JPH0439008A - Manufacture of organic foam glass molded product - Google Patents
Manufacture of organic foam glass molded productInfo
- Publication number
- JPH0439008A JPH0439008A JP14652290A JP14652290A JPH0439008A JP H0439008 A JPH0439008 A JP H0439008A JP 14652290 A JP14652290 A JP 14652290A JP 14652290 A JP14652290 A JP 14652290A JP H0439008 A JPH0439008 A JP H0439008A
- Authority
- JP
- Japan
- Prior art keywords
- beads
- organic glass
- mold
- monomer
- mixture
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 239000011494 foam glass Substances 0.000 title abstract 3
- 239000011521 glass Substances 0.000 claims abstract description 44
- 239000011324 bead Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- 230000001413 cellular effect Effects 0.000 claims description 11
- 239000000463 material Substances 0.000 abstract description 34
- 238000005266 casting Methods 0.000 abstract description 27
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 239000000654 additive Substances 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 abstract description 2
- 230000008961 swelling Effects 0.000 abstract 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000006116 polymerization reaction Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- 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 3
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000009415 formwork Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- -1 prepolymer Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000007527 glass casting Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
［産業上の利用分野コ
本発明は、各種光散乱材料乃至光反射材料として有用な
均一な気泡入り有機ガラス板の製造法に関する。
［従来の技術］
（１）背景
ポリメチルメタクリレートは、優れた光線透過性及び耐
候性を有するところから、開発以来６０年を経た今日で
も、装飾材、電灯のシェード、看板、水槽、透光性屋根
材等の産業材料から、コンタクトレンズ、人口水晶体な
どの医療用用途に到るまで極めて広く利用されている。
特に、本材料の端面から光線を入射させることにより光
路中の障害物（例えば気泡、孔、渭、窪み等）の形状に
応じて発光させようとするエツジライティングの技法は
、今後の発展が期待される重要な用途の一つである。
■ 従来技術の問題点
そこで本材料の内部に小気泡を含有させる技術が工夫さ
れ、
■ 例えば特公昭５２−１６１４８号公報に見られる如
く、アクリル樹脂板に対し適当量の水分を吸収させた後
、加熱して発泡させる方法。
■ 重合用材料（有機ガラスのモノマー若しくはプレポ
リマー又はそれらの混合物）中に空気を吹き込みつつ重
合させる方法。
■ 重合反応を促進させることにより、気化したモノマ
ーによる発泡を利用する方法。
■ 重合用材料中に発泡剤を添加する方法。
などが提案されている。
しかし■の方法によると、得られた発泡シートの表面が
加熱時に発生した泡により凹凸化して表面平滑性が失わ
れるのみでなく、発生した泡の内壁も不平滑で光沢に乏
しいので、エツジライティング用には利用できない ま
な■の方法によると、気泡が浮上するため、均一な気泡
入り板材が得られない。更に■の方法によっても気泡の
形成状態には均一性がなく、気泡の形状、大きさ、位置
がバラバラである。最後の■の方法でも成績は略々■と
同じである。
以上総しるに、公知のどの方法によっても、エツジライ
ティング用に利用できる程の均斉な気泡入り有機ガラス
板を得るのは困難である。
［発明が解決しようとする課題］
そこで本発明が解決を意図する課題は、エツジライティ
ング用、シェード、固型照明材料などとして利用するこ
とができる均整なく密度、大きさ、形状等の略々均しい
）気泡入り有機ガラス板を取得するための新規な手段を
開発することである。[Industrial Field of Application] The present invention relates to a method for producing a uniform cellular organic glass plate useful as various light-scattering materials or light-reflecting materials. [Prior art] (1) Background Polymethyl methacrylate has excellent light transmittance and weather resistance, and even today, 60 years after its development, polymethyl methacrylate is still used in decorative materials, lampshades, signboards, aquariums, and translucent materials. It is extremely widely used in everything from industrial materials such as roofing materials to medical applications such as contact lenses and artificial lenses. In particular, the edge lighting technique, which attempts to emit light according to the shape of obstacles in the optical path (e.g. bubbles, pores, ridges, depressions, etc.) by injecting light rays from the edge of this material, is expected to develop in the future. This is one of the important uses. ■ Problems with the conventional technology Therefore, a technique was devised to contain small air bubbles inside this material. , a method of heating and foaming. (2) A method of polymerizing while blowing air into the polymerization material (organic glass monomer, prepolymer, or mixture thereof). ■ A method that utilizes foaming caused by vaporized monomer by accelerating the polymerization reaction. ■ Adding a blowing agent to the material for polymerization. etc. have been proposed. However, according to the method (■), the surface of the obtained foam sheet becomes uneven due to the bubbles generated during heating, and the surface smoothness is not only lost, but also the inner wall of the generated bubbles is uneven and lacks gloss, so Edge Lighting According to Mana's method, the air bubbles float to the surface, making it impossible to obtain a uniform air-filled board. Furthermore, even with the method (2), there is no uniformity in the formation of bubbles, and the shapes, sizes, and positions of the bubbles vary. Even with the last method ■, the results are almost the same as ■. In summary, by any of the known methods, it is difficult to obtain a homogeneous organic glass plate with bubbles that can be used for edge lighting. [Problems to be Solved by the Invention] Therefore, the problem to be solved by the present invention is to provide materials that are not uniform and have approximately uniform density, size, shape, etc., and can be used as edge lighting, shades, solid lighting materials, etc. new) to develop a new means to obtain aerated organic glass plates.
（１）概念
従来、透明な有機ガラス成形品を得ようとするとき、注
型用原料を増粘させると共に、重合収縮によるヒゲを小
さくする目的で、原料モノマー、プレポリマー又はそれ
らの混合物中に相当する有機ガラスビーズを添加するの
は慣用の成形技術であるが、この場合は注型成形品中に
不規則に気泡が発生するのを防止するため、面圧８ｋｇ
／ｃｎｆ以上に加圧するのが常識であって、故意に気泡
を形成させる目的で加圧程度を低めるという発想は全く
顧みられたことはなかった。
しかるに、上の公知注型成形時の加圧を廃止して略々常
圧条件下に重合させると、意外なことに、殆ど均整な気
泡入り有機ガラス成形品が得られ、この気泡入り成形品
は、エツジライティング用、シェード用、固型照明材料
等として好適に利用できるものであることが知られた。
＋２１ 概要
本発明は、以上の知見に基づくもので、その要旨は、空
気連行剤として有機ガラスのビーズを添加した有機ガラ
スモノマー若しくはプレポリマー又はそれらの混合物を
略々常圧下に型内で重合させることを特徴とする気泡入
り有機ガラス板の製造法に存する。以下、発明の構成に
関連する事項につき項分けして説明する。
（３）有機ガラス成形用注型材料
本発明において、有機ガラス成形用の注型成形用材料と
しては、メチルメタクリレート、メチルメタクリレート
・スチレンコポリマー又はスチレン等の透明なポリマー
を与えるビニル系モノマー、プレポリマー又はそれらの
混合物が、単独で又は併用して使用される。しかし成形
品の透明度及び耐候性を考慮すれば、メチルメタクリレ
ートのモノマー、プレポリマー又はそれらの混合物の採
択が望ましい。モノマーとプレポリマーとの混合物に適
当な重合開始剤（例えばＡＩＢＮ等）及び要すればその
他の助剤を混合したものは俗に“シロップ”と呼ばれ、
最も一般的に利用される。
本発明では、上の注型用材料は、必須的に相当する有機
ガラス（ポリマー）のビーズを含む８ここにモノマー、
プレポリマー又はそれらの混合物（以下「注型用樹脂」
と総称する）に対するビーズの混合比率（重量比）は、
７０：３０〜２０ ＋ ８０、好埜しくは６０二４０〜
２５：７５である６ビーズの量が上記下限値より少ない
と、常圧下に重合させても殆ど透明な成形品が得られ、
逆にビーズ量が上限値より増えると、ビーズと注型用樹
脂との混合物の流動性が失われ、注型が困難となる。
なお、ここに使用するビーズは、成るべく真球形のもの
が望ましい、制御された重合条件下に製造された有機ガ
ラス粒子は、顕微鏡下における測長基準となるほどの形
状及び大きさの整った球状を呈するので、本発明の目的
上最適である。
Ｇ４１ 成形法
本発明による成形品は、所定の形状を有する型内で、有
機ガラスビーズを含む、相当する注型用樹脂及び重合触
媒を主とする液状材料を重合、硬化させることにより得
られる。従って、具体的に以下のような製法の類型があ
る。
（ａ）有機ガラスビーズと、予め触媒等の添加剤を配合
した注型用樹脂の脱気物とを混合しながら注型用型内に
仕込み、外部から加熱して該ビーズの溶解及び膨潤を促
進しつつ重合させる方法。
（ｂ）予め触媒等の添加剤を配合した注型用樹脂の脱気
物を注型用型内に仕込んだ後、ビーズを型内へ充填し、
以下（ａ）と同様に硬化させる方法。
（ｃ）予めビーズを低温状態に保たれた型内に充填し、
該型内を減圧に保ちながら低温下に冷モノマーを注入し
、以後（ａ）と同様に硬化させる方法。
本発明では、目的とする成形品の気泡的な均整度、内包
される気泡の大きさ及び密度並びに成形品の厚さなどに
応じて以上の各方法を適宜採択できる。
（ａ）の方法によれば、モノマーに対するビーズの混合
比を自由に変化させることができるのみならず、成形品
中の気泡分布を略々均一化することができる。これに反
し、型枠内の注型材料に対しビーズを、又はビーズに対
し注型材料を夫々添加する（ｂ）又は゛（ｃ）の方法で
は、ビーズと注型材料（殊にモノマー）との比重差のた
め、気泡分布の均一な成形品を得るのが多少困難である
。但しくｂ）の方法でもビーズの充填率を上記好適比の
上限である７５％付近に迄高めると、成形品中の気泡分
布を殆ど均斉化することができる。更に（ｃ）の方法に
よると、ビーズの充填量比を６２．５％程度にまでする
ことができるが、ビーズの項中にゲル化が起こり易いの
で、１０ｃｍ角程度０比較的小型の気泡入り成形品の製
造には適するが、より大型の成形品を得る目的には適し
ない。
従って、実用上最も汎用性があると思われるのは、（ａ
）の有機ガラスビーズと、予め触媒等の添加剤を配合し
た注型用樹脂の脱気物とを混合しながら注型用型内に仕
込む方法である。なお、この（ａ）方法に限らず、注型
材料とビーズとの混合物のゲル化を回避するため、重合
系設定時の温度（仕込み温度）は可及的低温であるのが
好ましい。
注型用型としては、板状成形品を得る目的には二枚の磨
きガラス板をポリ塩化ビニル等の柔軟なガスケットを介
して並列させた「セル」が広く利用される。しかし弧状
、円筒状、角筒状その他の異形成形品を得る目的には、
相当する型を準備しておく必要がある。但し、本発明に
係る気泡入り有機ガラス成形品の主たる使用形態は種々
の輪郭を持つ板状であるから、セルを用いて板状に成形
したものが汎用性において最も高い。
気泡径は０．１〜２．０′″／、φの範囲内にあるのが
好適であるが、一般に、成形時の圧力が高くなる程、生
成する気泡径が小さくなり、かつ使用した有機ガラスビ
ーズの粒径が大きくなる程、生成する気泡の径が大とな
ると共に、気泡数が減少する。また注型材料中のプレポ
リマー及びポリマー（有機ガラス粒子由来）の濃度が高
くなればなる程、気泡の径が小となる。さらに、重合温
度が高くなるにつれ気泡数が多くなる傾向がある。それ
故、実際の気泡入り有機ガラス成形品の製造に際しては
、目的に応じて使用有機ガラスビーズの粒径、添加量（
注型用材料との配合比）、反応温度等の諸条件を管理し
ながら行うのが好ましい。特に、成形時の圧力は気泡径
に重要な影響を及ぼすので、略々常圧下に行われるのが
好適である。
＋５１ 用途
本発明による気泡入り有機ガラス成形品は、内部の気泡
が入射光を反射する性質を有するから、光反射材料とし
て有用であって、例えば面型照明材料、非透視性窓材、
電灯用シェード、エツジライティング用形象表示材等の
用途に広く利用されることができる。例えば、比較的気
泡密度の低い気泡入り有機ガラス板材の端面から光を入
射させると、入射光が板材と直角の方向へ反射される結
果、板材の全面が発光するから、トレース、レントゲン
フィルムの観察などの目的に好適な固型照明材料となる
（なおこの際、本板材の他面は鏡により光の損失を抑え
ておくのが好ましい。
また、上記気泡入り有機ガラス板材を適宜の形状に切り
抜いものを表示すべき文字、図形、模様、記号などの形
象に応じてセル内に配置したのち、注型材料を流し込ん
で硬化させると、気泡部分が文字、図形等に応じて偏在
するエツジライティング用の有機ガラス板が得られる。
なお、この場合適宜の形状に切り抜かれた該気泡入り板
材を埋設する代わりに透明な無機又は有機ガラス板の表
面に貼着しても殆ど同じ効果が得られるから、埋設に比
し生産性を著増させることができる。
［作用コ
本発明の方法で使用される有機ガラスビーズは、粒子自
体微量の空気を溶存する他、その表面に存在する微細な
りラックやボイドにも多少の空気が付着又は吸着されて
いる。従って、該ビーズが注型用材料中へ添加されると
、その溶解や膨潤に伴って該同伴空気が気泡の核となり
、次第に大きな気泡に成長する０周知の有機ガラス注型
成形技術でも、ビーズの添加により同様の現象が起こっ
ていると考えられるが、この場合は気泡の発生を極力抑
制するため必須的に加圧が行われており、この点、硬化
を意図的に常圧下に行って気泡の生成を抑制しない本発
明とは技術思想を異にする。
適当な条件が選択される限り、生成した気泡の大きさ及
び分布密度は殆ど一定であって、しかも気泡の内壁は平
滑である。その結果、入射光の反射が平均的に起こるの
で、エツジライティングによる照度が一定であると共に
、優れた表示乃至装飾効果が得られる。
「実施ｇＡｌｌ
以下、実施例により発明実施の態様を説明するが、例示
は単に説明用のもので、発明思想の制限又は限定を意味
するものではない。
実施例１（方法（ａ））
メチルメタクリレート（ＭＭＡ）モノマー１００重量部
（以下同様）に重合開始剤（ＡＩＢＮ）等０．１部を混
合した後、約３０ｍｍＨｇに吸引、脱気した。この触媒
添加モノマーに、平均粒径２７０μｍ粒状のポリメチル
メタクリレート（ＰＭＭＡ）（住人化学工業■製（スミ
ペックス’ ＢＭＨ＞ 。
以下同様）６０部を混合し、開放系内で攪拌した。
攪拌につれ樹脂粒子は次第に溶解し、見掛は上粘稠なス
ラリー状となった。
別に、予め洗浄、乾燥させた二枚の磨きガラス板を内径
５■の間隙を隔てて並立させ、周囲をポリ塩化ビニル製
ガスケットで閉塞した型枠を用意し、該型枠内に上記ス
ラリーを流し込んだ後、注入口を封止後、恒温槽中で５
５〜６０℃で重合させた後、１２０℃の恒温槽中で熱処
理して重合を完結させた。
得られた重合物を徐々に４０℃まで徐冷してアニールし
た後、型枠を分解して硬化した気泡入り有機ガラス板（
粗発明製品）を取り出し、周縁部をカット後、切断端面
を水冷しながら研磨することにより、目的の気泡入り有
機ガラス板を得た。
この製品には、平均径約ＩＩＩＩφの気泡が均一に分布
しており、そのまま固型照明材料、シェード、非透視性
窓材として、またこれをレーザーカッターを用いて切り
抜くことにより、エツジライティング用装飾板又は表示
板における文字、記号、図形などの形象材として利用で
きる。
実施例２（方法（ｂ））
実施例１と同様の型枠内へ、メチルメタクリレート（Ｍ
ＭＡ）モノマー１００部にＡ Ｉ Ｂ Ｎ ０．１部及
び他の添加剤を添加し、攪拌混合して溶解させた後、脱
気した注型材料を仕込み、型枠の上部開放端から実施例
１で用いたＰＭＭＡビーズを連続的に流し込み、型枠の
高さの９５％まで充填した後、型枠の開放端を封止した
。
次いで、型枠を５５〜６０℃に調温された恒温槽内で予
備重合させた後、１２０℃の熱風循環式オーブン内にて
重合を完結させ、その後、徐々に４０℃まで冷却してア
ニールした。
その後、型を解体して成形物を取り出し、周縁部を常法
通りカットすることにより、目的の気泡入り有機ガラス
板を得た。
実施例３（方法（Ｃ））
実施例１と同様の型枠内へ実施例１で使用したビーズを
均一に充填した後、開口部を封止した。
次いで、上方のガスケットに小孔を穿ち、この孔に脱気
用ノズルを挿入して脱気後、該ノズルを通して冷いＭＭ
Ａモノマー（ＡＩＢＮ等の添加剤を混合済み）を注入し
、孔を封止後、以下前例と同様に重合させることにより
、所望の気泡入り有機ガラス板を得た。(1) Concept Conventionally, when trying to obtain a transparent organic glass molded product, in order to thicken the raw material for casting and reduce whiskers caused by polymerization shrinkage, the raw material monomer, prepolymer, or a mixture thereof was added to Adding the corresponding organic glass beads is a conventional molding technique, but in this case, a surface pressure of 8 kg was applied to prevent bubbles from forming irregularly in the cast molded product.
It is common knowledge to pressurize to a level higher than /cnf, and the idea of lowering the pressure to intentionally form bubbles has never been considered. However, when the pressure applied during the above-mentioned known cast molding is abolished and the polymerization is carried out under conditions of approximately normal pressure, an organic glass molded article containing almost uniform cells is surprisingly obtained. It has been found that these can be suitably used for edge lighting, shades, solid lighting materials, etc. +21 Overview The present invention is based on the above findings, and the gist thereof is to polymerize an organic glass monomer or prepolymer or a mixture thereof to which organic glass beads are added as an air entraining agent in a mold under approximately normal pressure. The present invention relates to a method for manufacturing a bubble-filled organic glass plate. Hereinafter, matters related to the structure of the invention will be explained in sections. (3) Casting material for molding organic glass In the present invention, the casting material for molding organic glass includes a vinyl monomer or prepolymer that provides a transparent polymer such as methyl methacrylate, methyl methacrylate/styrene copolymer, or styrene. or mixtures thereof are used alone or in combination. However, in consideration of the transparency and weather resistance of the molded article, it is desirable to use a methyl methacrylate monomer, a prepolymer, or a mixture thereof. A mixture of monomer and prepolymer mixed with a suitable polymerization initiator (for example, AIBN, etc.) and other auxiliary agents if necessary is commonly called "syrup".
Most commonly used. In the present invention, the above casting material essentially contains beads of the corresponding organic glass (polymer) 8 in which the monomer,
Prepolymers or mixtures thereof (hereinafter referred to as "casting resins")
The mixing ratio (weight ratio) of beads to
70:30~20+80, preferably 60240~
When the amount of 6 beads with a ratio of 25:75 is less than the above lower limit, an almost transparent molded product can be obtained even if polymerized under normal pressure.
Conversely, when the amount of beads increases beyond the upper limit, the mixture of beads and casting resin loses its fluidity, making casting difficult. The beads used here are preferably perfectly spherical.The organic glass particles produced under controlled polymerization conditions have a spherical shape and size that can be used as a length measurement standard under a microscope. Therefore, it is optimal for the purpose of the present invention. G41 Molding method The molded article according to the present invention is obtained by polymerizing and curing a liquid material containing organic glass beads, a corresponding casting resin, and a polymerization catalyst as main components, in a mold having a predetermined shape. Therefore, there are concrete types of manufacturing methods as follows. (a) Organic glass beads and degassed casting resin mixed with additives such as catalysts are mixed and charged into a casting mold, and heated from the outside to dissolve and swell the beads. A method of accelerating polymerization. (b) After charging the degassed material of the casting resin mixed with additives such as a catalyst in advance into the casting mold, filling the beads with the mold,
A method of curing in the same manner as in (a) below. (c) Fill beads in advance into a mold kept at a low temperature,
A method in which a cold monomer is injected at a low temperature while keeping the inside of the mold under reduced pressure, and then cured in the same manner as in (a). In the present invention, each of the above methods can be appropriately adopted depending on the degree of cellular symmetry of the target molded product, the size and density of the bubbles included, the thickness of the molded product, and the like. According to method (a), not only can the mixing ratio of beads to monomer be changed freely, but also the bubble distribution in the molded article can be made substantially uniform. On the other hand, in the method (b) or (c), in which the beads are added to the casting material in the mold, or the casting material is added to the beads, the beads and the casting material (especially monomer) are added. Due to the difference in specific gravity, it is somewhat difficult to obtain a molded product with a uniform bubble distribution. However, even with method b), if the bead filling rate is increased to around 75%, which is the upper limit of the preferred ratio, the air bubble distribution in the molded article can be made almost uniform. Furthermore, according to the method (c), the filling ratio of beads can be increased to about 62.5%, but since gelation tends to occur in the beads, relatively small air bubbles of about 10 cm square are used. Although it is suitable for producing molded products, it is not suitable for obtaining larger molded products. Therefore, the one that seems to have the most practical versatility is (a
This is a method in which the organic glass beads () and the degassed product of a casting resin that has been mixed with additives such as a catalyst are mixed and charged into a casting mold. In addition, in order to avoid not only this method (a) but also gelation of the mixture of casting material and beads, it is preferable that the temperature at the time of setting the polymerization system (preparation temperature) is as low as possible. As a casting mold, a "cell" in which two polished glass plates are placed side by side with a flexible gasket such as polyvinyl chloride interposed therebetween is widely used to obtain a plate-shaped molded product. However, for the purpose of obtaining arcuate, cylindrical, rectangular, and other irregularly shaped products,
It is necessary to prepare a corresponding mold. However, since the cellular organic glass molded product according to the present invention is mainly used in the form of a plate having various contours, a product molded into a plate shape using cells has the highest versatility. It is preferable that the bubble diameter is within the range of 0.1 to 2.0''/φ, but in general, the higher the pressure during molding, the smaller the produced bubble diameter, and As the particle size of the glass beads increases, the diameter of the bubbles that are generated increases and the number of bubbles decreases.Also, the higher the concentration of prepolymer and polymer (derived from organic glass particles) in the casting material. As the polymerization temperature increases, the diameter of the bubbles becomes smaller.Furthermore, as the polymerization temperature increases, the number of bubbles tends to increase.Therefore, when actually manufacturing a cellular organic glass molded product, the organic glass used should be selected depending on the purpose. Bead particle size, amount added (
It is preferable to carry out the reaction while controlling conditions such as the mixing ratio with the casting material and the reaction temperature. In particular, since the pressure during molding has an important effect on the cell diameter, it is preferable to perform the molding under approximately normal pressure. +51 Applications The bubble-containing organic glass molded article according to the present invention has the property of reflecting incident light due to the bubbles inside, and is therefore useful as a light-reflecting material, such as surface lighting materials, non-transparent window materials,
It can be widely used as shades for electric lights, visual display materials for edge lighting, etc. For example, when light is incident from the end face of a cellular organic glass plate with a relatively low bubble density, the incident light is reflected in a direction perpendicular to the plate, and the entire surface of the plate emits light, allowing tracing and X-ray film observation. It becomes a solid lighting material suitable for purposes such as For edge lighting, when objects are placed in cells according to the shape of the characters, figures, patterns, symbols, etc. to be displayed, when the casting material is poured and hardened, air bubbles are unevenly distributed according to the characters, figures, etc. In this case, almost the same effect can be obtained by adhering the bubble-containing plate cut out in an appropriate shape to the surface of a transparent inorganic or organic glass plate instead of burying it. [Operations] The organic glass beads used in the method of the present invention not only dissolve a small amount of air in the particles themselves, but also dissolve microscopic racks and other particles existing on the surface of the organic glass beads. Some air is also attached or adsorbed to the voids. Therefore, when the beads are added to the casting material, the entrained air becomes the nucleus of the bubbles as they dissolve and swell, and gradually become larger bubbles. It is thought that a similar phenomenon occurs with the addition of beads in the well-known organic glass casting technology, but in this case, pressure is essential to suppress the generation of bubbles as much as possible. In this respect, the technical idea is different from the present invention, which does not suppress the generation of bubbles by intentionally performing curing under normal pressure.As long as appropriate conditions are selected, the size and distribution density of the bubbles generated will be controlled. It is almost constant, and the inner wall of the bubble is smooth.As a result, the incident light is reflected evenly, so the illuminance by edge lighting is constant and an excellent display or decorative effect can be obtained. Embodiment g All The embodiments of the invention will be described below with reference to Examples, but the examples are merely for illustration purposes and do not imply any restriction or limitation on the idea of the invention. Example 1 (Method (a)) Methyl methacrylate ( After mixing 0.1 part of a polymerization initiator (AIBN) etc. with 100 parts by weight of MMA) monomer (the same applies hereinafter), the mixture was suctioned to about 30 mmHg and degassed.To this catalyst-added monomer, polymethyl granules with an average particle size of 270 μm were mixed. 60 parts of methacrylate (PMMA) (manufactured by Sumipex' BMH) were mixed and stirred in an open system. As the mixture was stirred, the resin particles gradually dissolved, and the appearance was a viscous slurry. It became. Separately, prepare a formwork in which two polished glass plates that have been cleaned and dried in advance are placed side by side with a gap of 5 mm in inner diameter, and the periphery is closed with a polyvinyl chloride gasket, and the slurry is poured into the formwork. After pouring, seal the injection port and leave in a constant temperature bath for 5 minutes.
After polymerization at 5 to 60°C, the polymerization was completed by heat treatment in a constant temperature bath at 120°C. After the obtained polymer was gradually cooled to 40°C and annealed, the mold was disassembled to form a cured cellular organic glass plate (
The crude invention product) was taken out, the peripheral portion was cut, and the cut end surface was polished while cooling with water, thereby obtaining the desired cellular organic glass plate. This product has bubbles with an average diameter of about IIIφ uniformly distributed, and can be used as a solid lighting material, shade, or non-transparent window material, or as a decoration for edge lighting by cutting it out with a laser cutter. It can be used as a figurative material for characters, symbols, figures, etc. on boards or display boards. Example 2 (Method (b)) Methyl methacrylate (M
MA) Add 0.1 part of A I B N and other additives to 100 parts of the monomer, stir and mix to dissolve, then charge the degassed casting material and pour the mold into the Example from the upper open end of the mold. The PMMA beads used in 1 were poured continuously to fill the mold to 95% of its height, and then the open end of the mold was sealed. Next, the formwork is prepolymerized in a constant temperature bath controlled at 55 to 60°C, and then polymerization is completed in a hot air circulation oven at 120°C, and then gradually cooled to 40°C for annealing. did. Thereafter, the mold was dismantled, the molded product was taken out, and the peripheral portion was cut in a conventional manner to obtain the desired cellular organic glass plate. Example 3 (Method (C)) After the beads used in Example 1 were uniformly filled into the same mold as in Example 1, the opening was sealed. Next, a small hole is made in the upper gasket, a deaeration nozzle is inserted into this hole, and after deaeration, cold MM is passed through the nozzle.
Monomer A (mixed with additives such as AIBN) was injected to seal the holes, and then polymerization was carried out in the same manner as in the previous example to obtain a desired cellular organic glass plate.
以上説明した通り、本発明は、エツジライティング用、
シェード、固型照明材料などとして利用することができ
る均整な（密度、大きさ、形状等の略々均しい）気泡入
り有機ガラス板を取得するための新規な手段を提供でき
たことを通じて関連産業及び民生の振興及び向上に寄与
する。As explained above, the present invention is for edge writing,
Related industries by providing a new means for obtaining a symmetrical (approximately uniform density, size, shape, etc.) cellular organic glass plate that can be used as shades, solid lighting materials, etc. and contribute to the promotion and improvement of people's livelihood.
Claims (1)
機ガラスモノマー若しくはプレポリマー又はそれらの混
合物を略々常圧下に型内で重合させることを特徴とする
気泡入り有機ガラス板の製造法。 ２ 有機ガラスモノマー若しくはプレポリマー又はそれ
らの混合物と有機ガラスビーズとの量比が、７０：３０
〜２０：８０、好ましくは６０：４０〜２５：７５であ
る請求項１記載の製造法。 ３ 型内への有機ガラスのビーズを添加した有機ガラス
モノマー若しくはプレポリマー又はそれらの混合物の仕
込みを低温下に行う請求項１記載の方法。[Claims] 1. A cellular organic glass plate characterized in that an organic glass monomer or prepolymer or a mixture thereof to which organic glass beads are added as an air-entraining agent is polymerized in a mold under approximately normal pressure. Manufacturing method. 2 The quantitative ratio of organic glass monomer or prepolymer or mixture thereof to organic glass beads is 70:30.
20:80, preferably 60:40 to 25:75. 3. The method according to claim 1, wherein the organic glass monomer or prepolymer or a mixture thereof to which organic glass beads are added is charged into the mold at a low temperature.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14652290A JP2994434B2 (en) | 1990-06-04 | 1990-06-04 | Manufacturing method of organic glass molded product with bubbles |
| US07/639,422 US5269977A (en) | 1990-01-12 | 1991-01-11 | Method of manufacturing a foam transparent organic glass plate |
| EP19910105167 EP0457009A3 (en) | 1990-05-17 | 1991-04-02 | Light reflective body, method of manufacturing the same, and use for the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14652290A JP2994434B2 (en) | 1990-06-04 | 1990-06-04 | Manufacturing method of organic glass molded product with bubbles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0439008A true JPH0439008A (en) | 1992-02-10 |
| JP2994434B2 JP2994434B2 (en) | 1999-12-27 |
Family
ID=15409557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14652290A Expired - Fee Related JP2994434B2 (en) | 1990-01-12 | 1990-06-04 | Manufacturing method of organic glass molded product with bubbles |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2994434B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5826508A (en) * | 1996-07-31 | 1998-10-27 | Komori Corporation | Inking apparatus for printing press |
| CN112902100A (en) * | 2019-11-19 | 2021-06-04 | 通用汽车环球科技运作有限责任公司 | Light bar for external lighting assembly |
-
1990
- 1990-06-04 JP JP14652290A patent/JP2994434B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5826508A (en) * | 1996-07-31 | 1998-10-27 | Komori Corporation | Inking apparatus for printing press |
| CN112902100A (en) * | 2019-11-19 | 2021-06-04 | 通用汽车环球科技运作有限责任公司 | Light bar for external lighting assembly |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2994434B2 (en) | 1999-12-27 |
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