WO2004090029A1 - 発泡性スチレン改質オレフィン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法 - Google Patents
発泡性スチレン改質オレフィン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法 Download PDFInfo
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- WO2004090029A1 WO2004090029A1 PCT/JP2004/003844 JP2004003844W WO2004090029A1 WO 2004090029 A1 WO2004090029 A1 WO 2004090029A1 JP 2004003844 W JP2004003844 W JP 2004003844W WO 2004090029 A1 WO2004090029 A1 WO 2004090029A1
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
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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
- C08J9/16—Making expandable particles
- C08J9/18—Making expandable particles by impregnating polymer particles with the blowing agent
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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
- C08J9/22—After-treatment of expandable particles; Forming foamed products
- C08J9/228—Forming foamed products
- C08J9/232—Forming foamed products by sintering expandable particles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
-
- 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
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
Definitions
- the present invention relates to a method for producing expandable styrene-modified oil-based luster particles, pre-expanded particles, and an expanded molded article.
- Expanded molded articles of styrene-modified olefin-based resin particles have been widely used as returnable boxes for machine parts such as automobile parts and cushioning packaging materials for electric products due to their excellent impact resistance, abrasion resistance and oil resistance. I have.
- styrene-modified olefin-based resin has high electrical insulation, so it is easily charged by friction and not only impairs the appearance of the foamed molded article due to dust, but also contaminates the contents due to dust collection and electrostatic breakdown. Therefore, there was a problem in using it as a packaging material for electronic components such as liquid crystal.
- Japanese Patent Publication No. 63-125357 shows the method of forming the surface of the foamable styrene resin particles.
- a specific antistatic agent on the surface Japanese Patent Publication No. Sho 59-35 9
- the method of coating the surface of the expandable styrene resin particles with a specific antistatic agent exhibits antistatic performance. Therefore, there is a problem that the amount of the antistatic agent added increases, the flowability of the pre-expanded particles after the end of the pre-expansion deteriorates, and the filling of the inside of the mold at the time of molding the foam becomes insufficient.
- the olefin resin is modified with a specific hydrophilic monomer and further contains a surfactant, as disclosed in Japanese Patent Application Laid-Open No. 10-147660.
- a foamed molded article having excellent antistatic properties and exhibiting an antistatic effect immediately even by cracking, chipping, and washing with water can be obtained, but the polymerization efficiency of the hydrophilic monomer is poor, and the The problem is that the cost is high because of the high cost. Disclosure of the invention
- the inventors of the present invention have conducted studies to solve these problems, and as a result, after impregnating the styrene-modified olefin-based resin particles with a readily volatile blowing agent, the surfactant was added under pressure. It has been found that foaming resin particles having excellent antistatic properties can be obtained by mixing and impregnating, and the present invention has been accomplished.
- the styrene-modified olefin-based resin particles are impregnated with an easily volatile foaming agent to obtain foamable resin particles, and then the foamable resin particles 100 0.1 to 2.0 parts by weight of a surfactant per 10 parts by weight at a temperature of 10 to 30 ° C and a pressure of 0.05 to 0.3 OMPa to improve the foaming styrene
- a method for producing expandable styrene-modified resin-based resin particles for obtaining high-quality resin-based resin particles is provided.
- the expandable styrene-modified olefin-based resin particles obtained by the above method are pre-foamed by heating with steam at a gauge pressure of 0.01 to 0.1 MPa.
- a method for producing pre-expanded particles for obtaining pre-expanded particles is provided.
- the pre-expanded particles obtained by the above method are foamed and molded by heating with steam at a gauge pressure of 0.05 to 0.15 MPa to obtain a foamed molded article.
- a method for producing a molded article is provided.
- FIG. 1 is a schematic view of an apparatus for producing expandable resin particles of Examples and Comparative Examples. BEST MODE FOR CARRYING OUT THE INVENTION
- the present invention is characterized in that a foaming resin particle impregnated with a volatile foaming agent is impregnated with a surfactant under pressure.
- a high concentration of a surfactant can be present near the surface of the expandable resin particles, so that an excellent antistatic effect can be imparted to the expandable resin particles.
- the foaming resin particles collide with each other, so that the surfactant is firmly attached to the particles, and the surfactant is partially washed into the resin particles. Can also maintain the antistatic effect.
- the cross section of the molded body can also exhibit an antistatic effect.
- the case where the expandable resin particles, the pre-expanded particles, and the molded article have a surface specific resistance (antistatic level) of 1 ⁇ 10 12 ⁇ or less is defined as having an antistatic property.
- the surfactant When such a large amount of surfactant is used, the surfactant is foamed when the foamable resin particles are taken out, so that the foamed resin particles stick and become difficult to take out, which may adversely affect the moldability. For this reason, production may be hindered.
- the styrene-modified oil-based resin S particles used in the present invention means resin particles obtained by modifying a polyolefin-based resin with a polystyrene-based resin.
- the modification means simply impregnating the polyolefin-based resin particles with a styrene-based monomer and polymerizing it, impregnating the polyolefin-based resin particles with the styrene-based monomer, and performing graft polymerization. Means the case.
- polystyrene-based resin examples include resins derived from monomers such as styrene, monomethylstyrene, vinyl toluene, and chlorostyrene.
- Polyolefin resins include polyethylene resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-methyl methacrylate copolymer.
- polyethylene resins such as low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear low-density polyethylene, ethylene-vinyl acetate copolymer, and ethylene-methyl methacrylate copolymer.
- polypropylene-based resins such as polypropylene, propylene-ethylene copolymer, and propylene-11-butene copolymer, and those obtained by crosslinking these polymers.
- polyethylene resins are preferred.
- the amount of polystyrene resin is based on 100 parts by weight of polyolefin resin.
- the proportion is preferably from 25 to 500 parts by weight, more preferably from 50 to 400 parts by weight, even more preferably from 100 to 250 parts by weight. If the amount is less than 25 parts by weight, the characteristic that the rigidity of the polystyrene resin component is good is hardly exhibited. Further, since the retention of the volatile volatile agent is extremely deteriorated, it is difficult to reduce the density, and the foaming moldability is also poor. If the amount exceeds 500 parts by weight, it is not preferable because the polyolefin resin component has high elasticity and has poor oil resistance and good impact resistance. Further, in this case, styrene is not sufficiently absorbed into the polyolefin resin component, and styrene is polymerized alone, so that a large amount of polymer powder may be generated, which is not preferable.
- Styrene-modified polyolefin-based resin particles are described in, for example,
- polyolefin resin particles are dispersed and maintained in an aqueous medium. It is obtained by adding and polymerizing a styrene monomer.
- the shape of the polyolefin-based resin particles is not particularly limited, but is preferably cylindrical or substantially spherical in consideration of the filling property into a mold.
- the average particle size of the polyolefin resin particles is 0.2 to 1.1. Preferably it is 5 mm. If the average particle size is less than 0.2 mm, the retention of the foaming agent will be low, and it will be difficult to reduce the density, which is not preferable. On the other hand, when the thickness exceeds 1.5 mm, not only is the filling property deteriorated, but also it becomes difficult to reduce the thickness of the molded product, which is not preferable.
- the modification of the polyolefin-based resin particles is performed in an aqueous suspension.
- the aqueous medium constituting the aqueous suspension include water and a mixed medium of water and a water-soluble solvent (for example, lower alcohol).
- a water-soluble solvent for example, lower alcohol.
- water may be mixed with a water-soluble solvent in an amount of about 0.50% by weight.
- a dispersant can be used to keep the polyolefin resin particles dispersed in the aqueous medium.
- the dispersant is not particularly limited, and any known dispersant can be used. Specific examples include poorly soluble inorganic substances such as calcium phosphate, magnesium pyrophosphate, and magnesium oxide.
- the polyolefin-based resin particles in the aqueous suspension are impregnated with a styrene-based monomer and polymerized to modify the polyolefin-based resin particles.
- a polymerization initiator can be used for the polymerization of the styrenic monomer.
- the polymerization initiator those generally used as a suspension polymerization initiator of a styrene-based monomer can be used.
- a styrene-based monomer in which a polymerization initiator is dissolved is gradually added to an aqueous suspension of polyolefin-based resin particles, and polymerization is carried out at 80 to 100 ° C for 3 to 5 hours. It is more preferable to raise the temperature to 130 to 140 ° C. after the polymerization and to maintain the temperature for 1 to 3 hours, because the remaining styrene-based monomer is reduced and the shrinkage of the foam molded article is suppressed.
- the amount of the polymerization initiator to be used is preferably 0.1 to 0.9 part by weight based on 100 parts by weight of the styrene monomer. If the amount is less than 0.1 part by weight, the polymerization of the styrene-based monomer tends to be insufficient, and a large amount of the styrene-based monomer remains in the polyolefin-based resin particles. Use of more than 0.9 parts by weight of the polymerization initiator lowers the molecular weight of the polystyrene resin. In order to obtain good physical properties, the molecular weight of the styrene component is preferably about 200,000 to 400,000, but if it exceeds 0.9 part by weight, it is often the case that a value lower than this is obtained.
- foamable resin particles can be obtained by impregnating the styrene-modified polyolefin-based resin particles during or after polymerization with a volatile volatile foaming agent.
- volatile foaming agents examples include hydrocarbons such as propane, butane, isobutane, pentane, isopentane, cyclopentane, and hexane, HCFC-142b, HFC-134a, HCFC-123. Can be used alone or in combination of two or more.
- the amount of the foaming agent to be used is determined by the expansion ratio of the target molded product, but is preferably 10 to 30 parts by weight based on 100 parts by weight of the styrene-modified polyolefin-based resin particles. Good
- a foaming aid such as toluene, cyclohexane, or ethylbenzene may be used to facilitate foaming and molding of the foamable styrene-modified polyolefin-based resin particles.
- the amount of the foaming aid is preferably 2 parts by weight or less based on 10.0 parts by weight of the styrene-modified polyolefin-based resin particles.
- the expandable resin particles obtained as described above can be mixed with a surfactant under pressure to obtain expandable styrene-modified olefin resin particles of the present invention.
- surfactant examples include nonionic surfactants such as polyoxetylene alkylamine, polyethylene glycol fatty acid ester, alkylgenolamide, alkylgenolamine, and polyalkyleneglycol derivatives, and alkyl.
- Anionic surfactants such as sulfonates, alkylbenzene sulfonates, and alkyl phosphates; cationic surfactants such as aliphatic alkyl quaternary ammonium salts and trialkylbenzylammonium salts;
- amphoteric surfactants such as alkyl imidazolium solvents.
- a surfactant having a total carbon number in the range of 5 to 20 it is preferable to use a surfactant having a total carbon number in the range of 5 to 20.
- the use of a surfactant dissolved in water or an aqueous medium is particularly preferred in that the surfactant can be uniformly attached to the surface of the expandable resin particles in a short time.
- surfactants include aliphatic alkyl quaternary ammonium salts, sodium alkylbenzenesulfonate, and lauryl betaine.
- the concentration for dissolution is preferably 15 to 75% by weight. If the concentration to be dissolved is less than 15% by weight, the efficiency of impregnating the surface of the expandable resin particles with the antistatic agent is deteriorated. It becomes difficult to attach the surfactant uniformly.
- the aqueous medium means water, a mixed medium of water and a water-soluble solvent (for example, lower alcohol) and the like.
- cationic surfactants are preferred because they do not impair the excellent antistatic properties and the fluidity of the expandable resin particles and do not adversely affect the filling property during molding.
- aliphatic alkyl quaternary ammonium salts are particularly preferred.
- Aliphatic al Kill quaternary ammonium salt has the general formula (1)
- R1 is preferably the same or different, and is an optionally branched alkyl group having 1 to 17 carbon atoms. Further, among the four R1, three are preferably alkyl groups having 1 to 3 carbon atoms. In addition, the remaining one of the four R1s is preferably an alkyl group having 5 to 20 carbon atoms, more preferably 9 to 14 carbon atoms, and particularly preferably 12 carbon atoms. . Particularly preferred aliphatic alkyl quaternary ammonium salts include salts represented by the following general formula (2).
- R2 means a linear or branched alkyl group having 5 to 20 carbon atoms).
- R2 is preferably a linear alkyl group.
- ESL is included when R 2 is a linear alkyl group.
- a surfactant that is liquid at a temperature of 10 to 30 ° C can uniformly adhere the surfactant to the surface of the expandable resin particles in a short time without being dissolved in an aqueous medium.
- a surfactant Polyoxy Examples include ciethylene laurylamine, polyoxyethylene oleyl ether, and polyoxyethylene glycol monoolate.
- the amount of the surfactant to be added is 0.1 to 2.0 parts by weight, preferably 0.5 to 1.5 parts by weight, based on 100 parts by weight of the foamed resin particles. If the amount is less than 0.1 part by weight, the desired antistatic property cannot be imparted to the expandable styrene-modified olefin-based resin particles, the pre-expanded particles, and the foamed molded product, which is not preferable. On the other hand, if the content exceeds 2.0 parts by weight, the expandable styrene-modified olefin-based resin particles and the pre-foamed particles become sticky, which makes the handling difficult, which is not preferable. Furthermore, it is difficult to fill the molding die with the pre-foamed particles, and the obtained foamed molded product is sticky, and dust is more likely to adhere thereto, which is not preferable.
- the impregnation of the surfactant is performed under pressure. Specifically, the impregnation is performed at an impregnation temperature of 10 to 30 ° C and an impregnation pressure of 0.05 to 0.30 MPa. A more preferred impregnation temperature is 15 to 25 ° C, and an impregnation pressure is 0.10 to 0.25 MPa.
- the impregnation temperature is less than 10 ° C and the impregnation pressure is less than 0.05 MPa, the surfactant will not penetrate well into the surface of the expandable resin particles, and sufficient antistatic properties will be obtained in the cross-section of the foamed molded product. I can't.
- the impregnation temperature exceeds 30 ° C and the impregnation pressure exceeds 0.30 MPa, the rate of penetration of the surfactant into the foamable resin particles is high. Sufficient antistatic properties cannot be obtained.
- the apparatus that can be used for mixing the expandable resin particles and the surfactant is not particularly limited, and includes, for example, a closed-type rotary mixer.
- the expandable styrene-modified olefin resin particles obtained as described above are pre-expanded to a predetermined density by a known method (for example, heating with a gauge pressure of 0.01 to 0.1 L OMPa steam). And pre-expanded particles. Further, the pre-expanded particles are filled in a mold, and heated again to heat-bond the pre-expanded particles to each other, whereby a foam molded article can be obtained.
- the heating medium is
- the density of the foam molded body is preferably from 12 to 200 kg / m 3 . If the density is lower than 12 kg / m 3 , sufficient strength cannot be obtained, and if the density is higher than 20 Okg / m 3 , the weight cannot be reduced, which is not preferable.
- the foamed molded article of the present invention can be used for various applications, and can be suitably used particularly for a returnable box of a mechanical part such as an automobile part, a cushioning packaging material of an electric product, and the like.
- the bulk multiple of the expanded particles was determined by the following equation in accordance with JIS K 6767.
- V Bulk volume of expanded particles (cm 3 )
- the surface of the foamed molded product was washed with pure water at a rate of 10 Oml per second for 1 minute from a tap having a diameter of 1 cm, and then the adhered water on the surface of the foamed molded product was removed with a paper roll. , Leave it in a constant temperature and humidity room with a humidity of 65% for 3 days or more, Measure the surface resistivity of the foamed molded product surface (C) washed with water.
- the surface resistivity is measured according to JISK 6911 using a super insulation meter SM-10E manufactured by Toa Denpa Kogyo. In any of (a), (b) and (c), if the surface specific resistance value is 1 ⁇ 10 12 ⁇ or less, it is determined that the foamed molded article has antistatic properties.
- Preparation of sample 5 Omg of styrene-modified polyethylene-based resin particles were divided into two along a center line with a cartridge, and immersed in 1 Oml of THF at 20 ° C for 24 hours to dissolve the styrene component in THF. Use THF solution as sample for measurement o
- the average molecular weight (Mw) of the polymer was measured by GPC (gel permeation ion chromatography) under the following conditions.
- Measuring device High-speed GPC device HLC-8020 manufactured by Tosoh Corporation
- the molecular weight distribution of the sample is within a range where the logarithm of the molecular weight and the count number of the calibration curve prepared from several monodisperse polystyrene standard samples are linear. The measurement conditions included in were selected.
- the calibration curve of polystyrene has a weight average molecular weight of 2.7. 4x l 0 3, 1. 91 x 10 ⁇ 1. 02x l 0 5, 3. 55x l 0 5, 2. 8 9x 10 6, 4. 48 x 10 6 is a Tosoh one company made six polystyrene It was prepared using a standard sample (TSK standard polystyrene).
- polyethylene containing 5% vinyl acetate (Novatek EVA LV121 manufactured by Nippon Polyethylene Co., Ltd.) was converted into particles having an average particle size of lmm using an extruder.
- a suspension of 12 kg of these particles in the aqueous medium, 40 g of dicumyl peroxide 85 s benzoyl peroxide and 4 g of t-butyl peroxide dissolved in 23 kg of styrene were gradually added, and 90 ° C
- the polymerization was carried out for 4 hours. Thereafter, the temperature was raised to 140 ° C. and maintained at the same temperature for 2 hours.
- the styrene-modified polyethylene-based resin particles (molecular weight: 100 parts by weight of the above polyethylene and 202 parts by weight of polystyrene) : About 300,000).
- R2 is a salt containing an alkyl group salt of — (CH 2 ) uCHs. %) 150 g into pressure vessel 2 Then, it was injected into the V-type blender 1 by pressurizing with nitrogen. Next, the mixture was stirred for 30 minutes under the conditions of a V-type blender internal temperature of 15 ° C. and an internal pressure of 0.17 MPa, and then foamable resin particles were taken out.
- 3 is a foaming agent holding container
- 4 is a surfactant inlet
- 5 is a thermometer
- 6 is a pressure gauge
- 7 is a depressurizing valve
- 8 is a particle inlet and outlet
- 9 is a hot or cold water inlet.
- Reference numeral 10 denotes a hot or cold water outlet
- 11 denotes the rotation direction of the stirrer of the V-shaped blender.
- the obtained foamed resin particles were immediately placed in a batch-type foaming machine, pre-foamed to a bulk factor of 20 times with steam at a gauge pressure of 0.03 MPa to obtain pre-foamed particles, and then stored at room temperature for 24 hours. .
- the pre-expanded particles were filled in a mold of a 400 ⁇ 300 ⁇ 100 mm molding machine, and steam with a gauge pressure of 0.08 MPa was injected for 60 seconds to be heated and foamed. After cooling for 5 minutes, the molded foam was taken out.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- a foam molded article was obtained in the same manner as in Example 1, except that the aqueous solution of the aliphatic alkyl quaternary ammonium salt was changed to 225 g.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the surface resistivity of the foamed molded product.
- a foam molded article was obtained in the same manner as in Example 1, except that the aqueous solution of the aliphatic alkyl quaternary ammonium salt was changed to 450 g.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the surface resistivity of the foamed molded product.
- a foamed molded article was obtained in the same manner as in Example 1, except that 150 g of S-100) was used.
- Table 1 shows the type, amount, addition time and mixing conditions of the surfactant, and the surface resistivity of the foamed molded product.
- sodium dodecylbenzenesulfonate (25% aqueous solution, Kao Corporation Neoperex F—25) is a yellow transparent viscous liquid at room temperature (25 ° C).
- Table 1 shows the type, amount, addition time and mixing conditions of the surfactant, and the surface resistivity of the foamed molded product.
- a foam molded article was obtained in the same manner as in Example 1, except that the aqueous solution of the aliphatic alkyl quaternary ammonium salt was changed to 300 g.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the surface resistivity value of the foam molded article.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- a foam molded article was obtained in the same manner as in Example 1 except that butane was changed to 1.5 kg of pentane (isopentane: normal pentane ratio: 2: 8).
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- a V-type blender 1 capable of sealing with a pressure resistance of 50 liters the same as in Example 1 and an aqueous solution of styrene-modified polyethylene resin particles 15 kg and an aliphatic alkyl quaternary ammonium salt 450 g was added, and while sealing and stirring, 2 kg of butane (isobutane: normal butane ratio: 3: 7) was injected. Next, the inside temperature of the V-shaped blender was maintained at 70 ° C for 4 hours, and then cooled to 15 ° C, and the expandable resin particles were taken out.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- Comparative Example 2 A foam molded article was obtained in the same manner as in Example 1, except that the aqueous solution of the aliphatic alkyl quaternary ammonium salt was changed to 24 g. Table 1 shows the type, amount, addition time, mixing condition, and surface resistivity of the foamed molded product.
- Expandable resin particles were obtained in the same manner as in Example 1, except that the aqueous solution of the aliphatic alkyl quaternary ammonium salt was 900 g. However, foaming when removing expandable resin particles from V-type blender-1 is severe, and the flow of pre-expanded particles obtained therefrom is poor. Can not get. Table 1 shows the types, amounts, timings and mixing conditions of surfactants.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- Example 2 The same V-type renderer as in Example 1 that can be sealed with a pressure resistance of 50 liters 1
- 15 kg of styrene-modified polyethylene-based S-like particles, the same as in Example 1 were calorie-closed and stirred.
- 2 kg of butane isobutane: normal butane ratio: 3: 7
- the temperature in the V-type blender was maintained at 70 ° C for 4 hours, and then cooled to 35 ° C.
- the pressure relief valve 7 was opened, and the internal pressure was set to 0 MPa (atmospheric pressure).
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the specific surface resistance of the foamed molded product.
- the pressure release valve 7 was opened, and the internal pressure was set to OMPa (atmospheric pressure). Then, 150 g of an aqueous solution of an aliphatic alkyl quaternary ammonium salt (same as in Example 1) was placed in the V-type blender 11 with the pressure release valve 7 kept open. Next, the mixture was stirred for 30 minutes at a V-type blender temperature of 15 ° C and an internal pressure of OMPa, and then the expandable resin particles were taken out.
- OMPa atmospheric pressure
- Example 15 kg of the same styrene-modified polyethylene resin particles as in Example 1 were applied to the same V-type renderer 11 as in Example 1 which was capable of sealing with a pressure resistance of 50 liters, tightly closed and stirred.
- 2 k of butane (the ratio of isobutane: normal butane was 3: 7) was weighed into a pressure vessel 2 connected to the V-shaped blender 11 and pressurized by pressurizing with nitrogen. Then, the temperature in the V-shaped blender was maintained at 70 ° C for 4 hours, and then cooled to 5 ° C.
- an aqueous solution of an aliphatic alkyl quaternary ammonium salt (same as in Example 1) was placed in a pressure vessel, and the mixture was pressed into a V-type blender-1 by pressurizing with nitrogen. Next, the mixture was stirred for 30 minutes at a temperature of 5 ° in the V-type blender (with an internal pressure of 0.06 MPa), and then the expandable resin particles were taken out.
- Table 1 shows the type, amount, timing of addition and mixing conditions of the surfactant, and the surface specific geometric value of the foamed molded product.
- Comparative Example 4 a butane 13.3 aliphatic 7 alkyl third grade ammonium :: ⁇ unsalted 0.5 After impregnation 30 ° C 0.35MPa 1 X 10 u 1X10 U 3X10 13
- Comparative Example 5 a butane 13.3 aliphatic alkyl quaternary Anmoniumu salt 0.5 impregnated After 35.
- Styrene-modified polyethylene-based resin particles composed of 100 parts by weight of polyethylene described in Example 1 and 202 parts by weight of polystyrene (molecular weight: about 300,000) o
- Styrene-modified polyethylene resin S particles containing 100 parts by weight of polyethylene described in Example 10 and 105 parts by weight of polystyrene (molecular weight: about 300,000)
- Styrene-modified polyethylene resin S particles comprising 100 parts by weight of the polyethylene described in Example 11 and 33 parts by weight of polystyrene (molecular weight: about 350,000)
- Butane Volume ratio of isobutane to normal malt is 3: 7.
- Pentane Isopentane to normal pentane with a volume ratio of 2 to 8. *: Severe foaming at the time of extraction from the reactor. Poor flowability of pre-expanded granules, molding not possible due to poor filling. From Example 1 and Comparative Examples 4 to 7, a foaming molded article having an excellent surface resistivity is obtained by impregnating the foaming resin particles with the surfactant under the temperature and pressure conditions in the range of the present invention. be able to.
- Example 3 From Example 3 and Comparative Example 1, by impregnating with a surfactant after impregnation with a foaming agent, a foam molded article having an excellent surface resistivity can be obtained.
- the foamed molded body obtained from the foamable styrene-modified resin-based resin particles contains a surfactant not only on the surface but also inside thereof, so that it is cracked, chipped, and prevented from being charged even when washed with water. Has the property. Therefore, it can be used as a packaging material for electronic components such as liquid crystals.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB200480003452XA CN100406504C (zh) | 2003-04-04 | 2004-03-22 | 发泡性苯乙烯改性烯烃基树脂粒子、预发泡粒子及发泡成型制品的制备方法 |
US10/541,589 US7901602B2 (en) | 2003-04-04 | 2004-03-22 | Expandable styrene-modified olefin resin particle, pre-expanded particle, and process for producing molded foam |
JP2005505187A JP4105195B2 (ja) | 2003-04-04 | 2004-03-22 | 発泡性スチレン改質オレフィン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法 |
KR1020057017290A KR100660432B1 (ko) | 2003-04-04 | 2004-03-22 | 발포성 스티렌 개질 올레핀계 수지입자, 예비발포 입자 및발포 성형체의 제조 방법 |
AT04722466T ATE555154T1 (de) | 2003-04-04 | 2004-03-22 | Expandierbare teilchen aus styrolmodifiziertem olefinharz, vorexpandierte teilchen und verfahren zur herstellung eines expandierten formgegenstands |
EP04722466A EP1612239B1 (en) | 2003-04-04 | 2004-03-22 | Expandable styrene-modified olefin resin particles, pre-expanded particles, and method for producing an expanded molded article |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2003-101557 | 2003-04-04 | ||
JP2003101557 | 2003-04-04 |
Publications (1)
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WO2004090029A1 true WO2004090029A1 (ja) | 2004-10-21 |
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PCT/JP2004/003844 WO2004090029A1 (ja) | 2003-04-04 | 2004-03-22 | 発泡性スチレン改質オレフィン系樹脂粒子、予備発泡粒子及び発泡成形体の製造方法 |
Country Status (8)
Country | Link |
---|---|
US (1) | US7901602B2 (ja) |
EP (1) | EP1612239B1 (ja) |
JP (1) | JP4105195B2 (ja) |
KR (1) | KR100660432B1 (ja) |
CN (1) | CN100406504C (ja) |
AT (1) | ATE555154T1 (ja) |
TW (1) | TWI250183B (ja) |
WO (1) | WO2004090029A1 (ja) |
Cited By (6)
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WO2010074246A1 (ja) | 2008-12-26 | 2010-07-01 | 積水化成品工業株式会社 | 予備発泡粒子、その製造方法及び発泡成形体 |
JP2010144004A (ja) * | 2008-12-17 | 2010-07-01 | Sekisui Plastics Co Ltd | 予備発泡粒子、その製造方法及び発泡成形体 |
JP2010222546A (ja) * | 2009-03-25 | 2010-10-07 | Sekisui Plastics Co Ltd | カーボン含有改質ポリスチレン系樹脂発泡粒子とその製造方法、カーボン含有改質ポリスチレン系樹脂発泡成形体とその製造方法 |
JP2011162749A (ja) * | 2010-02-15 | 2011-08-25 | Sekisui Plastics Co Ltd | 予備発泡粒子、その製造方法及び発泡成形体 |
JP2012214725A (ja) * | 2011-03-31 | 2012-11-08 | Sekisui Plastics Co Ltd | 帯電防止性を有する発泡性スチレン系樹脂粒子、その製造方法、予備発泡粒子及び発泡成形体 |
US8329294B2 (en) * | 2006-02-28 | 2012-12-11 | Sekisui Plastics Co., Ltd. | Styrene-modified polypropylene type resin particle, foamable styrene-modified polypropylene type resin particle, styrene-modified polypropylene type resin foamed particle, styrene-modified polypropylene type resin foamed molded product, and production methods thereof |
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US7837812B2 (en) | 2004-05-21 | 2010-11-23 | Ati Properties, Inc. | Metastable beta-titanium alloys and methods of processing the same by direct aging |
KR20100110788A (ko) * | 2007-12-28 | 2010-10-13 | 세키스이가세이힝코교가부시키가이샤 | 난연성 발포성 스티렌계 수지 입자 및 그 제조 방법 |
EP2452969A1 (de) * | 2010-11-11 | 2012-05-16 | Basf Se | Verfahren zur Herstellung von expandierbaren thermoplastischen Partikeln durch Nachimprägnierung |
JP7012960B2 (ja) | 2018-03-29 | 2022-01-31 | 株式会社奥村組 | カッタ盤およびそれを備えるシールド掘進機 |
CN116875128A (zh) * | 2023-07-18 | 2023-10-13 | 绍兴翔宇绿色包装有限公司 | 一种离型膜及其制备方法 |
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- 2004-03-22 EP EP04722466A patent/EP1612239B1/en not_active Expired - Lifetime
- 2004-03-22 US US10/541,589 patent/US7901602B2/en not_active Expired - Fee Related
- 2004-03-22 JP JP2005505187A patent/JP4105195B2/ja not_active Expired - Fee Related
- 2004-03-22 CN CNB200480003452XA patent/CN100406504C/zh not_active Expired - Fee Related
- 2004-03-22 WO PCT/JP2004/003844 patent/WO2004090029A1/ja active Application Filing
- 2004-03-22 AT AT04722466T patent/ATE555154T1/de active
- 2004-03-22 KR KR1020057017290A patent/KR100660432B1/ko not_active IP Right Cessation
- 2004-03-24 TW TW093107995A patent/TWI250183B/zh not_active IP Right Cessation
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Publication number | Priority date | Publication date | Assignee | Title |
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US8329294B2 (en) * | 2006-02-28 | 2012-12-11 | Sekisui Plastics Co., Ltd. | Styrene-modified polypropylene type resin particle, foamable styrene-modified polypropylene type resin particle, styrene-modified polypropylene type resin foamed particle, styrene-modified polypropylene type resin foamed molded product, and production methods thereof |
JP2010144004A (ja) * | 2008-12-17 | 2010-07-01 | Sekisui Plastics Co Ltd | 予備発泡粒子、その製造方法及び発泡成形体 |
WO2010074246A1 (ja) | 2008-12-26 | 2010-07-01 | 積水化成品工業株式会社 | 予備発泡粒子、その製造方法及び発泡成形体 |
KR20110115567A (ko) | 2008-12-26 | 2011-10-21 | 세키스이가세이힝코교가부시키가이샤 | 예비 발포 입자, 그 제조 방법 발포 성형체 |
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JP2010222546A (ja) * | 2009-03-25 | 2010-10-07 | Sekisui Plastics Co Ltd | カーボン含有改質ポリスチレン系樹脂発泡粒子とその製造方法、カーボン含有改質ポリスチレン系樹脂発泡成形体とその製造方法 |
JP2011162749A (ja) * | 2010-02-15 | 2011-08-25 | Sekisui Plastics Co Ltd | 予備発泡粒子、その製造方法及び発泡成形体 |
JP2012214725A (ja) * | 2011-03-31 | 2012-11-08 | Sekisui Plastics Co Ltd | 帯電防止性を有する発泡性スチレン系樹脂粒子、その製造方法、予備発泡粒子及び発泡成形体 |
Also Published As
Publication number | Publication date |
---|---|
TW200426176A (en) | 2004-12-01 |
EP1612239B1 (en) | 2012-04-25 |
JPWO2004090029A1 (ja) | 2006-07-06 |
US7901602B2 (en) | 2011-03-08 |
EP1612239A1 (en) | 2006-01-04 |
EP1612239A4 (en) | 2006-04-19 |
US20060038311A1 (en) | 2006-02-23 |
CN1747990A (zh) | 2006-03-15 |
JP4105195B2 (ja) | 2008-06-25 |
CN100406504C (zh) | 2008-07-30 |
KR100660432B1 (ko) | 2006-12-22 |
ATE555154T1 (de) | 2012-05-15 |
TWI250183B (en) | 2006-03-01 |
KR20050111772A (ko) | 2005-11-28 |
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