JPH0684059B2 - Resin coated metal body - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin-coated metal body suitable as a pipe material or an inner wall material of a tank, through which an organic solvent or oil flows at high temperature.

(Prior Art) A synthetic resin is coated on the surface (inner surface and / or outer surface) of a metal body mainly for the purpose of preventing corrosion of various metal products.

Polyaryletherketone resin has heat resistance, water resistance,
A crystalline resin with excellent acid resistance, alkali resistance, solvent resistance, and oil resistance. Therefore, it is expected that the resin-coated metal body having the above characteristics can be obtained by coating the surface of the metal body with this resin. In fact, when the surface of the metal body is coated with this polyaryletherketone resin, it is necessary to crystallize the resin in the manufacturing process of the resin-coated metal body or the like in order to sufficiently exhibit the above-mentioned characteristics.

However, when the crystallinity of this resin is increased, residual stress due to crystallization is generated, and the coating layer is likely to peel or crack. Even when the crystallization step is not provided in the manufacturing process of the resin-coated metal body, crystallization may spontaneously proceed depending on the use conditions, and in this case also, the coating layer may be peeled or cracked.

On the other hand, polyaryl ether sulfone resin has heat resistance,
It is a non-crystalline resin with excellent acid resistance and alkali resistance. Therefore, it exhibits very stable characteristics in the temperature range from room temperature to the glass transition point, and since it is an amorphous resin, coating the metal body surface with this resin causes residual stress due to crystallization of the coating layer. Has the advantage that no

However, such a polyaryl ether sulfone resin has a relatively large water absorption property, and particularly in applications where high temperature steam or the like comes into contact, blisters (peeling) or peeling are likely to occur in the coating layer, and also ketone series, ester series, amide series. There is a problem that it is vulnerable to strongly polar organic solvents such as systems, especially high temperature solvents and oils.

(Problems to be Solved by the Invention) The present invention is to solve the above problems, and an object thereof is to provide excellent adhesiveness between a coating layer and a metal body, heat resistance, water resistance, and acid resistance. Another object of the present invention is to provide a resin-coated metal body having excellent alkali resistance, solvent resistance, and oil resistance.

(Means for Solving the Problems) The resin-coated metal body of the present invention has the following formula [I] or / and [II] on the surface of the metal body that has been undercoated or sprayed.
A first resin comprising a mixture of a polyaryletherketone resin having a repeating unit represented by and a polyarylethersulfone resin having a repeating unit represented by the following formula [III] or / and [IV] A second resin composed of a polyaryletherketone resin having a repeating unit represented by the following formula [I] or / and [II] is coated thereon, whereby the above-mentioned object is achieved. Is achieved.

Among the polyaryl ether ketone resins used in the present invention, as the resin having the repeating unit represented by the above formula [I], there are listed as Imperial Chemical Industry (IC
I) Victrex PEEK manufactured by the company. This resin is a crystalline resin having a melting point of about 334 ° C and a glass transition point of about 143 ° C. Moreover, as the resin having the repeating unit represented by the above formula [II], for example, Victrex PEK manufactured by ICI is mentioned. This resin is a crystalline resin having a melting point of about 365 ° C and a glass transition point of about 165 ° C.

Among the polyaryl ether sulfone resins used in the present invention, examples of the resin having the repeating unit represented by the above formula [III] include Victrex PES manufactured by ICI. This resin is an amorphous resin having a glass transition point of about 225 ° C. Examples of the resin having the repeating unit represented by the above formula [IV] include UDEL P-1800 manufactured by Amoco Performance Products Co., Ltd. This resin is an amorphous resin having a glass transition point of about 190 ° C.

In the present invention, the above-mentioned polyaryletherketone resin and polyarylethersulfone resin are mixed to form the first resin. In this case, as the polyaryletherketone resin, only one of the resins having the repeating unit represented by the formula [I] or the formula [II] may be used, or both the resins may be mixed and used. May be. Further, polyaryl ether sulfone resin is also a resin having a repeating unit represented by the formula [III] or the formula [IV],
Only one of the resins may be used, or both resins may be mixed and used.

The polyaryl ether ketone resin and the polyaryl ether sulfone resin are generally mixed in a weight ratio of 10:90 to 90:10, preferably 40:60 to 80:20. When the amount of the polyaryletherketone resin increases, the coating layer tends to be cracked or peeled due to the shrinkage of the first resin coating layer due to crystallization. On the contrary, when the amount of the polyarylethersulfone resin increases, the absorbency of the first resin coating layer increases, so that the water resistance decreases and blisters easily occur.

An inorganic filler is contained in the first resin, if necessary. This inorganic filler increases the thermal conductivity and elastic modulus of the coating layer. Furthermore, it also has the effect of reducing the residual stress inside the coating layer. Therefore, the inorganic filler increases the strength of the coating layer and prevents the occurrence of cracks in the coating layer due to shrinkage due to crystallization.

As such an inorganic filler, excellent in water resistance and chemical resistance,
A material that is stable even at a high temperature of 400 ° C is used. For example, metal oxide, glass, carbon, ceramics, etc. are used. Examples of the metal oxide include alumina, iron oxide, titanium oxide, zirconium oxide, chromium oxide, nickel oxide and the like. Potassium titanate is also included in this. Ceramics include silicon nitride, titanium nitride, boron carbide, silicon carbide, etc. in addition to those contained in metal oxides.

These inorganic fillers are preferably contained as fine powder in the form of fibrous, granular or flake. The inorganic filler is preferably contained in the first resin in an amount of 40% by weight or less, more preferably 10 to 30% by weight.
If it exceeds 40% by weight, the binding force with the resin component of the coating layer is hindered, so that the adhesion of the coating layer to the metal body decreases.

The above-mentioned inorganic filler is also contained in the second resin, if necessary, for the same purpose as above. The content is similar to that of the first resin.

In the present invention, simple metals such as iron and aluminum, or various alloys such as stainless steel are used as the metal body as a raw material. The shape of these metal bodies is not particularly limited. Various shapes such as a flat plate shape, a tubular shape, and an irregular shape are used. The surface of such a metal body is subjected to an undercoating treatment using an undercoating composition or a thermal spraying treatment for spraying a thermal spray material onto the metal body.

As the undercoat composition, a composition containing a thermosetting resin and an inorganic filler, or a composition containing an inorganic binder and an inorganic filler is used. Thermosetting resin,
For example, there are imide resin, epoxy resin, phenol resin, amide imide resin, and furan resin. In particular, an imide resin is preferable because it has excellent heat resistance. Examples of the imide resin include a prepolymer containing bismaleimide and a diamine as polymerization components; a polyfunctional cyanate ester or a prepolymer of a polyfunctional cyanate ester and an amine, and a bismaleimide or a bismaleimide and an amine. A resin composition containing a prepolymer; an imide prepolymer containing a polyfunctional amine, polyanhydride, nadic anhydride, etc. as a polymerization component; a resin composition containing a resin containing bismaleimide and an alkenylphenol as a polymerization component There is.

When a thermosetting resin is used, a net-like structure is formed by baking after applying the undercoat composition, and the adhesion between the resin composition layer to be coated and the metal body is improved. In addition, the adhesive force of the thermosetting resin also improves the adhesiveness between the metal body and the undercoat layer.

The inorganic filler contained in the undercoat composition has a function of preventing peeling or cracking of the undercoat layer formed by the undercoat composition. Examples of such inorganic fillers include metals, metal oxides, glass, carbon, ceramics, and inorganic crystals.

The metal includes aluminum, zinc, nickel alloy, stainless steel, cast iron and the like. As the metal oxide, the glass and the ceramics, any of the same materials that can be contained in the first resin and the second resin can be used. The metal, metal oxide, glass, carbon and ceramics are all preferably in the form of fine powder. The average particle size is adjusted to 1 to 100 μm, preferably 5 to 30 μm.

Such an inorganic filler is a resin 10 used in the undercoat composition.
It is added in an amount of 10 to 800 parts by weight, preferably 25 to 400 parts by weight, based on 0 part by weight. When it is less than 10 parts by weight, the effect of adding the inorganic filler becomes small. If it exceeds 800 parts by weight, the bonding force of the thermosetting resin will be reduced and the adhesion between the resin coating layer and the metal body will be deteriorated.

The inorganic binder contained in the undercoat composition includes lithium polysilicate, amine silicate, alkyl silicate, silicon dioxide colloid and the like.

When a thermal spraying process is performed as a base treatment of a metal body, a metal, ceramics, etc. are used as a thermal spraying material used for this thermal spraying process. Especially the use of metal is the first
It is preferable for improving the adhesion between the resin coating layer and the metal body. Metals used as the thermal spray material include nickel alloy, stainless steel, cast iron, aluminum, zinc and the like. The sprayed layer is formed by arc spraying or plasma spraying.

To produce the coated metal body of the present invention, first, if necessary, the surface (inner surface and / or outer surface) of the metal body to be coated is subjected to suitable pretreatment such as sandblasting, degreasing, chemical conversion treatment, and the like. Processing is performed. When the undercoating treatment is performed as the base treatment, the undercoating composition is applied to the surface of the metal body by dissolving it in an organic solvent such as N-methyl-2pyrrolidone, dimethylformamide or dimethylacetamide, if necessary. Then heated and baked,
An undercoat layer is formed.

The layer thickness of the undercoat layer is 5 to 100 μm, preferably 10 to 30 μm
The range is m. When it is less than 5 μm, the undercoat layer is not uniformly formed, and pinholes and cracks are likely to occur. When it exceeds 100 μm, the adhesion between the undercoat layer and the metal body is deteriorated.

When the thermal spraying treatment is performed as the base treatment, the thermal sprayed layer is formed on the surface of the metal body by, for example, arc spraying or plasma spraying the metal for thermal spraying. The layer thickness of the sprayed layer is adjusted to 20 to 200 μm, preferably 30 to 80 μm.

On the surface of the thus-treated metal body, a polyaryletherketone resin having a repeating unit represented by the above formula [I] and / or the formula [II] and the above formula [II]
A first resin coating layer made of a mixture containing I] or / and the polyarylethersulfone resin represented by the formula [IV] and, if necessary, the inorganic filler is formed. The first resin coating layer is formed, for example, by a powder coating method, by coating the surface of the metal body that has been ground-treated in the powder state and baking the metal body at about 400 ° C., for example.

The layer thickness of the first resin coating layer is preferably 50 to 2000 μm, more preferably 250 to 1000 μm. When it is less than 50 μm, the coating layer is not uniformly formed, and pinholes and cracks are likely to occur. If it exceeds 2000 μm, it takes time for baking and the like, and foaming occurs, so that a dense resin coating layer cannot be obtained.

Thus, on the resin coating layer coated with the first resin,
A second resin coating layer composed of a polyaryletherketone resin having a repeating unit represented by the formula [I] or / and the formula [II] and a resin containing the inorganic filler as necessary is formed. . Similar to the formation of the first resin coating layer, this coating layer is also formed, for example, by applying the powder coating method on the first resin coating layer in a powder state and baking it at about 400 ° C. To be done.

The layer thickness of the second resin coating layer is preferably 50 to 2000 μm and thinner than the layer thickness of the first resin coating layer, and more preferably 100 to 500 μm. When it is less than 50 μm, it becomes difficult to completely cover the first resin coating layer. If it exceeds 2000 μm, the residual stress of the coating layer increases and cracks are likely to occur.

The metal body on which the second resin coating layer is formed is left to cool or rapidly cooled, and then, if necessary, heat-treated at an appropriate temperature. Thus, the resin-coated metal body of the present invention is obtained.

(Function) In the first resin coating layer of the resin coated metal body of the present invention,
The residual stress due to the crystallization of the polyaryletherketone resin is relieved by the polyarylethersulfone resin mixed therein. Further, the water absorption of the polyarylethersulfone resin is improved by the polyaryletherketone resin mixed therein.

Further, the polyaryletherketone resin forming the second resin coating layer has excellent adhesiveness to the first resin layer. Therefore, even if residual stress due to crystallization of the polyaryletherketone resin is generated in the second resin coating layer, it has almost no effect on the adhesion to the metal body, and the polyaryletherketone resin is not affected. The original performance that it has is fully demonstrated.

(Example) Below, the Example and comparative example of this invention are described.

Example 1 (A) Formation of undercoating layer 3,3 ′, 4,4′-benzophenone tetracarboxylic acid anhydride
3.222 g, 3,3'-diaminodiphenylsulfone 3.725 g and 5-norbornene-2,3-dicarboxylic acid anhydride (nadic anhydride) 1.642 g were added to molecular sieve dried N-methyl-2-pyrrolidone 30 g. Dissolved.

This solution was stirred at room temperature for 6 hours and reacted to obtain a thermosetting resin solution containing an imide oligomer. 25.8 g of high silicon cast iron powder (average particle size of 40 μm or less) was added to this solution as an inorganic filler and uniformly mixed to prepare an undercoat composition.

A 100 mm x 100 mm x 3 mm iron plate was grid blasted and then compressed air was blown to clean it. On one side of this iron plate, apply the undercoat composition with a brush and apply 250
It was dried at 30 ° C. for 30 minutes and baked. The thickness of the obtained undercoat layer was 30 μm on average.

(B) Formation of coating layer 80 g of a polyaryletherketone resin (Victrex PEEK 15P / F, manufactured by ICI) finely pulverized by a freeze pulverizer to about 10 to 20 μm and a polyarylethersulfone resin (Victrex PES) similarly finely pulverized 80 g of 5003P, manufactured by ICI) and 40 g of glass powder (diameter about 9 μm, length about 15 to 100 μm) were mixed to prepare a powdery first resin. Further, 80 g of the above polyaryl ether ketone resin and 20 g of the above glass powder were mixed to prepare a powdery second resin.

After baking the undercoated iron plate obtained in (A) above at 400 ° C. for 30 minutes, the first resin is applied to this undercoat layer with a static voltage.
Powder coating was performed at 60 KV in three steps, and the second resin was further powder coated once at a static voltage of 60 KV. Each coating was allowed to flow out at 400 ° C for 5 minutes. The iron plate coated with the first resin and the second resin was put into water and rapidly cooled. This was further heat-treated at 200 ° C. for 1 hour to obtain a resin-coated metal body. The layer thickness of the first resin coating layer of this coated metal body is 350 μm on average, and the layer thickness of the second resin coating layer is 120 μm.
Met.

(C) Performance Evaluation of Coated Metal Body The performance of the coated iron plate obtained in the item (B) was evaluated by the following test method. The results are shown in Table 1.

(1) Hot water test The coated metal body was immersed in hot water at 95 ° C on the coating layer side and 65 ° C on the steel plate side for 100 hours, and then the state of the coating layer was observed.

(2) Hot solvent / hot oil test The coated metal body was put in an autoclave in which two layers of a water layer and a toluene / A heavy oil mixed layer were formed by adding equal amounts of water, toluene and heavy oil A at a volume ratio of 150 ° C. After heating at 100 ° C. for 100 hours, the state of the coating layer was observed.

In the table, the degree of blister is shown as a percentage of the area where blister is generated.

Example 2 Example 1 was repeated except that the first resin was applied twice and the second resin was applied twice. In this case, the average thickness of the first resin coating layer is 240μ
The average thickness of the second resin coating layer was 230 μm.

Example 3 In the preparation of the first resin, 100 g of polyaryl ether ketone resin and 60 g of polyaryl ether sulfone resin were used.
The procedure was the same as in the example except that g was used.

Example 4 5 g of amino bismaleimide resin (Kerimd601, manufactured by Rhone Poulenc) was dissolved in 15 g of N-methyl-2-pyrrolidone, and a high silicon cast iron powder (average particle size of 40 μm or less) was added to this solution.
15 g was added and uniformly mixed to obtain an undercoat composition. The procedure of Example 1 was repeated except that this undercoat composition was used.

Example 5 The procedure of Example 1 was repeated, except that 40 g of glass powder was not mixed in the preparation of the first resin.

Example 6 The procedure of Example 1 was repeated, except that 40 g of the glass powder was mixed with 30 g of carbon fiber powder having a diameter of about 7.5 μm and a length of 20 to 100 μm in the preparation of the first resin.

Example 7 Polyaryletherketone resin (Victrex PEEK) 80 g
Instead, use a polyaryletherketone resin (Victrex PEK, manufactured by ICI) that has been pulverized to about 10 to 20 μm by freeze crushing, and put the iron plate coated with the first resin and the second resin into water. Heat treatment after quenching by
Example 1 was repeated except that the temperature was changed to ° C.

Example 8 Ethyl silicate # 40 (condensate of 5 molecules of ethyl silicate monomer, content calculated as SiO ₂ is 40% by weight) 10
0 parts by weight and 40 parts by weight of ethyl alcohol were placed in a glass reaction vessel, and 1 part by weight of 1N hydrochloric acid and 9 parts by weight of water were continuously added dropwise over 2 hours while mixing and stirring. After completion of dropping, the solution was stirred for 3 hours and then left for 20 hours to obtain an ethyl silicate condensate solution. The ethyl silicate condensate solution contained 50% by weight of the ethyl silicate condensate.

To 15 parts by weight of the obtained ethyl silicate condensate solution, 30 parts by weight of aluminum powder (diameter 40 μm or less) and 5 parts by weight of butyl cellosolve were added and uniformly mixed to obtain an undercoat composition. Example 1 except that this basecoat composition was used
It carried out similarly to.

Example 9 Instead of forming the undercoating layer, SUS306 is sprayed on the plast steel sheet by an arc spraying method to have a thickness of 50 to 60 μm.
The same procedure as in Example 1 was carried out except that a spray-treated layer of SUS306 was formed.

Comparative Example 1 The procedure of Example 1 was repeated except that the polyaryletherketone resin 80 g and the polyarylethersulfone resin 80 g were replaced with only the polyarylethersulfone resin 160 g in the preparation of the first resin. .

Comparative Example 2 Preparation of Example 1 was carried out in the same manner as in Example 1 except that the polyaryl ether ketone resin 80 g and the polyaryl ether sulfone resin 80 g were replaced with only the polyaryl ether ketone resin 160 g. .

Comparative Example 3 Comparative Example 3 was repeated except that the first resin was applied in four times and the second resin was not applied.

Further, in Examples 1 to 9 and Comparative Examples 1 to 3, polyaryl ether sulfone resin (Victrex PES 5003P, I
Example 1 to 9 and Comparative Examples 1 to 1 except that a polyarylethersulfone resin (UDEL P-1800, manufactured by Amoco Performance Products Co., Ltd.) was used instead of CI).
The same procedure as 3 was performed. As a result, the same results as the results corresponding to Table 1 of Examples 1 to 9 and Comparative Examples 1 to 3 were obtained.

(Effects of the Invention) As described above, the resin-coated metal body of the present invention comprises a mixture of a polyaryletherketone resin and a polyarylethersulfone resin on the surface of a metal body that has been undercoated or sprayed. Since the first resin coating layer is formed, the characteristics of both resins are combined, and this resin-coated metal body is unlikely to cause peeling or cracking of the first resin coating layer and cracking of the coating film. It also has excellent resistance to hot water, water vapor, acids and alkalis.

Further, since the second resin coating layer made of polyaryletherketone resin is formed on the first resin coating layer, the second resin coating layer firmly adheres to the first resin coating layer. However, the residual stress caused by the crystallization of the second resin coating layer has almost no effect on the metal body, and the adhesion between the coating layer and the metal body is excellent as a whole, and in addition to hot water, water vapor, acid, alkali, etc. Excellent resistance to organic solvents and oils.

Therefore, such a resin-coated metal body is used in various applications such as hot water, water vapor, acids and alkalis, especially chemical plants in which organic solvents and oil flow at high temperatures, oil well pipes and tank inner wall materials. It is preferably used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C09D 171/08 PLQ 9167-4J 181/06 PML 7308-4J

Claims (1)

[Claims] 1. A polyaryletherketone resin having a repeating unit represented by the following formula [I] or / and a formula [II] and a formula [III] or / And a first resin comprising a mixture with a polyarylethersulfone resin having a repeating unit represented by the formula [IV] is coated thereon, and a repeating resin represented by the following formula [I] or / and [II] A resin-coated metal body, which is coated with a second resin composed of a polyaryletherketone resin having units.