ODOR- AND EMISSION-REDUCED ANTI-CORROSION AGENT

Abstract

The invention relates to the use of a composition for the preparation of an odor- and emission-reduced corrosion inhibitor for cavity sealing or underbody protection of a component, wherein the composition comprises a resin, wherein the resin comprises a plurality of molecules, wherein the plurality of molecules comprise molecules without double allyl hydrogen atoms, and wherein the odor- and emission-reduced corrosion inhibitor is applied to the component with a wet film thickness of 40 μm to 1,000 μm.

Claims

1. A method for preparing an odor- and emission-reduced corrosion protection agent for cavity sealing or for underbody protection of a component, comprising: applying a composition to the component with a wet film thickness of 40 μm to 1,000 μm, wherein the composition comprises a resin, the resin comprising a plurality of molecules, the plurality of molecules comprising molecules without double allylic hydrogen atoms.

2. The method of claim 1, wherein the molecules without double allylic hydrogen atoms are first molecules, and the plurality of molecules comprise second molecules having double allylic hydrogen atoms, wherein a number ratio of the first molecules to the second molecules is at least 10.sup.3.

3. The method of claim 1, wherein the resin is a modified resin, the modified resin having a smaller number of double allylic hydrogen atoms than a non-modified resin.

4. The method of claim 1, wherein the composition comprises from 5 to 20% by weight of the resin based on 100% by weight of the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection.

5. The method of claim 4, wherein the resin is selected from the group consisting of an unsaturated polyester, an unsaturated alkyd, resin and an unsaturated binder.

6. The method of claim 1, wherein the resin comprises no more than one of an acrylate resin and an epoxy resin.

7. The method of claim 1, wherein the composition comprises 2 to 8% by weight of a wax, based on 100% by weight of the composition.

8. The method of claim 7, wherein the wax is selected from the group consisting of a mineral wax, a fossil wax, and a natural wax.

9. The method of claim 1, wherein the composition comprises from 40 to 70% by weight of an oil, based on 100% by weight of the composition.

10. The method of claim 9, wherein the oil is selected from the group consisting of a mineral oil.

11. The method of claim 1, wherein, after a reaction, the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection can be exposed to a temperature of 70° C. or more for a period of 5 minutes to 2 hours without the reacted odor- and emission-reduced corrosion inhibitor exhibiting detectable change.

12. The method of claim 1, wherein, after a reaction, the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection can be exposed to a temperature of −15° C. or less for a period of 5 minutes to 2 hours without the reacted odor- and emission-reduced corrosion protection agent exhibiting detectable changes.

13. The method of claim 1, wherein the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection comprises less than 100 ppm of at least one short-chain aldehyde.

14. The method of claim 13, wherein the at least one short-chain aldehyde comprises 3 to 9 C atoms.

15. The method of claim 1, wherein the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection comprises less than 100 ppm of at least one short-chain carboxylic acid.

16. The method of claim 15, wherein the at least one short-chain carboxylic acid comprises 3 to 9 C atoms.

17. The method of claim 1, wherein the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection has a rating of less than 3 in an odor test according to VDA 270.

18. The method of claim 1, wherein the odor- and emission-reduced corrosion protection agent for cavity sealing or underbody protection has a rating of less than 3 in an odor test according to PV 3900.

19. The method of claim 1, wherein the component is a vehicle component.

20. The method of claim 19, wherein the vehicle component is selected from the group consisting of a motor vehicle component, a rail vehicle component, a commercial vehicle component, an agricultural machine component, a forestry machine component, a construction machine component, an aircraft component, or a marine vehicle component.

Description

EMBODIMENTS

Example 1

[0115] The following is a procedure for odor evaluation of a corrosion inhibitor.

I. Purpose and scope: This method has been developed in accordance with VDA 270/PV 3900 and is used to evaluate the odor behavior of a corrosion protection agent, in particular HRK material, under the influence of temperature.
II. definition: Odor behavior is understood as the readiness of substances to emit volatile components that result in a perceptible odor.
III. principle: The odor is evaluated olfactorily by a selected odor panel of at least 3 persons, after preconditioning followed by temperature exposure. A size of the odor panel of 5 persons is recommended.
IV. Devices used: [0116] Laboratory stirrer, e.g., IKA stirrer 20.n and inclined blade stirrer, 4 blades made of stainless steel [0117] Cold-rolled steel sheet or odorless, clean aluminum foil (approx. 10 cm×20 cm) [0118] Odorless, clean aluminum foil [0119] Aluminum bowl: Canning jar ø 64 mm; Type: 550028; Mat.-No.: 3201964; Fa. Novelis Deutschland GmbH [0120] 1-liter glass containers with odorless seal and lid are used as testing devices, e.g., 1 L preserving jars from Leifheit (Frucht & Fun). [0121] Heating chamber with air circulation (drying oven), e.g., Heraeus UT 6200

V. Implementation:

V.1 Sample Preparation

a) Spray Waxes

[0122] Stir sample material (viscous cavity preservative) for 15 min at 1000 min.sup.−1 [0123] Apply sample material with a film drawing frame onto a steel sheet or aluminum foil (10 cm×20 cm) with a wet film thickness of 200 μm. [0124] Activation of the samples for 5 min at 65° C. in the drying oven [0125] Preconditioning of the sheets for 7 days at (23±2) ° C. and (50±5) % relative humidity. [0126] Apply mg of the dried product (100±5) to a piece of aluminum foil (5 cm×5 cm) with a spatula [0127] Place the 5 cm×5 cm piece of aluminum foil containing (100±5) mg of product on the bottom of the test vessel and seal it

(b) Flood Waxes:

[0128] Weigh 1 g of the sample material into an aluminum dish (ø 64 mm canning jar). [0129] Place aluminum dish with 1 g sample material on the bottom of the test vessel and close it

c) Raw Materials:

[0130] Weigh 1 g of the sample material into an aluminum dish (ø 64 mm canning jar). [0131] Place aluminum dish with 1 g sample material on the bottom of the test vessel and close it

V.2 Storage Conditions and Odor Test

[0132] All the tests listed below are performed.

a) Spray Waxes:

[0133]

TABLE-US-00001 TABLE 1.1 Storage conditions for spray waxes Temperature Storage Test Condition in ° C. condition note 1  40 ± 2 2 h ± 10 min a), b) 2.1  40 ± 2 7 d ± 0.5 d a), b) 2.2 105 ± 2 2 h ± 10 min c)

(b) Flood Waxes:

[0134]

TABLE-US-00002 TABLE 1.2 Storage conditions for flood waxes Temperature Storage Test Condition in ° C. condition note 3 80 ± 2 2 h ± 10 min d)

c) Raw Materials:

[0135]

TABLE-US-00003 TABLE 1.3 Storage conditions for raw materials Temperature Storage Test Condition in ° C. condition note 1 40 ± 2 2 h ± 10 min a), b) 2.1 40 ± 2 7 d ± 0.5 d a), b) 3 80 ± 2 2 h ± 10 min d)

Test Notes

[0136] The odor evaluation takes place directly after the test vessel has been removed from the drying oven. The test vessel is then closed again. [0137] Re-odor evaluation of the test vessel from a) after storage for 1 day at room temperature. [0138] Storage analogous to condition 2.1 and evaluation according to a) and b). The test vessel is then closed again and stored at 105° C. (condition 2.2). This is followed by an odor evaluation after storage for 7 days at room temperature. [0139] After removal from the oven, the test vessel is cooled for 5 min and then olfactorily evaluated

VI. Odor Evaluation

[0140] The odor evaluation is performed according to the current version of VDA 270. All possible conditions are evaluated with the grades described in Table 1.4. Grades are awarded from 1 to 6, with the award of half grades being possible.

TABLE-US-00004 TABLE 1.4 Grading scale odor evaluation Note Description 1 indiscernible 2 perceptible, not disturbing 3 clearly perceptible, but not yet disturbing 4 disturbing 5 strongly disturbing 6 unbearable

[0141] The result of the determination of odor behavior is given as an arithmetic mean. The scores are rounded in such a way that a gradation of half note increments is produced.

Example 2

[0142] The following is another method for emission assessment of a corrosion inhibitor.

I. Purpose and Scope:

[0143] This method is used to characterize the type and quantity of outgassable organic substances consisting of non-metallic materials used in vehicle interiors. The individual substances are quantified as toluene equivalent.

II. Principle:

[0144] For sampling, the materials are placed in a micro test chamber at a defined temperature and flow. Here, thermal extraction of the analytes on Tenax TA® takes place. The analytes (emissions) are subsequently separated by gas chromatography and detected by mass spectrometer. The measured values obtained from this test method are only valid for the conditions described here. The results obtained are not suitable for making health assessments of the detected substances. The measurement results are also not suitable for making estimates of the total emissions of a vehicle.

III. Devices:

[0145] Micro-Chamber/Thermal Extractor™ (μ-CTE™); 6 chamber model; Fa. Markes International [0146] Rotilabo® aluminium dishes with handle; ø 28 mm, 8 ml; order no. PP54.1; Carl Roth GmbH & Co. KG [0147] Glass tubes; ¼″×3½″; Tenax TA; C6-C30; Conditioned & Capped; Article no.: C1-BAXX-5039; Fa. Markes International [0148] FlowMark™ flowmeter; 0.5 ml/min to 500 ml/min; article no.: N9307086; Perkin Elmer Co. [0149] TD 100xr; Thermodesorber; Fa. Markes International [0150] Cold Trap “General Purpose Hydrophobic; Article No.: U-T2GPH-2S; QC: QQR-0145 [0151] GCMS 2010; Shimadzu Company [0152] GCMS QP 2010; Mass spectrometer; Fa. Shimadzu [0153] μl syringe for standard injection, e.g., 5 μl syringe; Fa. SGE Analytical Science

IV. Implementation:

IV.1 Sample Preparation

a) Spray Waxes:

[0154] Stir sample material (viscous cavity preservative) for 15 min at 1000 min.sup.−1 [0155] Weigh out approx. 150 mg of sample material exactly into an aluminum dish (Rotilabo® aluminum dishes with handle; ø 28 mm) (label the aluminum dish by scoring it with a pointed object, e.g., tweezers). [0156] Activation of the samples for 5 min at 65° C. in the drying oven [0157] Precondition the aluminum dishes for 7 days at (23±2) ° C. and (50±5) % relative humidity.

(b) Flood Waxes:

[0158] Weigh out approx. 150 mg of sample material exactly into an aluminum dish (Rotilabo® aluminum dishes with handle; ø 28 mm) (label the aluminum dish by scoring it with a pointed object, e.g., tweezers).

c) Raw Materials:

[0159] Stir sample material (if liquid) for 15 min at 1000 min.sup.−1 Weigh out approx. 150 mg of sample material exactly into an aluminum dish (Rotilabo® aluminum dishes with handle; ø 28 mm) (label the aluminum dish by scoring it with a pointed object, e.g., tweezers). [0160] Possibly activate the specimens for 5 min at 65° C. in the drying oven (see IV.3 Test instructions). [0161] Possibly precondition the aluminum dishes for 7 days at (23±2) ° C. and (50±5) % rel. humidity. (see IV.3 Test instructions)

IV.2 Sampling

[0162] Sampling is performed using a Micro-Chamber/Thermal Extractor™ (μ-CTE™). Before using the μ-CTE™, it is cleaned with isopropanol. To ensure that all isopropanol is removed before sampling, the chamber is heated to the maximum temperature of 120° C. for 30 min after cleaning and a flow of approx. 40 ml/min is set. The flow is set and checked with the aid of the FlowMark™ flowmeter from PerkinElmer. Sampling is performed on glass tubes filled with Tenax TA (TD tubes). These TD-Tubes are conditioned prior to use to eliminate contamination from the previous analysis, among other things. Conditioning is performed as described in section IV 4.4. For sampling, the TD-Tubes are attached to the outlet of the μ-CTE™.

[0163] For all samples, a reference must be co-measured as a benchmark, since an assessment should only be made relative to a co-measured sample. The sampling parameters can be Tablebe taken from Table 2.3. As a rule, test condition 1 is used. Test condition 2 is only used if an intensification of the signals (obtained from condition 1) is necessary or if the customer specification requires it.

a) Spray Waxes:

[0164]

TABLE-US-00005 TABLE 2.1 Sampling conditions for spray waxes Temperature Flow in Sampling Condition in ° C. ml/min time in min 1 65 ± 2 40 30 2 90 ± 2 40 30

(b) Flood Waxes:

[0165]

TABLE-US-00006 TABLE 2.2 Sampling conditions for flood waxes Temperature Flow in Sampling Condition in ° C. ml/min time in min 1 65 ± 2 40 30 2 90 ± 2 40 30

c) Raw Materials:

[0166]

TABLE-US-00007 TABLE 2.3 Sampling conditions for raw materials Temperature Flow in Sampling Test Condition in °C ml/min time in min notes 1 65 ± 2 40 30 2 90 ± 2 40 30 3 65 ± 2 40 30 a), b) 4 90 ± 2 40 30 a), b)

IV.3 Test Instructions

[0167] a) Activation of the samples for 5 min at 65° C. in the drying oven [0168] b) Precondition the aluminum dishes for 7 days at (23±2) ° C. and (50±5) % relative humidity.

IV.4 Analysis of the Samples

[0169] The analytical separation of the samples is performed by gas chromatography (GCMS 2010). Thermodesorption (TD 100xr) is used for sample application. Detection is performed using a mass spectrometer (GCMS QP 2010). The measurement is performed for all samples using the instrument parameters described in Section IV.4 Analysis of Samples, Tables 2.4 to 2.10. Once a week, an Auto-Tune must be performed on the gas chromatograph to ensure optimal detector voltage and to check the tightness of the system. The respective measurements must always be performed with the current Auto-Tune version.

IV.4.1 Thermodesorption

[0170] The TD 100xr device from Markes International is used for thermodesorption. The “General Purpose Hydrophobic” cold trap is used as the cold trap. It is designed for the analysis of VOCs (volatile organic compounds) in the range of C4/5 to C30/32.

TABLE-US-00008 TABLE 2.4 Cold trap parameters Cold trap parameters Maximum working temperature in ° C. 335 Typical conditioning temperature in ° C. 300 to 320 Typical desorption temperature in ° C. 250 to 300

TABLE-US-00009 TABLE 2.5 General information on the thermal desorber General information Name Marks TD Instrument TD100-S2, TD100 Split, TD100 Trap Mode TD 100-S2.2-3 Stepwise desorption Carrier gas Helium TD100 Type Series 2 Load Temperature in ° C. 50 Ultra Unload 100 Temperature in ° C.

TABLE-US-00010 TABLE 2.6 General setting on the thermodesorber General settings Standby Split On Standby flow in ml/min  25 Flow Path Temperature in ° C. 180 Overlap Off GC cycle time in min  30 Minimum Carrier Pressure in psi  10

TABLE-US-00011 TABLE 2.7 Settings for pre-desorption on the thermodesorber Predesorption Standard Injection Type Prepurge time (min) Prepurge Time in min  1 Prepurge Trap in Line in min Off Purge Trap Flow in ml/min 50 Prepurge Split On Prepurge Split flow in ml/min 40

TABLE-US-00012 TABLE 2.8 Settings for tube desorption on the thermodesorber Tube desorption Desorb Time in min  10 Desorb Temperature in ° C. 280 Trap in Line Desorb On Trap Desorb Flow in ml/min  40 Desorb Split Off Desorb Split Flow in ml/min  50 Tube Desorb 2 Off Desorb Time 2 in min  10 Desorb Temperature 2 in ° C. 250 Trap in Line Desorb 2 On Trap Desorb Flow 2 in ml/min  50 Desorb Split 2 Off Desorb Split Flow 2 in ml/min  50

TABLE-US-00013 TABLE 2.9 Settings on the cold trap on the thermodesorber Settings on the cold trap Trap Purge Time in min  1 Trap Purge Flow in ml/min  40 Trap Low Temperature in ° C.  5 Trap Heating Rate in ° C./s Max Trap High Temperature in ° C. 290 Trap Desorb Time in min  10 Trap Desorb Split in ml/min On Trap Desorb Flow in ml/min  20

IV.4.2 Chromatography

[0171] The GCMS 2010 from Shimadzu is used for gas chromatographic separation. An Optima 5 MS column from Macherey-Nagel with a length of 50.0 m, a thickness of 5.00 μm and a diameter of 0.32 mm or equivalent is used. The oven temperature at the start is 40° C. and the equilibration time is 3.00 min.

TABLE-US-00014 TABLE 2.10 Temperature program gas chromatograph Rate in Final temperature Holding time ° C./min in ° C. in min 0 —  40  4.00 1  3.00  92  2.00 2  5.00 160  2.00 3 10.00 280 14.07

IV.4.3 Mass Spectrometer

[0172] The GCMS QP 2010 mass spectrometer is directly connected to the gas chromatograph and is also from Shimadzu. It is a quadrupole MS with an electron impact ionization source.

TABLE-US-00015 TABLE 2.11 MS parameters Mass spectrometer Temperature ion source in ° C. 200 Interface temperature in ° C. 200 Solvent cutoff in min 5,00 Threshold 40 Start time MS in min 5 End time MS in min 65 ACQ mode Scan Event time in sec 0.5 Scanning speed 769 Start MS scan at m/z 29 End MS scan at m/z 400

IV.4.4 Conditioning of the Thermodesorption Tubes

[0173] The TD tubes are conditioned directly in the thermodesorber. For this purpose, the parameters given in Table 2.12, Table 2.13 and Table 2.14 are applied.

TABLE-US-00016 TABLE 2.12 General settings for conditioning thermodesorption tubes General settings Standby Split On Standby flow in ml/min  10 Flow Path Temperature in ° C. 150 Minimum Carrier Pressure in psi  5

TABLE-US-00017 TABLE 2.13 1Tube purge settings for conditioning thermodesorption tubes Tube Purge Prepurge Time in min  1 Prepurge Split flow in ml/min 50

TABLE-US-00018 TABLE 2.14 Tube desorption settings for conditioning thermodesorption tubes Tube desorption Desorb Time in min  10 Desorb Temperature in in ° C. 250 Tube Desorb Split in ml/min  50 Tube Desorb 2, 3 and 4 Off Desorb Time 2, 3 and 4 in min  10 Desorb Temperature 2, 3 and 4 in ° C. 250 Desorb Split 2, 3 and 4 in ml/min  50

V. Calibration

V.1 Preparation of the Calibration Solution

[0174] For calibration, a calibration solution of toluene in methanol with a concentration of 0.5 μg/μl is prepared. For this purpose, approx. 25 mg of toluene (p.a.) are weighed accurately into a 50 ml volumetric flask and filled up to the mark with methanol (p.a.). The shelf life of the solution is 3 months when stored in a refrigerator. Labeling of the solution with the date of manufacture, contents and expiration date must be clearly visible.

V.2 Measuring the Calibration Solution

[0175] The calibration solution is acclimatized to room temperature. For measurement, 4 μl of the calibration solution is added directly into a thermodesorption tube filled with Tenax TA using a μl pipette. The solution is dispensed as indicated on the thermodesorption tube by means of the arrow.

[0176] Subsequently, the TD tube is flown through with inert gas (helium or nitrogen) for one minute at a flow rate of about 1 l/min to 3 l/min. This ensures that the analyte is adsorbed by the Tenax-TA® and the content of excess solvent (methanol) is largely reduced. The measurement is conducted with the same method as the measurement of the samples (see section IV). A triplicate determination has to be performed.

V.3 Evaluation and Calculation of the Response Factor

[0177] The evaluation is conducted via the area of the peak. For this purpose, the toluene peak is integrated (“link point”) and the area is determined. This is done for all three measurements. Subsequently, with the aid of the peak areas determined, the response factor is calculated according to equation 1:

[00001]$\begin{array}{cc}{R}_f=\frac{\mu g\mathrm{toluene}\left(C16\right)}{\mathrm{peak}\mathrm{area}}*1000000& \mathrm{Equation}1\end{array}$

VI. Emission Evaluation

[0178] Emission evaluation is conducted according to the respective question. Peaks that must be evaluated in any case are aldehydes and carboxylic acids. The total content of organic compounds over the entire chromatogram (TVOC) is also evaluated. The emission values are given in each case as toluene equivalents in μg/g of sample weight. Toluene equivalents are calculated by using the peak areas and a previous calibration (see section 0). An evaluation of the respective samples is always conducted relative to a co-measured reference sample. Equation 2 is used to calculate the emission values. The response factor (Rf-value) is calculated from the calibration (see section 0).

[00002]$\begin{array}{cc}\mathrm{Emission}\left[\frac{\mu g}{g}\right]=R_f*\frac{\mathrm{peak}\mathrm{area}\left[\mathrm{counts}\right]}{1000*\mathrm{sample}\mathrm{weight}[\mathrm{mg}]}& \mathrm{Equation}2\end{array}$

Example 3

[0179] Three exemplary 100% cavity preservatives (HRK) have the ingredients listed in Table 3.1 below in weight percent:

[0180] Here, “100% HRK” is a conventional cavity preservative in which soybean oil is used as the alkyd resin. 100% HRK 1 and 100% HRK 2 show results for a cavity preservative according to the invention, in which once the soybean oil was reacted in advance with cyclopentadiene in a Diels-Alder reaction (100% HRK 1), or in which an alkyd resin with predominantly conjugated double bonds was used (100% HRK 2).

TABLE-US-00019 TABLE 3.1 Compositions of the tested cavity preservatives 100% 100% 100% CAS No. Trade name Functionality HRK HRK 1 HRK 2 64742-55-8 Mineral oil cut 75 Mineral oil  5.00  5.00  5.00 64742-54-7 Mineral oil cut 300 Mineral oil 46.00 46.00 46.00 68584-23-6, Calcium sulfonate Corrosion- 21.00 21.00 21.00 or protective 70024-69-0 additive 68333-62-0 Soybean oil alkyd resin Binder 10.00 — — 68512-80-1 Modified soybean oil alkyd resin Binder — 10.00 — Alkyd resin with pre-dominantly Binder — — 10.00 conjugated double bonds   96-29-7 MEKO Skin  0.15  0.15  0.15 preventer  136-52-7 Cobalt bis(2-hexylethanoate) Dryer  0.10  0.10  0.10 89749-78-0 Bentone sd 1 Layered  0.25  0.25  0.25 silicate  471-34-1 Precipitated CaCO.sub.3 Filler 13.50 13.50 13.50  8002-74-2 Kerosene wax Wax  4.00  4.00  4.00

Example 4

[0181] Results of odor determination 100% HRK, 100% HRK 1 and 100% HRK 2 from Example 3 according to the determination procedures in Example 1 (Table 4.1) and Example 2 (Table 4.2).

TABLE-US-00020 TABLE 4.1 Odor determination according to example 1 Odor in accordance 100% 100% 100% with VDA 270 HRK HRK 1 HRK 2 Odor grade:2 h/40° C. 3.5 2.5 3.0 Odor grade:2 h/40° C. + 1 d RT 3.5 3 3 Odor grade:7 d/40° C. 4.5 3 4 Odor grade:7 d/40° C. + 1 d RT 4 3.0 3.0 Odor grade:7 d/40° C. + 1 d RT + 3.5 3 3 2 h/105° C. + 7 d RT

[0182] Results of odor determination 100% HRK, 100% HRK 1 and 100% HRK 2 from Example 3 according to the determination procedures in Example 1 (Table 4.1) and Example 2 (Table 4.2).

Table 4.1: Odor Determination According to Example 1

[0183]

TABLE-US-00021 TABLE 4.2 Odor determination according to example 2 Emission determination according to DIN 100% 100% Reduction 100% Reduction 16000-6 HRK HRK 1 in % HRK 2 in % Pentanal in μg/g  5.77  1.97 65.93  2.35 59.27 Hexanal in μg/g 31.77 10.36 67.39 15.29 51.87 Heptanal in μg/g 16.32  0.56 96.54  2.10 87.13 Octanal in μg/g  8.66  0.53 93.85  1.25 85.57 Nonanal in μg/g  1.95  0.79 59.46  0.98 49.74

[0184] From Table 4.1 and, in particular, Table 4.2, it can be seen that the use of the corrosion inhibitor according to the invention results in a reduction in odor and emissions, which is in some cases considerable and is based on a reduced formation of short-chain aldehydes.