WO2016103347A1 - 末端シリル基樹脂組成物及びその製造方法 - Google Patents
末端シリル基樹脂組成物及びその製造方法 Download PDFInfo
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- WO2016103347A1 WO2016103347A1 PCT/JP2014/084079 JP2014084079W WO2016103347A1 WO 2016103347 A1 WO2016103347 A1 WO 2016103347A1 JP 2014084079 W JP2014084079 W JP 2014084079W WO 2016103347 A1 WO2016103347 A1 WO 2016103347A1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/288—Compounds containing at least one heteroatom other than oxygen or nitrogen
- C08G18/289—Compounds containing at least one heteroatom other than oxygen or nitrogen containing silicon
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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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4692—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/588—Epoxy resins having silicon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/32—Polymers modified by chemical after-treatment
- C08G65/329—Polymers modified by chemical after-treatment with organic compounds
- C08G65/336—Polymers modified by chemical after-treatment with organic compounds containing silicon
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- 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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- C—CHEMISTRY; METALLURGY
- 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
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
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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
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1021—Polyurethanes or derivatives thereof
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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
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
Definitions
- the present invention relates to a terminal silyl group resin composition and a method for producing the same.
- An object of the present invention is to provide a terminal silyl group resin composition having a low initial modulus of a cured product, capable of maintaining a low modulus even after a heating acceleration test, and excellent in storage stability before curing, and a method for producing the same. It is to provide.
- terminal silyl group resin composition of the present invention calcium carbonate having a BET specific surface area in the range of 1 m 2 / g to 60 m 2 / g is surface-treated with a fatty acid, and the alkali metal content is 500 ⁇ g / g to 2000 ⁇ g / g.
- the free fatty acid obtained by extraction with ethanol is characterized in that it contains surface-treated calcium carbonate in the range of 1.8 to 2.5% by mass and a terminal silyl group resin. .
- terminal silyl group resin examples include those containing a terminal silyl group polyether resin as a main component and those containing a terminal silyl group polyurethane resin as a main component.
- the content of the surface-treated calcium carbonate contained in the terminal silyl group resin composition is preferably in the range of 50 to 200 parts by mass with respect to 100 parts by mass of the terminal silyl group resin.
- the alkali metal is preferably at least one of sodium and potassium.
- the production method of the present invention is a method for producing the terminal silyl group resin composition of the present invention, wherein the surface of calcium carbonate is added with fatty acid so that the free fatty acid is in the range of 1.8 to 2.5% by mass. And a step of adding an alkali metal compound to the fatty acid-treated calcium carbonate to produce a surface-treated calcium carbonate, and a step of blending the surface-treated calcium carbonate with a terminal silyl group resin. .
- a terminal silyl group resin composition having a low initial modulus of a cured product, capable of maintaining a low modulus even after a heating acceleration test, and having excellent storage stability before curing.
- calcium carbonate For example, conventionally known calcium carbonate can be used as the surface-treated calcium carbonate.
- 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 BET specific surface area of calcium carbonate is preferably in the range of 1 m 2 / g to 60 m 2 / g, more preferably in the range of 3 m 2 / g to 30 m 2 / g, and from 7 m 2 / g to More preferably, it is within the range of 30 m 2 / g.
- the BET specific surface area of calcium carbonate is too low, it cannot have high thixotropy, and the function as surface-treated calcium carbonate is impaired. If the BET specific surface area of calcium carbonate is too high, the cohesive force generally becomes strong, the dispersibility is poor even when surface treatment is performed, and the viscosity does not develop even when blended in a sealing material.
- 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.
- lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid and the like are preferably used.
- the unsaturated fatty acid include obsylic 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, cetoleic acid, erucic acid, brassic acid, ceracolic acid, ximenoic acid, lumectric acid, sorbic acid, linoleic acid and the like.
- the form of the fatty acid when the surface treatment of calcium carbonate with the fatty acid is not particularly limited, and the surface treatment can be performed in the form of a fatty acid metal salt, an acid form, an ester form, or the like. If necessary, these forms may be used in combination for surface treatment.
- 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.
- fatty acid esters examples include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate, and the like.
- a sodium salt or potassium salt of a saturated fatty acid having 9 to 21 carbon atoms can be mentioned.
- sodium salts such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid are particularly preferable.
- Examples of the method for surface treatment of calcium carbonate include a wet treatment method and a dry treatment method.
- Examples of the wet processing method include a method of adding a solution containing a fatty acid to a slurry containing calcium carbonate and water, followed by dehydration and drying.
- Examples of the solution containing a fatty acid include a solution containing a fatty acid in the form of a metal salt such as an alkali metal salt, an acid form, or an ester form. Among these, those containing an alkali metal salt form of a fatty acid as the main component of the fatty acid are preferably used.
- Examples of the dry treatment method include a method of adding a surface treatment agent to calcium carbonate while stirring the calcium carbonate.
- the surface treatment agent may be added as a solution, or calcium carbonate may be added while heating to a temperature equal to or higher than the melting point of the surface treatment agent.
- the fatty acid may be in the form of an acid, may be in the form of an ester, or may be in the form of a metal salt.
- the calcium carbonate may be calcium carbonate that has been surface-treated by wet treatment or the like.
- the free fatty acid required by extraction with ethanol is in the range of 1.8 to 2.5% by mass.
- the “free fatty acid” in the present invention is the total amount of substances derived from the surface treatment agent that can be extracted with ethanol. That is, the total amount of fatty acids extracted with ethanol, metal salts of fatty acids, esters of fatty acids, and the like.
- the free fatty acid is less than 1.8% by mass, a low modulus cannot be maintained after the heating acceleration test.
- free fatty acid exceeds 2.5 mass%, the storage stability before hardening will fall.
- the free fatty acid is preferably in the range of 1.9 to 2.4% by mass, and more preferably in the range of 1.9 to 2.3% by mass.
- the value of the free fatty acid can be adjusted by adding the fatty acid to the alkali metal salt of the fatty acid in the form of an acid or an ester. Moreover, the value of the free fatty acid can also be adjusted by adjusting the amount of the surface treatment agent relative to the BET specific surface area of calcium carbonate. Moreover, when surface-treating using a wet processing method, the value of a free fatty acid can also be adjusted by adjusting the temperature of a calcium carbonate slurry. In this case, when the temperature of the calcium carbonate slurry is increased, the value of the free fatty acid decreases, and when the temperature of the calcium carbonate slurry is decreased, the value of the free fatty acid tends to increase.
- the measurement of the free fatty acid is obtained by extracting the surface-treated calcium carbonate with ethanol and using the following formula.
- 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
- the alkali metal content of the surface-treated calcium carbonate of the present invention is in the range of 500 ⁇ g / g to 2000 ⁇ g / g.
- the alkali metal content of the surface-treated calcium carbonate is preferably in the range of 700 ⁇ g / g to 1900 ⁇ g / g, more preferably in the range of 800 ⁇ g / g to 1800 ⁇ g / g, and 1000 ⁇ g / g to 1800 ⁇ g / g. More preferably, it is within the range of g.
- the alkali metal content is too low, it is difficult to obtain a low modulus in the cured product. If the alkali metal content is too high, the adhesiveness after the cured product is immersed in water is deteriorated, and it is disadvantageous economically, which is not desirable.
- the alkali metal is preferably at least one of sodium and potassium.
- the adjustment of the alkali metal content can be adjusted, for example, by adding an alkali metal compound in the step of producing the surface-treated calcium carbonate. For example, it can adjust by adding the aqueous solution of an alkali metal compound to the water slurry of the calcium carbonate surface-treated with the fatty acid. The addition amount of the alkali metal compound at this time can be adjusted, and alkali metal content can be adjusted. After adding the aqueous solution of the alkali metal compound, the surface-treated calcium carbonate can be obtained by performing dehydration and drying as usual.
- an aqueous solution of an alkali metal compound may be added after dehydrating the aqueous slurry of calcium carbonate surface-treated with a fatty acid. After adding the aqueous solution of the alkali metal compound, the surface-treated calcium carbonate can be obtained by drying as usual.
- alkali metal compound examples include sodium or potassium hydroxide and carbonate. Among these, sodium hydroxide and sodium carbonate are preferable as the alkali metal compound. Only one type of alkali metal compound may be used, or a plurality of types may be used.
- the alkali metal in the surface treatment agent is also included in the alkali metal content. Therefore, the alkali metal content in the surface-treated calcium carbonate including the alkali metal in the surface treatment agent is appropriately adjusted so as to be in the above range.
- Alkaline metal content is measured with an atomic absorption spectrophotometer. An example is described below.
- the content of the surface-treated calcium carbonate contained in the modified silyl group resin composition is preferably 50 parts by weight to 200 parts by weight with respect to 100 parts by weight of the modified silyl group resin, and 80 parts by weight to 150 parts by weight. It is more preferable that When the content of the surface-treated calcium carbonate contained in the modified silicone resin composition is within the above range, it is preferable before curing to ensure appropriate viscosity and thixotropic properties and improve workability. Further, after curing, the balance of modulus, elongation and strength is improved, which is preferable.
- terminal silyl group resin examples include a terminal silyl group polyether resin or a terminal silyl group polyurethane resin as a main component.
- the terminal silyl group polyether resin is known as a modified silicone resin.
- the modified silicone resin and the modified silicone resin composition will be described.
- the modified silicone resin is mainly composed of a silyl group-terminated polyether having a reactive silyl group introduced at the terminal.
- the modified silicone resin preferably forms a siloxane bond by moisture curing.
- the modified silicone resin include polymers formed by using a linear or branched polyoxyalkylene polymer as a main chain and introducing a silyl group at the hydroxyl group terminal.
- the modified silicone resin may be a known one. Commercial products are easily available for the modified silicone resin. Examples of commercial products of the modified silicone resin include MS polymer S810, MS polymer S202, MS polymer S203, MS polymer S303 manufactured by Kaneka Corporation, and EXESTER manufactured by Asahi Glass Co., Ltd.
- the modified silicone resin composition may contain a plasticizer, a filler, an adhesion-imparting agent, a dehydrating agent, a catalyst, and the like.
- 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), butyl benzyl 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 (light calcium carbonate, heavy calcium carbonate, etc.), calcium / magnesium carbonate, basic magnesium carbonate, quartz powder, silica powder, fine powdered silicic acid (dry product, wet product, Gel method product), finely powdered calcium silicate, finely powdered aluminum silicate, kaolin clay, pyrophyllite clay, talc, sericite, mica, bentonite, nepheline sinite, aluminum hydroxide, magnesium hydroxide, barium sulfate, carbon black (furnes , Thermal, acetylene), graphite, acicular / fibrous, sepiolite, wollastonite, zonotlite, potassium titanate, carbon fiber, mineral fiber, glass fiber, shirasu balun, fly ash balun, glass balun, silica beads, aluminabi 'S, such as glass beads,
- organic fillers examples include 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, etc.
- examples include powdery or bead-like materials, cellulose powder, pulp powder, synthetic fiber powder, amide wax, fatty acid amide, castor oil wax, and the like.
- adhesion imparting agent examples include hydrolyzable organic silicone compounds.
- hydrolyzable organic silicone compounds include vinyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane) Or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), silane compounds such as tetrapropyl orthosilicate, tetrabutyl orthosilicate, etc., or partial hydrolysis condensates thereof, ⁇ -aminopropyltrimethoxysilane, ⁇ -glycid Xylpropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltrime
- dehydrating agents include silane coupling agents.
- the silane coupling agent include silane coupling agents having functional groups such as amino group, mercapto group, epoxy group, carboxyl group, vinyl group, isocyanate group, isocyanurate, and halogen.
- Specific examples of the silane coupling agent having these functional groups include ⁇ -isocyanatopropyltrimethoxysilane, ⁇ -isocyanatopropyltriethoxysilane, ⁇ -isocyanatopropylmethyldiethoxysilane, and ⁇ -isocyanatepropylmethyldimethoxysilane.
- Isocyanate group-containing silanes ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltriisopropoxysilane, ⁇ -aminopropylmethyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, ⁇ - (2-aminoethyl) aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) aminopropylmethyldimethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriethoxysilane, ⁇ - (2 Aminoethyl) aminopropylmethyldiethoxysilane, ⁇ - (2-aminoethyl) aminopropyltriisopropoxysilane, ⁇ -ureidopropyltrimethoxysilane, N-phenyl- ⁇ -aminoprop
- Catalysts include dibutyltin diacetylacetonate, stannous octoate, dibutyltin dioctoate, dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin oxide, dibutyltin bistriethoxysilicate, dibutyltin distearate, dioctyltin dilaurate, Known curing catalysts such as organic tin compounds such as dioctyltin diversate, tin octylate and tin naphthenate can be mentioned.
- the modified silicone resin composition may contain one or more plasticizers, fillers, adhesion-imparting agents, dehydrating agents, and catalysts, respectively, or may contain a plurality of types.
- the modified silicone resin composition of the present invention has low modulus, high elongation and high storage stability, it can be suitably used as a sealing material, an adhesive and the like.
- the terminal silyl group polyurethane resin is mainly composed of a silyl group-terminated polyurethane having a reactive silyl group introduced at the terminal.
- the silyl group-terminated polyurethane resin preferably forms a siloxane bond by moisture curing.
- the silyl group-terminated polyurethane resin include a polymer formed by introducing a silyl group into the hydroxyl terminal of a polyurethane having a linear or branched polyoxyalkylene polymer as a main chain.
- the silyl group-terminated polyurethane resin may be a known one. Commercially available products are readily available for the silyl group-terminated polyurethane resin. Examples of commercially available silyl group-terminated polyurethane resins include GENIOSIL STP-E10, GENIOSIL STP-E15, GENIOSIL STP-E30, and GENIOSIL STP-E35 manufactured by WACHER.
- the silyl group-terminated polyurethane resin composition may contain a plasticizer, a filler, an adhesion-imparting agent, a dehydrating agent, a catalyst, and the like. These plasticizer, filler, adhesion-imparting agent, dehydrating agent, and catalyst may be the same as those used in the modified silicone resin composition.
- the silyl group-terminated polyurethane resin composition may contain one or more plasticizers, fillers, adhesion-imparting agents, dehydrating agents, and catalysts, respectively, or may contain a plurality of types.
- the silyl group-terminated polyurethane resin composition of the present invention has low modulus, high elongation, and high storage stability, and therefore can be suitably used as a sealing material, an adhesive and the like.
- the method for producing the terminal silyl group resin composition of the present invention comprises a step of surface-treating calcium carbonate with a fatty acid so that the free fatty acid is in the range of 1.8 to 2.5% by mass, and the fatty acid-treated calcium carbonate. And adding an alkali metal compound to produce a surface-treated calcium carbonate and blending the surface-treated calcium carbonate with a terminal silyl group resin.
- the surface treatment of calcium carbonate with a fatty acid is performed so that the free fatty acid of the surface-treated calcium carbonate after the addition of an alkali metal compound is within the range of 1.8 to 2.5% by mass. To do.
- the aqueous solution of the alkali metal compound is added to the fatty acid-treated calcium carbonate slurry, or the aqueous solution of the alkali metal compound is added after dehydrating the fatty acid-treated calcium carbonate slurry. By doing so, an alkali metal compound is added.
- the surface-treated calcium carbonate obtained as described above is mixed with the terminal silyl group resin.
- the method for mixing the surface-treated calcium carbonate with the terminal silyl group resin is not particularly limited.
- the surface-treated calcium carbonate and the terminal silyl group resin can be mixed by stirring with a stirrer or the like.
- a plasticizer, a filler, an adhesion-imparting agent, a dehydrating agent, a catalyst and the like may be mixed.
- a terminal silyl group resin composition having a low initial modulus of a cured product, capable of maintaining a low modulus even after a heating acceleration test, and excellent in storage stability before curing is produced. can do.
- fatty acid mass ratio
- a 10% by mass aqueous solution of a mixture of myristic acid: palmitic acid: stearic acid: oleic acid 2: 22: 22: 35, No. 0 fatty acid manufactured by NOF Corporation) at a predetermined ratio, and surface treatment An agent solution was obtained.
- This surface treating agent solution was added to the above calcium carbonate slurry to surface-treat calcium carbonate.
- the addition amount of the mixed fatty acid sodium salt with respect to 100 mass parts of calcium carbonate is 2.7 mass parts, and the addition amount of the fatty acid is 0.3 mass part.
- fatty acid mass ratio
- a 10% by mass aqueous solution of a mixture of myristic acid: palmitic acid: stearic acid: oleic acid 2: 22: 22: 35, No. 0 fatty acid manufactured by NOF Corporation) at a predetermined ratio, and surface treatment An agent solution was obtained.
- This surface treating agent solution was added to the above calcium carbonate slurry to surface-treat calcium carbonate.
- the addition amount of mixed fatty acid sodium salt with respect to 100 mass parts of calcium carbonate is 4.5 mass parts, and the addition amount of fatty acid is 0.5 mass part.
- the surface-treated calcium carbonate O was the same as the surface-treated calcium carbonate L except that the added amount of the mixed fatty acid sodium salt was 5.2 parts by mass and the added amount of the fatty acid was 1.3 parts by mass with respect to 100 parts by mass of the calcium carbonate. Got. About the obtained surface-treated calcium carbonate O, it was 2.5 mass% when the free fatty acid was measured by said measuring method.
- Comparison surface treatment calcium carbonate V A surface-treated calcium carbonate V was obtained in the same manner as the surface-treated calcium carbonate N except that an aqueous sodium hydroxide solution was added so that the alkali metal content contained in the surface-treated calcium carbonate was 2300 ⁇ g / g. About the obtained surface treatment calcium carbonate V, it was 2.2 mass% when the free fatty acid was measured by said measuring method.
- Tables 3 and 4 show the BET specific surface area, alkali metal content, and free fatty acid values of the obtained surface-treated calcium carbonate.
- modified silicone resin compositions of Examples 1 to 14 and Comparative Examples 1 to 8 were produced. Specifically, 120 parts by mass of surface-treated calcium carbonate, modified silicone resin (MS polymer S203 (60 parts by mass), MS polymer S303 (40 parts by mass) manufactured by Kaneka Corporation), 55 parts of diisononyl phthalate (DINP) 55 Parts by weight, 40 parts by weight of heavy calcium carbonate (Shiraishi Kogyo Co., Ltd., Whiten 305), 2 parts by weight of fatty acid amide (AS-A T1800 made by Ito Oil Co., Ltd.), and aminosilane (made by Toray Dow Corning) 2 parts by weight of SH2000), 3 parts by weight of vinylsilane (KBM1003 manufactured by Shin-Etsu Silicone), and 2 parts by weight of dibutyltin diacety
- the initial 50% modulus of the resin composition was measured as follows. A PP sheet is stretched on a glass plate, a glass spacer with a thickness of 3.0 mm is pasted on the sheet, and the obtained paste is filled in the frame so as not to contain air bubbles. Cured for 14 days at 30 ° C. The sheet is punched out in the dumbbell shape No. 2 specified in JIS K6251 and the test piece is left at 23 ° C. for one day or more, then the thickness of the test piece is measured, and the test is performed at a tensile speed of 200 mm / min by an autograph. The 50% modulus was measured.
- the 50% modulus after heating of the resin composition was measured as follows. Filling, curing, and punching were performed under the same conditions as the initial 50% modulus measurement. Then, after leaving at 80 ° C. for 7 days and 14 days, respectively, after leaving the test piece to stand at 23 ° C. for 1 day or longer, the thickness of the test piece is measured, and the autograph is tested at a tensile rate of 200 mm / min to accelerate heating. The 50% modulus after the test was measured.
- the storage stability of the obtained paste was measured as follows.
- the change rate of the initial viscosity and the viscosity after storage was used as an index of storage stability.
- the viscosity change rate was calculated according to the following formula.
- the initial viscosity was taken from the cartridge into a container and immediately measured with a B-type viscometer.
- the viscosity after storage was measured by a B-type viscometer after leaving the cartridge at 50 ° C. for 14 days, then leaving it at 20 ° C. for 3 hours or more, taking it into a container.
- Viscosity change rate (%) [(viscosity after storage ⁇ initial viscosity) / initial viscosity] ⁇ 100
- Tables 1 to 4 show this viscosity change rate as storage stability.
- Tables 1 to 4 show the storage stability, initial 50% modulus, 50% modulus after 7 days at 80 ° C., 50% modulus after 14 days at 80 ° C., and 50% modulus change rate in each example and each comparative example.
- the 50% modulus change rate is a value calculated by the following equation.
- 50% modulus change rate (%) [(50% modulus after 14 days at 80 ° C. ⁇ initial 50% modulus) / initial 50% modulus] ⁇ 100
- the water resistance adhesion of the resin composition was measured as follows. Use a 50 ⁇ 50 ⁇ 5 mm aluminum plate specified in 5.17 of JIS A1439: 2004, and make a space of 12 ⁇ 12 ⁇ 50 mm by combining spacers (1 type H-type specimen). The obtained paste was filled and cured under the same conditions as the initial 50% modulus measurement. After being immersed in water and allowed to stand for 7 days, the test piece was allowed to stand at 23 ° C. for 1 day or longer and then tested with an autograph at a tensile rate of 50 mm / min. (Cohesive failure) was marked with ⁇ , and peeling (interface peeling) was marked with ⁇ .
- Examples 1 to 4 in which the free fatty acid is within the range of 1.8 to 2.5% by mass according to the present invention are compared with Comparative Examples 1 and 2 in which the free fatty acid is outside the scope of the present invention.
- the storage stability is excellent and the 50% modulus change rate after the heating acceleration test is small.
- Comparative Example 1 in which the free fatty acid is smaller than the range of the present invention the 50% modulus change rate after the heating acceleration test is large.
- Comparative Example 2 where the free fatty acid is larger than the range of the present invention the storage stability is poor.
- Examples 3 and 5 to 7 in which the alkali metal content is within the range of 500 ⁇ g / g to 2000 ⁇ g / g according to the present invention are comparative examples in which the alkali metal content is outside the range of the present invention.
- the storage stability is excellent and the 50% modulus change rate after the heating acceleration test is small.
- Comparative Example 3 in which the alkali metal content is smaller than the range of the present invention the storage stability is poor and the 50% modulus change rate after the heating acceleration test is large.
- Comparative Example 4 in which the alkali metal content is larger than the range of the present invention the water-resistant adhesion is poor.
- Examples 10 and 12 to 14 in which the alkali metal content is within the range of 500 ⁇ g / g to 2000 ⁇ g / g according to the present invention are comparative examples in which the alkali metal content is outside the range of the present invention.
- the storage stability is excellent, and the 50% modulus change rate after the heating acceleration test is small.
- Comparative Example 7 in which the alkali metal content is smaller than the range of the present invention the storage stability is poor and the 50% modulus change rate after the heating acceleration test is large.
- Comparative Example 8 in which the alkali metal content is larger than the range of the present invention the water-resistant adhesion is poor.
- a modified silicone resin (terminal silyl group polyether resin) was used as the terminal silyl group resin, but another terminal silyl group resin such as a terminal silyl group polyurethane resin was used. In such a case, the same effect can be obtained.
- the value of the free fatty acid is adjusted by adding a fatty acid to the mixed fatty acid sodium salt, but the present invention is not limited to this.
- alkali metal content is adjusted by adding sodium hydroxide aqueous solution to the slurry of the calcium carbonate which processed the fatty acid, this invention is limited to this. It is not a thing.
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Abstract
Description
本発明の製造方法は、上記本発明の末端シリル基樹脂組成物を製造する方法であって、遊離脂肪酸が1.8~2.5質量%の範囲内となるように脂肪酸で炭酸カルシウムを表面処理する工程と、上記脂肪酸処理炭酸カルシウムに、アルカリ金属化合物を添加し、表面処理炭酸カルシウムを製造する工程と、表面処理炭酸カルシウムを末端シリル基樹脂に配合する工程とを備えることを特徴としている。
表面処理される炭酸カルシウムとしては、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。
脂肪酸としては、例えば炭素数6~31の飽和または不飽和の脂肪酸が挙げられる。
飽和脂肪酸の具体例としては、カプロン酸、カプリル酸、ペラルゴン酸、カプリン酸、ウンデカン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アライン酸、ベヘン酸、リグノセリン酸、セロチン酸、モンタン酸、メリシン酸などが挙げられる。これらの中でも、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アライン酸などが好ましく用いられる。
炭酸カルシウムを表面処理する方法としては、湿式処理方法及び乾式処理方法が挙げられる。
本発明の表面処理炭酸カルシウムにおいては、エタノールで抽出することにより求められる遊離脂肪酸が、1.8~2.5質量%の範囲内である。本発明における「遊離脂肪酸」は、エタノールで抽出することができる表面処理剤由来の物質の合計量である。すなわち、エタノールで抽出される脂肪酸、脂肪酸の金属塩、脂肪酸のエステル等の合計量である。遊離脂肪酸が1.8質量%未満であると、加熱促進試験後において低いモジュラスを維持することができない。また、遊離脂肪酸が2.5質量%を超えると、硬化前の貯蔵安定性が低下する。本発明において、遊離脂肪酸は、好ましくは、1.9~2.4質量%の範囲内であり、さらに好ましくは、1.9~2.3質量%の範囲内である。
抽出脂肪酸量(重量%)=〔(抽出前の表面処理炭酸カルシウムの重量-抽出後の表面処理炭酸カルシウムの重量)/(抽出前の表面処理炭酸カルシウムの重量)〕×100
本発明の表面処理炭酸カルシウムのアルカリ金属含有量は、500μg/g~2000μg/gの範囲内である。表面処理炭酸カルシウムのアルカリ金属含有量は、700μg/g~1900μg/gの範囲内であることが好ましく、800μg/g~1800μg/gの範囲内であることがより好ましく、1000μg/g~1800μg/gの範囲内であることがさらに好ましい。アルカリ金属含有量が低すぎると、硬化物において低いモジュラスが得られにくくなる。アルカリ金属含有量が高すぎると、硬化物を水に浸漬した後の接着性が悪くなることと、経済的にも不利益となるため望ましくない。
アルカリ金属含有量の調整は、例えば、表面処理炭酸カルシウムを製造する工程において、アルカリ金属化合物を添加することにより調整することができる。例えば、脂肪酸で表面処理された炭酸カルシウムの水スラリーにアルカリ金属化合物の水溶液を添加することにより調整することができる。このときのアルカリ金属化合物の添加量を調整し、アルカリ金属含有量を調整することができる。アルカリ金属化合物の水溶液を添加した後、通常のように、脱水、乾燥を行うことにより表面処理炭酸カルシウムを得ることができる。また、脂肪酸で表面処理された炭酸カルシウムの水スラリーを脱水した後、アルカリ金属化合物の水溶液を添加してもよい。アルカリ金属化合物の水溶液を添加した後、通常のように、乾燥を行うことにより表面処理炭酸カルシウムを得ることができる。
変成シリル基樹脂組成物中に含まれる表面処理炭酸カルシウムの含有量は、変成シリル基樹脂100重量部に対して、50重量部~200重量部であることが好ましく、80重量部~150重量部であることがより好ましい。変成シリコーン樹脂組成物中に含まれる表面処理炭酸カルシウムの含有量が、上記範囲内であると、硬化前では、適度な粘性と揺変性が確保され、作業性が良好となるため好ましい。また、硬化後では、モジュラス、伸び、強度のバランスがよくなるため好ましい。
変成シリコーン樹脂は、末端に反応性シリル基を導入したシリル基末端ポリエーテルを主成分とするものである。例えば、変成シリコーン樹脂組成物をシーラントとして用いる場合、変成シリコーン樹脂は、湿気硬化でシロキサン結合を形成するものであることが好ましい。変成シリコーン樹脂としては、例えば直鎖または分岐のポリオキシアルキレンポリマーを主鎖とし、その水酸基末端にシリル基を導入して形成したポリマーが挙げられる。変成シリコーン樹脂は、公知ものであってよい。変成シリコーン樹脂は、市販品が容易に入手可能である。変成シリコーン樹脂の市販品としては、例えば、カネカ社製のMSポリマーS810、MSポリマーS202、MSポリマーS203、MSポリマーS303、旭硝子社製のエクセスターなどが挙げられる。
末端シリル基ポリウレタン樹脂は、末端に反応性シリル基を導入したシリル基末端ポリウレタンを主成分とするものである。例えば、シリル基末端ポリウレタン樹脂組成物をシーラントとして用いる場合、シリル基末端ポリウレタン樹脂は、湿気硬化でシロキサン結合を形成するものであることが好ましい。シリル基末端ポリウレタン樹脂としては、例えば直鎖または分岐のポリオキシアルキレンポリマーを主鎖としたポリウレタンの、その水酸基末端にシリル基を導入して形成したポリマーが挙げられる。シリル基末端ポリウレタン樹脂は、公知ものであってよい。シリル基末端ポリウレタン樹脂は、市販品が容易に入手可能である。シリル基末端ポリウレタン樹脂の市販品としては、例えば、WACHER社製の、GENIOSIL STP-E10、GENIOSIL STP-E15、GENIOSIL STP-E30、GENIOSIL STP-E35などが挙げられる。
本発明の末端シリル基樹脂組成物の製造方法は、遊離脂肪酸が1.8~2.5質量%の範囲内となるように脂肪酸で炭酸カルシウムを表面処理する工程と、上記脂肪酸処理炭酸カルシウムに、アルカリ金属化合物を添加し、表面処理炭酸カルシウムを製造する工程と、表面処理炭酸カルシウムを末端シリル基樹脂に配合する工程とを備える。
(表面処理炭酸カルシウムA)
BET比表面積が13m2/gの合成炭酸カルシウム2000gに、固形分が10質量%となるように水を加え、40℃下で撹拌して、炭酸カルシウムのスラリーを調製した。次に、混合脂肪酸ナトリウム塩(質量比でラウリン酸:ミリスチン酸:パルミチン酸:ステアリン酸:オレイン酸=3:2:40:15:30、ミヨシ油脂社製のタンカルMH)と、脂肪酸(質量比でミリスチン酸:パルミチン酸:ステアリン酸:オレイン酸=2:22:22:35、日油社製の0号脂肪酸)とを所定の比率で混合した混合物の10質量%水溶液を調製し、表面処理剤溶液とした。この表面処理剤溶液を上記の炭酸カルシウムスラリーに添加し、炭酸カルシウムを表面処理した。なお、炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量は2.7質量部であり、脂肪酸の添加量は、0.3質量部である。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を2.5質量部とし、脂肪酸の添加量を0.5質量部とする以外は、表面処理炭酸カルシウムAと同様にして表面処理炭酸カルシウムBを得た。得られた表面処理炭酸カルシウムBについて、上記の測定方法で遊離脂肪酸を測定したところ、2.0質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を3.4質量部とし、脂肪酸の添加量を0.6質量部とする以外は、表面処理炭酸カルシウムAと同様にして表面処理炭酸カルシウムCを得た。得られた表面処理炭酸カルシウムCについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を3.2質量部とし、脂肪酸の添加量を0.8質量部とする以外は、表面処理炭酸カルシウムAと同様にして表面処理炭酸カルシウムDを得た。得られた表面処理炭酸カルシウムDについて、上記の測定方法で遊離脂肪酸を測定したところ、2.4質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が700μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムCと同様にして表面処理炭酸カルシウムEを得た。得られた表面処理炭酸カルシウムEについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が1200μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムCと同様にして表面処理炭酸カルシウムFを得た。得られた表面処理炭酸カルシウムFについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が1900μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムCと同様にして表面処理炭酸カルシウムGを得た。得られた表面処理炭酸カルシウムGについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を3.0質量部とし、混合脂肪酸ナトリウム塩のみを添加する以外は、表面処理炭酸カルシウムAと同様にして表面処理炭酸カルシウムHを得た。得られた表面処理炭酸カルシウムHについて、上記の測定方法で遊離脂肪酸を測定したところ、1.5質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を2.8質量部とし、脂肪酸の添加量を1.2質量部とする以外は、表面処理炭酸カルシウムAと同様にして表面処理炭酸カルシウムIを得た。得られた表面処理炭酸カルシウムIについて、上記の測定方法で遊離脂肪酸を測定したところ、2.8質量%であった。
脂肪酸処理した炭酸カルシウムのスラリーに水酸化ナトリウム水溶液を添加しない以外は、表面処理炭酸カルシウムCと同様にして表面処理炭酸カルシウムJを得た。表面処理炭酸カルシウムに含まれるアルカリ金属含有量は、250μg/gであった。得られた表面処理炭酸カルシウムJについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が2500μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムCと同様にして表面処理炭酸カルシウムKを得た。得られた表面処理炭酸カルシウムKについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
得られた表面処理炭酸カルシウムのBET比表面積、アルカリ金属含有量、及び遊離脂肪酸の値を表1及び表2に示す。
(表面処理炭酸カルシウムL)
BET比表面積が20m2/gの合成炭酸カルシウム2000gに、固形分が10質量%となるように水を加え、40℃下で撹拌して、炭酸カルシウムのスラリーを調製した。次に、混合脂肪酸ナトリウム塩(質量比でラウリン酸:ミリスチン酸:パルミチン酸:ステアリン酸:オレイン酸=3:2:40:15:30、ミヨシ油脂社製のタンカルMH)と、脂肪酸(質量比でミリスチン酸:パルミチン酸:ステアリン酸:オレイン酸=2:22:22:35、日油社製の0号脂肪酸)とを所定の比率で混合した混合物の10質量%水溶液を調製し、表面処理剤溶液とした。この表面処理剤溶液を上記の炭酸カルシウムスラリーに添加し、炭酸カルシウムを表面処理した。なお、炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量は4.5質量部であり、脂肪酸の添加量は、0.5質量部である。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を4.2質量部とし、脂肪酸の添加量を0.8質量部とする以外は、表面処理炭酸カルシウムLと同様にして表面処理炭酸カルシウムMを得た。得られた表面処理炭酸カルシウムMについて、上記の測定方法で遊離脂肪酸を測定したところ、2.0質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を5.5質量部とし、脂肪酸の添加量を1.0質量部とする以外は、表面処理炭酸カルシウムLと同様にして表面処理炭酸カルシウムNを得た。得られた表面処理炭酸カルシウムNについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を5.2質量部とし、脂肪酸の添加量を1.3質量部とする以外は、表面処理炭酸カルシウムLと同様にして表面処理炭酸カルシウムOを得た。得られた表面処理炭酸カルシウムOについて、上記の測定方法で遊離脂肪酸を測定したところ、2.5質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が800μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムNと同様にして表面処理炭酸カルシウムPを得た。得られた表面処理炭酸カルシウムPについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が1600μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムNと同様にして表面処理炭酸カルシウムQを得た。得られた表面処理炭酸カルシウムQについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が1800μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムNと同様にして表面処理炭酸カルシウムRを得た。得られた表面処理炭酸カルシウムRについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を5.0質量部とし、混合脂肪酸ナトリウム塩のみを添加する以外は、表面処理炭酸カルシウムLと同様にして表面処理炭酸カルシウムSを得た。得られた表面処理炭酸カルシウムSについて、上記の測定方法で遊離脂肪酸を測定したところ、1.6質量%であった。
炭酸カルシウム100質量部に対する混合脂肪酸ナトリウム塩の添加量を4.5質量部とし、脂肪酸の添加量を2.0質量部とする以外は、表面処理炭酸カルシウムLと同様にして表面処理炭酸カルシウムTを得た。得られた表面処理炭酸カルシウムTについて、上記の測定方法で遊離脂肪酸を測定したところ、2.8質量%であった。
脂肪酸処理した炭酸カルシウムのスラリーに水酸化ナトリウム水溶液を添加しない以外は、表面処理炭酸カルシウムNと同様にして表面処理炭酸カルシウムUを得た。表面処理炭酸カルシウムに含まれるアルカリ金属含有量は、300μg/gであった。得られた表面処理炭酸カルシウムUについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
表面処理炭酸カルシウムに含まれるアルカリ金属含有量が2300μg/gとなるように水酸化ナトリウム水溶液を添加する以外は、表面処理炭酸カルシウムNと同様にして表面処理炭酸カルシウムVを得た。得られた表面処理炭酸カルシウムVについて、上記の測定方法で遊離脂肪酸を測定したところ、2.2質量%であった。
(実施例1~14及び比較例1~8)
表1~表4に示す表面処理炭酸カルシウムを用いて、実施例1~14及び比較例1~8の変成シリコーン樹脂組成物を製造した。具体的には、表面処理炭酸カルシウム120質量部、変成シリコーン樹脂(カネカ社製のMSポリマーS203(60質量部)、MSポリマーS303(40質量部))100質量部、フタル酸ジイソノニル(DINP)55質量部、重質炭酸カルシウム(白石工業株式会社製のホワイトン305)40質量部、脂肪酸アミド(伊藤製油株式会社製のA-S-A T1800)2質量部と、アミノシラン(東レダウコーニング社製のSH2000)2質量部、ビニルシラン(信越シリコーン社製のKBM1003)3質量部、ジブチル錫ジアセチルアセトナート(日東化成社製のネオスタン-U220H)2質量部を混合して、変成シリコーン樹脂組成物のペーストを得、カートリッジに保管した。
樹脂組成物の初期50%モジュラスを以下のようにして測定した。ガラス板上にPPシートを張り、シート上に厚さ3.0mmのガラススペーサーを貼り付け、その枠内に、気泡が入らないよう得られたペーストを充填し、23℃で14日間、次いで、30℃で14日間養生した。JIS K6251に規定されたダンベル状2号形でシートを打ち抜き、試験片を23℃で1日以上放置後、試験片の厚みを測定し、オートグラフで引張速度200mm/minで試験を行い、初期50%モジュラスを測定した。
樹脂組成物の加熱後の50%モジュラスを以下のようにして測定した。初期50%モジュラス測定と同様の条件で充填、養生、打ち抜きを行った。その後80℃で7日、14日とそれぞれ放置した後、試験片を23℃で1日以上放置後、試験片の厚みを測定し、オートグラフで引張速度200mm/minで試験を行い、加熱促進試験後の50%モジュラスを測定した。
得られたペーストの貯蔵安定性を以下のようにして測定した。初期粘度と、貯蔵後粘度の変化率を貯蔵安定性の指標とした。粘度変化率は、下式に従い算出した。初期粘度は、カートリッジから容器にとり、直ちにB形粘度計で測定した。貯蔵後の粘度は、50℃下で14日カートリッジを静置した後、20℃下で3時間以上静置し、容器に取り、B型粘度計で測定した。
粘度変化率(%)=[(貯蔵後粘度-初期粘度)/初期粘度]×100
表1~表4に、各実施例及び各比較例における貯蔵安定性、初期50%モジュラス、80℃7日後の50%モジュラス、80℃14日後の50%モジュラス、及び50%モジュラス変化率を示す。なお、50%モジュラス変化率は、以下の式で算出される値である。
樹脂組成物の耐水接着性は以下のようにして測定した。JIS A1439:2004の5.17に規定された50×50×5mmのアルミ板を使用し、スペーサーを組み合わせて(H型試験体1形)、12×12×50mmのスペースを作り、その中に得られたペーストを充填し、初期50%モジュラス測定と同様の条件で養生を行った。その後水に浸漬させ7日間放置した後、試験片を23℃で1日以上放置後、オートグラフで引張速度50mm/minで試験を行い、剥離の度合いを目視で確認し、剥離のなかったもの(凝集破壊)を○、剥離のみられたもの(界面剥離)を×とした。
Claims (5)
- BET比表面積が1m2/g~60m2/gの範囲内である炭酸カルシウムを脂肪酸で表面処理し、アルカリ金属含有量が500μg/g~2000μg/gの範囲内であり、エタノールで抽出することにより求められる遊離脂肪酸が、1.8~2.5質量%の範囲内である表面処理炭酸カルシウムと、末端シリル基樹脂とを含む、末端シリル基樹脂組成物。
- 末端シリル基樹脂が、末端シリル基ポリエーテル樹脂、または末端シリル基ポリウレタン樹脂を主成分として含む、請求項1に記載の末端シリル基樹脂組成物。
- 末端シリル基樹脂組成物中に含まれる表面処理炭酸カルシウムの含有量は、末端シリル基樹脂100質量部に対して、50質量部~200質量部の範囲内である、請求項1または2に記載の末端シリル基樹脂組成物。
- 前記アルカリ金属は、ナトリウム及びカリウムの少なくとも1種である、請求項1~3のいずれか一項に記載の末端シリル基樹脂組成物。
- 請求項1~4のいずれか一項に記載の末端シリル基樹脂組成物を製造する方法であって、
前記遊離脂肪酸が1.8~2.5質量%の範囲内となるように脂肪酸で前記炭酸カルシウムを表面処理する工程と、
前記脂肪酸処理炭酸カルシウムに、アルカリ金属化合物を添加し、前記表面処理炭酸カルシウムを製造する工程と、
前記表面処理炭酸カルシウムを前記末端シリル基樹脂に配合する工程とを備える、末端シリル基樹脂組成物の製造方法。
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