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WO2014073593A1 - Composition durcissable et produit durci de celle-ci - Google Patents

Composition durcissable et produit durci de celle-ci Download PDF

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Publication number
WO2014073593A1
WO2014073593A1 PCT/JP2013/080082 JP2013080082W WO2014073593A1 WO 2014073593 A1 WO2014073593 A1 WO 2014073593A1 JP 2013080082 W JP2013080082 W JP 2013080082W WO 2014073593 A1 WO2014073593 A1 WO 2014073593A1
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component
curable composition
weight
group
parts
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Japanese (ja)
Inventor
川上　敦史
笠井　充弘
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Kaneka Corp
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Kaneka Corp
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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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • 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

Definitions

  • the present invention relates to a curable composition containing a polyoxyalkylene polymer having a reactive silicon group and a cured product thereof.
  • the polyoxyalkylene polymer having a reactive silicon group is a polymer that can react with moisture in the air even at room temperature and can be cured into a rubber-like shape, and has already been industrially produced. Widely used in applications such as adhesives.
  • silylated polyurethane which is a polymer in which a reactive silicon group is introduced into a urethane prepolymer.
  • Curable compositions obtained by adding a plasticizer, a filler, a stabilizer, a curing catalyst, etc. to a polyoxyalkylene polymer having a reactive silicon group are disclosed in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and the like. ing.
  • the curable compositions of these patent documents can be applied to sealing material applications.
  • An object of the present invention is to provide a curable composition applicable to industrial sealing materials and industrial adhesives which are excellent in tensile breaking strength and also excellent in the rise of tensile shear strength.
  • the present inventors have (A) a branched polyoxyalkylene polymer having a reactive silicon group, and (B) a linear polyoxyalkylene having a reactive silicon group.
  • the present inventors have found that the above problems can be solved by using a curable composition containing a polymer, (C) calcium carbonate, and (D) carbon black, and have completed the present invention.
  • a curable composition comprising (A) a branched polyoxyalkylene polymer having a reactive silicon group, (C) calcium carbonate, and (D) carbon black,
  • a curable composition characterized in that a reactive silicon group is represented by the following general formula (1): -SiX n R 3-n (1)
  • X represents a hydroxyl group or a hydrolyzable group
  • R represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent (excluding the hydrolyzable group).
  • Xs may be the same or different from each other, and when R is a plurality, R may be the same or different from each other.
  • the number average molecular weight of the component (A) and / or the component (B) is 15,000 to 50,000, respectively, and / or the number average molecular weight of the mixture of the component (A) and the component (B) is 15,000 to
  • the component (C) is at least one selected from heavy calcium carbonate, precipitated calcium carbonate, and calcium carbonate obtained by surface-treating these calcium carbonates.
  • the component (A) contains 60 to 200 parts by weight of the component (C) and 20 to 50 parts by weight of the component (D) with respect to 100 parts by weight of the total of the components (B) and (B).
  • the curable composition according to any one of
  • the curable composition of the present invention is excellent in the tensile strength at break of the cured product, and further excellent in the rise in tensile shear strength. It can also be used for adhesive applications.
  • the curable composition according to the present invention includes (A) a branched polyoxyalkylene polymer having a reactive silicon group, (C) calcium carbonate, and (D) carbon black.
  • the curable composition may further contain (B) a linear polyoxyalkylene polymer having a reactive silicon group.
  • the reactive silicon group possessed by (A) the branched polyoxyalkylene polymer having a reactive silicon group and (B) the linear polyoxyalkylene polymer having a reactive silicon group is represented by the following general formula (1). Is done. -SiX n R 3-n (1)
  • X represents a hydroxyl group or a hydrolyzable group
  • R represents a monovalent organic group having 1 to 20 carbon atoms which may have a substituent (excluding the hydrolyzable group).
  • . n represents 1, 2 or 3.
  • X is plural, X may be the same or different.
  • R plural, Rs may be the same or different.
  • R is preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms.
  • R include a methyl group, an ethyl group, a cyclohexyl group, a phenyl group, a benzyl group, a methoxymethyl group, a chloromethyl group, a tri group represented by R ′ 3 SiO— in which R ′ is a methyl group, a phenyl group, or the like.
  • organosiloxy groups are preferably an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and particularly preferably an alkyl group having 1 to 20 carbon atoms.
  • R include a methyl group, an ethyl
  • a methyl group and an ethyl group are more preferable.
  • the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
  • Specific examples of the hydrolyzable group include methoxy group, ethoxy group, isopropoxy group, methoxymethyl group, chloromethyl group and the like. In these, a methoxy group and an ethoxy group are more preferable.
  • reactive silicon groups include dimethoxymethylsilyl, diethoxymethylsilyl, diisopropoxymethylsilyl, (chloromethyl) dimethoxysilyl, (methoxymethyl) dimethoxysilyl, trimethoxysilyl, And ethoxysilyl group.
  • a dimethoxymethylsilyl group and a diethoxymethylsilyl group are preferable because a cured product having good mechanical properties can be obtained, and a dimethoxymethylsilyl group is particularly preferable.
  • the main chain skeleton of the component (A) and the component (B) is preferably a repeating unit represented by the general formula (2).
  • R 1 represents a linear or branched alkylene group having 1 to 14 carbon atoms.
  • the general formula (2) for example, -CH 2 O -, - CH 2 CH 2 O -, - CH 2 CH (CH 3) O -, - CH 2 CH (C 2 H 5) O -, - CH 2 C (CH 3 ) 2 O—, —CH 2 CH 2 CH 2 CH 2 O— and the like can be mentioned.
  • the main chain skeleton should have a propylene oxide unit represented by —CH 2 CH (CH 3 ) O— of 80% by weight or more. Preferably, it is 90% by weight or more.
  • the polymerization method in which an alkylene oxide is reacted with an initiator in the presence of a double metal cyanide complex catalyst has a narrow molecular weight distribution. It is preferable because a polymer can be obtained.
  • Examples of the double metal cyanide complex catalyst include a zinc hexacyanocobaltate complex represented by Zn 3 [Co (CN) 6 ] 2 .
  • a catalyst in which at least one compound selected from alcohol compounds such as tert-butanol and ether compounds such as glyme, diglyme and triglyme is coordinated as an organic ligand can also be used.
  • the initiator for synthesizing the component (A) is preferably a compound having 3 to 6 active hydrogens, more preferably a compound having 3 to 4 active hydrogens, and particularly preferably a compound having 3 active hydrogens. .
  • the functional group having active hydrogen a hydroxyl group is particularly preferable.
  • Specific examples of the initiator for synthesizing the component (A) include polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, glucose, and sorbitol. Further, polyoxyalkylene triol having a molecular weight lower than that of the component (A) and having a number average molecular weight of 500 to 20,000 can be used.
  • the initiator for synthesizing the component (B) is preferably a compound having two active hydrogens.
  • the functional group having active hydrogen a hydroxyl group is particularly preferable.
  • Specific examples of the initiator for synthesizing the component (B) include dihydric alcohols such as ethylene glycol, diethylene glycol, and propylene glycol. Further, polyoxyalkylene diol having a molecular weight lower than the number average molecular weight of the component (B) and having a number average molecular weight of 500 to 20,000 can be used.
  • alkylene oxide examples include ethylene oxide, propylene oxide, isobutylene oxide and the like.
  • the method for introducing a reactive silicon group into the main chain skeleton of the component (A) and the component (B) can be performed by, for example, the following known methods.
  • the terminal hydroxyl group of the polyoxyalkylene polymer is alcoholated to form -OM (M is an alkali metal), and then reacted with an unsaturated group-containing halogenated hydrocarbon (allyl chloride and / or methallyl chloride).
  • an unsaturated group-containing halogenated hydrocarbon allyl chloride and / or methallyl chloride.
  • a saturated terminal polyoxyalkylene polymer is produced.
  • a reactive silicon group is formed by hydrosilylating the unsaturated group with an alkoxysilane represented by HSiX n R 3-n (X, R, and n are the same as those in the general formula (1)). How to introduce.
  • (Ii) A method of reacting a mercaptosilane compound with an unsaturated group of an unsaturated group-terminated polyoxyalkylene polymer obtained in the same manner as in (i).
  • (Iii) A method of reacting an isocyanate silane compound with a terminal hydroxyl group of a polyoxyalkylene polymer.
  • (Iv) A method in which a polyisocyanate compound is reacted with a terminal hydroxyl group of a polyoxyalkylene polymer to convert the terminal hydroxyl group into an isocyanate group, and then this isocyanate group is reacted with an isocyanate silane compound and / or an aminosilane compound.
  • the method (ii) may cause a problem of odor based on the mercaptosilane compound, and the methods (iii) and (iv) increase the viscosity of the obtained polymer and cause workability. In some cases, storage stability may be a problem. Therefore, among these methods, the method (i) is particularly preferable.
  • the number average molecular weights of the component (A) and the component (B) are preferably 15,000 to 50,000, more preferably 17,000 to 45,000, and more preferably 18,000 to 40,000 in terms of molecular weight in terms of GPC. 19,000 to 35,000 is particularly preferable, and 21,000 to 35,000 is most preferable. If the number average molecular weight is less than 15,000, the tensile elongation at break of the resulting cured product tends to be insufficient. When the number average molecular weight exceeds 50,000, the workability tends to deteriorate because the curing rate of the curable composition decreases and the viscosity increases.
  • the number average molecular weight of the mixture of component (A) and component (B) is preferably 15,000 to 50,000, more preferably 17,000 to 45,000, and more preferably 18,000 to 40,000 in terms of GPC molecular weight. More preferably, 19,000 to 35,000 is particularly preferable, and 21,000 to 35,000 is most preferable. If the number average molecular weight is less than 15,000, the tensile elongation at break of the resulting cured product tends to be insufficient. When the number average molecular weight exceeds 50,000, the workability tends to deteriorate because the curing rate of the curable composition decreases and the viscosity increases.
  • the number average molecular weights of the component (A) and the component (B) are based on the polymer precursor before introduction of the reactive silicon group based on the method for measuring the hydroxyl value of JIS K 1557 and the method for measuring the iodine value of JIS K 0070.
  • the molecular weight (terminal group molecular weight) corresponding to the number average molecular weight obtained by titration analysis can be obtained.
  • the number of reactive silicon groups in the component (A) is preferably 1.5 to 3 on average in one molecule of the polymer, more preferably 1.7 to 3 on average, and 1.8 on average. 2.8 is more preferable, an average of 1.9 to 2.7 is particularly preferable, and an average of 2.0 to 2.5 is most preferable. If the average is less than 1.5, the tensile strength at break of the cured product tends to be insufficient. On the other hand, if the average number exceeds 3, the tensile elongation at break of the cured product tends to be insufficient.
  • the number of reactive silicon groups in the component (B) is preferably 1.1 to 2 on average in one molecule of the polymer, more preferably 1.2 to 1.9 on average, and 1 on average. 3 to 1.8 is more preferable, and an average of 1.4 to 1.7 is particularly preferable. If the average is less than 1.1, curing of the curable composition may be insufficient. Further, the tensile strength at break of the cured product tends to be insufficient. On the other hand, if the average number exceeds 2, the tensile elongation at break of the cured product tends to be insufficient.
  • the average number of reactive silicon groups in component (A) and component (B) is the average number determined by a method of quantifying protons on carbon directly bonded to reactive silicon groups using a high-resolution 1 H-NMR instrument.
  • the obtained polymer is also regarded as a part of a polyoxyalkylene polymer having a reactive silicon group having the same main chain structure, and a parameter (when calculating the average number of reactive silicon groups in one molecule ( The number of molecules is included in the calculation.
  • the reactive silicon group of the component (A) and / or the component (B) may exist as a side chain inside the molecular chain or may exist at the end of the molecular chain.
  • the reactive silicon group is more preferably present at the end of the molecular chain from the viewpoint of tensile properties and adhesiveness.
  • the molecular weight distribution (Mw / Mn) of the component (A) and / or the component (B) is preferably narrow from the viewpoint of lowering the viscosity of the resulting curable composition, preferably 1.6 or less, more preferably 1.5 or less. 1.4 or less is particularly preferable.
  • (A) component and (B) component may be used individually, respectively, and may use 2 or more types together.
  • the mixing ratio (A / B) of the component (A) and the component (B) is preferably 100/0 to 5/95 by weight.
  • the preferred lower limit of the range of the mixing ratio of the component (A) and the component (B) is A / B ⁇ 40/60, more preferably A / B ⁇ 50/50. More preferably, A / B ⁇ 60/40, particularly preferably A / B ⁇ 70/30, and most preferably A / B ⁇ 85/15.
  • the preferred upper limit is 80/20 ⁇ A / B, more preferably 100/0 ⁇ A / B. From the standpoint of rising tensile shear strength, the preferred upper limit is 100/0 ⁇ A / B. It is.
  • the component (A) is less than 40% by weight of the entire polymer, there may be cases where sufficient rise in tensile shear strength cannot be obtained.
  • the mixing ratio (A / B) of the component (A) and the component (B) is preferably 95/5 to 5/95 by weight.
  • a more preferable lower limit of the range of the mixing ratio is A / B ⁇ 10/90, more preferably A / B ⁇ 15/85, particularly preferably A / B ⁇ 25/75, most preferably A / B ⁇ 40/60.
  • the upper limit is 90/10 ⁇ A / B, more preferably 85/15 ⁇ A / B, particularly preferably 75/25 ⁇ A / B, and most preferably 60/40 ⁇ A / B.
  • Component and component (B) are mixed and used, and the tensile property value is more than the value obtained by simply averaging the tensile property values obtained by using each of component (A) and component (B) alone. Excellent tensile strength at break and tensile elongation at break can be obtained.
  • the mixture of the component (A) and the component (B) can be obtained by separately synthesizing the component (A) and the component (B) and then mixing them. Moreover, a mixture can also be obtained by synthesize
  • the polyoxyalkylene polymer is handled as a mixture of the component (A) and the component (B).
  • (C) calcium carbonate is blended as a filler.
  • the calcium carbonate at least one selected from heavy calcium carbonate, precipitated calcium carbonate, and calcium carbonate obtained by surface-treating these calcium carbonates can be used.
  • Precipitated calcium carbonate is classified into light calcium carbonate having a major axis of 1 ⁇ m or more and colloidal calcium carbonate having an average particle size of 1 ⁇ m or less, and any of them can be used. Of these, it is preferable to use colloidal calcium carbonate from the viewpoint of obtaining good mechanical properties.
  • Surface-treated colloidal calcium carbonate can also be used.
  • the surface treatment agent include fatty acids such as stearic acid, fatty acid esters, modified fatty acids, resin acids such as rosin, paraffin wax, polyethylene wax, and cationic surfactants.
  • surface-treated colloidal calcium carbonate is preferred, and fatty acid-treated or resin acid-treated colloidal calcium carbonate is particularly preferred.
  • the average particle diameter of the colloidal calcium carbonate is more preferably 0.5 ⁇ m or less, further preferably 0.2 ⁇ m or less, and particularly preferably 0.02 to 0.1 ⁇ m.
  • Colloidal calcium carbonate is available as a commercial product such as white glaze CCR, white glaze CC, white glaze O, Calmos, Vigot 10 (all manufactured by Shiroishi Calcium Co., Ltd.), Neolight SP (produced by Takehara Chemical Industry Co., Ltd.), and the like.
  • Heavy calcium carbonate preferably has an average particle size of 0.3 to 10 ⁇ m, more preferably 0.7 to 7 ⁇ m, particularly preferably 0.7 to 5 ⁇ m, and most preferably 1.1 to 4 ⁇ m. If it is less than 0.3 ⁇ m, the viscosity of the curable composition tends to be high and workability tends to be poor. If it exceeds 10 ⁇ m, sufficient adhesion tends to be not obtained.
  • the surface-treated heavy calcium carbonate can also be used.
  • the surface treatment agent include fatty acids such as stearic acid, fatty acid esters, modified fatty acids, paraffin wax, polyethylene wax, and cationic surfactants.
  • Heavy calcium carbonate is, for example, SS-88, NS-100, NS-400, NS-600, NS-1000, NS-2300, NS-2500, NCC-110, NCC-410, NCC-610, NCC- 1010, NCC-2510, NEW-F, NCC-P (all of which are manufactured by FORMOSA PLASTICS CORPORATION).
  • a component may be used independently and may use 2 or more types together.
  • the amount of component (C) used is preferably 60 to 200 parts by weight, more preferably 100 to 180 parts by weight, still more preferably 120 to 180 parts by weight, based on 100 parts by weight of the total of components (A) and (B). 130 to 170 parts by weight are particularly preferable.
  • the amount of heavy calcium carbonate used is less than that of precipitated calcium carbonate, more preferably less than 10 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B). It is particularly preferred not to do so.
  • (D) carbon black in order to obtain rises in tensile breaking strength and tensile shear strength.
  • D What can be obtained by a well-known manufacturing method can be used for a component. Examples thereof include furnace black, lamp black, gas black, channel black, thermal black, and acetylene black obtained by the oil furnace method or the gas furnace method. From the viewpoint of availability, the furnace method which is the mainstream of the current production method is preferred.
  • the oil absorption amount of component (D) is preferably 50 ml / 100 g or more, more preferably 50 to 150 ml / 100 g, more preferably 50 to 130 ml / 100 g is more preferred, 70 to 120 ml / 100 g is even more preferred, and 90 to 120 ml / 100 g is particularly preferred. If it is less than 50 ml / 100 g, sufficient tensile strength at break tends not to be obtained. If it exceeds 150 ml / 100 g, the viscosity of the curable composition tends to be high and workability tends to be poor.
  • component (D) is available as commercial products such as HIBLACK30, HIBLACK10, HIBLACK5L, HIBLACK20L, HIBLACK30L (manufactured by Orion Engineered Carbons Co., Ltd.).
  • a component may be used independently and may use 2 or more types together.
  • the amount of component (D) used is preferably 5 to 50 parts by weight, more preferably 10 to 50 parts by weight, even more preferably 20 to 50 parts by weight, based on 100 parts by weight of the total of components (A) and (B). 20 to 45 parts by weight is particularly preferable. If it is less than 5 parts by weight, sufficient tensile strength at break tends to be not obtained. When the amount exceeds 50 parts by weight, the viscosity increases, so that the workability tends to deteriorate or the curable composition cannot be produced.
  • fillers can also be blended with the curable composition of the present invention as long as the physical properties of the cured product are not impaired.
  • Other fillers include fumed silica, precipitated silica, crystalline silica, fused silica, calcined clay, clay and kaolin and other reinforcing fillers, dolomite, silicic anhydride, hydrous silicic acid, magnesium carbonate, diatomaceous earth, Examples include talc, titanium oxide, bentonite, organic bentonite, ferric oxide, aluminum fine powder, zinc oxide, activated zinc white, resin powder such as PVC powder and PMMA powder, and fibrous filler such as glass fiber.
  • a curing catalyst can be blended in order to accelerate the curing of the component (A) and / or the component (B).
  • the curing catalyst include organic tin compounds, carboxylic acids, carboxylic acid metal salts, and amine compounds.
  • Organic tin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin phthalate, dibutyltin dioctanoate, dibutyltin bis (2-ethylhexanoate), dibutyltin bis (methyl maleate), dibutyltin bis (ethyl maleate) , Dibutyltin bis (butyl maleate), dibutyltin bis (octylmaleate), dibutyltin bis (tridecylmaleate), dibutyltin bis (benzylmaleate), dibutyltin diacetate, dioctyltin bis (ethylmaleate) ), Dioctyltin bis (octyl maleate), dibutyltin dimethoxide, dibutyltin bis (nonylphenoxide), dibutenyltin oxide, dibutyltin oxide, dibuty
  • carboxylic acid examples include neodecanoic acid, versatic acid, 2,2-dimethyloctanoic acid, 2-ethyl-2,5-dimethylhexanoic acid and the like.
  • Carboxylic acid metal salts include tin carboxylate, lead carboxylate, bismuth carboxylate, potassium carboxylate, calcium carboxylate, barium carboxylate, titanium carboxylate, zirconium carboxylate, hafnium carboxylate, vanadium carboxylate, manganese carboxylate, Examples thereof include iron carboxylate, cobalt carboxylate, nickel carboxylate, and cerium carboxylate.
  • amine compound examples include laurylamine, diethylaminopropylamine, guanidine, diphenylguanidine, 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) and the like.
  • DBU 1,8-diazabicyclo (5,4,0) undecene-7
  • dibutyltin compounds and dioctyltin compounds are more preferred because of their high strength.
  • the amount of the curing catalyst used is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 15 parts by weight, with respect to 100 parts by weight in total of the components (A) and (B). Is more preferably 10 to 10 parts by weight, particularly preferably 1 to 7 parts by weight, and most preferably 1.5 to 5 parts by weight. If it is less than 0.05 parts by weight, the curing rate tends to be slow. On the other hand, if it exceeds 20 parts by weight, the curing rate becomes too fast, and a good cured product cannot be obtained.
  • a plasticizer can be added to the curable composition of the present invention.
  • the plasticizer By adding the plasticizer, the viscosity and slump property of the curable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the curable composition can be adjusted.
  • plasticizers include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate; non-aromatics such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, diisodecyl succinate Dibasic acid esters; Aliphatic esters such as butyl oleate and methyl acetylricinolinate; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Chlorinated paraffins; Alkyldiphenyl And hydrocarbon oils such as partially hydrogenated terphenyl; process oils; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate. Moreover, the compound obtained by hydrogenating a phthalate ester can also be used. This compound is industrially manufactured and
  • a polymeric plasticizer can be used.
  • a high-molecular plasticizer is used, the initial physical properties are maintained over a long period of time as compared with the case where a low-molecular plasticizer that is a plasticizer containing no polymer component in the molecule is used.
  • polymer plasticizer vinyl polymers obtained by polymerizing vinyl monomers by various methods; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, pentaerythritol ester; sebacic acid, Polyester plasticizers obtained from dibasic acids such as adipic acid, azelaic acid and phthalic acid and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; molecular weight of 500 or more, and more than 1000 Polyether polyols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc., or the hydroxy groups of these polyether polyols are ester groups, ethyl groups, etc.
  • Polystyrenes such as polystyrene and polymethyl - ⁇ - methyl styrene; polyethers such as converted derivative polybutadiene, polybutene, polyisobutylene, butadiene - acrylonitrile, etc. polychloroprene and the like.
  • a polyether plasticizer is more preferable from the point with the deep part sclerosis
  • the number average molecular weight of the polyether plasticizer is preferably 500 to 15,000, more preferably 800 to 10,000, and particularly preferably 1,000 to 5,000. If the molecular weight is small, the plasticizer will flow out and good physical properties cannot be maintained. Moreover, when molecular weight is too large, a viscosity will become high and workability
  • the molecular weight distribution of the polyether plasticizer is preferably narrow, preferably less than 1.8, more preferably 1.6 or less, and particularly preferably 1.4 or less.
  • the polyether plasticizer may have a reactive silicon group. In this case, it is preferable that the number average molecular weight is smaller than that of the components (A) and (B) and the number of reactive silicon groups is small.
  • a plasticizer may be used independently and may use 2 or more types together.
  • the amount of the plasticizer used is preferably 5 to 150 parts by weight, more preferably 10 to 120 parts by weight, particularly preferably 20 to 100 parts by weight based on 100 parts by weight of the total of the components (A) and (B). . If it is less than 5 parts by weight, the effect as a plasticizer will not be exhibited, and if it exceeds 150 parts by weight, the mechanical strength of the cured product will be insufficient.
  • Adhesive agents are ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyldimethoxymethylsilane, ⁇ -aminopropyldiethoxymethylsilane, N- ( ⁇ -aminoethyl) - ⁇ - Aminopropyltrimethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyldimethoxymethylsilane, N- ( ⁇ -aminoethyl) - ⁇ -aminopropyltriethoxysilane, N- ( ⁇ -aminoethyl) - ⁇ -Amino group-containing silane compounds such as aminopropyldiethoxymethylsilane, isocyanate group-containing silane compounds, mercapto group-containing silane compounds, epoxy group-containing
  • amino group-containing silane compounds are more preferable from the viewpoint of adhesiveness.
  • the amount of the adhesion-imparting agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the component (A) and the component (B). .
  • an ultraviolet absorber can be blended for the purpose of enhancing the surface weather resistance of the cured product.
  • ultraviolet absorbers include benzophenone, benzotriazole, salicylate, substituted tolyl, and metal chelate compounds, with benzotriazole being particularly preferred.
  • Benzotriazoles are commercially available such as Tinuvin P, Tinuvin 1130, Tinuvin 99-2, Tinuvin 928, Tinuvin 326, Tinuvin 329 (BASF).
  • the amount of the ultraviolet absorber used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
  • a light stabilizer can be blended with the curable composition of the present invention for the purpose of preventing photo-oxidative deterioration of the cured product.
  • the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable.
  • Hindered amines are commercially available such as Tinuvin 770, Tinuvin 770DF, Tinuvin 292, Tinuvin 5050, Tinuvin 5151, Tinuvin 5060 (manufactured by BASF).
  • the amount of the light stabilizer used is preferably 0.1 to 10 parts by weight, particularly preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the total of the components (A) and (B).
  • a heat stabilizer can be blended with the curable composition of the present invention for the purpose of preventing oxidative deterioration of the cured product due to heat.
  • the heat stabilizer include hindered phenols, monophenols, bisphenols, and polyphenols, with hindered phenols being particularly preferred.
  • the hindered phenol type is available as a commercial product such as IRGANOX 1010 and IRGANOX 1035 (manufactured by BASF).
  • the amount of the heat stabilizer used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B).
  • a dehydrating agent can be blended with the curable composition of the present invention for the purpose of enhancing storage stability.
  • the dehydrating agent include alkoxysilane compounds such as vinyltrimethoxysilane and vinylmethyldimethoxysilane.
  • the amount of the dehydrating agent used is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of component (A) and component (B).
  • a thixotropic agent can be blended with the curable composition of the present invention in order to improve workability.
  • the thixotropic agent include polyamide wax, hydrogenated castor oil, and metal soap.
  • the amount of the thixotropic agent used is preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the total of component (A) and component (B).
  • a tackifier resin for the purpose of improving various physical properties of the curable composition or the cured product to be obtained, a tackifier resin, a physical property modifier, a photocurable compound, an oxygen curable compound, if necessary.
  • Compound, epoxy compound, particulate matter, flame retardant, curability modifier, radical inhibitor, metal deactivator, ozone degradation inhibitor, phosphorus peroxide decomposer, lubricant, pigment, foaming agent, solvent, prevention A mold agent etc. can be mix
  • the curable composition of the present invention is a batch production method in which all compounding agents are mixed in a kneader such as a mixer and mixed, or a compounding agent is sequentially added and mixed in an extruder such as a screw type extruder. It can be manufactured by any method such as a continuous production method.
  • the curable composition of the present invention can also be prepared as a one-component curable composition in which all the ingredients are mixed and stored in advance, and cured by moisture in the air during construction. Further, it can be prepared as a two-component curable composition which is divided into a main agent containing a polymer and the like and a curing agent containing a curing catalyst and used by mixing at the time of construction.
  • the curable composition of the present invention can be used as a sealant for buildings, ships, automobiles, railways, roads and the like. It can also be used as a car repair agent, bus or truck sealant, or adhesive. Furthermore, it can also be used as a sealing composition and an adhesive composition that can be adhered to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or by applying a primer. In addition to a normal adhesive, it can be used as a contact adhesive.
  • the cured product of the present invention can be obtained by curing the curable composition of the present invention.
  • the resulting allyl group-terminated polyoxypropylene polymer is reacted with dimethoxymethylsilane using a platinum content of a platinum vinylsiloxane complex in an isopropanol solution having a platinum content of 3 wt% as a catalyst to give a branched polysiloxane having a dimethoxymethylsilyl group at the molecular end.
  • An oxypropylene polymer (polymer A-1) was obtained.
  • the number of dimethoxymethylsilyl groups was 2.4 on average per molecule.
  • the number average molecular weight in terms of GPC was 26,000.
  • Synthesis Example 2 The same procedure as in Synthesis Example 1 was performed except that a 1/1 (weight ratio) mixture of a polyoxypropylene triol molecular weight of about 3,000 and a polyoxypropylene diol of about 2,000 was used as an initiator, and converted to GPC Has a number average molecular weight of 19,700, has an average of 1.7 dimethoxymethylsilyl groups per molecule at the molecular end, and contains a branched structure and a linear structure in a ratio of 1/1 (weight ratio). A polyoxypropylene polymer (polymer AB-1) was obtained.
  • Synthesis Example 3 The same procedure as in Synthesis Example 1 was performed except that polyoxypropylene diol having a molecular weight of about 3,000 was used as an initiator, the number average molecular weight in terms of GPC was 25,500, and an average of 1.4 per molecule. A linear polyoxypropylene polymer (polymer B-1) having a dimethoxymethylsilyl group at the molecular end was obtained.
  • Example 1 For 100 parts by weight of the polymer A-1 obtained in Synthesis Example 1, 50 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals, Inc., trade name: Actol P-23) as a polyether plasticizer, surface-treated carbonic acid 140 parts by weight of calcium (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Neolight SP, surface-treated colloidal calcium carbonate, average particle size: 0.08 ⁇ m), carbon black (manufactured by Orion Engineered Carbons Co., Ltd.) , Trade name: HIBLACK 10, oil absorption: 97 ml / 100 g, average particle size: 30 nm) 40 parts by weight, heat stabilizer (BASF, trade name: IRGANOX 1010), 1 part by weight, UV absorber (BASF, trade name) : 1 part by weight of Tinuvin 326), 1 part by weight of light stabilizer (manufactured by BASF, trade name: Tinuvin 770
  • Examples 2 to 6 Comparative Example 1
  • Example 1 By the same method as Example 1, it prepared according to the compounding agent and usage-amount (parts by weight) of Table 1, and obtained the curable composition.
  • the physical property measurement was performed with the following method. (Tensile properties) In an atmosphere of 23 ° C. and a relative humidity of 50%, the curable composition was filled in a polyethylene mold having a thickness of 3 mm so that no bubbles would enter. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No.
  • dumbbell was punched in accordance with JIS K 6251, a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed, 50% tensile stress (M50), 100% Tensile stress (M100), tensile break strength (TB), and tensile break elongation (EB) were measured. The measurement results are shown in Table 1. (Rise of tensile shear strength) In a 23 ° C. and 50% relative humidity atmosphere, a curable composition was applied to have an adhesion area of 25 mm ⁇ 12.5 mm and a thickness of 1 mm, and a stainless steel as an adherend was bonded together to produce a test specimen. did.
  • the start time is the time of pasting, and then the tensile shear test (tensile speed 50 mm / min) is performed after 1 hour, 2 hours, and 3 hours in an atmosphere of 23 ° C. and 50% relative humidity. Intensity measurements were taken. Moreover, the destruction state was observed visually.
  • the fracture states were cohesive fracture (CF), thin layer fracture (TF), and interface fracture (AF).
  • Table 1 The evaluation results are shown in Table 1. As is apparent from Table 1, the curable compositions (Examples 1 to 6) in which the components (A) and (B) were mixed at a weight ratio of 100/0 to 50/50 were used as (B) It can be seen that the tensile shear strength is superior to that of the curable composition using only the components (Comparative Example 1).
  • Example 7 For 100 parts by weight of the polymer A-1 obtained in Synthesis Example 1, 50 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals, Inc., trade name: Actol P-23) as a polyether plasticizer, surface-treated carbonic acid Calcium (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Neolight SP, colloidal calcium carbonate surface-treated with fatty acid, average particle size: 0.08 ⁇ m) 130 parts by weight, carbon black (manufactured by Orion Engineered Carbons Co., Ltd.) , Trade name: HIBLACK 10, oil absorption: 97 ml / 100 g, average particle size: 30 nm, 50 parts by weight, heat stabilizer (BASF, trade name: IRGANOX 1010), 1 part by weight, UV absorber (BASF, trade name) : 1 part by weight of Tinuvin 326), 1 part by weight of light stabilizer (manufactured by BASF, trade name:
  • Example 8 By the same method as Example 7, it adjusted according to the compounding agent and usage-amount (parts by weight) of Table 2, and obtained the 1 liquid type curable composition.
  • the physical property measurement was performed with the following method. (Tensile properties) In an atmosphere of 23 ° C. and a relative humidity of 50%, the curable composition was filled in a polyethylene mold having a thickness of 3 mm so that no bubbles would enter. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No.
  • the test body was produced by curing for 7 days, 14 days and 21 days in an atmosphere of 23 ° C. and 50% relative humidity, and curing for 23 days ⁇ 7 days and 50 ° C. ⁇ 4 days.
  • a tensile shear test (tensile speed: 50 mm / min) was performed to measure the tensile shear strength.
  • the fracture states were cohesive fracture (CF), thin layer fracture (TF), and interface fracture (AF).
  • CF cohesive fracture
  • TF thin layer fracture
  • AF interface fracture
  • Table 2 “C50A50” means 50% cohesive failure and 50% interfacial failure
  • C40A60” means 40% cohesive failure and 60% interfacial failure.
  • excellent tensile shear strength can be obtained if the amount of carbon black used is within the range of 5 to 50 parts by weight per 100 parts by weight of component (A).
  • Example 11 For 100 parts by weight of the polymer AB-1 obtained in Synthesis Example 2, 50 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals, Inc., trade name: Actol P-23) as a polyether plasticizer, surface-treated carbonic acid 140 parts by weight of calcium (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Neolight SP, surface-treated colloidal calcium carbonate, average particle size: 0.08 ⁇ m), carbon black (manufactured by Orion Engineered Carbons Co., Ltd.) , Trade name: HIBLACK 10, oil absorption: 97 ml / 100 g, average particle size: 30 nm) 40 parts by weight, heat stabilizer (BASF, trade name: IRGANOX 1010), 1 part by weight, UV absorber (BASF, trade name) : Tinuvin 326) 1 part by weight, light stabilizer (manufactured by BASF, trade name: Tinuvin 770) 1 part by
  • Example 12 to 14 By the same method as Example 11, it prepared according to the compounding agent and usage-amount (parts by weight) of Table 3, and obtained the curable composition.
  • the average particle diameters of HIBLACK 10, 30, 5L, and 20L are 30 nm, 23 nm, 35 nm, and 28 nm, respectively.
  • the physical property measurement was performed with the following method. (Tensile properties) In an atmosphere of 23 ° C. and a relative humidity of 50%, the curable composition was filled in a polyethylene mold having a thickness of 3 mm so that no bubbles would enter. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No.
  • dumbbell was punched in accordance with JIS K 6251, a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed, 50% tensile stress (M50), 100% Tensile stress (M100), tensile break strength (TB), and tensile break elongation (EB) were measured. The measurement results are shown in Table 3. (Rise of tensile shear strength) In a 23 ° C. and 50% relative humidity atmosphere, a curable composition was applied to have an adhesion area of 25 mm ⁇ 12.5 mm and a thickness of 1 mm, and a stainless steel as an adherend was bonded together to produce a test specimen. did.
  • the start time is the time of pasting, and then the tensile shear test (tensile speed 50 mm / min) is performed after 1 hour, 2 hours, and 3 hours in an atmosphere of 23 ° C. and 50% relative humidity. Intensity measurements were taken. Moreover, the destruction state was observed visually.
  • the fracture states were cohesive fracture (CF), thin layer fracture (TF), and interface fracture (AF).
  • Table 3 As is apparent from Table 3, it can be seen that all of the curable compositions containing the carbon blacks of Examples 11 to 14 have an excellent rise in tensile shear strength.
  • Example 15 For 100 parts by weight of the polymer A-1 obtained in Synthesis Example 1, 50 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals, Inc., trade name: Actol P-23) as a polyether plasticizer, surface-treated carbonic acid 140 parts by weight of calcium (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Neolight SP, surface-treated colloidal calcium carbonate, average particle size: 0.08 ⁇ m), carbon black (manufactured by Orion Engineered Carbons Co., Ltd.) , Trade name: HIBLACK 10, oil absorption: 97 ml / 100 g, average particle size: 30 nm) 40 parts by weight, heat stabilizer (BASF, trade name: IRGANOX 1010), 1 part by weight, UV absorber (BASF, trade name) : 1 part by weight of Tinuvin 326), 1 part by weight of light stabilizer (manufactured by BASF, trade name: Tinuvin
  • Example 16 By the same method as Example 15, it prepared according to the compounding agent and usage-amount (parts by weight) of Table 4, and obtained 1 liquid type curable composition.
  • the physical property measurement was performed with the following method. (Tensile properties) In an atmosphere of 23 ° C. and a relative humidity of 50%, the curable composition was filled in a polyethylene mold having a thickness of 3 mm so that no bubbles would enter. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No.
  • the test body was produced by curing for 7 days and 14 days in an atmosphere of 23 ° C. and 50% relative humidity.
  • a tensile shear test (tensile speed: 50 mm / min) was performed to measure the tensile shear strength. Moreover, the destruction state was observed visually.
  • the fracture states were cohesive fracture (CF), thin layer fracture (TF), and interface fracture (AF).
  • Table 4 Haand peel adhesion
  • the curable composition was applied to the ceramic coated glass as the adherend while sufficiently adhering in a bead shape. Then, the test body was produced by curing at 23 ° C. and 50% relative humidity for 7 days and 14 days.
  • C40T40A20 means 40% cohesive failure, 40% thin layer failure, and 20% interface failure. As is apparent from Table 4, it can be seen that increasing the compounding amount of the amino group-containing silane compound as an adhesion-imparting agent improves the adhesion to the ceramic coat glass.
  • Example 17 For 100 parts by weight of the polymer A-1 obtained in Synthesis Example 1, 50 parts by weight of polypropylene glycol (manufactured by Mitsui Chemicals, Inc., trade name: Actol P-23) as a polyether plasticizer, surface-treated carbonic acid Calcium (manufactured by Takehara Chemical Industry Co., Ltd., trade name: Neolight SP), carbon black (manufactured by Orion Engineered Carbons Co., Ltd., trade name: HIBLACK30, oil absorption: 110 ml / 100 g, average particle size 23 nm) 20 parts by weight, 1 part by weight of an ultraviolet absorber (manufactured by BASF, trade name: Tinuvin 326) and 1 part by weight of a light stabilizer (manufactured by BASF, trade name: Tinuvin 770) were weighed and mixed.
  • polypropylene glycol manufactured by Mitsui Chemicals, Inc., trade name: Actol P-273
  • surface-treated carbonic acid Calcium
  • Example 18 to 23, Comparative Example 2 By the same method as Example 1, it adjusted according to the compounding agent and usage-amount of Table 5, and obtained the 1 liquid type curable composition.
  • HIBLACK 10 Orthogonal Engineered Carbons, oil absorption: 97 ml / 100 g, average particle size: 30 nm
  • Monarch 570 manufactured by CABOT, oil absorption: 115 ml / 100 g, average particle size: 24 nm
  • the physical property measurement was performed with the following method.
  • (Tensile properties) In an atmosphere of 23 ° C. and a relative humidity of 50%, the curable composition was filled in a polyethylene mold having a thickness of 3 mm so that no bubbles would enter. Thereafter, the cured product was obtained by curing at 23 ° C. and 50% relative humidity for 3 days and further at 50 ° C. for 4 days. From the resulting cured product, No. 3 dumbbell was punched in accordance with JIS K6251 and a tensile test (tensile speed 200 mm / min, 23 ° C., relative humidity 50%) was performed, 50% tensile stress (M50), 100% tensile.
  • M50 50% tensile stress
  • the fracture states were cohesive fracture (CF), thin layer fracture (TF), and interface fracture (AF).
  • the evaluation results are shown in Table 5.
  • the curable compositions containing the component (A) (Examples 17 to 23) had a tensile strength at break and tensile strength higher than those of the curable composition using only the component (B) (Comparative Example 2). It can be seen that the shear strength is excellent.
  • the curable compositions (Examples 18 to 20) in which the components (A) and (B) were mixed at a 1/1 (weight ratio) have excellent tensile breaking strength and tensile breaking elongation. I understand that. This result was derived from a simple average of the curable composition (Example 17) using the component (A) alone and the curable composition (Comparative Example 2) using the component (B) alone. The value is better than that.
  • the curable composition of the present invention can be used as a sealant for buildings, ships, automobiles, railways, roads and the like. It can also be used as a car repair agent, bus or truck sealant, or adhesive. Furthermore, it can also be used as a sealing composition and an adhesive composition that can be adhered to a wide range of substrates such as glass, porcelain, wood, metal, resin molding, etc. alone or by applying a primer. In addition to a normal adhesive, it can be used as a contact adhesive.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

L'invention concerne une composition durcissable qui contient (A) un polymère polyoxyalkylène ramifié ayant un groupe silicium réactif, (C) du carbonate de calcium et (D) du noir de carbone, et qui est caractérisée en ce que le groupe silicium réactif est représenté par la formule générale (1). -SiXnR3-n (1) (Dans la formule, X représente un groupe hydroxyle ou un groupe hydrolysable ; R représente un groupe organique monovalent facultativement substitué ayant 1-20 atomes de carbone (à l'exclusion d'un groupe hydrolysable) ; et n représente 1, 2 ou 3. Dans les cas où il y a une pluralité de fractions X, les fractions X peuvent être identiques ou différentes les unes des autres. Dans les cas où il y a une pluralité de fractions R, les fractions R peuvent être identiques ou différentes les unes des autres).
PCT/JP2013/080082 2012-11-09 2013-11-07 Composition durcissable et produit durci de celle-ci Ceased WO2014073593A1 (fr)

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
WO2017119396A1 (fr) 2016-01-08 2017-07-13 株式会社カネカ Mousse de résine de silicone modifiée
JP2018104670A (ja) * 2016-12-27 2018-07-05 旭硝子株式会社 硬化性組成物およびその製造方法、硬化物、ならびにシーリング材
WO2020203749A1 (fr) 2019-03-29 2020-10-08 株式会社カネカ Matériau de stockage de chaleur latente
WO2022122782A1 (fr) 2020-12-08 2022-06-16 Zephyros, Inc. Composition comprenant un prépolymère modifié par silyle et du noir de carbone hautement structuré
WO2024256486A1 (fr) 2023-06-13 2024-12-19 Zephyros, Inc. Système à deux composants durcissable à l'humidité comprenant un accélérateur

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CN110922940B (zh) * 2019-12-02 2022-04-26 广东高士高科实业有限公司 一种室温快固贮存稳定的环保ms密封胶及其制备方法

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JP2007091931A (ja) * 2005-09-29 2007-04-12 Kaneka Corp オルガノシロキサン変性ポリオキシアルキレン系重合体、および、該重合体を含有するパネル用接着剤
JP2007169441A (ja) * 2005-12-21 2007-07-05 Asahi Glass Co Ltd 伸び増強剤及びそれを含む硬化性組成物
JP2011219554A (ja) * 2010-04-06 2011-11-04 Kaneka Corp 硬化性組成物
WO2012020560A1 (fr) * 2010-08-10 2012-02-16 株式会社カネカ Composition polymérisable
JP2012057148A (ja) * 2010-08-10 2012-03-22 Kaneka Corp 硬化性組成物
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JP2006063335A (ja) * 2004-07-29 2006-03-09 Asahi Glass Co Ltd 室温硬化性組成物
JP2007091931A (ja) * 2005-09-29 2007-04-12 Kaneka Corp オルガノシロキサン変性ポリオキシアルキレン系重合体、および、該重合体を含有するパネル用接着剤
JP2007169441A (ja) * 2005-12-21 2007-07-05 Asahi Glass Co Ltd 伸び増強剤及びそれを含む硬化性組成物
JP2011219554A (ja) * 2010-04-06 2011-11-04 Kaneka Corp 硬化性組成物
WO2012020560A1 (fr) * 2010-08-10 2012-02-16 株式会社カネカ Composition polymérisable
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JP2013194197A (ja) * 2012-03-22 2013-09-30 Kaneka Corp 硬化性組成物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017119396A1 (fr) 2016-01-08 2017-07-13 株式会社カネカ Mousse de résine de silicone modifiée
JP2018104670A (ja) * 2016-12-27 2018-07-05 旭硝子株式会社 硬化性組成物およびその製造方法、硬化物、ならびにシーリング材
WO2020203749A1 (fr) 2019-03-29 2020-10-08 株式会社カネカ Matériau de stockage de chaleur latente
WO2022122782A1 (fr) 2020-12-08 2022-06-16 Zephyros, Inc. Composition comprenant un prépolymère modifié par silyle et du noir de carbone hautement structuré
WO2024256486A1 (fr) 2023-06-13 2024-12-19 Zephyros, Inc. Système à deux composants durcissable à l'humidité comprenant un accélérateur

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