JPH04337334A - Anticorrosive agent masterbatch - Google Patents

Abstract

PURPOSE:To provide the subject anticorrosive agent masterbatch product useful as a volatile anticorrosive material for metals by itself and capable of molding into various shapes after dilution with another plastics. CONSTITUTION:With (A) 10 pts.wt. volatile anticorrosive agent selected from aliphatic secondary amine nitrous acid salt, aliphatic secondary amine carbonic acid salt, benzotriazole, caffeine, etc., (B) 5-15 pts.wt. ester-based wax having 40-140 deg.C softening point, e.g. a higher fatty ester, a higher alcohol ester, an ethylene-vinyl acetate copolymer-based wax or a natural wax and (C) 50-200 pts.wt. polyolefin-based resin are kneaded at 50-170 deg.C followed by molding.

Description

[Detailed description of the invention]

0001

[Industrial Application Field] The present invention relates to a rust preventive masterbatch, which is diluted with other plastics such as polyolefin and molded into pellets, linear products, films, sheets, packing, packaging materials, containers, etc. By processing, we provide a rust preventive masterbatch product that is useful for the preservation and security of various metal products, and also serves as a volatile metal rust preventive material as it is.

0002

[Prior Art] Products known so far for rust preventive compositions include rust preventive oil, rust preventive paper, rust preventive film, rust preventive paint, rust preventive cutting fluid, rust preventive antifreeze liquid, and rust preventive powder. There are various types of rust preventive products such as , rust preventive wax, rust preventive tablets, and rust preventive detergents, but no rust preventive masterbatch product containing a high concentration of volatile rust preventive has been provided.

[0003] A "masterbatch" is generally a compound material that contains a high concentration of drugs and active ingredients that should be included in the final product, such as a compounded plastic product or a compounded rubber product. Alternatively, it is used to facilitate the compounding work in the manufacturing process leading to the final rubber product. For this reason, masterbatch is also called mother stock and has a wide range of applications. In addition, masterbatches not only improve workability in the production of final products, but also stably preserve drugs and active ingredients, store, transport, and
This makes handling in measuring and blending extremely convenient.

0004

[Problems to be Solved by the Invention] The present invention contains a highly concentrated volatile rust preventive agent, and is suitable for use in various resin molded products such as pellets, linear products, films, sheets, packing, packaging materials, and containers. A technical problem is to provide a rust preventive masterbatch that can be suitably used in production and can be stored for a long period of time when unused.

[0005]

Means and Effects for Solving the Problems In order to achieve the above-mentioned technical problems, the present inventors conducted systematic and detailed research and have now finally completed the present invention.

That is, the present invention consists of 10 parts of a volatile rust inhibitor, 5 to 15 parts of an ester wax having a softening point of 40 to 140°C, and 50 to 200 parts of a polyolefin resin.
This is a rust preventive masterbatch made by kneading and molding parts at 50 to 170°C.

[0007] The volatile rust inhibitor in the present invention includes aliphatic secondary amine nitrite, aliphatic secondary amine carbonate, aliphatic secondary amine benzoate, benzotriazole, nuclear-substituted benzotriazole, At least one rust inhibitor selected from the group consisting of caffeine and caffeine salts.

[0008] Further, the softening point in the present invention is 40 to 14
Ester waxes having a temperature of 0°C are those selected from the group consisting of higher fatty acid esters, higher alcohol esters, ethylene/vinyl acetate copolymer waxes, ethylene/(meth)acrylate copolymer waxes, animal and vegetable oils and fats, and natural waxes. At least one wax.

The structure and operation of the present invention will be explained in more detail as follows. First, typical aliphatic secondary amines are piperidine, morpholine, imidazole, diisopropylamine, ditert-butylamine, di-sec-butylamine, diisobutylamine, dicyclopentylamine, dicyclohexylamine,
isopropylcyclohexylamine, etc., and if the general formula is represented by R, R'NH, the nitrite is R, R'NH.
HNO2, carbonate is R,R'NH・H2 CO3,
Benzoate is represented by R,R'NH.C6 H5 COOH. These amine salts are considerably more volatile than other amine salts, and the industrially important ones are morpholine, diisopropylamine, and dicyclohexylamine salts, which may be used alone or in combination.
Used in the form of a mixture of more than one species. These are useful as volatile rust inhibitors for iron and iron alloys.

Benzotriazole and nuclear-substituted benzotriazole are represented by the following formula.

[Chemical formula 1]

In formula 1, when R is H, 1, 2, 3
-benzotriazole, when R is CH3, it is methylbenzotriazole, when R is C2H5, it is ethylbenzotriazole, and when R is i-C3
In the case of H7, it is isopropylbenzotriazole, and in the case of R is Cl, it is chlorobenzotriazole, which are volatile rust inhibitors for nonferrous metals (silver, copper, zinc, tin, aluminum, alloys containing these, etc.) It is useful as a.

Caffeine and caffeine salts are caffeine, caffeine benzoate, caffeine salicylate, caffeine soda benzoate, caffeine soda salicylate. These serve as volatile rust preventives for iron and non-ferrous metals, but since their vaporization properties are somewhat poor, they are often used in combination with the aforementioned aliphatic secondary amine salts and benzotriazoles.

Next, typical ester waxes having a softening point of 40 to 140°C are shown below (approximate values of melting point, freezing point, or softening point are mp.
). Rice wax (mp. 70-8
0°C), 12-hydroxystearate (mp
．． 50-60℃), palm oil (mp. 40-50℃)
, wood wax (mp. 40-50℃), beef tallow (mp. 40
~50℃), pork fat (mp. 40~50℃), horse fat (mp.
p. 40-50℃), mutton fat (mp. 44-55℃)
, whale wax (mp. 42-52°C), beeswax (mp.
63-66℃), carnauba wax (mp. 78-86
℃), candelilla wax (mp. 64-80℃), seratsuro (mp. 72-78℃), palm wax (mp.
．． 85-86℃), Montan wax (mp. 60-1
05°C), fish oil hydrogenated oil (mp. 40-60°C), whale oil hydrogenated oil (mp. 40-60°C), soybean oil hydrogenated oil (mp.
p. 60℃ or higher), hydrogenated palm oil (mp. 51~
56°C), hydrogenated jojoba oil (mp. 65-80°C),
Hydrogenated castor oil (mp. 70-90℃), hydrogenated rapeseed oil (mp. 57-60℃), hydrogenated wax (mp.
．． 50-60℃), reduced lanolin (mp. 40-5
5°C), dodecyl palmitate (mp. 41°C), monomyristin (mp. 50-70°C), monostearin (mp. 74.4°C), oil-based waxes (e.g., Itou Wax E, Kao Wax 85- P, Castor wax, Synchro wax, Cucina CP, Roxiol G: all trade names), Hoechst wax (mp.
80-90℃), ethylene/vinyl acetate copolymer wax, ethylene/vinyl acetate copolymer modified resin, ethylene/acrylate copolymer wax, ethylene/methacrylate copolymer wax, ethylene/acrylate/vinyl acetate copolymer wax, ethylene/methacrylate/vinyl acetate copolymer wax, etc.
These may be used alone or as a mixture of two or more thereof.

Examples of polyolefin resins (approximate values of melting point or softening point are indicated as mp.) include ethylene/α-olefin copolymer (mp. 120°C), ethylene/vinyl chloride copolymer (mp. 100-150
°C), polybutadiene (mp.170 °C or less),
Polybutylene (mp.126℃), polyethylene (mp.
．． 80-140℃), polypropylene (mp.12
0 to 170℃), composite polypropylene (mp.12
0-170℃), ethylene/vinyl acetate copolymer (m
p. 40-100℃), ethylene/vinyl acetate/vinyl chloride copolymer (mp. 60-120℃), ionomer (mp. 60-100℃), polystyrene (mp.
p. 70-120℃), modified polyolefin (mp
．． 150-170℃), but the industrially important ones are polyethylene, polypropylene, ethylene, etc.
It is a vinyl acetate copolymer, a mixture thereof, or a polymer alloy thereof.

10 parts of the volatile rust preventive agent of the present invention, 5 to 1 part of an ester wax having a softening point of 40 to 140°C
The blending ratio of 5 parts and 50 to 200 parts of the polyolefin resin is extremely important in ensuring the quality of the rust preventive masterbatch, and deviations from this blending ratio may cause various problems.

For example, A: The effect of the volatile rust inhibitor becomes unstable, and in some cases, significant bleeding or blooming occurs, making it difficult to further process the rust inhibitor masterbatch. B: The ester wax acts as a lubricant during the manufacturing process, making it difficult to mix uniformly with the polyolefin resin. C: Coloring agents, fragrances, or antioxidants may be mixed during the manufacturing process, but the presence of these agents may cause deterioration of the rust preventive agent. D: When adding inorganic powder as a filler, molding becomes difficult. E: In extreme cases, diffusion and movement of the volatile rust preventive agent in processed plastic products may be hindered, leading to a decline in quality. F: Significant coloring occurs in the rust preventive masterbatch and plastic processed products using the masterbatch, resulting in poor appearance.

The kneading temperature in the present invention is also important, and must be maintained at 50 to 170°C; if the temperature is lower than 50°C, uniform kneading becomes difficult;
If this is the case, foaming, coloring, and sublimation may become severe, resulting in deterioration (decomposition) or reduction of the active ingredients. Therefore, the kneading temperature is 50 to 170°C, particularly preferably 60 to 170°C.
It should be kept between 160°C.

The rust preventive masterbatch according to the present invention is usually provided as a product in the form of pellets (granules).

Since the volatile rust inhibitor used in the present invention is an amine compound, it often becomes slightly colored due to oxidation when operated in air. For example, dicyclohexylamine nitrite (decomposed at about 180°C) can be dispersed or dissolved in an ester wax at a low temperature below the decomposition point (preferably below 100°C) in an oxygen-free atmosphere to create a pale to white masterbatch intermediate. The body can produce it. The same applies to other rust preventives. However, unless the coloring is particularly severe, there is no major change in the properties as a rust preventive agent.

The following methods (a) to (d) are examples of general manufacturing procedures for the rust preventive masterbatch according to the present invention. (a) A volatile rust preventive agent, an ester wax, and a polyolefin resin are kneaded together. (b) Ester wax and polyolefin are kneaded and a volatile rust preventive agent is added thereto. (c) A volatile rust preventive agent is dispersed in ester wax, and this is mixed with a polyolefin resin. (d) A volatile rust preventive agent is dispersed in a polyolefin resin, and an ester wax is kneaded therein.

[0021] When it is desired to add inorganic fillers, fragrances, antioxidants, and colorants in the above (a) to (d), it is natural that these auxiliary materials may be added at any step of the operation as necessary.

A pelletizer is used to pelletize, ie, mold, the rust preventive masterbatch according to the present invention. Furthermore, if pelletizer molding is not desired, but a sheet, rod, or other shape is desired, an appropriate molding machine may of course be used. Furthermore, it may be extruded into a sheet and then cut.

[0023] When producing the rust preventive masterbatch according to the present invention, care must be taken to avoid severe blooming of the volatile rust preventive agent and severe bleeding of the ester wax. The terms "bleeding" and "blooming" are mostly visual or sensory evaluation terms, and although standard test methods (e.g. ASTM or ISO) are about to be established, they are not currently available. There is no way to accurately measure and quantify it. However, British Standard BS 2571-1955
, BS 1763, and BS 2739-1956 describe a plasticizer bleeding test method for vinyl chloride resin sheets, and it seems that the quality of the product is qualitatively determined based on this. To prevent excessive bleeding and blooming,
Of course, the above-mentioned mixing ratio must be maintained.

[0024] In order to prevent excessive bleeding and blooming, it is an effective means to add an appropriate amount of inorganic filler. silica, pearlite, dicalite), alumina powder (aerosil alumina, activated alumina), alkaline earth metal powder (light calcium carbonate, calcite, aragonite, dolomite, magnesium carbonate), aluminum silicate powder ( Kaolin, calcined kaolin, clay, aluminum silicate, bentonite, montmorillonite, waxite), magnesium silicate powder (talc, steatite, sepiolite), aluminum magnesium silicate powder (
Attapulgite, zeolite, sericite, feldspar, vermiculite) and other powders with the smallest possible particle size (average particle size of 50 μm or less) are used, and the amount added is preferably 25% by weight or less of the ester wax. is preferably 2 to 20% by weight.

[0025]

[Example] The present inventors have confirmed the superiority of the present invention through numerous experiments.In order to explain the technical content of the present invention, we have extracted a few representative examples below. This will be shown as an example.

[0026] If the rust preventive masterbatch product according to the present invention obtained in each example is used as a volatile rust preventive material by sealing it in a bag as it is, the effect will be reduced because it contains a high concentration of rust preventive agent. There are some remarkable results. Therefore, the rust preventive masterbatch product obtained in each example was diluted with polyolefin so that the content of the volatile rust preventive agent was 0.5 to 2.0% by weight, and then molded into a film, sheet, or plate. death,
The molded product was subjected to a rust prevention test in accordance with JIS-Z-1533, and the rust prevention effect was determined by determining the effect as excellent, good, fair, or poor. Such determination results are shown in Examples 1 to 19 and Comparative Examples 1 and 2, which will be described later.

Examples 1 to 9 1400 g of hardened jojoba oil was melted in a hot bath, 2000 g of the volatile rust preventive agent shown in Table 1 was added thereto, mixed and dispersed in a nitrogen stream, and then 130 g of jasmine fragrance was added. Add and mix well. The mixing temperature is 80 to 85°C, and while maintaining this temperature, 170 g of Aerosil silica is further sprinkled and thoroughly kneaded. After cooling, 1,630 g of ethylene/vinyl acetate copolymer powder (vinyl acetate content: 19%, softening point: 64 to 70°C) was added thereto, further kneaded, and pelletized using a pelletizer at 100°C. The rust inhibitor masterbatch obtained here contains about 10% of a volatile rust inhibitor, and is a high-quality pellet-like product without significant bleeding or blooming. Next, the above pelletized product was diluted with the polyolefin shown in Table 1 to have the volatile rust preventive content shown in Table 1, and extruded at about 130°C to form a sheet. The rust prevention effect on the metals shown was determined. The results are shown in Table 1.

[Table 1] Note that when the content of the volatile rust preventive agent was diluted to about 0.5%, the rust preventive effect became acceptable, and when it was diluted to 0.2%, it became poor.

Examples 10 to 19 500 g of the ester wax shown in Table 2 and 5000 g of the polyolefin resin shown in Table 2 were melted and mixed at 140°C or below, and 500 g of dicyclohexylamine nitrite was dispersed and kneaded. Pelletize using a pelletizer at 170°C or lower in a nitrogen stream. The rust preventive masterbatch obtained here contains about 10% dicyclohexylamine nitrite and is a pellet-like product of good quality without significant bleeding or blooming. Next, the above pellet-shaped product was diluted with polyethylene to have the volatile rust preventive content shown in Table 2, and extruded at about 130°C to form a sheet, and the rust preventive effect of the sheet on iron was determined. did. The results are shown in Table 2.

[Table 2]

Comparative Example 1 When paraffin wax was used in place of the jojoba hydrogenated oil in Examples 1 to 9, the vaporizable rust preventive agent from the obtained rust preventive masterbatch showed severe blooming and in some cases foaming. However, it was not easy to produce pellets and guarantee their quality.

Comparative Example 2 In Examples 10 to 19, when the amount of ester wax used was 250 g or less, bleeding or blooming was severe and a uniform rust preventive masterbatch could not be obtained. In addition, 1000% ester wax
When using g, the volatility of dicyclohexylamine nitrite deteriorated, resulting in a rust inhibitor masterbatch of low value. The ester waxes shown in Table 2 all have a softening point of 40 to 140°C, but instead of this, para rubber seed oil (mp. 26°C) and cashew seed oil (mp.
28-30°C) and cocoa butter (mp. 32-39
℃), the rust preventive masterbatch product was soft and had low commercial value, and severe bleeding occurred, making it difficult to store and handle the pellets.

Examples 20 to 30, Comparative Examples 3 to 5 300 g of palm wax and 200 g of lard were melted at 70°C, and 100 g of the volatile rust preventive agent shown in Table 3 was added thereto, followed by the inorganic filler shown in Table 3. Add 50 g (average particle size 1 μm or less) and mix vigorously. This operation was performed in a nitrogen stream. After cooling, the powder thus obtained was mixed with 2000 g of low-density polyethylene and extruded into a sheet using an extruder at 130°C or below. After cooling, the sheet was cut into an equilateral triangular shape with a side of 5 mm using a die cutter. After cutting, 50 g of the cut pieces were sealed in a nylon net, and each bag was placed in an automobile tool box (made of metal, internal volume: approximately 5 liters), and tested for two years. The materials of the tool box and its contents are as shown in Table 3, and the rust prevention effect on the contents is indicated by ◎, ○, △, and ×.

[Table 3]

[0032]

[Effects of the Invention] The rust preventive masterbatch product according to the present invention contains a high concentration of volatile rust preventive agent, and in addition to being a volatile rust preventive material for metals by itself, it can also be diluted with other plastics. By molding it into an appropriate shape, it becomes a final product that is suitable for various purposes. Therefore, we are confident that the effects of the present invention are extremely large and that it will be useful not only in the metal industry but also in various fields ranging from automobiles, machinery, packaging materials, electronic parts to daily necessities.

Claims (3)

[Claims] [Claim 1] 10 parts of a volatile rust preventive agent with a softening point of 40~
50 to 170 parts of ester wax at 140°C and 50 to 200 parts of polyolefin resin.
A rust preventive masterbatch made by kneading and molding at ℃. 2. The volatile rust inhibitor is an aliphatic secondary amine nitrite, an aliphatic secondary amine carbonate, an aliphatic secondary amine benzoate, a benzotriazole, a nuclear-substituted benzotriazole, caffeine, and The rust inhibitor masterbatch according to claim 1, which is at least one rust inhibitor selected from the group consisting of caffeine salts. 3. Ester waxes with a softening point of 40 to 140°C include higher fatty acid esters, higher alcohol esters, ethylene/vinyl acetate copolymer waxes, ethylene/(meth)acrylate copolymer waxes, animal and vegetable oils and fats, and natural waxes. The anticorrosive masterbatch according to claim 1, which is at least one wax selected from the group consisting of waxes.