JPS6329689B2 - - Google Patents
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- Publication number
- JPS6329689B2 JPS6329689B2 JP56069390A JP6939081A JPS6329689B2 JP S6329689 B2 JPS6329689 B2 JP S6329689B2 JP 56069390 A JP56069390 A JP 56069390A JP 6939081 A JP6939081 A JP 6939081A JP S6329689 B2 JPS6329689 B2 JP S6329689B2
- Authority
- JP
- Japan
- Prior art keywords
- component
- urethane resin
- resin composition
- solvent
- molecule
- 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
Links
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 22
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 16
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011342 resin composition Substances 0.000 claims description 12
- 238000004383 yellowing Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 229920005862 polyol Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- -1 caprolactone polyol Chemical class 0.000 claims description 4
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 150000005846 sugar alcohols Polymers 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 18
- 239000005056 polyisocyanate Substances 0.000 description 11
- 229920001228 polyisocyanate Polymers 0.000 description 11
- 125000005442 diisocyanate group Chemical group 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000007872 degassing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 150000003077 polyols Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- KCZQSKKNAGZQSZ-UHFFFAOYSA-N 1,3,5-tris(6-isocyanatohexyl)-1,3,5-triazin-2,4,6-trione Chemical compound O=C=NCCCCCCN1C(=O)N(CCCCCCN=C=O)C(=O)N(CCCCCCN=C=O)C1=O KCZQSKKNAGZQSZ-UHFFFAOYSA-N 0.000 description 1
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000012948 isocyanate Substances 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
- 239000004922 lacquer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 210000001331 nose Anatomy 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Description
本発明は、透明性、耐傷性に優れると共に耐候
性に優れた硬化物を与える無黄変ウレタン樹脂組
成物で、特にその組成物の製造時及び成形硬化時
にジイソシアネート蒸気の発生しない限り扱い易
い無黄変ウレタン樹脂組成物に関する。
レンズ、照明器具、装飾品、アクセサリー等の
分野で従来用いられてきた無機ガラスの代りに透
明樹脂が用いられる傾向は益々高くなつている。
このような透明樹脂として、従来よりポリ（メ
タ）アクリル酸メチル、ポリカーボネート等が知
られているが、これらの樹脂は耐傷性が劣ると言
う欠点を有している。
ウレタン樹脂は耐傷性に優れ、上記用途に適し
た樹脂であるが、芳香族イソシアネートを使用し
たウレタン樹脂は紫外線により黄変を生じる欠点
がある。特開昭52―86447号公報には耐候性に優
れた成形物を与え得る無黄変ウレタン樹脂組成物
が提案されている。しかし、この組成物は脂肪族
ジイソシアネートを多量に含むものであり、減圧
下での脱気、硬化時の加熱等において毒性の強い
ジイソシアネート蒸気の発生が多く、作業環境上
の問題を有している。
又、特開昭55―98172号公報には、ポリイソシ
アネートとして、特定のイソシアネート―イソシ
アヌレートとその製法及びポリウレタンラツカー
製造用出発材料としての使用が記載されており、
その低蒸気圧性、高い光安定性、耐候性等につい
て記載されているが、気泡の混入しない注型成形
品の製造に適したウレタン樹脂組成物は全く開示
されていない。
以上に鑑み、本発明者らは、ジイソシアネート
蒸気の発生がなく安全に、かつ、無溶剤で、取り
扱い得る耐候性に優れ、塗膜及び注型成形品特に
気泡混入のない注型成形品の製造用として好適な
無黄変ウレタン樹脂組成物を見いだすべく鋭意研
究をかさね、本発明をなすに至つた。
即ち、本発明は、
(a) 脂肪族ジイソシアネートをビウレツト結合又
は／及びイソシアヌレート結合により結合させ
た１分子中に３個以上のイソシアネート基を含
有し、30℃における粘度が3000センチポイズ以
下のポリイソシアネートと、
(b) （ｂ―１）分子量が300以上3000以下で１分
子中に水酸基を２個以上有する溶剤を含まない
水酸基含有化合物と（ｂ―２）分子量が200以
下で、１分子中に水酸基を２個以上有する多価
アルコールとからなり、（ｂ―１）成分と（ｂ
―２）成分の合計水酸基１当量に対して(a)成分
のイソシアネート基を0.8〜1.5当量の割合で含
み、溶剤を用いないことを特徴とする無黄変ウ
レタン樹脂組成物に関するものである。
本発明のウレタン樹脂組成物は、(a)、（ｂ―１）
及び（ｂ―２）の成分からなり、これら３種成分
を混合して、注型又はコーテイングした後、常温
又は加熱下で硬化され、所望の成形品又は塗膜を
与えるものであるが、前記せるとおり、得られる
成形品又は塗膜は透明性、耐傷性、耐候性に優
れ、かつ、混合、硬化時に毒性の強いジイソシア
ネート蒸気の発生のないものであり、注型成形品
は気泡の混入しないものである。
以下に本発明を詳細に説明する。
本発明組成物の(a)成分において、用いるジイソ
シアネートを脂肪族ジイソシアネートに限定した
理由は組成物を無黄変性とする為である。芳香族
ジイソシアネートでは無黄変性が得られない。
又、(a)成分において、ポリイソシアネートを用
いた理由は、ジイソシアネートの結合による高分
子量化により揮発性をなくし、脱気及び硬化時の
蒸発を防止した点にある。低分子量のジイソシア
ネートでは、毒性の強い蒸気が発生し作業者の目
や鼻を刺激し呼吸器障害を引き起こすからであ
る。
又、ポリイソシアネートの結合の種類をビウレ
ツト結合（biuret）結合とイソシアヌレート結合
に限定した理由は、これらの結合により得られる
ポリイソシアネートは、30℃における粘度が
3000cps以下のものが得易いため、流動性が高く
真空下で脱気する際の泡抜けが容易な事と、（ｂ
―１），（ｂ―２）成分の水酸基含有化合物との相
溶性が良好な為である。
本発明における脂肪族ジイソシアネートとは、
炭素数４から９までの直鎖、分岐鎖の飽和炭化水
素とイソシアネート基からなるジイソシアネート
であり、例えば、１，４―テトラメチレンジイソ
シアネート、１，５―ペンタメチレンジイソシア
ネート、１，６―ヘキサメチレンジイソシアネー
ト（HMDIと略称）、２，２，４（又は２，４，
４）―トリメチル―ヘキサメチレンジイソシアネ
ートなどが挙げられる。中でもHMDIが好まし
い。これらのジイソシアネートは１種を単独に又
は２種以上の混合物として用いられる。
上記ジイソシアネートをビウレツト結合又は／
及びイソシアヌレート結合させる方法は公知であ
り、例えば、特開昭53―106797号公報、特開昭52
―69497号公報に記載された方法を用いることが
できる。
上記ビウレツト又は／及びイソシアヌレート結
合により１分子中に３個以上のイソシアネート基
を含有するポリイソシアネートが本発明組成物の
(a)成分として有用であり、特にHMDIビウレツ
ト多量体、HMDIイソシアヌレート多量体が好
ましい。
本発明における（ｂ―１）成分としては、分子
量が300以上で3000以下の１分子中水酸基を２個
以上有する水酸基含有化合物から選ばれるが、そ
の中で、ポリエーテルポリオールとしては、炭素
数２〜４のポリオキシアルキレングリコール、例
えば、ポリエチレングリコール、ポリプロピレン
グリコール、ポリテトラメチレングリコールが挙
げられ、重量平均分子量3000以下、特に、300〜
2000のものが好ましく、２官能又は３官能性のポ
リエーテルポリオールが有効である。
ポリエステルポリオールとしては、ジカルボン
酸としてアジピン酸又はフタル酸、多価アルコー
ルとして炭素数２〜６の２価アルコール、トリメ
チロールプロパン、又はペンタエリスリトールの
各単独又は２種以上の混合物から合成される、重
量平均分子量3000以下、特に重量平均分子量300
〜2000の末端２〜４個の水酸基を有するポリエス
テルポリオール、又は、重量平均分子量300〜
3000の末端に２個以上の水酸基を有するポリカプ
ロラクトンポリオールが挙げられる。
水酸基末端ウレタンプレポリマーとしては、前
記脂肪族ジイソシアネートと前記ポリエーテルポ
リオール又はポリエステルポリオールのうち２官
能性のものとを、ポリオールの水酸基１当量に対
してイソシアネート基１当量未満の割合で反応さ
せて得られるプレポリマーが挙げられ、ポリプロ
ピレングリコールとHMDI又は／及びIPDIとを
反応させて得られるウレタンプレポリマーが好ま
しい。
（ｂ―２）成分である分子量が200以下で、１
分子中に水酸基を２個以上有する多価アルコール
としては、炭素数２〜６の２価アルコール、例え
ば、エチレングリコール、プロピレングリコー
ル、１，３―ブチレングリコール、１，４―ブチ
レングリコール、ペンタエリスリトール、１，５
―ペンタメチレングリコール、１，６―ヘキサメ
チレングリコール、更にトリメチロールプロパ
ン、ペンタエリスリトールが挙げられる。
（ｂ―１）成分の分子量が3000を超えたり、又
（ｂ―２）成分の分子量が200を超えた場合は、ポ
リイソシアネートとの相溶性が不充分な場合や真
空下で脱気し気泡を除く際に長時間かかつたり、
気泡が完全に取り除かれない場合が発生し、好ま
しくない。又、（ｂ―１）成分に溶剤が入つたも
のを用いた場合は、真空下で脱気する際に溶剤が
揮発し、脱気が充分にできないばかりか、溶剤を
含んだ混合物を注型すると発泡や硬化後の収縮が
起こり問題となる。
又、（ｂ―１）成分、（ｂ―２）成分を各々単独
で用いた場合は硬化が遅くなつたり、硬化しない
場合があり好ましくない。（ｂ―１）成分と（ｂ
―２）成分の比は、重量で１／99〜99／１が好ま
しい。
本発明の組成物は、（ｂ―１），（ｂ―２）成分
の合計の水酸基１当量に対して(a)成分のイソシア
ネート基0.8〜1.5当量、より好ましくは1.0〜1.2
当量からなる(a)、（ｂ―１），（ｂ―２）成分の混
合物であり、これら３成分の混合後硬化成形され
るものである。イソシアネート基の割合が0.8当
量より少ない場合は、成形品や塗膜の硬度、強度
が低下したり、耐候性が低下する。一方1.5当量
を超える場合は、硬化過程中に発泡が生じたり、
硬化物が硬く、脆すぎて、実用上好ましくないも
のとなる。
本発明の組成物を用いてウレタン樹脂の成形品
や塗膜を得る方法としては、慣用の方法を用いれ
ばよい。即ち、(a)成分と（ｂ―１），（ｂ―２）成
分とを混合し、注型成形又は塗布により硬化させ
るが、混合前又は混合後真空下に常温又は加熱下
で脱気し、常温又は加熱下に硬化させる。硬化条
件は工程上、製品の特性等により適宜選択すれば
良く、特段の制限はない。
又、組成物にイソシアネート基と水酸基の反応
促進触媒、酸化防止剤、紫外線吸収剤、レベリン
グ剤、離型剤、その他の添加剤を加えることは勿
論可能である。
本発明のウレンタン樹脂組成物は、樹脂レン
ズ、照明用品、装飾品、アクセサリー等の成形
品、表面保護膜等の製造に特に適するが、勿論こ
れ以外の用途を除外するものではない。
以下に実施例を示す。まず使用に供したポリイ
ソシアネートについて述べる。
ポリイソシアネートＡ：特開昭53―106797号公
報の実施例１に示されているヘキサメチレンジイ
ソシアネートビウレツト結合多量体、粘度
1200cps／30℃、イソシアネート基結合量23.9重
量％。
ポリイソシアネートＢ：特開昭52―69497号公
報の実施例１に示されているヘキサメチレンジイ
ソシアネートのイソシアヌレート結合多量体、粘
度2500cps／30℃、イソシアネート基含有量23.6
重量％。
実施例１〜７ 比較例１，２
第１表に示す(a)成分と（ｂ―１），（ｂ―２）成
分の所定量を夫々のビーカーに入れ、室温で加熱
した減圧（10mmHg以下）下で30分間放置し、内
部の水分や揮発性不純物を除去した。これを乾燥
空気下で放冷した後、(a)，（ｂ―１），（ｂ―２）
の成分を充分に混合する。均一に混合された状態
で再度真空脱気し、表面が発泡しなくなつた時点
でポリエチレン製の15×15×１（cm）（深さ）の型
に約５mmの厚さになるように注入し、真空下で５
分放置後85℃のオーブンに入れ、15分硬化させた
後室温に放冷し、型から取り出した。
上記操作中刺激臭等の発生はなく、操作は安全
容易に実施できた。
得られた物は第１表に示す物性を持つた透明な
シートであつた。
The present invention provides a non-yellowing urethane resin composition that provides a cured product with excellent transparency and scratch resistance as well as excellent weather resistance, and is particularly easy to handle as long as no diisocyanate vapor is generated during the production and molding and curing of the composition. The present invention relates to a yellowing urethane resin composition. There is an increasing trend for transparent resins to be used in place of inorganic glass, which has traditionally been used in fields such as lenses, lighting equipment, ornaments, and accessories.
As such transparent resins, methyl poly(meth)acrylate, polycarbonate, and the like are conventionally known, but these resins have the disadvantage of poor scratch resistance. Urethane resins have excellent scratch resistance and are suitable for the above-mentioned uses, but urethane resins using aromatic isocyanates have the disadvantage of yellowing when exposed to ultraviolet rays. JP-A-52-86447 proposes a non-yellowing urethane resin composition that can provide molded products with excellent weather resistance. However, this composition contains a large amount of aliphatic diisocyanate, and highly toxic diisocyanate vapor is often generated during degassing under reduced pressure and heating during curing, creating problems in the working environment. . Furthermore, JP-A-55-98172 describes a specific isocyanate-isocyanurate as a polyisocyanate, its production method, and its use as a starting material for producing polyurethane lacquer.
Although its low vapor pressure, high photostability, weather resistance, etc. are described, there is no disclosure of a urethane resin composition suitable for producing a cast-molded product without the inclusion of air bubbles. In view of the above, the present inventors have attempted to produce paint films and cast molded products that are safe, solvent-free, and have excellent weather resistance and can be handled without the generation of diisocyanate vapor, particularly without air bubbles. In order to find a non-yellowing urethane resin composition suitable for use, the present invention has been completed through extensive research. That is, the present invention provides (a) a polyisocyanate containing three or more isocyanate groups in one molecule, in which aliphatic diisocyanates are bonded through biuret bonds and/or isocyanurate bonds, and whose viscosity at 30° C. is 3000 centipoise or less; (b) (b-1) A solvent-free hydroxyl group-containing compound with a molecular weight of 300 to 3000 and two or more hydroxyl groups in one molecule, and (b-2) A solvent-free hydroxyl group-containing compound with a molecular weight of 200 or less and 2 or more hydroxyl groups in one molecule. It consists of a polyhydric alcohol having two or more hydroxyl groups, component (b-1) and component (b
-2) It relates to a non-yellowing urethane resin composition characterized in that it contains 0.8 to 1.5 equivalents of isocyanate groups as component (a) to 1 equivalent of total hydroxyl groups in components and does not use a solvent. The urethane resin composition of the present invention includes (a), (b-1)
and (b-2), and these three components are mixed, cast or coated, and then cured at room temperature or under heating to give the desired molded product or coating film. As shown, the resulting molded product or coating has excellent transparency, scratch resistance, and weather resistance, and does not generate highly toxic diisocyanate vapor during mixing and curing, and cast molded products do not contain air bubbles. It is something. The present invention will be explained in detail below. The reason why the diisocyanate used in component (a) of the composition of the present invention is limited to aliphatic diisocyanates is to make the composition non-yellowing. Non-yellowing cannot be obtained with aromatic diisocyanates. Furthermore, the reason for using polyisocyanate in component (a) is that volatility is eliminated by increasing the molecular weight by bonding with diisocyanate, thereby preventing evaporation during degassing and curing. This is because low molecular weight diisocyanates generate highly toxic vapors that irritate the eyes and noses of workers and cause respiratory problems. The reason why we limited the types of bonds in polyisocyanate to biuret bonds and isocyanurate bonds is that the polyisocyanate obtained by these bonds has a viscosity at 30°C.
Since it is easy to obtain a product of 3000 cps or less, it has high fluidity and can easily remove bubbles when degassing under vacuum.
This is because the compatibility with the hydroxyl group-containing compounds of components -1) and (b-2) is good. The aliphatic diisocyanate in the present invention is
A diisocyanate consisting of a linear or branched saturated hydrocarbon having 4 to 9 carbon atoms and an isocyanate group, such as 1,4-tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate. (abbreviated as HMDI), 2, 2, 4 (or 2, 4,
4)-trimethyl-hexamethylene diisocyanate and the like. Among them, HMDI is preferable. These diisocyanates may be used singly or as a mixture of two or more. Biuret bonding or/
and isocyanurate bonding methods are known, for example, JP-A-53-106797, JP-A-52
The method described in Publication No. 69497 can be used. The polyisocyanate containing three or more isocyanate groups in one molecule due to the above-mentioned biuret or/and isocyanurate bonds is used in the composition of the present invention.
It is useful as component (a), and HMDI biuret multimer and HMDI isocyanurate multimer are particularly preferred. The component (b-1) in the present invention is selected from hydroxyl group-containing compounds having a molecular weight of 300 or more and 3000 or more and having two or more hydroxyl groups in one molecule. ~4 polyoxyalkylene glycols, such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, with a weight average molecular weight of 3000 or less, especially 300~
2000 is preferred, and difunctional or trifunctional polyether polyols are effective. The polyester polyol is synthesized from adipic acid or phthalic acid as the dicarboxylic acid, a dihydric alcohol having 2 to 6 carbon atoms as the polyhydric alcohol, trimethylolpropane, or pentaerythritol, each singly or in a mixture of two or more. Average molecular weight 3000 or less, especially weight average molecular weight 300
Polyester polyol having 2 to 4 terminal hydroxyl groups of ~2000 or weight average molecular weight of 300~
Examples include polycaprolactone polyols having two or more hydroxyl groups at the ends of 3,000. The hydroxyl group-terminated urethane prepolymer is obtained by reacting the aliphatic diisocyanate with a difunctional polyether polyol or polyester polyol in a ratio of less than 1 equivalent of isocyanate group per 1 equivalent of hydroxyl group of the polyol. Urethane prepolymers obtained by reacting polypropylene glycol with HMDI or/and IPDI are preferred. (b-2) The molecular weight of the component is 200 or less, and 1
Examples of polyhydric alcohols having two or more hydroxyl groups in the molecule include dihydric alcohols having 2 to 6 carbon atoms, such as ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, pentaerythritol, 1,5
-pentamethylene glycol, 1,6-hexamethylene glycol, trimethylolpropane, and pentaerythritol. If the molecular weight of component (b-1) exceeds 3,000 or the molecular weight of component (b-2) exceeds 200, it may be due to insufficient compatibility with the polyisocyanate, or if the molecular weight of component (b-2) exceeds 3,000, bubbles may be formed by degassing under vacuum. It may take a long time to remove the
This is undesirable as there may be cases where the air bubbles are not completely removed. In addition, if component (b-1) contains a solvent, the solvent will volatilize during degassing under vacuum, and not only will degassing be insufficient, but the mixture containing the solvent will not be cast. This causes problems such as foaming and shrinkage after curing. Furthermore, if each of component (b-1) and component (b-2) is used alone, curing may be delayed or may not occur, which is not preferable. (b-1) component and (b
-2) The ratio of the components is preferably 1/99 to 99/1 by weight. The composition of the present invention has 0.8 to 1.5 equivalents of isocyanate groups in component (a), more preferably 1.0 to 1.2 equivalents of isocyanate groups in component (a) per 1 equivalent of hydroxyl groups in the total of components (b-1) and (b-2).
It is a mixture of components (a), (b-1), and (b-2) in equivalent amounts, and is cured and molded after mixing these three components. If the proportion of isocyanate groups is less than 0.8 equivalent, the hardness and strength of the molded product or coating film will decrease, and the weather resistance will decrease. On the other hand, if it exceeds 1.5 equivalents, foaming may occur during the curing process, or
The cured product is too hard and brittle, making it undesirable for practical use. A conventional method may be used to obtain a molded article or a coating film of urethane resin using the composition of the present invention. That is, component (a) and components (b-1) and (b-2) are mixed and cured by casting or coating, but before or after mixing, the mixture is degassed under vacuum at room temperature or under heating. , harden at room temperature or under heat. Curing conditions may be appropriately selected depending on the process, product characteristics, etc., and are not particularly limited. It is of course possible to add to the composition a catalyst for promoting the reaction between isocyanate groups and hydroxyl groups, antioxidants, ultraviolet absorbers, leveling agents, mold release agents, and other additives. The urethane resin composition of the present invention is particularly suitable for producing molded products such as resin lenses, lighting supplies, ornaments, accessories, surface protective films, etc., but of course other uses are not excluded. Examples are shown below. First, the polyisocyanate used will be described. Polyisocyanate A: Hexamethylene diisocyanate biuret bonded polymer shown in Example 1 of JP-A-53-106797, viscosity
1200cps/30℃, isocyanate group bonding amount 23.9% by weight. Polyisocyanate B: Isocyanurate-bonded polymer of hexamethylene diisocyanate shown in Example 1 of JP-A-52-69497, viscosity 2500 cps/30°C, isocyanate group content 23.6
weight%. Examples 1 to 7 Comparative Examples 1 and 2 Predetermined amounts of component (a) and components (b-1) and (b-2) shown in Table 1 were placed in respective beakers and heated at room temperature under reduced pressure (10 mmHg or less). ) for 30 minutes to remove internal moisture and volatile impurities. After cooling this under dry air, (a), (b-1), (b-2)
Mix the ingredients thoroughly. Once the mixture is homogeneously mixed, vacuum degas it again, and when the surface no longer foams, pour it into a polyethylene mold of 15 x 15 x 1 (cm) (depth) to a thickness of approximately 5 mm. 5 under vacuum
After being left for a few minutes, it was placed in an oven at 85°C, allowed to harden for 15 minutes, cooled to room temperature, and removed from the mold. No irritating odor was generated during the above operation, and the operation could be carried out safely and easily. The product obtained was a transparent sheet having the physical properties shown in Table 1.
【表】【table】
【表】
参考例
実施例１に示した(a)成分のポリイソシアネート
Ａに代えてビス（４―イソシアネートシクロヘキ
シル）メタンを使用して実施例１〜８で示したと
同じ操作によりウレタン樹脂を得た。しかし、
(a)，（ｂ―１），（ｂ―２）成分の混合、注型、オ
ーブンへの出し入れ等の操作時に強い刺激臭と眼
に対する刺激が有り、操作が行いにくく、又、減
圧に用いた真空ポンプにも刺激臭の強い物質がた
まつていた。
実施例８ 比較例３，４
第２表に示す(a)成分と（ｂ―１），（ｂ―２）成
分の所定量を実施例１と同様に操作を行い、加熱
硬化させた。操作中は、刺激臭の発生は無かつた
が、比較例３は、硬化に時間がかかり、比較例４
は硬化しなかつた。[Table] Reference Example A urethane resin was obtained by the same operation as shown in Examples 1 to 8, using bis(4-isocyanatecyclohexyl)methane in place of polyisocyanate A as component (a) shown in Example 1. . but,
(a), (b-1), (b-2) There is a strong irritating odor and irritation to the eyes during operations such as mixing the ingredients, pouring, and putting them in and out of the oven, making them difficult to operate, and not being used for decompression. A substance with a strong odor had accumulated in the vacuum pump. Example 8 Comparative Examples 3 and 4 Predetermined amounts of component (a) and components (b-1) and (b-2) shown in Table 2 were treated in the same manner as in Example 1 and heat-cured. During the operation, no irritating odor was generated, but Comparative Example 3 took a long time to cure, and Comparative Example 4
did not harden.
【表】【table】
【表】
実施例 ９
実施例１で用いたと同じ成分組成の混合物を作
り、アルミニウム板上に印刷を施した基板上に約
200μの厚さにコーテイングした後、常温真空下
で15分間脱泡し、120℃で10分間硬化を行つた。
室温で１日放置した後の塗膜の表面硬度は鉛筆硬
度（JIS Ｋ 5400）で3Hであつた。この塗膜は
耐傷性、基板との密着性に優れ、表面保護膜とし
て充分な特性を有していた。
以上により明らかなように、本発明の組成物は
有毒なジイソシアネートの発生がなく、簡単な設
備で安全に操作ができ、高温での硬化が可能であ
り、操業上大きな利点を有し、得られる成形品及
び塗膜の耐傷性、耐候性、透明性は優れたもので
あり、注型成形品には気泡の混入がないものであ
る。[Table] Example 9 A mixture having the same composition as that used in Example 1 was made, and approximately
After coating to a thickness of 200μ, defoaming was performed under vacuum at room temperature for 15 minutes, and curing was performed at 120°C for 10 minutes.
The surface hardness of the coating film after being left at room temperature for one day was 3H in terms of pencil hardness (JIS K 5400). This coating film had excellent scratch resistance and adhesion to the substrate, and had sufficient properties as a surface protective film. As is clear from the above, the composition of the present invention does not generate toxic diisocyanates, can be safely operated with simple equipment, and can be cured at high temperatures, and has great operational advantages. The molded product and coating have excellent scratch resistance, weather resistance, and transparency, and the cast molded product is free of air bubbles.
Claims (1)
合又は／及びイソシアヌレート結合により結合
させた１分子中に３個以上のイソシアネート基
を含有し、30℃における粘度が3000センチポイ
ズ以下のポリイソシアネートと、 (b) （ｂ―１）分子量が300以上3000以下で１分
子中に水酸基を２個以上有する溶剤を含まない
水酸基含有化合物と（ｂ―２）分子量が200以
下で、１分子中に水酸基を２個以上有する多価
アルコールとからなり、（ｂ―１）成分と（ｂ
―２）成分の合計水酸基１当量に対して(a)成分
のイソシアネート基を0.8〜1.5当量の割合で含
み、溶剤を用いないことを特徴とする無黄変ウ
レタン樹脂組成物。 ２ (a)成分の脂肪族ジイソシアネートが、１，６
―ヘキサメチレンジイソシアネートである特許請
求の範囲第１項記載の無黄変ウレタン樹脂組成
物。 ３ 成分（ｂ―１）の化合物が、炭素数２〜４の
ポリオキシアルキレングリコール、炭素数２〜６
の２価アルコールとアジピン酸より合成される末
端が水酸基のポリエステル、カプロラクトンポリ
オール、及びポリプロピレングリコールと脂肪族
ジイソシアネートより合成されるプレポリマーか
ら選ばれる少なくとも１種である特許請求の範囲
第１項記載の無黄変ウレタン樹脂組成物。 ４ 成分（ｂ―２）の化合物が、炭素数２〜６の
２価アルコール、トリメチロールプロパン、及び
ペンタエリスリトールから選ばれる少なくとも１
種である特許請求の範囲第１項記載の無黄変ウレ
タン樹脂組成物。[Scope of Claims] 1 (a) Polymer containing three or more isocyanate groups in one molecule, in which aliphatic diisocyanates are bonded through biuret bonds and/or isocyanurate bonds, and has a viscosity of 3000 centipoise or less at 30°C. (b) (b-1) A solvent-free hydroxyl-containing compound with a molecular weight of 300 to 3000 and two or more hydroxyl groups in one molecule, and (b-2) A solvent-free hydroxyl group-containing compound with a molecular weight of 200 or less and one molecule to consisting of a polyhydric alcohol having two or more hydroxyl groups, component (b-1) and component (b
-2) A non-yellowing urethane resin composition comprising component (a) isocyanate groups in a ratio of 0.8 to 1.5 equivalents per 1 equivalent of total hydroxyl groups in components, and does not use a solvent. 2 The aliphatic diisocyanate of component (a) is 1,6
- The non-yellowing urethane resin composition according to claim 1, which is hexamethylene diisocyanate. 3 The compound of component (b-1) is a polyoxyalkylene glycol having 2 to 4 carbon atoms, or a polyoxyalkylene glycol having 2 to 6 carbon atoms.
Claim 1, wherein the polymer is at least one selected from a polyester with a hydroxyl group at the end synthesized from a dihydric alcohol and adipic acid, a caprolactone polyol, and a prepolymer synthesized from a polypropylene glycol and an aliphatic diisocyanate. Non-yellowing urethane resin composition. 4. The compound of component (b-2) is at least one compound selected from dihydric alcohols having 2 to 6 carbon atoms, trimethylolpropane, and pentaerythritol.
The non-yellowing urethane resin composition according to claim 1, which is a seed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56069390A JPS57185315A (en) | 1981-05-11 | 1981-05-11 | Urethane resin composition without yellowing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56069390A JPS57185315A (en) | 1981-05-11 | 1981-05-11 | Urethane resin composition without yellowing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57185315A JPS57185315A (en) | 1982-11-15 |
| JPS6329689B2 true JPS6329689B2 (en) | 1988-06-15 |
Family
ID=13401217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56069390A Granted JPS57185315A (en) | 1981-05-11 | 1981-05-11 | Urethane resin composition without yellowing |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57185315A (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5753730A (en) * | 1986-12-15 | 1998-05-19 | Mitsui Toatsu Chemicals, Inc. | Plastic lenses having a high-refractive index, process for the preparation thereof and casting polymerization process for preparing sulfur-containing urethane resin lens and lens prepared thereby |
| DE3881570T2 (en) * | 1987-03-17 | 1994-02-03 | Asahi Glass Co Ltd | Reactive curable composition and products containing the cured products of this composition. |
| JP2707579B2 (en) * | 1987-03-17 | 1998-01-28 | 旭硝子株式会社 | Reaction curable composition and product having the reaction cured product |
| CA1320806C (en) * | 1988-02-17 | 1993-08-03 | Teruyuki Nagata | Plastic lenses having a high-refracting index and process for the preparation thereof |
| JP2680593B2 (en) * | 1988-02-22 | 1997-11-19 | 三井東圧化学株式会社 | Urethane resin lens and manufacturing method thereof |
| KR20060009384A (en) | 2003-06-09 | 2006-01-31 | 호야 가부시키가이샤 | Transparent shaped body |
| JP4810854B2 (en) * | 2005-03-29 | 2011-11-09 | Ｄｉｃ株式会社 | Polyurethane film with excellent blocking resistance |
| JP4851734B2 (en) * | 2005-06-13 | 2012-01-11 | スリーエム イノベイティブ プロパティズ カンパニー | Marking film for handrail belts on escalators or moving walkways |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598172A (en) * | 1979-01-16 | 1980-07-25 | Bayer Ag | Novel isocyanatooisocyanurate*its manufacture and use for polyurethane lacquer as isocyanate ingredient |
-
1981
- 1981-05-11 JP JP56069390A patent/JPS57185315A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5598172A (en) * | 1979-01-16 | 1980-07-25 | Bayer Ag | Novel isocyanatooisocyanurate*its manufacture and use for polyurethane lacquer as isocyanate ingredient |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57185315A (en) | 1982-11-15 |
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