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WO2011074473A1 - Composition élastomère thermoplastique et son procédé de fabrication - Google Patents

Composition élastomère thermoplastique et son procédé de fabrication Download PDF

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Publication number
WO2011074473A1
WO2011074473A1 PCT/JP2010/072131 JP2010072131W WO2011074473A1 WO 2011074473 A1 WO2011074473 A1 WO 2011074473A1 JP 2010072131 W JP2010072131 W JP 2010072131W WO 2011074473 A1 WO2011074473 A1 WO 2011074473A1
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Prior art keywords
thermoplastic elastomer
polyester oligomer
meth
cyclic polyester
elastomer
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PCT/JP2010/072131
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English (en)
Japanese (ja)
Inventor
円 古田
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アロン化成株式会社
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Priority to JP2011546080A priority Critical patent/JP5756025B2/ja
Publication of WO2011074473A1 publication Critical patent/WO2011074473A1/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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen

Definitions

  • the present invention is obtained by thermoplastic molding of a thermoplastic elastomer composition used for a sealing material, packing, vibration damping member, tube, automotive part, electrical / electronic part, etc., its production method, and thermoforming the thermoplastic elastomer composition. It relates to a molded body.
  • Thermoplastic elastomers have a molecular feature that combines a molecular structure called a hard segment with a high hardness at room temperature and a molecular structure called a soft segment with a low hardness, and can be extruded and injection-molded by heating and melting. Is widely used. Further, unlike a rubber material having a crosslinked molecular structure, it is used as a material that can be reused by heating and melting (see Non-Patent Document 1).
  • a dicarboxylic acid component (a) mainly composed of an aromatic dicarboxylic acid, a hydrogenated dimer diol (b-1), and a hydrogenation mainly composed of 1,4-butanediol.
  • Copolymerized polyester (A) obtained from diol component (b) containing diol (b-2) other than dimer diol as a main component, titanium compound (B), tin compound (C), and hindered Copolyester compositions containing a phenolic antioxidant (D) are described.
  • Patent Document 2 discloses a method for producing a rubber composition in which a vulcanized elastomer is dispersed in a thermoplastic polymer matrix formed by polymerization of reactive oligomers.
  • the glass transition temperature of the hard segment polystyrene is relatively low, so that the use is limited at a temperature of about 100 ° C., for example.
  • the polyester-type elastomer as described in Patent Document 1 has a high use temperature because of the high melting point of the crystalline hard segment, it is inferior in flexibility.
  • a polymer of a reactive oligomer that forms a continuous phase is a component having a high melting point and a high hardness even if the crosslinked elastomer that forms the dispersed phase is a low hardness component. For this reason, the contribution of the continuous phase is large in terms of hardness, and flexibility tends to be insufficient. Further, if the ratio of the crosslinked elastomer is increased for improving flexibility, the melt viscosity becomes high, so that the moldability tends to be insufficient.
  • An object of the present invention is to provide a thermoplastic elastomer composition excellent in flexibility, including a thermoplastic elastomer having a high melting point, a method for producing the same, and a molded product obtained by thermoforming the thermoplastic elastomer composition. There is.
  • the present invention (1) A raw material containing a (meth) acryl elastomer and a cyclic polyester oligomer in a weight ratio of 40/60 to 95/5 ((meth) acryl elastomer / cyclic polyester oligomer) is heated and mixed at a temperature of 120 to 300 ° C.
  • a thermoplastic elastomer composition comprising a thermoplastic elastomer having a melting point of 200 to 300 ° C.
  • thermoplastic elastomer having a melting point of 200 to 300 ° C.
  • thermoplastic elastomer and 1 to 50 parts by weight of a plasticizer are mixed with 100 parts by weight of the thermoplastic elastomer.
  • thermoplastic elastomer composition of the present invention includes a thermoplastic elastomer having a high melting point, and exhibits an excellent effect of good flexibility.
  • FIG. 1 is an electron micrograph (10,000 magnifications) of a cross section of a sheet sample obtained by molding the thermoplastic elastomer composition of Example 1-2.
  • FIG. 2 is an electron micrograph (48000 times) of a cross section of a sheet sample obtained by molding the thermoplastic elastomer composition of Example 1-2.
  • FIG. 3 is an electron micrograph (10,000 magnifications) of a cross section of a sheet sample obtained by molding the thermoplastic elastomer composition of Comparative Example 1-3.
  • FIG. 4 is an electron micrograph (48000 times) of a cross section of a sheet sample obtained by molding the thermoplastic elastomer composition of Comparative Example 1-3.
  • thermoplastic elastomer composition of the present invention comprises a thermoplastic elastomer having a high melting point obtained by heating and mixing (meth) acrylic elastomer and cyclic polyester oligomer at a specific weight ratio and at a specific temperature, It has good flexibility.
  • the melting point of the thermoplastic elastomer is 200 to 300 ° C., preferably 200 to 280 ° C. from the viewpoint of heat resistance and moldability.
  • the melting point does not exist, that is, when it is not thermoplastic, when the melting point exceeds 300 ° C., the moldability of the resulting thermoplastic elastomer composition deteriorates and the thermoplasticity is impaired.
  • the melting point is less than 200 ° C., use of the resulting thermoplastic elastomer composition in applications requiring high heat resistance is limited.
  • the durometer A hardness of the thermoplastic elastomer is preferably 20 to 90, more preferably 25 to 80, and still more preferably 30 to 70, from the viewpoint of flexibility of the thermoplastic elastomer composition obtained.
  • (Meth) acrylic elastomer is obtained by using one or two or more (meth) acrylic vinyl monomers and, if necessary, other copolymerizable vinyl monomers as constituent components and increasing the molecular weight by a polymerization reaction.
  • Examples of the (meth) acrylic vinyl monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth ) Cyclohexyl acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, glycidyl (meth) acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, acrylic Examples include acid phenoxyethyl.
  • copolymerizable vinyl monomers include styrene, ⁇ -methylstyrene, vinyl acetate, ethylene, propylene, butadiene, isoprene, maleic anhydride and the like.
  • (meth) acryl when it is indicated as (meth) acryl, it means both a methacrylate compound and an acrylate compound.
  • the amount of the (meth) acrylic vinyl monomer is preferably 20 mol% or more, more preferably 50 mol% or more in the constituent components.
  • copolymerizable vinyl monomers include styrene, ⁇ -methylstyrene and ethylene.
  • Examples of the monomer polymerization method for obtaining a (meth) acryl elastomer include a radical polymerization method, a living anion polymerization method, a living radical polymerization method, and the like.
  • Examples of the polymerization form include a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, and a bulk polymerization method.
  • the (meth) acrylic elastomer preferably has a glass transition temperature of 0 ° C. or lower, more preferably ⁇ 90 to ⁇ 5 ° C., and further preferably ⁇ 80 to ⁇ 10 ° C. It is.
  • a typical (meth) acrylic elastomer for example, a tri-core having one hard segment mainly composed of polymethyl methacrylate on each side of a soft segment mainly composed of one n-butyl polyacrylate.
  • a block copolymer is mentioned.
  • the hard segment may be polystyrene.
  • the glass transition temperature of the soft segment is preferably 0 ° C. or less, more preferably ⁇ 90 to ⁇ 5 ° C., and further preferably ⁇ 80 to ⁇ 10 ° C.
  • Examples of commercially available (meth) acrylic elastomers include LA polymer manufactured by Kuraray Co., Ltd., NABSTAR (registered trademark) manufactured by Kaneka Corporation, Nanostrength (registered trademark) manufactured by Arkema Corporation, and the like.
  • the cyclic polyester oligomer is preferably a polyester compound having a cyclic molecular structure having 2 to 10, preferably 2 to 8, ester units composed of aromatic dicarboxylic acid units and aliphatic diol units.
  • Examples of the aromatic dicarboxylic acid include terephthalic acid and isophthalic acid.
  • Examples of the aliphatic diol include ethylene glycol, propylene glycol, and tetramethylene glycol, and an aliphatic diol having 2 to 10 carbon atoms is preferable.
  • CBT-160 tin-based polyester polymerization catalyst-containing cyclic polybutylene terephthalate oligomer
  • the weight ratio of the (meth) acryl elastomer and the cyclic polyester oligomer ((meth) acryl elastomer / cyclic polyester oligomer) used for heating and mixing is 40/60 to 95/5, preferably 50/50 to 90/10, More preferably, it is 60/40 to 85/15.
  • this weight ratio is less than 40/60, that is, when there are too many cyclic polyester oligomers, a high molecular weight product is generated (may lead to crosslinking) due to excessive reaction between the (meth) acryl elastomer and the polyester.
  • thermoplasticity of the resulting composition precursor is impaired (becomes thermosetting and non-thermoplastic), and the moldability deteriorates. Even if a plasticizer is added to the composition precursor once the thermoplasticity is impaired, a composition having good flexibility cannot be obtained.
  • the weight ratio exceeds 95/5, that is, when the cyclic polyester oligomer is too small, the melting point of the resulting composition is lowered because the polyester concentration is low, and the heat resistance is lowered. Since the thermoplastic elastomer analog having too little cyclic polyester oligomer contains almost no crystalline component, the composition in which the plasticizer is added to the elastomer has a lower melting point and lower heat resistance.
  • the blending of the plasticizer is optional, and the plasticizer may be blended or not blended, but the weight ratio ((meth) acrylic) of the (meth) acryl elastomer and the cyclic polyester oligomer used for heating and mixing.
  • (Elastomer / cyclic polyester oligomer) is preferably 60/40 to 90/10, more preferably 65/35 to 88/12, still more preferably 70/30 to 86/14, and a plasticizer. Without it, the desired thermoplastic elastomer can be easily obtained.
  • the total content of the (meth) acryl elastomer and the cyclic polyester oligomer in the raw material is preferably 25% by weight or more, more preferably 50% by weight or more, and further preferably 75% by weight or more.
  • thermoplastic elastomer In the raw material of the thermoplastic elastomer, arbitrary resin materials, additives and the like may be added as long as the object of the present invention is not impaired.
  • the resin material examples include polyethylene resin, polypropylene resin, styrene resin, polymethyl methacrylate resin, polyvinyl acetate resin, polyvinyl chloride resin, acrylonitrile butadiene styrene resin, polycarbonate resin, polyamide resin, and polyurethane resin.
  • Additives include lubricants such as fatty acid metal salts and fatty acid esters; heat stabilizers such as phenolic compounds, amine compounds and sulfur compounds; benzotriazole compounds, benzophenone compounds, benzoate compounds and hindered phenol compounds
  • Light stabilizers Hydrolysis inhibitors such as epoxy compounds, acid anhydride compounds, carbodiimide compounds and oxazoline compounds; Plasticizers such as phthalate ester compounds, polyester compounds, (meth) acryl oligomers, process oils; sodium bicarbonate Inorganic foaming agents such as ammonium bicarbonate; organic foaming agents such as nitro compounds, azo compounds and sulfonyl hydrazides; fillers such as carbon black, calcium carbonate, talc and glass fiber; tetrabromophenol, ammonium polyphosphate, melamine cyanu Flame retardants such as silicate, magnesium hydroxide and aluminum hydroxide; silane coupling agents, titanate coupling agents, aluminate coupling agents and
  • the thermoplastic elastomer contains a phosphorus-containing heat stabilizer.
  • the phosphorus-containing heat stabilizer has an action of terminating the polymerization reaction of the cyclic polyester oligomer, and the reaction during heating and mixing is preferably controlled using the phosphorus-containing heat stabilizer. Therefore, from the viewpoint of suppressing excessive reaction (crosslinking reaction) and maintaining the thermoplasticity of the resulting thermoplastic elastomer and the thermoplastic elastomer composition, the phosphorus-containing thermal stabilizer is used in the process of producing a thermoplastic elastomer. When the polymerization reaction of the cyclic polyester oligomer has sufficiently progressed, it is preferably added to the system.
  • the phosphorus-containing heat stabilizer is added to the system after the polymerization reaction rate of the cyclic polyester oligomer is preferably 80% or more, more preferably 85% or more. .
  • the phosphorus-containing heat stabilizer also exhibits the effect of extending the pot life in the heated state when using (thermoforming) the thermoplastic elastomer composition. That is, the thermoplastic elastomer composition to which the phosphorus-containing heat stabilizer is added does not lose thermoplasticity even when heated for a relatively long time, and therefore has a higher degree of freedom in use conditions.
  • Phosphorus-containing thermal stabilizers include triphenyl phosphite, triisodecyl phosphite, tri-2-ethylhexyl phosphite, diphenylnonylphenyl phosphite, trinonylphenyl phosphite, 9,10-dihydro-9-oxa Phosphorus such as 10-phosphaphenant-10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphananthrene, O-cyclohexyl phosphite, trilauryl trithiophosphite, trioctadecyl phosphite Phyto compounds, diisodecyl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, dinonylphenyl pentaerythritol diphosphite,
  • the compounding amount of the phosphorus-containing heat stabilizer expresses the stopping action of the polymerization reaction of the cyclic polyester oligomer with respect to 100 parts by weight of the cyclic polyester oligomer, and reduces the thermoplasticity due to excessive high molecular weight or formation of crosslinks. From the viewpoint of prevention, 0.1 to 10 parts by weight is preferable, and 0.3 to 7 parts by weight is more preferable.
  • thermoplastic elastomer containing a heat stabilizer is also preferred. From the viewpoint of selecting the heat stabilizer, it has a function of stopping or suppressing the ester polymerization reaction or exchange reaction, or a function of deactivating or reducing the action of the catalyst of the ester polymerization reaction or exchange reaction. Can be mentioned.
  • the thermoplastic elastomer of the present invention preferably contains an aromatic polyester other than the cyclic polyester oligomer from the viewpoint of adjusting the hardness and strength of the composition.
  • aromatic polyester include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polyester elastomer.
  • the aromatic polyester may be added to the raw material before heating and mixing, or may be added to the raw material during the heating mixing or after the heating and mixing.
  • the melting point of the aromatic polyester is preferably 150 to 280 ° C., more preferably 170 to 250 ° C. in order to improve the balance between the heat resistance of the composition (the melting point of the composition is high) and the moldability of the composition.
  • the content of the aromatic polyester other than the cyclic polyester oligomer is preferably 5 to 250 parts by weight, more preferably 10 to 200 parts by weight, with respect to 100 parts by weight of the total amount of the (meth) acryl elastomer and the cyclic polyester oligomer. More preferred is 150 parts by weight.
  • the heating temperature is 120 to 300 ° C, preferably 150 to 290 ° C, more preferably 170 to 280 ° C.
  • the heating temperature is less than 120 ° C.
  • the cyclic polyester oligomer does not melt, so the polymerization reaction of the polyester does not proceed sufficiently, and the heat resistance of the resulting thermoplastic elastomer and thermoplastic elastomer composition does not improve.
  • the resulting composition loses thermoplasticity.
  • the heating temperature exceeds 300 ° C., the (meth) acryl elastomer is thermally decomposed, and the mechanical strength of the resulting thermoplastic elastomer and the thermoplastic elastomer composition is lowered.
  • the heating and mixing it is preferable to perform the heating and mixing until the polymerization reaction of the cyclic polyester oligomer sufficiently proceeds.
  • the cyclic polyester oligomer in the heat mixing, is preferably reacted so that the polymerization reaction rate is preferably 80% or more, more preferably 85% or more.
  • the appropriate heating and mixing time depends on the heating temperature.
  • the appropriate heating and mixing time is preferably adjusted so that the resulting thermoplastic elastomer has a melting point of 200 to 300 ° C. As a result, the melting point of the thermoplastic elastomer composition obtained is approximately 200 to 300 ° C.
  • the resulting composition will have a low melting point and insufficient heat resistance, and if it is too long, the resulting composition will be excessively high molecular weight or crosslinked (melting point is too high or not present) State), the thermoplasticity is lost and the flexibility is insufficient.
  • additives such as phosphorus-containing heat stabilizers or aromatic polyesters are added at the end of the polymerization reaction or after the completion of the polymerization reaction, moderate heating (for example, about 10 minutes) is added from the viewpoint of making the composition uniform. It is preferable to continue mixing.
  • a polyester polymerization catalyst for accelerating the polymerization reaction of the cyclic polyester oligomer can be used.
  • catalysts include antimony catalysts such as antimony trioxide, tin catalysts such as butyltin, octyltin, and stannoxane, titanium catalysts such as titanium alkoxide, and zirconium catalysts.
  • the amount of the polyester polymerization catalyst used is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 8 parts by weight, even more preferably 0.05 to 6 parts by weight with respect to 100 parts by weight of the cyclic polyester oligomer.
  • any apparatus can be used as long as it is a mixing apparatus having a tank capable of maintaining a heating state.
  • a mixing apparatus having a tank capable of maintaining a heating state.
  • examples thereof include a kneader, an extruder, and a polymerization can having a heating jacket.
  • the thermoplastic elastomer of the present invention preferably has a phase separation structure composed of a continuous phase and a dispersed phase.
  • the continuous phase includes a component derived from a (meth) acryl elastomer
  • the dispersed phase includes a component derived from a cyclic polyester oligomer.
  • the dispersed phase is finely dispersed in the continuous phase, and the maximum diameter of the dispersed phase in the composition observed with a transmission electron microscope is preferably 1 ⁇ m or less, preferably 0.8 ⁇ m or less. More preferred.
  • the diameter of the dispersed phase is a diameter in the case of a perfect circle, and a long diameter in the case of an ellipse.
  • thermoplastic elastomer Since the (meth) acryl elastomer that forms the continuous phase is a low hardness component, the thermoplastic elastomer is excellent in flexibility and moldability. Since the polymer derived from the cyclic polyester oligomer that forms the dispersed phase is a component having a high melting point, it imparts excellent heat resistance to the thermoplastic elastomer. Since a part of the cyclic polyester oligomer also reacts with the (meth) acryl elastomer to form a graft, it is presumed that the heat resistance of the composition is effectively improved.
  • the thermoplastic elastomer composition of the present invention preferably contains a plasticizer in addition to the thermoplastic elastomer.
  • a plasticizer is added to a thermoplastic resin composed of an amorphous component, the heat resistance is usually lowered.
  • the polymer component derived from the cyclic polyester oligomer is crystalline, the crystalline polymer It is presumed that the heat resistance does not decrease even when a plasticizer that is incompatible with the component is added. Rather, the increase in the crystallization temperature is presumed to be because the degree of freedom of molecular motion increases due to the presence of the plasticizer, and the crystalline component can form a denser crystal.
  • thermoplastic elastomer When the thermoplastic elastomer has a phase-separated structure, the phase-separated structure is usually maintained even when a plasticizer is added, and the plasticizer is hardly compatible with the crystalline component, so that it is substantially distributed in the continuous phase. .
  • the crystallization temperature of the thermoplastic elastomer is increased by mixing with the plasticizer (the melting point is small before and after mixing with the plasticizer, so the difference between the melting point and the crystallization temperature is reduced).
  • the cooling time when the elastomer composition is molded to produce a molded article can be shortened, and the productivity of the molded article production can be improved.
  • the plasticizer means a liquid additive that is added to a thermoplastic resin or rubber to impart flexibility and workability.
  • a plasticizer A phthalate ester plasticizer, a trimellitic ester plasticizer, an aliphatic dibasic ester plasticizer, a phosphate ester plasticizer, a polyester plasticizer, an acetate ester
  • plasticizers ricinoleic acid plasticizers, sulfonamide plasticizers, poly (meth) acrylate plasticizers, process oils, and paraffin oils.
  • phthalate ester plasticizer examples include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate and the like.
  • trimellitic acid ester plasticizers examples include tris (2-ethylhexyl) trimellitate and the like.
  • aliphatic dibasic acid ester plasticizer examples include dibutyl adipate, bis (2-ethylhexyl) adipate, bis (2-ethylhexyl) azelate, dibutyl sebacate, bis (2-ethylhexyl) sebacate and the like.
  • phosphate ester plasticizer examples include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate and the like.
  • polyester plasticizers include high molecular weight plasticizers mainly composed of poly (1,3-butanediol adipate).
  • poly (meth) acrylate plasticizers include low molecular weight polymers (weight average molecular weight of about 1000 to 20000) containing 2-ethylhexyl acrylate, n-butyl acrylate, and the like as main constituent monomer units. Can be mentioned.
  • the content of the plasticizer is 1 to 50 parts by weight, preferably 1.5 to 40 parts by weight, more preferably 2 to 30 parts by weight with respect to 100 parts by weight of the thermoplastic elastomer.
  • the content of the plasticizer is less than 1 part by weight, the effect of improving flexibility is not exhibited.
  • the crystallization temperature of the thermoplastic elastomer composition is not sufficiently increased, and the effect of improving the productivity of production of injection molded articles (shortening the cooling time) is not exhibited.
  • the content of the plasticizer exceeds 50 parts by weight, the molded product becomes too flexible, the mold release from the injection mold is poor, and production may be hindered.
  • any apparatus can be used as long as it is a mixing apparatus having a tank capable of maintaining a heated state.
  • a mixing apparatus having a tank capable of maintaining a heated state.
  • examples thereof include a kneader, an extruder, and a mixer having a heating jacket.
  • the mixing temperature is not particularly limited as long as the mixing operation is possible.
  • the heat mixing of the (meth) acryl elastomer and the cyclic polyester oligomer accelerates the polymerization by the ring-opening polymerization of the cyclic polyester oligomer, and there is a plasticizer from the viewpoint of obtaining a thermoplastic elastomer having higher heat resistance. It is preferable to carry out in such a state.
  • the plasticizer is added by heating and mixing the (meth) acryl elastomer and the cyclic polyester oligomer after the heating and mixing of the (meth) acryl elastomer and the cyclic polyester oligomer is completed or even during the heating and mixing. It is preferable after the melting point of the thermoplastic elastomer reaches 200 ° C.
  • thermoplastic elastomer composition of the present invention by a method of mixing the thermoplastic elastomer and the plasticizer obtained as necessary.
  • the plasticizer in the mixing apparatus used for the heating and mixing following the heating and mixing process of the (meth) acryl elastomer and the cyclic polyester oligomer.
  • thermoplastic elastomer composition there is a method of using an extruder having a plurality of raw material charging ports.
  • the (meth) acryl elastomer and the cyclic polyester oligomer are supplied from the first raw material inlet on the upstream side of the extruder, and these raw materials are fed to the downstream side of the extruder while being heated and mixed.
  • a plasticizer (preferably a plasticizer in which a phosphorus-containing heat stabilizer is dissolved or dispersed) is supplied from the second raw material inlet on the downstream side of the extruder, and the (meth) acryl elastomer sent from the upstream side It is mixed with a heated mixture with a cyclic polyester oligomer.
  • thermoplastic elastomer composition of the present invention may be one in which some component is added to the thermoplastic elastomer, or may be the thermoplastic elastomer itself. Therefore, the same resin materials and additives as described above may be added to the thermoplastic elastomer composition of the present invention as long as the object of the present invention is not impaired.
  • the total content of (meth) acrylic elastomer and cyclic polyester oligomer in the thermoplastic elastomer composition excluding the plasticizer is preferably 25% by weight or more. 50% by weight or more is more preferable, and 75% by weight or more is more preferable.
  • the melting point of the thermoplastic elastomer composition of the present invention is preferably 200 to 300 ° C., more preferably 200 to 280 ° C. from the viewpoint of moldability.
  • the melting point of the thermoplastic elastomer composition of the present invention obtained by mixing a thermoplastic elastomer having a melting point of 200 to 300 ° C. and a plasticizer in a predetermined ratio is, as a result, not much different from the melting point of the thermoplastic elastomer. Become.
  • thermoplastic elastomer hardly decreases even when a plasticizer is added is related to the fact that the crystal structure of the crystalline component of the thermoplastic elastomer composition becomes denser and the crystallization temperature rises as described above. It is presumed that
  • the crystallization temperature of the thermoplastic elastomer composition is preferably from 130 to 180 ° C, more preferably from 135 to 170 ° C, and even more preferably from 140 to 160 ° C from the viewpoint of heat resistance and molding productivity.
  • the amount of crystallization heat is preferably 5 to 30 J / g, more preferably 6 to 20 J / g, from the viewpoint of heat resistance.
  • the durometer A hardness of the thermoplastic elastomer composition is preferably 10 to 80, more preferably 15 to 70, from the viewpoint of flexibility of the thermoplastic elastomer composition obtained.
  • thermoplastic elastomer composition of the present invention can be molded by appropriately heating according to a conventional method.
  • the use of the molded product obtained by thermoforming the thermoplastic elastomer composition of the present invention is not particularly limited, but is a general styrene elastomer, polyolefin elastomer, polyurethane elastomer, polyamide elastomer, acrylic It can be used in fields where elastomers, polyester elastomers, and the like are used.
  • the apparatus used for manufacturing the molded body of the present invention can be any molding machine capable of melt-mixing molding materials. Examples thereof include a kneader, an extrusion molding machine, an injection molding machine, a press molding machine, a blow molding machine, and a mixing roll.
  • Examples 1-3, 1-4 and Comparative Example 1-3 (Meth) acrylic elastomer and cyclic polyester oligomer shown in Table 1 are put into a kneader (Plastograph EC 50 type mixer manufactured by Brabender Co., Ltd.) heated to the temperature shown in Table 1, and the blade rotation speed is 60 r / min. Were mixed for the time shown in Table 1. After mixing, a phosphorus-containing heat stabilizer (Examples 1-3 and 1-4 only) and an aromatic polyester (Examples 1-4 and Comparative Example 1-3 only) were added and the same conditions (temperature, rotational speed) were added. ) For 10 minutes, and the obtained thermoplastic elastomer was taken out.
  • the glass transition temperature of the (meth) acryl elastomer and the melting point of the aromatic polyester were measured by the following methods.
  • Glass transition temperature of (meth) acrylic elastomer Using a dynamic viscoelasticity measuring device (RSAIII manufactured by TA Instruments Co., Ltd.), tan ⁇ (loss tangent) under the conditions of -80 to 50 ° C temperature range, 5 ° C / min heating rate and frequency 10Hz ) was determined as the glass transition temperature.
  • thermoplastic elastomer The polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was measured by the following method. The results are shown in Table 1.
  • thermoplastic elastomers obtained in the examples and comparative examples were heated to 230 ° C for the thermoplastic elastomers obtained in the examples and comparative examples, using a 2mm thick ⁇ 10cm ⁇ 10cm mold for 5 minutes Press molded. Thereafter, a cooling press was applied for 5 minutes, and a 2 mm thick sheet sample was taken out.
  • thermoplastic elastomer sheet sample of Example 1-2 is shown in FIG. 1 (10000 times) and FIG. 2 (48000 times), and a photograph of the thermoplastic elastomer sheet sample of Comparative Example 1-2 is shown in FIG. ) And FIG. 4 (48000 times).
  • the continuous phase which exhibits white is a phase containing many components derived from the (meth) acryl elastomer. From the comparison between FIG. 1 and FIG. 3, it is clear that in Example 1-2, the dispersed phase is remarkably finely dispersed as compared with Comparative Example 1-3. 4 and FIG. 4, it can be seen that the boundary between the dispersed phase and the continuous phase is less clear in Example 1-2 than in Comparative Example 1-3. This suggests that in Example 1-2, the compatibility of each component of the thermoplastic elastomer is better.
  • the durometer A hardness and melting point of the thermoplastic elastomer obtained using the sheet sample were measured by the following methods. The results are shown in Table 1.
  • thermoplastic elastomers of Examples 1-1 to 1-6 also thermoplastic elastomer compositions
  • thermoplastic elastomer of Comparative Example 1-1 that does not use a cyclic polyester oligomer has a low melting point and lacks heat resistance
  • the thermoplastic elastomer of Comparative Example 1-2 has a (meth) acryl elastomer / cyclic polyester oligomer weight ratio (95/5) within a predetermined range, but has a low melting point (190 ° C.) and lacks heat resistance. Yes.
  • thermoplastic elastomer can be obtained (see Example 3-1).
  • the thermoplastic elastomer of Comparative Example 1-3 using a polybutylene terephthalate resin instead of the cyclic polyester oligomer has a low melting point and lacks heat resistance because the reaction between the (meth) acryl elastomer and the polyester resin does not proceed. ing.
  • the thermoplastic elastomer of Comparative Example 1-4 has poor thermoplasticity and lacks moldability.
  • the weight ratio (50/50) of (meth) acryl elastomer / cyclic polyester oligomer is within a predetermined range, but is non-thermoplastic. Similar to Comparative Example 1-4, even if the weight ratio of (meth) acryl elastomer / cyclic polyester oligomer is 40/60, the melting point is 200 to 300 ° C., for example, by shortening the heating and mixing time of these raw materials. A thermoplastic elastomer can be obtained (see Elastomer D (equivalent to Example 2-16)).
  • Example 1-1 Example 1-1
  • Example 1-3 Example 1-1
  • Example 1-1 and Example 1-3 the step (Step A) in which the (meth) acrylic acid elastomer and the cyclic polyester oligomer were reacted by heating and mixing at 240 ° C. for 20 minutes was under the same conditions.
  • Step A immediately after Step A, the product was taken out from the reactor (kneader), and the heating and mixing were completed to obtain a thermoplastic elastomer.
  • the polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was 91.2%.
  • a phosphorus-containing heat stabilizer was added, and the process of the process of heating and mixing at 240 ° C. for 10 minutes (process B) was performed.
  • thermoplastic elastomer was obtained.
  • the polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was 89.4%.
  • Example 1-3 Although the heating and mixing time at 240 ° C. was 10 minutes longer than that in Example 1-1, the polymerization reaction rate was almost the same. It is assumed that the reaction of the cyclic polyester oligomer is effectively suppressed. The polymerization reaction rate of the cyclic polyester oligomer in the thermoplastic elastomer obtained in Example 1-1 was observed to be slightly larger (+ 1.8%) than that of the thermoplastic elastomer obtained in Example 1-3. This seems to be an experimental error.
  • thermoplastic elastomer typically by heat molding
  • Test examples 1-6 Using a hot press set at 240 ° C., a molded test piece made of the thermoplastic elastomer obtained in Example 1-1 or Example 1-3 was produced. Except that the heating temperature was changed to 240 ° C. and the heating press time was variously changed, it was carried out in the same manner as in the preparation of the sheet sample. Table 2 shows the results of measuring the melting point of the molded specimens obtained under the same conditions as described above.
  • thermoplastic elastomer of Example 1-1 lost its thermoplasticity at 240 ° C. for 10 minutes (Test Example 2), whereas the thermoplastic elastomer of Example 1-3 at 240 ° C. for 30 minutes.
  • the thermoplasticity is maintained even during heating (Test Example 6). Therefore, it can be seen that the thermoplastic elastomer to which the phosphorus-containing heat stabilizer is added has a wider allowable range of conditions for producing a molded body by, for example, heating and melting.
  • thermoplastic elastomer 1-3 obtained in Example 1-3 was injection molded under the following conditions to produce a plate-shaped molded body having a length of 125 mm, a width of 125 mm, and a thickness of 2 mm.
  • ⁇ Injection molding machine Mitsubishi Heavy Industries, Ltd. 100MS III ⁇ Cylinder temperature: 230 °C ⁇ Injection pressure: 98MPa ⁇ Injection time: 3 seconds ⁇ Mold temperature: 25 °C
  • the glass transition temperature of the (meth) acryl elastomer was measured by the following method.
  • Glass transition temperature of (meth) acrylic elastomer Using a dynamic viscoelasticity measuring device (RSAIII manufactured by TA Instruments Co., Ltd.), tan ⁇ (loss tangent) under the conditions of -80 to 50 ° C temperature range, 5 ° C / min heating rate and frequency 10Hz ) was determined as the glass transition temperature.
  • thermoplastic elastomer The polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was measured by the following method. The results are shown in Table 3.
  • the durometer A hardness and melting point of the thermoplastic elastomer obtained using the sheet sample were measured by the following methods. The results are shown in Table 3.
  • Elastomer A and Elastomer C the (meth) acrylic acid elastomer and the cyclic polyester oligomer were reacted by heating and mixing at 240 ° C. for 20 minutes (Step A).
  • Step A immediately after Step A, the product was taken out from the reactor (kneader), and the heating and mixing were finished to obtain a thermoplastic elastomer.
  • the polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was 91.2%.
  • a phosphorous-containing heat stabilizer was added after Step A, and the process of Step (Step B) of heating and mixing at 240 ° C. for 10 minutes was performed.
  • thermoplastic elastomer was obtained.
  • the polymerization reaction rate of the cyclic polyester oligomer in the obtained thermoplastic elastomer was 89.4%.
  • thermoplastic elastomer and plasticizer shown in Table 4 were put into a kneader (Plastograph EC 50 type mixer manufactured by Brabender Co., Ltd.) heated to 240 ° C. and mixed for 5 minutes at a blade rotation speed of 60 r / min.
  • the obtained thermoplastic elastomer composition was taken out.
  • Table 4 shows the results of measuring the durometer A hardness and melting point under the same conditions as described above for the obtained thermoplastic elastomer composition.
  • thermoplastic elastomer composition 5 mg was sampled, and using a differential scanning calorimeter (DSC-60 manufactured by Shimadzu Corporation), the temperature was changed from 40 ° C. to 280 ° C. at a temperature condition of 20 ° C./min.
  • the temperature of the crystallization peak observed when cooling to 40 ° C. at 20 ° C./min was defined as the crystallization temperature, and the peak area was defined as the amount of crystallization heat.
  • Table 4 The results are shown in Table 4.
  • thermoplastic elastomer compositions of Examples 2-1 to 2-12 blended with a plasticizer have a durometer A hardness smaller than that of Examples 2-13 to 2-17, and are flexible. It has excellent properties, has an equivalent melting point and a high crystallization temperature, and has good heat resistance and productivity in the production of a molded body. Further, since the amount of heat of crystallization is large, there is also an effect that it is difficult to be deformed even if exposed to a high temperature for a short time.
  • thermoplastic elastomer Elastomer D except that the amount of (meth) acrylic elastomer / cyclic polyester oligomer used was changed to 15.6 g / 36.4 g (weight ratio 30/70) in the production conditions for elastomer D in Example 2-2.
  • Comparative Example 2-2 90 parts by weight of (meth) acrylic elastomer “NABSTAR N800AS” (equivalent to the composition of Comparative Example 1-1) and 10 parts by weight of plasticizer “TOTM” were mixed. The melting point of the obtained thermoplastic elastomer composition was lower than 190 ° C.
  • Example 2-18 The thermoplastic elastomer composition obtained in Example 2-2 was injection molded under the following conditions to produce a plate-like molded product having a length of 125 mm, a width of 125 mm, and a thickness of 2 mm.
  • ⁇ Injection molding machine Mitsubishi Heavy Industries, Ltd. 100MS III ⁇ Cylinder temperature: 230 °C ⁇ Injection pressure: 98MPa ⁇ Injection time: 3 seconds ⁇ Mold temperature: 25 °C
  • Example 2-19 Using a hot press set at 230 ° C., molded test pieces made of the thermoplastic elastomer composition obtained in Example 2-3 and Example 2-10 were produced.
  • the molded test piece was produced in the same manner as the sheet sample used for measuring the durometer A hardness and melting point of the thermoplastic elastomer.
  • the melting point after the obtained molded specimen was heated at 240 ° C. for a predetermined time was measured.
  • the test piece of Example 2-3 had a melting point of 228 ° C. after 3 minutes of heating at 240 ° C., and no melting point after 10 minutes of heating at 240 ° C. was observed (310 ° C. or higher or non-thermoplastic).
  • the test piece of Example 2-10 had a melting point of 222 ° C. after 3 minutes of heating at 240 ° C., a melting point of 224 ° C. after 10 minutes of heating at 240 ° C., and a melting point of 223 ° C. after 20 minutes of heating at 240 ° C. there were.
  • thermoplastic elastomer composition of Example 2-10 to which the phosphorus-containing heat stabilizer was added was more heated than the thermoplastic elastomer composition of Example 2-3 that did not contain the phosphorus-containing heat stabilizer. It can be seen that it is stable for a long time in the molten state, and the allowable range of conditions for producing a molded body by heating and melting is wider.
  • Example 3-1 A thermoplastic elastomer was obtained by performing the same operation as in Comparative Example 1-2, except that the heating and mixing time was changed to 60 minutes in the production conditions of the composition of Comparative Example 1-2.
  • the polymerization rate of the cyclic polyester oligomer of the obtained thermoplastic elastomer was 97.0%, the durometer A hardness was 18, and the melting point was 202 ° C.
  • thermoplastic elastomer composition of the present invention can be used for sealing materials, packings, vibration damping members, tubes, automotive parts, electrical and electronic parts, and the like.

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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)
  • Compositions Of Macromolecular Compounds (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne une composition élastomère thermoplastique qui contient un élastomère thermoplastique ayant un point de fusion de 200-300°C, l'élastomère thermoplastique étant obtenu par le mélange de matières de départ comprenant un élastomère (méth)acrylique et un polyester cyclique oligomère dans un rapport pondéral de 40/60 à 95/5 [(élastomère (méth)acrylique)/(polyester cyclique oligomère)], avec chauffage à une température de 120-300°C. L'invention concerne également un procédé de fabrication de la composition élastomère thermoplastique et un objet moulé obtenu par chauffage et moulage de la composition. La composition élastomère thermoplastique est utilisable dans des matériaux d'étanchéité, des garnitures d'étanchéité, des éléments d'amortissement des vibrations, des tubes, des pièces automobiles, des composants électriques/électroniques, etc.
PCT/JP2010/072131 2009-12-14 2010-12-09 Composition élastomère thermoplastique et son procédé de fabrication WO2011074473A1 (fr)

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JP2012193237A (ja) * 2011-03-15 2012-10-11 Aron Kasei Co Ltd 熱可塑性エラストマー組成物
JP2012246402A (ja) * 2011-05-27 2012-12-13 Bridgestone Corp エラストマー組成物の製造方法
CN103467899A (zh) * 2013-09-23 2013-12-25 句容市睿远科技有限公司 一种减振材料
JP2015021048A (ja) * 2013-07-18 2015-02-02 アロン化成株式会社 熱可塑性エラストマー組成物
JP2015021080A (ja) * 2013-07-19 2015-02-02 アロン化成株式会社 熱可塑性エラストマー組成物
WO2018193811A1 (fr) * 2017-04-18 2018-10-25 株式会社ブリヂストン Pneumatique

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JP2005213499A (ja) * 2004-01-26 2005-08-11 Freudenberg-Nok General Partnership インサイツ重合によるエラストマーの動的加硫
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JP2012193237A (ja) * 2011-03-15 2012-10-11 Aron Kasei Co Ltd 熱可塑性エラストマー組成物
JP2012246402A (ja) * 2011-05-27 2012-12-13 Bridgestone Corp エラストマー組成物の製造方法
JP2015021048A (ja) * 2013-07-18 2015-02-02 アロン化成株式会社 熱可塑性エラストマー組成物
JP2015021080A (ja) * 2013-07-19 2015-02-02 アロン化成株式会社 熱可塑性エラストマー組成物
CN103467899A (zh) * 2013-09-23 2013-12-25 句容市睿远科技有限公司 一种减振材料
WO2018193811A1 (fr) * 2017-04-18 2018-10-25 株式会社ブリヂストン Pneumatique
JP2018177091A (ja) * 2017-04-18 2018-11-15 株式会社ブリヂストン タイヤ
CN110546018A (zh) * 2017-04-18 2019-12-06 株式会社普利司通 轮胎
CN110546018B (zh) * 2017-04-18 2021-12-07 株式会社普利司通 轮胎

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