JP2015110293A - Method for producing cyclic olefin resin molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a cyclic olefin resin molding, in which black spots can be restrained from being mixed in the cyclic olefin resin molding and which is excellent in product yield.SOLUTION: The method for producing the cyclic olefin resin molding comprises the steps of: using a molding machine having a cylinder and a screw to be inserted into the cylinder; and molding a cyclic olefin resin in the molding machine. The screw has a screw body and a flight formed on the periphery of the screw body. When such a position is a melt completion position that the cyclic olefin resin is melted completely in the axial direction of the cylinder and the inside diameter of the cylinder is defined as D, the groove depth h of the screw at the melt completion position satisfies the inequality: h≤0.67D(when D≤20 mm) or h≤0.15D (when D>20 mm).

Description

  The present invention relates to a method for producing a cyclic olefin-based resin molded body.

  Among polyolefin resins, cyclic olefin polymers are particularly excellent in transparency. The cyclic olefin-based polymer has low water absorption and moisture permeability and does not have a polar group, so it is difficult to adsorb a chemical having a polar group. Utilizing such properties, the cyclic olefin polymer is suitably used as a transparent container for foods and pharmaceuticals, as well as lenses for optical devices such as spectacle lenses, pickup lenses, fθ lenses, MO, DVD, etc. It is also used for optical recording media such as CDs.

  A molded body for such use is molded by a molding machine such as an injection molding machine. When the molding machine is operated continuously for a long time, black spots are mixed in the molded body. In transparent resin products, particularly optical products, it is not allowed to mix substances that block light in the resin, and black spots mixed during molding cause a decrease in yield. It has been found that black spots mixed during resin molding are resin carbides. A black spot is obtained by carbonizing a molten resin staying behind a flight of a screw in a molding machine, for example, by heating with time.

  Conventionally, when molding a transparent resin, molding is performed at a lower resin temperature in order to prevent the inclusion of black spots. However, with cyclic olefin polymers, moldability is reduced, which adversely affects the appearance and transparency of the product. There is a risk of affecting. Accordingly, in actual continuous operation, the amount of black spots generated is monitored, and if the amount generated is increased, the inside of the molding machine is purged, which causes a reduction in the basic unit of the product.

JP 2000-233425 A

  The present invention was made based on the background as described above, and when molding a resin composed of a cyclic olefin polymer, the cyclic olefin resin is excellent in product yield during continuous operation by suppressing generation of black spots. It aims at providing the manufacturing method of a molded object.

In the present invention, in order to suppress the mixing of black spots into the cyclic olefin-based resin molded product, the resin is prevented from staying and adhering to the molding machine.
In order to suppress stagnation and adhesion of the resin in the molding machine, it is better to reduce the groove depth of the screw at the position where the melting of the resin is completed (melting completion position) in the molding machine. This is because the smaller the groove depth of the screw, the better the resin flow in the vicinity of the screw surface and the inner peripheral surface of the cylinder, and the black spots are less likely to adhere to the screw and cylinder. This is because the sunspot is easily washed away before the sunspot becomes large. In addition, the shallower the groove depth of the screw, the smaller the volume between the screw and the inner peripheral surface of the cylinder, and the shorter the residence time of the resin. Therefore, by reducing the groove depth of the screw, it is possible to extend the time until the black spot is generated and suppress the black spot. The groove depth of the screw is a distance between the inner peripheral surface of the cylinder and the screw body in the radial direction of the cylinder.
Alternatively, in order to suppress the stagnation and adhesion of the resin in the molding machine, it is better to increase the radius of curvature of the boundary between the screw body and the flight (the base portion of the flight). This is because the larger the radius of curvature of the base portion of the flight, the smaller the region where the resin stays.
Then, this invention provides the manufacturing method of the following cyclic olefin resin molded object.

That is, the present invention
A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
Provided is a method for producing a cyclic olefin-based resin molded product, wherein the screw groove depth h at the melting completion position is a relatively small value.

The present invention also provides:
A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
In a cross section along the axial center of the screw body, a radius of curvature r of a boundary portion between the flight and the screw body is relatively large for at least one of the front side and the rear side of the flight. A method for producing a cyclic olefin-based resin molded body is provided.

The present invention also provides:
A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position, and the inner diameter of the cylinder is D,
The screw groove depth h at the melting completion position is:
h ≦ 0.67D ^0.5 (D ≦ 20mm)
h ≦ 0.15D (D> 20mm)
The manufacturing method of the cyclic olefin resin molded object which satisfy | fills is provided.

The present invention also provides:
A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
A position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
When the groove depth of the screw at the melting completion position is h,
In at least one of the front side and the rear side of the flight, the radius of curvature r at the boundary between the flight and the screw body is not less than h in the cross section along the axis of the screw body. A method for producing a cyclic olefin-based resin molded body is provided.

  According to the present invention, when a cyclic olefin-based resin is molded by continuously operating a molding machine such as an injection molding machine, resin stagnation in the molding machine can be suppressed. As a result, mixing of black spots in the molded body can be suppressed and the continuous operation time of molding can be extended, so the frequency of purging and cleaning the resin during operation can be reduced, and the basic unit of the product is improved. .

It is the elements on larger scale of the screw and cylinder of an injection molding machine used for the manufacturing method of the cyclic olefin system resin fabrication object concerning an embodiment. It is the schematic of the screw of the injection molding machine used for the manufacturing method of the cyclic olefin resin molding which concerns on embodiment. It is a figure which shows an example of the injection molding machine used for the manufacturing method of the cyclic olefin resin molded object which concerns on embodiment. It is a figure which shows the specific example of the screw of the injection molding machine used for the manufacturing method of the cyclic olefin resin molded object which concerns on embodiment.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same components are denoted by the same reference numerals, and description thereof will be omitted as appropriate.

  A molding machine having a screw and a cylinder is used for the method for producing a cyclic olefin-based resin molded body according to the present embodiment. Examples of the molding machine include an extrusion molding machine, an injection molding machine, a blow molding machine, and an inflation molding machine. In the present embodiment, the effect is particularly remarkable when molding using an injection molding machine. Hereinafter, an injection molding machine will be described as an example.

  The injection molding machine includes a resin supply unit, a resin melting unit, an injection hydraulic cylinder, and a mold. The resin melting part is provided with a screw connected to the plunger of the injection hydraulic cylinder, and the resin material (for example, resin pellets) introduced from the resin supply part is fluidized by heating from the outside and transferred forward. The molten resin charged in the cylinder head is injected into the mold by the piston movement of the screw. For this reason, the screw performs a piston motion in the front-rear direction simultaneously with the rotation.

  That is, a resin material made of a cyclic olefin-based resin is introduced from a hopper and melted while being gradually transferred forward by a rotating screw to form a fluid. Molten cyclic olefin resin, that is, molten resin is filled in the cylinder head. As the cylinder head is filled with the molten resin, the screw moves backward, and when a predetermined amount is filled, the nozzle at the tip of the cylinder opens and the screw moves forward to inject the resin into the mold to obtain a molded body.

  This will be described with reference to the drawings. FIG. 1 is a view showing a part of a screw 2 and a cylinder 3 provided in an injection molding machine used in the method for producing a cyclic olefin-based resin molded body according to this embodiment. In FIG. 1, the upper half of the screw 2 is a cross-sectional view, and the lower half is a side view. FIG. 2 is a side view showing an example of the screw 2. FIG. 3 is a view showing an example of an injection molding machine used in the method for producing a cyclic olefin-based resin molding according to the present embodiment.

  As shown in FIG. 3, the injection molding machine includes a hopper 1, a cylinder 3, a screw 2 inserted into the cylinder 3, a heating unit such as a band heater 4, a mold 7, and the like.

  As shown in FIG. 2, the screw 2 includes a round rod-shaped screw body 21 and flights 22 formed around the screw body 21.

  The screw 2 is supplied from the upstream side (rear side: right side in FIG. 2) to the downstream side (front side: left side in FIG. 2), from the supply unit 2a, the first compression unit 2b, the melting completion unit 2c, and the second compression unit 2d. , And a measuring unit 2e in this order. Furthermore, the screw 2 includes a base end portion 2f on the upstream side of the supply portion 2a, and includes a tip end portion 2g on the downstream side of the measuring portion 2e.

  The flight 22 is a spiral rib formed along the peripheral surface of the screw body 21, and each part of the supply unit 2a, the first compression unit 2b, the melting completion unit 2c, the second compression unit 2d, and the measurement unit 2e. It is formed continuously over the gap. However, the flight 22 is not formed in the base end part 2f and the front-end | tip part 2g. That is, the upstream end portion of the flight 22 is located in the supply unit 2a. More specifically, for example, the upstream end of the flight 22 is located at the upstream end of the supply unit 2a. Further, the downstream end portion of the flight 22 is located in the measuring portion 2e. More specifically, for example, the downstream end of the flight 22 is located at the downstream end of the measuring unit 2e.

  The outer diameter of the screw body 21 is gradually increased from the upstream side to the downstream side in the axial direction of the screw body 21 in the first compression portion 2b. The outer diameter of the screw body 21 is also gradually increased from the upstream side to the downstream side in the axial direction of the screw body 21 also in the second compression portion 2d.

  The outer diameter of the screw main body 21 can be made constant, for example, in the base end portion 2f, the supply portion 2a, the melting completion portion 2c, the measuring portion 2e, and the distal end portion 2g. In this case, the outer diameter of the base end portion 2f and the outer diameter of the supply portion 2a are equal to the outer diameter of the upstream end portion of the first compression portion 2b, and the outer diameter of the downstream end portion of the first compression portion 2b is completely melted. The outer diameter of the portion 2c is equal to the outer diameter of the upstream end portion of the second compression portion 2d, and the outer diameter of the downstream end portion of the second compression portion 2d is equal to the outer diameter of the measuring portion 2e and the outer diameter of the tip portion 2g. equal. The outer diameter of the melting completion part 2c is larger than the outer diameter of the supply part 2a, and the outer diameter of the measuring part 2e is larger than the outer diameter of the melting completion part 2c.

  As described above, the diameter of the screw main body 21 is gradually increased from the upstream side toward the downstream side.

Here, the groove depth h of the screw is a distance between the cylinder inner peripheral surface 31 and the screw body 21 in the radial direction of the cylinder 3.
The groove depth of the screw 2 is gradually reduced from the upstream side toward the downstream side. In addition, the outer diameter of the screw 2 including the flight 22 can be made constant from the front end to the rear end of the screw 2, for example. For this reason, the height of the flight 22 is larger as the groove depth h of the screw 2 is deeper, and the height of the flight 22 is smaller as the groove depth h of the screw 2 is shallower.

The groove depth h of the screw 2 can be made constant, for example, in the supply unit 2a, the melting completion unit 2c, and the measuring unit 2e. And the groove depth h of the screw 2 in the supply part 2a is made equal to the groove depth h of the screw 2 in the upstream end part of the first compression part 2b, and the screw 2 in the downstream end part of the first compression part 2b. Is equal to the groove depth h of the screw 2 in the melting completion part 2c and the groove depth h of the screw 2 at the upstream end of the second compression part 2d, and is downstream of the second compression part 2d. The groove depth h of the screw 2 at the end can be made equal to the groove depth h of the screw 2 at the measuring part 2e. The groove depth h of the screw 2 in the supply part 2a is deeper than the groove depth h of the screw 2 in the melting completion part 2c, and the groove depth h of the screw 2 in the melting completion part 2c is the groove depth h of the screw 2 in the measuring part 2e. Deeper than the groove depth h.
In the first compression section 2b, the groove depth h of the screw 2 is gradually shallower toward the downstream side, and in the second compression section 2d, the groove depth h of the screw 2 is directed toward the downstream side. It is gradually getting shallower.

  In addition, the heating temperature of the cylinder 3 is set so that the cyclic olefin-based resin pellets are substantially completely melted and become a molten resin in the arrangement region of the melting completion part 2c. That is, when the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder 3 is referred to as a melting completion position, this melting completion position is any position in the arrangement region of the melting completion portion 2 c in the cylinder 3. . The position of the melting completion part 2c is not particularly limited. If the length of the region in which the flight 22 is formed in the axial direction of the screw 2 is referred to as the flight formation region length, the position of the melting completion portion 2c is the portion where the flight 22 starts (upstream end portion of the flight 22). In the portion where the flight 22 ends (the downstream end portion of the flight 22), it is preferably present at a position within a distance of 80% or less of the flight formation region length from the portion where the flight 22 starts to the downstream side.

  When supplying (injecting) the cyclic olefin-based resin to the hopper 1 of the molding machine in the form of pellets, the groove depth of the screw 2 at the cyclic olefin-based resin supply position is deeper than the groove depth of the screw 2 at the melting completion position. You may do it. By doing in this way, supply of a pellet becomes easy. In addition, by providing the 1st compression part 2b in the front | former stage (upstream side) of the fusion completion part 2c as mentioned above, such a structure is easily realizable.

  As described above, the inventors of the present invention preferably reduce the groove depth of the screw 2 at the melting completion position in order to suppress the resin stagnation in the molding machine. I thought it would be better to increase the radius of curvature at the boundary. Therefore, a simulation analyzing the three-dimensional flow state of the resin in the cylinder 3 was performed, and an appropriate groove depth of the screw 2 and an appropriate radius of curvature at the boundary between the screw body 21 and the flight 22 were examined.

  From the results of this simulation, when the inner diameter of the cylinder 3 is 20 mm, the shear depth in the vicinity of the surface of the screw 2 can be sufficiently increased by setting the groove depth of the screw 2 at the melting completion position to about 3.0 mm or less. It has been determined that the resin can be prevented from staying in the cylinder 3. That is, by setting the groove depth of the screw 2 within this range, it can be expected that black spots are prevented from being mixed into the molded product.

Here, the method of determining the dimension of the screw 2 by the 0.5 power law, 0.7 power law, 1 power law, or the like is known. That is, the groove depth of the screw 2 is obtained by A · D ^0.5 in the 0.5th power rule, and is obtained by A · D ^0.7 in the 0.7th power rule. * Calculated by D (where A is a coefficient).

Therefore, when the inner diameter of the cylinder 3 is 20 mm, the coefficient is determined so that the groove depth of the screw 2 is 3.0 mm in each of the 0.5th power law, 0.7th power law, and 1st power law. . Then, the groove depth of the screw 2 is 0.5 in the law determined in ^{0.67D 0.5,} determined in ^{0.37D 0.7} at 0.7 power law, in one law with 0.15D Desired.

As a result of further intensive studies by the inventors, when the inner diameter of the cylinder 3 is 20 mm or less, the upper limit value of the groove depth of the screw 2 is determined according to the 0.5 power law, and the inner diameter of the cylinder 3 exceeds 20 mm. In some cases, it has been found suitable to determine the upper limit value of the groove depth of the screw 2 according to the power law. That is, when the inner diameter of the cylinder 3 is D (FIG. 1), a preferable groove depth h (FIG. 1) of the screw 2 is, for example, h ≦ 0.67D ^0.5 when the inner diameter D is 20 mm or less. When the inner diameter D exceeds 20 mm, h ≦ 0.15D can be satisfied.

More specifically, for example, in the axial direction of the cylinder 3, when the inner diameter D is 20 mm or less with respect to the groove depth h of the screw 2 from the position upstream by 5D from the melting completion position to the melting completion position. H ≦ 0.67D ^0.5, and when the inner diameter D exceeds 20 mm, h ≦ 0.15D.

  Thus, by setting the groove depth h of the screw 2 to a predetermined upper limit value or less, it is possible to suppress the resin from staying in the cylinder 3.

  In addition, by providing the 1st compression part 2b in the front | former stage of the fusion completion part 2c as mentioned above, the structure which made shallow the groove depth in the fusion completion position more than a certain extent is easily realizable.

On the other hand, the lower limit of the groove depth h of the screw 2 is set to a value of 0.1 mm or more when the inner diameter of the cylinder 3 is 20 mm in order to ensure a certain level of resin material transport force by the screw 2. It turned out to be preferable. Therefore, when the inner diameter of the cylinder 3 is 20 mm, the coefficient A is set so that the groove depth of the screw 2 is 0.1 mm in each of the 0.5th power law, 0.7th power law, and 1st power law. Were determined. Then, the groove depth of the screw 2 is 0.5 in the law determined in 0.022D ^0.5, determined in 0.012D ^0.7 at 0.7 power law, in one law in 0.005D Desired.

As a result of further intensive studies by the inventors, when the inner diameter of the cylinder 3 is 20 mm or less, the lower limit value of the groove depth of the screw 2 is determined according to the first power rule, and the inner diameter of the cylinder 3 exceeds 20 mm. It has been found that it is preferable to determine the lower limit value of the groove depth of the screw 2 according to the 0.5 power law. That is, h> 0.005D when the inner diameter D is 20 mm or less, and h ≧ 0.022D ^0.5 when the inner diameter D exceeds 20 mm.

  Further, from the result of the above simulation, the resin stays in the cylinder 3 also by setting the radius of curvature r (FIG. 1) at the boundary between the screw body 21 and the flight 22 to be not less than the groove depth h of the screw 2. It turned out that it can suppress. That is, by setting the radius of curvature r within this range, it is possible to reduce the stay region where the shear rate is low, and expect to suppress the inclusion of black spots in the molded product.

  Therefore, in the cross section along the axial center of the screw main body 21, the curvature radius r of the boundary portion between the flight 22 and the screw main body 21 is set for at least one of the front surface 221 side and the rear surface 222 side of the flight 22. h or more. In the front surface 221 side and the rear surface 222 side, it is more effective to set the curvature radius r on the front surface 221 side to h or more. Moreover, it is preferable that the curvature radius r is set to h or more for both the front surface 221 side and the rear surface 222 side.

  In this way, the resin stay in the cylinder 3 can also be suppressed by increasing the radius of curvature r at the boundary between the screw body 21 and the flight 22.

  On the other hand, the upper limit value of the radius of curvature r is not particularly limited, but the radius of curvature r can be set to 5 h or less, for example, in order to ensure a certain level of transporting force of the resin material by the screw 2.

  Further, in the above simulation, when the temperature distribution in the cylinder and the melting completion position were examined, there was almost no change compared to the case where the conventional structure screw having the compression portion provided only at one position before the measuring portion was used. I found that there was no.

  In the present embodiment, as described above, the pressure of the molten resin in the measuring unit 2e can be sufficiently increased by providing the second compression unit 2d at the subsequent stage (downstream side) of the melting completion unit 2c.

Hereinafter, an example of the flow of operations for manufacturing the cyclic olefin-based resin molded body will be described.
The hopper 1 of the molding machine is charged with, for example, a cyclic olefin resin in the form of pellets (cyclic olefin resin pellets). Here, it is preferable that the raw materials such as the cyclic olefin resin pellets are sufficiently dried with nitrogen gas before being charged into the hopper 1. Thereby, since adsorption | suction of oxygen in a raw material can be suppressed, generation | occurrence | production of a black spot can be reduced more effectively. In addition, the shape and dimension of a pellet are not specifically limited.

  The cyclic olefin-based resin pellets charged into the hopper 1 are introduced into the arrangement region of the supply unit 2 a in the cylinder 3. In addition, the supply part 2a is arrange | positioned directly under the hopper 1, for example. The screw 2 is continuously driven to rotate around the axis of the screw 2 by an actuator (not shown), and the cylinder 3 is heated to an appropriate temperature by the band heater 4. The number of rotations of the screw 2 and the temperature of the cylinder 3 can be appropriately adjusted according to the physical properties of the cyclic olefin resin (physical properties such as [η] and MFR) and the structure of the device. The temperature can be set to 160 to 350 ° C., and the rotation speed can be set to 10 to 200 rpm.

  The cyclic olefin-based resin pellets introduced into the arrangement region of the supply unit 2 a in the cylinder 3 are transferred forward by the rotation of the screw 2 and are heated and gradually melted by the band heater 4 attached to the outer wall of the cylinder 3. , And sent to the arrangement region of the first compression portion 2b in the cylinder 3. In the arrangement region of the first compression section 2b, the cyclic olefin-based resin pellets are compressed and the resin material is melted and kneaded as the valley depth between the flights 22 gradually decreases toward the downstream side.

  The resin material in the cylinder 3 is transferred from the arrangement area of the first compression section 2b to the arrangement area of the subsequent melting completion section 2c.

  Further, the molten resin in the cylinder 3 is transferred from the arrangement region of the melting completion part 2c to the arrangement region of the second compression part 2d in the subsequent stage. In the arrangement region of the second compression portion 2d, the molten resin is compressed and the removal of bubbles from the molten resin (defoaming) proceeds as the depth of the valleys between the flights 22 gradually decreases toward the downstream side.

  Then, the molten resin is transferred to the arrangement area of the measuring portion 2 e in the cylinder 3, measured there, and stored in the cylinder head 5. At this time, since the nozzle 6 at the tip of the cylinder 3 is closed, the screw 2 moves backward. When a certain amount of molten resin is stored in the cylinder head 5, the nozzle 6 opens and the screw 2 moves forward to inject the molten resin into the mold 7. By repeating this, the cyclic olefin-based resin molding can be continuously molded.

  As described above, the cyclic olefin resin is molded by using the molding machine set in the above range for at least one of the groove depth h and the curvature radius r of the screw 2. A molded body is manufactured. Thereby, deterioration of the cyclic olefin-based resin in the molding machine can be suppressed, and the retention and carbonization of the molten resin in the cylinder 3 that causes black spots in the product can be reduced. Since mixing of black spots into the molded body can be suppressed and the continuous operation time of molding can be extended, the frequency of purging and washing the resin during operation can be reduced, and the basic unit of the product is improved.

  Each of FIGS. 4A and 4B is a side view showing an example of a more specific configuration of the screw 2. In FIGS. 4A and 4B, the base end 2f and the tip 2g are not shown.

  In the example of FIG. 4A, the length in the axial direction of the screw 2 is 30 mm in the supply unit 2a, 30 mm in the first compression unit 2b, 480 mm in the melting completion unit 2c, and the second compression unit. It is 30 mm for 2d and 30 mm for the weighing unit 2e. The inner diameter of the cylinder 3 is 30 mm. For each part of the screw 2, the groove depth h is 6.0 mm in the supply part 2a, 4.5 mm in the melting completion part 2c, and 1.5 mm in the measuring part 2e.

  In the example of FIG. 4B, the length of the screw 2 in the axial direction of each part of the screw 2 is 300 mm in the supply part 2a, 120 mm in the first compression part 2b, 60 mm in the melting completion part 2c, and the second compression part. It is 60 mm for 2d and 60 mm for the weighing unit 2e. The inner diameter of the cylinder 3 is 30 mm. For each part of the screw 2, the groove depth h is 6.0 mm in the supply part 2a, 4.5 mm in the melting completion part 2c, and 1.5 mm in the measuring part 2e.

(Cyclic olefin resin)
The cyclic olefin resin used in the method for producing a cyclic olefin resin molded body according to the present embodiment refers to a resin material containing a cyclic olefin polymer. The cyclic olefin-based resin may be composed of a cyclic olefin-based polymer, or may be a blend of a cyclic olefin-based polymer with another polymer such as an α-olefin. Hereinafter, examples of the cyclic olefin polymer in the present invention will be described.

<Cyclic olefin polymer>
In this embodiment, the cyclic olefin polymer is at least one cyclic olefin heavy selected from the group consisting of [A-1], [A-2], [A-3] and [A-4] below. Can be combined.

  [A-1]: α-olefin / cyclic olefin random copolymer obtained by copolymerizing an α-olefin having 2 to 20 carbon atoms and a cyclic olefin represented by formula (I) or formula (II) Compound (Random copolymer of α-olefin having 2 to 20 carbon atoms and cyclic olefin represented by formula (I) or (II))

In the formula (I), n is 0 or 1, m is 0 or an integer of 1 or more, q is 0 or 1, and R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently hydrogen. An atom, a halogen atom or a hydrocarbon group, R ^{15 to} R ¹⁸ may be bonded to each other to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring has a double bond; Alternatively, R ¹⁵ and R ¹⁶ , or R ¹⁷ and R ¹⁸ may form an alkylidene group.

In the formula (II), p and q are 0 or an integer of 1 or more, m and n are 0, 1 or 2, and R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom or an aliphatic hydrocarbon. Group, alicyclic hydrocarbon group, aromatic hydrocarbon group or alkoxy group, and the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ or R ¹¹ is bonded are directly or It may be bonded via an alkylene group having 1 to 3 carbon atoms, and when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ are bonded to each other to form a monocyclic or polycyclic ring. An aromatic ring may be formed.

  [A-2]: Ring-opening polymer or copolymer of cyclic olefin represented by formula (I) or (II)

  [A-3]: [A-2] hydride of ring-opening polymer or copolymer

[A-4]: Graft modified product of the above [A-1], [A-2] or [A-3].
In a preferred embodiment of the cyclic olefin polymer, the glass transition temperature (Tg) measured by DSC (differential scanning calorimeter) is preferably 70 ° C. or higher, more preferably 70 to 250 ° C., and particularly 80 -180 degreeC is preferable.

  The cyclic olefin polymer is amorphous or low crystalline, and the crystallinity measured by X-ray diffraction method is usually 20% or less, preferably 10% or less, more preferably 2% or less. .

  The cyclic olefin polymer has an intrinsic viscosity [η] measured in decalin at 135 ° C. of usually 0.01 to 20 dl / g, preferably 0.03 to 10 dl / g, more preferably 0. The melt flow index (MFR) measured at 260 ° C. and a load of 2.16 kg according to ASTM D1238 is usually 0.2 to 200 g / 10 minutes, preferably 1 to 100 g / 10. Min, more preferably 5 to 50 g / 10 min.

  Further, the softening point of the cyclic olefin polymer (A) is usually a softening point (TMA) measured by a thermal mechanical analyzer, which is usually 30 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 to 260 ° C. is there.

  Here, the cyclic olefin represented by the formula (I) or (II) which forms the cyclic olefin polymer used in the present embodiment will be described.

<Cyclic olefin>
The cyclic olefin forming the cyclic olefin polymer used in the present embodiment is represented by the formula (I) or (II).

In formula (I), n is 0 or 1, m is 0 or an integer of 1 or more, and q is 0 or 1. In addition, when q is 1, R ^a and R ^b are each independently the atoms or hydrocarbon groups shown below. When q is 0, each bond is bonded to form a 5-membered member. Form a ring.

R ^{1 to} R ¹⁸ and R ^a and R ^b are each independently a hydrogen atom, a halogen atom or a hydrocarbon group. Here, the halogen atom is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Moreover, as a hydrocarbon group, a C1-C20 alkyl group, a C3-C15 cycloalkyl group, and an aromatic hydrocarbon group are mentioned normally each independently. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group, and the cycloalkyl group includes a cyclohexyl group. Group, and examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group. These hydrocarbon groups may be substituted with a halogen atom. Furthermore, in the formula (I), R ^{15 to} R ¹⁸ may be bonded to each other (in cooperation with each other) to form a monocyclic or polycyclic ring, and the monocyclic or polycyclic ring thus formed May have a double bond.

In the formula (II), p and q are 0 or an integer of 1 or more, and m and n are 0, 1 or 2. R ^{1 to} R ¹⁹ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group or an alkoxy group.

  The halogen atom has the same meaning as the halogen atom in formula (I). Examples of the hydrocarbon group independently include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. . More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. As the cycloalkyl group, Examples of the aromatic hydrocarbon group include an aryl group and an aralkyl group. Specific examples include a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group.

  Examples of the alkoxy group include a methoxy group, an ethoxy group, and a propoxy group. In these hydrocarbon groups and alkoxy groups, the hydrogen bonded thereto may be substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Here, the carbon atom to which R ⁹ and R ¹⁰ are bonded and the carbon atom to which R ¹³ is bonded or the carbon atom to which R ¹¹ is bonded are directly or an alkylene group having 1 to 3 carbon atoms. It may be connected via. That is, when the two carbon atoms are bonded via an alkylene group, the groups represented by R ⁹ and R ¹³ , or the groups represented by R ¹⁰ and R ¹¹ are combined with each other. , An alkylene group of any one of a methylene group (—CH ₂ —), an ethylene group (—CH ₂ CH ₂ —), or a propylene group (—CH ₂ CH ₂ CH ₂ —) is formed.

Further, when n = m = 0, R ¹⁵ and R ¹² or R ¹⁵ and R ¹⁹ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of the monocyclic or polycyclic aromatic ring in this case include the following groups in which R ¹⁵ and R ¹² further form an aromatic ring.

  Here, q has the same meaning as q in formula (II).

で示されるビシクロ［２．２．１］−２−ヘプテン（２−ノルボルネン）（上記一般式中において、１〜７の数字は炭素の位置番号を示す。）および該化合物に炭化水素基が置換している誘導体が挙げられる。 The cyclic olefin represented by the formula (I) or the formula (II) as described above is more specifically exemplified below. As an example,

Bicyclo [2.2.1] -2-heptene (2-norbornene) represented by the formula (in the above general formula, the numbers 1 to 7 represent carbon position numbers) and the compound is substituted with a hydrocarbon group Derivatives thereof.

  Examples of the substituted hydrocarbon group include 5-methyl, 5,6-dimethyl, 1-methyl, 5-ethyl, 5-n-butyl, 5-isobutyl, 7-methyl, 5-phenyl, 5-methyl-5- Phenyl, 5-benzyl, 5-tolyl, 5- (ethylphenyl), 5- (isopropylphenyl), 5- (biphenyl), 5- (β-naphthyl), 5- (α-naphthyl), 5- (anthracenyl) ), 5,6-diphenyl and the like.

  Still other derivatives include cyclopentadiene-acenaphthylene adduct, 1,4-methano-1,4,4a, 9a-tetrahydrofluorene, 1,4-methano-1,4,4a, 5,10,10a-hexahydro. Bicyclo [2.2.1] -2-heptene derivatives such as anthracene can be exemplified.

で示されるテトラシクロ［４．４．０．１^２，５．１^７，１０］−３−ドデセン、およびこれに炭化水素基が置換した誘導体が挙げられる。 In addition, tricyclo [4.3.0.1 ^2,5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2,5 ] -3-decene, 5-methyltricyclo [4 .3.0.1 ^2,5 ] -3-decene and other tricyclo [4.3.0.1 ^2,5 ] -3-decene derivatives, tricyclo [4.4.0.1 ^2,5 ] -3 Tricyclo [4.4.0.1 ^2,5 ] -3-undecene derivatives such as -undecene, 10-methyltricyclo [4.4.0.1 ^2,5 ] -3-undecene,

Tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, and derivatives substituted with a hydrocarbon group.

  As the substituted hydrocarbon group, 8-methyl, 8-ethyl, 8-propyl, 8-butyl, 8-isobutyl, 8-hexyl, 8-cyclohexyl, 8-stearyl, 5,10-dimethyl, 2,10-dimethyl 8,9-dimethyl, 8-ethyl-9-methyl, 11,12-dimethyl, 2,7,9-trimethyl, 2,7-dimethyl-9-ethyl, 9-isobutyl-2,7-dimethyl, 9 , 11,12-trimethyl, 9-ethyl-11,12-dimethyl, 9-isobutyl-11,12-dimethyl, 5,8,9,10-tetramethyl, 8-ethylidene, 8-ethylidene-9-methyl, 8-ethylidene-9-ethyl, 8-ethylidene-9-isopropyl, 8-ethylidene-9-butyl, 8-n-propylidene, 8-n-propylidene-9-methyl, 8-n-propyl Pyridene-9-ethyl, 8-n-propylidene-9-isopropyl, 8-n-propylidene-9-butyl, 8-isopropylidene, 8-isopropylidene-9-methyl, 8-isopropylidene-9-ethyl, 8 -Isopropylidene-9-isopropyl, 8-isopropylidene-9-butyl, 8-chloro, 8-bromo, 8-fluoro, 8,9-dichloro, 8-phenyl, 8-methyl-8-phenyl, 8-benzyl , 8-tolyl, 8- (ethylphenyl), 8- (isopropylphenyl), 8,9-diphenyl, 8- (biphenyl), 8- (β-naphthyl), 8- (α-naphthyl), 8- ( Anthracenyl), 5,6-diphenyl and the like can be exemplified.

Further, tetracyclo [4.4.0.1 ^2,5 ... Adducts of (cyclopentadiene-acenaphthylene adduct) and cyclopentadiene. 1 ^7,10 ] -3-dodecene derivative, pentacyclo [6.5.1.1 ^3,6 . 0 ^2,7 . 0 ^9,13] -4-pentadecene and its derivatives, pentacyclo [7.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-pentadecene and its derivatives, pentacyclo [8.4.0.1 ^2,5. 1 ^9,12 . 0 ^8,13] -3-hexadecene and derivatives thereof, pentacyclo [6.6.1.1 ^{3, 6.} 0 ^2,7 . 0 ^9,14] -4-hexadecene and derivatives thereof, hexacyclo [6.6.1.1 ^{3, 6.} 1 ^10,13 . 0 ^2,7 . 0 ^9,14] -4-heptadecene and its derivatives, heptacyclo [8.7.0.1 ^2,9. 1 ^4,7 . 1 ^{11, 17} . 0 ^3,8 . 0 ^12,16 ] -5-eicosene and its derivatives, heptacyclo [8.7.0.1 ^3,6 . 1 ^{10, 17} . 1 ^{12, 15} . 0 ^2,7 . 0 ^11,16 ] -4-eicosene and its derivatives, heptacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 0 ^3,8 . 0 ^12,17 ] -5- ^Heneicosene and derivatives thereof, octacyclo [8.8.0.1 ^2,9 . 1 ^4,7 . 1 ^{11, 18} . 1 ^13,16 . 0 ^3,8 . 0 ^12,17] -5-docosene and its derivatives, Nonashikuro [10.9.1.1 ^{4, 7.} 1 ^13,20 . 1 ^{15, 18} . 0 ^2,10 . 0 ^3,8 . 0 ^{12, 21} . 0 ^14,19] -5-pentacosene and derivatives thereof.

  Specific examples of the formula (I) or the formula (II) that can be used in this embodiment are as described above, and more specific structures of these compounds are disclosed in JP-A-7-145213. In the present embodiment, those exemplified in this specification can be used as the cyclic olefin.

  Examples of the method for producing the cyclic olefin represented by the general formula (I) or (II) include Diels-Alder reaction between cyclopentadiene and olefins having a corresponding structure.

  These cyclic olefins can be used alone or in combination of two or more. The cyclic olefin polymer used in the present embodiment is a cyclic olefin represented by the above formula (I) or (II), for example, Japanese Patent Application Laid-Open Nos. 60-168708 and 61-120816. According to the methods described in publications such as 61-115912, 61-115916, 61-271308, 61-272216, 62-252406, and 62-252407, conditions are appropriately selected. Can be manufactured.

<[A-1] α-olefin / cyclic olefin random copolymer>
[A-1] The α-olefin / cyclic olefin random copolymer having 2 to 20 carbon atoms contains a structural unit derived from an α-olefin, usually 20 to 95 mol%, preferably 30 to 90 mol. The structural unit derived from the cyclic olefin is usually contained in an amount of 5 to 80 mol%, preferably 10 to 70 mol%. The composition ratio of α-olefin and cyclic olefin is measured by ¹³ C-NMR.

  Here, the α-olefin having 2 to 20 carbon atoms constituting the α-olefin / cyclic olefin random copolymer [A-1] will be described. The α-olefin may be linear or branched and may be ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene. , 1-octadecene, 1-eicosene, etc., a linear α-olefin having 2 to 20 carbon atoms; 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4 -Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene And branched α-olefins having 4 to 20 carbon atoms. Among these, a linear α-olefin having 2 to 4 carbon atoms is preferable, and ethylene is particularly preferable. Such linear or branched α-olefins can be used singly or in combination of two or more.

  In the α-olefin / cyclic olefin random copolymer [A-1], a structural unit derived from an α-olefin having 2 to 20 carbon atoms and a structural unit derived from a cyclic olefin are included. , Randomly arranged and bonded, and has a substantially linear structure. The fact that this copolymer is substantially linear and has substantially no gel-like cross-linked structure means that when this copolymer is dissolved in an organic solvent, the solution contains insoluble matter. It can be confirmed by not. For example, when the intrinsic viscosity [η] is measured, the copolymer can be confirmed by being completely dissolved in 135 ° C. decalin.

  In the [A-1] α-olefin / cyclic olefin random copolymer used in this embodiment, at least a part of the cyclic olefin represented by the formula (I) or (II) is represented by the following formula (IV) or ( V) is considered to constitute the repeating unit.

式（ＩＶ）において、ｎ、ｍ、ｑ、Ｒ^１〜Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、式（Ｉ）におけるｎ、ｍ、ｑ、Ｒ^１〜Ｒ^１８と同じ意味である。

In the formula (IV), n, m, q, R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as n, m, q, R ^{1 to} R ¹⁸ in the formula (I).

式（Ｖ）において、ｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９は、式（ＩＩ）におけるｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９と同じ意味である。

In formula (V), n, m, p, q and ^R 1 ^{to R 19} are the same meaning n in the formula (II), m, p, and q and ^R 1 ^{to R 19.}

  In addition, the [A-1] α-olefin / cyclic olefin random copolymer used in the present embodiment is derived from other copolymerizable monomers as necessary within the range not impairing the object of the present invention. You may have a unit. Examples of such other monomer include α-olefins having 2 to 20 carbon atoms as described above or olefins other than cyclic olefins. Specifically, cyclobutene, cyclopentene, cyclohexene, 3,4 Cycloolefins such as dimethylcyclopentene, 3-methylcyclohexene, 2- (2-methylbutyl) -1-cyclohexene and cyclooctene, 3a, 5,6,7a-tetrahydro-4,7-methano-1H-indene, 1, Non-conjugated dienes such as 4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 1,7-octadiene, dicyclopentadiene and 5-vinyl-2-norbornene Can do.

These other monomers can be used alone or in combination.
[A-1] In the α-olefin / cyclic olefin random copolymer, the structural unit derived from the other monomer as described above is usually contained in an amount of 20 mol% or less, preferably 10 mol% or less. It may be.

  The [A-1] α-olefin / cyclic olefin random copolymer used in the present embodiment is a cyclic represented by the above-described α-olefin having 2 to 20 carbon atoms and the formula (I) or (II). It can be produced by the production method disclosed in the above publication using olefin. Among these, the copolymerization is performed in a hydrocarbon solvent, and a catalyst formed from a vanadium compound and an organoaluminum compound soluble in the hydrocarbon solvent is used as a catalyst. [A-1] α-olefin / cyclic olefin It is preferable to produce a random copolymer.

  In this copolymerization reaction, a solid periodic table group IVB metallocene-based catalyst can also be used. Here, the solid group IVB metallocene catalyst is a catalyst comprising a transition metal compound containing a ligand having a cyclopentadienyl skeleton, an organoaluminum oxy compound, and an organoaluminum compound blended as necessary. . The Group IV transition metal is zirconium, titanium, or hafnium, and these transition metals have a ligand containing at least one cyclopentadienyl skeleton. Examples of the ligand containing a cyclopentadienyl skeleton include a cyclopentadienyl group, an indenyl group, a tetrahydroindenyl group, and a fluorenyl group, which may be substituted with an alkyl group. These groups may be bonded via other groups such as an alkylene group. Examples of ligands other than the ligand containing a cyclopentadienyl skeleton include an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group.

  Moreover, what is normally used for manufacture of an olefin resin can be used for an organoaluminum oxy compound and an organoaluminum compound. As such a solid group IVB metallocene catalyst, for example, those described in JP-A-61-221206, JP-A-64-106 and JP-A-2-173112 can be used.

<[A-2] Cyclic Olefin Ring-Opening Polymer or Copolymer>
[A-2] The ring-opening polymer or copolymer of a cyclic olefin is a ring-opening polymer of a cyclic olefin represented by the formula (I) or (II), or the formula (I) and / or (II) It is a copolymer containing the ring-opening polymerization unit of the cyclic olefin represented. In the case of a copolymer, two or more different cyclic olefins are used in combination.

  In the ring-opening polymer or ring-opening copolymer of a cyclic olefin, at least a part of the cyclic olefin represented by the formula (I) or (II) is a repeating unit represented by the following formula (VI) or (VII) It is thought that it constitutes.

式（ＶＩ）において、ｎ、ｍ、ｑおよびＲ^１〜Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、式（Ｉ）におけるｎ、ｍ、ｑおよびＲ^１〜Ｒ^１８と同じ意味である。

In the formula (VI), n, m, q and R ^{1 to} R ¹⁸ and R ^a and R ^b have the same meaning as n, m, q and R ^{1 to} R ¹⁸ in the formula (I).

式（ＶＩＩ）において、ｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９は、式（ＩＩ）におけるｎ、ｍ、ｐ、ｑおよびＲ^１〜Ｒ^１９と同じ意味である。

In formula (VII), n, m, p, q and ^R 1 ^{to R 19} are the same meaning n in the formula (II), m, p, and q and ^R 1 ^{to R 19.}

  Such a ring-opening polymer or ring-opening copolymer can be produced by the production method disclosed in the above publication, for example, the cyclic olefin represented by the formula (I) in the presence of a ring-opening polymerization catalyst. And can be produced by polymerization or copolymerization. As the ring-opening polymerization catalyst, a metal halide selected from ruthenium, rhodium, palladium, osmium, indium, platinum, etc., a catalyst comprising a nitrate or acetylacetone compound and a reducing agent, or titanium, palladium, zirconium, molybdenum, etc. A metal halide selected or a catalyst composed of an acetylacetone compound and an organoaluminum compound can be used.

<[A-3] Hydrogenated product of ring-opening polymer or copolymer>
The hydride of [A-3] ring-opening polymer or copolymer used in the present embodiment is obtained by replacing the ring-opening polymer or copolymer [A-2] obtained as described above with a conventionally known hydrogen. Obtained by hydrogenation in the presence of added catalyst.

  In the hydride of this [A-3] ring-opening polymer or copolymer, at least a part of the cyclic olefin represented by the formula (I) or (II) is represented by the following formula (VIII) or (IX): It is thought that it constitutes a repeating unit represented by

式（ＶＩＩＩ）において、ｎ、ｍ、ｑおよびＲ^１〜Ｒ^１８ならびにＲ^ａおよびＲ^ｂは、式（Ｉ）におけるｎ、ｍ、ｑおよびＲ^１〜Ｒ^１８ならびにＲ^ａおよびＲ^ｂと同じ意味である。

In formula (VIII), n, m, q and ^R 1 ^{to R 18} and ^{R a} and ^{R b,} n in formula (I), m, the same meaning as q and ^R 1 ^{to R 18, R a} and ^{R b} It is.

式（ＩＸ）においてｎ、ｍ、ｐ、ｑ、Ｒ^１〜Ｒ^１９は、式（ＩＩ）におけるｎ、ｍ、ｐ、ｑ、Ｒ^１〜Ｒ^１９と同じ意味である。

^{N, m, p, q,} R 1 ~R 19 in formula (IX) are the same meaning n in the formula ^{(II), m, p,} q, and R 1 ^{to R 19.}

<[A-4] Graft modified product>
The graft modified product of the cyclic olefin polymer is the above [A-1] α-olefin / cyclic olefin random copolymer, [A-2] a ring-opening polymer or copolymer of cyclic olefin, or [A -3] Graft-modified product of hydride of ring-opening polymer or copolymer.

Examples of the modifier used here include usually unsaturated carboxylic acids, and specifically, (meth) acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isocrotonic acid. , Unsaturated carboxylic acids such as endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ), and derivatives of these unsaturated carboxylic acids such as unsaturated carboxylic anhydrides And unsaturated carboxylic acid halides, unsaturated carboxylic acid amides, unsaturated carboxylic acid imides, ester compounds of unsaturated carboxylic acids, and the like.

  Specific examples of the unsaturated carboxylic acid derivative include maleic anhydride, citraconic anhydride, maleenyl chloride, maleimide, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

  Of these, α, β-unsaturated dicarboxylic acids and α, β-unsaturated dicarboxylic anhydrides such as maleic acid, nadic acid and anhydrides of these acids are preferably used. Two or more of these modifiers can be used in combination.

  Such a graft modified product of a cyclic olefin polymer can be produced by blending a cyclic olefin polymer with a modifier so as to obtain a desired modification rate, and can be produced by graft polymerization. It can also be produced by preparing a product, and then mixing this modified product and an unmodified cyclic olefin polymer so as to obtain a desired modification rate.

  In order to obtain a graft modified product of a cyclic olefin polymer from the cyclic olefin polymer and a modifier, conventionally known polymer modification methods can be widely applied. For example, a graft modified product may be obtained by adding a modifier to a cyclic olefin polymer in a molten state for graft polymerization (reaction), or adding a modifier to a solvent solution of the cyclic olefin polymer to cause a graft reaction. Can be obtained.

  Such a grafting reaction is usually performed at a temperature of 60 to 350 ° C. The graft reaction can be performed in the presence of a radical initiator such as an organic peroxide and an azo compound.

  In the present embodiment, any one of the above [A-1], [A-2], [A-3] and [A-4] can be used alone as the cyclic olefin polymer, These can also be used in combination. Among these, α-olefin / cyclic olefin random copolymer [A-1] is preferably used. Furthermore, an ethylene / tetracyclododecene copolymer or an ethylene / norbornene copolymer is preferable.

  In the present embodiment, as the cyclic olefin-based resin, a resin composition obtained by blending the cyclic olefin-based polymer with another resin as necessary can be used. Other resin is added in the range which does not impair the object of the present invention.

  Polymers (resin components) that can be blended with cyclic olefin polymers include polymers such as polyolefins derived from hydrocarbons having one or two unsaturated bonds; polyvinyl chloride, chlorinated rubber, etc. Halogen-containing vinyl polymers; polymers derived from α, β-unsaturated acids and their derivatives, specifically polyacrylates, polymethacrylates, acrylonitrile-butadiene-styrene copolymers, etc .; unsaturated alcohols and amines or their Polymers such as polyvinyl alcohol and polyvinyl acetate derived from acyl derivatives or acetals; Polymers derived from epoxides such as polyethylene oxide; Polyacetals; Polyphenylene oxides; Polycarbonates; Polysulfones; Polyurethanes and urea resins; Diamines and dicarboxylic acids Polyamides and copolyamides derived from acids and / or aminocarboxylic acids or corresponding lactams such as nylon 6, nylon 66, etc .;

  Furthermore, polyesters derived from dicarboxylic acids and dialcohols and / or oxycarboxylic acids or the corresponding lactones, such as polyethylene terephthalate; polymers with cross-linked structures derived from aldehydes and phenols, urea or melamine, etc. Alkyd resins; unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols and obtained using vinyl compounds as crosslinking agents; halogen-containing modified resins; natural materials such as cellulose and rubber Polymers: Soft polymers such as α-olefin copolymers and α-olefin / diene copolymers.

  In addition to the above-mentioned components, the cyclic olefin-based resin is a conventionally known weather resistance stabilizer, heat resistance stabilizer, antistatic agent, flame retardant, slip agent, anti-blocking agent, as long as the object of the present invention is not impaired. Antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers and the like may be added. As a method for mixing the cyclic olefin polymer with other resin components and additives, a method known per se can be applied. For example, a method of mixing each component simultaneously.

DESCRIPTION OF SYMBOLS 1 Hopper 2 Screw 2a Supply part 2b 1st compression part 2c Melting completion part 2d 2nd compression part 2e Weighing part 2f Base end part 2g Tip part 3 Cylinder 4 Band heater 5 Cylinder head 6 Nozzle 7 Mold 21 Screw main body 22 Flight 31 Inner surface

Claims (11)

A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
A method for producing a cyclic olefin-based resin molded product, wherein a groove depth h of the screw at the melting completion position is a relatively small value. A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
In a cross section along the axial center of the screw body, a radius of curvature r of a boundary portion between the flight and the screw body is relatively large for at least one of the front side and the rear side of the flight. The manufacturing method of the cyclic olefin resin molded object which is this. A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
When the position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position, and the inner diameter of the cylinder is D,
The screw groove depth h at the melting completion position is:
h ≦ 0.67D ^0.5 (D ≦ 20mm)
h ≦ 0.15D (D> 20mm)
The manufacturing method of the cyclic olefin resin molded object which satisfy | fills. In the axial direction of the cylinder, at least the groove depth h of the screw from the position upstream by 5D from the melting completion position to the melting completion position is
h ≦ 0.67D ^0.5 (D ≦ 20mm)
h ≦ 0.15D (D> 20mm)
The manufacturing method of the cyclic olefin resin molded object of Claim 1 which satisfy | fills. h> 0.005D (D ≦ 20 mm)
h ≧ 0.022D ^0.5 (D> 20 mm)
The manufacturing method of the cyclic olefin resin molded object of Claim 3 or 4 which satisfy | fills.   In at least one of the front side and the rear side of the flight, the radius of curvature r at the boundary between the flight and the screw body is not less than h in the cross section along the axis of the screw body. The manufacturing method of the cyclic olefin resin molded object as described in any one of Claims 3 thru | or 5. A method for producing a cyclic olefin-based resin molded body, wherein a cyclic olefin-based resin molded body is manufactured using a molding machine having a cylinder and a screw inserted into the cylinder,
Comprising a step of molding a cyclic olefin-based resin by the molding machine,
The screw has a screw body and a flight formed around the screw body,
A position where the melting of the cyclic olefin-based resin is completed in the axial direction of the cylinder is a melting completion position,
When the groove depth of the screw at the melting completion position is h,
In at least one of the front side and the rear side of the flight, the radius of curvature r at the boundary between the flight and the screw body is not less than h in the cross section along the axis of the screw body. A method for producing a cyclic olefin-based resin molding.   The method for producing a cyclic olefin-based resin molded article according to claim 6 or 7, wherein the curvature radius r is 5 h or less. Supplying the cyclic olefin-based resin to the molding machine in the form of pellets;
The cyclic olefin resin molded product according to any one of claims 1 to 8, wherein a groove depth of the screw at a supply position of the cyclic olefin resin is deeper than a groove depth of the screw at the melting completion position. Production method.   The method for producing a cyclic olefin-based resin molded body according to any one of claims 1 to 9, wherein the cyclic olefin-based resin is molded by heating under a temperature condition of 160 ° C or higher and 350 ° C or lower.   The method for producing a cyclic olefin-based resin molded body according to any one of claims 1 to 10, wherein the cyclic olefin-based resin is molded while the screw is rotated at a rotation speed of 10 rpm to 200 rpm.

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