JPH0443903B2 - - Google Patents
Info
- Publication number
- JPH0443903B2 JPH0443903B2 JP58062283A JP6228383A JPH0443903B2 JP H0443903 B2 JPH0443903 B2 JP H0443903B2 JP 58062283 A JP58062283 A JP 58062283A JP 6228383 A JP6228383 A JP 6228383A JP H0443903 B2 JPH0443903 B2 JP H0443903B2
- Authority
- JP
- Japan
- Prior art keywords
- polyisocyanate
- weight
- epichlorohydrin
- present
- added
- 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
- 239000005056 polyisocyanate Substances 0.000 claims description 22
- 229920001228 polyisocyanate Polymers 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 13
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000004040 coloring Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 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 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 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 2
- 241001550224 Apha Species 0.000 description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- VHYHRNYPVNFGNR-UHFFFAOYSA-N (3,5-ditert-butylphenyl)methanol Chemical compound CC(C)(C)C1=CC(CO)=CC(C(C)(C)C)=C1 VHYHRNYPVNFGNR-UHFFFAOYSA-N 0.000 description 1
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002513 isocyanates Chemical class 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
- GIWKOZXJDKMGQC-UHFFFAOYSA-L lead(2+);naphthalene-2-carboxylate Chemical compound [Pb+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 GIWKOZXJDKMGQC-UHFFFAOYSA-L 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Description
本発明は着色安定化したポリイソシアネート組
成物の製造方法に関する、更に詳しくはエピクロ
ルヒドリンを加えて着色安定性に優れたポリイソ
シアネート組成物の製造方法に関するものであ
る。
ポリイソシアネート化合物類は、ポリウレタン
樹脂などの原料として有用な物質であることは周
知である。
しかしながら、これらのポリイソシアネート化
合物は不安定な物質であり、特に着色については
製造直後から進行し、数週間〜数カ月後には使用
に耐えられなくなるほど着色する場合がある。着
色したポリソシアネート化合物は、白物あるいは
淡色物のレザー、塗料、フオームなどの原料とし
ては使用出来ない。
着色防止のための改良については、例えばポリ
イソシアネート化合物の純度を上げたり、空気と
の接触をさけたり、着色防止剤を添加したりして
行なわれてきたが、いづれも十分な効果は得られ
ていない。ポリイソシアネート化合物のなかで比
較的着色しにくいといわれる脂肪族系ポリイソシ
アネート化合物でも、重合のために加熱すると短
時間のうちに着色することがあり、この場合の着
色防止技術もまだ完成されていない。
本発明者らは、これらの問題点を解決するため
種々研究した結果、エピクロルヒドリンが優れた
着色防止効果をもつことが解り、本発明に至つ
た。
即ち、本発明は、
ポリイソシアネート化合物に0.001重量％のエ
ピクロルヒドリンを加えて、45℃〜100℃の温度
で加熱することを特徴とする着色安定性の優れた
ポリイソシアネート組成物の製造方法である。
本発明におけるエピクロルヒドリンの添加量
は、ポリイソシアネート化合物の種類あるいは純
度によつて異なるが0.001重量％〜0.1重量％の範
囲である。0.001重量％未満では大きな効果は期
待できず、又0.1重量％をこえて添加しても効果
的に差異は認められない。
本発明におけるポリイソシアネート化合物とし
ては、ジフエニルメタンジイソシアネート
（MDI）、ポリフエニルメタンポリイソシアネー
ト、ヘキサメチレンジイソシアネート（HDI）、
イソホロンジイソシアネート、フエニレンジイソ
シアネート、トリレンジイソシアネート（TDI）、
ナフチレンジイソシアネートなど又、これらポリ
イソシアネートのトリマー化体、カルボジイミド
化体などのイソシアネート変性体などが用いられ
る。エピクロルヒドリンをポリイソシアネート化
合物に加え45℃〜100℃の温度で加熱を行うこと
により着色安定性の優れたポリイソシアネート組
成物が得られる。
エピクロルヒドリンを添加したポリイソシアネ
ート化合物が無添加品にくらべ優れた着色安定性
を有する。又、本発明のポリイソシアネート組成
物を用いてトリマー化反応、カルボジイミド化反
応などを行なうに際して、あるいはこれら反応物
の熱処理などの後処理に際して反応物の着色が有
効に防止される。
本発明のポリイソシアネート組成物に通常用い
られる他の添加剤類、例えば３，５−ジタ−シヤ
リ−ブチルハイドロオキシトルエン、トリフエニ
ルフオスフアイトなどを併用することが出来る。
又、必要に応じて紫外線吸収剤、防カビ剤、染
料、充填剤、溶剤、可塑剤なども添加することが
出来る。
実施例 １
種々のポリイソシアネート化合物にエピクロル
ヒドリンを添加したものと、無添加のものについ
て表中の温度条件で経時させて色数変化を測定し
た結果、表．１のようになつた。
The present invention relates to a method for producing a polyisocyanate composition with stabilized coloring, and more particularly to a method for producing a polyisocyanate composition with excellent coloring stability by adding epichlorohydrin. It is well known that polyisocyanate compounds are useful substances as raw materials for polyurethane resins and the like. However, these polyisocyanate compounds are unstable substances, and in particular, coloration progresses immediately after production, and may become so colored that it becomes unusable after several weeks to several months. Colored polysocyanate compounds cannot be used as raw materials for white or light-colored leather, paints, foams, etc. Improvements to prevent coloration have been made, for example, by increasing the purity of the polyisocyanate compound, avoiding contact with air, and adding coloration inhibitors, but none of these methods have been sufficiently effective. Not yet. Even aliphatic polyisocyanate compounds, which are said to be relatively resistant to discoloration among polyisocyanate compounds, can become discolored within a short time when heated for polymerization, and the technology to prevent discoloration in this case has not yet been perfected. . As a result of various studies to solve these problems, the present inventors found that epichlorohydrin has an excellent anti-coloring effect, leading to the present invention. That is, the present invention is a method for producing a polyisocyanate composition with excellent coloring stability, which comprises adding 0.001% by weight of epichlorohydrin to a polyisocyanate compound and heating the mixture at a temperature of 45°C to 100°C. The amount of epichlorohydrin added in the present invention varies depending on the type or purity of the polyisocyanate compound, but is in the range of 0.001% by weight to 0.1% by weight. If it is less than 0.001% by weight, no great effect can be expected, and if it is added in excess of 0.1% by weight, no difference in effectiveness will be observed. Examples of the polyisocyanate compound in the present invention include diphenylmethane diisocyanate (MDI), polyphenylmethane polyisocyanate, hexamethylene diisocyanate (HDI),
Isophorone diisocyanate, phenylene diisocyanate, tolylene diisocyanate (TDI),
Also used are naphthylene diisocyanate and modified isocyanates such as trimerized polyisocyanates and carbodiimidized polyisocyanates. By adding epichlorohydrin to a polyisocyanate compound and heating at a temperature of 45°C to 100°C, a polyisocyanate composition with excellent coloring stability can be obtained. A polyisocyanate compound to which epichlorohydrin is added has superior coloring stability compared to a product without the additive. Furthermore, coloring of the reactants is effectively prevented when carrying out trimerization reactions, carbodiimidization reactions, etc. using the polyisocyanate composition of the present invention, or during post-treatments such as heat treatment of these reactants. Other additives commonly used in the polyisocyanate compositions of the present invention, such as 3,5-di-tert-butylhydroxytoluene and triphenyl phosphorite, can be used in combination.
Further, ultraviolet absorbers, fungicides, dyes, fillers, solvents, plasticizers, etc. can be added as necessary. Example 1 Changes in color number of various polyisocyanate compounds with and without epichlorohydrin added were measured over time under the temperature conditions shown in the table. It became like 1.
【表】
実施例 ２
TDI（２，４−／２，６−＝80／20）にエピク
ロルヒドリンを0.02重量％添加したものを1000重
量部、酢酸エチル1000重量部、およびナフテン酸
鉛2.0重量部を70℃で反応させ、反応液がイソシ
アネート基8.5重量％を含有するまでトリマー化
重合させて、次に触媒を燐酸で中和して色数
100APHAの生成物をえた。エピクロルヒドリン
無添加のTDIを用いて同様に反応させたところ、
色数350APHAの生成物をえた。[Table] Example 2 1000 parts by weight of TDI (2,4-/2,6-=80/20) with 0.02% by weight of epichlorohydrin added, 1000 parts by weight of ethyl acetate, and 2.0 parts by weight of lead naphthenate. The reaction was carried out at 70°C, and the reaction mixture was polymerized by trimerization until it contained 8.5% by weight of isocyanate groups, and then the catalyst was neutralized with phosphoric acid to determine the color number.
A product of 100 APHA was obtained. When a similar reaction was carried out using TDI without the addition of epichlorohydrin,
A product with a color number of 350 APHA was obtained.
Claims (1)
0.1重量％のエピクロルヒドリンを加えて、45℃
〜100℃の温度で加熱することを特徴とする着色
安定性の優れたポリイソシアネート組成物の製造
方法。1 0.001% by weight to polyisocyanate compound
Add 0.1% by weight epichlorohydrin and heat at 45°C.
A method for producing a polyisocyanate composition with excellent coloring stability, which comprises heating at a temperature of ~100°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58062283A JPS59189116A (en) | 1983-04-11 | 1983-04-11 | Production of discoloration-resistant polyisocyanate composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58062283A JPS59189116A (en) | 1983-04-11 | 1983-04-11 | Production of discoloration-resistant polyisocyanate composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59189116A JPS59189116A (en) | 1984-10-26 |
| JPH0443903B2 true JPH0443903B2 (en) | 1992-07-20 |
Family
ID=13195639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58062283A Granted JPS59189116A (en) | 1983-04-11 | 1983-04-11 | Production of discoloration-resistant polyisocyanate composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59189116A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2988755B2 (en) * | 1991-09-09 | 1999-12-13 | 住友バイエルウレタン株式会社 | Method for preventing coloring of aromatic isocyanate compounds |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5242596A (en) * | 1975-10-01 | 1977-04-02 | Nippon Soda Co Ltd | Process for preparing urethane prepolymer |
-
1983
- 1983-04-11 JP JP58062283A patent/JPS59189116A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5242596A (en) * | 1975-10-01 | 1977-04-02 | Nippon Soda Co Ltd | Process for preparing urethane prepolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59189116A (en) | 1984-10-26 |
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