WO2016147953A1 - トリメリット酸トリエステル可塑剤およびそれを含有する塩化ビニル系樹脂組成物 - Google Patents
トリメリット酸トリエステル可塑剤およびそれを含有する塩化ビニル系樹脂組成物 Download PDFInfo
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- WO2016147953A1 WO2016147953A1 PCT/JP2016/057174 JP2016057174W WO2016147953A1 WO 2016147953 A1 WO2016147953 A1 WO 2016147953A1 JP 2016057174 W JP2016057174 W JP 2016057174W WO 2016147953 A1 WO2016147953 A1 WO 2016147953A1
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- acid
- alcohol
- plasticizer
- vinyl chloride
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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
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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
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0016—Plasticisers
Definitions
- the present invention relates to a trimellitic acid triester plasticizer and a vinyl chloride resin composition containing the trimeric acid triester plasticizer (hereinafter also simply referred to as “plasticizer” or “resin composition”).
- plasticizer or “resin composition”.
- the present invention relates to a trimellitic acid triester plasticizer capable of imparting excellent press-coloring resistance and cold resistance to a product, and a vinyl chloride resin composition containing the plasticizer.
- plasticizers that plasticize the resin, but as plasticizers for vinyl chloride resins, polyester plasticizers, epoxidized vegetable oil plasticizers such as epoxidized soybean oil (ESBO), dioctyl phthalate (DOP), etc. ) And diisononyl phthalate (DINP) plasticizers such as phthalate, dioctyl adipate (DOA) and adipic acid plasticizer such as diisononyl adipate (DINA), and trimellitic acid such as trioctyl trimellito (TOTM)
- plasticizers such as plasticizers are widely used. It is known that mechanical properties such as flexibility and tensile properties can be improved by blending these plasticizers into resins. When processing plastics into various molded products such as building materials and electric wires, such blending can be performed. Has been done.
- the performance required for plasticizers is not only plastic, but also, for example, cold resistance is an important required performance for automobile electric wires.
- Patent Document 1 a vinyl chloride resin is used together with trimellitic acid and pyromellitic acid ester plasticizers and polyvalent carboxylic acid ester plasticizers, and further blended with basic silicate and metal soap to prevent cold resistance.
- a vinyl chloride soft resin composition having improved properties and the like is disclosed.
- Patent Document 2 discloses that electrical characteristics are improved by blending hydrotalcite.
- Patent Document 3 discloses that cold resistance and heat resistance are improved by a plasticizer of trimellitic acid triester having a C9 aliphatic alcohol as a main component.
- plasticizers such as trimellitic acid triesters cannot be said to be effective plasticizers that can simultaneously satisfy press coloration resistance and cold resistance against vinyl chloride resins, and are more excellent. There is a need for plasticizers.
- an object of the present invention is to provide a plasticizer excellent in press coloration resistance and cold resistance, and a vinyl chloride resin composition containing the plasticizer, which can solve the above-mentioned problems.
- a trimellitic triester compound having a specific structure has an excellent press coloring resistance and cold resistance against vinyl chloride resin compositions.
- the present invention is a plasticizer that imparts an effect.
- the plasticizer of the present invention is a trimellitic acid triester plasticizer composed of a saturated fatty alcohol and trimellitic acid triester compound, wherein the saturated aliphatic alcohol is a linear alcohol having 8 to 10 carbon atoms. It is composed of a branched alcohol having 8 to 10 carbon atoms, and the ratio (mass ratio) of the linear alcohol to the branched alcohol is 78/22 to 50/50.
- the ratio (mass ratio) of the linear alcohol to the branched alcohol is preferably 60/40 to 50/50.
- the linear alcohol having 8 to 10 carbon atoms and the branched alcohol having 8 to 10 carbon atoms may be used in combination with a linear alcohol and a branched alcohol having different carbon numbers.
- the vinyl chloride resin composition of the present invention is characterized in that 20 to 120 parts by mass of the trimellitic triester plasticizer of the present invention is blended with 100 parts by mass of the vinyl chloride resin. It is.
- the present invention it is possible to provide a plasticizer excellent in press coloration resistance and cold resistance, and a vinyl chloride resin composition containing the plasticizer.
- the plasticizer of the present invention is a triester compound of saturated aliphatic alcohol and trimellitic acid (hereinafter referred to as “the present ester compound”).
- the saturated aliphatic alcohol used in the present invention is a mixture containing a linear alcohol having 8 to 10 carbon atoms and a branched alcohol having 8 to 10 carbon atoms, and the ratio (mass ratio) between the linear alcohol and the branched alcohol is 78 / It is 22 to 50/50, and preferably 60/40 to 50/50 from the viewpoints of press color resistance, cold resistance, plasticity and economy.
- the press color resistance When the mass ratio of the linear alcohol exceeds 78, the press color resistance may be inferior or the compatibility when the resin composition is made may be inferior. On the other hand, if it is less than 50, the cold resistance may be inferior or The plasticity may be inferior.
- Examples of the straight-chain alcohol having 8 to 10 carbon atoms used as the saturated aliphatic alcohol in the plasticizer of the present invention include 1-octanol, 1-nonanol, 1-decanol and the like.
- the combined use of 1-octanol and 1-decanol, 1-octanol alone, 1-nonanol alone, and the combined use of 1-octanol and 1-nonanol are preferable, and the ratio (mass ratio) of 1-octanol and 1-decanol is 80/20 to 20/80, 1-octanol alone, the ratio (mass ratio) of 1-octanol and 1-nonanol is more preferably 5/95 to 95/5, and the ratio of 1-octanol to 1-decanol ( (Mass ratio) is 70/30 to 30/70, 1-octanol alone, the ratio (mass ratio) of 1-octanol and 1-nonanol is more
- Examples of the branched alcohol having 8 to 10 carbon atoms used as the saturated aliphatic alcohol in the plasticizer of the present invention include 2-ethylhexanol, 3,3-dimethyl-2-hexanol, and 3,4-dimethyl-1- Hexanol, 2-methyl-1-heptanol, 3-methyl-1-heptanol, 5,5-dimethyl-1-hexanol, 2-methyl-3-ethylpentanol, 4-methyl-1-heptanol, 4-methyl- Isooctanol such as 4-heptanol, 2-nonanol, 3-nonanol, 2,4-dimethyl-1-heptanol, 2,2,5-trimethylhexanol, 2,3,4-trimethyl-2-hexanol, 2,6 -Dimethyl-4-heptanol, 4,6-dimethyl-1-heptanol, 2-methyl-2-octanol, 7 Iso heptan
- the method for producing the plasticizer of the present invention is not particularly limited.
- trimellitic acid, the anhydride or the acid chloride is converted into a straight-chain saturated aliphatic alcohol having 8 to 10 carbon atoms and a branch having 8 to 10 carbon atoms.
- the plasticizer of the present invention is prepared by performing batchwise or divided charging in the presence or absence of a catalyst and a mixture of saturated fatty alcohols of Can be obtained.
- the plasticizer of this invention may be used independently and may be used in combination of 2 or more type.
- the resin composition of the present invention comprises 20 to 120 parts by mass, preferably 30 to 100 parts by mass, more preferably 50 to 90 parts by mass of the ester compound based on 100 parts by mass of the vinyl chloride resin. Is.
- this ester compound may be used independently and 2 or more types may be used together.
- the vinyl chloride resin used in the resin composition of the present invention is not particularly limited in its polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
- plasticizers other than the ester compound and various additives such as organic acid metal salts, hydrotalcite compounds, zinc-modified hydrotalcite, zeolite compounds, phenolic compounds, or sulfur System antioxidants, ultraviolet absorbers, hindered amine light stabilizers, polyols, and other inorganic compounds can also be blended.
- Plasticizers and various additives other than the present ester may be used alone or in combination of two or more.
- plasticizer other than the ester compound examples include phthalates such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.
- phthalates such as dibutyl phthalate, butyl hexyl phthalate, diheptyl phthalate, di- (2-ethylhexyl) phthalate, diisononyl phthalate, diisodecyl phthalate, dilauryl phthalate, dicyclohexyl phthalate, and dioctyl terephthalate.
- Adipate plasticizers such as dioctyl adipate, diisononyl adipate, diisodecyl adipate, di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate , Tributyl phosphate, trioctyl phosphate, tri (butoxyethyl) phosphate, octy Phosphate plasticizers such as diphenyl phosphate; ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, Polyhydric alcohols such as trimethylolpropane and oxalic acid
- Sebacic acid type plasticizer such as tetrahydrophthalic acid type plasticizer, azelaic acid type plasticizer, di-2-ethylhexyl sebacate (DOS), dibutyl sebacate (DBS), etc.
- Plasticizers stearic acid plasticizers, citric acid plasticizers, pyromellitic acid plasticizers, biphenylene polycarboxylic acid plasticizers, polyhydric alcohol aromatic acid ester plasticizers (trimethylolpropane tribenzoate, etc.) Etc.
- a phthalate plasticizer, an adipate plasticizer, a sebacic acid plasticizer, an epoxy plasticizer, and an aromatic acid ester plasticizer of a polyhydric alcohol are used.
- the plasticizer can be blended within a range that does not impair the effects of the present invention, but is preferably 1 to 90 parts by weight, and more preferably 10 to 80 parts by weight with respect to 100 parts by weight of the vinyl chloride resin.
- organic acid metal salt examples of the organic acid component of the organic acid metal salt include carboxylic acids, organic phosphoric acids, and phenols.
- carboxylic acid examples include caproic acid, caprylic acid, pelargonic acid, octylic acid, 2-ethylhexylic acid, capric acid, neodecanoic acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, 12 -Hydroxystearic acid, chlorostearic acid, 12-ketostearic acid, phenylstearic acid, ricinoleic acid, linoleic acid, linolenic acid, oleic acid, arachidic acid, behenic acid, erucic acid, brassic acid and similar acids and tallow fatty acid, palm Natural fatty acid mixtures such as oil fatty acid, tung oil fatty acid, soybean oil fatty acid and cottonseed oil fatty acid, benzoic acid, p-tert-butylbenzoic acid, ethylbenzoic acid, iso
- octylic acid 2-ethylhexylic acid, neodecanoic acid, stearic acid, lauric acid, oleic acid, ricinoleic acid, and benzoic acid are preferred.
- organic phosphoric acid examples include mono- or dioctyl phosphoric acid, mono- or dododecyl phosphoric acid, mono- or dioctadecyl phosphoric acid, mono- or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester, and the like. Can be mentioned.
- phenols examples include phenol, cresol, ethylphenol, cyclohexylphenol, nonylphenol, dodecylphenol and the like.
- the metal component of the organic acid metal salt includes lithium (Li), sodium (Na), potassium (K), calcium (Ca), magnesium (Mg), strontium (Sr), zinc (Zn), cesium (Cs). , Tin (Sn), barium (Ba), aluminum (Al), and the like.
- magnesium, aluminum, calcium, zinc, and barium are preferable, and magnesium, aluminum, calcium, and zinc are more preferable.
- the organic acid metal salt which is a salt of the organic acid component and the metal component, can form a normal salt, an acidic salt, a basic salt, or an overbased salt by the combination thereof. You may use, and may use 2 or more types together.
- metal stearate, metal laurate, metal oleate, metal ricinoleate, metal neodecanoate, metal 2-ethylhexylate, benzoic acid Acid metal salts are preferred, and magnesium, aluminum, calcium, zinc, and barium are preferred as the metal.
- the organic acid metal salt can be blended within a range that does not impair the effects of the present invention, but is 0.001 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and exhibits thermal stability and processability.
- 0.003 to 4 parts by mass is preferable, 0.005 to 3 parts by mass is more preferable, 0.01 to 2 parts by mass is further preferable, and 0.1 to 1 part by mass is particularly preferable. If the content is less than 0.001 part by mass, the thermal stability may be insufficient, and if it exceeds 5 parts by mass, the workability may be reduced.
- hydrotalcite compound examples include compounds represented by the following general formula (1).
- z is 1 or 2
- a y ⁇ is a z-valent anion, ie, (CO 3 ) 2 ⁇ or (ClO 4 ) ⁇
- x is 0 ⁇ x ⁇ 0.5
- n represents 0 or a positive number.
- Specific examples include the following compounds.
- the hydrotalcite compound can be blended within a range that does not impair the effects of the present invention, but is preferably 0.01 to 5 parts by mass, and 0.03 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Part is particularly preferred.
- Examples of the zinc-modified hydrotalcite compound include a compound represented by the following general formula (2).
- M in a formula is magnesium or magnesium and calcium
- p, q, and r are numbers which satisfy
- fill the conditions represented by the following formula, respectively, and m is 0 or arbitrary positive numbers; 0 ⁇ r ⁇ 0.5, p + q 1 ⁇ r, p ⁇ q, 0.3 ⁇ p ⁇ 1, 0 ⁇ q ⁇ 0.5.
- Specific examples of the zinc-modified hydrotalcite compound used in the present invention include, for example, Japanese Patent Publication No. 46-2280, Japanese Patent Publication No.
- the refractive index of the zinc-modified hydrotalcite compound is preferably 1.52 to 1.56 from the viewpoint of transparency.
- Commercially available products include Alkamizer 4 (Alkamizer P-93, trade name made by Kyowa Chemical Industry), Alkamizer 7 (trade name made by Kyowa Chemical Industry), and the like.
- Alkamizer 4 Alkamizer P-93
- the surface of the zinc-modified hydrotalcite compound is coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as alkali metal oleate, and alkali metal dodecylbenzenesulfonate.
- Zinc-modified hydrotalcite compounds coated with organic sulfonic acid metal salts, higher fatty acid amides, higher fatty acid esters or waxes can also be used.
- the zinc-modified hydrotalcite compound can be blended within a range that does not impair the effects of the present invention, but is usually 0.001 to 10 parts by mass with respect to 100 parts by mass of the vinyl chloride resin, and is thermally stable. Is preferably 0.003 to 8 parts by weight, more preferably 0.05 to 6 parts by weight, still more preferably 0.1 to 5 parts by weight, from the viewpoints of heat resistance, workability, and press coloration resistance. Is particularly preferred. If the content is less than 0.001 part by mass, the thermal stability and press coloration resistance may be insufficient, and if it exceeds 10 parts by mass, the workability may be reduced.
- the zeolite compound is an aluminosilicate of an alkali or alkaline earth metal having a unique three-dimensional zeolite crystal structure, and typical examples thereof include A-type, X-type, Y-type and P-type zeolite, monodenite, anal Sites, sodalite aluminosilicates, clinobutyrolite, erionite, chabazite, etc., and water containing zeolitic water of these zeolite compounds (so-called zeolitic water) or anhydrous water except for crystallization water Any of the objects may be used.
- the zeolite compound can be blended within a range that does not impair the effects of the present invention, but is preferably 0.01 to 5 parts by mass, and 0.03 to 3 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Particularly preferred.
- phenolic antioxidants examples include 2,6-ditert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-ditert-butyl-4-hydroxy). Phenyl) propionate, distearyl (3,5-ditert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-ditert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4′-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert-butyl- 4-hydroxyphenoxy) -s-triazine, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), bis [3,3- (4-hydroxy-3-tert-butylphen
- the phenolic antioxidant can be blended within a range that does not impair the effects of the present invention, but is preferably 0.01 to 1 part by weight, and 0.03 to 0 parts per 100 parts by weight of the vinyl chloride resin. More preferably, 8 parts by mass.
- sulfur-based antioxidants examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). and ⁇ -alkyl mercaptopropionic acid esters.
- the sulfur-based antioxidant can be blended within a range that does not impair the effects of the present invention, but is preferably 0.01 to 1 part by weight, and 0.03 to 0 parts per 100 parts by weight of the vinyl chloride resin. More preferably, 8 parts by mass.
- Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4-tert-butyl-4 ′-(2- 2-hydroxybenzophenones such as methacryloyloxyethoxyethoxy) benzophenone and 5,5′-methylenebis (2-hydroxy-4-methoxybenzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2 -Hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3,5-ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl- 5-methylphenyl) -5-chlorobenzotriazole, 2 (2-hydroxy-3-dodecyl-5-methylphenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-
- hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane Tetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2, , 6-tetramethyl-4-piperidyl) .bis (tridecyl
- the hindered amine light stabilizer can be blended within a range that does not impair the effects of the present invention, but is preferably 0.01 to 1 part by weight, and 0.03 to 0 parts per 100 parts by weight of the vinyl chloride resin. More preferably, 8 parts by mass.
- polyols examples include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate, glycerin, tris ( 2-hydroxyethyl) isocyanurate, sorbitol, mannitol, lactitol and the like.
- the polyols can be blended within a range that does not impair the effects of the present invention, but 0.01 to 2 parts by weight, preferably 0.01 to 1 part by weight with respect to 100 parts by weight of the vinyl chloride resin. More preferred.
- inorganic compounds examples include calcium silicate, calcium phosphate, calcium oxide, calcium hydroxide, magnesium silicate, magnesium phosphate, magnesium oxide, and magnesium hydroxide.
- Other inorganic compounds can be blended within a range that does not impair the effects of the present invention, but 0.01 to 5 parts by weight, preferably 0.03 to 3 parts by weight with respect to 100 parts by weight of the vinyl chloride resin. Is more preferable.
- additives such as a filler, a colorant, a crosslinking agent, an antistatic agent, an antifogging agent, a plate-out preventing agent, a surface treatment agent, Lubricants, flame retardants, fluorescent agents, antifungal agents, bactericides, metal deactivators, mold release agents, pigments, processing aids, foaming agents, and the like can be blended within a range that does not impair the effects of the present invention. .
- the resin composition of the present invention can be used regardless of the preparation method, mixing method and processing method.
- the preparation method include a method in which the present ester compound, a vinyl chloride resin, and other additive components as necessary are charged all at once, and a method in which the components are charged separately.
- the mixing method include a V-type blender, a ribbon blender, a Henschel mixer, a rocking mixer, a tumbler mixer, a planetary mixer, a Banbury mixer, a mill mixer, a mixing roll, a kneader and the like.
- the resin composition when the resin composition is in a powder form or a pellet form, for example, an injection molding process using an injection molding machine, an extrusion process using an extruder, a solution casting method, a pressure molding process, a vacuum molding process, a press
- the molding process include powder molding, calendering, and the like.
- examples include spread molding, dipping molding, gravure molding, slush molding, and screen processing molding.
- the shape of the molded body is not particularly limited.
- An irregular shape such as a polygonal shape is exemplified.
- the obtained molded body includes pipes such as water pipes, pipe fittings, rain gutters, window frame siding, flat plates, corrugated plates, automobile underbody coats, instrument panels, consoles, door seats, Automotive parts such as undercarpets, trunk seats, door trims, various leathers, decorative sheets, agricultural films, food packaging films, wire coatings, various foam products, hoses, medical tubes, food tubes, refrigerator gaskets , Packings, wallpaper, flooring, boots, curtains, shoe soles, gloves, waterproofing boards, toys, decorative boards, blood bags, infusion bags, tarpaulins, mats, waterproof sheets, civil engineering sheets, roofing, tarpaulins, Useful for insulating sheets, industrial tapes, glass films, erasers, etc.
- pipes such as water pipes, pipe fittings, rain gutters, window frame siding, flat plates, corrugated plates, automobile underbody coats, instrument panels, consoles, door seats, Automotive parts such as undercarpets, trunk seats, door trims, various leathers, decorative sheets, agricultural films, food
- Examples 1 to 10 Comparative Examples 1 to 6> 100 parts by mass of a vinyl chloride resin (ZEST1000Z made by Shin Daiichi Vinyl Co., Ltd.), 2.5 parts by mass of a barium / zinc stabilizer (AC-255 made by ADEKA Co., Ltd.), listed in Tables 1 and 2 below 80 parts by mass of the above plasticizer was blended and roll kneaded under the conditions of 170 ° C. ⁇ 30 rpm (roll rotational speed) ⁇ 7 minutes (kneading time) ⁇ 0.7 mm (sheet thickness) to prepare a sheet.
- a vinyl chloride resin ZEST1000Z made by Shin Daiichi Vinyl Co., Ltd.
- AC-255 barium / zinc stabilizer
- the flexible temperature here refers to a temperature at a low temperature limit indicating a predetermined torsional rigidity (3.17 ⁇ 10 3 kg / cm 2 ) in the above measurement. It can be said that the cold resistance is excellent when the softening temperature is ⁇ 40 ° C. or lower.
- plasticizers in Table 1 are as follows.
- Plasticizer A straight chain saturated aliphatic alcohol having 8 and 10 carbon atoms (mass ratio: 50/50), branched saturated aliphatic alcohol having 9 carbon atoms and trimellitic acid triester, straight chain
- the ratio (mass ratio) of alcohol to branched alcohol is 60/40
- Plasticizer B The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer A is 50/50.
- Plasticizer C Triester of linear saturated aliphatic alcohol having 8 carbon atoms, branched saturated aliphatic alcohol having 9 carbon atoms and trimellitic acid, and the ratio (mass ratio) of linear alcohol to branched alcohol is 60 / 40 Plasticizer D: The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer C is 50/50.
- Plasticizer E Triester of linear saturated aliphatic alcohol having 8 and 10 carbon atoms (mass ratio: 50/50), branched saturated aliphatic alcohol having 10 carbon atoms and trimellitic acid, linear The ratio (mass ratio) of alcohol to branched alcohol is 75/25
- Plasticizer F The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer E is 60/40.
- Plasticizer G The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer E is 50/50.
- Plasticizer H Triester of linear saturated aliphatic alcohol having 8 carbon atoms, branched saturated aliphatic alcohol having 10 carbon atoms and trimellitic acid, and the ratio (mass ratio) of linear alcohol to branched alcohol is 75. / 25
- Plasticizer I The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer H is 60/40.
- Plasticizer J The ratio (mass ratio) of linear alcohol and branched alcohol in the plasticizer H is 50
- the plasticizers in Table 2 are as follows. Comparative compound 1: straight chain saturated aliphatic alcohol having 8 and 10 carbon atoms (mass ratio: 50/50) and trimellitic acid triester, the ratio (mass ratio) of linear alcohol to branched alcohol is 100/0 Comparative compound 2: Triester of linear saturated aliphatic alcohol having 8 carbon atoms and trimellitic acid, the ratio (mass ratio) of linear alcohol to branched alcohol is 100/0 Comparative compound 3: Triester of branched saturated aliphatic alcohol having 9 carbon atoms and trimellitic acid, and the ratio (mass ratio) of linear alcohol to branched alcohol is 0/100 Comparative compound 4: C9 linear and branched saturated aliphatic alcohol and trimellitic acid ester, the ratio (mass ratio) of linear alcohol to branched alcohol is 80/20 Comparative compound 5: Trial ester of linear saturated aliphatic alcohol having 8 and 10 carbon atoms (mass ratio: 50/50), branched saturated aliphatic alcohol having
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Abstract
Description
本発明の可塑剤は、飽和脂肪族アルコールとトリメリット酸のトリエステル化合物(以下、「本エステル化合物」と称す)である。
この中でも、炭素数9の分岐アルコールが好ましい。
本発明の可塑剤は、単独で用いてもよく、2種以上を併用して用いてもよい。
Mg1-xAlx(OH)2(Ay-)x/z・nH2O(1)
但し、式中のzは1又は2であり、Ay-はz価のアニオン、即ち、(CO3)2-又は(ClO4)-であり、xは、0<x≦0.5、nは0又は正数を表す。具体例としては、次に示すような化合物が挙げられる。
Mg0.750Al0.250(OH)2(CO3)0.125・0.5H2O
Mg0.692Al0.308(OH)2(CO3)0.154・0.1H2O
Mg0.683Al0.317(OH)2(CO3)0.159・0.5H2O
Mg0.667Al0.333(OH)2(CO3)0.167・0.1H2O
Mg0.750Al0.250(OH)2(ClO4)0.250・0.5H2O
Mg0.692Al0.308(OH)2(ClO4)0.308・0.1H2O
Mg0.667Al0.333(OH)2(ClO4)0.333・0.1H2O
MpZnqAlr(OH)2(CO3)r/2・mH2O(2)
但し、式中のMはマグネシウム、又は、マグネシウム及びカルシウムであり、p、q及びrは各々下記の式で表される条件を満足する数であり、mは0又は任意の正数である;0<r≦0.5、p+q=1-r、p≧q、0.3≦p<1、0<q<0.5。
本発明で用いられる亜鉛変性ハイドロタルサイト化合物の具体例としては、例えば、特公昭46-2280号公報、特公昭47-32198号公報、特公昭50-30039号公報、特公昭48-29477号公報及び特公昭51-29129号公報等に記載されている。当然、本発明においては市販品を用いることもできる。具体例としては、次に示すような化合物が挙げられる。
Mg0.38Zn0.3Al0.32(OH)2(CO3)0.16・0.2H2O
Mg0.45Zn0.23Al0.32(OH)2(CO3)0.16
Mg0.48Zn0.18Al0.34(OH)2(CO3)0.17
Mg0.48Zn0.2Al0.32(OH)2(CO3)0.16
Mg0.50Zn0.17Al0.33(OH)2(CO3)0.165・0.45H2O
Mg0.58Zn0.17Al0.25(OH)2(CO3)0.125・0.5H2O
Mg0.50Zn0.18Al0.32(OH)2(CO3)0.15
Mg0.50Zn0.2Al0.30(OH)2(CO3)0.16
Mg0.50Zn0.2Al0.30(OH)2(CO3)0.15・0.52H2O
Mg0.50Zn0.25Al0.25(OH)2(CO3)0.125
Mg0.51Zn0.17Al0.32(OH)2(CO3)0.16
Mg0.52Zn0.16Al0.32(OH)2(CO3)0.16・0.5H2O
Mg0.55Zn0.15Al0.30(OH)2(CO3)0.15
Mg0.60Zn0.14Al0.26(OH)2(CO3)0.13
Mg0.60Zn0.16Al0.24(OH)2(CO3)0.12
Mg0.60Zn0.20Al0.20(OH)2(CO3)0.1
Mg0.40Ca0.10Zn0.18Al0.32(OH)2(CO3)0.16
Mg0.30Ca0.2Zn0.2Al0.30(OH)2(CO3)0.15
Mg0.50Zn0.17Al0.33(OH)2(CO3)0.17・0.5H2O
Mg0.50Zn0.17Al0.33(OH)2(CO3)0.17・0.42H2O
Mg0.60Zn0.16Al0.24(OH)2(CO3)0.12・0.45H2O
Mg0.50Zn0.25Al0.25(OH)2(CO3)0.13・0.39H2O
Mg0.67Zn0.08Al0.25(OH)2(CO3)0.125・0.5H2O
Mg0.50Zn0.17Al0.33(OH)2(CO3)0.17
Mg0.50Zn0.25Al0.25(OH)2(CO3)0.125
Mg0.50Zn0.17Al0.33(OH)2(CO3)0.17・0.5H2O
Mg0.58Zn0.08Al0.34(OH)2(CO3)0.17・0.5H2O
塩化ビニル系樹脂(新第一塩ビ(株)製 ZEST1000Z)100質量部、バリウム/亜鉛系安定剤((株)ADEKA製 AC-255)2.5質量部、下記の表1及び表2に記載の可塑剤80質量部を配合し、170℃×30rpm(ロール回転速度)×7分(混練時間)×0.7mm(シート厚)の条件でロール混練してシートを作製した。
クラッシュベルグ試験機を用いて、JIS K-6773(1999)に準拠して測定した。柔軟温度(℃)が低いほど耐寒性に優れている。ここでいう柔軟温度とは、上記測定において所定のねじり剛性率(3.17×103kg/cm2)を示す低温限界の温度を指す。耐寒性能は、この柔軟温度が-40℃以下であるとその性能として優れているといえる。
上記にて得られた0.7mm厚のシートを重ねあわせ、180℃5分間プレス加工を行ない1mm厚のシートを作製し、汎用型色差計カラーエースTC-8600A(有限会社東京電色製)を用いて黄色度(Y.I;Yellowness Index)を測定した。耐プレス着色性能は、この黄色度が5.0以下であるとその性能として優れているといえる。
得られた試験結果を下記の表1及び表2に示す。
可塑剤A:炭素数8及び炭素数10の直鎖の飽和脂肪族アルコール(質量比:50/50)と炭素数9の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が60/40
可塑剤B:上記可塑剤Aの、直鎖アルコールと分岐アルコールの割合(質量比)が50/50
可塑剤C:炭素数8の直鎖の飽和脂肪族アルコールと炭素数9の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が60/40
可塑剤D:上記可塑剤Cの、直鎖アルコールと分岐アルコールの割合(質量比)が50/50
可塑剤E:炭素数8及び炭素数10の直鎖の飽和脂肪族アルコール(質量比:50/50)と炭素数10の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が75/25
可塑剤F:上記可塑剤Eの、直鎖アルコールと分岐アルコールの割合(質量比)が60/40
可塑剤G:上記可塑剤Eの、直鎖アルコールと分岐アルコールの割合(質量比)が50/50
可塑剤H:炭素数8の直鎖の飽和脂肪族アルコールと炭素数10の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が75/25
可塑剤I:上記可塑剤Hの、直鎖アルコールと分岐アルコールの割合(質量比)が60/40
可塑剤J:上記可塑剤Hの、直鎖アルコールと分岐アルコールの割合(質量比)が50/50
比較化合物1:炭素数8及び炭素数10の直鎖の飽和脂肪族アルコール(質量比:50/50)とトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が100/0
比較化合物2:炭素数8の直鎖の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が100/0
比較化合物3:炭素数9の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が0/100
比較化合物4:炭素数9の直鎖及び分岐の飽和脂肪族アルコールとトリメリット酸のエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が80/20
比較化合物5:炭素数8及び10の直鎖の飽和脂肪族アルコール(質量比:50/50)と炭素数10の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が40/60
比較化合物6:炭素数8の直鎖の飽和脂肪族アルコールと炭素数10の分岐の飽和脂肪族アルコールとトリメリット酸のトリエステルであり、直鎖アルコールと分岐アルコールの割合(質量比)が40/60
Claims (4)
- 飽和脂肪族アルコールとトリメリット酸のトリエステル化合物からなるトリメリット酸トリエステル可塑剤であって、上記飽和脂肪族アルコールが炭素数8~10の直鎖アルコールと炭素数8~10の分岐アルコールからなり、上記直鎖アルコールと上記分岐アルコールの割合(質量比)が78/22~50/50であることを特徴とするトリメリット酸トリエステル可塑剤。
- 上記直鎖アルコールと分岐アルコールの割合(質量比)が60/40~50/50である請求項1記載のトリメリット酸トリエステル可塑剤。
- 上記炭素数8~10の直鎖アルコールおよび上記炭素数8~10の分岐アルコールが、夫々異なる炭素数の直鎖アルコールおよび分岐アルコールが併用されてなる請求項1記載のトリメリット酸トリエステル可塑剤。
- 塩化ビニル系樹脂100質量部に対して、請求項1記載のトリメリット酸トリエステル可塑剤が20~120質量部配合されてなることを特徴とする塩化ビニル系樹脂組成物。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03115448A (ja) * | 1989-09-29 | 1991-05-16 | Fujikura Ltd | 可塑化塩化ビニル樹脂組成物 |
JPH11176240A (ja) * | 1997-12-15 | 1999-07-02 | Sumitomo Bakelite Co Ltd | 耐熱電線被覆用塩化ビニル系樹脂組成物 |
JP2012233099A (ja) * | 2011-05-02 | 2012-11-29 | Three M Innovative Properties Co | 熱伝導性シート |
JP2013040268A (ja) * | 2011-08-12 | 2013-02-28 | Yazaki Energy System Corp | 薄肉耐摩耗電線被覆用塩化ビニル樹脂組成物、および、薄肉耐摩耗電線 |
JP2013129734A (ja) * | 2011-12-21 | 2013-07-04 | Hitachi Cable Ltd | ポリ塩化ビニル樹脂組成物、それを用いた電線およびケーブル |
JP2014189688A (ja) * | 2013-03-28 | 2014-10-06 | New Japan Chem Co Ltd | トリメリット酸トリエステルを含有する塩化ビニル系樹脂用可塑剤 |
WO2015147300A1 (ja) * | 2014-03-27 | 2015-10-01 | 新日本理化株式会社 | 非フタル酸系エステルを含有する塩化ビニル系樹脂用可塑剤、及び該可塑剤を含有する塩化ビニル系樹脂組成物 |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3706208B2 (ja) | 1995-09-05 | 2005-10-12 | プラス・テク株式会社 | 塩化ビニル系樹脂組成物 |
JP2004193138A (ja) | 1997-09-08 | 2004-07-08 | Mitsui Chemicals Inc | 塩化ビニル系樹脂被覆電線 |
US7361704B2 (en) * | 2003-09-30 | 2008-04-22 | Adeka Corporation | Vinyl chloride resin composition for vehicles |
CN1993309B (zh) * | 2004-08-04 | 2010-11-10 | 埃克森美孚化学专利公司 | C8-c10醇的混合物以及衍生的增塑剂和表面活性剂 |
CN101889054A (zh) * | 2008-02-29 | 2010-11-17 | 日本瑞翁株式会社 | 粉体成形用氯乙烯系树脂组合物、氯乙烯系树脂成形体、层压体、汽车内装材以及粉体成形用氯乙烯系树脂组合物的制造方法 |
JP2016141787A (ja) * | 2015-02-05 | 2016-08-08 | 新日本理化株式会社 | 非フタル酸エステル系の塩化ビニル系樹脂用可塑剤およびそれを含有してなる塩化ビニル系樹脂組成物 |
KR20160139001A (ko) * | 2014-03-27 | 2016-12-06 | 신닛폰 리카 가부시키가이샤 | 비프탈산계 에스테르를 함유하는 염화비닐계 수지용 가소제 및 해당 가소제를 함유하는 염화비닐계 수지 조성물 |
JP2016155938A (ja) * | 2015-02-25 | 2016-09-01 | 新日本理化株式会社 | トリメリット酸トリエステルを含有してなる医療用塩化ビニル系樹脂組成物及び医療用材料 |
-
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-
2016
- 2016-03-08 KR KR1020177029578A patent/KR102510923B1/ko active IP Right Grant
- 2016-03-08 US US15/554,878 patent/US20180044504A1/en not_active Abandoned
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- 2016-03-08 WO PCT/JP2016/057174 patent/WO2016147953A1/ja active Application Filing
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Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03115448A (ja) * | 1989-09-29 | 1991-05-16 | Fujikura Ltd | 可塑化塩化ビニル樹脂組成物 |
JPH11176240A (ja) * | 1997-12-15 | 1999-07-02 | Sumitomo Bakelite Co Ltd | 耐熱電線被覆用塩化ビニル系樹脂組成物 |
JP2012233099A (ja) * | 2011-05-02 | 2012-11-29 | Three M Innovative Properties Co | 熱伝導性シート |
JP2013040268A (ja) * | 2011-08-12 | 2013-02-28 | Yazaki Energy System Corp | 薄肉耐摩耗電線被覆用塩化ビニル樹脂組成物、および、薄肉耐摩耗電線 |
JP2013129734A (ja) * | 2011-12-21 | 2013-07-04 | Hitachi Cable Ltd | ポリ塩化ビニル樹脂組成物、それを用いた電線およびケーブル |
JP2014189688A (ja) * | 2013-03-28 | 2014-10-06 | New Japan Chem Co Ltd | トリメリット酸トリエステルを含有する塩化ビニル系樹脂用可塑剤 |
WO2015147300A1 (ja) * | 2014-03-27 | 2015-10-01 | 新日本理化株式会社 | 非フタル酸系エステルを含有する塩化ビニル系樹脂用可塑剤、及び該可塑剤を含有する塩化ビニル系樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3269766A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115558220A (zh) * | 2022-10-14 | 2023-01-03 | 深圳市好亚通防护用品有限公司 | 一种防静电spu鞋底材料及其制备方法 |
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