JPS60225749A - Anticorrosive iron plate and manufacture thereof - 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] Concerning boards and their manufacturing methods.

Conventional anti-corrosion iron plates require the surface of the iron plate to be treated with phosphate, then treated with chromic acid, and then coated with synthetic resin paint.

However, drums and oil cans made using anti-corrosive iron plates treated with anti-corrosion treatment have no anti-corrosion effect against surfactant solutions, which have extremely high rust-promoting properties, and will deteriorate within a few days. The present inventors came to the conclusion that phosphate-chromic acid treatment of the iron surface cannot prevent rusting caused by substances with strong rust-promoting properties. Instead of the phosphate-chromic acid treatment, various studies were conducted using a tin plating layer as a rust preventive layer.

Even if this tin plating layer was thick, it was not enough to prevent rust from occurring.

Therefore, various synthetic resin layers were placed on top of the tin plating layer to study the rust prevention properties, but the conventional resin layers that are formed have strong rust-promoting properties such as micationic surfactants. It was not possible to prevent the rusting effect of the substance.

However, when an epoxy resin layer is used as the second layer on the tin plating layer and a vinyl chloride resin layer is placed on top of it, it shows a superior rust prevention effect compared to other resin combinations. I discovered that.

However, these combinations of the resin layer and the tin plating layer did not achieve a sufficiently satisfactory rust prevention effect.

The inventors conducted further research and found that rust could be prevented by heat-treating an iron plate with an epoxy resin layer on top of the tin plating layer and a vinyl chloride resin layer on top. Ta.

According to research conducted by the present inventors, heat treatment causes a partial dechlorination reaction in vinyl chloride resin, resulting in cross-linking between vinyl chloride resins and between vinyl chloride resin and epoxy resin. It is thought that bonding occurs and this is effective in preventing the occurrence of rust.

However, although the rust prevention mechanism has not yet been fully elucidated, the rust prevention layer of the present invention consists of a tin plating layer, an epoxy resin layer, and a heat-treated vinyl chloride resin layer. shows an excellent rust prevention effect that is always reproducible.

And even if any one of these three layers is missing, or the order of the layers is changed, the rust prevention effect will not be exhibited.

5 The thickness of the tin plating layer in the present invention is 2 to 50% in terms of coating amount.
a/rl is appropriate. If it is less than 2 (1/f), there is a high risk of bottle holes occurring, and if it is more than 50 (1/m), the cost will increase and there is no particular benefit.

A preferred range is 5-15111/m''.

Next, the second layer is an epoxy resin layer, and this resin has better adhesion to the tin-plated surface and vinyl chloride resin than any other synthetic resin, which contributes to rust prevention.

As the epoxy resin layer used, epoxy/amino resin or epoxy/phenol resin is particularly preferred.

Epoxy/amino resins are polymer compounds containing two or more epoxy groups in the molecule, synthetic resins produced by ring-opening reactions of the epoxy groups, and resins produced by condensation reactions between compounds containing amino groups and aldehydes. is a crosslinked resin.

Epoxy/phenol resins include polymer compounds containing two or more epoxy groups in the molecule, synthetic resins produced by ring-opening of the epoxy groups, resins obtained from phenols and aldehydes, and modified resins thereof. It is a crosslinked resin.

The appropriate amount of these epoxy resin layers is 1 to 100 g/1 (solid content). If it is less than 1 a/m", the rust prevention property is insufficient, and if it exceeds 100 g/m", the flexibility will be inhibited and cause cracking, leading to deterioration of the rust prevention property.

It is always better to apply multiple times than once.

Next, the third layer is a vinyl chloride resin layer, and when this resin comes into close contact with the coating film of the epoxy resin layer, unlike other resins, this resin has extremely good adhesion and exhibits a rust-preventing effect.

The vinyl chloride resin used is usually one made with a plasticizer or a plasticizer and a diluent added to make it easier to paint.

The appropriate amount of vinyl chloride resin to adhere is 1 to 100 tJ/m" (solid content). If it is less than 1 (1/in), the rust prevention is insufficient, and if it exceeds 100 tJ/m", the adhesion will be poor. becomes defective, leading to a decrease in the rust prevention effect.

Heat treatment is performed after applying vinyl chloride resin.
One of the features of the present invention is that heat treatment is performed at 140 to 250
It is most effective to do it at ℃.

In vinyl chloride resin, a dechlorination reaction occurs at 130 to 160°C, and a crosslinking reaction occurs when the temperature is further raised.

It is thought that this reaction has a large effect on the rust prevention effect.

The rust-proof iron plate obtained in this way has extremely strong rust-proofing performance due to the synergistic effect of the 11th tin plating layer, the 2nd layer of epoxy resin layer, and the 3rd layer of vinyl chloride resin layer and the heat treatment. demonstrate.

The rust-proof iron plate of the present invention is made into a drum, oil color, storage tank, etc., and is suitable for storing rust-prone substances such as surfactant solutions, acid solutions, alkaline solutions, synthetic resin emulsions, or mixtures thereof. . In addition, it is used for transportation equipment and construction equipment.

Next, the present invention will be explained with reference to Examples and Comparative Examples.

Example 1 A tin plating layer with a thickness of 15 M'' was provided as the first layer on a 0.3 mm thick iron plate, and a heat-treated vinyl chloride resin layer with a plating amount of 50 g/uF (solid content) was provided as the second layer. Rust-proof iron plate.

This rust-proof iron plate was manufactured as follows.

A 0.3u thick iron plate is tin plated to a thickness of 15Q/m, then epoxy/amino resin paint is applied to a solid content of 50Q/i, and after drying at room temperature, vinyl chloride resin paint is applied. was applied so that the solid content was 50 g/dry, and after drying at room temperature, heat treatment was performed at 170° C. for 30 minutes to obtain a rust-proof iron plate.

Example 2 In Example 1, the amount of tin plating was 10 g/m, and the amount of epoxy/amino resin was 30 g/m' (solid content).
In addition, the amount of vinyl chloride resin applied was changed to 80 g/m'', and the heat treatment conditions were changed to 200°C x 30 minutes.

The manufacturing method was the same as in Example 1.

Example 3 In Example 1, the second layer was changed to an epoxy/phenol resin layer with a weight of 1800/m2 (solid content), and the amount of vinyl chloride resin in the third layer was changed to 10 g/m2 (solid content). Rust-proof iron plate.

The manufacturing method was the same as in Example 1.

Example 4 In Example 3, the amount of tin plating was changed to 10 g/l [12
and changed the amount of epoxy/phenol resin to 50o/r.
l (solid content), the amount of vinyl chloride resin applied is 80g/f
(solid content) and the heat treatment conditions were changed to 200℃ x 30 minutes.

The manufacturing method was the same as in Example 1.

Example 5 In Example 1, the amount of epoxy/amino resin applied was changed to 3 h/
m” (solid content), add the amount of vinyl chloride resin to 3h/f
(solid content) rust-proof iron plate. The manufacturing method was the same as in Example 1.

Example 6 In Example 4, the amount of epoxy/phenol resin applied was changed to 5
09/♂ (solid content), the amount of vinyl chloride resin applied is 301
Rust-proof iron plate changed to 7/ln”.

The manufacturing method was the same as in Example 1.

Comparative Example 1 A tin plating layer with a coating weight of 5 o/m'' was provided as the first layer on an iron plate with a thickness of 0.311, and a vinyl chloride resin layer with a coating weight of 50 g (solid content) was provided as the second layer. The amount of wear as 3 layers is so
A processed iron plate with an epoxy/amino resin layer of g/m” (solid content).

This processed iron plate was manufactured as follows.

A 0.3 mm thick iron plate was tin plated to a coating weight of 5 g/m, and then vinyl chloride resin paint was applied to the solid plate to give a coating weight of 5 g/m.
After drying at room temperature, an epoxy/amino resin paint was applied to give a solid content of 50 g/m'', and after drying at room temperature, heat treatment was performed at 170° C. for 30 minutes to obtain a processed iron plate.

Comparative Example 2 A tin plating layer with a coating weight of 10 g/m'' was provided as the first layer on an iron plate with a thickness of 0.31, and a vinyl chloride resin layer with a coating weight of 80 o/n? (solid content) was provided as the second layer, 5 pieces as the third layer
Processed iron plate with an epoxy/phenol resin layer of 0a/m" (solid content).

This processed iron plate was manufactured as follows.

Amount of 10g/m on a 0.3mm thick iron plate! Then, apply vinyl chloride resin paint to a solid content of 80A/m, and after drying at room temperature, apply epoxy/phenol resin paint to a solid content of 50Q/f. After drying at room temperature, heat treatment was performed at 200°C for 30 minutes to obtain a processed iron plate.

Comparative Example 3 In Example 2, the amount of epoxy/amino resin applied was changed to 8 h/
Processed iron plate changed to 1 nt and omitted the third layer.

The manufacturing method was the same as in Example 1, and heat treatment was performed after coating the second layer.

Comparative Example 4 In Example 4, the amount of epoxy/phenol resin applied was 80! J/III” and omitted the third layer.

The manufacturing method was the same as in Example 1, and heat treatment was performed after coating the second layer.

Comparative example 5 A processed iron plate in which the second layer was omitted in Example 2.

The manufacturing method was the same as in Example 1, and heat treatment was also performed.

Comparative Example 6 A processed iron plate in which the heat treatment conditions in Example 2 were changed to 100°C x 30 minutes.

The manufacturing method was the same as in Example 1.

Comparative Example 7 A processed iron plate in which the heat treatment conditions in Example 4 were changed to 100°C x 30 minutes.

The manufacturing method was the same as in Example 1.

Comparative Example 8 A processed iron plate made by providing a polyethylene resin layer with a coating weight of 80 g/m on a 0.3 g + - thick iron plate which was tin-plated with a coating weight of 10 g/m.

This processed iron plate was manufactured as follows.

Thickness 0.3g + anti-rust treatment with phosphate-chromic acid
The amount of polyethylene resin applied to the iron plate of S is 800/ solid content.
A processed iron plate was obtained by melt-coating to a thickness of

Comparative Example 9 In place of the polyethylene resin layer in Comparative Example 8, a coating weight of 8
Processed iron plate with a polypyrene resin layer of 0 o/m" (solid content).

The manufacturing method followed Comparative Example 8.

Comparative Example 10 A processed iron plate in which the epoxy/phenol resin layer in Example 4 was replaced with a polyester resin layer with a coverage of 8 h/m''.

The manufacturing method was based on Example 4.

Comparative Example 11 A processed iron plate in which the tin-plated iron plate in Example 1 was replaced with a 0.3 mm thick iron plate treated with phosphate-chromic acid.

This processed iron plate was manufactured as follows. - Phosphate - A 0.31 thick iron plate treated with anti-corrosion treatment with chromic acid.
Apply epoxy/amino resin paint to a solid content of 80 o/m" and dry at room temperature. Apply vinyl chloride resin paint to a solid content of SOQ/d. After drying at room temperature,
A processed iron plate was obtained by heat treatment at 0°C for 30 minutes.

Comparative Example 12 A processed iron plate in which the epoxy/amino resin layer in Comparative Example 11 was replaced with an epoxy/phenol resin layer with a coverage of 8047/m'' (solid content).

The manufacturing method followed Comparative Example 11.

A container with a capacity of about 1 liter was made using the rust-proof iron plate of the comparative test example and the processed iron plate of the comparative example, and about 8 liters of the chemicals shown in Table 1 were added to the container.
The tubes were filled to the brim and left in a constant temperature room for 21 days at 55°C±1°C. However, the acetone temperature was set at 35°C ± 1°C for 21 days.

The rust prevention performance was determined by examining the occurrence of rust at the boundary between the liquid phase and the gas phase and the state of the coating film.

◎: No rusting at all, no blistering of the coating film I/1°O: Blistering occurs in the coating film.

△: Slight rusting occurs.

X: Significant rusting occurs.

The results are shown in Table 1.

Comparative Examples 1 and 2 are the second
Although the coating order of the third layer and the third layer were changed, the rust prevention performance of both examples was inferior to that of the corresponding example.

Comparative Examples 3, 4 and 5 are in Example 2 or 4,
Either the third layer or the second layer was omitted and the amount of synthetic resin was adjusted to 80 g/]Tl2 (solid content), but both had poor rust prevention performance.

Comparative Examples 6 and 7 are obtained by changing the heat treatment conditions to 100° C. for 30 minutes in Examples 2 and 4, but both have inferior rust prevention performance to the corresponding Examples.

In Comparative Examples 8 and 9, tin-plated iron plates were coated with a resin different from the resin used in the second or third layer of the present invention, but both had poor rust prevention performance.

Comparative Example 10 is the same as Example 4 except that the second layer is made of polyester resin, but the rust prevention performance is poor.

In Comparative Examples 11 and 12, a conventional phosphate-chromic acid treated iron plate was used in place of the tin-plated iron plate in Examples 1 and 3, but both had poor rust prevention performance.

Patent applicant: Hoechst Synthesis Co., Ltd.
i'M♂police;? iT4 jl, irl-station (own)-
and) 1. Indication of matter f1 1982 Special Application No. 82552 2. Name of the invention Rust-preventing ridge grade and - Relationship with the old case involving the manufacturing method 3. Amendment 1. Patent 4 Applicant 5 Supplement 11: Target m Akira 7. i 0) I' fl Ilj! 7)
汀m'J iJ2 明J (7) Contents of III6 amendment (1) Details: IVB, rJ 151j "(solid content)
1-(solid content) of 1 bottle/amino resin layer was set up, and the amount of 50 CI/TIL (solid content) was applied between the 3rd F4.
Correct it.

(21rial, page 13, lines 8-9 [phosphoric acid...
...on an iron plate [thickness 0.3. 4 pieces of 10g/
Tin plating is applied so that it becomes the butt, and then the r J is corrected.

Below 1-

Claims (1)

[Scope of Claims] 1. A rust-preventing iron plate in which a rust-preventing layer is provided on an iron plate, the first layer being a tin plating layer, the second layer being an epoxy resin layer, and the third layer being a heat-treated vinyl chloride resin layer. -2 The amount of tin plating is 2 to 50 g/m", the amount of epoxy resin layer is 1 to 100 Mm" (solid content), and the amount of heat-treated vinyl chloride resin layer is 1 to 100 M
m" (solid content) of the rust-proofing iron plate according to claim 1. 3. The rust-proofing iron plate according to claim 1 or 2, wherein the epoxy resin layer is an epoxy/amino resin layer. 4. The rust-proof iron plate according to claim 1 or 2, wherein the epoxy resin layer is an epoxy/phenol resin layer. 5. The iron plate is tin-plated on one or both sides, and the epoxy resin is applied to the surface. A method for producing a rust-proof iron plate characterized by applying a hardening vinyl chloride resin and heat-treating the plate.6 The amount of tin plating is 2 to 50 tJ/lo'', and the amount of epoxy resin is 1 ~100 (]/m" (solid content), and the amount of vinyl chloride resin layer applied is 1 to 100 g/m
' (solid content). 7. The method for producing a rust-proof iron plate according to claim 5 or 6, wherein the epoxy resin is an epoxy/amino resin. 8. The method for producing a rust-proof iron plate according to claim 5 or 6, wherein the epoxy resin is an epoxy/phenol resin. 9. The method for manufacturing a rust-proof iron plate according to claim 5, 6, 7, or 8, wherein the temperature at which the vinyl chloride resin is applied and heat treated is 140 to 250°C.