JPH01256507A - Polymer composition - Google Patents
Polymer compositionInfo
- Publication number
- JPH01256507A JPH01256507A JP8464188A JP8464188A JPH01256507A JP H01256507 A JPH01256507 A JP H01256507A JP 8464188 A JP8464188 A JP 8464188A JP 8464188 A JP8464188 A JP 8464188A JP H01256507 A JPH01256507 A JP H01256507A
- Authority
- JP
- Japan
- Prior art keywords
- methacrylate
- monomer
- polymer
- acrylate
- light transmittance
- 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
- 229920000642 polymer Polymers 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 11
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 20
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 abstract description 16
- 230000003287 optical effect Effects 0.000 abstract description 14
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 9
- MUTNCGKQJGXKEM-UHFFFAOYSA-N tamibarotene Chemical compound C=1C=C2C(C)(C)CCC(C)(C)C2=CC=1NC(=O)C1=CC=C(C(O)=O)C=C1 MUTNCGKQJGXKEM-UHFFFAOYSA-N 0.000 abstract description 5
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 abstract description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 abstract description 4
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 abstract 1
- 238000002834 transmittance Methods 0.000 description 35
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- 239000000463 material Substances 0.000 description 20
- 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 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 9
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 6
- 239000004926 polymethyl methacrylate Substances 0.000 description 6
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-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 2
- NUXLDNTZFXDNBA-UHFFFAOYSA-N 6-bromo-2-methyl-4h-1,4-benzoxazin-3-one Chemical compound C1=C(Br)C=C2NC(=O)C(C)OC2=C1 NUXLDNTZFXDNBA-UHFFFAOYSA-N 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- DJKKWVGWYCKUFC-UHFFFAOYSA-N 2-butoxyethyl 2-methylprop-2-enoate Chemical compound CCCCOCCOC(=O)C(C)=C DJKKWVGWYCKUFC-UHFFFAOYSA-N 0.000 description 1
- YXYJVFYWCLAXHO-UHFFFAOYSA-N 2-methoxyethyl 2-methylprop-2-enoate Chemical compound COCCOC(=O)C(C)=C YXYJVFYWCLAXHO-UHFFFAOYSA-N 0.000 description 1
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 1
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- XWNVSPGTJSGNPU-UHFFFAOYSA-N ethyl 4-chloro-1h-indole-2-carboxylate Chemical compound C1=CC=C2NC(C(=O)OCC)=CC2=C1Cl XWNVSPGTJSGNPU-UHFFFAOYSA-N 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- CSVRUJBOWHSVMA-UHFFFAOYSA-N oxolan-2-yl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCO1 CSVRUJBOWHSVMA-UHFFFAOYSA-N 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 238000010558 suspension polymerization method Methods 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、レンズ、光ファイバーなどの光学部品に用い
られる重合体組成物に関するものである。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a polymer composition used for optical components such as lenses and optical fibers.
〈従来の技術と発明が解決しようとする課題〉レンズや
光ファイバーなどの光学部品に使用される光学材料とし
ては、先透過性に優れる石英や溶融シリカなどの無機系
ガラス材料が一般的である。しかし、これら無機系ガラ
ス材料は加工性に劣り、また、可撓性や耐衝撃性の点で
問題があるため、最近では、上記加工性に優れ、しかも
可撓性、耐衝撃性の点で無機系ガラス材料よりも有利な
熱可塑性樹脂材料が、前記光学材料として用いられるよ
うになってきた。<Prior art and problems to be solved by the invention> As optical materials used for optical parts such as lenses and optical fibers, inorganic glass materials such as quartz and fused silica, which have excellent forward transparency, are generally used. However, these inorganic glass materials have poor processability and problems with flexibility and impact resistance. Thermoplastic resin materials, which are more advantageous than inorganic glass materials, have come to be used as optical materials.
光学材料に用いられる樹脂材料には、初期の光透過性に
優れ着色のないことが要求されるだけでなく、吸湿によ
り光透過性が著しく低下しないことが要求されており、
従来からある樹脂材料の中ではポリメチルメタクリレー
トが、上記要求を最も良く満たすものとして、前記レン
ズや光ファイバーのコア材などに実用されている。例え
ば、上記ポリメチルメタクリレートの板体（厚み３．０
ＩＩＩ＋＊）の初期の透過率（波長４５０〜７Ｇ０ ｎ
ｍ）は９２〜９８％、７０℃９５％Ｒ１＋の吸湿条件下
で１０００時間暴露後の透過率は９２〜９５％であり、
初期の光透過性に優れると共にその低下が殆ど見られな
いのである。しかし、このポリメチルメタクリレートは
、熱可塑性樹脂材料の中では可撓性に乏しく柔軟性のな
いものに属しており、室温でも曲げによって容易に破断
する虞があるため、特に光ファイバーなどの長尺成形品
における耐久性が問題となる。Resin materials used in optical materials are required not only to have excellent initial light transmittance and no coloration, but also to not significantly reduce light transmittance due to moisture absorption.
Among conventional resin materials, polymethyl methacrylate satisfies the above-mentioned requirements the best and has been put to practical use in the core materials of lenses and optical fibers. For example, the above polymethyl methacrylate plate (thickness 3.0
III+*) initial transmittance (wavelength 450-7G0 n
m) is 92 to 98%, and the transmittance after exposure for 1000 hours under moisture absorption conditions of 70°C and 95% R1+ is 92 to 95%,
It has excellent initial light transmittance and shows almost no deterioration. However, polymethyl methacrylate is one of the less flexible thermoplastic resin materials, and can easily break when bent even at room temperature. The durability of the product is an issue.
光学材料に用いられる樹脂材料としては、上記ポリメチ
ルメタクリレートの他にも、例えばポリスチレンやポリ
カーボネートなどが知られているが、これらの樹脂材料
は、吸湿による光透過性の低下は比較的少ないものの、
初期の光透過性や無希色性の点で前記ポリメチルメタク
リレートよりも劣り、しかも、やはり可撓性に乏しく柔
軟性がないという問題を有している。In addition to the polymethyl methacrylate mentioned above, polystyrene and polycarbonate are also known as resin materials used in optical materials.Although these resin materials have a relatively small decrease in light transmittance due to moisture absorption,
It is inferior to the above-mentioned polymethyl methacrylate in terms of initial light transmittance and color-free property, and also has the problem of poor flexibility and lack of flexibility.
初期の光透過性に優れ、しかも可撓性にも優れた樹脂材
料として、ノルマルブチルメタクリレート、ノルマルペ
ンチルメタクリレート、ノルマルヘキシルメタクリレー
ト、２−エチルへキシルメタクリレート、ノルマルオク
チルメタクリレート、ノルマルノニルメタクリレート、
ラウリルメタクリレート等の単量体の重合体もしくは共
重合体、または、上記単量体とエチルメタクリレート、
ノルマルプロピルメタクリレート、イソプロピルメタク
リレート、イソブチルメタクリレート等の単量体との共
重合体など、メチルメタクリレート以外のアルキルメタ
クリレート単量体の重合体または共重合体がある。しか
し、これらの重合体または共重合体は、吸湿により光透
過性が著しく低下するという問題がある。例えば、上記
ノルマルブチルメタクリレートの重合体を厚み３．０關
の板体に成形したものでは、前記ポリメチルメタクリレ
−！・と同条件の暴露により、透過率が初期の９２〜９
５％から、僅か２〜５％まで低下してしまうのである。Resin materials with excellent initial light transmittance and flexibility include normal butyl methacrylate, normal pentyl methacrylate, normal hexyl methacrylate, 2-ethylhexyl methacrylate, normal octyl methacrylate, normal nonyl methacrylate,
A polymer or copolymer of monomers such as lauryl methacrylate, or the above monomers and ethyl methacrylate,
There are polymers or copolymers of alkyl methacrylate monomers other than methyl methacrylate, such as copolymers with monomers such as normal propyl methacrylate, isopropyl methacrylate, and isobutyl methacrylate. However, these polymers or copolymers have a problem in that their light transmittance is significantly reduced due to moisture absorption. For example, when the above-mentioned n-butyl methacrylate polymer is formed into a plate with a thickness of about 3.0 mm, the above-mentioned polymethyl methacrylate!・By exposure under the same conditions as ・, the transmittance decreased from 92 to 9.
It drops from 5% to only 2-5%.
本発明者は、上記重合体または共重合体の優れた可撓性
、初期の光透過性に着目し、種々検討を行った結果、前
記単量体に、分子内に水酸基を有するアクリレート単量
体、および分子内に水酸基を有するメタクリレート単量
体（以下ｒｏｌｌメタクリレート単量体」と記す）のう
ちの少なくとも一方を共重合させれば、吸湿による光透
過性の低下をある程度低減できることを見出し、先の出
願に至った（特願昭６２−１７２４７４号）。例えば、
前記ノルマルブチルメタクリレートに、２−ヒドロキシ
エチルアクリレートおよび２−ヒドロキシエチルメタク
リレートを、単量体の重量比６：２：２で重合させた共
重合体は、室温での曲げ破断の問題が全くなく、しかも
、該共重合体を厚み３．０器の板体に成形したものでは
、７０℃９５％ＲＨ，１０００時間の暴露により透過率
が初期の９２〜９４％から８４〜８６％に低下するのみ
であり、光透過性の低下を大きく低減できるようになる
。しかし、この共重合体においても、上記のように、依
然として約１０％程度の透過率の低下が見られ、光学材
料に要求される光透過性を吸湿後も維持できるまでには
至っていない。The present inventor paid attention to the excellent flexibility and initial light transmittance of the above polymer or copolymer, and as a result of various studies, discovered that an acrylate monomer having a hydroxyl group in the molecule was added to the above monomer. discovered that the reduction in light transmittance due to moisture absorption can be reduced to some extent by copolymerizing at least one of a methacrylate monomer having a hydroxyl group in the molecule (hereinafter referred to as "roll methacrylate monomer"), This resulted in the earlier application (Japanese Patent Application No. 172474/1982). for example,
The copolymer obtained by polymerizing n-butyl methacrylate with 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate at a monomer weight ratio of 6:2:2 has no problem of bending breakage at room temperature. Moreover, when the copolymer is molded into a plate with a thickness of 3.0 mm, the transmittance only decreases from the initial 92-94% to 84-86% after exposure at 70°C, 95% RH for 1000 hours. Therefore, it becomes possible to greatly reduce the decrease in light transmittance. However, even in this copolymer, as mentioned above, a decrease in transmittance of about 10% is still observed, and the light transmittance required for an optical material cannot be maintained even after moisture absorption.
以上のように、現在のところ、初期の光透過性、無青色
性、可撓性に優れ、しかも吸湿後も光学材料に要求され
る光透過性を維持できる重合体は見出されておらず、そ
のような重合体組成物の開発が望まれている。As described above, to date, no polymer has been found that has excellent initial light transmittance, no blue color, and flexibility, and can maintain the light transmittance required for optical materials even after absorbing moisture. , the development of such polymer compositions is desired.
く課題を解決するための手段および作用〉上記課題を解
決するため、本発明の重合体組成物は、アルキルメタク
リレート単量体と、０１１メタクリレ一ト単量体と、分
子内にエーテル結合を有するアクリレート単量体（以下
「エーテルアクリレート単量体」と記す）との重合体か
らなることを特徴とする。Means and Effects for Solving the Problems In order to solve the above problems, the polymer composition of the present invention comprises an alkyl methacrylate monomer, a 011 methacrylate monomer, and an ether bond in the molecule. It is characterized by being composed of a polymer with an acrylate monomer (hereinafter referred to as "ether acrylate monomer").
以下に、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明に用いられるアルキルメタクリレート単量体の種
類は特に限定されないが、例えば先に例示したノルマル
ブチルメタクリレートなどの各単量体や、メチルメタク
リレートが好ましいものとして例示される。これらアル
キルメタクリレート単量体は単独で、或いは２種以上混
合して使用される。The type of alkyl methacrylate monomer used in the present invention is not particularly limited, but preferred examples include the monomers exemplified above, such as n-butyl methacrylate, and methyl methacrylate. These alkyl methacrylate monomers may be used alone or in combination of two or more.
また、０１１メタクリレ一ト単量体としては、例えば、
２−ヒドロキシエチルメタクリレート、２−ヒドロキシ
プロピルメタクリレート、３−ヒドロキシプロピルメタ
クリレートなどが好ましいものとして例示され、これら
０１１メタクリレ一ト単量体は単独で、或いは２種以上
混合して使用される。Further, as the 011 methacrylate monomer, for example,
Preferred examples include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, and 3-hydroxypropyl methacrylate, and these 011 methacrylate monomers may be used alone or in combination of two or more.
また、エーテルアクリレート単量体としては、テトラヒ
ドロフルフリルアクリレート、２−メトキシエチルアク
リレート、２−エトキシエチルアクリレート、２−ブト
キシエチルアクリレートなどが好ましいものとして例示
され、これらエーテルアクリレート単量体も単独で、或
いは２種以上混合して使用される。なお、このエーテル
アクリレート単量体に代えて、テトラヒドロフルフリル
メタクリレート、２−メトキシエチルメタクリレート、
２−エトキシエチルメタクリレート、２−ブトキシエチ
ルメタクリレートなど、分子内にエーテル結合を有する
メタクリレート単量体を使用した共重合体は、吸湿によ
る光透過性の低下は少ないものの可撓性に欠け、室温で
も曲げにより容易に破断するという問題がある。Preferred examples of the ether acrylate monomer include tetrahydrofurfuryl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, and 2-butoxyethyl acrylate, and these ether acrylate monomers can also be used alone. Alternatively, two or more types may be used in combination. In addition, in place of this ether acrylate monomer, tetrahydrofurfuryl methacrylate, 2-methoxyethyl methacrylate,
Copolymers using methacrylate monomers with an ether bond in the molecule, such as 2-ethoxyethyl methacrylate and 2-butoxyethyl methacrylate, have little decrease in light transmittance due to moisture absorption, but lack flexibility and are difficult to use even at room temperature. There is a problem that it easily breaks when bent.
なお、前記各単量体は、その種類や重合体に要求される
機械的特性などの条件の違いにより適宜割合とすること
かできるが、特に重合体に要求される耐候性の程度の違
いにより、全単量体量に占めるＯ１１メタクリレート単
量体およびエーテルアクリレート単量体の割合の好まし
い範囲が設定される。例えば吸湿条件５０℃９０％Ｒ１
＋では、上記両車量体のうち前者の割合が１５重量％以
上、１５〜２０重量％の範囲内、後者の割合が５重量％
以上、５〜３０重量％の範囲内であることが好ましく、
吸湿条件６０℃９５％Ｒ１１では、前者の割合が２０重
量％以上、２０〜３０重量％の範囲内、後者の割合が１
０重量％以上、１０〜４０重量％の範囲内であることが
好ましく、吸湿条件７０℃９５％Ｒ１１では、前者の割
合が３０重量％以上、３０〜４０重量％の範囲内、後者
の割合が１０重量％以上、１０〜５０重量％の範囲内で
あることが好ましい。もし、前記両車量体の割合のうち
の一方でも、上記好ましい範囲の下限を下回ると、上記
各吸湿条件下での吸湿による光透過性低下の程度が大き
くなり、光学材料に要求される光透過性を維持できなく
なる虞がある。The proportions of each of the above monomers can be adjusted as appropriate depending on the type of the monomer and the mechanical properties required of the polymer. , a preferable range of the ratio of O11 methacrylate monomer and ether acrylate monomer to the total monomer amount is set. For example, moisture absorption condition 50℃90%R1
For +, the proportion of the former is 15% or more by weight, within the range of 15 to 20% by weight, and the proportion of the latter is 5% by weight.
Above, it is preferably within the range of 5 to 30% by weight,
Under the moisture absorption condition 60°C 95% R11, the former proportion is 20% by weight or more, within the range of 20 to 30% by weight, and the latter proportion is 1% by weight.
It is preferable that the proportion is 0% by weight or more and 10 to 40% by weight, and under the moisture absorption condition 70°C 95% R11, the proportion of the former is 30% by weight or more and is in the range of 30 to 40% by weight, and the proportion of the latter is It is preferably 10% by weight or more, and within the range of 10 to 50% by weight. If either of the above-mentioned ratios of both vehicle masses falls below the lower limit of the above-mentioned preferred range, the degree of decrease in light transmittance due to moisture absorption under each of the above-mentioned moisture absorption conditions will increase, and the light transmittance required for optical materials will increase. There is a risk that transparency may not be maintained.
上記構成からなる本発明の重合体組成物は、初期の光透
過性に優れ、また、この光透過性が吸湿によって大きく
低下することが防止されて光学材料に要求される光透過
性が維持され、しかも可撓性に優れて室温で破断する虞
のないものとなる。The polymer composition of the present invention having the above structure has excellent initial light transmittance, and this light transmittance is prevented from being significantly reduced due to moisture absorption, thereby maintaining the light transmittance required for optical materials. Moreover, it has excellent flexibility and there is no risk of breaking at room temperature.
例えば、前記ノルマルブチルメタクリレート、２−ヒド
ロキシエチルメタクリレートおよびテトラヒドロフルフ
リルアクリレートの各単量体（重量比５ ： ３ ：
２）が共重合された重合体組成物は可撓性に優れ、室温
における曲げ破断の問題が全くない。また、上記重合体
を、厚み３．０ｍｍの板体に成形したものでは、初期の
光透過率が９２〜９６％、７０’０９５％Ｒ１１の吸湿
条件下で１０００時間暴露後の透過率が９２〜９５％で
あり、初期の光透過性に優れると共にその低下が殆ど見
られない。For example, the monomers of n-butyl methacrylate, 2-hydroxyethyl methacrylate, and tetrahydrofurfuryl acrylate (weight ratio 5:3:
A polymer composition in which 2) is copolymerized has excellent flexibility and has no problem of bending breakage at room temperature. In addition, when the above polymer was molded into a plate with a thickness of 3.0 mm, the initial light transmittance was 92 to 96%, and the transmittance after 1000 hours of exposure under moisture absorption conditions of 70'095% R11 was 92%. ~95%, which is excellent in initial light transmittance and shows almost no decrease in light transmittance.
なお、前記各単量体から本発明の重合体組成物を製造す
る方法としては、塊状重合法、溶液重合法、乳化重合法
、懸濁重合法などの通常の重合方法が適用でき、重合開
始剤としては、アゾビスイソブチロニトリル等のアゾ化
合物や、過酸化ラウロイル、過酸化ベンゾイル等の過酸
化物など、通常のラジカル重合開始剤が使用できる。In addition, as a method for producing the polymer composition of the present invention from each of the above-mentioned monomers, ordinary polymerization methods such as bulk polymerization method, solution polymerization method, emulsion polymerization method, and suspension polymerization method can be applied. As the agent, common radical polymerization initiators can be used, such as azo compounds such as azobisisobutyronitrile, and peroxides such as lauroyl peroxide and benzoyl peroxide.
〈実施例〉
以下に、実施例並びに比較例に基づき、本発明をより詳
細に説明する。<Example> The present invention will be described in more detail below based on Examples and Comparative Examples.
実施例１
ノルマルブチルメタクリレ−１・、２−ヒドロキシエチ
ルメタクリレート、テトラヒドロフルフリルアクリレー
トの各単量体を重量比５０：３０：２０の割合で、アゾ
ビスイソブチロニトリルを重合開始剤として塊状重合さ
せて重合体を得た。得られた重合体をメチルエチルケト
ンに溶解後、冷メタノールで２回再沈澱させて精製した
。Example 1 Each monomer of n-butyl methacrylate-1., 2-hydroxyethyl methacrylate, and tetrahydrofurfuryl acrylate was formed into a mass at a weight ratio of 50:30:20 using azobisisobutyronitrile as a polymerization initiator. A polymer was obtained by polymerization. The obtained polymer was purified by dissolving it in methyl ethyl ketone and reprecipitating it twice with cold methanol.
実施例２
ノルマルヘキシルメタクリレート、エチルメタクリレー
ト、２−ヒドロキシプロピルメタクリレート、２−メト
キシエチルアクリレートの各単量体を重量比４０： １
０： ２０： ３０の割合で、アゾビスイソブチロニト
リルを重合開始剤としてメチルエチルケトン中で溶液重
合させた後、冷メタノールで２回再沈澱させて重合体を
得た。Example 2 Each monomer of n-hexyl methacrylate, ethyl methacrylate, 2-hydroxypropyl methacrylate, and 2-methoxyethyl acrylate was mixed in a weight ratio of 40:1.
Solution polymerization was carried out in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator at a ratio of 0:20:30, followed by reprecipitation twice with cold methanol to obtain a polymer.
実施例３
２−エチルへキシルメタクリレート、２−ヒドロキシエ
チルメタクリレート、テトラヒドロフルフリルアクリレ
ートの各単量体を重量比６０： ３０： １０の割合で
、アゾビスイソブチロニトリルを重合開始剤としてメチ
ルエチルケトン中で溶液重合させた後、冷メタノールで
２回再沈澱させて重合体を得た。Example 3 Each monomer of 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate, and tetrahydrofurfuryl acrylate was mixed in a weight ratio of 60:30:10 in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator. After solution polymerization, the mixture was reprecipitated twice with cold methanol to obtain a polymer.
実施例４
ラウリルメタクリレート、インブチルメタクリレート、
２−ヒドロキシプロピルメタクリレート、２−エトキシ
エチルアクリレートの各単量体を重量比１０： ４０：
２０： １０の割合で、過酸化ラウロイルを重合開始
剤としてメチルエチルケトン中で溶液重合させた後、冷
メタノールで２回再沈澱させて重合体を得た。Example 4 Lauryl methacrylate, inbutyl methacrylate,
The weight ratio of each monomer of 2-hydroxypropyl methacrylate and 2-ethoxyethyl acrylate was 10:40:
Solution polymerization was carried out in methyl ethyl ketone at a ratio of 20:10 using lauroyl peroxide as a polymerization initiator, followed by reprecipitation twice with cold methanol to obtain a polymer.
実施例５
ノルマルオクチルメタクリレート、２−ヒドロキシエチ
ルメタクリレート、テトラヒドロフッ１フリルアクリレ
ートの各単量体を重量比６０： ３０： ｔｏの割合で
、過酸化ラウロイルを重合開始剤として塊状重合させて
重合体を得た。得られた重合体をメチルエチルケトンに
溶解後、冷メタノールで２回再沈澱させて精製した。Example 5 Each monomer of normal octyl methacrylate, 2-hydroxyethyl methacrylate, and tetrahydrofuryl methacrylate was subjected to bulk polymerization at a weight ratio of 60:30:to using lauroyl peroxide as a polymerization initiator to obtain a polymer. Obtained. The obtained polymer was purified by dissolving it in methyl ethyl ketone and reprecipitating it twice with cold methanol.
比較例１
メチルメタクリレートを過酸化ラウロイルを重合開始剤
として塊状重合させて重合体を得た。得られた重合体を
メチルエチルケトンに溶解後、冷メタノールで２回再沈
澱させて精製した。Comparative Example 1 A polymer was obtained by bulk polymerizing methyl methacrylate using lauroyl peroxide as a polymerization initiator. The obtained polymer was purified by dissolving it in methyl ethyl ketone and reprecipitating it twice with cold methanol.
比較例２
ノルマルブチルメタクリレート、２−ヒドロキシエチル
アクリレート、２−ヒドロキシエチルメタクリレートの
各単量体を重量比６０：２０：２０の割合で、アゾビス
イソブチロニトリルを重合開始剤としてメチルエチルケ
トン中で溶液重合させた後、冷メタノールで２回再沈澱
させて重合体を得た。Comparative Example 2 Each monomer of n-butyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl methacrylate was dissolved in methyl ethyl ketone at a weight ratio of 60:20:20 using azobisisobutyronitrile as a polymerization initiator. After polymerization, reprecipitation was performed twice with cold methanol to obtain a polymer.
比較例３
ノルマルオクチルメタクリレート、２−ヒドロキシエチ
ルメタクリレート、２−エトキシエチルメタクリレート
の各単量体を重量比７０：２０：１Ｇの割合で、アゾビ
スイソブチロニトリルを重合開始剤としてメチルエチル
ケトン中で溶液重合させた後、冷メタノールで２回再沈
澱させて重合体を得た。Comparative Example 3 Each monomer of normal octyl methacrylate, 2-hydroxyethyl methacrylate, and 2-ethoxyethyl methacrylate was dissolved in methyl ethyl ketone at a weight ratio of 70:20:1G using azobisisobutyronitrile as a polymerization initiator. After polymerization, reprecipitation was performed twice with cold methanol to obtain a polymer.
比較例４
ノルマルブチルメタクリレートをアゾビスイソブチロニ
トリルを重合開始剤としてメチルエチルケトン中で溶液
重合させた後、冷メタノールで２回再沈澱させて重合体
を得た。Comparative Example 4 Normal butyl methacrylate was solution polymerized in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator, and then reprecipitated twice with cold methanol to obtain a polymer.
比較例５
エチルメタクリレートをアゾビスイソブチロニトリルを
重合開始剤としてメチルエチルケトン中で溶液重合させ
た後、冷メタノールで２回再沈澱させて重合体を得た。Comparative Example 5 Ethyl methacrylate was solution polymerized in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator, and then reprecipitated twice with cold methanol to obtain a polymer.
比較例６
２−エチルへキシルメタクリレートをアゾビスイソブチ
ロニトリルを重合開始剤としてメチルエチルケトン中で
溶液重合させた後、冷メタノールで２回再沈澱させて重
合体を得た。Comparative Example 6 2-Ethylhexyl methacrylate was solution polymerized in methyl ethyl ketone using azobisisobutyronitrile as a polymerization initiator, and then reprecipitated twice with cold methanol to obtain a polymer.
上記実施例１〜５、比較例１〜６で得られた重合体の数
平均分子量をΔＮ定すると共に、上記重合体から厚み１
．０ｍｍの板体を成形し、該板体を用いて１８０″の曲
げ試験（１１−１定の雰囲気温度２０℃）を行い重合体
の可撓性を調べた。また、上記重合体から厚み３．０園
讃の板体を成形し、該板体を用いて吸湿条件下１０００
時間暴露前後の、波長４５０〜７００１ｍの光の透過率
についてＡｌ１定した。結果を表に示す。The number average molecular weight of the polymers obtained in Examples 1 to 5 and Comparative Examples 1 to 6 was determined by ΔN, and a thickness of 1
．． A 0 mm thick plate was formed, and a 180" bending test (11-1 constant ambient temperature 20°C) was conducted using the plate to examine the flexibility of the polymer. A plate of .0 Sonosan was molded, and the plate was heated to 1000℃ under moisture absorption conditions.
Al1 was determined for the transmittance of light with a wavelength of 450 to 7001 m before and after time exposure. The results are shown in the table.
上記衣にみるように、アルキルメタクリレート単独で構
成された重合体のうち、比較例１、比較例５の重合体は
可撓性がなく、比較例４、比較例５、比較例６の重合体
は吸湿により光透過性が著しく低下した。また、上記ア
ルキルメタクリレートに他の単量体を併用した重合体の
うち比較例３の重合体は可撓性がなく、比較例２の重合
体は吸湿後の透過率の低下により光学材料に要求される
光透過性を維持できなかった。一方、実施例１〜５の重
合体は可撓性に優れ、しかも吸湿後も光透過性の低下は
殆ど見られなかった。As seen in the above clothing, among the polymers composed of alkyl methacrylate alone, the polymers of Comparative Examples 1 and 5 have no flexibility, while the polymers of Comparative Examples 4, 5, and 6 have no flexibility. The light transmittance decreased significantly due to moisture absorption. In addition, among the polymers in which the alkyl methacrylate and other monomers are used in combination, the polymer of Comparative Example 3 lacks flexibility, and the polymer of Comparative Example 2 is required for optical materials due to a decrease in transmittance after moisture absorption. It was not possible to maintain the desired light transmittance. On the other hand, the polymers of Examples 1 to 5 had excellent flexibility, and hardly any decrease in light transmittance was observed even after absorbing moisture.
〈発明の効果〉
本発明の重合体組成物は、アルキルメタクリレート単量
体と、０１１メタクリレ一ト単量体と、エーテルアクリ
レート単量体との重合体からなるものであるため、初期
の光透過性、可撓性に優れると共に、吸湿によって上記
光透過性が殆ど低下せず、光学材料に要求される光透過
性を吸湿後も維持できるものとなっている。<Effects of the Invention> Since the polymer composition of the present invention is composed of a polymer of an alkyl methacrylate monomer, a 011 methacrylate monomer, and an ether acrylate monomer, the initial light transmission is In addition to having excellent properties and flexibility, the above-mentioned light transmittance hardly decreases due to moisture absorption, and the light transmittance required of an optical material can be maintained even after moisture absorption.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8464188A JPH01256507A (en) | 1988-04-05 | 1988-04-05 | Polymer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8464188A JPH01256507A (en) | 1988-04-05 | 1988-04-05 | Polymer composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01256507A true JPH01256507A (en) | 1989-10-13 |
Family
ID=13836317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8464188A Pending JPH01256507A (en) | 1988-04-05 | 1988-04-05 | Polymer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01256507A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020036205A1 (en) * | 2018-08-16 | 2020-02-20 | Terumo Kabushiki Kaisha | Cell culture substrate |
| WO2020036206A1 (en) * | 2018-08-16 | 2020-02-20 | Terumo Kabushiki Kaisha | Cell culture substrate |
-
1988
- 1988-04-05 JP JP8464188A patent/JPH01256507A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020036205A1 (en) * | 2018-08-16 | 2020-02-20 | Terumo Kabushiki Kaisha | Cell culture substrate |
| WO2020036206A1 (en) * | 2018-08-16 | 2020-02-20 | Terumo Kabushiki Kaisha | Cell culture substrate |
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