WO2018061764A1 - Dispersion aqueuse - Google Patents

Dispersion aqueuse Download PDF

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Publication number
WO2018061764A1
WO2018061764A1 PCT/JP2017/032990 JP2017032990W WO2018061764A1 WO 2018061764 A1 WO2018061764 A1 WO 2018061764A1 JP 2017032990 W JP2017032990 W JP 2017032990W WO 2018061764 A1 WO2018061764 A1 WO 2018061764A1
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WO
WIPO (PCT)
Prior art keywords
group
nco
parts
urethane prepolymer
aqueous dispersion
Prior art date
Application number
PCT/JP2017/032990
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English (en)
Japanese (ja)
Inventor
秀一 和田
Original Assignee
第一工業製薬株式会社
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Application filed by 第一工業製薬株式会社 filed Critical 第一工業製薬株式会社
Priority to CN201780059315.5A priority Critical patent/CN109790266A/zh
Publication of WO2018061764A1 publication Critical patent/WO2018061764A1/fr

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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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the present invention relates to an aqueous dispersion.
  • Water-based polyurethane resins are conventionally useful materials as adhesives, coating agents, paints, modifiers, binders, etc., and are used in a wide range of applications.
  • aqueous polyurethane resin a method in which a hydrophilic group such as anionic, cationic, nonionic, etc. is contained in a urethane resin skeleton and self-emulsified and dispersed can make the particle diameter fine and in terms of performance. Although it is known to be excellent, further improvement in characteristics in various applications is required.
  • Patent Documents 1 and 2 an organic-inorganic composite resin with organosilane and its partially hydrolyzed condensate, an aqueous dispersion of polyurethane / urea and colloidal silica containing alkoxysilane groups are disclosed (Patent Documents 1 and 2).
  • a resin having a hydrolyzable silyl group introduced at the end of a urethane resin by using a monoamino group-containing silane compound or silane aspartate the molecular weight of the urethane resin portion is small, and its flexibility In addition, the film formability is inferior. Further, when the molecular weight of the urethane resin portion is increased, the amount of the hydrolyzable silyl group introduced is reduced, and a stable dispersion cannot be obtained, and improvement has been desired.
  • an aqueous dispersion that solves these problems, that is, has high environmental compatibility, does not require the use equipment to have an explosion-proof structure or the like, and is excellent in emulsion stability.
  • the present invention also provides an aqueous dispersion having good film properties, that is, appearance, water resistance, solvent resistance, hardness, scratch resistance, and heat resistance.
  • the inventors of the present invention have studied to solve the above problems. It has been found that the NCO-terminated urethane prepolymer having a specific structure can be solved by a specific amount of a reaction product with the silane coupling agent (E) having a specific structure, and the present invention has been completed.
  • An NCO-terminated urethane prepolymer (D) obtained by reacting an active hydrogen group-containing cationic salt-forming group-containing compound (A), a polyol component (B), and a polyisocyanate component (C); 1) An aqueous dispersion containing a reaction product with the silane coupling agent (E) described in 1), wherein the silane coupling agent is 1 / mol with respect to 1 mol of NCO groups of the NCO-terminated urethane prepolymer (D). Water dispersion (X) which is 2 mol or less.
  • An NCO-terminated urethane prepolymer (D) obtained by reacting an active hydrogen group-containing cationic salt-forming group-containing compound (A), a polyol component (B), and a polyisocyanate component (C).
  • the aqueous dispersion of the present invention is an aqueous dispersion, it is highly environmentally compatible and it is not necessary to use an explosion-proof structure for the equipment used. Excellent emulsification stability. Moreover, the film characteristics of the film obtained, that is, appearance, water resistance, solvent resistance, hardness, scratch resistance, and heat resistance are good.
  • the aqueous dispersion (X) of the present invention is an NCO-terminated urethane prepolymer obtained by reacting an active hydrogen group-containing cationic salt-forming group-containing compound (A), a polyol component (B), and a polyisocyanate component (C).
  • aqueous dispersion containing a reaction product of a polymer (D) and a silane coupling agent (E) described by the formula (1), wherein 1 mol of NCO groups of the NCO-terminated urethane prepolymer (D)
  • the aqueous dispersion (X) has a silane coupling agent of 1 ⁇ 2 mol or less.
  • R 1 O n Si (R 2 ) 3-n C 3 H 6 NHC 2 H 4 NH 2 (1) (Wherein R 1 is a hydrocarbon group having 1 to 2 carbon atoms, n is 2 or 3, and R 2 is a methyl group)
  • the active hydrogen group-containing cationic salt-forming group-containing compound (A) is not particularly limited as long as it is an active hydrogen group- and cationic salt-forming group-containing compound.
  • the active hydrogen group means a functional group containing a hydrogen atom having reactivity with an isocyanate group, and examples thereof include a hydroxyl group, an amino group, and a thiol group.
  • Examples of the cationic salt-forming group include compounds having a group that can be a tertiary group or a quaternary group that can be neutralized with an acid.
  • N-alkyl dialkanol amines examples thereof include N-alkyl dialkanol amines, N, N-dialkyl monoalkanol amines, trialkanol amines, alkylene oxide adducts having 2 to 4 carbon atoms, amino alcohols and amines.
  • the N-alkyl dialkanolamine is not particularly limited, and examples thereof include N-methyldiethanolamine and N-butyldiethanolamine.
  • the N, N-dialkylmonoalkanolamine is not particularly limited, and examples thereof include N, N-dimethylethanolamine and N, N-diethylethanolamine.
  • the trialkanolamines are not particularly limited, and examples thereof include triethanolamine and tripropanolamine.
  • the alkylene oxide having 2 to 4 carbon atoms is not particularly limited, and examples thereof include ethylene oxide and propylene oxide.
  • the amino alcohol is not particularly limited, and examples thereof include N-methyl-N- (3-aminopropyl) -ethanolamine and N, N-dimethylhydrazine. Of these, N-alkyl dialkanolamine is preferable, and N-methyldiethanolamine is more preferable. These can use 1 type, or 2 or more types.
  • the compound etc. which have organic acid and inorganic acid, and a reactive halogen atom are mention
  • the organic acid is not particularly limited, and examples thereof include hydrochloric acid, nitric acid, formic acid, acetic acid, dimethyl sulfate, diethyl sulfate, methyl chloride, and benzyl chloride. Of these, from the viewpoint of workability, formic acid neutralization of N-methyldiethanolamine and quaternized tertiary amine compounds with dimethyl sulfate are preferred. These can use 1 type, or 2 or more types.
  • the polyol component is not particularly limited as long as it is a compound having at least two hydroxyl groups (except for the compound corresponding to (A)).
  • polyhydric alcohol polyether polyol, polyester polyol, polyether ester polyol, polycarbonate polyol, polyolefin polyol, polyacryl polyol, polyacetal polyol, polybutadiene polyol, polysiloxane polyol, fluorine polyol, etc.
  • examples thereof include compounds having the above hydroxyl groups.
  • the polyhydric alcohol is not particularly limited, but for example, ethylene glycol, diethylene glycol, butanediol, propylene glycol, hexanediol, bisphenol A, bisphenol B, bisphenol S, hydrogenated bisphenol A, dibromobisphenol A, 1, 4 -Cyclohexanedimethanol, dihydroxyethyl terephthalate, hydroquinone dihydroxyethyl ether, trimethylolpropane, glycerin, pentaerythritol and the like.
  • the polyether polyol is not particularly limited, and examples thereof include alkylene oxide derivatives of polyhydric alcohols, polytetramethylene glycol, and polythioether polyols.
  • polyester polyol For example, polyhydric alcohol, polyhydric carboxylic acid, polyhydric carboxylic acid anhydride, polyether polyol, esterified product from polyhydric carboxylic acid ester, castor oil polyol, polycaprolactone polyol, etc. can give.
  • the polyolefin polyol is not particularly limited, and examples thereof include polybutadiene polyol, polyisoprene polyol, and hydrogenated polyols thereof. Of these, polyether polyol, polyester polyol, and polycarbonate polyol are preferred. These can use 1 type, or 2 or more types.
  • the number average molecular weight of the polyol component is not particularly limited, but is preferably 50 to 10,000, more preferably 500 to 5,000 from the viewpoints of emulsification and emulsion stability.
  • the polyol component contains an ethylene oxide adduct of a polyhydric alcohol.
  • the polyhydric alcohol is not particularly limited as long as it is a dihydric or higher alcohol, but a dihydric alcohol is preferable from the viewpoint of suppressing an increase in the prepolymer viscosity and a low emulsion viscosity.
  • the ethylene oxide adduct of the polyhydric alcohol may contain other alkylene oxide adducts as long as it contains ethylene oxide. Examples of other alkylene oxide adducts include propylene oxide and butylene oxide. As an addition form, either random addition or block addition may be used. From the viewpoint of reducing the number of blended parts and water resistance, it is preferable not to contain other alkylene oxide adducts.
  • the ethylene oxide adduct of polyhydric alcohol is preferably contained in an amount of 20 parts by weight or less, more preferably 3 to 10 parts by weight based on 100 parts by weight of the NCO-terminated urethane prepolymer (D). . Within these ranges, it is preferable from the viewpoints of transparency and strength of the film, improved flexibility, and water resistance.
  • the said weight part says the weight part of only an ethylene oxide adduct segment, and when other alkylene oxide is included, the weight part of the said other alkylene oxide is not included.
  • the polyisocyanate component (C) is not particularly limited, and examples thereof include organic polyisocyanates such as aromatic, aliphatic, alicyclic, and aromatic fats.
  • organic polyisocyanates such as aromatic, aliphatic, alicyclic, and aromatic fats.
  • organic polyisocyanates such as aliphatic, alicyclic, and araliphatic, and these Multi-modified products (dimers, trimers, etc.) or biuret-modified products produced by the reaction of the organic polyisocyanate with water are preferred.
  • Organic polyisocyanates such as 4,4'-dicyclohexylmethane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate [bis (isocyanenatomethyl) cyclohexane], hexamethylene diisocyanate, lysine diisocyanate, norbornane diisocyanate, xylylene diisocyanate, and modified products thereof Is more preferable. Further, 4,4′-dicyclohexylmethane diisocyanate and isophorone diisocyanate are more preferable. These can use 1 type, or 2 or more types.
  • NCO-terminated urethane prepolymer (D) The NCO-terminated urethane prepolymer (D) of the present invention is obtained by reacting an active hydrogen group-containing cationic salt-forming group-containing compound (A), a polyol component (B), and a polyisocyanate component (C).
  • the isocyanate group content per solid content of the NCO-terminated urethane prepolymer (D) of the present invention is not particularly limited as long as it is 0.1% or more, but the NCO-terminated urethane prepolymer has a low viscosity and a stable emulsion is obtained. Therefore, 0.5 to 10.0% is preferable.
  • the average molecular weight of the NCO-terminated urethane prepolymer (D) of the present invention is preferably 5000 or less, and more preferably 4000 or less, from the viewpoint of emulsifiability and emulsion stability.
  • the average molecular weight here means a theoretical value calculated from the number average molecular weight of the charged raw materials.
  • the amine value of the NCO-terminated urethane prepolymer (D) of the present invention is not particularly limited, but is preferably 7 to 60 mgKOH / g, more preferably 15 to 35 mgKOH / g. Within these ranges, the stability of the aqueous dispersion is good, and the transparency of the silica composite resin is high, which is preferable from the viewpoints of film formability, water resistance, and flexibility.
  • the silane coupling agent (E) is a compound described by the formula (1).
  • R 1 O n Si (R 2 ) 3-n C 3 H 6 NHC 2 H 4 NH 2
  • R 1 is a hydrocarbon group having 1 to 2 carbon atoms, and is preferably 1 from the viewpoint of hydrolyzability and availability.
  • n is 2 or 3.
  • R 2 is a methyl group.
  • the silane coupling agent (E) is 1 ⁇ 2 mol or less with respect to 1 mol of the NCO group of the NCO-terminated urethane prepolymer (D). More preferably, it is 1/4 to 1/2 mole. Within these ranges, the resin can have a high molecular weight, and the characteristics of the resin can be obtained. Moreover, the thermal coloring derived from the residual amino group in the silane coupling agent (E) can be suppressed.
  • a silane coupling agent (E ′) having one amino group may be used in combination, but the NCO group 1 of the NCO-terminated urethane prepolymer (D)
  • the silane coupling agent (E ′) is preferably 0.3 mol or less with respect to mol. More preferably, it is preferably 0.2 mol or less, and more preferably 0 mol. Within these ranges, the resin can have a high molecular weight, and the characteristics of the resin can be obtained.
  • the total of amino groups of the silane coupling agent (E) and the silane coupling agent (E ′) having one amino group is the NCO-terminated urethane prepolymer (D ) NCO group equivalent or less.
  • the silane coupling agent (E ′) having one amino group include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, and the like. . These can use 1 type, or 2 or more types.
  • the NCO group amount of the NCO-terminated urethane prepolymer (D) is the sum of the number of NCO groups of the polyisocyanate component (C), the active hydrogen group-containing cationic salt-forming group-containing compound (A), and the polyol component (B). Calculated from the difference from the number of active hydrogen groups.
  • the silane coupling agent (E) is preferably 0.01 to 0.12 mol and more preferably 0.02 to 0.08 mol with respect to 100 parts by mass of the NCO-terminated urethane prepolymer (D). Within these ranges, stability and resin characteristics can be obtained.
  • the water dispersion (X) further contains a condensate obtained by condensing the condensate (F ′) of the compound (F) and / or (F) represented by the formula (2).
  • Dispersion (Y) is also a preferred embodiment.
  • R 3 a Si (OR 4 ) b (2) (Wherein R 3 is a hydrocarbon group having 1 to 10 carbon atoms, a is 0 to 2, b is 2 to 4, and R 4 is a methyl group or an ethyl group)
  • the compound (F) is a compound described by the formula (2).
  • R 3 is a hydrocarbon group having 1 to 10 carbon atoms, and is preferably 1 or 2 or a phenyl group from the viewpoint of transparency, film formability, and flexibility of the silica composite resin.
  • b is 2-4.
  • R 4 is a methyl group or an ethyl group, and a methyl group is more preferable from the viewpoint of condensability.
  • the condensate (F ′) of (F) is not particularly limited, but (F ) Hydrolyzate condensate. These can use 1 type, or 2 or more types.
  • the total amount of the condensate (F ′) of the compound (F) and / or (F) is preferably 0 to 300 parts by mass with respect to 100 parts by mass of the NCO-terminated urethane prepolymer (D), and 50 to 200 More preferably, it is part by mass. Within these ranges, stability and film formability are good.
  • the amine value of the NCO-terminated urethane prepolymer (D) is preferably 7 to 60 mmKOH / g, more preferably 15 to 35 mmKOH / g. If it is these ranges, the emulsified particle diameter of the water dispersion is fine, and a stable dispersion of the organic-inorganic composite resin can be obtained. In addition, the film performance, water resistance, alkali resistance, and film formability are improved.
  • a polyvalent amine compound can be used.
  • the polyvalent amine compound is not particularly limited, and examples thereof include hydrazides and polyamines.
  • the hydrazides are not particularly limited, and examples thereof include hydrazine and adipic acid hydrazide.
  • polyamines examples include, but are not limited to, ethylenediamine, propylenediamine, hexylenediamine, isophoronediamine, xylylenediamine, piperazine, diphenylmethanediamine, ethyltolylenediamine, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetra Examples include ethylene pentamine. These can use 1 type, or 2 or more types. In order to suppress thermal coloring derived from amino groups, the total of amino groups of the silane coupling agent (E), the silane coupling agent (E ′) having one amino group, and the polyvalent amine compound is NCO terminal. It is necessary to make the NCO group equivalent or less of the urethane prepolymer (D).
  • the NCO-terminated urethane prepolymer (D) and the silane coupling agent (E) are 1 ⁇ 2 mol or less of the silane coupling agent with respect to 1 mol of the NCO group of the NCO-terminated urethane prepolymer (D).
  • a step of emulsifying the obtained resin (D or X ′) is included.
  • the step (i) is not particularly limited, and examples thereof include a method of reacting at 50 to 130 ° C. for 30 minutes to 3 hours in the absence of a solvent or in the presence of an organic solvent.
  • a catalyst usually used in the synthesis of urethane may be used.
  • the catalyst is not particularly limited, and examples thereof include tin octylate and bismuth octylate.
  • the step (ii) is not particularly limited, and examples thereof include a method of reacting at 10 to 40 ° C. for 10 to 45 minutes in the absence of a solvent or in the presence of an organic solvent. It is preferably in the presence of an organic solvent.
  • the step (iii) is not particularly limited, and examples thereof include a method of adding a neutralizing agent and water and emulsifying at 10 to 40 ° C. for 15 to 60 minutes and then removing the organic solvent. It can be carried out either after step (i) or after step (ii).
  • the silane coupling agent (E) may be reacted in an emulsified aqueous dispersion.
  • a chain extension step may be performed using a chain extender.
  • the production method of the aqueous dispersion (Y) of the present invention is not particularly limited, but in addition to the production method of the aqueous dispersion (X), step (i), step (ii), step (iii), (iv) A step of condensing the condensate (F ′) of the compound (F) and / or (F).
  • Step (iv) can be performed simultaneously with step (i) or step (ii), but from the viewpoint of emulsion stability, film transparency, flexibility, etc., it is preferable to perform condensation after step (iii). .
  • the emulsification stability of the aqueous dispersion of the present invention is not particularly limited, but in the methods described in the examples, it is preferable that there is no precipitation, and more preferable is ⁇ .
  • the film appearance of the aqueous dispersion of the present invention is not particularly limited, but in the methods described in the examples, it is preferably transparent and more preferably coarse particles are not seen.
  • the water resistance and MEK resistance of the film obtained from the aqueous dispersion of the present invention are not particularly limited, but in the methods described in the examples, it is preferably 30% or less, and can be measured without swelling, More preferably, it is 10% or less and 100% or less.
  • the pencil hardness of the film obtained from the aqueous dispersion of the present invention is not particularly limited, but is preferably B or more, more preferably F or more in the methods described in the examples.
  • the scratch resistance of the film obtained from the aqueous dispersion of the present invention is not particularly limited, it is preferably ⁇ in the method described in the examples.
  • the heat resistance of the film obtained from the aqueous dispersion of the present invention is not particularly limited, but in the methods described in the examples, it is preferably ⁇ , ⁇ ⁇ , or ⁇ , and ⁇ or ⁇ ⁇ . More preferably, it is ⁇ .
  • an emulsifier In the aqueous dispersion of the present invention, an emulsifier, a filler, a flame retardant, an antifoaming agent, an antibacterial agent, a rust preventive, a stabilizer, a plasticizer, a thickener and the like are within the range not inhibiting the effects of the present invention. Additives commonly used in aqueous dispersions of these resins can be included.
  • Example 3 A milky white translucent liquid aqueous dispersion was obtained in the same manner as in Example 2 except that tetraethoxysilane was changed to 500 parts of tetramethoxysilane.
  • Example 4 A milky white translucent liquid aqueous dispersion was obtained in the same manner as in Example 2 except that tetraethoxysilane was changed to 1000 parts of methyltrimethoxysilane.
  • Example 5 A milky white translucent liquid aqueous dispersion was obtained in the same manner as in Example 2 except that tetraethoxysilane was changed to 1000 parts of phenyltrimethoxysilane.
  • the obtained urethane prepolymer was mixed and diluted with 200 parts of MEK, mixed with 62 parts of dimethyl sulfate, and reacted at 50 ° C. for 15 minutes. Next, a mixed dilute solution of 105 parts of N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane and 500 parts of MEK was added and reacted with stirring to obtain urethane having an isocyanate group content of 0.8% (per solid content). A prepolymer was obtained. Next, 4000 parts of distilled water containing 46 parts of formic acid was added and mixed and emulsified. Then, after stirring at 40 ° C. for 3 hours, MEK was distilled off under reduced pressure to obtain a transparent liquid aqueous dispersion.
  • Example 7 In the same manner as in Example 6, a mixed diluted solution of 105 parts of N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane and 500 parts of MEK was added and reacted with stirring to obtain an isocyanate group content of 0.8%. After obtaining the urethane prepolymer (per solid content), 500 parts of tetramethoxysilane was mixed, and then 4000 parts of distilled water containing 46 parts of formic acid was added and mixed and emulsified. Then, after stirring at 40 ° C. for 3 hours, MEK was distilled off under reduced pressure to obtain a transparent liquid aqueous dispersion.
  • Example 8 A semitransparent liquid aqueous dispersion was obtained in the same manner as in Example 7 except that tetramethoxysilane was changed to 500 parts and mixed with tetraethoxysilane.
  • the urethane prepolymer was obtained.
  • the obtained urethane prepolymer was mixed and diluted with 1200 parts of MEK.
  • the obtained urethane prepolymer was mixed and diluted with 200 parts of MEK, mixed with 62 parts of dimethyl sulfate, reacted at 50 ° C. for 15 minutes, and then mixed and diluted with 500 parts of MEK.
  • 31 parts of ethylenediamine and 500 parts of MEK were added and reacted with stirring to obtain a urethane prepolymer having an isocyanate group content of 0.8% (per solid content).
  • 3500 parts of distilled water containing 23 parts of formic acid was added and mixed and emulsified. Then, after stirring at 40 ° C. for 3 hours, MEK was distilled off under reduced pressure to obtain a transparent liquid aqueous dispersion.
  • Comparative Example 4 In the same manner as in Comparative Example 3, after 3500 parts of distilled water containing 23 parts of formic acid was added and mixed and emulsified, 1000 parts of methyltrimethoxysilane was mixed, and then stirred at 40 ° C. for 3 hours, and then MEK was distilled off under reduced pressure. A white liquid aqueous dispersion was obtained.
  • a urethane dipolymer having an isocyanate group content of 0% (per solid content) was prepared by adding a mixed diluted solution of 153 parts of N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldimethoxysilane and 500 parts of MEK with stirring. Got. Thereafter, 64 parts of dimethyl sulfate was mixed and reacted at 50 ° C. for 15 minutes, and then 3500 parts of distilled water was added and mixed and emulsified. Then, after stirring at 40 ° C. for 3 hours, MEK was distilled off under reduced pressure to obtain a milky white liquid aqueous dispersion.
  • the obtained aqueous dispersion was applied onto a polypropylene film so as to have a film thickness of 30 ⁇ m, The test piece was dried at 80 ° C. for 60 minutes, peeled, and then dried at 120 ° C. for 30 minutes on a Teflon (registered trademark) petri dish.
  • Nonvolatile content weight Measured according to JIS K 6828. pH: Measured according to JIS Z8802. Viscosity: 20 ° C. using a B8M viscometer (manufactured by Tokyo Keiki Co., Ltd.) according to JIS Z8803 Measured with Particle size: Measured with MicrotracUPA-UZ152 (manufactured by Nikkiso Co., Ltd.), and the 50% average value was calculated as the particle size.
  • Emulsification stability Stored in a 40 ° C. incubator for 30 days and visually confirmed the emulsion stability. Comments were given for those with good emulsification stability, and for those with some problems. Film appearance: The appearance of the test film was visually observed.
  • Weight increase rate (weight after immersion ⁇ initial weight) / initial weight ⁇ 100
  • aqueous dispersion of the present invention has good emulsion stability, film appearance, water resistance, MEK resistance, pencil hardness, scratch resistance, and heat resistance.
  • the aqueous dispersion of the present invention is an aqueous dispersion, it has high environmental compatibility, and there is no need to use an explosion-proof structure for the equipment used. Moreover, the film

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
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Abstract

L'invention a pour objet de fournir une dispersion aqueuse qui se révèle excellente en termes de compatibilité du point de vue environnemental et de stabilité d'émulsion, et qui se révèle également satisfaisante en termes de caractéristiques de film obtenu, c'est-à-dire en termes d'apparence, de résistance à l'eau, de résistance au solvant, de dureté, de résistance aux éraflures et de résistance à la chaleur. La dispersion aqueuse (X) de l'invention est obtenue par réaction d'un composé (A) comprenant un groupe de formation de sel cationique à teneur en groupe hydrogène actif, d'un composant polyol (B) et d'un composant polyisocyanate (C), et comprend un produit de réaction d'un prépolymère uréthane à terminaison NCO (D) avec un agent de couplage au silane décrit dans la formule (1). L'agent de couplage au silane représente ½ mole par rapport à 1 mole du groupe NCO du prépolymère uréthane à terminaison NCO (D). （Ｒ１Ｏ）ｎＳｉ（Ｒ２）３－ｎＣ３Ｈ６ＮＨＣ２Ｈ４ＮＨ２ （１）(dans la formule, Ｒ１ représente un groupe hydrocarbure de 1 à 2 atomes de carbone, ｎ équivaut à 2 ou 3, et Ｒ２ représente un groupe méthyle)
PCT/JP2017/032990 2016-09-29 2017-09-13 Dispersion aqueuse WO2018061764A1 (fr)

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CN201780059315.5A CN109790266A (zh) 2016-09-29 2017-09-13 水分散体

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JP2016-190729 2016-09-29
JP2016190729A JP2018053109A (ja) 2016-09-29 2016-09-29 水分散体

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008274088A (ja) * 2007-04-27 2008-11-13 Nippon Nsc Ltd 水系反応性樹脂
JP2013241539A (ja) * 2012-05-22 2013-12-05 Dic Corp 水性複合樹脂組成物及びそれを用いたコーティング剤及び該コーティング剤の塗膜を有する物品
WO2015016069A1 (fr) * 2013-07-30 2015-02-05 三井化学株式会社 Dispersion de polyuréthane et stratifié de polyuréthane
JP2015182421A (ja) * 2014-03-26 2015-10-22 東レ株式会社 成型用積層フィルム
JP2015212347A (ja) * 2014-05-07 2015-11-26 オート化学工業株式会社 水性プライマー組成物

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100540584C (zh) * 2004-06-29 2009-09-16 大日本油墨化学工业株式会社 阳离子性聚氨酯树脂水分散体、含有其的喷墨接受剂以及使用其制成的喷墨记录介质
CN101967341B (zh) * 2010-09-29 2013-02-20 中国科学院长春应用化学研究所 一种水性耐磨紫外光固化的上光油及其制法
CN102796447B (zh) * 2012-07-12 2016-12-21 上海英诺威新材料科技有限公司 水性聚氨酯皮革涂饰剂及其制备方法
JP6124645B2 (ja) * 2013-03-27 2017-05-10 第一工業製薬株式会社 リチウム二次電池の電極用結着剤、該結着剤を用いて製造された電極を使用したリチウム二次電池
CN104610729A (zh) * 2015-02-11 2015-05-13 济南永昌利化工有限公司 一种阻燃水性聚氨酯及制备方法
CN110845696A (zh) * 2019-12-03 2020-02-28 山东天庆科技发展有限公司 一种水性聚氨酯树脂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008274088A (ja) * 2007-04-27 2008-11-13 Nippon Nsc Ltd 水系反応性樹脂
JP2013241539A (ja) * 2012-05-22 2013-12-05 Dic Corp 水性複合樹脂組成物及びそれを用いたコーティング剤及び該コーティング剤の塗膜を有する物品
WO2015016069A1 (fr) * 2013-07-30 2015-02-05 三井化学株式会社 Dispersion de polyuréthane et stratifié de polyuréthane
JP2015182421A (ja) * 2014-03-26 2015-10-22 東レ株式会社 成型用積層フィルム
JP2015212347A (ja) * 2014-05-07 2015-11-26 オート化学工業株式会社 水性プライマー組成物

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