JP6992208B1 - Resin composition manufacturing method and mixing device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a resin composition for efficiently producing a resin composition in which a resin material and an additive having a viscosity lower than that of the resin material are uniformly mixed. In the method for producing a resin composition of the present invention, a resin material 2 and an additive having a viscosity lower than that of the resin material 2 at a temperature at which the resin material 2 liquefies are placed in a container 1 and the resin material 2 is provided. The resin material 2 is repositioned in the container 1 so that the resin material 2 alternately repeats the first state and the second state at the temperature at which the resin material 2 liquefies, and the resin material 2 and the additive are mixed. including. The first state is a state in which the resin material 2 fills the first specific surface area. The second state is a state in which the resin material 2 satisfies the second specific surface area in which the ratio to the first specific surface area is 70% or less. The first specific surface area and the second specific surface area are specific surface areas obtained by the formula (1). Equation (1): Specific surface area [cm-1] = Surface area of resin material [cm2] / Volume of resin material [cm3] [Selection diagram] Fig. 1

Description

The present invention relates to a method for producing a resin composition and a mixing device.

Techniques for uniformly mixing two or more substances having different viscosities are useful in various technical fields. For example, when producing a material for an optical member, it may be necessary to mix a high-viscosity resin with a low-viscosity additive for the purpose of adjusting the refractive index. For example, the material (core material) of the core portion of a plastic optical fiber (hereinafter referred to as "POF") is generally a resin composition obtained by mixing various additives such as a refractive index adjuster with the resin. Things are used. The resin used for the core material generally has a high viscosity. On the other hand, as the refractive index adjusting agent, a compound having a relatively low molecular weight is generally used. Therefore, the refractive index adjuster has a low viscosity. Therefore, in order to prepare a resin composition that can be used as a core material for POF, it is usually required to uniformly mix a low-viscosity additive with a high-viscosity resin.

When two or more substances having different viscosities are uniformly mixed, a method of stirring the mixture using a stirring blade is generally used. However, when the stirring blade is used for producing the core material of the POF, the components constituting the stirring blade (for example, the metal component) are mixed in the core material, and the characteristics of the core material are impaired. Therefore, a method using a stirring blade cannot be used for manufacturing a material such as a core material of POF in which contamination of impurities must be avoided as much as possible.

As a method capable of uniformly mixing two or more substances having different viscosities without using a stirring blade, for example, Patent Document 1 describes a highly viscous viscous material in which a solid filler is mixed with a liquid resin raw material. Is disclosed as a stirring method capable of uniformly stirring the above. In the stirring method disclosed in Patent Document 1, a highly viscous viscous material is housed in a deformable bag-shaped container, and the viscous material in the bag-shaped container is stirred by repeatedly expanding and contracting the bag-shaped container.

Japanese Patent No. 6073726

According to the method disclosed in Patent Document 1, a highly viscous viscous material in which a solid filler is mixed with a liquid resin raw material can be uniformly agitated. However, when two or more substances having different viscosities are a high-viscosity liquid substance and a low-viscosity liquid substance, it is very difficult to efficiently and uniformly mix them. Therefore, in a method of repeatedly expanding and contracting a bag-shaped container as in the method disclosed in Patent Document 1, a high-viscosity liquid resin material and a low-viscosity liquid additive are efficiently and uniformly mixed. It is difficult to make a resin composition that can be used as a core material for POF.

Therefore, the present invention provides a method for producing a resin composition for efficiently producing a resin composition in which a resin material and an additive having a viscosity lower than that of the resin material are uniformly mixed. The purpose. Furthermore, it is also an object of the present invention to provide a mixing device capable of efficiently and uniformly mixing at least two substances having different viscosities.

In the method for producing a resin composition according to the first aspect of the present invention, a resin material and an additive having a viscosity lower than that of the resin material at a temperature at which the resin material liquefies are placed in a container, and the resin material is prepared. The resin material is repositioned in the container so that the resin material alternately repeats the first state and the second state at the temperature at which the resin material is liquefied, and the resin material and the additive are mixed. Including
The first state is a state in which the resin material fills the first specific surface area.
The second state is a state in which the resin material satisfies the second specific surface area in which the ratio to the first specific surface area is 70% or less.
The first specific surface area and the second specific surface area are specific surface areas obtained by the following formula (1).
Specific surface area [cm ^-1 ] = Surface area of resin material [cm ² ] / Volume of resin material [cm ³ ]… (1)

The mixing device according to the second aspect of the present invention is
A mixing device that mixes a first substance and a second substance having a viscosity lower than that of the first substance.
A container with a shape that extends in the uniaxial direction,
A mechanism for rotating or reversing the container in a direction in which the positions of one end and the other end in the longitudinal direction of the container are opposite to each other.
Equipped with
The rotation speed R and the inversion period of the container are the following formulas (4) and (when L [m] is the length in the uniaxial direction of the container and μ [Pa · s] is the viscosity of the first substance. 5) is satisfied,
1.5 <R [rpm] x L [m] x μ [Pa · s] <10 ... (4)
Inversion cycle [times / min] = R × 2… (5)
Here, the viscosity of the first substance is the viscosity of the first substance at the mixing temperature of the first substance and the second substance.

According to the method for producing a resin composition according to the first aspect of the present invention, a resin composition in which a resin material and an additive having a viscosity lower than that of the resin material are uniformly mixed is efficiently produced. be able to. Further, according to the mixing device according to the second aspect of the present invention, the first substance and the second substance having a viscosity lower than that of the first substance can be efficiently and uniformly mixed.

FIG. 1 is a schematic diagram illustrating an embodiment of a method for producing a resin composition of the present invention. FIG. 2A is a cross-sectional view schematically showing how the resin material is deformed along the shape of the bottom of the container, but is present only in a part of the bottom of the container and is not accumulated in the entire bottom. .. FIG. 2B is a cross-sectional view schematically showing the state of the resin material when it is assumed that the resin material is accumulated in the entire bottom of the container.

(Embodiment 1)
An embodiment of the method for producing a resin composition of the present invention will be described.

In the method for producing a resin composition of the present embodiment, a resin material and an additive having a viscosity lower than that of the resin material at the temperature at which the resin material is liquefied are placed in a container and brought to a temperature at which the resin material is liquefied. The resin material is repositioned in the container so that the resin material alternates between the first state and the second state, and the resin material and the additive are mixed. In the method for producing a resin composition of the present embodiment, for example, the container itself is operated so that the resin material contained therein repeats the first state and the second state alternately. For example, by rotating or inverting the container, a position change may be performed in which the resin material contained therein repeats the first state and the second state alternately. The resin material and the additive may be liquid at the time of mixing. Therefore, the resin material and the additive may be solid or liquid at the time of being placed in the container.

In the method for producing a resin composition of the present embodiment, the resin material is placed in a container so that the resin material alternates between the first state and the second state until the resin material and the additive are uniformly mixed. It is preferable to change the position.

Here, the first state of the resin material is a state in which the resin material satisfies the first specific surface area. The second state of the resin material is a state in which the resin material satisfies the second specific surface area in which the ratio to the first specific surface area is 70% or less. The first specific surface area and the second specific surface area are specific surface areas obtained by the following formula (1).

Specific surface area [cm ^-1 ]
= Surface area of resin material [cm ² ] / Volume of resin material [cm ³ ]… (1)

In the method for producing a resin composition of the present embodiment, the resin material and the additive having a viscosity lower than that of the resin material at the temperature at which the resin material is liquefied are resin at a temperature at which the resin material is liquefied. The resin material is repositioned in the container and mixed so that the material alternates between the first and second states. When the resin material and the additive are mixed with each other by a method that causes such a position change, the resin material and the additive can be mixed while changing the positions of contact with each other and contacting each other at the time of mixing. Therefore, according to the method for producing a resin composition of the present embodiment, two or more kinds of liquid substances, which have a large difference in viscosity and are difficult to be uniformly mixed by the conventional method, are efficiently and uniformly mixed. be able to.

The "surface area of the resin material" here means the surface area of the resin material in a liquefied state contained in a container used for mixing the resin material and the additive. Therefore, the surface area of the resin material can be determined from the shape and size of the container used for mixing the resin material and the additive, and the state of the resin material in the container. The state of the resin material in the container is, for example, in what part of the container the resin material is located and in what shape it exists. For example, in advance, the relationship between the positions that the containers can take when the containers are operated (for example, when rotated or inverted) and the surface area of the resin material inside at each position of those containers is determined. Thereby, the surface area of the resin material during the operation of the container can be obtained.

In the present embodiment, for example, when the container is operated by a predetermined method, the state in which the surface area of the resin material contained therein is the largest is the first state, and the state in which the surface area is the smallest is the second state. Can be done. That is, in the position change of the resin material in the container 1 that is repeated when the container is operated by a predetermined method, the state when the surface area of the resin material becomes the maximum and the state when the surface area of the resin material becomes the minimum are the above-mentioned first. When the relationship between the first state and the second state is satisfied, it can be certified that the manufacturing method of the present embodiment is carried out by operating the container by that method.

The container preferably has a shape such that the change in the surface area of the resin material inside the container becomes large when operated, and preferably has a shape extending in the uniaxial direction such as a prism and a cylinder. When the container has a shape extending in the uniaxial direction, the change in the surface area of the resin material inside the container is increased by rotating or reversing the container in the direction in which the positions of one end and the other end in the longitudinal direction of the container are opposite to each other. be able to. Therefore, by using such a container, it becomes easy to change the position of the resin material between the first state and the second state. That is, in the method for producing a resin composition of the present embodiment, a container having a shape extending in the uniaxial direction is used, and the container is rotated or inverted in the direction in which the positions of one end and the other end in the longitudinal direction of the container are reversed. It is preferable that the resin material and the additive in the container are mixed by allowing the mixture. The position change of the resin material in the container can be realized, for example, by adjusting the rotation speed or the inversion period when the container is rotated or inverted.

When a container having a shape extending in the uniaxial direction is used as the container, specifically, a case where a cylindrical container 1 as shown in FIG. 1 is used as an example, the first state and the second state are further described. This will be described in detail.

As shown in FIG. 1, by rotating or reversing the container 1 in a direction in which the positions of one end 1a and the other end 1b in the longitudinal direction of the container 1 are opposite to each other (states (a) to (e) of FIG. 1). ), The resin material 2 can be repositioned in the container 1. In that case, the resin material 2 may have the largest surface area in the container 1 when the long axis direction A of the container 1 is substantially parallel to the horizontal direction, that is, the container 1 is shown in the center of FIG. This is the state (c). On the other hand, the resin material 2 may have the smallest surface area in the container 1 when the long axis direction A of the container 1 is substantially parallel to the vertical direction, that is, the container 1 is shown at both ends of FIG. It is in the state (a) and the state (e).

The state of the resin material 2 in the container 1 can be confirmed by, for example, the following method. First, a transparent container having the same shape as the container 1 used for mixing and made of a transparent material (for example, glass) whose inside can be confirmed from the outside is prepared. In this transparent container, only the amount of resin material used for mixing is put, and the transparent container is operated by a method (for example, rotation or inversion) carried out at the time of mixing, and the operation of the transparent container and the inside of the container are performed. The relationship with the state (shape and position) of the resin material can be confirmed in advance.

When the rotation speed or inversion cycle of the container 1 is set so that the resin material 2 in the container 1 moves in the container 1 by gravity as the container 1 rotates or inverts, as shown in FIG. The resin material 2 has the maximum surface area in the state (c) and the minimum surface area in the state (a) and the state (e) in the container 1. In this case, when the major axis direction A of the container 1 is substantially parallel to the horizontal direction (c), the surface area of the resin material 2 accumulated at the bottom of the container 1 is obtained, and the surface area obtained is obtained from the obtained surface area. The specific surface area of one state is obtained. On the other hand, when the major axis direction of the container 1 is substantially parallel to the vertical direction (a) and the state (e), the surface area of the resin material 2 accumulated at the bottom of the container 1 is obtained. The specific surface area of the second state can be obtained from the surface area. Depending on the viscosity of the resin material 2 and the size of the container 1 in the longitudinal direction, the resin material 2 is deformed along the shape of the bottom of the container 1 in the state (c), but the container 1 is used. It is present only in a part of the bottom and may not be accumulated in the entire bottom (see FIG. 2A). In such a case, assuming that the resin material 2 is accumulated in the entire bottom of the container 1 (see FIG. 2B), the shape of the bottom portion of the container 1 in the volume and state (c) of the resin material 2 May be used to determine the surface area of the resin material 2.

The first specific surface area is preferably 0.3 cm ^-1 or more and 10 cm ^-1 or less, and more preferably 0.4 cm ^-1 or more and 5 cm ^-1 or less. The second specific surface area is preferably 0.2 cm ^-1 or more and 5 cm ^-1 or less, and more preferably 0.28 cm ^-1 or more and 3 cm ^-1 or less. When the first specific surface area and the second specific surface area of the resin material 2 satisfy the above ranges, the resin material 2 can be more efficiently and uniformly mixed with the low-viscosity additive.

When the resin material 2 and the additive 3 in the container 1 are mixed by rotating or reversing the container 1, the rotation speed R and the reversing cycle of the container 1 are L [m], which is the length in the uniaxial direction of the container 1. When μ [Pa · s] is the viscosity of the resin material 2, it is preferable to satisfy the following formulas (2) and (3).
1.5 <R [rpm] x L [m] x μ [Pa · s] <10 ... (2)
Inversion cycle [times / min] = R × 2… (3)
Here, the viscosity of the resin material is the viscosity of the resin material at the mixing temperature of the resin material and the additive.

When the container 1 satisfies the above formulas (2) and (3), the position change between the first state and the second state of the resin material 2 in the container 1 can be more reliably realized, and the resin material 2 and Mixing of the additive 3 becomes easy.

Here, the viscosity of the resin material 2 is a value measured by a rotary viscosity measuring method, and is measured by using a rotary rheometer. For example, as a measuring device, a rotary rheometer "HAAKE MARS III" (manufactured by Thermo Fisher Scientific Hook Co., Ltd.) is used. As the geometry, for example, a cone plate (φ20 mm, 4 °) is used. As a measurement method, for example, the setting of the resin sample is completed within 15 minutes on a cone plate stable at the measurement temperature, and the measurement is started. Viscosity measurement is carried out at a shear rate of 0.01-5 (1 / s) and a measurement time of 10 min.

The time during which all of the resin material 2 is repositioned from the position of one end 1a of the container 1 to the position of the other end 1b by the rotation or inversion of the container 1 is defined as the position conversion cycle of the resin material 2, and the rotation or reversal of the container 1 is performed. When the time for all of the additive 3 to be repositioned from the position of one end 1a of the container 1 to the position of the other end 1b by inversion is defined as the position conversion cycle of the additive 3, the position conversion cycle of the additive 3 is It is preferably smaller than the position conversion period of the resin material 2. When the position conversion cycle of the additive 3 and the position conversion cycle of the resin material 2 satisfy such a relationship, the resin material 2 and the additive 3 can be mixed more efficiently and uniformly.

By adjusting the rotation speed or the inversion cycle of the container 1, the position conversion cycle of the additive 3 and the position conversion cycle of the resin material 2 satisfying the above relationship can be realized. It is preferable to confirm the relationship between the position conversion cycle of the additive 3 and the position conversion cycle of the resin material 2 and the rotation speed or the inversion cycle of the container 1 by preliminary measurement in advance. For example, a transparent container having the same shape as the container 1 used for mixing and made of a transparent material (for example, glass) whose inside can be confirmed from the outside is prepared. In this transparent container, only the amount of the resin material 2 or the additive 3 used for mixing is put, and the transparent container is rotated or inverted. At this time, the resin material 2 or the additive 3 is one end of the transparent container. Measure the time to change the position from the position of to the position of the other end. It is preferable to repeat this while changing the rotation speed or the inversion period to obtain the relationship between the rotation speed or the inversion period and the position conversion period of the resin material 2 and the additive 3.

In order to sufficiently and uniformly mix the resin material 2 and the additive 3, it is desirable to rotate or invert the container 1. However, when the degree of uniformity may be low, or when the viscosity of the resin material is not so high, even the operation of the container 1 in which the container is rotated by about 90 degrees and returned to its original state has some effect. can get. However, in order to obtain a sufficiently uniform mixture, at least inversion is required.

The viscosity of the resin material 2 used in the method for producing the resin composition of the present embodiment is not particularly limited, but the viscosity of the resin material 2 is, for example, 10 Pa · s or more at the mixing temperature of the resin material 2 and the additive 3. It may be 1000 Pa · s or less. Even when the resin material 2 has such a very high viscosity, according to the production method of the present embodiment, uniform mixing with the low-viscosity additive 3 is possible.

The viscosity of the additive 3 used in the method for producing the resin composition of the present embodiment is not particularly limited. In consideration of uniform mixing with the resin material 2, the viscosity of the additive 3 may be, for example, 0.001 Pa · s or more and 1 Pa · s or less at the mixing temperature of the resin material 2 and the additive 3. Even when the additive 3 has such a low viscosity, according to the production method of the present embodiment, uniform mixing with the resin material 2 is possible.

The difference in viscosity between the resin material 2 and the additive 3 is not particularly limited. As described above, the viscosity of the resin material 2 is, for example, 10 Pa · s or more and 1000 Pa · s or less, and the viscosity of the additive 3 is, for example, 0.001 Pa · s or more and 1 Pa · s or less. According to the method for producing a resin composition of the present embodiment, substances having such a large difference in viscosity can be efficiently and uniformly mixed with each other.

The mixing temperature can be appropriately selected depending on the resin material 2 and the additive 3 used in the production method of the present embodiment. For example, mixing is performed in a temperature range in which the resin material 2 is melted and the additive 3 is not volatilized. When the produced resin composition is used, for example, as a core material for POF, the mixing temperature is, for example, in the range of 200 to 300 ° C., for example, about 270 ° C.

The resin material contains, for example, a fluorine-containing polymer. The fluorine-containing polymer is a useful substance used in a wide range of fields as an optical member such as a POF or an exposed member, or as a surface modifier or the like. Therefore, a resin material containing a fluorine-containing polymer is used, and the resin composition produced by the production method of the present embodiment can be used as a material for an optical member such as a POF, for example, a core material for a POF. Can be used as.

In the present embodiment, when the resin material contains a fluorinated polymer, the fluorinated polymer does not substantially contain hydrogen atoms from the viewpoint of suppressing light absorption due to the expansion and contraction energy of the CH bond. It is particularly preferable that all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. That is, it is preferable that the fluorinated polymer contained in the resin material does not substantially contain hydrogen atoms and is completely fluorinated. In the present specification, the fact that the fluorine-containing polymer does not substantially contain hydrogen atoms means that the content of hydrogen atoms in the fluorine-containing polymer is 1 mol% or less.

The fluorine-containing polymer preferably has a fluorine-containing aliphatic ring structure. The fluorinated aliphatic ring structure may be contained in the main chain of the fluorinated polymer, or may be contained in the side chain of the fluorinated polymer. The fluorine-containing polymer has, for example, a structural unit (A) represented by the following structural formula (1).

In the structural formula (1), R _ff ¹ to R _ff ⁴ independently represent a fluorine atom, a perfluoroalkyl group having 1 to 7 carbon atoms, or a perfluoroalkyl ether group having 1 to 7 carbon atoms. R _ff ¹ and R _ff ² may be connected to form a ring. "Perfluoro" means that all hydrogen atoms bonded to carbon atoms are replaced with fluorine atoms. In the structural formula (1), the number of carbon atoms of the perfluoroalkyl group is preferably 1 to 5, more preferably 1 to 3, and even more preferably 1. The perfluoroalkyl group may be linear or branched. Examples of the perfluoroalkyl group include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group and the like.

In the structural formula (1), the number of carbon atoms of the perfluoroalkyl ether group is preferably 1 to 5, and more preferably 1 to 3. The perfluoroalkyl ether group may be linear or branched chain. Examples of the perfluoroalkyl ether group include a perfluoromethoxymethyl group.

When R _ff ¹ and R _ff ² are connected to form a ring, the ring may be a 5-membered ring or a 6-membered ring. Examples of this ring include a perfluorotetrahydrofuran ring, a perfluorocyclopentane ring, and a perfluorocyclohexane ring.

Specific examples of the structural unit (A) include structural units represented by the following structural formulas (A1) to (A8).

The structural unit (A) is preferably a structural unit (A2), that is, a structural unit represented by the following structural formula (2), among the structural units represented by the structural formulas (A1) to (A8). ..

The fluorine-containing polymer may contain one or more constituent units (A). In the fluorine-containing polymer, the content of the structural unit (A) is preferably 20 mol% or more, more preferably 40 mol% or more, based on the total of all the structural units. When the structural unit (A) is contained in an amount of 20 mol% or more, the fluorine-containing polymer tends to have higher heat resistance. When the structural unit (A) is contained in an amount of 40 mol% or more, the fluorine-containing polymer tends to have higher transparency and higher mechanical strength in addition to high heat resistance. In the fluorine-containing polymer, the content of the structural unit (A) is preferably 95 mol% or less, more preferably 70 mol% or less, based on the total of all the structural units.

The structural unit (A) is derived from, for example, a compound represented by the following structural formula (3). In the structural formula (3), R _ff ¹ to R _ff ⁴ are the same as the structural formula (1). The compound represented by the structural formula (3) can be obtained by a production method already known, for example, the production method disclosed in JP-A-2007-504125.

Specific examples of the compound represented by the structural formula (3) include compounds represented by the following structural formulas (M1) to (M8).

The fluorine-containing polymer may further contain other structural units in addition to the structural unit (A). Examples of other structural units include the following structural units (B) to (D).

The structural unit (B) is represented by the following structural formula (4).

In the structural formula (4), R ¹ to R ³ independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms. R ⁴ represents a perfluoroalkyl group having 1 to 7 carbon atoms. The perfluoroalkyl group may have a ring structure. A part of the fluorine atom may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkyl group may be substituted with a halogen atom other than the fluorine atom.

The fluorine-containing polymer may contain one or more constituent units (B). In the fluorine-containing polymer, the content of the structural unit (B) is preferably 5 to 10 mol% with respect to the total of all the structural units. The content of the structural unit (B) may be 9 mol% or less, or may be 8 mol% or less.

The structural unit (B) is derived from, for example, a compound represented by the following structural formula (5). In the structural formula (5), R ¹ to R ⁴ are the same as the structural formula (4). The compound represented by the structural formula (5) is a fluorine-containing vinyl ether such as perfluorovinyl ether.

The structural unit (C) is represented by the following structural formula (6).

In the structural formula (6), R ⁵ to R ⁸ independently represent a fluorine atom or a perfluoroalkyl group having 1 to 7 carbon atoms. The perfluoroalkyl group may have a ring structure. A part of the fluorine atom may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkyl group may be substituted with a halogen atom other than the fluorine atom.

The fluorine-containing polymer may contain one or more constituent units (C). In the fluorine-containing polymer, the content of the structural unit (C) is preferably 5 to 10 mol% with respect to the total of all the structural units. The content of the structural unit (C) may be 9 mol% or less, or may be 8 mol% or less.

The structural unit (C) is derived from, for example, a compound represented by the following structural formula (7). In the structural formula (7), R ⁵ to R ⁸ are the same as the structural formula (6). The compound represented by the structural formula (7) is a fluorine-containing olefin such as tetrafluoroethylene and chlorotrifluoroethylene.

The structural unit (D) is represented by the following structural formula (8).

In the structural formula (8), Z represents an oxygen atom, a single bond, or -OC (R ¹⁹ R ²⁰ ) O-, and R ⁹ to R ²⁰ are independently fluorine atoms and pars having 1 to 5 carbon atoms. Represents a fluoroalkyl group or a perfluoroalkoxy group having 1 to 5 carbon atoms. A part of the fluorine atom may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkyl group may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkoxy group may be substituted with a halogen atom other than the fluorine atom. s and t independently represent integers of 0 to 5 and s + t of 1 to 6 (where Z is -OC (R ¹⁹ R ²⁰ ) O-, s + t may be 0).

The structural unit (D) is preferably represented by the following structural formula (9). The structural unit represented by the following structural formula (9) is a case where Z is an oxygen atom, s is 0, and t is 2 in the structural formula (8).

In structural formula (9), R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ , and R ¹⁵² each independently have a fluorine atom, a perfluoroalkyl group having 1 to 5 carbon atoms, or a perfluoroalkoxy group having 1 to 5 carbon atoms. show. A part of the fluorine atom may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkyl group may be substituted with a halogen atom other than the fluorine atom. A part of the fluorine atom in the perfluoroalkoxy group may be substituted with a halogen atom other than the fluorine atom.

The fluorine-containing polymer may contain one or more constituent units (D). In the fluorine-containing polymer, the content of the structural unit (D) is preferably 30 to 67 mol% with respect to the total of all the structural units. The content of the structural unit (D) is, for example, 35 mol% or more, 60 mol% or less, or 55 mol% or less.

The structural unit (D) is derived from, for example, a compound represented by the following structural formula (10). In the structural formula (10), Z, R ⁹ to R ¹⁸ , s and t are the same as those in the structural formula (8). The compound represented by the structural formula (10) is a fluorine-containing compound having two or more polymerizable double bonds and capable of cyclization polymerization.

The structural unit (D) is preferably derived from the compound represented by the following structural formula (11). In the structural formula (11), R ¹⁴¹ , R ¹⁴² , R ¹⁵¹ , and R ¹⁵² are the same as the structural formula (9).

Specific examples of the compound represented by the structural formula (10) or the structural formula (11) include the following compounds.
CF ₂ = CFOCF ₂ CF = CF ₂
CF ₂ = CFOCF (CF ₃ ) CF = CF ₂
CF ₂ = CFOCF ₂ CF ₂ CF = CF ₂
CF ₂ = CFOCF ₂ CF (CF ₃ ) CF = CF ₂
CF ₂ = CFOCF (CF ₃ ) CF ₂ CF = CF ₂
CF ₂ = CFOCFClCF ₂ CF = CF ₂
CF ₂ = CFOCCl ₂ CF ₂ CF = CF ₂
CF ₂ = CFOCF ₂ OCF = CF ₂
CF ₂ = CFOC (CF ₃ ) ₂ OCF = CF ₂
CF ₂ = CFOCF ₂ CF (OCF ₃ ) CF = CF ₂
CF ₂ = CFCF ₂ CF = CF ₂
CF ₂ = CFCF ₂ CF ₂ CF = CF ₂
CF ₂ = CFCF ₂ OCF ₂ CF = CF ₂
CF ₂ = CFOCF ₂ CFClCF = CF ₂
CF ₂ = CFOCF ₂ CF ₂ CCl = CF ₂
CF ₂ = CFOCF ₂ CF ₂ CF = CFCl
CF ₂ = CFOCF ₂ CF (CF ₃ ) CCl = CF ₂
CF ₂ = CFOCF ₂ OCF = CF ₂
CF ₂ = CFOCCl ₂ OCF = CF ₂
CF ₂ = CClOCF ₂ OCCl = CF ₂

The fluorine-containing polymer may further contain other structural units other than the structural units (A) to (D), but substantially contains other structural units other than the structural units (A) to (D). It is preferable that there is no such thing. It should be noted that the fact that the fluorine-containing polymer does not substantially contain other structural units other than the constituent units (A) to (D) means that the constituent units (A) to (A) to the total of all the constituent units in the fluorine-containing polymer. It means that the total of (D) is 95 mol% or more, preferably 98 mol% or more.

The polymerization method of the fluorine-containing polymer is not particularly limited, and for example, a general polymerization method such as radical polymerization can be used. The polymerization initiator for polymerizing the fluorinated polymer may be a fully fluorinated compound.

The glass transition temperature (Tg) of the fluorine-containing polymer is not particularly limited, and may be, for example, 100 ° C to 140 ° C, 105 ° C or higher, or 120 ° C or higher. As used herein, Tg means the midpoint glass transition temperature (T _mg ) determined in accordance with JIS K7121: 1987.

The resin material may contain a fluorine-containing polymer as a main component, and it is preferable that the resin material is substantially composed of only the fluorine-containing polymer.

The additive is, for example, a refractive index adjuster. As the refractive index adjusting agent, for example, a known refractive index adjusting agent used in a resin composition used as a material for an optical member can be used. For example, when the resin composition produced in the present embodiment is used as a material for POF, a known refractive index adjusting agent used for the material for POF can be used.

The resin composition produced by the production method of the present embodiment may contain additives other than the refractive index adjusting agent.

In the method for producing a resin composition of the present embodiment, the mass ratio of the resin material 2 and the additive 3 is appropriately determined according to the composition of the target resin composition, and is not particularly limited. However, in order to fully exert the function of the additive (for example, the refractive index adjuster) and to mix the resin material 2 and the additive 3 efficiently and uniformly, the mass ratio of the additive 3 to the resin material 2 (for example) The additive / resin material) is preferably 0.005 or more and 0.3 or less.

The resin composition obtained by the method for producing a resin composition of the present embodiment is then used as a member for a desired purpose through a molding step or the like.

(Embodiment 2)
An embodiment of the mixing device of the present invention will be described.

The mixing device of the present embodiment is a mixing device that mixes the first substance and the second substance having a viscosity lower than that of the first substance. Therefore, the mixing device of the present embodiment can be used for mixing the resin material and the additive having a viscosity lower than that of the resin material in the method for producing the resin composition described in the first embodiment.

The mixing device of the present embodiment will be described with reference to FIG.

The mixing device of the present embodiment has a mechanism for rotating or reversing the container 1 having a shape extending in the uniaxial direction and the positions of one end 1a and the other end 1b in the longitudinal direction of the container 1 in opposite directions. (Not shown) and.

The mechanism operates the container 1 so that the rotation speed R and the inversion period of the container 1 satisfy the following equations (4) and (5). In the following formula (4), L [m] is the length in the uniaxial direction of the container 1, and μ [Pa · s] is the viscosity of the first substance.
1.5 <R [rpm] x L [m] x μ [Pa · s] <10 ... (4)
Inversion cycle [times / min] = R × 2… (5)
Here, the viscosity of the first substance is the viscosity of the first substance at the mixing temperature of the first substance and the second substance.

According to the mixing device of the present embodiment, the first substance and the second substance can be efficiently and uniformly mixed.

The mixing device of the present embodiment may further include a control unit that controls the mechanism so that the mechanism rotates or reverses the container 1 at the rotation speed R and the inversion cycle.

In the mixing apparatus of the present embodiment, it is preferable that the mechanism further rotates or inverts the container 1 as follows:
The time during which all of the first substance is repositioned from the position of one end 1a of the container 1 to the position of the other end 1b by the rotation or inversion of the container 1 is defined as the position conversion cycle of the first substance, and the rotation or reversal of the container 1 is performed. When the time for all of the second substance to be repositioned from the position of one end 1a of the container 1 to the position of the other end 1b by inversion is defined as the position conversion cycle of the second substance, the position conversion cycle of the second substance is determined. The container 1 is rotated or inverted at a rotation speed or an inversion cycle that is larger than the position conversion cycle of the first substance.

When the position conversion cycle of the first substance and the position conversion cycle of the second substance satisfy the above relationship, the first substance and the additive can be mixed more efficiently and uniformly.

The preferable viscosities of the first substance and the second substance that are efficiently and uniformly mixed by the mixing device of the present embodiment correspond to the preferable viscosities of the resin material and the additive described in the first embodiment. The first substance and the second quality may be the resin material and the additive described in the first embodiment, respectively.

Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the examples shown below.

(Example 1)
As a resin material, a polymer obtained by polymerizing perfluoro-4-methyl-2-methylene-1,3-dioxolane (PFMMD) was produced. The specific production method was as follows.

10 g of PFMMD and 80 mg of perfluorobenzoyl peroxide were encapsulated in a glass tube. The glass tube was degassed in a 3-cycle freezing / thawing vacuum machine and refilled with argon. The glass tube was sealed and heated at 50 ° C. for 1 day. As a result, the contents of the glass tube became a solid, and the glass tube was further heated at 70 ° C. for 4 days to obtain 10 g of a transparent rod-shaped substance. A part of this transparent rod-shaped product was dissolved in a hexafluorobenzene solution, and chloroform was added to precipitate the product for purification. Solution polymerization of the monomers was carried out in Fluorinert FC-75 (manufactured by Sumitomo 3M) using perfluorobenzoyl peroxide as an initiator. As a result, a PFMMD polymer was obtained. This PFMMD polymer was used as a resin material.

The viscosity of the obtained resin material (PFMMD polymer) at 270 ° C. was 420 Pa · s, and the density was 1950 kg · m ^-3 . As an additive, 1,1,3,5,6-pentachloroperfluorohexane was used. The viscosity of the additive at 270 ° C. was 0.01 Pa · s. As a viscosity measuring device, a rotary rheometer "HAAKE MARS III" (manufactured by Thermo Fisher Scientific Hook Co., Ltd.) was used. A cone plate (φ20 mm, 4 °) was used as the geometry. The setting of the resin sample was completed within 15 minutes on the cone plate stable at the measurement temperature, and the measurement was started. Viscosity measurements were performed at a shear rate of 0.01-5 (1 / s) and a measurement time of 10 min.

200 g of the resin material and 22 g of the additive were put into a transparent cylindrical container having a diameter of 67 mm and a height (length in the uniaxial direction) of 180 mm, and the container was sealed with a lid. The volume of the resin material was 103 cm ³ .

The container containing the resin material and additives was vertically fixed in an oven with a grippable axis of rotation and the container was rotated at 270 ° C. for 6 hours. The rotation speed at this time was 0.067 rpm. In this example, R [rpm] × L [m] × μ [Pa · s] = 0.067 × 180 × 10 ^-3 × 420 = 5.0652, which satisfies the above formula (2).

When the container is rotating and the container is lying down (when the long axis direction of the container is almost parallel to the horizontal direction), the resin material is accumulated in almost the entire bottom of the container in the container. It was confirmed visually. That is, when the container was lying down, the specific surface area of the resin material was calculated to be about 2.3 cm ^-1 in the container. When the container was vertical (when the long axis direction of the container was almost parallel to the vertical direction), it was visually confirmed that the container was in a state of being accumulated in the entire bottom of the container. That is, when the container was vertical, the specific surface area of the high-density resin material was calculated to be about 1.3 cm ^-1 in the container. From these results, the state of the resin material when the container is lying down can be set as the first state, and the state of the high-density resin material when the container is lying down can be set as the second state. In the method of the example, the resin material was repositioned in the container so as to alternate between the first and second states and mixed with the additive.

After the container was rotated, the container was allowed to stand at 270 ° C. for 20 hours, and after cooling, the resin composition which was a mixture of the resin material and the additive was taken out from the container. As a result of visual confirmation, in the obtained resin composition, the resin material and the additive were uniformly mixed.

(Comparative Example 1)
The method for producing the resin composition of Comparative Example 1 was carried out in the same manner as in Example 1 except that the rotation speed of the container was changed to 0.13 rpm.

As a result of visual confirmation when the container was rotated, in Comparative Example 1, when the container was lying down (when the long axis direction of the container was almost parallel to the horizontal direction), the resin material was the container. It did not deform along the shape of the bottom and stayed in its original place (one end of the container). That is, in the method of Comparative Example 1, the position of the resin material was not changed in the container so as to alternately repeat the first state and the second state. The mixing was carried out for 40 hours by such a method that does not cause the position change of the resin material, but the resin material and the additive were not uniformly mixed.

From the results of Example 1 and Comparative Example 1 above, the viscosity of the resin material is mixed with the additive while the position of the resin material is changed in the container so that the resin material alternately repeats the first state and the second state. It was confirmed that even substances with a large difference can be mixed efficiently and uniformly.

According to the method for producing a resin composition of the present invention, a resin material and an additive having a viscosity lower than that of the resin material can be efficiently and uniformly mixed, and thus a material for all uses, for example, an optical member. It can be used for producing a resin composition (particularly a material for POF).

1 Container 1a One end of the container 1b The other end of the container 2 Resin material 3 Additives

Claims (4)

It is a method for manufacturing a resin composition.
In the manufacturing method, a resin material and an additive having a viscosity lower than that of the resin material at a temperature at which the resin material is liquefied are placed in a container, and the resin material is liquefied at a temperature at which the resin material is liquefied. The present invention comprises changing the position of the resin material in the container so as to alternately repeat the first state and the second state, and mixing the resin material and the additive.
The first state is a state in which the resin material fills the first specific surface area.
The second state is a state in which the resin material satisfies the second specific surface area in which the ratio to the first specific surface area is 70% or less.
The first specific surface area and the second specific surface area are specific surface areas obtained by the following formula (1) .
Specific surface area [cm ^-1 ] = Surface area of resin material [cm ² ] / Volume of resin material [cm ³ ]… (1)
The container has a shape extending in the uniaxial direction.
A method for producing a resin composition. The first specific surface area is 0.3 cm ^-1 or more and 10 cm ^-1 or less.
The second specific surface area is 0.2 cm ^-1 or more and 5 cm ^-1 or less.
The method for producing a resin composition according to claim 1. By rotating or reversing the container in a direction in which the positions of one end and the other end in the longitudinal direction of the container are reversed, the resin material and the additive in the container are mixed.
The method for producing a resin composition according to claim 1 or 2. The rotation speed R and the inversion period of the container are the following formulas (2) and (3), where L [m] is the length in the uniaxial direction of the container and μ [Pa · s] is the viscosity of the resin material. )The filling,
1.5 <R [rpm] x L [m] x μ [Pa · s] <10 ... (2)
Inversion cycle [times / min] = R × 2… (3)
Here, the viscosity of the resin material is the viscosity of the resin material at the mixing temperature of the resin material and the additive.
The method for producing a resin composition according to claim 3.

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