WO2023199756A1 - 化合物及びその製造方法、組成物、ウレタン樹脂、水性ウレタン樹脂分散体並びにコーティング剤 - Google Patents

化合物及びその製造方法、組成物、ウレタン樹脂、水性ウレタン樹脂分散体並びにコーティング剤 Download PDF

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WO2023199756A1
WO2023199756A1 PCT/JP2023/013493 JP2023013493W WO2023199756A1 WO 2023199756 A1 WO2023199756 A1 WO 2023199756A1 JP 2023013493 W JP2023013493 W JP 2023013493W WO 2023199756 A1 WO2023199756 A1 WO 2023199756A1
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formula
following formula
contained
moles
bond
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English (en)
French (fr)
Japanese (ja)
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康平 本田
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Tosoh Corp
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Tosoh Corp
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Priority to KR1020247036956A priority Critical patent/KR20250003702A/ko
Priority to US18/855,632 priority patent/US20250304741A1/en
Priority to EP23788176.8A priority patent/EP4495164A4/en
Priority to JP2023555844A priority patent/JP7452770B2/ja
Priority to CN202380033215.0A priority patent/CN118984846A/zh
Publication of WO2023199756A1 publication Critical patent/WO2023199756A1/ja
Priority to JP2024021190A priority patent/JP2024040465A/ja
Anticipated expiration legal-status Critical
Priority to JP2025058238A priority patent/JP2025089571A/ja
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    • C08G18/4269—Lactones
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a compound, a method for producing the same, a composition, a urethane resin, an aqueous urethane resin dispersion, and a coating agent.
  • polycarbonate polyols are useful as raw materials for producing urethane resins (also called polyurethane resins) by reacting with polyisocyanate compounds, and are useful as raw materials for adhesives, paints, etc. be.
  • polyester polyols have ester bonds
  • urethane resins obtained from polyester polyols have a drawback of poor hydrolysis resistance.
  • polyether polyol has an ether bond
  • urethane resin obtained from polyether polyol has a drawback of poor weather resistance and heat resistance.
  • urethane resins obtained from polycarbonate polyols tend to have excellent durability (heat resistance, weather resistance, hydrolysis resistance, chemical resistance, etc.).
  • a polycarbonate polyol is usually produced by reacting a carbonate ester and a diol in the presence of a transesterification catalyst (transesterification reaction).
  • Patent Documents 1 and 2 propose polycarbonate polyols obtained by transesterification of polycarbonate diols and triol compounds and/or tetraol compounds.
  • the present invention provides the following inventions.
  • R 1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 represents an alkanediyl group
  • R 3 represents an alkanediyl group
  • R 4 is an alkanediyl group
  • R a , R b , and R c each independently represent an alkanediyl group
  • *1 represents a bonding site with a carbonyl group
  • *2 represents a bonding site with an oxygen atom
  • n 1 and m 1 each represent an integer of 0 or more.
  • R 1 , R 2 and R 4 have the same meanings as above, and n 2 and m 2 each represent an integer of 0 or more.
  • a plurality of R 2 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • a plurality of R 3 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • C A1-1 is the total number of moles of groups represented by the following formula (a1-2) contained in the composition
  • C A1-2 is the total number of moles of the groups represented by the following formula (a1-2).
  • the total number of moles of groups represented by the following formula (a1-3) contained in the composition is defined as C A1-3
  • the total number of moles of groups represented by the following formula (a2-2) contained in the composition is defined as C A2 -2
  • the total number of moles of groups represented by the following formula (a2-3) contained in the composition is C A2-3
  • the molar ratio ((C A2-2 + C A2-3 )/(C The composition according to [2], wherein A1-1 +C A1-2 +C A1-3 )) is 0.01 to 0.750.
  • R 1 , R 2 and R 4 have the same meanings as above, and n 4 represents an integer of 0 or more.
  • R 4s When a plurality of R 4s exist, they may be the same or different from each other.
  • R 1 , R 3 and R 4 have the same meanings as above, and n 5 represents an integer of 0 or more.
  • n 5 represents an integer of 0 or more.
  • R 4s When a plurality of R 4s exist, they may be the same or different from each other.
  • the total number of moles of groups represented by the following formula (a1-2) contained in the composition is C A1-2
  • the total number of moles of groups represented by the following formula (I) contained in the composition is The composition according to any one of [2] to [5], wherein the molar ratio (C A1-2 /C T ) is 0.001 to 0.99, where C T is the number of moles.
  • C A1-2 the total number of moles of groups represented by the following formula (I) contained in the composition
  • R 1 has the same meaning as above, and * indicates a bond.
  • [In formula (I), R 1 has the same meaning as above, and * indicates a bond.
  • the total number of moles of groups represented by the following formula (a1-3) contained in the composition is C A1-3
  • the total number of moles of groups represented by the following formula (I) contained in the composition is The composition according to any one of [2] to [6], wherein the molar ratio (C A1-3 /C T ) is 0.005 to 0.34, where C T is the number of moles.
  • the total number of moles of groups represented by the following formula (a2-3) contained in the composition is C A2-3
  • the total number of moles of groups represented by the following formula (I) contained in the composition is The composition according to any one of [2] to [7], wherein the molar ratio (C A2-3 /C T ) is 0.001 to 0.234, where C T is the number of moles.
  • C A2-3 /C T is 0.001 to 0.234
  • C T is the number of moles.
  • R 1 has the same meaning as above, and * indicates a bond.
  • CD be the total number of moles of groups represented by the following formula (d) contained in the composition, and the total number of moles of groups represented by the following formula (a2-2) contained in the composition. is C A2-2 , and the total number of moles of groups represented by the following formula (a2-3) contained in the composition is C A2-3 , then the molar ratio (C A2-3 / (C A2-2 +C A2-3 +C D ) ⁇ 100) is 0.010 to 10.20, the composition according to any one of [2] to [8].
  • R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.
  • the total number of moles of groups represented by the following formula (f') contained in the composition is CF
  • the total number of moles of groups represented by the following formula (I) contained in the composition is The composition according to any one of [2] to [10], wherein the molar ratio (C F /C T ⁇ 100) is 1.70 to 45.0, where C T is 1.70 to 45.0.
  • a polyester polyol that is a reaction product of a polycarbonate polyol (B) and a polyester polyol (C), wherein the polyester polyol (C) is a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.
  • the polyol component contains a polycarbonate polyol represented by the following formula (A1-2) and a polyester polyol represented by the following formula (A1-3), and the polyol component contains the following formula:
  • the total number of moles of groups represented by (a1-1) is C A1-1
  • the total number of moles of groups represented by the following formula (a1-2) contained in the polyol component is C A1-2
  • If the total number of moles of groups represented by the following formula (a1-3) contained in the polyol component is C A1-3
  • the molar ratio (C A1-1 / (C A1-1 +C A1-2 +C A1- 3 )
  • the urethane resin according to [17], wherein ⁇ 100) is 5.3 to 99.
  • R 1 , R 2 and R 4 have the same meanings as above, and n 2 and m 2 each represent an integer of 0 or more.
  • a plurality of R 2 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • a plurality of R 3 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • the polyol component further contains a polycarbonate polyol represented by the following formula (A2-2) and a polyester polyol represented by the following formula (A2-3), and the following contained in the polyol component:
  • the total number of moles of groups represented by formula (a1-1) is C A1-1
  • the total number of moles of groups represented by formula (a1-2) below contained in the polyol component is C A1-2 .
  • the total number of moles of groups represented by the following formula (a1-3) contained in the polyol component is C A1-3
  • the total number of moles of groups represented by the following formula (a2-2) contained in the polyol component is If the number of moles is C A2-2 and the total number of moles of groups represented by the following formula (a2-3) contained in the polyol component is C A2-3 , then the molar ratio ((C A2-2 + C A2- 3 )/(C A1-1 +C A1-2 +C A1-3 )) is 0.01 to 0.750, the urethane resin according to [17] or [18].
  • R 1 , R 2 and R 4 have the same meanings as above, and n 4 represents an integer of 0 or more. When a plurality of R 4s exist, they may be the same or different from each other.
  • a plurality of R 4 's may be the same or different from each other.
  • R 4 has the same meaning as above, and n 6 represents an integer of 1 or more.
  • a plurality of R 4 's may be the same or different from each other.
  • the total number of moles of groups represented by the following formula (a1-1) contained in the polyol component is C A1-1
  • the total number of moles of groups represented by the following formula (I) contained in the polyol component is The urethane resin according to any one of [17] to [20], wherein the molar ratio (C A1-1 /C T ) is 0.02 to 0.99, where C T is the number of moles.
  • the total number of moles of groups represented by the following formula (a2-3) contained in the polyol component is C A2-3
  • the total number of moles of groups represented by the following formula (I) contained in the polyol component is The urethane resin according to any one of [17] to [23], wherein the molar ratio (C A2-3 /C T ) is 0.001 to 0.234, where C T is the number of moles.
  • C A2-3 /C T is 0.001 to 0.234
  • C T is the number of moles.
  • CD be the total number of moles of groups represented by the following formula (d) contained in the polyol component, and the total number of moles of groups represented by the following formula (a2-2) contained in the polyol component. is C A2-2 , and the total number of moles of groups represented by the following formula (a2-3) contained in the polyol component is C A2-3 , then the molar ratio (C A2-3 / (C A2-2 The urethane resin according to any one of [17] to [24], wherein +C A2-3 +C D ) ⁇ 100) is 0.010 to 10.20.
  • R is a hydrogen atom or an alkanediyl group, and * indicates a bond.
  • R may be the same or different.
  • [In formula (a2-2), R 1 has the same meaning as above, and * indicates a bond.
  • [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.
  • [26] The total number of moles of the group represented by the following formula (d) contained in the polyol component is CD , and the total number of moles of the group represented by the following formula (a2-2) contained in the polyol component is is C A2-2 , and if the total number of moles of groups represented by the following formula (a2-3) contained in the polyol component is C A2-3 , then the molar ratio ((C A2-2 + C A2-3 )/(C A2-2 +C A2-3 +C D ) ⁇ 100) is 0.100 to 12.00, the urethane resin according to any one of [17] to [25].
  • R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.
  • R 1 has the same meaning as above, and * indicates a bond.
  • [In formula (a2-3), R 1 has the same meaning as above, and * indicates a bond.
  • the total number of moles of groups represented by the following formula (f') contained in the polyol component is CF
  • the total number of moles of groups represented by the following formula (I) contained in the polyol component is The urethane resin according to any one of [17] to [26], where C T is a molar ratio (C F /C T ⁇ 100) of 1.70 to 45.0.
  • C T is a molar ratio (C F /C T ⁇ 100) of 1.70 to 45.0.
  • R 1 has the same meaning as above, and * indicates a bond.
  • [In formula (I), R 1 has the same meaning as above, and * indicates a bond.
  • the urethane resin according to any one of [17] to [28], wherein R 3 is an alkanediyl group, and R 4 is an alkanediyl group or *1-O-R c -*2.
  • the polyol component is a reaction product of a polycarbonate polyol (B) and a polyester polyol (C), and the polyester polyol (C) is a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.
  • polyester polyol ( ⁇ ') which is a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having 3 or more hydroxyl functional groups as an initiator, [17] ⁇
  • An aqueous urethane resin dispersion comprising an aqueous medium and the urethane resin or its neutralized product according to [30] dispersed in the aqueous medium.
  • the present invention it is possible to provide a novel compound useful as a raw material for urethane resins, a method for producing the same, and a urethane resin using the compound as a raw material. According to the present invention, it is also possible to provide a composition containing the compound and a urethane resin using the composition as a raw material. According to the present invention, it is also possible to provide an aqueous urethane resin dispersion containing the above-mentioned urethane resin having an acidic group.
  • FIG. 1 is a diagram showing a 1 H-NMR spectrum of a composition containing the polycarbonate polyol obtained in Example 5.
  • FIG. 2 is a 1 H-NMR spectrum of the composition containing the polycarbonate polyol obtained in Example 5, with the range from 3.300 ppm to 3.800 ppm being enlarged.
  • a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-” as the minimum value and maximum value, respectively.
  • the minimum or maximum value of a numerical range indicated using “ ⁇ ” can be arbitrarily combined with the maximum or minimum value of other numerical ranges indicated using " ⁇ ".
  • the upper limit values and lower limit values described individually can also be combined arbitrarily.
  • the compound of this embodiment is a compound represented by the following formula (A1-1) (hereinafter also referred to as "compound (A1-1)").
  • R 1 represents a hydrogen atom, an alkyl group or a hydroxyalkyl group
  • R 2 represents an alkanediyl group
  • R 3 represents an alkanediyl group
  • R 4 is an alkanediyl group
  • *1-R a -C( O)-O-R b -* 2
  • R a , R b , and R c each independently represent an alkanediyl group
  • *1 represents a bonding site with a carbonyl group
  • *2 represents a bonding site with an oxygen atom
  • n 1 and m 1 each represent an integer of 0 or more.
  • the alkyl group and hydroxyalkyl group represented by R 1 may be linear or branched.
  • the number of carbon atoms in the alkyl group and hydroxyalkyl group may be, for example, 1 to 6, 2 to 5, or 3 to 4.
  • Specific examples of alkyl groups and hydroxyalkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, hydroxymethyl group, hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, etc.
  • R 1 is preferably an alkyl group or a hydroxyalkyl group, more preferably an alkyl group or a hydroxyalkyl group having 1 to 2 carbon atoms.
  • the alkanediyl group represented by R 2 and R 3 may be linear or branched.
  • the alkanediyl group represented by R 2 and the alkanediyl group represented by R 3 may be the same or different.
  • the alkanediyl group represented by R 2 and R 3 may have, for example, 2 to 10 carbon atoms.
  • alkanediyl groups include ethanediyl group, 1,2-propanediyl group, 1,3-propanediyl group, 1,2-butanediyl group, 1,3-butanediyl group, 1,4-butanediyl group, 1 ,5-pentanediyl group, 2,2-dimethyl-1,3-propanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentanediyl group, 1,8-octanediyl group, 2-ethyl group -1,6-hexanediyl group, 1,9-nonanediyl group, 2-methyloctane-1,8-diyl group, 2-butyl-2-ethyl-1,3-propaned
  • the alkanediyl group represented by R 4 may be linear or branched. When two or more types of alkanediyl groups represented by R 4 are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, some of which are linear alkanediyl groups, and the other parts of which are linear alkanediyl groups. may be a branched alkanediyl group.
  • the number of carbon atoms in the alkanediyl group represented by R 4 is the same as the alkanediyl group mentioned in the explanation of R 2 and R 3 .
  • 1,4-butanediyl group, 1,5-pentanediyl group, 1,6-hexanediyl group, 3-methyl-1,5-pentanediyl group, 2-ethyl-1,6-hexanediyl group, 1, 9-nonanediyl group, 2-methyloctane-1,8-diyl group, etc. are preferred.
  • the alkanediyl groups represented by R a , R b , and R c may be the same as the alkanediyl groups described above.
  • the alkanediyl group represented by R a , R b , and R c may have, for example, 2 to 10 carbon atoms.
  • R a When two or more types of alkanediyl groups represented by R a are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, some of which are linear alkanediyl groups, and the other parts of which are linear alkanediyl groups. may be a branched alkanediyl group.
  • alkanediyl groups represented by R b When two or more types of alkanediyl groups represented by R b are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, some of which are linear alkanediyl groups, and the other parts are linear alkanediyl groups. may be a branched alkanediyl group.
  • R c When two or more types of alkanediyl groups represented by R c are present, all of them may be linear alkanediyl groups or branched alkanediyl groups, some of which are linear alkanediyl groups, and the other parts of which are linear alkanediyl groups. may be a branched alkanediyl group.
  • compound (A1-1) contains two or more types of alkanediyl groups as R 2 , R 3 , R 4 , R a , R b or R c , all of them are linear alkanediyl groups or branched alkanes. It may be a diyl group, with one part being a linear alkanediyl group and the other part being a branched alkanediyl group.
  • n 1 and m 1 may each be 0 to 65, 1 to 60, or 2 to 50.
  • the number average molecular weight of compound (A1-1) may be, for example, 200 to 6000 g/mol.
  • the number average molecular weight is a number average molecular weight in terms of a bifunctional polyoxypropylene polyol, which is measured using GPC (Gel Permeation Chromatography).
  • the hydroxyl value of compound (A1-1) may be, for example, 30 to 800 mgKOH/g.
  • the hydroxyl value means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of compound (A1-1), and is measured in accordance with JIS K1557-1.
  • the property of compound (A1-1) is not particularly limited, and may be solid at 25°C or liquid at 25°C.
  • the properties of compound (A1-1) are determined by the type of alkanediyl group (number of carbon atoms, presence or absence of branching) contained in compound (A1-1) as R 2 , R 3 , R 4 , R a , R b , or R c etc.), and can be further changed depending on the hydroxyl value of compound (A1-1).
  • the branched alkane in compound (A1-1) relative to the total number of moles of alkanediyl groups contained as R 2 , R 3 , R 4 , R a , R b or R c in compound (A1-1)
  • R 2 , R 3 , R 4 , R a , R b or R c in compound (A1-1) When the total number of moles of diyl groups is 0.2 to 1.0 and when the hydroxyl value of compound (A1-1) is high, compound (A1-1) tends to become liquid at 25°C.
  • R 3 contained in the compound (A1-1) is used from the viewpoint that when used as a raw material for a urethane resin, a urethane resin having excellent durability such as heat resistance, moist heat resistance/hot water resistance, etc. is likely to be formed.
  • R 4 is more preferably an alkanediyl group or *1-O-R c -*2.
  • compound (A1-1) contains R 2 , R 3 and R 4 from the viewpoint that a urethane resin having 100% modulus and excellent heat resistance is easily formed when used as a raw material for a urethane resin.
  • the ratio of the total number of moles of the alkanediyl group contained in R 4 and *1-O-R c -*2 contained as R 4 is 0.10 or more (for example, 0.10 to 0.90), It is more preferably 0.20 or more (for example, 0.20 to 0.80), even more preferably 0.30 or more (for example, 0.30 to 0.70), and even more preferably 0.40 or more (for example, 0. 40 to 0.60) is particularly preferred.
  • the compound (A1-1) explained above may be, for example, a reaction product of a polycarbonate polyol (B) and a polyester polyol (C).
  • Compound (A1-1) is a reaction product of polycarbonate polyol (B), polyester polyol (C), diol (D) and/or polyhydric alcohol (E) represented by the following formula (e). It may be a thing.
  • one of the oxy groups (-O-) in the group represented by the following formula (I) forms a carbonate bond derived from polycarbonate polyol (B), and one forms a carbonate bond derived from polyester polyol ( It is a molecule that forms an ester bond derived from C), one of which bonds with a hydrogen atom to form a hydroxyl group.
  • R 1 has the same meaning as above.
  • [In formula (I), R 1 has the same meaning as above. ]
  • the polycarbonate polyol (B) may be any polycarbonate polyol having a hydroxyl functional group of 2 or more, and may be a polycarbonate polyol (B-1) having a hydroxyl functional group of 2 (i.e., polycarbonate diol), with a hydroxyl functional group number of 2 or more. may be a polycarbonate polyol (B-2) having a polycarbonate polyol (B-2) of more than 2, or a combination of two or more selected from polycarbonate polyols (B-1) and polycarbonate polyols (B-2).
  • Examples of the polycarbonate polyol (B-1) include those obtained by reacting carbonates with diols.
  • Examples of carbonates that can be used in the reaction to obtain polycarbonate polyol (B-1) include dialkyl carbonates such as dimethyl carbonate and diethyl carbonate; alkylene carbonates such as ethylene carbonate and propylene carbonate; diphenyl carbonate and dinaphthyl. carbonate, diaryl carbonates such as dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate; and combinations of two or more of these.
  • Diols that can be used in the reaction to obtain polycarbonate polyol (B-1) include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, and 1,3-butanediol.
  • 1,4-butanediol 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 3,3- Dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis( ⁇ - hydroxyethyl)benzene, xylylene glycol, 1,8-octanediol, 2-ethyl-1,6-hexanediol, 1,9-nonanediol, 2-methyloctane-1,8-diol and 2-butyl-2 -ethyl-1,3-
  • polycarbonate polyol (B-2) examples include those obtained by reacting carbonates, diols, and polyhydric alcohols having 3 or more hydroxyl functional groups.
  • polycarbonate polyol (B-2) As carbonates that can be used in the reaction to obtain polycarbonate polyol (B-2), the same carbonates as mentioned in the explanation of polycarbonate polyol (B-1) can be mentioned. Among them, dimethyl carbonate, diethyl carbonate, and ethylene carbonate are preferred.
  • Diols that can be used in the reaction to obtain polycarbonate polyol (B-2) include the same diols as mentioned in the description of polycarbonate polyol (B-1). Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8- Octanediol is preferred.
  • Examples of the polyhydric alcohol having three or more hydroxyl functional groups that can be used in the reaction to obtain the polycarbonate polyol (B-2) include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, and any of these. Examples include combinations of two or more of the following.
  • the polyester polyol (C) may be any polyester polyol having a hydroxyl functional group of 2 or more, and may be a polyester polyol (C-1) having a hydroxyl functional group of 2 (i.e., polyester diol); may be a polyester polyol (C-2) having more than 2, or a combination of two or more selected from polyester polyols (C-1) and polyester polyols (C-2).
  • polyester polyol (C-1) examples include the following polyester polyols ( ⁇ ) to ( ⁇ ), and any combination of two or more thereof.
  • ( ⁇ ) Polyester polyol obtained from diol (C-1-1) and dicarboxylic acid and/or its anhydride (C-1-2) (polyester polyol ( ⁇ ))
  • ( ⁇ ) A polyester polyol obtained by ring-opening addition polymerization of a cyclic ester compound (C-1-4) such as a lactone using a diol (C-1-1) as an initiator (polyester polyol ( ⁇ ))
  • Polyester polyol ( ⁇ ) can be said to be a ring-opening addition polymer of a cyclic ester compound using a diol as an initiator.
  • diol (C-1-1) examples include the same diols mentioned in the explanation of the polycarbonate polyol (B-1). Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8- Octanediol is preferred.
  • dicarboxylic acid and/or its anhydride (C-1-2) examples include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, maleic acid, fumaric acid, and oxalic acid. , malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid, dodecanedioic acid, hydrogenated dimer fatty acid, etc., tartaric acid, anhydrides thereof, and combinations of two or more of these. can be mentioned.
  • Examples of the cyclic ester compound (C-1-4) include ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -valerolactone, ⁇ -caprolactone, ⁇ - Caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, ⁇ -methyl- ⁇ -caprolactone, 4-methylcaprolactone, ⁇ -caprylolactone, ⁇ -caprylolactone, ⁇ -palmi Tractone, etc., and combinations of two or more of these.
  • ring-opening addition polymers of ⁇ -caprolactone using trimethylolpropane as an initiator are preferred from the standpoint of stability and economy during polymerization.
  • polyester polyol (C-2) examples include the following polyester polyols ( ⁇ ') to ( ⁇ '), and any combination of two or more thereof.
  • Polyester polyol ( ⁇ ')) can be said to be a ring-opening addition polymer of a cyclic ester compound using a polyhydric alcohol having three or more hydroxyl functional groups as an initiator.
  • Examples of the diol (C-2-1) include the same diols mentioned in the explanation of the polycarbonate polyol (B-1).
  • dicarboxylic acid and/or its anhydride (C-2-2) the same ones mentioned in the explanation of the dicarboxylic acid and/or its anhydride (C-1-2) can be mentioned.
  • polyhydric alcohol (C-2-3) having 3 or more hydroxyl functional groups examples include trimethylolpropane, trimethylolethane, glycerin, pentaerythritol, sorbitol, etc., and combinations of any two or more of these. .
  • Examples of the cyclic ester compound (C-2-4) include those listed in the description of the cyclic ester compound (C-1-4).
  • polyester polyol (C) is used as polyester polyol ( ⁇ ) and/or It is more preferable that polyester polyol ( ⁇ ') is included.
  • diol (D) examples include the same diols mentioned in the explanation of the polycarbonate polyol (B-1). Among them, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8- Octanediol is preferred.
  • polyhydric alcohol (E) examples include trimethylolpropane, trimethylolethane, glycerin, and pentaerythritol. These may be used alone or in combination of two or more.
  • One of the hydroxy groups possessed by the above compound (A1-1) is, for example, represented by the following formula (e): [In formula (e), R 1 has the same meaning as above. ] It may be a hydroxy group derived from the compound represented by (the unreacted hydroxy group in the compound represented by formula (e) above). The hydroxy group tends to have lower reactivity than a hydroxy group bonded to a molecular chain containing R 2 , R 3 and/or R 4 due to the influence of steric hindrance.
  • the length from the hydroxyl group derived from the compound represented by the above formula (e) to the branch (bonding part with R 1 ) is the length from the hydroxyl group derived from the compound represented by the above formula (e) to the molecular chain containing R 2 , R 3 and/or R 4 .
  • the urethane resin obtained by the reaction of compound (A1-1) and an isocyanate compound tends to have higher rigidity because it is shorter than the length from the hydroxyl group to the branch.
  • Compound (A1-1) is expected to be used as a raw material for a variety of urethane resins by taking advantage of the reactivity and high rigidity of the hydroxyl group due to the difference in length up to branching of the hydroxyl group.
  • Carbonate bonds tend to contribute to improved heat resistance, and ester bonds tend to contribute to improved flexibility.
  • Compound (A1-1) is expected to be used as a variety of urethane raw materials by utilizing the above-mentioned carbonate bonds and ester bonds.
  • composition of this embodiment contains compound (A1-1).
  • the composition includes a polycarbonate polyol represented by the following formula (A1-2) (hereinafter referred to as “compound (A1-2)”) and a polyester polyol represented by the following formula (A1-3) (hereinafter referred to as “compound (A1-2)”). It may further contain at least one of compound (A1-3).
  • R 1 , R 2 and R 4 have the same meanings as above, and n 2 and m 2 each represent an integer of 0 or more.
  • a plurality of R 2 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • R 1 , R 3 and R 4 have the same meanings as above, and n 3 and m 3 each represent an integer of 0 or more.
  • a plurality of R 3 's may be the same or different from each other, and when a plurality of R 4 's exist, they may be the same or different from each other.
  • the atom or group contained as R 1 in compound (A1-2) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the atom or group contained as R 1 in compound (A1-3) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) in which the alkyl group and/or hydroxyalkyl group represented by R 1 are different, the composition contains the alkyl group and/or hydroxyalkyl group represented by R 1 It may contain two or more compounds (A1-2) having different groups, and/or two or more compounds (A1-3) having different alkyl groups and/or hydroxyalkyl groups represented by R 1 .
  • the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A1-2) and/or compound (A1-3) is the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A1-1). may be the same as the combination of groups included as .
  • the alkanediyl group contained as R 2 in compound (A1-2) may be the same as the alkanediyl group contained as R 2 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2
  • the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2 .
  • -2) may be included.
  • the combination of alkanediyl groups contained as R 2 in the plurality of compounds corresponding to compound (A1-2) is the combination of alkanediyl groups contained as R 2 in the plurality of compounds corresponding to compound (A1-1). It may be the same as the combination.
  • the group contained as R 3 in compound (A1-3) may be the same as the group contained as R 3 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) with different groups represented by R 3
  • the composition contains two or more compounds (A1-3) with different groups represented by R 3 . It may be included.
  • the combination of groups contained as R 3 in the plurality of compounds corresponding to compound (A1-3) is the same as the combination of groups contained as R 3 in the plurality of compounds corresponding to compound (A1-1). It's good.
  • the group contained as R 4 in compound (A1-2) may be the same as the group contained as R 4 in compound (A1-1).
  • the group contained as R 4 in compound (A1-3) may be the same as the group contained as R 4 in compound (A1-1).
  • compound (A1-1) contains two or more types of groups as R 4
  • compound (A1-2) and/or compound (A1-3) may contain two or more types of groups as R 4 .
  • the combination of groups contained as R 4 in compound (A1-2) and/or compound (A1-3) may be the same as the combination of groups contained as R 4 in compound (A1-1). .
  • n 2 , n 2 , m 3 and n 3 may each be 0-65, 1-60 or 2-50.
  • the total number of moles of the group represented by the following formula (a1-1) contained in the composition is referred to as C A1-1
  • the group represented by the following formula (a1-2) contained in the composition is The total number of moles of groups represented by the following formula ( a1-3 ) contained in the composition is defined as C A1-3 .
  • R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * is directly bonded to the carbon atom.
  • [In formula (a1-2), R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * is directly bonded to the carbon atom.
  • [In formula (a1-3), R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * is directly bonded to the carbon atom. ]
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is preferably 5.3 or more, more preferably 7.0 or more, and even more preferably 10 .0 or more, and even more preferably 20.0 or more.
  • a polyurethane resin particularly having excellent hot water resistance tends to be formed.
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is preferably 99 or less, more preferably 80 or less, even more preferably 70 or less, Particularly preferably, it is 60 or less.
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is 99 or less, a polyurethane resin with particularly excellent 100% modulus and heat resistance tends to be formed. be.
  • the molar ratio (C A1-1 /(C A1-1 +C A1-2 +C A1-3 ) ⁇ 100) may be from 5.3 to 99.
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is within the above range, when the composition is used as a raw material for urethane resin, 100% modulus, Polyurethane resins with good heat resistance and hot water resistance tend to be formed easily.
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is, for example, when deuterated chloroform is used as a solvent and tetramethylsilane is used as a reference substance. It can be determined from 1 H-NMR measurement of the composition and the integral value of the signal of the 1 H-NMR spectrum obtained by the measurement.
  • the integral value ⁇ S1-2 of the methylene signal (S1-2) located next to the hydroxyl group of the group represented by formula ( a1-2 ) (2 mol of hydrogen atoms) and the formula (a1-3) The molar ratio (C A1-1 / (C A1 -1 +C A1-2 +C A1-3 ) ⁇ 100) can be calculated.
  • the molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100) is the integral value ⁇ S1-1 of the signal (S1-1) and the signal (S1-2 ) of the integral value ⁇ S1-2 of the signal (S1-3), the sum of the integral value ⁇ S1-3 of the signal (S1-3), and the ratio of the integral value ⁇ S1-1 of the signal (S1-1) ( ⁇ S1-1 /( ⁇ S1-1 + ⁇ S1-2 + ⁇ S1-3 ) ⁇ 100).
  • the composition includes a polycarbonate polyol represented by the following formula (A2-2) (hereinafter referred to as "compound (A2-2)”) and a polyester polyol represented by the following formula (A2-3) (hereinafter referred to as “compound (A2-2)”). It may further contain at least one of compound (A2-3).
  • A2-2 polycarbonate polyol represented by the following formula (A2-2)
  • compound (A2-2) a polyester polyol represented by the following formula (A2-3)
  • It may further contain at least one of compound (A2-3).
  • R 1 , R 2 and R 4 have the same meanings as above, and n 4 represents an integer of 0 or more. When a plurality of R 4 's exist, they may be the same or different from each other.
  • [In formula (A2-3), R 1 , R 3 and R 4 have the same meanings as above, and n 5 represents an integer of 0 or more. When a plurality of R 4 's exist, they may be the same
  • the atom or group contained as R 1 in compound (A2-2) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the atom or group contained as R 1 in compound (A2-3) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) in which the alkyl group and/or hydroxyalkyl group represented by R 1 are different, the composition contains the alkyl group and/or hydroxyalkyl group represented by R 1 It may contain two or more compounds (A2-2) having different groups, and/or two or more compounds (A2-3) having different alkyl groups and/or hydroxyalkyl groups represented by R 1 .
  • the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A2-2) and/or compound (A2-3) is the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A1-1). may be the same as the combination of groups included as .
  • the alkanediyl group contained as R 2 in compound (A2-2) may be the same as the alkanediyl group contained as R 2 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2
  • the composition contains two or more compounds (A1-1) having different alkanediyl groups represented by R 2 .
  • -2) may be included.
  • the combination of alkanediyl groups contained as R 2 in the plurality of compounds corresponding to compound (A2-2) is the combination of alkanediyl groups contained as R 2 in the plurality of compounds corresponding to compound (A1-1). It may be the same as the combination.
  • the group contained as R 3 in compound (A2-3) may be the same as the group contained as R 3 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) with different groups represented by R 3
  • the composition contains two or more compounds (A2-2) with different groups represented by R 3 . It may be included.
  • the combination of groups contained as R 3 in the plurality of compounds corresponding to compound (A2-2) is the same as the combination of groups contained as R 3 in the plurality of compounds corresponding to compound (A1-1). It's good.
  • the group contained as R 4 in compound (A2-2) may be the same as the group contained as R 4 in compound (A1-1).
  • the group contained as R 4 in compound (A2-3) may be the same as the group contained as R 4 in compound (A1-1).
  • compound (A1-1) contains two or more types of groups as R 4
  • compound (A2-2) and/or compound (A2-3) may also contain two or more types of groups as R 4 .
  • the combination of groups included as R 4 in compound (A2-2) and/or compound (A2-3) may be the same as the combination of groups included as R 4 in compound (A1-1). .
  • n 4 and n 5 may each be 0-65, 1-60 or 2-50.
  • C A2-2 the total number of moles of groups represented by the following formula (a2-2) contained in the composition
  • C A2-2 the group represented by the following formula (a2-3) contained in the composition
  • C A2-2 Let the total number of moles of be C A2-3 .
  • R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * is directly bonded to the carbon atom.
  • R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * is directly bonded to the carbon atom.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) is 0.010 or more, 0.050 or more, 0.100 or more, 0.200 or more , or 0.300 or more.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) is 0.010 or more, especially 100% modulus, breaking strength, glass transition temperature and There is a tendency for polyurethane resins with excellent elongation to be formed.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) is 0.750 or less, 0.700 or less, 0.650 or less, or 0.600 It may be the following.
  • the polyurethane resin has particularly excellent hot water resistance and breaking strength. They tend to form easily.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) may be from 0.010 to 0.750.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) is, for example, the molar ratio (C A1-1 /(C A1-1 +C A1-2 + C A1-3 ) ⁇ 100), 1 H-NMR measurement of the composition using deuterated chloroform as a solvent and tetramethylsilane as a reference substance, and 1 H- obtained by the measurement It can be determined from the integral value of the signal of the NMR spectrum.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) can be calculated.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )) is the integral value ⁇ S1-1 of the signal (S1-1) and the signal
  • the composition may further contain a polyhydric alcohol represented by the following formula (e) (hereinafter also referred to as "polyhydric alcohol (E)").
  • a polyhydric alcohol represented by the following formula (e) hereinafter also referred to as "polyhydric alcohol (E)”
  • CE the total number of moles of the polyhydric alcohol represented by the following formula (e)
  • Se the signal of methylene located next to the hydroxyl group of the polyhydric alcohol represented by formula (e)
  • R 1 has the same meaning as above. ]
  • Polyhydric alcohol (E) has the same meaning as described above, and the alkyl group and hydroxyalkyl group that polyhydric alcohol (E) has as R 1 are the same as the atoms or groups contained as R 1 in compound (A1-1). It can be the same.
  • the atom or group contained as R 1 in the polyhydric alcohol (E) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) in which the alkyl group and/or hydroxyalkyl group represented by R 1 are different
  • the composition contains the alkyl group and/or hydroxyalkyl group represented by R 1 It may contain two or more types of polyhydric alcohols (E) having different groups.
  • the combination of groups contained as R 1 in the plurality of compounds corresponding to polyhydric alcohol (E) is the same as the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A1-1). It's good to be there.
  • composition may further contain an oxetane compound represented by the following formula (f) (hereinafter also referred to as “oxetane compound (F)").
  • oxetane compound (F) [In formula (f), R 1 has the same meaning as above. ]
  • the oxetane compound (F) has the same meaning as described above, and the alkyl group and hydroxyalkyl group that the oxetane compound (F) has as R 1 are the same as the atoms or groups contained as R 1 in compound (A1-1). It's good.
  • the atom or group contained as R 1 in the oxetane compound (F) may be the same as the atom or group contained as R 1 in the compound (A1-1).
  • the composition contains two or more compounds (A1-1) in which the alkyl group and/or hydroxyalkyl group represented by R 1 are different
  • the composition contains the alkyl group and/or hydroxyalkyl group represented by R 1 It may contain two or more types of oxetane compounds (F) having different groups.
  • the combination of groups contained as R 1 in the plurality of compounds corresponding to the oxetane compound (F) is the same as the combination of groups contained as R 1 in the plurality of compounds corresponding to the compound (A1-1). It's fine.
  • oxetane compound (F) examples include 3-ethyl-3-hydroxymethyloxetane, 3-methyl-3-hydroxymethyloxetane, and 3,3-dihydroxymethyloxetane. These may be used alone or in combination of two or more.
  • composition may further contain a polycarbonate polyol represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)").
  • A-3 a polycarbonate polyol represented by the following formula (A-3) (hereinafter referred to as "compound (A-3)").
  • R 1 and R 4 have the same meanings as above, and n 5 , m 5 and p 5 each represent an integer of 1 or more.
  • a plurality of R 4 's may be the same or different from each other.
  • the atom or group contained as R 1 in compound (A-3) may be the same as the atom or group contained as R 1 in compound (A1-1).
  • the composition contains two or more compounds (A1-1) in which the alkyl group and/or hydroxyalkyl group represented by R 1 are different
  • the composition contains the alkyl group and/or hydroxyalkyl group represented by R 1 It may contain two or more types of compounds (A-3) having different groups.
  • the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A-3) is the same as the combination of groups contained as R 1 in the plurality of compounds corresponding to compound (A1-1). It's good.
  • the group contained as R 4 in compound (A-3) may be the same as the group contained as R 4 in compound (A1-1).
  • compound (A-3) may also contain two or more types of groups as R 4 .
  • the combination of two or more groups contained as R 4 in compound (A-3) may be the same as the combination of two or more groups contained as R 4 in compound (A1-1).
  • n 5 , m 5 and p 5 may each be 1-65, 2-60 or 3-50.
  • composition may further contain a polycarbonate diol represented by the following formula (A-4) (hereinafter referred to as "compound (A-4)").
  • A-4 a polycarbonate diol represented by the following formula (A-4)
  • R 4 has the same meaning as above, and n 6 represents an integer of 1 or more.
  • a plurality of R 4 's may be the same or different from each other.
  • the group contained as R 4 in compound (A-4) may be the same as the group contained as R 4 in compound (A1-1).
  • compound (A-4) may also contain two or more types of groups as R 4 .
  • the combination of two or more groups contained as R 4 in compound (A-4) may be the same as the combination of two or more groups contained as R 4 in compound (A1-1).
  • n 6 may be 1-65, 2-60 or 3-50, respectively.
  • CT the total number of moles of groups represented by the following formula (I) contained in the composition.
  • R 1 has the same meaning as above, and * indicates a bond.
  • the bond represented by * in formula (I) is directly bonded to a carbon atom or a hydrogen atom.
  • the molar ratio (C A1-1 /C T ) may be 0.02 or more, 0.05 or more, or 0.1 or more. When the molar ratio (C A1-1 /C T ) is 0.02 or more, a polyurethane resin particularly having excellent hot water resistance tends to be formed. The molar ratio (C A1-1 /C T ) may be 0.990 or less, 0.800 or less, or 0.700 or less. When the molar ratio (C A1-1 /C T ) is 0.990 or less, a polyurethane resin having particularly excellent 100% modulus and heat resistance tends to be formed. The molar ratio (C A1-1 /C T ) may be from 0.02 to 0.99.
  • the molar ratio (C A1-2 /C T ) may be 0.001 or more, 0.010 or more, or 0.050 or more. When the molar ratio (C A1-2 /C T ) is 0.001 or more, a polyurethane resin particularly having excellent breaking strength and hot water resistance tends to be formed.
  • the molar ratio (C A1-2 /C T ) may be 0.990 or less, 0.400 or less, or 0.500 or less.
  • the molar ratio (C A1-2 /C T ) may be from 0.001 to 0.990.
  • the molar ratio (C A1-2 /C T ) is within the above range, when the composition is used as a raw material for a urethane resin, the polyurethane resin has good 100% modulus, heat resistance, breaking strength, and hot water resistance. tends to form.
  • the molar ratio (C A1-3 /C T ) is 0.005 or more, 0.010 or more, 0.050 or more, 0.100 or more, 0.150 or more, 0.200 or more, 0.250 or more, or 0 It may be .300 or more.
  • the molar ratio (C A1-3 /C T ) is 0.340 or less, 0.250 or less, 0.200 or less, 0.150 or less, 0.100 or less, 0.050 or less, or 0.020 or less. It's okay.
  • a polyurethane resin particularly having excellent hot water resistance tends to be formed.
  • the molar ratio (C A1-3 /C T ) may be between 0.005 and 0.340.
  • the molar ratio (C A2-3 /C T ) is 0.001 or more, 0.005 or more, 0.010 or more, 0.050 or more, 0.100 or more, 0.150 or more, 0.200 or more, or 0 It may be .220 or more.
  • a polyurethane resin particularly having excellent 100% modulus, breaking strength, glass transition temperature, and elongation rate tends to be formed.
  • the molar ratio (C A2-3 /C T ) may be 0.234 or less, 0.200 or less, 0.150 or less, 0.100 or less, 0.050 or less, or 0.015 or less.
  • the molar ratio (C A2-3 /C T ) is 0.234 or less, a polyurethane resin particularly having excellent hot water resistance and breaking strength tends to be formed.
  • the molar ratio (C A2-3 /C T ) may be from 0.001 to 0.234.
  • the molar ratio (C A2-3 /C T ) is within the above range, when the composition is used as a raw material for urethane resin, 100% modulus, heat resistance, hot water resistance, breaking strength, elongation rate, and glass transition There is a tendency for a polyurethane resin that is favorable at both temperatures to be easily formed.
  • the molar ratio (C A1-1 /C T ), the molar ratio (C A1-2 /C T ), the molar ratio (C A1-3 /C T ), and the molar ratio (C A2-3 /C T ) are all Within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin with better 100% modulus and heat resistance tends to be formed.
  • the molar ratio (C A1-1 /C T ), the molar ratio (C A1-2 /C T ), the molar ratio (C A1-3 /C T ), and the molar ratio (C A2-3 /C T ) are, for example, , (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100), the composition using deuterated chloroform as the solvent and tetramethylsilane as the reference substance. It can be determined from 1 H-NMR measurement of a substance and the integral value of the signal of the 1 H-NMR spectrum obtained by the measurement.
  • the integral value ⁇ S1-1 for 2 mol of hydrogen atoms of the above signal (S1-1)
  • the integral value ⁇ S1-2 for 2 mol of hydrogen atoms) of the above signal (S1-2)
  • the integral value ⁇ S1-3 for 2 mol of hydrogen atoms of the above signal (S1-3)
  • the integral value ⁇ S2-3 for 4 mol of hydrogen atoms of the above signal (S2-3)
  • R 1 is a linear alkyl group
  • the molar ratio ( C A1-1 /C T ), molar ratio (C A1-2 /C T ), molar ratio (C A1-3 /C T ) and molar ratio (C A2-3 /C T ) can be calculated.
  • the molar ratio (C A1-1 /C T ) is 1.5 times the ratio between the integral value ⁇ S1-1 of the signal (S1-1) and the integral value ⁇ SI of the signal (SI) (1 .5 ⁇ S1-1 / ⁇ SI ), the molar ratio (C A1-2 /C T ) is the difference between the integral value ⁇ S1-2 of the signal (S1-2) and the integral value ⁇ SI of the signal (SI).
  • the 1.5 times value of the ratio (1.5 ⁇ S1-2 / ⁇ SI ) and the molar ratio (C A1-3 /C T ) are the integral value ⁇ S1-3 of the signal (S1-3) and the signal ( SI) is 1.5 times the ratio of the integral value ⁇ SI (1.5 ⁇ S1-3 / ⁇ SI ), and the molar ratio (C A2-3 /C T ) is the signal (S2-3).
  • This can be expressed as 0.75 times the ratio between the integral value ⁇ S2-3 and the integral value ⁇ SI of the signal (SI) (0.75 ⁇ S2-3 / ⁇ SI ).
  • composition may further contain a diol (D).
  • Diol (D) has the same meaning as described above.
  • CD total number of moles of groups represented by the following formula (d) contained in the composition.
  • R is a hydrogen atom or an alkanediyl group, and * indicates a bond. R may be the same or different.
  • the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100) is 0.010 or more, 0.050 or more, 0.100 or more, 0.500 or more, 1.0 or more, It may be 3.0 or more, 5.0 or more, 7.0 or more, 8.5 or more, or 9.5 or more.
  • a polyurethane resin particularly having excellent heat resistance tends to be formed.
  • the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100) is 10.20 or less, 9.0 or less, 5.0 or less, 3.0 or less, 1.0 or less, It may be 0.900 or less, 0.600 or less, 0.300 or less, or 0.100 or less.
  • the molar ratio (C A2-3 /(C A2-2 +C A2-3 +C D ) ⁇ 100) may be from 0.010 to 10.20.
  • the molar ratio ((C A2-2 + C A2-3 )/(C A2-2 + C A2-3 + C D ) x 100) is 0.100 or more, 0.300 or more, 0.600 or more, 1.00 or more , 3.00 or more, 5.00 or more, 7.00 or more, or 9.00 or more.
  • the polyurethane resin has particularly excellent 100% modulus and heat resistance. tends to form.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A2-2 +C A2-3 +C D ) ⁇ 100) is 12.00 or less, 10.00 or less, 8.00 or less, 6.00 or less , 4.00 or less, 2.00 or less, or 1.000 or less.
  • the molar ratio ((C A2-2 +C A2-3 )/(C A2-2 +C A2-3 +C D ) ⁇ 100) may be from 0.100 to 12.00.
  • Molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100) and molar ratio ((C A2-2 + C A2-3 ) / (C A2-2 + C A2-3 + C D ) x100) is within the above range, when the composition is used as a raw material for a urethane resin, a polyurethane resin with better 100% modulus and heat resistance tends to be formed.
  • Molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100) and molar ratio ((C A2-2 + C A2-3 ) / (C A2-2 + C A2-3 + C D ) ⁇ 100) is, for example, similar to (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) ⁇ 100), when deuterated chloroform is used as the solvent and tetramethylsilane is used as the standard. It can be determined from the 1 H-NMR measurement of the composition used for the substance and the integral value of the signal of the 1 H-NMR spectrum obtained by the measurement.
  • the integral value ⁇ S2-2 for 4 mol of hydrogen atoms of the above signal (S2-2), the integral value ⁇ S2-3 (for 4 mol of hydrogen atoms) of the above signal (S2-3), , the integral value ⁇ Sd (2 mol of hydrogen atoms) of the methylene signal (Sd) located next to the hydroxyl group of the group represented by formula (d), and the molar ratio (C A2-3 / (C A2 -2 +C A2-3 +C D ) ⁇ 100) and the molar ratio ((C A2-2 +C A2-3 )/(C A2-2 +C A2-3 +C D ) ⁇ 100) can be calculated.
  • the molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100) is the integral value ⁇ S2-2 of the signal (S2-2) and the integral value ⁇ S2-2 of the signal (S2-3).
  • the molar ratio (C F /C T ⁇ 100) is 1.70 or more, 1.80 or more, 2.00 or more, 3.00 or more, 4.00 or more, 5.00 or more, 6.00 or more, 7. 00 or more, 8.00 or more, 9.00 or more, 10.00 or more, or 15.00 or more.
  • a polyurethane resin particularly excellent in heat resistance and 100% modulus tends to be easily formed due to self-crosslinking of the oxetane compound.
  • the molar ratio (C F /C T ⁇ 100) is 45.0 or less, 42.0 or less, 40.0 or less, 35.0 or less, 30.0 or less, 25.0 or less, 20.0 or less, 15. It may be 0 or less, or 10.0 or less.
  • the molar ratio (C F /C T ⁇ 100) is 1.70 to 45.0, 1.80 to 42.0, 2.00 to 40.0, 3.00 to 30.0, 4.00 to 20. 0, 5.00 to 15.0, or 6.00 to 10.0.
  • the molar ratio (C F /C T ⁇ 100) is, for example, similar to (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) ⁇ 100), when deuterated chloroform is used as a solvent. , and can be determined from 1 H-NMR measurement of the composition using tetramethylsilane as a reference substance and the integral value of the signal of the 1 H-NMR spectrum obtained by the measurement.
  • the molar ratio (C F /C T ⁇ 100) can be calculated from the ratio of ⁇ Sf (4 mol of hydrogen atoms). In this case, the molar ratio (C F /C T ⁇ 100) is 0.75 times the ratio of the integral value ⁇ SI of the signal (SI) and the integral value ⁇ Sf of the signal (Sf). ⁇ Sf / ⁇ SI ⁇ 100).
  • the composition is a reaction mixture of polycarbonate polyol (B), polyester polyol (C), and optionally added diol (D), polyhydric alcohol (E) and/or oxetane compound (F). It's fine. Since the above reaction is usually carried out in the presence of a transesterification catalyst, the composition may further contain a transesterification catalyst. As the transesterification catalyst, lithium acetylacetonate is preferably used. The content of the transesterification catalyst may be from 0.0001 to 0.100% by weight, based on the total weight of the composition.
  • the properties of the composition are not particularly limited, and may be solid at 25°C or liquid at 25°C.
  • the properties of the composition are determined by the components contained (for example, compounds (A1-1) to (A1-3), compounds (A2-2) to (A2-3), compound (A-3), compound (A- It can be changed depending on the type and content ratio of 4) and oxetane compound (F)).
  • the number average molecular weight of the composition may be, for example, 200 to 6000 g/mol.
  • the lower limit of the number average molecular weight of the composition is, for example, 200 g/mol or more, 400 g/mol or more, 600 g/mol or more, 800 g/mol or more, 1000 g/mol or more, 1200 g/mol or more, 1400 g/mol or more, 1600 g/mol or more, or It may be 1800 g/mol or more.
  • the upper limit of the number average molecular weight of the composition is, for example, 6000 g/mol or less, 5000 g/mol or less, 4000 g/mol or less, 3000 g/mol or less, 2500 g/mol or less, 2000 g/mol or less, 1800 g/mol or less, 1600 g/mol or less, It may be 1400 g/mol or less, 1200 g/mol or less, 1000 g/mol or less, or 800 g/mol or less.
  • the number average molecular weight of the composition is the number average molecular weight in terms of a bifunctional polyoxypropylene polyol, which is measured using GPC (Gel Permeation Chromatography) using the entire composition as a measurement target.
  • the hydroxyl value of the composition may be, for example, 30 to 800 mgKOH/g.
  • the lower limit of the hydroxyl value of the composition is, for example, 30 mgKOH/g or more, 40 mgKOH/g or more, 50 mgKOH/g or more, 60 mgKOH/g or more, 70 mgKOH/g or more, 80 mgKOH/g or more, 90 mgKOH/g or more, 100 mgKOH/g or more. , 120 mgKOH/g or more, 140 mgKOH/g or more, 160 mgKOH/g or more, or 180 mgKOH/g or more.
  • the upper limit of the hydroxyl value of the composition is, for example, 800 mgKOH/g or less, 700 mgKOH/g or less, 600 mgKOH/g or less, 500 mgKOH/g or less, 400 mgKOH/g or less, 300 mgKOH/g or less, 250 mgKOH/g or less, 200 mgKOH/g or less , 180 mgKOH/g or less, 160 mgKOH/g or less, 140 mgKOH/g or less, 120 mgKOH/g or less, 100 mgKOH/g or less, or 80 mgKOH/g or less.
  • the hydroxyl value of the composition refers to the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the composition, and is measured in accordance with JIS K1557-1.
  • the acid value of the composition may be, for example, 0.01 to 10.0 mgKOH/g.
  • the lower limit of the acid value of the composition is, for example, 0.01 mgKOH/g or more, 0.02 mgKOH/g or more, 0.03 mgKOH/g or more, 0.04 mgKOH/g or more, 0.05 mgKOH/g or more, 0.06 mgKOH/g. g or more, or 0.07 mgKOH/g or more.
  • the upper limit of the acid value of the composition is, for example, 10.0 mgKOH/g or less, 5.0 mgKOH/g or less, 3.0 mgKOH/g or less, 1.0 mgKOH/g or less, 0.5 mgKOH/g or less, 0.4 mgKOH/g. g or less, 0.3 mgKOH/g or less, or 0.2 mgKOH/g or less.
  • the acid value of the composition means the number of milligrams (mg) of potassium hydroxide equivalent to the hydroxyl group in 1 g of the composition, and is measured in accordance with JIS K1557-5.
  • the above signal (S1-1) is 1
  • the above signal (S1-2) is observed in the range of 3.475 ppm to 3.520 ppm of the H-NMR spectrum, and the above signal (S1-2) is observed in the range of 3.475 ppm to 3.520 ppm of the 1 H-NMR spectrum.
  • (S1-3) is observed in the range of 3.400 ppm to 3.435 ppm in the 1 H-NMR spectrum
  • the above signal (S2-2) is observed in the range of 3.595 ppm to 3.618 ppm in the 1 H-NMR spectrum.
  • the signal (S2-3) is observed in the range of 3.550 ppm to 3.595 ppm of the 1 H-NMR spectrum
  • the signal (Sd) is observed in the range of 3.550 ppm to 3.595 ppm of the 1 H-NMR spectrum. It was observed in the range of 618 ppm or more and 3.710 ppm or less, and in addition, the integral value ⁇ Se of the methylene signal (Se) located next to the hydroxy group of the polyhydric alcohol (E) was 3 in the 1 H-NMR spectrum.
  • the signal (Sf) is observed in the range of 4.390 ppm to 4.500 ppm in the 1 H-NMR spectrum.
  • R 1 in formula (I) is an ethyl group
  • the signal (SI) is observed in a range of 0.700 ppm to 1.000 ppm
  • R 1 in formula (I) is a methyl group
  • the above signal (SI) is observed in the range of 0.700 ppm or more and 1.130 ppm or less.
  • the compound (A1-1) of the above embodiment is prepared by, for example, reacting a polycarbonate polyol and a polyester polyol in a mixed solution containing a polycarbonate polyol (B), a polyester polyol (C), and a transesterification catalyst ( Compound (A1-1) can be obtained by a method including a reaction step of obtaining compound (A1-1) by conducting a transesterification reaction.
  • a reaction step of obtaining compound (A1-1) by conducting a transesterification reaction at least one of the polycarbonate polyol and the polyester polyol contains a group represented by the above formula (I), or the mixed solution further contains a polyhydric alcohol represented by the above formula (e).
  • the composition of the above embodiment can also be obtained as a reaction mixture containing compound (A1-1). Therefore, the above method can also be referred to as a method for producing the composition of the above embodiment.
  • the mixed solution may contain a diol (D) and/or an oxetane compound (F) as optional components. Even when the above method is a method in which at least one of the polycarbonate polyol (B) and the polyester polyol (C) contains a group represented by the above formula (I), the mixed solution may contain a polyhydric alcohol (E) as an optional component. may contain.
  • polycarbonate polyol (B), polyester polyol (C), diol (D), polyhydric alcohol (E), and oxetane compound (F) are as described above, and preferred examples thereof (preferred R 1 , R Examples of R 2 , R 3 , R 4 and R, and examples of preferred combinations) are also examples of preferred examples and preferred combinations of R 1 , R 2 , R 3 , R 4 and R possessed by compound (A1-1). is the same as As the transesterification catalyst, it is preferable to use lithium acetylacetonate from the viewpoint of making it easier to obtain the desired compound (A1-1).
  • the mixing ratio of polycarbonate polyol (B) and polyester polyol (C) is 95/ It is preferably from 5 to 5/95, more preferably from 90/10 to 10/90, even more preferably from 80/20 to 20/80, and even more preferably from 70/30 to 30/70. Particularly preferred.
  • compound (A-1) can be efficiently obtained.
  • polyester polyol ( ⁇ ) and/or polyester polyol ( ⁇ ') content of polycarbonate polyol (B) in mixed solution/polyester polyol ( ⁇ ) and/or in mixed solution
  • the content of polyester polyol ( ⁇ ') is preferably 95/5 to 5/95, more preferably 90/10 to 10/90, and 80/20 to 20/80 in terms of weight ratio. More preferably, the ratio is 70/30 to 30/70.
  • Compound (A-1) can be efficiently obtained by setting the mixing ratio of polycarbonate polyol (B) and polyester polyol ( ⁇ ) and/or polyester polyol ( ⁇ ') to the above range.
  • the content of the transesterification catalyst in the liquid mixture is determined based on 100 parts by mass of the total amount of polyol components in the liquid mixture, from the viewpoint of being able to easily control the reaction temperature appropriately and suppressing an increase in the color number of the reaction product. , 0.0001 to 0.1 parts by weight, 0.001 to 0.050 parts by weight, and 0.005 to 0.01 parts by weight.
  • the content of the transesterification catalyst is preferably as small as possible from the viewpoint of facilitating control of the reactivity of the urethanization reaction. When the content of the transesterification catalyst increases, the reactivity of the urethanization reaction tends to increase.
  • the content of the transesterification catalyst in the mixed liquid is preferably 0.001 parts by mass or more based on 100 parts by mass of the total amount of polyol components in the mixed liquid, from the viewpoint of facilitating the control of the urethanization reaction. , more preferably 0.002 parts by mass or more, and still more preferably 0.003 parts by mass or more.
  • the content of the transesterification catalyst in the mixed solution is 0.050 parts by mass or less based on 100 parts by mass of the total amount of polyol components in the mixed solution, from the viewpoint of suppressing an increase in the color number of the reaction product. It is preferably at most 0.040 parts by mass, even more preferably at most 0.030 parts by mass.
  • the content of the transesterification catalyst in the mixed solution is preferably 0.001 to 0.050 parts by mass, and 0.002 parts by mass, based on 100 parts by mass of the total amount of polyol components in the mixed solution. It is more preferably from 0.040 parts by mass, and even more preferably from 0.003 to 0.030 parts by mass.
  • the total amount of polyol components refers to compounds having two or more hydroxyl groups (for example, polycarbonate polyol (B), polyester polyol (C), polyhydric alcohol (E), and optionally added diol (D)) contained in the mixed liquid. ) and the optionally added oxetane compound (F).
  • the reaction may proceed by heating the liquid mixture, or the reaction may proceed without heating.
  • the reaction temperature of the mixed liquid is, for example, 0 to 250°C, and may be 100 to 220°C.
  • the reaction temperature is 0° C. or higher, the transesterification reaction easily proceeds and the desired compound (A1-1) is easily obtained.
  • the reaction temperature is 250° C. or lower, the number of colors of the resulting compound (A1-1) and composition (polyol-containing composition) can be suppressed. Furthermore, when the reaction temperature is 250° C.
  • an oxetane compound and/or oxetane structure derived from a trifunctional or higher-functional polyhydric alcohol is produced as a by-product due to the decarboxylation reaction of carbonate groups or the dehydration reaction between terminal hydroxyl groups. can be suppressed.
  • the transesterification reaction may be carried out while keeping the temperature constant, or may be carried out while increasing the temperature stepwise or continuously depending on the degree of reaction progress. From the viewpoint of making it easier to obtain the desired compound (A1-1), heating is performed at a temperature T1 that satisfies the relationship of the following formula ( ⁇ ), and then heating is performed at a temperature T2 that satisfies the relationship of the following formula ( ⁇ ). Preferably, heating is performed.
  • the temperature T1 and the temperature T2 satisfy the relationship of the following formula ( ⁇ ). Further, it is preferable that the average temperature T1 m of the first heating temperature and the average temperature T2 m of the second heating temperature satisfy the relationship of the following formula ( ⁇ ).
  • the degree of reaction progress can be estimated from the consumption amount of raw materials obtained from the GPC chart. 180°C ⁇ T1 ⁇ 200°C...( ⁇ ) 190°C ⁇ T2 ⁇ 200°C...( ⁇ ) T1 ⁇ T2...( ⁇ ) T1 m ⁇ T2 m ...( ⁇ )
  • Heating of the mixed liquid can be performed under normal pressure, but it can also be performed under reduced pressure (for example, under a pressure of 101 to 1 kPa). This makes it possible to remove water remaining in the liquid mixture, accelerate the progress of the reaction, and suppress coloring of the composition. Furthermore, under reduced pressure, it becomes possible to reduce the acid value of the composition.
  • normal pressure means a pressure of 101.325 kPa ⁇ 20.000 kPa. From the viewpoint of making it easier to obtain the desired compound (A1-1), the mixed solution is heated under a pressure of 101.325 kPa ⁇ 20.000 kPa (first heating) and then under a pressure of 20.000 kPa or less.
  • the temperature of the first heating is a temperature T1 that satisfies the relationship of formula ( ⁇ ) above
  • the temperature of the second heating is the temperature T1 that satisfies the relationship of formula ( ⁇ ) above. It is more preferable that the temperature T2 satisfies the relationship of formula ( ⁇ ), and the first heating temperature (temperature T1) and the second heating temperature (temperature T2) satisfy the relationship of formula ( ⁇ ) above. is even more preferable.
  • Heating of the mixed liquid can also be performed while flowing nitrogen. This makes it possible to remove water from the mixed liquid and accelerate the progress of the reaction. Furthermore, purging with nitrogen makes it possible to suppress coloring of the composition.
  • the nitrogen flow rate of the mixed solution is preferably 2 to 1000 ml/min/scale (kg), and 5 to 200 ml/min/scale (kg). It is even more preferable.
  • the obtained reaction mixture may be subjected to post-treatments such as distillation and drying.
  • post-treatments such as distillation and drying.
  • components such as the polyhydric alcohol (E) and/or the oxetane compound (F) may be added to prepare the compound. good.
  • the urethane resin is a polycondensate of a polyol component and a polyisocyanate component or a crosslinked product thereof.
  • crosslinked product means a product obtained by crosslinking polycondensates with each other using a chain extender or the like.
  • the polyol component contains the above compound (A1-1).
  • the polyol component may contain a polyol other than compound (A1-1) (a compound having two or more terminal hydroxyl groups) or an oxetane compound (F) (a compound having one hydroxyl group).
  • the polyol component is, for example, a polyol (compound (A1-2), compound (A1-3), compound (A2-2), compound (A2-3), compound (A-3), compound (A-4), polyhydric alcohol (E), diol (D), oxetane compound (F), etc.).
  • the content ratio of these polyols is determined by the content ratio of polyols in the above composition (for example, molar ratio (C A1-1 / (C A1-1 + C A1-2 + C A1-3 ) x 100), molar ratio ((C A2-2 +C A2-3 )/(C A1-1 +C A1-2 +C A1-3 )), molar ratio (C A1-1 /C T ), molar ratio (C A1-2 /C T ), mole Ratio (C A1-3 / C T ), molar ratio (C A2-3 / C T ), molar ratio (C A2-3 / (C A2-2 + C A2-3 + C D ) x 100), molar ratio ( (C A2-2 +C A2-3 )/(C A2-2 +C A2-3 +C D ) x 100) and the molar ratio (C F /C T x 100).
  • the polyol The component may include a polyol mixture from the composition described above,
  • the polyol component may further contain a polyol having an acidic group.
  • the urethane resin will contain acidic groups.
  • Urethane resins having acidic groups are suitably used in aqueous urethane resin dispersions. The aqueous urethane resin dispersion will be described later.
  • the acidic group is, for example, a functional group (hydrophilic group) that can impart hydrophilicity to an isocyanate group-terminated prepolymer obtained by reaction with an isocyanate.
  • a functional group hydrophilic group
  • polyols having such acidic groups include dimethylolalkanoic acids such as dimethylolpropionic acid (DMPA), dimethylolbutanoic acid (DMBA), dimethylolpentanoic acid, and dimethylolnonanoic acid.
  • Polyisocyanate component examples include aromatic polyisocyanates, araliphatic polyisocyanates, aliphatic polyisocyanates, and alicyclic polyisocyanates. Moreover, modified polyisocyanates which are modified products of these can also be used. Examples of the modified polyisocyanate include isocyanurate-modified polyisocyanate (isocyanate trimer), allophanate-modified polyisocyanate, uretdione-modified polyisocyanate, urethane-modified polyisocyanate, biuret-modified polyisocyanate, uretonimine-modified polyisocyanate, and acylurea-modified polyisocyanate. etc. These can be used alone or in combination of two or more.
  • aromatic isocyanates examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 4,4'-diphenylmethane diisocyanate, 2, 4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl -4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m
  • Examples of the araliphatic isocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, and mixtures thereof; 1,3-bis(1-isocyanato-1-methylethyl)benzene, 1,4- Examples include bis(1-isocyanato-1-methylethyl)benzene and mixtures thereof; ⁇ , ⁇ '-diisocyanato-1,4-diethylbenzene and the like.
  • aliphatic isocyanates examples include hexamethylene diisocyanate, pentamethylene diisocyanate, tetramethylene diisocyanate, 2-methylpentane-1,5-diisocyanate, 3-methylpentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, and ethylene.
  • alicyclic isocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexyl diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2'-dimethyldicyclohexylmethane diisocyanate, and bis(4-isocyanato).
  • the blending ratio of the polyol component and the polyisocyanate component is such that the molar ratio of active hydrogen in the polyol component to isocyanate groups in the polyisocyanate component is preferably 9:1 to 1:9, and 6:4 to 4. :6 is more preferable. When the blending ratio is within this range, the urethane resin tends to have better performance.
  • chain extender The chain extender can be appropriately selected depending on the purpose, use, etc.
  • chain extenders include water; ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,10-decane Diol, 1,1-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, tricyclodecanedimethanol, xylylene glycol, bis(p-hydroxy)diphenyl, bis(p-hydroxyphenyl)propane, 2,2-bis Low molecular weight polyols such as [4-(2-hydroxyethoxy)phenyl]propane, bis[4-(2-hydroxyethoxy)phenyl]sulfone, 1,1-bis[4-(2-hydroxyethoxy)phenyl]cyclohexane, etc.
  • Polymer polyols such as polyester polyol, polyester amide polyol, polyether polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol; ethylene diamine, isophorone diamine, 2-methyl-1,5-pentanediamine, aminoethyl ethanol Polyamines such as amines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine can be used.
  • the blending amount of the chain extender (the ratio of the structure derived from the chain extender contained in the urethane resin) may be 0.1 to 50 parts by mass based on 100 parts by mass of the total amount of the polyol component and the polyisocyanate component. .
  • the chain extender is a polyol, the content is calculated assuming that the polyol is included in both the chain extender and the polyol component.
  • the above urethane resin can be obtained by reacting a polyol component, a polyisocyanate component, and optionally a chain extender (urethanization reaction).
  • the urethanization reaction may be performed at room temperature (for example, 25°C) or under heating (for example, from 40 to 200°C).
  • a catalyst (urethanization catalyst) can be added for the purpose of shortening the reaction time, improving the reaction rate, etc.
  • catalysts include tertiary amine catalysts such as triethylamine, triethylenediamine, tetramethylethylenediamine, tetramethylpropylenediamine, and tetramethylhexamethylenediamine, and tin-based catalysts such as stannath octoate, stannath oleate, and dibutyltin dilaurate.
  • metal catalysts such as . These can be used alone or in combination of two or more. Among these, dibutyltin dilaurate is preferably used.
  • the amount of the catalyst used may be 0.001 to 100 parts by weight based on 100 parts by weight of the total amount of the polyol component and polyisocyanate component.
  • Phosphorus compounds are not particularly limited, but include, for example, phosphoric triesters such as trimethyl phosphate, triethyl phosphate, tributyl phosphate, di-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, and cresyl diphenyl phosphate; methyl acid phosphate , ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, lauryl acid phosphate, stearyl acid phosphate, 2-ethylhexyl acid phosphate, isodecyl acid phosphate, butoxyethyl acid phosphate, oleyl acid phosphate, tetracosyl Acid phosphate esters such as acid phosphate, ethylene glycol acid phosphate
  • the amount of the phosphorus compound used may be 10 to 2000 parts by mass based on 100 parts by mass of the catalyst.
  • the urethanization reaction can be performed in the presence of a solvent.
  • solvents include esters such as ethyl acetate, butyl acetate, propyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone; amides such as dimethylformamide, diethylformamide, and dimethylacetamide; and sulfoxides such as dimethylsulfoxide.
  • ethers such as tetrahydrofuran, dioxane and 2-ethoxyethanol; ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene and toluene.
  • the urethane resins described above have good elongation and texture, excellent durability, and, in some cases, good breaking strength. Therefore, the above urethane resin can be suitably used for synthetic leather, artificial leather, coating agents, etc.
  • the coating agent of this embodiment contains the urethane resin described above.
  • the specific embodiment of the urethane resin may be as described above.
  • An example of use as a coating agent is an in-mold coating method using RIM (Reaction Injection Molding). Specifically, this is a method in which a plastic base material is molded within an injection mold, and a urethane coating film is further formed on the surface of the molded product within the mold. With this method, the internal volume of the mold is constant, which not only stabilizes the density, thickness, and hardness of the urethane coating, but also faithfully reproduces the unevenness of the mold surface, making it possible to obtain a highly designed appearance. .
  • RIM Reaction Injection Molding
  • the aqueous urethane resin dispersion contains an aqueous medium and a urethane resin or its neutralized product dispersed in the aqueous medium.
  • the urethane resin is one having an acidic group (the polyol component contains a polyol having an acidic group) among the above-mentioned urethane resins.
  • aqueous medium in addition to water, solutions containing emulsifiers, dispersants, etc. can be used.
  • the aqueous medium preferably contains water, and more preferably consists only of water.
  • the acidic groups possessed by the urethane resin may be neutralized with a neutralizing agent.
  • the neutralizing agent include ammonia, ethylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, monoethanolamine, dimethylethanolamine, diethylethanolamine, and morpholine.
  • N-methylmorpholine N-methylmorpholine, 2-amino-2-ethyl-1-propanol, organic amines such as higher alkyl-modified morpholine, alkali metals such as lithium, potassium, and sodium, and inorganic alkalis such as sodium hydroxide and potassium hydroxide.
  • organic amines such as higher alkyl-modified morpholine
  • alkali metals such as lithium, potassium, and sodium
  • inorganic alkalis such as sodium hydroxide and potassium hydroxide.
  • Examples include. From the viewpoint of improving the durability, smoothness, etc. of the coating film, highly volatile neutralizing agents that are easily dissociated by heating, such as ammonia, trimethylamine, and triethylamine, are preferably used. These neutralizing agents can be used alone or in combination of two or more.
  • an anionic polar group-containing compound in producing the aqueous urethane resin dispersion, can also be used.
  • the anionic polar group-containing compound include compounds consisting of an organic acid having one or more active hydrogens and a neutralizing agent.
  • organic acids include carboxylates, sulfonates, phosphates, phosphonates, phosphinates, thiosulfonates, and the like. These anionic polar groups contained in the organic acid may be introduced alone or may be associated with metal ions like a chelate.
  • a cationic polar group-containing compound can also be used in producing the aqueous urethane resin dispersion.
  • the cationic polar group-containing compound is, for example, one selected from the group consisting of a tertiary amine having one or more active hydrogens, an inorganic acid neutralizer, an organic acid neutralizer, and a quaternizing agent. It consists of Further, as the cationic polar group-containing compound, cationic compounds such as primary amine salts, secondary amine salts, tertiary amine salts, pyridinium salts, etc. can also be used.
  • tertiary amines having one or more active hydrogens include N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dipropylethanolamine, N,N-diphenylethanolamine, N- Methyl-N-ethylethanolamine, N-methyl-N-phenylethanolamine, N,N-dimethylpropanolamine, N-methyl-N-ethylpropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-methyldiethanolamine Propanolamine, N-phenyldiethanolamine, N-phenyldipropanolamine, N-hydroxyethyl-N-hydroxypropyl-methylamine, N,N'-dihydroxyethylpiperazine, triethanolamine, trisisopropanolamine, N-methyl-bis -(3-aminopropyl)-amine, N-methyl-bis-(2-aminopropyl
  • inorganic acids and organic acids examples include hydrochloric acid, acetic acid, lactic acid, cyanoacetic acid, phosphoric acid, and sulfuric acid.
  • Examples of the quaternizing agent include dimethyl sulfate, benzyl chloride, bromoacetamide, and chloroacetamide. Further, alkyl halides such as ethyl bromide, propyl bromide, butyl bromide, etc. can also be used.
  • the aqueous urethane resin dispersion is produced by, for example, a step of reacting a polyol component containing a polyol having an acidic group and a polyisocyanate component in the presence of a solvent or in the absence of a solvent to obtain a urethane prepolymer. , a step of neutralizing the acidic groups in the prepolymer with a neutralizing agent, a step of dispersing the neutralized prepolymer in an aqueous medium, and a step of reacting the prepolymer dispersed in the aqueous medium with a chain extender. It can be manufactured by sequentially performing and. In addition, in each step, by using a catalyst as necessary, the reaction can be promoted and the amount of by-products can be controlled.
  • a film formed from the aqueous urethane resin dispersion described above (for example, a film formed by coating a base material with the aqueous urethane resin dispersion) has excellent adhesion, flexibility, feel, etc. Therefore, the aqueous urethane resin dispersion can be suitably used for artificial leather, synthetic leather, and coating agents.
  • the polyol component and polyisocyanate component for forming the urethane resin may be stored, transported, etc. in separate containers as a two-component composition set.
  • the two-part composition set includes a first part containing at least the polyol component and a second part containing at least the polyisocyanate component.
  • chain extender, catalyst, solvent, etc. these may be contained in the first liquid and/or the second liquid, or may be blended separately from the first liquid and the second liquid.
  • the above two-component composition set can be suitably used, for example, as a coating agent, and can also be suitably used in the production of artificial leather, synthetic leather, and the like.
  • the resulting mixed solution is applied onto the substrate and optionally heated.
  • a film for example, a cured film containing urethane resin
  • the two-component composition set when used as a coating agent, it can be suitably used in the production of artificial leather, synthetic leather, etc. as a resin composition that does not use organic solvents, and has excellent adhesion, flexibility, Forms a polyurethane resin with excellent texture.
  • the urethane resin-forming composition containing the above-mentioned polyol component and the above-mentioned polyisocyanate component, and the polyurethane resin composition containing the above-mentioned urethane resin may be an aqueous polyurethane resin emulsion, a polyurethane resin synthesized without a solvent, or a polyurethane resin synthesized without a solvent. Preferably used as a precursor. By curing this aqueous polyurethane resin emulsion or a polyurethane resin synthesized without a solvent, a coating film that is tough, has a 100% reduced modulus (good texture), and has a high softening temperature.
  • Molded objects such as films can be obtained, and can be suitably used for leather applications such as artificial leather and synthetic leather, and as a surface treatment agent for leather.
  • 100% modulus is one of the indicators to quantify the moist, elastic, and luxurious feeling when you touch synthetic leather, and if the value is within a certain numerical range, the urethane resin has good properties. becomes.
  • compositions, urethane resin, aqueous urethane resin dispersion, and coating agent of this embodiment described above can be used in a coating composition that is suitably used as a clear paint for automobile exteriors and a paint for automobile interiors. Furthermore, the composition, urethane resin, aqueous urethane resin dispersion, and coating agent of the present embodiment can be preferably used for home appliances, OA (office automation) products, surface treatment of leather, surface treatment of synthetic leather, and the like.
  • Example 1 Into a 0.5L four-necked glass reactor (reactor A) equipped with a stirrer, thermometer, heating device, and cooler, 322 g of N-980N, 140 g of Plaxel 220, 13 g of Plaxel 305, and 1,6-hexane were added. 24.6 g of diol (HG) and 0.05 g of lithium acetylacetonate were mixed. The mixture was heated at 180 to 200°C (initial 180°C, final 200°C) under normal pressure, and reacted for 5 hours at a flow rate of 50 ml/min under a nitrogen atmosphere.
  • reactor A Into a 0.5L four-necked glass reactor (reactor A) equipped with a stirrer, thermometer, heating device, and cooler, 322 g of N-980N, 140 g of Plaxel 220, 13 g of Plaxel 305, and 1,6-hexane were added. 24.6 g of diol (HG) and
  • Example 2 In reactor A, a mixed solution obtained by mixing 319 g of N-980N, 111 g of Plaxel 220, 51 g of Plaxel 305, 18.3 g of 1,6-hexanediol, and 0.05 g of lithium acetylacetonate was used. Except for this, a composition (PCP-2) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1.
  • Example 3 In reactor A, 153 g of polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 259 g of N-980N, 66 g of Plaxel 305, 21.8 g of trimethylolpropane (TMP), and 0 g of lithium acetylacetonate were added. A composition (PCP-3) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that the mixed solution obtained by mixing .05 g was used.
  • Example 4 In reactor A, 3.0 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 359 g of N-980N, 132 g of Plaxel 305, 5.6 g of trimethylolpropane, and 0.0 g of lithium acetylacetonate were placed in reactor A.
  • a composition (PCP-4) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that the mixed solution obtained by mixing 0.5 g was used.
  • Example 5 Except that a mixed solution obtained by mixing 300 g of polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 200 g of Plaxel 305, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-5) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 6 Except that a mixed solution obtained by mixing 212 g of N-980N, 149 g of Plaxel 220, 134 g of Plaxel 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-6) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 7 Except that a mixed solution obtained by mixing 112 g of N-980N, 249 g of Plaxel 220, 134 g of Plaxel 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-7) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 8 Except that a mixed solution obtained by mixing 12 g of N-980N, 349 g of Plaxel 220, 134 g of Plaxel 305, 5.3 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-8) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 9 In reactor A, 348 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 47 g of N-980N, 98 g of Plaxel 210, 6.9 g of Plaxel 305, and 0.05 g of lithium acetylacetonate were mixed. A composition (PCP-9) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that the mixed solution obtained in Example 1 was used.
  • Example 10 The above formula (A1 A composition (PCP-10) containing a polycarbonate polyol represented by -1) was obtained.
  • Reactor A was a 2L four-necked glass reactor equipped with a stirrer, a thermometer, a heating device, and a cooler, containing 1356 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 472 g of Plaxel 210, and 472 g of Plaxel 210.
  • a composition containing a polycarbonate polyol represented by the above formula (A1-1) was prepared in the same manner as in Example 1, except that a mixture obtained by mixing 171 g of 305 and 0.20 g of lithium acetylacetonate was used.
  • a product (PCP-12) was obtained.
  • Example 13 Except that a mixed solution obtained by mixing 250 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-13) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 14 The same procedure as in Example 1 was used, except that a mixed solution obtained by mixing 150 g of N-980N, 100 g of Plaxel 220, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in reactor A.
  • Example 15 The same procedure as in Example 1 was used, except that a mixed solution obtained by mixing 50 g of N-980N, 200 g of Plaxel 220, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in reactor A.
  • Example 16 The above formula (A1 A composition (PCP-16) containing a polycarbonate polyol represented by -1) was obtained.
  • Example 17 In reactor A, 90 g of the composition obtained in Example 13 (PCP-13) and 10 g of trimethylolpropane were mixed at 80°C, and a polycarbonate polyol represented by the above formula (A1-1) was prepared. A composition (PCP-17) containing the following was obtained.
  • Example 18 In reactor A, 305 g of polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 45 g of polycarbonate polyol (PC-2) obtained in Synthesis Example 2, 103 g of Plaxel 220, 47 g of Plaxel 210, and lithium. A composition containing a polycarbonate polyol represented by the above formula (A1-1) (PCP-18 ) was obtained.
  • Example 19 In reactor A, 289 g of the polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 126 g of the polycarbonate polyol (PC-2) obtained in Synthesis Example 2, 85 g of Plaxel 220, and 0% of lithium acetylacetonate were added.
  • a composition (PCP-19) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained in the same manner as in Example 1, except that the mixed solution obtained by mixing .05 g was used.
  • Example 20 Same as Example 1 except that a mixed solution obtained by mixing 318 g of N-980N, 150 g of N-135, 32 g of trimethylolpropane, and 0.05 g of lithium acetylacetonate was used in reactor A.
  • Example 21 Except that a mixed solution obtained by mixing 250 g of polycarbonate polyol (PC-3) obtained in Synthesis Example 3, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-21) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 22 Except that a mixed solution obtained by mixing 250 g of polycarbonate polyol (PC-4) obtained in Synthesis Example 4, 250 g of Plaxel 320, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-22) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Example 23 Except that a mixed solution obtained by mixing 250 g of N-980N, 250 g of Plaxel 320, 14.5 g of 3-ethyl-3hydroxymethyloxetane, and 0.05 g of lithium acetylacetonate was used in reactor A. In the same manner as in Example 1, a composition (PCP-23) containing a polycarbonate polyol represented by the above formula (A1-1) was obtained.
  • Comparative example 5 Comparative Example 4 except that a mixed solution obtained by mixing 300 g of polycarbonate polyol (PC-1) obtained in Synthesis Example 1, 200 g of Plaxel 305, and 0.05 g of barium acetate was used in reactor A.
  • a composition containing polycarbonate polyol (PCP-25) was obtained in the same manner as above.
  • Measuring device HLC-8420 (manufactured by Tosoh Corporation) (2) Column: TSKgel (manufactured by Tosoh Corporation) ⁇ G3000H-XL ⁇ G3000H-XL ⁇ G2000H-XL ⁇ G2000H-XL (3) Mobile phase: THF (tetrahydrofuran) (4) Detector: RI (refractive index) detector (HLC-8420 accessory) (5) Temperature: 40°C (6) Flow rate: 1.000ml/min (7) Calibration curve: A calibration curve was obtained using the following products (all bifunctional polyoxypropylene polyols manufactured by Sanyo Chemical Industries, Ltd.).
  • composition analysis Compositional analysis of the composition was performed using the following procedure.
  • the composition (sample) obtained above was dissolved in deuterated chloroform (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to obtain a solution.
  • Tetramethylsilane (TMS) was added to the solution as a chemical shift standard to obtain a test solution.
  • 1 H-NMR was measured for the obtained test solution using JNM-ECX400 manufactured by JEOL Ltd., and a 1 H-NMR spectrum was obtained with the TMS signal set at 0 ppm.
  • the 1 H-NMR spectrum of the composition obtained in Example 5 is shown in FIGS. 1 and 2. Note that the measurements were performed under the following conditions.
  • the integral value ⁇ S1-1 of the methylene signal (S1-1) located next to the hydroxyl group of the group represented by the above formula (a1-1) is determined. and the integral value ⁇ S1-2 of the methylene signal (S1-2) located next to the hydroxyl group of the group represented by the above formula (a1-2), and The integral value ⁇ S1-3 of the signal (S1-3) of methylene located next to the hydroxyl group of the group represented by the above formula (a2-2) and the methylene located next to the hydroxyl group of the group represented by the above formula (a2-2)
  • the integral value of the signal ( Se ) of methylene located next to ⁇ Sf was calculated. Further, when R 1 of the group represented by formula (I) is a methyl group or an ethyl group, the integral values of the signals of these terminal methyls were determined, and these were taken as the integral value ⁇ SI of the signal (SI).
  • a signal of 3.435 ppm to 3.475 ppm is defined as a signal (S1-1)
  • a signal of 3.475 ppm to 3.520 ppm is defined as a signal (S1-2)
  • a signal of 3.400 ppm to 3.435 ppm is defined as a signal (S1-2).
  • the following signal is defined as a signal (S1-3), the signal of 3.595 ppm or more and 3.618 ppm or less is defined as a signal (S2-2), the signal of 3.550 ppm or more and 3.595 ppm or less is defined as a signal (S2-3), A signal of 3.618 ppm or more and 3.710 ppm or less is a signal (Sd), a signal of 3.710 ppm or more and 3.760 ppm or less is a signal (Se), and a signal of 4.390 ppm or more and 4.500 ppm or less is a signal (Sf).
  • a signal of 0.700 ppm or more and 1.130 ppm or less is determined as a signal (SI ), and the signal of 0.700 ppm or more and 1.000 ppm or less is the signal when R 1 of the group represented by formula (I) is an ethyl group (when the polyhydric alcohol (E) is trimethylolpropane). (SI).
  • the baseline for integral value measurement was a straight line drawn horizontally based on the lowest spectral intensity after comparing the spectral intensities in a specified spectral range.
  • Signal (S1-1), Signal (S1-2), Signal (S2-2), and Signal (Se) usually show a single peak, but the peaks may be split due to the influence of trace amounts of water. . If they are detected as split peaks, they will deviate from the above integration range and accurate C A1-1 , C A1-2, C A2-2 , and C E cannot be obtained. Therefore, a case is adopted in which the integral value obtained from each signal shows a single peak.
  • C T is C A1-1 , C A1-2 , C A1- 3.
  • C A2-2 is the sum of C A2-2 , C A2-3 , C A3 , C E and C F.
  • PCP-1 19
  • composition (unit: g) of Examples 1 to 16, Examples 18 to 23, and Comparative Examples 4 to 5 indicates the reaction raw material, and "Composition” (unit: g) in Examples 1 to 3 indicates the blended components.
  • a cured urethane coating (film) was prepared by the following method, and the resulting film was used as a sample to evaluate its physical properties (tensile properties, heat resistance, hot water resistance).
  • Glass-transition temperature A test piece (width 0.4 cm, length 2.5 cm) was obtained from the obtained film using a dumbbell, and the thickness (approximately 100 to 200 ⁇ m) at the center of the marked line was measured.
  • the film may dissolve due to decomposition of carbonate bonds in polyurethane.
  • JP-508 Trade name, 2-ethylhexyl acid phosphate, manufactured by Johoku Chemical Industry Co., Ltd.
  • BYK-331 Silicone surface conditioner, manufactured by BYK Company ⁇ Methyl ethyl ketone: manufactured by Maruzen Petrochemical Co., Ltd. ⁇ Toluene : Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.

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US18/855,632 US20250304741A1 (en) 2022-04-15 2023-03-31 Compound, method for producing same, composition, urethane resin, aqueous urethane resin dispersion, and coating agent
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