JPH0689122B2 - Shape-recoverable norbornene-based polymer molded product - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a norbornene-based polymer molded product, and more particularly to a shape-recoverable norbornene-based polymer molded product.

[0002]

2. Description of the Related Art Norbornene-based polymers are polymers having a glass transition temperature in the range of about -20 DEG C. to 100 DEG C. and generally do not show rubber-like properties at room temperature. However, the norbornene-based polymer has a property of absorbing a large amount of oil, and by adding a large amount of oil, it is possible to lower the glass transition temperature and impart rubber properties, so that property is utilized. Like natural rubber and normal synthetic rubber, it is used to make vulcanized rubber products. Further, the norbornene-based polymer has a characteristic that it does not cause cold flow even in an unvulcanized state in which a large amount of oil is added due to its extremely large molecular weight, and by utilizing this property, caulking material, sealing material, It is also used as a floor undercoat material for vibration absorption. On the other hand, a norbornene-based polymer or a norbornene-based polymer to which an extremely small amount of oily component is added is molded by applying heat and pressure, and it is also considered to be used as an ordinary plastic, but it is an amorphous polymer and has a molecular weight of Since it is extremely large, the fluidity is poor even at the glass transition temperature or higher, and the compression molding method is generally used as the molding method, and it is difficult to use mass-production molding methods such as injection molding and transfer molding. From the viewpoint of the method, the range of application of the norbornene-based polymer alone was limited to a specific field.

[0003]

The inventors of the present invention have reached the present invention as a result of their efforts to develop the use of a resin-like or leather-like norbornene-based polymer to which a large amount of oil has not been added. . The present invention provides a norbornene-based polymer molding capable of recovering a shape.

[0004]

Thus, according to the present invention, the glass transition temperature is 10 ° C. or higher and the number average molecular weight is 10.
Provided is a shape-recoverable norbornene-based polymer molded product in which a molded product composed of 0,000 or more norbornene-based polymer is deformed at a temperature lower than the molding temperature and then cooled to a temperature not higher than the glass transition temperature of the polymer to fix the deformation. To be done.

The shape-recoverable norbornene-based polymer molding of the present invention is obtained by molding a norbornene-based polymer having a glass transition temperature of 10 ° C. or higher and a number average molecular weight of 1,000,000 or higher into an arbitrary shape required for actual use ( Hereinafter, after being subjected to primary molding), a deformation is applied at a temperature lower than a temperature at which the molding is performed (hereinafter referred to as a primary molding temperature), and then, while being deformed, cooled to a temperature not higher than a glass transition temperature of the norbornene-based polymer. The deformation is fixed. When the molded body with such a fixed deformation is used, the deformation is automatically removed by heating again to a temperature not lower than the glass transition temperature of the norbornene-based polymer and lower than the molding temperature to obtain the original shape or a shape close to it. Since the molded product of the present invention can be recovered, it can be used in various fields where such a function is required.

The norbornene-based polymer used in the present invention has a glass transition temperature of 10 ° C or higher, preferably 20 ° C or higher, more preferably 30 ° C to 60 ° C, and the number average molecular weight of the polymer is 1,000,000 or higher. is there. If the glass transition temperature is lower than 10 ° C. and the number average molecular weight is lower than 1,000,000, the object of the present invention cannot be achieved.

The norbornene-based polymer is a ring-opening polymer or copolymer of bicyclo (2.2.1) heptene-2 or its derivative.
It is a polymer obtained by polymerizing by the method described in 35800. Examples of the monomer used include bicyclo (2.2.1) heptene-2, methyl-5-bicyclo (2.2.1) heptene-2, ethyl-5-bicyclo (2.2.1) heptene- Alkyl-5-bicyclo (2.2.1) heptene-2 type monomer such as 2; methoxy-
5-bicyclo (2.2.1) heptene-2, ethoxy-
Alkoxy-5-bicyclo (2.2.1) heptene-2 type monomers such as 5-bicyclo (2.2.1) heptene-2; cyano-5-bicyclo (2.2.1) heptene-
2; ester-type monomers of bicyclo (2.2.1) heptene-2-5carboxylic acid; diester-type monomers of bicyclo (2.2.1) heptene-2-5,6dicarboxylic acid, and the like. In addition, mixtures of these can also be used. Among them, a representative polymer is polynorbornene which is a ring-opening polymer of bicyclo (2.2.1) heptene-2.

The norbornene-based polymer used in the present invention may be blended with an oily component in order to impart elasticity and adjust hardness, and the oily component used may be at least one of a softener and a plasticizer. Seeds are used.
As the plasticizer, those commonly used for vinyl chloride resin or rubber are used, including dibutyl phthalate,
Di-2-ethylhexyl phthalate, dioctyl sebacate, dioctyl adipate, tricresyl phosphate, epoxidized soybean oil, salad oil, sesame oil, polypropylene adipate and the like are included.

The softening agent is a process oil generally used for rubber or the like or a highly refined product thereof, and includes paraffin type process oil, naphthene type process oil, aromatic type process oil and the like.

The amount of the oily component to be blended is 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the norbornene polymer. If it is 10 parts by weight or more, it becomes too soft at room temperature and it becomes difficult to fix the shape.

A cross-linking agent may be used to adjust the performance of the shape-recoverable norbornene-based polymer molding of the present invention, and the cross-linking agent is commonly used in the fields of rubber and plastics such as sulfur and organic peroxides. There is no particular limitation as to what has been done. The amount of the cross-linking agent to be compounded is not limited as long as it does not impair its performance, but the range used for ordinary vulcanized rubber or cross-linked plastic products is appropriate. Further, vulcanization accelerators, activators, and other crosslinking aids can also be used together with the crosslinking agent. It should be noted that, in the case of compounding, compounding agents such as a stabilizer, a flame retardant, a colorant, an organic / inorganic reinforcing agent, and an organic / inorganic filler may be added and used within a range not departing from the gist of the present invention.

The method for producing the shape-recoverable norbornene-based polymer molded article of the present invention is as follows. First, a norbornene-based polymer is mixed with an oily component, a cross-linking agent and, if necessary, a stabilizer, a flame retardant, a colorant, an organic / inorganic reinforcing agent, a filler, etc. by a mixer such as a roll, Banbury, kneader, or Henschel mixer. After kneading to prepare a mixture of norbornene-based polymer and compounding agent,
The mixture is once molded into an arbitrary shape required for actual use by compression molding or the like (primary molding).

The temperature (primary molding temperature) and the pressure during the primary molding of the mixture of the norbornene-based polymer and the compounding agent, the obtained molded article can maintain a constant shape and exhibit strength characteristics without any practical problems. The conditions are not particularly limited, but the primary molding temperature is usually 100 ° C to 200 ° C.
C, preferably 140 to 180 ° C. The pressure during molding is usually 1 kg / cm ^{2 to} 200 kg / cm.
² , preferably 50 kg / cm ^{2 to} 150 kg / cm ²
Is.

The molded body thus molded by the primary molding is
Then, after applying a deformation at a temperature lower than the primary molding temperature,
A shape-recoverable norbornene-based polymer molded article can be manufactured by cooling the norbornene-based polymer to a temperature not higher than the glass transition temperature and fixing the deformation. If the temperature at which the deformation is applied is equal to or higher than the primary molding temperature, a new shape is given to the molded body, which is not preferable. It is preferably within the range of the glass transition temperature of the norbornene-based polymer to the glass transition temperature + 30 ° C, but it is also possible to give deformation at a temperature below the glass transition temperature.

There is also no particular limitation on the method of giving deformation, and usually, the temperature atmosphere (for example, in heated air, heated liquid, or the like) in which the molded body is easily deformed in accordance with the shape and wall thickness of the primary molded body. It can be deformed with bare hands or a suitable tool.

Further, in order to fix the deformation, when the temperature at which the deformation is applied is higher than the glass transition temperature of the norbornene-based polymer, it is necessary to immediately cool it below the glass transition temperature after the deformation. Further, when the deformation temperature is lower than the glass transition temperature, the deformation is fixed at that temperature, so that it is not necessary to cool it to a lower temperature.

The shape-recoverable norbornene-based molded article of the present invention may be heated to a temperature not lower than the glass transition temperature of the norbornene-based polymer and lower than the primary molding temperature (hereinafter referred to as shape-recovery temperature) before use. The deformation is automatically removed and the shape restored by the primary molding is restored. The higher the shape recovery temperature, the shorter the time required to recover the shape. The heating means is not particularly limited as in the case of applying the deformation, and heated air, steam or the like can be used.

By utilizing the properties of the shape-recoverable norbornene-based molded product of the present invention, for example, when it is difficult to mount, assemble, convey, etc. with a predetermined shape, it is suitable for easy handling. Since it becomes possible to recover the molded body of the present invention to a predetermined shape by heating after it is deformed into a different shape and after mounting, assembling, etc., (1) a joint material for pipes with different diameters, (2) Inner / outer laminating materials for pipes and rod-shaped objects, (3) Work such as tightening pins, architectural fixing materials, (4) Medical equipment materials such as casts,
(5) Portable containers, tableware, etc. that are folded when not in use and recover their shape when in use, (6) Members such as automobile bumpers that require deformation recovery after shock absorption,
(7) It can be used as a gap preventing material for partitioning a house, (8) member for toys, (9) stationery material such as straw, teaching material, (10) ornamental material such as artificial flower, brooch and the like. Note that the use is not limited to these, and applications such as not completely recovering the shape but utilizing the property of shape recovery to seal a space having a bound object in the front, rear, left, and right are also included.

A method of using the properties of the shape-recoverable norbornene-based molded product of the present invention will be described with reference to the cast of FIG. 1 as an example. First, (1) Gibbs A molded into a shape such as an arm or leg is immersed in warm water of 40 ° C to 50 ° C for a few minutes, and then the free end of the peripheral wall is spread like B so that it can be mounted, This shape is cooled and fixed. After that, (2) if it is attached to a predetermined part of the human body and heated by a hair dryer or the like, the original shape of A is automatically restored again and the part is fixed.

[0020]

The present invention will be described in detail with reference to the following examples. Example 1 Norbornene-based polymer (nor product manufactured by CdF, France)
sorex; glass transition temperature 35 ° C, molecular weight of 2,000,000 or more) Powder is charged into a mold and left for 10 minutes under the conditions of a molding temperature of 150 ° C and a molding pressure of 130 kg / cm ² to form a cylinder having a diameter of 5 mm and a length of 20 mm. 45
The both ends were sandwiched with pliers in warm water at ℃ and stretched to a diameter of about 3 mm, and then returned to room temperature to obtain a molded product whose shape was fixed in the stretched state. Next, when the molded body was immersed again in warm water at 45 ° C., it was completely restored to its original shape. The time required for shape recovery was about 10 seconds.

Example 2 In the same manner as in Example 1, the inner diameter was 30 mm and the wall thickness was 2 mm.
mm O-rings are molded and then 8 in warm air at 50 ° C.
It was immersed in water at 25 ° C. while being twisted 5 times in a square shape to obtain a molded body whose shape was fixed in the state of being twisted. Next, when the molded body was left again in warm air at 45 ° C., it was completely restored to its original shape. The time required for shape recovery was 15 seconds. Also, one part of the O-ring was cut and stretched about 3 times at room temperature to obtain a molded body having a rod-like shape fixed at room temperature. Then, when the molded body was immersed in warm water at 60 ° C., the shape immediately recovered to the original O-ring shape. The time required for shape recovery was about 5 seconds.

Example 3 The same norbornene-based polymer powder as in Example 1 was charged into a mold, and the molding temperature was 160 ° C. and the molding pressure was 100 kg / cm ^2.
Leave for 15 minutes under conditions of 0.3mm thickness and 30m width
m after obtaining a sheet-shaped molded product of 150 mm in length, 40
Wind in a 5 mm diameter iron core in warm air at ℃
C.) to obtain a roll-shaped molded product. Then, when the roll-shaped molded product was left again in warm air at 40 ° C., it was completely restored to its original shape and became a sheet. The time required for recovery was about 15 seconds.

Example 4 The same norbornene-based polymer powder as in Example 1 was mixed with a Henschel mixer in an amount of 2 parts by weight of an oil component (naphthene-based process oil, based on 100 parts by weight of the norbornene-based polymer powder).
Nippon Sun Oil Co., Sunthene-255) was added, the mixture was charged into a mold, and the molding temperature was 150 ° C.
Molding pressure 150kg / cm ² After leaving it for 15 minutes under the conditions described above to form a cylindrical molded product having a diameter of 25 mm and a height of 12 mm,
Compressed with pliers in warm water of 50 ° C. to give large deformation, and immediately immersed in water of 25 ° C. under deformation to obtain a molded body having a fixed shape. Then, when the molded body was immersed in warm water at 50 ° C., it was completely restored to its original shape. The time required for shape recovery was about 20 seconds.

Example 5 The same norbornene-based polymer powder as in Example 1 was mixed with a Henschel mixer in an amount of 2 parts by weight of an oily component (naphthene-based process oil, manufactured by Nippon Sun Oil Co., Sunthene-) with respect to 100 parts by weight of the norbornene-based polymer powder. 25
5), 5 parts by weight of zinc oxide, 1 part by weight of stearic acid, 1.5 parts by weight of sulfur, and 5 parts by weight of vulcanization accelerator cyclohexylbenzothiazylsulfenamide are added, and the mixture is charged into a mold and molded. Temperature 150 ℃, molding pressure 150kg /
Leave for 15 minutes under the condition of cm ² , thickness 2 mm, width 30 m
m after forming a sheet-like molded product with a length of 150 mm, then at 50 ° C
Was spirally twisted in warm water and immersed in water at 25 ° C. to obtain a molded body in which the shape in the twisted state was fixed.
Then, when the molded body was immersed again in warm water at 50 ° C.,
It completely recovered its original shape and became a sheet. The time required for recovery was about 15 seconds.

From the above examples, it can be seen that the molded product of the present invention is a molded product having shape recoverability. Further, it can be seen that a peculiar use method utilizing the properties of the molded article of the present invention can be obtained.

[0026]

As described above, according to the present invention, a shape-recoverable norbornene-based polymer molded body is obtained, and by utilizing the peculiar properties of the molded body, it can be mounted or assembled in its shape in use. In addition, it becomes possible to use a method in which the shape is changed so that it can be easily handled when it is difficult to carry, and then the shape is restored to a predetermined shape by heating after the mounting, the assembly and the like are completed.

[0027]

[Brief description of drawings]

[0028]

[Figure 1]

It is a diagram showing an example of use of the shape-recoverable norbornene-based polymer molded product of the present invention.

[0030]

[Explanation of symbols]

A molded product obtained by primary molding of norbornene-based polymer B Modified product of molded product A, shape-recoverable norbornene-based polymer molded product in which the deformation is fixed

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C08J 7/00 301 7310-4F E04C 1/00 7904-2E F16L 13/00 7123-3J

Claims (1)

[Claims] 1. A molded body composed of a norbornene-based polymer having a glass transition temperature of 10 ° C. or higher and a number average molecular weight of 1,000,000 or higher is deformed at a temperature lower than the molding temperature, and then to a temperature not higher than the glass transition temperature of the polymer. Shape-recoverable norbornene-based polymer moldings that are cooled and fixed in shape.