JPS59500866A - Perfluorocarbon resin containing deterioration retardant - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Name Background of perfluorocarbon resin containing deterioration retardant The present invention relates to a perfluorocarbon resin composition containing a deterioration retarder. Furthermore In particular, the present invention relates to heptaolide and tetrafluor, known as FIICP. A copolymer of oleoethylene (TFE) and hexafluoropropylene (RFP), TFE and perfluoropropyl vinyl ether (PP, known as PFA) copolymers with VE), terpolymers of TFK, HFP and PPVK and Such compositions with polytetrafluoroethylene (PTFE) homopolymers relating to things.

Delayed degradation of many polymeric systems when exposed to high temperatures or radiation, especially ultraviolet light. A variety of materials have been found useful in . often from the air Oxygen enhances deterioration.

Organosulfur compounds and various organometallic compounds and sterically hindered amines may be used, e.g. On the action of ultraviolet light on polymers intended for use at normal temperatures of ~100°C In contrast, it is used to delay deterioration by stabilizing the polymer. higher At high application temperatures, rubber, plastics and hydrogen-containing halogenated hydrocarbons, Base resins such as polyvinyl chloride (PVC), 1.6-rivinyl fluoride (PVF ) and polyvinylidene fluoride (PVF) of various types of zeolites. Protected from deterioration with use. Some patent documents describe the contained hydration water. It is important to use zeolite activated by removing more or less Others say that they are activated and should not be activated. ing. Some zeolites are ion-exchanged with monovalent metals such as sodium. For other things, divalent metals such as calcium, exchange ability is important. There are two types of zeolites with different pore size and water content. Lighttra is used, and still others are made in combination with small zeolite. It also requires additional retarders to be used.

However, the aforementioned patents and publications relate to hydrogen-containing resins and It does not relate to perfluorocarbon resins such as PTA and FEP.

ξ-Fluorocarbon resins such as PFA are actually i.e. PV at much higher temperatures than PVF2 without qualitative loss of function. F2 and 150℃ for PVF and 80-120℃ for PVC and probably 260°C for PFA and -PTI and 20°C for FEP. It can be used continuously at 5°C.・Oxidative effects of fluorocarbon resin Although the mechanisms of thermal and thermal degradation may not be completely understood, they are virtually Dehalation is one of the primary mechanisms of td, PVc, PVF and PVF2. Hydrogenation is not included. The reason is that chili-fluorocarbon resins are polymerized. This is because they do not contain hydrogen in their bodies.

The main mechanism of degradation of perfluorocarbon resins is the introduction of lower molecular weight species. peroxide formation and chain scission. In addition to that, perfle Orocarbon resins tend to have functional end groups such as carboxylic acid groups. this They particularly complicate the study of the degradation mechanism, where the resin molecular weight decreases during the degradation process. Ru. Higher temperature of PFA, PTFE and FEP when compared to PVF2 Considering the temperature capability, especially when used at temperatures higher than the maximum usable value of PVF2k. When applying ξ-fluorocarbon resin for PVF2, It is not possible to predict what will happen with perfluorocarbon resins because of the I can't.

Tetrafluoroethylene, known as FEP, for example hexafluoropropylene and furthermore chlorotrifluoroethylene (CTI) and PVF. However, polytetrafluoroethylene homopolymer IJ-7- itself contains The melt processable fluorine-containing resins excepted are those described in U.S. Pat. No. 4,248,763. The subject matter. This patent covers amine antioxidants, organic sulfur compounds, and carbon binders. melting using rack and at least one combination of iron, nickel or cobalt. Improved thermal stability in melt-processable fluorine-containing resins is obtained. these trees The greasy ones are perfluorocarbon resins, but the others contain hydrogen. ing. The maximum operating temperature for hydrogen-containing polymers is also the same for PFA and FEP. and some of the cited additives are not as high as PFA and FEr. It tends to be consumed quickly at temperatures below the maximum operating temperature.

Such quickly consumed additives are of course available for long term effectiveness at high temperatures. It is not something that depends on the state.

Individually or in combination in formulations suitable for industrial and cookware applications containing PTFE, FKP, PFA and other perfluorocarbon resins. A coating composition having a coating composition is disclosed in U.S. Patent No. h, 2s 2.8 s No. 9 [Con, cannon and vary (1981 February 24th) No. 4,123,401 [Berghmans et al. (October 61, 1978)] ], No. 44, 43. '204 (Fang (June 6, 1979)), No. 4 No. 4,45,325 [Vassiljou et al. (June 20, 1979)], No. No. 44, 47, 683 [Vassiljou et al. (April 3, 1979)], No. No. 4,150,008 [Vassi liou et al. (April 17, 1979)] , No. 4.169.083 [Vassjliou (September 25, 1979)] , No. 4,180,609 [Vassiljou] (December 25, 1979) )〕oh.

call No. 4,311,634 [Vassiljou (February 19, 1982)] It is known from several US patents, including the respective specifications.

Zeolites are sometimes ion-exchanged with other metals or with hydrogen. reversibly hydrated silicic acids, typically containing potash or alkaline earth metal oxides. It is luminium. The general structure is Mx/n[(AlO2)x(SiO2)yl-mH20 (where M is a positive valence n ion, and n is 1 or 2). The ratio of X and y is As is known in the art, it can vary from one to a dog number.

Heptaolides allow their use as molecular sieves after water removal It has a framework structure like this. This water removal is carried out in a narrow space of several microns. Up to 50% void volume (m) with well-defined bore size depending on the value). Zeolites include many natural minerals and synthetic materials do. A group of minerals known as feldspars are very closely related to zeolites. and this is sometimes subsumed within the meaning of the term zeolite. way soda Reversibly hydrated feldspars, including stones and ultramarines, are referred to herein as Encompassed within the term olite. They are anhydrous feldspars in their structure It has a more dog-like recess than the previous one and is more open. reversibly hydrated feldspar The zeolites are more closely related to other zeolites other than feldspar. In Seven Oride Hydrated sodium aluminum silicate such as Montmoly lonite, sodium bentonite, saponite and various clays are present. There is.

Summary of the invention The present invention includes perfluorocarbon resins (PFA, PTFE and EP) ) and a zeolite coating composition that acts as a degradation retardant at high temperatures. provide products.

Ultramarine blue contains sulfur species trapped in cage-like structures, which may then be released gradually over a long period of time (time release). ultramarine Blue is the preferred zeolite. Crystal structure that allows similar time release Other zeolites containing sulfur or phosphorus or even selenium or tellurium Lights can also be particularly desirable. The composition of the present invention can be used at temperatures below 380°C. Approximately 106 degrees. )? Example of a perfluorocarbon resin that provides a melt viscosity below Az For example, PFA and FEP fx and a melt viscosity of about 106 poise or more at 380°C. It includes perfluorocarbon resins that give. Polymers with lower melt viscosity melt It can be referred to as processability. Contains other perfluorocarbon resins Copolymers and blends can also be produced and classified in the same manner. Ru.

The unique features characterizing the invention within the meaning of the expression "consisting essentially of" Various perfluorocarbon resins can be blended while maintaining properties. . Such fluorocarbon resins include, for example, PTFE homopolymer, FE Copolymers of TFK and RFP, known as P, and terpolymer formation Therefore, copolymers of TFK and PPVE with or without HEP are mentioned. It will be done.

The coating composition preferably contains an unsaturated hydrocarbon polymer such as an acrylic resin. This is a perfluorocarbon resin that decomposes into a film form at high temperatures. Enhances cohesion. These coating compositions also generally include pigments, mica, pigment coatings, containing coated mica or metal flakes. Mica gives a shiny appearance and may have a tendency to hide penetrating stains. As is or on mica Pigments used as coatings are processed to produce certain colors. If the pigment is iron-containing for some other reason, the iron content may sometimes increase. It tends to increase the degradation of perfluorocarbon resins at high temperatures. The reason is strict Although it is not well known, iron oxide acts as a catalytic agent for the formation of peroxide, which Is there some kind of catalytic effect that causes the deterioration of the fluorocarbon resin? Maybe. Ultramarino Blue also appears to be able to alter the catalytic activity of iron oxide. It is.

DETAILED DISCLOSURE OF PREFERRED EMBODIMENTS Perfluorocarbon polymers such as PFA, PTFE at elevated temperatures in air and FEP degradation is difficult to monitor. PFAlPTFE and The inherent heating performance of FEP is so good that other Its temperature rise property is higher than that for lower temperature polymers such as pv, c and PVF2. It appears that less effort was put into further improvement of Noh. . However, above a certain temperature, PFA, PTFE and 'FEP are not useful. and they are non-resistant even at the high temperatures at which they are normally used. It always deteriorates gradually.

We found that iron oxide pigments sometimes accelerate the degradation of PFA and PTFE at elevated temperatures. The present inventors found that it has a tendency to Ultramarine blue and other zeolites provided counteract that tendency. and that it tends to degrade at high temperatures even in the absence of iron oxide. was found to act as a retardant.

As is known in the art, small amounts, e.g. 0.005% by weight of the coating. Zinc in the form of zinc oxide or zinc oxide is added to ultramarine blue to reduce the sulfur content. Total fixation of effluents (H2S etc.) or their effluent rate if desired It can help slow down the degree.

! To demonstrate these effects, we used a film of PFA itself, and an ultramarine film. Contains phosphorus blue, red iron oxide, and both red iron oxide and ultramarine blue A PFA film was produced. Manufacture these films on aluminum foil and 177°C for 15 minutes and 427°C.

Remove the aluminum foil by curing for 5 minutes in water and then dissolving in hydrochloric acid. did. Samples were prepared as shown in Tables I and H below (hereinafter referred to as Tables I and H). All parts, proportions and candy are by weight unless otherwise specified).

Table 1 A, PTA aqueous dispersion 55% inoctylphenoxypolyethoxylate from Rohm and Haas products Contains Triton 97 at 55% copolymer solids with an average diameter particle size of ~025 μm: Fluorinated ethylene perfluoroalkyl vinyl ether with TI and PPVK ratio of 6 copolymer.

B, acrylic resin solution notyl methacrylate in a ratio of 39157/4 at 40% concentration dispersed in water; Acrylic latex polymer of ethyl acrylate and methacrylic acid.

C, cerium octoate solution Contains 107% cerium and is a blend of:

Cerium octoate (23% cerium) 4.69% diethylene glycol mono Butyl ether 1243 Triethanolamine 3702 Oleic acid 985 Triton x-100 surfactant 4.99D, red iron oxide pigment millbase Deionized water 545 E, Ultramarine Blue Pigment Milbase Tridon X-100 Surfactant 0 25 Deionized water 5524 Blend each of these ingredients separately and then combine and blend them. 1 APFA dispersion 186.57 B Cerium octoate solution 18662APFA dispersion 186.57 B Cerium octoate solution 1866C red iron oxide mill (-S 44 3APFA dispersion liquid 186.57 B Cerium octoate solution 1866C Ultramarine Blue Milbase 4 44APFA dispersion liquid 186.57 B Cerium octoate solution 18.660 Red iron oxide millbase 44 D Ultramarine Blue Milbase 44 film sample without support f-+ red placed in a frame holder of the type used for external line analysis and held in air for 7 days. Heated to 290°C in a convection oven for 2 hours. At the end of this time Ultramari Samples containing no blue were partially broken apart, leaving a large hole in the center.

On the other hand, the ultramarine blue-containing sample is in the form of a single layer film and has much less It showed deterioration.

Effects of ultramarine blue and other heptaolides on PFA degradation A complete nuclear magnetic resonance (TMR) test was carried out for the determination. PFA is hot in the air When deteriorating with Closer to FB, but lower and more desirable than commercially available PTFE resins There is a tendency for the polymer to be converted into a polymer having a molecular weight of 1. Also, the benefits of PFA itself are lost. It will be done.

Certain molecules, including those identified for the ppvg perfluoropropyl group In order to show how large a proportion of fluorine atoms are present in the part, the 19F structure NMFt is used to monitor.

NMR data is characterized by peak height (intensity), peak width at half height (for many reasons) (broadening of the line), and the area under the peak. TFK of peaks for various fluorine configurations, including backbone and PPVE positions. The relative area quantitatively reflects the molar ratio of TFE to PPVE in the polymer.

The resonant frequency and line width of such a peak are pp of the frequency of the excitation radio frequency. It is reported in m. i.e. for example 184 ;'NM using a force-help magnetic field For R devices, 1 ppm is a frequency of 184 hertz. known to those skilled in the art As in, the sample to be analyzed is placed in a homogeneous magnetic field and a radio frequency oscillating Excited by the field. The NMR spectrometer is applied to the sample when the frequency is swept. It is obtained by detecting energy absorption by NMR spectrum with sufficient resolution The R vector is obtained at temperatures above 600°C, well above the melting point of the polymer.

The magnetic sensitivity of iron oxide complicates these NMR studies, but is considered here. The results obtained are believed to be independent of such effects.

One set of samples contained PFA, an acrylic polymer to aid film cohesion, and a pigment dispersion. Triton X-100 surfactant, and acrylic polymer and Cerium octoate helps Triton x-100 burn, accelerates deterioration. iron oxide pigments to simulate colors used commercially, and in some cases It contained more ultramarine blue. This formulation is given in Table 1H below. AP, FA 70.03 Triton X-1001,95 B Acrylic polymer 1169 C cerium octoate 1178 Deionized water 1088 (1ro) 6 Sample 5 1o6.33 D Red iron oxide 170 7 Sample 5 98.99 E Ultramarine Blue 1,70 8 Sample 5 106.33 D Red iron oxide 1.7゜ E Ultramarine Blue 170 Samples were prepared as described for Samples 1 to 4 above and subjected to NMR analysis at 40°C. , (A vector was obtained. The peak near 80-86 ppm indicates PPVE. 120 The peak near pl')m indicates TFE. Samples 5.7 and 8 had the same amount of PP VE but did not show any loss due to deterioration. Sample 6 is J: Tsuna It contained no peak, indicating that PPVE had disappeared.

If the sample contains similar proportions of PFA, acrylic polymer, cerium octoate and Added in the same proportion as YoV iron oxide, ultramarine blue and ultramarine blue. Other sets of zeolites containing several other types of zeolites obtained In the NMR test, the line width expansion of the o peak near 120 ppm was measured at 340°C. It was measured with The increase in iron oxide content shows a greater spread, which, among other phenomena, Also shows the rose magnetic effect of iron oxide. Iron oxide is kept constant In this case, differences in spreading were detected depending on the type of zeolite. such an increase The broadening of the line (as well as the total area under the 120 ppm peak) indicates the disappearance of PPVB. It is thought that it is related to. Cords containing sulfur and having an estimated time migration phenomenon Lutramarine Blue gave a line broadening of 7.6 ppm. Other zeolites gave a line broadening from 11.5 to 12.6 ppm i. in contrast to that For samples containing iron oxide but no heptaolide, (The ri was 16.5. This was the case for all seven tested) of PFA. be effective in retarding deterioration, and ultramarine blue is by far the best was also shown to be effective. The values obtained for certain heptaolides are as follows. is given to.

10’ LZY-8211,0 11 Omega (Omega) 11.3 12 28M3 11.4 13 M-811,5 14 Beta (Beta) 11.5 1' 5 LZY-8211,6 16 Ferrierite 11.7 17 Maizeite 11.7 18　ELZ-2011,9 19ZSM-412,0 22 Chabazite 126 23 ZSM-512,3 24EL, Z-L, 12.4 25 LZY-5212,6 26 iron oxide (no zeolite) 165 In the same NMR test, LZY = 8 2 is 0.8% PPVE' (z preserved, in contrast Ultramarine Blue - is 06% PPVE.

Save M-80.5%, LZY~52...04% and Sodastone...03% I let it happen.

In yet another set of NMR tests on similar samples, 27 PTA, Ce, Kurilo or without Fe 1428 PFA, ('e, Acrylic 1.429 PFA, Ce,’ Acrylic, Fe O, 130PFA, Fe, Ce i or A No Krill 0531 PFA, Ce, Acrylic, Fe, Ultramarine Blue 08ro2 PFA, Ce, Acrylic, Fe, Sodastone 0653 PFA, Ce, acrylic, Fe, M-3 zeolite 05PFA, Fe2O3 and X-ray diffraction analysis of the ultramarine blue mixture shows that Fe2o3 is PFA at 427°C. However, ultramarine blue iP reacts with iron oxyfluoride to form iron oxyfluoride. Inclusion in a mixture of FA and Fe2O3 inhibits the formation of iron oxyfluoride. It was shown that this is likely to happen. PPVE perfluorozolopyl group during the first reaction but during the second reaction it does not disappear and the magnetic sensitivity is significant. does not increase. This is due to ultramarine blue, which inactivates the iron catalyst function. This can explain the iron-derived deterioration mechanism of PFA, which is delayed by the iron-induced deterioration of PFA.

Determine what effect ultramarine blue has on deterioration Another series of tests used infrared analysis of thermal spills. discussed above Similar samples were tested with PFA alone, PFA with iron oxide, PFA with ultra Comparing marine blue, PFA, iron oxide, and ultramarine blue. Ta. The test was conducted by heating the sample from room temperature to 400℃ for 15 minutes, and then heating it to 400℃ for 85 minutes. holding and then increasing from 400° to 450°C for 80 minutes. It was carried out by Some RFP and some 4F between 400℃ and 450℃ Silicon oxide was detected, which is indicative of PFAO content. SiF4 is It may be derived from fluorine that reacts with the glass in the room. This result shows that iron oxide Increasing the degradation rate of PFA, while ultramarine blue has iron oxide. It was shown that the speed can be roughly halved regardless of the speed. Saita (17) A small amount of SO2 was detected between 400 and 450℃, which indicates a time release phenomenon. It is something. In addition to the generally indicated benefits of zeolites, ultramarine blue The time release of sulfur from the It is thought that it may cause injury.

PTFE, 50% p’ryg15o% PFA, and PFA samples (this control without oxide pigment and with iron oxide and ultramarine blue pigment. Other engineering rate tests were conducted using a sample with a

1002 sample samples in an oxygen-enriched atmosphere of 50 volumes of air and 150 volumes of oxygen. 4 in a glass-free stainless steel system at a flow rate of 13 m and 1.7 min. During a test period of 4 hours at 00°C (after heating for 15 minutes from 23°C) The following data were obtained. The numbers are HF, COF2, SiF4 and HFP' ( z represents the number of mg of fluorine in the generated fluorination effluent containing z. It is an unidentified small molecule amount of saturated fluorocarbons (which amount to less than 10% of the total fluorine generated) and Any fluorinated sublimate that may have formed should be washed away.

PTFE 34 vs. 09 35 Iron oxide 2.1 36 Ultramarine Blue 0.3 50PTFE150PFA 7 vs. 11.4 38 Iron oxide 250 39 Ultramarine Blue 95 F.A. 40 vs. 607 41 Iron oxide 234 42 Ultramarine Blue to 20 From one set of experiments, iron oxide increased degradation relative to each control containing PTFK. However, this is not the case for PFA samples, whereas ultramarine blue It can be seen that in each case the deterioration is delayed compared to the control and iron oxide samples. Wear. For each PFA-containing sample that concomitantly contains ultramarine, the so2 Occur. However, depending on the 50PTFE150 PFA sample, it is half that of the PTA sample. and by the PTFK sample it is not generated at all.

Ultramarine in place of cobalt blue pigment for a period of 6 to 12 months Aluminum frying pan with commercially available PTFK multilayer coating replacing roux Limited data from home use testing suggests that the ultramarine blue Excellent scratch and blister resistance against coating It was. Stain resistance was slightly better for Ultramarine Blue at 6 months. At 12 months, cobalt blue was slightly worse. Such a trial ( 19) The study is experimental and does not elucidate the mechanism of degradation. deer But they are at least ultramarine blue for PTFE coating. The model is shown to provide a longer useful life. This is clear This is due to the delay in the degradation of the coating in a certain manner. Sword multi-layer PTFK In the coating Nodame Zolaimer, ultramarine blue is cobalt. It has been found to give less oxidative degradation than blue. This thing is Indicated by haze and bloom, or localized deterioration of surface appearance.

In contrast to experience with PFA, where iron generally appears to exhibit increased degradation, Various tests on PTFE have shown that iron sometimes enhances the degradation of PTFK and sometimes indicates that it is delayed. However, whether or not iron is present , ultramarine blue consistently retards the degradation of both PFA and PTFE. it is conceivable that. Therefore, the present invention provides a method for treating fluorocarbons regardless of whether iron is present. Using ultramarine blue-marine or other zeolites for carbon resins is intended.

Thermogravimetric analysis to track the effect of various additives in delaying PTFK degradation Attempts to use (TGA) were unsuccessful.

It was difficult to determine the optimal sample size and geometry. TGA de Although the weight gain and weight loss phenomena accumulate over time at elevated temperatures, I can't tell you anything about what happened.

international search report

Claims (1)

[Claims] 1. The fluoropolymer is a perfluorocarbon resin, and the composition is 380 having a melt viscosity of less than about 106 Boas at a temperature of less than or equal to The fluorocarbon resin acts to retard the oxidative deterioration of the ξ-fluorocarbon resin at elevated temperatures. a composition consisting essentially of a fluoropolymer resin and a zeolite, characterized in that A product. 2. Perfluorocarbon resin consists of tetrafluoroethylene and hexafluoropolymer The composition according to item 1 above, which is a copolymer with lopyrene. 3 Perfluorocarbon resin is tetrafluoroethylene and perfluoropropylene The composition according to item 1 above, which is a copolymer with rubinyl ether. 4 The crystallographic structure of the zeolite allows for the gradual release of sulfur or phosphorus. 2. The composition according to item 1 above, which contains sulfur or phosphorus. 5. The composition according to item 1 above, wherein the zeolite is ultramarine blue. 6. A coating composition comprising the composition described in item 1 above. ZJj4. An unsaturated carbon that decomposes at high temperatures but below the melting point of the perfluorocarbon resin. It also contains hydrogenated polymers, and the unsaturated hydrocarbon polymers are perfluorinated. The aforementioned No. Coating composition according to item 6. 8. The unsaturated hydrocarbon polymer is an acrylic polymer and also an acrylic polymer The coating composition according to item 7, which also contains an oxidation catalyst that aids in the decomposition of . 9. At least one of pigments, mica, pigment-coated mica, and metal flakes 9. The coating composition according to claim 8, which also contains or contains seeds. 10. The coating composition according to item 9 above, wherein the pigment includes iron oxide. 11. The coating according to item 10 above, wherein the zeolite is ultramarine blue. composition.