JP2000345068A - Filling calcium carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide filling calcium carbonate excellent in dispersibility to polymeric materials and, at the same time, capable of imparting viscosity stability to polymeric materials. SOLUTION: The surface of a calcium carbonate particle is coated with a first treating agent containing at least one of a fatty acid, its derivative, a resin acid, and its derivative and further coated with a second treating agent containing a plasticizer. The first treating agent preferably contains at least one of a fatty acid, its metal salt and esterified product, a resin acid, and its mental salt and esterified product, and the second treating agent preferably contains at least one of a phthalic acid based plasticizer, a polyester based plasticizer, a sulfonic acid based plasticizer, and a phosphoric acid based plasticizer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel filling calcium carbonate.

[0002]

2. Description of the Related Art As an industrial application of calcium carbonate,
For example, it is used in many industrial fields as a filler for polymer materials such as plastics, rubber, ink, and sealing materials. For example, for sealing materials, plastics, rubber, etc., the viscosity characteristics (especially thixotropy), strength characteristics (especially tensile characteristics, impact strength, etc.) of the polymer material serving as the base material, and the adherend Used to improve adhesive strength to Further, with respect to ink and the like, it is used to improve the glossiness and the like of the coating film.

[0003] When calcium carbonate is used as a filler as described above, calcium carbonate is subjected to a surface treatment with a fatty acid, rosin acid or the like as necessary for the purpose of imparting various functions to the calcium carbonate. .

However, the above-mentioned surface-treated calcium carbonate causes another problem. That is, in order to uniformly disperse this in a polymer material, kneading must be performed for a long time with a high share, which causes a decrease in productivity and an increase in production cost.

[0005] In addition, the composition containing the surface-treated calcium carbonate may change over time in properties such as viscosity characteristics and thixotropy. For example, if these changes occur in the sealing material, poor productivity during the production of the sealing material, poor workability during the application of the sealing material (when used),
Problems such as sagging occur. Similar problems also occur when surface-treated calcium carbonate is mixed with plastics or the like.

[0006]

If calcium carbonate can be easily dispersed in various polymer materials and a stable viscosity characteristic can be ensured even in a composition containing the same, not only quality improvement but also production Simplification of the production process,
It also leads to improved workability during construction.

Accordingly, a main object of the present invention is to provide a calcium carbonate for filling which has excellent dispersibility in a polymer material and can impart excellent viscosity stability to the polymer material.

[0008]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that calcium carbonate having a specific surface treatment can achieve the above object. The present invention has been completed.

That is, according to the present invention, the surface of calcium carbonate particles is coated with (1) a first treating agent containing at least one of a fatty acid and a derivative thereof and a resin acid and a derivative thereof, and further contains (2) a plasticizer. The present invention relates to a calcium carbonate for filling which is coated with a second treating agent.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the calcium carbonate for filling of the present invention, the surface of calcium carbonate particles is coated with (1) a first treating agent containing at least one of a fatty acid and a derivative thereof and a resin acid and a derivative thereof. (2) It is coated with a second treating agent containing a plasticizer. That is, the present invention has at least a first layer made of the first treatment agent and a second layer made of the second treatment agent.

The calcium carbonate is not particularly limited, and a commercially available product can be used. Further, those obtained by any of the production methods can be used. Therefore, in the present invention, both natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (light calcium carbonate or colloidal calcium carbonate) can be used. The former is manufactured by mechanically pulverizing and classifying a rough limestone to a desired particle size. The latter uses raw limestone as coke or petroleum-based fuel (heavy oil, light oil), natural gas, LPG
Once mixed to produce calcium oxide (quicklime), which is then reacted with water to produce calcium hydroxide (slaked lime)
The carbon dioxide gas generated during firing is reacted with calcium hydroxide to obtain a desired particle size and particle shape.

The average particle size of calcium carbonate (particles) can be appropriately set according to the use of the final product.
Usually, the primary particle diameter is about 0.01 to 10 μm, preferably 0.02 to 3.0 μm, and most preferably 0.02 to 3.0 μm.
What is necessary is just to use the thing of the range of 0.5 micrometer. Further, those having a primary particle diameter in the range of 0.01 to 10 μm in which 80% by weight or more of the surface-treated calcium carbonate particles can be suitably used.

The first layer is formed by coating the surface of calcium carbonate particles with a first treating agent containing at least one of a fatty acid and a derivative thereof and a resin acid and a derivative thereof.

The first treating agent contains at least one selected from fatty acids and derivatives thereof and resin acids and derivatives thereof. The first treatment agent may contain other components such as various solvents and additives as needed, as long as the effects of the present invention are not impaired.

The fatty acid or a derivative thereof is not particularly limited. For example, a fatty acid, a metal salt thereof, an esterified product thereof and the like can be preferably used. Examples of the fatty acid include caproic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, palmitoleic acid, oleic acid, and erucic acid. Examples of the metal salt include alkali metal salts such as sodium salt and potassium salt of the above fatty acid, and alkaline earth metal salts such as magnesium salt and calcium salt. Examples of the esterified product include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate and the like. These can be used alone or in combination of two or more. Among these, fatty acids having 6 to 31 carbon atoms and derivatives thereof can be preferably used.

The resin acid and its derivative are not particularly limited, but, for example, resin acid, its metal salt, its esterified product and the like can be suitably used. As resin acid,
For example, abietic acid, repopimaric acid, neoabieticenic acid, palustric acid, dehydroapietic acid, dihydroabietic acid, tetraabietic acid, dextropimalic acid, isodextropimaric acid and the like can be mentioned. Examples of the metal salt include alkali metal salts such as sodium salt and potassium salt of the above-mentioned resin acid, and alkaline earth metal salts such as magnesium salt and calcium salt. In addition to these, examples of resin acid derivatives include hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin ester, maleated rosin, maleated rosin ester, and rosin-modified phenol.

The amount of coating with the first treating agent can be appropriately determined according to the properties of the calcium carbonate, the type of fatty acid, etc., but usually, the fatty acid and its derivative and the resin acid and At least one derivative thereof is about 0.1 to 30 parts by weight, preferably 0.2 to 20 parts by weight, more preferably 0.2 to 30 parts by weight.
What is necessary is just to make it 5 weight part.

Usually, in the first layer, some or all of at least one of the fatty acid and its derivative and the resin acid and its derivative in the first treating agent reacts with calcium carbonate to produce fatty acid calcium and the like. Unreacted substances may be present as long as the effects of the present invention are achieved.

The method for forming the first layer is not particularly limited as long as the surface of the calcium carbonate particles can be coated with the first treating agent. For example, coating can be performed by preparing a slurry of calcium carbonate in advance, blending the slurry with a first treating agent, and mixing and kneading.

The above slurry can be prepared by dispersing calcium carbonate (powder) in a solvent such as water, toluene, xylene, hexane or the like. The amount of dispersion (slurry concentration: solid content) in this case is not particularly limited, but may be usually about 0.1 to 50% by weight, preferably 1 to 20% by weight.

When the first treating agent is blended, stirring can be performed as required. The stirring may be performed by a known stirrer, mixer, or the like. In addition, the temperature (liquid temperature) in the case of compounding is not particularly limited, and it is usually good to be about 10 to 80 ° C.

After compounding the first treating agent, the solid content may be collected according to a known solid-liquid separation method such as filtration and centrifugation, if necessary, or the solid content may be dried and pulverized if necessary. And the like. These operations may be performed under known conditions. In the present invention, any of the slurry after blending the first treating agent, the wet cake after solid-liquid separation, and the solid after drying can be treated with the second treating agent.

Next, the surface is treated with a second treating agent containing a plasticizer to form a second layer. The second processing agent may contain other components in addition to the plasticizer as long as the effects of the present invention are not impaired.

The plasticizer is not particularly limited, and a known or commercially available plasticizer can be used. In the present invention,
In particular, plasticizers such as phthalic acid plasticizers, polyester plasticizers, sulfonic acid plasticizers, and phosphoric acid plasticizers can be suitably used. Examples of the phthalic acid-based plasticizer include di-ethylhexyl phthalate (DOP), dimethyl phthalate (DMP), and diisononyl phthalate (DIN).
P), dibutyl phthalate (DBP), diisodecyl phthalate (DlDP) and the like. Examples of the polyester plasticizer include propyl polyadipate and propyl polysebacate. Examples of the sulfonic acid-based plasticizer include benzenesulfonic acid butylamide. Examples of the phosphate plasticizer include tricresyl phosphate, trioctyl phosphate, triphenyl phosphate, and the like. These plasticizers can be used alone or in appropriate combination of two or more kinds.

The amount of coating with the second treating agent can be appropriately determined according to the properties of the calcium carbonate to be used, the type of plasticizer, and the like. Usually, the amount of the plasticizer is 0.01 to 100 parts by weight based on 100 parts by weight of calcium carbonate. About 30 parts by weight, preferably 0.05 to 20 parts by weight, more preferably 0.1 to
What is necessary is just to make it 5 weight part.

In the calcium carbonate for filling of the present invention,
Other layers may be included in addition to the first layer and the second layer as long as the effects of the present invention are not hindered. For example, another layer may be interposed between the first layer and the second layer.

The method for forming the second layer is not particularly limited as long as the second layer can be formed on the first layer. For example, the method of adding and mixing the second processing agent to any of the slurry after the first processing agent blending, the wet cake after the solid-liquid separation, and the solid after the drying, spraying the second processing agent Either a method of applying to the solid content, or a method of contacting the vaporized second treatment agent with the solid content may be used.

After coating with the second treating agent, the solid content may be recovered according to a known solid-liquid separation method such as filtration and centrifugation, and if necessary, the solid content may be subjected to treatment such as drying and grinding. May be applied. These operations may be performed under known conditions. The particle size after the formation of the second layer may be appropriately set according to the use of the final product.

The calcium carbonate of the present invention is excellent for filling various materials, and is particularly suitable for filling polymer materials. The amount of calcium carbonate to be filled may be appropriately set according to the type of the matrix material, the use of the final product, and the like.

[0030]

According to the present invention, the first layer is formed by surface treatment with one or more selected from fatty acids or derivatives thereof, or resin acids or derivatives thereof, and the surface is treated with a plasticizer to form a second layer. By forming a layer, it can function particularly effectively as a filler (particularly, a filler for a polymer material).

In the case where there is no first layer and only the second layer, that is, the surface-treated calcium carbonate surface-treated only with a plasticizer has a strong cohesiveness after unpulverized powder and is mixed with various polymer materials. In addition, they have poor dispersibility and cannot give excellent viscosity characteristics, for example, thixotropic properties, to the compounded polymer materials. Moreover, the mechanical strength of the polymer material containing the calcium carbonate is deteriorated.

Also, when only the first layer is used, similarly to the case where only the second layer is used, the dispersibility is deteriorated, and thixotropic properties and the like cannot be given to the compounded polymer material.

[0033]

Since the calcium carbonate of the present invention is covered with specific first and second layers, it has excellent dispersibility in various polymer materials. Further, the polymer material in which the calcium carbonate of the present invention is dispersed has excellent viscosity stability, and the change with time is effectively suppressed. Therefore, it is useful for filling (particularly for filling a polymer material).

That is, according to the calcium carbonate for filling of the present invention, it can be easily dispersed in plastics, rubbers, inks, sealing materials and the like, and the composition can have excellent stability in viscosity characteristics.

[0035]

The present invention will now be described more specifically with reference to examples and comparative examples.

Example 1 Slurry 10 of synthetic calcium carbonate having a solid content of 10% by weight
The kg was adjusted to 65 ° C. and the slurry was stirred with a disperser while the saponified oleic acid content was 75% by weight, the saponified stearic acid content was 11% by weight, and the saponified palmitic acid content was 14% by weight. Was added and stirred for 5 minutes, followed by press dewatering. The resulting dehydrated cake is dried and then pulverized, whereby about 1 calcium carbonate surface-treated with the fatty acid mixture is obtained.
kg was obtained. Dimethyl phthalate (DMP) 3 vaporized by heat while dispersing 1 kg of this surface-treated calcium carbonate with a dry disperser (Henschel mixer)
By spraying g, approximately 1 kg of calcium carbonate surface-treated with the fatty acid mixture and further surface-treated with dimethyl phthalate (DMP) was obtained.

Example 2 Dioctyl phthalate (DO) was used in place of dimethyl phthalate
About 1 kg of calcium carbonate surface-treated with a fatty acid mixture and dioctyl phthalate was obtained in the same manner as in Example 1 except that P) was used.

Example 3 Dibutyl phthalate (DBP) in place of dimethyl phthalate
Approximately 1 kg of calcium carbonate surface-treated with a mixture of fatty acids and dibutyl phthalate was obtained in the same manner as in Example 1 except for using.

Comparative Example 1 Example 1 was repeated except that the surface treatment by DMP was not performed.
About 1 kg of surface-treated calcium carbonate was obtained in the same manner as described above.

Comparative Example 2 Approximately 1 kg of surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that the surface treatment with the fatty acid mixture was not performed.

Test Example 1 A dispersibility and viscosity stability test for dioctyl phthalate (DOP) was performed.

100 parts by weight of the surface-treated calcium carbonate obtained in Examples and Comparative Examples and 100 parts by weight of a plasticizer, dioctyl phthalate (DOP), were mixed by stirring with a planetary mixer at a low shear for 20 minutes under reduced pressure. To prepare a DOP sol.

For each DOP sol, the degree of dispersion of the surface-treated calcium carbonate was measured. The degree of dispersion is the DOP obtained
The number of non-dispersed surface-treated calcium carbonate particles contained in the sol was visually examined. First, a black paper was coated with a DOP sol after the addition of surface-treated calcium carbonate using a 500 μm applicator, and the number of particles of 10 μm or more contained in 5 cm square on the coated surface was examined. Table 1 shows the results.

Further, the initial viscosity of the DOP sol and the viscosity after storage at 20 ° C. for 7 days were measured, and the changes were examined. The viscosity was measured at a temperature of 20 ° C. using a BH viscometer (TO
(Manufactured by KIMEC) under the conditions of 2 rpm and 20 rpm. The value of the rate of increase is represented by a relative value (%), and the viscosity of the DOP sol before storage (the initial viscosity of the DOP sol) is 1
The value is set to 00%. Table 1 shows the results.

[0045]

[Table 1]

From the results shown in Table 1, it can be seen that when the product of the present invention is blended with DOP, a composition which is easily dispersed in DOP and has a small change in viscosity can be obtained. From this,
It can be seen that an excellent effect can be exhibited as a filler (dispersing material) for a material containing DOP or the like (for example, a sealing material).

Test Example 2 A test for dispersibility and viscosity stability in polyvinyl chloride (PVC) was performed.

Table 2 was prepared in the same manner as in Test Example 1 except that the surface-treated calcium carbonate obtained in Examples and Comparative Examples was used.
Was prepared. In Table 2, polyamidoamine was used as an adhesion-imparting agent, and mineral terpene (A solvent) was used as a diluent.

[0049]

[Table 2]

The degree of dispersion of the surface-treated calcium carbonate was measured for each PVC sol. The degree of dispersion is determined by the obtained PVC
The number of non-dispersed surface-treated calcium carbonate particles contained in the sol was visually examined. First, a PVC sol after the surface treatment of calcium carbonate was applied to a black paper with a 500 μm applicator, and the number of particles of 10 μm or more contained in a 5 cm square of the coated surface was examined. Table 3 shows the results.

The initial viscosity of the PVC sol and the viscosity after storage at 45 ° C. for 7 days were measured, and the changes were examined. The viscosity was measured at a temperature of 20 ° C. using a BH viscometer (TO
(Manufactured by KIMEC) under the conditions of 2 rpm and 20 rpm. Table 3 shows the results. The value of the rate of increase is expressed as a relative value (%), and the viscosity of the PVC sol before storage (PV
(Initial viscosity of C sol) is 100%.

[0052]

[Table 3]

From the results shown in Table 3, it can be seen that when the product of the present invention is blended with PVC, a composition which is easily dispersed in PVC and has a small change in viscosity can be obtained.

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Claims (7)

[Claims] 1. The surface of calcium carbonate particles is coated with a first treating agent containing at least one of (1) a fatty acid and a derivative thereof and a resin acid and a derivative thereof, and (2) a second treating agent containing a plasticizer. Filling calcium carbonate coated with. 2. The calcium carbonate for filling according to claim 1, wherein the first treating agent contains at least one of a fatty acid, a metal salt thereof and an ester thereof, and a resin acid, a metal salt thereof and an ester thereof. 3. The calcium carbonate for filling according to claim 1, wherein the second treating agent contains at least one of a phthalic acid plasticizer, a polyester plasticizer, a sulfonic acid plasticizer and a phosphoric acid plasticizer. 4. The method according to claim 1, wherein the coating amount of at least one of the fatty acid and its derivative and the resin acid and its derivative is 0.1 to 30 parts by weight based on 100 parts by weight of calcium carbonate. The calcium carbonate for filling as described. 5. The calcium carbonate for filling according to claim 1, wherein the coating amount of the plasticizer is 0.01 to 30 parts by weight based on 100 parts by weight of calcium carbonate. 6. The method according to claim 1, wherein 80% by weight or more of the calcium carbonate particles surface-treated with the first and second treating agents have a primary particle size in the range of 0.01 to 10 μm. Calcium carbonate for filling. 7. The calcium carbonate for filling polymer material according to claim 1.