TW201125905A - Process for production of expandable resin particles, pre-expanded beads, and products of expansion molding - Google Patents

Abstract

A process for the production of expandable resin particles, which comprises bringing starting resin particles (which can form expandable resin particles) into contact with an ultraviolet absorber when impregnating the starting resin particles with a blowing agent. The expandable resin particles obtained by the process have ultraviolet-screening properties.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an expandable resin particle, a pre-expanded particle, and a foamed molded article. More specifically, the present invention relates to a method for producing an expandable resin particle to which an ultraviolet absorbing function is imparted, a pre-expanded particle, and a foamed molded article. The foamed molded article obtained from the expandable resin particles of the present invention is suitable for transporting and/or storing a container of an electrical product which may be damaged by ultraviolet rays. [Prior Art 3] Various articles or parts thereof are placed in a container in order to protect them from damage during transportation or storage. Such a container is usually a resin container, and it is particularly preferable to use a container having a foaming molding system which is shock-absorbing. However, in the case of products, sometimes the manufacturing location is separate from the location of the sale. In the case of a part, the location where the part is made and the place where the part is assembled into a product are sometimes separated. In recent years, with the globalization of the economy, these locations have been transnational. Therefore, the delivery or retention of the product or part will be extended. For example, electrical products are known to be degraded by ultraviolet radiation. In the case of long-term transportation or storage, the chance of exposure of electrical products to ultraviolet light increases. Therefore, the container not only needs excellent cushioning properties against impact, but also needs to be shielded from ultraviolet rays that are exposed during transportation or storage. In order to produce a foamed molded article to which a UV absorber has been applied, a method of preliminarily presenting a UV absorber in a resin component has been studied in the literature. Japanese Patent Publication No. Hei. 6 (Patent Document No.) In the extrusion machine, the bismuth component is mixed with the purple (four) shape, and the L coating agent is infiltrated into the extruded granules to obtain the foamable resin particles. PRIOR ART DOCUMENTS [Patent Document] Patent Document 1: Japan SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION The above publication is based on the use of an ultraviolet absorber for the purpose of improving weather resistance. Further, the ultraviolet absorber is mixed with a resin component by an extruder. The obtained foamed molded body can shield a certain degree of ultraviolet rays. However, it has been sought to more efficiently and easily mix the ultraviolet absorbers, and the ultraviolet light shielding property is further improved in the formation of the tree. Further, the foam molded article having both impact resistance and the method for producing the foamable resin particles for producing the foam molded article For the method of producing the resin particles, various methods such as an extrusion method, a suspension polymerization method, and an emulsion polymerization method are known. The inventors of the present invention have studied the period of addition of the ultraviolet absorber. As a result, it has been unexpectedly found that by adding the ultraviolet absorbing agent to the blowing agent at the time of impregnation of the blowing agent, rather than at the time of production of the resin particles, a foamable resin particle which can provide both high-order elements can be obtained. Thus, the object of the foaming molded body of ultraviolet shielding property and impact resistance is thus completed. Thus, according to the present invention, a method for producing foamable resin particles can be provided by impregnating a foaming agent to In the case of the resin particles of the foamable resin particles, the ultraviolet ray absorbing agent is brought into contact with the resin particles to obtain foamable resin particles having ultraviolet shielding properties. Further, according to the present invention, a pre-expanded particle can be provided. It is obtained by pre-expanding the expandable resin particles obtained by the above method to a volume ratio of 5 to 60 times. According to the present invention, it is possible to provide a foamed molded article which can be obtained from expandable resin particles containing an ultraviolet absorber, and which has 3% of a sample having a thickness of 5 mm cut from the skin thereof. The following 365 nm wavelength light transmittance. According to the present invention, the ultraviolet absorber can be easily and efficiently absorbed by the resin particles by the contact period of the resin particles with the ultraviolet absorber during the impregnation of the foaming agent. Therefore, according to the present invention, it is possible to obtain a foamable resin particle which can provide a foam molded article having both ultraviolet shielding properties and impact resistance. Further, when the ultraviolet absorber is a benzotriazole When a UV absorber of a diphenyl ketone type is used in an amount of 0.01 to 0.5 parts by weight based on 100 parts by weight of the resin particles, a foamable resin particle which can provide ultraviolet rays can be obtained. A foamed molded body with improved shielding properties. In the case where the resin particles contain resin particles of a polyolefin resin and a polystyrene resin, a foamable resin particle can be obtained, and the foamable resin particle can provide a foam molded body. In the foaming 201125905 molding system, even if the polystyrene resin component is added in order to improve the life of the bead, the ultraviolet shielding property can be maintained, and the impact resistance and the crack resistance are excellent. In the case where the resin particles contain 100 parts by weight of the polyolefin resin and 120 to 560 parts by weight of the resin particles of the polystyrene resin, one type of expandable resin particles can be obtained, and the bead life is further improved. It can be high-order and has both impact resistance and crack resistance, but UV shielding can still be maintained. The pre-expanded particles obtained by pre-expanding the expandable resin particles into a volume ratio of 5 to 60 times provide a foam molded body which can have high-order ultraviolet shielding properties. Impact resistant. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the wavelength of irradiation light and the transmittance of the foamed molded article of Example 1. Fig. 2 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 2. Fig. 3 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 3. Fig. 4 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 4. Fig. 5 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Comparative Example 1. Fig. 6 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 7. Fig. 7 is a schematic view showing a measuring device for ultraviolet transmittance of a foamed molded article. 201125905 Figures 8(a) and 8(b) are graphs showing the respective wavelengths of ultraviolet light, the foamed articles of Example 1 and Comparative Example 1. In the method for producing the foamable resin particles, the contact between the resin particles and the ultraviolet absorbing agent is carried out at the time of impregnation of the foaming agent. Here, the contact of the ultraviolet absorber with the resin particles is carried out by the presence of the ultraviolet absorber in the vicinity of the resin particles when the foaming agent is impregnated. The ultraviolet absorber may be added at the same time as the foaming agent is impregnated, or may be added to a system in which the resin particles are preliminarily present before the foaming agent is impregnated. (1) Resin Particles The resin particles may be particles of the foamable resin particles, in other words, the particles which are impregnable with the foaming agent are not particularly limited. For example, resin particles composed of a resin component such as a polyolefin resin, a polystyrene resin, or a mixture of these resins may be used. Further, the resin component may contain a rubber component (polybutadiene, butadiene-styrene copolymer, etc.) within a range that does not impair the effects of the present invention. The polyolefin resin is not particularly limited, and a known resin can be used. Further, the polyolefin resin may be crosslinked. For example, branched low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate copolymer, ethylene methyl methacrylate copolymer, such copolymers Polyethylene resin such as crosslinked body, propylene monomer, ethylene-propylene random copolymer, propylene-1-butene copolymer, ethylene-propylene-butene 201125905

. In the above illustration, the low density is

The alkyl acrylate@, and the second means that the stupid ethylene accounts for 70% by weight or more of the total monomer. Examples thereof include mercaptostyrene, p-methylstyrene, acrylonitrile, nitrile, acrylic acid, methacrylic acid, alkyl acrylate, methyl hydrazine, divinylbenzen, and polyethylene glycol dioxime. In the exemplification of the base, the "burning base" means a hospital base having 1 to 8 carbon atoms. The resin component preferably contains a polyolefin resin and a polystyrene resin. In this case, the polyolefin-based resin to be used is preferably a branched low-density polyethylene, a linear low-density polyethylene or an ethylene-vinyl acetate copolymer, and the polystyrene resin is polystyrene. A styrene-alkyl acrylate copolymer or a styrene-alkyl methacrylate copolymer is preferred. The content of the polystyrene resin is preferably in the range of 120 to 560 parts by weight based on 100 parts by weight of the polyolefin resin particles in the resin particles. When the content of the polyethylene-based cerium resin is more than 560 parts by weight, the crack resistance of the foamed molded article is lowered. On the other hand, when the amount is less than 12 parts by weight, the crack resistance is greatly improved, but the foaming agent tends to be dissipated from the surface of the foamable resin particles. As a result, the life of the beads of the expandable resin particles is shortened due to a decrease in the preservability of the foaming agent. The preferred polystyrene tree 201125905 has a fat content of 140 to 450 parts by weight, and a more preferred content is 15 〇 __ a replacement portion. For example, the polyolefin resin and the polystyrene resin are contained together, and the two resins are stirred and kneaded in an extruder, and the stupid vinyl monomer is impregnated in the aqueous medium. Among the particles composed of the olefin-based tree scorpion, the method of polymerizing the monomer, and the like. Among them, the latter method is preferable in that the two resins can be mixed more uniformly and can be obtained closer to the spherical particles, which is suitable. Here, the resin particles obtained by the latter method are referred to as a composite resin sheet composed of polyolefin and polystyrene. The latter method will be described below. First of all, 'the crude hydrocarbon system as a raw material can be known by a method = for example, first, after melt-extruding a poly-hydrocarbon resin using an extruder, It is cut by underwater, strand cut/polyolefin Coffee particles. Usually, "f)4 is known to be granulated, and the shape of the polyolefin-based resin used is, for example, a true spherical shape, an elliptical globule (y egg shape), a cylindrical shape, a prismatic shape, a particle 7 (Pellet) or Granular (referred to as fine particles (10) Township (4). Under the ice-cream fat-based polyolefin resin, 'can also contain a radical scavenger. Free radical trapping can be added to the resin in advance, or In the case of melt extrusion:: as a radical scavenger, it is a polymerization inhibitor (including a polymerization pump (4) oxime, a hindered amine light stabilizer, etc., which has a compound which is trapped as a radical (4) and is hardly soluble in water. Preferably, the amount of the domain capture d is preferably 0.005 to 0.5 parts by weight based on the weight of the thin smoke resin (10). The poly (four) filament cut contains other talc, calcium citrate, and stearin. 201125905 A nucleating agent such as calcium sulphate, synthetic or naturally occurring cerium oxide, bis-stearate, methacrylate copolymer, etc., triallyl isocyanate 6 bromide a coloring agent such as a burning agent, carbon black, iron oxide, or graphite, etc. Next, a polyolefin tree is used. The lipid particles are dispersed in an aqueous medium in the polymerization vessel, and the styrene-based monomer is polymerized while being impregnated into the polyolefin-based resin particles. The aqueous medium may be water, water or a water-soluble solvent (for example, an alcohol). The styrene monomer may be any of styrene and substituted styrene (the substituent includes a lower alkyl group, a halogen atom (especially a gas atom), etc.), and a styrene system can be used. a mixture of styrene and substituted styrene, styrene and a small amount of other monomers copolymerizable (for example, acrylonitrile, alkyl methacrylate (the alkyl moiety has a carbon number of about 1 to 8), and cis. Mono or dialkyl enedioic acid (about 1 to 4 carbon atoms in the alkyl moiety), divinylbenzene, mono or diacrylic acid of ethylene glycol or even decyl acrylate, maleic acid Sf, N- a mixture of phenylsuccinimide (N-phenylmaleimide, etc.). Among these mixtures, styrene is preferably present in a controlled amount (for example, 50% by weight or more). Further, the styrene monomer is also Toluene, xylene, cyclohexane can be added Solvent (plasticizer) such as alkane, ethyl acetate or dioctyl adipate. The impregnation of the styrene monomer toward the polyolefin resin particles can be carried out while polymerizing, or before starting the polymerization. In the case where the polymerization is carried out at the same time, it is easy to cause polymerization of 10 201125905 styrene monomer in the vicinity of the surface of the polyolefin resin particle. Further, the stupid ethylene monomer which is not impregnated into the polyolefin resin particles is easily polymerized alone, and as a result, a large amount of fine particles of the polystyrene resin particles are formed. An oil-soluble radical polymerization initiator is used. As the 5-molecular polymerization initiator, a polymerization initiator which is generally used for polymerization of a styrene monomer can be used. The method of adding a polymerization initiator to the aqueous medium in the polymerization container may be exemplified by various methods, for example, the following methods: (1) Dissolving the polymerization initiator in another container different from the polymerization container a method of supplying a styrene monomer to a polymerization vessel in a styrene monomer; (2) dissolving the polymerization initiator in a solvent such as an isoparaffin or a plasticizer which is a part of the styrene monomer Preparation of the solution. The solution is supplied to a polymerization vessel simultaneously with a predetermined amount of a styrene-based monomer; (3) A dispersion in which a polymerization initiator has been dispersed in an aqueous medium is prepared. A method of supplying the dispersion and the styrene monomer to a polymerization vessel. The amount of the polymerization initiator to be used is usually 0.02 to 2.0% by weight based on the total amount of the styrene-based monomer to be added. In the aqueous medium, it is preferred to dissolve the water-soluble radical polymerization inhibitor in advance. The water/grain free radical polymerization inhibitor can not only inhibit the polymerization of the phenethyl (10) monomer located on the surface of the polystyrene tree, and prevent the polymerization of the styrene monomer floating in the aqueous medium, thereby reducing the aggregation. Microparticles of styrene resin. As a hydrothermal radical polymerization inhibitor, it is possible to use a polymerization inhibitor which dissolves 1 g or more with respect to water 201125905 100 g. The amount of the water-soluble radical polymerization inhibitor to be used is preferably 0.001 to 0.04 parts by weight based on 100 parts by weight of the water of the aqueous medium. Further, in the aqueous medium, a dispersing agent such as an inorganic dispersing agent or a surfactant is preferably added in advance. The shape and structure of the polymerization vessel are not particularly limited as long as they are conventionally used for suspension polymerization of a styrene monomer. For example, a polymerization vessel equipped with a stirring slurry can be used. Further, the shape of the stirring slurry is not particularly limited, and specific examples thereof include a blade slurry of a V-shaped blade slurry, a Faudora de-slurry, a tilted blade slurry, a flat blade slurry, a feather slurry, and the like; a turbine type agitating slurry, a fan-type slurry Turbine pulp; such as propellers for marine propellers. Among the agitating slurries, vane pulp is preferred. Stir the slurry with a single-stage slurry or a multi-stage slurry. A baffle may also be provided in the polymerization vessel. Further, the temperature of the aqueous medium when the styrene monomer is polymerized in the fine particles is not particularly limited, but is preferably in the range of -30 to + 20 ° C of the melting point of the polyolefin resin to be used. More specifically, it is preferably 70 to 140 ° C, more preferably 80 to 135 ° C. Further, the temperature of the aqueous medium can be maintained at a fixed temperature from the start to the end of the polymerization of the styrene monomer, and the temperature can be increased stepwise. When the temperature of the aqueous medium is raised, it is preferable to increase the temperature at a temperature increase rate of 0.1 to 2 ° C /min. Further, if particles composed of a polyolefin resin which has been crosslinked are used, the crosslinking may be carried out before the styrene monomer is impregnated, or the styrene monomer may be impregnated and polymerized into the particles. The period of the period 12 201125905 can be carried out after the styrene monomer is impregnated and polymerized in the fine particles. The cross-linking agent for cross-linking the poly-smoke-based resin may, for example, be 2,2-di-tertiary butyl peroxy oxo, bis-propyl peroxide, 2,5-di-f-based _2 , organic peroxides such as 5_ di-tertiary butyl. Further, the crosslinking agent may be used singly or in combination of two or more. Further, the cross-linking amount is usually (parts by weight) of (9) parts by weight based on the hydrocarbons (fine particles) of the hydrocarbons, preferably (4) parts by weight. As a method of adding a crosslinking agent, for example, a method of directly adding a crosslinking agent to a polyolefin-based resin; a method of dissolving a crosslinking agent in a solvent, a plasticizer or a styrene-based monomer sheet; and adding a crosslinking agent; A method of dispersing in water and then adding it. Among them, a method in which a crosslinking agent is dissolved in a styrene monomer is preferably added. (2) Ultraviolet absorber The ultraviolet absorber is not particularly limited, and any known ultraviolet absorber can be used. Specifically, 2_(29_benzotriazole-2-yl)_p-methyl, 2-(2H-benzotrimethylene). 2-[5-Gas-(2H)- benzotriazole-2-yl]_4_fluorenyl_6_(tri-butyl)benzene, 2,4_-di-butyl-6-(5 - Benzene benzo. Sodium-2-yl) benzophenone quinone, such as 2- -4-(octyloxy)-octabenzone diphenyl ketone, such as 2- (4,6-Diphenyl-1,3,5-tripentyl 2-yl)-5-[(hexyl)oxy]phenol, a tri- or "malonate" ultraviolet absorber, etc. A stupid triazole system and a diphenyl ketone ultraviolet absorber are preferred. The ultraviolet absorber is present in the impregnation system when the foaming agent is impregnated. The inventors and the like presumed that the ultraviolet absorber is impregnated with a foaming agent. At the same time, 13 201125905 /, the tree scorpion particles are in contact with each other, and the surface layer of the resin particles is coated and penetrated into the inner layer σ Ρ °. The amount of use is preferably 0.01 to 0.5 psi with respect to 100 parts by weight of the resin particles. When the amount is less than 0.01 part by weight, the amount of 3 & Η and the external absorbent in the obtained expandable resin particles is small. If it is more than Q5 parts by weight, if it is more than Q5 parts by weight, the thickness of the foam will be from the usual use. If it is considered, even if the amount is more than this, it can only be equal. The effect of the heart' is not inconvenient to handle at the time of production, or it may be inferior. The impact resistance is inferior. The preferred amount is 0 to 0.4 parts by weight. (3) The foaming agent is used as a foaming agent. Any of various known volatile foaming agents can be used. Specific examples thereof include hexane, n-pentane, isopentane, neopentane, industrial pentane, petroleum ether, n-butane, isobutane, and propane. Cyclohexane, cyclopentane, etc., especially in the order of the simmering and the sputum. Further, a foaming auxiliary agent may be used. Examples of the foaming auxiliary agent include hexane, d-limonene, and the like. Solvent; diisobutyl adipate, glycerin, styrene monododecanoate, coconut oil and other plasticizers (high boiling point solvent). Further, the amount of foaming auxiliary added is relative to the resin particles. The weight fraction is preferably 5 to 10 parts by weight. The impregnation of the blowing agent is, for example, under a pressure or a normal pressure at a temperature of 30 to 140 ° C. It is carried out in a manner known per se for 0.5 to 6 hours. For example, a resin mixer can be used to flow resin particles in a sealed pressure vessel by a rotary mixer such as a V-type, a c-type or a DC type. A method for impregnating a solvent; a method of impregnating a resin particle with a foaming agent in a sealed pressure-resistant container; and a sealing system after the resin particle is manufactured by a polymerization method; A method of impregnating the foaming agent, etc. The foaming agent content in the expandable resin particles is preferably 7.5 to 11 parts by weight based on 100 parts by weight of the resin particles. When the content of the foaming agent is less than 7.5 parts by weight, the foaming property of the expandable resin particles may be lowered. On the other hand, when the foaming property is lowered, it is difficult to obtain a low-bulk-density pre-expanded particle having a large volume ratio, and the foamed molded article obtained by performing the in-mold forming of the pre-expanded particle may have a low melting ratio. Low cracking. On the other hand, when it exceeds 11 parts by weight, a pre-expanded particle having a low bulk density of 65 times or more by volume can be obtained. However, the size of the bubbles in the pre-expanded particles tends to be too large, and the formability is inferior, and the strength characteristics such as compression and deflection of the obtained foamed molded body are inferior. A preferred blowing agent content is in the range of 8 to 10.5 parts by weight. (4) Average particle diameter of the expandable resin particles The average particle diameter of the expandable resin particles is preferably 800 to 2400 μm. The foamable resin particles having an average particle diameter of less than 800 μm have a poor yield when the particles are obtained, and as a result, the cost is increased. Further, the retention of the foaming agent is low, and the life of the bead tends to be short. On the other hand, when it is more than 2,400 μm, the foaming molded body having a complicated shape is formed, and the filling property to the mold tends to be deteriorated. A suitable average particle diameter system is 1200~2〇〇〇μηι. (Pre-expanded particles) Next, the pre-expanded particles are obtained by pre-expanding the expandable resin particles to a volume ratio of 5 to 60 times. Specifically, if necessary, a heating medium such as steam is used to heat the foaming resin 15 which has been impregnated with a foaming agent, and the particles are pre-expanded to a predetermined bulk density, thereby obtaining pre-expansion. particle. The pre-expanded particles have a volume ratio of 5 to 6 〇 times (bulk density 0-016 to 〇. 2 g/cm 3 ) » Suitable volume multiples are 1 〇 to 55 times. When the volume ratio is more than 60 times, the closed cell ratio of the pre-expanded particles is low, and the strength of the foamed molded article obtained by foaming the pre-expanded particles is inferior. On the other hand, if it is less than a multiple, the weight of the foamed molded body obtained by foaming the pre-expanded particles will increase. (Foamed molded article) The foamed molded article of the present invention is obtained from a foamable resin particle containing an ultraviolet absorber. Further, the foam molding system had a transmittance of light of 365 nm wavelength of 3% or less in a sample cut into a thickness of 5 mm from the skin.吕要吕之' The foam forming system has high ultraviolet shielding properties in the field of 5 mm thickness from the skin. The transmittance is preferably 2% or less. The foam molding system is obtained by molding the above pre-expanded particles in a mold. Specifically, the pre-expanded particles are filled in a molding machine mold, and heated to be secondarily foamed, whereby the pre-expanded particles are fused and integrated with each other, whereby a foamed molded article having a desired shape can be obtained. As the above-mentioned molding machine, an EPS (expanded polystyrene) molding machine used for producing a foamed molded article from prepolymerized particles of polystyrene resin can be used. The obtained foamed molded article ' can be used for a cushioning material (mat) of an electric product or the like, an electronic component, a toner cartridge, a shipping container of various industrial materials, foods, and the like. The foam molding system is derived from foamable resin particles in which the ultraviolet absorber is not only present on the surface but also dispersed inside. Therefore, the ultraviolet light of 201125905 in the transmitted light is largely blocked on the surface of the foamed molded body, and at the same time, the inside of the foamed body passes through the multiple scattering and passes through the cell containing the ultraviolet absorber, whereby it can be efficiently interrupted. For example, when the transmittance of light of 350 nm, 500 nm, and 800 nm is measured in the case where the surface of the foamed molded body is sliced to a thickness of 1 mm, the present invention can obtain a foamed molded article having the following relationship. 'that is, the transmittance at 350 nm / the transmittance at 500 nm (ratio A) is 1/2 or less; and/or the transmittance at 35 〇 nm / the transmittance at 8 〇〇 0111 (ratio B) is 1 /3 or less. The lower the ratio a, the lower the value means that the wavelength of 350 nm is less transmitted than the wavelength of 500 nm. Similarly, the lower the ratio b, the lower the value means that the wavelength of 350 nm is less transmitted than the wavelength of 800 nm. In summary, the lower the ratio A and the ratio B, the higher the effect of selectively masking the ultraviolet rays. Further, the ratio A is preferably in the range of 0.4 to 0, and the ratio B is preferably in the range of 〇 3 to 〇. By having the transmittance in these ranges, a foam molded article having a higher effect of selectively shielding ultraviolet rays can be obtained. The shape of the foamed molded article is not particularly limited, and can be appropriately set in accordance with the shape of the product to be transported and/or retained. The foamed molded article of the present invention can efficiently transport not only ultraviolet rays but also impact resistance, and therefore can be transported over long distances or stored for a long period of time. EXAMPLES The following examples are further illustrated, but the invention is not limited to the examples. <Foaming agent content of expandable resin particles> 17 201125905 Precision weighing 5 to 20 mg of expandable resin particles is used as a measurement sample. The measurement sample was placed in a thermal decomposition furnace (PYR-1A manufactured by Shimadzu Corporation), which was kept at 180 to 200 ° C, and the measurement sample was sealed, and then heated for 12 seconds to prepare a foaming agent component. release. The foaming agent component to be released was obtained by gas chromatography (manufactured by Shimadzu Corporation: GC-14B, detector: FID) under the following conditions. The content of the foaming agent in the expandable resin particles (% by weight) is determined from the calibration curve of the foaming agent component which has been previously measured, and the measurement conditions of the gas chromatography are determined.

Pipe column: "Shimalite 60/80 NAW" manufactured by Shinwa Chemical Co., Ltd. (0 3mm><3mm) Column temperature: 70°C Detector temperature: 110°C Inlet temperature: ll〇°C Carrier gas: Nitrogen carrier gas Flow rate: 60 ml/min <pre-expansion condition> 500 to 2000 g of the foamable resin particles are placed in an atmospheric pre-expansion machine (50 L of internal volume) which has been preheated by steam, while stirring and simultaneously 0.0 2 Μ P a is set to introduce steam, and air is also supplied, which is foamed to a predetermined bulk density (volume multiple) during about 2 to 3 minutes. <Volume multiple of pre-expanded particles> The weight (a) of the pre-expanded particles of about 5 g was weighed to two decimal places. Next, the weighed pre-expanded particles were placed in a 500 cm3 graduated cylinder with a minimum memory unit of 5 cm3. Touching the extrusion tool to read the volume of the pre-expanded particles (b) 'The extrusion is a circular resin plate slightly smaller than the cylinder diameter, and in which 18 201125905 the heart is upright fixed with a width of about 1.5 cm, A rod-shaped resin plate of about 30 cm in length. Next, the volume multiple of the pre-expanded particles is obtained according to the formula (b)/(a). <Multipture of the foamed molded article> The test piece (for example, 75 x 300 x 35 mm) was cut out from the foamed molded article (after drying at 40 ° C for 20 hours or more). The weight of the piece (a) and volume (b). Then, according to the formula (.../(check the multiple of the foamed molded body. <Transmittance of the foamed molded body>>

(1) Method A A sample was obtained by cutting (cutting) a foamed molded body with respect to a skin portion by 5 〇 x 5 〇 x 5 mm (± 1 mm or less). As shown in Fig. 7, uv light (ultraviolet light) 1 (HLR100T-2 manufactured by SEN LIGHTS CORP, lamp: HL100) is placed in a spectroradiometer 2 (portable spectroradiometer (manufactured by Hidehiro Seiki Co., Ltd. 1^§_72) In the upper side of the illuminating unit 3, the illuminating unit 3 and the spectroradiometer 3 are provided so as to be 90±5 mm from the front end of the UV light 1 to the light receiving unit 3. In the figure, 4 indicates a light source, and 5 indicates a light cover. First, the spectroradiometer 丨 measures the original light radiance for the "allowed (7) wavelength light. Then, the sample is placed on the light receiving unit 3, and the transmission of the wavelength light for the milk handsome is measured. The original radiance and the sample transmission radiance are substituted for the following equations, and the transmittance of each sample is obtained. The so-called transmittance "(10) in this specification refers to the average value of the value of the 丨 sample measured three times. Transmittance ( %) = transmission radiance of the sample (365 η _ original radiance (365 nm) x 1 若 The average value of the transmittance obtained by the above δ 算 formula is 3.0% or less, 19 201125905 is judged to have good ultraviolet ray shielding Broken.

(2) Method B The foamed molded body was cut into a skin portion of 4 〇 x 4 〇 x about 1 mm (thickness). The transmittance of the cut sample was measured by an ultraviolet-visible spectrophotometer (UV-245 0PC manufactured by Shimadzu Corporation). Three points or more were simultaneously measured by changing the measurement point for one sample. The measurement conditions were a measurement wavelength range of 800 to 200 nm, a slit width of 2.0 nm, and a visible light ultraviolet light source switching wavelength of 360 nm, and a halogen lamp and an illuminating lamp were used as the light source. According to the measurement results obtained, the transmittance of 350 nm to the transmittance of 500 nm (ratio A) and the transmittance of 350 nm to the transmittance of 800 nm were calculated for each measurement point as shown by the following formulas 1 and 2, respectively. Ratio B). Next, the ratio A of the three or more measurement points and the average value of the ratio B were obtained. When the ratio A is 1 /2 or less and/or the ratio B is 1/3 or less, it is judged to have good ultraviolet ray blocking property. Moreover, this judgment was performed for the case where the transmittance of 500 nm and 800 nm was 1.0% or less. (Formula 1) (transmittance at 35 〇 nm) % / (transmittance at 500 nm) % = ι / 2 or less (formula 2) (transmittance at 350 nm) % / (transmittance at 800 nm) % = ι / 3 or less <Detection amount of ultraviolet absorber of the foamed molded article> The ultraviolet absorber was extracted from the sample into the acetonitrile solution by a high-speed solvent extraction apparatus (manufactured by Dionex). The amount of the ultraviolet absorber in the extract obtained was measured by ultra high speed liquid chromatography. The amount of detection of the ultraviolet absorber in the foamed molded body was calculated from the obtained value according to the following formula. The amount of the ultraviolet absorber to be detected in the foamed molded article (% by weight) = the concentration of the ultraviolet absorber in the extract (pg/mL) x 5 〇 (mL) / 0.2 (g) / 10000 20 201125905 Further, the extraction conditions and measurement conditions are as follows. (i) Extraction condition measuring device: high-speed solvent extraction device ASE-350 (manufactured by Di〇nex) Extraction temperature: l〇〇°C Extraction solvent: acetonitrile/extraction tank = 10 mL Extraction pressure: 10.5 MPa Heating time: 5 min/station Time: 15min Washing amount: 25% Washing time: 7〇sec/3 times (cycle number) Sample preparation method for extraction: Cut into 2mm width (about 2.5cm in length and height of about 5~15cm) with a small cutting machine The strip shape was such that the precision weighing value was 0.2 g, and a sample of 〇. 2 g was obtained. (Π) Measurement condition measuring device: Ultra-high speed liquid chromatography LaChromUltra column manufactured by Hitachi Global Advanced Technology Co., Ltd.: LaChr〇mUltraC18 2pm (2.0mmI.D.*50mmL) Measurement conditions: column temperature (40 ° C), mobile phase (A = 0.05% TFA B = acetonitrile), mobile phase flow (0.6 mL/min), mobile phase conditions (0-> 2 min = Bconc. 50% >2-> 4 min Bconc. 50% - > 〇〇% -4—l〇min=Bconc. 100%)' Pump temperature (room temperature), measurement time (l〇min), detection (UV=225nm), injection amount (2μί) : The extract made of acetonitrile was made up to 50 mL. The extracted extract was filtered through a non-aqueous chromatography disk having a diameter of 0·20 μηι, and used as an extract for measurement. 21 201125905 <falling ball impact strength of foamed molded article> According to JIS K 7211, a test piece of 215 mm (length) x 4 mm (width) x 20 mm (thickness) is cut out from a predetermined number of foam molded articles, and The test piece was placed at a distance of 150 mm between the fulcrums. The steel ball of 32 lg was dropped on the test piece, whereby the falling ball impact strength, i.e., the 破坏% destruction height, was calculated according to the following formula. Further, the test piece was made to have no skin on all six sides. H50=Hi+d[I(i - ni)/N±0.5] H5〇 . 5〇% destruction height (cm)

Hi : Test height when the level (1) is 0, the degree of damage of the test piece is predicted to be d: the height interval (cm) when the test height is moved up and down 1 : When Hi is 〇, the height level of each increase or decrease . (i=...-3, -2, -1, 〇, 1, 2, 3...) m • Number of test pieces destroyed (or not destroyed) at each level N. Destroyed (or not Total number of test pieces (破坏=Σηί) (use any of the more data, and 'whenever the same quantity is used, no matter which one is used.) ±0.5. Use negative data when using corrupted data, use is not used Take the positive when destroying the data. Example 1 (Production of Resin Particles) Ethylene-vinyl acetate copolymer resin particles (LV-211 'Hybrid Flow Index 〇々/1 〇, Ethyl acetate content 62% by weight, manufactured by Nippon Polyethylene Co., Ltd.) 1〇 In the 〇 part by weight, 3 parts by weight of 石 弼〇 与 与 与 与 硬 硬 硬 硬 硬 硬 以 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 均匀 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 2011 The copolymer resin particle system has been adjusted to 80 mg per 100 particles. 40 parts by weight of the above-mentioned particles, 120 parts by weight of pure water, 0.45 parts by weight of magnesium cokeate, and 0.02 parts by weight of sodium dodecylbenzenesulfonate were added to a pressure vessel having a volume of 100 liters. The mixture was stirred to suspend the particles in pure water. Then, a mixed liquid in which 0.03 part by weight of bisisophenylpropyl peroxide was dissolved in 20 parts by weight of a styrene monomer was dropped in the suspension for 30 minutes as a radical polymerization initiator. After holding for 30 minutes after dropping, the temperature of the reaction system was raised to 135 ° C, and after maintaining for 2 hours, it was cooled to normal temperature. Next, 0.16 parts by weight of sodium dodecyl benzoate was added to the suspension, and then the temperature of the reaction system was raised to 90 °C. Further, 40 parts by weight of the styrene monomer is obtained by dissolving benzoic acid benzoquinone_3 parts by weight, 0.02 parts by weight of butyl peroxybenzoate, and 0.8 parts by weight of bisisophenylpropyl peroxide. Mixture. The mixed liquid was dropped in the reaction system after the temperature rise described above for 4 hours, whereby the styrene monomer was absorbed by the particles while being polymerized on one side. Thereafter, the reaction system was kept at 90 ° C for 3 hours, and then heated to 135 ° C, and maintained at this temperature for 3 hours, whereby the completion of the polymerization was completed. After completion of the completion of the above polymerization, the mixture was cooled to room temperature to obtain composite resin particles. (Infiltration and pre-expansion of a foaming agent and an ultraviolet absorber) 100 parts by weight of polyethylene modified polystyrene resin particles are added to a pressure-resistant sealable V-type pulverizer having an internal volume of 50 liters. 2-(2H-benzotriazol-2-yl)-p-nonylphenol (23 201125905 TINUVIN® manufactured by Ciba Specialty Chemicals Co., Ltd.) 〇·10 parts by weight, diisobutyl adipate g 0.5 In parts by weight, an aliphatic fourth-grade ammonium salt (Kachiogen ES-〇W®, manufactured by Dai-ichi Kogyo Co., Ltd.) 2. The 〇 part by weight was sealed and stirred while 14 parts by weight of butane was pressed. Next, the inside of the apparatus was kept at 6 ° C for 2 hours, and the foamed resin particles were taken out by cooling. The foaming agent content in the obtained expandable resin particles was 9.0 parts by weight. The foamed resin particles which have been taken out are immediately pre-expanded by a batch type pre-expander to a volume ratio of 30 times to prepare pre-expanded particles, and are then stored in a greenhouse at a temperature of 23 °C. (Foaming Forming) In-mold foam molding of the obtained pre-expanded particles was carried out. The pre-expanded particles were introduced into a mold of 3 mm (width) x 400 mm (length) x 30 mm (thickness), and water vapor of 〇7 kgf/cm2 was introduced for 30 seconds to be heated. After the heating, the foaming pressure of the foamed molded article was lowered to 0.05 kgf/cm2 or less, and the foam molded article having a multiple of 30 times was taken out. The foamed molded body which had been taken out was allowed to stand in an environment of 35 ° C for 6 hours or more. The transmittance of the skin portion of the foamed molded article obtained was measured, and the results are shown in Fig. 1. Moreover, the transmittance obtained according to the method A, the transmittances at 350 nm, 500 nm, and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorber detection amount are shown in Table 1. Example 2 The same procedure as in Example 1 was carried out, except that 2-octa-4-(octyloxy) octabenzone (CHIMASSORB 81 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as the ultraviolet absorber. . Of the foamable resin particles obtained, 24 201125905 foaming agent contained 1 in 8.9 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured, and the results are shown in Fig. 2 . Further, the transmittance obtained according to the method A, the transmittance at 35 〇 nm, 5 〇〇 nm & 8 〇〇 nm calculated by the measurement result (method B), the ratios A and B, the falling ball impact strength value, The amount of ultraviolet absorber detected is shown in Table 1. Example 3 2-(2H-benzotriazol-2-yl)-4,6-di-trisylpentanol (T1NUVIN 328 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as an ultraviolet absorber, and The external system was carried out in the same manner as in Example 1. The foaming agent content in the obtained expandable resin particles was 8 to 9 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured, and the results are shown in Fig. 3. Further, the transmittance obtained according to the method a, the transmittance at 35 〇 nm, 500 nm and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorbing agent detection amount calculated from the measurement results are Shown in Table 1. Example 4 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-pyrophenol (TINUVIN 571 manufactured by Ciba Specialty Chemicals Co., Ltd.) was used as an ultraviolet absorber, except The external system was carried out in the same manner as in Example 1. The content of the foaming agent in the obtained expandable resin particles was 9.0 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured, and the results are shown in Fig. 4. Moreover, the transmittance obtained according to the method 、, the transmittance at 350 nm, 500 nm, and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorber detection amount calculated from the measurement results are shown in Table 1. Example 5 25 201125905 The same procedure as in Example 1 was carried out except that the foaming agent and the ultraviolet absorber were impregnated in a wet manner as described below. The foaming agent content in the obtained expandable resin particles was 8.5 parts by weight. Further, the transmittance of the obtained skin portion of the foamed molded body was measured. The transmittance obtained according to Method A, the transmittance at 35Onm, 5OOnm and 800nm (Method B), the ratios A and B, the falling impact strength value, and the UV absorber detection amount are shown in Table 1. . (wet impregnation) 100 parts by weight of composite resin particles and 0.04 parts by weight of sodium dodecylbenzenesulfonate in 100 parts by weight of water in a pressure-resistant container with a pressure of 5 liters of internal pressure. Alkyl monoolamine (Nippon Oil Co., Ltd. N-Ming L-201) 0.3 parts by weight, as a UV absorber, 2_(2H-benzotriazol-2-yl)-p-cresol (Ciba Specialty Chemicals Co., Ltd.) Company made TINUVIN Ρ) 0·10 parts by weight, stir to suspend. Thereafter, 14 parts by weight of butane was introduced into the vessel. Thereafter, the temperature of the suspension was raised to 70 ° C for 3 hours. After cooling, the obtained expandable resin particles were taken out. Comparative Example 1 The same procedure as in Example 1 was carried out except that the ultraviolet absorber was not added. The foaming agent content in the obtained expandable resin particles was 89 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured, and the results are shown in Fig. 5. Further, the transmittance obtained according to the method A, the transmittance at 350 nm, 500 nm and 800 nm (method b), the ratios A and B, and the falling ball impact strength values calculated from the measurement results are shown in Table 1. 26 201125905 Comparative Example 2 In the same manner as in Example 5, the impregnation of the foaming agent was carried out in a wet manner, and the same procedure as in Comparative Example 1 was carried out in the same manner. The yield of the foamable resin particles obtained was 8.6 parts by weight. Further, the transmittance of the obtained foam molded body skin portion = was measured. The transmittances obtained by the method A, the transmittances at 350 nm, 500 nm, and 800 nm (method β), the ratio a, and the falling ball impact strength values calculated from the measurement of 蛀, J, and the leaves are shown in Table 1. (Example 6) The amount of the ultraviolet absorber added was 0.05 parts by weight, and the same procedure as in Example 1 was carried out. The foaming agent content in the obtained expandable resin particles was 8 to 8 parts by weight. Further, the transmittance of the obtained portion of the foamed molded body was measured. The transmittance obtained according to the method A, the transmittance at 350 nm, 500 nm and 800 nm (method b), the ratios a and B, the falling ball impact strength value, and the ultraviolet absorber detection amount are shown in the table. 2. (Example 7) The same procedure as in Example 1 was carried out except that the amount of the ultraviolet absorber added was 0.05 parts by weight. The foaming agent content in the obtained expandable resin particles was 9.2 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured, and the results are shown in Fig. 6. Further, the transmittance obtained according to the method A, the transmittance at 350 nm, 500 nm, and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorber detection amount are shown in Table 2. Example 8 The amount of the ultraviolet absorber added was 0.02 parts by weight, in addition to 27 201125905

The same procedure as in Example 1 was carried out. The foaming agent content in the obtained expandable resin particles was 9.0 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured. The transmittance obtained according to the method A, the transmittance at 350 nm, 500 nm and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorber detection amount calculated from the measurement results are shown in Table 2. . (Example 9) The same procedure as in Example 1 was carried out except that the amount of the ultraviolet absorber added was changed to 5 parts by weight. The foaming agent content in the obtained expandable resin particles was 8.9 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured. According to the method, the transmittance obtained by the method, the transmittance at 350 nm, 500 nm and 800 nm (method B), the ratios A and B, the falling ball impact strength value, and the ultraviolet absorber detection amount calculated in the measurement results are shown in Table 2. . (Example 10) The same procedure as in Example 5 was carried out except that the amount of the ultraviolet absorber added was changed to 0. 02 parts by weight. The foaming agent content in the obtained expandable resin particles was 8.9 parts by weight. Further, the transmittance of the skin portion of the obtained foam molded body was measured. According to the method, the transmittance obtained by the method, the transmittance at 350 nm, 500 nm and 800 nm (method b), the ratios A and B, the falling impact strength value, and the ultraviolet absorber detection amount calculated in the measurement results are shown in Table 2. . Example 11 The same procedure as in Example 1 was carried out except that the volume multiple of the pre-expanded particles and the multiple of the foamed molded article were 15 times. The foaming agent content in the obtained expandable resin particles was 8.8 parts by weight. The transmittance and falling ball impact strength values obtained according to the method α are shown in Table 3. 28 201125905 Example 12 (Production of Resin Particles) LLDPE (trade name "NF-444A" manufactured by Sakamoto Polyethylene Co., Ltd., melt flow index (MI) = 2.0 g/10 min. , density: 0.912 g/cm3) as a non-crosslinked linear low-density polyethylene resin. The resin is placed in an extruder and melted and kneaded. The kneaded product was formed into granulated particles by a sub-cutting method (slightly spherical, and the polyethylene-based resin particle system was adjusted to about 60 mg per 100 particles). In a pressure-resistant container with a volume of 100 liters, 0.8 parts by weight of magnesium pyrophosphate and 0.02 parts by weight of sodium dodecylbenzenesulfonate were dispersed in 100 parts by weight of water to obtain a dispersion medium. The polyethylene resin particles were dispersed in 100 parts by weight in a dispersion medium to obtain a suspension. Then, 0.2 part by weight of bisisophenylpropyl peroxide was previously dissolved as a polymerization initiator in 100 parts by weight of the styrene monomer to obtain a first styrene monomer solution. The temperature of the above suspension was adjusted to 60 ° C, and it was taken for 30 minutes to quantitatively add the first stupid ethylene monomer solution to the suspension. Thereafter, the mixture was stirred at 60 ° C for 1 hour to impregnate the styrene monomer into the polyethylene resin particles. Then, the temperature of the dispersion was raised to 130 ° C, and the styrene monomer was polymerized in the polyethylene resin particles by maintaining at 130 ° C for 2 hours. Next, 0.35 parts by weight of bisisophenylpropyl peroxide was dissolved as a polymerization initiator in 300 parts by weight of a styrene monomer to obtain a second styrene monomer solution. The second styrene monomer solution was continuously dropped into the previous polymerization system in a ratio of 60 parts by weight per hour for 5 hours. The styrene monomer in the second styrene monomer solution is impregnated into the polyethylene resin particles at the same time. After the above polymerization, the mixture was cooled to room temperature to obtain composite resin particles. (Infiltration and pre-expansion of a foaming agent and an ultraviolet absorber) The amount of diisobutyl adipate is made into 9 parts by weight, the amount of butane is made to 18 parts by weight, and the aliphatic level 4 is not used. In the same manner as in Example 1, except that the ammonium salt was used, the expandable resin particles were obtained. The foaming agent content in the obtained expandable resin particles was 9.1 parts by weight. The foamable resin particles were preliminarily foamed in the same manner as in Example 1 to obtain pre-expanded particles having a volume ratio of 5 〇 and then stored in a constant temperature chamber at a temperature of 23 °C. (Foaming molding) In-mold expansion molding was carried out in the same manner as in Example 1 to obtain a foam molded article having a magnification of 5 times. The transmittance and ball drop impact strength values obtained according to Method A are shown in Table 3. The same procedure as in Example 12 was carried out except that the amount of the external absorbent was 2 parts by weight. The content of the foaming agent in the obtained expandable resin particles was 9 to 1 part by weight. The transmittance and ball drop impact strength values obtained according to Method A are shown in Table 3. Example 14 (Manufacturing of Resin Particles) In a 100-liter internal container of a mixer, 40,000 parts by weight of water, 1 part by weight of tertiary calcium phosphate, and 2,10% of calcium dodecylbenzenesulfonate were supplied. A dispersion was obtained in parts by weight. Next, 40,000 parts by weight of a stupid ethylene monomer, 96 parts by weight of alum, and 2,8.0 parts by weight of peroxy 30 201125905 butyl benzoate were added to the dispersion under stirring. After the addition, the temperature was raised to 90 ° C to polymerize the styrene monomer. Then, the temperature was maintained at this temperature for 6 hours, and the temperature was further raised to 125 °C. Two hours after the temperature rise, the mixture was cooled to room temperature, whereby polystyrene resin particles (A) were obtained. The polystyrene resin particles were sieved to obtain polystyrene resin particles (B) having a particle diameter of 0.5 to 0.71 mm as seed particles. Next, 2000 parts by weight of water, 500 parts by weight of polystyrene-based resin particles (B), 6.0 parts by weight of magnesium pyrophosphate, and 0.3 weight of calcium dodecylbenzenesulfonate were placed in a mixer polymerization vessel having an internal volume of 5 liters. Share. The supply was stirred while being heated to 70 ° C while being heated. Then, 4.5 parts by weight of benzoquinone peroxide and 1.1 parts by weight of butyl benzoate were dissolved in 200 parts by weight of a styrene monomer to obtain a solution. This solution was supplied to the above-mentioned internal volume of 5 liters of the polymerization vessel. After 30 minutes from the supply, the temperature was raised to 100 ° C, and 1300 parts by weight of the styrene monomer was supplied to the above-mentioned internal volume of 5 liters of the polymerization container by the pump for 2 hours. After the supply, the temperature was raised to 120 ° C, and after cooling for 2 hours from the temperature rise, the mixture was cooled to room temperature to obtain polystyrene resin particles (C). (Infiltration of a foaming agent and an ultraviolet absorber) Next, 2200 parts by weight of water, 1800 parts by weight of polystyrene resin particles (B), and pyrophosphoric acid were supplied to another 5 liter mixer equipped with a polymerization vessel. 6.0 parts by weight of magnesium and 0.4 parts by weight of calcium dodecylbenzenesulfonate, and 1.8 parts by weight of 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P) as a UV absorber (relative In the case of 0.1 part by weight of the polystyrene resin, the surface was lifted to 70 C while the surface was 31 201125905. Next, 18 to 90 parts by weight of cyclohexane as a foaming auxiliary agent and 12.6 parts by weight of hexamethylene diisobutyl acrylate as a plasticizer were placed in a polymerization vessel, and the temperature was raised to 1 〇〇° (:. Next, 100 parts by weight of n-butane was placed in a polymerization container in which the polystyrene resin particles (C) were placed, and the mixture was kept as a foaming agent for 3 hours. Thereafter, after cooling to 30 ° C or lower, the polymerization container was taken out from the polymerization container. The foamable resin particles are dried and placed in a constant temperature room at 13 ° C for 5 days. (Pre-expansion and foam molding) The above-mentioned expandable resin particles are used. The foaming agent content in the obtained expandable resin particles was 8.5 parts by weight, and the transmittance and falling ball impact strength values obtained according to the method A are shown in Table 3. Table 1 In the case of 3, the 〇, △, and χ in the evaluation results are based on the following criteria. That is, we hope that both the ultraviolet shielding property and the falling ball impact strength value of the foam molding system are both combined. Accordingly, in the present specification, ultraviolet shielding is specified. Sex line to meet the following The component (I) is preferred, and the falling ball impact strength value is preferably such that the following conditions (Π) are satisfied. Condition (I): The transmittance obtained according to the method 在 is less than 3 〇% (π): falling ball impact The intensity value is 35 cm or more, △, △ and X are in the following conditions (1) and (1[), as in the following evaluation examples and comparative examples. 〇: Compliance with condition U) and condition (π) △: only One of the conditions (][) and condition (]1) 32 201125905 χ: Non-conforming (I) In Table 3, the meanings of the codes are: EVA means ethylene-vinyl acetate copolymer, PS is Polystyrene is used, and mLLDPE is a non-crosslinked linear low-density polyethylene resin which is obtained by a metal aromatic catalyst. 5 33 201125905 a€-^ —οοο/οιηε v Spider q-ΙΛ iloe (錤奴茛1) 目 008/0^ V5ige (%)(钹矽茛1) 朱某 if 008 i oscn (%) ^5 € #«) ¥一趣趣(take ¥¥) 黩鄕$ 〇j SOS I 6ΙΌ 8Γ0 0Γ0 | ΖΖΌι(Νε9Ό 6S inch Ό sICNro ^.0 S6O IldsltNe NIAONLL ^ ΙΟΙς·6 inch IsllolI i inch 6ε·0 SOS 8 O.OICNIS Z.6Q IQ _ 18 §QSSVMH3Yl^ll(Ni4l^Kk 〇ς·ΐς ^ ΓΓ5 ^ ^~lrll6SO AW7OI690Ό Is ^ Γ5 dNIAONIl ^ XX ΙΟΙ 〇

Sloo inch S.8 inch S.Z. inch TZF 6glo § ΙΌ Is Ζ.Ζ.Ό ^.0 £ΙΌ 2 ι<ν9ό 8S ι(νιιό (ΝΙΓΟ ε8·0 inchΖ.Ό 6ΙΌ 02 11 inch.0 8§ Ι9Ό ζ9οι

Inch 0£Ό66s —.0 I

Es ΙΖΖΌ si 6EIOI s.lp! m ss Is 86Ό IlddsAnNIl 96Ό 10ICNIAnMl

s W~ s "W

If-sq on 34 201125905 CN< 〇 ο 〇

V 〇 ϊ CB-^Tlr^TX-TSrn) (钹铋茛1) (%)(钹矽茛1) 5.817

SOS

Irl.ls loos $.6 inch as-08/olocn vs-oie 33^3⁄4 i08_ vs. 008 i ose (%)^5v^^ (take ¥¥) §¥*) ^Ds $ $ inch 0Ό 80Ό inch 0Ό 900 69s 8(ΝεΌ 1 0-.0 6Γ0 s cuNIAnNIl 9f杳Save

Is 8<νό ΙΓ0 630 190

SO Ιειο <Ns_o 6 inch 00 sd

dNIAHNLL

Is 9 inch Ό

3S lo inch Ό

Inch SO 9 inch Ό § i i inch (ΝΓ0 3ς·Ι ooIOd sd αΗΝΙΛηΝΙΙ oof# 驷 ειοΌ 190 /. One inch.0 S2

I l (N_ inch §.0 id

dNIAHNLL inch 2 inch inch Ό 96s 602 9αο

9 inches · I 6100 sd α, ΜΛΠΝΙΙ 3 §s^ 35 201125905 Table 3

From the examples 1 to 14 and the comparative examples 1 and 2, it is found that the foamed molded article obtained as a raw material by the foamable resin particles contains an ultraviolet absorber, and the ultraviolet shielding property is improved. The increase in UV shielding is also clear from the 1st to 6th +. That is, in the drawing, the examples 1 to 5 are significantly smaller than those of the comparative example 1 with respect to the wavelength of 400 to 300 nm which is in the ultraviolet wavelength region. Therefore, it is shown that the ultraviolet shielding property can be improved by the inclusion of the ultraviolet absorber. Further, according to the first to fourth embodiments, it is understood that the ultraviolet ray shielding property of the foamed molded article obtained by using the expandable resin particles as a raw material is improved even if the ultraviolet absorbing agent is changed. Further, it is conventionally known that the ultraviolet absorber is dispersed in the resin particles by kneading with a resin which requires a higher temperature. However, in Examples 1 to 5, the foaming agent impregnation step carried out at a low temperature of 50 to 70 °C causes the ultraviolet absorber to impregnate the inside of the resin. Therefore, it has been found that a foamed molded body capable of shielding ultraviolet rays can be easily obtained. Further, the foamed molded article obtained in Examples 1 to 14 was found to have a falling ball impact strength value sufficient for use in a transport and storage container for electrical products. Further, as is apparent from Examples 1 and 5, good ultraviolet shielding properties can be obtained by applying the ultraviolet absorber to either dry or wet type. 36 201125905 Further, it can be seen from Examples 1 and 6 to 9 that the ultraviolet shielding property can be enhanced by the addition of the amount of the ultraviolet absorbing agent. Moreover, it can be seen from Examples 1, 12, and 14 that good ultraviolet shielding properties can be obtained even if the resin type is changed. Further, it was found that the falling ball impact strength value was good in the case of containing a polyolefin component. Further, it can be seen from the examples 1 and 11 that good ultraviolet shielding properties can be obtained even if the expansion ratio is changed. Next, 'the coordinate pattern of the respective wavelength radiances of the UV light which has been used in the method A' is shown in Fig. 8(a), and the respective wavelength radiances of the foamed molded bodies of the first embodiment and the comparative example 1 are shown. The coordinate figure is shown in Figure 8(b). In the figure 8(b), the broken line represents the first embodiment, and the solid line represents the comparative example. From the eighth (b), it can be seen that the foamed molding system of the embodiment 1 can meaningfully shield the light having a wavelength of around 365 nm. . BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph showing the relationship between the wavelength of irradiation light and the transmittance of the foamed molded article of Example 1. Fig. 2 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 2. Fig. 3 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 3. Fig. 4 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 4. Fig. 5 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Comparative Example 1. 37 201125905 Fig. 6 is a graph showing the relationship between the wavelength of the irradiation light and the transmittance of the foamed molded article of Example 7. Fig. 7 is a schematic view showing a measuring device for ultraviolet transmittance of a foamed molded article. Figs. 8(a) and 8(b) are graphs showing the respective wavelengths of ultraviolet light, the foam molded bodies of Example 1 and Comparative Example 1. [Explanation of main component symbols] 1···υν光(ultraviolet light) 4···light source 2.. Spectroradiometer 5...shade 3.. .light receiving unit 38

Claims (1)

201125905 VII. Patent application scope: i. The method for producing an expandable resin particle is to contact the resin particle by an absorbent when the foaming agent is impregnated into the resin particle which can be an expandable resin particle In addition, foamable resin particles having ultraviolet shielding properties were obtained. 2. The method for producing an expandable resin particle according to the first aspect of the invention, wherein the ultraviolet absorber is a benzotriazole-based or diphenylketone-based ultraviolet absorber, and the weight thereof is 100% with respect to the resin particles. The parts used were 0·01~〇·5 parts by weight. 3. The method for producing an expandable resin particle according to the first aspect of the invention, wherein the resin particle contains a resin particle of a polyolefin resin and a polystyrene resin. 4. The method for producing an expandable resin particle according to the first aspect of the invention, wherein the resin particle contains a resin particle of a polyolefin resin bismuth and a polystyrene resin in an amount of 120 to 560 parts by weight. 5. A pre-expanded particle obtained by pre-expansion of a foamable resin obtained by the method for producing a foaming hawed enamel particle according to the above-mentioned Patent Application No. 5 to a volume ratio of 5 to 60 times. By. 6. The foamed molded article may be obtained from an expandable resin particle containing an ultraviolet absorber, and the foamed molded article has a wavelength of 365 nm of 3% or less in a sample having a thickness of 5 mm cut from the skin thereof. Transmittance of light. 7. The foamed molded article according to claim 6, wherein the resin contains a polyolefin resin and a polystyrene resin, and the ultraviolet absorber is a benzotriazole-based or diphenylketone-based ultraviolet absorber. Further, it is used in an amount of 〇.〇1 to 5.5 parts by weight based on 100 parts by weight of the above resin. 39