JPH0717798B2 - Upper open container made of poly-3-methylbutene-1 resin - Google Patents

Description

The present invention relates to a heat-resistant container made of poly-3-methylbutene-1 resin. More specifically, a rubbery α-olefin copolymer-containing poly 3-, which can withstand heating in a microwave oven and use in an oven at 160 ° C. or higher, preferably 200 ° C. or higher.
The present invention relates to a heat-resistant upper opening container made of methylbutene-1 resin.

In recent years, the demand for instant foods for the purpose of shortening the cooking time or simplifying the cooking is increasing with the increase in the number of households where the couple live together or the number of people living alone. With such a tendency and the recent widespread use of microwave ovens, heat-resistant containers used for both microwave ovens and ovens have been attracting attention.

[Conventional technology]

Conventionally, expanded polystyrene is often used as a container for instant foods, but polystyrene has a low softening temperature and its heat resistance is insufficient for use in microwave ovens, ovens and the like.

Polypropylene is a resin having higher heat resistance than polystyrene. Polypropylene resin containers usually have sufficient heat resistance when putting foods with high water content and heating in a microwave oven, but they do not withstand oily fats or use in ovens at 160 ° C or higher. .

On the other hand, a so-called easily crystallizable polyethylene terephthalate (hereinafter referred to as C-PE) containing an additive that accelerates the crystallization rate and blended with polyolefin or the like in order to enhance the impact resistance.
The thin-walled container (called T) is also oil resistant, and
It is being used as a container that can be used in both ovens.

[Problems to be solved by the invention]

However, such a polyethylene terephthalate container has the following disadvantages.

First, although instant foods of this type are often stored frozen, C-PET containers have insufficient impact resistance at low temperatures.

Also regarding heat resistance, the C-PET container is 220 ° C to 230 ° C.
Although it is said that the C-PET container is actually applied to a household microwave oven, it is easily deformed at high temperatures and cannot be put to practical use. In addition, crystallization proceeds after cooking, and impact resistance is greatly reduced. Further, when the C-PET container is heated at the same output as compared with the glass container, the temperature rise of the contents is slow, that is, the high frequency utilization efficiency is low.

[Means for solving problems]

In view of the current state of the heat-resistant container as described above, the present inventors have earnestly studied the application of the high melting point, poly-3-methylbutene-1, which is a highly crystalline polyolefin, to the heat-resistant container. The present invention has been accomplished by finding that a heat-resistant container having good performance in which the drawbacks of the heat-resistant container made of another resin are improved can be obtained.

That is, the present invention is a rubber-like α- olefin copolymer 1 to 30
The poly-3-methylbutene-1 resin, which is contained in a weight percentage, is formed into a sheet and then thermoformed, and the poly-3-methylbutene-1 resin is present in an upper opening type container.

Hereinafter, the present invention will be described in detail.

Poly-3-methylbutene-1 containing 1 to 30% by weight of the rubbery α-olefin copolymer used in the present invention.
As the resin (hereinafter, this may be simply referred to as a poly-3-methylbutene-1 resin composition), a 3-methylbutene-1 homopolymer, or a copolymer of 3-methylbutene-1 and another α-olefin is used. It is possible to use a blend of a polymer and a saturated rubber-like substance. The rubbery substance used here is preferably a rubbery copolymer of an α-olefin having 2 to 20 carbon atoms, particularly 3-methylbutene, from the viewpoint of compatibility with a 3-methylbutene-1 (co) polymer. -3 units containing 3 to 50% by weight, 3-methylbutene-1
And a binary or ternary rubber-like copolymer of α-olefin with 2 to 20 carbon atoms is used.

The content of the rubber-like substance in the poly-3-methylbutene-1 resin composition is 1 to 30% by weight, preferably 3 to 25% by weight. When the content of the rubber-like substance is more than the upper limit, heat resistance becomes insufficient. When the content of the rubber-like substance is less than the lower limit, moldability and impact resistance are insufficient.

The method of blending is not particularly limited, and a method such as blending in a solution, blending with a single-screw or twin-screw extruder, or a kneading machine such as a Banbury mixer can be used, but preferably 3 -Methylbutene-
A method of blending by homopolymerization 1 or copolymerization of 3-methylbutene 1 with another α-olefin and polymerization of a rubbery copolymer in multiple stages is preferable. The method of polymerizing in multiple stages will be described later.

320 of the poly-3-methylbutene-1 resin composition of the present invention
The melt index measured according to ASTM D1238 at 0 ° C. is 0.1 to 100 g / 10 min, preferably 0.5.
~ 70g / 10min. When the melt index is higher than the upper limit, the fluidity is good and the sheet moldability is good,
On the other hand, there is drawdown of the sheet during thermoforming, and the formability in thermoforming is reduced. In addition, impact resistance is also reduced. When the melt index is lower than the lower limit, the impact strength is high, but molding becomes impossible or the productivity becomes low.

Since the melt index of the poly-3-methylbutene-1 resin composition may change during molding, it is preferable that the melt index of the molded product be within the above range in order to obtain good physical property values.

The melting point of the poly-3-methylbutene-1 resin composition of the present invention measured by DSC is 250 ° C to 310 ° C. Particularly preferably, the melting point is 270 ° C to 305 ° C. When the melting point is higher than the upper limit, the molding temperature becomes too high, and the polymer is likely to deteriorate during molding. When the melting point is lower than the lower limit, the heat resistance is insufficient.

In addition, the poly-3-methylbutene-1 resin composition of the present invention
The heat of fusion measured by DSC is 4 cal / g or more, preferably 6 cal / g
That is all. If the heat of fusion is small, it means that the degree of crystallinity is low and the heat resistance is lowered.

Next, a multi-step polymerization method for obtaining the poly-3-methylbutene-1 resin composition of the present invention will be described.

As a multi-stage polymerization method, a homopolymer of 3-methylbutene-1 in the first stage, or more preferably, a random mixture of 3-methylbutene-1 and a small amount of another α-olefin having 2 to 20 carbon atoms. A method is conceivable in which a rubber-like copolymer is produced by producing a copolymer and then copolymerizing 3-methylbutene-1 with another α-olefin in the presence of the polymer and the catalyst in the first step. Other α-olefins having 2 to 20 carbon atoms include ethylene, propylene, butene-1,
Hexene-1, octene-1, decene-1, dodecene-
1, straight chain α-, such as tetradecene-1 and octadecene-1
Examples include branched α-olefins such as olefins, 4-methylpentene-1, 3-methylpentene-1, and vinylcyclohexene. Usually, a linear α-olefin is used.

In this case, the content of the monomers other than 3-methylbutene-1 in the random copolymer in the first step is 15% by weight or less,
It is preferably 10% by weight or less.

The second stage rubbery copolymer is 3-methylbutene-
1-content is 50% by weight or less, 3-methylbutene-1
And a C2-C20 other α-olefin, or a copolymer of two or more C2-C20 α-olefins. The other α-olefin is selected from those that can be used in the first step. The copolymerization method is preferably a so-called random copolymerization method. Branched α-olefins are also used in the same manner as linear α-olefins.

As a copolymer of two or more kinds of α-olefins other than 3-methylbutene-1, for example, ethylene-propylene, ethylene-4-methylpentene-1, propylene-4-methylpentene-1, 4-methylpentene-1. Octene-1,4-methylpentene-1 to decene-1,4-methylpentene-1 to dodecene-1,4-methylpentene-
It may be a copolymer such as 1-decene-1 to tetradecene-1, and the comonomer content of each is about 30 to 70% by weight, but preferably the same component is 3-methylbutene-
It is a copolymer of 1 and another α-olefin. Other α-
As the olefin, two or more kinds may be used. The content of 3-methylbutene-1 in the copolymer is 50% by weight or less, preferably 3 to 50% by weight. Outside this range, improvement in tear strength and impact strength of the molded product is insufficient. The proportion of the second stage component in the whole polymer is 1 to 30% by weight as described above,
It is preferably selected from the range of 3 to 25% by weight.

Further, as the multi-step polymerization method, a three-step polymerization method in which the first step of the above-mentioned two-step polymerization method is further divided into two steps is preferably used.

When the components obtained in the first stage, the second stage and the third stage of the three-stage polymerization method are referred to as components (a), (b) and (c), respectively, the component (a) is 3-methylbutene. -1 homopolymer or a copolymer of 3-methylbutene-1 having a 3-methylbutene-1 content of more than 90% by weight and another α-olefin having 2 to 20 carbon atoms. The other α-olefin having 2 to 20 carbon atoms in the copolymer is selected from those which can be used in the first stage of the two-step polymerization method. The copolymerization method is preferably a so-called random copolymerization method. When the content of 3-methylbutene-1 in the component (a) is 90% by weight or less, the melting point and crystallinity of the final three-stage polymer are insufficient,
The heat resistance becomes insufficient.

The proportion of component (a) in the three-stage polymerization composition is 10 to 85% by weight, preferably 30 to 70% by weight. Component (b) is 3-
It is a copolymer of 3-methylbutene-1 and another α-olefin having 2 to 20 carbon atoms and having a methylbutene-1 content of 90 to 60% by weight. Other α-olefins include (a)
It is selected from those that can be used in the component. Two or more kinds of these other α-olefins may be used, and the copolymerization method is preferably a so-called random copolymerization method. The content of 3-methylbutene-1 in the copolymer is 90 to 60% by weight,
It is preferably 85 to 60% by weight. 3-methylbutene-1
If the content of is too large, the impact strength decreases. If it is too small, the heat resistance will be insufficient. The proportion of component (b) in the three-stage polymer composition is 10-85% by weight, preferably 20-50.
It is selected from the range of weight%. If the proportion of component (b) is too small, the impact strength will decrease, and if it is too large, the heat resistance will be insufficient.

Regarding the component (c), both the composition and the content in the three-stage polymer are considered to be the same as the second-stage component in the two-stage polymer.

The polymer obtained by the three-step polymerization is superior to the polymer obtained by the two-step polymerization in the uniform dispersibility of the rubber-like component, and higher heat resistance and impact resistance are simultaneously obtained.

The characteristics of the poly-3-methylbutene-1 resin composition of the present invention are its excellent impact resistance and thermoformability, and such a performance cannot be obtained with a random copolymer containing no rubber component.

Next, the polymerization method will be described.

In an aliphatic, alicyclic or aromatic hydrocarbon such as butane, hexane, heptane, cyclohexane, benzene, etc.,
3-methylbutene-1 or 3-methylbutene-1 and α-olefin in the presence of a transition metal compound and an organometallic compound of a metal of Group 1 to Group 3 of the periodic table in a liquid olefin or without a solvent Polymerize.

In the case of three-step polymerization, the components (a) and (b) are produced, and then the component (c) is produced. It is particularly preferable to form the component (a) first, then the component (b), and finally the component (c) in this order in order to prevent the elution of the component (c) into the solvent in the catalyst removal step.

Also in the case of two-step polymerization, it is preferable to finish the polymerization of the rubber-like component in the same manner.

The transition metal compound as a catalyst and the organometallic compound of a metal of Groups 1 to 3 of the periodic table are not particularly limited, and those usually used for olefin polymerization are used. Preferred is a combination of a solid catalyst component containing an electron-donating compound such as Mg, Ti, a halogen and an ether or an ester with an organoaluminum compound and optionally an electron-donating compound such as an ether. Such solid catalyst components are disclosed in JP-A-52-98076, JP-A-53-24378, JP-A-53-85877, JP-A-53-117083, and JP-A-59-6.
No. 204, No. 59-11306, etc. Further, the aluminum content is 0.15 or less in the atomic ratio of aluminum to titanium, and a solid titanium trichloride catalyst component containing a complexing agent and an organic aluminum compound, especially aluminum dialkyl monohalide and optionally an ether, an ester, etc. Combinations with electron donating compounds such as Such solid titanium trichloride catalyst components are disclosed in JP-B-55-8451, JP-B-55-8452, JP-B-55-8003, JP-B-54-27871 and JP-B-55-391.
No. 65, No. 55-14054, No. 53-44958 and the like.

The polymerization temperature is 0 to 150 ° C. If necessary, a molecular weight modifier such as hydrogen may be used.

The melting point of the polymer composition thus obtained is 250 ° C or higher, preferably 260 ° C or higher, more preferably 270 ° C or higher.

The multi-step polymerization method is described in JP-A-67-1349 and Japanese Patent Application No. 62-72.
083 etc.

Since the container of the present invention is used at a high temperature, it is important to select a heat stabilizer, and it is particularly preferable that the container has less scattering at a high temperature.

Examples of such additives include Iganox 1010 (trade name; manufactured by Nippon Ciba Geigy) and Irgaphos P-EP.
Q (trade name; manufactured by Nippon Ciba Geigy) and, in some cases, a combination of dihydroanthracene, Irganox 10
Combination of 10 and MARKAO-412S (trade name; made by ADEKA ARGUS) and, in some cases, Irgaphos P-EPQ, M
ARKAO-18 (trade name; made by Adeka Argus), MARKAO-4
12S (trade name; manufactured by ADEKA ARGUS CORPORATION) and, in some cases, a combination of Irgafoss P-EPQ and the like are used.
In addition, Rasmit HPM-12 (trade name; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.), Irgafos 168 (trade name; manufactured by Nippon Ciba Geigy), DSTDP, etc. are also effective.

More preferably, the antioxidant used in the present invention has a 1.0 wt% reduction temperature of 290 as measured by a thermobalance (TGA).
Use a hindered phenolic compound that satisfies the requirement of not less than ° C.

The 1.0% by weight reduction temperature measured by TGA here means the polymerization reduction was measured at a temperature rising rate of 15 ° C / min under an air flow rate of 100 ml / min, and a 1.0% by weight reduction was observed. Is the temperature of.

Examples of the special hindered phenolic antioxidant used in the composition of the present invention include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-
4-hydroxyphenyl) propionate] and 3,9-
Bis [1,1-dimethyl-2- {β- (3-t-butyl-
4-hydroxy-5-methylphenyl) propynyloxy} ethyl] -2,4,8,10-tetraoxysuspyro [5,
5] It is desirable to use undecane alone or in combination.

The amount of the antioxidant added is 0.1 to 3 parts by weight based on 100 parts by weight of 3-methylbutene-1 homopolymer or a copolymer of 3-methylbutene-1 and another α-olefin having 2 to 20 carbon atoms, It is preferably 0.2 to 2 parts by weight.

If the amount is less than 0.1 parts by weight, sufficient effect cannot be obtained. Even if it is used in excess of 3 parts by weight, the effect is not improved and it is economically disadvantageous. May occur, which is not preferable.

As a method for molding the container of the poly-3-methylbutene-1 resin composition of the present invention, a thermoforming method is preferably used. The thermoforming method is the "Practical Plastics Glossary" (edited by Shoji Seto, Plastic Age, 1975) or the on-site manual "Heat processing (vacuum forming, pressure forming)" (edited by Sogo Chemical Research Institute, Inc. ) Asano Laboratory, Kazuo Asano), etc., is a method of processing a sheet of thermoplastic resin, which is a method of cooling a heat-softened sheet while deforming it with some external force to form a molded article, Ridge molding, matched moulding molding, straight molding (vacuum, pressure molding), drape molding, reverse draw molding, air slip molding, plug assist molding, plug assist reverse draw molding, contact heating pressure pneumatic molding and the like. Usually, a vacuum-assisted vacuum or pressure-assisted molding with a plug assist can sufficiently obtain a molded product of a desired shape.

To describe the outline of vacuum and pressure molding, a sheet of the above-mentioned poly-3-methylbutene-1 resin composition is molded, and then the sheet is softened by heating, and the softened sheet is placed in a mold by vacuum and / or pressure. Spread uniformly and stretch. Then, after the crystallization is sufficiently advanced in the mold, the molded product is taken out from the mold. The sheet can be formed by a usual method such as T-die extrusion. The thickness of the sheet is usually 200 μm to 2.5 mm, preferably 300 μm to 1.5
mm. If the thickness of the sheet exceeds this value, it becomes difficult to uniformly heat the sheet, and the progress of crystallization in each part of the sheet becomes uneven, which is not preferable.

The heating temperature of the sheet is 220 to 310 ° C, preferably 250 to 300
The melting point of the resin composition is preferably in the range of ± 20 ° C., and the melting point of −5 + 10 ° C. is usually optimum.

Next, when the sheet becomes semitransparent by heating, it is desirable to apply vacuum or pressure to the sheet for molding.

If the heating time is long or the heating temperature is too high,
This is not preferable because the resin deteriorates and the physical properties deteriorate.
The heating time is usually 30 seconds or less.

The mold varies depending on the type of resin, but the temperature is set between 100 and 250 ℃, preferably between 150 and 220 ℃, after the resin crystal has sufficiently advanced and residual stress is reduced, the molded product is better than the mold. Taken out. The wall thickness of the molded container is 100 μm to 2 mm, preferably 200 μm to 1 mm.

If the molding temperature is too low, molding stress remains and the heat distortion temperature decreases, which is a practical problem.

Since the poly-3-methylbutene-1 resin composition of the present invention is far from crystallized, the mold holding time may be short, 2 seconds or more,
Usually 5 seconds or less is sufficient. Therefore, it is possible to mold in a very short cycle. In addition, the poly 3-of the present invention
Since the methylbutene-1 resin has a good mold releasability, it has an advantage that it can be easily taken out from the mold after molding and the defective rate is small.
Regarding cooling of the container after taking it out of the mold, a cooling mold can be used if necessary.

The container used as a molded product in the present invention is an upper opening type container. The upper opening type container means a container having an open upper part and having a self-shape retaining property, such as a tray shape, a dish shape, a cup shape, a box shape, and a container provided with a partition. For example, a soft container such as a bag is not referred to as an upper opening type container in the present invention.

The poly-3-methylbutene of the present invention molded as described above
The container made of 1 resin composition has high heat resistance, and even if it is kept at an ambient temperature of 160 ° C. which causes deformation in polypropylene,
There is no distortion such as twisting or warping, and there is no problem of yellowing. Furthermore, by selecting appropriate resin and molding conditions, it does not cause problems such as deformation or discoloration even at 200 ° C or higher, and has heat resistance up to 240 ° C.

Also, compared to C-PET, there is no reduction in impact strength after heating,
Also in this sense, it can be said that the heat resistance is high.

Moreover, the impact strength is particularly high at low temperatures, and the falling weight impact strength at -20 ° C is 10 kg · cm / cm or more. In addition, the difference in impact strength between 30 ℃ and -20 ℃ is 1/2 for commercial C-PET products.
While it will be 0 or less, in the container of the present invention 1/2 ~
It is about 1/5, and is characterized by a small decrease from impact strength at room temperature.

〔Example〕

Examples will be shown below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

Physical property values in the following examples were measured by the following methods.

-The melt index (MI) is ASTM D1238 (320
C., 2.16 kg load).

The melting point and heat of fusion of the copolymer were determined by measuring with a 9900 type differential scanning calorimeter (DSC) manufactured by Dupont. The melting curve was measured on a sample that was once cooled in the DSC apparatus after being melted.

The peak top was adopted as the melting point. When two or more peak tops were shown, each was regarded as a melting point. The heat of fusion was calculated from the area enclosed by the melting curve and the same tangent line, in principle.

・ The content of each component of the copolymer is ¹³ C high resolution at 310 ° C by JEOL FX200 type NMR system (high temperature temperature variable device installed)
The NMR spectrum was measured and determined.

-Vacuum and pressure molding were performed using a vacuum pressure molding machine (with plug assist) manufactured by Asano Laboratory Co., Ltd. The molding conditions such as molding temperature and mold temperature are shown in Table 2 together with the results of physical property evaluation. In addition, about the resin composition which has two or more melting | fusing points, the average value was calculated | required and the molding temperature was determined based on the value.

The shape of the mold is a rectangular container with a size of 15 cm x 12.5 cm x depth 2.5 cm.

・ Measurement of heat resistance (oven test) Using a RO-1900 type microwave oven manufactured by Mitsubishi Electric Corp., measure the time until the deformation starts by heating from room temperature in an oven with a temperature setting of 250 ° C. did.

The molded product was placed in a gear oven set to 200 ° C, 230 ° C, and 240 ° C, and after 15 minutes, the appearance was taken out and the appearance was confirmed.
(The gear oven is Tabai Gear Oven GPS-112.
The mold was used. ) ・ Measurement of heating rate of contents by microwave oven 100 cc of salad oil was put into a molded mold, and the internal temperature was measured with time to measure the easiness of heating the contents. (RO-1900 type microwave oven manufactured by Mitsubishi Electric Corp. was used as the microwave oven.) ・ The sample of the poly-3-methylbutene-1 resin composition used for measuring the falling weight impact strength was 200 ° C.-1 hr after molding. The heat-treated product was measured, and the commercially available C-PET container was measured as it was. The measuring device is a drop tester manufactured by Rheometrics Co., the height of the falling weight is 50.292 cm, and the weight of the falling weight is 3.
It was measured at 6197 kg and a falling weight velocity of 3.3337 M / S. Measurement temperature is 30
℃ and -20 ℃.

The measurement at low temperature was performed after cooling the temperature of the measurement chamber with liquid nitrogen to a predetermined temperature. The measured value was expressed by dividing the amount of energy required for destruction by the sample thickness.

The sample piece was cut out from the bottom of the container, fixed to a clamp having an inner diameter of 1.5 inches, and used for the measurement.

Example of catalyst preparation At room temperature, 515 ml of purified toluene was put into an autoclave with a volume of 1 which was sufficiently replaced with nitrogen, and n-butyl ether 65.1 g (0.5 mol) titanium tetrachloride 94.9 g (0.5 mol) was added with stirring.
And diethylaluminum chloride 28.6g (0.24mol)
Was added to obtain a brown homogeneous solution. Then, the temperature is raised to 30 ° C. After 30 minutes have passed, the temperature is raised to 40 ° C and left for 2 hours at 40 ° C.
Hold. Then 32 g of titanium tetrachloride (0.17 mol) and
15.5 g of tridecyl methacrylate (0.058 mol) was added and the temperature was raised to 98 ° C. After holding at 98 ° C for 2 hours, a granular purple solid was separated and washed with toluene to obtain solid titanium trichloride.

Resin Production Example-1 Diethyl aluminum monochloride 1 was placed in an induction-stirring autoclave with a volume of 5 that was fully dried and purged with argon.
1.2 mmol and 3-methylbutene-1, 3000 ml were charged. After raising the internal temperature to 80 ° C., 3078 mg of the solid titanium trichloride catalyst component obtained in the catalyst production example was pressure-inserted with argon gas to start the first stage polymerization. Octene-1 continuously at the same time
Copolymerization of 3-methylbutene-1 and octene-1 was carried out at 80 ° C. for 90 minutes while supplying hydrogen. The total amount of octene-1 supplied to the first stage was 19.3g, and the total hydrogen amount was 0.12mmol.
And

Next, the supply of octene-1 was increased at the same time as the supply of hydrogen was stopped, and the second stage copolymerization of 3-methylbutene-1 was carried out at 80 ° C. for 42 minutes. The total supply of Octene-1 in the second stage was 49.3 g.

Then, the temperature was immediately lowered to 40 ° C., and simultaneously 575 ml of octene-1 and 322 ml of 4-methylpentene-1 were charged under pressure with argon, and the third stage polymerization was carried out at 40 ° C. for 30 minutes.

200 ml of isobutanol was injected with argon to terminate the polymerization, and at the same time, unreacted monomer was expelled to remove n-hexane 20.
After charging 00 ml and stirring at 40 ° C. for 60 minutes, the temperature was lowered to room temperature and the supernatant was extracted. This operation was repeated 6 times to wash and remove the catalyst component in the polymer, and then dried to obtain 793 g of a white powdery 3-methylbutene-1 polymer composition.

The proportions of the respective components in the polymer sampled in small amounts at the end of the first stage, the second stage and the third stage were 60% by weight for the first stage polymer (component (a)), respectively. The content of octene-1 in the component a) is 3% by weight, the content of the second stage polymer (component (b)) is 30% by weight, and the octene-1 in the component (b) is
1 content is 17% by weight and the content of the third stage polymer (component (c)) is 10
% By weight, octene content in component (c) is 40% by weight, 4
-Methylpentene-1 content was 30% by weight.

In addition, the amorphous and low molecular weight components soluble in n-hexane (hereinafter n-hexane soluble components) were 1.
It was 9% by weight.

Based on 100 parts by weight of the obtained polymer composition, MARKAO-18, M
ARKAO-412S (trade name; all manufactured by Adeka Argus)
After adding each 0.25 part by weight and 0.2 part by weight of Irgafoss P-EPQ (trade name; manufactured by Nippon Ciba-Geigy Co., Ltd.), pelletization was performed by an extruder at 320 ° C.

This product had melting points of 294 and 289 ° C and a melt index (hereinafter referred to as MI) of 0.99 g / 10 minutes. A sheet having a thickness of 600 μm was formed from the pellets and subjected to vacuum and pressure forming.

The polymerization results are shown in Table 1.

Resin Production Examples-2 to 4 Other than Resin Production Example-1 except that the composition ratios of the components (a), (b), and (c), the comonomer content, and the type of comonomer were changed as shown in Table 1. Was done in the same way. The polymerization results are shown in Table 1. However, in Resin Production Examples 3 and 4, the heat stabilizer was Irganox 1010, Irgafoss P-EPQ (trade name; all manufactured by Ciba-Geigy Co., Ltd.), and 0.2 parts by weight of hydroanthracene.

Resin Production Example-5 Diethyl aluminum monochloride 39 was placed in an induction-stirring autoclave with a volume of 5 which was thoroughly dried and purged with argon.
mmol and 3-methylbutene-1 3500 ml, butene-1
103 ml was charged. After the internal temperature was raised to 80 ° C., 3000 mg of the solid titanium trichloride catalyst component obtained in the catalyst production example was injected under pressure with argon gas to start polymerization.

While supplying 195 ml of butene-1 continuously, at 80 ° C. 3-
Copolymerization of methylbutene-1 and butene-1 was carried out for 180 minutes. The total butene-1 fed was 298 ml.

Then, 200 ml of isobutanol was press-fitted with argon to stop the polymerization, and the unreacted monomer was expelled.
-2000 ml of hexane was charged, and the mixture was stirred at 60 ° C for 60 minutes and then cooled to room temperature, and the supernatant was extracted. This operation was repeated 5 times to wash and remove the catalyst component in the polymer and then dried to obtain 945 g of a white powdery 3-methylbutene-1 copolymer. The additives were the same as in Resin Production Examples-3 and 4. The results are shown in Table 1.

Resin Production Examples 6 to 9 Except that in Resin Production Example-1, the composition ratios of the components (a), (b), and (c), the comonomer content, and the type of comonomer were changed as shown in Table 1. The same was done. The polymerization results are shown in Table 2.

However, in Resin Production Examples 6, 7 and 9, the heat stabilizer was Irganox 1
010 (trade name; manufactured by Nippon Ciba Geigy) was 0.8 parts by weight.

Further, in Resin Production Example 8, the heat stabilizer was Irganox 10
10, Irgafos-P-EPQ (trade name; all manufactured by Ciba-Geigy Co., Ltd.) 0.2 parts by weight each.

Example-1 The sheet having a thickness of 600 µm obtained in Resin Production Example-1 was vacuum-pressure formed by a vacuum-pressure forming machine manufactured by Asano Laboratory.

The temperature of the heater was set to 600 ° C for both upper and lower sides. When the surface temperature of the resin reached 295 ° C. by heating, the heater was moved by automatic control, the mold was set instead, and vacuum pressure molding was performed.

The mold temperature was set to 190 ° C. and the holding time was 5 seconds. 5
After a few seconds, the mold was opened, and at the same time, compressed air spouted from below, and the molded resin was removed from the mold. The releasability was good.

After trimming the obtained molded product, a heat resistance test and an impact resistance test were performed. As a heat resistance test, 200
It was placed in each gear oven at ℃, 230 ℃ and 240 ℃, taken out after 15 minutes, and the deformed appearance of the molded product was observed.

No deformation was observed at each temperature. Drop weight impact strength at 30 ℃ / -20 ℃ is 170 and 95kg respectively at thickness of 400μm.
It was cm / cm. The physical property evaluation results are summarized in Table 2.

Example-2 The sheet having a thickness of 600 μm obtained in Resin Production Example-2 was molded in the same manner as in Example-1.

However, the resin surface temperature during molding was set to 285 ° C and the mold temperature was set to 190 ° C. The mold holding time was 4 seconds.

For evaluation of heat resistance, measurement of deformation time by a microwave oven was additionally added. The results of evaluation of physical properties are summarized in Table 3.

Example-3,4,5,6,7,8 Each of the resins obtained in Resin Production Examples-3,4,6,7,8,9 was molded. Resin surface temperature, mold temperature, mold holding time,
Table 3 shows the appearance test using a gear oven and the measured impact strength. For Example 6, the gear oven test was conducted at 250 ° C instead of 240 ° C.

Comparative Example-1 A commercially available C-PET container (Pet Cooker manufactured by Lispack Co., Ltd.) was placed in a gear oven at 200 ° C, 230 ° C, and 240 ° C for 15 minutes, heated, taken out, and the appearance was observed. At 200 ° C and 230 ° C, there was no change in appearance, but at 240 ° C, deformation due to heat shrinkage was observed. The results are shown in Table 2.

Comparative Example-2 A commercially available C-PET container (Pet Cooker, manufactured by Lispack Co., Ltd.) was placed in a microwave oven and heated at a preset temperature of 250 ° C. to measure the time until the start of deformation.

The deformation start time was 9.0 minutes. The results are shown in Table 2.

Comparative Example-3 The impact strength of a commercially available C-PET container (Pet Cooker, manufactured by Lispack Co., Ltd.) was measured at 30 ° C / -20 ° C. In particular, the impact strength at -20 ° C was as low as 4 kg · cm / cm. Second result
Shown in the table.

Comparative Example-4 The resin obtained in Resin Production Example-5 was molded. A 500 μm sheet made from this resin is molded at a molding temperature of 275 ° C.
Molding was performed at a mold temperature of 160 ° C. and a holding time of 5 seconds.

When the molded product was left in a gear oven at 200 ° C for 15 minutes, deformation occurred.

Further, the temperature was set to 250 ° C. in a microwave oven and the temperature was raised from room temperature, but deformation occurred within 9 minutes of heating.

The low temperature impact strength was 9 kg · cm / cm, which was higher than that of C-PET, but lower than that of the rubbery copolymer-containing poly-3-methylbutene-1 resin of the present invention.

Example-5, Comparative Example-5 The molded product of Example-1 was charged with 100 cc of salad oil and heated with a microwave oven at a power of 500 W. Example 5 In a commercially available C-PET container (Pet Cooker manufactured by Lispack Co., Ltd.) of the same shape, 100 cc of salad oil was also added.
And heated by the same method.

(Comparative Example-5) Fig. 1 shows the relationship between the heating time and the temperature of the salad oil.

As is apparent from the figure, the container made of poly-3-methylbutene-1 resin according to the present invention has a higher utilization efficiency of high frequency and a better heating of contents than the container made of C-PET.

[Effects of the Invention] The upper open container made of poly-3-methylbutene-1 resin according to the present invention has high heat resistance as a container that can be used in both an oven and a microwave oven. Withstands use and can be used at 240 ℃.

Further, when heated in a microwave oven, since the absorption or reflection of high frequency is less than that of a container made of C-PET, the food in the container has good heating efficiency and the temperature of the food rises in a short time.
Alternatively, there is an advantage that the food temperature rises with less power consumption.

Further, in most cases, foods cooked in a microwave oven, oven, etc. are frozen, stored and transported in a container, but the container made of the poly-3-methylbutene-1 resin of the present invention is used. Has an extremely high impact resistance at freezing temperature as compared with a C-PET container, so that there is a great advantage that the container is less damaged during frozen storage.

Further, on the molding surface, crystallization is fast and the mold releasability from the mold is good, so that it is possible to shorten the molding cycle and mold the container with high production efficiency.

[Brief description of drawings]

FIG. 1 is a diagram showing the relationship between the heating time and the temperature of salad oil based on Example-5 and Comparative example-5. In the figure, 1 shows the result of Example-5, that is, the case of using the container made of the poly-3-methylbutene-1 resin according to the present invention. Reference numeral 2 in the figure shows the result when Comparative Example-5, that is, when a commercially available C-PET container was used.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number within the agency FI technology display location (C08L 23/20 23:02) B29K 23:00 (72) Inventor Hidehito Kato Midori Yokohama City, Kanagawa Prefecture Sanryo Kasei Industry Co., Ltd. 1000, Kamoshida-cho, Tokyo (72) Inventor Katsuji Shibata 1000 Kamoshita-cho Sanroku Kasei Co., Ltd., Midori-ku, Yokohama, Kanagawa Sanryo Kasei Kogyo Co., Ltd. (56) References 16897 (JP, B2)

Claims (6)

[Claims] 1. A poly-3-methylbutene-1 resin obtained by forming a poly-3-methylbutene-1 resin containing 1 to 30% by weight of a rubbery α-olefin copolymer into a sheet and then thermoforming the sheet. Top open container. 2. The container according to claim 1, wherein the container has a wall thickness of 100 μm to 2 mm. 3. The container according to claim 1, wherein the rubbery α-olefin copolymer contains 3 to 50% by weight of 3-methylbutene-1 unit. 4. A poly-3-methylbutene-1 resin containing a rubbery α-olefin copolymer produced by a multi-step polymerization method including a polymerization step of the rubbery α-olefin copolymer. The container according to claim 1, characterized in that 5. A melting point of poly-3-methylbutene-1 resin containing a rubbery α-olefin copolymer is 250 ° C. to 310 ° C.
℃, heat of fusion 4cal / g or more, melt index 0.1 to 1
The container according to claim 1, wherein the container has a weight of 00 g / 10 minutes. 6. No deformation occurs at a temperature of 160 ° C., and −2
The container according to claim 1, which is a heat-resistant container having a falling weight impact strength of 10 kg · cm / cm or more at 0 ° C.