JP5728333B2 - Process for producing modified silicone resin composition - Google Patents

Description

  The present invention relates to a modified silicone resin composition and a method for producing the same.

  Conventionally, for the purpose of imparting thixotropic properties (thixotropic properties) to a resin, it has been practiced to add calcium carbonate surface-treated with a fatty acid or the like to the resin.

  When such a resin composition is used as, for example, a sealant, the sealant is required to have high followability to the adherend. Therefore, in addition to thixotropic properties, the resin composition has low modulus and high elongation. It is required to have.

  For example, Patent Document 1 proposes a two-component curable resin composition that is superior in terms of modulus and elongation by blending calcium carbonate surface-treated with a fatty acid into a resin.

  Patent Document 2 discloses a resin composition containing a surface-treated calcium carbonate which is treated with a fatty acid-based surface treating agent and contains an alkali metal. However, it is disclosed that the resin composition disclosed in Patent Document 2 is unsuitable from the viewpoint of storage stability when used as a long-term sealant such as a cartridge type. This is considered to be caused by the deterioration of the storage stability of the resin composition due to alkali metal ions contained in the resin composition, as disclosed in Patent Document 3.

For this reason, in patent document 3, 1 liquid which has favorable storage stability by making the alkali metal content in the resin composition containing the surface-treated calcium carbonate 1.0 × 10 ⁻³ mol / 100 g CaCO ₃ or less. It has been proposed to provide a mold curable resin composition.

JP 2011-94134 A JP 2007-169485 A JP 2001-158863 A

  The main object of the present invention is to provide a modified silicone resin composition having low modulus, high elongation, and good storage stability, a method for producing the same, and a surface-treated calcium carbonate for the modified silicone resin composition.

  The modified silicone resin composition of the present invention includes a surface-treated calcium carbonate and a modified silicone resin. The surface-treated calcium carbonate is obtained by surface-treating calcium carbonate with at least one of fatty acid, resin acid, and derivatives thereof. The surface-treated calcium carbonate contains 500 μg / g to 2000 μg / g alkali metal.

BET specific surface area of the surface-treated calcium carbonate ^is preferably 1m ² / g~60m 2 / g.

  It is preferable that the processing amount of at least one kind of fatty acid, resin acid and derivatives thereof with respect to calcium carbonate is 0.1 to 20 parts by weight with respect to 100 parts by weight of calcium carbonate.

  The alkali metal is preferably at least one of sodium and potassium.

  The surface-treated calcium carbonate for the modified silicone resin composition of the present invention is obtained by surface-treating calcium carbonate with at least one of fatty acids, resin acids, and derivatives thereof. The surface-treated calcium carbonate contains 500 μg / g to 2000 μg / g alkali metal.

  In the method for producing the modified silicone resin composition of the present invention, calcium carbonate is surface-treated with at least one of fatty acid, resin acid and derivatives thereof. The surface-treated calcium carbonate is obtained by mixing the surface-treated calcium carbonate and an alkali metal compound so that the amount of the alkali metal is 500 μg / g to 2000 μg / g. The surface-treated calcium carbonate and the modified silicone resin are mixed.

  ADVANTAGE OF THE INVENTION According to this invention, the modified silicone resin composition which has a low modulus, high elongation, and favorable storage stability, its manufacturing method, and the surface treatment calcium carbonate for modified silicone resin compositions can be provided.

  Hereinafter, an example of the preferable form which implemented this invention is demonstrated. However, the following embodiment is merely an example. The present invention is not limited to the following embodiments.

  The modified silicone resin composition of this embodiment contains surface-treated calcium carbonate. In the surface-treated calcium carbonate, the surface of calcium carbonate is surface-treated with at least one of fatty acids, resin acids and derivatives thereof (hereinafter sometimes referred to as fatty acids), and further contains 500 μg / g to 2000 μg / g of alkali metal. It is a waste.

(Calcium carbonate)
The calcium carbonate which comprises surface treatment calcium carbonate is not specifically limited. As calcium carbonate, conventionally well-known calcium carbonate can be used, for example. Specific examples of calcium carbonate include synthetic calcium carbonate and natural calcium carbonate (heavy calcium carbonate). The calcium carbonate is preferably synthetic calcium carbonate.

  Synthetic calcium carbonate is not particularly limited. Examples of the synthetic calcium carbonate include precipitated (collaged) calcium carbonate and light calcium carbonate. Synthetic calcium carbonate can be produced, for example, by reacting calcium hydroxide with carbon dioxide. Calcium hydroxide can be produced, for example, by reacting calcium oxide with water. Calcium oxide can be produced, for example, by co-firing raw limestone with coke. In this case, since carbon dioxide gas is generated during firing, calcium carbonate can be produced by reacting this carbon dioxide gas with calcium hydroxide.

  Natural calcium carbonate is obtained by pulverizing naturally produced calcium carbonate ore by a known method. Examples of the method for pulverizing the raw calcium carbonate include a roller mill, a high-speed rotation mill (impact shear mill), a container drive medium mill (ball mill), a medium stirring mill, a planetary ball mill, and a jet mill.

  The average particle diameter of calcium carbonate is usually about 20 nm to 10000 nm, preferably about 30 nm to 2000 nm, and more preferably about 30 nm to 150 nm. The average particle size of calcium carbonate is a value measured by image analysis using a transmission electron microscope.

(Fatty acids, resin acids and their derivatives)
Fatty acids and their derivatives are not particularly limited. Examples of fatty acids and derivatives thereof include fatty acids, metal salts thereof, and esterified products thereof.

  Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms.

  Specific examples of saturated fatty acids include caproic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, alignic acid, behenic acid, lignoceric acid, serotic acid, montanic acid, Examples include melicic acid. Among these, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like are preferably used.

  Specific examples of 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.

  Examples of the metal salt of fatty acid include alkali metal salts such as sodium salt and potassium salt of the above fatty acid, and alkaline earth metal salts such as magnesium salt and calcium salt. Among these, alkali metal salts such as sodium salts and potassium salts of the above fatty acids are preferable.

  Examples of the esterified fatty acid include stearyl stearate, lauryl stearate, stearyl palmitate, lauryl palmitate and the like.

  More preferable fatty acids and derivatives thereof include sodium salts and potassium salts of saturated fatty acids having 9 to 21 carbon atoms. Among these, sodium salts such as lauric acid, myristic acid, palmitic acid, stearic acid, and oleic acid are particularly preferable.

  The resin acid and its derivative are not particularly limited. Examples of the resin acid and derivatives thereof include resin acid, metal salts thereof, and other derivatives.

  Specific examples of the resin acid include abietic acid, pimaric acid, repopimaric acid, neoabietic acid, pulstriic acid, dehydroabietic acid, dihydroabietic acid, tetraabietic acid, dextropimaric acid, and isodextropimaric acid. .

  Examples of the metal salt of the resin acid include alkali metal salts such as sodium salt and potassium salt of the above resin acid, and alkaline earth metal salts such as magnesium salt and calcium salt.

  Examples of the resin acid derivative include hydrogenated rosin, disproportionated rosin, polymerized rosin, rosin ester, maleated rosin, maleated rosin ester, and rosin modified phenol.

  Preferred resin acids and derivatives thereof include abietic acid, neoabietic acid, dehydroabietic acid, tetraabietic acid, pimaric acid, dextropimaric acid, hydrogenated rosin, disproportionated rosin, and maleated rosin.

  The processing amount of at least one of fatty acid, resin acid and derivatives thereof relative to calcium carbonate is preferably about 0.1 to 20 parts by weight with respect to 100 parts by weight of calcium carbonate, and preferably 1 to 10 parts by weight. More preferably, it is about 2 parts by weight, and more preferably about 2 to 5 parts by weight. If the treatment amount of at least one of fatty acid, resin acid and derivatives thereof with respect to calcium carbonate is too small, an unsurface-treated portion is formed, and the effect as surface-treated calcium carbonate cannot be sufficiently exhibited, which is not preferable. On the other hand, if the amount of at least one of fatty acid, resin acid and derivatives thereof is too large, an effect proportional to the surface treatment amount cannot be obtained and the cost is increased, which is not preferable because it is economically disadvantageous.

  The method for surface-treating calcium carbonate with at least one of fatty acids, resin acids and derivatives thereof is not particularly limited.

  As the surface treatment, for example, a method in which a fatty acid, a resin acid and at least one of these derivatives are added to a slurry containing calcium carbonate and water, followed by dehydration and drying can be employed. For example, the following method is mentioned as a specific method of surface-treating calcium carbonate with an alkali metal salt of a fatty acid.

  While heating the fatty acid in an aqueous alkali metal solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution, the fatty acid is converted into an aqueous alkali metal solution. Next, an alkali metal aqueous solution of a fatty acid is added to a slurry of calcium carbonate and water and stirred. Thereby, the surface of calcium carbonate can be surface-treated with a fatty acid.

  The solid content of calcium carbonate in the slurry of calcium carbonate and water can be adjusted as appropriate in consideration of the average particle diameter of calcium carbonate, the dispersibility of the calcium carbonate in the slurry, the ease of slurry dehydration, etc. Good. In general, a slurry with an appropriate viscosity can be obtained by adjusting the solid content of the slurry to about 2 to 30% by weight, preferably about 5 to 20% by weight.

  The slurry may be dehydrated by a method such as a filter press. Further, the drying may be performed by, for example, a box type dryer.

  Further, the surface of calcium carbonate can be treated with a fatty acid without using the fatty acid as a metal salt of the fatty acid. For example, the surface of calcium carbonate can be treated with a fatty acid by stirring the calcium carbonate while heating it to a temperature equal to or higher than the melting point of the fatty acid, adding the fatty acid thereto, and stirring. Similarly, the surface of calcium carbonate can be treated with the fatty acid ester by adding the fatty acid ester thereto while stirring the calcium carbonate while heating it above the melting point of the fatty acid ester.

(Alkali metal)
The surface-treated calcium carbonate of this embodiment contains an alkali metal.

  The content of the alkali metal contained in the surface-treated calcium carbonate is about 500 μg / g to 2000 μg / g. The content of the alkali metal contained in the surface-treated calcium carbonate is preferably about 800 μg / g to 1800 μg / g, and more preferably about 1000 μg / g to 1800 μg / g.

  The alkali metal is preferably at least one of sodium and potassium.

  The modified silicone resin composition of the present embodiment exhibits a low modulus by containing 500 μg / g to 2000 μg / g alkali metal in the surface-treated calcium carbonate. The modified silicone resin composition of the present embodiment exhibiting low modulus, particularly when used as a sealant, relieves stress even when a building such as a siding board expands and contracts over time, and the followability increases. . Therefore, the adhesive force of the sealant is improved, and as a result, the durability of the building can be improved.

50% modulus of modified silicone resin composition according to the present embodiment is usually 0.23N ^/ mm ² ~0.27N ^/ mm 2 ^{approximately,} is 0.15N / mm ² ~0.23N / mm 2 approximately It is preferable.

  In the present invention, the 50% modulus of the modified silicone resin composition is a value measured by an autograph after curing according to JIS.

  Furthermore, the modified silicone resin composition of the present embodiment exhibits high elongation by including 500 μg / g to 2000 μg / g alkali metal in the surface-treated calcium carbonate. The modified silicone resin composition of the present embodiment having a high elongation, particularly when used as a sealant, relieves stress and enhances followability when a building such as a siding board expands and contracts over time. Therefore, the adhesive force of the sealant is improved, and as a result, the durability of the building can be improved.

  The elongation of the modified silicone resin composition of the present embodiment is usually about 600% to 800%, and preferably about 700% to 900%.

  In the present invention, the elongation percentage of the modified silicone resin composition is a value measured by autograph after curing based on JIS as in the modulus measurement.

  In addition, as described above, conventionally, when a surface-treated calcium carbonate is blended with a resin to obtain a resin composition, from the viewpoint of storage stability of the resin composition, the alkali metal content in the resin composition can be as much as possible. It was thought to be less. On the other hand, as a result of intensive studies by the present inventors, when surface-treated calcium carbonate is blended with the modified silicone resin, the surface-treated calcium carbonate contains 500 μg / g to 2000 μg / g alkali metal to reduce the amount. It has been found that a modified silicone resin composition having not only a modulus and high elongation but also excellent storage stability can be obtained. The modified silicone resin composition of this embodiment having excellent storage stability can be suitably used as a one-component curable resin composition that requires particularly high storage stability.

  The surface-treated calcium carbonate can be obtained, for example, by adding an aqueous solution of an alkali metal compound to an aqueous slurry of calcium carbonate surface-treated with a fatty acid or the like, followed by dehydration and drying. The surface-treated calcium carbonate can also be obtained by dehydrating an aqueous slurry of calcium carbonate surface-treated with a fatty acid or the like, adding an aqueous solution of an alkali metal compound, and then drying.

  Examples of the alkali metal compound 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.

  In addition, when surface treating calcium carbonate with a fatty acid or the like, when the surface treatment is performed with an alkali metal salt of a fatty acid or a resin acid, the surface-treated calcium carbonate contains an alkali metal without mixing calcium carbonate and an alkali metal compound. included. In this case, the alkali metal compound may be appropriately adjusted and mixed so that the content of the alkali metal in the surface-treated calcium carbonate falls within the above range.

BET specific surface area of the surface-treated calcium carbonate ^is preferably 1m ² / g~60m 2 / g ^{approximately,} more preferably from 3m ² / g~30m 2 / g ^{approximately,} 7m ² / ^g~30m 2 More preferably, it is about / g.

  The average particle diameter of the surface-treated calcium carbonate is preferably about 20 nm to 1000 m, more preferably about 30 nm to 2000 nm, and further preferably about 30 nm to 150 nm. In the present invention, the average particle diameter of the surface-treated calcium carbonate is a value measured by image analysis using a transmission electron microscope.

(Modified silicone resin composition)
The modified silicone resin composition includes surface-treated calcium carbonate and a modified silicone resin.

  The content of the surface-treated calcium carbonate contained in the modified silicone resin composition is preferably about 50 to 200 parts by weight, and about 80 to 150 parts by weight with respect to 100 parts by weight of the modified silicone resin. It is more preferable that When the content of the surface-treated calcium carbonate contained in the modified silicone resin composition is about 80 parts by weight to 150 parts by weight, an appropriate viscosity and thixotropic property are ensured before curing, and workability is improved. Therefore, it is preferable. Further, after curing, the balance of modulus, elongation and strength is improved, which is preferable.

  The modified silicone resin is mainly composed of a silyl group-terminated polyether having a reactive silyl group introduced at the terminal. For example, when the modified silicone resin composition is used as a sealant, the modified silicone resin preferably forms a siloxane bond by moisture curing. Examples of 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 in addition to the modified silicone resin.

  Examples of the plasticizer include dimethyl phthalate (DMP), diethyl phthalate (DEP), di-n-butyl phthalate (DBP), diheptyl phthalate (DHP), dioctyl phthalate (DOP), diisononyl phthalate ( DINP), diisodecyl phthalate (DIDP), ditridecyl phthalate (DTDP), butylbenzyl phthalate (BBP), dicyclohexyl phthalate (DCHP), tetrahydrophthalic acid ester, dioctyl adipate (DOA), diisononyl adipate (DINA) , Diisodecyl adipate (DIDA), di-n-alkyl adipate, dibutyl diglycol adipate (BXA), bis (2-ethylhexyl) azelate (DOZ), dibutyl sebacate (DBS), dioctyl sebacate (DOS), male Dibutyl phosphate (DBM), di-2-ethylhexyl maleate (DOM), dibutyl fumarate (DBF), tricresyl phosphate (TCP), triethyl phosphate (TEP), tributyl phosphate (TBP), tris- (2-ethylhexyl) ) Phosphate (TOP), tri (chloroethyl) phosphate (TCEP), trisdichloropropyl phosphate (CRP), tributoxyethyl phosphate (TBXP), tris (β-chloropropyl) phosphate (TMCPP), triphenyl phosphate (TPP), Octyl diphenyl phosphate (CDP), acetyl triethyl citrate, tributyl acetyl citrate, trimellitic acid plasticizer, polyester plasticizer, chlorinated paraffin, stearic acid plasticizer, dimethyl And rupolysiloxane.

  Examples of the filler (including a thickener) include inorganic fillers and organic fillers. Examples of 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, and the like. Examples of organic fillers 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.

  Examples of the adhesion-imparting agent include hydrolyzable organic silicon compounds. Specific examples of hydrolyzable organic silicon compounds include vinyltrimethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltriacetoxysilane, tetramethyl orthosilicate (tetramethoxysilane) Or methyl silicate), tetraethyl orthosilicate (tetraethoxysilane or ethyl silicate), tetrapropyl orthosilicate, tetrabutyl orthosilicate, etc., or partial hydrolysis condensates thereof, γ-aminopropyltrimethoxysilane, γ-glycid Xylpropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-methacryloxypropi Silane coupling agents such as trimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, or partial hydrolysis thereof Examples include decomposition condensates. The hydrolyzable organosilicon compound may consist of only one of these, or may contain two or more.

  Examples of the dehydrating agent include a silane coupling agent. Specific examples of 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 silane coupling agents having these functional groups include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, and γ-isocyanatepropylmethyldimethoxysilane. Isocyanate group-containing silanes; γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltriethoxysilane, γ- (2 Aminoethyl) aminopropylmethyldiethoxysilane, γ- (2-aminoethyl) aminopropyltriisopropoxysilane, γ-ureidopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-benzyl-γ Amino group-containing silanes such as aminopropyltrimethoxysilane and N-vinylbenzyl-γ-aminopropyltriethoxysilane; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane , Γ-mercaptopropylmethyldiethoxysilane and other mercapto group-containing silanes; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxy Epoxy group-containing silanes such as silane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; β-carboxyethyltriethoxysilane, β-carboxy Carboxysilanes such as ethylphenylbis (2-methoxyethoxy) silane and N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropyl Vinyl-type unsaturated group-containing silanes such as methyldimethoxysilane and γ-acryloyloxypropylmethyltriethoxysilane; Halogen-containing silanes such as γ-chloropropyltrimethoxysilane; Tris (trimethoxysilyl) isocyanurate Socia isocyanurate silanes, bis (3-triethoxysilylpropyl) polysulfane such as tetrasulfane, and the like.

  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 embodiment can be suitably used as a sealing material, an adhesive, and the like because it has low modulus, high elongation, and high storage stability.

  In general, the one-component curable resin composition has a larger compounding restriction than the two-component curable resin composition, and it is relatively difficult to impart low modulus and high elongation. On the other hand, the modified silicone resin composition according to the present embodiment is obtained by blending a surface-treated calcium carbonate containing an alkali metal with a silicone resin, and is not easily limited by blending, and is suitable as a one-pack type resin composition. Can be used for

  The above-mentioned surface-treated calcium carbonate contained in the modified silicone resin composition of the present embodiment can be suitably used as the surface-treated calcium carbonate for the modified silicone resin composition.

(Method for producing modified silicone resin composition)
The method for producing a modified silicone resin composition according to the present embodiment includes a step of surface-treating calcium carbonate with a fatty acid or the like. Examples of the method for surface-treating calcium carbonate with a fatty acid or the like include the methods described above.

  Moreover, the manufacturing method of the modified silicone resin composition which concerns on this embodiment has the process of mixing the calcium carbonate surface-treated with the fatty acid etc. and the alkali metal compound, and obtaining the surface-treated calcium carbonate. The alkali metal is mixed so that the amount of the alkali metal contained in the surface-treated calcium carbonate is 500 μg / g to 2000 μg / g.

  Examples of the method of mixing calcium carbonate surface-treated with a fatty acid or the like and an alkali metal compound include the above-described methods.

  Furthermore, the manufacturing method of the modified silicone resin composition which concerns on this embodiment has the process of mixing surface treatment calcium carbonate and modified silicone resin. The method for mixing the surface-treated calcium carbonate and the modified silicone resin is not particularly limited. For example, the surface-treated calcium carbonate and the modified silicone resin can be mixed by stirring with a stirrer or the like. At this time, a plasticizer, a filler, an adhesion-imparting agent, a dehydrating agent, a catalyst, and the like may be mixed.

  According to the method for producing a modified silicone resin composition of this embodiment, the modified silicone resin composition according to this embodiment can be suitably produced.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

Example 1
Water was added to 2000 g of synthetic calcium carbonate having a BET specific surface area of 13 m ² / g so that the solid content would be 10% by weight, and stirred at 40 ° C. to prepare a calcium carbonate slurry. Next, a mixed fatty acid sodium salt adjusted to 10% by weight in this slurry (by weight ratio, lauric acid: myristic acid: palmitic acid: stearic acid: oleic acid = 3: 2: 40: 15: 30, manufactured by Miyoshi Oil & Fats Co., Ltd.) (Tangkar MH) 600 g was mixed to prepare a slurry of calcium carbonate and fatty acid salt. Next, 300 g of an aqueous sodium hydroxide solution having a concentration of 2.5 mol / l was added to the slurry and stirred. Next, the obtained slurry was dehydrated to obtain a cake having a solid content of 60% by weight. The obtained cake was dried with a dryer to obtain surface-treated calcium carbonate. The amount of sodium hydroxide aqueous solution was adjusted so that the amount of sodium contained in the surface-treated calcium carbonate after dehydration and drying was 800 μg / g.

  Next, 120 parts by weight of the surface-treated calcium carbonate obtained, modified silicone resin (MS polymer S203 (60 parts by weight), MS polymer S303 (40 parts by weight) manufactured by Kaneka), 100 parts by weight, diisononyl phthalate (DINP) 55 parts by weight, heavy calcium carbonate (Whiten 305 manufactured by Shiraishi Kogyo Co., Ltd.) 40 parts by weight, fatty acid amide (A-S-A T1800 manufactured by Ito Oil Co., Ltd.), and aminosilane (Toray Dow Corning) 2 parts by weight of SH2000 manufactured by Shin-Etsu Silicone Co., Ltd., 3 parts by weight of vinyl silane (KBM1003 manufactured by Shin-Etsu Silicone Co., Ltd.) and 2 parts by weight of dibutyltin diacetylacetonate (Neostan-U220H manufactured by Nitto Kasei Co., Ltd.) A paste was obtained and stored in a cartridge.

[Measurement of 50% modulus]
The 50% modulus of the paste obtained in Example 1 was measured as follows. The results are shown in Table 1.

  A PP sheet is stretched on a glass plate, a glass spacer having a thickness of 3.0 mm is pasted on the sheet, and a sealant is filled in the frame so that bubbles do not enter. Cured under 14 days. The sheet is punched out in the dumbbell shape No. 2 specified in JIS K6251 and the specimen is left to stand at 23 ° C. for 1 day or more. Then, the thickness of the specimen is measured, and the test is conducted at an extension rate of 200 mm / min with an autograph. The modulus was measured.

[Measurement of elongation]
The elongation percentage of the paste obtained in Example 1 was measured as follows. The results are shown in Table 1.

  Cured under the same conditions as the modulus measurement, punched out the sheet with dumbbell-shaped No. 2 specified in JIS K6251, left the test piece at 23 ° C for 1 day or more, measured the thickness of the test piece, and measured the tensile speed with an autograph. The test was performed at 200 mm / min, and the elongation between 20 mm marked lines was measured.

[Measurement of storage stability]
The storage stability of the paste obtained in Example 1 was measured as follows. The results are shown in Table 1.

  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 measured from a cartridge in a container and immediately measured with a B-type viscometer. After storage, the viscosity was measured for 14 days at 50 ° C., then left at 20 ° C. for 3 hours or longer, taken in a container, and measured with a B-type viscometer.

  Viscosity change rate = (viscosity after storage−initial viscosity) / initial viscosity × 100

(Example 2)
A modified silicone resin composition paste was obtained in the same manner as in Example 1 except that the sodium hydroxide aqueous solution was mixed so that the amount of sodium in the surface-treated calcium carbonate was 1600 μg / g. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 1.

(Example 3)
A paste of the modified silicone resin composition was obtained in the same manner as in Example 1 except that the sodium hydroxide aqueous solution was mixed so that the amount of sodium in the surface-treated calcium carbonate was 1400 μg / g. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 1.

Example 4
Instead of adding an aqueous sodium hydroxide solution to an aqueous slurry of surface-treated calcium carbonate, an aqueous sodium hydroxide solution was added to a cake of surface-treated calcium carbonate having a solid content of 60% by weight, and the amount of sodium in the surface-treated calcium carbonate However, except having mixed sodium hydroxide aqueous solution so that it might become 1200 microgram / g, it carried out similarly to Example 1, and obtained the paste of the modified silicone resin composition. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 1.

(Example 5)
A modified silicone resin composition paste was obtained in the same manner as in Example 4 except that the sodium hydroxide aqueous solution was mixed so that the amount of sodium in the surface-treated calcium carbonate was 1600 μg / g. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 1.

(Comparative Example 1)
A modified silicone resin composition paste was obtained in the same manner as in Example 1 except that the aqueous sodium hydroxide solution was not mixed. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 1.

  As is clear from the results shown in Table 1, it can be seen that the modified silicone resin composition pastes obtained in Examples 1 to 5 have a small value of 50% modulus and a low modulus. Moreover, it turns out that the modified silicone resin composition paste obtained in Examples 1-5 has a high elongation rate and a high elongation. Furthermore, the modified silicone resin composition pastes obtained in Examples 1 to 5 show the storage stability equivalent to that of Comparative Example 1 despite containing 800 μg / g to 1600 μg / g of sodium. . On the other hand, it can be seen that the modified silicone resin composition paste obtained in Comparative Example 1 has a higher 50% modulus and a higher modulus than the pastes obtained in Examples 1 to 5. Moreover, it turns out that the modified | denatured silicone resin composition paste obtained by the comparative example 1 has a low elongation rate compared with the paste obtained by Examples 1-5.

(Example 6)
The synthetic calcium carbonate having a BET specific surface area of 20 m ² / g was used, 600 g of the mixed fatty acid sodium salt adjusted to 10% by weight was changed to 1000 g, and the amount of sodium in the surface-treated calcium carbonate was 600 μg / g. Thus, a modified silicone resin composition paste was obtained in the same manner as in Example 1 except that a sodium hydroxide aqueous solution was mixed. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 2.

(Comparative Example 2)
A modified silicone resin composition paste was obtained in the same manner as in Example 6 except that the aqueous sodium hydroxide solution was not mixed. Next, in the same manner as in Example 1, 50% modulus, elongation rate, and storage stability of the obtained paste were measured. The results are shown in Table 2.

  As is apparent from the results shown in Table 2, it can be seen that the modified silicone resin composition paste obtained in Example 6 has a small value of 50% modulus and a low modulus. Moreover, it turns out that the modified silicone resin composition paste obtained in Example 6 has a high elongation and a high elongation. Furthermore, although the modified silicone resin composition paste obtained in Example 6 contains 600 μg / g of sodium, it shows the same storage stability as Comparative Example 2. On the other hand, it can be seen that the modified silicone resin composition paste obtained in Comparative Example 2 has a higher 50% modulus and a higher modulus than the paste obtained in Example 6. Further, it can be seen that the modified silicone resin composition paste obtained in Comparative Example 2 has a lower elongation than the paste obtained in Example 6.

Claims (4)

Surface treatment of calcium carbonate with at least one of fatty acids, resin acids and derivatives thereof,
Mixing the surface-treated calcium carbonate with an alkali metal compound so that the amount of alkali metal is 500 μg / g to 2000 μg / g to obtain surface-treated calcium carbonate; and the surface-treated calcium carbonate and modified silicone Mixing the resin,
A process for producing a modified silicone resin composition. BET specific surface area of the surface-treated calcium carbonate ^is 1m ² / g~60m 2 / g, the production method of the modified silicone resin composition according to claim 1. The processing amount of at least one kind of fatty acid, resin acid and derivatives thereof with respect to the calcium carbonate is 0.1 to 20 parts by weight with respect to 100 parts by weight of the calcium carbonate. the method for producing modified silicone resin composition. The method for producing a modified silicone resin composition according to any one of claims 1 to 3, wherein the alkali metal is at least one of sodium and potassium.