WO2016104456A1 - Composition de résine de polyuréthane et article moulé de résine de polyuréthane - Google Patents

Composition de résine de polyuréthane et article moulé de résine de polyuréthane Download PDF

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Publication number
WO2016104456A1
WO2016104456A1 PCT/JP2015/085727 JP2015085727W WO2016104456A1 WO 2016104456 A1 WO2016104456 A1 WO 2016104456A1 JP 2015085727 W JP2015085727 W JP 2015085727W WO 2016104456 A1 WO2016104456 A1 WO 2016104456A1
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substituent
group
iminoether
general formula
polyurethane resin
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PCT/JP2015/085727
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English (en)
Japanese (ja)
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福田　誠
上平　茂生
倫弘 小川
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富士フイルム株式会社
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Priority to JP2016566368A priority Critical patent/JP6316455B2/ja
Publication of WO2016104456A1 publication Critical patent/WO2016104456A1/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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters

Definitions

  • the present disclosure relates to a polyurethane resin composition and a polyurethane resin molded article.
  • Polyurethane is excellent in various properties such as mechanical properties, abrasion resistance, elastic recovery and flex resistance, and can be melt-molded. Therefore, polyurethane is used in various applications as a substitute material for synthetic rubbers and plastics. Furthermore, polyurethane is a material with high heat resistance, hydrolysis stability and abrasion resistance due to recent expansion of usage applications such as urethane foams such as sealing materials and heat insulating materials, shoe products, and automotive parts applications such as bumpers and headrests. There is a need for further improvement of
  • Japanese Patent Application Laid-Open No. 2011-246550 proposes that a polyurethane having improved hydrolysis resistance and heat resistance be produced by adding a cyclic carbodiimide at the time of synthesis of the polyurethane.
  • the method of adding a cyclic carbodiimide at the time of synthesis of polyurethane does not lead to the improvement of a commercially available polyurethane, and is not a general method.
  • the screw portion is carried out at 220 ° C. or lower even at high temperature, and it is about 230 ° C. at a part of the tip (nozzle). Therefore, if cyclic carbodiimide is added when molding using a commercially available polyurethane, the molding temperature of the polyurethane is usually less than 220 ° C., whereas the melting point of the cyclic carbodiimide is as high as 230 to 250 ° C. Therefore, it is difficult to react, and the improvement effect of heat resistance etc. is small.
  • the present invention has been made in view of the above-mentioned circumstances, and a polyurethane resin composition capable of producing a polyurethane resin molded article excellent in hydrolysis resistance and moldability even if general-purpose polyurethane is used Intended to be provided.
  • Another object of the present invention is to provide a polyurethane resin molded article excellent in hydrolysis resistance and moldability even when general-purpose polyurethane is used.
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 3 represents R 11 represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3)
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent. R 31 , R 32 and R 33 may be linked to each other to form a ring.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • * represents a position to be bonded to a nitrogen atom.
  • ⁇ 2> is an aryl group R 3 is represented by the general formula (3) in the general formula (1) polyurethane resin composition according to ⁇ 1>.
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R 21 represents a substituent
  • m represents an integer of 0 to 5, when R 21 there are a plurality, even more R 21 is the same as each other or different, a ring together You may form.
  • R 41 represents a substituent
  • n represents an integer of 0 to 5, when R 41 there are a plurality, even more R 41 is the same as each other or different, a ring together You may form.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (6)
  • the polyurethane resin composition as described in one.
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • p represents an integer of 2 to 4
  • L 1 has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.
  • ⁇ 5> Any one of ⁇ 1> to ⁇ 3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (7)
  • the polyurethane resin composition as described in one.
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 11 and R 12 And R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent
  • p represents an integer of 2 to 4
  • p represents a p-valent group in which L 2 is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent.
  • ⁇ 6> Any one of ⁇ 1> to ⁇ 3>, wherein the multimer of the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound represented by the following general formula (8) The polyurethane resin composition as described in one.
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • p represents an integer of 2 to 4
  • L 3 represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L 3 , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • thermoplastic polyurethane is a polyester-based polyurethane.
  • ⁇ 9> A polyurethane resin molded article molded using the polyurethane resin composition according to any one of ⁇ 1> to ⁇ 8>.
  • a polyurethane resin composition capable of producing a polyurethane resin molded article excellent in hydrolysis resistance and moldability, even when a general purpose polyurethane is used. Further, according to the present disclosure, a polyurethane resin molded article excellent in hydrolysis resistance and moldability is provided even when a general purpose polyurethane is used.
  • the polyurethane resin composition of the present disclosure is represented by a thermoplastic polyurethane (hereinafter sometimes simply referred to as “polyurethane”), an iminoether compound represented by the following general formula (1), and a general formula (1) And at least one chained iminoether group-containing compound (hereinafter sometimes simply referred to as "chained iminoether group-containing compound”) selected from multimers of iminoether compounds.
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 3 represents R 11 represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3)
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent. R 31 , R 32 and R 33 may be linked to each other to form a ring.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • * represents a position to be bonded to a nitrogen atom.
  • a chain iminoether group-containing compound synthesized via an iminoether compound represented by the general formula (1) which means a chain iminoether group-containing compound which has two or more partial structures other than a linking group
  • a chain iminoether group-containing compound synthesized without passing through the iminoether compound represented by the general formula (1) is also included.
  • the polyurethane resin composition of the present disclosure can produce a polyurethane resin molded article excellent in hydrolysis resistance and moldability, even when a general-purpose polyurethane is used. The reason is presumed as follows.
  • Polyurethanes are mainly classified into polyester-based polyurethanes having a polyester-based polyol as a raw material and polyether-based polyurethanes having a polyether-based polyol as a raw material.
  • polyester-based polyurethanes a trace amount of carboxylic acid is contained in the raw material polyester polyol, and the polyester portion is thermally decomposed during melt molding to form a carboxy group.
  • carboxy group promotes hydrolysis
  • the chain iminoether group-containing compound contained in the polyurethane resin composition of the present disclosure is more reactive than the cyclic iminoether compound, and reacts at the molding temperature of the polyurethane to form a carboxy group. It is believed that the hydrolysis resistance is improved by sealing the
  • a cyclic iminoether compound in which the iminoether moiety containing an iminoether group is cyclic is lower in reactivity than a chain iminoether group-containing compound, and when molded at a high temperature, a state in which polyurethane is added to the iminoether moiety It is considered that the viscosity of the polymer increases greatly as the molecular weight of the polymer increases. In particular, when the cyclic iminoether moiety is bifunctional or more (dimer or more), it is considered that a large number of polyurethanes are added to cause significant thickening.
  • Synthesis method of imino ether compound As a method of synthesizing the iminoether compound represented by the general formula (1), a method in which an amide compound is imidoyl chloride, reaction with an alkoxide, and a method in which an aniline compound and an ortho ester compound are reacted. Although any method may be used as a synthesis method of the iminoether compound represented by General formula (1), it is preferable to use the method of making an aniline compound and an ortho ester compound react. A polyurethane resin composition to which an iminoether compound synthesized by a method of reacting an aniline compound and an ortho ester compound is added is preferable because hydrolysis resistance and color tone become better.
  • the ortho ester compound used for the synthesis of the iminoether compound represented by the general formula (1) is preferably a compound represented by the following general formula (9).
  • R 4 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 51 and R 52 And R 53 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • ortho ester compounds used for the synthesis of iminoether compounds represented by the general formula (1) include trimethyl orthoacetate, triethyl orthoacetate, tripropyl orthoacetate, tributyl orthoacetate, tribenzyl orthoacetate, trimethyl orthoformate, Triethyl orthoformate, tripropyl orthoformate, tributyl orthoformate, tribenzyl orthoformate, trimethyl orthopropionate, triethyl orthopropionate, tripropyl orthopropionate, tributyl orthopropionate, tributyl orthopropionate, trimethyl orthobenzoate, trimethyl orthobenzoate And triethyl orthobenzoate, tributyl orthobenzoate, and tribenzyl orthobenzoate.
  • the ortho ester compound may be a commercially available product or may be synthesized. In the case of synthesis, it can be synthesized by imidating a nitrile compound such as hydrogen cyanide, acetonitrile, propionitrile, n-butyronitrile, benzonitrile or the like and reacting with an alcohol or a method of reacting trichlorobenzene with an alkoxide.
  • a nitrile compound such as hydrogen cyanide, acetonitrile, propionitrile, n-butyronitrile, benzonitrile or the like
  • thermoplastic polyurethane used in the present disclosure is a rubber-like elastic body having a urethane group (—NHCOO—) in its molecular structure, and is also called a urethane rubber or a urethane resin.
  • Thermoplastic polyurethanes are generally constructed by the polyaddition reaction of long chain glycols (polyols), polyisocyanates and short chain glycols (chain extenders).
  • the type of polyurethane used in the present disclosure is not particularly limited, and may be polyester-based polyurethane or polyether-based polyurethane.
  • polyester-based polyurethane a trace amount of carboxylic acid is contained in the raw material polyester polyol, and the polyester portion is thermally decomposed during molding or moist heat to generate carboxylic acid. Since a carboxylic acid acts as a catalyst for hydrolysis, polyester-based polyurethanes are easily hydrolyzable, but it is believed that the chain iminoether group-containing compound seals the carboxylic acid during molding and in wet heat. Therefore, when the polyurethane resin composition of the present disclosure contains a polyester-based polyurethane as the polyurethane, the hydrolysis resistance can be significantly improved.
  • thermoplastic polyurethanes can be suitably used.
  • thermoplastic polyurethane for example, Milactolan (registered trademark) E 580 (polyester polyurethane, manufactured by Nippon Polyurethane Co., Ltd.), Milactolan (registered trademark) E 180 (polyester polyurethane, manufactured by Nippon Polyurethane Co., Ltd.), Milactolan (registered trademark) E 380 (Polyether-based polyurethane, manufactured by Nippon Polyurethane Co., Ltd.) and the like.
  • thermoplastic polyurethane used in the present disclosure may be obtained synthetically.
  • the manufacturing method of the thermoplastic polyurethane used by this indication is not specifically limited, A well-known method is applied suitably. For example, a method of mixing and stirring the polyol component, the chain extender component and the polyisocyanate component simultaneously (one-shot method), a method of adding the chain extender to the prepolymer formed from the polyol component and the polyisocyanate component, and mixing and stirring (Prepolymer method) etc. are illustrated.
  • the polyol component which is a long chain glycol having terminal active hydrogen is not particularly limited, and a known polyol component is exemplified. That is, polyester type, polyether type, polycarbonate type, acrylic type, silicone type, 1,4-polybutadiene type, 1,2-polybutadiene type, phenolic type, castor oil type etc. having a molecular weight of 500 to 6000, preferably 1000 to 3000 And various polyols, flame retardant polyols and the like.
  • polyester-based polyols caprolactone-based, adipate-based, copolyester-based polyols and the like are generally preferably used.
  • polycaprolactone, polycarbonate polyol, or dicarboxylic acid such as adipic acid, isophthalic acid or terephthalic acid and ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexanediol, trimethylolpropane, neole
  • condensation reaction products with polyols such as pentyl glycol.
  • polyether-based polyols examples include polypropylene glycol-based polyols, polyethylene glycol-based glycols or ethylene oxide-modified products thereof, amine-modified products, or polyoxytetramethylene glycol. These can be used alone or, if desired, in combination of two or more.
  • polyol components are preferably used in a proportion of 30 to 90% by mass, more preferably 40 to 70% by mass, based on the total of the polyol component, the chain extender and the polyisocyanate component.
  • the polyol component is used in an amount of 30% by mass or more, the reduction in moldability tends to be suppressed, while when it is used in a proportion of 90% by mass or less, the reduction in hydrolysis resistance tends to be suppressed.
  • isocyanate component which can be used by this indication, there is no limitation in particular and well-known polyisocyanate can be illustrated.
  • polyisocyanate such as 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, etc.
  • Aliphatic diisocyanates or aromatic diisocyanates such as xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, tolidine diisocyanate, p-phenylene diisocyanate, 1,5-naphthyl diisocyanate, etc. can be exemplified. These may be used alone or in combination of two or more.
  • the polyisocyanate component is preferably used in a proportion of 5 to 70% by mass, more preferably 15 to 40% by mass, based on the total amount of the polyisocyanate component, the polyol component and the chain extender.
  • the chain extender is not particularly limited, and known chain extenders are exemplified. Specifically, for example, 1,4-butanediol, 1,6-hexanediol, 2,3-butanediol, p-phenylenedi ( ⁇ -hydroxyethyl) ether, p-xylylene glycol, glycerin monoallyl ether, di- At least one of glycols such as methylol dihydropyran, diamines such as ethylenediamine, 3,3'-dichloro-4,4'-diaminodiphenylmethane and diethyltoluylene diamine, water, etc. is used.
  • Catalysts can also be used to make polyurethanes.
  • a catalyst used for manufacture of polyurethane there is no limitation in particular and a well-known catalyst system can be used conveniently. Specific examples thereof include organic metal compounds such as tin-based, lead-based, iron-based and titanium-based and amine-based compounds.
  • amine catalysts such as triethyl
  • These catalysts are used in a proportion of 0.5 to 10 parts by mass, preferably 1 to 3 parts by mass, per 100 parts by mass of the total amount of polyurethane raw materials consisting of the polyol component, the polyisocyanate component and the chain extender. If the addition amount of the catalyst is 0.5 parts by mass or more, the effect of improving the heat resistance, the abrasion resistance and the hydrolysis resistance is observed, while if it is 10 parts by mass or less, foaming or strength, Degradation of mechanical properties such as elongation is suppressed.
  • the polyurethane formation reaction using each of the above components is performed, for example, by a one-shot method or a prepolymer method.
  • a urethanization catalyst is added simultaneously with each component, or in the prepolymer formation step in the prepolymer method, and in the prepolymer method, a chain extender is then added and reacted.
  • thermoplastic polyurethane which can be used in the present disclosure.
  • the chain iminoether group-containing compound used in the present disclosure is an iminoether compound represented by the following general formula (1) or a multimer of the iminoether compound represented by the general formula (1).
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 3 represents R 11 represents an alkyl group represented by Formula (2) or an aryl group represented by the following General Formula (3)
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom or an alkyl which may have a substituent Represents an aryl group which may have a group or a substituent.
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent. R 31 , R 32 and R 33 may be linked to each other to form a ring.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • * represents a position to be bonded to a nitrogen atom.
  • the alkyl group represented by R 2 is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 12 carbon atoms.
  • the number of carbon atoms of the alkyl group represented by R 2 indicate the number of carbon that does not contain a substituent group.
  • the alkyl group represented by R 2 may be linear or branched.
  • the alkyl group represented by R 2 may be a cycloalkyl group.
  • the alkyl group represented by R 2 is methyl, ethyl, n-propyl, iso-propyl, n-butyl, tert-butyl, sec-butyl, iso-butyl, n-pentyl, A sec-pentyl group, an iso-pentyl group, an n-hexyl group, a sec-hexyl group, an iso-hexyl group, a cyclohexyl group and the like can be mentioned.
  • the alkyl group represented by R 2 is more preferably methyl, ethyl, n-propyl, iso-propyl, iso-butyl or cyclohexyl.
  • the alkyl group represented by R 2 may further have a substituent.
  • substituents include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like.
  • the aryl group represented by R 2 is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. Number of carbon atoms of the aryl group represented by R 2, indicate the number of carbon that does not contain a substituent group.
  • the aryl group represented by R 2 may further have a substituent.
  • the above-mentioned substituents that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified.
  • the substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.
  • the alkoxy group represented by R 2 is preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and an alkoxy group having 2 to 6 carbon atoms Is particularly preferred.
  • Number of carbon atoms of the alkoxy group represented by R 2 indicate the number of carbon that does not contain a substituent group.
  • the alkoxy group represented by R 2 may be linear, branched or cyclic. Preferred examples of the alkoxy group represented by R 2 may be a group at the end of the alkyl group represented by R 2 -O- is linked.
  • the alkoxy group represented by R 2 may further have a substituent.
  • the above-mentioned substituents that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified.
  • the substituent is not particularly limited as long as it does not interfere with the reaction of the iminoether group with the carboxy group.
  • R 3 represents an alkyl group represented by the above general formula (2) or an aryl group represented by the above general formula (3).
  • R 31 , R 32 and R 33 each independently represent a hydrogen atom or a substituent.
  • the substituents represented by R 31 , R 32 and R 33 may be linked to each other to form a ring.
  • the substituent include the above-mentioned alkyl group, aryl group, alkoxy group, halogen atom, nitro group, amido group, hydroxyl group, ester group, ether group, aldehyde group and the like.
  • R 31 , R 32 and R 33 may all be hydrogen atoms or may be the same substituent, or may be different substituents.
  • the alkyl group represented by the general formula (2) may be linear or branched.
  • the alkyl group represented by the general formula (2) may be a cycloalkyl group.
  • R 41 represents a substituent, and n represents an integer of 0 to 5. When n is 2 or more, a plurality of R 41 may be the same as or different from each other, and may be linked to each other to form a ring.
  • substituents that is, an alkyl group, an aryl group, an alkoxy group, a halogen atom, a nitro group, an amido group, a hydroxyl group, an ester group, an ether group, an aldehyde group and the like can be exemplified.
  • n is more preferably 0 to 3, and still more preferably 0 to 2.
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • the alkyl group and the aryl group the alkyl group and the aryl group that can be taken by R 2 can be similarly exemplified.
  • R 11 , R 12 and R 13 may be bonded to each other to form a ring.
  • the polyurethane resin composition of the present disclosure may contain, as a chain iminoether group-containing compound, a multimer of the iminoether compound represented by General Formula (1).
  • a chain iminoether group-containing compound containing as a repeating unit a structure excluding at least one of R 2 , R 3 or R 11 to R 13 in the general formula (1) is preferable.
  • the iminoether compound represented by the general formula (1) is preferably represented by the following general formula (4) from the viewpoint of easiness of synthesis.
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 11 and R 12 And R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • R 2 , R 11 , R 12 and R 13 have the same meaning as each other in the general formula (1), and preferred ranges are also the same.
  • R 41 has the same meaning as R 41 in Formula (3), and the preferred range is also the same.
  • n is preferably 0 to 3, and more preferably 0 to 2.
  • the iminoether compound represented by the general formula (1) is a chain iminoether group-containing compound in which R 3 in the general formula (1) is represented by the general formula (3) from the ease of synthesis, that is, It is preferable to be represented by Formula (5).
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent.
  • R 21 represents a substituent
  • m represents an integer of 0 to 5, when R 21 there are a plurality, even more R 21 is the same as each other or different, a ring together You may form.
  • R 41 represents a substituent
  • n represents an integer of 0 to 5, when R 41 there are a plurality, even more R 41 is the same as each other or different, a ring together You may form.
  • R 11, R 12 and R 13 are the same as those in formula (1), and preferred ranges are also the same.
  • R 41 has the same meaning as R 41 in formula (3), and the preferred range is also the same.
  • the R 21 can also be exemplified the same substituents as R 41 in the general formula (3).
  • n is preferably 0 to 3, and more preferably 0 to 2.
  • m is preferably 0 to 3, and more preferably 0 to 2.
  • a chain iminoether group-containing compound represented by the following general formula (6) is preferable from the ease of synthesis.
  • R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • p represents an integer of 2 to 4
  • L 1 has an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent at the end of bonding to a carbon atom It also represents a p-valent group which is a good alkoxylene moiety.
  • the alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
  • R 11, R 12 and R 13 are the same as those in formula (1), and preferred ranges are also the same.
  • R 41 has the same meaning as R 41 in Formula (3), and the preferred range is also the same.
  • n is preferably 0 to 3, and more preferably 0 to 2.
  • L 1 is an alkoxy moiety which may have a substituent, an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or a substituent, at the end of the bond to a carbon atom
  • a p-valent group which is a ren moiety p is an integer of 2 to 4, and p is preferably 2 or 3.
  • the alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
  • the divalent group include, for example, an alkylene group which may have a substituent, an arylene group which may have a substituent, and an alkoxylene group which may have a substituent.
  • the terminal of the bond with the carbon atom is an alkylene moiety which may have a substituent, an arylene moiety which may have a substituent, or an alkoxylene moiety which may have a substituent, as a partial structure, -SO 2- , -CO-, substituted or unsubstituted alkylene moiety, substituted or unsubstituted alkenylene moiety, alkynylene moiety, substituted or unsubstituted phenylene moiety, substituted or unsubstituted biphenylene moiety, substituted or unsubstituted naphthylene And groups containing at least one selected from -O-, -S- and -SO-.
  • the alkylene moiety which may have a substituent may be a cycloalkylene moiety which may have a substituent.
  • a trivalent group the group which remove
  • a tetravalent group the group which remove
  • a compound having two or more iminoether moieties in one molecule can be obtained, and a more excellent end capping effect can be exhibited. it can. Furthermore, the iminoether value (total molecular weight / number of iminoether groups) can be lowered by using a compound having two or more iminoether moieties in one molecule, and an iminoether compound can be efficiently reacted with a carboxy group. it can.
  • the chain-like iminoether group containing compound represented by following General formula (7) is also preferable from the easiness of a synthesis
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 11 and R 12 And R 13 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent
  • p represents an integer of 2 to 4
  • p represents a p-valent group in which L 2 is a arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent.
  • R 2 , R 11 , R 12 and R 13 have the same meanings as each other in the general formula (1), and the preferred ranges are also the same.
  • L 2 represents a p-valent group which is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, at the end of the bond to the nitrogen atom.
  • L 2 is preferably a p-valent group in which the end of the bond to the nitrogen atom is an arylene moiety which may have a substituent.
  • p is an integer of 2 to 4, and p is preferably 2 or 3.
  • Specific examples of L 2 include an arylene group which may have a substituent, and a cycloalkylene group which may have a substituent.
  • the end of the bond to the nitrogen atom is an arylene moiety which may have a substituent or a cycloalkylene moiety which may have a substituent, and as a partial structure, —SO 2 —, —CO—, substituted or unsubstituted ,
  • the chain-like iminoether group containing compound represented by following General formula (8) is also preferable from the easiness of a synthesis
  • R 2 represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent
  • R 41 represents a substituent
  • n represents an integer of 0 to 5. If R 41 there are a plurality, even more R 41 is the same as each other or different, may form a ring.
  • p represents an integer of 2 to 4
  • L 3 represents a p-valent group in which the bonding end with the oxygen atom is an alkylene part. In the alkylene moiety of L 3 , part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • R 2 is synonymous with R 2 in General Formula (1), and its preferable range is also the same.
  • R 41 has the same meaning as R 41 in Formula (3), and the preferred range is also the same.
  • n is preferably 0 to 3, and more preferably 0 to 2.
  • R 2 may link to R 41 to form a ring.
  • L 3 represents a p-valent group in which the end of the bond to the oxygen atom is an alkylene part.
  • part or all of the hydrogen atoms may be substituted with an alkyl group which may have a substituent or an aryl group which may have a substituent.
  • p is an integer of 2 to 4, and p is preferably 2 or 3.
  • Specific examples of L 3, include an alkylene group.
  • the end of the bond to the oxygen atom is an alkylene moiety, and as a partial structure, -SO 2- , -CO-, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkenylene group, an alkynylene group, a substituted or unsubstituted Examples thereof include a group containing at least one selected from a phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthylene group, -O-, -S- and -SO-.
  • ethylene group n-butylene group, substituted or unsubstituted -CH 2 -C (CH 3 ) 2 -CH 2- , substituted or unsubstituted -CH 2 -C 6 H 4 -CH 2- , Etc.
  • the molecular weight (total molecular weight / number of iminoether groups) per iminoether group of the chain iminoether group-containing compound used in the present disclosure is preferably 1000 or less, more preferably 750 or less, and 500 or less Is more preferred. By setting the molecular weight per iminoether group to 1000 or less, it becomes possible to seal the terminal carboxy group of the polyurethane with a low addition amount.
  • the polyurethane resin composition of the present disclosure includes a polyurethane and at least one linear iminoether group-containing compound selected from an iminoether compound represented by the general formula (1) and an oligomer thereof, at the time of molding. Can be effectively suppressed, and a polyurethane resin molded product having hydrolysis resistance can be produced. Moreover, the color taste of a molded object can also be controlled by adjusting the addition amount of a chain-like iminoether group containing compound.
  • the polyurethane resin composition of the present disclosure preferably contains 0.05 to 3 parts by mass of a chain iminoether group-containing compound with respect to 100 parts by mass of polyurethane.
  • the hydrolysis resistance of the polyurethane resin molded article can be further improved by setting the addition amount of the chain iminoether group-containing compound to preferably 0.05 parts by mass or more with respect to 100 parts by mass of the polyurethane, 3 By setting it as mass part or less, the heat resistance and hydrolysis resistance of a polyurethane resin molding can be improved more.
  • a chain iminoether group-containing compound is added to 100 parts by mass of the polyurethane. It is more preferable to include 0.1 to 2.0 parts by mass.
  • the polyurethane resin composition of this indication may use chain-like iminoether group containing compound individually by 1 type, and may use multiple types together, the chain-type iminoether group containing compound of multiple types may be used. When using together, it is preferable that a total amount is the said range.
  • the polyurethane resin composition of the present disclosure can be added to various additives such as a compatibilizer, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, and the like, as long as the effects of the present invention are not significantly impaired.
  • the composition may contain an inhibitor, a brightener, a colorant, a conductive agent, an ultraviolet absorber, a flame retardant, a flame retardant aid, a pigment, a dye and the like.
  • the polyurethane resin composition of the present disclosure does not refuse to contain an end capping agent other than the iminoether compound described above, as long as the effects of the present invention are not significantly impaired.
  • the polyurethane resin composition of this indication can also use together the terminal blocker chosen from a carbodiimide compound, an epoxy compound, and an oxazoline compound other than the iminoether compound mentioned above, for example.
  • the method for producing a polyurethane resin molded product using the polyurethane resin composition of the present disclosure is not particularly limited, and a known molding method may be applied depending on the use.
  • the polyurethane resin composition of the present disclosure is used as a raw material, and molded into a molded article of a desired shape such as a sheet using an injection molding machine, an extruder, a casting machine or the like, preferably 5 to 24 at 80 to 150 ° C. Secondary crosslink (anneal) about time.
  • a polyurethane resin molded product excellent in hydrolysis resistance and moldability can be obtained.
  • the application of the polyurethane resin composition of the present disclosure is not particularly limited, and for example, it is suitably used for the production of polyurethane resin molded articles such as urethane foams such as sealing materials and heat insulators, shoe products, and automotive parts such as bumpers and headrests. Can.
  • Example 1 1 part by mass of iminoether (1) is added to 100 parts by mass of Milactolan (registered trademark) E 580 (polyester-based polyurethane synthesized using caprolactone-based polyol as a raw material as a raw material, manufactured by Nippon Polyurethanes Co.) , Molded by injection molding machine under the forming conditions of nozzle temperature 190 ° C, cylinder front temperature 180 ° C, cylinder middle temperature 170 ° C, cylinder rear temperature 150 ° C, and sheet-like molded product (150 ⁇ 150 ⁇ 2 mm) And heated in an oven at 85 ° C. for 16 hours to prepare a test piece.
  • Milactolan registered trademark
  • E 580 polyurethane synthesized using caprolactone-based polyol as a raw material as a raw material, manufactured by Nippon Polyurethanes Co.
  • Examples 2 to 8 Comparative Examples 2 to 3, 6
  • Test pieces were prepared and evaluated in the same manner as in Example 1 except that the compounds described in Table 1 were added instead of the iminoether (1).
  • the cyclic carbodiimide (1) and the cyclic carbodiimide (2) used in Comparative Examples 2 and 3 were synthesized with reference to JP 2011-256337A.
  • Test pieces were prepared and evaluated in the same manner as in Example 1 except that the addition amount of the iminoether (1) was changed as described in Table 1, respectively.
  • Example 13 Same as Example 1 except that Milactolan (registered trademark) E 580 (manufactured by Nippon Polyurethane Co., Ltd.) is changed to Milactolan (registered trademark) E 180 (polyester polyurethane synthesized from adipate based polyol as a raw material as a raw material, manufactured by Nippon Polyurethane Co., Ltd.) Test pieces were prepared and evaluated.
  • Milactolan (registered trademark) E 580 manufactured by Nippon Polyurethane Co., Ltd.
  • Milactolan (registered trademark) E 180 polyester polyurethane synthesized from adipate based polyol as a raw material as a raw material, manufactured by Nippon Polyurethane Co., Ltd.
  • Example 14 Example 1 except that Milactolan (registered trademark) E 580 (manufactured by Nippon Polyurethane Co., Ltd.) is changed to Milactolan (registered trademark) E 380 (polyether polyurethane synthesized from polyether-based polyol as a polyol component, manufactured by Nippon Polyurethane Co., Ltd.) Test pieces were prepared and evaluated in the same manner as in.
  • Milactolan (registered trademark) E 580 manufactured by Nippon Polyurethane Co., Ltd.
  • Milactolan (registered trademark) E 380 polyether polyurethane synthesized from polyether-based polyol as a polyol component, manufactured by Nippon Polyurethane Co., Ltd.
  • Comparative Example 4 Test pieces were prepared and evaluated in the same manner as in Example 1 except that tetramethylenebisoxazoline (TMBO) having the following structure synthesized in the following Synthesis Example 10 was added instead of the iminoether (1) and added.
  • TMBO tetramethylenebisoxazoline
  • the reaction solution was cooled to room temperature, filtered, and the solvent was evaporated under reduced pressure. Then, 1.0 L of ethyl acetate was added, and after filtering, ethyl acetate was evaporated under reduced pressure.
  • the obtained oily compound was distilled and purified at 128 ° C. and 133.3 Pa (1 Torr) to obtain 118 g (75% yield) of TMBO. The obtained compound was identified by 1 H-NMR.
  • Comparative Example 5 Test pieces were prepared and evaluated in the same manner as in Example 1 except that Epocross (registered trademark) RPS (an oxazoline group-containing reactive polystyrene, manufactured by Nippon Shokubai Co., Ltd.) was added instead of the iminoether (1).
  • Epocross registered trademark
  • RPS an oxazoline group-containing reactive polystyrene, manufactured by Nippon Shokubai Co., Ltd.
  • Resins used in Examples and Comparative Examples, chain iminoether group-containing compounds and comparative compounds and evaluation results are shown in Table 1 below.
  • the symbol of resin in Table 1 means the following.
  • -PU-A Milactolan E 580 (polyester polyurethane synthesized from caprolactone polyol as a polyol component) manufactured by Nippon Polyurethane Industry Co., Ltd.
  • -PU-B Milactolan E 180 manufactured by Nippon Polyurethane Industry Co., Ltd.
  • -PU-C Milactolan E 380 manufactured by Nippon Polyurethane Co., Ltd.
  • Polyether-based polyurethane synthesized from an ether-based polyol as a polyol component
  • the polyurethane resin composition of each Example which added the chain-like iminoether group containing compound which concerns on this indication was excellent in hydrolysis resistance (wet heat resistance) and a moldability.
  • Comparative Example 6 since the reactivity of the cyclic iminoether (7) is low, the hydrolysis resistance of the molded product is inferior, and it is considered that the moldability is lowered by the partial reaction, high molecular weight formation and thickening. .

Abstract

La présente invention concerne une composition de résine de polyuréthane comprenant un polyuréthane thermoplastique et au moins un type de composé contenant un groupe iminoéther de type chaîne sélectionné parmi un composé iminoéther représenté par la formule générale (1) et un polymère de ce dernier, et un article moulé de la résine de polyuréthane. Dans la formule générale (1) : R2 représente un groupe alkyle, un groupe aryle ou un groupe alcoxy; R3 représente un groupe alkyle ou un groupe aryle représenté par la formule générale (2) ou (3) [où : R31 à R33 représentent indépendamment un atome d'hydrogène ou un substituant qui peuvent être liés ensemble pour former un cycle; R41 représente un substituant; n est un nombre entier d'une valeur de 0 à 5, à condition que lorsqu'il existe deux ou plusieurs R41, ces R41 peuvent être soit identiques soit différents; et * représente une position de liaison à l'atome d'azote]; et R11 à R13 représentent indépendamment un atome d'hydrogène, un groupe alkyle ou un groupe aryle.
PCT/JP2015/085727 2014-12-26 2015-12-21 Composition de résine de polyuréthane et article moulé de résine de polyuréthane WO2016104456A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230212347A1 (en) * 2016-06-28 2023-07-06 Lubrizol Advanced Materials, Inc. Articles Made from Hydrophilic Thermoplastic Polyurethane Compositions

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5144576A (fr) * 1974-07-29 1976-04-16 Ici Ltd
JPS63273623A (ja) * 1987-03-11 1988-11-10 インペリアル・ケミカル・インダストリーズ・ピーエルシー 反応射出成形エラストマー製造用組成物
JPH02107625A (ja) * 1988-09-09 1990-04-19 Ici Americas Inc イミノ／エナミン官能性化合物を用いるポリウレタン／尿素フォーム

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5144576A (fr) * 1974-07-29 1976-04-16 Ici Ltd
JPS63273623A (ja) * 1987-03-11 1988-11-10 インペリアル・ケミカル・インダストリーズ・ピーエルシー 反応射出成形エラストマー製造用組成物
JPH02107625A (ja) * 1988-09-09 1990-04-19 Ici Americas Inc イミノ／エナミン官能性化合物を用いるポリウレタン／尿素フォーム

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20230212347A1 (en) * 2016-06-28 2023-07-06 Lubrizol Advanced Materials, Inc. Articles Made from Hydrophilic Thermoplastic Polyurethane Compositions
US20230212348A1 (en) * 2016-06-28 2023-07-06 Lubrizol Advanced Materials, Inc. Articles Made from Hydrophilic Thermoplastic Polyurethane Compositions

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