JP2021054914A - Method for manufacturing polymerizable composition for optical member, apparatus for manufacturing polymerizable composition for optical member, and method for manufacturing optical member - Google Patents

Abstract

To provide a method for manufacturing a polymerizable composition for an optical member in which a high-quality polymerizable composition for an optical member can be obtained without extending the manufacturing time even if froth is generated in agitating ingredients under reduced pressure.SOLUTION: A method for manufacturing a polymerizable composition for an optical member comprises: putting ingredients of the polymerizable composition for an optical member into a container; agitating the ingredients in the container; reducing the pressure in the container while agitating the ingredients; and mechanically destroying froth generated from the ingredients during the agitation in the container under the reduced pressure.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a method for producing a polymerizable composition for an optical member, an apparatus for producing a polymerizable composition for an optical member, and a method for producing an optical member.

A resin lens has the advantages of being lighter in weight, less likely to break, and capable of dyeing than a lens made of an inorganic material such as inorganic glass. For this reason, resin lenses are currently the mainstream as optical members for spectacle lenses, camera lenses, and the like.
Patent Document 1 describes a polymerizable composition containing an isocyanate compound (A) having a predetermined cyclic structure, an aliphatic isocyanate compound (B) having 4 to 11 carbon atoms, and a thiol compound (C). Has been done. According to the polymerizable composition, it has excellent impact resistance, an excellent balance of optical properties such as refractive index and Abbe number, handleability, transparency, and heat resistance, and also has excellent alkali resistance. It is stated that a molded product having excellent impact resistance can be provided even when the primer layer is not provided between the coat layer and the antireflection coat layer.

International Publication No. 2016/021680

As shown in Patent Document 1, at the time of manufacturing an optical member, an optical member is manufactured by injecting and polymerizing a polymerizable composition containing a polythiol component and a polyisocyanate component into a molding die. To. When a large number of optical members were manufactured, the generation of bubbles was sometimes confirmed in those products.
Further, in the preparation of the composition, each raw material is stirred and mixed, and in order to remove unnecessary components such as water contained in the composition, the raw materials are arranged in a reduced pressure environment. There is. On the other hand, it is known to add a mold release agent to the composition in order to release the resin lens from the molding mold. However, when an additive such as a mold release agent is added to a raw material such as a polymerizable monomer when preparing a polymerizable composition, bubbles are likely to be generated during the arrangement under a reduced pressure environment, and in particular, When the pressure is reduced while stirring, a large amount of bubbles are generated and accumulated on the liquid surface of the raw material.
Then, when the bubbles accumulated on the liquid surface of the raw material are sucked into the filter, trap, or vacuum pump installed in the vacuum line, the vacuum pump cannot exhibit sufficient performance and the degree of vacuum decreases, and unnecessary components from the raw material. It may not be possible to remove the vacuum pump sufficiently, or the vacuum pump may break down. Therefore, the operator monitors the stirring condition so as not to generate excessive bubbles, and manually or automatically leaks the composition, or adjusts the stirring speed appropriately, and the polymerizable composition is prepared under mild conditions. The reality is that preparations are being made. As a result, the production time is generally long, which tends to cause a decrease in production efficiency and a decrease in the quality of the polymerizable composition. In order to solve this problem, it is not necessary for the operator to monitor and adjust the stirring conditions, and the manufacturing time is not long, and the optical member can obtain a high-quality composition and, by extension, a high-quality optical member. There is a demand for a method for producing a polymerizable composition for use.

Therefore, in one embodiment of the present disclosure, even if bubbles are generated when the raw materials are stirred under reduced pressure, the production time is not long, and a high-quality polymerizable composition for an optical member can be obtained. The present invention relates to a method for producing a polymerizable composition for use.

In the method for producing a polymerizable composition for an optical member according to an embodiment of the present disclosure, the raw material of the polymerizable composition for an optical member is put into a container, the raw material in the container is stirred, and the raw material is stirred. This is a method for producing a polymerizable composition for an optical member, in which the inside of the container is depressurized while stirring in the depressurized container while mechanically destroying bubbles generated from the raw material.
Further, the apparatus for producing a polymerizable composition for an optical member according to an embodiment of the present disclosure is connected to a container for accommodating a liquid raw material and a drive source, and is rotatably arranged in the container. The container comprises a rotating shaft, a stirring blade attached to the rotating shaft, and a defoaming member arranged above the stirring blade and in contact with bubbles generated from the raw material to destroy the bubbles. It has an exhaust port for exhausting the internal gas to the outside.
Further, the method for manufacturing an optical member according to an embodiment of the present disclosure is to manufacture an optical member for molding an optical member using the polymerizable composition for an optical member obtained by the above-mentioned method for producing a polymerizable composition for an optical member. The method.

According to the method for producing a polymerizable composition for an optical material according to an embodiment of the present disclosure, the production time is not long, and a high-quality polymerizable composition for an optical member can be obtained.
Further, according to the apparatus for producing a polymerizable composition for an optical member according to an embodiment of the present disclosure, a high-quality polymerizable composition for an optical member can be obtained without lengthening the production time. According to the method for manufacturing an optical member according to one embodiment, a high-quality optical member can be efficiently manufactured.

It is sectional drawing which shows the 1st Embodiment of the manufacturing apparatus of the polymerizable composition for an optical member. FIG. 1A shows a vertical cross-sectional view of the manufacturing apparatus according to the first embodiment, and FIG. 1B shows a cross-sectional view taken along the line IB-IB of FIG. 1A. It is a figure which shows the state in the manufacturing apparatus at the time of stirring of the polymerizable composition for an optical member. It is a figure which shows the state in the manufacturing apparatus in the state which the bubble was generated at the time of stirring of the polymerizable composition for an optical member. It is sectional drawing which shows the 2nd Embodiment of the manufacturing apparatus of the polymerizable composition for an optical member. FIG. 4 (A) shows a vertical sectional view of the manufacturing apparatus according to the second embodiment, and FIG. 4 (B) shows a cross-sectional view shown by the line IIB-IIB of FIG. 4 (A). C) is a schematic external view for explaining the configuration of the foam breaking member. It is sectional drawing which shows the 3rd Embodiment of the manufacturing apparatus of the polymerizable composition for an optical member. 5 (A) is a vertical cross-sectional view of the manufacturing apparatus according to the third embodiment, and FIG. 5 (B) is a cross-sectional view taken along the line IIIB-IIIB of FIG. 5 (A).

In the present specification, the lower limit value and the upper limit value described stepwise for a preferable numerical range (for example, a range such as content) can be independently combined. For example, from the description of "preferably 10 to 90, more preferably 30 to 60", the "preferable lower limit value (10)" and the "more preferable upper limit value (60)" are combined to obtain "10 to 60". You can also do it.

[Method for Producing Polymerizable Compositions for Optical Members]
The method for producing a polymerizable composition for an optical member according to an embodiment of the present disclosure is as follows.
The raw material of the polymerizable composition for an optical member is put into a container, and
The raw material in the container is stirred and
The inside of the container is depressurized while stirring the raw material,
This is a method for producing a polymerizable composition for an optical member, which mechanically destroys bubbles generated from the raw material while stirring in the container under reduced pressure.

The method for producing a polymerizable composition for an optical member according to an embodiment of the present disclosure is provided with each of the above steps, so that bubbles generated from the raw material during stirring under reduced pressure are mechanically destroyed. Controls such as adjustment of stirring conditions to suppress the occurrence of bubbles are no longer essential. Therefore, it is avoided that the manufacturing time becomes long. Further, if the production time is long, the composition may be deteriorated, or in some cases, the ratio between the compounding components may be biased. However, since it is avoided that the production time is long, such a situation may occur. It is possible to prevent defects, and by extension, a high-quality polymerizable composition for an optical member can be obtained. Further, by polymerizing the polymerizable composition for an optical member, a high quality optical member can be obtained.
Hereinafter, embodiments of a method for producing a polymerizable composition for an optical member will be described in detail. In the following description, the process of removing unnecessary components such as water from the raw material by reducing the pressure while stirring is referred to as "deaeration treatment". Further, the raw materials of the polymerizable composition for optical members will be described in detail later.

In one aspect, the raw material comprises at least two types of material. For example, it is a raw material containing two or more kinds of polymerizable monomers. Alternatively, it is a raw material containing a polymerizable monomer and an additive.
Then, after putting one raw material into the container, the other raw material may be added to the raw material in the container, or both may be put into the container at the same time. Generally, since the amount of the polymerizable monomer used is larger than that of the additive, it is desirable to put the polymerizable monomer into the container first.
In the former case, the degassing treatment is performed at least one of the timing after the one raw material is put into the container and the timing after the other raw material is added.
In the latter case (that is, when at least two kinds of raw materials are charged at the same time), the degassing treatment is performed after the batch charging.
When the polymerizable monomer contains a large amount of water or the like, the water or the like can be vaporized and removed by performing a degassing treatment after adding or adding the polymerizable monomer.
If the degassing treatment is performed after adding the additive, in addition to being able to remove unnecessary components contained in the additive, the addition of the additive makes it easier to remove from the raw material previously charged in the container. Moisture and the like can be removed.

In one aspect, the raw material comprises a polymerizable monomer and a mold release agent. Then, the mold release agent is charged into the container following the polymerizable monomer, stirring of the raw material is started after the mold release agent is charged, and then the pressure in the container is reduced and bubbles are destroyed.
Due to the addition of the release agent, the generation of bubbles during stirring under reduced pressure tends to be remarkable, but by mechanically destroying the bubbles, it is possible to more reliably avoid a long production time. The release agent will be described later.

Also, in one aspect, the raw material comprises a first material, a second material and a third material. Then, after the first material and the second material are put into the container, and after the third material is put into the mixture of the first material and the second material, the stirring and the depressurization are performed, respectively. And bubble breaking are performed in sequence.
By sequentially executing stirring, depressurizing, and foam breaking each time the material constituting the raw material is put in, the bubbles can be broken more reliably, and it is possible to more reliably prevent the production time from becoming long.
The first material, the second material, and the third material include, for example,
(1) Combination of 3 types of polymerizable monomers (2) Combination of 2 types of polymerizable monomers and additives (3) Combination of polymerizable monomers and 2 types of additives, etc. Be done. Either of them may be a release agent, for example, the first material is a first polymerizable monomer, the second material is a second polymerizable monomer, and the third material is a release agent. Is.

In another aspect, the raw material comprises four or more kinds of materials. For example
(A) Combination of two types of polymerizable monomers and two types of additives (b) Combination of three or more types of polymerizable monomers and two types of additives (c) Two types of polymerizable singles Combination of mer and 3 or more types of additives (d) Combination of 3 or more types of polymerizable monomers and 3 types of additives,
And so on.
When there are two or more types of polymerizable monomers, the first polymerizable monomer is first charged into the container. Then, one of the second polymerizable monomer and the additive is added, and then the other of the second polymerizable monomer and the additive is added, or the second polymerizable monomer is added. And the additive are added at the same time.

The additive may be added at a plurality of timings, or may be added at the same time. When two or more kinds of additives are used, they may be added at different timings, or a plurality of types of additives may be added at one time.
After the additive is added, and when a plurality of types of polymerizable monomers are used, the degassing treatment is performed after adding the second and subsequent polymerizable monomers. The degassing treatment may be performed for each addition of the additive or the polymerizable monomer, or the degassing treatment may be performed for only a part of the additive or the polymerizable monomer.

<First Embodiment of Method for Producing Polymerizable Composition for Optical Member>
The first embodiment of the method for producing a polymerizable composition for an optical member will be described. The manufacturing method of this embodiment has the following steps (1A) to (6A).
Step (1A): A step of adding a first additive (for example, an ultraviolet absorber) to the composition containing the first polymerizable monomer and stirring the composition.
Step (2A): A step of adding and stirring a composition containing a second polymerizable monomer following the step (1A).
Step (3A): A step of adding and stirring a second additive (for example, at least one of a polymerization catalyst and a colorant) following the step (2A).
-Step (4A): A step of performing the first degassing treatment following the step (3A).
-Step (5A): A step of adding a release agent as a third additive following the step (4A) and stirring.
-Step (6A): A step of performing a second degassing process following the step (5A).

<Second Embodiment of Method for Producing Polymerizable Composition for Optical Member>
The first embodiment of the method for producing a polymerizable composition for an optical member will be described. The manufacturing method of this embodiment has the following steps (1B) to (7B).
Step (1B): A step of adding a first additive (for example, an ultraviolet absorber) to the composition containing the first polymerizable monomer and stirring the composition.
-Step (2B): A step of performing the first degassing treatment following the step (1B).
Step (3B): A step of adding and stirring the composition containing the second polymerizable monomer following the step (2B).
Step (4B): Following step (3B), a second additive (for example, at least one of a polymerization catalyst and a colorant) is added and stirred.
-Step (5B): A step of performing a second degassing process following the step (4B).
-Step (6B): A step of adding a release agent as a third additive following the step (5B) and stirring.
-Step (7B): A step of performing a third degassing process following the step (6B).

<Third Embodiment of the method for producing a polymerizable composition for an optical member>
A third embodiment of a method for producing a polymerizable composition for an optical member will be described.
The manufacturing method of this embodiment has the following steps (1C) to (5C).
Step (1C): A step of adding a first additive (for example, at least one of an ultraviolet absorber and a polymerization catalyst) to a composition containing the first polymerizable monomer and stirring the composition.
-Step (2C): A step of adding and stirring a composition containing a second polymerizable monomer following the step (1C).
-Step (3C): A step of performing the first degassing treatment following the step (2C).
-Step (4C): A step of adding a mold release agent or a mold release agent and a colorant as a second additive following the step (3C) and stirring.
-Step (5C): A step of performing a second degassing process following the step (4C).

<Fourth Embodiment of Method for Producing Polymerizable Composition for Optical Member>
A fourth embodiment of a method for producing a polymerizable composition for an optical member will be described.
The manufacturing method of this embodiment has the following steps (1D) to (6D).
Step (1D): A step of adding a first additive (for example, at least one of an ultraviolet absorber and a polymerization catalyst) to a composition containing the first polymerizable monomer and stirring the composition.
-Step (2D): A step of performing the first degassing treatment following the step (1D).
-Step (3D): A step of adding and stirring a composition containing a second polymerizable monomer following the step (2D).
-Step (4D): A step of performing a second degassing process following the step (3D).
-Step (5D): A step of adding a mold release agent or a mold release agent and a colorant as a second additive following the step (4D) and stirring.
-Step (6D): A step of performing a third degassing process following the step (5D).

In the above-described first to fourth embodiments, by executing the degassing treatment in a plurality of times, unnecessary components can be more reliably removed from the raw material. In addition, by adding the release agent at the end of the entire process, it is possible to prevent the foam from accumulating on the liquid surface of the raw material for a long time, and to avoid malfunction of the vacuum pump due to the generation of foam as much as possible. It will be easier.

Further, in the above-described first to fourth embodiments, the degassing treatment performed last among the plurality of degassing treatments is particularly likely to generate bubbles because the release agent is added immediately before the degassing treatment, so that the other degassing treatments can be used. It is preferable to set the degassing time longer and set the value of the ultimate vacuum degree smaller than that of other degassing treatments. The other degassing treatment may be omitted if it is known that the raw material used at that stage contains sufficiently little unnecessary components such as water.

When the colorant is added in the step (3A), the step (4B), the step (4C), the step (5D), etc., the colorant is added to the composition containing the second polymerizable monomer in advance. You may prepare a thing (master liquid) and add this master liquid.
When a polymerization catalyst is added in steps (3A), step (4B), step (1C), step (1D), etc., a mixture in which the polymerization catalyst is added to the composition containing the first polymerizable monomer in advance. May be prepared and this mixture may be added.
In one aspect, in step (4C) and step (5D), the release agent and the colorant are added simultaneously to the raw material containing the polymerizable monomer. By adding the release agent and the colorant at the same time, it becomes easy to prevent the colorant from being decomposed by the presence of the release agent.

(Stirring)
In each of the above embodiments and embodiments, the stirring method performed after adding each raw material is not particularly limited, and for example, it can be performed using a rotating stirring blade as used in the manufacturing apparatus described later. From the viewpoint of uniformity, the stirring speed is preferably 100 to 1000 rpm, more preferably 200 to 600 rpm, and even more preferably 300 to 500 rpm. The temperature of the raw material during stirring is preferably 5 to 30 ° C., more preferably 5 to 20 ° C., still more preferably 5 to 10 ° C. from the viewpoint of solubility of solid additives.

(Degassing process)
The degassing treatment of each of the above embodiments and embodiments can be performed by placing the raw material in a pressure-resistant container and depressurizing the inside of the container with a vacuum pump while stirring the raw material. In the degassing treatment, stirring and depressurization are continued for a predetermined time, and after the inside of the container reaches a predetermined vacuum degree (hereinafter referred to as ultimate vacuum degree), the stirring and depressurization are terminated.
A predetermined degree of vacuum is measured in advance so that the content of unnecessary components such as water contained in the composition does not affect the production of the optical member, and when the predetermined degree of vacuum is reached. By terminating the stirring and depressurizing, it is possible to prevent the production time from becoming excessively long.
The ultimate vacuum degree in the degassing treatment is preferably 800 Pa or less, more preferably 400 Pa or less, still more preferably 200 Pa or less, from the viewpoint of suppressing the generation of bubbles as much as possible. Further, from the viewpoint of improving work efficiency, it is preferably 10 Pa or more, more preferably 20 Pa or more, and further preferably 40 Pa or more.
In the degassing treatment after adding an additive other than the release agent and after adding the second polymerizable monomer, 10 to 20 Pa is particularly preferable from the viewpoint of productivity. Further, in the degassing treatment after adding the release agent, 10 to 40 Pa is particularly preferable from the viewpoint of uniformity.

The degassing treatment time is preferably 10 minutes or more and 120 minutes or less, more preferably 10 minutes or more and 110 minutes or less, still more preferably 20 minutes or more and 110 minutes or less, and even more preferably 25 minutes or more and 100 minutes or less. By setting the degassing time within this range, it is possible to suppress an increase in viscosity.
In the degassing treatment after adding an additive other than the release agent and after adding the second polymerizable monomer, 10 to 40 minutes is particularly preferable from the viewpoint of preventing an increase in viscosity. Further, in the degassing treatment after adding the release agent, 20 to 60 minutes is particularly preferable.
The raw material is agitated during the degassing treatment by adding an additive other than the release agent, adding a second polymerizable monomer, and after adding the release agent. Also, the stirring conditions can be the same as the stirring conditions of the raw materials performed in the steps other than the above-mentioned degassing treatment.

Further, in order to efficiently mix the raw materials and remove unnecessary components, it is preferable to control the temperature so that the raw materials reach a predetermined temperature when performing the stirring and depressurizing operations. The temperature of the raw material during the degassing treatment is preferably 0 to 20 ° C, more preferably 5 to 15 ° C, still more preferably 5 to 10 ° C.
The temperature control can be performed by arranging a cooling element, a heater, or the like in the container or in the vicinity of the container, and appropriately switching or turning these outputs on and off.

[manufacturing device]
Next, a manufacturing apparatus used for a method for manufacturing a polymerizable composition for an optical member will be described.
The apparatus for producing a polymerizable composition for an optical member according to an embodiment of the present invention includes a container for accommodating a liquid raw material and a rotating shaft connected to a drive source and rotatably arranged in the container. The container includes a stirring blade attached to the rotating shaft and a defoaming member which is arranged above the stirring blade and comes into contact with bubbles generated from the raw material to destroy the bubbles. It has an exhaust port for exhausting the air to the outside.
Hereinafter, specific embodiments of the manufacturing apparatus will be described with reference to the drawings.

(First Embodiment of Manufacturing Equipment)
FIG. 1 is a schematic cross-sectional view showing a first embodiment of an apparatus for producing a polymerizable composition for an optical member. FIG. 1A shows a vertical cross-sectional view of the manufacturing apparatus according to the first embodiment, and FIG. 1B shows a cross-sectional view taken along the line IB-IB of FIG. 1A. For ease of understanding, in FIG. 1A, the rotary shaft, the stirring blade, and the defoaming member, which will be described later, are shown as a side view, and the position of the liquid level S0 of the raw material 20 is shown. Therefore, the raw materials are illustrated with halftone dots. The same applies to FIGS. 2, 3, 4 (A) and 5 (A), which will be described later.

As shown in FIG. 1, the manufacturing apparatus 100A rotates a container 1 for accommodating the raw material 20 of the polymerizable composition for an optical member, a stirring blade 2 arranged in the container 1, and a stirring blade 2. The rotary shaft 4 and the drive source 5 including a motor or the like to which the rotary shaft 4 is connected are provided. The stirring blade 2 is provided below the inside of the container 1 so that the raw material 20 can be stirred.
Container 1 has at least strength that can withstand reduced pressure. The container 1 is provided with an exhaust port 1a and an exhaust port 1b. An exhaust line 6 for exhausting the gas in the container 1 to the outside of the container is connected to the exhaust port 1a, and the exhaust port 1b is connected to the exhaust port 1b. A liquid discharge line 7 for discharging the liquid in the container 1 to the outside of the container is connected. The exhaust line 6 includes a trap 9 to which an exhaust pipe is connected to the front and rear, and is connected to the vacuum pump 8 via the trap 9.
The upper part of the container 1 is held openable and closable by a hinge 11, and the container 1 is sealed by fixing the upper part of the container 1 with a lock 10.
The rotating shaft 4 is provided with a propeller-shaped defoaming member 30 for mechanically destroying bubbles generated from the raw material 20. The defoaming member 30 is arranged above the stirring blade 2.
In the example shown in FIG. 1B, the defoaming member 30 has two blades and the stirring blade 2 has three blades, but the number and shape of the blades, the angle of the blades with respect to the rotation axis, and the like are not particularly limited. , Appropriate ones can be adopted according to the viscosity of the raw material and the like. Regarding the number of blades, for example, the number of blades of the defoaming member 30 may be 3 or more, or the number of blades of the stirring blade may be 2 or 4 or more. The same applies to each embodiment described later.

FIG. 2 is a diagram showing a state inside the manufacturing apparatus when the polymerizable composition for an optical member is stirred. As shown in FIG. 2, by rotating the stirring blade 2 at high speed, the raw material 20 becomes spiral around the rotation shaft 4, and the liquid level S1 of the raw material 20 drops most in the vicinity of the rotation shaft 4. It rises toward the vicinity of container 1.
The defoaming member 30 is arranged so that the height at its lowest position is at a height h2 equal to or higher than the highest position h1 of the liquid level S1 of the raw material 20 when the raw material 20 is agitated by the stirring blade 2. .. By arranging the defoaming member 30 in such a positional relationship, it is possible to prevent the defoaming member 30 from coming into contact with the liquid level S1 of the raw material 20.

While the raw material 20 is being agitated, the vacuum pump 8 is operated to depressurize the inside of the container 1 to degas the raw material 20 to remove unnecessary components such as water contained in the raw material 20. can do.
At this time, for example, the water or the like mixed in the raw material 20 becomes bubbles and appears on the liquid surface S1. In particular, when a mold release agent is added to the raw material, the generation of bubbles becomes remarkable.
FIG. 3 is a diagram showing the inside of the manufacturing apparatus in a state where bubbles are generated during stirring of the polymerizable composition for an optical member. As shown in FIG. 3, when the raw material 20 is stirred and depressurized, bubbles 21 may be thickly deposited on the liquid surface S1 of the raw material 20. When the accumulated bubbles 21 reach the vicinity of the exhaust port 1a, they may enter the vacuum pump 8 via the vacuum line 6 and may damage the vacuum pump 8.

In the manufacturing apparatus 100A of the present embodiment, the foam 21 is mechanically destroyed when the defoaming member 30 comes into contact with the foam 21. Further, since the defoaming member 30 is rotated by the rotation of the rotation shaft 4, the defoaming member 30 continuously destroys the bubbles regardless of the position of the liquid surface S1 of the raw material. In this way, the bubbles 21 deposited on the liquid surface S1 are prevented from reaching the exhaust port 1a.

In the present embodiment, the defoaming member 30 has a propeller shape. As will be described later, the defoaming member may have a rod shape.

A decompression pump 8 which is an exhaust device is connected to the exhaust port 1a via an exhaust line 6 including an exhaust pipe, and the exhaust pipe included in the exhaust line 6 is sucked by the vacuum pump 8, such as gas or bubbles. It has a trap 9 for trapping the suction material of the above.

(Second Embodiment of Manufacturing Equipment)
The defoaming member may be rotated in the rotation direction of the rotation shaft at a rotation speed slower than that of the rotation shaft.
By making the rotation speed of the defoaming member different from the rotation speed of the rotation shaft, it is possible to control the stirring of the raw material and the mechanical destruction of the foam separately. Specifically, by making the rotation speed of the defoaming member slower than the rotation speed of the rotation shaft, it becomes easy to surely destroy the bubbles while appropriately stirring the raw materials. In addition, it is possible to make it difficult for bubbles to scatter.
In this case, the rotation speed of the defoaming member is preferably 15 to 400 rpm, more preferably 30 to 200 rpm, and even more preferably 60 to 100 rpm.

FIG. 4 is a schematic cross-sectional view showing a second embodiment of an apparatus for producing a polymerizable composition for an optical member. 4 (A) shows a vertical sectional view of the manufacturing apparatus 100B according to the second embodiment, FIG. 4 (B) shows a horizontal sectional view shown by line IIB-IIB of FIG. 4 (A), and FIG. (C) is a schematic external view for explaining the configuration of the foam breaking member.

The defoaming member 31 and the holding method thereof of the manufacturing apparatus 100B are different from those of the manufacturing apparatus 100A. Other configurations are the same as those in the first embodiment.
The defoaming member 31 of the manufacturing apparatus 100B is a rod-shaped member provided on the movable flange 32, and the rotating shaft 4 is pierced through the opening of the movable flange 32. A fixed flange 40 is provided on the shaft 4 directly below the movable flange 32. The fixing flange 40 is fixed to the rotating shaft 4 by tightening the fixing screw 41, for example, as shown in FIG. 4 (C).
The defoaming member 31 is held in a state of being rotatable with respect to the rotation direction of the rotating shaft 4 and fixed by a fixed flange 40 in the axial direction of the rotating shaft 4. As a result, when the rotating shaft 4 rotates, the defoaming member 31 also rotates, but since the defoaming member 31 rotates with the frictional force between the rotating shaft 4 and the rotating shaft 4, the rotation speed of the stirring blade 2 is higher than that of the stirring blade 2. It spins at a slow speed. Since the high-speed rotation required for the stirring blade 2 is not always required for the destruction of the bubbles 21, there is no particular problem in the destruction of the bubbles 21 even if the rotation speed is slow. Further, since the defoaming member 31 does not rotate at an unnecessarily high speed, the foam 21 does not scatter.

The defoaming member 31 of the manufacturing apparatus 100B has a simple rod-shaped shape, but may be a propeller-shaped one such as the defoaming member 30 of the manufacturing apparatus 100A. Further, in the manufacturing apparatus 100B, the fixed flange 40 is fixed to the rotating shaft 4 by tightening the screw 41, but the present invention is not limited to this. For example, the fixed flange is welded to the rotating shaft or the flange portion is integrated. A modified rotation axis may be used.

(Third Embodiment of the manufacturing apparatus)
FIG. 5 is a schematic cross-sectional view showing a third embodiment of an apparatus for producing a polymerizable composition for an optical member. 5 (A) shows a vertical cross-sectional view of the manufacturing apparatus 100C according to the third embodiment, and FIG. 5 (B) shows a cross-sectional view taken along the line IIIB-IIIB of FIG. 5 (A). FIG. 5 (C) shows
The shape of the defoaming member of the manufacturing apparatus 100C is different from that of other embodiments. As shown in FIGS. 5A and 5B, the defoaming member 50 of the manufacturing apparatus 100C has a net unit that spreads two-dimensionally with respect to the liquid level S0 of the raw material 20. A protrusion 12 is provided on the inner wall of the container 1 of the manufacturing apparatus 100C in a direction intersecting the rotation shaft 4, and a defoaming member 50 is fixed to the protrusion 12. Although FIG. 5B shows an example in which the protrusions 12 are provided at a plurality of locations, the protrusions 12 may have a structure in which the protrusions 12 are continuous in an annular shape.
An opening 51 is formed in the center of the net portion of the defoaming member 50, and the rotating shaft 4 penetrates the opening 51. Other configurations are the same as those in the first embodiment.

Also in the present embodiment, the defoaming member 50 is arranged so that the height of the lowest position thereof is higher than the height of the highest position of the liquid level of the raw material 20 when the raw material 20 is agitated by the stirring blade 2. ing.
Then, when the bubbles 21 generated by the stirring of the raw material 20 reach the net unit of the defoaming member 50, they are mechanically destroyed by the defoaming member 50. Since the net portion of the defoaming member 50 spreads in a two-dimensional manner, the bubbles 21 can be reliably destroyed regardless of the position and shape in which the bubbles 21 are generated. Since the defoaming member 50 of the manufacturing apparatus 100C has no moving portion, the apparatus configuration can be simplified.

[Polymerizable composition for optical members]
The polymerizable composition for an optical member according to an embodiment of the present invention contains a polymerizable monomer as a raw material for a resin component forming the optical member. The resin component forming the optical member preferably contains at least one selected from the group consisting of (thio) urethane resin, episulfide resin, polycarbonate resin, polyamide resin, acrylic resin, vinyl resin and polyester resin, and therefore, these It is preferable to contain a polymerizable monomer capable of producing the resin component of. When the optical member obtained by polymerizing the polymerizable composition for an optical member is a lens or a base material for a lens, the polymerizable composition for an optical member is a (thio) urethane resin from the viewpoint of exhibiting a high refractive index. And more preferably it contains a polymerizable monomer capable of producing at least one of the episulfide resins.
The (thio) urethane resin means at least one selected from urethane resin and thiourethane resin.
Examples of the polymerizable monomer capable of producing the (thio) urethane resin include a combination of the polyiso (thio) cyanate compound (A) and the polythiol compound (B).

<Polyisocyanate compound (A)>
Examples of the polyisocyanate compound (A) include a polyisocyanate compound having an aromatic ring, an alicyclic polyisocyanate compound, and a linear or branched aliphatic polyisocyanate compound.

Examples of the polyisocyanate compound having an aromatic ring include diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylenediocyanate, isopropylphenylenediocyanate, dimethylphenylenediocyanate, diethylphenylenediocyanate, diisopropylphenylenediocyanate, and trimethylbenzenetriisocyanate. , Benzene triisocyanate, biphenyl diisocyanate, toluidin diisocyanate, 4,4'-methylenebis (phenylisocyanate), 4,4'-methylenebis (2-methylphenylisocyanate), bibenzyl-4,4'-diisocyanate, bis (isocyanatophenyl) ) Ethylene, bis (isocyanatomethyl) benzene, bis (isocyanatoethyl) benzene, bis (isocyanatopropyl) benzene, α, α, α', α'-tetramethylxylylene diisocyanate, bis (isocyanatobutyl) benzene , Bis (isocyanatomethyl) naphthalene, bis (isocyanatomethylphenyl) ether, 2-isocyanatophenyl-4-isocyanatophenyl sulfide, bis (4-isocyanatophenyl) sulfide, bis (4-isocyanatomethylphenyl) Sulfate, bis (4-isocyanatophenyl) disulfide, bis (2-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-5-isocyanatophenyl) disulfide, bis (3-methyl-6-isocyanato) Examples thereof include phenyl) disulfide, bis (4-methyl-5-isocyanatophenyl) disulfide, bis (3-methoxy-4-isocyanatophenyl) disulfide, and bis (4-methoxy-3-isocyanatophenyl) disulfide.

Examples of the alicyclic polyisocyanate compound include diisocyanatocyclohexane, isophoronediisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethanediisocyanate, bis (isocyanatomethyl) bicycloheptane, 2,5-diisocyanato-1,4-dithiane, and so on. 2,5-bis (isocyanatomethyl) -1,4-dithiane, 4,5-diisocyanato-1,3-dithiolane, 4,5-bis (isocyanatomethyl) -1,3-dithiolan, 4,5- Examples thereof include bis (isocyanatomethyl) -2-methyl-1,3-dithiolane.

Examples of the linear or branched aliphatic polyisocyanate compound include hexamethylene diisocyanate, 2,2-dimethylpentanediisocyanate, 2,2,4-trimethylhexanediisocyanate, butenediisocyanate, and 1,3-butadiene-1,4-. Diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecantryisocyanate, 1,3,6-hexamethylenetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, bis (isocyanate) Natoethyl) carbonate, bis (isocyanatoethyl) ether, lysine diisocyanatomethyl ester, lysine triisocyanate, bis (isocyanatomethyl) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, bis ( Isocyanatohexyl sulfide, bis (isocyanatomethyl) sulfone, bis (isocyanatomethyl) disulfide, bis (isocyanatoethyl) disulfide, bis (isocyanatopropyl) disulfide, bis (isocyanatomethylthio) methane, bis (isocyanato) Ethylthio) methane, bis (isocyanatomethylthio) ethane, bis (isocyanatoethylthio) ethane, 1,5-diisocyanate-2-isocyanatomethyl-3-pentane, 1,2,3-tris (isocyanatomethylthio) Propane, 1,2,3-tris (isocyanatoethylthio) propane, 3,5-dithia-1,2,6,7-heptanetetraisocyanate, 2,6-diisocyanatomethyl-3,5-dithia- 1,7-Heptane diisocyanate, 2,5-diisocyanate methylthiophenate, 4-isocyanatoethylthio-2,6-dithia-1,8-octanediisocyanate, 1,2-diisocyanatoetane, 1,6 − Diisocyanatohexane is mentioned.
As the polyisocyanate compound (A), one kind or two or more kinds may be used.

The polyisocyanate compound (A) is preferably a group consisting of bis (isocyanatomethyl) benzene, isophorone diisocyanate, hexamethylene diisocyanate, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, and bis (isocyanatomethyl) bicycloheptane. One or more selected from the group consisting of bis (isocyanatomethyl) benzene, bis (isocyanatomethyl) cyclohexane, dicyclohexylmethane diisocyanate, and bis (isocyanatomethyl) bicycloheptane. Is.

<Polythiol compound (B)>
Examples of the polythiol compound (B) include an ester compound of a polyol compound and a mercapto group-containing carboxylic acid compound, a linear or branched aliphatic polythiol compound, a polythiol compound having an alicyclic structure, an aromatic polythiol compound, and the like. ..
Among the ester compounds of the polyol compound and the mercapto group-containing carboxylic acid compound, examples of the polyol compound include compounds having two or more hydroxyl groups in the molecule, and examples thereof include ethylene glycol, diethylene glycol, propanediol, propanetriol, and butanediol. , Trimethylol propane, bis (2-hydroxyethyl) disulfide, pentaerythritol, dipentaerythritol and the like.
Examples of the mercapto group-containing carboxylic acid compound include thioglycolic acid, mercaptopropionic acid, thiolactic acid compound, thiosalicylic acid and the like.
Examples of the ester compound of the polyol compound and the mercapto group-containing carboxylic acid compound include ethylene glycol bis (2-mercaptoacetate), diethylene glycolbis (2-mercaptoacetate), propanetrioltris (2-mercaptoacetate), and propanediolbis. (2-Mercaptoacetate), Butanediol bis (2-Mercaptoacetate), Trimethylol propanetris (2-Mercaptoacetate), Trimethylol propanetris (3-mercaptopropionate), Ethylene bis (hydroxyethyl sulfide) bis ( 2-Mercaptoacetate), Butanediolbis (2-Mercaptoacetate), Butanediolbis (3-Mercaptopropionate), Ethylene Glycolbis (3-Mercaptopropionate), Diethylene Glycolbis (3-Mercaptopropionate) , Trimethylol propanbis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoacetate), dipenta Examples thereof include erythritol hexakis (3-mercaptopropionate).
Examples of the linear or branched aliphatic polythiol compound include 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, and 1, , 6-Hexanedithiol, 1,2,3-propanetrithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2,3-dimercapto-1- Compoundol, 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl ether, 2,2-bis (mercaptomethyl) -1,3-propanedithiol, bis (2-mercaptoethyl) ether, bis ( 2-mercaptoethyl) sulfide, bis (2-mercaptoethyl) disulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, bis (mercaptomethyl) -3,6,9-trithiaundecandithiol Can be mentioned.

Examples of the polythiol compound having an alicyclic structure include 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, methylcyclohexanedithiol, bis (mercaptomethyl) cyclohexane, and bis (mercaptomethyl) dithiane.
Examples of the aromatic polythiol compound include dimercaptobenzene, bis (mercaptomethyl) benzene, bis (mercaptoethyl) benzene, trimercaptobenzene, tris (mercaptomethyl) benzene, tris (mercaptoethyl) benzene, dimercaptobiphenyl, and 4 , 4'-Dimercaptobibenzyl, 2,5-toluenedithiol, naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracene Dimethanethiol, 1,3-di (p-methoxyphenyl) propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-bis Examples thereof include (p-mercaptophenyl) pentane and the like.
One of these polythiol compounds may be used alone or in combination of two or more.
The polythiol compound (B) is preferably bis (mercaptomethyl) dithiane, pentaerythritoltetrakis (2-mercaptoacetacetase), pentaerythritoltetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto-. 3,6-Dithiaoctane, Bis (Mercaptomethyl) -3,6,9-Trithiandecandithiol, Trimethylol Propantris (2-Mercaptoacetacet), Trimethylol Propantris (3-Mercaptopropionate), Butanediolbis Selected from the group consisting of (2-mercaptoacetate), butanediolbis (3-mercaptopropionate), dipentaerythritol hexakis (2-mercaptoaceto), and dipentaerythritol hexakis (3-mercaptopropionate). More preferably, bis (mercaptomethyl) -3,6,9-trithiaundecandithiol, pentaerythritoltetrakis (3-mercaptopropionate), 4-mercaptomethyl-1,8-dimercapto. One or more selected from the group consisting of -3,6-dithiaoctane.
The bis (mercaptomethyl) -3,6,9-trithiaundecanedithiol is preferably 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 4 , 8-bis (mercaptomethyl) -3,6,9-trichiaundecane-1,11-dithiol, and 5,7-bis (mercaptomethyl) -3,6,9-trichiaundecane-1,11- It is a mixture of dithiol.

One aspect of the polythiol compound (B) comprises a polythiol compound having two or more sulfide bonds and two or more mercapto groups.
Further, one aspect of the polythiol compound (B) includes a polythiol compound having two or more sulfide bonds and three or more mercapto groups.
Further, one aspect of the polythiol compound (B) is a mixture of a plurality of types of polythiol compounds.

The polythiol compound (B) is preferably selected from the group consisting of the following mixtures.
[1] A mixture of 2,5-bis (mercaptomethyl) -1,4-dithiane and pentaerythritol tetrakis (2-mercaptoacetate) [2] 4-mercaptomethyl-1,8-dimercapto-3,6- Mixture of dithiane octane with pentaerythritol tetrakis (3-mercaptopropionate) [3] 4,7-bis (mercaptomethyl) -3,6,9-trithiandecane-1,11-dithiol, 4,8- Bis (mercaptomethyl) -3,6,9-trithiandecan-1,11-dithiol and 5,7-bis (mercaptomethyl) -3,6,9-trithiandecan-1,11-dithiol mixture

Preferable examples of the combination of the polyisocyanate compound (A) and the polythiol compound (B) include the following [1] to [3].
[1] 1,3-bis (isocyanatomethyl) benzene, 4,7-bis (mercaptomethyl) -3,6,9-trithiandecan-1,11-dithiol, 4,8-bis (mercapto) Methyl) -3,6,9-trithiandecan-1,11-dithiol, 5,7-bis (mercaptomethyl) -3,6,9-trithiandecan-1,11-dithiol mixture [2] 1 , 3-Bis (isocyanatomethyl) cyclohexane, and a mixture of 2,5-bis (mercaptomethyl) -1,4-dithiane and pentaerythritol tetrakis (2-mercaptoacetate) [3] 2,5-bis (isosia) A mixture of natomethyl) -bicyclo [2.2.1] heptane and 2,6-bis (isocyanatomethyl) -bicyclo [2.2.1] heptane, and 4-mercaptomethyl-1,8-dimercapto- Mixture of 3,6-dithiane octane and pentaerythritol tetrakis (3-mercaptopropionate)

<Additives>
Various additives such as an ultraviolet absorber, a polymerization catalyst, a mold release agent, an antioxidant, an antioxidant, and a fluorescent whitening agent may be added to the polymerizable composition for an optical member.

(UV absorber)
The UV absorber preferably has a maximum absorption wavelength of 345 nm or more in a chloroform solution.
Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, dibenzoylmethane, 4-tert-butyl-4'-methoxybenzoylmethane and the like.
Examples of the benzophenone compound include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, and 2-hydroxy-4-n-octoxybenzophenone. , 2-Hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone and the like.
Examples of the benzotriazole-based compound include 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole and 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chloro-. 2H-benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chloro-2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) ) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole , 2- (2-Hydroxy-5-tert-octylphenyl) -2H-benzotriazole and 2- (2-hydroxy-4-octyloxyphenyl) -2H-benzotriazole and other benzotriazole compounds. These may be used individually by 1 type or in combination of 2 or more type.
The amount of the ultraviolet absorber added is preferably 0.01 part by mass or more, more preferably 0.05 part by mass or more, still more preferably 0.1 part by mass or more, based on 100 parts by mass of the total of the polythiol compound and the polyisocyanate compound. , More preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, still more preferably 0.8 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, more preferably. Is 2 parts by mass or less, more preferably 1 part by mass or less.

(Polymerization catalyst)
The polymerization catalyst is preferably an organotin compound, more preferably an alkyltin halide compound or an alkyltin compound.
Examples of the alkyltin halide compound include dibutyltin dichloride, dimethyltin dichloride, monomethyltin trichloride, trimethyltin chloride, tributyltin chloride, tributyltin flolide, and dimethyltin dibromide.
Examples of the alkyltin compound include dibutyltin diacetate and dibutyltin dilaurate.
Among these, dibutyltin dichloride, dimethyltin dichloride, dibutyltin diacetate, and dibutyltin dilaurate are preferable.
The amount of the polymerization catalyst added is preferably 0.001 part by mass or more, more preferably 0.005 part by mass or more, and preferably 1 part by mass or less, based on 100 parts by mass of the total of the polythiol compound and the polyisocyanate compound. It is more preferably 0.5 parts by mass or less, still more preferably 0.1 parts by mass or less.

(Release agent)
Examples of the release agent include isopropylacid phosphate, butyl acid phosphate, octyl acid phosphate, nonyl acid phosphate, decyl acid phosphate, isodecyl acid phosphate, isodecyl acid phosphate, and tridecyl acid phosphate. , Stearyl Acid Phosphate, Propylphenyl Acid Phosphate, Butylphenyl Acid Phosphate, Butoxyethyl Acid Phosphate and other phosphoric acid ester compounds. The phosphoric acid ester compound may be either a phosphoric acid monoester compound or a phosphoric acid diester compound, but a mixture of the phosphoric acid monoester compound and the phosphoric acid diester compound is preferable.
The amount of the release agent added is preferably 0.01 parts by mass or more, preferably 0.05 parts by mass or more, preferably 0.05 parts by mass or more, based on 100 parts by mass of the total of the polyisocyanate compound (A) and the polythiol compound (B). Is 1.00 parts by mass or less, preferably 0.50 parts by mass or less.

(Colorant)
Examples of the colorant include blue and red dyes or pigments. The amount of the colorant added is preferably 2 to 20 ppm, more preferably 3 to 35 ppm, still more preferably 6 to 30 ppm with respect to the iso (thio) cyanate compound.

[Optical member]
An optical member can be obtained by polymerizing the above-mentioned polymerizable composition for an optical member to produce a polymer.
Examples of the optical member include a spectacle lens, a camera lens, a prism, an optical fiber, a base material used for these, a substrate for a recording medium used for an optical disk or a magnetic disk, an optical filter attached to a computer display, and the like. .. Among these, the base material of the spectacle lens and the spectacle lens is preferable, and the base material of the spectacle lens is more preferable.
The polymerization conditions of the polymerizable composition for an optical member can be appropriately set depending on the polymerizable composition.
The polymerization start temperature is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, preferably 50 ° C. or lower, and more preferably 40 ° C. or lower. It is preferable to raise the temperature from the polymerization start temperature and then heat to cure and form. For example, the maximum temperature rise is usually 110 ° C. or higher and 130 ° C. or lower.
After the polymerization is completed, the spectacle lens may be released and annealed. The temperature of the annealing treatment is preferably 100 to 150 ° C.
When the optical member is a spectacle lens, the polymerization is preferably a casting polymerization method. The spectacle lens is obtained, for example, by injecting a polymerizable composition into a mold mold in which a glass or metal mold and a tape or a gasket are combined to carry out polymerization.

(Glasses lens)
When the optical member is used as a spectacle lens, the optical member may be used as it is as a spectacle lens, or a functional layer may be formed or processed on a base material for a spectacle lens to form a spectacle lens.
The surface shape of the spectacle lens is not particularly limited, and may be a flat surface, a convex surface, a concave surface, or the like.
The spectacle lens may be any of a single focus lens, a multifocal lens, a progressive power lens and the like. For example, as an example, for a progressive power lens, the near portion region (near portion) and the progressive portion region (intermediate region) are usually included in the lower region, and the distance portion region (distance portion) is upward. Included in the area.
The spectacle lens may be a finish type spectacle lens or a semi-finish type spectacle lens. Since the semi-finish type spectacle lens is processed into a spectacle lens actually used by polishing or grinding, it is generally thick. However, when the polymerizable composition for an optical member according to the embodiment of the present invention is used, the occurrence of veins can be sufficiently suppressed even with a thick semi-finish type spectacle lens.
The thickness and diameter of the spectacle lens are not particularly limited, but the thickness is usually about 1 to 30 mm, and the diameter is usually about 50 to 100 mm.
The refractive index ne of the spectacle lens is preferably 1.53 or more, more preferably 1.55 or more, more preferably 1.58 or more, still more preferably 1.60 or more, still more preferably 1.67 or more, still more preferably. It is 1.70 or more, preferably 1.80 or less.
Examples of the functional layer that can be provided on the spectacle lens include one or more selected from the group consisting of a hard coat layer, a primer layer, an antireflection film, and a water repellent film.
The hard coat layer is provided for improving scratch resistance, and is preferably formed by applying a coating liquid having a fine particle inorganic substance such as an organosilicon compound, tin oxide, silicon oxide, zirconium oxide, or titanium oxide. Can be done.
The primer layer is provided to improve impact resistance, and for example, polyurethane is the main component. Here, the content of polyurethane is preferably 50% by mass or more in the primer layer.
Examples of the antireflection film include a film in which silicon oxide, titanium dioxide, zirconium oxide, tantalum oxide and the like are laminated.
The water-repellent film can be formed by using an organosilicon compound having a fluorine atom.

[Manufacturing method of optical member]
In the method for producing an optical member according to the present embodiment, the optical member is molded by a molding die using the polymerizable composition for an optical member obtained by the method for producing a polymerizable composition for an optical member described above.

In the present invention, the above-mentioned examples, contents, and various physical properties of each component may be arbitrarily combined with the matters described as examples or preferable ranges in the detailed description of the invention.
Further, if the composition described in the examples is adjusted to the composition described in the detailed description of the invention, the invention can be carried out in the same manner as in the examples over the entire claimed composition range.

Hereinafter, the present invention will be specifically described with reference to Examples. The evaluation of foam defects, the evaluation of the outer peripheral chipping, and the evaluation of the pulse suppression property in the optical member, which is a polymer of the polymerizable composition for the optical member, were carried out by the following procedure.

<Evaluation of defective bubbles>
In a dark box, a diameter of 30 mm or less from the geometric center of the lens base material for spectacles was visually observed under a fluorescent lamp, and those in which the presence of bubbles could be confirmed were rejected. The inspection was performed on the spectacle lens base material manufactured under each condition, and the occurrence rate of rejected products is shown in the table.

<Evaluation of outer circumference chipping>
The entire end (outer circumference) of the lens base material for spectacles was visually and microscopically confirmed, and those found to be chipped were regarded as defective products. Then, the ratio of the defective product to the total of the non-defective product (non-defective product) and the defective product was calculated and used as the evaluation of the outer peripheral chipping. It is preferable that this ratio is as small as possible, and if it is 1% or less, there is no problem in practical use.

<Evaluation of pulse>
Projection inspection was performed using Optical Modurex SX-UI251HQ manufactured by Ushio, Inc. A white screen was installed at a distance of 1 m using a high-pressure UV lamp USH-102D as a light source, the test resin was inserted between the light source and the screen, the projected image on the screen was observed, and based on the following criteria. Judgment was made. A to C were passed, and D and E were rejected.
A: There is no linear irregularity in the projected image.
B: The projected image has a very thin linear irregularity.
C: There is a thin linear irregularity in the projected image.
D: The projected image has dark linear irregularities.
E: The projected image has significant linear irregularities.
Then, the ratio of defective products to the total of passed products (non-defective products) and rejected products (defective products) was calculated and used as the evaluation of the pulse.

<Example 1>
50.6 parts by mass of 1,3-bis (isocyanatomethyl) benzene as the polyisocyanate compound (A) was put into the container (capacity 100 L) of the type of manufacturing apparatus shown in FIG. 1 that can withstand reduced pressure. Further, 0.50 parts by mass of Seasorb 701 manufactured by Cipro Kasei Co., Ltd. was added as an ultraviolet absorber, and 0.01 part by mass of dimethyltindichloride was added as a polymerization catalyst, and these were stirred at a stirring speed of 500 rpm for 15 minutes. Additives were mixed and dissolved. Further, as the polythiol compound (B), 4,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol, 4,8-bis (mercaptomethyl) -3,6,9 Add 49.4 parts by mass of a mixture of −trithiaundecane-1,11-dithiol and 5,7-bis (mercaptomethyl) -3,6,9-trithiaundecane-1,11-dithiol and stir. The mixture was stirred at a speed of 500 rpm for 5 minutes.
After that, the inside of the container is sealed, and the vacuum pump is operated while continuing to stir the mixed solution to reduce the pressure inside the container, and the raw material temperature is set to 20 ° C. to reach 80 Pa in 30 minutes (that is, the ultimate vacuum degree is reached). By setting the temperature to 80 Pa), the first degassing treatment was performed.
After returning the inside of the container to normal pressure, 0.10 parts by mass of butoxyethyl acid phosphate (JP-506H manufactured by Johoku Chemical Industry Co., Ltd.) was added as a release agent, and the mixture was stirred at a stirring speed of 500 rpm for 5 minutes. After that, the inside of the container is sealed again, the vacuum pump is operated while continuing stirring, the inside of the container is depressurized, and the inside of the container reaches 40 Pa in 30 minutes (that is, the ultimate vacuum degree is set to 40 Pa). The second degassing process was performed.
The solution thus obtained was filtered through a polypropylene (PP) filter having a pore size of 5.0 μm to obtain a polymerizable composition 1 for an optical member.
The obtained polymerizable composition 1 for an optical member is injected into a molding die composed of a glass mold having a lens shape of -4.00D and a gasket, and the molding die is put into a polymerization furnace to rise from 15 ° C. to 120 ° C. It was warmed and the polymerizable composition for an optical member was polymerized over 24 hours. After completion of the polymerization, the molding die was taken out from the polymerization furnace and released to obtain a lens base material for spectacles before annealing treatment. The obtained spectacle lens base material before the annealing treatment was further placed in an annealing furnace having an internal temperature of 120 ° C. and annealed for 3 hours to prepare a spectacle lens base material.

<Examples 2 to 9>
The procedure is the same as that of Example 1 except that the type of manufacturing equipment to be used, the degassing time, the ultimate vacuum degree, the temperature of the raw material, and the stirring speed are as shown in Table 1. , A lens base material for spectacles having the same shape as that of Example 1 was produced. The numerical values shown in the “Device type” column of Table 1 indicate which type of the above-mentioned first to third embodiments the manufacturing equipment used corresponded to, and “1” indicates. The type of manufacturing equipment shown in the first embodiment was used, "2" used the type of manufacturing equipment shown in the second embodiment, and "3" used the type of manufacturing equipment shown in the third embodiment. means. In Examples 2, 5 and 8 using the type of manufacturing apparatus shown in the second embodiment, the defoaming member was rotated at about 120 rpm.

<Comparative Examples 1 to 3>
The degassing time, the ultimate vacuum, the temperature of the raw material, and the stirring speed are set to the values shown in Table 1, and the raw material is put into the container of the manufacturing device in which the defoaming member is removed from the manufacturing device of the type shown in the first embodiment. Then, a polymerizable composition for an optical member was prepared. Then, using this polymerizable composition for optical members, a lens base material for spectacles having the same shape as in Example 1 was produced by the same procedure as in Example 1.

The measurement results of Examples and Comparative Examples are shown in Table 1 together with the manufacturing conditions.

As is clear from Table 1, although the degassing time of Examples 1 to 9 was shorter than that of Comparative Examples 1 to 3, the obtained lens base material for spectacles was evaluated for defective foam and chipped outer circumference. No defects were found, and it can be seen that high-quality optical members could be manufactured efficiently. In the evaluation of the veins of Examples 1 to 9, the lower the temperature at which the raw materials are agitated, the larger the difference from the polymerization temperature of the polymerizable composition for optical members, and therefore the defective rate slightly increases. However, better results are obtained as compared with Comparative Examples 1 to 3.
On the other hand, in Comparative Examples 1 to 3, the degassing treatment was performed by lowering the stirring speed, lengthening the degassing time, and increasing the degree of vacuum arrival so that the bubbles generated from the raw materials would not easily accumulate on the liquid surface. Nevertheless, it can be seen that the incidence of defective products in which any of bubbles, chipping of the outer circumference, and veins occurred is higher than that of the examples. Further, in Comparative Examples 1 to 3, it can be seen that the time required for the degassing process cannot be shortened, and as a result, it takes a long time to manufacture the optical member. Since the defoaming member is not arranged in Comparative Examples 1 to 3, the polymerizable composition cannot be removed well during the production of the polymerizable composition for optical members, or the polymerizable composition takes time to produce. It is thought that alteration is having an effect.

Finally, the embodiments of the present disclosure are summarized. The method for producing a polymerizable composition for an optical member according to the embodiment of the present disclosure is as follows.
The raw material of the polymerizable composition for an optical member is put into a container, and
The raw material in the container is stirred and
The inside of the container is depressurized while stirring the raw material,
This is a method for producing a polymerizable composition for an optical member, which mechanically destroys bubbles generated from the raw material while stirring in the container under reduced pressure.
According to the above-described embodiment, it is possible to obtain a method for producing a polymerizable composition for an optical member, which does not require a long production time and can obtain a high-quality polymerizable composition for an optical member.

It should be considered that the embodiments disclosed this time are exemplary in all respects and not restrictive. The scope of the present invention is shown not by the above description but by the scope of claims, and is intended to include all modifications within the meaning and scope equivalent to the scope of claims.
In the present disclosure, items described as examples or preferable ranges in the detailed description of the invention may be arbitrarily combined with respect to examples, contents, and various physical properties of each of the above components.
Further, if the composition described in the examples is adjusted so as to have the composition described in the detailed description of the invention, the disclosed embodiment can be implemented in the same manner as in the examples over the entire claimed composition range. it can.

1: Container 1a: Exhaust port 1b: Discharge port 2: Stirring blade 4: Rotating shaft 5: Drive source 6: Exhaust line 7: Liquid discharge line 8: Vacuum pump 9: Trap 10: Lock 11: Hinge 20: For optical members Raw material of polymerizable composition 21: Accumulated foam 30: Propeller-shaped defoaming member 31: Rod-shaped defoaming member 32: Movable flange 40: Fixed flange 41: Screw 50: Defoaming member having a mesh portion 51: Opening S0 , S1: Liquid level 100A, 100B, 100C: Manufacturing equipment

Claims (14)

The raw material of the polymerizable composition for an optical member is put into a container, and
The raw material in the container is stirred and
The inside of the container is depressurized while stirring the raw material,
A method for producing a polymerizable composition for an optical member, which mechanically destroys bubbles generated from the raw material while stirring in the depressurized container. The raw material contains a polymerizable material and a mold release agent.
Following the polymerizable material, the release agent is charged into the container.
The method for producing a polymerizable composition for an optical member according to claim 1, wherein stirring of the raw material is started after the release agent is added, and then the pressure in the container is reduced and bubbles are destroyed. The raw material includes a first material, a second material, and a third material.
After the first material and the second material are put into the container, and after the third material is put into the mixture of the first material and the second material, the above, respectively. The method for producing a polymerizable composition for an optical member according to claim 1, wherein stirring, depressurization, and foam breaking are sequentially performed. The polymerizable composition for an optical member according to any one of claims 1 to 3, wherein the stirring and depressurization are continued for a predetermined time, and after the inside of the container reaches a predetermined degree of vacuum, the stirring and depressurization are terminated. Manufacturing method of things. The method for producing a polymerizable composition for an optical member according to any one of claims 1 to 4, wherein the temperature is controlled so that the raw material has a predetermined temperature. A container for storing liquid raw materials and
A rotating shaft connected to the drive source and rotatably arranged in the container,
With the stirring blade attached to the rotating shaft,
A defoaming member, which is arranged above the stirring blade and comes into contact with bubbles generated from the raw material to destroy the bubbles, is provided.
The container is an apparatus for producing a polymerizable composition for an optical member, which has an exhaust port for exhausting an internal gas to the outside. The polymerizable composition for an optical member according to claim 6, wherein the defoaming member is arranged at a height equal to or higher than the highest position of the liquid surface of the raw material when the raw material is stirred by the stirring blade. manufacturing device. The apparatus for producing a polymerizable composition for an optical member according to claim 6 or 7, wherein the defoaming member is rotated by rotation of the rotation shaft. The apparatus for producing a polymerizable composition for an optical member according to any one of claims 6 to 8, wherein the defoaming member rotates at a rotation speed slower than the rotation axis in the rotation direction of the rotation axis. The polymerizable property for an optical member according to any one of claims 6 to 9, wherein the defoaming member is fixed in the axial direction of the rotating shaft and rotatably held in the rotating direction of the rotating shaft. Composition manufacturing equipment. The apparatus for producing a polymerizable composition for an optical member according to any one of claims 6 to 10, wherein the defoaming member has a propeller shape or a rod shape. The apparatus for producing a polymerizable composition for an optical member according to claim 6 or 7, wherein the defoaming member has a net unit that spreads two-dimensionally with respect to the liquid surface of the raw material. The polymerizable composition for an optical member according to any one of claims 6 to 12, wherein an exhaust device is connected to the exhaust port via an exhaust pipe, and the exhaust pipe has a trap for trapping an attracted material. Manufacturing equipment. A method for producing an optical member, which comprises molding an optical member using the polymerizable composition for an optical member obtained by the method for producing a polymerizable composition for an optical member according to any one of claims 1 to 5.

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