CN1939958A - Foaming shaping product, producing method thereof and packaging for foodstuff - Google Patents
Foaming shaping product, producing method thereof and packaging for foodstuff Download PDFInfo
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- CN1939958A CN1939958A CN 200610139748 CN200610139748A CN1939958A CN 1939958 A CN1939958 A CN 1939958A CN 200610139748 CN200610139748 CN 200610139748 CN 200610139748 A CN200610139748 A CN 200610139748A CN 1939958 A CN1939958 A CN 1939958A
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Abstract
The invention provides a foamed molded article capable of preventing oozing of oil and coloring matter, and a method for producing the same, and a food package obtained by containing and packaging food or the like in the foamed molded article. The foamed molded article is obtained by foaming expandable polystyrene-based resin particles for foaming, wherein the expandable polystyrene-based resin particles has a surface layer formed by polymerizing a crosslinkable monomer and a styrene-based monomer on the surface of polystyrene-based resin particles, and the surface layer is impregnated with an easily volatile blowing agent. Voids are observed between foamed particles on the cross section of the foamed molded article, wherein the number of voids having a major axis of 100-500 mum and a minor axis of 10-100 mum is 5 pieces/cm2 or less.
Description
Technical field
The present invention relates to use the expansion-molded article and the manufacture method thereof of expandable polystyrene resin beads manufacturing, and in containing the container of described expansion-molded article, pack the foodstuff package that food is arranged.
The application require according on September 27th, 2005 spy in Japanese publication be willing to 2005-279408 number right of priority, here cite its content.
Background technology
In the past, the expandable polystyrene resin beads that the whipping agent that infiltrates in styrene resin particles is formed prepares foaming and makes 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 the visual fine kapillary that can not confirm down connects between the interior outside of foaming and molding container.
This situation can be confirmed by following phenomenon occurring: add the dyestuff that contains tensio-active agent in the foaming and molding container, 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 bag trapped fuel foodstuff 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 is shaped 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.
For the foaming and molding container that obtains preventing that such wet goods from oozing out to the outside, its problem is: eliminate the kapillary occur between the expanded particle of foaming and molding container, its immediate cause that to be oil component and moisture ooze out in the molding container.In order to solve this problem, following method is arranged: improve the Heating temperature when being shaped, the fused film of making resin on the surface of foaming and molding container, perhaps, Heating temperature when being shaped by reducing prolongs heat-up time and fully heats molding inside, thereby eliminates the space between expanded particle.Yet if when bringing up to the forming temperature that can form fused film, the part of molding container can be shunk, thereby appearance damage; In addition, if when forming temperature is low, the blow(ing) pressure of preparation expanded particle self becomes insufficient, thereby the fusion of molding worsens, and productivity is also poor, therefore industrial be not useful method.
In the past, when being used in container etc., the conventional art as the expansion-molded article that soaks into of the content that can reduce wet goods disclosed for example patent documentation 1,2.
In patent documentation 1, the technical scheme at the surface-coated super absorbent resin of foamable polystyrene resin particle has been proposed.
In patent documentation 2, the technical scheme of lining fluorinated block copolymer on expandable thermoplastic resin has been proposed.
Patent documentation 1: the spy opens flat 4-272942 communique
Patent documentation 2: the spy opens flat 11-322995 communique
Yet in above-mentioned conventional art, there are the following problems.
The expandable styrene resin beads that use is put down in writing in patent documentation 1 and the foaming grain that obtains, because super absorbent resin moisture absorption when the preparation foaming, and in the foaming grain, be clamminess, consequently, because the flowability of foaming grain worsens, thereby the problem in the bad production of fillibility takes place easily.
In addition, the expandable styrene resin beads that use is put down in writing in patent documentation 2 and the expansion-molded article that obtains, though have the perviousness that prevents for lubricant component and water phase surfactant mixture, but the fluorinated block copolymer price is high, and also have report to confirm that a part of fluorine cpd can accumulate in vivo, worrying for the use of the food product containers aspect of safety-sensitive.
Summary of the invention
The purpose of this invention is to provide expansion-molded article and manufacture method thereof, and packing has the foodstuff package of food in containing the container of described expansion-molded article, even pigment such as oil component that described foaminess molding contains in inside continue to be preserved food etc. for a long time and curry powder or continue to hold under the situation of the liquid that contains tensio-active agent etc. in the specified time in inside, do not ooze out to the outside yet, and foaming and molding, outward appearance excellence.
In order to achieve the above object, the invention provides expansion-molded article, its expandable polystyrene resin beads foaming and molding that foaming and molding is used obtains, the expandable polystyrene resin beads that this foaming and molding is used is to be provided with on the surface of polystyrene resin beads cross-linkable monomer and styrenic monomers polymerization and the top layer that forms, and the easy volatile whipping agent that infiltrates therein forms, it is characterized by, the major diameter that exists between the expanded particle of described expansion-molded article section is 100 μ m～500 μ m, minor axis is that the number in the space of 10～100 μ m is 5/cm
2Or still less.
For expansion-molded article of the present invention, preferably making described expandable polystyrene resin beads skin depth during saturated swelling in tetrahydrofuran (THF) is the scope of 10～50 μ m.
For expansion-molded article of the present invention, the gel fraction of preferred polystyrene resin is 20～30 quality %.
The present invention also provides the manufacture method of expansion-molded article, 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 20～100 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 were supplied with certain proportion with 60～180 minutes, grown up in the top layer of containing the polystyrene resin that the styrenic monomers that will contain cross-linkable monomer is polymerized, and after supplying with described monomer solution, the easy volatile whipping agent is infiltrated and make expandable polystyrene resin beads, then make described expandable polystyrene resin beads foaming and molding obtain each described expansion-molded article in 3 of the fronts.
In addition, the present invention also provides foodstuff package, and it is in the container that contains the described expansion-molded article of the invention described above, and packing has the food that contains oily food or food oils and pigment to form.
Expansion-molded article of the present invention, since between the foaming grain they heat fusion is integrated securely at the interface, thereby almost there is not the space between expanded particle, in addition, owing to being provided with the top layer that cross-linkable monomer and styrenic monomers polymerization are formed in the heat fusion interface portion, thereby the oil-proofness excellence.So even minister continues to hold the food that contains oil component the phase or holds under the situation of the liquid that contains tensio-active agent within it, the heat fusion interface between the foam particle can be by intrusions such as oil component, pigment or tensio-active agents yet.Thereby 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.
And then because the outward appearance excellence of expansion-molded article of the present invention, the space between the expanded particle on surface is few, thereby the surface printing excellence.
Description of drawings
Figure 1A: the figure that is the section of expression expansion-molded article of the present invention.
Figure 1B: the figure of section that is the expansion-molded article of expression comparative example.
Fig. 2: the summary pie graph that is the order of the expression skin depth of measuring expandable polystyrene resin beads.
Fig. 3: be the expanded view on top layer that expression is fixed in the resin particle of PMMA cured body.
Nomenclature
A: the section of expansion-molded article; B: space;
1,2: resin particle; The 3:PMMA cured body; 4: cut surface; 5: the top layer; 6: the PMMA phase of particle outside; 7: the PMMA phase of particle inside.
Embodiment
The expandable polystyrene resin beads foaming and molding that the expansion-molded article of this aspect is used foaming and molding obtains, the expandable polystyrene resin beads that this foaming and molding is used is to be provided with on the surface of polystyrene resin beads cross-linkable monomer and styrenic monomers polymerization and the top layer that forms, and the easy volatile whipping agent that infiltrates therein forms, it is characterized by, the major diameter that exists between the expanded particle of described expansion-molded article section is that 100 μ m～500 μ m, minor axis are that the number in the space of 10～100 μ m is 5/cm
2Or still less.
Number for measuring space between this expanded particle at first is cut into 1cm with razor with expansion-molded article
2Size, with electron microscope observation cut section, measure the number in the space fall into described size range, promptly obtain every 1cm
2The space number.
Figure 1A, Figure 1B are presented at the expansion-molded article section (Figure 1A) of the embodiment of the present invention that makes among the embodiment described later and the figure of the expansion-molded article section (Figure 1B) of comparative example, and symbol A is the section of expansion-molded article among the figure, and B is described space.By Figure 1A, Figure 1B as can be known, the number of the space B between the expanded particle of expansion-molded article of the present invention in this section A tails off.
Expansion-molded article of the present invention is because the major diameter that exists between expanded particle is 100 μ m～500 μ m, minor axis is that the number in the space of 10～100 μ m is 5/cm
2Or still less, even thereby within it minister continue to hold the food that contains oil component the phase or hold under the situation of the liquid that contains tensio-active agent, the heat fusion interface between the foam particle is not also by intrusions such as oil component, pigment or tensio-active agents.Thereby 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.
And then because the outward appearance excellence of expansion-molded article of the present invention, the space between the expanded particle on surface is few, thereby the surface printing excellence.
If this space outnumber 5/cm
2, then oil component ooze out increase, in expansion-molded article, continue for a long time to hold the food that contains oil component or hold under the situation of the liquid that contains tensio-active agent, oil components etc. are exuded to the outside by the space.
Formation is as the polystyrene resin of the part beyond the top layer of the expandable polystyrene resin beads of the manufacturing raw material of expansion-molded article of the present invention, there is no particular limitation, for example can enumerate 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 plant the polystyrene resin of part can also 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 fumarate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid cetyl ester etc. etc.
In addition, constitute the polystyrene resin on above-mentioned top layer, 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. etc., wherein, preferred divinylbenzene.In addition, constitute the polystyrene resin of resin surface layer, 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 fumarate of (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) vinylformic acid cetyl ester etc. etc.That is, can in the monomer solution that contains styrenic monomers, cross-linkable monomer and polymerization starter, supply with above-mentioned vinyl monomer.
Become the expandable styrene resin beads of the manufacturing raw material of expansion-molded article of the present invention, be the scope of 10～50 μ m preferably with above-mentioned resin particle skin depth during saturated swelling in tetrahydrofuran (THF) (hereinafter referred to as THF), the more preferably scope of 15～40 μ m, the more preferably scope of 20～30 μ m.If this skin depth is during less than 10 μ m, the oil-proofness of expansion-molded article reduces, and the liquid that contains oil component or pigment or tensio-active agent etc. is exuded to the outside by expansion-molded article easily.On the other hand, skin depth is during greater than 50 μ m, and 2 times foaminess reduces, and the fusion rate between expanded particle reduces, and oozing out and problem that molding intensity reduces of oil component etc. occur.
As the operation of the measuring method of described skin depth, as shown in Figure 2, preferably implement in the following manner: (1) is immersed in saturated swellingization among the THF (with reference to (a) among Fig. 2) with resin particle 1 under 25 ℃, normal pressure; (2) then, will from THF, isolate through the resin particle 2 of saturated swellingization (with reference to (b) among Fig. 2); (3) then, the resin particle 2 that separation is obtained impregnated in (with reference to (c) among Fig. 2) in the methyl methacrylate (hereinafter referred to as MMA), with the THF (with reference to (d) in Fig. 2) of MMA displacement through resin particle 2 inside of saturated swellingization; (4) then, make the MMA polymerization and make polymethylmethacrylate (hereinafter referred to as PMMA) cured body 3, resin particle is fixed in (with reference to (e) among Fig. 2) in the above-mentioned PMMA cured body 3 with the swelling state; (5) then, cut off (cutting) described PMMA cured body 3 (with reference to (f) among Fig. 2) along face by the resin particle center; (6) then, observe above-mentioned cut surface 4, measure the skin depth (with reference to (g) among Fig. 2) of resin particle.
Fig. 3 is the expanded view of major portion of the cut surface of the PMMA cured body 3 made with above-mentioned measuring method, the top layer of the resin particle that symbol 5 expressions are fixed among this figure, the PMMA phase of 6 expression particle outsides, the PMMA phase of 7 expression particle inside.
As shown in Figure 3, expandable styrene resin beads of the present invention is handled by the operation of carrying out above-mentioned (1)～(6) successively, top layer 5 remains in the cut surface of PMMA cured body 3, it is amplified observation (amplifying the represented round portion of with dashed lines of observing (g) among Fig. 2), can measure thickness.
And then in the present invention, the gel fraction that constitutes the polystyrene resin of expansion-molded article is preferably the scope of 20～30 quality %, the more preferably scope of 20～25 weight %.If this gel fraction is less than 20 quality %, even then the skin depth of expandable polystyrene resin beads is in scope, owing to be filled in 2 foaming power height of the preparation expanded particle in the shaping die, thereby the surface of expansion-molded article is bonding at once, make the enter variation of steam to expansion-molded article inside, the result becomes the many expansion-molded articles in space between expanded particle, and the liquid that contains oil component, pigment or interfacial agent etc. is oozed out to the outside by expansion-molded article easily.On the other hand, if gel fraction is during greater than 30 quality %, 2 foaming powers that then prepare expanded particle are low excessively, fusion variation during foaming and molding between the expanded particle, not only the intensity of gained expansion-molded article reduces, and the space between the preparation expanded particle becomes many, the problem that the content of molding oozes out occurs.
Below, the manufacture method of expansion-molded article of the present invention is described.
In order to make expandable styrene resin beads, use known kind of polymerization (seeding polymerization method) as the manufacturing raw material of expansion-molded article of the present invention.Plant as employed grain among the present invention, can use by the resulting material of manufacture method of known styrene resin particles in the past.Can exemplify out following method: in above-mentioned styrenic monomers, add cross-linkable monomer, in water, make its suspension polymerization make the method for polystyrene resin grain kind then; Perhaps phenylethylene resin series is supplied in the forcing machine, carry out melting mixing, from forcing machine,, cut off every specified length with strand form or spherical the extruding of cardinal principle, thus the method for manufacturing phenylethylene resin series grain kind etc.Consider that from the angle of foaming and molding, rerum natura the weight-average molecular weight of above-mentioned styrene resin particles is preferred 150,000～400,000, more preferably 250,000～350,000.
The problem that will solve as the present invention for the pigment of the oil component that prevents to contain and curry powder etc. is exuded to the outside, preferably improves the oil-proofness on expansion-molded article surface in food etc.Aspect the oil-proofness raising that makes the expansion-molded article that obtains by the such foaming and molding method that is called as pearl method (PVC one ズ method) of the present invention, because the top layer of expandable styrene resin beads is a lot of in the situation that the surface of expansion-molded article exposes, so the essential cross-linking density that improves above-mentioned resin particle surface.And then, keeping excellent foaming and molding in order to make above-mentioned expandable styrene resin beads, the central part of preferred resin particle contains the alap phenylethylene resin series of cross-linking density.
Then, after being scattered in above-mentioned grain kind 100 mass parts in the aqueous medium, remain on 80 ℃～110 ℃, then in this dispersion liquid, the styrenic monomers that will contain 20～100 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 were supplied with certain proportion with 60～180 minutes, grown up in the top layer of containing the polystyrene resin that the styrenic monomers that will contain cross-linkable monomer is polymerized, and then the easy volatile whipping agent is infiltrated make expandable polystyrene resin beads.
For the present invention, in above-mentioned polymerization process, add cross-linkable monomer, 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 in crosslinking structure, produce inequality, can not get uniform expandable styrene resin beads probably.
Plant 100 mass parts with respect to grain, the addition of styrenic monomers is made as the scope of 20～100 mass parts.If the skin depth of the expandable styrene resin beads that styrenic monomers less than 20 mass parts, is then made is thin, appearance can not be brought into play the problem of sufficient oil-proofness.In addition, if styrenic monomers surpasses 100 mass parts, then in the grain kind, permeate too much, the top layer of the expandable styrene resin beads that obtains is blocked up, thereby foaming power is impaired, between the particle bonding dying down, to ooze out change many from interparticle for the oil component that content not only occurs, and the problem that the intensity of molding reduces occurs.
In addition, with respect to the quality of the styrenic monomers of adding, the addition of cross-linkable monomer is set in the scope of 0.2～1.0 quality %.If cross-linkable monomer less than 0.2 quality %, the crosslinking structure deficiency on the top layer of the expandable styrene resin beads of then making, appearance can not be brought into play the problem of sufficient oil-proofness.On the other hand, then excessively crosslinked if cross-linkable monomer surpasses 1.0 quality %, have that foaming power is impaired, the expanded particle gap of molding becomes the problem of oozing out increase big, oil component.
The temperature of adding above-mentioned monomer solution is made as 80～110 ℃ scope.If this temperature is lower than 80 ℃, then polymerization velocity is slack-off, and styrenic monomers becomes and penetrates into the inside of phenylethylene resin series grain kind easily, can not carry out crosslinked in skin section efficiently.In addition, if than 110 ℃ of high temperature, then the styrenic monomers of Tian Jiaing was just carried out polymerization before being absorbed into polystyrene resin grain kind, the assimilated efficiency variation in polystyrene resin beads, and production efficiency worsens, thereby is not preferred.
As making above-mentioned styrenic monomers absorb grain employed polymerization starter when carrying out polymerization in planting, 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-3,3, the 5-tri-methyl hexanoic acid tert-butyl ester, organo-peroxide or Diisopropyl azodicarboxylates such as peroxidation six hydrogen terephthalic acid di tert butyl carbonates, azo two azo-compounds such as (methyl pentane nitriles) etc., can be with they independent uses, or a plurality of merging is used.
As above-mentioned polymerization starter, 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, preferred 0.01～3 mass parts of the addition of polymerization starter.
In above-mentioned dispersion liquid,, can add suspension stabilizer or stabilization aid in order to improve the dispersion stabilization that polystyrene grain kind and grain are planted.
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, merge usually and use anion surfactant.
As such anion surfactant, can exemplify out senior soap such as alkylbenzene sulfonates such as alkyl-sulphate, Sodium dodecylbenzene sulfonate, sodium oleate, β-tetrahydroxy naphthalenesulfonates etc. such as Sodium Lauryl Sulphate BP/USP.
Then, make the infiltration of easy volatile whipping agent in the styrene resin particles that obtains by above-mentioned kind of polymerization, make the expandable styrene resin beads.
As above-mentioned easy volatile 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, the preferred fat hydrocarbon.At this, the easy volatile whipping agent can use separately, also can merge use.And then, in above-mentioned expandable styrene 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.
The median size of expandable styrene 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, be made as 0.2～1mm, preferably be made as 0.2～0.8mm, further preferably be made as 0.3～0.7mm, but be not limited thereto.
The expandable styrene resin beads that so obtains is made the preparation expanded particle prepare foaming in the preparation foaming machine after, after the preparation expanded particle that obtains is filled in the mould of foaming and molding machine, heating medium with heating steam etc. makes its foaming, make their mutual heat fusions integrated by the foaming pressure, make expansion-molded article with desirable shape.At this, the preferred 0.015～0.20g/cm of tap density of preparation expanded particle
3Scope, but be not limited thereto.
Can enumerate the material of various forms as above-mentioned expansion-molded article, consider, the foaming and molding container of preferred cup-shaped, bowl-shape, plate-like, case shape etc. from the angle of bringing into play effect of the present invention, effect effectively.
In this foaming and molding container, can hold oily food and fatty foods such as soybean oil, rapeseed oil, perilla oil, sweet oil, sesame oil, Thistle oil, corn wet goods vegetables oil, butter, lard, instant noodles, 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, owing to above-mentioned expansion-molded article is the material that the expandable styrene resin beads foaming of regulation is obtained, thereby 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 also by intrusions such as oil component, pigment or tensio-active agents, and the liquid etc. that therefore can solve oil component, pigment, contains tensio-active agent is exuded to the problem of the outside of expansion-molded article by the heat fusion interface between the expanded particle.And then, can obtain also excellent foam moldings such as outward appearance is beautiful, printing is excellent, intensity.
Foodstuff package of the present invention is in containing the foaming and molding container of above-mentioned expansion-molded article, and packing has the food that contains oily food or food oils and pigment to form.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 formed in filling food in this container, seal up cover material at peristome to seal, and then the form of as required integral body being packed with synthetic resin film etc.
Below, further describe by embodiment, but the present invention is not limited to these.
Embodiment
[embodiment 1]
In the autoclave of the 5L 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 1600g, magnesium pyrophosphate 20g and Sodium dodecylbenzene sulfonate 1g, stir, and make dispersion liquid.
Adding will be dissolved in the material that obtains in the styrene monomer of 400g as divinylbenzene 1.6g, 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 its milkiness with the stirring of homogeneous agitator, make styrene solution.
Then, above-mentioned dispersion liquid is remained on 90 ℃ of polymerization temperatures, in above-mentioned dispersion liquid, supplied with above-mentioned styrene solution in continuous 120 minutes.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 90 ℃ 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 expandable styrene resin beads that obtains is implemented mensuration of (1) skin depth and the mensuration of (2) gel fraction.
(1) mensuration of skin depth is as follows: (a) select the material that diameter is 0.3～0.4mm from the expandable styrene resin beads that obtains, precision weighing 1.00g is impregnated among the THF100ml;
(b) behind the dipping, under 25 ℃, atmospheric pressure, placed 24 hours, make its saturated swelling in THF;
(c) after 24 hours, filter, obtain the swelling resin particle with 80 purpose wire nettings;
(d) in the commercially available test tube of external diameter 17mm that can be airtight, long 105mm, capacity 10ml, with the state of the above-mentioned swelling resin particle of swelling, add above-mentioned swelling resin particle 2g, MMA3g, 2,2-azo two-(2, the 4-methyl pentane nitrile) 0.003g impregnated in the swelling resin particle among the MMA;
(e) with 40 ℃ thermostatic bath with air-tight state to above-mentioned MMA macerate heating 20 hours;
(f) after the heating,, from test tube, take out the PMMA in the polymerization process with the cold water cooling indeformablely;
(g) with the face of cutting knife, cut the PMMA in the resulting polymerization process along the center by being fixed in inner resin particle;
(h) will cut material with 70 ℃ baking box reheat 2 hours;
(i) behind the reheat, solidify the skin depth of intravital resin particle with determination of electron microscopy PMMA;
(j) mean value of the numerical value that 10 places are recorded is as skin depth (μ m).
The measurement result of the skin depth of the expandable polystyrene resin beads of embodiment 1 is 20 μ m.
(2) mensuration of gel fraction
Expandable polystyrene resin beads is continued heating 1 hour in 140 ℃ baking box, remove the whipping agent in the expandable polystyrene resin beads, make working sample, measure the quality W of this working sample
1Then, working sample is flooded in toluene 100g, after 140 ℃ continue backflow in 20 hours down, 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
The measurement result of the gel fraction of the expandable polystyrene resin beads that obtains in embodiment 1 is 22.0 quality %.
And then, with the expandable polystyrene resin beads foaming and molding that obtains, the expansion-molded article that obtains is carried out following evaluation: the mensuration of (3) space number, the mensuration of (4) molding fusion rate and
(5) prevent that oil component from oozing out the evaluation of performance.
At first, with the expandable polystyrene resin beads foaming and molding, make the foaming and molding container with following condition.
In expandable styrene resin beads 1.0kg, add Zinic stearas (it is 20 μ m that the product of pulverizing on average greatly enhance most) 3g, in high speed flow ejector half mixing machine, stirred 2 minutes.Then, supply with polyoxyethylene glycol 1g, further stirred 2 minutes, be covered with Zinic stearas.Then, preserved 3 days at dark cold place.
Then, above-mentioned expandable styrene 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 foaming and molding machine, fill, use the water vapour of 0.20MPa that the preparation expanded particle is continued to heat for 6 seconds, 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 the shape that forms from the surrounding wall portion that the outer peripheral edges of flat circle shape bottom surface sections are established certain altitude to dashing forward obliquely upward.
(3) mensuration of space number
Begin to cut out the square that the length of side is 1cm from the sidewall of gained foaming and molding container, this test film that cuts out further is divided into 2 parts with razor on thickness direction, with electron microscope observation divisional plane (1cm with razor
2), measuring major diameter is that 100～500 μ m, minor axis are the number in the space of 10～100 μ m, obtains every 1cm
2The space number.Here said major diameter is meant the maximum length in space, and minor axis is meant the maximum width with the vertical space of major diameter.
The measurement result of the space number in the foaming and molding container of embodiment 1 is 2/cm
2
(4) mensuration of molding fusion rate
Fusion rate between the expanded particle of gained foaming and molding container (molding fusion rate) is measured as follows.
The sidewall of above-mentioned foaming and molding container is divided into 2 parts with hand, for the expanded particle in this broadwise out section, calculate the number (a) of particle disrumpent feelings in the particle and the number (b) that broken particle is interrupted at the interface between particle, and be updated in the formula [(a)/((a)+(b))] * 100, the value of gained is fusion rate (%).Estimate with following evaluation method.
◎ ... the fusion rate is 80% or higher, and molding fusion rate is very good.
Zero ... the fusion rate is for being equal to or greater than 50% and less than 80%, molding fusion rate is good
* ... fusion rate less than 50%, molding fusion rate is bad.
The evaluating and measuring result of the molding fusion rate in the foaming and molding container of embodiment 1 is ◎.
(5) prevent the exudative evaluation of oil component
(internal volume is 450cm at the foaming and molding container that obtains
3) in, will contain the food flavouring of curry powder used in the commercially available instant noodles (curried flavor) and 80% (the volume 360cm that auxiliary material is loaded to container
3), with commercially available food overlay film packaging vessel integral body, this packaging vessel is put into the baking box that remains on 60 ℃ then, measure the time that curried lubricant component is exuded to the packaging vessel outside.
Prevent the performance that oil component oozes out with following evaluation method evaluation.
◎ ... after 48 hours, curried lubricant component does not ooze out, and prevents that the performance that oil component oozes out is splendid.
Zero ... less than 48 hours, oozing out appearred in curried lubricant component being equal to or greater than 24 hours, and it is functional to prevent that oil component from oozing out.
* ... less than 24 hours, oozing out appears in curried lubricant component, prevents the poor performance that oil component oozes out.
The measurement result that prevents the performance that oil component oozes out of the foaming and molding container of embodiment 1 is ◎.
These the results are shown in the table 1.
[embodiment 2]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1100g, divinylbenzene 3.6g, benzoyl peroxide 2.0g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 900g, make styrene solution, supply with styrene solution 120 minutes.The results are shown in the table 1.
[embodiment 3]
Except divinylbenzene is made as the 0.8g, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 4]
Except divinylbenzene is made as the 2.8g, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 5]
Except supply styrene solution 60 minutes, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 6]
Except supply styrene solution 180 minutes, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 7]
Except polymerization temperature being made as 80 ℃, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
Except polymerization temperature being made as 105 ℃, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 1]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1900g, divinylbenzene 0.4g, benzoyl peroxide 0.2g and peroxidized t-butyl perbenzoate 0.1g are dissolved in the styrene monomer of 100g, make styrene solution.The results are shown in the table 1.
[comparative example 2]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1000g, divinylbenzene 4.0g, benzoyl peroxide 2.0g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 1000g, make styrene solution.The results are shown in the table 1.
[comparative example 3]
Except divinylbenzene is made as the 4.8g, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 4]
Except divinylbenzene is made as the 0.4g, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 5]
Except supply styrene solution 30 minutes, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 6]
Except supply styrene solution 200 minutes, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 7]
Except polymerization temperature being made as 75 ℃, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example]
Except polymerization temperature being made as 115 ℃, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
Table 1
| Plant amount of resin (mass parts) | Styrenic monomers (mass parts) | Cross-linkable monomer (quality %) | Monomer solution Drain time (branch) | Polymerization temperature (℃) | Skin depth (μ m) | Gel fraction (quality %) | The space number is (individual/cm 2) | Molding fusion rate | Prevent that oil component from oozing out performance | |
| Embodiment 1 | 100 | 25 | 0.40 | 120 | 90 | 20 | 22.0 | 2 | ◎ | ◎ |
| Embodiment 2 | 100 | 82 | 0.40 | 120 | 90 | 50 | 20.5 | 4 | ◎ | ○ |
| Embodiment 3 | 100 | 25 | 0.20 | 120 | 90 | 15 | 20.5 | 3 | ◎ | ◎ |
| Embodiment 4 | 100 | 25 | 0.70 | 120 | 90 | 40 | 24.5 | 1 | ○ | ◎ |
| Embodiment 5 | 100 | 25 | 0.40 | 60 | 90 | 15 | 20.5 | 3 | ◎ | ◎ |
| Embodiment 6 | 100 | 25 | 0.40 | 180 | 90 | 45 | 28.5 | 3 | ○ | ◎ |
| Embodiment 7 | 100 | 25 | 0.40 | 120 | 80 | 30 | 23.0 | 1 | ◎ | ◎ |
| Embodiment 8 | 100 | 25 | 0.40 | 120 | 105 | 15 | 21.0 | 5 | ◎ | ○ |
| Comparative example 1 | 100 | 5.3 | 0.40 | 120 | 90 | 10 | 15.0 | 10 | ◎ | × |
| Comparative example 2 | 100 | 100 | 0.40 | 120 | 90 | 100 | 32.0 | 30 | × | × |
| Comparative example 3 | 100 | 25 | 1.20 | 120 | 90 | 300 | 35.0 | 30 | × | × |
| Comparative example 4 | 100 | 25 | 0.10 | 120 | 90 | 10 | 10.0 | 20 | ◎ | × |
| Comparative example 5 | 100 | 25 | 0.40 | 30 | 90 | 10 | 15.0 | 15 | ○ | × |
| Comparative example 6 | 100 | 25 | 0.40 | 200 | 90 | 55 | 33.5 | 10 | ○ | × |
| Comparative example 7 | 100 | 25 | 0.40 | 120 | 75 | 40 | 18.0 | 10 | ○ | × |
| Comparative example 8 | 100 | 25 | 0.40 | 120 | 115 | 10 | 15.0 | 15 | ○ | × |
As shown in Table 1, the foaming and molding container of making among the embodiment 1～8 of the present invention, viewed major diameter is that 100 μ m～500 μ m, minor axis are that the number in space of 10～100 μ m is few to 5/cm in its section
2Or still less, has the performance that oil component oozes out that prevents of good molding fusion rate and excellence.
On the other hand, the number in the space of the foaming and molding container of making in comparative example 1～8 is more than embodiment, prevents the poor performance that oil component oozes out.
Claims (7)
1. expansion-molded article, its expandable polystyrene resin beads that foaming and molding is used carries out foaming and molding and obtains, the expandable polystyrene resin beads that this foaming and molding is used is to be provided with on the surface of polystyrene resin beads cross-linkable monomer and styrenic monomers polymerization and the top layer that forms, and the easy volatile whipping agent that infiltrates therein forms, it is characterized by, the major diameter that exists between the expanded particle of described expansion-molded article section is that 100 μ m～500 μ m, minor axis are that the number in the space of 10～100 μ m is 5/cm
2Or still less.
2. expansion-molded article according to claim 1 is characterized by, and making described expandable polystyrene resin beads skin depth during saturated swelling in tetrahydrofuran (THF) is the scope of 10～50 μ m.
3. expansion-molded article according to claim 1 and 2 is characterized by, and the gel fraction of polystyrene resin is 20～30 quality %.
4. the manufacture method of expansion-molded article, 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 20～100 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 were supplied with certain proportion with 60～180 minutes, grown up in the top layer of containing the polystyrene resin that the styrenic monomers that will contain cross-linkable monomer is polymerized, and after supplying with described monomer solution the easy volatile whipping agent being infiltrated makes expandable polystyrene resin beads, then makes described expandable polystyrene resin beads foaming and molding obtain claim 1 or 2 described expansion-molded articles.
5. the manufacture method of expansion-molded article, 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 20～100 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 were supplied with certain proportion with 60～180 minutes, grown up in the top layer of containing the polystyrene resin that the styrenic monomers that will contain cross-linkable monomer is polymerized, and after supplying with described monomer solution the easy volatile whipping agent being infiltrated makes expandable polystyrene resin beads, then makes described expandable polystyrene resin beads foaming and molding obtain the described expansion-molded article of claim 3.
6. foodstuff package is characterized by, and in the container that contains claim 1 or 2 described expansion-molded articles, packing has the food that contains oily food or food oils and pigment.
7. foodstuff package is characterized by, and in the container that contains the described expansion-molded article of claim 3, packing has the food that contains oily food or food oils and pigment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005279408 | 2005-09-27 | ||
| JP2005279408A JP2007091781A (en) | 2005-09-27 | 2005-09-27 | Foamed molded article, method for producing the same, and food package |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1939958A true CN1939958A (en) | 2007-04-04 |
Family
ID=37958501
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200610139748 Pending CN1939958A (en) | 2005-09-27 | 2006-09-22 | Foaming shaping product, producing method thereof and packaging for foodstuff |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2007091781A (en) |
| CN (1) | CN1939958A (en) |
| TW (1) | TWI344971B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898673A (en) * | 2012-11-15 | 2013-01-30 | 无锡兴达泡塑新材料股份有限公司 | Food-grade expandable polystyrene particles for food containers and preparation method thereof |
-
2005
- 2005-09-27 JP JP2005279408A patent/JP2007091781A/en not_active Withdrawn
-
2006
- 2006-09-22 CN CN 200610139748 patent/CN1939958A/en active Pending
- 2006-09-25 TW TW95135641A patent/TWI344971B/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898673A (en) * | 2012-11-15 | 2013-01-30 | 无锡兴达泡塑新材料股份有限公司 | Food-grade expandable polystyrene particles for food containers and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2007091781A (en) | 2007-04-12 |
| TW200716696A (en) | 2007-05-01 |
| TWI344971B (en) | 2011-07-11 |
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