Title of Invention

A NOVEL PROCESS FOR THE ELIMINATION OF FREE FOR MALDEHYDE PRESENT IN LEATHER''

Abstract

A process for elimination of formaldehyde from leather has been developed wherein leather which is to be subjected to the treatment of formaldehyde or its derivatives during post tanning operations is rehydrated by conventional method and is then taken in 200 - 350% by volume of water based on the weight of the leather under consideration, pH of the bathe is adjusted in the range of 4 - 6.5 by known method and 8-16 times w/w of deformaldehyde agent on the total potential presence of free formaldehyde in the leather considering the present content of free formaldehyde as well as the formaldehyde derivatives, which are going to be added, during the subsequent operations, is added to the leather in dynamic condition either in the absence or presence of syntan or dye. Leather is treated with the deformaldehyde agent preferably in the presence of conventional fatliquor, the addition which may be either simultaneous with or preceding or succeeding the addition of the said agent. Finally the acidification is done by adjusting pH in the range of 2 - 4 and the resulting leather is washed in water by conventional method before it is taken out of the processing bath.

Full Text

The present invention relates to a novel process for the elimination of free formaldehyde present in leather. This process finds potential use in the leather industry either to restrict the free formaldehyde content of leather within a permissible limit or even to render leather completely free from unbound formaldehyde. Formaldehyde has multifarious uses in leather industry as pretanning agent, tanning agent, retanning agent and also as a fixative in protein finishes. Walker (Formaldehyde, Reinhold Publishing Corporation, New York, Third Edition, Chapter 20, p-598,1964) quoted the reference of German patent No.694, 488 of 1940 to report that formaldehyde may even be used as a preservative in the soaking process. According to Walker (Formaldehyde, Reinhold Publishing Corporation, New York, Third Edition, Chapter 20, p-592, 1964), the most important application of formaldehyde in leather manufacture is found not only directly in tanning as well as finishing operation, but also in the form of formaldehyde derivatives, which are used as synthetic tanning agents and dyeing auxiliaries in the post tanning operations. Winton (Journal of Society of Dyers Colourists, 65, 33,1949) used formaldehyde for giving fur or hair a permanent set in hair-on tanning process. As reported by Walker (Formaldehyde, Third Edition, Reinhold Publishing Corporation, New York, 1964), formaldehyde is not only used as blend with mineral tanning agents like chromium, aluminum etc. in the processing of various types of leathers, but also for improving the felting and dyeing properties. Walker (Formaldehyde, Reinhold Publishing Corporation, New York, Third Edition, Chapter 20, p-598, 1964) has reported that the penetration of vegetable tannins is accelerated while making heavy leathers by using formaldehyde as pretanning agent. Formaldehyde also fixes loose vegetable tannins in vegetable tanned leathers. One of the very important uses of formaldehyde, as reported by Dutta (An introduction to the Principles of Leather Manufacture, Third edition, published by Indian Leather Technologists Association, Calcutta, Chapter 12, p-391,1985) is in combination with oil to produce chamois leather. The growing public awareness to protect the environment has of late persuaded all processing industries to use environmentally safe processes and eco-friendly chemicals/ formulations/ auxiliaries. Moreover, the restrictions imposed recently by the European countries on the usage of hazardous/carcinogenic chemicals in consumer goods have gone a long way to look for better and environmentally safer alternatives. Efforts are, therefore, being made to eliminate the use of chemicals, which are toxic or hazardous. Formaldehyde is known to be mutagenic. The macromolecular binding leads to the mutagenesis. These mutational events may serve to initiate the process of carcinogenesis in specific cells. As reported by Clary et al (Formaldehyde Toxicology and Epidemiology and mechanisms, Marcel Dekker, Inc., New York, Chapter 1, 1983), formaldehyde is carcinogenic as soon as it comes in contact with human skin and there has been definite complaints of irritations to eye, nose and throat with its concentration going beyond 4 ppm. Formaldehyde that is taken up by the cells is readily metabolised. It affects the nasal mucocillary apparacetur during the inhalation. Exposure to toxic concentration of formaldehyde develops mild to severe lesion in the epithelium, lining the nasal cavity. Such toxic injury induces an increase in cell proliferation in the respiratory epithelium resulting ultimately in chemical carcinogenesis. In the wake of ever increasing efforts for developing eco-friendly technologies in the recent days, the toxic nature of formaldehyde has swung into prominence causing a major concern to the mankind. Accordingly, the maximum permissible limit has been set by many countries regarding the concentration of formaldehyde in leathers and that of formaldehyde vapor in the workplace. It has been reported (ECO-TEXTILE MATERIALS REQUIREMENTS, Standard 116 for Leather and Leather clothing by OTTO Quality Associations, Germany, March 1993) that leathers, likely to be be in direct contact with skin of the user, should contain less than 75 ppm of formaldehyde, which may, however, be maximum 300 ppm in case of those leathers, which are not supposed to be in direct contact with human skin, while baby wear leather should not contain more than 20 ppm of formaldehyde. According to the Gazette of India, Part II, Section 3,No. 228, New Delhi, Tuesday, June 23, 1998, the concentration of formaldehyde in leather should not exceed 200 ppm. As reported in a publication brought out by the Badische Aniline Soda Fabrik, Germany (The Ecological aspects of Leather manufacture , January, 1997), the airborne emission of formaldehyde has been restricted to 20 mg/m3 at a mass flow rate of 0.1 kg/hr or more. Paramaraj et al (Thesis entitled Formaldehyde-free leather with required characteristics submitted for the award of the degree Bachelor of Technology in Leather Technology, Anna University, p-59,1998) did not find any free formaldehyde in leathers undergoing conventional pretanning operations using no formaldehyde condensation product. Free formaldehyde was however detected in leathers tanned with either formaldehyde or a combination of formaldehyde and oil. Moreover, the formaldehyde condensation products, which are usually used in the post tanning wet operations, have been found to contribute to the free formaldehyde content in the resulting leather. The free formaldehyde content in the leather has, however, been reported by Paramaraj et al (Thesis entitled Formaldehyde-free leather with required characteristics submitted for the award of the degree Bachelor of Technology in Leather Technology, Anna University, 1998) to vary with the type of the product contributing to it, its free formaldehyde content and also the amount of the same used for a particular process. Formaldehyde used for fixation in protein finishes also contributes to the free formaldehyde content in leather. The formaldehyde condensation products are usually used either as syntan for pretanning, retanning and bleaching or as dyeing auxiliaries. They are basically the condensation products of organic compounds with formaldehyde. Considerable amount of free formaldehyde has been detected in most of the syntans, which also exhibit variation in the content of free formaldehyde depending on their manufacturing process. After detailed analysis of various commonly available syntans, Paramaraj et al (Thesis entitled Formaldehyde free leather with required characteristics submitted for the award of the degree Bachelor of Technology in Leather Technology, Anna University, p-59, 1998) reported the wide ranges of free formaldehyde content in different products, which are listed in the TABLE-I below. TABLE-I (Table Removed) The wide variation of the free formaldehyde content among different commercially available formaldehyde condensation products has been attributed to the reaction conditions like temperature, time of reaction, molar ratio of the reactants, catalyst and the additives, if any, used. The free formaldehyde, present in these syntans, actually contributes to the unbound formaldehyde in the leather treated with these syntans. The conventional method of post tanning wet operation involves the use of different formaldehyde condensation products at different stages of operation. Depending on the type of final leather required, the rechromed or semichrome leather is neutralised to different extents in both surface and cross section using sodium formate, sodium bicarbonate or neutralising syntan in different combinations with variation of drumming time. While conventional rechromed leathers are not likely to contain free formaldehyde before neutralisation, semi chrome leathers may contain a certain amount of free formaldehyde, if it has been bleached with a syntan, which is a formaldehyde condensation product. Drumming is, however, sometimes done with a grain tightening syntan before neutralisation and any formaldehyde condensation product used for this purpose is also likely to contribute to the free formaldehyde in the resulting leather. Retanning is done in fresh bath with vegetable tanning material or syntans of various kinds depending on the requirement of properties in the final leather. Leather is sometimes prefatliquored before taking for retanning operation. Anionic dyeing follows retanning, which is usually done at around 50- 60°C by adding the dyestuff in different installments, while checking dye penetration or surface dyeing depending on the specific requirement. Then the leather is fatliquored by selecting suitable fatliquor emulsion and adding the same in different installments, while continuing the drumming. Finally the bath is acidified with formic acid, thereby resulting in the fixation of the dye/faliquor. The leather surface may sometimes be topped with cationic dye or even fatliquor depending upon the specific requirement of process depending upon the final product. Finally the bath is drained and the leather is washed in running water before it is piled up. The resulting leather is then subjected to drying and different mechanical operations to produce crust leather. Formaldehyde condensation products, which are used as syntans, have been reported(Journal of American Leather Chemists Association, 76, 320, 1981) to impart fullness with softness, fine/firm grain pattern, heat resistance, fine break, good intensity and level shade dyeing to the leather. They also improve the fullness of leather, especially in the loose areas and ensure that the fullness of the leather is as even as possible across the whole surface of the hide/skin. They also improve the grain tightness of the resulting leather. Moreover, the neutral syntans based on formaldehyde condensation are preferred as neutralising agent because the problem of under-neutralisation or over-neutralisation may be better controlled by using these syntans rather than the conventional alkalies. Therefore, these formaldehyde condensation products are not only very important for different operations in leather processing but also instrumental in contributing to the regulation of the major properties of the final leather, thereby leaving the tanners with hardly any option to eliminate the same. The only possibility in this context is perhaps to make efforts for the removal of the formaldehyde, present in the leather in free form, preferably by an economical method, which seems to be the crying need of the hour. No prior art is available on the process for the elimination of free formaldehyde present in leather. The main object of the present invention is to provide a novel process for the elimination of free formaldehyde present in leather. Another object of the present invention is to provide a process to ensure that the free formaldehyde content of leather is either reduced to below detectable limits or restricted to a minimum permissible limit Yet another object of the present invention is to provide a simple process, whereby the leather produced even by using such chemicals as are likely to contribute to the free formaldehyde in the resulting leather, will be finally free from any formaldehyde in the unbound form. Still another object of the present invention is to provide an economically feasible process, to reduce the free formaldehyde content of leather. Accordingly, the present invention provides, a process for the elimination of free formaldehyde present in leather, which comprises treating rehydrated leather in a fresh bath, with deformaldehyde agent selected from sulphites and bisulphites of ammonium and alkaline earth materials, either individually or in combination, wherein the amount of deformaldehyde agent used is in the range of 8 - 16 times w/w on the total potential presence of free formaldehyde in leather, in a aqueous medium at a pH in the range of 2 - 4 , in the presence of a syntan or dye, but preferably in the presence of fatliquor, wherein float of said aqueous medium is in the range of 100% - 350% by volume on the weight of leather, and temperature of the bath while adding the deformaldehyde agent is in the range of 40 - 65°C , followed by acidification and subsequent washing by conventional method. In an embodiment of the present invention, the leather used may be such as tanned leather containing free formaldehyde, tanned leather to be subjected to the treatment of formaldehyde or its derivatives during post tanning operations, crust leather containing free formaldehyde, crust leather to be treated with formaldehyde or its derivatives during wet operations. In another embodiment of the present invention, the float used may be in the range of 100% - 350% by volume on the weight of leather. In yet another embodiment of the present invention, the temperature of the bath while adding the deformaldehyde agent may be in the range of 40 -65°C. In still another embodiment of the present invention, the chemicals used for adjusting pH may be such as sodium formate, sodium bicarbonate, neutralizing syntan, either individually or in combination. In yet another embodiement of the present invention, the deformaldehyde agent used may be such as, sulphites and bisulphites of ammonium and alkaline earth materials, either individually or in combination. well as the formaldehyde derivatives, which are going to be added, if any, during the subsequent operations, is added to the leather in dynamic condition either in the absence or presence of syntan or dye. Syntans and dyeing auxiliaries used may be with or without any free formaldehyde, contained therein. Leather is, however, treated with the deformaldehyde agent preferably in the presence of conventional fatliquor, the addition of which may be either simultaneous with or preceding or succeeding the addition of the said agent. In case of retanning or dyeing operations, the addition of the deformaldehyde agent is either simultaneous with the retanning agents or at any stage following conventional retanning, dyeing or fatliquoring operation, in single or multiple installments. Finally the acidification is done by adjusting pH in the range of 2-4 and the resulting leather is washed in water by conventional method before it is taken out of the processing bath. The novelty of the present invention lies not only in identifying the cost effective deformaldehyde agent, but also in providing a process of post tanning wet operation either by using formaldehyde-free syntan or by adding the identified deformaldehyde agent either along with retanning agents or in the retanning or dyeing/fatliquoring bath to produce formaldehyde free leather without affecting its usual functional properties, thereby suggesting an eco-friendly method to eliminate the hazards •resulting from the free formaldehyde present in leather even while using the conventional syntans for achieving the required characteristics in the resulting leather. The following examples are given by way of illustration of the present invention and therefore should not be construed to limit the scope of the present invention. EXAMPLE -1 One chrome tanned Cow side leather, shaved to a thickness of 1.2mm, was weighed and the shaved weight was noted to be 2.5 kgs, based on which all subsequent chemicals were added. No free formaldehyde could be detected in the said side leather. The side was taken in a leather processing drum and was washed in running water over a period of 10 minutes. It was then neutralised at a float of 4 Its water using 0.01875 kgs of formaldehyde condensate neutralising agent containing 1500 ppm of free formaldehyde for 30 minutes followed by 0.01875 kgs of sodium bicarbonate for 20 minutes and 0.0125 kgs of sodium formate, given in three feeds at 10 minutes interval and finally running the drum for another 30 minutes. pH of the cross section of the leather was found to be 4.8. The bath was drained. The leather was then taken in a fresh bath of float of 4 Its water and the temperature was raised to 55°C. Prefatliquoring was done with 0.05 kgs of synthetic fatliquor for 20 minutes. Then 0.075 kgs of Acrylic grain tightening syntan was added and the drum was run for 30 minutes. 0.2 kgs of Naphthalene-phenol formaldehyde Syntan containing 1500 ppm free formaldehyde was added and 0.1 kgs Melamine formaldehyde syntan Containing 20,000 ppm free formaldehyde, 0.1 kg Protein based syntan, 0.125 kg Vegetable tannins were added simultaneously along with 0.05 kg of syntan, 0.125 kg Vegetable tannins were added simultaneously along with 0.05 kg of Synthetic fatliquor and 0.45 kg of sodium sulfite. The drum was run for 75 minutes and the retanning bath was drained. The leather was washed in running water for 5 minutes. It was then taken in drum with fresh float of 3.0 Its of water and 0.0625 kg of yellow dye was added to it while continuing the drumming for 30 minutes. 0.2 kg of synthetic fatliquor was then added to the drum while running it for another 60 minutes. Then 0.05 kg of formic acid dissolved in 0.5 It. of water was added to the drum through the axle in two feeds at 10 minutes interval and the drum was finally run for 30 minutes. pH was found to be 2. Exhaustion of dye and fatliquor was checked. The bath was found to be clear and was drained. Finally the leather was washed in running water for 10 minutes and taken out of the drum. It was then piled over night for subsequent operations on the next day. After drying the leather was checked for free formaldehyde which could not be detected in the leather. EXAMPLE - II One chrome tanned sheep leather, shaved to a thickness of 1.0mm, was weighed and the shaved weight was noted to be 0.9 kgs, based on which all subsequent chemicals were added. No free formaldehyde could be detected in the said leather The leather was taken in a leather processing drum and was washed in running water over a period of 10 minutes. It was then neutralised at a float of 1.35 Its. of water using 0.00675 kgs of formaldehyde condensate neutralising agent containing 1500 ppm of free formaldehyde for 30 minutes followed by 0.00675 kgs of sodium bicarbonate for 20 minutes and 0.0045 kgs of sodium formate, given in three feeds at 10 minutes interval and finally running the drum for another 30 minutes. pH of the cross section of the leather was found to be 5.5. The bath was drained. The leather was then taken in a fresh bath of float of 1.35 Its of water and the temperature was raised to 65°C. Then 0.018 kg of Acrylic grain tightening syntan was added and the drum was run for 30 minutes. 0.054 kg of Naphthalene-phenol formaldehyde Syntan containing 1500 ppm free formaldehyde was added and 0.036 kg of Protein based syntan was added simultaneously and the drum was run for 45 minutes. 0.032 kgs of sodium bisulphite was added and the drum was run for 30 minutes and the bath was drained. The leather was washed in running water for 5 minutes. It was then taken in drum with fresh float of 1 It. of water and 0.018 kg of brown dye was added to it while continuing the drumming for 30 minutes. 0.108 kg of synthetic fatliquor was then added to the drum while running it for another 60 minutes. Then 0.032 kgs of sodium bisulphite was added to the bath while running the drum for another 30 minutes. Then 0.018 kg of formic acid dissolved in 0.18 It. water was added to the drum through the axle in two feeds at 10 minutes interval and the drum was finally run for 30 minutes. pH was found to be 3. Exhaustion of dye and fatliquor was checked. The bath was found to be clear and was drained. Finally the leather was washed in running water for 10 minutes and taken out of the drum. It was then piled over night for subsequent operations on the next day. After drying the leather was checked for free formaldehyde which could not be detected in the leather. EXAMPLE - III One Vegetable tanned goat leather, duly stripped and bleached, was weighed and the weight was noted to be 0.4 kg, based on which all subsequent chemicals were added. No free formaldehyde could be detected in the said leather. It was neutralised at a float of 0.6 It. of water using 0.006 kgs of sodium formate, given in three feeds at 10 minutes interval and finally running the drum for another 30 minutes. pH of the cross section of the leather was found to be 4.8. The bath was drained. The leather was then taken in a fresh bath of float of 0.6 It. of water and the temperature was raised to 40°C. Prefatliquoring was done with 0.008 kgs of synthetic fatliquor for 20 minutes. Then 0.008 kgs of Acrylic syntan was added and the drum was run for 20 minutes. 0.024 kgs of Naphthalene-phenol formaldehyde Syntan containing 1500 ppm free formaldehyde and 0.02 kgs of Vegetable tannins were added simultaneously along with 0.008 of Synthetic fatliquor and 0.009 kgs of ammonium sulphite. The drum was run for 75 minutes and the retanning bath was drained. The leather was washed in running water for 5 minutes. It was then taken in drum with fresh float of 0.4 It. of water and 0.008 kgs of black dye was added to it while continuing the drumming for 30 minutes. 0.024 kgs of synthetic fatliquor was then added to the drum while running it for another 60 minutes. Then 0.008 kgs of formic acid dissolved in 0.08lts of water was added to the drum through the axle in two feeds at 10 minutes interval and the drum was finally run for 30 minutes. Exhaustion of dye and fatliquor was checked. The bath was found to be clear and was drained. Finally the leather was washed in running water for 10 minutes and taken out of the drum. It was then piled over night for subsequent operations on the next day. After drying the leather was checked for free formaldehyde content, which was found to be 20 ppm. EXAMPLE - IV One crust sheep leather of thickness 1.0mm was weighed and the weight was noted to be 0.250 kgs, based on which all subsequent chemicals were added. The free formaldehyde content of the said leather was found to be 250 ppm. The leather was taken in a leather processing drum and was left overnight at a float of 200% along with 0.00125 kg of a wetting agent to soak it back. Next morning, the leather was drummmed for 10 minutes and then washed in running water over a period of 15 minutes. The bath was drained. The leather was then taken in a fresh bath of float of 1.2 It. of water and the temperature was raised to 55°C. 0.048 kgs of Naphthalene-phenol formaldehyde Syntan containing 1500 ppm free formaldehyde was added and 0.032 kgs of Protein based syntan was added simultaneously and the drum was run for 45 minutes and 0.016 kgs of brown dye was added to it while continuing the drumming for 30 minutes. 0.096 kgs of synthetic fatliquor was then added to the drum while running it for another 60 minutes. Then 0.016 kgs of formic acid dissolved in 0.16 kgs of water was added to the drum through the axle in two feeds at 10 minutes interval and the drum was finally run for 30 minutes. Then 0.032 kgs of sodium bisulphite and 0.012 kgs of sodium sulphite were added to the bath and the drum was run for 30 minutes. 0.024 It of formic acid was diluted with 0.24 It of water and the same was added to the bath for fixation in three feeds at 10 minutes interval. Exhaustion of dye and fatliquor was checked after 30 minutes. pH was found to be 3.5. The bath was found to be clear and was drained. Finally the leather was washed in running water for 10 minutes and taken out of the drum. It was then piled over night for subsequent operations on the next day. After drying the leather was checked for free formaldehyde which could not be detected in the leather. EXAMPLE - V One chrome tanned Cow side leather, shaved to a thickness of 1.2mm, was weighed and the shaved weight was noted to be 2.5 kgs, based on which all subsequent chemicals were added. No free formaldehyde could be detected in the said side leather. The side was taken in a leather processing drum and was washed in running water over a period of 10 minutes. It was then neutralised at a float of 4 Its water using 0.01875 kgs of sodium bicarbonate for 20 minutes and 0.0125 kgs of sodium formate, given in three feeds at 10 minutes interval and finally running the drum for another 30 minutes. pH of the cross section of the leather was found to be 4.5. The bath was drained. The leather was then taken in a fresh bath of float of 4 Its water and the temperature was raised to 55°C. Prefatliquoring was done with 0.05 kgs of synthetic fatliquor for 20 minutes. Then 0.075 kgs of Acrylic grain tightening syntan was added and the drum was run for 30 minutes. 0.2 kgs of acrylic Syntan and 0.2 kg of resin syntan was then added along with 0.1 kg Protein based syntan, 0.180 kg Vegetable tannins and 0.05 kg of Synthetic fatliquor. The drum was run for 75 minutes and the retanning bath was drained. The leather was washed in running water for 5 minutes. It was then taken in drum with fresh float of 3.0 Its of water and 0.0625 kg of yellow dye was added to it while continuing the drumming for 30 minutes. 0.2 kg of synthetic fatliquor was then added to the drum while running it for another 60 minutes. Then 0.05 kg of aceticacid dissolved in 0.5 It. of water was added to the drum through the axle in two feeds at 10 minutes interval and the drum was finally run for 30 minutes. pH was f6und to be 4. Exhaustion of dye and fatliquor was checked. The bath was found to be clear and was drained. Finally the leather was washed in running water for 10 minutes and taken out of the drum. It was then piled over night for subsequent operations on the next day. After drying the leather was checked for free formaldehyde which could not be detected in the leather. The main advantages of the present invention are the following. 1. The process enables elimination of free formaldehyde in final leather even without changing the conventional formaldehyde condensates. 2. The process is very simple and economically feasible. 3. The process ensures that by varying the amount of the deformaldehyde agent, it is possible to control the free formaldehyde content in leather. 4. The process provides an eco-friendly option to eliminate free formaldehyde present in leather. 5. This process can even be used to eliminate free formaldehyde, even if it is detected at the crust stage. We Claim: 1. A novel process for the elimination of free formaldehyde present in leather, which comprises treating rehydrated leather in a fresh bath, with deform aldehyde agent selected from sulphites and bisulphites of ammonium and alkaline earth materials, either individually or in combination, wherein the amount of deformaldehyde agent used is in the range of 8 - 16 times w/w on the total potential presence of free formaldehyde in leather, in a aqueous medium at a pH in the range of 2 - 4 , in the presence of a syntan or dye, but preferably in the presence of fatliquor, wherein float of said aqueous medium is in the range of 100% - 350% by volume on the weight of leather, and temperature of the bath while adding the deformaldehyde agent is in the range of 40 - 65°C, followed by acidification and subsequent washing by conventional method. 2. A novel process , as claimed in claim 1 , wherein the leather used is such as tanned leather containing free formaldehyde, tanned leather to be subjected to the treatment of formaldehyde or its derivatives during post tanning operations, crust leather containing free formaldehyde, crust leather to be treated with formaldehyde or its derivatives during wet operations. 3. A novel process, as claimed in claims 1 to 2, wherein the chemicals used for adjusting pH are such as sodium formate, sodium bicarbonate, neutralizing syntan, either individually or in combination. 4. A novel process, as claimed in claims 1 to 3, wherein the addition of the deformaldehyde agent with respect to that of fatliquor is such as to precede, to succeed or to be simultaneous. 5. A novel process, as claimed in claims 1 to 4, wherein syntans and dyeing auxiliaries used are with or without the content of free formaldehyde. 6. A novel process, as claimed in claims 1 to 5, wherein acids used for acidification are such as formic acid, acetic acid. 7. A novel process for the elimination of free formaldehyde present in leather, substantially as herein described with reference to the examples.

Documents:

136-del-1999-abstract.pdf

136-del-1999-claims.pdf

136-del-1999-correspondence-others.pdf

136-del-1999-correspondence-po.pdf

136-del-1999-description (complete).pdf

136-del-1999-form-1.pdf

136-del-1999-form-19.pdf

136-del-1999-form-2.pdf

136-del-1999-form-3.pdf