CN1939959A - Expandable polystyrene resin beads, process for the preparation of them, and use thereof - Google Patents
Expandable polystyrene resin beads, process for the preparation of them, and use thereof Download PDFInfo
- Publication number
- CN1939959A CN1939959A CN 200610139793 CN200610139793A CN1939959A CN 1939959 A CN1939959 A CN 1939959A CN 200610139793 CN200610139793 CN 200610139793 CN 200610139793 A CN200610139793 A CN 200610139793A CN 1939959 A CN1939959 A CN 1939959A
- Authority
- CN
- China
- Prior art keywords
- particle
- foaming
- resin beads
- resin
- resin particle
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Packging For Living Organisms, Food Or Medicinal Products That Are Sensitive To Environmental Conditiond (AREA)
- Wrappers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a foamable polystyrene-based resin particle which gives a foamed molded article capable of preventing an oil and a pigment from oozing out and is excellent in foamability, and a production method thereof, and a pre-foamed particle obtained from the particle, and a foamed molded article, and a food package prepared by receiving and packaging a food or the like in a container comprising the foamed molded article. The foamable polystyrene-based resin particle for foaming molding, prepared by polymerizing a cross-linkable monomer and a styrenic monomer on the surface of the polystyrene-based resin particle to form a surface layer, and then impregnating the surface with an easily evaporable foaming agent, is characterized in that the thickness of the surface layer is 3 to 100 mum, when the resin is saturated and swollen with tetrahydrofuran, and tetrahydrofuran-insoluble gel content is 10 to 50 mass% based on the total amount of the resin particle.
Description
Technical field
The present invention relates to expandable polystyrene resin beads and manufacture method thereof, the preparation expanded particle, the expansion-molded article that use expandable polystyrene resin beads to make, and in containing the container of this expansion-molded article, pack the foodstuff package that food is arranged.
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.
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 the weight-average molecular weight that the described polyoxyethylene glycol aqueous solution contains 20～50 quality % is 100～600 polyoxyethylene glycol.
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 is all being 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 quality %, 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 cross-linkable monomer 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, be not suitable as the container of 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 foaming polystyrene series 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 cross-linkable monomer of 0.005～0.02 mass parts
Yet, the foaming polystyrene series 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 foaming polystyrene series 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 xanthein.
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: the spy opens flat 9-221563 communique
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.
The present invention for achieving the above object, the expandable styrene resin beads is provided, it is to be provided with the top layer that makes cross-linkable monomer and styrenic monomers polymerization and form on the surface of polystyrene resin beads, and the expandable polystyrene resin beads used of the foaming and molding that forms of the easy volatile whipping agent that infiltrates therein, it is characterized by, skin depth with the saturated swelling of this resin particle in tetrahydrofuran (THF) the time is the scope of 3～100 μ m, and with respect to the total amount of this resin particle, the gel component that is insoluble to tetrahydrofuran (THF) is the scope of 10～50 quality %.
In the expandable styrene resin beads of the present invention, the mensuration of described skin depth is preferably implemented by following operation: (1) impregnated in resin particle and carries out saturated swellingization in the tetrahydrofuran (THF); (2) then, with saturated swelling change resin particle from tetrahydrofuran (THF), separate; (3) then, isolating resin particle be impregnated in the methyl methacrylate, replace the tetrahydrofuran (THF) of the resin particle inside of saturated swellingization with methyl methacrylate; (4) then, make methyl methacrylate polymerization make the polymethylmethacrylate cured body, resin particle is fixed in this polymethylmethacrylate cured body with the swelling state; (5) then, the face along the center by resin particle cuts off described polymethylmethacrylate cured body; (6) then, observe this cut surface, measure the skin depth of resin particle.
In addition, the invention provides the manufacture method of expandable styrene resin beads, it is the grain that contains phenylethylene resin series to be planted 100 mass parts be scattered in the aqueous medium, then, in this dispersion liquid, add the styrenic monomers of 15～100 mass parts, and the cross-linkable monomer of 0.03～1.0 mass parts, make its absorption, polymerization is planted and after obtaining styrene resin particles in described grain, infiltration easy volatile whipping agent is made the method for expandable styrene resin beads, it is characterized by, the ratio of the phenylethylene resin series in the growth particle in polymerization process is made as the scope of 80～100 quality %, thereby obtains the described expandable styrene resin beads of the invention described above.
In addition, the invention provides the preparation expanded particle that makes the invention described above described expandable polystyrene resin beads preparation foaming and obtain.
In addition, the invention provides expansion-molded article, it is characterized by, make the invention described above described preparation expanded particle foaming and molding and obtain.
In addition, the invention provides foodstuff package, it is characterized by, in the container that contains the described expansion-molded article of the invention described above, packing has the food that contains oily food or food oils and pigment.
Make expandable polystyrene resin beads preparation foaming of the present invention obtain preparing expanded particle, should prepare the expanded particle foaming and molding and obtain expansion-molded article, even when continuing to hold the food that contains oil component in expansion-molded article inside for a long time or holding the liquid that contains tensio-active agent, 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
Fig. 1: the summary pie graph that shows the working order of the skin depth of measuring expandable polystyrene resin beads.
Fig. 2: the expanded view that shows the top layer that is fixed on the resin particle on the PMMA cured body.
Nomenclature
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
Expandable styrene resin beads of the present invention, it is that the top layer make cross-linkable monomer and styrenic monomers polymerization and to form is set on the surface of polystyrene resin beads, the infiltration of easy volatile whipping agent is wherein formed, it is characterized by, the skin depth of this resin particle when saturated swelling is in tetrahydrofuran (THF) (hereinafter referred to as THF) under 25 ℃, normal pressure is the scope of 3～100 μ m, and with respect to the total amount of this resin particle, the gel component that is insoluble to THF is the scope of 10～50 quality %.
Constitute the polystyrene resin of the top layer part in addition of expandable polystyrene resin beads of the present invention, 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 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 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.
In expandable styrene resin beads of the present invention, above-mentioned skin depth is made as the scope of 3～100 μ m, the scope of preferred 5～80 μ m, the more preferably scope of 5～70 μ m, the most preferably scope of 10～50 μ m.If this skin depth is less than 3 μ m, then the oil-proofness of expansion-molded article reduces, and the liquid that contains oil component, pigment or tensio-active agent etc. oozes out to the outside by molding easily.In addition-aspect, if skin depth greater than 100 μ m, then 2 foaminess reduce, the fusion rate between expanded particle reduces, and the oozing out of oil component etc., and the problem that reduces of the intensity of molding occur.
The operation of the measuring method of above-mentioned skin depth, as shown in Figure 1, preferably implement according to following operation: (1) impregnated in resin particle 1 and carries out saturated swellingization (with reference to Fig. 1 (a)) among the THF under 25 ℃, normal pressure; (2) then, with saturated swelling change resin particle 2 from THF, separate (with reference to Fig. 1 (b)); (3) then, isolating resin particle 2 be impregnated in (with reference to Fig. 1 (c)) in the methyl methacrylate (hereinafter referred to as MMA), replace the THF (with reference to Fig. 1 (d)) of resin particle 2 inside of saturated swellingization with MMA; (4) then, make the MMA polymerization make polymethylmethacrylate (hereinafter referred to as PMMA) cured body 3, resin particle is fixed in (with reference to Fig. 1 (e)) in this PMMA cured body 3 with the swelling state; (5) then, the face along the center by resin particle cuts off described PMMA cured body 3 (with reference to Fig. 1 (f)); (6) then, observe this cut surface 4, measure the skin depth (with reference to Fig. 1 (g)) of resin particle.
Fig. 2 is the expanded view of wanting portion with the cut surface of the PMMA cured body 3 of above-mentioned measuring method making, 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 2, expandable styrene resin beads of the present invention is handled by the order according to the operation of above-mentioned (1)～(6), and top layer 5 remains on the cut surface of PMMA cured body 3, can amplify to observe to it and measure thickness.
And then with respect to the total amount of this resin particle, the gel component that is insoluble to THF of this expandable styrene resin beads is in the scope of 10～50 quality %, the scope of preferred 15～50 quality %, the more preferably scope of 15～40 quality %.The insoluble gel component of this THF is during less than 10 quality %, and the oil-proofness of the expansion-molded article that obtains reduces, and the liquid that contains oil component, pigment or tensio-active agent etc. oozes out to the outside by molding easily.In addition, the insoluble gel component of THF is during greater than 50 quality %, the fusion variation during foaming and molding between the preparation expanded particle, and the space between not only intensity variation, and preparation expanded particle becomes many, the problem that the content of molding oozes out easily occurs.
Below, the manufacture method of expandable styrene resin beads of the present invention is described.
In order to make expandable styrene resin beads of the present invention, use known kind of polymerization (seeding polymerization method).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 this 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, in this dispersion liquid, add styrenic monomers, and the cross-linkable monomer of 0.03～1.0 mass parts of 15～100 mass parts, its absorption, polymerization are planted upward in described grain obtain styrene resin particles, the easy volatile whipping agent is infiltrated make expandable polystyrene resin beads.Being characterized as in manufacture method of the present invention, the ratio of the phenylethylene resin series in the growth particle in the polymerization process is made as the scope of 80～100 quality %, thereby obtains the expandable styrene resin beads.Below, the grain kind in the developmental process is called " grain of growing up is planted ".
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 15～100 mass parts.If the skin depth of the expandable styrene resin beads that styrenic monomers less than 15 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.
Plant 100 mass parts with respect to grain, the addition of cross-linkable monomer is set in the scope of 0.03～1.0 mass parts.If the crosslinking structure deficiency on the top layer of the expandable styrene resin beads that cross-linkable monomer less than 0.03 mass parts, is then made, 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 mass parts, have that foaming power is impaired, the expanded particle gap of molding becomes the problem of oozing out increase big, oil component.
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.
In the present invention, begin during finish from polymerization, the content of the phenylethylene resin series during the grain of growing up in the polymerization process is planted maintains 80～100 quality %, preferred 85～100 quality %, the more preferably scope of 90～100 quality %.As the method for keeping above-mentioned scope, can wait with the amount of the feed speed of the temperature of reaction system, styrenic monomers, polymerization starter and adjust.For example, though temperature of reaction is different because of the kind of polymerization starter, preferred 80～110 ℃.If less than 80 ℃, polymeric speed is slack-off, and styrenic monomers penetrates into the inside that grain is planted easily, causes carrying out on the top layer efficiently crosslinked.In addition, if surpass 110 ℃, then the styrenic monomers of Tian Jiaing was just carried out polymerization before being absorbed into the grain kind, made the assimilated efficiency variation to the grain kind, become out of use Powdered, production efficiency variation, thereby not preferred.
The content of the phenylethylene resin series during the grain of growing up is planted can be measured with the following method.
Growth grain kind in the polyreaction is taken out from aggregation container on a small quantity, after aqueous medium separates, remove the moisture that the grain of growing up is planted the surface with gauze etc., as working sample.
Then, precision weighing 0.08g working sample is dissolved in the 24ml toluene.
In this lysate, add Webster reagent 10ml, 5 quality % potassium iodide aqueous solution 30ml, reach the about 30ml of 1 quality % amidin, use the N/40 sodium thiosulfate solution titrated, obtain sample drop fixed number (ml).At this, Webster reagent makes by iodine 8.7g and iodine trichloride 7.9g are dissolved in the 2L Glacial acetic acid.
On the other hand, sample dissolution and similarly carry out titration with above-mentioned is not obtained blank titration number (ml).
Then, calculate the content of the styrenic monomers in the grain kind of growing up with following formula.
The content of styrenic monomers (quality %)=0.1322 * (blank titration number-sample drop fixed number)/working sample quality (g).
This operation is that the sample of taking with 10 minutes interval till beginning from polymerization to finish to polymerization is carried out, thereby obtains the content of styrenic monomers.
Then, the quality of growth particle is deducted the amount of amount after the styrenic monomers amount phenylethylene resin series in planting as the grain of growing up, the amount in the growth particle (quality %) is calculated with following formula.
Phenylethylene resin series content (quality %)=100 * (working sample quality-styrenic monomers amount)/working sample quality.
Then, the easy volatile whipping agent is infiltrated up in the styrene resin particles that obtains by above-mentioned kind of polymerization, makes 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
3, 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 expanded 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 oily food or contains food oils and the food of pigment forms.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.
Because foodstuff package of the present invention is oily food to be arranged or contain food oils and the food of pigment forms in the foaming and molding container internal packing that contains above-mentioned expansion-molded article, 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 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 1.4g, 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 ℃, in this dispersion liquid, supplied with above-mentioned styrene solution in continuous 1.5 hours.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 90 ℃ of further down maintenances.
Measure the ratio of the phenylethylene resin series in the grain kind of growing up in this polymerization process, its result is that the minimum ratio of the resin in the growth particle is 88%.
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 that (2) are insoluble to the gel component of THF.
(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 THF 100ml;
(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 swelling the state of above-mentioned swelling resin particle, add this 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 15 μ m.
(2) be insoluble to the mensuration of the gel component of THF
The value that the gel component that is insoluble to THF is under the following conditions to be measured.
Working sample W with expandable polystyrene resin beads
1(precision weighing 1.00g ± 0.02g) impregnated among the THF100ml 24 hours under 25 ℃, normal pressure.Dipping back is with 80 purpose metal mesh filters, and residue pressure with-60cmHg under 80 ℃ was carried out drying under reduced pressure 2 hours.Dry back naturally cools to room temperature in moisture eliminator, measure the quality W of dry residue
2
With the value of following formula, calculate the gel component that is insoluble to THF by said determination.
Be insoluble to gel component (quality %)=100 * W of THF
2/ W
1
The measurement result of the gel component that is insoluble to THF of the expandable polystyrene resin beads of embodiment 1 is 32 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) molding fusion rate, (4) 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 internal shaping mould, 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 molding fusion rate
With the fusion rate (molding fusion rate) between the expanded particle of the foaming and molding container that obtains, measure in order to method down.
With the sidewall of above-mentioned foaming and molding container in two with hand, expanded particle to this section, counting disrumpent feelings population (a) and interparticle disrumpent feelings at the interface population (b) in particle is updated in the formula [(a)/((a)+(b))] * 100, with the value that obtains as fusion rate (%).Estimate with following evaluation method.
◎ fusion rate is 80% or higher, and molding fusion rate is very good.
Zero fusion rate is more than or equal to 50% and less than 80%, and molding fusion rate is good.
* fusion rate is less than 50%, and molding fusion rate is bad.
Molding fusion rate in the foaming and molding container of embodiment 1 is 90%, and the evaluating and measuring result is ◎.
(4) 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.
◎ is through after 48 hours, and curried lubricant component does not ooze out, and prevents that the performance that oil component oozes out is splendid.
Zero being equal to or greater than 24 hours less than 48 hours, oozing out appearred in curried lubricant component, 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 evaluation 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 styrene monomer solution was supplied with 2.0 hours continuously, other working orders were similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 3]
Except styrene monomer solution was supplied with 0.5 hour continuously, other working orders were similarly to Example 1 carried out.The results are shown in the table 1.
[embodiment 4]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1720g, divinylbenzene 1.0g, benzoyl peroxide 1.3g and peroxidized t-butyl perbenzoate 0.3g are dissolved in the styrene monomer of 280g, make styrene solution, supply with styrene solution 1.5 hours.The results are shown in the table 1.
[embodiment 5]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1200g, divinylbenzene 2.8g, benzoyl peroxide 3.8g and peroxidized t-butyl perbenzoate 0.8g are dissolved in the styrene monomer of 800g, make styrene solution, supply with styrene solution 2.0 hours.The results are shown in the table 1.
[embodiment 6]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1050g, divinylbenzene 3.3g, benzoyl peroxide 4.4g and peroxidized t-butyl perbenzoate 0.95g are dissolved in the styrene monomer of 950g, make styrene solution, supply with styrene solution 3.0 hours.The results are shown in the table 1.
[comparative example 1]
Except not using the divinylbenzene, other working orders are similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 2]
Except styrene solution was supplied with 4 hours, other working orders were similarly to Example 1 carried out.The results are shown in the table 1.
[comparative example 3]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1800g, divinylbenzene 0.7g, benzoyl peroxide 1.0g and peroxidized t-butyl perbenzoate 0.2g are dissolved in the styrene monomer of 200g, make styrene solution, styrene solution is supplied with 1.5 hours.The results are shown in the table 1.
[comparative example 4]
Except following difference, other working orders are similarly to Example 1 carried out.That is, polystyrene grain kind 1050g, divinylbenzene 3.3g, benzoyl peroxide 4.6g and peroxidized t-butyl perbenzoate 1.0g are dissolved in the styrene monomer of 950g, make styrene solution, styrene solution is supplied with 1.0 hours.The results are shown in the table 1.
Table 1
| Plant amount of resin (mass parts) | Styrenic monomers (mass parts) | Cross-linkable monomer (mass parts) | The minimum proportion of the resin in the growth particle (quality %) | Skin depth (μ m) | Be insoluble to the gel component (quality %) of THF | Molding fusion rate | Prevent that oil component from oozing out performance | |
| Embodiment 1 | 100 | 25 | 0.09 | 88 | 15 | 32 | ◎ | ◎ |
| | 100 | 25 | 0.09 | 96 | 6 | 35 | ◎ | ◎ |
| Embodiment 3 | 100 | 25 | 0.09 | 81 | 70 | 24 | ◎ | ◎ |
| | 100 | 16 | 0.06 | 93 | 4 | 13 | ◎ | ◎ |
| | 100 | 67 | 0.23 | 83 | 35 | 41 | ◎ | ◎ |
| | 100 | 90 | 0.32 | 85 | 93 | 48 | ○ | ◎ |
| Comparative example 1 | 100 | 25 | Do not have | 87 | - | 0 | ◎ | × |
| Comparative example 2 | 100 | 25 | 0.09 | 98 | 1 | 29 | ◎ | × |
| Comparative example 3 | 100 | 10 | 0.04 | 95 | 1 | 8 | ○ | × |
| Comparative example 4 | 100 | 95 | 0.32 | 75 | 110 | 57 | × | × |
As shown in Table 1, the expandable polystyrene resin beads of making among the embodiment 1～6 of the present invention and use it and the foaming and molding container made has excellent molding fusion rate and prevents the performance that oil component oozes out.
That on the other hand, does not use foaming and molding container that the comparative example 1 of cross-linkable monomer obtains prevents that the performance that oil component oozes out is bad.
In addition, skin depth be the comparative example 2 of scope of the skin depth among the not enough the present invention of 1 μ m and 3 foaming and molding container prevent that the performance that oil component oozes out is bad.
And then skin depth is the molding fusion rate of the 110 μ m comparative example 4 thicker than the scope of the skin depth among the present invention and prevents that the performance that oil component oozes out is bad.
Claims (6)
1. expandable styrene resin beads, it is to be provided with the top layer that makes cross-linkable monomer and styrenic monomers polymerization and form on the surface of polystyrene resin beads, and the expandable polystyrene resin beads used of the foaming and molding that forms of the easy volatile whipping agent that infiltrates therein, it is characterized by, skin depth with the saturated swelling of this resin particle in tetrahydrofuran (THF) the time is the scope of 3～100 μ m, and with respect to the total amount of this resin particle, the gel component that is insoluble to tetrahydrofuran (THF) is the scope of 10～50 quality %.
2. expandable styrene resin beads according to claim 1 is characterized by, and the mensuration of described skin depth is implemented by following operation: (1) impregnated in resin particle and carries out saturated swellingization in the tetrahydrofuran (THF); (2) then, with saturated swelling change resin particle from tetrahydrofuran (THF), separate; (3) then, isolating resin particle be impregnated in the methyl methacrylate, replace the tetrahydrofuran (THF) of the resin particle inside of saturated swellingization with methyl methacrylate; (4) then, make methyl methacrylate polymerization make the polymethylmethacrylate cured body, resin particle is fixed in this polymethylmethacrylate cured body with the swelling state; (5) then, the face along the center by resin particle cuts off described polymethylmethacrylate cured body; (6) then, observe this cut surface, measure the skin depth of resin particle.
3. the manufacture method of expandable styrene resin beads, it is the grain that contains phenylethylene resin series to be planted 100 mass parts be scattered in the aqueous medium, then, in this dispersion liquid, add the styrenic monomers of 15～100 mass parts, and the cross-linkable monomer of 0.03～1.0 mass parts, make its absorption, polymerization is planted and after obtaining styrene resin particles in described grain, the easy volatile whipping agent is infiltrated make the method for expandable styrene resin beads, it is characterized by, the ratio of the phenylethylene resin series in the growth particle in polymerization process is made as the scope of 80～100 quality %, thereby obtains claim 1 or 2 described expandable styrene resin beads.
4. the preparation expanded particle is characterized by, and makes claim 1 or 2 described expandable polystyrene resin beads preparation foaming and obtains.
5. expansion-molded article is characterized by, and makes claim 4 described preparation expanded particle foaming and molding and obtains.
6. foodstuff package is characterized by, and in the container that contains the described expansion-molded article of claim 5, packing has the food that contains oily food or food oils and pigment.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005279407A JP4806551B2 (en) | 2005-09-27 | 2005-09-27 | Expandable polystyrene resin particles and process for producing the same, pre-expanded particles, foamed molded product, and food packaging |
| JP2005279407 | 2005-09-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1939959A true CN1939959A (en) | 2007-04-04 |
| CN100469824C CN100469824C (en) | 2009-03-18 |
Family
ID=37958502
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101397930A Active CN100469824C (en) | 2005-09-27 | 2006-09-25 | Expandable polystyrene resin beads, process for the preparation of them, and use thereof |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4806551B2 (en) |
| CN (1) | CN100469824C (en) |
| TW (1) | TWI325435B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910408A (en) * | 2010-03-26 | 2015-09-16 | 积水化成品工业株式会社 | Expanded polystyrene resin particle and method of manufacture for same, polystyrene resin pre-expansion particle |
| CN109906242A (en) * | 2016-11-11 | 2019-06-18 | 株式会社Jsp | Expanded particle and expanded particle formed body |
| CN111418099A (en) * | 2017-11-30 | 2020-07-14 | 日本瑞翁株式会社 | Binder composition for nonaqueous secondary battery electrode, slurry composition for nonaqueous secondary battery electrode, electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| US11225562B2 (en) | 2016-09-16 | 2022-01-18 | Jsp Corporation | Expanded beads and molded object thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5284987B2 (en) * | 2008-01-30 | 2013-09-11 | 積水化成品工業株式会社 | Expandable polystyrene resin particles and method for producing the same, pre-expanded particles, and expanded molded body |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4626554A (en) * | 1985-11-29 | 1986-12-02 | Atlantic Richfield Company | Process for producing modified styrenic polymer beads for high strength foamed articles |
| JP3732418B2 (en) * | 2001-03-26 | 2006-01-05 | 積水化成品工業株式会社 | Expandable styrene resin particles |
-
2005
- 2005-09-27 JP JP2005279407A patent/JP4806551B2/en not_active Expired - Fee Related
-
2006
- 2006-09-25 CN CNB2006101397930A patent/CN100469824C/en active Active
- 2006-09-26 TW TW95135588A patent/TWI325435B/en not_active IP Right Cessation
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104910408A (en) * | 2010-03-26 | 2015-09-16 | 积水化成品工业株式会社 | Expanded polystyrene resin particle and method of manufacture for same, polystyrene resin pre-expansion particle |
| CN104910408B (en) * | 2010-03-26 | 2018-08-03 | 积水化成品工业株式会社 | Foaming polystyrene series resin particle and its manufacturing method, polystyrene resin pre-expanded particles |
| US11225562B2 (en) | 2016-09-16 | 2022-01-18 | Jsp Corporation | Expanded beads and molded object thereof |
| CN109906242A (en) * | 2016-11-11 | 2019-06-18 | 株式会社Jsp | Expanded particle and expanded particle formed body |
| CN109906242B (en) * | 2016-11-11 | 2021-11-23 | 株式会社Jsp | Expanded particles and expanded particle molded article |
| US11466137B2 (en) | 2016-11-11 | 2022-10-11 | Jsp Corporation | Foam particles, and moulded article thereof |
| CN111418099A (en) * | 2017-11-30 | 2020-07-14 | 日本瑞翁株式会社 | Binder composition for nonaqueous secondary battery electrode, slurry composition for nonaqueous secondary battery electrode, electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| CN111418099B (en) * | 2017-11-30 | 2022-12-27 | 日本瑞翁株式会社 | Binder composition for nonaqueous secondary battery electrode, slurry composition for nonaqueous secondary battery electrode, electrode for nonaqueous secondary battery, and nonaqueous secondary battery |
| US11578164B2 (en) | 2017-11-30 | 2023-02-14 | Zeon Corporation | Binder composition for non-aqueous secondary battery electrode, slurry composition for non-aqueous secondary battery electrode, electrode for non-aqueous secondary battery, and non-aqueous secondary battery |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI325435B (en) | 2010-06-01 |
| CN100469824C (en) | 2009-03-18 |
| JP2007091780A (en) | 2007-04-12 |
| JP4806551B2 (en) | 2011-11-02 |
| TW200716695A (en) | 2007-05-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1756652A (en) | Coating composition for thermoplastic resin particles for forming foam containers | |
| CN1939959A (en) | Expandable polystyrene resin beads, process for the preparation of them, and use thereof | |
| CN1067625C (en) | Expanded foamed bead of rubber-modified styrene polymer | |
| CN1450860A (en) | Leavened dough extrusion process | |
| CN1034956C (en) | Aerated and freeze bar soap compositions containing sucrose as mildness aid and processing aid | |
| CN1643121A (en) | Low-trans fats for confectionery and bakery fat compositions | |
| CN1150266C (en) | Expandable polystyrene composition, expanded beads and moulded parts | |
| CN1240763C (en) | Polyvinylidene chloride composition and its prepn | |
| CN101039989A (en) | Plasticizer in alkyl acrylate vinylidene chloride polymer | |
| CN85108437A (en) | Synthetical resin products and manufacture method thereof | |
| KR20150052876A (en) | Eva recycling method | |
| CN1408004A (en) | Water unstable foam | |
| CN1840567A (en) | Expanded polypropylene resin beads, method of producing foam molding of expanded polypropylene resin beads and foam molding obtained by the method | |
| CN1098888C (en) | Expandable polystyrene resin beads, process for the preparation of them, and foam made by using the same | |
| CN1048549A (en) | What contain disordered structure starch is the blend compositions of base-material with the polymkeric substance | |
| CN1048863A (en) | What contain disordered structure starch is the blend compositions of base-material with the polymkeric substance | |
| CN1903920A (en) | Foaming polystyrene series resin particle and its manufacturing method, foaming shaped article and foodstuff package | |
| CN1829768A (en) | 1,1-vinylidene chloride resin film, casing for meat paste product, and packed meat paste product | |
| CN1939958A (en) | Foaming shaping product, producing method thereof and packaging for foodstuff | |
| CN1249767A (en) | Granular powder of modified polytetrafluoroethylene | |
| JP2005272665A (en) | Expandable styrene-based resin particle, method for producing the same and foamed product | |
| CN1324395A (en) | Fat compositions and process for producing the same | |
| TWI329058B (en) | Polystyrene system plastic foam molding material formed in mold and packaging material for food | |
| CN1675294A (en) | Formable styrenic resin particle, and pre-formed particle and foamed moldings using the same | |
| CN1902302A (en) | Fatty acid soap/fatty acid bars which process and have good lather |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |