CN1903920A - Foaming polystyrene series resin particle and its manufacturing method, foaming shaped article and foodstuff package - Google Patents
Foaming polystyrene series resin particle and its manufacturing method, foaming shaped article and foodstuff package Download PDFInfo
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- CN1903920A CN1903920A CN 200610099108 CN200610099108A CN1903920A CN 1903920 A CN1903920 A CN 1903920A CN 200610099108 CN200610099108 CN 200610099108 CN 200610099108 A CN200610099108 A CN 200610099108A CN 1903920 A CN1903920 A CN 1903920A
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Abstract
The invention provides expandable polystyrene resin particles being capable of giving an expanded molding proof against exudation of oils and coloring matters and being excellent in expandability, to provide a method for producing the same, to provide an expanded molding obtained therefrom, and to provide a packaged food prepared by packaging food in the expanded molding. The expandable polystyrene resin particles are characterized in that an outer layer of a polystyrene resin formed by polymerizing a styrene monomer containing a crosslinkable monomer is formed on the surface of a polystyrene resin particle, an easily volatile blowing agent is infiltrated into the particles, the gel fraction of the polystyrene resin constituting the particles is 10 to 50 mass%, the ratio (Mw<SB>1</SB>/Mw<SB>2</SB>) lies in the range of 0.5 to 0.8 (wherein Mw<SB>1</SB>is the weight-average molecular weight of the polystyrene resin extracted with tetrahydrofuran; and Mw<SB>2</SB>is the weight-average molecular weight of the polystyrene resin extracted after splitting each particle into two; and Mw<SB>2</SB>lies in the range of 150,000 to 400,000).
Description
Technical field
The present invention relates to expandable polystyrene resin beads and manufacture method thereof, the expansion-molded article that uses this expandable polystyrene resin beads to make reaches and pack the foodstuff package that food is arranged in containing the container of this expansion-molded article.
Background technology
In the past, make in styrene resin particles the expandable polystyrene resin beads of infiltration whipping agent prepare foaming and make the preparation expanded particle, this preparation expanded particle is filled in the shaping die of forming mill, heating then, make its foaming, mutually fuse integrated, thereby make foaming and molding container with desired shape.
As mentioned above, the foaming and molding container is the blow(ing) pressure by preparation expanded particle self, make the foaming of preparation expanded particle, heat fusion is integrated between the expanded particle forms, but the contact part office between these expanded particles, be not to be heat fusion all sidedly between the expanded particle, and just partly heat fusion is integrated.
Therefore, even be in good state between the foaming and molding container expanded particle, promptly, in the section of foaming and molding container, be in the visual incorporate state of complete heat fusion down between the surface of expanded particle, because gap in the contact part between the expanded particle, that result from non-heat fusion part is continuous to inward-outward direction, thereby has formed the state that connects between the interior outside of foaming and molding container with the visual fine kapillary that can not confirm.
This situation can be confirmed by following phenomenon occurring, promptly in the foaming and molding container, add the dyestuff that contains tensio-active agent, after continuing to place the specified time, the dyestuff in the foaming and molding container oozes out to the outside by the kapillary that forms between expanded particle.
When using such foaming and molding container to use cup as the such beverage of coffee, though in practicality, can not produce any obstacle, but there are the following problems: the long-time preservation oily food class that continues in the foaming and molding container, the salad oil of for example fried cake circle, hamburger, fried chicken, oleomargarine etc., when containing the food of grease etc., the kapillary that the oil component that contains in these oily food classes forms in can be by the foaming and molding container oozes out to the outside.
Equally, in the foaming and molding container, if the auxiliary material class of holding instant noodles and containing curry powder is preserved, then the xanthein of curry powder oozes out to foaming and molding container outside by the kapillary of foaming and molding container, has the impaired problem of commodity value.
Therefore, in patent documentation 1, expandable polystyrene resin beads has been proposed, it is characterized by, the surface of expandable polystyrene resin beads is covered with upper layer, with respect to expandable polystyrene resin beads 100 mass parts, this epidermal area contains Zinic stearas 0.3～0.6 mass parts and the polyoxyethylene glycol aqueous solution 0.1～0.4 mass parts, and it is 100～600 polyoxyethylene glycol that the described polyoxyethylene glycol aqueous solution contains 20～50 quality % weight-average molecular weight.
Yet, the expansion-molded article that above-mentioned expandable polystyrene resin beads is carried out foaming and molding and obtain, though visible to a certain degree prevent the effect that oil component oozes out, but because molding is to the patience deficiency of oil component, thereby under the situation of long-term keeping, for preventing that oil component from being inadequate for oozing out.
In polystyrene resin beads, in order to give oil-proofness to a certain degree, can enumerate the method that makes polystyrene resin have crosslinking structure.Though prevent that oil component from oozing out from molding is not its direct purpose, the trial that makes polystyrene resin beads have crosslinking structure all is carried out all the time.
In patent documentation 2, the manufacture method of expandable polystyrene resin beads has been proposed, it is can be purpose with the foaming polystyrene series resin of polystyrene resin hybrid shaping to make, in the following way, on the surface of foamable polystyrene, form styrene-divinylbenzene copolymer, promptly, in the outstanding turbid aqueous medium that the foamable polystyrene particle arranged, slowly add the polymerizable monomer mixture that contains divinylbenzene 0.05～1.0 quality % and styrene monomer 99.95～99.0 quality, make above-mentioned expandable polystyrene resin beads reach 90～50 quality %, above-mentioned polymerizable monomer mixture reaches 10～50 weight %, makes it carry out polymerization in the presence of polymerizing catalyst then.
Though this method can make the skin section branch have crosslinking structure, but because whipping agent makes the polystyrene resin swelling, when the styrene monomer that will contain linking agent is contained in wherein, styrene monomer be impregnated into particle than central part, though the degree of crosslinking than particle top layer is low, particle inside also forms crosslinking structure.
If as the cup packaging vessel of face and the little resin particle of normally used particle diameter, then crosslinked meeting is carried out to particle inside more significantly.In order to keep the foaming power of such particle,, then do not have good foaming power if styrene monomer that does not have non-reacted parts etc. can become the composition of solvent.Yet, contain the container of a large amount of solvent compositions, improper container as wrap food.
In addition, in patent documentation 3,, the scheme with the styrenic pearl of styrene-divinylbenzene copolymer modification has been proposed in order to improve the intensity of glass molding.Yet, though the intensity of molding is improved in the method, owing to particle integral body is modified by crosslinking structure more equably, thereby the foaming power scarcity, want extra heating for the molding that obtains good surface appearance is essential, diminish productivity.
In addition, in patent documentation 4, the manufacture method (seeding polymerization method) of expandable styrene based polymer particle is disclosed, it is by in the aqueous suspension that contains styrenic grain kind, add styrenic monomers and polymerization starter continuously or intermittently, this styrenic monomers is aggregated in this styrenic grain kind, obtain the styrenic particle, the manufacture method of the expandable styrene based polymer particle of infiltration easy volatile whipping agent in this styrenic particle; It is characterized by, when being made as 100 mass parts with the amount of above-mentioned styrenic grain kind with for the total amount of the amount of the necessary styrenic monomers of styrenic particle that obtains purpose, from the styrenic monomers of the amount of this styrenic grain kind and interpolation amount to 90 mass parts the time, until the interpolation that finishes this styrenic monomers, finish polyreaction during, measure 100 mass parts with respect to this total, add the linking agent of 0.005～0.02 mass parts.
Yet, the expandable styrene based polymer particle of making by above-mentioned manufacture method, effective for the gap between the preparation expanded particle that stops up the expansion-molded article that obtains with this expandable styrene based polymer particle, but it is be exuded to outside problem by the formed kapillary of foaming and molding container, because not enough and can not fully solve to the patience of oil component for above-mentioned oil component and butter pigment.
Patent documentation 1: the spy opens the 2005-8797 communique
Patent documentation 2: special public clear 48-44656 communique
Patent documentation 3: the spy opens clear 62-181344 communique
Patent documentation 4: specially permit communique No. 3474995
Summary of the invention
The inventor etc. found that through studying intensively repeatedly: the place that oil component and xanthein ooze out in the foaming and molding container, the heat fusion of expanded particle partly rise and fall and form wrinkle, because of oil component and xanthein go bad; On the other hand, do not have the part of oozing out at oil component and xanthein, fluctuation does not take place in the heat fusion part of expanded particle, is the state that not have distortion, less than going bad because of oil component or xanthein.And then in order to prevent oozing out of oil component and xanthein in the foaming and molding container, the essential oil-proofness that improves expansion-molded article particularly improves the oil-proofness of the heat fusion part between the expanded particle of expansion-molded article.
The purpose of this invention is to provide expandable polystyrene resin beads and manufacture method thereof, and the expansion-molded article made from this expandable polystyrene resin beads and in containing the container of this expansion-molded article, pack the foodstuff package of food, even described expandable polystyrene resin beads can access pigments such as the oil component that contains and curry powder in inside continue to be preserved food etc. for a long time, or continue to hold the expansion-molded article that does not also ooze out under the situation of the liquid that contains tensio-active agent etc. in the specified time in inside to the outside, and, the foaminess excellence.
For achieving the above object, the invention provides expandable polystyrene resin beads, it is on the surface of polystyrene resin grain kind, setting makes the polystyrene monomer polymerization that contains cross-linkable monomer and the polystyrene resin skin that forms, the expandable polystyrene resin beads that the foaming and molding that the infiltration of easy volatile whipping agent is wherein formed is used, it is characterized by, the gel fraction that constitutes the polystyrene resin of this particle is 10～50 quality %, the weight-average molecular weight Mw of the polystyrene resin that extracts with tetrahydrofuran (THF)
1With the weight-average molecular weight Mw of particle being cut apart the polystyrene resin that extracts after 2 parts
2Ratio (Mw
1/ Mw
2) be 0.5～0.8 scope, and this Mw
2It is 150,000～400,000 scope.
In expandable polystyrene resin beads of the present invention, the scope of preferred 20～35 quality % of gel fraction.
In addition, the present invention also provides the manufacture method of expandable polystyrene resin beads, it is characterized by, making is scattered in dispersion liquid in the aqueous medium with polystyrene resin grain kind, remain on 80～110 ℃, then in this dispersion liquid, to contain with respect to described grain kind 100 mass parts is the styrenic monomers of 12～100 mass parts, quality with respect to described styrenic monomers is that the cross-linkable monomer of 0.2～1.0 quality % and the monomer solution of polymerization starter are supplied with the ratio of per 1 hour 1～18 mass parts with respect to total 100 mass parts of described grain kind and described styrenic monomers, the outer growth of polystyrene resin that the styrenic monomers that contains cross-linkable monomer is polymerized, and, after supplying with described monomer solution, make the infiltration of easy volatile whipping agent wherein.
The manufacture method of expandable polystyrene resin beads of the present invention with respect to total 100 mass parts of described grain kind and described styrenic monomers, is preferably supplied with monomer solution with the ratio of per 1 hour 5～16 mass parts.
In addition, the invention provides expansion-molded article, it is characterized by, preparation expanded particle foaming and molding is obtained, described preparation expanded particle makes above-mentioned expandable polystyrene resin beads preparation foaming of the present invention and obtains.
Expansion-molded article of the present invention, the center line average roughness on molding surface (this center line average roughness is the center line average roughness of JIS B0601-1994 defined) is preferably the scope of 0.1～1.5 μ m.
In addition, the invention provides foodstuff package, it is to form at the food that the container internal packing that contains described expansion-molded article contains oily food or food oils and pigment.
Expandable polystyrene resin beads of the present invention, the gel fraction that constitutes resin is 10～50 quality %, the weight-average molecular weight Mw of the polystyrene resin that extracts with tetrahydrofuran (THF)
1With the weight-average molecular weight Mw of particle being cut apart the polystyrene resin that extracts after 2 parts
2Ratio (Mw
1/ Mw
2) be 0.5～0.8 scope, Mw
2It is 150,000～400,000 scope.Therefore, keep sufficient foaminess as the expandable polystyrene resin beads that foaming and molding is used, and, this expandable polystyrene resin beads foamed and the expansion-molded article that obtains, the cross-linking density height at the heat fusion interface between its expanded particle, the oil-proofness excellence.So, the expansion-molded article of the present invention that this expandable polystyrene resin beads is foamed and obtain, even continue to hold the food that contains oil component for a long time or contain the food of pigments such as curry powder or hold in expansion-molded article under the situation of liquid of containing tensio-active agent etc. in expansion-molded article, the heat fusion interface between the foam particle is not also by intrusions such as oil component, pigment or tensio-active agents.Therefore, the liquid etc. that can prevent to contain oil component, pigment, tensio-active agent is exuded to the problem of the outside of expansion-molded article by the heat fusion interface between the expanded particle.
Embodiment
The expandable polystyrene resin beads that foaming and molding of the present invention is used, it is on the surface of polystyrene resin grain kind, setting makes the polystyrene monomer polymerization that contains cross-linkable monomer and the polystyrene resin skin that forms, the infiltration of easy volatile whipping agent is formed, it is characterized by, the gel fraction that constitutes the polystyrene resin of this particle is 10～50 quality %, the weight-average molecular weight Mw of the polystyrene resin that extracts with tetrahydrofuran (THF)
1With the weight-average molecular weight Mw of particle being cut apart the polystyrene resin that extracts after 2 parts
2Ratio (Mw
1/ Mw
2) be 0.5～0.8 scope, and this Mw
2It is 150,000～400,000 scope.
The grain that becomes the nuclear of expandable polystyrene resin beads of the present invention is planted the polystyrene resin of part, there is no particular limitation, can exemplify out the homopolymer of styrenic monomers such as vinylbenzene, alpha-methyl styrene, Vinyl toluene, chloro-styrene, ethyl styrene, isopropyl benzene ethene, dimethyl styrene or their multipolymer etc.In addition, constitute grain and plant the polystyrene resin of part, can be above-mentioned styrenic monomers and can with the multipolymer of the vinyl monomer of this styrenic monomers copolymerization, vinyl monomer as such can exemplify out (methyl) alkyl acrylate, (methyl) vinyl cyanide, dimethyl maleate, dimethyl fumarate, DEF, ethyl fumarates etc. such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid cetyl ester.
In addition, constitute the outer field polystyrene resin of above-mentioned polystyrene resin, it forms the styrenic monomers polymerization that contains cross-linkable monomer.As above-mentioned cross-linkable monomer, so long as can give the material of expandable polystyrene resin beads with crosslinking structure, just there is no particular limitation, can exemplify out the multi-functional monomers such as aklylene glycol dimethacrylate of divinylbenzene, polyethylene glycol dimethacrylate etc., wherein, preferred divinylbenzene.In addition, constitute the outer field polystyrene resin of resin, can be above-mentioned cross-linkable monomer and above-mentioned styrenic monomers and the multipolymer that can carry out the vinyl monomer of copolymerization with this styrenic monomers, vinyl monomer as such can exemplify out (methyl) alkyl acrylate, (methyl) vinyl cyanide, dimethyl maleate, dimethyl fumarate, DEF, ethyl fumarates etc. such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid cetyl ester.That is, can in the monomer solution that contains styrenic monomers, cross-linkable monomer and polymerization starter, supply with above-mentioned vinyl monomer.
The gel fraction of expandable polystyrene resin beads of the present invention is limited at the scope of 10～50 quality %, the scope of preferred 20～35 quality %.If this gel fraction is lower than 10 quality %, then the oil-proofness of the expansion-molded article that obtains with expandable polystyrene resin beads reduces, and the liquid that probably contains oil component, pigment or tensio-active agent etc. can ooze out to the outside by expansion-molded article.On the other hand, if gel fraction is higher than 50 quality %, then the foaminess of expandable polystyrene resin beads reduces, essential heating for a long time when the foaming and molding of expandable polystyrene resin beads, and probably productivity can reduce.
At this, the gel fraction of expandable polystyrene resin beads is meant to be measured by following outline.
That is, expandable polystyrene resin beads is continued heating 1 hour in 140 ℃ baking oven, remove the whipping agent in the expandable polystyrene resin beads, make working sample, measure the quality W of this working sample
1
Then, working sample be impregnated among the toluene 100g, in 140 ℃, continue after the backflow in 20 hours, with 80 purpose metal mesh filters, metal net shaped residue is supplied in the moisture eliminator, 140 ℃ continue down 2 hours pressure and carry out drying under reduced pressure with-60cmHg after, in moisture eliminator, naturally cool to room temperature, measure the quality W of dry residue
2, calculate gel fraction with following formula.
Gel fraction (quality %)=100 * W
2/ W
1
In the present invention, the weight-average molecular weight Mw of the polystyrene resin that extracts with tetrahydrofuran (THF) (THF) of expandable polystyrene resin beads
1With the weight-average molecular weight Mw of particle being cut apart the polystyrene resin that extracts after 2 parts
2Ratio (Mw
1/ Mw
2) be limited at 0.5～0.8 scope.
Ooze out for outside portions of pigment such as the oil component that prevents to contain in food etc. or curry powders, preferably improve the method for oil-proofness,, preferably make crosslinking structure in order to improve oil-proofness.
Preferably pass through the cross-linking density of the skin section of raising particle, oil-proofness is improved, the cross-linking density of particle central part is low, thereby keeps foaming power.
The ratio of above-mentioned weight-average molecular weight is the index that is used to distinguish that the cross-linking density of skin section uprises.That is, if the cross-linking density height of top layer part, then the particle skin section is divided into a kind of molecular sieve, is difficult to extract high-molecular weight resin, the molecular weight Mw that is measured with THF from the particle central part
1Diminish.In addition, the crosslinking structural body of particle central part after a little while, particle cut apart 2 parts after because the molecular sieve that divides by skin section not, the high-molecular weight material also is extracted out, thereby the molecular weight Mw that is measured
2Be higher than Mw
1That is,, can know cross-linking density poor of particle skin section and particle inside by weight-average molecular weight that directly extracts from particle and the ratio of particle being cut apart the molecular weight that extracts after 2 parts.
If the ratio of weight-average molecular weight is greater than 0.8, then crosslinked can't efficiently the carrying out in the particle skin section forms the state of not bringing into play the necessary cross-linking density of oil-proofness, perhaps forms the crosslinked state that proceeds to particle inside, can not get sufficient foaming power.In addition, if this ratio less than 0.5, then the cross-linking density of particle skin section is too high, owing to suppressed the foaming power of particle inside, and can not get the good molding of outward appearance.In addition, because foaming power is suppressed, the particle of molding becomes greatly at interval, makes the increase of oozing out of oil component on the contrary.More preferably 0.55～0.77 scope.
The weight-average molecular weight Mw of cutting apart the polystyrene resin beads that extracts after 2 parts
2Be limited at 150,000～400,000 scope.If be lower than 150,000, the weakened of expansion-molded article then.If be higher than 400,000, then the foaming power step-down can not obtain good expansion-molded article.Mw
2Preferably be made as 250,000～350,000 scope.
The weight-average molecular weight of expandable polystyrene resin beads is by following mensuration.
The about 30mg of sample be impregnated among THF (tetrahydrofuran (THF)) 10mL, preserved at ambient temperature 24 hours, after filtering with the chromatodisk of 0.45 μ m of non-water system, measure the polystyrene conversion molecular weight with the system HPLC (Detector 484, Pump 510) of Waters company.This condition determination is that chromatographic column is used 2 clear and electrician's corporate system Shodex GPC K-806L ( 8.0 * 300mm), column temperature (40 ℃), moving phase (THF), mobile phase flow rate (1.2mL/min), injection pump temperature (room temperature), detection (UV254nm), injection rate (50 μ L), calibration curve standard P S (clear and electrician's corporate system (Shodex) molecular weight 1030000 and TOSOH corporate system molecular weight 5480000,3840000,355000,102000,37900,9100,2630 and 495).
At this, when expandable polystyrene resin beads is cut apart 2 parts, be to cut into 2 parts at face roughly by the particle center of gravity with razor.
Below, the manufacture method of above-mentioned expandable polystyrene resin beads is described.
At first, making is scattered in the dispersion liquid that forms in the water with polystyrene resin grain kind.Manufacture method as this polystyrene resin grain kind, can use method in common, can exemplify out as required and in above-mentioned styrenic monomers, add vinyl monomer, make its suspension polymerization in water make the method for polystyrene resin grain kind then, above-mentioned polystyrene resin is supplied in the forcing machine, carries out melting mixing, from the forcing machine strand form extrude, cut off every specified length, thus the method for manufacturing polystyrene resin grain kind etc.Preferred 150,000～400,000 the scope of the weight-average molecular weight of above-mentioned polystyrene resin grain kind, more preferably 250,000～350,000 scope.
Then, in the dispersion liquid that above-mentioned polystyrene resin grain kind is scattered in the water, supply with the monomer solution that contains styrenic monomers, above-mentioned cross-linkable monomer and polymerization starter continuously or intermittently, under the condition that polymerization starter exists, make monomer carry out seeding polymerization, make the outer growth of polystyrene resin on the surface of polystyrene resin grain kind, thereby make polystyrene resin beads.
At this moment, cross-linkable monomer preferably in part or all of styrenic monomers the dissolving back add.If add cross-linkable monomer and styrenic monomers individually, then probably in crosslinking structure, produce uneven.
Plant 100 mass parts with respect to the polystyrene resin grain, the amount of styrenic monomers is limited at 12～100 mass parts.If styrenic monomers less than 12 mass parts, the crosslinked body ratio of the expandable polystyrene resin beads of then making is few, can not bring into play sufficient oil-proofness.In addition, if styrenic monomers surpasses 100 mass parts, the crosslinked body ratio of the expandable polystyrene resin beads of then making is too much, and foaming power is impaired, between the particle bonding dying down, oozing out of content becomes many on the contrary, or can not get expansion-molded article.
In addition, with respect to the quality of the styrenic monomers of adding, the addition of cross-linkable monomer is limited at the scope of 0.2～1.0 quality %.If less than 0.2 quality %, then the crosslinking structure deficiency can not be brought into play sufficient oil-proofness.And if surpass 1.0 quality %, then crosslinked many degree, foaming power is impaired, it is big that the expanded particle gap of molding becomes, oil component to ooze out change many, maybe can not obtain expansion-molded article.
When supplying with above-mentioned monomer solution in above-mentioned dispersion liquid, the maintenance temperature of dispersion liquid is limited at 80 ℃～110 ℃ scope.If be lower than 80 ℃ temperature, then polymerization velocity is slack-off, and styrenic monomers becomes and is incorporated into the inside of polystyrene resin grain kind easily, can not carry out crosslinked in skin section efficiently.In addition, just carry out polymerization before being absorbed into polystyrene resin grain kind being higher than the styrenic monomers of adding under 110 ℃ the temperature, to the assimilated efficiency variation of polystyrene resin grain kind, production efficiency variation.
In addition, with respect to total 100 mass parts of above-mentioned polystyrene resin grain kind and above-mentioned styrenic monomers, the amount of supplying with above-mentioned monomer solution in above-mentioned dispersion liquid is restricted to the ratio of per 1 hour 1～18 mass parts to be supplied with.If this feed rate is lower than per 1 hour 1 mass parts, then produce the overlong time that is spent.In addition, if more than 18 mass parts, then styrenic monomers becomes and is incorporated into the inside of polystyrene resin grain kind easily, can not carry out crosslinked in skin section efficiently.Be preferably the scope of per 1 hour 5～16 mass parts.The scope of 8.9～12.6 mass parts more preferably.
In addition, employed polymerization starter when above-mentioned styrenic monomers being infiltrated in polystyrene resin grain kind, carry out seeding polymerization, be not particularly limited, can exemplify out benzoyl peroxide, lauryl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxide, the peroxidation trimethylacetic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate, peroxide acetic acid butyl ester, 2,2-pair-(t-butyl peroxy) butane, peroxidation-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, organo-peroxides such as peroxidation six hydrogen terephthalic acid di tert butyl carbonates reach or azo di-isopropyl butyronitrile, azo two azo-compounds such as (methyl pentane nitriles) etc.These polymerization starters can use separately, also can merge use, but the preferred decomposition temperature that merges the transformation period that is used to obtain 10 hours is to be equal to or greater than 50 ℃ and be 80 ℃～120 ℃ polymerization starter less than 80 ℃ polymerization starter and the decomposition temperature that is used to obtain 10 hours transformation period.With respect to styrenic monomers 100 mass parts, the addition of polymerization starter is preferably in the scope of 0.01～3 mass parts.
In above-mentioned dispersion liquid, for improve polystyrene resin grain kind and with it as the phenylethylene resin series growth dispersion of particles stability in the growth of grain kind, can add suspension stabilizer or stabilization aid.
As above-mentioned suspension stabilizer, can exemplify out water-soluble polymer or insoluble mineral compound such as calcium phosphate, magnesium pyrophosphate such as polyvinyl alcohol, methylcellulose gum, polyacrylamide, polyvinylpyrrolidone.Under the situation of using the insoluble mineral compound, usually and use anion surfactant.
Such anion surfactant can exemplify out higher fatty acid salt, β-tetrahydroxy naphthalenesulfonate of alkylbenzene sulfonate, the sodium oleate etc. such as alkyl-sulphate, Sodium dodecylbenzene sulfonate of Sodium Lauryl Sulphate BP/USP etc. etc.
Then, make the whipping agent infiltration in the styrene resin particles that obtains by above-mentioned seeding polymerization, make expandable polystyrene resin beads.
As above-mentioned whipping agent, can use general material, can exemplify out aliphatic hydrocarbons, 1 such as propane, butane, pentane, 1-two chloro-1-fluoroethanes (HCFC-141b), 1-chloro-1,1-C2H4F2 C2H4F2 (HCFC-142b), 2-chloro-1,1,1,2-Tetrafluoroethane (HCFC-124), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1-C2H4F2 C2H4F2 fluorine such as (HFC-152a) is a whipping agent, wherein, and the preferred fat hydrocarbon.At this, whipping agent can use separately, also two or more can be merged and use.
And then, in above-mentioned expandable polystyrene resin beads, also can add general additives such as bladder regulator, UV light absorber, extender, tinting material such as thiodipropionate, sulfo-dibutyrate, ethylene bis stearamide.
In addition, the median size of expandable polystyrene resin beads can be adjusted according to the purposes of gained expansion-molded article, but expansion-molded article is when being foaming and molding container, thin thickness, preferred 0.2～1mm.
The expandable polystyrene resin beads that so obtains is made the preparation expanded particle prepare foaming in the preparation foaming machine after, fill gained preparation expanded particle after the shaping die of foaming and molding machine is interior, make its foaming with heating mediums such as heating steams, make their mutual heat fusions integrated by the foaming pressure, make expansion-molded article with desired shape.At this, the preferred 0.015～0.20g/cm of tap density of preparation expanded particle
3Scope, but be not limited thereto.
Above-mentioned expansion-molded article can be enumerated the material of various forms, considers from the angle of bringing into play effect of the present invention, effect effectively, the foaming and molding container of preferred cup-shaped, bowl-shape, plate-like, case shape etc.
In this foaming and molding container, can hold soybean oil, rapeseed oil, perilla oil, sweet oil, sesame oil, Thistle oil, corn wet goods vegetables oil, lard (lard) and butter animal oil such as (tallows), contain oily food and fatty foods such as these instant noodles (comprising auxiliary material), stew, mayonnaise, salad sauce, curried piece, butter, oleomargarine, white dip, sour milk class, ice cream, fried cake circle, hamburger, fried chicken, contain the aqueous solution of tensio-active agent etc.
As previously mentioned, above-mentioned expansion-molded article makes expandable polystyrene resin beads foaming of the present invention and obtains, therefore between the foam particle they heat fusion is integrated securely at the interface, and, the cross-linking density height of the interface portion of heat fusion between the expanded particle, the oil-proofness excellence.
So, even in expansion-molded article, continue to hold the food that contains oil component for a long time or contain the food of pigments such as curry powder or in expansion-molded article, hold under the situation of liquid of containing tensio-active agent etc., heat fusion interface between the foam particle is not also by intrusions such as oil component, pigment or tensio-active agents, therefore, can prevent that oil component, pigment, the liquid etc. that contains tensio-active agent are exuded to the problem of the outside of expansion-molded article by the heat fusion interface between the expanded particle.
In addition, owing to making expandable polystyrene resin beads foaming of the present invention, expansion-molded article of the present invention obtains, therefore, between the foam particle they heat fusion is integrated securely at the interface, it is very level and smooth that the surface of molding becomes, can make appearance looks elegant, have feeling of high class.Of the present invention preferred embodiment in, the center line average roughness of expansion-molded article (this center line average roughness is the center line average roughness of JIS B0601-1994 defined) is the scope of 0.1～1.5 μ m, more preferably the scope of 0.1～1.0 μ m.If center line average roughness surpasses 1.5 μ m, then the particle gap is showy, is difficult to obtain outward appearance attractive in appearance, as to have feeling of high class.In addition, when making center line average roughness, on making, be irrealizable less than 0.1 μ m.
Foodstuff package of the present invention is to form at the food that the foaming and molding container internal packing that contains above-mentioned expansion-molded article contains oily food or food oils and pigment.The kind of the food of being filled in the foaming and molding container, just there is no particular limitation so long as contain greasy material, consider from the angle of bringing into play effect of the present invention, effect effectively, preferably contain oily foods such as aforesaid greasy instant noodles (comprising auxiliary material), stew, mayonnaise, salad sauce, curried piece, butter, oleomargarine, white dip, sour milk class, ice cream, fried cake circle, hamburger, fried chicken, or contain the food of food oils and pigment.The packaged configuration of these foodstuff packages is not particularly limited, and can select suitable packaged configuration according to the shape of expansion-molded article.For example when using the foaming and molding container of cup-shaped, bowl-shape, plate-like etc., can be in this container filling food, seal up cover material at peristome to seal, and then the form of as required integral body being packed with synthetic resin film etc.
Because foodstuff package of the present invention is to form at the food that the foaming and molding container internal packing that contains above-mentioned expansion-molded article contains oily food or food oils and pigment, therefore, even continue to hold the food that contains oil component for a long time or contain the food of pigments such as curry powder in the foaming and molding container, the liquid etc. that also can prevent oil component, pigment, contains tensio-active agent is exuded to the problem of the outside of foaming and molding container by the heat fusion interface between the expanded particle.
Below, further describe by embodiment, but the present invention is not limited to these.
[embodiment]
[embodiment 1]
In the autoclave of the 5L of the stainless steel that has whipping appts, supply ion exchanged water 2.0L, median size are that 0.3mm and weight-average molecular weight are 280,000 polystyrene grain kind 1.5kg, magnesium pyrophosphate 20g and Sodium dodecylbenzene sulfonate 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
To be dissolved in the styrene monomer of 500g as divinylbenzene 2.0g, benzoyl peroxide (10 hour transformation period was 74 ℃) 2.0g and peroxidized t-butyl perbenzoate (10 hour transformation period the was 104 ℃) 1.0g of cross-linkable monomer, make monomer solution.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, the above-mentioned monomer solution of continuous 2 hours supply normal temperature.During as 100 mass parts, the feed rate of monomer solution is the ratio of per 1 hour 12.6 mass parts with the total of polystyrene grain kind and styrene monomer.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, keep intact, continue to keep to supply with in 3 hours Skellysolve A 110g, iso-pentane 30g at 125 ℃.Then, be cooled to 30 ℃, remove dispersion medium, wash, drying, obtain expandable polystyrene resin beads through 2 hours.
The gel fraction and the molecular weight ratio of gained expandable polystyrene resin beads are shown in Table 1.
[embodiment 2]
Polystyrene grain kind 1.1kg, divinylbenzene 4.5g, benzoyl peroxide 3.6g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 900g and make monomer solution, supply with monomer solution 3 hours, the feed rate of monomer solution is made as the ratio of 15.2 mass parts, in addition, undertaken by working order similarly to Example 1.
[embodiment 3]
Polystyrene grain kind 1.65kg, divinylbenzene 1.8g, benzoyl peroxide 1.4g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 350g and make monomer solution, supply with monomer solution 2 hours, the feed rate of monomer solution is made as the ratio of 8.9 mass parts, in addition, undertaken by working order similarly to Example 1.
[embodiment 4]
Polystyrene grain kind 1.75kg, divinylbenzene 2.5g, benzoyl peroxide 1.0g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 250g and make monomer solution, supply with monomer solution 1 hour, the feed rate of monomer solution is made as the ratio of 12.7 mass parts, in addition, undertaken by working order similarly to Example 1.
[embodiment 5]
Except monomer solution being supplied in the dispersion liquid that remains on 80 ℃, undertaken by working order similarly to Example 1.
[embodiment 6]
Except monomer solution being supplied in the dispersion liquid that remains on 105 ℃, undertaken by working order similarly to Example 1.
[comparative example 1]
Except not using the divinylbenzene, undertaken by working order similarly to Example 1.
[comparative example 2]
Except divinylbenzene is made as the 0.5g, undertaken by working order similarly to Example 1.
[comparative example 3]
Except divinylbenzene is made as 6g, the feed rate of monomer solution is made as outside the ratio of 12.7 mass parts, undertaken by working order similarly to Example 1.
[comparative example 4]
Except monomer solution being supplied in the dispersion liquid that remains on 75 ℃, undertaken by working order similarly to Example 1.
[comparative example 5]
Except the supply with monomer solution was made as 2 hours, the feed rate of monomer solution is made as outside the ratio of 22.7 mass parts, undertaken by working order similarly to Example 2.
[comparative example 6]
Polystyrene grain kind 0.90kg, divinylbenzene 5.5g, benzoyl peroxide 4.4g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 1100g and make monomer solution, supply with monomer solution 4 hours, the feed rate of monomer solution is made as the ratio of 13.9 mass parts, in addition, undertaken by working order similarly to Example 1.
[comparative example 7]
Polystyrene grain kind 1.9kg, divinylbenzene 0.5g, benzoyl peroxide 0.4g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 100g and make monomer solution, supply with monomer solution 0.5 hour, the feed rate of monomer solution is made as the ratio of 10.2 mass parts, in addition, undertaken by working order similarly to Example 1.
[comparative example 8]
In the autoclave of the 5L of the stainless steel that has whipping appts, supply ion exchanged water 2.0L, median size are that 0.3mm and weight-average molecular weight are 280,000 polystyrene grain kind 1.1kg, magnesium pyrophosphate 20g and Sodium dodecylbenzene sulfonate 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
Then, above-mentioned dispersion liquid is remained on 125 ℃, continue to keep to supply with in 3 hours Skellysolve A 110g, iso-pentane 30g.Then, cool off, remain on 85 ℃.
Divinylbenzene 4.0g, benzoyl peroxide 3.6g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 900g, make monomer solution.
Then, in above-mentioned dispersion liquid, supplied with above-mentioned monomer solution in continuous 3 hours.The feed rate of monomer solution is the ratio of 15.1 mass parts.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, be cooled to 30 ℃, remove dispersion medium, wash, drying, obtain expandable polystyrene resin beads through 2 hours.
To the expandable polystyrene resin beads of making respectively in the foregoing description 1～6, the comparative example 1～8, press commentary valency method and metewand, mensuration prevents performance, organic compound amount, the tap density of preparation expanded particle and the center line average roughness of molding that oil component oozes out, compare, it the results are shown in the table 1.
＜prevent the evaluation of the performance that oil component oozes out 〉
In the expandable polystyrene resin beads 1.0kg that obtains, add Zinic stearas (pulverizing product, average maximum length are 20 μ m) 3g, in high speed flow ejector half mixing machine, stirred 2 minutes.Then, supply with polyoxyethylene glycol 1g, further stirred 2 minutes, Zinic stearas is covered on particle surface.Then, preserved 3 days at dark cold place.
Then, above-mentioned expandable polystyrene resin beads is supplied in the preparation foaming machine, its preparation is foamed to tap density 0.1g/cm with water vapour
3, obtain preparing expanded particle.Should prepare expanded particle and preserve at normal temperatures 1 day, make its drying.
Then, above-mentioned preparation expanded particle is supplied in the shaping die in the foaming and molding machine, fill, with the water vapour of 0.2MPa the preparation expanded particle is continued 6 seconds of heating, make its foaming, obtaining internal capacity is 450cm
3And wall thickness is the foaming and molding container of the cup-shaped of 2mm.At this, the foaming and molding container of cup-shaped is made the shape that forms to prominent surrounding wall portion of establishing certain altitude obliquely upward from the outer peripheral edges of flat circle shape bottom surface sections.
In the foaming and molding container that obtains, supply with used food flavouring that contains curry powder of commercially available instant noodles (curried flavor) and auxiliary material till filling with, then so that state winding 1 circle on the full surface of the perisporium outside of copy paper (the MY RECYCLE PAPER 100W of NBS RICOH corporate system) contact foaming and molding container.Use to cut in advance to cover the outside complete surperficial shape of perisporium and the copy paper of size, and measure the quality W of the copy paper that cuts in advance
3Then, with stretched polypropene film with the integral container package encapsulation.Then, this packaging vessel is put into the baking oven 96 hours that remains on 60 ℃.Then, packaging vessel is taken out from baking oven, untie film packaging, take off the copy paper of winding from container.If the part because of the oil component variable color of oozing out from internal tank is arranged on the copy paper, then this part is cut.After cutting, mensuration opens the quality W of foraminous, residual copy paper
4, calculate percentage with following formula, prevent the performance that oil component oozes out according to following benchmark evaluation.
Prevent performance (%)=100 * (W that oil component oozes out
3-W
4)/W
3
◎ ... less than 10%, prevent that the performance that oil component oozes out is extremely excellent
Zero ... be equal to or greater than 10% and, prevent the excellent performance that oil component oozes out less than 20%
* ... be equal to or greater than 20%, prevent the poor performance that oil component oozes out
＜organic compound amount 〉
Precision weighing expandable polystyrene resin beads 1.0g, in the expandable polystyrene resin beads of this precision weighing, behind the dimethyl formamide solution 1mL that contains 0.1 volume % cyclopentanol of adding as reference liquid, further adding dimethyl formamide makes volume reach 25mL, this solution was placed 24 hours, made mensuration solution.From this mensuration solution, remove insoluble composition, 1.8mL supplied in 230 ℃ the sample vaporizer, obtain becoming the gas chromatogram of the organic compound of determination object by gas-chromatography, according to the calibration curve of the organic compound of measuring in advance, become determination object, calculate the organic compound amount by above-mentioned collection of illustrative plates.At this, the organic compound that becomes object is styrenic monomers, ethylbenzene, toluene, n-proplbenzene, isopropyl benzene and dimethylbenzene.Their total, few more good more in the container of wrap food, preferred 500ppm or still less, more preferably 400ppm or still less.
At this, the content of organic compound can be used gas chromatograph (Shimadzu Seisakusho Ltd.'s corporate system trade(brand)name " GC-14A ") in the phenylethylene resin series expansion-molded article, measures under following condition determination.
Detector: FID
Chromatographic column: GL SCIENCES corporate system (the 3mm diameter * 2.5m)
Liquid phase: PEG-20M PT 25 quality %
Carrier: Chromosorb W AW-DMCS
Order: 60/80
Column temperature: 100 ℃
Detector temperature: 230 ℃
Inlet temperature: 230 ℃
Carrier gas: nitrogen
Carrier gas flux: 40mL/ branch
The tap density of＜preparation expanded particle 〉
Working sample uses the material of making by following outline.At first, expandable polystyrene resin beads be impregnated in 100 ℃ the water 5 minutes, makes its preparation foaming, with the preparation expanded particle that obtains with 80 purpose wire nettings after separating from hot water, on wire netting, make its dry 20 hours, the thing of use gained in 40 ℃.Then, measure according to JIS K6911:1995 " thermosetting resin ordinary test method ".That is, will prepare expanded particle and record Wg, this working sample is fallen in graduated cylinder naturally, measure the volume Vcm that drops to the working sample in the graduated cylinder with the apparent density determinator according to JIS K6911 as measuring material
3, measure the tap density of preparing expanded particle according to following formula.
Tap density (the g/cm of preparation expanded particle
3The volume (V) of the weight of)=working sample (W)/working sample.
＜average surface roughness 〉
With above-mentioned＜prevent the evaluation of the performance that oil component oozes out in the production process of foaming and molding container identical, make the foaming and molding container of embodiment 1～6, comparative example 1～8, separately center line average roughness is performed as follows mensuration respectively.Center line average roughness is to use the surfaceness meter HANDYSURF E-35A of Tokyo Micronics Inc. system to measure.This HANDYSURFE-35A has following function: the sectional curve to sample surfaces is measured, and according to the method for JISB0601-1994 " surfaceness one definition and expression " defined, is calculated automatically by its result, draws center line average roughness.At this, condition determination all is that the sideway stance of cup-shaped molding is measured, and will cut base mouth value and be made as 0.8mm, measured length is made as the 4mm that cuts 5 times of base mouth values.
Table 1
| Grain kind amount (mass parts) | Styrenic monomers (mass parts) | Cross-linkable monomer (with respect to the quality % of styrenic monomers) | The ratio of the feed rate of monomer solution (mass parts) | Polymerization temperature (℃) | Gel fraction (quality %) | Molecular weight Mw 2 (×10 4) | Molecular weight ratio (Mw 1/Mw 2) | Organic compound amount (ppm) | Tap density (g/cm 3) | Prevent the performance (96hr) that oil component oozes out | Center line average roughness (μ m) | |
| Embodiment 1 | 100 | 33 | 0.50 | 12.6 | 85 | 27 | 29 | 0.66 | 359 | 0.033 | ◎ | 0.9 |
| Embodiment 2 | 100 | 82 | 0.50 | 15.2 | 85 | 47 | 26 | 0.54 | 386 | 0.045 | ○ | 1.5 |
| Embodiment 3 | 100 | 18 | 0.51 | 8.9 | 85 | 22 | 28 | 0.76 | 333 | 0.032 | ◎ | 0.9 |
| Embodiment 4 | 100 | 14 | 1.00 | 12.7 | 85 | 14 | 29 | 0.78 | 352 | 0.029 | ○ | 1.4 |
| Embodiment 5 | 100 | 33 | 0.50 | 12.6 | 80 | 26 | 28 | 0.76 | 376 | 0.033 | ◎ | 1.3 |
| Embodiment 6 | 100 | 33 | 0.50 | 12.6 | 105 | 25 | 28 | 0.59 | 391 | 0.029 | ◎ | 0.6 |
| Comparative example 1 | 100 | 33 | Do not have | 12.6 | 85 | 0 | 28 | 0.98 | 361 | 0.023 | × | 6.2 |
| Comparative example 2 | 100 | 33 | 0.10 | 12.6 | 85 | 19 | 29 | 0.91 | 381 | 0.025 | × | 1.5 |
| Comparative example 3 | 100 | 33 | 1.20 | 12.7 | 85 | 30 | 26 | 0.40 | 357 | 0.067 | Can not be shaped | |
| Comparative example 4 | 100 | 33 | 0.50 | 12.6 | 75 | 26 | 27 | 0.87 | 349 | 0.042 | × | 6.1 |
| Comparative example 5 | 100 | 82 | 0.50 | 22.7 | 85 | 47 | 26 | 0.87 | 388 | 0.052 | × | 5.3 |
| Comparative example 6 | 100 | 122 | 0.50 | 13.9 | 85 | 60 | 22 | 0.80 | 344 | 0.100 | Can not be shaped | |
| Comparative example 7 | 100 | 5 | 0.50 | 10.2 | 85 | 5 | 28 | 0.94 | 372 | 0.023 | × | 2.3 |
| Comparative example 8 | 100 | 82 | 0.50 | 15.1 | 85 | 48 | 25 | 0.85 | 958 | 0.050 | × | 4.8 |
As shown in Table 1, gel fraction is at scope, the molecular weight ratio (Mw of 10～50 quality %
1/ Mw
2) scope and Mw 0.5～0.8
2The expandable polystyrene resin beads of the embodiment of the present invention 1～6 of scope 150,000～400,000, its organic compound amount is low to moderate less than 400ppm, and tap density is at 0.029～0.045g/cm
3, have suitable foaminess.In addition, the expandable polystyrene resin beads of embodiment 1～6 is carried out foaming and molding and the expansion-molded article that obtains has the excellent performance that oil component oozes out that prevents.And then the center line average roughness of the foaming and molding container that is obtained by embodiment 1～6 is 1.5 μ m or littler.
On the other hand, the gel fraction of comparative example 1 becomes 0%, and molecular weight ratio (Mw
1/ Mw
2) high to 0.98, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 1 prevent the poor performance that oil component oozes out, in addition, center line average roughness is 6.2 μ m, and is thicker than embodiment 1～6, the outward appearance of particle becomes showy.
Molecular weight ratio (the Mw of comparative example 2
1/ Mw
2) high to 0.91, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 2 prevent the poor performance that oil component oozes out.
Molecular weight ratio (the Mw of comparative example 3
1/ Mw
2) be low to moderate 0.40, outside scope of the present invention.Expandable polystyrene resin beads by this comparative example 3 can not foaming and molding.
Molecular weight ratio (the Mw of comparative example 4
1/ Mw
2) high to 0.87, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 4 prevent the poor performance that oil component oozes out, in addition, center line average roughness is 6.1 μ m, and is thicker than embodiment 1～6, the outward appearance of particle becomes showy.
Molecular weight ratio (the Mw of comparative example 5
1/ Mw
2) high to 0.87, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 5 prevent the poor performance that oil component oozes out, in addition, center line average roughness is 5.3 μ m, and is thicker than embodiment 1～6, the outward appearance of particle becomes showy.
The gel fraction height to 60% of comparative example 6 is outside scope of the present invention.The expandable polystyrene resin beads of this comparative example 6 can not foaming and molding.
The gel fraction of comparative example 7 is low to moderate 5%, and molecular weight ratio (Mw
1/ Mw
2) high to 0.94, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 7 prevent the poor performance that oil component oozes out, in addition, center line average roughness is 2.3 μ m, and is thicker than embodiment 1～6.
Molecular weight ratio (the Mw of comparative example 8
1/ Mw
2) high to 0.87, outside scope of the present invention.The foaming and molding container that obtains by this comparative example 8 prevent the poor performance that oil component oozes out, in addition, center line average roughness is 4.8 μ m, and is thicker than embodiment 1～6, the outward appearance of particle becomes showy.
Claims (7)
1. expandable polystyrene resin beads, it is to be provided with to make the styrenic monomers polymerization that contains cross-linkable monomer and the polystyrene resin skin that forms on the surface of polystyrene resin grain kind, the expandable polystyrene resin beads that the foaming and molding that infiltration therein has the easy volatile whipping agent to form is used, it is characterized by, the gel fraction that constitutes the polystyrene resin of this particle is 10～50 quality %, the weight-average molecular weight Mw of the polystyrene resin that extracts with tetrahydrofuran (THF)
1With the weight-average molecular weight Mw of particle being cut apart the polystyrene resin that extracts after 2 parts
2Ratio Mw
1/ Mw
2Be 0.5～0.8 scope, and this Mw
2It is 150,000～400,000 scope.
2. expandable polystyrene resin beads as claimed in claim 1 is characterized by, and gel fraction is in the scope of 20～35 quality %.
3. the manufacture method of expandable polystyrene resin beads, it is characterized by, making is scattered in dispersion liquid in the aqueous medium with polystyrene resin grain kind, remain on 80～110 ℃, then in this dispersion liquid, to contain with respect to described grain kind 100 mass parts is the styrenic monomers of 12～100 mass parts, quality with respect to described styrenic monomers is that the cross-linkable monomer of 0.2～1.0 quality % and the monomer solution of polymerization starter are supplied with the ratio of per 1 hour 1～18 mass parts with respect to total 100 mass parts of described grain kind and described styrenic monomers, the outer growth of polystyrene resin that the styrenic monomers that contains cross-linkable monomer is polymerized, and, after supplying with described monomer solution, make the infiltration of easy volatile whipping agent.
4. the manufacture method of expandable polystyrene resin beads as claimed in claim 3 is characterized by, and with respect to total 100 mass parts of described grain kind and described styrenic monomers, supplies with monomer solution with the ratio of per 1 hour 5～16 mass parts.
5. expansion-molded article is characterized by, and preparation expanded particle foaming and molding is obtained, and described preparation expanded particle makes claim 1 or 2 described expandable polystyrene resin beads prepare foaming and obtains.
6. expansion-molded article as claimed in claim 5 is characterized by, and the center line average roughness on molding surface is the scope of 0.1～1.5 μ m, and described center line average roughness is the center line average roughness of JISB0601-1994 defined.
7. foodstuff package is characterized by, and in the container that contains claim 5 or 6 described expansion-molded articles, packing has the food that contains oily food or food oils and pigment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005220403A JP4664148B2 (en) | 2005-07-29 | 2005-07-29 | Expandable polystyrene resin particles and method for producing the same, foam molded product, and food packaging body |
| JP2005220403 | 2005-07-29 |
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| Publication Number | Publication Date |
|---|---|
| CN1903920A true CN1903920A (en) | 2007-01-31 |
| CN100478382C CN100478382C (en) | 2009-04-15 |
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Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4664148B2 (en) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101925647B (en) * | 2008-01-30 | 2013-01-23 | 积水化成品工业株式会社 | Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings |
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103121549A (en) * | 2013-01-28 | 2013-05-29 | 熊建珍 | Packing box made of expandable polystyrene (EPS) material and manufacture method thereof |
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| JP3474995B2 (en) * | 1996-02-15 | 2003-12-08 | 鐘淵化学工業株式会社 | Method for producing expandable styrene polymer particles |
| JP2005187778A (en) * | 2003-12-26 | 2005-07-14 | Kaneka Corp | Temperature-controlled process for producing styrene-based prefoamed particle |
-
2005
- 2005-07-29 JP JP2005220403A patent/JP4664148B2/en not_active Expired - Fee Related
-
2006
- 2006-07-27 TW TW95127476A patent/TWI325434B/en not_active IP Right Cessation
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101925647B (en) * | 2008-01-30 | 2013-01-23 | 积水化成品工业株式会社 | Expandable polystyrene resin beads, process for production thereof, pre-expanded beads and expanded moldings |
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
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| JP2007031641A (en) | 2007-02-08 |
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| TWI325434B (en) | 2010-06-01 |
| TW200722467A (en) | 2007-06-16 |
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