JP2007169584A - Vinyl chloride-based resin and vinyl chloride-based resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a vinyl chloride-based resin capable of thermally forming a molded product having a less irregular structure, low yellowing properties and excellent transparency, and a vinyl chloride-based resin molded product causing less yellowing and having excellent transparency. <P>SOLUTION: The vinyl chloride-based resin is provided being a (co)polymer or chloride thereof obtained by polymerization and copolymerization of a monomer copolymerizable with a vinyl chloride monomer and/or vinyl chloride, wherein the (co)polymer or chloride thereof has a titanium content of 1.0 ppm or less, and (1) when a peak intensity based on a methylene hydrocarbon chain is taken as 100, a peak intensity of a methyl branch generated in 18.5 to 22.5 ppm is 0.15 or less, or (2) a period of time until a total amount of hydrogen chloride generated from initiation of heating reaches 2,000 ppm under heating at 200°C is 30 minutes or more, or (3) a plate form body made by powder pressing at 180°C has a yellowness index (YI) measured according to JIS K7105 of 20 or less. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

   The present invention relates to a vinyl chloride resin and a molded body thereof.

   Conventionally, vinyl chloride resins have been used as plant plates, pipes, pipes as materials with excellent properties such as mechanical strength, heat resistance, flame resistance, weather resistance, chemical resistance, moisture absorption resistance, and transparency. It is used in many applications such as joints, sheets and films. In addition, chlorinated vinyl chloride resins, which are post-chlorinated products of vinyl chloride resins, have higher heat resistance and flame retardancy, and are used for applications that require higher heat resistance and flame retardancy. ing.

  However, the vinyl chloride resin has a defect that it is easily yellowed during thermoforming, and is unsuitable for applications requiring transparency or light color. Among them, a vinyl chloride resin having a high chlorine content has improved heat resistance, but it must be thermoformed at a high temperature and is more easily yellowed.

  This is based on irregular or unstable structures such as branched structures or head-to-head structures contained in vinyl chloride resins. (Tertiary chlorine at the branch points of branched structures is thermally unstable. This is due to the fact that dehydrochlorination occurs and double bonds are generated. By reducing this irregular structure, the development of vinyl chloride resins that are less prone to yellowing and generate less hydrochloric acid is possible. It was expected.

  On the other hand, for example, a method for lowering the reaction temperature during the polymerization reaction (for example, see Patent Document 1), a polymerization method using a metallocene compound (for example, see Patent Document 2), and a polymerization method using a titanium compound as a catalyst (For example, Patent Documents 3 to 5) have been proposed.

JP-A-35-7588 JP 2002-80518 A JP 2005-36216 A JP 2005-36196 A JP 2005-36195 A

  However, the vinyl chloride resin obtained by the above polymerization method has a less irregular structure than a general vinyl chloride resin, but is still insufficient for applications requiring high transparency.

  The present invention has been made in view of the above-mentioned problems of the prior art, and includes a vinyl chloride resin and a yellowing which can thermoform a molded article having a small irregular structure, a low yellowing property, and an excellent transparency. An object of the present invention is to provide a vinyl chloride-based resin molded article with less transparency and excellent transparency.

In order to further improve the transparency of the vinyl chloride resin that was still insufficient, the inventors have conducted intensive research on the trace components contained in the obtained resin and the method for producing the resin. As a result, the catalyst residue used in the vinyl chloride resin was found to have factors that adversely affect the quality such as coloring and transparency, and the present invention was completed.
That is, the vinyl chloride resin of the present invention is a (co) polymer obtained by polymerizing or copolymerizing a vinyl chloride monomer and / or a monomer copolymerizable with vinyl chloride, or a chlorinated product thereof. ) The polymer or the chlorinated product thereof has a titanium content of 1.0 ppm or less, (1) hydrocarbonated in the presence of 2,2-azobisisobutyronitrile and tributyltin hydride, and ¹³ C-NMR When the peak intensity based on the methylene hydrocarbon chain is 100, the peak intensity of methyl branching generated at 18.5 to 22.5 ppm is 0.15 or less, or (2) 200 ° C. Under heating, the time from the start of heating until the total amount of generated hydrogen chloride reaches 2000 ppm is 30 minutes or more, or (3) produced by a 180 ° C powder press. A yellowness YI of the obtained plate-like body measured in accordance with JIS K7105 is 20 or less.
Moreover, the vinyl chloride resin molded body of the present invention is formed by molding the above-described vinyl chloride resin.

  According to the present invention, a molded body having few irregular structures, excellent heat resistance, dehydrochlorination reaction during thermoforming, low yellowing, and excellent transparency can be thermoformed. A vinyl chloride resin can be obtained. As a result, it is possible to obtain a vinyl chloride resin molded body with little yellowing and excellent transparency.

  As described above, the vinyl chloride resin of the present invention is a (co) polymer obtained by polymerizing or copolymerizing a vinyl chloride monomer and / or a monomer copolymerizable with vinyl chloride, or a chlorinated product thereafter.

  The vinyl chloride monomer or the monomer copolymerizable with vinyl chloride is not particularly limited as long as it is a known vinyl monomer. For example, α-olefins such as ethylene, propylene, butylene: vinyl acetate, vinyl propionate Vinyl esters such as: ethyl vinyl ether, vinyl ethers such as butyl vinyl ether: (meth) acrylic acid esters such as methyl (meth) acrylate, butyl (meth) acrylate, and hydroxyethyl (meth) acrylate. These may be used alone or in combination of two or more.

  Any known method can be adopted as the method of polymerization or copolymerization of the present invention. For example, a method called an ionic polymerization method can be suitably used. From another viewpoint, a bulk polymerization method, a solution polymerization method, and the like can be given. In addition, as a solvent in the case of performing solution polymerization, although it does not specifically limit, what the solvent itself does not modify | denature during polymerization is selected. For example, hexane, dichloromethane, toluene and the like can be mentioned.

  When practicing the present invention, a sufficiently dried reaction vessel is replaced under an inert gas atmosphere such as nitrogen or argon, then degassed, and copolymerized with vinyl chloride monomer and / or vinyl chloride monomer. A monomer, a zirconium compound, an aluminum compound, and optionally a solvent are added to initiate the polymerization reaction. In addition to the reactor, it may be dissolved or diluted with a solvent or the like.

  The polymerization temperature of the vinyl chloride resin in the present invention is not particularly limited, but the reaction rate becomes slow when it becomes low, it takes time to polymerize to a predetermined yield, and the chain transfer of the monomer occurs when it becomes high. Considering the point that it becomes easy and it becomes difficult to obtain a high molecular weight (co) polymer, 0 ° C. to 60 ° C. is appropriate. The reaction pressure is not particularly limited.

After adding a deactivator such as methanol or water to the reaction mixture obtained by the above polymerization and performing deactivation treatment, deashing treatment with acid / alkali, residual catalyst removal treatment with a porous adsorbent, etc. By performing, a (co) polymer can be obtained.
However, in the (co) polymer obtained by this ionic polymerization method or the subsequent chloride, the titanium content is preferably 1.0 ppm or less, more preferably 0.9 ppm or less and 0.8 ppm or less.

  In the present invention, the (co) polymer having a titanium content obtained by polymerization exceeding 1.0 ppm or a chloride thereafter is subjected to a removal step such as purification, washing, etc. It is theoretically possible to make the titanium content of the polymer or the chloride thereafter 1.0 ppm or less. However, in reality, the removal process using a large amount of organic solvent and acid / alkaline solution must be repeated many times, and it is analyzed whether the titanium content is removed to 1.0 ppm or less. When the content of titanium is confirmed, it is necessary to repeat the removal process.For example, the production efficiency is greatly reduced, and the titanium content of the obtained resin is not realistic. Polymerization or copolymerization methods exceeding 1.0 ppm are preferably not included in the present invention. That is, as a polymerization method in which the titanium content exceeds 1.0 ppm, a method using a titanium compound as a catalyst is usually used in the polymerization. However, in such a method, a large amount of an organic solvent, an acid is used. -Unless unreliable removal treatment is repeated, such as using an alkaline solution many times, the titanium content of the (co) polymer or chloride should be 1.0 ppm or less. It is difficult.

Further, in a general radical polymerization method not using a titanium compound, a chain transfer reaction to a polymer of a radical active species occurs, so that a branched structure is likely to occur. It is considered that the tertiary chlorine at the branching point of the branched structure becomes thermally unstable and tends to cause a dehydrochlorination reaction. Therefore, the polymerization or copolymerization method of the present invention is not a method using a titanium compound as a catalyst, but a polymerization method using a zirconium compound and an aluminum compound as a catalyst in an ionic polymerization method, for example. It is done.
That is, if the titanium compound remains in the resin in excess of 1.0 ppm, yellowing cannot be avoided and cannot be used for applications requiring high transparency. On the other hand, when the titanium compound is not more than 1.0 ppm in the resin, the catalyst removal process is not complicated and complicated, the production efficiency is improved, the influence of color development is eliminated, and strict transparency is required. It can also be used for other purposes. Moreover, despite the high quality, the manufacturing cost can be suppressed and the cost can be reduced.

As the zirconium-based compound, a resin having a small branched structure of the polymerization product and excellent thermal stability can be obtained. Therefore, the general formula ZrX ¹ X ² X ³ X ⁴ (wherein X ¹ , X ² , X ³ , X ⁴ is suitably a zirconium compound represented by a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group or the like.
Examples of the halogen atom for X ¹ , X ² , X ³ and X ⁴ include fluorine, chlorine, bromine and iodine atoms.

As the alkyl group, those having 1 to 6 carbon atoms are suitable, and examples thereof include methyl, ethyl, propyl, i-propyl, n-butyl, t-butyl and the like.
As the alkoxy group, those having 1 to 6 carbon atoms are suitable, and examples thereof include methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, t-butoxy and the like.
As the substituted or unsubstituted aryl group, those having 6 to 9 carbon atoms are suitable. Moreover, a halogen atom is mentioned as a substituent. Examples thereof include phenyl, tolyl, xylyl, cumenyl, mesityl, naphthyl, phenyl chloride, tolyl chloride, xylyl chloride and the like.

As the substituted or unsubstituted aryloxy group, those having 6 to 9 carbon atoms are suitable. Moreover, a halogen atom is mentioned as a substituent. Examples include phenoxy, tolyloxy, xyloxy, cumenyloxy, mesityloxy, naphthyloxy, phenoxy chloride, tolyloxy chloride, xylyloxy chloride, and the like.
Of these, zirconium alkoxides and zirconium aryloxides, which are tetra-substituted alkoxy groups and aryloxy groups, are preferred in that the resulting vinyl chloride resin has fewer branched structures, and X ¹ to X ⁴ More preferably, all are the same substituent.

  Specific examples of the zirconium compound include zirconium alkoxides such as zirconium tetra-n-butoxide, zirconium tetra-t-butoxide and zirconium tetraisopropoxide; zirconium aryloxides such as zirconium tetraphenoxide; dicyclopentadienyl; Zirconenes such as zirconium dichloride and dicyclopentadienyl zirconium dibutoxide; cyclopentadienyl zirconium trichloride, cyclopentadienyl zirconium tributoxide, pentamethylcyclopentadienyl zirconium tributoxide, pentamethylcyclopentadi And half-zirconocenes such as enilzirconium triphenoxide.

The concentration of the zirconium compound in the polymerization system is not particularly limited, but from the viewpoint of securing the polymerization degree of the vinyl chloride resin, reducing the amount of remaining zirconium, and improving the polymerization efficiency, the concentration of zirconium is 10 ^−1. It is preferably in the range of -10 ^-8 mol / l.

As the aluminum compound, an aluminum compound represented by the general formula AlY ¹ Y ² Y ³ (wherein Y ¹ , Y ² , Y ³ are a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, etc.) or Alkylaluminoxanes can be used.
Examples of Y ¹ , Y ² and Y ³ are the same as those exemplified for X ¹ to X ⁴ .
Specific examples of the aluminum compound include trimethylaluminum, triethylaluminum, tri-i-butylaluminum, tri-n-hexylaluminum, ethylaluminum sesquichloride, diethylaluminum chloride, ethylaluminum dichloride, i-butylaluminum dichloride, diethylaluminum. Examples include ethoxide.
Examples of the alkylaluminoxane include methylaluminoxane and ethylaluminoxane.

  In the present invention, trimethylaluminum, triethylaluminum, ethylaluminum dichloride, and methylaluminoxane are more preferred because the production efficiency and branched structure of the resulting vinyl chloride resin are less. These can be used alone or in combination of two or more.

The concentration of the aluminum compound and / or alkylaluminoxane in the polymerization system is such that the molar ratio of aluminum / zirconium is 1 to 10 ^{5 in} terms of the molar ratio with zirconium from the viewpoint of improving the polymerization yield and suppressing the increase in the amount of remaining metal. It is preferable that it is the range of these.

In the present invention, the subsequent chlorination product of the (co) polymer can be obtained by using any conventionally known chlorination method for the obtained (co) polymer. Examples of the chlorination method include a water suspension thermal chlorination method, a water suspension photochlorination method, and a solution chlorination method. Especially, since the yellowing of the obtained resin is lower, the water suspension thermal chlorination method is preferable. However, if a radical generator such as hydrogen peroxide is added at the time of chlorination, the resulting chlorinated product may form a structure serving as a base point for dehydrochlorination in the main chain. It is preferable not to add as much as possible. When a radical generator is added, the amount added is preferably 50 ppm or less.
The vinyl chloride resin of the present invention is preferably a post-chlorinated product from the viewpoint that yellowing is reduced and transparency is improved.

The vinyl chloride resin of the present invention is hydrocarbonated in the presence of 2,2-azobisisobutyronitrile and tributyltin hydride, and measured by ¹³ C-NMR, a peak based on a methylene hydrocarbon chain. When the intensity is 100, the peak intensity of methyl branched methyl carbon generated at 18.5 to 22.5 ppm is 0.15 or less.

Such a vinyl chloride resin is a vinyl chloride resin having substantially no branched structure other than the terminal branched structure derived from the polymerization initiator in the main chain.
When it has a branched structure, it is hydrocarbonated in the presence of 2,2-azobisisobutyronitrile and tributyltin hydride and measured by ¹³ C-NMR, the methyl branched methyl carbon peak is 18.5-22. When it appears in the vicinity of 0.5 ppm, but the branch structure is extremely small, the peak intensity generated in the vicinity of 18.5 to 22.5 ppm is less than the peak intensity (29.6 ppm) based on the methylene hydrocarbon chain. It is preferably 15 or less, 0.10 or less, 0.9 or less, and more preferably less than 0.8.

The measurement method of the ¹³ C-NMR is as follows.
First, in a solution obtained by dissolving 1 g of a vinyl chloride resin in a mixed solvent of 90 ml of p-xylene at 90 ° C. and 30 ml of tetrahydrofuran, 60 mg of 2,2-azobisisobutyronitrile and 3 ml of tributyltin hydride were added to p-xylene. A solution dissolved in 20 ml is added and reacted at 90 ° C. for 1 hour.

Next, a solution prepared by dissolving 30 mg of 2,2-azobisisobutyronitrile and 1 ml of tributyltin hydride in 5 ml of p-xylene is added and reacted at 90 ° C. for 2 hours to convert it into hydrocarbon.
After completion of the reaction, the reaction solution is supplied to 500 ml of methanol to precipitate hydrocarbons, filtered, washed with methanol, and dried to obtain hydrocarbons.
The obtained hydrocarbon was supplied to a nuclear magnetic resonance apparatus, ¹³ C-NMR was measured, and when the peak intensity based on the methylene hydrocarbon chain was taken as 100, the peak intensity generated at 18.5 to 22.5 ppm Measure the total.

  From another point of view, the vinyl chloride resin of the present invention has a time of 30 minutes or more until the total amount of generated hydrogen chloride from the start of heating reaches 2000 ppm under heating at 200 ° C. Thereby, the yellowness of a product is improved and an external appearance and transparency can be improved.

The method for measuring the amount of generated hydrogen chloride is as follows.
First, 1 g of the obtained vinyl chloride resin is supplied to a test tube, sealed with a heat-resistant rubber stopper with a tube, and the test tube is immersed in a 200 ° C. oil bath from the bottom 2/3 and heated. The gas generated from the test tube is collected with 100 ml of ion exchange water through the tube, and the pH change of the ion exchange water is measured every minute. The amount of hydrogen chloride generated is calculated from the difference from the pH of ion-exchanged water before the start of collection, and the time when the total amount of hydrogen chloride generated from the start of measurement reaches 2000 ppm is defined as 2000 ppm hydrogen chloride generation time. The unit is minutes.

  Furthermore, from another point of view, the vinyl chloride resin of the present invention preferably has a yellowness YI of 20 or less, more preferably 18 or less, measured on a plate-like body prepared by a powder press at 180 ° C. according to JIS K7105. 16 or less and 15 or less are preferable. This yellowness YI is the yellowness of the vinyl chloride resin alone. Thereby, yellowing is suppressed and an external appearance and transparency can be improved.

The measuring method of yellowness YI is as follows.
First, powdery vinyl chloride resin is supplied to a press molding machine set at 180 ° C., preheated for 1 minute, and then pressed at 200 MPa for 1 minute to produce a plate having a thickness of 1 mm and a 5 cm square. To do. Next, the yellowness YI of the obtained plate-like body is measured according to JIS K7105.

Moreover, the zirconium content in the vinyl chloride resin of the present invention is not particularly limited, but if it is excessively contained, the transmittance and haze deteriorate due to coloring and turbidity, so 0.05-100 ppm is preferable.
The aluminum content in the vinyl chloride resin is not particularly limited, but if it is excessively contained, the transmittance and haze deteriorate due to coloring and turbidity after molding, so 0.1 to 300 ppm is preferable.
The method of bringing the zirconium and / or aluminum in the vinyl chloride resin within the desired range is not particularly limited, but a method of adjusting the amount of these compounds used in the reaction system, during or after polymerization. And a method of washing the resin with a suitable solvent by a method known in the art. Specifically, after removing insoluble matter by centrifugation from a solution in which a vinyl chloride resin is dissolved in a good solvent such as tetrahydrofuran, a porous substance such as activated carbon or zeolite is used to remove zirconium and / or Or the method of adsorbing and removing aluminum etc. is mentioned.

  The chlorine content of the vinyl chloride resin of the present invention is not particularly limited. However, when it is high, thermoforming processability is lowered, gelation is insufficient, and a molded product is hardly obtained. Therefore, about 73 wt% or less, about 70 wt% or less, and further about 68 wt% or less are preferable.

The vinyl chloride resin molded body of the present invention can be formed by any conventionally known method, such as an extrusion molding method, an injection molding method, a blow molding method, a roll molding method, a calendar molding method, and a press molding method. Etc.
When molding a molded body from a vinyl chloride resin, a compounding agent generally added when producing a vinyl chloride resin molded body, for example, a heat stabilizer, a heat stabilization aid, if necessary. , Lubricants, processing aids, impact modifiers, heat resistance improvers, antioxidants, light stabilizers, ultraviolet absorbers, pigments, plasticizers, and the like can be used. If these compounding agents are used when shape | molding vinyl chloride-type resin, the kind will not be limited, respectively, It can use individually or in combination of 2 or more types, respectively.

  For example, the heat stabilizer includes dimethyltin mercapto, dibutyltin mercapto, dioctyltin mercapto, dibutyltin malate, dibutyltin malate polymer, dioctyltin malate, dioctyltin malate polymer, dibutyltin laurate, dibutyltin laurate polymer, etc. Organic tin stabilizers, lead stearate, dibasic lead phosphite, tribasic lead sulfate and other lead stabilizers, calcium-zinc stabilizers, barium-zinc stabilizers, barium-cadmium stabilizers Agents and the like.

Examples of the stabilizing aid include epoxidized soybean oil, epoxidized linseed bean oil, epoxidized tetrahydrophthalate, epoxidized polybutadiene, and phosphate ester.
Examples of the lubricant include an internal lubricant and an external lubricant used when molding a vinyl chloride resin composition.
The internal lubricant is a lubricant added for the purpose of lowering the flow viscosity of the molten resin during thermoforming and preventing frictional heat generation. Examples include lauryl alcohol, stearyl alcohol, stearic acid, butyl stearate, glycerin monostearate, epoxidized soybean oil, bisamide and the like.

  The external lubricant is a lubricant added for the purpose of enhancing the sliding effect between the molten resin and the mold surface during thermoforming. Examples thereof include montanic acid wax, paraffin wax, polyethylene wax, ester wax and the like.

Examples of the processing aid include an acrylic processing aid that is an alkyl acrylate-alkyl methacrylate copolymer having a weight average molecular weight of 100,000 to 2,000,000. Specific examples include n-butyl acrylate-methyl methacrylate copolymer, 2-ethylhexyl acrylate-methyl methacrylate-butyl methacrylate copolymer, and the like.
Examples of the impact modifier include methyl methacrylate-butadiene-styrene copolymer (MBS resin), chlorinated polyethylene, acrylic rubber, and the like.
Examples of the heat resistance improver include a heat resistance improver such as an α-methylstyrene type and an N-phenylmaleimide type.

Examples of the antioxidant include phenolic antioxidants.
Examples of the light stabilizer include hindered amine light stabilizers.
Examples of the ultraviolet absorber include salicylic acid ester-based, benzophenone-based, benzotriazole-based, and cyanoacrylate-based ultraviolet absorbers.

Examples of the pigment include organic pigments such as azo, phthalocyanine, selenium, and dye lake, and inorganic pigments such as oxide, molybdenum chromate, sulfide / selenide, ferrocyanide, and the like. It is done. When the molded body is required to be transparent, it is necessary to add it in consideration of the required transparency.
The plasticizer is added for the purpose of improving the molten resin and processability during thermoforming. For example, dibutyl phthalate, di-2-ethylhexyl phthalate, di-2-ethylhexyl adipate and the like can be mentioned.

  The method for mixing these blends with the vinyl chloride resin is not particularly limited, and examples thereof include a hot blend method and a cold blend method.

  Hereinafter, the present invention will be specifically described by showing examples and comparative examples of the vinyl chloride resin of the present invention and molded articles thereof.

Example 1
70 ° C. warm water was passed through a 23 liter jacketed autoclave jacket, the inside of the autoclave was decompressed with a vacuum pump for 30 minutes, sufficiently dehydrated and dried, and then cooled to room temperature. After cooling, 8000 ml of dehydrated hexane, 400 ml of 10 wt% toluene solution of zirconium tetra-n-butoxide, and 400 ml of 10 wt% toluene solution of methylaluminoxane were sequentially injected through a rubber stopper with a syringe into an autoclave under reduced pressure. 8 kg of vinyl chloride monomer sufficiently dehydrated with molecular sieves was injected, adjusted to 20 ° C. and polymerized for 24 hours.

After completion of the polymerization, unreacted vinyl chloride monomer was discharged from the autoclave, and methanol was supplied to deactivate the reaction. The obtained reaction product was taken out from the polymerization vessel, methanol was removed, and the vinyl chloride resin content was dried under vacuum.
After the dried vinyl chloride resin was dissolved in 30 liters of tetrahydrofuran, the insoluble matter was removed by centrifugation, 1 kg of powdered zeolite was added to the solution and stirred for 1 hour, and then a 0.5 μm PTFT filter was used. Filtered off. The filtrate was poured into 60 liters of methanol under stirring to precipitate a vinyl chloride resin. A vinyl chloride resin was filtered from methanol, washed with a large amount of methanol, and dried to obtain a powdery vinyl chloride resin.

(Example 2)
300 g of the vinyl chloride resin obtained in Example 1 was supplied together with 1800 g of deionized water to a 3 liter jacketed glass-lined pressure-resistant reactor equipped with a stirrer and stirred to remove the vinyl chloride resin from the deionized water. While being dispersed, the air in the reaction vessel was sucked with a vacuum pump, the pressure was reduced to −78.4 kPa, and then nitrogen gas was supplied until the pressure became normal. Subsequently, it was again sucked with a vacuum pump to remove oxygen in the reaction vessel.

The heated oil was supplied to the jacket and heated to raise the temperature in the reaction vessel to 70 ° C. When the temperature in the reaction vessel reached 70 ° C., chlorine gas began to be supplied, and the chlorination reaction was advanced to 110 ° C. The generated hydrogen chloride concentration in the reaction vessel was measured, the chlorine content of the vinyl chloride resin was calculated, and the supply of chlorine gas was stopped when the chlorine content reached 66% by weight.
Next, unreacted chlorine gas was removed, and the resulting resin was washed with deionized water, dehydrated and dried to obtain a powdery chlorinated vinyl chloride resin.

(Example 3)
Hot water at 70 ° C. was passed through a jacket of a 23 liter jacketed autoclave, the inside of the autoclave was depressurized with a vacuum pump for 30 minutes, sufficiently dehydrated and dried, and then cooled to room temperature. After cooling, 800 ml of a 10 wt% toluene solution of zirconium tetra-n-butoxide and 800 ml of a 10 wt% toluene solution of methylaluminoxane were sequentially injected through a rubber stopper with a syringe into an autoclave under reduced pressure. Thereafter, 16 kg of vinyl chloride monomer sufficiently dehydrated with molecular sieves was injected, adjusted to 20 ° C. and polymerized for 24 hours.

  After the polymerization was completed, unreacted vinyl chloride monomer was discharged from the autoclave. The reaction was deactivated by supplying methanol, and the resulting reaction product was taken out from the polymerization vessel, methanol was removed, and the vinyl chloride resin was dried under vacuum. The dried vinyl chloride resin was dissolved in 50 L of tetrahydrofuran. Insoluble matter was removed by centrifugation, and 1 kg of powdered zeolite was added to the solution and stirred for 1 hour, followed by filtration with a 0.5 μm PTFT filter. The filtrate was put into 100 L of methanol under stirring to precipitate a vinyl chloride resin. A vinyl chloride resin was filtered from methanol, washed with a large amount of methanol, and dried to obtain a powdery vinyl chloride resin.

Example 4
Using the vinyl chloride resin obtained in Example 3, a chlorinated vinyl chloride resin was obtained in the same manner as in Example 2.

(Example 5)
A vinyl chloride resin was obtained in the same manner as in Example 1 except that zirconium tetraphenoxide was used as the zirconium compound.

(Example 6)
Using the vinyl chloride resin obtained in Example 5, a chlorinated vinyl chloride resin was obtained in the same manner as in Example 2.

(Example 7)
A vinyl chloride resin was obtained in the same manner as in Example 1 except that ethylaluminum dichloride was used as the aluminum compound.

(Example 8)
Using the vinyl chloride resin obtained in Example 7, a chlorinated vinyl chloride resin was obtained in the same manner as in Example 2.

(Comparative Example 1)
A 50-liter jacketed stainless steel polymerization vessel equipped with a stirrer and a reflux condenser was degassed, and then steam was blown from the reflux condenser to raise the temperature in the polymerization vessel to 80 ° C. 25,000 g of deionized water at 50 ° C., 300 g of 3% solution partially saponified polyvinyl alcohol and 150 g of 3% hydroxypropylmethylcellulose are fed into the reaction vessel of the polymerization vessel, and the inside of the reaction vessel is degassed to water vapor pressure +0.01 kPa and stirred. However, 15 kg of vinyl chloride monomer was supplied. Subsequently, 6 g of di-2-ethylhexyl peroxydicarbonate was supplied into the polymerization vessel, and the temperature was raised to 57 ° C. to perform polymerization.

When the temperature in the polymerization reactor reached 57 ° C, the operation of the reflux condenser was started, and the temperature in the polymerization reactor was maintained at 57 ° C.
When the pressure in the polymerization vessel decreased to 0.7 MPa, water was passed through the jacket to cool the inside of the polymerization vessel, and the unreacted vinyl chloride monomer was removed. The obtained resin was washed with deionized water, dehydrated and dried to obtain a powdered vinyl chloride resin.

(Comparative Example 2)
Using the vinyl chloride resin obtained in Comparative Example 1, post-chlorination was performed in the same manner as in Example 2 to obtain a powdery chlorinated vinyl chloride resin.

(Comparative Example 3)
A 50-liter jacketed stainless steel polymerization vessel equipped with a stirrer and a reflux condenser was degassed, and then steam was blown from the reflux condenser to raise the temperature in the polymerization vessel to 80 ° C. 25000 g of deionized water at 50 ° C., 300 g of 3% solution partially saponified polyvinyl alcohol, and 150 g of 3% hydroxypropylmethylcellulose were fed into the reaction vessel of the polymerization vessel, and the inside of the reaction vessel was deaerated to a water vapor pressure of +0.01 kPa. While stirring, 12000 g of vinylidene chloride monomer and 4000 g of vinyl chloride monomer were supplied. Subsequently, 6 g of di-2-ethylhexyl peroxydicarbonate was supplied into the polymerization vessel, and the temperature was raised to 57 ° C. to perform polymerization.
When the temperature in the polymerization reactor reached 57 ° C, the operation of the reflux condenser was started, and the temperature in the polymerization reactor was maintained at 57 ° C.

  When the pressure in the polymerization vessel decreased to 0.7 MPa, water was passed through the jacket to cool the inside of the polymerization vessel, and the unreacted vinyl chloride monomer was removed. The obtained resin was washed with deionized water, dehydrated and dried to obtain a powdered vinyl chloride resin.

(Comparative Example 4)
A vinyl chloride resin was obtained in the same manner as in Example 1 except that pentamethylcyclopentadienyl titanium tri-n-butoxide was used as a catalyst.

(Comparative Example 5)
Using the vinyl chloride resin obtained in Comparative Example 4, a chlorinated vinyl chloride resin was obtained in the same manner as in Example 2.

(Physical property measurement)
Using the obtained vinyl chloride resin, chlorinated vinyl chloride resin, vinyl chloride-vinylidene chloride copolymer (hereinafter referred to as “vinyl chloride resin”), measurement of the amount of metal in the resin, chlorine content, peak (Methyl carbon) strength was measured. The results are shown in Tables 1 and 2.
In addition, a plate-shaped test piece was prepared using the obtained vinyl chloride resin, and the total light transmittance, 650 nm transmittance, haze, yellowness, water absorption, and Vicat softening temperature were measured. It was shown to.

In addition, the preparation method and each measuring method of a plate-shaped test piece were as follows.
(1) Measurement of amount of metal in resin 0.1 g of the obtained vinyl chloride resin was added to 5 ml of nitric acid, 2 ml of hydrochloric acid and 3 ml of hydrogen fluoride and treated with microwave, and then an ICP emission spectrometer (Yamato Scientific Co., Ltd.) Manufactured under the trade name “SPS5100”), and the amounts of titanium, zirconium and aluminum were measured. The unit is ppm.
(2) Chlorine content It measured based on JISK7229 using the obtained vinyl chloride resin. The unit is% by weight.

(3) Methyl carbon strength In a solution of 1 g of the obtained vinyl chloride resin dissolved in a mixed solvent of 90 ml of p-xylene and 90 ml of tetrahydrofuran, 60 mg of 2,2-azobisisobutyronitrile and tributyltin hydride A solution of 3 ml dissolved in 20 ml of p-xylene was added and reacted at 90 ° C. for 1 hour, and then 30 mg of 2,2-azobisisobutyronitrile and 1 ml of tributyltin hydride were dissolved in 5 ml of p-xylene. And reacted at 90 ° C. for 2 hours to convert to hydrocarbon. After completion of the reaction, the reaction solution was supplied to 500 ml of methanol to precipitate hydrocarbons, filtered, washed with methanol, and dried to obtain hydrocarbons.
When the obtained hydrocarbon was supplied to a nuclear magnetic resonance apparatus (manufactured by JEOL Datum, trade name “Lambada400”), ¹³ C-NMR was measured, and the peak intensity based on the methylene hydrocarbon chain was taken as 100, The methyl carbon peak intensity of the methyl branch occurring at 18.5 to 22.5 ppm was measured (POINT: 32768, PD: 10, PW 1: 4.1, TEMP: 130).

(4) Powder yellowness YI
The obtained powdered vinyl chloride resin is supplied to a press molding machine (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) set at 180 ° C., preheated for 1 minute, and then pressed at 200 MPa for 1 minute. A 5 cm square plate-like body was prepared.
Next, the obtained plate-like body was supplied to a handy color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NR-3000”) and measured according to JIS K7105.

(5) 2000 ppm hydrogen chloride generation time 1 g of the obtained vinyl chloride resin is supplied to a test tube, sealed with a heat-resistant rubber stopper with a tube, and immersed in a 200 ° C. oil bath for 2/3 from the bottom and heated. To do. The gas generated from the test tube is collected with 100 ml of ion exchange water through the tube, and the pH change of the ion exchange water is measured every minute. The amount of hydrogen chloride generated is calculated from the difference from the pH of ion-exchanged water before the start of collection, and the time when the total amount of hydrogen chloride generated from the start of measurement reaches 2000 ppm is defined as 2000 ppm hydrogen chloride generation time. The unit is minutes.

(6) Preparation of vinyl chloride resin and vinyl chloride-vinylidene chloride copolymer plate test piece 100 parts by weight of the obtained vinyl chloride resin or vinyl chloride-vinylidene chloride copolymer, organotin stabilizer (Three-shared machine synthesis) 2 parts by weight of a trade name “STANNJF-10B” manufactured by the company and 0.5 parts by weight of a lubricant (trade name “Metablene P-710” manufactured by Mitsubishi Rayon Co., Ltd.) were stirred and mixed to obtain a resin composition.
The obtained resin composition was supplied to an 8-inch mixing roll (manufactured by Yasuda Seisakusho Co., Ltd.), wound at 170 ° C. and kneaded for 30 seconds to obtain a sheet-like material. And preheated at 180 ° C. for 2 minutes, then pressed at 200 MPa for 2 minutes, and cooled to obtain a plate-shaped test piece having a thickness of 3 mm.

(7) Preparation of chlorinated vinyl chloride resin plate test piece 100 parts by weight of the obtained chlorinated vinyl chloride resin, organotin stabilizer (trade name “KH-220” manufactured by Nitto Kasei Co., Ltd.) 2 parts by weight , 3 parts by weight of impact modifier (trade name “C-150S” manufactured by Mitsubishi Rayon Co., Ltd.) and 0.5 part by weight of lubricant (trade name “Metablene P-710” manufactured by Mitsubishi Rayon Co., Ltd.) I got a thing.
The obtained resin composition is supplied to an 8-inch mixing roll (manufactured by Yasuda Seisakusho Co., Ltd.), wound at 170 ° C. and kneaded for 30 seconds to obtain a sheet-like material, and the obtained sheet-like material is subjected to a press molding machine ( Toho Machinery Co., Ltd.) was preheated at 180 ° C. for 2 minutes, then pressed at 200 MPa for 2 minutes, and cooled to obtain a plate-like test piece having a thickness of 3 mm.

(8) 650 nm transmittance A plate-shaped test piece having a thickness of 3 mm and a 50 mm square was supplied to a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “U-3000”), and the transmittance at a wavelength of 650 nm was measured. . The unit is%.
(9) Haze A 3 mm thick, 50 mm square plate-shaped test piece was supplied to a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., trade name “NDH-2000”) and measured according to JIS K7136. The unit is%.

(10) Molded plate yellowness (YI)
A plate test piece having a thickness of 3 mm and a square of 50 mm was supplied to a handy color difference meter (trade name “NR-3000” manufactured by Nippon Denshoku Industries Co., Ltd.) and measured according to JIS K7105.
(11) Vicat softening temperature A 3 mm thick plate-like test piece was cut to create a test piece for measuring the Vicat softening temperature.
Measured according to K7206. A 1 kg weight was used for the measurement. The unit is ° C.

  As is clear from Tables 1 and 2, in the examples of the present invention, heat resistance is excellent, the occurrence of dehydrochlorination reaction during thermoforming is suppressed, low yellowing, and transparency is excellent. As a result, according to the vinyl chloride resin, a vinyl chloride resin molded article with little yellowing and excellent transparency was obtained.

The present invention can be used in any field where the use of a vinyl chloride resin is expected. In particular, it is useful in the field having high transparency, and is useful, for example, as a component of an optical system, specifically, an optical fiber, various lenses, and various optical devices.

Claims (11)

A (co) polymer obtained by polymerizing or copolymerizing a vinyl chloride monomer and / or a monomer copolymerizable with vinyl chloride, or a chlorinated product thereafter, and the titanium content of the (co) polymer or chlorinated product thereafter In the presence of 2,2-azobisisobutyronitrile and tributyltin hydride and measured by ¹³ C-NMR, the peak intensity based on the methylene hydrocarbon chain A vinyl chloride resin characterized in that the peak intensity of methyl branching generated at 18.5 to 22.5 ppm is 0.15 or less, when 100 is 100. A (co) polymer obtained by polymerizing or copolymerizing a vinyl chloride monomer and / or a monomer copolymerizable with vinyl chloride, or a chlorinated product thereafter, and the titanium content of the (co) polymer or chlorinated product thereafter Is 1.0 ppm or less, and the time until the total amount of hydrogen chloride generated from the start of heating reaches 2000 ppm under heating at 200 ° C. is 30 minutes or more.   A (co) polymer obtained by polymerizing or copolymerizing a vinyl chloride monomer and / or a monomer copolymerizable with vinyl chloride, or a chlorinated product thereafter, and the titanium content of the (co) polymer or chlorinated product thereafter Is a vinyl chloride resin characterized by having a yellowness YI of a plate-like body prepared by a powder press at 180 ° C. measured in accordance with JIS K7105 of 20 or less. The vinyl chloride resin according to claim 1 or 3, wherein the time until the total amount of generated hydrogen chloride reaches 2000 ppm under heating at 200 ° C is 30 minutes or more.   Further, the vinyl chloride resin according to claim 1 or 2, wherein the yellowness YI measured by a powder press at 180 ° C according to JIS K7105 is 20 or less.   The vinyl chloride resin according to any one of claims 1 to 5, wherein a zirconium content in the (co) polymer or a chlorinated product thereafter is 0.05 to 100 ppm.   The vinyl chloride resin according to any one of claims 1 to 6, wherein the aluminum content in the (co) polymer or chlorinated product thereafter is 0.1 to 300 ppm. Polymerization or copolymerization is represented by the general formula ZrX ¹ X ² X ³ X ⁴ (wherein X ¹ , X ² , X ³ , X ⁴ are halogen atoms, alkyl groups, alkoxy groups, substituted or unsubstituted aryl groups, substituted or The vinyl chloride resin according to any one of claims 1 to 7, which is carried out in the presence of a zirconium compound represented by an unsubstituted aryloxy group or the like. Polymerization or copolymerization may be represented by the general formula AlY ¹ Y ² Y ³ (wherein Y ¹ , Y ² and Y ³ are halogen atoms, alkyl groups, alkoxy groups, substituted or unsubstituted aryl groups, substituted or unsubstituted aryloxy groups. Etc.) The vinyl chloride resin according to any one of claims 1 to 8, which is carried out in the presence of an aluminum compound or an alkylaluminoxane represented by: X < ¹ > -X < ⁴ > is the same alkoxy group or aryloxy group, The vinyl chloride-type resin as described in any one of Claims 1-9.   A vinyl chloride resin molded article obtained by molding the vinyl chloride resin according to claim 1.