Classifications

• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/12—Powdering or granulating
  • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/06—Preparatory processes
• • 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
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
  • C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2383/04—Polysiloxanes
  • C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/04—Polysiloxanes
  • C08J2483/06—Polysiloxanes containing silicon bound to oxygen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
  • C08J2483/04—Polysiloxanes
  • C08J2483/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups

Definitions

• the present invention relates to a silicone particle in which the surface of a silicone elastomer spherical particle is coated with polyorganosilsesquioxane, and a method for producing the same.
• Silicone elastomer particles having rubber elasticity are used as a resin stress relaxation agent.
• thermosetting resins such as epoxy resins are used for packaging electronic and electrical components, but in order to make the package difficult to break even if stress is applied to the package due to the expansion of the resin due to the heat generated by the electrical components.
• silicone elastomer particles are blended in the resin.
• the silicone elastomer particles have high cohesiveness and low dispersibility in the resin, the stress relaxation effect of the resin due to the silicone elastomer particles cannot be sufficiently obtained. There was a problem that the strength decreased.
• silicone particles in which silicone rubber spherical fine particles are coated with a polyorganosilsesquioxane resin Patent Document 1
• the silicone particles are characterized by rubber elasticity, low cohesiveness, and high dispersibility in the resin.
• silicone particles in which polyorganosilsesquioxane is polymethylsilsesquioxane have the lowest cohesiveness and high dispersibility.
• the silicone particles can be obtained by adding organotrialkoxysilane to an aqueous dispersion of silicone rubber spherical fine particles and subjecting organotrialkoxysilane to hydrolysis and condensation reaction under predetermined conditions.
• the silicone particles do not fall off if the adhesion between the resin and the silicone particles is improved.
• the polyorganosilsesquioxane contains an organic group reactive with the resin.
• a part of organotrialkoxysilane, which is a raw material of polyorganosilsesquioxane is poly (meth) acryloxyalkyltrialkoxysilane. And it is sufficient.
• silicone particles in which the silicone elastomer spherical particles are coated with poly (meth) acryloxyalkylsilsesquioxane-containing polyorganosilsesquioxane have a problem of strong cohesion and poor dispersibility in the resin. is there.
• the present invention has been made in view of the above circumstances. Silicone particles having rubber elasticity, low cohesiveness, high dispersibility in resins, and containing (meth) acryloxyalkyl groups on the particle surface, and the same An object is to provide a manufacturing method.
• the present invention provides the following silicone particles and a method for producing the same. [1].
• silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m water, an alkaline substance, and one or more selected from a cationic surfactant and a cationic water-soluble polymer compound, Obtained by hydrolyzing and condensing trimethoxysilane and (meth) acryloxyalkyltrimethoxysilane
• the surface of the silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m is represented by the following composition formula (1): CH 3 SiO 3/2 (1)
• the molar ratio of the methyl silsesquioxane unit of the polyorganosilsesquioxane to the (meth) acryloxyalkylsilsesquioxane unit is The silicone particle according to [1], which is 99: 1 to 10:90. [3].
• silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m, water, an alkaline substance, and one or more selected from a cationic surfactant and a cationic water-soluble polymer compound Including the step of coating the surface of the silicone elastomer spherical particles with polyorganosilsesquioxane by hydrolyzing and condensing trimethoxysilane and (meth) acryloxyalkyltrimethoxysilane,
• the surface of the silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m is represented by the following composition formula (1): CH 3 SiO 3/2 (1)
• the silicone particles of the present invention have low cohesiveness and therefore high dispersibility in the resin, the stress relaxation effect of the resin is high.
• the particle surface contains a (meth) acryloxyalkyl group, the adhesion with the resin capable of reacting with the (meth) acryloxyalkyl group is improved, and the silicone particles are removed when the resin is cut. Can be prevented.
• silicone particles of the present invention the surface of a silicone elastomer spherical particle having a volume average particle size of 0.1 to 100 ⁇ m is coated with a polyorganosilsesquioxane containing (meth) acryloxyalkylsilsesquioxane units. Silicone particles having a polyorganosilsesquioxane mass of 0.5 to 25 parts by mass with respect to 100 parts by mass of the silicone elastomer spherical particles, and obtained by the following production method .
• the volume average particle size of the silicone elastomer spherical particles used in the silicone particles of the present invention is 0.1 to 100 ⁇ m, preferably 0.5 to 40 ⁇ m, more preferably 1 to 20 ⁇ m.
• the volume average particle diameter of the silicone elastomer spherical particles is less than 0.1 ⁇ m, the silicone particles obtained using the silicone elastomer particles are highly cohesive and do not easily disperse to the primary particles in the resin.
• the volume average particle diameter of the silicone elastomer spherical particles is larger than 100 ⁇ m, the silicone particles obtained using the spherical particles impair the strength of the resin and do not sufficiently exhibit the stress relaxation effect of the resin.
• the volume average particle diameter (MV value) of the silicone elastomer spherical particles is a method appropriately selected from a microscope method, a light scattering method, a laser diffraction method, a liquid phase precipitation method, an electric resistance method, and the like according to the particle size. Measured by For example, in the case of 0.1 ⁇ m or more and less than 1 ⁇ m, the light scattering method and the range of 1-100 ⁇ m may be measured by the electric resistance method.
• the term “spherical” does not mean that the particle shape is only a true sphere, and the average length of the longest axis / length of the shortest axis (aspect ratio) is It is meant to include deformed ellipsoids that are in the range of 1 to 4, preferably 1 to 2, more preferably 1 to 1.6, and even more preferably 1 to 1.4.
• the shape of the particles can be confirmed by observing the particles with an optical microscope or an electron microscope.
• the silicone elastomer constituting the silicone elastomer spherical particles is preferably non-sticky, and its rubber hardness is preferably 5 to 90, more preferably 20 to 70, as measured by a type A durometer stipulated in JIS K 6253. Range. If the rubber hardness is less than 5, the silicone particles obtained by using this have high cohesiveness and may be difficult to disperse to primary particles in the resin. Moreover, when rubber hardness exceeds 90, there exists a possibility that the stress relaxation effect of resin by the silicone particle obtained using this may fall.
• the rubber hardness is a value measured by preparing a test piece having a shape and size defined in JIS K 6253 with the composition of silicone elastomer spherical particles.
• the silicone elastomer is, for example, a cured product having a linear organosiloxane block represented by the formula — (R 3 2 SiO 2/2 ) n —.
• R 3 in the formula is the same or different substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms, and n is a positive number of 5 to 5,000.
• R 3 for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetrasil group, triacyl group and other alkyl groups; phenyl group, tolyl group, naphthyl group and other aryl groups; benzyl group, Aralkyl groups such as phenethyl group; alkenyl groups such as vinyl group and allyl group; cycloalkyl groups such as cyclopentyl group
• the silicone elastomer can be obtained from, for example, a curable liquid silicone.
• the curing is performed by condensation reaction of methoxysilyl group ( ⁇ SiOCH 3 ) and hydroxysilyl group ( ⁇ SiOH), mercaptopropylsilyl group ( ⁇ Si—C 3 H 6 SH) and vinylsilyl group ( ⁇ SiCH ⁇ CH 2 ). And the like, and the like, by the addition reaction between a vinylsilyl group ( ⁇ SiCH ⁇ CH 2 ) and a hydrosilyl group ( ⁇ SiH), and the like. From the viewpoint of reactivity, curing by addition reaction is preferable.
• the organopolysiloxane having a monovalent olefinically unsaturated group and the organohydrogenpolysiloxane are monovalent olefinically unsaturated groups.
• a curable liquid silicone composition blended at a ratio of 0.5 to 2 hydrosilyl groups per one may be subjected to an addition reaction in the presence of a platinum group metal catalyst.
• R 4 in the formula is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group
• R 5 is a monovalent olefinic group having 2 to 6 carbon atoms.
• a and b are positive numbers represented by 0 ⁇ a ⁇ 3, 0 ⁇ b ⁇ 3, 0.1 ⁇ a + b ⁇ 3, and preferably 0 ⁇ a ⁇ 2.295, 0.005 ⁇ b ⁇ 2. 3, 0.5 ⁇ a + b ⁇ 2.3.
• R 6 is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 30 carbon atoms excluding an aliphatic unsaturated group.
• c and d are positive numbers represented by 0 ⁇ c ⁇ 3, 0 ⁇ d ⁇ 3, and 0.1 ⁇ c + d ⁇ 3, preferably 0 ⁇ c ⁇ 2.295, 0.005 ⁇ d ⁇ 2.3. 0.5 ⁇ c + d ⁇ 2.3.
• R 4 examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, undecyl group, dodecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group.
• octadecyl group nonadecyl group, icosyl group, henicosyl group, docosyl group, tricosyl group, tetrasyl group, triacotyl group and other alkyl groups; phenyl group, tolyl group, naphthyl group and other aryl groups; benzyl group, phenethyl group and the like Aralkyl group; Cycloalkyl group such as cyclopentyl group, cyclohexyl group, cycloheptyl group; and some or all of hydrogen atoms bonded to carbon atoms of these groups are halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom) ) Etc.
• halogen atoms fluorine atom, chlorine atom, bromine atom, iodine atom
• R 5 examples include a vinyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, and the like, but a vinyl group is preferred industrially.
• R 6 examples of R 6 are the same as R 4 described above.
• the kinematic viscosity at 25 ° C. of the organopolysiloxane and organohydrogenpolysiloxane having a monovalent olefinically unsaturated group exceeds 100,000 mm 2 / s, particles having a narrow distribution can be obtained in the production method described later. since it is difficult, it is preferably in the range of 1 ⁇ 100,000mm 2 / s, more preferably not more than 10,000 mm 2 / s.
• the structure of the organopolysiloxane and organohydrogenpolysiloxane having an olefinically unsaturated group may be any of linear, cyclic, and branched structures, with linear structures being particularly preferred.
• the kinematic viscosity is a value measured with an Ostwald viscometer.
• 2h + f corresponds to the above average composition formula (4), it is selected so as to have at least two monovalent olefinically unsaturated groups in one molecule, and corresponds to the above average composition formula (4 ′). In this case, it is selected so as to have at least 3 monovalent olefinically unsaturated groups in one molecule.
• linear organohydrogenpolysiloxane examples include those represented by the following general formula (7).
• R 6 is the same as the above average composition formula (5) or (5 ′).
• I is an integer of 1 to 1,500
• j is 0 or an integer of 1 to 500
• 2l + j corresponds to the above average composition formula (5), it is selected to have at least three hydrogen atoms (H) bonded to silicon atoms (Si) in one molecule, and the above average composition formula ( In the case of 5 ′), it is selected so as to have at least two hydrogen atoms bonded to silicon atoms in one molecule.
• the organopolysiloxane having an olefinically unsaturated group has at least two monovalent olefinically unsaturated groups in one molecule
• Genpolysiloxane is a combination having at least three hydrogen atoms bonded to silicon atoms
• an organopolysiloxane having an olefinically unsaturated group has at least 3 monovalent olefinically unsaturated groups in one molecule. It is preferable to carry out an addition reaction as a combination in which the organohydrogenpolysiloxane has at least two hydrogen atoms bonded to silicon atoms.
• platinum group metal catalysts used in these reactions include well-known catalysts used in hydrosilylation reactions. Specific examples thereof include platinum groups such as platinum (including platinum black), rhodium, and palladium.
• Metal simple substance H 2 PtCl 4 ⁇ mH 2 O, H 2 PtCl 6 ⁇ mH 2 O, NaHPtCl 6 ⁇ mH 2 O, KHPtCl 6 ⁇ mH 2 O, Na 2 PtCl 6 ⁇ mH 2 O, K 2 PtCl 4 ⁇ mH
• Platinum chloride such as 2 O, PtCl 4 ⁇ mH 2 O, PtCl 2 , Na 2 HPtCl 4 ⁇ mH 2 O (wherein, m is an integer of 0 to 6, preferably 0 or 6), Chloroplatinic acid and chloroplatinate; alcohol-modified chloroplatinic acid (see US Pat.
• the compounding amount of the platinum group metal catalyst may be an effective amount as a hydrosilylation reaction catalyst.
• the amount of the platinum group metal in the catalyst relative to the total amount of the curable liquid silicone composition is usually 0.1 to 500 ppm in terms of mass.
• the amount is about 0.1, preferably about 0.1 to 200 ppm, more preferably about 0.5 to 100 ppm.
• the silicone elastomer spherical particles constituting the silicone particles of the present invention may contain silicone oil, organosilane, inorganic powder, organic powder, etc. in the particles.
• Silicone elastomer spherical particles can be produced in the form of an aqueous dispersion by a known method.
• a surfactant and water are added to the curable liquid silicone composition comprising the organopolysiloxane having an olefinically unsaturated group and the organohydrogenpolysiloxane, There is a method of emulsifying and making an emulsion, and then adding a platinum group metal catalyst to carry out an addition reaction.
• the surfactant used here is a nonionic surfactant, a cationic surfactant or an amphoteric surfactant.
• the anionic surfactant suppresses the action of the cationic surfactant or cationic water-soluble polymer used in the step of coating the polyorganosilsesquioxane described later, and the cationic surfactant or cationic water-soluble surfactant.
• aggregation may be caused by impairing the dispersibility of the silicone elastomer spherical particles.
• nonionic surfactant examples include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, polyethylene glycol fatty acid ester, sorbitan fatty acid ester, and polyoxyethylene sorbitan.
• Fatty acid ester polyoxyethylene sorbite fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene hydrogenated castor oil Fatty acid ester, polyoxyethylene alkylamine, polyoxyethylene fatty acid amide, polyoxyethylene Down-modified organopolysiloxane, polyoxyethylene polyoxypropylene-modified organopolysiloxanes, and the like.
• Cationic surfactants include alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, polyoxyethylene alkyl dimethyl ammonium salts, dipolyoxyethylene alkyl methyl ammonium salts, tripolyoxyethylene alkyl ammonium salts, alkyl benzyl dimethyl ammonium salts, alkyl pyrimethylene salts. Examples thereof include a sodium salt, a monoalkylamine salt and a monoalkylamidoamine salt.
• amphoteric surfactant examples include alkyl dimethylamine oxide, alkyl dimethyl carboxy betaine, alkyl amidopropyl dimethyl carboxy betaine, alkyl hydroxy sulfobetaine, alkyl carboxymethyl hydroxyethyl imidazolinium betaine and the like.
• surfactants can be used singly or in appropriate combination of two or more.
• nonionic surfactants that can emulsify the curable liquid silicone composition in a small amount and make fine particles are preferable.
• cover polyorgano silsesquioxane with the manufacturing method of a postscript.
• the usage-amount of surfactant is 20 mass parts or less with respect to 100 mass parts of curable liquid silicone compositions.
• the amount of the surfactant used relative to 100 parts by mass of the curable liquid silicone composition is less than 0.01 parts by mass, it becomes difficult to make the curable liquid silicone composition into fine particles.
• the range is preferably 20 parts by mass, more preferably 0.05 to 5 parts by mass.
• a general emulsifier / disperser may be used.
• the general emulsifier / disperser include a high-speed rotary centrifugal stirrer such as a homodisper, a high-speed rotary shear stirrer such as a homomixer, and a homogenizer.
• examples thereof include a high-pressure jet type emulsifying disperser, a colloid mill, and an ultrasonic emulsifier.
• the platinum group metal catalyst When the dispersibility of the platinum group metal catalyst in water is poor, it is preferable to add the platinum group metal catalyst to the emulsion in a state dissolved in a surfactant.
• a surfactant examples include those described above, and nonionic surfactants are particularly preferable.
• the addition reaction may be performed at room temperature, but may be performed under heating at less than 100 ° C. if the reaction is not completed.
• the polyorganosilsesquioxane covering the surface of the silicone elastomer spherical particles preferably has a granular shape, and the particle diameter is preferably 200 nm or less, preferably 1 to 200 nm. . Dispersibility becomes higher when the particle diameter of the polyorganosilsesquioxane particles is 200 nm or less. This can be confirmed by observing the surface of the silicone particles with an electron microscope.
• the amount of the polyorganosilsesquioxane is 0.5 to 25 parts by mass, preferably 1 to 15 parts by mass with respect to 100 parts by mass of the silicone elastomer spherical particles.
• the polyorganosilsesquioxane is less than 0.5 parts by mass, the cohesiveness of the silicone particles is high and the dispersibility is low, and when it is more than 25 parts by mass, the stress relaxation performance of the resin by the silicone particles becomes poor.
• Polyorganosilsesquioxane has the following compositional formula (1) CH 3 SiO 3/2 (1)
• R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms.
• Specific examples of the alkylene group having 2 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and a propylene group is particularly preferable.
• the molar ratio of the methylsilsesquioxane unit of the polyorganosilsesquioxane to the (meth) acryloxyalkylsilsesquioxane unit is 99: 1 to 10:90 are preferred, 99: 1 to 50:50 are more preferred, and 95: 5 to 70:30 are even more preferred. If the amount of (meth) acryloxyalkylsilsesquioxane units is too small, the adhesion with the resin that can react with the (meth) acryloxyalkyl group may be low, and if too large, the cohesiveness of the silicone particles will increase. , Dispersibility may be lowered.
• the polyorganosilsesquioxane is composed of methylsilsesquioxane units and (meth) acryloxyalkylsilsesquioxane units within a range that does not impair the properties of the resulting silicone particles such as non-aggregation and dispersibility in the resin.
• one or more selected from R 7 SiO 3/2 units, R 8 2 SiO 2/2 units, R 8 3 SiO 1/2 units, and SiO 4/2 units may be included.
• the total of the methylsilsesquioxane unit and the (meth) acryloxyalkylsilsesquioxane unit may be 100 mol (units)% or more than 80 mol (units)% based on the total units. It may be less than 100 mol (unit)%, and the balance may be the above unit.
• R 7 in the formula is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms excluding a methyl group and a (meth) acryloxyalkyl group.
• R 7 includes ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Alkyl groups such as nonadecyl group and icosyl group; aryl groups such as phenyl group, tolyl group and naphthyl group; aralkyl groups such as benzyl group and phenethyl group; alkenyl groups such as vinyl group and allyl group; cyclopentyl group, cyclohexyl group and
• R 8 in the formula is independently a substituted or unsubstituted monovalent hydrocarbon group having 1 to 20 carbon atoms.
• R 8 include the same as R 7 , a methyl group, and a (meth) acryloxyalkyl group.
• the silicone particles of the present invention are, for example, selected from silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m, water, an alkaline substance, a cationic surfactant and a cationic water-soluble polymer compound.
• silicone elastomer spherical particles having a volume average particle size of 0.1 to 100 ⁇ m, water, an alkaline substance, a cationic surfactant and a cationic water-soluble polymer compound.
• silicone elastomer spherical particles those having a volume average particle size of 0.1 to 100 ⁇ m are used, and for example, those manufactured in the form of the aqueous dispersion may be used.
• the silicone elastomer spherical particles produced in the form of an aqueous dispersion are used, the aqueous dispersion may be used as it is or a water-added one may be used.
• silicone elastomer spherical particles selected from silicone elastomer spherical particles, water, an alkaline substance, a cationic surfactant and a cationic water-soluble polymer compound before adding methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane
• the content of the silicone elastomer spherical particles in a dispersion containing at least a seed is preferably 1 to 150 parts by mass with respect to 100 parts by mass of water. More preferably, it is in the range of 5 to 70 parts by mass.
• the content is less than 1 part by mass, the production efficiency of the desired silicone particles will be low, and if it exceeds 150 parts by mass, it will be difficult to coat the surface of the silicone elastomer spherical particles with the polyorganosilsesquioxane resin.
• the silicone particles may be aggregated and fused.
• alkaline substance acts as a catalyst for hydrolysis and condensation reaction of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane.
• An alkaline substance may be used individually by 1 type, or may use 2 or more types together.
• the alkaline substance is not particularly limited, and examples thereof include alkali metal hydroxides such as potassium hydroxide, sodium hydroxide and lithium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide; potassium carbonate and carbonate Alkali metal carbonates such as sodium; ammonia; tetraalkylammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide; or monomethylamine, monoethylamine, monopropylamine, monobutylamine, monopentylamine, dimethylamine, diethylamine Further, amines such as trimethylamine, triethanolamine and ethylenediamine can be used. Among these, ammonia is most suitable because it can be easily removed from the resulting powder of silicone particles by volatilization. As ammonia, a commercially available aqueous ammonia solution can be used.
• the alkaline substance may be added as it is or as an alkaline aqueous solution.
• the alkaline substance is preferably blended before adding methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane to the hydrolysis / condensation reaction solution. If an alkaline substance is added after the addition of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane, the surface of the silicone elastomer spherical particles may not be coated with polyorganosilsesquioxane.
• the amount of the alkaline substance added is such that the pH of the hydrolysis / condensation reaction solution is preferably in the range of 10.0 to 13.0, more preferably 10.5 to 12.5.
• the hydrolysis / condensation reaction of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane progresses, and polyorganosilsesquioxane
• the coating on the surface of the silicone elastomer spherical particles will be sufficient.
• cationic surfactants and cationic water-soluble polymer compounds These components can be used individually by 1 type or in combination of 2 or more types, and are polyorganosilsesquioxane containing a methylsilsesquioxane unit and a (meth) acryloxyalkylsilsesquioxane unit.
• action which makes the covering property to the surface of a silicone elastomer spherical particle high. Thereby, it is possible to obtain silicone particles having low cohesion and high dispersibility in the resin.
• the cationic surfactant is not particularly limited, and examples thereof are the same as the cationic surfactants described above.
• the cationic water-soluble polymer compound is not particularly limited.
• the addition amount of one or more selected from a cationic surfactant and a cationic water-soluble polymer compound is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0. The range is 5 parts by mass. If the amount added is less than 0.001 part by mass, the coating property of the polyorganosilsesquioxane on the surface of the silicone elastomer spherical particles may be lowered. There is a risk that sesquioxane is difficult to be coated.
• the amount of the cationic surfactant in the aqueous dispersion is included in the above amount.
• Methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane has the following general formula (8) CH 3 Si (OCH 3 ) 3 (8)
• the (meth) acryloxyalkyltrimethoxysilane is represented by the following formula (9) or (10). (In the formula, R 1 is an alkylene group having 2 to 6 carbon atoms, and R 2 is an alkylene group having 2 to 6 carbon atoms.)
• R 1 and R 2 are alkylene groups having 2 to 6 carbon atoms.
• Specific examples of the alkylene group having 2 to 6 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and a propylene group is particularly preferable.
• the molar ratio of methyltrimethoxysilane to (meth) acryloxyalkyltrimethoxysilane is determined by the hydrolysis and condensation of polyorganosilsesquioxane methylsilsesquioxane units and (meth) acryloxyalkylsilsesquioxanes. Molar ratio of sun units. Therefore, the preferred range of the ratio of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane is the above-mentioned polysilsilsesquioxane methylsilsesquioxane unit and (meth) acryloxyalkylsilsesquioxane unit.
• the ratio of methyltrimethoxysilane: (meth) acryloxyalkyltrimethoxysilane is preferably 99: 1 to 10:90, more preferably 99: 1 to 50:50, and 95: 5 to 70:30. Is more preferable.
• R 7 2 SiO 3/2 units, R 8 2 SiO 2/2 units, R 8 3 SiO 1/2 units, and SiO 4/2 units into polyorganosilsesquioxane
• at least one selected from R 7 2 Si (OR 9 ) 3 , R 8 2 Si (OR 9 ) 2 , R 8 3 SiOR 9 , and Si (OR 9 ) 4 corresponding to each of them is added. That's fine.
• R 7 and R 8 are as described above.
• R 9 is an unsubstituted monovalent hydrocarbon group having 1 to 6 carbon atoms.
• R 9 examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and a methyl group is preferable from the viewpoint of reactivity.
• the addition amount of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane is such that the amount of polyorganosilsesquioxane is 0.5 to 25 parts by mass, preferably 100 parts by mass of the above-mentioned silicone elastomer spherical particles.
• the amount is in the range of 1 to 15 parts by mass.
• a dispersion liquid (hydrolysis / condensation reaction liquid) containing at least one selected from silicone elastomer spherical particles, water, an alkaline substance, and a cationic surfactant and a cationic water-soluble polymer compound
• methyltrimethoxysilane and (Meth) acryloxyalkyltrimethoxysilane is added to cause hydrolysis and condensation.
• the condensate that is, polyorganosilsesquioxane adheres to the surface of the silicone elastomer spherical particles, whereby the surface of the silicone elastomer spherical particles is coated with the polyorganosilsesquioxane.
• methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane is preferably performed with stirring using a normal stirrer such as a propeller blade or a flat blade.
• Methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane may be added at once, but it is preferable to add them over time.
• the dropping time is in the range of 1 minute to 3 hours, more preferably 10 minutes to 1 hour.
• methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane may be mixed and dissolved, or may be added separately.
• the temperature at this time is preferably 0 to 60 ° C., more preferably in the range of 0 to 40 ° C.
• the surface of the silicone elastomer spherical particles can be more easily coated with polyorganosilsesquioxane.
• Stirring may continue after the addition of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane until the hydrolysis / condensation reaction of methyltrimethoxysilane and (meth) acryloxyalkyltrimethoxysilane is complete.
• the reaction may be carried out at room temperature or under heating at about 40 to 100 ° C.
• water is removed from the obtained aqueous dispersion of the silicone particles of the present invention.
• the removal of water can be performed, for example, by heating the aqueous dispersion after the reaction under normal pressure or reduced pressure, specifically, a method of removing the water by leaving the dispersion still under heating, A method of removing moisture while stirring and flowing the dispersion under heating, a method of spraying and dispersing the dispersion in a hot air stream like a spray dryer, a method of using a fluidized heat medium, and the like can be used.
• the dispersion liquid may be concentrated by a method such as heat dehydration, filtration separation, centrifugation, decantation or the like, and the dispersion liquid may be washed with water or alcohol if necessary.
• silicone particles by crushing with a pulverizer such as a jet mill, ball mill, hammer mill or the like. Can do.
• the volume average particle size of the silicone particles of the present invention is preferably from 0.1 to 100 ⁇ m, more preferably from 0.5 to 40 ⁇ m, and even more preferably from 1 to 20 ⁇ m.
• the method for measuring the volume average particle size is the same as the method for measuring the volume average particle size of the silicone elastomer spherical particles, and the silicone particles are measured by dispersing them in water using a surfactant.
• the silicone particle of this invention contains the (meth) acryloxyalkyl group on the particle
• silicone particles of the present invention have rubber elasticity, low cohesiveness, and high dispersibility in resin, they are useful for packaging of electronic and electric parts, printed boards, adhesives and the like.
• the kinematic viscosity is a value measured by an Ostwald viscometer at 25 ° C.
• “%” representing the concentration and the content rate represents “% by mass”. Further, the evaluation of dispersibility was performed as follows.
• Example 1 Represented by the below-described formula (11), and methyl vinyl polysiloxane 150g kinematic viscosity of 8 mm 2 / s, represented by the following formula (12), methylhydrogenpolysiloxane 50g kinematic viscosity of 117 mm 2 / s (olefinic A blending amount of 1.15 hydrosilyl groups per unsaturated group) was charged into a glass beaker having a capacity of 1 liter, and stirred and dissolved at 2,000 rpm using a homomixer.
• the shape of the silicone elastomer particles in the obtained aqueous dispersion was observed with an optical microscope, it was spherical and the volume average particle size was measured by an electric resistance method particle size distribution analyzer (Multisizer 3, manufactured by Beckman Coulter, Inc.). ) was 2 ⁇ m.
• the hardness of the silicone elastomer which comprises a silicone elastomer particle was measured as follows.
• Isododecane solution of methylvinylpolysiloxane represented by the above formula (11), methylhydrogenpolysiloxane represented by the above formula (12), and chloroplatinic acid-vinyl group-containing disiloxane complex (platinum content: 0.5%)
• platinum content 0.5%
• the hardness of the silicone elastomer was 75 as measured with a durometer A hardness meter.
• a solution obtained by hydrolyzing and condensing methyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane in an aqueous dispersion of silicone elastomer particles was dehydrated to about 30% moisture using a pressure filter.
• the dehydrated product was transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was again transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was dried at a temperature of 105 ° C. in a hot air fluid dryer, and the dried product was pulverized with a jet mill to obtain fluid silicone particles.
• the obtained silicone particles were dispersed in water using a surfactant and measured using an electric resistance method particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). The volume average particle diameter was 2 ⁇ m.
• an electric resistance method particle size distribution measuring device Multisizer 3, manufactured by Beckman Coulter, Inc.
• the volume average particle diameter was 2 ⁇ m.
• the silicone particles were observed with an electron microscope, it was confirmed that the surface of the silicone elastomer spherical particles was coated with granular polyorganosilsesquioxane.
• a C ⁇ O group was detected, and the polyorganosilsesquioxane that was coated contained 3-methacryloxypropylsilsesquioxane units. It was determined that
• Example 2 750 g of an aqueous dispersion of silicone elastomer spherical particles obtained by the same procedure as in Example 1 was transferred, and 212 g of water, 19 g of 28% ammonia water, and 40% aqueous dimethyldiallylammonium chloride polymer (trade name: ME polymer H40W, Toho) Chemical Industry Co., Ltd.) 1 g (amount such that dimethyldiallylammonium chloride polymer is 0.05 parts by mass with respect to 100 parts by mass of water) is charged into a 2-liter glass flask equipped with a stirrer with a vertical stirring blade. , Stirred. The pH of the liquid at this time was 11.3.
• a solution obtained by hydrolyzing and condensing methyltrimethoxysilane and 3-methacryloxypropyltrimethoxysilane in an aqueous dispersion of silicone elastomer particles was dehydrated to about 30% moisture using a pressure filter.
• the dehydrated product was transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was again transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was dried at a temperature of 105 ° C. in a hot air fluid dryer, and the dried product was pulverized with a jet mill to obtain fluid silicone particles.
• the obtained silicone particles were dispersed in water using a surfactant and measured using an electric resistance method particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). The volume average particle diameter was 2 ⁇ m.
• an electric resistance method particle size distribution measuring device Multisizer 3, manufactured by Beckman Coulter, Inc.
• the volume average particle diameter was 2 ⁇ m.
• the silicone particles were observed with an electron microscope, it was confirmed that the surface of the silicone elastomer spherical particles was coated with granular polyorganosilsesquioxane.
• a C ⁇ O group was detected, and the polyorganosilsesquioxane that was coated contained 3-methacryloxypropylsilsesquioxane units. It was determined that
• a solution obtained by hydrolyzing and condensing methyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane in an aqueous dispersion of silicone elastomer particles was dehydrated to about 30% water using a pressure filter.
• the dehydrated product was transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was again transferred to a glass flask having a capacity of 2 liters equipped with a stirrer with a vertical stirring blade, added with 1,000 g of water, stirred for 30 minutes, and then dehydrated using a pressure filter.
• the dehydrated product was dried at a temperature of 105 ° C. in a hot air fluid dryer, and the dried product was pulverized with a jet mill to obtain fluid silicone particles.
• the obtained silicone particles were dispersed in water using a surfactant and measured using an electric resistance method particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.).
• the volume average particle diameter was 2 ⁇ m.
• Example 4 In Example 1, instead of 1 g of 40% dimethyldiallylammonium chloride polymer aqueous solution (trade name: ME polymer H40W, manufactured by Toho Chemical Co., Ltd.), 30% dodecyltrimethylammonium chloride (trade name: cation BB, NOF Corporation) Silicone particles were obtained in the same manner as in Example 1 except that 1.3 g (amount by which dodecyltrimethylammonium chloride was 0.05 parts by mass with respect to 100 parts by mass of water) was used. The obtained silicone particles were dispersed in water using a surfactant and measured using an electric resistance method particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). The volume average particle diameter was 2 ⁇ m. When the silicone particles were observed with an electron microscope, it was confirmed that the surface of the silicone elastomer spherical fine particles was coated with granular polyorganosilsesquioxane.
• ME polymer H40W manufactured by Toho Chemical Co
• Example 1 silicone particles were obtained in the same manner as in Example 1 except that 40% dimethyldiallylammonium chloride polymer aqueous solution (trade name: ME polymer H40W, manufactured by Toho Chemical Industry Co., Ltd.) was not used.
• the obtained silicone particles were dispersed in water using a surfactant and measured using an electric resistance method particle size distribution measuring device (Multisizer 3, manufactured by Beckman Coulter, Inc.). In comparison with the aqueous dispersion of silicone elastomer particles, the particle size was larger in particle size and the volume average particle size was 3 ⁇ m.
• the silicone particles obtained above were evaluated for non-aggregation (measuring the mesh pass amount) by the following method.
• the results are shown in Table 1.
• Non-aggregating From above, 60 mesh sieve, 100 mesh sieve, and 200 mesh sieve are stacked in this order, and about 2 g of particle sample is weighed on the 60 mesh sieve, and a powder property apparatus (Powder Tester PT-E type, Hosokawa Micron Corporation) The vibration was applied for 90 seconds, and the path amount of each mesh was measured. The mesh pass amount is expressed in%, and it is judged that the non-aggregation property is higher as the pass amount is larger.
• the silicone particles of Examples 1 to 4 are obtained by hydrolyzing and condensing methyltrimethoxysilane and (meth) acryloxypropyltrimethoxysilane in the presence of a cationic surfactant or a cationic water-soluble polymer compound.
• the surface of the silicone elastomer spherical particles is coated with polyorganosilsesquioxane containing (meth) acryloxypropylsilsesquioxane units, which is highly non-aggregating and therefore presumed to have good dispersibility in the resin.
• Comparative Example 1 does not use a cationic surfactant or a cationic water-soluble polymer compound, has poor polyorganosilsesquioxane coverage on the surface of the silicone elastomer spherical particles, and is non-aggregating. Is low, and it is estimated that the dispersibility with respect to resin is bad.

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