JPH03168259A - Metal substrate coated with polyetheramideimide resin and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title metal substrate useful for electrical and electronic components, kitchen equipments, etc., and having excellent deterioration resistance, etc., by dissolving a specific polyetheramideimide resin in an organic solvent and applying the solution to the surface of metal substrate and baking the coating film. CONSTITUTION:Trimellitic acid or reactive acid derivative thereof (preferably trimellitic anhydride) is reacted with 4,4'-diaminodiphenyl ether or 4,4'- diisocyanatediphenyl ether to afford a polyetheramideimide resin having >=26000 number-average molecular weight and a solution obtained by dissolving the resultant resin in an organic solvent such as N-methylpyrrolidone and further adding fluorine resin, etc., having 0.1-10mum grain size thereto is applied to the surface of metal substrate (e.g. aluminum substrate) and preliminarily dried at 80-150 deg.C and then baked at 200-400 deg.C to provide the aimed metal substrate having 0.1-100mum dried film thickness.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a metal substrate coated with a Bolier,-Telua ξ dimide resin and a method for producing the same.

[Conventional technology]

BACKGROUND ART Conventionally, as heat-resistant paints and heat-resistant adhesives for various metal substrates, polyide-based resins with excellent heat resistance, such as boria-ξ-dimide resins, polyimide resins, and boria-ξ-nobismaleimide resins, have been used. Among them, polyamide-imide resin has an excellent balance of heat resistance, adhesion to substrates, solvent solubility, and price, and is highly evaluated as a heat-resistant material.

[Problem to be solved by the invention]

On the other hand, in recent years, general industrial machinery parts, electric/electronic parts,
Release molds and the like are increasingly used in high-temperature atmospheres for long periods of time, and along with this, the heat resistance required of heat-resistant resin-coated metal substrates is also becoming more sophisticated. In particular, deterioration resistance (adhesion after heat treatment) is an indicator of heat resistance.
The heat treatment temperatures required are also increasing. However, conventional polyamide-imide resin-coated metal substrates have been useful materials for applications requiring moderate deterioration resistance at heat treatment temperatures of around 200°C, but at high heat treatment temperatures of around 300°C. There was a problem that it could not be applied to applications that required high deterioration resistance.

It is an object of the present invention to solve the problems of the prior art described above, and to provide a metal substrate coated with a polyester ago doimide resin which has particularly excellent resistance to deterioration, and a method for producing the same.

[Means to solve the problem]

The present invention provides trimellitic acid or its reactive acid derivatives and 4
, 4'-diaminodiphenyl ether or 4,4'-diisocyanate diphenyl ether, the number average molecular weight (determined by gel permeation chromatography using boristyrene of known molecular weight as a calibration curve) is 26,000. The present invention relates to a metal substrate coated with a polyether amide-imide resin, which is obtained by applying and baking a solution of the polyether amide-imide resin dissolved in an organic solvent onto the surface of the metal substrate, and a method for producing the same.

Examples of the reactive acid derivative of trimellitic acid in the present invention include trimellitic anhydride, trimellitic anhydride monochloride, 1. 4-dicarboxy-3-
N,N-dimethylrubamoylbenzene, 1 4-dicarboxy-3-carbophenoxybenzene, 1.4-
Ammonium salts such as dicarbomethoxy-3-carboxybenzene, trimellitic acid and ammonia, dimethylamine, triethylamine, etc. are used. Particularly preferred are trimellitic anhydride and trimellitic anhydride monochloride.

To produce the polyetheramide ξ-do resin of the present invention, trimellitic acid or its reactive acid derivative and 4.4'-
Diaminodiphenyl ether or 4,4'-diisocyanate diphenyl ether is preferably used in approximately equimolar amounts for the reaction. This reaction can be carried out using a solution polymerization method (for example, Japanese Patent Publication No. 44-19274, Japanese Patent Publication No. 49-40
Publication No. 77, Japanese Patent Publication No. 15637/1977, Japanese Patent Application Publication No. 1977
7-14622), precipitation polymerization method (for example, Japanese Patent Publication No. 54-44719), non-aqueous dispersion polymerization method (for example,
USP 4,427.822), melt polymerization method (Special Publication No. 40
It can be obtained by condensation polymerization using a known production method such as JP-A-8910). In consideration of cost, a solution polymerization method in which trimellitic anhydride and 4,4'-diaminodiphenyl ether are condensed and polymerized in the presence of a dehydration catalyst such as phosphoric acid is preferred.

The polyetheramide-imide resin of the present invention is, for example, a resin containing a bond structure such as the following general formula (1), (II), or (III).

(1) In formula C, R represents 10-0 similar zeta].

As the polyether adimide resin in the present invention, one having a number average molecular weight of 26,000 or more is used. 2
If it is less than 6,000, the deterioration resistance is poor. Particularly preferably,
It is in the range of 30,000 to 70,000. 7
When it exceeds 0.0 0 0, the viscosity of the solution increases, making handling and coating operations difficult.

In this specification, the number average molecular weight is determined by Gelper 5 Acidine chromatography using boristyrene of known molecular weight as a calibration curve. Specifically, the measurement was performed under the following conditions.

Equipment: Hitachi 655A column: Gelpak GL-S manufactured by Hitachi Chemical Co., Ltd.
300MDT-S (300mmX 8+n
+++φ) 2 eluents: Tetrahydrofuran/dimethylformamide = 1/1 (volume), H3PO4 (0.06 mol/l)/L i B
r-HzO (0.03 mol/E) Flow rate: 1 relative/min Detector: UV (270 nm) The polyether a≧dimide resin of the present invention is applied to the surface of a metal substrate as a solution dissolved in an organic solvent. Here, the organic solvents include N-methylpyrrolidone, dimethylformamide, dimethylacetate, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3.4,
It is preferable to use a nitrogen-containing polar solvent such as 5.6-tetrahydro-2(IH)-pyrimidinone.

As described above, in the present invention, a solution in which the polyether ξ dimide resin of the present invention is dissolved in an organic solvent is applied to a metal substrate. The amide-imide resin solution may be used as it is, or a solution obtained by dissolving a solid polyether amide-imide resin substantially free of a solvent in the above-mentioned organic solvent may be used.

In the present invention, the following substances are added to the polyether amide resin solution as necessary, preferably at 0.000% relative to the polyether amide resin in the solution. It can be used in a range of 1 to 200% by weight.

One or more of these substances may be used. Specifically, for example, metals, metal oxides, metal nitrides, metal carbides, metal silicides, boron, boron oxides, boron nitrides, silicon, silicon oxides, silicon nitrides, silicon carbides, etc. Modification of fine particles, silane coupling agents such as γ-aminoprobyltriethoxysilane and glycidoxybrobyltriethoxysilane, melamine resins, phenol resins, epoxy resins, borissulfone resins, polyethersulfone resins, fluorine resins, etc. materials, organic, inorganic or extender pigments such as red iron, titanium dioxide, carbon black, barium sulfate, mica, talc, yellow lead, cyanine blue, dispersants such as surfactants, leveling agents, anti-settling agents,
Antioxidants, ultraviolet absorbers, etc. are used. In particular, non-adhesion and abrasion resistance can be imparted by using a fluororesin powder or aqueous dispersion having an average particle size of 0.1 to 10 μm. Examples of the fluororesin include polytetrafluoroethylene, a copolymer of tetrafluoroethylene and a fluorine-containing monoethylenically unsaturated monomer other than tetrafluoroethylene, and the like.

Examples of metal base materials used in the present invention include pure iron, steel and carbon, silicon, tungsten, nickel, chromium, manganese, iron base materials such as alloys of molybdenum and iron, argonium and steel, magnesium, manganese, etc. , silicon, zinc,
Aluminum base materials such as alloys of chromium and aluminum,
Copper-based materials such as steel and brass, nickel-based materials, molybdenum-based materials, tungsten-based materials, and various plated products of these materials such as zinc, chromium, aluminum, copper, and nickel, chromic acid-based materials,
It is preferable to use a surface-treated product with a phosphoric acid-based chemical coating or an anodic oxide coating, a surface-polished product, or the like.

Aluminum base materials and iron base materials are preferably used. In particular, it is preferable to use an iron base material, which is superior in terms of cost.

The polyetheramide-imide resin-coated metal base material of the present invention is obtained by applying the above-mentioned polyetheramide-imide resin solution onto the surface of the metal base material and baking it. As the coating method, commonly used methods such as brush coating, spray coating, dip coating, roller coating, and electrodeposition coating are used.

As for the baking method, after pre-drying at 80-150'C, drying at 200-1500 C in air atmosphere or non-oxygen atmosphere.
A method of baking at 400"C for a desired time is preferable. Baking in a non-oxygen atmosphere suppresses thermal oxidative deterioration of polyethera≧dimide resin and improves heat resistance, adhesion, and mechanical strength. Metal substrate surface The dry film thickness of the polyether amide ξ-dos resin solution to be applied and baked can be arbitrarily adjusted depending on the purpose, but is usually preferably in the range of 0.1 to 100 μm.

〔Example〕

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Example 1 (1) Preparation of polyetheramide-imide resin solution-l Removal Mol trimellitic acid chloride 128.1 0.608
4 4'-Zia Dannojife 121.8 0.608
Nyl ether triethylane 123.1 1.21
6N-methylpyrrolidone 7 5 0. 0 trimellitic acid chloride (hereinafter abbreviated as TMA-CL)
and the above ingredients except triethylamine were placed in a four-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, and moisture meter, and kept at -5°C while stirring in a nitrogen stream.4.4' -Diaminodiphenyl ether (hereinafter referred to as D
After completely dissolving TMA-CL (abbreviated as DE), TMA-CL was added and completely dissolved. Triethylamine was added dropwise to this. The temperature within the reaction system rose to about 25°C.

Then, the temperature was raised to 30°C, and the reaction was continued at the same temperature for 5 hours. To this, 310 g of acetic anhydride and 155 g of pyridine were added while stirring, and the mixture was left at room temperature for 24 hours. The obtained solution was diluted with dimethylformamide to a resin concentration of about 8% by weight, and the solution was poured into methanol, and the precipitated solid resin in the form of fine particles was recovered. This solid resin was sufficiently boiled and washed with water and methanol, and then dried under reduced pressure at 80°C for 10 hours to obtain a powdered polyetheramide-imide resin.

The number average molecular weight of this polyetheramideimide resin is
46,000, and the infrared absorption spectrum has 1780
Characteristic absorptions of an imide group at cm-' and a 75-do group at 1660 cm-' were clearly observed.

20g of this powdered polyetheramideimide resin was
Dissolved in 80g of methylpyrrolidone to give a resin concentration of 20% by weight.
A polyether amide-imide resin solution was obtained.

(2) Preparation of polyether a5-dimide resin-coated iron base material Polished with JIS R6252 (abrasive paper) #240 to have a surface roughness (Ra) of 0. The polyether adimide resin solution of (1) above was applied to the polished surface of a 4-0.5 μm carbon fjI steel material for mechanical structures (JIS G4051, S10C, dimensions: 50 x 150 x 1.6 area) to a dry film thickness of about 30 μm.
Coat to a thickness of μm and heat at 80°C for 1 hour at 250°C.
The product was baked at 380° C. for 0.5 hours and 15 minutes at 380° C. to obtain a polyetheramide-imide resin-coated iron base material.

Comparative Example 1 (1) Preparation of polyetheramide imide citrus solution DDE 1 2 1.8 g (0.6 0
The reaction was carried out in exactly the same manner as in (1) of Example 1, except that 120.5 g (0.608 mol) of 4.4'-diaξnodiphenylmethane (hereinafter abbreviated as DAM) was used. A powdered polyamide-imide resin was obtained. The number average molecular weight of this boria cumulative ξ-do resin was 34,000, and in the infrared absorption spectrum, absorption of an imide group at 1780 cm-' and absorption of an amide group at 1660 cm-' were clearly observed.

20 g of this powdered polyamide-imide resin was dissolved in 80 g of N-methylpyrrolidone to obtain a polyamide-imide resin solution having a resin concentration of 20% by weight.

(2) Preparation of polyamide-imide resin-coated iron base material (2) of Example 1 except that the resin solution was that of Kaminagi (1).
The same procedure as above was carried out to obtain a polyamide-imide resin-coated iron base material.

Comparative Example 2 (1) Preparation of polyamide-imide resin solution Example 1 (1)
) of DDE 1 2 1.8 g (0.6 0 8 mol) was mixed with 249.6 g of 2.2-bis[(4-anophenoxy)phenyl]propane (hereinafter abbreviated as BAPP).
(1) of Example 1 except that it was changed to (0.608 mol)
The reaction was carried out in exactly the same manner as above to obtain a powdered polyamideimide resin. The number average molecular weight of this polyamide ξ-do resin is 36,000, and the infrared absorption spectrum shows 17
Significant absorption of an imide group at 80c+r' and an amide group at 1660Cll-' were observed.

20 g of this powdered polyamide-imide resin was dissolved in 80 g of N-methylpyrrolidone to obtain a polyamide-imide resin solution with a resin concentration of 20% by weight. (2) Preparation of polyamide-imide resin-coated iron base material A polyamide-imide resin-coated iron base material was prepared in the same manner as in (2) of Example I except that the resin solution in (1) above was used. Obtained.

Examples 2 and 3 and Comparative Examples 3 and 4 (1) Preparation of polyether agodoimide resin solution
-L±5 Mol trimellitic anhydride 261.1 1.359
(hereinafter abbreviated as TMA) DDE 269.5 1.34
6 phosphoric acid aqueous solution 9.4 0.080
7 (phosphoric acid content 85%) 1.3-dimethyl-2- 2160.0 imidazolidinone Stir the above ingredients in a four-lobe flask equipped with a thermometer, stirrer, nitrogen inlet tube and moisture meter. The temperature was raised to 160°C while passing nitrogen gas. The temperature was gradually raised to 215°C without removing distilled water from the system, and the reaction was continued at the same temperature. The reaction end point is controlled by the number average molecular weight, and the number average molecular weight is 21000, 25000, 3
Four types of polyether axidimide resin solutions of 0,000 and 36,000 were obtained. In addition, the infrared absorption spectrum of the powdered polyether amide imide resin from which the solvent has been removed shows that the 166
Absorption of amide groups was observed at 0 cm=.

(2) Preparation of iron base material coated with polyetheramide-imide resin. Four types of polyether amide resin-coated iron substrates shown in Table 1 were obtained.

Table 1 Example 4 (1) Preparation of polyether aqueous diimide resin solution - 1 mol TM. A 261.1 1.3
59DDE Triphenyl phosphite 8.8 0.0284
N-Methylpyrrolidone 2160.0 Put the above ingredients into a four-bottle flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a moisture meter while stirring, and raise the temperature to 160'C while passing nitrogen gas. did. Gradually raise the temperature,
The temperature was raised to 200° C. while removing distilled water from the system, and the reaction proceeded at the same temperature. The number average molecular weight was measured, and when the number average molecular weight reached tsooo, the temperature was lowered to 185°C, and 10% by weight of triphenyl phosphite prepared in advance was added.
N-methylpyrrolidone solution 2 6 4. 4g to 1.
The reaction was carried out by adding the mixture in 6 portions at 5 hour intervals. The reaction was stopped when the number average molecular weight reached 30,000, and a polyetheramide ξ-dos resin solution was obtained. In the infrared absorption spectrum of the powdered polyether amide imide resin obtained by removing the solvent from this solution, absorption of an imide group at 1780 CI-' and an absorption of an amide group at 1660 CI-' were observed.

(2) Preparation of polyetheramide-imide resin-coated iron base material Example 1 except that the resin solution in (1) above was used.
The same procedure as in (2) above was carried out to obtain a polyether-imide resin-coated iron base material.

Comparative Example 5 Torlon 4000T (trade name manufactured by Amoco, polyether amide ξ-do resin with a number average molecular weight of 24000) 25 g
It was dissolved in 75 g of @N-methylpyrrolidone to obtain a polyether axidimide resin solution. Using this resin solution, the same procedure as in Example 1 (2) was carried out to obtain a polyetheramide-imide resin-coated iron base material.

Example 5 Surface roughness (Ra) polished with JIS R6252 (abrasive paper) #240 was 0.4 to 0. 5μm aluminum plate (JIS H4000, A1050P, dimensions:
The polyetheramide-imide resin solution of (1) in Example 1 was applied to the polished surface of a 50X1 50X1.6 mm so that the dry film thickness was about 30 μm, and the mixture was heated at 80°C for 1 hour and at 250°C for 0. ．． After baking for 5 hours and 15 minutes at 380''C, a polyetheramide-imide resin-coated aluminum substrate was obtained.

Comparative Example 6 Except for using the resin solution of Comparative Example 1 (1) as the resin solution,
In exactly the same manner as in Example 5, a polyamide-imide resin-coated aluminum base material was obtained.

The resin-coated iron base materials and resin-coated aluminum base materials obtained in Examples 1 to 5 and Comparative Examples 1 to 6 were evaluated for heat loss of the coating resin and adhesion and deterioration resistance of the resin coated base materials. The results are summarized in Table 2.

The heating loss is approximately 30μ when the resin solution is dried on a glass plate.
250″C for 1 hour at 80°C.
So 0. The film obtained by baking at 380°C for 15 minutes for 5 hours was measured using a high-temperature differential thermogravimetric simultaneous measurement device TG/DTA320 manufactured by Seiko Electronics Co., Ltd.
, measured in atmospheric air.

Adhesion was determined using the square test method, JIS D202.
0. Reaching the iron substrate with a single-edged razor
100 mm saws (IOXIO) were prepared and evaluated based on the percentage of remaining squares that were not completely peeled off after a peel test using cellophane adhesive tape.

Deterioration resistance was evaluated by adhesion after heat treating the resin-coated base material at 300"C.Adhesion was the same as the above method [Effects of the invention] As is clear from the above results, the present invention is effective. Polyetheramide-imide resin-coated metal substrates are coated with high-molecular-weight polyetheramide-imide resins having a specific diamine skeleton or other resins. It has significantly superior deterioration resistance compared to the comparative polyamide-imide resin-coated metal base material in which the metal base material is coated with a polyamide-imide resin having a diamine skeleton. It has a wide range of uses, including molds for molds and kitchen utensils.

Claims (1)

[Claims] 1. trimellitic acid or its reactive acid derivative and 4,4'
- obtained by reacting with diaminodiphenyl ether or 4,4'-diisocyanate diphenyl ether,
A metal substrate coated with a polyetheramide-imide resin, which is obtained by applying a solution of a polyetheramide-imide resin having a number average molecular weight of 26,000 or more dissolved in an organic solvent to the surface of the metal substrate and baking it. 2. The polyetheramide-imide resin-coated metal base material according to claim 2, wherein the metal base material is an aluminum base material or an iron base material. 3. A method for producing a polyetheramide-imide resin-coated metal substrate, which comprises coating and baking the solution according to claim 1 on the surface of the metal substrate.