WO2000061690A1 - Charge de carbonate de calcium traitee en surface, procede permettant de la produire et composition de resine la contenant - Google Patents

Charge de carbonate de calcium traitee en surface, procede permettant de la produire et composition de resine la contenant Download PDF

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Publication number
WO2000061690A1
WO2000061690A1 PCT/JP1999/006568 JP9906568W WO0061690A1 WO 2000061690 A1 WO2000061690 A1 WO 2000061690A1 JP 9906568 W JP9906568 W JP 9906568W WO 0061690 A1 WO0061690 A1 WO 0061690A1
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Prior art keywords
calcium carbonate
resin
treated
acid
acids
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PCT/JP1999/006568
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English (en)
Japanese (ja)
Inventor
Katsunori Fukumoto
Hiroaki Katayama
Ryoji Utsumi
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Maruo Calcium Company Limited
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Priority claimed from JP10213099A external-priority patent/JP3151196B2/ja
Application filed by Maruo Calcium Company Limited filed Critical Maruo Calcium Company Limited
Publication of WO2000061690A1 publication Critical patent/WO2000061690A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00—Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02—Inorganic compounds
    • C09K2200/0239—Oxides, hydroxides, carbonates

Definitions

  • the present invention relates to a surface-treated calcium carbonate filler, a method for producing the same, and a resin composition containing the filler. More specifically, for example, when used in a curable resin, it exhibits excellent thixotropic properties. And M Slump properties and excellent storage stability and excellent heat resistance during drying.For example, when used in electronic materials, it provides good insulation, and is used for paints and inks, for example.
  • the present invention relates to a surface-treated carbonic acid filler that exhibits excellent gloss and water resistance, a method for producing the same, and a resin composition containing the same. Background art
  • Calcium carbonate is widely used as a pigment in paints, paper, rubber, plastics, sealing materials, and as a pigment.
  • one-pack type resin composition the moisture-curable one-pack type resin composition
  • the moisture-curable one-pack type resin composition does not need to mix the components of the two-package at the time of construction compared to the two-pack type resin composition. Because of the great advantages in construction, such as no mixing technology is required and the work time can be shortened, the production volume is increasing rapidly.
  • one-component resin composition applications especially for jointing materials, sealing materials, etc., they are often applied to vertical parts, and as a matter of course, they do not drip from application to hardening.
  • thixotropy and slump resistance it is necessary and must have high thixotropy and slump resistance, as it may affect workability during construction.
  • colloidal silica, calcium carbonate, and the like have been conventionally used.
  • these thixotropic agents include many problems such as squeezing during storage, foaming and cracking at the adhesive interface during curing with urethane.
  • colloidal silica has been proposed more than before, such as Japanese Patent Publication No. 45-41110 and Japanese Patent Publication No. 53-5899, but its superiority is recognized. Disadvantages of this colloidal silica are that the modulus after curing is very high and the adherence to the adherend is poor, and a small amount of high thixotropic properties makes it difficult to finely adjust the narrowing properties. There are many problems, such as deterioration of weather resistance, poor weather resistance, and the possibility of lung injury, making it difficult to handle in occupational health.
  • modified silicone generally uses calcium carbonate surface-treated with a fatty acid metal salt.However, it has a poor water removal rate and requires the use of very expensive dehydrating agents such as coupling agents. If it is not practical.
  • JP-A-2-38309 proposes calcium carbonate surface-treated with a fatty acid ester. According to this technique, the above problems can be solved to a considerable extent, and a typical one-pack type resin composition has been proposed. In the field of sealing materials, a considerably advantageous direction has been found.
  • the ester bond of the fatty acid ester is hardly thermally stable, and thus has a problem in heat resistance during drying.
  • the water removal rate for example, when heating at 13 O'C or more for a long time, When heating at 150 ° C. or 150 ° C. for several hours, there is a problem that the treatment agent is thermally degraded and the original characteristics are impaired.
  • Japanese Patent Application Laid-Open No. 10-245221 discloses a compound represented by the general formula (1) having a melting point of 50 or more, a carboxylic acid, a sulfonic acid, and a metal salt thereof.
  • a surface-treated calcium carbonate that has been surface-treated with at least one type selected has been proposed.However, when such a surface-treated calcium carbonate is used for, for example, a one-pack type polyurethane, a sealant is required. Since the color becomes brownish, an expensive colorant must be used, especially when a white sealant is used, and since the curing is slow, problems such as adhesion of dirt to the surface of the sealant after application are caused. is there. H 0
  • n is an integer of 1 to 4
  • R is a hydrocarbon group, and at least one of R is C 8 or more hydrocarbon group o
  • calcium carbonate In the field of resin compositions such as plastics, paints and inks, calcium carbonate has conventionally been used as a tumulus or pigment.
  • the calcium carbonate used in resin compositions such as plastics, paints and inks both the above-mentioned heavy calcium carbonate and the one called precipitated calcium carbonate are used.
  • lucium is used after surface treating an alkali metal salt of a fatty acid, an alkali metal salt of a resin acid, or a fatty acid ester.
  • the present invention is particularly suitable as a resin material.
  • the present invention when used in a curable resin composition, the present invention has excellent heat resistance during drying, excellent thixotropy and slump resistance, and Gives good storage stability, for example When used for plastics, they exhibit excellent dispersibility and insulation properties.For example, when used for paints and inks, surface-treated calcium carbonate paints exhibiting excellent water resistance, etc. And a resin composition obtained by combining the same.
  • the present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, a specific surface-treated calcium carbonate material, and a resin composition obtained by blending the surface-treated calcium carbonate material with an intended purpose. We have found that we have achieved it and have completed this invention. Disclosure of the invention
  • the first aspect of the present invention relates to a surface-treated calcium carbonate filler characterized by being wet-treated with at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids and resin acids.
  • (Claim 1) saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids and resin acids.
  • a second aspect of the present invention is at least one selected from the group consisting of a saturated fatty acid metal stone, an unsaturated fatty acid metal stone, an alicyclic rubonic acid metal stone, and a resin acid metal stone.
  • the alkali metal content of 1 0 X 1 0 -. 3 and content of the surface treated calcium carbonate filler to Toku ⁇ that mol / 1 0 is 0 g CAC0 3 below (claim 2 ).
  • the surface-treated carbonated calcium chloride material according to claim 1 or 2 wherein the calcium carbonate has a BET specific surface area of 3 to 120 m 2 ng (claim 3).
  • a third aspect of the present invention is to add at least one selected from the group consisting of a saturated fatty acid, an unsaturated fatty acid, an alicyclic carboxylic acid, and a resin acid to a water slurry of calcium carbonate,
  • a fourth aspect of the present invention is that, in the aqueous slurry of calcium carbonate, at least one selected from the group consisting of (A) a saturated fatty acid, an unsaturated fatty acid, an alicyclic carboxylic acid, and a resin acid, and (B) the (A) ), And a metal hydroxide or metal oxide that forms water-insoluble goldstone is added, and ( ⁇ ) is obtained by reacting ( ⁇ ) with ( ⁇ ).
  • the method for producing a surface-treated carbonated pitting material according to claim 2 or 3, wherein the calcium carbonate is subjected to wet surface treatment (claim 5).
  • a fifth aspect of the present invention is a group comprising a metal slurry of a saturated fatty acid, a metal stone of an unsaturated fatty acid, a gold stone of an alicyclic carboxylic acid, and a gold stone of a resin acid in a water slurry of calcium carbonate. At least one selected from the group consisting of a slurry of an organic solvent, dehydration and drying, and heating to a temperature equal to or higher than the melting point of the added metal stone to perform a surface treatment on the carbonated calcium carbonate.
  • a method for producing a surface-treated carbonic acid-filled filler according to item 2 or 3 is described (claim 6).
  • No. 6 of the present invention is that (C) alkali metal salt of saturated fatty acid, alkali metal salt of unsaturated fatty acid, alkaline metal salt of alicyclic carboxylic acid and alkaline metal salt of resin acid in water slurry of calcium carbonate. At least one selected from the group consisting of lithium metal salts is added, the calcium carbonate is subjected to a surface treatment, and then washed with water to reduce the metal content of aluminum oxide to 1.0 X 10 " 3 mol / 100.
  • CAC0 3 the process according to claim 2 or 3 Ki ⁇ surface treated calcium carbonate ⁇ charges characterized by the following the content (claim 7).
  • a seventh aspect of the present invention is that an aqueous metal slurry of calcium carbonate comprises: (C) an alkali metal salt of a saturated fatty acid, an alkali metal salt of an unsaturated fatty acid, an alkali metal salt of an alicyclic carboxylic acid, and an alkali metal salt of a resin acid. After adding at least one selected from the group consisting of metal salts and surface-treating the calcium carbonate, (C )) To add a metal compound that reacts with the metal salt of
  • An eighth aspect of the present invention is directed to a resin composition obtained by blending the surface-treated calcium carbonate pigment according to any one of claims 1 to 3 with various resins. ).
  • the resin composition according to claim 9, wherein the resin is used for a coating material (claim 10).
  • the resin composition according to claim 9, wherein the resin is used for ink (claim 11).
  • the resin composition according to claim 9, wherein the resin is used for plastics (claim 12).
  • the resin composition according to claim 9, wherein the resin is used for a sealant (claim 13).
  • the resin composition according to claim 9, wherein the resin is used for a curable resin (claim 14).
  • the resin composition according to claim 9, wherein the resin is used for a moisture-curable composition (claim 15).
  • a surface-treated carbonic acid solution according to any one of claims 1 to 3, (D) a fatty acid ester, and / or a melting point represented by the general formula (1) of 5 (TC or more).
  • a moisture-curable composition characterized by comprising a compound of formula (I) and calcium carbonate surface-treated with at least one selected from the group consisting of carboxylic acids, sulfonic acids, and metal salts thereof.
  • the surface treatment agent used in the present invention may be a saturated fatty acid, an unsaturated fatty acid, an alicyclic carboxylic acid, a resin acid, or a metal stone thereof (the gold stone in the present damage is a metal other than an alkali metal). These are used alone or in combination of two or more. Since these treating agents are not surfactants, they are hydrophobic, and can be coated on the surface of calcium carbonate by wet treatment. For this reason, it has good dispersibility in various resins, is more mature and more stable than fatty acid esters, and has high heat stability of carbonated calcium sulfate surface-treated with these treating agents. Therefore, it is possible to dry at high temperature.
  • the surface-treated calcium carbonate according to the present invention when used for, for example, a capacitor film, it imparts excellent dispersibility and insulation properties, and when used, for example, for paints and inks, it exhibits excellent properties. Demonstrates excellent water resistance.
  • the surface-treated carbonated lucimate material of the present invention is produced by the following method. be able to.
  • At least one selected from saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids is directly added to a calcium carbonate slurry, heated to a temperature equal to or higher than its melting point and stirred. Dehydration-drying / powder finishing by the method.
  • (A) at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids is added to a water slurry of calcium carbonate; )
  • the metal stone of (A) obtained by adding a metal hydroxide or metal oxide which reacts with (A) to form metal stone and reacting (A) with (B).
  • the calcium carbonate is subjected to a surface treatment, followed by dehydration, drying, and powder finishing by a conventional method.
  • (B) may be added before or after the addition of (A), or may be added at the same time.
  • the metal hydroxide which reacts with at least one selected from the group consisting of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids of (A) to form goldstone is, for example, water.
  • Examples include barium oxide, calcium hydroxide, magnesium hydroxide, strontium hydroxide, and the like.
  • metal oxides that react with (A) to form metal stone include barium oxide, calcium oxide, and oxides. Examples include magnesium and strontium oxide. These can be used alone or in combination of two or more.
  • a calcium carbonate slurry is directly charged with at least one selected from the group consisting of metal stones of saturated fatty acids, unsaturated fatty acids, alicyclic carboxylic acids, and resin acids, and vigorously stirred. This is a method of surface treatment. Since these metal stones have very high water repellency and do not adjust to water as they are, it is preferable to add them with a slurry of a water-soluble organic solvent.
  • Water-soluble organic solvents include methyl alcohol and ethyl alcohol , Alcohols such as propyl alcohol, and ketones such as acetone, ethyl methyl ketone, and methyl propyl ketone.
  • the metal stone used is preferably as fine as possible for the purpose of making the coating state uniform. After dehydration and drying, heat treatment at a temperature equal to or higher than the melting point of the used gold and silver bean paste makes the coating more complete.
  • the fourth method is as follows: (C) Alkali metal salt of a saturated fatty acid, Alali metal salt of an unsaturated fatty acid, Alali metal salt of an alicyclic carboxylic acid is added to an aqueous slurry of calcium carbonate. After adding at least one selected from the group consisting of a salt and an alkali metal salt of a resin acid and subjecting the calcium carbonate to a surface treatment, the surface-treated calcium carbonate slurry is used as an alkali metal to obtain a calcium carbonate. 1. a 0 X 10- 3 method of washing with water until the mo 1 or less with respect to g. What is important in this method is that those containing alkali metal ions have a problem in storage stability due to their hydrophilicity.
  • Alkali metal in (C) is replaced with calcium, and the calcium salts of saturated fatty acids, calcium and calcium, respectively.
  • Alkali metal is produced by producing saturated fatty acid calcium lime, alicyclic carboxylic acid calcium limestone, and resin acid calcium lime. The content is 1.0 xi (T 3 mo 1 or less) per 100 g of calcium carbonate.
  • a fifth method is to add (C) an alkali metal salt of a saturated fatty acid, an alkali metal salt of an unsaturated fatty acid, an alkali metal salt of an alicyclic carboxylic acid, and a resin acid to a water slurry of calcium carbonate.
  • (D) reacts with the alkali metal salt of (C) to form metal stone.
  • Metal compounds that react with (C) to form metal stone include chlorides such as aluminum chloride, calcium chloride, iron chloride, magnesium chloride, lead chloride, zinc chloride, and sulfates such as magnesium sulfate and aluminum sulfate. These are used singly or in combination of two or more.
  • the above five methods may be used alone or in combination of two or more.
  • the saturated fatty acid, unsaturated fatty acid, alicyclic carboxylic acid, and resin used in the present invention are not particularly limited, but preferably have as many carbon violet numbers as possible. In this case, it is preferable that the number of carbon atoms is 8 or more because high thixotropy and slump resistance can be obtained in addition to storage stability.
  • saturated fatty acids such as cabrylic acid, lauric acid, myristic acid, balmitic acid, stearic acid, and arginic acid
  • unsaturated fatty acids such as oleic acid, elaidic acid, linoleic acid, and ricinoleic acid
  • fats such as naphthenic acid.
  • Resin acids such as cyclic carboxylic acid, abietic acid, pimaric acid, parastolic acid, and neo-vietic acid.
  • metal stones include metal stones such as Ag, Al, Ba, Ca, Cu, Fe, Mg, Mn, Pb, Sn, Sr, and Zn. These are used alone or in combination of two or more.
  • the surface treatment amount of the surface treatment agent in the present invention is not particularly limited, but is preferably in the range of 0.1 to 20.0 parts by weight with respect to 100 parts by weight of calcium carbonate. If the surface treatment halo is less than 0.1 part by weight, the surface treatment effect may not be sufficient, and if it exceeds 20.0 parts by weight, no further remarkable effect can be expected, which is economically disadvantageous. There are cases.
  • the effect of the present invention can be obtained as long as the content of the alkali metal according to the present invention is 1. OXI O-Smol Zl 100 gCaCOs or less. More demonstrated. Therefore, Al force Li alloy ⁇ content is preferably 7, 0 X 1 0 "' mol / 1 00 and the CaCO 3 or less, more preferably 5. 0 X 1 0 - 4 mol / 1 00 gCaCOa hereinafter with is there.
  • the calcium carbonate used in the present invention should be selected according to the desired properties of the resin composition, and is not particularly limited.
  • limestone is used as a raw material, and so-called heavy carbonated lime, which has a desired particle size by crushing and classification, and limestone are calcined once to produce quick lime, and carbon dioxide gas is added to a slaked lime water slurry prepared by hydration.
  • Precipitated calcium carbonate produced by conduction, a solution method carbonic acid solution produced by reacting a carbonate solution and a calcium salt solution can be selected as appropriate according to the purpose.For example, it is used for a curable resin composition.
  • the BET specific surface area is preferably 3 m 2 / g to 20 m 2 Zg, more preferably 5 m 2 / g to 10 Om 2 g of carbonic acid. Calcium is used.
  • the BET specific surface plant is less than 3 m 2 Zg, it is difficult to impart high viscosity, and when it exceeds 120 m 2 / g, it is necessary to increase the amount of the surface treatment agent to cover the hydrophilic surface. Therefore, it is expensive and not economically favorable. More preferably, precipitated calcium carbonate, which provides a higher BET specific surface area, is preferred.
  • the calcium carbonate is mechanically pulverized and classified, so that the calcium carbonate contains a small amount of alkali. Has a low water removal rate and therefore has a good water removal rate. Therefore, for example, when used in a curable composition, it is advantageous in terms of storage stability.
  • the surface-treated calcium carbonate tumuli of the present invention are particularly excellent in dispersibility.
  • Suitable for various resins For example, when used as a material for hardening type resin compositions such as sealing materials, adhesives, flooring materials, etc., they exhibit excellent thixotropy, slump resistance and excellent storage stability, and are used in paints, inks, etc. When used, they exhibit excellent gloss and water resistance, and when used plastically, they exhibit excellent mechanical strength and thermal stability. In such cases, they exhibit excellent anti-blocking properties and insulation properties, and are particularly effective when used in capacitor films and the like.
  • liquid resins such as polyurethane-based, polysulfide-based, silicone-based, modified silicone-based, and polyisobutylene-based liquids used for sealing materials are used.
  • Liquid resins such as urea, phenol, epoxy, silicone, and acrylic used for resins and adhesives, liquid resins such as eboxy, polyurethane, and polyester used for flooring, and paints Rosin used in liquid resins and inks such as phenolic, alkyd, unsaturated polyester, amino, ethoxy, vinyl, acrylic, polyurethane, silicone, and fluorine based resins System, phenol system, alkyd system, polyamide system, urethane system, epoxy system, polyester system, Thermosetting resins such as phenolic, urea-based, melamine-based, unsaturated polyester-based, epoxy-based, polyurethane-based and polyimid-based resins used in plastics such as liquid resins such as rill-based, vinyl chloride, and polyethylene-based And thermoplastic resins such as polypropylene-based, polystyrene-based, ABS-based, boronamide-based, polyacetal-based, polycarbonate-based, flu
  • the amount of the surface-treated calcium carbonate paint of the present invention to be mixed with the resin depends on the type of the resin. Although it depends on the type and application, for example, in the case of modified silicone, resin
  • fillers such as colloidal silica, talc, kaolin, zeolite, resin balloons, glass balloons, etc.
  • plasticizers such as dioctyl phthalate and dibutyl phthalate; aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as hexane and butane; gasoline and other petroleum solvents; acetone and methyl ethyl ketone Solvents such as ketones, ether esters such as cellosolve acetate, etc., for example, additives such as silicone oil, fatty acid ester-modified silicone oil, etc., and, if necessary, one or more of various additives, coloring agents, etc. Two or more can be added in combination.
  • the curing rate of the curable composition is adjusted by using the substance in combination with a conventionally used tongue.
  • the moisture-curable resin composition comprises a fatty acid ester, and a compound represented by the general formula (1) having a melting point of 50 or more, carboxylic acid, sulfonic acid, and a metal salt thereof.
  • Calcium carbonate or the like, which is surface-treated with at least one selected from the group, is used.
  • the combination ratio of the surface-treated calcium carbonate of the present invention and the conventionally used surface-treated calcium carbonate is not particularly limited, and the ratio is appropriately varied so as to obtain a desired curing time. Just do it.
  • the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these.
  • Example 1 was the same as Example 1 except that stearic acid was changed to lauric acid (melting point: 44 ° C) and 75 ° C to 50.
  • Example 3 80 g of stearic acid was added to 10 kg of an aqueous slurry of precipitated calcium carbonate having a BET specific surface area of 20 m 2 / g adjusted to a concentration of 160 g CaCO s / kg and a temperature of 75 e C. After adding 104.2 g of a 10% by weight calcium hydroxide slurry, the mixture was stirred for 5 hours to perform a surface treatment. Thereafter, the solid content was dehydrated, dried and pulverized to a solid content of 60% to obtain a carbonated calcium powder having calcium stearate surface-treated.
  • Example 5 Calcium carbonate powder surface-treated with calcium stearate in the same manner as in Example 3 except that the calcium hydroxide slurry having a concentration of 10% by weight was changed from 104.2 g to 105.8 g of calcium oxide in Example 3. I got Example 5
  • Example 3 was the same as Example 3 except that stearic acid was changed to lauric acid, 75 and 50 were changed to 50, and the added amount of calcium hydroxide slurry was changed to 104 and 2 g to 148 g. Thus, calcium carbonate powder surface-treated with calcium laurate was obtained.
  • Example 6 magnesium stearate was changed to magnesium laurate (melting point: 15 O'C), and 140 to 160. Same as Example 5 except for changing to C
  • the obtained fluorescent X-line analysis apparatus for calcium carbonate (manufactured by Shimadzu Corporation: XRF-1500) Quantitatively the potassium in, were 5, 2 10 "4 ⁇ 1 / 100gCaC0 3.
  • Example 8 was the same as Example 8 except that the dilution with water of 5 times while stirring was changed to 2 times.
  • the amount of potassium in the obtained calcium carbonate surface-treated with calcium stearate was determined by a fluorescent X-ray diffractometer (XRF-00, manufactured by Shimadzu Corporation) to find that it was 8.5 ⁇ 10 ′′ ′′ mol / 10 OgCaCOs.
  • Example 8 was the same as Example 8 except that 800 g of a hot aqueous solution of potassium stearate at a concentration of 10% by weight was changed to 800 g of a hot aqueous solution of potassium aviate acid at a concentration of 10% by weight. did. Quantitative determination of potassium in the resulting calcium carbonate surface-treated with calcium abietic acid using a fluorescent X-ray analyzer (XRF-1500, manufactured by Shimadzu Corporation) gave 5.0 X10 mol / lOOgCaCOa.
  • XRF-1500 fluorescent X-ray analyzer
  • Example 2 8 kg of the precipitated calcium carbonate powder powdered without surface treatment in Example 1 was mixed with 20 liters of a 20-liter supermixer (Kawada SMV-20 type, stirring blade: S type and BL type). Used), heated to 90, charged with 400 g of stearic acid, mixed at 2000 rpm for 30 minutes, surface-treated in a dry system, and dry-treated calcium carbonate with stearic acid. A powder was obtained.
  • Example 1 except that the slurry temperature was changed from 75 ° C to 5 O'C in Example 1. Same as.
  • Example 3 was the same as Example 3 except that the concentration of 10 wt. Calcium hydroxide slurry 104.2 g was changed to 10 wt. did.
  • Example 6 was the same as Example 6 except that the heat treatment at 140 and 1 hour was changed to 1 hour and the heat treatment at 120 was changed to 1 hour.
  • Example 8 was the same as Example 8 except that water dilution 5 times was changed to no water dilution. Quantitative determination of potassium in the obtained calcium carbonate using a fluorescent X-ray analyzer was 2.0 xiCT 3 ino 1 ZlOOgCaCC. Comparative Example 6
  • Example 1 was the same as Example 1 except that stearic acid was changed to sodium stearate. Quantitative determination of sodium in the obtained calcium carbonate using a fluorescent X-ray analyzer revealed that 2,2xlO-'mo1 / lOOgCa
  • Example 1 was the same as Example 1 except that stearic acid was changed to sodium laurate.
  • Example 10 was the same as Example 10 except that the 5-fold dilution with water was carried out while stirring in Example 10. When attached to the resulting calcium carbonate to quantify the potassium by the fluorescent X-ray analyzer, 2. 1 xl0- 3 mo It was 1 / 100gCaC0 3.
  • Example 11 was the same as Example 11 except that the 5-fold dilution with water was performed without stirring, while stirring.
  • the amount of potassium in the obtained calcium carbonate was determined by a fluorescent X-ray analyzer, and was found to be 1.g x io- ⁇ mo1 / lOOgCaCOa.
  • Example 1 was the same as Example 1 except that stearic acid was changed to stearyl glycerol ester.
  • the above compound was kneaded with a small kneader to prepare a sealing material.
  • the kneaded sealing material was packed in a cylindrical cartridge for a one-component sealing material and sealed.
  • a B8 U-type viscometer was used (rotor No. 7).
  • the state of the vertical construction was visually determined based on the following criteria.
  • composition containing the surface-treated calcium carbonate of the present invention is very excellent in storage stability, thixotropy and slump resistance ⁇
  • the above compound was kneaded with a small kneader to prepare a sealing material.
  • the kneaded sealing material was packed in a cylindrical cartridge for one-component sealing material and sealed.
  • Evaluation was made based on the temperatures measured immediately after kneading (2 O'C X 1 day) and after aging (in an oven at 40 ° C. for 2 weeks).
  • a B8 U-type densitometer was used (rotor No. 7).
  • the sealing material was extruded from the force cartridge, and the time required for the sealing material to cure with 2 O'C until it did not adhere to the finger was measured.
  • Example 36 Sample of Example 4 1 20 parts by weight 2.5
  • Example 37 80 parts by weight of sample of 3 + specific ratio 40 parts by weight of TO of Example 10 3.5
  • Example 38 60 parts by weight of Example 3 + Ratio 60% by weight of sample of Example 10 5.5
  • Example 40 80 parts by weight of the sample of Example 4 + Comparative Example 11 40 parts by weight of the sample of 1 4.0
  • Example 4 60 parts by weight of 1 m4 sample + 60 parts by weight of sample of Example 11
  • Example 42 Sample of Example 4 40 weights + Specific squeezing example 1 1 (DU 80 parts by weight 8.0 Comparative example 34 Comparative example 10 1 TO 20 parts by weight 9.0
  • composition containing the surface-treated calcium carbonate of the present invention is very excellent in storage stability, thixotropy and slump resistance.
  • the surface-treated calcium carbonate of the present invention is used in a moisture-curable composition by using it together with a surface-treated calcium carbonate conventionally used in a moisture-curable composition. It can be seen that the disadvantage of long curing time, which was a disadvantage of surface-treated carbonated rubber, can be improved and shortened.
  • PVC resin S-1001 manufactured by Nippon Vinyl Co., Ltd. 100 parts by weight DOP 50 parts by weight Tribase (TS-100 manufactured by Kikuchi Pigment Co., Ltd.) 3 parts by weight Lead stearate (NS— 100 Kikuchi Dye Co., Ltd.) 1 part by weight Sample Surface treated calcium carbonate pigment 50 parts by weight
  • the above composition is kneaded with a roll at a temperature of 165'C for 6 minutes and taken out as a 2 mm thick sheet.
  • the obtained sheet was sandwiched between two hues, and the result was 170.
  • pressurize at 7.8 MPa (8 O kg / cm 2 ) for 3 minutes.
  • the sheet is taken out after the pressure of the hue plate is allowed to cool.
  • the thickness shall be 1 mm.
  • the surface of the obtained sheet was visually determined according to the following criteria.
  • composition containing the surface-treated calcium carbonate of the present invention is very excellent in dispersibility and insulating properties.
  • Example 10 and Comparative Example 8 were kneaded with sandmill in the following composition to prepare a water-based ink resin composition, and the effects were evaluated by the following test methods. Table 5 shows the results.
  • Each water-based printing ink composition was spread on a coated paper, Rengo I CRC (manufactured by Rengo I) using a hand bull fur.
  • Rengo I CRC manufactured by Rengo I
  • a Gakushin-type dyed color rub fastness tester manufactured by Daiei Kagaku Seiki Seisakusho Co., Ltd.
  • the developed color was applied with a cloth moistened with water and a load of 2, ON (200 g). It was rubbed 5 times below, and evaluated based on how the ink was absorbed into the cloth.
  • composition containing the surface-treated calcium carbonate of the present invention is very excellent in water resistance.
  • Alkyd resin (Bekkosol P-470-70, manufactured by Dainippon Ink and Chemicals, Inc.)
  • Titanium oxide (Taibe R-820, manufactured by Ishihara Sangyo) 120 parts by weight Heavy calcium carbonate (Super SS S, manufactured by Maruo Calcium Co., Ltd.)
  • Each alkyd paint composition was applied to a glass plate on one side at 4 mi 1 s abrique overnight, dried at room temperature for 24 hours, and measured at 60 ° gloss using a Murakami gloss meter. Thereafter, the glass plate was immersed in water, and the gloss retention after 3 days was evaluated.
  • Example 6 "gloss 60 ⁇ (%) Room 55
  • Example 1 87. 8 86. 1 98. 1 Room 1 i 6 ⁇
  • Example 2 8 6.9 B 5.5 5 98. 4 Room 57 ⁇
  • Example 3 9 1.2 90.7 99.5
  • Example 5 Example 4 92.3 92.2 99.9
  • Example 59 9 i. 7 9 1.3 99.6
  • Example 60 Example 6 92.1 9 1.5 99.3
  • Example 3 Example 9 90. 9 8 9.1 98.0 Room puncture R 4 ⁇ Example 1 1 90.5 8 9.8 99.2 Room rent R Treasure Example 1 9 7 9 8 79.3 99.3 Example 45 Example 1 78.1 65.9 84.4 Reference example 46 Example 2 76.6 63.5 82.9 Comparative example 47 Example 3 75.4 67.7 89 8 8 7 4 7 8 5 8 7 8 9 5 5 66.6 7 7. 5 8 9 5 Comparison ⁇ 50 Example 6 85. 4 77.2 90 4 Comparative example 5 1 Implementation 8 3.8 72. 9 87.0 Comparative example 52 Example 9 7 4. 4 62. 9 84.5
  • the surface-treated calcium carbonate clay of the present invention is particularly suitable as a resin lantern.
  • the surface-treated calcium carbonate clay when used in a curable resin composition, has excellent heat resistance when dried, and has excellent thixotropic properties. And provides excellent slump resistance and good storage stability.For example, when used for plastics, it exhibits excellent dispersibility and insulation properties.For example, when used for paints and inks, it is excellent. Demonstrates water resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Charge de carbonate de calcium traitée en surface, caractérisée en ce que la surface a été traitée par voie humide avec au moins un élément choisi dans le groupe comprenant les acides gras saturés, les acides gras insaturés, les acides carboxyliques alicycliques et les acides résiniques. La charge convient notamment pour les résines. Quand elle est contenue dans une composition de résine durcissable, elle ne confère pas seulement une excellente résistance à la chaleur à l'état sec, mais aussi d'excellentes propriétés thixotropiques, une excellente résistance à l'affaissement et une stabilité satisfaisante au stockage. Quand elle est utilisée dans un plastique, elle possède une excellente dispersibilité et confère d'excellentes propriétés d'isolation, etc. Quand elle est utilisée dans un matériau de revêtement ou de l'encre, elle confère une excellente résistance à l'eau, etc.
PCT/JP1999/006568 1999-04-09 1999-11-25 Charge de carbonate de calcium traitee en surface, procede permettant de la produire et composition de resine la contenant WO2000061690A1 (fr)

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JP10213099A JP3151196B2 (ja) 1998-04-10 1999-04-09 表面処理炭酸カルシウム填料、その製造方法、並びに該填料を配合してなる樹脂組成物
JP11/102130 1999-04-09

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CN116656158B (zh) * 2023-04-04 2024-10-18 仲恺农业工程学院 一种超疏水疏油涂料溶液及其制备方法和应用
KR102643134B1 (ko) * 2023-08-09 2024-03-05 주식회사 유로드 일반 차선 및 돌출형 차선 도장용 상온경화형 노면표지 도료 조성물 및 이를 이용한 노면표지 도료의 시공방법

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US8324301B2 (en) 2004-12-22 2012-12-04 Solvay (Société Anonyme) Acid resistant particles of an alkaline earth metal carbonate
CN116925573A (zh) * 2023-07-20 2023-10-24 浙江钦堂钙业有限公司 活化改性重质碳酸钙及其制备方法
CN116925573B (zh) * 2023-07-20 2024-04-05 浙江钦堂钙业有限公司 活化改性重质碳酸钙及其制备方法

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CN1506409A (zh) 2004-06-23
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