WO2010147067A1 - Agent générateur de gaz - Google Patents

Agent générateur de gaz Download PDF

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Publication number
WO2010147067A1
WO2010147067A1 PCT/JP2010/059981 JP2010059981W WO2010147067A1 WO 2010147067 A1 WO2010147067 A1 WO 2010147067A1 JP 2010059981 W JP2010059981 W JP 2010059981W WO 2010147067 A1 WO2010147067 A1 WO 2010147067A1
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WO
WIPO (PCT)
Prior art keywords
gas
generating agent
gas generating
foam
amount
Prior art date
Application number
PCT/JP2010/059981
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English (en)
Japanese (ja)
Inventor
間山　憲和
Original Assignee
永和化成工業株式会社
三菱瓦斯化学株式会社
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Application filed by 永和化成工業株式会社, 三菱瓦斯化学株式会社 filed Critical 永和化成工業株式会社
Priority to JP2011519759A priority Critical patent/JP5647606B2/ja
Priority to KR1020127001460A priority patent/KR101768431B1/ko
Priority to DE112010002570T priority patent/DE112010002570A5/de
Priority to CN201080026810.4A priority patent/CN102803424B/zh
Publication of WO2010147067A1 publication Critical patent/WO2010147067A1/fr

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/35—Component parts; Details or accessories
    • B29C44/355—Characteristics of the foam, e.g. having particular surface properties or structure
    • B29C44/357—Auxetic foams, i.e. material with negative Poisson ratio; anti rubber; dilatational; re-entrant
    • 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
    • C08J9/10—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 nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

Definitions

  • the present invention relates to a gas generating agent used for producing a foamed material such as a thermoplastic resin or rubber.
  • azodicarbonamide In the production of foams such as thermoplastic resins and rubbers, chemical foaming agents such as azodicarbonamide (ADCA) and foaming aids such as urea are used to adjust the decomposition temperature.
  • azodicarbonamide is known to generate cyanuric acid, biurea (hydrazodicarbonamide), urea, and the like as decomposition residues during thermal decomposition.
  • the heating temperature is 220 ° C. or higher, a part of biurea is decomposed to generate ammonia (see Non-Patent Documents 1 to 3).
  • Urea compounds produce ammonia by heating, but ammonia gas does not contribute to the expansion ratio.
  • To produce a high-magnification foam it is necessary to increase the amount of foaming agent added, and ammonia is generated. Therefore, odor countermeasures are required at the foam manufacturing site.
  • Patent Document 1 A method of adding molybdenum and a molybdate compound to the foaming agent in order to increase the amount of gas generated by the chemical foaming agent (see Patent Document 1), or a method of supporting a fatty acid alkaline earth metal salt and a quaternary ammonium salt (Patent Document 2)
  • Patent Document 2 discloses a method for decomposing and removing organic nitrogen by adding nitrite to water containing organic nitrogen, which is a decomposition treatment of organic nitrogen in an aqueous solution. It cannot be applied to the body manufacturing field.
  • the purpose of the present invention is to suppress the generation of ammonia and nitrous acid gas and produce nitrogen gas when producing foams such as resin materials and rubber using a compound that generates ammonia gas by heating.
  • An object of the present invention is to provide a gas generating agent capable of obtaining a foam having uniform and fine bubbles and high magnification and high whiteness.
  • a gas generating agent used for the production of a foam which comprises (A) a nitrogen-containing compound that generates ammonia gas by thermal decomposition, (B) nitrite, and (C) hydrotalcite. Gas generating agent.
  • the gas generating agent according to (1) wherein the nitrogen-containing compound (A) is a compound having a urea bond.
  • the total amount of the nitrogen-containing compound (A), nitrite (B) and hydrotalcite (C) is 0.5 to 95% by weight of the nitrogen-containing compound (A) and 0% of nitrite (B).
  • the gas generating agent according to (1) or (2) characterized by containing 5 to 60% by weight and 1 to 40% by weight of hydrotalcite (C).
  • M 2+ is a divalent metal ion of a metal selected from the group consisting of Mg, Mn, Fe and Zn
  • M 3+ is a trivalent metal ion of a metal selected from the group consisting of Al, Fe and Cr
  • a n ⁇ is an n-valent anion of a group selected from the group consisting of OH, F, Cl, Br, NO 3 , CO 3 and SO 4
  • x is in the range of 0 ⁇ x ⁇ 0.33
  • n Is an integer and m is 0 or more.
  • a foaming composition comprising the gas generating agent according to any one of (1) to (6) in a foamed material.
  • a method for producing a foam comprising a step of heating the foaming composition according to (7) or (8).
  • urea compounds that are usually used as foaming aids such as urea can be used as foaming agents for synthetic resin materials and rubber materials, and when used as foaming aids for chemical foaming agents, While maintaining the function of adjusting the decomposition temperature of the chemical foaming agent, in addition to the generation of gas of the chemical foaming agent, the amount of gas generated can be increased by generating nitrogen gas from the foaming aid.
  • the reason why high magnification can be achieved without requiring countermeasures for odor in the present invention is that ammonia generated by thermal decomposition of a nitrogen-containing compound is reacted with nitrous acid and changed to nitrogen gas as a foaming gas. It is considered that the use of hydrotalcite at this time increases the reactivity of nitrous acid with ammonia to suppress the generation of nitrous acid gas.
  • the whiteness is improved by the method of using nitrous acid and hydrotalcite of the present invention in combination with a foaming agent that becomes orange-yellow before pyrolysis and becomes white after decomposition (thermal decomposition) like azodicarbonamide. It is considered that the problem of the residual color occurs when the color is insufficient) because the thermal decomposition is accelerated and the residual color disappears.
  • the gas generating agent of the present invention is characterized by containing a nitrogen-containing compound (A), a nitrite (B), and a hydrotalcite (C).
  • the nitrogen-containing compound (A) of the present invention generates ammonia gas by thermal decomposition.
  • ammonia gas is generated by thermal decomposition.
  • the main component of the gas generated by thermal decomposition is ammonia gas
  • the main component of the gas generated by thermal decomposition is ammonia such as nitrogen gas. It may be a gas other than a gas, and a small amount of ammonia gas may be generated as a by-product in addition to the gas.
  • ADCA 4,4′-oxybis (benzenesulfonylhydrazide)
  • DNPT N
  • one of these may be used alone, or two or more may be used in combination.
  • compounds having a urea bond are preferable, and urea and HDCA can be suitably used.
  • urea commercially available fine powder urea or fine powder urea whose hygroscopicity is improved by a surface treatment agent such as fatty acid, fatty acid metal salt, fatty acid ester, silane coupling agent, or the like can also be used.
  • thermal decomposition in the nitrogen-containing compound (A) of the present invention means heating when kneading the foam production raw material containing the nitrogen-containing compound (A), and heating when foaming the kneaded product (
  • thermal decomposition by heating in the press mold can be exemplified.
  • the heating temperature during the production of the foam is about 130 to 250 ° C.
  • nitrite (B) used in the present invention examples include sodium nitrite, potassium nitrite, calcium nitrite and the like, and one kind selected from these may be used alone or in combination of two or more kinds. it can. These nitrites are preferably finely divided powder.
  • the hydrotalcite (C) used in the present invention is a crystalline composite metal hydroxide, and is preferably a hydrotalcite represented by the following general formula (1).
  • M 2+ is a divalent metal ion of a metal selected from the group consisting of Mg, Mn, Fe, and Zn
  • M 3+ is a metal selected from the group consisting of Al, Fe, and Cr.
  • Trivalent metal ion, A n ⁇ is an n-valent anion of a group selected from the group consisting of OH, F, Cl, Br, NO 3 , CO 3 and SO 4
  • x is in the range of 0 ⁇ x ⁇ 0.33 Where n is an integer and m is 0 or greater.
  • n is the valence of the anion, preferably 1 or 2, and more preferably 2.
  • hydrotalcite in which M 2+ is Mg 2+ and M 3+ is Al 3+ is preferable, and the molar ratio of Al: Mg is preferably 2: 5 to 2:10 from the viewpoint of availability.
  • the molar ratio of Al: Mg is 2: 5
  • the molar ratio of Al to Mg is 2:10.
  • the molar fraction x of Al 0.17.
  • the hydrotalcite of the present invention has an action of improving the reactivity of nitrite.
  • hydrotalcite By adding hydrotalcite, it promotes the decomposition of ammonia generated when the nitrogen-containing compound (A) is thermally decomposed, and improves the reactivity of nitrite, thereby suppressing the generation of nitrous acid gas, nitrogen gas It is possible to improve the foaming property.
  • the particle diameter of the hydrotalcite of the present invention is not particularly limited, but in order to effectively act on the reaction between the nitrogen-containing compound (A) and nitrite, the dispersibility in the gas generant is increased. It is preferable to use finely divided hydrotalcite having a maximum particle size of 80 ⁇ m or less.
  • the gas generating agent of the present invention contains a nitrogen-containing compound (A), nitrite (B), and hydrotalcite (C) that generate gas by thermal decomposition and generate ammonia gas.
  • A nitrogen-containing compound
  • B nitrite
  • C hydrotalcite
  • the ratio of each component in the gas generating agent of this invention for example, the compounding quantity with respect to the nitrogen-containing compound (A) of the said nitrite (B) and hydrotalcite (C) depends on the amount of generated ammonia gas, and is generated. Since the amount of ammonia gas to be used varies greatly depending on the type of nitrogen-containing compound (A) used, it cannot be generally limited.
  • the nitrogen-containing compound (A) is preferably 0.5 to 95% by weight. is there.
  • the blending amount of nitrite (B) is varied depending on the amount of ammonia gas generated, but is preferably 0.5 to 60% by weight.
  • the blending amount of hydrotalcite (C) is also changed according to the amount of ammonia gas generated, but is preferably 1 to 40% by weight.
  • constituents other than (A), (B) and (C) in the gas generating agent of the present invention are not limited as long as the effects of the present invention are not impaired, and the blending amount thereof is also limited.
  • Specific examples of components other than (A), (B) and (C) include fatty acids such as stearic acid or salts of fatty acids such as calcium stearate.
  • the gas generating agent of the present invention can be used for producing foams such as various synthetic resin materials and rubber materials to obtain a suitable foam.
  • a gas generating agent can be blended and used as a composite gas generating agent.
  • thermal decomposition type chemical foaming agent examples include general chemical foaming agents that generate nitrogen gas or carbon dioxide gas by thermal decomposition.
  • general chemical foaming agents that generate nitrogen gas or carbon dioxide gas by thermal decomposition.
  • azodicarbonamide, 4,4 ′ -Chemical foaming agents such as oxybis (benzenesulfonylhydrazide), N, N'-dinitrosopentamethylenetetramine, 5-phenyl-1,2,3,4-tetrazole, and organic acids such as monosodium citrate and sodium tartrate
  • organic chemical foaming agents for metal salts and inorganic chemical foaming agents such as sodium hydrogen carbonate. You may use these individually by 1 type or in combination of 2 or more types.
  • the gas generating agent of the present invention when used in combination with a pyrolytic chemical foaming agent, the pyrolytic chemical foaming agent first generates a decomposing foaming gas as the heating temperature rises, and then the gas generating of the present invention
  • a two-stage decomposition foaming agent can be obtained by selecting and combining gas generating agents having different gas generation temperatures such that the agent generates nitrogen gas (or vice versa). By using such a two-stage decomposition type foaming agent, it becomes possible to produce a characteristic foam having a high foaming ratio.
  • the method for producing the gas generating agent of the present invention is not particularly limited, and a general mixing method can be used.
  • the nitrogen-containing compound (A), nitrite (B), and hydrotalcite (C) are uniformly applied using a high-speed mixer, ribbon blender, corn blender, etc. under conditions of a temperature of 60 ° C. or less and a time of about 5 minutes. What is necessary is just to mix so that it may disperse
  • the method for producing the composite gas generating agent of the present invention is not particularly limited, and a general mixing method can be used.
  • the pyrolytic chemical foaming agent may be mixed together, or after producing the gas generating agent of the present invention, the pyrolytic chemical foaming agent may be mixed.
  • the composite gas generating agent may be mixed using, for example, a high-speed mixer, ribbon blender, cone blender, or the like so as to be uniformly dispersed under conditions of a temperature of 60 ° C. or less and a time of about 5 minutes.
  • the gas generating agent or composite gas generating agent of the present invention can be suitably used for foam molding of synthetic resin materials or rubber materials.
  • the gas generating agent or composite gas generating agent of the present invention can suppress generation of ammonia and nitrous acid gas and generate nitrogen gas at a foam molding temperature (for example, about 130 to 250 ° C.) of a synthetic resin material or rubber material.
  • a foam molding temperature for example, about 130 to 250 ° C.
  • the foaming composition of the present invention is obtained by blending the above-described gas generating agent of the present invention into a material to be foamed.
  • the foamed material include synthetic resin materials and rubber materials.
  • the synthetic resin material of the present invention include a vinyl chloride resin, a vinyl chloride copolymer resin, polyethylene, polypropylene, a polyolefin copolymer resin exemplified by an ethylene-propylene copolymer, a polystyrene resin, and an acrylonitrile-butadiene-styrene copolymer. (ABS resin) and the like are exemplified, but not limited thereto.
  • the foaming composition (unfoamed resin composition) can be prepared by kneading the synthetic resin material, the crosslinking agent, and the gas generating agent or composite gas generating agent of the present invention with a heated kneading roll. .
  • the kneading temperature is preferably 90 to 130 ° C.
  • the unfoamed resin composition thus obtained is filled in a mold and pressed with a press to obtain a foam of a synthetic resin material.
  • a foam of a resin composition can be obtained by filling 100% in a mold having a thickness of 5 to 30 mm and pressurizing with a press machine at 145 to 170 ° C. and 150 kg / cm 2 for 5 to 60 minutes.
  • the blending ratio of each component in the foaming composition is not particularly limited, but the crosslinking agent is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the synthetic resin material. Partly formulated. If the blending ratio of the cross-linking agent is too small, the cross-linking may become under, resulting in insufficient foaming due to outgassing, and if too large, the cross-linking may be over and the foam may be cracked or roughened.
  • the amount of the gas generating agent of the present invention can be appropriately selected according to the target foaming ratio and is not particularly limited, but is preferably 1 to 7 parts by weight per 100 parts by weight of the synthetic resin material. .
  • the amount of the composite gas generating agent used can be appropriately selected according to the target foaming ratio and is not particularly limited. 1 to 7 parts by weight is blended with 100 parts by weight of the resin material.
  • the nitrogen-containing compound (A) contained in the gas generating agent of the present invention is the one conventionally used as a foaming aid for a chemical foaming agent, composite gas generation containing the gas generating agent of the present invention is used.
  • the agent also has a function of adjusting the decomposition temperature for the chemical foaming agent as the foaming aid.
  • urea-based foaming aids conventionally did not contribute to foaming even when ammonia was generated by thermal decomposition, but the gas generating agent of the present invention generates nitrogen gas by combining nitrite and hydrotalcite. Can contribute to foaming.
  • the nitrogen gas derived from the foaming aid can also be used as the foaming gas, so that the generated gas can be increased with the same amount of chemical foaming agent used.
  • a foam having the same expansion ratio can be produced with a smaller amount of chemical foaming agent than in the past.
  • the ratio of the gas generating agent of the present invention in the composite gas generating agent is not particularly limited, and can be appropriately selected according to the target expansion ratio.
  • it can be used according to the ratio of the foaming aid to the chemical foaming agent in the case of combining a conventional chemical foaming agent and a foaming aid.
  • crosslinking agent examples include dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di- (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di -(T-butylperoxy) hexyne-3,1,3-bis (t-butylperoxyisopropyl) benzene, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl- 4,4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperbenzoate, t-butylperoxyisopropyl carbonate, diacetyl Peroxide, lauroyl peroxide, t
  • Examples of the rubber material of the present invention include natural rubber (NR), polyisoprene rubber, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, butadiene rubber and the like. However, it is not limited to these.
  • a method for preparing a foaming composition by blending the gas generating agent or composite gas generating agent of the present invention into a rubber material, and thereby manufacturing a foam general manufacturing conditions for the foam can be used.
  • a rubber material, a vulcanizing agent, a filler, a vulcanization accelerator, and the gas generating agent or composite gas generating agent of the present invention are uniformly dispersed with a kneading roll to obtain a foaming composition.
  • the obtained foaming composition is put into an extruder heated to about 70 to 90 ° C. to prepare an unvulcanized molded body.
  • the resulting unvulcanized molded body is heated in an oven heated to about 60 to 220 ° C. for about 5 to 15 minutes to vulcanize and foam to obtain a foam of rubber material.
  • the blending ratio of each component in the foaming composition is not particularly limited, but the vulcanizing agent is preferably blended in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the rubber material.
  • the filler is preferably blended in an amount of 10 to 150 parts by weight per 100 parts by weight of the rubber material.
  • the vulcanization accelerator is preferably blended in an amount of 0.1 to 20 parts by weight per 100 parts by weight of the rubber material.
  • the amount of the gas generating agent of the present invention can be appropriately selected according to the target foaming ratio and is not particularly limited, but is preferably 1 to 20 parts by weight per 100 parts by weight of the rubber material.
  • the usage amount of the composite gas generating agent can be appropriately selected according to the target foaming ratio and is not particularly limited, but preferably rubber. 1 to 20 parts by weight per 100 parts by weight of the material.
  • Specific examples of the vulcanizing agent used in the present invention include sulfur.
  • Specific examples of the filler used in the present invention include heavy and light calcium carbonate.
  • Specific examples of the vulcanization accelerator used in the present invention include DM (dibenzylthiazol disulfide).
  • the gas generating agent of the present invention is economical because it is possible to produce a foam having the same magnification with an addition amount smaller than that of a conventional product.
  • problems such as poor adhesion and fogging of resin foam caused by urea compounds by using nitrogen gas as a by-product such as ammonia odor generated from chemical blowing agents and urea compounds, urea compounds and biurea (hydrazodicarbonamide) Can also be improved.
  • the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples.
  • the amount of gas generated, the amount of nitrous acid gas generated, the amount of ammonia generated, the specific gravity of the foam, and the bubble state of the foam were evaluated by the following methods.
  • ⁇ Measurement of nitrous acid generation amount> The gas generated during pyrolysis was absorbed in an absorption bottle containing 400 ml of 1N aqueous sodium hydroxide solution, and the amount of nitrous acid gas generated in the absorbing solution was measured according to JIS-K0102 (naphthylethylenediamine absorptiometry).
  • Specific gravity of foam The specific gravity of the foam of the resin composition and the rubber composition was determined by an electronic hydrometer (manufactured by Alpha Mirage, product name MD-200S).
  • urea manufactured by Mitsui Chemicals, Inc., industrial mole
  • sodium nitrite 1 mole
  • hydrotalcite [Mg 2+ 0.83 Al 3+ 0.17 (OH) 2 ] 0.17+ [(CO 3 ) 2 ⁇ 0.17 /
  • the amount of generated gas was measured using 1 g of the obtained gas generating agent. When the amount of generated gas was measured, gas generation was observed from 120 ° C., gas was rapidly generated at 155 ° C., and rapid gas generation was completed at 158 ° C., but slow gas generation was observed up to 180 ° C., and thereafter 220 ° C. Until now, no gas generation was observed. Table 1 shows the measurement results of the generated gas amount, the nitrous acid gas generated amount, and the ammonia generated amount.
  • EVA ethylene-vinyl acetate copolymer
  • DCP dicumyl peroxide
  • Table 1 shows the blending amount and evaluation result of the gas generating agent
  • Table 2 shows the blending amount and evaluation result of the foam.
  • the obtained foam was colored light yellow and the degree of crosslinking was low, so that the foam adhered to the mold and could not be taken out.
  • Example 2 Using 1 g of the gas generant, the amount of gas generated, the amount of nitrous acid gas generated, and the amount of ammonia generated were measured in the same manner as in Example 1 to produce a foam.
  • Table 1 shows the blending amount and evaluation result of the gas generating agent
  • Table 2 shows the blending amount and evaluation result of the foam.
  • Example 2 Except that hydrotalcite was removed from the formulation of Example 2, the amount of gas generated, the amount of nitrous acid generated, and the amount of ammonia generated were measured in the same manner as in Example 2 to produce a foam.
  • Table 1 shows the blending amount and evaluation result of the gas generating agent, and Table 2 shows the blending amount and evaluation result of the foam. The obtained foam was pale yellow and adhered to the mold and could not be taken out.
  • a gas generating agent was obtained by mixing at room temperature for 5 minutes using a bag. Using 1 g of the resulting gas generant, the amount of gas generated, the amount of nitrous acid gas generated, and the amount of ammonia generated were measured in the same manner as in Example 1. Table 1 shows the blending amount of the gas generating agent and the evaluation results.
  • Example 3 The chemical foaming agent azodicarbonamide (ADCA) (trade name “Binihol AC # 3”, Eiwa Kasei Co., Ltd.) was used in the same manner as in Example 3 except that the hydrotalcite was replaced with aluminum silicate (Wako Pure Chemical Industries, Ltd., aluminum silicate). Industrial Co., Ltd.) and zinc oxide (manufactured by Sakai Chemical Co., Ltd., 2 types of zinc oxide) were mixed to obtain a gas generating agent. In the same manner as in Example 1, the amount of gas generated, the amount of nitrous acid gas generated, and the amount of ammonia generated were measured, and then a foam was produced in the same manner as in Example 3. Table 1 shows the blending amount and evaluation result of the gas generating agent, and Table 2 shows the blending amount and evaluation result of the foam. The obtained foam was colored light yellow, and the bubbles inside the foam were also non-uniform.
  • ADCA chemical foaming agent azodicarbonamide
  • Table 1 shows the blending amount and evaluation result of
  • Carplex # 80 20 parts by weight, titanium dioxide (manufactured by Wako Pure Chemical Industries, titanium oxide) 10 parts by weight, zinc oxide (manufactured by Sakai Chemical Co., Ltd., 2 types of zinc oxide), 5 parts by weight, stearic acid (manufactured by Kao Corporation, 3 parts by weight of Lunac S-20) and 5 parts by weight of naphthenic oil (Sansen 410, manufactured by Nippon San Oil Co., Ltd.) were added and further kneaded and taken out.
  • titanium dioxide manufactured by Wako Pure Chemical Industries, titanium oxide
  • zinc oxide manufactured by Sakai Chemical Co., Ltd., 2 types of zinc oxide
  • stearic acid manufactured by Kao Corporation, 3 parts by weight of Lunac S-20
  • naphthenic oil Sansen 410, manufactured by Nippon San Oil Co., Ltd.
  • This kneaded product is wound around a mixing roll, 2.5 parts of sulfur (manufactured by Tsurumi Chemical Co., Ltd., fine powdered sulfur) and 1 part of vulcanization accelerator DM are added and kneaded for 3 minutes as a vulcanizing agent, and then a foaming agent mixture 15 Part was added and kneaded for 3 minutes.
  • the kneaded material was charged so that the inner volume of the mold (124 mm ⁇ 124 mm ⁇ 11 mm) of the press apparatus heated to 150 ° C. was filled to 100%, and pressurized at a press pressure of 150 kg / cm 2 . After 15 minutes, the press pressure was released to normal pressure all at once, and a foam was obtained.
  • the amount of foam blended and the evaluation results are shown in Table 2.
  • Example 4 Except that hydrotalcite was removed from the formulation of Example 4, the same operations as in Example 4 were performed, and the amount of generated gas, the amount of nitrous acid gas generated, and the amount of ammonia generated were measured to produce a foam.
  • Table 1 shows the blending amount and evaluation result of the gas generating agent, and Table 2 shows the blending amount and evaluation result of the foam. The bubbles inside the foam were not uniform.
  • Example 5 118 g (1 mol) of biurea (hydrazodicarbonamide, manufactured by Eiwa Kasei Kogyo Co., Ltd., FE-823), 42.5 g (0.5 mol) of potassium nitrite (manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade potassium nitrite), hydro Talsite ([Mg 2+ 0.83 Al 3+ 0.17 (OH) 2 ] 0.17+ [(CO3) 2 ⁇ 0.17 / 2 ⁇ 0.33H 2 O] 0.17 ⁇ , Al: Mg mole A ratio of 2:10) 12 g was mixed at room temperature for 5 minutes using a polyethylene bag, and then pulverized to 150 mesh pass with a ball mill to obtain a gas generating agent.
  • biurea hydro nitrite
  • potassium nitrite manufactured by Wako Pure Chemical Industries, Ltd., Wako special grade potassium nitrite
  • hydro Talsite [Mg 2+ 0.83 Al 3+ 0.17 (OH) 2 ]
  • Example 5 Except for removing hydrotalcite from the formulation of Example 5, the amount of generated gas, the amount of nitrous acid generated, and the amount of ammonia generated were measured in the same manner as in Example 5 to produce a foam.
  • Table 1 shows the blending amount and evaluation result of the gas generating agent, and Table 2 shows the blending amount and evaluation result of the foam. The obtained foam was colored pale yellow and almost no bubbles were observed.
  • Example 1 As shown in Table 1, in Examples 1 to 5, the amount of generated gas was improved, the detected amount of nitrous acid was decreased, and ammonia was not detected in all gas generating agents. Therefore, in Examples 1 to 5, it was confirmed that the nitrite reactivity was improved by hydrotalcite, nitrous acid gas was reduced, ammonia was further decomposed, and the amount of nitrogen gas generated during foaming was increased. It was done.
  • Examples 1 to 5 are excellent in whiteness of the foam, and the bubbles inside the foam are fine and uniform bubbles. As can be seen from the specific gravity of the foam, the expansion ratio is as follows. It was confirmed to improve.
  • thermoplastic resin or rubber when producing a foam of thermoplastic resin or rubber, it is possible to produce a high-magnification foam without increasing the amount of the chemical foaming agent, and at the same time, it is possible to suppress ammonia, and thus the production site This eliminates the need for ammonia odor countermeasures, and is extremely advantageous industrially.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Selon l'invention, en mélangeant un agent générateur de gaz, qui est obtenu en combinant (A) un composé azoté (tels que des agents chimiques contenant une liaison urée comprenant de l'urée et de l'hydrazodicarbonamide) qui produit du gaz ammoniac par chauffage, (B) un nitrite, et (C) un hydrotalcite, avec un matériau de résine synthétique ou un matériau caoutchouc à titre de composition destinée à produire une mousse, puis en chauffant ledit mélange et en le mettant en forme de manière à obtenir un corps alvéolaire, il est possible de générer du gaz azote tout en supprimant la génération de gaz ammoniac ou acide nitreux, et il est, par conséquent, possible d'obtenir un corps alvéolaire contenant de fines bulles gazeuses uniformes et ayant un degré élevé de blancheur et un rapport d'aspect élevé.
PCT/JP2010/059981 2009-06-19 2010-06-11 Agent générateur de gaz WO2010147067A1 (fr)

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JP2011519759A JP5647606B2 (ja) 2009-06-19 2010-06-11 ガス発生剤
KR1020127001460A KR101768431B1 (ko) 2009-06-19 2010-06-11 가스 발생제
DE112010002570T DE112010002570A5 (de) 2009-06-19 2010-06-11 Gaserzeugungsmittel
CN201080026810.4A CN102803424B (zh) 2009-06-19 2010-06-11 气体发生剂

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JP2009-146119 2009-06-19

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KR (1) KR101768431B1 (fr)
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DE (1) DE112010002570A5 (fr)
WO (1) WO2010147067A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032427A (ja) * 2011-08-01 2013-02-14 Eiwa Kasei Kogyo Kk 発泡体製造用のガス発生剤

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
CN106661422B (zh) * 2015-04-23 2018-10-09 三菱瓦斯化学株式会社 气体发生剂以及使用该气体发生剂的发泡体的制造方法
US20180155277A1 (en) 2015-04-23 2018-06-07 Mitsubishi Gas Chemical Company, Inc. Gas generating agent, and method for producing foam using the same
KR101966289B1 (ko) * 2017-12-01 2019-04-08 주식회사 동진쎄미켐 악취 생성이 저감된 발포제 및 이를 이용하여 형성된 발포체
CN112624888A (zh) * 2020-09-29 2021-04-09 陈肇明 一种新型安全气囊装置用气体发生剂

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49369A (fr) * 1972-04-14 1974-01-05
JPS63113033A (ja) * 1986-05-09 1988-05-18 Sekisui Chem Co Ltd 発泡剤組成物
JPH059321A (ja) * 1991-07-02 1993-01-19 Eiwa Kasei Kogyo Kk アゾジカルボンアミド系発泡剤組成物
JPH08100075A (ja) * 1994-09-29 1996-04-16 Asahi Denka Kogyo Kk 発泡用硬質塩素含有樹脂組成物
JPH08295803A (ja) * 1995-04-26 1996-11-12 Konan Kasei:Kk 樹脂成形機加熱塔内用洗浄材料および洗浄方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS49369A (fr) * 1972-04-14 1974-01-05
JPS63113033A (ja) * 1986-05-09 1988-05-18 Sekisui Chem Co Ltd 発泡剤組成物
JPH059321A (ja) * 1991-07-02 1993-01-19 Eiwa Kasei Kogyo Kk アゾジカルボンアミド系発泡剤組成物
JPH08100075A (ja) * 1994-09-29 1996-04-16 Asahi Denka Kogyo Kk 発泡用硬質塩素含有樹脂組成物
JPH08295803A (ja) * 1995-04-26 1996-11-12 Konan Kasei:Kk 樹脂成形機加熱塔内用洗浄材料および洗浄方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013032427A (ja) * 2011-08-01 2013-02-14 Eiwa Kasei Kogyo Kk 発泡体製造用のガス発生剤

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CN102803424A (zh) 2012-11-28
KR101768431B1 (ko) 2017-08-16
DE112010002570A5 (de) 2012-04-26
JP5647606B2 (ja) 2015-01-07
KR20120101322A (ko) 2012-09-13
CN102803424B (zh) 2014-09-03
JPWO2010147067A1 (ja) 2012-12-06

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