WO2022196221A1 - Composition d'agent moussant chimique, mélange maître d'agent moussant chimique, mousse et procédé de production de mousse - Google Patents

Composition d'agent moussant chimique, mélange maître d'agent moussant chimique, mousse et procédé de production de mousse Download PDF

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WO2022196221A1
WO2022196221A1 PCT/JP2022/005949 JP2022005949W WO2022196221A1 WO 2022196221 A1 WO2022196221 A1 WO 2022196221A1 JP 2022005949 W JP2022005949 W JP 2022005949W WO 2022196221 A1 WO2022196221 A1 WO 2022196221A1
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foam
resin
agent composition
foaming agent
chemical
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PCT/JP2022/005949
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English (en)
Japanese (ja)
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賀文 今津
基 森
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コニカミノルタ株式会社
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Priority to JP2023506880A priority Critical patent/JPWO2022196221A1/ja
Publication of WO2022196221A1 publication Critical patent/WO2022196221A1/fr

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    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
    • C08J9/08—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing carbon dioxide
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • 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 a chemical foaming agent composition, a chemical foaming agent masterbatch, a foam, and a method for producing a foam. More specifically, the present invention provides a chemical foaming agent composition and a chemical foaming agent masterbatch that are capable of both miniaturizing cells and suppressing deterioration of flame retardancy when used for molding a foam, and furthermore, the chemical foaming agent composition.
  • the present invention relates to a foam produced by using a physical or chemical foaming agent masterbatch, in which both cell miniaturization and reduction in flame retardancy are suppressed, and a method for producing the same.
  • Injection foam molding is used to suppress sink marks (dents caused by molding shrinkage) and warpage in the molding of resin or elastomer foams used for exterior parts and structural parts used in automobiles and electrical appliances. things are increasing. In particular, for parts that are produced in small lots, if the chemical foaming method, which requires less equipment investment, is selected, the unit price of the product will be reduced, which is advantageous in terms of cost.
  • the chemical foaming method uses a chemical foaming agent that generates gas through thermal decomposition or chemical reaction.
  • foams obtained by the chemical foaming method had problems of deterioration in appearance quality and reduction in strength due to large internal cell diameters.
  • a technology has been developed to refine the air bubbles by adding a chemical foaming agent and a foaming aid to resins or elastomers.
  • “Chemical foaming agent” refers to a compound that generates gas (bubbles) by thermal decomposition or chemical reaction, among the chemicals used to obtain a foam by mixing with resin or the like.
  • “Chemical foaming agent composition” refers to a composition comprising a chemical foaming agent and an auxiliary agent other than the chemical foaming agent.
  • a “chemical blowing agent masterbatch” is a composition that combines a thermoplastic resin or thermoplastic elastomer with a chemical blowing agent or chemical blowing agent composition.
  • Patent Document 1 a foaming agent composition containing a citrate and a lithium compound (but excluding lithium salt) or zinc oxide is added to a thermally decomposable foaming agent to a thermoplastic resin to obtain fine particles.
  • a blowing agent composition that is foam molded with fine cells and a method for producing a thermoplastic resin foam are described.
  • Patent Document 2 discloses a foaming agent composition used for molding a resin foam, comprising sodium bicarbonate, which is a thermally decomposable foaming agent, lithium stearate, monosodium citrate, Blowing agent compositions are described that contain predetermined amounts of at least one of zinc, talc, and silica.
  • a foaming agent composition used for molding a resin foam comprising sodium bicarbonate, which is a thermally decomposable foaming agent, lithium stearate, monosodium citrate, Blowing agent compositions are described that contain predetermined amounts of at least one of zinc, talc, and silica.
  • by foam molding a resin using this foaming agent composition fine and uniform distribution of cells can be achieved, and appearance such as planar smoothness and substrate performance are improved. Excellent foams are said to be obtained.
  • the present invention has been made in view of the above-mentioned problems and circumstances, and the problem to be solved is a chemical foaming agent composition that can achieve both miniaturization of cells and suppression of deterioration in flame retardancy when used for molding foams. and to provide a chemical blowing agent masterbatch.
  • Another object of the present invention is to provide a foam produced using the above-mentioned chemical foaming agent composition or chemical foaming agent masterbatch, which achieves both miniaturization of cells and suppression of deterioration in flame retardancy, and a method for producing the same.
  • the present inventors selected sodium bicarbonate as a chemical foaming agent and selected a specific acidic substance as a foaming aid combined with it in the process of studying the causes of the above problems. It has been found that by using a chemical blowing agent composition, the foam obtained using the chemical blowing agent composition is a foam that achieves both miniaturization of cells and suppression of deterioration in flame retardancy. reached. That is, the above problems related to the present invention are solved by the following means.
  • a foaming material containing the chemical blowing agent composition according to any one of items 1 to 3 or the chemical blowing agent masterbatch according to item 4, and a thermoplastic resin or thermoplastic elastomer A foam molded by foaming.
  • thermoplastic resin or thermoplastic elastomer contains at least one selected from polyolefin resins, acrylonitrile-butadiene-styrene resins, polystyrene resins, polyamide resins, polyvinyl chloride resins, ethylene vinyl acetate resins and thermoplastic elastomers.
  • a foaming material is produced by mixing the chemical blowing agent composition according to any one of items 1 to 3 or the chemical blowing agent masterbatch according to item 4 with a thermoplastic resin or a thermoplastic elastomer. and foam-molding the foam material with an injection molding machine.
  • the inventors of the present invention have investigated inorganic compounds from the viewpoint of suppressing the deterioration of the flame retardancy of the obtained foam, and found that, among inorganic compounds, acidic substances in particular suppress the deterioration of the flame retardancy of the foam.
  • acidic substances in particular suppress the deterioration of the flame retardancy of the foam.
  • sodium bicarbonate is also excellent in the ability to make air bubbles fine.
  • the inventors have found that even if an organic compound is used, an acidic substance having a melting point of 400° C. or higher can provide the same effect as an inorganic acidic substance.
  • sodium bicarbonate causes the chemical reaction represented by the above acidic substance and formula (2) to generate bubbles (CO 2 gas).
  • the decomposition temperature of sodium hydrogen carbonate is 270°C, but it is known that the decomposition reaction of formula (1) occurs gradually from about 50°C.
  • the chemical reaction of formula (2) is believed to occur at a lower temperature than the reaction of formula (1).
  • sodium bicarbonate generates bubbles ( CO2 gas) at a lower temperature when it reacts with an acidic substance as in equation (2).
  • foaming occurs at such a low temperature, the viscosity of the matrix such as resin or elastomer is in a state of high viscosity, so it is difficult for the foamed gas bubbles to coalesce.
  • the chemical blowing agent composition of the present invention is a chemical blowing agent composition containing sodium hydrogencarbonate and an acidic substance, wherein the acidic substance is an inorganic compound or an organic compound having a melting point of 400° C. or higher. and This feature is a technical feature common to each embodiment of the chemical blowing agent composition below.
  • the chemical blowing agent composition may contain an organic compound having a melting point of less than 400°C. It is preferable that the content of the organic compound having a melting point of less than 400° C. is within a range of 58% by mass or less with respect to the total amount of the foaming agent composition.
  • the acidic substance is at least one selected from boric acid, diboron trioxide, sodium dihydrogen phosphate and sodium hydrogen sulfite. It preferably contains seeds.
  • the chemical blowing agent masterbatch of the present invention contains the chemical blowing agent composition of the present invention and a thermoplastic resin or thermoplastic elastomer.
  • the foam of the present invention is obtained by foam-molding a foam material containing the chemical foaming agent composition of the present invention or the chemical foaming agent masterbatch of the present invention and a thermoplastic resin or thermoplastic elastomer. is.
  • the content of the organic compound derived from the chemical foaming agent composition and having a melting point of less than 400° C. relative to the total amount of the foam is 1% by mass or less. is preferably within the range of
  • the thermoplastic resin or thermoplastic elastomer is polyolefin resin, acrylonitrile-butadiene-styrene resin, polystyrene resin, polyamide resin, polyvinyl chloride resin. , ethylene vinyl acetate resin and thermoplastic elastomer.
  • the foam may further contain a flame retardant from the viewpoint of exhibiting the effects of the present invention.
  • the method for producing the foam of the present invention comprises the step of mixing the chemical foaming agent composition of the present invention or the chemical foaming agent masterbatch of the present invention with a thermoplastic resin or thermoplastic elastomer to obtain a foam material; and a step of foam-molding the material with an injection molding machine.
  • the ratio of the chemical foaming agent composition to the total amount of the thermoplastic resin or thermoplastic elastomer in the foam material is 0.1 to 1. It is preferably in the range of 0.7% by weight.
  • the chemical blowing agent composition of the present invention is a chemical blowing agent composition containing sodium hydrogencarbonate and an acidic substance, wherein the acidic substance is an inorganic compound or an organic compound having a melting point of 400° C. or higher. and As described above, the chemical foaming agent composition is a composition comprising a chemical foaming agent and an auxiliary agent that is a component other than the chemical foaming agent. Auxiliaries include foaming aids, anti-drip agents, antioxidants, lubricants, dispersants, nucleating agents, and the like.
  • the chemical foaming agent composition of the present invention contains sodium hydrogen carbonate as a chemical foaming agent and the acidic substance as an auxiliary agent (foaming auxiliary agent).
  • Sodium bicarbonate is used as a chemical blowing agent in the chemical blowing agent composition of the present invention.
  • Sodium bicarbonate decomposes as in the above formula (1) or formula (2) to generate CO 2 gas, for example, thermoplastic resin or thermoplastic elastomer (hereinafter sometimes referred to as "resin etc.”). form air bubbles within the matrix of
  • the chemical blowing agent composition of the present invention is used to form foams.
  • the foam is composed of a matrix containing a resin or the like as a main component and cells.
  • the acidic substance contained in the chemical foaming agent composition of the present invention (hereinafter referred to as "acidic substance A”) is an inorganic compound or an organic compound having a melting point of 400°C or higher.
  • the acidic substance according to the present invention also includes a substance (for example, diboron trioxide) that generates an acid capable of dissociating protons H 3 + in the coexistence of water or an aqueous medium.
  • the acidic substance A functions as a foaming aid that aids foaming of the chemical foaming agent, sodium hydrogen carbonate.
  • an acidic substance that is an inorganic compound is also referred to as “acidic substance A1”, and an acidic substance that is an organic compound having a melting point of 400° C. or higher is also referred to as “acidic substance A2”.
  • the acidic substance A functions to cause the CO 2 gas generated from sodium hydrogen carbonate to exist as fine bubbles in a matrix such as a resin.
  • the acidic substance A preferably has a property of improving the flame retardancy without causing deterioration of the flame retardancy of the resin constituting the matrix of the foam. The method for evaluating the cell diameter and flame retardancy of the foam will be described later.
  • the chemical foaming agent composition of the present invention may contain optional components other than sodium hydrogen carbonate and acidic substance A within a range that does not impair the effects of the present invention.
  • optional components include chemical foaming agents other than sodium hydrogencarbonate, foaming aids other than acidic substance A, anti-drip agents, antioxidants, lubricants, dispersants, and nucleating agents.
  • the content of the organic compound having a melting point of less than 400° C. may be 58% by mass or less with respect to the total amount of the chemical blowing agent composition. It is preferably 22% by mass or less, more preferably 22% by mass or less. It is particularly preferred that the chemical blowing agent composition of the present invention does not contain organic compounds with a melting point of less than 400°C.
  • composition of chemical foaming agent composition contains sodium bicarbonate and acidic substance A. Furthermore, optional components may be contained within the above ranges. Each component contained in the chemical foaming agent composition of the present invention will be described below.
  • sodium hydrogen carbonate is a chemical foaming agent that is solid (typically powdery) at room temperature (25° C.), and thermally decomposes as a single unit of sodium hydrogen carbonate as shown in formula (1). Decomposition of sodium bicarbonate according to formula (1) is said to begin gradually at 50°C.
  • sodium hydrogen carbonate reacts with acidic substance A according to formula (2).
  • the reaction temperature is not particularly fixed, cells can be generated simply by adding to the thermoplastic resin or thermoplastic elastomer that mainly constitutes the matrix of the foam and performing molding.
  • the acidic substance A is typically solid at room temperature (25° C.) and preferably powder.
  • the acidic substance A can dissociate protons H + in the presence of water or an aqueous medium. It is a pH of an aqueous solution of the substance measured at a temperature of 23° C.) is less than 7.0.
  • the pH of the acidic substance A is preferably 4.6 or less, more preferably in the range of 2.1 to 4.6, from the viewpoint of miniaturization of cells when formed into a foam.
  • the particle shape and average particle size of the acidic substance A are preferably the same as those of sodium hydrogen carbonate used together, for example.
  • Examples of the acidic substance A1 include solid acids or acid salts such as boric acid, its anhydrides, borates, phosphates, sulfites, and acidic metal oxides.
  • As the acidic substance A among these, one or more selected from boric acid, diboron trioxide, sodium dihydrogen phosphate and sodium hydrogen sulfite are preferable.
  • the content ratio of sodium hydrogen carbonate and acidic substance A in the chemical blowing agent composition is 100% by mass for the total of sodium hydrogen carbonate and acidic substance A. It is preferably in the range of 5 to 90 mass %, and the acidic substance A is in the range of 95 to 10 mass %. More preferably, sodium hydrogen carbonate is in the range of 10 to 85% by mass, and acidic substance A is in the range of 90 to 15% by mass. More preferably, sodium hydrogen carbonate is in the range of 15 to 80% by mass, and acidic substance A is in the range of 85 to 20% by mass.
  • the chemical foaming agent composition may contain other chemical foaming agents other than sodium hydrogencarbonate as optional components within a range that does not impair the effects of the present invention.
  • Other chemical blowing agents specifically include azodicarbonamide (ADCA), P,P'-oxybis(benzenesulfonylhydrazide) (OBSH), N,N'-dinitrosopentamethylenetetramine, 5-phenyl-1 , 2,3,4-tetrazole and organic acid metal salts.
  • organic chemical blowing agents having a melting point of less than 400°C are It is preferable that the total content of organic compounds (hereinafter also referred to as “low-melting-point organic compounds”) is 58% by mass or less. More preferably, the chemical blowing agent composition does not contain low-melting organic chemical blowing agents, and particularly preferably does not contain other chemical blowing agents.
  • the chemical foaming agent composition may contain optional components, such as auxiliary agents other than acidic substance A, foaming assistants other than acidic substance A, anti-drip agents, antioxidants, lubricants, etc. , dispersants, nucleating agents and the like.
  • auxiliary agents include inorganic compounds that are not acidic substances, such as talc, calcium carbonate, lithium carbonate, and lithium borate.
  • organic acidic compounds with a melting point of less than 400°C such as citric acid and monosodium citrate, and non-acidic organic compounds such as lithium stearate, lithium acetate, lithium oxalate, lithium citrate, sodium oxalate and sodium benzoate. compound.
  • the total content of low-melting organic compounds in the chemical foaming agent composition It is preferably contained in an amount of 58% by mass or less. More preferably, the chemical blowing agent composition does not contain a low-melting organic blowing aid, and particularly preferably does not contain other aids.
  • the compounds described as specific examples of anti-drip agents, antioxidants, lubricants, etc. in the later-described foaming material can be used as specific examples of other auxiliary agents in the chemical foaming agent composition.
  • the chemical blowing agent composition contains aids other than these blowing aids, the total content of low-melting organic compounds in the chemical blowing agent composition should be 58% by mass or less. is preferred. It is more preferable that the chemical blowing agent composition does not contain low-melting-point organic compounds among aids other than these foaming aids, and particularly preferably does not contain aids other than these foaming aids.
  • the chemical foaming agent composition of the present invention preferably does not contain components other than sodium hydrogen carbonate and acidic substance A. That is, the chemical foaming agent composition of the present invention preferably comprises sodium hydrogen carbonate and acidic substance A.
  • the chemical blowing agent composition of the present invention may be in the form of a mixture of sodium bicarbonate and acidic substance A, or a mixture of these essential ingredients and optional ingredients.
  • the sodium hydrogen carbonate and the acidic substance A are prepared separately, or when optional ingredients are used in addition to these essential ingredients, the optional ingredients are further prepared.
  • it may be in the form of a two-component or multi-component type composition in which each component prepared separately is used in combination at the time of use.
  • the chemical foaming agent masterbatch of the present invention is characterized by containing the chemical foaming agent composition of the present invention and a thermoplastic resin or thermoplastic elastomer (resin or the like).
  • a foam material is produced by directly blending the chemical foaming agent composition into a resin or the like that mainly constitutes the matrix of the foam. , a method of foam-molding the foam material to form a foam.
  • the foam material may be produced by blending the chemical foaming agent masterbatch of the present invention with a resin or the like.
  • the chemical foaming agent masterbatch of the present invention By using the chemical foaming agent masterbatch of the present invention, uniform mixing with enhanced dispersibility of the chemical foaming agent composition in the resin or the like can be facilitated. By uniformly dispersing the chemical foaming agent composition, bonding of cells can be suppressed, and the cell diameter can be made finer.
  • the resin or the like contained in the chemical foaming agent masterbatch of the present invention can be part of the resin or the like contained in the foaming material in the foam to be described later.
  • the sum of the resin etc. derived from the chemical foaming agent masterbatch and the resin etc. added later in the foaming material is the resin etc. which mainly constitutes the matrix of the foam. .
  • X [mass%] is, for example, preferably 1 to 5% by mass, more preferably 2 to 4% by mass.
  • the content of the chemical foaming agent composition in the chemical foaming agent masterbatch of the present invention can be calculated from the content of the chemical foaming agent composition with respect to the total amount of resins and the like in the foaming material described later.
  • the content of the chemical foaming agent composition with respect to the total amount of resin etc. in the foaming material is Y [% by mass]
  • the content of the chemical foaming agent composition in the chemical foaming agent masterbatch is, with respect to the total amount of resin etc. Y/(X/100) [% by mass].
  • the resins, etc. that mainly constitute the matrix of the foam, the resins, etc. in the chemical foaming agent masterbatch and the resins, etc. added later may be the same or different.
  • the chemical foaming agent masterbatch of the present invention may further contain other additives as necessary.
  • specific examples of other additives include the same specific examples as the additives in the foamed material described later.
  • the method for producing the chemical blowing agent masterbatch of the present invention is not particularly limited.
  • the mixture thus obtained is used as a chemical foaming agent masterbatch.
  • a method of melting and kneading the mixture obtained above to form a chemical foaming agent masterbatch may be used.
  • the following operations may be performed to suppress the decomposition of sodium hydrogencarbonate and the reaction between sodium hydrogencarbonate and the acidic substance A as much as possible, that is, to suppress foaming.
  • the operations include applying pressure to the melt-kneaded material, setting the temperature of the melt-kneaded material to a low temperature, and cooling the melt-kneaded material immediately after melt-kneading.
  • the foam of the present invention is obtained by foam-molding a foam material containing the chemical foaming agent composition of the present invention or the chemical foaming agent masterbatch of the present invention and a thermoplastic resin or thermoplastic elastomer. is.
  • a “foaming material” is a composition in which a thermoplastic resin or thermoplastic elastomer is mixed with a chemical foaming agent, a chemical foaming agent composition, or a chemical foaming masterbatch.
  • a “foam” is a molded article obtained by foam-molding a composition obtained by mixing a thermoplastic resin or thermoplastic elastomer with a chemical foaming agent, a chemical foaming agent composition, or a chemical foaming agent masterbatch into a predetermined shape. It may also be said that it is a molded product obtained by foam-molding a foam material into a predetermined shape.
  • the foaming material according to the present invention is a composition containing the chemical foaming agent composition of the present invention or the chemical foaming agent masterbatch of the present invention and a thermoplastic resin or thermoplastic elastomer.
  • the foam of the present invention is a molded article obtained by foam-molding the foam material of the present invention into a predetermined shape.
  • the foaming material for obtaining the foam of the present invention contains the chemical foaming agent composition of the present invention or the chemical foaming agent masterbatch of the present invention and a thermoplastic resin or thermoplastic elastomer (resin or the like).
  • the foam material may be produced by directly blending the chemical foaming agent composition into the resin or the like that mainly constitutes the matrix of the foam of the present invention. It may be produced by compounding.
  • the chemical foaming agent masterbatch of the present invention is used for the foaming material, the resins and the like contained in the foaming material are the sum of the resins and the like contained in the chemical foaming agent masterbatch of the present invention and the resins and the like added later.
  • any thermoplastic resin or thermoplastic elastomer normally used for foam molding can be used without particular limitation. That is, according to the foam of the present invention, by using the chemical foaming agent composition of the present invention, it is possible to miniaturize cells and suppress deterioration of flame retardancy due to the effects described above. Therefore, according to the foam of the present invention, by using the chemical blowing agent composition of the present invention, it is possible to use any kind of thermoplastic resin and thermoplastic elastomer regardless of the kind of thermoplastic resin and thermoplastic elastomer. Similarly, microbubbles can be made finer and flame retardancy can be suppressed.
  • thermoplastic resin or thermoplastic elastomer contained in the foam material is not particularly limited, but polyolefin resin, acrylonitrile-butadiene-styrene resin (ABS resin), polystyrene resin, polyamide resin, polychlorinated It preferably contains at least one selected from vinyl resins, ethylene vinyl acetate resins and thermoplastic elastomers.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • polystyrene resin polyamide resin
  • polychlorinated It preferably contains at least one selected from vinyl resins, ethylene vinyl acetate resins and thermoplastic elastomers.
  • thermoplastic resin examples include polyolefin resins, polystyrene resins, polyamide resins, polyimide resins, polyester resins, acrylic resins, polyurethane resins, polyvinyl chloride resins, vinyl acetate resins, ethylene vinyl acetate resins, epoxy resins, and phenol resins.
  • melamine resin polycarbonate resin, polyacetal resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, styrene-acrylonitrile resin (AS resin), styrene-(meth)acrylic acid resin, styrene-methyl methacrylate resin, acrylonitrile-butadiene -Styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), and the like.
  • AS resin styrene-acrylonitrile resin
  • ABS resin acrylonitrile-butadiene -Styrene resin
  • MFS resin methyl methacrylate-butadiene-styrene resin
  • thermoplastic resins used for the foam of the present invention.
  • Polyolefin resins are homopolymers or copolymers polymerized with olefin as the main monomer component.
  • olefin means the aliphatic chain type unsaturated hydrocarbon which has one double bond.
  • the main component that constitutes the resin refers to a component that accounts for 50% by mass or more of the total monomer components that constitute the polymer.
  • the polyolefin resin is a homopolymer or copolymer containing olefin in an amount of preferably 60 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80 to 100% by mass in the total monomer components. .
  • Olefin copolymers include copolymers of olefins with other olefins, or copolymers of olefins with other monomers that can be copolymerized with olefins.
  • the content of the other monomers in the polyolefin resin is preferably 30% by mass or less, more preferably 0 to 20% by mass, based on the total monomer components.
  • an ⁇ -olefin having 2 to 12 carbon atoms is preferable.
  • examples of olefins include ethylene, propylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 1-octene, and 1-decene.
  • the olefins may be used singly or in combination of two or more.
  • Examples of other monomers copolymerizable with olefins include cyclic olefins such as cyclopentene and norbornene, and dienes such as 1,4-hexadiene and 5-ethylidene-2-norbornene. Furthermore, monomers such as vinyl acetate, styrene, (meth)acrylic acid and its derivatives, vinyl ether, maleic anhydride, carbon monoxide, and N-vinylcarbazole may be used. These other monomers may be used singly or in combination of two or more in the polymerization of the polyolefin resin.
  • “(meth)acrylic acid” means at least one of acrylic acid and methacrylic acid.
  • polyolefin resins include polyethylene resins containing ethylene as a main component, such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE); polypropylene (propylene homopolymer); , ethylene-propylene copolymers, propylene-butene copolymers, ethylene-propylene-butene copolymers, and ethylene-propylene-diene copolymers.
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • LLDPE linear low-density polyethylene
  • polypropylene propylene homopolymer
  • ethylene-propylene copolymers propylene-butene copolymers
  • ethylene-propylene-butene copolymers ethylene-propylene-butene copolymers
  • ethylene-propylene-diene copolymers ethylene-propylene-diene
  • polyethylene resin and polypropylene resin are preferable, and polypropylene resin is more preferable.
  • the stereoregularity of the structure derived from propylene in the polypropylene resin may be isotactic, syndiotactic, or atactic.
  • Polypropylene is more preferable as the polypropylene resin.
  • a polystyrene resin is a homopolymer or copolymer polymerized with a styrene-based monomer as the main monomer component.
  • Styrenic monomers include, for example, styrene, ⁇ -methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, i-propylstyrene, dimethylstyrene, bromostyrene and the like.
  • polystyrene resin a polystyrene resin containing styrene as a main component, that is, containing 50% by mass or more of styrene is preferable, and polystyrene (styrene homopolymer) is more preferable.
  • the polystyrene resin may be a copolymer of a styrene-based monomer and a vinyl monomer copolymerizable with the styrene-based monomer, the main component of which is a styrene-based monomer.
  • vinyl monomers examples include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cetyl (meth)acrylate; (meth)acrylonitrile; ate, dimethyl fumarate, diethyl fumarate, ethyl fumarate, divinylbenzene, alkylene glycol dimethacrylate, and other bifunctional monomers.
  • ABS resin acrylonitrile-butadiene-styrene resin
  • BR polybutadiene
  • SBR styrene-butadiene copolymer
  • ABS resin can also be produced by a blending method in which rubber and AS resin are mechanically mixed.
  • An ABS resin obtained by a graft-blending method of mixing a polymer and an AS resin is preferred.
  • ABS resin for example, part of styrene can be replaced with ⁇ -methylstyrene for the purpose of improving heat resistance.
  • ABS resins it is also possible to introduce methyl methacrylate into the AS resin phase.
  • Polyamide resins include, for example, aliphatic, aromatic, and aliphatic-aromatic polyamide homopolymers, aliphatic and aromatic polyamide copolymers, and mixtures thereof.
  • Polyamide homopolymers specifically include polyhexamethyleneadipamide (polyamide 66), polyhexamethyleneazelaamide (polyamide 69), polyhexamethylenesebacamide (polyamide 610), polyhexamethylenedodecanediamide (polyamide 612), polytetramethylene adipamide (polyamide 46), polydodecanmethylenedodecanamide (polyamide 1212), polycyclamide Q2 (polyamide C8), and the like.
  • Polyamide homopolymers further include lactams such as polycaprolactam (polyamide 6), polylaurolactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11) and di(p-aminocyclohexyl)methandodecanediamide.
  • lactams such as polycaprolactam (polyamide 6), polylaurolactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11) and di(p-aminocyclohexyl)methandodecanediamide.
  • Polyamides and the like prepared by ring opening are included.
  • polyxylylene adipamide polyamide MXD6
  • polytrimethylhexamethylene terephthalamide polyamide 6-3-T
  • polyhexamethylenediamine terephthalamide polyamide 6T
  • polyhexamethylene isophthalamide polyamide 6I
  • Aliphatic and aromatic polyamide copolymers include polyamides prepared by copolymerization of at least two of the above polymers or their constituents. Specific examples of these copolymers include polyamide 6/66 copolymer, polyamide 6/12 copolymer, polyamide 6/6T copolymer, and polyamide 6I/6T copolymer.
  • thermoplastic resin used for the foam of the present invention one of the thermoplastic resins listed above may be used alone, or two or more of them may be used in combination.
  • a polystyrene resin may be used as a main component, and a combination of the polystyrene resin and other resins may be used.
  • other resins in that case, polyethylene resins, polypropylene resins, acrylic resins, AS resins, ABS resins and the like are preferable.
  • thermoplastic elastomer are polymers or polymer blends that have properties similar to vulcanized rubber at the temperature of use, but can be molded and remolded like thermoplastics at elevated temperatures. It consists of In the present invention, thermoplastic elastomers are preferred as resins and the like, as with polyolefin resins, ABS resins, polystyrene resins, polyamide resins, polyvinyl chloride resins, and ethylene vinyl acetate resins in the above thermoplastic resins.
  • Thermoplastic elastomers contain both a flexible component (rubber phase or soft segment) and a molecularly constrained component (resin phase or hard segment) within the material.
  • the chemical composition and structure of various raw rubbers can be adopted for the soft segment, and various resin components are applied for the hard segment.
  • Thermoplastic elastomers are generally classified according to the chemical composition of the hard segments.
  • Thermoplastic elastomers classified in this way include styrene elastomers, chlorinated polyethylene, vinyl chloride elastomers, olefin elastomers, urethane elastomers, ester elastomers, amide elastomers, and ionomers.
  • Styrenic elastomers include block copolymers of styrene and butadiene or isoprene (SBS or SIS) and their hydrogenated (hydrogenated) polymers (SEBS or SEPS).
  • SBS styrene-based elastomers
  • diene-based rubber-like polymers such as polybutadiene (BR), styrene-butadiene copolymer (SBR), and ethylene-propylene-nonconjugated diene three-dimensional copolymer are added to polystyrene resin. and high impact polystyrene (HIPS).
  • PVC-based elastomers examples include a blend of polyvinyl chloride (PVC) with a high degree of polymerization and a plasticizer, a blend of partially crosslinked PVC to which a crosslinked structure is imparted during PVC synthesis and plasticized PVC, and PVC and acrylonitrile-butadiene rubber (NBR). and blended products with urethane rubber.
  • PVC polyvinyl chloride
  • NBR acrylonitrile-butadiene rubber
  • the olefinic elastomers include polyolefins, preferably polypropylene, and rubbers such as ethylene-propylene rubber (EPM), ethylene-propylene-diene rubber (EPDM), isobutylene-isoprene rubber (IIR), natural rubber (NR), NBR and the like.
  • EPM ethylene-propylene rubber
  • EPDM ethylene-propylene-diene rubber
  • IIR isobutylene-isoprene rubber
  • NR natural rubber
  • NBR NBR
  • a dynamic vulcanization type in which crosslinked rubber particles are finely dispersed in polyolefin by vulcanizing rubber when mixing polyolefin and rubber.
  • urethane-based elastomer a block copolymer in which the hard segment is polyurethane and the soft segment is aliphatic polyether or polyester can be applied.
  • ester-based elastomer a block copolymer having an aromatic polyester hard segment and an aliphatic polyether or polyester soft segment can be applied.
  • amide elastomer a block copolymer having an aliphatic polyamide (mainly polyamide 12 and 11) as the hard segment and an aliphatic polyether or polyester as the soft segment can be applied.
  • thermoplastic resin or thermoplastic elastomer contained in the foamed material of the present invention one selected from the above thermoplastic resins and thermoplastic elastomers may be used alone, or two or more thereof may be used in combination.
  • the foaming material according to the present invention contains the chemical foaming agent composition of the present invention in the range of 0.1 to 1.7% by mass with respect to the total amount of the thermoplastic resin and thermoplastic elastomer (resin etc.) in the foaming material. is preferably contained in the range of 0.2 to 0.5% by mass.
  • the content of the organic compound having a melting point of less than 400° C. derived from the chemical foaming agent composition, relative to the total amount of the foaming material, is preferably within the range of 1% by mass or less, and is 0.3% by mass or less. is more preferable, and it is particularly preferable that it is 0% by mass, that is, it does not contain.
  • the content of the organic compound having a melting point of less than 400° C. derived from the chemical foaming agent composition is 1% by mass or less, further 0.3% by mass.
  • it can be set to 0 mass % especially.
  • by using a chemical foaming agent composition to form a foam from a resin or the like that does not contain a chemical foaming agent composition it is difficult to A decrease in combustibility can be suppressed.
  • the foam material according to the present invention preferably contains a flame retardant as an optional component depending on the type of thermoplastic resin or thermoplastic elastomer. Whether or not to add a flame retardant to the foam material is appropriately selected, for example, in the evaluation of flame retardancy described later, using the burning time of the resin or the like as an index. Examples of resins having flame retardancy without the addition of flame retardants include polyamide resins.
  • flame retardants examples include brominated flame retardants, phosphorus flame retardants, and inorganic flame retardants such as antimony compounds and metal hydroxides.
  • a flame retardant may be used individually by 1 type, and may use 2 or more types together.
  • Brominated flame retardants include tetrabromobisphenol A (TBBA), decabromodiphenyl ether (Deca-BDE), tribromophenol, hexabromocyclododecane (HBCD), ethylenebis(tetrabromophthalimide), TBBA carbonate oligomer, TBBA Epoxy oligomers, brominated polystyrene, bis(pentabromophenyl)ethane, TBBA-bis(dibromopropyl ether), poly(dibromophenol), hexabromobenzene (HBB), and the like.
  • TBBA tetrabromobisphenol A
  • Deca-BDE decabromodiphenyl ether
  • HBCD hexabromocyclododecane
  • ethylenebis(tetrabromophthalimide) ethylenebis(tetrabromophthalimide
  • brominated flame retardant bis(hydroxyphenyl)sulfone derivatives, bis(alkoxyphenyl)sulfone derivatives, etc. may be used. Specific examples include bis[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfone.
  • non-drip type brominated flame retardants that prevent resin from dripping during combustion include, for example, bis(pentabromophenyl)ethane.
  • an anti-drip agent which will be described later, may be used in combination.
  • the phosphorus-based flame retardant may be an organic phosphorus-based flame retardant or an inorganic phosphorus-based flame retardant.
  • Organic phosphorus flame retardants include, for example, organic phosphoric acid esters.
  • organic phosphates include phosphate compounds such as phosphites, phosphates and phosphonates. Among these, it is particularly preferable to use phosphates.
  • the inorganic phosphorus-based flame retardant a high-molecular-weight inorganic phosphorus-based compound is preferable, and examples thereof include ammonium polyphosphate and derivatives thereof.
  • phosphites include triphenylphosphite, tris(nonylphenyl)phosphite, tris(2,4-di-t-butylphenyl)phosphite, distearylpentaerythritol diphosphite, bis(2 ,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite and the like.
  • phosphate esters include triphenyl phosphate, tris(nonylphenyl) phosphate, tris(2,4-di-t-butylphenyl) phosphate, distearylpentaerythritol diphosphate, bis(2,6-di- t-butyl-4-methylphenyl)pentaerythritol diphosphate, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphate, tributyl phosphate, bisphenol A bis-diphenyl phosphate, aromatic condensed phosphate ester, etc. mentioned.
  • aromatic condensed phosphate esters examples include 1,3-phenylene bis(di-2,6 xylenyl phosphate), bisphenol A bis(diphenyl phosphate) and 1,3-phenylene bis(diphenyl phosphate).
  • phosphonate examples include dimethyl benzenephosphonate and benzenephosphonate.
  • the content of the flame retardant in the foamed material according to the present invention is preferably in the range of 1 to 30% by mass with respect to the total amount of the resin and the like.
  • the content of the flame retardant in the foam material is within the above range, the resulting foam has good flame retardancy and foam moldability is likely to be ensured. More preferably, the content of the flame retardant is in the range of 1 to 25% by mass with respect to the total amount of the resin and the like.
  • the foaming material according to the present invention contains a resin or the like and the chemical foaming agent composition of the present invention as essential components, and further contains a flame retardant as an optional component.
  • the foam material according to the present invention may contain additives other than the flame retardant as long as the effects of the present invention are not impaired.
  • known additives generally added to foams can be applied.
  • Other additives include anti-drip agents, antioxidants, lubricants, hindered amine compounds, ultraviolet absorbers, antistatic agents, fluorescent whitening agents, pigments, dyes, and the like.
  • Anti-drip agents are added for the purpose of preventing dripping of resin materials during combustion and improving flame retardancy. silicates and the like.
  • An anti-drip agent may be used individually by 1 type, or may be used in combination of 2 or more types.
  • Antioxidants include hindered phenol antioxidants, phosphite ester antioxidants, or a mixture of both.
  • Lubricants include fatty acid salts, fatty acid amides, silane polymers, solid paraffin, liquid paraffin, calcium stearate, zinc stearate, stearamide, silicone powder, methylene bis stearamide and N,N'-ethylene bis stearamide.
  • fatty acid salts include fatty acid salts, fatty acid amides, silane polymers, solid paraffin, liquid paraffin, calcium stearate, zinc stearate, stearamide, silicone powder, methylene bis stearamide and N,N'-ethylene bis stearamide.
  • the content of other additives in the foamed material according to the present invention is within a range that does not impair the effects of the present invention. and the total content is preferably in the range of 0.1 to 22.5% by mass.
  • the foamed material according to the present invention is obtained by appropriately mixing the above-mentioned components. Specifically, a mixture obtained by dry blending a resin or the like, the chemical foaming agent composition of the present invention, an optionally contained flame retardant, and other additives that may be contained as necessary. is used as a foam material.
  • the chemical foaming agent masterbatch of the present invention may be used instead of the chemical foaming agent composition of the present invention. That is, a mixture obtained by dry blending a resin or the like, the chemical foaming agent masterbatch of the present invention, an optionally contained flame retardant, and other additives that may be contained as necessary is used as a foaming material. may be When a chemical foaming agent masterbatch is used to prepare a foaming material, the content of the resin, etc. in the foaming material is the sum of the amount of the resin, etc. in the chemical foaming agent masterbatch and the amount of the resin, etc. added separately. be.
  • a foaming material may be formed by melt-kneading the mixture obtained above.
  • the following operations may be performed to suppress the decomposition of sodium hydrogencarbonate and the reaction between sodium hydrogencarbonate and the acidic substance A as much as possible, that is, to suppress foaming.
  • the operations include applying pressure to the melt-kneaded material, setting the temperature of the melt-kneaded material to a low temperature, and cooling the melt-kneaded material immediately after melt-kneading.
  • the foaming material according to the present invention can take various forms such as powder, granules, tablets, pellets, flakes, fibers, and liquid, depending on the preparation method described above. can.
  • the foam of the present invention is obtained by foam-molding the above foam material.
  • the foam molding method is not particularly limited, and a known foam molding method using sodium hydrogen carbonate as a chemical foaming agent can be applied.
  • a foam is obtained by molding the above-mentioned foam material and heating it to the decomposition temperature of sodium hydrogen carbonate or higher.
  • a preferable foam-molding method for obtaining the foam of the present invention is the production method of the present invention, which will be described later.
  • the foam of the present invention is a foam in which the cell diameter of the foam is fine and the decrease in flame retardancy is suppressed.
  • the cell diameter of the foam of the present invention is preferably 0.4 mm or less, more preferably 0.2 mm or less, as an average cell diameter measured by the following method.
  • the foam is cut with a cutter or the like, and the cross section is observed with a transmission electron microscope such as JEM-2000FX (manufactured by JEOL Ltd.) to take an image of the foamed portion.
  • the foamed part means, for example, when the foam is molded in a mold, the foamed part has a dense skin layer in which the foam has almost no cells, and the foamed part has uniform cells. The region where uniform bubbles can be observed near the center of the cross section, excluding the skin layer vicinity where the
  • the maximum diameter of all existing bubbles was measured for a randomly selected measurement area of 2 mm ⁇ 8 mm using an image measuring machine (NEXIV VMR3020), and the average bubble diameter was averaged.
  • the flame retardancy of the foam of the present invention can be evaluated using, for example, the burning time measured in the following burning test as an index.
  • the burning time measured in the following burning test as an index.
  • a molded article obtained by molding a molding material that does not contain the chemical foaming agent composition of the present invention is subjected to the following combustion test with a combustion time T1, and the foam of the present invention is obtained. Assuming that the combustion time is T2 in the following combustion test, it is preferable that T2 does not greatly increase compared to T1.
  • T2/T1 is preferably 2.0 or less, more preferably 1.5 or less.
  • T2 is preferably 30 seconds or less, more preferably 10 seconds or less, in consideration of the ASTM D3801 standard.
  • the burning time is measured by a 20 mm vertical burning test according to ASTM D3801.
  • test pieces three test pieces having a size of 125 ⁇ 5 mm ⁇ 13 ⁇ 0.5 mm and a thickness of 2 mm are prepared. Each test piece is vertically attached to a clamp, and a burner is used at the lower end of the test piece to apply two 10-second indirect flames with a 20 mm flame, and the combustion behavior is judged.
  • the burning time was obtained by the following method. That is, for each test piece, the longer of the flaming combustion times in two flame contact times is adopted as the combustion time. The average of the burning times for the three test pieces was taken as the burning time.
  • the use of the foam of the present invention is not particularly limited, and examples include electric and electronic parts, electrical components, exterior parts, and interior parts in the fields of home appliances and automobiles, as well as various packaging materials, household goods, and office supplies. , piping, and agricultural materials.
  • the method for producing a foam of the present invention is characterized by having the following (1) foam material preparation step and (2) foam molding step.
  • a step of mixing the chemical blowing agent composition of the present invention or the chemical blowing agent masterbatch of the present invention with a thermoplastic resin or thermoplastic elastomer (resin or the like) to obtain a foaming material (foaming material preparation step)
  • a step of foam-molding the foamed material obtained in (1) above with an injection molding machine (foam molding step)
  • the production method of the present invention may have steps other than (1) foam material preparation step and (2) foam molding step, if necessary. Each step will be described below.
  • the foaming material preparation step in the production method of the present invention can be carried out in the same manner as the foaming material preparation method described in the above foam.
  • the content of each component in the foam material can also be set to the same amount as the content of each component in the foam material described above for the foam.
  • a mixture obtained by dry blending a resin or the like, the chemical foaming agent composition of the present invention, an optionally contained flame retardant, and other additives that may be contained as necessary. is used as a foam material.
  • the foaming material may be prepared using the chemical blowing agent masterbatch of the present invention instead of the chemical blowing agent composition of the present invention.
  • the content of the resin, etc. in the foaming material is the sum of the amount of the resin, etc. in the chemical foaming agent masterbatch and the amount of the resin, etc. added separately. be.
  • the foaming material may be prepared by melt-kneading.
  • the following operations may be performed to suppress the decomposition of sodium hydrogencarbonate and the reaction between sodium hydrogencarbonate and the acidic substance A as much as possible, that is, to suppress foaming.
  • the operations include applying pressure to the melt-kneaded material, setting the temperature of the melt-kneaded material to a low temperature, and cooling the melt-kneaded material immediately after melt-kneading.
  • melt-kneading is generally performed using a kneading device such as a Banbury mixer, roll, plastograph, extruder (single-screw extruder, multi-screw extruder (e.g., twin-screw extruder), etc.), and kneader.
  • a kneading device such as a Banbury mixer, roll, plastograph, extruder (single-screw extruder, multi-screw extruder (e.g., twin-screw extruder), etc.), and kneader.
  • melt-kneading is preferably carried out using an extruder because of its high production efficiency.
  • a multi-screw extruder is preferably used for melt-kneading, and a twin-screw extruder is more preferably used, since high shearability can be imparted.
  • the term extruder is used in a category
  • the temperature and pressure during melt-kneading should be such that the decomposition of sodium hydrogen carbonate and the reaction between sodium hydrogen carbonate and acidic substance A are suppressed as much as possible.
  • the kneading melt temperature corresponds to the cylinder temperature.
  • the screw rotation speed is preferably in the range of 50 to 300 rpm. Further, the discharge rate of the foamed material from the extruder is preferably in the range of 1 to 50 kg/hr.
  • the strand-shaped kneaded material can be processed into pellets, flakes, or the like.
  • the foam molding step in the production method of the present invention is a step of foam molding the foamed material obtained above using an injection molding machine.
  • the injection molding machine includes, for example, a cylinder that heats the foam material, an injection part that communicates with the cylinder and injects the heated foam material from the cylinder, and a mold for molding the injected foam material into a predetermined shape.
  • a general injection molding machine can be used.
  • the heating of the foaming material in the cylinder is the temperature at which the foaming material can be injected from the injection part (viscosity).
  • the heating temperature is, for example, a temperature equal to or higher than the melting temperature of resin or the like contained in the foam material.
  • the heating temperature of the foam material is preferably in the range of 190 to 220°C, more preferably 200 to 210°C.
  • the heating temperature of the foam material is preferably in the range of 220-240.degree. It should be noted that the temperature of the foaming material inside the cylinder can be treated as substantially the same as the temperature of the cylinder. Even if the temperature of the foaming material rises above the decomposition temperature of sodium bicarbonate in the cylinder filled with the foaming material, foaming does not occur because the foaming material cannot increase its volume under the sealed condition.
  • the injection conditions are adjusted as appropriate according to the structure of the injection molding machine, especially the structure of the injection section.
  • the injection pressure is the pressure at which the heated foaming material can be injected from the cylinder into the cavity of the mold, and can be in the range of approximately 10 to 200 MPa.
  • the injection time that is, the time from the start of injection to the end of injection, is preferably within 2 seconds, for example.
  • the injection speed is appropriately adjusted according to, for example, the type of resin used, the shape of the product, the thickness of the product, and the like.
  • the foam material injected into the mold cavity is foam-molded into the shape of the cavity.
  • the volume of the cavity of the mold used is set larger than the volume of the raw foaming material, and the foaming material injected by injection expands in the cavity of the mold, thereby filling the entire cavity with foam. .
  • a value obtained by dividing the volume of the mold cavity by the volume of the foaming material used corresponds to the expansion ratio.
  • the temperature of the foam material during foam molding is a temperature equal to or higher than the decomposition temperature of sodium hydrogencarbonate, preferably in the range of 170 to 230°C.
  • the temperature of the foam material during foam molding may be estimated, for example, as the temperature of the foam material during injection, that is, the temperature of the cylinder.
  • the mold may be a mold with a fixed cavity volume, or a mold with a variable cavity volume.
  • a mold with a variable cavity volume the volume is kept small when the foam material is filled, and by expanding the cavity volume after filling, the generation and expansion of air bubbles can be actively promoted.
  • Such a molding method is called core-back molding. According to core-back molding, a skin layer is formed when the foam material contacts the mold, so a foam with a good surface appearance can be obtained.
  • the conditions for core-back molding from the viewpoint of performing uniform foaming, it is preferable to shorten the time from the end of filling the cavity with the foaming material to the start of expanding the volume of the cavity, for example, within 2 seconds.
  • the temperature of the mold can be set to the cooling temperature from the time of injection of the foam material.
  • the cooling temperature (the temperature of the mold and foam) is preferably 40 to 80°C, for example.
  • the cooling time is appropriately adjusted according to, for example, the type of resin used, the shape of the product, the thickness of the product, and the like.
  • Chemical Blowing Agent Compositions 10 to 13 of the present invention and Chemical Blowing Agent Compositions 1 to 9 of Comparative Examples were prepared by mixing 1 part by mass of each of the compounds shown in Table I with 0.2 part by mass of sodium hydrogen carbonate.
  • Chemical Blowing Agent Compositions 14-15 were prepared.
  • Table I shows the melting point of the compound, the pH when the compound is made into an aqueous solution, and whether the compound is an organic compound or an inorganic compound.
  • Table I also shows the content of the organic compound having a melting point of less than 400°C in the chemical foaming agent composition as a content B [% by mass].
  • a foam with an expansion ratio of 1.1 under the following injection molding condition 1 (the size of the foam is for measuring the burning time (which is the same size as the test piece of ) was molded.
  • the cylinder temperature corresponds to the foam temperature in the cylinder and during injection.
  • a mold having a fixed volume was used. Also, no pressure was applied to the mold during foam molding.
  • the mold temperature corresponds to the cooling temperature.
  • injection molding condition 1 Cylinder temperature (foaming material temperature); 200°C Injection pressure; 20MPa Injection time (time from injection start to injection end); 0.9 seconds Injection speed; 40 [mm/s] Mold temperature; 50°C Cooling time; 15 seconds
  • the cell diameter and burning time (T2) were measured by the methods described above.
  • a resin composition that does not contain the chemical foaming agent composition 1 was prepared, and the molded body obtained by injection molding was measured for the combustion time (T1), which was 4.9 [sec. ]Met.
  • Table I shows T2/T1 and T2-T1 along with bubble diameter and burning time (T2).
  • FIG. 1 shows a graph showing the relationship between the pH of the compound used in combination with sodium hydrogen carbonate (measurement temperature 23° C.) and the cell diameter of the resulting foam.
  • Foaming materials 21 to 29 shown in Table II were prepared using the chemical foaming agent compositions 10 to 13 obtained above and the following thermoplastic resins and flame retardants.
  • Foam materials 33-35 were prepared using chemical blowing agent composition 3 consisting of (outside the range of acidic substance A).
  • thermoplastic resin Polypropylene; Novatec PP_MG03BD (product name, manufactured by Japan Polypropylene Corporation, hereinafter referred to as "PP”.
  • ABS resin Cebian V_660SF (product name, manufactured by Daicel Polymer Ltd., hereinafter referred to as "ABS”).
  • Polyamide resin Amilan_CM1017 (product name, manufactured by Toray Industries, Inc., hereinafter referred to as "PA”.
  • Flame retardant 1 Bis[3,5-dibromo-4-(2,3-dibromopropoxy)phenyl]sulfone (hereinafter referred to as “flame retardant 1”) Bis(pentabromophenyl)ethane (hereinafter referred to as “flame retardant 2”) Condensed phosphate ester (PX-200 (product name, manufactured by Daihachi Chemical Industry Co., Ltd., hereinafter referred to as “flame retardant 3”)
  • injection molding condition 2 Cylinder temperature (foaming material temperature); 220°C Injection pressure; 20MPa Injection time (time from injection start to injection end); 0.9 seconds Injection speed; 40 [mm/s] Mold temperature; 50°C Cooling time; 15 seconds
  • injection molding condition 3 Cylinder temperature (foaming material temperature); 250°C Injection pressure; 20MPa Injection time (time from injection start to injection end); 0.9 seconds Injection speed; 40 [mm/s] Mold temperature; 70°C Cooling time; 15 seconds
  • the cell diameter and burning time (T2) were measured by the methods described above. Also, for each foaming material, a chemical foaming agent composition or a resin composition containing no sodium hydrogencarbonate was prepared, and the combustion time (T1) was measured for the molding obtained by injection molding. Table III shows T2/T1 and T2-T1, along with bubble diameter, combustion time (T2), and combustion time (T1).
  • the foam of the present invention achieves the effect of the present invention, that is, both miniaturization of cells and suppression of deterioration in flame retardancy.
  • a chemical foaming agent composition and a chemical foaming agent masterbatch that can achieve both miniaturization of cells and suppression of deterioration in flame retardancy when used for molding a foam.
  • a foam produced using the chemical foaming agent composition or the chemical foaming agent masterbatch which achieves both miniaturization of cells and suppression of deterioration in flame retardancy, and a method for producing the same.

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Abstract

La présente invention aborde le problème de la fourniture d'une composition d'agent moussant chimique et d'un mélange maître d'agent moussant chimique, chacun de ceux-ci permettant d'obtenir un bon équilibre entre la miniaturisation de bulles d'air et la suppression de la diminution de l'ininflammabilité si elle est utilisée pour le moulage d'une mousse. La présente invention concerne : une mousse qui est produite à l'aide de la composition d'agent moussant chimique décrite ci-dessus ou du mélange maître d'agent moussant chimique, et qui a atteint à la fois la miniaturisation de bulles d'air et la suppression de la diminution de l'ininflammabilité ; et un procédé de production de cette mousse. Une composition de résine thermoplastique selon la présente invention est une composition d'agent moussant chimique qui contient du carbonate d'hydrogène de sodium et une substance acide, la substance acide étant un composé inorganique ou un composé organique qui a un point de fusion de 400 °C ou plus.
PCT/JP2022/005949 2021-03-19 2022-02-15 Composition d'agent moussant chimique, mélange maître d'agent moussant chimique, mousse et procédé de production de mousse WO2022196221A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006131719A (ja) * 2004-11-04 2006-05-25 Kaneka Corp 断熱性の改良された熱可塑性樹脂発泡体およびその製造方法
JP2014159541A (ja) * 2013-01-22 2014-09-04 Sekisui Chem Co Ltd 熱膨張性耐火樹脂組成物
JP2016505659A (ja) * 2012-11-29 2016-02-25 コンパニー ゼネラール デ エタブリッスマン ミシュラン 熱発泡性ゴム組成物を含むトレッドを有する車両用タイヤ
CN111205503A (zh) * 2020-02-21 2020-05-29 中化石化销售有限公司 发泡剂材料、发泡剂母粒及其制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006131719A (ja) * 2004-11-04 2006-05-25 Kaneka Corp 断熱性の改良された熱可塑性樹脂発泡体およびその製造方法
JP2016505659A (ja) * 2012-11-29 2016-02-25 コンパニー ゼネラール デ エタブリッスマン ミシュラン 熱発泡性ゴム組成物を含むトレッドを有する車両用タイヤ
JP2014159541A (ja) * 2013-01-22 2014-09-04 Sekisui Chem Co Ltd 熱膨張性耐火樹脂組成物
CN111205503A (zh) * 2020-02-21 2020-05-29 中化石化销售有限公司 发泡剂材料、发泡剂母粒及其制备方法

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