Surface-treated calcium carbonate filler for curable resin composition, and curable resin composition using same

Abstract

A surface-treated calcium carbonate filler according to the present invention is used in a curable resin having a resin viscosity of at least 30 Pa·s at 23°C, and includes surface-treated calcium carbonate particles that have been surface-treated with a surface treatment agent. In the surface-treated calcium carbonate filler according to the present invention, Sw is 5-50 (m2 / g), Mp is 50-100 (mass%), UFa is 45-80 (mass%), Nr is 20-50 (mass%), and Es is 1.00-4.50 (mg / m2).

Description

Surface-treated calcium carbonate filler for curable resin composition, and curable resin composition using the same

[0001] The present invention relates to a surface-treated calcium carbonate filler for a curable resin composition, and a curable resin composition using the same, more particularly to a surface-treated calcium carbonate filler for a curable resin composition that can be used in a curable resin composition containing a high-viscosity resin, and a curable resin composition using the same.

[0002] In recent years, there has been a demand for longer service life for general buildings such as buildings and condominiums, as well as prefabricated houses. Accordingly, there is a demand for the waterproofing performance of sealants applied to exterior wall joints to be maintained for a long period of time. There is also a demand for preventing the occurrence of dirt on the sealant surface or around the joints, as well as dirt and peeling of the coating film applied to the sealant surface, thereby improving aesthetics and / or design.

[0003] To extend the life of the above-mentioned performance, the sealant needs to have low modulus and high elongation. Furthermore, it is desired to maintain the various performance properties of the sealant for a longer period by improving heat resistance and water resistance, suppressing deterioration of physical properties, and maintaining adhesiveness.

[0004] Sealant is paste-like during application, and after joint filling and finishing, it acquires rubber elasticity through moisture and reactive hardening. Since the sealant is manually filled into joints by on-site workers using a cartridge gun or caulking gun, it must maintain a moderate softness that allows for spatula-like finishing of the joints. In particular, in construction environments with low temperatures in winter, the sealant paste becomes sticky and its viscosity increases, which can easily hinder workability. Therefore, there is a need to design a resin composition that is easy to work with even at low temperatures.

[0005] Silicone sealants based on organopolysiloxanes are known to best meet the requirements for long life. They have high heat resistance, low modulus and high elongation properties over a long period of time, and little increase in viscosity at low temperatures, making them easy to work with.

[0006] However, silicone sealants have the drawback of being easily contaminated and conspicuous when placed around joints. Furthermore, the surface of this sealant is difficult to paint. For these reasons, they are used only in high-rise buildings and other structures, and are rarely used in ordinary homes.

[0007] Recently, various resin compositions have been proposed that are useful as sealing materials and have low modulus and high elongation properties.

[0008] For example, Patent Document 1 describes a resin composition containing a surface-treated calcium carbonate containing a predetermined amount of alkali metal and a modified silicone resin. This surface-treated calcium carbonate is obtained by surface-treating calcium carbonate with a fatty acid or the like and adding an alkali metal-containing compound. However, the modified silicone resins that can be used are only those with a low resin viscosity and a polyoxyalkylene main chain. The resin composition of Patent Document 1 also has drawbacks such as being unable to maintain heat resistance for a long period of time, being relatively easily decomposed, and having poor water-resistant adhesion.

[0009] Patent Document 2 describes that a curable composition containing a (meth)acrylic polymer having an alkoxysilyl group, a polyoxyalkylene polymer having an alkoxysilyl group, and heavy calcium carbonate has excellent weather resistance and suppresses an increase in viscosity in a low-temperature environment. However, such a curable composition has a drawback in that it lacks workability (has stringiness).

[0010] Patent Document 3 describes a surface-treated calcium carbonate filler that can provide a curable resin composition with excellent heat resistance, strength, and elongation, and a curable resin composition using the same. However, the curable resin composition described in Patent Document 3 has an excessively high viscosity, particularly at low temperatures, resulting in low thixotropy, which may impair workability for contractors.

[0011] Japanese Patent No. 5728616 Japanese Patent Application Laid-Open No. 2021-155604 International Publication No. 2016 / 152762

[0012] An object of the present invention is to solve the above-mentioned problems, and an object of the present invention is to provide a surface-treated calcium carbonate filler for a curable resin composition, which can give a curable resin composition having high thixotropy, improving workability during application in a low-temperature atmosphere, and having a low modulus and high elongation, even when a curable resin having a high viscosity is blended therein, and a curable resin composition using the same.

[0013] The present invention provides a surface-treated calcium carbonate filler for use in a curable resin having a resin viscosity of 30 Pa s or more at 23°C, the surface-treated calcium carbonate filler for a curable resin composition comprising surface-treated calcium carbonate particles that have been surface-treated with a surface treatment agent, and satisfying the following formulas (1) to (5): (1) 5≦Sw≦50 (m ２ / g) (2) 50≦Mp≦100 (mass%) (3) 45≦UFa≦80 (mass%) (4) 20≦Nr≦50 (mass%) (5) 1.00≦Es≦4.50 (mg / m ２ ) Sw is the BET specific surface area (m ２ / g), Mp is the content (mass%) of fatty acids contained in the surface treatment agent, which is at least one fatty acid selected from the group consisting of fatty acids having a melting point of 46°C or less and salts thereof, Nr is the ratio (mass%) of a monovalent fatty acid salt constituting a counter ion obtained by refluxing the surface-treated calcium carbonate particles with ethanol to the total surface treatment amount of the surface treatment agent, and Es is the amount (mg / m) of the surface treatment agent per unit specific surface area of ​​the surface-treated calcium carbonate particles. ２ )

[0014] In one embodiment, the fatty acids contained in the surface treatment agent and having a melting point of 46°C or less are at least one compound selected from the group consisting of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, and salts thereof.

[0015] In one embodiment, the curable resin is at least one selected from the group consisting of a (meth)acrylic homopolymer having an alkoxysilyl group and a mixture of a polyoxyalkylene polymer having an alkoxysilyl group and a (meth)acrylic polymer.

[0016] The present invention also relates to a curable resin composition containing the above-mentioned surface-treated calcium carbonate filler for a curable resin composition and a curable resin.

[0017] In one embodiment, the curable resin composition of the present invention is used as a sealant or adhesive.

[0018] In one embodiment, the curable resin composition of the present invention is a one-component resin composition or a two-component resin composition.

[0019] In one embodiment, the curable resin composition of the present invention contains 5% by mass or less of a phthalate plasticizer based on the total mass.

[0020] According to the present invention, it is possible to provide a curable resin composition which maintains workability in a low-temperature application environment, can achieve a low modulus and high elongation, and has excellent heat resistance and high thixotropy. The curable resin composition obtained using the surface-treated calcium carbonate filler of the present invention can prevent or suppress deterioration in workability during application, for example, even in a low-temperature atmosphere.

[0021] Regarding the increase in viscosity at low temperatures, resins with high viscosity, such as polymers containing a (meth)acrylic polymer and having an alkoxysilyl group, have a difference in viscosity even at 23°C compared to resins containing a general polyoxyalkylene polymer and having an alkoxysilyl group, and have the property of being prone to a sudden increase in viscosity at temperatures of 5°C or lower.

[0022] By adding surface-treated calcium carbonate particles, which have been surface-treated with a surface treatment agent containing fatty acids having a melting point of 46° C. or less, to such a curable resin as a filler, compatibility with the curable resin is improved, and a rapid increase in viscosity at temperatures of 5° C. or less can be suppressed, thereby improving the low-temperature workability of the resulting curable resin composition.

[0023] Furthermore, by using, as a filler, surface-treated calcium carbonate particles that have been surface-treated with a surface treatment agent having a low melting point and containing unsaturated fatty acids in a specific ratio, the thixotropy of the resulting curable resin composition can be improved, and the curable resin composition can be endowed with low modulus and high elongation performance.

[0024] 1. Surface-Treated Calcium Carbonate Filler First, the surface-treated calcium carbonate filler of the present invention will be described.

[0025] The surface-treated calcium carbonate filler of the present invention includes surface-treated calcium carbonate particles that have been surface-treated with a surface treatment agent. The surface-treated calcium carbonate particles are particles made of synthetic calcium carbonate and satisfy the following formulas (1) to (5):

[0026] (1) BET specific surface area (Sw) The surface-treated calcium carbonate particles of the present invention have a predetermined BET specific surface area (Sw; m ２ In the present invention, the Sw of the surface-treated calcium carbonate particles is 5 to 50 m ２ / g, preferably 10 to 40m ２ / g, more preferably 15 to 35m ２ / g. When the Sw of the surface-treated calcium carbonate particles is 5m ２ When the Sw of the surface-treated calcium carbonate particles is less than 50 m / g, the primary particles become too large, and it may be difficult to impart sufficient thixotropy to the resulting curable resin composition. ２ When the surface-treated calcium carbonate particle surface treatment coefficient exceeds 1 / g, the amount of surface treatment agent required to coat the surface of the raw material calcium carbonate particles increases, and the rate of change in physical properties of the obtained curable resin composition after heat resistance may increase. Note that Sw is a value measured by the nitrogen adsorption method (BET method) of the surface-treated calcium carbonate particles, and is measured by the following test method.

[0027] (Method of Measuring Sw) The Sw of the surface-treated calcium carbonate particles can be measured, for example, using a Macsorb HM model-1201 manufactured by Mountech Co., Ltd. as follows.

[0028] Specifically, 200 to 300 mg of surface-treated calcium carbonate particles to be measured as a sample are placed in a glass cell, which is then set in a measuring device. As a pretreatment, the cell is subjected to a heat treatment at 200°C for 10 minutes in a mixed gas atmosphere of nitrogen and helium, and then low-temperature, low-humidity physical adsorption is performed in a liquid nitrogen environment, thereby measuring Sw.

[0029] Sw can be controlled by varying various conditions during the production of the surface-treated calcium carbonate particles of the present invention. Conditions that can control Sw within the above range include, for example, the concentration of milk of lime used in the carbonation reaction, the temperature employed in the carbonation reaction, the concentration of carbon dioxide gas used, the type of additive used in the carbonation reaction, and combinations of these, as described below. If these conditions are not set properly, it may be difficult to obtain surface-treated calcium carbonate particles that satisfy the above Sw range.

[0030] (2) Amount of Fatty Acids in the Surface Treatment Agent (Mp) The surface-treated calcium carbonate particles of the present invention also contain a predetermined amount of fatty acids in the surface treatment agent applied to the particles. Here, the term “fatty acids” includes any of fatty acids, fatty acid salts, and combinations thereof.

[0031] Fatty acids have various melting points depending on the chain length. For example, according to Keiichi Inaba et al., New Edition, Fatty Acid Chemistry, 2nd Edition, 2nd Printing, Saiwai Shobo, 1997, representative fatty acids have the following melting points: hexanoic acid (-4.0°C), heptanoic acid (-7.0°C), octanoic acid (16.0°C), nonanoic acid (12.5°C), decanoic acid (31.6°C), undecanoic acid (28.7°C), lauric acid (44.2°C), oleic acid (13.4°C), linoleic acid (-5.1°C), and linolenic acid (-11.2°C).

[0032] In the present invention, examples of such fatty acids include fatty acids having a melting point of 46°C or less, salts of such fatty acids, and combinations thereof. Examples of fatty acids having a melting point of 46°C or less include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, oleic acid, linoleic acid, and linolenic acid, as well as combinations thereof. Examples of fatty acid salts of fatty acids include alkali metal salts (e.g., sodium salts, potassium salts), alkaline earth metal salts (e.g., calcium salts, magnesium salts), ammonium salts, and amine salts of the above fatty acids, as well as combinations thereof. In the present invention, the fatty acids having a melting point of 46°C or less are preferably lauric acid, oleic acid, and combinations thereof, because they are more effective in terms of poor workability at low temperatures.

[0033] In addition, when calcium carbonate particles surface-treated with a fatty acid having a melting point of more than 46°C, as opposed to the fatty acid having a melting point of 46°C or less, are blended with a curable resin having a high viscosity, it becomes difficult to reduce the rapid increase in viscosity of the resulting curable resin composition at low temperatures.

[0034] The content (Mp) of fatty acids having a melting point of 46°C or less contained in the surface treatment agent of the present invention is 50 to 100 mass%, preferably 50 to 80 mass%, and more preferably 55 to 65 mass%. If Mp is less than 50 mass%, the plasticizing effect of the resulting curable resin composition at low temperatures will be weak, and the thixotropy will decrease significantly at low temperatures, and the viscosity will also increase significantly, which will not lead to improvement in workability during application.

[0035] (3) Proportion (UFa) of Unsaturated Fatty Acid Moiety Contained in Monovalent Water-Soluble Fatty Acid Salt Constituting the Surface Treatment Agent The surface-treated calcium carbonate particles of the present invention also contain a predetermined range of proportion (UFa; mass g) of unsaturated fatty acid moiety contained in the monovalent water-soluble fatty acid salt constituting the surface treatment agent applied to the particles. In the present invention, the proportion (UFa) of unsaturated fatty acid moiety contained in the monovalent water-soluble fatty acid salt constituting the surface treatment agent applied to the surface-treated calcium carbonate particles is 45 to 80 mass%, preferably 50 to 70 mass%, and more preferably 55 to 65 mass%. If the UFa in the surface treatment agent applied to the surface-treated calcium carbonate particles is less than 45 mass%, the viscosity of the resulting curable resin composition increases at low temperatures, reducing workability for contractors. If the UFa in the surface treatment agent applied to the surface-treated calcium carbonate particles is more than 80 mass%, the heat resistance of the resulting curable resin composition decreases, discoloration is likely to occur, and the elongation decreases.

[0036] (Method for Measuring UFa) The UFa of the surface-treated calcium carbonate particles can be measured, for example, as follows using a gas chromatograph mass spectrometer (GCMS-QP2010A manufactured by Shimadzu Corporation) equipped with a pyrolysis apparatus (PY-2020D manufactured by Frontier Labs Co., Ltd.) as a gas chromatograph.

[0037] Specifically, the surface-treated calcium carbonate particles are immersed in a tetramethylammonium hydroxide solution, which is then thermally decomposed at 300° C., and the components are passed through a gas chromatograph for measurement.

[0038] From the resulting gas chromatogram, the peaks of the five major fatty acid compositions (i.e., the saturated fatty acids lauric acid (C12), myristic acid (C14), palmitic acid (C16), and stearic acid (C18), as well as the unsaturated fatty acid oleic acid (C18F1)) are analyzed, and the sum of these peaks is adjusted to 100%.

[0039] The proportion (mass %) of the unsaturated fatty acid moiety thus obtained is used as UFa.

[0040] (4) The ratio (Nr) of the monovalent fatty acid salt constituting the counter ion obtained by refluxing surface-treated calcium carbonate particles with ethanol to the total surface treatment amount of the surface treatment agent. The surface-treated calcium carbonate particles of the present invention also have a ratio (Nr) of the monovalent fatty acid salt constituting the counter ion obtained by refluxing the particles with ethanol to the total surface treatment amount of the surface treatment agent that satisfies a predetermined range. In the present invention, the Nr of the surface-treated calcium carbonate particles is 20 to 50 mass%, preferably 25 to 45 mass%, and more preferably 30 to 40 mass%. If the Nr of the surface-treated calcium carbonate particles is less than 20 mass%, the elongation of the resulting curable resin composition decreases, making it difficult to obtain a resin composition with a long life. If the Nr of the surface-treated calcium carbonate particles exceeds 50 mass%, the resulting curable resin composition has a low modulus and high elongation, but suffers from reduced water resistance and reduced adhesion, resulting in impaired long-term waterproofing performance.

[0041] (Method for Measuring Nr) The Nr of the surface-treated calcium carbonate particles can be measured as follows.

[0042] (a) First, 5 g of surface-treated calcium carbonate particles are placed in a 300 mL Erlenmeyer flask as a sample, and 80 g of 95% ethanol is added to it. (b) Next, the flask's neck is lightly covered with aluminum foil and placed in a water bath at 90°C or higher, and heated for an additional hour after boiling begins. After that, the flask is removed from the water bath and allowed to cool at room temperature for one day. (c) The temperature is adjusted to 30°C, and the contents of the flask are suction-filtered using a PTFE membrane filter (pore size 0.5 μm), and the filtrate is collected in a beaker. (d) The resulting filtrate is placed in a weighed 200 mL beaker and immersed in a water bath at 80°C or higher to evaporate the 95% ethanol. After cooling, the mass of the beaker is measured (note that the mass of the empty beaker is also measured before the filtration). (e) The amount of free matter F (mg / g) per 1 g of surface-treated calcium carbonate particles is then calculated as follows: F (mg / g) = [mass of beaker after filtration and cooling (mg) - mass of empty beaker (mg)] / mass of calcium carbonate sample (g) (f) Next, the free substance obtained in (e) above is dissolved in 25 mL of 2-propanol to which a few drops of phenolphthalein solution have been added. (g) The 2-propanol solution obtained in (f) above is subjected to neutralization titration with a 0.1 mol / L aqueous potassium hydroxide solution. (h) From the potassium hydroxide titration amount in (g) above, the amount of free fatty acid (a (mg / g)) in the amount of free substance per 1 g of surface-treated calcium carbonate particles can be calculated based on the following formula: Amount of free fatty acid a (mg / g) = Titration amount of 0.1 mol / L potassium hydroxide (mL) × 10 －４ × molecular weight of the surface treatment agent applied to the surface-treated calcium carbonate particles × 10 ３(mg) / mass (g) of sample of surface-treated calcium carbonate particles Here, when the thermal loss (total amount of surface treatment agent) per 1 g of surface-treated calcium carbonate particles at 200 to 500°C is Tg (mg / g), the ratio Zf of the amount of free fatty acid obtained by extracting the surface-treated calcium carbonate particles with ethanol to the total amount of surface treatment agent can be calculated as follows: Zf = (a / Tg) x 100 (% by mass) Similarly, the amount s (mg / g) of monovalent fatty acid salt constituting the counter ion in the free substance per 1 g of surface-treated calcium carbonate particles can be calculated from the titration amount of potassium hydroxide (g) as follows: Amount s of monovalent fatty acid salt = Amount of free substance F - Amount a of free fatty acid a (mg / g) The ratio Nr of the monovalent fatty acid salt constituting the counter ion in the free substance obtained by refluxing the surface-treated calcium carbonate with ethanol to the total amount of surface treatment agent can be calculated as follows: Nr = (s / Tg) x 100 (% by mass)

[0043] (5) Amount of Surface Treatment Agent per Unit Specific Surface Area of ​​Surface-Treated Calcium Carbonate Particles (Es) The amount of the surface treatment agent per unit specific surface area of ​​the surface-treated calcium carbonate particles in the present invention (Es) also satisfies a predetermined range. In the present invention, Es of the surface-treated calcium carbonate particles is 1.00 to 4.50 mg / m ２ and preferably 1.50 to 4.00 mg / m ２ and more preferably 2.00 to 3.00 mg / m ２ The surface-treated calcium carbonate particles have an Es of 1.00 mg / m ２ If the Es of the surface-treated calcium carbonate particles is less than 4.50 mg / m, the effect of the surface treatment of the surface-treated calcium carbonate particles tends to be insufficient, and the untreated surface is exposed due to insufficient treatment, which makes it more likely to adsorb moisture. ２ If the amount of the surface treatment agent exceeds 100%, the excess surface treatment agent will act as a lubricant, which may adversely affect the heat resistance of the resulting curable resin composition and is economically disadvantageous. It is preferable to vary the amount of the surface treatment depending on the BET specific surface area Sw of the specific surface area (particle size) of the surface-treated calcium carbonate particles.

[0044] (Calculation method of Es) Es of the surface-treated calcium carbonate particles is calculated by multiplying the thermal loss (mg / g) per 1 g of surface-treated calcium carbonate (Tg; also referred to as the total amount of surface treatment agent) by the BET specific surface area (m ２ / g) (Sw): Es (mg / m ２ )=Tg(mg / g) / Sw(m ２ / g)

[0045] (Method for Measuring Tg) Here, Tg can be obtained as the thermal loss (mg / g) per gram of surface-treated calcium carbonate by measuring the thermal loss from 200°C to 500°C when 100 mg of surface-treated calcium carbonate is placed in a sample pan (made of platinum) having a diameter of 10 mm and heated from room temperature to 510°C at a heating rate of 15°C / min using a thermal analyzer (ThermoPlusEV02 manufactured by Rigaku Corporation).

[0046] Es can be controlled by varying various conditions during the production of the surface-treated calcium carbonate particles of the present invention. Conditions that can control Es within the above range include, for example, the amount of the surface treatment agent, the BET specific surface area, and a combination thereof. If these conditions are not set properly, it may be difficult to obtain surface-treated calcium carbonate particles that satisfy the above Es range.

[0047] (Surface-treated calcium carbonate filler surface-treated with a surface treatment agent) As described above, the surface-treated calcium carbonate filler of the present invention is a filler in which surface-treated calcium carbonate particles, which are constituent components thereof, satisfy all of the formulas (1) to (5). Such surface-treated calcium carbonate particles are surface-treated with a surface treatment agent.

[0048] Here, the term “surface-treated” used in this specification is used to mean the “state” of the surface of the surface-treated calcium carbonate filler and / or the surface-treated calcium carbonate particles.

[0049] The surface-treated calcium carbonate particles in the present invention are unmodified (before surface treatment) calcium carbonate particles that have been surface-treated with a surface treatment agent.

[0050] (Unmodified calcium carbonate particles) Here, the unmodified calcium carbonate particles are particles of synthetic calcium carbonate (e.g., light / colloidal calcium carbonate) prepared by a synthesis method in which natural gray dense limestone is fired, rather than natural white saccharinous limestone (heavy calcium carbonate) which contains a large amount of fine particles, from the viewpoint of degassing properties during kneading with a resin.

[0051] Such unmodified calcium carbonate particles can be produced by a known carbon dioxide gas method, for example, by adding water to quicklime obtained by calcining gray dense limestone to form calcium hydroxide, which is then reacted with carbon dioxide gas generated during calcination. Furthermore, the calcium carbonate slurry reacted by this carbon dioxide gas method can be adjusted by Ostwald aging to have a desired BET specific surface area, thereby obtaining desired calcium carbonate particles.

[0052] (Surface Treatment Agent) A surface treatment agent is used on the unmodified calcium carbonate particles for the purpose of improving the fluidity of the particles, the alkali resistance and activity resistance of calcium carbonate, and other properties of the calcium carbonate filler. Examples of the surface treatment agent include the fatty acids.

[0053] In the present invention, the surface treatment agent may contain, in addition to the above-mentioned fatty acids, one or more of other saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, resin acids, and sodium salts, potassium salts, ammonium salts, and amine salts thereof.

[0054] Such other saturated fatty acids preferably include saturated fatty acids having 6 to 31 carbon atoms, more preferably 8 to 26 carbon atoms, and even more preferably 9 to 21 carbon atoms. Specific examples of other fatty acids include butyric acid, caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alaic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, and melissic acid, and combinations thereof.

[0055] Other unsaturated fatty acids are fatty acids having one or more double bonds in the molecule, and include, for example, those synthesized in vivo by dehydration of saturated fatty acids. Examples of other unsaturated fatty acids include unsaturated fatty acids having 6 to 31 carbon atoms. Specific examples of other unsaturated fatty acids include obsiclic acid, caroleic acid, undecylenic acid, linderic acid, tsuzuic acid, physeteric acid, moristoleic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, asclebic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, brassidic acid, selacholeic acid, ximenic acid, lumecic acid, sorbic acid, linoleic acid, and linolenic acid, as well as combinations thereof.

[0056] In the present invention, fatty acids derived from animal raw materials such as beef tallow and lard, which contain the other unsaturated fatty acids described above, and fatty acids derived from plant raw materials such as palm and coconut may also be used as one of the constituent components of the surface treatment agent.

[0057] Furthermore, as long as the effects of the present invention are not impaired, the surface treatment agent may include alicyclic carboxylic acids (e.g., naphthenic acid), resin acids (e.g., abietic acid, pimaric acid, palustric acid, neoabietic acid), modified rosins (e.g., disproportionated rosins, hydrogenated rosins, dimeric rosins, and trimeric rosins), sulfonic acids (e.g., alkylbenzenesulfonic acid), and sodium salts, potassium salts, ammonium salts, and amine salts thereof, which may be used alone or in combination of two or more.

[0058] (Surface Treatment of Unmodified Calcium Carbonate Particles) The surface treatment of unmodified calcium carbonate particles using the above surface treatment agent is carried out, for example, as follows.

[0059] The surface treatment of unmodified calcium carbonate particles may be carried out by either a general dry treatment or a general wet treatment. Preferably, a method of adding the above-mentioned surface treatment agent to an aqueous slurry containing unmodified calcium carbonate particles can be employed. Such a method is generally called a wet treatment, and is preferred in that it can appropriately achieve both the degree of surface treatment of the calcium carbonate particles and production efficiency.

[0060] The amount of the surface treatment agent used is not particularly limited and can be appropriately selected by those skilled in the art as long as the resulting surface-treated calcium carbonate particles satisfy the above formulas (1) to (5). The temperature employed for the surface treatment is not particularly limited and can be appropriately selected by those skilled in the art.

[0061] After the surface treatment, the resulting particles may be powdered through any operation such as dehydration, drying, or pulverization according to a conventional method.

[0062] The dehydration can be carried out by using a filter press or a centrifugal dehydrator to dehydrate the slurry containing the surface-treated calcium carbonate particles. For drying, a hot air dryer such as a micron dryer, which can dry the surface-treated calcium carbonate particles efficiently by directly contacting them with high-temperature hot air, or a heat transfer dryer such as a CD dryer, which brings the surface-treated calcium carbonate particles into contact with a heating plate and dries them indirectly through the heating plate, may be used.

[0063] In this manner, surface-treated calcium carbonate particles that have been surface-treated with a surface treatment agent can be obtained. The surface-treated calcium carbonate particles can be used as they are as a surface-treated calcium carbonate filler that satisfies all of the above formulas (1) to (5).

[0064] The surface-treated calcium carbonate filler of the present invention is used in combination with a curable resin, for example, a curable resin described later having a resin viscosity of 30 Pa s or more at 23° C.

[0065] 2. Curable Resin Composition Next, the curable resin composition of the present invention will be described.

[0066] The curable resin composition of the present invention contains the surface-treated calcium carbonate filler and a curable resin.

[0067] (Curable Resin) The curable resin has a resin viscosity of preferably 30 Pa s or more, more preferably 50 to 100 Pa s, at 23° C., for example. A resin having a viscosity of less than 30 Pa s, for example, does not have any problem in low-temperature workability and therefore does not necessarily need to be used in combination with the surface-treated calcium carbonate filler.

[0068] Here, the resin viscosity of the curable resin can be measured, for example, as follows.

[0069] (Method for measuring resin viscosity of curable resin) Specifically, 300 g of resin is placed in a 300 mL cup in an environment of 23°C, and stirred at 10 rpm for 1 minute, and then the viscosity can be measured using a viscometer (for example, VISCOMETER TV-100 manufactured by Toki Sangyo Co., Ltd. (Range U, Rotor No. H6)).

[0070] The curable resin has, for example, a crosslinkable silicon group such as a silanol group or a reactive silyl group at the end of the constituent molecule, and includes a silicone resin or modified silicone resin that forms a siloxane bond by hydrolysis and condensation reaction. Specific examples of the curable resin include acrylic silicone resins containing (meth)acrylic polymers, such as those commercially available from Kaneka Corporation under the trade names XMAP and S-943.

[0071] As long as the resin viscosity is within the above range, other resins may include a modified silicone resin having a polyoxyalkylene (e.g., MS Polymer S-203, 303, S-810, etc., manufactured by Kaneka Corporation), a modified silicone resin having an epoxy group (Silyl, manufactured by Kaneka Corporation), or a silylated urethane resin having an isocyanate group. However, when such other resins are used in combination with the acrylic silicone resin containing a (meth)acrylic polymer, the ratio of the other resins used in combination can be determined by those skilled in the art within a range that does not impair the effects achieved by the surface-treated calcium carbonate filler of the present invention.

[0072] In the curable resin composition of the present invention, the amount of the surface-treated calcium carbonate filler to be blended into the curable resin varies depending on the type and application of the curable resin to be used and is therefore not particularly limited, but is preferably 5 to 200 parts by mass, and more preferably 20 to 150 parts by mass, relative to 100 parts by mass of the curable resin. When the amount of the surface-treated calcium carbonate filler to be blended is less than 5 parts by mass, it may not be possible to impart sufficient thixotropy to the obtained curable resin composition. When the amount of the surface-treated calcium carbonate filler to be blended exceeds 200 parts by mass, the viscosity of the obtained curable resin composition may become too high, resulting in poor workability.

[0073] (Plasticizer) The curable resin composition of the present invention may contain a plasticizer. Examples of usable plasticizers include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis(2-ethylhexyl)azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dibutyl maleate (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TB20P), tris(2-ethylhexyl)phosphate (TOP), tri(chloroethene) phosphate (TBP), tris ... Examples of suitable plasticizers include tris(β-chloropropyl)phosphate (TCEP), tris(dichloropropyl)phosphate (CRP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl)phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (CDP), acetyltriethyl citrate, acetyltributyl citrate, trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffin, stearic acid-based plasticizers, silicone oils (e.g., dimethylpolysiloxane), and petroleum-based high-boiling solvents (e.g., polyoxypropylene glycol-based, paraffin-based, naphthene-based, isoparaffin-based, and other petroleum-based high-boiling solvents). Specific examples of plasticizers include acrylic polymers (e.g., Arfon UP-1000, 1110, 1120, and the like, manufactured by Toagosei Co., Ltd.). The plasticizer is not particularly limited, but is used in an amount of, for example, 80 to 150 parts by mass per 100 parts by mass of the curable resin.

[0074] In the present invention, it is preferable to minimize or avoid the use of phthalic acid plasticizers as much as possible. Phthalic acid plasticizers are well-known in the art, but when the resulting resin composition is used as a sealant, the coating film applied to the surface of the sealant may suffer from bleeding contamination. Furthermore, the elongation rate may decrease significantly after heat curing, which may impair aesthetics and design and make the composition unsuitable for long-life performance. Therefore, in the curable resin composition of the present invention, it is preferable to set the content of phthalic acid plasticizers to 5% by mass or less relative to the total mass.

[0075] Examples of such phthalate plasticizers include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisonodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), and tetrahydrophthalic acid esters.

[0076] (Other Fillers) The curable resin composition of the present invention may contain other fillers in addition to the surface-treated calcium carbonate filler. Examples of the other fillers that can be used include inorganic fillers, organic fillers, and combinations thereof.

[0077] Examples of inorganic fillers include heavy calcium carbonate, calcium-magnesium carbonate (e.g., natural products and synthetic products), basic magnesium carbonate, quartz powder, silica powder, finely powdered silicic acid (e.g., dry-process, wet-process, and gel-process products), finely powdered calcium silicate, finely powdered aluminum silicate, kaolin clay, pyrophyllite clay, talc, sericite, mica, bentonite, nepheline sannelite, aluminum hydroxide, magnesium hydroxide, barium sulfate, carbon black (e.g., furnace black, thermal black, and acetylene black), graphite, sepiolite, wollastonite, xonotlite, potassium titanate, carbon fiber, mineral fiber, glass fiber, shirasu balloon, fly ash balloon, glass balloon, silica beads, alumina beads, and glass beads.

[0078] Examples of organic fillers include acrylonitrile resin balloons, vinylidene chloride resin balloons, wood flour, walnut flour, cork flour, wheat flour, starch, ebonite powder, rubber powder, lignin, phenolic resin, high styrene resin, polyethylene resin, cellulose powder, pulp powder, and synthetic fiber powder.

[0079] The content of the other filler in the curable resin composition of the present invention is not particularly limited as long as the surface-treated calcium carbonate particles contained therein satisfy the above formulas (1) to (5), and an appropriate amount can be appropriately selected by a person skilled in the art.

[0080] (Other Additives) The curable resin composition of the present invention may contain other additives, such as a curing catalyst, an antioxidant, a colorant, a silane coupling agent, a wax, a foaming agent, a diluent, and a solvent.

[0081] Examples of the curing catalyst include organic tin compounds (e.g., dibutyltin laurate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin acetate, dioctyltin stearate, dioctyltin laurate, dioctyltin diversatate, dibutyltin bistriethoxysilicate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisacetylacetonate, dibutyltin bis(o-phenylphenoxide), dibutyltin bisisooctylthioglycolate, dibutyltin oxide, and dioctyltin oxide); inorganic tin compounds (e.g., bis(2-ethylhexane)tin and bistin neodecanoate); titanium chelate catalysts (e.g., titanium tetramethoxide, titanium tetraethoxide, titanium acryloxide, titanium n-propoxide, titanium tetraisopropoxide, titanium ethylacetoacetate, and titanium acetylacetonate); organoaluminum compounds (e.g., aluminum trisacetylacetonate, aluminum trisethylacetoacetate, and diisopropoxyaluminum ethylacetoacetate); bismuth catalysts (e.g., bismuth tris(neodecanoate)); zirconium metal catalysts (e.g., zirconium tetraacetylacetonate); and the like.

[0082] Examples of the antioxidant include ultraviolet absorbers (for example, benzotriazole-based compounds), antioxidants (for example, phenol-based antioxidants and amine-based antioxidants), and light stabilizers.

[0083] Examples of colorants include inorganic pigments (for example, titanium dioxide, carbon black, etc.) and organic pigments (for example, azo pigments, phthalocyanine pigments, etc.).

[0084] The silane coupling agent is preferably an amino group-containing silane compound, for example, 3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltriethoxysilane, N,N'-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N'-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, N,N'-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine, N,N'-bis-[3-(methyldimethoxysilyl)propyl]hexamethylenediamine, N,N-bis-[3-(trimethoxysilyl)propyl]ethylenediamine, N,N-bis-[3-(methyldimethoxysilyl)propyl]ethylenediamine, N,N-bis-[3-(triethoxysilyl)propyl]ethylenediamine, N,N-bis-[3-(trimethoxysilyl)propyl]hexamethylenediamine, N,N-bis-[3-(methyldimethoxysilyl)propyl]hexamethylenediamine, N,N-bis-[3-(triethoxysilyl)propyl]hexamethylenediamine, N,N-bis-[3-(trimethoxysilyl)propyl]amine, N,N-bis-[3-(triethoxysilyl)propyl]amine, and N,N-bis-[3-(methyldimethoxysilyl)propyl]amine, and combinations thereof. If necessary, a silane coupling agent such as vinyl silane or epoxy silane may be used in combination.

[0085] Examples of waxes include amide wax and castor oil wax.

[0086] As the foaming agent, a foaming agent that generates gas when heated can be used, for example, an azo-based foaming agent such as azodicarbonamide or azobisformamide.

[0087] Examples of diluents include xylene and mineral turpentine.

[0088] Examples of solvents include aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and butane; petroleum solvents such as gasoline; ketones such as acetone and methyl ethyl ketone; ether esters such as cellosolve acetate; silicone oils such as silicone oils and fatty acid ester-modified silicone oils; and combinations thereof. However, it is desirable not to use solvents, as they may impair the heat resistance and / or durability of the resulting curable resin composition.

[0089] The content of the other additives in the curable resin composition of the present invention is not particularly limited as long as the surface-treated calcium carbonate particles contained therein satisfy the above formulae (1) to (5), and an appropriate amount can be appropriately selected by a person skilled in the art.

[0090] The curable resin composition of the present invention can be used, for example, as a sealant or adhesive to be filled in the joints of exterior walls of buildings. In such applications, the curable resin composition of the present invention exhibits little increase in viscosity at low temperatures and excellent workability. In addition, the curable resin composition of the present invention exhibits low modulus and high elongation performance over a long period of time, and also has excellent heat resistance.

[0091] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following description, % means % by mass and parts means parts by mass unless otherwise specified.

[0092] The materials and surface-treated calcium carbonate fillers described in each of the examples and comparative examples were evaluated as follows.

[0093] (A) fatty acid composition, (B) BET specific surface area (Sw) of the surface-treated calcium carbonate, (C) ratio of unsaturated fatty acid moieties contained in monovalent water-soluble fatty acid salts constituting the surface treatment agent (UFa), (D) ratio of monovalent fatty acid salts constituting counter ions obtained by dry distillation of surface-treated calcium carbonate particles with ethanol to the total surface treatment amount of the surface treatment agent (Nr), and (E) amount of surface treatment agent per unit specific surface area of ​​the surface-treated calcium carbonate particles (Es). (A) to (E) were measured by the above-mentioned measurement methods.

[0094] Viscosity of Sealant The sealants obtained in each of the Examples and Comparative Examples were allowed to stand at 23°C for one day, then filled into 100 mL polypropylene (PP) cups using a cartridge gun, and the viscosity was measured using a TV-type viscometer (VISCOMETER TV-100, manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H7).

[0095] The viscosity values ​​were measured 3 minutes after the start of measurement at 1 rpm, 2 minutes after the start of measurement at 2 rpm, and 1 minute after the start of measurement at 10 rpm. The TI value was calculated by dividing the viscosity value at 2 rpm by the viscosity value at 10 rpm.

[0096] Low-Temperature Workability of Sealant Cartridges filled with the sealants obtained in each Example and Comparative Example were stored for one day in a low-temperature environment (5°C), and the sealants were then filled into 100 mL PP cups using a cartridge gun. The sealants were then measured using a TV-type viscometer (VISCOMETER TV-100, manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H7). The viscosity was measured 2 minutes after the start of measurement at 2 rpm and 1 minute after the start of measurement at 10 rpm, and these were used as viscosity values. The TI value was calculated by dividing the viscosity value at 2 rpm by the viscosity value at 10 rpm, and the resulting values ​​were evaluated according to the following criteria.

[0097] However, for those whose viscosity value at 10 rpm in such a low-temperature environment was 600 Pa s or more, all were evaluated as x, regardless of whether the calculated TI value fell into any of "A" to "D". A: TI was 2.8 or more. B: TI was 2.3 or more but less than 2.8. C: TI was 1.8 or more but less than 2.3. D: TI was less than 1.8, or the viscosity value at 10 rpm was 600 Pa s or more.

[0098] Tensile Adhesion of Sealant A primer (No. 40 manufactured by Yokohama Rubber Co., Ltd.) was applied to the surface of an aluminum plate (50 mm × 50 mm × 3 mm), and after drying for 60 minutes, the sealant obtained in each Example and Comparative Example was filled in (shape: 12 mm × 12 mm × 50 mm) to prepare an H-type test specimen in accordance with JIS A 1439:2016 (Architectural sealant 5.12.2, Preparation of tensile test specimen).

[0099] The specimens were heated at 23°C for 14 days and at 30°C for 14 days, and then held at 23°C for one day. The maximum strength and maximum elongation measured using a tensile tester (Autograph AG-1, manufactured by Shimadzu Corporation) were designated as the initial strength and initial elongation. The specimens were further heated at 100°C for 42 days, and then held at 23°C for one day. The maximum strength and maximum elongation measured after this were designated as the post-heating strength and post-heating elongation.

[0100] The maximum strength (Tmax) was determined by pulling the sealant from the test specimen at a rate of 50 mm per minute and applying the maximum load to the cross-sectional area of ​​the sealant (600 mm ２ ) is the value obtained by dividing

[0101] The maximum elongation (Emax) is a value obtained by dividing the amount of displacement when the maximum strength is measured by one side (12 mm) that constitutes the shape of the sealant when the sealant is filled into the aluminum plate, and multiplying the result by 100.

[0102] Furthermore, the initial strength (maximum strength) and initial elongation (maximum elongation), and the strength after heating (maximum strength) and elongation after heating (maximum elongation) obtained above were evaluated according to the following criteria.

[0103] (Initial tensile test criteria) Initial strength (maximum strength / Tmax): A: 0.40 N / mm ２ B: 0.30 N / mm or more. ２ 0.40N / mm or more ２ C: 0.20 N / mm ２ 0.30N / mm or more ２ D: less than 0.20 N / mm ２ It was less than.

[0104] Initial elongation (maximum elongation / Emax): A: 600% or more. B: 450% or more and less than 600%. C: 300% or more and less than 450%. D: Less than 300%.

[0105] (Criteria for tensile test after heating) Strength after heating (maximum strength / Tmax): A: 0.30 N / mm ２ B: 0.20 N / mm or more. ２ 0.30N / mm or more ２ C: less than 0.10 N / mm ２ 0.20N / mm or more ２ D: Less than 0.1 N / mm ２ It was less than.

[0106] Elongation after heating (maximum elongation / Emax): A: 350% or more. B: 250% or more and less than 350%. C: 150% or more and less than 250%. D: Less than 150%.

[0107] (Adhesion) It is preferable that the resulting sealant does not break at the adhesion surface but at the interior (center) of the sealant.

[0108] The CF value indicates the percentage of cohesive failure, and the AF value indicates the percentage of interfacial delamination, where a CF value of 100% indicates 100% cohesive failure and thus desirable adhesion, while an AF value of 100% indicates interfacial delamination and thus undesirable adhesion.

[0109] Using the CF values ​​thus obtained, the adhesiveness of the sealant both initially and after heating was evaluated according to the following evaluation criteria.

[0110] Evaluation criteria for initial adhesion A: CF 100% B: CF 50% to CF 99% C: CF less than 50% (AF 50% or more).

[0111] Evaluation criteria for adhesiveness after heating: A: CF 100% B: CF 50% to CF 99% C: CF less than 50% (AF 50% or more).

[0112] Example 1: Preparation of surface-treated calcium carbonate particles (E1) The solid content concentration was 10.0 wt %, the temperature was adjusted to 50°C, and the BET specific surface area was 27 m ２ To 10 L of an aqueous slurry of synthetic calcium carbonate with a BET specific surface area of ​​23 m, 65 g of mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 6:6:22:16:50 (mass ratio)) whose composition had been adjusted in 1 L of hot water at 80°C were neutralized with caustic soda to prepare mixed fatty acid sodium salts, which were then added to the calcium carbonate slurry and vigorously stirred. This 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 calcium carbonate slurry with a BET specific surface area of ​​23 m. ２ The characteristics of the obtained surface-treated calcium carbonate particles (E1) are shown in Table 1.

[0113] Example 2: Preparation of surface-treated calcium carbonate particles (E2) Surface-treated calcium carbonate particles (E2) were obtained in the same manner as in Example 1, except that the composition of the mixed fatty acid used as the surface treatment agent was changed to lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=10:4:28:4:54 (mass ratio) (65 g of the surface treatment agent was added and neutralized with caustic soda). The characteristics of the obtained surface-treated calcium carbonate particles (E2) are shown in Table 1.

[0114] Example 3: Preparation of surface-treated calcium carbonate particles (E3) Surface-treated calcium carbonate particles (E3) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acids as in Example 1 was used and the amount of the surface treatment agent added was changed to 53 g, which was neutralized with caustic soda. The characteristics of the obtained surface-treated calcium carbonate particles (E3) are shown in Table 1.

[0115] Example 4: Preparation of surface-treated calcium carbonate particles (E4) Surface-treated calcium carbonate particles (E4) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acids as in Example 1 was used and the amount of the surface treatment agent added was changed to 77 g, which was neutralized with caustic soda. The characteristics of the obtained surface-treated calcium carbonate particles (E4) are shown in Table 1.

[0116] Example 5: Preparation of surface-treated calcium carbonate particles (E5) Surface-treated calcium carbonate particles (E5) were obtained in the same manner as in Example 1, except that the surface treatment agent used in Example 1 was changed to a mixed fatty acid composition (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=0:1:25:22:52 (mass ratio)) neutralized with caustic soda, and the amount of the surface treatment agent added was changed to 63 g. The characteristics of the obtained surface-treated calcium carbonate particles (E5) are shown in Table 1.

[0117] Example 6: Preparation of surface-treated calcium carbonate particles (E6) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 17 m ２ / g, the composition of the treatment agent was the same as in Example 1, and the amount of the surface treatment agent added was changed to 42 g, so that surface-treated calcium carbonate particles (E6) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E6) are shown in Table 1.

[0118] Example 7: Preparation of surface-treated calcium carbonate particles (E7) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 55 m ２ / g, the composition of the treatment agent was the same as in Example 1, and the amount of the surface treatment agent added was changed to 109 g, so that surface-treated calcium carbonate particles (E7) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E7) are shown in Table 1.

[0119] Example 8: Preparation of surface-treated calcium carbonate particles (E8) Surface-treated calcium carbonate particles (E8) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent in Example 1 was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=2:5:30:20:43 (mass ratio); 65 g of the surface treatment agent was added and neutralized with caustic soda before use). The characteristics of the obtained surface-treated calcium carbonate particles (E8) are shown in Table 1.

[0120] Example 9: Preparation of surface-treated calcium carbonate particles (E9) Surface-treated calcium carbonate particles (E9) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent in Example 1 was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=60:0:0:0:40 (mass ratio); 65 g of the surface treatment agent was added and neutralized with caustic soda before use). The characteristics of the obtained surface-treated calcium carbonate particles (E9) are shown in Table 1.

[0121] Example 10: Preparation of surface-treated calcium carbonate particles (E10) Surface-treated calcium carbonate particles (E10) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent in Example 1 was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=6:6:26:24:38 (mass ratio); 65 g of the surface treatment agent was neutralized with caustic soda before use). The characteristics of the obtained surface-treated calcium carbonate particles (E10) are shown in Table 1.

[0122] Example 11: Preparation of surface-treated calcium carbonate particles (E11) Surface-treated calcium carbonate particles (E11) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent in Example 1 was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=4:2:12:10:72 (mass ratio); 65 g of the surface treatment agent was added and neutralized with caustic soda before use). The characteristics of the obtained surface-treated calcium carbonate particles (E11) are shown in Table 1.

[0123] Example 12: Preparation of surface-treated calcium carbonate particles (E12) Surface-treated calcium carbonate particles (E12) were obtained in the same manner as in Example 1, except that a fatty acid having the same composition as in Example 1 was neutralized with caustic soda and then a fatty acid having the same composition was added thereto for surface treatment (fatty acid Na salt:fatty acid=8:2 (mass ratio), and the amounts of the surface treatment agent added were 52 g of fatty acid Na salt and 13 g of fatty acid). The characteristics of the obtained surface-treated calcium carbonate particles (E12) are shown in Table 1.

[0124] Example 13: Preparation of surface-treated calcium carbonate particles (E13) Surface-treated calcium carbonate particles (E13) were obtained in the same manner as in Example 1, except that 0.5% of caustic soda was added to the calcium carbonate slurry before surface treatment to adjust the pH to 11 or higher. The characteristics of the obtained surface-treated calcium carbonate particles (E13) are shown in Table 1.

[0125] Example 14: Preparation of surface-treated calcium carbonate particles (E14) Surface-treated calcium carbonate particles (E14) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acids as in Example 1 was neutralized with caustic soda and the amount of surface treatment agent added was changed to 32 g. The characteristics of the obtained surface-treated calcium carbonate particles (E14) are shown in Table 1.

[0126] Example 15: Preparation of surface-treated calcium carbonate particles (E15) Surface-treated calcium carbonate particles (E15) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acid as in Example 1 was neutralized with caustic soda and the amount of surface treatment agent added was changed to 111 g. The characteristics of the obtained surface-treated calcium carbonate particles (E15) are shown in Table 1.

[0127] Example 16: Preparation of surface-treated calcium carbonate particles (E16) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 65 m ２ / g, the composition of the treatment agent was the same as in Example 1, and the amount of the surface treatment agent added was changed to 139 g, so that surface-treated calcium carbonate particles (E16) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E16) are shown in Table 1.

[0128] Example 17: Preparation of surface-treated calcium carbonate particles (E17) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 12 m ２ / g, the composition of the treatment agent was the same as in Example 1, and the amount of the surface treatment agent added was changed to 28 g, so that surface-treated calcium carbonate particles (E17) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E17) are shown in Table 1.

[0129] Example 18: Preparation of surface-treated calcium carbonate particles (E18) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 8 m ２ / g, the composition of the treatment agent was the same as in Example 1, and the amount of the surface treatment agent added was changed to 17 g, so that surface-treated calcium carbonate particles (E18) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E18) are shown in Table 1.

[0130]

[0131] Comparative Example 1: Preparation of surface-treated calcium carbonate particles (C1) Surface-treated calcium carbonate particles (C1) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=0:0:28:52:20 (mass ratio), 65 g of the surface treatment agent was neutralized with caustic soda). The characteristics of the obtained surface-treated calcium carbonate particles (C1) are shown in Table 2.

[0132] Comparative Example 2: Preparation of surface-treated calcium carbonate particles (C2) Surface-treated calcium carbonate particles (C2) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=100:0:0:0:0 (mass ratio), 65 g of the surface treatment agent was neutralized with caustic soda). The characteristics of the obtained surface-treated calcium carbonate particles (C2) are shown in Table 2.

[0133] Comparative Example 3: Preparation of surface-treated calcium carbonate particles (C3) Surface-treated calcium carbonate particles (C3) were obtained in the same manner as in Example 1, except that the composition of the surface treatment agent was changed to a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=0:0:0:0:100 (mass ratio), 65 g of the surface treatment agent was neutralized with caustic soda). The characteristics of the obtained surface-treated calcium carbonate particles (C3) are shown in Table 2.

[0134] Comparative Example 4: Preparation of surface-treated calcium carbonate particles (C4) Surface-treated calcium carbonate particles (C4) were obtained in the same manner as in Example 1, except that a fatty acid having the same composition as in Example 1 was neutralized with caustic soda and then surface-treated by adding a fatty acid having the same composition (fatty acid Na salt: fatty acid = 1:1 (mass ratio), and the amounts of the surface treatment agent added were 38 g of fatty acid Na salt and 38 g of fatty acid). The characteristics of the obtained surface-treated calcium carbonate particles (C4) are shown in Table 2.

[0135] Comparative Example 5: Preparation of surface-treated calcium carbonate particles (C5) Surface-treated calcium carbonate particles (C5) were obtained in the same manner as in Example 1, except that 1.0% of caustic soda was added to the calcium carbonate slurry before surface treatment to adjust the pH to 12 or higher, and the same treating agent composition as in Example 1 was used, but the amount of the surface treatment agent added was changed to 76 g. The characteristics of the obtained surface-treated calcium carbonate particles (C5) are shown in Table 2.

[0136] Comparative Example 6: Preparation of surface-treated calcium carbonate particles (C6) Surface-treated calcium carbonate particles (C6) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acid sodium salt as in Example 1 was used and the amount of the surface treatment agent added was changed to 27 g. The characteristics of the obtained surface-treated calcium carbonate particles (C6) are shown in Table 2.

[0137] Comparative Example 7: Preparation of surface-treated calcium carbonate particles (C7) Surface-treated calcium carbonate particles (C7) were obtained in the same manner as in Example 1, except that the same composition of mixed fatty acid sodium salt as in Example 1 was used and the amount of the surface treatment agent added was changed to 120 g. The characteristics of the obtained surface-treated calcium carbonate particles (C7) are shown in Table 2.

[0138] Comparative Example 8: Preparation of surface-treated calcium carbonate particles (C8) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 19 m ２ / g, and the composition of the mixed fatty acids was changed (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=5:4:25:24:42 (mass ratio), 50 g of the surface treatment agent was neutralized with caustic soda), and the same procedure as in Example 1 was repeated to obtain surface-treated calcium carbonate particles (C8). The characteristics of the obtained surface-treated calcium carbonate particles (C8) are shown in Table 2.

[0139] Comparative Example 9: Preparation of surface-treated calcium carbonate particles (C9) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 18 m ２ / g, and the composition of the mixed fatty acids was changed to (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid=6:3:40:22:29 (mass ratio), 35 g of the surface treatment agent was neutralized with caustic soda), and the same procedure as in Example 1 was repeated to obtain surface-treated calcium carbonate particles (C9). The characteristics of the obtained surface-treated calcium carbonate particles (C9) are shown in Table 2.

[0140] Comparative Example 10: Preparation of surface-treated calcium carbonate particles (C10) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 60 m ２ / g, and the same treating agent composition as in Example 1 was used, except that the amount of the surface treatment agent added was changed to 170 g. Surface-treated calcium carbonate particles (C10) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C10) are shown in Table 2.

[0141] Comparative Example 11: Preparation of surface-treated calcium carbonate particles (C11) The BET specific surface area of ​​the synthetic calcium carbonate used in Example 1 was adjusted to 6 m ２ / g, and the same treating agent composition as in Example 1 was used, except that the amount of the surface treatment agent added was changed to 11 g, and surface-treated calcium carbonate particles (C11) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C11) are shown in Table 2.

[0142]

[0143] Examples 19 to 34: Preparation of sealants (SE19) to (SE34) The surface-treated calcium carbonate particles (E1) to (E18) obtained in Examples 1 to 18 were used as fillers as they were and kneaded with the components shown below to prepare one-component modified silicone sealants (SE19) to (SE34). Modified silicone resin containing methacrylic polymer (XMAP SB-802 manufactured by Kaneka Corporation) 100 parts by mass Antioxidant (ADEKA STAB AO-60 manufactured by ADEKA Corporation) 1 part by mass Plasticizer (acrylic plasticizer) (ALFON UP-1000 manufactured by Toagosei Co., Ltd.) 80 parts by mass Heavy calcium carbonate (Super S manufactured by Maruo Calcium Co., Ltd.) 80 parts by mass Surface-treated calcium carbonate particles obtained in Examples 1 to 16 120 parts by mass Dehydrating agent (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass Tin catalyst (Neostan U-220H manufactured by Nitto Kasei Co., Ltd.) 2 parts by mass Aminosilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass Total 390 parts by mass

[0144] This kneading was carried out as follows.

[0145] The modified silicone resin was placed in a 5 L universal mixer (manufactured by Dalton Co., Ltd.), along with surface-treated calcium carbonate particles and ground calcium carbonate that had been dried at 105°C for at least 2 hours, and pre-mixed at low speed for 15 minutes. The surface-treated calcium carbonate particles adhering to the inside of the mixer were then scraped off, and the mixture was immediately kneaded at high speed for 30 minutes under a vacuum atmosphere. The dehydrating agent, tin catalyst, and aminosilane were then added, and the mixture was mixed at low speed for 15 minutes under a vacuum atmosphere. The mixture was then filled into an aluminum foil-laminated cartridge and sealed with a metal plunger, yielding the one-component modified silicone sealant (sealants (SE19) to (SE34)) of each example.

[0146] The evaluation results of the obtained sealants (SE19) to (SE34) are shown in Table 5.

[0147] Example 35: Preparation of sealant (SE35) A sealant (SE35) was obtained in the same manner as in Example 19, except that the content of heavy calcium carbonate was changed to 50 parts by mass and the surface-treated calcium carbonate particles were changed to 150 parts by mass of the surface-treated calcium carbonate particles (E17) obtained in Example 17. The components of the obtained sealant (SE35) are shown in Table 3, and the evaluation results of the sealant (SE35) are shown in Table 5.

[0148] Example 36: Preparation of sealant (SE36) A sealant (SE36) was obtained in the same manner as in Example 19, except that the content of heavy calcium carbonate was changed to 50 parts by mass and the surface-treated calcium carbonate particles were changed to 50 parts by mass of the surface-treated calcium carbonate particles (E18) obtained in Example 18. The components of the obtained sealant (SE36) are shown in Table 3, and the evaluation results of the sealant (SE36) are shown in Table 5.

[0149] Example 37: Preparation of sealant (SE37) A sealant (SE37) was obtained in the same manner as in Example 19, except that the modified silicone resin used was changed to 70 parts by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802, manufactured by Kaneka Corporation) and 30 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203, manufactured by Kaneka Corporation). The components of the obtained sealant (SE37) are shown in Table 3, and the evaluation results of the sealant (SE37) are shown in Table 5.

[0150] Example 38: Preparation of sealant (SE38) A sealant (SE38) was obtained in the same manner as in Example 19, except that the modified silicone resin used was changed to 51 parts by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802, manufactured by Kaneka Corporation) and 49 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203, manufactured by Kaneka Corporation). The components of the obtained sealant (SE38) are shown in Table 3, and the evaluation results of the sealant (SE38) are shown in Table 5.

[0151] Example 39: Preparation of sealant (SE39) A sealant (SE39) was obtained in the same manner as in Example 19, except that the plasticizers used were changed to 61 parts by mass of an acrylic plasticizer (Alphon UP-1000 manufactured by Toagosei Co., Ltd.) and 19 parts by mass of a phthalate plasticizer (DINP manufactured by J-Plus Corporation). The components of the obtained sealant (SE39) are shown in Table 3, and the evaluation results of the sealant (SE39) are shown in Table 5.

[0152] Example 40: Preparation of sealant (SE40)

[0073] The modified silicone resin used was changed to 70 parts by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802 manufactured by Kaneka Corporation) and 30 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203 manufactured by Kaneka Corporation), and the plasticizer used was changed to 61 parts by mass of an acrylic plasticizer (Alfon UP-1000 manufactured by Toagosei Co., Ltd.) and 19 parts by mass of a phthalate plasticizer (DINP manufactured by J-Plus Corporation). A sealant (SE40) was obtained in the same manner as in Example 19. The components of the obtained sealant (SE40) are shown in Table 3, and the evaluation results of the sealant (SE40) are shown in Table 5.

[0153] Example 41: Preparation of sealant (SE41)

[0073] The modified silicone resin used was changed to 51 parts by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802 manufactured by Kaneka Corporation) and 49 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203 manufactured by Kaneka Corporation), and the plasticizer used was changed to 61 parts by mass of an acrylic plasticizer (Alfon UP-1000 manufactured by Toagosei Co., Ltd.) and 19 parts by mass of a phthalate plasticizer (DINP manufactured by J-Plus Corporation). A sealant (SE41) was obtained in the same manner as in Example 19. The components of the obtained sealant (SE41) are shown in Table 3, and the evaluation results of the sealant (SE41) are shown in Table 5.

[0154]

[0155] Comparative Examples 12 to 21: Preparation of sealants (SC12) to (SC21) The surface-treated calcium carbonate particles (C1) to (C11) obtained in Comparative Examples 1 to 11 were used as fillers as they were and mixed with the components shown below to prepare one-component modified silicone sealants (SC12) to (SC21). Modified silicone resin containing methacrylic polymer (XMAP SB-802 manufactured by Kaneka Corporation) 100 parts by mass Antioxidant (ADEKA STAB AO-60 manufactured by ADEKA Corporation) 1 part by mass Plasticizer (acrylic plasticizer) (ALFON UP-1000 manufactured by Toagosei Co., Ltd.) 80 parts by mass Heavy calcium carbonate (Super S manufactured by Maruo Calcium Co., Ltd.) 80 parts by mass Surface-treated calcium carbonate particles obtained in Comparative Examples 1 to 12 120 parts by mass Dehydrating agent (KBM-1003 manufactured by Shin-Etsu Chemical Co., Ltd.) 5 parts by mass Tin catalyst (Neostan U-220H manufactured by Nitto Kasei Co., Ltd.) 2 parts by mass Aminosilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass Total 390 parts by mass

[0156] This kneading was carried out as follows.

[0157] The modified silicone resin was placed in a 5 L universal mixer (manufactured by Dalton Co., Ltd.), along with surface-treated calcium carbonate particles and ground calcium carbonate that had been dried at 105°C for at least 2 hours, and pre-mixed at low speed for 15 minutes. The surface-treated calcium carbonate particles adhering to the inside of the mixer were then scraped off, and the mixture was immediately kneaded at high speed for 30 minutes under a vacuum. The dehydrating agent, tin catalyst, and aminosilane were then added, and the mixture was mixed at low speed for 15 minutes under a vacuum. The mixture was then filled into an aluminum foil-laminated cartridge and sealed with a metal plunger to obtain the one-component modified silicone sealants (sealants (SC12) to (SC21)) of each comparative example.

[0158] The evaluation results of the obtained sealants (SC1) to (SC21) are shown in Table 6.

[0159] Comparative Example 22: Preparation of sealant (SC22) A sealant (SC22) was obtained in the same manner as in Comparative Example 12, except that the content of heavy calcium carbonate was changed to 50 parts by mass and the surface-treated calcium carbonate particles were changed to 150 parts by mass of the surface-treated calcium carbonate particles obtained in Comparative Example 11. The components of the obtained sealant (SC22) are shown in Table 4, and the evaluation results of the sealant (SC22) are shown in Table 6.

[0160] Comparative Example 23: Preparation of sealant (SC23) A sealant (SC23) was obtained in the same manner as in Comparative Example 12, except that the modified silicone resin used was changed to 50 parts by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802, manufactured by Kaneka Corporation) and 50 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203, manufactured by Kaneka Corporation). The components of the obtained sealant (SC23) are shown in Table 4, and the evaluation results of the sealant (SC23) are shown in Table 6.

[0161] Comparative Example 24: Preparation of sealant (SC24) A sealant (SC24) was obtained in the same manner as in Comparative Example 12, except that the modified silicone resin used was changed to 30 parts by mass of a modified silicone resin containing a methacrylic polymer (Kaneka Corporation XMAP SB-802) and 70 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (Kaneka Corporation S-203). The components of the obtained sealant (SC24) are shown in Table 4, and the evaluation results of the sealant (SC24) are shown in Table 6.

[0162] Comparative Example 25: Preparation of sealant (SC25) A sealant (SC25) was obtained in the same manner as in Comparative Example 12, except that the modified silicone resin used was changed to 0 part by mass of a modified silicone resin containing a methacrylic polymer (XMAP SB-802, manufactured by Kaneka Corporation) and 100 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203, manufactured by Kaneka Corporation). The components of the obtained sealant (SC25) are shown in Table 4, and the evaluation results of the sealant (SC25) are shown in Table 6.

[0163]

[0164]

[0165]

[0166] As shown in Tables 5 and 6, the sealants (SE19) to (SE41) prepared using any of the surface-treated calcium carbonate particles (E1) to (E18) obtained in Examples 1 to 18 all had good low-temperature workability and good adhesive properties both initially and after heating. In contrast, some of the sealants (SC12) to (SC27) prepared using any of the surface-treated calcium carbonate particles (C1) to (C11) obtained in Comparative Examples 1 to 11 had poor low-temperature workability (e.g., Comparative Examples 12, 13, 18, 20 to 22), and even if the low-temperature workability was good, the adhesive properties were poor both initially and after heating.

[0167] This shows that the sealants (SE19) to (SE41) prepared using any of the surface-treated calcium carbonate particles (E1) to (E18) obtained in Examples 1 to 18 improved both the low-temperature workability and the initial adhesion and the adhesion after heating.

[0168] The present invention is useful in, for example, the fields of resin molding, construction and housing, paint, and a wide range of related technical fields.

Claims

1. A surface-treated calcium carbonate filler for use in a curable resin having a resin viscosity of 30 Pa·s or more at 23°C, the surface-treated calcium carbonate filler for a curable resin composition, which comprises surface-treated calcium carbonate particles surface-treated with a surface treatment agent and satisfies the following formulas (1) to (5). (1) 5 ≤ Sw ≤ 50 (m ２ / g) (2) 50 ≤ Mp ≤ 100 (mass%) (3) 45 ≤ UFa ≤ 80 (mass%) (4) 20 ≤ Nr ≤ 50 (mass%) (5) 1.00 ≤ Es ≤ 4.50 (mg / m ２ ) The Sw is the BET specific surface area (m ２ / g) of the surface-treated calcium carbonate particles. The Mp is the content (mass%) of fatty acids contained in the surface treatment agent, which is at least one selected from the group consisting of fatty acids having a melting point of 46°C or lower and salts thereof. The UFa is the proportion (mass%) of the unsaturated fatty acid moiety contained in the monovalent water-soluble fatty acid salt constituting the surface treatment agent. The Nr is the proportion (mass%) of the monovalent fatty acid salt constituting the counter ion obtained by refluxing the surface-treated calcium carbonate particles with ethanol to the total surface treatment amount of the surface treatment agent. The Es is the amount (mg / m ２ ) of the surface treatment agent per unit specific surface area of the surface-treated calcium carbonate particles.

2. The surface-treated calcium carbonate filler for a curable resin composition according to claim 1, wherein the fatty acids having a melting point of 46° C. or lower contained in the surface treatment agent are at least one compound selected from the group consisting of hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, oleic acid, linoleic acid, linolenic acid, and salts thereof.

3. The surface-treated calcium carbonate filler for a curable resin composition according to claim 1, wherein the curable resin is at least one selected from the group consisting of a (meth)acrylic homopolymer having an alkoxysilyl group, a mixture of a polyoxyalkylene polymer having an alkoxysilyl group and a (meth)acrylic polymer.

4. A curable resin composition containing the surface-treated calcium carbonate filler for a curable resin composition according to claim 1 and a curable resin.

5. The curable resin composition according to claim 4, wherein the curable resin is at least one selected from the group consisting of a (meth)acrylic homopolymer having an alkoxysilyl group, a mixture of a polyoxyalkylene polymer having an alkoxysilyl group and a (meth)acrylic polymer.

6. The curable resin composition according to claim 4, which is used as a sealing material or an adhesive.

7. The curable resin composition according to claim 4, which is a one-component resin composition or a two-component resin composition.

8. The curable resin composition according to claim 4, which contains a phthalic plasticizer in an amount of 5% by mass or less based on the total mass.

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