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WO2012121311A1 - Composé de polyuréthane, composition le contenant, composition aqueuse de dispersion de polyuréthane et substances résultant de son durcissement - Google Patents

Composé de polyuréthane, composition le contenant, composition aqueuse de dispersion de polyuréthane et substances résultant de son durcissement Download PDF

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Publication number
WO2012121311A1
WO2012121311A1 PCT/JP2012/055896 JP2012055896W WO2012121311A1 WO 2012121311 A1 WO2012121311 A1 WO 2012121311A1 JP 2012055896 W JP2012055896 W JP 2012055896W WO 2012121311 A1 WO2012121311 A1 WO 2012121311A1
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Prior art keywords
polyurethane
compound
group
meth
acrylate
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English (en)
Japanese (ja)
Inventor
昌彦 渡部
貴文 平川
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Ube Corp
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Ube Industries Ltd
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    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • 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
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • 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
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • 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
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds

Definitions

  • the present invention relates to a polyurethane compound, a composition containing the polyurethane compound, a dispersion of the polyurethane compound, and a cured product thereof.
  • Polyurethane compounds are widely used, for example, for interior and exterior materials for aircraft and automobiles, exterior wall and floor materials for homes, parts for home appliances and electronic materials, or as raw materials for paints, coating agents, or adhesives.
  • the above-mentioned coating films such as paints and coating agents not only produce a beautiful appearance, but also serve to protect the base material, so that hardness, strength, durability and the like are required.
  • polyurethane compounds that give a harder coating are strongly desired.
  • an active energy ray-curable resin is used from the viewpoint of workability and the like.
  • acrylic-modified urethane resins are cured immediately upon irradiation with active energy rays, resulting in high processing speed and low total cost. Therefore, they can be used in various fields such as various coating agents such as hard coating agents, paints, and adhesives. It's being used.
  • Hard coating agents are required to have various functions such as weather resistance, abrasion resistance, heat resistance, and hydrolysis resistance, and are polycarbonate-based acrylic modified that is superior in functionality to polyester-based and polyether-based acrylic-modified urethane resins. Urethane resins are being considered. For example, since a polyester system has an ester bond, a hard coat agent produced using this has a disadvantage that it is inferior in hydrolysis resistance. A polyether system has an ether bond, so a hard coat agent produced using this has a weather resistance. There is a disadvantage that it is inferior in heat resistance and heat resistance. Patent Document 1 proposes a 1,6-hexanediol-type polycarbonate diol resin composition from the viewpoint of excellent wear resistance, adhesion, and weather resistance. However, there is a problem that the hardness which is one of the important functions of the hard coat agent is not yet sufficient.
  • An object of the present invention is to provide a novel polyurethane compound, a composition containing the same, an aqueous polyurethane dispersion composition, and a cured product thereof, which give a cured product having a high elastic modulus and high hardness.
  • the present invention has been made to solve the above problems, and specifically has the following configuration.
  • Z 1 and Z 2 each independently represent a linear or branched alkanediyl group having 1 to 10 carbon atoms.
  • the polycarbonate diol (A) has a repeating unit represented by the formula (1) and a repeating unit represented by the formula (2) and has one hydroxyl group at both ends of the molecular chain.
  • Z 3 represents an optionally substituted linear or branched alkanediyl group having 2 to 10 carbon atoms, or an optionally substituted cycloalkanediyl group having 3 to 10 carbon atoms.
  • An aqueous polyurethane dispersion composition dispersed in an aqueous medium [10] A cured product obtained by applying the aqueous polyurethane dispersion composition according to [9], drying and curing. [11] After reacting the polycarbonate diol (A) with the polyisocyanate compound (B) to obtain a polyurethane prepolymer having an isocyanato group at the end, the polyurethane prepolymer and the molecule have one or more hydroxyl groups.
  • the polyurethane compound of the present invention a composition containing the same and a cured product thereof are excellent in elastic modulus and hardness, and are optimal in various fields requiring high hardness, such as metal, wood, paper, plastic, electric / electronic. -Suitable for use in many fields, such as coating agents in the automotive field, automobile interior and exterior, furniture, paints for floors and walls of building materials, various adhesives, inks, decorative films (especially hard coat layers for decorative films) be able to.
  • Polycarbonate diol (A) The polycarbonate diol (A) according to the present invention has a repeating unit represented by the following formula (1).
  • Z 1 and Z 2 each independently represent a linear or branched alkanediyl group having 1 to 10 carbon atoms.
  • alkanediyl group represented by Z 1 and Z 2 include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, a butane-1,3-diyl group, a pentamethylene group, and a hexamethylene group.
  • Examples include a methylene group, a heptamethylene group, an octamethylene group, and a decamethylene group.
  • the alkanediyl group represented by Z 1 and Z 2 is a straight chain having 1 to 4 carbon atoms or the alkanediyl group represented by Z 1 and Z 2 from the viewpoint that the cured product obtained by curing the polymerizable composition containing the resulting polyurethane compound has a higher elastic modulus.
  • Branched alkanediyl groups are more preferred.
  • Examples of the linear or branched alkanediyl group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, and a butane-1,3-diyl group. Groups.
  • the bond of Z 1 and Z 2 to the benzene ring is preferably a 1,4-bond (para form) or a 1,3-bond (meta form), and more preferably a 1,4-bond (para form).
  • the polycarbonate diol (A) according to the present invention has one hydroxyl group at both ends of the molecular chain. Therefore, the polycarbonate diol (A) according to the present invention is composed of only the repeating unit represented by the formula (1) and two hydroxyl groups at both ends of the molecular chain, for example, the following formula (3):
  • n is an integer representing the number of repeating units.
  • a polycarbonate diol composed of a repeating unit represented by the formula (1), one or more other repeating units, and two hydroxyl groups at both ends of the molecular chain.
  • a copolymer may also be used.
  • the ratio of the repeating unit represented by the formula (1) to other repeating units is preferably 1:99 to 99: 1, more preferably 30:70 to 99: 1, and 50:50 to 99: 1. Is more preferable, and 55:45 to 99: 1 is particularly preferable.
  • a polycarbonate diol particularly suitable as a polycarbonate diol represented by only the repeating unit represented by the formula (1) and two hydroxyl groups is represented by the following formula (3a).
  • n is an integer representing the number of repeating units.
  • the number, content, number average molecular weight and the like of the repeating unit represented by the formula (1) of the polycarbonate diol (A) according to the present invention are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, weather resistance, From the viewpoint of applicability in various fields, it is as follows.
  • the number of repeating units represented by the formula (1) is preferably 1 to 18, more preferably 2 to 13.
  • the number average molecular weight of the polycarbonate diol (A) according to the present invention is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 400 to 1,000. If the number average molecular weight is too high, the melting point becomes high and handling may be difficult. On the other hand, if the number average molecular weight is too low, the number of carbonate bonds decreases, and it may be difficult to express the properties as a polycarbonate diol.
  • the polycarbonate diol (A) according to the present invention 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 (4) and a carbonate ester (5) are subjected to a transesterification reaction in the presence or absence of a catalyst to give polycarbonate diol (3 ).
  • R 1 and R 2 represent a hydrocarbon group having 1 to 6 carbon atoms which may have a substituent, or together, alkanediyl having 2 to 4 carbon atoms Indicates a group.
  • n represents the number of repeating units, and is preferably 1 to 18, more preferably 2 to 13.
  • alcohols (R 1 OH, R 2 OH, etc.) derived from the carbonate ester (5) are by-produced during the transesterification reaction, and therefore it is preferable to proceed the reaction while extracting it by distillation or the like. .
  • carbonate carbonates such as ethylene carbonate
  • glycols derived from alkylene carbonate since glycols derived from alkylene carbonate are by-produced, it is preferable to advance reaction, extracting this by distillation etc. .
  • the details of the aromatic dihydroxyl compound (4), the carbonate ester (5), and the transesterification will be described later in [Production Method B].
  • the polycarbonate diol (A) according to the present invention is a polycarbonate diol composed of a repeating unit represented by the formula (1), one or more other repeating units, and two hydroxyl groups at both ends of the molecular chain.
  • the other repeating unit is not particularly limited as long as it has a carbonate structure.
  • the melting point and glass transition temperature of the obtained polyurethane compound can be lowered, the following formula (2 ) Is preferred.
  • Z 3 is a linear or branched alkanediyl group having 2 to 10 carbon atoms which may have a substituent, a cycloalkanediyl group having 3 to 10 carbon atoms which may have a substituent, Or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent.
  • the “substituent” may be any group that does not participate in the subsequent urethanization reaction.
  • Examples of the linear or branched alkanediyl group having 2 to 10 carbon atoms represented by Z 3 include an ethylene group, a trimethylene group, a propane-1,2-diyl group, a tetramethylene group, and a butane-1,3-diyl group. , Pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, decamethylene group and the like.
  • Examples of the cycloalkanediyl group having 3 to 10 carbon atoms represented by Z 3 include cyclopropane-1,2-diyl group, cyclobutane-1,3-diyl group, cyclopentane-1,2-diyl group, cyclohexane-1 , 2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group, cyclononane-1,5- A diyl group, a cyclodecane-1,6-diyl group, an adamantane-1,3-diyl group and the like can be mentioned.
  • Examples of the alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain represented by Z 3 include a cyclopropane-1,2-dimethylene group, a cyclobutane-1,3-dimethylene group, a cyclopentane-1, 2-dimethylene group, cyclopentane-1,3-dimethylene group, cyclohexane-1,2-dimethylene group, cyclohexane-1,3-dimethylene group, cyclohexane-1,4-dimethylene group, cyclohexane-1,2-diethylene group And cyclohexane-1,3-diethylene group, cyclohexane-1,4-diethylene group, cycloheptane-1,4-dimethylene group, cyclooctane-1,5-dimethylene group and the like.
  • Z 3 is preferably a linear alkanediyl group having 3 to 6 carbon atoms or an alkanediyl group having 6 to 8 carbon atoms having an alicyclic structure in the main chain.
  • Said Z 3 is in particular trimethylene group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, cyclohexane-1,3-dimethylene group, cyclohexane-1, It is preferably one or more selected from the group consisting of 4-dimethylene groups.
  • the polycarbonate diol (A) according to the present invention is composed of a repeating unit represented by the formula (1), a repeating unit represented by the formula (2), and two hydroxyl groups at both ends of the molecular chain.
  • n is an integer representing the number of repeating units.
  • the polycarbonate diol copolymer of the random copolymer represented by these may be sufficient.
  • the molar ratio of [(repeating unit represented by formula (1)) / (repeating unit represented by formula (2))] is preferably 1/9 to 9/1, 5 to 5/1 is more preferable, and 1/3 to 3/1 is still more preferable.
  • the number of repeating units represented by the formulas (1) and (2) of the polycarbonate diol copolymer, the content, the number average molecular weight, etc. are from the viewpoint of mechanical performance, hydrolysis resistance, heat resistance, 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 (2) 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 10 to 20 in the polycarbonate diol copolymer. 90 mol%, more preferably 25 to 75 mol%.
  • the number of the repeating unit represented by the formula (2) is preferably 1 to 30, more preferably 2 to 20, and the content of the repeating unit is preferably 10 to 10 in the polycarbonate diol copolymer. 90 mol%, more preferably 25 to 75 mol%.
  • the number average molecular weight of the polycarbonate diol copolymer according to the present invention is preferably 200 to 3,000, more preferably 300 to 2,000, and still more preferably 900 to 1,500.
  • the Hazen unit color number (APHA) defined in JIS K 1557 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 10 to 10,000 cp (75 ° C.), more preferably 50 to 5,000 cp (75 ° C.), and still more preferably 100 to 1,500 cp (75 ° C.).
  • Examples of the method for producing the polycarbonate diol copolymer include a method of reacting an aromatic diol compound, an aliphatic dihydroxyl compound, carbonate ester, phosgene, and the like by a known method such as a carbonate ester method or a phosgene method. Of these, the carbonate method is preferred. As a carbonate method, the following manufacturing method B is mentioned preferably, for example.
  • the terminal is not limited to a structural unit derived from the aliphatic dihydroxyl compound (6).
  • R 1 , R 2 , Z 3 and n are the same as described above.
  • alcohols (R 1 OH, R 2 OH, etc.) derived from the carbonic ester (5) are by-produced during the transesterification reaction. Therefore, it is preferable to proceed the reaction while extracting this by distillation or the like.
  • carbonate carbonate such as ethylene carbonate
  • glycols derived from alkylene carbonate are by-produced, reaction can be advanced while extracting this by distillation etc. preferable.
  • the aromatic dihydroxyl compound used in the polycarbonate diol according to the present invention is represented by the following formula (4).
  • Z 1 and Z 2 are the same as described above, and each independently represents a linear or branched alkanediyl group having 1 to 10 carbon atoms. Specific examples and preferred examples of the alkanediyl group are as described above, and a linear or branched alkanediyl group having 1 to 4 carbon atoms is preferable.
  • Z 1 and Z 2 are preferably 1,4-bond (para-form) or 1,3-bond (meta-form), and more preferably 1,4-bond (para-form).
  • Particularly preferred aromatic dihydroxyl compounds (a) include 1,4-benzenedimethanol, 1,4-benzenediethanol, 1,4-benzenedipropanol, 1,4-benzenedibutanol, and 1,3-benzene.
  • Examples thereof include compounds having a linear or branched alkanediyl group having 1 to 4 carbon atoms such as propanol.
  • the carbonate ester (5) that can be used in the polycarbonate diol according to the present invention is not particularly limited, but it is desirable to appropriately select one that can efficiently extract by-product alcohols derived from the carbonate 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 carbonate having an alkyl group having 1 to 4 carbon atoms is preferable, and dimethyl carbonate is particularly preferable.
  • the aliphatic dihydroxyl compound that can be used in the polycarbonate diol according to the present invention is represented by the following formula (6).
  • Z 3 is the same as described above, and may have a linear or branched alkanediyl group having 2 to 10 carbon atoms, which may have a substituent, or may have 3 to 10 carbon atoms which may have a substituent. It represents either a cycloalkanediyl group or an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain which may have a substituent.
  • alkanediols in which Z 3 is an alkanediyl group having 2 to 10 carbon atoms include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol. 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and the like.
  • Examples of the branched carbon chain of the alkanediyl 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 cycloalkanediol in which Z 3 is a cycloalkanediyl group having 3 to 10 carbon atoms include cyclopropane-1,2-diol, cyclobutane-1,3-diol, cyclopentane-1,2-diol, cyclohexane- 1,2-diol, cyclohexane-1,3-diol, cyclohexane-1,4-diol, cycloheptane-1,4-diol, cyclooctane-1,5-diol, cyclononane-1,5-diol, cyclodecane- Examples include 1,6-diol and adamantane-1,3-diol.
  • Examples of cycloalkanediol in which Z 3 is an alkanediyl group having 5 to 10 carbon atoms having an alicyclic structure in the main chain include cyclopropane-1,2-dimethanol, cyclobutane-1,3-dimethanol, cyclo Examples include pentane-1,3-dimethanol and 1,4-cyclohexanedimethanol.
  • alkanes having 4 to 8 carbon atoms, particularly 4 to 6 carbon atoms, such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and the like are easy to handle and easy to obtain.
  • Aliphatic diols having an alicyclic structure having 5 to 8 carbon atoms such as diol and 1,4-cyclohexanedimethanol are more preferred.
  • Examples of the catalyst used for the production of the polycarbonate diol according to the present invention 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 hydroxides include alkaline earth metal hydroxides. Products (magnesium hydroxide, etc.), alkaline earth metal alkoxides (magnesium methoxide, etc.) and the like.
  • Examples of the aluminum compound include aluminum compounds such as aluminum alkoxide (aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, etc.) and aluminum acetylacetonate.
  • Examples of the zinc compound include zinc carboxylates (such as zinc acetate) and zinc acetylacetonate.
  • Examples of the 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.
  • antimony compound examples include antimony carboxylates (such as antimony acetate) and antimony alkoxide
  • zirconium compound examples include zirconium alkoxide (zirconium propoxide, zirconium butoxide, etc.) and zirconium acetylacetonate.
  • titanium compound examples include titanium alkoxide (titanium tetraethoxide, titanium tetrapropoxide, titanium tetrabutoxide, tetracyclohexyl titanate, tetrabenzyl titanate, etc.), titanium acylate (tributoxy titanium stearate, isopropoxy titanium stearate, etc.) , Titanium chelates (diisopropoxy titanium bisacetylacetonate, dihydroxy bis lactato titanium, etc.) and the like.
  • organotin compound examples include dibutyltin oxide, dibutyltin diacetate, and dibutyltin dilaurate.
  • the carboxylic acid in each carboxylate is preferably a carboxylic acid having 2 to 30 carbon atoms, and more preferably a carboxylic acid having 2 to 18 carbon atoms.
  • Each alkoxide is preferably an alkoxy group having 1 to 30 carbon atoms, and more preferably an alkoxy group having 2 to 18 carbon atoms.
  • 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.
  • said aromatic dihydroxyl compound (4), carbonate ester (5), aliphatic dihydroxyl compound (6), and a catalyst can be used individually by 1 type or in combination of 2 or more types.
  • the transesterification reaction in the method for producing a polycarbonate diol according to the present invention can be performed in the presence or absence of a catalyst, but it is preferably performed in the presence of a catalyst from the viewpoint of reaction efficiency.
  • the reaction temperature and reaction pressure in the transesterification reaction vary depending on the types of the carbonic acid ester (5) and the aliphatic dihydroxyl compound (6) to be used.
  • aromatic dihydroxyl such as 1,4-benzenedimethanol
  • compound (4) and production method B it is preferable that the aromatic dihydroxyl compound (4) and the aliphatic dihydroxyl compound (6) are not substantially distilled off.
  • the reaction temperature is preferably 90 to 230 ° C.
  • the reaction pressure is preferably reduced from normal pressure to 30 to 500 mmHg.
  • the reaction can be performed in an atmosphere of air, carbon dioxide gas, or inert gas (nitrogen, argon, helium, etc.) or in an air stream, but is preferably performed in an inert gas atmosphere or in an air stream.
  • the amount used in the case of using a catalyst is the production method with respect to the total charged amount of aromatic dihydroxyl compound (4) and carbonate ester (5) at the start of the reaction.
  • a polycarbonate diol copolymer can also be obtained by transesterification in the presence or absence of.
  • a polycarbonate diol copolymer can also be obtained by transesterification in the presence or absence of.
  • the average molecular weight of the polycarbonate diol (A) according to the present invention is prepared by changing the reaction molar ratio of the aromatic dihydroxyl compound (4), the carbonate ester (5), and the aliphatic dihydroxyl compound (6) to be used. be able to.
  • the average molecular weight of the produced polycarbonate diol or polycarbonate diol copolymer is smaller than the target average molecular weight, the aromatic dihydroxyl compound (4) and / or the aliphatic dihydroxyl compound (6) are further reduced under reduced pressure.
  • the aromatic dihydroxyl compound (4) and / or the aliphatic dihydroxyl compound (6) is added to cause further ester exchange reaction.
  • a polycarbonate diol or a polycarbonate diol copolymer having a target average molecular weight can be obtained.
  • the constituent molar ratio of the repeating unit of the polycarbonate diol copolymer according to the present invention can be prepared by changing the molar ratio of the aromatic dihydroxyl compound (4) and the aliphatic dihydroxyl compound (6). .
  • the polyisocyanate compound (B) that can be used in the present invention is not particularly limited. Specifically, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate (TDI), 2, 6-tolylene diisocyanate, 4,4'-diphenylenemethane diisocyanate (MDI), 2,4-diphenylmethane diisocyanate, 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ′, 4 ′′ -triphenylmethane triisocyanate, m-isocyanatophenylsulfonyl isocyanate P-isocyana
  • the number of isocyanate groups per molecule of the polyisocyanate compound is usually two, but polyisocyanates having three or more isocyanato groups such as triphenylmethane triisocyanate can be used as long as the polyurethane compound in the present invention does not gel. Can be used.
  • MDI 4,4'-diphenylenemethane diisocyanate
  • IPDI isophorone diisocyanate
  • hydrogenation 4,4'-dicyclohexylmethane diisocyanate
  • ((Meth) acrylate compound having hydroxyl group (C)) Although it does not restrict
  • numerator which can be used by this invention For example, ethylene glycol mono (Meth) acrylate, propylene glycol mono (meth) acrylate, butanediol mono (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meta ) Acrylate, triethylene glycol mono (meth) acrylate, tripropylene glycol mono (meth) acrylate, tetraethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Monohydric alcohol mono (me
  • (Meth) acrylate trimethylolpropane mono (meth) acrylate, ethoxylated trimethylolpropane mono (meth) acrylate, propoxylated trimethylolpropane mono (meth) acrylate, tris (2-hydroxyethyl) isocyanurate mono (meth) acrylate, Glycerin mono (meth) acrylate, trimethylolpropane di (meth) acrylate, ethoxylated trimethylolpropane di (meth) acrylate, propoxylation Mono (meth) acrylates and di (meth) acrylates of trivalent alcohols such as limethylolpropane di (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, glycerin di (meth) acrylate, Mono and di (meth) acrylates in which some of the hydroxyl groups of these alcohols are modified with alkyl groups or
  • dihydric alcohols such as ethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate and butanediol mono (meth) acrylate from the viewpoint of low viscosity and low cost.
  • the mono (meth) acrylate is preferably ethylene glycol mono (meth) acrylate.
  • the polyurethane compound of the present invention is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. Details of the reaction are as described later, but may be carried out according to a known method for producing a polyurethane compound. Also, for example, after reacting the polycarbonate diol (A) and the polyisocyanate compound (B) to obtain a polyurethane prepolymer having an isocyanato group at the terminal, one or more hydroxyl groups in the molecule are added to the polyurethane prepolymer.
  • the polyurethane compound of the present invention may be produced by reacting the (meth) acrylate compound (C).
  • the polyurethane compound of the present invention includes an acidic group-containing polyol (D ) May be obtained.
  • the acidic group-containing polyol (D) is not particularly limited as long as it is a compound containing two or more hydroxyl groups and one or more acidic groups in one molecule. Examples of the acidic group include a carboxy group, a sulfonyl group, a phosphoric acid group, and a phenolic hydroxyl group.
  • a compound having two or more hydroxyl groups and one or more carboxy groups in one molecule is preferable, and a compound having two hydroxyl groups and one carboxy group in one molecule. Is more preferable.
  • the acidic group-containing polyol (D) include, for example, dimethylol alkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid, N, N-bishydroxyethylglycine, N , N-bishydroxyethylalanine, 3,4-dihydroxybutanesulfonic acid, 3,6-dihydroxy-2-toluenesulfonic acid, acidic group-containing polyether polyol, acidic group-containing polyester polyol, and the like.
  • dimethylol alkanoic acid such as 2,2-dimethylolpropionic acid and 2,2-dimethylolbutanoic acid
  • N N-bishydroxyethylglycine
  • N N-bishydroxyethylalanine
  • 3,4-dihydroxybutanesulfonic acid 3,6-dihydroxy-2-toluenesulfonic acid
  • acidic group-containing polyether polyol acidic group-containing polyester
  • dimethylolalkanoic acid is preferable from the viewpoint of availability, and in this case, the alkanoic acid preferably has 4 or less carbon atoms, and more preferably 2,2-dimethylolpropionic acid.
  • the said acidic group containing polyol (D) only 1 type may be used independently and 2 or more types may be used together.
  • the polyurethane compound of the present invention also includes a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, and an acidic group-containing polyol (D). Obtained by reacting with. Details of the reaction are as described later, but may be carried out according to a known method for producing a polyurethane compound.
  • polyurethane prepolymer having an isocyanate group at the terminal
  • the polyurethane compound of the present invention may be produced by reacting (meth) acrylate compound (C) having one or more hydroxyl groups therein.
  • the polyurethane compound of the present invention comprises a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule, and an acidic group-containing polyol as an optional component. It may be obtained by reacting (D) with a chain extender (E). Examples of the chain extender (E) include compounds having reactivity with isocyanato groups.
  • 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. And the like. These may be used alone or in combination of two or more.
  • the method for adding the chain extender (E) may be a one-shot method in which each raw material is reacted at once, or a prepolymer method in which it is reacted with a polyurethane prepolymer having an isocyanato group at the molecular end.
  • the polyurethane prepolymer is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and an optional acidic group-containing polyol (D).
  • the polyurethane prepolymer comprises a polycarbonate diol (A), a polyisocyanate compound (B), an optional acidic group-containing polyol (D), and a (meth) acrylate having one or more hydroxyl groups in the molecule.
  • What reacted with the compound (C) may be used.
  • the (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule has only one hydroxyl group in the molecule, it has one or more hydroxyl groups in the molecule (meta )
  • the isocyanate group of the polyurethane prepolymer is almost sealed with (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule.
  • E) may not be allowed to react.
  • the amount of the chain extender (E) can be appropriately selected.
  • the number of moles of the group having reactivity with the isocyanate group in the chain extender other than water is not more than twice the number of moles of the isocyanate group in the polyurethane prepolymer.
  • a chain extender can be added as follows. More preferably, the molar ratio of the polyurethane prepolymer to the chain extender is mixed at 1: 1 to 0.8: 1.
  • the polyurethane compound of the present invention can be produced by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) containing at least one hydroxyl group.
  • the reaction temperature is 0 to 150 ° C, preferably 20 to 100 ° C.
  • this reaction may be performed in an inert gas atmosphere, in an air atmosphere, or in a mixed atmosphere of an inert gas and air, but when air is used, it is dried. It is preferred to use air.
  • the ratio (OH / NCO) is preferably a ratio of 100/100 to 110/100.
  • the catalyst that can be used in the above reaction examples include a catalyst (urethanization catalyst) used in a normal urethanization reaction.
  • a catalyst urethanization catalyst
  • organotin compounds such as dibutyltin diacetate and dibutyltin dilaurate
  • organotitanium compounds such as titanium tetraacetylacetonate and titanium diisopropoxybis (ethylacetoacetate)
  • zirconium tetraacetylacetonate and zirconium di Specific examples include organic zirconium compounds such as butoxybis (ethylacetoacetate); tertiary amine compounds such as triethylamine.
  • These urethanization catalysts may be used individually by 1 type, and may use multiple types together.
  • organotin compounds and organozirconium compounds are preferred, with dibutyltin dilaurate and zirconium tetraacetylacetonate being more preferred.
  • the addition amount of the urethanization catalyst is 0.00005% by weight to 0% based on the total weight of the polycarbonate diol (A), the polyisocyanate compound (B) and the (meth) acrylate compound (C) having a hydroxyl group to be used. 0.01% by weight is preferable, 0.0001% by weight to 0.005% by weight is more preferable, and 0.0003% by weight to 0.003% by weight is particularly preferable.
  • a polymerization inhibitor and antioxidant can be used.
  • Specific examples include hydroquinone, p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, p-benzoquinone, and 2,5-dihydroxy-p-benzoquinone.
  • These polymerization inhibitors and antioxidants may be used alone or in combination of two or more.
  • the addition amount of the polymerization inhibitor and the antioxidant is 0.00005 weight with respect to the total weight of the polycarbonate diol (A), the polyisocyanate compound (B), and the (meth) acrylate compound (C) having a hydroxyl group.
  • % To 0.01% by weight, more preferably 0.0001% to 0.005% by weight, particularly preferably 0.0003% to 0.003% by weight.
  • the organic solvent is not particularly limited, but for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl Ester solvents such as ether acetate, ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, benzene, toluene, Specific examples include aromatic
  • organic solvents may be used individually by 1 type, and may use multiple types together.
  • the amount of the organic solvent used is such that the ratio of the total weight of the polycarbonate diol (A), the polyisocyanate compound (B) and the (meth) acrylate compound (C) to be used is 1/9 to 9 / A ratio of 1 is preferable, a ratio of 2/8 to 8/2 is more preferable, and a ratio of 3/7 to 7/3 is particularly preferable.
  • the isolated polyurethane compound can be dissolved or dispersed in an organic solvent to form a liquid or pasty polyurethane solution.
  • the solid content concentration of the polyurethane compound is preferably 3 to 95% by weight.
  • a liquid or pasty polyurethane solution can be used as an adhesive, a coating agent, or a paint.
  • the organic solvent to be used is not particularly limited, but is the same as those listed as usable for the above-mentioned reaction.
  • the polyurethane composition (curable resin composition) of the present invention is a compound (F) having a polymerizable unsaturated bond other than the polyurethane compound of the present invention, if necessary, the polyurethane compound of the present invention, a polymerization initiator (G). It is characterized by containing.
  • Examples of the polymerization initiator (G) used in the polyurethane composition of the present invention include commonly used photopolymerization initiators.
  • the photopolymerization initiator is not particularly limited.
  • Preferred examples include 1-hydroxycyclohexyl phenyl ketone and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide. These photoinitiators may be used individually by 1 type, and may use multiple types together.
  • the addition amount of the photopolymerization initiator is preferably 0.3% by weight to 10% by weight and more preferably 0.5% by weight to 5% by weight with respect to the weight of the polyurethane compound.
  • the compound (F) having a polymerizable unsaturated bond used in the polyurethane composition of the present invention is not particularly limited.
  • polymerizable compounds may be used individually by 1 type, and may use multiple types together.
  • the addition amount of the compound (F) having a polymerizable unsaturated bond is preferably 100 parts by weight or less with respect to 100 parts by weight of the polyurethane compound.
  • the polyurethane composition of the present invention includes a coloring pigment, an extender pigment, a bright pigment, a thickening agent, a curing catalyst, an ultraviolet absorber, a light stabilizer, an antifoaming agent, depending on the use and if necessary.
  • Usual paint additives such as plasticizers, surface conditioners and anti-settling agents can be used. These paint additives may be used alone or in combination of two or more. Moreover, if these additives are well-known, they can be used without any limitation as long as the properties of the polyurethane composition and the cured product thereof are not impaired.
  • the cured product of the present invention is prepared by adjusting the polyurethane composition to an appropriate viscosity with an organic solvent or the like, if necessary, and then ultraviolet rays, visible light, laser light, electron beams, X rays, ⁇ rays, plasma, microwaves. It can be produced by polymerization and curing by irradiating energy rays such as. Alternatively, it can be produced by polymerization and curing by heat.
  • the solvent that can be used as the organic solvent is not particularly limited.
  • ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate , Ester solvents such as dipropylene glycol monomethyl ether acetate; ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether; benzene Fragrance such as toluene, xylene, tetramethylbenzene Such as system solvent is exemplified specifically.
  • These organic solvents may be used individually by 1 type, and may use multiple types together
  • Examples of the material to be coated or the material to be coated when the cured product of the present invention is obtained as a coating or coating include metals, plastics, inorganic materials, wood, and resins such as ABS resin and polycarbonate resin.
  • the polyurethane compound of the present invention can also be dispersed in an aqueous medium to form an aqueous polyurethane dispersion.
  • the polycarbonate diol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), and the aqueous medium are essential components, but acidic groups
  • the contained polyol (D) and the chain extender (E) are optional components.
  • a polyurethane compound obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), and a (meth) acrylate compound (C) is dispersed in an aqueous medium.
  • An aqueous polyurethane dispersion; a polyurethane compound obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C), and an acidic group-containing polyol (D) is an aqueous medium.
  • the polyurethane compound obtained by reacting the todiol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), the acidic group-containing polyol (D), and the chain extender (E) is an aqueous medium.
  • An aqueous polyurethane dispersion dispersed therein can be mentioned.
  • the polyurethane compound of the present invention is obtained by reacting a polycarbonate diol (A), a polyisocyanate compound (B), a (meth) acrylate compound (C), and an acidic group-containing polyol (D), At least the polycarbonate diol (A), the polyisocyanate compound (B), the (meth) acrylate compound (C), and the acidic group-containing polyol (D) are reacted, and then the acidic group is neutralized with a base.
  • an aqueous polyurethane dispersion can be obtained.
  • the (meth) acrylate compound (C) may be reacted with the polyurethane prepolymer before the polyurethane prepolymer is dispersed in the aqueous medium, or the polyurethane together with the aqueous medium. You may make it react with a prepolymer, and after making it disperse
  • polyurethane compound of the present invention is reacted with polycarbonate diol (A), polyisocyanate compound (B), (meth) acrylate compound (C), acidic group-containing polyol (D), and chain extender (E).
  • the acidic group derived from the contained polyol is neutralized, dispersed in an aqueous medium, reacted with a chain extender (E), and then a (meth) acrylate compound (C) having one or more hydroxyl groups in the molecule. ).
  • the (meth) acrylate compound (C) and the chain extender (E) may be reacted with the polyurethane prepolymer before the polyurethane prepolymer is dispersed in the aqueous medium. It may be reacted with the polyurethane prepolymer together with the aqueous medium, or may be reacted with the polyurethane prepolymer after being dispersed in the aqueous medium.
  • Examples of the base for neutralizing the acidic group include trimethylamine, triethylamine, triisopropylamine, tributylamine, triethanolamine, N-methyldiethanolamine, N-phenyldiethanolamine, dimethylethanolamine, diethylethanolamine, N-methylmorpholine.
  • organic amines such as pyridine; inorganic alkalis such as sodium hydroxide and potassium hydroxide; ammonia and the like. Among these, organic amines are preferable, tertiary amines are more preferable, and triethylamine is most preferable. These may be used alone or in combination of two or more.
  • aqueous medium examples include water and a mixed medium of water and a hydrophilic organic solvent.
  • the aqueous medium is preferably used in such an amount that the proportion of the polyurethane resin in the aqueous polyurethane resin dispersion is 5 to 60% by weight, more preferably 20 to 50% by weight.
  • Examples of the water include clean water, ion-exchanged water, distilled water, and ultrapure water, but preferably ion-exchanged in consideration of availability and particle instability due to the influence of salt.
  • Water is mentioned.
  • Examples of the hydrophilic organic solvent include ketones such as acetone and ethyl methyl ketone, esters, ethers such as tetrahydrofuran and N-methylmorpholine, and amides such as dimethylformamide, N-methylpyrrolidone and N-ethylpyrrolidone. And alcohols. These may be used alone or in combination of two or more.
  • the aqueous polyurethane dispersion composition can be prepared by adding the compound (F) having the polymerizable unsaturated bond and the polymerization initiator (G) to the aqueous polyurethane dispersion of the present invention.
  • the compound (F) having the polymerizable unsaturated bond and the polymerization initiator (G) can be used for the above composition.
  • pigments, dyes, thickeners, curing catalysts, UV absorbers, light stabilizers, antifoaming agents, plasticizers, surface conditioners, anti-settling agents and the like are used for ordinary paints as necessary. Additives can be contained alone or in combination of two or more.
  • aqueous polyurethane dispersion composition of the present invention can be applied to a substrate or a release material by a method such as bell coating, spray coating, roll coating, shower coating, or dip coating. By heating this at a temperature of 50 to 250 ° C. or leaving it at room temperature for a long time, it can be dried to obtain a cured product.
  • the hydroxyl value of the polycarbonate diol was measured by a method based on JIS K 1577.
  • the acid value was measured according to JIS K 1557 method B.
  • the moisture was measured by a coulometric titration method using a Karl Fischer moisture meter.
  • APHA measured the Hazen unit color number (APHA) as follows based on JIS K 1557 based on JIS K 1557. (Standard solution adjustment) 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 were placed in a 1 liter measuring flask and completely dissolved, and then water was added up to the marked line was standardized. . This solution is APHA standard solution no. No. 500 and various standard solutions are No. Dilute 500 standard solution with water and adjust. For example, APHA standard solution No. 100 is No. 100. Dilute 20.0 ml of 500 standard solution with 80.0 ml of water.
  • Measurement method It is a colorless, transparent, flat-bottomed glass tube with the same diameter and the same diameter with the same wall thickness of 23 mm, and a colorimetric tube with a marked line at the same height from the bottom so that the liquid volume is 100 ml. Insert the sample up to the marked line, taking care to avoid bubbles. Next, a suitable APHA standard solution was placed on a white plate and compared from above, and a standard solution having a concentration closest to the sample was obtained. The number of the standard solution was designated as APHA.
  • the conversion rate of the isocyanate group at the time of synthesizing the polyurethane compound was calculated from the isocyanate group content measured by a method according to JIS K 1603.
  • the solid content concentration of the polyurethane compound solution was calculated from the weight loss before and after drying after the polyurethane compound solution was dried at 140 ° C. for 3 hours.
  • the viscosity was measured with an E-type viscometer.
  • An ultraviolet curing device manufactured by Sen Special Light Source, HM15001C-4, lamp: SE-1500M was used for curing the polyurethane compound.
  • the hardness of the cured product was measured by measuring the amplitude decay time with a pen drum type hardness tester (manufactured by BYK-Gardner GmbH, a pen drum hardness tester) by placing a coating film sample made of a glass plate on a sample stage. The longer the amplitude decay time, the greater the hardness.
  • the elastic modulus, tensile strength, and elongation at break of the cured product were measured by a method in accordance with JIS K 7311 by forming a film sample from a polystyrene resin plate into a film.
  • the measurement conditions were a measurement temperature of 23 ° C., a humidity of 50%, and a tensile speed of 100 mm / min.
  • the abrasion of the cured product was determined by setting a coating film sample made of a polycarbonate resin plate on a sample stage, and using a taper abrasion tester (manufactured by TOYOSEIKI, HS), rotating speed: 60 rpm, load: 500 g, worn wheel: H- 18 was used to measure the weight loss of the coating. The smaller the weight loss, the better the wear resistance.
  • Example 1 (1) Synthesis of Polycarbonate Diol Into a 500 ml glass round bottom flask equipped with a rectifying tower, a stirrer, a thermometer, and a nitrogen introduction tube, 199.3 g (2.21 mol) of dimethyl carbonate and 1,4-benzenedimethanol 65 .2 g (0.47 mol), 1,6-hexanediol 167.2 g (1.41 mol), and titanium tetrabutoxide 0.03 g were charged while distilling off a mixture of methanol and dimethyl carbonate under normal pressure and stirring. The transesterification reaction was carried out for 6 hours. During this time, the reaction temperature was gradually raised from 95 ° C. to 200 ° C., and the composition of the distillate was adjusted to be the azeotropic composition of methanol and dimethyl carbonate or in the vicinity thereof.
  • the pressure was gradually reduced to 100 mmHg, and the ester exchange reaction was further carried out at 195 ° C. for 4 hours while distilling off the mixture of methanol and dimethyl carbonate with stirring.
  • the reaction solution was cooled to room temperature to obtain 280 g of a polycarbonate diol copolymer.
  • the transesterification reaction was performed in a nitrogen stream.
  • the obtained polycarbonate diol copolymer had a number average molecular weight of 996, APHA of 60, hydroxyl value of 112.6 mgKOH / g, acid value of 0.01 mgKOH / g, and water content of 120 ppm.
  • Example 2 A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of 2-hydroxyethyl methacrylate, and a butyl acetate solution 80 of the polyurethane compound obtained in Example 1 (2) Part by weight was mixed well to prepare a polyurethane composition (cured resin composition).
  • the polyurethane composition was applied to a glass plate using a 50 ⁇ m applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm 2 of ultraviolet rays using an ultraviolet curing device to obtain a cured product.
  • the hardness of the obtained cured product was 162 seconds in terms of amplitude decay time, the elastic modulus was 210 MPa, the tensile strength was 27 MPa, the elongation at break was 89%, and the wear resistance was a weight loss of 32.9 mg at 400 revolutions. .
  • Comparative Example 2 A mixture of 1 part by weight of bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 19 parts by weight of 2-hydroxyethyl methacrylate and a butyl acetate solution of the polyurethane compound obtained in Comparative Example 1 (1)
  • a polyurethane composition (curable resin composition) was prepared by thoroughly mixing 80 parts by weight. Each of the polyurethane compositions was applied to a glass plate using a 50 ⁇ m applicator, dried at 80 ° C. for 30 minutes, and then irradiated with 1000 mJ / cm 2 of ultraviolet rays using an ultraviolet curing device to obtain a cured product.
  • the hardness of the obtained cured product was 55 seconds in terms of amplitude decay time, elastic modulus was 46 MPa, tensile strength was 27 MPa, elongation at break was 113%, and abrasion was a weight loss of 55.8 mg at 400 revolutions. .
  • the polyurethane compound, aqueous polyurethane dispersion, and polyurethane solution of the present invention can be used as materials such as energy ray curable paints and energy ray curable coating agents.
  • the polyurethane composition of the present invention can also be used as a raw material for the energy ray-curable coating material and the energy ray-curable coating agent or as such.
  • the cured product of the present invention can be used as a film in various fields such as a decorative film and a cutting film.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne : un nouveau composé de polyuréthane qui, quand il est durci, possède un module d'élasticité élevé et une grande dureté ; une composition contenant ledit composé ; une composition aqueuse de dispersion de polyuréthane ; et des substances résultant du durcissement desdites compositions. Le composé de polyuréthane est obtenu par la réaction d'un composé de (méth)acrylate (C) contenant au moins un groupe hydroxyle par molécule, d'un composé de polyisocyanate (B) et d'un polycarbonate diol (A) contenant un groupe hydroxyle à chaque extrémité de la chaîne moléculaire et comporte un motif répétitif représenté par la formule (1).
PCT/JP2012/055896 2011-03-08 2012-03-08 Composé de polyuréthane, composition le contenant, composition aqueuse de dispersion de polyuréthane et substances résultant de son durcissement Ceased WO2012121311A1 (fr)

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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
WO2014106939A1 (fr) * 2013-01-07 2014-07-10 宇部興産株式会社 Dispersion aqueuse de résine et son utilisation
JP2016199617A (ja) * 2015-04-07 2016-12-01 日本合成化学工業株式会社 光硬化性組成物
JPWO2017122759A1 (ja) * 2016-01-15 2018-11-29 株式会社Ｇｓユアサ 蓄電素子
JP2019067608A (ja) * 2017-09-29 2019-04-25 三洋化成工業株式会社 リチウムイオン電池
JP2019070108A (ja) * 2017-08-02 2019-05-09 宇部興産株式会社 水性ポリウレタン樹脂分散体及びその製造方法
JP2019109997A (ja) * 2017-12-18 2019-07-04 三菱ケミカル株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
JP2020164586A (ja) * 2019-03-28 2020-10-08 宇部興産株式会社 土木建築用ウレタン（メタ）アクリレート

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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
WO2014106939A1 (fr) * 2013-01-07 2014-07-10 宇部興産株式会社 Dispersion aqueuse de résine et son utilisation
JP2016199617A (ja) * 2015-04-07 2016-12-01 日本合成化学工業株式会社 光硬化性組成物
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JP2019067608A (ja) * 2017-09-29 2019-04-25 三洋化成工業株式会社 リチウムイオン電池
JP2019109997A (ja) * 2017-12-18 2019-07-04 三菱ケミカル株式会社 非水系電解液、及びそれを用いた非水系電解液二次電池
JP2020164586A (ja) * 2019-03-28 2020-10-08 宇部興産株式会社 土木建築用ウレタン（メタ）アクリレート

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