WO2012173114A1 - 含浸処理炭酸カルシウム、その製造方法、ポリマー組成物及びポリマー前駆体組成物 - Google Patents
含浸処理炭酸カルシウム、その製造方法、ポリマー組成物及びポリマー前駆体組成物 Download PDFInfo
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/18—Carbonates
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- 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
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
Definitions
- the present invention relates to impregnated calcium carbonate, a production method thereof, a polymer composition containing impregnated calcium carbonate, and a polymer precursor composition.
- calcium carbonate is blended with a polymer for the purpose of imparting various properties to a polymer composition such as a resin or rubber.
- a polymer composition such as a resin or rubber.
- fine calcium carbonate having a BET specific surface area of about 10 to 40 m 2 / g may be used.
- Patent Document 1 discloses that calcium carbonate having a BET specific surface area of 10 m 2 / g or more surface-treated with a fatty acid salt is blended in a resin or the like.
- the main object of the present invention is to provide an impregnated calcium carbonate that is difficult to disperse and has excellent dispersibility in a polymer composition, a method for producing the impregnated calcium carbonate, a polymer composition containing the impregnated calcium carbonate, and a polymer precursor composition.
- the impregnated calcium carbonate of the present invention is obtained by impregnating a surface-treated calcium carbonate obtained by surface-treating calcium carbonate with at least one of a fatty acid, a resin acid and a derivative thereof with a liquid organic compound at room temperature.
- the impregnation amount of the organic compound that is liquid at room temperature is 3 to 22 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the impregnated calcium carbonate of the present invention is impregnated with 3 parts by weight or more of a liquid organic compound at room temperature with respect to 100 parts by weight of the surface-treated calcium carbonate, it is difficult to scatter. Therefore, the impregnated calcium carbonate of the present invention is easy to handle.
- the impregnated calcium carbonate of the present invention is impregnated with 3 to 22 parts by weight of an organic compound that is liquid at room temperature with respect to 100 parts by weight of the surface-treated calcium carbonate. Dispersed quickly and uniformly in polymers.
- impregnation refers to impregnating the surface-treated calcium carbonate particles with a liquid organic compound at room temperature.
- the organic compound that is liquid at room temperature is preferably at least one of a plasticizer, an oil agent, and polypropylene glycols.
- examples of the oil agent include mineral oil, synthetic oil, vegetable oil and the like.
- the calcium carbonate is preferably synthetic calcium carbonate.
- the average particle diameter of the surface-treated calcium carbonate is preferably 20 nm to 200 nm.
- the BET specific surface area of the surface-treated calcium carbonate is preferably 10 m 2 / g to 100 m 2 / g.
- the treatment amount of at least one of fatty acid, resin acid and derivatives thereof with respect to calcium carbonate is preferably 2 to 15 parts by weight with respect to 100 parts by weight of calcium carbonate.
- the polymer composition of the present invention contains a polymer and impregnated calcium carbonate.
- the impregnated calcium carbonate is uniformly dispersed in the polymer composition. Therefore, the polymer composition of the present invention can be suitably used for various applications.
- the polymer precursor composition of the present invention includes a polymer precursor and impregnated calcium carbonate.
- the impregnated calcium carbonate is uniformly dispersed in the polymer precursor composition. Therefore, the polymer precursor composition of the present invention can be suitably used for various applications.
- the method for producing impregnated calcium carbonate of the present invention comprises a step of surface-treating calcium carbonate with at least one of fatty acids, resin acids and derivatives thereof to obtain surface-treated calcium carbonate, and an organic compound that is liquid at room temperature, A step of impregnating 3 to 22 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the present invention it is possible to provide impregnated calcium carbonate that is difficult to scatter and has excellent dispersibility in a polymer composition or a polymer precursor composition.
- FIG. 1 is a schematic diagram of a powder tester used for scattering evaluation in Examples 1 to 4 and Comparative Examples 1 to 3.
- FIG. 2 is a graph showing the relationship between dispersibility and kneading time in Examples 1 to 4 and Comparative Examples 1 to 3.
- FIG. 3 is a graph showing the time required to reach the degree of dispersion A in Examples 1 to 4 and Comparative Examples 1 to 3.
- FIG. 4 is a graph showing the relationship between dispersibility and kneading time in Example 5 and Example 6.
- FIG. 5 is a graph showing the time until the degree of dispersion A is reached in Example 5 and Example 6.
- FIG. 6 is a graph showing the relationship between dispersibility and kneading time in Example 7 and Comparative Example 4.
- FIG. 7 is a graph showing the relationship between dispersibility and kneading time in Example 8 and Comparative Example 5.
- FIG. 8 is a graph showing the relationship between dispersibility and kneading time in Example 9
- the impregnated calcium carbonate is obtained by impregnating calcium carbonate formed by surface-treating calcium carbonate with at least one of fatty acid, resin acid and derivatives thereof at room temperature.
- the calcium carbonate constituting the impregnated calcium carbonate is not particularly limited.
- conventionally known calcium carbonate can be used.
- Specific examples of calcium carbonate include synthetic calcium carbonate and natural calcium carbonate (heavy calcium carbonate).
- the calcium carbonate is preferably synthetic calcium carbonate.
- Synthetic calcium carbonate is not particularly limited.
- Examples of the synthetic calcium carbonate include precipitated (collaged) calcium carbonate and light calcium carbonate.
- Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide.
- Calcium hydroxide can be produced, for example, by reacting calcium oxide with water.
- Calcium oxide can be produced, for example, by co-firing raw limestone with coke. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.
- Natural calcium carbonate is obtained by pulverizing naturally produced calcium carbonate ore by a known method.
- Examples of the method for pulverizing the raw calcium carbonate include a roller mill, a high-speed rotation mill (impact shear mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, and a jet mill.
- the average particle size of calcium carbonate is usually about 20 nm to 200 nm, preferably about 20 nm to 150 nm, and more preferably about 30 nm to 100 nm.
- the average particle size of calcium carbonate is a value measured by image analysis using a transmission electron microscope.
- Fatty acids, resin acids and their derivatives are not particularly limited. Examples of fatty acids and derivatives thereof include fatty acids, metal salts thereof, and esterified products thereof.
- fatty acid examples include saturated or unsaturated fatty acids having 6 to 31 carbon atoms.
- saturated fatty acids include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, Examples include melicic acid. Among these, palmitic acid, stearic acid, and lauric acid are preferably used.
- Unsaturated fatty acids include obsilic acid, carloleic acid, undecylenic acid, Linderic acid, tuzuic acid, fizeteric acid, molistoleic acid, palmitoleic acid, petrothelic acid, oleic acid, elaidic acid, asclebic acid, vaccenic acid , Gadoleic acid, gondoic acid, cetreic acid, erucic acid, brassic acid, ceracoleic acid, ximenoic acid, lumectric acid, sorbic acid, linoleic acid and the like.
- fatty acid metal salts examples include alkali metal salts such as sodium salts and potassium salts of the above fatty acids, and alkaline earth metal salts such as magnesium salts and calcium salts. Among these, alkali metal salts such as sodium salts and potassium salts of the above fatty acids are preferable.
- esterified fatty acid examples include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate and the like.
- More preferable fatty acids and derivatives thereof include sodium salts and potassium salts of saturated fatty acids having 9 to 21 carbon atoms.
- sodium palmitate, sodium stearate, and sodium laurate are particularly preferable.
- Resin acid and its derivatives are not particularly limited. Examples of the resin acid and derivatives thereof include resin acid, metal salts thereof, and other derivatives.
- resin acid examples include abietic acid, pimaric acid, repopimaric acid, neoabietic acid, pulpstriic acid, dehydroapitic acid, dihydroabietic acid, tetraabietic acid, dextropimaric acid, isodextropimaric acid and the like. It is done.
- metal salt of the resin acid examples include alkali metal salts such as sodium salt and potassium salt of the above resin acid, and alkaline earth metal salts such as magnesium salt and calcium salt.
- examples of the resin acid derivative include hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin ester, maleated rosin, maleated rosin ester, and rosin-modified phenol.
- Preferred resin acids and derivatives thereof include abietic acid, neoabietic acid, dehydroabietic acid, tetraabietic acid, pimaric acid, dextropimaric acid, hydrogenated rosin, disproportionated rosin, and maleated rosin.
- the treatment amount of at least one of fatty acid, resin acid and derivatives thereof with respect to calcium carbonate is usually about 2 to 15 parts by weight and about 2 to 10 parts by weight with respect to 100 parts by weight of calcium carbonate. It is preferably about 2.5 to 5 parts by weight. If the treatment amount of at least one of fatty acid, resin acid and derivatives thereof relative to calcium carbonate is too small, the surface-treated calcium carbonate tends to aggregate, which is not preferable. On the other hand, if the amount of at least one of fatty acid, resin acid and derivatives thereof is too large, an effect proportional to the surface treatment amount cannot be obtained and the cost is increased, which is not preferable because it is economically disadvantageous.
- the adhesion amount of at least one of fatty acid, resin acid and derivatives thereof to 100 parts by weight of calcium carbonate is usually about 1.6 parts by weight to 14.9 parts by weight, and 1.6 parts by weight to 9.9 parts by weight.
- the amount is preferably about parts by weight, more preferably about 2.0 parts by weight to 4.9 parts by weight.
- Organic compounds that are liquid at room temperature is not particularly limited.
- the liquid at normal temperature means a liquid at 25 ° C. under 1 atm.
- the average molecular weight of an organic compound that is liquid at room temperature is usually about 30 to 6000 g / mol.
- the viscosity of the organic compound that is liquid at room temperature is preferably about 5 mPa ⁇ s / 20 ° C. to 3500 mPa ⁇ s / 20 ° C.
- the plasticizer is not particularly limited.
- a plasticizer the well-known plasticizer added to polymer compositions, such as resin and rubber
- the plasticizer phthalic acid plasticizers, polyester plasticizers, sulfonic acid plasticizers, phosphoric acid plasticizers and the like are preferable.
- the phthalic acid plasticizer include di-2-ethylhexyl phthalate (DOP), dimethyl phthalate (DMP), diisononyl phthalate (DlNP), diptyl phthalate (DBP), diisodecyl phthalate (DlDP), and the like. It is done.
- Specific examples of the polyester plasticizer include propyl polyadipate and propyl sebacate.
- sulfonic acid plasticizer examples include benzenesulfonic acid butyramide.
- phosphate plasticizer examples include tricresyl phosphate, trioctyl phosphate, and triphenyl phosphate.
- oil agent examples include mineral oil, synthetic oil, and vegetable oil.
- Mineral oil is a heavy oil obtained in the process of producing crude oil.
- Mineral oil is not particularly limited.
- the viscosity of the mineral oil is preferably about 5 mPa ⁇ s / 20 ° C. to 3500 mPa ⁇ s / 20 ° C., more preferably about 10 mPa ⁇ s / 20 ° C. to 1000 mPa ⁇ s / 20 ° C.
- the mineral oil is preferably at least one selected from the group consisting of paraffinic mineral oil, naphthenic mineral oil and aromatic mineral oil, more preferably paraffinic mineral oil or naphthenic mineral oil. More preferably, it is a naphthenic mineral oil.
- Paraffinic mineral oils include those used as process oils. Specific examples of paraffinic mineral oil include Diana Process Oil PW-32, PW-90, PW-380, PS-32, PS-90, PS-430 (all trade names) manufactured by Idemitsu Kosan Co., Ltd. Can be mentioned.
- naphthenic mineral oils include those used as process oils.
- Specific examples of the naphthenic mineral oil include Diana Process Oil NS-24, NS-100, NR-68, NM-26, NM-280, NP-24 manufactured by Idemitsu Kosan Co., Ltd.
- Aromatic mineral oils include those used as process oils. Specific examples of the aromatic mineral oil include Diana Process Oil AC-12, AC460, AH-16, AH-24 manufactured by Idemitsu Kosan Co., Ltd.
- Synthetic oil is not particularly limited. Synthetic oils include chemically synthesized oils such as polyalphaolefins and polyol esters.
- Plant oils include castor oil, soybean oil, rapeseed oil, corn oil, safflower oil, rice oil, cottonseed oil, sesame oil, peanut oil, olive oil, palm oil and the like.
- the amount of impregnation of the surface-treated calcium carbonate with an organic compound that is liquid at room temperature is about 3 to 22 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the impregnation amount of the organic compound that is liquid at room temperature is preferably about 5 to 20 parts by weight, and more preferably about 5 to 15 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate. That is, the adhesion amount of the organic compound that is liquid at normal temperature to the surface-treated calcium carbonate is usually about 3 to 22 parts by weight and about 5 to 20 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the amount is preferably about 5 to 15 parts by weight.
- the amount of impregnation of the organic compound that is liquid at room temperature is not affected by the average particle diameter of the surface-treated calcium carbonate, the BET specific surface area, the amount of fatty acid surface treatment, and the like.
- the impregnated calcium carbonate is obtained by impregnating a surface-treated calcium carbonate obtained by surface-treating calcium carbonate with at least one of fatty acid, resin acid and derivatives thereof with an organic compound that is liquid at room temperature.
- the method for producing impregnated calcium carbonate includes a surface treatment step of surface-treating calcium carbonate with at least one of fatty acid, resin acid and derivatives thereof to obtain surface-treated calcium carbonate, and an organic compound that is liquid at room temperature.
- the method for surface-treating calcium carbonate with at least one of fatty acids, resin acids and derivatives thereof is not particularly limited.
- a method of adding a fatty acid, a resin acid and at least one of these derivatives to a slurry containing calcium carbonate and water, followed by dehydration and drying can be employed.
- the following method is mentioned as a specific method of surface-treating calcium carbonate with an alkali metal salt of a fatty acid.
- the fatty acid is saponified while being heated in an alkali metal aqueous solution such as NaOH aqueous solution or KOH aqueous solution to obtain an alkali metal aqueous solution of fatty acid.
- an alkali metal aqueous solution of a fatty acid is added to a slurry of calcium carbonate and water and stirred. Thereby, the surface of calcium carbonate can be surface-treated with a fatty acid.
- the solid content of calcium carbonate in the slurry of calcium carbonate and water can be adjusted as appropriate in consideration of the average particle diameter of calcium carbonate, the dispersibility of the calcium carbonate in the slurry, the ease of slurry dehydration, etc. Good. In general, by adjusting the solid content of the slurry to about 2 to 30% by weight, preferably about 5 to 20% by weight, a slurry with an appropriate viscosity can be obtained.
- the slurry may be dehydrated by a method such as a filter press. Further, the drying may be performed by, for example, a box type dryer.
- the surface of calcium carbonate can be treated with a fatty acid without saponifying the fatty acid into a metal salt of the fatty acid.
- the surface of calcium carbonate can be treated with a fatty acid by stirring the calcium carbonate while heating it to a temperature equal to or higher than the melting point of the fatty acid, adding the fatty acid thereto, and stirring.
- the surface of calcium carbonate can be treated with the fatty acid ester by adding the fatty acid ester thereto while stirring the calcium carbonate while heating it above the melting point of the fatty acid ester.
- the BET specific surface area of the surface-treated calcium carbonate is usually about 10 m 2 / g to 100 m 2 / g, preferably about 10 m 2 / g to 60 m 2 / g, and about 15 m 2 / g to 40 m 2 / g. It is more preferable that
- the average particle diameter of the surface-treated calcium carbonate is usually about 20 nm to 200 nm, preferably about 20 nm to 150 nm, more preferably about 30 nm to 100 nm.
- the average particle diameter of the surface-treated calcium carbonate is a value measured by image analysis using a transmission electron microscope.
- the method for impregnating the surface-treated calcium carbonate with a liquid organic compound at room temperature is not particularly limited.
- impregnated calcium carbonate is obtained by mixing surface-treated calcium carbonate and an organic compound that is liquid at room temperature.
- a specific example of the impregnation treatment there may be mentioned a method of spraying a liquid organic compound at normal temperature onto the dried surface-treated calcium carbonate, followed by stirring.
- the stirring method is not particularly limited, and stirring may be performed using, for example, a mixer or a super mixer.
- the temperature at which the surface-treated calcium carbonate and the liquid organic compound are mixed at normal temperature is not particularly limited. For example, what is necessary is just to mix under room temperature (25 degreeC).
- the mixing time is usually about 0.1 seconds to 10 minutes.
- the polymer composition includes a polymer and impregnated calcium carbonate.
- Examples of the polymer composition include a resin composition and a rubber composition.
- the polymer contained in the polymer composition is not particularly limited. Examples of the polymer include resin and rubber.
- the resin contained in the resin composition is not particularly limited.
- the resin include known resins such as polyvinyl chloride resin, polyurethane resin, modified silicone resin, polysulfide resin, acrylic resin, silicone resin, and polypropylene glycols.
- the resin composition may further contain a resin plasticizer, a filler, a crosslinking agent, and other additives as necessary.
- the resin plasticizer, filler, cross-linking agent, and other additives may be composed of only one type or may be composed of a plurality of types.
- the resin plasticizer examples include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate ( DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butylbenzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA) Diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl se
- fillers include inorganic fillers and organic fillers.
- inorganic fillers include calcium carbonate (natural products and synthetic products) other than calcium carbonate used in the impregnated calcium carbonate of the present invention (natural products and synthetic products), calcium magnesium carbonate (natural products and synthetic products), and basic properties.
- organic fillers examples include powders such as wood powder, walnut powder, cork powder, wheat flour, starch, ebonite powder, rubber powder, lignin, phenol resin, high styrene resin, polyethylene resin, silicon resin, urea resin, or Examples include beads, cellulose powder, pulp powder, synthetic fiber powder, amide wax, and castor oil wax.
- the resin composition is obtained by mixing a resin, impregnated calcium carbonate, and, if necessary, a resin plasticizer, a filler, a crosslinking agent, and other additives.
- a resin plasticizer e.g., ethylene glycol dimethacrylate
- a filler e.g., polyethylene glycol dimethacrylate
- a crosslinking agent e.g., polyethylene glycol dimethacrylate
- other additives e.g., polyst copolymer, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, polyurethane, poly
- the rubber contained in the rubber composition is not particularly limited. Examples of the rubber include natural rubber and synthetic rubber.
- Natural rubber is a rubbery polymer obtained from natural plants. As long as the natural rubber has a cis-1,4-polyisoprene structure, the shape, color tone and the like are not particularly limited.
- Synthetic rubbers include, for example, isoprene rubber, styrene butadiene rubber, butadiene rubber, chloroprene rubber, acrylonitrile butadiene rubber, butyl rubber, halogenated butyl rubber, ethylene propylene rubber, urethane rubber, silicone rubber, fluorine rubber, chlorosulfonated polyethylene, epichlorohydride. Rubber, polysulfide rubber and the like.
- the rubber may be a latex mainly composed of rubber.
- the rubber composition may contain various commonly used rubber compounding agents.
- rubber compounding agents include carbon black, silica, clay, other fillers such as calcium carbonate, silane coupling agents, vulcanization accelerators, activators, oils, zinc white, stearic acid, softeners, and aging.
- examples thereof include additives such as inhibitors, retarders, and vulcanizing agents such as sulfur vulcanization accelerators.
- vulcanization accelerator examples include thiazoles such as di-2-benzothiazolyl disulfide (DM) and 2-mercaptobenzothiazole (M), N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), Sulfenamides such as N-tert-butyl-2-benzothiazolylsulfenamide (NS) and N, N-dicyclohexyl-2-benzothiazole sulfenamide (DZ), tetramethylthiuram monosulfide (TS), Examples thereof include thiuram compounds such as tetramethylthiuram disulfide (TT), thiocarbamic acid compounds such as zinc dimethylthiocarbamate (PZ), and xanthate salt vulcanization accelerators such as zinc isopropylxanthate (ZIX).
- thiazoles such as di-2-benzothiazolyl disulfide (DM) and 2-mercaptobenzothiazo
- the rubber composition can be produced by mixing rubber and impregnated calcium carbonate.
- Examples of the method of mixing the rubber and impregnated calcium carbonate include a Banbury mixer, a pressure kneader, a closed kneader such as an intermix, a method of mixing the impregnated calcium carbonate while kneading the rubber with an open roll or the like. It is done.
- the content of the impregnated calcium carbonate in the polymer composition is usually about 10 to 400 parts by weight and preferably about 10 to 300 parts by weight with respect to 100 parts by weight of the polymer composition.
- the polymer precursor composition includes a polymer precursor and impregnated calcium carbonate.
- the polymer precursor composition include a composition containing the above resin precursor, a composition containing the above rubber precursor, and the like.
- the polymer precursor composition may further contain the same resin plasticizer, filler, cross-linking agent, other additives, various rubber compounding agents and the like as described above, if necessary.
- the content of the impregnated calcium carbonate in the polymer precursor composition is usually about 10 parts by weight to 400 parts by weight and about 10 parts by weight to 300 parts by weight with respect to 100 parts by weight of the polymer precursor composition. It is preferable.
- the impregnated calcium carbonate of the present invention is excellent in dispersibility with respect to the polymer composition and the polymer precursor composition, it is suitable as a compounding agent for inks, paints, sealing materials, PVC sols, acrylic sols, resins, rubbers and the like. Can be used.
- the resin composition and the resin precursor composition of the present invention can be suitably used as a sealant material, PVC sol, acrylic sol, adhesive, and the like.
- the rubber composition and rubber precursor composition of the present invention can be suitably used as vibration-proof rubber, packing, weather strip, hose, gasket, O-ring, and the like.
- the value of BET specific surface area is about 10 to 40 m 2 / g, and the average particle size is several tens of nm to several hundreds. Mixing fine calcium carbonate of about nm is performed.
- the impregnated calcium carbonate of the present invention is impregnated with 3 to 22 parts by weight of an organic compound that is liquid at room temperature with respect to 100 parts by weight of the surface-treated calcium carbonate. Thereby, even if the average particle diameter of the surface-treated calcium carbonate is very fine, for example, about 20 nm to 200 nm, it is difficult to be scattered and easy to handle.
- the impregnated calcium carbonate of the present invention is very excellent in terms of dispersibility in a polymer composition such as a resin and rubber and a polymer precursor composition.
- the impregnated calcium carbonate of the present invention has a very short time until it becomes uniform when mixed with a polymer such as a resin or rubber, or a polymer precursor.
- the impregnated calcium carbonate of the present invention is uniformly dispersed very quickly even when mixed with a resin plasticizer or the like. Therefore, the impregnated calcium carbonate of the present invention can be easily mixed with a polymer or a polymer precursor to form a polymer composition or a polymer precursor composition.
- the impregnated calcium carbonate is uniformly dispersed. Therefore, the polymer composition of the present invention can be suitably used for various applications.
- inorganic particles such as calcium oxide and calcium hydroxide may be impregnated with a liquid organic compound at room temperature to obtain impregnated inorganic particles.
- Such impregnated inorganic particles are also excellent in dispersibility in the polymer composition and the polymer precursor composition. Further, even if the impregnated inorganic particles are very fine, for example, about 20 nm to 200 nm, they are difficult to scatter and are easy to handle.
- Example 1 Warm water was added to 2 kg of synthetic calcium carbonate having a BET specific surface area of 20 m 2 / g so that the solid content would be 10% by weight, and a calcium carbonate slurry solution was prepared using a stirring type disperser. While stirring the slurry with a disperser, 60 g of sodium stearate was added and further stirred for 5 minutes. Next, the obtained slurry was dehydrated by a filter press, dried by a box dryer, and powdered to obtain about 2 kg of surface-treated calcium carbonate whose surface was treated with sodium stearate.
- a powder tester PT-D manufactured by Hosokawa Micron Corporation was used for the evaluation of scattering properties. As shown in FIG. 1, using a powder tester 1, a circular watch glass 4 (radius 5 cm) is provided below a glass cylinder 2 (radius 5 cm, length 35 cm), and a circular sample table 3 (radius 2. 10 g of sample 5 (impregnated calcium carbonate) was naturally dropped from 5 cm). The distance from the lower part of the sample stage 3 to the upper part of the glass cylinder was 16 cm, and the distance from the lower part of the glass cylinder 2 to the watch glass 4 was 11 cm. Scatterability (dispersion degree) was evaluated based on the value obtained by the following equation. The results are shown in Table 1 below.
- Example 2 Impregnated calcium carbonate was obtained in the same manner as in Example 1 except that the amount of Diana Process Oil NP-24 (trade name) was 10 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the scattering property (dispersion degree) of the impregnated calcium carbonate obtained in Example 2 was evaluated. The results are shown in Table 1 below.
- a resin paste was prepared by mixing the impregnated calcium carbonate obtained in Example 2 and a resin, and the dispersibility of the impregnated calcium carbonate in the obtained resin paste was adjusted. evaluated.
- Table 2 shows the ratio of the amount of each component contained in the resin paste to which the impregnated calcium carbonate was added. The evaluation results of dispersibility are shown in Table 4, FIG. 2 and FIG.
- Example 3 Impregnated calcium carbonate was obtained in the same manner as in Example 1, except that the amount of Diana Process Oil NP-24 (trade name) was 14 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate.
- the scattering property (dispersion degree) of the impregnated calcium carbonate obtained in Example 3 was evaluated. The results are shown in Table 1 below.
- the impregnated calcium carbonate obtained in Example 3 and a resin were mixed to prepare a resin paste, and the dispersibility of the impregnated calcium carbonate in the resin paste was evaluated.
- Table 2 shows the ratio of the amount of each component contained in the resin paste to which the impregnated calcium carbonate was added. The evaluation results of dispersibility are shown in Table 4, FIG. 2 and FIG.
- Example 4 Impregnated calcium carbonate was obtained in the same manner as in Example 1 except that the amount of Diana Process Oil NP-24 (trade name) was 20 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate. Next, in the same manner as in Example 1, the scattering property (dispersion degree) of the impregnated calcium carbonate obtained in Example 4 was evaluated. The results are shown in Table 1 below. Next, in the same manner as in Example 1, the impregnated calcium carbonate obtained in Example 4 and a resin were mixed to prepare a resin paste, and the dispersibility of the impregnated calcium carbonate in the resin paste was evaluated. Table 2 shows the ratio of the amount of each component contained in the resin paste to which the impregnated calcium carbonate was added. The evaluation results of dispersibility are shown in Table 4, FIG. 2 and FIG.
- Comparative Example 1 In the same manner as in Example 1, a surface-treated calcium carbonate having a surface treated with sodium stearate was obtained. Next, the impregnation treatment was not performed, and the scattering property (dispersion degree) of the surface-treated calcium carbonate whose surface was treated with sodium stearate obtained in Comparative Example 1 was evaluated in the same manner as in Example 1. The results are shown in Table 1 below.
- a resin paste was prepared in the same manner as in Example 1, and Diana Process Oil NP-24 (trade name) was further added to the resin paste and stirred to obtain a resin paste.
- the amount of Diana Process Oil NP-24 (trade name) added was 10 parts by weight with respect to 100 parts by weight of the surface-treated calcium carbonate added to the resin.
- the surface-treated calcium carbonate obtained in Comparative Example 1 was added to the obtained resin paste, and the dispersibility of the surface-treated calcium carbonate in the resin paste was evaluated in the same manner as in Example 1.
- Table 2 shows the ratio of the amount of each component contained in the resin paste to which the surface-treated calcium carbonate is added. The evaluation results of dispersibility are shown in Table 4, FIG. 2 and FIG.
- the surface-treated calcium carbonate particles are covered with a liquid organic compound at room temperature, and the affinity between the surface-treated calcium carbonates is weakened by the liquid organic compound at room temperature, As a result, it is considered that the resin is excellent in dispersibility.
- Comparative Example 3 where 25 parts by weight of Diana Process Oil NP-24 was used, 1500 seconds longer than Comparative Example 1 was required until the impregnated calcium carbonate was uniformly dispersed in the resin. . From this result, impregnation with a large amount of liquid organic compound at room temperature does not improve the dispersibility of the surface-treated calcium carbonate in the resin, but the amount of impregnation of the liquid organic compound at room temperature is set within a specific range. It turns out that is important. If the amount of the liquid organic compound impregnated at room temperature is too large, the surface-treated calcium carbonate is covered with a large amount of the liquid organic compound at room temperature, and conversely, it is considered that dispersion into a resin or the like is hindered.
- Impregnated calcium carbonate was obtained in the same manner as in Example 2 except that diisononyl phthalate (DINP) was used instead of Diana Process Oil NP-24 (trade name).
- DINP diisononyl phthalate
- the scattering property (dispersion degree) of the impregnated calcium carbonate obtained in Example 5 was evaluated. The results are shown in Table 5 below.
- the impregnated calcium carbonate obtained in Example 5 and the resin were mixed to prepare a resin paste, and the dispersibility of the impregnated calcium carbonate in the resin paste was evaluated.
- Table 6 shows the ratio of the amount of each component contained in the resin paste to which the impregnated calcium carbonate was added. The evaluation results of dispersibility are shown in Table 7, FIG. 4 and FIG.
- Impregnated calcium carbonate was obtained in the same manner as in Example 2 except that polypropylene glycol (Uniol D-250 manufactured by NOF Corporation) was used instead of Diana Process Oil NP-24 (trade name).
- the scattering property (dispersion degree) of the impregnated calcium carbonate obtained in Example 6 was evaluated. The results are shown in Table 5 below.
- the impregnated calcium carbonate obtained in Example 6 and the resin were mixed to prepare a resin paste, and the dispersibility of the impregnated calcium carbonate in the resin paste was evaluated.
- Table 6 shows the ratio of the amount of each component contained in the resin paste to which the impregnated calcium carbonate was added. The evaluation results of dispersibility are shown in Table 7, FIG. 4 and FIG.
- Example 7 In accordance with the formulation shown in Table 8 below, 92 parts by weight of polypropylene glycol (EXCENOL 3020 manufactured by Asahi Glass Co., Ltd.) and 88 parts by weight of impregnated calcium carbonate prepared in Example 6 were added as a resin precursor and kneaded to obtain a paste. It was. Evaluation of dispersibility of the obtained paste was performed in the same manner as in Example 1. The results are shown in Table 9 and FIG.
- Comparative Example 4 According to the formulation shown in Table 8 below, 100 parts by weight of polypropylene glycol (EXCENOL 3020 manufactured by Asahi Glass Co., Ltd.) as a resin precursor and 80 parts by weight of the surface-treated calcium carbonate obtained in Comparative Example 1 were added, and the paste was kneaded. Obtained. Evaluation of dispersibility of the obtained paste was performed in the same manner as in Example 1. The results are shown in Table 9 and FIG.
- Example 8 According to the formulation shown in Table 8 below, 94 parts by weight of a modified silicone polymer (MS polymer S203 manufactured by Kaneka Corporation) as a resin precursor and 66 parts by weight of impregnated calcium carbonate prepared in Example 6 were added, kneaded and paste Got. Evaluation of dispersibility of the obtained paste was performed in the same manner as in Example 1. The results are shown in Table 9 and FIG.
- Comparative Example 5 (Comparative Example 5)
- 100 parts by weight of a modified silicone polymer (MS polymer S203 manufactured by Kaneka Corporation) as a resin precursor and 60 parts by weight of the surface-treated calcium carbonate obtained in Comparative Example 1 were added and kneaded.
- a paste was obtained. Evaluation of dispersibility of the obtained paste was performed in the same manner as in Example 1. The results are shown in Table 9 and FIG.
- Example 9 In accordance with the formulation shown in Table 8 below, 90 parts by weight of diisononyl phthalate (Sansoizer DINP manufactured by Shin Nippon Rika Co., Ltd.) and 110 parts by weight of impregnated calcium carbonate prepared in Example 6 were added and kneaded as a resin precursor. A paste was obtained. Evaluation of dispersibility of the obtained paste was performed in the same manner as in Example 1. The results are shown in Table 9 and FIG.
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Abstract
Description
含浸処理炭酸カルシウムを構成する炭酸カルシウムは、特に限定されない。例えば、従来公知の炭酸カルシウムを用いることができる。炭酸カルシウムの具体例としては、合成炭酸カルシウム、天然炭酸カルシウム(重質炭酸カルシウム)などが挙げられる。炭酸カルシウムは、合成炭酸カルシウムであることが好ましい。
脂肪酸及びその誘導体は、特に限定されない。脂肪酸及びその誘導体としては、例えば脂肪酸、その金属塩、そのエステル化物などが挙げられる。
より好ましい。炭酸カルシウムに対する脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種の処理量が少なすぎると、表面処理炭酸カルシウムが凝集しやすくなり好ましくない。また、脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種の処理量が多すぎると、表面処理量に比例した効果が得られなくなると共にコストが高くなり、経済的に不利となり好ましくない。
常温で液体の有機化合物は、特に限定されない。なお、常温で液体とは、1気圧下、25℃で液体であることをいう。
炭酸カルシウムを脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種で表面処理する方法は特に限定されない。
表面処理炭酸カルシウムに常温で液体の有機化合物を含浸処理する方法は、特に限定されない。例えば、表面処理炭酸カルシウムと、常温で液体の有機化合物とを混合することにより、含浸処理炭酸カルシウムが得られる。含浸処理の具体例としては、乾燥した表面処理炭酸カルシウムに常温で液体の有機化合物を噴霧し、撹拌する方法が挙げられる。撹拌する方法は、特に限定されず、例えばミキサー、スーパーミキサーなどによって撹拌すればよい。
ポリマー組成物は、ポリマーと含浸処理炭酸カルシウムとを含む。ポリマー組成物としては、例えば、樹脂組成物、ゴム組成物などが挙げられる。ポリマー組成物に含まれるポリマーは、特に限定されない。ポリマーとしては、例えば樹脂、ゴムなどが挙げられる。
樹脂組成物に含まれる樹脂は、特に限定されない。樹脂としては、ポリ塩化ビニル樹脂、ポリウレタン樹脂、変成シリコーン樹脂、ポリサルファイド樹脂、アクリル樹脂、シリコーン樹脂、ポリプロピレングリコール類などの公知の樹脂が挙げられる。
ゴム組成物に含まれるゴムは、特に限定されない。ゴムとしては、天然ゴム及び合成ゴムが挙げられる。
ポリマー前駆体組成物は、ポリマーの前駆体と含浸処理炭酸カルシウムとを含む。ポリマーの前駆体組成物としては、上記の樹脂の前駆体を含む組成物、上記のゴムの前駆体を含む組成物などが挙げられる。ポリマーの前駆体組成物は、必要に応じて、上記と同様の樹脂可塑剤、充填剤、架橋剤、その他の添加剤、各種ゴム用配合剤などをさらに含んでいてもよい。ポリマー前駆体組成物中の含浸処理炭酸カルシウムの含有量は、ポリマー前駆体組成物100重量部に対して、通常10重量部~400重量部程度であり、10重量部~300重量部程度であることが好ましい。
なお、本発明における含浸処理炭酸カルシウムと同様に、酸化カルシウムや水酸化カルシウムなどの無機粒子を常温で液体の有機化合物を含浸処理して含浸処理無機粒子としてもよい。このような含浸処理無機粒子も、ポリマー組成物及びポリマー前駆体組成物に対する分散性に優れている。また、含浸処理無機粒子は、平均粒子径が例えば20nm~200nm程度と非常に微細であっても、飛散しにくく、取り扱いが容易である。
BET比表面積が20m2/gである合成炭酸カルシウム2kgに、固形分が10重量%となるように温水を加え、撹拌型分散機を用いて炭酸カルシウムスラリー液を調製した。このスラリー液を分散機で撹拌しながら、ステアリン酸ナトリウム60gを加え、さらに5分間撹拌した。次に、得られたスラリーをフィルタープレスによって脱水した後、箱型乾燥機によって乾燥して、粉末化することによりステアリン酸ナトリウムで表面が処理された表面処理炭酸カルシウム約2kgを得た。
飛散性評価には、ホソカワミクロン株式会社製のパウダーテスターPT-D型を用いた。図1に示すように、パウダーテスター1を用いて、ガラス円筒2(半径5cm、長さ35cm)の下部に、円形のウォッチグラス4(半径5cm)を設け、円形のサンプル台3(半径2.5cm)からサンプル5(含浸処理炭酸カルシウム)10gを自然落下させた。サンプル台3の下部からガラス円筒の上部までの距離は、16cm、ガラス円筒2の下部からウォッチグラス4までの距離は、11cmとした。飛散性(分散度)は、以下の式で得られた値により評価した。結果を下記表1に示す。
次に、下記表2に示す配合に従い、樹脂としてポリ塩化ビニル(第一塩ビ株式会社製のPVCペーストレジンZEST P21)150重量部と、樹脂可塑剤としてフタル酸ジイソノニル(新日本理化株式会社製のフタル酸系エステルサンソサイザーDINP)95重量部と、充填剤として重質炭酸カルシウム(備北粉化工株式会社製の重質炭酸カルシウムBF300)75重量部とを混練機に加え、混合して樹脂ペーストとした。得られた樹脂ペーストに上記含浸処理炭酸カルシウム105重量部を加え、さらに混練した。樹脂ペーストへの含浸処理炭酸カルシウムの分散性を以下のようにして評価した。
樹脂ペーストと含浸処理炭酸カルシウムとを混練中に経時でサンプルを採取した。採取したサンプルを、黒色紙に適量載せ、500μmアプリケーターで塗布した。下記表3の分散性評価基準のとおり、塗布したサンプルの塗膜中に存在する、粒の数とそのサイズとによって、A~Eの5段階に分けて分散性を評価した。結果を下記表4に示す。また、分散性と混練時間との関係を表したグラフを図2に示す。分散度Aに至るまでの時間を示したグラフを図3に示す。
ダイアナプロセスオイルNP-24(商品名)の量を表面処理炭酸カルシウム100重量部に対して10重量部としたこと以外は、実施例1と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、実施例2で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表1に示す。次に、実施例1と同様にして、実施例2で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、得られた樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表2に示す。分散性の評価結果を表4、図2及び図3に示す。
ダイアナプロセスオイルNP-24(商品名)の量を表面処理炭酸カルシウム100重量部に対して14重量部としたこと以外は、実施例1と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、実施例3で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表1に示す。次に、実施例1と同様にして、実施例3で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表2に示す。分散性の評価結果を表4、図2及び図3に示す。
ダイアナプロセスオイルNP-24(商品名)の量を表面処理炭酸カルシウム100重量部に対して20重量部としたこと以外は、実施例1と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、実施例4で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表1に示す。次に、実施例1と同様にして、実施例4で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表2に示す。分散性の評価結果を表4、図2及び図3に示す。
実施例1と同様にして、ステアリン酸ナトリウムで表面が処理された表面処理炭酸カルシウムを得た。次に、含浸処理は行わず、比較例1で得られたステアリン酸ナトリウムで表面が処理された表面処理炭酸カルシウムの飛散性(分散度)について実施例1と同様にして評価した。結果を下記表1に示す。
ダイアナプロセスオイルNP-24(商品名)の量を表面処理炭酸カルシウム100重量部に対して2重量部としたこと以外は、実施例1と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、比較例2で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表1に示す。次に、実施例1と同様にして、比較例2で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表2に示す。分散性の評価結果を表4、図2及び図3に示す。
ダイアナプロセスオイルNP-24(商品名)の量を表面処理炭酸カルシウム100重量部に対して25重量部としたこと以外は、実施例1と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、比較例3で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表1に示す。実施例1と同様にして、比較例3で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表2に示す。分散性の評価結果を表4、図2及び図3に示す。
ダイアナプロセスオイルNP-24(商品名)の代わりにフタル酸ジイソノニル(DINP)を用いたこと以外は、実施例2と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、実施例5で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表5に示す。次に、実施例1と同様にして、実施例5で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表6に示す。分散性の評価結果を表7、図4及び図5に示す。
ダイアナプロセスオイルNP-24(商品名)の代わりにポリプロピレングリコール(日油株式会社製のユニオールD-250)を用いたこと以外は、実施例2と同様にして含浸処理炭酸カルシウムを得た。次に、実施例1と同様にして、実施例6で得られた含浸処理炭酸カルシウムの飛散性(分散度)を評価した。結果を下記表5に示す。次に、実施例1と同様にして、実施例6で得られた含浸処理炭酸カルシウムと樹脂とを混合して樹脂ペーストを調製し、樹脂ペーストへの含浸処理炭酸カルシウムの分散性を評価した。含浸処理炭酸カルシウムを加えた樹脂ペーストに含まれる各成分の配合量の比を表6に示す。分散性の評価結果を表7、図4及び図5に示す。
下記表8に示す配合に従い、樹脂の前駆体としてポリプロピレングリコール(旭硝子株式会社製のEXCENOL3020)92重量部と、実施例6で作製した含浸処理炭酸カルシウム88重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図6に示す。
下記表8に示す配合に従い、樹脂の前駆体としてポリプロピレングリコール(旭硝子株式会社製のEXCENOL3020)100重量部と、比較例1で得られた表面処理炭酸カルシウム80重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図6に示す。
下記表8に示す配合に従い、樹脂の前駆体として変成シリコーンポリマー(株式会社カネカ製MSポリマーS203)94重量部と、実施例6で作製した含浸処理炭酸カルシウム66重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図7に示す。
下記表8に示す配合に従い、樹脂の前駆体として変成シリコーンポリマー(株式会社カネカ製MSポリマーS203)100重量部と、比較例1で得られた表面処理炭酸カルシウム60重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図7に示す。
下記表8に示す配合に従い、樹脂の前駆体としてフタル酸ジイソノニル(新日本理化株式会社製サンソザイザーDINP)90重量部と、実施例6で作製した含浸処理炭酸カルシウム110重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図8に示す。
下記表8に示す配合に従い、樹脂の前駆体としてフタル酸ジイソノニル(新日本理化株式会社製サンソザイザーDINP)100重量部と、比較例1で得られた表面処理炭酸カルシウム100重量部を加え、混練してペーストを得た。得られたペーストの分散性評価を実施例1と同様にして行った。結果を表9及び図8に示す。
2…ガラス円筒
3…サンプル台
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Claims (10)
- 脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種で炭酸カルシウムを表面処理してなる表面処理炭酸カルシウムに、常温で液体の有機化合物を、前記表面処理炭酸カルシウム100重量部に対して3~22重量部含浸してなる含浸処理炭酸カルシウム。
- 前記有機化合物は、可塑剤、油剤及びポリプロピレングリコール類の少なくとも1種である、請求項1に記載の含浸処理炭酸カルシウム。
- 前記油剤は、鉱物油である、請求項1または2に記載の含浸処理炭酸カルシウム。
- 前記炭酸カルシウムは、合成炭酸カルシウムである、請求項1~3のいずれか一項に記載の含浸処理炭酸カルシウム。
- 前記表面処理炭酸カルシウムの平均粒子径は、20nm~200nmである、請求項1~4のいずれか一項に記載の含浸処理炭酸カルシウム。
- 前記表面処理炭酸カルシウムのBET比表面積は、10m2/g~100m2/gである、請求項1~5のいずれか一項に記載の含浸処理炭酸カルシウム。
- 前記炭酸カルシウムに対する脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種の処理量は、前記炭酸カルシウム100重量部に対して、2重量部~15重量部である、請求項1~6のいずれか一項に記載の含浸処理炭酸カルシウム。
- 請求項1~7のいずれか一項に記載の含浸処理炭酸カルシウムを含むポリマー組成物。
- 請求項1~7のいずれか一項に記載の含浸処理炭酸カルシウムを含むポリマー前駆体組成物。
- 脂肪酸、樹脂酸及びこれらの誘導体の少なくとも1種で炭酸カルシウムを表面処理して、表面処理炭酸カルシウムを得る工程、及び
常温で液体の有機化合物を、前記表面処理炭酸カルシウム100重量部に対して3~22重量部含浸する工程
を備える、含浸処理炭酸カルシウムの製造方法。
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JP2013520556A JP5312714B2 (ja) | 2011-06-13 | 2012-06-12 | 含浸処理炭酸カルシウム、その製造方法、ポリマー組成物及びポリマー前駆体組成物 |
CN201280028883.6A CN103608292B (zh) | 2011-06-13 | 2012-06-12 | 含浸处理碳酸钙、其制造方法、聚合物组合物和聚合物前体组合物 |
EP12799794.8A EP2719665A4 (en) | 2011-06-13 | 2012-06-12 | IMPREGNATED CALCIUM CARBONATE, METHOD OF MANUFACTURING THEREOF, POLYMER COMPOSITION AND POLYMER PREPARATION COMPOSITION |
KR20137032884A KR20140033114A (ko) | 2011-06-13 | 2012-06-12 | 함침 처리 탄산칼슘, 그 제조 방법, 폴리머 조성물 및 폴리머 전구체 조성물 |
US14/126,144 US9085668B2 (en) | 2011-06-13 | 2012-06-12 | Impregnated calcium carbonate, method for producing same, polymer composition, and polymer precursor composition |
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CN103819935A (zh) * | 2014-01-31 | 2014-05-28 | 许营春 | 复合湿法表面改性处理制备氢氧化镁阻燃剂的方法 |
US20160168431A1 (en) * | 2014-12-12 | 2016-06-16 | Illinois Tool Works Inc. | High performance sealant composition for tire repair |
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US9921509B2 (en) | 2014-11-18 | 2018-03-20 | Esprix Technologies, Lp | Process for preparing novel composite charge control agents and novel composite charge control agents prepared by the process |
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US9963620B2 (en) | 2015-04-01 | 2018-05-08 | Illinois Tool Works Inc. | High performance environmentally friendly sealant composition for tire repair |
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WO2024029811A1 (ko) * | 2022-08-02 | 2024-02-08 | 에스케이티비엠지오스톤 주식회사 | 생분해성 수지 조성물의 제조 방법, 이에 의해 제조된 생분해성 수지 조성물, 이를 포함하는 생분해성 성형품 |
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EP2719665A1 (en) | 2014-04-16 |
JPWO2012173114A1 (ja) | 2015-02-23 |
KR20140033114A (ko) | 2014-03-17 |
JP5312714B2 (ja) | 2013-10-09 |
CN103608292B (zh) | 2015-12-09 |
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US9085668B2 (en) | 2015-07-21 |
US20140128529A1 (en) | 2014-05-08 |
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