TW201202317A - Expandable polystyrene type resin particle and production method thereof, polystyrene type resin pre-expanded particle, polystyrene type resin expanded form, thermoplastic resin pre-expanded particle and production method thereof, and thermoplastic resi - Google Patents

Abstract

The present invention relates to an expandable polystyrene type resin particle containing bubbles, wherein the value N which is denoted by the formula N=n/(1/ ρ ) is 400 or higher, wherein ''n'' represents the number of bubbles per square millimeter existing in a predetermined area of a cross-section passing through the center of the expandable polystyrene type resin particle containing bubbles but excluding an area of 200 μ m from a surface of the particle, and '' ρ '' represents a bulk density (g/cm<SP>3</SP>) of the particle. Moreover, a thermoplastic resin containing a forming agent which has been obtained by melting and kneading the thermoplastic resin and the forming agent in a resin supplying apparatus is cut immediately after being pushed through small holes of a die to a cooling media, and expanded in the cooling media to obtain a thermoplastic resin pre-expanded particle having a bulk expansion multiple of 1.6 or more, and separated from the cooling media, to obtain the thermoplastic resin pre-expanded particle. Moreover, an expandable polystyrene type resin particle, which is obtained by melting and kneading a polystyrene type resin and a foaming agent in a resin supplying apparatus and pushing the melted polystyrene type resin containing the foaming agent through small holes of a die, and cooling and cutting the resin, has a white degree of 75 or less which is measured based on JIS K7105: 1981.

Description

201202317 VI. [Technical Field] The present invention relates to a foamable polystyrene-based resin particle which is excellent in mechanical strength such as bending strength, compressive strength, and impact resistance even at a high expansion ratio. The polystyrene resin foam molded body. Further, the present invention relates to a thermoplastic resin-prepared foamed particle for producing a thermoplastic resin foam molded article such as a polystyrene-based resin foam molded body, and a method for producing the same, and more specifically relates to a melt-containing content The thermoplastic resin of the foaming agent is extruded from a small hole of a mold into a cooling medium such as water, and is cut immediately to produce a resin particle. The manufacturing process of producing the foamable thermoplastic resin particle by a so-called melt extrusion method is performed. The resin particles are foamed in a cooling medium to directly produce a thermoplastic resin-prepared foamed particle used in the production of the foamed molded article. Further, the present invention relates to a polystyrene-based resin foam molded article having excellent strength, and the foaming agent is stably dispersed from the foamable resin particles, and can be stored during a long period of time (beads). A foaming polystyrene-based resin particle. This patent application claims Japanese Patent Application No. 2010-72319, filed on March 26, 2010 in Japan, and Japanese Patent Application No. 2010-72320, filed on March 26, 2010, and on March 26, 2010. Japanese Patent Application No. 2010-72321, the priority of which is hereby incorporated by reference. [Prior Art] Polyphenylene 4 322950 obtained by foam molding of expandable polystyrene resin particles

201202317 Ethylene-based resin foam molded body is widely used as a heat insulating material or a packing material due to its resistance to compression, light weight, and barrier properties. In the field of high foaming multiplication of a foamed molded body which is close to a small amount of resin, it is urgent to develop a high-strength = field-based resin foaming into a hybrid even if it is a high foaming multiple. i. The method for producing the ethyl styrene foamable polystyrene resin particles is to melt the foaming agent into the 5 in the melted polystyrene resin in the extruder, and to melt the resin containing the foaming agent. Extrusion from the small hole attached to the front end of the extruder to the cooling liquid, the extrusion is cut off at the same time as the high-speed rotary knife, and the extrudate is cooled and solidified by contact with the liquid to obtain foaming property. Polystyrene-based resin particles, that is, a so-called melt-melt method, and a method for producing foamable polystyrene glycol particles by a melt extrusion method, for example, a technique disclosed in Patent Document No. 2 is proposed. The method disclosed in Patent Document 1 discloses a method for producing foamable bismuth diester particles having the following steps. The tree is melted and kneaded (step 丨) by the thermoplastic resin (A) and the foaming agent (B), and the obtained melted kneaded material is extruded from the die head to a temperature/pressure at which the melted kneaded material does not foam. After being extruded into the heated/pressurized heating and pressing liquid, it is cut off immediately (step 2), and the obtained particles are cooled at normal pressure to a temperature at which no foaming is performed (step 3), and the differential thermal analysis device is used. (DSC) When measuring a foamable thermoplastic resin, the temperature in the temperature range of 30 to (τι+15) C at the low temperature side is taken as the south peak temperature at the low temperature side among the two endothermic peaks appearing in the region of 40 to 120 Ϊ. 'Aging treatment in a liquid at normal pressure (step 4). 322950 5 201202317 Patent Document 2 discloses a method of producing foamable particles from a styrene-based resin recycled product. (a) pulverizing the recovered product of the styrene resin to prepare a batch of the pulverized product; (b) determining the content of butadiene contained in each batch of the resin; (c) different single batch or different butadiene content The mixture of the styrene resin is adjusted to a total of 1 to 6 mass%; The extruder of the net; (e) the pulverized product is melted in the extruder, the foreign matter is removed by the metal mesh, and the foaming agent is pressed into the melt, and the molten metal is attached from the front end of the extruder. In the case of extrusion, the molten material is cut and rapidly cooled to suppress foaming, and foaming particles are formed. Further, conventionally, the expandable polystyrene resin particles are produced by a melt extrusion method. The method disclosed, for example, is disclosed in Patent Documents 3 and 4. Patent Document 3 discloses a method for producing a pre-expanded particle of a thermoplastic resin, in which an thermoplastic resin is melted using an extruder, and a foaming agent is mixed, followed by Cool down And the foam is extruded to a diameter of 1.5 to 10.5 times the diameter of the nozzle of the extrusion die, and the extruded foam obtained before the completion of the foaming after the completion of the foaming is cut off as In the patent document 4, 100 parts by mass of a mixed resin of 70 to 90% by mass of a styrene-based resin and 10 to 30% by mass of an olefin-based resin, and 0 to 15 parts by mass of a styrene-based elastomer are disclosed. a mixture of a resin composition and a volatile blowing agent is extruded in a liquid while cutting the obtained foam

6 322950 _ S 201202317 !·The raw particles are also less than 5 times and the volatile organic compound content other than the volatile foaming agent is 5QQppm or less in the stupid ethyl ester foaming! · Raw particles, X in Patent Document 4 A method for producing a styrene-based resin foamable particle is disclosed, which is a mixed resin of 7 to 9 wt% of styrene resin and 10 to 9% by mass of an olefin resin, and a styrene-based elastomer. The body is supplied to the extruder at a mass ratio of 15 parts by mass, and is heated and melted to become a 1-fat composition, and the amount of the volatile foaming agent is 3 to 15 f by pressing 'with respect to 100 parts by mass of the resin composition' on the way in the extruder. For the portion, the molten tree broth containing the foaming agent is extruded in the (four) towel, and the foaming of the resin is suppressed to 1.5 times or less... while the resin is cut in the liquid towel to obtain a volatile hair. An expandable particle having a volatile organic compound content of 500 ppm or less other than the foaming agent. In the prior art, a method for producing expandable polystyrene resin particles by a melt extrusion method is disclosed, for example, in the techniques disclosed in Patent Documents 5 and 6. Patent Document 5 discloses a method for producing a styrene resin foamable particle, in which a styrene resin is melted in an extruder, and a foaming agent is pressed into a melted resin to contain a foaming agent. The molten resin is directly extruded into a cooling liquid to form a resin into a foamable particle, and the foaming agent is selected to have a boiling point of 20 to 60. (: The relatively high ^ 'The molten resin is extruded from the extruder at a low temperature of 16 〇 or less and a high pressure of 2 MPa (Megapasca 丨) or higher, and the cooling liquid is set to 60 t at normal pressure. In the following Patent Document 6, a method for producing foamable thermoplastic resin particles is described as a thermoplastic resin such as polystyrene, a foaming agent such as butyl baking, and a phase 7 322950 201202317

Si: The thermoplastic resin of the mass fraction is melted and kneaded with less than 1,5 parts by mass of the talc powder, and then extruded from the extrusion hole of the die head, and extruded, and immediately cooled and cooled. The relationship between the color of the polyphenylene-based resin particles (especially whiteness) and the mechanical strength of the foamed molded article obtained by using the polystyrene-based resin particles as a raw material is known, for example, as disclosed in Patent Document 7. Know the technology. Patent Document 7 discloses a polystyrene-based resin particle which is obtained by suspending an ethylene-based polymer particle in an aqueous medium as a seed crystal, and adding a styrene-based monomer while swelling it. The polystyrene resin particles used for producing the expandable polystyrene resin particles are produced by a seed polymerization method, and the whiteness measured by an integrating sphere type color difference meter is 40 to 60. Further, the polystyrene resin particles of Patent Document 7 are particles produced by a seed polymerization method, and the expandable polystyrene resin particles by melt extrusion method are completely in the whiteness of the process or the resin particles. different. [PATENT DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Bulletin 8 322950

S 201202317 [Summary of the Invention] (Problems to be Solved by the Invention) However, the above-mentioned prior art has the following problems. The manufacturing method of Patent Document 1 is a method for obtaining preliminary expanded particles having a large crystal grain diameter. However, if the diameter of the cell in the bubble structure of the preliminary expanded particle is increased, the strength of the foamed molded article obtained by foam molding the expanded particles in the mold is lowered. In addition, the thermal conductivity is high, and the barrier property is too much. In the production method of Patent Document 2, when the foamable particles obtained are preliminarily foamed, the obtained preliminary expanded particles have the outer layer portion. The bubble of the bubble has a small number of bubbles and the bubble structure k is foamed in the mold to obtain the surface smoothness of the filament (4). However, the #发/&amp;formed body is made of pre-foamed particles, because in the internal = 2 dressings, the money in the mold is obtained in the mold. The frequency is small. The number is provided even if the high foaming multiple is high. The two 2 fruits are t-bubbles. This E-winter resin is also a 'patent literature; 3's job will be foamed into its straight county (four) mold nozzle material, cut from the foam of the hunting, to obtain the preliminary foaming particles = U to 讥When the shape of the mouth is _, the shape of the mouth is S) (4) ^ = in the column shape (the sprayed particles are not recorded as the axis (4). The particles of the preliminary foaming of the material (4) are difficult to fill, and are filled into _ ^ light ligament ratio Spherical filling, gaps are likely to occur between the particles. Due to the inside, it is difficult to be foamed in the mold. The foamed molded body of 322950 9 201202317 has a pit, which has a poor appearance and mechanical strength reduction. The manufacturing method of the document 4 is a step of obtaining the expandable resin particles by the melt extrusion method; (2) the step of heating the obtained foamable resin = sub-heat to obtain the preliminary expanded particles; (3) The obtained preliminary foamed particles are filled in a cavity of a molding die, heated, and molded in a mold to obtain various steps of the step of foaming the molded body to produce a foamed molded body. Low production efficiency, requiring foaming resin particles or pre-expanded particles In the production method of the expandable polystyrene resin particles of Patent Document 5, in the production of the foamable resin particles by the melt extrusion method, the molten resin is extruded in a cooling liquid at normal pressure. Therefore, it is not possible to suppress the occurrence of bubbles in the obtained expandable polystyrene resin particles, and the bulk density is lowered, and the transportation efficiency is lowered. Further, since foaming occurs, the resin particles are broken and are easily disintegrated. When the foamed molded article produced by using the expandable polystyrene resin particles having a high whiteness during foaming has a mechanical strength lowering, the foaming polystyrene resin particles having a high whiteness during foaming are used. Since the foaming agent is fast to escape, the storage period (hereinafter referred to as particle life) is short. Therefore, it is difficult to store for a long period of time. The manufacturing method of Patent Document 6 is mainly used as a blowing agent, and is released in the agent. The particle life is short, and there is a case where it is not possible to store it for a long period of time. In addition, in the manufacturing method of Patent Document 6, the calcination is mainly used as a hair/packing agent in the pressurized water temperature as described in the examples to 9 generations. Heating 322950 10 201202317 Manufactured under the conditions of a pressurized water pressure of 10 to 15 kg/cm2. When the foaming polystyrene-based resin particles are produced under these conditions, the molten resin is extruded in the twisted water and cut to completion. Foaming occurs between the curing, and it is estimated that a foaming polystyrene resin miscellaneous having a miscellaneous density of less than 0.58 g/cm3 and a high whiteness is obtained. Resin tweezers also have a low bulk density of resin particles due to foaming, and require an extra space for storage or transportation due to an increase in the volume of a certain mass, and the resin particles are broken and easily disintegrated due to foaming. And the problem that the mechanical strength of the foamed molded article produced is lowered, etc. Patent Document 7 for producing polystyrene resin particles by a seed polymerization method is the object of the present invention, and by melt extrusion method. The above problem of the foaming polyphenylene (IV) fine particle is irrelevant. The present invention has been made in view of the above, and an object of the invention is to provide a foamable polystyrene resin particle which can produce a polystyrene material or a resin foam molded article having high strength even at a multiple expansion ratio, and a method for producing the same . Further, an object of the present invention is to provide a pre-expanded particle for directly forming a foamed molded article by a melt extrusion method, and to obtain a foamed molded article excellent in filling property and excellent in strength in a molding die cavity. A method for producing a thermoplastic resin-prepared expanded particle. Further, an object of the present invention is to provide a foamable polystyrene resin particle which is excellent in the strength of a polystyrene resin which is excellent in strength and which is stable in dispersion and has a long particle life. (Means for Solving the Problem) In order to achieve the above object, the first invention of the present invention provides a foam-containing expandable polystyrene resin particle containing a foaming agent and bubbles in a polyphenylene 322950 11 201202317 olefin resin particle. When the number of bubbles existing in the surface of the cross section of the center of the foamed polystyrene-based resin particle containing the bubble is 200 Å, the number of bubbles is η/mm2, and the bulk density is pg/cm3. The foamable polystyrene-based resin particles having a bubble value of 400 or more calculated by the formula (1). N=n/(1/p) (1) In the foam-containing expandable polystyrene resin particles, the N value is preferably in the range of 400 to 2,000. The foamable polystyrene resin particles containing bubbles preferably have a bulk density of 0.4 g/cm3 or more. According to a second aspect of the present invention, there is provided a method for producing foamable polystyrene resin particles containing bubbles, wherein a foaming agent and a foaming agent are added to a polystyrene resin in a resin supply device. The molten resin containing the foaming agent is extruded from a small hole of a mold attached to the tip end of the resin supply device into the cooling liquid, and the extrudate is cut while being extruded, and the extrudate is brought into contact with the liquid to make it A method of obtaining a foamable polystyrene resin particle by cooling and solidifying, wherein the expandable polystyrene resin particle is microfoamed in the particle before cooling and solidifying to obtain a cross section through the center of the resin particle. When the number of bubbles existing in the cross section of 200 / im removed from the surface of the particle is η / nun 2 and the bulk density is pg / cm 3 , the foaming property of the bubble containing the N value of 400 or more calculated by the formula (1) is 400 or more. Polystyrene resin particles. N = n / (l / / 〇 ) (1) In the method of producing the bubble-containing expandable polystyrene resin particles, the above N value is preferably in the range of 400 to 2,000. The method for producing the bubble-containing expandable polystyrene resin particles is preferably a bulk density of 〇4 g/cm3 or more. In the method for producing the foam-containing expandable polystyrene-based resin particles, the above-mentioned foaming nucleating agent is preferably a master batch which can uniformly disperse inorganic powder or chemically-coated steel in a base resin. The foaming agent prepares the foamed particles. Further, the present invention provides a polystyrene-based eucalyptus which is obtained by heating the air-packable foamable polyethylene-based resin particles of the first or second invention, and the present invention provides the polystyrene system. The resin-prepared foamed particles are filled in a cavity of a molding die and heated, and the present Ethylene-based resin foam molded body obtained by foam molding is molded in a mold. Further, the present invention provides the polystyrene obtained by foaming the foamed polystyrene-based resin particles containing the above-described first or second invention in a cavity of a molding die and heating them in a mold. A resin chrome foam molded body. Further, a third invention of the present invention provides a method for producing a thermoplastic resin-prepared expanded particle by subjecting a thermoplastic resin and a foaming agent to melt-kneading in a resin supply device to pass a molten thermoplastic resin containing a foaming agent. The small hole of the mold is extruded into a cooling medium and cut off immediately after extrusion, and foamed into a foaming multiple of 热.6 times or more of the thermoplastic resin pre-expanded particles in a cooling medium, and then the foamed particles are removed from The above cooling medium is separated to obtain thermoplastic resin pre-expanded particles. In the method for producing the thermoplastic resin-prepared expanded particles, it is preferred that the volume expansion ratio of the thermoplastic resin-prepared expanded particles is in the range of 1.6 to 50 times. In the method for producing the thermoplastic resin-prepared expanded particles, the thermoplastic resin containing the foaming agent preferably contains 1 to 1 part by mass of the foaming agent per part by mass of the thermoplastic resin. In the method for producing the thermoplastic resin-prepared expanded particles, the foaming agent is preferably one of ortho-sinter and normal pentane or a mixture of the two. In the method for producing the thermoplastic resin-prepared expanded particles, the thermoplastic resin is preferably a polystyrene resin. Further, the present invention provides a thermoplastic resin-prepared expanded particle obtained by the method for producing a thermoplastic resin-prepared expanded particle of the above third invention. Further, the present invention provides that the foamed particle is prepared by the thermoplastic resin. The thermoplastic resin-prepared foamed particles obtained by the production method are filled in a cavity of a molding die and heated, and are foam-molded in a mold to obtain a thermoplastic resin foam molded body of a thermoplastic resin foam molded body. method. Further, the present invention provides a thermoplastic resin foam molded article obtained by the method for producing a thermoplastic resin foam molded article. According to a fourth aspect of the present invention, a polystyrene-based resin and a foaming agent are melted and kneaded in a resin supply device, and the melted polystyrene-based resin containing a foaming agent is extruded through a small hole of a mold and cooled. The foaming property obtained by cutting off 14 322950 201202317 polystyrene resin particles, and a foaming polystyrene resin _ of an integrating sphere of 75 or less. The whiteness measured is based on the foamable polyphenylene-based resin particles. The resin is preferably contained in an amount of not less than 0.08 parts by mass based on 10 parts by mass of the resin, and the amount of the styrene resin is reduced as the foaming amount. ~, machine _ end 1 · 〇 mass parts in degrees compared to the tree tree, the tree recorded by Zhao Ji Mi B == ί tree relatives (four) Ping 乂 t t 3 have foaming agent 2 to 1 [^ 皙The foamable polyphenylene-based resin particles and the foaming agent are preferably ruthenium. A mixture of an alkane and n-pentane or a mixture of the two. In addition, the fifth invention of the present invention provides a method for producing a foamable polystyrene resin particle, which is obtained by refining a polystyrene resin and a foaming agent in a resin supply device (4). The method for producing a foamable polystyrene tree filament obtained by extruding, cooling and cutting the olefinic core m containing the hair (4) through a small hole of a mold, wherein the melted foaming agent is aggregated The styrene-based resin is extruded, cooled, and cut in a pressurized cooling medium to obtain a foamable polystyrene-based resin particle having a whiteness measured by an integrating sphere type color difference meter. In the method for producing the foamable polystyrene resin particles, it is preferred to add a refractive index of ±0.08 or less to the polystyrene resin with respect to the polystyrene resin. Inorganic material powder 1. The amount of 〇 by mass or less is used as a foaming nucleating agent. 322950 15 201202317 In the method for producing the expandable polystyrene resin particles, it is preferred to obtain expandable polystyrene resin particles having a bulk density of 0.58 g/cm3 or more. In the method for producing the expandable polystyrene resin particles, it is preferred to contain 2 to 15 parts by mass of the foaming agent based on 100 parts by mass of the polystyrene resin. In the method for producing the expandable polystyrene resin particles, the foaming agent is preferably one of isopentane and n-pentane or a mixture of the two. Furthermore, the present invention provides a polystyrene-based resin pre-expanded particle obtained by thermally foaming the expandable polystyrene-based resin particles of the fourth or fifth invention. In addition, the present invention provides a polystyrene-based resin foam molded article obtained by filling the polystyrene-based resin pre-expanded particles in a cavity of a molding die and heating the film in a mold. (Effect of the Invention) The foam-containing expandable polystyrene resin particles according to the first or second aspect of the present invention can provide a foam which is excellent in mechanical strength and excellent in appearance and high in meltability even at a high magnification. Shaped body. Further, since the foamable resin particles have been foamed, the foamable polystyrene resin particles containing the bubbles can be directly filled in a cavity of a molding die, and foam molded in the mold to obtain a foamed body. As a result, the manufacturing steps of the foamed molded body can be reduced, and the cost can be reduced. Moreover, since the amount of energy consumption can be reduced, it is expected to reduce the load on the environment. Production of thermoplastic resin pre-expanded foamed particles according to the third invention of the present invention 16 322950 201202317 The method is to melt and knead a thermoplastic resin and a foaming agent in a resin supply device, and to pass a molten thermoplastic resin containing a foaming agent through a mold. After the small hole is extruded into the cooling medium, the thermoplastic resin is preliminarily foamed into a volume expansion ratio of 1.6 times or more in the cooling medium, whereby the foamed molded body can be used for the production of the foamed molded body. The thermoplastic resin-prepared foamed particles are directly produced by a melt extrusion method. Therefore, compared with the conventional method of producing foamable resin particles and heating them to obtain preliminary expanded particles, the foamed molded article can be produced in a smaller number of steps, and the production efficiency of the foamed molded article becomes higher. Further, the storage space of the expandable resin particles can be reduced. Moreover, the thermoplastic resin pre-expanded foam particles obtained by the method are spherical to slightly spherical, and have better filling property in the cavity of the forming mold than in the column-shaped preliminary expanded particles. It can be filled without gaps. Further, the foamed particles can be well melted during the molding and the internal foam molding, and a foam molded article having excellent strength can be obtained. In the expandable polystyrene resin particles of the fourth invention of the present invention, the number of bubbles in the resin particles is small, and the whiteness measured by an integrating sphere type color difference meter is 75. Therefore, the bulk density is higher than that of the expandable polystyrene resin particles obtained by the melt extrusion method in the past, and the volume of a certain mass is smaller than that of the conventional product having a high whiteness. As a result, the storage space of the particles can be reduced, and the handling of the particles becomes easy. Further, the foamable polystyrene-based resin particles have excellent gas/package v strength in the resin particles, and are less likely to be cracked or disintegrated. In addition, according to the foamable polystyrene-based resin particles, when foaming is performed during heating and preliminary foaming, uniform foaming can be achieved, and 17 322950 201202317 preliminary expanded beads having a uniform particle diameter or (4) uniform density can be obtained. Therefore, the foamed molded body obtained by the foaming and forming of (4) _ hair's coke is excellent in strength. Further, the foamable polyphenylene-based resin particles are stable due to the dispersion of the foaming agent. The particle life is long and can be stored for a long period of time. The method for producing the foamable polystyrene-based resin particles according to the fifth invention of the present invention is a method for producing a foamed polystyrene resin particle by a melt extrusion method. The saponin is extruded, cooled and cut in a medium of pressurized Δ, and a foaming polystyrene resin particle having a whiteness of 75 or less by an integrating sphere is obtained. Therefore, it is possible to produce a foamable polystyrene resin particle having a superior effect as compared with the above-mentioned conventional product. In addition, the polyphenylene resin pre-foamed particles obtained by heating and pre-expanding the foamable polystyrene-based resin particles of the fourth or fifth invention of the present invention are uniformly foamed during preliminary foaming. A ready-to-use granule with uniform granules or bulk density can be obtained. Therefore, the strength of the foamed molded body obtained by foam molding the prepared expanded beads in a mold is excellent. [Embodiment] Hereinafter, embodiments of the present invention will be described based on the drawings. In the first embodiment, the foam-containing foamed polystyrene resin particles of the present embodiment are characterized in that the polystyrene benzene has a (four) ship bubble, and is present in the bubble-containing polystyrene. When the cross-section of the cross-section of the resin particle is removed from the surface of the particle, the number of gas nucleus is n/ca, and the volume density is Μ3, the N value calculated by the formula (1) is above the shed.

322950 S 18 201202317 N=n/(1/p )...(1). In the foamed polystyrene-based resin particles of the present embodiment, the N value calculated by the above formula (1) is 400 or more, and the particles are in comparison with the ordinary expandable polystyrene resin particles. There are internal internal structures of many fine bubbles in the interior. In the present specification and the scope of the patent application, the "bubble" is a diameter of 5 μ in or more of the inside of the resin particle when the cross section of the foamable polystyrene resin particle containing the bubble is magnified by a scanning electron microscope or the like. bubble. The foam-containing expandable polystyrene resin particles of the present embodiment have a structure in which the N value calculated by the above formula (1) is 400 or more, and are obtained from the foamable polystyrene resin particles containing bubbles. The bubbles of the foamed molded body are dense and uniform. As a result, it is possible to obtain a foamed molded body which is excellent in mechanical properties and excellent in appearance even at a high magnification. Further, since the foamable resin particles have been foamed, the foamable polystyrene resin particles containing bubbles can be directly filled in a cavity of a molding die, and foam molded in the mold to obtain a foamed body. . As a result, the manufacturing steps of the foamed molded body can be reduced, the cost can be reduced, and since the energy consumption can be reduced, it is expected to reduce the load on the environment. If the above N value is less than 400, the performance of the obtained foamed molded article is not much different from that of the conventional expandable polystyrene resin particles. Therefore, the effect of the foamed molded body excellent in mechanical strength even in the case of a high-magnification appearance and superior fusion property can not be sufficiently obtained. Further, the upper limit of the above-mentioned N value of 19 322950 201202317 is not particularly set, but if the value of N is too large, it becomes difficult to manufacture the foamable polystyrene-based resin particles, and the bubble of the obtained foamed molded body may be Thinning and weakening. Therefore, the upper limit of the N value is preferably about 2 。. Therefore, the above N value is preferably in the range of 400 to 2,000, more preferably in the range of 5 Torr to 1600. In the bubble-containing expandable polystyrene resin particles of the present embodiment, the bulk density is preferably 〇4 g/cm3 or more, more preferably 〇5 g/cm3 or more. Further, the bulk density of the foam-containing foamed polystyrene resin particles of the present embodiment is a value measured by ns K6911: 1995 "Testing method for thermosetting plastics". The method for measuring the bulk density of the foamable polystyrene resin particles having bubbles is as follows. The measuring cylinder was filled with foaming polystyrene resin particles containing bubbles to a mark of 500 cm3. However, by visually observing the cylinder from the horizontal direction, the foamed polystyrene resin particles containing bubbles are not filled as long as one of the particles reaches a scale of 5 〇〇 cm 3 . Then, the mass of the foam-containing expandable polystyrene resin particles filled in the measuring cylinder to the effective number of two points below the decimal point was weighed and the mass was W (g). Subsequently, the bulk density of the foamable one ethylene-based resin particles containing the bubbles was calculated by the following formula. Bulk density (g/cm3) = W/500 The foamable polystyrene resin particles containing bubbles in the present embodiment are not particularly limited, and examples thereof include styrene, nail, and styrene. , ethyl benzene, toluene, chlorostyrene, ethyl styrene, isopropyl styrene, sulfhydryl, styrene and other stupid ethylene monomers 322950 20 201202317 Or the copolymers of the above: polyjia: two = as the main component of the above-mentioned stupid fat, which may be a copolymer of the above-mentioned styrene-ethyl succinimide and the stupid ethylenic monomer ) ^^tn® can be like (meth) methacrylic acid, hexadecyl vinegar, etc. (methyl 9 (methyl) acrylate vinegar, (methyl formic acid, fumaric acid (methyl) propylene) Guess, horse divinyl benzene, hydrazine dimethyl hydrazine: diethyl urate, ethyl fumarate, and, also, di-functional monomers such as october vinegar, etc. Resin. Add The tree; as the resin' can also add other examples such as the addition of polybutadiene, stupid" shaped body to impact, the non-co-doprene dilute three-dimensional copolymer Silk, Ethylene-C-modified polystyrene resin, so-called:: rubber-like polymer rubber P〇lystyrene), or exemplified by poly-ethylene (h_ i climbing ct-propionic acid resin, Acrylonitrile-phenethyl: resin, polypropylene resin, styrene copolymer, etc. Ethylene copolymer, acrylonitrile-butanyl-ethylene == ί = can be re-made In addition to the polystyrene system, it is also a heart; 5 polybenzyl resin (non-recycled polystyrene) Recycled virtual two Xiao will be Μ &quot; ° poly 6 6 resin foam molded body for regeneration treatment The recovered raw material is a styrene-butadiene-based resin foam molded body;: = is a buffer material or a food package from a used polymer product, etc.; === container, motor disk, etc., by using lemon Acid 322950 21 201202317 (1 imonene) Among the recovered raw materials in the dissolution mode or the heating and volume reduction mode, a raw material having a weight average molecular weight Mw of 120,000 to 300,000 is appropriately selected, and a plurality of kinds of recycled raw materials having different weight average molecular weights Mw may be used. Use in combination with foaming polystyrene containing bubbles in this embodiment The foaming agent to be used for the resin particles is not particularly limited, and for example, an aliphatic hydrocarbon such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane or cyclopentane, or a diterpene ether can be used. And ethers such as diethyl ether, various alcohols such as decyl alcohol and ethanol, carbonic acid gas, nitrogen gas, water, etc. Among them, aliphatic hydrocarbons are preferred, and n-butane, isobutane and n-pentane are more preferred. Isopentane alone or a mixture of the same. It is preferably a mixture of n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene or a mixture of such hydrocarbons having a carbon number of 5, wherein Preferably, one of isopentane and n-pentane or a mixture of the two is used. The hydrocarbon having 5 carbon atoms as a main component may contain a foam having a boiling point of 20 ° C or higher and a hydrocarbon having 5 carbon atoms. Agent (for example, n-butyl, isobutyl, propyl, carbonic acid, etc.). The amount of the foaming agent to be added is preferably from 2 to 15 parts by mass, more preferably from 3 to 8 parts by mass, most preferably from 4 to 7 parts by mass, per 100 parts by mass of the polystyrene resin. range. The foam-containing expandable polystyrene resin particles are preferably added to the talc powder as a foaming nucleating agent, calcium silicate, synthetic or naturally occurring cerium oxide, based on 100 parts by mass of the polystyrene resin. Such as inorganic fine powder or chemical foaming agent. 5质量的范围范围的范围内。 The amount of the above-mentioned amount of the amount of the foaming agent is preferably in the range of 0.5 parts by mass. The above chemical foaming agent may, for example, be azodicarboxyfluorene 22 322950

201202317 Amine, hydrazine, hydrazine --dinitrosopentamethylenetetramine, 4, 4'-oxybis(phenylsulfonylhydrazine), sodium hydrogencarbonate, and the like. In the present embodiment, the foaming nucleating agent is preferably a masterbatch type foaming nucleating agent which is obtained by uniformly dispersing an inorganic powder such as talc or a chemical foaming agent in a base resin, preferably in a polystyrene resin. Since the masterbatch type foaming nucleating agent is used, when the polystyrene resin is mixed with the foaming nucleating agent in the resin supply device, the inorganic powder or the chemical foaming agent can be made very uniform in the polystyrene resin. The state is scattered. After the foaming agent is mixed in the molten resin, it is extruded and cut into water from a small hole of a mold to produce a foamable polystyrene resin particle, and the above-mentioned enthalpy value of 400 or more can be easily obtained. The foamable polystyrene resin particles containing bubbles in the fine bubbles. In addition to the foaming agent and the foaming nucleating agent, the foamable polystyrene resin particles of the present embodiment do not damage the obtained foamable polystyrene resin particles containing bubbles and Additives such as a binding inhibitor, a bubble regulator, a crosslinking agent, a filler, a flame retardant, a flame retardant, a lubricant, a colorant, and the like may be added to the physical properties of the foamed molded article. An embodiment of the method for producing foamed polystyrene resin particles containing bubbles according to the present invention. Fig. 1 is a view showing an example of a manufacturing apparatus used in a method for producing expandable polystyrene resin particles. The manufacturing apparatus of the present embodiment includes an extruder 1 as a resin supply device, a mold 2 having a plurality of small holes attached to the front end of the extruder 1, and a raw material supply hopper 3 for introducing a resin material or the like into the extruder 1. a high-pressure pump 4 that presses a blowing agent into the melted resin in the broadcaster 1 through the blowing agent supply port 5; so that the cooling water is in contact with the resin discharge surface of the mold 2 having a small hole in the penetration setting 23 322950 201202317 a cutting chamber 7 for supplying cooling water in a chamber; a rotatable cutter 6 capable of cutting the resin extruded from the small hole of the mold 2; and cooling from the cutting chamber 7 The foamable resin particles which are transported by the flow of water are separated from the cooling water, and dehydrated and dried to obtain a dehydration dryer 10 having a solid-liquid separation function of the expandable resin particles; and dehydration drying by a solid-liquid separation function The water tank 8 in which the cooling water separated by the machine 10 is stored; the high-pressure pump 9 that delivers the cooling water in the water tank 8 to the cutting chamber 7; and the dehydrated and dried hair dryer 10 which is provided with the solid-liquid separation function Storage of foaming resin particles 11. Further, the extruder 1 can use any one of an extruder using a screw or an extruder not using a screw. Examples of the extruder using the screw include a single-shaft extruder, a multi-axis extruder, a curved extrusion, a tandem extruder, and the like. Examples of the extruder that does not use a screw include a ram extruder, a gear pump extruder, and the like. In addition, static mixers can be used with any extruder. Among these extruders, from the viewpoint of productivity, an extruder using a screw is preferred. Further, the cutting chamber 7 accommodating the cutter 6 can also be used in a conventionally known method for use in a granulation method in which a resin is melted and extruded. By using the manufacturing apparatus shown in Fig. 1 to produce foamable polystyrene resin particles containing bubbles, first, a desired additive such as a polystyrene resin, a foaming nucleating agent, and a flame retardant to be added if necessary is weighed. The raw material supply hopper 3 is put into the extruder 1. The polystyrene resin of the raw material may be used as a pellet or a pellet, and may be sufficiently mixed beforehand to be supplied from one raw material supply hopper, or may be used in a plurality of batches, for example, in a plurality of batches.

24 322950 S 201202317 The multiple feed hoppers that adjust the supply amount are injected and mixed in the extruder. Further, when a plurality of batches of the recovered raw materials are used in combination, it is preferable to thoroughly mix the raw materials of the plurality of batches 4 beforehand, and remove the foreign matter by an appropriate selection method such as magnetic gas selection, sieving, specific gravity selection, and air supply selection. After the polystyrene resin, the foaming auxiliary agent, and other additives are supplied into the extruder 1, the resin is heated and melted, and the molten resin is transferred to the side of the mold 2 while the high pressure is supplied from the foaming agent supply port 5 The pump 4 presses the foaming agent, mixes the foaming agent in the molten resin, and passes the sieve for removing the foreign matter which is provided in the extruder 1 as necessary, and moves the melt to the front end while re-kneading. The melt added with the blowing agent is extruded from a small hole of the mold 2 attached to the front end of the extruder 1. The resin discharge surface penetrating through the small hole in which the mold 2 is provided is disposed in the cutting chamber 7 in which the cooling water is circulated in the room, and the resin in the cutting chamber 7 is cut off from the resin extruded from the small hole of the mold 2. Rotary cutter 6° If the melt agent added with the blowing agent is extruded from the small hole of the mold 2 attached to the front end of the extruder 1, the melt is cut into pellets while being in contact with the cooling water. 'Rapid cooling' produces micro-foaming inside the cut resin particles until the resin is completely cured. As a result, the bubble-containing expandable polystyrene resin particles of the present invention having the N value calculated by the above formula (1) of 400 or more can be obtained. The foam-containing polystyrene-based resin particles obtained by the bubble are transported from the cutting chamber 7 to the dehydration dryer 10 having the solid-liquid separation function, and the expandable polystyrene resin particles are supplied along with the flow of the cooling water. Dehydrated and dried while being separated from the cooling water. The dried foamy polystyrene containing bubbles 25 322950 201202317 The resin particles are stored in the storage container 11. In the method for producing the foamed polystyrene-based resin particles, the cooling water is suspended by a weight of 0. 2 MPa in order to pressurize the cooling water, and it is possible to flow through the cooling water. The portion on the inlet side of the dehydration dryer 10 from the discharge side of the high pressure fruit 9 through the chamber 7 to the liquid separation function is used as a pressurizing region, and the discharge pressure of the high pressure pump 9 is increased. The pressure of the above cooling water is preferably in the range of from 0.5 to 1.5 MPa, more preferably in the range of Ha. The foam-containing foamed polystyrene resin particles of the present embodiment are used in a device and a method known in the field of production of a foamed resin molded body, and are heated by steam heating or the like to prepare foaming. Resin-prepared expanded particles (hereinafter referred to as preliminary expanded particles). The preliminary foaming particles are prepared in the same bulk density as the density of the polystyrene and the resin foam molded article (hereinafter referred to as "foam molded article"). In the present embodiment, the bulk density is not limited, and is usually in the range of 3 { 1{) to 〇. (7) in the range of coffee 3, preferably in the range of 0.015 to 〇.〇5〇g/cm3.

Further, in the present embodiment, the bulk density of the preliminary expanded beads is a value measured in accordance with JIS K6911: 1995 "Testing method for thermosetting plastics". The method for measuring the bulk density of the preliminary foamed particles is as follows. The pre-expanded particles were filled in a graduated cylinder to a scale of 5 〇〇 cm 3 . However, visual inspection of the graduated cylinder from the horizontal direction is completed as long as one particle reaches the 500 cm3 scale. Next, weigh the mass of the pre-expanded particles filled in the measuring cylinder to two significant digits below the decimal point, the quality of which is 26 32295〇

S 201202317 The quantity is w(g). The bulk density of the preliminary expanded particles is obtained according to the following formula. Bulk density (g/cm3) = W/500 Further, the volume expansion ratio of the "prepared expanded particles" is a value calculated according to the following formula. Volume expansion ratio = 1 / volume density (g/cm3) Next, using a device and a method known in the field of manufacturing a foamed resin molded body, the preliminary expanded particles are filled in a cavity of a molding die by water vapor. Heating such as heating is carried out by foam molding in a mold to produce a polystyrene resin foam molded body (hereinafter referred to as a foam molded body). The density of the foamed molded article of the present embodiment is not particularly limited, but is usually in the range of from 0. 010 to 0.1 g/cm 3 and is preferably in the range of from 0.015 to 〇. 05 〇 g/cm 3 . Further, in the present embodiment, the density of the foamed molded article is the density of the foamed molded article measured by the method described in jis K7122: 1999 "Foamed Plastic and Rubber - Appearance Density". The method for measuring the density of the foamed molded body is as follows. A test piece of 50 cm 3 or more (1 〇〇 cm 3 or more for semi-rigid and soft materials) was cut without changing the original grain structure of the material, and the mass was measured and calculated according to the following formula. Density (g/cm3) = test piece mass (g) / test piece volume (cm3) Test piece state adjustment, measurement test piece is taken from a sample which has passed 72 hours or more after molding, and is cut at 23t ± 2t x 50% ± 5% or 27 ° C ± 2t: x 65% ± 5% of the environmental conditions for more than 16 hours. Further, the expansion ratio of the foamed molded article is a value of 27 322950 201202317 calculated according to the following formula. Foaming ratio = 1 / density (cm3) In addition, since the foamable polystyrene resin particles containing bubbles of the present embodiment are foamed, the foamable polystyrene resin particles containing bubbles can be directly filled. In the cavity of the molding die, a foamed molded body is obtained by foam molding in a mold, that is, a foamed molded body is produced by a so-called original particle foam molding method. When the foamed molded article is obtained by the above-described raw particle foaming molding method, the foaming polystyrene resin particles containing the bubbles are directly filled in the cavity of the molding die without performing the preliminary foaming step described above. Internal foam forming. Therefore, it is possible to reduce preparation by preparing foaming of the expandable polystyrene-based resin particles and filling the obtained preliminary foamed particles in a cavity of the molding die to perform foam molding in the mold. The foaming step, the cost reduction, and the reduction in energy consumption are expected to reduce the load on the environment. [Examples] [Example 1] (Production of foamable polystyrene resin particles containing bubbles) As a base resin, it is based on a polystyrene resin (manufactured by Toyo Styrene Co., Ltd., trade name "HRM_1〇N" "1" by mass of a mixture of talc masterbatch (54% by mass of polystyrene resin, 40% by mass of talc, 3% by mass of stearic acid, and 3% by mass of stearic acid monoglyceride) The mixture was uniformly mixed in a rolling mixer in advance, and the resultant was supplied to a single-axis extruder having a diameter of 9 〇mm at a rate of 160 kg/hour, and 322950 28 201202317, after heating and melting the resin, 100 parts by mass relative to the resin. 6 parts by mass of isopentane as a foaming agent was injected from the extruder. Then, the resin and the foaming agent were kneaded in the extruder, and the temperature of the resin at the front end portion of the extruder was cooled to 190°. The granulation mold is extruded to a water pressure by a granulation mold having a diameter of 0.6 mro and a length of 3. 0 mm of the forming section by means of a die attached to the extruder and maintained at 320 ° C by a heater. OMPa, 40 ° C cooling water circulation in the tank ' A high-speed rotary cutter having a one-blade cutting edge in the circumferential direction is adhered to the mold, cut at 3,000 rpm, and dehydrated and dried to obtain spherical foam-containing expandable polystyrene-based resin particles. The foamed polystyrene resin particles containing the bubbles are not deformed and have a long whisker, and the average particle diameter is 1.1 mm. The polymer is obtained by 100 parts by mass of the foamable polystyrene resin particles obtained by the bubbles. The amount of the ethylene glycol is 0.03 parts by mass, the zinc stearate bismuth. 15 parts by mass, the stearic acid monoglyceride, 0.05 parts by mass, the hydroxystearic acid triglyceride, 0.05 parts by mass, uniformly coated on the surface of the resin particles. (Production of Foamed Molded Body) The foamed polystyrene resin particles containing bubbles prepared as described above were placed in a cold storage at 15 ° C, and left for 72 hours before being supplied to a cylindrical batch preparation. The foaming machine was heated by steaming with a pressure of 0 〇 5 MPa to obtain preliminary foamed expanded particles. The obtained preliminary expanded foam had a bulk density of 〇·〇2 g/cm 3 (volume expansion ratio of 50 times). Next, the pre-expanded particles will be obtained at room temperature. After being placed in the environment for 24 hours, the pre-expanded foamed particles are filled in a forming mold having a rectangular mold groove having a length of 400 mm x 300 mm x 50 mm and a height of 50 mm. After that, the water in the cavity of the forming mold is pressed with water vapor. 〇 8Mpa 322950 29 201202317 The pressure was heated for 20 seconds, and then the pressure in the cavity of the forming mold was cooled to 0. OIMPa, and then the forming mold was opened, and a rectangular foam molded body having a length of 400 mm and a width of 300 mm x a height of 50 mm was taken out. The maleity is 0. 02 g/cm3 (foaming multiple of 50 times). The following evaluation test was carried out on the foam-containing expandable polystyrene resin particles, the preliminary expanded beads, and the foamed molded article of Example 1 produced as described above. Further, the bulk density of the foamable polystyrene resin particles containing bubbles and the expansion ratio of the foamed molded article were determined by the above-described measurement methods. Further, the number of bubbles per 1 mm 2 was determined by the following method. A cross section near the center of the foamable polystyrene resin particles containing bubbles was observed with a scanning electron microscope, and a photograph magnified 70 times was taken. The cross section of the foamed polystyrene-based resin particles containing the bubbles in the photograph was removed from the surface of the particle by 2 〇〇am, and was taken at 5 places where the range of 0. 2 mm x 0 · 2 was not repeated as much as possible. The number of all the bubbles existing in each range is counted (even if the part of the bubble is included, the average of the number of bubbles in the five places is calculated, and the value is calculated as the value per lmm2. Further, the value of N is obtained by the following method. The calculation is based on the number of bubbles η per W calculated by the above-mentioned &lt;number of bubbles per lmm2&gt;, and the formula (1) of the following formula, thereby calculating Ν Value. Ν=η/(1/Ρ)...(1) In addition 'foaming forming

ASTM D-2842 69 is used as a standard, and the bubble diameter (average bubble diameter) of the body is measured under the following conditions. 30 322950

S 2012300017 Scanning Electron Microscope The S-3000N manufactured by Hitachi, Ltd. was used to take a photo of the profile of the foamed molded body (photographing magnification: 1〇〇), from the straight line (60 colors) of the cut surface on the photo. The number of bubbles present was measured as the average chord length (t), and the diameter (d) of the bubble was calculated by the following formula. Average chord length (t) = 60 / (number of bubbles X: multiples of shot) Average bubble diameter (d) = t / 0. 616 In addition, for the obtained foamed molded body, JIS A9511 : 2006 "foamed plastic insulation material" The method described is a standard and the bending strength is measured. That is, using a tensilon universal testing machine UCT-l〇T (manufactured by Orientec), the size of the test body is 75 mm x 300 mm x 30 inm, the compression speed is 10 mm/min, and the front end aid is at the pressure wedge i〇r, the bracket 1〇R, The measurement was carried out under the condition that the distance between the fulcrums was 200 mm, and the bending strength was calculated by the following formula. The number of test pieces was three, and the average value was obtained. Bending strength (MPa) = 3FL / 2bh2 . (where 'F is the maximum bending load (N), L is the distance between the fulcrums (mm), b is the width of the s-type test piece (mm), and h is the thickness of the test piece. (mm)). Further, the foam molded body was cut into a length of 50 μm and a thickness of 2.5 mm, and as a test piece, the 5% compression strength of the foam molded body was measured based on JIS Z0234. Further, the falling ball value of the obtained foamed molded body was measured in accordance with JIS K7211; 1976. In other words, the foamed molded body was cut into 2 brilliant, 40 mm wide, and 25 mm thick, and as a test piece, a steel ball having a mass of 255 g was vertically dropped in the test piece, and when the foam molded body was 50% broken, Falling height. [Example 2] ex C; 31 322950 201202317 A foam molded article was produced in the same manner as in Example 1 except that the foaming nucleating agent used was 2.0 parts by mass. [Example 3] The foaming nucleating agent was produced in the same manner as in Example 1 except that the foaming nucleating agent was used in the same manner as in Example 1 except that the product name "polythlene ES275" was 0.85 parts and the water pressure was 0.7 MPa. Shaped body. [Example 4] A foam molded article was produced in the same manner as in Example 1 except that the foaming nucleating agent used was 4.0 parts by mass. [Example 5] A foam molded article was produced in the same manner as in Example 1 except that the foaming nucleating agent used was 5.0 parts by mass. [Example 6] A foaming resin particle containing bubbles was produced in the same manner as in Example 1 except that the coating agent was not used. Then, the bubble-containing foamable resin particles were filled in a mold groove (length 400 mm x 300 mm x 50 mm thick) in which a molding die of a molding machine was attached, and heated in water vapor of 0.08 MPa for 35 seconds to be cooled to obtain a density. 0. 641 g / cm3, a foaming multiple of 1. 6 times, a size 400mmx300mmx50min low-expansion molded body. [Comparative Example 1] A foamed molded body was produced in the same manner as in Example 1 except that the foaming nucleating agent was used in an amount of 0.3 part by weight of talc, and the water pressure was 0.3 MPa. [Comparative Example 2] 32 322950 201202317 A foamed molded body was produced in the same manner as in Example 1 except that the foaming nucleating agent was used in an amount of 0.3 part by weight of talc, and the water pressure was 1.0 MPa. The results obtained in the above Examples 1 to 6 and Comparative Examples 1 to 2 are summarized in Table 1. 33 322950 201202317 Γ--ιΙί Comparative Example 2 Talc 0.3 parts by mass 〇 Λ Λ CO Ο · r·^ ο 50 times (NI CO CO 0.28 (ΝΪ 〇CO o Comparative Example 1 Talc 0.3 parts by mass CO Ό 0.568 CO o CO 50 times 〇〇C&lt;l 05 CS3 CD CO o to Example 6 Talc powder masterbatch 1.0 parts by mass ο CO ο 1234 1.6 times in CO 〇CO 〇· CN] 1 12.96 LO tn 03 Example 5 Talc powder 5.0 parts by mass ο σ &gt; ◦ CO ο 1 3456 ! 2104 ji 50 times CO m 0.29 C&gt; O Example 4 Talc masterbatch 4.0 parts by mass ο rH 0.628 2938 1845 50 times in 0.30 1 (&gt;3 rH o CO CO Example 3 _ 1 Polythlene ES275 0.85 parts by mass of dip 0.558 03 3 414 50 times 03 ah 05 oa G &lt; NJ G&gt; CO Example 2 Talc powder masterbatch 2.0 parts by mass ο Η CO in CO o 1584 1034 50 times呀CO o CO o CD r-H Example 1 Talc powder masterbatch 1.0 parts by mass G CO d 1234 1 03 50 times CO CO oo Bu· Foaming agent addition amount (parts by mass) Water pressure (MPa) 〈 Foaming resin particles containing bubbles> Number of bubbles per 1 mm 2 of bulk density (number / mm 2 ) N value <foaming into Product> 气泡 rate bubble diameter (//m) Bending strength (MPa) 53⁄4 compression strength (MPa) Falling ball value (cm) 34 322950 S' 201202317 From the results of Table 1, it is clear that Examples 1 to 6 of the present invention contain bubbles. The N value of the foamable polystyrene resin particles was 400 or more. In Examples 1 to 5, the resin particles were preliminarily foamed, and the obtained preliminary expanded particles were foam molded in a mold to obtain a foaming multiple of 50 times. In the case of the foamed molded article, the foamed molded article has superior bending strength, compressive strength, and falling ball value as compared with the conventional products having the smaller N values described in Comparative Examples 1 and 2, and the foam of the present invention is superior in strength to the conventional product. Further, in the sixth embodiment, the foamable polystyrene resin particles containing bubbles are directly molded in a mold to produce a low-expansion molded article, and the low-speed foaming can be obtained in a short time. Further, in Example 5, the N value was 2000 or more, the strength was slightly lowered as compared with the foam molded articles of Examples 1 to 4. It is understood from the relevant points that the upper limit of the N value is preferably below 2000. On the other hand, in Comparative Examples 1 and 2, the N value of the expandable polystyrene resin particles did not reach the lower limit of the n value of the present invention (400) 'foamed molded body produced using the above' and the present invention In comparison with Examples 1 to 5, the strength was low, and in particular, the falling ball value was low. The second embodiment of the method for producing a thermoplastic resin-prepared foamed particle (hereinafter referred to as a preliminary expanded particle) according to the present embodiment is characterized in that the thermoplastic resin and the foaming agent are melted and kneaded in the resin supply and take place. The molten thermoplastic resin containing the foaming agent is extruded into a cooling medium through a small hole of the mold, and immediately cuts off the pre-expanded particles which are foamed into a volume expansion ratio of 1.6 times or more in the cooling medium, and then, The pre-expanded particles 35 322950 201202317 were separated from the above-mentioned cooling medium, and the pre-expanded particles were directly produced by a melt extrusion method. In the present embodiment, the type of the thermoplastic resin is not particularly limited, and for example, a polystyrene resin, a polyethylene resin, a polypropylene resin, a polyester resin, a vaporized vinyl resin, an ABS resin, or an AS resin can be used. Either alone or in combination of two or more. Further, as the resin product, a recycled resin from a thermoplastic resin obtained by one-time recovery can also be used. A polystyrene resin such as non-crystalline polystyrene (GPPS) or impact polystyrene (HIps) is preferably used. π乐树月曰 can be exemplified by, for example, styrene, α-mercaptostyrene, methyl benzene, styrene, ethyl styrene, isopropyl styrene, diene, silk, and ethylene. The polymer alone or the like contains polystyrene oxime which is 50% by mass or more of stupid oxime, and more preferably polystyrene. Further, the above-mentioned f styrene can be a copolymer of the above-mentioned styrene and the alkenyl group, and the octagonal vinyl monomer. These B are intended to be t (exemplified by, for example, (mercapto) methic acid methyl vinegar, (mercapto) acrylic acid ethyl sulphate, slightly W methyl) propyl fumaric acid diethyl bromide, nitrile maleic acid Dimethyl ester, dimethyl fumarate, propylene-based axis, f 3 B-, di-glycol stupid, extended-blowing diol, dimethicone, 4 g g-energy monomer, etc. • Xk· j 〇 resin. The knives are made of poly-ethylene resin, and others may be added: in addition, the resin is used for improving the impact resistance of the foamed molded body, and the non-North yoke: polybutadiene, stupid ethylene-butadiene copolymer Rubber modification of two rare rubbery polymers such as ethylene-propylene-three-dimensional copolymer

322950 S 36 201202317 Polystyrene resin, so-called impact-resistant polystyrene. Further, a polyethylene resin, a polypropylene resin, an acrylic resin, an acrylonitrile-styrene copolymer, an acrylonitrile-butadiene-styrene copolymer, or the like can be given. In addition, as the polystyrene resin which is a raw material, a polystyrene resin which is a raw material which is not recovered by using a commercially available polystyrene resin or a polystyrene resin which has been newly produced by a suspension polymerization method or the like ( In addition to the non-re-polystyrene (vi r η polystyrene), a recycled raw material obtained by regenerating the used polystyrene-based resin foam molded body may be used. For the recycled raw material, a polystyrene-based resin foam molded body to be used, for example, a storage container such as a fish, a cushioning material such as a motor product, a food packaging tray, or the like can be used, and the solution can be dissolved or heated by a citric acid solution. Recycling and recycling of raw materials. In addition, the recycled raw material that can be used may be obtained by regenerating the used polystyrene-based resin foam molded body, or may be used for household appliances (for example, televisions, refrigerators, washing machines, air conditioners, etc.) or services. The non-foaming polystyrene resin molded body collected by a machine (for example, a photocopying machine, a facsimile machine, a printer, etc.) is pulverized, melted and kneaded, and then rounded and granulated. The foaming agent used in the preliminary expanded beads of the present embodiment is not particularly limited, and for example, an aliphatic such as propane, n-butane, isobutane, n-pentane, isopentane, neopentane or cyclopentane can be used. Hydrocarbon; ethers such as dimethyl ether and diethyl ether; various alcohols such as decyl alcohol and ethanol; carbonic acid gas, nitrogen gas, water, and the like. Among them, aliphatic hydrocarbons are preferred. Further, it is preferably n-butane, isobutane, n-pentane, isoprene or the like alone or a mixture thereof. Further, n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene or a mixture of these hydrocarbons having a carbon number of 5 is preferred. Among them, a mixture of isopentane and one of n-pentane or 37 322950 201202317 is preferred. Further, the above-mentioned cigarette having 5 carbon atoms as a main component may also contain a foaming agent having a boiling point of 20 ° C or more and a hydrocarbon having 5 or less carbon atoms (for example, Orthodox, Isobutyl, Propylene, Carbonic Acid) Wait). The blowing agent is preferably added in an amount of from 1 to 15 parts by mass, more preferably from 1 to 10 parts by mass, even more preferably from 2 to 6 parts by mass, based on 100 parts by mass of the thermoplastic resin. In the method for producing the pre-expanded particles of the present invention, the thermoplastic resin is preferably added with talc powder as a foaming nucleating agent, calcium ruthenate, synthetic or naturally occurring cerium oxide, bismuth ethylene bisamine citrate, hydrazine. An inorganic or organic fine powder such as a acrylate-based copolymer. The amount of the above-mentioned foaming nucleating agent is preferably in the range of 0.1 parts by mass or less, more preferably in the range of 0.1 parts by mass to 1.0 parts by mass, based on 100 parts by mass of the thermoplastic resin. In the method for producing the pre-expanded particles of the present invention, in addition to the foaming agent and the foaming nucleating agent, the thermoplastic resin may be added with a binding preventing agent in a range that does not impair the physical properties of the obtained preliminary expanded particles. Additives such as bubble modifiers, crosslinkers, fillers, flame retardants, flame retardant aids, lubricants, colorants, and the like. Fig. 1 is a view showing an example of a manufacturing apparatus used in the method for producing preliminary expanded beads of the present invention. The manufacturing apparatus of the present example includes an extruder 1 as a resin supply device, a die 2 having a plurality of small holes attached to the front end of the extruder 1, and a raw material supply hopper 3 in which a resin material or the like is introduced into the extruder 1. The high-pressure pump 4 that presses the foaming agent into the molten resin in the extruder 1 through the blowing agent supply port 5; the cooling water is placed in contact with the resin discharge surface provided with the small hole of the mold 2; In the indoor circulation supply 38 322950 201202317 I extrusion knives cutting chamber 7; in the cutting chamber 7 can be set from the small 2 of the mold 2, the rotary cutter 6 cut off; from the cutting chamber 7 = The pre-expanded particles that have been transported are separated from the cooling water, and are separated by two: to obtain the dewatering function of the pre-expanded particles with the solid-liquid separation function == by the dehydration dryer 10 with the solid-liquid separation function 2 = the water tank 8 for the water to be stored; the cooling water in the water tank 8 = the fiber 9 of the chamber 7; and the pre-expanded particles which are dehydrated and dried by the retention of the solid-liquid separation function iTu 10 The stored storage machine 1 can use an extruder using a screw or an unused screw W / The extruder for the (four) rod can be exemplified by, for example, single or the like: a non-rotary extruder, a curved extrusion, a tandem extruder, a pile of a screw, an extrusion of a screw, such as a plunger extrusion. Machines, gears and other extruders γ ° Any type of extruder can use static mixer. In terms of productivity, it is preferable to use the extrusion of the screw, and the cutting chamber 7 of the cutter 6 can also be used in a bicycle which is extruded by a resin or a cavity. The pre-expanded foam particles are produced by the 31s 1 device of the tree, and the first system: a thermoplastic resin such as a polyethylene-based resin, a foaming branch, a non-flammable agent such as a ruthenium, and the like, which are supplied from a raw material. Wide 'recognition ί ί machine 1 inside. The hot sleeve of the raw material or the :: shape is fully-closed beforehand, and can be supplied from one raw material, or can be used, for example, by using a plurality of supplementary materials of a plurality of batches of technology, and reading «(10) the amount of the ^^ 322950 39 201202317 When using a combination of recycled materials, it is better to mix the raw materials in multiple batches beforehand, and remove the foreign matter by appropriate selection methods such as magnetic gas selection or sieving, specific gravity selection, and air supply selection. After supplying the thermoplastic resin resin, the foaming auxiliary agent, and other additives in the extruder 1, the resin is heated and melted, and the molten resin is transferred to the side of the mold 2 while the high-pressure pump is supplied from the foaming agent supply port 5 (4) The foaming agent is injected into the molten resin, and the foaming agent is mixed in the melter, and the molten material is removed from the extruder, and the molten material is moved to the front end side while being kneaded. The melt of the blowing agent is extruded from a small hole of the mold 2 attached to the front end of the extruder 1. The resin discharge surface of the mold 2 through which the small holes are formed is disposed in the cutting chamber 7 in which the cooling water is circulated indoors, and the cutting chamber 7 is provided with a resin which can be extruded from the small holes of the mold 2. Rotary cutter 6 ° If the melt agent added with the blowing agent is extruded from the small hole of the mold 2 attached to the front end of the extruder 1, the melt is cut into pellets and contacted with the cooling water. Rapidly cooling, the cut resin is foamed between completions and becomes a thermoplastic resin pre-expanded foamed particle having a volume expansion ratio of 1.6 times or more. 0 The volume of the preliminary expanded foam obtained by the foamed foam is preferably better. In the range of from 6 to 50 times, more preferably from 1.6 to 40 times. In addition, the volume expansion ratio of the preliminary expanded beads of the present embodiment is a value obtained by measuring the bulk density based on JIS K6911: 1995 "Testing method for thermosetting plastics", based on the following measurement method. First, fill the cylinder with the pre-expanded particles to a scale of 500cm3 for 40 322950

S 201202317. However, by visually observing the cylinder from the horizontal direction, it is indicated that the filling of the foamed particles reaches the 500 cm mark. Next, the mass of the preliminary expanded particles filled in the amount 'in the cylinder was weighed to a significant number of two decimal places, and the mass was 5 (W). Next, the preliminary foaming bulk density was calculated by the following formula. (Volume Density (g/cm3)=W/500 Next, the volume of the pre-expanded particles was calculated by the following formula, and the volume expansion ratio of the package (times) = 1 / volume density (g/cm3) The volume expansion ratio of the particles can be adjusted according to the pressure water temperature of the cooling water. For example, when manufacturing a low volume expansion ratio (high volume density and bubble at high pressure = low water temperature), when the hair is released, 2 Under the conditions of low pressure and high water temperature ^:): =: Γ edge manufacturing. The pressure of the cooling water is, for example, in the cold part 2 solid-liquid separation function of the dehydration dryer 1Q on the population side to the holy area 'via high pressure If the #刀# is the pressure, it is better. 誃懕...Du* pressurizes and presses the pressure, and adjusts it appropriately. '戋是进: '寺别限' is usually attached to the heater without pressure (or In the cooling water circulation flow path - any. The water temperature does not have two systems = both), to adjust the water temperature as well in the range of 3 〇 to 7 rc in the range of 2G to the age, compared with the preparation of 322950 41 201202317 The foaming particles flow from the cutting chamber 7 along with the cooling water, and the dehydration dryer with the function of solid-liquid separation is 1〇, The prepared foamed particles are separated from the cold water, and the dehydrated teachings are stored in the storage container U. The dried pre-formed foamed deer is prepared by foaming metal particles such as zinc stearate. Thereby, it is possible to prevent agglomeration between the pre-expanded particles, and it is possible to perform a good preparation operation, particularly in the mold cavity of the forming mold. The obtained preliminary foaming is a tree-like to slightly mixed. Compared with the pre-expanded particles which are columnar, the filling property in the cavity of the forming mold is good. 'There is no filling in the cavity. Moreover, when foaming in the mold, it can be well-ridden The foamed molded body is obtained by melting between the foamed particles. The foamed molded article having excellent strength can be obtained by mixing the heat-recoverable resin and the foaming agent in the resin supply device, and melting the melted product. The thermoplastic resin of the foaming agent is cut off immediately after being extruded into the cooling medium through the small hole of the mold, and is sprayed into a cooling medium to form a volume of the foaming multiple of h 6 times or more. Foaming into _ It can be directly produced by a melt extrusion method. Therefore, the foamed molded body can be produced in a smaller number of steps than the conventional method of producing the expandable resin particles and heating them to obtain the preliminary expanded particles. The production efficiency of the molded article is reduced, and the storage space of the expandable resin particles can be reduced. The apparatus and method for preparing the pre-expanded particles of the present embodiment in the foamed resin molding system 322950 42 201202317 The foam is filled in a cavity of a molding die, and heated by steam heating or the like to form a thermoplastic resin foam molded body (hereinafter referred to as a foam molded body) by foam molding in a mold. 020。 The density of the volume is 0. 020g / cm3 or less (expansion ratio of more than 1.6 times), preferably density of 0. 020 To the range of 625 g/cm3 (expansion ratio of 1.6 to 50 times). Further, in the present embodiment, the density and the expansion ratio of the foamed molded article are the density of the foamed molded article measured by the method described in JIS K7122: 1999 "Measurement of foamed plastic and rubber-appearance density". The method for measuring the density of the foamed molded body is as follows. A test piece of 50 cm 3 or more (100 cm 3 or more for semi-rigid and soft materials) was cut without changing the original grain structure of the material, and the mass was measured and calculated according to the following formula. Density (g/cm3) = mass of test piece (g) / volume of test piece (cm3) Further, the test piece for measurement described above was cut out from a sample which was over 72 hours after molding, at 23 ° C ± 2 ° C x 50% ± 5 % or 27ΐ ± 2Χ: χ 65% ± 5% of the environment for more than 16 hours. Further, the expansion ratio of the foamed molded article is a value calculated according to the following formula. Foaming ratio = 1 / density (g/cm3) [Examples] The following examples are merely illustrative of the effects of the present invention, but the following examples are merely illustrative of the present invention, and the present invention is not limited to the embodiments described below. 322950 43 201202317 example. [Example 7] (Production of preliminary foamed particles) 3 parts by mass of micro-powder talcum powder was added to 1 part by mass of polystyrene resin (manufactured by Toyo Styrene Co., Ltd., trade name "HRM10N"). Wait for a single-axis extruder with a diameter of 90 dirty 1 at 13 〇kg per hour. The temperature in the extruder is set to the maximum temperature of 21 (the ratio of pentane to n-pentane = 20:80 (mass ratio) of 3 parts by mass relative to 100 parts by mass of the resin as a foaming agent after rc is melted. )) Pressing in the middle of the extruder. The resin and the foaming agent are kneaded in the extruder and cooled. The resin temperature at the front end of the extruder is maintained at 17 〇. (: The resin introduction portion of the mold The pressure was maintained at 15 MPa' from a mold having 200 holes having a diameter of 〇. 6 mm and a length of the forming section of 3.0 mm, and the molten resin containing the blowing agent was extruded to the discharge side connected to the mold at 40 ° C The water was circulated and the water pressure was set to cut within 0.05 MPa. At the same time, the extrudate was cut at 3000 rpm by a rotary cutter having a one-blade knife in the circumferential direction. The cut particles were cooled by circulating water. Transported to the particle separator to separate the particles from the circulating water. Further, the trapped particles are dehydrated/dried to obtain pre-expanded particles. The obtained pre-expanded particles are not deformed, long-bearing, etc., and are almost spherical. The volume density is 0. 6g / cm3, volume foaming The amount of the polyethylene glycol is 0.03 parts by weight, and the surface of the resin particles is uniformly coated uniformly with respect to 100 parts by mass of the obtained preliminary expanded particles. Manufacture of foamed moldings)

322950 44 201202317 After the obtained preliminary expanded particles are allowed to stand in a room temperature environment for 24 hours, the preliminary expanded particles are filled in a molding die having a rectangular cavity having a length of 400 mm x 300 mm x a height of 25 mm, and then the mold of the molding die is formed. After the water is vaporized in the tank at a pressure of 08 MPa for 2 sec., the pressure in the cavity of the forming mold is reduced to 0.01 MPa and cooled, and then the forming mold is opened to take out a rectangular foam having a length of 400 mm x 300 mm x a height of 25 mm. Shaped body. The obtained foamed molded body has a density of 〇. 6 g/cm 3 (foaming multiple of 1. γ times). The mold filling property was evaluated for the measurement/evaluation of the preliminary expanded particles produced as described above, as described in the following &lt;Evaluation of mold filling property&gt;. Further, the foam molded article produced as described above was subjected to evaluation of the appearance and measurement of the melting rate of the foamed molded article as described below. In addition, the results of the evaluation of the mold filling property described below, the evaluation of the appearance of the foamed molded article, and the measurement of the melting ratio were carried out by referring to the following criteria. The results are shown in Table 2. Here, the evaluation of the mold filling property is performed as follows. The bulk density of the obtained preliminary expanded beads and the degree of expansion of the foamed molded article were determined, and the filling property was calculated according to the following formula, and the mold filling property was evaluated on the basis of the following criteria. A mold filling property = density of the foamed molded body / volume of the preliminary expanded foamed material The evaluation criteria of the mold filling property are as follows. Good (〇): When the mold filling property is 〇. 95 or more, the defect (x): the mold filling property is less than 95. 95 hrs. Further, the appearance evaluation of the foam molded body was carried out as follows. 45 322950 201202317 The pre-expanded foamed particles were filled in a mold of a foam molding machine, and foam molded into a mold having a length of 400 nm, a width of 3 Å, and a thickness of 25 mm was obtained by foam molding in a mold using steam. The appearance of the obtained foamed molded article was visually observed and evaluated on the basis of the following. Good (〇): When the fused portion between the expanded particles is smooth (B): When the fused portion between the expanded particles is uneven, the melting ratio is performed as follows. First, a slit line of a deep one is formed by a dicing blade on any surface of the foamed molded body, and the foamed molded body is divided into two by hand or a hammer along the slit line. Any 100 to 150 expanded particles exposed on the fracture surface of the foamed molded article' counts the number of particles broken in the expanded particles (a) and the number of particles that are thermally melted at the interface between the expanded particles (b) The melting ratio of the foamed molded body was calculated based on the following formula. Melting rate of the hair/package molded body (%) = 1 〇〇χ particle number (a) / (number of particles (a) / number of particles (b)) The evaluation criteria of the melting ratio are as follows. Good: When the melting rate is 70% or more, the evaluation is as follows: After the melting rate is less than 70%, the evaluation of the above-mentioned mold filling property, the evaluation of the appearance of the foamed molded body, and the measurement of the melting rate are referred to the following judgments. The benchmark is comprehensively determined. Good (〇): When there are no defects in the evaluation results of (3), (X): When one or more of the three evaluation results are bad (x) [Example 8]

46 322950 S 201202317 The same procedure as in Example 7 was carried out except that the amount of the pentyl alcohol added was 5 parts by mass and the water temperature was 5 Å «&gt; The 粒径 预备 预备 预备 预备 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪 匪. The results are shown in Table 2 实施 [Example 9] Except that a mold having a diameter of 0.5 mm and a small length of a molding section of 2·5 mni was used, the amount of pentane added was 7 parts by mass and the water temperature was 50° C. 7 is carried out in the same manner. The obtained preliminary expanded particles were free from deformation and long whiskers, and almost the sphere had a bulk density of 0.03 g/cm3, a volume expansion ratio of 33 times, and an average particle diameter of about 3.2 mm. The results are shown in Table 2. [Comparative Example 3] The same procedure as in Example 2 was carried out except that the amount of pentane added was 5 parts by mass, the water temperature was 85 ° C, and the rod-shaped foam was extruded in a cutting chamber and cut after foaming. . The obtained pre-expanded foamed particles are in the form of a cylinder having a bulk density of 0.04 g/cm 3 ′. The volume expansion ratio is 27.3 times, and the straightness of the cylinder is about 2. 5 mm, and the height of the cylinder is about 1.7 mm. The results are shown in Table 2. [Table 2] Bulk Density of Prepared Expanded Particles (g/cm3) Foaming Multiple of Foam Molded Body Filling Property (Multiplier) Appearance of Foamed Molded Body Melting Rate (3⁄4) Comprehensive Judgment

322950 47 201202317 From the results of Table 2, the preliminary foam particles obtained in Examples 7 to 9 of the present invention had a particle shape of impurities and a good mold filling. The foamed molded article obtained in Examples 7 to 9 had a good appearance and a high melting ratio of the foamed beads, and a high-quality foamed molded article was obtained. On the other hand, in the comparative example 3', the molten resin extruded in water was cut in a state of being foamed. The shape of the preliminary expanded particles obtained was cylindrical. The pre-expanded particle mold of Comparative Example 1 had a low filling property, and the appearance and melt ratio of the obtained foamed molded article were lowered. In the third embodiment, the foamable polystyrene resin particles of the present embodiment are characterized in that a polystyrene resin and a foaming agent are melted and kneaded in a resin supply device. The ethylenic resin is extruded, cooled, and cut through a small hole of the mold, and the whiteness of the expandable polystyrene-based resin particles obtained by an integrating sphere type color difference meter is 75 or less. In the present embodiment, the whiteness of the expandable polystyrene resin particles is a value obtained by the measurement by the following method, and is an index of transparency of the foamable polystyrene resin particles. The measurement of whiteness was carried out as follows. The foaming polystyrene resin particles were used as a sample, and the whiteness was measured under the following conditions based on JIS K-7105: 1981. Device: Integral sphere type color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name "ZE2000") Method: The expandable polystyrene resin particles were filled in a sample container made of quartz (3〇1111110&gt;&lt;13111111, sample) The area is 3〇〇1110), and the standard extension 322950 〇48 201202317 is used as the Υ=94. 95, X=92. 94, Z=111 · 82 'determined by the reflection method. The expandable polystyrene resin particles of the present embodiment have a whiteness of 75 or less, preferably 73 or less, more preferably 70 or less. When the whiteness is more than 75, the foaming polystyrene resin particles produced by the melt extrusion method are the same, and many fine bubbles are present in the resin particles. As a result, there is a possibility that the bulk density of the resin particles is lowered due to the occurrence of foaming, the volume of a certain mass is increased, and an extra space is required for storage or transportation; since the foaming is caused, the resin particles are easily broken and disintegrated. Problem: The problem that the mechanical strength of the produced foamed molded article deteriorates is caused by the problem that the life of the particle is short and it is difficult to store for a long time. The foamable polystyrene resin particles of the present embodiment are not particularly limited as the polyethylene-based resin, and examples thereof include phenethyl styrene, α-methyl styrene, vinyl fluorene, and benzene. A single polymer of a styrene monomer such as ethylene, ethyl styrene, isopropyl basic ethylene, dimercaptophenone or isopropyl ethylene or a copolymer of the above. Among them, a polystyrene resin having a mass% or more of styrene is preferable, and polystyrene is more preferable. Further, the above-mentioned one vinyl oxime resin may be a copolymer of the styrene monomer having the styrene monomer as a main component and a vinyl monomer copolymerizable with the styrene monomer. Examples of the vinyl monomer include alkyl (meth)acrylate such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and hexadecyl (meth)acrylate; (Meth)acrylonitrile, dinonyl maleate, dinonyl fumarate, diethyl fumarate, ethyl fumarate, divinylbenzene, alkylene glycol dimercapto acrylate, etc. Functional monomer and the like. b 322950 49 201202317 In, tree 浐. The main component is a polystyrene resin, and other resins which can be used as a rebel/additive resin, for example, for improving the impact resistance of the foamed molded body, butadiene, stupid ethylene-butadiene copolymer Rubber modification of a diene rubber-like polymer such as ethylene-propylene-polyphenylene enelate copolymer. *Resin' so-called impact-resistant polystyrene. Further, examples thereof include polyethylene θ, a polypropylene resin, an acrylic resin, an acrylonitrile-benzene copolymer, a acrylonitrile-butadiene-stuppy copolymer, and the like. For the polystyrene-based resin which is a raw material, a commercially available polystyrene resin, a polystyrene resin which is re-formed by a suspension polymerization method, or the like, and a polystyrene resin which is a raw material can be used. In addition to polystyrene), the I$$ poly-batch, the smelting foam is mixed into the regenerating place? Looking for recycled raw materials. The recycled raw material is a polystyrene-fat foam molded body to be used, for example, a storage container such as a fish, a motor material, a buffer material, a food packaging tray, and the like, and the citric acid dissolution method is added to reduce the volume. Among the raw materials for regeneration and recovery, a raw material having a weight average knives Mw of from 120,000 to 30,000 mils may be appropriately selected, and a plurality of recycled raw materials having different weight average molecular weights Mw may be appropriately used in combination. The foaming agent to be added to the foamable polystyrene resin particles is mainly composed of a hydrocarbon having a carbon number of 5 and may have a boiling point of 2 Å &lt; 3 (: or more, other than the carbon number 5) The foaming agent is preferably one or more hydrocarbon groups having 5 or more carbon atoms, preferably a mixture of isopentyl and pentylene or a mixture of the two. The amount to be added is preferably in the range of 3 to 8 parts by mass, more preferably 4 to 7 parts by mass, based on 100 parts by mass of the resin. 50 322950

S 201202317 The foamable polystyrene-ethylated resin particles: two parts by mass, preferably containing a phase II C-branched tree having a refractive index of ±0.08 or less (preferably Q Q6 A vinyl tree) The refractive index of the inorganic material powder is preferably in the range of G.04 〇·〇5 to U parts by mass, preferably the amount=the lower amount (better in the circumference) as the foaming nucleating agent. As a refractive resin powder having a refractive index of ± 质量 parts by mass relative to the refractive index of ± 〇 shoulder, mica, shiqi acid town, gas oxidation lock, etc., such as sliding on the foaming polystyrene The resin is good for talc. In addition to the above-mentioned foaming nucleating agent, additives such as the above-mentioned foaming agent and the finishing agent, the crosslinking agent, the filler, the flame retardant, the flame retardant auxiliary, and the coloring agent are not impaired. When the surface of the powdery metal-foaming polystyrene resin particles such as stearyl zinc is used, the polystyrene resin-prepared foam particles can be reduced in the preliminary foaming step of the foaming//day/day particles. The combination of the two is therefore preferred. The foamed polystyrene resin particles preferably have a bulk density of g. 58 g/cm 3 or more, more preferably Q 6 6 g/cm 3 or more, more preferably 〇 62 。. If the bulk density is less than G 58 g/Gm3, most of the bubbles may be present in the tree filaments. As a result, there is a possibility that the volume density of the resin particles becomes lower than the volume of nf due to the occurrence of foaming, and the space required for storage or transportation 2 is excessive, and the resin particles are easily broken and disintegrated due to foaming. The problem, the mechanical strength of the foamed molded body to be produced is inferior between the problem and the problem that it is difficult to store for a long period of time due to the short life of the particle. ^ 0 322950 51 201202317 Further, in the present embodiment, the foaming polystyrene system The bulk density of the resin particles is a bulk density measured in accordance with JIS K6911: 1995 "General Test Method for Thermosetting Plastics". The method for measuring the bulk density of the preliminary expanded particles is as follows. The expandable polystyrene resin particles were filled in a graduated cylinder to a scale of 500 cra3. However, when the cylinder is visually observed from the horizontal direction, the foaming polystyrene resin particles have a particle size of 5 〇〇 cm 3 to indicate that the filling is completed. Next, the mass of the expandable polystyrene resin particles filled in the graduated cylinder was weighed to a significant number of two digits below the decimal point, and the mass was w (g). Then, the expandable polystyrene was calculated according to the following formula. Bulk density of the resin particles 0 Bulk density (g/cm3) = W/500 The expandable polystyrene resin particles of the present embodiment have few bubbles in the resin particles, and the whiteness measured by an integrating sphere type color difference meter is 75 or less. Therefore, compared with the foamable polystyrene-based resin particles obtained by the melt extrusion method, the bulk density is high, and as a result, the volume of a certain mass is reduced, so that it can be stored securely and transported easily. . In addition, the expandable polystyrene resin particles of the present embodiment have excellent strength and are not easily broken and disintegrated, and the expandable polystyrene resin particles of the present embodiment are excellent. When heating and preliminary foaming, since the foaming is uniform, preliminary foamed particles having a uniform particle diameter or bulk density can be obtained. As a result, the foamed molded article obtained by foam molding the expandable polystyrene resin particles in a mold is excellent in strength. 322950 ^

In addition, the foamable polystyrene resin particles of the present embodiment are stable in dispersion of the foaming agent, and have a long life of the particles, and can be stored for a long period of time. Next, an embodiment of a method for producing the expandable polystyrene resin particles of the present invention will be described with reference to the drawings. This production method is a method of producing expandable polystyrene resin particles by a melt extrusion method in which a polystyrene resin and a foaming agent are melted and kneaded in a resin supply device. The melted polystyrene-based resin containing a foaming agent is passed through a small hole of a mold, extruded, cooled, and cut in a cooling medium to obtain expandable polystyrene resin particles. In the production method, The molten polystyrene-based resin containing the foaming agent is extruded into a pressurized cooling medium, and cooled and cut to obtain a foaming polycondensation having a whiteness of 75 or less as measured by an integrating sphere color difference meter. Styrene resin particles. The foaming agent to be used for the foamable polystyrene resin particles is not particularly limited, and for example, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, cyclopentane, or the like can be used. An ether such as an aliphatic hydrocarbon, dimethyl ether or diethyl ether; various alcohols such as methanol and ethanol; carbonic acid gas, nitrogen gas, water, and the like. Of these, it is preferably an aliphatic hydrocarbon, more preferably n-butane, isobutane, n-pentane, isoprene or the like alone or a mixture thereof. Further, n-pentane, isopentane, neopentane, cyclopentane, cyclopentadiene, or a mixture thereof, of a hydrocarbon having 5 carbon atoms is preferred. Among them, one of isovalerone and n-pentose or a mixture of the two is preferred. Further, the above-mentioned hydrocarbon having 5 carbon atoms may mainly contain a foaming agent (e.g., n-butylene oxide, isobutane, propane, carbonic acid gas, or the like) having a boiling point of 20 ° C or higher and a hydrocarbon having 5 or less carbon atoms. 53 322950 201202317 The addition of H to the foaming agent is preferably in the range of 2 to 15 parts by mass, preferably in the range of 4 to 7 parts by mass, more preferably in the range of 3 to 8 parts by mass. The foaming nucleating agent 'preferably has an inorganic material powder having a refractive index of ±0.08 or less, preferably 〇, hereinafter, or lower, with respect to the polystyrene-based resin, for example, slipping*'' 1 Λ 』 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Fig. 1 is a view showing an example of a manufacturing apparatus used in the method for producing the foamable polystyrene resin particles. The manufacturing apparatus of the present example includes an extruder 1 as a resin supply device, a die 2 having a plurality of small holes attached to the front end of the extruder i, and a raw material supply hopper 3 in which a resin material or the like is introduced into the extruder 1. a high-pressure pump 4 that presses a foaming agent into a molten resin in the extruder 1 through a blowing agent supply port 5; in such a manner that pressurized cooling water contacts a resin discharge surface through which a small hole of the mold 2 is provided Provided that a cutting chamber 7 having pressurized cooling water is circulated indoors; a rotatable cutter 6 capable of cutting the resin extruded from the small hole of the mold 2 is disposed in the cutting chamber 7; The foamable resin particles which are transported by the flow of the cooling water are separated from the hydrazine water, and dehydrated and dried to obtain a dehydration dryer 10 having a solid-liquid separation function of the foamable resin particles; a water tank 8 in which the cooling water separated by the dehydration dryer 10 is stored; a high-pressure pump 9 for supplying the cooling water in the water tank 8 to the cutting chamber 7; and a dehydration dryer 10 to which a solid-liquid separation function is attached Dehydrated and dried foaming resin particles are stored for storage 11. 201202317 Further, the extruder 1 can use an extruder using a screw or an extruder without any H-type screw in the extruder, for example, a type T outlet, a multi-axis extruder, and a bending machine. Extrusion, tandem extruder. Examples of the (four) machine that has not been used are, for example, a ram extruder, a pump extruder, and the like. In addition, static mixers can be used with any extruder. Among these extruders, from the viewpoint of productivity, an extruder using a screw is preferred. Further, the cutting chamber 7 accommodating the cutter 6 can also be used in a conventionally known method for use in a granulation method in which a resin is melted and extruded. This manufacturing method requires at least the inside of the chamber 7 to be maintained in a pressurized environment by extruding the melted polystyrene resin containing the foaming agent in the pressurized cooling medium. In this (4), in the cooling right cycle, the pressure of the cooling water is maintained in the portion from the discharge side of the high pressure pump 9 through the cutting chamber 7 to the population side of the dehydration dryer 1G with the solid-liquid separation function. 4 MPa or more 'only' is not limited thereto, and may be a configuration in which the entire circulation flow path is pressurized. By using the manufacturing apparatus shown in Fig. 1, the expandable polystyrene resin particles are produced, and the desired additives such as the polyphenylene (tetra) resin, the foaming nucleating agent, and the flame retardant added if necessary are first weighed. The raw material supply hopper 3 is put into the extrusion ^1. The polystyrene resin of the raw material may be round or granular, and may be sufficiently mixed first, and may be supplied from one raw material supply hopper, or, for example, when the plurality of batches are used, the respective batches will be adjusted from the plural amount to be supplied. The raw material supply hoppers are put into 'mixing in the extruder. Further, it is preferable to combine the raw materials of the plurality of batches in (4), and it is preferred to thoroughly mix the raw materials of the plurality of batches beforehand, and remove the foreign matter by appropriate selection methods such as magnetic gas selection or sieving, specific gravity selection, and air supply 322950 55 201202317. After supplying the ethylene-based resin, the foaming nucleating agent, and other additives in the extruder 1, the resin is heated and melted, and the molten resin is transferred to the side of the mold 2 while passing through the high-pressure agent from the blowing agent supply port 5. In the pump 4, the foaming agent is pushed in, and the foaming agent is mixed in the molten resin, and the sieve for removing foreign matter, which is attached to the extruder, is moved to the front end side while being kneaded. The melt of the blowing agent is extruded from a small hole of the mold 2 attached to the extruder 1 before creeping. The resin discharge surface penetrating through the small hole in which the mold 2 is provided is disposed in the cutting chamber 7 in which the cooling water is circulated in the room, and the cutting chamber 7 is provided with a resin which can be extruded from the small hole of the mold 2. Rotary cutter g. In the circulation path of the cooling water, the cooling water is pressurized to 0.4 MPa or more from the discharge side of the high pressure pump 9 through the cutting chamber 7 to the inlet side of the dehydration dryer 10 to which the solid-liquid separation function is attached. When the molten material to which the foaming agent is added is extruded from the small hole of the mold 2 attached to the front end of the extruder 1, the molten material is extruded in pressurized water, and the pressure can be cut off while suppressing foaming. It is granulated, and is rapidly cooled by contact with pressurized water, and is solidified under the suppression of foaming to form foamable polyethylene-based resin particles. When the pressure of the pressurized water is less than 0.4 MPa, the molten resin is extruded in cooling water and cut until the resin is completely cured, and foaming is likely to occur, which may result in high whiteness and low bulk density. Polystyrene resin particles. The force of the pressurized water is preferably in the range of 〇6 MPa or more, more preferably in the range of 〇.6 to 17 MPa. The foamed polystyrene resin particles formed are transported from the cutting chamber γ to the dehydration dryer having the solid-liquid separation function, along with the flow of the cold water.

322950 S 201202317 The expandable polystyrene resin particles are dehydrated and dried while being separated from the cooling water. The dried expandable polystyrene resin particles are stored in the storage container 11 » In the method for producing the expandable polystyrene resin pellets, the expandable polystyrene system is produced by a melt extrusion method Resin Particles 'The molten polystyrene-based resin containing a foaming agent is extruded, cooled, and cut in a pressurized cooling medium to obtain a foaming property of 75 or less measured by an integrating sphere square color difference meter. Polystyrene resin particles. Therefore, as described above, the expandable polystyrene resin particles having superior effects can be efficiently produced as compared with the conventional products. The foamable polystyrene resin particles of the present embodiment are heated by steam heating or the like using an apparatus and method known in the field of production of a foamed resin molded body to prepare a polystyrene. Resin-prepared expanded particles (hereinafter referred to as preliminary expanded particles). The preliminary expanded beads are preliminarily foamed to have the same bulk density as that of all of the produced polystyrene resin foam molded articles (hereinafter referred to as foam molded articles). 015至0·050克/厘米的范围内。 In the present embodiment, the bulk density is not limited, usually in the range of 010. 010 to 0. l〇g / cm3, preferably in the range of 0. 015 to 0. 050g / cm3. Further, in the present embodiment, the bulk density of the preliminary expanded particles is a value measured in accordance with JIS K6911: 1995 "Testing method for thermosetting plastics". The method for measuring the bulk density of the preliminary expanded particles is as follows. Fill the cylinder with the pre-expanded particles to a scale of 5 〇〇 cm 3 ; However, the cylinder is visually observed from the horizontal direction, and the preparation of the expanded particles is completed as long as the granules reach 322950 57 201202317 500 cm3. Next, the weighing amount is filled in the quantity of the prepared transcript, and the effective number of 2 digits of the number of points is 4 = ^ W(g). Next, calculate the volumetric density (g/cm3) of the prepared pure element according to the following formula = W/500

Further, the volume expansion ratio of the preliminary expanded particles is a value calculated according to the formula. A. Volume expansion ratio = 1/volume density (g/cm3) The polystyrene-based resin-prepared expanded particles of the present embodiment are obtained by heating the upper expandable polystyrene-based resin particles to prepare for preliminary foaming. The foam of the polystyrene-based resin-prepared foamed particles is foamed uniformly during the preliminary foaming, and a ready-made girl of the particle (four) bulk density can be obtained. The foamed molded body obtained by using the polystyrene pure aliphatic foaming particles in the mold is excellent in strength. $

The pre-expanded particles are filled in a cavity of a molding die by a device and a method known in the field of the production of a foamed resin molded body, and are heated by steam heating or the like to be foam-formed in a mold to produce a foamed molding. body. The density of the foamed molded body is not particularly limited and is usually in the range of from 151〇 to preferably from 0.015 to 0.050 g/cm3. In the present embodiment, the density of the foamed molded body is K7122: "The density of the foamed molded body measured by the method of measuring the foaming and twisting of the outer yarn. The method for measuring the density of the foamed molded body is as follows. For the 322950 58 201202317 described in JIS", 50 cm 3 or more is used. The test piece having a semi-rigid and soft material of 100 cm 3 or more was cut without changing the original grain structure of the material, and the mass thereof was measured, and then calculated according to the following formula. Density (g/cin3)^Test piece mass (g)/test piece volume (cm3) Further, the above-mentioned test piece for measurement is cut out from a sample which has passed 72 hours or more after molding, at 23 ° C ± 2 ° C x 5 % ± 5% or 27 ° C ± 2 ° C x 65% soil 5% of the environment for more than 16 hours. Further, the expansion ratio of the foamed molded article is a value calculated according to the following formula. Foaming ratio = 1 / density (cm3) [Examples] The following examples are merely illustrative of the invention, and the present invention is not limited to the examples described below. [Example 10] (Production of expandable polystyrene resin particles) 3 parts by mass of micro-powder talcum powder was added to 100 parts by mass of a polystyrene resin (trade name "HRM10N" manufactured by Toyo Styrene Co., Ltd.). These were continuously supplied to a single-axis extruder having a diameter of 9 mm at 130 kg per hour. The temperature in the extruder was set to a maximum temperature of 210 ° C, and after the resin was melted, 7 parts by mass of pentane as a foaming agent was used with respect to 100 parts by mass of the resin (Yiwuyuan. Zhengwuyuan = 20:80 (mass ratio) )) Pressed in from the middle of the extruder. The resin and the foaming agent are kneaded in the extruder while being cooled. The temperature of the resin at the front end of the extruder was maintained at 170 t, and the pressure of the resin introduction portion of the mold was c: 322950 59 201202317 held at 15 MPa, and 200 small holes having a diameter of 0.6 mm and a length of 2.5 mm were formed. In the mold, the molten resin containing the blowing agent is extruded to the discharge side connected to the mold and is 40. (: The water is circulated and the water pressure is set to 1.2 MPa in the cutting chamber, and the extrudate is cut by a high-speed rotary cutter having a one-blade knife in the circumferential direction. The cut particles are cooled by circulating water. The particles are separated from the circulating water while being transported to the particle separator. Further, the collected particles are dehydrated/dried to obtain a foamable polystyrene resin particle containing a pentylene. The resin particles are not deformed, long-bearing, etc., and are almost spherical, and the average particle diameter is about 1.1 mm, and the bulk density is 0.64 g/cm3. Relative to the obtained expandable polystyrene resin particles. 0质量份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份份。 The surface of the resin particles was completely uniformly coated. (Production of the foamed molded body) The foamable polystyrene-based resin particles produced as described above were placed in a 15 C cold storage, and allowed to stand for 72 hours. Cylindrical batch type pre-expansion foaming machine, by blowing pressure 0 The steam of .05 MPa was heated to obtain pre-expanded particles, and the obtained pre-expanded particles had a bulk density of 0.0166 g/cm3 (volume expansion ratio of 60 times). Next, the obtained preliminary expanded particles were placed at room temperature. The aging of the surface of the mold is 0. 08MPa The pressure is heated for 2 sec seconds, after which it will become 322950

S 60 201202317 The pressure in the cavity of the mold was reduced to 0. OIMPa and cooled, and the forming mold was opened. A rectangular foam molded body having a length of 400 mm x 300 mm x a height of 50 mm was taken out. The obtained foam molded body had a density of 〇166 g/cm3 (foaming multiple of 60 times). With respect to the expandable polystyrene resin particles produced as described above, whiteness measurement, volume density measurement, particle life evaluation, and foaming deviation were evaluated based on the Cv value. The measurement of whiteness and the measurement of bulk density were carried out according to the measurement described in the above measurement method. Further, the evaluation of the particle life and the evaluation of the foaming deviation based on the Cv value were carried out according to the following measurement/evaluation method. Further, the evaluation of the bending strength was carried out on the foamed molded body produced as described above. The measurement method and evaluation criteria are as follows. Further, comprehensive determination is made from the respective measurement/evaluation results. This criterion is as follows: <Comprehensive judgment>. The results are shown in Table 3. The evaluation of particle lifetime was carried out as follows. The secret polyphenylene (10) resin particles obtained in the examples (and the ratio (4)) are stored in the muscle for a month, and then supplied to the _ type batch type preliminary foaming machine, and the steam is vaporized by blowing human vapor. After heating for 2 minutes, the volume expansion ratio of the obtained preliminary expanded particles was determined, and the particle life was evaluated by referring to the following evaluation criteria. Particularly good (◎): When the volume expansion ratio is 55 times or more, good (〇): When the volume expansion ratio 45 is less than 55 times as described above, the defect (X): when the volume expansion ratio is less than 45 times. Further, 'for the preliminary foamed particles obtained by the actual _ (and comparative example), 322950 61 201202317 == evaluation of the foaming bias L is evaluated according to the cv value _ deviation to prepare the coefficient of variation of the particle size distribution in the expanded particles as follows: granule: granule The standard deviation of the diameter is divided by the preliminary foaming particles = the reserver, and is calculated according to the following formula. Variation of the particle size distribution of the nucleus of the nucleus of the syllabus/average particle size value The variation coefficient of the particle size distribution Cv value is calculated from the average particle size and the standard deviation as described above. First, the particle average::= ί: = There are 6: a variety of screens of different meshes (: Mesh •, Weeks 6.70_, Mesh 5.60_, Mesh 4 75, Mesh 3·35 with, Mesh 2, _, Mesh 2.36 Coffee, Mesh 2.00 Mm, mesh n, mesh 14 〇, mesh ιΐ8_, mesh 1. 00_) 'Prepared the foamed particles 1〇g from the large mesh screen to the mesh small screen. Then, the particles correspond to (10) of the respective particles, and are in a state in which they are left on the respective screens without passing through a mesh having a fixed mesh size. 675毫米。 The average particle size of the particles remaining on each of the screens is determined by the size of the screen mesh, for example, the average particle size of the particles remaining on the screen of the mesh 3 · 35mm is 3. 675mm. The average particle size of the resin particles remaining on each of the screens is the summed average of the mesh of the screen and the mesh of the screen having the next size mesh of the screen. In the case of a mesh of 3.35 coffee, since the mesh of the sieve having the size of the next large mesh of the screen is 400 mm, the average value of the mesh with the mesh is 4.0 OOmin. 322950 62 201202317 Next, 'measure the mass w of each particle remaining on each sieve, and calculate the mass ratio R (mass Z) of the particles remaining on each sieve relative to the total particles. The average particle diameter 〇 of the sieve particles is multiplied by the value of the mass enthalpy ratio R of the particles, and the sum of the values is taken as the average particle diameter of the particles. The average particle diameter of the preliminary expanded particles = Σ (the average particle diameter of the particles on each sieve j) x the mass ratio of the particles R) Further, the standard deviation of the preliminary foamed particles is determined by the average particle diameter of the above-mentioned preliminary expanded particles The average particle diameter D of each particle of each of the sieves obtained in the measurement method and the mass ratio R (% by mass) based on the total particles remaining on the sieve particles were calculated. From this, the Cv value is obtained and evaluated by referring to the following evaluation criteria. Good (〇): When the Cv value is 〇.〇5 or less, the defect (X): When the Cv value exceeds 〇.〇5, the evaluation of the bending strength is carried out as follows. The foamed molded articles obtained in the examples (and comparative examples) were measured for bending strength based on the method described in JIS A9511: 2006 "foamed plastic heat insulating material". That is, 'Using the tensilon universal testing machine UCT-10T (manufactured by Orientec)', the size of the test body is 75mmx300mmx50inm, and the compression speed is 10mm/min. 'The apex aid is at the pressure wedge 10R and the bracket 1〇R, and the distance between the fulcrums is The condition of 200 mm was measured, and then the bending strength was calculated by the following formula. The number of test pieces was 3 pieces, and the average value was obtained. Bending strength (MPa)=3FL/2bh2 63 322950 201202317 [F, where F is the maximum bending load (N), l is the distance between the fulcrums (mm), b is the width of the test piece (mm), and h is the test piece. Thickness (dirty. From this, the average value of the bending strength is obtained, and the strength is evaluated with reference to the following evaluation criteria. Particularly good (?): good bending strength at 0.25 MPa or more (〇): bending strength is less than 2323 MPa. .25MPa bad (X): When the bending strength is less than 〇23.23 MPa, therefore, the evaluation of the above-mentioned particle life, the evaluation of the foaming difference based on the Cv value, and the evaluation result of the § flattening of the test intensity are referred to the following judgment. The standard is comprehensively judged. Particularly good (◎): no bad (x), especially good ((10) or more is good (〇): no bad (X), especially good (©μ bad (χ): bad 1 In the above [Example 11] The results are shown in Table 3 except that the water pressure was 1.7 MPa. [Example 12] The results are shown in Table 3 except that the water pressure was 〇. 7 MPa. [Comparative Example 4] The pressure is 〇. IMPa is used. The results are shown in Table 3. Example 5 The same operation as in Example 10 was carried out and the same operation as in Example 10 was carried out. The same operation as in Example 10 was carried out. 322950 201202317 except that the blowing agent was butane (isobutane: n-butane = 3 〇: 7 〇) (=)) The same operation as in Example 1 () was carried out except that the main water pressure was UMPa. The results are shown in Table 3. [Table 3]

Whiteness of foamable polystyrene resin particles _ (WB) Bulk density of foamable polystyrene resin particles (g/cm3) Particle life Cv value Bending strength (MPa) Comprehensive judgment Example 10 67 0. 64 ◎ 0. 043 〇0. 25 ◎ ◎ Example 11 62 0. 65 ◎ 0. 024 〇0. 26 ◎ ◎ Example 12 72 0. 61 ◎ 0. 048 〇0. 24 〇〇Comparative Example 4 78 0 52 〇0. 074 X 0. 22 XX Comparative Example 5 81 0. 35 X 0. 113 X 0. 24 〇X From the results of Table 3, in Examples 1 to 12 of the present invention, by melt extrusion The method produces a polystyrene tree filament, and obtains foaming polystyrene particles having a whiteness as low as 62 to 72 and having transparency and a bulk density as high as 0.61 to 65.65 g/cm3. The foaming polyphenylene enelate (IV) obtained in Examples 1 to 3 has a good particle life evaluation (IV) and can be stored for a long period of time. In Examples 丨 to 3, particles having a small Cv value, small variation in particle size distribution, and uniform particle size. Further, the foamed molded article obtained in Examples 丨 to 3 had a high bending strength, and even at a high expansion ratio (10) times, a good strength of 322950 65 201202317 was obtained. Particularly in the foam molded articles of Examples 10 and 11, the bending strength was particularly good. On the other hand, in Comparative Example 4, the water pressure was lower than that of Examples 10 to 12, and the whiteness of the expandable polystyrene resin particles obtained was 78, which exceeded the whiteness standard (75 or less) of the present invention. Further, the bulk density was lowered to 0.52 g/cm3, and white and lightly foamable polystyrene-based resin particles were obtained. In Comparative Example 4, the Cv value became large, and the deviation of the particle diameter was observed. In addition, the flexural strength of the foamed molded article obtained in Comparative Example 1 was lowered, and it was judged as poor (X) 0 in total, and Comparative Example 5 in which Dingyuan was used as a foaming agent, although the water pressure was increased to 1.7 MPa, the obtained hair was obtained. The whiteness of the foamy polystyrene-based resin particles is 81, which is more than the whiteness standard (75 or less) of the present invention, and the bulk density is lowered to 0.35 g/cm3 to obtain a white and lightly foamable polystyrene. Resin particles. The expandable polystyrene-based resin particle particles obtained in Comparative Example 5 had a poor life (X) and could not be stored for a long period of time. Further, when the Cv value was increased, the deviation of the particle diameter was observed, and it was judged to be poor (X). (Probability of industrial use) The foaming property of the polystyrene-based resin foam molded article having excellent mechanical strength such as bending strength, compressive strength, and impact resistance can be obtained even at a high expansion ratio. Polystyrene resin particles. The polystyrene resin foam molded article of the present invention can be used for various purposes such as a heat insulating material or a packaging material. Moreover, the present invention relates to a thermoplastic resin pre-formed foamed pellet for use in the production of a thermoplastic resin foamed molded article such as a polystyrene-based resin foam molded article.

66 322950 S 201202317 Sub-manufacturer and its manufacturing method 'Furthermore, in detail, the pores of the thermoplastic mold-making mold of the melt-blown foaming agent are extruded into the water and the like, and then cut off immediately to make the tree. The production of the foamable thermoplastic tree filament by the so-called melt extrusion method is carried out, and the cut particles are foamed in a cooling medium, and are directly produced in the production of the foamed molded body: the thermoplastic resin is prepared The technology of bubble particles. According to the present invention, the thermoplastic resin-prepared foamed particles used in the production of the foamed molded article can be directly produced by melt extrusion, and the foamed filaments are conventionally produced and fined (4) preliminary foamed particles. Compared with the method, the foamed molded article can be produced in a smaller number of steps, and the production efficiency of the foamed molded article is reduced, which can reduce the storage space of the expandable resin particles. The thermoplastic resin pre-expanded particles obtained by the method of the present invention are spherical to slightly spherical, and are better in the cavity of the forming mold than in the pre-expanded particles which are in the form of a crucible. It can be filled without a gap, and the 'foaming between the expanded particles can be satisfactorily performed in the mold (4). The foamed molded body having excellent strength can be obtained. Further, the foamable polystyrene-based lipid particles provided by the present invention are obtained by melt-extrusion method, and are obtained from a foamed molded body having excellent strength and a foaming agent. The dispersion from the foamable resin particles is stable, and the storage period (particle life) is long. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an example of a manufacturing apparatus used in a method for producing foamable polystyrene resin particles containing bubbles according to the present invention. [Main component symbol description] 67 322950 201202317 1 Extruder (resin supply device) 2 Mold 3 Raw material supply hopper 4 High pressure pump 5 Foaming agent supply port 6 Cutter 7 Cutting chamber 8 Sink 9 rfj pressure pump 10 Solid-liquid separation function Dehydration dryer 11 storage container 68 322950

S

Claims (1)

201202317 VII. Patent application scope: 1. A foamable polystyrene resin particle containing bubbles, which is a foaming polystyrene resin containing a foaming agent and bubbles in a polystyrene resin particle. When the number of the bubbles existing in the cross section of the cross section of the foam-containing expandable polystyrene-based resin particle-containing cross-section removed from the particle surface is 200, the resin particles are η/mm2 and the bulk density is pg/cm3. Equation (丄) The calculated N value is 400 or more, Ν = η / (1/ρ ) (1). 2. The foamable polystyrene according to the first aspect of the invention, wherein the enthalpy is in the range of from 400 to 2,000. 3. The foamed polystyrene-based resin particles containing bubbles according to the first or second aspect of the invention, wherein the bulk density is 0.4 g/cm3 or more. 4. A method for producing foamable polystyrene-based resin particles containing bubbles, wherein a foaming agent and a foaming agent are added to a polystyrene resin in a resin supply device, and a foaming agent is contained. The molten resin is extruded from a small hole of a mold attached to the front end of the resin supply device into the cooling liquid, extruded while cutting the extrudate 'and cooled and solidified' by bringing the extrudate into contact with the liquid. The method of foaming polystyrene-based resin particles, wherein the foaming polystyrene-based resin particles are micro-foamed in the particles before cooling and solidifying, to obtain: a cross-section of the particle center from the grain 1 322950 201202317 ^When the number of bubbles in the cross section of 200#m is 11/mm2, and the bulk density is pg/cm3, the bubble-like polycondensation containing the bubble with the N value of 400 or more calculated by the formula (1) Stupid vinyl resin particles, N = n / (l / p) (1). 5. The method for producing foam-containing foamable polystyrene-based resin particles according to Item 4, wherein the N value is in the range of 4 Å to 2,000. 6. The method for producing foam-containing expandable polystyrene-based resin particles according to the fourth or fifth aspect of the invention, wherein the bulk density is 〇.4 g/cm3 or more. The method for producing a foam-containing foamable polyethylene-based resin particle according to any one of claims 4 to 6, wherein the foaming nucleating agent is an inorganic powder or A masterbatch type foaming nucleating agent in which a chemical foaming agent is uniformly dispersed in a base resin. The foamed polystyrene resin particles containing the bubbles according to any one of the first to third aspects of the invention are obtained by heating the foamed polystyrene resin particles containing the bubbles according to any one of claims 1 to 3. A polystyrene-based resin foam molded article obtained by filling the polystyrene-based resin pre-expanded particles described in claim 8 in a cavity of a molding die and heating the same in the mold. The bubble is formed by the person. (1) A polystyrene-based resin foamed molded article, which is filled with a foamed polystyrene-based resin particle containing bubbles as described in any one of claims 1 to 3, which is filled in a molding die. It is heated in the cavity and 2 322950 S 201202317 is foamed and formed in the mold. 11. A method for producing a thermoplastic resin-prepared expanded particle by melt-kneading a thermoplastic resin and a foaming agent in a resin supply device, and extruding the melted thermoplastic resin containing a foaming agent through a small hole of the mold Immediately after being cooled in the cooling medium, the foamed foam is expanded into a volume expansion ratio of 1.6 times or more of the thermoplastic resin-prepared foamed particles, and then the foamed particles are separated from the above-mentioned cooling medium to obtain heat. The plastic resin is used to prepare the expanded particles. 1. The method of the present invention, wherein the volume expansion ratio of the thermoplastic resin-prepared foamed particles is in the range of 1.6 to 50 times. The method for producing a thermoplastic resin-prepared foamed particle according to the above-mentioned item, wherein the foaming agent-containing thermoplastic resin is used in an amount of 1 part by mass based on the thermoplastic resin. It contains 1 to 10 parts by mass of a foaming agent. The method for producing a thermoplastic resin-prepared expanded particle according to any one of the preceding claims, wherein the foaming agent is one or both of isoprene and n-pentyl a mixture. The method for producing a thermoplastic resin-prepared expanded particle according to any one of the preceding claims, wherein the thermoplastic resin is a polystyrene resin. The thermoplastic resin-prepared foamed particle is obtained by the method for producing a thermoplastic resin-prepared foamed particle according to any one of the above-mentioned items of the present invention. 322950 3 201202317 π. A method for producing a thermoplastic resin foamed molded article, which is a method for producing a thermoplastic resin-prepared foamed particle according to any one of claims 11 to 15 The obtained thermoplastic resin-prepared foamed particles are filled in a cavity of a molding die and heated to be foam-molded in a mold to obtain a thermoplastic resin foam molded body. A thermoplastic resin foam molded article obtained by the method for producing a thermoplastic resin foam molded article according to claim 17 of the invention. 19. A foamable polystyrene resin particle in which a polystyrene resin and a foaming agent are melted and kneaded in a resin supply device, and a melted polystyrene resin containing a foaming agent is passed through a mold. The expandable polystyrene resin particles obtained by extrusion, cooling, and cutting of the small holes are those having a whiteness of 75 or less as measured by an integrating sphere type color difference meter. The foamable polystyrene resin particle according to claim 19, which contains a refractive index relative to the polystyrene resin relative to 100 parts by mass of the polystyrene resin. The amount of the inorganic material powder having a refractive index of ±0.08 or less is 1. G parts by mass or less as a foaming nucleating agent. 21. The foamable polycrystalline resin particles as described in the above-mentioned _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The intermediate f contains 2 to 15 parts by mass of a foaming agent. 322950 The foamable polystyrene resin particle according to any one of the items 19 to 22, wherein the foaming agent is one of isopentane and n-pentane or a mixture of the two. 24. A method for producing foamable polystyrene resin particles, wherein a polystyrene resin and a foaming agent are melted and kneaded in a resin supply device, and a melted polystyrene containing a foaming agent is used. The resin is extruded into a cooling medium through a small hole of a mold, cooled, and cut, to obtain a method for producing expandable polystyrene resin particles, wherein the melted polystyrene resin containing a foaming agent is extruded. The foamed polystyrene resin particles having a whiteness of 75 or less as measured by an integrating sphere type color difference meter were obtained by cooling to a cooled cooling medium. The method for producing the expandable polystyrene-based resin particles according to claim 24, wherein the refractive index is added to the polystyrene resin with respect to 100 parts by mass of the polystyrene resin. The amount of the inorganic material powder having a refractive index of ±0. 08 or less is 1.0 part by mass or less as a foaming nucleating agent. The foaming polystyrene resin having a bulk density of 0. 58 g/cm 3 or more is obtained by the method of producing the expandable polystyrene resin particles according to the above-mentioned application. Particles. The method for producing the expandable polystyrene-based resin particles according to any one of the present invention, wherein the foaming is contained in 100 parts by mass of the polystyrene resin. The agent is 2 to 15 parts by mass. The method for producing a foamed 5 322950 201202317-type polystyrene-based resin particle according to any one of claims 24 to 27, wherein the foaming agent is isopentyl and n-pental One or a mixture of the two. (2) A polystyrene-based resin-prepared foamed particle obtained by heat-expanding the expandable polystyrene-based resin particles according to any one of the items of the present invention. 30. A polystyrene-based resin foam molded article obtained by filling the polystyrene-based resin pre-expanded particles described in claim 29 in a cavity of a molding die and heating the same in the mold Foamed by 0 6 322950 S