Subject of the Invention and Technical Field

This invention is related to precise determination of the formaldehyde chemical which is used intensively in non-creasing chemical finish substances of the products in the textile sector, is used in developing fastness of some dyestuff and is used in cross linking substances in pigment printing and is a carcinogen.

State of the Art

Today it is known that various chemical substances are used in many sectors such as textile, food, chemistry and plastic etc. These chemical substances are used during the process phases of the products, negative effects of some of them to human health and the environment are eliminated totally or minimized by means of various methods. However, some chemicals cannot be removed from the product and they not only give harm to human health and environment but also they do not degrade in nature during long years.

Formaldehyde known with its chemical formula CH ₂ 0 is an organic component and is toxic. Formaldehyde is very widely used in chemistry such as in medical field for sterilization and protection, in agriculture (for sterilization in mushroom cultivation), animal breeding (for sterilization in fish and animal farms), in drug industry and in the production of wood construction materials, in the production of resin, in non-creasing chemical finish substances in the textile sector, in developing the fastness of some dyestuff, in cross linking substances in pigment printing. As it can be understood from the formaldehyde examples, it is a chemical component which is used in many fields.

Besides many benefits it has, formaldehyde has much harm to human health and environment. Effect of formaldehyde mostly occur during it is in gas form by means of receiving via respiration system. However, it is known that liquid formaldehyde can be absorbed by the skin. The workers can be influenced during the production, treatment of the substances and production of the resin. Heath personnel, lecturers and students are under high influence risk due to materials which are kept in formaldehyde and in which formaldehyde is used during preparation thereof. The consumers can be influenced from the formaldehyde dispersed through some materials used In the construction, house furniture and woven products. Sudden formaldehyde influence can cause death. Odor threshold is 1 ppm (parts per million: it is about 1 unit per million of the total substance amount in any mixture). It is very difficult to accept the odor as a warning factor since perception of formaldehyde odor threshold can be increased in time due to the tiredness in the sense of smell. Being subject to formaldehyde during long terms with low does may lead to respiratory distress, eczema and allergic reactions. Formaldehyde is among the carcinogen substances in human it is thought that it is connected with the nose and lung cancer and it is related to the brain cancer and leukemia. When it is present in the amount of 0, 1 ppm in the air, it leads to watering of eyes, cough, shortness of breath, wheezing, skin rash, allergic reactions, burning sensation in the eyes, nose and ears. Because it leads to sensation, the following influences with the same concentrations may lead to severe reactions in 2 ppm concentration, it leads to irritation in the eyes, in 20 ppm influence it leads to permanent dullness in the cornea. Due to these well-known side effects, a limitation is put into force for the usage of formaldehyde in the products. Products which are subject to various tests gain their freedom of usage according to the formaldehyde ratio in its content.

In the present state of the art, in order to determine the formaldehyde in the textile products, there is a formaldehyde determination test known as ISO-14148-1 of ISO known as the International Standards Organization. Said test is designed to be used on a fabric between 16mg/ kg and 3.500 mg/ kg free and hydrolyzed formaldehyde. The lower limit is 16 mg/ kg. The result under this limit is reported as“non-perceivable”. Particularly the formaldehyde amount shall be tested with very precise methods in baby textile products.

In the Turkish patent application no. TR2015/17637, usage of fluorescent neon pigment based oil paints without formaldehyde in the textile sector is disclosed.

In the American patent application no. US20060351718, fabric treatment components that include formaldehyde adsorbents are disclosed.

As it can be seen in the above mentioned patent applications, in the present state of the art, it is known that there are studies in terms of the reduction in usage of formaldehyde in the textile products. However, in the current patent applications, there is no method related to the determination of formaldehyde. Technical Problems aimed to be solved with the Invention

It is aimed to limit the usage of textile products with high formaldehyde amount by means of precisely measuring the amount of formaldehyde which is a carcinogen substance when absorbed by the skin in the textile products together with the inventive formaldehyde analysis,.

It is aimed to keep the amount of formaldehyde level is particularly baby textile products by means of measuring the amount of formaldehyde up to 3 ppm Together with the inventive formaldehyde analysis method which can be measured up to 16 ppm with the current analysis methods. It is aimed to provide high level of safety in the measurement results by means of subjecting the materials used during the measurement of formaldehyde chemical which is carcinogen during absorption by the skin and forms thread for the human health, in the laboratory conditions to degradation tests together with the inventive formaldehyde analysis method. In order to understand the inventive method better, the figures will be taken into consideration.

Description of the Figures

Figure-1 : shows a perspective view of the volumetric flask used in the inventive formaldehyde analysis. Figure-2: shows a perspective view of the water bath used in the inventive formaldehyde analysis.

Figure-3: shows a projection view of the glass filter used in the inventive formaldehyde analysis.

Figure-4: shows a projection view of the conical flask used in the inventive formaldehyde analysis.

Figure-5: shows a perspective view of the vial used in the inventive formaldehyde analysis.

Figure-6: shows a perspective view of the burette used in the inventive formaldehyde analysis. Sections and Part Reference Numbers for clarifying the Invention

1- Volumetric flask

2- Water bath

3- Glass filter 4 Conical flask

5- Vial

6- Burette

Phases of the Analysis Method; 100: Reactive preparation phase

1 10: Main stock solution preparation phase 120: Buffer stock solution preparation phase 130: Test samples preparation phase 140: Calibration solution preparation phase 150: Calibration standard preparation phase

160: Conditioning phase 170: Measurement phase 180: Main stock control phase 190: Impurity control phase

Detailed Description of the Invention

Together with this invention it is provided to measure the formaldehyde amount in the products produced particularly in the textile sector up to 3 ppm levels. It is concluded that the formaldehyde which is a carcinogen chemical substance must be removed from the textile products at a maximum level.

In the inventive analysis method, in Figure 1 , the views of the laboratory products used in the analysis phases are given. In Figure 2, the flow chart showing the basic phases of the inventive analysis method is given.

Phases of the inventive formaldehyde analysis method are basically as the following;

- Reactive preparation phase (100)

- Main stock solution preparation phase (1 10)

- Buffer stock solution preparation phase (120) - Test samples preparation phase (130)

- Calibration solution preparation phase (140)

- Calibration standard preparation phase (150)

- Conditioning phase (160)

- Measurement phase (170) - Main stock control phase (180)

-Impurity control phase (190)

In the inventive analysis method, the test phases to be followed for making the formaldehyde determination in the textile products are shown respectively. The steps include within the phases are explained as follows. Reactive preparation phase (100): In this phase, 150 grams of ammonium acetate is dissolved in 800 milliliters distilled water. Then 3 ml glacial acetic acid and 2 ml acetyl ketone is added to this solution. After this mixture is stirred during a period then it is taken into a volumetric flask (1 ) with 1000 ml volume and 45 ml distilled water is added onto thereof. After this, the mixture is kept in the dark for 12 hours and it can be used for 6 weeks.

Main stock solution preparation phase (110): In this phase, 3, 8 ml is taken from the solution comprising 37 % ratio formaldehyde and distilled water and put into the volumetric flask (1 ) with 1 liter volume and onto it distilled water is added until it reaches to 1 liter volume. The formed solution is the main stock solution and hereinafter it will be called as S1.

Buffer stock solution preparation phase (120): 10 ml from S1 as the main stock solution is taken and added into the volumetric flask (1 ) with 200 ml volume and 190 ml distilled water is added for filling the 200 ml volume of the flask. This mixture is the buffer stock solution and hereinafter it will be called as S2.

Test samples preparation phase (130): In this phase 7 test samples are prepared. For the first test sample distilled water is added into the volumetric flask (1 ) with 100 ml volume. For the second test sample 4 ml buffer stock solution S2 is added into the volumetric flask (1 ) with 100 ml volume and 96 ml distilled water is added thereon. For the third test sample, 2,5 gram raw fabric is added into the volumetric flask (1 ) with 100 ml volume and onto it 4 ml buffer stock solution and distilled water for filling the volumetric flask (1 ) are added. For the fourth test sample 2,5 gram test fabric is added into the volumetric flask (1 ) with 100 ml volume and distilled water is added onto it for filling the volumetric flask (1 ). For the fifth test sample, 2 ml is taken from the buffer stock solution S2 and together with 98 ml distilled water they are added into the volumetric flask (1 ) with 100 ml volume. The volumetric flasks (2) including 5 test samples are agitated during 1 hour at 85-100 rpm (revolutions per minute= in a constant axis, number or rotations/ cycles realized within 1 minute) in 40 °C water bath (2) in a manner such that water passes the vials. After 1 hour period has passed, it is filtered into 100 ml conical flasks (4) by means of 50 ml glass filter (2). 5 ml is taken from the samples within the volumetric flask (1 ) in a manner such that it is taken in the following manner 2 portions from the third test sample comprising 2,5 grams of raw fabric, 4 ml buffer stock solution and distilled water and the fourth test sample comprising 2,5 grams of test fabric and distilled water, 1 portion each from other samples and they are places in 25 ml small amber vials (5).

Calibration solution preparation phase (140): In this phase, 10 calibration solutions are prepared in the volumetric flasks (1 ) with 50 ml volume. In this first volumetric flask (1 ) there is 50 ml distilled water. In the second volumetric flask (1 ) there is 0,05 ml buffer stock solution S2 and 49,95 ml distilled water, in the third volumetric flask (1 ) there is 0,1 ml buffer stock solution S2 and 49,9 ml distilled water, in the fourth volumetric flask (1 ) there is 0,2 ml S2 and 49,8 ml distilled water, in the fifth volumetric flask (1 ) there is 0,5 ml S2 and 49,5 ml distilled water, in the sixth volumetric flask (1 ) there is 1 ml S2 and 49 ml distilled water, in the seventh volumetric flask (1 ) there is 1 ,5 ml S2 and 48,5 ml distilled water, in the eight volumetric flask (1 ) there is 2 ml S2 and 48 ml distilled water, in the ninth volumetric flask (1 ) there is 3 ml S2 and 47 ml distilled water, in the tenth volumetric flask (1 ) there is 4 ml S2 and 46 ml distilled water.

Calibration standard preparation phase (150): In this phase, 5 ml is taken from the solutions which were prepared during calibration solution preparation phase (140), they are added in amber vials (25) with 25 ml volume, and 5 ml reactive substance is added on each of these solutions.

Conditioning phase (160): In this phase, 7 test sample vials (5) prepared during the test samples preparation phase (130) and 10 calibration solution vials (5) prepared during the calibration solution preparation phase (140) are kept during 30 minutes in the water bath with 40°C temperature without agitation, at the end of said 30 minute waiting period, the vials (5) removed out of the water bath (2) are rested in a dark environment during 30 minutes.

Measurement phase (170): In this phase, the spectrophotometry is activated which a photometry device, is used for determining the substance amounts in the solution for measurement. 1 cm cells are used by means of selecting 412 nm wavelengths from the device. The calibration curve is drawn for the measurement. In order to draw the calibration curve, from the spectrophotometer, new method, mg/ 1, linear and 10 points (0- 0,075-0,15-0,3-0,75-1 ,5-2,25-3-4,5-6 ppm) is selected. Separately 10 measurements are made for each vale. For the measurement of test samples, from the spectrophotometer open method, mg/ I, linear is selected and measurements are made for 7 test samples. Wherein ((ST-BT-MTD) ^* 100) / 2,5 formula is applied by using the following;

- Measurement result of the test sample comprising ST: 2,5 grams of fabric, 4 ml S2, water and reactive.

- Measurement result of the test sample comprising BT: 2,5 grams of fabric and water

- Measurement result of the test sample comprising MTD: Distilled water and reactive.

The value obtained as a result of the formula is the concentration of the test sample.

Main stock control phase (180): In this phase, control is made for the degradation status of the main stock solution S1 which has 6 weeks usage life. For this, 126 grams of sodium sulfide is taken. It is added into the volumetric flask (1 ) with 1 liter volume and distilled water is added onto it until the volumetric flask (1 ) is full. Therefore 1 molarity sodium sulfide solution is obtained. Then 0,1 gram thymolphthalein is taken and added into the volumetric flask (1 ) with 10 mil volume and ethanol is added thereon until the volumetric flask (1 ) is full. This solution is an indicator solution. Then 2,78 ml H2SO4 is taken and added into the volumetric flask (1 ) with 1 liter volume and distilled water is added thereon until the volumetric flask (1 ) is full. Then 50 ml sodium sulfide is added into the conical flask (4) and 2 drops of indicator solution are dropped. Then 10 ml of main stock solution S1 is added into this conical flask (4). Then prepared H2SO4 solution is added into the burette (6) as titrisol. Titration process is started and H2SO4 is added until the color disappears. The volume of H2SO4 as soon as the color is diminished is recorded. This value is written in value volume (V) as ml. Here (V ^* 0,6 ^* 1000) / 10 ml formula is used. As a result, 1500 mg/ L value is obtained. In this value deviations up to 5 % more or less are acceptable. In case a value out of this value is obtained, S1 main stock solution cannot be used.

Impurity control phase (190): In this phase, first of all 1 gram dimedone is added into the volumetric flask (100) with 100 ml volume and dimedone solution is formed by means of adding ethanol thereon until the volumetric flask (1 ) is full. Then 5 ml amount is taken from each of the following samples; the sample comprising 2,5 grams of raw fabric, 4 ml buffer stock solution and distilled water and the fourth test sample comprising 2,5 grams of test fabric and distilled water and 1 ml of dimedone solution is added to each these. These mixtures are kept during 10 minutes within the water bath (2) at temperature of 40°C without agitation. At the end of 10 minutes, 5 milliliters of distilled water are added to the mixture comprising 2,5 gram test fabric, distilled water and dimedone; and 5 milliliters of reactive is added to the mixture comprising 2,5 grams of raw fabric, 4 ml buffer stock solution, distilled water and dimedone. Both solutions are kept during 30 minutes within the water bath (2) at temperature of 40°C without agitation. At the end of 30 minutes, the vials (5) which are taken out of the water bath (2) are rested in the dark for 30 minutes. Then the measurement phase (160) is reapplied. A new value is found by using ((ST-BT- MTD) ^* 100) / 2,5 formula again. This value is the contamination result of the sample. The final formaldehyde amount is found by subtracting the sample contamination value from the sample concentration value which was found in the measurement phase. Applicability of the Invention to Industry

In the inventive formaldehyde analysis method for the textile materials, the usage of textile products with high formaldehyde content will be limited by means of determining the formaldehyde ratio in the textile products up to 3 ppm level in the readymade clothing sector. Together with said method, particularly it will be possible to precisely determine the formaldehyde within the baby textile products.