JPH01272551A - Polymerizable bifunctional acrylate monomer - Google Patents
Polymerizable bifunctional acrylate monomerInfo
- Publication number
- JPH01272551A JPH01272551A JP9988588A JP9988588A JPH01272551A JP H01272551 A JPH01272551 A JP H01272551A JP 9988588 A JP9988588 A JP 9988588A JP 9988588 A JP9988588 A JP 9988588A JP H01272551 A JPH01272551 A JP H01272551A
- Authority
- JP
- Japan
- Prior art keywords
- acrylate monomer
- formula
- meth
- group
- bifunctional acrylate
- 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
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 title claims description 20
- 230000001588 bifunctional effect Effects 0.000 title claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims description 5
- 150000002430 hydrocarbons Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 19
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 abstract description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 150000001408 amides Chemical class 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 125000001424 substituent group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000004132 cross linking Methods 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 238000010894 electron beam technology Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000004990 Smectic liquid crystal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- -1 benzoin alkyl ether Chemical class 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規な重合性２官能アクリレートモノマーに
関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a novel polymerizable bifunctional acrylate monomer.
従来、２官能アクリレートモノマーとしては、主として
、放射線および紫外線硬化型のモノマーが多数知られて
いるが、従来の重合性アクリレートモノマーは、アクリ
レート間の骨格構造が分子配向性に欠けるため、その硬
化物の力学的および熱的等の諸物性において十分満足で
きるのちはないのが現状である。Conventionally, many radiation-curable and ultraviolet-curable monomers have been known as difunctional acrylate monomers, but conventional polymerizable acrylate monomers lack molecular orientation in the skeletal structure between acrylates, so their cured products cannot be cured. At present, there is no way to fully satisfy the physical properties such as mechanical and thermal properties.
一方、力学的、熱的等の諸物性に優れた高分子材料とし
ては、従来より全芳香族高分子、液晶高分子等が種々開
発されてきた。しかしながら、これら従来の材料は溶解
性および溶融性の点で劣るものが多く、そのため材料と
しての用途や加工性の点で大きく制限されるという問題
がある。On the other hand, various kinds of polymer materials having excellent physical properties such as mechanical and thermal properties have been developed, such as wholly aromatic polymers and liquid crystal polymers. However, many of these conventional materials have poor solubility and meltability, and therefore have the problem of being severely limited in terms of their use as materials and processability.
本発明は上述した点を鑑みてなされたものであり、一般
の溶剤に可溶でしかも比較的低融点であり、加工性に優
れた重合性アクリレートモノマーを提供することを目的
とし、具体的には、液晶性を発現する骨格構造を分子中
に導入することによって、その硬化樹脂の力学的、熱的
等の物性において従来の２官能アクリレートモノマーを
凌駕する２官能性アクリレートモノマーを提供すること
を目的としている。The present invention has been made in view of the above-mentioned points, and aims to provide a polymerizable acrylate monomer that is soluble in common solvents, has a relatively low melting point, and has excellent processability. aims to provide a bifunctional acrylate monomer that surpasses conventional bifunctional acrylate monomers in physical properties such as mechanical and thermal properties of the cured resin by introducing a skeleton structure that exhibits liquid crystallinity into the molecule. The purpose is
本発明に係る重合性２官能アクリレートモノマーは、下
記−最大（１）で表されることを特徴としている。The polymerizable bifunctional acrylate monomer according to the present invention is characterized by being represented by the following maximum (1).
・・・・・・（１）
（但し、上式（１）中、Ｒ１は、−Ｈまたは−ＣＨ３で
あり、Ｒ２は、無置換基であるが、エーテル結合、アミ
ド結合、エステル結合またはウレタン結合の少なくとも
１浬を有する炭化水素基であり、ｎ−２〜１１である。......(1) (However, in the above formula (1), R1 is -H or -CH3, and R2 is an unsubstituted group, but may be an ether bond, an amide bond, an ester bond, or a urethane bond. A hydrocarbon group having at least one bond, n-2 to 11.
）
本発明の重合性アクリレートモノマーは、液晶性を付与
することができるメソーゲン基として知られている配向
性の高いビフェニル基を、比較的分子量の低いメチレン
スペーサーを介して（メタ）アクリレートと結合させ、
メチレン基の数によっては液晶性をも有するアクリレー
トモノマーを合成することによって得られる。) The polymerizable acrylate monomer of the present invention combines a highly oriented biphenyl group, known as a mesogenic group that can impart liquid crystallinity, with (meth)acrylate via a methylene spacer with a relatively low molecular weight. ,
It can be obtained by synthesizing an acrylate monomer that also has liquid crystallinity depending on the number of methylene groups.
本発明においては、上記−最大（１）において、Ｒ２は
、好ましくは、下記の基すなわち、−ＣＨ２−ＣＨ（Ｏ
Ｈ）−ＣＨ２−０−１−（ＣＨ２） ｌｌ−ＮＨ−ＣＯ
−０−（ｍ−２〜４）、から選ぶことができる。本発明
においては、Ｒ２の種類に応じて種々の性質を有する重
合体を得ることが可能なモノマーが得られる。In the present invention, in the above-mentioned maximum (1), R2 is preferably the following group, namely -CH2-CH(O
H)-CH2-0-1-(CH2)ll-NH-CO
-0-(m-2 to 4). In the present invention, monomers are obtained that allow polymers having various properties to be obtained depending on the type of R2.
また、本発明の重合性アクリレートモノマーにおいては
、上記−最大（１）中のｎが奇数の場合に、液晶相とし
て安定性に優れたものが得られるという傾向がある。Moreover, in the polymerizable acrylate monomer of the present invention, when n in the above-mentioned maximum (1) is an odd number, there is a tendency that a liquid crystal phase with excellent stability can be obtained.
次に、本発明の重合性アクリレートモノマーの製造方法
について説明する。Next, the method for producing the polymerizable acrylate monomer of the present invention will be explained.
まず、下記式（１）の化合物、
をＮａＯＨ１に２ＣＯ３等の塩基性触媒を用いて、下記
式（２）の化合物
Ｘ−（ＣＨ２） ｎ−０Ｈ
（但し、Ｘ：Ｃ１，Ｂｒ、ＩＳ ｎ：２〜１１）・・・
・・・・・・・・・・・・（２）と反応させて、下記式
（３）を得る。First, a compound of the following formula (1) is mixed with NaOH1 using a basic catalyst such as 2CO3, and a compound of the following formula (2) X-(CH2) n-0H (where X: C1, Br, IS n: 2-11)...
By reacting with (2), the following formula (3) is obtained.
・・・（３）
この化合物＜３）と、たとえば、（メタ）アクリル酸ク
ロライド、（メタ）アクリル酸、グリシジル（メタ）ア
クリレート、イソシアネートエチル（メタ）アクリレー
ト、イソシアネートブチル（メタ）アクリレート、２−
ヒドロキシエチル（メタ）アクリレート／２．４−）ル
イレンジイソシアネート付加体、２−ヒドロキシエチル
（メタ）アクリレート／イソホロンジイソシアネート付
加体などを適当な触媒存在下で反応させることによって
目的とする前記一般式（１）の新規化合物が得られる。...(3) With this compound <3), for example, (meth)acrylic acid chloride, (meth)acrylic acid, glycidyl (meth)acrylate, isocyanate ethyl (meth)acrylate, isocyanate butyl (meth)acrylate, 2-
The desired general formula ( 1) A new compound is obtained.
なお、上記製造方法において、ｎ−４の化合物を得る場
合においては、通常、上記式（２）の化合物の一〇Ｈ基
を常法に従って保護基化したのちに上記式（１）の化合
物と反応させることが、好ましくない環化反応を防止し
収率を向上させる上で好ましい。In addition, in the above production method, when obtaining the compound n-4, the 10H group of the compound of formula (2) above is usually converted into a protective group according to a conventional method, and then the compound of formula (1) is combined with the compound of formula (1) above. It is preferable to carry out the reaction in order to prevent undesirable cyclization reactions and improve the yield.
本発明の重合性２官能アクリレートモノマーは、それ自
体、溶媒溶解性あるいは溶融性にすぐれているので、材
料としての使用に際しては、溶媒に溶かしてコーティン
グした後、あるいは溶融成形した後、放射線、紫外線の
照射あるいは熱エネルギーの印加、あるいは触媒の添加
によって重合架橋が生じ硬化され得る。The polymerizable bifunctional acrylate monomer of the present invention itself has excellent solvent solubility or meltability. Polymerization crosslinking can be caused by irradiation or application of thermal energy, or addition of a catalyst to cure the material.
また、本発明の重合性２官能アクリレートモノマーは、
それ自体、液晶ともなり得るが、他の液晶化合物との相
溶性にもすぐれているので、他の液晶化合物との混合物
としても用いられ得る。この場合、これを所望状態に架
橋させることによって、２次元的ないし３次元的ミクロ
構造を有する液晶構造体を形成することができ、これら
の構造体は耐熱性にすぐれると共に高弾性率、高強度の
構造体となり得る。Moreover, the polymerizable bifunctional acrylate monomer of the present invention is
Although it can be a liquid crystal itself, it also has excellent compatibility with other liquid crystal compounds, so it can also be used as a mixture with other liquid crystal compounds. In this case, by crosslinking this to a desired state, it is possible to form a liquid crystal structure having a two-dimensional or three-dimensional microstructure, and these structures have excellent heat resistance, high elastic modulus, and high It can be a strong structure.
以下、本発明の実施例を示す。 Examples of the present invention will be shown below.
実施例１
ｐ、ｐ’ −ビフェノール１ ｍｏｌ に対してエピク
ロルヒドリン２． １ｍｏｌを、ＮａＯＨ触媒下、エタ
ノール中で、還流しながら２０時間反応させた。Example 1 For 1 mol of p,p'-biphenol, 2. 1 mol was reacted in ethanol under NaOH catalyst for 20 hours at reflux.
反応終了後冷却し、沈澱物を再結晶法によって精製した
。このようにして得られた化合物、ｐ、ｐ’−ジ（ヒド
ロキシエチルオキシ）ビフェノールの同定は、元素分析
、ＩＲＳＮＭＲで行った。収率は５０％であった。After the reaction was completed, the mixture was cooled and the precipitate was purified by recrystallization. The thus obtained compound, p,p'-di(hydroxyethyloxy)biphenol, was identified by elemental analysis and IRSNMR. Yield was 50%.
次いで、得られた上記化合物１ａ＋ｏｌを、トリエチル
アミン触媒下ジメチルホル′ムアミド中５０”Ｃで１時
間、アクリル酸クロライド３ｍｏｌ と反応させた。反
応終了後、蒸溜水を投入し、沈澱物を集めた。この反応
生成物は、カラム（塩化メチレン、シリカゲル）で分離
精製後、さらに再結晶により精製した。このようにして
、目的とする新規化合物、ｐ、ｐ’−ジ（アクリロイル
オキシエチルオキシ）ビフェノールを得ることができた
。この反応の収率は５５％であった。化学構造は下記の
示す通りである。Next, the obtained compound 1a + ol was reacted with 3 mol of acrylic acid chloride in dimethylformamide under a triethylamine catalyst at 50"C for 1 hour. After the reaction was completed, distilled water was added and the precipitate was collected. The reaction product was separated and purified using a column (methylene chloride, silica gel) and further purified by recrystallization. In this way, the desired new compound, p,p'-di(acryloyloxyethyloxy)biphenol, was obtained. The yield of this reaction was 55%.The chemical structure is shown below.
この化合物の同定は、元素分析、ＩＲＳＮ〜ＩＲで行っ
た。そのデータを、それぞれ下記表１、および第１図、
第２図に示す。Identification of this compound was performed by elemental analysis, IRSN-IR. The data are shown in Table 1 below and Figure 1, respectively.
Shown in Figure 2.
衣１（元素分析値）
実測値 理論値
Ｃ６９，３１６９，１０
Ｈ５，９７５，８０
０２４，７２２５，１０
このようにして得られた化合物の特性について調べたと
ころ以下の通りであった。Cloth 1 (elemental analysis values) Actual value Theoretical value C69,3169,10 H5,975,80 024,7225,10 The properties of the compound thus obtained were investigated and found to be as follows.
溶媒溶解性：
極性溶媒に溶解するが、特に塩素系、ケトン系、エーテ
ル系溶剤に溶解する。Solvent solubility: Soluble in polar solvents, especially chlorine-based, ketone-based, and ether-based solvents.
融解性：
前記一般式（１）におけるｎが３以上の場合、１００℃
以下で等方性流体となる。Meltability: 100°C when n in the general formula (1) is 3 or more
The following becomes an isotropic fluid.
架橋特性：
（１）溶媒に溶解した状態ないし溶融状態においては、
５Ｍｒａｄの電子線照射によって架橋反応は完了する。Crosslinking properties: (1) In a state dissolved in a solvent or in a molten state,
The crosslinking reaction is completed by electron beam irradiation at 5 Mrad.
（２）固相状態での架橋反応の場合は、３０Ｍｒａｄま
での電子線照射によって架橋反応は完了する。(2) In the case of a crosslinking reaction in a solid phase state, the crosslinking reaction is completed by electron beam irradiation up to 30 Mrad.
（３）紫外線照射の場合は、触媒としてベンゾメチルケ
タール、ベンゾインアルキルエーテルなどを使用して硬
化させることが可能である。(3) In the case of ultraviolet irradiation, it is possible to cure using benzomethyl ketal, benzoin alkyl ether, etc. as a catalyst.
液晶特性：
前記一般式（１）におけるｎが３以上の場合で、スメク
チック相を示すが、特にｎの値が奇数の場合においては
、液晶特性を示す温度範囲が広く、相転移熱が大きい安
定なスメクチック相を示す。Liquid crystal properties: When n in the general formula (1) is 3 or more, a smectic phase is exhibited, but especially when the value of n is an odd number, the temperature range exhibiting liquid crystal properties is wide and the phase transition heat is large and stable. It shows a smectic phase.
その他ニ
一般的なアクリレートモノマーの架橋剤として使用する
ことが可能である。この場合、架橋手段としては電子線
だけではなく、通常のアクリレートモノマーと同様の重
合性を有している。特に電子線で架橋したものは、ｎが
４以下ではほぼ完全な非品性を示し、Ｔｇ（ガラス転移
温度）は２３０℃以上を示す。また、ｎが５以上では結
晶性を有し、ｎが６までは約２５０℃の融点を示す。It can also be used as a crosslinking agent for other common acrylate monomers. In this case, the crosslinking means is not only electron beams, but also has the same polymerizability as ordinary acrylate monomers. In particular, those crosslinked with electron beams exhibit almost complete quality when n is 4 or less, and exhibit a Tg (glass transition temperature) of 230° C. or higher. Further, when n is 5 or more, it has crystallinity, and when n is up to 6, it exhibits a melting point of about 250°C.
さらに、ｎが７〜１１の場合においても１６０℃以上の
融点を有している。Furthermore, even when n is 7 to 11, it has a melting point of 160°C or higher.
実施例２
実施例１と同様の方法で合成したｐ、ｐ−−ジ（ヒドロ
キシエチルオキシ）ビフェノール１ｍｏｌを５０℃でジ
メチルホルムアミドに溶解し、別途、常法により調製し
た２−ヒドロキシエチルアクリレート／２．４−トルイ
レンジインシアナート付加に２．１ｍｏｌをジブチルチ
ンジラウレートと共に添加した。Example 2 1 mol of p,p-di(hydroxyethyloxy)biphenol synthesized in the same manner as in Example 1 was dissolved in dimethylformamide at 50°C, and 2-hydroxyethyl acrylate/2 prepared separately by a conventional method was added. For the 4-toluylene diine cyanate addition, 2.1 mol was added together with dibutyltin dilaurate.
反応終了後、水を投入し、沈澱物を集めて乾燥した。精
製は、イソプロパツールからの再結晶により行った。こ
れにより、下記に示す化学構造の化合物を得た。収率は
６０％であった。After the reaction was completed, water was added, and the precipitate was collected and dried. Purification was performed by recrystallization from isopropanol. As a result, a compound having the chemical structure shown below was obtained. The yield was 60%.
第１図は、本発明の実施例に係る化合物を同定下ときの
ＩＲスペクトルの吸収曲線、第２図はＮ ！ｖｌ Ｒス
ペクトルの吸収曲線である。FIG. 1 shows the absorption curve of the IR spectrum when identifying the compound according to the example of the present invention, and FIG. 2 shows the absorption curve of N! It is an absorption curve of vl R spectrum.
Claims (1)
重合性２官能アクリレートモノマー。 ▲数式、化学式、表等があります▼ ・・・・・・（ I ） （但し、上式（ I ）中、Ｒ＿１は、−Ｈまたは−ＣＨ
＿３であり、Ｒ＿２は、無置換基であるか、エーテル結
合、アミド結合、エステル結合またはウレタン結合の少
なくとも１種を有する炭化水素基であり、ｎ＝２〜１１
である。） ２、前記一般式（ I ）において、Ｒ＿２が下記の基 すなわち、 −ＣＨ＿２−ＣＨ（ＯＨ）−ＣＨ＿２−Ｏ−、−（ＣＨ
＿２）＿ｍ−ＮＨ−ＣＯ−Ｏ−（ｍ＝２〜４）、▲数式
、化学式、表等があります▼、または ▲数式、化学式、表等があります▼ から選ばれる、請求項１の重合性２官能アクリレートモ
ノマー。[Claims] 1. Characterized by being represented by the following general formula (I),
Polymerizable bifunctional acrylate monomer. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ・・・・・・(I) (However, in the above formula (I), R_1 is -H or -CH
_3, R_2 is an unsubstituted group or a hydrocarbon group having at least one of an ether bond, an amide bond, an ester bond, or a urethane bond, and n = 2 to 11
It is. ) 2. In the general formula (I), R_2 is the following group, namely, -CH_2-CH(OH)-CH_2-O-, -(CH
＿2) ＿m-NH-CO-O- (m=2 to 4), ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, the polymerizability of claim 1 Bifunctional acrylate monomer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9988588A JPH01272551A (en) | 1988-04-22 | 1988-04-22 | Polymerizable bifunctional acrylate monomer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9988588A JPH01272551A (en) | 1988-04-22 | 1988-04-22 | Polymerizable bifunctional acrylate monomer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01272551A true JPH01272551A (en) | 1989-10-31 |
Family
ID=14259239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9988588A Pending JPH01272551A (en) | 1988-04-22 | 1988-04-22 | Polymerizable bifunctional acrylate monomer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01272551A (en) |
Cited By (41)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023539A1 (en) * | 1998-10-20 | 2000-04-27 | Asahi Glass Company Ltd. | Liquid crystal optical element and method for preparing the same |
| JP2003064025A (en) * | 2001-08-24 | 2003-03-05 | Toagosei Co Ltd | Method for manufacturing (meth)acrylate having biphenyl skeleton |
| WO2010143682A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Process for production of light reflection film |
| WO2010143683A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Infrared reflecting plate and infrared reflective bonded glass sheet |
| WO2010143684A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Infrared light reflector, infrared light reflecting laminated glass, and laminated glass and laminate having cholesteric liquid crystal layers |
| EP2362248A2 (en) | 2010-01-27 | 2011-08-31 | Fujifilm Corporation | Infrared light reflecting plate, laminated interlayer film sheet for laminated glass and its production method, and laminated glass |
| WO2012111715A1 (en) | 2011-02-18 | 2012-08-23 | 富士フイルム株式会社 | Infrared reflection plate, interlayer sheet for laminated glass, and laminated glass, and production method therefor |
| WO2012124719A1 (en) | 2011-03-16 | 2012-09-20 | 富士フイルム株式会社 | Polymerizable compound, polymerizable liquid crystal composition, polymeric compound, and film |
| CN102816088A (en) * | 2012-07-06 | 2012-12-12 | 华南理工大学 | Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof |
| WO2013035733A1 (en) | 2011-09-08 | 2013-03-14 | 富士フイルム株式会社 | Polymerizable liquid crystal compound, polymerizable composition, polymer material, and film |
| WO2014045878A1 (en) | 2012-09-18 | 2014-03-27 | 富士フイルム株式会社 | Heat ray cutting film and method for producing same, and laminated glass and heat ray cutting member |
| WO2014061279A1 (en) | 2012-10-19 | 2014-04-24 | 日本化薬株式会社 | Heat-ray-shielding sheet |
| WO2015050203A1 (en) | 2013-10-03 | 2015-04-09 | 富士フイルム株式会社 | Half mirror for displaying projected image, method for producing same, and projected image display system |
| WO2015050256A1 (en) | 2013-10-04 | 2015-04-09 | 富士フイルム株式会社 | Film for thermal compression bonding, which contains cholesteric liquid crystal layer, and application thereof |
| WO2017130683A1 (en) | 2016-01-29 | 2017-08-03 | 富士フイルム株式会社 | Half mirror and mirror with image display function |
| WO2017183428A1 (en) | 2016-04-21 | 2017-10-26 | 富士フイルム株式会社 | Mirror with image display function and half mirror |
| WO2018084076A1 (en) | 2016-11-04 | 2018-05-11 | 富士フイルム株式会社 | Windshield glass, head-up display system, and half-mirror film |
| WO2018146958A1 (en) | 2017-02-09 | 2018-08-16 | 富士フイルム株式会社 | Half mirror, method for producing half mirror, and mirror provided with image display function |
| WO2018198559A1 (en) | 2017-04-28 | 2018-11-01 | 富士フイルム株式会社 | Image display function-equipped anti-glare mirror |
| WO2019009252A1 (en) | 2017-07-04 | 2019-01-10 | 富士フイルム株式会社 | Half mirror |
| WO2019050019A1 (en) | 2017-09-07 | 2019-03-14 | 富士フイルム株式会社 | One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system |
| US10386569B2 (en) | 2015-02-10 | 2019-08-20 | Fujifilm Corporation | Optical member, optical element, liquid crystal display device, and near-to-eye optical member |
| WO2019163969A1 (en) | 2018-02-23 | 2019-08-29 | 富士フイルム株式会社 | Method for manufacturing laminated glass for displaying image, laminated glass for displaying image, and image display system |
| WO2019188846A1 (en) | 2018-03-29 | 2019-10-03 | 富士フイルム株式会社 | Image-forming method |
| WO2020008961A1 (en) | 2018-07-02 | 2020-01-09 | 富士フイルム株式会社 | Decorative film, decoration method, decorative molded body production method, and decorative molded film |
| WO2020080355A1 (en) | 2018-10-17 | 2020-04-23 | 富士フイルム株式会社 | Projection image display member, windshield glass, and head-up display system |
| WO2020122023A1 (en) | 2018-12-10 | 2020-06-18 | 富士フイルム株式会社 | Projection image displaying member, windshield glass, and head-up display system |
| WO2020179787A1 (en) | 2019-03-06 | 2020-09-10 | 富士フイルム株式会社 | Laminated film for displaying projection image, laminated glass for displaying projection image, and image display system |
| WO2020194831A1 (en) | 2019-03-28 | 2020-10-01 | 富士フイルム株式会社 | Ink set for inkjet recording, and image recording method |
| US10816709B2 (en) | 2014-12-19 | 2020-10-27 | Nippon Kayaku Kabushiki Kaisha | Light reflection film and laminate having the light reflection film |
| WO2020262474A1 (en) | 2019-06-27 | 2020-12-30 | 富士フイルム株式会社 | Decorative film for molding, molded article, and display |
| WO2021060402A1 (en) | 2019-09-27 | 2021-04-01 | 富士フイルム株式会社 | Projector for head-up display |
| WO2021059879A1 (en) | 2019-09-27 | 2021-04-01 | 富士フイルム株式会社 | Image recording method |
| WO2021200655A1 (en) | 2020-03-30 | 2021-10-07 | 富士フイルム株式会社 | Reflective film, windshield glass, and head-up display system |
| WO2021246402A1 (en) | 2020-06-03 | 2021-12-09 | 富士フイルム株式会社 | Reflective film, laminated glass production method, and laminated glass |
| WO2022075184A1 (en) | 2020-10-09 | 2022-04-14 | 富士フイルム株式会社 | Reflective film, windshield glass, and head-up display system |
| WO2022123946A1 (en) | 2020-12-09 | 2022-06-16 | 富士フイルム株式会社 | Reflection film, windshield glass, and head-up display system |
| WO2022138142A1 (en) | 2020-12-25 | 2022-06-30 | 富士フイルム株式会社 | Image recording method and ink jet recorded matter |
| WO2023054324A1 (en) | 2021-09-30 | 2023-04-06 | 富士フイルム株式会社 | Head-up display system and transport |
| WO2023080115A1 (en) | 2021-11-05 | 2023-05-11 | 富士フイルム株式会社 | Virtual image display device, head-up display system, and transport machine |
| WO2023085370A1 (en) | 2021-11-12 | 2023-05-19 | 富士フイルム株式会社 | Image recorded object and image recording method |
-
1988
- 1988-04-22 JP JP9988588A patent/JPH01272551A/en active Pending
Cited By (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000023539A1 (en) * | 1998-10-20 | 2000-04-27 | Asahi Glass Company Ltd. | Liquid crystal optical element and method for preparing the same |
| US6723393B1 (en) | 1998-10-20 | 2004-04-20 | Asahi Glass Company, Limited | Liquid crystal optical element and method for preparing the same |
| US7011870B2 (en) | 1998-10-20 | 2006-03-14 | Asahi Glass Company, Limited | Liquid crystal optical element and method for its production |
| EP1690918A2 (en) | 1998-10-20 | 2006-08-16 | Asahi Glass Company Ltd. | Liquid crystal optical element and method for its production |
| EP1690918A3 (en) * | 1998-10-20 | 2006-11-08 | Asahi Glass Company Ltd. | Liquid crystal optical element and method for its production |
| JP2003064025A (en) * | 2001-08-24 | 2003-03-05 | Toagosei Co Ltd | Method for manufacturing (meth)acrylate having biphenyl skeleton |
| WO2010143684A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Infrared light reflector, infrared light reflecting laminated glass, and laminated glass and laminate having cholesteric liquid crystal layers |
| WO2010143683A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Infrared reflecting plate and infrared reflective bonded glass sheet |
| WO2010143682A1 (en) | 2009-06-11 | 2010-12-16 | 富士フイルム株式会社 | Process for production of light reflection film |
| EP2362248A2 (en) | 2010-01-27 | 2011-08-31 | Fujifilm Corporation | Infrared light reflecting plate, laminated interlayer film sheet for laminated glass and its production method, and laminated glass |
| WO2012111715A1 (en) | 2011-02-18 | 2012-08-23 | 富士フイルム株式会社 | Infrared reflection plate, interlayer sheet for laminated glass, and laminated glass, and production method therefor |
| WO2012124719A1 (en) | 2011-03-16 | 2012-09-20 | 富士フイルム株式会社 | Polymerizable compound, polymerizable liquid crystal composition, polymeric compound, and film |
| WO2013035733A1 (en) | 2011-09-08 | 2013-03-14 | 富士フイルム株式会社 | Polymerizable liquid crystal compound, polymerizable composition, polymer material, and film |
| CN102816088A (en) * | 2012-07-06 | 2012-12-12 | 华南理工大学 | Tertiary amine structure containing methacrylate macromonomer without bisphenol A structure, preparation method and application thereof |
| WO2014045878A1 (en) | 2012-09-18 | 2014-03-27 | 富士フイルム株式会社 | Heat ray cutting film and method for producing same, and laminated glass and heat ray cutting member |
| WO2014061279A1 (en) | 2012-10-19 | 2014-04-24 | 日本化薬株式会社 | Heat-ray-shielding sheet |
| WO2015050203A1 (en) | 2013-10-03 | 2015-04-09 | 富士フイルム株式会社 | Half mirror for displaying projected image, method for producing same, and projected image display system |
| WO2015050256A1 (en) | 2013-10-04 | 2015-04-09 | 富士フイルム株式会社 | Film for thermal compression bonding, which contains cholesteric liquid crystal layer, and application thereof |
| US10816709B2 (en) | 2014-12-19 | 2020-10-27 | Nippon Kayaku Kabushiki Kaisha | Light reflection film and laminate having the light reflection film |
| US10386569B2 (en) | 2015-02-10 | 2019-08-20 | Fujifilm Corporation | Optical member, optical element, liquid crystal display device, and near-to-eye optical member |
| WO2017130683A1 (en) | 2016-01-29 | 2017-08-03 | 富士フイルム株式会社 | Half mirror and mirror with image display function |
| WO2017183428A1 (en) | 2016-04-21 | 2017-10-26 | 富士フイルム株式会社 | Mirror with image display function and half mirror |
| WO2018084076A1 (en) | 2016-11-04 | 2018-05-11 | 富士フイルム株式会社 | Windshield glass, head-up display system, and half-mirror film |
| WO2018146958A1 (en) | 2017-02-09 | 2018-08-16 | 富士フイルム株式会社 | Half mirror, method for producing half mirror, and mirror provided with image display function |
| WO2018198559A1 (en) | 2017-04-28 | 2018-11-01 | 富士フイルム株式会社 | Image display function-equipped anti-glare mirror |
| WO2019009252A1 (en) | 2017-07-04 | 2019-01-10 | 富士フイルム株式会社 | Half mirror |
| WO2019050019A1 (en) | 2017-09-07 | 2019-03-14 | 富士フイルム株式会社 | One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system |
| EP4312066A2 (en) | 2017-09-07 | 2024-01-31 | FUJIFILM Corporation | One-way mirror film for displaying projected images, laminated glass for displaying projected images, and image display system |
| WO2019163969A1 (en) | 2018-02-23 | 2019-08-29 | 富士フイルム株式会社 | Method for manufacturing laminated glass for displaying image, laminated glass for displaying image, and image display system |
| WO2019188846A1 (en) | 2018-03-29 | 2019-10-03 | 富士フイルム株式会社 | Image-forming method |
| WO2020008961A1 (en) | 2018-07-02 | 2020-01-09 | 富士フイルム株式会社 | Decorative film, decoration method, decorative molded body production method, and decorative molded film |
| WO2020080355A1 (en) | 2018-10-17 | 2020-04-23 | 富士フイルム株式会社 | Projection image display member, windshield glass, and head-up display system |
| WO2020122023A1 (en) | 2018-12-10 | 2020-06-18 | 富士フイルム株式会社 | Projection image displaying member, windshield glass, and head-up display system |
| WO2020179787A1 (en) | 2019-03-06 | 2020-09-10 | 富士フイルム株式会社 | Laminated film for displaying projection image, laminated glass for displaying projection image, and image display system |
| WO2020194831A1 (en) | 2019-03-28 | 2020-10-01 | 富士フイルム株式会社 | Ink set for inkjet recording, and image recording method |
| WO2020262474A1 (en) | 2019-06-27 | 2020-12-30 | 富士フイルム株式会社 | Decorative film for molding, molded article, and display |
| WO2021060402A1 (en) | 2019-09-27 | 2021-04-01 | 富士フイルム株式会社 | Projector for head-up display |
| WO2021059879A1 (en) | 2019-09-27 | 2021-04-01 | 富士フイルム株式会社 | Image recording method |
| WO2021200655A1 (en) | 2020-03-30 | 2021-10-07 | 富士フイルム株式会社 | Reflective film, windshield glass, and head-up display system |
| WO2021246402A1 (en) | 2020-06-03 | 2021-12-09 | 富士フイルム株式会社 | Reflective film, laminated glass production method, and laminated glass |
| WO2022075184A1 (en) | 2020-10-09 | 2022-04-14 | 富士フイルム株式会社 | Reflective film, windshield glass, and head-up display system |
| WO2022123946A1 (en) | 2020-12-09 | 2022-06-16 | 富士フイルム株式会社 | Reflection film, windshield glass, and head-up display system |
| WO2022138142A1 (en) | 2020-12-25 | 2022-06-30 | 富士フイルム株式会社 | Image recording method and ink jet recorded matter |
| WO2023054324A1 (en) | 2021-09-30 | 2023-04-06 | 富士フイルム株式会社 | Head-up display system and transport |
| WO2023080115A1 (en) | 2021-11-05 | 2023-05-11 | 富士フイルム株式会社 | Virtual image display device, head-up display system, and transport machine |
| WO2023085370A1 (en) | 2021-11-12 | 2023-05-19 | 富士フイルム株式会社 | Image recorded object and image recording method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH01272551A (en) | Polymerizable bifunctional acrylate monomer | |
| KR100413871B1 (en) | Polymerizable liquid crystal compound | |
| US4647648A (en) | Polyhydroxyethers from hydroxybiphenyls | |
| EP0521453B1 (en) | Polymeric vehicle for coatings | |
| EP1944287A1 (en) | Polymerizable liquid crystal compounds having fused rings and homo- or co-polymers of the same | |
| JPWO2008105538A1 (en) | Polymerizable liquid crystal compound, polymerizable liquid crystal composition, liquid crystal polymer and optical anisotropic body | |
| CA1107293A (en) | Halogenated bis-acrylates and bis-methacrylates | |
| US5426234A (en) | Phenylethynyl terminated reactive oligomer | |
| Andersson et al. | Preparation of ordered, crosslinked and thermally stable liquid crystalline poly (vinyl ether) films | |
| KR20100086922A (en) | Polymerizable biphenyl compound | |
| US5078910A (en) | Polimerization of liquid crystalline monomers | |
| EP0617110A1 (en) | Liquid crystal monomer compound and polymer obtained therefrom | |
| US4400519A (en) | Benzil ketal derivatives | |
| Jonsson et al. | Molecular engineering of liquid crystal polymers by living polymerization: 4. Synthesis and cationic polymerization of some mesogenic vinyl ethers containing various functional groups | |
| JP2000191640A (en) | Bismaleimide containing mesogenic group | |
| Mormann et al. | Synthesis and mesogenic properties of diaromatic cyanates and isocyanates-monomers for liquid crystalline thermosets | |
| JP4010583B2 (en) | Monofunctional polymerizable compound and liquid crystalline polymer comprising the polymer | |
| JPH01271402A (en) | Material curable with energetic radiation | |
| JPH05170860A (en) | High-molecular liquid-crystal polyurethane and its manufacture | |
| JPS63277208A (en) | Side chain liquid crystal polymer derived from 1-(phenyl)-2-(4-cyanophenyl)ethane | |
| US5171765A (en) | Water dispersible polymers for coatings based on polymers containing mesogenic groups | |
| JP3073256B2 (en) | Polymer liquid crystal polyurethane | |
| JPH07258202A (en) | Polymerizable betaine compound | |
| JPH0354204A (en) | Radiation-polymerizable liquid crystalline monomer and polymer thereof | |
| JP2772960B2 (en) | Polymer liquid crystal material |