JP3486744B2 - Expanded styrenic resin laminated sheet for thermoforming, method for producing the same, and molded article - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a foamed styrene resin laminated sheet for thermoforming in which a thermoplastic resin film and a foamed styrene resin sheet are laminated, a method for producing the same, and a molded article, and more specifically, a mold The present invention relates to a foamed styrene-based resin laminated sheet for thermoforming, which has good extrusion or which can be deep-drawn, a method for producing the same, and a molded article.

[0002]

2. Description of the Related Art Conventionally, a product obtained by molding a foamed styrene resin laminated sheet in which a foamed styrene resin sheet and a film are laminated into a tray, a container or the like is used for fruits, foods and industrial materials. Widely used as a molded article for packaging. However, it is extremely difficult to mold a container having a deep drawing ratio of 1.0, which is obtained by dividing the depth of the container by the inner size of the container opening, with this expanded styrene resin laminated sheet. Met.

As a solution to this, Japanese Patent Publication No. 63-
In 20702, a proposal is made to obtain a molded product with an average number of cells in the thickness direction of a foamed styrene resin laminated sheet of 25 to 400 cells / m ² and an amount of residual blowing agent of 0.5% by weight or more. There is. However, specifying the average number of bubbles and the amount of residual foaming agent in this way is not sufficient to obtain a deep-bottomed container, and there is a problem in moldability and distribution of the wall thickness of the container, and physical properties such as cup strength There was a flaw. That is, a part of the side surface of the container is soft, and the strength when held by hand is weak,
It was also deformed when hot water was added and when it was held by the hand. In addition, the taking efficiency (the area of the upper opening of the molded product × the number of molded products taken / the molded area) is uneconomical at about 40% or less, and it is difficult to mold if the deep drawing ratio is 1.0 or more.

Further, in JP-A-6-335988, JP-A-8-85532 and JP-A-9-11380, a thermoplastic resin film is laminated in order to form such a deep-drawn molded article. Using the foam sheet
It is proposed that the area needs to be increased by about 1 to 11% with respect to the area before heating. However, this was good for forming a bowl container with a deep drawing ratio of about 0.5, but depending on the material and basis weight of the film and foam, the container side could be formed with a deep drawing ratio of 1.0 or more. There was a problem that it becomes thinner and the strength becomes weaker.

Further, Japanese Patent Laid-Open No. 9-52304 discloses that
Weight per unit area of laminated foam sheet is 650 g / m
It has been proposed to increase the thickness to ² or more and to increase the thickness during molding to 6 to 9 mm. However, in this case, since the thickness of the laminated foam sheet is large, the molding cycle is long and the weight per container is increased, resulting in an increase in cost. Further, there is a problem that the container is thick and bulky. In addition, when the tray has a complicated partition structure and rib structure in the molded product, the accuracy of the partition structure is poor and the rib structure cannot be clearly molded. There was a problem that the pattern was so out of shape. Further, when the printed laminated foam sheet is molded, there is a problem that it is difficult to align the molded shapes of the tray and the container with the printed pattern.

The present invention solves many of these problems,
As a result of diligent research conducted by the present inventors, there is provided a laminated foam sheet having a strong side wall, capable of forming a deep-drawing container more economically, and capable of forming a mold well. In order to form a deep-drawing container, and to form a mold well including the matching of printed patterns, the cell structure inside the foam sheet, that is, the cell size in the MD direction, the TD direction, and the VD direction, It was discovered that it was important to adjust the cell structure ratio, which is the ratio, and the shrinkage ratio of the laminated foam sheet, and it was completed.

[0007]

The present invention is a laminated sheet in which a foamed styrene resin sheet and a thermoplastic resin film are laminated, and the density of the foamed styrene resin sheet is 0.095 to 0.77 g / cm3. , Thickness is 0.3-3.
The cell structure ratio, which is the ratio of the cell size in the MD direction in the sheet excluding the skin layer: the cell size in the TD direction: the cell size in the VD direction, is 0.72: 1.42: 0.9 at 0 mm.
8 to 1.54: 0.90: 0.72, the amount of the foaming agent remaining in the foamed sheet is 0.01 to 0.3 mol / kg, and the thickness of the thermoplastic resin film is 0. 00
5 to 0.6 mm, and the shrinkage rate of the laminated sheet is -9%
It is a foamed styrene resin laminated sheet for thermoforming, which is characterized by being 19% . Here, the MD of the foam sheet
The direction is the extruding direction of the foamed sheet, the TD direction is the direction perpendicular to the extruding direction of the foamed sheet, and the VD direction is the thickness direction of the foamed sheet. Further, the present invention, when laminating a thermoplastic resin film on a foamed styrenic resin sheet, laminating the foamed sheet and the film with a heating roll, or in a state of a molten film immediately after the film is extruded. The method for producing a foamed styrene resin laminated sheet for thermoforming according to claim 1, wherein the foamed sheet is laminated with the foamed sheet, or the foamed sheet and the film are coextruded and laminated. Further, the present invention is a molded article characterized by thermoforming the foamed styrene resin laminated sheet for thermoforming.

In the present invention, the polystyrene-based resin used for the foamed styrene-based resin sheet is styrene,
Homopolymers or copolymers of methylstyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, paramethylstyrene, chlorostyrene, promostyrene, vinyltoluene, vinylxylene, styrene-maleic anhydride copolymer, styrene-acrylic acid Examples thereof include copolymers, styrene-acrylonitrile resins and acrylonitrile-butadiene-styrene resins. Further, polyphenylene ether or polypropylene may be mixed with the styrene resin. When heat resistance is required, a styrene copolymer containing acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, phenylene ether, or propylene in an amount of 1 to 50% by weight is preferable as the heat resistant polystyrene resin.

At least one selected from butadiene rubber, ethylene-propylene rubber and styrene-butadiene rubber is mixed with the above-mentioned styrene resin, or a styrene copolymer resin obtained by copolymerizing butadiene, isoprene and chloroprene is used. It is preferably used as a mixed impact-resistant styrene resin. Further, the amount to be mixed is preferably about 0.05 to 15% by weight.
The reason for this is that if it is less than 0.05% by weight, it may crack during handling depending on the combination with the thermoplastic resin film to be laminated, and if it exceeds 15% by weight, insufficient strength may occur and the size of the cup, This is because the printability may deteriorate depending on the shape.

Further, the above rubber component is mixed with a styrene resin, and then a polyolefin resin such as polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-vinyl acetate copolymer is mixed in an amount of 1.0 to 50% by weight. The heat resistance and brittleness can be improved. However, when strength is required, it is necessary to control the rubber content to 5% by weight or less.

A foaming agent or the like is added to the styrene resin, and extrusion foam molding is performed to obtain a foam sheet. At this time, 0.2 to 20% by weight of a filler can be added to improve the appearance of the mold surface, the appearance of the surface, the heat resistance and the like. Such fillers include talc, calcium carbonate, shirasu, gypsum,
Examples include general inorganic fillers such as carbon black, white carbon, magnesium carbonate, clay, natural silicic acid, and metal powder, which may be used as a masterbatch before being charged into an extruder. Further, as a compounding agent, for example, a cell regulator, a pigment or the like may be added.

As the foaming agent usable in the present invention, various volatile foaming agents, decomposable foaming agents and the like can be used. Examples of the volatile foaming agent include hydrocarbon, propane, i-butane,
n- butane, i- pentane, n- pentane or a mixture thereof, _{and, N 2, CO 2, N} 2 / CO 2, water,
Water and _{-OH, -COOH, -CN, -NH 3} , -OSO 3
_{H, -NH, CO, NH 2} , -CONH 2, -COOR,
_{-CHSO 3 H, -SO 3 H,} -COON 4, -COON
Examples thereof include a mixture with H ₄ and a group having H ₄ .

As the decomposition type foaming agent, for example, azodicarboxylic acid amide, dinitropentamethylenetetramine,
4,4'oxybis (benzenesulfonyl hydrazide)
And the like. Furthermore, a combination of an organic acid such as sodium bicarbonate or citric acid or a salt thereof with a bicarbonate can be used. Further, for example, a combination of an organic acid such as sodium bicarbonate or citric acid or a salt thereof and bicarbonate can be used by coating with a low molecular weight olefin, liquid paraffin, tallow oil or the like. In addition, it is also possible to use a mixture thereof, and two or more kinds thereof may be mixed. All of these are also available as a masterbatch with powder, flakes, or a thermoplastic resin. In particular, when a polyolefin resin is mixed with a styrene resin and a decomposable foaming agent is used, the polyolefin resin has an effect as a cell regulator. In addition, a decomposing type foaming agent and N ₂ , CO ₂ , i
When -butane, n-butane, i-pentane, and n-pentane are used in combination, the bubbles are fine and the moldability is good.

The density of the expanded styrene resin sheet of the present invention is 0.095 to 0.77 g / cm ³ . It is preferably 0.11 to 0.75 g / cm ³ . Density 0.09
If it is less than 5 g / cm ^3, it is not suitable for deep drawing and is 0.77.
If it exceeds g / cm ³ , the molding cycle becomes long, which is not preferable. The thickness of the foamed styrene resin sheet is
It is 0.3 to 3.0 mm. Preferably 0.5-2.
It is 7 mm. If it is less than 0.3 mm, the strength is insufficient and the molded product has few uses. When it exceeds 3.0 mm, it is difficult to balance the thickness of the wall surface and the bottom surface in the case of a deep-drawn molded product, and it is difficult to control the amount of the remaining foaming agent. Here, when the foamed sheet is extruded and foamed, what is important is that when the foamed sheet is pulled from the circular mold to the plug, the foamed sheet is manufactured so that a chrysanthemum pattern that becomes a wavy pattern does not occur in the TD direction. If the chrysanthemum pattern is present, the cell structure and the cell diameter of the chrysanthemum pattern are different, and the chrysanthemum pattern is expanded by heating for molding, so that a molded product with a good mold and a deep-drawn molded product cannot be molded.

In the present invention, the above-mentioned polystyrene resin can be used as the resin forming the thermoplastic resin film laminated on the expanded styrene resin sheet. In addition, a mixed resin of styrene-based resin and high-impact polystyrene, or high-impact polystyrene, which is a styrene-butadiene block copolymer and is dispersed in a salami structure, may be used. . The particle size of the dispersed styrene-butadiene block copolymer is 0.3 to 10 μm.
Those containing a large amount of m are preferable. Other resins that can be used for the thermoplastic resin film include linear low density polyethylene, high density polyethylene, low density polyethylene, polypropylene, ethylene / propylene random polymer, ethylene / propylene block polymer, ethylene / propylene butene copolymer, ethylene- Vinyl acetate copolymer, ethylene-unsaturated carboxylic acid ester copolymer (for example, ethylene-methyl methacrylate copolymer), engineered ethylene-unsaturated carboxylic acid metal salt copolymer (for example, ethylene-acrylic acid) Magnesium (or zinc)
Copolymer), propylene-vinyl chloride copolymer, propylene-butene copolymer, propylene-maleic anhydride copolymer, propylene-olefin copolymer (propylene-ethylene copolymer, propylene-butene-1 copolymer) polyethylene or polypropylene Unsaturated carboxylic acid (for example, maleic anhydride) modified product, ethylene-
Propylene rubber, atactic polypropylene and the like, polyethylene, ethylene-propylene copolymer,
Examples thereof include a propylene-butene-1 copolymer, a mixture of two or more kinds thereof, and films of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and the like. The polypropylene resin film may be unstretched, uniaxially stretched, or biaxially stretched, but is particularly preferably a nonstretched film (CPP) because of good moldability.

Silicone oil may be mixed in the thermoplastic resin film in an amount of 0.01 to 3% by weight. If the silicone oil content is 0.01% by weight or less, the effect of improving the mold release property and blocking prevention when the container is molded cannot be expected so much.
In addition, the slippage between the container and the blanket of the printing machine becomes poor, and the printability also deteriorates. On the other hand, if the content is 3% by weight or more, the extrusion stability during film production is deteriorated and the appearance of the film is also deteriorated, which is not preferable.

When the silicone oil is kneaded into the thermoplastic film, up to about 0.2% by weight of the resin can be kneaded into the resin by blending, and above this, the resin slips and does not bite stably into the screw. Therefore, in order to mix more than 0.2% by weight to 3% by weight, the resin is kneaded into a resin with a mixing roll such as a calender roll, pelletized, or added in the course of polymerization or pelletization after polymerization. Etc., or press-fitting in the middle of the extruder is preferably performed by a so-called injection method. In addition, silicon oil is 0.0
1 wt% to 0.2 wt% resin is kneaded, and when a further effect is required, kneaded into 0.01 wt% to 0.2 wt% resin and then silicon oil is applied onto the film. It was found that the coating did not become uneven even if it was applied. Therefore, printing unevenness does not occur in the case of kneading with 0.01 wt% to 0.2 wt% resin and further applying silicone oil. Further, an antistatic material such as stearic acid monoglyceride can be kneaded at the same time with the silicone oil. Further, silicone oil may be mixed with the polystyrene resin foam sheet, so that the foamability and the like can be improved. In addition, printing may be performed on a thermoplastic resin film in which silicon is kneaded, and then the printed surface or the unprinted surface may be attached to a polystyrene resin foam sheet.

Further, a white filler such as titanium white or calcium carbonate is added to the thermoplastic resin film in an amount of 0.1-3.
When 0% by weight is mixed, the printability is improved and the unevenness of the surface of the molded product becomes inconspicuous.

When laminating the thermoplastic resin film on the foamed styrene resin sheet, the thermoplastic resin film prepared in advance after extrusion of the foamed sheet is laminated using a heating roll, or the film is extruded. It can be laminated with a foamed sheet in a state of being a molten film immediately after being heated, or can be coextruded and laminated with the foamed sheet and the film. In addition, it is a preferred embodiment that a film provided with an adhesive layer is used to adhere to the foam sheet. In this case, ethylene-vinyl acetate copolymer, partially saponified ethylene-vinyl acetate copolymer,
Chlorinated polyethylene, layers formed by extrusion laminating chlorinated polypropylene, etc., and polybutadiene, polyisoprene, styrene-butadiene copolymer, styrene-isoprene copolymer, etc., with a polyolefin resin such as polypropylene or polyethylene. It is preferable to use, as the adhesive layer, a layer or the like formed by extruding the mixed material and laminating it in a state of being a molten film.

The adhesive layer is made of vinyl-based resin such as polyvinyl acetate, polyvinyl chloride, polyvinylidene chloride,
Adhesive prepared by dissolving cellulose resin such as nitrocellulose, ethyl cellulose, cellulose acetate, etc., epoxy resin, acrylonitrile-butadiene copolymer, etc. in organic solvent, urethane adhesive or polyester adhesive is a thermoplastic resin film. It is also possible to laminate the film formed by applying it on the substrate and drying it by using a heating roll or the like. As another method, there is a method of coextrusion in which a thermoplastic resin film is laminated on a sheet-shaped foam in a die, and in this case, a merging die (for example, a crosshead die) may be used. The resin may be flown in before the slit to perform lamination.

When used as a food container, in order to prolong the shelf life of the contents, a gas barrier resin film is attached to a foamed styrene resin sheet, and a gas barrier film is attached to a thermoplastic resin film in advance. Laminated sheets are used. Specific examples of the gas barrier resin film include ethylene / vinyl acetate copolymer, polyvinyl alcohol, polyvinylidene chloride, polyamide, polyester, polyacrylonitrile, vinylidene chloride / acrylonitrile copolymer, and acrylonitrile methyl methacrylate. -Butadiene copolymer, nylon 6, biaxially oriented nylon, biaxially oriented polyethylene terephthalate, biaxially oriented polypropylene.
Examples thereof include high-density polyethylene, ionomer resin (for example, Surlyn (registered trademark)), or metal vapor-deposited films, or a laminate of these films.

In the present invention, in the lamination of the foamed styrene resin sheet and the gas barrier resin film,
In addition to the co-extrusion method, the film may be heated and pressure-bonded with a hot roll from the side opposite to the bonding surface to be laminated. In this case, it is preferable that the surface of the roll to be heated and pressure-bonded is plated with chrome or coated with Teflon to prevent stickiness with the heated film. In the present invention, it is more preferable that the joint surface is also heated by the heating device together with the thermocompression bonding by the hot roll.

By laminating the above thermoplastic resin film, a thermoplastic resin laminated foamed sheet suitable for forming a deep drawing container having strength can be obtained. The thermoplastic resin film is
It is suitable to use the one having a thickness of 5 to 600 μm. If the thickness of the film is less than 5 μm, the elongation at the time of molding will be poor, and the mechanical strength of the molded product obtained will be low and unsuitable. On the other hand, if it exceeds 600 μm, when punching after molding, air bubbles in the lip portion are easily crushed and communication is caused, and a problem that the film and the foamed sheet are peeled off easily occurs, which is disadvantageous from the economical point of view. So not suitable. A more preferable thickness of the thermoplastic resin film is 30 to 500 μm. In some cases, thermoplastic resin films may be laminated on both sides.

As described above, the thermoplastic resin laminated foam sheet of the present invention has a blow-up ratio (BUR) which is a ratio of the plug diameter divided by the die slit diameter when extrusion foam molding is performed using a circular die. ) To 1.8-3.
5, the gap of the die slit is 0.25 to 1.2 mm, the extruder temperature is 150 to 265 ° C., and the temperature of the molten resin near the die exit is 145 to 185 ° C.
The extrusion rate varies depending on the extruder used, but in general,
It may be appropriately set at 75 to 400 kg / H depending on the extruder used. Furthermore, after extruding from a circular mold and foam-molding into an annular sheet shape, the inside and outside of the balloon are cooled by air. At this time, the cooling air amount is about 0.
04 to 0.3 m ³ / m ² , and the temperature is about 10 ° C to 80 ° C
It is preferable to perform the treatment within 5 seconds immediately after the extrusion.

In particular, the blow-up ratio is 2/5 of the expansion ratio.
It is preferable to adjust the extrusion amount, the take-up speed, and the cooling conditions so that the chrysanthemum pattern of the foam sheet disappears within 1/3 of the distance from the die slit to the plug by setting the interval between the third power and the third power.
It is important to reduce chrysanthemum patterns and make bubbles uniform. If the chrysanthemum pattern becomes remarkable, the cell structure and cell size of the chrysanthemum pattern will be different, and the chrysanthemum pattern will expand due to secondary foaming during molding. It becomes difficult to form a combined molded product.

Next, the bubbles of the foamed sheet of the present invention will be described. The cell structure ratio, which is the ratio of the cell size in the MD direction: the cell size in the TD direction: the cell size in the VD direction, inside the extruded and foamed polystyrene-based resin foam sheet excluding the skin layer, is generally MD: TD: VD = 0.
64: 1.49: 1.05 to 1.95: 0.87: 0.
59, but in the foamed sheet of the present invention, 0.72:
It should be in the range of 1.42: 0.98 to 1.54: 0.90: 0.72. When the cell structure ratio is less than 0.72 in the MD direction, during molding and heating, the cell expands in the MD direction and undulates, resulting in partial heating unevenness. In the present invention, it should be 0.72 or more. Cell structure ratio is T
When it is less than 0.90 in the D direction, during molding heating,
It expands in the TD direction and the chrysanthemum pattern becomes stronger. Therefore, uneven heating occurs partially. The cell structure ratio in the VD direction is determined by controlling the cell structure ratio in the MD direction and the TD direction. If the cell structure ratio exceeds 1.42 in the TD direction, or if the cell structure ratio in the TD direction exceeds 1.42 or the cell structure ratio in the MD direction exceeds 1.54, the elongation at molding is become worse.

A method of measuring the cell size will be described with reference to FIG. In the present invention, by controlling the cell structure ratio in the three-dimensional direction, the volume expansion of the foamed sheet can be accurately controlled in the molding machine, and a molded product with a good weight balance can be obtained. The cell size measuring method in each of the three-dimensional directions is based on ASTM-2842-67. That is, the cross section of the bubble sheet in the MD direction and the cross section in the TD direction are each magnified 20 times.
The length (L) was measured and calculated from the number of bubbles during that period. V
Number of bubbles in D (N _VD ): Count the number of bubbles in A, B, and C on the VD surface in the MD direction, the average is N _MD , and similarly, the TD direction is N _TD , Number of air bubbles in MD (N _MD ): The number of air bubbles in abc in the figure is counted with a length of 6 l, and the average is N _MD . Number of bubbles in TD (N _TD ): The number of bubbles in abc in the figure is counted with a length of 6 l and the average is taken as N _TD . The cell size of VD is calculated by t (average chord length of cell) = L (length of foam thickness 1 excluding 1/6 from both sides) /
Calculation of the cell size of N _VD MD is t (average bubble chord length) = 6 l /
To calculate the cell size of N _MD TD, t (average bubble chord length) = 6 l /
The N _TD bubble average diameter (d) is a numerical value obtained by dividing the chord length t in each direction of VD, TD, and MD by 0.616 (d = t /
0.616) Then, assuming that the cell size in the MD direction is d _MD , the cell size in the TD direction is d _TD , and the cell size in the VD direction is d _VD , the cell sizes in these three directions are multiplied to obtain a ratio of 1. Was defined as the cell structure ratio.

[0028]

[Equation 1]

The ratio of the cell size to the center of the surface layer of the foamed sheet is 0.
2 or more is preferable. Furthermore, 0.3 or more is suitable.
If this ratio is less than 0.2, elongation at the time of molding becomes poor and cracks occur. Further, when the density of the foamed sheet becomes small, the cells near the surface are connected by the heating of the heater at the time of molding, or the cells are shaken by the film heat at the time of lamination, and a good molded product cannot be obtained.

The method of measuring the cell size ratio is as follows. After removing the skin layer of the foamed sheet, the cross section in the thickness direction is photographed and divided into 6 equal parts in the thickness direction. The cell size of the surface layer is 1 / thickness from the both sides in the thickness direction.
6 is the bubble diameter in the MD and TD directions at the position of the central portion of 6.
The cell size in the center is 2/6, 3 /
These are the average bubble diameters in the MD and TD directions at the positions of the central portions of 6, 4/6, and 5/6. The cell size ratio of the surface layer portion to the center portion in the VD direction has little influence on the moldability, but the cell size ratio of the surface layer portion of the foamed sheet to the center portion is preferably 0.2 or more.

The shrinkage of the foamed styrene resin laminated sheet for thermoforming of the present invention must be -10% to 20%,
Further, it is preferable that the shrinkage rate is −5% to 15%. If the shrinkage rate is less than -10%, that is, if it expands over 10%, the sheet is wavy in that direction (expansion) when heated by the molding machine, uneven heating of the sheet, and multiple molding dies are individually clamped. However, vacuum leakage during molding and sheet misalignment may occur. Also, when the shrinkage ratio exceeds 20%, it is possible to mold a bowl, but when molding a molded product with a deep drawing ratio of 1.0 or more, even if the drawing ratio of the sheet is increased, the lip of the molded product is increased. Wrinkles and insufficient elongation occur near. Here, the pull-in rate is expressed as follows.

Next, a method of measuring the shrinkage ratio will be described. The foamed styrene-based resin laminated sheet for thermoforming is cut into 10 cm squares, which are covered with a wire mesh and heated in a gear oven at 125 to 150 ° C. on the wire mesh to stop the volume expansion of the 10 cm square sheet and reduce the volume of the sheet. The number of seconds at the start is read, and the number of seconds obtained by multiplying the number of seconds by 0.8 is set as the heating second (t). 10 cm
The diced sheet is heated on a wire net in a gear oven, for example, at 150 ° C. for t seconds to measure the dimensional change in the center of the sheet. Specifically, if MD is Mcm (M
cm is calculated from the average of contracted front and back sides) and is represented by the following formula. MD shrinkage (%) = {(10 cm-Mcm) / 10 c
m} × 100 TD shrinkage (%) = {(10 cm-Tcm) / 10 c
m} × 100

The shrinkage is adjusted by stretching the surface layer (1/6 of the total thickness on one side and 1/3 on both sides) of the foamed sheet and the film. The shrinkage of the surface layer is adjusted mainly by the temperature of the air roll, the heat roll, the heating roll and the tension applied to the foamed sheet. Adjust the shrinkage of the film, slit,
This is done by changing the resin temperature and tension. The cell structure is mainly determined by the composition, slits, and BUR, but the surface layer is a separate control because it has a great influence after extrusion as described above.

The amount of residual foaming agent in the foamed sheet of the present invention is
It should be 0.01 to 0.3 mol / kg. 0.3
If the amount exceeds mol / kg, the inside of the bubbles will be decompressed due to the escape of the foaming agent and the cooling of the sheet after extrusion foaming even if air inflow occurs, and it will take a long time to replace the foaming agent with air, and the aging will take a long time. Is required. If the amount is 0.3 mol / kg or less, the amount of the foaming agent in the bubbles does not move largely and the amount of the foaming agent escaped is very small even if air flows into the bubbles. Therefore, the inside of the bubble is not large and the pressure is not reduced, and the subsequent moldability is good.
If it is less than 0.01 mol / kg, the secondary foaming force of the sheet at the time of molding is small, and the physical properties (formation, strength) of the molded product vary depending on the position of the molding die.

The amount of residual foaming agent in the molded product after molding is preferably 0.26 mol / kg or less. Molding varies depending on the molding time and temperature, but in general, molding is often performed after the foaming is completed in the molding machine, and physical properties are deteriorated even with the same sheet (molded product is soft and strength is weak). Therefore, in the product of the present invention, the sheet is put into a mold and molded before the completion of foaming, that is, at the time of foaming. At this time, in order to obtain a molded product having good physical properties in a form in which air bubbles are expanded as much as possible, it is necessary to perform molding without allowing the foaming agent to escape from the inside of the molded product. However, when a sheet having a density of 0.3 g / cm ³ or more is formed, some physical properties can be secured without forming a residual gas in the formed product.

Inorganic foaming agents such as N ₂ , CO ₂ and air, decomposable foaming agents such as azodicarbonamide, heavy soot,
When using a foaming agent that decomposes to generate inorganic gas, such as an organic foaming agent such as citric acid, sodium citrate, or citric acid ester, a density of less than 0.3 g / cm ³ is used in combination with a volatile foaming agent. It is necessary to do so to secure the physical properties for the above reasons. On the contrary, if the residual gas in the molded product exceeds 0.26 mol / kg, the molded product may be soft and may be deformed, which is not good in physical properties. Further, the higher the density of the foamed sheet, the shorter the time required for extrusion to molding, but the density of 0.
Even at 77 g / cm ³ , 15 seconds or more is required for cooling and stabilization.

The amount of the residual foaming agent was measured by wrapping the test piece in an aluminum foil, heating it in a gear oven at 150 ° C. for 1 hour, cooling it in a desiccator for about 30 minutes, and then measuring the weight (g) of each. The amount of residual foaming agent was expressed by the formula shown below. However, the identification of the foaming agent and the ratio of the types were performed by gas chromatography.

[0038]

【Example】

Example 1. A foam molded article was manufactured using the apparatus shown in FIG. Impact-resistant polystyrene containing 95% by weight of polystyrene resin (manufactured by Sekisui Plastics Co., Ltd., trade name: MS620) and 6% by weight of styrene-butadiene copolymer (trade name: DENKA HIE-4, manufactured by Denki Kagaku Co., Ltd.). ) 1.2 parts by weight of talc and 0.1 parts by weight of liquid paraffin were added to 100 parts by weight of the mixed resin with 5% by weight, and these were uniformly mixed with a mixer to obtain a mixture. Extruder (2) with these mixtures having a screw with a diameter of 115 mm
Continuously supplied from the hopper (1) of
Melt kneading into a molten resin in an extruder heated to ℃, and from the foaming agent supply device (3) to the foaming agent supply pipe (4)
Through a blowing agent consisting of a mixture ratio of n-butane and i-butane of 65% to 35% (n-butane / i-butane = 65/35) at a rate of 0.28 mol per 1 kg of the mixture. Pressure, mix with the molten resin, cool the mixture to a proper foaming temperature, and use a die (circular die) (5) with a slit of 0.35 mm provided at the tip of the extruder to measure the die temperature. Extrusion was carried out at 115 ° C. with a discharge rate of about 125 kg (125 kg / Hr) per hour.

On the foaming foam extruded from the die, the outside air device (6) and the inside air device (7) were set to a temperature of 35 ° ± 3 ° C. The foam was biaxially stretched and cooled while blowing Table 1), and the foam was passed through a cooling plug (8) to bring the surface temperature of the foam to about 84 ° C. In the method of the present invention, it is necessary to complete the foaming at least by the time when the cooling plug (8) has passed. This is to prevent variations in the content of the color former in the foam.

Then, it was spread on a foamed sheet with a cutter knife (9). The width of this expanded foam sheet is 104
It was 5 mm. The expanded foam sheet is heated to about 65 ° C.
The temperature is controlled by a Nidax processing roll (10a, 10b) with a circumference of 1000 mm, and the take-up speed is about 16 m / min. The diameter is 2 between the rolls (11a, 11b).
While adjusting the feed with the 00 mm step hole (12),
A 25 μm stretched polystyrene sheet (hereinafter referred to as “O”) printed using a Nidax processed roll (16) (this roll also serves as a heating roll and a delivery roll).
It is called PS. ) Was passed through while heat-sealing (roll heat lamination). The surface temperature of the foamed sheet after passing was about 47 ° C.

Further, a part of the foamed sheet after passing was sampled, and the thickness, density, residual foaming agent amount, and shrinkage ratio were determined. The thickness was 0.75 mm and the density was 0.16 g / c.
m ³ , the residual foaming agent amount was 0.18 mol / kg, and the shrinkage ratio was 10% in the MD direction and 7% in the TD direction. The cell structure ratio in each direction of MD, TD and VD inside the foam sheet is MD: T
It was D: VD = 1.12: 1.22: 0.73. Further, the cell size ratio (surface layer portion / center portion) between the surface layer portion and the center portion of the foamed sheet was 0.64 in the MD direction and 0.6 in the TD direction. This foam sheet is heated in a furnace (17)
While pulling on the feed chain (18),
I sent it to 0). The heating furnace (17) has a pair of upper and lower 39
Far-infrared heater (19a, 1a set to a temperature of 5 ° C)
9b) is provided, and the foam sheet has a surface temperature of 105.
It was heated above ℃ and increased in volume.

The foamed sheet sent to the molding machine (20) is attached to the molding machine (20) and has a width of 1 shown in FIGS.
A tray-shaped product having a size of 03 mm, a length of 195 mm, and a depth of 21 mm was molded by a molding die (22a, 22b) having a width of 1000 mm and a length of 600 mm having a 9 × 3 array. The feed length was 645 mm per shot. Further, at the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 2.4 seconds. During molding, the foamed sheet is a Nidax processed roll (16)
Between the heating furnace (17) and the heating furnace (17), at least one shot slack (26) was provided. After molding, the cutter (2
By 3), each shot was cut, and at the same time, 27 trays shown in FIGS. 3 to 8 were obtained by molding once. Twenty-seven trays were collected on the moving conveyor (25).

The size of the obtained tray is the same as that of the mold (22
The width was 103 mm, the length was 195 mm, and the depth was 21 mm. The alignment of the printed part was also good. The residual foaming agent content of the obtained tray was 0.
It was 06 mol / kg. The detailed specifications of the obtained tray other than the above are as follows.

Example 2. A foam molded article was manufactured using an apparatus as shown in FIG. 2.6 parts by weight of talc and hydrocerol CF are added to 100 parts by weight of high-impact polystyrene containing 6% by weight of styrene-butadiene copolymer (trade name: Denka HlE-4 manufactured by Denki Kagaku KK).
0.3 parts by weight of liquid paraffin and 0.1 parts by weight of liquid paraffin were added, and these were uniformly mixed with a mixer to obtain a mixture.
These mixtures are continuously fed from a hopper (1) of an extruder (2) having a screw having a diameter of 115 mm,
In the extruder heated to the maximum temperature of 235 ° C., the mixture is melt-kneaded to form a molten resin, and the foaming agent i-butane is passed from the foaming agent supply device (3) through the foaming agent supply pipe (4) to 0 per 1 kg of the mixture. Continuously press-fitted at a rate of 29 mol, mixed with the molten resin, cooled these mixtures to a proper foaming temperature, and provided a cylindrical die (circular die) with a slit of 0.39 mm provided at the tip of the extruder. (5)
From a die temperature of 122 ° C, the discharge rate per hour is about 8
It was extruded at 7 kg (87 kg / Hr).

On the foaming foam extruded from the die, the air (air-volume table 1) set by the outer air device (6) and the inner air device (7) to a temperature of 35 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the foam to 85 ° C. The foaming was completed at least by the time when the cooling plug (8) passed. This is to prevent variations in the content of the foaming agent in the foam.

Next, the foamed sheet was developed with a cutter knife (9). The width of this expanded foam sheet is 104
It was 5 mm. The expanded foam sheet is heated to about 70 ° C.
With a temperature-controlled two-duck processing roll (10a, 10b) with a circumference of 1000 mm, the take-up speed was taken at about 3.5 m / min, and a step roll with a diameter of 200 mm was provided between the rolls (11a, 11b). While adjusting the feed with the roll (12), print a 25 μm OPS printed over the entire surface using a Nidax processed roll (16) (this roll also serves as a heating roll and a delivery roll). The surface was turned to the side of the foamed sheet and was passed through while being heat-fused. The surface temperature of the foamed sheet after passing was about 48 ° C.

A portion of the foamed sheet after passing was sampled and the thickness, density, residual foaming agent amount, and shrinkage were measured, and the thickness was 1.9 mm and the density was 0.21 g / cm.
³ , residual foaming agent amount is 0.19 mol / kg, shrinkage is MD
The direction was 12% and the TD direction was 2%. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD:
TD: VD = 1.18: 1.05: 0.81.
Further, the cell size ratio (surface layer portion / central portion) of the surface layer portion and the center portion of the foamed sheet was 0.81 in the MD direction and 0.73 in the TD direction. This foamed sheet is heated in a heating furnace (1
7) was fed into the molding machine (20) while being pulled by the feed chain (18). The heating furnace (17) has a pair of upper and lower far infrared heaters (19) set at a temperature of 340 ° C.
a, 19b) are provided, the foamed sheet is heated to a surface temperature of 105 ° C. or higher and its volume is increased.

The foamed sheet sent to the molding machine (20) was attached to the molding machine (20) and had a diameter of 10 shown in FIG.
A cup with a size of 6 mm, a depth of 106 mm, and a taper angle of 7 degrees is 4 × in a size of width 600 mm × length 600 mm.
16 pieces of one shot were formed at one time by the forming dies (22a, 22b) arranged in four pieces, and cut in the same manner as in Example 1 to collect the cups. The feed length to the molding machine was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 11 seconds. During molding, the foam sheet is rolled (1
A slack (26) of at least one shot was provided between the heating furnace (17) and 6). Cup (51)
The size was 106 mm, the depth was 106 mm, and the taper angle was 7 degrees. In addition, it was a molded product with little printing position deviation. The amount of residual foaming agent in the cup (51) is
It was 0.12 mol / kg. The state of the cup (51) was good in elongation, thickness was almost uniform, and cracks were not generated.

Example 3. A foam molded article was manufactured using an apparatus as shown in FIG. 90% by weight of a styrene-acrylic acid copolymer (Asahi Kasei Co., Ltd., trade name: G9001) which is a heat-resistant styrene resin, and a styrene-saturated thermoplastic elastomer (Asahi Kasei Co., Ltd.)
Made, trade name: Tuftec) 10 wt% mixed resin 10
0.4 parts by weight of talc and 7 parts of polystyrene for 0 parts by weight
5% by weight of talc and 23% by weight of talc and 2% by weight of magnesium stearate were added at a ratio of 3.0 parts by weight of masterbatch and 0.1 parts by weight of liquid paraffin, and these were uniformly mixed with a mixer to obtain a mixture. did. Extruder (2) with these mixtures having a screw with a diameter of 115 mm
Continuously supplied from the hopper (1) of the
Melt kneading into a molten resin in an extruder heated to ℃, and from the foaming agent supply device (3) to the foaming agent supply pipe (4)
The blowing agent i-butane is continuously introduced under pressure at a rate of 0.45 mol per 1 kg of the mixture, mixed with the molten resin, and the mixture is cooled to a proper foaming temperature and provided at the tip of the extruder. From the cylindrical die (circular die) (5) with a slit of 0.65 mm, the die temperature 1
At 40 ° C, the discharge rate per hour is about 78 kg (78 kg
/ Hr).

On the foaming body extruded from the die, the air (air-volume table 1) set by the outer air device (6) and the inner air device (7) at a temperature of 40 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the foam to 99 ° C. In the method of the present invention, it is necessary to complete the foaming at least by the time when the cooling plug (8) has passed. This is to prevent variations in the content of the foaming agent in the foam.

Next, the foamed sheet was developed with a cutter knife (9). The width of this expanded foam sheet is 104
It was 5 mm. The expanded foam sheet is heated to about 90 ° C.
A two-duck processing roll (10a, 10b) having a temperature of 1000 mm and a circumference of 1000 mm was taken at a take-up speed of about 5.3 m / min, and a step roll (12) having a diameter of 200 mm provided between the rolls (11a, 11b) While adjusting the feed with, a Nidax processed roll (16) (which also serves as a heating roll and a delivery roll) is used, and 30 μm CPP / 4 μm adhesive (urethane type) / 30 μm HIPS is used. The multilayer film of No. 1 was passed through while being heat-sealed. The surface temperature of the foamed sheet after passing was about 60 ° C.

A part of the foamed sheet after passing was sampled, and the thickness, density, residual foaming agent amount, and shrinkage ratio were measured. The thickness was 1.8 mm and the density was 0.13 g / cm.
³ , residual foaming agent amount is 0.28 mol / kg, shrinkage is MD
The direction was 19% and the TD direction was -6%. The cell structure ratio in the MD, TD and VD directions inside the foam sheet is M
It was D: TD: VD = 1.49: 0.91: 0.74. Further, the cell size ratio (surface layer portion / center portion) between the surface layer portion and the center portion of the foamed sheet is 0.41 in the MD direction, and TD
It was 0.38 in the direction. This foamed sheet was fed into the heating furnace (17) while being pulled by the feed chain (18) into the molding machine (20). In the heating furnace (17), a pair of upper and lower far infrared heaters (1
9a, 19b), and the foamed sheet was heated to a surface temperature of 124 ° C. or higher and increased in volume.

The foamed sheet sent to the molding machine (20) was placed in the molding machine (20), and a lunch box having a width of 175 mm, a length of 225 mm, and a depth of 27 mm was placed in a 700 mm width.
Nine pieces of one shot were molded at once by the molding dies (22a, 22b) arranged in a size of 600 mm in length of 3 × 3, and the lunch box was collected in the same manner as in Example 2 below. The feed length to the molding machine was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 7.3 seconds. During molding,
Foamed sheet is sent out by roll (30) and heating furnace (17)
Slack of at least one shot between and (26)
Need to be provided. The size of the lunch box is 175 width
mm, the length was 225 mm, and the depth was 27 mm. The amount of residual foaming agent in the lunch box was 0.23 mol / kg. In addition, the state of the lunch box has good elongation, thickness is almost uniform,
It did not cause cracks. The above results are shown in Table 1.

[0054]

[Table 1]

Example 4. Foam molded articles were manufactured using a three-layer laminating apparatus. Polystyrene (Electrochemical Co., Ltd.)
Made, brand name: Denkastyrol HRM-2) 40% by weight
And (made by GE Plastics Trade name: Noryl (PPO34
%)), 50% by weight, styrene saturated thermoplastic elastomer (trade name: Tuftec, manufactured by Asahi Kasei Co., Ltd.)
1.1 parts by weight of talc, 0.2 parts by weight of Hydrocerol CF (sold by Nissei Chemical Co., Ltd.), and 0.1 parts by weight of liquid paraffin were added to 100 parts by weight of the mixed resin with 10% by weight, These were uniformly mixed with a mixer to obtain a mixture. These mixtures are continuously supplied from a hopper (1) of an extruder (2) having a screw with a diameter of 115 mm, melt-kneaded in an extruder heated to a maximum temperature of 270 ° C. to obtain a molten resin, and foaming is performed. A foaming agent comprising a mixture ratio of i-butane and i-pentane of 75% to 25% (i-butane / i-pentane = 75/25) from the agent supply device (3) through the foaming agent supply pipe (4). The above mixture 1k
It is continuously pressed at a ratio of 0.20 mol per g, mixed with the molten resin, and cooled to a proper foaming temperature of the mixture, and a cylindrical die (circular die) (5) provided at the tip of the extruder (5) ), A flat die (coat hanger die) with a slit of 0.45 mm is used, and the die temperature is 135 ° C. and the discharge amount per hour is about 85 kg (85
Kg / Hr) was extruded.

On the foaming body extruded from the die, which is being foamed, an upper air unit and a lower air unit (not shown) are blown with an air-air set at a temperature of 35 ° ± 3 ° -amount table 2). At the same time, the foam was uniaxially stretched and cooled while being lightly pressure-bonded to a cooling roll, and cooled, and passed through the cooling roll to bring the surface temperature of the foam to about 81 ° C. In this example, it is necessary to complete the foaming at least by the time of passing through the cooling roll. This is to prevent variations in the content of the foaming agent in the foam.

This foamed sheet was adjusted to a temperature of about 102.degree.
At 0b), both ears of the foamed sheet were slit while the take-up speed was about 5.3 m / min. The width of this foamed sheet was 1040 mm. Then, it is passed between a roll (14) and a roll (13) each having a diameter of 200 mm and formed with an uneven shape. By using the roll having the uneven shape formed as described above, the remaining foaming agent in the foamed sheet can be significantly reduced, and the influence of uneven thickness of the foamed sheet during molding can be reduced. When wound into a roll, it is possible to impart a function such that the foaming agent comes off quickly and the aging time of the foamed sheet can be shortened. On this roll (14), ridges having a width of 10 mm and a height of 2 mm are evenly arranged at 15 mm intervals in the axial direction. The surface temperature of the foamed sheet after passing was about 53 ° C. When the foamed sheet passed through the roll (13) and the roll (14), a pressure of ² kg / cm ² was applied by an air cylinder.

A 30 μm crystalline polyethylene terephthalate resin film (urethane type adhesive + PET film =) in which a urethane type adhesive is coated on this foamed sheet while extruding a HIPS film (65 μm) with an extruder
30 μm) was laminated (extrusion laminating). A part of the foamed sheet was sampled and the thickness, density, residual foaming agent amount, and shrinkage were measured, and the thickness was 0.8 mm and the density was 0.32.
g / cm ³ , residual foaming agent amount was 0.08 mol / kg, shrinkage was 18% in MD direction and -9% in TD direction. Also,
The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD: VD = 1.50: 0.91: 0.73.
Met. Further, the cell size ratio of the surface layer portion and the center portion of the foamed sheet (surface layer portion / center portion) is 0.4 in the MD direction.
4 and 0.23 in the TD direction. This foamed sheet was fed into the heating furnace (17) while being pulled by the feed chain (18) into the molding machine (20). The heating furnace (17) is provided with a pair of upper and lower far infrared heaters (19a, 19b) set at a temperature of 430 ° C., and the foamed sheet is heated to a surface temperature of about 122 ° C. or more and its volume increases. did.

The foamed sheet sent to the molding machine (20) has a width 1 shown in FIGS.
A tray-shaped product having a size of 03 mm, a length of 195 mm, and a depth of 21 mm was molded by a molding die (22a, 22b) having a width of 1000 mm and a length of 600 mm having a 9 × 3 array. The feed length was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 7.3 seconds. During molding,
The foamed sheet needs to have at least one shot slack (26) between the Nidax processed roll (16) and the heating furnace (17). After the molding, a cutter (23) was used to cut each shot, and at the same time, 27 trays were obtained by one molding. Twenty-seven trays were collected on the moving conveyor (25). The size of the tray is the same as the mold (22b), width 103 mm, length 19
It was 5 mm and the depth was 21 mm. The residual foaming agent amount in the tray was 0.03 mol / kg.

Example 5. Polystyrene (Electrochemical Co., Ltd.)
Made, brand name: Denkastyrol HRM-2) 70% by weight, homopolypropylene (manufactured by Highmont, PF81)
4) 25% by weight and styrene-butadiene elastomer 6
0.2 parts by weight of talc and 0.3 parts by weight of hydrocerol CF based on 100 parts by weight of a mixed resin with 5% by weight of a polybutadiene block aggregate containing 0% (trade name: Tafprene manufactured by Asahi Kasei Co., Ltd.) , Calcium laurate 0.
Add 2 parts by weight and 0.1 parts by weight of liquid paraffin,
These were uniformly mixed with a mixer to obtain a mixture. These mixtures are continuously supplied from a hopper (1) of an extruder (2) having a screw having a diameter of 115 mm shown in FIG. 2 and melt-kneaded in the extruder heated to a maximum temperature of 220 ° C. to form a molten resin. In addition, the mixing ratio of n-butane and i-butane was 60% to 40% (n-butane and i-butane = 60/40) from the foaming agent supply device (3) through the foaming agent supply pipe (4). 1 kg of the above mixture,
0.35 mol of CO ₂ and 0.12 mol of CO ₂ are continuously injected under pressure, mixed with the molten resin, and the mixture is cooled to a proper foaming temperature. The circular gold is provided at the tip of the extruder. Slit 0.41 in place of mold (5)
mm flat die (coat hanger die) at a die temperature of 119 ° C., discharge rate of about 89 kg (8
It was extruded at 9 kg / Hr).

On the foaming foam extruded from the die, air set at a temperature of 35 ° ± 3 ° by an upper air device and a lower air device (not shown) (air amount table 2). While being blown, the foam was uniaxially stretched and cooled while being lightly pressure-bonded to a cooling roll, passed through the cooling roll, and the surface temperature of the foam was adjusted to about 82 ° C. In this example, it is necessary to complete the foaming at least by the time of passing through the cooling roll. This is to prevent variations in the content of the foaming agent in the foam. This foamed sheet was adjusted to a temperature of about 55 ° C with a circumference of 100.
With 0 mm Ni-Dax processing rolls (10a, 10b),
The take-up speed was about 5.3 m / min. Then, it is passed between a roll (14) and a roll (13) each having a diameter of 200 mm and formed with an uneven shape. The surface temperature of the foamed sheet after passing was about 44 ° C. This roll (14) has a ridge 15 mm wide and 10 mm wide in the axial direction.
They are evenly spaced. Foam sheet roll (1
When passing through 3) and the roll (14), a pressure of ² kg / cm ² was applied with an air cylinder.

On the other hand, the same impact-resistant polystyrene as in Example 1 was added to dimethylpolysiloxane (trade name: 98.9% by weight).
The mixed resin containing 1.1% by weight of silicone was melt-kneaded in an extruder (27) having a screw diameter of 65 mm, and then a T-die (28) attached to the tip of the extruder (27). It was extruded into a film. This film was joined with the foamed sheet with a temperature control roll (29) to have a film thickness of 265 μm and laminated with the foamed sheet to obtain a laminated sheet.

A part of the foamed sheet after passing was sampled, and the thickness, density, residual foaming agent amount, and shrinkage were measured, and the thickness was 1.5 mm and the density was 0.14 g / cm.
³ , residual foaming agent amount is 0.21 mol / kg, shrinkage is MD
The direction was 5% and the TD direction was -1%. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD:
It was TD: VD = 1.16: 1.02: 0.85.
Further, the cell size ratio of the surface layer portion and the center portion of the foamed sheet (surface layer portion / center portion) was 0.83 in the MD direction and 0.71 in the TD direction.

This laminated sheet was sent into the heating furnace (17). The laminated sheet sent into the heating furnace (17) was heated to a surface temperature of 110 ° C. or higher by a far infrared heater (19) whose temperature was set to about 390 ° C. The heated laminated sheet is a molding die (22a, in which a cup having a diameter of 106 mm, a depth of 106 mm and a taper angle of 7 degrees shown in FIG. 9 is arranged in 4 × 4 pieces in a size of width 600 mm × length 600 mm. According to 22b), 16 pieces of one shot were molded at one time, and the cup was collected in the same manner as in Example 2 below. The feed length to the molding machine was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle is
It was 5.7 seconds. During the forming, the laminate sheet needs to have at least one shot of slack (26) between the delivery roll (30) and the heating furnace (17). The size of the cup is 106 mm in diameter and 106 in depth.
The taper angle was 7 mm and the taper angle was 7 degrees. The residual foaming agent amount in the cup was 0.09 mol / kg. The state of the cup is
Good elongation, uniform thickness, very fine bubbles,
It did not cause cracks. When curved surface printing was performed on the surface of the cup, clear printing was possible.

Example 6. Polystyrene resin (trade name: Denkastyrol HRM-5, manufactured by Denki Kagaku Co., Ltd.) 75
Polybutadiene block agglomerates containing 50% by weight and 60% styrene-butadiene elastomer (manufactured by Asahi Kasei Corporation)
(Trade name: Tafprene) 25 parts by weight of a mixed resin with 25 parts by weight of polystyrene, 75 parts by weight of polystyrene, 25 parts by weight of talc, 20 parts by weight of a kneaded masterbatch, and 0.6 parts by weight of talc. Was evenly mixed with a mixer to obtain a mixture. These mixtures are continuously supplied from a hopper (1) of an extruder (2) having a screw having a diameter of 115 mm shown in FIG. 2 and melt-kneaded in the extruder heated to a maximum temperature of 250 ° C. to obtain a molten resin. In addition, the mixing ratio of n-butane and i-butane was 70% to 30 from the foaming agent supply device (3) through the foaming agent supply pipe (4).
% (N-butane / i-butane = 70/30) at a rate of 0.46 mol per 1 kg of the mixture, and the mixture was mixed with the molten resin to form a mixture. Cool to the proper foaming temperature, and use a cylindrical die (circular die) (5) with a slit of 0.61 mm provided at the tip of the extruder to discharge the die at a temperature of 122 ° C and discharge about 121 kg (121 kg / Hr) per hour. Extruded.

On the foaming foam extruded from the die, the air (air-volume table 2) set by the outer air device (6) and the inner air device (7) to a temperature of 35 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the foam to about 84 ° C.

Then, it was developed into a foamed sheet with a cutter knife (9). The width of this expanded foam sheet is 10
It was 45 mm. This expanded foam sheet is about 62
It was taken up at a take-up speed of about 6.5 m / min with a Ni-Dax processing roll (10a, 10b) having a temperature of 1000 ° C. and a circumference of 1000 mm. After that, the uneven shape is formed with a diameter of 200 m
m rolls (14) and (13). On this roll (14), ridges having a width of 10 mm and a height of 2 mm are evenly arranged at 15 mm intervals in the axial direction. The surface temperature of the foamed sheet after passing was about 51 ° C.

The foamed sheet was rolled (13) and rolled (1
4) 2kg / c with an air cylinder when passing through
A pressure of m ² was applied. On the other hand, a mixed resin obtained by containing 1.1% by weight of dimethylpolysiloxane (trade name: silicone) in 98.9% by weight of the same impact-resistant polystyrene as in Example 1 was used in an extruder (2 having a screw diameter of 65 mm.
After melt-kneading in 7), it was extruded into a film form from a T die (28) attached to the tip of the extruder (27). This film was joined with the foamed sheet with a temperature control roll (29) to make the film thickness 245 μm and laminated with the foamed sheet to obtain a laminated sheet. The shrinkage ratio after laminating was 8% in the MD direction and -4% in the TD direction.

A portion of the foamed sheet was sampled and the thickness, density, residual foaming agent amount, and shrinkage were measured. The thickness was 2.1 mm, the density was 0.145 g / cm ³ , and the residual foaming agent amount was 0. 23 mol / kg, shrinkage is 16 in MD
%, -1% in the TD direction. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD:
VD = 1.11: 1.18: 0.76. The cell size ratio of the surface layer portion and the center portion of the foamed sheet after lamination (surface layer portion / center portion) is 0.73 in the MD direction, TD
It was 0.67 in the direction.

This laminated sheet was sent into the heating furnace (17). The laminate sheet sent to the heating furnace (17) was heated to a surface temperature of 105 ° C. or higher by the far infrared heater (19) whose temperature was set to about 410 ° C. The heated laminated sheet is a molding die (22a, in which cups having a diameter of 106 mm, a depth of 106 mm, and a taper angle of 7 degrees shown in FIG. 9 are arranged in 4 × 4 pieces in a size of width 600 mm × length 600 mm. According to 22b), 16 pieces of one shot were molded at one time, and the cup was collected in the same manner as in Example 1 below. The feed length to the molding machine was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle is
It was 6.0 seconds. During the forming, the laminate sheet needs to have at least one shot of slack (26) between the delivery roll (30) and the heating furnace (17). The size of the cup is 106 mm in diameter and 106 in depth.
The taper angle was 7 mm and the taper angle was 7 degrees. The residual foaming agent amount in the cup was 0.10 mol / kg. The state of the cup is
The elongation was good, the thickness was almost uniform, and cracks did not occur. When curved surface printing was performed on the surface of the cup, clear printing was possible. The above results are shown in Table 2.

[0071]

[Table 2]

Example 7. A molded product was manufactured using the same apparatus as shown in FIG. Screw diameter 115m
Externally-used waste collection product (tray container) 100 for m extruder
%, 0.2 parts by weight of powdered talc was added to 8.0 parts by weight of talc masterbatch (talc MB) (20% talc was kneaded into PS resin), and the mixture was charged from a hopper. About 225
NC ₄ / iC ₄ = 3 as a foaming agent while being heated to ℃
It was melted and kneaded by press-fitting it at a ratio of 0.03 mol / kg at 5/65. The melt was brought to a proper foaming temperature, a die temperature of 132 ° C. and a discharge rate of 7 from a circular die (slit 0.35 mm) provided at the tip of the extruder.
It was extruded and foamed at 5 kg / H.

While extending the obtained cylindrical foam biaxially, the inner air amount was 0.08 m ³ / m ² from the inside and outside of the balloon.
Nidax processing roll with a diameter of about 320 mm, which was cooled with an outside air amount of 0.07 m ³ / m ² , cooled through a plug and cooled to 85 ° C.
It is taken out with l and then 2 with a width of 10 mm and a height of 2 mm.
The ridges extending over the entire length in the axial direction of the roller having a diameter of 00 mm were arranged at intervals of about 15 mm in the circumferential direction of the roll. A pressure of 2.2 kg / cm ² was applied to the foamed sheet between the irregularity forming rolls.
Then, the pressure of the air cylinder was applied to push it out. At this time, the temperature of the sheet after passing through the unevenness forming roll was 30 ° C.

This foamed sheet was filled with Hl having a thickness of about 285 μm.
The PS film was extrusion-laminated from the extruder using a T-die.
The shrinkage ratio after laminating was MD5% and TD1%, the residual foaming agent amount of the foamed sheet was 0.02 mol / kg, the density was 0.46 g / cm ³ , and the thickness was 0.62 mm. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD: ∨D = 1.10: 1.08: 0.
It was 84. Further, the cell size ratio (surface layer portion / central portion) of the surface layer portion and the center portion of the foamed sheet was 0.95 in the MD direction and 0.91 in the TD direction. The laminated sheet is sent to a far infrared heater heating chamber at about 380 ° C by a chain and heated to a sheet surface temperature of 112 ° C or higher, and a 15 ton press presses the caliber 106 mm and the depth 106 m.
m, taper 7 ° C cup effective width 600mmX600
In 16 mm, it was possible to obtain a good formed product having a good appearance by taking 16 pieces.
The residual foaming agent amount in the cup was 0.012 mol / kg.

Example 8. Resin (MI = 4.7) 10 for collecting externally used PSP tray containers and pelletizing them
75 parts by weight of polystyrene and 2 parts of talc to 0 parts by weight
Masterbatch containing 5% by weight (talc MB) 1
0 parts by weight and 2.5 parts by weight of talc were added, and these were uniformly mixed with a mixer to obtain a mixture. These mixtures are continuously supplied from a hopper (1) of an extruder (2) having a screw with a diameter of 115 mm shown in FIG. In addition, the mixture ratio of n-butane and i-butane 35% to 65% (n-butane / i-butane = 35 / from the foaming agent supply device (3) through the foaming agent supply pipe (4).
65) and a foaming agent consisting of 0.03 mol per 1 kg of the mixture are continuously injected, mixed with the molten resin, and the mixture is cooled to a proper foaming temperature.
From the cylindrical die (circular die) (5) with a slit of 0.35 mm provided at the tip of the extruder, a die temperature of 132
Discharge rate per hour at 75 ℃ (75kg / H
Extruded in r).

On the foaming body extruded from the die, the air (air-volume table 3) set by the outer air device (6) and the inner air device (7) at a temperature of 35 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the foam to about 85 ° C.

Then, it was developed into a foamed sheet with a cutter knife (9). The width of this expanded foam sheet is 10
It was 45 mm. About 32 of this expanded foam sheet
A two-duck processing roll (10a, 10b) having a temperature of 1000 ° C. and a circumference of 1000 mm was used, and the take-up speed was about 4.2 m / min. After that, the uneven shape is formed with a diameter of 200 m
m rolls (14) and (13). The surface temperature of the foamed sheet after passing was about 30 ° C. On this roll (14), ridges having a width of 10 mm and a height of 2 mm are evenly arranged at 15 mm intervals in the axial direction. When the foamed sheet passes through the roll (13) and the roll (14), it is 2.2 kg / cm ² with an air cylinder.
Was put under pressure. MD / TD / V inside the foam sheet
The cell structure ratio in each D direction is MD: TD: VD = 1.0.
It was 0: 1.03: 0.97.

On the other hand, the same impact-resistant polystyrene as in Example 1 was added to dimethylpolysiloxane (trade name: 98.9% by weight).
The mixed resin containing 1.1% by weight of silicone was melt-kneaded in an extruder (27) having a screw diameter of 65 mm, and then a T-die (28) attached to the tip of the extruder (27). It was extruded into a film. This film was joined with the foam sheet with a temperature control roll (29) to have a film thickness of 285 μm and laminated with the foam sheet to obtain a laminated sheet. Shrinkage after laminating is M
It was 5% in the D direction and 1% in the TD direction.

A part of the foamed sheet was sampled, and the thickness, density, residual foaming agent amount, and shrinkage ratio were measured. The thickness was 0.61 mm, the density was 0.46 g / cm ³ , and the residual foaming agent amount was 0. It was 02 mol / kg. MD: TD: VD = 1.04: 0.99 inside the foamed sheets after lamination:
It was 0.97. Further, the cell size ratio (surface layer portion / central portion) between the surface layer portion and the center portion of the foamed sheet was 0.74 in the MD direction and 0.68 in the TD direction. This laminated sheet was sent into a heating furnace (17). The laminated sheet sent to the heating furnace (17) is about 380
By far infrared heater (19) with temperature set at ℃,
The surface temperature was heated to a temperature of 112 ° C. or higher.

The heated laminated sheet is a molding die in which cups having a diameter of 106 mm, a depth of 106 mm and a taper angle of 7 degrees shown in FIG. 9 are arranged in 4 × 4 pieces in a size of width 600 mm × length 600 mm. Sixteen (16) shots were molded at once with (22a, 22b), and the cups were collected in the same manner as in Example 1 below. The feed length to the molding machine was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 9.1 seconds. During the forming, the laminate sheet needs to have at least one shot of slack (26) between the delivery roll (30) and the heating furnace (17). The size of the cup is 106mm, 1 depth
The taper angle was 06 mm and the taper angle was 7 degrees. The amount of residual foaming agent in the cup was 0.01 mol / kg. The cup was in a state of good elongation, a uniform thickness, and no cracks. When curved surface printing was performed on the surface of the cup, clear printing was possible.

Further, the resin used for collecting and pelletizing the externally used Zumi PSP tray container has a width 103 shown in FIGS.
A tray-shaped product having a size of mm, a length of 195 mm, and a depth of 21 mm was molded, but could be molded without problems. When sandwiching the foamed sheet of recovered pellets with virgin material, PS
P (GP) / Recovered PSP / PSP (GP), Film
(GP) / Recovered PSP / Film (GP), Film
(GP) / recovered PSP / PSP (GP) was performed, but molding could be performed without problems.

Example 9. A foam molded article was manufactured using an apparatus as shown in FIG. Impact-resistant polystyrene (trade name: Denka HIE-4) manufactured by Denki Styrol HRM-2 90% by weight and styrene-butadiene copolymer 6% by weight 10
For 100 parts by weight of mixed resin with 100% by weight, talc is 0.6
Parts by weight, hydrocerol CF (trade name of Dainichi Seika)
0.3 parts by weight of liquid paraffin and 0.1 parts by weight of liquid paraffin were added, and these were uniformly mixed with a mixer to obtain a mixture.
These mixtures were continuously fed from a hopper (1) of an extruder (2) having a screw with a diameter of 115 mm,
In the extruder heated to a maximum temperature of 220 ° C., the mixture is melt-kneaded to form a molten resin, and the foaming agent i-butane is passed from the foaming agent supply device (3) through the foaming agent supply pipe (4) to 0 per 1 kg of the mixture. The mixture was continuously pressed in at a ratio of 0.29 mol and mixed with the molten resin to cool these mixtures to a foaming suitable temperature, and a cylindrical die (circular) having a slit 0.77 mm provided at the tip of the extruder. -Die) (5)
From a die temperature of 122 ° C, the discharge rate per hour is about 8
It was extruded at 7 kg (87 kg / Hr). The outside air device (6) is attached to the foaming foam extruded from the die.
While blowing air (air amount table 3) set to a temperature of 35 ° ± 3 ° from the internal air device (7), the foam is biaxially stretched and cooled, and a cooling plug ( 8), and the surface temperature of the foam was set to 85 ° C.
The foaming was completed at least by the time when the cooling plug (8) passed. This is to prevent variations in the content of the foaming agent in the foam. Then the cutter
It was developed into a foamed sheet with a knife (9). The expanded foam sheet had a width of 1045 mm. The expanded foam sheet was adjusted to a temperature of about 70 ° C and the circumference was 1000 mm.
With the Nidax processing rolls (10a, 10b), the take-up speed was about 3.3 m / min.
b) 200 mm diameter step rolls (1)
While adjusting the feed in 2), the butadiene-styrene copolymer (BS) / BS was used using a Nidax-processed roll (16) (this roll was heated to about 150 ° C.).
A modified ethylene vinyl acetate copolymer (MEVA) / Eval (E) / modified ethylene vinyl acetate copolymer / butadiene-styrene copolymer film having a thickness of about 80 μm was used for about 190 μm.
Lamination was performed using a Nidax processing roll (16) whose heating was controlled at 0 ° C.

A part of the foamed sheet after passing was sampled, and the thickness, density, residual foaming agent amount, and shrinkage ratio were measured. The thickness was 1.76 mm and the density was 0.23 g / c.
m ³ , and the amount of residual foaming agent was 0.15 mol / kg. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD: VD = 1.33: 1.04: 0.
It was 72. This laminated sheet shrinkage rate is 18 in the MD direction.
% And 1% in the TD direction. Further, the cell size ratio of the surface layer portion and the center portion of the foamed sheet (surface layer portion / center portion) is M
The value was 0.60 in the D direction and 0.52 in the TD direction.

The foamed sheet was sent to the heating furnace (17),
It was sent to the molding machine (20) while being pulled by the chain (18). The heating furnace (17) was provided with a pair of upper and lower far infrared heaters (19a, 19b) set at a temperature of 345 ° C., and the foam sheet was heated to a surface temperature of 115 ° C. or higher and its volume increased.

The foamed sheet sent to the molding machine (20) has a width 1 shown in FIGS.
A tray-shaped product having a size of 03 mm, a length of 195 mm, and a depth of 21 mm was formed by a forming die (22a, 22b) having a width of 1000 mm and a length of 600 mm having a 9 × 3 arrangement. The feed length was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 10 seconds. During molding, the foamed sheet should be provided with a slack (26) between the Nidax processed roll (16) and the heating furnace (17) for at least one shot or more. After the molding, each shot was cut by a cutter (23), and at the same time, 27 trays shown in FIGS. 3 to 8 were obtained by one molding. Twenty-seven trays were collected on the moving conveyor (25). The size of the tray is the same width 103 of the mold (22b).
mm, length 195 mm, and depth 21 mm. The residual foaming agent amount in the tray was 0.08 mol / kg. The above results are shown in Table 3.

[0086]

[Table 3]

Example 10. A foam molded article was manufactured using an apparatus as shown in FIG. Impact-resistant polystyrene (trade name: Denka HlE-4) manufactured by Denki Kagaku Co., Ltd. containing 90% by weight of polystyrene (Dencastylol HRM-2) and 6% by weight of styrene-butadiene copolymer.
For 100 parts by weight of mixed resin with 100% by weight, talc is 0.6
Parts by weight, hydrocerol CF (trade name of Dainichi Seika)
0.3 parts by weight of liquid paraffin and 0.1 parts by weight of liquid paraffin were added, and these were uniformly mixed with a mixer to obtain a mixture.
These mixtures are continuously fed from a hopper (1) of an extruder (2) having a screw having a diameter of 115 mm,
In the extruder heated to a maximum temperature of 220 ° C., the mixture is melt-kneaded to form a molten resin, and the foaming agent i-butane is supplied from the foaming agent supply device (3) through the foaming agent supply pipe (4) at 0 per 1 kg of the mixture. Continuously press-fitted at a ratio of 29 mol, mixed with the molten resin, cooled these mixtures to a proper foaming temperature, and provided a cylindrical die (circular die) with a slit 0.77 mm provided at the tip of the extruder. (5)
From a die temperature of 122 ° C, the discharge rate per hour is about 8
It was extruded at 7 kg (87 kg / Hr).

On the foaming foam extruded from the die, the air (air-amount table 4) set by the outside air device (6) and the inside air device (7) at a temperature of 35 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the foam to 85 ° C. The foaming was completed at least by the time when the cooling plug (8) passed. This is to prevent variations in the content of the foaming agent in the foam. Then, it was developed into a foamed sheet with a cutter knife (9). The width of the expanded foam sheet is 1045
It was mm.

This expanded foam sheet was adjusted to a temperature of about 70.degree.
a, 10b) with a take-up speed of about 3.3 m / min and a diameter of 20 provided between the rolls (11a, 11b).
While adjusting the feed with the 0 mm step roll (12), the Nidax processed roll (16) (this roll is about 1
Hot-mettle binder of ethylene-vinyl acetate copolymer (EVA) of about 15μ
A polyethylene terephthalate film (about 55 μm) coated with m was laminated.

The surface temperature of the laminated sheet after passing is 4
It was 9 ° C. Then, a part of the sample was sampled, and the thickness, density and residual foaming agent amount of the foam were measured. The thickness was 2.77 mm, the density was 0.15 g / cm ³ , and the residual foaming agent amount was 0.16 mol / kg. Met. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD:
It was TD: VD = 1.32: 1.04: 0.73.
The shrinkage of this laminated sheet is 17% in MD and 1 in TD.
%Met. Further, the cell size ratio (surface layer portion / center portion) between the surface layer portion and the center portion of the foamed sheet is 0.
59 and 0.52 in the TD direction.

This foamed sheet was fed into the heating furnace (17) while being pulled by the feed chain (18) into the molding machine (20). In the heating furnace (17), a pair of upper and lower far infrared heaters (19a, 19b) set at a temperature of about 335 ° C.
Is provided, the laminated sheet is heated to a surface temperature of 115 ° C. or higher and its volume increases. The foamed sheet sent to the molding machine (20) is attached to the molding machine (20) and has a width of 103 mm, a length of 195 mm, and a depth of 21 shown in FIGS.
mm tray shape with 9x3 array, width 1
Mold (22a, 22a)
Molded according to b). The feed length is 6 per shot
It was 45 mm. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 11.7 seconds. During molding, the foamed sheet was provided with slack (26) between the Nidax processed roll (16) and the heating furnace (17) for at least one shot or more. After the molding, each shot was cut by a cutter (23), and at the same time, 27 trays shown in FIGS. 3 to 8 were obtained by one molding. 27
The individual trays were collected by the moving conveyor (25).
The size of the tray was 103 mm in width, 195 mm in length, and 21 mm in depth of the same size of the molding die (22b).
The residual foaming agent amount in the tray was 0.10 mol / kg.

Example 11. A foam molded article was manufactured using an apparatus as shown in FIG. Polystyrene (produced by Denki Kagaku Co., Ltd., trade name: Denkastyrol HRM-
5) 40 wt%, polybutadiene block aggregates about 30
% (Asa Kasei Co., Ltd. trade name: Asaflex 8
10) With respect to 100 parts by weight of the mixed resin with 60% by weight,
Sodium bicarbonate coated with paraffin and liquor and similarly coated with citric acid at a ratio of 2: 1 mixed at a ratio of 0.6 parts by weight and mixed at a ratio of 0.6 parts by weight. In addition, these were uniformly mixed with a ribbon blender to obtain a mixture. These mixtures are continuously supplied from a hopper (1) of an extruder (2) having a screw having a diameter of 90 mm shown in FIG. 10, and melt-kneaded in the extruder heated to a maximum temperature of 220 ° C. to obtain a molten resin. In addition, i-C ₄ was continuously injected from the foaming agent supply device (3) through the foaming agent supply pipe (4) at a ratio of 0.01 mol per 1 kg of the mixture and 0.05 mol of CO _2. Then, the mixture was mixed with the molten resin, the mixture was cooled to a proper foaming temperature, and the mixture was flown into a merging die provided at the tip of the extruder. At the same time, high impact polystyrene (trade name: Denka HlE-4 manufactured by Denki Kagaku Co., Ltd.)
Was continuously fed from the hopper (1 ') of the extruder (2') having a screw with a diameter of 65 mm, and the maximum temperature was 200
Melt kneading in an extruder heated to ℃ to obtain a molten resin, and n-butane 0.07 mol kg as a resin viscosity modifier
While the molten resin is being cooled, the molten resin is flown into the merging die, and the molten resin cooled to the proper foaming temperature is merged in the merging die to form a cylindrical die having a slit of 0.46 mm (circular die). From (5), die temperature 137
Discharge rate per hour at ℃ 93kg (93kg / H
Extruded in r).

On the laminated sheet (coextrusion) extruded from the die, the air (air-amount table 4) set by the outer air device (6) and the inner air device (7) at a temperature of 45 ° ± 3 ° ) Was blown, the foam was biaxially stretched and cooled, and passed through a cooling plug (8) to bring the surface temperature of the laminated sheet to about 92 ° C.

Next, a laminated sheet was developed with a cutter knife (9). The width of the developed laminated sheet is 104
It was 5 mm. The developed laminated sheet is heated to about 86 ° C.
The temperature was controlled by a two-duck processing roll (10a, 10b) having a circumference of 1000 mm and the take-up speed was about 2.9 m / min. The surface temperature of the laminated sheet after passing through the roll was about 64 ° C.

Further, a part of the laminated sheet after passing was sampled, and the thickness, density, and
When the residual foaming agent amount was measured, the thickness was 0.51 mm,
The density was 0.76 g / cm ³ , and the residual foaming agent amount was 0.01 mol / kg. In addition, MD / T inside the foam sheet
The cell structure ratio in each direction of D and VD is MD: TD: VD =
It was 0.99: 1.04: 0.97. The thickness of the film was 0.112 mm. The cell size ratio between the surface layer and the center of the foamed sheet (surface layer / center) is
It was 0.9 in the MD direction and 0.9 in the TD direction. The shrinkage rate of this laminated sheet is 7% in the MD direction and -1.
It was 5%.

This laminated sheet was sent into the heating furnace (17). The laminated sheet sent to the heating furnace (17) was heated to a surface temperature of 116 ° C. or higher by a far infrared heater (not shown) whose temperature was set to about 370 ° C. The heated laminated sheet has a caliber of 106 mm, a depth of 106 mm and a taper angle of 7 as shown in FIG.
Molds (22a, 22b) in which 4 × 4 cups are arranged in a size of width 600 mm × length 600 mm.
16 pieces of one shot are molded at once by
The cup was collected in the same manner as in. Feed length to the molding machine is 1
It was 645 mm per shot. 15 when molding
It was molded by using both ton pressure and vacuum. The molding cycle was 13 seconds. During molding, the laminate sheet needs to be provided with slack of at least one shot or more between the delivery roll (30) and the heating furnace (17).
The size of the cup is caliber 106mm, depth 106mm,
The taper angle was 7 degrees. The amount of residual foaming agent in the cup is
It was 0.006 mol / kg. The state of the cup was such that it was well stretched, had a substantially uniform thickness, and had no cracks.

Example 12. A foam molded article was manufactured using an apparatus as shown in FIG. Impact-resistant polystyrene (trade name: Denka HlE-4, manufactured by Denki Kagaku Co., Ltd.) containing 95% by weight of polystyrene (Denkastyrol HRM-5, manufactured by Denki Kagaku Co., Ltd.) and 6 wt% of styrene-butadiene copolymer 5 wt. %, Talc 0.6 parts by weight, hydrocerol CF to 100 parts by weight mixed resin
0.4 parts by weight (trade name of Dainichiseika Co., Ltd.) and 0.1 parts by weight of liquid paraffin were added, and these were uniformly mixed with a ribbon blender to obtain a mixture. A mixture of these
It is continuously supplied from a hopper (1) of an extruder (2) having a screw having a diameter of 90 mm shown in FIG. 10 and melt-kneaded in the extruder heated to a maximum temperature of 215 ° C. to obtain a molten resin, and a foaming agent. From the supply device (3) through the foaming agent supply pipe (4), n-C ₄ was continuously injected at a rate of 0.25 mol per 1 kg of the mixture, and mixed with the molten resin to form a mixture of these. Cool to the proper foaming temperature,
It flowed into a merging die provided at the tip of the extruder. At the same time, with respect to 100 parts by weight of impact-resistant polystyrene (trade name: Denka HlE-2 manufactured by Denki Kagaku Co., Ltd.), 0.7 parts of titanium oxide was used.
Parts by weight were mixed with a ribbon blender to obtain a mixture. This mixture was continuously supplied from an hopper of an extruder having a screw having a diameter of 65 mm, melted and kneaded in an extruder heated to a maximum temperature of 200 ° C. to obtain a molten resin, and the molten resin was cooled while a merging die was used. Into the melted resin that has been cooled to the appropriate foaming temperature in the merging die, and has a slit 0.45 mm cylindrical die (circular die).
From (5), extrusion was carried out at a die temperature of 123 ° C. with a discharge rate of about 96 kg (96 kg / Hr) per hour.

While the laminated sheet extruded from the die was blown with air (air-quantity table 4) set at a temperature of 35 ° ± 3 ° from the outer air device (6) and the inner air device (7). The foam was biaxially stretched, cooled, and passed through a cooling plug (8) to bring the surface temperature of the laminated sheet to about 91 ° C.

Next, a laminated sheet was developed with a cutter knife (9). The width of the developed laminated sheet is 104
It was 5 mm. The developed laminated sheet is heated to about 82 ° C.
It was taken up by a take-up speed of about 10.2 m / min with a two-dachsh processing roll (10a, 10b) having a temperature of 1000 mm and a circumference of 1000 mm. The surface temperature of the laminated sheet after passing the roll is
It was about 48 ° C.

Further, a part of the laminated sheet after passing was sampled, and the thickness, density, and
When the residual foaming agent amount was measured, the thickness was 0.46 mm,
The density was 0.31 g / cm ³ , and the residual foaming agent amount was 0.2 mol / kg. In addition, MD / TD inside the foam sheet
The cell structure ratio in each direction of VD is MD: TD: VD = 0.
It was 75: 1.41: 0.95. The thickness of the film was 7 μm. Further, the cell size ratio (surface layer / center) of the surface layer portion and the center portion of the foamed sheet was 0.34 in the MD direction and 0.49 in the TD direction. The shrinkage rate of this laminated sheet was −8% in the MD direction and 13% in the TD direction.

This laminated sheet was sent into a heating furnace (17). The laminated sheet sent to the heating furnace (17) was heated to a surface temperature of 105 ° C. or higher by the far infrared heater (19) whose temperature was set to about 360 ° C. The foamed sheet sent to the molding machine (20) has a width of 1 shown in FIGS.
A tray-shaped product having a size of 03 mm, a length of 195 mm, and a depth of 21 mm was formed by a forming die (22a, 22b) having a width of 1000 mm and a length of 600 mm having a 9 × 3 arrangement. The feed length was 645 mm per shot. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 3.8 seconds. During molding,
The foamed sheet needs to have at least one shot slack (26) between the Nidax processed roll (16) and the heating furnace (17). After the molding, the cutter (23) was used to cut each shot, and at the same time, 27 trays shown in FIGS. Twenty-seven trays were collected on the moving conveyor (25). The size of the tray is the same width 103 of the mold (22b).
mm, length 195 mm, and depth 21 mm. The residual foaming agent amount in the tray was 0.15 mol / kg. The above results are shown in Table 4.

[0102]

[Table 4]

Example 13. A foam sheet was prepared using the same raw materials and method as in Example 2. This foamed sheet was developed into a foamed sheet with a cutter knife (9). The expanded foam sheet had a width of 1045 mm. The expanded foamed sheet was taken up by a two-dax processing roll (10a, 10b) having a circumference of 1000 mm, whose temperature was adjusted to about 70 ° C., at a take-up speed of about 3.5 m / min, and the rolls (11a, 11b) were taken.
Adjusting the feed with a step roll (12) with a diameter of 200 mm provided between the rolls (1
6) A non-stretched polypropylene (CPP) film coated with a polyester adhesive layer of about 15 μm (this roll also serves as a heating roll and a delivery roll).
0 μ was passed while heating and fusing. The surface temperature of the foamed sheet after passing was about 54 ° C.

Further, a part of the foamed sheet after passing was sampled, and the thickness, density, residual foaming agent amount, and shrinkage ratio were measured. As a result, the thickness was 2.0 mm and the density was 0.23 g / cm.
³ , residual foaming agent amount is 0.17 mol / kg, shrinkage is MD
The direction was 10% and the TD direction was 5%. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD:
It was TD: VD = 1.13: 1.05: 0.84.
Further, the cell size ratio (surface layer portion / central portion) of the surface layer portion and the center portion of the foamed sheet was 0.83 in the MD direction and 0.73 in the TD direction. This foamed sheet is heated in a heating furnace (1
7) was fed into the molding machine (20) while being pulled by the feed chain (18). The heating furnace (17) has a pair of upper and lower far infrared heaters (19) set at a temperature of 347 ° C.
a, 19b) are provided, the foamed sheet is heated to a surface temperature of 105 ° C. or higher and its volume is increased.

The laminated foam sheet sent to the molding machine (20) was attached to the molding machine (20) by a cup having a diameter of 106 mm, a depth of 106 mm and a taper angle of 7 degrees as shown in FIG. 4 in a 600mm length
1 by the molding dies (22a, 22b) arranged in 4 ×
Sixteen shots were molded at one time so that the film would be inside the container, and then cut in the same manner as in Example 1 to recover the cup. Feed length to the molding machine is 645 per shot
It was mm. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 11 seconds.
During molding, the foam sheet is rolled (16) and heated (17)
Slack of at least one shot between and (26)
Was set up. The size of the cup (51) is 10
The depth was 6 mm, the depth was 106 mm, and the taper angle was 7 degrees.
The residual foaming agent amount in the cup (51) is 0.11 mol / kg.
Met. The state of the cup (51) was good in elongation, thickness was almost uniform, and cracks were not generated.

Example 14. A molded product was manufactured using the same apparatus as shown in FIG. Screw diameter 115
mm product extruder for external use recovery product (tray container) 10
To 0%, 0.2 parts by weight of powdered talc was added to 8.0 parts by weight of talc masterbatch (20% talc was kneaded in PS resin), and the mixture was charged from a hopper. The mixture was heated to about 225 ° C. and, as a foaming agent, nC ₄ / iC ₄ = 35/65 at a density of 0.
Melt by press-fitting at a ratio of 27 mol / kg,
Kneaded. The melt was brought to a proper foaming temperature, and a circular die (slit 0.39) provided at the tip of the extruder was used.
(mm) with a die temperature of 122 ° C. and a discharge rate of 75 kg / H.

While biaxially stretching the obtained cylindrical foam, the inner air amount was 0.08 m ³ / m ² from the inside and outside of the balloon,
Nidax processing roll with a diameter of about 320 mm, which was cooled with an outside air amount of 0.07 m ³ / m ² , cooled through a plug and cooled to 85 ° C.
Take it off with l and then remove it with a width of 10 mm and a height of 2 mm.
The ridges extending over the entire length in the axial direction of the roller having a diameter of 00 mm were arranged at intervals of about 15 mm in the circumferential direction of the roll. A pressure of 2.2 kg / cm ² was applied to the foamed sheet between the irregularity forming rolls.
Then, the pressure of the air cylinder was applied to push it out.

This foamed sheet was coated with Hl having a thickness of about 200 μm.
The PS film was extrusion-laminated from the extruder using a T-die, and then, using a heat roll as shown in FIG. The surface temperature of the foamed sheet after passing was about 50 ° C.

[0109] Also, after sampling a part of the foam sheet, thickness, density, residual blowing agent weight, was measured shrinkage, thickness 2.0 mm, density of 0.21 g / cm ^3, the residual blowing agent weight 0.15 mol / kg, shrinkage is 8 in MD
% And 3% in the TD direction. In addition, M inside the foam sheet
The cell structure ratio in each direction of D / TD / VD is MD: TD: V
It was D = 1.16: 1.06: 0.82. Further, the cell size ratio (surface layer portion / center portion) between the surface layer portion and the center portion of the foamed sheet is 0.82 in the MD direction and 0.
It was 74. This foamed sheet was fed into the heating furnace (17) while being pulled by the feed chain (18) into the molding machine (20). The heating furnace (17) has a pair of upper and lower far infrared heaters (19a, 19b) set at a temperature of 380 ° C.
The foamed sheet was heated to a surface temperature of 112 ° C. or higher and its volume increased.

The laminated foamed sheet sent to the molding machine (20) was attached to the molding machine (20) by a cup having a diameter of 106 mm, a depth of 106 mm and a taper angle of 7 degrees as shown in FIG. 4 in a 600mm length
1 by the molding dies (22a, 22b) arranged in 4 ×
Sixteen shots were molded at one time so that the film would be inside the container, and then cut in the same manner as in Example 1 to recover the cup. Feed length to the molding machine is 645 per shot
It was mm. At the time of molding, a pressure of 15 tons and a vacuum were used together. The molding cycle was 11 seconds.
During molding, the foam sheet is rolled (16) and heated (17)
Slack of at least one shot between and (26)
Was set up. The size of the cup (51) is 10
The depth was 6 mm, the depth was 106 mm, and the taper angle was 7 degrees.
The amount of residual foaming agent in the cup (51) is 0.09 mol / kg.
Met. The state of the cup (51) was good in elongation, thickness was almost uniform, and cracks were not generated.

[0111]

[Table 5]

Comparative Example 1. With the same composition as in Example 2, the amount of the blowing agent was increased to 0.36 mol / kg, and the die temperature was set to 119 ° C.,
The foam was extruded at a discharge rate of 89 kg / H. While biaxially stretching the obtained cylindrical foam, air-cooling from inside and outside,
It was cooled to about 81 ° C. through a cooling plug. At this time, the air amount of Example 2 was 0.08 m ³ / m ² (sheet area) on the outside and 0.11 m ³ / m ² on the outside.
It was raised to 0.23 m ³ / m ² , outside, to 0.32 m ³ / m ² . The foamed sheet was passed through the same roll as in Actual Example 1, and the surface temperature was lowered by 45 ° C. After laminating the OPS film 25 μm, the shrinkage ratio is 6% in the MD direction and 12% in the TD direction.
The residual foaming agent amount was 0.32 mol / kg at 1.6 mm and a density of 0.25 g / cm ³ . M inside the foam sheet
It was D: TD: VD = 0.89: 1.32: 0.85. This cup was heated by a molding machine without cutting, and a cup was molded. The molded product had a residual foaming agent content of 0.29 mol / kg, was soft and lacked in strength. Also, the moldability was not good. Thus, it can be seen that the amount of gas left in the molded product is greatly affected by cooling or the like immediately after extrusion. Further, the cell size ratio of the surface layer portion and the center portion of the foamed sheet (surface layer portion / center portion) was 0.44 in the MD direction and 0.37 in the TD direction.

Comparative Example 2. In Example 3, the additive was changed to 1.0 part by weight of talc and 0.2 part by weight of Mg stearate, and the amount of the foaming agent i-C ₄ was increased to 0.5 mol / kg,
When the 90 ° C temperature control roll was lowered to 35 ° C, the residual foaming agent amount became 0.33 mol / kg, and the thickness of the molded product did not appear even after molding (zide thickness 2.7 mm), and strength was improved. There was a problem. The residual foaming agent amount of the molded product is 0.28 mol / k
The molded article was softened by g. Further, the cell size ratio of the surface layer portion and the center portion of the foamed sheet (surface layer portion / center portion) is 0.53 in the MD direction and 0.48 in the TD direction.
Met. Other sheet properties are shown in Table 6.

Comparative Example 3. In Example 3, the additive was changed to 1.0 part by weight of talc and 0.2 part by weight of Mg stearate, and the take-up speed was increased to 6 m / min.
The sheet thickness was 1.6 mm, the density was 0.11 g / cm ³ , the shrinkage ratio was about 24% in the MD direction and about 4% in the TD direction, and the residual foaming agent amount was 0.27 mol / kg. The cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD: VD = I. 65: 0.86: 0.
It was 70. This sheet was subjected to almost the same conditions as in Example 5,
When the bento box was molded, whether the foamed sheet undulates in the TD direction when heated, causing uneven heating partially,
Or, did the sheets overlap? In addition, the elongation in the MD direction was poor and holes were formed in the molded product. The residual foaming agent content of the molded product was 0.16 mol / kg. After extrusion and packaging,
The time until the molding was heated was about 147 seconds and the molding cycle was 6.4 seconds. Further, the cell size ratio (surface layer portion / center portion) of the surface layer portion and the center portion of the foamed sheet was 0.17 in the MD direction and 0.41 in the TD direction. The above results are shown in Table 6.

[0115]

[Table 6]

Comparative Example 4. A molded product was manufactured using the same apparatus as shown in FIG. In the extruder with a screw diameter of 115 mm, the polystyrene resin (Denriki Styrol HRM
-2) A mixture in which 100 parts by weight, 0.9 parts by weight of talc, 0.1 part by weight of hydrocerol CF and 0.1 part by weight of liquid paraffin are uniformly mixed with a tumbler is supplied from a hopper and heated to about 225 ° C. Together with i-butane 4.62 mol / kg as a foaming agent, press-fitted in such a ratio that
It was melt-kneaded. This molten mixture was extruded and foamed from a cylindrical die (slit 0.46 mm) provided at the tip of the extruder at a die temperature of 118 ° C. and a discharge rate of 83 kg / H. The resulting cylindrical foam was biaxially stretched, cooled from the inside and outside (air-volume table 7), passed through a cooling plug, and heated to about 82 ° C.
The temperature of the foamed sheet cooled to 110 ℃ was adjusted to about 320
The surface temperature of the foamed sheet was about 51 ° C. after 2 rolls of 2 mm roll having a diameter of 2 mm were drawn and passed through 2 rolls of a 200 mm diameter step roll.

The ratio of PS resin and high-impact resin from the extruder to this sheet was set to 1/1, charged into the extruder hopper, melted, 0.2% of silicon was injected, and extruded from the T-die to obtain about 170 μm. Laminated by the thickness. The foam sheet has a shrinkage ratio of 9% in the MD direction and 5% in the TD direction, the residual foaming agent amount is 0.43 mol / kg, and the density is 0.07.
It was 7 g / cm ³ and the thickness was 2.53 mm. This laminated sheet is continuously fed without cutting with a far-infrared heater heating chamber of about 315 ° C., heated to a sheet surface temperature of 105 ° C. or higher by a 15-ton press and a diameter of 106 m.
m, depth 106 mm, cup with taper 7 degrees, effective width 60
It was molded in 16 pieces of 0 mm × 600 mm. During this time,
About 100 until the foamed sheet is extruded and heated in the molding machine
It was seconds. The residual gas of the molded product is 0.26 mol / kg
Met. MD / TD / V inside the foam sheet before thermoforming
The cell structure ratio in each direction D is MD: TD: VD = 1.5.
It was 4: 0.99: 0.66. A complete cup could not be molded. Further, the cell size ratio (surface layer / center) of the surface layer portion and the center portion of the foamed sheet was 0.33 in the MD direction and 0.28 in the TD direction.

Comparative Example 5. In Example 5, blowing agent nC_Four/
i-C_Four= 6/4 to 0.47 mol / kg and C0 ₂0.1
1 mol / kg was press-fitted into the extruder, the die temperature was 112 ° C,
The discharge rate was changed to 87 kg / H. Emission after passing the cooling plug
The foam sheet temperature was 79 ° C. Also, heat the roll to 90 ° C.
Approximately 265 μm HlP is heated up and passed through the uneven forming roll
After extrusion laminating the S film, the sheet thickness is 2.3 mm
The shrinkage ratio was MD13% and TD-5%.
In addition, cells in the MD, TD, and VD directions inside the foam sheet
The structure ratio is MD: TD: VD = 0.99: 1.29: 7.
8, the residual blowing agent amount was 0.32 mol / kg, and the density was
0.11 g / cm³Met. Met. Cup molding
Even if it is carried out, the thickness of the molded product does not appear and the cup side thickness is actual.
In Example 1, what was 1.8 mm became 1.1 mm
It was The residual foaming agent in the molded product was 0.21 mol / kg.
It was Next, use a heating roll to reduce the amount of residual foaming agent.
When the temperature was raised to ℃
Caused. Also, the section between the surface layer and the center of the foam sheet is
The size ratio (surface layer / center) is 0.
67 and 0.61 in the TD direction.

Comparative Example 6. In Example 12, the discharge amount is 75 kg
/ H to reduce the amount of n-C4 blowing agent to 0.26 mol / k
The sheet extruded and foamed to g is cooled to 86 ° C.,
Pass S-roll temperature controlled to ℃
And slackened. The shrinkage rate of this sheet is MD-
10%, 16% in TD direction, residual foaming agent amount is 0.22
Mol / kg (foam only), density about 0.30 g
/ Cm ³ , thickness 0.47 mm (foam only), the film was about 6 μm. When this sheet was heated by a tray molding machine, clamp misalignment occurred and molding could not be performed.
However, when the molding temperature was lowered, waviness was generated in the MD direction, but the molding was not impossible. Was considered the limit. At this time, the cell structure ratio in each direction of MD, TD and VD inside the foamed sheet is MD: TD: VD = 0.72: 1.4.
It was 5: 0.96. Further, the cell size ratio (surface layer portion / center portion) between the surface layer portion and the center portion of the foamed sheet was 0.63 in the MD direction and 0.51 in the TD direction. The above results are shown in Table 6.

[0120]

[Table 7]

[0121]

The present invention has a density of 0.095 to 0.77 g.
/ Cm ³ , thickness 0.3 to 3.0 mm, and the cell structure ratio in the MD, TD, and VD directions inside the foam sheet excluding the skin layer is 0.72: 1.42: 0.98 to 1.54. : 0.9
0: 0.72, and the residual foaming agent amount is 0.01 to
Foam for thermoforming, which is a laminate of a polystyrene resin foam sheet of 0.3 mol / kg and a thermoplastic resin film having a thickness of 0.005 to 0.6 mm, and a shrinkage rate of -10% to 20%. Since it is a styrene resin laminated sheet,
No significant expansion in the MD and TD directions, no heating unevenness during molding, and no expansion of the chrysanthemum pattern. Further, since it can be uniformly stretched in the MD and TD directions, a molded product such as a container having a deep drawing ratio of 1 to 1.8 can be molded. In addition, it is possible to form a molded product having a structure matching the printed pattern and a molded product having a good mold appearance and matching the mold structure and having a good appearance.

From the foamed styrene resin laminated sheet for thermoforming of the present invention, a molded product having a deep drawing ratio of 1 or more and a side wall rising at a right angle can be molded. The molded product obtained by thermoforming the foamed styrene resin laminate sheet for thermoforming of the present invention has a small difference in wall thickness between upper, lower and lower side walls, and a difference in wall thickness around each side wall. The grammage is uniform. Therefore, unevenness in drawing and strength defects do not occur on any side wall of the molded product. Also, lip curl processing can be easily applied to the molded product such as the container of the present invention.

[Brief description of drawings]

FIG. 1 is a schematic side view showing a specific example of an apparatus used for continuously producing a foamed styrene resin laminated sheet for thermoforming and a molded article of the present invention.

FIG. 2 is a schematic side view showing another specific example of an apparatus used for continuously producing a foamed styrene resin laminated sheet for thermoforming and a molded article of the present invention.

FIG. 3 is a plan view showing an example of a tray which is a specific example of a molded product obtained by the present invention.

FIG. 4 is a partial cross-sectional view taken along the line IV-IV ′ in FIG.

5 is a sectional view taken along line V-V ′ in FIG.

6 is a sectional view taken along the line VI-VI ′ in FIG.

7 is a partially enlarged view of VII-VII 'in FIG.

FIG. 8 is an enlarged view of part VII in FIG.

9A and 9B are a plan view and a side view showing an example of a cup which is a specific example of the molded product obtained by the present invention.

FIG. 10 is a schematic plan view showing another specific example of an apparatus used for continuously producing the foamed styrene resin laminate sheet for thermoforming of the present invention and a molded product.

FIG. 11 is a schematic side view showing another specific example of the apparatus used for continuously producing the foamed styrene resin laminated sheet for thermoforming and the molded article of the present invention.

FIG. 12 is a diagram illustrating a cell size measuring method.

[Explanation of symbols]

1, 1 ': Hopper 2, 2': Extruder 3: Foaming agent supply control device 5: Circular mold (cylindrical die) 6: Outer air device 7: Inner air device 8: Cooling plug 9: Cutter
17: heating furnace 20: molding machine 101: tray 102: bottom wall 10
3: Collar 104: Side wall 105, 109, 110, 112, 114 to 121, 1
25: Rib

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI B29K 105: 04 B29L 7:00 B29L 7:00 9:00 9:00 9:00 B65D 81/16 D (56) References -364920 (JP, A) JP 59-179633 (JP, A) JP 5-96673 (JP, A) JP 4-91920 (JP, A) JP 53-108179 (JP, A) ) JP-A-57-129727 (JP, A) JP-B 2-335664 (JP, B2) (58) Fields investigated (Int.Cl. ⁷ , DB name) B32B 1/00 -35/00 B29C 47 / 00-47/96 B29C 51/00-51/46 B65D 81/133 C08J 9/00-9/42

Claims (10)

(57) [Claims] 1. A laminated sheet obtained by laminating a foamed styrene resin sheet and a thermoplastic resin film, wherein the density of the foamed styrene resin sheet is 0.095 to.
0.77 g / cm ³ , thickness 0.3 to 3.0 mm, cell size in the MD direction inside the sheet excluding the skin layer: TD
The cell structure ratio, which is the ratio of the cell size in the VD direction to the cell size in the VD direction, is 0.72: 1.42: 0.98 to 1.5.
4: 0.90: 0.72, the amount of the foaming agent remaining in the foamed sheet is 0.01 to 0.3 mol / kg, and the thickness of the thermoplastic resin film is 0.005 to 0. 6
mm, and the shrinkage rate of the laminated sheet is -9% to 19% , a foamed styrene resin laminated sheet for thermoforming. 2. The expanded styrene resin laminate sheet for thermoforming according to claim 1, wherein the shrinkage ratio is −5% to 15%. 3. A ratio obtained by dividing the cell size of the surface layer portion of the expanded styrene resin sheet excluding the skin layer by the cell size of the center portion of the foamed sheet is 0.2 or more in both MD and TD directions. The foamed styrene resin laminated sheet for thermoforming according to claim 1, characterized in that. 4. A styrenic resin obtained by mixing at least one selected from butadiene rubber, ethylene-propylene rubber, and styrene-butadiene rubber, or a styrene-based resin obtained by copolymerizing butadiene, isoprene, and chloroprene. A foamed styrene-based resin laminated sheet for thermoforming according to claim 1, which is an impact-resistant styrene-based resin mixed with a polymer resin. 5. A styrenic copolymer containing 1 to 50% by weight of at least one of acrylic acid, methacrylic acid, acrylonitrile, maleic anhydride, phenylene ether and propylene, or the above-mentioned foamed styrene resin sheet. The foamed styrene-based resin laminated sheet for thermoforming according to claim 1, which is a heat-resistant styrene-based resin made of a mixture containing a polymer of monomers in an amount of 1 to 50% by weight. 6. The expanded styrene resin laminate sheet for thermoforming according to claim 1, wherein the expanded styrene resin sheet contains 0.2 to 20% by weight of a filler. 7. The thermoplastic resin film is a gas barrier resin film, or is further laminated with a gas barrier resin film.
The foamed styrene resin laminated sheet for thermoforming according to item 1. 8. A thermoplastic resin film previously formed on a foamed styrene resin sheet is laminated by a heating roll, and a thermoplastic resin film in a molten state immediately after extrusion is laminated on a foamed styrene resin sheet, Alternatively, the method for producing a foamed styrene resin laminated sheet for thermoforming according to claim 1, wherein the foamed styrene resin sheet and the thermoplastic resin film are coextruded and laminated. 9. A molded article obtained by thermoforming the foamed styrene resin laminated sheet for thermoforming according to claim 1. 10. A container obtained by thermoforming the foamed styrenic resin laminated sheet for thermoforming according to claim 1.
A container characterized in that at least a thermoplastic resin film is inside the container.