WO2010023872A1 - Aqueous polyurethane dispersion and method for producing same - Google Patents
Aqueous polyurethane dispersion and method for producing same Download PDFInfo
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- WO2010023872A1 WO2010023872A1 PCT/JP2009/004082 JP2009004082W WO2010023872A1 WO 2010023872 A1 WO2010023872 A1 WO 2010023872A1 JP 2009004082 W JP2009004082 W JP 2009004082W WO 2010023872 A1 WO2010023872 A1 WO 2010023872A1
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- Prior art keywords
- diisocyanate
- polyurethane dispersion
- aqueous polyurethane
- mdi
- mass
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Classifications
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- 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
-
- 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation 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
- C08G18/28—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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
- C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
Definitions
- the present invention relates to an aqueous polyurethane dispersion using diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) and an alicyclic diisocyanate as an organic diisocyanate, and a method for producing the dispersion.
- MDI diphenylmethane diisocyanate
- alicyclic diisocyanate as an organic diisocyanate
- Paints, adhesives and coatings containing organic solvents have adverse effects on the human body, safety and health problems such as explosion and fire, and pollution problems such as air pollution and water pollution. In order to improve these problems, the development of water system has been actively conducted in recent years.
- Patent Document 1 discloses a water-dispersible polyurethane-based paint
- Patent Document 2 discloses a water-dispersible polyurethane-based adhesive.
- Patent Document 1 and Patent Document 2 basically do not satisfy all required performances such as adhesiveness, adhesion, and alkali resistance, and the appearance of such resins has been desired. .
- Patent Document 3 discloses a water-dispersed urethane-urea using a specific aromatic diisocyanate and an aliphatic diisocyanate that is price competitive and has excellent heat resistance, chemical resistance, mechanical strength, and the like. It is shown. However, the aromatic diisocyanate in Patent Document 3 has a reactivity that is too high, so that the amount of introduction in the production method and the polyurethane resin is limited.
- the present invention can stably disperse even when MDI is used as an organic diisocyanate, even if the production (stirring) equipment is not extremely sophisticated, and even when using ordinary synthesis equipment. It is an object of the present invention to obtain an aqueous polyurethane dispersion excellent in water resistance.
- Another object of the present invention is to obtain an aqueous polyurethane dispersion capable of providing a resin having both performances such as toughness and flexibility.
- the present invention further provides an aqueous polyurethane dispersion having excellent productivity (specifically, reaction control is easy, and the resulting polyurethane dispersion can be supplied to the market with stable quality). It aims to provide a method.
- MDI is 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “4,4′-MDI”), 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “2,2′-MDI”), It consists of three isomers of 2'-diphenylmethane diisocyanate (hereinafter abbreviated as "2,2'-MDI”).
- 4,4′-MDI 4,4′-diphenylmethane diisocyanate
- 2,2′-MDI 2,4′-diphenylmethane diisocyanate
- It consists of three isomers of 2'-diphenylmethane diisocyanate (hereinafter abbreviated as "2,2'-MDI”).
- the present invention is shown in the following (1) to (4).
- a polyurethane resin obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizer (D), and a chain extender (E) in water.
- the organic diisocyanate (A) is composed of diphenylmethane diisocyanate (A1) containing 75% by mass or more of 2,4′-diphenylmethane diisocyanate and alicyclic diisocyanate (A2), and the mass of (A1) and (A2)
- An aqueous polyurethane dispersion characterized in that the ratio is (A1) / (A2) 30/70 to 80/20.
- an aqueous polyurethane dispersion excellent in dispersibility can be obtained even if the production (stirring) equipment is not extremely sophisticated.
- an aqueous polyurethane dispersion capable of obtaining a resin having both performances such as toughness and flexibility as described above.
- the aqueous polyurethane dispersion of the present invention is obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizer (D), and a chain extender (E).
- an organic diisocyanate (A) a polymer polyol
- C carboxyl group-containing low molecular glycol
- D neutralizer
- E chain extender
- the organic diisocyanate (A) MDI (A1) containing 75% by mass or more of 2,4′-MDI and an alicyclic diisocyanate ( A2), and (A1) and (A2) are used in a mass ratio of 30/70 to 80/20.
- MDI ⁇ MDI (A1) containing 75% by mass or more of 2,4′-MDI>
- MDI is composed of three isomers: 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI.
- the isomer composition ratios of these MDIs in the present invention can ensure excellent dispersibility in the obtained aqueous polyurethane dispersion, and also can improve productivity (specifically, reaction control is easy and the resulting polyurethane dispersion can be obtained).
- the content of 2,4′-MDI is 75 mass% or more (preferably 80 mass%).
- the isomer composition ratio of MDI can be obtained from a calibration curve based on the area percentage of each peak obtained by GPC or gas chromatography (hereinafter abbreviated as “GC”).
- alicyclic diisocyanate (A2) examples include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, urethanized products, urea compounds, allophanates, biurets, carbodiimidides, uretoniminates, uretdiones, isocyanurates, and the like obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series alicyclic diisocyanate is also mentioned.
- hydrogenated diphenylmethane diisocyanate (4,4′-dicyclohexylmethane) is used as the alicyclic diisocyanate (A2) from the viewpoint of relatively mild reactivity and easy to obtain a desired aqueous polyurethane dispersion.
- Diisocyanate is preferably selected and used.
- isophorone diisocyanate is used as the alicyclic diisocyanate (A2) from the viewpoint that it is relatively mild in reactivity like the hydrogenated diphenylmethane diisocyanate and it is easy to obtain a desired aqueous polyurethane dispersion. It is also preferable to select and use.
- an MDI (A1 containing 75% by mass or more of the above 2,4′-MDI as the organic diisocyanate component (A) as necessary, on the premise that the performance desired in the present invention is satisfied. ) And an isocyanate group-containing component other than the alicyclic diisocyanate (A2).
- Examples of the isocyanate component that can be used in combination include MDI containing less than 75% by mass of 2,4′-MDI, an MDI-based condensate (a so-called dinuclear MDI having two benzene rings and two isocyanate groups, An organic polyisocyanate containing both MDI-based polynuclear condensates each having three or more benzene rings and isocyanate groups called so-called polynuclear bodies (in this case, the total of MDI and MDI-based multinuclear condensates is 100% by mass); Aromatics such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate Diisocyanate, tetramethylene di
- urethanized products urea compounds, allophanate compounds, biuret compounds, carbodiimide compounds, uretoniminate compounds, uretdione compounds, isocyanurate compounds obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series of isocyanate group containing compounds is also mentioned.
- polyester polyol, polyether polyol, polycarbonate polyol, or the like is used, and a normal one as a raw material of the polyurethane resin is used and is not particularly defined.
- the polymer polyol used in the present invention has a number average molecular weight of 500 to 6,000 (more preferably a number average molecular weight of 500 to 2,500, and particularly preferably a more stable dispersibility of an aqueous polyurethane dispersion, In addition, those having a number average molecular weight of 1,000 to 2,000 are preferable from the viewpoint that productivity can be reliably obtained.
- PPG polypropylene ethylene polyol
- PTG polytetramethylene ether glycol
- polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, malonic acid, adipic acid, 1,4-cyclohexyl dicarboxylic acid, maleic acid, fumaric acid, and other two types.
- Basic acids and the like ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, or glycerin, trimethylolpropane, pentaerythritol, etc.
- Polyester polyols obtained by the polycondensation reaction are employed. Furthermore, cyclic esters such as ⁇ -caprolactone, polyester amide polyols in which a part of the diol is changed to amines such as hexamethylene diamine and isophorone diamine can be used.
- Polyether polyols include the above diols, polyols, or these and amines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, alkylene oxides such as ethylene oxide and propylene oxide, and methylglycidyl.
- a polyether polyol obtained by addition polymerization of an ether, an alkyl such as phenyl glycidyl ether or an aryl glycidyl ether, a cyclic ether such as tetrahydrofuran is used.
- polycarbonate polyol a polycarbonate polyol obtained by a reaction of the diols or polyols with ethylene carbonate, diethyl carbonate, diphenyl carbonate or the like is used.
- a fatty acid having two terminal hydroxyl groups is preferably used as the carboxyl group-containing low molecular glycol (C) used in the present invention.
- This fatty acid has two terminal hydroxyl groups as active hydrogen groups.
- the active hydrogen groups at both ends react with isocyanate groups and are incorporated into the main chain of the prepolymer, and the free carboxyl groups are hydrophilic, so It works to increase dispersibility.
- the fatty acid compound having an active hydrogen group include dimethylolpropionic acid and dimethylolbutanoic acid having two terminal hydroxyl groups.
- the neutralizing agent (D) used in the present invention neutralizes the carboxyl group of the carboxyl group-containing low molecular glycol incorporated in the urethane prepolymer main chain, and gives the effect of further improving the water dispersibility of the polyurethane resin.
- Examples of the neutralizing agent (D) include tertiary amines (such as triethylamine).
- ⁇ Chain extender (E)> As the chain extender (D) used in the present invention, a compound having 3 or more active hydrogens is used.
- the compound having 3 or more active hydrogens include ethylenediamine (EDA), ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, diethanolamine, diethylenetriamine (DETA), and triethylene. Examples include tetramine, tetraethylenepentamine, and pentaethylenehexamine.
- the aqueous polyurethane dispersion in the present invention comprises the specific organic diisocyanate (A), the polymer polyol (B), the carboxyl group-containing low molecular glycol (C), the neutralizer (D), and the chain extender (E). If necessary, a viscosity reducing agent having an effect of promoting dispersion in water (solubility in water of 0.1 to 40% by mass and flash point of 50 ° C. or more) can be added. .
- the viscosity reducing agent examples include dipropylene glycol dimethyl ether (trade name: dimethylpropylene diglycol (abbreviation: DMFDG, solubility in water: 37.0 mass%, flash point: 65 ° C.), diethylene glycol dibutyl ether (commercial product). Name: Dibutyldiglycol, Abbreviation: DBDG, Solubility in water: 0.3 mass%, Flash point: 122 ° C., N-methylpyrrolidone (abbreviation: NMP, Solubility in water: (optional) mass%, Flash point) : 91 ° C).
- DMFDG dimethylpropylene diglycol
- NMP N-methylpyrrolidone
- a metal catalyst such as dibutyltin dilaurate or zinc naphthenate, or triethylenediamine, if necessary, for the purpose of accelerating the reaction in forming a polyurethane resin.
- An amine catalyst such as N-methylmorpholine and the like, and a resinification catalyst (urethanization catalyst) as a urethane reaction curing catalyst (polymerization catalyst) can be used together.
- various additives include flame retardants, plasticizers, antioxidants, ultraviolet absorbers, fillers, Internal release agents, reinforcing materials, matting agents, conductivity imparting agents, charge control agents, antistatic agents, lubricants, and other processing aids can be used.
- the carboxyl group is neutralized with the tertiary amine (D) to obtain an isocyanate group-terminated prepolymer having a carboxylic acid amine salt and having improved water dispersibility.
- the aqueous polyurethane dispersion of the present invention is obtained by performing a chain extension reaction with the chain extender (E).
- the step of emulsifying by dispersing the isocyanate group-terminated prepolymer in water is a system in which water is pre-charged rather than adding and dispersing water in the system in which the isocyanate group-terminated prepolymer is preliminarily charged. It is preferable to add and disperse an isocyanate group-terminated prepolymer therein to emulsify.
- Example 1 In order to lower the viscosity of 217.0 g of polyol A, 23.7 g of dimethylolpropionic acid (DMPA), and 2,000 ml of reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser As an optional component, 70.0 g of dipropylene glycol dimethyl ether (DMFDG) was charged, and the mixture was stirred at 90 ° C. and uniformly mixed. Next, after cooling to 60 ° C., 133.6 g of 2,4′-MDI and 33.4 g of hydrogenated diphenylmethane diisocyanate (hereinafter abbreviated as “H12-MDI” if necessary) were charged at 80 ° C. for 2 hours.
- DMPA dimethylolpropionic acid
- H12-MDI hydrogenated diphenylmethane diisocyanate
- amine water (15% aqueous solution) consisting of 66.3 g of water and 11.7 g of ethylenediamine (EDA) was charged in advance to carry out emulsification and chain extension reaction between water and amine.
- EDA ethylenediamine
- the reaction was terminated to obtain “PH-A1” which is an aqueous polyurethane dispersion (resin emulsion).
- Dispersion “PH-A1” has a solid content of 30%, a pH of 8.0, a viscosity at 25 ° C.
- an average particle diameter (measuring device: manufactured by Otsuka Electronics Co., Ltd .: electrophoretic light scattering system “ELS”) (Measured with ⁇ 800 ”) was 180 nm.
- compositions (each component) in Tables 1 and 2 are as follows.
- MDI (A1) having a 2,4′-MDI ratio of 75% by mass or more and hydrogenated diphenylmethane diisocyanate or isophorone diisocyanate were used as the alicyclic diisocyanate (A2).
- the average particle size was increased as the proportion of MDI (A1) having a proportion of 2,4′-MDI of 75% by mass or more was increased.
- aqueous polyurethane dispersion obtained by the present invention is suitably used in various water-based polyurethane resin applications such as aqueous paints and aqueous adhesives, particularly in fields where both excellent toughness and excellent flexibility are desired. be able to.
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Abstract
Disclosed is an aqueous polyurethane dispersion having excellent dispersibility and productivity (specifically, a polyurethane dispersion, reactions of which can be easily controlled, and which can be supplied to the market with a stable quality). The aqueous polyurethane dispersion can provide a resin which has toughness and flexibility at the same time. Also disclosed is a method for producing the dispersion. The aqueous polyurethane dispersion uses a diphenylmethane diisocyanate, which contains 2,4'-diphenylmethane diisocyanate at a ratio not less than a specific ratio, and an alicyclic diisocyanate at a ratio within a specific range.
Description
本発明は、ジフェニルメタンジイソシアネート（以下「ＭＤＩ」と略記。）と脂環族系ジイソシアネートを有機ジイソシアネートとして併せ用いた水性ポリウレタン分散体、及び、該分散体の製造方法に関する。
The present invention relates to an aqueous polyurethane dispersion using diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) and an alicyclic diisocyanate as an organic diisocyanate, and a method for producing the dispersion.
有機溶剤を含有する塗料、接着剤及びコーティング剤は、人体への悪影響、爆発火災等の安全衛生上の問題や、また、大気汚染、水質汚濁等の公害問題を有する。これらの問題点を改善するため、近年水系システムの開発が活発に行われている。
∙ Paints, adhesives and coatings containing organic solvents have adverse effects on the human body, safety and health problems such as explosion and fire, and pollution problems such as air pollution and water pollution. In order to improve these problems, the development of water system has been actively conducted in recent years.
この水系システム用の樹脂としては、アクリル樹脂、ポリウレタン樹脂、ポリエステル樹脂、ラテックス等様々な樹脂が用いられている。中でもポリウレタン樹脂は、耐久性、耐磨耗性等に優れているため、様々な使用用途で水系システムに応用する試みが広く行われている。例えば、特許文献１は水分散性ポリウレタン系塗料が開示され、特許文献２は水分散性ポリウレタン系接着剤が開示されている。これらは、水系ポリウレタン樹脂単独系であるが、各樹脂の特徴を組み合わせるため、アクリルエマルジョンとポリウレタンエマルジョン等、様々な樹脂の組み合わせた系も検討されている。
As the resin for the aqueous system, various resins such as acrylic resin, polyurethane resin, polyester resin, and latex are used. Among them, polyurethane resin is excellent in durability, abrasion resistance, and the like, and therefore, attempts to apply it to an aqueous system in various usages are widely made. For example, Patent Document 1 discloses a water-dispersible polyurethane-based paint, and Patent Document 2 discloses a water-dispersible polyurethane-based adhesive. These are water-based polyurethane resins alone, but in order to combine the characteristics of each resin, a combination of various resins such as an acrylic emulsion and a polyurethane emulsion has been studied.
しかし、特許文献１及び特許文献２記載の水系ポリウレタン樹脂は、基本的に接着性、密着性、耐アルカリ性等、全ての要求性能を満たすものではなく、このような樹脂の出現が望まれていた。
However, the water-based polyurethane resins described in Patent Document 1 and Patent Document 2 basically do not satisfy all required performances such as adhesiveness, adhesion, and alkali resistance, and the appearance of such resins has been desired. .
これらを改良するものとして、特許文献３は、価格競争力があり、耐熱性・耐化学性、機械的強度等に優れた特定の芳香族ジイソシアネートと脂肪族ジイソシアネートを用いた水分散ウレタン－ウレアが示されている。しかしながら、特許文献３における芳香族ジイソシアネートでは、高すぎる反応性のため、製造方法やポリウレタン樹脂中に占める導入量が限定される。
As an improvement, Patent Document 3 discloses a water-dispersed urethane-urea using a specific aromatic diisocyanate and an aliphatic diisocyanate that is price competitive and has excellent heat resistance, chemical resistance, mechanical strength, and the like. It is shown. However, the aromatic diisocyanate in Patent Document 3 has a reactivity that is too high, so that the amount of introduction in the production method and the polyurethane resin is limited.
また、得られる樹脂のより高い機械的強度を得ることを目的に、芳香族ジイソシアネートとしてＭＤＩのみを導入する方法が検討されている（例えば、特許文献４並びに特許文献５を参照）。しかし、芳香族ジイソシアネートとしてＭＤＩを用いる場合、前記のとおり反応性が高すぎることから、極めて優れた製造（攪拌）設備が高度なものである必要である。また、製造（攪拌）設備が高度なものであるとしても、前記の反応性の高さから、分散体の製造が極めて困難である。
Also, for the purpose of obtaining higher mechanical strength of the obtained resin, a method of introducing only MDI as an aromatic diisocyanate has been studied (for example, see Patent Document 4 and Patent Document 5). However, when MDI is used as the aromatic diisocyanate, the reactivity is too high as described above, and therefore an extremely excellent production (stirring) facility needs to be sophisticated. Moreover, even if the production (stirring) equipment is sophisticated, it is extremely difficult to produce a dispersion because of the high reactivity.
さらに、近年、得られる樹脂について、強靱さと柔軟性といった両方の性能を併せ有することが要求される分野（用途）が出始めている。
Furthermore, in recent years, fields (uses) in which the obtained resin is required to have both performances such as toughness and flexibility have begun to appear.
本発明は、前記のような背景を鑑み、ＭＤＩを有機ジイソシアネートとして用いた場合
において、製造（攪拌）設備が極めて高度なものでなくても、通常の合成設備を用いても安定して分散性に優れた水性ポリウレタン分散体を得ること目的とする。 In view of the background as described above, the present invention can stably disperse even when MDI is used as an organic diisocyanate, even if the production (stirring) equipment is not extremely sophisticated, and even when using ordinary synthesis equipment. It is an object of the present invention to obtain an aqueous polyurethane dispersion excellent in water resistance.
において、製造（攪拌）設備が極めて高度なものでなくても、通常の合成設備を用いても安定して分散性に優れた水性ポリウレタン分散体を得ること目的とする。 In view of the background as described above, the present invention can stably disperse even when MDI is used as an organic diisocyanate, even if the production (stirring) equipment is not extremely sophisticated, and even when using ordinary synthesis equipment. It is an object of the present invention to obtain an aqueous polyurethane dispersion excellent in water resistance.
本発明はまた、前記のような強靱さと柔軟性といった両方の性能を併せ有する樹脂を供することが可能な、水性ポリウレタン分散体を得ること目的とする。
Another object of the present invention is to obtain an aqueous polyurethane dispersion capable of providing a resin having both performances such as toughness and flexibility.
本発明はさらに、生産性（具体的には、反応制御が容易であり、得られるポリウレタン分散体も安定した品質で市場への供給が可能であること）に優れた、水性ポリウレタン分散体の製造方法を提供することを目的とする。
The present invention further provides an aqueous polyurethane dispersion having excellent productivity (specifically, reaction control is easy, and the resulting polyurethane dispersion can be supplied to the market with stable quality). It aims to provide a method.
ＭＤＩは、４，４′－ジフェニルメタンジイソシアネート（以下「４，４′－ＭＤＩ」と略記。）、２，４′－ジフェニルメタンジイソシアネート（以下「２，２′－ＭＤＩ」と略記。）、並びに２，２′－ジフェニルメタンジイソシアネート（以下「２，２′－ＭＤＩ」と略記。）の３種類の異性体から構成される。本発明者らは、前記の一連の課題を解決すべく鋭意検討を重ねた結果、有機ジイソシアネートとして、２，４′－ＭＤＩを特定以上の比率で含有するＭＤＩと脂環族系ジイソシアネートとを特定の比率（質量比）で併せ用いることにより、前記の一連の課題を解決できることを見いだし、本発明を完成させるに至った。
MDI is 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “4,4′-MDI”), 2,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “2,2′-MDI”), It consists of three isomers of 2'-diphenylmethane diisocyanate (hereinafter abbreviated as "2,2'-MDI"). As a result of intensive studies to solve the above-mentioned series of problems, the present inventors have identified MDI containing 2,4′-MDI in a ratio exceeding a specific ratio and alicyclic diisocyanate as organic diisocyanate. It was found that the above-mentioned series of problems can be solved by using the above in combination (mass ratio), and the present invention has been completed.
即ち、本発明は以下の（１）～（４）に示されるものである。
That is, the present invention is shown in the following (1) to (4).
（１） 有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）、中和剤（Ｄ）、鎖延長剤（Ｅ）を反応させて得られるポリウレタン樹脂を水中に乳化させてなる水性ポリウレタン分散体において、
有機ジイソシアネート（Ａ）が、２，４′－ジフェニルメタンジイソシアネートを７５質量％以上含有するジフェニルメタンジイソシアネート（Ａ１）と、脂環族系ジイソシアネート（Ａ２）からなり、かつ、（Ａ１）と（Ａ２）の質量比が（Ａ１）／（Ａ２）＝３０／７０～８０／２０であることを特徴とする、水性ポリウレタン分散体。
（２） 脂環族系ジイソシアネート（Ａ２）が、水素添加ジフェニルメタンジイソシアネートであることを特徴とする、（１）に記載の水性ポリウレタン分散体。
（３） 脂環族系ジイソシアネート（Ａ２）が、イソホロンジイソシアネートであることを特徴とする、（１）に記載の水性ポリウレタン分散体。
（４） 有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基を含有する低分子グリコール（Ｃ）を反応させて得られるイソシアネート基末端プレポリマーを、中和剤（Ｄ）にて中和してから水中に分散させた後、鎖延長剤（Ｅ）にて鎖延長反応を行うことを特徴とする、（１）～（３）のいずれかに記載の水性ポリウレタン分散体の製造方法。 (1) A polyurethane resin obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizer (D), and a chain extender (E) in water. In the aqueous polyurethane dispersion obtained by emulsification,
The organic diisocyanate (A) is composed of diphenylmethane diisocyanate (A1) containing 75% by mass or more of 2,4′-diphenylmethane diisocyanate and alicyclic diisocyanate (A2), and the mass of (A1) and (A2) An aqueous polyurethane dispersion characterized in that the ratio is (A1) / (A2) = 30/70 to 80/20.
(2) The aqueous polyurethane dispersion according to (1), wherein the alicyclic diisocyanate (A2) is hydrogenated diphenylmethane diisocyanate.
(3) The aqueous polyurethane dispersion according to (1), wherein the alicyclic diisocyanate (A2) is isophorone diisocyanate.
(4) Neutralizing an isocyanate group-terminated prepolymer obtained by reacting an organic diisocyanate (A), a polymer polyol (B), and a low molecular glycol (C) containing a carboxyl group with a neutralizing agent (D). Then, after being dispersed in water, a chain extension reaction is performed with a chain extender (E), and the method for producing an aqueous polyurethane dispersion according to any one of (1) to (3),
有機ジイソシアネート（Ａ）が、２，４′－ジフェニルメタンジイソシアネートを７５質量％以上含有するジフェニルメタンジイソシアネート（Ａ１）と、脂環族系ジイソシアネート（Ａ２）からなり、かつ、（Ａ１）と（Ａ２）の質量比が（Ａ１）／（Ａ２）＝３０／７０～８０／２０であることを特徴とする、水性ポリウレタン分散体。
（２） 脂環族系ジイソシアネート（Ａ２）が、水素添加ジフェニルメタンジイソシアネートであることを特徴とする、（１）に記載の水性ポリウレタン分散体。
（３） 脂環族系ジイソシアネート（Ａ２）が、イソホロンジイソシアネートであることを特徴とする、（１）に記載の水性ポリウレタン分散体。
（４） 有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基を含有する低分子グリコール（Ｃ）を反応させて得られるイソシアネート基末端プレポリマーを、中和剤（Ｄ）にて中和してから水中に分散させた後、鎖延長剤（Ｅ）にて鎖延長反応を行うことを特徴とする、（１）～（３）のいずれかに記載の水性ポリウレタン分散体の製造方法。 (1) A polyurethane resin obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizer (D), and a chain extender (E) in water. In the aqueous polyurethane dispersion obtained by emulsification,
The organic diisocyanate (A) is composed of diphenylmethane diisocyanate (A1) containing 75% by mass or more of 2,4′-diphenylmethane diisocyanate and alicyclic diisocyanate (A2), and the mass of (A1) and (A2) An aqueous polyurethane dispersion characterized in that the ratio is (A1) / (A2) = 30/70 to 80/20.
(2) The aqueous polyurethane dispersion according to (1), wherein the alicyclic diisocyanate (A2) is hydrogenated diphenylmethane diisocyanate.
(3) The aqueous polyurethane dispersion according to (1), wherein the alicyclic diisocyanate (A2) is isophorone diisocyanate.
(4) Neutralizing an isocyanate group-terminated prepolymer obtained by reacting an organic diisocyanate (A), a polymer polyol (B), and a low molecular glycol (C) containing a carboxyl group with a neutralizing agent (D). Then, after being dispersed in water, a chain extension reaction is performed with a chain extender (E), and the method for producing an aqueous polyurethane dispersion according to any one of (1) to (3),
本発明により、ＭＤＩを有機ジイソシアネートとして用いた場合において、製造（攪拌）設備が極めて高度なものでなくても分散性に優れた水性ポリウレタン分散体を得ることが可能となった。
According to the present invention, when MDI is used as an organic diisocyanate, an aqueous polyurethane dispersion excellent in dispersibility can be obtained even if the production (stirring) equipment is not extremely sophisticated.
また、本発明により、前記のような強靱さと柔軟性といった両方の性能を併せ有する樹脂を得ることが可能な水性ポリウレタン分散体を供することも可能となった。
In addition, according to the present invention, it is also possible to provide an aqueous polyurethane dispersion capable of obtaining a resin having both performances such as toughness and flexibility as described above.
さらに、本発明により、ＭＤＩを有機ジイソシアネートとして用いた場合でも、生産性（具体的には、反応制御が容易であり、得られるポリウレタン分散体も安定した品質で市場への供給が可能であること）に優れた水性ポリウレタン分散体の製造方法を提供するこ
とすることも可能となった。 Furthermore, according to the present invention, even when MDI is used as an organic diisocyanate, productivity (specifically, reaction control is easy, and the resulting polyurethane dispersion can be supplied to the market with stable quality. It is also possible to provide a method for producing an aqueous polyurethane dispersion excellent in
とすることも可能となった。 Furthermore, according to the present invention, even when MDI is used as an organic diisocyanate, productivity (specifically, reaction control is easy, and the resulting polyurethane dispersion can be supplied to the market with stable quality. It is also possible to provide a method for producing an aqueous polyurethane dispersion excellent in
本発明をさらに詳細に説明する。
The present invention will be described in further detail.
本発明の水性ポリウレタン分散体は、有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）、中和剤（Ｄ）、鎖延長剤（Ｅ）を反応させて得られるポリウレタン樹脂を水中に乳化させてなる水性ポリウレタン分散体において、前記の有機ジイソシアネート（Ａ）として、２，４′－ＭＤＩを７５質量％以上含有するＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）からなり、かつ、（Ａ１）と（Ａ２）を質量比が３０／７０～８０／２０で併せ用いることを特徴としている。
The aqueous polyurethane dispersion of the present invention is obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizer (D), and a chain extender (E). In the aqueous polyurethane dispersion obtained by emulsifying the obtained polyurethane resin in water, as the organic diisocyanate (A), MDI (A1) containing 75% by mass or more of 2,4′-MDI and an alicyclic diisocyanate ( A2), and (A1) and (A2) are used in a mass ratio of 30/70 to 80/20.
＜有機ジイソシアネート（Ａ）＞
本発明の水性ポリウレタン分散体に用いられる有機ジイソシアネート（Ａ）としては、前記のとおり、２，４′－ＭＤＩを７５質量％以上含有するＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）とを、質量比で（Ａ１）／（Ａ２）＝３０／７０～８０／２０（好ましくは質量比で（Ａ１）／（Ａ２）＝４０／６０～７５／２５、中でも、得られる樹脂において極めて優れた強靱さと柔軟性の両方の性能として併せ有する樹脂が得られるとの観点から、とりわけ好ましくは、質量比で（Ａ１）／（Ａ２）＝４５／５５～７０／３０）の比率で併せ用いる。この比率を外れる場合、具体的には（Ａ１）／（Ａ２）＝０／１００～２９／７１の場合、優れた強靱さと柔軟性のいずれかまたは両方の性能を有さない樹脂が得られる（換言すれば、本発明の所望する性能を有する樹脂を得ることができない）といった不具合が生じる。また（Ａ１）／（Ａ２）＝８１／１９～１００／０の場合も、優れた強靱さと柔軟性のいずれかまたは両方の性能を有さない樹脂が得られる（換言すれば、本発明の所望する性能を有する樹脂を得ることができない）といった不具合が生じる。 <Organic diisocyanate (A)>
As described above, the organic diisocyanate (A) used in the aqueous polyurethane dispersion of the present invention includes MDI (A1) containing 75% by mass or more of 2,4′-MDI, alicyclic diisocyanate (A2), In terms of mass ratio (A1) / (A2) = 30/70 to 80/20 (preferably (A1) / (A2) = 40/60 to 75/25 in mass ratio, among which the resin obtained is extremely excellent. From the standpoint that a resin having both high toughness and flexibility properties can be obtained, it is particularly preferably used in a mass ratio of (A1) / (A2) = 45/55 to 70/30). When this ratio is not satisfied, specifically, when (A1) / (A2) = 0/100 to 29/71, a resin having excellent toughness and / or flexibility is obtained ( In other words, there is a problem that a resin having the performance desired by the present invention cannot be obtained. In the case of (A1) / (A2) = 81/19 to 100/0, a resin that does not have excellent toughness and / or flexibility can be obtained (in other words, desired resin of the present invention). Inability to obtain a resin having the performance to achieve this) occurs.
本発明の水性ポリウレタン分散体に用いられる有機ジイソシアネート（Ａ）としては、前記のとおり、２，４′－ＭＤＩを７５質量％以上含有するＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）とを、質量比で（Ａ１）／（Ａ２）＝３０／７０～８０／２０（好ましくは質量比で（Ａ１）／（Ａ２）＝４０／６０～７５／２５、中でも、得られる樹脂において極めて優れた強靱さと柔軟性の両方の性能として併せ有する樹脂が得られるとの観点から、とりわけ好ましくは、質量比で（Ａ１）／（Ａ２）＝４５／５５～７０／３０）の比率で併せ用いる。この比率を外れる場合、具体的には（Ａ１）／（Ａ２）＝０／１００～２９／７１の場合、優れた強靱さと柔軟性のいずれかまたは両方の性能を有さない樹脂が得られる（換言すれば、本発明の所望する性能を有する樹脂を得ることができない）といった不具合が生じる。また（Ａ１）／（Ａ２）＝８１／１９～１００／０の場合も、優れた強靱さと柔軟性のいずれかまたは両方の性能を有さない樹脂が得られる（換言すれば、本発明の所望する性能を有する樹脂を得ることができない）といった不具合が生じる。 <Organic diisocyanate (A)>
As described above, the organic diisocyanate (A) used in the aqueous polyurethane dispersion of the present invention includes MDI (A1) containing 75% by mass or more of 2,4′-MDI, alicyclic diisocyanate (A2), In terms of mass ratio (A1) / (A2) = 30/70 to 80/20 (preferably (A1) / (A2) = 40/60 to 75/25 in mass ratio, among which the resin obtained is extremely excellent. From the standpoint that a resin having both high toughness and flexibility properties can be obtained, it is particularly preferably used in a mass ratio of (A1) / (A2) = 45/55 to 70/30). When this ratio is not satisfied, specifically, when (A1) / (A2) = 0/100 to 29/71, a resin having excellent toughness and / or flexibility is obtained ( In other words, there is a problem that a resin having the performance desired by the present invention cannot be obtained. In the case of (A1) / (A2) = 81/19 to 100/0, a resin that does not have excellent toughness and / or flexibility can be obtained (in other words, desired resin of the present invention). Inability to obtain a resin having the performance to achieve this) occurs.
＜２，４′－ＭＤＩを７５質量％以上含有するＭＤＩ（Ａ１）＞
ＭＤＩは、前記のとおり、４，４′－ＭＤＩ、２，４′－ＭＤＩ、並びに２，２′－ＭＤＩの３種類の異性体から構成される。本発明におけるこれらのＭＤＩの異性体構成比は、得られる水性ポリウレタン分散体における優れた分散性を確保でき、また、生産性（具体的には、反応制御が容易であり、得られるポリウレタン分散体も安定した品質で市場への供給が可能であること）にも優れるとの観点から、ＭＤＩを１００質量％とした場合、２，４′－ＭＤＩの含有量が７５質量％以上（好ましくは８０質量％以上、とりわけ好ましくは、より安定した水性ポリウレタン分散体の分散性、並びに生産性を確実に併せ得られるとの観点から９５．０質量％以上）である必要がある。なお、ＭＤＩの異性体構成比は、ＧＰＣやガスクロマトグラフィー（以下「ＧＣ」と略記。）によって得られる各ピークの面積百分率を基に検量線から求めることができる。 <MDI (A1) containing 75% by mass or more of 2,4′-MDI>
As described above, MDI is composed of three isomers: 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI. The isomer composition ratios of these MDIs in the present invention can ensure excellent dispersibility in the obtained aqueous polyurethane dispersion, and also can improve productivity (specifically, reaction control is easy and the resulting polyurethane dispersion can be obtained). In view of the fact that the MDI is 100 mass%, the content of 2,4′-MDI is 75 mass% or more (preferably 80 mass%). It is necessary to be 95.0% by mass or more, particularly preferably from the viewpoint that the more stable dispersibility of the aqueous polyurethane dispersion and productivity can be reliably obtained. The isomer composition ratio of MDI can be obtained from a calibration curve based on the area percentage of each peak obtained by GPC or gas chromatography (hereinafter abbreviated as “GC”).
ＭＤＩは、前記のとおり、４，４′－ＭＤＩ、２，４′－ＭＤＩ、並びに２，２′－ＭＤＩの３種類の異性体から構成される。本発明におけるこれらのＭＤＩの異性体構成比は、得られる水性ポリウレタン分散体における優れた分散性を確保でき、また、生産性（具体的には、反応制御が容易であり、得られるポリウレタン分散体も安定した品質で市場への供給が可能であること）にも優れるとの観点から、ＭＤＩを１００質量％とした場合、２，４′－ＭＤＩの含有量が７５質量％以上（好ましくは８０質量％以上、とりわけ好ましくは、より安定した水性ポリウレタン分散体の分散性、並びに生産性を確実に併せ得られるとの観点から９５．０質量％以上）である必要がある。なお、ＭＤＩの異性体構成比は、ＧＰＣやガスクロマトグラフィー（以下「ＧＣ」と略記。）によって得られる各ピークの面積百分率を基に検量線から求めることができる。 <MDI (A1) containing 75% by mass or more of 2,4′-MDI>
As described above, MDI is composed of three isomers: 4,4'-MDI, 2,4'-MDI, and 2,2'-MDI. The isomer composition ratios of these MDIs in the present invention can ensure excellent dispersibility in the obtained aqueous polyurethane dispersion, and also can improve productivity (specifically, reaction control is easy and the resulting polyurethane dispersion can be obtained). In view of the fact that the MDI is 100 mass%, the content of 2,4′-MDI is 75 mass% or more (preferably 80 mass%). It is necessary to be 95.0% by mass or more, particularly preferably from the viewpoint that the more stable dispersibility of the aqueous polyurethane dispersion and productivity can be reliably obtained. The isomer composition ratio of MDI can be obtained from a calibration curve based on the area percentage of each peak obtained by GPC or gas chromatography (hereinafter abbreviated as “GC”).
＜脂環族系ジイソシアネート（Ａ２）＞
本発明に用いられる脂環族系ジイソシアネート（Ａ２）としては、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等が挙げられる。また、これらのポリメリック体、活性水素基含有化合物と反応させて得られるウレタン化物、ウレア化物、アロファネート化物、ビウレット化物、カルボジイミド化物、ウレトンイミン化物、ウレトジオン化物、イソシアヌレート化物等も挙げられる。さらに、これら一連の脂環族系ジイソシアネートの２種以上からなる混合物も挙げられる。 <Alicyclic diisocyanate (A2)>
Examples of the alicyclic diisocyanate (A2) used in the present invention include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, urethanized products, urea compounds, allophanates, biurets, carbodiimidides, uretoniminates, uretdiones, isocyanurates, and the like obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series alicyclic diisocyanate is also mentioned.
本発明に用いられる脂環族系ジイソシアネート（Ａ２）としては、イソホロンジイソシアネート、水素添加トリレンジイソシアネート、水素添加キシレンジイソシアネート、水素添加ジフェニルメタンジイソシアネート等が挙げられる。また、これらのポリメリック体、活性水素基含有化合物と反応させて得られるウレタン化物、ウレア化物、アロファネート化物、ビウレット化物、カルボジイミド化物、ウレトンイミン化物、ウレトジオン化物、イソシアヌレート化物等も挙げられる。さらに、これら一連の脂環族系ジイソシアネートの２種以上からなる混合物も挙げられる。 <Alicyclic diisocyanate (A2)>
Examples of the alicyclic diisocyanate (A2) used in the present invention include isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. Further, urethanized products, urea compounds, allophanates, biurets, carbodiimidides, uretoniminates, uretdiones, isocyanurates, and the like obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series alicyclic diisocyanate is also mentioned.
本発明においては、比較的反応性がマイルドであり、所望される水性ポリウレタン分散体を得やすいとの観点から、脂環族系ジイソシアネート（Ａ２）として水素添加ジフェニ
ルメタンジイソシアネート（４，４′－ジシクロヘキシルメタンジイソシアネート）を選択して用いるのが好ましい。 In the present invention, hydrogenated diphenylmethane diisocyanate (4,4′-dicyclohexylmethane) is used as the alicyclic diisocyanate (A2) from the viewpoint of relatively mild reactivity and easy to obtain a desired aqueous polyurethane dispersion. Diisocyanate) is preferably selected and used.
ルメタンジイソシアネート（４，４′－ジシクロヘキシルメタンジイソシアネート）を選択して用いるのが好ましい。 In the present invention, hydrogenated diphenylmethane diisocyanate (4,4′-dicyclohexylmethane) is used as the alicyclic diisocyanate (A2) from the viewpoint of relatively mild reactivity and easy to obtain a desired aqueous polyurethane dispersion. Diisocyanate) is preferably selected and used.
本発明においては、前記の水素添加ジフェニルメタンジイソシアネートと同様に比較的反応性がマイルドであり、所望される水性ポリウレタン分散体を得やすいとの観点から、脂環族系ジイソシアネート（Ａ２）としてイソホロンジイソシアネートを選択して用いるのも好ましい。
In the present invention, isophorone diisocyanate is used as the alicyclic diisocyanate (A2) from the viewpoint that it is relatively mild in reactivity like the hydrogenated diphenylmethane diisocyanate and it is easy to obtain a desired aqueous polyurethane dispersion. It is also preferable to select and use.
本発明においては、本発明において所望される性能を満たすことを前提として、必要に応じて、有機ジイソシアネート成分（Ａ）として、前記の２，４′－ＭＤＩを７５質量％以上含有するＭＤＩ（Ａ１）、並びに、脂環族系ジイソシアネート（Ａ２）以外のイソシアネート基含有成分を併用することが出来る。併用できるイソシアネート成分としては、例えば、２，４′－ＭＤＩを７５質量％未満含有するＭＤＩ、ＭＤＩ系縮合体（いわゆる二核体と称されるベンゼン環及びイソシアネート基を各２個有するＭＤＩと、いわゆる多核体と称されるベンゼン環及びイソシアネート基を各３個以上有するＭＤＩ系多核縮合体を双方含有（この場合、ＭＤＩとＭＤＩ系多核縮合体の合計が１００質量％）する有機ポリイソシアネート）、２，４－トリレンジイソシアネート、２，６－トリレンジイソシアネート、キシレン－１，４－ジイソシアネート、キシレン－１，３－ジイソシアネート、テトラメチルキシレンジイソシアネート、ｍ－フェニレンジイソシアネート、ｐ－フェニレンジイソシアネート等の芳香族ジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、３－メチル－１，５－ペンタンジイソシアネート、リジンジイソシアネート等の脂肪族ジイソシアネート等が挙げられる。また、これらのポリメリック体、活性水素基含有化合物と反応させて得られるウレタン化物、ウレア化物、アロファネート化物、ビウレット化物、カルボジイミド化物、ウレトンイミン化物、ウレトジオン化物、イソシアヌレート化物等も挙げられる。さらに、これら一連のイソシアネート基含有化合物の２種以上からなる混合物も挙げられる。
In the present invention, an MDI (A1 containing 75% by mass or more of the above 2,4′-MDI as the organic diisocyanate component (A) as necessary, on the premise that the performance desired in the present invention is satisfied. ) And an isocyanate group-containing component other than the alicyclic diisocyanate (A2). Examples of the isocyanate component that can be used in combination include MDI containing less than 75% by mass of 2,4′-MDI, an MDI-based condensate (a so-called dinuclear MDI having two benzene rings and two isocyanate groups, An organic polyisocyanate containing both MDI-based polynuclear condensates each having three or more benzene rings and isocyanate groups called so-called polynuclear bodies (in this case, the total of MDI and MDI-based multinuclear condensates is 100% by mass); Aromatics such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene-1,4-diisocyanate, xylene-1,3-diisocyanate, tetramethylxylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate Diisocyanate, tetramethylene diiso Aneto, hexamethylene diisocyanate, 3-methyl-1,5-pentane diisocyanate, and aliphatic diisocyanates such as lysine diisocyanate. Further, urethanized products, urea compounds, allophanate compounds, biuret compounds, carbodiimide compounds, uretoniminate compounds, uretdione compounds, isocyanurate compounds obtained by reacting with these polymeric substances and active hydrogen group-containing compounds are also included. Furthermore, the mixture which consists of 2 or more types of these series of isocyanate group containing compounds is also mentioned.
＜高分子ポリオール（Ｂ）＞
本発明において使用される高分子ポリオールとしては、ポリエステルポリオール又はポリエーテルポリオール或いはポリカーボネートポリオールなどが使用され、それらにはポリウレタン樹脂の原材料としての通常のものが用いられて、特に規定はされない。 <Polymer polyol (B)>
As the polymer polyol used in the present invention, polyester polyol, polyether polyol, polycarbonate polyol, or the like is used, and a normal one as a raw material of the polyurethane resin is used and is not particularly defined.
本発明において使用される高分子ポリオールとしては、ポリエステルポリオール又はポリエーテルポリオール或いはポリカーボネートポリオールなどが使用され、それらにはポリウレタン樹脂の原材料としての通常のものが用いられて、特に規定はされない。 <Polymer polyol (B)>
As the polymer polyol used in the present invention, polyester polyol, polyether polyol, polycarbonate polyol, or the like is used, and a normal one as a raw material of the polyurethane resin is used and is not particularly defined.
本発明において使用される高分子ポリオールとしては、数平均分子量が５００～６，０００（より好ましくは数平均分子量が５００～２，５００、とりわけ好ましくは、より安定した水性ポリウレタン分散体の分散性、並びに生産性を確実に併せ得られるとの観点から、数平均分子量が１，０００～２，０００）のものが好ましく、代表的には、ポリプロピレンエチレンポリオール（ＰＰＧ）、ポリテトラメチレンエーテルグリコール（ＰＴＧ）などが例示される。
The polymer polyol used in the present invention has a number average molecular weight of 500 to 6,000 (more preferably a number average molecular weight of 500 to 2,500, and particularly preferably a more stable dispersibility of an aqueous polyurethane dispersion, In addition, those having a number average molecular weight of 1,000 to 2,000 are preferable from the viewpoint that productivity can be reliably obtained. Typically, polypropylene ethylene polyol (PPG), polytetramethylene ether glycol (PTG) And the like.
より具体的には、ポリエステルポリオールとしては、フタル酸、イソフタル酸、テレフタル酸、ナフタレンジカルボン酸、コハク酸、マロン酸、アジピン酸、１，４－シクロヘキシルジカルボン酸、マレイン酸、フマル酸、その他の二塩基酸などと、エチレングリコール、１，２－プロパンジオール、１，３－プロパンジオール、１，２－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、１，９－ノナンジオール、３，３－ジメチロールヘプタン、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、シクロヘキサン－１，４－ジオール、或いはグリセリン、トリメチロールプロパン、ペンタエリスリトールなどのポリオール類とからの重縮合反応により得られるポリエステルポリオールが使用される。さらに、ε－カプロラクトンなどの環状エステル、ジオールの一部をヘキサメチレンジアミンやイソホロンジアミンなどのアミン類に変更したポリエステルアミドポリ
オールなども使用し得る。 More specifically, polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, malonic acid, adipic acid, 1,4-cyclohexyl dicarboxylic acid, maleic acid, fumaric acid, and other two types. Basic acids and the like, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, or glycerin, trimethylolpropane, pentaerythritol, etc. From the polyols Polyester polyols obtained by the polycondensation reaction are employed. Furthermore, cyclic esters such as ε-caprolactone, polyester amide polyols in which a part of the diol is changed to amines such as hexamethylene diamine and isophorone diamine can be used.
オールなども使用し得る。 More specifically, polyester polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid, succinic acid, malonic acid, adipic acid, 1,4-cyclohexyl dicarboxylic acid, maleic acid, fumaric acid, and other two types. Basic acids and the like, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3,3-dimethylol heptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, or glycerin, trimethylolpropane, pentaerythritol, etc. From the polyols Polyester polyols obtained by the polycondensation reaction are employed. Furthermore, cyclic esters such as ε-caprolactone, polyester amide polyols in which a part of the diol is changed to amines such as hexamethylene diamine and isophorone diamine can be used.
ポリエーテルポリオールとしては、前記のジオール類、ポリオール類と、或いはこれらとエチレンジアミン、プロピレンジアミン、トルエンジアミン、メタフェニレンジアミン、ジフェニルメタンジアミンなどのアミン類と共に、エチレンオキサイド、プロピレンオキサイドなどのアルキレンオキサイド、メチルグリシジルエーテル、フェニルグリシジルエーテルなどのアルキル或いはアリールグリシジルエーテル、テトラヒドロフランなどの環状エーテルなどを付加重合することにより得られるポリエーテルポリオールが使用される。
Polyether polyols include the above diols, polyols, or these and amines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, alkylene oxides such as ethylene oxide and propylene oxide, and methylglycidyl. A polyether polyol obtained by addition polymerization of an ether, an alkyl such as phenyl glycidyl ether or an aryl glycidyl ether, a cyclic ether such as tetrahydrofuran is used.
ポリカーボネートポリオールとしては、前記のジオール類、ポリオール類と、エチレンカーボネート、ジエチルカーボネート、ジフェニルカーボネートなどとの反応により得られるポリカーボネートポリオールが使用される。
As the polycarbonate polyol, a polycarbonate polyol obtained by a reaction of the diols or polyols with ethylene carbonate, diethyl carbonate, diphenyl carbonate or the like is used.
＜カルボキシル基含有低分子グリコール（Ｃ）＞
本発明において用いられるカルボキシル基含有低分子グリコール（Ｃ）としては、末端水酸基を二個有す脂肪酸が好適に使用される。当脂肪酸は末端水酸基を活性水素基として二個有し、例えば両末端の活性水素基がイソシアネート基と反応してプレポリマーの主鎖に組み込まれ、遊離のカルボキシル基が親水性なのでプレポリマーの水分散性を高める作用をなす。活性水素基を有す脂肪酸化合物としては、例えば、末端水酸基を二個有すジメチロールプロピオン酸、ジメチロールブタン酸等が挙げられる。 <Carboxyl group-containing low molecular weight glycol (C)>
As the carboxyl group-containing low molecular glycol (C) used in the present invention, a fatty acid having two terminal hydroxyl groups is preferably used. This fatty acid has two terminal hydroxyl groups as active hydrogen groups. For example, the active hydrogen groups at both ends react with isocyanate groups and are incorporated into the main chain of the prepolymer, and the free carboxyl groups are hydrophilic, so It works to increase dispersibility. Examples of the fatty acid compound having an active hydrogen group include dimethylolpropionic acid and dimethylolbutanoic acid having two terminal hydroxyl groups.
本発明において用いられるカルボキシル基含有低分子グリコール（Ｃ）としては、末端水酸基を二個有す脂肪酸が好適に使用される。当脂肪酸は末端水酸基を活性水素基として二個有し、例えば両末端の活性水素基がイソシアネート基と反応してプレポリマーの主鎖に組み込まれ、遊離のカルボキシル基が親水性なのでプレポリマーの水分散性を高める作用をなす。活性水素基を有す脂肪酸化合物としては、例えば、末端水酸基を二個有すジメチロールプロピオン酸、ジメチロールブタン酸等が挙げられる。 <Carboxyl group-containing low molecular weight glycol (C)>
As the carboxyl group-containing low molecular glycol (C) used in the present invention, a fatty acid having two terminal hydroxyl groups is preferably used. This fatty acid has two terminal hydroxyl groups as active hydrogen groups. For example, the active hydrogen groups at both ends react with isocyanate groups and are incorporated into the main chain of the prepolymer, and the free carboxyl groups are hydrophilic, so It works to increase dispersibility. Examples of the fatty acid compound having an active hydrogen group include dimethylolpropionic acid and dimethylolbutanoic acid having two terminal hydroxyl groups.
＜中和剤（Ｄ）＞
本発明において用いられる中和剤（Ｄ）は、ウレタンプレポリマー主鎖に組み込まれたカルボキシル基含有低分子グリコールのカルボキシル基を中和して、ポリウレタン樹脂の水分散性をより高める効果を付与する。この中和剤（Ｄ）としては、例えば、第三級アミン（トリエチルアミン等）が挙げられる。 <Neutralizing agent (D)>
The neutralizing agent (D) used in the present invention neutralizes the carboxyl group of the carboxyl group-containing low molecular glycol incorporated in the urethane prepolymer main chain, and gives the effect of further improving the water dispersibility of the polyurethane resin. . Examples of the neutralizing agent (D) include tertiary amines (such as triethylamine).
本発明において用いられる中和剤（Ｄ）は、ウレタンプレポリマー主鎖に組み込まれたカルボキシル基含有低分子グリコールのカルボキシル基を中和して、ポリウレタン樹脂の水分散性をより高める効果を付与する。この中和剤（Ｄ）としては、例えば、第三級アミン（トリエチルアミン等）が挙げられる。 <Neutralizing agent (D)>
The neutralizing agent (D) used in the present invention neutralizes the carboxyl group of the carboxyl group-containing low molecular glycol incorporated in the urethane prepolymer main chain, and gives the effect of further improving the water dispersibility of the polyurethane resin. . Examples of the neutralizing agent (D) include tertiary amines (such as triethylamine).
＜鎖延長剤（Ｅ）＞
本発明において用いられる鎖延長剤（Ｄ）は、活性水素を３以上有する化合物が使用される。活性水素を３以上有する化合物としては、例えば、エチレンジアミン（ＥＤＡ）、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、ジエタノールアミン、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が挙げられる。 <Chain extender (E)>
As the chain extender (D) used in the present invention, a compound having 3 or more active hydrogens is used. Examples of the compound having 3 or more active hydrogens include ethylenediamine (EDA), ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, diethanolamine, diethylenetriamine (DETA), and triethylene. Examples include tetramine, tetraethylenepentamine, and pentaethylenehexamine.
本発明において用いられる鎖延長剤（Ｄ）は、活性水素を３以上有する化合物が使用される。活性水素を３以上有する化合物としては、例えば、エチレンジアミン（ＥＤＡ）、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、ネオペンチルグリコール、ジエタノールアミン、ジエチレントリアミン（ＤＥＴＡ）、トリエチレンテトラミン、テトラエチレンペンタミン、ペンタエチレンヘキサミン等が挙げられる。 <Chain extender (E)>
As the chain extender (D) used in the present invention, a compound having 3 or more active hydrogens is used. Examples of the compound having 3 or more active hydrogens include ethylenediamine (EDA), ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, diethanolamine, diethylenetriamine (DETA), and triethylene. Examples include tetramine, tetraethylenepentamine, and pentaethylenehexamine.
＜任意成分＞
本発明における水性ポリウレタン分散体は、前記の特定の有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）、中和剤（Ｄ）、並びに鎖延長剤（Ｅ）を必須とするが、必要に応じて、水への分散を促す効果を有する粘度低下剤（水への溶解度が０．１～４０質量％で引火点が５０℃以上）を添加することができる。該粘度低下剤の具体例としては、ジプロピレングリコールジメチルエーテル（商品名：ジメチルプロピレンジグリコール（略称：ＤＭＦＤＧ、水への溶解度：３７．０質量％、引火点：６５℃）、ジエチレングリコールジブチルエーテル（商品名：ジブチルジグリコール、略称：ＤＢＤＧ、水への溶解度：０．３質量％、引火点：１２２℃）、Ｎ－メチルピロリドン（略称：ＮＭＰ、水への溶解度：（任意）質量％、引火点：９１℃）等が挙げられる。 <Optional component>
The aqueous polyurethane dispersion in the present invention comprises the specific organic diisocyanate (A), the polymer polyol (B), the carboxyl group-containing low molecular glycol (C), the neutralizer (D), and the chain extender (E). If necessary, a viscosity reducing agent having an effect of promoting dispersion in water (solubility in water of 0.1 to 40% by mass and flash point of 50 ° C. or more) can be added. . Specific examples of the viscosity reducing agent include dipropylene glycol dimethyl ether (trade name: dimethylpropylene diglycol (abbreviation: DMFDG, solubility in water: 37.0 mass%, flash point: 65 ° C.), diethylene glycol dibutyl ether (commercial product). Name: Dibutyldiglycol, Abbreviation: DBDG, Solubility in water: 0.3 mass%, Flash point: 122 ° C., N-methylpyrrolidone (abbreviation: NMP, Solubility in water: (optional) mass%, Flash point) : 91 ° C).
本発明における水性ポリウレタン分散体は、前記の特定の有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）、中和剤（Ｄ）、並びに鎖延長剤（Ｅ）を必須とするが、必要に応じて、水への分散を促す効果を有する粘度低下剤（水への溶解度が０．１～４０質量％で引火点が５０℃以上）を添加することができる。該粘度低下剤の具体例としては、ジプロピレングリコールジメチルエーテル（商品名：ジメチルプロピレンジグリコール（略称：ＤＭＦＤＧ、水への溶解度：３７．０質量％、引火点：６５℃）、ジエチレングリコールジブチルエーテル（商品名：ジブチルジグリコール、略称：ＤＢＤＧ、水への溶解度：０．３質量％、引火点：１２２℃）、Ｎ－メチルピロリドン（略称：ＮＭＰ、水への溶解度：（任意）質量％、引火点：９１℃）等が挙げられる。 <Optional component>
The aqueous polyurethane dispersion in the present invention comprises the specific organic diisocyanate (A), the polymer polyol (B), the carboxyl group-containing low molecular glycol (C), the neutralizer (D), and the chain extender (E). If necessary, a viscosity reducing agent having an effect of promoting dispersion in water (solubility in water of 0.1 to 40% by mass and flash point of 50 ° C. or more) can be added. . Specific examples of the viscosity reducing agent include dipropylene glycol dimethyl ether (trade name: dimethylpropylene diglycol (abbreviation: DMFDG, solubility in water: 37.0 mass%, flash point: 65 ° C.), diethylene glycol dibutyl ether (commercial product). Name: Dibutyldiglycol, Abbreviation: DBDG, Solubility in water: 0.3 mass%, Flash point: 122 ° C., N-methylpyrrolidone (abbreviation: NMP, Solubility in water: (optional) mass%, Flash point) : 91 ° C).
また、本発明における水性ポリウレタン分散体には、ポリウレタン樹脂を形成するうえで反応を促進させる目的から、必要に応じて、ジブチルチンジラウレートやナフテン酸亜
鉛のような金属系触媒、或いは、トリエチレンジアミン、Ｎ－メチルモルホリン等のようなアミン系触媒等、ウレタン反応の硬化触媒（重合触媒）としての樹脂化触媒（ウレタン化触媒）を併せ用いることができる。 Further, in the aqueous polyurethane dispersion in the present invention, a metal catalyst such as dibutyltin dilaurate or zinc naphthenate, or triethylenediamine, if necessary, for the purpose of accelerating the reaction in forming a polyurethane resin. An amine catalyst such as N-methylmorpholine and the like, and a resinification catalyst (urethanization catalyst) as a urethane reaction curing catalyst (polymerization catalyst) can be used together.
鉛のような金属系触媒、或いは、トリエチレンジアミン、Ｎ－メチルモルホリン等のようなアミン系触媒等、ウレタン反応の硬化触媒（重合触媒）としての樹脂化触媒（ウレタン化触媒）を併せ用いることができる。 Further, in the aqueous polyurethane dispersion in the present invention, a metal catalyst such as dibutyltin dilaurate or zinc naphthenate, or triethylenediamine, if necessary, for the purpose of accelerating the reaction in forming a polyurethane resin. An amine catalyst such as N-methylmorpholine and the like, and a resinification catalyst (urethanization catalyst) as a urethane reaction curing catalyst (polymerization catalyst) can be used together.
さらに、本発明の水性ポリウレタン分散体に所望される物性を高め、また、各種物性を付加する目的から、各種の添加剤として、難燃剤、可塑剤、酸化防止剤、紫外線吸収剤、充填剤、内部離型剤、補強材、艶消し剤、導電性付与剤、帯電制御剤、帯電防止剤、滑剤、その他の加工助剤を用いることができる。
Furthermore, for the purpose of enhancing the desired physical properties of the aqueous polyurethane dispersion of the present invention and adding various physical properties, various additives include flame retardants, plasticizers, antioxidants, ultraviolet absorbers, fillers, Internal release agents, reinforcing materials, matting agents, conductivity imparting agents, charge control agents, antistatic agents, lubricants, and other processing aids can be used.
＜水性ポリウレタン分散体の製造方法＞
次に、本発明の水性ポリウレタン分散体の製造方法について述べる。前記一連の特定の有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）を反応させる。この際、前記の任意成分として挙げた水への分散を促す効果を有する粘度低下剤、並びに、ウレタン化触媒を反応系内に介在させてもよい。次いで、第三級アミン（Ｄ）にてカルボキシル基を中和して、カルボン酸アミン塩を含有して水分散性の高められたイソシアネート基末端プレポリマーを得る。このイソシアネート基末端プレポリマーを水に分散させて乳化させた後に、鎖延長剤（Ｅ）にて鎖延長反応を行うこととにより、本発明の水性ポリウレタン分散体が得られる。 <Method for producing aqueous polyurethane dispersion>
Next, a method for producing the aqueous polyurethane dispersion of the present invention will be described. The series of specific organic diisocyanate (A), polymer polyol (B), and carboxyl group-containing low molecular glycol (C) are reacted. Under the present circumstances, you may interpose the viscosity reducing agent which has the effect which promotes the dispersion | distribution to the water mentioned as said arbitrary component, and a urethanization catalyst in a reaction system. Next, the carboxyl group is neutralized with the tertiary amine (D) to obtain an isocyanate group-terminated prepolymer having a carboxylic acid amine salt and having improved water dispersibility. After this isocyanate group-terminated prepolymer is dispersed in water and emulsified, the aqueous polyurethane dispersion of the present invention is obtained by performing a chain extension reaction with the chain extender (E).
次に、本発明の水性ポリウレタン分散体の製造方法について述べる。前記一連の特定の有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）を反応させる。この際、前記の任意成分として挙げた水への分散を促す効果を有する粘度低下剤、並びに、ウレタン化触媒を反応系内に介在させてもよい。次いで、第三級アミン（Ｄ）にてカルボキシル基を中和して、カルボン酸アミン塩を含有して水分散性の高められたイソシアネート基末端プレポリマーを得る。このイソシアネート基末端プレポリマーを水に分散させて乳化させた後に、鎖延長剤（Ｅ）にて鎖延長反応を行うこととにより、本発明の水性ポリウレタン分散体が得られる。 <Method for producing aqueous polyurethane dispersion>
Next, a method for producing the aqueous polyurethane dispersion of the present invention will be described. The series of specific organic diisocyanate (A), polymer polyol (B), and carboxyl group-containing low molecular glycol (C) are reacted. Under the present circumstances, you may interpose the viscosity reducing agent which has the effect which promotes the dispersion | distribution to the water mentioned as said arbitrary component, and a urethanization catalyst in a reaction system. Next, the carboxyl group is neutralized with the tertiary amine (D) to obtain an isocyanate group-terminated prepolymer having a carboxylic acid amine salt and having improved water dispersibility. After this isocyanate group-terminated prepolymer is dispersed in water and emulsified, the aqueous polyurethane dispersion of the present invention is obtained by performing a chain extension reaction with the chain extender (E).
この場合、イソシアネート基末端プレポリマーを水に分散させて乳化する工程は、イソシアネート基末端プレポリマーを予め仕込んだ系内に水を追加投入して分散させて乳化するより、水を予め仕込んだ系内にイソシアネート基末端プレポリマーを追加投入して分散させて乳化するのが好ましい。
In this case, the step of emulsifying by dispersing the isocyanate group-terminated prepolymer in water is a system in which water is pre-charged rather than adding and dispersing water in the system in which the isocyanate group-terminated prepolymer is preliminarily charged. It is preferable to add and disperse an isocyanate group-terminated prepolymer therein to emulsify.
以下、本発明を実施例により更に詳しく説明するが、本発明はこれらに限定して解釈されるものではない。なお、実施例及び比較例中において「部」並びに「％」は、断り書きがない限り各々「質量部」並びに「質量％」を示す。
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention should not be construed as being limited thereto. In the examples and comparative examples, “parts” and “%” indicate “parts by mass” and “mass%”, respectively, unless otherwise specified.
＜実施例１＞
撹拌機、温度計、窒素シール管、及び冷却器を装着した容量２，０００ｍｌの反応器に、ポリオールＡを２１７．０ｇ、ジメチロールプロピオン酸（ＤＭＰＡ）を２３．７ｇ、並びに低粘度化するための任意成分としてジプロピレングリコールジメチルエーテル（ＤＭＦＤＧ）を７０．０ｇ各々仕込み、９０℃にて攪拌を行い、均一に混合した。次いで、６０℃まで冷却した後２，４′－ＭＤＩを１３３．６ｇ、水素添加ジフェニルメタンジイソシアネート（以下、必要に応じて「Ｈ１２－ＭＤＩ」と略記。）を３３．４ｇ各々仕込み８０℃で２時間、攪拌を行いながら反応させた。次いで、低粘度化するための任意成分としてＮ－メチルピロリドン（ＮＭＰ）を７０．０ｇ仕込み、さらに１時間攪拌を行った。攪拌後、中和前のイソシアネート基含有量が４．１質量％であることを確認した後、トリエチルアミン（ＴＥＡ）を１７．９ｇ仕込んでカルボキシル基を中和して、末端にイソシアネート基を有するポリウレタンプレポリマーを得た。
次に、撹拌機（特殊機化工業（株）製ホモミクサー）を用いて、撹拌しながら水を７７３．７ｇ仕込んで転相させた。転相したらすぐに、あらかじめ水が６６．３ｇ、エチレンジアミン（ＥＤＡ）が１１．７ｇからなるアミン水（１５％水溶液）を仕込み、乳化・水とアミンによる鎖延長反応を行った。
ＦＴ－ＩＲによりイソシアネート基の存在が確認されなくなったところで反応を終了して、水性ポリウレタン分散体（樹脂エマルジョン）である「ＰＨ－Ａ１」を得た。分散体「ＰＨ－Ａ１」の固形分は３０％、ｐＨは８．０、２５℃の粘度は１５０ｍＰａ・ｓ、平均粒径（測定装置：大塚電子（株）製：電気泳動光散乱系「ＥＬＳ－８００」を用いて測定）は１８０ｎｍであった。 <Example 1>
In order to lower the viscosity of 217.0 g of polyol A, 23.7 g of dimethylolpropionic acid (DMPA), and 2,000 ml of reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser As an optional component, 70.0 g of dipropylene glycol dimethyl ether (DMFDG) was charged, and the mixture was stirred at 90 ° C. and uniformly mixed. Next, after cooling to 60 ° C., 133.6 g of 2,4′-MDI and 33.4 g of hydrogenated diphenylmethane diisocyanate (hereinafter abbreviated as “H12-MDI” if necessary) were charged at 80 ° C. for 2 hours. The reaction was conducted while stirring. Next, 70.0 g of N-methylpyrrolidone (NMP) was charged as an optional component for reducing the viscosity, and the mixture was further stirred for 1 hour. After stirring, after confirming that the isocyanate group content before neutralization is 4.1% by mass, 17.9 g of triethylamine (TEA) was added to neutralize the carboxyl group, and the polyurethane having an isocyanate group at the terminal A prepolymer was obtained.
Next, using a stirrer (Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.), 773.7 g of water was charged and the phases were changed while stirring. Immediately after the phase inversion, amine water (15% aqueous solution) consisting of 66.3 g of water and 11.7 g of ethylenediamine (EDA) was charged in advance to carry out emulsification and chain extension reaction between water and amine.
When the presence of isocyanate groups was no longer confirmed by FT-IR, the reaction was terminated to obtain “PH-A1” which is an aqueous polyurethane dispersion (resin emulsion). Dispersion “PH-A1” has a solid content of 30%, a pH of 8.0, a viscosity at 25 ° C. of 150 mPa · s, an average particle diameter (measuring device: manufactured by Otsuka Electronics Co., Ltd .: electrophoretic light scattering system “ELS”) (Measured with −800 ”) was 180 nm.
撹拌機、温度計、窒素シール管、及び冷却器を装着した容量２，０００ｍｌの反応器に、ポリオールＡを２１７．０ｇ、ジメチロールプロピオン酸（ＤＭＰＡ）を２３．７ｇ、並びに低粘度化するための任意成分としてジプロピレングリコールジメチルエーテル（ＤＭＦＤＧ）を７０．０ｇ各々仕込み、９０℃にて攪拌を行い、均一に混合した。次いで、６０℃まで冷却した後２，４′－ＭＤＩを１３３．６ｇ、水素添加ジフェニルメタンジイソシアネート（以下、必要に応じて「Ｈ１２－ＭＤＩ」と略記。）を３３．４ｇ各々仕込み８０℃で２時間、攪拌を行いながら反応させた。次いで、低粘度化するための任意成分としてＮ－メチルピロリドン（ＮＭＰ）を７０．０ｇ仕込み、さらに１時間攪拌を行った。攪拌後、中和前のイソシアネート基含有量が４．１質量％であることを確認した後、トリエチルアミン（ＴＥＡ）を１７．９ｇ仕込んでカルボキシル基を中和して、末端にイソシアネート基を有するポリウレタンプレポリマーを得た。
次に、撹拌機（特殊機化工業（株）製ホモミクサー）を用いて、撹拌しながら水を７７３．７ｇ仕込んで転相させた。転相したらすぐに、あらかじめ水が６６．３ｇ、エチレンジアミン（ＥＤＡ）が１１．７ｇからなるアミン水（１５％水溶液）を仕込み、乳化・水とアミンによる鎖延長反応を行った。
ＦＴ－ＩＲによりイソシアネート基の存在が確認されなくなったところで反応を終了して、水性ポリウレタン分散体（樹脂エマルジョン）である「ＰＨ－Ａ１」を得た。分散体「ＰＨ－Ａ１」の固形分は３０％、ｐＨは８．０、２５℃の粘度は１５０ｍＰａ・ｓ、平均粒径（測定装置：大塚電子（株）製：電気泳動光散乱系「ＥＬＳ－８００」を用いて測定）は１８０ｎｍであった。 <Example 1>
In order to lower the viscosity of 217.0 g of polyol A, 23.7 g of dimethylolpropionic acid (DMPA), and 2,000 ml of reactor equipped with a stirrer, thermometer, nitrogen seal tube and condenser As an optional component, 70.0 g of dipropylene glycol dimethyl ether (DMFDG) was charged, and the mixture was stirred at 90 ° C. and uniformly mixed. Next, after cooling to 60 ° C., 133.6 g of 2,4′-MDI and 33.4 g of hydrogenated diphenylmethane diisocyanate (hereinafter abbreviated as “H12-MDI” if necessary) were charged at 80 ° C. for 2 hours. The reaction was conducted while stirring. Next, 70.0 g of N-methylpyrrolidone (NMP) was charged as an optional component for reducing the viscosity, and the mixture was further stirred for 1 hour. After stirring, after confirming that the isocyanate group content before neutralization is 4.1% by mass, 17.9 g of triethylamine (TEA) was added to neutralize the carboxyl group, and the polyurethane having an isocyanate group at the terminal A prepolymer was obtained.
Next, using a stirrer (Homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.), 773.7 g of water was charged and the phases were changed while stirring. Immediately after the phase inversion, amine water (15% aqueous solution) consisting of 66.3 g of water and 11.7 g of ethylenediamine (EDA) was charged in advance to carry out emulsification and chain extension reaction between water and amine.
When the presence of isocyanate groups was no longer confirmed by FT-IR, the reaction was terminated to obtain “PH-A1” which is an aqueous polyurethane dispersion (resin emulsion). Dispersion “PH-A1” has a solid content of 30%, a pH of 8.0, a viscosity at 25 ° C. of 150 mPa · s, an average particle diameter (measuring device: manufactured by Otsuka Electronics Co., Ltd .: electrophoretic light scattering system “ELS”) (Measured with −800 ”) was 180 nm.
＜実施例２～１４、比較例１～１０＞
表１並びに表２に示す組成（配合比）に従って、前記の実施例１と同じ方法に基づいて、水性ポリウレタン分散体（樹脂エマルジョン）である「ＰＨ－Ａ２」～「ＰＨ－Ａ７」、「ＰＨ－Ｂ１」～「ＰＨ－Ｂ５」、「ＰＩ－Ａ１」～「ＰＩ－Ａ７」、並びに「ＰＩ－Ｂ１」～「ＰＩ－Ｂ５」、を得た。但し、これらのうち「ＰＨ－Ｂ４」（比較例４）と「ＰＩ－Ｂ４」（比較例９）については、水を仕込み始めた時点で、イソシアネート基と水との過度な反応性の高さに起因すると思われる発泡が起きたため、水性ポリウレタン分散体の製造を中止した。 <Examples 2 to 14, Comparative Examples 1 to 10>
According to the composition (blending ratio) shown in Table 1 and Table 2, the aqueous polyurethane dispersions (resin emulsions) “PH-A2” to “PH-A7”, “PH” -B1 "to" PH-B5 "," PI-A1 "to" PI-A7 ", and" PI-B1 "to" PI-B5 "were obtained. However, among these, “PH-B4” (Comparative Example 4) and “PI-B4” (Comparative Example 9) have an excessively high reactivity between isocyanate groups and water at the time when charging of water begins. The production of the aqueous polyurethane dispersion was discontinued due to foaming that was believed to be due to.
表１並びに表２に示す組成（配合比）に従って、前記の実施例１と同じ方法に基づいて、水性ポリウレタン分散体（樹脂エマルジョン）である「ＰＨ－Ａ２」～「ＰＨ－Ａ７」、「ＰＨ－Ｂ１」～「ＰＨ－Ｂ５」、「ＰＩ－Ａ１」～「ＰＩ－Ａ７」、並びに「ＰＩ－Ｂ１」～「ＰＩ－Ｂ５」、を得た。但し、これらのうち「ＰＨ－Ｂ４」（比較例４）と「ＰＩ－Ｂ４」（比較例９）については、水を仕込み始めた時点で、イソシアネート基と水との過度な反応性の高さに起因すると思われる発泡が起きたため、水性ポリウレタン分散体の製造を中止した。 <Examples 2 to 14, Comparative Examples 1 to 10>
According to the composition (blending ratio) shown in Table 1 and Table 2, the aqueous polyurethane dispersions (resin emulsions) “PH-A2” to “PH-A7”, “PH” -B1 "to" PH-B5 "," PI-A1 "to" PI-A7 ", and" PI-B1 "to" PI-B5 "were obtained. However, among these, “PH-B4” (Comparative Example 4) and “PI-B4” (Comparative Example 9) have an excessively high reactivity between isocyanate groups and water at the time when charging of water begins. The production of the aqueous polyurethane dispersion was discontinued due to foaming that was believed to be due to.
前記の表１並びに表２における組成（各成分）の詳細は、以下のとおりである。
Details of the compositions (each component) in Tables 1 and 2 are as follows.
＜２，４′－ＭＤＩ（本発明の有機ジイソシアネート（Ａ１）に相当）＞
（ｉ） ＧＰＣによるＭＤＩのピーク面積比＝１００％
（ｉｉ） ＭＤＩ中の４，４′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｉｉｉ）ＭＤＩ中の２，４′－ＭＤＩの割合＝９８％（ＧＣによる測定）
（ｉｖ） ＭＤＩ中の２，２′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｖ） イソシアネート基含有量＝３３．６％
＜４，４′－ＭＤＩ＞
（ｉ） ＧＰＣによるＭＤＩのピーク面積比＝１００％
（ｉｉ） ＭＤＩ中の４，４′－ＭＤＩの割合＝９８％（ＧＣによる測定）
（ｉｉｉ）ＭＤＩ中の２，４′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｉｖ） ＭＤＩ中の２，２′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｖ） イソシアネート基含有量＝３３．６％
＜Ｈ１２－ＭＤＩ（本発明の有機ジイソシアネート（Ａ２）に相当）＞
水素添加ジフェニルメタンジイソシアネート
＜ＩＰＤＩ（本発明の有機ジイソシアネート（Ａ２）に相当）＞
イソホロンジイソシアネート
＜ポリオールＡ（本発明の高分子ポリオール（Ｂ）に相当）＞
ジエチルカーボネートと１，６－ヘキサンジオールを反応させて得られるポリカーボネートジオール
数平均分子量＝１，０００
公称官能基数＝２
公称水酸基価＝１１２．２（ｍｇＫＯＨ／ｇ）
＜ＤＭＰＡ（本発明のカルボキシル基含有低分子グリコール（Ｃ）に相当）＞
ジメチロールプロピオン酸
商品名「ＤＭＰＡ」（ＧＥＯスペシャリティケミカルズ社製）
＜ＤＭＦＤＧ（任意成分）＞
ジメチルプロピレンジグリコール（略称：ＤＭＦＤＧ）
水への溶解度：３７．０質量％
引火点：６５℃
商品名「ジメチルプロピレンジグリコール」（日本乳化剤（株）製）
＜ＮＭＰ（任意成分）＞
Ｎ－メチル－２－ピロリドン
水への溶解度：（任意）質量％
引火点：９１℃
商品名「Ｎ－メチル－２－ピロリドン」（三菱化学（株）製）
＜ＴＥＡ（本発明の中和剤（Ｄ）に相当）＞
トリエチルアミン
商品名「トリエチルアミン」（キシダ化学（株）製）
＜ＥＤＡ（本発明の鎖延長剤（Ｅ）に相当）＞
エチレンジアミン
商品名「エチレンジアミン」（東ソー（株）製）
＜水＞
精製水 <2,4′-MDI (corresponding to the organic diisocyanate (A1) of the present invention)>
(I) MDI peak area ratio by GPC = 100%
(Ii) Ratio of 4,4′-MDI in MDI = 1% (measured by GC)
(Iii) Ratio of 2,4′-MDI in MDI = 98% (measured by GC)
(Iv) Ratio of 2,2′-MDI in MDI = 1% (measured by GC)
(V) Isocyanate group content = 33.6%
<4,4'-MDI>
(I) MDI peak area ratio by GPC = 100%
(Ii) 4,4′-MDI ratio in MDI = 98% (measured by GC)
(Iii) Ratio of 2,4′-MDI in MDI = 1% (measured by GC)
(Iv) Ratio of 2,2′-MDI in MDI = 1% (measured by GC)
(V) Isocyanate group content = 33.6%
<H12-MDI (corresponding to the organic diisocyanate (A2) of the present invention)>
Hydrogenated diphenylmethane diisocyanate <IPDI (corresponding to the organic diisocyanate (A2) of the present invention)>
Isophorone diisocyanate <Polyol A (corresponding to the polymer polyol (B) of the present invention)>
Polycarbonate diol obtained by reacting diethyl carbonate and 1,6-hexanediol Number average molecular weight = 1,000
Nominal functional group = 2
Nominal hydroxyl value = 112.2 (mgKOH / g)
<DMPA (corresponding to carboxyl group-containing low molecular glycol (C) of the present invention)>
Dimethylolpropionic acid Trade name “DMPA” (manufactured by GEO Specialty Chemicals)
<DMFDG (optional component)>
Dimethylpropylene diglycol (abbreviation: DMFDG)
Solubility in water: 37.0% by mass
Flash point: 65 ° C
Product name "dimethylpropylene diglycol" (manufactured by Nippon Emulsifier Co., Ltd.)
<NMP (optional component)>
N-methyl-2-pyrrolidone Solubility in water: (optional) mass%
Flash point: 91 ° C
Product name "N-methyl-2-pyrrolidone" (Mitsubishi Chemical Corporation)
<TEA (corresponding to the neutralizing agent (D) of the present invention)>
Triethylamine Trade name "Triethylamine" (manufactured by Kishida Chemical Co., Ltd.)
<EDA (corresponding to the chain extender (E) of the present invention)>
Ethylenediamine Product name "Ethylenediamine" (manufactured by Tosoh Corporation)
<Water>
purified water
（ｉ） ＧＰＣによるＭＤＩのピーク面積比＝１００％
（ｉｉ） ＭＤＩ中の４，４′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｉｉｉ）ＭＤＩ中の２，４′－ＭＤＩの割合＝９８％（ＧＣによる測定）
（ｉｖ） ＭＤＩ中の２，２′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｖ） イソシアネート基含有量＝３３．６％
＜４，４′－ＭＤＩ＞
（ｉ） ＧＰＣによるＭＤＩのピーク面積比＝１００％
（ｉｉ） ＭＤＩ中の４，４′－ＭＤＩの割合＝９８％（ＧＣによる測定）
（ｉｉｉ）ＭＤＩ中の２，４′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｉｖ） ＭＤＩ中の２，２′－ＭＤＩの割合＝１％（ＧＣによる測定）
（ｖ） イソシアネート基含有量＝３３．６％
＜Ｈ１２－ＭＤＩ（本発明の有機ジイソシアネート（Ａ２）に相当）＞
水素添加ジフェニルメタンジイソシアネート
＜ＩＰＤＩ（本発明の有機ジイソシアネート（Ａ２）に相当）＞
イソホロンジイソシアネート
＜ポリオールＡ（本発明の高分子ポリオール（Ｂ）に相当）＞
ジエチルカーボネートと１，６－ヘキサンジオールを反応させて得られるポリカーボネートジオール
数平均分子量＝１，０００
公称官能基数＝２
公称水酸基価＝１１２．２（ｍｇＫＯＨ／ｇ）
＜ＤＭＰＡ（本発明のカルボキシル基含有低分子グリコール（Ｃ）に相当）＞
ジメチロールプロピオン酸
商品名「ＤＭＰＡ」（ＧＥＯスペシャリティケミカルズ社製）
＜ＤＭＦＤＧ（任意成分）＞
ジメチルプロピレンジグリコール（略称：ＤＭＦＤＧ）
水への溶解度：３７．０質量％
引火点：６５℃
商品名「ジメチルプロピレンジグリコール」（日本乳化剤（株）製）
＜ＮＭＰ（任意成分）＞
Ｎ－メチル－２－ピロリドン
水への溶解度：（任意）質量％
引火点：９１℃
商品名「Ｎ－メチル－２－ピロリドン」（三菱化学（株）製）
＜ＴＥＡ（本発明の中和剤（Ｄ）に相当）＞
トリエチルアミン
商品名「トリエチルアミン」（キシダ化学（株）製）
＜ＥＤＡ（本発明の鎖延長剤（Ｅ）に相当）＞
エチレンジアミン
商品名「エチレンジアミン」（東ソー（株）製）
＜水＞
精製水 <2,4′-MDI (corresponding to the organic diisocyanate (A1) of the present invention)>
(I) MDI peak area ratio by GPC = 100%
(Ii) Ratio of 4,4′-MDI in MDI = 1% (measured by GC)
(Iii) Ratio of 2,4′-MDI in MDI = 98% (measured by GC)
(Iv) Ratio of 2,2′-MDI in MDI = 1% (measured by GC)
(V) Isocyanate group content = 33.6%
<4,4'-MDI>
(I) MDI peak area ratio by GPC = 100%
(Ii) 4,4′-MDI ratio in MDI = 98% (measured by GC)
(Iii) Ratio of 2,4′-MDI in MDI = 1% (measured by GC)
(Iv) Ratio of 2,2′-MDI in MDI = 1% (measured by GC)
(V) Isocyanate group content = 33.6%
<H12-MDI (corresponding to the organic diisocyanate (A2) of the present invention)>
Hydrogenated diphenylmethane diisocyanate <IPDI (corresponding to the organic diisocyanate (A2) of the present invention)>
Isophorone diisocyanate <Polyol A (corresponding to the polymer polyol (B) of the present invention)>
Polycarbonate diol obtained by reacting diethyl carbonate and 1,6-hexanediol Number average molecular weight = 1,000
Nominal functional group = 2
Nominal hydroxyl value = 112.2 (mgKOH / g)
<DMPA (corresponding to carboxyl group-containing low molecular glycol (C) of the present invention)>
Dimethylolpropionic acid Trade name “DMPA” (manufactured by GEO Specialty Chemicals)
<DMFDG (optional component)>
Dimethylpropylene diglycol (abbreviation: DMFDG)
Solubility in water: 37.0% by mass
Flash point: 65 ° C
Product name "dimethylpropylene diglycol" (manufactured by Nippon Emulsifier Co., Ltd.)
<NMP (optional component)>
N-methyl-2-pyrrolidone Solubility in water: (optional) mass%
Flash point: 91 ° C
Product name "N-methyl-2-pyrrolidone" (Mitsubishi Chemical Corporation)
<TEA (corresponding to the neutralizing agent (D) of the present invention)>
Triethylamine Trade name "Triethylamine" (manufactured by Kishida Chemical Co., Ltd.)
<EDA (corresponding to the chain extender (E) of the present invention)>
Ethylenediamine Product name "Ethylenediamine" (manufactured by Tosoh Corporation)
<Water>
purified water
＜水性ポリウレタン分散体における分散状態の評価＞
各実施例並びに比較例（一部を除く）において得られた各々の水性ポリウレタン分散体について、各々２００ｇをガラス製サンプル瓶に仕込み、２５℃雰囲気下で２４時間静置
した。静置後、目視による分散状態の確認・評価を行った。結果を表１並びに表２に示す。
「○」：均一な分散状態が保持されている。
「△」：若干ながら液の相分離の兆候が見られる。
「×」：液の相分離が生じている。 <Evaluation of dispersion state in aqueous polyurethane dispersion>
About each water-based polyurethane dispersion obtained in each Example and comparative example (except one part), 200g was prepared for each in the glass sample bottle, and it left still in 25 degreeC atmosphere for 24 hours. After standing, the dispersion state was visually confirmed and evaluated. The results are shown in Table 1 and Table 2.
“◯”: A uniform dispersion state is maintained.
“Δ”: Some signs of liquid phase separation are observed.
“X”: Phase separation of the liquid occurs.
各実施例並びに比較例（一部を除く）において得られた各々の水性ポリウレタン分散体について、各々２００ｇをガラス製サンプル瓶に仕込み、２５℃雰囲気下で２４時間静置
した。静置後、目視による分散状態の確認・評価を行った。結果を表１並びに表２に示す。
「○」：均一な分散状態が保持されている。
「△」：若干ながら液の相分離の兆候が見られる。
「×」：液の相分離が生じている。 <Evaluation of dispersion state in aqueous polyurethane dispersion>
About each water-based polyurethane dispersion obtained in each Example and comparative example (except one part), 200g was prepared for each in the glass sample bottle, and it left still in 25 degreeC atmosphere for 24 hours. After standing, the dispersion state was visually confirmed and evaluated. The results are shown in Table 1 and Table 2.
“◯”: A uniform dispersion state is maintained.
“Δ”: Some signs of liquid phase separation are observed.
“X”: Phase separation of the liquid occurs.
＜水性ポリウレタン分散体を用いた膜物性の評価＞
＜参考実施例１～１４、参考比較例１～１０＞
各実施例並びに比較例（一部を除く）において得られた各々の水性ポリウレタン分散体について、板ガラスに水性ポリウレタン分散体をキャストして２５℃で５日間乾燥させて、所定の膜厚を有する乾式フィルムを作成し、以下に記載する物性測定を行った。一連の結果を表３並びに表４に示す。
＜引張物性＞
引張試験（２５℃：１００％モジュラス、破断時強度、伸び）：
引張速度＝２００ｍｍ／分
ＪＩＳ Ｋ６３０１（１９９５）の４号ダンベルにて打ち抜いてサンプルを作成した。
引張物性測定装置：オリエンテック（株）製 テンシロン ＵＴＡ－５００
＜引き裂き物性＞
引き裂き試験（２５℃：引き裂き強度）：
ＪＩＳ Ｋ７３１２に従って測定した。 <Evaluation of film properties using aqueous polyurethane dispersion>
<Reference Examples 1 to 14 and Reference Comparative Examples 1 to 10>
For each of the aqueous polyurethane dispersions obtained in each of the examples and comparative examples (excluding some), the aqueous polyurethane dispersion was cast on a plate glass and dried at 25 ° C. for 5 days to have a predetermined film thickness. A film was prepared and the physical properties described below were measured. A series of results are shown in Tables 3 and 4.
<Tensile properties>
Tensile test (25 ° C .: 100% modulus, strength at break, elongation):
Tensile speed = 200 mm / min. A sample was prepared by punching with a No. 4 dumbbell of JIS K6301 (1995).
Tensile property measuring device: Tensilon UTA-500 manufactured by Orientec Co., Ltd.
<Tear properties>
Tear test (25 ° C .: tear strength):
It measured according to JIS K7312.
＜参考実施例１～１４、参考比較例１～１０＞
各実施例並びに比較例（一部を除く）において得られた各々の水性ポリウレタン分散体について、板ガラスに水性ポリウレタン分散体をキャストして２５℃で５日間乾燥させて、所定の膜厚を有する乾式フィルムを作成し、以下に記載する物性測定を行った。一連の結果を表３並びに表４に示す。
＜引張物性＞
引張試験（２５℃：１００％モジュラス、破断時強度、伸び）：
引張速度＝２００ｍｍ／分
ＪＩＳ Ｋ６３０１（１９９５）の４号ダンベルにて打ち抜いてサンプルを作成した。
引張物性測定装置：オリエンテック（株）製 テンシロン ＵＴＡ－５００
＜引き裂き物性＞
引き裂き試験（２５℃：引き裂き強度）：
ＪＩＳ Ｋ７３１２に従って測定した。 <Evaluation of film properties using aqueous polyurethane dispersion>
<Reference Examples 1 to 14 and Reference Comparative Examples 1 to 10>
For each of the aqueous polyurethane dispersions obtained in each of the examples and comparative examples (excluding some), the aqueous polyurethane dispersion was cast on a plate glass and dried at 25 ° C. for 5 days to have a predetermined film thickness. A film was prepared and the physical properties described below were measured. A series of results are shown in Tables 3 and 4.
<Tensile properties>
Tensile test (25 ° C .: 100% modulus, strength at break, elongation):
Tensile speed = 200 mm / min. A sample was prepared by punching with a No. 4 dumbbell of JIS K6301 (1995).
Tensile property measuring device: Tensilon UTA-500 manufactured by Orientec Co., Ltd.
<Tear properties>
Tear test (25 ° C .: tear strength):
It measured according to JIS K7312.
表１並びに表２に記載のとおり、２，４′－ＭＤＩの割合が７５質量％以上のＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）として水素添加ジフェニルメタンジイソシアネートまたはイソホロンジイソシアネートを併せ用いた場合、いずれも良好な水性ポリウレタン分散体が得られた。傾向として、２，４′－ＭＤＩの割合が７５質量％以上のＭＤＩ（Ａ１）の比率が高いほど平均粒径が大きいものが得られた。また、表１に記載のとおり、比較例として２，４′－ＭＤＩの割合が７５質量％以上のＭＤＩ（Ａ１）のみを用いた場合、または、同じく比較例として脂環族系ジイソシアネート（Ａ２）である水素添加ジフェニルメタンジイソシアネートまたはイソホロンジイソシアネートのいずれかを単独で用いた場合も、良好な水性ポリウレタン分散体が得られた。
As shown in Tables 1 and 2, MDI (A1) having a 2,4′-MDI ratio of 75% by mass or more and hydrogenated diphenylmethane diisocyanate or isophorone diisocyanate were used as the alicyclic diisocyanate (A2). In all cases, a good aqueous polyurethane dispersion was obtained. As a tendency, the average particle size was increased as the proportion of MDI (A1) having a proportion of 2,4′-MDI of 75% by mass or more was increased. Further, as described in Table 1, when only MDI (A1) having a 2,4′-MDI ratio of 75% by mass or more was used as a comparative example, or as a comparative example, alicyclic diisocyanate (A2) When either hydrogenated diphenylmethane diisocyanate or isophorone diisocyanate as above was used alone, a good aqueous polyurethane dispersion was obtained.
しかし、これら一連の水性ポリウレタン分散体を用いて得られた膜の物性を評価したところ、表３並びに表４に記載のとおり、本発明において所望される性能、即ち、強靱さと柔軟性といった両方の性能を併せ有する樹脂（膜）が得られるのは、２，４′－ＭＤＩの割合が７５質量％以上のＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）の質量比が（Ａ１）／（Ａ２）＝３０／７０～８０／２０の範囲内であるとの結果が得られた。また、これらの質量比が（Ａ１）／（Ａ２）＝４５／５５～７０／３０の範囲内においては、この優れた強靱さと優れた柔軟性の両方の性能を顕著に発現する結果が得られた。この結果は、脂環族系ジイソシアネート（Ａ２）として、水素添加ジフェニルメタンジイソシアネートまたはイソホロンジイソシアネートのいずれを用いた場合でも同じであった。この特定の質量比、即ち、２，４′－ＭＤＩの割合が７５質量％以上のＭＤＩ（Ａ１）と、脂環族系ジイソシアネート（Ａ２）の質量比が（Ａ１）／（Ａ２）＝３０／７０～８０／２０の範囲から外れた場合、優れた強靱さと柔軟性のいずれかまたは両方の性能を有さないといった結果が得られた。
However, when the physical properties of the films obtained using these series of aqueous polyurethane dispersions were evaluated, as shown in Table 3 and Table 4, the performance desired in the present invention, that is, both toughness and flexibility were obtained. A resin (film) having both performances is obtained when the mass ratio of MDI (A1) having a ratio of 2,4′-MDI of 75% by mass or more and alicyclic diisocyanate (A2) is (A1) / The result that (A2) was in the range of 30/70 to 80/20 was obtained. In addition, when these mass ratios are within the range of (A1) / (A2) = 45/55 to 70/30, a result of remarkably expressing both the performance of this excellent toughness and excellent flexibility is obtained. It was. This result was the same when either hydrogenated diphenylmethane diisocyanate or isophorone diisocyanate was used as the alicyclic diisocyanate (A2). This specific mass ratio, that is, the mass ratio of MDI (A1) in which the ratio of 2,4′-MDI is 75 mass% or more and the alicyclic diisocyanate (A2) is (A1) / (A2) = 30 / Out of the 70-80 / 20 range, results were obtained that did not have either superior toughness and / or flexibility performance.
本発明により得られる水性ポリウレタン分散体は、水性塗料や水性接着剤等といった各種の水系ポリウレタン樹脂用途、特に、優れた強靱さと優れた柔軟性といった両方の性能が所望される分野において、好適に用いることができる。
The aqueous polyurethane dispersion obtained by the present invention is suitably used in various water-based polyurethane resin applications such as aqueous paints and aqueous adhesives, particularly in fields where both excellent toughness and excellent flexibility are desired. be able to.
Claims (4)
- 有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基含有低分子グリコール（Ｃ）、中和剤（Ｄ）、鎖延長剤（Ｅ）を反応させて得られるポリウレタン樹脂を水中に乳化させてなる水性ポリウレタン分散体において、
有機ジイソシアネート（Ａ）が、２，４′－ジフェニルメタンジイソシアネートを７５質量％以上含有するジフェニルメタンジイソシアネート（Ａ１）と、脂環族系ジイソシアネート（Ａ２）からなり、かつ、（Ａ１）と（Ａ２）の質量比が（Ａ１）／（Ａ２）＝３０／７０～８０／２０であることを特徴とする、水性ポリウレタン分散体。 A polyurethane resin obtained by reacting an organic diisocyanate (A), a polymer polyol (B), a carboxyl group-containing low molecular glycol (C), a neutralizing agent (D), and a chain extender (E) is emulsified in water. In the aqueous polyurethane dispersion,
The organic diisocyanate (A) is composed of diphenylmethane diisocyanate (A1) containing 75% by mass or more of 2,4′-diphenylmethane diisocyanate and alicyclic diisocyanate (A2), and the mass of (A1) and (A2) An aqueous polyurethane dispersion characterized in that the ratio is (A1) / (A2) = 30/70 to 80/20. - 脂環族系ジイソシアネート（Ａ２）が、水素添加ジフェニルメタンジイソシアネートであることを特徴とする、請求項１に記載の水性ポリウレタン分散体。 The aqueous polyurethane dispersion according to claim 1, wherein the alicyclic diisocyanate (A2) is hydrogenated diphenylmethane diisocyanate.
- 脂環族系ジイソシアネート（Ａ２）が、イソホロンジイソシアネートであることを特徴とする、請求項１に記載の水性ポリウレタン分散体。 The aqueous polyurethane dispersion according to claim 1, wherein the alicyclic diisocyanate (A2) is isophorone diisocyanate.
- 有機ジイソシアネート（Ａ）、高分子ポリオール（Ｂ）、カルボキシル基を含有する低分子グリコール（Ｃ）を反応させて得られるイソシアネート基末端プレポリマーを、中和剤（Ｄ）にて中和してから水中に分散させた後、鎖延長剤（Ｅ）にて鎖延長反応を行うことを特徴とする、請求項１～３のいずれかに記載の水性ポリウレタン分散体の製造方法。 After neutralizing an isocyanate group-terminated prepolymer obtained by reacting an organic diisocyanate (A), a high-molecular polyol (B), and a low-molecular glycol (C) containing a carboxyl group with a neutralizing agent (D). The method for producing an aqueous polyurethane dispersion according to any one of claims 1 to 3, wherein a chain extension reaction is carried out with a chain extender (E) after being dispersed in water.
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| WO2013176256A1 (en) * | 2012-05-25 | 2013-11-28 | トーヨーポリマー株式会社 | Aqueous polyurethane dispersing element |
| JP5588570B2 (en) * | 2012-05-25 | 2014-09-10 | トーヨーポリマー株式会社 | Polyurethane aqueous dispersion, and film molded product and glove obtained therefrom |
| JP6705445B2 (en) * | 2015-04-07 | 2020-06-03 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, method for producing the same and use thereof |
| KR102077681B1 (en) * | 2018-09-20 | 2020-02-14 | 주식회사 터치그린 | method of preparing polyurea resin composition, polyurea resin composition prepared thereby, and industrial glove coated with polyurea resin composition |
| JP6828854B1 (en) * | 2019-05-14 | 2021-02-10 | Dic株式会社 | Urethane resin composition and synthetic leather |
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| JPH07507086A (en) * | 1992-06-04 | 1995-08-03 | アベシア ベスローテム ベンノットシヤップ | Aqueous polyurethane dispersion |
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| JPH10110094A (en) * | 1996-10-08 | 1998-04-28 | Nippon Polyurethane Ind Co Ltd | Water-base polyurethane emulsion composition and water-base emulsion coating material obtained therefrom |
| JP2003055431A (en) * | 2001-08-17 | 2003-02-26 | Nippon Polyurethane Ind Co Ltd | Aqueous polyurethane emulsion, and water-based adhesive and water-based coating material made by using it |
| JP2004501252A (en) * | 2000-06-22 | 2004-01-15 | ポーハング アイアン アンド スティール シーオー．，エルティディ． | Method for producing aqueous urethane resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07507086A (en) * | 1992-06-04 | 1995-08-03 | アベシア ベスローテム ベンノットシヤップ | Aqueous polyurethane dispersion |
| JPH10110095A (en) * | 1996-10-08 | 1998-04-28 | Nippon Polyurethane Ind Co Ltd | Water-base polyurethane-acrylic emulsion and water-base emulsion coating material obtained therefrom |
| JPH10110094A (en) * | 1996-10-08 | 1998-04-28 | Nippon Polyurethane Ind Co Ltd | Water-base polyurethane emulsion composition and water-base emulsion coating material obtained therefrom |
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| JP2010195977A (en) * | 2009-02-26 | 2010-09-09 | Nippon Polyurethane Ind Co Ltd | Aqueous polyurethane dispersion and method for producing the same |
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