JP2014156525A - Surface-treated calcium carbonate filler and curable resin composition obtained by blending the filler - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface-treated calcium carbonate filler capable of providing a resin composition which is excellent in dispersibility in blending in a curable resin, for example, excellent in adhesion strength, elongation and warm water adhesion when blended in a sealing material and in which a blended composition has excellent storage stability.SOLUTION: There are provided: a calcium carbonate filler which is calcium carbonate surface-treated by a fatty acid-based organic material containing at least one selected from a fatty acid and a water-soluble salt thereof, in which the specific surface area Sw after the surface treatment, the amount As of a surface treatment agent, the amount Cr of the surface treatment agent left on the calcium carbonate side during an ethanol extraction, the amount Ar of a free fatty acid determined by the ethanol extraction and the ratio Sr of a counter-ion in the free material to amount of the total surface treatment agent of the monovalent fatty acid and the ratio Ar/(Ar+Sr) of the free fatty acid in the free material are specific values; and a curable resin composition obtained by blending the calcium carbonate filler.

Description

  The present invention relates to a surface-treated calcium carbonate filler and a curable resin composition comprising the same, and more specifically, the BET specific surface area of the surface-treated calcium carbonate filler and the surface treatment amount by a fatty acid-based surface treatment agent are specified. When blended into a curable resin composition by controlling the amount of the surface treatment agent that does not elute from the surface treated calcium carbonate by ethanol extraction and the amount of the surface treatment agent extracted by ethanol to a specific range In addition, it is excellent in dispersibility at the time of blending and storage stability after blending.For example, when blended in a sealing material, it has excellent adhesive strength and elongation, particularly hot water adhesion, and blended in an adhesive. The surface-treated carbonic acid can provide a curable resin composition having excellent adhesion and, when blended in plastisol, excellent slip resistance and adhesion to the electrodeposition plate. Calcium fillers, and to a curable resin composition obtained by blending it.

  In sealing materials, adhesives, plastisols and the like, characteristics are improved by blending surface-treated calcium carbonate with a curable resin. However, the surface-treated calcium carbonate filler that has been surface-treated using a commonly used fatty acid soap as a surface treatment agent, the free fatty acid and soap remaining on the calcium carbonate surface are dissolved into the resin composition and bonded. It may have adverse effects such as deterioration of adhesion, deterioration of adhesion, and decrease in adhesive strength.

  In addition, when a surface-treated calcium carbonate filler surface-treated using a fatty acid soap and an emulsifier as a surface treatment agent is blended in, for example, a two-component urethane sealant, the surface-treated calcium carbonate filler surface-treated with a fatty acid soap alone Although the foaming property is good, if soap (Na salt, K salt, etc.) remains on the surface of calcium carbonate, moisture that causes foaming is easily drawn, and storage stability may be deteriorated.

  Moreover, when calcium carbonate surface-treated with a fatty acid ester is added to a moisture-curing one-pack type resin composition, the resin composition is provided with excellent thixotropy and slump resistance, and good storage stability. Has been reported (see Patent Document 1). However, since the surface-treated calcium carbonate of Patent Document 1 has a weak binding force between the fatty acid ester and the calcium carbonate, the fatty acid ester may dissolve into the resin composition, which may have adverse effects such as deterioration in adhesiveness and reduction in adhesive strength. .

  In addition, it has been reported that the surface-treated calcium carbonate obtained by wet surface treatment of a single fatty acid imparts excellent thixotropy, slump resistance and good storage stability in a curable resin composition (Patent Document 2). reference). However, since fatty acids are extremely insoluble in water, for example, when wet-treated, the surface treatment may become non-uniform, resulting in poor dispersibility in curable resins and reduced hot water adhesion. There is.

Further, the surface treatment is a wet treatment with a saturated fatty acid metal soap, an unsaturated fatty acid metal soap, an alicyclic carboxylic acid metal soap, and an alkali metal content of 1.0 × 10 ⁻³ mol / 100 g CaCO ³ or less. It has been reported that a curable resin composition having excellent thixotropy, slump resistance and good storage stability can be obtained by blending calcium carbonate into the curable resin composition (see Patent Document 3). ). However, as described above, the free fatty acid and soap remaining on the calcium carbonate surface may dissolve into the resin composition, which may have adverse effects such as deterioration of adhesion, deterioration of adhesion, and reduction of adhesive strength.

  In addition, surface-treated calcium carbonate that has been surface-treated using a soap made of a nonmetal such as an ammonium ion as a counter ion of fatty acid as a surface treatment agent has excellent thixotropy and slump resistance in a curable resin composition. In addition, it has been reported that excellent storage stability and adhesiveness that have never been obtained are provided (see Patent Document 4). However, it can give good storage stability by not containing alkali metal, but free fatty acid and soap remaining on the surface of calcium carbonate dissolves during compounding, resulting in poor adhesion, poor adhesion, and adhesive strength. There may be adverse effects such as decline.

  Further, a surface-treated calcium carbonate that is surface-treated with a fatty acid metal soap having 8 or more carbon atoms and does not contain an alkali metal, or a method for producing calcium carbonate in which a surface treatment is performed by adding a fatty acid metal soap to a water-soluble organic solvent. However, it is reported that the sealing material has excellent thixotropy and storage stability (see Patent Document 5). However, since metal soaps such as calcium soap and magnesium soap are water-insoluble soaps, it takes a very long time for surface treatment in a water slurry, and it is difficult to obtain a stable surface treatment state. Therefore, storage stability often deteriorates. In addition, when the water-soluble organic solvent is treated at a temperature higher than the melting point of the fatty acid, it tends to volatilize and there is a problem in safety.

Japanese Patent No. 2652044 Japanese Patent No. 3151196 Japanese Patent No. 3685031 JP 2004-331963 A Japanese Patent No. 3650381

    The main object of the present invention is to solve the above-mentioned problems of the prior art in view of the above circumstances, and is excellent in dispersibility when blended in a curable resin, and the blended composition is excellent in storage stability, for example, For sealing materials and adhesives, it is excellent in all of adhesive strength, elongation rate, hot water adhesion, etc., and for plastisol, a surface that can give a resin composition excellent in slip resistance and adhesion to an electrodeposition plate, The object is to provide a treated calcium carbonate filler and a curable resin composition containing the filler.

  As a result of diligent research to solve the above-mentioned problems, the present inventors have controlled the BET specific surface area of the surface-treated calcium carbonate filler and the surface treatment amount of the fatty acid system to a specific range, and from the surface-treated calcium carbonate also by ethanol extraction. By controlling the amount of the surface treatment agent that does not elute to a specific range, when blended in a curable resin composition, it is superior in dispersibility and storage stability compared to conventional surface treated calcium carbonate fillers, for example, sealing. With regard to materials and adhesives, necessary physical properties such as adhesive strength, elongation, and hot water adhesion can be imparted, and regarding plastisol, it has been found that it has excellent slip resistance and adhesion to an electrodeposition plate, It came to be completed.

A feature of the present invention is that calcium carbonate is surface-treated with a surface treatment agent containing at least one selected from fatty acids and water-soluble salts thereof, and satisfies the following formulas (1) to (5): The content is a surface-treated calcium carbonate filler.
(1) 3 ≦ Sw ≦ 40 [m ² / g]
(2) 0.40 ≦ As ≦ 5.50 [mg / m ² ]
(3) 85 ≦ Cr ≦ 100 [wt%]
(4) 0 ≦ Ar ≦ 10 [wt%]
(5) 0.15 ≦ Ar / (Ar + Sr) ≦ 1.00 [−]
However,
Sw: BET specific surface area of surface-treated calcium carbonate [m ² / g]
As: surface treatment agent amount per unit specific surface area determined by the following formula: As = Tg / Sw [mg / m ² ]
Tg: Heat loss per gram of surface-treated calcium carbonate at 200 ° C. to 500 ° C. [mg / g]
Cr: Ratio of the amount of the surface treatment agent that is not eluted as a free substance and remains on the calcium carbonate side when the surface treatment calcium carbonate is extracted with ethanol to the total surface treatment agent amount [% by weight]
Ar: Ratio of the amount of free fatty acid in the amount of free substances obtained by extracting the surface-treated calcium carbonate with ethanol to the amount of the total surface treatment agent [wt%]
Sr: The ratio of the amount of monovalent fatty acid salt to the total amount of the surface treatment agent in the amount of free ions obtained by extracting the surface-treated calcium carbonate with ethanol [wt%]

  Another feature of the present invention is a surface-treated calcium carbonate filler in which the unsaturated component in the surface treatment agent is 0 to 30% by weight.

  Another feature of the present invention is a curable resin composition obtained by blending the surface-treated calcium carbonate filler with a curable resin.

  Another feature of the present invention is that the curable resin is at least one selected from the group consisting of polyurethane resin, polysulfide resin, modified silicone resin, silicone resin, polyisobutylene resin, modified acrylic resin, and acrylic urethane resin. It is a composition.

  Another feature of the present invention is that the curable resin composition is a sealing material.

  Still another feature of the present invention is that the curable resin composition is an adhesive.

  Still another feature of the present invention is a curable resin composition obtained by blending the above-mentioned surface-treated calcium carbonate filler into plastisol.

  Still another feature of the present invention is a curable resin composition in which the plastisol resin is an acrylic resin or a vinyl chloride resin.

  The surface-treated calcium carbonate filler of the present invention is blended in a curable resin composition and is excellent in dispersibility at the time of blending and storage stability after blending. For example, regarding a sealing material and an adhesive, adhesive strength, elongation rate Further, it is possible to provide a curable resin composition which is excellent in hot water adhesiveness and the like, and has excellent slip resistance and adhesion to an electrodeposition plate with respect to plastisol.

  The calcium carbonate used in the present invention is not particularly limited. For example, it is obtained by mechanically pulverizing and classifying precipitated calcium carbonate and limestone produced by introducing CO2 gas into an aqueous slurry of Ca (OH) 2. Any of the heavy calcium carbonates can be used. In general, precipitated calcium carbonate can be preferably used because finer particles can be easily obtained.

The calcium carbonate is subjected to surface treatment (coating treatment) with a surface treatment agent.
In the present invention, the fatty acid used as the surface treatment agent and its water-soluble salt indicate that the fatty acid is a saturated fatty acid or unsaturated fatty acid having a melting point of less than 100 ° C., and for the water-soluble salt, the fatty acid sodium salt, It is a potassium salt, an ammonium salt or the like, and the counter ion indicates a monovalent fatty acid salt. There are no particular restrictions on saturated fatty acids and unsaturated fatty acids, but it is preferable to have as many carbon atoms as possible. For example, when used in a curable resin composition, it has high thixotropy and slump resistance in addition to storage stability. Therefore, it is preferable that carbon is 8 or more. However, unsaturated fatty acids (for example, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, etc.) are likely to elute as free substances when extracted with ethanol, so 0 to 30% by weight of the total surface treatment amount Preferably, it is 0 to 20% by weight, more preferably 0 to 10% by weight. It should be noted that the fatty acid ammonium salt alone, the fatty acid alone, or the combination of the fatty acid and a water-soluble salt such as sodium salt, potassium salt, or ammonium salt can easily obtain the desired physical properties, but the fatty acid sodium salt, potassium salt, etc. The alkali metal salt alone is not preferable because the fatty acid soap ratio may be increased depending on the surface treatment amount, and it becomes easy to attract moisture.

  Specifically, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, 2-ethylbutyric acid, 2-ethylhexanoic acid, isononane Acid, isodecanoic acid, neodecanoic acid, isotridecanoic acid, isopalmitic acid, isostearic acid, myristoleic acid, palmitoleic acid, oleic acid, linoleic acid, linolenic acid, beef tallow stearic acid, palm kernel fatty acid, palm fatty acid, palm fatty acid, palm stearin Acid, beef tallow fatty acid, soybean fatty acid, partially cured palm kernel fatty acid, partially cured palm fatty acid, partially cured beef tallow fatty acid, partially cured soybean fatty acid, extremely cured palm kernel fatty acid, extremely cured palm fatty acid, extremely cured beef tallow fatty acid, extremely cured soybean fatty acid, etc. Saturated fatty acids, unsaturated fatty acids and saturated Fatty acids such as saturated mixed fatty acids. These can be used alone or in combination of two or more.

  Preferred among the above are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, beef tallow stearic acid, palm kernel fatty acid, partially cured palm fatty acid, extremely cured palm fatty acid, coconut fatty acid, partially cured coconut fatty acid, Examples include extremely hardened coconut fatty acid, palm fatty acid, palm stearic acid, beef tallow fatty acid, partially cured beef tallow fatty acid, extremely hardened beef tallow fatty acid, soy fatty acid, partially hardened soy fatty acid, and saturated fatty acid such as extremely hardened soy fatty acid.

  In the present invention, as described above, fatty acids and water-soluble salts thereof are preferably used. However, as long as the formulas (1) to (5) are satisfied, a part of the other surface treatment agent may be included. . For example, as long as the effects of the present invention are not lost, sulfonic acids such as alkylbenzene sulfonic acids, salts thereof, fatty acid esters such as stearyl stearate, resin acids such as abietic acid, salts thereof, metal soaps such as calcium soap, etc. , A portion may be included as long as the effects of the present invention are not lost.

The method of surface treatment of calcium carbonate is not particularly limited, but when treating a fatty acid, it is preferable to treat it at a temperature equal to or higher than the melting point of the fatty acid to be used because it is easy to uniformly treat the surface.
Since surface treatment of precipitated calcium carbonate is a gas-liquid reaction, the prepared treatment agent is added to the aqueous slurry of precipitated calcium carbonate and stirred, or kneaded into the hydrous cake of precipitated calcium carbonate. It is preferable to process. In the case of heavy calcium carbonate, since it is often pulverized dry, it is usually subjected to surface treatment in a dry manner, but free fatty acids may increase, so in order to make the surface treatment better It is preferable to perform the surface treatment by a wet method. For example, a heating / stirring device such as a Henschel mixer may be used.
A concentration of 10 to 800 g CaCO 3 / L is preferable for the aqueous slurry of precipitated calcium carbonate when the surface treatment is performed in the water slurry. When the concentration is lower than 10 g CaCO 3 / L, it is disadvantageous in terms of productivity. On the other hand, when the concentration is higher than 800 g CaCO 3 / L, the viscosity of the water slurry becomes high and the surface treatment agent may not permeate sufficiently, and the target filler may not be obtained. There is sex.
About the surface treatment temperature in the case of surface treatment in water slurry, it is preferable to surface-treat at the temperature more than melting | fusing point of the fatty acid and fatty acid salt used as a surface treating agent, Preferably it is 20-98 degreeC, More preferably, it is 40-90. ° C, more preferably 60 to 80 ° C. When the surface treatment temperature is lower than 20 ° C., it is difficult to cause adsorption bonding of the surface treatment agent to calcium carbonate and the surface treatment becomes non-uniform, which is not preferable. Further, if the treatment temperature is higher than 98 ° C., the effect of the present invention can be obtained sufficiently, but there is a risk of bumping and it is dangerous, so it is preferable to use a pressure resistant device.
Moreover, in the case of a water-containing cake or a dry process, Preferably it is 20-150 degreeC, More preferably, it is 40-130 degreeC, More preferably, it is 60-120 degreeC. When the surface treatment temperature is lower than 20 ° C., it is not preferable because the surface treatment agent is less likely to be adsorbed and bonded to calcium carbonate, and the surface treatment may become uneven. Further, when the surface treatment temperature is higher than 150 ° C., in the case of a surface treatment agent having a low heat-resistant temperature, the surface treatment agent may be deteriorated due to heat and may be deteriorated, but in that case, an inert gas (nitrogen or the like) The atmosphere should be.

In the present invention, the formula (1) is a specific surface area Sw when measured by the BET method by the nitrogen adsorption method of the surface-treated calcium carbonate, and this value needs to be 3 to 40 m ² / g, and 8 to 40 m. ² / g is preferable, and 10 to 40 m ² / g is more preferable. When the specific surface area is less than 3 m ² / g (particles are large), even if it is a curable resin composition blended with surface-treated calcium carbonate, excellent storage stability and adhesion can be obtained, but thixotropy is achieved. It may be insufficient. Further, when the specific surface area is larger than 40 m ² / g (particles are small), the particles are strongly aggregated, and even in the curable resin composition containing the surface-treated calcium carbonate, Not only does the dispersibility worsen, but the water content of the surface-treated calcium carbonate filler tends to increase with adsorbed water, crystal water, and the like, leading to a decrease in storage stability.

In the present invention, Sw is measured by the following test method.
[Sample preparation method]
A glass cell is charged with 300 mg of sample, pretreated for 10 minutes at 200 ° C. while nitrogen is conducted, and then cooled to room temperature to obtain a measurement sample.
[Measurement method of BET specific surface area]
Measured by a one-point method with a BET specific surface area meter (Macsorb HM model-1210, manufactured by Mountec).

In the present invention, the formula (2) is a surface treatment agent amount As (Tg / Sw) per unit specific surface area of the surface treated calcium carbonate, and needs to be 0.40 to 5.50 mg / m ^2. preferably 0.80~5.00mg / m ² are, 1.50~4.00mg / m ² is more preferable. If it is less than 0.40 mg / m ² , the effect of the surface treatment tends to be insufficient, and the untreated surface is exposed due to insufficient treatment, so that moisture tends to be adsorbed. On the other hand, if it exceeds 5.50 mg / m ² , the surplus treatment agent acts as a lubricant, which may cause adverse effects such as a decrease in adhesiveness, adhesion, and slip resistance, and is economically disadvantageous. . In addition, it is preferable to vary according to the BET specific surface area Sw of calcium carbonate.

In the present invention, Tg is measured by the following test method.
[Measurement method of heat loss]
Using a thermal analyzer (Thermo Plus EVO II, manufactured by Rigaku Corporation), 30 mg of surface-treated calcium carbonate was sampled on a sample pan (platinum) having a diameter of 5 mm and a depth of 5 mm, and the temperature was increased from room temperature to 510 ° C. at a temperature increase rate of 15 ° C./min. The heat loss at 200 ° C. to 500 ° C. when the temperature is raised to 0 ° C. is measured, and the heat loss (surface treatment agent amount) per 1 g of the surface treated calcium carbonate (mg / g) is determined.

In this invention, Formula (3) is ratio Cr which the surface treatment agent amount which is not eluted as a free substance but remains on the calcium carbonate side when ethanol is extracted from the surface treatment calcium carbonate in the total surface treatment agent amount.
In the present invention, Cr needs to satisfy 85 ≦ Cr ≦ 100 [wt%], and this value is preferably 90 to 98 wt%, and more preferably 95 to 98 wt%. If it is less than 85% by weight, the hot water adhesiveness and adhesive strength tend to be insufficient. On the other hand, if it exceeds 98% by weight, the surface treatment state tends to be poor, and the storage stability tends to be insufficient.

In the present invention, the formula (4) is the ratio Ar of the amount of free fatty acid obtained by extracting the surface-treated calcium carbonate with ethanol with respect to the total amount of the surface treatment agent [wt%].
In the present invention, Ar needs to satisfy 0 ≦ Ar ≦ 15 [wt%], and this value is preferably 0 to 10 wt%, and more preferably 0 to 5 wt%. If it exceeds 15% by weight, the hot water adhesiveness and adhesive strength tend to be insufficient. On the other hand, 0% by weight is the theoretical lower limit.

In the present invention, the formula (5) is the ratio Ar / (Ar + Sr) of the amount of free fatty acid in the amount of free products obtained by extracting the surface-treated calcium carbonate with ethanol [−].
In the present invention, the ratio Ar / (Ar + Sr) of the amount of free fatty acid in the amount of free products must be 0.15 ≦ Ar / (Ar + Sr) ≦ 1.00, and this value is 0.25 to 0.90. Preferably, 0.40 to 0.80 is more preferable. Below 0.15, dispersibility and thixotropy decrease, for example, plastisol tends to have poor adhesion to the electrodeposition plate, and sealing materials and adhesives tend to decrease storage stability and hot water adhesion. There is. In addition, 1.00 is a value when the counter ion in the amount of free substances does not have a monovalent fatty acid salt amount. In addition, in the equations (3) to (5), there is theoretically a relationship of Cr + Ar + Sr = 100 [wt%].

[Measurement method of Ar, Sr and Cr]
(1) Collect 5g of calcium carbonate sample in a 300ml Erlenmeyer flask and add 80g of 95% ethanol.
(2) Lightly cover the flask mouth with aluminum foil, heat on a water bath at 90 ° C or higher for 1 hour, and let it cool at room temperature for 1 day.
(3) Adjust the temperature to 30 ° C., suction filter using a PTFE membrane filter (pore size 0.5 μm), and take the filtrate in a beaker.
(4) Take the filtrate into a weighed 200 ml beaker and immerse it in a hot water bath at 80 ° C or higher to evaporate 95% ethanol. After cooling, the weight of the beaker is measured (the weight of the empty beaker is also measured before filtration).
(5) The amount of free substances F [mg / g] per 1 g of surface-treated calcium carbonate is calculated.
F [mg / g] = [beaker weight after filtration and cooling (mg) −empty beaker weight (mg)] / calcium carbonate sample weight (g)
(6) The above eluate (5) is dissolved in 25 ml of 2-propanol to which several drops of phenolphthalein solution are added.
(7) The solution of (6) is neutralized and titrated with a 0.1 mol / l potassium hydroxide aqueous solution.
(8) When the amount of free fatty acid in the amount of free substance per 1 g of surface-treated calcium carbonate is defined as a [mg / g] from the potassium hydroxide titration in (7) above,
Free fatty acid amount a [mg / g] = 0.1 mol / l Potassium hydroxide titer (ml) × 10 ⁻⁴ × Molecular weight of treatment agent × 10 ³ (mg) / Calcium carbonate sample weight (g)
When the heat loss per 1 g of surface-treated calcium carbonate at 200 ° C. to 500 ° C. (total surface treatment agent amount) is Tg [mg / g],
The ratio Ar of the amount of free fatty acid obtained by extracting the surface-treated calcium carbonate with ethanol with respect to the total amount of the surface treatment agent is:
Ar = (a / Tg) × 100 [% by weight]
Similarly, when the amount of monovalent fatty acid salt is s [mg / g] when the counter ion in the amount of free substance per 1 g of surface-treated calcium carbonate is determined from potassium hydroxide titration in (7),
Monovalent fatty acid salt amount s = free product amount F-free fatty acid amount a [mg / g]
The ratio Sr of the amount of monovalent fatty acid salt with respect to the total amount of surface treatment agent in the amount of free ions obtained by extracting the surface-treated calcium carbonate with ethanol is:
Sr = (s / Tg) × 100 [% by weight]
(9) The amount of free treatment (Ar, Sr) is subtracted from the total amount of surface treatment agent to obtain the surface treatment agent amount Cr remaining on the calcium carbonate side without being eluted as free matter in the system. (95% ethanol insoluble matter is Cr)
Cr = 100−Ar—Sr [wt%]

As described above, the surface-treated calcium carbonate filler of the present invention is surface-treated using a surface-treating agent, and then pulverized according to conventional methods through steps such as dehydration, drying, and pulverization. The surface treatment agent is not particularly limited except that the surface treatment agent of the present invention is used, and the surface treatment method may be either wet or dry.
However, in order to sufficiently surface-treat the surface treatment agent of the present invention to calcium carbonate, it is necessary that the surface treatment agent sufficiently penetrates into the secondary aggregate of calcium carbonate. The effect becomes remarkable particularly when the amount of heat applied during drying becomes a certain level or more. Although drying conditions depend on the type of surface treatment agent and the amount of surface treatment, in order to obtain the effects of the present invention sufficiently, it is usually 100 ° C. or higher, preferably 110 ° C. or higher, over a certain period of time. It is desirable to dry, in particular, 5 hours or more if 110 ° C. or more and less than 120 ° C., 4 hours or more if 120 ° C. or more and less than 140 ° C. Is desirable. In order to obtain desired physical properties by drying at less than 100 ° C., it is necessary to lengthen the drying time accordingly, but the drying efficiency may be reduced and the running cost may be more than necessary. In addition, when the drying temperature is 110 ° C. or more and less than 120 ° C. for less than 5 hours, or 120 ° C. or more and less than 140 ° C. for less than 4 hours, or 140 ° C. or more and 150 ° C. or less and less than 2 hours, Although the treatment agent penetrates into the surface, the proportion of fatty acids and monovalent fatty acid salts present as free products tends to increase, making it difficult to obtain a sufficient treatment state and obtaining the desired physical properties. It becomes difficult. Further, when the drying temperature is higher than 150 ° C., the surface treatment agent having a low heat resistance temperature is not preferable because the surface treatment agent may be thermally deteriorated and deteriorated, but in that case, an inert gas (nitrogen or the like) atmosphere In this way, desired physical properties can be obtained even in a short time of 1 hour or less. Furthermore, in methods such as freeze drying, vacuum drying, wind drying, etc., the penetration of the surface treatment agent is difficult to occur, and it takes a considerable amount of time or other energy to obtain the desired physical properties. Therefore, a dryer having a sufficient residence time such as an oven dryer, a Henschel mixer, a band dryer, or a paddle dryer is preferable for the drying of the present invention.
The surface-treated calcium carbonate dried by the above method is pulverized through a pulverization step. The pulverization method may follow a conventional method, and a pin mill, a hammer mill or the like is used.
In order to obtain the desired physical properties, it is necessary to add a certain amount of heat in the drying step after the surface treatment, and to infiltrate the surface treatment agent into the secondary aggregate, once less than a certain amount of heat. Even if the powder obtained by drying with powder is reheated at a certain amount of heat or more, the surface treatment agent does not penetrate into the secondary aggregate, and it is difficult to obtain desired physical properties.

The surface-treated calcium carbonate filler obtained as described above is particularly useful for curable resin compositions such as sealing materials, adhesives, and plastisols. Examples of the sealing material include polyurethane, polysulfide, silicone, modified silicone, polyisobutylene, modified acrylic, acrylic urethane, butyl rubber, epoxy, and fluorine resins. Examples of the adhesive include resins such as urea, phenol, polyester, and vinyl acetate in addition to those exemplified as the sealing material. These may be used alone or in combination of two or more as required. Examples of plastisol include acrylic and vinyl chloride.
By blending the surface-treated calcium carbonate filler of the present invention into a sealing material and an adhesive, not only excellent dispersibility, thixotropy, and storage stability, but also excellent adhesive strength, elongation, and hot water adhesiveness are imparted. In addition, slip resistance and adhesion to the electrodeposition plate can be imparted by blending with plastisol.

  What is necessary is just to set the compounding quantity of the surface treatment calcium carbonate filler of this invention suitably according to the use of a resin composition. In the case of a sealing material, depending on the type of the sealing material, for example, in the case of a polyurethane resin or a modified silicone resin, it is usually 10 to 200 parts by weight, preferably about 20 to 150 parts by weight per 100 parts by weight of the resin. is there. In the case of a paint or an adhesive, the amount is usually 2 to 100 parts by weight, preferably about 5 to 80 parts by weight per 100 parts by weight of the resin. Since moisture greatly affects storage stability, it becomes even more reliable when dried before use. For example, the drying condition may be left in an oven at around 100 ° C. for several hours. In either case, if the number of blended parts is too small, the effect of thixotropy and slump resistance cannot be expected, while if too large, the storage stability and elongation rate are adversely affected.

In the case of a polyurethane sealant or an adhesive, the polyisocyanate urethane prepolymer having an isocyanate group at the molecular end used in the present invention can be synthesized by a reaction between a polyol and an excess polyisocyanate compound. As the polyol, various polyether polyols, polyester polyols, and other polyols can be used.
For example, examples of the polyether polyol include polyoxyethylene polyol, polyoxypropylene polyol, polyoxyethylene-propylene copolymer polyol, polytetramethylene polyol and the like alone or a mixture thereof.
Polyester polyols include dicarboxylic acids (adipic acid, succinic acid, maleic acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol, 1,4-butylene glycol, 1,6-hexane glycol, neopentyl glycol, etc.) Polyols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polypropylene adipate, polyethylene-propylene adipate and the like, and polylactone polyols such as polycaprolactone polyol alone. Alternatively, a mixture thereof, polycarbonate polyol and the like can be mentioned.
Examples of the polyisocyanate compound include aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, carbodiimide-modified MDI, and naphthalene diisocyanate. Examples include hexamethylene diisocyanate, isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and alicyclic polyisocyanate. The above polyisocyanates can be used alone or as a mixture thereof.
Curing catalysts include stannous oleate, stannous laurate, stannous acetate, zinc octylate, lead octylate, tin octylate, lead naphthenate, manganese naphthenate, cobalt manganate, ferric chloride , Stannic chloride, stannous chloride, antimony trichloride, triethylamine, N-methylmorpholine, triethanolamine, triethylenediamine, acetylacetone, and the like, and these are used alone or in combination of two or more. . Among these, lead octylate, tin octylate, lead naphthenate, and tin naphthenate are preferable in terms of cost. The blending amount of the catalyst is preferably 0.1 to 1 part by weight with respect to 100 parts by weight of the urethane prepolymer.
The amount of the surface-treated calcium carbonate filler of the present invention is usually about 10 to 200 parts by weight, preferably about 20 to 150 parts by weight with respect to 100 parts by weight of the polyurethane resin. If the content of the surface-treated calcium carbonate is less than 10 parts by weight, the effects of thixotropy and slump resistance cannot be expected. On the other hand, if it exceeds 200 parts by weight, storage stability, adhesiveness, etc. may be deteriorated. .

The polyurethane sealing material or adhesive of the present invention may contain a solvent, a plasticizer, a filler, a pigment, a thickener (or) a thixotropic agent, a stabilizer, or other additives as necessary. .
Examples of the solvent include aromatic hydrocarbons such as xylene and toluene, mineral spirits, and methyl ethyl ketone. As for the compounding quantity of a solvent, 3-20 weight part is preferable with respect to 100 weight part of urethane prepolymers.
Examples of the plasticizer include monomer plasticizers such as dioctyl adipate (DOA), dioctyl phthalate (DOP), diisononyl phthalate (DINP), dibutyl phthalate (DBP), tricresyl phosphate (TCP), polyester, and urethanization. Examples include oligomer plasticizers such as polyester and urethanized polyether. As for the compounding quantity of a plasticizer, 5-30 weight part is preferable with respect to 100 weight part of urethane prepolymers.
Examples of the filler include calcium carbonate, talc, clay, carbon, shirasu balloon, glass balloon, and polyvinyl chloride fine powder.
Examples of the thixotropic agent include colloidal silica, finely divided carbon black, fatty acid amide, and fatty acid metal soap.

Further, in the case of a polysulfide sealing material or an adhesive, it has a reactive mercaptan group (—SH) at the molecular end, and the polymer skeleton portion is represented by the general formula (A) or (A) and (B). A liquid polysulfide polymer having fluidity at room temperature can be used.
-(-R1-SX-) n-R1-SX (A)
-(-R2-SX-) n-(-R3-O-) m-SX- (b)
[X is an integer of 1 to 5, and n and m are integers of 2 to 200. R1, R2, and R3 each represent a divalent organic group (an alkylene group, an alkylene ether group, a hydroxyalkylene group, or the like). ]
Such a polysulfide polymer has fluidity at room temperature and has a number average molecular weight (Mn) of usually 100 to 200,000, preferably 800 to 50,000. Preferred examples of such polysulfide polymers are described in US Pat. No. 2,466,963 and JP-A-4-363325.

A compound containing two or more isocyanate groups in the molecule used in the present invention (hereinafter simply referred to as an isocyanate group-containing compound) is obtained by reacting an organic polyisocyanate compound and / or an active hydrogen-containing compound with an organic polyisocyanate compound. A urethane prepolymer is preferred.
Specific examples of the organic polyisocyanate compound include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate (crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, and the like.
Examples of the active hydrogen-containing compound include a hydroxyl group-terminated polyester, a polyvalent polyalkylene ether, a hydroxyl group-terminated polyurethane polymer, and a mixture thereof.
As said urethane prepolymer, what was obtained by making the above-mentioned active hydrogen containing compound and organic polyisocyanate compound react on the conditions of an isocyanate compound excess can be used.
In the present invention, it is preferable that the molar ratio of the isocyanate group in the isocyanate group-containing compound to the thiol group in the thiol group-containing compound (isocyanate group / thiol group) is 0.5 to 4.0. Preferably it mix | blends so that it may become 0.7-3.0. If the molar ratio is less than 0.5, the composition does not have a sufficiently high molecular weight. On the other hand, if it exceeds 4.0, the cured product tends to be hard and brittle, such being undesirable.
As the curing catalyst, a tertiary amine and / or an organometallic compound is used. Tertiary amines include monoamines, diamines, triamines, polyamines, cyclic amines, alcohol amines, ether amines, etc. Specific examples include triethylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropane-1,3-diamine, tetramethylguanidine, N, N-dipolyoxyethylene stearylamine, N, N -Dipolyoxyethylene beef tallow alkylamine and triethylenediamine are mentioned. These tertiary amines are used alone or in combination of two or more as required.
Examples of organometallic compounds include organotin compounds, organomercury compounds, organolead compounds, etc., specifically tin octylate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin maleate, dioctyltin mercaptide, Examples thereof include phenylmercury propionate and lead octenoate. These may be used alone or in combination of two or more as required. Among these, an organic tin compound that is less affected by discoloration or the like is preferable.
The content of the curing catalyst is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight with respect to 100 parts by weight of the polysulfide polymer. If the content is less than 0.001 part by weight, curing does not proceed and if it exceeds 5 parts by weight, the pot life tends to be short, which is not preferable.
The polysulfide sealing material or adhesive of the present invention can contain other additives as required. Examples of additives that can be used include other inorganic fillers, plasticizers, pigments, rubber vulcanizing agents, reinforcing agents, adhesion-imparting agents, ultraviolet rays and ozone degradation inhibitors, and the like. As other inorganic fillers, for example, calcium carbonate powder (untreated), heavy calcium carbonate powder, quartz powder, alumina, calcium oxide, talc, glass powder, various aggregates, and the like can be used.

In the case of a modified silicone sealant or adhesive, the modified silicone resin is known per se and is hydrolyzable such as an Si group with an alkoxy group, a halogen atom, an acyloxy group, an alkenyloxy group, an amide group, an oxime group. It is a polymer containing a hydrolyzable silyl group to which a group is bonded at the molecular chain end and having a repeating unit of propylene oxide as a skeleton.
The amount of the surface-treated calcium carbonate filler of the present invention is usually about 10 to 200 parts by weight, preferably about 20 to 150 parts by weight with respect to 100 parts by weight of the modified silicone resin. If the content of the surface-treated calcium carbonate is less than 10 parts by weight, the effects of thixotropy and slump resistance cannot be expected. On the other hand, if it exceeds 200 parts by weight, storage stability, adhesiveness, etc. may be deteriorated. .
As the filler, for example, heavy calcium carbonate, colloidal calcium carbonate, clay, talc, titanium oxide, zinc oxide, colloidal silica or the like can be used as a filler extender or viscosity modifier. These may be used alone or in combination of two or more.
As the curing catalyst, for example, a tin-based catalyst such as tin octylate, dibutyltin laurate, dibutyltin dioctoate, dibutyltin oxide, dioctyltin oxide, or an amine can be used. These may be used alone or in combination of two or more. The amount of the curing catalyst is used in the range of 0.5 to 6.0 parts by weight with respect to 100 parts by weight of the resin.
As the plasticizer, phthalic esters such as dioctyl phthalate (DOP), fatty acid esters, glycol esters, and the like can be used. These may be used alone or in combination of two or more. The amount of the plasticizer is used in the range of 20 to 80 parts by weight with respect to 100 parts by weight of the modified silicone resin.
The modified silicone sealant or adhesive of the present invention may further include a color pigment, an ultraviolet absorber, an antioxidant, an adhesion improver, an anti-aging agent, a metal deactivator, an ozone degradation inhibitor, if necessary. You may add 1 type, or 2 or more types, such as a light stabilizer and a foaming agent.

In the case of a silicone sealant or an adhesive, the silicone resin is known per se, and a linear organopolysiloxane having reactive silanol groups at both ends is used as the main agent.
As the crosslinking agent (curing agent), cyclic and linear siloxanes having aminoxy groups and organopolysiloxanes having alkoxylane functional groups are used. The amount of the crosslinking agent used is in the range of 50 to 150 parts by weight with respect to 100 parts by weight of the resin.
In addition, an organopolysiloxane having one hydroxyl group at one end and a silanol group at the other end is used as the main agent, and an inert organopolysiloxane having no such functional group and a curing catalyst for the above-described modified silicone sealant are blended. It can also be used in combination with a curing agent, and the blending amount of the curing catalyst is in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the resin.
In the present invention, a solvent, a plasticizer, a filler, a pigment, a thickener, a thixotropic agent, a stabilizer, and other additives can be blended as necessary.
Examples of the plasticizer include straight silicone oils such as dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, polyether modified, epoxy modified, amino modified, carboxyl modified, carbinol modified silicone oil, and the like.
The compounding quantity of a plasticizer is the range of 0-30 weight part with respect to 100 weight part of resin. Other examples of the adhesion-imparting agent include titanium-based chelate compounds, amine-based and epoxy-based coupling agents.

  In addition, the acrylic plastisol formed by blending the surface-treated calcium carbonate filler of the present invention is composed of acrylic polymer particles, a plasticizer, and a filler. However, a block type urethane resin and a curing agent can be blended. In addition, other conventionally known additives such as colorants, antioxidants, foaming agents, diluents, ultraviolet absorbers and the like can be blended.

  As the acrylic polymer particles constituting the acrylic plastisol, any acrylic polymer particles usually used as a composition of an acrylic plastisol can be used. For example, a homopolymer or copolymer of a monomer selected from alkyl acrylate, alkyl methacrylate and the like can be used. As these monomers, specifically, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, decyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl Examples include methacrylate, octyl methacrylate, decyl methacrylate, hydroxymethethyl acrylate, and hydroxypropyl methacrylate, and these are used alone or in combination of two or more. Among these, polymer particles having a core / shell structure are preferably used from the viewpoint of storage stability and ease of adjusting the gel speed. For example, the core is composed of alkyl acrylate, hydroxy acrylate, alkyl methacrylate, hydroxy methacrylate homopolymers, copolymers thereof, and copolymers of these with acrylic acid, methacrylic acid, maleic acid, itaconic acid, styrene, etc. Formed from polymer to plasticizer compatible, shell part is methyl methacrylate homopolymer, methyl methacrylate and alkyl acrylate or hydroxy acrylate, alkyl methacrylate, hydroxy methacrylate, acrylic acid, methacrylic acid, maleic acid, itacon Examples thereof include those formed incompatible with a plasticizer from a copolymer with an acid, styrene or the like.

  Moreover, as a plasticizer which comprises acrylic plastisol, well-known plasticizers, such as a phthalic acid ester, phosphoric acid ester, adipic acid ester, and a sebacic acid ester plasticizer, can be used. As phthalate ester plasticizers, dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), diisodecyl phthalate (DIDP), butyl Examples of phosphate plasticizers such as benzyl phthalate (BBP), diisononyl phthalate (DINP), dinonyl phthalate (DNP) include tricresyl phosphate (TCP), triphenyl phosphate (TPP), and trixylylene phosphate (TXP) Examples of adipate plasticizers include dioctyl adipate (DOA) and diisodecyl adipate (DIDA). Examples of sebate ester plasticizers include dibutyl sebacate (DBS) and dioctylsecetate. Kate (DOS) can be exemplified, and epoxy plasticizers such as epoxidized soybean oil, benzoic acid plasticizers, polyester plasticizers and the like can be used alone or in combination of two or more. However, phthalic acid plasticizers are particularly preferable.

Furthermore, in the present invention, a low boiling point plasticizer having a boiling point of 150 to 250 ° C., for example, a petroleum hydrocarbon (paraffinic, naphthenic, aromatic) plasticizer, etc. is used if necessary for improving spray workability. Can be blended.
As the filler, in addition to the filler of the present invention, precipitated calcium carbonate, heavy calcium carbonate, colloidal silica, talc, kaolin, zeolite, resin balloon, glass balloon, etc. These general fillers may be used in combination.
The acrylic plastisol preferably contains a block type urethane resin. Examples of the block type urethane resin include polyols such as polyether polyol and polyester polyol, diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, 1 Urethane resins obtained by reacting isocyanates such as 1,3-biscyclohexane diisocyanate, tetramethylxylylene diisocyanate, m-isopropenyl dimethyl benzyl isocyanate, etc. with a blocking agent such as oxime or amine, , Oxybenzoic ester of diisocyanate polymer, or alkylphenol block product, nuray of diisocyanate polymer One or a combination of two or more such as ring formation member is preferably used.
As the colorant, for example, inorganic pigments such as titanium dioxide and carbon black, azo-based and phthalocyanine-based organic pigments, and the like can be used. As the antioxidant, for example, a phenol-based or amine-based antioxidant can be used. As the foaming agent, a type of foaming agent that generates gas when heated can be used, and for example, azo foaming agents such as azodicarbonamide and azobisformamide can be used. As the diluent, for example, a solvent such as xylene or mineral terpene can be used. A benzotriazole type etc. can be used as a ultraviolet absorber.
The blending ratio of the surface-treated calcium carbonate filler of the present invention and these resins is not particularly limited, and may be appropriately determined according to the type and use of the resin, desired physical properties, and other filling as described above. Of course, various additives such as materials, plasticizers and stabilizers may be added. For example, in the case of acrylic plastisol, it is usually about 10 to 300 parts by weight, preferably 20 to 250 parts by weight, and more preferably about 30 to 200 parts by weight with respect to 100 parts by weight of the resin.

In the case of vinyl chloride plastisol, a vinyl chloride resin is used as a base polymer, and an organic foaming agent, if necessary, a foaming aid, a filler, a plasticizer, and an adhesive component are blended, and if necessary, moisture is absorbed. Agents, stabilizers, colorants and the like can be blended.
The vinyl chloride resin (PVC) that constitutes the vinyl chloride plastisol is mainly composed of vinyl chloride homopolymer, vinyl chloride, and other copolymerizable monomers such as vinyl acetate (including vinyl chloride) 1 type in an amount of 50% by weight or more, particularly 70% by weight or more) can be used alone or in combination of two or more.
In this case, PVC has an average particle size of 5 μm or less, preferably 3 μm or less, and more preferably 1.5 μm or less. Use of a PVC having a large average particle diameter exceeding 5 μm reduces chipping resistance and causes abnormal foaming on the foamed surface, which may be undesirable in terms of appearance. In addition, as the PVC, those having two peaks in the particle size distribution in the above average particle size range are preferably used from the viewpoint of workability and physical properties of the obtained foamed PVC. It is done. The PVC having a particle size distribution having two peaks here is different from a mixture of two types of PVC having different average particle sizes, and a part of the primary particles having a small particle size is in the manufacturing process. The secondary particles are obtained by agglomeration in the above, and the primary particles having a small particle diameter and the secondary particles obtained by agglomerating the secondary particles coexist, thereby having two peaks in the particle size distribution.
Further, as the PVC, an average degree of polymerization of 2500 or less, preferably 2000 or less, more preferably 1900 or less is desirable. When the average degree of polymerization is too high, physical properties of the foamed PVC such as chipping resistance may be deteriorated. The lower limit of the average degree of polymerization is usually 500, preferably 850, and more preferably 1000.
As the copolymer, vinyl chloride-vinyl acetate copolymer is preferably used from the viewpoint of swelling gelation. In this vinyl chloride-vinyl acetate copolymer, the vinyl acetate content is 1 to 15% by weight, particularly 3 to 10%. A weight percent is preferred. In this case, the vinyl chloride homopolymer is somewhat inferior in adhesion to the metal surface compared to the vinyl chloride-vinyl acetate copolymer, while the vinyl chloride-vinyl acetate copolymer has a good swelling gelling property for the plasticizer and adheres when heated. Although it is good, the cost is high, so it is preferable to use both in combination. The ratio of the combined use is appropriately selected, but it is preferable that the vinyl chloride homopolymer: vinyl chloride-vinyl acetate copolymer = 4: 1 to 1: 4 (weight ratio).
Moreover, a crosslinkable copolymer having a —CH 2 ROH group can also be used as the copolymer. This OH group reacts with blocked isocyanate as an adhesion component, which will be described later, upon heating to produce a urethane bond, thereby improving adhesion and water resistance.

As the organic foaming agent constituting the vinyl chloride plastisol, a foaming agent that generates gas by heating can be used. For example, 4,4′-oxybis (benzenesulfonylhydrazide (OBSH) is preferably used. Thus, p-toluenesulfonyl azide, p-methylurethanebenzenesulfonyl hydrazide, etc. can be used, and as a foaming agent mixture, a mixture of OBSH and azodicarbonamide (ADCA) is preferably used. be able to.
As the foaming auxiliary agent constituting the vinyl chloride plastisol, known ones can be used, and various metal oxides (for example, zinc oxide and magnesium oxide), metal soap (for example, zinc stearate), urea compounds, An amine etc. are mentioned. In addition, such a foaming auxiliary agent can be blended for other purposes at the same time.
Examples of the filler include calcium carbonate, barium sulfate, clay, diatomaceous earth, silica, talc and the like, and one of these can be used alone or two or more can be used in combination. If necessary, hollow particles such as glass balloons and resin balloons can be blended.
As the plasticizer constituting the vinyl chloride plastisol, one or more of a phthalate plasticizer or a benzoate plasticizer and one or two of a trimellitic ester plasticizer or a polyester plasticizer More than seeds can be used. As the phthalate ester plasticizer, dibutyl phthalate (DBP), dihexyl phthalate (DHP), di-2-ethylhexyl phthalate (DOP), di-n-octyl phthalate (DnOP), diisooctyl phthalate (DIOP), di Decyl phthalate (DDP), dinonyl phthalate (DNP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), C6 to C10 mixed higher alcohol phthalate, butyl benzyl phthalate (BBP), octyl benzyl phthalate, nonyl benzyl phthalate, butyl phthalate Tar butyl glycolate (BPBG) and the like, and benzoate plasticizers include dipropylene glycol benzoate, N-butyl benzoate, 2,2,4-trimethyl-1,3-pen Examples thereof include tandiol isobutyrate benzoate and 2,2,4-trimethyl-1,3-pentanediol dibenzoate. Trimellitic acid ester plasticizers include tri- (2-ethylhexyl) trimellitate (TOTM), tri-n-octyl trimellitate, triisodecyl trimellitate, triisooctyl trimellitate, and the like. . Polyester plasticizers include epoxidized double bonds of unsaturated fatty acid glycerides such as soybean oil with hydrogen peroxide or peracetic acid (ESBO), and epoxy compounds such as butyl or octyl alkyl oleates. A viscous low-polymerization polyester having an average molecular weight of about 500 to 8000, in which several to dozens of propylene glycol ester units of a dibasic acid such as adipic acid are connected in a straight chain. Adipic acid polyesters having an average molecular weight of 500 to 2200 and phthalic acid-based polyesters (oligoesters of phthalic acid and alkylene glycol, terminal alkanols, alkanes or alkenoic acid modified products) are suitable.

As a plasticizer, in addition to the above, other plasticizers can be further blended. Other plasticizers include tricresyl phosphate (TCP), trioctyl phosphate (TOF), trixylenyl phosphate (TXP), monooctyl diphenyl phosphate, monobutyl-dixylenyl phosphate (BZX), etc. Phosphate esters, phenolic alkyl sulfonate esters, dioctyl adipate (DOA), dioctyl azelate (DOZ), dioctyl sebacate (DOS) and other linear dibasic acid esters, 2,2,4-trimethyl -1,3-pentadiol mono- or diisobutyrate, tributyl citrate ester, trioctyl acetyl citrate ester, tri- or tetraethylene glycol ester of C6 to C10 fatty acid, methyl acetyl ricinolate and other ester systems Plasticizers, Examples thereof include nitrile synthetic rubbers, chlorinated products, and petroleum auxiliary plasticizers.
Furthermore, in the present invention, a low boiling point plasticizer having a boiling point of 150 to 250 ° C., for example, a petroleum hydrocarbon (paraffinic, naphthenic, aromatic) plasticizer, etc. is used if necessary for improving spray workability. Can be blended.

The vinyl chloride plastisol can be used in combination with a polyamidoamine and a blocked isocyanate as an adhesion component, thereby improving the adhesion of the foamed PVC coating to the substrate. In particular, the polyamidoamine and the blocked isocyanate are used. When used together, water resistance and corrosion resistance are remarkably improved, and noise prevention is also remarkably improved. This is because the polyamidoamine and the blocked isocyanate are cross-linked to form a urethane bond, the PVC coating film is given flexibility and elasticity, the impact absorption is improved, and the sound evaluation is excellent. Conceivable.
Hygroscopic agents such as calcium oxide and magnesium oxide can be added to the vinyl chloride plastisol, catching moisture in the sol to prevent foaming due to moisture, and improving the water resistance and corrosion resistance of foamed PVC Furthermore, PVC stabilizers such as dibutyltin laurate-based and zinc-based organic composites can be blended as the bubble regulator. In addition, pigments such as carbon black, titanium oxide, cadmium yellow, and phthalocyanine blue can be used as the colorant. The blending ratio of the surface-treated calcium carbonate filler of the present invention and these resins is not particularly limited. Of course, it may be determined appropriately according to the type and application of the material, and the desired physical properties, and various additives such as other fillers, plasticizers and stabilizers as described above may be added. In the case of vinyl chloride plastisol, it is usually 160 to 500 parts by weight, preferably 180 to 450 parts by weight, and more preferably about 200 to 400 parts by weight with respect to 100 parts by weight of the resin.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention does not receive a restriction | limiting at all by these.

Example 1
48 g of sodium laurate (alkyl composition: C12: 100%) in 1 L of warm water at 80 ° C. with respect to 10 L of precipitated calcium carbonate water slurry having a BET specific surface area of 17 m ² / g adjusted to a concentration of 160 g CaCO 3 / L and a temperature of 50 ° C. , The same applies hereinafter) and a surface treatment agent prepared with 16 g of extremely hardened palm fatty acid (alkyl composition: C16: 56%, C18: 44%, the same applies hereinafter) and vigorously stirred together with the calcium carbonate slurry. The calcium carbonate slurry was dehydrated to a solid content of 60%, dried in a box dryer at 110 ° C. for 12 hours, and then pulverized to obtain a surface-treated calcium carbonate powder having a BET specific surface area of 15 m ² / g. Drying temperature, drying time, BET specific surface area Sw, heat loss Tg, surface treatment agent amount As per unit specific surface area, and calcium carbonate that is not eluted as a free product when the surface-treated calcium carbonate is extracted with ethanol. The ratio of the amount of the surface treatment agent remaining on the side to the total surface treatment agent amount Cr, the ratio Ar of the amount of free fatty acid in the free substance to the amount of the total surface treatment agent, the counter ion in the free substance is a monovalent fatty acid salt amount Table 1 shows the ratio Sr to the total amount of the surface treatment agent and the ratio Ar / (Ar + Sr) of the amount of free fatty acid in the amount of free products.
In addition, about the surface treating agent, the surface treatment amount, the drying temperature, the drying time, and the obtained powder Sw, Tg, As, Cr, Ar, Sr, Ar / (Ar + Sr) in Examples 2 to 13 below. It is shown in Table 1.

Example 2
Example 1 was the same as Example 1 except that it was changed to drying for 5 hours using a 120 ° C box dryer.

Example 3
Example 1 was the same as Example 1 except that it was changed to drying for 5 hours using a box dryer at 140 ° C.

Example 4
In Example 1, everything was the same as Example 1 except changing to drying for 5 hours.

Example 5
The same procedure as in Example 1 was performed except that the surface treatment agent was changed to 16 g of sodium laurate and 48 g of extremely hardened palm fatty acid in Example 1.

Example 6
In Example 1, 32 g of sodium laurate and 32 g of beef tallow fatty acid (alkyl composition: C14: 5%, C16: 28%, C18: 22%, C18F1: 40%, C18F2: 5%, F1 is the surface treatment agent) All were the same as in Example 1 except that one double bond and F2 were changed to two double bonds, the same applies hereinafter. The unsaturated component in the surface treatment agent was 22.5% by weight.

Example 7
Example 1 was the same as Example 1 except that the surface treatment agent was changed to 16 g of sodium laurate and 48 g of beef tallow fatty acid. The unsaturated component in the surface treatment agent was 33.8% by weight.

Example 8
The same procedure as in Example 1 was conducted except that the surface treatment agent was changed to 64 g of ammonium stearate (alkyl composition: C18: 100%) in Example 1.

Example 9
In Example 1, except that the precipitated calcium carbonate water slurry with a BET specific surface area of 45 m ² / g was changed to a BET specific surface area of 40 m ² / g, and the surface treatment agent was changed to 96 g of sodium laurate and 96 g of extremely hardened palm fatty acid. All were the same as in Example 1.

Example 10
In Example 1, the aqueous slurry of precipitated made calcium carbonate having a BET specific surface area of 3m ² / g, a BET specific surface area 3m ² / g, except for changing the surface treatment agent to sodium laurate 16g and extremely hydrogenated palm fatty acid 16g is All were the same as in Example 1.

Example 11
The same procedure as in Example 1 was performed except that the surface treatment agent was changed to 32 g of sodium laurate and 32 g of extremely hardened palm fatty acid in Example 1.

Example 12
The same procedure as in Example 1 was performed except that the surface treatment agent was changed to 32 g of lauric acid and 32 g of extremely hardened palm fatty acid in Example 1.

Example 13
The same procedure as in Example 1 was conducted except that the surface treatment agent was changed to 32 g of sodium laurate and 32 g of extremely hardened palm fatty acid sodium in Example 1.

Comparative Example 1
Example 1 was the same as Example 1 except that the drying time was changed to 3 hours. Table 2 shows the surface treatment agent, surface treatment amount, drying temperature, drying time, and Sw, Tg, As, Cr, Ar, Sr, and Ar / (Ar + Sr) of the obtained powder. In addition, it showed in Table 2 similarly about Comparative Examples 2-7.

Comparative Example 2
Example 1 was the same as Example 1 except that the drying temperature was changed to 80 ° C.

Comparative Example 3
In Example 1, the aqueous slurry of precipitated made calcium carbonate having a BET specific surface area of 2m ² / g, a BET specific surface area 2m ² / g, except for changing the surface treatment agent to sodium laurate 12g and extremely hydrogenated palm fatty acid 8g is All were the same as in Example 1.

Comparative Example 4
In Example 1, except that the precipitated calcium carbonate water slurry having a BET specific surface area of 47 m ² / g, the BET specific surface area was changed to 41 m ² / g, and the surface treatment agent was changed to 96 g of sodium laurate and 96 g of extremely hardened palm fatty acid. All were the same as in Example 1.

Comparative Example 5
In Example 1, except that the precipitated calcium carbonate water slurry with a BET specific surface area of 45 m ² / g was changed to a BET specific surface area of 40 m ² / g and the surface treatment agent was changed to 16 g of sodium laurate and 8 g of extremely hardened palm fatty acid sodium. Were all the same as in Example 1.

Comparative Example 6
In Example 1, except that the water slurry of precipitated calcium carbonate having a BET specific surface area of 45 m ² / g was changed to a BET specific surface area of 40 m ² / g, and the surface treatment agent was changed to 16 g of lauric acid and 16 g of extremely hardened palm fatty acid sodium. All were the same as in Example 1.

Comparative Example 7
The same procedure as in Example 1 was performed except that the surface treatment agent was changed to 32 g of sodium laurate and 32 g of sodium hardened palm fatty acid after drying for 12 hours in a box dryer at 80 ° C.

Examples 14 to 26, Comparative Examples 8 to 14
An acrylic plastisol was prepared from the surface-treated calcium carbonate filler obtained in Examples 1 to 13 and Comparative Examples 1 to 7 by the following test method (1), and the physical properties thereof were tested. The results are shown in Tables 3 and 4.

(Test method (1) Acrylic plastisol)
[Combination]
Acrylic resin ZEON acrylic resin F345 (manufactured by Shin-Daiichi Vinyl Industrial Co., Ltd.)
250 parts by weight urethane block polymer (manufactured by Mitsui Takeda Chemical Co., Ltd.) 100 parts by weight urethane curing agent (manufactured by Mitsui Takeda Chemical Co., Ltd.) 5 parts by weight DINP 350 parts by weight Terpen 75 parts by weight Surface treated calcium carbonate filler 180-425 parts by weight Calcium carbonate 0-245 parts by weight
The total amount of 1205 parts by weight The amount of the surface-treated calcium carbonate filler varies depending on the BET specific surface area of the base calcium carbonate, so that the amount of heavy calcium carbonate varies depending on the amount of heavy calcium carbonate. The total amount was the same and was selected according to the actual use viscosity.

[Kneading method]
Each compounding agent is put into a 5 L universal mixing stirrer (manufactured by Dalton) and kneaded for 3 minutes. After the lid is opened, the compounding agent adhering to the wall surface is scraped off, and then kneaded again in a vacuum atmosphere for 10 minutes. The sol after kneading was defoamed with a planetary defoaming kneader (Kurabo Co., Ltd./KK-500) under kneading conditions 5-5-18 to prepare an acrylic sol.
In the kneading conditions “abc”, “a” represents revolution conditions, “b” represents rotation conditions, “c” represents time, and means c × 10 seconds.

[Sol viscosity measurement]
The acrylic sol after kneading is packed in a 100 ml PP (polypropylene) cup, left to stand at 23 ° C. for 3 days, and then used with a TV-type viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) (Range H Spindle No. H7) The viscosity at 2 rpm and 20 rpm was measured as the initial viscosity.
The 2 rpm viscosity was the value after 2 minutes, and 20 rpm was the value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 2 rpm viscosity value by the 20 rpm viscosity value. The kneaded acrylic sol was filled in a 100 ml PP cup and allowed to stand at 40 ° C. for 3 days. After being allowed to cool at 23 ° C. for 3 hours, the viscosity at 2 rpm and 20 rpm was stored, and then the viscosity was 2 rpm / A numerical value of 20 rpm was measured as a TI value after storage.

[Sol viscosity criteria]
The determination was made according to the following criteria according to the TI value (2 rpm viscosity / 20 rpm viscosity).
◎: 6.00 or more ○: 5.50 or more and less than 6.00 Δ: 5.00 or more and less than 5.50 ×: less than 5.00

[Storage stability test]
The initial viscosity value measured after 23 ° C. × 3 days and the post-storage viscosity value measured after 40 ° C. × 3 days (23 ° C. × 3 hours standing) are obtained by storing the viscosity change ratio and the TI value change ratio based on the following equations and stored. Stability (rate of change%) was evaluated.
Viscosity change rate:
[(Viscosity value at each rotational speed after storage) / (Viscosity value at each initial rotational speed)] × 100
TI value change rate:
[(TI value after storage / initial TI value)] × 100
[Storage stability criteria]
The determination was made according to the following criteria according to the viscosity change rate and the TI value change rate.
◎: Viscosity change rate less than 105% and TI value change rate 95% or more ○: Viscosity change rate 105% or more and less than 120%, TI value change rate 85% or more and less than 95% △: Viscosity change rate 120% or more and less than 130% TI value change rate 80% or more and less than 85% ×: Viscosity change rate 130% or more and TI value change rate less than 80%

[Dispersibility test]
The surface-treated calcium carbonate filler was weighed and put into a paper bag. The paper bag was put on a weight so that a load of 1 t was applied per 1 m ² , and compacted at 50 ° C. for 7 days. (In the case of paper bag size 20cm x 20cm, 40kg load)
5L universal mixing stirrer (manufactured by Dalton Co.) was charged with each compounding agent and surface-treated calcium carbonate subjected to compaction conditions, kneaded for 3 minutes, and once the lid was opened, the compounding agent adhering to the wall surface was scraped off. Again knead for 10 minutes in a vacuum atmosphere. The sol after kneading was defoamed with a planetary defoaming kneader (Kurabo Co., Ltd./KK-500) under kneading conditions 5-5-18 to prepare an acrylic sol.
After mixing, the acrylic sol was thinly spread on a glass plate with a spatula so that it had a length of 5 cm or more, a width of 5 cm or more, and a thickness of 1 mm or less. In the kneading conditions “abc”, “a” represents revolution conditions, “b” represents rotation conditions, “c” represents time, and means c × 10 seconds.
[Dispersibility test criteria]
The number of particles of 0.5 mm or more per 5 cm square was measured on the acrylic sol surface coated on the glass plate, and the dispersibility was determined according to the following criteria based on the measured number.
○: 0 or more grains of 0.5 mm or more Δ: 1 or 2 grains of 0.5 mm or more ×: 3 or more grains of 0.5 mm or more

[Slip resistance test]
The acrylic sol after kneading is packed in a 100 ml PP cup, left to stand at 23 ° C. for 3 days, applied to a 130 × 60 mm adherend with a length of 100 mm on a 12 mm semi-circular bead, and then allowed to stand at 23 ° C. Then, the distance the sol slipped after 30 minutes was measured with a ruler.
[Slip resistance test criteria]
The determination was made according to the following criteria.
○: 0 mm
Δ: Over 0 mm and less than 10 mm ×: 10 mm or more

[Electrodeposition plate adhesion test method]
The acrylic sol after kneading is applied to a fully polished 70 mm x 150 mm steel plate to a thickness of 3 mm, baked and cured in a constant temperature bath at 100 ° C for 30 minutes, and exposed to room temperature for 15 minutes to cool. After that, after further cooling, the cured coating film was peeled off with a nail after cooling for 30 minutes, and the state where the cured coating film remained on the electrodeposition plate was expressed as a cohesive fracture ratio (CF%). The adhesion was confirmed. Judgment was made according to the following criteria.
[Electrodeposition plate adhesion criteria]
○: Extremely excellent adhesion, and when it is peeled off, it breaks with the cured coating film remaining on the electrodeposition plate (CF100%)
Δ: Excellent adhesion, but breaks when peeled off with the cured coating remaining 70% or more and less than 100% on the electrodeposition plate (70% ≦ CF <100%)
X: Easily peeled off and fractured in a state where the cured coating film remains less than 70% on the electrodeposition plate when removed (CF <70%)
In Tables 3 and 4, the acrylic plastisols of Examples 14 to 26 blended with the surface-treated calcium carbonate fillers of Examples 1 to 13 are excellent in dispersibility and thixotropy, and have storage stability, slip resistance, electrical properties, and the like. It can be seen that it also shows excellent performance in adhesion to the landing plate.

Examples 27-39, Comparative Examples 15-21
A vinyl chloride plastisol was prepared from the surface-treated calcium carbonate filler obtained in Examples 1 to 13 and Comparative Examples 1 to 7 by the following test method (2), and the physical properties thereof were tested. The results are shown in Tables 5 and 6.
In addition, (Test method (2) Vinyl chloride plastisol) was carried out according to the above (Test method (1) Acrylic plastisol) except for the following composition.

[Combination]
PVC paste resin PCH-22 (manufactured by Kaneka Corporation) 250 parts by weight polyamide (manufactured by Henkel Co., Ltd.) 15 parts by weight DINP 250 parts by weight Turpen 37 parts by weight Quicklime (manufactured by Wako Pure Chemical Industries, Ltd.) 15 parts by weight Surface-treated calcium carbonate Filler 75-200 parts by weight Heavy calcium carbonate Super S (manufactured by Maruo Calcium Co., Ltd.) 250-375 parts by weight
The total amount of 1017 parts by weight The amount of the surface-treated calcium carbonate filler varies depending on the BET specific surface area of the base calcium carbonate. The total amount was the same with the amount selected in accordance with the actual use viscosity.
In Tables 5 and 6, the vinyl chloride plastisols of Examples 27 to 39 blended with the surface-treated calcium carbonate filler of Examples 1 to 13 are excellent in dispersibility and thixotropy, and have storage stability, slip resistance, It turns out that the performance which was excellent also in the adhesiveness with an electrodeposition board is shown.

Examples 40-52, Comparative Examples 22-28
Using the surface-treated calcium carbonate filler obtained in Examples 1 to 13 and Comparative Examples 1 to 7, a one-component polyurethane sealant was prepared by the following test method (3), and the effect test was performed. The results are shown in Tables 7 and 8.

(Test method (3) One-component polyurethane sealant)
[Combination]
Polyurethane resin Takenate L-1036 (Mitsui Takeda Chemical Co., Ltd.)
540 parts by weight Surface-treated calcium carbonate 390 parts by weight Heavy calcium carbonate 90 parts by weight Mineral terpenes 120 parts by weight
Total 1140 parts by weight The amount of the surface-treated calcium carbonate filler varies depending on the BET specific surface area of the calcium carbonate used as the base, but there are low and high viscosity types depending on the adhesive application. I went there.

[Kneading method]
Put polyurethane resin into 5L universal mixing stirrer (manufactured by Dalton Co., Ltd.) and put it together with surface-treated calcium carbonate filler and heavy calcium carbonate that have been dried at 105 ° C for 2 hours or more in advance. It was. Then, after scraping off the filler adhering in the mixing stirrer, the mixture was immediately kneaded at a high speed for 30 minutes in a vacuum atmosphere. Finally, a mineral turpent was put in and mixed at a low speed for 15 minutes in a vacuum atmosphere. This was filled in an aluminum foil laminate-coated cartridge and sealed with a metal plunger to prepare a one-component polyurethane sealant.

[Viscosity measurement method]
A sealant that was allowed to stand at 23 ° C. for one day was packed into a 100 ml PP cup with a cartridge gun and measured using a TV-type viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) (range S, spindle No. H7). did.
1 rpm viscosity was a value after 3 minutes, and 10 rpm was a value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 1 rpm viscosity value by the 10 rpm viscosity value. Note that Example 49 and Comparative Example 24 were measured in the range H because of low viscosity.

[Viscosity criteria]
The determination was made according to the following criteria according to the TI value (1 rpm viscosity / 10 rpm viscosity).
◎: 6.00 or more ○: 5.50 or more and less than 6.00 Δ: 5.00 or more and less than 5.50 ×: less than 5.00

[Storage stability test]
The initial viscosity value measured after 23 ° C. × 1 day and the post-storage viscosity value measured after 50 ° C. × 7 days (23 ° C. × 3 hours cooling) are obtained by determining the viscosity change rate and the TI value change rate based on the following equations and stored. Stability (rate of change%) was evaluated.
Viscosity change rate:
[(Viscosity value at each rotation speed after storage) / (Viscosity value at each initial rotation speed)] × 100
TI value change rate:
[(TI value after storage) / (initial TI value)] × 100
[Storage stability criteria]
The determination was made according to the following criteria according to the viscosity change rate and the TI value change rate.
◎: Viscosity change rate is less than 120% and TI value change rate is 95% or more ○: Viscosity change rate is 120% or more and less than 140%, TI value change rate is 80% or more and less than 95% △: Viscosity change rate is 140% or more and less than 150% TI value change rate 70% or more and less than 80% ×: Viscosity change rate 150% or more and TI value change rate less than 70%

[Dispersibility test]
390 g of the surface treated calcium carbonate filler was weighed and put into a paper bag. The paper bag was put on a weight so that a load of 1 t was applied per 1 m ² , and compacted at 50 ° C. for 7 days. The surface-treated calcium carbonate after the consolidation condition is dried at 105 ° C. for 2 hours or more.
After adding polyurethane resin to a 5 L universal mixing stirrer (manufactured by Dalton Co., Ltd.), 540 g of the surface-treated calcium carbonate filler and 90 g of heavy calcium carbonate, which were dried in advance at 105 ° C. for 2 hours or more, were added. Pre-stirring was performed at low speed for 15 minutes. Then, after scraping off the filler adhering in the mixing stirrer, the mixture was immediately kneaded at a high speed for 30 minutes in a vacuum atmosphere. Finally, 120 g of mineral terpenes were added and mixed at a low speed for 15 minutes in a vacuum atmosphere. The sealant after mixing was spread thinly on a glass plate with a spatula so that the length was 5 cm or more, the width was 5 cm or more, and the thickness was 1 mm or less.
[Dispersibility test criteria]
The number of particles of 0.5 mm or more per 5 cm square was measured on the surface of the sealant coated on the glass plate, and the dispersibility was determined according to the following criteria based on the measured number.
○: 0 or more grains of 0.5 mm or more Δ: 1 or 2 grains of 0.5 mm or more ×: 3 or more grains of 0.5 mm or more

[Tensile test method]
A primer (NO.30 made by Yokohama Rubber Co., Ltd.) is applied to the surface of an aluminum plate (50mm x 50mm x 3mm), dried for 60 minutes, then filled with the above sealant (shape 12mm x 12mm x 50mm), JIS A 1439 Architectural sealant 5.17.2 Durability and tensile test specimens were produced in accordance with the H-type specimens.
This specimen was cured at 23 ° C. × 14 days + 35 ° C. × 14 days, and measured at 23 ° C. × 1 day using a tensile tester (manufactured by Shimadzu Corp., Autograph AG-1).
50% tensile stress: Value obtained by dividing the load when stretched at a rate of 50 mm per minute and stretched at 50% (6 mm) elongation by the cross-sectional area of the sealant (600 mm ² ) Maximum strength: At a rate of 50 mm per minute Tensile, value obtained by dividing the largest load by the cross-sectional area of the sealant Elongation rate: Value obtained by dividing the displacement at the time of maximum strength by the shape at the time of filling (12 mm) and multiplying by 100 Adhesiveness (initial): 23 ° C × 14 days + 35 ° C x 14 days, 23 ° C x 1 day later Judged by the ratio of the sealant remaining on the bonded aluminum surface when the tensile test was performed Adhesiveness (hot water): After initial curing, 50 ° C hot water x 7 A tensile test is performed after sun soaking, and it is determined by the ratio of the sealant remaining on the broken aluminum adhesive surface.
[Criteria for tensile test]
50% tensile stress: ○: Less than 0.20 N / mm ²
×: 0.20N / mm ² or more maximum intensity: ◎: 1.00 N / mm ² or more
○: 0.60 N / mm ² or more and less than 1.00 N / mm ²
Δ: 0.50 N / mm ² or more and less than 0.60 N / mm ²
×: Less than 0.50 N / mm ² Elongation: ◎: 700% or more
○: 600% or more and less than 700%
Δ: 500% or more and less than 600%
X: Less than 500% Adhesiveness: The state in which the sealant remained on the aluminum bonded surface was expressed in terms of the cohesive failure rate (CF%) and evaluated according to the following criteria.
○: Destruction with 100% sealant remaining (CF100%)
Δ: Destruction in a state where the sealant remains 50% or more and less than 100% (CF50% to CF99%)
×: Less than 50% remaining sealant CF <50% or peeled off (AF)
In Tables 7 and 8, the polyurethane sealants of Examples 40 to 52 blended with the surface-treated calcium carbonate fillers of Examples 1 to 13 are excellent in dispersibility and thixotropy, and have storage stability, adhesive strength, and elongation. It can be seen that the performance is excellent in hot water adhesion.

Examples 53 to 65, Comparative Examples 29 to 35
Using the surface-treated calcium carbonate filler obtained in Examples 1 to 13 and Comparative Examples 1 to 7, a one-component modified silicone sealant was prepared by the following test method (4), and the effect test was performed. The results are shown in Tables 9 and 10.

(Test method (4) one-component modified silicone sealant)
[Combination]
Modified silicone resin (MS polymer S203, manufactured by Kaneka Corporation) 300 parts by weight Plasticizer DINP (manufactured by J-Plus Co., Ltd.) 180 parts by weight Heavy calcium carbonate (Super S, manufactured by Maruo Calcium Co., Ltd.) 90 parts by weight Surface treatment Calcium carbonate filler 420 parts by weight Dehydrating agent KBM-1003 (Shin-Etsu Chemical Co., Ltd.) 18 parts by weight Tin catalyst Neostan U220H (Nitto Kasei Co., Ltd.) 6 parts by weight Aminosilane KBM-603 (Shin-Etsu Chemical Co., Ltd.) 6 parts by weight Part
Total 1020 parts by weight

[Kneading method]
Put the modified silicone resin in a 5L universal mixing stirrer (manufactured by Dalton Co., Ltd.) and put it together with the surface-treated calcium carbonate filler and heavy calcium carbonate that have been dried at 105 ° C for 2 hours or more in advance. went. Then, after scraping off the filler adhering in the mixing stirrer, the mixture was immediately kneaded at a high speed for 30 minutes in a vacuum atmosphere. Thereafter, a dehydrating agent, a tin catalyst, and aminosilane were added and mixed in a vacuum atmosphere for 15 minutes at a low speed. This was filled in an aluminum foil laminate-coated cartridge and sealed with a metal plunger to prepare a one-component modified silicone sealant.

[Viscosity measurement method]
A sealant that was allowed to stand at 23 ° C. for one day was packed into a 100 ml PP cup with a cartridge gun and measured using a TV-type viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) (range S, spindle No. H7). did.
The 1 rpm viscosity was the value after 3 minutes, and the 10 rpm viscosity was the value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 1 rpm viscosity value by the 10 rpm viscosity value. In addition, since Example 62 and the comparative example 31 were low viscosity, it measured using the range H.
[Viscosity criteria]
The determination was made according to the following criteria according to the TI value (1 rpm viscosity / 10 rpm viscosity).
◎: 6.00 or more ○: 5.50 or more and less than 6.00 Δ: 5.00 or more and less than 5.50 ×: less than 5.00

[Storage stability test]
The initial viscosity value measured after 23 ° C. × 1 day and the viscosity value after storage measured after 50 ° C. × 7 days (cooling at 23 ° C. × 3 hours) were determined based on the following formulas for the viscosity change ratio and the TI value change ratio, Storage stability (% change) was evaluated.
Viscosity change rate:
[(Viscosity value at each rotational speed after storage) / (Viscosity value at each initial rotational speed)] × 100
TI value change rate:
[(TI value after storage) / (initial TI value)] × 100
[Storage stability criteria]
The determination was made according to the following criteria according to the viscosity change rate and the TI value change rate.
◎: Viscosity change rate is less than 120% and TI value change rate is 95% or more ○: Viscosity change rate is 120% or more and less than 140%, TI value change rate is 80% or more and less than 95% △: Viscosity change rate is 140% or more and less than 150% TI value change rate 70% or more and less than 80% ×: Viscosity change rate 150% or more and TI value change rate less than 70%

[Dispersibility test]
420 g of the surface treated calcium carbonate filler was weighed and put into a paper bag. The paper bag was put on a weight so that a load of 1 t was applied per 1 m ² , and compacted at 50 ° C. for 7 days. The surface-treated calcium carbonate filler after the compaction condition is dried at 105 ° C. for 2 hours or more.
Surface-treated calcium carbonate filler and heavy calcium carbonate 90 g after being consolidated in a 5 L universal mixing stirrer (manufactured by Dalton Co., Ltd.) after being charged with 300 g of modified silicone resin and 180 g of plasticizer and dried in advance at 105 ° C. for 2 hours or more. Were put together and pre-stirred at low speed for 15 minutes. Then, after scraping off the filler adhering in the mixing stirrer, the mixture was immediately kneaded at a high speed for 30 minutes in a vacuum atmosphere. Thereafter, 18 g of a dehydrating agent, 6 g of a tin catalyst, and 6 g of aminosilane were added and mixed in a vacuum atmosphere for 15 minutes at a low speed. The sealant after mixing was spread thinly on a glass plate with a spatula so that the length was 5 cm or more, the width was 5 cm or more, and the thickness was 1 mm or less.
[Dispersibility test criteria]
The number of grains of 0.5 mm or more per 5 cm square was measured on the surface of the sealant applied on the glass plate, and the following dispersibility was determined based on the measured number.
○: 0 or more grains of 0.5 mm or more Δ: 1 or 2 grains of 0.5 mm or more ×: 3 or more grains of 0.5 mm or more

[Tensile test method]
Apply a primer (NO. 40 made by Yokohama Rubber Co., Ltd.) to the surface of an aluminum plate (50mm x 50mm x 3mm), let it dry for 60 minutes, fill with the above sealant (shape 12mm x 12mm x 50mm), JIS A 1439 Architectural sealant 5.17.2 Durability and tensile test specimens were produced in accordance with the H-type specimens.
This specimen was cured at 23 ° C. × 14 days + 35 ° C. × 14 days, and measured after 23 ° C. × 1 day using a tensile tester (manufactured by Shimadzu Corp., Autograph AG-1).
50% tensile stress: Value obtained by dividing the load when stretched at a rate of 50 mm per minute and stretched at 50% (6 mm) elongation by the cross-sectional area of the sealant (600 mm ² ) Maximum strength: At a rate of 50 mm per minute Tensile, value obtained by dividing the largest load by the cross-sectional area of the sealant Elongation rate: Value obtained by dividing the displacement at the time of maximum strength by the shape at the time of filling (12 mm) and multiplying by 100 Adhesiveness (initial): 23 ° C × 14 days + 35 ° C x 14 days, 23 ° C x 1 day later Judged by the ratio of the sealant remaining on the bonded aluminum surface when the tensile test was performed Adhesiveness (hot water): After initial curing, 50 ° C hot water x 7 A tensile test is performed after sun soaking, and it is determined by the ratio of the sealant remaining on the broken aluminum adhesive surface.
[Criteria for tensile test]
50% tensile stress: ○: Less than 0.20 N / mm ²
×: 0.20N / mm ² or more maximum intensity: ◎: 1.00 N / mm ² or more
○: 0.40 N / mm ² or more and less than 1.00 N / mm ²
Δ: 0.30 N / mm ² or more and less than 0.4 N / mm ²
×: Less than 0.30 N / mm ² Elongation: ◎: 700% or more
○: 600% or more and less than 700%
Δ: 500% or more and less than 600%
X: Less than 500% Adhesiveness: The state in which the sealant remained on the aluminum bonded surface was expressed by the ratio of cohesive failure (CF%) and evaluated according to the following criteria.
○: Destruction with 100% sealant remaining (CF100%)
Δ: Destruction in a state where the sealant remains 50% or more and less than 100% (CF50% to CF99%)
×: Less than 50% remaining sealant CF <50% or peeled off (AF)
In Table 9 and Table 10, the modified silicone-based sealants of Examples 53 to 65 blended with the surface-treated calcium carbonate filler of Examples 1 to 13 are excellent in dispersibility and thixotropy, and have storage stability, adhesive strength, and elongation. It can be seen that the rate is large and the hot water adhesion is excellent.

Examples 66-78, Comparative Examples 36-42
Using the surface-treated calcium carbonate filler obtained in Examples 1 to 13 and Comparative Examples 1 to 7, a one-component silicone sealant was prepared by the following test method (5), and the effect test was performed. The results are shown in Tables 11 and 12.

(Test method (4) One-component silicone sealant)
[Combination]
Silicone Resin (Made in USA) 420 parts Silicone Oil SH-200 (Toray Dow Corning Silicone made 30 parts by weight Oximesilane (Made in USA) 48 parts by weight Surface treated calcium carbonate filler 450 parts by weight Dehydrating agent KBM-1003 (Shin-Etsu Chemical) 18 parts by weight Tin catalyst Neostan U-100 (manufactured by Nitto Kasei Co., Ltd.) 1 part by weight
957 parts by weight in total

[Kneading method]
Silicone resin, silicone oil, and oxime silane are put into a 5L universal mixing stirrer (manufactured by Dalton Co., Ltd.) and added together with a surface-treated calcium carbonate filler that has been dried at 105 ° C for 2 hours or more in advance. went. Then, after scraping off the filler adhering in the mixing stirrer, the mixture was immediately kneaded at a high speed for 30 minutes in a vacuum atmosphere. Thereafter, a dehydrating agent and a tin catalyst were added and mixed at a low speed for 15 minutes in a vacuum atmosphere. This was filled in an aluminum foil laminate-coated cartridge and sealed with a metal plunger to prepare a one-component silicone sealant.

[Viscosity measurement method]
A sealant that was allowed to stand at 23 ° C. for one day was packed into a 100 ml PP cup with a cartridge gun and measured using a TV-type viscometer (VISCOMETER TV-22, manufactured by Toki Sangyo Co., Ltd.) (range S, spindle No. H7). did.
1 rpm viscosity was a value after 3 minutes, and 10 rpm was a value after 1 minute. Moreover, the TI value was represented by a value obtained by dividing the 1 rpm viscosity value by the 10 rpm viscosity value. In addition, since Example 75 and Comparative Example 38 were low-viscosity, it measured using the range H.
[Viscosity criteria]
The determination was made according to the following criteria according to the TI value (1 rpm viscosity / 10 rpm viscosity).
◎: 5.50 or more ○: 5.00 or more and less than 5.50 Δ: 4.50 or more and less than 5.00 ×: less than 4.50

[Storage stability test]
The initial viscosity value measured after 23 ° C. × 1 day and the viscosity value after storage measured after 50 ° C. × 7 days (cooling at 23 ° C. × 3 hours) were determined based on the following formulas for the viscosity change ratio and the TI value change ratio, Storage stability (% change) was evaluated.
Viscosity change rate:
[(Viscosity value at each rotational speed after storage) / (Viscosity value at each initial rotational speed)] × 100
TI value change rate:
[(TI value after storage) / (initial TI value)] × 100
[Storage stability criteria]
The determination was made according to the following criteria according to the viscosity change rate and the TI value change rate.
◎: Viscosity change rate less than 110% and TI value change rate 95% or more ○: Viscosity change rate 110% or more and less than 120%, TI value change rate 90% or more and less than 95% △: Viscosity change rate 120% or more and less than 130% TI value change rate of 80% or more and less than 90% ×: Viscosity change rate of 130% or more and TI value change rate of less than 80%

[Dispersibility test]
450 g of the surface treated calcium carbonate filler was weighed and put into a paper bag. The paper bag was put on a weight so that a load of 1 t was applied per 1 m ² , and compacted at 50 ° C. for 7 days. The surface-treated calcium carbonate after the consolidation condition is dried at 105 ° C. for 2 hours or more.
Silicone resin 420g, silicone oil 30g, and oxime silane 48g were put into a 5L universal mixing stirrer (manufactured by Dalton Co., Ltd.) and charged together with the surface-treated calcium carbonate filler after compaction conditions that had been dried at 105 ° C for 2 hours or more in advance. Pre-stirring was performed at low speed for 15 minutes. Thereafter, the filler adhering to the mixing stirrer was scraped off and immediately kneaded at high speed for 30 minutes under vacuum conditions. Thereafter, 18 g of a dehydrating agent and 1 g of a tin catalyst were added and mixed under low speed for 15 minutes. This was filled in an aluminum foil laminate-coated cartridge and sealed with a metal plunger to prepare a one-component silicone sealant. The sealant after mixing was spread thinly on a glass plate with a spatula so that the length was 5 cm or more, the width was 5 cm or more, and the thickness was 1 mm or less.
[Dispersibility test criteria]
The number of particles of 0.5 mm or more per 5 cm square was measured on the surface of the sealant applied on the glass plate, and the following dispersibility was determined based on the recognized number.
○: 0 or more grains of 0.5 mm or more Δ: 1 or 2 grains of 0.5 mm or more ×: 3 or more grains of 0.5 mm or more

[Tensile test method]
Apply a primer (#D manufactured by Shin-Etsu Chemical Co., Ltd.) to the surface of an aluminum plate (50 mm x 50 mm x 3 mm), dry it for 60 minutes, and then fill the sealant (shape 12 mm x 12 mm x 50 mm). A 1439 Architectural sealant 5.17.2 Durability and tensile test specimens were produced in accordance with the H-type specimens.
This specimen was cured at 23 ° C. × 14 days + 35 ° C. × 14 days, and measured at 23 ° C. × 1 day using a tensile tester (manufactured by Shimadzu Corp., Autograph AG-1).
50% tensile stress: Value obtained by dividing the load when stretched at a rate of 50 mm per minute and stretched at 50% (6 mm) elongation by the cross-sectional area of the sealant (600 mm ² ) Maximum strength: At a rate of 50 mm per minute Tensile, value obtained by dividing the largest load by the cross-sectional area of the sealant Elongation rate: Value obtained by dividing the displacement at the time of maximum strength by the shape at the time of filling (12 mm) and multiplying by 100 Adhesiveness (initial): 23 ° C × 14 days + 35 ° C x 14 days, 23 ° C x 1 day later Judged by the ratio of the sealant remaining on the bonded aluminum surface when the tensile test was performed Adhesiveness (hot water): After initial curing, 50 ° C hot water x 7 A tensile test is performed after sun soaking, and it is determined by the ratio of the sealant remaining on the broken aluminum adhesive surface.
[Criteria for tensile test]
50% tensile stress: ○: Less than 0.60 N / mm ²
×: 0.60N / mm ² or more maximum intensity: ◎: 0.80 N / mm ² or more
○: 0.70 N / mm ² or more and less than 0.8 N / mm ²
Δ: 0.60 N / mm ² or more and less than 0.7 N / mm ²
×: Less than 0.60 N / mm ² Elongation: ◎: 200% or more
○: 150% to less than 200%
Δ: 100% or more and less than 150%
X: Less than 100% Adhesiveness: The state in which the sealant remained on the aluminum bonded surface was expressed by cohesive failure (CF) and evaluated according to the following criteria.
○: Destruction with 100% sealant remaining (CF100%)
Δ: Destruction in a state where the sealant remains 50% or more and less than 100% (CF50% to CF99%)
×: Less than 50% remaining sealant CF <50% or peeled off (AF)
In Tables 11 and 12, the silicone sealants of Examples 66 to 78 blended with the surface-treated calcium carbonate filler of Examples 1 to 13 are excellent in dispersibility and thixotropy, and have storage stability, adhesive strength, and elongation. It can be seen that the performance is excellent in hot water adhesion.

  As described above, the surface-treated calcium carbonate filler of the present invention is particularly useful for a curable resin composition and is blended in a curable resin composition, and has excellent thixotropy, slump resistance, slip resistance, and storage stability. It is possible to provide a curable resin composition having good balance of properties, adhesiveness, adhesion, hot water adhesiveness, adhesive strength, elongation, and the like.

Claims (8)

The surface-treated calcium carbonate, wherein the calcium carbonate is surface-treated with a surface treatment agent containing at least one selected from fatty acids and water-soluble salts thereof and satisfies the following formulas (1) to (5): Filler.
(1) 3 ≦ Sw ≦ 40 [m ² / g]
(2) 0.40 ≦ As ≦ 5.50 [mg / m ² ]
(3) 85 ≦ Cr ≦ 100 [wt%]
(4) 0 ≦ Ar ≦ 10 [wt%]
(5) 0.15 ≦ Ar / (Ar + Sr) ≦ 1.00 [−]
However,
Sw: BET specific surface area of surface-treated calcium carbonate [m ² / g]
As: surface treatment agent amount per unit specific surface area determined by the following formula: As = Tg / Sw [mg / m ² ]
Tg: Heat loss per gram of surface-treated calcium carbonate at 200 ° C. to 500 ° C. [mg / g]
Cr: Ratio of the amount of the surface treatment agent that is not eluted as a free substance and remains on the calcium carbonate side when the surface treatment calcium carbonate is extracted with ethanol to the total surface treatment agent amount [% by weight]
Ar: Ratio of the amount of free fatty acid in the amount of free substances obtained by extracting the surface-treated calcium carbonate with ethanol to the amount of the total surface treatment agent [wt%]
Sr: The ratio of the amount of monovalent fatty acid salt to the total amount of the surface treatment agent in the amount of free ions obtained by extracting the surface-treated calcium carbonate with ethanol [wt%]   The surface-treated calcium carbonate filler according to claim 1, wherein the unsaturated component in the surface treatment agent is 0 to 30% by weight.   A curable resin composition comprising the surface-treated calcium carbonate filler according to claim 1 or 2 blended with a curable resin.   The curable resin composition according to claim 3, wherein the curable resin is at least one selected from a polyurethane resin, a polysulfide resin, a modified silicone resin, a silicone resin, a polyisobutylene resin, a modified acrylic resin, and an acrylic urethane resin. object.   The curable resin composition according to claim 3, which is a sealing material.   The curable resin composition according to claim 3 or 4, which is an adhesive.   A curable resin composition comprising the surface-treated calcium carbonate filler according to claim 1 or 2 in a plastisol.   The curable resin composition according to claim 7, wherein the plastisol resin is an acrylic resin or a vinyl chloride resin.