JPS6230160A - Two-pack type urethane coating material - Google Patents
Two-pack type urethane coating materialInfo
- Publication number
- JPS6230160A JPS6230160A JP60170197A JP17019785A JPS6230160A JP S6230160 A JPS6230160 A JP S6230160A JP 60170197 A JP60170197 A JP 60170197A JP 17019785 A JP17019785 A JP 17019785A JP S6230160 A JPS6230160 A JP S6230160A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polyisocyanate
- coating material
- tertiary amine
- polyol
- 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.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
- Paints Or Removers (AREA)
Abstract
Description
【発明の詳細な説明】
技術分野
本発明は二液型ウレタン塗料に係り、さらに詳しくはポ
ットライフが充分長く、且つ初期乾燥性に優れ、高外観
、高塗膜性能の塗膜を与えうる二液型ウレタン塗料に関
するものである。DETAILED DESCRIPTION OF THE INVENTION Technical Field The present invention relates to a two-component urethane paint, and more particularly to a two-component urethane paint that has a sufficiently long pot life, excellent initial drying properties, and can provide a coating film with a high appearance and high coating performance. This relates to liquid urethane paint.
従来技術
ポリオール成分とポリイソシアナート成分とからなる二
液型ウレタン塗料は、塗膜が柔軟性に富み、割れに対し
て抵抗性があり、耐候性、硬度。Conventional technology A two-component urethane paint consisting of a polyol component and a polyisocyanate component has a coating film that is highly flexible, resistant to cracking, weather resistant, and hard.
光沢、耐薬品性、耐摩耗性等多くの塗膜性能に優れてお
り、自動車補修用をはじめ、木工用塗料などとして広く
実用に供されている6しかしながらラッカーなどに比し
乾燥が遅く、またその過程で表面にゴミなどが付着する
為、乾燥性の改善が望まれている。触媒として有機錫化
合物を加えれば乾燥は速くなるが、反面二液配合後のポ
ットライフが短かく、より迅速な操作を要し、操作のわ
ずられしさを併う。ウレタン塗料の乾燥性を大ならしめ
る目的にはまた、例えばセルローズ系樹脂をブレンド乃
至はグラフトする技術があるが、希釈で固形分が低下し
高外観の得られぬ欠点があり、IPDI系ハードナーを
用いると硬度には優れるが反応性が劣るため初期塗膜品
質例えば耐ガソリン性、耐ウオータースポット性に劣る
問題があり、IPDI系ハードナーと錫系触媒を用いる
とポットライフや外観に問題があり、また錫系以外の金
属系触媒を用いても反応性が十分にはあがらぬ等いずれ
も満足すべき結果を得ていない。It has excellent coating properties such as gloss, chemical resistance, and abrasion resistance, and is widely used as paint for car repair and woodworking.6However, it dries more slowly than lacquer, etc. Since dust and other substances adhere to the surface during this process, it is desired to improve drying performance. Adding an organic tin compound as a catalyst speeds up drying, but on the other hand, the pot life after the two-component formulation is short, requiring faster operation and making the operation more cumbersome. For the purpose of increasing the drying properties of urethane paints, for example, there is a technique of blending or grafting cellulose resin, but this has the drawback that the solid content decreases with dilution and a high appearance cannot be obtained. When using IPDI-based hardeners and tin-based catalysts, there are problems with pot life and appearance when using IPDI hardeners and tin-based catalysts. Furthermore, even when metal catalysts other than tin-based catalysts are used, the reactivity is not sufficiently increased, and satisfactory results have not been obtained in either case.
他方ウレタン塗料で高外観を得る目的に対しては低分子
量ポリオールを用いるとか、多量のポリイソシアネート
成分を使用するなどの方法がとられているがいずれも初
期乾燥性、初期硬度が出ない欠点を有し、特に後者では
コスト高となり満足な結果は得られていない。On the other hand, in order to obtain a high appearance with urethane paints, methods such as using low molecular weight polyols or using large amounts of polyisocyanate components have been used, but both have the disadvantage of poor initial drying properties and initial hardness. In particular, the latter method is expensive and has not produced satisfactory results.
発明が解決しようとする問題点
そこで二液型ウレタン塗料であってそのポットライフを
可及的に大ならしめると共に、乾燥性、特に初期乾燥性
と外観、品質を改善することができれば自動車補修その
他、各種工業分野にウレタン塗料の優れた特性を生かす
ことが出来、本発明は係る目的達成のためになされたも
のである。Problems to be Solved by the Invention Therefore, if a two-component urethane paint could be used to maximize its pot life and improve drying properties, especially initial drying properties, appearance, and quality, it would be useful for automobile repair and other purposes. The excellent characteristics of urethane paints can be utilized in various industrial fields, and the present invention has been made to achieve this purpose.
問題点を解決するための手段
本発明に従えば、上記諸口的がポリオール成分とイソシ
アナート成分とからなる二液型ウレタン塗料において、
前記ポリイソシアナートが脂環族ポリイソシアナートで
あり、且つポリオール成分あるいはポリイソシアナート
成分の何れかに窒素原子一個当りの炭素数が20以下、
pKa 9以上の第3級アミン触媒を含有せしめたこと
を特徴とする塗料により達成せられる。Means for Solving the Problems According to the present invention, in the two-component urethane paint consisting of a polyol component and an isocyanate component,
the polyisocyanate is an alicyclic polyisocyanate, and the number of carbon atoms per nitrogen atom in either the polyol component or the polyisocyanate component is 20 or less,
This can be achieved by a coating material characterized by containing a tertiary amine catalyst having a pKa of 9 or more.
ウレタン塗料に於ては、通常ポリオール成分とポリイソ
シアナート成分とが使用直前に混合され適用せられるが
、ポリイソシアナート成分として芳香族ポリインシアナ
ートを用いると黄変の傾向があり、また脂肪族鎖状ポリ
イソシアナートではその構造上、初期乾燥性に劣り初期
硬度が低いことが認められ、多くの場合触媒が使用され
てきた。In urethane paints, the polyol component and polyisocyanate component are usually mixed and applied immediately before use, but if aromatic polyincyanate is used as the polyisocyanate component, it tends to yellow, and aliphatic Due to its structure, chain polyisocyanates are known to have poor initial drying properties and low initial hardness, and catalysts have been used in many cases.
係る触媒としてはジブチル錫シラウリレートなどの錫系
触媒あるいは錫系触媒と酸との組合せなどが最も実用的
とされている。しかしながら乾燥性とポットライフの両
立は極めて困難で、触媒量を多くするとポットライフが
非常に短くなり、また反応速度の急激な上昇でチヂミ、
ツヤボケなどを生じ外観への悪影響が避けられず、乾燥
性と高外観の両立が得られぬことが指摘されていた。ま
た、アミン触媒の使用も提案されてきたが従来、アミン
触媒を使用すると、一般に塗膜耐水性が悪くなったり、
さらにメタリック塗料などの場合、耐水アルミ変色の原
因となりその有効な制御手段は見出されていなかった。As such a catalyst, a tin-based catalyst such as dibutyltin silaurylate or a combination of a tin-based catalyst and an acid is considered to be the most practical. However, it is extremely difficult to achieve both dryness and pot life; increasing the amount of catalyst will result in a very short pot life, and a rapid increase in the reaction rate will cause sagging,
It has been pointed out that it is not possible to achieve both dryness and high appearance because it inevitably has an adverse effect on the appearance, such as causing dullness. Additionally, the use of amine catalysts has been proposed, but in the past, when amine catalysts were used, the water resistance of the coating film generally deteriorated.
Furthermore, in the case of metallic paints, etc., it causes discoloration of water-resistant aluminum, and no effective means for controlling this has been found.
尚、ポリイソシアナートとしては脂環族のものも用いら
れるが、この場合には反応性が劣り、従って塗膜性能に
問題があり、錫系触媒を用いるとしても通常の使用量で
は反応性を十分にあげることが出来ず、過剰量添加でポ
ットライフの悪化や外観への悪影響を避けることが出来
なかった。Incidentally, alicyclic polyisocyanates are also used, but in this case they have poor reactivity and therefore have problems with coating film performance.Even if a tin-based catalyst is used, the reactivity is low in the normal amount used. It was not possible to increase the amount sufficiently, and it was not possible to avoid deterioration of the pot life and adverse effects on the appearance by adding an excessive amount.
本発明者らはポリイソシアナート成分及び触媒につき種
々の検討の結果、脂環族ポリイソシアネートと第3級ア
ミン触媒の組合せが独特な挙動を示し、初期乾燥性に優
れ、高外観、高品質塗膜を与えうろことを見出した。As a result of various studies on polyisocyanate components and catalysts, the present inventors found that the combination of alicyclic polyisocyanate and tertiary amine catalyst exhibits unique behavior, exhibits excellent initial drying properties, and produces high-quality coatings with excellent appearance. They discovered scales that provide a membrane.
すなわち、本発明ではポリイソシアネートとして初期乾
燥性に優れ、高外観の得られる脂環族ポリイソシアネー
トが選択使用せられる。係るポリイソシアネートとして
は、例えばIPDI系(タケネートD−14ON (武
田薬品社製)、デスモジュールZ−4370(住人バイ
エルウレタン社製))、HXDI系(タケネートD−1
2ON(武田薬品社製))などがあげられるが、勿論こ
れらのみに限定されず、任意の脂環族のポリイソシアネ
ートが本発明目的に好適に使用せられる。That is, in the present invention, as the polyisocyanate, an alicyclic polyisocyanate that has excellent initial drying properties and provides a high appearance is selectively used. Examples of such polyisocyanates include IPDI series (Takenate D-14ON (manufactured by Takeda Pharmaceutical Co., Ltd.), Desmodur Z-4370 (manufactured by Sumitomo Bayer Urethane Co., Ltd.)), HXDI series (Takenate D-1),
2ON (manufactured by Takeda Pharmaceutical Co., Ltd.), but of course the polyisocyanate is not limited to these, and any alicyclic polyisocyanate can be suitably used for the purpose of the present invention.
本発明に於ては、上記ポリイソシアネートとポリオール
との反応性を第3級アミンの選択使用により解決したも
のである。触媒として用いられる第3級アミンはその窒
素原子一個当りの炭素数が20以下であり、且つpKa
が9以上である点に於て特徴づけられる。というのは前
記炭素数が21以上では立体障害が大きく触媒効果が悪
くなるし、また、pKaが9に満たぬ所謂、親水性アミ
ン(従来提案されてきた型のアミン)では脂環族ポリイ
ソシアナートとポリオールの触媒活性が悪く、また塗膜
の耐水劣化、あるいはメタリック塗料での耐水アルミ変
色等の問題を生じるからである。上記要件を満たす限り
任意の第3級アミンが用いられるが、それらの代表例を
示せば下記の通りである。In the present invention, the reactivity between the polyisocyanate and polyol is solved by selectively using a tertiary amine. The tertiary amine used as a catalyst has 20 or less carbon atoms per nitrogen atom, and has a pKa of
is 9 or more. This is because if the number of carbon atoms is 21 or more, steric hindrance will be large and the catalytic effect will be poor, and in the case of so-called hydrophilic amines (the type of amines that have been proposed in the past) with a pKa of less than 9, alicyclic polyisocyanate This is because the catalytic activity of the inert and polyol is poor, and problems such as deterioration of the water resistance of the coating film or discoloration of water resistant aluminum in metallic paints occur. Any tertiary amine can be used as long as it satisfies the above requirements, and representative examples thereof are as follows.
1.4−ジアザビシクロ(2,2,2)オクタン(以下
DABC○と略す。)
CH,−CH。1.4-Diazabicyclo(2,2,2)octane (hereinafter abbreviated as DABC○) CH, -CH.
1.4−ジアザ−メチル−(2,2,2)−ビシクロオ
クタンCH−CH2
CH3
ジシクロヘキシルメチルアミン(以下DCHAと略す。1.4-Diaza-methyl-(2,2,2)-bicyclooctane CH-CH2 CH3 dicyclohexylmethylamine (hereinafter abbreviated as DCHA).
)シクロへキシルジメチルアミン(以下CHAと略す。) Cyclohexyldimethylamine (hereinafter abbreviated as CHA).
)CH。)CH.
トリーn−プロピルアミン N −+c s H7)3 ジメチル−し−ブチルアミン CH,−N −C−CH3 CH。tri-n-propylamine N-+cs H7)3 dimethyl-butylamine CH, -N -C-CH3 CH.
トリーn−ブチルアミン N−4C,H,)。tri-n-butylamine N-4C,H,).
1.8−ジアザビシクロ[5,4,01ウンデセン−7
(以下DBUと略す。)
N、N、N’ 、N’ 、N’−ペンタメチルジエチレ
ントリアミンN、 N、 N’ 、 N’−テトラメチ
ルプロピレンジアミンCH,−N−CH,CH,CH2
−N−CH31,5−ジアザビジクロロ4,3.O]ノ
ネン−5これら触媒中、塩基仕度が高く触媒活性の特に
優れたものとしてジシクロヘキシルメチルアミン、シク
ロヘキシルジメチルアミンなどの使用が好ましく推奨せ
られる6
本発明では、これら触媒がポリオール成分あるいはポリ
イソシアネート成分のいずれかに添加せられるが、その
使用量は通常の触媒量、即ち一般に樹脂固形分に対し0
.3〜10%の範囲内で用いられる。というのは0.3
%未満では触媒作用を十分発揮できず、また10%を越
えると塗膜の黄変といった悪影響を及ぼす傾向が認めら
れるからである。1.8-diazabicyclo[5,4,01 undecene-7
(Hereinafter abbreviated as DBU.) N, N, N', N', N'-pentamethyldiethylenetriamine N, N, N', N'-tetramethylpropylenediamine CH, -N-CH, CH, CH2
-N-CH31,5-diazabidichloro4,3. O]Nonene-5 Among these catalysts, dicyclohexylmethylamine, cyclohexyldimethylamine, etc. are preferably used because they have a high base content and particularly excellent catalytic activity.6 In the present invention, these catalysts are used as polyol components or polyisocyanate components. However, the amount used is the usual catalyst amount, that is, generally 0% based on the resin solid content.
.. It is used within the range of 3 to 10%. That is 0.3
If it is less than 10%, the catalytic effect cannot be sufficiently exerted, and if it exceeds 10%, there is a tendency for adverse effects such as yellowing of the coating film.
このように本発明に於てはポリイソシアネート成分とし
て脂環族ポリイソシアネートを選択し、またポリオール
成分あるいはポリイソシアネート成分のいづれかに、窒
素原子一個当りの炭素数が20以下で、pKaが9以上
の第3級アミン触媒を添加したこ波型ポリウレタン塗料
が提供され、ポットライフが従来のものより大巾に改善
されると共に、初期乾燥性に優れ、高外観、高品質塗膜
を与えることができ、従来かえりみられなかった自動車
補修用塗料その他の適用に広い門戸を開くものである。In this way, in the present invention, an alicyclic polyisocyanate is selected as the polyisocyanate component, and either the polyol component or the polyisocyanate component has a carbon number of 20 or less per nitrogen atom and a pKa of 9 or more. A wave-type polyurethane paint containing a tertiary amine catalyst is provided, and the pot life is greatly improved compared to conventional paints, and it also has excellent initial drying properties and can provide a high-quality paint film with a high appearance. This opens the door to a wide range of applications, including automobile refinishing paints, which have not been considered before.
以下実施例により本発明を説明する。特にことわりなき
限り部および%は重量による。The present invention will be explained below with reference to Examples. Parts and percentages are by weight unless otherwise specified.
実施例1
ポリオールとしてアクリディックA−801(大日本イ
ンキ社製、以下Aと称す)またIPDI系ポリイソシア
ネートとしてタケネートD−14ON(武田薬品社製)
を各々当モル量用いた。Example 1 Acridic A-801 (manufactured by Dainippon Ink Co., Ltd., hereinafter referred to as A) was used as a polyol, and Takenate D-14ON (manufactured by Takeda Pharmaceutical Co., Ltd.) was used as an IPDI polyisocyanate.
were used in equimolar amounts.
ポリオールならびにポリイソシアネート合計量に対し1
%に相当する量のDABC○を触媒としてポリオール成
分に加え二液型ポリウレタンクリヤー塗料を得た。1 per total amount of polyol and polyisocyanate
% of DABC○ was added to the polyol component as a catalyst to obtain a two-component polyurethane clear paint.
実施例2〜5及び比較例1〜6
実施例1と同様、下記第1表に示した配合により各々二
液型ウレタン塗料を得た。Examples 2 to 5 and Comparative Examples 1 to 6 Similarly to Example 1, two-component urethane paints were obtained using the formulations shown in Table 1 below.
上記の各実施例ならびに比較例のウレタン塗料を20’
Cでのポットライフ、試験板に塗布し、60℃で30分
間反応させた時の反応率ならびに塗膜の初期硬度、外観
を調べ第1表に示す結果を得た。The urethane paint of each of the above examples and comparative examples was applied for 20'
The pot life at C, the reaction rate when applied to a test plate and reacted for 30 minutes at 60°C, and the initial hardness and appearance of the coating film were investigated, and the results shown in Table 1 were obtained.
尚、上記に於て
反応率は日本分光社製赤外分光光度計A−3型を用い、
大阪硝工社製IR加熱セルを用い吸光度でNC○の最大
吸収波長に固定し、次式で反応率を算出した。In addition, in the above, the reaction rate was measured using an infrared spectrophotometer A-3 model manufactured by JASCO Corporation.
Using an IR heating cell manufactured by Osaka Glass Industries, the absorbance was fixed at the maximum absorption wavelength of NC○, and the reaction rate was calculated using the following formula.
初期硬度は試験板に塗装後、60℃で30分間反応させ
、次に塗膜の鉛筆硬度を測定した(J I S−に54
00.6.14)。The initial hardness was determined by coating the test plate, reacting at 60°C for 30 minutes, and then measuring the pencil hardness of the coating (JIS-54).
00.6.14).
外観は同じく60℃で30分反応させたあとの塗膜外観
を肉眼で観察し
○・・平滑で光沢のある肌
△・ツヤピケ
×・・・チヂミ肌
として判定したものである。The appearance of the coating film was similarly observed with the naked eye after reacting at 60° C. for 30 minutes, and was judged as ○: smooth and glossy skin △: glossy pique ×: wrinkled skin.
特許出願代理人patent application agent
Claims (1)
液型ウレタン塗料において前記ポリイソシアナートが脂
環族ポリイソシアナートであり、且つポリオール成分あ
るいはポリイソシアナート成分の何れかに窒素原子一個
当りの炭素数が20以下、pKa9以上の第3級アミン
触媒を含有せしめたことを特徴とする塗料。In a two-component urethane paint consisting of a polyol component and a polyisocyanate component, the polyisocyanate is an alicyclic polyisocyanate, and either the polyol component or the polyisocyanate component has a carbon number per nitrogen atom. A paint characterized by containing a tertiary amine catalyst having a pKa of 20 or less and a pKa of 9 or more.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60170197A JPS6230160A (en) | 1985-07-31 | 1985-07-31 | Two-pack type urethane coating material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP60170197A JPS6230160A (en) | 1985-07-31 | 1985-07-31 | Two-pack type urethane coating material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6230160A true JPS6230160A (en) | 1987-02-09 |
Family
ID=15900468
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP60170197A Pending JPS6230160A (en) | 1985-07-31 | 1985-07-31 | Two-pack type urethane coating material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6230160A (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585370A (en) * | 1981-07-01 | 1983-01-12 | Takeda Chem Ind Ltd | Composition for polyurethane coating and adhesive |
JPS58109527A (en) * | 1981-12-23 | 1983-06-29 | Takeda Chem Ind Ltd | Polyurethane resin composition |
JPS58109528A (en) * | 1981-12-23 | 1983-06-29 | Takeda Chem Ind Ltd | Polyurethane resin composition |
JPS60110716A (en) * | 1983-11-18 | 1985-06-17 | Takeda Chem Ind Ltd | Production of polyurethane resin |
-
1985
- 1985-07-31 JP JP60170197A patent/JPS6230160A/en active Pending
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS585370A (en) * | 1981-07-01 | 1983-01-12 | Takeda Chem Ind Ltd | Composition for polyurethane coating and adhesive |
JPS58109527A (en) * | 1981-12-23 | 1983-06-29 | Takeda Chem Ind Ltd | Polyurethane resin composition |
JPS58109528A (en) * | 1981-12-23 | 1983-06-29 | Takeda Chem Ind Ltd | Polyurethane resin composition |
JPS60110716A (en) * | 1983-11-18 | 1985-06-17 | Takeda Chem Ind Ltd | Production of polyurethane resin |
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