JPH0367530B2 - - Google Patents
Info
- Publication number
- JPH0367530B2 JPH0367530B2 JP59151968A JP15196884A JPH0367530B2 JP H0367530 B2 JPH0367530 B2 JP H0367530B2 JP 59151968 A JP59151968 A JP 59151968A JP 15196884 A JP15196884 A JP 15196884A JP H0367530 B2 JPH0367530 B2 JP H0367530B2
- Authority
- JP
- Japan
- Prior art keywords
- isocyanate
- water
- weight
- added
- blocked isocyanate
- 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.)
- Expired - Lifetime
Links
- 239000012948 isocyanate Substances 0.000 claims description 40
- 150000002513 isocyanates Chemical class 0.000 claims description 36
- 239000002981 blocking agent Substances 0.000 claims description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 230000000903 blocking effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000839 emulsion Substances 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920005862 polyol Polymers 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 5
- -1 isocyanate compound Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 229920003169 water-soluble polymer Polymers 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000004814 polyurethane Substances 0.000 description 3
- 229920002635 polyurethane Polymers 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001718 carbodiimides Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は水に分散可能なブロツクイソシアネー
トの製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a process for producing water-dispersible blocked isocyanates.
水溶性高分子、水分散型高分子の産業界への応
用はその安全衛生面から近年次第に広がりつつあ
る。これらの高分子体は他の非水系高分子に較ら
べ本質的な欠点を有している。つまり親水基を高
分子体に何らかの手段で導入させているためによ
る耐水性、耐湿性の低下である。 The industrial applications of water-soluble polymers and water-dispersible polymers have been gradually expanding in recent years due to their safety and health aspects. These polymers have essential drawbacks compared to other non-aqueous polymers. In other words, the water resistance and moisture resistance are reduced due to the introduction of hydrophilic groups into the polymer by some means.
これらの改善のため架橋剤を添加して樹脂化時
に網状化させる方法をとることがある。この架橋
剤の１つにブロツクイソシアネート化合物があ
り、これは樹脂化時に加熱してブロツク剤を解離
させ遊離のイソシアネートを再生させ、高分子体
の活性水素と反応させて網状化させるものであ
る。 In order to improve these, a method is sometimes used in which a crosslinking agent is added to create a network during resin formation. One of these crosslinking agents is a blocked isocyanate compound, which is heated during resin formation to dissociate the blocking agent and regenerate free isocyanate, which reacts with the active hydrogen of the polymer to form a network.
従来この目的に用いるブロツクイソシアネート
は、トリメチロールプロパン、ジエチレングリコ
ールなどのような比較的低分子のポリオールとト
リレンジイソシアネートによるイソシアネート末
端プレポリマーにフエノールのようなブロツク剤
を反応させたものが代表的である。 The blocking isocyanate conventionally used for this purpose is typically one obtained by reacting a blocking agent such as phenol with an isocyanate-terminated prepolymer made of a relatively low-molecular polyol such as trimethylolpropane or diethylene glycol and tolylene diisocyanate. .
このブロツクイソシアネートは、通常常温で固
体であるから微細に粉末化して使用時水溶性高分
子に混合する。この際ブロツクイソシアネートの
分散は困難で均一にさせるために長時間を要す
る。また分散後も不安定で、ブロツクイソシアネ
ートは経時と共に分離するので作業上大きな制約
がある。 Since this blocked isocyanate is normally solid at room temperature, it is finely powdered and mixed with the water-soluble polymer when used. At this time, it is difficult to disperse the blocked isocyanate and it takes a long time to achieve uniformity. Furthermore, it is unstable even after dispersion, and the blocked isocyanate separates over time, which poses major operational constraints.
この欠点を解消するるために、界面活性剤の添
加、強い親水性基を有したブロツクの使用、ある
いは分子量1000以上の親水性ポリオールを用いた
プレポリマーの形をしたブロツクイソシアネート
を用いるなどの方法をとつている。界面活性剤を
用いる方法は、活性剤としてイオン系を使う場
合、得られた最終製品の経時物性に悪影響を与え
るし、非イオン系の場合は、添加量が全体の10％
以上にもなり好ましくない。 To overcome this drawback, methods such as adding surfactants, using blocks with strong hydrophilic groups, or using blocked isocyanates in the form of prepolymers using hydrophilic polyols with a molecular weight of 1000 or more are available. I'm taking it. In the method of using a surfactant, if an ionic surfactant is used as the surfactant, it will have a negative effect on the physical properties of the final product obtained over time, and if a nonionic surfactant is used, the amount added will be 10% of the total.
This is not desirable.
親水性にブロツク剤を用いる方法は、ブロツク
剤が焼付時系外へ出ないので製品の物性に悪影響
を与える欠点を有する。 The method of using a blocking agent for hydrophilic properties has the disadvantage that the blocking agent does not come out during baking, which adversely affects the physical properties of the product.
また高分子量の親水性ポリオールを用いるプレ
ポリマー形ブロツクイソシアネートは、ポリオー
ルの影響で製品硬度が低下したり、有効イソシア
ネート濃度も低下するので、架橋剤としての効果
が発揮されず好ましくない。 Furthermore, prepolymer-type blocked isocyanates using high molecular weight hydrophilic polyols are not preferred because they are not effective as crosslinking agents because the product hardness decreases and the effective isocyanate concentration decreases due to the influence of the polyol.
本発明者等は、上記のような欠点のない、水に
分散可能なブロツクイソシアネートを提供すべく
研究を重ねた結果、有機イソシアネートに
RO（CH2CH2O）oＨ
及び／または
R′（OCH2CH2）nOOCCH2COO（CH2CH2O）oR′
で示されるポリエチレンオキシド誘導体（ここで
ＲおよびR′は１〜４の炭素数のアルキル基、ｎ
およびｍは平均５〜120）を反応させて、残りの
イソシアネートをブロツク剤でブロツクした有効
NCO含量7.5〜17.5重量％ブロツクイソシアネー
トがこの目的に適うことを見出し本発明に到達し
たものである。 The present inventors have conducted repeated research to provide a water-dispersible blocked isocyanate free from the drawbacks mentioned above. OCH 2 CH 2 ) n OOCCH 2 COO (CH 2 CH 2 O) o Polyethylene oxide derivative represented by R' (where R and R' are an alkyl group having 1 to 4 carbon atoms, n
and m is 5 to 120 on average), and the remaining isocyanate was blocked with a blocking agent.
The present invention was achieved by discovering that a blocked isocyanate having an NCO content of 7.5 to 17.5% by weight is suitable for this purpose.
本発明で使用することのできる有機イソシアネ
ートとしては、工業的に用いられているイソシア
ネートが使用出来る。例えば、トリレンジイソシ
アネート、ジフエニルメタンジイソシアネート、
ポリフエニルメタンポリイソシアネート、ナフチ
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、イソホロンジイソシアネート、および
これらのイソシアネート化合物と分子量150以下
のポリオール類によるイソシアネート末端アダク
ト体、あるいはこれらのイソシアネート化合物の
カルボジイミド変性体、三量体などの変性イソシ
アネート化合物などがある。 As the organic isocyanate that can be used in the present invention, industrially used isocyanates can be used. For example, tolylene diisocyanate, diphenylmethane diisocyanate,
Polyphenylmethane polyisocyanate, naphthylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isocyanate-terminated adducts of these isocyanate compounds and polyols with a molecular weight of 150 or less, or carbodiimide modified products and trimers of these isocyanate compounds. Examples include modified isocyanate compounds.
有機イソシアネートと反応させるポリエチレン
オキシド誘導体としては下式で示される。 The polyethylene oxide derivative to be reacted with the organic isocyanate is represented by the following formula.
RO（CH2CH2O）oＨ (1)
または
R′（OCH2CH2）nOOCCH2COO（CH2CH2O）oR′ (2)
ここでＲおよびR′は１〜４の炭素数のアルキ
ル基、ｎおよびｍは平均５〜120である。Ｒおよ
びR′は特にメチル基が好ましく、またｎおよび
ｍは特に10〜30が好ましい。 RO (CH 2 CH 2 O) o H (1) or R' (OCH 2 CH 2 ) n OOCCH 2 COO (CH 2 CH 2 O) o R' (2) where R and R' are 1 to 4. The alkyl groups having carbon atoms, n and m, have an average number of 5 to 120 carbon atoms. R and R' are particularly preferably methyl groups, and n and m are particularly preferably 10-30.
例えば、(1)式でｎ＝14のメトキシポリエチレン
グリコール（分子量650）、(2)式でｎ＋ｍ＝28.8の
ビス（メトキシポリエチレンオキシ）マロネート
（分子量1400）などが使用される。この(1)及び(2)
をそれぞれ単独あるいは併用して用いることがで
きる。 For example, methoxypolyethylene glycol (molecular weight 650) where n=14 in formula (1) and bis(methoxypolyethyleneoxy)malonate (molecular weight 1400) where n+m=28.8 in formula (2) are used. This (1) and (2)
Each can be used alone or in combination.
有機イソシアネート100重量部に対して反応さ
せるポリエチレンオキシド誘導体の量は１〜20重
量部である。イソシアネートの種類、ブロツク剤
の種類、(1)または(2)式中のｎの値によつて使用す
る量が変わるけれども特に１〜10重量部が好まし
い。 The amount of polyethylene oxide derivative reacted with 100 parts by weight of organic isocyanate is 1 to 20 parts by weight. Although the amount used varies depending on the type of isocyanate, the type of blocking agent, and the value of n in formula (1) or (2), 1 to 10 parts by weight is particularly preferred.
この場合、ポリエチレンオキシド誘導体の使用
量が１重量部よりも少なくなると水分散性が低下
し好ましくない、また20重量部よりも多くなると
水分散性は問題ないが塗膜にしたとき物性の低下
をもたらす。 In this case, if the amount of the polyethylene oxide derivative used is less than 1 part by weight, the water dispersibility will decrease, which is undesirable, and if it exceeds 20 parts by weight, the water dispersibility will not be a problem, but the physical properties will deteriorate when formed into a coating film. bring.
本発明に使用することのできるブロツク剤とし
ては、例えばフエノール、クレゾールなどのフエ
ノール類、メチルエチルケトオキシム、シクロヘ
キサノンオキシムなどのオキシム類、ε−カプロ
ラクタムなどのラクタム類などがある。 Blocking agents that can be used in the present invention include, for example, phenols such as phenol and cresol, oximes such as methyl ethyl ketoxime and cyclohexanone oxime, and lactams such as ε-caprolactam.
有機イソシアネートとポリエチレンオキシド誘
導体の反応は通常のウレタン化条件で行なうこと
ができる。例えば反応温度は20℃〜150℃の範囲
が適当である。ブロツク剤とイソシアネート基の
反応は50〜200℃の通常のブロツク化反応条件に
従つて行なう。ブロツク剤の仕込み量は遊離のイ
ソシアネートに対して1.0〜1.5倍モル量が適して
いる。ブロツクはポリエチレンオキシド誘導体と
同時に反応させることも出来る。このようにして
得られたブロツクイソシアネートは、有効NCO
含量、7.5〜17.5重量％である。 The reaction between the organic isocyanate and the polyethylene oxide derivative can be carried out under normal urethanization conditions. For example, the reaction temperature is suitably in the range of 20°C to 150°C. The reaction between the blocking agent and the isocyanate group is carried out at 50 DEG to 200 DEG C. under conventional blocking reaction conditions. The appropriate amount of blocking agent to be added is 1.0 to 1.5 times the molar amount of free isocyanate. The block can also be reacted simultaneously with the polyethylene oxide derivative. The blocked isocyanate thus obtained has an effective NCO
content, 7.5-17.5% by weight.
また、必要に応じて適当な溶剤を使用すること
もできる。適当な溶剤としては例えば酢酸エチ
ル、酢酸ブチル、酢酸セロソルブなどのエステル
類、アセトン、メチルエチルケトン、メチルイソ
ブチルケトン、シクロヘキサノンなどのケトン
類、トルエン、キシレンなどの芳香族類、テトラ
ヒドロフランのごときエーテル類、その他ジメチ
ルホルムアミドなどが挙げられる。 Moreover, a suitable solvent can also be used if necessary. Suitable solvents include, for example, esters such as ethyl acetate, butyl acetate, cellosolve acetate, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatics such as toluene and xylene, ethers such as tetrahydrofuran, and other dimethyl esters. Examples include formamide.
本発明のブロツクイソシアネートの水分散をさ
らに改良するため通常使われる手段を併用するこ
とができる。少量の界面活性剤の添加、無機系の
分散助剤の添加、乳化安定剤の添加等が併用でき
る。 In order to further improve the aqueous dispersion of the blocked isocyanate of the present invention, commonly used means can be used in combination. Addition of a small amount of surfactant, addition of inorganic dispersion aid, addition of emulsion stabilizer, etc. can be used in combination.
さらにエチレンオキシド重合体あるいはエチレ
ンオキシド、プロピレンオキシドのブロツク共重
合体のような親水性基を含んだポリオールをブロ
ツクイソシアネート組成の中に適宜導入すること
も効果がある。 Furthermore, it is also effective to appropriately introduce a polyol containing a hydrophilic group, such as an ethylene oxide polymer or a block copolymer of ethylene oxide and propylene oxide, into the block isocyanate composition.
得られたブロツクイソシアネートは水をブロツ
クイソシアネート100重量部に対して50〜500重量
部加え、ボールミルのような粉砕機で分散させ
る。 The obtained blocked isocyanate is dispersed by adding 50 to 500 parts by weight of water to 100 parts by weight of the blocked isocyanate using a grinder such as a ball mill.
ブロツクイソシアネートが液状の場合は水を添
加して高速撹拌するだけで分散体がえられる。 When the blocked isocyanate is in liquid form, a dispersion can be obtained simply by adding water and stirring at high speed.
本発明で得られたブロツクイソシアネートは通
常の溶液型としても使用することができる。 The blocked isocyanate obtained in the present invention can also be used in a conventional solution form.
本発明で得られるブロツクイソシアネート分散
体は、水溶性高分子、水分散型高分子等の硬化
剤、改質剤、架橋剤として用いられる。 The blocked isocyanate dispersion obtained in the present invention is used as a curing agent, modifier, or crosslinking agent for water-soluble polymers, water-dispersible polymers, and the like.
これらの用途は極めて多岐にわたるが、例え
ば、本発明のブロツクイソシアネートを硬化剤と
して用いた樹脂は繊維、木質材、紙、多孔質無機
材の接着剤、バインダー、塗料等に用いられる。 These uses are extremely diverse, and for example, resins using the blocked isocyanate of the present invention as a curing agent are used for fibers, wood materials, paper, adhesives for porous inorganic materials, binders, paints, etc.
ここで水分散型高分子とは、例えばエポキシエ
マルジヨン、ブタジエン系エマルジヨン、アクリ
レートラテツクス、塩ビ酢ビ系エマルジヨンなど
のプラスチツクエマルジヨンや、天然ゴムラテツ
クス、水溶性セルロース誘導体などの天然系エマ
ルジヨンなどである。 Here, water-dispersed polymers include, for example, plastic emulsions such as epoxy emulsions, butadiene emulsions, acrylate latexes, and vinyl chloride-vinyl acetate emulsions, and natural emulsions such as natural rubber latex and water-soluble cellulose derivatives. .
又水溶性高分子とは、ポリビニールアルコー
ル、ポリエチレングリコール、ポリエチレングリ
コールポリプロピレングリコール共重合体、水性
アルキツド樹脂、水ガラスなどの無機系化合物等
が挙げられる。 Examples of water-soluble polymers include inorganic compounds such as polyvinyl alcohol, polyethylene glycol, polyethylene glycol polypropylene glycol copolymers, water-based alkyd resins, and water glass.
これらの分野で必要とされる各種添加剤、例え
ば酸化防止剤、顔料、フイラー、分散安定剤など
を本発明のブロツクイソシアネートおよびその分
散体に添加して使用することもできる。 Various additives required in these fields, such as antioxidants, pigments, fillers, and dispersion stabilizers, can also be added to the blocked isocyanate and its dispersion of the present invention.
次に本発明について実施例および比較例により
更に詳細に説明する。 Next, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
例における％とは重量％である。 % in the examples is weight %.
実施例 １
温度計、冷却器、撹拌機および滴下ロートを備
えた１容の反応器にコロネートHL（日本ポリ
ウレタン工業製 商品名、ヘキサメチレンジイソ
シアネートアダクト体、NCO濃度12.8％）328
ｇ、メトオキシポリエチレングリコール（分子量
650）13.5ｇおよびε−カプロラクタム124ｇを秤
り取り、撹拌混合しながら加熱する。70℃で３時
間反応させた後、ジブチルチンジラウレートを
0.02ｇ添加し、70℃、10時間反応させて反応を完
結した。水400ｇを加え、高速撹拌により、分散
性の優れた安定な水乳化物が得られた。有効
NCO含量は8.8％であつた。Example 1 Coronate HL (manufactured by Nippon Polyurethane Industries, trade name, hexamethylene diisocyanate adduct, NCO concentration 12.8%) 328 was placed in a 1-volume reactor equipped with a thermometer, condenser, stirrer, and dropping funnel.
g, methoxypolyethylene glycol (molecular weight
650) Weigh out 13.5 g and 124 g of ε-caprolactam, and heat while stirring and mixing. After reacting at 70℃ for 3 hours, dibutyltin dilaurate was added.
0.02g was added and the reaction was completed at 70°C for 10 hours. By adding 400 g of water and stirring at high speed, a stable water emulsion with excellent dispersibility was obtained. valid
The NCO content was 8.8%.
実施例 ２
実施例１と同様の反応器にミリオネートMTL
（日本ポリウレタン工業製 商品名、ジフエニル
メタンジイソシアネートのカルボジイミド変性
体、NCO濃度28.9％）262ｇ、酢酸エチル262ｇ、
ε−カプロラクタム223ｇおよびメトキシポリエ
チレングリコール（分子量650）15ｇを秤り取り、
撹拌混合しながら70℃に加熱した。70℃、10時間
で反応を終らせ、スラリー状の反応生成物をろ過
し固形分を得た。有効NCO含量は14.5％であつ
た。水700ｇを加えて、ボールミルで粉砕分散さ
せた。分散性の優れた安定な水乳化物がえられ
た。Example 2 Millionate MTL was added to the same reactor as Example 1.
(Product name manufactured by Nippon Polyurethane Industries, carbodiimide modified product of diphenylmethane diisocyanate, NCO concentration 28.9%) 262g, ethyl acetate 262g,
Weigh out 223 g of ε-caprolactam and 15 g of methoxypolyethylene glycol (molecular weight 650),
The mixture was heated to 70° C. while stirring and mixing. The reaction was completed at 70°C for 10 hours, and the slurry-like reaction product was filtered to obtain a solid content. The effective NCO content was 14.5%. 700 g of water was added and the mixture was pulverized and dispersed using a ball mill. A stable water emulsion with excellent dispersibility was obtained.
実施例 ３
実施例１と同様の反応器にミリオネートMTL
（実施例２で使用したもの）284ｇ、酢酸エチル
484ｇ、およびメトキシポリエチレングリコール
（分子量650）20ｇを秤り取り、撹拌混合しながら
70℃に加熱する。200ｇのフエノールを３時間か
けて滴下した。反応生成物は半固形状で酢酸エチ
ルを除くためろ過した。固形分を60℃のオーブン
に16時間入れて反応を終了させた。有効NCO含
量は15.8％であつた。水1000ｇを加えて、ボール
ミルで粉砕分散させた。分散性の優れた安定な水
乳化物がえられた。Example 3 Millionate MTL was added to the same reactor as Example 1.
(Used in Example 2) 284g, ethyl acetate
Weigh out 484g and 20g of methoxypolyethylene glycol (molecular weight 650) and mix while stirring.
Heat to 70°C. 200 g of phenol was added dropwise over 3 hours. The reaction product was semi-solid and was filtered to remove ethyl acetate. The reaction was completed by placing the solids in an oven at 60°C for 16 hours. The effective NCO content was 15.8%. 1000 g of water was added and the mixture was pulverized and dispersed using a ball mill. A stable water emulsion with excellent dispersibility was obtained.
実施例 ４
実施例１と同様の２の反応器にミリオネート
MT（日本ポリウレタン工業製 商品名、ジフエ
ニルメタンジイソシアネート）250ｇ、酢酸エチ
ル470ｇ、および分子量1400のビス（メトキシポ
リエチレンオキシ）マロネート25ｇを秤り取り、
70℃、２時間反応させた。その後、220ｇのフエ
ノールを３時間かけて滴下した。反応生成物は半
固形状で、酢酸エチルを除くためろ過した。固形
分を60℃のオーブンに16時間入れて反応を終了さ
せた。有効NCO含量は16.5％であつた。水1000
ｇを加えてボールミルで粉砕分散させた。分散性
の優れた安定な水乳化物がえられた。この乳化物
は被覆材、接着材などの焼付け型硬化剤として有
用であつた。Example 4 Millionate was added to two reactors similar to Example 1.
Weigh out 250 g of MT (trade name, diphenylmethane diisocyanate, manufactured by Nippon Polyurethane Industries), 470 g of ethyl acetate, and 25 g of bis(methoxypolyethyleneoxy) malonate with a molecular weight of 1400.
The reaction was carried out at 70°C for 2 hours. Thereafter, 220 g of phenol was added dropwise over 3 hours. The reaction product was semi-solid and was filtered to remove ethyl acetate. The reaction was completed by placing the solids in an oven at 60°C for 16 hours. The effective NCO content was 16.5%. water 1000
g was added and the mixture was pulverized and dispersed using a ball mill. A stable water emulsion with excellent dispersibility was obtained. This emulsion was useful as a baking type curing agent for coating materials, adhesives, etc.
比較例 １
実施例１の合成組成で、メトオキシポリエチレ
ングリコール（分子量650）13.5ｇを除いたブロ
ツクイソシアネートを合成した。このブロツクイ
ソシアネート452ｇにラウリルアルコールにエチ
レンオキシド15モルに附加した非イオン界面活性
剤17.0ｇを加えて均一に混合した。この混合物に
水400ｇを加え、高速撹拌により乳化した結果、
分散性の悪い乳化物しかえられなかつた。Comparative Example 1 Blocked isocyanate was synthesized using the synthesis composition of Example 1 except that 13.5 g of methoxypolyethylene glycol (molecular weight 650) was removed. To 452 g of this blocked isocyanate, 17.0 g of a nonionic surfactant prepared by adding 15 moles of ethylene oxide to lauryl alcohol was added and mixed uniformly. Add 400g of water to this mixture and emulsify it by high speed stirring.
Only emulsions with poor dispersibility could be obtained.
比較例 ２
比較例１で合成したブロツクイソシアネート
452ｇにメトオキシポリエチレングリコール（分
子量650）を13.5ｇに加えて均一に混合した。こ
の混合物に水400ｇを加え、高速撹拌により乳化
した結果、分散性の悪い乳化物しかえられなかつ
た。Comparative Example 2 Blocked isocyanate synthesized in Comparative Example 1
13.5 g of methoxypolyethylene glycol (molecular weight 650) was added to 452 g and mixed uniformly. When 400 g of water was added to this mixture and emulsified by high-speed stirring, only an emulsion with poor dispersibility was obtained.
Claims (1)
ＲおよびR′は１〜４の炭素数のアルキル基、ｎ
およびｍは平均５〜120）１〜20重量部を反応さ
せ、残りの遊離のイソシアネートをブロツク剤で
ブロツクして得られる有効イソシアネート含有
7.5〜17.5重量％であることを特徴とするブロツ
クイソシアネートの製造法。[Claims] 1. RO(CH 2 CH 2 O) o H (1) and/or R′(OCH 2 CH 2 ) n OOCCH 2 COO(CH 2 CH 2 O) o R to 100 parts by weight of organic isocyanate. '(2) A polyethylene oxide derivative represented by (where R and R' are an alkyl group having 1 to 4 carbon atoms, n
and m is an average of 5 to 120) containing effective isocyanate obtained by reacting 1 to 20 parts by weight and blocking the remaining free isocyanate with a blocking agent.
A method for producing blocked isocyanate, characterized in that the content is 7.5 to 17.5% by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59151968A JPS6131422A (en) | 1984-07-24 | 1984-07-24 | Preparation of water-dispersible blocked isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59151968A JPS6131422A (en) | 1984-07-24 | 1984-07-24 | Preparation of water-dispersible blocked isocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6131422A JPS6131422A (en) | 1986-02-13 |
| JPH0367530B2 true JPH0367530B2 (en) | 1991-10-23 |
Family
ID=15530150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59151968A Granted JPS6131422A (en) | 1984-07-24 | 1984-07-24 | Preparation of water-dispersible blocked isocyanate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6131422A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0826217B2 (en) * | 1987-04-09 | 1996-03-13 | 大日本インキ化学工業株式会社 | Urethane modifier |
| JPS63285454A (en) * | 1987-05-18 | 1988-11-22 | Shinkosumosu Denki Kk | Detection of city gas leaked from buried pipe |
| JP2575068B2 (en) * | 1990-10-23 | 1997-01-22 | 日本ポリウレタン工業株式会社 | Water-dispersible blocked isocyanate composition |
| DE69728346T2 (en) * | 1996-10-08 | 2005-02-10 | Nippon Polyurethane Industry Co., Ltd. | A water-dispersible blocked isocyanate-containing composition and aqueous coating composition and adhesive composition using the same |
| KR100538846B1 (en) * | 1997-12-31 | 2006-03-27 | 주식회사 케이씨씨 | Core / shell microgel containing alkylene monoisocyanate / poly (ethylene oxide) monoalcohol monomer and coating composition containing same |
| JP5170499B2 (en) * | 2006-08-18 | 2013-03-27 | 日本ポリウレタン工業株式会社 | Emulsion composition containing blocked isocyanate, method for producing the same, and composition for baking type paint or adhesive |
| JP5446077B2 (en) * | 2007-08-17 | 2014-03-19 | 日本ポリウレタン工業株式会社 | Aqueous resin composition comprising a blocked isocyanate-containing aqueous emulsion composition as a curing agent, and an aqueous baking type paint or adhesive composition using the same |
| JP5299420B2 (en) * | 2008-03-14 | 2013-09-25 | 日本ポリウレタン工業株式会社 | Emulsion composition containing blocked isocyanate, method for producing the same, aqueous base treatment agent for porous substrate, and aqueous baking coating composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5043198A (en) * | 1973-08-21 | 1975-04-18 |
-
1984
- 1984-07-24 JP JP59151968A patent/JPS6131422A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5043198A (en) * | 1973-08-21 | 1975-04-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6131422A (en) | 1986-02-13 |
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