CN114391036A

CN114391036A - Coolant for plastic working die

Info

Publication number: CN114391036A
Application number: CN202080063591.0A
Authority: CN
Inventors: 水野淳也; 内田香织; 青山充
Original assignee: Nihon Parkerizing Co Ltd
Current assignee: Nihon Parkerizing Co Ltd
Priority date: 2019-10-11
Filing date: 2020-09-28
Publication date: 2022-04-22
Also published as: JP2024024129A; WO2021070664A1; KR20220047331A; JP2021063172A

Abstract

The invention provides a novel coolant for a plastic working die. A coolant for a plastic working mold, comprising the following component A and component B. Component A: one or more than two 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 die

Technical Field

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

Background

When a plastic worked article is produced using a mold, the mold sometimes becomes very hot. When the mold is at a high temperature, it is deteriorated by heat, so that there is a problem that the life of the mold is shortened. From the viewpoint of improving the production efficiency of plastic-worked products and reducing the production cost, it is desirable to prevent the mold from thermally deteriorating. Therefore, a method of cooling the mold using a coolant has been proposed.

For example, patent document 1 discloses a method of spraying a coolant onto an inner surface of a mold of a hot press apparatus, and discloses cooling water as the coolant.

Documents of the prior art

Patent document

[ patent document 1] Japanese patent application laid-open No. 8-197295

Disclosure of Invention

Technical problem to be solved by the invention

The invention aims to provide a novel coolant for a plastic processing die.

Means for solving the problems

As a result of intensive studies by the inventors in order to solve the above-mentioned problems, it was found that a coolant comprising a silicate-containing mineral and a hydrocarbon compound having a predetermined carboxyl group has an excellent cooling effect on a plastic working mold, and the present invention was thereby completed.

Examples of the invention are as follows:

a coolant for a plastic working mold, comprising the following component A and component B.

Component A: one or more than two 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.

Effects of the invention

The present invention can provide a novel coolant for a plastic working die. Therefore, the present invention is expected to contribute to improvement in production efficiency of plastic-worked articles and reduction in production cost.

Detailed Description

Embodiments of the present invention including plastic working mold coolant are described in detail below. The present invention can be arbitrarily changed without departing from the scope of the present invention, and is not limited to the following embodiments.

In one embodiment, the coolant for plastic working molds of the present invention comprises the following component a and component B. Thus, the plastic working mold can exhibit an excellent cooling effect.

Component A: one or more than two silicate-containing minerals;

< ingredient A >

One or more silicate-containing minerals are used as the component A. The silicate-containing mineral may be a natural mineral or a synthetic product. The silicate-containing mineral preferably comprises alumina and/or magnesia. In addition, 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 SiO₄The tetrahedron is bonded to form a surface. For example, the phyllosilicate mineral may include: kaolinite, halloysite, antigorite, monoclinic serpentine, orthofibrous serpentine, ledikite, garnierite, bentonite, montmorillonite, hectorite, pyrophyllite, talc, mica (muscovite, sericite, phlogopite, ferromica, biotite, lepidoliteEtc.), illite, sea stone (clinochloronite, blackish chlorite, etc.), vermiculite, whitlockite, sillimanite, grape stone, fluoroeulite, hydroxyeulite, peacock stone, etc.

The silicate-containing mineral having a network structure is not particularly limited as long as SiO₄The tetrahedron is combined into a net. For example, the network silicate minerals may include: feldspar such as orthoclase, diaclase, askeite (アノーソクレース), albite, ash alluvial, petalite, etc.; kalsilite, cancrinite, leucite, sodalite, bluestone, chrysolite, tetrahedrite, and like feldspar; andalusite such as sodalite and calcialite; clinoptilolite, analcime, mazzite, bestilbite, sillimanite, boggsite, brewsterite, bartonite, chabazite-calcium, chabazite-sodium, chabazite-potassium, canavanillite-beryllite, clinoptilolite-potassium, clinoptilolite-sodium, clinoptilolite-calcium, reslolite, dachiardite-calcium, dacryotanite-sodium, barbiturate, heulandite, erionite-sodium, erionite-potassium, erionite-calcium, faujasite-sodium, faujasite-calcium, faujasite-magnesium, ferrierite-potassium, ferrierite-sodium, phillipsite, williamonite, ferrierite, gmelinite-sodium, gmelinite-calcium, gmelinite-potassium, gowsonite-magnesium, gmelinite-potassium, gmelinite-calcium, gmelinite, gm, Zeolithite, gustalite, gatadite, barbituric cruciate, heulandite-calcium, heulandite-strontium, heulandite-sodium, heulandite-potassium, chrysotile, caribbittate (カリボルサイト), laumontite, levyne-calcium, levyne-sodium, beryllite, mollienite, mazzite, merkalite, mesolite, montesommaite, mordenite, mutalite, natrolite, offretite, prasudillite, petalite (パルテ zeolite), boellite-sodium, boellite-potassium, boellite-calcium, vesuvite, heulandite-sodium, heulandite-potassium, philliphate-calcium, garesite, lawsonia (ロッジァン), scolecite, laumontite, brewsterite, nauplite, laumontite, nauplite, peruvite, gabonite, gaboneset, Terranova zeolite (テラノヴァ zeolite), thomsonite, zenik zeolite (ツァーニック zeolite), zolmithrate zeolite (ツョルトナー zeolite), monocalciumZeolites such as zeolite, hydrocerussite, monetite, thomsonite, leucite, ammonium leucite, huntite, cerberlite, heliolite, beryllite, and the like. 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. The silicate-containing mineral may be used alone or in combination of two or more thereof.

< ingredient B >

Component B is 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 aliphatic carboxylic acid and the aliphatic hydroxy acid are not particularly limited, and for example, aliphatic carboxylic acids and aliphatic hydroxy acids having 7 to 30 carbon atoms can be used, aliphatic carboxylic acids and aliphatic hydroxy acids having 8 to 28 carbon atoms are preferably used, and aliphatic carboxylic acids and aliphatic hydroxy acids having 12 to 22 carbon atoms are more preferably used.

The aliphatic carboxylic acid is a compound in which one or two or more hydrogen atoms in a hydrocarbon are substituted with a carboxyl group. The hydrocarbon may have one or more double or triple bonds. The carbons in the aliphatic carboxylic acid may be linear, branched and/or cyclic, but are preferably linear. The ring formed by connecting into a ring shape may be, for example, a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, etc., 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 or more aliphatic carboxylic acids may be used in combination.

The aliphatic carboxylic acids may include, for example: butyric acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, octacosanoic acid, 2-ethylhexanoic 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-octadecenoic acid, 9, 12-octadecanoic acid, 6,9, 12-octadecatrienoic acid, γ -linolenic acid, arachidonic acid, dihomo- γ -linolenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, and the like.

The aliphatic hydroxy acid is a compound in which one or two or more hydrogen atoms in the hydrocarbon of the aliphatic carboxylic acid are substituted with a hydroxyl group. Aliphatic hydroxy acids may include, for example: 2-hydroxymyristic acid, 3-hydroxymyristic acid, 2-hydroxypalmitic acid, 12-hydroxystearic acid, 2-hydroxyeicosanoic acid, 3-hydroxy-3-methylhexanoic acid, 4-hydroxycyclohexanecarboxylic acid, 3-hydroxy-4-methylcyclohexane-1-carboxylic acid, and the like. One or a combination of two or more of the aliphatic hydroxy acids may be used.

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, an aromatic carboxylic acid and an aromatic hydroxy acid having 8 to 28 carbon atoms are preferably used, and an aromatic carboxylic acid and an aromatic hydroxy acid having 12 to 22 carbon atoms are more preferably used.

The aromatic carboxylic acid is a compound in which one or two or more hydrogen atoms are substituted with a carboxyl group in a hydrocarbon compound having an aromatic ring. The aromatic ring may be a monocyclic ring or a polycyclic ring having two or more rings, and in the case of the polycyclic ring, the aromatic ring may have a condensed ring. The hydrocarbon may have one or more double or triple bonds. The hydrocarbon bonded to the aromatic ring may be linear or branched. One or more kinds of aromatic carboxylic acids may be used in combination.

Aromatic carboxylic acids may include, for example: benzoic acid, phthalic acid, terephthalic acid, 3-phenyl-2-propenoic acid, 4-methoxysilicic acid, p-ethylbenzoic acid, 4-vinylbenzoic acid, and the like.

The aromatic hydroxy acid may include a compound in which one or two or more hydrogen atoms in the above aromatic carboxylic acid are substituted with a hydroxyl group. Examples of aromatic hydroxy acids may include: monohydroxybenzoic acid (salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid), dihydroxybenzoic acid (2-pyrocatechol, etc.), trihydroxybenzoic acid (gallic acid, etc.), 4-methylsalicylic acid, sinapinic acid, mandelic acid, 3-hydroxy-2-phenylpropionic acid, hydroxycinnamic acid, 3, 4-dihydroxycinnamic acid, 1-hydroxy-2-naphthoic acid, 3-hydroxy-2-naphthoic acid, etc. One or a combination of two or more of the aromatic hydroxy acids may be used.

The aliphatic carboxylate, aliphatic hydroxy acid salt, aromatic carboxylate and aromatic hydroxy acid salt may include metal salts of the above aliphatic carboxylic acids, aliphatic hydroxy acids, aromatic carboxylic acids and aromatic hydroxy acids, respectively. The metal salt is not limited and may include: 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. Other salts may include tin, iron, silver, antimony, manganese and ammonium salts. These salts may be used singly or in combination of two or more kinds.

In the coolant, the ratio of the total mass of the component a to the total mass of the component B is preferably in the range of 1.0 to 35.5, more preferably in the range of 2.0 to 26.0, and further preferably in the range of 3.0 to 15.0.

< solvent >

In one embodiment, the coolant of the present invention may be provided as a liquid in which the component a and the component B are dispersed in a solvent. The solvent may be water, and the following water-miscible organic solvents may also be used, for example: ketone solvents such as acetone and methyl ethyl ketone; amide solvents such as N, N' -dimethylformamide and dimethylacetamide; alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as ethylene glycol monobutyl ether and ethylene glycol monohexyl ether; pyrrolidone-based solvents such as 1-methyl-2-pyrrolidone and 1-ethyl-2-pyrrolidone, and the like. When the water-miscible organic solvent is mixed with water, there is no particular limitation as long as the ratio of the mass of the water-miscible organic solvent to the total mass of the water-miscible organic solvent and water is 50 mass% or less, and may be 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less.

< other ingredients >

In one embodiment, the coolant of the present invention may contain additives in addition to the components a, B and the solvent. Examples of the additives include, but are not limited to, resin components, dispersants, surfactants, and additives used in conventional lubricants.

Further, it is preferable that the coolant contains no silica (シリカ) other than the component a, the component B, and the solvent. Therefore, in one embodiment of the coolant of the present invention, the content concentration of silica is 0.4% by mass or less, preferably 0.2% by mass or less, more preferably 0.1% by mass or less, and most preferably 0% by mass, relative to 100% by mass of the coolant.

The coolant of the present invention may be used as it is or after being diluted with a solvent such as water. The dilution ratio of the coolant may be appropriately adjusted depending on the object to be processed, the mold, the contact manner of the coolant with the mold, and the like, and may be, for example, in the range of 1.0 times or more and 15 times or less, and typically may be in the range of 1.2 times or more and 10 times or less.

< method for producing Coolant >

The coolant can be produced by mixing the component a and the component B with a solvent, and adding a desired additive as needed.

In the present embodiment, the coolant is useful for plastic working of a metal material. Specifically, by bringing the coolant into contact with a metal material subjected to plastic working or a plastic working mold, plastic working using the mold can be efficiently performed. The coating film may be formed by bringing a coolant into contact with a metal material or a mold, or a coolant may be attached thereto. The metal material is not particularly limited herein, and may include: iron, steel, alloy steels (e.g., stainless steel, chrome molybdenum steel, die steel), copper or copper alloys, aluminum or aluminum alloys, titanium or titanium alloys, and the like. The plastic working may include: forging, metal stamping, rolling, extrusion, wire drawing, deep drawing, spinning, and bending, but not limited to these processing methods. The method for producing a plastic worked product of the present invention can be suitably used for warm working and hot working in which the temperature of a mold is easily raised. The contact of the coolant with the metal material or the mold is not particularly limited, and may include, for example: dipping, flow coating, spraying or a combination thereof.

Examples

Hereinafter, examples that contribute to better understanding of the present invention and advantages thereof are shown together with comparative examples. However, the present invention is not limited to this embodiment.

(1. preparation of Coolant)

As component a, silicate-containing minerals shown in table 1 or silica were used. As component B, various aliphatic carboxylic acids or salts thereof, salts of aliphatic hydroxy acids, and aromatic hydroxy acids shown in table 1 were used.

The coolant of examples 1 to 16 and comparative examples 1 to 5 was prepared by adding the component A to water and stirring at 25 ℃ for 30 minutes, then adding the component B and further stirring at 25 ℃ for 1 hour. The compositions of the respective coolants are 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 die size: phi 200mm x thickness 20mm

Material of the disc-shaped mold: SS400

Mold heating temperature: 300 deg.C

Spray gun: LPH-100 spray gun (A nai si te tian manufacturing)

Spray air pressure: 0.2MPa

Distance between mold and spray gun: 200mm

Coolant spray amount: 5g

Mold temperature measurement method: a thermocouple was inserted from the side of the mold to a depth of 5mm from the center of the upper surface of the mold, and the temperature of the mold was measured.

Hot plate: AS ONE ceramic hot plate (product number: CHP-250DF)

Size of aluminum plate for soaking: 250mm x thickness 10mm

< test procedure >

(1) An aluminum plate for soaking is placed on the top plate of the hot plate, and then a disc-shaped mold is placed on the aluminum plate for soaking.

(2) Heating was started on a hot plate to bring the mold temperature to 300 ℃.

(3) After confirming that the mold temperature reached 300 ℃ and stabilized, the mold was cooled as follows.

Charging the lance with a predetermined amount of coolant.

Start measuring the temperature of the mold with the data logger.

The heating of the hot plate is stopped, and the coolant is sprayed onto the upper surface of the mold by 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.

After confirming that the mold temperature was once lowered by the coolant injection and then shifted to be raised, the measurement by the data logger was ended.

(4) The coolant adhering to the mold was removed, and the process was returned to the step (2) to conduct the next test.

After the mold cooling test, the lowest temperature value of the mold at which the mold temperature was once lowered by each coolant injection was confirmed based on the results of the data recorder, and the maximum lowering amount (. degree. C.) of the mold temperature from 300 ℃ was obtained. The evaluation of the mold cooling performance of each coolant was classified as follows based on the maximum drop amount of the mold temperature, and the results are shown in tables 1 and 2.

S: above 45 DEG C

A: 40 deg.C or higher and less than 45 deg.C

B: more than 35 ℃ and less than 40 DEG C

C: more than 30 ℃ and less than 35 DEG C

D: less than 30 deg.C

(3. measuring coefficient of friction by Ring compression test method)

For each of the above prepared coolants, the friction coefficient was measured by the ring compression test method.

A ring of a spherical annealing material having a size of 30mm in outer diameter, 15mm in inner diameter, 10mm in thickness and made of S45C was heated in a muffle furnace to 1000 ℃ and held for 5 minutes. The temperature of the ring was measured by welding a thermocouple to the ring.

A flat mold having a dimension of phi 50.8mm x a thickness of 10mm and made of SKD61 (quenching) was prepared. After the upper and lower molds were heated to 300 ℃, each coolant was sprayed to the surface of the upper and lower molds which was in contact with the ring by a spray gun (LPH-100 (manufactured by alaster rock) under a spray pressure of 0.2MPa for a spray time of 2 seconds.

Next, the ring heated to 1000 ℃ was sandwiched between the upper and lower molds coated with the coolant, and compressed using a 2000kN crank press (MSF200 (manufactured by fujiu machine)) at a processing speed of 30spm and a compression rate of 52%.

The inner diameter and thickness of the ring after compression were measured, the inner diameter change rate was calculated, and a theoretical curve of the compression rate-inner diameter change rate was plotted using CAE analysis software (COLD FORM), thereby obtaining the friction coefficient (μ) of each coolant. The evaluation of the friction coefficient of each coolant was classified as follows, and 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 or more and less than 0.22

D: 0.22 or more

[ tables 1-1]

[ tables 1-2]

(upper connection table 1-1)

[ Table 2]

Claims

1. A coolant for a plastic working mold comprising the following component A and component B,

component A: one or more than two silicate-containing minerals;