JPH02650A - Top-opening container made of poly(3-methylbutene-1) resin - Google Patents

Abstract

PURPOSE:To provide the subject container excellent in heat resistance, low- temperature impact resistance and heating efficiency and desirable as a container for both a microwave range and a microwave over by forming a specified poly(3-methylbutene-1) resin into a sheet and thermoforming this sheet. CONSTITUTION:A poly(3-methylbutene-1) resin containing 1-30wt.% rubberlike alpha-olefin copolymer (e.g., octene-1/3-methylbutene-1 copolymer) is produced and formed into a sheet. This sheet is thermoformed by, for example, softening the sheet by heating, uniformly developing the softened sheet in a mold by applying a vacuum and/or compressed air and sufficiently causing its orientation and crystallization to produce a top-opening container made of the poly(3- methylbutene-1) resin. The obtained container does not undergo deformation at 160 deg.C and has a falling weight impact resistance >=10kg.cm at -20 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a heat-resistant container made of poly-3-methylbutene-1 resin. More specifically, it is a heat-resistant top-opening type made of poly-3-methylbutene-1 resin containing a rubbery α-olefin copolymer, which can withstand heating in a microwave oven and open use at temperatures of 160° C. or higher, preferably 200° C. or higher. Regarding containers.

BACKGROUND ART In recent years, with the increase in the number of dual-earner households and the increase in the number of single-income households, there has been an increase in demand for instant foods that shorten cooking time or are convenient to prepare beforehand. These trends, together with the widespread use of microwave ovens in recent years, have attracted attention to heat-resistant containers that can be used in both microwave ovens and ovens.

[Conventional technology]

Expanded polystyrene has conventionally been widely used as containers for instant foods, but polystyrene has a low softening temperature and insufficient heat resistance for use in microwave ovens, ovens, and the like.

Polypropylene is a resin with higher heat resistance than polystyrene. Polypropylene resin containers usually have sufficient heat resistance when heating foods with a high moisture content in a microwave oven, but containers with a high oil content or 160"
Cannot withstand use in ovens above C.

On the other hand, so-called easily crystallized polyethylene terephthalate (C-P
Thin-walled containers made by (referred to as ET) are also oil-resistant and are being used as containers that can be used both in microwave and ovens.

- [Problems to be Solved by the Invention] However, such polyethylene terephthalate containers have the following inadequacies.

First, although this type of instant food is often stored frozen, C-PET containers have insufficient #Ji impact resistance at low temperatures.

In addition, regarding heat resistance, C-PET containers can reach up to 220°C.
Although it is said that it can withstand use at temperatures of up to 230°C, in reality, when a CPETPET container is used in a household microwave oven, it easily deforms at high temperatures and cannot be put to practical use. In addition, crystallization progresses after cooking, resulting in a significant drop in impact resistance. Furthermore, compared to glass containers, C-PET containers raise the temperature of the contents more slowly when heated at the same output, that is, have lower efficiency in using high frequencies.

[Means for solving problems]

In view of the current state of heat-resistant containers as described above, the present inventors conducted intensive studies on the application of poly-3-methylbutene-1, which is a polyolefin with a high melting point and high crystallinity, to the heat-resistant containers. The inventors have discovered that it is possible to obtain a heat-resistant container with good performance that improves the drawbacks of heat-resistant containers made of other resins, and has arrived at the present invention.

That is, the present invention uses 1 to 3 rubbery α-olefin copolymers.
A poly 3-methylbutene-1 resin containing 0% by weight is formed into a sheet and then thermoformed to form a poly 3-methylbutene-1 resin container with an open top.

The present invention will be explained in detail below.

Poly-3-methylbutene containing 1 to 30% by weight of the rubbery α-olefin copolymer used in the present invention
1 resin (hereinafter, this may be simply referred to as a poly-3-methylbutene-1 resin composition) is a 3-methylbutene-1 homopolymer, or a combination of 3-methylbutene-1 and another α-olefin. A copolymer blended with a saturated rubbery substance can be used. The rubbery substance used here is 3-methylbutene-1 (co-)
From the viewpoint of compatibility with the polymer, a rubber-like copolymer of α-olefin having 2 to 20 carbon atoms is preferable, and in particular, a rubbery copolymer containing 3-methylbutene-1 units in an amount of 3 to 50% by weight. A binary or ternary rubbery copolymer with another α-olefin having 2 to 20 carbon atoms is used.

The content of the rubbery substance in the poly-3-methylbutene-1 resin composition is 1 to 30% by weight, preferably 3 to 25% by weight.
It is. If the content of the rubbery substance is more than the upper limit, heat resistance will be insufficient. Moreover, if the content of the rubbery substance is less than the lower limit, moldability and impact resistance will be insufficient.

The blending method is not particularly limited, and methods such as blending in a solution, blending using an axle or twin-screw pusher, or a kneader such as a Banbury mixer can also be carried out, but preferably, 3-methylbutene-
A method of blending by carrying out homopolymerization of 1 or copolymerization of 3-methylbutene 1 and other α-olefins and polymerization of a rubber-like copolymer in multiple stages is preferable. The multi-stage polymerization method will be described later.

32 of the poly-3-methylbutene-1 resin composition of the present invention.
The melt index measured according to ASTM D1238 at 0°C is between 0.1 and 100 g/10 min, preferably between 0.5 and 70 g/10 min. If the melt index is higher than the upper limit, the fluidity is good and the sheet formability is good, but on the other hand, there is drawdown of the sheet during thermoforming, and the formability during thermoforming (reduced considerably). Impact strength also decreases.If the melt index is lower than the lower limit, impact strength is high, but
Molding becomes impossible or 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 article be within the above-mentioned range in order to obtain good physical properties.

DSC of poly3-methylbutene-1 resin composition of the present invention
The melting point measured at is 250°C to 310°C. Particularly preferably, the melting point is between 270°C and 305°C. When the melting point is higher than the upper limit, the molding temperature becomes too high and the polymer tends to deteriorate during molding. Moreover, if the melting point is lower than the lower limit, (1) the thermal properties are insufficient.

Further, the heat of fusion of the poly-3-methylbutene-1 resin composition of the present invention measured by DSC is 4 cal/g or more, preferably 6 cal/g or more. A low heat of fusion means a low degree of crystallinity, which is undesirable because it leads to a decrease in heat resistance.

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-step polymerization method, in the first step, a homopolymer of 3-methylbutene-1, or more preferably a random polymerization of 3-methylbutene-1 and a small amount of other α-olefin having 2 to 2 carbon atoms is used. A method of producing a copolymer and subsequently producing a rubbery copolymer by copolymerizing 3-methylbutene-1 and other α-olefins in the presence of the first-stage polymer and a catalyst is conceivable. Other α- having 2 to 2 carbon atoms
As olefins, ethylene, propylene, butene
1. Straight chain α such as hexene-1, octene-1, decene-1, dodecene-1, tetradecene-1, octadecene-1, etc.
Branched α-olefins such as -olefin, 4-methylpentene-1,3-methylpentene-1, and vinylcyclohexene are mentioned. Normally, linear α-olefins are used.

In this case, the content of heptamers other than 3-methylbutene-1 in the first-stage random copolymer is 15% by weight or less,
Preferably it is 10% by weight or less.

The rubbery copolymer in the second stage is 3-methylbutene-
3-methylbutene-1, the content of which is not more than 50% by weight
and another α-olefin having 2 to 20 carbon atoms, or a copolymer of two or more types of α-olefins having 2 to 20 carbon atoms.

Other α-olefins are selected from those that can be used in the first stage. The copolymerization method is preferably a so-called random copolymerization method. Branched α-olefins are also linear α-olefins.
-Used in the same way as olefins.

Copolymers of two or more α-olefins other than 3-methylbutene-1 include, for example, ethylene-propylene, ethylene-4-methylpentene-1, propylene-4-methylpentene-1,4-methylpentene-1 ~octene-1,4-methylpentene-1 ~decene-1,4-methylpentene-1 ~dodecene-1,4-methylpentene-
Copolymers such as 1-decene-1 and tetradecene-1, each having a comonomer content of about 30 to 70% by weight, may also be used, but preferably the same components are 3-methylbutene-1 and other comonomers. It is a copolymer with α-olefin. Two or more types of other α-olefins 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, the tear strength and impact strength of the molded article are insufficiently improved. As mentioned above, the proportion of the second stage component in the total polymer is 1 to 3.
0% by weight, preferably from 3 to 25% by weight.

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

When the components obtained in the first, second, and third stages of the three-stage polymerization method are respectively called (a+, (bL) components, the (al component is 3-methylbutene-1 monomer). Combination, or 3-methylbutene-1 with a 3-methylbutene-1 content of more than 90% by weight and other α having 2 to 20 carbon atoms
- It is a copolymer with an olefin.

The other α-olefin having 2 to 20 carbon atoms in the copolymer is selected from those that can be used in the first stage of the two-stage polymerization method. The copolymerization method is preferably a so-called random copolymerization method. (3-methylbutene-1 in the al component
If the content is less than 90% by weight, the final three-stage polymer will have insufficient melting point and crystallinity, resulting in insufficient heat resistance.

The proportion of the (al component) in the three-stage polymerization composition is 10 to 85% by weight, preferably 30 to 70% by weight.

Component (b) has a 3-methylbutene-1 content of 90 to 60
Weight% of 3-methylbutene-1 and carbon number 2-20
It is a copolymer with other α-olefins. Other α-olefins are selected from those that can be used in component (a). Two or more 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, preferably 85 to 60% by weight. If the content of 3-methylbutene-1 is too high, impact strength will decrease. Moreover, if it is too small, heat resistance will be insufficient. The proportion of the BL component in the three-stage polymer composition is selected from the range of 10 to 85% by weight, preferably 20 to 50% by weight. and lack of heat resistance.

(As for the C1 component, 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.

A polymer obtained by three-stage polymerization has excellent uniform dispersibility of rubbery components and can simultaneously obtain higher heat resistance and impact resistance than a polymer obtained by two-stage polymerization.

The poly-3-methylbutene-1 resin composition of the present invention is characterized by its excellent impact resistance and thermoformability, and such properties cannot be obtained with a random copolymer that does not contain a rubbery component.

Next, the polymerization method will be explained.

In aliphatic, cycloaliphatic or aromatic hydrocarbons 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 Group 1 to 3 metal of the periodic table in a liquid olefin or in the absence of a solvent. polymerize.

In the case of three-step polymerization, the (al component and (b) component are produced, and then the (C) component is produced. Preferably, the (al component, then the (bl component), and finally the (C) component are produced in this order. This is because (
This is particularly good in terms of preventing elution of the C1 component.

In the case of two-stage polymerization, it is also preferable to polymerize the rubbery component last.

There are no particular restrictions on the transition metal compound and the organometallic compound of Group 1 to Group 3 metals of the periodic table, which are catalysts, and those commonly used in the polymerization of olefins can be used. Preferably, it is a combination of a solid catalyst component containing Mg, Ti, halogen, and an electron-donating compound such as an ether or ester, an organoaluminium compound, and, if necessary, an electron-donating compound such as an ether. Such a solid catalyst component is disclosed in Japanese Patent Application Laid-open No. 52-98076,
-24378 publication, 53-85877 publication, 53-85877 publication
It is described in Publication No. 3-117083, Publication No. 59-6204, Publication No. 59-11306, etc. Further, a solid titanium trichloride catalyst component having an aluminum content in an atomic ratio of aluminum to titanium of 0.15 or less and containing a complexing agent, an organoaluminum compound, especially an aluminum dialkyl monohalide, and optionally an ether Combinations with electron-donating compounds such as esters, esters, etc. are also preferably used. Such a solid titanium trichloride catalyst component is disclosed in Japanese Patent Publication No. 55-8451 and Japanese Patent Publication No. 55-8451.
No. 8452, No. 558003, No. 54-27
No. 871, No. 55-39165, No. 55-1
It is described in Publication No. 4054, Publication No. 53-44958, etc.

The polymerization temperature is 0-150°C. Further, a molecular weight regulator such as hydrogen may be used if necessary.

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

Further, multi-stage polymerization methods are described in Japanese Patent Application Laid-open No. 6)-7349 and Japanese Patent Application No. 62-72083.

Since the container of the present invention is used at high temperatures, it is important to select a heat stabilizer, and in particular, one that is less likely to scatter at high temperatures is preferred.

An example of such an additive is Iganox 1010.
(product name; manufactured by Nippon Ciba Geigy Co., Ltd.), Irgafuos P-EPQ (product name; manufactured by Nippon Ciba Geigy Co., Ltd.) and in some cases, a combination of dihydroanthracene, Irganox 1010, and MARKAO-412S (product name; manufactured by Adeka Argus Co., Ltd.) and in some cases, a combination of Irgafuos PEPQ, MARKAO-18 (product name; manufactured by Adeka Argus), MARKAO-412
3 (trade name; manufactured by Adeka Argus) and, in some cases, a combination of Irgafuos P-EPQ.

In addition, Lasmit HPM-12 (trade name: Dai-Kogyo Seiyaku Layer), Irgafuos 168 (trade name; manufactured by Nippon Ciba Geigy Co., Ltd.), DSTDP, etc. are also effective.

As the antioxidant used in the present invention, it is more preferable to use a hindered phenol compound that satisfies the requirement that the 1.0% weight loss temperature measured by a thermal balance analyzer (TGA) is 290° C. or higher.

The 1.0% weight loss temperature measured by TGA here refers to the polymerization zone measured at a heating rate of 15°C/min under an air flow of 11,100 ml for 11 minutes, and a weight loss of 1.0 weight% was observed. This is the temperature when

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[l,1-dimethyl-2-(β-(3-t-butyl-4-hydroxy-5-methylphenyl)propynyloxy)ethyl)-2,4,8,10-tetraoxysuspiro f :5.5) It is desirable to use undecane alone or in combination.

The amount of antioxidant added is 3-methylbutene-1 homopolymer or 3-methylbutene-1 and other α-
0.1 to 100 parts by weight of copolymer with olefin
The amount is 3 parts by weight, preferably 0.2 to 2 parts by weight.

If the amount is less than 0.1 part by weight, a sufficient effect cannot be obtained, and 3
If it is used in excess of 1 part by weight, the effect will not be improved and it will be economically disadvantageous, and in some cases, the antioxidant may bleed or the physical properties may deteriorate, which is not preferable.

As a method for molding the container of the poly-3-methylbutene-1 resin composition of the present invention, preferably a thermoforming method is used. The thermoforming method is described in the "Practical Plastic Terminology Dictionary" (edited by Shoji Seto, Plastic Age, 1975) or the on-site manual "Thermoforming (vacuum forming, pressure forming)".
(Shigeru Institute of Chemical Research, (ISS Kano Research Institute Kazuo Asano)
It is a method of processing a sheet of thermoplastic resin, in which the heated and softened sheet is cooled while being deformed by some external force, and a molded product is made. Examples include molding (vacuum, pressure forming), drape molding, reverse draw molding, air slip molding, plug assist molding, plug assist reverse draw molding, contact heating pressure molding, and the like. Normally, vacuum or pressure forming with plug assist is sufficient to obtain a molded product in the desired shape.

To give an overview of vacuum and pressure forming, a sheet of the poly3-methylbutene-1 resin composition described above is formed, then the sheet is heated and softened, and the softened sheet is placed in a mold by vacuum and/or pressure. Spread and stretch uniformly. Thereafter, after crystallization has sufficiently progressed within the mold, the molded product is taken out from the mold. The sheet can be formed by a conventional method such as T-die extrusion. The thickness of the sheet is usually 200 μm to 2.51 μm, preferably 300 μm
μm~l, 5 * seal. If the thickness of the sheet exceeds this value, it becomes difficult to uniformly heat the sheet, and crystallization progresses unevenly in various parts of the sheet, which is undesirable.

The heating temperature of the sheet is 220 to 310°C, preferably 2
50 to 300°C, but ±20°C of the melting point of the resin composition
A range of 15+10° C., which is the melting point, is usually optimal.

Next, when the sheet becomes translucent by heating, it is desirable to apply vacuum or compressed air to form the sheet.

If the heating time is too long or the heating temperature is too high,
This is not preferable because it causes deterioration of the resin and decreases its physical properties.

The heating time is usually 30 seconds or less.

The mold temperature varies depending on the type of resin, but the temperature is 100-250℃,
The temperature is preferably set between 150 and 220° C., and after the resin has sufficiently crystallized and residual stress has been reduced, the molded product is removed from the mold.

The wall thickness of the molded container is 100 μm to 2B, preferably 200 μm to 11 m.

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

Since the poly-3-methylbutene-1 resin composition of the present invention is slow to crystallize, the mold holding time may be short, and may be held for 2 seconds or more.
Usually 5 seconds or less is sufficient. Therefore, it is possible to mold in a very short cycle. Moreover, the poly 3-
Methylbutene-1 resin has good mold releasability, so it is easy to take out from the mold after molding, and has the advantage of having a low defect rate.

Regarding cooling of the container after being taken out from the mold, a cooling mold can be used as necessary.

The container used as a molded article in the present invention is a top-opening container. The term "open-top container" refers to a container that is open at the top and has self-shape retention, such as a tray-shaped, dish-shaped, cup-shaped, box-shaped container, or a container having a partition. For example, soft containers such as bags are not referred to as top-open containers in the present invention.

Poly 3-methylbutene of the present invention molded as described above
Containers made from the No. 1 resin composition have high heat resistance, and even when maintained at an ambient temperature of 160° C., which causes deformation in polypropylene, there is no deformation such as twisting or warping, and there is no problem of yellowing. Furthermore, by selecting appropriate resins and molding conditions, there will be no problems such as deformation or discoloration even under conditions of 200°C or higher.
Heat resistant up to 0℃.

Furthermore, compared to C-PET, there is no drop in impact strength after heating, and in this sense, it can be said that it has high heat resistance.

In addition, the impact strength is especially high at low temperatures, and the falling weight impact strength at -20°C is 10 kg -cm/cTf1 or more. Furthermore, while the difference in impact strength between 30°C and -20°C is less than 1/20 for commercially available C-PET products, it is about 1/2 to 115 for the container of the present invention.
It is characterized by a small drop in impact strength from normal temperature.

〔Example〕

Examples will be shown below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

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

Melt index (MI) is ASTM D1238
(320°C, 16kg load).

The melting point and heat of fusion of the copolymer are as follows: 1) 99 manufactured by Upont
It was determined by measuring with a 00 type differential scanning calorimeter (DSC). The melting curve was measured on a sample that was melted in a -degree DSC apparatus and then slowly cooled.

The peak top was used for the melting point. In cases where two or more peak tops were shown, each was also regarded as the melting point. In principle, the heat of fusion was calculated by drawing a tangent to the base of the peak and calculating the area surrounded by the tangent to the melting curve.

The content of each component of the copolymer is JEOL FX200 type NM.
I at 310°C with R device (equipped with high temperature variable device)
It was determined by measuring a 3C high-resolution NMR spectrum.

Vacuum and pressure forming were performed using a vacuum and pressure forming machine (with plug assist) manufactured by Asano Laboratory Co., Ltd. molding temperature,
The molding conditions such as mold temperature are shown in Table 2 together with the physical property evaluation results. For resin compositions having two or more melting points, the average value was determined, and the molding temperature was determined based on that value.

The shape of the mold is 15em x 12.5 mark x depth 2.5cm
It is a square container.

(Oven test) ■ Using a Mitsubishi Electric RO-1900 microwave oven, the temperature was raised from room temperature in an oven set at 250°C, and the time until deformation started due to heating was measured.

■ The molded product was placed in a gear oven set at 200°C, 230°C, and 240°C, and after 15 minutes, it was taken out and its appearance was checked. (Tabai Gear Oven GPS-112 model was used as the gear oven.) 100cc of salad oil was placed in a mold that had been heated in the microwave, and the internal temperature was measured over time to determine how easily the contents were heated. did.

(The microwave oven used was a Mitsubishi Electric RO-1900 model microwave oven.) The sample of the poly-3-methylbutene-1 resin composition used for the 1" U1 prong measurement was 200" C-1 after molding. Measurements were made on containers that had been heat-treated for 1 hour, and measurements were taken on commercially available C-PET containers as they were.The measurement device was a drop tester manufactured by Rheometrinx, and the drop weight height was 50, 29.
2 cm, falling weight weight 3.6) 97 kg, falling weight speed 3.3
Measured at 337M/S. The measurement temperature is 30°C and -20°C.
It is °C.

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

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

Catalyst Production Example At room temperature, 515 ffil of purified toluene was placed in an 11 capacity autoclave which had been sufficiently purged with nitrogen, and with stirring, n
-butyl ether 65.1 g (0.5 mol), titanium tetrachloride 94.9 g (0.5 mol) and diethylaluminum chloride 28.6 g (0.24
mol ) was added to obtain a brown homogeneous solution. then 3
Raise the temperature to 0°C. After 30 minutes, the temperature was raised to 40°C and kept at 40°C for 2 hours. Thereafter, 32 g of titanium tetrachloride (0.17 mol) and 15.5 g of tridecyl methacrylate (0,058 mol) were added, and the temperature was raised to 98°C. After being kept 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 Capacity 5 after being thoroughly dried and replaced with argon! Diethylaluminum monochloride 1 in an induction stirred autoclave
1.2 mmol and 3-methylbutene 1.3000
mf! , was prepared. After raising the internal temperature to 80°C, the solid titanium trichloride catalyst component 3078 obtained in the catalyst production example
(2) was pressurized with argon gas to start the first stage polymerization. 80° while continuously supplying octene-1 and hydrogen at the same time.
Copolymerization of 3-methylbutene-1 and octene-1 with C
This was done for 0 minutes. The total amount of octene-1 supplied to the first stage was 19.3 g, and the total amount of hydrogen was 0.12 mmol.

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

Then, the temperature was immediately lowered to 40°C, and at the same time, octene-1575d and 4-methylpentene-1322d were introduced under pressure with argon, and the third stage polymerization was carried out at 40°C for 30 minutes.

200 ml of isobutanol was pressurized with argon to stop the polymerization, and at the same time unreacted monomers were expelled, 2000 ml of n-hexane was added, and the mixture was stirred at 40°C for 60 minutes.
The temperature was lowered to room temperature and the supernatant liquid was extracted. This operation was repeated six times to wash and remove the catalyst component in the polymer, and then dried to form a white powdery 3-methylbutene-1 polymer composition 793.
I got g.

The proportions of each component determined by catalyst analysis in a small amount of the polymer sampled at the end of the first, second and third stages are 60% by weight for the first stage polymer (component (a)), 60% by weight for the first stage polymer (component (a)), The octene-1 content in the al component is 3% by weight, and the second stage polymer (
(b) component) is 30% by weight, octene in component (b)
1 content is 17% by weight, the third stage polymer ((C) component) is 10% by weight, the octene content in the (C) component is 40% by weight, and the 4-methylpentene-1 content is 30% by weight. Met.

In addition, in the cleaning process of catalyst components, non-grade and low molecular weight components that are soluble in n-hexane (hereinafter referred to as n-hexane soluble components) are
．． It was 9% by weight.

With respect to 100 parts by weight of the obtained polymer composition, MARKA
0.25 parts by weight each of O-18, MARKAO-4123 (product name: both manufactured by Adeka Argus) and Irgafuos P-EPQ (product name: manufactured by Nippon Ciba Geigy) 0
．． After adding 2 parts by weight, pelletization was performed using an extruder at 320°C.

The melting point of this product was 294.289°C, and the melt index (hereinafter referred to as MI) was 0.99 g/10 minutes.

A sheet with a thickness of 600 μm was formed from this pellet and subjected to vacuum and pressure forming.

The polymerization results are shown in Table 1.

Resin Production Examples-2 to 4 Resin Production Examples-1 were carried out in the same manner as in Resin Production Example-1 except that the composition ratios, comonomer contents, and types of comonomers of the (al component, (bl component, and (C1 component) were changed as shown in Table 1. The polymerization results are shown in Table 1.However, resin production example 3
．． In No. 4, the heat stabilizers were each 0.2 parts by weight of Irganox 1010, Irgafuos P-BPQ (trade names; all manufactured by Nippon Ciba Geigy), and hydroanthracene.

Resin production example-5 39 mm off of diethylaluminum monochloride and 13500 ml of 3-methylbutene were placed in an induction stirring type autoclave with a capacity of 51 which was sufficiently dried and replaced with argon.
, butene-1103ml was charged. After raising the internal temperature to 80°C, 3000 nw of the solid titanium trichloride catalyst component obtained in the catalyst production example was compressed with argon gas to initiate polymerization.

80° while continuously supplying butene-1195mj2
Copolymerization of 3-methylbutene-1 and butene-1 at C
This was done for 0 minutes. The total amount of butene-1 to be supplied is 298m
It was 1.

Next, 200 mf of isobutanol was injected with argon to stop the polymerization, and after expelling unreacted monomers, 2000 m+2 of n-hexane was charged, and the mixture was heated at 60°C for 6 hours.
After stirring for 0 minutes, the temperature was lowered to room temperature, and the supernatant liquid was taken out. This operation was repeated 5 times to wash and remove the catalyst component in the polymer, and then dried to form a white powder of 3-methylbutene-1.
945 g of copolymer was obtained. Additives are resin production examples-3 and 4
I made it the same as The results are shown in Table 1.

Resin Production Examples 6 to 9 Same as Resin Production Example-1 except that the composition ratio of component (a), (bl component, and [C) component, comonomer content, and type of comonomer were changed as shown in Table 1. I went to The polymerization results are shown in Table 2.

However, in resin production examples 6 and 7.9, the heat stabilizer was Irganox 1010 (trade name; manufactured by Nippon Ciba Geigy) 0
．． The amount was 8 parts by weight.

In addition, in Resin Production Example 8, the heat stabilizer was Irganox 1.
010. Irgafuos-P-EPQ (trade name; both manufactured by Nippon Ciba Geigy) 0.2 parts by weight each.

Example-1 The sheet with a thickness of 600 μm obtained in Resin Production Example-1 was vacuum-pressure formed using a vacuum-pressure forming machine manufactured by Kano Institute.

The temperature of both the upper and lower heaters was 600°C. When the surface temperature of the resin reached 295° C. by heating, the heater was moved under automatic control, the mold was replaced, and vacuum-pressure molding was performed.

The mold temperature was set at 190°C and the holding time was 5 seconds. Five seconds later, as the mold opened, compressed air was blown out from below, and the molded resin was removed from the mold.

The mold releasability was good.

After trimming the obtained molded product, a heat resistance test and an impact resistance test were conducted. For heat resistance testing, molded products were tested at 20
The molded product was placed in a gear oven at 0°C, 1230°C, and 1240°C, and taken out after 15 minutes to observe the deformed appearance of the molded product.

No deformation was observed at any temperature. 30°C/20°
The falling weight impact strength of C is 1 at a thickness of approximately 400 μm.
It was 70.95 kg-c+n/cm. The physical property evaluation results are summarized in Table 2.

Example 2 The 600 μm thick sheet obtained in Resin Production Example 2 was molded in the same manner as in Example 1.

However, the molding resin surface temperature is 285℃, and the mold temperature is 19℃.
The temperature was set at 0°C. The mold holding time was 4 seconds.

As an evaluation of heat resistance, we added measurement of deformation time using a microwave oven. The physical property evaluation results are summarized in Table 3.

Examples 3, 4, 5, 6, 7, 8 The resins obtained in Resin Production Examples 3, 4, 6, 7, 8, and 9 were molded. Table 3 shows the resin surface temperature, mold temperature, mold holding time, appearance test using a gear oven, and measured impact strength. Regarding Example 6,
Gear oven tests were conducted at 240°C (250°C).

Comparative Example 1 A commercially available C-PET container (Pet Kutsuka manufactured by Rispack Co., Ltd.) was placed in a gear oven at 200°C, 230°C, and 240°C for 15 minutes, and after heating, it was 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 (Lispack 02, manufactured by Lispack Co., Ltd., Pet Kutsuka) was placed in a microwave oven, heated at a set temperature of 250° C., and the time until deformation started was measured.

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 (manufactured by Rispack Co., Ltd., Betku 7 Car) was measured at 30°C/-20°C. In particular, the impact strength at -20°C is 4 kg-cm/c.
It was as low as m. The results are shown in Table 2.

Comparative Example-4 The resin obtained in Resin Production Example-5 was molded. A 500 μm sheet made from this resin was molded at a temperature of 27
Molding was carried out at 5°C, 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 at 250°C in a microwave oven and the temperature was raised from room temperature, but deformation occurred after 9 minutes of heating time.

The low temperature impact strength is 9 kg-am/cm and C
Although it was higher than that of -PET, it was lower than that of the rubbery copolymer-containing poly-3-methylbutene-1 resin of the present invention.

Example-5, Comparative Example-5 For the molded product of Example-1, add 100 c of salad oil.
c and heated in a microwave oven with a power of 500W.

(Example-5) In a commercially available C-PET container of a similar shape (manufactured by Lisback 01, Petcutska), 100% of salad oil was also added.
cc and heated in the same manner.

(Comparative Example-5) The relationship between heating time and salad oil temperature is shown in FIG. 1.

As is clear from the figure, the poly-3-methylbutene-1 resin container according to the present invention utilizes high frequency waves more efficiently and the contents are heated better than the C-PET container.

〔Effect of the invention〕

The poly-3-methylbutene-1 resin-type top-opening container according to the present invention has high heat resistance as a container that can be used in both ovens and microwaves, so it can withstand use at high temperatures of 160°C and even 200°C or higher. , 240°C.

In addition, when heating in a microwave oven, compared to C-PET containers, there is less absorption or reflection of high frequencies, so the heating efficiency of the food inside the container is good (the temperature of the food rises in a short time, Alternatively, there are advantages such as increasing the temperature of food with less power consumption.

Furthermore, most foods that are cooked in microwave ovens, ovens, etc. are frozen, stored, and transported in containers, but the poly3methylbutene-1PA fat container of the present invention Compared to containers made of C-PET, it has much higher impact resistance at freezing temperatures, so it has the great advantage of being less likely to be damaged during frozen storage.

Furthermore, on the molding surface, crystallization is fast and release from the mold is good, so it is possible to shorten the molding cycle and mold containers with high production efficiency.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing the relationship between heating time and salad oil temperature based on Example-5 and Comparative Example-5. In the figure, 1 shows the results of Example 5, that is, the case where the container made of poly3-methylbutene-1 resin according to the present invention was used. 2 in the figure shows the results of Comparative Example-5, that is, when a commercially available C-PET container was used.

Claims (6)

[Claims] (1) 1 to 30% by weight of rubbery α-olefin copolymer
A poly-3-methylbutene-1 resin containing poly-3-methylbutene-1 is formed into a sheet and then thermoformed.
1. Top-opening container made of resin. (2) The container according to claim 1, wherein the container has a wall thickness of 100 μm to 2 mm. (3) The rubbery α-olefin copolymer contains 3 to 50% by weight of 3-methylbutene-1 unit,
A container according to claim 1. (4) The poly-3-methylbutene-1 resin containing a rubbery α-olefin copolymer is produced by a multi-step polymerization method including a step of polymerizing the rubbery α-olefin copolymer. A container according to claim 1, characterized in that: (5) The melting point of the poly-3-methylbutene-1 resin containing the rubbery α-olefin copolymer is 250°C to 310°C.
The container according to claim 1, characterized in that the container has a heat of fusion of 4 cal/g or more and a melt index of 0.1 to 100 g/10 minutes. (6) No deformation at a temperature of 160°C, and -20°C
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 °C.