyloxy-2-hydroxypropyl)aminoethylethylene 10 urea, N-acryloyloxyethylethylene urea, N-methacryoyloxyethylethylene urea, N-acryloylaminoethylethylene urea, N-methacryloylaminoethylethylene urea, N-methacryloyloxyacetoxyethylene urea, N-methacryloyloxyacetamino ethyl ethylene urea and N-di(3-allyloxy-2-hydroxypropyl)aminoethylethylene urea. 15

3. Material according to Claim 1, characterized in that the compounds comprising active methylene(s) correspond to the following formula (1): 0 0) RI (0h (O6 R% R3 n(i in which: R and R, which are identical or different, represent a hydrogen atom, a CC23, preferably Q-C6, alkyi radical, an amino radical or a radical of formula (CH2)p=0...C -.. lR4 in which R 4 represents a radical CO C OH 3 0 WO 2011/058172 PCT/EP2010/06747. or . C= CH 2 R5 where Rs = H or -CH 3 and p is an integer varying from 1 to 6 5 Ra epresents a hydrogen atom, a CICc alkyi radical, a pheny radical or a halogen atom a is equal to 0 or 1 b is equal to 0 or I -n is equal to 1 or 2. 10

4, Material according to Claim 3, characterized in that acetoacetamide is concerned,

5, Material according to Claim 1, characterized in that the sulphites are chosen from ammonium bisulphite, potassium bisulphite, sodium bisuiphite and alkali metal or alkaline earth metal metabisuiphites, 15

6. Material according to Claim 5, characterized in that sodium bisuiphite is concerned.

7. Material according to Claim 1, characterized in that the tannin is chosen from non-condensed or condensed tannins.

8& Material according to Claim 7, characterized in that the tannin is an 20 acacia, mimosa, quebracho, pine, pecan nut, hemlock wood and sumac tannin.

9. Material according to Claim 8, characterized in that the tannin is an acacia tannin.

10. Material according to one of Claims I to 9, characterized in that the amount of agent capable of reacting with formaldehyde varies from 0.001 to 25 5 parts by weight per 100 parts by weight of gypsum, preferably from 0.01 to 1 and advantageously from 0.02 to 0.2 part.

11. Material according to one of Claims I to 10, characterized in that it additionally comprises the following additives in the following proportions by weight, expressed per 100 parts by weight of gypsum: 30 - 0.1 - 15 parts of an adhesion agent, for example a starch, in particular pretreated with an acid, or a dextrin, - 0.0001 - 5 parts of a setting accelerator, for example calcium sulphate WO 2011/058172 PCT/EP2010/067475 hydrate or potassium sulphate, - 0,0001 to 1 part of a foaming agent, for example, of sodium lauryl sulphate.

12, Material according to one of Claims 1 to 11, characterized in that it 5 is provided in the form of a powder, of a paste or of a plaster panels

13. Material according to Claim 12, characterized in that a plasterboard is concerned.

14. Use of a material according to one of Claims I to 13 for reducing the amount of formaldehyde in the air inside buildings. 10C