Classifications

• • 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
  • C08F214/00—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
  • C08F214/02—Monomers containing chlorine
  • C08F214/04—Monomers containing two carbon atoms
  • C08F214/06—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
  • C08F8/18—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
  • C08F114/00—Homopolymers 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
  • C08F114/02—Monomers containing chlorine
  • C08F114/04—Monomers containing two carbon atoms
  • C08F114/06—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
  • 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
  • C08F8/18—Introducing halogen atoms or halogen-containing groups
  • C08F8/20—Halogenation
  • C08F8/22—Halogenation by reaction with free halogens
• • 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
  • 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
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

• the present invention is a chlorinated vinyl chloride resin capable of producing a molded product that maintains high adhesive strength even when used in a form in which a high pressure is applied and is less likely to cause defects such as cracks due to insufficient strength.
• the present invention also relates to a molding resin composition and a molded product using the chlorinated vinyl chloride 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 post-chlorinated polyvinyl chloride and a specific stabilizer are used in combination, and such a resin can withstand thermal stress and mechanical stress during processing. It is disclosed.
• a molded product for example, a pipe, a joint, etc. obtained by using a chlorinated vinyl chloride resin as described in Patent Document 1 has insufficient adhesive strength especially when used in a form in which a high pressure is applied. , There is a problem that water leakage and water leakage occur. Further, when the obtained molded product is used for a pipe, the refusion strength at the spider portion is low, and when it is used for a joint, the refusion strength at the weld portion is low. Therefore, when it is used for a joint or the like. There is a problem that cracks occur in the pipe.
• the present invention can produce a molded product that maintains high adhesive strength even when used in a form in which a high pressure is applied and is less likely to cause defects such as cracks due to insufficient strength. It is an object of the present invention to provide a chlorinated vinyl chloride-based resin, and a molding resin composition and a molded product using the chlorinated vinyl chloride-based 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 0.1 or more and 3.5 or less. The present invention will be described in detail below.
• the average value of A / B is such that a preferable lower limit is 0.2, a more preferable lower limit is 0.3, a further preferable lower limit is 0.5, a further preferable lower limit is 1.0, and a particularly preferable lower limit is 2.0, particularly.
• the preferred lower limit is 3.0.
• the average value of A / B is preferably less than 3.5, the more preferable upper limit is 3.0, the further preferable upper limit is 2.5, the further preferable upper limit is 2.0, and the particularly preferable upper limit is 2.0. It is 1.5.
• 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, 150 parts by mass of an acrylic UV curable resin is added to 100 parts by mass of a chlorinated vinyl chloride resin, and ultraviolet rays having a wavelength of around 375 nm are irradiated at an intensity of 10 mW / cm 2 for 3 minutes to obtain an acrylic resin. After curing the UV curable resin, a sample is prepared by embedding it in an epoxy resin.
• the obtained sample is polished by mechanical polishing, and the obtained cross section is subjected to imaging Raman measurement using a micro-Raman spectrophotometer [burying method], or a chlorinated vinyl chloride resin is dissolved in THF. Then, after separating and filtering the insoluble part with a centrifuge, add an excess amount of methanol to reprecipitate, separate by suction filtration, and dry at 80 ° C. with a vacuum dryer. Examples thereof include a method of performing imaging Raman measurement using a Raman spectroscopic analyzer [THF precipitation method].
• 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 it can be measured by calculating the average of the peak intensities of 10,000 points.
• the average value 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-mentioned implantation method or the THF precipitation method is preferable, and when measuring a molded product, unheated using the THF precipitation method is preferable. It is preferable to measure the sample of.
• chlorinated vinyl chloride resin of the present invention in the Raman measurement by Raman spectroscopy, 1450 - to the peak intensity B observed in the range of 1550 cm -1, 300 - of the peak intensity A observed in a range of 340 cm -1
• the standard deviation of the ratio (A / B) is preferably 0.10 to 10.0.
• 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 A / B is such that the more preferable lower limit is 0.20, the further preferable lower limit is 0.30, the further preferable lower limit is 0.40, the particularly preferable lower limit is 0.50, and the particularly preferable lower limit is 0.6.
• a very preferred lower limit is 0.8, especially 1.0 or higher, especially 3.0 or higher, for example 5.0 or higher.
• the standard deviation of A / B is such that the more preferable upper limit is 9.0, the more preferable upper limit is 8.0, the more preferable upper limit is 7.0, the particularly preferable upper limit is 6.5, and the particularly preferable upper limit is 6. 0, a very preferred upper limit is 5.5, especially 5.0, especially 4.0, eg 3.0.
• the average value of the A / B and the standard deviation of the A / B satisfy the relationship of the following formula (1). 0.50 ⁇ [mean value of A / B] + [standard deviation of A / B] 1/2 ⁇ 5.0 (1) Within the above range, it is possible to manufacture a molded product that maintains high adhesive strength even when used in a form in which a high pressure is applied and is less likely to cause defects such as cracks due to insufficient strength. Can be provided.
• 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.
• a vinyl chloride adhesive is used, the swelling property of the solvent on the surface of the molded product is improved, and the adhesive strength can be improved. Further, since the melting start time when heat is applied is shortened, the re-fusion strength in the mold having the molten resin confluence portion at the time of molding can be improved.
• 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. Is more preferable, 35.0 mol% or more is further preferable, 90.0 mol% or less is preferable, and 60.0 mol% or less is more preferable. Further, the ratio of the structural unit (b) is preferably 5.0 mol% or more, preferably 15.0 mol% or more, with respect to the total number of moles of the structural units (a), (b) and (c). Is more preferable, 30.0 mol% or less is more preferable, and 25.0 mol% or less is further preferable.
• the ratio of the structural unit (c) is preferably 5.0 mol% or more, preferably 25.0 mol% or more, with respect to the total number of moles of the structural units (a), (b) and (c). It is more preferably 55.0 mol% or less, and further 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.
• a vinyl chloride adhesive is used, the swelling property of the solvent on the surface of the molded product is improved, and the adhesive strength can be improved. Further, since the melting start time when heat is applied is shortened, the re-fusion strength in the mold having the molten resin confluence portion at the time of molding can be improved.
• 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. Among them, it is preferable to 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 above sulfur is bonded to the resin. Therefore, it can be seen that the chlorinated vinyl chloride resin of the present invention has a substituent containing sulfur.
• Examples of the sulfur-containing substituent include a substituent derived from a sulfur compound. Examples of the sulfur compound include compounds described later.
• At least one thioglycolic acid-based compound selected from the group consisting of thioglycolic acid and thioglycolic acid esters is preferable.
• 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 1 mass ppm or more and 1000 mass ppm or less. More preferably, it is 5 mass ppm or more and 500 mass ppm or less. More preferably, it is 10 mass ppm or more and 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% by mass or more, and preferably 16.0% by mass or less.
• 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. 0.1 ⁇ [Additional chlorination amount (% by mass)] / [Average value of A / B] ⁇ 160 (2)
• the uniformity of the chlorinated vinyl chloride resin is increased, high adhesive strength is maintained even when used in a form in which a high pressure is applied, and defects such as cracks due to insufficient strength are unlikely to occur. It is possible to obtain a molded product capable of producing a molded product.
• the more preferable lower limit of the above formula (2) is 1.0, the further preferable lower limit is 2.0, the further preferable lower limit is 2.5, the more preferable upper limit is 100, and the further preferable upper limit is 80.
• An even more preferred upper limit is 65.
• the added chlorinated amount and the average value of A / B satisfy the relationship of the following formula (3). 2 ⁇ 10 -4 ⁇ [Average value of A / B] / ([Additional chlorination amount] ⁇ [Ratio of constituent unit b (%)]) ⁇ 2 (3)
• the uniformity of the chlorinated vinyl chloride resin is increased, high adhesive strength is maintained even when used in a form in which a high pressure is applied, and defects such as cracks due to insufficient strength are unlikely to occur. It is possible to obtain a molded product capable of producing a molded product.
• the more preferable lower limit of the above formula (3) is 0.0003, the further preferable lower limit is 0.0004, the further preferable lower limit is 0.001, the more preferable upper limit is 1.0, and the further preferable upper limit is 1.0. 0.1, and even more preferably the upper limit is 0.05.
• 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 during molding and strength of the molded product.
• 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 performing a step of chlorinating the vinyl chloride resin by heating the suspension (chlorination step) can be mentioned.
• the mean value of the ratio of 1450 to to the peak intensity B observed in the range of 1550 cm -1, 300 peak intensity A observed in the range of ⁇ 340 cm -1 (A / B) is 0
• adjust the method of chlorination step, reaction temperature, reaction pressure, average chlorine consumption rate, and after performing the above chlorination step add sulfur compounds. It can be manufactured by adding it. Further, adjusting the addition amount of the sulfur compound, controlling the drying temperature and drying time in the drying step, the added chlorination amount of the chlorinated vinyl chloride resin, the structural units (a), (b), (c). ) Can also be produced by adjusting the ratio of the constituent unit (b) to the total number of moles.
• 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) is not particularly limited, but the higher the chlorine pressure, the easier it is for chlorine to permeate into the PVC particles.
• the range of 01 to 1.5 MPa is more preferable.
• the method of chlorinating PVC in the suspended state is not particularly limited, and for example, a method of irradiating light energy such as ultraviolet rays to promote photoreactive chlorination (hereinafter referred to as photochlorination) and the like. Can be mentioned.
• a method of irradiating light energy such as ultraviolet rays to promote photoreactive chlorination (hereinafter referred to as photochlorination) and the like.
• photochlorination a method of irradiating light energy such as ultraviolet rays to promote photoreactive chlorination
• the chlorination reaction temperature is preferably 40 to 80 ° C.
• the ratio of the irradiation intensity (W) of light energy in the case of photochlorination to the total amount (kg) of raw material PVC and water is preferably 0.001 to 6 (W / kg), and irradiation is performed.
• the wavelength of light is preferably 280 to 420 nm.
• the chlorinated vinyl chloride resin obtained by photochlorination can produce a molded product having high heat resistance and mechanical strength, and further excellent glossiness.
• 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 10 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 lower limit is 0.002 parts by mass, and a more preferable lower limit is 0.005 parts by mass.
• a more preferable upper limit is 5 parts by mass, a further preferable upper limit is 1.5 parts by mass, a further preferable upper limit is 1 part by mass, and a particularly preferable upper limit is 0.5 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 can be used as a stabilizer, a lubricant, a processing aid, an impact-resistant modifier, a heat-resistant improver, an antioxidant, an ultraviolet absorber, a light stabilizer, a filler, and heat, if necessary.
• Additives such as thermoplastic elastomers, pigments and reinforcing materials 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-resistant 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 content of the impact-resistant modifier in the molding resin composition of the present invention has a preferable lower limit of 1% by mass, a more preferable lower limit of 2% by mass, a preferable upper limit of 30% by mass, and a more preferable upper limit of 15% by mass. be. Within the above range, the strength of the obtained molded product can be sufficiently increased.
• the antioxidant is not particularly limited, and examples thereof include phenolic antioxidants.
• 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.
• the reinforcing material is not particularly limited, and examples thereof include a fiber-based reinforcing material and a non-fiber-based reinforcing material. Examples of the fiber-based reinforcing material include glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, cellulose nanofiber (CNF), kenaf and the like. Examples of the non-fiber reinforcing material include graphite, graphene and the like.
• 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 300 to 1550 cm -1 peak intensity B in the above imaging Raman measurement.
• a chlorinated vinyl chloride resin having an average value of the peak intensity A ratio (A / B) of 340 cm -1 of 0.1 or more and 3.5 or less can be measured.
• the molded product may contain a reinforcing material such as glass fiber or carbon fiber.
• 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.
• a chlorinated vinyl chloride type that can maintain high adhesive strength even when used in a form in which a high pressure is applied and can produce a molded product in which defects such as cracks due to insufficient strength are unlikely to occur.
• a resin, a resin composition for molding using the chlorinated vinyl chloride resin, and a molded product can be provided.
• Example 1 130 kg of deionized water and 50 kg of vinyl chloride resin having an average degree of polymerization of 1000 are put into 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 70 ° 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 0.04 MPa while stirring, and a high-pressure mercury lamp was used.
• oxygen oxygen
• chlorine oxygen content 50 ppm
• the chlorination reaction was started by irradiating ultraviolet rays having a wavelength of 365 nm with an irradiation intensity of 160 W. After that, the chlorination temperature was maintained at 70 ° C., the chlorine partial pressure was maintained at 0.04 MPa, the average chlorine consumption rate was adjusted to 0.02 kg / PVC-kg ⁇ 5 min, and the amount of added chlorinated amount was 9.5% by mass. When it reached, the irradiation of ultraviolet rays with a high-pressure mercury lamp and the supply of chlorine gas were stopped, and chlorination was completed.
• 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.
• 0.1 parts by mass (0.05 kg) of 2-ethylhexyl thioglycolate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as a sulfur compound with respect to 100 parts by mass (50 kg) of chlorinated vinyl chloride resin. was added at 200 g / min. Then, it was allowed to stand dry at 90 degreeC for 12 hours to obtain a photochlorinated powdery chlorinated vinyl chloride resin (additional chlorination amount was 9.5% by mass).
• chlorinated vinyl chloride resin slurry was neutralized with sodium hydroxide, washed with water, and a centrifuge (manufactured by Tanabe Iron Works Co., Ltd.). , O-15 type) and dehydrated for 3 minutes. Then, it was allowed to stand dry at 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 15, Comparative Examples 2 to 3 After chlorination at the reaction temperature, reaction pressure, and average chlorine consumption rate shown in Table 1 (upper part of the table: 5% by mass or later from the final added chlorinated amount, lower part: 3% by mass or more from the final added chlorinated amount). , A sulfur compound was added in the stated amount, and the chlorinated vinyl chloride resin was obtained in the same manner as in Example 1 except that the mixture was dried at the described drying temperature and drying time.
• Comparative Example 4 A powdery chlorinated vinyl chloride resin in the same manner as in Comparative Example 1 except that after chlorination was performed at the average chlorine consumption rate shown in Table 1 and then dried at the described drying temperature and drying time.
• Example 16 The same as in Example 3 except that the sulfur compound was added in the amount shown in Table 1 and dried at 100 ° C. for 45 hours using a vibration flow dryer (manufactured by Chuo Kakoki Co., Ltd., VU-75 type). A chlorinated vinyl chloride resin (additional chlorination amount: 10.7% by mass) was obtained.
• 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 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.
• Adhesiveness evaluation (manufacturing of pipe) 4.0 parts by mass of an 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.
• a heat stabilizer As the impact-resistant modifier, Kaneka B-564 (Methylmethacrylate-butadiene-styrene copolymer manufactured by Kaneka Corporation) was used.
• As the heat stabilizer TVS # 1380 (manufactured by Nitto Kasei Co., Ltd., organic tin-based stability) was used.
• a polyethylene-based lubricant Hiwax 220MP manufactured by Mitsui Chemicals, Inc.
• LOXIOL G-32 fatty acid ester-based lubricant
• 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. A 2.4 mm pipe was made.
• a polyethylene-based lubricant Hiwax 220MP manufactured by Mitsui Chemicals, Inc.
• LOXIOL G-32 a fatty acid ester-based lubricant manufactured by Emery Oleo Chemicals Japan Co., Ltd.
• the obtained chlorinated vinyl chloride resin composition was supplied to a twin-screw non-directional conical extruder (Nagata Seisakusho, OSC-30) having a diameter of 30 mm, and pellets were prepared at a resin temperature of 190 ° C.
• the obtained pellets were supplied to an injection molding machine (J350 ADS, manufactured by JSW) to prepare a socket having an outer diameter of 34.7 mm and an inner diameter of 26.9 mm.
• Adhesion evaluation Fill the inside of the obtained assembly sample with water, and use a hydrostatic pressure tester (manufactured by IPT, 1662-0021) in an oven to create an atmosphere of 65 ° C. so that the hoop stress of the pipe is 15.93 MPa. The test was started by pressurizing the pipe, and the time until a disconnection occurred between the pipe and the joint to which the adhesive was applied was measured. The case where there was no omission 1000 hours after the start of the test was evaluated as ⁇ , and the case where the omission occurred within 1000 hours was evaluated as x. In addition, when the omission occurred by 1000 hours, the time when the omission occurred was described.
• a chlorinated vinyl chloride type that can maintain high adhesive strength even when used in a form in which a high pressure is applied and can produce a molded product in which defects such as cracks due to insufficient strength are unlikely to occur.
• a resin, a resin composition for molding using the chlorinated vinyl chloride resin, and a molded product can be provided.

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• 2021
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