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WO1999006484A1 - Compositions de resines de chlorure de vinylidene, procede pour les produire et film a base de ces compositions - Google Patents

Compositions de resines de chlorure de vinylidene, procede pour les produire et film a base de ces compositions Download PDF

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Publication number
WO1999006484A1
WO1999006484A1 PCT/JP1998/003230 JP9803230W WO9906484A1 WO 1999006484 A1 WO1999006484 A1 WO 1999006484A1 JP 9803230 W JP9803230 W JP 9803230W WO 9906484 A1 WO9906484 A1 WO 9906484A1
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Prior art keywords
vinylidene chloride
weight
resin composition
parts
acid
Prior art date
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PCT/JP1998/003230
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English (en)
Japanese (ja)
Inventor
Mitsuru Hoshino
Shusaku Shibata
Original Assignee
Kureha Kagaku Kogyo Kabushiki Kaisha
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Publication of WO1999006484A1 publication Critical patent/WO1999006484A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/175—Amines; Quaternary ammonium compounds containing COOH-groups; Esters or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/08—Homopolymers or copolymers of vinylidene chloride

Definitions

  • the present invention relates to a vinylidene chloride-based resin composition having excellent heat stability, less coloring due to heat deterioration, and excellent extrusion productivity, a method for producing the same, and the vinylidene chloride-based resin.
  • a film comprising the composition as a material.
  • Chlorine-containing ethylene-based resins such as vinylidene chloride-based resins are formed into films, bottles, yarns, etc. by hot melt extrusion. At that time, the resin is susceptible to partial thermal deterioration due to heat and oxidative deterioration due to oxygen, which causes the molded product to be colored and the value of the product to be significantly impaired. There are many. Also, when these products are exposed to light, they may be colored and their product value may be impaired. In order to prevent such coloring by heat and light, a heat stabilizer is generally used. Especially in the food packaging field, heat stability that is harmless to hygiene Agents have been required and a number of studies have been conducted to address this.
  • epoxy stabilizers have been proposed as heat stabilizers for suppressing the coloration of vinylidene chloride resin due to thermal deterioration, and vinylidene chloride extruded under heat and melt. It has been widely used as an essential component of resin-based resin compositions.
  • heat stabilizers include weak acid salts, for example, sodium pyrophosphate and / or sodium primary phosphate (Japanese Patent Publication No. 6-1889) No. 63), non-alkane weak acid salts (Japanese Patent Application Laid-Open No. 4-517127), and alkali metal citrate (Japanese Patent Application Laid-Open No. 6-192325) Gazettes), citric acid or alkaline citrate gold salts (Jpn. Pat. Appln. KOKAI Publication No. 8-165,394), inorganic phosphates (JP-A-9-137702) No. 3) has been proposed.
  • weak acid salts for example, sodium pyrophosphate and / or sodium primary phosphate
  • non-alkane weak acid salts Japanese Patent Application Laid-Open No. 4-517127
  • alkali metal citrate Japanese Patent Application Laid-Open No. 6-1923205 Gazettes
  • citric acid or alkaline citrate gold salts Jpn.
  • a vinylidene chloride resin with improved thermal stability characterized in that the resin is a combination of ethylenediamine tetraacetate and inorganic silicate.
  • a composition and a method for producing the composition are provided.
  • An object of the present invention is to provide a vinylidene chloride resin composition excellent in extrudability, further improved in thermal stability and light stability achieved by the prior art. It is here.
  • Another object of the present invention is to provide a method for producing the above vinylidene chloride-based resin composition and a film produced from the vinylidene chloride-based resin composition. It is to provide.
  • EDTA salts acetic acid and its salts
  • organic weak acids organic weak acids
  • a phenolic antioxidant One or more antioxidants selected from the group consisting of one-cell antioxidants and phosphite-based antioxidants are mixed with vinylidene chloride resin at a specific ratio.
  • the reduced viscosity of the vinylidene chloride ⁇ polymer is 0.0400.711, and the ⁇ acid salt is It was confirmed that a vinylidene chloride-based resin composition selected from the group consisting of organic weak acid salts that do not contain nitrogen atoms and m-phosphate salts is effective in solving the above problems. I found it.
  • the present invention has been completed based on these findings. That is, according to the present invention, in the first aspect, the present invention is characterized in that a vinylidene chloride system ⁇ , an ED ⁇ A salt, and a ft machine weak acid salt are obtained. The vinylidene chloride resin composition is flooded.
  • Preferred embodiment of ED salt and organic weak acid salt content Is 100 parts by weight of vinylidene chloride resin
  • a phenolic antioxidant if necessary, a phenolic antioxidant, One or more antioxidants selected from the group consisting of a carbonate antioxidant and a phosphate antioxidant may be added to the vinylidene chloride-based tree composition. And can be done.
  • a vinylidene chloride monomer is added to an aqueous medium.
  • a phenolic antioxidant or a thioether antioxidant is added.
  • a small amount of one or more antioxidants selected from the group consisting of oxidation and phosphate antioxidants is added, and the pH of the polymerization system is adjusted to 3 to 8 to obtain vinylidene chloride.
  • a method for producing a vinylidene chloride resin composition characterized by obtaining a resin is provided.
  • the copolymer comprises a vinylidene chloride copolymer and a weak acid salt
  • the reduced viscosity of the vinylidene chloride copolymer is 0.040 to 0.057.
  • the weak acid salts are nitrogen
  • a vinylidene chloride resin composition excellent in extrusion productivity selected from the group consisting of organic weak acid salts and inorganic phosphates containing no atoms. With this resin composition, it is possible to obtain a heat stability improving effect that cannot be obtained by itself, that is, a synergistic ripening stability improving effect.
  • the content of the organic weak acid salt and the inorganic phosphate in the vinylidene chloride-based resin is 100 parts by weight per 100 parts by weight, respectively.
  • Vinylidene chloride resin in the present invention is vinylidene chloride.
  • a copolymer comprising 60 to 98% by weight and at least one other monomer copolymerizable with 2 to 40% by weight, or 100% by weight of these copolymers.
  • a mixed resin obtained by mixing the other polymer or copolymer at a ratio of 30 parts by weight or less, wherein the vinylidene chloride component is contained in the mixed resin in an amount of 50 to 9 parts by weight. It contains 8% by weight.
  • chloride The reduced viscosity of the vinylidene resin is usually at least 0.4 g, preferably from 0.04 to 0.62, more preferably 0.04 g.
  • a particularly preferred embodiment is one having a) original viscosity of 0.042420 lZg.
  • the vinylidene chloride resin may be a mixture with a vinylidene chloride resin having a different reduced viscosity and a different composition.
  • the reduced viscosity of the mixture in this case is preferably from 0.040 to 0.061 / g, more preferably from 0.040 to ⁇ 0.05. It is in the range of 71 / g.
  • the vinylidene chloride resin is a mixture with a vinylidene chloride resin having a reduced reduced viscosity, the vinylidene chloride resin The fluidity of the fat is increased, and heat generation during melt molding is suppressed, so that coloring is prevented.
  • the above mixture may have, for example, a reduced viscosity of 0.481 / g or more, preferably 0.052 to 0.0751 / g, or more preferably ⁇ . 0.055 to 0.056 g / g of the first vinylidene chloride copolymer and a reduced viscosity of less than 0.048 1 / g, preferably 0.038. ⁇ 0.04 8 1 / g, more preferably 0 3
  • vinylidene chloride in the present invention examples include (in the order of a line, vinyl chloride; methyl acrylate, acrylyl) Acid esters, acrylic acid 2—ethylhexyl, acrylyl acrylates such as acrylyl acrylates, etc.
  • an epoxy group-containing vinyl polymerizable monomer such as glycidyl acrylate or glycidyl methacrylate; butadiene, Jenogen compounds such as soprene or chlorinated gen compounds such as chloroprene; divinyl benzene, ethylene glycol )
  • an epoxy group-containing vinyl polymerizable monomer such as glycidyl acrylate or glycidyl methacrylate
  • Jenogen compounds such as soprene or chlorinated gen compounds such as chloroprene; divinyl benzene, ethylene glycol
  • At least two or more copolymerizable carboxylic acids in the molecule such as acrylic acid
  • Pluripotency with a complex bond can be used, but polyvinyl chloride and methyl acrylate are preferred.
  • vinylidene chloride copolymer when these other copolymerizable mono-a-components exceed 40% by weight, a gasoline copolymer obtained is obtained. If the amount is less than 2% by weight, the melt processability of the obtained copolymer may be reduced.
  • polymers or copolymers that can be mixed with the vinylidene chloride copolymer of the present invention include, for example, ethylene-vinyl acetate copolymer, ethylene Vinyl monochloride copolymer, ethylene and acrylic acid, methyl acrylate, alkyl (meth) acrylate Copolymers with at least one monomer selected from (alkyl having 1 to 18 carbon atoms) or (meth) glycidyl acrylate, ethylene Ionomer, (meth) acrylic polymer, methyl methacrylate-butadiene-styrene copolymer, nylon, polystyrene Can be mentioned.
  • the mixing ratio of these other polymers or copolymers exceeds 30 parts by weight m with respect to 100 parts by weight of vinylidene chloride copolymer, it is obtained.
  • the gas barrier properties of the mixed resin may decrease, and the vinylidene chloride component may be reduced to less than 50% by mass in the mixed resin. If the gasoline content of the mixed resin exceeds (98% by mass), the melt processability may be reduced.
  • the mixture removes waste (recycled product) generated during extrusion molding of a multilayer film containing the copolymer and the vinylidene chloride copolymer. It may be obtained by mixing it with a copolymer and reusing it effectively, but as the amount of addition increases, the transparency of the film tends to be impaired.
  • EDTA salts added as essential components include ethylenediaminetetraacetic acid; and ethylenediaminetetraacetic acid.
  • Alkyli metal salts of ethylenediaminetetraacetic acid such as trisium salts and potassium salts, may be mentioned.
  • these EDTA salts the preferred example is alkylene alkylamine tetrametallic alkali metal salt, and the more preferred example is the sodium salt thereof.
  • Lithium salts can be mentioned.
  • at least one selected from these ethylenediamine tetraacetates is blended with a vinylidene chloride resin.
  • the reason that the EDTA salt enhances the thermal stability of the vinylidene chloride resin is that the iron ion and the chlorine ion combine to form vinyl chloride. It is thought to suppress the action of dendine or vinylidene chloride resin that promotes the dehydrochlorination reaction, and it is necessary to make the action more effective. 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.1 part by weight, per 100 parts by weight of the vinylidene chloride resin It is hoped that it is contained in the proportion of If the amount of EDTA salts is too small, sufficient improvement effect cannot be obtained.On the other hand, even if it is used in a large amount, the effect of improving thermal stability in proportion to the added amount is difficult and economically favorable. Absent.
  • the organic weak acid salt used in combination with the EDTA salt has a dissociation constant Ka (25 ° C.) All of the Ka values are greater than or equal to 2.5, preferably 2.5 to 6.0, more preferably all are greater than or equal to 2.5 and at least one is between 4 and 6. It is a nitrogen atom-free organic weak acid and / or its metal salt (Chemical Handbook, 3rd Edition, edited by The Chemical Society of Japan, II, p. 339). Preferably, different ionic species of organic weak acid salts coexist.
  • organic weak acid salts include, for example, saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, and propionic acid, and metal salts thereof; malon; Saturated aliphatic dicarboxylic acids such as acid, succinic acid, glutaric acid, and adipic acid, and alkali metal salts thereof; hydrochlorides such as glycolic acid and lactic acid Xyl-saturated aliphatic monocarbonic acid and its metal salts; hydroxysaturated aliphatic dicarboxylic acids such as hydroxyxmalonic acid and lingic acid; Alkali metal salts; dihydroxy saturated aliphatic monocarboxylic acids such as glyceric acid and its alkali metal salts; dihydroxy saturated salts such as tartaric acid Aliphatic dicarboxylic acids and their alkali metal salts; hydroxysaturated aliphatic toxins such as citric acid and isocunic acid Carboxylic acid and its alkali
  • the vinylidene chloride-based resin composition of the present invention one or more of these organic weak acid salts are added to the vinylidene chloride-based resin.
  • the compounding ratio of the organic weak acid salt is 0.0001 to 1 part by weight, preferably 0.00001, based on 100 parts by weight of the vinylidene chloride resin. ⁇ 0.8 parts by weight, more preferably 0.001 to 0.5 parts by weight.
  • the amount of the organic weak acid salt is too small, the effect of improving the heat stability by the combined use is small, while if the amount is too large, the effect of improving the thermal stability is in proportion to the amount added and the effect of improving the heat stability is difficult.
  • the transparency of the object may be reduced. .
  • the ratio of the weight of the organic weak acid salt to the total weight of the EDTA salt and the organic weak acid salt is preferably from 20 to 95% by weight, and more preferably from 30 to 90% by weight. At these ratios, the effect of improving the thermal stability is significant.
  • the antioxidant to be used is one or more antioxidants selected from a phenolic antioxidant, a carbonate antioxidant, and a phosphite antioxidant. .
  • a phenolic antioxidant is used, and in a more preferred embodiment, a phenolic antioxidant is used.
  • a mixture of a vinylidene-based resin and a phosphate-based antioxidant and / or a phosphate-based antioxidant is used in combination.
  • phenolic antioxidants examples include 2 »6-di-tert-butyl 4-methyl fur (BHT), butyr-hydroxy-aniso-phenol. , 2,2'-methyl-one-vis (1-6-tert-butyl), octadecyl
  • the phenolic antioxidant used in the present invention may be a mixture of two or more.
  • the mixing ratio of the above-mentioned phenolic antioxidant is 0.005 to 1 part by weight, preferably 0 to 100 parts by weight of vinylidene chloride resin. 0.05 to 0.5 ⁇ 3 ⁇ 4 ⁇ . If the ratio of the 1-unit is too small, the effect of improving the thermal stability cannot be obtained, while the effect of the thermal stability in proportion to the added S is difficult even with a large amount of fl. Not really good
  • thioether-based antioxidants examples include, for example, thiocarboxylic acid pionic acid; dilaurylthiodipropionate, dimyristylthiodipropionate, and distear. Alkyl esters of thiodipropionate, such as lylthiodiopene pioneate; pentaerythritol tetrakisu (3—rauriluthiopropione) Erythritol-based alkyl esters of thiopropionate And so on.
  • the titanium-based antioxidant used in the present invention may be a mixture of two or more.
  • phosphite-based antioxidants examples include tris nonylphenyl phosphite, tris (mono and / or dinonylphenyl). ) Phosphite, 4, 4, 1-isoproviridene diphenyl phenyl phosphite, distair lipene Examples include slit phosphites (for example, Asahi Denka's PEP-8).
  • the phosphite antioxidant used in the present invention may be a mixture of two or more.
  • the mixing ratio of the vinyl ether antioxidant and the phosphite antioxidant is 0 parts by weight with respect to 100 parts by weight of the vinylidene chloride resin. It is 0.005 to 0.2 part by weight, preferably 0.001 to 0.1 part by weight. If the proportion is too small, the effect of improving the thermal stability is small.On the other hand, even if it is used in a large amount, the effect of improving the thermal stability in proportion to the added amount is difficult, and it is economically favorable. Not good.
  • the vinylidene chloride resin used in the present invention may be obtained by any polymerization method such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method. Those obtained by a polymerization method are preferred.
  • the vinylidene chloride-based monomer In order to make the vinylidene chloride-based resin contain EDTA salts and organic weak acid salts, the vinylidene chloride-based monomer should be replaced with another polymerization aid in the polymerization step for producing the resin. It may be added and mixed with the agent, or may be mixed in the slurry after polymerization of the vinylidene chloride-based monomer. In addition, it can be added and mixed with other processing aids in a powder state before processing of vinylidene chloride resin.
  • EDTA salts and Organic weak acid salts may be added in the whole amount at the same time, or may be added separately in separate portions.
  • the EDTA salt and the organic weak acid salt may be contained in the vinylidene chloride resin at the above-mentioned ratio.
  • EDTA salts and organic weak acid salts are previously contained in the polymerization system in the polymerization stage of the vinylidene chloride-based monomer.
  • the kind and the amount of the EDTA salt and the organic weak acid salt are appropriately adjusted, and the pH of the polymerization system is usually polymerized at 3 or more, preferably after the polymerization.
  • the pH of the polymerization system is usually polymerized at 3 or more, preferably after the polymerization.
  • the pH of this system can be adjusted by appropriately adjusting EDTA salts and organic weak acid HIs and ⁇ iJIli. Not only salts, but also strong bases that are hydroxides of aluminum metal such as sodium hydroxide using EDTA or organic weak acid that forms salts, not only salts, or By adding an alkali metal salt of inorganic phosphoric acid, etc., and conversely, by adding a strong acid such as hydrochloric acid to EDTA salts and organic weak acid salts, the polymerization p H can also be adjusted to the above range.
  • 100 parts by weight of vinylidene chloride-based monomer is 0% by weight of ethylenediamine tetraacetate.
  • the antioxidant to be used can be divided and a small amount thereof can be added in advance to the polymerization system.
  • the details of its mechanism of action are unknown, but it is possible to obtain better thermal stability than when adding all the antioxidant used after polymerization. And can be done.
  • the method for producing the vinylidene chloride-based resin composition described above can be applied to an emulsion polymerization method or a suspension polymerization method, but is preferably applied to a suspension polymerization method from the viewpoint of productivity. No. Further, even when the method for producing the vinylidene chloride-based resin composition according to the present invention is carried out using a stainless steel polymerization can, the effect of improving the thermal stability is remarkable. Exerted on So preferred
  • the vinylidene chloride-based resin composition of the present invention contains an EDTA salt and an organic weak acid salt and, if necessary, an antioxidant in the vinylidene chloride-based resin. It is characterized by the fact that, if necessary, it also contains various other commonly used additives, such as plasticizers, stabilizers, etc. Can contain ultraviolet absorbers, lubricants, surfactants, pigments, fillers, etc.
  • additives include, for example, dioctyl phthalate, acetyl tributyl citrate, dibutyl ceno 'kate dioctyl cellulose.
  • Polyesters consisting of plasticizers such as silicates, acetylated monoglycerides, etc., or saturated aliphatic dicarboxylic acids and polyhydric alcohols
  • Plasticizers Epoxylated soybean oil, Epoxylated flavonoid oil Epoxy-based stabilizers such as epoxylated octyl stearate, epoxy-containing resin, etc .;
  • Magnesium hydroxide Stabilizers for inorganic bases such as um, magnesium oxide, potassium hydroxide, phosphate, etc .
  • oxidized polyethylene wax, noraphy Waxes such as waxes, polyethylene wax, ester monate wax, etc.
  • the amount of each of the plasticizer and the stabilizer was adjusted according to the vinylidene chloride resin.
  • the amount is preferably 1 to 10 parts by weight, more preferably 2 to 6 parts by weight, based on 100 parts by weight.
  • these additives are usually mixed with a vinylidene chloride resin in a powder form before processing, but are added to the vinylidene chloride resin. May be mixed in a slurry state after the completion of the polymerization, or may be added to the vinylidene chloride-based monomer before the ⁇ combination to be polymerized and mixed. .
  • each component of the composition according to the second embodiment of the vinylidene chloride resin composition of the present invention will be described.
  • the organic weak acid salts used in the second embodiment of the vinylidene chloride-based resin composition of the present invention include all of the pKa values of the dissociation constant Ka (25 ° C) in an aqueous solution.
  • the organic acid is a nitrogen-free organic weak acid having a content of 2.5 to 6.0 and an alkali metal salt thereof.
  • organic weak acid salts include, for example, saturated fats such as formic acid, acetic acid, and propionic acid.
  • Hydroxy-saturated aliphatic monocarboxylic acids such as citric acid and its alkali metal salts; hydroxy-saturated fatty acids such as hydroxymalonic acid and lingic acid Dicarboxylic acid and its alkali metal salt; dihydroxy saturated aliphatic monocarboxylic acid such as glyceric acid and its alkali metal salt; Dihydroxy saturated aliphatic dicarboxylic acid such as tartaric acid and its alkali metal salt; Hydroxy saturated aliphatic triglyceride such as citric acid and isocunic acid Carboxylic acid and its alkali metal salts; aromatic monocarboxylic acid of benzoic acid, phthalic acid, and isophthalic acid; or dicarboxylic acid and its alcohol Can be cited.
  • Preferred examples include citric acid and its alkali metal salts.
  • Inorganic phosphates used in the second embodiment of the vinylidene chloride resin composition of the present invention include inorganic phosphates such as phosphoric acid, metallic acid, and polyphosphoric acid.
  • Phosphoric acid salts such as phosphoric acid and alkali metal salts thereof, or alkaline earth metal salts are preferred.
  • potassium acid, etc. especially in combination with sodium pyrronate and sodium dihydrogen pyrophosphate, or sodium pyrrolate.
  • the combined system with sodium phosphate is preferable because the pH adjustment of the polymerization system can be relatively easily performed.
  • the mixing ratio of the organic weak acid salt or the inorganic phosphate is 0.001 to 1 part by weight, relative to 100 parts by weight of the vinylidene chloride resin. It is preferably from 0.0001 to 0.8 part by weight, more preferably from 0.01 to 0.5 part by weight. If the amount of the organic weak acid salt or the inorganic phosphate is too small, the effect of improving the ripening stability is small, while if it is too large, the heat stability is proportional to the amount added. It is difficult to obtain the effect of improving the transparency of the molded product, and the transparency of the molded product may be reduced.
  • the vinylidene chloride-based resin composition of the present invention in order to exhibit the effect of improving the thermal stability of the organic weak acid salt or the inorganic phosphoric acid salt, it is necessary to use vinylidene chloride. It is an essential requirement that the reduced viscosity of the copolymer is from 0.040 to 0.0571 / g. The preferred embodiment of the wrap film is from 0.042 to 0.0481 / g. Extrusion molding conditions have become harsher due to the improvement in productivity.In recent years, vinylidene chloride copolymers have only recently been used.
  • the glyceride used in the second embodiment of the vinylidene chloride resin composition of the present invention is preferably a lower fatty acid having an acyl group of 2 to 6 carbon atoms. Or acetic acid, and a glycerol formed from an acetyl group and a tertiary fatty acid having 8 to 22 carbon atoms, preferably 10 to 16 carbon atoms, and particularly preferably 12 carbon atoms. It is a mixture of at least one of the cellulose esters.
  • diacetyl cabril glyceride diacetyl cabril glyceride, diacetyl cabril glyceride, diacetyl laurel glyceride, Chilemi-Ristinole Glyceride, Diacetinol-Military Glyceride, Diacetylstearil Glyceride, Diacetyl Elysyl Glyceride, Diasetil El Sirrug Lyceride, dipropionyl laurel glyceride, dibutanol laurel glyceride, zikabu ylurauril glyceride, etc.
  • the blending ratio of the above glyceride is as follows: vinylidene chloride copolymer 10 It is 1 to 10 parts by weight, preferably 2 to 6 parts by weight, per 0 parts by weight.
  • the use of the above-mentioned glyceride in the present invention not only prevents the film appearance from being deteriorated during extrusion production with a large amount of extrusion, but also enhances the stretch processability and the rubber film. It is effective for imparting adhesiveness, and the addition amount of other plasticizers can be reduced. If the added amount of the plasticizer is large, properties such as gas-nollability, stickiness of the film, and film appearance during extrusion production with a large amount of extrusion are deteriorated. In addition, when the production amount is large like a wrap film, the amount of the plasticizer added can be reduced by the cost (reduced.
  • the slate rate is effective as a plasticizer for vinylidene chloride resin
  • the film appearance during extrusion production with a large amount of extrusion (easy to reduce.
  • the lowering of the film appearance is suppressed and high extrusion productivity is easily obtained, and the mixing ratio of glycerides is the same as that of other plasticizers. Or less than the total amount of other plasticizers.Even if it is added in too large a quantity, the effect does not change because gasoline and / or lubricity is reduced.
  • the glides of the invention may be used alone, improving extrudability and improving thermal stability. Price is rather cheap, even high safety.
  • an antioxidant can be used if necessary.
  • the antioxidant used is one or more antioxidants selected from phenolic antioxidants, polycarbonate antioxidants, and phosphate antioxidants. is there .
  • a phenolic antioxidant and / or a phosphite antioxidant are used in combination with a chloride. It is blended with two resin resins.
  • EDTA salts may not be added.However, if iron components are present in the production process during the contact with vinylidene chloride resin, iron salts may be added. When added, it is effective in improving ripening stability. When the EDTA salt is added / added, the pH of the polymerization system increases to less than 2.5 acidity and to more than 8 basicity, the coloration increases. E D
  • Examples of the TA salt include ethylenediaminetetraacetic acid; a sodium salt of ethylenediaminetetraacetic acid.
  • the vinylidene chloride resin used in the present invention may be obtained by any polymerization method such as a suspension polymerization method, an emulsion polymerization method, and a solution polymerization method.
  • An extrudable material obtained by a polymerization method is preferred.
  • the vinyl chloride is required at the polymerization stage for producing the resin. It may be added to the nilidene monomer together with other polymerization aids and mixed, or in a slurry state after polymerization of the vinylidene chloride simple substance. May be mixed. Further, in the powder state of the vinylidene chloride resin before processing, it can be added and mixed together with other processing aids.
  • the organic weak salts or the inorganic phosphates may be added at the same time in their entirety, or may be added separately in separate portions.
  • the organic weak acid salt or the inorganic phosphate may be contained in the vinylidene chloride-based resin in the ratio described in the above item 1.
  • these additives When these additives are added to vinylidene chloride resin, they may be added by dissolving them in a solvent or water, or they may be added directly in powder form. It is also good.
  • the pH is between 3 and 1 °, preferably between 3 and 8 for organic weak acid salts, between 2.5 and 8 for inorganic phosphates, preferably between 2.5 and 5 or less. . If the pH of the polymerization system is too low, or if the pH is too high, the resulting vinylidene chloride-based polymer tends to have poor thermal stability.
  • the pH of the polymerization system can be adjusted by appropriately selecting the type and the amount of the organic weak acid salt or the inorganic phosphoric acid salt.
  • the pH of the polymerization system is adjusted to the above range by adding a strong base such as sodium hydroxide or a strong base that is a hydrate of gold ⁇ or a strong acid such as hydrochloric acid. You can also do it.
  • a vinylidene chloride resin having a specific reduced viscosity has an organic weak acid salt or It is characterized by containing inorganic phosphates, and if necessary, further contains various other commonly used additives such as plasticizers and stabilizers. , An ultraviolet absorber, a lubricant, a surfactant, a pigment, a filler, and the like.
  • additives include, for example, dioctyl phthalate.
  • Plasticizers such as butyl, acetyl tributyl citrate, dibutyl cenote, and dioctyl sebacate, or saturated aliphatic dicarboxylic acids and polyhydric alcohols.
  • polyester-based plasticizers epoxidized soybean oil, epoxidized linseed oil, epoxylated octyl stearate, epoxy resin containing epoxy group, etc.
  • Stabilizers for inorganic bases such as magnesium hydroxide and magnesium oxide; Polyethylene wax, paraffin wax Wax, polyester resin wax, etc., fatty acid ester such as glycerone monoester, etc.
  • Lubricants such as fatty acid mono and visamide; sorbitan fat ll / j acid ester, polyg Nonionic surfactants such as glycerol fatty acid ester and polyoxyethylene sulfonyl fatty acid ester; 2-(2, UV-absorbing agents such as oxy-3,5,1-di-tert-butylphenyl) -15-chlorobenzotriazole.
  • the amount of each of the plasticizer and the stabilizer is usually 1 to 10 parts by weight, preferably 2 to 6 parts by weight, based on 100 parts by weight of the vinylidene chloride-based resin.
  • these additives are usually mixed in a powder form before the processing of the vinylidene chloride-based resin, but are added after the polymerization of the vinylidene chloride-based monomer is completed. It can be mixed in a rally state, or it can be pre-polymerized It may be added to the previous vinylidene chloride-based monomer, polymerized and mixed.
  • the vinylidene chloride-based resin composition of the present invention has greatly improved thermal stability. Immediately after the extrusion productivity of the molded product obtained is improved, even if the molding speed such as the extrusion rate and the rolling speed is increased, the molded product with a small yellowing degree and excellent color tone is more efficient. Can be obtained.
  • the resin compositions obtained in the examples and comparative examples were preheated at 175 V for 2 minutes without pressurization using a press machine, and then at 15 MPa for 5 minutes. It was pressurized and then cooled with a cooling press under a load of 5 MPa for 2 minutes to produce a 3 mm thick press sheet. Using this press sheet as a test piece, the b value of the color of the test piece was measured using a color difference meter (manufactured by Minolta Co., Ltd .: CR—200). . Based on Comparative Example 4, the difference ⁇ b was determined. The larger the ⁇ b value is on the + side, the greater the yellowness due to thermal degradation is, and the smaller the value is on the one side, the smaller the yellow value is.
  • the reduced viscosity of the vinylidene chloride-based resin is determined using a soxhlet extractor using a polymer dehydrated and dried from a polymer slurry using methanol as a solvent. After the extraction process, the dried material is used as a sample, and
  • the obtained vinylidene chloride-based string composition was subjected to a ripening stability test.
  • the results are shown in Table 1 together with the antioxidant formulation and the contents of EDTA, citric acid and DLTDP contained in the vinylidene chloride resin composition. Since EDTA and citric acid dissolve in water and change their forms, their content is reduced to sodium ethylenediaminetetraacetate and citric acid. Calculated in parts by weight per 100 parts by weight of vinylidene resin
  • Example 1 Polymerization was carried out in the same manner as in Example 1. The pH of the polymerization system during the preparation was adjusted to 5.2 using an aqueous solution of sodium hydroxide. The pH of the slurry after the polymerization was 4.4 before dehydration, and the polymerization yield was 86.7 reduced viscosity of 0.0461 / g. Table 1 shows the results of a thermal stability test of the obtained resin composition.
  • the amount of ethylenediamine tetrasodium nitrate sodium dihydrate added was adjusted.
  • the reduced viscosity was 1% and the reduced viscosity was 0.046 1 / g.
  • Table 1 shows the results of a thermal stability test of the obtained resin composition.
  • Polymerization was carried out in the same manner as in Example 1 except that 975 g was added and the pH of the polymerization system was adjusted to 5.2.
  • the pH of the slurry after the polymerization was 4.4 before dehydration, the polymerization yield was 86.9%, and the reduced viscosity was 0.046. It was 1 / g.
  • Table 1 shows the results of the thermal stability test of the obtained resin composition.
  • the polymerization was carried out in the same manner as in Example 1 except that the addition of citric acid was not carried out to 4.375 g.
  • the pH of the polymerization system at the time of preparation was adjusted to 5.2 using an aqueous sodium hydroxide solution. Before the slurry was dehydrated, the slurry had a pH of 4.1, a polymerization yield of 87.2%, and a reduced viscosity of 0.0461 / g.
  • Table 1 shows the results of the thermal stability test of the obtained resin composition.
  • Comparative Example 3 Same as Example 1 except that the addition of citric acid was changed to 4.3375 g without adding ethylenediaminetetranadinium dihydrate dihydrate. Polymerization was carried out. The pH of the polymerization system at the time of preparation was adjusted to 5.2 using an aqueous sodium hydroxide solution. The slurry after the completion of polymerization and before dehydration had a pH of 4.7, a polymerization yield of 86.9%, and a reduced viscosity of 0.461 / g. Table 1 shows the results of the thermal stability test of the obtained resin composition.
  • Example 1 U. U 0. 0 1 5 56 5.2.4.4-1.0.0 Example 20.006.0.022 79 5.2.4.4-2.5 Example 3 0.0.190 008 30 5.2.4-0.8 Example 4 0.01 2 0 .0 1 5 56 5.2.4-1.5 Comparative example 1 0 0 6.3.3.3 + 3 .5 Comparative Example 2 0 0 .029 5.2.4.7 +0.8 Comparative Example 3 0.026 0 5.2 3.5 +0.9 Comparison (column 4 ( "0.01 2 0 1 5 .9 Standard
  • Inorganic phosphates (tetrasodium pyrophosphate and disodium dihydrogen pyrophosphate) were added to 100 parts by weight of the vinylidene chloride-based copolymer at 0.010 parts and 0.016 parts, respectively.
  • an antioxidant T manufactured by Ciba-Geigi Co., Ltd .: "IRGANOX 245"
  • an antioxidant S diilauryl thiodibutone pionate
  • vinylidene chloride-based resin compositions obtained by ffl of ethylenediaminetetraacetate and citric acid together and polymerizing are ethylene chloride.
  • Vinylidene chloride-based resin composition obtained by using diammine tetraacetate and sodium phosphate together and performing a ⁇ stage (Comparative Example 4; 0 9 — 1 3 7 ⁇ 23 3), the heat stability was further improved, and the degree of coloring was found to be small.
  • Vinylidene chloride resin composition obtained by the same method as in Comparative Example 1.
  • the amount of ethylenediamine tetraacetic acid sodium and / or citric acid shown in Table 2 was added.
  • citric acid a 10% by weight aqueous solution was prepared, and the pH was adjusted to 4.0 with sodium hydroxide.
  • the converted amount as citric acid is shown in Table 2. It was added so that it might become an amount.
  • Ethylenediamine sodium tetraacetate is 1
  • the conversion amount as sodium ethylenediaminetetraacetate is shown in Table 2.
  • the obtained resin lacquer was dried at 50 ° C for 5 hours and subjected to a thermal stability test.Table 2 shows the results.
  • the pH of the polymer slurry which was polymerized in the same manner as in Example 1, was adjusted in the range of 2 to 11 to obtain the pH values shown in Table 3.
  • the pH of the polymer slurry before dehydration is adjusted to be acidic by the addition of aqueous hydrochloric acid, and adjusted to be more acidic by the addition of aqueous sodium hydroxide. And maintained at the various pH values shown in Table 3.
  • the polymer slurry adjusted to each pH was dehydrated and dried to obtain a copolymer powder.
  • Table 3 shows the results of a thermal stability test of the obtained resin composition.
  • Polymerization was carried out in the same manner as in Example 1 except that the pH of the polymerization system at the time of preparation was adjusted to 2.3 using an aqueous hydrochloric acid solution.
  • the pH of the slurry after polymerization and before dehydration was 2.2.
  • the polymerization slurry was dehydrated and dried to obtain a copolymer powder.
  • Thermal stability of the obtained resin composition Table 3 shows the results of the tests.
  • Polymerization was carried out in the same manner as in Example 1 except that the pH of the polymerization system at the time of the preparation was changed to 10.0 using an aqueous sodium hydroxide solution.
  • the H before the slurry was dehydrated after the polymerization was 7.0.
  • the polymerization slurry was dehydrated and dried to obtain a copolymer powder.
  • Table 3 shows the results of a thermal stability test of the obtained resin composition.
  • antioxidant T manufactured by Ciba-Geigy Corporation: "Ir ganox 245"
  • antioxidant S diilaurylthiodibutionate pionate
  • the color tone of the film 20M wound from the resin composition obtained by Run was measured using a color difference meter (manufactured by Minolta Co., Ltd .: CR—200) to determine the b value. It was measured. The larger the b value is to the + side, the greater the degree of yellowing due to thermal degradation.
  • Methoxycellulose weak in the reactor (made of glass lining) After adding deionized water in which acid salts are dissolved and purging the system with nitrogen, diso-propyl carboxylic acid carbonate carbonated soybean oil is added to the system. Or epoxidized linseed oil, triethylene glycol 3-(3-butyl alcohol 4-hydroxy 5-methyl ⁇ Nil) Propionate (Chiba Gayi Co., Ltd.):
  • a mixture of RGANOx24 ”) dissolved in a mixture of vinylidene chloride monomer and vinyl chloride in a single S bath was injected.
  • the pH of the polymerization system at the time of preparation was adjusted using sodium hydroxide or hydrochloric acid.
  • vinylidene chloride resins having different reduced viscosities can be obtained by adding diisopropyl propyl carbonate as a polymerization temperature and a catalyst. It was prepared by changing the amount added.
  • the thickness of the obtained film is 12 m in single ⁇ :
  • the weak acid salt is 0.022 parts by weight of cynic acid, 1 part by weight of epoxidized linoleic oil, 2 parts by weight of diacetol It was made the same as Run 1 except that it was a 6.0 mass part, which is mainly composed of receride.
  • Quenoic acid ( 1) pyrophosphate ( 2) PH thermal stability (part ( 3) ) (part ( 3) ) ⁇ b value ( 4)
  • citric acid equivalent citric acid is dissolved in water and decomposed by carohydrate water to change its form.
  • vinylidene chloride resin is used as citric acid. (Calculated in parts by weight per 100 parts by weight)
  • citric acid equivalent ffi citric acid is dissolved in water and hydrolyzed to change its form, but as citric acid, vinylidene chloride resin 1 0 Calculated in parts by weight per part by weight
  • citric acid equivalent amount citric acid is dissolved in water and hydrolyzed to change its form, but as citric acid, vinylidene chloride resin 1 (Calculated in parts by weight per 0 parts by weight)
  • the method of adding the antioxidant of the present experimental system were the same as R un 1 ⁇ 3.
  • Quanic acid 1) pyrophosphate ( 2 ) EDTA 5) PH thermal stability (parts ( 3) ) (parts ( 3 )) (parts ( 3) ) ⁇ b value ( 4)
  • Run 9 0.022 2 4 -0.2 Run 10 0.022 3 0 1 1 5
  • Run 1 1 0 022 7 0 -2 0 Run 12 0 022 10 0 1 0 1 Run 13 (2) 2 2 1 0 1 Run 14 (2) 3 0 1 16 Run 1 5 (2) 8 0 + 0 2 Run 1 6 (2) 10 0 + 1 0 Run 17 (2) 0.012 8 0 + 0 3 Run 18 (2) 0.002 10 0 + 1 2
  • Citric acid equivalent citric acid is dissolved in water and hydrolyzed to change its form, but as citric acid, vinylidene chloride resin 1 (Calculated in parts by weight per 0 parts by weight)
  • FIG. 8 shows that the thermal stability of the resin composition was significantly improved when the pH was adjusted to about 3 in the case of an inorganic phosphate.
  • the vinylidene chloride resin composition of the present invention contains (1) ethylenediaminetetraacetic acid salts and citrate salts, and optionally contains triethylene as an antioxidant.
  • Lengol alcohol 1-vis- 3-(3-tert-butyl-4-hydroxy-1-5-methylphenyl) bromineate and, if necessary, giraffe By polymerizing a vinylidene chloride-based monomer in the presence of urithiothiop-opening pioneate, or (2) during or after the polymerization, Reduced viscosity from 0.040 to 0.0571 / g vinylidene chloride copolymer, selected from the group of organic weak acid salts and nitrogen-free organic weak acid salts By adding weak acid salts, the thermal stability of the resin composition is further improved.

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Abstract

Cette invention se rapporte à des compositions de résines copolymères de chlorure de vinylidène, ayant une excellente stabilité thermique lors du moulage par extrusion et un ternissage réduit sous l'effet de la détérioration thermique. L'une de ces compositions contient une résine de chlorure de vinylidène, un sel d'acide éthylèndiaminetétraacétique, et une sel d'un acide faible organique. Le procédé pour produire une telle composition de résine de chlorure de vinylidène consiste à polymériser un monomère de chlorure de vinylidène avec au moins un sel d'acide d'éthylèndiaminetétraacétique en présence d'au moins un sel d'acide faible organique à un pH du système de polymérisation égal ou supérieur à 3 et à régler le pH de la phase aqueuse à la fin de la polymérisation sur une valeur comprise entre 3 et 6. Une autre de ces compositions contient un copolymère de chlorure de vinylidène et un sel d'un acide faible, le copolymère ayant une viscosité réduite comprise entre 0,040 et 0,057 l/g et le sel étant choisi dans le groupe des sels d'acides faibles organiques ne contenant pas d'atome d'azote et des sels d'acide phosphorique, une telle composition se caractérisant par une excellente productivité lors de l'extrusion. On obtient le film faisant l'objet de cette invention en extrudant une telle composition de résine de chlorure de vinylidène en utilisant une trémie sous vide d'air.
PCT/JP1998/003230 1997-08-01 1998-07-17 Compositions de resines de chlorure de vinylidene, procede pour les produire et film a base de ces compositions WO1999006484A1 (fr)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171492A (ja) * 1997-06-20 1999-03-16 Kureha Chem Ind Co Ltd 塩化ビニリデン共重合体樹脂組成物、そのフィルム、その押出加工方法
JP2005513239A (ja) * 2001-12-20 2005-05-12 フエロ コーポレーション グリセリントリエステル可塑剤
JP2008074908A (ja) * 2006-09-19 2008-04-03 Asahi Kasei Chemicals Corp 塩化ビニリデン−アクリル酸メチル共重合体樹脂組成物及びその樹脂組成物から成るフィルム
JP2010286824A (ja) * 2009-05-15 2010-12-24 Sony Corp 光学体およびその製造方法、窓材、建具、ならびに日射遮蔽装置
JP2017537200A (ja) * 2014-12-09 2017-12-14 ロッテ アドバンスト マテリアルズ カンパニー リミテッド 自動車用熱可塑性樹脂組成物及びこれから製造された自動車用成形品
JP2018529005A (ja) * 2015-08-28 2018-10-04 ロッテ アドバンスト マテリアルズ カンパニー リミテッド 熱可塑性樹脂組成物及びこれから製造された成形品
US10316188B2 (en) 2014-12-19 2019-06-11 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and molded part for automobiles using the same
WO2023167198A1 (fr) * 2022-03-04 2023-09-07 株式会社クレハ Film d'emballage

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104149367A (zh) * 2014-06-30 2014-11-19 苏州博云塑业有限公司 一种肠衣薄膜的制备方法

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JPS57141437A (en) * 1981-02-25 1982-09-01 Sakai Chem Ind Co Ltd Chlorine-containing resin composition
JPS5834843A (ja) * 1981-08-26 1983-03-01 Asahi Chem Ind Co Ltd 塩化ビニリデン系樹脂組成物およびその製造方法
JPS5980456A (ja) * 1982-09-28 1984-05-09 ザ・ビ−・エフ・グツドリツチ・カンパニ− クエン酸塩により安定化されたポリマ−組成物
JPH01163245A (ja) * 1987-12-20 1989-06-27 Nippon Synthetic Chem Ind Co Ltd:The 含ハロゲン熱可塑性樹脂組成物
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1171492A (ja) * 1997-06-20 1999-03-16 Kureha Chem Ind Co Ltd 塩化ビニリデン共重合体樹脂組成物、そのフィルム、その押出加工方法
JP2005513239A (ja) * 2001-12-20 2005-05-12 フエロ コーポレーション グリセリントリエステル可塑剤
JP2008074908A (ja) * 2006-09-19 2008-04-03 Asahi Kasei Chemicals Corp 塩化ビニリデン−アクリル酸メチル共重合体樹脂組成物及びその樹脂組成物から成るフィルム
JP2010286824A (ja) * 2009-05-15 2010-12-24 Sony Corp 光学体およびその製造方法、窓材、建具、ならびに日射遮蔽装置
JP2017537200A (ja) * 2014-12-09 2017-12-14 ロッテ アドバンスト マテリアルズ カンパニー リミテッド 自動車用熱可塑性樹脂組成物及びこれから製造された自動車用成形品
US10266692B2 (en) 2014-12-09 2019-04-23 Lotte Advanced Materials Co., Ltd. Automobile-use thermoplastic resin composition, and automobile-use molded product manufactured therefrom
US10316188B2 (en) 2014-12-19 2019-06-11 Lotte Advanced Materials Co., Ltd. Thermoplastic resin composition and molded part for automobiles using the same
JP2018529005A (ja) * 2015-08-28 2018-10-04 ロッテ アドバンスト マテリアルズ カンパニー リミテッド 熱可塑性樹脂組成物及びこれから製造された成形品
WO2023167198A1 (fr) * 2022-03-04 2023-09-07 株式会社クレハ Film d'emballage

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