JPH09156923A - Calcium-based filler and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a calcium-based filler excellent in dispersibility and redispersibility. SOLUTION: This filler contains, as active ingredient, a calcium compound surface-coated with a saccharide containg β-2,1-bond fructose polymer bearing glucose on the reduced terminal. This filler is obtained by reaction of an aqueous suspension of calcium hydroxide with carbon dioxide or a mineral acid (salt) in the presence of a saccharide containing β-2,1-bond fructose polymer bearing glucose on the reduced terminal.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel calcium-based filler and a method for producing the same, and more particularly to a calcium-based filler excellent in dispersibility and redispersibility and a method for producing the same.

[0002]

2. Description of the Related Art Various calcium-based fillers have been used in a wide variety of fields since ancient times. For example, calcium carbonate is used for rubber and plastic fillers, papermaking fillers and coatings, extender pigments, dentifrices, synthetic papers, synthetic wood fillers, etc.Calcium phosphate is a swelling agent for bread and cake mixes, Dough viscoelasticity improver, pH buffer, powdered drink acid, toothpaste base, animal feed additive,
It is used as a resin stabilizer, a phosphor additive, a glass additive, an auxiliary carrier for pharmaceutical preparations, an abrasive, and the like. Calcium sulfoaluminate is used as a cement expansive material, a coated pigment for papermaking, and the like.

As a production method, calcium carbonate is produced by blowing carbon dioxide gas into lime milk which is an aqueous suspension of calcium hydroxide (Japanese Patent Publication No. 37-519, Japanese Patent Publication No. 47-22944, Japanese Patent Publication No. 47-22944). Japanese Patent Publication No. 56-40118) is known. Calcium phosphate is a method of producing α-type tricalcium phosphate, and then performing an underwater conversion reaction of a phosphate compound in a system in which agar or sodium dodecylbenzenesulfonate is added to produce fine crystal aggregate particles (Takafumi Kanazawa Editing, Inorganic Phosphorus Chemistry, 168-1
70) Alternatively, a method of reacting lime milk with an aqueous phosphoric acid solution while grinding, or a method of producing fine hydroxyapatite which is calcium phosphate by mixing and then carrying out a grinding reaction (Japanese Patent Publication No. 62-4324). Are known. For calcium sulfoaluminate, there is a method (Japanese Unexamined Patent Publication No. 53-14692) in which an aqueous solution of lime milk and aluminum sulfate is continuously mixed and reacted at about 40 ° C. with a high-speed, high-shear mixing agitator. Are known.

These methods are based on the dispersibility indicating the particle size of the powder filler dispersed in rubber, plastics, paints, inks, etc., and the powder filler obtained by drying the slurry filler in a solvent. Strict temperature control of the reaction system, addition of a third substance such as an organic substance or an inorganic substance, in order to improve the properties such as redispersibility that indicates the degree of dispersion when the agent is dispersed again in the solvent. The crystal grain size and crystal grain shape are controlled by mechanochemical reaction such as grinding and high shearing force. However, this has a problem that the number of manufacturing steps increases and the cost increases.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that these calcium compounds contain β-2,1-bonded fructose polymers having glucose at the reducing end. By using a complex calcium compound with saccharides, the crystal particle diameter and crystal particle shape are controlled, and a calcium-based filler having excellent dispersibility and redispersibility is obtained, and ink, paint, rubber, plastic, paper , And found to be useful as a filler for cosmetics, foods, pharmaceuticals, etc. Furthermore, for the first time, the calcium compound can be easily synthesized by adding a saccharide containing a β-2,1-bond fructose polymer having glucose at the reducing end to various reactions using an aqueous suspension of calcium hydroxide as a raw material. Heading out, the present invention has been completed.

That is, the gist of the present invention is to provide a calcium-based filler containing a calcium compound treated with a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end as an active ingredient, and calcium hydroxide. And a carbonic acid gas or a mineral acid or a salt thereof in the presence of a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end. .

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The calcium compound in the present invention means calcium carbonate, calcium dihydrogen phosphate, calcium hydrogen phosphate, tricalcium phosphate, hydroxyapatite, fluoroapatite, etc. which are synthesized from lime milk which is an aqueous suspension of calcium hydroxide. Examples thereof include calcium phosphate and calcium sulfoaluminate.

The saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end used in the present invention is not particularly limited, and examples thereof include inulin. Inulin is a β-2,1-bonded fructan having glucose at the reducing end and having a molecular weight of about 5000, which is obtained from rhizomes of Jerusalem artichoke, chicory, dahlia, and the like.
It is commercially available.

The complex calcium compound of the present invention comprises the calcium compound and β-2, which has glucose at the reducing end.
A composite particle composed of a saccharide containing a 1-bond fructose polymer, and preferably a composite particle in which a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end is attached to the particle surface of a calcium compound. .

The complex calcium compound of the present invention is obtained by allowing a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end to be present in the production of the calcium compound, and preferably the above-mentioned compound. When a calcium compound is produced by a precipitation reaction from an aqueous suspension of calcium hydroxide as a calcium raw material of the calcium compound, the precipitation reaction system contains a β-2,1-bonded fructose polymer having glucose at the reducing end. It is obtained by precipitating a calcium compound in the presence of sugar.

Specifically, an aqueous suspension of calcium hydroxide as a calcium raw material of the above-mentioned calcium compound and a β-2,1-bonded fructose polymer having carbon dioxide gas or a mineral acid or a salt thereof having glucose at the reducing terminal. It is obtained by reacting in the presence of a saccharide containing The mineral acid or salt thereof used in the present invention is selected according to the calcium compound to be produced, and examples thereof include phosphoric acid, ammonium dihydrogen phosphate, triammonium phosphate, aluminum sulfate and the like.

The calcium-based filler obtained in the present invention may be used as the reaction solution after completion of the reaction as it is, or in a paste state by dehydrating the reaction solution. Further, the reaction solution may be dried, pulverized and classified to give a powdery product. Hereinafter, specific embodiments of the method for producing a complex calcium compound will be described. (1) Synthesis of Calcium Carbonate The method for producing calcium carbonate by blowing carbon dioxide gas into lime milk can be classified into two types depending on the conditions of carbonation. As a normal condition, one is cubic particles called colloidal calcium carbonate having an average particle size of 0.1 μm or less, which is usually used in lime milk having a calcium hydroxide concentration of 15% or less at a compounding start temperature of 25 ° C. or less. The carbon dioxide gas can be reacted at a blowing rate of 2.0 L / min or more in terms of 100% carbon dioxide gas per 1 kg of calcium hydroxide. On the other hand, spindle-shaped particles called light calcium carbonate having an average particle diameter of 0.5 μm or more are added to lime milk having a calcium hydroxide concentration of 15% or more and a compounding start temperature of 25 ° C.
With the above, carbon dioxide gas is 10 per 1 kg of calcium hydroxide.
The reaction can be performed at a blowing rate of 2.0 L / min or less in terms of 0% carbon dioxide gas. In the present invention, lime milk, without particularly controlling the compounding temperature, the blowing rate of carbon dioxide, etc.
Preferably, a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end is added to lime milk having a calcium hydroxide concentration of 4 to 20% by weight per 0.1 part by weight of the calcium hydroxide. Add ~ 30 parts by weight,
The desired composite calcium carbonate particles are obtained by stirring well and forming a uniform slurry and then carbonating. (2) Synthesis of calcium phosphate Hydroxyapatite, which is a kind of calcium phosphate, usually has a Ca / P molar ratio of about 1.6 to 1.7 while stirring lime milk having a calcium hydroxide concentration of 4 to 20% by weight (stoichiometric amount). The theoretical molar ratio can be obtained by a wet compounding method in which an aqueous solution of phosphoric acid or its salt is gradually added until it reaches 1.67). The saccharide containing the β-2,1-bonded fructose polymer having glucose at the reducing end is added to lime milk in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of calcium hydroxide. The addition method is preferably such that saccharides containing a β-2,1-bonded fructose polymer having glucose at the reducing end are added to lime milk, stirred well to form a uniform slurry, and then phosphorylated. By such a method, fine acicular composite hydroxyapatite particles can be obtained. (3) Synthesis of calcium sulfoaluminate Calcium sulfoaluminate is usually CaO / CaO / aluminum sulfate aqueous solution having an aluminum sulfate concentration of about 5 to 30% by weight in lime milk having a calcium hydroxide concentration of about 4 to 20% by weight. It can be obtained by adding Al ₂ O _{3 in} a molar ratio of 6 to 8 and reacting. Β with glucose at the reducing end
The saccharide containing a -1,2-bonded fructose polymer is added to lime milk in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of calcium hydroxide. As a method of addition, it is preferable to add saccharide containing β-2,1-bonded fructose polymer having glucose at the reducing end to lime milk, stir well to form a uniform slurry, and then add aluminum sulfate. By this method, fine acicular composite calcium sulfoaluminate particles can be obtained.

[0013]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. <Example 1> 6% by weight in a 2 L stainless beaker
To 1000 g of concentrated lime milk, 4.1 g of 10 wt% inulin (manufactured by Tenen Sugar Co., Inulin LS) was added with stirring, and the mixture was stirred and mixed for 10 minutes.
Carbon dioxide gas having a concentration of 30% was blown at 7 ° C at a rate of 0.3 L / min, and the reaction was continued until the conductivity of the suspension secondarily dropped and became stable. The reaction liquid was suction filtered with a Nutsche, the mother liquor was separated, and then dried and pulverized to obtain calcium carbonate particles.
The calcium carbonate particles have a BET specific surface area of 25 m ^2.
/ G of colloidal particles. BET specific surface area is N ₂
The measurement was carried out by a gas adsorption method (apparatus used: Flow soap II2300 manufactured by Micromeritics).

Further, the loss on heating of inulin up to the complete thermal decomposition temperature of 500 ° C. was measured and found to be 3.1%.
In addition, the heating loss is a high temperature type differential heat manufactured by Seiko Electronics
A thermal mass measurement device TG / DTA320 type was used to determine the heating loss from room temperature to 500 ° C. <Examples 2, 3 and Comparative Example 1> Under the conditions shown in Table 1, Example 2 is an inulin of Example 1 (manufactured by Tenen Sugar Co., Ltd.,
Inulin LS is an inulin (manufactured by Koskra, Inulin L
T), Example 3 was added with inulin (manufactured by Tenen Sugar Co., Inulin LS) in the same manner as in Example 1, and Comparative Example 1 was prepared in the same manner as in Example 1 without adding inulin. To obtain calcium carbonate particles.

The difference between the weight loss on heating shown in Examples 1 and 2 and the weight loss on heating in Comparative Example 1 when heated to 500 ° C., which is the temperature at which inulin is completely decomposed below the decomposition temperature of calcium carbonate, is Adhesion (physical or chemical adsorption) to composite calcium carbonate particles obtained by drying and pulverizing in examples
The amount of inulin that is being used is shown. It can be seen that the calcium carbonate particles of the present invention have an improved particle size as compared with the BET specific surface area and that they contain inulin due to the loss on heating.

[0016]

[Table 1]

Example 4 In a 2 L stainless beaker, 710 g of 10% by weight lime milk was added with stirring 5 g of 10% by weight aqueous solution of inulin (Inulin ST manufactured by Koskra) and stirred for 10 minutes. After mixing, 42.
133 g of a 5% strength phosphoric acid aqueous solution was gradually added over about 30 minutes. After that, the reaction solution was heated to 80 ° C., and was heated and maintained for 24 hours while continuing stirring to perform aging. The reaction solution is suction filtered with a nutsche, the mother liquor is separated, dried and ground,
Hydroxyapatite particles were obtained. The hydroxyapatite particles are needle-like particles having a BET specific surface area of 92 m ² / g, and have a sedimentation volume of 32 m after standing for 1 hour at a particle concentration of 1%.
l.

The sedimentation volume means that 1 g of the obtained particles and 99 g of ion-exchanged water are put into a 100 ml stoppered sedimentation tube, shaken vigorously for 20 seconds to uniformly mix the contents, and allowed to stand for 1 hour. It is a reading of the settling volume (ml) scale. <Examples 5 and 6 and Comparative Example 2> Under the conditions shown in Table 2, Example 4 was carried out by changing the inulin of Example 3 (manufactured by Koskra, Inulin ST) to inulin (manufactured by Koscler, Inulin LT). In Example 5, the inulin of Example 3 (manufactured by Koskra, Inulin ST) was changed to inulin (manufactured by Tenen Sugar, Inulin LS), and in Comparative Example 2, inulin was not added, and the same production as in Example 3 was performed. Hydroxyapatite particles were obtained by the method. FIG. 1 shows the particle shape (transmission electron micrograph (× 5000)) obtained in Example 6, and FIG. 2 shows the particle shape (transmission electron micrograph (× 5000)) obtained in Comparative Example 2. .

It can be seen that the hydroxyapatite particles of the present invention have improved dispersibility as compared with the sedimentation volume.

[0020]

[Table 2]

Example 7 In a 500 ml stainless beaker, 1.9 g of a 10 wt% aqueous solution of inulin (Inulin LT manufactured by Koscler) was added to 68 g of 13 wt% lime milk while stirring. After stirring and mixing for 10 minutes, an aluminum sulfate aqueous solution having a concentration of 8% at a temperature of 50 ° C. 6
4 g were added. Then, while continuing stirring, the mixture was heated at 50 ° C. for 1 hour for aging. The reaction solution was suction filtered with a nutsche, the mother liquor was separated, and the mixture was dried and pulverized to obtain calcium sulfoaluminate particles. The calcium sulfoaluminate particles produced at this time have a BET specific surface area of 20 m ² / g,
Observation by transmission electron microscope: major axis 1.0 μm, minor axis 0.05
The particles were acicular particles with a mean of μm. <Example 8 and Comparative Example 3> Under the conditions shown in Table 3, Example 8 is the same manufacturing method as Example 4, and Comparative Example 3 is the same manufacturing method as Example 4 without the addition of inulin. To obtain calcium sulfoaluminate particles.

[0022]

[Table 3]

<Application Example 1> Redispersibility in water 2 g of the calcium carbonate particles obtained in Example 3 and 98 g of ion-exchanged water were placed in a 100 ml stoppered sedimentation tube, and 2
After vigorously shaking for 0 seconds to uniformly mix the contents, the mixture was allowed to stand and the sedimentation volume (ml) scale was read after 1, 3 and 24 hours, and the redispersibility and dispersion stability of the particles were examined. As a comparative sample, the physical properties of a commercially available colloidal calcium carbonate (manufactured by Shiraishi Industry Co., Ltd.) were also measured. Table 4 shows the results.

The evaluation criteria of redispersibility are shown below. ⊚: After re-dispersion, the sample was left undisturbed for 3 hours, and the supernatant could not be obtained. ○: After re-dispersion, it was left undisturbed for 1 hour, and could not be supernatant. Those having a sedimentation volume of 2 ml or less after standing for 1 hour after dispersion The evaluation criteria for dispersion stability are shown below.

◯: What is left undisturbed for 24 hours after re-dispersion and cannot be supernatant. Less than 2 ml

[0026]

[Table 4]

<Application Example 2> Redispersibility in food (application to calcium-fortified milk) 175 g of calcium carbonate particles obtained in Example 2 and sterilized water 326 in a 1000 ml stainless beaker.
g, dispa (blade diameter 50 mm, 5000 rpm
The mixture was stirred for 30 minutes) to redisperse the calcium carbonate particles in water to obtain a calcium carbonate slurry. Into another stainless beaker, collect 496.4 ml of raw milk,
After adding 3.6 g of the 35 wt% calcium carbonate slurry obtained by the above redispersion, the mixture was stirred and dispersed by a high-pressure homogenizer (150 Kg / cm ² ) to obtain 500 ml of homogeneous calcium-fortified milk. With respect to this calcium-fortified milk, the dispersion stability of calcium carbonate was examined.
As a comparative sample, the commercially available calcium carbonate for food additives was similarly examined for the dispersion stability of calcium carbonate. As the evaluation standard of dispersion stability, the dispersion stability was determined by the following centrifugal sedimentation test.

Take 50 ml of trial milk in a centrifuge tube and
After applying a centrifugal force of G × 15 minutes, discard the upper layer, drain well, dry the sediment remaining at the bottom of the centrifuge tube at 95 ° C. until a constant weight is reached, and weigh it. The dispersion stability is calculated by the formula.

[0029]

[Table 5]

[0030]

INDUSTRIAL APPLICABILITY According to the present invention, when a calcium compound is produced, a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end is added to obtain a particle size of the compound. The crystal form can be controlled, and it can be used as a filler having excellent dispersibility and redispersibility.

[Brief description of the drawings]

FIG. 1 is a photograph (transmission electron micrograph (× 5000)) showing the shape of hydroxyapatite particles obtained in Example 6 instead of a drawing.

FIG. 2 is a photograph (transmission electron micrograph (× 5000)) showing the shape of hydroxyapatite particles obtained in Comparative Example 2 instead of a drawing.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kiai Sawanoi 6-26 Nagisa-cho, Nishinomiya-shi, Hyogo

Claims (14)

[Claims] 1. A calcium-based filler comprising, as an active ingredient, a complex calcium compound composed of a calcium compound and a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end. 2. The calcium-based filler according to claim 1, which comprises a complex calcium compound having a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end attached to the surface of the calcium compound as an active ingredient. 3. β-2,1 having glucose at the reducing end
The calcium-based filler according to claim 1 or 2, wherein the saccharide containing a bound fructose polymer is inulin. 4. The calcium compound is calcium carbonate,
The calcium-based filler according to any one of claims 1 to 3, which is calcium phosphate or calcium sulfoaluminate. 5. A method for producing a calcium compound from an aqueous suspension of calcium hydroxide by a precipitation reaction, wherein β-2,1 having glucose at the reducing terminal in the precipitation reaction system.
A method for producing a complex calcium compound, wherein a saccharide containing a bound fructose polymer is present. 6. An aqueous suspension of calcium hydroxide is reacted with carbon dioxide gas or a mineral acid or a salt thereof in the presence of a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end. A method for producing a complex calcium compound, comprising the steps of: 7. β-2,1 having glucose at the reducing end
The amount of the saccharide containing the bound fructose polymer added is 0.1 to 3 with respect to 100 parts by weight of calcium hydroxide.
It is 0 weight part, The manufacturing method of Claim 5 or 6 characterized by the above-mentioned. 8. β-2,1 having glucose at the reducing end
8. The method according to claim 5, wherein the saccharide containing the bound fructose polymer is inulin. 9. The calcium hydroxide concentration is 4 to 20% by weight.
After adding 0.1 to 30 parts by weight of a saccharide containing a β-2,1-bonded fructose polymer having glucose at the reducing end to 100 parts by weight of calcium hydroxide, a uniform slurry was obtained. A method for producing composite calcium carbonate particles, comprising the step of adding carbon dioxide gas or carbonate to the slurry. 10. β-2 having glucose at the reducing end,
The method for producing composite calcium carbonate particles according to claim 9, wherein the saccharide containing a 1-bond fructose polymer is inulin. 11. β-2,1 having lime milk having a calcium hydroxide concentration of 4 to 20% by weight and glucose at the reducing end.
0.1 to 30 parts by weight of a saccharide containing a bound fructose polymer is added to 100 parts by weight of calcium hydroxide to form a uniform slurry, and an aqueous solution of phosphoric acid or a salt thereof is gradually added while stirring the slurry. A method for producing composite hydroxyapatite particles, which comprises the step of adding and reacting. 12. β-2 having glucose at the reducing end,
The method for producing hydroxyapatite particles according to claim 11, wherein the saccharide containing a 1-bond fructose polymer is inulin. 13. A lime milk having a calcium hydroxide concentration of about 4 to 20% by weight, and β-having glucose at the reducing end.
A saccharide containing a 2,1-linked fructose polymer,
After adding 0.1 to 30 parts by weight to 100 parts by weight of calcium hydroxide to form a uniform slurry, while stirring the slurry, an aqueous solution of aluminum sulfate having an aluminum sulfate concentration of about 5 to 30% by weight is added to CaO / Al. _A method for producing composite calcium sulfoaluminate particles, which comprises the step of adding and reacting so that the molar ratio of ₂ O ₃ becomes 6 to 8. 14. β-2 having glucose at the reducing end,
The method for producing composite calcium sulfoaluminate particles according to claim 13, wherein the saccharide containing a 1-bond fructose polymer is inulin.