CN1903549A - Polystyrene series resin in-mould foaming shaped article and foodstuff package - Google Patents
Polystyrene series resin in-mould foaming shaped article and foodstuff package Download PDFInfo
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- CN1903549A CN1903549A CN 200610099107 CN200610099107A CN1903549A CN 1903549 A CN1903549 A CN 1903549A CN 200610099107 CN200610099107 CN 200610099107 CN 200610099107 A CN200610099107 A CN 200610099107A CN 1903549 A CN1903549 A CN 1903549A
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Abstract
The invention provides an in-mold expanded molding having excellent surface smoothness and high capability of being beautifully printed and to provide a packaged food using the same. The polystyrene resin in-mold expanded molding is one prepared by effecting the in-mold expansion of expandable polystyrene resin particles, wherein the centerline surface roughness (as specified in JIS B0601-1994) on the surface of the molding is in the range of 0.1 to 1.5 [mu]m, and at least part of the surface is a printed surface. The packaged food is prepared by stowing food into the polystyrene resin in-mold expanded molding and packaging the food in the molding.
Description
Technical field
The present invention relates to polystyrene series resin in-mould foaming shaped article and foodstuff package
Background technology
The foaminess resin particle that contains polystyrene resin widely uses in making foam molding.For making the foam-in-mould formed products by the foaminess resin particle, adopt following method: at first, it is foamed the foam particle heating and make polystyrene resin expanded particle (preparation expanded particle), then, the finishing die of the preparation expanded particle being put into the foaming and molding machine adds hot particle, in finishing die, further make preparation expanded particle foaming, and, make between the expanded particle fusion mutually and make the foam-in-mould formed products.Therefore, making the preparation foamed process for preparing expanded particle and making in finishing die in the foam-in-mould forming process that fuses between the preparation expanded particle, the foaminess resin particle must be operated with suitable destination and make good foam-in-mould formed products.
By the foam-in-mould formed products that the foaminess resin particle is made, as mentioned above, can make, but the gap between expanded particle is difficult to abundant landfill by the fusion of Foamex particle, at the remained on surface of formed products the gap that does not have complete landfill is arranged.This gap is that the ditch of circular V word shape exists, continues brokenly to intersect with zigzag and be netted with the cross section.Yet, because the ditch width of cloth and the ditch depth of this ditch all become very important size, so the surface of foam-in-mould formed products is rough state, and degraded appearance.
Particularly when being used for coffee container and instant noodles container, can implement printing on the surface of foam-in-mould formed products.After the printing, residual owing to just not being printed, having in interparticle gap, so it is uneven printing to occur, thereby printing effect significantly weakens.So the special strong request of people makes the gap between expanded particle unshowy as much as possible.
Constantly carry out in order to make the inconspicuous as much as possible trial in gap all the time.For example, by in the foaminess resin particle, containing the trial of a large amount of blowing agents, owing to can make the expansive force increase of preparation expanded particle, the therefore amplitude and the degree of depth of the ditch that can reduce to produce in the gap.Yet, there is following shortcoming in the method: owing to remaining in the foam-in-mould formed products a large amount of blowing agents arranged, even after the foam-in-mould formed products that obtains taken out from finishing die, the foam-in-mould formed products still keeps very big foaming power, thereby must in finishing die, cool off fully the foam-in-mould formed products, cause the foaming and molding operation will spend more time thus, can not carry out the foaming and molding operation high-effectly.And even form the interior cooling of mould fully, the central portion projection of the expanded particle of gained foam-in-mould formed products forms concavo-convex significantly.
In addition, because the difference of the blowing agent that uses makes the resin of blowing agent overbate sometimes, resin molding is destroyed when being shaped heating, and the expansive force of the preparation expanded particle in the finishing die is reduced.
In addition, also carried out the aromatic compound of styrene, dimethylbenzene, toluene and ethylo benzene etc. is used as the trial of blowing promotor, but coffee container or in directly edible food such as instant noodles is housed and in the purposes that heats, such aromatic compound is preferably few, does not preferably use as blowing promotor.
Thereby, in patent documentation 1, the manufacture method (seeding polymerization method) of expandable styrene based polymer particle is disclosed, it is by in the waterborne suspension that contains styrenic grain kind, add styrenic monomers and polymerization initiator continuously or intermittently, make this styrenic monomers polymerization in this styrenic grain kind, obtain the styrenic particle, in this styrenic particle, make the manufacture method of the expandable styrene based polymer particle of effumability blowing agent infiltration; 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 polymerisation during, measure 100 mass parts with respect to this total, add the crosslinking agent of 0.005～0.02 mass parts.
The aesthetic appearance of the foam-in-mould formed products that the expandable styrene based polymer particle that use is made by above-mentioned manufacture method obtains is improved really, but for printing was uneven, it is still insufficient that it improves effect.
No. 3474995 communique of [patent documentation 1] special permission
Summary of the invention
The present invention In view of the foregoing finishes, and its purpose is to provide the good foam-in-mould formed products of surface smoothing excellence, printing aesthetic property and uses its foodstuff package.
To achieve these goals, the invention provides polystyrene series resin in-mould foaming shaped article, it is the foam-in-mould formed products that the polystyrene resin expanded particle is carried out foam-in-mould, it is characterized by, the center line average roughness on formed products surface (this center line average roughness is the center line average roughness of JISB0601-1994 defined) is the scope of 0.1～1.5 μ m, with at least a portion on surface as printing surface.
In polystyrene series resin in-mould foaming shaped article of the present invention, the center line average roughness on formed products surface is preferably the scope of 0.1～1.0 μ m.
In polystyrene series resin in-mould foaming shaped article of the present invention, the gel fraction of polystyrene resin is preferably the scope of 5～50 quality %.
In polystyrene series resin in-mould foaming shaped article of the present invention, polystyrene resin preferably contains the zinc stearate of 0.3～1.0 quality %.
In polystyrene series resin in-mould foaming shaped article of the present invention, formed products is preferably made cup-shaped.
In polystyrene series resin in-mould foaming shaped article of the present invention, the total amount that contains the organic compound that is selected from a kind of in styrenic monomers, ethylo benzene, toluene, n-propylbenzene, cumene and the dimethylbenzene or two kinds or more kinds of aromatic compound is preferably all scopes of 0～500ppm of amount of polystyrene series resin in-mould foaming shaped article.
In addition, the invention provides foodstuff package, it is characterized by, in containing the container of above-mentioned polystyrene series resin in-mould foaming shaped article, hold, pack food.
The center line average roughness on the formed products surface of polystyrene series resin in-mould foaming shaped article of the present invention is the scope of 0.1～1.5 μ m, the interparticle gap on its surface is little, when particularly printing on the surface as coffee container or instant noodles container, be difficult to take place only interparticle gap and be not printed and residual such bad situation is arranged, can obtain having the formed products of printing surface attractive in appearance.
The specific embodiment
Being characterized as of polystyrene series resin in-mould foaming shaped article of the present invention, the center line average roughness on formed products surface are the scope of 0.1～1.5 μ m, with at least a portion on surface as printing surface.
The center line average roughness on surface is following mensuration.Center line average roughness is to use the surface roughness meter HANDYSURF E-35A of Tokyo Micronics Inc. system to measure.This HANDYSURF E-35A has following function: the sectional curve to sample surfaces is measured, and according to the method for JIS B0601-1994 " surface roughness-definition and expression " defined, is calculated automatically by its result, draws center line average roughness.At this, condition determination all is that the surface of foam-in-mould formed products is measured, and will cut base mouth value and be made as 0.8mm, measured length is made as the 4mm that cuts 5 times of base mouth values.
At this, the value of center line average roughness is the smaller the better, gets the scope of 0.1～1.5 μ m, more preferably 0.1～1.0 μ m.If center line average roughness surpasses 1.5 μ m, then the particle gap is showy, can not bring into play the flatness of formed products and the aesthetic property of printing.In addition, when center line average roughness is made as less than 0.1 μ m, can not realize using the foaminess resin particle and the foam-in-mould formed products that is shaped.
The gel fraction that constitutes the polystyrene resin of polystyrene series resin in-mould foaming shaped article of the present invention is limited at the scope of 5～50 quality %, the scope of preferred 15～35 quality %.If this gel fraction is lower than 5 quality %, then the oil resistivity of the foam-in-mould formed products that obtains with expandable polystyrene resin beads reduces, and probably can contain the situation that the liquid of oil component, pigment or interfacial agent etc. oozes out to the outside by the foam-in-mould formed products.On the other hand, if gel fraction is higher than 50 quality %, then the foaminess of expandable polystyrene resin beads reduces, and expandable polystyrene resin beads is essential heating for a long time when foam-in-mould is shaped, and the situation that productivity ratio reduces probably can take place.
At this, the gel fraction of expandable polystyrene resin beads is meant to be measured by following outline.
That is, expandable polystyrene resin beads is continued heating 1 hour in 140 ℃ baking oven, remove the blowing agent in the expandable polystyrene resin beads, make working sample, measure the quality W of this working sample
1
Then, working sample be impregnated among the toluene 100g, after 140 ℃ continue backflow in 20 hours down, with 80 purpose metal mesh filters, metal net shaped residue is supplied in the drier, 140 ℃ continue down 2 hours pressure and carry out drying under reduced pressure with-60cmHg after, in drier, 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
There is no particular limitation as the polystyrene resin that constitutes polystyrene series resin in-mould foaming shaped article of the present invention, can exemplify out the homopolymers of styrenic monomers such as styrene, AMS, vinyltoluene, chlorostyrene, ethyl styrene, cumene ethene, dimethyl styrene, bromstyrol or their copolymer etc.
As above-mentioned polystyrene resin, with above-mentioned styrenic monomers as main component, can be above-mentioned styrenic monomers and can with the copolymer of the vinyl monomer of this styrenic monomers copolymerization.Vinyl monomer as such can exemplify out (methyl) alkyl acrylate, (methyl) acrylonitrile, dimethyl maleate, dimethyl fumarate, DEF, ethyl fumarates etc. such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid cetyl ester.
Manufacture method to above-mentioned polystyrene series resin in-mould foaming shaped article describes below.At first, making is dispersed in the dispersion liquid that forms in the water with polystyrene resin grain kind.As the manufacture method of this polystyrene resin grain kind, can use method in common, can exemplify out as required and in above-mentioned styrenic monomers, add vinyl monomer, make its suspension polymerisation in water make the method for polystyrene resin grain kind then; Above-mentioned polystyrene resin supplied to carries out melting mixing in the extruder, from the extruder strand form extrude, cut off every specific length, thereby make the method etc. of polystyrene resin grain kind.Preferred 150,000～400,000 the scope of the weight average molecular weight of above-mentioned polystyrene resin beads, more preferably 250,000～350,000 scope.
Then, to above-mentioned polystyrene resin grain kind is scattered in the dispersion liquid that forms in the water, supply with the monomer solution that contains styrenic monomers, cross-linkable monomer and polymerization initiator continuously or intermittently, under the condition that polymerization initiator exists, make monomer carry out seeding polymerization, make the outer growth of polystyrene resin on the surface of polystyrene resin grain kind, thereby make polystyrene resin beads.
At this moment, cross-linkable monomer preferably in part or all of styrenic monomers the dissolving back add.If add cross-linkable monomer and styrenic monomers individually, then probably in cross-linked structure, produce uneven.
At this, as above-mentioned cross-linkable monomer, so long as can give the material of expandable polystyrene resin beads with cross-linked structure, just there is no particular limitation, can exemplify out the multi-functional monomer of aklylene glycol dimethylacrylates such as divinylbenzene, polyethylene glycol dimethacrylate etc., wherein, preferred divinylbenzene.In addition, constitute the outer field polystyrene resin of resin, can be above-mentioned cross-linkable monomer and above-mentioned styrenic monomers and can with the copolymer of the vinyl monomer of this styrenic monomers copolymerization, vinyl monomer as such can exemplify out (methyl) alkyl acrylate, (methyl) acrylonitrile, dimethyl maleate, dimethyl fumarate, DEF, ethyl fumarates etc. such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid cetyl ester.That is, can in the monomer solution that contains styrenic monomers, cross-linkable monomer and polymerization initiator, supply with above-mentioned vinyl monomer.
With respect to the quality of the styrenic monomers of adding, the scope of preferred 0.1～1.0 quality % of the addition of above-mentioned cross-linkable monomer.If less than 0.1 quality %, then the cross-linked structure deficiency is broken in the resin molding when carrying out the mould internal shaping, is difficult to obtain the formed products of appearance looks elegant.In addition, then crosslinked excessive if surpass 1.0 quality %, diminish foaming capacity, be difficult to obtain the formed products of appearance looks elegant.
Employed polymerization initiator when above-mentioned styrenic monomers being infiltrated in polystyrene resin grain kind, carry out seeding polymerization, be not particularly limited, can exemplify out benzoyl peroxide, lauryl peroxide, peroxidized t-butyl perbenzoate, tert-butyl peroxide, the peroxidating pivalic acid tert-butyl ester, tert-butylperoxy isopropyl carbonate, peroxide acetic acid butyl ester, 2,2-pair-(t-butyl peroxy) butane, peroxidating-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester, organic peroxide or azodiisobutyronitriles such as peroxidating six hydrogen terephthalic acid (TPA) di tert butyl carbonates, azo two azo-compounds such as (methyl pentane nitriles) etc.These polymerization initiators can use separately, also can merge use, but the preferred decomposition temperature that is used to obtain 10 hour half-life that merges is to be equal to or greater than 50 ℃ and be 80 ℃～120 ℃ polymerization initiator less than 80 ℃ polymerization initiator and the decomposition temperature that is used to obtain 10 hour half-life.With respect to styrenic monomers 100 mass parts, the addition of polymerization initiator is preferably in the scope of 0.01～3 mass parts.
In above-mentioned dispersion liquid, for improve polystyrene resin grain kind and with it as the polystyrene resin growth dispersion of nano-particles stability in the growth of grain kind, can add suspension stabilizer or stabilization aid.
As above-mentioned suspension stabilizer, can exemplify out water soluble polymer or slightly solubility inorganic compounds such as calcium phosphate, magnesium pyrophosphate such as polyvinyl alcohol, methylcellulose, polyacrylamide, polyvinylpyrrolidone.Under the situation of using the slightly solubility inorganic compound, usually and use anion surfactant.
Such anion surfactant can exemplify out senior soap such as alkylbenzenesulfonates such as alkyl sulfate, neopelex, enuatrol, β-tetrahydroxy naphthalene sulfonates etc. such as lauryl sodium sulfate.
Then, make the blowing agent infiltration in the polystyrene resin beads that obtains by above-mentioned seeding polymerization, make expandable polystyrene resin beads.
As above-mentioned blowing 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-Difluoroethane (HCFC-142b), 2-chloro-1,1,1,2-HFC-134a (HCFC-124), 1,1,1,2-HFC-134a (HFC-134a), 1,1-Difluoroethane fluorine such as (HFC-152a) is a blowing agent, wherein, and the preferred fat hydrocarbon.At this, blowing agent can use separately, also two or more can be merged and use.
And then, in above-mentioned expandable polystyrene resin beads, also can add general additives such as bladder regulator, ultra-violet absorber, extender, colouring agent such as thiodipropionate, sulfo-dibutyrate, ethylene bis stearamide.
Then, on the expandable polystyrene resin beads that obtains, the be covered zinc stearate of 0.3～1.0 quality %.By the lining zinc stearate, the sliding of preparation expanded particle and finishing die is improved, thus, can obtain outward appearance formed body more attractive in appearance.If the amount of coating deficiency of zinc stearate 0.3 quality % then is difficult to obtain to improve the effect of cosmetic look.In addition, more measure than 1.0 quality even use, also better effect can not occur, zinc stearate excessive in the operation of foaming and molding can come off, and from the angle consideration of production line pollution etc., is not preferred.
In addition, the mixer as the zinc stearate that is used to be covered can use V-Mixer, double cone type mixer, trochoid spiral type mixer, high velocity stream ejector half mixer etc.
The expandable polystyrene resin beads that so obtains prepares foaming in the preparation foaming machine, make polystyrene resin expanded particle (preparation expanded particle), after preparing gained in the finishing die that expanded particle is filled into the foaming and molding machine, heat medium with heating steam etc. further makes its foaming, press by foaming to make their mutual heat fuseds and integrated, make foam-in-mould formed products with desirable shape.At this, the preferred 0.015～0.20g/cm of bulk density of preparation expanded particle
3Scope, but be not limited thereto.
Above-mentioned foam-in-mould formed products can be enumerated the material of various forms, considers from the angle of bringing into play effect of the present invention, effect effectively, the foam-in-mould forming containers of preferred cup-shaped, bowl-shape, plate-like, case shape etc.
Polystyrene series resin in-mould foaming shaped article of the present invention, its surperficial at least a portion is used as printing surface.On the surface of above-mentioned foam-in-mould formed products, implement method of printing, there is no particular limitation, can carry out with various printing processes such as letterpress, lithographic printing, hectographic printing, dry type hectographic printing, intaglio printing, photogravure, screen painting, ink jet printing, mold pressing printings, wherein, preferred especially letterpress, dry type hectographic printing.There is no particular limitation for the China ink that uses in this printing, can suitably select to use from the commercially available various China inks of the printing that was used for polystyrene series resin in-mould foaming shaped containers such as instant noodles in the past.
The formed products of polystyrene series resin in-mould foaming shaped article of the present invention, its center line average roughness is the scope of 0.1～1.5 μ m, gap between this surface particle is little, particularly as coffee container or instant noodles container, when printing, be difficult to take place only interparticle gap and be not printed and residual such bad situation is arranged, can obtain having the formed products of printing surface attractive in appearance.
Foodstuff package of the present invention holds, packs food in containing the foam-in-mould forming containers of above-mentioned polystyrene series resin in-mould foaming shaped article.As the food that holds in the foam-in-mould forming containers, there is no particular limitation, for example can hold oily food and fatty foodstuffs such as soybean oil, rapeseed oil, perilla herb oil, olive oil, sesame oil, safflower oil, corn wet goods vegetable oil, lard (lard) and butter animal oil such as (tallows), the instant noodles (comprising auxiliary material) that contain these, stew, mayonnaise, salad baste, curried piece, butter, margarine, white dip, sour milk class, ice cream, fried cake circle, hamburger, fried chicken, contain the aqueous solution of surfactant etc.The packaged configuration of these foodstuff packages is not particularly limited, and can select suitable packaged configuration according to the shape of foam-in-mould formed products.For example can be under the situation of the foam-in-mould forming containers that uses cup-shaped, bowl-shape, plate-like etc., filling food in this container is sealed up cover material at peristome to seal, and then can make the form that integral body is packed with synthetic resin film etc. as required.
[embodiment]
Below, further describe by embodiment, but the present invention is not limited to these.
In addition, the total content of the organic compound of the polystyrene series resin in-mould foaming shaped article in embodiment, the comparative example is by following mensuration.
＜organic compound amount 〉
Precision weighing polystyrene series resin in-mould foaming shaped article 1.0g, in the foam-in-mould formed products of this precision weighing, after the dimethyl formamide solution 1mL that contains 0.1 volume % cyclopentanol of adding as titer, further adding dimethyl formamide makes volume reach 25mL, this solution was placed 24 hours, made mensuration solution.From this mensuration solution, remove insoluble composition, 1.8mL supplied in 230 ℃ the sample vaporizer, obtain becoming the gas chromatogram of the organic compound of determination object by gas-chromatography, according to the calibration curve of the organic compound of measuring in advance, become determination object, calculate the organic compound amount by above-mentioned collection of illustrative plates.At this, the organic compound that becomes object is styrenic monomers, ethylo benzene, toluene, n-proplbenzene, isopropylbenzene and dimethylbenzene.Their total, particularly few more good more in the foam-in-mould formed products of packaged food, be preferably 500ppm or still less, more preferably 400ppm or still less.
At this, the content of organic compound can be used gas chromatograph (Shimadzu Seisakusho Ltd.'s corporate system trade name " GC-14A ") in the polystyrene series resin in-mould foaming shaped article, measures under following condition determination.
Detector: FID
Chromatographic column: GL SCIENCES corporate system (the 3mm diameter * 2.5m)
Liquid phase: PEG-20M PT 25 quality %
Carrier: Chromosorb W AW-DMCS
Order: 60/80
Column temperature: 100 ℃
Detector temperature: 230 ℃
Inlet temperature: 230 ℃
Carrier gas: nitrogen
Carrier gas flux: 40mL/ branch
Be expressed as " organic compound amount " in the table 1.
[embodiment 1]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 1.5L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 1.5kg, magnesium pyrophosphate 20g and neopelex 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 500g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 2.0g, benzoyl peroxide (10 hour half-life the was 74 ℃) 2.0g that are dissolved with in the styrene monomer of 500g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate (10 hour half-life was 104 ℃) 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 2 hours.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, keep intact, keep supplying with in 3 hours pentane 110g, isopentane 30g continuously at 125 ℃.Then, be cooled to 30 ℃, remove decentralized medium, wash, drying, obtain expandable polystyrene resin beads through 2 hours.
Then, as adding zinc stearate (pulverizing the average maximum length of product is 20 μ m) 5g among the above-mentioned expandable polystyrene resin beads 1.0kg that makes, in high velocity stream ejector half mixer, stirred 2 minutes.Then, supply with polyethylene glycol 1g, further stirred 2 minutes, be covered with zinc stearate.Then, preserved 3 days at dark cold place.
Then, above-mentioned expandable polystyrene resin beads is supplied in the preparation foaming machine, with steam its preparation is foamed to bulk density and reach 0.1g/cm
3, obtain polystyrene resin expanded particle (preparation 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 finishing die of foaming and molding machine, fill, with the steam of 0.2MPa the preparation expanded particle was heated for 6 seconds, make its foaming, obtaining internal capacity is 450cm
3And wall thickness is the foam-in-mould forming containers of the cup-shaped of 2mm.At this, the foam-in-mould forming containers of cup-shaped is made the shape that forms to prominent surrounding wall portion of establishing certain altitude obliquely upward from the outer peripheral edges of flat circle shape bottom surface sections.
Measure center line average roughness, gel fraction, organic compound amount that this foam-in-mould forms container, the results are shown in the table 1.
Then, the cup-shaped foam-in-mould forming containers that obtains is put among the CUPPRINTER KH-6100 of Hubei Seiko corporate system, with the China ink of TOYO INK manufacturing company system is that 6 mouthfuls of linings of FLASH DRY FDCMedium are printed on the formed products surface, use the UV-cured supply unit of using of EYE of EYE GRAPHICS corporate system, form coated film by UV curing, thereby obtain the cup-shaped foam-in-mould forming containers of printing.
Residual with the printing of the interparticle clearance portion of visualization foaming body coating, the aesthetic property of following judgement printing.
Interparticle gap is unshowy ... ◎
Interparticle gap is showy hardly ... zero
Interparticle gap is showy a bit ... △
Interparticle gap is showy ... *
[embodiment 2]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 1.1L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 1.1kg, magnesium pyrophosphate 20g and neopelex 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 900g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 3.6g, the benzoyl peroxide 3.6g that are dissolved with in the styrene monomer of 900g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 3 hours.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, operation sequence is carried out similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[embodiment 3]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 1.65L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 1.65kg, magnesium pyrophosphate 20g and neopelex 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 350g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 1.8g, the benzoyl peroxide 1.4g that are dissolved with in the styrene monomer of 350g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 1 hour.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, operation sequence is carried out similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing, the results are shown in the table 1.
[embodiment 4]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 1.75L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 1.75kg, magnesium pyrophosphate 20g and dodecylbenzene sodium sulfonate 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 250g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 2.5g, the benzoyl peroxide 1.0g that are dissolved with in the styrene monomer of 250g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 1 hour.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, operation sequence is carried out similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing, the results are shown in the table 1.
[embodiment 5]
Except zinc stearate being made as 8g, other are undertaken by operation sequence similarly to Example 1.The gel fraction of mensuration gained formed products and center line average roughness, organic compound amount the results are shown in the table 1.
[comparative example 1]
Except not using divinylbenzene and zinc stearate being made as the 8g, other are undertaken by operation sequence similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[comparative example 2]
Except the use amount with divinylbenzene is made as 0.2g and zinc stearate is made as the 8g, other are undertaken by operation sequence similarly to Example 1.The gel fraction of mensuration gained formed products and center line average roughness, organic compound amount the results are shown in the table 1.
[comparative example 3]
Except zinc stearate being made as 2g, other are undertaken by operation sequence similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[comparative example 4]
Except the use amount with divinylbenzene was made as 13.5g, other were undertaken by operation sequence similarly to Example 2.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[comparative example 5]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 0.9L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 0.9kg, magnesium pyrophosphate 20g and neopelex 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 1100g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 2.8g, the benzoyl peroxide 4.4g that are dissolved with in the styrene monomer of 250g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 1 hour.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, operation sequence is carried out similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[comparative example 6]
Except the use amount with divinylbenzene was made as 0.36g, other were undertaken by operation sequence similarly to Example 2.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
[comparative example 7]
In the autoclave of the 5L of the stainless steel that has agitating device, supply ion exchange water 1.85L, average grain diameter are that 0.3mm and weight average molecular weight are 280,000 polystyrene grain kind 1.85kg, magnesium pyrophosphate 20g and dodecylbenzene sodium sulfonate 1g, speed with commentaries on classics in per 1 minute 300 stirs, and makes dispersion liquid.
On the other hand, in the ion exchange water of 150g, make after the neopelex 0.2g dissolving, be added in the divinylbenzene 1.2g, the benzoyl peroxide 0.6g that are dissolved with in the styrene monomer of 150g as cross-linkable monomer and the material of peroxidized t-butyl perbenzoate 1.0g, stirring makes its milkiness, makes styrene emulsion.
Then, above-mentioned dispersion liquid is remained on 85 ℃, after in the nitrogen replacement reaction vessel, in this dispersion liquid, supplied with above-mentioned styrene emulsion in continuous 1 hour.Then, after 1 hour, be warming up to 125 ℃ and kept 1 hour, finish polymerization 85 ℃ of further down maintenances.
Then, operation sequence is carried out similarly to Example 1.Measure center line average roughness, gel fraction, the organic compound amount of gained foam-in-mould forming containers, and then estimate the aesthetic property of printing back printing.The results are shown in the table 1.
Table 1
| Grain kind amount (mass parts) | Styrenic monomers (mass parts) | Cross-linkable monomer (with respect to the quality % of styrenic monomers) | The amount of coating of zinc stearate (is the quality % of resin with respect to expandable styrene) | Center line average roughness (μ m) | The printing aesthetic property | Gel fraction (quality %) | Organic compound amount (ppm) | |
| Embodiment 1 | 100 | 33 | 0.40 | 0.5 | 0.7 | ◎ | 26 | 295 |
| Embodiment 2 | 100 | 82 | 0.40 | 0.5 | 1.4 | ○ | 47 | 318 |
| Embodiment 3 | 100 | 21 | 0.51 | 0.5 | 0.6 | ◎ | 22 | 274 |
| Embodiment 4 | 100 | 14 | 1.0 | 0.5 | 1.3 | ○ | 14 | 289 |
| Embodiment 5 | 100 | 33 | 0.40 | 0.8 | 0.3 | ◎ | 26 | 295 |
| Comparative example 1 | 100 | 33 | Do not have | 0.8 | 5.3 | × | 0 | 280 |
| Comparative example 2 | 100 | 33 | 0.04 | 0.8 | 2.0 | △ | 3 | 311 |
| Comparative example 3 | 100 | 33 | 0.40 | 0.2 | 2.5 | △ | 26 | 303 |
| Comparative example 4 | 100 | 82 | 1.5 | 0.5 | Can not be shaped | 48 | 323 | |
| Comparative example 5 | 100 | 122 | 0.25 | 0.5 | 10.5 | × | 59 | 313 |
| Comparative example 6 | 100 | 82 | 0.04 | 0.5 | 1.9 | △ | 6 | 291 |
| Comparative example 7 | 100 | 8 | 0.8 | 0.5 | 3.5 | △ | 9 | 305 |
As shown in Table 1, the foam-in-mould forming containers of embodiment 1～5 of the present invention, its surperficial center line average roughness is 1.5 μ m or littler, has good printing aesthetic property.
On the other hand, the foam-in-mould forming containers of comparative example 1～7, its surperficial center line average roughness surpasses 1.5 μ m, and the printing aesthetic property is poor, and in addition, comparative example 4 can not be shaped.
Claims (17)
1. polystyrene series resin in-mould foaming shaped article, it is the foam-in-mould formed products that the polystyrene resin expanded particle is carried out foam-in-mould, it is characterized by, the center line average roughness on formed products surface is the scope of 0.1～1.5 μ m, as printing surface, described center line average roughness is the center line average roughness of JIS B0601-1994 defined with at least a portion on surface.
2. polystyrene series resin in-mould foaming shaped article as claimed in claim 1 is characterized by, and the center line average roughness on formed products surface is the scope of 0.1～1.0 μ m.
3. polystyrene series resin in-mould foaming shaped article as claimed in claim 1 or 2 is characterized by, and the gel fraction of polystyrene resin is the scope of 5～50 quality %.
4. polystyrene series resin in-mould foaming shaped article as claimed in claim 1 or 2 is characterized by, and polystyrene resin contains the zinc stearate of 0.3～1.0 quality %.
5. polystyrene series resin in-mould foaming shaped article as claimed in claim 3 is characterized by, and polystyrene resin contains the zinc stearate of 0.3～1.0 quality %.
6. as each the described polystyrene series resin in-mould foaming shaped article in the claim 1,2,5, it is characterized by, make cup-shaped.
7. polystyrene series resin in-mould foaming shaped article as claimed in claim 3 is characterized by, and makes cup-shaped.
8. polystyrene series resin in-mould foaming shaped article as claimed in claim 4 is characterized by, and makes cup-shaped.
9. as each the described polystyrene series resin in-mould foaming shaped article in the claim 1,2,5,7,8, it is characterized by, the total amount that contains the organic compound that is selected from a kind of in styrenic monomers, ethylo benzene, toluene, n-propylbenzene, cumene and the dimethylbenzene or two kinds or more kinds of aromatic compound is all scopes of 0～500ppm of amount of polystyrene series resin in-mould foaming shaped article.
10. polystyrene series resin in-mould foaming shaped article as claimed in claim 3, it is characterized by, the total amount that contains the organic compound that is selected from a kind of in styrenic monomers, ethylo benzene, toluene, n-propylbenzene, cumene and the dimethylbenzene or two kinds or more kinds of aromatic compound is all scopes of 0～500ppm of amount of polystyrene series resin in-mould foaming shaped article.
11. polystyrene series resin in-mould foaming shaped article as claimed in claim 4, it is characterized by, the total amount that contains the organic compound that is selected from a kind of in styrenic monomers, ethylo benzene, toluene, n-propylbenzene, cumene and the dimethylbenzene or two kinds or more kinds of aromatic compound is all scopes of 0～500ppm of amount of polystyrene series resin in-mould foaming shaped article.
12. polystyrene series resin in-mould foaming shaped article as claimed in claim 6, it is characterized by, the total amount that contains the organic compound that is selected from a kind of in styrenic monomers, ethylo benzene, toluene, n-propylbenzene, cumene and the dimethylbenzene or two kinds or more kinds of aromatic compound is all scopes of 0～500ppm of amount of polystyrene series resin in-mould foaming shaped article.
13. foodstuff package is characterized by, and in the container of each the described polystyrene series resin in-mould foaming shaped article in containing claim 1,2,5,7,8,10,11,12, holds, packs food.
14. foodstuff package is characterized by, and in the container that contains the described polystyrene series resin in-mould foaming shaped article of claim 3, holds, packs food.
15. foodstuff package is characterized by, and in the container that contains the described polystyrene series resin in-mould foaming shaped article of claim 4, holds, packs food.
16. foodstuff package is characterized by, and in the container that contains the described polystyrene series resin in-mould foaming shaped article of claim 6, holds, packs food.
17. foodstuff package is characterized by, and in the container that contains the described polystyrene series resin in-mould foaming shaped article of claim 9, holds, packs food.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005-220404 | 2005-07-29 | ||
| JP2005220404A JP4925620B2 (en) | 2005-07-29 | 2005-07-29 | Polystyrene resin in-mold foam molded product and food packaging |
| JP2005220404 | 2005-07-29 |
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| Publication Number | Publication Date |
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| CN1903549A true CN1903549A (en) | 2007-01-31 |
| CN1903549B CN1903549B (en) | 2010-09-29 |
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| CN2006100991071A Expired - Fee Related CN1903549B (en) | 2005-07-29 | 2006-07-27 | Polystyrene series resin in-mould foaming shaped article and foodstuff package |
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| Country | Link |
|---|---|
| JP (1) | JP4925620B2 (en) |
| CN (1) | CN1903549B (en) |
| TW (1) | TWI329058B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5234919B2 (en) * | 2008-03-17 | 2013-07-10 | 株式会社ジェイエスピー | Polystyrene resin foam plate and display panel |
| JP6118749B2 (en) * | 2014-03-26 | 2017-04-19 | 積水化成品工業株式会社 | Expandable composite resin particles, pre-expanded particles, and foamed molded body |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4622346A (en) * | 1985-11-29 | 1986-11-11 | Atlantic Richfield Company | Process for producing modified styrenic polymer beads for high strength foamed articles |
| US4626554A (en) * | 1985-11-29 | 1986-12-02 | Atlantic Richfield Company | Process for producing modified styrenic polymer beads for high strength foamed articles |
| US4692472A (en) * | 1986-05-05 | 1987-09-08 | Atlantic Richfield Company | Divinylbenzene in expandable beads for cup molding |
| JPS63159447A (en) * | 1986-12-22 | 1988-07-02 | Japan Styrene Paper Co Ltd | Crosslinked polyolefin resin foam and its production |
| JPH0415234A (en) * | 1990-05-09 | 1992-01-20 | Sekisui Chem Co Ltd | Production of crosslikned polyolefin resin foam |
| JP3308584B2 (en) * | 1992-02-24 | 2002-07-29 | 積水化学工業株式会社 | Method for producing highly filled inorganic resin foam and foam |
| JP3474995B2 (en) * | 1996-02-15 | 2003-12-08 | 鐘淵化学工業株式会社 | Method for producing expandable styrene polymer particles |
| JP2000119435A (en) * | 1998-10-16 | 2000-04-25 | Mitsubishi Kagaku Form Plastic Kk | Antifungal styrene-based expandable resin beads |
| JP4234832B2 (en) * | 1999-01-29 | 2009-03-04 | 株式会社ジェイエスピー | Recycled foamed styrene resin particle production method and recycled foamed styrene resin molded product |
| JP4832716B2 (en) * | 2003-11-06 | 2011-12-07 | 株式会社ジェイエスピー | Small particle size styrenic expandable resin particles, expanded beads and molded products |
| JP2005187778A (en) * | 2003-12-26 | 2005-07-14 | Kaneka Corp | Temperature-controlled process for producing styrene-based prefoamed particle |
| JP4480435B2 (en) * | 2004-03-25 | 2010-06-16 | 積水化成品工業株式会社 | Expandable styrene resin particles, method for producing the same, and foam molded product |
| JP4494113B2 (en) * | 2004-07-29 | 2010-06-30 | 積水化成品工業株式会社 | Method for producing expandable styrene resin particles |
-
2005
- 2005-07-29 JP JP2005220404A patent/JP4925620B2/en active Active
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- 2006-07-27 CN CN2006100991071A patent/CN1903549B/en not_active Expired - Fee Related
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
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| TWI329058B (en) | 2010-08-21 |
| TW200716346A (en) | 2007-05-01 |
| CN1903549B (en) | 2010-09-29 |
| JP2007031642A (en) | 2007-02-08 |
| JP4925620B2 (en) | 2012-05-09 |
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