Surface-treated calcium carbonate filler for curable resin compositions and curable resin compositions using the filler

Abstract

The surface-treated calcium carbonate filler of the present invention is used in curable resins having a resin viscosity of 30 Pa·s or higher at 23°C, and includes surface-treated calcium carbonate particles that have been surface-treated using a surface-treatment agent. Here, in the surface-treated calcium carbonate filler of the present invention, Sw is 5 to 50 (m). 2 / g), Mp 50 to 100 (mass%), UFa 45 to 80 (mass%), Nr 20 to 50 (mass%), Es 1.00 to 4.50 (mg / m³). 2 ).

Description

Technical Field

[0001] This invention relates to surface-treated calcium carbonate filler for use in curable resin compositions and curable resin compositions using the filler, and more specifically, to surface-treated calcium carbonate filler for use in curable resin compositions comprising high-viscosity resins and curable resin compositions using the filler. Background Technology

[0002] In recent years, there has been a growing demand for longer lifespans in general buildings such as high-rises and apartments, as well as in prefabricated residential buildings. Accompanying this demand is the requirement to maintain the waterproof performance of sealants applied to exterior wall joints over extended periods. Furthermore, there is a need to prevent contamination on the surface of the sealant or around the joints, as well as to prevent contamination or peeling of the coating applied to the sealant surface, thereby improving aesthetics and / or design appeal.

[0003] To extend the lifespan of the aforementioned properties, sealing materials need to possess low modulus and high elongation. Furthermore, it is desirable to maintain the various properties of the sealing material for a longer period by improving heat and water resistance, suppressing property degradation, and maintaining adhesion.

[0004] The sealant is in paste form during application, but after joint filling and finishing, it hardens due to moisture or reaction, becoming rubbery. Since on-site workers use caulking guns or filler guns to manually fill the joints, the sealant must maintain a suitable degree of flexibility during the caulking process. Especially in low-temperature winter environments, the sealant paste becomes sticky, increasing viscosity and hindering workability. Therefore, it is necessary to design resin compositions that are easy to apply even at low temperatures.

[0005] It is known that silicone sealants based on organopolysiloxanes meet the requirements for maximum service life. These silicone sealants exhibit excellent workability in the following aspects: high heat resistance, low modulus and high elongation over extended periods, and minimal viscosity increase at low temperatures.

[0006] However, silicone sealants have the following drawback: they are prone to staining and becoming noticeable when applied around joints. Additionally, they are difficult to coat. Therefore, their use is limited to high-rise buildings and almost never in ordinary residential buildings.

[0007] In recent years, various resin compositions with low modulus and high elongation properties have been proposed as sealing materials.

[0008] For example, Patent Document 1 describes a resin composition comprising 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 fatty acids or the like and adding a compound containing the alkali metal. However, the modified silicone resin that can be used is simply a low-viscosity resin with a polyoxyethylene main chain. The resin composition of Patent Document 1 also has the following disadvantages: it cannot maintain heat resistance over a long period, it decomposes relatively easily, and it has poor water resistance and adhesion.

[0009] Patent Document 2 describes a curable composition comprising an alkoxysilyl (meth)acrylic acid polymer, an alkoxysilyl polyoxyolefin polymer, and heavy calcium carbonate, which exhibits excellent weather resistance and suppresses viscosity increase at low temperatures. However, such a curable composition has the drawback of lacking workability (fiber-drawing properties).

[0010] Patent Document 3 describes a surface-treated calcium carbonate filler that provides excellent heat resistance, strength, and elongation to a cured resin composition, and a cured resin composition using the filler. However, the cured resin composition described in Patent Document 3 has an excessively high viscosity and low thixotropy, particularly at low temperatures, which may hinder the workability of the applicator.

[0011] Prior art literature Patent documents Patent Document 1: Japanese Patent No. 5728616; Patent Document 2: Japanese Patent Application Publication No. 2021-155604; Patent document 3: International Publication No. 2016 / 152762. Summary of the Invention

[0012] The problem that the invention aims to solve The present invention addresses the above-mentioned problems and aims to provide a surface-treated calcium carbonate filler for curable resin compositions and a curable resin composition using the filler, which, even when combined with a curable resin having high viscosity, can produce a curable resin composition with high thixotropy, improved workability during construction in a low-temperature atmosphere, low modulus, and high elongation.

[0013] Solution for solving the problem This invention relates to a surface-treated calcium carbonate filler for use in curable resin compositions. It is a surface-treated calcium carbonate filler used in curable resins having a viscosity of 30 Pa·s or higher at 23°C. This includes surface-treated calcium carbonate particles treated with surface treatment agents, and satisfying the following equations (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 / m2) Sw is the BET specific surface area (m²) of the surface-treated calcium carbonate particles. 2 / g), Mp is the content (mass %) of fatty acids included in the surface treatment agent, which is at least one type selected from the group consisting of fatty acids and their salts having a melting point below 46°C. Nr is the ratio (mass %) of the monovalent fatty acid salt containing anti-charged ions obtained by refluxing the surface-treated calcium carbonate particles with ethanol to the total surface-treated amount of the surface treatment agent. Es is the amount of the surface-treating agent per unit specific surface area of ​​the surface-treated calcium carbonate particles (mg / m²). 2 ).

[0014] In one embodiment, the fatty acids included in the surface treatment agent having a melting point of 46°C or below 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 their salts.

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

[0016] The present invention is also a cured resin composition containing the above-mentioned cured resin composition, surface-treated calcium carbonate filler and cured resin.

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

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

[0019] In one embodiment, the cured resin composition of the present invention contains less than 5% by weight of phthalic acid plasticizer relative to the total mass.

[0020] Invention Effects According to the present invention, a curable resin composition can be provided that maintains workability in low-temperature application environments, achieves low modulus and high elongation, and exhibits 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 a decrease in workability during application, even in low-temperature atmospheres, for example.

[0021] Regarding viscosity increase at low temperatures, resins with high viscosity, including (meth)acrylic polymers and polymers containing alkoxysilyl groups, have the following property compared to resins containing alkoxysilyl groups, including general polyoxyethylene polymers: even at 23°C, there is a high viscosity difference, and the viscosity tends to increase rapidly at temperatures below 5°C.

[0022] For such curing resins, surface-treated calcium carbonate particles, which are surface-treated with a fatty acid-based surface treatment agent with a melting point below 46°C, are used as fillers. This not only improves the compatibility with the curing resin but also suppresses the sharp increase in viscosity at temperatures below 5°C. Consequently, the low-temperature workability of the resulting curing resin composition is improved.

[0023] Furthermore, by using surface-treated calcium carbonate particles, which are surface-treated with a surface-treatment agent containing unsaturated fatty acids in a specific ratio and have a low melting point, as a filler, the thixotropic properties of the resulting cured resin composition can be improved, resulting in low modulus and high elongation properties. Detailed Implementation

[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 comprises surface-treated calcium carbonate particles that have undergone surface treatment using a surface treatment agent. These surface-treated calcium carbonate particles are composed of synthetic calcium carbonate particles that satisfy the following formulas (1) to (5).

[0026] (1) BET specific surface area (Sw) The surface-treated calcium carbonate particles in this invention have a predetermined BET specific surface area (Sw; m²). 2 / g). In this invention, the Sw of the surface-treated calcium carbonate particles is 5 to 50m. 2 / g, preferably 10 to 40m 2 / g, more preferably 15 to 35m 2 / g. If the Sw of surface-treated calcium carbonate particles is less than 5m 2If the sw of the surface-treated calcium carbonate particles exceeds 50 μm, the primary particles become too large, sometimes making it difficult to impart sufficient thixotropy to the resulting cured resin composition. 2 If the amount of surface treatment required to cover the surface of the calcium carbonate particles used as raw materials increases, the rate of change in the physical properties of the resulting cured resin composition after heat resistance may increase.

[0027] In addition, Sw is the value for surface-treated calcium carbonate particles determined using the nitrogen adsorption method (BET method), and is determined by the following test method.

[0028] (Method for determining Sw) Sw of surface-treated calcium carbonate particles can be measured, for example, using Macsorb HMmodel-1201 manufactured by Mounttech Corporation as follows.

[0029] Specifically, 200 to 300 mg of surface-treated calcium carbonate particles for testing are placed as a sample into a glass colorimetric cell and set in the measuring device. After being heated at 200°C for 10 minutes in a nitrogen and helium mixed gas atmosphere as a pretreatment, low-temperature and low-humidity physical adsorption is performed in a liquid nitrogen environment to determine Sw.

[0030] Sw can be controlled by varying the conditions used in manufacturing the surface-treated calcium carbonate particles of this invention. Examples of conditions that allow Sw to be controlled within the aforementioned range include, for instance, the concentration of lime slurry used in the carbonation reaction, the temperature employed in the carbonation reaction, the concentration of carbonic acid gas used, and the types and combinations of additives used in the carbonation reaction. If these conditions are not sufficiently set, it can be difficult to obtain surface-treated calcium carbonate particles that satisfy the aforementioned Sw range.

[0031] (2) The content of fatty acids (Mp) in the surface treatment agent The surface-treated calcium carbonate particles of this invention also contain a predetermined amount of fatty acids in the surface-treated agent applied to the particles. Here, the term "fatty acids" also includes any one of fatty acids, fatty acid salts, and combinations thereof.

[0032] Fatty acids have a wide variety of melting points corresponding to the length of their chains. For example, according to the second edition of Fatty Acid Chemistry edited by Keiichi Inaba et al., published by Koshobo in 1997, the representative fatty acids have the following melting points: hexanoic acid (-4.0℃), heptanoic acid (-7.0℃), octanoic acid (16.0℃), nonanoic acid (12.5℃), decanoic acid (31.6℃), undecanoic acid (28.7℃), lauric acid (44.2℃), oleic acid (13.4℃), linoleic acid (-5.1℃), and linolenic acid (-11.2℃).

[0033] In this 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 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 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-mentioned fatty acids, and combinations thereof. In this invention, fatty acids having a melting point of 46°C or lower are preferably lauric acid and oleic acid, and combinations thereof, because they offer better performance in terms of poor workability at low temperatures.

[0034] Furthermore, compared to the fatty acids with melting points below 46°C, if calcium carbonate particles that have been surface-treated with fatty acids exceeding 46°C are incorporated into a high-viscosity curing resin, it is difficult to mitigate the sharp increase in viscosity at low temperatures in the resulting curing resin composition.

[0035] The surface treatment agent of this invention comprises a fatty acid content (Mp) having a melting point below 46°C of 50 to 100% by mass, preferably 50 to 80% by mass, and more preferably 55 to 65% by mass. If Mp is less than 50% by mass, the plasticizing effect of the resulting cured resin composition weakens at low temperatures, the thixotropic decreases significantly at low temperatures, and the viscosity increases significantly, thus failing to improve workability during application.

[0036] (3) The proportion of unsaturated fatty acid portion (UFa) included in the monovalent water-soluble fatty acid salt constituting the surface treatment agent. The surface-treated calcium carbonate particles of this invention also include, within a predetermined range (UFa; mass g), the unsaturated fatty acid portion comprising the monovalent water-soluble fatty acid salt constituting the surface-treated agent applied to the particles. In this invention, the proportion (UFa) of the unsaturated fatty acid portion comprising the monovalent water-soluble fatty acid salt constituting the surface-treated calcium carbonate particles is 45 to 80% by mass, preferably 50 to 70% by mass, more preferably 55 to 65% by mass. If the UFa in the surface-treated agent applied to the surface-treated calcium carbonate particles is less than 45% by mass, the viscosity of the resulting cured resin composition increases at low temperatures, reducing workability for the applicator. If the UFa in the surface-treated agent applied to the surface-treated calcium carbonate particles exceeds 80% by mass, the heat resistance of the resulting cured resin composition decreases, and it is prone to discoloration and elongation.

[0037] (Method for determining UFa) UFa of surface-treated calcium carbonate particles can be measured, for example, using a gas chromatograph equipped with a thermal decomposition device (Frontier Labs Co., Ltd. PY-2020D) and a gas chromatograph-mass analyzer (Shimadzu Corporation GCMS-QP2010A) as follows.

[0038] Specifically, the method involves immersing surface-treated calcium carbonate particles in a tetramethylammonium hydroxide solution and thermally decomposing them at 300°C, then determining their composition using a gas chromatograph.

[0039] Based on the obtained gas chromatograms, the peak values ​​of the five main fatty acid compositions (i.e., lauric acid (C12), myristic acid (C14), palmitic acid (C16), and stearic acid (C18) as saturated fatty acids, and oleic acid (C18F1) as an unsaturated fatty acid) were analyzed and adjusted so that the sum of their peak values ​​was 100%.

[0040] The proportion (mass%) of the unsaturated fatty acid fraction obtained in this way is used as UFa.

[0041] (4) The ratio (Nr) of the anti-charged monovalent fatty acid salt obtained by refluxing surface-treated calcium carbonate particles with ethanol to the total surface treatment amount of the surface treatment agent. Regarding the surface-treated calcium carbonate particles in this invention, the ratio (Nr) of the monovalent fatty acid salt containing anti-charged ions obtained by refluxing the particles with ethanol to the total surface-treated amount of the surface-treated agent satisfies a predetermined range. In this invention, the 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. If the Nr of the surface-treated calcium carbonate particles is less than 20% by mass, the elongation of the resulting cured resin composition decreases, making it difficult to obtain a resin composition with a long service life. If the Nr of the surface-treated calcium carbonate particles exceeds 50% by mass, the resulting cured resin composition has a low modulus and high elongation, but its water resistance and adhesion decrease, hindering long-term waterproof performance.

[0042] (Methods for determining Nr) The Nr content of surface-treated calcium carbonate particles can be determined as follows.

[0043] (a) First, as a sample, 5g of surface-treated calcium carbonate particles were collected in a 300mL Erlenmeyer flask and 80g of 95% ethanol was added to them.

[0044] (b) Next, gently cover the mouth of the flask with aluminum foil and bring it to a boil in a water bath at 90°C or higher. After boiling for another hour, remove it from the water bath and let it cool at room temperature for one day.

[0045] (c) Adjust the temperature to 30°C and use a PTFE membrane filter (0.5 μm pore size) to filter the contents of the flask. The filtrate is collected in a beaker.

[0046] (d) Transfer the obtained filtrate to a weighed 200 mL beaker and immerse it in a hot water bath at 80°C or higher to evaporate 95% of the ethanol. After cooling, measure the mass of the beaker (in addition, measure the mass of the empty beaker before the above filtration).

[0047] (e) Thereafter, the amount of free matter F (mg / g) per 1g of surface-treated calcium carbonate particles is calculated as follows.

[0048] F (mg / g) = [Mass of the beaker after filtration / cooling (mg) - Mass of the empty beaker (mg)] / Mass of the calcium carbonate sample (g) (f) Next, the free product obtained in (e) above was dissolved in 25 mL of 2-propanol with a few drops of phenolphthalein solution added.

[0049] (g) The 2-propanol solution obtained in (f) above was neutralized and titrated using a 0.1 mol / L potassium hydroxide aqueous solution.

[0050] (h) The amount of free fatty acids (a (mg / g)) in 1 g of surface-treated calcium carbonate particles can be calculated based on the following formula using the potassium hydroxide titration amount of (g) above: Free fatty acid amount a (mg / g) = titration volume 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) / Sample mass of surface-treated calcium carbonate particles (g) Here, if the heat loss per 1g of surface-treated calcium carbonate particles at 200 to 500°C (total surface treatment dose) is set as Tg (mg / g), then the ratio Zf of the amount of free fatty acids obtained by ethanol extraction of surface-treated calcium carbonate particles to the total surface treatment dose can be calculated as follows: Zf = (a / Tg) × 100 (mass%) Similarly, the amount of monovalent fatty acid salt constituting the anti-charge ion in the free matter of 1 g of surface-treated calcium carbonate particles can be calculated (mg / g) based on the potassium hydroxide titration amount of (g) above as follows: Monovalent fatty acid salt content s = Free matter content F - Free fatty acid content a (mg / g) The ratio Nr of the monovalent fatty acid salt constituting the anti-charge ion in the free product obtained by ethanol reflux of surface-treated calcium carbonate to the total surface treatment agent dosage can be calculated as follows: Nr = (s / Tg) × 100 (mass%) (5) Amount of surface treatment agent per unit specific surface area of ​​surface-treated calcium carbonate particles (Es) Regarding the surface-treated calcium carbonate particles of this invention, the amount (Es) of the surface-treated agent per unit specific surface area of ​​the surface-treated calcium carbonate particles falls within a predetermined range. In this invention, the Es of the surface-treated calcium carbonate particles is 1.00 to 4.50 mg / m³. 2 Preferably, the concentration is 1.50 to 4.00 mg / m³. 2 More preferably, 2.00 to 3.00 mg / m³ 2 If the Es of the surface-treated calcium carbonate particles is less than 1.00 mg / m³ 2 If the surface treatment effect of the calcium carbonate particles is insufficient, the untreated surface will be exposed and easily absorb moisture. Furthermore, if the Es of the surface-treated calcium carbonate particles exceeds 4.50 mg / m³, the surface treatment may become ineffective. 2If the remaining surface treatment agent acts as a lubricant, it may negatively impact the heat resistance of the resulting cured resin composition and is also economically disadvantageous. Furthermore, it is preferable to adjust the surface treatment amount accordingly to the BET specific surface area Sw of the surface-treated calcium carbonate particles.

[0051] (Method for calculating Es) Es of surface-treated calcium carbonate particles can be obtained by dividing the heat loss per 1g of surface-treated calcium carbonate (mg / g) (Tg; also known as the total surface treatment dose) by the aforementioned BET specific surface area (m²) as follows. 2 Calculate using / g)(Sw): Es (mg / m 2 = Tg (mg / g) / Sw (m 2 / g) (Methods for determining Tg) Here, Tg used a thermal analysis apparatus (ThermoPlus EV02 manufactured by Rigaku Corporation) to collect 100 mg of surface-treated calcium carbonate in a sample pan (platinum) with a diameter of 10 mm, and measured the heat loss from 200°C to 500°C when the temperature was increased from room temperature to 510°C at a heating rate of 15°C / min, so that it could be obtained as the heat loss per 1 g of surface-treated calcium carbonate (mg / g).

[0052] Es can be controlled by varying the conditions used in manufacturing the surface-treated calcium carbonate particles of this invention. Examples of conditions that can control Es within the aforementioned range include, for instance, the surface treatment dosage and BET specific surface area, and combinations thereof. When such conditions are not sufficiently set, it is sometimes difficult to obtain surface-treated calcium carbonate particles that satisfy the aforementioned Es range.

[0053] (Surface-treated calcium carbonate filler using surface treatment agents) As described above, the surface-treated calcium carbonate filler of the present invention comprises surface-treated calcium carbonate particles that satisfy all of formulas (1) to (5). Such surface-treated calcium carbonate particles are surface-treated calcium carbonate particles that have undergone surface treatment using a surface-treatment agent.

[0054] Hereinafter, the term "surface treated" as used in this specification is used to mean the "state" of the surface of the surface treated calcium carbonate filler and / or surface treated calcium carbonate particles.

[0055] The surface-treated calcium carbonate particles in this invention are particles on which unmodified (before surface treatment) calcium carbonate particles have been surface-treated using a surface treatment agent.

[0056] (Unmodified calcium carbonate particles) Here, from the perspective of degassing when mixed with resin, the unmodified calcium carbonate particles are less like natural white sugar crystal limestone (heavy calcium carbonate) containing many fine powder particles, and more like synthetic calcium carbonate (e.g., light / colloidal calcium carbonate) particles prepared by a synthetic method of calcining natural gray dense limestone.

[0057] As a well-known method using carbon dioxide gas, such unmodified calcium carbonate particles can be produced, for example, by adding water to quicklime obtained by calcining gray dense limestone to form calcium hydroxide, and reacting it with the carbon dioxide gas generated during calcination. Alternatively, the calcium carbonate slurry reacted using this method can be adjusted to have a desired BET specific surface area through Ostwald slaking to obtain the desired calcium carbonate particles.

[0058] (Surface treatment agent) Surface treatment agents are used on the aforementioned unmodified calcium carbonate particles to improve particle flowability, enhance the alkali resistance or activity resistance of calcium carbonate, and improve other properties of calcium carbonate fillers. Examples of surface treatment agents include the aforementioned fatty acids.

[0059] In this invention, the surface treatment agent may also contain, in addition to the fatty acids mentioned above, one or more of other saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids and resin acids, as well as their sodium salts, potassium salts, ammonium salts and amine salts.

[0060] Other saturated fatty acids include, but notably, saturated fatty acids with 6 to 31 carbon atoms, more preferably saturated fatty acids with 8 to 26 carbon atoms, and even more preferably saturated fatty acids with 9 to 21 carbon atoms. Specific examples of other fatty acids include butyric acid, hexanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, linaloic acid, and triacontanic acid, as well as combinations thereof.

[0061] Other unsaturated fatty acids are fatty acids that have one or more double bonds in their molecules. For example, fatty acids synthesized in organisms through the dehydration reaction of saturated fatty acids can be listed. Other unsaturated fatty acids include, for example, unsaturated fatty acids with 6 to 31 carbon atoms. Specific examples of other unsaturated fatty acids include decacarbon-4-enoic acid, decenoic acid, undecenoic acid, dodecacarbon-5-enoic acid, tetradecenoic acid, spermicidal acid, myristenoic acid, palmitoleic acid, apigenic acid, oleic acid, transoleic acid, cis-11-octadecenoic acid, isoleic acid, codenoic acid, squalene, cetyl oleate, erucic acid, brassinolic acid, squalene, simulenoic acid, triacontaenoic acid, sorbic acid, linoleic acid, and linolenic acid, as well as combinations thereof.

[0062] Furthermore, in this invention, fatty acids derived from animal materials such as butter or lard, or fatty acids derived from plant materials such as palm or coconut, containing the aforementioned other unsaturated fatty acids, may also be used as one of the components of the surface treatment agent.

[0063] Furthermore, to the extent that the effects of the present invention are not impaired, alicyclic carboxylic acids (e.g., naphthenic acids), resin acids (e.g., abietic acid, piratic acid, longleaf abietic acid, neoabietic acid), modified rosin (e.g., their disproportionated rosin, hydrogenated rosin, dimer rosin, trimer rosin), sulfonic acids (e.g., alkylbenzene sulfonic acid), and their sodium, potassium, ammonium, and amine salts can be used alone or in combination of two or more types.

[0064] (Surface treatment of unmodified calcium carbonate particles) The above-mentioned surface treatment agent is used to perform surface treatment on unmodified calcium carbonate particles, for example, as follows.

[0065] The surface treatment of unmodified calcium carbonate particles can also be performed using either a general dry treatment or a wet treatment. Preferably, a method is used where the aforementioned surface treatment agent is added to an aqueous slurry comprising the unmodified calcium carbonate particles. Such a method is generally referred to as a wet treatment, and is preferred in that it can appropriately balance the degree of surface treatment of the calcium carbonate particles and manufacturing efficiency.

[0066] The amount of surface treatment agent used is not particularly limited as long as the obtained surface-treated calcium carbonate particles satisfy the above formulas (1) to (5), and can be appropriately selected by those skilled in the art. In addition, the temperature used for surface treatment is not particularly limited, and can be appropriately selected by those skilled in the art.

[0067] After the above surface treatment, the resulting particles can be pulverized by any conventional method, such as dehydration, drying, or pulverization.

[0068] Furthermore, dewatering can be performed on slurries containing surface-treated calcium carbonate particles using a filter press or centrifugal dewatering machine. For drying, hot air dryers such as micron dryers, which efficiently dry the surface-treated calcium carbonate particles by directly contacting them with high-temperature hot air, can be used; alternatively, heat transfer dryers such as CD dryers, which indirectly dry the surface-treated calcium carbonate particles by contacting them with a heating plate, can also be used.

[0069] In this way, surface-treated calcium carbonate particles can be obtained by surface treatment with a surface treatment agent. These surface-treated calcium carbonate particles are used as surface-treated calcium carbonate fillers that can satisfy all of the above formulas (1) to (5).

[0070] The surface-treated calcium carbonate filler of the present invention is used in combination with a curing resin (for example, a curing resin having a resin viscosity of 30 Pa·s or more at 23°C as described later).

[0071] 2. Curing resin composition Next, the curable resin composition of the present invention will be described.

[0072] The curable resin composition of the present invention contains the above-mentioned surface-treated calcium carbonate filler and the curable resin.

[0073] (Curing resin) Curing resins, for example, have a viscosity preferably of 30 Pa·s or more, more preferably 50 to 100 Pa·s, at 23°C. For example, resins with a viscosity of less than 30 Pa·s do not have problems with low-temperature workability, and therefore do not need to be used in combination with the aforementioned surface-treated calcium carbonate filler.

[0074] Here, the viscosity of the cured resin can be measured, for example, as follows.

[0075] (Method for determining the viscosity of cured resins) Specifically, after placing 300g of resin into a 300mL cup at 23°C and stirring at 10rpm for 1 minute, the viscosity can be measured using a viscometer (e.g., VISCOMETER TV-100 manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H6).

[0076] The aforementioned curable resins, for example, have crosslinked silanol groups or reactive silyl groups at the ends of their constituent molecules. Examples include silicone resins or modified silicone resins that form siloxane bonds through hydrolysis and condensation reactions. Specific examples of curable resins include acrylic silicone resins comprising (meth)acrylic polymers, such as those commercially available from Kaneka Corporation under the trade names XMAP or S-943.

[0077] Furthermore, other resins can also be used as long as they fall within the aforementioned resin viscosity range, including modified silicone resins containing polyoxyethylene (e.g., MS Polymer S-203, 303, S-810, etc. manufactured by Kaneka Corporation), modified silicone resins containing epoxy groups (SILYL manufactured by Kaneka Corporation), and silylated urethane resins containing isocyanate groups. However, when such other resins are used in combination with acrylic silicone resins including (meth)acrylic polymers, the proportions can be set by those skilled in the art within a range that does not impair the effects of the surface-treated calcium carbonate filler of the present invention.

[0078] In the cured resin composition of the present invention, the amount of the surface-treated calcium carbonate filler added to the cured resin varies depending on the type or application of the cured resin used, and is therefore not particularly limited. However, it is preferably 5 to 200 parts by weight, more preferably 20 to 150 parts by weight, relative to 100 parts by weight of the cured resin. If the amount of surface-treated calcium carbonate filler added is less than 5 parts by weight, the resulting cured resin composition may not be able to impart sufficient thixotropy. If the amount of surface-treated calcium carbonate filler added exceeds 200 parts by weight, the viscosity of the resulting cured resin composition becomes too high, and sometimes the workability deteriorates.

[0079] (Plasticizer) The cured resin composition of the present invention may also contain a plasticizer. Examples of plasticizers that can be used include dioctyl adipate (DOA), diisononyl adipate (DINA), diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutoxyethoxyethyl adipate (BXA), bis(2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), dibutyl maleate (DBM), bis(2-ethylhexyl) maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), and tri(2-ethylhexyl) phosphate. Plasticizers include hydroxypropyl phosphate (TOP), trichloroethyl phosphate (TCEP), trichloroisopropyl phosphate (CRP), tributoxyethyl phosphate (TBXP), tri(β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), octyl diphenyl phosphate (CDP), triethyl acetylglucosinolate, tributyl acetylglucosinolate, trimellitic acid ester plasticizers, polyester plasticizers, chlorinated paraffins, stearate plasticizers, silicone oils (e.g., polydimethylsiloxane), and petroleum-based high-boiling solvents (e.g., polypropylene glycol, alkanes, cycloalkanes, isoparaffins, etc.). Specific examples of plasticizers include acrylic polymers (manufactured by Toa Synthetic Co., Ltd., trade names: ARON UX-1000, UX-1110, UX-1120, etc.).

[0080] The plasticizers mentioned above are not specifically limited, but for example, 80 to 150 parts by weight are used relative to 100 parts by weight of the cured resin.

[0081] Furthermore, in this invention, it is preferable to suppress or avoid the use of phthalic acid plasticizers as much as possible. Phthalic acid plasticizers are well-known plasticizers in this art, but when the resulting resin composition is used as a sealing material, the coating film applied to the surface of the sealing material sometimes causes exudation contamination. In addition, the decrease in elongation after heat curing is sometimes significantly worsened, thus sometimes impairing aesthetics and appearance design and making it unsuitable for long-life performance. Therefore, in the curable resin composition of this invention, it is preferable to set the content of phthalic acid plasticizers to 5% by mass or less relative to the total mass.

[0082] Examples of such phthalic acid 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), tridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), and tetrahydrophthalate.

[0083] (Other fillers) The cured resin composition of the present invention may also contain other fillers in addition to the surface-treated calcium carbonate filler described above. Examples of other fillers that can be used include inorganic fillers, organic fillers, and combinations thereof.

[0084] Examples of inorganic fillers include heavy calcium carbonate, calcium / magnesium carbonates (e.g., natural and synthetic products), basic magnesium carbonate, quartz powder, silica powder, micronized silica (e.g., dry-process, wet-process, and gel-process products), micronized calcium silicate, micronized aluminum silicate, kaolin, pyrophyllite clay, talc, sericite, mica, bentonite, nepheline syenite, aluminum hydroxide, magnesium hydroxide, barium sulfate, carbon black (e.g., furnace black, pyrolysis black, and acetylene black), graphite, sepiolite, wollastonite, calcium silicate, potassium titanate, carbon fiber, mineral fiber, glass fiber, volcanic ash hollow microspheres, fly ash hollow microspheres, glass hollow microspheres, silica microspheres, alumina microspheres, and glass microspheres.

[0085] Examples of organic fillers include acrylonitrile resin hollow microspheres, vinylidene chloride resin hollow microspheres, wood flour, walnut shell powder, cork powder, wheat flour, starch, hard rubber powder, rubber powder, lignin, phenolic resin, high-styrene resin, polyethylene resin, cellulose powder, pulp powder, and synthetic fiber powder.

[0086] The amount of the other fillers in the cured 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 appropriate amounts can be selected by those skilled in the art.

[0087] (Other additives) The curable resin composition of the present invention may also contain other additives. Examples of other additives include curing catalysts, antioxidants, colorants, silane coupling agents, waxes, foaming agents, diluents, solvents, etc.

[0088] Examples of curing catalysts include organotin compounds (such as dibutyltin dilaurate, dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin acetate, dioctyltin stearate, dioctyltin dilaurate, di(2-ethylhexanoate)dioctyltin, dibutyltin bis(triethoxysilicate), dibutyltin bis(isononyl-3-mercaptopropionate), dibutyltin diacetylacetonate, dibutyltin bis(o-phenylbenzene oxide), dibutyltin bis(isooctylthioglycolate), di(di(2-ethylhexanoate)) bis(o-phenylbenzene oxide), dibutyltin bis(isooctylthioglycolate), di(2-ethylhexanoate ... Butyltin and dioctyltin oxide); inorganic tin compounds (e.g., bis(2-ethylhexanoate)tin and neodecanoatetin); titanium chelating catalysts (e.g., methoxytitanium, ethoxytitanium, acrylate oxytitanium, n-propoxytitanium, tetraisopropoxytitanium, ethyl acetoacetate titanium and acetylacetonate titanium); organoaluminum compounds (e.g., aluminum triacetylacetonate, aluminum triethylacetoacetate and aluminum diisopropoxyacetate); bismuth catalysts (e.g., bismuth trinedecanoate); zirconium metal catalysts (e.g., zirconium tetraacetylacetonate); etc.

[0089] Examples of anti-aging agents include ultraviolet absorbers (e.g., benzotriazole compounds), antioxidants (e.g., phenolic antioxidants and amine antioxidants), and light stabilizers.

[0090] Examples of colorants include inorganic pigments (such as titanium dioxide, carbon black, etc.) and organic pigments (such as azo pigments, phthalocyanine pigments, etc.).

[0091] The silane coupling agent is preferably an amino-functionalized silane compound, such as 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-(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,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, as well as combinations thereof. Furthermore, they can be used in combination with other silane coupling agents such as vinylsilanes and epoxysilanes as needed.

[0092] Examples of waxes include amide waxes and castor oil waxes.

[0093] As a foaming agent, the type that produces gas when heated can be used, such as azo dicarboxamide and other azo-based foaming agents.

[0094] Examples of diluents include xylene and terpineol.

[0095] Examples of solvents include: aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and butane; gasoline and other petroleum solvents; ketones such as acetone and methyl ethyl ketone; ether esters such as cellosol acetate; silicone oils such as fatty acid ester modified silicone oils; and combinations thereof. However, solvents may impair the heat resistance and / or durability of the resulting curable resin composition, and ideally, they should not be used.

[0096] The content of the other additives in the cured 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 appropriate amounts can be selected by those skilled in the art.

[0097] The curable resin composition of the present invention can be used, for example, as a sealant or adhesive for filling joints in building exteriors. In such applications, the curable resin composition of the present invention exhibits minimal viscosity increase at low temperatures and excellent workability. Furthermore, it possesses high elongation at a low modulus over extended periods and also exhibits excellent heat resistance. Example

[0098] The present invention will now be described in detail with reference to specific embodiments, but the present invention is not limited to these embodiments. Furthermore, in the following description, unless otherwise specified, % means mass, and parts mean parts by mass.

[0099] The evaluation of the materials and surface treatment calcium carbonate fillers described in the various embodiments and comparative examples is carried out as follows.

[0100] (A) Fatty acid composition, (B) BET specific surface area (Sw) of surface-treated calcium carbonate. (C) The proportion of unsaturated fatty acid fractions (UFa) included in the monovalent water-soluble fatty acid salts constituting the surface treatment agent. (D) The proportion (Nr) of the surface treatment agent (obtained by dry distillation of surface-treated calcium carbonate particles using ethanol) to the total amount of surface treatment. (E) Amount of surface treatment agent per unit specific surface area of ​​surface-treated calcium carbonate particles (Es) Regarding (A) to (E), the aforementioned measurement methods were used for determination.

[0101] Viscosity of sealant After the sealants obtained in each example and comparative example were allowed to stand at 23°C for 1 day, they were filled into a 100 mL polypropylene (PP) cup using a tube gun and measured using a TV type viscometer (VISCOMETER TV-100 manufactured by Toki Sangyo Co., Ltd.) (range U, rotor No. H7).

[0102] Viscosity values ​​were measured at 1 rpm for 3 minutes, at 2 rpm for 2 minutes, and at 10 rpm for 1 minute. The Ti value was calculated by dividing the viscosity value at 2 rpm by the viscosity value at 10 rpm.

[0103] Low-temperature performance of sealant After storing the sealant-filled cartridges obtained in the various examples and comparative examples at a low temperature (5°C) for one day, the sealant was filled into 100mL PP cups 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). Regarding viscosity, the values ​​were measured at 2 rpm for 2 minutes after the start of measurement and at 10 rpm for 1 minute after the start of measurement, and these were taken as viscosity values. Furthermore, regarding the TI value, it 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.

[0104] However, for viscosity values ​​above 600 Pa·s at 10 rpm in such low-temperature environments, all are rated as ×, regardless of whether the calculated TI value falls under "A" to "D".

[0105] A: TI is 2.8 or higher.

[0106] B: TI is 2.3 or higher but less than 2.8.

[0107] C: TI is 1.8 or higher but less than 2.3.

[0108] D: TI less than 1.8, or viscosity value of 600 Pa·s or more at 10 rpm.

[0109] Tensile adhesion of sealant After applying a primer (Yokohama Rubber Co., Ltd. No. 40) to the surface of an aluminum plate (50mm × 50mm × 3mm) and allowing it to dry for 60 minutes, an H-type test specimen was prepared by filling it with the sealant (shape 12mm × 12mm × 50mm) obtained in each of the examples and comparative examples, in accordance with JIS A 1439:2016 (Sealing materials for building use 5.12.2, preparation of tensile test specimens).

[0110] The maximum strength and maximum elongation measured using a tensile testing machine (Autograph AG-1, Shimadzu Corporation) after heating the test specimen at 23°C for 14 days and at 30°C for 14 days, followed by holding it at 23°C for 1 day, are referred to as initial strength and initial elongation, respectively. The maximum strength and maximum elongation measured after further heating at 100°C for 42 days, followed by holding it at 23°C for 1 day, are referred to as post-heat strength and post-heat elongation, respectively.

[0111] Furthermore, the aforementioned maximum strength (Tmax) is determined by stretching the sealant from the test specimen at a speed of 50 mm for 1 minute and dividing the maximum load by the cross-sectional area of ​​the sealant (600 mm²). 2 The value obtained is from ).

[0112] The aforementioned maximum elongation (Emax) is obtained by dividing the displacement when the maximum strength is measured by the side (12 mm) of the shape that constitutes the sealant when the sealant is filled into the aluminum plate and multiplying by 100.

[0113] Furthermore, the values ​​of initial strength (maximum strength) and initial elongation (maximum elongation) obtained above, as well as the values ​​of strength after heating (maximum strength) and elongation after heating (maximum elongation) obtained above, are determined according to the following criteria.

[0114] (Judgment criteria for initial tensile test) Initial strength (maximum strength / Tmax): A: 0.40 N / mm 2 above.

[0115] B: 0.30 N / mm 2 Above but less than 0.40 N / mm 2 .

[0116] C: 0.20 N / mm 2 The above is less than 0.30 N / mm 2 .

[0117] D: less than 0.20 N / mm 2 .

[0118] Initial elongation (maximum elongation / Emax): A: Over 600%.

[0119] B: 450% or more but less than 600%.

[0120] C: More than 300% but less than 450%.

[0121] D: Less than 300%.

[0122] (Judgment criteria for tensile test after heating) Strength after heating (maximum strength / Tmax): A: 0.30 N / mm 2 above.

[0123] B: 0.20 N / mm 2 Above but less than 0.30 N / mm 2 .

[0124] C: 0.10 N / mm 2 Above but less than 0.20 N / mm 2 .

[0125] D: less than 0.1 N / mm 2 .

[0126] Elongation after heating (maximum elongation / Emax): A: More than 350%.

[0127] B: More than 250% but less than 350%.

[0128] C: 150% or more but less than 250%.

[0129] D: Less than 150%.

[0130] (Adhesiveness) Furthermore, preferably, the sealant fracture does not occur at the bonding surface, but rather inside (center) of the sealant.

[0131] The CF value indicates the percentage of agglomeration failure (%), and the AF value indicates the percentage of interfacial delamination (%). Here, a CF value of 100% indicates 100% agglomeration failure, indicating ideal adhesion, while an AF value of 100% indicates interfacial delamination, indicating unsatisfactory adhesion.

[0132] The CF value obtained in this way is used to determine the adhesion of the sealant in the initial stage and after heating, according to the following criteria.

[0133] Initial adhesion assessment criteria A: CF100%.

[0134] B: CF50% to CF99%.

[0135] C: Less than CF50% (AF50% or more).

[0136] Criteria for determining adhesion after heating A: CF100%.

[0137] B: CF50% to CF99%.

[0138] C: Less than CF50% (AF50% or more).

[0139] Example 1: Preparation of surface-treated calcium carbonate particles (E1) Compared to a BET specific surface area of ​​27 m², adjusted to a solid component concentration of 10.0 wt% and a temperature of 50°C. 210 L of a slurry containing 1 g of synthetic calcium carbonate was prepared by neutralizing 65 g of a mixed fatty acid (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 6:6:22:16:50 (mass ratio)) in 1 L of warm water at 80°C with sodium hydroxide. This mixed fatty acid sodium salt was added and vigorously stirred with the calcium carbonate slurry. The calcium carbonate slurry was dehydrated to 60% solids, dried in a box dryer at 110°C for 12 hours, and then pulverized to obtain a BET specific surface area of ​​23 m². 2 / g of surface-treated calcium carbonate particles (E1). The characteristics of the obtained surface-treated calcium carbonate particles (E1) are shown in Table 1.

[0140] Example 2: Preparation of surface-treated calcium carbonate particles (E2) As a surface treatment agent, the composition of the mixed fatty acids was changed to lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 10:4:28:4:54 (mass ratio) (the amount of surface treatment agent added was neutralized by sodium hydroxide to 65g), otherwise, surface-treated calcium carbonate particles (E2) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E2) are shown in Table 1.

[0141] Example 3: Preparation of surface-treated calcium carbonate particles (E3) Using the same mixed fatty acid composition as in Example 1, but instead of using sodium hydroxide to neutralize the addition of 53g of surface treatment agent, surface-treated calcium carbonate particles (E3) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E3) are shown in Table 1.

[0142] Example 4: Preparation of surface-treated calcium carbonate particles (E4) Using the same mixed fatty acid composition as in Example 1, but instead of using sodium hydroxide to neutralize the added amount of 77g of surface treatment agent, surface-treated calcium carbonate particles (E4) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E4) are shown in Table 1.

[0143] Example 5: Preparation of surface-treated calcium carbonate particles (E5) In Example 1, the surface treatment agent was changed to sodium hydroxide to neutralize the composition of the mixed fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 0:1:25:22:52 (mass ratio)), and the amount of surface treatment agent added was changed to 63g. Otherwise, surface-treated calcium carbonate particles (E5) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E5) are shown in Table 1.

[0144] 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 m². 2 / g, making the treatment agent composition the same as in Example 1, but changing the amount of surface treatment agent added to 42g, otherwise, 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.

[0145] 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 m². 2 / g, making the treatment agent composition the same as in Example 1, but changing the amount of surface treatment agent added to 109g, otherwise, 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.

[0146] Example 8: Preparation of surface-treated calcium carbonate particles (E8) In Example 1, the surface treatment agent was changed to a mixture of fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 2:5:30:20:43 (mass ratio), and 65g of surface treatment agent was added using sodium hydroxide to neutralize it). Otherwise, calcium carbonate particles (E8) were obtained with the same surface treatment as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E8) are shown in Table 1.

[0147] Example 9: Preparation of surface-treated calcium carbonate particles (E9) In Example 1, the composition of the surface treatment agent was changed to a mixture of fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 60:0:0:0:40 (mass ratio), and the amount of surface treatment agent added was 65g neutralized with sodium hydroxide). Otherwise, 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.

[0148] Example 10: Preparation of surface-treated calcium carbonate particles (E10) In Example 1, the composition of the surface treatment agent was changed to a mixture of fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 6:6:26:24:38 (mass ratio), and the amount of surface treatment agent added was 65g using sodium hydroxide to neutralize it). Otherwise, 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.

[0149] Example 11: Preparation of surface-treated calcium carbonate particles (E11) In Example 1, the composition of the surface treatment agent was changed to a mixture of fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 4:2:12:10:72 (mass ratio), and the amount of surface treatment agent added was 65g using sodium hydroxide to neutralize it). Otherwise, 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.

[0150] Example 12: Preparation of surface-treated calcium carbonate particles (E12) Surface treatment was performed by adding fatty acids of the same composition as in Example 1, which were neutralized with sodium hydroxide (fatty acid Na salt: fatty acid = 8:2 (mass ratio), and the amount of surface treatment agent added was 52 g of fatty acid Na salt and 13 g of fatty acid). Otherwise, 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.

[0151] Example 13: Preparation of surface-treated calcium carbonate particles (E13) 0.5% sodium hydroxide was added to the calcium carbonate slurry before surface treatment to make the pH above 11. Otherwise, surface-treated calcium carbonate particles (E13) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E13) are shown in Table 1.

[0152] Example 14: Preparation of surface-treated calcium carbonate particles (E14) The same mixed fatty acid composition as in Example 1 was neutralized with sodium hydroxide, and the amount of surface treatment agent added was changed to 32g. Otherwise, surface-treated calcium carbonate particles (E14) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E14) are shown in Table 1.

[0153] Example 15: Preparation of surface-treated calcium carbonate particles (E15) Using the same mixed fatty acid composition as in Example 1, neutralized with sodium hydroxide, and with the amount of surface treatment agent added changed to 111g, surface-treated calcium carbonate particles (E15) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (E15) are shown in Table 1.

[0154] 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 m². 2 / g, the composition of the treatment agent is the same as in Example 1, except that the amount of surface treatment agent added is changed to 139g, otherwise, surface-treated calcium carbonate particles (E16) are 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.

[0155] 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 m². 2 / g, the treatment agent composition is the same as in Example 1, except that the amount of surface treatment agent added is changed to 28g, otherwise, surface-treated calcium carbonate particles (E17) are 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.

[0156] 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 m² / g, and the composition of the treatment agent was the same as in Example 1, except that the amount of surface treatment agent added was changed to 17 g. Otherwise, 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.

[0157] [Table 1] Comparative Example 1: Preparation of Surface-Treated Calcium Carbonate Particles (C1) As a surface treatment agent, the composition of the mixed fatty acids was changed (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 0:0:28:52:20 (mass ratio), and the amount of surface treatment agent added was neutralized with sodium hydroxide to 65g). Otherwise, surface-treated calcium carbonate particles (C1) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C1) are shown in Table 2.

[0158] Comparative Example 2: Preparation of Surface-Treated Calcium Carbonate Particles (C2) As a surface treatment agent, the composition of the mixed fatty acids was changed (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 100:0:0:0:0 (mass ratio), and the amount of surface treatment agent added was neutralized with sodium hydroxide to 65g). Otherwise, surface-treated calcium carbonate particles (C2) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C2) are shown in Table 2.

[0159] Comparative Example 3: Preparation of Surface-Treated Calcium Carbonate Particles (C3) As a surface treatment agent, 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 amount of surface treatment agent added was neutralized with sodium hydroxide to 65g). Otherwise, surface-treated calcium carbonate particles (C3) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C3) are shown in Table 2.

[0160] Comparative Example 4: Preparation of Surface-Treated Calcium Carbonate Particles (C4) Surface treatment was performed by adding fatty acids of the same composition as in Example 1, which were neutralized with sodium hydroxide (fatty acid Na salt: fatty acid = 1:1 (mass ratio), and the amount of surface treatment agent added was 38 g of fatty acid Na salt and 38 g of fatty acid). Otherwise, surface-treated calcium carbonate particles (C4) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C4) are shown in Table 2.

[0161] Comparative Example 5: Preparation of Surface-Treated Calcium Carbonate Particles (C5) 1.0% sodium hydroxide was added to the calcium carbonate slurry before surface treatment to adjust the pH to above 12. The same treatment agent composition as in Example 1 was used, but the amount of surface treatment agent added was changed to 76g. Otherwise, surface-treated calcium carbonate particles (C5) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C5) are shown in Table 2.

[0162] Comparative Example 6: Preparation of Surface-Treated Calcium Carbonate Particles (C6) Using the same composition of mixed fatty acid sodium salts as in Example 1, but with the amount of surface treatment agent added changed to 27g, surface-treated calcium carbonate particles (C6) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C6) are shown in Table 2.

[0163] Comparative Example 7: Preparation of Surface-Treated Calcium Carbonate Particles (C7) Using the same composition of mixed fatty acid sodium salts as in Example 1, but with the amount of surface treatment agent added changed to 120 g, surface-treated calcium carbonate particles (C7) were obtained in the same manner as in Example 1. The characteristics of the obtained surface-treated calcium carbonate particles (C7) are shown in Table 2.

[0164] 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 m². 2 / g, changed to a mixed fatty acid composition (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 5:4:25:24:42 (mass ratio), the amount of surface treatment agent added was neutralized with sodium hydroxide 50g), otherwise, 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.

[0165] 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 m². 2 / g, the composition of the mixed fatty acids (lauric acid:myristic acid:palmitic acid:stearic acid:oleic acid = 6:3:40:22:29 (mass ratio), changed to the amount of surface treatment agent added by neutralizing with sodium hydroxide 35g), except that, 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.

[0166] 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 m² / g, and the same treatment agent composition as in Example 1 was used, but the amount of surface treatment agent added was changed to 170 g. Otherwise, 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.

[0167] 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 changed to 6 m² / g, and the same treatment agent composition as in Example 1 was used, except that the amount of surface treatment agent added was changed to 11 g. Otherwise, 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.

[0168] [Table 2] 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 and mixed with the components shown below to produce single-component modified silicone sealants (SE19) to (SE34).

[0169] Modified silicone resins including methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) 100 parts by weight Antioxidants (ADK STAB AO-60 manufactured by ADEKA Co., Ltd.) 1 part by weight Plasticizers (acrylic plasticizers) (ARUFON UP-1000 manufactured by Toa Synthetic Co., Ltd.) 80 parts by weight Heavy calcium carbonate (Super S, manufactured by Maruo Calcium Co., Ltd.) 80 parts by weight 120 parts by weight of surface-treated calcium carbonate particles obtained in Examples 1 to 16 Dehydrating agent (KBM-1003 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 5 parts by weight Tin catalyst (NEOSTANN U-220H manufactured by Nitto Kasei Corporation) 2 parts by weight aminosilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight A total of 390 parts by weight The mixing process is as follows.

[0170] Modified silicone resin was added to a 5L universal mixer (manufactured by Dalton Co., Ltd.), along with surface-treated calcium carbonate particles that had been dried at 105°C for more than 2 hours and heavy calcium carbonate. The mixture was then pre-stirred at low speed for 15 minutes. After scraping off the surface-treated calcium carbonate particles adhering to the mixer, the mixture was immediately kneaded at high speed under vacuum for 30 minutes. A dehydrating agent, a tin catalyst, and aminosilane were then added, and the mixture was kneaded at low speed under vacuum for 15 minutes. The mixture was then filled into an aluminum foil-coated cylinder and sealed with a metal plunger to obtain the single-component modified silicone sealants (sealants (SE19) to (SE34)) of each embodiment.

[0171] The evaluation results of the obtained sealants (SE19) to (SE34) are shown in Table 5.

[0172] Example 35: Preparation of sealant (SE35) 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. Otherwise, the sealant (SE35) was obtained in the same manner as in Example 19. 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.

[0173] Example 36: Preparation of sealant (SE36) 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. Otherwise, the sealant (SE36) was obtained in the same manner as in Example 19. 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.

[0174] Example 37: Preparation of sealant (SE37) The modified silicone resin used was changed to 70 parts by weight of a modified silicone resin comprising methacrylic acid polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) and 30 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Co., Ltd.). Otherwise, the sealant (SE37) was obtained in the same manner as in Example 19. 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.

[0175] Example 38: Preparation of sealant (SE38) The modified silicone resin used was changed to 51 parts by weight of a modified silicone resin comprising methacrylic acid polymers (XMAP SB-802 manufactured by Kaneka Corporation) and 49 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Corporation). Otherwise, the sealant (SE38) was obtained in the same manner as in Example 19. 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.

[0176] Example 39: Preparation of sealant (SE39) The plasticizer used was changed to 61 parts by weight of an acrylic plasticizer (ARUFONUP-1000 manufactured by Toa Synthetic Co., Ltd.) and 19 parts by weight of a phthalic acid plasticizer (DINP manufactured by J-PLUS Co., Ltd.). Otherwise, the sealant (SE39) was obtained in the same manner as in Example 19. 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.

[0177] Example 40: Preparation of sealant (SE40) The modified silicone resin used was changed to 70 parts by weight of a modified silicone resin comprising methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) and 30 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Co., Ltd.), and the plasticizer used was changed to 61 parts by weight of an acrylic plasticizer (ARUFON UP-1000 manufactured by Toa Synthetic Co., Ltd.) and 19 parts by weight of a phthalic acid plasticizer (DINP manufactured by J-PLUS Co., Ltd.). Otherwise, the 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.

[0178] Example 41: Preparation of sealant (SE41) The modified silicone resin used was changed to 51 parts by weight of a modified silicone resin comprising methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) and 49 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Co., Ltd.), and the plasticizer used was changed to 61 parts by weight of an acrylic plasticizer (ARUFON UP-1000 manufactured by Toa Synthetic Co., Ltd.) and 19 parts by weight of a phthalic acid plasticizer (DINP manufactured by J-PLUS Co., Ltd.). Otherwise, the 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.

[0179] [Table 3] 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 and mixed with the components shown below to produce single-component modified silicone sealants (SC12) to (SC21).

[0180] Modified silicone resins including methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) 100 parts by weight Antioxidants (ADK STAB AO-60 manufactured by ADEKA Co., Ltd.) 1 part by weight Plasticizers (acrylic plasticizers) (ARUFON UP-1000 manufactured by Toa Synthetic Co., Ltd.) 80 parts by weight Heavy calcium carbonate (Super S, manufactured by Maruo Calcium Co., Ltd.) 80 parts by weight 120 parts by mass of surface-treated calcium carbonate particles obtained in Comparative Examples 1 to 12 Dehydrating agent (KBM-1003 manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 5 parts by weight Tin catalyst (NEOSTANN U-220H manufactured by Nitto Kasei Corporation) 2 parts by weight aminosilane (KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by weight A total of 390 parts by weight The mixing process is as follows.

[0181] Modified silicone resin was added to a 5L universal mixer (manufactured by Dalton Co., Ltd.), along with surface-treated calcium carbonate particles that had been dried at 105°C for more than 2 hours and heavy calcium carbonate. The mixture was then pre-mixed at low speed for 15 minutes. After scraping off the surface-treated calcium carbonate particles adhering to the mixer, it was immediately mixed at high speed under vacuum for 30 minutes. Then, a dehydrating agent, a tin catalyst, and aminosilane were added, and the mixture was mixed at low speed under vacuum for 15 minutes. The mixture was then filled into aluminum foil-coated cylinders and sealed with metal plungers to obtain the single-component modified silicone sealants (sealants (SC12) to (SC21)) of each comparative example.

[0182] The evaluation results of the obtained sealants (SC1) to (SC21) are shown in Table 6.

[0183] 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. Otherwise, the sealant (SC22) was obtained in the same manner as in Comparative Example 12. 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.

[0184] Comparative Example 23: Preparation of Sealant (SC23) The modified silicone resin used was changed to 50 parts by weight of a modified silicone resin comprising methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) and 50 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Co., Ltd.). Otherwise, the sealant (SC23) was obtained in the same manner as in Comparative Example 12. 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.

[0185] Comparative Example 24: Preparation of Sealant (SC24) The modified silicone resin used was changed to 30 parts by weight of a modified silicone resin comprising methacrylic polymers (Kaneka XMAP SB-802, Co., Ltd.) and 70 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (Kaneka S-203, Co., Ltd.). Otherwise, the sealant (SC24) was obtained in the same manner as in Comparative Example 12. 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.

[0186] Comparative Example 25: Preparation of Sealant (SC25) The modified silicone resin used was changed to 0 parts by weight of a modified silicone resin comprising methacrylic polymers (XMAP SB-802 manufactured by Kaneka Co., Ltd.) and 100 parts by weight of a modified silicone resin comprising polyoxyethylene polymers (S-203 manufactured by Kaneka Co., Ltd.). Otherwise, the sealant (SC25) was obtained in the same manner as in Comparative Example 12. 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.

[0187] [Table 4] [Table 5] [Table 6] As shown in Tables 5 and 6, the sealants (SE19) to (SE41) prepared using any one of the surface-treated calcium carbonate particles (E1) to (E18) obtained in Examples 1 to 18 all exhibited good low-temperature workability, and good adhesion both initially and after heating. In contrast, among the sealants (SC12) to (SC27) prepared using any one of the surface-treated calcium carbonate particles (C1) to (C11) obtained in Comparative Examples 1 to 11, there were sealants with poor low-temperature workability (e.g., Comparative Examples 12, 13, 18, 20 to 22), and even assuming good low-temperature workability, poor adhesion both initially and after heating.

[0188] It is thus evident that sealants (SE19) to (SE41) made using any one of the surface-treated calcium carbonate particles (E1) to (E18) obtained in Examples 1 to 18 improve both low-temperature workability and adhesion in either the initial stage or after heating.

[0189] Industrial availability According to the present invention, it is useful, for example, in the fields of resin molding, construction / housing, coatings, and a wide range of related technical fields.

Claims

1. A surface-treated calcium carbonate filler for use in curable resin compositions, wherein the surface-treated calcium carbonate filler is used in curable resins having a resin viscosity of 30 Pa·s or higher at 23°C. This includes surface-treated calcium carbonate particles that have undergone surface treatment using surface treatment agents and satisfy the following equations (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 / m2) Sw is the BET specific surface area (m²) of the surface-treated calcium carbonate particles. 2 / g), Mp is the content (mass %) of fatty acids included in the surface treatment agent, wherein the fatty acids are at least one selected from the group consisting of fatty acids and their salts having a melting point below 46°C. UFa is the proportion (by mass%) of the unsaturated fatty acid portion included in the monovalent water-soluble fatty acid salt that constitutes the surface treatment agent. Nr is the ratio (mass %) of the monovalent fatty acid salt containing anti-charged ions obtained by refluxing the surface-treated calcium carbonate particles with ethanol to the total surface-treated amount of the surface treatment agent. Es is the amount of the surface-treating agent per unit specific surface area of ​​the surface-treated calcium carbonate particles (mg / m²). 2 ).

2. The surface-treated calcium carbonate filler for the curable resin composition according to claim 1, wherein, The fatty acids included in the surface treatment agent, having a melting point below 46°C, 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 their salts.

3. The surface-treated calcium carbonate filler for the curable resin composition according to claim 1, wherein, The cured resin is selected from at least one of the following groups: homopolymers of (meth)acrylic acid having alkoxysilyl groups and mixtures of polyoxyalkylene polymers and (meth)acrylic acid polymers having alkoxysilyl groups.

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

5. The curable resin composition according to claim 4, wherein, The cured resin is selected from at least one of the following groups: homopolymers of (meth)acrylic acid having alkoxysilyl groups and mixtures of polyoxyalkylene polymers and (meth)acrylic acid polymers having alkoxysilyl groups.

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

7. The curable resin composition according to claim 4, wherein it is a single-component resin composition or a two-component resin composition.

8. The curable resin composition according to claim 4, wherein it contains less than 5% by weight of phthalic acid plasticizer relative to the total mass.

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