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WO2022257008A1 - Cationic urethane resin composition - Google Patents

Cationic urethane resin composition Download PDF

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Publication number
WO2022257008A1
WO2022257008A1 PCT/CN2021/098872 CN2021098872W WO2022257008A1 WO 2022257008 A1 WO2022257008 A1 WO 2022257008A1 CN 2021098872 W CN2021098872 W CN 2021098872W WO 2022257008 A1 WO2022257008 A1 WO 2022257008A1
Authority
WO
WIPO (PCT)
Prior art keywords
urethane resin
cationic urethane
resin composition
formula
polyol
Prior art date
Application number
PCT/CN2021/098872
Other languages
French (fr)
Inventor
Zhiqiang Liu
Shuma Uchida
Sadamu Nagahama
Xiaoni LI
Original Assignee
Dic Corporation
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 Dic Corporation filed Critical Dic Corporation
Priority to CN202180098996.2A priority Critical patent/CN117425697A/en
Priority to JP2023547254A priority patent/JP7658448B2/en
Priority to PCT/CN2021/098872 priority patent/WO2022257008A1/en
Publication of WO2022257008A1 publication Critical patent/WO2022257008A1/en

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Classifications

    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium 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
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
    • 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
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic 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
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3819—Low-molecular-weight compounds having heteroatoms other than oxygen having nitrogen
    • C08G18/3821—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • 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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings

Definitions

  • the present invention relates to a cationic urethane resin composition.
  • a urethane resin composition having a urethane resin dispersed in water can reduce the environmental burden and, for this reason, has been recently increasingly used as a material suitable for the production of coating agents for synthetic leathers, gloves, curtains, sheets, and the like (see, e.g., PTL 1) .
  • An object of the invention is to provide a cationic urethane resin composition that yields a polyurethane film with excellent durability.
  • the invention provides a cationic urethane resin composition containing a cationic urethane resin (A) and water (B) .
  • the cationic urethane resin composition is configured such that the cationic urethane resin (A) has a structural unit represented by the following formula (1) .
  • R 1 represents a structure represented by the following formula (2) or formula (3)
  • R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure
  • R 4 represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction
  • X - represents an anionic counter ion
  • two benzene rings and oxygen atoms are each independently linked at the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring, and R 1 and R 2 each independently represent a hydrogen atom, a C 1-4 alkyl group, or a benzene ring) .
  • the cationic urethane resin composition of the invention can provide a polyurethane film with excellent durability.
  • the cationic urethane resin composition of the invention is excellent in dispersibility in water and stability during long-term storage.
  • the cationic urethane resin composition of the invention contains a cationic urethane resin (A) having a specific structural unit and water (B) .
  • the cationic urethane resin (A) In order to obtain excellent durability, it is indispensable for the cationic urethane resin (A) to have a structural unit represented by the following formula (1) .
  • R 1 represents a structure represented by the following formula (2) or formula (3)
  • R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure
  • R 4 represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction
  • X - represents an anionic counter ion
  • two benzene rings and oxygen atoms are each independently linked at the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring, and R 1 and R 2 each independently represent a hydrogen atom, a C 1-4 alkyl group, or a benzene ring) .
  • R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure, preferably a propyl group, a butyl group, or a pentyl group, and more preferably a butyl group.
  • the residue of a quaternizing agent is preferably a methyl group or an ethyl group.
  • the X - is preferably an anionic ion formed upon use of acetic acid, phosphoric acid, dibutyl acid, benzyl chloride, or the like as the below-described acid or quaternizing agent.
  • the epoxy raw material having a rigid chemical structure described above is used for the cationic urethane resin (A) , the elongation stress of a polyurethane film can be particularly improved, and further the heat resistance can also be improved.
  • the cationic urethane resin (A) for example, it is possible to use a reaction product of a polyol (a1) and a polyisocyanate (a2) , the polyol (a1) containing an amino group-containing polyol (a1-1) that is a reaction product of a diglycidyl ether (s1) having a structure represented by the above formula (2) or formula (3) and a secondary amine (s2) .
  • the diglycidyl ether having a structure represented by the above formula (2) for example, bisphenol-A diglycidyl ether, bisphenol-AP diglycidyl ether, bisphenol-B diglycidyl ether, bisphenol-BP diglycidyl ether, bisphenol-E diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-C diglycidyl ether, or the like can be used. These compounds may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability can be obtained, bisphenol-F diglycidyl ether is preferable.
  • a compound represented by the following formula (3-1) for example, a compound represented by the following formula (3-1) , a compound represented by the following formula (3-2) , or the like can be used. These compounds may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability can be obtained, a compound represented by the following formula (3-1) is preferable.
  • the secondary amine (s2) for example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-pentylamine, di-tert-butylamine, di-sec-butylamine, di-n-butylamine, di-n-pentylamine, di-n-peptylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-eicosylamine, or the like can be used.
  • These compounds may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability and water dispersion stability can be obtained, an aliphatic amine having 2 to 18 carbon atoms is preferable, and an aliphatic amine having 3 to 8 carbon atoms is more preferable.
  • the diglycidyl ether (s1) and the secondary amine (s2) may be formulated to have 1 equivalent of NH groups per equivalent of epoxy groups, and subjected to a ring-opening addition reaction in the absence of a catalyst at ambient temperature or with heating.
  • the reaction may be performed in the presence of an organic solvent as necessary, and may also be performed, for example, at a temperature within a range of 60 to 120°C for 30 minutes to 14 hours.
  • organic solvent for example, a ketone solvent such as acetone, diethyl ketone, methyl ethyl ketone, or methyl isobutyl ketone; an ether solvent such as diethyl ether or ethylene glycol dimethyl ether; an acetic acid ester solvent such as ethyl acetate or butyl acetate; a hydrocarbon solvent such as benzene, hexane, toluene, or xylene; an amide solvent such as dimethylformamide, or the like can be used.
  • a ketone solvent such as acetone, diethyl ketone, methyl ethyl ketone, or methyl isobutyl ketone
  • an ether solvent such as diethyl ether or ethylene glycol dimethyl ether
  • an acetic acid ester solvent such as ethyl acetate or butyl acetate
  • a hydrocarbon solvent such as benzene, he
  • the amount of the amino group-containing polyol (a1-1) used is, for the reason that even more excellent durability can be obtained, preferably within a range of 0.1 to 30 mass%, more preferably within a range of 1 to 15 mass%, in the total mass of the cationic urethane resin (A) .
  • the polyol (a1) contains the amino group-containing polyol (a1-1) as an essential component, and may also contain an additional polyol as necessary.
  • the content of the amino group-containing polyol (a1-1) in the polyol (a1) is, for the reason that even more excellent durability can be obtained, preferably within a range of 0.2 to 50 mass%, and preferably within a range of 0.5 to 30 mass%.
  • polycarbonate polyol for example, polycarbonate polyol, polyester polyol, polyether polyol, or the like can be used. These polyols may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent weatherability can be obtained, polycarbonate polyol is preferable.
  • the number average molecular weight of the additional polyol is, for the reason that even more excellent durability can be obtained, preferably within a range of 500 to 10,000, and more preferably within a range of 700 to 5,000.
  • the number average molecular weight of an additional polyol refers to a value measured by a gel permeation chromatography (GPC) method.
  • amino group-containing polyol (a1-1) in order to obtain even more excellent water dispersion stability, it is preferable that some or all of its tertiary amino groups are neutralized with an acid or quaternized with a quaternizing agent.
  • an organic acid such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, butanoic acid, lactic acid, malic acid, citric acid, tartaric acid, malonic acid, or adipic acid; an organic sulfonic acid such as sulfonic acid, p-toluenesulfonic acid, or methanesulfonic acid; an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, or fluoric acid, or the like can be used. These acids may be used alone, and it is also possible to use two or more kinds together.
  • a dialkyl sulfuric acid such as dimethyl sulfate or diethyl sulfate
  • a halogenated alkyl compound such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, or benzyl iodide
  • a methyl sulfonate compound such as methyl methanesulfonate, methyl p-toluenesulfonate, or methyl methanesulfonate
  • an epoxy compound such as ethylene oxide, propylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, or phenyl gly
  • the amount of the acid or quaternizing agent used may be, for example, within a range of 0.1 to 3 equivalents per equivalent of tertiary amino groups in the amino group-containing polyol (a1-1) .
  • polyisocyanate (a2) for example, an aliphatic polyisocyanate such as hexamethylene diisocyanate or lysine diisocyanate; an alicyclic polyisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or norbornane diisocyanate; an aromatic polyisocyanate such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylenepolyphenyl polyisocyanate, or carbodiimidized diphenylmethane polyisocyanate, or the like can be used.
  • These polyisocyanates may be used alone, and it is also possible to use two or more kinds together
  • the amount of the polyisocyanate (a2) used is, for the reason that even more excellent durability can be obtained, preferably within a range of 5 to 60 mass%, more preferably within a range of 10 to 45 mass%, in the total mass of the cationic urethane resin (A) .
  • a method for producing the cationic urethane resin (A) for example, a method in which the amino group-containing polyol (a1-1) , additional polyols, and the polyisocyanate (a2) are placed in bulk in a vessel and allowed to react in an organic solvent or in the absence of a solvent to give a polyurethane resin, further some or all of the tertiary amino groups in the polyurethane resin are neutralized with an acid and/or quaternized with the quaternizing agent, and then water (B) is added to cause dispersion in water, and the like can be mentioned.
  • the amino group-containing polyol (a1-1) , additional polyols, and the polyisocyanate (a2) are placed in bulk in a vessel and allowed to react in an organic solvent or in the absence of a solvent to give a polyurethane resin, further some or all of the tertiary amino groups in the polyurethane resin are neutralized with an acid and/or quaternized
  • the weight average molecular weight of the cationic urethane resin (A) is, for the reason that even more excellent durability and water dispersion stability can be obtained, preferably within a range of 4,000 to 300,000, and more preferably within a range of 7,000 to 200,000.
  • the weight average molecular weight of the cationic urethane resin (A) refers to a value measured by a gel permeation chromatography (GPC) method.
  • water (B) for example, ion exchange water, distilled water, or the like can be used. These waters may be used alone, and it is also possible to use two or more kinds together.
  • the content of the water (B) is within a range of 35 to 90 mass%, for example.
  • the cationic urethane resin composition of the invention contains the cationic urethane resin (A) and the water (B) , and may further contain other additives as necessary.
  • additives for example, neutralizers, emulsifiers, crosslinkers, thickeners, urethanization catalysts, fillers, foaming agent, pigments, dyes, oil repellents, hollow foams, flame retardants, defoamants, leveling agents, antiblocking agents, and the like can be used.
  • these additives may be used alone, and it is also possible to use two or more kinds together.
  • the cationic urethane resin composition of the invention can provide a polyurethane film with excellent durability.
  • the cationic urethane resin composition of the invention is excellent in dispersibility in water and stability during long-term storage. Accordingly, the cationic urethane resin composition of the invention is particularly suitable for use in the production of building materials and steel plates for household appliances, plastic films and plastic molded articles, receiving agents for recording substrates for ink-jet printing, and binders for glass fibers.
  • An amino group-containing polyol (a1-1-2) was obtained in the same manner as in Synthesis Example 1, except that 56 parts by mass of bisphenol-F diglycidyl ether was replaced with 56 parts by mass of a compound represented by formula (3-1) .
  • a cationic urethane resin composition (2) was obtained in the same manner as in Example 1, except that 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was replaced with 3.2 parts by mass of the amino group-containing polyol (a1-1-2) obtained in Synthesis Example 2.
  • a cationic urethane resin composition (R1) was obtained in the same manner as in Example 1, except that 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was replaced with 3.5 parts by mass of the amino group-containing polyol (aR1) obtained in Comparative Synthesis Example 1.
  • the number average molecular weight of a polyol and the weight average molecular weight of a cationic urethane resin each refer to a value measured by a gel permeation column chromatography (GPC) method under the following conditions.
  • High-performance GPC device High-performance GPC device ( “HLC-8220GPC” manufactured by Tosoh Corporation)
  • TKgel G4000 (7.8 mm I.D. ⁇ 30 cm) ⁇ 1
  • TKgel G2000 (7.8 mm I.D. ⁇ 30 cm) ⁇ 1
  • RI differential refractometer
  • Injection volume 100 ⁇ L (tetrahydrofuran solution having a sample concentration of 0.4 mass%)
  • Standard sample The following standard polystyrenes were used to prepare calibration curves.
  • the cationic urethane resin compositions obtained in the examples and comparative examples were each applied onto a release paper to a dried film thickness of 150 ⁇ m, dried at 23°C and a humidity of 65%for one day, and then dried at 150°C for 5 minutes to give a polyurethane film.
  • the film was separated from the release paper and cut to a width of 5 mm to give a specimen.
  • the specimen was stretched at 300 mm/min using “TENSILON Universal Testing Machine” manufactured by A&D Company, Limited, and the elongation stresses (MPa) at 100%stretch, 200%stretch, and 300%stretch were measured. Incidentally, a higher elongation stress value indicates better durability.
  • the cationic urethane resin compositions obtained in the examples and comparative examples were each applied onto a release paper to a dried film thickness of 150 ⁇ m, dried at 23°C and a humidity of 65%for one day, and then dried at 150°C for 5 minutes to give a polyurethane film.
  • the specimen released from the release paper was heated at 200°C for 1 hour, and the color difference ⁇ E before and after heating was measured using “CM-5” manufactured by Konica Minolta, Inc. Incidentally, a lower ⁇ E value indicates better durability.
  • the cationic urethane resin composition of the invention can yield a polyurethane film with excellent durability.
  • Comparative Example 1 which is a mode where a cationic urethane resin composition other than those specified in the invention was used, the durability was insufficient.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Provided is a cationic urethane resin composition containing a cationic urethane resin (A) and water (B). The cationic urethane resin composition is configured such that the cationic urethane resin (A) has a specific structural unit. The cationic urethane resin composition of the invention can provide a polyurethane film with excellent durability. In addition, the cationic urethane resin composition of the invention is excellent in dispersibility in water and stability during long-term storage. Accordingly, the cationic urethane resin composition of the invention is particularly suitable for use in the production of building materials and steel plates for household appliances, plastic films and plastic molded articles, receiving agents for recording substrates for ink-jet printing, and binders for glass fibers.

Description

CATIONIC URETHANE RESIN COMPOSITION Technical Field
The present invention relates to a cationic urethane resin composition.
Background Art
As compared with conventional organic solvent-based urethane resin compositions, a urethane resin composition having a urethane resin dispersed in water can reduce the environmental burden and, for this reason, has been recently increasingly used as a material suitable for the production of coating agents for synthetic leathers, gloves, curtains, sheets, and the like (see, e.g., PTL 1) .
As required properties of a urethane resin composition, not to mention excellent dispersibility in water and stability during long-term storage, further improvement in the durability of a polyurethane film has been demanded.
Citation List
Patent Literature
PTL 1: JP-A-2016-222921
Summary of Invention
Technical Problem
An object of the invention is to provide a cationic urethane resin composition that yields a polyurethane film with excellent durability.
Solution to Problem
The invention provides a cationic urethane resin composition containing a cationic urethane resin (A) and water (B) . The cationic urethane resin composition is configured such that the cationic urethane resin (A) has a structural unit represented by the following formula (1) .
[Formula 1]
Figure PCTCN2021098872-appb-000001
(In formula (1) , R 1 represents a structure represented by the following formula (2) or formula (3) , R 2 and R 3 each independently represent an alkyl group optionally having an  alicyclic structure, R 4 represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X - represents an anionic counter ion) .
[Formula 2]
Figure PCTCN2021098872-appb-000002
(In formula (2) , two benzene rings and oxygen atoms are each independently linked at the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring, and R 1 and R 2 each independently represent a hydrogen atom, a C 1-4 alkyl group, or a benzene ring) .
[Formula 3]
Figure PCTCN2021098872-appb-000003
(In formula (3) , two substituents linked to the cyclic ring are located in the ortho-, meta-, or para-positions) . Advantageous Effects of Invention
The cationic urethane resin composition of the invention  can provide a polyurethane film with excellent durability. In addition, the cationic urethane resin composition of the invention is excellent in dispersibility in water and stability during long-term storage.
Description of Embodiments
The cationic urethane resin composition of the invention contains a cationic urethane resin (A) having a specific structural unit and water (B) .
In order to obtain excellent durability, it is indispensable for the cationic urethane resin (A) to have a structural unit represented by the following formula (1) .
[Formula 1]
Figure PCTCN2021098872-appb-000004
(In formula (1) , R 1 represents a structure represented by the following formula (2) or formula (3) , R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure, R 4 represents a hydrogen atom or a residue  of a quaternizing agent introduced by a quaternization reaction, and X - represents an anionic counter ion) .
[Formula 2]
Figure PCTCN2021098872-appb-000005
(In formula (2) , two benzene rings and oxygen atoms are each independently linked at the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring, and R 1 and R 2 each independently represent a hydrogen atom, a C 1-4 alkyl group, or a benzene ring) .
[Formula 3]
Figure PCTCN2021098872-appb-000006
(In formula (3) , two substituents linked to the cyclic ring are located in the ortho-, meta-, or para-positions) .
In the above formula (1) , R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure, preferably a propyl group, a butyl group, or a pentyl  group, and more preferably a butyl group. The residue of a quaternizing agent is preferably a methyl group or an ethyl group. The X -is preferably an anionic ion formed upon use of acetic acid, phosphoric acid, dibutyl acid, benzyl chloride, or the like as the below-described acid or quaternizing agent.
When the epoxy raw material having a rigid chemical structure described above is used for the cationic urethane resin (A) , the elongation stress of a polyurethane film can be particularly improved, and further the heat resistance can also be improved.
As the cationic urethane resin (A) , for example, it is possible to use a reaction product of a polyol (a1) and a polyisocyanate (a2) , the polyol (a1) containing an amino group-containing polyol (a1-1) that is a reaction product of a diglycidyl ether (s1) having a structure represented by the above formula (2) or formula (3) and a secondary amine (s2) .
As the diglycidyl ether having a structure represented by the above formula (2) , for example, bisphenol-A diglycidyl ether, bisphenol-AP diglycidyl ether, bisphenol-B diglycidyl ether, bisphenol-BP diglycidyl ether, bisphenol-E diglycidyl ether, bisphenol-F diglycidyl ether, bisphenol-C diglycidyl ether, or the like can be used. These compounds may be used  alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability can be obtained, bisphenol-F diglycidyl ether is preferable.
As the diglycidyl ether having a structure represented by the above formula (3) , for example, a compound represented by the following formula (3-1) , a compound represented by the following formula (3-2) , or the like can be used. These compounds may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability can be obtained, a compound represented by the following formula (3-1) is preferable.
[Formula 4]
Figure PCTCN2021098872-appb-000007
[Formula 4]
Figure PCTCN2021098872-appb-000008
As the secondary amine (s2) , for example, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-pentylamine, di-tert-butylamine, di-sec-butylamine, di-n-butylamine, di-n-pentylamine, di-n-peptylamine, di-n-octylamine, diisooctylamine, dinonylamine, diisononylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine, di-n-pentadecylamine, di-n-octadecylamine, di-n-nonadecylamine, di-n-eicosylamine, or the like can be used. These compounds may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent durability and water dispersion stability can be obtained, an aliphatic amine having 2 to 18 carbon atoms is preferable, and an aliphatic amine having 3 to 8 carbon atoms is more preferable.
As a method for producing the amino group-containing polyol (a1-1) , for example, the diglycidyl ether (s1) and the secondary amine (s2) may be formulated to have 1 equivalent of NH groups per equivalent of epoxy groups, and subjected to a ring-opening addition reaction in the absence of a catalyst at ambient temperature or with heating. The reaction may be performed in the presence of an organic solvent as necessary, and may also be performed, for example, at a temperature within a range of 60 to 120℃ for 30 minutes to 14 hours.
As the organic solvent, for example, a ketone solvent such as acetone, diethyl ketone, methyl ethyl ketone, or methyl isobutyl ketone; an ether solvent such as diethyl ether or ethylene glycol dimethyl ether; an acetic acid ester solvent such as ethyl acetate or butyl acetate; a hydrocarbon solvent such as benzene, hexane, toluene, or xylene; an amide solvent such as dimethylformamide, or the like can be used. These organic solvents may be used alone, and it is also possible to use two or more kinds together.
The amount of the amino group-containing polyol (a1-1) used is, for the reason that even more excellent durability can be obtained, preferably within a range of 0.1 to 30 mass%, more preferably within a range of 1 to 15 mass%, in the total mass of the cationic urethane resin (A) .
The polyol (a1) contains the amino group-containing polyol (a1-1) as an essential component, and may also contain an additional polyol as necessary. The content of the amino group-containing polyol (a1-1) in the polyol (a1) is, for the reason that even more excellent durability can be obtained, preferably within a range of 0.2 to 50 mass%, and preferably within a range of 0.5 to 30 mass%.
As the additional polyol, for example, polycarbonate polyol, polyester polyol, polyether polyol, or the like can be used. These polyols may be used alone, and it is also possible to use two or more kinds together. Among them, for the reason that even more excellent weatherability can be obtained, polycarbonate polyol is preferable.
The number average molecular weight of the additional polyol is, for the reason that even more excellent durability can be obtained, preferably within a range of 500 to 10,000, and more preferably within a range of 700 to 5,000. Incidentally, the number average molecular weight of an additional polyol refers to a value measured by a gel permeation chromatography (GPC) method.
In the amino group-containing polyol (a1-1) , in order to obtain even more excellent water dispersion stability, it is preferable that some or all of its tertiary amino groups are neutralized with an acid or quaternized with a quaternizing agent.
As the acid, for example, an organic acid such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, butanoic acid, lactic acid, malic acid, citric acid, tartaric acid, malonic acid, or adipic acid; an organic  sulfonic acid such as sulfonic acid, p-toluenesulfonic acid, or methanesulfonic acid; an inorganic acid such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, phosphorous acid, or fluoric acid, or the like can be used. These acids may be used alone, and it is also possible to use two or more kinds together.
As the quaternizing agent, for example, a dialkyl sulfuric acid such as dimethyl sulfate or diethyl sulfate; a halogenated alkyl compound such as methyl chloride, ethyl chloride, benzyl chloride, methyl bromide, ethyl bromide, benzyl bromide, methyl iodide, ethyl iodide, or benzyl iodide; a methyl sulfonate compound such as methyl methanesulfonate, methyl p-toluenesulfonate, or methyl methanesulfonate; an epoxy compound such as ethylene oxide, propylene oxide, styrene oxide, epichlorohydrin, allyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, or phenyl glycidyl ether, or the like can be used. These compounds may be used alone, and it is also possible to use two or more kinds together.
The amount of the acid or quaternizing agent used may be, for example, within a range of 0.1 to 3 equivalents per equivalent of tertiary amino groups in the amino group-containing polyol (a1-1) .
As the polyisocyanate (a2) , for example, an aliphatic polyisocyanate such as hexamethylene diisocyanate or lysine diisocyanate; an alicyclic polyisocyanate such as cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, or norbornane diisocyanate; an aromatic polyisocyanate such as phenylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, naphthalene diisocyanate, polymethylenepolyphenyl polyisocyanate, or carbodiimidized diphenylmethane polyisocyanate, or the like can be used. These polyisocyanates may be used alone, and it is also possible to use two or more kinds together.
The amount of the polyisocyanate (a2) used is, for the reason that even more excellent durability can be obtained, preferably within a range of 5 to 60 mass%, more preferably within a range of 10 to 45 mass%, in the total mass of the cationic urethane resin (A) .
As a method for producing the cationic urethane resin (A) , for example, a method in which the amino group-containing polyol (a1-1) , additional polyols, and the polyisocyanate (a2) are placed in bulk in a vessel and allowed to react in an organic  solvent or in the absence of a solvent to give a polyurethane resin, further some or all of the tertiary amino groups in the polyurethane resin are neutralized with an acid and/or quaternized with the quaternizing agent, and then water (B) is added to cause dispersion in water, and the like can be mentioned.
The weight average molecular weight of the cationic urethane resin (A) is, for the reason that even more excellent durability and water dispersion stability can be obtained, preferably within a range of 4,000 to 300,000, and more preferably within a range of 7,000 to 200,000. Incidentally, the weight average molecular weight of the cationic urethane resin (A) refers to a value measured by a gel permeation chromatography (GPC) method.
As the water (B) , for example, ion exchange water, distilled water, or the like can be used. These waters may be used alone, and it is also possible to use two or more kinds together. The content of the water (B) is within a range of 35 to 90 mass%, for example.
The cationic urethane resin composition of the invention contains the cationic urethane resin (A) and the water (B) , and may further contain other additives as necessary.
As the other additives, for example, neutralizers, emulsifiers, crosslinkers, thickeners, urethanization catalysts, fillers, foaming agent, pigments, dyes, oil repellents, hollow foams, flame retardants, defoamants, leveling agents, antiblocking agents, and the like can be used. These additives may be used alone, and it is also possible to use two or more kinds together.
Thus, the cationic urethane resin composition of the invention can provide a polyurethane film with excellent durability. In addition, the cationic urethane resin composition of the invention is excellent in dispersibility in water and stability during long-term storage. Accordingly, the cationic urethane resin composition of the invention is particularly suitable for use in the production of building materials and steel plates for household appliances, plastic films and plastic molded articles, receiving agents for recording substrates for ink-jet printing, and binders for glass fibers.
Examples
Hereinafter, the present invention will be described in further detail using examples.
[Synthesis Example 1] Synthesis of Amino Group-Containing Polyol (a1-1-1)
56 Parts by mass of bisphenol-F diglycidyl ether was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dripping device, and then the inside of the flask was purged with nitrogen. Next, heating was performed until the temperature in the flask reached 70℃. Subsequently, using the dripping device, 44 parts by mass of di-n-butylamine was dripped for 30 minutes, and, after completion, the mixture was allowed to react at 90℃ for 10 hours to give an amino group-containing polyol (a1-1-1) .
[Synthesis Example 2] Synthesis of Amino Group-Containing Polyol (a1-1-2)
An amino group-containing polyol (a1-1-2) was obtained in the same manner as in Synthesis Example 1, except that 56 parts by mass of bisphenol-F diglycidyl ether was replaced with 56 parts by mass of a compound represented by formula (3-1) .
[Comparative Synthesis Example 1] Synthesis of Amino Group-Containing Polyol (aR1)
590 Parts by mass of polypropylene glycol diglycidyl ether (epoxy equivalent: 201 g/eq) was placed in a four-necked flask equipped with a stirrer, a reflux condenser, a thermometer, and a dripping device, and then the inside of the  flask was purged with nitrogen. Next, heating was performed until the temperature in the flask reached 70℃. Subsequently, using the dripping device, 380 parts by mass of di-n-butylamine was dripped for 30 minutes, and, after completion, the mixture was allowed to react at 90℃ for 10 hours to give an amino group-containing polyol (aR1) .
[Example 1]
To a four-necked flask equipped with a thermometer, a stirring device, a reflux condenser tube, and a dripping device, 30.6 parts by mass of polycarbonate polyol ( “NIPPORAN 980R” manufactured by Nippon Polyurethane Industry Co., Ltd. ) and 18.7 parts by mass of MEK were added, and stirred while cooling to 50℃. After stirring, 8.7 parts by mass of 4, 4’-dicyclohexylmethane diisocyanate and 0.01 parts by mass of stannous octoate were added, and allowed to react at 70℃ for 2 hours.
Subsequently, 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was added, and allowed to react for 4 hours. Subsequently, 0.85 parts by mass of aminoethylethanolamine was added, and subjected to a chain elongation reaction for 1 hour.
Next, 10.6 parts by mass of MEK and 0.75 parts by mass of acetic acid were added, retained at 55℃ for 1 hour, and then cooled to 40℃, and 85 parts by mass of ion exchange water  was added, thereby preparing a water dispersion. The water dispersion was distilled off at reduced pressure to give a cationic urethane resin composition (1) having a nonvolatile content of 35 mass%.
[Example 2]
A cationic urethane resin composition (2) was obtained in the same manner as in Example 1, except that 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was replaced with 3.2 parts by mass of the amino group-containing polyol (a1-1-2) obtained in Synthesis Example 2.
[Comparative Example 1]
A cationic urethane resin composition (R1) was obtained in the same manner as in Example 1, except that 3.1 parts by mass of the amino group-containing polyol (a1-1-1) obtained in Synthesis Example 1 was replaced with 3.5 parts by mass of the amino group-containing polyol (aR1) obtained in Comparative Synthesis Example 1.
[Measurement Method for Number Average Molecular Weight/Weight Average Molecular Weight]
The number average molecular weight of a polyol and the weight average molecular weight of a cationic urethane resin  each refer to a value measured by a gel permeation column chromatography (GPC) method under the following conditions.
Measuring device: High-performance GPC device ( “HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
“TSKgel G5000” (7.8 mm I.D. × 30 cm) × 1
“TSKgel G4000” (7.8 mm I.D. × 30 cm) × 1
“TSKgel G3000” (7.8 mm I.D. × 30 cm) × 1
“TSKgel G2000” (7.8 mm I.D. × 30 cm) × 1
Detector: RI (differential refractometer)
Column temperature: 40℃
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL/min
Injection volume: 100 μL (tetrahydrofuran solution having a sample concentration of 0.4 mass%)
Standard sample: The following standard polystyrenes were used to prepare calibration curves.
(Standard Polystyrene)
“TSKgel Standard Polystyrene A-500” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene A-1000” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene A-2500” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene A-5000” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-1” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-2” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-4” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-10” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-20” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-40” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-80” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-128” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-288” manufactured by Tosoh Corporation
“TSKgel Standard Polystyrene F-550” manufactured by Tosoh Corporation
[Durability Evaluation Method]
(1) Evaluation of Elongation Stress
The cationic urethane resin compositions obtained in the examples and comparative examples were each applied onto a release paper to a dried film thickness of 150 μm, dried at 23℃ and a humidity of 65%for one day, and then dried at 150℃ for 5 minutes to give a polyurethane film. The film was separated from the release paper and cut to a width of 5 mm to give a specimen. The specimen was stretched at 300 mm/min using “TENSILON Universal Testing Machine” manufactured by A&D Company, Limited, and the elongation stresses (MPa) at 100%stretch, 200%stretch, and 300%stretch were measured. Incidentally, a higher elongation stress value indicates better durability.
(2) Evaluation of Resistance to Heat Discoloration
The cationic urethane resin compositions obtained in the examples and comparative examples were each applied onto a release paper to a dried film thickness of 150 μm, dried at 23℃ and a humidity of 65%for one day, and then dried at 150℃ for 5 minutes to give a polyurethane film. The specimen released from the release paper was heated at 200℃ for 1 hour, and the color difference ΔE before and after heating was measured using “CM-5” manufactured by Konica Minolta, Inc. Incidentally, a lower ΔE value indicates better durability.
[Table 1]
Figure PCTCN2021098872-appb-000009
As shown by Examples 1 and 2, it turned out that the cationic urethane resin composition of the invention can yield a polyurethane film with excellent durability.
Meanwhile, in Comparative Example 1, which is a mode where a cationic urethane resin composition other than those specified in the invention was used, the durability was insufficient.

Claims (2)

  1. A cationic urethane resin composition comprising a cationic urethane resin (A) and water (B) ,
    the cationic urethane resin composition being configured such that the cationic urethane resin (A) has a structural unit represented by the following formula (1) :
    [Formula 1]
    Figure PCTCN2021098872-appb-100001
    (wherein R 1 represents a structure represented by the following formula (2) or formula (3) , R 2 and R 3 each independently represent an alkyl group optionally having an alicyclic structure, R 4 represents a hydrogen atom or a residue of a quaternizing agent introduced by a quaternization reaction, and X - represents an anionic counter ion) ,
    [Formula 2]
    Figure PCTCN2021098872-appb-100002
    (wherein two benzene rings and oxygen atoms are each independently linked at the 2-position, 3-position, 4-position, 5-position, or 6-position of the benzene ring, and R 1 and R 2 each independently represent a hydrogen atom, a C 1-4 alkyl group, or a benzene ring) ,
    [Formula 3]
    Figure PCTCN2021098872-appb-100003
    (wherein two substituents linked to the cyclic ring are located in the ortho-, meta-, or para-positions) .
  2. The cationic urethane resin composition according to claim 1, wherein the cationic urethane resins (A) is a reaction product of a polyol (a1) and a polyisocyanate (a2) , the polyol (a1) containing an amino group-containing polyol (a1-1) that is a reaction product of a diglycidyl ether (s1) having a structure represented by the formula (2) or formula (3) and a secondary amine (s2) .
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GB1531621A (en) * 1976-01-21 1978-11-08 Ppg Industries Inc Cationic electrodepositable compositions
CN1961015A (en) * 2004-06-29 2007-05-09 大日本油墨化学工业株式会社 Aqueous dispersions of cationic polyurethane resins, ink-jet receiving agents containing the same, and ink-jet recording media made by using the agents
JP2007168164A (en) * 2005-12-20 2007-07-05 Dainippon Ink & Chem Inc Ink jet receiving agent and ink jet recording medium using the same
CN102822220A (en) * 2010-04-08 2012-12-12 蓝宝迪有限公司 Aqueous anionic polyurethane dispersions
JP2012211284A (en) * 2011-03-31 2012-11-01 Dic Corp Cationic urethane resin composition and metal coating agent
CN103265686A (en) * 2013-04-19 2013-08-28 淮海工学院 Antibacterial polyether type polyurethane and preparation method thereof
CN105176155A (en) * 2015-07-29 2015-12-23 华南理工大学 UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN108929424A (en) * 2018-06-13 2018-12-04 三晃树脂（佛山）有限公司 A kind of novel cation hydrophilic agent and its preparation, application method

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