Classifications

• • 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
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/10—Encapsulated ingredients
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/08—Organic materials containing halogen
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K21/00—Fireproofing materials
  • C09K21/06—Organic materials
  • C09K21/12—Organic materials containing phosphorus
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present invention relates to thermally expandable microcapsules, a foamable masterbatch, a foamed molded article, and a foamable resin composition using the thermally expandable microcapsules.
• Thermally expandable microcapsules are used in a wide range of applications as design agents and weight-reducing agents, and are also used in foaming inks, wallpapers, and other light-weight paints.
• thermally expandable microcapsules those in which a thermoplastic shell polymer encapsulates a volatile expansion agent that becomes gaseous at a temperature below the softening point of the shell polymer are widely known.
• Patent Document 1 discloses that an oil-based liquid mixture containing a monomer and a volatile expanding agent such as a low-boiling aliphatic hydrocarbon is mixed with an oil-soluble polymerization catalyst and a dispersant.
• a thermally expandable microcapsule containing a volatile expanding agent is disclosed, which is obtained by adding the volatile expanding agent to an aqueous dispersion medium with stirring and carrying out suspension polymerization.
• Patent Document 2 discloses thermally expandable microspheres containing a polymer made of a crosslinkable monomer having a (meth)acryloyl group and a reactive carbon-carbon double bond and having a molecular weight of 500 or more. .
• thermally expandable microcapsules thermoly expandable microspheres
• a resin such as a thermoplastic resin
• foaming process to produce a foamed molded product.
• there is a need to impart flame retardancy to the resulting foamed molded product but when creating a foamed molded product by mixing a general flame retardant with conventional thermally expandable microcapsules, foaming properties There is a problem that it becomes insufficient.
• the present invention relates to a thermally expandable microcapsule capable of obtaining a foamed molded product having high foamability and excellent flame retardancy, a foamable masterbatch using the thermally expandable microcapsule, and a foamable resin.
• the object of the present invention is to provide a composition and a foam molded article.
• the present disclosure (1) is a thermally expandable microcapsule in which a volatile expansion agent is encapsulated in a shell as a core agent, and the shell is a thermally expandable microcapsule containing a flame retardant.
• the present disclosure (2) is the thermally expandable microcapsule according to the present disclosure (1), wherein the flame retardant includes at least one selected from the group consisting of phosphorus-based flame retardants and halogen-based flame retardants.
• the present disclosure (3) is the thermally expandable microcapsule according to the present disclosure (1) or (2), wherein the average particle diameter of the flame retardant is 10 nm or more and 5000 nm or less.
• the present disclosure (4) provides the present disclosure (1) to (4), wherein the ratio (A/B) between the average particle diameter (A) of the flame retardant and the thickness (B) of the shell is 0.002 to 0.8.
• the present disclosure (5) provides any of the present disclosure (1) to (4), wherein the content of the flame retardant is 0.01% by weight or more and 10% by weight or less based on the entire thermally expandable microcapsule.
• the present disclosure (6) is the thermally expandable microcapsule according to any one of the present disclosure (1) to (5), wherein the flame retardant is contained inside the shell.
• the present disclosure (7) provides any of the present disclosure (1) to (6), wherein the content of the flame retardant element is 0.001% by weight or more and 10% by weight or less based on the entire thermally expandable microcapsule.
• the thermally expandable microcapsule described in The present disclosure (8) further provides the heat exchanger according to any one of the present disclosure (1) to (7), further containing at least one inorganic compound selected from the group consisting of Si-based compounds and Mg-based compounds. Expandable microcapsules.
• the present disclosure (9) is the thermally expandable microcapsule according to the present disclosure (8), wherein the content of the inorganic compound is 0.01 to 10% by weight based on the entire thermally expandable microcapsule.
• the present disclosure (10) provides thermally expandable microcapsules according to the present disclosure (8) or (9), wherein the weight ratio of the inorganic compound to the flame retardant (inorganic compound/flame retardant) is 0.01 to 10,000. It is.
• the present disclosure (11) is a foamable masterbatch containing the thermally expandable microcapsules and thermoplastic resin according to any one of the present disclosures (1) to (10).
• the present disclosure (12) is a foamable resin composition containing the thermally expandable microcapsules according to any one of the present disclosures (1) to (10), a flame retardant compound, and a thermoplastic resin. .
• the present disclosure (13) is characterized in that the ratio (A/C) of the average particle diameter (A) of the flame retardant contained in the thermally expandable microcapsules to the average particle diameter (C) of the flame retardant compound is 0.0003 to 1.0, the foamable resin composition according to the present disclosure (12).
• the present disclosure (14) provides the thermally expandable microcapsules according to any one of the present disclosures (1) to (10), the foamable masterbatch according to the present disclosure (11), or the present disclosure (12) or ( 13) A foamed molded article using the foamable resin composition described in item 13). The present invention will be explained in detail below.
• the shell may contain a component equivalent to a flame retardant, the shell may contain a flame retardant and a polymer compound separately, or the shell may contain a flame retardant and a polymer compound separately. It may also be included in the form.
• the above-mentioned flame retardant is a substance that, when added to a flammable substance such as plastic, wood, and fiber, can impart flame retardancy to the resulting substance.
• the flame retardant examples include phosphorus-based flame retardants, halogen-based flame retardants, nitrogen-containing flame retardants, and inorganic flame retardants. Among them, it is preferable to include at least one kind selected from the group consisting of phosphorus-based flame retardants and halogen-based flame retardants because of their high flame retardant properties. Preferred are flame retardants.
• Examples of the phosphorus flame retardant include aromatic phosphate esters, aliphatic phosphate esters, halogen-containing phosphate esters, polymerizable phosphorus compounds, phosphates, polyphosphates, phosphorus spiro compounds, and the like.
• Examples of the aromatic phosphate ester include triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, aromatic pentaerythritol diphosphonate, and the like.
• Examples of the fatty acid phosphate include trioctyl phosphate and the like.
• halogen-containing phosphate ester examples include tris(halopropyl)phosphate, tris(haloethyl)phosphate, and the like.
• polymerizable phosphorus compound examples include vinyl phosphonate, allyl phosphonate, and the like.
• Examples of the phosphates include melamine orthophosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, calcium phosphate, magnesium phosphate, and the like.
• Examples of the polyphosphates include ammonium polyphosphate, melamine polyphosphate, melamine/melam/melem polyphosphate, and piperazine polyphosphate. Among these, ammonium polyphosphate is preferred.
• Melamine or "piperazine" in the above examples of phosphates and polyphosphates include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'- Diethylethylenediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-diethylethylenediamine, 1,2-propanediamine , 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans- 2,5-dimethylpiperazine, 1,4-bis(
• one of the above phosphates and polyphosphates may be used alone, or two or more selected from the above phosphates and polyphosphates may be mixed as an intomescent flame retardant.
• one or more selected from the above phosphates and polyphosphates and a metal oxide may be used in combination.
• metal oxides used in combination with one or more selected from the above phosphates and polyphosphates include zinc oxide, magnesium oxide, calcium oxide, silicon dioxide, titanium oxide, manganese oxide (MnO, MnO 2 ), Examples include iron (FeO, Fe 2 O 3 , Fe 3 O 4 ), copper oxide, nickel oxide, tin oxide, aluminum oxide, calcium aluminate, and the like.
• the mass ratio thereof is preferably adjusted as follows.
• the mass ratio of one or more selected from phosphates and polyphosphates to the metal oxide [total mass of phosphates and polyphosphates/mass of metal oxide] is preferably from the viewpoint of improving flame retardancy. is 4 or more and 100 or less, more preferably 6 or more and 50 or less, even more preferably 10 or more and 35 or less. That is, the total mass of the phosphate and polyphosphate/mass of the metal oxide is preferably from 4 to 100, more preferably from 6 to 50, even more preferably from 10 to 35.
• the phosphazene-based compound is preferably one represented by the following general formula (1) because it has a relatively high decomposition temperature.
• R 1 to R 6 each independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, an amino group, or a halogen atom. Indicates one of the following. Examples of such phosphazene compounds include "SPB-100" commercially available from Otsuka Chemical Co., Ltd.
• the above-mentioned phosphorus-based spiro compound is not particularly limited as long as it is a spiro compound having a phosphorus atom.
• a spiro compound is a compound having a structure in which two cyclic compounds share one carbon
• a spiro compound having a phosphorus atom is a compound in which at least one of the elements constituting the two cyclic compounds is a phosphorus atom. It is a certain compound.
• the phosphorus-based spiro compound for example, it is preferable to use a compound having a structure represented by the following formula (2) in the molecule. Note that in formula (2), * indicates a connecting portion with another substituent.
• nitrogen-containing flame retardants examples include triazine derivatives, tris(2-bidrocyquiethyl)isocyanurate, tris(2,3-epoxypropyl)isocyanurate, melamine cyanurate, benzoguanamine, and melamine, which contain oxygen in their structure.
• the nitrogen-containing flame retardant in this specification is a flame retardant that does not contain phosphorus.
• halogen flame retardant chlorine flame retardants and bromine flame retardants are preferred.
• chlorinated flame retardant include chlorinated paraffin, chlorinated polyethylene perchloropentacyclodecane, and the like.
• brominated flame retardant is not particularly limited as long as it contains bromine in its molecular structure.
• brominated flame retardants examples include decabromodiphenyl ether, octabromodiphenyl ether, tetrabromobisphenol A (TBBA), TBBA epoxy oligomer, TBBA carbonate oligomer, TBBA bis(dibromopropyl ether), TBBA bis(aryl ether), and decabromodiphenyl ether.
• TBBA tetrabromobisphenol A
• TBBA epoxy oligomer examples include TBBA epoxy oligomer, TBBA carbonate oligomer, TBBA bis(dibromopropyl ether), TBBA bis(aryl ether), and decabromodiphenyl ether.
• Bromodiphenylethane [bis(pentabromophenyl)ethane], 1,2-bis(2,4,6-tribromophenoxy)ethane, 2,4,6-tris(2,4,6-thyrobromophenoxy)- 1,3,5-triazine, 2,6-or(2,4-)dibromophenol homopolymer, brominated polystyrene, polybrominated styrene, ethylenebistetrabromophthalimide, hexabromocyclododecane, hexabromobenzene, pentabromo Examples include benzyl acrylate monomer, pentabromobenzyl acrylate polymer, and the like.
• decabromodiphenylethane is preferred from the viewpoint of flame retardancy and foamability.
• These brominated flame retardants may be used alone or in combination of two or more.
• the halogen-based flame retardant does not include halogen-based phosphorus-based flame retardants, nitrogen-containing flame retardants, and inorganic flame retardants.
• Examples of the inorganic flame retardant include metal compounds such as metal oxides, metal hydroxides, and metal salts.
• the above metal compounds include zirconium oxide, aluminum hydroxide, dawsonite, aluminized calcium oxide, dihydrated gypsum, calcium hydroxide, zinc borate, barium metaborate, borax, kaolin clay, calcium carbonate, molybdenum compounds, ammonium aluminum hydro Examples include oxycarbonate, ferrocene, and tin compounds.
• a flame retardant aid may be used in combination with the above flame retardant.
• flame retardancy due to the synergistic effect with the flame retardant, flame retardancy can be improved and the content of the flame retardant can be reduced.
• a halogen-based flame retardant when used as the above-mentioned flame retardant, by using it together with a flame retardant aid, it reacts with the halogen-based flame retardant during combustion and becomes a nonflammable halide. This creates an oxygen shielding effect.
• an antimony-based flame retardant aid is preferred.
• the antimony-based flame retardant aid include antimony trioxide, antimony pentoxide, etc.
• Commercially available products include, for example, “PATOX-M”, “PATOX-MK”, and “PATOX-MK” manufactured by Nippon Seiko Co., Ltd. PATOX-K” etc.
• the content of the flame retardant aid is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of the flame retardant.
• the amount is preferably 40 to 60 parts by weight, and more preferably 40 to 60 parts by weight.
• the content of the flame retardant may be calculated from the amount charged, or may be measured using X-ray structural analysis of thermally expandable microcapsules.
• the melting point of the flame retardant is preferably 240 to 600°C, more preferably 250 to 550°C, even more preferably 255 to 500°C. By setting it within the above range, it becomes easy to melt due to the heat during combustion, and combustion of the foamed molded article can be suppressed.
• the flame retardant is preferably in the form of fine particles (flame-retardant fine particles).
• the flame retardant preferably has an average particle diameter of 10 nm or more and 5000 nm or less, more preferably 50 nm or more and 1000 nm or less.
• flame retardant fine particles are dispersed in the resin. That is, the average particle diameter of the flame retardant is preferably 10 to 5000 nm, more preferably 50 to 1000 nm.
• the average particle size can be measured by observation using a particle size distribution measuring device (ELSZ-2000ZS, manufactured by Otsuka Electronics Co., Ltd.).
• the above-mentioned epoxy resin is not particularly limited, and examples thereof include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolak epoxy resin, dicyclopentadiene epoxy resin, glycidylamine epoxy resin, etc. Can be mentioned.
• examples of the above-mentioned phenolic resins include novolac type phenolic resins, resol type phenolic resins, benzylic ether type phenolic resins, and the like. Among these, novolac type phenolic resins are preferred.
• volatile swelling agent examples include ethane, ethylene, propane, propene, n-butane, isobutane, butene, isobutene, n-pentane, isopentane, neopentane, n-hexane, heptane, petroleum ether, isooctane, octane, Examples include low molecular weight hydrocarbons such as decane, isododecane, dodecane, and hexanedecane.
• the preferable lower limit of the maximum foaming temperature (Tmax) of the thermally expandable microcapsule that is one embodiment of the present invention is 150°C.
• Tmax maximum foaming temperature
• the preferable lower limit of the maximum foaming temperature (Tmax) of the thermally expandable microcapsule that is one embodiment of the present invention is 150°C.
• the maximum foaming temperature is the temperature at which the diameter of the thermally expandable microcapsule reaches its maximum (maximum displacement amount) when the diameter of the thermally expandable microcapsule is measured while heating the thermally expandable microcapsule from room temperature. means temperature.
• the preferred lower limit of the volume average particle diameter of the thermally expandable microcapsules that is an embodiment of the present invention is 3 ⁇ m, and the preferred upper limit is 45 ⁇ m. If it is 3 ⁇ m or more, the bubbles in the molded product obtained will be moderate and the expansion ratio can be made sufficient, and if it is 45 ⁇ m or less, the bubbles in the molded product obtained will not become too large. , the appearance is excellent.
• a more preferable lower limit is 5 ⁇ m, and a more preferable upper limit is 35 ⁇ m. That is, the volume average particle diameter of the thermally expandable microcapsules is preferably 3 to 45 ⁇ m, more preferably 5 to 35 ⁇ m.
• the CV value (coefficient of variation) of the volume average particle diameter of the thermally expandable microcapsules is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less. When it is 40% or less, the air bubbles in the obtained molded product will be uniform, and the thickness can be made uniform. Furthermore, since the bubbles present on the surface of the molded product are uniform, the molded product has an excellent appearance. Note that the preferable lower limit is not particularly limited, but is preferably 0%.
• the volume average particle diameter of the thermally expandable microcapsules can be measured using a laser diffraction/scattering method particle size distribution analyzer or the like. Furthermore, the CV value can also be calculated at the time of the measurement.
• the first step is to prepare an aqueous dispersion medium.
• an aqueous dispersion medium containing a flame retardant and an inorganic compound is prepared by adding water, a flame retardant, an inorganic compound, and, if necessary, a co-stabilizer to a polymerization reaction vessel.
• condensation product in addition to the co-stabilizer, a condensation product or a water-soluble nitrogen compound may be added.
• the condensation product is preferably a condensation product of diethanolamine and an aliphatic dicarboxylic acid, particularly a condensation product of diethanolamine and adipic acid or a condensation product of diethanolamine and itaconic acid.
• water-soluble nitrogen compound examples include polyvinylpyrrolidone, polyethyleneimine, polyoxyethylenealkylamine, polydialkylaminoalkyl (meth)acrylate represented by polydimethylaminoethyl methacrylate and polydimethylaminoethyl acrylate.
• polyvinylpyrrolidone is preferably used.
• the method for producing thermally expandable microcapsules includes a step of dispersing an oily mixture containing a monomer composition and a volatile swelling agent in an aqueous dispersion medium. Specifically, a step is performed in which an oily liquid mixture containing a monomer composition and a volatile swelling agent is dispersed in an aqueous dispersion medium.
• the monomer composition and the volatile swelling agent may be separately added to the aqueous dispersion medium to prepare an oily mixture in the aqueous dispersion medium, but usually the two are mixed in advance and the oily mixture is and then added to the aqueous dispersion medium.
• the above flame retardant may be added after adjusting the average particle diameter by performing pulverization and dispersion treatment or the like.
• Examples of the method for the above-mentioned pulverization and dispersion treatment include crushers, mills (wet or dry bead mills, ball mills, jet mills, planetary mills, etc.), blenders, and the like.
• Thermally expandable microcapsules which are an embodiment of the present invention, can be produced by performing a step of polymerizing monomers by heating the dispersion obtained through the above-mentioned steps, and a step of washing. I can do it. Thermally expandable microcapsules produced by such a method have a high maximum foaming temperature, excellent heat resistance, and do not burst or shrink even when molded in a high temperature range.
• the above-mentioned flame-retardant compound refers to a flame-retardant component contained separately from the thermally expandable microcapsules.
• the above-mentioned flame retardant compound the same ones as the above-mentioned flame retardants can be used.
• the content of the flame retardant compound in the foamable resin composition is not particularly limited, but the preferable lower limit is 10 parts by weight and the preferable upper limit is 90 parts by weight based on 100 parts by weight of the thermoplastic resin.
• the ratio (A/C) of the average particle diameter (A) of the flame retardant contained in the thermally expandable microcapsules to the average particle diameter (C) of the flame retardant compound is 0.0003. It is preferable that it is 1.0 to 1.0. By being within the above range, both high foamability and excellent flame retardancy can be achieved.
• the average particle diameter of the said flame retardant compound is 1 micrometer or more and 50 micrometers or less, More preferably, it is 5 micrometers or more and 30 micrometers or less. That is, the average particle diameter of the flame retardant compound is preferably 1 to 50 ⁇ m, more preferably 5 to 30 ⁇ m.
• the average particle diameter can be measured by observation using a scanning electron microscope (Regulus 8220, manufactured by Hitachi High-Technologies).
• the method for producing the foamable masterbatch is not particularly limited, but for example, raw materials such as a base resin such as a thermoplastic resin and various additives are kneaded in advance using a co-directional twin-screw extruder or the like. Next, after heating to a predetermined temperature and adding a foaming agent such as thermally expandable microcapsules, the kneaded product obtained by further kneading is cut into a desired size with a pelletizer to form pellets into a master. Examples include a method of making a batch.
• the molding method for the foam molded product is not particularly limited, and examples thereof include kneading molding, calendar molding, extrusion molding, injection molding, and the like.
• the method is not particularly limited, and includes the short-short method in which a portion of the resin material is placed in the mold and foamed, and the core-back method in which the mold is fully filled with the resin material and then the mold is opened to the desired point of foaming. etc.
• Example 1 [Preparation of thermally expandable microcapsules]
• an inorganic compound disersant
• 19 parts by weight of colloidal silica manufactured by Asahi Denka Co., Ltd., primary average particle diameter: 20 nm
• polyvinylpyrrolidone manufactured by BASF
• an aqueous dispersion medium was prepared. 20% by weight of acrylonitrile, 30% by weight of methacrylonitrile, 40% by weight of methacrylic acid, and 10% by weight of methyl methacrylate were mixed to form a monomer composition in the form of a homogeneous solution.
• the obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain thermally expandable microcapsules.
• the obtained thermally expandable microcapsules were added to an embedding resin (Technovit 4000, manufactured by Kulzer) so that the particle content was 3% by weight, and dispersed to form a thermally expandable microcapsule embedding resin. was created.
• a thin film was prepared using a microtome (EM UC7, manufactured by LEICA) so as to pass near the center of thermally expandable microcapsules dispersed in the embedding resin, and flame retardant was examined using a transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.). When the location of the flame retardant was confirmed, it was confirmed that the flame retardant was present inside the shell.
• a roll sheet was prepared from the obtained foamable resin composition at 130° C. using an 8-inch roll (191-TM, manufactured by Yasuda Seiki Seisakusho Co., Ltd.). This rolled sheet was cut and heated at 170° C. with a press machine (PA-40E/40C, manufactured by Kodaira Seisakusho Co., Ltd.) to obtain a foam molded product having a sheet thickness of 7 mm.
• a press machine PA-40E/40C, manufactured by Kodaira Seisakusho Co., Ltd.
• the average particle size of phosphorus flame retardants 2 and 3 and decabromodiphenylethane in the oily mixture was 150 nm.
• Example 4 decabromodiphenylethane (SAYTEX8010, manufactured by Albemarle Japan Co., Ltd.) was used as a flame retardant compound, and antimony trioxide (PATOX-M, manufactured by Nippon Seiko Co., Ltd.) was further used as a flame retardant aid.
• SAYTEX8010 manufactured by Albemarle Japan Co., Ltd.
• PATOX-M antimony trioxide
• Example 10 [Preparation of thermally expandable microcapsules] Thermally expandable microcapsules were obtained in the same manner as in Example 1, except that the monomer composition, flame retardant, and inorganic compound were mixed in the composition shown in Table 1.
• ammonium polyphosphate AP423, pulverized
• the average particle diameter after pulverization and dispersion treatment with a bead mill was 10 nm.
• ammonium polyphosphate AP423, pulverized
• Example 11 ammonium polyphosphate (AP423, pulverized) was used as the flame retardant, and the average particle diameter after pulverization and dispersion treatment using a bead mill was 100 nm.
• Example 15 [Preparation of thermally expandable microcapsules] After adding 2.7 parts by weight of ammonium polyphosphate (pulverized) as a flame retardant and 0.2 parts by weight of a copolymer having acidic groups (DISPERBYK-102, manufactured by BYK) as an additive to 100 parts by weight of ion-exchanged water and mixing. The mixture was pulverized and dispersed in a bead mill to obtain a flame retardant dispersion.
• ammonium polyphosphate pulverized
• a copolymer having acidic groups DISPERBYK-102, manufactured by BYK
• the resulting dispersion was stirred and mixed using a homogenizer, charged into a pressure polymerization vessel purged with nitrogen, and reacted at 60° C. for 20 hours under pressure (0.5 MPa) to obtain a reaction product.
• the obtained reaction product was repeatedly filtered and washed with water, and then dried to obtain thermally expandable microcapsules.
• the obtained thermally expandable microcapsules were added to an embedding resin (Technovit 4000, manufactured by Kulzer) so that the particle content was 3% by weight, and dispersed to form a thermally expandable microcapsule embedding resin. was created.
• a thin film was prepared using a microtome (EM UC7, manufactured by LEICA) so as to pass near the center of thermally expandable microcapsules dispersed in the embedding resin, and flame retardant was examined using a transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.). When the location of the particles was confirmed, it was confirmed that the flame retardant was present on the surface of the particles.
• EM UC7 microtome
• LEICA transmission electron microscope
• foamable resin composition and foam molded product A foamable resin composition and a foamed molded article were obtained in the same manner as in Example 1, except that the obtained thermally expandable microcapsules were mixed in the composition shown in Table 2.
• thermally expandable microcapsules were prepared in the same manner as in Example 1, except that 0.4 parts by weight of Florene DOPA-15BHFS (manufactured by Kyoeisha Chemical Co., Ltd.) was added as an additive to the oily mixture. I got it.
• the obtained thermally expandable microcapsules were added to an embedding resin (Technovit 4000, manufactured by Kulzer) so that the particle content was 3% by weight, and dispersed to form a thermally expandable microcapsule embedding resin. was created.
• a thin film was prepared using a microtome (EM UC7, manufactured by LEICA) so as to pass near the center of thermally expandable microcapsules dispersed in the embedding resin, and flame retardant was examined using a transmission electron microscope (JEM-2100, manufactured by JEOL Ltd.). When the location of the flame retardant was confirmed, it was confirmed that the flame retardant was present at the interface between the shell and core agent. Further, a foamable resin composition and a foamed molded article were obtained in the same manner as in Example 1, except that the obtained thermally expandable microcapsules were mixed in the composition shown in Table 3.
• Example 17 A monomer composition of a homogeneous solution was used by mixing 20% by weight of acrylonitrile, 30% by weight of methacrylonitrile, 35% by weight of methacrylic acid, 5% by weight of 2-(methacryloyloxy)ethyl phosphate, and 10% by weight of methyl methacrylate. Except for this, thermally expandable microcapsules, a foamable resin composition, and a foamed molded article were obtained in the same manner as in Example 1.
• Example 18-19 A thermally expandable microcapsule, a foamable resin composition, and a foamed molded product were obtained in the same manner as in Example 1, except that the sheet thickness of the foamed molded product was changed as shown in Table 3.
• thermoly expandable microcapsules In [Preparation of thermally expandable microcapsules], thermally expandable microcapsules, a foamable resin composition, and a foamed molded article were obtained in the same manner as in Example 1 except that no flame retardant was added.
• Comparative Examples 2 to 9 The thermally expandable microcapsules of Comparative Example 1 were used.
• a foamable resin composition and foam molding were prepared in the same manner as in Example 1, except that the thermoplastic resin, thermally expandable microcapsules, antioxidant, crosslinking aid, and flame retardant compound were mixed in the composition shown in Table 3. I got a body.
• thermally expandable microcapsules (1-1) Measurement of volume average particle size (manufactured by). Specifically, 100 mg of thermally expandable microcapsules were dispersed in 3 ml of water, and then placed in a laser diffraction/scattering particle size distribution analyzer to measure the volume average particle diameter.
• Thickness of the shell is determined by measuring the cross section of 10 thermally expandable microcapsules fixed on a silicon wafer by FIB-SEM (Helios 650, FEI The thickness was measured at 5 arbitrary locations using the following method (Company) and the average value was calculated.
• the total combustion time was measured and judged in accordance with the official standards for evaluation of flame retardancy (ISO3582, JIS K6400-6, ASTM D4986). Specifically, after holding the test piece (150 ⁇ 1 ⁇ 50 ⁇ 1 ⁇ t [mm]) horizontally, a 38 mm flame was heated indirectly for 60 seconds, and the total combustion was determined by the combustion rate and combustion behavior with a distance of 100 mm between the gauge lines. Time measurements were taken.
• thermally expandable microcapsules that can obtain a foamed molded product having high foamability and excellent flame retardancy, a foamable masterbatch using the thermally expandable microcapsules, and foamable A resin composition and a foamed molded article can be provided.

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• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

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• 2023
  • 2023-03-27 JP JP2023524755A patent/JPWO2023190294A1/ja active Pending
  • 2023-03-27 WO PCT/JP2023/012116 patent/WO2023190294A1/ja not_active Ceased

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