WO2014024847A1 - 熱可塑性ポリウレタンおよびその組成物 - Google Patents
熱可塑性ポリウレタンおよびその組成物 Download PDFInfo
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- WO2014024847A1 WO2014024847A1 PCT/JP2013/071162 JP2013071162W WO2014024847A1 WO 2014024847 A1 WO2014024847 A1 WO 2014024847A1 JP 2013071162 W JP2013071162 W JP 2013071162W WO 2014024847 A1 WO2014024847 A1 WO 2014024847A1
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- thermoplastic polyurethane
- polyol
- diol
- alkyl group
- side chain
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Definitions
- the present invention relates to a thermoplastic polyurethane, a thermoplastic polyurethane composition, and a molded product obtained therefrom.
- Thermoplastic polyurethane is used in a wide range of fields due to its excellent elastic properties and abrasion resistance.
- molded products such as films, sheets, tubes, and pipes manufactured by extrusion molding, and various molded products obtained by injection molding or the like are used for various applications due to their excellent characteristics.
- polyether-based thermoplastic polyurethanes are widely used mainly in the above-mentioned applications, taking advantage of excellent properties such as hydrolysis resistance and cold resistance.
- thermoplastic polyurethanes in which a chain extender having a different number of carbon atoms and a chain extender having a branch as a chain extender are used together as a chain extender when producing a thermoplastic polyurethane are known as polyether thermoplastic polyurethanes. It is known that polyurethane has good long-term continuous productivity (see Patent Document 1).
- thermoplastic polyurethane described in Patent Document 1 has room for further improvement in the transparency and cold resistance of the molded product.
- the thermoplastic polyurethane has a high viscosity increase rate at the time of melt residence, and there has been a problem that the torque of the screw is increased and the molding cannot be stably performed particularly in film molding which requires time for melt molding. Due to these problems, the thermoplastic polyurethane has excellent properties such as wear resistance, mechanical strength, and hydrolysis resistance, but is required to have a functional film requiring transparency and cold resistance. It could not be used in the technical field.
- the present invention has been made in view of the above circumstances, and is excellent in transparency and cold resistance, has a small increase in viscosity even during long-term melt retention, and has excellent abrasion resistance and mechanical properties. Provide polyurethane.
- the present invention provides [1] an organic diisocyanate (A), A polymer polyol (B) having a number average molecular weight (Mn) of 1000 to 5000; A thermoplastic polyurethane obtained by reacting with a chain extender (C), The chain extender (C) comprises a straight chain diol (c-1) and a side chain alkyl group-containing diol (c-2), The molar ratio of the straight chain diol (c-1) to the side chain alkyl group-containing diol (c-2) in the chain extender (C) (straight chain diol (c-1) / side chain alkyl group-containing diol (c-2 )) Is 97/3 to 60/40, A thermoplastic polyurethane having a nitrogen atom content of 1.5% by mass or more and less than 4.0% by mass; [2] The thermoplastic polyurethane according to the above [1], wherein the proportion of the organic diisocyanate (A) is 30% by mass or less; [
- thermoplastic polyurethane according to any one of the above [1] to [3]; [5] The thermoplastic polyurethane according to the above [4], wherein the other polyol (b-2) is a polyester polyol; [6] The thermoplastic polyurethane according to the above [5], wherein the polyol component constituting the polyester polyol is a side chain alkyl group-containing diol (d); [7] The thermoplastic polyurethane according to the above [6], wherein the side chain alkyl group-containing diol (d) is 3-methyl-1,5-pentanediol; [8] The linear diol (c-1) is 1,4-butanediol, The side chain alkyl group-containing diol (c-2) is represented by the following formula (I):
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an alkyl group, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is at least one alkyl group, and l, m and n each independently represent an integer of 0 or more satisfying the relationship of l + n ⁇ 1, 2 ⁇ l + m + n ⁇ 10.
- thermoplastic polyurethane according to any one of the above [1] to [7]; [9]
- the side chain alkyl group-containing diol (c-2) is propylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol and 2-methyl-1,4-butanediol.
- thermoplastic polyurethane according to the above [8] which is at least one selected from the group consisting of: [10] The thermoplastic polyurethane according to the above [8], wherein the side chain alkyl group-containing diol (c-2) is propylene glycol and / or 3-methyl-1,5-pentanediol; [11] A molded article containing the thermoplastic polyurethane according to any one of the above [1] to [10]; [12] The thermoplastic polyurethane according to any one of [1] to [10] above, A thermoplastic polyurethane composition containing 1 to 20 parts by mass of a crosslinking agent with respect to 100 parts by mass of the thermoplastic polyurethane; [13] A molded article comprising the thermoplastic polyurethane composition according to [12] above; [14] A crosslinked molded product obtained by crosslinking the molded product of [13] above; About.
- thermoplastic polyurethane which is excellent in transparency and cold resistance, has a small viscosity increase rate even in a long-time melt residence, and further has excellent wear resistance and mechanical properties.
- thermoplastic polyurethane of the present invention is a thermoplastic polyurethane obtained by reacting an organic diisocyanate (A), a polymer polyol (B) having a number average molecular weight (Mn) of 1000 to 5000, and a chain extender (C).
- A organic diisocyanate
- B polymer polyol
- C chain extender
- the chain extender (C) comprises a linear diol (c-1) and a side chain alkyl group-containing diol (c-2), and the linear diol (c-1) in the chain extender (C)
- the molar ratio of the side chain alkyl group-containing diol (c-2) (straight chain diol (c-1) / (side chain alkyl group-containing diol (c-2))) is 97/3 to 60/40, and the nitrogen atom
- the content is 1.5% by mass or more and less than 4.0% by mass
- “linear diol” means a hydroxy group at both ends of a linear main chain (preferably alkanediyl group).
- the term “kill group-containing diol” means a compound in which an alkyl group is bonded to the linear diol as a side chain.
- the main chain of the linear diol and the side chain alkyl group-containing diol preferably has 2 or more carbon atoms. 10 or less.
- organic diisocyanate (A) As the organic diisocyanate (A) used in the present invention, any organic diisocyanate conventionally used in the production of thermoplastic polyurethanes can be used.
- examples of the organic diisocyanate (A) include 4,4′-diphenylmethane diisocyanate, tolylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, phenylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane.
- Aromatic diisocyanates such as diisocyanate and toluylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate. These may use only 1 type and may use 2 or more types together. Of these, aromatic diisocyanates are preferable and 4,4′-diphenylmethane diisocyanate is more preferable from the viewpoint of mechanical performance, moldability, durability and the like of the obtained thermoplastic polyurethane.
- the polymer polyol (B) used in the present invention is a polymer polyol having a number average molecular weight (Mn) of 1000 to 5000.
- Mn number average molecular weight
- the Mn of the polymer polyol (B) is preferably 1000 to 4000, more preferably 1500 to 3000. Mn can be calculated from the value of the hydroxyl value by measuring the hydroxyl value (according to JIS K 1557).
- the polymer polyol (B) is preferably composed of polyether polyol (b-1), and may contain other polyol (b-2) as necessary.
- the polyether polyol (b-1) is preferably a linear polyether polyol, more preferably a linear polyether diol.
- the Mn of the polyether polyol (b-1) is 1000 to 5000, preferably 1000 to 4000, more preferably 1500 to 3000. When the Mn of the polyether polyol (b-1) is less than 1000, the resulting thermoplastic polyurethane is deteriorated in cold resistance and impact resistance and becomes brittle. On the other hand, when the Mn is greater than 5000, the resulting thermoplasticity The moldability of polyurethane is reduced.
- polyether polyol (b-1) examples include polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
- polytetramethylene ether glycol is preferable from the viewpoint of mechanical properties, moldability, and cold resistance of the obtained thermoplastic polyurethane.
- the Mn of other polyol (b-2) is 1000 to 5000, preferably 1000 to 4000, more preferably 1500 to 3000.
- the Mn of the other polyol (b-2) is less than 1000, the resulting thermoplastic polyurethane is deteriorated in cold resistance and impact resistance, and becomes brittle.
- the Mn is greater than 5000, the resulting thermoplasticity The moldability of polyurethane is reduced.
- Examples of other polyols (b-2) include polyester polyols obtained from aliphatic polycarboxylic acids and aliphatic polyols (eg, polyester diols obtained from aliphatic dicarboxylic acids and aliphatic diols); aliphatic polycarboxylic acids Polyols obtained from an aromatic polycarboxylic acid and an aliphatic polyol (for example, a polyester diol obtained from an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid and an aliphatic diol); a polycaprolactone polyol (eg, a polycaprolactone diol); Polyol (for example, polycarbonate diol); and the like.
- polyester polyols obtained from aliphatic polycarboxylic acids and aliphatic polyols eg, polyester diols obtained from aliphatic dicarboxylic acids and aliphatic diols
- polyester polyols that is, polyester polyols obtained from aliphatic polycarboxylic acids and aliphatic polyols, polyester polyols obtained from aliphatic polycarboxylic acids, aromatic polycarboxylic acids and aliphatic polyols
- polyester polyols obtained from aliphatic polycarboxylic acids and aromatic polycarboxylic acids and aliphatic polyols
- the polyester polyol can be obtained by, for example, the following method: (1) A method in which a polyol component and a polycarboxylic acid component such as a polycarboxylic acid, an ester-forming derivative such as an ester or an acid anhydride thereof are directly esterified or transesterified, (2) A method of ring-opening polymerization of a lactone using a polyol component as an initiator.
- polyol component used in the production of the polyester polyol those generally used in the production of polyester can be used.
- the polyol component include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,7-heptanediol.
- Linear diols such as 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol; propylene glycol, 1-ethyl-1,2-ethanediol, 1,2-dimethyl-1,2 -Ethanediol, 1-methyl-2-ethyl-1,2-ethanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-dimethyl-1,2 -Propanediol, 1,3-dimethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanedi 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1-methyl-1,4-butanediol, 2-methyl-1,4- Butanediol, 2,3-di
- a dihydric alcohol that is, a diol
- the above-mentioned side chain alkyl group-containing diol (d) is more preferable because it is excellent in cold resistance and transparency of the obtained thermoplastic polyurethane.
- 3-methyl-1,5-pentanediol is more preferable.
- polycarboxylic acid component used in the production of the polyester polyol a polycarboxylic acid component generally used in the production of polyester can be used.
- the polycarboxylic acid component include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, methylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, trimethyl.
- adipic acid for example, 2,2,4-trimethyladipic acid
- 2-methyloctanedioic acid for example, 2,2,4-trimethyladipic acid
- 3-methyloctanedioic acid for example, 2,2,4-trimethyladipic acid
- 3-methyloctanedioic acid for example, 2,2,4-trimethyladipic acid
- 3-methyldecanedioic acid 3,7-dimethyldecanedioic acid
- Aliphatic dicarboxylic acids having 6 to 12 carbon atoms include cycloaliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid (for example, 1,4-cyclohexanedicarboxylic acid), dimer acid, hydrogenated dimer acid; terephthalic acid, isophthalic acid, orthophthalic acid , Aromatic dicarboxylic acids such as naphthalenedicarboxylic acid; trifunctional or higher functional groups such as trimellitic acid and pyromellitic acid Polycarboxylic acids; their ester-forming derivatives; and the like. These polycarboxylic acids and ester-forming derivatives may be used alone or in combination of two or more. Of these, aliphatic dicarboxylic acids having 6 to 12 carbon atoms, particularly adipic acid, azelaic acid and sebacic acid are preferred.
- the polyester polyol is preferably a polyester diol obtained by a reaction between an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and a side chain alkyl group-containing diol (d).
- the aliphatic dicarboxylic acid having 6 to 12 carbon atoms and the side chain alkyl are preferable.
- the polyester diol obtained by the reaction with the group-containing diol (d) is more preferable, and obtained by the reaction of at least one selected from the group consisting of adipic acid, azelaic acid and sebacic acid with 3-methyl-1,5-pentanediol. More preferred are polyester diols.
- lactones used in the production of polyester polyols obtained by ring-opening polymerization of lactones include ⁇ -caprolactone and ⁇ -methyl- ⁇ -valerolactone.
- Examples of the polycarbonate polyol include those obtained by a reaction between a polyol and a carbonate compound such as dialkyl carbonate, alkylene carbonate, and diaryl carbonate.
- a polyol which comprises a polycarbonate polyol the polyol component illustrated previously as a component used for manufacture of a polyester polyol can be used.
- examples of the dialkyl carbonate include dimethyl carbonate and diethyl carbonate
- examples of the alkylene carbonate include ethylene carbonate
- examples of the diaryl carbonate include diphenyl carbonate.
- the molar ratio of the other polyol (b-2) to the polyether polyol (b-1) (other polyol (b-2) / polyether polyol (b-1)) is preferably 0/100 to 40/60. More preferably, it is 0/100 to 30/70.
- the chain extender (C) used in the present invention is a mixture of a linear diol (c-1) and a side chain alkyl group-containing diol (c-2).
- the molar ratio of the linear diol (c-1) to the side chain alkyl group-containing diol (c-2) is It must be 97/3 to 60/40. This molar ratio is preferably 95/5 to 80/20.
- linear diol (c-1) examples include ethylene glycol, diethylene glycol, triethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, , 9-nonanediol and the like. These may use only 1 type and may use 2 or more types together. Among them, the thermoplastic polyurethane from which 1,4-butanediol can be obtained is preferable from the viewpoint of mechanical properties and moldability.
- Examples of the side chain alkyl group-containing diol (c-2) include the following formula (I):
- R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom or an alkyl group, and R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is at least one alkyl group, and l, m, and n each independently represent an integer of 0 or more that satisfies the relationship of l + n ⁇ 1, 2 ⁇ l + m + n ⁇ 10.
- l, m, and n each independently represent an integer of 0 or more that satisfies the relationship of l + n ⁇ 1, 2 ⁇ l + m + n ⁇ 10.
- d side chain alkyl group containing diol
- the side chain alkyl group-containing diol (c-2) may be used alone or in combination of two or more.
- thermoplastic polyurethane propylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol and 2-methyl-1,4- Butanediol is preferred, propylene glycol and 3-methyl-1,5-pentanediol are more preferred, and 3-methyl-1,5-pentanediol is more preferred.
- chain extender (C) together with the linear diol (c-1) and the side chain alkyl group-containing diol (c-2), it is necessary as long as the effects of the present invention are not impaired.
- Other low molecular compounds having two or more hydroxy groups capable of reacting with an isocyanate group also known as an isocyanato group
- examples of other low molecular weight compounds include trifunctional or higher functional low molecular weight polyols such as glycerin and pentaerythritol.
- the thermoplastic polyurethane of the present invention needs to have a nitrogen atom content of 1.5% by mass or more and less than 4.0% by mass.
- the nitrogen atom content is preferably 1.5 to 3.2% by mass, more preferably 2.0 to 2.8% by mass. If the nitrogen atom content in the thermoplastic polyurethane is less than 1.5% by mass, the mechanical properties and durability may be inferior. If it is 4.0% by mass or more, the cold resistance and transparency will deteriorate, and further melting will occur. The thickening at the time of retention is remarkable, and long-time melt molding becomes difficult.
- thermoplastic polyurethane of the present invention all active hydrogen atoms (hydrogen atoms capable of reacting with isocyanate) 1 contained in the polymer polyol (B), the chain extender (C) and other components 1
- the organic diisocyanate (A) is preferably used so that the isocyanate group is about 0.9 to 1.5 equivalents per equivalent, and the organic diisocyanate (A) is preferably adjusted so that the isocyanate group is about 1 equivalent. It is preferred to use.
- the ratio of the organic diisocyanate (A) in the thermoplastic polyurethane of the present invention is 30% by mass or less.
- the thermoplastic polyurethane obtained is preferable from the viewpoints of cold resistance, transparency, and a decrease in the thickening rate when melted and retained.
- the proportion of the organic diisocyanate (A) is more preferably 27% by mass or less.
- thermoplastic polyurethane of the present invention has a logarithmic viscosity of 0.5 to 2.0 dl / g measured as a 0.5 g / dl dimethylformamide solution at 30 ° C. It is preferable from the point of property etc., and it is good to select the kind and combination of a raw material component, polymerization conditions, etc. so that the thermoplastic polyurethane of such a viscosity may be obtained.
- the number average molecular weight (Mn) of the thermoplastic polyurethane is preferably 50,000 to 500,000, more preferably 100,000 to 300,000.
- Mn of thermoplastic polyurethane can be measured by gel permeation chromatography (GPC).
- GPC is a differential refractometer detector (“RID6A” manufactured by Shimadzu Corporation) and high performance liquid chromatography (HPLC) (“LC-9A” manufactured by Shimadzu Corporation), column: “Shodex KD-806M” and “Shodex KD” manufactured by Tosoh Corporation. -802.5 "can be linked and developing solvent: dimethylformamide, standard sample: polystyrene) can be used.
- the organic diisocyanate (A) is an aromatic diisocyanate
- the polymer polyol (B) is a polyether polyol (b-1) having an Mn of 1,000 to 5,000, or a polyether polyol (b-1) having an Mn of 1,000 to 5,000 and other Mn of 1,000 to 5,000.
- a polyol (b-2), The molar ratio of the other polyol (b-2) to the polyether polyol (b-1) (other polyol (b-2) / polyether polyol (b-1)) is 0/100 to 40/60
- the polyether polyol (b-1) is at least one selected from the group consisting of polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol and polyhexamethylene ether glycol
- Another polyol (b-2) is an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, propylene glycol, 1-ethyl-1,2-ethanediol, 1,2-dimethyl-1,2-ethanediol, -Methyl-2-ethyl-1,2-ethanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-dimethyl-1,2-propanedi
- the side chain alkyl group-containing diol (c-2) is propylene glycol, 1-ethyl-1,2-ethanediol, 1,2-dimethyl-1,2-ethanediol, 1-methyl-2-ethyl-1, 2-ethanediol, 1-methyl-1,3-propanediol, 2-methyl-1,3-propanediol, 1,2-dimethyl-1,2-propanediol, 1,3-dimethyl-1,3- Propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 1-methyl-1, 4-butanediol, 2-methyl-1,4-butanediol, 2,3-dimethyl-1,4-butanediol,
- the organic diisocyanate (A) is an aromatic diisocyanate
- the polymer polyol (B) is a polyether polyol (b-1) having an Mn of 1000 to 4000, or a polyether polyol (b-1) having an Mn of 1000 to 4000 and other Mn of 1000 to 4000 A polyol (b-2),
- the molar ratio of the other polyol (b-2) to the polyether polyol (b-1) is 0/100 to 30/70
- the polyether polyol (b-1) is at least one selected from the group consisting of polyethylene glycol, polytrimethylene ether glycol, polytetramethylene ether glycol and polyhexamethylene ether glycol
- Another polyol (b-2) is a polyester diol obtained by reacting an aliphatic dicarboxylic acid having 6 to 12 carbon atoms with 3-methyl-1,5-pentanediol
- the chain extender (C) comprises
- the side chain alkyl group-containing diol (c-2) comprises propylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol and 2-methyl-1,4-butanediol. At least one selected from the group,
- the nitrogen content of the thermoplastic polyurethane is 1.5 to 3.2% by mass,
- the Mn of the thermoplastic polyurethane is 50,000 to 500,000.
- the organic diisocyanate (A) is 4,4′-diphenylmethane diisocyanate;
- the polymer polyol (B) is a polyether polyol (b-1) having an Mn of 1500 to 3000, or a polyether polyol (b-1) having an Mn of 1500 to 3000 and other Mn of 1500 to 3000 A polyol (b-2),
- the molar ratio of the other polyol (b-2) to the polyether polyol (b-1) is 0/100 to 30/70
- the polyether polyol (b-1) is polytetramethylene ether glycol
- the other polyol (b-2) is a polyester diol obtained by reaction of at least one selected from the group consisting of adipic acid, azelaic acid and sebacic acid with 3-methyl-1,5-pentanediol,
- the chain extender (C) comprises a straight chain diol (c-1) and a side chain al
- thermoplastic polyurethane composition The present invention provides a thermoplastic polyurethane composition containing the thermoplastic polyurethane and other components.
- Other components are not particularly limited as long as they are components that are usually used in the production of thermoplastic polyurethane compositions.
- internal mold release agents fillers, plasticizers, colorants (dyes, pigments) ), Stabilizers (for example, antioxidants, UV stabilizers, heat stabilizers, etc.), flame retardants, crosslinking agents, reaction accelerators, reinforcing agents and the like.
- Examples of the internal mold release agent include fatty acid amides, fatty acid esters, fatty acids, fatty acid salts and the like.
- Examples of the fatty acid amide include caproic acid amide, lauric acid amide, myristic acid amide, stearic acid amide, oleic acid amide, ethylene bis stearic acid amide, and ethylene bis oleic acid amide.
- Examples of fatty acid esters include esters of long chain fatty acids and alcohols, and specific examples include sorbitan monolaurate, butyl stearate, butyl laurate, octyl palmitate, stearyl stearate, and the like.
- fatty acid examples include capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, montanic acid, lindenic acid, oleic acid, erucic acid, linoleic acid, and the like.
- fatty acid salts include metal salts of the fatty acids (eg, barium, zinc, magnesium, calcium, etc.).
- filler examples include talc, calcium carbonate, chalk, calcium sulfate, clay, kaolin, silica, glass, fumed silica, mica, wollastonite, feldspar, aluminum silicate, calcium silicate, alumina, alumina trihydrate, and the like.
- the filler is preferably talc, calcium carbonate, barium sulfate, silica, glass, glass fiber, alumina, titanium dioxide or combinations thereof, more preferably talc, calcium carbonate, barium sulfate, glass fibers or combinations thereof. is there.
- the filler those described in Zweifel Hans et al., “Plastics Additives Handbook”, Hanser Gardner Publications, cinCincinnati, Ohio, 5th Edition, Chapter 17, 901-948 (2001) can be used. .
- plasticizer examples include mineral oil, abietic acid ester, adipic acid ester, alkyl sulfonic acid ester, azelaic acid ester, benzoic acid ester, chlorinated paraffin, citrate ester, epoxide, glycol ether and its ester, glutaric acid ester, Hydrocarbon oil, isobutyric acid ester, oleic acid ester, pentaerythritol derivative, phosphoric acid ester, phthalic acid ester, polybutene, ricinoleic acid ester, sebacic acid ester, sulfonamide, trimellitic acid ester, pyromellitic acid ester, biphenyl derivative, stearic acid Esters, difurandiesters, fluorine-containing plasticizers, hydroxybenzoic acid esters, isocyanate ester adducts, polycyclic aromatic compounds, natural product derivatives, siloxane plasticizers, tar System products, thioest
- the content of the plasticizer in the thermoplastic polyurethane composition is preferably 0 to 15% by mass, more preferably 0.5 to 10% by mass, and further preferably 1 to 5% by mass.
- plasticizer those described in George Wypych, “Handbook of Plasticizers,” ChemTec, Publishing, Toronto-Scarborough, Ontario (2004) can be used.
- the colorant examples include inorganic pigments such as metal oxides (eg, iron oxide, zinc oxide, titanium dioxide), mixed metal oxides, carbon black, combinations thereof, and the like; organic pigments such as, for example, Anthraquinone, anthanthrone, azo compound, monoazo compound, arylamide, benzimidazolone, BONA lake, diketopyrrolopyrrole, dioxazine, diazo compound, diarylide compound, flavantron, indanthrone, isoindolinone, isoindoline, monoazo salt, Naphthol, ⁇ -naphthol, naphthol AS, naphthol lake, perylene, perinone, phthalocyanine, pyrantrone, quinacridone, quinophthalone, combinations thereof, and the like; combinations of inorganic pigments and organic pigments;
- the content of the colorant in the thermoplastic polyurethane composition is preferably 0 to 10% by mass
- antioxidants examples include aromatic amines such as alkyldiphenylamine, phenyl- ⁇ -naphthylamine, alkyl-substituted phenyl- ⁇ -naphthylamine, aralkyl-substituted phenyl- ⁇ -naphthylamine, alkylated p-phenylenediamine, and tetramethyl-diaminodiphenylamine.
- aromatic amines such as alkyldiphenylamine, phenyl- ⁇ -naphthylamine, alkyl-substituted phenyl- ⁇ -naphthylamine, aralkyl-substituted phenyl- ⁇ -naphthylamine, alkylated p-phenylenediamine, and tetramethyl-diaminodiphenylamine.
- UV stabilizer examples include benzophenone, benzotriazole, aryl ester, oxanilide, acrylic ester, formamidine, carbon black, hindered amine, nickel quencher, hindered amine, phenol compound, metal salt, zinc compound, and combinations thereof. It is done.
- the content of the UV stabilizer in the thermoplastic polyurethane composition is preferably 0 to 5% by mass, more preferably 0.01 to 3% by mass, still more preferably 0.1 to 2% by mass, and particularly preferably 0. 1 to 1% by mass.
- UV stabilizers described in Zweifel Hans et al., “Plastics Additives Handbook,” Hanser Gardiner Publications, Cincinnati, Ohio, 5th edition, Chapter 2, pages 141-426 (2001) are used. it can.
- a heat stabilizer may be used for the purpose of improving the heat stability during the molding process of the thermoplastic polyurethane.
- the heat stabilizer include phosphorus heat stabilizers, and commercially available products thereof include, for example, trade names manufactured by Ciba Specialty Chemicals: Irgaphos 38, 126, P-EPQ, Asahi Denka Trade names manufactured by Kogyo Co., Ltd .: ADK STAB PEP-4C, 11C, 24, 36, and the like.
- its content in the thermoplastic polyurethane composition is preferably 0.05 to 1% by mass.
- the flame retardant examples include halogen-based organic flame retardants such as polybromodiphenyl ether, ethylenebisbrominated phthalimide, bis (brominated phenyl) ethane, bis (brominated phenyl) terephthalamide, and perchloropentacyclodecane; Organic flame retardants of nitrogen; inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide; and the like.
- halogen-based organic flame retardants such as polybromodiphenyl ether, ethylenebisbrominated phthalimide, bis (brominated phenyl) ethane, bis (brominated phenyl) terephthalamide, and perchloropentacyclodecane
- Organic flame retardants of nitrogen inorganic flame retardants such as antimony trioxide, aluminum hydroxide, magnesium hydroxide; and the like.
- thermoplastic polyurethane composition of the present invention preferably contains a crosslinking agent.
- a cross-linked molded article having good physical properties such as mechanical properties and wear resistance can be obtained.
- crosslinking agent examples include organic peroxides such as alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, and cyclic peroxides; vinyltrimethoxysilane, vinyltriethoxysilane Silane compounds such as vinyltris (2-methoxyethoxy) silane, vinyltriacetoxysilane, vinylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane; trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, toluacryl formal, etc.
- organic peroxides such as alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, and cyclic peroxides
- vinyltrimethoxysilane, vinyltriethoxysilane Silane compounds such as vinyltris (2-me
- radical crosslinking agent having a plurality of carbon-carbon double bonds (preferably 3 or more) in the molecule.
- crosslinking agent those described in ZweifelifHans et al., “Plastics Additives Handbook” Hanser Gardner Publications, atiCincinnati, Ohio, 5th edition, Chapter 14, pages 725-812 (2001) can be used.
- radical crosslinking agents are preferable, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and toluacryl formal are more preferable, and trimethylolpropane triacrylate and trimethylolpropane trimethacrylate are more preferable.
- the content of the radical crosslinking agent in the thermoplastic polyurethane composition is preferably 1 to 20 parts by mass and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic polyurethane.
- content of a radical crosslinking agent exceeds 20 mass parts, the viscosity of a thermoplastic polyurethane composition falls, a moldability falls, and handling may become difficult.
- content of a radical crosslinking agent is less than 1 mass part, the physical properties of crosslinked molded articles, such as a mechanical characteristic and abrasion resistance, may not fully be improved.
- thermoplastic polyurethane of the present invention can be produced by a known urethanization reaction technique, and can be produced by either a prepolymer method or a one-shot method.
- a prepolymer method for example, (1) Continuous supply of polymer polyol (B), chain extender (C) and organic diisocyanate (A) and other components as necessary to a single-screw or multi-screw extruder simultaneously or almost simultaneously
- active hydrogen atom-containing compounds such as polymer polyol (B) and chain extender (C) and heating to 60 to 90 ° C.
- Method for producing thermoplastic polyurethane by adding organic diisocyanate (A) in such an amount that active hydrogen atom / isocyanate group) is
- An organic diisocyanate (A) and a polymer polyol (B) are reacted in advance in an extruder or other reaction apparatus to form an isocyanate group-terminated prepolymer, and then reacted with a chain extender (C) to be thermoplastic.
- thermoplastic polyurethane having excellent melt moldability and mechanical properties
- the thermoplastic polyurethane obtained by the continuous melt polymerization method is generally superior in strength compared to the thermoplastic polyurethane obtained by solid phase polymerization at 80 to 130 ° C.
- the method (1) is preferable because the desired thermoplastic polyurethane can be continuously produced very simply by supplying all or all of the reaction components to the extruder simultaneously or substantially simultaneously.
- a catalyst may be used for the urethanization reaction.
- the urethanization reaction catalyst include organic tin compounds, organic zinc compounds, organic bismuth compounds, organic titanium compounds, organic zirconium compounds, and amine compounds. Only one type of urethanization reaction catalyst may be used, or two or more types may be used in combination.
- a urethanization reaction catalyst it is recommended to adjust the mass to 0.1 to 100 ppm by mass with respect to the mass of the thermoplastic polyurethane. If a urethanization reaction catalyst of 0.1 mass ppm or more is used, the original molecular weight is maintained at a sufficiently high level after molding the thermoplastic polyurethane, and the original properties of the thermoplastic polyurethane are effective even in the molded product. It becomes easy to be demonstrated.
- organotin compounds are preferable.
- the organic tin compounds include tin-containing acylate compounds, tin-containing mercaptocarboxylates, and the like. Specifically, tin octylate, monomethyltin mercaptoacetate, monobutyltin triacetate, monobutyltin monooctylate, Monobutyltin monoacetate, monobutyltin maleate, monobutyltin maleic acid benzyl ester salt, monooctyltin maleate, monooctyltin thiodipropionate, monooctyltin tris (isooctylthioglycolate), monophenyl Tin triacetate, dimethyltin maleate, dimethyltin bis (ethylene glycol monothioglycolate), dimethyltin bis (mercaptoacetic acid) salt, dimethyltin bis (3-mercaptopropion)
- thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention By molding the thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention, sheets, films, rolls, gears, solid tires, belts, hoses, tubes, packing materials, anti-vibration materials, excellent in transparency and cold resistance, Molded articles such as shoe soles, sports shoes, machine parts, automobile parts, sporting goods, and elastic fibers can be manufactured smoothly.
- the molding method include casting, dipping in which a thermoplastic polyurethane or a thermoplastic polyurethane composition is dissolved in a solvent to form a uniform solution and then formed into a sheet or film; extrusion, injection molding in which molding is performed after heating and kneading. , Calender molding, cast molding, blow molding, inflation molding, foam molding, rotational molding, slush molding, and the like.
- the obtained molded article may be formed only of a thermoplastic polyurethane or a thermoplastic polyurethane composition, and a composite molded article of these and other materials (for example, thermoplastic polyurethane or thermoplastic polyurethane composition and other materials). And the like.
- the composite molded product can be manufactured by insert molding, coextrusion molding, or the like, for example.
- thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention is a member (X) and a member formed from another material is a member (Y)
- the composition of the composite molded article is, for example, , A composite molded article having one member (X) and one member (Y); A composite molded article in which a member (X) is interposed between two members (Y); A composite molded article in which a member (Y) is interposed between two members (X); A composite molded article in which the member (X) and the member (Y) are alternately contacted; Etc.
- the member (X) and the member (Y) may be layered, and therefore the composite molded product of the present invention is a laminate in which the layered member (X) and the layered member (Y) are laminated. It may be a structure.
- Examples of the material of the member (Y) include polyamide, polyester, polyvinylidene chloride, polyvinyl chloride, polycarbonate, acrylic resin, polyoxymethylene resin, saponified ethylene-vinyl acetate copolymer, aromatic vinyl compound, and the like. , Vinyl cyanide compounds, copolymers with at least one selected from conjugated dienes and olefins; polyurethanes other than the thermoplastic polyurethane of the present invention; styrenic polymers; polyolefins; These may use only 1 type and may use 2 or more types together.
- the method for producing the composite molded article is not particularly limited.
- a method of melt-coating the member (Y) with the thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention A method of introducing the thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention in a molten state between two or more members (Y), and bonding and integrating them; A method in which the member (Y) is placed (inserted) in a mold and then filled with the molten thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention, and these are bonded and integrated; A method of coextruding the thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention and the material constituting the member (Y), and bonding and integrating them; A method of pressing the member (X) and the member (Y); A method of bonding and integrating the member (X) and the member (Y) with an adhesive; Etc.
- thermoplastic polyurethane composition examples include chemical crosslinking with an organic peroxide, water crosslinking with a silane, and electron beam crosslinking with a radical crosslinking agent.
- a radical crosslinking agent from the viewpoint of the crosslinking treatment speed, it is preferable to crosslink the thermoplastic polyurethane composition containing a radical crosslinking agent by irradiating it with ionizing radiation such as an accelerated electron beam (that is, electron beam crosslinking).
- ionizing radiation such as an accelerated electron beam (that is, electron beam crosslinking).
- the processing temperature is 180 ° C.
- thermoplastic polyurethane of the present invention is suitable for molding a melt-molded product because the viscosity increase rate is small even during long-time melt residence, and in particular, it is suitable for melting sheets, films, belts, hoses, tubes, elastic fibers, etc. Suitable for forming extruded products.
- Nitrogen atom content The nitrogen atom content (% by mass) of the thermoplastic polyurethane obtained in the following examples and comparative examples was measured with an elemental analyzer ("2400-2 type" manufactured by PerkinElmer). .
- thermoplastic polyurethane obtained in the following Examples and Comparative Examples was press-molded with a press molding machine (temperature 180 to 200 ° C.) to produce a 20 cm ⁇ 20 cm ⁇ 2 mm sheet.
- haze of the thermoplastic polyurethane sheet was measured with a transmittance meter (“HR-100” manufactured by Murakami Color Research Laboratory).
- Taber wear amount Injection mold (FS-80S12ASE made by Nissei Plastic Industry Co., Ltd., cylinder temperature 190-220 ° C, mold temperature 30 ° C, injection time 5-8 seconds, cooling using a mold with a mirror-finished surface. 30 seconds), a disk-shaped molded product (diameter 120 mm, thickness 2 mm) was produced from the thermoplastic polyurethane obtained in the following examples and comparative examples, and the obtained molded product was treated at 25 ° C. for 3 days. After being allowed to stand, the amount of Taber abrasion was measured according to JIS K 7311 using a Taber abrasion tester (load 1 kg, abrasion wheel H-22).
- MDI 4,4′-diphenylmethane diisocyanate
- BD 1,4-butanediol
- MPD 3-methyl-1,5-pentanediol
- Examples 2 to 18 Except having changed the kind and ratio of a thermoplastic polyurethane raw material as shown in Table 1, it supplied continuously to the twin-screw extruder like Example 1, and polymerized at 260 degreeC, and manufactured the thermoplastic polyurethane.
- thermoplastic polyurethane raw material As shown in Table 2, it was continuously supplied to the twin-screw extruder in the same manner as in Example 1 and polymerized at 260 ° C. to produce a thermoplastic polyurethane.
- thermoplastic polyurethanes of Examples 1 to 18 are excellent in transparency and cold resistance, have high breaking strength, and excellent in mechanical properties. .
- thermoplastic polyurethanes of Examples 1 to 18 all have a small viscosity increase rate.
- Examples 8 and 13 further comprising a polyether polyol (b-1) having an Mn of 1000 to 5000 as a polymer polyol (B) and another polyol (b-2) (ie, a polyester polyol) having an Mn of 1000 to 5000.
- the thickening rate is particularly suppressed small.
- Comparative Examples 1, 5, 8 and 10 obtained by using only the linear diol (c-1) without using the side chain alkyl group-containing diol (c-2) as the chain extender (C).
- thermoplastic polyurethane With thermoplastic polyurethane, the cold resistance of the molded product was not sufficient.
- the molar ratio of the straight chain diol (c-1) to the side chain alkyl group-containing diol (c-2) as the chain extender (C) is outside the scope of the present invention (that is, the side chain alkyl group-containing diol ( In Comparative Examples 2 and 7 where the proportion of c-2) is small, the cold resistance of the molded products was not sufficient.
- thermoplastic polyurethane raw material As shown in Table 5, it supplied continuously to the twin-screw extruder similarly to Example 1, and it polymerized at 260 degreeC and manufactured the thermoplastic polyurethane. With respect to 100 parts by mass of the thermoplastic polyurethane obtained here, 3 to 10 parts by mass of the crosslinking agent shown in Table 5 was melt-kneaded at 200 ° C. with a twin screw extruder to obtain a thermoplastic polyurethane composition.
- thermoplastic polyurethane composition After molding the thermoplastic polyurethane composition into a 0.5 mm thick sheet by press molding, the sheet is accelerated by an electron beam accelerator [manufactured by Nissin High Voltage, model name “Curetron EB200-100”]. Crosslinking was performed by irradiating an electron beam with a voltage of 200 kV and an irradiation dose of 200 kGy to obtain a crosslinked sheet (crosslinked molded product). Cold resistance, transparency and breaking strength were measured in the same manner as described above except that the crosslinked sheet was used instead of the thermoplastic polyurethane sheet.
- the crosslinked molded articles obtained from the thermoplastic polyurethane compositions of Examples 19 to 26 are excellent in transparency and cold resistance, and are not yet obtained from the thermoplastic polyurethanes of Examples 1 to 18. It can be seen that the breaking strength and the Taber abrasion amount are further superior to the cross-linked molded product.
- thermoplastic polyurethane of the present invention is excellent in transparency and cold resistance, has a small viscosity increase rate even during long-time melt retention, and is also excellent in wear resistance and mechanical properties.
- thermoplastic polyurethane or thermoplastic polyurethane composition of the present invention a sheet, film, roll, gear, solid tire, belt, hose, tube, packing material, anti-vibration material, shoe sole, sports excellent in transparency and cold resistance Various products such as shoes, machine parts, automobile parts, sporting goods and elastic fibers can be obtained.
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Abstract
Description
これらの問題により、該熱可塑性ポリウレタンは耐磨耗性、機械的強度等の特性、耐加水分解性という優れた特性を有するものの、透明性が要求される機能性フィルムや耐寒性の要求される技術分野では使用できなかった。
本発明は、前記事情に鑑みてなされたものであり、透明性、耐寒性に優れ、長時間の溶融滞留においても増粘率が小さく、さらに耐摩耗性、機械的性質にも優れた熱可塑性ポリウレタンを提供する。
[1] 有機ジイソシアネート(A)と、
数平均分子量(Mn)が1000~5000の高分子ポリオール(B)と、
鎖伸長剤(C)と
を反応させて得られる熱可塑性ポリウレタンであって、
鎖伸長剤(C)が直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)からなり、
鎖伸長剤(C)における直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比(直鎖ジオール(c-1)/側鎖アルキル基含有ジオール(c-2))が97/3~60/40であり、
窒素原子含有率が1.5質量%以上4.0質量%未満であることを特徴とする、熱可塑性ポリウレタン;
[2] 有機ジイソシアネート(A)の割合が30質量%以下である上記[1]の熱可塑性ポリウレタン;
[3] 有機ジイソシアネート(A)が4,4’-ジフェニルメタンジイソシアネートである、上記[1]または[2]の熱可塑性ポリウレタン;
[4] 高分子ポリオール(B)がポリエーテルポリオール(b-1)であるか、またはポリエーテルポリオール(b-1)および他のポリオール(b-2)からなり、
他のポリオール(b-2)とポリエーテルポリオール(b-1)のモル比(他のポリオール(b-2)/ポリエーテルポリオール(b-1))が0/100~40/60である、上記[1]~[3]のいずれかの熱可塑性ポリウレタン;
[5] 他のポリオール(b-2)がポリエステルポリオールである、上記[4]の熱可塑性ポリウレタン;
[6] ポリエステルポリオールを構成するポリオール成分が側鎖アルキル基含有ジオール(d)である、上記[5]の熱可塑性ポリウレタン;
[7] 側鎖アルキル基含有ジオール(d)が3-メチル-1,5-ペンタンジオールである、上記[6]の熱可塑性ポリウレタン;
[8] 直鎖ジオール(c-1)が1,4-ブタンジオールであり、
側鎖アルキル基含有ジオール(c-2)が下記式(I):
[9] 側鎖アルキル基含有ジオール(c-2)がプロピレングリコール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオールおよび2-メチル-1,4-ブタンジオールからなる群から選ばれる少なくとも一つである、上記[8]の熱可塑性ポリウレタン;
[10] 側鎖アルキル基含有ジオール(c-2)がプロピレングリコールおよび/または3-メチル-1,5-ペンタンジオールである、上記[8]の熱可塑性ポリウレタン;
[11] 上記[1]~[10]のいずれかの熱可塑性ポリウレタンを含む成形品;
[12] 上記[1]~[10]のいずれかの熱可塑性ポリウレタンと、
熱可塑性ポリウレタン100質量部に対して1~20質量部の架橋剤と
を含有する、熱可塑性ポリウレタン組成物;
[13] 上記[12]の熱可塑性ポリウレタン組成物を含む成形品;
[14] 上記[13]の成形品を架橋することによって得られる架橋成形品;
に関する。
本発明で用いる有機ジイソシアネート(A)は、熱可塑性ポリウレタンの製造に従来から使用されている有機ジイソシアネートのいずれもが使用できる。有機ジイソシアネート(A)としては、例えば、4,4’-ジフェニルメタンジイソシアネート、トリレンジイソシアネート、1,5-ナフチレンジイソシアネート、キシリレンジイソシアネート、フェニレンジイソシアネート、3,3’-ジクロロ-4,4’-ジフェニルメタンジイソシアネート、トルイレンジイソシアネート等の芳香族ジイソシアネート;ヘキサメチレンジイソシアネート、イソホロンジイソシアネート、4,4’-ジシクロヘキシルメタンジイソシアネート、水添化キシリレンジイソシアネート等の脂肪族または脂環式ジイソシアネート;が挙げられる。これらは1種のみを使用してもよく、2種以上を併用してもよい。中でも、得られる熱可塑性ポリウレタンの力学的性能、成形性、耐久性等の点から、芳香族ジイソシアネートが好ましく、4,4’-ジフェニルメタンジイソシアネートがより好ましい。
本発明で用いる高分子ポリオール(B)は、数平均分子量(Mn)が1000~5000の高分子ポリオールである。高分子ポリオール(B)のMnが1000よりも小さいと、得られる熱可塑性ポリウレタンの耐寒性および耐衝撃性が低下して脆弱になり、Mnが5000よりも大きいと得られる熱可塑性ポリウレタンの成形性が低下する。高分子ポリオール(B)のMnは、好ましくは1000~4000、より好ましくは1500~3000である。なおMnは、水酸基価を測定し(JIS K 1557に準拠)、この水酸基価の値より算出することができる。
(1)ポリオール成分と、ポリカルボン酸、そのエステルや酸無水物等のエステル形成性誘導体等のポリカルボン酸成分とを直接エステル化反応させるか、またはエステル交換反応させる方法、
(2)ポリオール成分を開始剤としてラクトンを開環重合する方法。
ポリカーボネートポリオールを構成するポリオールとしては、ポリエステルポリオールの製造に用いる成分として先に例示したポリオール成分を用いることができる。また、ジアルキルカーボネートとしてはジメチルカーボネート、ジエチルカーボネート等を、アルキレンカーボネートとしてはエチレンカーボネート等を、ジアリールカーボネートとしてはジフェニルカーボネート等を、それぞれ挙げることができる。
本発明で用いる鎖伸長剤(C)は、直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)の混合物である。本発明において、直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比(直鎖ジオール(c-1)/側鎖アルキル基含有ジオール(c-2))が97/3~60/40であることが必要である。このモル比は95/5~80/20であることが好ましい。直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)の合計中で、側鎖アルキル基含有ジオール(c-2)の割合が3モル%よりも少なくなると、得られる熱可塑性ポリウレタンの透明性および耐寒性の改良効果は小さくなり、この割合が40モル%を超えると得られる成形品の破断強度等が低下する。
本発明の熱可塑性ポリウレタンは、その窒素原子含有率が1.5質量%以上4.0質量%未満であることが必要である。この窒素原子含有率が1.5~3.2質量%であるのが好ましく、2.0~2.8質量%であるのがより好ましい。熱可塑性ポリウレタンにおける窒素原子含有率が1.5質量%未満であると力学特性および耐久性が劣る場合があり、4.0質量%以上であると、耐寒性および透明性が低下し、さらに溶融滞留した際の増粘が著しく、長時間の溶融成形が困難になる。
有機ジイソシアネート(A)が芳香族ジイソシアネートであり、
高分子ポリオール(B)が、Mnが1000~5000のポリエーテルポリオール(b-1)であるか、またはMnが1000~5000のポリエーテルポリオール(b-1)およびMnが1000~5000の他のポリオール(b-2)からなり、
他のポリオール(b-2)とポリエーテルポリオール(b-1)のモル比(他のポリオール(b-2)/ポリエーテルポリオール(b-1))が0/100~40/60であり、
ポリエーテルポリオール(b-1)が、ポリエチレングリコール、ポリトリメチレンエーテルグリコール、ポリテトラメチレンエーテルグリコールおよびポリヘキサメチレンエーテルグリコールからなる群から選ばれる少なくとも一つであり、
他のポリオール(b-2)が、炭素数4~12の脂肪族ジカルボン酸と、プロピレングリコール、1-エチル-1,2-エタンジオール、1,2-ジメチル-1,2-エタンジオール、1-メチル-2-エチル-1,2-エタンジオール、1-メチル-1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、1,2-ジメチル-1,2-プロパンジオール、1,3-ジメチル-1,3-プロパンジオール、2,2-ジメチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、1-メチル-1,4-ブタンジオール、2-メチル-1,4-ブタンジオール、2,3-ジメチル-1,4-ブタンジオール、2-メチル-1,5-ペンタンジオール、3-メチル-1,5-ペンタンジオール、2-エチル-1,5-ペンタンジオール、3-エチル-1,5-ペンタンジオール、2,4-ジメチル-1,5-ペンタンジオール、3-メチル-1,6-ヘキサンジオール、2-メチル-1,8-オクタンジオール、2,7-ジメチル-1,8-オクタンジオール、2-メチル-1,9-ノナンジオールおよび2,8-ジメチル-1,9-ノナンジオールからなる群から選ばれる少なくとも一つとの反応によって得られるポリエステルジオールであり、
鎖伸長剤(C)が直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)からなり、
直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比が97/3~60/40であり、
直鎖ジオール(c-1)が、エチレングリコール、ジエチレングリコール、トリエチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオールおよび1,9-ノナンジオールからなる群から選ばれる少なくとも一つであり、
側鎖アルキル基含有ジオール(c-2)が、プロピレングリコール、1-エチル-1,2-エタンジオール、1,2-ジメチル-1,2-エタンジオール、1-メチル-2-エチル-1,2-エタンジオール、1-メチル-1,3-プロパンジオール、2-メチル-1,3-プロパンジオール、1,2-ジメチル-1,2-プロパンジオール、1,3-ジメチル-1,3-プロパンジオール、2,2-ジメチル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、2-エチル-2-ブチル-1,3-プロパンジオール、1-メチル-1,4-ブタンジオール、2-メチル-1,4-ブタンジオール、2,3-ジメチル-1,4-ブタンジオール、2-メチル-1,5-ペンタンジオール、3-メチル-1,5-ペンタンジオール、2-エチル-1,5-ペンタンジオール、3-エチル-1,5-ペンタンジオール、2,4-ジメチル-1,5-ペンタンジオール、3-メチル-1,6-ヘキサンジオール、2-メチル-1,8-オクタンジオール、2,7-ジメチル-1,8-オクタンジオール、2-メチル-1,9-ノナンジオールおよび2,8-ジメチル-1,9-ノナンジオールからなる群から選ばれる少なくとも一つであり、
熱可塑性ポリウレタンの窒素含有率が1.5質量%以上4.0質量%未満であり、
熱可塑性ポリウレタンのMnが50,000~500,000である。
有機ジイソシアネート(A)が芳香族ジイソシアネートであり、
高分子ポリオール(B)が、Mnが1000~4000のポリエーテルポリオール(b-1)であるか、またはMnが1000~4000のポリエーテルポリオール(b-1)およびMnが1000~4000の他のポリオール(b-2)からなり、
他のポリオール(b-2)とポリエーテルポリオール(b-1)のモル比が0/100~30/70であり、
ポリエーテルポリオール(b-1)が、ポリエチレングリコール、ポリトリメチレンエーテルグリコール、ポリテトラメチレンエーテルグリコールおよびポリヘキサメチレンエーテルグリコールからなる群から選ばれる少なくとも一つであり、
他のポリオール(b-2)が、炭素数6~12の脂肪族ジカルボン酸と3-メチル-1,5-ペンタンジオールとの反応によって得られるポリエステルジオールであり、
鎖伸長剤(C)が直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)からなり、
直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比が95/5~80/20であり、
直鎖ジオール(c-1)が、エチレングリコール、ジエチレングリコール、トリエチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、1,6-ヘキサンジオールおよび1,9-ノナンジオールからなる群から選ばれる少なくとも一つであり、
側鎖アルキル基含有ジオール(c-2)が、プロピレングリコール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオールおよび2-メチル-1,4-ブタンジオールからなる群から選ばれる少なくとも一つであり、
熱可塑性ポリウレタンの窒素含有率が1.5~3.2質量%であり、
熱可塑性ポリウレタンのMnが50,000~500,000である。
有機ジイソシアネート(A)が4,4’-ジフェニルメタンジイソシアネートであり、
高分子ポリオール(B)が、Mnが1500~3000のポリエーテルポリオール(b-1)であるか、またはMnが1500~3000のポリエーテルポリオール(b-1)およびMnが1500~3000の他のポリオール(b-2)からなり、
他のポリオール(b-2)とポリエーテルポリオール(b-1)のモル比が0/100~30/70であり、
ポリエーテルポリオール(b-1)がポリテトラメチレンエーテルグリコールであり、
他のポリオール(b-2)が、アジピン酸、アゼライン酸およびセバシン酸からなる群から選ばれる少なくとも一つと3-メチル-1,5-ペンタンジオールとの反応によって得られるポリエステルジオールであり、
鎖伸長剤(C)が直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)からなり、
直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比が95/5~80/20であり、
直鎖ジオール(c-1)が1,4-ブタンジオールであり、
側鎖アルキル基含有ジオール(c-2)がプロピレングリコールおよび/または3-メチル-1,5-ペンタンジオールであり、
熱可塑性ポリウレタンの窒素含有率が2.0~2.8質量%であり、
熱可塑性ポリウレタンのMnが50,000~500,000である。
本発明は、前記熱可塑性ポリウレタンと他の成分とを含有する熱可塑性ポリウレタン組成物を提供する。他の成分としては、熱可塑性ポリウレタン組成物を製造する際に通常使用されている成分であれば、特に限定は無く、例えば、内部離型剤、充填剤、可塑剤、着色剤(染料、顔料)、安定剤(例えば、酸化防止剤、UV安定剤、熱安定剤等)、難燃剤、架橋剤、反応促進剤、補強剤等が挙げられる。
本発明の熱可塑性ポリウレタンは、公知のウレタン化反応技術により製造でき、プレポリマー法またはワンショット法のいずれによっても製造できる。例えば、
(1)単軸または多軸スクリュー型押出機に高分子ポリオール(B)、鎖伸長剤(C)および有機ジイソシアネート(A)並びに必要に応じて他の成分を、同時またはほぼ同時に連続的に供給して60~280℃、好ましくは200~260℃で連続溶融重合させて熱可塑性ポリウレタンを製造する方法;
(2)高分子ポリオール(B)および鎖伸長剤(C)等の活性水素原子含有化合物を混合して60~90℃に加熱した後、これらの混合物における活性水素原子とイソシアネート基のモル比(活性水素原子/イソシアネート基)が1/1~1/1.5となる量の有機ジイソシアネート(A)を加えて短時間撹拌した後に、200~260℃に加熱して熱可塑性ポリウレタンを製造する方法;
(3)有機ジイソシアネート(A)と高分子ポリオール(B)を押出機またはその他の反応装置内で予め反応させてイソシアネート基末端プレポリマーを形成した後に鎖伸長剤(C)を反応させて熱可塑性ポリウレタンを製造する方法;
(4)高分子ポリオール(B)、鎖伸長剤(C)および有機ジイソシアネート(A)並びに必要に応じて他の成分を有機溶媒に添加して有機溶媒中で熱可塑性ポリウレタンを製造する方法;
等が挙げられる。中でも溶融成形性および力学的特性に優れる熱可塑性ポリウレタンを製造する場合、実質的に溶媒の不存在下で溶融重合することが好ましく、多軸スクリュー型押出機を用いる連続溶融重合法がより好ましい。連続溶融重合法で得られた熱可塑性ポリウレタンは、一般に、80~130℃の固相重合で得られた熱可塑性ポリウレタンに比べて、強度の点において優れている。また、(1)の方法による場合は、押出機に反応成分のすべてを同時またはほぼ同時に供給するだけで、極めて簡単に目的とする熱可塑性ポリウレタンを連続して製造することができるので好ましい。
本発明の熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物を成形することにより、透明性および耐寒性に優れたシート、フィルム、ロール、ギア、ソリッドタイヤ、ベルト、ホース、チューブ、パッキング材、防振材、靴底、スポーツ靴、機械部品、自動車部品、スポーツ用品、弾性繊維等の成形品を円滑に製造することができる。成形方法としては、例えば、熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物を溶剤に溶かして均一溶液とした上でシート化またはフィルム化するキャスティング、ディッピング;加熱、混練した後に成形を行う押出成形、射出成形、カレンダー成形、注型成形、ブロー成形、インフレーション成形、発泡成形、回転成形、スラッシュ成形;等が挙げられる。
一つの部材(X)と一つの部材(Y)とを有する複合成形品;
二つの部材(Y)の間に部材(X)が介在する複合成形品;
二つの部材(X)の間に部材(Y)が介在する複合成形品;
部材(X)と部材(Y)とが交互に接触した複合成形品;
等が挙げられる。
また、前記の部材(X)および部材(Y)の一方または両方は層状であってもよく、従って本発明の複合成形品は、層状部材(X)と層状部材(Y)とが積層した積層構造体であってもよい。このような積層構造体の構成としては、例えば、
一つの層状部材(X)と一つの層状部材(Y)とを有する2層構造体;
二つの層状部材(Y)の間に層状部材(X)が中間層として存在する3層構造体;
二つの層状部材(X)の間に層状部材(Y)が中間層として存在する3層構造体;
層状の部材(X)と層状の部材(Y)とが交互に4層以上に積層された多層構造体;
等が挙げられる。
部材(Y)を本発明の熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物で溶融被覆する方法;
二つ以上の部材(Y)の間に、溶融状態の本発明の熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物を導入して、これらを接着・一体化させる方法;
部材(Y)を金型内に配置(インサート)した後、溶融状態の本発明の熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物を充填して、これらを接着・一体化させる方法;
本発明の熱可塑性ポリウレタンまたは熱可塑性ポリウレタン組成物と部材(Y)を構成する材料とを共押出成形して、これらを接着・一体化させる方法;
部材(X)と部材(Y)とをプレスする方法;
部材(X)と部材(Y)とを接着剤で接着・一体化させる方法;
等を挙げることができる。
熱可塑性ポリウレタン組成物の溶融成形を行う場合は、加工温度が180℃以上であり、有機過酸化物の分解温度以上であるため、有機過酸化物による化学架橋では、溶融成形中に架橋が過度に進んでしまうことがある。また、シランによる水架橋では、使用量と架橋量の制御が難しいことがある。これらの理由からも、ラジカル架橋剤による電子線架橋が好ましい。
[有機ジイソシアネート(A)]
MDI:4,4’-ジフェニルメタンジイソシアネート
[高分子ポリオール(B)]
・Mnが1000未満のポリエーテルポリオール(b-1)
PTMG850:ポリテトラメチレンエーテルグリコール(Mn:850、三菱化学社製)
・Mnが1000~5000のポリエーテルポリオール(b-1)
PTMG1000:ポリテトラメチレンエーテルグリコール(Mn:1000、三菱化学社製)
PTMG1500:ポリテトラメチレンエーテルグリコール(Mn:1500、三菱化学社製)
PTMG2000:ポリテトラメチレンエーテルグリコール(Mn:2000、三菱化学社製)
PTMG3000:ポリテトラメチレンエーテルグリコール(Mn:3000、三菱化学社製)
PTRMG2000:ポリトリメチレンエーテルグリコール(Mn:2000、デュポン社製)
・Mnが1000~5000の他のポリオール(b-2)
PMPA1500:アジピン酸と3-メチル-1,5-ペンタンジオールからなるポリエステルポリオール(Mn:1500、クラレ社製)
PMPA2000:アジピン酸と3-メチル-1,5-ペンタンジオールからなるポリエステルポリオール(Mn:2000、クラレ社製)
[鎖伸長剤(C)]
・直鎖ジオール(c-1)
BD:1,4-ブタンジオール
1,3-PD:1,3-プロパンジオール(デュポン社製)
・側鎖アルキル基含有ジオール(c-2)
MPD:3-メチル-1,5-ペンタンジオール(クラレ社製)
1,2-PD:プロピレングリコール(ダウ・ケミカル社製)
2MPD:2-メチル-1,3-プロパンジオール(東京化成工業社製)
MBD:2-メチル-1,4-ブタンジオール(東京化成工業社製)
[ウレタン化反応触媒]
SN:ジブチルスズジアセテート
[架橋剤]
TMPTA:トリメチロールプロパントリアクリレート
TMPTMA:トリメチロールプロパントリメタクリレート
以下の実施例および比較例で得られた熱可塑性ポリウレタンの窒素原子含有率(質量%)を元素分析計(パーキンエルマー社製「2400-2型」)にて測定した。
以下の実施例および比較例で得られた熱可塑性ポリウレタンをプレス成形機(温度180~200℃)でプレス成形して、20cm×20cm×2mmのシートを作製した。次いで、熱可塑性ポリウレタンシートのヘーズを透過率計(村上カラーリサーチラボラトリー製「HR-100」)にて測定した。
前記(2)で得た熱可塑性ポリウレタンシートを用いて、動的粘弾性の測定(オリエンテック社製「RHEOVIBRON」、測定条件:11Hz、引張り、3℃/分昇温)を行い、-30~0℃における貯蔵弾性率の最大値を(E’-1)とし、25℃における貯蔵弾性率の値を(E’-2)とし、以下の基準で耐寒性を評価した。
(E’-1)/(E’-2)≦5 ・・・耐寒性良好(〇)
(E’-1)/(E’-2)>5 ・・・耐寒性不良(×)
前記(2)で得た熱可塑性ポリウレタンシートを用いて、その破断強度をJIS K 7311に準じて測定した。
前記(2)で得た熱可塑性ポリウレタンシートを用いて、180~200℃における動的粘弾性の測定(測定装置:レオメトリックサイエンティフィック社製「RDA-III」、測定条件:1Hz、Shear:10%)を行い、そこで得られたG0’(測定開始直後のせん断弾性率)およびG’(1時間の溶融滞留後のせん断弾性率)をもとに以下の式から増粘率を算出した。
増粘率=G’/G0’
表面を鏡面仕上げした金型を用いて、射出成形(日精樹脂工業社製FS-80S12ASE、シリンダー温度190~220℃、金型温度30℃、射出時間5~8秒、冷却時間30秒)によって、以下の実施例および比較例で得られた熱可塑性ポリウレタンから円板状の成形品(直径120mm、厚さ2mm)を製造し、得られた成形品を25℃で3日間放置した後、テーバー摩耗試験機(荷重1kg、摩耗輪H-22)を使用して、JIS K 7311に準じて、テーバー摩耗量を測定した。
以下の実施例および比較例で得られた熱可塑性ポリウレタンの数平均分子量を、示差屈折計検出器(島津製作所製、「RID6A」)および高速液体クロマトグラフィー(HPLC)(島津製作所製「LC-9A」、カラム:東ソー株式会社製「Shodex KD-806M」および「Shodex KD-802.5」を連結、展開溶媒:ジメチルホルムアミド、標準試料:ポリスチレン)を用いるGPCによって測定した。
20質量ppmのSNを含むポリテトラメチレンエーテルグリコール(PTMG2000)74.2質量%、4,4’-ジフェニルメタンジイソシアネート(MDI)21.4質量%、1,4-ブタンジオール(BD)3.9質量%および3-メチル-1,5-ペンタンジオール(MPD)0.6質量%の割合で、加熱下に液状状態で一括して定量ポンプによって2軸押出機(L/D=34;φ=30mm)に連続供給して、260℃で重合を行って熱可塑性ポリウレタンを製造した。
熱可塑性ポリウレタン原料の種類および比率を表1のように変更した以外は実施例1と同様にして2軸押出機に連続供給して、260℃で重合して熱可塑性ポリウレタンを製造した。
熱可塑性ポリウレタン原料の種類および比率を表2のように変更した以外は実施例1と同様にして2軸押出機に連続供給して、260℃で重合して熱可塑性ポリウレタンを製造した。
有機ジイソシアネート(A)、高分子ポリオール(B)および鎖伸長剤(C)の種類および割合(質量%);
高分子ポリオール(B)が2種のポリオールを含有する場合にはそれらのモル比;
鎖伸長剤(C)中の2種のジオールのモル比;および
得られた熱可塑性ポリウレタンの窒素原子含有率(質量%);
を記載する。
熱可塑性ポリウレタン原料の種類および比率を表5のように変更した以外は実施例1と同様にして2軸押出機に連続供給して、260℃で重合して熱可塑性ポリウレタンを製造した。ここで得られた熱可塑性ポリウレタン100質量部に対し、表5に示す架橋剤3~10質量部を2軸押出機にて200℃で溶融混練して、熱可塑性ポリウレタン組成物を得た。
前記熱可塑性ポリウレタン組成物をプレス成形にて0.5mm厚のシートに成形した後、そのシートに電子線加速機[日新ハイボルテージ社製、機種名「キュアトロンEB200-100」]により、加速電圧200kV、照射線量200kGyの電子線を照射して架橋を行って、架橋シート(架橋成形品)を得た。前記熱可塑性ポリウレタンシートに替えて該架橋シートを用いたこと以外は前記と同様にして、耐寒性、透明性および破断強度を測定した。また、得られた架橋シートから円板状シートを形成し、前記円板状の成形品に替えて該円板状シートを用いたこと以外は前記と同様にして、テーバー摩耗量を測定した。これらの結果を下記表6に示す。
有機ジイソシアネート(A)、高分子ポリオール(B)および鎖伸長剤(C)の種類および割合(質量%);
高分子ポリオール(B)が2種のポリオールを含有する場合にはそれらのモル比;
鎖伸長剤(C)中の2種のジオールのモル比;
得られた熱可塑性ポリウレタンの窒素原子含有率(質量%);並びに
架橋剤の種類および熱可塑性ポリウレタン100質量部に対する架橋剤の使用量(質量部);
を記載する。
Claims (14)
- 有機ジイソシアネート(A)と、
数平均分子量(Mn)が1000~5000の高分子ポリオール(B)と、
鎖伸長剤(C)と
を反応させて得られる熱可塑性ポリウレタンであって、
鎖伸長剤(C)が直鎖ジオール(c-1)および側鎖アルキル基含有ジオール(c-2)からなり、
鎖伸長剤(C)における直鎖ジオール(c-1)と側鎖アルキル基含有ジオール(c-2)のモル比(直鎖ジオール(c-1)/側鎖アルキル基含有ジオール(c-2))が97/3~60/40であり、
窒素原子含有率が1.5質量%以上4.0質量%未満であることを特徴とする、熱可塑性ポリウレタン。 - 有機ジイソシアネート(A)の割合が30質量%以下である請求項1に記載の熱可塑性ポリウレタン。
- 有機ジイソシアネート(A)が4,4’-ジフェニルメタンジイソシアネートである、請求項1または2に記載の熱可塑性ポリウレタン。
- 高分子ポリオール(B)がポリエーテルポリオール(b-1)であるか、またはポリエーテルポリオール(b-1)および他のポリオール(b-2)からなり、
他のポリオール(b-2)とポリエーテルポリオール(b-1)のモル比(他のポリオール(b-2)/ポリエーテルポリオール(b-1))が0/100~40/60である、請求項1~3のいずれか一項に記載の熱可塑性ポリウレタン。 - 他のポリオール(b-2)がポリエステルポリオールである、請求項4に記載の熱可塑性ポリウレタン。
- ポリエステルポリオールを構成するポリオール成分が側鎖アルキル基含有ジオール(d)である、請求項5に記載の熱可塑性ポリウレタン。
- 側鎖アルキル基含有ジオール(d)が3-メチル-1,5-ペンタンジオールである、請求項6に記載の熱可塑性ポリウレタン。
- 側鎖アルキル基含有ジオール(c-2)がプロピレングリコール、3-メチル-1,5-ペンタンジオール、2-メチル-1,3-プロパンジオールおよび2-メチル-1,4-ブタンジオールからなる群から選ばれる少なくとも一つである、請求項8に記載の熱可塑性ポリウレタン。
- 側鎖アルキル基含有ジオール(c-2)がプロピレングリコールおよび/または3-メチル-1,5-ペンタンジオールである、請求項8に記載の熱可塑性ポリウレタン。
- 請求項1~10のいずれか一項に記載の熱可塑性ポリウレタンを含む成形品。
- 請求項1~10のいずれか一項に記載の熱可塑性ポリウレタンと、
熱可塑性ポリウレタン100質量部に対して1~20質量部の架橋剤と
を含有する、熱可塑性ポリウレタン組成物。 - 請求項12に記載の熱可塑性ポリウレタン組成物を含む成形品。
- 請求項13に記載の成形品を架橋することによって得られる架橋成形品。
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US10647098B2 (en) | 2015-07-01 | 2020-05-12 | Lg Chem, Ltd. | Base film |
US11203678B2 (en) | 2017-04-28 | 2021-12-21 | Derrick Corporation | Thermoplastic compositions, methods, apparatus, and uses |
US11505638B2 (en) | 2017-04-28 | 2022-11-22 | Derrick Corporation | Thermoplastic compositions, methods, apparatus, and uses |
Also Published As
Publication number | Publication date |
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EP2881412A1 (en) | 2015-06-10 |
CN104619738A (zh) | 2015-05-13 |
US20150210799A1 (en) | 2015-07-30 |
JPWO2014024847A1 (ja) | 2016-07-25 |
CA2880729A1 (en) | 2014-02-13 |
RU2615137C2 (ru) | 2017-04-04 |
EP2881412B1 (en) | 2019-06-26 |
EP2881412A4 (en) | 2016-03-23 |
JP6450592B2 (ja) | 2019-01-09 |
RU2015107832A (ru) | 2016-09-27 |
US9593200B2 (en) | 2017-03-14 |
KR20150041067A (ko) | 2015-04-15 |
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