WO2014178362A1 - Appareil et procédé de production de résine de chlorure de vinyle chlorée - Google Patents

Appareil et procédé de production de résine de chlorure de vinyle chlorée Download PDF

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Publication number
WO2014178362A1
WO2014178362A1 PCT/JP2014/061822 JP2014061822W WO2014178362A1 WO 2014178362 A1 WO2014178362 A1 WO 2014178362A1 JP 2014061822 W JP2014061822 W JP 2014061822W WO 2014178362 A1 WO2014178362 A1 WO 2014178362A1
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Prior art keywords
vinyl chloride
ultraviolet
chloride resin
suspension
pipe
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Ceased
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PCT/JP2014/061822
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English (en)
Japanese (ja)
Inventor
大知 小原
知昭 中川
裕啓 塩田
清史 堀内
武浩 中関
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Kaneka Corp
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Kaneka Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/18—Introducing halogen atoms or halogen-containing groups
    • C08F8/20—Halogenation
    • C08F8/22—Halogenation by reaction with free halogens
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/121—Coherent waves, e.g. laser beams
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/123—Ultraviolet light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
    • B01J19/122—Incoherent waves
    • B01J19/127—Sunlight; Visible light
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/28—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
    • B01J2219/0873—Materials to be treated
    • B01J2219/0881—Two or more materials
    • B01J2219/0884—Gas-liquid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the present invention relates to a manufacturing apparatus and a manufacturing method for a chlorinated vinyl chloride resin. More specifically, the present invention relates to a manufacturing apparatus and a manufacturing method for a chlorinated vinyl chloride resin using a photochlorination method.
  • the heat resistance temperature of the chlorinated vinyl chloride resin becomes higher than the heat resistance temperature of the vinyl chloride resin due to chlorination. Therefore, chlorinated vinyl chloride resins are used in various fields such as heat-resistant pipes, heat-resistant industrial plates, heat-resistant films and heat-resistant sheets.
  • a chlorinated vinyl chloride resin is produced by chlorinating a vinyl chloride resin while supplying chlorine to an aqueous suspension obtained by suspending vinyl chloride resin particles in an aqueous medium. It is common. Usually, when chlorination is performed by a photochlorination method, ultraviolet irradiation with a mercury lamp is performed to generate chlorine radicals (Patent Document 1).
  • Japanese Patent Publication Japanese Patent Laid-Open No. 10-279627 (published on Oct. 20, 1998)”
  • An apparatus for producing a chlorinated vinyl chloride resin of the present invention is an apparatus for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin by irradiating with ultraviolet rays in order to solve the above-mentioned problems.
  • a cross-sectional shape in the width direction of the glass pipe and / or the metal pipe having a glass window is an ellipse or a rectangle at least in the ultraviolet irradiation section.
  • the method for producing a chlorinated vinyl chloride resin of the present invention has a glass pipe and / or a glass window whose cross-sectional shape in the width direction, at least in the ultraviolet irradiation section, is elliptical or rectangular. It is characterized by having an irradiation step of irradiating the suspension with ultraviolet rays while circulating a suspension of vinyl chloride resin into which chlorine has been introduced into the metal pipe.
  • the reaction efficiency in producing the chlorinated vinyl chloride resin Has the effect of improving.
  • the cross-sectional shape at least in the ultraviolet irradiation section in the width direction of the glass pipe and / or the metal pipe having the glass window is an ellipse or a rectangle, the length of the inner diameter of the metal pipe having the glass pipe and / or the glass window
  • the ratio of the ultraviolet reach distance in the suspension to the thickness can be increased. If the above-mentioned ratio increases, the suspension (specifically, vinyl chloride resin in the suspension) can be more efficiently irradiated with ultraviolet rays. And as a result, the reaction efficiency at the time of manufacturing a chlorinated vinyl chloride-type resin can be improved.
  • FIG. 1 It is a sectional side view which shows typically the manufacturing apparatus of the chlorinated vinyl chloride-type resin containing the ultraviolet LED light source device and reactor which were used in Reference Example 1. It is a figure which shows an example of the emission spectrum of ultraviolet LED used by the reference example 1.
  • FIG. It is a sectional side view which shows typically the ultraviolet LED light source device used in the reference example 2.
  • FIG. It is a sectional side view which shows typically the manufacturing apparatus of the chlorinated vinyl chloride-type resin containing the ultraviolet LED light source device and reactor which were used in Reference Example 2.
  • It is a plane sectional view which shows typically the manufacturing apparatus of the chlorinated vinyl chloride-type resin containing the ultraviolet LED light source device and reactor which were used in Reference Example 2.
  • An apparatus for producing a chlorinated vinyl chloride resin according to the present invention is an apparatus for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin by irradiating with ultraviolet rays, wherein chlorine is introduced into the chloride.
  • the cross-sectional shape in the width direction of the glass pipe and / or the metal pipe having the glass window is an ellipse or a rectangle at least in the ultraviolet irradiation section.
  • the “width direction” refers to the direction in which the suspension flows in the metal pipe intersects (for example, the direction in which the suspension flows in the metal pipe). Intended to be perpendicular to each other).
  • the metal pipe having the glass pipe and / or the glass window, and the light source reach the ultraviolet ray in the suspension with respect to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window.
  • the distance ratio may be 30 to 100%.
  • the cross-sectional shape at least in the ultraviolet irradiation section in the width direction of the metal pipe having the glass pipe and / or the glass window, and the strength of the light source have the glass pipe and / or the glass window.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the length of the inner diameter of the metal pipe may be 30 to 100%.
  • chlorine is introduced into a glass pipe and / or a metal pipe having a glass window whose cross-sectional shape in the width direction, at least in the ultraviolet irradiation section, is elliptical or rectangular.
  • the ratio of the ultraviolet reach distance in the suspension to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window is 30 to 100%. It may be a step of irradiating the suspension with ultraviolet rays.
  • the chlorinated vinyl chloride resin produced in the present invention is obtained by irradiating a suspension of vinyl chloride resin into which chlorine has been introduced with ultraviolet rays, that is, using the photochlorination method. It is obtained by chlorinating.
  • the width of a glass pipe and / or a metal pipe having a glass window is an ellipse or a rectangle at least in the ultraviolet irradiation section.
  • the ultraviolet irradiation section of the present invention includes a region where the cross-sectional shape of the pipe 20 in the width direction is an ellipse (or a rectangle). That is, a region where the pipe 20 is thin is formed in the ultraviolet irradiation section of the present invention.
  • the configuration shown in FIG. 20A is merely an example, and details of each configuration will be described later.
  • the ultraviolet light emitted from the light source 19 is directed from the wall surface of the pipe 20 on the side irradiated with the ultraviolet light to another wall surface facing the wall surface.
  • the light source 19 is arranged in the thinned area of the pipe 20 described above, the section of the pipe 20 in the width direction of the area irradiated with ultraviolet rays with respect to the area of the area not irradiated with ultraviolet rays.
  • a cross section having a large area ratio can be formed. Specifically, in FIG.
  • the ratio of the area of the white portion (in other words, the region irradiated with ultraviolet rays) in the total area of the cross section in the width direction of the internal space of the pipe 20 is increased. be able to. If the ratio of the ultraviolet ray reaching distance in the suspension 12 is 30 to 100%, the above ratio can be further increased.
  • the cross-sectional shape of the pipe 20 in the width direction is a circle (or a regular polygon such as a square), an area where the pipe 20 is thin is not formed. Therefore, as compared with the case where the cross-sectional shape of the pipe 20 in the width direction is an ellipse (or a rectangle), the ultraviolet rays emitted from the light source 19 reach the inside of the pipe 20 shallower.
  • the ratio of the area of the white portion in other words, the region irradiated with ultraviolet rays
  • the ratio of the area of the white portion in other words, the region irradiated with ultraviolet rays
  • the entire amount of the suspension 12 is irradiated with ultraviolet rays as compared with the case where the cross-sectional shape of the pipe 20 in the width direction is an ellipse (or a rectangle).
  • the ratio of the amount of suspension is reduced.
  • the photochlorination reaction does not occur.
  • the suspension 12 passes through the vicinity of the center of the cross section (circle or regular polygon)
  • the suspension 12 is not irradiated with ultraviolet rays, and in the suspension 12, a photochlorination reaction is performed. Does not occur.
  • the cross-sectional shape in the width direction of the pipe 20 is a circle (or a regular polygon such as a square). And it can be said that the structure where the cross-sectional shape of the pipe 20 in the width direction is an ellipse (or a rectangle) is a more preferable structure.
  • a manufacturing apparatus 11 for a chlorinated vinyl chloride resin that can be used in the manufacturing method according to the present invention chlorinates a vinyl chloride resin by irradiating ultraviolet rays to chlorinate vinyl chloride resin.
  • a chlorine introduction part 1 for introducing chlorine gas Is a chlorine introduction tank 2 for introducing chlorine into a suspension 12 of vinyl chloride resin, and a suspension 12 into which chlorine is introduced.
  • the pressure of the slurry extraction part 3 for transferring the water from the chlorine introduction tank 2 to the reactor 6 having a glass pipe and / or a metal pipe having a glass window, and the pressure of the suspension 12 taken out from the chlorine introduction tank 2 are reduced.
  • Pressure reducing valve 4 reactor 6 for performing photochlorination reaction by irradiating the suspension 12 with ultraviolet light, slurry circulation for circulating the suspension 12 from the reactor 6 to the chlorine introduction tank 2 Line 7, chlorine was introduced
  • a stirring portion 9 for stirring the suspension 12 and a jacket portion 10 covering the chlorine introduction tank 2 are provided.
  • the chlorine introduction tank 2 may be a pressure-resistant container that can be sealed, and there are no particular limitations, and various reaction containers can be used, and the specific configuration is not limited.
  • a tank for producing a known chlorinated vinyl chloride resin can be suitably used.
  • a suspension 12 in which a vinyl chloride resin is dispersed is placed in the chlorine introduction tank 2, and is stirred by the stirring unit 9 disposed in the chlorine introduction tank 2.
  • Chlorine gas is supplied from the chlorine inlet 1 to the stirred suspension 12.
  • the stirring unit 9 disposed in the chlorine introduction tank 2 is not particularly limited, and a stirring blade or the like can be used.
  • the agitating blade may be an axial flow type such as a propeller blade or a wide flow type such as a paddle blade or a turbine blade.
  • the jacket portion 10 covering the chlorine introduction tank 2 is a member having a function of controlling the internal temperature of the chlorine introduction tank 2.
  • a cooling jacket for cooling the internal temperature of the reactor can be exemplified.
  • the internal temperature of the chlorine introduction tank 2 can be controlled by balancing the heat removal amount and the heat generation amount with the cooling jacket.
  • the manufacturing apparatus 11 includes a pressurizing unit (pressurizing means) for pressurizing the chlorine introduction tank 2.
  • a pressurizing unit pressurizing means
  • the inside of the chlorine introduction tank 2 can be pressurized.
  • the pressure in the chlorine introduction tank 2 is not particularly limited, but may be, for example, 0.02 to 2.00 MPa. More specifically, the pressure is preferably 0.05 to 2.00 MPa, more preferably 0.06 to 1.80 MPa, and more preferably 0.06 to 1.50 MPa.
  • the pressure is more preferably 0.08 to 1.20 MPa.
  • the pressure is more preferably from 0.10 to 1.00 MPa, and particularly preferably from 0.12 to 0.50 MPa. If the pressure is within the above range, the amount of dissolved chlorine can be improved.
  • the chlorine introduction tank 2 preferably has a strength that can withstand the pressure described above.
  • the chlorine introduction tank 2 preferably has a strength that allows the internal pressure to be set in the range of 0.02 to 2.00 MPa. More specifically, the chlorine introduction tank 2 preferably has a strength capable of setting the internal pressure in the range of 0.05 to 2.00 MPa, and the internal pressure is set in the range of 0.06 to 1.80 MPa. More preferably, it has a possible strength, more preferably it has a strength capable of setting the internal pressure in the range of 0.06 to 1.50 MPa, and the internal pressure is in the range of 0.08 to 1.20 MPa. More preferably, it has a strength that can be set.
  • the chlorine introduction tank 2 preferably has a strength capable of setting the internal pressure in the range of 0.10 to 1.00 MPa, and the internal pressure can be set in the range of 0.12 to 0.50 MPa. It is particularly preferable to have strength.
  • the suspension 12 supplied with chlorine is taken out from the slurry extraction section 3 provided at the bottom of the chlorine introduction tank 2 and passes through the pressure reducing valve 4 for reducing the pressure of the suspension 12. It is transferred to the reactor 6.
  • a slurry circulation pump 5 for example, ceramic, titanium palladium, or the like can be used.
  • the pump material is preferably a material satisfying resistance to wet chlorine and hydrogen chloride.
  • the suspension 12 introduced into the reactor 6 flows through a glass pipe and / or a metal pipe having a glass window, and is irradiated with ultraviolet rays from a light source to be chlorinated by a photochlorination reaction. Thereafter, the suspension 12 led out from the reactor 6 is returned to the chlorine introduction tank 2 via the slurry circulation line 7, the slurry circulation pump 5, and the check valve 8.
  • the chlorine in the suspension 12 is consumed in the reactor 6 by the photochlorination reaction. For this reason, it is preferable to supply chlorine gas from the chlorine inlet 15 to the suspension 12 taken out from the reactor 6. It is preferable that the chlorine introduction part 15 introduces chlorine gas into the suspension 12 before the suspension 12 taken out from the reactor 6 is returned to the chlorine introduction tank 2.
  • the chlorine introduction unit 15 prevents the inside of the slurry circulation line 7 from becoming a negative pressure with respect to the suspension 12 taken out from the reactor 6, in other words, the inside of the slurry circulation line 7 is set to a negative pressure or more. As such, it is preferable to supply chlorine gas.
  • the production apparatus 11 preferably includes a circulation part (circulation means) for circulating the suspension 12 irradiated with ultraviolet rays in the reactor 6 to the chlorine introduction tank 2, and the production according to the present invention.
  • a circulation part for circulating the suspension 12 irradiated with ultraviolet rays in the reactor 6 to the chlorine introduction tank 2, and the production according to the present invention.
  • the circulation unit include the slurry circulation line 7, the slurry circulation pump 5, the check valve 8, and the like. According to this configuration, the supply of chlorine and the chlorination by ultraviolet irradiation can be repeated, so that a chlorinated vinyl chloride resin can be easily produced.
  • FIG. 1 shows only one reactor 6 in FIG. 1, but the number of reactors 6 is not particularly limited, and a plurality of reactors 6 may be provided. When a plurality of reactors 6 are provided, the respective reactors 6 may be installed in series or in parallel. However, in consideration of reaction efficiency, it is preferable to install them in parallel.
  • the suspension 12 When the suspension 12 is circulated from the reactor 6 to the chlorine introduction tank 2, the suspension 12 is preferably circulated so as to be efficiently mixed inside the chlorine introduction tank 2.
  • the circulation part is preferably configured to introduce the suspension 12 into the gas phase part of the chlorine introduction tank 2 or the vicinity of the gas-liquid interface.
  • the suspension 12 when the suspension 12 is circulated from the reactor 6 to the chlorine introduction tank 2, the suspension 12 can be suspended at any location as long as the suspension 12 can be efficiently mixed inside the chlorine introduction tank 2.
  • the turbid liquid 12 may be circulated.
  • the suspension 12 that has passed through the reactor 6 may be discharged to a liquid receiving tank (not shown).
  • the reactor 6 is connected to the reactor 6 through a pipe 20 through which a suspension 12 of vinyl chloride resin into which chlorine has been introduced, a glass pipe, and / or the glass window. And at least one light source 19 for irradiating the suspension 12 with ultraviolet rays. That is, the said piping 20 and the light source 19 are accommodated in the reactor 6 of the manufacturing apparatus 11 shown in FIG.
  • the piping 20 can be vacuum degassed and replaced with nitrogen.
  • a temperature control jacket is provided in the section of the pipe 20 where the ultraviolet rays are not irradiated.
  • a suspension 12 of vinyl chloride resin into which chlorine has been introduced is continuously introduced into the pipe 20 through the chlorine introduction tank 2 (FIG. 1).
  • the number of the light sources 19 may be arbitrarily set according to the length of the pipe 20, the width of the pipe 20, and the like. From the viewpoint of efficiently irradiating the suspension 12 with ultraviolet rays, the number of light sources 19 is preferably plural.
  • positioning of the light source 19 is not specifically limited, It may be arrange
  • the plurality of light sources 19 are preferably arranged along the width direction of the pipe 20.
  • the light source 19 As a form of the light source 19, a surface light source or a point light source may be used. However, from the viewpoint of efficiently irradiating ultraviolet rays over the entire suspension 12, the surface light source may be used. preferable.
  • the surface light source 19 When the light source 19 is a surface light source, the surface light source may have a shape covering a part of the ultraviolet irradiation section or a shape covering the entire ultraviolet irradiation section. From the viewpoint of efficiently irradiating the entire suspension 12 with ultraviolet rays, the light source 19 is preferably a surface light source having a shape covering the entire ultraviolet irradiation section.
  • the cross-sectional shape of at least the ultraviolet irradiation section in the width direction of the pipe 20 is an ellipse or a rectangle.
  • the cross-sectional shape in the width direction of at least the ultraviolet irradiation section ⁇ of the pipe 20 is a section ⁇ that is not irradiated with ultraviolet light.
  • the shape is flat.
  • FIG. 2 shows a case where the cross-sectional shape of the pipe 20 in the width direction is an ellipse or a rectangle.
  • the white portion in the suspension 12 represents an area irradiated with ultraviolet rays (the same applies to FIGS. 3 to 5).
  • the cross-sectional shape in the width direction of the ultraviolet irradiation section ⁇ is an ellipse (or rectangle), and the length of the major axis (or long side) of the ellipse (or rectangle) is “L 1 ”, and the ellipse (or The length of the short axis (or short side) of the rectangle is “L 2 ”.
  • the cross-sectional shape in the width direction of the section ⁇ that is not irradiated with ultraviolet rays is also an ellipse (or rectangle), and the length of the major axis (or long side) of the ellipse (or rectangle) is “L 3 ”.
  • the length of the short axis (or short side) of (or a rectangle) is “L 4 ”.
  • the cross-sectional shape in the width direction of the ultraviolet irradiation section ⁇ is a flat shape as compared with the cross-sectional shape in the width direction of the section ⁇ that does not irradiate ultraviolet light”. 1 / L 2 > L 3 / L 4 ”(hereinafter referred to as relational expression A).
  • FIG. 2 is a cross-sectional view of the pipe 20 along the direction in which the pipe 20 extends.
  • the plurality of light sources 19 are arranged along the direction in which the pipe 20 extends (in other words, the length direction of the pipe 20). Therefore, in FIG. 2, for example, the suspension 12 moves from the left side of the drawing to the right side of the drawing or from the right side of the drawing to the left side of the drawing.
  • the “width direction” is intended to be a direction from the front of the paper to the back of the paper, or a direction from the back of the paper to the front of the paper.
  • the “region irradiated with ultraviolet rays” refers to a region irradiated with ultraviolet rays having a light amount per unit area of 1 ⁇ w / cm 2 or more.
  • the amount of ultraviolet light per unit area was measured by attaching a sensor (TOPCON, product number “UD-36”) to a light amount measuring device (TOPCON, product number “UVR-2”). Points to the value.
  • the “ultraviolet irradiation section” includes a region (irradiation region in the length direction) where the ultraviolet rays from the light source 19 are irradiated in the pipe 20, and both end portions in the length direction of the irradiation region. Is a section in the length direction including a region (non-irradiation region in the length direction) not included in the ultraviolet irradiation section ⁇ in the pipe 20. refers to ⁇ .
  • the section ⁇ where the ultraviolet rays are not irradiated is an area between the adjacent ultraviolet irradiation section ⁇ and the ultraviolet irradiation section ⁇ , and an end of the pipe 20.
  • the region between the ultraviolet irradiation section ⁇ and the inlet or outlet of the reactor 6, and when there is one ultraviolet irradiation section ⁇ , between the ultraviolet irradiation section ⁇ and the inlet or outlet of the reactor 6 in the pipe 20. Refers to the area.
  • the cross-sectional area in the width direction of the ultraviolet irradiation section ⁇ (the cross-sectional area of the portion through which the suspension 12 flows) is the cross-sectional area in the width direction of the section ⁇ where the ultraviolet light is not irradiated (the portion through which the suspension 12 flows).
  • the cross-sectional area may be the same as or smaller than the cross-sectional area in the width direction of the section ⁇ that is not irradiated with ultraviolet rays, but is preferably the same or smaller.
  • the pipe 20 has a cross-sectional shape in the width direction at least in the ultraviolet irradiation section ⁇ which is an ellipse as shown in FIG. 3 or a rectangle as shown in FIG.
  • the pipe 20 has a flat shape at least in the cross-sectional shape in the width direction of the ultraviolet irradiation section ⁇ as compared with the cross-sectional shape in the width direction of the section ⁇ in which the ultraviolet light is not irradiated.
  • the cross-sectional shape in the width direction of the section ⁇ that does not irradiate ultraviolet rays, which is a normal pipe portion, is a circle
  • the cross-sectional shape in the width direction of the ultraviolet irradiation section ⁇ is a flat shape (preferably an ellipse) Or rectangular).
  • the ratio of the major axis length (A) to the minor axis length (B) of the ellipse is not particularly limited. “A / B” only needs to be larger than 1, preferably 2 or more, more preferably 5 or more, more preferably 10 or more, more preferably 100 or more, and 1000 The above is most preferable.
  • the ratio of the long side length (C) to the short side length (D) of the rectangle is not particularly limited.
  • C / D only needs to be larger than 1, preferably 2 or more, more preferably 5 or more, more preferably 10 or more, and more preferably 100 or more. , 1000 or more is most preferable.
  • the suspension can be efficiently irradiated with ultraviolet rays, so that the reaction efficiency in producing the chlorinated vinyl chloride resin can be further improved.
  • the size of the cross-sectional area in the width direction of the ultraviolet irradiation section ⁇ is not particularly limited, in the present invention, at least the cross-sectional shape in the width direction of the glass pipe and / or metal pipe having a glass window is elliptical. Or since it is a rectangle, even if the cross-sectional area of the width direction of the ultraviolet irradiation section (alpha) is large, the irradiation efficiency of the ultraviolet-ray with respect to the suspension 12 of a vinyl chloride resin can be improved.
  • the reaction efficiency in producing the chlorinated vinyl chloride resin can be improved.
  • the light source 19 is a light source that irradiates ultraviolet rays, specifically, for example, ultraviolet LED, organic EL, inorganic EL, ultraviolet laser, and mercury lamp (mercury lamp), preferably ultraviolet LED, organic EL, inorganic EL, and ultraviolet light. There may be mentioned at least one light source selected from the group consisting of lasers.
  • the installation location of the light source 19 with respect to the pipe 20 is, for example, when the cross-sectional shape in the width direction in the ultraviolet irradiation section ⁇ of the pipe 20 is an ellipse, FIG. 3 (a), (b), (e), ( As shown in f), it may be installed so that ultraviolet rays are irradiated toward the minor axis direction in the pipe 20, and as shown in FIG. 3C, the ultraviolet rays are emitted toward the major axis direction in the pipe 20.
  • the pipe 20 may be installed so that ultraviolet rays are irradiated in directions other than the minor axis direction and the major axis direction.
  • the light source 19 may be installed so that the light source 19 is in contact with the pipe 20 as shown in FIG. 3A, or the light source 19 is installed away from the pipe 20 as shown in FIG. May be.
  • the light source 19 may be formed by a plurality of light sources, or a plurality of light sources 19 may be formed. In this case, the number of the light sources that form the light source 19 and the number of the light sources 19 are not limited.
  • the pipe 20 when the cross-sectional shape in the width direction in the ultraviolet irradiation section ⁇ of the pipe 20 is rectangular, as shown in FIGS. 4A, 4B, 4E, and 4F, the pipe 20 It may be installed so that ultraviolet rays are irradiated toward the short side direction in FIG. 4, or as shown in FIG. 4C, it may be installed so that ultraviolet rays are irradiated toward the long side direction in the pipe 20. Alternatively, as shown in FIG. 4D, the pipe 20 may be installed so that the ultraviolet rays are irradiated in a direction other than the short side direction and the long side direction.
  • the light source 19 may be installed so that the light source 19 is in contact with the pipe 20 as shown in FIG. 4A, or the light source 19 is installed away from the pipe 20 as shown in FIG. 4B. May be.
  • the light source 19 may be formed by a plurality of light sources, or a plurality of light sources 19 may be formed. In this case, the number of the light sources that form the light source 19 and the number of the light sources 19 are not limited.
  • the four corners are not necessarily formed at right angles, and have a certain curvature (R) in order to maintain the mechanical strength of the pipe 20. It may be formed in a curved shape.
  • the pipe 20 can be produced by, for example, alternately connecting a glass pipe corresponding to the ultraviolet irradiation section ⁇ and a metal pipe such as a titanium-palladium alloy corresponding to the section ⁇ not irradiated with ultraviolet light. Although it is good, it is not particularly limited, and it can be produced by various conventionally known methods. Furthermore, a method for producing a metal pipe having a glass window may be produced by, for example, cutting a part of a metal pipe such as titanium-palladium alloy and fitting the glass into the part, but is not particularly limited. However, it can be produced by various conventionally known methods.
  • the diameter of the flow portion of the suspension 12 in the cross section in the width direction of the ultraviolet irradiation section ⁇ , preferably the short diameter or short side of the flow portion of the suspension 12 is sufficient for the suspension 12 of the vinyl chloride resin.
  • the number of the light sources 19 arranged along the pipe 20 is not particularly limited as long as it is a number that can sufficiently irradiate the vinyl chloride resin suspension 12 with ultraviolet rays.
  • the “suspension circulation portion” refers to a region surrounded by the inner peripheral surface of the pipe 20.
  • the cross-sectional shape in the width direction is an ellipse as shown in FIGS. They may be arranged point-symmetrically or line-symmetrically with respect to the pipe 20, and as shown in FIGS. 5B and 5D, they are point-symmetrical or line-symmetrical with respect to the pipe 20 whose cross-sectional shape in the width direction is rectangular. You may arrange in.
  • FIG. 5 illustrates the case where the two light sources 19 are installed so that the pipe 20 is sandwiched in the width direction, but three or more light sources 19 may be installed so that the pipe 20 is sandwiched in the width direction.
  • a plurality of light sources 19 are arranged point-symmetrically or line-symmetrically with respect to the pipe 20 when viewed in the cross-section in the width direction of the pipe 20.
  • positions so that the piping 20 may be enclosed is included.
  • FIGS. 5D and 5E An example of the combination is shown in FIGS. 5D and 5E, but the combination in the present invention is not limited to the combination shown in FIGS. 5D and 5E.
  • the suspension 20 of the vinyl chloride resin is continuously supplied to the pipe 20 while the pipe 20 is connected to the suspension 12. Then, ultraviolet rays are irradiated from the light source 19 (irradiation step).
  • the suspension 12 is irradiated with ultraviolet rays from the light source 19 while circulating the suspension 12 of the vinyl chloride resin into which chlorine has been introduced. Thereby, chlorination reaction is started.
  • the temperature in the piping 20 is controlled by letting warm water pass through a jacket during an irradiation process.
  • the suspension 12 of the vinyl chloride resin is preferably an aqueous suspension.
  • the irradiation step it is more preferable to circulate the vinyl chloride resin suspension 12 and irradiate the suspension 12 with ultraviolet rays a plurality of times. Thereby, an ultraviolet-ray can be efficiently irradiated with a vinyl chloride resin.
  • the number of times the suspension 12 is circulated may be set as appropriate according to, for example, the number of the light sources 19, the thickness of the pipe 20, the chlorine content of the desired chlorinated vinyl chloride resin, and the like. It is not a thing.
  • the chlorination reaction proceeds and the chlorine content of the chlorinated vinyl chloride resin reaches a desired value, the irradiation of ultraviolet light from the light source 19 is terminated, and the chlorination reaction is terminated. Thereafter, for example, the suspension 12 containing the chlorinated vinyl chloride resin is taken out from the chlorine introduction tank 2 (FIG. 1), and after remaining unreacted chlorine in the chlorinated vinyl chloride resin is purged with nitrogen gas. The hydrochloric acid is removed by washing with water and dried (washing process, drying process). Thereby, a chlorinated vinyl chloride resin can be produced.
  • the inventors preferably use at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser, more preferably an ultraviolet LED to introduce chlorine into which chlorine has been introduced. It was found that a chlorinated vinyl chloride resin can be obtained more efficiently by irradiating a suspension of vinyl resin with ultraviolet rays and chlorinating the vinyl chloride resin. In addition, if the stirrability in the reaction tank and the UV irradiation range for the vinyl chloride resin are similar, at least one light source selected from the group consisting of UV LED, organic EL, inorganic EL, and UV laser is used.
  • the total power consumption in the step of chlorinating the vinyl chloride resin is reduced and the production cost can be reduced by irradiating with ultraviolet rays.
  • at least one kind of light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL and ultraviolet laser, particularly ultraviolet LED has less decrease in luminous intensity due to long-term use than mercury lamp, The number of renewals (replacements) can be reduced, and the productivity of the chlorinated vinyl chloride resin can be improved.
  • at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser can shorten the reaction time as compared with mercury lamps if the total power consumption is comparable. it can.
  • the total power consumption is expressed by the following formula (1), where I (A) is the current value of the light source, V (V) is the voltage value of the light source, and t (h) is the chlorination reaction time. ).
  • Ultraviolet LED should just be LED which can irradiate an ultraviolet-ray,
  • the structure is not specifically limited.
  • the ultraviolet LED a semiconductor light emitting device using a nitride semiconductor material such as AlN, AlGaN, or AlInGaN for a light emitting layer, or a semiconductor light emitting device using a diamond thin film for a light emitting layer, or the like is used. More preferably, an ultraviolet LED having a single peak wavelength is used. Moreover, the peak wavelength of the ultraviolet rays irradiated by the ultraviolet LED can be adjusted by changing the ratio of each composition of the light emitting layer.
  • the peak wavelength of the ultraviolet light can be shortened by increasing the Al content.
  • a light source such as an organic EL, an inorganic EL, and an ultraviolet laser that can irradiate the ultraviolet light can be used for the ultraviolet irradiation.
  • an ultraviolet LED it is preferable to use an ultraviolet LED as the light source.
  • a light source such as an organic EL, an inorganic EL, and an ultraviolet laser can irradiate ultraviolet rays having the same peak wavelength and / or wavelength range as the ultraviolet rays emitted from the ultraviolet LED.
  • the peak wavelengths and wavelength ranges of ultraviolet rays emitted by ultraviolet LEDs are as follows.
  • the peak wavelength of ultraviolet light emitted from the ultraviolet LED is preferably 290 nm or more and 400 nm or less from the viewpoint of suppressing initial coloring during heat molding and improving thermal stability. Moreover, it is preferable that the peak wavelength of the ultraviolet-ray which an ultraviolet LED irradiates is 340 nm or more and 400 nm or less from a viewpoint of durability of a reaction tank. Note that 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 light having a peak wavelength of 365 nm or an ultraviolet LED that emits ultraviolet light having a peak wavelength of 385 nm can be suitably used.
  • the wavelength range of ultraviolet rays emitted from the ultraviolet LED is preferably 260 nm or more and 430 nm or less.
  • the “ultraviolet wavelength range” means a wavelength range having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
  • the wavelength range is 350 nm to 392 nm
  • the wavelength range is 355 nm to 415 nm.
  • an ultraviolet LED that emits ultraviolet rays having a wavelength range of 300 nm or more and 430 nm or less and a peak wavelength of 350 nm or more and 400 nm or less.
  • an ultraviolet LED that emits ultraviolet rays having a wavelength range of 350 nm to 392 nm and a peak wavelength of 365 nm is preferable.
  • the reaction efficiency of chlorination in the present invention is the total amount of light and / or reaction time required when producing a chlorinated vinyl chloride resin having the same chlorine content using a vinyl chloride resin having the same composition. Can be evaluated. Therefore, the smaller the total amount of light required and the shorter the reaction time, the higher the chlorination reaction efficiency.
  • the “total light amount” is a value measured and calculated by the following method.
  • the light quantity per unit area of the ultraviolet rays emitted from the light source is measured at the position where the distance between the light source and the light source is closest.
  • the irradiation area where the ultraviolet ray irradiated from the light source hits the chlorinated vinyl resin is measured at the position where the distance between the vinyl chloride resin present in the reaction tank and the light source is the shortest.
  • a value obtained by multiplying the value of the irradiation area obtained by the above measurement with the value of the light amount per unit area is defined as the total light amount.
  • the production apparatus shown in FIG. 6 as a reference example is used for producing a chlorinated vinyl chloride resin
  • the light amount per unit area and the irradiation area are measured at the position of the inner wall of the reactor 600
  • chlorine when the manufacturing apparatus shown in FIG. 12 as a reference example is used for manufacturing the vinyl chloride resin, the light quantity per unit area and the irradiation area at the position of the outer wall of the cylindrical container 300b in which the ultraviolet LED light source device is inserted. Measure.
  • the measurement of the light amount per unit area and the irradiation area is performed in an air atmosphere and with the reactor inside empty.
  • ultraviolet LED refers to both an ultraviolet LED element and an ultraviolet LED light source device having a plurality of ultraviolet LED elements.
  • a mercury lamp (mercury lamp) may be used as a light source, if necessary.
  • the number of UV LEDs used for chlorination of vinyl chloride resin may be one or plural. In the case of using a plurality of ultraviolet LEDs, ultraviolet LEDs having the same peak wavelength of ultraviolet rays to be irradiated may be used in combination, or ultraviolet LEDs having different peak wavelengths of irradiated ultraviolet rays may be used in combination. Good.
  • the vinyl chloride resin used in the present invention is introduced into a reaction vessel (a glass pipe and / or a metal pipe having a glass window) as a suspension, more preferably 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 an aqueous medium and a vinyl chloride resin and water are mixed, an aqueous suspension of the vinyl chloride resin can be obtained.
  • the vinyl chloride resin used as a raw material for the chlorinated vinyl chloride resin is a vinyl chloride monomer homopolymer, or a copolymer of a vinyl chloride monomer and another copolymerizable monomer. It is. Although it does not specifically limit as another copolymerizable monomer, For example, ethylene, propylene, vinyl acetate, allyl chloride, allyl glycidyl ether, acrylic acid ester, vinyl ether etc. are mentioned.
  • a dispersant When the vinyl chloride monomer is homopolymerized, or when the vinyl chloride monomer is copolymerized with another copolymerizable monomer, a dispersant, an oil-soluble polymerization initiator, or the like can be used.
  • a polymerization regulator When performing the above polymerization, a polymerization regulator, a chain transfer agent, a pH regulator, an antistatic agent, a crosslinking agent, a stabilizer, a filler, an antioxidant, a scale inhibitor, and the like may be further used. .
  • Examples of the dispersant include partially saponified polyvinyl acetate, methyl cellulose, and hydroxypropyl methyl cellulose.
  • Examples of the oil-soluble polymerization initiator include lauroyl peroxide, di-2-ethylhexyl peroxyneodecanoate, t-butylperoxyneodecanoate, ⁇ , ⁇ ′-azobis-2,4-dimethylvaleronitrile. Etc.
  • the particle size of the vinyl chloride resin is not particularly limited, but the average particle size is preferably 0.1 to 350 ⁇ m, more preferably 80 to 200 ⁇ m. In the present invention, the average particle size of the vinyl chloride resin is measured according to 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 and water and suspending the vinyl chloride resin in water. .
  • the aqueous suspension of the vinyl chloride resin is preferably prepared in a mixing tank provided on the upstream side of these pipes before being introduced into the glass pipe and / or the metal pipe having the glass window. That is, the aqueous suspension of the vinyl chloride resin is preferably prepared in advance in a mixing tank and then introduced into a metal pipe having a glass pipe and / or a glass window.
  • the obtained aqueous suspension of the vinyl chloride resin is introduced into a reaction tank (a glass pipe and / or a metal pipe having a glass window), and a stirring blade disposed in the reaction tank or, if necessary, a glass pipe. And / or agitated by a static mixer placed in a metal pipe with a glass window. Chlorine is supplied to the aqueous suspension of the vinyl chloride resin in the mixing tank while stirring.
  • the aqueous suspension of the vinyl chloride resin in the mixing tank is introduced into a metal pipe having a glass pipe and / or a glass window while further supplying chlorine as necessary, and is irradiated with ultraviolet rays by an ultraviolet LED. By starting the irradiation of ultraviolet rays from the ultraviolet LED, the chlorination reaction of the vinyl chloride resin starts.
  • the vinyl chloride resin in the aqueous suspension is chlorinated until the desired chlorine content is reached.
  • the chlorination reaction is terminated by terminating the irradiation with ultraviolet rays.
  • unreacted chlorine in the chlorinated vinyl chloride resin is purged with nitrogen gas or the like, and further, hot water having a temperature lower than Tg (glass transition temperature) of the chlorinated vinyl chloride resin is used.
  • Tg glass transition temperature
  • the concentration of the vinyl chloride resin in the aqueous suspension depends on the molecular weight of the vinyl chloride resin. It is preferably 10% by weight or more and 40% by weight or less, and more preferably 20% by weight or more and 35% by weight or less.
  • chlorine When supplying chlorine to the mixing tank, chlorine may be either gaseous or liquid, but is more preferably gaseous from the viewpoint of ease of handling.
  • the method for supplying chlorine is not particularly limited as long as it can supply chlorine into the aqueous suspension.
  • chlorine supply methods include a method of supplying chlorine in a lump before the start of the chlorination reaction (initial stage), a method of supplying chlorine intermittently during the chlorination reaction, and a continuous supply of chlorine during the chlorination reaction.
  • the mixing tank may be configured to be supplied with powdered or particulate vinyl chloride resin, water, and chlorine.
  • aqueous suspension of a vinyl chloride resin into which chlorine is introduced into a reaction vessel exists at the time of irradiation with ultraviolet rays. Therefore, the method for supplying the aqueous suspension and chlorine is not particularly limited.
  • the chlorination reaction is started by starting the irradiation of ultraviolet rays, and is ended by ending the irradiation of ultraviolet rays.
  • the maximum reaction temperature during the chlorination reaction is not particularly limited, but is preferably 90 ° C. or lower, more preferably 88 ° C. or lower, and further preferably 86 ° C. or lower. When the maximum reaction temperature is 90 ° C. or lower, deterioration of the vinyl chloride resin is suppressed and coloring of the obtained chlorinated vinyl chloride resin is suppressed.
  • the minimum reaction temperature during the chlorination reaction is preferably more than 0 ° C. from the viewpoint of facilitating the flow of the aqueous suspension in the glass pipe and / or metal pipe having a glass window. In addition, the minimum reaction temperature is preferably 30 ° C. or higher, more preferably 50 ° C. or higher, from the viewpoint of shortening the reaction time.
  • this invention is not limited to the irradiation process demonstrated below and the metal piping which has a glass piping and / or a glass window.
  • the irradiation process demonstrated below and the structure of metal piping which has glass piping and / or a glass window are combined with the irradiation process already demonstrated and the structure of metal piping which has glass piping and / or a glass window. Is also possible.
  • the irradiation step is such that the ratio of the ultraviolet ray reaching distance in the suspension to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window is 30 to 100%. It may be a step of irradiating the liquid with ultraviolet rays.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window is more preferably 40 to 100%, and further preferably 50 to 100%. 60 to 100% is more preferable, 70 to 100% is further preferable, 80 to 100% is further preferable, and 90 to 100% is most preferable.
  • the cross-sectional shape in the width direction of the metal pipe having the glass pipe and / or the glass window at least in the ultraviolet irradiation section is an ellipse or a rectangle, the inner diameter of the metal pipe having the glass pipe and / or the glass window can be easily obtained.
  • the ratio of the ultraviolet reach distance in the suspension to the length of can be adjusted to the above-mentioned range.
  • FIG. 15 is a schematic cross-sectional view showing a main part of a chlorinated vinyl chloride resin production apparatus which is a reference example of the present invention
  • FIG. FIGS. 15B to 15E are sectional views of the pipe 20 in the width direction.
  • FIGS. 16 and 17 are schematic cross-sectional views showing the main part of the chlorinated vinyl chloride resin production apparatus according to the present invention.
  • FIGS. It is sectional drawing of the width direction.
  • the suspension 12 of vinyl chloride resin into which chlorine has been introduced circulates in the pipe 20.
  • the light source 19 is disposed to face the pipe 20.
  • the white portions in the suspension 12 represent regions irradiated with ultraviolet rays (hereinafter referred to as “ultraviolet irradiation regions 22”).
  • the “ultraviolet irradiation region” refers to a region irradiated with ultraviolet rays having a light amount per unit area of 1 ⁇ w / cm 2 or more.
  • the amount of UV light per unit area was measured by attaching a sensor (TOPCON, product number “UD-36”) to a light amount measuring device (TOPCON, product number “UVR-2”). Is.
  • the point b is the point where the distance from the light source 19 is the longest in the ultraviolet irradiation region 22, that is, the ultraviolet ray whose light amount per unit area is 1 ⁇ w / cm 2 or more. Represents the point farthest from 19. In the present specification, for convenience, the point b is referred to as “the longest arrival point of ultraviolet rays”.
  • the “inner diameter of the metal pipe having a glass pipe and / or glass window” refers to, for example, the cross-sectional shape in the width direction of the flow portion of the suspension 12 in the pipe 20 shown in FIG. If the circle as shown in ⁇ (e), refers to the length D 1 of the diameter of the circle. Further, for example, the width direction of the cross-sectional shape of the circulation portion of the suspension 12, in the case of an ellipse, as shown in (a) ⁇ (d) in FIG. 16, refers to the length D 2 of the minor axis of the ellipse . For example, when the cross-sectional shape in the width direction of the flow part of the suspension 12 is a rectangle as shown in FIGS.
  • the length D 3 of the short side of the rectangle is referred to. .
  • circulation part of the suspension liquid 12 is a square
  • the length of one side of the said square is said.
  • the cross-sectional shape in the width direction of the flow part of the suspension 12 is a polygon other than a rectangle and a square, it means the length of the diameter of a circle inscribed in the polygon.
  • the “suspension circulation part” refers to a region surrounded by the inner peripheral surface of the pipe 20.
  • the “ultraviolet ray reaching distance in the suspension” refers to the maximum value of the distance reached by the ultraviolet ray having a light amount per unit area of 1 ⁇ w / cm 2 or more in the suspension. That is, as shown in FIG. 15B, the center of the light source 19 (hereinafter referred to as “light source center”) (for example, the point c shown in FIG. 15B) and the longest ultraviolet ray in the ultraviolet irradiation region 22.
  • the length d 1 of the straight line ab when the point close to the light source 19 among the contact points between the straight line cb connecting the reaching point b and the inner peripheral surface of the pipe 20 is the point a.
  • the “light source center” refers to the center of the light emitting region of the light source 19, and more specifically refers to the position corresponding to the peak of the light emission intensity distribution in the light emitting region of the light source.
  • the suspension 12 when the suspension 12 is irradiated with ultraviolet rays so that the ratio of the ultraviolet ray reaching distance in the suspension to the inner diameter of the pipe 20 is 30 to 100%, for example, as shown in FIG.
  • the cross-sectional shape in the width direction of the flow part of the suspension 12 is a circle
  • the ratio of the ultraviolet ray reaching distance (the length d 1 of the straight line ab) to the length D 1 of the diameter of the circle is 30 to 100%. In this way, the suspension 12 is irradiated with ultraviolet rays.
  • FIGS. 18A to 18C are longitudinal sectional views of a model device used for measuring the ultraviolet reach distance in the suspension
  • FIG. 18D is a transverse sectional view of the model device.
  • the ultraviolet reach distance in the suspension can be calculated based on data obtained in advance in a model apparatus as shown in FIG.
  • a model apparatus is designed by imitating an apparatus for actually producing a chlorinated vinyl chloride resin and reaction conditions (type of light source and pipe, concentration of vinyl chloride resin, temperature, light output, etc.).
  • the tank 30 is manufactured by imitating piping of an apparatus that actually manufactures a chlorinated vinyl chloride resin.
  • the light source 19 is stored in the sheath tube 24.
  • FIG. 19 shows an outline of this measurement method.
  • the purpose of this measurement method is to calculate the light source distance (ultraviolet ray reachable distance in the suspension) from the intensity (ultraviolet ray intensity) of the ultraviolet rays irradiated to the suspension into which chlorine is introduced. Since the intensity of ultraviolet light varies depending on the presence or absence of chlorine, calculations from Experiment 1 to Experiment 3 cannot be performed directly. For this reason, it is necessary to consider the calculation from Experiment 3 to the purpose from the relationship between Experiments 1 and 2.
  • the model apparatus measures the ultraviolet intensity at each distance while changing the distance A between the light source 19 and the sensor 23. Since the sensor 23 is provided so as to contact the outer peripheral surface of the tank 30, the distance A is changed by moving the position of the light source 19 in the inner diameter direction of the tank 30. For example, when the tank 30 having a circular cross-sectional shape as shown in FIG. 18D is used, the position of the light source 19 is moved in the diameter direction of the circle. The measurement is performed while stirring the suspension 12 with the stirring blade 26. In Experiment 1, chlorine is not introduced into the suspension 12 of the vinyl chloride resin. Thus, the relationship between the distance A and the ultraviolet intensity when the current value (Amp) is constant is confirmed. Since the distance A includes the thickness of the wall of the tank 30, the ultraviolet ray reach distance (the length d shown in FIG. 18D) in the actual suspension is from the distance A to the tank 30. The value is obtained by reducing the wall thickness.
  • Experiment 2 As shown in FIG. 18B, in the model device, the same intensity as the ultraviolet intensity at each distance in Experiment 1 is obtained when the light source 19 is fixed and the distance A is constant. Measure the current value. The current value of the light source 19 is controlled by the light source control unit 25. The measurement is performed while stirring the suspension 12 with the stirring blade 26. In Experiment 2, as in Experiment 1, chlorine is not introduced into the suspension 12 of the vinyl chloride resin. Thereby, the relationship between the ultraviolet intensity and the current value when the distance A is constant is confirmed.
  • the ultraviolet intensity at the current value corresponding to each distance was measured while introducing chlorine into the suspension 12 of the vinyl chloride resin.
  • the current value of the light source 19 is controlled by the light source control unit 25.
  • the measurement is performed while stirring the suspension 12 with the stirring blade 26. Thereby, the relationship between the current value and the ultraviolet intensity in the suspension 12 into which chlorine is introduced is confirmed.
  • the ultraviolet reach distance is indirectly calculated from the ultraviolet intensity in the suspension 12 into which chlorine is measured, which is measured in an actual manufacturing apparatus. Can do.
  • the ultraviolet rays in order to irradiate the ultraviolet rays so that the ratio of the ultraviolet ray reaching distance to the inner diameter of the pipe is 30 to 100%, the ultraviolet rays reachable in the suspension of the vinyl chloride resin as described above. Considering various factors that affect the distance, light source conditions (type, position, output, etc.), piping conditions (shape, material, etc.), the ratio of UV reach to the inner diameter of the pipe is 30 to 100%. What is necessary is just to set suitably the optimal ultraviolet irradiation conditions which become. Note that the method of measuring the ultraviolet reach distance is not limited to the method described above.
  • the ratio of the ultraviolet ray reaching distance to the inner diameter of the pipe is 30 to 100%, the ratio of the ultraviolet ray reaching distance to the inner diameter of the pipe is lower than 30%, compared with the case where vinyl chloride is present in the suspension. It can be said that the amount of ultraviolet rays irradiated to the resin is large.
  • the chlorination of the vinyl chloride resin is started by irradiation with ultraviolet rays and stopped by ending the irradiation with ultraviolet rays. For this reason, if the ratio of the ultraviolet ray reaching distance to the inner diameter of the pipe is 30 to 100%, the chlorination is theoretically less than the case where the ratio of the ultraviolet ray reaching distance to the inner diameter of the pipe is lower than 30%.
  • the ratio of the vinyl chloride resin started is high. It can be said that the higher the ratio of the chlorinated vinyl chloride resin, the higher the reaction efficiency. Therefore, if the ratio of the ultraviolet ray reaching distance to the pipe inner diameter is 30 to 100%, the ultraviolet ray reaching distance relative to the pipe inner diameter is It can be said that the reaction efficiency is high as compared with the case where the ratio is lower than 30%.
  • the irradiation step it is more preferable to circulate the vinyl chloride resin suspension 12 and irradiate the suspension 12 with ultraviolet rays a plurality of times. Thereby, an ultraviolet-ray can be efficiently irradiated with a vinyl chloride resin.
  • the number of times the suspension 12 is circulated may be set as appropriate according to, for example, the number of the light sources 19, the thickness of the pipe 20, the chlorine content of the desired chlorinated vinyl chloride resin, and the like. It is not a thing.
  • the suspension can be irradiated with ultraviolet rays so that the ratio of the ultraviolet ray reaching distance in the suspension 12 to the inner diameter of the pipe is 30 to 100%, the position where the light source 19 is provided in the manufacturing apparatus of the present invention,
  • the distance between the pipe 20 and the light source 19, the ultraviolet irradiation direction of the light source 19 with respect to the pipe 20, the output of the light source 19, the size and shape of the pipe 20 are not particularly limited, and can be set as appropriate.
  • a metal pipe having a glass pipe and / or a glass window (hereinafter sometimes simply referred to as a pipe) will be described in detail below.
  • the shape of the pipe 20 used in the manufacturing method of the present invention and the manufacturing apparatus of the present invention is not particularly limited, but the cross-sectional shape in the width direction of the flow part of the suspension 12 is preferably flat. .
  • the cross-sectional shape in the width direction of the flow portion of the suspension 12 is an ellipse or a rectangle. Say something.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the inner diameter of the glass pipe and / or the metal pipe having the glass window is 30 to 100%. Easy to do. That is, when the cross-sectional area in the width direction of the pipe 20 is the same, if the cross-sectional shape in the width direction of the flow portion of the suspension 12 is flat, the width direction of the flow portion in the suspension 12 Compared with the case where the cross-sectional shape is a circle, the inner diameter of the pipe 20 becomes shorter.
  • the chlorinated chloride can be more efficiently performed.
  • Vinyl resin can be manufactured.
  • the diameter of the cross-section in the width direction of the flow portion of the suspension 12 (also simply referred to as “inner diameter of the pipe”) is such that the ratio of the UV reach distance in the suspension to the diameter is 30 to 100%.
  • the length is not particularly limited as long as it can be irradiated.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the inner diameter is 30 to 100% when the inner diameter of the pipe 20 is shorter. Therefore, since the irradiation energy for irradiating the necessary ultraviolet rays can be reduced, the chlorinated vinyl chloride resin can be produced more efficiently.
  • the production method of the pipe 20 is not particularly limited, and can be produced by various conventionally known methods.
  • a glass pipe corresponding to the ultraviolet irradiation section and a metal pipe such as a titanium-palladium alloy corresponding to the section not irradiated with ultraviolet light may be alternately connected.
  • a method for producing a metal pipe having a glass window may be produced by, for example, cutting a part of a metal pipe such as titanium-palladium alloy and fitting the glass into the part, but is not particularly limited.
  • it can be produced by various conventionally known methods.
  • the “ultraviolet irradiation section” includes a region (irradiation region in the length direction) of the pipe 20 that is irradiated with the ultraviolet light from the light source 19, and both ends of the irradiation region in the length direction.
  • the section ⁇ where the ultraviolet rays are not irradiated is an area between the adjacent ultraviolet irradiation section ⁇ and the ultraviolet irradiation section ⁇ , and an end of the pipe 20.
  • the ultraviolet irradiation section ⁇ and the reactor 6 (FIG. 1) in the pipe 20 are shown. 1) refers to the area between the entrance and the exit.
  • the irradiation step it is preferable to irradiate ultraviolet rays in the direction passing through the center of the cross-sectional shape in the inner diameter direction of the metal pipe 20 having a glass pipe and / or glass window and in the width direction of the pipe.
  • the light source 19 can irradiate ultraviolet rays in a direction passing through the center of the cross-sectional shape in the inner diameter direction of the metal pipe 20 having the glass pipe and / or the glass window and in the width direction of the pipe. Is preferably provided.
  • the “inner diameter direction of the metal pipe having a glass pipe and / or a glass window” is, for example, when the cross-sectional shape in the width direction of the flow part of the suspension 12 is a circle, the diameter of the circle is
  • the cross-sectional shape in the width direction of the flow part of the suspension 12 is an ellipse
  • the direction parallel to the minor axis of the ellipse is referred to.
  • the cross-sectional shape in the width direction is a rectangle, it means a direction parallel to the short side of the rectangle.
  • the “direction passing through the center of the cross-sectional shape in the width direction of the pipe” is a direction passing through the center of the cross-sectional shape in the width direction of the flow portion of the suspension 12, that is, for example, the flow portion of the suspension 12.
  • the cross-sectional shape in the width direction is a circle, it means the direction passing through the center of the circle, and when the cross-sectional shape in the width direction of the flow part of the suspension 12 is an ellipse, the direction passing through the center of the ellipse
  • the cross-sectional shape in the width direction of the circulation part of the suspension 12 is a rectangle, it means a direction passing through the center of the rectangle.
  • the above-mentioned “irradiate ultraviolet rays in the direction passing through the center of the cross-sectional shape in the inner diameter direction of the glass pipe and / or the metal pipe having the glass window and in the width direction of the pipe” is shown in FIGS.
  • the cross-sectional shape in the width direction of the flow part of the suspension 12 is a circle
  • the direction of the straight line cb connecting the light source center c and the longest arrival point b of ultraviolet rays, and the diameter of the circle Refers to irradiating with ultraviolet rays so that the orientation of Further, as shown in FIGS.
  • ultraviolet rays are irradiated in a direction perpendicular to the outer peripheral surface of the pipe 20, and therefore, the pipes 20 are irradiated with ultraviolet rays obliquely (for example, (d) in FIG. 15, (d) in FIG. 16).
  • the amount of ultraviolet light that hits the outer peripheral surface of the pipe 20 and is reflected can be reduced.
  • the suspension is more efficiently performed so that the ratio of the ultraviolet ray reaching distance in the suspension to the inner diameter of the pipe is 30 to 100%. It becomes possible to irradiate the liquid with ultraviolet rays.
  • the “perpendicular direction with respect to the outer peripheral surface of the pipe” is, as shown in FIG. 15B, a straight line cb connecting the light source center c and the longest arrival point b of ultraviolet rays in the ultraviolet irradiation region 22;
  • the straight line cb exists on the same plane as the cross-section in the width direction of the pipe 20 passing through the point a ′, and
  • the straight line cb indicates that it is perpendicular to the tangent S of the outer periphery of the cross-sectional shape in the width direction of the pipe 20 at the point a ′.
  • the light source 19 is preferably provided at a position where the distance from the glass pipe and / or the metal pipe 20 having the glass window is the shortest.
  • the light source 19 is preferably installed so that the light source 19 is in contact with the pipe 20 as shown in FIG. 15B, FIG. 16A, and FIG.
  • the suspension can be made more efficient so that the ratio of the ultraviolet ray reaching distance in the suspension 12 to the inner diameter of the pipe is 30 to 100%. It is possible to irradiate ultraviolet rays.
  • the number of light sources 19 is not limited to one.
  • the number of the light sources 19 may be any number that can sufficiently irradiate the vinyl chloride resin suspension 12 with ultraviolet rays, and may be arbitrarily set according to the length, thickness, and the like of the pipe 20.
  • the arrangement of the light sources 19 with respect to the pipe 20 is not particularly limited.
  • the light sources 19 may be arranged point-symmetrically or line-symmetrically with respect to the pipe 20 whose cross-sectional shape in the width direction is a circle.
  • a plurality of light sources 19 are arranged point-symmetrically or line-symmetrically with respect to the pipe 20 when viewed in the cross-section in the width direction of the pipe 20.
  • positions so that the piping 20 may be enclosed is included.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the inner diameter of the pipe should be 30 to 100% for at least one light source.
  • the ratio of the reach distance of ultraviolet rays in the suspension to the inner diameter of the pipe is 30 to 100%.
  • the present invention can be configured as follows, for example.
  • ⁇ 2> The cross-sectional shape in the width direction of the ultraviolet irradiation section in the glass pipe and / or the metal pipe having the glass window is flatter than the cross-sectional shape in the width direction of the section not irradiated with ultraviolet light.
  • ⁇ 1> The apparatus for producing a chlorinated vinyl chloride resin according to ⁇ 1>.
  • ⁇ 4> The chlorinated chloride according to any one of ⁇ 1> to ⁇ 3>, wherein the light source is at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser. Vinyl resin production equipment.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window is 30.
  • the suspension of the chlorinated vinyl chloride resin according to ⁇ 6> or ⁇ 7> wherein the suspension of the vinyl chloride resin is circulated and the suspension is irradiated with ultraviolet rays a plurality of times. Production method.
  • ultraviolet rays are emitted from at least one light source selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser.
  • a chlorinated vinyl chloride resin Of producing a chlorinated vinyl chloride resin.
  • the ratio of the ultraviolet ray reaching distance in the suspension to the length of the inner diameter of the glass pipe and / or the metal pipe having the glass window is 30 to 100%.
  • the present invention can be configured as follows, for example.
  • An irradiation step of irradiating the suspension with ultraviolet light while circulating a suspension of the resin, wherein in the irradiation step, the suspension with respect to the inner diameter of the metal pipe having the glass pipe and / or glass window A method for producing a chlorinated vinyl chloride resin, comprising irradiating the suspension with ultraviolet rays so that the proportion of the ultraviolet ray reaching distance in water becomes 30 to 100%.
  • ⁇ 12> The method for producing a chlorinated vinyl chloride resin according to ⁇ 11>, wherein in the irradiation step, a suspension of the vinyl chloride resin is circulated and the suspension is irradiated with ultraviolet rays a plurality of times.
  • ⁇ 13> ⁇ 11> or characterized in that, in the irradiation step, the glass pipe and / or the metal pipe having a glass window is irradiated with ultraviolet rays in a direction passing through the center of the cross-sectional shape in the width direction of the pipe and the width direction of the pipe.
  • ⁇ 12> The method for producing a chlorinated vinyl chloride resin according to ⁇ 12>.
  • ultraviolet rays are irradiated from at least one light source selected from the group consisting of an ultraviolet LED, an organic EL, an inorganic EL, and an ultraviolet laser, according to any one of ⁇ 11> to ⁇ 15> Of producing a chlorinated vinyl chloride resin.
  • An apparatus for producing a chlorinated vinyl chloride resin by chlorinating a vinyl chloride resin by irradiating ultraviolet rays wherein a suspension of the vinyl chloride resin introduced with chlorine is circulated, and / or Or a metal pipe having a glass window, and a glass pipe and / or a light source for irradiating the suspension with ultraviolet light through the glass window, and the metal pipe having the glass pipe and / or the glass window, and The light source can irradiate the suspension with ultraviolet rays such that a ratio of an ultraviolet ray reaching distance in the suspension to an inner diameter of the glass pipe and / or metal pipe having a glass window is 30 to 100%.
  • An apparatus for producing a chlorinated vinyl chloride resin characterized by being configured as described above.
  • the light source is provided so as to be able to irradiate ultraviolet rays in a direction passing through a center of a cross-sectional shape in a width direction of the pipe and / or a metal pipe having a glass window.
  • ⁇ 20> The chlorinated vinyl chloride resin according to any one of ⁇ 17> to ⁇ 19>, wherein a cross-sectional shape in the width direction of the metal pipe having the glass pipe and / or the glass window is an ellipse or a rectangle Manufacturing equipment.
  • ⁇ 21> The chlorinated vinyl chloride according to any one of ⁇ 17> to ⁇ 20>, wherein the light source is at least one selected from the group consisting of ultraviolet LED, organic EL, inorganic EL, and ultraviolet laser -Based resin manufacturing equipment.
  • UV-LED light source unit manufactured by Sentec Co., Ltd., model number “OX223”
  • the ultraviolet LED light source device 100 has three ultraviolet LED elements 110 (manufactured by Nichia Corporation, product number “NC4U133”, forward current 500 mA, forward voltage 14.9 V) having a peak wavelength of 365 nm.
  • the emission spectrum of the ultraviolet LED element used in Reference Example 1 is as shown in FIG.
  • the ultraviolet light emitted from the ultraviolet LED element 110 has a wavelength range of 350 nm to 392 nm, one peak, and a peak wavelength of 365 nm.
  • the wavelength range means a range of wavelengths having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
  • the ultraviolet LED light source device 100 is placed on an aluminum support 200 having a length of 20 mm, a width of 20 mm, and a height of 300 mm, and then a transparent glass cylindrical container 300 having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm. (PYREX (registered trademark)).
  • an ultraviolet LED light source device 100 placed in a cylindrical container 300 and a reactor 600 (capacity 3 L, capacity 3.6 mm) made of a transparent glass container having a thickness of 3.6 mm. PYREX (registered trademark)).
  • the ultraviolet LED light source device 100 disposed in the water bath 500 is opposed to the reactor 600, and three ultraviolet LED elements 110 are arranged in a row in the height direction at equal intervals of 15 mm. Is arranged in. At this time, the distance A between the reactor 600 and the ultraviolet LED element 110 was 80 mm.
  • the water bath 500 is provided with a heat source (not shown) for maintaining the hot water 400 at a predetermined temperature.
  • the inside of the reactor 600 was degassed and purged with nitrogen. Thereafter, chlorine gas was blown into the aqueous suspension 700 of the vinyl chloride resin.
  • the ultraviolet LED element 110 was irradiated with ultraviolet rays to the aqueous suspension 700 of the vinyl chloride resin to start the chlorination reaction. .
  • chlorine gas was blown in, care was taken not to depressurize the reactor 600.
  • the temperature of the hot water 400 in the water bath 500 was maintained at 60 ° C.
  • the chlorine content of the chlorinated vinyl chloride resin was calculated from the neutralization titration value of hydrochloric acid by-produced in the chlorination reaction (the same applies to the following values).
  • 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 ultraviolet irradiation to the end of irradiation was 96 minutes.
  • Comparative Example 1 Reference example except that one UV LED light source device 100 supported by the support 200 was used instead of one 100 W high-pressure mercury lamp (manufactured by Toshiba Lighting & Technology Corp., current value 1.3 A, voltage value 100 V). In the same manner as in Example 1, a chlorinated vinyl chloride resin was obtained.
  • 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 ultraviolet irradiation to the end of irradiation is 120 For minutes.
  • the initial coloration, thermal stability measurement and evaluation at the time of thermoforming the chlorinated vinyl chloride resins obtained in Reference Example 1 and Comparative Example 1 were performed as follows. Moreover, the heat resistance was measured and evaluated by measuring and evaluating the Vicat softening point as follows.
  • the pressure is adjusted in the range of 3 MPa to 5 MPa at 200 ° C. for 10 minutes.
  • a plate having a thickness of 5 mm was produced by pressing.
  • the yellow 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., product number “ZE-2000”).
  • ⁇ Thermal stability 10 parts by weight of methyl methacrylate / butadiene / styrene (MBS) resin (manufactured by Kaneka Corporation, product number “Kane Ace (registered trademark) B31”), 100 parts by weight of chlorinated vinyl chloride resin, liquid tin stabilizer 1 part by weight (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8831”), 1 part by weight of powdered tin stabilizer (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8813”), stearic acid as a lubricant 8 parts after blending 1 part by weight (product number “Lunac (registered trademark) S-90V” manufactured by Kao Corporation) and 0.3 part by weight polyethylene wax (part number “Hiwax220MP” manufactured by Mitsui Chemicals, Inc.) A roll was kneaded at 195 ° C.
  • the obtained sheet was cut into a length of 3 cm and a width of 5 cm, heated in an oven at 200 ° C., and the time until the sheet turned black was measured.
  • Blackening means that the L value of the sheet is 20 or less.
  • the L value was measured using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number “ZE-2000”).
  • ⁇ Softening point of Vicat> 10 parts by weight of methyl methacrylate / butadiene / styrene (MBS) resin (manufactured by Kaneka Corporation, product number “Kane Ace (registered trademark) B31”), 100 parts by weight of chlorinated vinyl chloride resin, liquid tin stabilizer 1 part by weight (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8831”), 1 part by weight of powdered tin stabilizer (manufactured by Nitto Kasei Co., Ltd., product number “TVS # 8813”), stearic acid as a lubricant 8 parts after blending 1 part by weight (product number “Lunac (registered trademark) S-90V” manufactured by Kao Corporation) and 0.3 part by weight polyethylene wax (part number “Hiwax220MP” manufactured by Mitsui Chemicals, Inc.) A roll was kneaded at 195
  • the pressure is adjusted in the range of 3 MPa to 5 MPa at 200 ° C. for 10 minutes.
  • a plate having a thickness of 5 mm was produced by pressing.
  • the Vicat softening point (Vicat softening point) of the chlorinated vinyl chloride resin was measured according to JIS-K7206. However, the load was 5 kg, and the temperature elevation rate was 50 ° C./h (B50 method).
  • 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, so that it can be measured at the time of heat molding. The initial colorability was good, and the time required for blackening was long, so the thermal stability was also good.
  • the chlorinated vinyl chloride resin obtained in Reference Example 1 had a higher Vicat softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 1, and therefore had good heat resistance.
  • the reference example 1 in which the ultraviolet ray was irradiated using the ultraviolet LED was used in comparison with the comparative example 1 in which the ultraviolet ray was irradiated using the mercury lamp.
  • the total power consumption required for the chlorination reaction is remarkably small, which has an energy saving effect and the cost is reduced.
  • a UV-LED light source unit manufactured by Sentec Co., Ltd., model number “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 Corporation, product number “NC4U133”, forward current 500 mA, forward voltage 14.9 V) that irradiates ultraviolet rays having a peak wavelength of 365 nm. ing.
  • the emission spectrum of the ultraviolet LED element used in Reference Example 2 is as shown in FIG.
  • a transparent glass cylindrical container 300a (PYREX (registered trademark) having an inner diameter of 74 mm, a height of 600 mm, and a thickness of 7 mm is provided. )) Inserted in.
  • one UV LED light source device 100a placed in a cylindrical container 300a was placed in a jacketed reactor 600a (capacity 100L).
  • the ultraviolet LED light source device 100a has a distance between the center of the cylindrical reactor 600a and the center of the cylindrical container 300a in the top view, that is, the length of B represented by a one-dot chain line in FIG. It arrange
  • the 12 ultraviolet LED elements 110a are arranged in a line in the height direction at equal intervals of 15 mm.
  • the ultraviolet LED element 110a disposed at the lowest position was at a position where the distance from the bottom surface of the reactor 600a was 132 mm.
  • the ultraviolet LED element 110a was arrange
  • the reactor 600a is charged with 45 kg of pure water, a K value of 57.1, an average particle size of 125 ⁇ m, and an apparent density of 0.496 g / ml, a vinyl chloride resin (manufactured by Kaneka Corporation). 5 kg was charged and the reactor 600a was sealed with a lid 620a. Then, an aqueous suspension 700a of vinyl chloride resin, which is a mixed liquid of pure water and vinyl chloride resin, was stirred at a rotational speed of 590 rpm using a turbine blade 610a (diameter 180 mm) of the reactor 600a.
  • the inside of the reactor 600a was vacuum degassed and purged with nitrogen, and then vacuum degassed again. Next, chlorine gas was blown into the aqueous suspension 700a of the vinyl chloride resin.
  • the UV suspension from the ultraviolet LED element 110a was applied to the aqueous suspension 700a of the vinyl chloride resin to start the chlorination reaction.
  • the temperature in the reactor 600a is raised to 50 ° C. in 25 minutes after the start of nitrogen substitution, cooled to 40 ° C. in 15 minutes from the start of the chlorination reaction (start of ultraviolet irradiation), and during the subsequent chlorination reaction ( During UV irradiation, the temperature was maintained at 40 ° C.
  • 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 ultraviolet irradiation to the end of irradiation, 234 minutes.
  • MVS methyl methacrylate / butadiene / styrene
  • the pressure was adjusted to a range of 3 MPa to 5 MPa at 190 ° C.
  • the plate was pressed for 5 minutes to produce a 5 mm thick plate.
  • the obtained plate was measured for YI according to JIS-K7373 using a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., product number “ZE-2000”).
  • MVS methyl methacrylate / butadiene / styrene
  • ⁇ Vicat softening point> 5 parts by weight of methyl methacrylate / butadiene / styrene (MBS) resin manufactured by Kaneka Corporation, product number “Kane Ace (registered trademark) B11A”), 100 parts by weight of chlorinated vinyl chloride resin, liquid tin stabilizer 3 parts by weight (manufactured by Nitto Kasei Co., Ltd., product number “N2000C”), 1 part by weight of PMMA resin (manufactured by Kaneka Corp., product number “Kane Ace (registered trademark) PA-20”), composite lubricant (Kawaken Fine Chemical Co., Ltd.) 1 part by weight of a product number “VLTN-4”) was blended and kneaded for 3 minutes at 180 ° C.
  • MVS methyl methacrylate / butadiene / styrene
  • the pressure was adjusted to a range of 3 MPa to 5 MPa at 200 ° C.
  • the plate was pressed for 5 minutes to produce a 5 mm thick plate.
  • the Vicat softening point of the chlorinated vinyl chloride resin was measured in accordance with JIS-K7206. However, the load was 5 kg, and the temperature elevation rate was 50 ° C./h (B50 method).
  • YI of the chlorinated vinyl chloride resin obtained in Reference Example 2 is 77.6, the time required for blackening is 80 minutes, and the Vicat softening point is 98.6 ° C. Met.
  • the YI of the chlorinated vinyl chloride resin obtained in Comparative Example 2 was 87.1, the time required for blackening was 70 minutes, and the Vicat softening point was 97.2 ° C.
  • 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, so that the initial value during thermoforming The colorability was good, and the heat stability was also good because the time required for blackening was long. Further, the chlorinated vinyl chloride resin obtained in Reference Example 2 had a higher Vicat softening point than the chlorinated vinyl chloride resin obtained in Comparative Example 2, and therefore had good heat resistance.
  • the reference example 2 in which ultraviolet rays were irradiated using an ultraviolet LED was compared with the comparative example 2 in which ultraviolet rays were irradiated using a mercury lamp. The total power consumption required for this is significantly less, which has the effect of energy saving and reduced costs.
  • a UV-LED light source unit (manufactured by Sentec Co., Ltd., model number “OX558”) was prepared as the ultraviolet LED light source device 100b.
  • the ultraviolet LED light source device 100b has three ultraviolet LED elements 110b (manufactured by Nichia Corporation, product number “NC4U133A”, forward current 500 mA, forward voltage 14.9 V) having a peak wavelength of 365 nm.
  • the emission spectrum of the ultraviolet LED element used in Reference Example 3 is as shown in FIG. As shown in FIG. 7, 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 transparent glass cylindrical container 300b (PYREX (registered trademark)) having an inner diameter of 25 mm, a height of 360 mm, and a thickness of 2.5 mm.
  • a transparent glass cylindrical container 300b PYREX (registered trademark) having an inner diameter of 25 mm, a height of 360 mm, and a thickness of 2.5 mm.
  • a reactor 600b (capacity 10L, PYREX (registered trademark)), which is a transparent glass container, is placed in a water bath 500a containing warm water 400a at 25 ° C., and a cylindrical container 300b.
  • One UV LED light source device 100b placed in the reactor was placed in the reactor 600b.
  • the three ultraviolet LED elements 110b were arranged in a line in the height direction at equal intervals of 15 mm.
  • the ultraviolet LED element 110b disposed at the lowest position was at a position 90 mm from the bottom surface of the reactor 600b.
  • the ultraviolet LED element 110b was arrange
  • the water bath 500a is provided with a heat source (not shown) for maintaining the hot water 400a at a predetermined temperature.
  • the chlorine content of the chlorinated vinyl chloride resin reached 67.1%
  • the ultraviolet irradiation by the ultraviolet LED element 110b was terminated, and the chlorination reaction was terminated.
  • the reaction time of the chlorination reaction that 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 irradiation to the end of irradiation was 120 minutes. .
  • the remaining hydrochloric acid was removed by washing with water, and then the chlorinated vinyl chloride resin was dried. Thereby, a chlorinated vinyl chloride resin was obtained.
  • Reference Example 4 Chlorinated vinyl chloride in the same manner as in Reference Example 3 except that one UV-LED light source unit (manufactured by Sentec Co., Ltd., model number “OX559”) was used instead of the ultraviolet LED light source device 100b. A system resin was obtained.
  • the ultraviolet LED light source device has three ultraviolet LED elements (manufactured by Nichia Corporation, product number “NC4U134A”, forward current 500 mA, forward voltage 14.8 V) having a peak wavelength of 385 nm.
  • the emission spectrum of the ultraviolet LED used in Reference Example 4 is as shown in FIG. As shown in FIG. 13, the ultraviolet light emitted from the ultraviolet LED element has a wavelength range of 355 nm to 415 nm, one peak, and a peak wavelength of 385 nm.
  • the wavelength range means a range of wavelengths having a relative emission intensity of 2% or more with respect to the relative emission intensity of the peak wavelength in the emission spectrum.
  • 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 ultraviolet irradiation to the end of irradiation, It was 135 minutes.
  • 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 ultraviolet irradiation to the end of irradiation, 93 minutes.
  • the YI of the chlorinated vinyl chloride resin obtained in Reference Example 3 was 91.1, the time required for blackening was 60 minutes, and the Vicat softening point was 117.8 ° C.
  • the YI of the chlorinated vinyl chloride resin obtained in Reference Example 4 was 93.3, the time required for blackening was 50 minutes, and the Vicat softening point was 115.2 ° C.
  • the YI of the chlorinated vinyl chloride resin obtained in Comparative Example 3 was 132.3, the time required for blackening was 20 minutes, and the Vicat softening point was 114.3 ° C.
  • the total light amount in Reference Example 3, Reference Example 4 and Comparative Example 3 was measured and calculated as follows.
  • the light quantity per unit area of the ultraviolet rays emitted from the light source was measured at the position where the distance between the light source and the light source was closest.
  • the irradiation area where the ultraviolet rays irradiated from the light source hit the chlorinated vinyl resin was measured at the position where the distance between the vinyl chloride resin present in the reactor and the light source was the shortest when the chlorination reaction was performed.
  • a value obtained by multiplying the value of the irradiation area obtained by the above measurement with the value of the light amount per unit area was defined as the total light amount.
  • the amount of light per unit area and the irradiation area were measured in an air atmosphere and with the reactor inside empty. The results are shown in Table 3 below.
  • 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.
  • the initial colorability at the time of heat molding was good, and since the time required for blackening was long, the thermal stability was also good.
  • the chlorinated vinyl chloride resins obtained in Reference Example 3 and Reference Example 4 had a higher Vicat softening point than the chlorinated vinyl chloride resins obtained in Comparative Example 3, and thus had good heat resistance. .
  • Reference Example 3 using an ultraviolet LED that irradiates ultraviolet light with a peak wavelength of 365 nm is used in Reference Example 4 that uses an ultraviolet LED that irradiates ultraviolet light with a peak wavelength of 385 nm.
  • a chlorinated vinyl chloride resin having improved initial colorability and thermal stability during thermoforming was obtained.
  • UV light having a peak wavelength of 365 nm is applied to Reference Example 4 using an UV LED that emits UV light having a peak wavelength of 385 nm. It was found that Reference Example 3 using an ultraviolet LED requires less total light, has a shorter reaction time, and has a higher reaction efficiency.
  • the ultraviolet LED light source device 100b was inserted into a transparent glass cylindrical container 300 (PYREX (registered trademark)) having an inner diameter of 75 mm, a height of 400 mm, and a thickness of 2.5 mm.
  • the LED light source device 100b is surrounded by aluminum foil for the purpose of collecting light, and the front surface of the ultraviolet LED element 110b is cut out to 50 mm in length and 50 mm in width so that light does not leak from other than that portion.
  • an ultraviolet LED light source device 100b placed in a cylindrical container 300, and a reactor 600b (capacity 10L) that is a transparent glass container. , PYREX (registered trademark)).
  • the ultraviolet LED light source device 100b disposed in the water bath 500a is opposed to the reactor 600b, and three ultraviolet LED elements 110b are arranged in a row in the height direction at equal intervals of 15 mm. Arranged. At this time, the distance A between the reactor 600b and the ultraviolet LED element 110b was 60 mm.
  • the water bath 500a is provided with a heat source (not shown) for maintaining the hot water 400a at a predetermined temperature.
  • 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 irradiation to the end of irradiation was 309 minutes. .
  • the remaining hydrochloric acid was removed by washing with water, and then the chlorinated vinyl chloride resin was dried. Thereby, a chlorinated vinyl chloride resin was obtained.
  • 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 ultraviolet irradiation to the end of irradiation, It was 300 minutes.
  • Reference Example 5 using an ultraviolet LED that emits ultraviolet light having a peak wavelength of 365 nm is used in Reference Example 5 that uses an ultraviolet LED that emits ultraviolet light having a peak wavelength of 385 nm.
  • a chlorinated vinyl chloride resin having better initial colorability during thermoforming was obtained.
  • ultraviolet light having a peak wavelength of 365 nm is applied to Reference Example 6 using an ultraviolet LED that emits ultraviolet light having a peak wavelength of 385 nm. It was found that the reaction time of Reference Example 5 using an ultraviolet LED was almost the same, but the required total light amount was almost half and the reaction efficiency was high. There was no difference between Reference Example 5 and Reference Example 6 in terms of total power consumption.
  • the vinyl chloride resin is efficiently irradiated with ultraviolet rays, for example, it is possible to produce a chlorinated vinyl chloride resin having improved reaction efficiency when producing a chlorinated vinyl chloride resin. it can.
  • the chlorinated vinyl chloride resin obtained by the present invention has excellent characteristics such as high mechanical strength, weather resistance, chemical resistance and the like of vinyl chloride resin, and further has better heat resistance than vinyl chloride resin. Therefore, it can be used in various industrial fields.
  • the chlorinated vinyl chloride resin can be used for various applications such as heat-resistant pipes, heat-resistant industrial plates, heat-resistant films and heat-resistant sheets.

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Abstract

　Résines de chlorure de vinyle chlorées pouvant être produite de manière efficace au moyen d'un appareil de production de résines de chlorure de vinyle chlorées, lequel comprend une source de lumière (19) et un tube (20) pour faire circuler une suspension de résine de chlorure de vinyle (12) dans lequel le chlore a été introduit, la section transversale du tube (20) dans le sens de la largeur ayant une forme elliptique ou rectangulaire dans au moins certaines régions d'irradiation UV (α).
PCT/JP2014/061822 2013-05-01 2014-04-28 Appareil et procédé de production de résine de chlorure de vinyle chlorée Ceased WO2014178362A1 (fr)

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WO2017065224A1 (fr) * 2015-10-15 2017-04-20 株式会社カネカ Procédé de production de résine de chlorure de vinyle chlorée
WO2020203828A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203835A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203840A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203858A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
US12187883B2 (en) 2019-03-29 2025-01-07 Sekisui Chemical Co., Ltd. Chlorinated vinyl chloride resin
US12351672B2 (en) 2019-03-29 2025-07-08 Sekisui Chemical Co., Ltd. Chlorinated vinyl-chloride-based resin
US12486394B2 (en) 2019-09-30 2025-12-02 Sekisui Chemical Co., Ltd. Molding resin composition and molded article

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JP2008031265A (ja) * 2006-07-27 2008-02-14 Kaneka Corp 塩素化塩化ビニル系樹脂の製造方法
WO2013069542A1 (fr) * 2011-11-07 2013-05-16 株式会社カネカ Procédé de production de résine de chlorure de vinyle chlorée

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Publication number Priority date Publication date Assignee Title
WO2017065224A1 (fr) * 2015-10-15 2017-04-20 株式会社カネカ Procédé de production de résine de chlorure de vinyle chlorée
JPWO2017065224A1 (ja) * 2015-10-15 2018-08-02 株式会社カネカ 塩素化塩化ビニル系樹脂の製造方法
WO2020203828A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203835A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203840A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
WO2020203858A1 (fr) 2019-03-29 2020-10-08 積水化学工業株式会社 Resine de chlorure de vinyle chloree
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