WO1995027006A1 - Plastisol stable donnant un film a durete et resistance a la chaleur excellentes - Google Patents

Plastisol stable donnant un film a durete et resistance a la chaleur excellentes Download PDF

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Publication number
WO1995027006A1
WO1995027006A1 PCT/JP1995/000554 JP9500554W WO9527006A1 WO 1995027006 A1 WO1995027006 A1 WO 1995027006A1 JP 9500554 W JP9500554 W JP 9500554W WO 9527006 A1 WO9527006 A1 WO 9527006A1
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weight
plastisol
parts
compound
polymer
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PCT/JP1995/000554
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English (en)
Japanese (ja)
Inventor
Hideo Maehata
Soichi Muroi
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W.R. Grace & Co. - Conn.
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Priority to AU20831/95A priority Critical patent/AU2083195A/en
Publication of WO1995027006A1 publication Critical patent/WO1995027006A1/fr

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    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters

Definitions

  • the present invention relates to a non-vinyl chloride plastisol that withstands long-term storage at room temperature, and is excellent in toughness and heat resistance.
  • a plastisol is a liquid or paste-like product made by dispersing polymer particles in a liquid plasticizer and adding a filler and other additives as necessary.
  • the material becomes a soft solid at room temperature by heating. Change. That is, the polymer particles maintain their original shape without dissolving in the plasticizer or expanding when stored at room temperature, but rapidly absorb the plasticizer and gel when heated. Utilizing this property, which is suitable for painting and bonding, plastisols are usefully used in the fields of transportation vehicles, ships, toys, processed textiles, and packing materials.
  • vinyl chloride polymer By far the best polymer for plastisols is vinyl chloride polymer.
  • This polymer uses the most versatile dioctyl phthalate as a plasticizer to give a stable plastisol at ⁇ , room temperature, for more than a few months.
  • the soft plastic obtained by heating this vinyl chloride-based blastisol is tough.
  • the problems of polyvinyl chloride polymer products have become increasingly close-up. In other words, incineration of vinyl chloride polymer products produces hydrochloric acid and dioxin, both of which are harmful to the human body and seriously pollute the environment.In particular, hydrochloric acid corrodes incineration equipment. . From this perspective, there is a move to exclude vinyl chloride polymers from products that could enter municipal solid waste. PVC Of course, nil plastisol is also included in it.
  • Acrylic polymer-styrene polymer has been proposed as a polymer particle for plastisol instead of vinyl chloride polymer.
  • a simple acrylyl polymer cannot satisfy the requirements of plastisol particles, so various conditions are set.
  • German Patent Nos. 2, 454, 235 and 2, 529, 732 the particle size and particle composition determined with T g above 35 ° C are determined.
  • acrylic polymer particles have been proposed.
  • U.S. Pat. No. 4,071,656 acryloyl polymer particles having a coreosyl structure composed of a core having excellent compatibility with a plasticizer and a sealer having poor compatibility with a plasticizer are provided. Is being planned.
  • acryl polymer particles containing carboxy or amino groups are used for plastisols in which gas phase is neutralized with volatile alcohol or acid. Particles have been proposed, and U.S. Pat. Nos. 4,613,639 propose styrene copolymer plastisol particles bound with a protected colloid. However, none of them have reached the level of vinyl chloride polymer in terms of the storage stability of plastisol and the toughness and heat resistance of the formed film.
  • the inventor of the present application in Japanese Patent Application No. 4-325151, filed earlier, prepared a polymer particle by copolymerizing a polymerizable unsaturated compound and an unsaturated carboxylic acid compound in water.
  • the carboxyl groups of the polymer particles are alkaline It is obtained by preparing polymer particles having a number average particle size of 0.1 zm to 100 / im by neutralizing with a metal compound, and dispersing the polymer particles in a plasticizer.
  • a plastisol having a high level of storage stability has been disclosed.
  • a copolymer composition formed from an unsaturated carboxylic acid compound and a polymerizable unsaturated compound as described above has By adding a small amount of an ethylenically unsaturated compound having a functional group capable of reacting with a group, it is possible to provide a non-vinyl chloride plastisol that far exceeds the heat resistance of a vinyl chloride plastisol film without significantly lowering the film forming property. It has been disclosed that it can be.
  • the present inventor further studied the above-mentioned copolymer composition, and as a result, in the copolymer composition disclosed in Japanese Patent Application No. 4-324508, a polymerizable unsaturated compound component
  • a mixture of styrene or ⁇ -methylstyrene and acrylonitrile or methacrylonitrile at a certain fixed ratio in addition to the above-mentioned storage stability and heat resistance of the film, it is practically important as a plastisol film.
  • the inventors have found that a blastisol having very excellent film toughness, which is a characteristic, can be obtained, and have completed the present invention.
  • An object of the present invention is to provide a polymer composition that does not contain chlorine, has a high level of storage stability that cannot be achieved by conventional techniques, and has improved heat resistance and toughness when heated.
  • An object of the present invention is to provide a plastisol that gives a plastisol film having excellent properties.
  • Another object of the present invention is to provide a method for producing a plastisol having the characteristics described above.
  • the plastisol according to the present invention comprises 3 to 20 parts by weight of an unsaturated carboxylic acid compound, 0.2 to 10 parts by weight of an ethylenically unsaturated compound having a functional group capable of reacting with a boxyl group, 30 to 91.8 parts by weight of styrene or ⁇ -methylstyrene, and 5 to 5 parts by weight of acrylonitrile or methacrylonitrile 40 parts by weight of a copolymer, wherein at least 5% of the carboxyl groups are neutralized with an alkaline metal compound, having a number average particle diameter of 0.1 m to 100 m. It is characterized in that 100 parts by weight are dispersed in 50 to 200 parts by weight of a plasticizer.
  • the present invention relates to a method for producing a plastisol, comprising the steps of:
  • the figure is a graph showing the relationship between stress and elongation in a tensile test for films obtained from plastisols of Examples and Comparative Examples of the present invention.
  • All of the plastisol copolymers of the present invention are converted to copolymers.
  • the unsaturated carboxylic acid compound is 3 to 20 parts by weight, preferably 4 to 12 parts by weight, an ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group, 0.2 to 10 parts by weight, Preferably 0.5 to 5 parts by weight, styrene or ⁇ -methylstyrene 30 to 9 1.
  • '8 parts by weight preferably 53 to 85.5 parts by weight, and acrylonitrile or methacrylonitrile 5 to 40 It is a polymer obtained by copolymerization of 10 parts by weight, preferably 10 to 30 parts by weight.
  • the unsaturated carboxylic acid compound used as a monomer constituting the plastisol copolymer of the present invention contributes to the improvement of the storage stability of the obtained plastisol.
  • Examples of the unsaturated carboxylic acid compound that can be used in the present invention include acrylic acid, methacrylic acid, maleic acid and its monoester, itaconic acid and its monoester, fumaric acid and its monoester. These unsaturated carboxylic acid compounds can be used alone or as a mixture.
  • the amount of unsaturated carboxylic acid in the copolymer is between 3 and 20 parts by weight, preferably between 4 and 12 parts by weight. If this amount is less than 3 parts by weight, a practically recognizable level of storage stability cannot be expected. When the amount of the unsaturated carboxylic acid exceeds 20 parts by weight, the storage stability of the plastisol is improved, but at the same time, the temperature required for heating the plastisol to form a film increases.
  • Examples of the ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group that can be used in the present invention include glycidyl methacrylate and glycidyl. Noreacrylate, arylglycidyl ether, 2-hydroxyquinethyl acrylate and methacrylate, 2-hydroxypropyl acrylate and methacrylate, N-methylol acrylamide or N-methylol methacrylamide and its Alkoxylated products. These ethylenically unsaturated compounds can be used alone or as a mixture.
  • the amount of the ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group is 0.2 to 10 parts by weight, preferably 0.1 to 100 parts by weight, based on 100 parts by weight of all monomers constituting the plastisol copolymer. 5 to 5 parts by weight.
  • the amount is less than 0.2 part by weight, the effect of improving heat resistance is small, and when the amount exceeds 10 parts by weight, it becomes difficult to form a film by heating the plastisol.
  • styrene or -methylstyrene and acrylonitrile or methacrylonitrile used as monomers constituting the plastisol copolymer of the present invention are considered to contribute to the toughness of the formed film.
  • styrene or n-methylstyrene has very good compatibility with commonly used plasticizers such as octyl phthalate, and has excellent film elongation represented by a soft vinyl chloride resin.
  • plasticizers such as octyl phthalate
  • due to its high compatibility it is excessively plasticized, so that the mechanical strength of the film becomes very low, which has a practical problem.
  • copolymerizing acrylonitrile or methacrylonitrile in an appropriate amount the mechanical strength of styrene or ⁇ -methylstyrene is greatly improved without impairing the excellent film elongation, and the toughness is improved. Excellent film can be obtained.
  • the amount of styrene or ⁇ -methylstyrene used is 30 to 91.8 parts by weight, preferably 53 to 85.5 parts by weight. If it is less than this value, the compatibility with the plasticizer is inferior, and it is difficult to form a film. Even if the film can be formed, the film has a very small elongation and gives a brittle film. Also exceeds this value In such a case, although high elongation is exhibited, even if acrylonitrile or methacrylonitrile is copolymerized, the mechanical strength is very small, and improvement in the toughness of the film cannot be expected.
  • the amount of acrylonitrile or methacrylonitrile used in the present invention is 5 to 40 parts by weight, preferably 10 to 30 parts by weight. If this value is not ⁇ , the effect of improving the mechanical strength of the film with respect to styrene or monomethyl styrene described above cannot be obtained, and if it exceeds this value, the compatibility of the plastisol polymer with the plasticizer is significantly impaired. It not only reduces film formability, but also causes bleeding of plasticizer from the film.
  • composition of the copolymer for the plastisol of the present invention should be determined by the properties of the plastisol resin required within the above composition ranges.
  • copolymer particles according to the present invention can be produced by emulsion polymerization or suspension polymerization.
  • Emulsion polymerization is carried out by heating to 50 to 95 while stirring water containing 0.2 to 2% of emulsifier and 0.05 to 5% of a polymerization initiator with respect to all monomers. This can be done by adding 5 to 60% by weight of the monomer. It takes 3 to 8 hours to complete the polymerization.
  • polymerization initiators can be used in the emulsion polymerization, for example, aqueous solubility of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, etc.
  • An initiator a combination of such a water-soluble initiator with an oil-soluble initiator such as benzoyl peroxide, lauroyl peroxide, cumenehydriodropoxide, azobisisobutyronitrile and azobisdimethylvaleronitrile;
  • a combination of a solubility initiator or an oil solubility initiator with a reducing agent such as sodium sulfite, ammonium sulfite, ferrous oxide, cuprous oxide, sorbic acid and sucrose.
  • the size of the copolymer particles obtained in one emulsion polymerization is not so large. The size depends on the selected monomer composition and the method used, but is at most about 0.05 to 0.3 m. Therefore, if larger particles are desired, it is necessary to perform seed polymerization.
  • seed polymerization the dispersion of the already polymerized copolymer particles is stabilized by adding an emulsifier in an amount that does not generate new emulsifier micelles, and then the polymerization initiator is added to the stabilized dispersion, and The polymerization can be carried out by adding the monomer to a dispersion obtained under the above conditions and polymerizing the resultant. According to this seed polymerization method, the particles can be enlarged almost as calculated. In order to increase the size of the particles as calculated, it is desirable to repeat the seed polymerization as little as possible.
  • 0.05 to 5% by weight of the monomer in which the oil-soluble initiator described above is dissolved, based on the total amount of the monomer, and 0.5 to 5% by weight of water based on the total amount of the monomer are used.
  • Emulsification obtained by using a water-soluble polymer and / or inorganic fine particles or a water-soluble polymer Z surfactant mixture and emulsifying in water with vigorous stirring at a monomer concentration of 15 to 50% by weight, and gently stirring. Can be carried out by heating at 50 to 95 ° C. for 3 to 8 hours to complete the polymerization.
  • water-soluble polymers examples include polyvinyl alcohol, Examples include salts of hydroxyxethyl cellulose, sodium polyacrylate and styrene-maleic acid copolymer.
  • examples of the inorganic particles include calcium phosphate, calcium carbonate, magnesium hydroxide, talc, and clay.
  • surfactant tt agents include sodium stearate, sodium oleate, sodium laurate, sodium lauryl sulfate, sodium polyoxyethylene nonylphenyl ether sulfate, sodium sodium dodecylbenzenesulfonate, dibutyl Examples include sodium sulfosuccinate, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether, and polyoxyethylene sorbitan monolaurate.
  • the size of the copolymer particles obtained is much larger than that produced by emulsion polymerization.
  • the resulting particle size is from a few / zm to a few hundred / zm.
  • seed polymerization cannot be applied to suspension polymerization, so it is impossible to control the diameter of copolymer particles after the first suspension polymerization is completed.
  • the carboxyl group of the polymer particles obtained by the above-mentioned method is obtained by adding an alkyl ft metal compound to a polymer dispersion obtained by the emulsion polymerization or suspension polymerization described above at 5 ° C to 95 ° C. Neutralization by addition at a temperature of 7 and pH 7-14. In neutralization, an alkaline metal compound is added in the form of an aqueous solution and the temperature is 1
  • the temperature is preferably 5 to 30 ° C.
  • the polymer particles thus neutralized are dried into powdery plastisol polymer particles, usually by using a spray dryer.
  • the number average particle diameter of the particles (primary particles) produced by emulsion polymerization or suspension polymerization is usually 0.1 to: 100 / zm, preferably 0.3 to 20 / m. . If the particle size is less than 0.1 l ⁇ m, the amount of plasticizer required for pasting is increased, resulting in an overly flexible plastisol film. On the other hand, when the particle size is ⁇ ⁇ ⁇ ⁇ ⁇ O
  • the diameter of the particles obtained by spray drying is in the range of several ⁇ m to several hundreds of m, but these particles are secondary particles in which many primary particles (polymer particles formed by polymerization in water) are aggregated and coagulated. is there.
  • This particle size is basically not important. This is because when the secondary particles are dispersed in the plasticizer, they are partially dispersed to the primary particles by a stirring action. Therefore, the primary properties governing the important properties of the plastisol, such as the amount of plasticizer required to form the plastisol, the flowability and storage stability of the plastisol, and the rate of film formation (ie, the rate of plasticizer absorption) are determined by the primary Particles.
  • the present invention it is produced by copolymerization of an unsaturated carboxylic acid compound, an ethylenically unsaturated compound having a functional group capable of reacting with a carboxyl group, styrene or ⁇ -methylstyrene, and acrylonitrile or methacrylonitrile. Only by neutralizing the carboxyl group of the copolymer with the alkali metal compound, it is possible to achieve the object of the present invention to improve the storage stability and heat resistance of the blastisol and at the same time to increase the toughness of the obtained blastisol film. Becomes possible.
  • alkali metal compounds examples include monovalent alkali metal compounds such as sodium hydroxide and lithium hydroxide; divalent alkali metal compounds such as hydroxide Calcium, barium hydroxide, magnesium acetate, zirconium acetate, zinc ammonium chloride, zinc ammonium acetate and zirconium ammonium carbonate; trivalent alkaline metal compounds, such as aluminum hydroxide and basic acetic acid Aluminum.
  • Alkaline metals that are divalent rather than monovalent and trivalent than divalent provide better stability and higher heat resistance, but also increase the film formation temperature. Therefore, the type of alkaline metal used must be selected according to the purpose of the plastisol. No.
  • the degree of carboxyl neutralization also has a significant effect on important plastisol performance.
  • the higher the neutrality the higher the storage stability and the heat resistance of the plastisol film, but at the same time, the higher the film forming temperature. In actual neutralization, it is impossible to neutralize 100% of the carboxyl groups of the polymer.
  • the degree of neutralization differs depending on the type of unsaturated carboxylic acid compound used and the particle size of the polymer. For example,
  • the degree of neutralization is about 18%. Become. Further, if the styrene polymer particles are obtained by copolymerizing 7% by weight of acrylic acid and 1% by weight of glycidyl methacrylate, the degree of neutralization is 69% when the number average particle size is about 0.5 m. is there.
  • the degree of neutralization need not be 100%, but in the plastisol of the present invention, at least 5% of the carboxy groups of the polymer must be neutralized. If the degree of neutralization is less than 5%, a plastisol having storage stability sufficient for practical use and a plastisol film having sufficient heat resistance cannot be obtained. More preferably, it has a degree of neutralization of 10 to 80%.
  • the secondary particles produced by spray drying be as easily dispersible as possible in the primary particles during plastisol preparation. Because the secondary particles are porous This is because the amount of plasticizer used increases because plasticizers not related to fluidization are absorbed inside. As the amount of plasticizer used increases, the plastisol film becomes more flexible and loses its applicability to applications requiring a tough film.
  • the spray drying temperature be as low as possible and the Tg of the polymer be as high as possible.
  • the spray-drying temperature is at least 50 ° C, so the Tg of the polymer is of course limited.
  • the spray drying temperature should be at least 50 ° C.
  • plasticizers examples include: di-2-ethylhexyl phthalate, dibutyl phthalate, diisooctyl phthalate, butylcyclohexyl phthalate, butyl octyl phthalate, diisononyl phthalate, dicapryl Phthalates such as phthalate and disodecylphthalate; adipic esters such as di-2-ethylhexyl adipate and diisodecyl adipate; sebacates such as di-2-ethylhexyl sebaguet; dio Azelaic acid esters such as octyl azelate; phosphates such as tricresyl phosphate and tri-2-ethylhexyl phosphate; tri-2-ethylhexyl citrate and acetyl tributyl citrate Cuenoic acid Ter; acet
  • Plasticizers affect plastisol flow, film formation and film properties. Basically, the compatibility between the plasticizer and the polymer is an important factor.If the compatibility is extremely poor, it will not melt and form a continuous film even if heated, but Even if the properties are slightly inferior, practical problems arise such as the plasticizer oozing out from the inside to the film surface after the film is formed. Therefore, it is important to carefully consider the compatibility of the plasticizer with the polymer and carefully select it.
  • the amount of the plasticizer is usually in the range of 50 to 200 parts by weight (50 to 200 Phr) based on 100 parts by weight of the plastisol polymer particles.
  • the fluidity and film properties of plastisols can be adjusted with various additives. If necessary or desired, the above properties are adjusted by adding additives such as surfactants, pigments, fillers, foaming agents and solvents.
  • additives such as surfactants, pigments, fillers, foaming agents and solvents.
  • the solvent is functionally the same as the plasticizer, but volatilizes after the film is formed, so that the fluidity of the plastisol can be improved without softening the formed film.
  • the addition of too much solvent impairs the characteristics of the plastisol, so the amount of solvent added should be kept within 10 parts by weight per 100 parts by weight of the plastisol polymer.
  • Parts are “parts by weight” unless otherwise indicated.
  • a styrene (hereinafter, referred to as "St”) nomethacrylic acid (hereinafter, referred to as "MA A”) is placed in a 1,000 ml glass polymerization apparatus equipped with a stirrer and a reflux condenser.
  • the temperature was raised to 90 ° C. while stirring the mixture at 250 rpm. 4 hours heating Then, no reflux of the monomer was observed. Further, the reaction was continued under the same conditions for 2 hours to complete the reaction.
  • the particles were enlarged by a conventional seed polymerization method. Since the surface tension of the seed polymer dispersion was 65 dyne / cm, a 10% aqueous solution of sodium alkyldiphenyletherdisulfonate was added first to reduce the surface tension to below the critical micelle concentration of this surfactant. After reducing the surface tension to 30 dyneZcm, the concentration was adjusted to 20%.
  • the ratio was 98%, and the number average particle diameter was 0.23 im.This was again used as a seed polymer dispersion, and was again used in the same procedure to obtain a 20-fold amount of St / MAA / GMA (91 The polymerization rate was 98%, and the number average particle diameter was 0.52 // m. Was measured using an electrophoretic light scattering photometer ELS-800 manufactured by Otsuka Electronics Co., Ltd.
  • the polymer dispersion thus obtained was neutralized by adding a 5% aqueous sodium hydroxide solution to adjust the pH to 9.5.
  • the amount of sodium hydroxide added here was equivalent to the amount that neutralized 18% of the carboxyl groups of the copolymerized methacrylic acid.
  • the inlet temperature was set to 120 ° C using a spray dryer (Palvis GS-31, manufactured by Yamato Scientific Co., Ltd.) equipped with a 711-diameter nozzle.
  • the outlet temperature was 6 (spray-dried at TC.
  • the obtained particles were porous secondary particles having a diameter of 5 to 200 m.
  • This polymer powder was dispersed in a DOP to form a plastisol.
  • Table 1 shows the amount of DOP added to form, the initial viscosity of the obtained plastisol
  • Table 2 shows the storage stability (viscosity increase) at 23 ° C, the minimum film forming temperature, the heat resistance temperature and transparency of the formed film, and the 100% modulus, breaking strength and elongation of the formed film.
  • Table 3 shows the product of breaking strength and elongation (tensile product) as a measure of the toughness of the formed film.
  • the storage stability of plastisol, the minimum film formation temperature, the heat resistance temperature and the mechanical strength (100% modulus, breaking strength, elongation) of the formed film were measured by the following methods.
  • the viscosity of plastisol was measured at room temperature (23 ° C) using a B-type viscometer (BM type) manufactured by Tokyo Keiki Co., Ltd. Since plastisols exhibit thixotropic properties, the viscosity was taken as the value when equilibrium was reached.
  • the storage stability was expressed as a ratio obtained by dividing the viscosity measured after leaving the plastisol at room temperature for a predetermined period of time by the viscosity immediately after the preparation of the plastisol (initial viscosity).
  • the plastisol was heated at 180 ° C for 20 minutes to produce a plastisol sheet about 4 mm thick.
  • the heat resistance temperature was measured using TMA (120 C type manufactured by Seiko Denshi Kogyo). The measurement was carried out with a weight of 10 g using a needle probe having a diameter of 2 mm.
  • the sample sheet was cooled to -5 ° C, set, and heated at a rate of 4 ° C / min. Penetration was started after the temperature rose to 0 ° C, and the penetration was measured as a function of temperature. Penetration stays at zero at the beginning of temperature rise, or slow speed However, when the temperature exceeded the heat resistance of the sample sheet, the speed rapidly increased, and the sample sheet hit the quartz glass table and stopped.
  • the heat-resistant temperature was the temperature at which the probe penetrated 50% of the thickness of the measurement sample sheet.
  • the plastisol was heated at 180 ° C for 20 minutes to form a plastisol sheet having a thickness of about 2 mm, which was punched out with a JIS No. 2 type dumbbell to prepare a test sample.
  • This sample was subjected to a tensile tester Autograph AG5000B manufactured by Shimadzu Corporation to measure 100% modulus, breaking strength and elongation.
  • the test conditions were in accordance with JIS K7113 at a test speed of 10 OmmZ and a test temperature of 25 ° C.
  • a graph showing the relationship between stress and elongation until the film breaks obtained in this test is shown in Fig. 1 (line 1) in comparison with data on other plastisol films. Comparative Example 2
  • Glycerol diacetate monolaurate (manufactured by Riken Vitamin Co., Ltd., trade name Rikemar PL-002: hereinafter referred to as "GDML") was added to the polymer powder of StZMAAZGMA (91/7/2) obtained in Comparative Example 1. ) was added to form a plastisol, and its properties were measured.
  • Acetyl tributyl citrate (trade name CI TROFL EX A-4: manufactured by Fiza-1 Co., Ltd .; hereinafter referred to as "ATBC") was added to the polymer powder of StZMAAZGMA (91/7/2) obtained in Comparative Example 1. was blended into a plastisol, and its properties were measured.
  • Epoxidized soybean oil manufactured by Asahi Denka Kogyo Co., Ltd., trade name: Adeniki Sizer-1 0-130 P: "ESB" to form a plastisol and measure its properties "-.
  • the polymer powder of St / MAA / GMA (91/7/2) obtained in Comparative Example 1 was epoxidized with amaji oil (made by Asahi Denka Kogyo Co., Ltd., trade name: Adeiki Sizer-1 0-18 OA: below) , And "ELS '") were blended into plastisols, and their properties were measured.
  • Comparative Example 1 The procedure of Comparative Example 1 was repeated except that a mixed monomer of StZ acrylonitrile (hereinafter referred to as “AN”) ZMAAZGMA (weight ratio of 88Z3Z7-2) was used to obtain St / AN / MAA / GMA (88Z37 / 2) A copolymer dispersion was obtained. The polymerization rate was 98% and the number average particle size was 0.50 m. After the dispersion was neutralized with sodium hydroxide, the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain a polymer powder. The obtained polymer powder was blended into DOP to form a plastisol.
  • AN StZ acrylonitrile
  • ZMAAZGMA weight ratio of 88Z3Z7-2
  • Comparative Example 1 The procedure of Comparative Example 1 was repeated, except that a mixed monomer of St / AN / MAA / GMA (weight ratio: 81/10 Z7 Z2) was used, and the weight of StZANZMAAZGMA (81 / 10/7/2) was repeated. A combined dispersion was obtained. The polymerization rate was 98%, and the number average particle size was 0.50 m. After the dispersion was neutralized with sodium hydroxide, the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain polymer powder. The obtained polymer powder was blended into DOP to form a plastisol. Various properties of the obtained plastisol were measured, and the results are shown in the table. In addition, a graph showing the relationship between stress and elongation in a tensile test is shown with data on other plastisol films. A comparison is shown in Figure 1 (line 3).
  • Comparative Example 1 The procedure of Comparative Example 1 was repeated except that a mixed monomer of St / AN / MAA / GMA (weight ratio 71 20 Z 72) was used to obtain a copolymer of StZANZMAAZGMA (7 ⁇ / 20/7/2). A dispersion was obtained. The polymerization rate was 98%, and the number average particle size was 0.49 m. After the dispersion was neutralized with sodium hydroxide, the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain polymer powder. The obtained polymer powder was blended into DOP to form a plastisol. Various properties of the obtained plastisol were measured, and the results are shown in the table. Also, a graph showing the relationship between stress and elongation in the tensile test is shown in Fig. 1 (line 5) in comparison with data on other plastisol films.
  • Comparative Example 1 The procedure of Comparative Example 1 was repeated except that a mixed monomer of St / AN / MAA / GMA (weight ratio 61/30/7/2) was used, and the weight of StZANZMAAZGMA (61/30/7/2) was A combined dispersion was obtained.
  • the polymerization rate is 98% and the number average particle size is 0. 49 was 11.
  • the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain polymer powder.
  • the obtained polymer powder was blended into DOP to form a plastisol.
  • Various properties of the obtained plastisol were measured, and the results are shown in the table.
  • a graph showing the relationship between stress and elongation in the tensile test is shown in Fig. 1 (line 6) in comparison with data on other plastisol films.
  • Example 6 G DML was blended with the polymer powder of St / AN / MAA / GMA (weight ratio of 76/15/7/2) obtained in Example 2 to obtain a plastisol, and its properties were measured.
  • Example 6
  • Example 7 A TBC was blended with the polymer powder of St / AN / MAA / GMA (weight ratio 76/15/7/2) obtained in Example 2 to obtain a plastisol, and various properties were measured.
  • Example 7 A TBC was blended with the polymer powder of St / AN / MAA / GMA (weight ratio 76/15/7/2) obtained in Example 2 to obtain a plastisol, and various properties were measured.
  • Example 8 The polymer powder of St / AN / MAA / GMA (weight ratio of 76/15/7/2) obtained in Example 2 to form a plastisol, and its properties were measured.
  • Example 8 The polymer powder of St / AN / MAA / GMA (weight ratio of 76/15/7/2) obtained in Example 2 to form a plastisol, and its properties were measured.
  • a blastisol was prepared by mixing ELS with the polymer powder of St / AN / MAA / GMA (weight ratio 76/15/7/2) obtained in Example 2 and measuring its properties. Comparative Example 7
  • Comparative Example 1 The procedure of Comparative Example 1 was repeated except that a mixed monomer of methyl methacrylate (hereinafter referred to as "MMA") / ANZMAAZGMA (weight ratio 76Z15 / 7/2) was used to repeat MMAZANZMAAZGMA (76/15/7/2) A copolymer dispersion was obtained. The polymerization rate was 98%, and the number average particle size was 0.52 m. Hydroxyl dispersion After neutralization with sodium chloride, the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain a polymer powder. The obtained polymer powder was blended into ATBC to form a plastisol. Various properties of the obtained plastisol were measured, and the results are shown in the table.
  • MMA methyl methacrylate
  • ANZMAAZGMA weight ratio 76Z15 / 7/2
  • MMAZANZMAAZGMA weight ratio 76Z15 / 7/2
  • StZ methacrylonitrile MAAZGMA (76/15/7/2) was repeated by repeating the procedure of Comparative Example 1 except that a mixed monomer of StZ methacrylonitrile ZMAA / GMA (weight ratio: 7615Z7 / 2) was used.
  • a copolymer dispersion was obtained. The polymerization rate was 98%, and the number average particle size was 0.50 m. After the dispersion was neutralized with sodium hydroxide, the concentration of the neutralized polymer particles was adjusted to 12.5%, and the polymer particles were spray-dried to obtain a polymer powder. The obtained polymer powder was blended into DOP to make a blastisol. Various properties of the obtained plastisol were measured, and the results are shown in the table.
  • Example 3 71-20 7 2 0.49 NaOH 18 D0P 80
  • Example 4 61-30 7 2 0.49 NaOH 18 D0P 80
  • Example 5 76-15 7 20.50 NaOH 18 GDML 80
  • Example 6 76-15 7 2 0.50 NaOH 18 ATBC 80
  • Example 7 76-15 7 2 0.50 NaOH 18 ESB 80
  • Example 8 76-15 7 2 0.50 NaOH 18 ELS 80
  • Example 9 76 1 : '-15 7 2.0.50 NaOH 18 D0P 80
  • Example 10 76-15 2: 1 7 2 0.50 50 NaOH 18 DOP 80 n ⁇ -Methyl styrene
  • Comparative example 1 220 1 0 1 3 1 8 120 180 or more Almost transparent moon Comparative example 2 292 1 n 1 7 9 Q 120 180 or less _ ⁇ Semi-transparent Comparative example 3 290 1 0 1 1 1? 120 Almost comparable Comparative example 4 280 1 0 1 1 Q 120 180 or more translucent Comparative Example 5 290 1 1 1 1 1 ⁇ ⁇ u Q 120 180 or more semi-transparent Comparative Example 6 290 1 1 1 1 1 120 180 or less J "Almost transparent Comparative Example 7 210 1 n U 1 Q ⁇ Q 0. nu inn ion Almost ⁇ Bfl Example 1 225 1 ⁇ . ⁇ ⁇ 1 ⁇ , ⁇ U 1.
  • Example 2 40.0 125.0 450 5.6
  • the type of unsaturated carboxylic acid compound, the amount of unsaturated carboxylic acid compound in the copolymer, and the neutralization is governed by the type of alkaline metal compound and primary particle size.
  • storage stability improves as the amount of unsaturated carboxylic acid compound in the copolymer increases.
  • a type that is more easily distributed on the particle surface that is, a type that exhibits a higher neutralization rate with an alkaline metal compound, provides higher storage stability.
  • a combination of styrene or -methylstyrene and acrylonitrile or methacrylonitrile as a component constituting a plastisol polymer is a functional compound that chemically reacts with an unsaturated compound containing a carboxylic acid group and a carboxylic acid group.
  • the elongation of the plastisol film is almost impaired by forming a plastisol polymer using a certain amount of styrene or ⁇ -methylstyrene and acrylonitrile or methacrylonitrile as a copolymerization component.
  • the 100% modulus and breaking strength of the film could be dramatically increased without any increase, and the tensile product, which is a measure of the toughness of the film, could be increased by more than three times. In this case, as apparent from the film stress-elongation curve shown in FIG. 1, the film did not break near the yield point, and the shape of the fracture was tough fracture.
  • a film having a polymer composition containing no chlorine, having a high level of storage stability that cannot be achieved by conventional techniques, and exhibiting remarkable heat resistance and toughness is provided.
  • the plastisol according to the present invention not only contributes to environmental pollution but also replaces it in the fields of transportation vehicles, ships, toys, processed textile products, packing materials, and the like, in which vinyl chloride-based plastisols were conventionally used. , Not possible with vinyl chloride plastisol Utilizing the high heat resistance temperature and the excellent weather resistance, which have been able to do so, it is possible to cultivate new L and applications that have not been possible with a vinyl chloride blastisol.

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

Abstract

Un plastisol dépourvu de chlorure de vinyle peut être conservé à température ambiante pendant une longue période et il présente une dureté et une résistance à la chaleur excellentes. On le prépare en dispersant 100 parties en poids de particules d'un copolymère, d'un diamètre de particules moyen au nombre de 0,1 à 100 νm, dans 50 à 200 parties en poids d'un plastifiant. Ce copolymère se compose de 3 à 20 parties en poids d'un composé carboxylique insaturé, de 0,2 à 10 parties en poids d'un composé éthylénique doté d'un groupe fonctionnel réagissant avec un groupe carboxyle, de 30 à 91,8 parties en poids de styrène ou d'α-méthylstyrène, et de 5 à 40 parties en poids d'acrylonitrile ou de méthacrylonitrile, au moins 5 % des groupes carboxyle ayant été neutralisés par un composé d'un métal alcalin.
PCT/JP1995/000554 1994-04-01 1995-03-27 Plastisol stable donnant un film a durete et resistance a la chaleur excellentes WO1995027006A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU20831/95A AU2083195A (en) 1994-04-01 1995-03-27 Stable plastisol which gives film excellent in toughness and heat resistance

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP6/65085 1994-04-01
JP6508594A JPH07268154A (ja) 1994-04-01 1994-04-01 強靭性、耐熱性に優れたフィルムを与える安定なプラスチゾル

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WO1995027006A1 true WO1995027006A1 (fr) 1995-10-12

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1400572A4 (fr) * 2001-05-23 2004-12-15 Mitsubishi Rayon Co Composition de plastisol et objet moule et article prepares avec cette composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53140340A (en) * 1977-05-14 1978-12-07 Matsushita Electric Works Ltd Fumigated color tone development on copper surface
JPS6395248A (ja) * 1986-09-22 1988-04-26 グーリトーエセツクス・アクテイエンゲゼルシヤフト 貯蔵安定性の良いプラスチゾルおよびオルガノゾル

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53140340A (en) * 1977-05-14 1978-12-07 Matsushita Electric Works Ltd Fumigated color tone development on copper surface
JPS6395248A (ja) * 1986-09-22 1988-04-26 グーリトーエセツクス・アクテイエンゲゼルシヤフト 貯蔵安定性の良いプラスチゾルおよびオルガノゾル

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1400572A4 (fr) * 2001-05-23 2004-12-15 Mitsubishi Rayon Co Composition de plastisol et objet moule et article prepares avec cette composition

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JPH07268154A (ja) 1995-10-17

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