CN1989072B - Magnesium compound sol, method for producing same, and method for producing ceramic material using same - Google Patents

Magnesium compound sol, method for producing same, and method for producing ceramic material using same Download PDF

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CN1989072B
CN1989072B CN2006800004453A CN200680000445A CN1989072B CN 1989072 B CN1989072 B CN 1989072B CN 2006800004453 A CN2006800004453 A CN 2006800004453A CN 200680000445 A CN200680000445 A CN 200680000445A CN 1989072 B CN1989072 B CN 1989072B
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magnesium
magnesium compound
sol
water solvent
carboxylic acid
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CN1989072A (en
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长谷川贵志
西山俊树
中村泰也
儿岛昌造
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Murata Manufacturing Co Ltd
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    • C01F5/14—Magnesium hydroxide
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    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
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    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate

Abstract

Disclosed is a magnesium compound sol using an aqueous solvent which is suitable for uniformly dispersing a magnesium compound in a ceramic powder. When a magnesium compound sol wherein magnesium micelle particles coordinated with a carboxylic acid having a carbonyl group are dispersed in an aqueous solvent is produced, stable magnesium micelle particles can be obtained by reacting magnesium ions with a carboxylic acid selected from citric acid, succinic acid and EDTA in an aqueous solvent so that the molar ratio of the carbonyl groups to magnesium is not less than 1.2 and not more than 2.

Description

Its manufacture method of magnesium compound sol, and use the manufacture method of its ceramic raw material
Technical field
The present invention relates to use the magnesium compound solvent of water solvent and manufacture method thereof, and the manufacture method of ceramic raw material.
Background technology
In the past, be dielectric substance, be extensive use of BaTiO as the high-dielectric constant that constitutes stacked capacitor 3System's pottery.Also have, as the purposes such as raising of the raising holmium coking property of the adjusting of the temperature profile of specific inductivity, reliability, the situation of adding various ancillary components is common example.
Stacked capacitor is owing to the necessity of its miniaturization and high capacity, and thin layer is all making progress every year, and in recent years, also having the thickness of each layer is a few μ m's.In the stacked capacitor of such thin layer progress, bigger than in the past to the requirement of the raising of the dispersiveness of ancillary component.Therefore, need become necessity with the micronize of the ancillary component headed by the magnesium.
For micronized ancillary component of uniform mixing and BaTiO 3Etc. principal constituent, have to prevent the particle coagulation of ancillary component, therefore, with BaTiO 3Before the principal constituent mixing, wish that ancillary component exists with colloidal sol (micellar solution).In addition, the solvent of wishing colloidal sol is a water system.Suppose under the situation of organic system solvent explosion-proof equipment to be set, the manufacturing cost height, therefore, not preferred.
As the typical example of ancillary component, can enumerate magnesium.For example, in patent documentation 1, advised using the method for the manufacturing magnesium compound sol of water solvent.In this manufacture method, be dispersed in the water by magnesium acetate or the Glacial acetic acid magnesium of the magnesium acetate tetrahydrate having been implemented processed, obtain stable micella particle.
Patent documentation 1: the spy opens flat 9-312132 communique
Yet, in patent documentation 1, in the manufacture method of the magnesium compound sol of record, need Dichlorodiphenyl Acetate magnesium tetrahydrate to implement processed, make that its operation is miscellaneous.In addition, the supply source of magnesium is defined in the magnesium acetate compound, and therefore, starting material are selected limited.And then, with the magnesium compound sol of patent documentation 1 as BaTiO 3Be under the ancillary component of the ceramic raw material situation about using, if with other ancillary component colloidal sols coexistences such as rare-earth compounds colloidal sol, then have the trouble of improper situations such as producing cohesion or solation.
Summary of the invention
The present invention makes in view of described situation, share the magnesium compound sol that the stability in the water solvent is also high even its purpose is to provide with various metallic compound colloidal sols.
In addition, other purpose of the present invention is to provide the restriction of the kind that is not subjected to the magnesium supply source, in addition, can be without miscellaneous operations such as dehydration procedures and make the manufacture method of the magnesium compound sol of the magnesium compound sol that stability is high in the water solvent easily.
And then other purpose of the present invention is to provide can be made the manufacture method of magnesium compound sol of the present invention as the ceramic raw material of ancillary component blended ceramic raw material.
Technical scheme 1 described magnesium compound sol of the present invention, it is the magnesium compound sol of carboxylic acid coordinate magnesium micella particles dispersed in water solvent with carbonyl, it is characterized in that, described carboxylic acid is select from citric acid, succsinic acid and EDTA at least a, and the mol ratio with respect to described magnesium of described carbonyl is more than 1.2 below 2.
In addition, technical scheme 2 described magnesium compound sols of the present invention, in technical scheme 1 described invention, the pH of described water solvent is more than 4 below 11.
In addition, technical scheme 3 described magnesium compound sols of the present invention, in technical scheme 1 described invention, the pH of described water solvent is more than 8 below 11.
In addition, the manufacture method of technical scheme 4 described magnesium compound sols of the present invention, it is the method for each described magnesium compound sol in the manufacturing technology scheme 1～3, it is characterized in that, comprising: the operation of the water solvent of preparation magnesium ion or magnesium compound particles dispersed; Carboxylic acid or described carboxylate salt are thrown in the described water solvent, made the operation of carboxylic acid or described carboxylate salt and described magnesium ion or magnesium compound particle reaction.
In addition, the manufacture method of technical scheme 5 described magnesium compound sols of the present invention in technical scheme 4 described inventions, comprising: by alkaline matter is dissolved in the described water solvent, regulate the operation of the pH of described water solvent.
In addition, the manufacture method of technical scheme 6 described ceramic raw materials of the present invention, in ceramic powder, each described magnesium compound sol is as ancillary component in the hybrid technology scheme 1～3.
In addition, the manufacture method of technical scheme 7 described ceramic raw materials of the present invention, described ancillary component comprises the colloidal sol of the metallic element beyond the magnesium as principal constituent.
(effect of invention)
According to the present invention as can be known, share the magnesium compound sol that the stability in the water solvent is also high even can provide with various metallic compound colloidal sols.
In addition, according to the manufacture method of magnesium compound sol of the present invention as can be known, be not subjected to the restriction of the kind of magnesium supply source, in addition, can be without miscellaneous operations such as dehydration procedures and make the magnesium compound sol of the magnesium compound sol that stability is high in the water solvent easily.
And then, according to the manufacture method of ceramic raw material of the present invention as can be known, can make the manufacture method of water solvent magnesium compound sol of the present invention as the ceramic raw material of ancillary component blended ceramic raw material.
Embodiment
Magnesium compound sol of the present invention comprises: water solvent, be dispersed in magnesium micella particle wherein.This magnesium micella particle forms complex compound by the carboxylic acid coordination with carbonyl on magnesium, this complex compound is assembled and formed.
At this, the solvent principal constituent of water solvent is a water, means the solvent that is not organic system.Wherein, the solvent that is dissolved with water-soluble organic compounds such as a spot of ethanol in the water solvent is also included within the water solvent of the present invention.At this, the so-called amount that is meant the degree that does not need antiknock device etc. on a small quantity.
For magnesium micella particle is existed as stable colloidal particles in water solvent, coordination is most important in the kind and the amount of the carboxylic acid of magnesium.When supposing to exist, be dissolved in the water solvent with the state of stable colloidal particles, on the contrary or gelation or generation precipitation.
Coordination, and can generate magnesium micella particulate carboxylic acid by the coordination to magnesium and just do not limit especially so long as have carbonyl at the carboxylic acid of magnesium.As the carboxylic acid of coordination, use from citric acid, succsinic acid and EDTA, select at least a at magnesium.
When generating magnesium micella particle the amount of the carboxylic acid of relative magnesium most important be self-evident.Therefore, the amount to the carboxylic acid of the relative magnesium under the situation of using citric acid, succsinic acid, EDTA as carboxylic acid describes.What magnesium micella particulate stability was played effect is the mol ratio (carbonyl/magnesium) of the carbonyl of relative magnesium, and its mol ratio is more than 1.2 below 2.For example, using under the situation of citric acid as carboxylic acid, each molecule of citric acid has three carbonyls, and therefore, the reactive magnesium citric acid with respect to a mole gets final product for 0.4～0.666 mole.
If described mol ratio is less than 1.2, then magnesium micella particulate solubleness descends, and gel or precipitation take place.In addition, greater than 2.0, then magnesium micella particle becomes too small as if mol ratio, is dissolved in the water solvent, has the trouble that can not get colloidal sol.Under the situation of the stability that further improves magnesium compound sol, be preferably more than 1.5 below 1.8 with respect to the mol ratio of the carbonyl of magnesium.
In addition, stable in water solvent in order to make described magnesium micella particle, the pH of preferably water series solvent is more than 4 below 11.If pH is less than 4, then magnesium compound dissolves easily in water in the series solvent, can not generate stable magnesium micella particle, does not become colloidal sol.In addition, greater than 11, then magnesium compound precipitates, and can not generate stable magnesium micella particle, does not become colloidal sol as if pH.
With magnesium compound sol of the present invention as situation about for example the barium titanate series compound being used as the ancillary component of the ceramic raw materials such as dielectric ceramics raw material of principal constituent under, the pH of water solvent is preferably more than 8 below 11.Because pH is less than 8, then the barium titanate series compound is eluted in the water easily.
Also have, in magnesium compound sol of the present invention, only otherwise hinder under the prerequisite of purpose of the present invention, the ion etc. that mixes other also can.For example, use at magnesium compound under the situation of magnesium acetate, in water solvent, have the acetic acid ion of a great deal of as the supply source that becomes magnesium, in addition, sometimes Wei Liang acetic acid also coordination in magnesium micella particle.But this does not produce bad influence to the stability of magnesium compound sol of the present invention.In addition, other impurity such as metal ingredient that mix trace under the prerequisite that does not hinder purpose of the present invention also can.
Secondly, the manufacture method to magnesium compound sol of the present invention describes.
The manufacture method of magnesium compound sol of the present invention possesses: first operation, the water solvent of its preparation magnesium ion or magnesium compound particles dispersed; Second operation, it throws in carboxylic acid or described carboxylate salt in described water solvent, make the reaction of carboxylic acid or described carboxylate salt and described magnesium ion or magnesium compound particle.
In first operation, at first, will be dissolved in the water solvent as the magnesium compound of magnesium supply source, make the water solvent that contains magnesium ion.At this moment, the kind of magnesium compound so long as getting final product of the particle stabilized colloidal particles of described carboxylic acid coordinate magnesium micella do not limit especially.In addition, the solubleness that the preceding magnesium compound monomer of carboxylic acid coordination is dissolved in the water does not become problem.For example, be preferably dissolved in the high magnesium acetate of solubleness in the water (comprise hydrate also can).On the other hand, magnesium oxide when dissolving heat release is many, according to circumstances, has the miscellaneous trouble of manufacturing process, but the stability of the magnesium compound sol that generates is not produced bad influence.Be difficult to be dissolved in use under the situation of magnesium compound, for example magnesium hydroxide etc. of water solvent, magnesium hydroxide particle is dispersed in the water, it also can as water solvent.
In addition, in second operation, in the water solvent that makes the magnesium ion for preparing in first operation or magnesium compound particles dispersed, throw in the carboxylic acid or the carboxylate salt of regulation, when stirring this water solvent well, make the reaction of carboxylic acid and magnesium ion or magnesium compound particle.Temperature during stirring be room temperature also can, but if heat, then Fan Ying speed accelerates.By this reaction, generate the magnesium micella particle of carboxylic acid coordination at magnesium.By making this magnesium micella particle become the state of stable colloidal particles, generate stable magnesium compound sol.
In addition, by adding described carboxylic acid or carboxylate salt, the pH step-down of water solvent sometimes.At this moment, alkaline matters such as sodium hydroxide, potassium hydroxide, amine compound, ammonia based compound can be added as the pH regulator agent, be adjusted to suitable pH value.
Secondly, the manufacture method to ceramic raw material of the present invention describes.In the present invention, in ceramic powder, mix described magnesium compound sol as ancillary component.As the preferred dielectric ceramics of ceramic powder, as the principal constituent of dielectric ceramics, for example, preferred barium titanate series compound.
As the method for mixing magnesium compound sol,, just do not limit especially as long as the magnesium compound uniform particles is disperseed.For example, preferred preparation is starched ceramic powder and pure water blended, when this slurry is stirred in container, drips the method for magnesium compound sol of the present invention.
As the ancillary component of described ceramic raw material, except magnesium compound sol of the present invention, can also add other metallic element, for example, the colloidal sol of rare-earth element compound.Even the colloidal sol coexistence of other metallic element is arranged in the magnesium compound sol of the present invention simultaneously, its stability does not suffer damage yet.
Embodiment
Secondly, according to embodiment more specifically the present invention is described.So long as the mode that can implement in the scope of the present invention, the embodiments of the invention that not only are defined in following explanation are self-evident.
Embodiment 1
In the present embodiment, investigate to the kind of carboxylic acid and with respect to the influence of the mol ratio of the carbonyl of magnesium.Promptly, as the raw material of magnesium compound sol, the powder of the magnesium acetate (comprising hydrate) of preparation specified amount, magnesium chloride, magnesium nitrate is dissolved in the water it.In addition, during the powder of magnesium hydroxide aborted, stir, magnesium hydroxide particle is dispersed in the water.To this, the carboxylic acid of the regulation shown in the table 1 or carboxylate salt so that the mode that its mol ratio with respect to magnesium becomes the value shown in the table 1 is thrown in when stirring, and then are added the Monoethanolamine MEA BASF of specified amount and stir and make its pH become 9.5.By the DT1200 of Japanese Le Off ト corporate system, measure state and its median size of the product that obtains, its result is illustrated in the table 1.In addition, in sample separately, the solubleness when obtaining the mol ratio that makes magnesium and carboxylic acid separately and reaching the reaction of 1: 1 ground is illustrated in its result in the table 1.Also have, in table 1, the sample that has the * mark is a thing outside the scope of the present invention.
According to the result shown in the table 2 as can be known, the sample of specimen coding 1～12 is that carboxylic acid uses citric acid, succsinic acid, EDTA or their salt, make carbonyl become 2 samples that react more than 1.2 followingly, therefore, obtain stable magnesium compound sol with respect to the mol ratio of magnesium.
Yet specimen coding 13,14 is to use tartrate and the tartrate sample as carboxylic acid, but tartrate and tartrate are not the carboxylic acids that uses among the present invention, therefore, the tartrate coordination is low in the magnesium micellar solubleness of magnesium, and magnesium micella particle becomes the white gels shape, can not get colloidal sol.
Specimen coding the 15, the 16th uses lactic acid and the oxalic acid sample as carboxylic acid respectively, but lactic acid and oxalic acid any one be not the carboxylic acid that uses among the present invention, therefore, lactic acid and oxalic acid coordination fully produce the precipitation of magnesium hydroxide at magnesium, can not get colloidal sol.
Specimen coding 17 is to use the sample of citric acid as carboxylic acid, but little with respect to the mol ratio of the carbonyl of magnesium, is 0.6, and therefore, magnesium micella particulate solubleness is low, becomes the gel state of white, can not get colloidal sol.
Specimen coding the 18, the 19th uses the sample of citric acid as carboxylic acid respectively, but bigger than 2 respectively with respect to the mol ratio of the carbonyl of magnesium, therefore, does not generate magnesium micella particle, becomes the solution shape, can not get colloidal sol.
[table 1]
Specimen coding Magnesium raw material Carboxylic acid Carboxylic acid/magnesium mol ratio Carbonyl/magnesium mol ratio Solubleness [weight %] The state of product Median size [nm]
1 Magnesium acetate Citric acid 0.55 1.65 27 Colloidal sol 60
2 Magnesium acetate Triammonium citrate 0.55 1.65 27 Colloidal sol 60
3 Magnesium acetate Succsinic acid 0.83 1.66 20 Colloidal sol 34
4 Magnesium acetate The EDTA dipotassium 0.97 1.94 10 Colloidal sol 40
5 Magnesium oxide Citric acid 0.65 1.95 27 Colloidal sol 60
6 Magnesium hydroxide Citric acid 0.60 1.80 27 Colloidal sol 75
7 Magnesium chloride Citric acid 0.55 1.65 27 Colloidal sol 65
8 Magnesium nitrate Citric acid 0.55 1.65 27 Colloidal sol 65
9 Magnesium acetate Citric acid 0.40 1.20 27 Colloidal sol 68
10 Magnesium acetate Citric acid 0.50 1.50 27 Colloidal sol 50
11 Magnesium acetate Citric acid 0.60 1.80 27 Colloidal sol 70
12 Magnesium acetate Citric acid 0.67 2.00 27 Colloidal sol 72
Specimen coding Magnesium raw material Carboxylic acid Carboxylic acid/magnesium mol ratio Carbonyl/magnesium mol ratio Solubleness [weight %] The state of product Median size [nm]
*13 Magnesium acetate Tartrate 0.83 1.66 0.05 Leucosol -
*14 Magnesium acetate Disodium tartrate 0.83 1.66 0.05 Leucosol -
*15 Magnesium acetate Lactic acid 1.65 1.65 0.10 Precipitation -
*16 Magnesium acetate Oxalic acid 0.83 1.66 0.02 Precipitation -
*17 Magnesium acetate Citric acid 0.20 0.60 27 Leucosol -
*18 Magnesium acetate Citric acid 0.70 2.10 27 Solution -
*19 Magnesium acetate Citric acid 1.00 3.00 27 Solution -
Embodiment 2
The influence of the pH of the water solvent during in the present embodiment, to use citric acid or succsinic acid describes.Promptly, the preparation magnesium acetate (comprising hydrate) powder, it is dissolved in the water.Afterwards, carbonyl is become the carboxylic acid shown in the table 2 with respect to the mol ratio of one mole of magnesium and throw in when the value ground shown in the table 2 stirs, and then add as the alkaline matter shown in the table 2 of the pH regulator agent of water solvent and stir, make it become the pH shown in the table 2.The state of the product that obtains and its median size are illustrated in the table 2.Also have, in table 1, the sample that has the * mark is a thing outside the scope of the present invention.
According to the result shown in the table 2 as can be known, specimen coding 22～28, and the sample of specimen coding 31～37 be that alkaline matter with water solvent is that scope of the present invention is 4～11 sample with pH regulator, therefore, obtain stable magnesium compound sol.
To this, the sample of specimen coding 21,30 be pH than 4 low samples, therefore, do not generate magnesium micella particle, become the solution shape, can not get colloidal sol.
The sample of specimen coding 29 be pH than 11 high samples, therefore, produce the precipitation of magnesium hydroxide, can not get colloidal sol.
[table 2]
Specimen coding Carboxylic acid Carboxylic acid/magnesium mol ratio Carbonyl/magnesium mol ratio Alkaline matter pH The state of product Median size [nm]
*21 Citric acid 0.55 1.65 Do not have 3.9 Solution -
22 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 4.2 Colloidal sol 43
23 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 4.9 Colloidal sol 39
24 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 6.0 Colloidal sol 46
25 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 7.8 Colloidal sol 48
26 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 8.9 Colloidal sol 49
27 Citric acid 0.55 1.65 Monoethanolamine MEA BASF 10.0 Colloidal sol 60
28 Citric acid 0.55 1.65 Sodium hydroxide 11.0 Colloidal sol 80
*29 Citric acid 0.55 1.65 Sodium hydroxide 12.0 Precipitation -
*30 Succsinic acid 0.83 1.66 Do not have 3.8 Solution -
31 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 4.1 Colloidal sol 43
32 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 4.5 Colloidal sol 45
33 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 5.3 Colloidal sol 63
Specimen coding Carboxylic acid Carboxylic acid/magnesium mol ratio Carbonyl/magnesium mol ratio Alkaline matter pH The state of product Median size [nm]
34 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 6.0 Colloidal sol 66
35 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 7.2 Colloidal sol 71
36 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 8.7 Colloidal sol 81
37 Succsinic acid 0.83 1.66 Monoethanolamine MEA BASF 9.5 Colloidal sol 34
Embodiment 3
In the present embodiment, magnesium compound sol of the present invention and other metallic compound colloidal sol are made ceramic raw material as ancillary component.Promptly, prepare the powder of barium titanate, it is mixed with water by ball mill, make the slurry that contains barium carbonate powder as ceramic powder.Secondly, the magnesium compound sol of the specimen coding 1 of preparation embodiments of the invention 1.In addition, as with the metallic compound colloidal sol of the metallic element beyond the magnesium, prepare holmium micella particles dispersed the holmium compound colloidal sol in water of citric acid coordination at holmium as principal constituent.
When stirring described slurry, drippage magnesium compound sol and holmium compound colloidal sol in described slurry.At this moment, the control drainage, making magnesium, holmium is 2 moles, 1 mole with respect to 100 moles of barium titanates.Well-beaten result, magnesium compound sol and holmium compound colloidal sol are well dispersed in the slurry, and improper situations such as cohesion or gelation do not take place.Dry should slurry, obtain the abundant dispersive barium titanate of magnesium and holmium powder, be the raw material of dielectric ceramics.

Claims (6)

1. magnesium compound sol, it is the magnesium compound sol of carboxylic acid coordinate magnesium micella particles dispersed in water solvent with carbonyl, it is characterized in that,
Described carboxylic acid is select from citric acid, succsinic acid and EDTA at least a, and the mol ratio with respect to described magnesium of described carbonyl is more than 1.2 below 2,
The pH of described water solvent is more than 4 below 11.
2. magnesium compound sol according to claim 1 is characterized in that,
The pH of described water solvent is more than 8 below 11.
3. the manufacture method of a magnesium compound sol, it is characterized in that for making the method for each described magnesium compound sol in the claim 1～2, comprising:
The operation of the water solvent of preparation magnesium ion or magnesium compound particles dispersed;
Carboxylic acid or described carboxylate salt are thrown in the described water solvent, made the operation of carboxylic acid or described carboxylate salt and described magnesium ion or magnesium compound particle reaction.
4. the manufacture method of magnesium compound sol according to claim 3 is characterized in that,
Comprise:, regulate the operation of the pH of described water solvent by alkaline matter is dissolved in the described water solvent.
5. the manufacture method of a ceramic raw material is characterized in that,
In ceramic powder, each described magnesium compound sol is as ancillary component in the hybrid right requirement 1～2.
6. the manufacture method of ceramic raw material according to claim 5 is characterized in that,
Described ancillary component comprises the colloidal sol of the metallic element beyond the magnesium as principal constituent.
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