WO2021070664A1

WO2021070664A1 - Cooling agent for molds for plastic working

Info

Publication number: WO2021070664A1
Application number: PCT/JP2020/036692
Authority: WO
Inventors: 淳也水野; 香織内田; 充青山
Original assignee: 日本パーカライジング株式会社
Priority date: 2019-10-11
Filing date: 2020-09-28
Publication date: 2021-04-15
Also published as: KR20220047331A; JP2021063172A; CN114391036A; JP2024024129A

Abstract

The present invention provides a novel cooling agent which is useful for molds for plastic working. A cooling agent for molds for plastic working, said cooling agent containing the component A and the component B described below. Component A: one or more silicate-containing minerals Component B: one or more compounds selected from the group consisting of aliphatic carboxylic acids and salts thereof, aliphatic hydroxy acids and salts thereof, aromatic carboxylic acids and salts thereof, and aromatic hydroxy acids and salts thereof

Description

Coolant for plastic working dies

The present invention relates to a coolant for a plastic working die.

When manufacturing a plastically processed product using a mold, the mold may become hot. There is a problem that the mold life is shortened due to thermal deterioration when the mold is exposed to a high temperature. From the viewpoint of improving the production efficiency of plastically worked products and reducing the production cost, it is desirable to prevent thermal deterioration of the mold. Therefore, a method of cooling the mold by using a coolant has been conventionally proposed.
For example, Patent Document 1 discloses a method of injecting a coolant onto the inner surface of a mold of a hot press device. Cooling water is disclosed as a coolant.

Japanese Unexamined Patent Publication No. 8-197295

An object of the present invention is to provide a novel coolant useful for plastic working dies.

As a result of diligent studies to solve the above problems, the present inventors have found that a coolant containing a silicate-containing mineral and a hydrocarbon compound having a predetermined carboxy group is excellent for plastic working dies. It has been found that it has a cooling effect, and the present invention has been completed.

The present invention is exemplified as follows.
[1]
A coolant for plastic working dies containing the following components A and B.
Ingredient A: One or more silicate-containing minerals;
Component B: One or more compounds selected from the group consisting of aliphatic carboxylic acids and salts thereof, aliphatic hydroxy acids and salts thereof, aromatic carboxylic acids and salts thereof, and aromatic hydroxy acids and salts thereof. ..

The present invention can provide a novel coolant useful for plastic working dies. Therefore, the present invention can be expected to contribute to the improvement of production efficiency and the reduction of production cost of plastically processed products.

Hereinafter, an embodiment of the present invention including a coolant for a plastic working die will be described in detail. The present invention can be arbitrarily modified without departing from the spirit of the present invention, and is not limited to the following embodiments.

In one embodiment, the coolant for the plastic working die according to the present invention contains the following components A and B. As a result, an excellent cooling effect can be exhibited for the composition processing die.
Ingredient A: One or more silicate-containing minerals;
Component B: One or more compounds selected from the group consisting of aliphatic carboxylic acids and salts thereof, aliphatic hydroxy acids and salts thereof, aromatic carboxylic acids and salts thereof, and aromatic hydroxy acids and salts thereof. ..

<Ingredient A>
As the component A, one or more kinds of silicate-containing minerals are used. The silicate-containing mineral may be a natural mineral or a synthetic product. The silicate-containing mineral preferably contains aluminum oxide and / or magnesium oxide. Further, the silicate-containing mineral may be a hydrous mineral or a hydrate. The silicate-containing mineral is not particularly limited, and examples thereof include layered silicate-containing minerals and network-structured silicate-containing minerals.

The layered silicate-containing mineral is _{not particularly limited as long as the SiO 4} tetrahedron is bonded in a planar manner. , Diagonal chrysotile stone, lizard stone, silicate nickel ore, bentonite, montmorillonite, hectrite, leaf wax, talc, mica (white mica, silk mica, gold mica, iron mica, black mica, trilicio mica, polylithio mica, litia Mica, Chinwald mica, pearl mica, etc.), illite, sea green stone, (clinocloa stone, stirpnomerene, etc.), bitter melon stone, gailol stone, oken stone, grape stone, fluorine apophyllite, hydroacid apophyllite, silica Examples include phyllosilicate minerals such as apophyllite.

The network-type silicate-containing mineral is _{not particularly limited as long as the SiO 4} tetrahedron is bonded in a network shape, and is not particularly limited. , Zeolite, Zeolite, etc .; Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite, Zeolite Amichi Zeolites, Square Zeolites, Barrel Zeolites, Berberch Zeolites, Bikita Zeolites, Boggs Zeolites, Strontium Zeolite Bolites, Heavy Earth Zeolite Zeolites, Ashishi Zeolites, Soda Zeolites, Cali Zeolites, Kiavenna Stones, Cali Diagonal Petitrol Zeolites, Soda Oblique Petitrol Zeolites, Ash Oblique Petitrol Zeolites, Courus Zeolites, Ash Dachiardi Zeolites, Soda Dakiardi Zeolites, Edington Zeolites, Stripped Zeolites, Soda Elion Zeolites, Carierion Zeolites, Ash Elion Zeolites, Soda Forjas Zeolites, Ash Forjas Zeolites, Bitter Earth Forjas Zeolites, Bitter Ferrier Zeolites, Califerie Zeolites, Soda Ferrier Zeolites, Galon Zeolites, Galt Zeolites, Gismond Zeolites, Soda Gumerin Zeolites, Ash Gumerin Zeolites, Caligmerin Zeolites, Govins Zeolites, Gonald Zeolites, Goose Creek Zeolites Cross Zeolites, Ash Zeolites, Strontium Zeolites, Soda Zeolites, Potassium Zeolites, Shanfa Stones, Calibolcite Muddy Zeolites, Ash Levi Zeolites, Soda Zeolites, Rovdal Stones, Marikopa Stones, Massy Zeolites, Merlino Zeolites, Medium Zeolite, Montesonma Zeolites, Morden Zeolites, Mutina Zeolites, Soda Zeolites, O'Fre Zeolites, Pahasapa Zeolites, Parte Zeolites, Sodatsu Polling Zeolites, Cali Polling Zeolites, Calcium Polling Zeolites, Perial Zeolites, Soda Zeolites, Potassium Zeolites, Ash Cross Zeolites, Polx Zeolites , Lodge stone, Scores zeolite, Stella zeolite, Ash bundle zeolite, Soda zeolite, Terranova zeolite, Thomson zeolite, Zernick zeolite, Zoltner zeolite, Weilake zeolite, Weinebene zeolite, Wilhenderson zeolite, Yugawara zeolite, White gemstone, Ammonium white Examples thereof include tectate silicate minerals such as boiled stones (zeolites) such as gemstones, ines stones, dumbli stones, herbites, and dana stones. The crystal structure of the zeolite may be any of A-type, X-type, beta-type, ZSM-5-type, ferrierite-type, mordenite-type, L-type, and Y-type. One type of silicate-containing mineral may be used, or two or more types may be used in combination.

<Component B>
The component B is one or more selected from the group consisting of an aliphatic carboxylic acid and a salt thereof, an aliphatic hydroxy acid and a salt thereof, an aromatic carboxylic acid and a salt thereof, and an aromatic hydroxy acid and a salt thereof. Compounds are used.

The aliphatic carboxylic acid and the aliphatic hydroxy acid are not particularly limited, and for example, an aliphatic carboxylic acid and an aliphatic hydroxy acid having 7 to 30 carbon atoms can be used and have 8 carbon atoms. It is preferable to use an aliphatic carboxylic acid of ~ 28 and an aliphatic hydroxy acid, and more preferably, an aliphatic carboxylic acid and an aliphatic hydroxy acid having 12 to 22 carbon atoms are used.

Aliphatic carboxylic acid means a compound in which one or more hydrogen atoms in a hydrocarbon are substituted with a carboxyl group. Hydrocarbons may have one or more double or triple bonds. The carbon in the aliphatic carboxylic acid may be linearly, branchedly chained, and / or cyclically linked, but is preferably linearly linked. The ring formed by connecting in a ring may be, for example, a 3-membered ring, a 4-membered ring, a 5-membered ring, a 6-membered ring, or the like, but is not limited thereto. The ring is not particularly limited as long as it is a non-aromatic ring, and may be a saturated ring or an unsaturated ring. One type of aliphatic carboxylic acid may be used, or two or more types may be used in combination.

Examples of the aliphatic carboxylic acid include butyric acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, icosanoic acid, docosanoic acid, octacosanoic acid and 2-ethyl. Hexanoic acid, 3,5,5-trimethylhexanoic acid, isopalmitic acid, isostearic acid, cyclohexanoic acid, 4-methylcyclohexanecarboxylic acid, carboxymethylcyclohexanoic acid, 2- (carboxymethyl) cyclohexaneacrylic acid, 9-Tetradecenoic acid, 2-hexadecenoic acid, 9-hexadecenoic acid, 9-octadecenoic acid, 9,12-octadecandienoic acid, 6,9,12-octadecantrienoic acid, γ-linolenic acid, arachidonic acid, dihomo-γ- Examples thereof include linolenic acid, eikosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid and the like.

The aliphatic hydroxy acid means a compound in which one or more hydrogen atoms in the hydrocarbon in the above-mentioned aliphatic carboxylic acid are replaced with hydroxyl groups. Examples of the aliphatic hydroxy acid include 2-hydroxymyristic acid, 3-hydroxymyristic acid, 2-hydroxypalmitic acid, 12-hydroxystearic acid, 2-hydroxyicosanoic acid, 3-hydroxy-3-methylhexanoic acid, and the like. Examples thereof include 4-hydroxycyclohexanecarboxylic acid and 3-hydroxy-4-methylcyclohexane-1-carboxylic acid. One type of aliphatic hydroxy acid may be used, or two or more types may be used in combination.

The aromatic carboxylic acid and the aromatic hydroxy acid are not particularly limited, and for example, an aromatic carboxylic acid and an aromatic hydroxy acid having 7 to 30 carbon atoms can be used and have 8 carbon atoms. It is preferable to use an aromatic carboxylic acid and an aromatic hydroxy acid of to 28, and more preferably an aromatic carboxylic acid and an aromatic hydroxy acid having 12 to 22 carbon atoms.

Aromatic carboxylic acid means a hydrocarbon compound having an aromatic ring in which one or more hydrogen atoms are substituted with a carboxyl group. The aromatic ring may be either a monocyclic type or a polycyclic type having two or more rings, and in the case of the polycyclic type, it may have a fused ring. Hydrocarbons may have one or more double or triple bonds. The hydrocarbon bonded to the aromatic ring may be linear or branched. One type of aromatic carboxylic acid may be used, or two or more types may be used in combination.

Examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, terephthalic acid, 3-phenyl-2-propenic acid, 4-methoxysilicate skin acid, p-ethylbenzoic acid, 4-vinylbenzoic acid and the like.

Examples of the aromatic hydroxy acid include compounds in which one or more hydrogen atoms are replaced with hydroxyl groups in the above-mentioned aromatic carboxylic acid. Examples of aromatic hydroxy acids include monohydroxybenzoic acid (salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid), dihydroxybenzoic acid (2-pyrocatechuic acid, etc.), trihydroxybenzoic acid (calcoic acid, etc.), 4-Methylsalicylic acid, synapic acid, mandelic acid, 3-hydroxy-2-phenylpropanoic acid, hydroxysilicate acid, 3,4-dihydroxysilicate acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2- Examples include naphthoic acid. Aromatic hydroxy acids may be used alone or in combination of two or more.

The aliphatic carboxylic acid salt, aliphatic hydroxy acid salt, aromatic carboxylic acid salt and aromatic hydroxy acid salt include the above-mentioned aliphatic carboxylic acid, aliphatic hydroxy acid, aromatic carboxylic acid and aromatic hydroxy acid, respectively. Examples include metal salts. Examples of the metal salt include, but are not limited to, alkali metal salts (sodium salt, potassium salt, lithium salt, etc.), alkaline earth metal salts (calcium salt, barium salt, etc.), magnesium salt, zinc salt, aluminum salt, etc. Be done. Other salts include salts of tin, iron, silver, antimony, manganese and ammonium. These salts may be used alone or in combination of two or more.

The ratio of the total mass of the component A to the total mass of the component B in the coolant is preferably in the range of 1.0 or more and 35.5 or less, and preferably in the range of 2.0 or more and 26.0 or less. More preferably, it is in the range of 3.0 or more and 15.0 or less.

<Solvent>
In one embodiment, the coolant according to the present invention can be provided as a liquid in which component A and component B are dispersed in a solvent. The solvent can be water, for example, a ketone solvent such as acetone or methyl ethyl ketone; an amide solvent such as N, N'-dimethylformamide or dimethylacetamide; an alcohol solvent such as methanol, ethanol or isopropanol; ethylene glycol. Ether-based solvents such as monobutyl ether and ethylene glycol monohexyl ether; water-miscible organic solvents such as pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone can also be used. .. When the water-miscible organic solvent is mixed with water, it is not particularly limited as long as it is 50% by mass or less with respect to the total mass of the water-miscible organic solvent and water, and is 40% by mass or less and 30% by mass. Hereinafter, it may be 20% by mass or less and 10% by mass or less.

<Other ingredients>
In one embodiment, the coolant according to the present invention may contain an additive in addition to the component A, the component B and the solvent. The additive is not limited, but for example, an additive used in an existing lubricant such as a resin component, a dispersant, and a surfactant can be added.

It is preferable that the coolant does not contain silica other than the component A, the component B and the solvent. Therefore, in one embodiment of the coolant according to the present invention, the silica content is preferably 0.4% by mass or less, preferably 0.2% by mass or less, based on 100% by mass of the coolant. It is more preferably 0.1% by mass or less, and most preferably 0% by mass.

The coolant according to the present invention may be used as it is, or may be diluted with a solvent such as water before use. The dilution ratio of the coolant may be appropriately adjusted depending on the processing target, the mold, the method of contacting the coolant with the mold, etc., but can be, for example, in the range of 1.0 times or more and 15 times or less. Typically, it can be in the range of 1.2 times or more and 10 times or less.

<Manufacturing method of coolant>
The coolant can be produced by mixing component A and component B with a solvent, and if necessary, a desired additive.

In the present embodiment, the coolant is useful when plastic working a metal material. Specifically, by bringing the coolant into contact with a metal material to be subjected to plastic working or a mold for plastic working, plastic working using the mold can be efficiently performed. A film may be formed by contacting the coolant with the metal material or the mold, or the liquid may be adhered to the film. Here, the metal material is not particularly limited, but iron, steel, alloy steel (eg, stainless steel, chromium molybdenum steel, die steel), copper or copper alloy, aluminum or aluminum alloy, titanium or Examples include metal materials such as titanium alloys. Plastic working includes, but is not limited to, forging, metal pressing, rolling, extrusion, wire drawing, drawing, drawing, spinning and bending. The method for producing a plastically worked product according to the present invention can be suitably used for warm working and hot working in which the mold temperature tends to be high. The contact of the coolant with the metal material or the mold is not particularly limited, and examples thereof include a dipping method, a flow coating method, a spray method, or a combination thereof.

Below, examples for better understanding the present invention and its advantages are shown together with comparative examples. However, the present invention is not limited by the present embodiment.

(1. Preparation of coolant)
As the component A, the silicate-containing mineral or silica shown in Table 1 was used. As the component B, various aliphatic carboxylic acids or salts thereof shown in Table 1, salts of aliphatic hydroxy acids, and aromatic hydroxy acids were used.

The coolants of Examples 1 to 16 and Comparative Examples 1 to 5 are prepared by adding component A to water and stirring at 25 ° C. for 30 minutes, then adding component B and further stirring at 25 ° C. for 1 hour. did. The composition of each coolant is as shown in Tables 1 and 2.

(2. Mold cooling test)
The following mold cooling test was performed on each of the coolants prepared above.
<Test conditions>
-Disc-shaped mold size: φ200 mm x thickness 20 mm
-Disc-shaped mold material: SS400
・ Mold heating temperature: 300 ℃
・ Spray gun: LPH-100 spray gun (manufactured by Anest Iwata)
・ Spray air pressure: 0.2MPa
・ Distance between mold and spray gun: 200 mm
・ Coolant spray amount: 5g
・ Mold temperature measurement method: Measure the mold temperature by inserting a thermocouple from the side of the mold at a depth of 5 mm from the center of the upper surface of the mold. ・ Hot plate: AS ONE Ceramic Hot Plate (Product No .: CHP-250DF)
-Aluminum plate for soaking heat: 250 mm x 250 mm x thickness 10 mm
<Test procedure>
(1) An aluminum plate for heat equalization was placed on the top plate of the hot plate, and a disk-shaped mold was further placed on the aluminum plate for heat equalization.
(2) Heating was started on a hot plate so that the mold temperature became 300 ° C.
(3) After confirming that the mold temperature reached 300 ° C. and became stable, the mold was cooled by the following procedure.
-The spray gun was filled with a predetermined amount of coolant.
・ Measurement of mold temperature was started with a data logger.
-The heating of the hot plate was stopped, and the coolant was sprayed toward the upper surface of the mold using the spray gun under the conditions of the distance between the mold and the spray gun, the spray air pressure, and the amount of the coolant sprayed.
-After confirming that the mold temperature dropped once due to the spray of the coolant and then rose again, the measurement with the data logger was completed.
(4) The coolant adhering to the mold was removed, and the process returned to step (2) to perform the next test.

After the mold cooling test, based on the results of the data logger, confirm the minimum value of the mold temperature when the mold temperature drops once by spraying each coolant, and the maximum amount of drop of the mold temperature from 300 ° C ( ℃) was calculated. The evaluation of the mold cooling property of each coolant was classified as follows based on the maximum amount of decrease in the mold temperature. The results are shown in Tables 1 and 2.
S: 45 ° C or higher A: 40 ° C or higher and lower than 45 ° C B: 35 ° C or higher and lower than 40 ° C C: 30 ° C or higher and lower than 35 ° C D: Less than 30 ° C

(3. Measurement of friction coefficient by ring compression test method)
For each of the coolants prepared above, the coefficient of friction was measured by the ring compression test method.
A ring having an outer diameter of 30 mm, an inner diameter of 15 mm, and a thickness of 10 mm and made of S45C spheroidized annealed material was heated to 1000 ° C. in a muffle furnace and held for 5 minutes. The temperature of the ring was measured by welding a thermocouple to the ring.
One upper and lower flat mold with a size of φ50.8 mm × thickness of 10 mm and a material of SKD61 (quenched) were prepared. After heating the upper and lower molds to 300 ° C., a spray gun (LPH-100 (manufactured by Anest Iwata)) is used on the contact surface of the upper and lower molds with a spray air pressure of 0.2 MPa and a spraying time of 2 seconds. Each coolant was sprayed under the conditions of.
Next, the ring heated to 1000 ° C. was sandwiched between the upper and lower dies after applying the coolant, and compressed using a 2000 kN crank press machine (MSF200 (manufactured by Fukui Machinery Co., Ltd.)) at a processing speed of 30 spm and a compression rate of 52%.

The inner diameter and thickness of the ring after compression are measured, the inner diameter change rate is calculated, and using CAE analysis software (COLD FORM), it is plotted on the theoretical curve of compression rate-inner diameter change rate, and the friction coefficient of each coolant is used. (Μ) was calculated. The evaluation of the coefficient of friction of each coolant was classified as follows. The results are shown in Tables 1 and 2.
S: Less than 0.1 A: 0.1 or more and less than 0.14 B: 0.14 or more and less than 0.18 C: 0.18 and less than 0.22 D: 0.22 or more

Claims

A coolant for plastic working dies containing the following components A and B.
Ingredient A: One or more silicate-containing minerals;
Component B: One or more compounds selected from the group consisting of aliphatic carboxylic acids and salts thereof, aliphatic hydroxy acids and salts thereof, aromatic carboxylic acids and salts thereof, and aromatic hydroxy acids and salts thereof. ..