JP2011011924A - Calcium carbonate based filler for resin, covered with amorphous calcium phosphate and resin composition obtained by blending the filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a filler for resins, which is blended in an adhesive or a sealant to improve the adhesive strength and hot water resistance of the adhesive or the sealant and to provide a method for producing the filler for resins and a resin composition obtained by blending the filler for resins.SOLUTION: The calcium carbonate-based filler for resins is characterized in that the surface of a calcium carbonate particle is covered with amorphous calcium phosphate. The method for producing the calcium carbonate-based filler for resins and the resin composition obtained by blending the calcium carbonate-based filler for resins are provided.

Description

  The present invention relates to a resin filler, a method for producing the same, and a resin composition obtained by blending the resin filler. More specifically, the present invention relates to a workability, adhesive strength, and resistance to resistance by blending with an adhesive or sealant. The present invention relates to a resin filler capable of improving warm water, a method for producing the same, and a resin composition obtained by blending the resin filler.

  Conventionally, inorganic particles have been widely used as an extender for adhesives and sealants, or for viscosity adjustment, workability improvement, etc. Among them, calcium carbonate is used in large quantities as one of the cheapest inorganic particles. Yes. For example, as a tile adhesive, calcium carbonate particles of about several μm to 5 mm are blended for facilitating troweling and improving the design of the mat and the joint.

  Such calcium carbonate particles are required to have strong adhesion to the substrate in order to prevent detachment from the joint. For example, when a tile is bonded to a vertical wall, strong adhesive strength and quick drying must be maintained in order to prevent sliding off and falling. Furthermore, in order to prevent the resin from swelling due to moisture entering from the interface between the resin and the calcium carbonate particles and degrading the performance, airtight adhesion between the surface of the calcium carbonate particles and the resin is also required. In order to impart such properties to calcium carbonate particles, various surface treatments have been conventionally proposed.

  Among these, as the surface treatment with phosphoric acid, for example, a second calcium phosphate-calcium carbonate composite structure and a production method thereof have been proposed (Patent Document 1). However, in such a composite structure, the secondary calcium phosphate on the surface layer is rich in moisture, and further grows by taking in calcium carbonate particles, and may become giant plate-like particles. As a result, the adhesive strength may be lowered, so that it is not suitable when a high strength is required such as when a tile is adhered to a vertical wall.

  Further, for example, a method of forming a surface layer of second calcium phosphate by a surface treatment method in which heavy calcium carbonate particles are put in a Henschel mixer to suppress a temperature rise has been proposed (Patent Document 2). According to this method, calcium carbonate particles coated with a thin second calcium phosphate layer can be obtained which can improve whiteness and gloss when used as an extender for inks or paints or as a compounding agent for plastics. However, according to this method, in order to form the second calcium phosphate layer, it is necessary to form a paste with a lot of moisture, and therefore, a pulverization step is also required because of agglomeration after the drying step and drying. The reaction must be performed at a low temperature, which increases the cost. Moreover, since phosphoric acid takes in the heavy calcium carbonate particles and grows the particles, the particle size is larger than the original particle size, and some of the particles are likely to be coarse particles. When blended in a resin, the adhesive strength may be weakened.

  Furthermore, a porous calcium carbonate compound whose surface and porous portion are hydroxyapatite and a method for producing the same have been proposed (Patent Document 3). However, since this porous calcium carbonate compound has a large specific surface area and a high oil absorption, an appropriate viscosity cannot be maintained when the blending amount is large. In addition, a portion where hydroxyapatite crystallizes by taking in calcium carbonate particles may be coarse particles having a particle size several times larger than the original particles. Furthermore, since the surface of the calcium carbonate is exposed easily in the porous portion having a petal shape on the surface layer, the adhesive strength does not increase as expected.

JP-A-53-56174 JP-A-6-57167 Japanese Patent Laid-Open No. 7-223813

  In view of the above circumstances, the present inventors have a resin filler having a small particle diameter and a surface layer that is difficult to peel off, a method for producing the same, and an adhesive strength and warm water resistance that are blended with the resin filler. As a result of intensive studies on the resin composition, it was found that the problems described above can be solved by coating the surface of the calcium carbonate particles with an amorphous calcium phosphate layer, and the present invention has been completed.

  The present invention was made to achieve the above object, and claim 1 of the present invention includes a filler for a calcium carbonate resin characterized in that the surface of calcium carbonate particles is coated with amorphous calcium phosphate. And

  According to claim 2 of the present invention, by adding a phosphoric acid aqueous solution having a concentration of 5% or more to calcium carbonate particles and reacting with stirring at a temperature of 50 ° C. or higher, the surface of the calcium carbonate particles is reacted. The present invention includes a method for producing a filler for a calcium carbonate resin, wherein an amorphous calcium phosphate layer is formed at least partially.

  A third aspect of the present invention is the method for producing a filler for a calcium carbonate resin according to the second aspect, wherein the amount of phosphoric acid added is 0.05 to 5% by weight with respect to the calcium carbonate particles. Content.

  A fourth aspect of the present invention includes the method for producing a filler for a calcium carbonate resin according to the second or third aspect, wherein the concentration of phosphoric acid to be added is 10 to 50%.

  A fifth aspect of the present invention includes a resin composition comprising the calcium carbonate resin filler according to the first aspect mixed with a resin.

  Claim 6 of the present invention is characterized in that the resin is at least one selected from urethane epoxy resins, epoxy resins, modified silicone resins, modified silicone epoxy resins, silicone resins, polysulfide resins, and acrylic resins. The content is the resin composition described.

  A seventh aspect of the present invention includes the resin composition according to the sixth aspect, wherein the resin is an adhesive or a resin for a sealing material.

In the resin filler of the present invention, since the surface of the calcium carbonate particles is coated with amorphous calcium phosphate, the adhesion between the resin filler and the resin containing the filler is improved, and the adhesive strength, A synthetic resin composition excellent in warm water can be provided.
Moreover, according to the manufacturing method of the filler for resin of this invention, the filler for resin consisting of the calcium carbonate particle | grains coat | covered with the amorphous calcium phosphate can be manufactured efficiently.
Furthermore, since the resin in which the filler for resin is blended has high adhesive strength and excellent hot water resistance, it can be suitably used as an adhesive or sealant.
The reason why the resin filler of the present invention improves the adhesive strength and hot water resistance of the resin is not clear, but amorphous calcium phosphate contributes to the acceleration of resin curing, strengthens the interface with the resin, and is airtight. It is thought that this is caused by holding. For example, the reason why the warm water resistance is improved in the polysulfide sealant is considered to be that the adhesion at the filler particle resin interface is airtight and strong, so that the penetration of warm water is prevented and the swelling is suppressed.

FIG. 1 is an electron micrograph (10,000 times) of the filler for resin prepared in Example 10 of the present invention. FIG. 2 is an electron micrograph (10,000 times) of the resin filler whose surface prepared in Comparative Example 9 is coated with dicalcium phosphate. FIG. 3 is an electron micrograph (10,000 times) of the resin filler whose surface prepared in Comparative Example 10 is coated with hydroxyapatite. FIG. 4 is an X-ray diffraction pattern of the resin filler prepared in Example 10 of the present invention. FIG. 5 is an X-ray diffraction pattern of the resin filler prepared in Comparative Example 9. FIG. 6 is an X-ray diffraction pattern of the resin filler prepared in Comparative Example 10.

The filler for calcium carbonate resin of the present invention is characterized in that the surface of calcium carbonate particles is coated with amorphous calcium phosphate.
Moreover, the manufacturing method of the filler for calcium carbonate-type resin of this invention adds the phosphoric acid aqueous solution whose density | concentration is 5% or more to the calcium carbonate particle heated to 50 degreeC or more, and makes it react with stirring with a dry type. An amorphous calcium phosphate layer is formed on the surface of the calcium carbonate particles.
The calcium carbonate resin filler of the present invention includes not only the entire surface of the calcium carbonate particles but also a case where a part thereof is coated with amorphous calcium phosphate.

  The calcium carbonate used in the present invention is not particularly limited as long as it is a conventional calcium carbonate filler and can react with phosphoric acid. However, the surface-treated fine particle calcium carbonate produced by chemical synthesis called colloidal calcium carbonate is treated with a treatment agent that tends to aggregate during reaction with phosphoric acid and makes it less reactive with phosphoric acid. Therefore, it is preferable to avoid such a case.

  In general, light calcium carbonate and heavy calcium carbonate are well known as calcium carbonate, but these are preferable as the calcium carbonate particles of the present invention because they have good reactivity with phosphoric acid and are relatively difficult to aggregate. Can be used. Among these, heavy calcium carbonate from which products of various particle sizes can be obtained as a filler is preferable from the viewpoint of versatility and design. In the sealant application used for tiles and sand-like ceramic siding boards, calcite having a particle diameter of several millimeters called cold water sand can be suitably used as a raw material of the present invention in terms of design. Here, cold water sand is treated as being contained in heavy calcium carbonate.

  Heavy calcium carbonate refers to mechanically pulverized and classified natural calcium carbonate such as calcite (limestone, chalk, marble, etc.), shells, corals and the like. The method for pulverizing heavy calcium carbonate may be either wet or dry, but dry pulverization without a step that increases costs such as dehydration and drying is preferred. Specifically, commercially available granular calcium carbonate, cold water sand NO. A (trade name, manufactured by Maruo Calcium Co., Ltd.) or Super 3S (trade name, manufactured by Maruo Calcium Co., Ltd.), which is a commercially available heavy calcium carbonate, can be used. The particle diameter of the calcium carbonate particles used varies depending on the application, but for example, the granular particles used for improving workability (trowel handling) and suppressing dropping from the joints are preferably 100 to 3000 μm, more preferably 200 to 2000 μm. When the thickness is 100 μm or less, the thread drawing property tends to be deteriorated, and the workability tends to be deteriorated. When the thickness is 3000 μm or more, it tends to be detached from the joint portion. On the other hand, in the case of blending with an emphasis on adhesive strength, it is basically advantageous that the particle size is smaller, preferably 10 μm or less, more preferably 1 to 5 μm. If aggregation does not occur even if the thickness is less than 1 μm, the expected strength can be obtained, but aggregation is inevitable as long as dry treatment is performed.

  In the present invention, phosphoric acid (orthophosphoric acid) is added to the above calcium carbonate particles to form an amorphous calcium phosphate layer on the surface of the particles.

  The phosphoric acid used in the present invention is added to the calcium carbonate particles in the form of an aqueous solution, and the concentration of the added phosphoric acid aqueous solution is 5% or more, preferably 10% or more. If it is less than 5%, hydroxyapatite and dicalcium phosphate are liable to crystallize on the surface of the calcium carbonate particles, which not only increases the particle diameter but also deteriorates the adhesion between the resin and the filler, which is not preferable. In addition, although the phosphoric acid currently marketed is about 75% normally, if it is a granular material whose average particle diameter of a calcium carbonate particle is several hundred micrometers, it can be used without diluting. In the case of using calcium carbonate having an average particle size of several μm or less, it is preferable to use a 10 to 50% aqueous solution. If the surface treatment is performed at a higher concentration than that, phosphoric acid may not be coated on the entire particle, and phosphoric acid tends to become a binder and easily aggregate.

  In addition, the aqueous phosphoric acid solution forms an amorphous calcium phosphate layer uniformly, and in order to prevent crystallization of hydroxyapatite or dicalcium phosphate in an excessive portion of the aqueous phosphoric acid solution, it is gradually added by a method such as dripping or spraying. It is preferable to add.

The amount of phosphoric acid added is preferably 0.05 to 5% by weight, more preferably 0.2 to 3% by weight, based on the calcium carbonate particles. If the amount is less than 0.05% by weight, the amount of amorphous calcium phosphate formed on the particle surface is small, and the adhesiveness between the obtained filler and the resin tends to be small.
On the other hand, when the amount exceeds 5% by weight, phosphoric acid serves as a binder, and particularly when fine particle calcium carbonate is used, the particles tend to aggregate with each other, and the particle diameter of the obtained particles becomes large. There is a tendency to become smaller. Further, it is easy to form hydroxyapatite crystals as impurities, and unreacted phosphoric acid may deteriorate storage stability, and the surface treatment agent cost also increases.

  The reaction of the calcium carbonate particles and phosphoric acid in the present invention is carried out dry and while heating and stirring. The specific heating method and stirring method are not particularly limited, but a Henschel type mixer can be exemplified as a simple device that can satisfy such conditions. An amorphous calcium phosphate layer can be formed on the surface of the calcium carbonate particles by adding phosphoric acid diluted to a level that can be handled while stirring the calcium carbonate particles with a Henschel type mixer.

  About the reaction temperature at the time of surface treatment, it is necessary to set it as 50 degreeC or more. When the reaction temperature is less than 50 ° C., dicalcium phosphate is easily crystallized on the surface, which causes enlargement of the particle diameter and deterioration of adhesiveness with the resin. The upper limit of the reaction temperature is not particularly limited from the principle of the invention, and it is sufficient to evaporate the water sufficiently at 100 ° C. or higher. preferable.

  The dry type as used in the present invention may mean that there is a certain amount of water in the system, but the slurry is not in a slurry or paste form, but is treated with a water content such that the calcium carbonate particles behave as a powder and are easy to handle. . Of course, the resin filler of the present invention can also be produced by wet treatment in which phosphoric acid is added to calcium carbonate particles in a water slurry state, but costs are required for dehydration and drying, and phosphoric acid, calcium carbonate particles and When the treatment is carried out in an aqueous system rich in water intervening in this reaction, crystallization is likely to proceed, and second calcium phosphate and hydroxyapatite are easily formed. The water content in the system is preferably 10% by weight or less.

  As described above, in the production method of the present invention, the reaction temperature of phosphoric acid and calcium carbonate particles is kept sufficiently high, and the concentration of the phosphoric acid aqueous solution charged into the calcium carbonate particles is increased to cause a dry reaction. By reducing the amount of water intervening in the reaction system of phosphoric acid and calcium carbonate particles, the progress of crystallization of the second calcium phosphate and hydroxyapatite is suppressed.

The type of resin suitable for the resin filler of the present invention is not particularly limited, but urethane epoxy resin, epoxy resin, modified silicone resin, modified silicone epoxy resin, silicone resin, polysulfide resin, acrylic resin, and the like can be suitably used. .
The blending amount of the resin filler of the present invention with respect to these resins varies depending on the application, but is generally about 5 to 200 parts by weight with respect to 100 parts by weight of the resin. A method of blending a calcium carbonate filler can be used.

  In addition, when the filler for resin of this invention is mix | blended with the adhesive agent or resin for sealants, although adhesive strength improves notably, a modulus also becomes high in connection with it. Therefore, when high modulus becomes a problem, surface treatment is performed by using phosphoric acid together with a fatty acid or the like, or phosphoric acid is surface-treated using commercially available surface-treated calcium carbonate particles coated with a fatty acid or the like. By doing so, it is possible to balance the adhesive strength and the modulus.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, it cannot be overemphasized that this invention is not limited at all by these.

Example 1
Cold water sand NO. Which is a commercially available granular calcium carbonate. 7 kg of A (manufactured by Maruo Calcium Co., Ltd.) was put into a high speed mixer (FS-GS-10J type: manufactured by Fukae Kogyo Co., Ltd.) and stirred while heating. When the product temperature reached 50 ° C., 560 g of a 50% orthophosphoric acid aqueous solution was added to cold water sand NO. The mixture was gradually added to A (the amount of orthophosphoric acid added was 4% by weight of the amount of chilled sand NO.A), and stirring was continued until the product temperature reached 105 ° C. Thereafter, the product was taken out from the high speed mixer, left in the air and cooled to room temperature (about 20 ° C.) to prepare a resin filler.
The blades of the high-speed mixer were disk-shaped and operated with an agitator of 150 rpm and a chopper of 600 rpm, and 135 ° C. oil was circulated through the jacket.

Example 2
Resin filler as in Example 1, except that the concentration of the orthophosphoric acid aqueous solution was 40% and the addition amount was 175 g (the amount of added orthophosphoric acid was 1% by weight of the amount of the cold sand NO.A). Was prepared.

Example 3
The resin was used in the same manner as in Example 1 except that the concentration of the orthophosphoric acid aqueous solution was 30% and the addition amount was 70 g (the amount of orthophosphoric acid added was 0.3 wt% of the amount of chilled sand NO.A). A filler was prepared.

Example 4
6 kg of super 3S (manufactured by Maruo Calcium Co., Ltd .; specific surface area 12000 cm ² / g), a commercially available heavy calcium carbonate, is charged into a super mixer (SMG-20 type: manufactured by Kawata Co., Ltd.) and heated while being slow. (1000 rpm). When the product temperature reaches 50 ° C., 300 g of a 40% orthophosphoric acid aqueous solution is gradually added (the amount of orthophosphoric acid added is 2% by weight of the amount of chilled water sand NO.A). The stirring process was continued at 2000 rpm until the product temperature reached 130 ° C. Thereafter, the product was taken out from the supermixer, left in the air and cooled to room temperature (about 20 ° C.) to prepare a resin filler. In addition, 135 degreeC oil was circulated through the jacket of the super mixer.

Example 5
The resin filler was prepared in the same manner as in Example 4 except that the concentration of the orthophosphoric acid aqueous solution was 30% and the addition amount was 160 g (the amount of added orthophosphoric acid was 0.8% by weight of the amount of Super 3S). Prepared.

Example 6
The resin filler was prepared in the same manner as in Example 4 except that the concentration of the orthophosphoric acid aqueous solution was 30% and the addition amount was 80 g (the amount of added orthophosphoric acid was 0.4% by weight of the amount of Super 3S). Prepared.

Example 7
A resin filler was prepared in the same manner as in Example 6 except that 24 g of oleic acid (the amount of oleic acid added was 0.4% by weight of the amount of Super 3S) was added simultaneously with the addition of the orthophosphoric acid aqueous solution.

Example 8
The calcium carbonate is 6 kg of commercially available light calcium carbonate (manufactured by Maruo Calcium Co., Ltd .; specific surface area 18000 cm ² / g), the concentration of the orthophosphoric acid aqueous solution is 30%, and the added amount is 180 g (the amount of added orthophosphoric acid is super A resin filler was prepared in the same manner as in Example 4 except that 1% by weight of the amount of S).

Example 9
The calcium carbonate used is 5 kg of Nanox # 25 (manufactured by Maruo Calcium Co., Ltd .; specific surface area 25000 cm ² / g), which is a commercially available heavy calcium carbonate, the concentration of the orthophosphoric acid aqueous solution is 30%, and the addition amount is 200 g ( A resin filler was prepared in the same manner as in Example 4 except that the amount of orthophosphoric acid added was 1.2% by weight of the amount of Nanox # 25.

Example 10
The calcium carbonate to be used is 5 kg of super # 2000 (manufactured by Maruo Calcium Co., Ltd .; specific surface area 20000 cm ² / g) which is a commercially available heavy calcium carbonate, the concentration of the orthophosphoric acid aqueous solution is 40%, and the addition amount is 625 g ( A resin filler was prepared in the same manner as in Example 4 except that the amount of orthophosphoric acid added was 5% by weight of Super # 2000. An electron micrograph (10,000 times) of the obtained filler for resin is shown in FIG. 1, and an X-ray analysis pattern is shown in FIG. There is no diffraction pattern other than calcite, and calcium phosphate is considered to exist in an amorphous state.

Comparative Example 1
Cold water sand NO. Which is the commercially available granular calcium carbonate used in Examples 1-3. A (manufactured by Maruo Calcium Co., Ltd.) was used as a resin filler.

Comparative Example 2
Cold water sand NO. The solution added to A was a potassium stearate aqueous solution having a concentration of 10%, and the amount added was 210 g (the amount of added potassium stearate was 0.3% by weight of the amount of cold water sand NO.A). In the same manner as in Example 1, a resin filler was prepared.

Comparative Example 3
Super 3S, which is commercially available calcium carbonate used in Example 4, was used as a filler for resin.

Comparative Example 4
Commercially available light calcium carbonate used in Example 8 was used as a filler for resin.

Comparative Example 5
Nanox # 25, which is commercially available calcium carbonate used in Example 9, was used as the filler for the resin.

Comparative Example 6
Super # 2000, which is commercially available calcium carbonate used in Example 10, was used as the filler for the resin.

Comparative Example 7
Nanocoat S-25 (manufactured by Maruo Calcium Co., Ltd .: specific surface area 25000 cm ² / g), which is a commercially available surface-treated heavy calcium carbonate (fatty acid treatment), was used as a filler for resin.

Comparative Example 8
Commercially available surface-treated heavy calcium carbonate (fatty acid soap treatment) M-300L (manufactured by Maruo Calcium Co., Ltd .: specific surface area 23000 cm ² / g) was used as a filler for resin.

Comparative Example 9
100 g of super calcium carbonate # 2000, which is commercially available calcium carbonate used in Example 10, was taken as a 10% aqueous solution and charged into a super mixer, and 50 g of an orthophosphoric acid aqueous solution having a concentration of 10% was stirred while maintaining the treatment temperature at 15 ° C. or lower. A resin filler consisting of calcium carbonate particles coated with DCPD (dibasic calcium phosphate) was prepared by dropping dropwise over 10 minutes (the amount of orthophosphoric acid added was 5% by weight of Super # 2000). FIG. 2 shows an electron micrograph (10,000 times) of the obtained filler for resin, and plate-like crystal DCPD (dibasic calcium phosphate) is confirmed on the particle surface. An X-ray analysis pattern is shown in FIG. Presence of diffraction images can be seen in the vicinity of 7.52 mm and 3.03 mm, which are the characteristics of DCPD (dibasic calcium phosphate).

Comparative Example 10
100 g of super calcium carbonate # 2000, which is commercially available calcium carbonate used in Example 10, was taken as a 10% aqueous solution into a supermixer, and 10 g of 10% orthophosphoric acid aqueous solution having a concentration of 10% was stirred while maintaining the treatment temperature at 50 ° C. A resin filler consisting of calcium carbonate particles coated with HAP (hydroxyapatite) was prepared by dropping dropwise over 5 minutes (the amount of orthophosphoric acid added was 5% by weight of the amount of Super # 2000). An electron micrograph (10,000 times) of the obtained filler for resin is shown in FIG. 3, and an X-ray analysis pattern is shown in FIG. Presence of a diffraction image is observed in the vicinity of 3.43 ヒ ド ロ キ シ which seems to be hydroxyapatite which cannot be confirmed with untreated Super # 2000.

Comparative Example 11
Super # 2000, a commercially available calcium carbonate used in Example 10, was put into a 5 kg high-speed mixer, and 12500 g of an orthophosphoric acid aqueous solution having a concentration of 2% was gradually added (the amount of orthophosphoric acid added was super # 2000). Of 5% by weight). During this time, cold water was circulated through the jacket so that the product temperature was 15 ° C. or lower. 200 g of the pasty product was taken from the mixer and dried at low temperature to prepare a resin filler consisting of calcium carbonate particles coated with DCPD (dibasic calcium phosphate).
The production conditions of Examples 1 to 10 and Comparative Examples 1 to 11 and substances constituting the coating layer are shown in Table 1.

Examples 11-13, Comparative Examples 12, 13
Using the resin fillers obtained in Examples 1 to 3 and Comparative Examples 1 and 2, each resin composition was prepared by the following composition and method. Next, a test piece was prepared from each of the obtained filling compositions, and a tensile test according to JIS A1439 was performed using the test piece. In the following description, parts represent parts by weight.

(Modified silicone epoxy resin adhesive)
SAT-200 silyl resin [manufactured by Kaneka Corporation (modified silicone epoxy resin)]
70 parts Neostan U-100 [manufactured by Nitto Kasei Co., Ltd. (tin-based curing catalyst)] 2 parts KBM-603 [manufactured by Shin-Etsu Chemical Co., Ltd. (silane coupling agent; adhesion promoter)]
2 parts Calfine N-350 [manufactured by Maruo Calcium Co., Ltd. (colloidal calcium carbonate; thixo-fading agent)] 38 parts Resin filler 76 parts

  Using the above-mentioned formulation, planetary agitation / demolition device Mazerustar KK-500 (manufactured by Kurashiki Boseki Co., Ltd.) is used to first premix other than the resin filler, and then mix and re-stir and mix the resin filler. Thus, a resin composition was obtained. This was packed into an H shape, cured at 23 ° C. for 10 days and 50 ° C. for 4 days, and subjected to a strength test (primer: No. 45; silicone-based solution, manufactured by Yokohama Rubber Co., Ltd.). The test results are shown in Table 2. Interfacial adhesion was evaluated by the following method.

(Interface adhesion)
The composition prepared by the above method is put into a 100 ml PP cup, cured at 23 ° C. × 10 days, 50 ° C. × 4 days, then cut with a cutter knife, and the detachment of filler particles from the cross section (40 mmΦ). Observed. Table 1 shows the results of evaluating the number of detached filler particles according to the following criteria.
○: 10 or less filler particles are detached from the interface when cut. Δ: 11 or more and 30 or less filler particles are detached from the interface when cut. ×: Filler is separated from the interface when cut. More than 31 particles detached

  From the results in Table 2, the strength physical properties of the modified silicone epoxy resin adhesive containing the resin filler of the present invention are clearly improved. Furthermore, the interfacial adhesion between the resin and the filler particles is excellent, and there is little separation of the filler particles from the composition.

Examples 14-17, Comparative Examples 14-15
Using the resin fillers obtained in Examples 4 to 7 and Comparative Examples 3 to 4, each resin composition was prepared in the same manner as in Example 11 with the following composition. Next, a test piece was prepared from each of the obtained filling compositions, and a tensile test according to JIS A1439 was performed using the test piece. The test results are shown in Table 3.

(Modified silicone epoxy resin adhesive)
SAT-200 silyl resin [manufactured by Kaneka Corporation (modified silicone epoxy resin)]
70 parts Neostan U-100 [manufactured by Nitto Kasei Co., Ltd. (tin-based curing catalyst)] 2 parts KBM-603 [manufactured by Shin-Etsu Chemical Co., Ltd. (silane coupling agent; adhesion promoter)]
2 parts Calfine N-350 [manufactured by Maruo Calcium Co., Ltd. (colloidal calcium carbonate; thixo-fading agent)] 30 parts A [Maruo Calcium Co., Ltd. (calcium carbonate)] 36 parts Resin filler 40 parts

  From the results in Table 3, the strength physical properties of the modified silicone epoxy resin adhesive with the resin filler of the present invention clearly improved.

Examples 18-20, Comparative Examples 16-17
Using the resin fillers obtained in Examples 8 to 10 and Comparative Examples 5, 6, and 9, each resin composition was prepared by the following composition and method. Next, a test piece was prepared from each of the obtained resin compositions, and a tensile test was performed according to JIS A1439 using the test piece.

(Silicone sealant)
DMS-S42 [Gerest Co., Ltd. (silicone resin)] 72 parts SH-200 [Toray Dow Corning Silicone Co., Ltd. (silicone oil; plasticizer)] 3 parts SIM-6590 [Gerest Co., Ltd. (oxime crosslinking agent) ] 8 parts Aerosil R974 [manufactured by Nippon Aerosil Co., Ltd. (silica; thixo-fading agent)]
4 parts STAN BL [manufactured by Sansha Co., Ltd. (tin-based curing catalyst)] 0.2 parts Resin filler 71 parts

  The resin composition was obtained by stirring and mixing with the above-mentioned blending, using a planetary stirring / demolding device Mazerustar KK-500 (manufactured by Kurashiki Boseki Co., Ltd.). This was packed in an H shape, cured at 23 ° C. for 14 days, and subjected to a strength test. The resin filler was used after drying at 105 ° C. for 2 hours. The test results are shown in Table 4.

  From the results in Table 4, the strength properties of the silicone sealant containing the resin filler of the present invention are clearly improved.

Examples 21-23, Comparative Examples 19-21
Using the resin fillers obtained in Examples 6, 9, and 10 and Comparative Examples 3, 5, and 6, each resin composition was prepared by the following composition and method. Next, a test piece was prepared from each of the obtained resin compositions, and a tensile test according to JIS A1439 was performed using the test piece.

(Modified silicone sealant)
Main agent S810 [manufactured by Kaneka (modified silicone resin)] 50 parts DOP [manufactured by Jplus (dioctyl phthalate; plasticizer)] 30 parts N-350 [manufactured by Maruo calcium (colloid calcium carbonate; thixo)・ Temperature imparting agent)] 55 parts Resin filler 30 parts

Curing agent Neostan U-28 [manufactured by Kaneka Corporation (tin-based curing catalyst)] 6 parts Laurylamine [manufactured by Wako Pure Chemical Industries, Ltd. (reaction modifier)] 1.5 parts DOP [manufactured by JPLUS Inc. (Dioctyl phthalate; plasticizer) 14 parts Super 3S [manufactured by Maruo Calcium Co., Ltd. (heavy calcium carbonate; viscosity modifier)]
40 parts Calfine 200M [manufactured by Maruo Calcium Co., Ltd. (colloidal calcium carbonate; thixo-wrinkling agent)] 5 parts

  In the above composition, using a planetary agitation / demolition device Mazerustar KK-500 (manufactured by Kurashiki Boseki Co., Ltd.), first, the main agent and the curing agent are separately stirred and mixed, and the main agent / curing agent = 10/1. Two liquids were mixed to obtain a resin composition. This was packed into an H shape, and cured at 23 ° C. for 3 days and 50 ° C. for 4 days, and a strength test was performed (primer: NO. 40; urethane-based solution, manufactured by Yokohama Rubber Co., Ltd.). The test results are shown in Table 5.

  From the results of Table 5, by comparing Example 21 and Comparative Example 9, Example 22 and Comparative Example 20, Example 23 and Comparative Example 21, the modified silicone sealant containing the resin filler of the present invention is Obviously, the strength properties are improved over the modified silicone sealant containing untreated calcium carbonate.

Examples 24-25, Comparative Examples 22-25
Using the resin fillers obtained in Examples 9 and 10 and Comparative Examples 7, 8, 10, and 11, each resin composition was prepared by the following composition and method. Next, a test piece was prepared from each of the obtained resin compositions, and a tensile test according to JIS A1439 was performed using the test piece.

(Polysulfide sealant)
Main component LP-23 [Toray Fine Chemical Co., Ltd. (polysulfide resin)] 54 parts BBP [Wako Pure Chemical Industries, Ltd. (butylbenzyl phthalate; plasticizer) 18 parts Shiraka Hana CC [Shiraishi Calcium Co., Ltd. (colloid carbonic acid) 18 parts KBM-403 [manufactured by Shin-Etsu Chemical Co., Ltd. (silane coupling agent; adhesion promoter)]
0.5 parts Resin filler 72 parts

Curing agent Mn02 [Wako Pure Chemical Industries, Ltd. (curing catalyst)] 10 parts BBP [Wako Pure Chemical Industries, Ltd. (butylbenzyl phthalate; plasticizer) 13 parts TET-G [Ouchi Shinsei Chemical Co., Ltd. ) (Tetraethylene thiuram disulfide curing accelerator)] 2.5 parts Super S [manufactured by Maruo Calcium Co., Ltd. (viscosity modifier)] 3.5 parts

  In the above composition, using a planetary agitation / demolition device Mazerustar KK-500 (manufactured by Kurashiki Boseki Co., Ltd.), first, the main agent and the curing agent are separately stirred and mixed, and the main agent / curing agent = 10/1. Two liquids were mixed to obtain a resin composition. This was packed in an H shape and cured at 23 ° C. for 3 days and 50 ° C. for 4 days to conduct a strength test (standard curing). Further, a strength test was performed by immersing in 80 ° C. warm water for 7 days (warm water curing). The test results are shown in Table 6. In Comparative Example 24, the viscosity of the main agent was high, and the test was stopped because a specified amount of resin filler could not be blended.

  From the results in Table 6, the polysulfide sealant blended with the filler for resin of the present invention clearly has improved strength properties and little decrease in strength after warm water curing.

Examples 26 to 27, Comparative Examples 26 to 27
Using the resin fillers obtained in Examples 9 and 10 and Comparative Examples 7 and 11, polysulfide compositions were prepared in the same manner as in Examples 24 and 25 and Comparative Examples 22 to 25, and 5 cmφ × 1 cm. It was formed into a disk shape. It was subjected to standard curing at 23 ° C. × 3 days and 50 ° C. × 4 days, then immersed in warm water at 80 ° C., and the warm water resistance (swelling resistance) was evaluated by the weight change (increase rate) due to the warm water immersion. The results are shown in Table 7.

  From the results in Table 7, the polysulfide sealant containing the resin filler of the present invention clearly has little swelling due to hot water.

  As described above, the resin filler of the present invention can greatly increase the adhesive strength and hot water resistance of the resin. Moreover, according to the manufacturing method of this invention, the resin filler of this invention can be manufactured efficiently.

Claims (7)

  A filler for a calcium carbonate resin, wherein the surface of the calcium carbonate particles is coated with amorphous calcium phosphate.   An aqueous solution of phosphoric acid having a concentration of 5% or more is added to the calcium carbonate particles, and the mixture is reacted with stirring at a temperature of 50 ° C. or higher to form an amorphous calcium phosphate layer on at least a part of the surface of the calcium carbonate particles. A method for producing a filler for a calcium carbonate resin, characterized by comprising forming the filler.   The method for producing a filler for a calcium carbonate resin according to claim 2, wherein the addition amount of phosphoric acid is 0.05 to 5% by weight with respect to the calcium carbonate particles.   The method for producing a filler for calcium carbonate resin according to claim 2 or 3, wherein the concentration of phosphoric acid to be added is 10 to 50%.   A resin composition comprising the calcium carbonate resin filler according to claim 1 blended in a resin.   6. The resin composition according to claim 5, wherein the resin comprises at least one selected from urethane epoxy resins, epoxy resins, modified silicone resins, modified silicone epoxy resins, silicone resins, polysulfide resins, and acrylic resins.   The resin composition according to claim 6, wherein the resin is an adhesive or a resin for a sealing material.