TW460519B - Surface-treated calcium carbonate filler, method for making said filler and resinous compositions obtained by mixing with said filler - Google Patents

Abstract

A surface-treated calcium carbonate filler is provided in which calcium carbonate is surface-treated by a wet method with at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, aliphatic carboxylic acids and resin acids. The filler is particularly suited for a filler for resins and, for example, when it is used in curable resinous compositions, the obtained compositions are not only excellent in heat resistance at the time of drying, but in thixotropy, anti-slump property and storage stability, and when it is used in plastics, excellent dispersibility and insulation property are obtained, and when it is used in paints and inks, excellent water resistance is obtained.

Description

a 60519 V. Description of the Invention (1) Technical Field The present invention relates to a calcium carbonate filler for surface treatment, a method for manufacturing the same, and a resin composition composed of the filler; if it is more detailed, for example, it is used in In the state of hardened resin, it can produce very good thixotropic properties, resistance to slump, and excellent storage stability. At the same time, it also has superior heat resistance during drying treatment and also, for example, In the state of being used in electronic materials, it can exhibit quite good insulation properties. In addition, for example, in the state of being used in coatings and inks, it can exhibit good gloss and water resistance. A production method and a resin composition composed of the fillers. BACKGROUND OF THE INVENTION Calcium carbonate is widely used as a filler or pigment for sealing materials and the like. Among the foregoing, for example, in the construction field, it is a material for waterproofing and sealing. Among these applications, the material is a moisture-curable one-liquid type resin group resin composition. ), Considerable advantages in construction: For the purpose of coatings, paper, rubber, plastics and dense building, automotive and flooring materials, etc., the two-liquid type is widely used for sealing than moisture hardening Resin composition products (hereinafter, simply referred to as one-liquid type) are equipped with the following construction and the production volume is sharply increased. In particular, it is not necessary to mix various components of two-liquids for bonding; and The so-called mixing technology is not required; and the so-called operation time can be shortened; therefore, the growth can be achieved. Uses of the one-liquid resin composition

8S121028.ptd Page 5 ^ 60519 V. Description of the invention (2) Most of the materials such as materials and sealing materials are used in the vertical part of the construction. 'Of course', the construction must be carried out and the road must be removed to avoid the so-called sagging county. Hanging from the regulations * until L refers to the operational efficiency during construction: two; if this happens, it will also affect the trend ^ sheep must have very good resistance to change (th 1 χο) and resistance Speak Yi Yi. 1 a &amp; + <碉 ω m L ^ + is steep. In order to be able to produce as described above, the P A system uses colloidal silica and calcium carbonate. The value is, the former (thix〇) sex-imparting agent, system, contains-narrated quite a lot of problems: the thickening phenomenon in the storage; and, like: the hardening of the ethyl acetate, etc. in the interface Foaming and cracking have always been, for example, in colloidal silica, there are quite a few proposals as described in Japanese Patent Publication No. 45-4111 0, Japanese Patent Publication No. 53 5899, and the like. In addition, the aforementioned proposals are also considered to be superior, but the disadvantages of the colloidal silica are caused by a number of problems described below: The modulus after curing is so high that The followability of the so-called adherend becomes rather poor; and since only a small amount of colloidal silicon oxide is present, a relatively high thixo property is generated, so it is not easy to perform Subtle viscosity adjustments; and, as thixotropy decreases over time, fiscal characteristics become worse, and silicosis may occur, so it ’s not easy to deal with so-called Moving on the health situation.

460519 V. Description of the invention (3) In addition, also in the carbonated carbonate, the raw material limestone is only pulverized and has coarse particles, which makes the so-called poor and insufficient thixotropy and other physical properties insufficient. In addition to fatty acids or stone fibers, the general treatment is carried out by heating carbonic acid; | dry treatment of bow and calcium and surface treatment, on the surface of carbonic acid, so that the hydrophilic surface of the absorbed water is good influences. Also, the results were not achieved. On the other hand, even in sediments that are deposited by moisture in the air, they react on the surface of calcium carbonate. In addition, the surface treatment with strong metal salts and surfactants of common acids and resin acids is strong. Therefore, the interface is active, and the reaction theory with water is in any of the states. Deterioration or the occurrence of so-called foaming. Carbonic acid has been treated with a hydrophilic surface treatment beforehand. In the case of a sword, which is generally referred to as a heavy calcium carbonate, and a classification treatment, the residual processing feeling (completion) ) Becomes thixo, and it also makes "the heavy calcium carbonate is treated with a fat surface, but because the surface treatment agent is also agitated with carbonic acid," it cannot be applied without restriction. The so-called hydrophilic surface will remain after the application. "Score" will not cause thixotropy (thixo) in the state of storage stability. In the state of carbonated feed, the moisture absorbed on one of the liquid resin groups under the hardened mechanism will start to develop. In the surface treatment agent, for example, calcium carbonate, which is bounded by a fatty acid or a salt thereof, the hydrophilic phase agent is relatively easy to adsorb water to facilitate the polymerization reaction. It is said that the stability of storage has become extreme, and the reason for the cracks. Therefore, of course, during the drying process, but especially the calcium carbonate ’, its water removal rate is similar.

Λ 6 Ο 5 1 9 V. Description of the invention (4) Local difference, and it will also make non-values of moisture and binding agent stored in the fatty acid tester for sealing. It is carried out in Japanese sour vinegar. It can solve the advantage of the fat composition. However, the characterization of lipids, so that the moisture removal rate is hot, or under the condition, will result in the characteristics. In addition, the general formula acid, acid Calcium is selected; however, the surface of the sample is brown. Because of the influence of the hydrophilicity of the alkaline metal ions contained in it, the stability of Tibet becomes poor. In the material, in the modified silicone, the calcium carbonate which has been surface-treated with the salt of the moon is generally used, but the ^ $ rate is quite poor, so that it is necessary to use the so-called point often expensive Dehydrating agent, therefore, does not have a practical value Patent No. 2-38309, it is proposed that calcium carbonate by surface treatment of fat; If this technology is adopted, a considerable degree of the aforementioned problems, especially It is found in the field of sealing materials that are representative of a liquid type tree. Fatty acid esters are not easy to be considered to have thermal safety, and may cause the problem of heat resistance during drying. In order to improve this, for example, it is added for a long time at 130 ° C or more. 1 5 0. (: And the thermal degradation of the raw surface treatment agent in the state of heating for several hours will cause damage to the original problem. 'Japanese Patent Laid-Open No. 10-245221, it is proposed that: (1) The compound with a melting point of 50 ° C or higher and one of the group consisting of metal salts of these acids and surface treatment with carbonic acid such as liquid polyurethane In the state of using calcium carbonate as described above, the color of the sealant is the same, especially in the state of the white series sealant.

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V. Description of the invention (5) Due to the hardening speed of the sealant, pollutants will adhere to the seal

It is necessary to use an expensive coloring agent, and it is relatively slow '. Therefore, after the application, problems such as the surface of the agent also occur. General formula (1) Η 〇

I II A— (N — C —〇—η (In the general formula (i), A is the residue of the isocyanate &amp; acid ester group or the amine compound II :: The integer ⑴ system of Bu 4 is a hydrocarbon group, and the residual group of the amine group is a smoke group of C3 or higher.) At least resistant! A hydrocarbon group of a resin composition such as an ink and a p is a filler or a pigment. This becomes And other resin compositions, such as calcium carbonate, calcium carbonate, calcium carbonate, and any of the so-called ma, and the basicity of the above-mentioned test metal salts and resin acids. In addition, even in the field of plastics and coatings Calcium carbonate has traditionally been used in plastics, coatings, and oil calcium. It is a calcium carbonate produced using the aforementioned process called heavy sedimentation. These calcium carbonates use fatty acid metal salts and fatty acid esters. The basic metal salt of the fatty acid, the basic metal salt of the resin acid, and the fatty acid ester are subjected to surface treatment. For example, in a state where carbamic acid calcium which is subjected to surface treatment is used on plastics , The dispersion is quite poor Further, the requirements' of insulating months art, for example, in a state where electric wires, etc., the so-called system requirements

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4 60519 V. Description of the invention (6) ----- Can obtain practically usable calcium carbonate, even insulating properties. In addition, under actual conditions, such as in the state of capacitor films, calcium carbonate It does not have sufficient insulation, so the acid cannot be used. In addition, under actual conditions, in the state where calcium acid is used for coatings and inks, it is required to obtain carbonic acid having practical usability = calcium acid, and even water resistance. In view of the actual situation like the foregoing, the present invention provides a calcium carbonate filler for surface treatment, which is particularly suitable as a filler for resins, a method for producing the same, and a resin composition composed by mixing the filler. In the state of the curable resin composition, it has quite good heat resistance during drying, and can also produce very good thixo, slump resistance, and very good storage stability, and 'For example, when it is used in plastics, it can show quite good dispersibility and insulation. In addition, for example, when it is used in paints and inks,' it can show quite good water resistance. The present inventors conducted a thorough review in order to solve the aforementioned problems. As a result, it was found that the specific surface treatment calcium carbonate filler and the resin composition composed of the surface treatment calcium carbonate filler can meet expectations. The purpose is to complete the present invention. The inventor discloses the content of the first embodiment of the present invention (item 1 in the scope of patent application), which is a calcium carbonate filler for surface treatment, and is characterized by: saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid And resin acid, at least one was selected, and a wet method was also performed.

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V. Description of the invention (7) Surface treatment. The content of the second embodiment of the present invention (item 2 of the scope of the patent application) is a carbonic acid # 5 filler for surface treatment, and is characterized by:, is composed of metal soaps of saturated fatty acids, metal daggers of unsaturated fatty acids 〇X l At least one kind is selected from the group consisting of a metal soap of a cyclic carboxylic acid and a metal soap of a resin acid. Moreover, a wet surface treatment is also performed, and at the same time, the content of the metal is 1. 〇X l 〇-3mol / lOOg Cac03. As an ideal embodiment (item 3 of the scope of patent application), the calcium carbonate filler for surface treatment of Leru's scope of patent application, the BET specific surface area of calcium carbonate is 3 to 1 2 Om 2 / g. As an ideal implementation form (item 4 of the scope of patent application), if the application of acid-breaking hair is made from one material, the temperature of fat is at least, and the hair is the second item of blindly seeking profit. The calcium carbonate filler for surface treatment has a BET specific surface area of 3 to 120 m2 / g. ', The content of the third embodiment of the Ming (the method for surface treatment of the scope of application for the scope of the patent application No. 5 of the scope of the patent application' ') and its characteristics is:' adding the saturated fatty acid to the dan 2 acid 5 water slurry ' Unsaturated-a species of s !, t? Acid and resin acid, and selected to correct the current, '., And also heated to the sun and the moon's carbonic acid mom' above the melting point of these acids to wet The surface treatment is as described in the application of the true application // (item 6 in the scope of the patent application), and the surface treatment of the item 2 or 4 in the patent scope is filled with calcium carbonate.

88121028.ptd Page 11 460519 V. Description of the invention (8) The method of manufacturing materials, which is characterized by: It is added to the calcium carbonate aqueous slurry, and added (A): from saturated fatty acids, unsaturated fatty acids, alicyclic At least one acid is selected from the group consisting of a group of carboxylic acids and resin acids, and (B): reacts with the at least one acid selected by (A) above to generate metal hydrogen of water-insoluble metal soap Oxides or metal oxides; and (A) metal soap obtained by reacting the aforementioned (A) and (B), and the aforementioned carbon base calcium is subjected to wet surface treatment. The content of the fifth embodiment of the present invention (item 7 of the scope of patent application) is a method for manufacturing a carbonic acid dance filler for surface treatment, such as the scope of the patent application scope 2 or 4, and its characteristics are as follows: At least one metal soap is selected from the group consisting of metal soaps of saturated fatty acids, metal soaps of small palladium and fatty acids, metal soaps of cycloaliphatic reciprocating acid, and metal soaps of resin acids. It is added to the water slurry of carbonic acid, and after dehydration and drying treatment, it is heated to a temperature above the melting point of the added metal soap above the carbonic acid mother, and subjected to wet surface treatment. . The content of the sixth embodiment of the present invention (please = is a method such as the item 2 or 4 of the patent application park; / item of the figure), and its feature is: carbonic acid for surface treatment Ma filling is added to the calcium carbonate aqueous slurry, adding (c) the test metal salt of unsaturated fatty acid, basic gold of saturated fatty acid, basic metal salt of fatty acid, and test metal salt of resin acid. , Cycloaliphatic carboxylic acid selected at least one basic metal salt; and in the group consisting of +

460519 V. Description of the invention (9) 'Calcium, after the surface treatment, the technical equipment, so that the inspection metal content becomes! 〇 ， Washing treatment is carried out so as to take 1.0 Xl0-3m〇1 / 100g CaC〇3 λΛ ρ ° According to the seventh embodiment of the present invention, it is a type such as the scope of patent application 2 or 4 Item 9), a method of manufacturing materials, and characterized in that the surface treatment of the item is filled with carbonated water in a calcium carbonate aqueous slurry, λ, an alkali metal salt, and an unsaturated fatty acid base: C): By the test of saturated fatty acid metal salt and resin acid test = metal shaw, cycloaliphatic rebel acid selected at least one test metal salt; salt; in the group consisting of 4. Ya and in the aforementioned After the carbonic acid U is subjected to a surface treatment, 'Taiwan then added the test with ⑴, the metal salt reacts to form a metal compound with a metal soap, and the metal soap of (C) undergoes a metathesis reaction'. Then, it is washed with water. In order to make the content of alkaline metal '1 () &lt; 10, 〇1 / 100g CaC03 or less. The content of the eighth embodiment of the present invention (item 10 in the scope of patent application) is "a resin composition" and its characteristics are: carbonic acid for surface treatment according to any one of the scope of patent applications 1 to 4 Filling and mixing into various resins. The ideal embodiment (item 丨 of the scope of patent application) is as follows: For example, the resin composition ′ of the scope of patent application No. 10, wherein the resin is used in coatings. This is an ideal embodiment (item 12 of the scope of patent application), which is

88121028.ptd Page 13 :: 519 V. Description of the Invention (ίο): For example, the resin composition in the scope of patent application No. 10, wherein the resin is used in the ink. As an ideal embodiment (item 13 of the scope of patent application), the resin composition is the same as the scope of application of the scope of patent application 10. The resin is used in plastics. As an ideal embodiment (item 14 of the scope of patent application), the resin composition is as follows: the resin composition of the scope of patent application 10, wherein the resin is used in a sealant. As an ideal embodiment (item 15 of the scope of patent application), the resin composition is as follows: the resin composition of the scope of patent application 10, wherein the resin is used in the hardening resin. This ideal embodiment (the 16th in the scope of patent application) is the resin composition of the 10th in the scope of patent application, where the resin is used in a moisture-curable composition. The content of the ninth embodiment of the present invention (item 17 of the scope of patent application) 1 is a moisture-curable resin composition, which is characterized in that it is any one of the scope of patent applications 1 to 4 Carbonated feed for surface treatment, feed, (D): fatty acid esters and / or compounds having a melting point of 50 t or more as shown by the following general formula (1), and carboxylic acids, sulfonic acids and the foregoing

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The calcium carbonate selected from the group is mixed with at least one of the following:-5. Description of the invention (11) Composition of acid metal salts Surface treatment composition General formula (1) Η

II (1) Residues of isocyano groups are removed; η is less than 1 hydrocarbon group, is a fatty acid, unsaturated metal soaps other than the metal genus of metal soap alone or is not an interface wet treatment, described everywhere The dispersibility of these surface treatments, as well as the thermal stability of calcium acid, can also be A- (NCOr) η at high temperatures (in the general formula (1), A series is the The residual group is an integer of 1 to 4 except that the amine system is removed by the amination compound; R is a hydrocarbon group, and R is a hydrocarbon group of C3 or more.). The best implementation of the invention The surface treatment agent used in the present invention, after &amp; &amp; γ is a saturated fatty acid, alicyclic carboxylic acid, resin hydrazone, or the foregoing (the metal soap in the description of the present invention refers to the metal soap Two gold salts.): A combination of two or more of these acids or their metals. These surface treatment agents and active agents are hydrophobic, and can be generally coated on the surface of calcium carbonate. Therefore, the β pro-agent is contained in various resins, and it has a very good heat resistance. In terms of properties, it is also compared to fatty acid esters, and in addition, the carbon for the surface treatment of these performers is quite ground. Therefore, the surface treatment agent of the present invention, iHil mm 88121028.ptd Page 15 460519 V. Description of the invention (12)-Drying treatment is performed, and for example, a one-liquid denatured silicon snapper sealant can be used, and an expensive dehydrating agent can be omitted. In addition, it is also very suitable as a rapid hardening sealant and a filler for adjusting the curing time. In addition, in the case where the calcium carbonate for surface treatment of the present invention is used in a capacitor film or the like, it can exhibit relatively good dispersibility and insulation properties. For example, the surface treatment of the present invention is used for coatings and ink With carbonic acid, it can also play a very good financial performance. The calcium carbonate filler for surface treatment of the present invention can be produced by the method described below. The first manufacturing method of the calcium carbonate filler for surface treatment is as follows: at least one acid selected from saturated fatty acids, unsaturated fatty acids, alicyclic acid and resin acid is directly charged into the calcium carbonate slurry. In addition, the above calcium carbonate slurry is heated to a temperature above the melting point and stirred, and then dehydrated, dried, and powdered by a general method. The second manufacturing method of the calcium carbonate filler for surface treatment is as follows: (A) is added to the aqueous slurry of carbonic acid, which is composed of a saturated fatty acid, an unsaturated fatty acid, an alicyclic carboxylic acid, and a resin acid. At least one acid selected from the group consisting of, and (B): reacting with the at least one acid selected from (A) above to form a metal hydroxide or metal oxide of a metal name; and 'also The metal soap (A) obtained by the reaction between (A) and (B), and the calcium carbonate

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Δ 60519 V. Description of the invention (13) Wet surface treatment, and then the dehydration, drying, and powder finishing treatment ("B") in the general method can be called the addition (A) Either before or after, and (A) and (B) may be added at the same time. The metal hydroxide is a metal hydroxide that reacts with at least one acid selected from the group consisting of a saturated fatty acid, an unsaturated fatty acid, an alicyclic carboxylic acid, and a resin acid to generate a metal soap. Examples include barium hydroxide, calcium hydroxide, magnesium hydroxide, and strontium hydroxide. In addition, as the metal emulsion that reacts with (A) to form a metal soap, examples include barium oxide. , Calcium oxide, magnesium oxide, and thorium oxide. Any of these metal hydroxides and metal oxides may be used alone, or two or more of these metal hydroxides and metal oxides may be used in combination. The third manufacturing method of the calcium carbonate filler for surface treatment is to select the group consisting of various metal soaps of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids. One or more kinds of metals 4 'are directly charged into the calcium carbonate slurry, and the complex acid slurry is also subjected to a strong stirring treatment and a surface treatment method. It is stated that these metal soaps have a very strong water repellency, and really, in a state like the above, the metal soaps will not dissolve in it. Therefore, it is best to use a water-soluble organic solvent slurry ^ : Add these metal soaps. As the water-soluble organic solvent, examples include methanol and ethyl alcohol.

5. Description of the invention (14) Alcohols, alcohols such as propanol, and ketones such as acetone, fluorenyl ethyl ketone, and fluorenyl propyl ketone, etc., and the aforementioned alcohols and ketones can be used alone Any one of these alcohols, or two or more of these alcohols and ketones may be combined and used. Here, for the purpose of making the coating state uniform, it is desirable that the metal soap used is a fine powder as much as possible. In addition, after the dehydration and drying treatment, if the heat treatment is performed at a temperature higher than the melting point of the metal soap used, the application is further completed. The fourth manufacturing method of the calcium carbonate filler for surface treatment is as follows: It is added to the aqueous slurry of calcium carbonate, and (C): an alkali metal salt of a saturated fatty acid and an alkali metal of an unsaturated fatty acid are added. At least one qualitative metal salt selected from the group consisting of a salt, a basic metal salt of an alicyclic carboxylic acid and a basic metal salt of a resin acid; and After surface treatment 'Next, the calcium carbonate slurry for surface treatment was subjected to water washing treatment until the content of the alkaline metal became 100 × 100-3 mol / 100% m relative to 100 g of calcium carbonate. 〇1 to the following methods. In terms of the importance of the above-mentioned method for producing a carbonic acid filler for surface treatment, the so-called test metal ions may have problems in storage stability due to the hydrophilicity of the basic metal ions. 'Therefore, the basic metal in (C) is substituted with calcium to form a calcium metal salt of a saturated fatty acid, a calcium metal salt of an unsaturated fatty acid, a calcium metal salt of an alicyclic carboxylic acid, and a resin acid, respectively. The dance metal salt 'results' by watering metal ions in a free state

88121028.ptd Page 18 460519 V. Description of the invention (15) Wash treatment so that the content of the alkaline metal becomes 1.0 X l0-3mol / l00g mol relative to 100g of calcium carbonate. the following. The fifth manufacturing method of the manufacturing method of the calcium carbonate filler for surface treatment is to add (C): an alkali metal salt of a saturated fatty acid and an alkali of an unsaturated fatty acid to an aqueous slurry of calcium carbonate; At least one basic metal salt selected from the group consisting of alkaline metal salts, basic metal salts of alicyclic carboxylic acids, and basic metal salts of resin acids; and, for the aforementioned calcium carbonate, After the surface treatment, (D) is added to react with the basic metal salt of (C) to form a metal compound with a metal soap, and the metal soap of (C) undergoes a metathesis reaction. . Even in the 5th manufacturing method, 'for the same reason as in the 4th manufacturing method described above, it is necessary to perform a water washing treatment until the content of the alkaline metal is made to 100g of calcium carbonate, 1. 〇χ 1 0-3mol / 100g mol or less. When the content of the alkaline metal is more than 1.0 X 1 0-3 mol, the storage stability becomes insufficient. Examples of the metal compound that forms a metal soap by reacting with the basic metal salt of (C) above include aluminum chloride, calcium gas, ferric chloride, sodium chloride, magnesium gas, and gas. Gases such as lead, zinc gas, etc., sulfates, sulfates, etc. can be used alone, or any two or more of these metals can be used in combination. Compound. In addition, any of the five methods described above can be used alone,

88121028, ptd page 19 460519 V. Description of the invention (16) Or you can combine two or more of the above five methods. As far as the saturated fatty acids, unsaturated carboxylic acids and resin acids used in the present invention are concerned, the purpose of fatty acids and organic acids is to use as many acids as possible with a relatively large number of carbons. In order to use the aforementioned R-off τ, it is necessary to have X in addition to the qualitative properties of the hardening resin. Due to the so-called storage safety-ahshuang, η 1X 〇) and resistance to regulations, therefore, the number of carbons in the acids described above is preferably 8 or more. To be more specific, examples include caprylic acid, lauric acid, palmitic acid, stearic acid, and #Shilu cage * meat and linoleic acid, linoleic acid, and pen fatty acids, oleic acid, Specially alicyclic carboxylic acids, and resin acids such as abietic acid, pimaric acid = fragrant acid, etc. In addition, the aforementioned ":::: Xihe can be" silver ", A1" S), heart-of: U :, (iron), Mg (town), (，): two. ^, Sr (gill ), And 21 &quot; (鍅), etc. can be used alone or in combination of two or more of these metals. "The species, or the surface treatment amount of the He Dagger treatment agent, is not underfilled. .1 part by weight, then = = =" physical effect, in addition, the pn address a magic industry ...,渌 Where the surface is full. ^ In order to achieve a surface treatment amount of more than 20_ 0 parts by weight: economical and more significant effect 'Cause &quot;

88121028.ptd Page 20 460519 V. Description of the invention (17) If the content of the basic metal in the present invention is 10 × 10-3mol / 10 0g mol CaC03w, the invention can be obtained. Desired Purpose Effect 'Also, the smaller the content of the alkaline metal, the more the effect of the present invention can be exhibited. Therefore, the content and amount of the alkali metal should preferably be 7. 〇X 1〇-4m〇1 / 1〇〇gm〇1 CaC〇3 or less, if more ideal, the 'system is preferably 5. 〇X 丨〇-4 (n〇 丨 / 丨 〇 爪 〇! CaC03 or less. In addition, the calcium carbonate used in the present invention, but there is no particular limitation on the calcium carbonate used in the present invention. For example, limestone, As a raw material, once the heavy calcium carbonate and limestone having the required particle size obtained by the pulverization and classification treatment are subjected to firing treatment, 2 limes are formed, and the quicklime is hydrated. And f is an aqueous slurry of slaked lime, and then the carbon dioxide gas is conducted to the aqueous slurry of distant ash to facilitate the production of the ^ L sentence produced by the sedimentation method. In addition, it also makes the carbonate The solution and the calcium salt solution react with each other. The osmium carbonate is produced by mixing rhenium and the like, and is appropriately selected.

Jj ί® ΑϊΕ, j * 'If the aforementioned carbonic acid is used in a hardening resin composition,' in order to obtain a relatively high thixotropy and good financial properties', therefore, the best Use a BET specific surface area of 3 m 2 / g to 120 m 1 = calcium acid. If it is more desirable, it is best to use a calcium carbonate with a BETA ratio of 5 m 2 / § to 100 m 2 / g. In the state where the BET specific surface area of calcium carbonate is 4 to 3 m2 / g, 'the system does not easily produce a relatively high viscosity'. In addition, when the BET specific surface area of calcium carbonate exceeds 120 m2 / g, the amount must be increased. Number of surface treatment agents to cover the hydrophilic surface

88121028.ptd Page 21 Side € 0519 V. Description of the invention (18) The quantity ’will therefore be so expensive that it is not very economical. In addition, it is more desirable to use calcium carbonate produced by the sedimentation method which can obtain a higher BET specific surface area. In addition, under the condition of using the calcium carbonate filler for heavy texture, the alkaline components mechanically entered into the crushing and classification place will become lower in surface activity than calcium, and the set rate will also become lower. Quite well. In the state of the heavy calcium carbonate used, it is quite advantageous. Due to the good dispersibility of the surface treatment of the present invention, in the state of suitable sealing materials, adhesives and flooring fillers, it is possible to exert collapsibility and excellent storage coatings and inks. Water-soluble, etc. In addition, for example, the surface treatment of the present invention can be performed in a state where the present invention is used in a fairly good mechanical strength and hot glue, and it can be used in a capacitor film, etc. The watch system is not particularly limited, but calcium carbonate as the surface of the present invention is due to the mechanism of the heavy carbonate, so it is less contained in calcium carbonate, and because of the heavy carbonate, The removal of the water of the calcium carbonate is, for example, a calcium carbonate filler in terms of the stability of the storage of the calcium carbonate in the case of the hardening type composition, and it is particularly provided with a resin compatible with various types. For example, the thixo and stability of hardened resin composition as a dense material, etc., is good, and the stability is good, for example, when it is used in order to develop a fairly good gloss and resistance to plastic. In addition, even if the calcium carbonate filler is used in a film, it has good anti-adhesion and insulation properties, and it is especially effective. The resin of calcium carbonate filler for processing is ‘system’. Examples include: sealing

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V. Description of the invention (19) Liquid resins, adhesives such as polyurethane, polysulfide, silicon class, denatured silicone type, and polyisobutylene type, etc. used materials ^ Urea-based, phenol-based, epoxy-based, silicone-based, acrylic-based, etc.

Liquid resins for flooring, epoxy resins used for flooring, polyurethane resins, polyester resins, and other liquid resins for coatings, paints 2 ^ Phenolic, alkyd, unsaturated polymer Ester-based, amine-based, epoxy-based, ethyl-based, benzoic acid-based, polyurethane-based, stone-based, and gas-based, etc. Rosin ester-based, phenol-based, alkyd-based, scopolamine-based, urethane-based, epoxy-based, polyester-based, and phenol-based liquid resins such as phenol-based, Thermosetting resins such as urea, dicyandiamide, unsaturated polyester, epoxy, polyurethane, polyimide, etc., vinyl, polyethylene, poly °, etc. Polystyrene-based, ABS-based, polyamide-based, polyacetal-based, ester-based, fluorine-based, and poly-p-titanate thermoplastic resins, etc. In addition, the system can be used alone Any one of these resins may be used, or two or more of these resins may be combined. The amount of the resin mixed into the calcium carbonate filler for surface treatment of the present invention varies with the type and use of the resin; for example, in the state of denatured stone, the amount of denatured silicon The resin is suitably 20 to 200 parts by weight, and preferably about 40 to 150 parts by weight. When the blending amount of denatured silicone is less than 200 parts by weight, the carbonic acid carbonate cannot produce sufficient thixotropic properties. In addition, when the blending amount of denatured silicone is more than 2000 parts by weight When 'then the viscosity of calcium carbonate is too high', the work efficiency becomes relatively poor.

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V. Description of the invention (20) As far as the resin composition of the present invention is concerned, in addition to the foregoing description, in order to adjust the viscosity and other physical properties, it can be combined with one or two in combination with other needs. And various kinds of additives and colorants, and fillers such as silica, talc, sinter, zeolite, resin spheroids, and glass spheroids, such as dioctyl caprylate , Plasticizers such as dibutyl titanate, aromatic hydrocarbons such as toluene and dioxan, aliphatic hydrocarbons such as hexane and butane, petroleum solvents such as gasoline, diketones, methyl ethyl Examples of the solvents include ketones such as ketones, ether esters such as acetic acid cellosolve, and additives such as syrup oil and fatty acid vinegar-modified syrup oil. For example, in a state where the calcium carbonate for surface treatment of the present invention is used in a moisture-curable resin composition, it is possible to adjust the full gas by using and combining the fillers used in the conventional conventional technology. Curing speed of the curable resin composition. In the moisture-curable resin composition, conventionally, fatty acid esters and / or compounds having a melting point of 50 t or more represented by the following general formula (1) are used, and carboxylic acids, sulfonic acids, and the foregoing are used. At least one selected from the group consisting of metal salts of acids and formed by surface treatment, etc. · General formula (1) Η 0

I II A- (N-C-O-R) η ⑴

88121028.ptd Page 24, 4605) 9 V. Description of the invention (21) (In the general formula (1), the residue of the ester group is an integer of 1 to 4; it is (: a hydrocarbon group of 3 or more.) The surface moisture-curing resin group of conventionally used surface moisture-curing resins has therefore had to be combined with the short-moisture-curing resin of carbonic acid for surface treatment of the present invention in combination with the carbonic acid for surface treatment of the present invention. There is no particular limitation on the surface used for surface surgery. Therefore, "the number of the previously used ratios which can be appropriately used in the foregoing" is listed below, the present invention is enumerated. However, this example is subject to any limitation. Example 1 Concentration 1 6 0 g ^, A is a storage composition required for isocyanates by amine compounds and R is a nicotinic group, and R is in the conventional prior art surface treatment with calcium carbonate. The hardening time depends on the adjustment of the amount of the catalyst, such as calcium carbonate for surface treatment, in order to improve the disadvantages of the hardening time. In the examples and comparative examples, the invention is not due to the pre-production.

CaC03 / kg and adjust the S compound to remove the heterogeneous residues of the amine residue; at least one hydrocarbon group of n, which is a moisture-curable resin. The word "system" does not exhibit Tibetan stability, and It's not short-lived. However, it is possible to reduce the proportion of the previously known prior art and the use of the previously known prior art, and the required curing time, calcium carbonate for surface treatment, and The combination of calcium carbonate for surface treatment will explain the examples and comparison in more detail.

Becomes a BET at a temperature of 75 ° C

I 46051 9 V. Description of the invention (22)-1Okg of calcium carbonate body produced by sedimentation method with a specific surface area of 20M / g, and 80g of stearic acid (melting point: 70t ^ ^ hours) Stir 're-surface treatment. Then go to the lighted carbonic acid water slurry' for dehydration, drying and pulverization, and "until the solid content is 60% by weight" in order to obtain the hard wall acid_ Surface-treated calcium carbonate powder. Example 2 Except that the stearic acid 'in Example 1 was changed to lauric acid (melting point 44 t), the temperature was 75. (: changed to a temperature of 50 t) 'The rest are treated in exactly the same manner as in Example 1 above. D Example 3 Carbonic acid produced by a sedimentation method with a concentration of 160 g CaCOg / kg and adjusted to a temperature of 75 &lt; &gt; C2BET specific surface area of 20 m2 / g To 10 kg of calcium water slurry, 80 g of stearic acid was added, and then 104_2 g of calcium hydroxide slurry with a concentration of 10% by weight was added, followed by stirring for 5 hours, and then the surface was further added. Treatment. Next, for the aforementioned calcium carbonate aqueous slurry Dehydration, drying, and pulverization were performed until the solid content was 60% by weight, so as to obtain the calcium carbonate powder which had been surface-treated in calcium stearate. The concentration in Example 3 was 10 104.2g by weight of calcium hydroxide slurry was changed to 15.8g of calcium oxide, and the rest were treated in exactly the same manner as in Example 3 to obtain the stearic acid feed. Surface treated carbonic acid powder.

8S121028.ptd

4605) 9 * --------- 5. Description of the invention (23) Example 5 In addition to changing the stearic acid in Example 3 to lauric acid, and changing the temperature from 75 ° C to 50 ° C, at the same time, 'the addition of 104.2g of hydrogen hydroxide was changed to 148g, and the rest were treated in exactly the same manner as in the previous Example 3' in order to obtain the Surface-treated calcium carbonate powder. Example 6 10 kg of calcium carbonate aqueous slurry prepared by a sedimentation method having a concentration of 160 g of CaC03 / kg and a BET specific surface area of 20 m2 / g was added with 10 wt% magnesium stearate ( After melting 800 g of methanol slurry having a melting point of 132 ° C), stirring was continued for 1 hour, and then surface treatment was performed. Next, the above-mentioned aqueous calcium carbonate slurry was subjected to dehydration and drying treatment to a solid content of 60% by weight, and then subjected to a heating treatment at 14 ° C for 1 hour, and then, A pulverization treatment is performed in order to obtain the calcium carbonate powder which has been surface-treated in magnesium stearate.訾 Example 7 Except that the magnesium stearate in Example 6 was changed to lauric acid (melting point 150C) and the temperature of heat treatment was changed from 140 C to 160 ° C, the rest were performed. The same treatment as in Example 5 described above was performed. For 10 kg of calcium carbonate aqueous slurry produced by the sedimentation method with a concentration of 160 g CaC03 / kg and a BET specific surface area of 20 m2 / g, the concentration was added.

88121028.Ptd Page 27 460513

V. Description of the invention (24) 10 g of a warm aqueous solution of 10% by weight potassium stearate, followed by stirring at ^, and then surface treatment. Next, the aforesaid calcium carbonate aqueous slurry was' stirred ', and water was also added: ^ $ release becomes 5 times', and a dehydration treatment was performed until the solid content was 60% by weight, and then' re-performed ' Drying and pulverizing treatments are carried out in order to obtain the carbonated feed powder which has been surface-treated in magnesium stearate. As for the obtained calcium carbonate, a fluorescent X-ray analyzer was used. θ (manufactured by Shimadzu Corporation: model XRF- 1 500), and when the potassium content was quantitatively analyzed, it was 5.2 乂 10_41] 10/1/100063 (^ 0. Example 9 3 In Example 8, the solution was stirred while adding water to dilute it to a 5-fold aqueous solution, and changed to a 2-fold aqueous solution. The rest was added to the same treatment as in Example 8 described above. No .: For carbonated feeds that have been surface-treated with stearic acid feed, when the potassium content is determined by a fluorescent and ray analysis device (manufactured by Shimadzu Corporation: type -1500), it is 8.5 x10, Ql / 100g of LaLOg. Example 10: The temperature of 10% by weight of potassium stearate in Example 8 was dissolved in warm water = 0g 'to change the concentration to 10% of the weight. Except for the aqueous solution of 8 0 g, the rest were treated with spot ^ β β 仃 f /, the embodiment 8 described above is exactly the same

= And Π:; Carbonized surface carbonized by rosin ΐϊ xRr2 Λχ ray analysis ... Shimadzu Corporation: Model wins 15GQ) and quantitative analysis_ X

460519 V. Description of the invention (25) 1 0'4mol / 1 00g CaC03 ° Example 11 An acid-breaking water slurry produced by a sedimentation method having a concentration of 160 g CaC03 / kg and a BET specific surface area of 20 m2 / g To 10 kg of the body, 800 g of a 10% by weight aqueous solution of stearic acid in warm water was added. Next, 236 g of a 10% by weight magnesium carbonate slurry was added, and then mixed for 5 hours. 'Then, surface treatment is performed. Next, the above-mentioned carbonic acid-containing aqueous slurry was stirred, and at the same time, water was added and diluted 5 times', and 'dehydration treatment was also performed' until the solid content was 60 weight &quot; amount! Then, it is dried and pulverized to obtain the surface-treated calcium carbonate powder in magnesium stearate. As for the obtained calcium carbonate, when the potassium content was quantitatively analyzed by a fluorescent X-ray analysis device (made by Shimadzu Corporation, model XRF-1500), it was 4.1 X l0- 4m0i / 100g caCO3. Example] 2 A wet-type pulverizer was used, and for a heavy carbonaceous water with a concentration of 200 cac0 / kg and a BE? Specific surface area 2 &quot; g, a pulverization treatment was performed in order to obtain a BET Heavy calcium carbonate ^ water paddle with a specific surface area of 15 m2 / g. To 10 kg of the obtained water polymer, 800 g of a warm aqueous solution of potassium stearate at a concentration of 10% by weight was added and proceeded. Surface treatment of potassium stearate. Next, the aforementioned heavy calcium carbonate was taught ^, and at the same time, water was added to dilute it 5 times, and it was also added to the solid content of 60%. The weight% is *, and then 'mashed and pulverized in order to obtain this by calcium stearate

460519 V. Description of the invention (26) Surface treated calcium carbonate powder. In other words, when the calcium carbonate obtained by fluorescent X-ray analysis was used to obtain calcium carbonate and XRH 500, the unloaded content was measured (made by the amount, made by: model 10-4mol / 100g CaC03 。 ”Is 2,5 x Comparative Example 1 In Example 1, the method of“ removing the hydrangea sedimentation method ”,“, ”, the surface descending method and powdered state descending method Manufactured super mixer of carbon and calcium powder (made by Kawata m 匍 .π us) and put in 20 ^ 'liter. ^ U * made by Zhanzo * Model SMV-20, stirring blade. Use 2 pieces (S and BL type), after $ 1 is missing for the well search, then, 40kil ί will be heated directly to 90 ° C φ,. Ιν9ηηη μ g of stearic acid, In the super mixer, the speed of U 2000rpni is 308, and the surface is processed by the dry type, and then the surface is treated by the combination of / and 隹, which is named after the name + The calcium carbonate powder which had been subjected to dry surface treatment with hard moon acid was obtained. Comparative Example 2 Except that the temperature of the slurry in Example 1 was changed from 75t to 50 ° C, the rest were processed with The foregoing example 丨 showed exactly the same treatment. Comparative Example 3 Except changing 104.2 g of a 10% by weight osmium hydroxide slurry in Example 3 to a potassium hydroxide solution having a concentration of 10% by weight 157.78 'The rest are treated in exactly the same way as in Example 3. Comparative Example 4 Except that the heating time of 1 hour at 140 ° C in Example 6 was changed to a temperature of 1 2 0 C Except for the heating time of 1 hour, the rest are processed in exactly the same manner as in Example 6 described above.

88121028.ptd Page 30 460519 V. Description of the invention (27) Comparative Example 5 Except that the sample was diluted 5 times by water in Example 8 and changed to a case where there is no water for dilution, the rest were processed. The foregoing embodiment 8 is processed in exactly the same manner. As for the calcium carbonate obtained, the potassium content was quantitatively analyzed by a fluorescent X-ray analysis device = 2. 0 X 10-3 mol / 10Og CaC03. &quot; Comparative Example 6 Except that the stearic acid in Example 1 was changed to sodium stearate, the same treatment as in the foregoing Example i was performed. As far as the calcium carbonate is concerned, when the sodium content is quantitatively determined by a fluorescent X-ray analysis device, it is 2.2 × 10, 〇1 / 1 (), which is too low. In Example 1, Except that the stearic acid 'was changed to sodium laurate, π 1 was treated in exactly the same manner as in Example 1 described above. As for the calcium carbonate of this fraction i, when the sodium content is quantified by a fluorescence X-ray analysis device, then it is ^^^^^^ / 丨 ^ ⑶ 6 3 dilute the above implementation In Example 10, stirring was performed while using water and the rest was pushed t times, and changed to those without dilution without water, which resulted in exactly the same treatment as in Example 10 described above. As far as the fold out = calcium gallate is concerned, when the potassium content is quantitatively determined by a fluorescent x-ray analysis device, it is 21 x 10_3 mol / 10 π except ^ &quot; While stirring

460519

Those diluted 5 times were changed to those which were diluted without moisture, and the same treatment as in Example 11 described above was performed. ^ 'As for the calcium carbonate served by him, when the amount is determined by a fluorescent X-ray analysis device ^ When the potassium content is precipitated by Xuanba' is 1.9 X 10-3m〇1 / 1〇〇 g CaC0 ^. Except that the stearic acid 'in Example 1 was changed to glyceryl stearate, the same operation as in the foregoing Example 1 was performed. Comparative example 1 添加 In this ^ lkg of carbonic acid which has been surface-treated with sodium laurate obtained in Comparative Example 7 is added 50 g of an average particle size of 30 / zm as shown in the following general formula (2): The surface treating agent shown below is then a dry process using a Nautamixer at room temperature for 15 minutes under stirring, and at a temperature of 110 ° C for 1 hour. Stirring treatment: General formula (2) 0

NHCOCmH * 7 to 23, Comparative Examples 12 to 22 For the powders obtained in the aforementioned Examples 1 to 9, U, 12, and Comparative Examples 1 to 7, 9 to 11, at a temperature of 150 ° C, For 5 hours

88121D28.ptd Page 32 460519 V. Description of the invention (29)-After the drying process, the mixing and kneading method described below is used to manufacture the denatured silicone type sealing material. The test method is described to facilitate the evaluation of the aforementioned modified silicone-type sealing materials. Further, in Comparative Example 21, the powder 'was dried for 5 hours at a temperature of 20 t. The evaluation results are shown in Table 1. [Mixing] Resin (MS polymer-S203, manufactured by Zhongyuan Chemical Co., Ltd.) 50 parts by weight Resin (MS polymer-S303, manufactured by Zhongyuan Chemical Co., Ltd.) 50 parts by weight 50 parts by weight 120 parts by weight 2 parts by weight

Plasticizer D0P Sample-Calcium Carbonate Filler Catalyst for Surface Treatment (Neostan U220, manufactured by Toto Kasei Co., Ltd.) [Kneading method] The aforementioned mixture is kneaded with a small mixer to make a sealing material. The above-mentioned kneaded sealing material is put into a cylindrical box of a liquid type sealing material and sealed. [Storage stability test method] Immediately after the kneading process (20 ° CX 1 day), the "viscosity measured by the time-based treatment (in the oven, 50 CX 2 weeks)" was used to evaluate the storage Stability. [Viscosity measurement method] A B8U viscometer (No. 7 rotor) is used.

88121028.ptd Page 33 4 60519 V. Explanation of the invention (30) [Slump resistance] By visual inspection, it is determined that the state of the vertical system is based on the reference work described below. 〇: Good △: Slightly bad X: Bad

88121028.ptd Page 34 A 6 0 51 9 5 'Description of the invention (31) Table 1 Slump resistance 1 000 000 00 00 00 00 00 χ 〇〇〇〇〇χ χ 〇〇〇〇. Storage stability (50 ° C oven) (XI 0 4 c P) 1 rpin / 1 Οιρηι crjoooco ^ coooco ^ cNio ^ JiOLO ^ LOCOCSli-HOCQ ^ -if · »·· * ·«. * ·卜卜 cd 卜 to 卜卜卜 m-! — 1 6. 90 6.60 6.82 1 Orpm csOCMOCJOOiCOCO ^ tDt ^ OO Inch ΙΛ—ΙΛΟ »^ ►—i 1 ~~ 1 Amine WWW 抿 m m MM MMMm f ? t? f? ^ t? t? Transport another 3 K ~ Κ-Κ &quot; Κ ~ Κ-Κ-Κ-Ιν 1 rpm j 1030 .782 1050 1030 1035 1091 891 1102 1520 1150 551 fc! W.¾ mm Μ Μ MM M ί ^ ΐΗ'ΐΡίΞΜΞΊΞΊΕΜΞ 'Sgg ^ If if If K- K- | Immediately after mixing (2 ° CX 1 day) C〇0 * ^ ri / 5i—lOO ^ C ^- LOO ^ CS COCQOOOOCOCQOOOOCCE ^ Oco ODC ^ C〇LT) &lt; = &gt; E-C〇LT5 "C〇CD C5 ^ oooo〇i〇a5 ^ 〇o〇CD co ^^ irJcdodcooOLoedcxj 1 Orpm L03.0 84.5 99.0 96.1 90 · 4 96.4. 86.4 1 97.6 99.7 95.2 62.1 44.2 41.9 102.5 60.5 98.1. 96.5 95.9 98.3 51.2 103.0 91.2 1 rpm tnococsiiooaoocD e ^^ LO ΙΛ CO CD tNJ C〇〇OL〇Ln t— OOCDOOOOI &gt; -0〇t ^ OOCOO〇tf〇CDLOLrt ^^ r to — &gt; cc 〇o C ^ OO &lt; OLTi ^ Cv3 &lt; £ 5C〇 tn »-iC3i i-it— &lt; t ^ c〇ooc〇cc &gt; aa〇4〇3t * powder hue TT [jTi ~ ΓΠ ΤΠ 411 · ΓΠ fJI * ΓΠ ^ ΓΠ &gt; [[&quot; [ &quot; | Π iniD ίΠ ΈΠ ίΟ Royalty -in Luo powder hue before drying ¢ 3 ¢ 3 ¢ 0 unloaded in I ¢ 3 ¢ 3 φ] 'but φ] twist) ίΠ ΊΕ ΊΠ ίΠ ΐΠ ίΠ ΊΉ ffi ΈΈ Unloading拗 unloading buckle unloading 佃 ΊΠ {ΠίΟ ΰ] ΐΠ Ό] ΊΠ ¢ 1 · ΙΠ ΊΠ fine [\ ^ 目 目 料 \ ^ Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example Example 8 Example 9 Example 1 1 Example 1 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 9 Comparative Example 1 0 Comparative Example 1 0 Comparative Example 1 1 CT ^ mC〇C &quot; O〇CT &gt; 0- ^ iMCO, ΐ τ-4 〇 &gt; iJ C ^ J CvJ «Κκ κκκκκκ« κ κ C ^ CO- ^ LfiCC &gt; I ^ O〇cri〇 ^ Cv5 -rH 1 ~ ^ r · ^ C vJ CO CsJ Kuang Kuang Kuang Kuang Kui Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kuang Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Kwong Those who have the calcium carbonate for surface treatment of the present invention have very good storage stability, thixotropic properties, and anti-collapse properties. Examples 24 to 42, Comparative Examples 23 to π For the powders obtained in the foregoing Examples 1 to 9, 11, 12 and Comparative Examples 1 to 7, 9 to 11, at a temperature of 150 ° C, After performing a drying process for 5 hours, the method of mixing and kneading described below is used to manufacture a one-liquid aminoethyl acetonate sealing material, and the test method described below is also used. 'In order to facilitate the evaluation of one of the aforementioned liquid urethane sealing materials. Further, in Comparative Example 32, the powder was subjected to a drying treatment at 0 1 20 ° C for 5 hours. i comment: two results are shown in Table 2. / ,. Ding 1 and Comparative Example 1 〇Easy evaluation— "The evaluation result of the liquid type. In addition, the sealing material using calcium carbonate was also adjusted. 〇 [Mixed] The mixing ratios of Examples 3 and 4 were changed to Available time. The urethane at the surface of 11 and 11 is shown in Table 3. Resin (Takenate L1 0 78, Takeda Pharmaceutical Co., Ltd. Industrial Co., Ltd.) Co.) Sample-Surface treatment calcium carbonate filler 1 20 weight 1 part [kneading method] 80 parts by weight are kneaded with a small mixer to produce the sealing material. The above-mentioned kneaded and dense ^ is used to make a cylindrical E-box of liquid-type loose and sealing material, and π is sealed. Load it to 1 '4 6 Ο 5 f 9 V. Description of the invention (33) [Storage stability test method] After kneading (20 ° CX 1 day), immediately process by time (in the oven, 50 ° CX 2 weeks) to determine the storage stability. [Viscosity measurement method] A type 8811 viscometer (rotor of ^ 0.7) was used. [Slumpability] The state of vertical construction is determined by visual inspection based on the criteria described below. 〇: Good △: Slightly bad X: Bad [hardenability] The sealing material is squeezed out of the box so that the sealing material is hardened from 20 ° C and cannot adhere to the finger The time required to determine the hardenability. 〇: Hardened within 3 hours. X: It takes 3 hours or more to harden. [Hardening time] The sealing material is squeezed out of the box to measure the time required until the sealing material at 20 ° C hardens and cannot adhere to the finger.

88121028.ptd Page 37 4 6〇5] 9 V. Description of the invention (34) Hardenability ◦ 〇〇〇〇〇〇〇〇〇〇 '〇〇〇〇〇〇〇〇〇 X X Slump resistance i 〇〇〇〇〇〇〇〇〇〇〇 〇χχ〇 &lt; 3000 〇00〇00 Storage stability (¢ 0¾ oven) (xltTcP) Two weeks after standing 2.5rpm / 20rpm rpmΛίΛοο Buoaostot— 〇— 卜 1 Μ Μ 1 Μ 1 ιλ 20rpm 49.5 46.5 56.5 56.2 67.8 67.2 48.6 5L7 78.5 53.1 38.5 Exhibition Exhibition_Evil Exhibition Exhibition ~ 1 ^ ΙϊΙηΊηίϊϊεΜ? ^^ 2.5rpm C ^ oeor—〇〇 &gt; Cs3- ^ t ^ ijrt) C〇CrjcOtfOeO ^ COCOCO ^ COi— 1 藤 藤 展 葳 展 苐 蒺 t? 向 f? (? (Ξ1 向 g wear K-KrK-if | Immediately after mixing (20ec XI days) 2.5rpm / 20rpm 1—to ^ eoh-coco- ^ cscocDfo csacft ^ iroNCNjO '^ v-Hiroo * »k« ·. »^ *« «C · &quot; ζ〇t— t—bu c ··· t- ~ bu c · — C ^ COOCnJOO—cocncooit— ^« CDLOOOt 'NLnOOS 20rpia 41.0 40.8 47.4 47.2 48.7 49.1 44.9 43.5 44.6 44.7 35.2 29.7 29.2 45.3 31.9 39.1 38.4 41.0 43.2 36.9 41.2 47.6 1 2.5rpm 〇Lrsc ^ C5cgif &gt; c〇csaeoc ^ c ^ 〇σαΐΓί' ^ τιΛί-Ο -^ ίΝϊτ—icMr- · COCOCOCOCOCOCOCOCQCOi—l CO〇〇rtC〇t ^ C7SLnif5CvJCN3Cs3 CDCDOOt—OCTi · —icrQC5CT5 cococvjjjcs3co ^ cgco The color of the powder after drying is also 1 φ] Φ) ¢ Twist | button φ] ¢ 3 Ό] Ή · Π Ίχΐ ΊΠ Ή * Π3 {Π Ό φ ¢ 1 ffiioin-raffifflmingiog Powder hue before drying • mm ίπίΐκπίπ ΰΐ $ {π * π] · [π ¢ 3 also 1 ¢ 1 ifl} ifl} φ] φ] ip ¢ 3 ¢ 3 ¢ 3 ΕΠ'ίΙΙΌϋΌΠΐΠΐΠ'ΏΦΐΠ'ΠΙ ^^ \ item \ sample \ — (CM KUANGtaili Ning Kuanguo Kuangkuo Kuangwei Kuangyui Cuixiu trousers revealing boudoir grip Ghost girl &lt; = ι Ο —f — CNicrs'rrinco Bu Song basket Nao prison so far Song Song Song ugly ± ugly wife: five ugly women CqC〇t> JC \ iC ^ tNIC〇CnCOfOCO mound Kuang Kuang 窣 Kuang Guozhang Kuang Kuang Kuang Kwong's boudoirs compose burial nirvana boudoir c ^^ lococ *-. Οοσ ^ ο- ^ CNJco cvJC \ JCs5C ^ i ^ cqcM &lt; roc〇cT5c〇 Marina Kuang Kuang Raspberry Marina Kuang Ning extracting and transporting S steroids 埴 镒 埴 镒 趦 11111 88121028.ptd page 38 4 60519 V. Description of the invention (35) Table 3 Sample hardening time (time) Example 3 5 Sample 1 of Example 3 2 0 weight 2.0 Example 3 6 Sample of Example 4 1 2 0 parts by weight 2.5 Example 3 7 Sample of Example 3 8 0 parts by weight + Sample of Comparative Example 10 4 0 parts by weight 3.5 Example 3 8 Sample of Example 3 60 parts by weight + sample of Comparative Example 10 60 parts by weight 5.5 Example 3 9 sample of Example 3 40 parts by weight + sample 80 of Comparative Example 80 part by weight 7.5 Example 4 0 sample 8 of Example 4 0 parts by weight + 40 parts by weight of the sample of Comparative Example 4.0 4.0 Example 41 Sample 6 of Example 4 0 parts by weight + 60 parts by weight of the sample of Comparative Example 1 6.0 Example 4 2 Sample 4 of Example 4 0 parts by weight + 80 parts by weight of Comparative Example 11 2.0 0 8.0 Comparative Example 3 4 Comparative Example 1 0 by sample 1 2 0 parts by weight 9.0 Comparative Example 3 5 Comparative Example 11 by sample 1 2 0 parts by weight 10. 0 Results from Table 2 Then, it can be known that those who are mixed with the calcium carbonate for surface treatment of the present invention have very good storage stability, thixotropic properties, and financial collapse properties. In addition, from the results in Table 3, it can be known that the calcium carbonate for surface treatment of the present invention can be used in combination with the conventionally known prior art.

88121028.ptd P.39 4 4605ig 5. The surface treatment of the moisture-hardening composition of the description of the invention (36) is used to improve the moisture hardness of the so-called conventional prior art =: in order to use When the surface treatment of calcium carbonate has the disadvantages of hardening, and it is formed, in order to shorten the curing time of the resin composition. $ β is relatively long ~ 5 3, Comparative Example 3 6 ~ 4 3 is the powder obtained by using the foregoing Examples 1 ~ 9, 11, 1 and 2. Hitting 9 with η μμ, and described below The mixing method is used to make the vinyl chloride sheet, and the test method is also used to evaluate the valence of the vinyl chloride sheet. The results are shown in Table 4. fruit. Evaluation [Mixed] Vinyl chloride resin (Si〇〇i plasticizer DOP tribasic acid (TS-100 lead stearate (NS-10 0 manufactured by Ben Ethylene Co., Ltd.) 100 parts by weight 5 〇 Parts by weight of Kikuchi Pigment Co., Ltd.) ^ 3 parts by weight of Kikuchi Pigment Co., Ltd.) 1 part by weight of sample-calcium carbonate filler for surface treatment 50 wt. [Manufacturing method of vinyl chloride sheet] 73 + by temperature 1 6 5. (: Roller, and for the aforementioned mixture, it is mixed with each other for 6 minutes in order to become a thin sheet, and the 2 mm thick sheet of the mixture is taken out. The obtained sheet is sandwiched between 2 sheets In the iron plate, and by borrowing * 17 (Γ &lt;:

4 60519 V. Description of the invention (37) After performing a 7-minute pre-heat treatment, a pressure treatment of 7.8 MPa (kg / cm2) was performed for 3 minutes. After the aforementioned iron plate has been subjected to pressure and cooling treatment, the aforementioned sheet is then taken out. In addition, the thickness of the sheet is 1 mm. [Volume resistivity test method] The volume resistivity of the obtained sheet was measured in accordance with J IS (Japanese Standards Association). [Dispersion test method] The surface state of the obtained sheet was determined by visual inspection based on the criteria described below. 〇Good Δ Slightly bad X Bad Table 4 \ ^ Item sample ^ \ Volume resistivity (X 10_12 Qcm) Dispersibility Example 43 Example 1 80. 5 〇Example 44 Example 2 71. 2 〇Example 4 5 Implementation Example 3 77. 4 Example 46 Example 4 65.8 Example 47 Example 5 70. 6 Example 4 8 Example 6 88. 1 Example 49 Example 7 82.9

88121028.ptd Page 41 4 60519 V. Description of the invention (38) Example 5 0 Example 8 66. 2 〇 Example 5 1 Example 9 44. 0 〇 Example 5 2 Example 1 1 52. 4 〇 Implementation Example 5 3 Example 1 2 63. 1 〇 Comparative Example 36 Comparative Example 1 55.3 X Comparative Example 37 Comparative Example 2 31.6 X Comparative Example 38 Comparative Example 3 4, 4 〇 Comparative Example 3 9 Comparative Example 4 45.3 X Comparative Example 4 0 Comparative Example 5 2. 9 〇Comparative Example 4 1 Comparative Example 6 5.1 〇Comparative Example 4 2 Comparative Example 7 6.2 〇Comparative Example 4 3 Comparative Example 9 3.3 〇 From the results in Table 4, it can be seen that the blend has the present invention Those who use calcium carbonate for surface treatment have very good dispersibility and insulation properties. Example 54 and Comparative Example 44 use the powders obtained in Example I 0 and Comparative Example 8 described above, and according to the mixing method described below, the kneading process is performed by a sand mixer to facilitate the production of water. In order to evaluate the effect of the above-mentioned water-based ink resin composition, the test method described below is also used. The evaluation results are shown in Table 5. [Mixing] resin (Jonkulear J-68 'Johnson polymer (manufactured by Johnson Polymer)) 100 parts by weight

8812] 〇28, ptd Page 42 460519 V. Description of the invention (39) 18 parts by weight 0.8 parts by weight Dainippon Ink Chemical Industry Co. 20 parts by weight moisture silicone defoamer colorant (Fast Genbul-TGR Division (Manufactured) Samples-15 parts by weight of calcium carbonate filler for surface treatment [Water resistance test method] A manual color development machine is used to facilitate the development of various water-based printing ink compositions on coating paper_Leng0U CRC (Lengou Company system). The vibration-type dyeing material rubbing fastness tester (made by Daiei Scientific Seiki Seisakusho Co., Ltd.) was used, and the cloth containing moisture was loaded under a load of 2.0 〇N (200g). The rubbing was performed 5 times to facilitate the evaluation of the water resistance by the state of the ink adhered to the cloth. 〇: No ink was found to stain the cloth. X · A considerable amount of ink was found to contaminate the fabric.

From the result of Table 5 ', it can be seen that the carbonic acid for surface treatment # 5 |' mixed with the present invention has very good water resistance.

460519 V. Description of the invention (40) Examples 5 5 to 6 5 and Comparative Examples 4 5 to 5 2 are obtained by using the foregoing Examples 1 to 9, 11, 12, and Comparative Examples 1 to 7, 9 The powder is dispersed by a disperser to a particle size of 25 / zm or less according to the mixing method described below, so as to produce an alkyd resin coating composition, and also by the test method described below, so that The effect of the aforementioned alkyd resin coating composition was evaluated. The evaluation results are shown in Table 6. [Mixed] Alkyd resin (made by Dainippon Ink Chemical Industry Co., Ltd., Beckozor P_470_70) 250 parts by weight of titanium oxide (manufactured by Ishihara Sangyo, Tiepec R-820) 1 2 0 parts by weight of carbonic acid Mai (manufactured by Maruo Yoko Corporation, Super SSS) Mineral oil desiccant, skin inhibitor (33 parts by weight, 70 parts by weight, 14 parts by weight, manufactured by Nanmoto Chemical Co., Ltd., Di sbaron # 50 1), 1.5 parts by weight, glass particles, 3 50 parts by weight, carbonic acid for surface treatment 58 parts by weight of calcium filler [Gloss, water resistance test method] Various alkyd coating compositions were coated on a glass plate 'by a 4mi Is coating machine', and at room temperature, the aforementioned alkyd After the coating composition has been dried for 24 hours, the gloss is then applied.

88121028.ptd p. 44 460519

88121028.ptd Page 45 V. Description of the invention (41) meter, in order to determine the 60 ° gloss. Then, this glass plate was immersed in water in order to evaluate the gloss retention after 3 days. Table 6 Initial gloss 60 0 Gloss after water-based test 60 ° Gloss retention (%) Example 5 5 Example 1 87. 8 86. 1 98.1 Example 56 Example 2 86.9 85.5 98. 4 Example 5 7 Implementation Example 3 91. 2 90. 7 99.5 Example 58 Example 4 92. 3 92.2 99. 9 Example 5 9 Example 5 91. 7 91.3 99. 6 Example 6 0 Example 6 92. 1 91.5 99.3 Example 6 1 Example 7 91. 8 91.2 99.3 Example 6 2 Example 8 91. 1 90. 4 99.2 Example 6 3 Example 9 90.9 89. 1 98. 0 Example 64 Example 11 90.5 89. 8 99. 2 Example 6 5 Example 1 2 79.8 79. 3 99. 3 Comparative Example 4 5 Comparative Example 1 78.1 65.9 84. 4 Comparative Example 4 6 Comparative Example 2 76. 6 63. 5 82.9 Comparative Example 4 7 Comparative Example 3 75 4 67. 7 89. 8 Comparative Example 4 8 Comparative Example 4 85. 4 78.1 91.5 Comparative Example 4 9 Comparative Example 5 86.6 77. 5 89. 5 Comparative Example 5 0 Comparative Example 6 85.4 77.2 90. 4 Comparative Example 5 1 Comparative Example 7 83.8 72. 9 87. 0 Comparative Example 5 2 Comparative Example 9 74.4 62. 9 84. 5 460519 V. Explanation of the invention (42) From Table 6, it can be known that the mixture is used for the surface treatment of the present invention. Calcium carbonate filler &gt; The system has very good financial and water properties. ○ [Comprehensive evaluation] Based on the above test results, based on the standards described below, in order to determine the comprehensive evaluation of the various filling materials of Implementation Examples 1-12 and Comparative Example 11. The results of the comprehensive evaluation of the aforementioned various fillers are shown in Table 7. 0 ◎ can show very good performance 0 〇 can show good performance 0 Δ Although 9 can be used, its performance cannot be improved 0 X When used ) Will reduce its physical properties. Table 7 Comprehensive Evaluation Example 1 〇 Example 2 〇 Example 3 ◎ Example 4 ◎ Example 5 ◎ Example 6 ◎ Example 7 ◎ Example 8 ◎ Example 9 〇 Example 10 ◎ Example 11 ◎

88121028.ptd Page 46 ^ 460519 V. Description of the Invention (43)

Example 1 2 ◎ Comparative Example 1 X Comparative Example 2 X Comparative Example 3 Δ Comparative Example 4 X Comparative Example 5 Δ Comparative Example 6 Δ Comparative Example 7 Δ Comparative Example 8 Δ Comparative Example 9 Δ Comparative Example 1 0 Δ Comparative Example 11 A Industrial Applicability As described above, the calcium carbonate filler for surface treatment of the present invention is particularly suitable as a resin filler. For example, in the case of being used in a hardened resin composition, it has a fairly good drying treatment. It also has excellent heat resistance at the same time, and can also produce very good thixotropic properties, financial collapse properties, and very good storage stability, and, for example, can be used in a state where it is used in plastics. Good dispersibility and insulation, etc. In addition, for example, when used in paints and inks, it can show quite good water resistance.

8S121028.ptd p. 47 4 6051 9 Simple illustration of drawings 88121028.ptd p. 48

Claims (1)

Bulletin 460519__ VI. Scope of patent application 1. A rhenium carbonate filler for surface treatment, characterized by: at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids 'In addition, wet surface treatment is also performed. 2. —Carbonate filler for surface treatment, which is characterized by the group consisting of metal soaps of saturated fatty acids, metal soaps of unsaturated fatty acids, metal soaps of alicyclic carboxylic acids and metal soaps of resin acids. At least one kind of 'and' was also subjected to a wet surface treatment, and at the same time, the content of the alkaline metal was 1.0 X 1 〇_3mol / 1 〇〇g CaC03 or less. 3. For example, the calcium carbonate filler for surface treatment in the first patent application scope, wherein the BET specific surface area of the calcium carbonate is 3 to 120 m 2 / g. 4. If the carbonic acid feed filler for surface treatment of item 2 of the patent application scope, the BET specific surface area of calcium carbonate is 3 ~ 120V / g. 5. —A method for manufacturing a carbonic acid filler for surface treatment such as the scope of application for patents No. 1 or 3 'wherein the aqueous slurry of carbonic acid 1¾ is added with the saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid From the group consisting of acids and resin acids, at least one kind of acid is selected, and it is also heated to a temperature above the melting point of the aforementioned acids, and a wet surface treatment is performed on the aforementioned acid breaking agent. 6. —A kind of manufacturing method of calcium carbonate filler for surface treatment, such as the scope of application for patents No. 2 or 4 ', wherein the calcium carbonate is added to the aqueous slurry of calcium carbonate, and (A) is added: from residual fatty acids, unsaturated fatty acids, At least one acid is selected from the group consisting of alicyclic carboxylic acids and resin acids, and (B): reacts with at least one acid selected in (A) above to generate water, 460519 Soluble from the foregoing and for the preparation of 7.-material and fat soap, the dehydration of the metal hydrogen (A) and (B) of the surface metal soap of the soap type surface metal soap of the foregoing calcium carbonate, such as the patent application The manufacturing method is a state in which the acid is composed of metal soap and fat, and the temperature is above the melting point after adding and drying. The porosity or metal reacts to carry out the wet surface enumeration item 2 or 4. The water selected from the saturated alicyclic carboxylic acid gold is at least one to the carbonic acid carbonate. ; And, also borrowed (A) metal soap 'surface treatment. Surface treatment: Dish yogurt filled with fatty acid metal soaps, unsaturated soaps and resin acid gold metal seed soaps, in an organic solution, and heated to the calcium carbonate added to the gold Wet 8. —A method for manufacturing carbonic acid fishing fillers for surface treatment such as the scope of the patent application No. 2 or 4, which is in a calcium carbonate aqueous slurry, and is added (C): an alkali metal salt of a saturated fatty acid At least one basic metal salt is selected from the group consisting of a basic metal salt of an unsaturated fatty acid, a cyclic metal salt of an alicyclic acid, and a qualitative metal salt of a resin acid; and After the calcium carbonate has been subjected to a surface treatment, it is then subjected to a water washing treatment so that the alkaline metal content 'is 1.0 × 10-3 mol / 100 g CaC03 or less. 9. A method for manufacturing a calcium carbonate filler for surface treatment as described in claim 2 or 4 in the patent application, which is added to the aqueous slurry of carbonic acid, and is added to (C): alkali gold from saturated fatty acid Selected from the group consisting of salts, basic metal salts of unsaturated fatty acids, basic gold salts of alicyclic carboxylic acids, and basic metal salts of resin acids; and, in 88121028.ptd Page 50 460519 Sixth, the scope of the patent application After the aforementioned calcium carbonate has been subjected to a surface treatment, and then 'added to the metal compound which reacts with the experimental metal salt of (C) to form a metal compound with metal rhenium, and The metal soap of (c) undergoes a metathesis reaction 'then' and is subjected to a water washing treatment so that the content of the alkaline metal 'becomes 1 · OX 10-3 mol / 100 g CaC03 or less. 1. A resin composition characterized in that: a calcium carbonate filler for surface treatment according to any one of claims 1 to 4 of the scope of patent application is mixed into the resin. 11. The resin composition according to claim 10, wherein the resin is used in a coating. 1 2. The resin composition according to item No. 丨 0 of the patent application scope, wherein the resin is used in the ink. 1 3, such as the resin composition in the scope of patent application No. 丨 0, wherein the resin is used in plastic. 1 4. The resin composition according to item i 0 of the scope of patent application is used in a sealant. 1 5. The resin composition according to item i 0 of the patent application range, wherein the resin is used in a hardening resin. 1 6. The resin composition according to the scope of the patent application, wherein the resin is used in a fish gas hardening type composition. 1 7. A moisture-curable resin composition, characterized in that it is a carbonic acid filler for surface treatment according to any one of claims 1 to 4 of the scope of application for patents (D): fatty acid ester and / or the following Compounds having a melting point of 50 t or more represented by general formula (i), and carboxylic acids, sulfonic acids, and the foregoing άβΟί) 9 VI. Calcium carbonate composed of at least one selected from the group consisting of metal salts of acids in the scope of patent application and subjected to surface treatment, mixed together:-general formula (1) Η 0 I II A _ (N-C-0 _ R) η (I> (In the general formula (1), A is a residue in which an isocyanate compound is removed from an isocyanate compound or an residue in which an amine group is removed by an amine compound; η Is an integer of 1 to 4; R is a hydrocarbon group, and at least one hydrocarbon group in R is a hydrocarbon group of C3 or more.). 88121028.ptd Page 52