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

Abstract

To provide a surface-treated calcium carbonate filler for curable resin compositions which enables production of a curable resin composition having high thixotropy, improved workability during application under a low-temperature atmosphere, as well as low modulus and high elongation, even when blended with a high-viscosity curable resin, and also to provide a curable resin composition comprising the surface-treated calcium carbonate filler.SOLUTION: 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, wherein 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).SELECTED DRAWING: None

Description

Technical Field

[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, and 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.

Background Art

[0002] In recent years, longer service life has been required for general buildings such as buildings and condominiums, and prefabricated houses. Along with this, it is required that the waterproof performance of the sealing material applied to the exterior joints be maintained over a long period. In addition, it is also required to prevent the occurrence of dirt on the surface of the sealing material and around the joints, and the dirt and peeling of the coating film disposed on the sealing surface, thereby enhancing the aesthetic appearance and / or design.

[0003] For the sealing material to have a longer service life with the above performances, it is necessary for the sealing material to have low modulus and high elongation performance. Further, while improving heat resistance and water resistance, it is desired to suppress the deterioration of physical properties and maintain adhesiveness, so as to maintain various performances of the sealing material over a longer period.

[0004] The sealing material is also in a paste form during construction and has rubber elasticity after joint filling and finishing by moisture or reaction curing. Here, since the sealing material is manually filled into the joints by on-site workers using a cartridge gun or a caulking gun, it must maintain appropriate softness for trowel finishing of the joints. Particularly in the construction environment at low temperatures in winter, stickiness occurs in the sealing material paste and the viscosity increases, which easily hinders workability. Therefore, a design of a resin composition that is easy to work with even at low temperatures is required.

[0005] Silicone sealing materials based on organopolysiloxanes are known as those that meet the most demanding performance requirements for long service life. Silicone sealing materials have high heat resistance, have low modulus and high elongation performance over a long period of time, and are excellent in workability in that the viscosity increase at low temperatures is small.

[0006] However, silicone sealing materials have the drawback of being easily contaminated and conspicuous when placed around joints. In addition, it is difficult to paint the surface of this sealing material. Therefore, it is used only limitedly in buildings such as high-rise buildings and is hardly used in ordinary houses.

[0007] Here, in recent years, various resin compositions having low modulus and high elongation performance, which are useful as sealing materials, have been proposed.

[0008] For example, Patent Document 1 describes a resin composition containing surface-treated calcium carbonate containing a predetermined amount of an 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 resin that can be used is only one with a low resin viscosity having polyoxyalkylene as the main chain. The resin composition of Patent Document 1 also has drawbacks such as being unable to maintain heat resistance over a long period of time, being relatively easily decomposed, and having low water-resistant adhesiveness.

[0009] Patent Document 2 describes that a curable composition containing a (meth)acrylic polymer having an alkoxysilyl group, a polyoxyalkylene-based polymer having an alkoxysilyl group, and heavy calcium carbonate is excellent in weather resistance and suppresses the 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 excellent heat resistance, strength, and elongation to a curable resin composition, and a curable resin composition using the same. However, the curable resin composition described in Patent Document 3 has a problem that its viscosity becomes too high especially at low temperatures, resulting in low thixotropy, which may hinder the workability of construction workers.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

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

Means for Solving the Problems

[0013] The present invention is 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, comprising surface-treated calcium carbonate particles 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 ) 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 Nr is the ratio (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.

[0014] In one embodiment, 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.

[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, a mixture of a polyoxyalkylene polymer having an alkoxysilyl group and a (meth)acrylic polymer.

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

[0017] In one embodiment, the curable resin composition of the present invention is used as a sealing material or an 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 a phthalic acid-based plasticizer of 5% by mass or less based on the total mass.

Advantages of the Invention

[0020] According to the present invention, it is possible to provide a curable resin composition that maintains workability in a low-temperature construction environment, can achieve low modulus and high elongation, and has excellent heat resistance and high thixotropy. The curable resin composition obtained by using the surface-treated calcium carbonate filler of the present invention can prevent or suppress a decrease in workability during construction 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 higher viscosity difference even under the condition of 23°C compared to resins having an alkoxysilyl group containing a general polyoxyalkylene polymer, and have the property that the viscosity easily increases rapidly at an air temperature (temperature) of 5°C or lower.

[0022] By coexisting surface-treated calcium carbonate particles surface-treated with a surface treatment agent containing fatty acids having a melting point of 46°C or lower as a filler with such a curable resin, in addition to improving the compatibility with the curable resin, a rapid increase in viscosity at an air temperature (temperature) of 5°C or lower can be suppressed. Thereby, the low-temperature workability of the obtained curable resin composition is improved.

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

Modes for Carrying Out the Invention

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

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

[0028] Specifically, 200 to 300 mg of surface-treated calcium carbonate particles to be used as a sample are placed in a glass cell, set in a measuring device, and after being heat-treated at 200°C for 10 minutes in a mixed gas atmosphere of nitrogen and helium as a pretreatment, Sw is measured by performing low-temperature and low-humidity physical adsorption in an environment of liquid nitrogen.

[0029] Sw can be controlled by varying various conditions when manufacturing the surface-treated calcium carbonate particles in the present invention. Conditions that can control Sw within the above range include, for example, the concentration of lime milk used in the carbonation reaction as described later, the temperature adopted in the carbonation reaction, the concentration of carbon dioxide gas used, the type of additive used during the carbonation reaction, and combinations thereof. If the setting of such conditions is insufficient, it may be difficult to obtain surface-treated calcium carbonate particles that satisfy the above range of Sw.

[0030] (2) Content (Mp) of fatty acids contained in the surface treatment agent The surface-treated calcium carbonate particles in 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 of their composition. For example, according to Keiichi Inaba et al., New Edition Fatty Acid Chemistry, 2nd Edition, 2nd Printing, Kosei Publishing Co., 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), 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 lower, salts of such fatty acids, and combinations thereof. Examples of fatty acids having a melting point of 46°C or lower among the fatty acids include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, oleic acid, linoleic acid, and linolenic acid, and combinations thereof. Examples of fatty acid salts among the fatty acids include alkali metal salts of the above fatty acids (e.g., sodium salt, potassium salt), alkaline earth metal salts (e.g., calcium salt, magnesium salt), ammonium salts, and amine salts, and combinations thereof. In the present invention, since a higher effect can be obtained in terms of poor workability at low temperatures, the fatty acids having a melting point of 46°C or lower are preferably lauric acid, oleic acid, and combinations thereof.

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

[0034] The content (Mp) of fatty acids having a melting point of 46°C or lower contained in the surface treatment agent in the present invention is 50 to 100% by mass, preferably 50 to 80% by mass, and more preferably 55 to 65% by mass. When Mp is less than 50% by mass, the plasticizing effect at low temperatures of the resulting curable resin composition becomes weak, the thixotropy decrease at low temperatures is large, and the viscosity increase is also large, so that the workability during construction is not improved.

[0035] (3) Ratio (UFa) of the unsaturated fatty acid moiety contained in the monovalent water-soluble fatty acid salt constituting the surface treatment agent The surface-treated calcium carbonate particles in the present invention also contain an unsaturated fatty acid moiety contained in the monovalent water-soluble fatty acid salt constituting the surface treatment agent applied to the particles in a predetermined proportion (UFa; mass %). In the present invention, the proportion (UFa) of the 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% by mass, preferably 50 to 70% by mass, and more preferably 55 to 65% by mass. When the UFa in the surface treatment agent applied to the surface-treated calcium carbonate particles is less than 45% by mass, the viscosity of the resulting curable resin composition becomes high at low temperatures, deteriorating the workability of the constructor. When the UFa in the surface treatment agent applied to the surface-treated calcium carbonate particles exceeds 80% by mass, the heat resistance of the resulting curable resin composition decreases, it is liable to discolor, and the elongation rate decreases.

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

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

[0038] From the obtained gas chromatograph, the peaks of the main five types of fatty acid compositions (that is, lauric acid (C12), myristic acid (C14), palmitic acid (C16), and stearic acid (C18) which are saturated fatty acids, and oleic acid (C18F1) which is an unsaturated fatty acid) are analyzed and adjusted so that the sum of these peaks is 100%.

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

[0040] (4) The ratio (Nr) 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 In the surface-treated calcium carbonate particles of the present invention, the 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 satisfies within a predetermined range. In the present invention, Nr of the surface-treated calcium carbonate particles is 20 to 50% by mass, preferably 25 to 45% by mass, more preferably 30 to 40% by mass. When Nr of the surface-treated calcium carbonate particles is less than 20% by mass, the elongation rate of the obtained curable resin composition decreases, and it becomes difficult to obtain a resin composition with a long service life. When Nr of the surface-treated calcium carbonate particles exceeds 50% by mass, the obtained curable resin composition has low modulus and high elongation, but its water resistance decreases and its adhesiveness also decreases, which hinders the long-term waterproof performance.

[0041] (Measurement method of Nr) Nr of the surface-treated calcium carbonate particles can be measured as follows.

[0042] (a) First, 5 g of the surface-treated calcium carbonate particles are collected as a sample in a 300 mL Erlenmeyer flask, and 80 g of 95% ethanol is added thereto. (b) Next, the mouth of the flask is lightly covered with aluminum foil, boiled on a water bath at 90 °C or higher, and heated for 1 hour after the start of the boiling, then taken out from the water bath and allowed to cool at room temperature for 1 day. (c) The temperature is adjusted to 30 °C, and the content in the flask is suction filtered using a PTFE membrane filter (pore size 0.5 μm), and the filtrate is collected in a beaker. (d) The obtained filtrate is taken into a weighed 200 mL beaker, immersed in a hot water bath at 80 °C or higher to evaporate 95% ethanol. After cooling, the mass of the beaker is measured (note that the mass of the empty beaker is also measured before the above filtration). (e) Subsequently, the amount F (mg / g) of the free substance per 1 g of the surface-treated calcium carbonate particles is calculated as follows. F (mg / g) = [Mass of the beaker (mg) after filtration and cooling - Mass of the empty beaker (mg)] / Mass of the 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 neutralized and titrated 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 free substance per 1 g of the 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 on the surface-treated calcium carbonate particles × 10 3 (mg) / Mass of the surface-treated calcium carbonate particle sample (g) Here, assuming that the thermal weight loss (total amount of surface treatment agent) per 1 g of the 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 ethanol extraction of the surface-treated calcium carbonate particles to the total amount of surface treatment agent can be calculated as follows: Zf = (a / Tg) × 100 (mass %) Similarly, from the potassium hydroxide titration amount in (g) above, the amount s (mg / g) of the monovalent fatty acid salt constituting the counter ion in the free substance per 1 g of the surface-treated calcium carbonate particles can be calculated as follows: Amount of monovalent fatty acid salt s = Amount of free substance F - Amount 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) × 100 (mass %)

[0043] (5) Amount of surface treatment agent per unit specific surface area of surface-treated calcium carbonate particles (Es) The surface-treated calcium carbonate particles in the present invention also satisfy that the amount (Es) of the surface treatment agent per unit specific surface area of the surface-treated calcium carbonate particles is within 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 If Es of the surface-treated calcium carbonate particles is less than 1.00 mg / m 2 , the effect of surface treatment on the surface-treated calcium carbonate particles tends to be insufficient, and also, due to insufficient treatment, the untreated surface is exposed and it becomes easy to adsorb moisture. If Es of the surface-treated calcium carbonate particles exceeds 4.50 mg / m 2 , the excess surface treatment agent will act as a lubricant, which may adversely affect the heat resistance of the resulting curable resin composition, and in addition, it is economically disadvantageous. It is preferable to vary the amount of surface treatment according to 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 can be calculated by dividing the weight loss on heating (mg / g) (Tg; also referred to as the total amount of surface treatment agent) per 1 g of surface-treated calcium carbonate as follows by the above BET specific surface area (m 2 / g) (Sw): Es (mg / m 2 ) = Tg (mg / g) / Sw (m 2 / g)

[0045] (Measurement method of Tg) Here, Tg can be obtained as the weight loss per gram of the surface-treated calcium carbonate (mg / g) by measuring the weight loss from 200°C to 500°C when 100 mg of the surface-treated calcium carbonate is collected in a sample pan (made of platinum) with a diameter of 10 mm using a thermal analyzer (ThermoPlus EV02 manufactured by Rigaku Corporation) and heating from room temperature to 510°C at a heating rate of 15°C / min.

[0046] Es can be controlled by varying various conditions when manufacturing the surface-treated calcium carbonate particles in the present invention. Examples of the conditions under which Es can be controlled within the above range include the amount of surface treatment agent, the BET specific surface area, and combinations thereof. If the setting of such conditions is insufficient, it may be difficult to obtain surface-treated calcium carbonate particles that satisfy the above range of Es.

[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 such that the surface-treated calcium carbonate particles, which are its constituent components, satisfy all of formulas (1) to (5). Such surface-treated calcium carbonate particles are surface-treated calcium carbonate particles surface-treated with a surface treatment agent.

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

[0049] The surface-treated calcium carbonate particles in the present invention are those obtained by surface-treating unmodified (before surface treatment) calcium carbonate particles with a surface treatment agent.

[0050] (Unmodified calcium carbonate particles) Here, the unmodified calcium carbonate particles are rather particles of synthetic calcium carbonate (for example, light and colloidal calcium carbonate) prepared by a synthetic method of calcining natural gray dense limestone, rather than natural white saccharine limestone (heavy calcium carbonate) containing a large amount of fine particles from the viewpoint of the degassing property during kneading with a resin.

[0051] Such unmodified calcium carbonate particles can be produced, as a known carbon dioxide gas method, for example, by adding water to quicklime obtained by calcining gray dense limestone to make calcium hydroxide and reacting it with the carbon dioxide gas emitted during calcination. Further, the calcium carbonate slurry reacted by this carbon dioxide gas method can be adjusted by Ostwald ripening until it has a desired BET specific surface area to obtain desired calcium carbonate particles.

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

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

[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 still 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, araic 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 examples thereof include those synthesized in vivo by dehydration reaction 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 obtusilic acid, carlonic acid, undecylenic acid, linderic acid, tsuzuic acid, physeteric acid, moristenic acid, palmitoleic acid, petroselinic acid, oleic acid, elaidic acid, ascorbic acid, vaccenic acid, gadoleic acid, gondoic acid, cetoleic acid, erucic acid, brassidic acid, selacoleic acid, ximenic acid, rumelenic 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 containing the above other unsaturated fatty acids, fatty acids derived from plant raw materials such as palm and coconut, etc. may also be used as one of the components of the surface treatment agent.

[0057] Also, within a range that does not inhibit the effects of the present invention, the surface treatment agent may contain alicyclic carboxylic acids (e.g., naphthenic acid), resin acids (e.g., abietic acid, pimaric acid, palustric acid, neoabietic acid), and modified rosins (e.g., disproportionated rosins, hydrogenated rosins, dimer rosins, trimer rosins), sulfonic acids (e.g., alkylbenzene sulfonic acid), as well as their sodium salts, potassium salts, ammonium salts, and amine salts, which can 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 is carried out, for example, as follows using the above surface treatment agent.

[0059] Either a general dry treatment or wet treatment may be employed for the surface treatment of the unmodified calcium carbonate particles. Preferably, a method of adding the above surface treatment agent to an aqueous slurry containing the unmodified calcium carbonate particles can be adopted. Such a method is generally called a wet treatment and is preferable in that it can appropriately balance the degree of surface treatment and the production efficiency with respect to the calcium carbonate particles.

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

[0061] After the above surface treatment, the obtained particles may be powdered through optional operations such as dehydration, drying, and pulverization according to a conventional method, for example.

[0062] Note that dehydration can be performed on the slurry containing the surface-treated calcium carbonate particles using a filter press or a centrifugal dehydrator. For drying, a hot air dryer such as a micron dryer that can efficiently dry by directly contacting the surface-treated calcium carbonate particles with hot air at a high temperature may be used, or a heat transfer dryer such as a CD dryer that contacts the surface-treated calcium carbonate particles with a heating plate and indirectly dries them through the heating plate may be used.

[0063] In this way, surface-treated calcium carbonate particles surface-treated with the surface treatment agent can be obtained. These 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 having a resin viscosity of 30 Pa·s or more at 23°C described later.

[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 preferably has a resin viscosity of 30 Pa·s or more, more preferably 50 to 100 Pa·s at 23°C. For example, a resin with a viscosity of less than 30 Pa·s does not have a problem with low-temperature workability, so it is not necessarily required to be used in combination with the surface-treated calcium carbonate filler.

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

[0069] (Method for measuring the resin viscosity of the curable resin) Specifically, 300 g of the resin is placed in a 300 mL cup under an environment of 23°C and stirred at 10 rpm for 1 minute, and then it 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 terminal of the constituent molecules, and examples thereof include silicone resins and modified silicone resins that form siloxane bonds by hydrolysis and condensation reactions. Specific examples of the curable resin include acrylic silicone resins containing (meth)acrylic polymers, and are commercially available from Kaneka Corporation under the trade names of XMAP and S-943, for example.

[0071] In addition, as long as it is within the range having the above resin viscosity, as other resins, modified silicone resins having polyoxyalkylene (for example, MS polymers S-203, 303, S-810, etc. manufactured by Kaneka Corporation), modified silicone resins having an epoxy group (Silyl manufactured by Kaneka Corporation), and silylated urethane resins having an isocyanate group may be included. However, when such other resins are used in combination with an acrylic silicone resin containing a (meth)acrylic polymer, the mixing ratio can be set by those skilled in the art within a range that does not impair the effects exhibited by the surface-treated calcium carbonate filler of the present invention.

[0072] In the curable resin composition of the present invention, the blending amount of the surface-treated calcium carbonate filler in the curable resin varies depending on the type and use of the curable resin to be used, and thus is not particularly limited. However, it is preferably 5 to 200 parts by mass, more preferably 20 to 150 parts by mass, based on 100 parts by mass of the curable resin. If the blending amount of the surface-treated calcium carbonate filler is less than 5 parts by mass, sufficient thixotropy may not be imparted to the resulting curable resin composition. If the blending amount of the surface-treated calcium carbonate filler exceeds 200 parts by mass, the viscosity of the resulting 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 plasticizers that can be used include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyldiglycol 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), tris(chloroethyl) phosphate (TCEP), tris(dichloropropyl) phosphate (CRP), tributoxyethyl phosphate (TBXP), tris(β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyldiphenyl phosphate (CDP), acetyltriethyl citrate, tributyl acetylcitrate, trimellitic acid-based plasticizers, polyester-based plasticizers, chlorinated paraffin, stearic acid-based plasticizers, silicone oil (e.g., dimethylpolysiloxane), petroleum-based high-boiling solvents (e.g., petroleum-based high-boiling solvents such as polyoxypropylene glycol-based, paraffin-based, naphthene-based, isoparaffin-based, etc.). Specific examples of plasticizers include acrylic polymers (Alfon UP-1000, 1110, 1120, etc. manufactured by Toagosei Co., Ltd.). The above plasticizer is not particularly limited, but for example, 80 to 150 parts by mass is used with respect to 100 parts by mass of the curable resin.

[0074] In the present invention, it is preferable to suppress or avoid the use of phthalate plasticizers as much as possible. Phthalate plasticizers are well-known plasticizers in the art, but when the resulting resin composition is used as a sealing material, the coating film applied to the surface of the sealing material may cause bleed contamination. In addition, the elongation rate after heat curing may be significantly deteriorated, which may impair the aesthetic appearance and design, and may not be conducive to the performance of extending the service life. Therefore, in the cured resin composition of the present invention, it is preferable to set the content of the phthalate plasticizer to 5% by mass or less based on 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), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), and tetrahydrophthalic acid esters.

[0076] (Other fillers) The cured resin composition of the present invention may contain other fillers in addition to the above surface-treated calcium carbonate filler. Examples of 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 and synthetic products), basic magnesium carbonate, quartz powder, silica powder, precipitated silica (e.g., dry products, wet products, and gel method products), microcrystalline calcium silicate, microcrystalline aluminum silicate, kaolin clay, pyrophyllite clay, talc, sericite, mica, bentonite, nepheline syenite, aluminum hydroxide, magnesium hydroxide, barium sulfate, carbon black (e.g., furnace black, thermal black, and acetylene black), graphite, sepiolite, wollastonite, zonnolite, potassium titanate, carbon fiber, mineral fiber, glass fiber, shirasu balloon, fly ash balloon, glass balloon, silica beads, alumina beads, glass beads, etc.

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

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

[0080] (Other additives) The curable resin composition of the present invention may contain other additives. Examples of other additives include curing catalysts, anti-aging agents, colorants, silane coupling agents, waxes, foaming agents, diluents, solvents, etc.

[0081] Examples of curing catalysts include organotin compounds (e.g., dibutyltin laurate, dibutyltin dilaurate, dibutyltin dioctoate, dibutyltin acetate, dioctyltin stearate, dioctyltin laurate, dioctyltin diversatate, dibutyltin bis(triethoxysilicate), dibutyltin bis(isononyl 3-mercaptopropionate), dibutyltin bis(acetylacetonate), dibutyltin bis(o-phenylphenoxide), dibutyltin bis(isooctyl thioglycolate), dibutyltin oxide, and dioctyltin oxide); inorganic tin compounds (e.g., bis(2-ethylhexane)tin and tin bis(neodecanoate)); titanium chelate catalysts (e.g., titanium tetramethoxide, titanium tetraethoxide, titanium acryloxide, titanium n-propoxide, titanium tetraisopropoxide, titanium ethyl acetoacetate, and titanium acetylacetonate); organoaluminum compounds (e.g., aluminum tris(acetylacetonate), aluminum tris(ethyl acetoacetate), and diisopropoxyaluminum ethyl acetoacetate); bismuth catalysts (e.g., bismuth tris(neodecanoate)); zirconium metal catalysts (e.g., zirconium tetraacetylacetonate); and the like.

[0082] Examples of anti-aging agents include ultraviolet absorbers (e.g., benzotriazole-based compounds), antioxidants (e.g., phenolic antioxidants and amine-based antioxidants), and light stabilizers.

[0083] Examples of colorants include inorganic pigments (e.g., titanium dioxide, carbon black, etc.) and organic pigments (e.g., azo-based pigments, phthalocyanine-based 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 can be mentioned. If necessary, other silane coupling agents such as vinyl silane and epoxy silane may be used in combination.

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

[0086] As the foaming agent, a type of foaming agent that generates gas by heating can be used. For example, azo-based foaming agents such as azodicarbonamide and azobisformamide can be used.

[0087] Examples of the diluent include xylene, mineral terpene, and the like.

[0088] Examples of the solvent 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 oil and fatty acid ester-modified silicone oil; and combinations thereof. However, the solvent may impair the heat resistance and / or durability of the resulting curable resin composition, and it is desirable not to use it.

[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 together satisfy the above formulas (1) to (5), and an appropriate amount can be appropriately selected by those skilled in the art.

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

Examples

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

[0092] The materials and evaluation of the surface-treated calcium carbonate fillers described in each example and comparative example were carried out as follows.

[0093] (A) Fatty acid composition, (B) BET specific surface area (Sw) of the surface-treated calcium carbonate, (C) The proportion (UFa) of the unsaturated fatty acid part contained in the monovalent water-soluble fatty acid salts constituting the surface treatment agent (D) The ratio (Nr) to the total surface treatment amount of the surface treatment agent of the monovalent fatty acid salt constituting the counter ion obtained by dry distilling the surface-treated calcium carbonate particles with ethanol (E) The amount (Es) of the surface treatment agent per unit specific surface area of the surface-treated calcium carbonate particles (A) to (E) were each measured by the above-described measurement methods.

[0094] The viscosity of the sealant After allowing the sealants obtained in each of the examples and comparative examples to stand at 23°C for 1 day, they were filled into a 100 mL polypropylene (PP) cup using a cartridge gun and measured using a TV-type viscometer (VISCOMETER TV-100 manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H7).

[0095] At 1 rpm, the value 3 minutes after the start of measurement was taken as the viscosity value, at 2 rpm, the value 2 minutes after the start of measurement was taken as the viscosity value, and at 10 rpm, the value 1 minute after the start of measurement was taken as the viscosity value. Also, the TI value was calculated by dividing the viscosity value at 2 rpm by the viscosity value at 10 rpm.

[0096] The low-temperature workability of the sealant After storing the cartridges filled with the sealants obtained in each of the examples and comparative examples in a low-temperature environment (5°C) for 1 day, the sealants were filled into a 100 mL PP cup using a cartridge gun and measured using a TV-type viscometer (VISCOMETER TV-100 manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H7). For the viscosity, the value 2 minutes after the start of measurement at 2 rpm and the value 1 minute after the start of measurement at 10 rpm were measured and taken as the viscosity values respectively. Also, the TI value was calculated by dividing the viscosity value at 2 rpm by the viscosity value at 10 rpm, and the obtained value was judged according to the following criteria.

[0097] However, for those with a viscosity value of 600 Pa·s or more at 10 rpm under such low-temperature environments, all were evaluated as × regardless of whether the calculated TI value corresponded to ◎ to △. ◎: TI was 2.8 or more. ○: TI was 2.3 or more and less than 2.8. △: TI was 1.8 or more and less than 2.3. ×: TI was less than 1.8 or the viscosity value at 10 rpm was 600 Pa·s or more.

[0098] Tensile adhesion of the 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 dried for 60 minutes. Then, the sealants obtained in each example and comparative example were filled (shape: 12 mm × 12 mm × 50 mm), and an H-type test specimen was prepared in accordance with JIS A 1439:2016 (Building sealing materials 5.12.2, Preparation of tensile test specimens).

[0099] This test specimen was heated at 23°C for 14 days and at 30°C for 14 days, and then held at 23°C for 1 day. After that, the maximum strength and maximum elongation rate measured using a tensile testing machine (Autograph AG-1 manufactured by Shimadzu Corporation) were referred to as the initial strength and initial elongation rate, respectively. Furthermore, it was heated at 100°C for 42 days and then held at 23°C for 1 day, and the maximum strength and maximum elongation rate measured after that were referred to as the strength after heating and elongation rate after heating, respectively.

[0100] The above maximum strength (Tmax) is a value obtained by dividing the maximum load by the cross-sectional area of the sealant (600 mm 2 ) when the sealant is pulled from the test specimen at a speed of 50 mm per minute for 1 minute.

[0101] The above maximum elongation rate (Emax) is a value obtained by dividing the displacement amount when measuring the above maximum strength by one side (12 mm) of the shape of the sealant when the sealant is filled in the aluminum plate and multiplying by 100.

[0102] Furthermore, with respect to the initial strength (maximum strength) and initial elongation ratio (maximum elongation ratio) obtained above, and each value of the strength after heating (maximum strength) and elongation ratio after heating (maximum elongation ratio), the determination was made according to the following criteria.

[0103] (Determination Criteria for Initial Tensile Test) Initial strength (maximum strength / Tmax): ◎: 0.40 N / mm 2 or more. ○: 0.30 N / mm 2 or more and less than 0.40 N / mm 2 .[[]END]] △: 0.20 N / mm 2 or more and less than 0.30 N / mm 2 .[[]END]] ×: less than 0.20 N / mm 2 .[[]END]]

[0104] Initial elongation ratio (maximum elongation ratio / Emax): ◎: 600% or more. ○: 450% or more and less than 600%. △: 300% or more and less than 450%. ×: less than 300%.

[0105] (Determination Criteria for Tensile Test after Heating) Strength after heating (maximum strength / Tmax): ◎: 0.30 N / mm 2 or more. ○: 0.20 N / mm 2 or more and less than 0.30 N / mm 2 .[[]END]] △: 0.10 N / mm 2 or more and less than 0.20 N / mm 2 .[[]END]] ×: less than 0.1 N / mm 2 .[[]END]]

[0106] Elongation ratio after heating (maximum elongation ratio / Emax): ◎: 350% or more. ○: It was 250% or more and less than 350%. △: It was 150% or more and less than 250%. ×: It was less than 150%.

[0107] (Adhesion) Regarding the obtained sealant, it is preferable that the breakage of the sealant occurs inside (the center) of the sealant rather than on the adhesion surface.

[0108] The CF value indicates the ratio (%) of cohesive failure, and the AF value indicates the ratio (%) of interfacial peeling. Here, a CF value of 100% indicates 100% cohesive failure and shows having desirable adhesion. On the other hand, an AF value of 100% represents that interfacial peeling has occurred and shows having undesirable adhesion.

[0109] Using the CF value obtained in this way, the adhesion of the sealant at each of the initial and after heating was judged according to the following criteria.

[0110] Judgment criteria for initial adhesion ○: CF was 100%. △: CF was 50% to CF 99%. ×: CF was less than 50% (AF was 50% or more).

[0111] Judgment criteria for adhesion after heating ○: CF was 100% △: CF was 50% to CF 99%. ×: CF was less than 50% (AF was 50% or more).

[0112] Example 1: Preparation of surface-treated calcium carbonate particles (E1) Solid content concentration adjusted to 10.0 wt%, temperature 50 °C, BET specific surface area 27 m 2To 10 L of an aqueous slurry of synthetic calcium carbonate at 1 g, 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 was adjusted in 1 L of warm water at 80 °C were neutralized with caustic soda, added as sodium salt of mixed fatty acids, and strongly stirred together with the calcium carbonate slurry. 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 surface-treated calcium carbonate particles (E1) with a BET specific surface area of 23 m 2 / g. 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 acids 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) (the addition amount of the surface treatment agent was 65 g 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 addition amount of the surface treatment agent was changed to 53 g neutralized with caustic soda for use. 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 addition amount of the surface treatment agent was changed to 77 g neutralized with caustic soda for use. 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) In Example 1, as the surface treatment agent, the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 0:1:25:22:52 (mass ratio)) was neutralized with caustic soda and changed for use, and surface-treated calcium carbonate particles (E5) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent 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 changed to 17 m 2 / g, the treatment agent composition was the same as in Example 1, and surface-treated calcium carbonate particles (E6) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent was changed to 42 g. 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 changed to 55 m 2 / g, the treatment agent composition was the same as in Example 1, and surface-treated calcium carbonate particles (E7) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent was changed to 109 g. 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) In Example 1, as the surface treatment agent, the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 2:5:30:20:43 (mass ratio), and the addition amount of the surface treatment agent was used after neutralization with caustic soda) was changed, and surface-treated calcium carbonate particles (E8) were obtained in the same manner as in Example 1. 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) In Example 1, except that the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 60:0:0:0:40 (mass ratio)) used as the surface treatment agent and the addition amount of the surface treatment agent was 65 g neutralized with caustic soda, surface-treated calcium carbonate particles (E9) were obtained in the same manner as in Example 1. 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) In Example 1, except that the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 6:6:26:24:38 (mass ratio)) used as the surface treatment agent and the addition amount of the surface treatment agent was 65 g neutralized with caustic soda, surface-treated calcium carbonate particles (E10) were obtained in the same manner as in Example 1. 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) In Example 1, except that the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 4:2:12:10:72 (mass ratio)) used as the surface treatment agent and the addition amount of the surface treatment agent was 65 g neutralized with caustic soda, surface-treated calcium carbonate particles (E11) were obtained in the same manner as in Example 1. 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) Except that fatty acids of the same composition were added to the fatty acids neutralized with caustic soda in the same composition as in Example 1 for surface treatment (fatty acid Na salt: fatty acid = 8:2 (mass ratio), and the addition amount of the surface treatment agent was 52 g of fatty acid Na salt and 13 g of fatty acid), surface-treated calcium carbonate particles (E12) were obtained in the same manner as in Example 1. 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) Calcium carbonate slurry before surface treatment was added with 0.5% caustic soda to make the pH 11 or higher, and surface-treated calcium carbonate particles (E13) were obtained in the same manner as in Example 1 except for this. 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) Calcium carbonate particles (E14) were obtained in the same manner as in Example 1 except that the mixed fatty acids having the same composition as in Example 1 were neutralized with caustic soda and the addition amount of the surface treatment agent 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) Calcium carbonate particles (E15) were obtained in the same manner as in Example 1 except that the mixed fatty acids having the same composition as in Example 1 were neutralized with caustic soda and the addition amount of the surface treatment agent 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 changed to 65 m 2 / g, the treatment agent composition was the same as in Example 1, and surface-treated calcium carbonate particles (E16) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent was changed to 139 g. 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 changed to 12 m 2 / g, the treatment agent composition was the same as in Example 1, and surface-treated calcium carbonate particles (E17) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent was changed to 28 g. 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 changed to 8 m 2 / g, the treatment agent composition was the same as in Example 1, and surface-treated calcium carbonate particles (E18) were obtained in the same manner as in Example 1 except that the addition amount of the surface treatment agent was changed to 17 g. The characteristics of the obtained surface-treated calcium carbonate particles (E18) are shown in Table 1.

[0130]

Table 1

[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 mixed fatty acids as the surface treatment agent (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 0:0:28:52:20 (mass ratio), and the addition amount of the surface treatment agent was neutralized with caustic soda at 65 g). 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 mixed fatty acids as the surface treatment agent (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 100:0:0:0:0 (mass ratio), and the addition amount of the surface treatment agent was neutralized with caustic soda at 65 g). 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) As the surface treatment agent, surface-treated calcium carbonate particles (C3) were obtained in the same manner as in Example 1 except that the composition of the mixed fatty acids was changed (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 0:0:0:0:100 (mass ratio), and the addition amount of the surface treatment agent was neutralized with 65 g of 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 treatment was carried out by adding fatty acids of the same composition to a fatty acid neutralized with caustic soda having the same composition as in Example 1 (fatty acid Na salt: fatty acid = 1:1 (mass ratio), and the addition amount of the surface treatment agent was 38 g of fatty acid Na salt and 38 g of fatty acid). Surface-treated calcium carbonate particles (C4) were obtained in the same manner as in Example 1 except for the above. 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) 1.0% of caustic soda was added to the calcium carbonate slurry before surface treatment to adjust the pH to 12 or higher. Surface-treated calcium carbonate particles (C5) were obtained in the same manner as in Example 1 except that the same treatment agent composition was used and the addition amount of the surface treatment agent 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 composition of the same sodium salt of mixed fatty acids as in Example 1 was used and the addition amount of the surface treatment agent 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) Using the same composition of sodium salt of mixed fatty acids as in Example 1, surface-treated calcium carbonate particles (C7) were obtained in the same manner as in Example 1, except that the addition amount of the surface treatment agent 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 changed to 19 m 2 / g, and the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 5:4:25:24:42 (mass ratio), and the addition amount of the surface treatment agent was neutralized with 50 g of caustic soda) was changed. Surface-treated calcium carbonate particles (C8) were obtained in the same manner as in Example 1. 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 changed to 18 m 2 / g, and the composition of the mixed fatty acids (lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 6:3:40:22:29 (mass ratio), and the addition amount of the surface treatment agent was neutralized with 35 g of caustic soda) was changed. Surface-treated calcium carbonate particles (C9) were obtained in the same manner as in Example 1. 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 changed to 60 m 2 / g, and using the same treatment agent composition as in Example 1, surface-treated calcium carbonate particles (C10) were obtained in the same manner as in Example 1, except that the addition amount of the surface treatment agent was changed to 170 g. 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 6 m 2 / g, and the same treatment 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] [Table 2]

[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 produce one-component modified silicone sealants (SE19) to (SE34). Modified silicone resin containing methacrylic polymer (Kaneka Corporation XMAP SB-802) 100 parts by weight antioxidants (ADEKA Corporation ADK STAB AO-60) 1 part by mass Plasticizer (acrylic plasticizer) (Toagosei Co., Ltd., Alphon UP-1000) 80 parts by weight Ground calcium carbonate (Maruo Calcium Co., Ltd. Super S) 80 parts by weight 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 (Nitto Kasei Co., Ltd. Neostan U-220H) 2 parts by weight 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] 5 L of a universal mixing stirrer (manufactured by Dalton Co., Ltd.) was charged with a modified silicone resin, and surface-treated calcium carbonate particles and heavy calcium carbonate that had been previously dried at 105°C for 2 hours or more were charged together, followed by preliminary stirring at a low speed for 15 minutes. After that, the surface-treated calcium carbonate particles adhering to the inside of the mixing stirrer were scraped off, and immediately, kneading was carried out at a high speed for 30 minutes under a vacuum atmosphere. Then, a dehydrating agent, a tin catalyst, and an aminosilane were added, and mixing was carried out at a low speed for 15 minutes under a vacuum atmosphere. This was filled into a cartridge coated with an aluminum foil laminate, sealed with a metal plunger, and one-component modified silicone sealants (sealants (SE19) to (SE34)) of each example were obtained.

[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) 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). A sealant (SE37) was obtained in the same manner as in Example 19 except for this change. 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) 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). A sealant (SE38) was obtained in the same manner as in Example 19 except for this change. 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) The plasticizer used was 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 phthalic plasticizer (DINP manufactured by J-PLUS Co., Ltd.). A sealant (SE39) was obtained in the same manner as in Example 19 except for this change. 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) 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 (Alphon UP-1000 manufactured by Toagosei Co., Ltd.) and 19 parts by mass of a phthalate plasticizer (DINP manufactured by Jay Plus Co., Ltd.). A sealant (SE) was obtained in the same manner as in Example 19 except for the above changes. 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) 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 (Alphon UP-1000 manufactured by Toagosei Co., Ltd.) and 19 parts by mass of a phthalate plasticizer (DINP manufactured by Jay Plus Co., Ltd.). A sealant (SE41) was obtained in the same manner as in Example 19 except for the above changes. 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]

Table 3

[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 following components to prepare one-component modified silicone-based sealants (SC12) to (SC21). Modified silicone resin containing methacrylic polymer (XMAP SB-802 manufactured by Kaneka Corporation) 100 parts by mass Antioxidant 1 part by mass of Adekastab AO-60 (manufactured by ADEKA CORPORATION) Plasticizer (acrylic plasticizer) 80 parts by mass of Alphon UP-1000 (manufactured by Toagosei Co., Ltd.) Heavy calcium carbonate 80 parts by mass of Super S (manufactured by Maruo Calcium Co., Ltd.) 120 parts by mass of the surface-treated calcium carbonate particles obtained in Comparative Examples 1 to 12 Dehydrating agent 5 parts by mass of KBM-1003 (manufactured by Shin-Etsu Chemical Co., Ltd.) Tin catalyst 2 parts by mass of Neo-Stann U-220H (manufactured by Nitto Kasei Co., Ltd.) Aminosilane 2 parts by mass of KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.) Total: 390 parts by mass

[0156] This kneading was carried out as follows.

[0157] The modified silicone resin was put into a 5 L universal mixing stirrer (manufactured by Dalton Co., Ltd.), and the surface-treated calcium carbonate particles and heavy calcium carbonate that had been dried in advance at 105°C for 2 hours or more were put together, and preliminary stirring was carried out at a low speed for 15 minutes. Then, after scraping off the surface-treated calcium carbonate particles adhering to the inside of the mixing stirrer, kneading was immediately carried out at a high speed for 30 minutes under a vacuum atmosphere. Then, a dehydrating agent, a tin catalyst, and an aminosilane were added, and mixing was carried out at a low speed for 15 minutes under a vacuum atmosphere. This was filled into a cartridge coated with aluminum foil laminate and sealed with a metal plunger to obtain a one-component modified silicone sealant (sealants (SC12) to (SC21)) for 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) 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. A sealant (SC22) was obtained in the same manner as in Comparative Example 12 except for the above changes. 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 (XMAP SB-802 manufactured by Kaneka Corporation) and 70 parts by mass of a modified silicone resin containing a polyoxyalkylene polymer (S-203 manufactured by Kaneka Corporation). 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 parts 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]

Table 4

[0164]

Table 5

[0165]

Table 6

[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 adhesiveness both initially and after heating. In contrast, among 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, there were those with poor low-temperature workability (for example, Comparative Examples 12, 13, 18, 20 to 22), and even if the low-temperature workability was good, they were inferior in adhesiveness both initially and after heating.

[0167] From this, it can be seen 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 adhesiveness both initially and after heating.

Industrial Applicability

[0168] According to the present invention, for example, it is useful in the fields of resin molding, construction and housing, paints, and a wide range of technical fields related thereto.

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, comprising surface-treated calcium carbonate particles surface-treated with a surface treatment agent and satisfying the following formulas (1) to (5), a surface-treated calcium carbonate filler for a curable resin composition. (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, and 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 ratio (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 ratio (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, 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, containing a phthalic acid-based plasticizer in an amount of 5% by mass or less based on the total mass.

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