Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C08L27/06—Homopolymers or copolymers of vinyl chloride
• • 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
• • 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
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/34—Introducing sulfur atoms or sulfur-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
  • C08L27/22—Compositions 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; Compositions of derivatives of such polymers modified by chemical after-treatment
  • C08L27/24—Compositions 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; Compositions of derivatives of such polymers modified by chemical after-treatment halogenated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2201/00—Properties
  • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

• the present invention relates to a chlorinated vinyl chloride-based resin in which the obtained molded product has excellent heat cycle properties and weather resistance, and a molding resin composition and a molded product using the chlorinated vinyl chloride-based resin.
• Vinyl chloride resins are generally excellent in mechanical strength, weather resistance and chemical resistance. For this reason, vinyl chloride resins are processed into various molded products and are used in many fields.
• Patent Document 1 discloses a composition in which chlorinated polyvinyl chloride and a specific stabilizer are used in combination, and discloses that such a resin can withstand thermal stress and mechanical stress during processing. Has been done.
• a molded product for example, a hot water supply pipe
• a chlorinated vinyl chloride resin as described in Patent Document 1 is desorbed by sunlight when it is installed outdoors for a long period of time. Therefore, there is a problem that the deterioration of the molded product is remarkably observed. Further, since the obtained molded product is installed outdoors for a long period of time or used for flowing hot water into the pipe, there is a problem that the molded product is bent due to an increase in the outside air temperature or the temperature inside the pipe.
• An object of the present invention is to provide a chlorinated vinyl chloride resin.
• the present invention is the ratio (A / B) of the peak intensity A observed in the range of 300 to 340 cm -1 to the peak intensity B observed in the range of 1450 to 1550 cm -1 in the imaging Raman measurement by Raman spectroscopy. It is a chlorinated vinyl chloride resin having an average value of 3.5 to 40. The present invention will be described in detail below.
• Chlorinated vinyl chloride resin of the present invention in an imaging Raman measurement by Raman spectroscopy under the conditions described above, 1450 ⁇ 1550 cm - to the peak intensity B observed in the range of, are observed in the range of 300 ⁇ 340 cm -1
• the average value of the ratio (A / B) of the peak intensities A is 3.5 to 40.
• the average value of A / B is such that the preferable lower limit is 3.6, the more preferable lower limit is 3.8, the further preferable lower limit is 4.0, the further preferable lower limit is 5.0, and the particularly preferable lower limit is 6.0, particularly.
• the preferred lower limit is 8.0 and the very preferred lower limit is 10.0.
• the average value of A / B is such that the preferable upper limit is 35, the more preferable upper limit is 30, the further preferable upper limit is 25, the more preferable upper limit is 23, the particularly preferable upper limit is 20, and the very preferable upper limit is 15.
• the average value of the ratio (A / B) of the peak intensity A to the peak intensity B can be calculated by measuring the Raman spectrum using a microscopic Raman spectroscopic analyzer.
• the method for preparing the sample is not particularly limited, but it is preferable to obtain a Raman spectrum of only the chlorinated vinyl chloride resin. Specifically, a sample obtained by adding an acrylic UV curable resin to a chlorinated vinyl chloride resin, irradiating with ultraviolet rays to cure the acrylic UV curable resin, and then embedding the sample with an epoxy resin is used.
• a method of performing imaging Raman measurement [THF precipitation method] and the like can be mentioned.
• the imaging Raman spectrum performs baseline correction by linear approximation, measured 1450 and peak intensity B observed in the range of ⁇ 1550 cm -1, and the peak intensity A observed in the range of 300 ⁇ 340 cm -1 Then, A / B is calculated, and the measurement can be performed by calculating the average value for the peak intensities of 10,000 points.
• the average value of A / B can be measured using, for example, inVia Quantor (manufactured by Renishaw). Further, it is preferable that the imaging Raman measurement is performed after heating.
• the heating temperature is preferably 100 ° C. or higher.
• the heating time is preferably 5 minutes or more.
• a sample heated at 150 ° C. for 10 minutes using the above THF precipitation method is preferable, and when measuring a molded product, an unheated sample using the THF precipitation method is used. It is preferable to measure.
• the peak intensity A observed in the range of 300 to 340 cm -1 is compared with the peak intensity B observed in the range of 1450 to 1550 cm -1 in the imaging Raman measurement by Raman spectroscopy.
• the standard deviation of the ratio (A / B) of is preferably 0.01 to 10.
• Vinyl chloride resin (PVC) which is a raw material for chlorinated vinyl chloride resin, has a particle size distribution, and there are variations in void ratio, bulk relative density, etc., so the chlorinated state becomes non-uniform and the degree of chlorination is distributed. Will vary. In the present invention, it can be said that the chlorinated state is uniform when the standard deviation of the A / B is within the above range.
• the standard deviation of the ratio (A / B) of the peak intensity A to the peak intensity B can be calculated based on, for example, the peak intensity ratio obtained in the imaging Raman measurement.
• the standard deviation of the A / B is 0.02 for a more preferable lower limit, 0.05 for a more preferable lower limit, 0.07 for a further preferable lower limit, and 0.10 for a particularly preferable lower limit.
• the standard deviation of A / B is such that the more preferable upper limit is 8.0, the further preferable upper limit is 7.0, the further preferable upper limit is 6.0, the particularly preferable upper limit is 5.0, and the particularly preferable upper limit is 4. 0, a very preferred upper limit is 3.0, for example 2.0 or higher.
• the average value of the A / B and the standard deviation of the A / B satisfy the relationship of the following formula (1). 0.500 ⁇ [mean value of A / B] + [standard deviation of A / B] 1/2 ⁇ 50 (1)
• the more preferable lower limit of the formula (1) is 1.0
• the further preferable lower limit is 3.0
• the further preferable lower limit is 4.0
• the particularly preferable lower limit is 5.0
• the more preferable upper limit is 45.
• An even more preferred upper limit is 40, an even more preferred upper limit is 35, and a particularly preferred upper limit is 30.
• the chlorinated vinyl chloride resin of the present invention has an average value (B / C) of the ratio (B / C) of the peak intensity B to the peak intensity C observed in the range of 1400 to 1450 cm -1 in Raman measurement by Raman spectroscopy. It is preferably 01 to 30.
• the average value of the B / C is within the above range, the heat resistance of the chlorinated vinyl chloride resin is improved and heat shrinkage is suppressed, so that the heat cycle property is good and there is little heat deterioration due to repetition. It is possible to obtain a molded product having a small rate of change in the amount of bending before and after heating.
• the average value of the B / C has a more preferable lower limit of 0.3, a further preferable lower limit of 2.0, and a further preferable lower limit of 10. Further, the average value of the B / C has a more preferable upper limit of 20, a further preferable upper limit of 15, and a further preferable upper limit of 10.
• the chlorinated vinyl chloride resin of the present invention preferably has the structural units (a) to (c) represented by the following formulas (a) to (c). Further, the ratio of the structural unit (a) is 5.0 mol% or more and the ratio of the structural unit (b) is 40.0 with respect to the total number of moles of the following structural units (a), (b) and (c). It is preferable that the molar% or less and the ratio of the constituent unit (c) are 55.0 mol% or less.
• Such a chlorinated vinyl chloride resin has improved heat resistance of the characteristics of the chlorinated vinyl chloride resin, improved heat shrinkage, good heat cycle property, and reduced thermal deterioration due to repetition.
• the ratio of the constituent unit (a) to the total number of moles of the constituent units (a), (b) and (c) is 30.0 mol% or more. More preferably, it is more preferably 35.0 mol% or more, more preferably 90.0 mol% or less, and further preferably 60.0 mol% or less. Further, the ratio of the structural unit (b) is preferably 5.0 mol% or more with respect to the total number of moles of the structural units (a), (b) and (c), and 15.0 mol% or more. It is more preferably 30.0 mol% or less, and further preferably 25.0 mol% or less.
• the ratio of the structural unit (c) to the total number of moles of the structural units (a), (b) and (c) is preferably 5.0 mol% or more, preferably 25.0 mol% or more. It is more preferably 55.0 mol% or less, and more preferably 40.0 mol% or less.
• the molar ratios of the constituent units (a), (b) and (c) of the chlorinated vinyl chloride resin of the present invention reflect the site where chlorine is introduced when the vinyl chloride resin (PVC) is chlorinated. It was done.
• the PVC before chlorination is in a state where the constituent unit (a) is 100 mol% and the constituent units (b) and (c) are 0 mol%, but the constituent unit (a) decreases with chlorination, and the constituent unit (a) decreases.
• the building blocks (b) and (c) increase.
• the chlorinated state becomes non-uniform. Becomes larger.
• the uniformity of the chlorinated vinyl chloride resin is increased, and the heat resistance and heat shrinkage are improved. It is possible to obtain a molded product having a good heat cycle property and a small rate of change in the amount of bending before and after heating.
• the molar ratios of the structural units (a), (b) and (c) of the chlorinated vinyl chloride resin of the present invention can be measured by molecular structure analysis using NMR. NMR analysis is performed by R. A. Komoroski, R.M. G. Parker, J.M. P. It can be carried out according to the method described in Shocker, Macromolecules, 1985, 18, 1257-1265.
• the chlorinated vinyl chloride resin of the present invention may contain other structural units other than the above-mentioned structural units (a), (b) and (c) as long as the effects of the present invention are not impaired.
• the content of the other structural units is preferably 0% by mass or more, and preferably less than 10% by mass in the chlorinated vinyl chloride resin.
• Examples of the other structural unit include a structural unit having a substituent containing sulfur.
• the chlorinated vinyl chloride resin of the present invention when the sulfur content in the chlorinated vinyl chloride resin shown below is 0% by mass or more, sulfur is present in the resin, and the sulfur is bonded to the resin. Therefore, it can be seen that the chlorinated vinyl chloride-based resin of the present invention contains a structural unit having a sulfur-containing substituent.
• the sulfur-containing substituent include a substituent derived from a sulfur compound.
• Examples of the sulfur compound include compounds described later. Among them, at least one thioglycolic acid-based compound selected from the group consisting of thioglycolic acid and thioglycolic acid esters is preferable.
• Examples of the structural unit having a substituent containing sulfur include the structural unit (d) represented by the following formula (d).
• R in the structural unit (d) a group to which at least one selected from the group consisting of an alkylene group, an ester group, an alkyl group and a thiol group is bonded is preferable, and it is composed of an alkylene group, an ester group and an alkyl group. More preferably, it is a group to which at least one selected from the group is bound.
• the sulfur content in the chlorinated vinyl chloride resin of the present invention is preferably 10 mass ppm or more and 1000 mass ppm or less. It is more preferably 15 mass ppm or more, 800 mass ppm or less, and further preferably 500 mass ppm or less. Even more preferably, it is 200 mass ppm or less.
• the sulfur content in the chlorinated vinyl chloride resin can be detected by quantitative analysis using IC (ion chromatography). Specifically, a chlorinated vinyl chloride resin is dissolved in THF, the insoluble part is separated and filtered by a centrifuge, an excess amount of methanol is added and reprecipitated, and the mixture is separated by suction filtration and used in a vacuum dryer. The sample obtained by drying at 80 ° C.
• the chlorinated vinyl chloride resin of the present invention preferably has an added chlorinated amount of 1.0 to 16.0% by mass.
• the amount of added chlorination is more preferably 3.2% by mass or more, further preferably 6.2% by mass or more, more preferably 15.2% by mass or less, and 12.2% by mass. It is more preferably% or less.
• the chlorine content of the vinyl chloride resin is usually 56.8% by mass, but the added chlorine content means the introduction ratio of chlorine to the vinyl chloride resin, and is described in JIS K 7229. It can be measured by the method.
• the added chlorinated amount and the average value of A / B satisfy the following relationship. 0.01 ⁇ [Additional chlorination amount (% by mass)] / [Average value of A / B] ⁇ 30 (2)
• the uniformity of the chlorinated vinyl chloride resin is increased, the heat resistance and heat shrinkage are improved, the heat cycle property is good, and the rate of change in the amount of deflection before and after heating is small. can.
• the more preferable lower limit of the above formula (2) is 0.05, the further preferable lower limit is 0.1, the further preferable lower limit is 0.2, the more preferable upper limit is 25, and the further preferable upper limit is 20.
• An even more preferred upper limit is 15, a particularly preferred upper limit is 10, a particularly preferred upper limit is 5, and a very preferred upper limit is 3, for example 1.
• the degree of polymerization of the chlorinated vinyl chloride resin of the present invention is preferably 100 or more, more preferably 400 or more, further preferably 500 or more, preferably 2000 or less, and 1500 or less. Is more preferable. By setting the degree of polymerization within the above range, it is possible to achieve both fluidity at the time of injection and strength of the molded product.
• the chlorinated vinyl chloride resin of the present invention is a resin obtained by chlorinating a vinyl chloride resin.
• the vinyl chloride-based resin includes a vinyl chloride homopolymer, a copolymer of a monomer having an unsaturated bond copolymerizable with a vinyl chloride monomer and a vinyl chloride monomer, and a vinyl chloride monomer graft-copolymerized with the polymer.
• a graft copolymer or the like can be used. These polymers may be used alone or in combination of two or more.
• the vinyl chloride resin is a copolymer of a vinyl chloride monomer and a monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer, or a graft copolymer obtained by graft-copolymerizing a vinyl chloride monomer with the polymer.
• the content of the component derived from the vinyl chloride monomer in the vinyl chloride resin is preferably 90% by mass or more.
• the content of the component derived from the vinyl chloride monomer in the vinyl chloride resin is preferably 100% by mass or less.
• Examples of the monomer having an unsaturated bond copolymerizable with the vinyl chloride monomer include ⁇ -olefins, vinyl esters, vinyl ethers, (meth) acrylic acid esters, aromatic vinyls, vinyl halides, and the like. Examples thereof include N-substituted maleimides, and one or more of these are used.
• Examples of the ⁇ -olefins include ethylene, propylene and butylene
• examples of the vinyl esters include vinyl acetate and vinyl propionate
• examples of the vinyl ethers include butyl vinyl ether and cetyl vinyl ether. Be done.
• Examples of the (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, butyl acrylate, and phenyl methacrylate, and examples of the aromatic vinyls include styrene and ⁇ -methylstyrene.
• examples of the vinyl halides include vinylidene chloride and vinylidene fluoride
• examples of the N-substituted maleimides include N-phenylmaleimide and N-cyclohexylmaleimide. Of these, ethylene and vinyl acetate are preferable.
• the polymer for graft-copolymerizing vinyl chloride is not particularly limited as long as it is for graft-polymerizing vinyl chloride.
• examples of such a polymer include ethylene-vinyl acetate copolymer, ethylene-vinyl acetate-carbon monoxide copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate-carbon monoxide copolymer, and the like.
• Examples thereof include ethylene-methylmethacrylate copolymers and ethylene-propylene copolymers.
• examples thereof include acrylonitrile-butadiene copolymer, polyurethane, chlorinated polyethylene, chlorinated polypropylene and the like, and these may be used alone or in combination of two or more.
• the polymerization method of the vinyl chloride resin is not particularly limited, and conventionally known water suspension polymerization, bulk polymerization, solution polymerization, emulsion polymerization and the like can be used.
• a suspension is prepared by suspending the vinyl chloride resin in an aqueous medium in a reaction vessel, and chlorine is introduced into the reaction vessel.
• a method of chlorinating the vinyl chloride resin by heating the suspension can be mentioned.
• the chlorinated vinyl chloride resin in which the ratio (A / B) of the peak intensity A to the peak intensity B of the present invention is within a predetermined range is the amount of added chlorinated vinyl chloride resin and the constituent unit (a). ), (B) and (c), the ratio of the constituent unit (b) to the total number of moles is adjusted, the sulfur compound is added after the chlorination step, and the amount of the sulfur compound added is adjusted. It can be produced by controlling the amount of chlorine consumed in the chlorination step, the drying temperature in the drying step, and the drying time.
• reaction vessel for example, a commonly used vessel such as a stainless steel reaction vessel with a glass lining or a titanium reaction vessel can be used.
• the method for preparing a suspension by suspending the vinyl chloride resin in an aqueous medium is not particularly limited, and a cake-like PVC obtained by demonomerizing the polymerized PVC may be used or dried. May be suspended again in an aqueous medium. Further, a suspension from which substances unfavorable for the chlorination reaction have been removed may be used from the polymerization system, but it is preferable to use a cake-like resin obtained by demonomerizing PVC after polymerization.
• aqueous medium for example, pure water subjected to ion exchange treatment can be used.
• the amount of the aqueous medium is not particularly limited, but is generally preferably 150 to 400 parts by mass with respect to 100 parts by mass of PVC.
• the chlorine introduced into the reaction vessel may be either liquid chlorine or gaseous chlorine. It is efficient to use liquid chlorine because a large amount of chlorine can be charged in a short time. Chlorine may be added during the reaction to regulate pressure or replenish chlorine. At this time, in addition to liquid chlorine, gaseous chlorine can be appropriately blown. It is preferable to use chlorine after purging 5 to 10% by mass of cylinder chlorine.
• the reaction pressure (gauge pressure in the reaction vessel) in the chlorination step is not particularly limited, but is preferably in the range of 0 to 2 MPa because the higher the chlorine pressure, the easier it is for chlorine to permeate the inside of the PVC particles.
• the method of chlorinating PVC in the suspended state is not particularly limited, and examples thereof include a method of accelerating chlorination by exciting PVC binding and chlorine with thermal energy (hereinafter referred to as thermal chlorination). Be done.
• the heating method for chlorination by thermal energy is not particularly limited, and for example, heating by an external jacket method from the reactor wall is effective. In the method of chlorinating by heat, a more uniform chlorination reaction becomes possible, and a highly uniform CPVC can be obtained. Further, when light energy such as ultraviolet rays is used, a device capable of irradiating light energy such as ultraviolet irradiation under high temperature and high pressure conditions is required.
• the heating temperature in the thermal chlorination is preferably in the range of 40 to 160 ° C. If the temperature is too low, the chlorination rate will decrease. If the temperature is too high, a deHCl reaction will occur in parallel with the chlorination reaction and the resulting CPVC will be colored.
• the heating temperature is more preferably in the range of 50 to 150 ° C.
• the heating method is not particularly limited, and for example, heating can be performed from the reaction vessel wall by an outer jacket method.
• the added chlorinated amount and the average value of A / B satisfy the relationship of the following formula (3).
• the more preferable lower limit of the above formula (3) is 0.001, the further preferable lower limit is 0.01, the further preferable lower limit is 0.05, the more preferable upper limit is 15, and the further preferable upper limit is 10.
• An even more preferred upper limit is 8, a particularly preferred upper limit is 5, a particularly preferred upper limit is 3, and a very preferred upper limit is 2, for example 1.
• the rate of chlorination can be improved.
• Hydrogen peroxide is preferably added in an amount of 5 to 500 ppm with respect to PVC every 1 hour of reaction time. If the amount added is too small, the effect of improving the rate of chlorination cannot be obtained. If the amount added is too large, the thermal stability of CPVC will decrease.
• the chlorination rate is improved, so that the heating temperature can be made relatively low. For example, it may be in the range of 65 to 110 ° C.
• chlorination after the time when it reaches 5% by mass before the final added chlorination amount is performed in a chlorine consumption rate of 0.010 to 0.015 kg / PVC-Kg / 5 min, and further. It is preferable that the chlorine consumption rate is in the range of 0.005 to 0.010 kg / PVC-Kg ⁇ 5 min after the time when it reaches 3% by mass before the final added chlorine amount.
• the chlorine consumption rate refers to the amount of chlorine consumed for 5 minutes per 1 kg of raw material PVC.
• the average chlorine consumption rate in the chlorination step is preferably in the range of 0.01 to 0.1 kg / PVC-Kg / 5 min. Further, the chlorine consumption in the chlorination step is preferably in the range of 0.50 to 8.00 kg, more preferably in the range of 2.80 to 7.00 kg, with respect to 50 kg of the vinyl chloride resin.
• the concentration of chlorine introduced into the reaction vessel is preferably 99.5% or more.
• a sulfur compound after performing the chlorination step.
• a neutralization step a washing step, a dehydration step and a drying step are carried out in order.
• the step of adding the sulfur compound is preferably performed during the dehydration step or after the dehydration step.
• the total amount of the sulfur compound may be added at one time, or may be added in a plurality of times. Alternatively, it may be added as it is, or it may be diluted with a solvent such as water and added.
• the sulfur compound When the above sulfur compound is added, the sulfur compound is added in place of chlorine desorbed from the main chain of the chlorinated vinyl chloride resin in the subsequent drying step, so that the amount of dehydrochloric acid dehydrochlorated during molding is reduced. Thermal stability is improved.
• the sulfur compound is preferably an organic sulfur compound, and specific examples thereof include thioglycolic acid-based compounds, thiourea, thioglycerin, thioacetic acid, potassium thioacetate, thiodiacetic acid, thiosemicarbazide, and thioacetamide. .. Of these, at least one thioglycolic acid-based compound selected from the group consisting of thioglycolic acid and thioglycolic acid esters is more preferable.
• the thioglycolic acid includes not only thioglycolic acid but also thioglycolic acid salts such as metal salts, ammonium salts and amine salts of thioglycolic acid.
• thioglycolate include sodium thioglycolate, calcium thioglycolate, ammonium thioglycolate, methylamine thioglycolate, ethylamine thioglycolate, monoethanolamine thioglycolate, diethanolamine thioglycolate, and trithioglycolate. Examples thereof include ethanolamine.
• ester of thioglycolic acid examples include methyl thioglycolate, ethyl thioglycolate, n-butyl thioglycolic acid, t-butyl thioglycolic acid, 2-ethylhexyl thioglycolate, octyl thioglycolate, and thioglycolic acid.
• alkyl esters of thioglycolic acid such as isooctyl, decyl thioglycolate, and dodecyl thioglycolate.
• an ester with a hydrocarbon having an alkoxy group such as methoxybutyl thioglycolate may be used.
• a hydrocarbon having an alkoxy group such as methoxybutyl thioglycolate
• 2-ethylhexyl thioglycolate and isooctyl thioglycolate are preferable.
• alcandiol dithioglycolate which is a thioglycolic acid ester of alcandiol
• alcanpolyol polythioglycolate which is a thioglycolic acid ester of alcan polyol
• thioglycolic acid ester of polyalkylene glycol polyalkylene glycol
• alkanediol dithioglycolate examples include ethylene glycol bisthioglycolate, butanediol bisthioglycolate, neopentyl glycol bisthioglycolate, and hexanediol bisthioglycolate. Of these, butanediol bisthioglycolate is preferable.
• alkane polyol polythioglycolate examples include trimethylolpropane tristhioglycolate, pentaerythritol tristhioglycolate, pentaerythritol tetrakisthioglycolate, and dipentaerythritol hexathioglycolate.
• examples of the polyalkylene glycol dithioglycolate include diethylene glycol dithioglycolate.
• the thioglycolic acid-based compound is preferably a compound represented by HSCH 2 COOR (R represents H or an alkyl group). Further, the alkyl group preferably has 1 to 8 carbon atoms.
• the amount of the sulfur compound added is preferably 0.001 part by mass and a preferable upper limit of 15 parts by mass with respect to 100 parts by mass of the chlorinated vinyl chloride resin.
• the chlorinated vinyl chloride resin of the present invention can be obtained.
• a more preferable upper limit is 10 parts by mass, a further preferable upper limit is 8 parts by mass, and a further preferable upper limit is 0.5 parts by mass.
• a more preferable lower limit is 0.01 parts by mass, and a more preferable lower limit is 0.05 parts by mass.
• the method for adding the sulfur compound is not particularly limited, but it is preferable to add the sulfur compound at an addition rate of 20 to 500 g / min.
• the drying temperature after the addition of the sulfur compound is preferably 60 to 120 ° C. Further, the drying time is preferably 6 to 48 hours. When the drying temperature and the drying time are within the above ranges, the addition reaction of the sulfur compound is promoted. Examples of the above-mentioned drying method include static drying, hot air drying, blast drying, far-infrared heat drying, vacuum vacuum drying and the like.
• a molded product can be produced by molding a molding resin composition containing the chlorinated vinyl chloride resin of the present invention.
• the molding resin composition containing the chlorinated vinyl chloride resin of the present invention is also one of the present inventions.
• a preferable lower limit is 65% by mass
• a more preferable lower limit is 70% by mass
• a preferable upper limit is 96% by mass
• a more preferable upper limit is 93. It is mass%.
• the molding resin composition of the present invention is, if necessary, a stabilizer, a lubricant, a processing aid, an impact modifier, a heat improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, and a thermoplastic. Additives such as elastomers and pigments may be added.
• the stabilizer is not particularly limited, and examples thereof include a heat stabilizer and a heat stabilization aid.
• the heat stabilizer is not particularly limited, and examples thereof include an organotin-based stabilizer, a lead-based stabilizer, a calcium-zinc-based stabilizer; a barium-zinc-based stabilizer; and a barium-cadmium-based stabilizer.
• organic tin stabilizer examples include dibutyl tin mercapto, dioctyl tin mercapto, dimethyl tin mercapto, dibutyl tin mercapto, dibutyl tin malate, dibutyl tin malate polymer, dioctyl tin malate, dioctyl tin malate polymer, and dibutyl tin laurate. , Dibutyltin laurate polymer and the like.
• the lead-based stabilizer examples include lead stearate, dibasic lead phosphite, and tribasic lead sulfate. These may be used alone or in combination of two or more.
• the heat stabilizing aid is not particularly limited, and examples thereof include epoxidized soybean oil, phosphoric acid ester, polyol, hydrotalcite, and zeolite. These may be used alone or in combination of two or more.
• the lubricant examples include an internal lubricant and an external lubricant.
• the internal lubricant is used for the purpose of lowering the flow viscosity of the molten resin during molding and preventing frictional heat generation.
• the internal lubricant is not particularly limited, and examples thereof include butyl stearate, lauryl alcohol, stearyl alcohol, epoxy soybean oil, glycerin monostearate, stearic acid, and bisamide. These may be used alone or in combination of two or more.
• the external lubricant is used for the purpose of enhancing the sliding effect between the molten resin and the metal surface during the molding process.
• the external lubricant is not particularly limited, and examples thereof include paraffin wax, polyolefin wax, ester wax, and montanic acid wax. These may be used alone or in combination of two or more.
• the processing aid is not particularly limited, and examples thereof include an acrylic processing aid such as an alkyl acrylate-alkyl methacrylate copolymer having a mass average molecular weight of 100,000 to 2 million.
• the acrylic processing aid is not particularly limited, and examples thereof include an n-butyl acrylate-methyl methacrylate copolymer and a 2-ethylhexyl acrylate-methyl methacrylate-butyl methacrylate copolymer. These may be used alone or in combination of two or more.
• the impact modifier is not particularly limited, and examples thereof include methyl methacrylate-butadiene-styrene copolymer (MBS), chlorinated polyethylene, and acrylic rubber.
• MFS methyl methacrylate-butadiene-styrene copolymer
• the heat resistance improving agent is not particularly limited, and examples thereof include ⁇ -methylstyrene-based resins and N-phenylmaleimide-based resins.
• the antioxidant is not particularly limited, and examples thereof include a phenolic antioxidant and the like.
• the light stabilizer is not particularly limited, and examples thereof include a hindered amine-based light stabilizer and the like.
• the ultraviolet absorber is not particularly limited, and examples thereof include ultraviolet absorbers such as salicylic acid ester type, benzophenone type, benzotriazole type, and cyanoacrylate type.
• the filler is not particularly limited, and examples thereof include calcium carbonate and talc.
• the pigment is not particularly limited, and for example, organic pigments such as azo-based, phthalocyanine-based, slene-based, and dye lake-based; oxide-based, molybdenum chromate-based, sulfide / serene-based, ferrocyanine-based, and the like. Examples include inorganic pigments.
• a molded product molded from the molding resin composition of the present invention is provided.
• Such a molded product is also one of the present inventions.
• the present invention is a molded product, by extracting the chlorinated vinyl chloride resin in the molded product with an organic solvent or the like, 300 to 340 cm with respect to the peak intensity B observed in the range of 1450 to 1550 cm -1.
• the average value of the ratio (A / B) of the peak intensities A observed in the range of -1 can be measured.
• any conventionally known molding method may be adopted, and examples thereof include an extrusion molding method and an injection molding method.
• the molded product of the present invention has excellent thermal stability and is in a good appearance, it can be suitably used for applications such as building members, pipework equipment, and housing materials.
• the hydrogen tank is becoming smaller and lighter, and if the number of locations where the hydrogen tank is placed increases, it may not be possible to identify the part that may be in contact with the flame. .. Therefore, it is necessary to take measures against heating and ignition of the battery pack and the cover that covers the entire hydrogen tank.
• the molded product is a member for a transport aircraft and a battery device. It can be suitably used as a member for.
• Examples of the above-mentioned transport aircraft include automobiles such as gasoline vehicles, hybrid vehicles, electric vehicles and fuel cell vehicles, motorcycles such as gasoline bikes, hybrid bikes and electric bikes, bicycles such as electrically assisted bicycles, railway vehicles, ships and aircraft. Be done.
• examples of the member for the transport aircraft include a mechanical member, an interior member, an exterior member, glass, a light cover, and the like.
• examples of the mechanical member include a cooling pipe, an airbag cover, an air duct, a heater unit, and the like.
• Examples of the interior members include ceilings, instrumental panels, console boxes, armrests, seatbelt buckles, switches, door trims, and the like.
• Examples of the exterior member include an emblem, a license plate housing, a bumper core material, an undercover, and the like.
• Battery devices include primary batteries such as nickel manganese batteries, lithium batteries, and air zinc batteries, secondary batteries such as nickel hydrogen batteries, lithium ion batteries, and lead storage batteries, silicon-based solar cells, dye-sensitized solar cells, and perovskite-type sun. Examples thereof include solar cells such as batteries, solid polymer type fuel cells, alkaline type fuel cells, phosphoric acid type fuel cells, fuel cells such as solid oxide type fuel cells, and the like. Examples of the battery device member include a battery case, a water jacket for cooling the battery, a hydrogen tank cover, a connector, an insulating sheet and the like.
• the molded product molded from the present invention preferably has a dimensional change rate of 0.01 to 2% before and after the heat cycle test.
• the dimensional change rate before and after the heat cycle test was measured by repeating a cycle in which a test piece having a width of 13 mm, a length of 127 mm, and a thickness of 3.2 mm was left at 100 ° C. for 30 minutes five times. It can be measured by calculating the dimensional change rate from before the heat cycle to after the heat cycle.
• the molded product molded from the present invention preferably has a bending amount change [before heating-after heating] of 0.01 to 1 mm before and after heating.
• a test piece having a width of 13 mm, a length of 127 mm, and a thickness of 3.2 mm is used and heated by a method conforming to JIS K7195 (however, heating temperature: 90 ° C., heating time: 30 minutes). This is done by measuring the amount of deflection and calculating the change in the amount of deflection before and after heating.
• the present invention it is possible to provide a chlorinated vinyl chloride-based resin in which the obtained molded body has excellent heat cycle property and weather resistance, and a molded body using the chlorinated vinyl chloride-based resin. Further, according to the present invention, the obtained molded product can maintain the color tone for a long period of time.
• Example 1 130 kg of ion-exchanged water and 50 kg of vinyl chloride resin having an average degree of polymerization of 1000 are placed in a glass-lined reaction vessel having an internal volume of 300 L, and the mixture is stirred to disperse the vinyl chloride resin in water and suspended in water. The inside was heated to raise the temperature of the aqueous suspension to 140 ° C. Next, after depressurizing the inside of the reaction vessel to remove oxygen (oxygen content 100 ppm), chlorine (oxygen content 50 ppm) was introduced so that the chlorine partial pressure became 0.40 MPa while stirring, and thermal chlorination was started. bottom. After that, the chlorination temperature was maintained at 140 ° C.
• chlorinated vinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, and centrifuged (Tanabe Iron Works Co., Ltd.). , O-15 type) and dehydrated for 3 minutes.
• 0.05 kg of 2-ethylhexyl thioglycolate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• sulfur compound was dehydrated to 50 kg of chlorinated vinyl chloride resin at 200 g / min. Was added in.
• chlorinated vinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, and centrifuged (Tanabe Iron Works Co., Ltd.). , O-15 type) and dehydrated for 3 minutes. Then, it was allowed to stand and dried at a drying temperature of 90 degreeC for 12 hours to obtain a hot chlorinated powdery chlorinated vinyl chloride resin (additional chlorination amount was 9.5% by mass).
• Examples 2 to 7, Comparative Examples 4 to 6 A powdery chlorinated vinyl chloride resin was added in the same manner as in Example 1 except that the sulfur compounds shown in Table 1 were added in the amounts shown and dried at the chlorine consumption, drying temperature, and drying time shown in Table 1.
• Examples 8 to 9, Comparative Examples 7 to 8) Using the vinyl chloride resin having the average degree of polymerization shown in Table 1, the sulfur compound was added in the amount shown, and the mixture was dried in the chlorine consumption, drying temperature, and drying time shown in Table 1 in the same manner as in Example 1. , A powdered chlorinated vinyl chloride resin was obtained. Then, 4.0 parts by mass of the impact-resistant modifier was added to 100 parts by mass of the obtained chlorinated vinyl chloride resin. Further, 0.5 parts by mass of a heat stabilizer was added and mixed. As the impact-resistant modifier, Kaneka B-564 (Methylmethacrylate-butadiene-styrene copolymer manufactured by Kaneka Corporation) was used.
• Kaneka B-564 Metalmethacrylate-butadiene-styrene copolymer manufactured by Kaneka Corporation
• the obtained chlorinated vinyl chloride resin composition is supplied to a twin-screw non-directional conical extruder (manufactured by Nagata Seisakusho Co., Ltd., SLM-50) having a diameter of 50 mm, and has an outer diameter of 26.7 mm and a wall thickness at a resin temperature of 200 ° C.
• SLM-50 twin-screw non-directional conical extruder
• Example 10 Using the vinyl chloride resin having the average degree of polymerization shown in Table 1, a powdery chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the sulfur compound was added in the stated amount. Then, 5.0 parts by mass of the impact resistance modifier was added to 100 parts by mass of the obtained chlorinated vinyl chloride resin. Further, 3.0 parts by mass of a heat stabilizer was added and mixed.
• the impact-resistant modifier Kaneka M-511 (Methylmethacrylate-butadiene-styrene copolymer manufactured by Kaneka Corporation) was used.
• the obtained chlorinated vinyl chloride resin composition was supplied to a twin-screw non-directional conical extruder (manufactured by Nagata Seisakusho Co., Ltd., OSC-30) having a diameter of 30 mm, and pellets were prepared at a resin temperature of 190 ° C.
• a twin-screw non-directional conical extruder manufactured by Nagata Seisakusho Co., Ltd., OSC-30
• pellets were prepared at a resin temperature of 190 ° C.
• a sample was prepared by placing the obtained resin in a vacuum dryer (VOS-451SD, manufactured by Tokyo Rika Kikai Co., Ltd.) and drying at 80 ° C. for 24 hours. Then, a sample heated at 150 ° C. for 10 minutes in a gear oven (CO-O2 manufactured by Toyo Seiki Seisakusho Co., Ltd.) was measured for Raman spectrum using a microscopic Raman spectroscope (inVia Quantor, manufactured by Renishaw Co., Ltd.).
• the obtained resin was placed in a vacuum dryer (VOS-451SD, manufactured by Tokyo Rika Kikai Co., Ltd.) and dried at 80 ° C. for 24 hours, and the Raman spectrum was measured using a sample.
• VS-451SD manufactured by Tokyo Rika Kikai Co., Ltd.
• the spectrum of the resin sheet is measured at intervals of 5 ⁇ m in the x direction and 5 ⁇ m in the y direction with respect to a region of 500 ⁇ m ⁇ 500 ⁇ m under the conditions of an objective lens of 100 times and an excitation wavelength of 532 nm.
• a Raman spectrum was obtained for 10201 points in the cross section.
• the ratio of peak intensity A to peak intensity B (A / B) was calculated, and the average value and standard deviation of A / B were calculated.
• the region of the acrylic resin was excluded and only the region of the chlorinated vinyl chloride resin was adopted.
• the obtained chlorinated vinyl chloride resin composition was kneaded with an 8-inch roll (manufactured by Yasuda Seiki Co., Ltd .: NO.191-TM) at a temperature of 200 ° C. for 3 minutes, and the obtained roll sheet was heated and cooled by a heating and cooling press (Kodaira).
• a plate having a thickness of 3.2 mm was prepared by pressing at a temperature of 200 ° C. and a pressure of 20 MPa (preheating 3 minutes, pressurization 4 minutes) using PA-40E / 40C manufactured by Mfg. Co., Ltd. Then, by cutting with an automatic cutting machine, a test piece having a width of 13 mm, a length of 127 mm, and a thickness of 3.2 mm was produced.
• Heat cycle test The obtained test piece was placed in a tank at 23 ° C., and the dimensions (dimensions before heat cycle) were measured. Then, the cycle of leaving at 100 ° C. for 30 minutes, then cooling the inside of the tank to 23 ° C. and leaving for 30 minutes was repeated 5 times. The dimensions (dimensions after the heat cycle) after being left at 23 ° C. for 30 minutes for the fifth time were measured, and the dimensional change rate from before the heat cycle to after the heat cycle was calculated.
• the amount of deflection before and after heating was calculated by a method conforming to JIS K7195 except for the heating temperature and heating time. Specifically, the method shown below was used. One end of the obtained test piece was sandwiched from above and below on the test piece holding table and fixed in a cantilever manner. Next, the test piece holding table was placed in a gear oven (CO-O2 manufactured by Toyo Seiki Seisakusho Co., Ltd.) and left at 90 ° C. for 30 minutes for heating. After being left to stand, the test piece was left to stand at a temperature of 23 ° C.
• CO-O2 manufactured by Toyo Seiki Seisakusho Co., Ltd.
• a chlorinated vinyl chloride-based resin in which the obtained molded product has excellent heat cycle properties and weather resistance, and a molding resin composition and a molded product using the chlorinated vinyl chloride-based resin. can.

Landscapes

• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)

Priority Applications (4)

Applications Claiming Priority (2)

Publications (1)

Family

ID=77930010

Family Applications (1)

Country Status (4)

Citations (2)

Family Cites Families (2)

• 2021
  • 2021-03-29 US US17/912,185 patent/US12486392B2/en active Active
  • 2021-03-29 KR KR1020227037248A patent/KR20220162731A/ko active Pending
  • 2021-03-29 WO PCT/JP2021/013357 patent/WO2021200848A1/ja not_active Ceased
  • 2021-03-29 JP JP2021519180A patent/JP7221382B2/ja active Active
• 2023
  • 2023-02-01 JP JP2023014201A patent/JP2023052832A/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events