JPH02261816A - Preparation of urethane prepolymer for coating - Google Patents
Preparation of urethane prepolymer for coatingInfo
- Publication number
- JPH02261816A JPH02261816A JP1081580A JP8158089A JPH02261816A JP H02261816 A JPH02261816 A JP H02261816A JP 1081580 A JP1081580 A JP 1081580A JP 8158089 A JP8158089 A JP 8158089A JP H02261816 A JPH02261816 A JP H02261816A
- Authority
- JP
- Japan
- Prior art keywords
- prepolymer
- urethane prepolymer
- tolylene diisocyanate
- trimethylolpropane
- diol
- 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
Links
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000576 coating method Methods 0.000 title claims description 9
- 239000011248 coating agent Substances 0.000 title description 5
- 238000002360 preparation method Methods 0.000 title 1
- 150000002009 diols Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003973 paint Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 abstract description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 30
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002904 solvent Substances 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 150000002430 hydrocarbons Chemical class 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- 239000012299 nitrogen atmosphere Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 8
- 125000005442 diisocyanate group Chemical class 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 229920005862 polyol Polymers 0.000 description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 150000003077 polyols Chemical class 0.000 description 6
- 239000010409 thin film Substances 0.000 description 6
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- -1 acyclic hydrocarbon Chemical class 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012948 isocyanate Substances 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 150000004072 triols Chemical class 0.000 description 3
- 150000003673 urethanes Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical class NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003759 ester based solvent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はジオール類およびトリメチロールプロパン（以
下、ＴＭＰと略記する）とトルエンジイソシアネート（
以下、ＴＤＩと略記する）を反応させ、塗料用ウレタン
プレポリマーとする製造方法に関する。更に詳しくは、
末端に水酸基を有するプレポリマーとしたのちＴＭＰを
加え過剰のＴＤＩ と反応させる、改良された塗料用ウ
レタンプレポリマーの製造方法に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to diols, trimethylolpropane (hereinafter abbreviated as TMP) and toluene diisocyanate (
The present invention relates to a method for producing a urethane prepolymer for coatings by reacting urethane prepolymer (hereinafter abbreviated as TDI). For more details,
This invention relates to an improved method for producing a urethane prepolymer for paints, which involves preparing a prepolymer having a hydroxyl group at the end, adding TMP and reacting with excess TDI.
〔従来の技術］
塗料用ウレタンプレポリマーはジイソシアネートをポリ
オールでウレタン変性したものや、水でビユレット変性
したものトリマー変性したものなどが広く使用されてい
る。[Prior Art] As urethane prepolymers for coatings, diisocyanate modified with urethane with polyol, biuret modified with water, trimer modified, etc. are widely used.
ジイソシアネートをポリオールでウレタン変性する場合
、長鎖ジオールを使用すると、ｌとして使用した場合、
塗膜にたわみ性とゴム弾性性状を与える。一方、短鎖の
ジオール、トリオールを使用すると、連鎖延長または橋
かけ（三次元構造）をして塗膜に靭性と剛性を与える。When a diisocyanate is urethane modified with a polyol, when a long chain diol is used, when used as l,
Gives flexibility and rubber elasticity to the coating film. On the other hand, when short-chain diols and triols are used, chain extension or cross-linking (three-dimensional structure) imparts toughness and rigidity to the coating film.
ジイソシアネ−！・、例えばＴＤ［を用いた場合、問題
点としては、ＴＤＩの分子量が小さく揮発性があり、さ
らに有毒であることである。この揮発性と存毒性のため
にＴＤＩを取り扱う場合性、ａが必要である。このよう
な観点からＴ、ＤＩのようなジイソシアネートをポリオ
ールと反応させ分子量を増加させることによって揮発性
を減少させることは有効な方法といえる。これらポリオ
ールによる延長芳香族ジイソシアネートの代表的組成と
合成法に関するものが下記の文献中に開示されている。Diisocyanate! - For example, when using TD, the problem is that TDI has a small molecular weight, is volatile, and is also toxic. Due to its volatility and toxicity, certain precautions are required when handling TDI. From this point of view, it can be said that it is an effective method to reduce volatility by reacting diisocyanates such as T and DI with polyols to increase their molecular weight. Representative compositions and synthetic methods of extended aromatic diisocyanates using these polyols are disclosed in the following documents.
米国特許第２，９６９．３８６号は、ＴＤｌのような芳
香族ジイソシアネートをエチレングリコールやＴＭＰの
ような短連類ジオールまたはトリオールとで反応させた
ウレタンポリイソノアネートの製法を示している。U.S. Pat. No. 2,969,386 describes a process for making urethane polyisonoanates by reacting an aromatic diisocyanate, such as TDl, with a short chain diol or triol, such as ethylene glycol or TMP.
米国特許第２．９６９，３８６号は遊、！４ＴＤＩを１
％以下とし、さらに高分子量のポリイソンア矛−１−の
生成を抑制することを目的としている。U.S. Patent No. 2,969,386 is a play! 4 TDI to 1
% or less, and further aims to suppress the formation of high molecular weight polyisomer-1-.
すなわち（ａ）化学！ｉ論量以上のジイソシアネートを
ポリオールと反応させて、好ましくない高分子化合物を
抑制する（ｂ）前記反応混合物を脂肪族または非環式炭
化水素と接触させて、前記混合物から未反応ジイソシア
ネートを抽出する（ｃ）未反応ジイソシア名−１・およ
びポリオールを含有する溶剤層を分離することによって
除去する。Namely (a) Chemistry! (b) contacting said reaction mixture with an aliphatic or acyclic hydrocarbon to extract unreacted diisocyanate from said mixture; (c) The solvent layer containing unreacted diisocyanate-1 and polyol is removed by separation.
この方法により、未反応ジイソシアネートと高分子化合
物を含有しないウレタン結合芳香族ジイソシア２−トを
得ている。By this method, a urethane-bonded aromatic diisocyanate containing no unreacted diisocyanate and a polymer compound is obtained.
また他の合成法として、エステル系の溶剤中にＴＤｌを
溶解した後、末端がイソシアネート基となるために必要
な化学量論量の１．３−ブタンジオールのようなジオー
ル類とＴＭＰのようなトリオール類を反応させてウレタ
ンプレポリマーを得ている。In addition, as another synthesis method, after dissolving TDl in an ester solvent, a stoichiometric amount of a diol such as 1,3-butanediol and a diol such as TMP necessary for the terminal to become an isocyanate group is used. Urethane prepolymers are obtained by reacting triols.
この方法はＴＤＩ とポリオールをＮＣ０１０１１官能
基モル比をほぼ２．０で使用するため反応終了時の未反
応Ｔｉ１ｌは１％以下となり、未反応ＴＯ＋を除去する
必要がなく、長期貯蔵安定性は良好であるが、しかし、
この方法は高分子化合物の生成量が多くなり硬化剤とし
て使用するポリエステルポリオール、アクリルポリオー
ル、稀釈剤として使用するトルエン、キシレン等の各種
溶媒との相溶性が悪くなり塗料用イソシアネートとして
必要なＮＣＯ基含有量が低下し、さらに溶液粘度が亮く
なる等、塗料とした場合の品質及び作業性に問題がある
。This method uses TDI and polyol at a molar ratio of NC01011 functional groups of approximately 2.0, so the amount of unreacted Ti11 at the end of the reaction is less than 1%, there is no need to remove unreacted TO+, and long-term storage stability is good. However,
This method produces a large amount of polymeric compounds, which deteriorates their compatibility with various solvents such as polyester polyols and acrylic polyols used as curing agents, and toluene and xylene used as diluents. There are problems with quality and workability when used as a paint, such as a decrease in content and an increase in solution viscosity.
前記米国特許第２．９６９．３８６号はＴＤｌのような
芳香族ジイソシアネートをエチレングリコールやＴＭＰ
のような短連鎖、ジオールまたはトリオールとで反応さ
せたウレタンプレポリマーの製法を示したものであり、
この方法により未反応ジイソシアネートと高分子化合物
の少ないウレタン結合芳香族ジイソシアネートを得るこ
とが可能である。またこの方法によって得られるウレタ
ンプレポリマーを塗料として使用した場合、連鎖延長と
橋かけ三次元構造をとるため強靭な塗膜が得られる。The above-mentioned U.S. Pat.
A method for producing urethane prepolymers reacted with short chains, diols or triols, such as
By this method, it is possible to obtain a urethane-bonded aromatic diisocyanate containing less unreacted diisocyanate and polymer compounds. Furthermore, when the urethane prepolymer obtained by this method is used as a paint, a tough paint film can be obtained due to the chain extension and cross-linked three-dimensional structure.
このウレタンプレポリマーは、通常、酢酸エチル等のエ
ステル系あるいはキシレン等の芳香族炭化水素の溶剤に
溶解して使用する。このウレタンプレポリマーを直ちに
塗料として使用すれば問題はないが、溶剤に溶解した状
態でも長時間保存すると、ウレタンプレポリマー、特に
トリメチロールプロパン１分子にＴＤｌ ３分子が付加
したトリメチロールプロパン３ＴＤＩ（以下、ＴＭＰ−
３ＴＤＴ と略す）が結晶化を起こし、析出するという
問題があった。This urethane prepolymer is usually used after being dissolved in an ester solvent such as ethyl acetate or an aromatic hydrocarbon solvent such as xylene. There is no problem if this urethane prepolymer is used immediately as a paint, but if it is stored for a long time even when dissolved in a solvent, urethane prepolymer, especially trimethylolpropane 3TDI (hereinafter referred to as trimethylolpropane 3TDI), which has 3 molecules of TDl added to 1 molecule of trimethylolpropane, , TMP-
There was a problem that 3TDT) caused crystallization and precipitated.
ＴＭＰ−３７ＤＩは、塗料として使用した際、橋かけ三
次元構造をとるため、塗膜に強度を与える反面、ＴＭＰ
−３７ＤＩが結晶化しやすく、溶剤に溶解しても長期間
保存すると結晶が析出してしまうため、製造後の長期貯
蔵安定性が悪くこの欠点を改良するためには■重々の方
法があるが各々欠点がある。例えばＴＭＰ／ジオールの
モル比を下げてＴＭＰ−３ＴＤｌを減少させると塗料と
した場合の塗膜の強度が悪くなるまた、プレポリマー製
造時のイソシアネート基過剰率を下げプレポリマー中の
高分子体を多くすると貯蔵安定性は改良されるがプレポ
リマーのＮＣＯχが低下する、粘度が高くなる、溶剤ｆ
希釈性が悪くなる等の欠点が生しる為これらの欠点を生
じることなく長期貯蔵安定性の改善された塗料用ウレタ
ンプレポリマーが望まれていた。When TMP-37DI is used as a paint, it takes on a three-dimensional bridged structure, which gives strength to the paint film, but on the other hand, TMP-37DI
-37DI tends to crystallize, and even if it is dissolved in a solvent, crystals will precipitate when stored for a long time, resulting in poor long-term storage stability after production.There are many ways to improve this drawback, but each method is different. There are drawbacks. For example, if the molar ratio of TMP/diol is lowered to reduce TMP-3TDl, the strength of the coating film will deteriorate, and the excess ratio of isocyanate groups during prepolymer production will be lowered to reduce the polymer content in the prepolymer. If the amount is increased, the storage stability will be improved, but the NCOχ of the prepolymer will decrease, the viscosity will increase, and the solvent f
Since there are drawbacks such as poor dilutability, there has been a desire for a urethane prepolymer for paints that does not have these drawbacks and has improved long-term storage stability.
Ｔｈｐ−３ｒｏｒは結晶化を起こしやすい。ならばウレ
タンプレポリマー中のＴＭＰ−３ＴＯ＋の絶対量を減ら
せば結晶化を防ぐことは可能である。しかし、ＴＭＰ３
ＴＤ Ｉは三官能イソシアネート成分として、塗料に使
用した際、三次元の橋かけ構造をとり、塗膜に強度を与
えるため三官能のイソシアネート成分の絶対量はできる
かぎり減らしたくない。Thp-3ror is prone to crystallization. If so, it is possible to prevent crystallization by reducing the absolute amount of TMP-3TO+ in the urethane prepolymer. However, TMP3
When TDI is used as a trifunctional isocyanate component in a paint, it forms a three-dimensional crosslinked structure and provides strength to the coating film, so it is desirable not to reduce the absolute amount of the trifunctional isocyanate component as much as possible.
本発明者等は鋭意検討した結果、塗料用ウレタンプレポ
リマーとする場合、ジオール１分子にＴＤ［２分子が付
加したものよりもＴＭＰ−３ＴＯ＋に分子量が近いジオ
ール２分子にＴＯｌ ３分子が付加したポリウクンイソ
シアネートを混合したほうがＴＭＰ−３７ＤＩの結晶化
を抑制する働きが強くさらにこのジオール２分子に７０
１３分子が付加したポリウレタンイソシアネートを含む
プレポリマーはキシレン、トルエン等の各種溶媒との相
溶性が良いことを見出した。 そこでウレタンプレポリ
マー組成物の中にジオール２分子に７０１３分子が付加
したウレタンプレポリマー成分を多くするにはジオール
成分に少量のＴＤＩを加え反応させ、一部、ジオールＴ
Ｄｒ−ジオールのような末端に水酸基をもつプレポリマ
ーとし、これにＴＭＰを加え、又は別々に過剰のＴＤｌ
を加えることによりウレタンプレポリマー中のジオール
２分子に ＴＤｌ ３分子が付加したウレタンプレポリ
マー成分を多くする処方を検討した。その結果、改良さ
れたウレタンプレポリマー組成物はＴ？ＩＰ−３７Ｄｒ
の結晶化が抑制され、かつ溶剤との相溶性が良いことを
を確認し、本発明を完成した。As a result of extensive studies, the present inventors found that when making a urethane prepolymer for paints, three molecules of TOl were added to two molecules of diol, which has a molecular weight closer to that of TMP-3TO+, than the one in which two molecules of TD were added to one molecule of diol. Mixing polyurethane isocyanate has a stronger effect of suppressing the crystallization of TMP-37DI, and furthermore, 70
It has been found that a prepolymer containing polyurethane isocyanate to which 13 molecules have been added has good compatibility with various solvents such as xylene and toluene. Therefore, in order to increase the urethane prepolymer component in which 7013 molecules are added to 2 diol molecules in the urethane prepolymer composition, a small amount of TDI is added to the diol component and reacted, and some of the diol T
A prepolymer with terminal hydroxyl groups such as Dr-diol is prepared, and TMP is added to this, or an excess of TDl is added separately.
We investigated a formulation in which the amount of the urethane prepolymer component in which 3 molecules of TDl were added to 2 molecules of diol in the urethane prepolymer by adding . As a result, the improved urethane prepolymer composition is T? IP-37Dr
The present invention was completed by confirming that crystallization was suppressed and the compatibility with solvents was good.
すなわち、本発明は、一種又は二種以上のジオール類お
よびＴ？ＩＰとＴＤｒを反応し塗料用ウレタンプレポリ
マーを製造する方法に於いて、ＴＤ［に対し２倍モル以
上のジオール類と反応させ、末端に水酸基を有するプレ
ポリマーとしたのち該反応液にＴＩ’ＩＰを混合し、更
に、水酸基に対し過剰のＴＤＩと反応させ、末端にイソ
シアネート基を有するウレタンプレポリマーとし、未反
応のＴＤＩを除去することを特徴とする塗料用ウレタン
プレポリマーの製造方法である。That is, the present invention provides one or more diols and T? In a method for producing a urethane prepolymer for paints by reacting IP and TDr, TD is reacted with diols in an amount of at least twice the mole to form a prepolymer having a hydroxyl group at the terminal, and then TI' is added to the reaction solution. A method for producing a urethane prepolymer for paints, which comprises mixing IP, reacting with TDI in excess of hydroxyl groups to obtain a urethane prepolymer having isocyanate groups at the terminals, and removing unreacted TDI. .
本発明の目的は酢酸エチル等のエステル系あるいはトル
エン等の芳香族炭化水素系の溶剤に溶解し長期間、安定
に保存できる改良された塗料用ウレタンプレポリマーの
製造方法を提供するものである。An object of the present invention is to provide an improved method for producing a urethane prepolymer for paints that can be dissolved in an ester-based solvent such as ethyl acetate or an aromatic hydrocarbon-based solvent such as toluene and can be stored stably for a long period of time.
本発明の方法に使用するジオール類としては、脂肪族ジ
オールであり、例えばエチレングリコール、ジエチレン
グリコール、トリエチレングリコール、プロピレングリ
コール、ジプロピレングリコール、トリプロピレングリ
コール、１．２−ブタンジオール、１．３−ブタンジオ
ール、１．４−ブタンジオール等が挙げられる。トリオ
ールとしてはトリメチロールプロパンが用いられる。更
に、ｔルエンジイソシアネートとしては２．４−）ルエ
ンジイソシアネート、２．６−）ルエンジイソシアネー
トあるいはそれらの混合物が用いられる。The diols used in the method of the present invention are aliphatic diols, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3- Examples include butanediol, 1,4-butanediol, and the like. Trimethylolpropane is used as the triol. Further, as the t-toluene diisocyanate, 2.4-) toluene diisocyanate, 2.6-) toluene diisocyanate, or a mixture thereof is used.
本発明の方法は、２段階の操作からなる。第１段階とし
ては、反応容器にジオール類を装入し、不活性ガス雰囲
気下、好ましくは窒素雰囲気下、ＴＤＩを滴下、反応し
末端に水酸基を有するジオールプレポリマーとする０反
応に使用するジオールは一種又は二種以上の混合物とし
て用いる。ジオール類とＴＤＩの使用割合はＮＧＯｌｏ
）ｌ官能基モル比が通常０．０１〜０．５の範囲内、好
ましくは０．１−０．４の範囲である。The method of the invention consists of a two-step operation. In the first step, diols are charged into a reaction vessel, TDI is added dropwise under an inert gas atmosphere, preferably a nitrogen atmosphere, and the diol used in the reaction is reacted to obtain a diol prepolymer having a hydroxyl group at the terminal. are used singly or as a mixture of two or more. The usage ratio of diols and TDI is NGOlo
)l functional group molar ratio is usually in the range of 0.01 to 0.5, preferably in the range of 0.1 to 0.4.
反応温度及び反応時間は２０〜１００”Ｃ１好ましくは
４０〜６０°Ｃの範囲で３０分〜５時間、好ましくは１
〜２時間である。The reaction temperature and reaction time are 30 minutes to 5 hours, preferably 1
~2 hours.
第２段階の操作は不活性ガスの雰囲気下、好ましくは窒
素雰囲気下、大過剰のＴＤｌ中に１段階の反応で得られ
た末端に水酸基を有するジオールプレポリマーとＴＭＰ
を滴下し、ウレタンプレポリマーとする。末端に水酸基
を有するジオールプレポリマーとトリメチロールプロパ
ンを滴下する順序は同時あるいはいずれが先でもかまわ
ない。反応温度および反応時間は２０〜１００’Ｃ１好
ましくは５゜〜８０°Ｃの範囲で３０分〜５時間、好ま
しくは１〜２時間である。The second stage operation is carried out under an inert gas atmosphere, preferably a nitrogen atmosphere, in a large excess of TDl, using the diol prepolymer having a hydroxyl group at the end obtained in the first stage reaction and TMP.
is added dropwise to form a urethane prepolymer. The diol prepolymer having a hydroxyl group at the end and the trimethylolpropane may be added dropwise at the same time or in either order. The reaction temperature and reaction time are 30 minutes to 5 hours, preferably 1 to 2 hours, in the range of 20 to 100'C1, preferably 5 to 80C.
反応に使用するＴＤＩの使用割合はＮＣ０１０１１官能
基モル比が通常１．５〜１０の範囲、好ましくは４〜６
の範囲である。The proportion of TDI used in the reaction is such that the molar ratio of NC01011 functional groups is usually in the range of 1.5 to 10, preferably 4 to 6.
is within the range of
このようにして得た、反応液から過剰の未反応ＴＤＩを
一般的な分Ｍｆｆ方法、例えばボア）遺留、薄膜蒸留、
フラッジａ蒸留、あるいは抽出などの操作によって除去
し、ウレタンプレポリマー組成物を得る。The excess unreacted TDI thus obtained is removed from the reaction solution using a general fraction Mff method, e.g., bore) retention, thin film distillation,
A urethane prepolymer composition is obtained by removing the fluorine by distillation or extraction.
ウレタンプレポリマー組成物は、各種の溶剤、例えば酢
酸エチル、酢酸ブチルなどのエステル類あるいはトルエ
ン、キシレンなどの芳香族炭化水素に熔解し４０〜８０
％のウレタンプレポリマー溶液の形態で塗料用として用
いられる。The urethane prepolymer composition is dissolved in various solvents such as esters such as ethyl acetate and butyl acetate, or aromatic hydrocarbons such as toluene and xylene.
% urethane prepolymer solution for coatings.
（発明の効果］
本発明の方法で得られるウレタンプレポリマーは各種溶
剤中で長期間、安定に保存が出来、かつＮＣＯχが高く
、低粘度で、溶剤稀釈性が良い製品であり工業的に経済
性のメリットが大きい。(Effect of the invention) The urethane prepolymer obtained by the method of the present invention can be stored stably for a long period of time in various solvents, has a high NCOχ, has a low viscosity, and has good solvent dilutability, and is industrially economical. There are great sexual benefits.
次に本発明の方法を実施例によって具体的に説明する。 Next, the method of the present invention will be specifically explained using examples.
（貯蔵）安定性試験方法
０２０ｍ１のサンプル管に試料１５ｇ、ｎ−ヘキサン３
．７５ｇを加え十分に振った後、３０°Ｃにて２週間保
管し、目視により観察する。(Storage) Stability test method 15 g of sample in a 020 ml sample tube, 3 ml of n-hexane
．． After adding 75 g and shaking thoroughly, store at 30°C for 2 weeks and visually observe.
０２０ｍ１のサンプル管に試料１５ｇ、キシレン２．２
５ｇ、、Ｔ門Ｐ−３７ＤＩの固体１ ｍｇを加え十分に
振って混合した後、−５“Ｃにて２週間保管し、目視に
より観察する。15 g of sample in a 0.020 ml sample tube, 2.2 xylene
After adding 5 g and 1 mg of solid P-37DI and shaking thoroughly to mix, the mixture was stored at -5"C for 2 weeks and visually observed.
０２０ｍ１のサンプル管に試料１５ｇをとり、ＴＭＰ−
３７ＤＩ固体０．２〜０．３ｇを加え十分に混合した後
２０°Ｃで２週間保管し、目視により観察する。Take 15g of sample into a 020ml sample tube and add TMP-
After adding 0.2 to 0.3 g of 37DI solid and mixing thoroughly, the mixture was stored at 20°C for 2 weeks and visually observed.
■２０Ｉｄのサンプル管に試料１５ｇ、ｎ−へキサン３
．７５ｇをとり、ＴＭＰ−３ＴＯ＋の固体１ｍＨを加え
、十分に振った後３０°Ｃで２週間保管し、目視により
観察する。■15g of sample in a 20Id sample tube, 3g of n-hexane
．． Take 75 g, add 1 mH of solid TMP-3TO+, shake thoroughly, store at 30°C for 2 weeks, and visually observe.
（判定は濁り、又は沈澱物がない場合は○、濁り、又は
沈澱物を生じた場合は×とする。）溶剤稀釈性試験方法
２０ｄのサンプル管に試ネ４１ｇ、キシレン１０ｇを加
え充分に混合し目視により白濁の有無を観察する。(The judgment is ○ if there is no turbidity or precipitate, and × if turbidity or precipitate is formed.) Add 41 g of sample and 10 g of xylene to the sample tube of Solvent Dilubility Test Method 20d and mix thoroughly. Visually observe the presence or absence of cloudiness.
（判定は濁り、又は沈澱物がない場合はＯ，濁り、又は
沈澱物を生じた場合は×とする。）実施例１
プロピレングリコール８ｇ１ジプロピレングリコール８
ｇ、１．３−ブタンジオール８ｇを反応容器にいれ窒素
雰囲気下５０°Ｃに加熱した後、ＴＤＩ６５／３５４．
４ｇを滴下後５０°Ｃで１時間反応させた。これを窒素
雰囲気下ＴＤ１．６５／３５．４３３．８ｇ中に滴下後
、６０°Ｃで２時間反応させ、次にＴＭＰ２１．５ｇを
滴下し、６０°Ｃで２時間反応させた。(The rating is O if there is no turbidity or precipitate, and × if there is turbidity or precipitate.) Example 1 Propylene glycol 8g 1 Dipropylene glycol 8
After putting 8 g of 1,3-butanediol into a reaction vessel and heating it to 50°C under a nitrogen atmosphere, TDI65/354.
After dropping 4 g, the reaction was carried out at 50°C for 1 hour. This was added dropwise to TD1.65/35.433.8g under a nitrogen atmosphere and reacted at 60°C for 2 hours. Next, 21.5g of TMP was added dropwise and reacted at 60°C for 2 hours.
この反応液から過剰のＴＤＩを薄膜蒸留（１７０°Ｃ／
１ｍｌｍｍ１ｌによって除去した後、得られた無色の固
体２３０．８２ｇに酢酸エチル７６．９４ｇを加えて溶
解し、７５％稀釈品を得た。この溶液の粘度は１２２０
ｃｐｓ／２５°Ｃであった。Excess TDI was removed from this reaction solution by thin film distillation (170°C/
After removal by 1 ml mm 1 liter, 76.94 g of ethyl acetate was added to and dissolved in 230.82 g of the obtained colorless solid to obtain a 75% diluted product. The viscosity of this solution is 1220
cps/25°C.
ジプチルアミンによるＮＣＯ基含有率は１３．６１χで
トルエンに対する溶解性も良好であった。また、ＴＭＰ
−３ＴＤＩの結晶化も見られなかった。The NCO group content due to diptylamine was 13.61χ, and the solubility in toluene was also good. Also, TMP
-3TDI crystallization was also not observed.
実施例２
プロピレングリコール６ｇ１ジプロピレングリコール６
ｇ、１．３−ブタンジオール６ｇを反応容器にいれ、窒
素雰囲気下８０°Ｃに加熱した後、ＴＤＩ６５／３５．
８．４ｇを滴下後８０°Ｃで１時間反応させた。これを
窒素雰囲気下ＴＤ１６５／３５．４６２．５ｇ中にＴ門
Ｐ２１．５ｇと同時に滴下し、８０°Ｃで２時間反応さ
せた。Example 2 Propylene glycol 6g1 Dipropylene glycol 6
After putting 6 g of 1,3-butanediol into a reaction vessel and heating it to 80°C under a nitrogen atmosphere, TDI65/35.
After dropping 8.4 g, the reaction was carried out at 80°C for 1 hour. This was added dropwise into TD165/35.462.5g under a nitrogen atmosphere at the same time as 21.5g of T gate P, and reacted at 80°C for 2 hours.
この反応液から過剰のＴＤＩを薄膜蒸留（１７０°Ｃ／
１ｍｍＨｇ）によって除去した後、得られた無色の固体
２００．５ｇに酢酸エチル６９．１７ｇを加えて溶解し
７５％稀釈品を得た。この溶液の粘度は１１６０ｃｐｓ
／２５゛Ｃであった。Excess TDI was removed from this reaction solution by thin film distillation (170°C/
1 mmHg), 69.17 g of ethyl acetate was added and dissolved in 200.5 g of the obtained colorless solid to obtain a 75% diluted product. The viscosity of this solution is 1160 cps
/25°C.
ジブチルアミンによるＮＣＯ基含打率は１３．２８χで
トルエンに対する溶解性も良好であった。The NCO group content by dibutylamine was 13.28χ, and the solubility in toluene was also good.
実施例３
プロピレングリコール８ｇ、ジプロピレングリコール８
ｇ、１，３−ブタンジオール８ｇを反応容器にいれ、窒
素雰囲気下５０″Ｃに加熱した後、ＴＤＩ６５／３５．
１１．２ｇ＠滴下後５０°Ｃで１時間反応させた。これ
を窒素雰囲気下、ＴＤ１６５／３５．４９５．９ｇ中に
滴下後、直ちにＴＭＰ２１．５ｇを滴下して５０°Ｃで
２時間反応させた。Example 3 8 g of propylene glycol, 8 g of dipropylene glycol
After putting 8 g of 1,3-butanediol into a reaction vessel and heating it to 50''C under nitrogen atmosphere, TDI65/35.
After dropping 11.2 g @, it was reacted at 50°C for 1 hour. This was added dropwise to TD165/35.495.9g under a nitrogen atmosphere, and immediately 21.5g of TMP was added dropwise to react at 50°C for 2 hours.
この反応液から過剰のＴＤ［を薄膜蒸留（１７０’Ｃ／
１ｍｍ１ｇ）によって除去した後、得られた無色の固体
２２８．５０ｇに酢酸エチル７６、１７ｇを加えて溶解
し、７５％稀釈品を得た。この溶液の粘度は１５６０ｃ
ｐｓ／２５°Ｃであった。Excess TD was removed from this reaction solution by thin film distillation (170'C/
76.17 g of ethyl acetate was added to and dissolved in 228.50 g of the obtained colorless solid to obtain a 75% diluted product. The viscosity of this solution is 1560c
ps/25°C.
ジプチルアミンによるＮＣＯ基含有率は１３．６５χで
トルエンに対する溶解性も良好であった。The NCO group content due to diptylamine was 13.65χ, and the solubility in toluene was also good.
比較例１
窒素雰囲気下の反応容器にＴＤ１６５／３５を３５０．
２２ｇいれ、５０°Ｃに加熱した加熱後、１．３−ブタ
ンジオール１１．４２ｇを滴下して５０゛Ｃで２時間反
応させた後、ＴＭＰ ２７．７６ｇを滴下し、５０°Ｃ
でさらに２時間反応させた。Comparative Example 1 TD165/35 was placed in a reaction vessel under nitrogen atmosphere at 350.
After heating at 50°C, 11.42g of 1.3-butanediol was added dropwise and reacted at 50°C for 2 hours, then 27.76g of TMP was added dropwise and heated to 50°C.
The reaction was continued for an additional 2 hours.
この反応液から、過剰のＴＤＩを薄膜蒸留（１７０°Ｃ
／１ｍｌｍｍ１ｌによって除去した後、得られた無色の
固］、５１．８５ｇに酢酸エチル５０．６２ｇを加えて
溶解し、７５％稀釈品を得た。この溶液の粘度は８２０
ｃｐｓ／２５°Ｃであった。Excess TDI was removed from this reaction solution by thin film distillation (170°C).
50.62 g of ethyl acetate was added to 51.85 g of the obtained colorless solid and dissolved therein to obtain a 75% diluted product. The viscosity of this solution is 820
cps/25°C.
ジプチルアミンによるＮＣＯ基含有率は１３．７０χで
トルエンに対する溶解性が良好であった。The NCO group content due to diptylamine was 13.70χ, and the solubility in toluene was good.
比較例２
窒素雰囲気下の反応容器にＴＤ１６５／３５を４０５．
１ｇいれ、５０°Ｃに加熱した後、１．３−ブタンジオ
ール４ｇ。Comparative Example 2 TD165/35 was placed in a reaction vessel under a nitrogen atmosphere at a temperature of 405.
Add 1g and heat to 50°C, then add 4g of 1.3-butanediol.
プロピレングリコール４ｇ、ジプロピレングリコール４
ｇを混合したものを滴下して５０°Ｃで２時間反応させ
た後、ＴＭＰ２１．５ｇを滴下し、さらに５０’Ｃで２
時間反応した。この反応液から、過剰のＴＤＩを薄膜蒸
留（１７０’Ｃ／１ｍｍＨｇ）によって除去した後、得
られた無色の固体１６０．５４ｇに酢酸エチル５３．５
１ｇ加えて溶解し、７５％稀釈品を得た。この溶液の粘
度は１２４０ｃｐｓ／２５°Ｃであった。4g propylene glycol, 4g dipropylene glycol
After adding dropwise a mixture of 50g and reacting at 50°C for 2 hours, 21.5g of TMP was added dropwise, and the mixture was further reacted at 50°C for 2 hours.
Time reacted. After removing excess TDI from this reaction solution by thin film distillation (170'C/1 mmHg), 53.5 g of ethyl acetate was added to 160.54 g of the resulting colorless solid.
1 g was added and dissolved to obtain a 75% diluted product. The viscosity of this solution was 1240 cps/25°C.
ジブチルアミンによるＮＣＯ基含有率は１３．６８χで
トルエンに対する溶解性も良好であった。The NCO group content due to dibutylamine was 13.68χ, and the solubility in toluene was also good.
比較例３
窒素雰囲気下の反応容器に、酢酸エチル５０．９２ｇと
、ＴＤ１６５／３５．１０４．０４ｇをいれ３５°Ｃに
昇温した後、２４．４４ｇを滴下して３５°Ｃで２時間
反応させた。Comparative Example 3 50.92 g of ethyl acetate and 104.04 g of TD165/35 were put into a reaction vessel under a nitrogen atmosphere and the temperature was raised to 35°C, and then 24.44g was added dropwise and reacted at 35°C for 2 hours. I let it happen.
次に１．３−ブタンジオール６、１ｇを滴下し３５°Ｃ
でさらに２時間反応させた。得られたプレポリマーのジ
ブチルアミンによるＮＣＯ基含有率は１１．２０χで、
粘度は７８００ｃｐｓ／２５”Ｃであった。Next, add 6.1 g of 1,3-butanediol dropwise at 35°C.
The reaction was continued for an additional 2 hours. The NCO group content due to dibutylamine in the obtained prepolymer was 11.20χ,
The viscosity was 7800 cps/25"C.
実施例１〜３、比較例１〜３の貯蔵安定性試験、及び溶
剤稀釈性試験の結果を表−１に記載した。The results of the storage stability test and solvent dilutability test of Examples 1 to 3 and Comparative Examples 1 to 3 are shown in Table-1.
Claims (1)
ロパンとトルエンジイソシアネートを反応し塗料用ウレ
タンプレポリマーを製造する方法に於いて、トルエンジ
イソシアネートに対し２倍モル以上のジオール類と反応
させ、末端に水酸基を有するプレポリマーとしたのち該
反応液にトリメチロールプロパンを混合、又は別々に、
水酸基に対し過剰のトルエンジイソシアネートと反応さ
せ、ウレタンプレポリマーとし、未反応のトルエンジイ
ソシアネートを除去することを特徴とする塗料用ウレタ
ンプレポリマーの製造方法。In a method for producing a urethane prepolymer for coatings by reacting one or more diols and trimethylolpropane with toluene diisocyanate, toluene diisocyanate is reacted with at least twice the mole of diols to form a hydroxyl group at the terminal. After forming a prepolymer with trimethylolpropane into the reaction solution, or separately,
A method for producing a urethane prepolymer for paints, which comprises reacting hydroxyl groups with excess toluene diisocyanate to obtain a urethane prepolymer, and removing unreacted toluene diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1081580A JPH0689095B2 (en) | 1989-04-03 | 1989-04-03 | Method for producing urethane prepolymer for paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1081580A JPH0689095B2 (en) | 1989-04-03 | 1989-04-03 | Method for producing urethane prepolymer for paint |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02261816A true JPH02261816A (en) | 1990-10-24 |
| JPH0689095B2 JPH0689095B2 (en) | 1994-11-09 |
Family
ID=13750253
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1081580A Expired - Fee Related JPH0689095B2 (en) | 1989-04-03 | 1989-04-03 | Method for producing urethane prepolymer for paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689095B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231116A (en) * | 1990-07-23 | 1993-07-27 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Hydrophilic urethane prepolymer composition |
| CN110105518A (en) * | 2019-06-06 | 2019-08-09 | 浙江多邦新材料有限公司 | A kind of preparation method of polycyanate ester performed polymer |
-
1989
- 1989-04-03 JP JP1081580A patent/JPH0689095B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5231116A (en) * | 1990-07-23 | 1993-07-27 | Dai-Ichi Kogyo Seiyaku Co., Ltd. | Hydrophilic urethane prepolymer composition |
| CN110105518A (en) * | 2019-06-06 | 2019-08-09 | 浙江多邦新材料有限公司 | A kind of preparation method of polycyanate ester performed polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0689095B2 (en) | 1994-11-09 |
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|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |