JP2017066338A - Manufacturing method of emulsifier and dispersant and manufacturing method of water emulsification and water dispersion composition - Google Patents
Manufacturing method of emulsifier and dispersant and manufacturing method of water emulsification and water dispersion composition Download PDFInfo
- Publication number
- JP2017066338A JP2017066338A JP2015196598A JP2015196598A JP2017066338A JP 2017066338 A JP2017066338 A JP 2017066338A JP 2015196598 A JP2015196598 A JP 2015196598A JP 2015196598 A JP2015196598 A JP 2015196598A JP 2017066338 A JP2017066338 A JP 2017066338A
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- Japan
- Prior art keywords
- water
- producing
- emulsifying
- group
- dispersing agent
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000002270 dispersing agent Substances 0.000 title claims abstract description 63
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 60
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 55
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000004945 emulsification Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims abstract description 19
- 239000006185 dispersion Substances 0.000 title claims abstract description 17
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 31
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 31
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 30
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 28
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004821 distillation Methods 0.000 claims abstract description 14
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 31
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 25
- 239000000839 emulsion Substances 0.000 claims description 21
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 20
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 20
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 239000002574 poison Substances 0.000 claims description 11
- 231100000614 poison Toxicity 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000003960 organic solvent Substances 0.000 abstract description 14
- 239000000178 monomer Substances 0.000 abstract 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 19
- -1 glycol monoalkyl ether Chemical class 0.000 description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 14
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 13
- 239000007795 chemical reaction product Substances 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 11
- 229920000126 latex Polymers 0.000 description 10
- 229920005862 polyol Polymers 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 9
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 239000004816 latex Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 8
- 150000003077 polyols Chemical class 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 235000014113 dietary fatty acids Nutrition 0.000 description 7
- 229930195729 fatty acid Natural products 0.000 description 7
- 239000000194 fatty acid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000010409 thin film Substances 0.000 description 7
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229920000180 alkyd Polymers 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 2
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002075 main ingredient Substances 0.000 description 2
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Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
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- Paints Or Removers (AREA)
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- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、アロファネート変性イソシアネートからなる乳化性及びその安定性に優れた乳化・分散剤、これを用いた水乳化イソシアネート硬化剤及び水乳化硬化性組成物に関する。 The present invention relates to an emulsifying / dispersing agent excellent in emulsifiability and stability thereof composed of allophanate-modified isocyanate, a water emulsifying isocyanate curing agent and a water emulsifying curable composition using the same.
従来、接着剤や塗料等として使用される水性の(硬化性)組成物には、ポリイソシアネート成分として、水性のポリイソシアネートや、疎水性ポリイソシアネートをイソシアネート基含有ノニオン性化合物により水に乳化、分散して使用することが知られている。具体的には例えば、疎水性ポリイソシアネートをノニオン性基及びイソシアネート基含有ビニル系重合体で水分散したポリイソシアネート組成物、並びに水性硬化性組成物が知られている(例えば、特許文献1参照)。こうしたビニル系重合体を作製した場合、製造工程で有機溶剤を使用するため環境負荷が生じるという問題点がある。また、有機ジイソシアネートに疎水性基含有モノアルコールとノニオン性親水基含有一官能アルコールを同時にウレタン化反応、次いでアロファネート化反応させる乳化・分散剤が知られている(例えば、特許文献2参照)。しかしながら、これらに記載の乳化・分散剤は、臭気とポットライフが短いといった問題点があった。 Conventionally, aqueous (curable) compositions used as adhesives and paints are emulsified and dispersed in water with an isocyanate group-containing nonionic compound as an aqueous polyisocyanate or hydrophobic polyisocyanate as a polyisocyanate component. And is known to be used. Specifically, for example, a polyisocyanate composition in which a hydrophobic polyisocyanate is dispersed in water with a nonionic group and an isocyanate group-containing vinyl polymer, and an aqueous curable composition are known (for example, see Patent Document 1). . When such a vinyl polymer is produced, an organic solvent is used in the production process, resulting in a problem that an environmental load is generated. Also known is an emulsifying / dispersing agent in which a hydrophobic group-containing monoalcohol and a nonionic hydrophilic group-containing monofunctional alcohol are simultaneously urethanated and then allophanatized to an organic diisocyanate (see, for example, Patent Document 2). However, the emulsifying / dispersing agents described in these publications have a problem that odor and pot life are short.
近年、水系の接着剤や塗料等の分野においては、有機溶剤系の接着剤や塗料等と比較して塗膜物性を落とすことなく、効率的で作業しやすいように、乳化、分散が容易かつ長期に渡って安定であることが望まれている。本発明の目的は、有機溶剤を使用せず、また遊離の有機ジイソシアネートを蒸留により除去し、更に改善されたポットライフを有する、有機ポリイソシアネートおよび、これに用いる高分子化合物からなる主剤を乳化・分散させる、乳化・分散剤を提供することにある。 In recent years, in the field of water-based adhesives and paints, it is easy to emulsify and disperse so that it is efficient and easy to work without degrading the physical properties of the coating film compared to organic solvent-based adhesives and paints. It is desired to be stable over a long period of time. The object of the present invention is to emulsify an organic polyisocyanate having an improved pot life by removing organic diisocyanate by distillation without using an organic solvent and a polymer compound used therefor. It is to provide an emulsifying / dispersing agent to be dispersed.
本発明は、前述の課題を解決するために鋭意検討した結果、見出されたものである。すなわち本発明は以下の(1)〜(11)に示す実施形態を含むものである。 The present invention has been found as a result of intensive studies to solve the above-described problems. That is, the present invention includes embodiments shown in the following (1) to (11).
(1)以下の工程から得られる、乳化・分散剤の製造方法。
第一工程:有機ジイソシアネート(a)と、疎水性基含有モノアルコール(b)をアロファネート触媒の存在下で反応させる工程。
第二工程:触媒毒を添加して、アロファネート化反応を停止させる工程。
第三工程:遊離の有機ジイソシアネート(a)を蒸留により除去する工程。
第四工程:第三工程から得られたアロファネート変性イソシアネートと、ノニオン性親水基含有一官能アルコール(c)をアロファネート触媒の存在下で反応させる工程。
第五工程:触媒毒を添加して、アロファネート化反応を停止させる工程。
(1) A method for producing an emulsifier / dispersant obtained from the following steps.
First step: a step of reacting the organic diisocyanate (a) with a hydrophobic group-containing monoalcohol (b) in the presence of an allophanate catalyst.
Second step: A step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction.
(2)前記の有機ジイソシアネート(a)が、ヘキサメチレンジイソシアネートであることを特徴とする、上記(1)に記載の乳化・分散剤の製造方法。 (2) The method for producing an emulsifying / dispersing agent according to (1) above, wherein the organic diisocyanate (a) is hexamethylene diisocyanate.
(3)前記の遊離の有機ジイソシアネート(a)が0.5質量%以下であることを特徴とする、上記(1)又は(2)に記載の乳化・分散剤の製造方法。 (3) The method for producing an emulsifying / dispersing agent according to (1) or (2) above, wherein the free organic diisocyanate (a) is 0.5% by mass or less.
(4)前記の疎水性基含有モノアルコール(b)が、炭素数1〜20のアルキルモノアルコールであることを特徴とする、上記(1)乃至(3)のいずれかに記載の乳化・分散剤の製造方法。 (4) The emulsification / dispersion according to any one of (1) to (3) above, wherein the hydrophobic group-containing monoalcohol (b) is an alkyl monoalcohol having 1 to 20 carbon atoms. Manufacturing method.
(5)前記のノニオン性親水基含有一官能アルコール(c)が、下記(式1)で示されることを特徴とする、上記(1)乃至(4)のいずれかに記載の乳化・分散剤の製造方法
R1−O−(−R2−O−)n−H ・・・(式1)
(但し、R1はアルキル基を示し、R2はエチレン基を30モル%以上含有するアルキレン基を示す。nは1以上の整数を示す。)
(5) The emulsifying / dispersing agent according to any one of (1) to (4) above, wherein the nonionic hydrophilic group-containing monofunctional alcohol (c) is represented by the following (formula 1): R 1 —O — (— R 2 —O—) n—H (Formula 1)
(However, R 1 represents an alkyl group, R 2 represents an alkylene group containing 30 mol% or more of an ethylene group. N represents an integer of 1 or more.)
(6)前記の疎水性基含有モノアルコール(b)/ノニオン性親水基含有一官能アルコール(c)のモル比が(b)/(c)=10/90〜90/10であることを特徴とする、上記(1)乃至(5)のいずれかに記載の乳化・分散剤の製造方法。 (6) A molar ratio of the hydrophobic group-containing monoalcohol (b) / nonionic hydrophilic group-containing monofunctional alcohol (c) is (b) / (c) = 10/90 to 90/10. The method for producing an emulsifying / dispersing agent according to any one of (1) to (5) above.
(7)前記のノニオン性親水基含有一官能アルコール(c)の使用量が、前記の(a)、(b)、及び(c)の合計量中において10〜60質量%であることを特徴とする、上記(1)乃至(6)のいずれかに記載の乳化・分散剤の製造方法。 (7) The amount of the nonionic hydrophilic group-containing monofunctional alcohol (c) used is 10 to 60% by mass in the total amount of the above (a), (b), and (c). The method for producing an emulsifying / dispersing agent according to any one of (1) to (6) above.
(8)有機ポリイソシアネートを水に乳化、又は分散させてなることを特徴とする水乳化、又は水分散イソシアネート硬化剤の製造方法であって、上記(1)乃至(7)のいずれかに記載の乳化・分散剤の製造方法により得られた乳化・分散剤を用いることを特徴とする水乳化、又は水分散イソシアネート硬化剤の製造方法。 (8) A method for producing a water-emulsified or water-dispersed isocyanate curing agent, wherein the organic polyisocyanate is emulsified or dispersed in water, and is described in any one of (1) to (7) above. A method for producing a water-emulsified or water-dispersed isocyanate curing agent, comprising using an emulsifier / dispersant obtained by the method for producing an emulsifier / dispersant.
(9)水酸基含有化合物又は水酸基非含有化合物を水に乳化、又は分散させてなることを特徴とする水乳化、又は水分散体の製造方法であって、上記(1)乃至(7)のいずれかに記載の乳化・分散剤の製造方法により得られた乳化・分散剤を用いることを特徴とする水乳化、又は水分散体の製造方法。 (9) A method for producing a water-emulsified or water-dispersed product comprising emulsifying or dispersing a hydroxyl group-containing compound or a hydroxyl group-free compound in water, wherein any of (1) to (7) above A method for producing a water emulsification or water dispersion, comprising using the emulsification / dispersant obtained by the method for producing an emulsification / dispersing agent according to claim 1.
(10)有機ポリイソシアネートと、水酸基含有化合物又は水酸基非含有化合物を含む組成物を、水に乳化、又は分散させてなることを特徴とする水乳化、又は水分散体の製造方法であって、上記(1)乃至(7)のいずれかに記載の乳化・分散剤の製造方法により得られた乳化・分散剤を用いることを特徴とする水乳化、又は水分散体の製造方法。 (10) A method for producing a water emulsion or a water dispersion, comprising emulsifying or dispersing a composition containing an organic polyisocyanate and a hydroxyl group-containing compound or a hydroxyl group-free compound in water, A method for producing a water emulsion or a water dispersion, wherein the emulsion / dispersant obtained by the method for producing an emulsion / dispersant according to any one of (1) to (7) is used.
(11)上記(8)に記載の水乳化、又は水分散イソシアネート硬化剤の製造方法により得られた水乳化、又は水分散イソシアネート硬化剤と、水酸基含有化合物又は水酸基非含有化合物とを含むことを特徴とする水乳化又は水分散硬化性組成物の製造方法。 (11) It contains water emulsification obtained by the method for producing water emulsification or water-dispersed isocyanate curing agent described in (8) above, or water-dispersed isocyanate curing agent, and a hydroxyl group-containing compound or a hydroxyl group-free compound. A method for producing a water-emulsified or water-dispersed curable composition.
本発明により、主剤や硬化剤を乳化、分散させる能力、及びポットライフに優れた乳化・分散剤、並びにこれを用いた水乳化ポリイソシアネート硬化剤及び水乳化硬化性組成物を提供することが可能となった。そのため、本発明の水乳化ポリイソシアネート硬化剤及び水乳化硬化性組成物は、塗料、接着剤、各種結合剤、印刷インキ、記録磁気媒体、コーティング剤、シーリング剤、エラストマー、封止剤、合成皮革、各種フォーム、土木関係の発泡充填剤等、広い範囲に適用できる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide an emulsifier / dispersant excellent in pot life and the ability to emulsify and disperse a main agent and a curing agent, and a water-emulsified polyisocyanate curing agent and a water-emulsion curable composition using the same. It became. Therefore, the water-emulsified polyisocyanate curing agent and the water-emulsion curable composition of the present invention are paints, adhesives, various binders, printing inks, recording magnetic media, coating agents, sealing agents, elastomers, sealants, synthetic leathers. It can be applied to a wide range of foams, foams for civil engineering, etc.
以下、本発明について詳しく説明する。 The present invention will be described in detail below.
本発明に用いられる有機ジイソシアネート(a)としては、例えば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、4,4’−ジフェニルメタンジイソシアネート、2,4’−ジフェニルメタンジイソシアネート、2,2’−ジフェニルメタンジイソシアネート、4,4’−ジフェニルエーテルジイソシアネート、2−ニトロジフェニル−4,4’−ジイソシアネート、2,2’−ジフェニルプロパン−4,4’−ジイソシアネート、3,3’−ジメチルジフェニルメタン−4,4’−ジイソシアネート、4,4’−ジフェニルプロパ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、ナフチレン−1,4−ジイソシアネート、ナフチレン−1,5−ジイソシアネート、3,3’−ジメトキシジフェニル−4,4’−ジイソシアネート等の芳香族ジイソシアネート;ヘキサメチレンジイソシアネート、テトラメチレンジイソシアネート、2−メチル−ペンタン−1,5−ジイソシアネート、3−メチル−ペンタン−1,5−ジイソシアネート、リジンジイソシアネート、トリオキシエチレンジイソシアネート等の脂肪族ジイソシアネート;キシリレン−1,4−ジイソシアネート、キシリレン−1,3−ジイソシアネート、テトラメチルキシリレンジイソシアネート等の芳香脂肪族ジイソシアネート;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、水素添加テトラメチルキシレンジイソシアネート等の脂環族ジイソシアネート等が挙げられる。これらはいずれも単独であるいは2種以上を混合して用いてもよい。本発明においては、得られる乳化・分散剤の耐候性等を考慮すると、脂肪族ジイソシアネートと脂環族ジイソシアネートが好ましく、特にヘキサメチレンジイソシアネートが好ましい。 Examples of the organic diisocyanate (a) used in the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate, and 2,2 ′. -Diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4 '-Diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3 Aromatic diisocyanates such as 3′-dimethoxydiphenyl-4,4′-diisocyanate; hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, Aliphatic diisocyanates such as lysine diisocyanate and trioxyethylene diisocyanate; aromatic aliphatic diisocyanates such as xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate and tetramethylxylylene diisocyanate; isophorone diisocyanate, hydrogenated tolylene diisocyanate, Alicyclic rings such as hydrogenated xylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate Diisocyanate, and the like. Any of these may be used alone or in admixture of two or more. In the present invention, aliphatic diisocyanate and alicyclic diisocyanate are preferable, and hexamethylene diisocyanate is particularly preferable in consideration of the weather resistance of the resulting emulsifier / dispersant.
疎水性基含有モノアルコール(b)としては、例えばメタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、デカノール、ラウリルアルコール、ミリスチルアルコール、ペンタデカノール、セチルアルコール、ヘプタデカノール、ステアリルアルコール、ノナデカノール、オレイルアルコール、これらの異性体等の脂肪族モノアルコール類、シクロヘキサノール、メチルシクロヘキサノール等の脂環族モノアルコール類、ベンジルアルコール等の芳香脂肪族モノアルコール類、また、α−オキシプロピオン酸、オキシコハク酸、ε−オキシプロパン−1,2,3−トリカルボン酸、ヒドロキシ酢酸、α−ヒドロキシ酪酸、ヒドロキシステアリン酸、リシノール酸、リシノエライジン酸、リシノステアロール酸、サリチル酸、マンデル酸等のオキシカルボン酸と前述のモノアルコール類とから得られるエステルモノアルコール類等が挙げられる。これらはいずれも単独であるいは2種以上混合して使用することができる。本発明においては、原料としての取り扱い易さ、得られる乳化・分散剤自身の乳化性、乳化能や粘度等を考慮すると、炭素数1〜20のアルキルモノアルコールが好ましく、炭素数1〜13のアルキルモノアルコールがさらに好ましい。なお「乳化能」とは、乳化・分散剤自身のみならず、被乳化物も一緒に乳化させる能力のことである。 Examples of the hydrophobic group-containing monoalcohol (b) include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, lauryl alcohol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol. , Stearyl alcohol, nonadecanol, oleyl alcohol, aliphatic monoalcohols such as isomers thereof, alicyclic monoalcohols such as cyclohexanol and methylcyclohexanol, araliphatic monoalcohols such as benzyl alcohol, and α -Oxypropionic acid, oxysuccinic acid, ε-oxypropane-1,2,3-tricarboxylic acid, hydroxyacetic acid, α-hydroxybutyric acid, hydroxystearic acid, ricinoleic acid, ricin Elaidic acid, ricinoleate stearolic acid, salicylic acid, esters monoalcohols obtained from hydroxycarboxylic acid and monoalcohols described above, such as mandelic acid and the like. Any of these may be used alone or in admixture of two or more. In the present invention, considering the ease of handling as a raw material, the emulsifying property of the resulting emulsifying / dispersing agent itself, emulsifying ability, viscosity, etc., alkyl monoalcohols having 1 to 20 carbon atoms are preferred, and those having 1 to 13 carbon atoms are preferred. More preferred are alkyl monoalcohols. The “emulsifying ability” refers to the ability to emulsify not only the emulsifying / dispersing agent itself but also the product to be emulsified together.
本発明に用いられるノニオン性親水基含有一官能アルコール(c)としては、例えばポリオキシアルキレングリコールモノアルキルエーテル、ポリオキシアルキレン脂肪酸エステルモノアルコール等が挙げられる。これらはいずれも単独であるいは2種以上混合して使用することができる。これらのうちポリオキシアルキレングリコールモノアルキルエーテルが好ましい。 Examples of the nonionic hydrophilic group-containing monofunctional alcohol (c) used in the present invention include polyoxyalkylene glycol monoalkyl ether and polyoxyalkylene fatty acid ester monoalcohol. Any of these may be used alone or in admixture of two or more. Of these, polyoxyalkylene glycol monoalkyl ether is preferred.
ポリオキシアルキレングリコールモノアルキルエーテルの製造のための開始剤としては、メタノール、n−ブタノール等が挙げられる。これらのうち、低級アルコールを用いると親水性がより高いものとなるため好ましい。また、ポリオキシアルキレン脂肪酸エステルモノアルコールの製造に用いられる脂肪酸としては、酢酸、プロピオン酸、酪酸等が挙げられる。これらのうち、低級脂肪酸を用いると親水性がより高いものとなるため好ましい。 Examples of the initiator for producing the polyoxyalkylene glycol monoalkyl ether include methanol and n-butanol. Among these, it is preferable to use a lower alcohol because the hydrophilicity is higher. Examples of the fatty acid used for the production of the polyoxyalkylene fatty acid ester monoalcohol include acetic acid, propionic acid, butyric acid, and the like. Among these, it is preferable to use a lower fatty acid because it has higher hydrophilicity.
ポリオキシアルキレングリコールモノアルキルエーテル、ポリオキシアルキレン脂肪酸エステルモノアルコール等に存在するポリエーテル鎖は、一般的には3〜90個、好ましくは5〜30個、特に好ましくは8〜10個のアルキレンオキシドユニットであるが、全アルキレンオキシドユニット中にエチレンオキシドユニットを少なくとも70%以上含むものが好ましく、全てエチレンオキシドユニットであることが最も好ましい。 The number of polyether chains present in polyoxyalkylene glycol monoalkyl ether, polyoxyalkylene fatty acid ester monoalcohol and the like is generally 3 to 90, preferably 5 to 30, particularly preferably 8 to 10 alkylene oxides. Although it is a unit, what contains at least 70% or more of ethylene oxide units in all alkylene oxide units is preferable, and it is most preferable that all are ethylene oxide units.
本発明に用いられるアロファネート化触媒としては、カルボン酸のジルコニウム塩を好適に例示することができる。このカルボン酸としては、酢酸、プロピオン酸、酪酸、カプロン酸、オクチル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、2−エチルヘキサン酸等の飽和脂肪族カルボン酸、シクロヘキサンカルボン酸、シクロペンタンカルボン酸等の飽和単環カルボン酸、ビシクロ[4.4.0]デカン−2−カルボン酸等の飽和複環カルボン酸、ナフテン酸等の上記したカルボン酸の混合物、オレイン酸、リノール酸、リノレン酸、大豆油脂肪酸、トール油脂肪酸等の不飽和脂肪族カルボン酸、ジフェニル酢酸等の芳香脂肪族カルボン酸、安息香酸、トルイル酸等の芳香族カルボン酸等のモノカルボン酸類、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、酒石酸、シュウ酸、マロン酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、クルタコン酸、アゼライン酸、セバシン酸、1,4−シクロヘキシルジカルボン酸、α−ハイドロムコン酸、β−ハイドロムコン酸、α−ブチル−α−エチルグルタル酸、α,β−ジエチルサクシン酸、マレイン酸、フマル酸、トリメリット酸、ピロメリット酸等のポリカルボン酸類等が挙げられる。これらはいずれも単独であるいは2種以上を混合して用いてもよい。本発明において特に好ましいアロファネート化触媒は、炭素数10以下のモノカルボン酸ジルコニウム塩である。このアロファネート化触媒を使用することにより、助触媒等を使用しなくても、実質的に着色のない乳化・分散剤を比較的容易に得ることができる。 A preferred example of the allophanatization catalyst used in the present invention is a zirconium salt of a carboxylic acid. Examples of the carboxylic acid include acetic acid, propionic acid, butyric acid, caproic acid, octylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, 2-ethylhexanoic acid and other saturated aliphatic carboxylic acids, cyclohexanecarboxylic acid, and cyclopentane. Saturated monocyclic carboxylic acids such as carboxylic acids, saturated polycyclic carboxylic acids such as bicyclo [4.4.0] decane-2-carboxylic acid, mixtures of the above carboxylic acids such as naphthenic acid, oleic acid, linoleic acid, linolenic acid Acids, unsaturated aliphatic carboxylic acids such as soybean oil fatty acid and tall oil fatty acid, araliphatic carboxylic acids such as diphenylacetic acid, monocarboxylic acids such as aromatic carboxylic acids such as benzoic acid and toluic acid, phthalic acid, isophthalic acid , Terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, Pinic acid, pimelic acid, suberic acid, kurtaconic acid, azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, Examples thereof include polycarboxylic acids such as β-diethylsuccinic acid, maleic acid, fumaric acid, trimellitic acid, and pyromellitic acid. Any of these may be used alone or in admixture of two or more. A particularly preferred allophanatization catalyst in the present invention is a monocarboxylic acid zirconium salt having 10 or less carbon atoms. By using this allophanatization catalyst, an emulsifying / dispersing agent having substantially no color can be obtained relatively easily without using a promoter or the like.
次に、本発明における乳化・分散剤の具体的な製造手順について説明する。 Next, a specific production procedure of the emulsifying / dispersing agent in the present invention will be described.
本発明は以下の工程からなる。
第一工程:有機ジイソシアネート(a)と、疎水性基含有モノアルコール(b)をアロファネート触媒の存在下で反応させる工程。
第二工程:触媒毒を添加して、アロファネート化反応を停止させる工程。
第三工程:遊離の有機ジイソシアネート(a)を蒸留により除去する工程。
第四工程:第三工程から得られたアロファネート変性イソシアネートと、ノニオン性親水基含有一官能アルコール(c)をアロファネート触媒の存在下で反応させる工程。
第五工程:触媒毒を添加して、アロファネート化反応を停止させる工程。
The present invention comprises the following steps.
First step: a step of reacting the organic diisocyanate (a) with a hydrophobic group-containing monoalcohol (b) in the presence of an allophanate catalyst.
Second step: A step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction.
第一工程は、ウレタン化反応とアロファネート化反応からなる。具体的な手順は、有機ジイソシアネート(a)と、疎水性基含有モノアルコール(b)を、イソシアネート基を水酸基に対して過剰となる量を仕込んで、20〜100℃でウレタン化反応させた後、70〜150℃にてアロファネート化触媒の存在下でウレタン基が実質的に存在しなくなるまでアロファネート化反応させる、という手順である。 The first step consists of a urethanization reaction and an allophanatization reaction. Specifically, the organic diisocyanate (a) and the hydrophobic group-containing monoalcohol (b) are urethanated at a temperature of 20 to 100 ° C. after adding an excess amount of the isocyanate group to the hydroxyl group. The allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until substantially no urethane group is present.
ここで「イソシアネート基を水酸基に対して過剰となる量」とは、原料仕込みの際、イソシアネート基を水酸基に対して過剰となるという意味であり、イソシアネート基と水酸基のモル比がイソシアネート基/水酸基=8以上が好ましく、10〜50が特に好ましい。 Here, the “amount of isocyanate group in excess with respect to the hydroxyl group” means that the isocyanate group becomes excessive with respect to the hydroxyl group when the raw material is charged, and the molar ratio of isocyanate group to hydroxyl group is isocyanate group / hydroxyl group. = 8 or more is preferable, and 10 to 50 is particularly preferable.
ウレタン化反応の反応温度は20〜120℃であり、好ましくは50〜100℃である。なお、ウレタン化反応の際、公知のウレタン化触媒を用いることができる。具体的には、ジブチルチンジラウレート、ジオクチルチンジラウレート等の有機金属化合物や、トリエチレンジアミンやトリエチルアミン等の有機アミンやその塩等が挙げられる。 The reaction temperature of the urethanization reaction is 20 to 120 ° C, preferably 50 to 100 ° C. In the urethanization reaction, a known urethanization catalyst can be used. Specific examples thereof include organic metal compounds such as dibutyltin dilaurate and dioctyltin dilaurate, organic amines such as triethylenediamine and triethylamine, and salts thereof.
ウレタン化反応の反応時間は、触媒の有無や種類、反応温度により異なるが、一般には10時間以内、好ましくは1〜5時間である。 The reaction time of the urethanization reaction varies depending on the presence / absence and type of the catalyst and the reaction temperature, but is generally within 10 hours, preferably 1 to 5 hours.
ウレタン化反応が終了したら、アロファネート化反応を行う。アロファネート化反応は、前述のアロファネート化触媒を添加し、反応温度を70〜150℃、好ましくは80〜130℃にして行う。反応温度が低すぎる場合は、アロファネート基があまり生成せず、得られる乳化・分散剤の乳化能力が低下することがある。このような乳化・分散剤を有機ポリイソシアネート硬化剤に用いると、乳化が不十分となりやすい。反応温度が高すぎる場合は、得られる乳化・分散剤を不必要に加熱することになり、着色する原因になることがある。 When the urethanization reaction is completed, an allophanatization reaction is performed. The allophanatization reaction is carried out by adding the above-mentioned allophanate catalyst and setting the reaction temperature to 70 to 150 ° C, preferably 80 to 130 ° C. When the reaction temperature is too low, allophanate groups are not generated so much, and the emulsifying ability of the resulting emulsifying / dispersing agent may be lowered. When such an emulsifying / dispersing agent is used for the organic polyisocyanate curing agent, emulsification tends to be insufficient. When the reaction temperature is too high, the resulting emulsifying / dispersing agent is unnecessarily heated, which may cause coloring.
なお、本発明においては、ウレタン化反応とアロファネート化反応を同時に行うこともできる。この場合は、有機ジイソシアネート(a)と、疎水性基含有モノアルコール(b)を、イソシアネート基を水酸基に対して過剰となる量を仕込んで、70〜150℃にてアロファネート化触媒の存在下でウレタン化反応及びアロファネート化反応を同時に行う。 In the present invention, the urethanization reaction and the allophanatization reaction can be performed simultaneously. In this case, the organic diisocyanate (a) and the hydrophobic group-containing monoalcohol (b) are charged in an amount that makes the isocyanate group excessive with respect to the hydroxyl group, and in the presence of the allophanate catalyst at 70 to 150 ° C. The urethanization reaction and the allophanatization reaction are performed simultaneously.
アロファネート化触媒の使用量はその種類により異なるが、上記(a)と(b)の総和量に対して、0.0005〜1質量%が好ましく、0.001〜0.1質量%がより好ましい。触媒使用量が0.0005質量%未満の場合は、反応に長時間を要し、熱履歴による着色が起こる場合がある。一方触媒使用量が1質量%を超える場合は、反応制御が難しくなり、副反応である二量化反応(ウレトジオン化反応)や三量化反応(イソシアヌレート化反応)が起こる場合があり、また得られた乳化・分散剤を用いた場合、塗料のポットライフが短くなる等の問題が生じることがある。 The amount of allophanate catalyst used varies depending on the type, but is preferably 0.0005 to 1% by mass, more preferably 0.001 to 0.1% by mass, based on the total amount of (a) and (b). . When the amount of the catalyst used is less than 0.0005% by mass, the reaction takes a long time, and coloring due to thermal history may occur. On the other hand, when the amount of the catalyst used exceeds 1% by mass, it becomes difficult to control the reaction, and a dimerization reaction (uretodione reaction) or a trimerization reaction (isocyanurate reaction) may occur and are obtained. When using an emulsifying / dispersing agent, problems such as shortening the pot life of the paint may occur.
反応時間は、触媒の種類や添加量、反応温度により異なるが、一般には10時間以内、好ましくは1〜5時間である。 The reaction time varies depending on the type of catalyst, the amount added, and the reaction temperature, but is generally within 10 hours, preferably 1 to 5 hours.
なお、このとき必要に応じて有機溶剤を用いることができる。有機溶剤としては、n−ヘキサン、オクタン等の脂肪族炭化水素系有機溶剤、シクロヘキサン、メチルシクロヘキサン等の脂環族炭化水素系有機溶剤、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン系有機溶剤、酢酸メチル、酢酸エチル、酢酸ブチル、酢酸イソブチル等のエステル系有機溶剤、エチレングリコールエチルエーテルアセテート、プロピレングリコールメチルエーテルアセテート、3−メチル−3−メトキシブチルアセテート、エチル−3−エトキシプロピオネート等のグリコールエーテルエステル系有機溶剤、ジエチルエーテル、テトラヒドロフラン、ジオキサン等のエーテル系有機溶剤、塩化メチル、塩化メチレン、クロロホルム、四塩化炭素、臭化メチル、ヨウ化メチレン、ジクロロエタン等のハロゲン化脂肪族炭化水素系有機溶剤、N−メチルピロリドン、ジメチルホルムアミド、ジメチルアセトアミド、ジメチルスルホキシド、ヘキサメチルホスホニルアミド等の極性非プロトン溶剤等が挙げられる。前記有機溶剤は1種又は2種以上を併用することができる。 At this time, an organic solvent can be used as necessary. Examples of organic solvents include aliphatic hydrocarbon organic solvents such as n-hexane and octane, alicyclic hydrocarbon organic solvents such as cyclohexane and methylcyclohexane, and ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ester organic solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol methyl ether acetate, 3-methyl-3-methoxybutyl acetate, ethyl-3-ethoxypropionate, etc. Glycol ether ester organic solvents, diethyl ether, tetrahydrofuran, dioxane and other ether organic solvents, methyl chloride, methylene chloride, chloroform, carbon tetrachloride, methyl bromide, methylene iodide, dichloride Halogenated aliphatic hydrocarbon organic solvents such as Roetan, N- methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, polar aprotic solvents such as hexamethylphosphoric phosphonyl amides. The said organic solvent can use together 1 type, or 2 or more types.
第二工程は、アロファネート化反応後、触媒毒を添加してアロファネート化反応を停止させる工程である。触媒毒の添加時期は、アロファネート化反応後であれば特に制限はないが、第三工程における、遊離の有機ジイソシアネート(a)を除去する方法に薄膜蒸留を行う場合は、アロファネート反応後かつ薄膜蒸留前に触媒毒の添加を行うのが好ましい。これは、薄膜蒸留時の熱により、副反応が起こるのを防止するためである。 The second step is a step of adding the catalyst poison after the allophanate reaction to stop the allophanate reaction. The catalyst poisoning time is not particularly limited as long as it is after the allophanatization reaction. However, when thin film distillation is performed in the method of removing free organic diisocyanate (a) in the third step, after the allophanate reaction and thin film distillation. It is preferred to add the catalyst poison before. This is to prevent side reactions from occurring due to heat during thin film distillation.
この触媒毒としては、リン酸、塩酸等の無機酸、スルホン酸基、スルファミン酸基等を有する有機酸及びこれらのエステル類、アシルハライド等公知の物が挙げられる。 Examples of the catalyst poison include inorganic acids such as phosphoric acid and hydrochloric acid, organic acids having a sulfonic acid group, a sulfamic acid group and the like, and esters thereof, known substances such as acyl halides.
第三工程は、遊離の有機ジイソシアネート(a)を除去する工程である。遊離の有機ジイソシアネートを除去する方法としては、蒸留、再沈、抽出等公知の方法が挙げられ、蒸留法、特に薄膜蒸留法を使用すると、溶剤等を用いる必要がないので好ましい。また、好ましい薄膜蒸留の条件としては、圧力:0.1kPa以下、温度:100〜200℃であり、特に好ましい条件は圧力:0.05kPa以下、温度:120〜180℃である。 The third step is a step of removing free organic diisocyanate (a). As a method for removing free organic diisocyanate, known methods such as distillation, reprecipitation, extraction and the like can be mentioned, and it is preferable to use a distillation method, particularly a thin film distillation method, because it is not necessary to use a solvent. Further, preferable conditions for thin film distillation are pressure: 0.1 kPa or less, temperature: 100 to 200 ° C., and particularly preferable conditions are pressure: 0.05 kPa or less and temperature: 120 to 180 ° C.
第四工程は、ウレタン化反応とアロファネート化反応の工程である。具体的な手順は、第三工程で得られたアロファネート変性ポリイソシアネートと、ノニオン性親水基含有一官能アルコール(c)を、アロファネート変性ポリイソシアネートのイソシアネート基を水酸基に対して過剰となる量を仕込んで、20〜100℃でウレタン化反応させた後、70〜150℃にてアロファネート化触媒の存在下でウレタン基が実質的に存在しなくなるまでアロファネート化反応させる、という手順である。 The fourth step is a step of urethanization reaction and allophanatization reaction. Specifically, the allophanate-modified polyisocyanate obtained in the third step and the nonionic hydrophilic group-containing monofunctional alcohol (c) are charged in an amount in which the isocyanate group of the allophanate-modified polyisocyanate is excessive with respect to the hydroxyl group. Then, after the urethanization reaction at 20 to 100 ° C., the allophanatization reaction is carried out at 70 to 150 ° C. in the presence of the allophanatization catalyst until substantially no urethane group is present.
第五工程は、アロファネート化反応後、触媒毒を添加してアロファネート化反応を停止させる工程である。触媒毒の添加時期は、アロファネート化反応後であれば特に制限はない。 The fifth step is a step of stopping the allophanatization reaction by adding a catalyst poison after the allophanatization reaction. The addition timing of the catalyst poison is not particularly limited as long as it is after the allophanatization reaction.
このようにして得られるアロファネート変性ポリイソシアネート(乳化・分散剤)のノニオン性親水基含有一官能アルコール(c)の含有量は10〜60質量%であり、好ましくは20〜50質量%である。ノニオン性親水基含有一官能アルコール(c)含有量がこの範囲を超えると、乳化、分散性が不十分となる。 The content of the nonionic hydrophilic group-containing monofunctional alcohol (c) in the allophanate-modified polyisocyanate (emulsifier / dispersant) thus obtained is 10 to 60% by mass, preferably 20 to 50% by mass. When the content of the nonionic hydrophilic group-containing monofunctional alcohol (c) exceeds this range, emulsification and dispersibility become insufficient.
本発明の乳化・分散剤の使用において、分散させる被乳化物の有機ポリイソシアネートとしては、有機ジイソシアネートのウレタン変性体、イソシアヌレート変性体、アロファネート変性体等が挙げられる。 In the use of the emulsifying / dispersing agent of the present invention, examples of the organic polyisocyanate to be emulsified include urethane-modified products, isocyanurate-modified products, and allophanate-modified products of organic diisocyanates.
本発明の乳化・分散剤の使用において、前述の有機ポリイソシアネートを水に乳化、分散する乳化・分散剤の配合量は、有機ポリイソシアネート100質量部に対して10〜1000質量部が好ましく、20〜500質量部が更に好ましく、50〜300質量部であることが最も好ましい。 In the use of the emulsifying / dispersing agent of the present invention, the amount of the emulsifying / dispersing agent for emulsifying and dispersing the organic polyisocyanate in water is preferably 10 to 1000 parts by mass with respect to 100 parts by mass of the organic polyisocyanate. -500 mass parts is still more preferable, and it is most preferable that it is 50-300 mass parts.
本発明の水乳化・分散硬化性組成物に使用される主剤としての高分子化合物は、常温液体で水に溶解性或いは親和性を有しない物が挙げられる。もしくは、水に対して溶解性或いはある程度の親和性を有する水溶性樹脂及び/又は水系エマルジョンを使用することも可能である。これらの高分子化合物は分子内にイソシアネート基と反応する活性水素を含有するものが好ましく、特に2個以上の活性水素を含有するものが好ましい。高分子化合物は、イソシアネート基と反応しうる活性水素を含有していない場合又は少ししか含有していない場合でも、最終的には水乳化・分散ポリイソシアネート硬化剤が水と反応してポリウレア化合物となり、硬くて強靭な塗膜となる。また、イソシアネート基が被着材表面に存在する活性水素(基)と反応するため、密着性も向上する。しかし、常温においてイソシアネート基と反応しうる活性水素を含有する高分子化合物を使用した場合は、高分子化合物中の活性水素と水乳化・分散ポリイソシアネート硬化剤中のイソシアネート基が反応し、架橋構造を形成するため、耐候性、耐溶剤性などが更に向上することになる。 Examples of the polymer compound as the main agent used in the water emulsification / dispersion curable composition of the present invention include liquids at room temperature that are not soluble or compatible with water. Alternatively, it is also possible to use a water-soluble resin and / or an aqueous emulsion having solubility or a certain degree of affinity for water. These polymer compounds preferably contain active hydrogen that reacts with an isocyanate group in the molecule, and particularly those containing two or more active hydrogens. Even if the polymer compound does not contain active hydrogen that can react with isocyanate groups or contains little hydrogen, the water-emulsified / dispersed polyisocyanate curing agent eventually reacts with water to become a polyurea compound. It becomes a hard and tough coating film. Moreover, since an isocyanate group reacts with the active hydrogen (group) existing on the surface of the adherend, adhesion is also improved. However, when a polymer compound containing active hydrogen that can react with an isocyanate group at room temperature is used, the active hydrogen in the polymer compound reacts with the isocyanate group in the water-emulsified / dispersed polyisocyanate curing agent to form a crosslinked structure. Therefore, weather resistance, solvent resistance and the like are further improved.
具体的には、例えば飽和或いは不飽和ポリエステルポリオール、ポリカプロラクトンポリオール、飽和或いは不飽和の脂肪酸変性アルキッドポリオール、アミノアルキッドポリオール、ポリカーボネートポリオール、アクリルポリオール、ポリエーテルポリオール、エポキシポリオール、含フッ素ポリオール、更には飽和或いは不飽和ポリエステル樹脂、ポリカプロラクトン樹脂、脂肪酸変性アルキッド樹脂、アミノアルキッド樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリエーテル樹脂、エポキシ樹脂、ポリウレタン樹脂、セルロースアセテートブチラート樹脂、含フッ素樹脂などが挙げられる。 Specifically, for example, saturated or unsaturated polyester polyol, polycaprolactone polyol, saturated or unsaturated fatty acid-modified alkyd polyol, amino alkyd polyol, polycarbonate polyol, acrylic polyol, polyether polyol, epoxy polyol, fluorine-containing polyol, and Examples thereof include saturated or unsaturated polyester resins, polycaprolactone resins, fatty acid-modified alkyd resins, amino alkyd resins, polycarbonate resins, acrylic resins, polyether resins, epoxy resins, polyurethane resins, cellulose acetate butyrate resins, and fluorine-containing resins.
水溶性樹脂としては、例えば、ポリビニルアルコール、ポリエチレンオキサイド、水溶性エチレン−酢酸ビニル共重合体、水溶性アクリル樹脂、水溶性エポキシ樹脂、水溶性セルロース誘導体、水溶性ポリエステル、水溶性リグニン誘導体、水溶性フッ素樹脂、水溶性シリコーン樹脂などが挙げられる。 Examples of the water-soluble resin include polyvinyl alcohol, polyethylene oxide, water-soluble ethylene-vinyl acetate copolymer, water-soluble acrylic resin, water-soluble epoxy resin, water-soluble cellulose derivative, water-soluble polyester, water-soluble lignin derivative, water-soluble A fluororesin, a water-soluble silicone resin, etc. are mentioned.
水系エマルジョンとしては、いわゆるラテックス、エマルジョンと表現されるもの全てを包含し、例えば、スチレンブタジエン共重合体ラテックス、アクリロニトリルブタジエン共重合体ラテックス、メチルメタアクリレートブタジエン共重合体ラテックス、クロロプレンラテックス、ポリブタジエンラテックス等のゴム系ラテックス、ポリアクリル酸エステルラテックス、ポリ塩化ビニリデンラテックス、ポリブタジエンラテックス、或いはこれらのラテックスをカルボキシル変性したもの、また、ポリ塩化ビニルエマルジョン、ウレタンアクリルエマルジョン、シリコーンアクリルエマルジョン、酢酸ビニルアクリルエマルジョン、ポリウレタンエマルジョン、アクリルエマルジョンなどが挙げられる。 Examples of water-based emulsions include what are called latexes and emulsions. For example, styrene butadiene copolymer latex, acrylonitrile butadiene copolymer latex, methyl methacrylate butadiene copolymer latex, chloroprene latex, polybutadiene latex, etc. Rubber latex, polyacrylate ester latex, polyvinylidene chloride latex, polybutadiene latex, or carboxyl-modified latex of these latexes, polyvinyl chloride emulsion, urethane acrylic emulsion, silicone acrylic emulsion, vinyl acetate acrylic emulsion, polyurethane An emulsion, an acrylic emulsion, etc. are mentioned.
これらのうち、光沢、耐候性等の塗膜性能や接着強度の点で、アクリルポリオール、アクリル樹脂、水溶性アクリル樹脂、アクリルエマルジョン、ウレタンアクリルエマルジョン、ポリウレタンエマルジョンが特に好ましい。 Of these, acrylic polyols, acrylic resins, water-soluble acrylic resins, acrylic emulsions, urethane acrylic emulsions, and polyurethane emulsions are particularly preferable in terms of coating performance such as gloss and weather resistance, and adhesive strength.
これら主剤としての高分子化合物の数平均分子量は、好ましくは1000〜100万であり、さらに好ましくは10000〜10万である。 The number average molecular weight of the polymer compound as the main agent is preferably 1,000 to 1,000,000, and more preferably 10,000 to 100,000.
本発明の乳化・分散剤の使用において、有機ポリイソシアネートと主剤としての高分子化合物を水に乳化、分散する乳化・分散剤の配合量は、有機ポリイソシアネート100質量部に対して10〜1000質量部が好ましく、20〜500質量部が更に好ましく、50〜300質量部であることが最も好ましい。 In the use of the emulsifying / dispersing agent of the present invention, the blending amount of the emulsifying / dispersing agent for emulsifying and dispersing the organic polyisocyanate and the polymer compound as the main component in water is 10 to 1000 parts by mass with respect to 100 parts by mass of the organic polyisocyanate. Part is preferable, 20-500 mass parts is still more preferable, and it is most preferable that it is 50-300 mass parts.
本発明の水乳化・分散硬化性組成物において、高分子化合物として分子中に活性水素を含有するものを使用する場合、水乳化・分散イソシアネート硬化剤中のイソシアネート基と主剤としての活性水素含有高分子化合物中の活性水素基とのモル比は、9:1〜1:9が好ましく、更に好ましくは6:4〜4:6の範囲である。 In the water emulsification / dispersion curable composition of the present invention, when using a polymer compound containing active hydrogen in the molecule, the isocyanate group in the water emulsification / dispersion isocyanate curing agent and the content of active hydrogen as the main component are high. The molar ratio with the active hydrogen group in the molecular compound is preferably 9: 1 to 1: 9, more preferably 6: 4 to 4: 6.
本発明の水乳化・分散硬化性組成物において、水と乳化・分散剤と有機ポリイソシアネートと高分子化合物との配合方法は、そのまま全原料を配合し乳化、分散させる、また、まず乳化・分散剤により有機ポリイソシアネートを水に乳化、分散させ、この中に主剤としての高分子化合物を配合して乳化、分散させる、また、まず主剤としての高分子化合物を乳化・分散剤により水に乳化、分散させ、この中に有機ポリイソシアネートを配合して乳化、分散させる等の方法が挙げられる。好ましい方法は、まず、乳化・分散剤により有機ポリイソシアネートを水に乳化、分散させ、次いでこの中に高分子化合物を配合して乳化、分散させる方法である。 In the water emulsification / dispersion curable composition of the present invention, the blending method of water, the emulsification / dispersant, the organic polyisocyanate, and the polymer compound is blended with all the raw materials as they are, and emulsified and dispersed. An organic polyisocyanate is emulsified and dispersed in water by an agent, and a polymer compound as a main ingredient is blended and emulsified and dispersed therein, and the polymer compound as a main ingredient is first emulsified in water by an emulsifier / dispersant. Examples thereof include a method of dispersing, emulsifying and dispersing by mixing organic polyisocyanate therein. A preferred method is a method in which an organic polyisocyanate is first emulsified and dispersed in water using an emulsifying / dispersing agent, and then a polymer compound is blended and emulsified and dispersed therein.
水と乳化・分散剤及び有機ポリイソシアネート(硬化剤)との配合比率は、水100質量部に対して、乳化・分散剤と有機ポリイソシアネート(硬化剤)との合計量は好ましくは0.1〜500質量部、更に好ましくは1〜100質量部、最も好ましくは3〜50質量部である。また、水と、乳化・分散剤、有機ポリイソシアネート(硬化剤)及び高分子化合物(主剤)との配合比率は、水100質量部に対して、乳化・分散剤と有機ポリイソシアネート(硬化剤)と高分子化合物(主剤)との合計量は好ましくは0.1〜500質量部、更に好ましくは1〜100質量部、最も好ましくは3〜50質量部である。この水乳化・分散イソシアネート硬化剤又は水乳化・分散硬化性組成物は、乳化、分散後も安定に存在している。イソシアネート基が主剤の他に適用する基材表面に存在する活性水素(基)とも反応するため、非常に密着性の良い塗料或いは接着剤などとなる。また、乳化、分散後かなりの時間が経過し、イソシアネート基が消滅した後も、粒径が0.05〜5μm程度のエマルジョン状態として安定に存在し、それを常温乾燥或いは加熱乾燥して得られる塗膜は、硬くて強靭なものとなるため、フィルム又はシートの形態或いは各種基材のコーティング剤等として使用することが可能である。なお、基材との密着性が重視される場合は、イソシアネート基が存在している状態で使用することが好ましい。 The blending ratio of water, the emulsifying / dispersing agent, and the organic polyisocyanate (curing agent) is preferably 0.1 with respect to 100 parts by mass of water. -500 mass parts, More preferably, it is 1-100 mass parts, Most preferably, it is 3-50 mass parts. The mixing ratio of water to the emulsifying / dispersing agent, organic polyisocyanate (curing agent) and polymer compound (main agent) is 100 parts by weight of the emulsifying / dispersing agent and organic polyisocyanate (curing agent). The total amount of the polymer compound (main agent) is preferably 0.1 to 500 parts by mass, more preferably 1 to 100 parts by mass, and most preferably 3 to 50 parts by mass. This water-emulsified / dispersed isocyanate curing agent or water-emulsified / dispersed curable composition is stably present after emulsification and dispersion. Since the isocyanate group also reacts with active hydrogen (group) present on the surface of the base material to be applied in addition to the main agent, it becomes a paint or adhesive with very good adhesion. In addition, even after a considerable time has passed after emulsification and dispersion and the isocyanate group has disappeared, it is stably present as an emulsion state having a particle size of about 0.05 to 5 μm, and can be obtained by drying at room temperature or heating. Since the coating film is hard and tough, it can be used in the form of a film or sheet or as a coating agent for various substrates. In addition, when importance is attached to adhesiveness with a base material, it is preferable to use it in the state in which an isocyanate group exists.
本発明における乳化・分散剤、水乳化・分散イソシアネート硬化剤、水乳化・分散硬化性組成物には、必要に応じて、例えば、酸化防止剤や、紫外線吸収剤、顔料、染料、難燃剤、加水分解防止剤、潤滑剤、可塑剤、充填剤、貯蔵安定剤といった添加剤を適宜配合することができる。 In the emulsifying / dispersing agent, water emulsifying / dispersing isocyanate curing agent, water emulsifying / dispersing curable composition in the present invention, for example, an antioxidant, an ultraviolet absorber, a pigment, a dye, a flame retardant, Additives such as hydrolysis inhibitors, lubricants, plasticizers, fillers, and storage stabilizers can be appropriately blended.
さらに、本発明の水乳化・分散硬化性組成物は従来より行なわれている通常の塗装方法によって塗装することができ、塗装にはエアレススプレー機、エアスプレー機、静電塗装機、浸漬、ロールコーター、ナイフコーター、ハケ等を用いることができる。 Furthermore, the water emulsification / dispersion curable composition of the present invention can be applied by a conventional coating method conventionally used. An airless spray machine, an air spray machine, an electrostatic coating machine, an immersion, a roll A coater, knife coater, brush or the like can be used.
以下、合成実施例、応用実施例等により本発明について更に詳細に説明するが、本発明はこれらにより何ら限定して解釈されるものではない。なお、製造実施例、製造比較例等において「%」は「質量%」を意味する。 Hereinafter, the present invention will be described in more detail with reference to synthesis examples and application examples, but the present invention should not be construed as being limited thereto. In the production examples, production comparison examples, etc., “%” means “mass%”.
[アロファネート乳化・分散剤の製造]
<製造実施例1>
攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、ヘキサメチレンジイソシアネートを950g、イソプロパノールを50g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行って、遊離のヘキサメチレンジイソシアネートを薄膜蒸留にて除去し、イソシアネート含量が19.2%のアロファネート変性イソシアネートを得た(NCO−1)。攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、NCO−1を600g、メトキシポリエチレングリコール(分子量約400)を400g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行った。こうして、イソシアネート含量3.3%、25℃における粘度8700mPa・s、GPC測定にて分析したところ、遊離のヘキサメチレンジイソシアネートが0.1%の乳化・分散剤EA−1を得た。ポットライフは23時間であった。
[Production of allophanate emulsifier / dispersant]
<Production Example 1>
Urethane reaction was performed at 90 ° C. for 2 hours at 950 g of hexamethylene diisocyanate and 50 g of isopropanol in a reactor of 1 L with a stirrer, a thermometer, a cooler, and a nitrogen gas introduction tube. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour, and free hexamethylene diisocyanate was removed by thin-film distillation to obtain an allophanate-modified isocyanate having an isocyanate content of 19.2% (NCO -1). A volume of 1 L reactor equipped with a stirrer, thermometer, cooler and nitrogen gas inlet tube: NCO-1 (600 g), methoxypolyethylene glycol (molecular weight of about 400) 400 g, and urethanization reaction at 90 ° C. for 2 hours It was. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity of 8700 mPa · s at 25 ° C., an emulsifying / dispersing agent EA-1 having a free hexamethylene diisocyanate of 0.1% was obtained. The pot life was 23 hours.
<製造実施例2>
攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、ヘキサメチレンジイソシアネートを880g、2−エチルヘキサノールを120g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行って、遊離のヘキサメチレンジイソシアネートを薄膜蒸留にて除去し、イソシアネート含量が14.4%のアロファネート変性イソシアネートを得た(NCO−2)。攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、NCO−2を700g、メトキシポリエチレングリコール(分子量約400)を300g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行った。こうして、イソシアネート含量3.3%、25℃における粘度6500mPa・s、GPC測定にて分析したところ、遊離のヘキサメチレンジイソシアネートが0.1%の乳化・分散剤EA−2を得た。ポットライフは23時間であった。
<Production Example 2>
A urethanization reaction was performed at 90 ° C. for 2 hours at 880 g of hexamethylene diisocyanate and 120 g of 2-ethylhexanol in a reactor of 1 L with a stirrer, a thermometer, a cooler and a nitrogen gas introduction tube. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour, and free hexamethylene diisocyanate was removed by thin-film distillation to obtain an allophanate-modified isocyanate having an isocyanate content of 14.4% (NCO -2). A capacity of 1L reactor equipped with stirrer, thermometer, cooler and nitrogen gas inlet tube: 700g of NCO-2, 300g of methoxypolyethylene glycol (molecular weight about 400), and urethanization reaction at 90 ° C for 2 hours It was. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity of 6500 mPa · s at 25 ° C., an emulsifier / dispersant EA-2 having a free hexamethylene diisocyanate of 0.1% was obtained. The pot life was 23 hours.
<製造比較例1>
攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、ヘキサメチレンジイソシアネートを510g、イソプロパノールを95g、メトキシポリエチレングリコール(分子量約400)を395g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行った。こうして、イソシアネート含量3.3%、25℃における粘度10000mPa・s、GPC測定にて分析したところ、遊離のヘキサメチレンジイソシアネートが1%の乳化・分散剤EA−3を得た。ポットライフは12時間であった。
<Production Comparative Example 1>
Volume with a stirrer, thermometer, condenser and nitrogen gas inlet tube: In a 1 L reactor, 510 g of hexamethylene diisocyanate, 95 g of isopropanol, 395 g of methoxypolyethylene glycol (molecular weight about 400), urethane at 90 ° C. for 2 hours The reaction was carried out. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 3.3%, a viscosity at 25 ° C. of 10,000 mPa · s, an emulsifier / dispersant EA-3 having 1% of free hexamethylene diisocyanate was obtained. The pot life was 12 hours.
<製造比較例2>
攪拌機、温度計、冷却器及び窒素ガス導入管の付いた容量:1Lの反応器に、ヘキサメチレンジイソシアネートを500g、イソプロパノールを100g、メトキシポリエチレングリコール(分子量約400)を400g、90℃で2時間ウレタン化反応を行った。反応生成物をFT−IRにて分析したところ、水酸基は消失していた。次に、2−エチルヘキサン酸ジルコニウムを0.36g仕込み、90℃にて3時間アロファネート化反応させた。反応生成物をFT−IR及び13C−NMRにて分析したところ、ウレタン基は消失していた。次いで、リン酸を0.1g仕込み、50℃で1時間停止反応を行った。こうして、イソシアネート含量2.4%、25℃における粘度160000mPa・s、GPC測定にて分析したところ、遊離のヘキサメチレンジイソシアネートが0.1%の乳化・分散剤EA−4を得た。臭気は確認されなかったが、高粘度のため水に乳化・分散はしなかった。
<Production Comparative Example 2>
Volume with a stirrer, thermometer, condenser and nitrogen gas inlet tube: 500 g of hexamethylene diisocyanate, 100 g of isopropanol, 400 g of methoxypolyethylene glycol (molecular weight about 400), urethane at 90 ° C. for 2 hours in a 1 L reactor The reaction was carried out. When the reaction product was analyzed by FT-IR, the hydroxyl group had disappeared. Next, 0.36 g of zirconium 2-ethylhexanoate was charged and allophanated at 90 ° C. for 3 hours. When the reaction product was analyzed by FT-IR and 13 C-NMR, the urethane group had disappeared. Next, 0.1 g of phosphoric acid was added, and a stop reaction was performed at 50 ° C. for 1 hour. Thus, when analyzed by GPC measurement with an isocyanate content of 2.4%, a viscosity at 25 ° C. of 160000 mPa · s, an emulsifier / dispersant EA-4 having 0.1% free hexamethylene diisocyanate was obtained. Odor was not confirmed, but it was not emulsified or dispersed in water due to its high viscosity.
製造実施例1、2、製造比較例1、2における各分析値の測定方法は以下の通り。 The measurement method of each analytical value in Production Examples 1 and 2 and Production Comparative Examples 1 and 2 is as follows.
[イソシアネート含量]
JIS K1603に準じて測定。
[Isocyanate content]
Measured according to JIS K1603.
[官能基の分析]
FT−IR(サーモフィッシャー製AVATAR−360)、13C−NMR(日本電子製JNM−ECX400)の各官能基のピーク強度でその存否を判断。
[Analysis of functional groups]
The presence or absence is determined by the peak intensity of each functional group of FT-IR (Thermo Fisher AVATAR-360), 13 C-NMR (JEOL JNM-ECX400).
[遊離のヘキサメチレンジイソシアネート含量]
GPC(東ソー製HLC−8120)のヘキサメチレンジイソシアネートのピークの面積比から算出。
[Free hexamethylene diisocyanate content]
Calculated from the area ratio of the hexamethylene diisocyanate peak of GPC (HLC-8120 manufactured by Tosoh Corporation).
[ポットライフの評価]
製造実施例1、2、製造比較例1、2で得られた各乳化・分散剤EA−1〜4を5gとヘキサメチレンジイソシアネートのイソシアヌレート変性体(東ソー株式会社製コロネートHXLV、イソシアネート含量=23.3%)を5gと水を90g使用してホモミキサーを用いて2000rpmで30秒間高速撹拌し、イソシアネート基が消失するまでの時間を測定した。
[Evaluation of pot life]
5 g of each emulsifier / dispersant EA-1 to 4 obtained in Production Examples 1 and 2 and Production Comparative Examples 1 and 2 and an isocyanurate modified product of hexamethylene diisocyanate (Coronate HXLV manufactured by Tosoh Corporation, isocyanate content = 23) 3%) and 90 g of water were stirred at 2000 rpm for 30 seconds at a high speed using a homomixer, and the time until the isocyanate group disappeared was measured.
[乳化・分散評価および臭気の確認]
製造実施例1、2、製造比較例1で得られた各乳化・分散剤EA−1〜3を4gとヘキサメチレンジイソシアネートのイソシアヌレート変性体(東ソー製コロネートHXLV、イソシアネート含量=23.3%)を6gと水を90g使用して、ホモミキサーを用いて2000rpmで30秒間高速攪拌し、乳化、分散させ、ヘキサメチレンジイソシアネートの臭気の有無を調べた。
[Emulsification / dispersion evaluation and odor confirmation]
4 g of each emulsifying and dispersing agent EA-1 to 3 obtained in Production Examples 1 and 2 and Production Comparative Example 1 and an isocyanurate modified product of hexamethylene diisocyanate (Tosoh Coronate HXLV, isocyanate content = 23.3%) 6 g and 90 g of water were stirred at 2000 rpm for 30 seconds at high speed using a homomixer, emulsified and dispersed, and the presence of odor of hexamethylene diisocyanate was examined.
乳化試験において、製造例EA−1、EA−2を用いたものについては臭気は無かったが、製造比較例EA−3のものは臭気が確認された。これはEA−3の製造過程において、遊離のヘキサメチレンジイソシアネートを蒸留・除去しなかったためと思われる。製造比較例EA−4では臭気はなかったが、高粘度のため水に乳化・分散しなかった。 In the emulsification test, there was no odor for those using Production Examples EA-1 and EA-2, but the odor was confirmed for those of Production Comparative Example EA-3. This seems to be because free hexamethylene diisocyanate was not distilled and removed in the production process of EA-3. Production Comparative Example EA-4 had no odor but was not emulsified / dispersed in water due to its high viscosity.
Claims (11)
第一工程:有機ジイソシアネート(a)と、疎水性基含有モノアルコール(b)をアロファネート触媒の存在下で反応させる工程。
第二工程:触媒毒を添加して、アロファネート化反応を停止させる工程。
第三工程:遊離の有機ジイソシアネート(a)を蒸留により除去する工程。
第四工程:第三工程から得られたアロファネート変性イソシアネートと、ノニオン性親水基含有一官能アルコール(c)をアロファネート触媒の存在下で反応させる工程。
第五工程:触媒毒を添加して、アロファネート化反応を停止させる工程。 A method for producing an emulsifying / dispersing agent obtained from the following steps.
First step: a step of reacting the organic diisocyanate (a) with a hydrophobic group-containing monoalcohol (b) in the presence of an allophanate catalyst.
Second step: A step of adding a catalyst poison to stop the allophanatization reaction.
Third step: a step of removing free organic diisocyanate (a) by distillation.
Fourth step: A step of reacting the allophanate-modified isocyanate obtained from the third step with a nonionic hydrophilic group-containing monofunctional alcohol (c) in the presence of an allophanate catalyst.
Fifth step: a step of adding a catalyst poison to stop the allophanatization reaction.
R1−O−(−R2−O−)n−H ・・・(式1)
(但し、R1はアルキル基を示し、R2はエチレン基を30モル%以上含有するアルキレン基を示す。nは1以上の整数を示す。) The method for producing an emulsifying / dispersing agent according to any one of claims 1 to 4, wherein the nonionic hydrophilic group-containing monofunctional alcohol (c) is represented by the following (formula 1).
R 1 —O — (— R 2 —O—) n—H (Formula 1)
(However, R 1 represents an alkyl group, R 2 represents an alkylene group containing 30 mol% or more of an ethylene group. N represents an integer of 1 or more.)
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JP2003055427A (en) * | 2001-08-21 | 2003-02-26 | Nippon Polyurethane Ind Co Ltd | Process for producing self-emulsifiable allophanate- modified polyisocyanate |
JP2004195385A (en) * | 2002-12-19 | 2004-07-15 | Nippon Polyurethane Ind Co Ltd | Emulsifying and dispersing agent, water emulsifying and dispersing isocyanate curing agent using the same, and water emulsifying and dispersing curable composition |
JP2004315598A (en) * | 2003-04-14 | 2004-11-11 | Nippon Polyurethane Ind Co Ltd | Emulsifying agent, water-emulsified isocyanate curing agent and water-emulsified curable composition using the same |
JP2009007409A (en) * | 2007-06-26 | 2009-01-15 | Mitsui Chemicals Polyurethanes Inc | Water-dispersible isocyanate composition and aqueous polyurethane resin composition |
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JP2003055427A (en) * | 2001-08-21 | 2003-02-26 | Nippon Polyurethane Ind Co Ltd | Process for producing self-emulsifiable allophanate- modified polyisocyanate |
JP2004195385A (en) * | 2002-12-19 | 2004-07-15 | Nippon Polyurethane Ind Co Ltd | Emulsifying and dispersing agent, water emulsifying and dispersing isocyanate curing agent using the same, and water emulsifying and dispersing curable composition |
JP2004315598A (en) * | 2003-04-14 | 2004-11-11 | Nippon Polyurethane Ind Co Ltd | Emulsifying agent, water-emulsified isocyanate curing agent and water-emulsified curable composition using the same |
JP2009007409A (en) * | 2007-06-26 | 2009-01-15 | Mitsui Chemicals Polyurethanes Inc | Water-dispersible isocyanate composition and aqueous polyurethane resin composition |
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WO2018180120A1 (en) | 2017-03-29 | 2018-10-04 | セントラル硝子株式会社 | Antenna and window glass |
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