WO2010110161A1 - 表面処理炭酸カルシウム及びそれを含むペースト状樹脂組成物 - Google Patents
表面処理炭酸カルシウム及びそれを含むペースト状樹脂組成物 Download PDFInfo
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- WO2010110161A1 WO2010110161A1 PCT/JP2010/054636 JP2010054636W WO2010110161A1 WO 2010110161 A1 WO2010110161 A1 WO 2010110161A1 JP 2010054636 W JP2010054636 W JP 2010054636W WO 2010110161 A1 WO2010110161 A1 WO 2010110161A1
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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
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/04—Polysulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01—INORGANIC CHEMISTRY
- 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
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
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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
- 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
- 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
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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
- 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
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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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to surface-treated calcium carbonate and a paste-like resin composition containing the same.
- paste sols are prepared, and coating, painting, construction and mixing are performed using these sols.
- a filler such as fumed silica that can impart a high viscosity to the sol in a small amount is used.
- fumed silica exhibits high thixotropic properties (thixotropic properties), but at the same time the viscosity increases. There is also a problem that the viscosity changes extremely due to a small difference in the amount of addition.
- calcium carbonate is used as a filler for various polymer materials such as plastic, rubber, ink, paint, sealing material, PVC sol, acrylic sol and the like. Therefore, if high thixotropic properties can be imparted by adding calcium carbonate, it can be used as a relatively inexpensive thixotropic agent.
- Patent Document 1 discloses surface-treated calcium carbonate obtained by surface-treating unsaturated fatty acids and saturated fatty acids at a predetermined mixing ratio. By using this surface-treated calcium carbonate, it can be added to ink, paint, sealing material, PVC sol, acrylic sol and the like to impart high thixotropic properties.
- Patent Document 2 also proposes a surface-treated calcium carbonate for imparting high thixotropy, but even if the surface-treated calcium carbonate disclosed in this prior art is used, low viscosity and high thixotropy are achieved. It was difficult to give.
- Patent Document 3 proposes calcium carbonate surface-treated with a surface treatment agent containing 85% or more of lauric acid and myristic acid. However, even when such surface-treated calcium carbonate is used, it has been difficult to impart low thixotropy and high thixotropic properties.
- An object of the present invention is to provide a surface-treated calcium carbonate that has a low viscosity and can impart high thixotropic properties when blended in a paste-like resin, and provides good storage stability, and a paste-like resin composition containing the same. Is to provide.
- the surface-treated calcium carbonate of the present invention is a carbonic acid surface-treated with a surface treatment agent containing a sodium salt or potassium salt of lauric acid and a sodium salt or potassium salt of palmitic acid and / or a sodium salt or potassium salt of stearic acid. It is calcium, and the total content of the sodium salt or potassium salt of lauric acid, the sodium salt or potassium salt of palmitic acid, and the sodium salt or potassium salt of stearic acid in the surface treatment agent is 80% by weight or more.
- the content of sodium salt and potassium salt of lauric acid is in the range of 30 to 60% by weight, and the content of sodium salt and potassium salt of unsaturated fatty acid in the surface treatment agent is 5% by weight or less,
- the BET specific surface area is 10 m 2 / g or more.
- the surface-treated calcium carbonate when blended in a paste-like resin, can be provided with low viscosity and high thixotropic properties, and good storage stability can be obtained.
- the sodium salt or potassium salt of the other fatty acid is preferably a sodium salt or potassium salt of a fatty acid having 14 to 22 carbon atoms.
- the BET specific surface area of the surface-treated calcium carbonate is preferably in the range of 10 to 100 m 2 / g.
- the surface treatment agent 2 to 15 parts by weight of the surface treatment agent is preferably treated with respect to 100 parts by weight of calcium carbonate.
- the amount of fatty acid extracted by extracting the surface-treated calcium carbonate with diethyl ether is 0.4% by weight or less.
- the polyurethane paste resin composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the modified silicone paste resin composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the polysulfide paste resin composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the polyvinyl chloride sol resin composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the acrylic sol resin composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the printing ink composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the coating composition of the present invention is characterized by containing the surface-treated calcium carbonate of the present invention.
- the surface-treated calcium carbonate of the present invention When the surface-treated calcium carbonate of the present invention is blended in a paste-like resin, the surface-treated calcium carbonate can be provided with low viscosity and high thixotropic properties, and good storage stability can be obtained.
- the paste-like resin composition of the present invention contains the surface-treated calcium carbonate of the present invention, it has low viscosity and high thixotropic properties, and is excellent in storage stability.
- FIG. 1 is a diagram schematically showing the surface state of the surface-treated calcium carbonate according to the present invention.
- the calcium carbonate particles used as a target for the surface treatment are not particularly limited as long as they can be used as fillers for various polymer materials excluding silicone.
- Calcium carbonate includes natural calcium carbonate (heavy calcium carbonate) and synthetic calcium carbonate (light (glue) calcium carbonate). Natural calcium carbonate is produced directly from limestone ore, and can be produced, for example, by mechanically crushing and classifying limestone ore.
- Synthetic calcium carbonate is produced from calcium hydroxide, and can be produced, for example, by reacting calcium hydroxide with carbon dioxide gas.
- 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 or the like. 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.
- the BET specific surface area is slightly reduced by surface treatment.
- the surface-treated calcium carbonate of the present invention has a BET specific surface area of 10 m 2 / g or more. Therefore, it is preferable to use calcium carbonate having a value slightly larger than 10 m 2 / g for the BET specific surface area of calcium carbonate before the surface treatment.
- the calcium carbonate is surface-treated with a surface treatment agent containing 30 to 60% by weight of at least one of sodium salt and potassium salt of lauric acid.
- a more preferable content ratio of the sodium salt and potassium salt of lauric acid is in the range of 30 to 55% by weight, more preferably in the range of 35 to 55% by weight, and still more preferably in the range of 40 to 55% by weight. .
- the content ratio of the sodium salt and potassium salt of lauric acid is too small, the viscosity when blended in the paste-like resin is high, the viscosity is low, and high thixotropic properties cannot be imparted.
- Either the sodium salt of lauric acid or the potassium salt of lauric acid may be used alone or in combination.
- a sodium salt is particularly preferably used.
- the surface treatment agent in the present invention contains at least one of sodium and potassium salts of palmitic acid and sodium and potassium salts of stearic acid in addition to the sodium and potassium salts of lauric acid.
- the total content of the sodium salt and potassium salt of lauric acid, the sodium salt and potassium salt of palmitic acid, and the sodium salt and potassium salt of stearic acid in the surface treatment agent is 80% by weight or more.
- the content ratio of the sodium salt and potassium salt of lauric acid is 60% by weight at maximum, the total content ratio of the sodium salt and potassium salt of palmitic acid and the sodium salt and potassium salt of stearic acid is 20%. % By weight or more.
- the viscosity is low and high. Can not impart thixotropy.
- the sodium salt and potassium salt of lauric acid are contained in the above-mentioned predetermined ratio, and are treated with at least one of sodium salt and potassium salt of palmitic acid and sodium salt and potassium salt of stearic acid. Therefore, high thixotropy can be imparted with low viscosity. The details of this reason are not clear, but are presumed as follows.
- FIG. 1 is a diagram schematically showing the surface of calcium carbonate surface-treated according to the present invention.
- lauric acid 2 having a relatively short chain length and palmitic acid or stearic acid 3 having a relatively long chain length are adsorbed on the surface of calcium carbonate 1 by surface treatment. Yes.
- lauric acid 2 and palmitic acid and / or stearic acid 3 are mixed in a predetermined ratio, and the chain length is short between palmitic acid and / or stearic acid 3 having a long chain length. Lauric acid 2 is present. For this reason, the organic chain 4 of the matrix resin can enter the region of lauric acid 2 having a short chain length.
- organic chain 4 and palmitic acid and / or stearic acid 3 and lauric acid 2 which are surface treatment agents on the surface of calcium carbonate 1 are likely to interact with each other, and the structural viscosity is increased. It is considered that high thixotropic properties can be obtained.
- Palmitic acid and stearic acid may be in the form of sodium salt or potassium salt, but are preferably used in the form of sodium salt.
- the surface treatment agent includes the sodium salt and potassium salt of lauric acid, the sodium salt and potassium salt of palmitic acid, and the sodium salt and potassium salt of other fatty acids in addition to the sodium salt and potassium salt of stearic acid. May be included.
- fatty acids include, for example, fatty acids having 14 and 20 to 31 carbon atoms. More preferred are fatty acids having 14 and 20 to 26 carbon atoms, and more preferred are fatty acids having 14 and 20 to 22 carbon atoms. Specific examples of the fatty acid include myristic acid, aligning acid, behenic acid, lignoceric acid, serotic acid, montanic acid, melicic acid and the like. Other fatty acids are used in the form of fatty acid sodium salt and / or fatty acid potassium salt. In the present invention, the sodium salt form is particularly preferably used.
- sodium and potassium salts of unsaturated fatty acids In the present invention, as described above, calcium carbonate is surface-treated with a surface treatment agent containing a sodium salt or potassium salt of lauric acid and a sodium salt or potassium salt of palmitic acid and / or stearic acid.
- the sodium salt or potassium salt of unsaturated fatty acid may be contained as the sodium salt or potassium salt of other fatty acids, the content is preferably 5% by weight or less.
- the more preferable content ratio of the sodium salt and potassium salt of the unsaturated fatty acid is 4% by weight or less, more preferably 3% by weight or less, and further preferably 2% by weight or less.
- unsaturated fatty acids include oleic acid, erucic acid, linoleic acid and the like.
- the surface treatment agent in the present invention has a total ratio of 80% by weight or more of sodium salt and potassium salt of lauric acid, sodium salt and potassium salt of palmitic acid, and sodium salt and potassium salt of stearic acid. And the ratio of sodium salt and potassium salt of lauric acid is in the range of 30 to 60% by weight, and the content ratio of sodium salt and potassium salt of unsaturated fatty acid is 5% by weight or less. If these conditions are satisfied, the surface treatment agents include sodium and potassium laurate, sodium and potassium palmitate, sodium and potassium stearates, and other fatty acid sodium and potassium salts. A surface treatment agent other than salt may be included.
- lauric acid, palmitic acid, stearic acid, and other fatty acids may be included in the form of an acid as long as the effects of the present invention are not lost.
- sulfonates such as alkylbenzene sulfonic acids, sodium salts or potassium salts of resin acids may be included as long as the effects of the present invention are not lost.
- the surface-treated calcium carbonate of the present invention is calcium carbonate surface-treated with the surface treatment agent.
- the BET specific surface area of the surface-treated calcium carbonate of the present invention is 10 m 2 / g or more. If the BET specific surface area is less than 10 m 2 / g, it cannot have high thixotropic properties.
- the BET specific surface area is more preferably in the range of 10 to 100 m 2 / g. In general, it is often difficult to produce calcium carbonate having a BET specific surface area of greater than 100 m 2 / g.
- a more preferable value of the BET specific surface area is in the range of 10 to 60 m 2 / g, and more preferably in the range of 15 to 40 m 2 / g.
- the treatment amount with the surface treatment agent is preferably 2 to 15 parts by weight, more preferably 2 to 10 parts by weight, and further preferably 2.5 to 5 parts by weight with respect to 100 parts by weight of calcium carbonate. is there.
- the treatment amount with the surface treatment agent can be appropriately adjusted in consideration of the BET specific surface area of the calcium carbonate to be surface treated.
- the amount of surface treatment is too small, the effect of the present invention that low viscosity and high thixotropic properties can be imparted may not be sufficiently obtained.
- the surface treatment amount is too large, an effect proportional to the surface treatment amount cannot be obtained, the cost is increased, and this is economically disadvantageous.
- the amount of extracted fatty acid obtained by extracting the surface-treated calcium carbonate with diethyl ether is preferably 0.4% by weight or less.
- calcium carbonate is surface-treated with a surface treatment agent containing sodium salt or potassium salt of lauric acid and sodium salt or potassium salt of palmitic acid and / or stearic acid.
- a surface treatment agent containing sodium salt or potassium salt of lauric acid and sodium salt or potassium salt of palmitic acid and / or stearic acid.
- the surface treatment method include a method in which a surface treatment agent is added to a slurry solution of calcium carbonate particles and stirred for treatment as described later. It is considered that the sodium salt or potassium salt of a fatty acid such as lauric acid added to the slurry solution of calcium carbonate particles reacts with calcium present on the surface of the calcium carbonate to become a calcium salt of a fatty acid such as lauric acid.
- the form of the acid attached to the surface of the surface-treated calcium carbonate by extracting the surface-treated calcium carbonate with diethyl ether as described above Lauric acid, palmitic acid, stearic acid and other fatty acids and fatty acid salts present in the form of sodium or potassium salts can be dissolved and extracted.
- the amount of extracted fatty acid is defined as an index indicating the content ratio of the fatty acid adhered in the form of such an acid and the fatty acid salt adhered in the form of a sodium salt or potassium salt.
- the amount of extracted fatty acid can be determined from the following equation.
- Extracted fatty acid amount (% by weight) [(weight of surface-treated calcium carbonate before extraction ⁇ weight of surface-treated calcium carbonate after extraction) / (weight of surface-treated calcium carbonate before extraction)] ⁇ 100 From the amount of extracted fatty acid, the content ratio of fatty acid such as lauric acid and its salt adhering to the surface of the surface-treated calcium carbonate in the form of acid and sodium salt or calcium salt can be determined.
- the amount of extracted fatty acid is preferably 0.4% by weight or less, more preferably 0.3% by weight or less, and further preferably 0.25% by weight or less.
- the amount of the extracted fatty acid is too large, high thixotropy cannot be obtained, and the viscosity increases during long-term storage, resulting in poor storage stability.
- the lower limit of the amount of extracted fatty acids is not particularly limited, it is, for example, 0.05% by weight or more.
- the composition of the surface treatment agent in the surface treated calcium carbonate can be determined by measuring the components of the surface treatment agent obtained after decomposing the surface treated calcium carbonate with an acid, for example, by gas chromatography. .
- the content of the surface treatment agent can be measured, for example, by differential thermal analysis.
- the surface-treated calcium carbonate of the present invention can be produced by adding the above-mentioned surface treatment agent to a slurry liquid of calcium carbonate particles and stirring.
- the sodium salt or potassium salt of a fatty acid such as lauric acid can be surface-treated by reacting with calcium on the surface of calcium carbonate to form an insoluble calcium salt.
- the surface-treated calcium carbonate slurry can be dehydrated and dried to obtain a surface-treated calcium carbonate powder.
- the solid content of calcium carbonate in the calcium carbonate slurry can be appropriately adjusted in consideration of the dispersibility of the calcium carbonate particles, the ease of dehydration, and the like. Moreover, it can adjust suitably with the particle diameter etc. of a calcium carbonate particle.
- a slurry liquid with an appropriate viscosity can be obtained by adjusting the solid content of the slurry to 2 to 30% by weight, preferably about 5 to 20% by weight. If the amount of water used is too large, dehydration becomes difficult, which is not preferable in terms of wastewater treatment.
- the surface-treated calcium carbonate of the present invention can impart a high thixotropic property with a low viscosity when blended with a paste-like resin such as ink, paint, sealing material, PVC sol, DOP sol, acrylic sol, etc. Gives good storage stability.
- the blending amount of the surface-treated calcium carbonate with respect to the pasty resin can be appropriately adjusted according to the blending purpose, characteristics required for the pasty resin, and the like.
- the polyurethane paste-like resin composition that can be used as a polyurethane sealant or the like mainly contains an isocyanate, a polyol, a plasticizer, a filler, and other additives.
- Isocyanates include tolylene diisocyanate (TDI), 4,4-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate, tolidine diisocyanate (TODI), xylene diisocyanate and its modified products, dicyclohexylmethane diisocyanate (water) Added MDI), isophorone diisocyanate (IPDI) and the like.
- TDI tolylene diisocyanate
- MDI 4,4-diphenylmethane diisocyanate
- TODI 1,5-naphthalene diisocyanate
- TODI tolidine diisocyanate
- xylene diisocyanate and its modified products dicyclohexylmethane diisocyanate (water) Added MDI
- IPDI isophorone diisocyanate
- polystyrene resin examples include dicarboxylic acids such as adipic acid, phthalic acid, sebacic acid, and dimer acid, and glycols such as ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, 1,3-butanediol, hexanetriol, and trimethylolpropane. Can be mentioned.
- examples of other polyols include esters of the type obtained by ring-opening polymerization of caprolactone.
- Plasticizers include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate (DINP) , Diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butyl benzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA), adipine Diisodecyl acid (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioct
- Fillers include inorganic and organic ones.
- Inorganic fillers include calcium carbonate (natural and synthetic products), calcium and magnesium carbonate (natural and synthetic products), basic magnesium carbonate, quartz powder, quartzite powder, and finely divided silicic acid (dry and wet products).
- Organic fillers include wood powder, walnut powder, cork powder, wheat flour, starch, ebonite powder, rubber powder, lignin, phenolic resin, high styrene resin, polyethylene resin, silicon resin, urea resin, etc. or beads And fibrous materials such as cellulose powder, pulp powder, synthetic fiber powder, amide wax, and castor oil wax.
- the blending ratio of the surface-treated calcium carbonate in the polyurethane paste resin composition of the present invention is 10 to 400 parts by weight with respect to 100 parts by weight as a total of the resin component (including the plasticizer) and the liquid additive.
- the amount is preferably 10 to 300 parts by weight.
- a modified silicone paste resin composition such as a modified silicone sealant mainly comprises a modified silicone resin, a plasticizer, a filler, and other additives. This resin is modified by introducing a reactive silicone functional group at the end of the polymer, and is a resin having a completely different molecular structure from the silicone resin.
- Plasticizers, fillers, and other additives can be the same as those described for the polyurethane paste resin composition.
- the blending ratio of the surface-treated calcium carbonate is preferably 10 to 400 parts by weight, more preferably 10 to 300 parts by weight with respect to 100 parts by weight as a total of the modified silicone resin, the plasticizer, and the liquid additive. .
- a polysulfide paste-like resin composition such as a polysulfide sealant mainly contains a polysulfide resin, a plasticizer, a filler, and other additives.
- polysulfide resin for example, those manufactured as follows are used. Colloidal suspension of sodium polysulfide, a small amount of activator and magnesium hydroxide, starting from dichloroethyl formal obtained by reacting ethylene chlorohydrin obtained by the reaction of ethylene oxide and hydrochloric acid with paraformaldehyde Into this, dichloroformal can be added with stirring and heating to produce a polysulfide resin.
- the same materials as those described for the polyurethane paste resin composition can be used.
- the blending ratio of the surface-treated calcium carbonate is preferably 10 to 400 parts by weight with respect to 100 parts by weight in total of the polysulfide resin (modified polysulfide resin), the plasticizer, and the liquid additive. More preferably.
- the polyvinyl chloride resin composition mainly contains a vinyl chloride resin, a plasticizer, a filler, and other additives.
- a plasticizer, a filler, and other additives the same ones as described in the polyurethane paste resin composition can be used.
- the blending ratio of the surface-treated calcium carbonate is preferably 10 to 400 parts by weight, more preferably 10 to 300 parts by weight with respect to 100 parts by weight of the total of the vinyl chloride resin, the plasticizer, and the liquid additive. .
- the acrylic sol resin composition mainly includes an acrylic resin, a crosslinking agent, a plasticizer, a filler, and other additives.
- the monomers constituting the acrylic resin can be roughly classified into a non-functional monomer, a monofunctional monomer, and a polyfunctional monomer when roughly classified by methacrylic monomers.
- Non-functional monomers include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, tertbutyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, methacryl Examples include lauryl toludecyl acid, tridecyl methacrylate, cetyl-stearyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate.
- Monofunctional monomers include methacrylic acid, 2-hydroxyethyl methacrylate, and methacrylic acid 2 Hydroxypropyl, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, tertbutylaminoethyl methacrylate, methacrylate
- polyfunctional monomers include ethylene dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, decaethylene glycol dimethacrylate, and the like.
- the acrylic resin can be produced by copolymerizing the above non-functional monomer with a monofunctional monomer and / or a polyfunctional monomer.
- crosslinking agent examples include amino resins, isocyanate compounds, and epoxy resins.
- the plasticizer and filler the same materials as those described for the polyurethane sealant can be used.
- the blending ratio of the surface-treated calcium carbonate is preferably 10 to 400 parts by weight, more preferably 10 to 300 parts by weight with respect to 100 parts by weight of the total of the acrylic resin, the plasticizer, and the liquid additive. .
- the printing ink composition mainly contains colorants, vehicles, additives and the like.
- Color materials include inorganic and organic pigments and dyes.
- inorganic pigments include titanium oxide, carbon black, bronze powder, disazo yellow, brilliant carmine 6B, lake red C, phthalocyanine blue, methyl violet lake, and daylight fluorescent pigment.
- organic pigments include insoluble azo pigments, azo lake pigments, phthalocyanine pigments, and dyed lake pigments.
- the dye include eosin, Victoria blue, nigrosine, C.I. I.
- extender pigments are known, and calcium carbonate and the like are usually used as extender pigments. The extender pigment is used for adjusting fluidity, coloring power, hiding power, gloss, etc. of the printing ink.
- the vehicle is mainly composed of oil, resin, solvent, and additives.
- oils such as vegetable oil, processed oil, mineral oil, vegetable oil is mainly linseed oil and cinnabar oil, processed oil is heat-modified vegetable oil, maleated oil, urethane oil, vinylated oil, mineral oil is machine oil, Spindle oil is used.
- resins natural resin gum rosin, wood rosin, tall oil rosin, derivatives thereof, synthetic resin rosin modified phenolic resin, urea resin and melanin resin, ketone resin, polyvinyl chloride, polyvinyl chloride / vinyl acetate copolymer resin, polyvinyl Butyral (butyral resin), styrene / maleic resin, chlorinated polypropylene, acrylic resin, coumarone / indene resin, petroleum resin, polyester resin, alkyd resin, polyamide resin, epoxy resin, polyurethane, nitrocellulose (nitrified cotton), ethylcellulose, Examples thereof include ethyl hydroxyethyl cellulose (EHEC), cyclized rubber, and chlorinated rubber.
- EHEC ethyl hydroxyethyl cellulose
- Solvents include n-hexane, n-heptane, rubber volatile oil (industrial gasoline 2), mineral spirit, high boiling petroleum solvent (ink oil), cyclohexane, toluene, xylene, solvent naphtha, tetralin, dipentene, methyl alcohol, Ethyl alcohol, n-propyl alcohol, isopropyl alcohol (IPA), n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, cyclohexyl alcohol, 2-methylcyclohexyl alcohol, tridecyl alcohol (tridecanol), methyl acetate, ethyl acetate, acetic acid Isopropyl, butyl acetate, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone (anone), methylcyclohexanone, diacetone alcohol (DAA), isophorone
- Additives include waxes, dryers, dispersants and lubricants.
- the waxes are plant wax carnauba wax, wood wax, animal wax honey wax, anhydrous lanolin (wool wax), mineral wax paraffin wax, microcrystalline wax, Montan wax, ozokerite (ground wax), petrolatum and petroleum jelly, synthetic wax polyethylene wax, polytetrafluoroethylene (PTFE), chlorinated paraffin, fatty acid amide and the like are used.
- the dryer include a liquid dryer in which metal soap is dissolved in oil and fat, a paste dryer in which manganese borate, lead borate, lead acetate and the like are dispersed in a drying oil varnish.
- Dispersants and lubricants include oily dispersants and aqueous dispersants, and oily dispersants include lecithin, sorbitan fatty acid esters, polyacrylic acid partial fatty acid esters, alkylamine fatty acid salts, alkyldiamines, alkyltriamines, naphthenic acid metal soaps,
- the trade name is Solpis from ICI, Antiterra from Bigmalinklot, Dispalon from Enomoto Chemicals, and the aqueous dispersant is formalin condensate of sodium naphthalenesulfonate, sodium ligninsulfonate, sodium alkylsulfate, sodium alkylarylsulfonate, etc.
- Anionic surfactants nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene aryl ethers, alkali-soluble resins such as styrene maleic acid resins and polyacrylic acid derivatives, etc. It has been used.
- the blending ratio of the surface-treated calcium carbonate is preferably 0.01 to 50 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of the total of the colorant, vehicle and additive. 20 parts by weight.
- the coating composition mainly contains pigments, vehicles, additives and the like.
- organic pigments such as zinc white, titanium dioxide, ben, iron black, chromium oxide, cobalt blue, titanium yellow, silica, red lead, yellow iron oxide, alumina white, yellow lead, Zinc chromate, molybdenum red, bitumen, cadmium yellow, cadmium red, barium sulfate, calcium carbonate, ultramarine, manganese violet, carbon black, aluminum powder, bronze powder, zinc dust, organic pigments are naphthol red, benzimidazolone Bordeaux, first Yellow G, disazo yellow HR, condensed azo yellow, condensed azo red, lake red C, brilliant carmine 6B, nickel azo yellow, quinacridone red, quinacridone scarlet, perylene red, perylene maroon, perinone orange Thioindigo Bordeaux, flavanthrone yellow, Jian slide Kino Lil Red, Indus Ren blue, dioxazine violet, quinophthalone yellow, pyrrole red, phthal
- the vehicle is mainly composed of a resin, a curing agent, and a solvent.
- Resin is acrylic resin, alkyd resin, polyester resin, epoxy resin, vinyl resin, cellulose resin, natural resin, curing agent is melanin resin, polyisocyanate, polyamine resin, solvent is hydrocarbon solvent, ketone solvent, ester solvent Ether solvents, alcohol solvents, water and the like are used.
- Additives are mainly leveling agents, rheology modifiers, plasticizers, emulsifiers, pigment dispersants, light stabilizers, etc.
- the blending ratio of the surface-treated calcium carbonate is preferably 0.1 to 100 parts by weight, more preferably 0.3 to 50 parts by weight with respect to 100 parts by weight of the total of the pigment, vehicle and additives. Part.
- Example 1 Water adjusted to 60 ° C. was added to 2 kg of synthetic calcium carbonate having a BET specific surface area of 24 m 2 / g so as to have a solid content of 10% by weight, and a calcium carbonate slurry liquid was prepared using a stirring type disperser. While stirring the slurry with a disperser, 75 g of a mixed fatty acid sodium salt obtained by mixing 35 g of sodium laurate, 17.5 g of sodium stearate and 17.5 g of sodium palmitate (50% sodium laurate, 25% sodium stearate) , Sodium palmitate (25%) was added to the calcium carbonate slurry and stirred for 5 minutes, followed by press dehydration.
- the obtained dehydrated cake was dried and then powdered to obtain about 2 kg of surface treated calcium carbonate.
- Example 2 Surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that total calcium carbonate having a BET specific surface area of 20 m 2 / g was used.
- Example 3 75 g of a mixed fatty acid sodium salt obtained by mixing 35 g of sodium laurate, 16.4 g of sodium palmitate, 16.5 g of sodium stearate, and 2.1 g of sodium oleate (50% sodium laurate, 23.4% sodium palmitate, stearin Surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that 23.6% sodium acid and 3% sodium oleate were used.
- Example 4 70 g of a mixed fatty acid sodium salt obtained by mixing 24.5 g of sodium laurate, 22.8 g of sodium palmitate, and 22.8 g of sodium stearate (35% sodium laurate, 32.5% sodium palmitate, 32.5% sodium stearate %) was used in the same manner as in Example 1 to obtain surface-treated calcium carbonate.
- Example 5 Example above except that 70 g of mixed fatty acid sodium salt (sodium laurate 60%, sodium palmitate 20%, sodium stearate 20%) mixed with 42 g of sodium laurate, 14 g of sodium palmitate and 14 g of sodium stearate In the same manner as in No. 1, surface-treated calcium carbonate was obtained.
- mixed fatty acid sodium salt sodium laurate 60%, sodium palmitate 20%, sodium stearate 20%
- Example 6 Synthetic calcium carbonate having a BET specific surface area of 35 m 2 / g, mixed fatty acid sodium salt 200 g mixed with 100 g of sodium laurate, 50 g of sodium palmitate and 50 g of sodium stearate (50% sodium laurate, 25% sodium palmitate Surface treated calcium carbonate was obtained in the same manner as in Example 1 except that sodium stearate (25%) was used.
- Example 7 70 g of mixed fatty acid sodium salt (sodium laurate 50%, myristic acid) mixed with 35 g of sodium laurate, 11.2 g of sodium myristate, 11.9 g of sodium palmitate, 11.9 g of sodium stearate and 1.4 g of sodium oleate
- Surface-treated calcium carbonate was obtained in the same manner as in Example 1 except that sodium 16%, sodium palmitate 17%, sodium stearate 17%, and sodium oleate 2% were used.
- Example 7 70 g of a mixed fatty acid sodium salt obtained by mixing 33.6 g of sodium laurate, 28 g of sodium myristate, 4.2 g of sodium palmitate, and 4.2 g of sodium stearate (sodium laurate 48%, sodium myristate 40%, sodium palmitate 6 %, Sodium stearate 6%) was used in the same manner as in Example 1 to obtain surface-treated calcium carbonate.
- the BET specific surface area was measured for the calcium carbonate before and after the surface treatment.
- the BET specific surface area was measured using a specific surface area measuring apparatus Flow Soap II 2300 (manufactured by Micromeritic). The measurement results are shown in Table 1.
- “Lauric acid”, “myristic acid”, “palmitic acid”, “stearic acid”, and “oleic acid” shown in Table 1 are the same as those in Examples 1 to 7 and Comparative Examples 1 to 4 and 7.
- the content ratio of the fatty acid as a sodium salt is shown.
- Comparative Examples 5 to 6 the content ratio as each fatty acid is shown.
- DOP sol viscosity test> For the surface-treated calcium carbonates of Examples 1 to 7 and Comparative Examples 1 to 7, DOP sols were prepared and their viscosities were measured.
- the DOP sol was prepared by stirring 100 g of surface-treated calcium carbonate and 100 g of DOP (dioctyl phthalate, manufactured by J Plus) with a hybrid mixer (HM-500 Keyence) for 40 seconds.
- the initial viscosity of the obtained DOP sol was 20 ° C. It was measured.
- the viscosity after 20 degreeC x 7 days was measured at 20 degreeC.
- the viscosity was measured at 2 rpm and 20 rpm with a BH viscometer (manufactured by TOKIMEC).
- the measurement results are shown in Table 1.
- the viscosity increase rate indicates the rate of increase in viscosity after 7 days with respect to the viscosity immediately after kneading.
- Comparative Example 2 in which the content of sodium laurate is less than the range of the present invention, good thixotropic properties are obtained, but the viscosity is high.
- Comparative Example 3 containing more sodium oleate than in the range of the present invention, the viscosity after 7 days was lowered, and the storage stability was inferior to Examples 1 to 7. Recognize.
- the total of sodium laurate, sodium palmitate, and sodium stearate is less than 80% by weight.
- the sum of sodium salt of lauric acid having 12 carbon atoms and sodium salt of myristic acid having 14 carbon atoms is 88%. Since the content ratio of sodium palmitate having 16 carbon atoms and sodium stearate having 18 carbon atoms is less than the range of the present invention, good thixotropic properties are not obtained.
- the PPG sol using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention has a low viscosity and good thixotropic properties. Moreover, it turns out that it is excellent also in storage stability.
- PPG is used as a curing agent for a two-component polyurethane sealant
- the viscosity of the two-component polyurethane sealant shows a good correlation with the viscosity of the PPG sol. Therefore, it can be said that the two-component polyurethane sealant using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention also exhibits high viscosity and good thixotropic properties.
- One-pack type modified silicone sealant consists of 85 g of Shiraka Hana CCR (manufactured by Shiraishi Kogyo Co., Ltd.), 100 g of modified silicone polymer (trade name “MS Polymer S203” manufactured by Kaneka Chemical Co., Ltd.), 50 g of DOP, heavy calcium carbonate (trade name “White” 305 "manufactured by Shiroishi Kogyo Co., Ltd.) 35g, surface treated calcium carbonate 15g, trimethoxyvinylsilane (trade name" KBM # 1003 "manufactured by Shin-Etsu Chemical Co., Ltd.) 3.4g, and catalyst (trade name"# 918 ”) 2.5 g (manufactured by Synthesizer) was sufficiently
- the one-component modified silicone sealant using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention has a low viscosity and good thixotropic properties. Moreover, it turns out that storage stability is also favorable.
- ⁇ Viscosity test of two-component modified silicone sealant> For the surface-treated calcium carbonate of Examples 1 to 7 and Comparative Examples 1 to 7, two-component modified silicone sealants were prepared and their viscosities were measured.
- the formulation of the two-component modified silicone sealant is as follows: Shiraka Hana CCR (manufactured by Shiraishi Kogyo Co., Ltd.) 120 g, modified silicone polymer (trade name “MS Polymer S203” Kaneka Chemical Co., Ltd.) 35 g, DOP 50 g , Using a mixture of 20 g of heavy calcium carbonate (trade name “Whiten P-30 Shiraishi Kogyo Co., Ltd.”), 15 g of surface-treated calcium carbonate, and 5 g of Epicoat 828 (manufactured by Yuka Shell Epoxy) As an agent, a mixture of heavy calcium carbonate (trade name “Whiten P-30 Shiraishi Kogyo Co., Ltd.” 20 g, DOP 6.3 g, t
- the two-component modified silicone sealant base using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention has a low viscosity and good thixotropic properties. Moreover, it turns out that storage stability is also favorable. Moreover, the viscosity characteristic of such a base was similarly obtained immediately after mixing with the curing agent.
- Polyvinyl chloride sols were prepared for the surface-treated calcium carbonates of Examples 1 to 7 and Comparative Examples 1 to 7, and their viscosities were measured.
- Polyvinyl chloride sol consists of 200g of surface-treated calcium carbonate, 300g of polyvinyl chloride resin (trade name "ZEST P21", Shin-Daiichi PVC Co., Ltd.), DINP 300g, heavy calcium carbonate (trade name "Whiteon P-30", Shiraishi Kogyo Co., Ltd.
- the polyvinyl chloride sol using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention has a low viscosity and good thixotropic properties. Moreover, it turns out that storage stability is also favorable.
- ⁇ Acrylic sol viscosity test> For the surface-treated calcium carbonates of Examples 1 to 7 and Comparative Examples 1 to 7, acrylic sols were prepared and their viscosities were measured.
- the composition of the acrylic sol is 150g of surface treated calcium carbonate, 300g of acrylic resin, 300g of DINP, 100g of heavy calcium carbonate (trade name "Whiten P-30 Shiraishi Kogyo Co., Ltd.”), diluent (trade name "Mineral Turpen” mountain 50 g of Katsura Sangyo Co., Ltd.), 100 g of an adhesion imparting agent (trade name “Versamide 140” manufactured by Henkel Japan), and 2.5 g of an isocyanate resin were sufficiently kneaded and prepared.
- the obtained acrylic sol the initial viscosity and the viscosity after 7 days were measured in the same manner as described above. Table 6 shows the measurement results.
- the acrylic sol using the surface-treated calcium carbonate of Examples 1 to 7 according to the present invention has a low viscosity and good thixotropic properties. Moreover, it turns out that storage stability is also favorable.
- the paste resin can be imparted with low viscosity and high thixotropic properties. Also, good storage stability can be obtained.
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Abstract
Description
本発明において、表面処理の対象として用いる炭酸カルシウム粒子は、特に限定されるものではなく、シリコーンを除く各種高分子材料の充填剤として使用することができるものであればよい。炭酸カルシウムには、天然炭酸カルシウム(重質炭酸カルシウム)及び合成炭酸カルシウム(軽質(膠質)炭酸カルシウム)がある。天然炭酸カルシウムは、石灰石原石から直接製造されるもので、例えば、石灰石原石を機械的に粉砕・分級することにより製造することができる。
本発明においては、ラウリン酸のナトリウム塩及びカリウム塩のうちの少なくとも1種を30~60重量%含む表面処理剤で炭酸カルシウムを表面処理する。ラウリン酸のナトリウム塩及びカリウム塩のさらに好ましい含有割合は、30~55重量%の範囲であり、さらに好ましくは35~55重量%の範囲であり、さらに好ましくは40~55重量%の範囲である。ラウリン酸のナトリウム塩及びカリウム塩の含有割合が少なすぎると、ペースト状樹脂に配合した際の粘度が高くなり、低粘度で、高い揺変性を付与することができない。また、ラウリン酸のナトリウム塩及びカリウム塩の含有割合が多すぎると、高い揺変性を得ることが困難になる。
本発明における表面処理剤は、ラウリン酸のナトリウム塩及びカリウム塩以外に、パルミチン酸のナトリウム塩及びカリウム塩並びにステアリン酸のナトリウム塩及びカリウム塩の内の少なくとも1種を含む。表面処理剤中のラウリン酸のナトリウム塩及びカリウム塩と、パルミチン酸のナトリウム塩及びカリウム塩と、ステアリン酸のナトリウム塩及びカリウム塩の合計の含有割合は80重量%以上である。上述のように、ラウリン酸のナトリウム塩及びカリウム塩の含有割合は最大で60重量%であるので、パルミチン酸のナトリウム塩及びカリウム塩並びにステアリン酸のナトリウム塩及びカリウム塩の合計の含有割合は20重量%以上である。
本発明における表面処理剤は、上記のラウリン酸のナトリウム塩及びカリウム塩、パルミチン酸のナトリウム塩及びカリウム塩、並びにステアリン酸のナトリウム塩及びカリウム塩以外に、その他の脂肪酸のナトリウム塩またはカリウム塩を含んでいてもよい。
本発明においては、上述のように、ラウリン酸のナトリウム塩またはカリウム塩と、パルミチン酸及び/またはステアリン酸のナトリウム塩またはカリウム塩とを含む表面処理剤により炭酸カルシウムが表面処理される。その他の脂肪酸のナトリウム塩またはカリウム塩として、不飽和脂肪酸のナトリウム塩またはカリウム塩を含んでいてもよいが、その含有割合は、5重量%以下であることが好ましい。不飽和脂肪酸のナトリウム塩及びカリウム塩の含有割合が、5重量%を越えると、貯蔵安定性が低下する。特に、長時間の保存により粘度が低下する傾向にある。不飽和脂肪酸のナトリウム塩及びカリウム塩のさらに好ましい含有割合は、4重量%以下であり、さらに好ましくは3重量%以下であり、さらに好ましくは2重量%以下である。
本発明における表面処理剤は、上述のように、ラウリン酸のナトリウム塩及びカリウム塩と、パルミチン酸のナトリウム塩及びカリウム塩と、ステアリン酸のナトリウム塩及びカリウム塩の合計の割合が80重量%以上であり、かつラウリン酸のナトリウム塩及びカリウム塩の割合が30~60重量%の範囲内であり、不飽和脂肪酸のナトリウム塩及びカリウム塩の含有割合が5重量%以下である。このような条件を満たすならば、表面処理剤として、ラウリン酸のナトリウム塩及びカリウム塩、パルミチン酸のナトリウム塩及びカリウム塩、ステアリン酸のナトリウム塩及びカリウム塩、並びにその他の脂肪酸のナトリウム塩及びカリウム塩以外の表面処理剤を含んでいてもよい。例えば、本発明の効果が失われない範囲において、ラウリン酸、パルミチン酸、ステアリン酸、及びその他の脂肪酸を酸の形態で含んでいてもよい。また、アルキルベンゼンスルホン酸などのスルホン酸塩や、樹脂酸のナトリウム塩またはカリウム塩なども、本発明の効果が失われない範囲において含まれていてもよい。
本発明の表面処理炭酸カルシウムは、上記表面処理剤で表面処理された炭酸カルシウムである。
抽出脂肪酸量から、酸の形態及びナトリウム塩もしくはカルシウム塩の形態のままで表面処理炭酸カルシウムの表面に付着しているラウリン酸等の脂肪酸及びその塩の含有割合を求めることができる。
本発明の表面処理炭酸カルシウムは、炭酸カルシウム粒子のスラリー液に、上記表面処理剤を添加して攪拌することにより製造することができる。上述のように、ラウリン酸等の脂肪酸のナトリウム塩またはカリウム塩は、炭酸カルシウム表面のカルシウムと反応し、不溶性のカルシウム塩となることにより表面処理することができる。表面処理した炭酸カルシウムのスラリー液は、その後脱水、乾燥することにより、表面処理炭酸カルシウムの粉末を得ることができる。
本発明の表面処理炭酸カルシウムは、インキ、塗料、シーリング材、PVCゾル、DOPゾル、アクリルゾル等のペースト状樹脂に配合した際、低い粘度で、かつ高い揺変性を付与することができ、さらには良好な貯蔵安定性が得られる。ペースト状樹脂に対する表面処理炭酸カルシウムの配合量は、配合目的、ペースト状樹脂に求められる特性等に応じて適宜調整することができる。
ポリウレタンシーラントなどとして用いることができるポリウレタンペースト状樹脂組成物は、主にイソシアネート、ポリオール、可塑剤、充填剤、その他の添加剤を含む。
変性シリコーンシーラントなどの変性シリコーンペースト状樹脂組成物は、主に変性シリコーン樹脂、可塑剤、充填剤、及びその他の添加剤からなる。高分子の末端に反応性のシリコーン官能基を導入して変性させた樹脂であり、シリコーン樹脂とは分子構造が全く異なる樹脂である。
ポリサルファイドシーラントなどのポリサルファイドペースト状樹脂組成物は、主にポリサルファイド樹脂、可塑剤、充填剤、及びその他の添加剤を含む。
ポリ塩化ビニル樹脂組成物は、主に塩化ビニル樹脂、可塑剤、充填剤、その他の添加剤を含む。可塑剤、充填剤、及びその他の添加剤としては、ポリウレタンペースト状樹脂組成物において説明したものと同様のものを用いることができる。
アクリルゾル樹脂組成物は、主にアクリル樹脂、架橋剤、可塑剤、充填剤、及びその他の添加剤を含む。
印刷インキ組成物は、主に、色料、ビヒクル、添加剤などを含む。
塗料組成物は、主に、顔料、ビヒクル、及び添加剤などを含む。
(実施例1)
BET比表面積が24m2/gである合成炭酸カルシウム2kgに、固形分10重量%となるように、60℃に調整した水を加え、攪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。該スラリー液を分散機で攪拌しながら、ラウリン酸ナトリウム35g、ステアリン酸ナトリウム17.5g、及びパルミチン酸ナトリウム17.5gを混合した混合脂肪酸ナトリウム塩75g(ラウリン酸ナトリウム50%、ステアリン酸ナトリウム25%、パルミチン酸ナトリウム25%)を、この炭酸カルシウムスラリー液に添加し、5分間攪拌した後、プレス脱水した。
BET比表面積が20m2/gの合計炭酸カルシウムを用いる以外は、上記の実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム35g、パルミチン酸ナトリウム16.4g、ステアリン酸ナトリウム16.5g、及びオレイン酸ナトリウム2.1gを混合した混合脂肪酸ナトリウム塩75g(ラウリン酸ナトリウム50%、パルミチン酸ナトリウム23.4%、ステアリン酸ナトリウム23.6%、オレイン酸ナトリウム3%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム24.5g、パルミチン酸ナトリウム22.8g、及びステアリン酸ナトリウム22.8gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム35%、パルミチン酸ナトリウム32.5%、ステアリン酸ナトリウム32.5%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム42g、パルミチン酸ナトリウム14g、及びステアリン酸ナトリウム14gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム60%、パルミチン酸ナトリウム20%、ステアリン酸ナトリウム20%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
BET比表面積が35m2/gの合成炭酸カルシウムを用い、ラウリン酸ナトリウム100g、パルミチン酸ナトリウム50g、及びステアリン酸ナトリウム50gを混合した混合脂肪酸ナトリウム塩200g(ラウリン酸ナトリウム50%、パルミチン酸ナトリウム25%、ステアリン酸ナトリウム25%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム35g、ミリスチン酸ナトリウム11.2g、パルミチン酸ナトリウム11.9g、ステアリン酸ナトリウム11.9g、及びオレイン酸ナトリウム1.4gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム50%、ミリスチン酸ナトリウム16%、パルミチン酸ナトリウム17%、ステアリン酸ナトリウム17%、オレイン酸ナトリウム2%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム49g、パルミチン酸ナトリウム10.5g、及びステアリン酸ナトリウム10.5gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム70%、パルミチン酸ナトリウム15%、ステアリン酸ナトリウム15%)を用いる以外は、上記実施例1と同様にして表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム14g、パルミチン酸ナトリウム28g、及びステアリン酸ナトリウム28gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム20%、パルミチン酸ナトリウム40%、ステアリン酸ナトリウム40%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
ラウリン酸ナトリウム35g、パルミチン酸ナトリウム15g、ステアリン酸ナトリウム15g、及びオレイン酸ナトリウム5gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム50%、パルミチン酸ナトリウム21.5%、ステアリン酸ナトリウム21.5%、オレイン酸ナトリウム7%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
BET比表面積が9m2/gの合成炭酸カルシウムを用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
本比較例では、脂肪酸ナトリウム塩を用いずに、脂肪酸を用いて表面処理した。
本比較例においては、脂肪酸ナトリウム塩を用いずに、脂肪酸と乳化剤とを用いて表面処理した。
ラウリン酸ナトリウム33.6g、ミリスチン酸ナトリウム28g、パルミチン酸ナトリウム4.2g、ステアリン酸ナトリウム4.2gを混合した混合脂肪酸ナトリウム塩70g(ラウリン酸ナトリウム48%、ミリスチン酸ナトリウム40%、パルミチン酸ナトリウム6%、ステアリン酸ナトリウム6%)を用いる以外は、上記実施例1と同様にして、表面処理炭酸カルシウムを得た。
表面処理前及び表面処理後の炭酸カルシウムについて、BET比表面積を測定した。BET比表面積は、比表面積測定装置 フローソープII2300(マイクロメリチック社製)を用いて測定した。測定結果を表1に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、抽出脂肪酸量を測定した。表面処理炭酸カルシウム15gを、ソックスレー抽出器に入れ、ジエチルエーテル100mlで、表面処理炭酸カルシウム中の遊離脂肪酸及び遊離脂肪酸塩を抽出した。抽出前及び抽出後の表面処理炭酸カルシウムの重量変化と、表面処理炭酸カルシウムの試料重量から、抽出脂肪酸量を求めた。測定結果を表1に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、DOPゾルを作製し、その粘度を測定した。DOPゾルは、表面処理炭酸カルシウム100gとDOP(ジオクチルフタレート、ジェイ・プラス社製)100gとをハイブリッドミキサー(HM-500 キーエンス製)で40秒間攪拌、得られたDOPゾルの初期粘度を20℃で測定した。また、20℃×7日後の粘度を20℃で測定した。粘度は、BH型粘度計(TOKIMEC製)によって、2rpmと20rpmで測定した。測定結果を表1に示す。なお、粘度上昇率は、混練直後の粘度に対する7日後の粘度の上昇率を示している。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、PPG(ポリプロピレングリコール)ゾルの粘度を測定した。PPGゾルの配合は、表面処理炭酸カルシウム200gとPPG(ポリプロピレングリコール、商品名「スミフェン3086」、住化バイエルウレタン社製)200gとを十分に混練し、得られたPPGゾルの初期粘度及び7日後の粘度を、上記と同様にして測定した。測定結果を表2に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、1液型変性シリコーンシーラントを調製し、その粘度を測定した。1液型変性シリコーンシーラントは、白艶華CCR(白石工業株式会社製)85g、変性シリコーンポリマー(商品名「MSポリマーS203」鐘淵化学株式会社製)100g、DOP50g、重質炭酸カルシウム(商品名「ホワイトン305」白石工業株式会社製)35g、表面処理炭酸カルシウム15g、トリメトキシビニルシラン(商品名「KBM#1003」信越化学株式会社製)3.4g、及び触媒(商品名「#918」三共有機合成社製)2.5gを十分に混練して調製した。得られた1液型変性シリコーンシーラントについて、初期粘度及び7日後の粘度を上記と同様にして測定した。測定結果を表3に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、2液型変性シリコーンシーラントを調製し、その粘度を測定した。2液型変性シリコーンシーラントの配合は、基剤として、白艶華CCR(白石工業株式会社製)を120g、変性シリコーンポリマー(商品名「MSポリマーS203」鐘淵化学株式会社製)を35g、DOPを50g、重質炭酸カルシウム(商品名「ホワイトンP-30白石工業株式会社製」)を20g、表面処理炭酸カルシウムを15g、及びエピコート828(油化シェルエポキシ製)5gを混合したものを用い、硬化剤として、重質炭酸カルシウム(商品名「ホワイトンP-30白石工業株式会社製」20g、DOP6.3g、オクチル酸錫(製)3g、及びラウリルアミン(製)0.7gを混合したものを用いた。基剤及び硬化剤のそれぞれを十分に混練し、得られた2液型変性シリコーンシーラントの基剤について混練直後の粘度及び7日後の粘度を上記と同様にして測定した。ただし、本評価に限ってBH型粘度計で1rpm及び10rpmの値を測定した。測定結果を表4に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、ポリ塩化ビニルゾルを調製し、その粘度を測定した。ポリ塩化ビニルゾルは、表面処理炭酸カルシウム200g、ポリ塩化ビニル樹脂(商品名「ZEST P21」新第一塩ビ社製)300g、DINP300g、重質炭酸カルシウム(商品名「ホワイトンP-30」白石工業株式会社製)150g、接着付与剤(商品名「バーサミド140」ヘンケルジャパン製)10g、及び希釈剤(商品名「ミネラルターペン」山桂産業株式会社製)40gを十分に混練して調製した。得られたポリ塩化ビニルゾルについて初期粘度及び7日後の粘度を、上記と同様にして測定した。測定結果を表5に示す。
実施例1~7及び比較例1~7の表面処理炭酸カルシウムについて、アクリルゾルを調製し、その粘度を測定した。アクリルゾルの配合は、表面処理炭酸カルシウム150g、アクリル樹脂300g、DINP300g、重質炭酸カルシウム(商品名「ホワイトンP-30白石工業株式会社製」)100g、希釈剤(商品名「ミネラルターペン」山桂産業株式会社製)50g、接着付与剤(商品名「バーサミド140」ヘンケルジャパン製)100g、及びイソシアネート樹脂2.5gを十分に混練して調製した。得られたアクリルゾルについて初期粘度及び7日後の粘度を、上記と同様にして測定した。測定結果を表6に示す。
2…ラウリン酸
3…パルミチン酸及び/またはステアリン酸
4…マトリックス樹脂の有機物鎖
Claims (12)
- 脂肪酸のナトリウム塩またはカリウム塩を含む表面処理剤で表面処理された炭酸カルシウムであって、表面処理剤中のラウリン酸のナトリウム塩及びカリウム塩と、パルミチン酸のナトリウム塩及びカリウム塩と、ステアリン酸のナトリウム塩及びカリウム塩の合計の含有割合が80重量%以上であり、かつラウリン酸のナトリウム塩及びカリウム塩の含有割合が30~60重量%の範囲内であり、表面処理剤中の不飽和脂肪酸のナトリウム塩及びカリウム塩の含有割合が5重量%以下であり、BET比表面積が10m2/g以上であることを特徴とする表面処理炭酸カルシウム。
- その他の脂肪酸のナトリウム塩またはカリウム塩が、炭素数14~22の脂肪酸のナトリウム塩またはカリウム塩であることを特徴とする請求項1に記載の表面処理炭酸カルシウム。
- BET比表面積が、10~100m2/gであることを特徴とする請求項1または2に記載の表面処理炭酸カルシウム。
- 炭酸カルシウム100重量部に対して、2~15重量部の表面処理剤が処理されていることを特徴とする請求項1~3のいずれか1項に記載の表面処理炭酸カルシウム。
- 表面処理炭酸カルシウムをジエチルエーテルで抽出することにより求められる抽出脂肪酸量が0.4重量%以下であることを特徴とする請求項1~4のいずれか1項に記載の表面処理炭酸カルシウム。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とするポリウレタンペースト状樹脂組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とする変性シリコーンペースト状樹脂組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とするポリサルファイドペースト状樹脂組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とするポリ塩化ビニルゾル樹脂組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とするアクリルゾル樹脂組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とする印刷インキ組成物。
- 請求項1~5のいずれか1項に記載の表面処理炭酸カルシウムが含有されたことを特徴とする塗料組成物。
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KR100872191B1 (ko) | 2002-09-27 | 2008-12-09 | 인터내셔널 비지네스 머신즈 코포레이션 | 발표 하이퍼링크 타임 테이블 생성 방법, 발표 처리 방법, 컴퓨팅 시스템 및 컴퓨터 판독가능한 기록 매체 |
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- 2009-03-27 JP JP2009078831A patent/JP4565040B2/ja not_active Expired - Fee Related
-
2010
- 2010-03-18 KR KR20117022380A patent/KR20110138220A/ko not_active Application Discontinuation
- 2010-03-18 RU RU2011143308/05A patent/RU2011143308A/ru unknown
- 2010-03-18 WO PCT/JP2010/054636 patent/WO2010110161A1/ja active Application Filing
- 2010-03-18 US US13/258,673 patent/US8329802B2/en not_active Expired - Fee Related
- 2010-03-18 CN CN201080014114.1A patent/CN102365236B/zh not_active Expired - Fee Related
- 2010-03-18 EP EP10755959A patent/EP2412673A1/en not_active Withdrawn
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9422416B2 (en) | 2010-11-30 | 2016-08-23 | Shiraishi Central Laboratories Co., Ltd. | Resin composition |
JPWO2018180393A1 (ja) * | 2017-03-27 | 2020-02-06 | 株式会社カネカ | 塩化ビニル−酢酸ビニル共重合体樹脂組成物 |
JP7149535B2 (ja) | 2017-03-27 | 2022-10-07 | 株式会社カネカ | 塩化ビニル-酢酸ビニル共重合体樹脂組成物 |
Also Published As
Publication number | Publication date |
---|---|
JP2010228976A (ja) | 2010-10-14 |
CN102365236A (zh) | 2012-02-29 |
EP2412673A1 (en) | 2012-02-01 |
KR20110138220A (ko) | 2011-12-26 |
JP4565040B2 (ja) | 2010-10-20 |
RU2011143308A (ru) | 2013-05-10 |
US20120035312A1 (en) | 2012-02-09 |
US8329802B2 (en) | 2012-12-11 |
CN102365236B (zh) | 2014-09-17 |
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