WO2010140566A1 - Solution de polymère polyuréthane et son procédé de fabrication - Google Patents

Solution de polymère polyuréthane et son procédé de fabrication Download PDF

Info

Publication number
WO2010140566A1
WO2010140566A1 PCT/JP2010/059202 JP2010059202W WO2010140566A1 WO 2010140566 A1 WO2010140566 A1 WO 2010140566A1 JP 2010059202 W JP2010059202 W JP 2010059202W WO 2010140566 A1 WO2010140566 A1 WO 2010140566A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyurethane polymer
polymer solution
formula
repeating unit
polycarbonate polyol
Prior art date
Application number
PCT/JP2010/059202
Other languages
English (en)
Japanese (ja)
Inventor
昌彦 渡部
学 高橋
真弥 滝川
Original Assignee
宇部興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 宇部興産株式会社 filed Critical 宇部興産株式会社
Priority to JP2011518438A priority Critical patent/JP5751169B2/ja
Publication of WO2010140566A1 publication Critical patent/WO2010140566A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • the present invention relates to a polyurethane polymer solution and a method for producing the same.
  • the polycarbonate polyol is useful as a raw material for producing a polyurethane polymer by reacting with a polyisocyanate compound, as well as a polyester polyol and a polyether polyol, and a raw material for engineer plastics, adhesives, paints and the like.
  • the polyester polyol has an ester bond
  • the polyurethane polymer produced using the polyester polyol has a disadvantage that it is inferior in hydrolysis resistance.
  • a polyether polyol has an ether bond
  • a polyurethane polymer produced using the polyether polyol has a disadvantage that it is inferior in weather resistance and heat resistance.
  • the polycarbonate polyol having a repeating unit represented by — [O—R—O (CO)] — does not have the above-described drawbacks
  • the polyurethane polymer produced using this polycarbonate polyol has the advantage that it is excellent in hydrolysis resistance, weather resistance, heat resistance and the like and is easy to produce industrially.
  • Patent Document 1 discloses a polyurethane coating agent made from a polycarbonate polyol using an aliphatic polyol as a raw material, and the polyurethane resin used in this coating agent exhibits good adhesion to a plastic film, and after coating the film. It is described that it is excellent in blocking resistance after winding, wear resistance when used as a building material, solvent resistance, weather resistance and the like.
  • the present invention provides a polyurethane polymer solution excellent in dispersibility in an organic solvent, and having a coating film obtained by applying, drying, and baking as required, and a method for producing the same. Let it be an issue.
  • the present inventors have found that the above problem can be solved by using a polyurethane polymer obtained using a polycarbonate polyol containing a specific repeating unit. That is, the present invention provides the following [1] and [2].
  • [1] A polyurethane polymer obtained by reacting at least a repeating unit represented by the following formula (1) and having a hydroxyl group at both ends and a polyisocyanate compound (c) and an organic solvent: Containing polyurethane polymer solution.
  • Z 1 and Z 2 each independently represent a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
  • a polyurethane polymer is produced by reacting a polycarbonate polyol (a) containing at least a repeating unit represented by the formula (1) and having hydroxyl groups at both ends with a polyisocyanate compound (c) in an organic solvent.
  • the polyurethane polymer solution of the present invention is excellent in dispersibility in an organic solvent, and particularly excellent in the strength of a coating film obtained by coating and drying, and has hydrolysis resistance, durability, heat resistance, and abrasion resistance. It has sex. According to the production method of the present invention, a polyurethane polymer solution having the above characteristics can be produced efficiently.
  • the polyurethane polymer solution of the present invention is characterized by being synthesized from a polycarbonate polyol (a) containing at least a repeating unit represented by the above formula (1) as a raw material.
  • the polyurethane polymer solution of the present invention contains a polyurethane polymer comprising a polycarbonate polyol unit (a) and a polyisocyanate unit (c), and the polycarbonate polyol unit (a) is represented by at least the formula (1). Containing repeating units.
  • the polyurethane polymer is a polyurethane prepolymer obtained by reacting the polycarbonate polyol (a) containing the repeating unit represented by the above formula (1) with the polyisocyanate compound (c).
  • a polyurethane polymer obtained by reacting the agent (B) may also be used.
  • a polycarbonate polyol (a) having at least a repeating unit represented by the following formula (1) and having both ends being hydroxyl groups is used.
  • the polycarbonate polyol (a) (i) a polycarbonate polyol (a-1) having a repeating unit represented by the following formula (1) as a main component and both ends being hydroxyl groups, and (ii) the following formula (
  • Preferable examples include polycarbonate polyol (a-2) having a repeating unit represented by 1) and a repeating unit represented by the following formula (3) and having both ends being hydroxyl groups.
  • the polycarbonate polyol (a-1) and the polycarbonate polyol (a-2) are collectively referred to as “polycarbonate polyol (a)” or “component (a)”.
  • Z 1 and Z 2 each independently represent a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
  • Z 1 and Z 2 are each independently a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
  • R 3 represents a substituent.
  • the polycarbonate polyol (a) preferably has the following physical properties. Based on JIS K 1557, the Hazen unit color number (APHA) defined in JIS K 0071-1 is preferably 200 or less, more preferably 100 or less, still more preferably 70 or less, and particularly preferably 1 to 60.
  • the hydroxyl value is preferably 35 to 600 mgKOH / g, more preferably 50 to 400 mgKOH / g, still more preferably 100 to 150 mgKOH / g, and particularly preferably 110 to 130 mgKOH / g.
  • the acid value is preferably 1 mgKOH / g or less, more preferably 0.1 mgKOH / g or less, and still more preferably 0.01 to 0.05 mgKOH / g.
  • the melting point is preferably ⁇ 100 to + 250 ° C., more preferably ⁇ 80 to + 200 ° C., still more preferably ⁇ 20 to + 170 ° C., and particularly preferably 0 to 160 ° C.
  • the glass transition point is preferably ⁇ 80 to + 50 ° C., more preferably ⁇ 60 to + 20 ° C., and further preferably ⁇ 55 to ⁇ 20 ° C.
  • the viscosity is preferably 0.01 to 10 Pa ⁇ s (75 ° C.), more preferably 0.05 to 5 Pa ⁇ s (75 ° C.), and still more preferably 0.1 to 1.5 Pa ⁇ s (75 ° C.). .
  • the methods for measuring the Hazen unit color number (APHA), hydroxyl value, acid value, melting point, glass transition point, and viscosity are as described in the Examples.
  • the polycarbonate polyol (a-1) is a polyol having a repeating unit represented by the formula (1) and having hydroxyl groups at both ends.
  • Z 1 and Z 2 in formula (1) are divalent aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may have a substituent, but the substituent does not participate in the urethanization reaction.
  • a group is preferable, and the carbon chain may contain a hetero atom or an ester bond, and may contain an alicyclic structure, an ether bond, or the like.
  • divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, and a tetramethylene group.
  • a linear or branched alkanediyl group having 1 to 4 carbon atoms is preferable.
  • the bonding position of Z 1 and Z 2 with respect to the benzene ring is preferably 1,4-bond (para form) or 1,3-bond (meta form), and more preferably 1,4-bond (para form).
  • Particularly preferred polycarbonate polyol (a-1) is a polyol having a repeating unit represented by the following formula (2) and having both ends being hydroxyl groups.
  • the number, content, number average molecular weight and the like of the repeating unit represented by the formula (1) or (2) of the polycarbonate polyol (a-1) are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, and weather resistance. From the viewpoint of applicability in various fields, it is as follows.
  • the number of repeating units represented by the formula (1) or (2) is preferably 1 to 18, more preferably 2 to 13.
  • the content of the repeating unit represented by the formula (1) or (2) is preferably 80 to 100 mol%, more preferably 90 to 100 mol% in the polycarbonate polyol (a-1).
  • the number average molecular weight of the polycarbonate polyol (a-1) is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 400 to 1,000.
  • the measuring method of a number average molecular weight is as describing in an Example.
  • the polycarbonate polyol (a-1) can be produced by reacting an aromatic diol compound with carbonate ester, phosgene or the like by a known method such as a carbonate method or a phosgene method. Of these, the carbonate method is preferred.
  • a carbonate method the following manufacturing method A is mentioned preferably, for example.
  • an aromatic dihydroxyl compound (a-1-1) and a carbonate ester (a-1-2) are transesterified in the presence or absence of a catalyst.
  • polycarbonate polyol (a′-1) is obtained by reaction.
  • production method A a reaction example in which 1,4-benzenedimethanol is used as the aromatic dihydroxyl compound (a-1-1) is shown, but the same can be done when other aromatic dihydroxyl compounds are used. Can do.
  • R 1 and R 2 each independently represent a hydrocarbon group which may have a substituent.
  • the hydrocarbon group is preferably a hydrocarbon group having 1 to 6 carbon atoms.
  • n represents the number of repeating units, preferably 1 to 18, more preferably 2 to 13.
  • alcohols (R 1 OH, R 2 OH, etc.) derived from the carbonate ester (a-1-2) are by-produced during the transesterification reaction. It is preferable to proceed.
  • an alkylene carbonate such as ethylene carbonate can be used instead of the carbonate ester (a-1-2), but in this case, glycols derived from the alkylene carbonate are by-produced. It is preferable to proceed the reaction while extracting this by distillation or the like.
  • the details of the aromatic dihydroxyl compound (a-1-1), the carbonate ester (a-1-2), and the transesterification will be described later.
  • the polycarbonate polyol (a-2) is a polycarbonate polyol copolymer having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (3), and both terminals are hydroxyl groups.
  • a polycarbonate diol copolymer is preferred.
  • R 3 represents an optionally substituted divalent hydrocarbon group having 3 to 20 carbon atoms, and the substituent is preferably a group that does not participate in the urethanization reaction,
  • the carbon chain may contain a hetero atom or an ester bond, and may contain an alicyclic structure, an ether bond, or the like.
  • R 3 examples include trimethylene group, propane-1,2-diyl group, tetramethylene group, butane-1,3-diyl group, pentamethylene group, hexamethylene group, 3-methylpentane-1,5- Examples include diyl group, octamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group, hexadecamethylene group, octadecamethylene group, cyclohexane group, and 1,4-cyclohexanedimethano group. Of these, a linear or branched alkanediyl group having 3 to 14 carbon atoms, preferably 3 to 6 carbon atoms is preferable.
  • the molar ratio of [(repeating unit represented by formula (1)) / (repeating unit represented by formula (3))] is preferably 1/9 to 9/1. 1/5 to 5/1 is more preferable, and 1/3 to 3/1 is still more preferable.
  • the ratio of the repeating unit represented by the formula (1) is high, the viscosity of the polycarbonate polyol (a-2) increases, and therefore, the handling of the polycarbonate polyol (a-2) during the urethanization reaction tends to be difficult.
  • the ratio of the repeating unit represented by formula (1) is low, the hardness of the coating film obtained using the polyurethane polymer solution of the present invention tends to be low.
  • the number, content, number average molecular weight and the like of the repeating unit represented by the formulas (1) and (3) of the polycarbonate polyol (a-2) are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, and weather resistance. From the viewpoint of applicability in various fields, it is as follows.
  • the repeating unit represented by the formula (1) and the repeating unit represented by the formula (3) may be block copolymerized or randomly copolymerized.
  • the number of repeating units represented by the formula (1) is preferably 1 to 20, more preferably 2 to 15, and the content of the repeating units is preferably in the polycarbonate polyol (a-2). It is 10 to 90 mol%, more preferably 25 to 75 mol%.
  • the number of the repeating unit represented by the formula (3) is preferably 1 to 30, more preferably 2 to 20, and the content of the repeating unit is preferably in the polycarbonate polyol (a-2). It is 10 to 90 mol%, more preferably 25 to 75 mol%.
  • the number average molecular weight of the polycarbonate polyol (a-2) is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 900 to 1,500.
  • the measuring method of a number average molecular weight is as describing in an Example.
  • Examples of the method for producing the polycarbonate polyol (a-2) include a method of reacting an aromatic polyol compound, a dihydroxyl compound, carbonate ester, phosgene and the like by a known method such as a carbonate ester method and a phosgene method. Of these, the carbonate method is preferred.
  • the following manufacturing method B is mentioned preferably, for example.
  • an aromatic dihydroxyl compound (a-1-1), a carbonate (a-1-2), and a dihydroxyl compound (a-1-3) In this method, a polycarbonate polyol (a′-2) is obtained by an ester exchange reaction in the presence or absence of a catalyst.
  • reaction formula of the following production method B there is a structural unit derived from the aromatic dihydroxyl compound (a-1-1) at both ends as polycarbonate polyol (a′-2) in order to express the reaction formula simply. Only the case is described. However, the terminal is not limited to the structural unit derived from the aromatic dihydroxyl compound (a-1-1).
  • R 1 and R 2 each independently represent a hydrocarbon group which may have a substituent, and preferably has 1 to 6 carbon atoms.
  • R 3 represents a divalent hydrocarbon group having 3 to 20 carbon atoms which may have a substituent as described above.
  • p represents the number of repeating units, and is preferably 1 to 20, more preferably 2 to 15.
  • q represents the number of repeating units, and is preferably 1 to 30, more preferably 2 to 20.
  • alcohols (R 1 OH, R 2 OH, etc.) derived from the carbonate ester (a-1-2) are by-produced during the transesterification reaction. It is preferable to proceed.
  • an alkylene carbonate such as ethylene carbonate can be used instead of the carbonate ester (a-1-2).
  • glycols derived from the alkylene carbonate are by-produced. It is preferable to proceed the reaction while extracting this by distillation or the like.
  • Aromatic dihydroxyl compound (a-1-1) The aromatic dihydroxyl compound (a-1-1) that can be used in the production methods A and B is represented by the following formula (4).
  • aromatic dihydroxyl compounds (a-1-1) include 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,4-benzenedipropanol, 1,4-benzenedibutanol, , 3-benzenedimethanol, 1,3-benzenediethanol, 1,3-benzenedipropanol, 1,3-benzenedibutanol, 4- (4-hydroxymethylphenyl) butanol, 3- [4- (2-hydroxy And compounds having a linear or branched divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, such as ethyl) phenyl] propanol.
  • the carbonic acid ester (a-1-2) that can be used in the production methods A and B is not particularly limited, but it is desirable to appropriately select one that can efficiently extract by-product alcohols derived from the carbonic acid ester.
  • Examples thereof include dialkyl carbonate, diaryl carbonate, and alkylene carbonate.
  • the dialkyl carbonate is preferably a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include dimethyl carbonate and diethyl carbonate.
  • Examples of the diaryl carbonate include diphenyl carbonate.
  • the alkylene carbonate is preferably an alkylene carbonate having an alkanediyl group having 2 to 4 carbon atoms, and specific examples thereof include ethylene carbonate, propylene carbonate, butylene carbonate and the like. Among these, from the viewpoint of easy extraction of by-product alcohols, dialkyl carbonates having an alkyl group having 1 to 4 carbon atoms are preferred, dimethyl carbonate or diethyl carbonate is particularly preferred, and dimethyl carbonate is most preferred.
  • the dihydroxyl compound (a-1-3) that can be used in the production method B is not particularly limited.
  • an alkanediol having 3 to 20 carbon atoms when R 3 is a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms
  • a branched carbon chain of the alkylene group portion of the alkanediol examples include those in which the carbon chain of the alkylene group portion of the alkanediol contains an alicyclic structure or an ether bond.
  • alkanediol having 3 to 20 carbon atoms, preferably 3 to 14 carbon atoms examples include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7 -Pentanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol and the like.
  • Examples of the compound having a branched carbon chain of the alkylene group include 1,3-butanediol, 3-methylpentane-1,5-diol, 2-ethylhexane-1,6-diol, neopentyl glycol, 2 -Methyl-1,8-octanediol and the like.
  • Examples of the compound in which the carbon chain of the alkylene group part includes an alicyclic structure include 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2,2′-bis (4-hydroxycyclohexyl) propane, 1,4- And cyclohexanedimethanol.
  • Examples of the compound in which the carbon chain of the alkylene group part includes an ether bond include diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, and polytetramethylene glycol.
  • the dihydroxyl compound (a-1-3) may be carbon such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, etc.
  • Diols having an alicyclic structure having 5 to 8 carbon atoms such as alkanediol having 4 to 8 carbon atoms, particularly 4 to 6 carbon atoms, 1,4-cyclohexanedimethanol are more preferable.
  • Examples of the catalyst that can be used in the reaction in the production methods A and B include a catalyst (transesterification catalyst) used in a normal transesterification reaction.
  • a catalyst transesterification catalyst
  • alkali metal compounds include alkali metal hydroxides (lithium hydroxide, sodium hydroxide, potassium hydroxide, etc.), alkali metal carbonates (lithium carbonate, sodium carbonate, potassium carbonate, etc.), and alkali metal carboxylates.
  • Alkaline earth metal compounds include alkaline earth metal water. Examples thereof include oxides (magnesium hydroxide and the like), alkaline earth metal alkoxides (magnesium methoxide and the like), and the like.
  • Examples of the aluminum compound include aluminum alkoxide (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.), aluminum compounds such as aluminum acetylacetonate, and the like.
  • Examples of zinc compounds include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate.
  • Examples of manganese compounds include manganese carboxylates (such as manganese acetate) and manganese acetylacetonate.
  • Examples of nickel compounds include nickel carboxylates (such as nickel acetate) and nickel acetylacetonate.
  • Examples of antimony compounds include antimony carboxylates (such as antimony acetate) and antimony alkoxides.
  • zirconium compounds include zirconium alkoxides (zirconium propoxide, zirconium butoxide, etc.), zirconium acetylacetonate, and the like.
  • Titanium compounds include titanium alkoxide (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylate (tributoxy titanium stearate, isopropoxy systemate, etc.), titanium Chelates (diisopropoxytitanium bisacetylacetonate, dihydroxy bislactotitanium, etc.) and the like.
  • the organic tin compound include dibutyltin oxide, dibutyltin diacetate, and dibutyltin dilaurate.
  • Each carboxylate preferably has 2 to 30 carbon atoms, more preferably 2 to 18 carbon atoms, and each alkoxide preferably has 1 to 30 carbon atoms in the alkoxy group. 18 is more preferable.
  • a titanium compound and an organotin compound are preferable, a titanium compound is more preferable, and a titanium alkoxide is still more preferable.
  • titanium alkoxides titanium tetraethoxide, titanium tetrapropoxide, and titanium tetrabutoxide are more preferable, and titanium tetrabutoxide is particularly preferable.
  • the above aromatic dihydroxyl compound (a-1-1), carbonate ester (a-1-2), dihydroxyl compound (a-1-3), and catalyst may be used alone or in combination of two or more. Can be used in combination.
  • additives can be added to the polyurethane polymer solution of the present invention as necessary.
  • the additive include various resin components, resin particles, inorganic particles, fillers, pigments, dyes, light stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, and the like. be able to.
  • the reaction can be performed in an atmosphere of air, carbon dioxide gas, or an inert gas (nitrogen, argon, helium, or the like) or in an air stream, but is preferably performed in an inert gas atmosphere or an air stream.
  • the amount used in the case of using a catalyst is, in terms of reactivity, in the case of production method A, the aromatic dihydroxyl compound (a-1-1) and the carbonate ester (a-1-2) at the start of the reaction.
  • aromatic dihydroxyl compound (a-1-1), carbonic acid ester (a-1-2) and dihydroxyl compound (a-1-3) at the start of the reaction ) Based on the mass of the catalyst, preferably 1 to 20,000 ppm, more preferably 10 to 5,000 ppm, and even more preferably 100 to 4,000 ppm.
  • a high molecular weight polycarbonate polyol obtained by reacting a dihydroxyl compound (a-1-3) with a carbonate ester (a-1-2), and an aromatic dihydroxyl compound such as 1,4-benzenedimethanol
  • the polycarbonate polyol (a-2) can also be obtained by subjecting (a-1-1) to a transesterification reaction in the presence or absence of a catalyst.
  • a polycarbonate polyol having a high molecular weight obtained by reacting an aromatic dihydroxyl compound (a-1-1) such as 1,4-benzenedimethanol with a carbonate ester (a-1-2), and a dihydroxyl compound
  • a polycarbonate polyol (a-2) can also be obtained by subjecting (a-1-3) to a transesterification reaction in the presence or absence.
  • the average molecular weights of the polycarbonate polyols (a-1) and (a-2) used in the present invention are the aromatic dihydroxyl compound (a-1-1), carbonate (a-1-2), and dihydroxy used. It can be prepared by changing the reaction molar ratio of the compound (a-1-3).
  • the aromatic dihydroxyl compound (a-1-1) and dihydroxy compound (a-1-3) are distilled and the average molecular weight is larger than the target average molecular weight, aromatic dihydroxyl compound (a-1-1) and / or dihydroxyl
  • the compound (a-1-3) can be added and further subjected to a transesterification to obtain a polycarbonate polyol (a-1) or (a-2) having a target average molecular weight.
  • the constituent molar ratio of the repeating unit of the polycarbonate polyol (a-2) of the present invention is a change in the molar ratio of the aromatic dihydroxyl compound (a-1-1) and the dihydroxyl compound (a-1-3). Etc. can be prepared.
  • polyol (b) other than component (a) for example, a high molecular weight diol or a low molecular weight diol can be further used.
  • the high molecular weight diol that can be used is not particularly limited, and examples thereof include polycarbonate diol, polyester diol, polyether diol, acrylic diol, and polyether polyester polyol having an ether bond and an ester bond.
  • the polycarbonate diol include polytetramethylene carbonate diol and polyhexamethylene carbonate diol.
  • polyester diol examples include polyethylene adipate diol, polybutylene adipate diol, polyethylene butylene adipate diol, polyhexamethylene isophthalate adipate diol, polyethylene succinate diol, polybutylene succinate diol, polyethylene sebacate diol, polybutylene sebacate And diol, poly- ⁇ -caprolactone diol, poly (3-methyl-1,5-pentylene adipate) diol, polycondensate of 1,6-hexanediol and dimer acid, and the like.
  • polyether diol examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, ethylene oxide and propylene oxide, ethylene oxide and butylene oxide random copolymers, and block copolymers.
  • the low molecular weight diol that can be used is not particularly limited, and examples thereof include ethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,9 -Aliphatic diols having 2 to 9 carbon atoms such as nonanediol, 2-methyl-1,8-octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol; 1,4-cyclohexanedimethanol, 1,3-cyclohexanedi Methanol, 1,4-cyclohexanediol, 1,4-bis (hydroxyethy
  • the total number of hydroxyl equivalents of the polycarbonate polyol (a) and the polyol (b) is preferably 70 to 270. If the number of hydroxyl equivalents is less than 70, it may be difficult to produce a polyurethane polymer solution substantially. If it exceeds 270, the hardness of the coating film obtained by applying the obtained polyurethane polymer solution is low. It may become too much.
  • the number of hydroxyl equivalents is preferably 130 to 270, more preferably 160 to 265, and particularly preferably 180 to 260, from the viewpoint of the hardness of the coating film obtained by applying the polyurethane polymer solution obtained. The number of hydroxyl equivalents can be calculated by the following formula.
  • Number of hydroxyl equivalents of each polyol molecular weight of each polyol / number of OH groups of each polyol
  • Total number of hydroxyl equivalents M / total number of moles of polyol
  • M is the number of hydroxyl equivalents of [polycarbonate polyol (a). X number of moles of polycarbonate polyol (a)] + [number of hydroxyl equivalents of polyol (b) x number of moles of polyol (b))].
  • the polyisocyanate compound (c) used in the present invention is not particularly limited. Specific examples thereof include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2,6-tolylene diisocyanate, 4,4′-diphenylenemethane diisocyanate (MDI).
  • Aromatic polyisocyanate compounds such as natodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ′′ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate, p-isocyanatophenylsulfonyl isocyanate; ethylene diisocyanate , Tet Ramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecane methylene diisocyanate, 1,6,11-undecane triisocyanate, 2,2,4-trimethylhexamethylene diisocyanate,
  • the number of isocyanate groups per molecule of the polyisocyanate compound is usually 2, but a polyisocyanate compound having 3 or more isocyanate groups such as triphenylmethane triisocyanate is also within the range where the resulting polyurethane polymer does not gel. Can be used.
  • a polyisocyanate compound having 3 or more isocyanate groups such as triphenylmethane triisocyanate is also within the range where the resulting polyurethane polymer does not gel.
  • 4,4′-diphenylenemethane diisocyanate (MDI), isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate (hydrogenated) from the viewpoint of controlling reactivity and imparting elastic modulus. MDI) is preferred.
  • a polyisocyanate compound (c) can be used individually by 1 type or in combination of 2 or more types.
  • a chain extender (B) having reactivity with the isocyanate group of the polyurethane prepolymer (A) can be used.
  • chain extenders include ethylenediamine, 1,4-tetramethylenediamine, 2-methyl-1,5-pentanediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-hexamethylene.
  • Amine compounds such as diamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, 1,3-bis (aminomethyl) cyclohexane, xylylenediamine, piperazine, 2,5-dimethylpiperazine, diethylenetriamine, triethylenetetramine
  • Diol compounds such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, polyalkylene glycols typified by polyethylene glycol, water, etc., among which primary diamine compounds are preferred.
  • a chain extender (B) can be used individually by 1 type or in combination of 2 or more types. By using a chain extender, it becomes easy to improve the molecular weight of the polyurethane polymer, and the hardness of the coating film obtained using the polyurethane polymer solution tends to increase.
  • the polyurethane polymer used in the present invention can be obtained by any of the following methods.
  • Iv A method of reacting the polycarbonate polyol (a), the polyol (b), the polyisocyanate compound (c), and the chain extender (B).
  • the reaction temperature between the polyol component and the polyisocyanate compound (c) is preferably 40 to 150 ° C., more preferably 60 to 120 ° C.
  • the reaction temperature between the polyol (a) and the chain extender (B) is usually It is 0 to 80 ° C, preferably 0 to 60 ° C. Details of the reaction conditions and the like will be described in the section of [Method for producing polyurethane polymer solution] described later.
  • the organic solvent is not particularly limited as long as each component can be dissolved.
  • aliphatic hydrocarbons such as n-hexane, n-heptane and n-octane
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogenated hydrocarbons such as chloroform and carbon tetrachloride
  • dibutyl ether Ethers such as tetrahydrofuran and 1,4-dioxane
  • ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
  • esters such as ethyl acetate, n-propyl acetate and n-butyl acetate
  • amides such as N, N-dimethylacetamide And the like.
  • the blending method of each component, the luster pigment, the color pigment, the organic solvent, various additives, and the resin addition method are not particularly limited and can be performed by various methods, and the mixing order and the addition order are various. Can be done in order.
  • the proportion of the polyurethane polymer in the polyurethane polymer solution is preferably 5 to 60% by mass, more preferably 20 to 50% by mass.
  • Step (1) Polyurethane obtained by reacting a polycarbonate polyol (a) having at least a repeating unit represented by the following formula (1) and having both ends being hydroxyl groups and a polyisocyanate compound (c) in an organic solvent. Step of obtaining prepolymer (A)
  • Step (2) A step of obtaining a polyurethane polymer solution by reacting a polyurethane prepolymer (A) with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A) in an organic solvent.
  • the step (1) includes at least a repeating unit represented by the formula (1), a polycarbonate polyol (a) having both ends of a hydroxyl group, a polyisocyanate compound (c), and, if necessary, a polyol ( In this step, b) is reacted to obtain a polyurethane prepolymer (A).
  • Step (1) can be carried out in the presence or absence of a catalyst.
  • the catalyst examples include salts of metals and organic acids or inorganic acids such as tin catalysts (trimethyltin laurate, dibutyltin dilaurate, etc.) and lead catalysts (lead octylate, etc.), organometallic derivatives, amine catalysts (triethylamine). N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts and the like.
  • tin catalysts trimethyltin laurate, dibutyltin dilaurate, etc.
  • lead catalysts lead catalysts (lead octylate, etc.), organometallic derivatives, amine catalysts (triethylamine). N-ethylmorpholine, triethylenediamine, etc.), diazabicycloundecene catalysts and the like.
  • dibutyltin dilaurate is preferable from the viewpoint of reactivity.
  • Step (1) examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, N-ethylpyrrolidone, and ethyl acetate.
  • N-methylpyrrolidone and N-ethylpyrrolidone are preferable because they function as a film-forming aid when forming a coating film of the obtained polyurethane polymer solution.
  • Step (1) may be performed in an inert gas atmosphere or in an air atmosphere.
  • the reaction temperature is preferably 40 to 150 ° C, more preferably 60 to 120 ° C.
  • reaction temperature is less than 40 ° C., the raw material may not be dissolved, or the resulting urethane prepolymer (A) may have a high viscosity and cannot be sufficiently stirred. If the reaction temperature exceeds 150 ° C., side reactions may occur. May occur.
  • the ratio of each component in the step (1) is as follows when the total amount of the polycarbonate polyol (a) and the polyol (b) is 100 parts by mass.
  • the proportion of the polycarbonate polyol (a) is preferably 60 to 95 parts by mass, more preferably 65 to 90 parts by mass, and still more preferably 75 to 90 parts by mass. If this ratio is less than 60 parts by mass, the hardness of the coating film obtained by applying the resulting polyurethane polymer solution tends to be low, and if it exceeds 95 parts by mass, the coating film may become too hard.
  • the proportion of the polyol (b) is preferably 0 to 30 parts by mass, more preferably 0 to 10 parts by mass, and still more preferably 0 to 5 parts by mass.
  • the ratio of the number of moles of isocyanate groups in the polyisocyanate compound (c) to the number of moles of all hydroxyl groups in the polyol component comprising the polycarbonate polyol (a) and polyol (b) is preferably 0.8 to 2.0. If the number of moles of hydroxyl groups in the polyol component is too large, the molecular weight becomes too small, and the resulting coating film may not be sufficiently stretched. If the number of moles of hydroxyl groups in the polyol component is too small, a large amount of the unreacted polyisocyanate compound (c) remains in the reaction system and may react with the chain extender or react with water.
  • the coating film obtained by applying the polyurethane polymer solution of the present invention may be uneven.
  • the reaction between the polyol component consisting of the polycarbonate polyol (a) and the polyol (b) and the polyisocyanate compound (c) is performed in any order between the components (a) and (b) ( You may make it react with c) component and may make it react with (c) component, after mixing 2 or more types of components previously.
  • Examples of the organic solvent include those described above.
  • a method of adding a urethane prepolymer or a urethane prepolymer solution while stirring an organic solvent with a homomixer or a homogenizer and (ii) an organic solvent while stirring the urethane prepolymer with a homomixer or a homogenizer And the like.
  • Step (2) is a step of obtaining a polyurethane polymer solution by reacting a polyurethane prepolymer (A) in an organic solvent with a chain extender (B) having reactivity with an isocyanate group of the polyurethane prepolymer (A). It is.
  • the reaction temperature in step (2) is usually 0 to 80 ° C., preferably 0 to 60 ° C.
  • the reaction may be performed slowly under cooling, or in some cases, the reaction may be promoted under heating conditions of 60 ° C. or lower.
  • the addition amount of the chain extender (B) is preferably equal to or less than the equivalent of the isocyanate group that is the starting point of chain extension in the urethane prepolymer to be obtained, and is preferably 0.7 to 0.99 equivalent of the isocyanate group. More preferred.
  • the chain extender (B) is added in excess of the equivalent of isocyanate groups, the molecular weight of the chain-extended urethane polymer may decrease, and the coating film obtained by applying the obtained polyurethane polymer solution The strength may decrease.
  • the polyurethane polymer solution obtained by the production method of the present invention is particularly excellent in the strength of a coating film obtained by coating and drying, and has hydrolysis resistance, durability, heat resistance, and abrasion resistance. .
  • the polyurethane polymer solution of the present invention can be preferably applied to uses such as coating agents, paints, primers, urethane films, synthetic leather / artificial leather, glass fiber sizing agents and the like.
  • a color pigment or extender can be used.
  • the color pigment include organic pigments such as azo lake pigments, phthalocyanine pigments, indigo pigments, perinone pigments, perylene pigments, quinophthalone pigments, dioxazine pigments, quinacridone pigments, yellow lead, yellow iron oxide, Examples thereof include inorganic pigments such as bengara and titanium dioxide.
  • extender pigments include kaolin and talc.
  • a plasticizer examples include dibutyl phthalate and dioctyl phthalate.
  • the stabilizer examples include an antioxidant and an ultraviolet absorber.
  • the inorganic filler examples include calcium carbonate, titanium oxide, calcium oxide, calcium oxide, talc, clay, aluminum sulfate, vinyl chloride paste resin, and the like. These can be used singly or in combination of one or more, and those subjected to surface treatment can also be used as appropriate.
  • Measurement of Hazen unit color number (APHA): Based on JIS K 1557, the Hazen unit color number was measured in accordance with JIS K 0071-1 as follows. (Preparation of standard solution) A solution in which 1.245 g of potassium chloroplatinate, 1.000 g of cobalt chloride hexahydrate, 500 ml of water and 100 ml of hydrochloric acid are placed in a 1 L measuring flask and completely dissolved and then water is added up to the marked line is prepared. This solution is APHA standard solution no. No. 500 and various standard solutions are No. Prepare a 500 standard solution by diluting with water. For example, APHA standard solution No. 100 is No. 100.
  • the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof. Thereafter, the pressure was gradually reduced to 100 mmHg, and a transesterification reaction was further carried out at 195 ° C. for 4 hours while distilling off a mixture of methanol and dimethyl carbonate with stirring. After completion of the reaction (after completion of distillation of methanol and dimethyl carbonate), the reaction solution was cooled to room temperature to obtain 280 g of polycarbonate diol (A).
  • the obtained polycarbonate diol (A) has a number average molecular weight of 950, a hydroxyl value of 118 mgKOH / g, an acid value of 0.02 mgKOH / g, a water content of 32 ppm, a melting point of 33 ° C., and a glass transition point of ⁇ 50.9 ° C.
  • the viscosity was 0.6 Pa ⁇ s (75 ° C.) and the Hazen unit color number was 40.
  • Production Example 2 [Production of polycarbonate diol (B)] 170.2 g (1.89 mol) of dimethyl carbonate, 109.9 g (0.80 mol) of 1,4-benzenedimethanol, 94.0 g (0.80 mol) of 1,6-hexanediol, and 0.02 g of titanium tetrabutoxide Except that it was charged, 230 g of polycarbonate diol copolymer was obtained in the same manner as in Production Example 1.
  • polycarbonate diol (B) To the obtained polycarbonate diol copolymer, 2.78 g (0.021 mol) of 1,4-benzenedimethanol and 2.38 g (0.020 mol) of 1,6-hexanediol were further added, and 200 mmHg, 180 ° C. The ester exchange reaction was carried out to obtain 235 g of polycarbonate diol (B).
  • the obtained polycarbonate diol (B) has a number average molecular weight of 999, a hydroxyl value of 112 mgKOH / g, an acid value of 0.02 mgKOH / g, a water content of 26 ppm, a melting point of 120 ° C., and a glass transition point of ⁇ 38.3 ° C.
  • the Hazen unit color number was 50.
  • Example 1 (1) Production of polyurethane polymer solution (I) Into a glass separable flask having an internal volume of 300 ml equipped with a stirrer and a thermometer, 30.46 g of polycarbonate diol (A) obtained in Production Example 1 and 1,4- 5.55 g of butanediol and 235.23 g of dimethylacetamide were added, and the mixture was stirred at a bath temperature of 85 ° C. (internal temperature: 75 to 85 ° C.). After 30 minutes, 24.03 g of 4,4′-diphenylmethane diisocyanate was added and stirred at the same temperature.
  • Example 2 A polyurethane polymer solution (II) was produced in the same manner as in Example 1 except that the polycarbonate diol (A) was changed to the polycarbonate diol (B). Further, in the same manner as in Example 1, a polyurethane film (II) was produced from the polyurethane polymer solution (II). The hardness of the obtained polyurethane film (II) was 317 seconds in terms of amplitude decay time.
  • Comparative Example 1 (1) Production of polyurethane polymer solution (III) A 1-liter glass separable flask equipped with a stirrer and a thermometer was placed in an ETERNACOLL (registered trademark) “UH-100” (1, 6) manufactured by Ube Industries, Ltd. -Polycarbonate diol produced using hexanediol and carbonate ester as raw materials, molar mass: 1000 g / mol, hydroxyl value: 112.2 mg KOH / g) 30.30 g, 1,4-butanediol 5.50 g, dimethylacetamide 235.30 g And stirred at a bath temperature of 85 ° C. (inner temperature 75 ° C. to 85 ° C.).
  • the polyurethane polymer solution of the present invention is excellent in the strength of a coating film obtained by coating and drying. In addition, it has hydrolysis resistance, durability, heat resistance, and abrasion resistance, and is particularly excellent in hardness, so that it is useful as a raw material for coating agents, paint compositions and the like. Moreover, according to the manufacturing method of this invention, the polyurethane polymer solution which has the said characteristic can be manufactured efficiently.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention a pour objet une solution de polymère polyuréthane contenant un polymère polyuréthane et un solvant organique, et son procédé de fabrication. Le polymère polyuréthane est obtenu par la réaction d'au moins un composé polyisocyanate (c) et d'un polyol de polycarbonate (a) qui contient un motif de répétition représenté par la formule générale (1) et possède des groupes hydroxyle aux deux extrémités. (Dans la formule, Z1 et Z2 représentent indépendamment un groupe hydrocarbure aliphatique bivalent facultativement substitué ayant de 1 à 10 atomes de carbone.)
PCT/JP2010/059202 2009-06-02 2010-05-31 Solution de polymère polyuréthane et son procédé de fabrication WO2010140566A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011518438A JP5751169B2 (ja) 2009-06-02 2010-05-31 ポリウレタンポリマー溶液及びその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2009-132975 2009-06-02
JP2009132975 2009-06-02

Publications (1)

Publication Number Publication Date
WO2010140566A1 true WO2010140566A1 (fr) 2010-12-09

Family

ID=43297700

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2010/059202 WO2010140566A1 (fr) 2009-06-02 2010-05-31 Solution de polymère polyuréthane et son procédé de fabrication

Country Status (2)

Country Link
JP (1) JP5751169B2 (fr)
WO (1) WO2010140566A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011157487A (ja) * 2010-02-01 2011-08-18 Ube Industries Ltd ポリウレタン樹脂、及びポリウレタン樹脂組成物
WO2012121311A1 (fr) * 2011-03-08 2012-09-13 宇部興産株式会社 Composé de polyuréthane, composition le contenant, composition aqueuse de dispersion de polyuréthane et substances résultant de son durcissement
WO2022191102A1 (fr) * 2021-03-08 2022-09-15 旭化成株式会社 Composition durcissable et cuir synthétique
JP7555473B2 (ja) 2021-03-08 2024-09-24 旭化成株式会社 硬化性組成物及び合成皮革

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547889A (en) * 1967-03-17 1970-12-15 Huels Chemische Werke Ag Coatings based on polycarbonates condensed with trifunctional isocyanates
JPH02251523A (ja) * 1989-03-27 1990-10-09 Mitsui Petrochem Ind Ltd 芳香族ポリカーボネートジオールの製造方法
DE4100589A1 (de) * 1991-01-11 1992-07-16 Bayer Ag Konzentrate von zusatzstoffen auf basis polymerer bindemittel und ihre verwendung
JPH11322887A (ja) * 1998-04-15 1999-11-26 Basf Ag 熱可塑性ポリウレタンの製造方法
WO2010013579A1 (fr) * 2008-08-01 2010-02-04 宇部興産株式会社 Polycarbonate diol et copolymère de polycarbonate diol
WO2010090186A1 (fr) * 2009-02-06 2010-08-12 宇部興産株式会社 Dispersion aqueuse de résine de polyuréthane, et procédé de fabrication correspondant

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH024736A (ja) * 1988-06-22 1990-01-09 Hitachi Maxell Ltd ポリカーボネートポリオール、芳香族ポリカーボネートポリウレタン樹脂、コーティング材、キャストフィルム、磁気記録媒体
JPH0289214A (ja) * 1988-09-26 1990-03-29 Hitachi Maxell Ltd 磁気記録媒体
SE528577C2 (sv) * 2005-03-23 2006-12-19 Perstorp Specialty Chem Ab Vattenburen polyuretandispersion samt användning därav

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3547889A (en) * 1967-03-17 1970-12-15 Huels Chemische Werke Ag Coatings based on polycarbonates condensed with trifunctional isocyanates
JPH02251523A (ja) * 1989-03-27 1990-10-09 Mitsui Petrochem Ind Ltd 芳香族ポリカーボネートジオールの製造方法
DE4100589A1 (de) * 1991-01-11 1992-07-16 Bayer Ag Konzentrate von zusatzstoffen auf basis polymerer bindemittel und ihre verwendung
JPH11322887A (ja) * 1998-04-15 1999-11-26 Basf Ag 熱可塑性ポリウレタンの製造方法
WO2010013579A1 (fr) * 2008-08-01 2010-02-04 宇部興産株式会社 Polycarbonate diol et copolymère de polycarbonate diol
WO2010090186A1 (fr) * 2009-02-06 2010-08-12 宇部興産株式会社 Dispersion aqueuse de résine de polyuréthane, et procédé de fabrication correspondant

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011157487A (ja) * 2010-02-01 2011-08-18 Ube Industries Ltd ポリウレタン樹脂、及びポリウレタン樹脂組成物
WO2012121311A1 (fr) * 2011-03-08 2012-09-13 宇部興産株式会社 Composé de polyuréthane, composition le contenant, composition aqueuse de dispersion de polyuréthane et substances résultant de son durcissement
JPWO2012121311A1 (ja) * 2011-03-08 2014-07-17 宇部興産株式会社 ポリウレタン化合物、それを含む組成物、水性ポリウレタン分散体組成物及びこれらの硬化物
WO2022191102A1 (fr) * 2021-03-08 2022-09-15 旭化成株式会社 Composition durcissable et cuir synthétique
JP7555473B2 (ja) 2021-03-08 2024-09-24 旭化成株式会社 硬化性組成物及び合成皮革

Also Published As

Publication number Publication date
JP5751169B2 (ja) 2015-07-22
JPWO2010140566A1 (ja) 2012-11-22

Similar Documents

Publication Publication Date Title
JP5668478B2 (ja) ポリウレタン樹脂水系分散体及びその製造方法
TWI443125B (zh) Polycarbonate diol
JP5720246B2 (ja) 水性ポリウレタン樹脂分散体、その製造方法、及びそれを含有する塗料組成物
JP5553020B2 (ja) 水性ポリウレタン樹脂分散体及びその製造方法
JP6252070B2 (ja) ポリカーボネートジオール
JP6078988B2 (ja) ポリカーボネートポリオールの製造方法
CN110041484B (zh) 高支化聚碳酸酯多元醇组合物
CN108409955A (zh) 汽车部件和汽车
JP6578636B2 (ja) 水性ポリウレタン樹脂エマルジョン組成物、該組成物を用いた合成皮革、人工皮革用表面処理剤
JPWO2012121311A1 (ja) ポリウレタン化合物、それを含む組成物、水性ポリウレタン分散体組成物及びこれらの硬化物
JP2013209492A (ja) ポリカーボネートジオール
JP2020512430A (ja) 低いブルーミング効果、及び良好な低温フレキシビリティーを示すポリウレタンを、ウレタン含有ポリマー性ヒドロキシル化合物に基づいて製造する方法。
WO2016125893A1 (fr) Composition de résine uréthanne pour revêtement et revêtement texturé l'utilisant
JP5751169B2 (ja) ポリウレタンポリマー溶液及びその製造方法
JP2020084163A (ja) ポリカーボネートポリオール及びポリウレタン樹脂形成用組成物
JP4969175B2 (ja) コーティング剤組成物
JP2009235291A (ja) ポリカ−ボネートポリオール及びその製造方法
JP2014198808A (ja) ポリカーボネートジオール
JP2013166852A (ja) ポリカーボネートジオール
WO2021075503A1 (fr) Composition de polycarbonate diol
JP2019044003A (ja) 二液硬化型ウレタン樹脂組成物及びフィルム成形品
JP2011126945A (ja) 水性ポリウレタン樹脂組成物並びにそれを用いた水性塗料組成物
JP2019019211A (ja) ポリウレタン、及びその硬化物
WO2022158606A1 (fr) Polycarbonate polyol, son procédé de production, et composition associée
EP4342927A1 (fr) Composition de résine de polyuréthanne, objet durci, cuir artificiel, cuir synthétique et agent de traitement de surface pour cuir

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10783349

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2011518438

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10783349

Country of ref document: EP

Kind code of ref document: A1