JPS59136249A - Composite material having excellent heat resistance and chemical resistance - 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 The present invention relates to a composite having excellent heat resistance 2 and chemical resistance. More specifically, the lining layer is a highly crystallized layer of a crystalline thermoplastic polyether ketone having a specific chemical structure, melt viscosity, and gold. Either 2 or 6 bodies or 17, depending on the lining layer other thermoplastic resin or /
It is a composite material in which a lining layer and a base layer are fully mixed together with 2 and a tentacle-like inorganic compound, and it provides a material suitable for tanks, vibrators, etc. for manufacturing and transporting chemicals etc. at high temperatures. .

Traditionally, equipment for manufacturing, storing, and transporting medicines and foodstuffs includes
Due to its corrosive nature, all metal materials cannot be used.
Materials such as vinyl chloride resin, polyethylene, and 47-ethylene chloride resin are sometimes used, but they lack heat resistance and durability and cannot withstand long-term use. In addition, surface lining of metal materials with epoxy resins or the above-mentioned thermoplastic resins has been carried out, but the chemical resistance and heat resistance are not satisfactory, and ethylene tetrafluoride, which has a high degree of chemical resistance. Even though it is a resin, it is very soft and easily scratched, so it cannot be used, for example, in the production of high-temperature slurry products. It also has poor gas barrier properties and is ineffective with a thin lining layer.

In this field, the surface of the glass container is lined with an inorganic compound such as wax, but the lining is expensive and is brittle, making the container unusable even if it cracks in one place. It has the following drawbacks.

In view of the above-mentioned current situation, the present inventors have developed a method that can be easily cut out onto the surface of a substrate such as metal, like a conventional resin lining.
The present invention was developed as a result of intensive research to develop a composite material consisting of a lining layer and the base layer, which also has excellent heat resistance and chemical resistance, and has appropriate hardness and impact resistance even when exposed to extremely high temperatures. reached.

That is, the first layer contains at least 70 mol of a repeating unit represented by the following formula I -Q-O<ΣC C-01, and is heated for 102 to 103 sec at a temperature of 360 to 400°C.
Melt viscosity at sliding speed of 50 to 500 Pa-s
The main component is a crystalline thermoplastic aromatic polyether ketone in the range of ee, and 20 to 50 weight percent of the molecular chains of the resin are in a crystalline state ffi! The lining layer has a thickness of 0.05 to 5 cm, and the second
A composite in which the layer is a base layer made of metal, metal oxide, or inorganic sintered body, and the first layer and the second layer are integrated, overcomes all of the drawbacks of the conventional lining composite described above. It also satisfies all requirements for high heat resistance 2 and chemical resistance. Furthermore, if necessary, other thermoplastic resins and/or inorganic powders may be mixed with the crystalline thermoplastic aromatic polyetherketone of the first layer in an amount not exceeding 50% by volume. It is also possible to appropriately select the hardness and impact resistance required depending on the purpose of use. Therefore, tanks and pipes obtained from the composite material according to the present invention can be widely used in various plants in the fields of inorganic/Morganic chemicals, gas, food products, etc.

Aromatic polyetherketone, which is a crystalline thermoplastic resin mainly used in the first layer (lining layer) of the invention, has at least 70 moles of repeating units of the above-mentioned chemical structure, and has recently been developed in the UK. It is a resin with excellent heat resistance that was developed by the company and is mainly used for covering electric wires. The method for producing the resin is described in, for example, Japanese Patent Application Laid-Open No. 54-90296.
However, in the present invention, any product obtained by any manufacturing method can be used as long as it has the chemical structure of formula 1. And, as long as it is less than 30 moles, it may contain units other than one type. Examples of such units include: As shown in, for example, "Kogyo Zaizai" Vol. 30, No. 9, page 32, such resins have excellent chemical resistance in that they are insoluble in chemicals other than concentrated sulfuric acid, and can be used continuously at temperatures of 240 to 250°C. Based on these findings, those skilled in the art will be able to easily come up with the idea of applying this resin to fields such as steel pipe lining. but,
As a result of research conducted by the present inventors, we found that even if this resin was applied to the above-mentioned field, it would be difficult to form a good-looking coating layer without pinholes. often lacks hardness and impact resistance, making it impossible to obtain the desired composite.

As a result of further research, the present inventors found that in order to obtain the desired composite, it is safe to treat the resin having a specific molecular chain to a specific crystalline-amorphous state. This is what led us to the formula of the present invention.

The aromatic polyetherketone resin used in the 11th (lining layer) in the second aspect of the present invention has a polymorphism of 102 to 103 sec-1 at a temperature of 360 to 400°C.
6 Melt viscosity is 50-500 Pa-5ee tD range 17
(D Mo (must be D) Generally, the length of the molecular chain of a polymeric substance is expressed in terms of weight or molecular weight, but in order to measure these parameters, it is necessary to make it into some kind of solution. However, as mentioned above, it has been confirmed that the resin does not dissolve in anything other than concentrated sulfuric acid, and that it also decomposes in concentrated sulfuric acid, making it virtually impossible to measure intrinsic viscosity, etc. On the other hand, it is known that a certain relationship exists between melt viscosity and molecular weight for general linear polymeric substances, and the melt viscosity used in the present invention specifies the molecular weight, that is, the length of the molecular chain. The melt viscosity in the above state is 500 Pa.
If the resin has a long molecular chain of -see or more, it is difficult to coat the substrate uniformly, and especially when powder raw materials are used, defoaming is not successful and pinholes occur. If a resin having a melt viscosity as low as 5 QPa-5ec is used, sagging may occur during melt lining, and the impact strength, hardness, and heat resistance of the resulting lining layer may be reduced. Therefore, the resin is preferably in the range of 50 to 5 Q Q Pa-5ec.

For measuring the bath melt viscosity, a capillary-type viscosity probe such as a Koka type flow tester is preferred.

Next, in order to obtain a lining layer with the desired heat resistance, chemical resistance, hardness, and impact resistance, the melt-bonded resin layer is crystallized under appropriate temperature conditions, and the proportion of the crystalline portion is adjusted. It is necessary to have a weight of 20 to 50 percent. If the degree of crystallinity is less than 20%, it will not only be inferior in terms of heat resistance, chemical resistance, and hardness, but also crystallization will progress due to heat history during use, and there is a risk that cracks will occur. Unfortunately, when the degree of crystallinity exceeds 50% by weight, the adhesion to the base layer decreases. As a method for measuring such crystallinity, X-ray diffraction method or density measurement can be applied. To determine the degree of crystallinity from the X-ray diffraction method, the 4bJ fat piece taken out from the obtained lining layer is measured by a normal wide-angle X-ray diffraction method, and the peak area (Sc+Sa+A) of the obtained diffraction intensity curve is , is determined by the following equation from the peak m product (Sa+A) obtained by similar measurement of the amorphous resin piece specially prepared by quenching and the surface m (A) due to air scattering.

However, the degree of crystallinity can be determined by density measurement using the following formula from the density dc of the perfect crystals of the resin, the density da of the completely amorphous resin, and the density d of the resin piece taken out from the second-inning pigeon. When the aromatic polyetherketone is entirely composed of repeating units represented by the above formula 1, dc is 1
．． 400. da is 1.265. d can be measured by a density gradient tube method, a float-sink method, or the like.

-da Crystallinity Other thermoplastic resins may be used in the first layer in combination with the aromatic polyetherketone in an amount not exceeding 50 volume percent. The thermoplastic resin to be used in combination can be selected from a wide range depending on the application, but examples include 47-ethylene chloride resin, trifluoroethylene chloride resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, and tetrafluoroethylene-propylene hexafluoride copolymer resin. Fluorine-containing resins such as perfluorinated alkyl vinyl ether copolymer resin, ethylene-47-fluorinated tyrene copolymer resin, ethylene-trifluorinated vinyl chloride copolymer resin, vinylidene fluoride resin, vinyl fluoride resin, and polyethylene are preferred. In addition, in the present invention, if there is a need to improve heat resistance, abrasion resistance, and impact resistance even if it sacrifices some chemical resistance and moldability, it may be combined with the aromatic polyether ketone. The inorganic powder may be mixed in an amount not exceeding 50 volume percent and used in the first layer. The inorganic powder used in combination is preferably a scaly inorganic compound such as glass flakes, back matrix or layered graphite.

The thickness of the first layer in the present invention varies depending on the purpose and use, but generally a thickness of 0.05 to 5H is preferable.

The material of the second base layer in the present invention may be a material used in ordinary plants, such as a metal material, a metal oxide, or an inorganic sintered body, and may have a melting point higher than the forming temperature of the lining layer. Any metal material can be used, such as general cast iron, carbon steel, chrome steel, various stainless steels, Monel alloys, corrosion-resistant and heat-resistant alloys such as Inconel, Stelloy, Stellite, copper and its alloys, nickel and Examples include alloys thereof, aluminum and alloys thereof, titanium and alloys thereof, and the like. Also, gold M
Examples of oxides and inorganic sintered bodies include alumina, cordierite, zirconia, carbon materials, silicon carbide, glass, ceramics, stoneware, etc. Special mortars and concrete can also be used. 1.These materials are 450℃
It is preferable that the composition does not change in the following temperature range and the coefficient of thermal expansion is as close as possible to the coefficient of thermal expansion of the resin of the first layer.

In the present invention, the stronger the adhesion between the first lining layer and the second base layer, the better, and for this purpose, it is advisable to pre-treat the base surface in the same way as the usual resin lining treatment. be. As for pretreatment, it is preferable to first remove rust by pickling and degrease by washing with a solvent, and then roughen the surface of the base layer by dry sandblasting with alumina, silica sand, etc., or by chemical etching. Primer treatment used in general resin lining is not preferred in the present invention.

Next, to specifically describe the method for manufacturing the composite according to the present invention, first, the relevant parts such as the tank and the nozzle are pretreated by the above-mentioned method and then heated to 360 to 450°C.The heating method is an electric furnace, Any method such as heating in a gas furnace, infrared furnace, or high frequency induction heating may be used.The resin used for the first layer is preferably in powder form or sheet form, and other thermoplastic resins,
When a scale-like inorganic compound is used together, it is necessary to mix them uniformly in advance. Lining methods include spraying powdered resin, fluid dipping, and electrostatic coating.
A sheet formed in advance may be pasted. In the case of powdered resins, the selection of particle size distribution is also important. At this time, it is important to make the thickness of the adhesive uniform, to make the adhesive strength strong, and to sufficiently remove bubbles to form a lining layer that is free of pinhonyl. For example, in the case of inner lining of a pipe, rotational molding is necessary. It's good to do it. The resin adhered to the surface of the substrate is once completely melted and then slowly cooled to grow crystals to a predetermined degree of crystallinity.As a method of crystallization, the resin is once solidified and rapidly cooled by water sprinkling, etc., and then cooled to a predetermined temperature. A commonly used method is to crystallize by raising the temperature again to or solidify and crystallize by slow cooling, for example 2 in the slow cooling process
It is preferable to keep the temperature around 00° C. for a certain period of time to crystallize it. The lining layer, which has been sufficiently crystallized in this way, becomes opalescent and opaque. The composite obtained through the above steps is finally used after confirming that there are no pinholes in a spark test using a high frequency tester or the like.

The composite according to the present invention obtained by the above method has excellent chemical resistance that will not be corroded by any chemicals other than concentrated sulfuric acid, and can be used continuously for a long time at temperatures below 250°C. Not only does it have excellent heat resistance, but its surface hardness is comparable to that of aluminum, making it outstanding among resin linings.It also has excellent impact resistance and abrasion resistance, and is extremely easy to mold. Therefore, the composite according to the present invention can be used not only in various organic and inorganic chemicals, food products such as soybean oil, industrial fields such as petroleum refining and plating, but also in a wide range of fields such as nuclear power and geothermal power generation. Items that can be used as tanks, piping, boilers, heat exchangers, agitators, classifiers, etc. used in unit operations such as storage, heating/cooling, condensation, evaporation, distillation, classification, absorption, filtration, transportation, and measurement. be.

The present invention will be specifically explained below using practical examples, but the present invention is not limited to these examples in any way. , Example 1 One side of a steel plate of 31 to 31 mm was sandblasted, then acid-purified and degreased.
Aromatic polyetherketone resin powder (average particle size 56 μm) having a melt viscosity of 1801'a-see at 0°C and a sliding speed of 5 x 102 sec'' was heated in an electric furnace maintained at 380'C to form the steel plate. The resin bath melt was spread thinly and uniformly on the sandblasted surface of the copper plate and melted. After repeating this operation three times and uniformly removing the resin from the surface of the copper plate, the electric furnace was maintained at 200'C for about 1 hour. The average thickness of the lining layer of the obtained composite was 0.83+no+ as a result of measurement using an electromagnetic film thickness meter. The density measurement result is ・1.313?/
crA, and the crystallinity calculated by the method described above was 35.6%. Furthermore, as a result of a pinhole test using a spark tester, no pinholes were found. The Percoll hardness of the lining layer of the composite is 48 at a room temperature of 3.14.0°C, which is extremely hard compared to commercially available resin shells. Further, the taper abrasion test result based on ASTM D-1175 was 17, which was excellent and no change was observed. Next, the composite was immersed in each container containing a 30% hydrochloric acid aqueous solution, a 20% circulating soda aqueous solution, toluene, and trichlene, kept at 80°C for 30 days, and then taken out. After washing with water, the lining layer was removed. As a result of microscopic observation of changes, no changes were observed in 30% hydrochloric acid aqueous solution, 20% strength soda aqueous solution, and Trichlorene shell, while toluene shell had a slight loss of surface gloss and had excellent abrasion resistance and hardness. It is suitable for a wide range of chemical containers, piping, etc.

Comparative Example 1 Actual: Melt viscosity measured under the same conditions as Mii Example 1 was 63
Aromatic polyetherketone resin powder (average particle size 210 μm) of 0 Pa-5ec was pretreated in the same manner as in Example 1, and a steel plate of the same thickness 3 was preheated in an electric furnace at 400 °C. It was sprinkled on a surface, melted, and then crystallized in the same manner. The thickness of the lining layer of the obtained composite is 1.31111, and the crystallinity of the resin is 2.
It was 7.396, but the fetal result of the pinhole test was
There are countless pinholes on the object.1. It was not possible to carry out the same chemical resistance test as in Example 1. As described above, when using a resin with a molecular chain length longer than the molecular chain length specified in the present invention (that is, a melt viscosity of 500 Pa-see or higher), no pinholes were produced despite the high molding temperature. It is difficult to form a uniform lining layer, and such resins are not suitable for the field targeted by the present invention.

Example 2 Aromatic polyetherketone resin powder 1 used in Example 1
00 parts by weight and 6Q heavy parts (about 31 volume percent) of commercially available polyvinylidene fluoride resin powder of corrosion-resistant coating grade (average particle size 45 μm) were dry-dried in a Hennel mixer. The mixed resin powder was then sprayed and melted onto a pretreated steel plate at 380°C in the same manner as in Example 1, and then crystallized at 200°C. The thickness of the lining layer of the resulting composite was 0.95 wrm and there were no pinholes. The Percoll hardness of the V compound C lining layer was 32 at room temperature, and the taper abrasion test was 12. The blend reduces hardness but improves wear resistance. It also passed the falling ball impact test, and in the high-temperature chemical resistance test under the same conditions as Example 1, there was only a slight loss of surface gloss against toluene and trichlorene, and there were no pinholes. Suitable for plants that require chemical resistance.

Example 3 Aromatic polyetherketone resin powder 1 used in Example 1
00 parts by weight and 75 parts by weight (about 29 volume percent) of glass flakes of 60 mesh passes were uniformly mixed using a Henschel mixer.

First, the mixed powder was sprinkled on a pretreated steel plate at 395°C in the same manner as in Example 1, and after bath melt coating, it was heated at 200°C.
It was crystallized at C. The thickness of the lining layer of the resulting composite was approximately 1.5 mm and there were no pinholes. The Percoll hardness of the lining layer of the composite was 71 at room temperature, the taper abrasion test result was 10, and it passed the falling ball impact test. By blending glass flakes in this way, hardness and abrasion resistance are improved. Furthermore, as a result of a high-temperature chemical resistance test under the same conditions as in Example 1, there was only a slight loss of surface gloss against toluene and trichlorene, and there were no pinholes, indicating that high-temperature chemical resistance is widely required. Suitable for plants that

Comparative Example 2 The polyvinylidene fluoride resin powder used in Example 2 was used as the lining resin, and baking was performed in an electric furnace at 320°C. The thickness of the lining layer of the resulting composite was about 1.3 mm and there were no pinholes. The Percoll hardness of the lining layer of the composite was O at room temperature, the taper abrasion test result was 11, and the falling ball impact test was also passed. As described above, polyvinylidene fluoride resin has poor hardness and is not suitable for internal lining of pipes such as slurry. Further, as a result of a high temperature chemical resistance test under the same conditions as in Example 1, crazing occurred when exposed to toluene, and a portion dissolved when exposed to trichlene, making it unusable. As described above, even the highest grade conventional lining resin has poor high temperature chemical resistance, especially to polar organic solvents, and is inferior to Example 1 according to the present invention.

Comparative Example 3 A commercially available high-density polyethylene resin powder (average particle size: 100 μm) was used as a lining resin, and a steel plate was coated with the resin in the same manner as in Example 1 in an electric furnace at 220°C. The thickness of the lining layer of the resulting composite was about 1.15 ffff and there were no pinholes. The Percoll hardness of the lining layer of the composite was 0 at room temperature, the taper wear test result was 13, and the falling ball impact test was passed. Further, as a result of a high temperature chemical resistance test under the same conditions F as in Example 1, it was partially dissolved in toluene and trichlene. As described above, polyethylene resin, which is commonly used as a conventional resin lining, has low hardness and is effective against inorganic chemicals, but has poor high-temperature chemical resistance against organic chemicals. Inferior in comparison.

Comparative Example 4 In Example 1, the resin was melted and coated in an electric furnace at 380° C., and then immediately taken out of the electric furnace and put into cold water to be rapidly cooled. The lining layer of the obtained composite was brown and translucent, and is considered to be close to an amorphous state. Each time the composite was crystallized in a hot press at 200°C for about 20 minutes, the lining layer became light brown and devitrified, and its thickness was about 0.92 mm.

The density of the lining layer resin of the composite is 1.28,
The calculated crystallinity was 11. Also, no pinholes were observed. The Percoll hardness of the lining layer of the composite was 37 at room temperature, the taper abrasion test result was 17, and it passed the falling ball impact test. Furthermore, as a result of a high temperature chemical resistance test under the same conditions as in Example 1, it was observed that crazing occurred slightly only in response to toluene, which is a concern for long-term use. As described above, even if the aromatic polyetherketone resin according to the present invention is used in the lining layer, if the crystallinity is less than 20, the surface hardness and high temperature chemical resistance will be poor. Although this resin is known to be insoluble in chemicals other than concentrated sulfuric acid, it also has the property of swelling in some organic solvents, making it suitable for high-grade resin lining applications that require high-temperature chemical resistance. Crystallinity is also an important factor.

Example 4 The inner surface of a steel pipe with an outer diameter of 3 inches, a length of 5.5 m, and a wall thickness of 4.21 m was sandblasted and then acid washed and water washed. While rotating the steel pipe preheated in an electric furnace at 400°C, the resin used in Example 1 was sprinkled on the inner surface of the steel pipe.
% melt coating, and was further slowly cooled to crystallize. The thickness of the lining layer of the obtained composite steel pipe was 1.5 mm,
There were no pinholes. The resin crystallinity of a separately prepared test piece that underwent the same process was 25.9'1. The internally lined steel pipe obtained in this way was used as part of the piping of an actual benzene distillation plant, and after three months of continuous use, it was removed and fI! As a result, it was found that there were no changes in the appearance of the lining layer and no pinholes, and that the lining layer had excellent resistance to high-temperature organic solvents.

Patent applicant Kurashi Co., Ltd. Representative Patent Attorney Tate Honda 331-

Claims (1)

Scope of Claims: (1) The first layer contains at least 70 moles of repeating units represented by the following formula I, and at a temperature of 360 to 400°C,
- Melt viscosity at 50 to 500 Pa
The main component is a crystalline thermoplastic aromatic polyetherketone in the range of -5ec, and 20% of the molecular chains of the resin are
0 thickness at which ~50 weight percent forms a crystalline state
．． A lining layer with a thickness of 0.05 to 5 mm is used, the second layer is a base J made of metal, a metal bide, or an inorganic sintered body, and the first layer and the second layer are integrated into a composite. thing. (2) The composite according to claim 1, wherein the first layer contains not more than 50 percent by volume of a thermoplastic resin other than crystalline thermoplastic aromatic polyetherketone. (8) Thermoplastic resins other than crystalline thermoplastic aromatic polyether ketone include tetrafluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene- Perfluorinated alkyl vinyl ether copolymer resin, ethylene-tetrafluoroethylene copolymer resin, ethylene-trifluorinated vinyl chloride copolymer resin,
The composite according to claim 2, which is any one of vinylidene heptadide resin, vinyl fluoride resin, and polyethylene. (4) The composite according to claim 1, wherein the first layer contains an inorganic powder in an amount not exceeding 50% by volume. (5) The composite according to claim 4, wherein the inorganic powder is a scaly inorganic compound. (6) The composite according to claim 5, wherein the scaly inorganic compound is glass flakes, layered graphite, or mica.