TW201444880A - Apparatus and method for manufacturing chlorinated vinyl chloride resin - Google Patents

Abstract

The purpose of the present invention is to provide a production device and a production method for a chlorinated vinyl chloride-based resin which are capable of efficiently producing a chlorinated vinyl chloride-based resin. This production device is provided with a reaction tank (1) into which chlorine and an aqueous suspension (7) of a vinyl chloride-based resin are introduced. The reaction tank (1) has, provided therein, an optical fibre (5a) which radiates ultraviolet rays.

Description

Manufacturing device and manufacturing method of chlorinated vinyl chloride resin

The present invention relates to a manufacturing apparatus and a manufacturing method of a chlorinated vinyl chloride resin. More specifically, it relates to a manufacturing apparatus and a manufacturing method of a chlorinated vinyl chloride resin using a photochlorination method.

The heat resistant temperature of the chlorinated vinyl chloride resin is higher than the heat resistant temperature of the vinyl chloride resin by chlorination. Therefore, the chlorinated vinyl chloride resin is used in various fields such as heat-resistant tubes, heat-resistant industrial sheets, heat-resistant films, and heat-resistant sheets.

The chlorinated vinyl chloride resin is usually produced by chlorinating a vinyl chloride resin while supplying chlorine to an aqueous suspension obtained by suspending the vinyl chloride resin particles in an aqueous medium. In the case of chlorination by a photo-chlorination method, ultraviolet irradiation by a mercury lamp is performed in order to generate a chlorine radical (Patent Document 1).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Publication No. Hei 10-128627 (published on October 20, 1998)

In the above method for producing a chlorinated vinyl chloride resin, the vinyl chloride is dispersed in the direction When chlorine is supplied to the aqueous suspension of the resin, the inside of the reactor is usually pressurized in order to increase the amount of chlorine dissolved in the suspension. At this time, if the internal pressure of the reactor is excessively increased, the glass tube covering the mercury lamp is damaged. On the other hand, when the thickness of the glass tube is increased, the pressure resistance is improved. However, if the thickness of the glass tube is increased, the ultraviolet ray irradiated from the mercury lamp is absorbed by the glass, and the reaction efficiency is lowered.

In order to solve the problem, the inventors of the present invention have conducted an effort to find that an ultraviolet ray having an ultraviolet ray emitting portion is used to introduce and emit ultraviolet rays irradiated from a light source provided outside the reaction vessel into the reaction vessel. Since the glass tube is not required to be disposed in the reaction tank, the internal pressure of the reaction tank can be increased, and the amount of chlorine dissolved in the suspension can be increased. As a result, the production efficiency of the chlorinated vinyl chloride resin can be improved. this invention. In other words, the main object of the present invention is to provide an apparatus for producing a chlorinated vinyl chloride resin which improves the reaction efficiency in the production of a chlorinated vinyl chloride resin, for example, by increasing the amount of chlorine dissolved in a suspension of a vinyl chloride resin. Production method.

In order to solve the problem, the apparatus for producing a chlorinated vinyl chloride resin according to the present invention is characterized in that the chloroethylene resin is chlorinated by irradiation of ultraviolet rays to produce a chlorinated vinyl chloride resin, and the chlorine is contained. a reaction tank for introducing a vinyl resin and chlorine, and a light source provided outside the reaction tank, wherein the reaction tank includes an ultraviolet light introduction unit that introduces ultraviolet light irradiated from the light source into the reaction tank, and the ultraviolet light introduction unit includes the light in the reaction chamber. UV-emitting part of ultraviolet light.

In order to solve the problem, the method for producing a chlorinated vinyl chloride resin according to the present invention is characterized in that the ultraviolet ray-emitting portion contained in the inside of the reaction vessel is irradiated with ultraviolet rays by irradiating the chlorine-containing vinyl chloride resin.

According to the apparatus for producing a chlorinated vinyl chloride resin of the present invention or the method for producing a chlorinated vinyl chloride resin, the following effects are obtained: for example, a suspension of a vinyl chloride resin is improved. The amount of chlorine dissolved therein increases the reaction efficiency in the production of, for example, a chlorinated vinyl chloride resin.

1‧‧‧Reaction tank

2‧‧‧ casing

3‧‧‧Agitating wing

4‧‧‧Agitator shaft

5, 5b‧‧ ‧ fiber group (ultraviolet introduction)

5a‧‧‧Optical fiber (UV emission department)

6‧‧‧Lighting Department

7‧‧‧Aqueous suspension of vinyl chloride resin

8‧‧‧Supply tube

9‧‧‧Light source

10, 10a‧‧ ‧ glass rod (ultraviolet emission department)

20, 20a‧‧‧Support

40‧‧‧Parts

50‧‧‧ Full length

60‧‧‧ cross section

100, 100a, 100b, 100c‧‧‧ ultraviolet LED light source device

110, 110a, 110b‧‧‧ UV LED components

120‧‧‧UV exit

200, 200a‧‧‧Support

300, 300a, 300b, 300c‧‧‧ cylindrical containers

400, 400a‧‧‧ warm water

500, 500a‧‧ ‧ water bath

600, 600a, 600b, 600c, 600d‧‧‧ reactor

610, 610a, 610b, 610c‧‧‧ turbine wings

620, 620a, 620b, 620c, 620d‧ ‧ cover

700, 700a, 700b, 700c, 700d‧‧‧Aqueous suspension of vinyl chloride resin

A‧‧‧distance between reactor 600b and ultraviolet LED element 110b

B‧‧‧Little chain

C‧‧‧ arrow

Fig. 1 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin comprising an ultraviolet LED (Light Emitting Diode) light source device and a reactor used in Reference Example 1.

Fig. 2 is a view showing an example of an emission spectrum of an ultraviolet LED used in Reference Example 1.

Fig. 3 is a side sectional view schematically showing an ultraviolet LED light source device used in Reference Example 2.

4 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin containing an ultraviolet LED light source device and a reactor used in Reference Example 2.

Fig. 5 is a plan cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin containing an ultraviolet LED light source device and a reactor used in Reference Example 2.

Fig. 6 is a side sectional view schematically showing an ultraviolet LED light source device used in Reference Example 3.

Fig. 7 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin comprising an ultraviolet LED light source device and a reactor used in Reference Example 3.

Fig. 8 is a view showing an example of an emission spectrum of an ultraviolet LED used in Reference Example 4.

Fig. 9 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin comprising an ultraviolet LED light source device and a reactor used in Reference Example 5.

10(A) and (B) are schematic cross-sectional views showing an embodiment of the apparatus for producing a chlorinated vinyl chloride resin of the present invention.

(A) and (B) are schematic cross-sectional views showing another embodiment of the apparatus for producing a chlorinated vinyl chloride resin of the present invention.

12(A) and (B) are views showing a device for producing a chlorinated vinyl chloride resin of the present invention. Further, it is a schematic cross-sectional view showing still another embodiment.

Fig. 13 is a schematic side view showing another embodiment of the apparatus for producing a chlorinated vinyl chloride resin of the present invention.

Fig. 14 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin comprising an ultraviolet LED light source device and a reactor used in the examples.

Fig. 15 is a view schematically showing a glass rod used in the examples.

Fig. 16 is a side cross-sectional view schematically showing a manufacturing apparatus of a chlorinated vinyl chloride resin containing an ultraviolet LED light source device and a reactor used in a comparative example.

Hereinafter, the apparatus and method for producing a chlorinated vinyl chloride resin of the present invention will be described in detail, but the scope of the present invention is not limited by the above description, and the present invention may be omitted without departing from the following examples. It is implemented by appropriately changing the scope. Specifically, the present invention is not limited to the embodiments described below, and various modifications can be made within the scope of the invention. The embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included. It is within the technical scope of the present invention.

The apparatus for producing a chlorinated vinyl chloride resin of the present invention is a device for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin by irradiation with ultraviolet rays, and a reaction tank for introducing a vinyl chloride resin and chlorine, and The light source provided outside the reaction tank includes an ultraviolet light introduction portion that introduces ultraviolet light irradiated from the light source into the reaction tank, and the ultraviolet light introduction portion has an ultraviolet light emitting portion that irradiates the reaction chamber with ultraviolet rays. Moreover, the method for producing a chlorinated vinyl chloride resin of the present invention has an irradiation step of irradiating ultraviolet rays to the chlorine-containing vinyl chloride resin introduced from the inside of the reaction vessel.

The chlorinated vinyl chloride resin produced in the present invention is obtained by irradiating ultraviolet rays to a chlorine-based resin into which chlorine is introduced, that is, by chlorinating the vinyl chloride resin by photochlorination.

<Manufacturing apparatus and manufacturing method of chlorinated vinyl chloride resin>

The apparatus and method for producing a chlorinated vinyl chloride resin of the present invention will be described below. In the following description, the following cases are exemplified, that is, a vinyl chloride resin is introduced as a suspension.

As shown in Fig. 10 (A) and (B), the apparatus for producing a chlorinated vinyl chloride resin according to an embodiment is a device for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin by irradiation with ultraviolet rays. Further, the reaction vessel 1 can be sealed, and the inside of the reactor can be vacuum degassed and replaced with nitrogen, and the light source 9 disposed outside the reaction vessel 1. The reaction tank 1 is provided with a sleeve 2 for temperature adjustment around it. In the reaction tank 1, a suspension of a vinyl chloride resin, preferably an aqueous suspension 7, is introduced through a tube (not shown), and is supplied to the aqueous suspension through a supply pipe 8 inserted into the bottom of the reaction vessel 1. Chlorine gas is introduced into 7 . Further, the reaction tank 1 includes an agitating shaft 4 including the stirring blade 3 and an ultraviolet light introducing unit that introduces ultraviolet light irradiated by the light source 9 into the reaction tank 1, specifically, the optical fiber group 5. The above-mentioned optical fiber group 5 has an ultraviolet light emitting portion that irradiates ultraviolet rays into the reaction bath 1, specifically, an optical fiber 5a. In other words, since the optical fiber 5a provided in the inside of the reaction tank 1 is irradiated with ultraviolet rays, the light source 9 can be disposed outside the reaction tank 1, and the glass tube for covering the light source is not required to be disposed in the reaction tank 1, so that the reaction tank is provided. The degree of design freedom of 1 is increased, and for example, it can be produced by a titanium palladium alloy.

As the ultraviolet light emitting portion, a glass rod may be mentioned in addition to the optical fiber. In other words, the ultraviolet light-emitting portion is not particularly limited as long as it has a pressure resistance, an acid resistance, and a chlorine resistance which can withstand the production of a chlorinated vinyl chloride resin, and can introduce ultraviolet rays into the inside of the reaction vessel 1 . Preferably, it is an optical fiber or a glass rod. The manufacturing apparatus shown in Figs. 10(A) and (B) is an example in which an optical fiber is used as the ultraviolet light emitting portion.

The ultraviolet light emitting unit provided in the apparatus for producing a chlorinated vinyl chloride resin (for example, the optical fiber 5a shown in Figs. 10(A) and (B), the glass rod 10 shown in Figs. 11(A) and (B), and Fig. 12 ( The number of the optical fibers 5a and the like of A) and (B) is not particularly limited and may be one or plural. In view of shortening the reaction time of the chlorination reaction, the number of the ultraviolet light-emitting portions provided in the apparatus for producing the chlorinated vinyl chloride resin is preferably plural.

Further, in the case where the number of the ultraviolet light-emitting portions is plural, the amount is preferably as large as possible within the range of stirring of the aqueous suspension 7 in the reaction tank 1. The greater the number of ultraviolet emitters, the more time the chlorination reaction can be shortened.

When a plurality of ultraviolet light emitting units are provided, the number of the ultraviolet light emitting units provided in one reaction tank is not particularly limited, and two or more, three or more, four or more, five or more, or six or more, 7 or more, 8 or more, 9 or more, 10 or more, 20 or more, 30 or more, 40 or more, or 50 or more. In this case, the upper limit of the number of the ultraviolet light emitting portions provided in one reaction tank is not particularly limited, and may be appropriately set depending on the volume of the reaction tank 1 or the like. For example, the above upper limit may be 100, 500 or 100, but the present invention is not limited to the upper limit.

In the case where a plurality of ultraviolet light emitting portions are provided, the arrangement of the plurality of ultraviolet light emitting portions in the reaction tank is not particularly limited, and it is preferably arranged uniformly and dispersed in the reaction tank.

The method of supplying the aqueous suspension 7 or chlorine to the reaction tank 1 is not particularly limited. For example, the aqueous suspension 7 of chlorine-based resin and chlorine may be introduced into the reaction tank 1 after being mixed in advance. In other words, the reaction vessel 1 may be configured to supply an aqueous suspension 7 in which a chlorine-based vinyl chloride resin is introduced. Further, for example, the reaction tank 1 may be configured to supply a powder or a particulate vinyl chloride resin, water, and chlorine. In other words, the reaction vessel 1 may have a configuration in which an aqueous suspension 7 of a vinyl chloride resin is formed in the tank. In the production apparatus of the present invention, the aqueous suspension 7 into which the chlorine-based vinyl chloride resin is introduced may be present in the reaction tank 1 when ultraviolet rays are irradiated.

The optical fiber 5a is disposed in a region other than the rotation region of the stirring blade 3 in the reaction tank 1. That is, the optical fiber 5a is disposed in the reaction tank 1 in a region that does not interfere with the rotation operation of the stirring blade 3. The optical fiber 5a may be partially disposed in the reaction tank 1, or may be disposed in the reaction tank 1 as follows, for example, as shown in Figs. 10(A) and (B), radially expanding and including The surface of the stirring shaft 4 of the stirring blade 3 becomes substantially symmetrical. In other words, the optical fibers 5a may be disposed non-locally in the reaction tank 1 so that the mutual distances thereof are substantially equal. Figure 10 (A) and In the embodiment shown in (B), the end portion of the inside of the reaction vessel 1 of the optical fiber 5a is disposed in a non-local manner in the reaction tank 1 in such a manner that it does not interfere with the rotation operation of the stirring blade 3, that is, radially expands. Further, the surface of the stirring shaft 4 including the stirring blade 3 becomes substantially symmetrical. By disposing the optical fiber 5a in the reaction vessel 1 so as to be substantially symmetrical with respect to the surface including the stirring shaft 4 of the stirring blade 3, the aqueous suspension 7 of the vinyl chloride resin can be uniformly irradiated with ultraviolet rays. The plurality of optical fibers 5a disposed in the region other than the rotation region of the stirring blade 3 in the reaction tank 1 are disposed in such a manner that they are not in contact with the rotating stirring blade 3 and are immersed in the aqueous suspension of the vinyl chloride resin. . That is, the optical fiber 5a is irradiated with ultraviolet rays in the aqueous suspension 7 of the vinyl chloride resin.

The optical fiber 5a is brittle, and is broken by contact with the stirring blade 3, or is broken by the force applied to the optical fiber 5a by the flowing aqueous suspension 7. Therefore, it is preferable that the apparatus for producing a chlorinated vinyl chloride resin of the present invention has a structure for protecting the optical fiber 5a from damage (for example, the support 20 and the support 20a).

When the optical fiber 5a is disposed in a region other than the rotation region of the stirring blade 3 in the reaction tank 1, the optical fiber 5a may be fixed to the support 20 as shown in Figs. 10(A) and (B). In the body 20a), the support body 20 (the support body 20a) is disposed in a region other than the rotation region of the stirring blade 3, and is not in contact with the stirring blade 3. According to this configuration, it is possible to prevent the optical fiber 5a from being broken by being wound around the stirring blade 3, and the optical fiber 5a being damaged by the force applied by the flowing aqueous suspension 7 by the optical fiber 5a.

When the optical fiber 5a is fixed to the support 20 (the support 20a), the position of the optical fiber 5a with respect to the support 20 (support 20a) is not specifically limited. For example, the optical fiber 5a may be embedded inside the support 20 (support 20a), or the optical fiber 5a may be fixed to the surface of the support 20 (support 20a).

The support 20 (support 20a) may be formed of a material that is difficult to be deformed (or not deformed) by the flowing aqueous suspension 7 and gravity or the like. For example, it may be formed of titanium palladium or the like. According to this configuration, even if a force is applied to the support 20 (the support 20a), the support 20 (support 20a) is also It is not deformed, in other words, the optical fiber 5a is not deformed, so that the optical fiber 5a becomes difficult to be broken.

The shape of the support body 20 (the support body 20a) is not particularly limited, and may be a shape having an internal space and a shape in which the stirring blade 3 can be accommodated in the internal space. Examples of the shape of the support 20 include a shape of a bell, a cone shape (for example, a cone or a polygonal pyramid), and a cylindrical shape (for example, a cylinder or a polygonal column).

The support 20 may also be a hole having a flow through which the aqueous suspension 7 flows. More specifically, the support 20 may be a member having at least a part of a mesh structure. If the support 20 is provided with a hole, the flowing aqueous suspension 7 can pass through the hole, and the force applied to the support 20 can be reduced. That is, it is possible to more suitably prevent deformation of the support 20 (in other words, the optical fiber 5a), in other words, the optical fiber 5a is deformed, so that the optical fiber 5a becomes difficult to be broken.

A light source 9 that emits ultraviolet rays is disposed outside the reaction tank 1, and specifically, for example, an ultraviolet LED, an organic EL, an inorganic EL, an ultraviolet laser, and a mercury lamp, preferably selected from the group consisting of ultraviolet LEDs and organic ELs At least one of the group consisting of inorganic EL and ultraviolet laser. Further, the above-described optical fiber group 5 is formed by, for example, bundling a plurality of optical fibers 5a. Further, a light collecting portion 6 such as a collecting lens that collects ultraviolet rays irradiated by the light source 9 is provided at an end portion of the outer side of the reaction vessel 1 of the optical fiber group 5. Therefore, the optical fiber group 5 as the ultraviolet light-introducing portion collects the ultraviolet light irradiated from the light source 9 by the light collecting portion 6, and introduces it into the reaction vessel 1 to form an aqueous suspension of the vinyl chloride resin through the optical fiber 5a as the ultraviolet light-emitting portion. 7 is irradiated with ultraviolet light. Thereby, the optical fiber 5a can uniformly irradiate the ultraviolet ray to the aqueous suspension 7 of the vinyl chloride resin. The degree of the thickness of the optical fiber 5a is not particularly limited as long as it can maintain the strength of the agitation of the agitation blade 3 or more. Further, the optical fiber 5a is not only irradiated with ultraviolet rays from the tip end thereof, but also irradiates ultraviolet rays from the side surface by forming a slit or the like.

Further, the reaction vessel 1 is preferably made of a pressure-resistant structure by being produced, for example, of a titanium-palladium alloy. Specifically, the reaction tank 1 preferably has a strength capable of setting the internal pressure to a range of 0.02 to 2.00 MPa.

Further, the reaction vessel 1 preferably has a strength capable of setting the internal pressure to a range of 0.05 to 2.00 MPa, more preferably a strength capable of setting the internal pressure to a range of 0.06 to 1.50 MPa, and further preferably has a strength The internal pressure is set to a strength in the range of 0.08 to 1.20 MPa. In addition, the reaction tank 1 preferably has a strength in which the internal pressure can be set in the range of 0.10 to 1.00 MPa, and more preferably has a strength in which the internal pressure can be set in the range of 0.12 to 0.50 MPa.

If it is in the above range, the reaction efficiency of chlorination can be improved.

In the manufacturing apparatus of the present invention, since the optical fiber 5a provided in the inside of the reaction tank 1 is irradiated with ultraviolet rays, the light source 9 can be disposed outside the reaction tank 1, and it is not necessary to arrange a glass tube for covering the light source in the reaction tank 1. Thereby, since the manufacturing apparatus can pressurize the inside of the reaction tank 1, the inside of the vinyl chloride resin can fully absorb chlorine, and the reaction efficiency can be improved.

In the production of the chlorinated vinyl chloride resin using the reaction vessel 1 having the above-described configuration, first, after the inside of the reaction vessel 1 is purged with nitrogen, a suspension of, for example, a vinyl chloride resin is supplied to the inside of the reaction vessel 1, preferably aqueous suspension. The liquid 7 is introduced with chlorine gas while stirring the aqueous suspension 7 by the stirring blade 3 (introduction step). At this time, it is preferable that the inside of the reaction tank 1 is pressurized by the introduced chlorine gas, and for example, it may be pressurized to 0.02 to 2.00 MPa. More specifically, it is preferably pressurized to 0.05 to 2.00 MPa, more preferably pressurized to 0.06 to 1.50 MPa, and further preferably pressurized to 0.08 to 1.20 MPa. In addition, it is more preferably pressurized to 0.10 to 1.00 MPa, and particularly preferably pressurized to 0.12 to 0.50 MPa.

If it is in the above range, the reaction efficiency of chlorination can be improved.

Then, while the aqueous suspension 7 of the vinyl chloride resin is stirred by the stirring blade 3, the ultraviolet ray irradiated by the light source 9 is introduced into the reaction vessel 1 by the optical fiber group 5, and the optical fiber 5a disposed inside the reaction vessel 1 is passed. The aqueous suspension 7 of the vinyl chloride resin was irradiated (irradiation step). Thereby, the chlorination reaction is started. Further, during the irradiation step, the temperature in the reaction tank 1 is preferably controlled by pouring warm water into the sleeve 2.

The chlorination reaction proceeds, and the chlorine content of the chlorinated vinyl chloride resin reaches the desired value. At this time, the ultraviolet irradiation by the light source 9 is ended, and the chlorination reaction is completed. Thereafter, nitrogen gas was supplied into the reaction vessel 1, and unreacted chlorine in the chlorinated vinyl chloride resin was purged with nitrogen, and then the residual hydrochloric acid was washed with water (cleaning step). Then, the chlorinated vinyl chloride resin was taken out from the reaction tank 1 and dried. Thereby, a chlorinated vinyl chloride resin can be produced.

The apparatus for producing a chlorinated vinyl chloride resin of the present invention may have a configuration in which a plurality of optical fibers 5a are partially or non-locally provided in the reaction vessel 1, and as a modification, as shown in Figs. 11(A) and (B). The glass rod 10 inserted into the reaction tank 1 is provided as shown. Further, the number of the glass rods 10 is not particularly limited, and may be, for example, the same as the number of the optical fibers 5a described above, or may be smaller than the number of the optical fibers 5a.

At this time, as shown in FIG. 11(A), after the one bundle of the optical fiber groups 5 is branched, the branched optical fiber groups 5 are connected to the respective glass rods 10.

Further, as shown in FIG. 11(B), the plurality of bundles of optical fibers 5 may be connected to the respective glass rods 10 without branching. Further, in Fig. 11(B), one light source 9 is shown, but the number of the light sources 9 is not limited to one. For example, a plurality of light sources 9 respectively corresponding to the plurality of light collecting portions 6 may be provided. Furthermore, in the case where a plurality of light sources 9 are provided, the same type of light source 9 may be provided, and different types of light sources 9 may be provided. When different types of light sources 9 are provided, ultraviolet rays having different wavelengths can be introduced into the reaction tank 1.

Further, the apparatus for producing a chlorinated vinyl chloride resin of the present invention may have a configuration in which a plurality of optical fibers 5a are provided in a non-local manner instead of the reaction vessel 1, and as a modification, as shown in Figs. 12(A) and (B). As shown, a plurality of optical fibers 5a are attached to the inner wall of the reaction vessel 1, and a plurality of optical fibers 5a are partially provided. In this case, the risk of the optical fiber 5a being broken due to agitation can be reduced. In this case, the optical fiber 5a may be fixed to the inner wall of the reaction tank 1, or may not be fixed to the inner wall of the reaction tank 1.

At this time, as shown in FIG. 12(A), after one bundle of the optical fiber groups 5 is branched, the optical fibers 5a are formed by the optical fiber groups 5 of the respective branches.

Further, as shown in FIG. 12(B), the plurality of bundles of optical fibers 5 may be branched without forming light. Fiber 5a. Further, in Fig. 12(B), one light source 9 is shown, but the number of the light sources 9 is not limited to one. For example, a plurality of light sources 9 respectively corresponding to the plurality of light collecting portions 6 may be provided. Furthermore, in the case where a plurality of light sources 9 are provided, the same type of light source 9 may be provided, and different types of light sources 9 may be provided. When different types of light sources 9 are provided, ultraviolet rays having different wavelengths can be introduced into the reaction tank 1.

Furthermore, the apparatus for producing a chlorinated vinyl chloride resin of the present invention may have a configuration in which a plurality of optical fibers 5a are partially or non-locally provided in the reaction vessel 1, and as a modification, as shown in FIG. The strip fiber 5a is embedded in the inner wall of the reaction tank 1. In this case, the optical fiber 5a is not in contact with the aqueous suspension 7 of the vinyl chloride resin, so that the risk of damage of the optical fiber 5a can be avoided. The portion of the reaction vessel 1 in which the optical fiber 5a is embedded is made of a material that transmits ultraviolet rays (such as ultraviolet rays transmitted through the glass) so as to be irradiated with ultraviolet rays. Further, in order to remove the heat of the reaction vessel 1, the optical fiber 5a is not embedded in the entire surface of the inner wall of the reaction vessel 1, but is preferably embedded in a portion of the inner wall of the reaction vessel 1 so that the embedded portion and the unembedded portion alternate.

In the apparatus for producing a chlorinated vinyl chloride resin of the present invention, the above three modifications may be used alone, or the above three modifications may be used in combination. Further, it may be used in combination with a configuration in which a plurality of optical fibers 5a that are non-locally expanded in the reaction vessel 1 are provided, and at least one of the above three modifications.

The vinyl chloride resin used in the present invention is introduced into the reaction tank as a suspension, more preferably as an aqueous suspension. An aqueous suspension of a vinyl chloride resin can be obtained by suspending a vinyl chloride resin in an aqueous medium. Specifically, for example, when water is used as the aqueous medium and the vinyl chloride resin is mixed with water, an aqueous suspension of the vinyl chloride resin can be obtained.

A vinyl chloride resin used as a raw material of a chlorinated vinyl chloride resin is a homopolymer of a vinyl chloride monomer or a copolymer of a vinyl chloride monomer and another copolymerizable monomer. The other copolymerizable monomer is not particularly limited, and examples thereof include ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylate, and vinyl ether.

When the vinyl chloride monomer is uniformly polymerized, or when the vinyl chloride monomer is copolymerized with another copolymerizable monomer, a dispersing agent, an oil-soluble polymerization initiator, or the like can be used. Further, in the above polymerization, a polymerization regulator, a chain transfer agent, a pH adjuster, an antistatic agent, a crosslinking agent, a stabilizer, a filler, an antioxidant, a scale inhibitor, or the like may be further used.

Examples of the dispersant include partially saponified polyvinyl acetate, methyl cellulose, hydroxypropyl methyl cellulose, and the like. Examples of the oil-soluble polymerization initiator include barium laurate peroxide, di-2-ethylhexyl peroxy neodecanoate, tert-butyl peroxy neodecanoate, and α,α'-azobis- 2,4-dimethylvaleronitrile and the like.

The particle diameter of the vinyl chloride resin is not particularly limited, and the average particle diameter is preferably from 0.1 to 350 μm, more preferably from 80 to 200 μm. In the present invention, the average particle diameter of the vinyl chloride resin is measured in accordance with JIS-K0069.

The aqueous suspension of the vinyl chloride resin is not particularly limited, and can be obtained, for example, by mixing a vinyl chloride resin with water and suspending the vinyl chloride resin in water. The aqueous suspension of the obtained vinyl chloride resin was introduced into a reaction vessel, and stirred by a stirring blade disposed in the reaction vessel. The aqueous suspension of the vinyl chloride resin in the reaction tank is supplied with chlorine while stirring, and if necessary, chlorine is supplied, and the ultraviolet ray is disposed through the ultraviolet ray in the reaction tank, for example, by ultraviolet rays. The irradiation of ultraviolet rays is started by the ultraviolet LED, whereby the chlorination reaction of the vinyl chloride resin is started.

The vinyl chloride resin in the aqueous suspension is chlorinated until it becomes the desired chlorine content. The chlorination reaction is terminated by the end of the irradiation of ultraviolet rays. After the completion of the chlorination reaction, unreacted chlorine in the chlorinated vinyl chloride resin is ejected by nitrogen gas or the like, and further, warm water having a temperature equal to or lower than the Tg (glass transition temperature) of the chlorinated vinyl chloride resin is used. The hydrochloric acid remaining in the chlorinated vinyl chloride resin is removed. Thereafter, a chlorinated vinyl chloride resin is obtained through a dehydration and drying step.

Viscosity stability of productive, aqueous suspensions and uniform mixing during agitation In view of the above, the concentration of the vinyl chloride resin in the aqueous suspension is usually preferably 10% by weight or more and 40% by weight or less, more preferably 20% by weight or more, depending on the molecular weight of the vinyl chloride resin. 35 wt% or less.

In the case where chlorine is supplied to the reaction tank, the chlorine may be either a gas or a liquid, but it is more preferably a gas in view of ease of handling. The method of supplying chlorine is not particularly limited as long as it can supply chlorine to the aqueous suspension. For example, as a method of supplying chlorine, a method of adding chlorine once before the start of the chlorination reaction (initial), a method of intermittently supplying chlorine to the chlorination reaction, and continuously supplying chlorine in the chlorination reaction may be mentioned. In the method, a part of chlorine is added before the start of the chlorination reaction (initial), and the remaining chlorine is supplied intermittently or continuously in the chlorination reaction. As described above, in the present invention, the chlorination reaction starts the reaction by starting to irradiate the ultraviolet ray, and the reaction is terminated by ending the irradiation of the ultraviolet ray.

The maximum reaction temperature in the case of the chlorination reaction is not particularly limited, but is preferably 90 ° C or lower, more preferably 88 ° C or lower, and still more preferably 86 ° C or lower. When the maximum reaction temperature is 90° C. or less, the deterioration of the vinyl chloride resin is suppressed, and the coloration of the obtained chlorinated vinyl chloride resin is suppressed. The lowest reaction temperature in the chlorination reaction is preferably more than 0 ° C from the viewpoint of facilitating the flow of the aqueous suspension by the stirring blade. Further, from the viewpoint of shortening the reaction time, the minimum reaction temperature is preferably 30 ° C or higher, more preferably 50 ° C or higher.

Since the chlorination reaction is an exothermic reaction, in order to control the internal temperature of the reaction vessel, for example, it is preferred to equip the reaction vessel with a cooling jacket. The cooling jacket is used to obtain a balance between heat removal and heat generation, thereby controlling the internal temperature of the reaction tank. The agitating blades arranged in the reaction tank may be an axial flow type such as a propeller wing, or may be a radial type such as a blade wing or a turbine wing.

A light source 9 that irradiates ultraviolet light into a reaction tank in which an aqueous suspension of a vinyl chloride resin and chlorine are introduced through an ultraviolet light emitting unit, specifically, for example, an ultraviolet LED, an organic EL, an inorganic EL, an ultraviolet laser, and a mercury lamp ( Mercury lamp), preferably selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser By irradiating ultraviolet rays with less than one kind of light source, the vinyl chloride resin is efficiently chlorinated to obtain a chlorinated vinyl chloride resin.

However, in the present invention, the initial coloring during the thermoforming of the chlorinated vinyl chloride resin is evaluated by using a sample prepared by heating and molding a chlorinated vinyl chloride resin, and measuring it according to JIS-K7373. Yellowing index. The lower the value of the yellowing index means that the initial coloring at the time of heat molding is suppressed, that is, the initial coloring property at the time of heat molding is good. Further, the thermal stability of the chlorinated vinyl chloride resin was evaluated by using a sample (sheet) prepared using a chlorinated vinyl chloride resin, and heating was carried out in an oven at 200 ° C to measure the sheet. Blackening, that is, the L value (brightness) of the sheet becomes 20 or less. The longer the blackening time, the higher the thermal stability. Further, the heat resistance of the chlorinated vinyl chloride resin was evaluated by measuring the softening point of Vicat by the B50 method in accordance with JIS-K7206. The higher the value of the Vickers softening point, the higher the heat resistance. In addition, the details of the evaluation of initial coloring, thermal stability, and heat resistance at the time of thermoforming of a chlorinated vinyl chloride resin are demonstrated by the following reference examples.

Further, in the present invention, the chlorinated vinyl chloride resin is obtained by chlorinating a suspension of a vinyl chloride resin, preferably an aqueous suspension, as described above, and may also be obtained by a gas. It is obtained by chlorination (vapor phase chlorination) or the like. The gas phase chlorination refers to a case where chlorine is directly blown into a powder of a vinyl chloride resin, and a light source that irradiates ultraviolet rays is used for the vinyl chloride resin and chlorine, specifically, for example, an ultraviolet LED, Organic EL, inorganic EL, ultraviolet laser, and mercury lamp, preferably at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser, irradiates ultraviolet rays to cause chlorine The vinyl resin is chlorinated.

<light source>

Next, the light source 9 will be described in detail. The present inventors have found that at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser is used, and it is more preferable to use an ultraviolet LED to introduce a chlorine-based vinyl chloride resin. suspension By irradiating ultraviolet rays and chlorinating the vinyl chloride resin, the chlorinated vinyl chloride resin can be obtained more efficiently. Further, it has been found that when the stirring property in the reaction tank or the irradiation range of the ultraviolet ray to the vinyl chloride resin is the same, at least one selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser is used. One type of light source is irradiated with ultraviolet rays, so that the total power consumption in the step of chlorinating the vinyl chloride resin is reduced, and the production cost can be reduced. Further, at least one type of light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser, in particular, an ultraviolet LED has a lower luminosity caused by long-term use than a mercury lamp. The number of times of replacement (replacement) of the light source is reduced, and the productivity of the chlorinated vinyl chloride resin is improved. Further, with respect to at least one kind of light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser, if the total amount of consumed electric power is the same, the reaction time can be made shorter than that of the mercury lamp. In the present invention, the total power consumption amount is when the current value of the light source is I (A), the voltage value of the light source is V (V), and the reaction time of chlorination is t (h). It is calculated by the following formula (1).

Total power consumption (W.h) = I × V × t × (number of light sources) (1)

The ultraviolet LED is not particularly limited as long as it is an LED that can emit ultraviolet light. For example, a semiconductor light-emitting element using a nitride semiconductor material such as AlN, AlGaN, or AlInGaN as a light-emitting layer, or a semiconductor light-emitting element using a diamond thin film as a light-emitting layer can be used as the ultraviolet LED. More preferably, an ultraviolet LED having a peak wavelength of one is used. Further, the peak wavelength of the ultraviolet ray irradiated by the ultraviolet ray LED can be adjusted by changing the ratio of each component of the luminescent layer. For example, when a nitride semiconductor material is used as the light-emitting layer of the ultraviolet LED, the peak wavelength of the ultraviolet light can be shortened by increasing the content of Al. In the ultraviolet irradiation, in addition to the ultraviolet LED, a light source such as an organic EL that can emit ultraviolet rays, an inorganic EL, and an ultraviolet laser can be used. Among them, it is preferred to use an ultraviolet LED as a light source. Further, it is more preferable that the light source such as the organic EL, the inorganic EL, and the ultraviolet laser emits ultraviolet rays having the same peak wavelength and/or wavelength range as the ultraviolet rays irradiated by the ultraviolet LED. Ultraviolet light The peak wavelength or wavelength range of the ultraviolet light irradiated by the LED is as follows.

The peak wavelength of the ultraviolet ray irradiated by the ultraviolet ray LED is preferably 290 nm or more and 400 nm or less from the viewpoint of suppressing initial coloration during heating molding and improving thermal stability. Further, from the viewpoint of the durability of the reaction vessel, the peak wavelength of the ultraviolet ray irradiated by the ultraviolet ray LED is preferably 340 nm or more and 400 nm or less. Further, ultraviolet rays having a peak wavelength of 315 nm or more and 400 nm or less are also referred to as UVA. In the present invention, an ultraviolet LED that emits ultraviolet rays having a peak wavelength of 365 nm or an ultraviolet LED that emits ultraviolet rays having a peak wavelength of 385 nm can be preferably used.

The wavelength range of the ultraviolet light to be irradiated by the ultraviolet LED is preferably 260 nm or more and 430 nm or less. In the present invention, the "wavelength range of ultraviolet rays" means a range of wavelengths of relative luminescence intensity having a relative luminescence intensity of 2% or more with respect to a peak wavelength in an luminescence spectrum. For example, in the ultraviolet light emission spectrum shown in FIG. 2, the wavelength range is from 350 nm to 392 nm, and in the ultraviolet light emission spectrum shown in FIG. 8, the wavelength range is from 355 nm to 415 nm.

Further, from the viewpoint of thermal stability, an ultraviolet LED having an irradiation wavelength of 300 nm or more and 430 nm or less and a peak wavelength of 350 nm or more and 400 nm or less is preferably used. Alternatively, from the viewpoint of high reaction efficiency of chlorination, an ultraviolet LED having an ultraviolet wavelength of 350 nm or more and 392 nm or less and a peak wavelength of 365 nm is preferably used. In the case where the chlorinated vinyl chloride resin having the same degree of chlorine content is used to produce a chlorinated vinyl chloride resin having the same degree of chlorine content, the reaction efficiency of the chlorination in the present invention can be evaluated by the total amount of light and/or the reaction time. . Therefore, the smaller the total amount of light necessary, and the shorter the reaction time, the higher the reaction efficiency of chlorination becomes.

In the present invention, the "total amount of light" is a value measured and calculated by the following method. A photosensor (manufactured by TOPCON, No. "UVR-2") is equipped with a sensor (No. UD-36, manufactured by TOPCON Co., Ltd.), and a vinyl chloride resin present in the reaction tank during the chlorination reaction. The distance from the light source becomes the closest position, and the light source is illuminated The amount of light per unit area of the ultraviolet light was measured. In addition, the distance between the vinyl chloride resin present in the reaction tank and the light source at the time of the chlorination reaction is the closest, and the ultraviolet ray irradiated from the light source is measured on the irradiation area of the vinyl chloride resin. Then, the value obtained by multiplying the value of the irradiation area obtained in the above measurement by the value of the light amount per unit area is defined as the total amount of light. For example, in the case of using a production apparatus shown in Fig. 1 as a reference example in the production of a chlorinated vinyl chloride resin, the amount of light per unit area and the irradiation area are measured at the position of the inner wall of the reactor 600, and In the production of the chlorinated vinyl chloride resin, when the manufacturing apparatus shown in Fig. 7 as a reference example is used, the amount of light per unit area is at the position of the outer wall of the cylindrical container 300b in which the ultraviolet LED light source device is inserted. The area of the irradiation was measured. Further, in the above measurement, the measurement of the amount of light per unit area and the irradiation area were carried out in an air atmosphere and the inside of the reactor was empty.

Here, the term "ultraviolet LED" means both an ultraviolet LED element and an ultraviolet LED light source device having a plurality of ultraviolet LED elements. Further, instead of using at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser, a mercury lamp may be used as a light source as needed.

The invention includes the following invention.

(1) A device for producing a chlorinated vinyl chloride resin, which is obtained by chlorinating a vinyl chloride resin by irradiation with ultraviolet rays to produce a chlorinated vinyl chloride resin, and is provided with a vinyl chloride resin. a reaction tank with chlorine and a light source provided outside the reaction tank, wherein the reaction tank includes an ultraviolet light introduction unit that introduces ultraviolet light irradiated from the light source into the reaction tank, and the ultraviolet light introduction unit has an ultraviolet light emitting unit that irradiates the reaction chamber with ultraviolet rays. .

(2) The apparatus for producing a chlorinated vinyl chloride resin according to (1), wherein the vinyl chloride resin is a suspension.

(3) The apparatus for producing a chlorinated vinyl chloride resin according to (1) or (2), wherein the reaction vessel has a pressure resistant structure.

(4) The apparatus for producing a chlorinated vinyl chloride resin according to (3), wherein the reaction tank has The internal pressure can be set to an intensity of 0.02 to 2.00 MPa.

(5) The apparatus for producing a chlorinated vinyl chloride resin according to any one of (1) to (4), wherein the reaction vessel is provided with a stirring blade, and the ultraviolet emitting portion is disposed in a rotation of the stirring blade in the reaction vessel. Areas outside the area.

(6) The apparatus for producing a chlorinated vinyl chloride resin according to any one of (1) to (5) wherein the light source is selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser. At least 1 light source.

(7) The apparatus for producing a chlorinated vinyl chloride resin according to any one of (1) to (6) wherein the ultraviolet emitting portion is an optical fiber.

(8) The apparatus for producing a chlorinated vinyl chloride resin according to any one of (1) to (7), comprising a plurality of the ultraviolet ray emitting portions.

(9) A method for producing a chlorinated vinyl chloride-based resin, comprising the step of irradiating ultraviolet rays emitted from a chlorine-containing resin introduced into the inside of the reaction vessel.

(10) The method for producing a chlorinated vinyl chloride resin according to (9), wherein the vinyl chloride resin is a suspension.

(11) The method for producing a chlorinated vinyl chloride resin according to (9) or (10), which has an introduction step of introducing chlorine into the vinyl chloride resin in the reaction vessel before the irradiation step.

(12) A method for producing a chlorinated vinyl chloride resin according to (11), wherein the inside of the reaction tank is pressurized in the introducing step.

(13) A method for producing a chlorinated vinyl chloride resin according to (12), wherein the inside of the reaction vessel is pressurized to 0.02 to 2.00 MPa.

(14) The method for producing a chlorinated vinyl chloride resin according to any one of (9) to (13), wherein, in the above-mentioned irradiation step, it is selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser. At least one kind of light source in the group is irradiated with ultraviolet rays and supplied to the ultraviolet emitting portion.

(15) The method for producing a chlorinated vinyl chloride resin according to any one of (9) to (14) wherein the ultraviolet emitting portion is an optical fiber.

(16) The method for producing a chlorinated vinyl chloride resin according to any one of (9) to (15), wherein, in the irradiating step, a plurality of ultraviolet light emitting portions provided inside the reaction tank are introduced with chlorine The vinyl chloride resin is irradiated with ultraviolet rays.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the invention. The embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the present invention. Within the technical scope.

<Production of chlorinated vinyl chloride resin>

(Example 1)

As shown in Fig. 14, two cylindrical glass rods 10a each having a length of 600 mm and a diameter of 90 mm were inserted into the jacketed reactor 600c.

As shown in Fig. 15, the portion of the glass rod 10a which is disposed outside the range of 5 cm from the end of the inside of the reactor 600c is covered with metal. That is, only a part of the length 40 of the glass rod 10a in the entire length 50 of the glass rod is covered with metal. Further, the glass rod 10a has a structure in which light does not leak from a portion not covered with metal. Further, the cross section 60 of the glass rod 10a is a circle having a diameter of about 9 cm.

An optical fiber group 5b that functions as an ultraviolet light introducing unit is connected to an end of the glass rod 10a that is not disposed on the inner side of the reactor 600c.

The optical fiber group 5b connected to each of the two glass rods 10a is bundled into one bundle, and is connected to an ultraviolet light exit port 120 of one ultraviolet light source device 100c (UV-LED light source unit (manufactured by SENTEC Co., Ltd., model "OX223")). The ultraviolet LED light source device 100c has a structure in which ultraviolet light irradiated by all of the ultraviolet LEDs provided therein is irradiated from the ultraviolet light exit port 120 to the optical fiber group 5b.

The luminescence spectrum of the ultraviolet LED element used in Example 1 is as shown in FIG. As shown in Figure 2, the ultraviolet light irradiated by the ultraviolet LED element has a wavelength range of 350 nm. Up to 392 nm, the peak is one and the peak wavelength is 365 nm. Here, the wavelength range means a range of wavelengths of relative luminescence intensity having a relative luminescence intensity of 2% or more with respect to the peak wavelength in the luminescence spectrum.

Then, 10 kg of a vinyl chloride-based resin (manufactured by Kaneka Co., Ltd.) having 40 kg of pure water, a K value of 66.7, an average particle diameter of 170 μm, and an apparent density of 0.568 g/ml was placed in the reactor 600c, and the reactor was placed by a lid 620c. Sealed inside 600c. Further, the K value of the vinyl chloride resin is a value obtained in accordance with JIS-K7367-2, the average particle diameter is a value obtained in accordance with JIS-K0069, and the apparent density is a value obtained based on JIS-K7365 ( The same is true for the following values). Then, the turbine suspension 610b (180 mm in diameter) of the reactor 600c was used to stir the aqueous suspension 700c of the vinyl chloride resin as a mixture of pure water and vinyl chloride resin at a number of revolutions of 590 rpm.

After vacuum degassing and nitrogen substitution in the reactor 600c, vacuum degassing was performed again. Thereafter, chlorine gas is blown into the aqueous suspension 700c of the vinyl chloride resin. At the same time, while stirring the aqueous suspension 700c of the vinyl chloride resin by the turbine blade 610b, the ultraviolet LED light source device 100c is activated (output: 0.25 Amp for each glass rod 10a), and the reactor is passed through the optical fiber group 5b and the glass rod 10a. The aqueous suspension 700c in 600c is irradiated with ultraviolet rays to start the chlorination reaction.

The temperature in the reactor 600c is raised by heating for 25 minutes to 50 ° C after the start of nitrogen substitution, and the chlorination reaction is started (onset of ultraviolet irradiation) and then heated for 100 minutes to 85 ° C, followed by chlorination (in ultraviolet irradiation). The system was maintained at 85 °C.

Further, the pressure inside the reactor 600c in the chlorination reaction was set to 0.02 MPa.

When the chlorine content of the chlorinated vinyl chloride resin reaches 67.1%, the ultraviolet ray irradiation by the glass rod 10a is completed, and the chlorination reaction is completed. The chlorine content of the chlorinated vinyl chloride resin is calculated based on the neutralization titration value of the hydrochloric acid produced by the chlorination reaction (the same applies to the following values). The reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, from the start of ultraviolet irradiation until the end of irradiation The time is 144 minutes. Then, the unreacted chlorine in the chlorinated vinyl chloride resin is removed by nitrogen, and the residual hydrochloric acid is removed by washing with water, and then the chlorinated vinyl chloride resin is dried. Thereby, a chlorinated vinyl chloride resin was obtained.

(Example 2)

One of the two glass rods 10a shown in FIG. 14 is cut and connected to the optical fiber group 5b, and only one glass rod 10a is irradiated with ultraviolet rays for chlorination reaction, and other methods are implemented. In the same manner as in Example 1, a chlorinated vinyl chloride resin was obtained. The total output of the ultraviolet LED light source device 100c is also the same as in the first embodiment (output: 0.50 Amp for the glass rod 10a). In other words, in Example 2, ultraviolet rays having the same intensity as the ultraviolet rays irradiated by the two glass rods 10a in Example 1 were irradiated through one glass rod 10a.

Further, the pressure inside the reactor 600c in the chlorination reaction was set to 0.02 MPa.

In the second embodiment, the reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 162 minutes.

As is clear from the above Table 1, the greater the number of glass rods (in other words, the ultraviolet emitting portion), the shorter the reaction time of the chlorination reaction.

(Example 3)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.06 MPa.

In the third embodiment, the reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, from the start of ultraviolet irradiation to the irradiation of the junction The bundle time is 137 minutes.

(Example 4)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.10 MPa.

In the fourth embodiment, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 128 minutes.

(Example 5)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.12 MPa.

In Example 5, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 123 minutes.

(Example 6)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.14 MPa.

In the sixth embodiment, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 125 minutes.

(Comparative Example 4)

As shown in Fig. 16, one glass cylindrical container 300c was placed in a jacketed reactor 600d. In the same manner as in Example 1, water and a vinyl chloride resin were introduced into the reactor 600d, and the inside of the reactor 600d was sealed by a lid 620d. Then, using a turbine blade 610c (180 mm in diameter) of the reactor 600d, an aqueous suspension 700d of a vinyl chloride resin as a mixed liquid of pure water and a vinyl chloride resin was stirred at a number of revolutions of 590 rpm.

The inside of the reactor 600d was pressurized with chlorine to 0.02 MPa, and the cylindrical container was obtained. The 300c is broken, so it is difficult to judge the experiment.

(Comparative Example 5)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the reactor 600d with a sleeve in the chlorination reaction was changed to 0.01 MPa. In the comparative example, the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1% was 155 minutes.

As is clear from the data in Table 2 above, the higher the internal pressure of the reactor in the chlorination reaction, the shorter the reaction time of the chlorination reaction.

(Example 7)

The vinyl chloride resin used as a raw material was changed to a vinyl chloride resin (Kaneka Co., Ltd.) having a K value of 58.4, an average particle diameter of 150 μm, and an apparent density of 0.574 g/ml, and the reaction in the chlorination reaction was carried out. A chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the pressure inside the device 600c was set to 0.04 MPa.

In the eighth embodiment, the reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 140 minutes.

(Example 8)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 7 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.06 MPa.

In the ninth embodiment, the reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, from the start of ultraviolet irradiation to the irradiation of the junction The bundle time is 135 minutes.

(Example 9)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 7 except that the pressure inside the reactor 600c in the chlorination reaction was changed to 0.08 MPa.

In the tenth embodiment, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 128 minutes.

(Embodiment 10)

A chlorinated vinyl chloride resin was obtained in the same manner as in Example 7 except that the pressure inside the reactor 600c in the chlorination reaction was 0.02 MPa.

In the eleventh embodiment, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 153 minutes.

As is clear from the data in Table 3 above, the higher the internal pressure of the reactor in the chlorination reaction, the shorter the reaction time of the chlorination reaction.

[Reference example]

Here, instead of using a mercury lamp as a light source, at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser, specifically, a case where an ultraviolet LED is used as a light source is used. The effect of the case where the ultraviolet LED is used as the light source is represented by the reference example. In the following reference examples and comparative examples, "parts" and "%" are based on weight unless otherwise specified.

(Reference example 1)

<Production of chlorinated vinyl chloride resin>

As shown in FIG. 1, a UV-LED light source unit (manufactured by SENTEC Co., Ltd., model "OX223") was prepared as the ultraviolet LED light source device 100. The ultraviolet LED light source device 100 has three ultraviolet LED elements 110 having a peak wavelength of 365 nm (manufactured by Nichia Chemical Industry Co., Ltd., model number "NC4U133", forward current 500 mA, forward voltage 14.9 V).

The luminescence spectrum of the ultraviolet LED element used in Reference Example 1 is as shown in FIG. As shown in FIG. 2, the ultraviolet light irradiated by the ultraviolet LED element 110 has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm. Here, the wavelength range is as described above, and means a range of wavelengths of relative luminescence intensity having a relative luminescence intensity of 2% or more with respect to the peak wavelength in the luminescence spectrum.

After the ultraviolet LED light source device 100 is placed in an aluminum support body 200 having a length of 20 mm, a width of 20 mm, and a height of 300 mm, a cylindrical container 300 made of transparent glass having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm is inserted (PYREX (registered trademark) ))in.

In the water bath 500 containing the warm water 400 of 60 ° C, the ultraviolet LED light source device 100 incorporated in the cylindrical container 300 and the container made of transparent glass having a thickness of 3.6 mm, that is, the reactor 600 (capacity 3 L, PYREX (registered trademark)). Specifically, the ultraviolet LED light source device 100 disposed in the water bath 500 is disposed in a state of being opposed to the reactor 600, and the three ultraviolet LED elements 110 are arranged in a row at a height of 15 mm at equal intervals. . At this time, the distance A between the reactor 600 and the ultraviolet LED element 110 was set to 80 mm. Further, a heat source (not shown) for maintaining the warm water 400 at a specific temperature is provided in the water bath 500.

Then, 1.8 kg of pure water and 0.2 kg of a vinyl chloride resin (manufactured by Kaneka Co., Ltd.) having a K value of 66.7, an average particle diameter of 170 μm, and an apparent density of 0.568 g/ml were placed in the reactor 600, and the lid 620 was used. The reactor 600 is sealed inside. Furthermore, vinyl chloride resin The K value is a value obtained in accordance with JIS-K7367-2, the average particle diameter is a value obtained in accordance with JIS-K0069, and the apparent density is a value obtained in accordance with JIS-K7365 (the same applies to the following values). Then, using the turbine blade 610 of the reactor 600, the aqueous suspension 700 of the vinyl chloride resin as a mixed liquid of pure water and a vinyl chloride resin was stirred at a number of revolutions of 340 rpm.

The inside of the reactor 600 was subjected to vacuum degassing and nitrogen replacement. Thereafter, chlorine gas is blown into the aqueous suspension 700 of the vinyl chloride resin. At the same time, while the aqueous suspension 700 of the vinyl chloride resin is stirred by the turbine blade 610, the aqueous suspension 700 of the vinyl chloride resin is irradiated with ultraviolet rays by the ultraviolet LED element 110 to start the chlorination reaction. Further, when blowing chlorine gas, care should be taken not to depressurize the inside of the reactor 600. In the chlorination reaction, the temperature of the warm water 400 in the water bath 500 was maintained at 60 °C.

When the chlorine content of the chlorinated vinyl chloride resin reaches 66.3%, the ultraviolet irradiation by the ultraviolet LED element 110 is completed, and the chlorination reaction is completed. The chlorine content of the chlorinated vinyl chloride resin is calculated based on the neutralization titration value of the hydrochloric acid produced by the chlorination reaction (the same values are also used for the following). The reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 66.3%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 96 minutes. Then, the unreacted chlorine in the chlorinated vinyl chloride resin is removed by nitrogen, and the residual hydrochloric acid is removed by washing with water, and then the chlorinated vinyl chloride resin is dried. Thereby, a chlorinated vinyl chloride resin was obtained.

(Comparative Example 1)

One 100W high-pressure mercury lamp (manufactured by Toshiba Lighting & Technology Co., Ltd., current value: 1.3A, voltage value: 100V) was used instead of one ultraviolet LED light source device 100 supported by the support 200, and the reference example 1 was used. In the same manner, a chlorinated vinyl chloride resin was obtained.

In Comparative Example 1, the reaction time of the chlorination reaction as the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 66.3%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 120 minutes.

The initial coloring and thermal stability measurement and evaluation at the time of heat molding of the chlorinated vinyl chloride resin obtained in Reference Example 1 and Comparative Example 1 were carried out in the following manner. Further, the Vickers softening point was measured and evaluated in the following manner, whereby the heat resistance was measured and evaluated.

<Initial coloring at the time of heat forming>

10 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B31") was added to 100 parts by weight of a chlorinated vinyl chloride resin. 1 part by weight, a powdery tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8813"), 1 part by weight, of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8831") 1 part by weight of stearic acid (manufactured by Kao Co., Ltd., model "Lunac (registered trademark) S-90V)) as a lubricant, and polyethylene wax (manufactured by Mitsui Chemicals Co., Ltd., model "Hiwax220MP") 0.3 weight After the portion, the mixture was kneaded at 195 ° C for 5 minutes using a 8 inch roll to prepare a sheet having a thickness of 0.6 mm.

The sheet obtained by laminating 15 sheets was sandwiched between iron plates which were chrome-plated and mirror-polished, and the pressure was adjusted to 3 MPa to 5 MPa at 200 ° C for 10 minutes. And make a plate with a thickness of 5 mm. The yellowing index (hereinafter also referred to as "YI") of the obtained plate was measured in accordance with JIS-K7373 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model "ZE-2000").

<thermal stability>

10 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B31") was added to 100 parts by weight of a chlorinated vinyl chloride resin. 1 part by weight, a powdery tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8813"), 1 part by weight, of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8831") 1 part by weight of stearic acid (manufactured by Kao Co., Ltd., model "Lunac (registered trademark) S-90V)) and polyethylene wax (manufactured by Mitsui Chemicals, Inc., model number) After 0.3 parts by weight of "Hiwax 220MP"), the sheet was kneaded at 195 ° C for 5 minutes using an 8-inch roll to prepare a sheet having a thickness of 0.6 mm.

The obtained sheet was cut into a length of 3 cm and a width of 5 cm, and heated in an oven at 200 ° C, and the time until the blackening of the sheet was measured was measured. The term "blackening" means that the sheet has an L value of 20 or less. The L value was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model "ZE-2000").

<Vicat softening point>

10 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B31") was added to 100 parts by weight of a chlorinated vinyl chloride resin. 1 part by weight, a powdery tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8813"), 1 part by weight, of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "TVS #8831") 1 part by weight of stearic acid (manufactured by Kao Co., Ltd., model "Lunac (registered trademark) S-90V)) as a lubricant, and polyethylene wax (manufactured by Mitsui Chemicals Co., Ltd., model "Hiwax220MP") 0.3 weight After the portion, the mixture was kneaded at 195 ° C for 5 minutes using a 8 inch roll to prepare a sheet having a thickness of 0.6 mm.

The sheet obtained by laminating 15 sheets is sandwiched between iron plates which are chrome-plated and mirror-polished, and then the pressure is adjusted to a range of 3 MPa to 5 MPa at 200 ° C for 10 minutes. And make a plate with a thickness of 5 mm. Using the obtained plate, the Vickers softening point (Vicat softening point) of the chlorinated vinyl chloride resin was measured in accordance with JIS-K7206. Here, the load was set to 5 kg, and the temperature increase rate was set to 50 ° C / h (B50 method).

As a result of the above measurement, the chlorinated vinyl chloride resin obtained in Reference Example 1 had a YI of 136, a time required for blackening was 40 minutes, and a Vickers softening point was 112.3 °C. On the other hand, the chlorinated vinyl chloride resin obtained in Comparative Example 1 had a YI of 142, a time required for blackening was 30 minutes, and a Vickers softening point was 111.6 °C. These results are shown together in Table 4 below.

As is clear from the data in Table 4, the chlorinated vinyl chloride resin obtained in Reference Example 1 has a lower YI than the chlorinated vinyl chloride resin obtained in Comparative Example 1, and therefore the initial coloration at the time of heat forming. The properties are good, and the time required for blackening is long, so the thermal stability is also good. Further, the chlorinated vinyl chloride resin obtained in Reference Example 1 had a higher Vickers softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 1, and thus the heat resistance was also good. In the case of producing a chlorinated vinyl chloride resin having the same chlorine content, the reference example 1 in which ultraviolet light is irradiated using an ultraviolet LED is compared with the comparative example 1 in which ultraviolet irradiation is performed using a mercury lamp, and the total amount necessary for the chlorination reaction is required. The amount of power consumed is significantly less, and there is an energy saving effect and a reduction in cost.

(Reference example 2)

<Production of chlorinated vinyl chloride resin>

As shown in FIG. 3, a UV-LED light source unit (manufactured by SENTEC Co., Ltd., model "OX224") was prepared as the ultraviolet LED light source device 100a. The ultraviolet LED light source device 100a has 12 ultraviolet LED elements 110a (manufactured by Nichia Chemical Industry Co., Ltd., model number "NC4U133", forward current 500 mA, forward voltage 14.9 V), which emits ultraviolet light having a peak wavelength of 365 nm. Further, the luminescence spectrum of the ultraviolet LED element used in Reference Example 2 is as shown in FIG.

As shown in Fig. 3, the ultraviolet LED light source device 100a is placed so as to be supported by the support 200a, and then inserted into a cylindrical container 300a made of transparent glass having an inner diameter of 74 mm, a height of 600 mm, and a thickness of 7 mm (PYREX (registered trademark)) )in.

As shown in FIGS. 4 and 5, one ultraviolet light source device 100a incorporated in the cylindrical container 300a is placed in a jacketed reactor 600a (capacity: 100 L). Specifically, the ultraviolet LED light source device 100a is disposed such that the distance between the center of the cylindrical reactor 600a and the center of the cylindrical container 300a in plan view, that is, the B indicated by the one-dot chain line in FIG. The length becomes 210mm. At this time, the twelve ultraviolet LED elements 110a are arranged in a row in the height direction at intervals of 15 mm. Further, the ultraviolet LED element 110a disposed at the lowest position is at a position of 132 mm from the bottom surface of the reactor 600a. Then, the ultraviolet LED element 110a is disposed such that the direction in which the ultraviolet light is irradiated is directed toward the flow direction of the stirring (the direction of the arrow C in FIG. 5).

Then, 45 kg of pure water and 5 kg of a vinyl chloride resin (manufactured by Kaneka Co., Ltd.) having a K value of 57.1, an average particle diameter of 125 μm, and an apparent density of 0.496 g/ml were placed in the reactor 600a, and the lid was closed with a lid 620a. The inside of the device 600a is sealed. Then, using the turbine blade 610a (180 mm in diameter) of the reactor 600a, the aqueous suspension 700a of the vinyl chloride resin which is a mixed liquid of pure water and a vinyl chloride resin was stirred at a number of revolutions of 590 rpm.

After the inside of the reactor 600a was subjected to vacuum degassing and nitrogen substitution, vacuum degassing was again performed. Then, chlorine gas is blown into the aqueous suspension 700a of the vinyl chloride resin. At the same time, the aqueous suspension 700a of the vinyl chloride resin is stirred by the turbine blade 610a, and the aqueous suspension 700a of the vinyl chloride resin is irradiated with ultraviolet rays by the ultraviolet LED element 110a to start the chlorination reaction. The temperature in the reactor 600a was raised to 50 ° C for 25 minutes after the start of the nitrogen substitution, and the chlorination reaction was started (after the start of the ultraviolet irradiation), and then cooled to 40 ° C for 15 minutes, followed by the chlorination reaction (in the ultraviolet irradiation). The system is maintained at 40 °C.

When the chlorine content of the chlorinated vinyl chloride resin reaches 64.4%, the ultraviolet irradiation by the ultraviolet LED element 110a is completed, and the chlorination reaction is completed. Chlorinated vinyl chloride The reaction time of the chlorination reaction, which is the time required for the chlorine content of the resin to reach 64.4%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 147 minutes. Then, the unreacted chlorine in the chlorinated vinyl chloride resin is removed by nitrogen, and the residual hydrochloric acid is removed by washing with water to dry the chlorinated vinyl chloride resin. Thereby, a chlorinated vinyl chloride resin was obtained.

(Comparative Example 2)

One 100W high-pressure mercury lamp (manufactured by Sunenergy Co., Ltd., model "SEH1002J01", forward current 1.1±0.1A, forward voltage 110±10V) is used instead of one ultraviolet LED light source device 100a supported by the support 200a. Otherwise, a chlorinated vinyl chloride resin was obtained in the same manner as in Reference Example 2.

In Comparative Example 2, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 64.4%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 234 minutes.

The measurement and evaluation of the initial coloration, thermal stability, and heat resistance (Vickers softening point) at the time of heat molding of the chlorinated vinyl chloride resin obtained in Reference Example 2 and Comparative Example 2 were carried out in the following manner.

<Initial coloring at the time of heat forming>

5 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B11A)) was added to 100 parts by weight of a chlorinated vinyl chloride resin. 3 parts by weight of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "N2000C"), 1 part by weight of PMMA resin (Kaneka Co., Ltd., model "Kanes (registered trademark) PA-20"), compound lubrication One part by weight of a solvent (manufactured by Kawaken Fine Chemicals Co., Ltd., model "VLTN-4") was kneaded at 180 ° C for 3 minutes using an 8-inch roll to prepare a sheet having a thickness of 0.6 mm.

The sheet obtained by laminating 15 sheets was sandwiched between iron plates which were chrome-plated and mirror-polished, and then the pressure was adjusted to a range of 3 MPa to 5 MPa at 190 ° C for 10 minutes. And make a plate with a thickness of 5 mm. Using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model "ZE-2000"), the YI of the obtained board was measured in accordance with JIS-K7373.

<thermal stability>

5 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B11A)) was added to 100 parts by weight of a chlorinated vinyl chloride resin. 3 parts by weight of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "N2000C"), 1 part by weight of PMMA resin (Kaneka Co., Ltd., model "Kanes (registered trademark) PA-20"), compound lubrication One part by weight of a solvent (manufactured by Kawaken Fine Chemicals Co., Ltd., model "VLTN-4") was kneaded at 180 ° C for 3 minutes using an 8-inch roll to prepare a sheet having a thickness of 0.6 mm. The obtained sheet was cut into a length of 3 cm and a width of 3.5 cm, and heated in an oven at 200 ° C, and the time until the blackening of the sheet was measured was measured. The term "blackening" means that the sheet has an L value of 20 or less. The L value was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., model "ZE-2000").

<Vickers softening point>

5 parts by weight of a methyl methacrylate-butadiene-styrene (MBS) resin (Kaneka Co., Ltd., model "Kanes (registered trademark) B11A)) was added to 100 parts by weight of a chlorinated vinyl chloride resin. 3 parts by weight of a tin-based stabilizer (manufactured by Nitto Chemical Co., Ltd., model "N2000C"), 1 part by weight of PMMA resin (Kaneka Co., Ltd., model "Kanes (registered trademark) PA-20"), compound lubrication One part by weight of a solvent (manufactured by Kawaken Fine Chemicals Co., Ltd., model "VLTN-4") was kneaded at 180 ° C for 3 minutes using an 8-inch roll to prepare a sheet having a thickness of 0.6 mm. The sheet obtained by laminating 15 sheets is sandwiched between iron plates which are chrome-plated and mirror-polished, and then the pressure is adjusted to a range of 3 MPa to 5 MPa at 200 ° C for 10 minutes. And make a plate with a thickness of 5 mm. Using the obtained plate, the Vickers softening point of the chlorinated vinyl chloride resin was measured in accordance with JIS-K7206. Among them, the load will be It was set to 5 kg, and the temperature increase rate was set to 50 ° C / h (B50 method).

As a result of the above measurement, the chlorinated vinyl chloride resin obtained in Reference Example 2 had a YI of 77.6, a blackening time of 80 minutes, and a Vickers softening point of 98.6 °C. The chlorinated vinyl chloride resin obtained in Comparative Example 2 had a YI of 87.1, a time required for blackening of 70 minutes, and a Vickers softening point of 97.2 °C. These results are shown together in Table 5 below.

As is clear from the information in Table 5, the chlorinated vinyl chloride resin obtained in Reference Example 2 has a lower YI than the chlorinated vinyl chloride resin obtained in Comparative Example 2, and thus the initial coloration at the time of heat forming. Good sex, because the time required for blackening is longer, so the thermal stability is also good. Further, the chlorinated vinyl chloride resin obtained in Reference Example 2 had a higher Vickers softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 2, and therefore had good heat resistance. In the case of producing a chlorinated vinyl chloride resin having the same chlorine content, the total power consumption required for the chlorination reaction is higher than that of Comparative Example 2 in which ultraviolet light is irradiated using ultraviolet LEDs and Comparative Example 2 in which ultraviolet light is irradiated using a mercury lamp. The amount is significantly less, but it has the effect of saving energy and reducing costs.

(Reference Example 3)

<Production of chlorinated vinyl chloride resin>

As shown in Fig. 6, prepare a UV-LED light source unit (manufactured by SENTEC Co., Ltd.) The model "OX558" is used as the ultraviolet LED light source device 100b. The ultraviolet LED light source device 100b has three ultraviolet LED elements 110b having a peak wavelength of 365 nm (manufactured by Nichia Corporation, model number "NC4U133A", forward current 500 mA, forward voltage 14.9 V).

The luminescence spectrum of the ultraviolet LED element used in Reference Example 3 is as shown in FIG. As shown in FIG. 2, the ultraviolet light irradiated by the ultraviolet LED element 110b has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm.

The ultraviolet LED light source device 100b was inserted into a cylindrical container 300b (PYREX (registered trademark)) made of transparent glass having an inner diameter of 25 mm, a height of 360 mm, and a thickness of 2.5 mm.

As shown in Fig. 7, a reactor 600b (capacity: 10 L, PYREX (registered trademark)) as a container made of transparent glass is placed in a water bath 500a containing warm water 400a at 25 ° C, and one unit is placed in a cylindrical shape. The ultraviolet LED light source device 100b in the container 300b is disposed in the reactor 600b. At this time, the three ultraviolet LED elements 110b are arranged in a row in the height direction at intervals of 15 mm. Further, the ultraviolet LED element 110b disposed at the lowest position is located 90 mm from the bottom surface of the reactor 600b. Then, the ultraviolet LED element 110b is disposed in a direction in which the direction in which the ultraviolet rays are irradiated and the direction in which the stirring flows. Further, a heat source (not shown) for maintaining the warm water 400a at a specific temperature is provided in the water bath 500a.

Then, 5.4 kg of pure water, 0.6 kg of a vinyl chloride resin (manufactured by Kaneka Co., Ltd.) having a K value of 66.7, an average particle diameter of 170 μm, and an apparent density of 0.568 g/ml were placed in the reactor 600b, and the lid 620b was placed thereon. The inside of the reactor 600b was sealed. Then, the aqueous suspension 700b of the vinyl chloride resin which is a mixed liquid of pure water and a vinyl chloride resin was stirred at 800 rpm using the turbine blade 610 of the reactor 600b.

After the inside of the reactor 600b was subjected to vacuum degassing and nitrogen substitution, chlorine gas was blown into the aqueous suspension 700b of the vinyl chloride resin. At the same time, the aqueous suspension 700b of the vinyl chloride resin is stirred by the turbine blade 610, and the aqueous suspension 700b is irradiated with ultraviolet rays by the ultraviolet LED element 110b to start the chlorination reaction. In addition, when blowing in chlorine, be careful not to The inside of the reactor 600b was decompressed. In the chlorination reaction, the warm water 400a in the water bath 500a was maintained at 70 °C.

When the chlorine content of the chlorinated vinyl chloride resin reaches 67.1%, the ultraviolet irradiation by the ultraviolet LED element 110b is completed, and the chlorination reaction is completed. The reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 120 minutes. Then, the unreacted chlorine in the chlorinated vinyl chloride resin is removed by nitrogen, and the residual hydrochloric acid is removed by washing with water, and then the chlorinated vinyl chloride resin is dried. Thereby, a chlorinated vinyl chloride resin was obtained.

(Reference example 4)

In the same manner as in Reference Example 3, chlorine chloride was obtained in the same manner as in Reference Example 3 except that the UV-LED light source unit 100b (manufactured by SENTEC Co., Ltd., model "OX559") was used as the ultraviolet light source device. Vinyl resin. The ultraviolet LED light source device has three ultraviolet LED elements having a peak wavelength of 385 nm (manufactured by Nichia Chemical Industry Co., Ltd., model "NC4U134A", forward current 500 mA, forward voltage 14.8 V).

The luminescence spectrum of the ultraviolet LED used in Reference Example 4 is as shown in FIG. As shown in FIG. 8, the ultraviolet light irradiated by the ultraviolet LED element has a wavelength range of 355 nm to 415 nm, one peak, and a peak wavelength of 385 nm. Here, the wavelength range is as described above, and means a range of wavelengths of relative luminescence intensity having a relative luminescence intensity of 2% or more with respect to the peak wavelength in the luminescence spectrum.

In Reference Example 4, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 135 minutes.

(Comparative Example 3)

Replace a UV LED light source with a 100W high pressure mercury lamp (manufactured by Toshiba Lighting & Technology Co., Ltd., forward current 1.3A, forward voltage 100V) A chlorinated vinyl chloride resin was obtained in the same manner as in Reference Example 3 except for the apparatus 100b.

In Comparative Example 3, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.1%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 93 minutes.

In the same manner as in Reference Example 1, the chlorinated vinyl chloride resin obtained in Reference Example 3, Reference Example 4, and Comparative Example 3 was subjected to initial coloring, thermal stability, and thermal stability during heating molding of a chlorinated vinyl chloride resin. Determination and evaluation of Vickers softening point.

As a result, the chlorinated vinyl chloride resin obtained in Reference Example 3 had a YI of 91.1, a time required for blackening of 60 minutes, and a Vickers softening point of 117.8 °C. The chlorinated vinyl chloride resin obtained in Reference Example 4 had a YI of 93.3, a time required for blackening of 50 minutes, and a Vickers softening point of 115.2 °C. The chlorinated vinyl chloride resin obtained in Comparative Example 3 had a YI of 132.3, a time required for blackening of 20 minutes, and a Vickers softening point of 114.3 °C. These results are shown together in Table 6 below.

Further, the total amount of light in Reference Example 3, Reference Example 4, and Comparative Example 3 was measured and calculated in the following manner. A sensor (a model "UD-36" manufactured by TOPCON Co., Ltd.) was installed in a light measuring device (model "UVR-2" manufactured by TOPCON Co., Ltd.), and a vinyl chloride resin present in the reactor during the chlorination reaction. The amount of light per unit area of the ultraviolet ray irradiated from the light source is measured at a position closest to the distance from the light source. In the chlorination reaction, the distance between the vinyl chloride resin and the light source in the reactor is the closest, and the irradiation area of the ultraviolet ray-treated resin irradiated with the ultraviolet ray is measured. The value obtained by multiplying the value of the irradiation area obtained in the above measurement by the value of the light amount per unit area is defined as the total amount of light. Further, in the above measurement, the measurement of the amount of light per unit area and the irradiation area were carried out in an air atmosphere and the inside of the reactor was empty. The results are shown in Table 6 below.

As is clear from the above Table 6, the chlorinated vinyl chloride resin obtained in Reference Example 3 and Reference Example 4 has a lower YI value than the chlorinated vinyl chloride resin obtained in Comparative Example 3, and thus is heated. The initial coloring property at the time of molding is good, and the time required for blackening is long, so that the thermal stability is also good. Further, the chlorinated vinyl chloride resin obtained in Reference Example 3 and Reference Example 4 had a higher Vickers softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 3, and therefore had good heat resistance. In the case of producing a chlorinated vinyl chloride resin having the same chlorine content, reference example 3 and reference example 4 in which ultraviolet light is irradiated using an ultraviolet LED are required for the chlorination reaction as compared with the comparative example 3 in which ultraviolet irradiation is performed using a mercury lamp. The total power consumption is significantly less, and there is an energy saving effect and a reduction in cost.

As can be seen from the data of Table 6, the initial coloring property at the time of heat molding can be obtained by referring to Reference Example 4 using an ultraviolet light having an ultraviolet ray having a peak wavelength of 365 nm, in Reference Example 4 using an ultraviolet light having an ultraviolet ray having a peak wavelength of 385 nm. A chlorinated vinyl chloride resin with improved thermal stability. In addition, when the chlorinated vinyl chloride resin having the same chlorine content is produced, the reference to the ultraviolet light LED using the ultraviolet light having a peak wavelength of 365 nm is used as a reference for the ultraviolet light having an ultraviolet ray having a peak wavelength of 365 nm. In Example 3, not only the total amount of light required but also the reaction time is shorter, and the reaction efficiency is shorter. Bureau.

(Reference example 5)

<Production of chlorinated vinyl chloride resin>

In the same manner as in Reference Example 3, the ultraviolet LED light source device 100b was used.

As shown in Fig. 9, the ultraviolet LED light source device 100b was inserted into a cylindrical container 300 (PYREX (registered trademark)) made of transparent glass having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm. Although not shown, in order to collect light, the periphery of the LED light source device 100b is surrounded by aluminum foil, and the front surface of the ultraviolet LED element 110b is cut to a length of 50 mm and a width of 50 mm, and light is not leaked from the outside of the portion.

As shown in Fig. 9, the ultraviolet LED light source device 100b incorporated in the cylindrical container 300 and the container made of transparent glass, that is, the reactor 600b (capacity 10 L, are placed in the water bath 500a containing the warm water 400a at 25 °C. PYREX (registered trademark)). Specifically, the ultraviolet LED light source device 100b disposed in the water bath 500a is disposed in a state of being opposed to the reactor 600b, and the three ultraviolet LED elements 110b are arranged in a row at a height of 15 mm. At this time, the distance A between the reactor 600b and the ultraviolet LED element 110b was set to 60 mm. Further, a heat source (not shown) for maintaining the warm water 400a at a specific temperature is provided in the water bath 500a.

Then, 5.4 kg of pure water, 0.6 kg of a vinyl chloride resin (manufactured by Kaneka Co., Ltd.) having a K value of 66.7, an average particle diameter of 170 μm, and an apparent density of 0.568 g/ml were placed in the reactor 600b, and the lid 620b was placed thereon. The inside of the reactor 600b was sealed. Then, the aqueous suspension 700b of the vinyl chloride resin which is a mixed liquid of pure water and a vinyl chloride resin was stirred at 800 rpm using the turbine blade 610 of the reactor 600b.

After the inside of the reactor 600b was subjected to vacuum degassing and nitrogen substitution, chlorine gas was blown into the aqueous suspension 700b of the vinyl chloride resin. At the same time, the aqueous suspension 700b of the vinyl chloride resin is stirred by the turbine blade 610, and the aqueous suspension 700b is irradiated with ultraviolet rays by the ultraviolet LED element 110b to start the chlorination reaction. In addition, when blowing in chlorine, be careful not to The inside of the reactor 600b was decompressed. In the chlorination reaction, the warm water 400a in the water bath 500a was maintained at 70 °C.

When the chlorine content of the chlorinated vinyl chloride resin reaches 67.2%, the ultraviolet irradiation by the ultraviolet LED element 110b is completed, and the chlorination reaction is completed. The reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 309 minutes. Then, the unreacted chlorine in the chlorinated vinyl chloride resin is removed by nitrogen, and the residual hydrochloric acid is removed by washing with water, and then the chlorinated vinyl chloride resin is dried. Thereby, a chlorinated vinyl chloride resin was obtained.

(Reference example 6)

A chlorinated vinyl chloride resin was obtained in the same manner as in Reference Example 5 except that one ultraviolet light source device similar to that of Reference Example 4 was used as the ultraviolet light source device.

In Reference Example 6, the reaction time of the chlorination reaction, which is the time required for the chlorine content of the chlorinated vinyl chloride resin to reach 67.2%, that is, the time from the start of the ultraviolet irradiation to the end of the irradiation was 300 minutes.

In the same manner as in Reference Example 1, the chlorinated vinyl chloride resin obtained in Reference Example 5 and Reference Example 6 was subjected to initial coloring, thermal stability, and Vickers softening at the time of thermoforming of a chlorinated vinyl chloride resin. Determination and evaluation of points.

As a result, the chlorinated vinyl chloride resin obtained in Reference Example 5 had a YI of 91.9, a time required for blackening was 90 minutes, and a Vickers softening point of 117.1 °C. The chlorinated vinyl chloride resin obtained in Reference Example 6 had a YI of 93.8, a time required for blackening of 90 minutes, and a Vickers softening point of 117.1 °C. These results are shown together in Table 7 below.

Further, in the same manner as in Reference Example 3, the total amount of light in Reference Example 5 and Reference Example 6 was measured and calculated. The results are shown in Table 7 below.

As can be seen from the data of Table 7, with reference to Example 6 using an ultraviolet LED having an ultraviolet ray having an irradiation peak wavelength of 385 nm, the initial coloring property at the time of heating molding can be obtained by using Reference Example 5 of an ultraviolet ray having an ultraviolet ray having a peak wavelength of 365 nm. It is a good chlorinated vinyl chloride resin. In addition, when the chlorinated vinyl chloride resin having the same chlorine content was produced, the reference example 6 using the ultraviolet ray having an ultraviolet ray having a peak wavelength of 385 nm was used as a reference for the ultraviolet ray having an ultraviolet ray having a peak wavelength of 365 nm. In Example 5, the reaction time was substantially the same as that of Reference Example 6, but the total amount of light required was approximately half of Reference Example 6, and the reaction efficiency was high. There is no difference between Reference Example 5 and Reference Example 6 in terms of total power consumption.

[Industrial availability]

According to the present invention, it is possible to produce a chlorinated vinyl chloride resin having an improved solubility in chlorine, for example, in a suspension of a vinyl chloride resin, for example, in the case of producing a chlorinated vinyl chloride resin. The chlorinated vinyl chloride resin obtained by the present invention not only has characteristics of high mechanical strength, weather resistance, chemical resistance, and the like of the vinyl chloride resin, but also has superior heat resistance to vinyl chloride resin, and thus can be applied. In various industrial fields. Specifically, the chlorinated vinyl chloride resin can be used for various purposes such as heat-resistant pipe, heat-resistant industrial board, heat-resistant film, and heat-resistant sheet.

1‧‧‧Reaction tank

2‧‧‧ casing

3‧‧‧Agitating wing

4‧‧‧Agitator shaft

5‧‧‧Fiber group (ultraviolet introduction unit)

5a‧‧‧Optical fiber (UV emission department)

6‧‧‧Lighting Department

7‧‧‧Aqueous suspension of vinyl chloride resin

8‧‧‧Supply tube

9‧‧‧Light source

20, 20a‧‧‧Support

Claims (16)

An apparatus for producing a chlorinated vinyl chloride resin, which is obtained by chlorinating a vinyl chloride resin by irradiation of ultraviolet rays to produce a chlorinated vinyl chloride resin, and comprising a vinyl chloride resin and chlorine. The reaction tank includes a light source provided outside the reaction tank, and the reaction tank includes an ultraviolet light introduction unit that introduces ultraviolet light irradiated from the light source into the reaction tank, and the ultraviolet light introduction unit includes an ultraviolet light emitting unit that irradiates the reaction chamber with ultraviolet rays. The apparatus for producing a chlorinated vinyl chloride resin according to claim 1, wherein the vinyl chloride resin is a suspension. The apparatus for producing a chlorinated vinyl chloride resin according to claim 1, wherein the reaction vessel has a pressure resistant structure. The apparatus for producing a chlorinated vinyl chloride resin according to claim 3, wherein the reaction vessel has a strength capable of setting the internal pressure to 0.02 to 2.00 MPa. The apparatus for producing a chlorinated vinyl chloride resin according to claim 1, wherein the reaction vessel includes a stirring blade, and the ultraviolet emitting portion is disposed in a region other than a rotation region of the stirring blade in the reaction vessel. The apparatus for producing a chlorinated vinyl chloride resin according to claim 1, wherein the light source is at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser. The apparatus for producing a chlorinated vinyl chloride resin according to claim 1, wherein the ultraviolet light emitting portion is an optical fiber. A device for producing a chlorinated vinyl chloride resin according to claim 1, which comprises a plurality of the above-mentioned ultraviolet light emitting portions. Method for producing chlorinated vinyl chloride resin, characterized by containing self-reaction tank The ultraviolet light emitting unit included in the interior is irradiated with ultraviolet rays by introducing a chlorine-based vinyl chloride resin. The method for producing a chlorinated vinyl chloride resin according to claim 9, wherein the vinyl chloride resin is a suspension. The method for producing a chlorinated vinyl chloride resin according to claim 9, comprising the step of introducing chlorine into the vinyl chloride resin in the reaction vessel before the irradiation step. The method for producing a chlorinated vinyl chloride resin according to claim 11, wherein the inside of the reaction vessel is pressurized in the introducing step. The method for producing a chlorinated vinyl chloride resin according to claim 12, wherein the inside of the reaction vessel is pressurized to 0.02 to 2.00 MPa. The method for producing a chlorinated vinyl chloride resin according to claim 9, wherein in the irradiating step, at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser is irradiated with ultraviolet rays and supplied In the above ultraviolet emitting portion. The method for producing a chlorinated vinyl chloride resin according to claim 9, wherein the ultraviolet light emitting portion is an optical fiber. The method for producing a chlorinated vinyl chloride resin according to claim 9, wherein in the irradiation step, ultraviolet rays are introduced from the plurality of ultraviolet light-emitting portions contained in the inside of the reaction tank to the chlorine-based resin into which chlorine is introduced.