JPS6320255B2 - - Google Patents
Info
- Publication number
- JPS6320255B2 JPS6320255B2 JP15812379A JP15812379A JPS6320255B2 JP S6320255 B2 JPS6320255 B2 JP S6320255B2 JP 15812379 A JP15812379 A JP 15812379A JP 15812379 A JP15812379 A JP 15812379A JP S6320255 B2 JPS6320255 B2 JP S6320255B2
- Authority
- JP
- Japan
- Prior art keywords
- composition
- general formula
- polyene
- polythiol
- formula
- 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
- 239000000203 mixture Substances 0.000 claims description 24
- 229920006295 polythiol Polymers 0.000 claims description 17
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 3
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 2
- 150000004291 polyenes Chemical class 0.000 description 14
- 239000011521 glass Substances 0.000 description 8
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 238000002845 discoloration Methods 0.000 description 5
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000003504 photosensitizing agent Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 3
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 239000005340 laminated glass Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- HCZMHWVFVZAHCR-UHFFFAOYSA-N 2-[2-(2-sulfanylethoxy)ethoxy]ethanethiol Chemical compound SCCOCCOCCS HCZMHWVFVZAHCR-UHFFFAOYSA-N 0.000 description 2
- DZZAHLOABNWIFA-UHFFFAOYSA-N 2-butoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCCCC)C(=O)C1=CC=CC=C1 DZZAHLOABNWIFA-UHFFFAOYSA-N 0.000 description 2
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- -1 diene hydrocarbons Chemical class 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- SWFHGTMLYIBPPA-UHFFFAOYSA-N (4-methoxyphenyl)-phenylmethanone Chemical compound C1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 SWFHGTMLYIBPPA-UHFFFAOYSA-N 0.000 description 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- QWQFVUQPHUKAMY-UHFFFAOYSA-N 1,2-diphenyl-2-propoxyethanone Chemical compound C=1C=CC=CC=1C(OCCC)C(=O)C1=CC=CC=C1 QWQFVUQPHUKAMY-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- LPUUPYOHXHWKAR-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol 3,3,3-tris(sulfanyl)propanoic acid Chemical compound SC(CC(=O)O)(S)S.C(O)C(CC)(CO)CO LPUUPYOHXHWKAR-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- VLCCKNLIFIJYOQ-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] 2,2,3,3-tetrakis(sulfanyl)propanoate Chemical compound OCC(CO)(CO)COC(=O)C(S)(S)C(S)S VLCCKNLIFIJYOQ-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000005304 optical glass Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- KOODSCBKXPPKHE-UHFFFAOYSA-N propanethioic s-acid Chemical compound CCC(S)=O KOODSCBKXPPKHE-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- CWERGRDVMFNCDR-UHFFFAOYSA-M thioglycolate(1-) Chemical compound [O-]C(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-M 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Landscapes
- Joining Of Glass To Other Materials (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Description
本発明はポリエンとポリチオールと成分とする
光硬化性組成物に関する。
ポリエンとポリチオールが活性光線の照射など
のラジカル発生手段により重付加反応すること
は、例えばジヤーナル・オブ・ザ・アメリカン・
ケミカル・ソサイテイ（J.Am.Chem.Soc.）第70
巻第993頁（1948年）により知られている。米国
特許第3338810号明細書には、ポリエンとして炭
素数４〜６のジエン炭化水素からつくられる液状
のポリマー、例えばポリブタジエンを使うことが
記載されている。しかし、特公昭47−3269号公報
ではポリブタジエン、ポリイソプレンの如き内部
に不飽和結合を持つ重合体のポリチオールによる
硬化物は、硬化後にも内部に不飽和結合を残すの
で、熱酸化、紫外線の触媒作用による酸化に対し
不安定であり、オゾンにより迅速に侵され、その
結果内部に二重結合をもつ重合体には時として減
成、脆化が起り、その使用寿命が短縮してしまう
旨記載されており、同公報はポリエンとして内部
に反応性炭素数―炭素不飽和結合を含まないある
種の官能基を有するものを用いることを提案して
いる。
しかしながら、米国特許第3338810号明細書や
特公昭47−3269号公報で提案しているポリエン
は、ポリエンそのものの二重結合当り分子量が高
く、通常のポリチオールと組合わせた場合、粘度
が非常に高くなり、コーテイング、接着剤又は塗
料などとして利用する場合特に制限を受ける。
本発明はこれらの欠点を有しないポリエン―ポ
リチオール組成物を提供することを目的とする。
本発明者は内部に例えばマレイン酸又靖はフマ
ール酸に基づく炭素―炭素二重結合を含む特定の
ポリエンと１分子中に２個以上のチオール基をも
つポリチオールを用いれば、前記特公昭47−3269
号公報に記載される如く、ポリエン―ポリチオー
ル組成物においてポリエンの内部の二重結合が未
反応のまま残存することはなく、ポリエン内部の
二重結合も未端二重結合と同様にチオール基と高
い反応性を示し、三次元構造をとることを知得
し、本発明を完成した。
即ち、本発明によれば下記(1)及び(2)の成分を含
むことを特徴とする光硬化可能な組成物が提供さ
れる。
(1) 一般式
（式中Ｒは水素原子、塩素原子、弗素原子、ア
ルキル基、置換アルキル基、アルコキシ基又は置
換アルコキシ基であり、ｎは０又は１〜10の整数
である。）で表わされるポリエン。
(2) 一般式
Ｚ（―SH）n （）
（式中Ｚはｍ個の官能基を有する有機残基であ
り、ｍは２以上の整数である）で表わされ、平均
分子量が80〜150000の範囲にあるポリチオール。
本発明に用いられるポリエンは一般式（）で
表わされるものであり、その式中Ｒがアルキル基
又はアルコキシ基である場合はそれぞれ炭素原子
１〜３個有するものが好ましく、そして置換アル
キル基又は置換アルコキシ基である場合は、炭素
原子１〜３個を有するハロゲン化アルキル又はア
ルコキシ基が好ましい。
一般式（）で表わされるポリエンの代表的な
ものは、マレイン酸又はフマール酸のジエステル
が挙げられ、特にマレイン酸ジアリルエステル又
はフマール酸ジアリルエステルが好ましく使用さ
れるが、これらの例に限定されるものではない。
本発明に用いられるポリチオールは一般式
（）で表わされるものであり、その式中ｍは２
〜10のものが好ましい。ポリチオールは平均分子
量が80〜150000のものが用いられ、平均分子量が
80未満のものは組成物の硬化性が不十分であり、
150000をこえるものは高粘度であるため取り扱い
が困難である。本発明では、ポリチオールとし
て、エチレングリコール、ポリエチレングリコー
ル、ブタンジオール、ジフエニルシランジオー
ル、トリメチロールエタン、トリメチロールプロ
パン、ペンタエリスリトール、ジペンタエリスリ
トール、ポリビニルアルコール若しくはビスフエ
ノールＡなどの多価アルコールと、チオグリコー
ル酸若しくはチオプロピオン酸などとのエステル
化物、又はトリエチレグリコールジメルカプタ
ン、又は下記一般式（）若しくは（）で表わ
される多価チオールが好ましく使用される。
一般式
（式中ｎは１〜２の整数である。）
一般式
（式中Ｒ及びR′は炭素原子数１〜４のアルキ
レン基である。）
本発明の組成物において、特にポリチオール成
分として、一般式（）で示されるトリアジン環
を有するポリチオールを用いた場合は耐候性、耐
水性及び表面硬化性が特にすぐれた硬化物を得る
ことができる。
本発明の組成物において、ポリエンとポリチオ
ールの重量割合は49：１〜１：49の範囲が好まし
く、特にポリエン中の二重結合とポリチオール中
のチオール基が化学当量であるときが最も好まし
い。
本発明の組成物は光硬化を促進するために光増
感剤を含むことができる。光増感剤としては、例
えばベンゾフエノン、ｐ―メトキシベンゾフエノ
ン、アセトフエノン、ｍ―クロルアセトン、ベン
ゾイン、ベンゾインメチルエーテル、ベンゾイン
エチルエーテル、ベンゾインプロピルエーテル、
ベンゾインブチルエーテル、アゾビスイソブチロ
ニトリル、アカライトグリーンなどがあげられ
る。光増感剤の量は特に制限されないが、ポリエ
ンとポリチオールの重量和100重量部に対し0.001
〜50重量部が好適である。又、光増感剤を予めポ
リエン及び／又はポリチオールに反応させておく
ことも可能である。
更に必要であれば、本発明の組成物は酸化防止
剤、PH調節剤、キレート化剤、染料、顔料、充填
剤、シランカツプリング剤、粘度調節剤、界面活
性剤、防炎剤、帯電防止剤、可塑剤、チクソトロ
ピー賦与剤などを適合含むことができる。
本発明の組成物は活性光線の照射によつて硬化
し、耐候性のすぐれたポリチオエーテルを生成す
る。本発明の組成物は強度の接着力を有しガラス
などの接着剤として使用できる。特にその硬化物
は紫外線分光透過率の変化が小さいのでレンズな
どの光学ガラスの接着に最適である。
以下、実施例をもつて説明する。
実施例 １
マレイン酸ジアリルエステル196ｇ（１モル）
とトリメチロールプロパントリスメルカプトプロ
ピオネート398ｇ（１モル）とベンゾインイソプ
ロピルエーテル5.9ｇを簡単に混合し、この混合
物を金型に流し込み、それに400Wの紫外線を30
cmの距離から照射した。混合物は10秒で硬化し、
従20mm×横10×厚さ２mmのシートを得た。このシ
ートをウエザーメーターにかけて、下記の条件に
より、シートの変色の度合及び表面の状態を観察
したところ、いずれも変化が認められなかつた。
ウエザーメーター試験条件
光源 カーボンアーク
温度 60℃
散水 １時間中に12分間散水する
時間 2000時間
実施例 ２
フマール酸ジアリルエステル78.4ｇ（0.4モル）
とペンタエリスリトールテトラキスメルカプトプ
ロピオネート146.4ｇ（0.3モル）とベンゾインブ
チルエーテル2.2ｇを簡単に混合し、実施例１と
同様にして硬化させた。硬化に要した時間は８秒
であつた。この硬化シートについても実施例１と
同一条件でウエザーメーターにより試験したが、
変色及び表面変色は認められなかつた。
実施例 ３
マレイン酸ジアリルエステル39.2（0.2モル）と
トリエチレングリコールジメルカプタン54.6ｇ
（0.3モル）とベンゾインメチルエーテル0.9ｇを
簡単に混合し、実施例１と同様にして硬化させ
た。硬化には20秒を要した。この硬化シートにつ
いても実施例１と同一条件でウエザーメーターに
より試験したが、変色及び表面変化は認められな
かつた。
実施例 ４
マレイン酸ジアリルエステル196ｇ（１モル）
とトリス（２―ヒドロキシエチル）イソシアヌレ
ートトリス（β―メルカプトプロピオネート）
525ｇ（１モル）とベンゾインイソプロピルエー
テル1.4ｇを簡単に混合し、組成物Ａを得た。こ
れに400Wの紫外線ランプを30cmの距離から照射
した。組成物Ａは20秒で硬化し、60秒で表面は乾
燥状態となつた。
実施例 ５
実施例４でつくられた組成物Ａを用い、厚さ１
mmのガラス板２枚を接着層の厚さ100μmで接着さ
せた。接着は組成物の塗布面に100Wの紫外線ラ
ンプを用いて10cmの距離から照射することによつ
てなされた。
0.1及び10時間照射し硬化接着した合わせガラ
スについて、実施例１と同一条件でウエザーメー
ターにより試験を行なつた。いずれも接着面の剥
離はなく、変色及び表面状態は認められなかつ
た。
又、接着した合わせガラスについて、分光透過
率を測定した。結果を第１表に示す。分光透過率
の変化は0.1％以内であつた。
The present invention relates to a photocurable composition containing polyene and polythiol as components. For example, the Journal of the American
Chemical Society (J.Am.Chem.Soc.) No. 70
Volume 993 (1948). US Pat. No. 3,338,810 describes the use of liquid polymers made from diene hydrocarbons having 4 to 6 carbon atoms, such as polybutadiene, as polyenes. However, Japanese Patent Publication No. 47-3269 states that polythiol cured products of polymers with internal unsaturated bonds, such as polybutadiene and polyisoprene, leave unsaturated bonds internally even after curing, so thermal oxidation and ultraviolet ray catalysis It is stated that the polymer is unstable to oxidation caused by the action and is rapidly attacked by ozone, and as a result, polymers with internal double bonds sometimes deteriorate and become brittle, shortening their service life. The publication proposes the use of a polyene having a certain type of functional group which does not contain any reactive carbon number-carbon unsaturated bond. However, the polyenes proposed in U.S. Pat. However, there are particular restrictions when using it as a coating, adhesive, or paint. The present invention aims to provide polyene-polythiol compositions which do not have these disadvantages. The inventor of the present invention has found that if a specific polyene containing a carbon-carbon double bond based on maleic acid or fumaric acid is used inside, and a polythiol having two or more thiol groups in one molecule, 3269
As described in the publication, in the polyene-polythiol composition, the double bonds inside the polyene do not remain unreacted, and the double bonds inside the polyene also form a thiol group in the same way as the terminal double bonds. They discovered that it exhibits high reactivity and has a three-dimensional structure, and completed the present invention. That is, according to the present invention, there is provided a photocurable composition characterized by containing the following components (1) and (2). (1) General formula (In the formula, R is a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group, and n is 0 or an integer from 1 to 10.) (2) It is represented by the general formula Z(-SH) n () (in the formula, Z is an organic residue having m functional groups, and m is an integer of 2 or more), and has an average molecular weight of 80 to Polythiols in the range of 150,000. The polyene used in the present invention is represented by the general formula (), and when R in the formula is an alkyl group or an alkoxy group, it preferably has 1 to 3 carbon atoms, and a substituted alkyl group or a substituted When it is an alkoxy group, a halogenated alkyl or alkoxy group having 1 to 3 carbon atoms is preferred. Typical polyenes represented by the general formula () include diesters of maleic acid or fumaric acid, with maleic acid diallyl ester or fumaric acid diallyl ester being particularly preferably used, but the polyenes are limited to these examples. It's not a thing. The polythiol used in the present invention is represented by the general formula (), where m is 2
~10 is preferred. Polythiols with an average molecular weight of 80 to 150,000 are used;
If it is less than 80, the curing properties of the composition are insufficient.
Anything over 150,000 is difficult to handle due to its high viscosity. In the present invention, polyhydric alcohols such as ethylene glycol, polyethylene glycol, butanediol, diphenylsilanediol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol, polyvinyl alcohol or bisphenol A, and thiols are used as polythiols. Esterified products with glycolic acid or thiopropionic acid, triethylene glycol dimercaptan, or polyvalent thiols represented by the following general formula () or () are preferably used. general formula (In the formula, n is an integer of 1 to 2.) General formula (In the formula, R and R' are alkylene groups having 1 to 4 carbon atoms.) In the composition of the present invention, especially when a polythiol having a triazine ring represented by the general formula () is used as the polythiol component, A cured product with particularly excellent weather resistance, water resistance, and surface hardening properties can be obtained. In the composition of the present invention, the weight ratio of polyene to polythiol is preferably in the range of 49:1 to 1:49, most preferably when the double bond in the polyene and the thiol group in the polythiol are in chemical equivalents. The compositions of the present invention can include a photosensitizer to promote photocuring. Examples of the photosensitizer include benzophenone, p-methoxybenzophenone, acetophenone, m-chloroacetone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether,
Examples include benzoin butyl ether, azobisisobutyronitrile, and acalite green. The amount of photosensitizer is not particularly limited, but it is 0.001 parts by weight per 100 parts by weight of the total weight of polyene and polythiol.
~50 parts by weight is preferred. It is also possible to react the photosensitizer with the polyene and/or polythiol in advance. Additionally, if necessary, the compositions of the present invention may contain antioxidants, PH modifiers, chelating agents, dyes, pigments, fillers, silane coupling agents, viscosity modifiers, surfactants, flame retardants, antistatic agents. Agents, plasticizers, thixotropic agents, etc. may be included. The composition of the present invention is cured by irradiation with actinic light to produce a polythioether with excellent weather resistance. The composition of the present invention has strong adhesive strength and can be used as an adhesive for glass and the like. In particular, the cured product exhibits small changes in ultraviolet spectral transmittance, making it ideal for bonding optical glasses such as lenses. Examples will be described below. Example 1 Maleic acid diallyl ester 196g (1 mol)
398 g (1 mol) of trimethylolpropane trismercaptopropionate and 5.9 g of benzoin isopropyl ether are mixed briefly, this mixture is poured into a mold, and 400W ultraviolet light is applied to it for 30 minutes.
Irradiated from a distance of cm. The mixture hardens in 10 seconds,
A sheet measuring 20 mm wide x 10 mm wide x 2 mm thick was obtained. When this sheet was subjected to a weather meter and the degree of discoloration and surface condition of the sheet were observed under the following conditions, no change was observed in either case. Weather meter test conditions Light source Carbon arc temperature 60℃ Water sprinkling Duration of water sprinkling for 12 minutes per hour 2000 hours Example 2 Fumaric acid diallyl ester 78.4 g (0.4 mol)
146.4 g (0.3 mol) of pentaerythritol tetrakis mercaptopropionate and 2.2 g of benzoin butyl ether were mixed briefly and cured in the same manner as in Example 1. The time required for curing was 8 seconds. This cured sheet was also tested using a weather meter under the same conditions as Example 1.
No discoloration or surface discoloration was observed. Example 3 Maleic acid diallyl ester 39.2 (0.2 mol) and triethylene glycol dimercaptan 54.6 g
(0.3 mol) and 0.9 g of benzoin methyl ether were briefly mixed and cured in the same manner as in Example 1. It took 20 seconds to cure. This cured sheet was also tested using a weather meter under the same conditions as in Example 1, but no discoloration or surface change was observed. Example 4 Maleic acid diallyl ester 196g (1 mol)
and tris(2-hydroxyethyl)isocyanurate tris(β-mercaptopropionate)
Composition A was obtained by simply mixing 525 g (1 mole) and 1.4 g of benzoin isopropyl ether. This was irradiated with a 400W ultraviolet lamp from a distance of 30cm. Composition A cured in 20 seconds, and the surface became dry in 60 seconds. Example 5 Using composition A made in Example 4, a thickness of 1
Two mm glass plates were bonded together with an adhesive layer having a thickness of 100 μm. Adhesion was achieved by irradiating the coated surface of the composition with a 100 W ultraviolet lamp from a distance of 10 cm. The laminated glasses cured and bonded by irradiation for 0.1 and 10 hours were tested using a weather meter under the same conditions as in Example 1. In all cases, there was no peeling of the adhesive surface, and no discoloration or surface condition was observed. In addition, the spectral transmittance of the bonded laminated glass was measured. The results are shown in Table 1. The change in spectral transmittance was within 0.1%.
【表】
実施例 ６
組成物Ａを接着剤として、ガラス／ガラスの接
着を行なつた。接着は２枚のガラス間の厚さ10μ
の接着層に、400Wの紫外線ランプを10cmの距離
から30分間照射して行なつた。接着直後及び60
℃、95％RHに500時間保存後の引張剪断強度は
それぞれ47Kg／cm2及び49Kg／cm2であつた。
実施例 ７
フマール酸ジアリルエステル196ｇ（１モル）
とトリス（２―ヒドロキシエチル）イソシアヌレ
ートトリス（メルカプトアセテート）483ｇ（１
モル）とベンゾインイソプロピルエーテル1.4ｇ
を簡単に混合し組成物Ｂを製造した。この組成物
に400Wの紫外線ランプを30cmの距離から照射し
た。組成物は15秒間で硬化し、45秒後には乾燥状
態となつた。
実施例 ８
実施例７でつくられた組成物Ｂを用い、厚さ１
mmのガラス板２枚を厚さ100μで接着した。光源
は100Wの紫外線ランプを10cmの距離から照射し
た。接着した合わせガラスの分光透過率を測定し
た。結果を第２表に示す。[Table] Example 6 Glass/glass bonding was performed using Composition A as an adhesive. Adhesion is done with a thickness of 10μ between the two pieces of glass.
The adhesive layer was irradiated with a 400W ultraviolet lamp from a distance of 10cm for 30 minutes. Immediately after adhesion and 60
The tensile shear strengths after storage at 95% RH for 500 hours were 47 Kg/cm 2 and 49 Kg/cm 2 , respectively. Example 7 Fumaric acid diallyl ester 196g (1 mol)
and tris(2-hydroxyethyl)isocyanurate tris(mercaptoacetate) 483g (1
mole) and benzoin isopropyl ether 1.4g
were simply mixed to produce Composition B. This composition was irradiated with a 400 W ultraviolet lamp from a distance of 30 cm. The composition cured in 15 seconds and was dry after 45 seconds. Example 8 Using composition B made in Example 7, a thickness of 1
Two mm glass plates were glued to a thickness of 100μ. The light source was a 100W ultraviolet lamp irradiated from a distance of 10cm. The spectral transmittance of the bonded laminated glass was measured. The results are shown in Table 2.
【表】
実施例 ９
実施例７でつくられた組成物Ｂを接着剤として
用いガラス／ガラスの接着をした。接着は400W
の紫外線ランプを10cmの距離から30分間照射によ
り行なつた。接着層の厚さは10μであつた。接着
直後及び60℃、95％RHで500時間保存後の引張
剪断強度はそれぞれ49Kg／cm2及び48Kg／cm2であつ
た。[Table] Example 9 Composition B prepared in Example 7 was used as an adhesive to bond glass to glass. Adhesion is 400W
This was done by irradiating with an ultraviolet lamp from a distance of 10 cm for 30 minutes. The thickness of the adhesive layer was 10μ. The tensile shear strengths immediately after adhesion and after storage at 60° C. and 95% RH for 500 hours were 49 Kg/cm 2 and 48 Kg/cm 2 , respectively.
Claims (1)
光硬化可能な組成物。 (1) 一般式 （式中Ｒは水素原子、塩素原子、弗素原子、ア
ルキル基、置換アルキル基、アルコキシ基又は置
換アルコキシ基であり、ｎは０又は１〜10の整数
である。）で表わされるポリエン。 (2) 一般式 Ｚ（―SH）n （式中Ｚはｍ個の官能基を有する有機残基であ
り、ｍは２以上の整数である）で表わされ、平均
分子量が80〜150000の範囲にあるポリチオール。[Claims] 1. A photocurable composition comprising the following components (1) and (2). (1) General formula (In the formula, R is a hydrogen atom, a chlorine atom, a fluorine atom, an alkyl group, a substituted alkyl group, an alkoxy group, or a substituted alkoxy group, and n is 0 or an integer from 1 to 10.) (2) It is represented by the general formula Z(-SH) n (in the formula, Z is an organic residue having m functional groups, and m is an integer of 2 or more) and has an average molecular weight of 80 to 150,000. Polythiols in the range.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15812379A JPS5681338A (en) | 1979-12-07 | 1979-12-07 | Photocurable composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15812379A JPS5681338A (en) | 1979-12-07 | 1979-12-07 | Photocurable composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5681338A JPS5681338A (en) | 1981-07-03 |
| JPS6320255B2 true JPS6320255B2 (en) | 1988-04-27 |
Family
ID=15664792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15812379A Granted JPS5681338A (en) | 1979-12-07 | 1979-12-07 | Photocurable composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5681338A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013047435A1 (en) | 2011-09-29 | 2013-04-04 | 日産化学工業株式会社 | Light-curing resin composition |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61157529A (en) * | 1984-12-28 | 1986-07-17 | Denki Kagaku Kogyo Kk | Composition curable with electron radiation |
| JPS61157530A (en) * | 1984-12-28 | 1986-07-17 | Denki Kagaku Kogyo Kk | Curable composition |
| JP5144852B2 (en) * | 2007-06-27 | 2013-02-13 | 電気化学工業株式会社 | Photo-curable composition, adhesive |
-
1979
- 1979-12-07 JP JP15812379A patent/JPS5681338A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013047435A1 (en) | 2011-09-29 | 2013-04-04 | 日産化学工業株式会社 | Light-curing resin composition |
| US9714364B2 (en) | 2011-09-29 | 2017-07-25 | Nissan Chemical Industries, Ltd. | Photo-curable resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5681338A (en) | 1981-07-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4139385A (en) | Coating method and composition using cationic photoinitiators polythio components and polyolefin components | |
| KR101528082B1 (en) | Methods for making cured sealants by actinic radiation and realted compositions | |
| EP0549228B1 (en) | Photocurable resin composition | |
| JPS61261365A (en) | Photo-curable coating composition | |
| EP0217506A2 (en) | Modified disulphur polymer composition and method for making same | |
| US4479860A (en) | Photo-curable epoxy resin composition | |
| RU2670901C9 (en) | Options for use of uv-curing sealants based on polythioethers for sealing of fastening devices and for leveling of surfaces | |
| US4272586A (en) | Laminated glass product | |
| JP2583435B2 (en) | Thiolene compositions based on bicyclic ene compounds | |
| KR20100092947A (en) | Salt compound, cationic polymerization initiator and cationically polymerizable composition | |
| EP1277776A1 (en) | Photocurable resin composition for sealing material and method of sealing | |
| JP4132397B2 (en) | Photocurable resin composition, liquid crystal inlet sealing agent and liquid crystal display cell | |
| JP4034098B2 (en) | Polyene-polythiol-based photocurable resin composition | |
| JPS6084375A (en) | Primer composition | |
| JPS6320255B2 (en) | ||
| KR20060061821A (en) | Photo-curable resin composition and sealing agent for flat panel display using the same | |
| TWI774893B (en) | Organopolysiloxane compound and active energy ray curable composition containing the same | |
| JP2019019339A (en) | Methods for making cured sealants by actinic radiation and related compositions | |
| JPS6158085B2 (en) | ||
| EP0014785B1 (en) | Coating method and curable compositions | |
| JP2005187636A (en) | Photo-curable resin composition, adhesive for display device, method of bonding and display device | |
| KR100555290B1 (en) | Adhesive Silicone Elastomer Films, and Coatings and Constructions Using the Same | |
| JP2000319577A (en) | Ultraviolet-curable composition for coating, coating material therefrom and production thereof | |
| JP4805216B2 (en) | Photocurable resin composition | |
| JPS60147425A (en) | Curable resin composition |