JPS59145076A - Steel sheet excellent in rust-preventing property and direct coatability - Google Patents

Abstract

PURPOSE:To obtain a steel sheet useful as a canning material or the like excellent in a rust-preventing property and direct coatability, which can be used for both temper rolling and two-pass cold rolling, by coating said steel sheet with the proper amount of the oily composition consisting of specified substance permitted under FDA. CONSTITUTION:Among substances permitted as the components of an oily composition under FDA, 10-60wt% a proper one or more of petroleum wax, synthetic wax and lanoline regulated under Paragraph No. 178-3910 of FDA, 5- 40wt% a fatty acid under the same No., 5-30wt% triethanolamine under the same No. and 10-40wt% a mineral oil under the same No. are prepared. In addition, 1-20wt% polyethylene glycol monostearate as a nonionic surfactant or a nonionic surfactant regulated under Paragraph No. 178-3400 of FDA is properly added. An oily composition obtd. by mixing these substances with an aqueous medium and emulsifying them is applied onto a steel sheet by a proper means such as temper rolling or coating.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a steel plate with excellent rust prevention properties and direct paintability.

In the United States, the packaging materials used to package food and drink materials are the Food and Drug Administration.
It must pass the strict standards of FDA (hereinafter abbreviated as FDA). The same applies to steel sheets used as materials for cans, and it goes without saying that care must also be taken regarding the composition of oil used for temper rolling of copper strips. Conventionally, many oil compositions have been known for use in skin pass rolling of steel plates, etc., as described below, but these are mixed with water to emulsify and used at a relatively low concentration. In addition, these do not satisfy rust prevention and direct paintability,
It also did not allow temper rolling or cold rolling twice. Typical conventional examples will be described below.

(1) Temper rolling with conventional oil Conventional oils include sodium nitrite, sodium molybdate,
Water-soluble inorganic temper rolling oils containing boric acid and the like and alkanolamines and water-soluble organic temper rolling oils containing pt-butylbenzoic acid, adipic acid, sebacic acid, etc. and alkanolamines have been used. However, conventional temper rolling oils have poor long-term rust prevention properties and are not approved by the FDA, which poses problems especially when used in the United States. Here, temper rolling refers to rolling performed at a reduction rate of several percent, and double cold rolling, which will be described next, refers to rolling performed at a reduction rate of more than ten percent, and conventional oil can be used for both of these purposes. There was no.

(2) Double cold rolling with conventional oil Conventional oils include natural oils such as beef tallow, palm oil, and lard oil, or synthetic esters and mineral oils with various additives and emulsifiers added.
roll ) oils and QAR (Qualityas)
rolled) has been used as an oil. However, conventional rolling oils have poor long-term rust prevention properties, and direct coating is not possible. In addition, QAR oil has a composition of F.
Although a material approved by the DA was used, the emulsion particles were large and the amount of adhesion was large, making it impossible to obtain a steel plate that satisfied the FDA's quantitative regulations.

(3) Dry skin pass rolling This is done by dry skin pass rolling (no oil), followed by temper rolling and then applying anti-corrosion oil approved by the FDA (for example, Di0ethyl 5ebacate, hereinafter DO8) during shearing.
It is abbreviated as T)K coating. This method has the problem that rust prevention and paintability are not compatible, and the workability is poor because the application is performed using separate equipment. In addition, as shown in Table 1, if the amount of oil applied is large ((100 g/, 1?), the rust resistance will be excellent, but the paintability will be poor, so the amount of oil applied will be reduced (20 g/W?) Although the paintability improved if it was used, the rust resistance was poor.
Conventionally, the amount of oil applied was 100m9/fr? In many cases, the user had to clean the product.

All of the conventional typical methods mentioned above have problems, and there is no composition oil that can be used for temper rolling etc. that satisfies all the characteristics such as rust resistance, direct paintability, and workability. .

The present invention was developed to solve all of the above-mentioned problems, and has excellent rust prevention properties and coating properties that could not be obtained with conventional oil-treated skin-rolled materials or materials coated with rust-preventive oil after dry skin pass. The object of the present invention is to provide a steel plate coated with an appropriate amount of a composition oil composed of FDA-approved substances.

Another object of the present invention is to provide a coating with a composition oil that can be used for both temper rolling and cold rolling, and that can keep the coating amount within the FDA-approved range. We are currently trying to provide steel sheets that have been improved.

The present inventors selected a suitable number of substances suitable for the above characteristics from among the substances approved by the FDA as components of the composition oil for each FDA paragraph A, and variously changed the composition of the selected substances. As a result of the experiment, (a) FDA (Foo
d and Drug Administration
(abbreviation) 10-60% by weight of petroleum waxes and/or synthetic waxes and/or lanolin as specified in Paragraph 4178-3910; (b) 5-40% by weight of fatty acids as specified in FDA Paragraph A178-3910fC; (c) 5-30% by weight of triethanolamine as specified in FDA paragraph 4178-3910, (d)
10 to 40% by weight of mineral oil as specified in FDA paragraph 4178-3910; (e) nonionic active agent polyethylene glycol monostearate and or FDA paragraph 41;
1 to 2 nonionic active agents specified in 78-3400
It has been discovered that the above object can be achieved by using a composition oil that can be dispersed and emulsified in an aqueous medium containing 0% by weight, and coating the steel plate with the oil by appropriate means such as temper rolling or coating, and has developed the present invention. reached.

Next, each component of the composition oil of the present invention and its appropriate range will be explained.

Waxes specified in FDA Paragraph A178-3910 include petroleum waxes such as paraffin wax, synthetic waxes such as stearic acid amide, palmitic acid amide, oleic acid amide, etc., and natural wax lanolin, etc., and their appropriate content is It is 10 to 60% by weight. If this wax is less than 10% by weight, the desired antirust ability cannot be obtained, and if it exceeds 60% by weight, the emulsifying property becomes poor.

Fatty acids defined in FDA paragraph 4178-3910 include monocarboxylic acids such as stearic acid, palmitic acid, lauric acid, and oleic acid, which are derived from animal and vegetable oils, and dimer acids and trimer acids, and their appropriate content is 5 to 40% heavy view. If this fatty acid is less than 5% by weight, the specified antirust ability cannot be obtained, and if it exceeds 40% by weight, the emulsifying property becomes poor (and deterioration occurs when stored for a long period of time, and direct paintability cannot be obtained).

The amine specified in FDA Paragraph 178-3910 includes triethanolamine, the suitable content of which is 5-30% by weight. This triethanolamine is
If it is less than 5% by weight, the desired antirust ability cannot be obtained, and if it exceeds 30% by weight, emulsifying properties become poor and direct coating properties cannot be obtained.

Mineral oils specified in FDA Paragraph A178-3910 include white mineral oil, industrial white mineral oil, etc., and the appropriate content thereof is 10 to 40% by weight. If this mineral oil is less than 10% by weight, it is difficult to adjust the friction coefficient during temper rolling and the desired rolling properties cannot be obtained, and if it exceeds 40% by weight, the desired antirust ability cannot be obtained.

Usable nonionic surfactants as specified in FDA Paragraph/I & 178-3400 include sorbitan monolaurate, sorbitan monooleate, sorbitan monopalmitate, sorbitan monostearate, sorbitan triolate, sorbitan tristearate, Polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, polyoxyethylene (20) There are sorbitan triolate, etc., and the above-mentioned FDA paragraph A17
Although not specified in 8-3400, polyethylene glycol (400) is an FDA-approved nonionic active agent.
There are monostearates, and the appropriate content of these nonionic active agents is 1 to 20% by weight. If the nonionic surfactant is less than 1% by weight, emulsifying properties cannot be obtained, and if it exceeds 20% by weight, the antirust ability will decrease.

These substances are used as a diluted liquid (composition oil) by dispersing and emulsifying them in an aqueous medium. The degree of dilution is appropriately selected depending on the amount of coating, coating method, etc.

The aqueous medium may be general water, but in order to obtain long-term stability, alcohols such as t-butyl alcohol, ingropyl alcohol, fatty alcohols, synthetic primary alcohols, dipropylene glycol, etc. are used.

Glycols such as triethylene glycol and polyethylene glycol can also be used by adding about 0.1 to 10% by weight to water, and have almost the same effect as water alone. If the amount of alcohol and/or glycol added is out of the above range, it will adversely affect the dispersion and emulsification properties.

It is convenient to add a predetermined amount of an emulsion stabilizer such as a water-soluble polymer such as polyvinyl alcohol or a soap such as an aliphatic soda salt or potassium salt to such a composition oil. Furthermore, in order to improve rust prevention properties, aluminum salts, magnesium salts, potassium salts, soda salts, and zinc salts of fatty acids can be added, and depending on the type of water used, soda salts of EDTA are also effective. Further, antioxidants such as t-butylnohydroquinone (TBI(Q), 2,4.5-)lyhydroxybutylophenone (THBP) are also effective in preventing oxidative deterioration of the coating film.

-Next, the rust prevention properties, paintability, etc. of the composition oil used for temper rolling etc. of the present invention having the following composition made of FDA approved substances will be explained in detail.

Application methods include using it as rolling oil during temper rolling or double cold rolling, spraying or roll coater.
There are methods such as applying it, but the effect is the same. However, when used as rolling oil for temper rolling etc.
With the above composition, it is difficult to coat more than 30 kg/d, and when it is desired to increase the coating amount, a method using a roll coater is preferred.

[Rust prevention]

The composition oil coating material of the present invention having the above composition (the material is a material equivalent to SPB-T3 of 0.21 m) and the static coating material of DO8 (dioctyl sebacate), which is known as a rust preventive oil for tin plate, as a comparative material. Electric oil material (Material is 0.21 pus SPB)
-T3 equivalent material) was subjected to a rust resistance test (wet test and packaging test) under the following conditions. The evaluation was performed on a 6-level scale based on the rust occurrence area ratio (%) as shown below.

Rating 50 4 0~0.5 3 0.5~5.0 2 5.0~20,0 1 20.0~50.0 o so, o~100 (1) Humidity test temperature 49±1℃, relative A 24-time rusting test was conducted in a constant temperature and humidity chamber with a humidity of 98% or higher, with the test piece suspended in the chamber and rotated. The results are shown in Figure 1. From FIG. 1, it can be seen that the composition oil coating material of the present invention (marked with ・) has excellent rust resistance even in a small amount, compared to the unoiled original plate (marked with x) and the coated material with DO8 (marked with ○). Recognize.

(2) Packing test In a constant temperature and humidity chamber with a temperature of 38 ± 1℃ and a relative humidity of 85% or more, stack 10 or more test pieces, seal about 10 edges with adhesive tape, and conduct a rusting test for 7 days. I did it. The results are shown in FIG. From Figure 2, the original plate (x mark) and DO
8 coating material (marked with ○), the composition oil coating material of the present invention (・
) shows that it has excellent rust resistance with a small amount of coating.

[Paintability]

It is known that paintability, that is, paint repellency and paint adhesion, deteriorate when the amount of oil on the plate surface increases or when it is unevenly distributed. It is well known that when applying DO8 oil, in particular, when a large amount of oil is applied for the purpose of achieving the rust prevention effect mentioned above, the paint is locally repelled and defects called eye holes occur. There is.

A paint repellency test (eyehole generation test) was conducted on the DO8 coating material and the composition oil coating material of the present invention using an epoxyphenol paint. The results are shown in FIG.

From Fig. 3, eyeholes occur with the DO8 coating material when the amount of oil applied is large, but with the composition oil coating material of the present invention, even when the amount of oil applied is considerably large (one-sided xooq/m"). It can be seen that there are almost no eye holes.

The evaluation method for the occurrence of eyeholes is as follows: 1 Rating: 4 Very good, no eyeholes 3 Good, almost no eyeholes 2 Fairly good, a few eyeholes 1 Poor, eyeholes The coating amount of the composition oil of the present invention applied to the entire surface will be explained with reference to FIGS. 1 to 3. As shown in Figures 1 and 2, the material of the present invention shows little rust even with an extremely small amount of application, and the amount of application is 3/3.
- Sufficient rust resistance has been confirmed. 3■/? Although it is thought that there is an effect even if the amount is less than 7/Z, there is also the problem of accuracy in measuring the coating amount, so in the present invention, the minimum effective coating amount of ji is set to 3/Z.

As shown in Figure 3, the DO8 coating material was 20/1
? On the other hand, with the material of the present invention, no eyeholes occur at all up to 10(lf/i).At higher than that, eyeholes appear, so the upper limit of the coating amount was set at 100%. ■/R.

Thus, the composition oil of the present invention has a dry weight of 3 to 100
It can be seen that a coating of 41 tT in y/m is excellent in both rust resistance and paintability.By the way, even for composition oils made of FDA-approved substances, there is an upper limit on the amount applied to food and beverage can stock. provided (by rolling, 23.25q/r
r? ). Therefore, in the case of materials used for food and beverage cans,
The coating amount of the composition oil should be within the range of 3 to 23 η/-.

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

〔Example〕

Various oil compositions containing TFDA-approved substances shown in Table 2 were diluted with water appropriately and applied to a 0.21 mm thick steel plate in varying amounts. As described above, the coating method used appropriate methods such as temper rolling, roll coater, and spraying. The obtained samples were subjected to rust prevention and paintability tests as described above.

[Comparative example]

A conventional temper-rolled oil-coated material having the composition described in (1) at the beginning of the specification, a material coated with DO8 after a normal dry skin pass, and a non-oil-coated material were used as comparative materials and subjected to the same tests as described above. .

From the T test results shown in Table 3, it is clear that steel materials coated with the pre-composition of the present invention have excellent rust prevention properties and paintability when within the predetermined range of the present invention.

[Brief explanation of drawings]

FIGS. 1, 2, and 301 are graphs showing the relationship between the temper rolling oil and DO8 lubricant of the present invention and the results of a wetness test, a packaging test, and a paintability test, respectively. -LD! Patent Applicant: Kawasaki Steel Co., Ltd., Japan Quaker Chemical Co., Ltd. Patent Attorney Minoru Watanabe 411-ku Deaf Ujo 1 Fig. 3 Coating amount (-97m) Fig. 2 Fig. 3 Coating amount (m9/mυ Makoto) 3 Diagram Room Cloth L (m9/m2) Continued from page 10 Author: Yoshino Kiyono - Chiba Works, Kawasaki Steel Corporation, Kawasaki Steel Corporation, 1, Kawasaki-cho, Chiba City 0 Author: Yoshio Nakazato, Kawasaki Steel, 1, Kawasaki-cho, Chiba City 0 inventions within the Chiba Works of Kawasaki Steel Corporation, 1 Kawasaki-cho, Chiba City. 0 occurrences within the Chiba Works of Kawasaki Steel Corporation, 1 Kawasaki-cho, Chiba City. Author: Sadao Izumiyama. Person: Kyushu Furukawa, 2-2-3 Uchisaiwai-cho, Chiyoda-ku, Tokyo, Tokyo Headquarters of Kawasaki Steel Corporation, 2-2-3 Uchisaiwai-cho, Chiyoda-ku, Tokyo, Japan 0 Inventor: Hidenori Kurosu, 2-2-3 Uchisaiwai-cho, Chiyoda-ku, Tokyo, Tokyo Head Office of Kawasaki Steel Corporation, 0 Inventor: Mitsufuji Naotoshi, 2-13, Shibuyo-cho, Yao-shi, Nippon Rinika Chemical Co., Ltd. 0 inventors Yasumasa Inoue, 2-13 Shibuyou-cho, Yao-shi, Nippon Rinika Chemical Co., Ltd., 9 inventors Ikeda Toshiwa 2-13, Shibuyo-cho, Yao-shi Nippon Rinika Chemical Co., Ltd. Applicant: Japan Quaker Chemical Co., Ltd. 2-13, Shibukawa-cho, Yao-shi

Claims (4)

[Claims] (1) (a) FD, A (pood and
(abbreviation for Drug Administration) petroleum wax and/or synthetic wax and/or lanolin specified in Paragram 178-3910.
(b) 5-40% by weight of fatty acids specified in FDA Paragraph 4178-3910, (c) 5-30% by weight of triethanolamine specified in FDA Paragraph A178-3910, (d) 10-40% by weight of mineral oil as specified in FDA Paragraph 178-3910, (e) nonionic active agent polyethylene glycol monostearate and or FDA Paragraph A 17 g-3400
Excellent anti-rust properties and direct paintability, made by coating the surface with a composition oil made by dispersing and emulsifying 1 to 20% by weight of a nonionic active agent defined in steel plate. (2) The steel plate with excellent rust prevention properties and direct paintability according to claim 1, wherein the coating amount of the composition oil is 3 to 23 q/-. (3) Claim 1, wherein the aqueous medium is water.
The steel plate according to item 1 or 2. (4) The plate (1) according to claim 1 or 2, wherein the aqueous medium is water to which 0.1 to 10% by weight of alcohol or glycol is added.