JP2001172462A - Methacrylic resin composition and method for producing its molded product - Google Patents
Methacrylic resin composition and method for producing its molded productInfo
- Publication number
- JP2001172462A JP2001172462A JP35773399A JP35773399A JP2001172462A JP 2001172462 A JP2001172462 A JP 2001172462A JP 35773399 A JP35773399 A JP 35773399A JP 35773399 A JP35773399 A JP 35773399A JP 2001172462 A JP2001172462 A JP 2001172462A
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- Japan
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- mass
- mold
- parts
- methacrylic resin
- resin plate
- 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.)
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- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、透明性に優れ、外
観欠陥のないメタクリル系樹脂組成物およびその成形品
の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a methacrylic resin composition having excellent transparency and having no appearance defect, and a method for producing a molded article thereof.
【０００２】[0002]
【従来の技術】メタクリル系樹脂板の製造法には鋳型製
板方式や押出製板方式等があるが、溶融成形した押出板
に比べ、鋳型重合させて得られるメタクリル系樹脂板は
光学歪も少ない上、分子量の選択範囲が広いので、耐薬
品性、加工性、機械的強度等を高めることができること
から、多くの分野で使用されている。2. Description of the Related Art A methacrylic resin plate can be produced by a mold-making method or an extrusion-making method. The methacrylic resin plate obtained by mold polymerization has a smaller optical distortion than a melt-molded extruded plate. Since it is small and has a wide selection range of molecular weight, chemical resistance, processability, mechanical strength and the like can be enhanced, and thus it is used in many fields.
【０００３】従来のメタクリル系樹脂板の重合には、離
型性の改善のために、種々の離型剤が用いられて来た。
例えば特許第２５７１７８７号には成型金型内での加圧
・加熱条件下では炭素数が８〜１３のアルキルアシッド
フォスフェートのモノエステルをメタクリル系樹脂に添
加することで、樹脂の離型性が向上することが開示され
ている。また、特開昭５８−８４８０７号にはガラスや
金属からなる鋳型内での重合時に炭素数が８〜１８の有
機リン酸エステルのジエステルをメタクリル系樹脂に添
加することで、樹脂の離型性が向上することが開示され
ている。さらに、特開平２―１４２０７号にはガラス、
金属、セラミック等からなる鋳型内での重合時に炭素数
が８〜１３のアルキルアシッドフォスフェートのモノエ
ステルとジエステルとの混合物をメタクリル系樹脂に添
加することで、樹脂の室温での離型性が向上することが
開示されている。[0003] In the polymerization of conventional methacrylic resin plates, various release agents have been used to improve the releasability.
For example, Japanese Patent No. 2571787 discloses that under pressurizing and heating conditions in a molding die, a monoester of an alkyl acid phosphate having 8 to 13 carbon atoms is added to a methacrylic resin to improve the releasability of the resin. It is disclosed to improve. Japanese Patent Application Laid-Open No. 58-84807 discloses a method of adding a diester of an organic phosphoric acid ester having 8 to 18 carbon atoms to a methacrylic resin during polymerization in a mold made of glass or metal. Is disclosed to be improved. Further, JP-A-2-14207 discloses glass,
By adding a mixture of a monoester and a diester of an alkyl acid phosphate having 8 to 13 carbon atoms to a methacrylic resin at the time of polymerization in a mold made of metal, ceramic, etc., the releasability of the resin at room temperature is improved. It is disclosed to improve.
【０００４】しかし、これら離型剤を用いた場合は、種
類や添加量により離型効果の過不足のため、高温での離
型性が不良となったり、高温での離型時に樹脂表面に欠
陥を生じたり、離型剤成分が表面に移行し、鋳型を汚染
して製品歩留まりが低下するといった問題があった。However, when these release agents are used, the release effect at high temperatures becomes poor due to the excess or deficiency of the release effect depending on the type and the amount of addition. There has been a problem that defects occur or the release agent component migrates to the surface, contaminates the mold, and lowers the product yield.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、重合
後の高温離型性に優れ、且つ鋳型を繰り返し使用しても
鋳型を汚染しない、透明性に優れた、外観欠陥のないメ
タクリル系樹脂を提供することにある。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a methacrylic compound which is excellent in high-temperature release property after polymerization, does not contaminate the mold even when the mold is used repeatedly, has excellent transparency, and has no appearance defect. It is to provide a resin.
【０００６】[0006]
【課題を解決するための手段】本発明者等は鋭意検討を
進めた結果、メタクリル酸メチルと他の共重合可能なビ
ニル系モノマーからなる単量体混合物あるいは部分重合
体混合物に、特定の酸性アルキルリン酸エステルとスル
ホ琥珀酸エステル塩とを併用して添加混合して重合する
ことにより、高温で剥離可能で表面欠陥が無く、メタク
リル系樹脂の特徴である優れた光学的性質や機械的性質
を維持したまま、収率良くメタクリル系樹脂板が得られ
ることを見い出し、本発明を完成するに至った。Means for Solving the Problems As a result of intensive studies, the present inventors have found that a specific acid mixture is added to a monomer mixture composed of methyl methacrylate and another copolymerizable vinyl monomer or a partial polymer mixture. Excellent optical and mechanical properties that are characteristic of methacrylic resin by peeling at high temperature and free of surface defects by adding, mixing and polymerizing alkyl phosphate ester and sulfosuccinate salt in combination. It has been found that a methacrylic resin plate can be obtained with good yield while maintaining the above, and the present invention has been completed.
【０００７】すなわち本発明は、メタクリル酸メチル単
量体単位６０〜１００質量％と他の共重合可能なビニル
系モノマー単位４０〜０質量％とからなる重合体１００
質量部に対して、０．００１〜０．０５質量部の２−エ
チルヘキシルアシッドフォスフェートおよび０．００２
〜０．１質量部のスルホ琥珀酸エステル塩が添加されて
なるメタクリル系樹脂組成物である。That is, the present invention relates to a polymer 100 comprising 60 to 100% by mass of a methyl methacrylate monomer unit and 40 to 0% by mass of another copolymerizable vinyl monomer unit.
0.001 to 0.05 parts by mass of 2-ethylhexyl acid phosphate and 0.002 parts by mass with respect to parts by mass.
It is a methacrylic resin composition to which about 0.1 part by mass of a sulfosuccinate salt is added.
【０００８】また、本発明の製造方法は、メタクリル酸
メチル６０〜１００質量％と他の共重合可能なビニル系
モノマー４０〜０質量％とからなる単量体混合物または
該単量体混合物と該単量体混合物の重合体との混合物１
００質量部、２−エチルヘキシルアシッドフォスフェー
ト０．００１〜０．０５質量部およびスルホ琥珀酸エス
テル塩０．００２〜０．１質量部を、ラジカル重合開始
剤の存在下、鋳型内で重合し、重合硬化物を７０〜１１
０℃の温度下で鋳型から取り出すことを特徴とするメタ
クリル系樹脂成形品の製造方法である。Further, the production method of the present invention relates to a monomer mixture comprising 60 to 100% by mass of methyl methacrylate and 40 to 0% by mass of another copolymerizable vinyl monomer, or Mixture 1 of monomer mixture with polymer
00 parts by mass, 0.001 to 0.05 parts by mass of 2-ethylhexyl acid phosphate and 0.002 to 0.1 parts by mass of a sulfosuccinate salt are polymerized in a mold in the presence of a radical polymerization initiator, 70 to 11 polymerized cured products
This is a method for producing a methacrylic resin molded product, which is taken out of a mold at a temperature of 0 ° C.
【０００９】[0009]
【発明の実施の形態】本発明において用いる単量体は、
メタクリル酸メチルの単独単量体のほか、それと共重合
可能なビニル系モノマーとの単量体混合物であってもよ
い。なお、本発明においては単独単量体であっても、便
宜的に「単量体混合物」という。メタクリル酸メチルと
共重合されるビニル系モノマーは、例えばメタクリル酸
エチル、メタクリル酸イソプロピル、メタクリル酸ｔ−
ブチル、メタクリル酸ｓ−ブチル、メタクリル酸ｎ−ブ
チル、メタクリル酸アミル、メタクリル酸オクチル、メ
タクリル酸２−エチルヘキシル、メタクリル酸ラウリ
ル、メタクリル酸フェニル、メタクリル酸シクロヘキシ
ル、メタクリル酸ベンジル等のシクロアルキル基、ベン
ジル基を含むアルキル基の炭素数１〜１２のメタクリル
酸エステル類；メタクリル酸ボルニル、メタクリル酸イ
ソボルニル、メタクリル酸フェンチル、メタクリル酸１
−メンチル、メタクリル酸アダマンチル、メタクリル酸
ジメチルアダマンチルなどの炭素数８〜２０のアルキル
基または脂環式炭化水素基を有するメタクリル酸エステ
ル類；アクリル酸メチル、アクリル酸エチル、アクリル
酸イソプロピル、アクリル酸ブチル、アクリル酸ｔ−ブ
チル、アクリル酸アミル、アクリル酸オクチル、アクリ
ル酸２−エチルヘキシル、アクリル酸ラウリル、アクリ
ル酸シクロヘキシル、アクリル酸フェニル、アクリル酸
ベンジル等のアクリル酸エステル類；スチレン、α−メ
チルスチレン、パラメチルスチレン、イソプロペニルス
チレン、ビニルトルエン等のビニル芳香族類；アクリロ
ニトリル、メタクリロニトリル等の不飽和ニトリル類；
メタクリル酸、アクリル酸、無水マレイン酸等の不飽和
カルボン酸類；エチレングリコールジ（メタ）アクリレ
ート、ジエチレングリコールジ（メタ）アクリレート、
ジビニルベンゼン等の多不飽和化合物等が挙げられる
が、これらに限定されるものではなく、これらは単独で
または２種以上を併用して用いることができる。BEST MODE FOR CARRYING OUT THE INVENTION The monomers used in the present invention are:
In addition to a single monomer of methyl methacrylate, a monomer mixture of a vinyl monomer copolymerizable therewith may be used. In the present invention, even a single monomer is referred to as a “monomer mixture” for convenience. Vinyl monomers copolymerized with methyl methacrylate include, for example, ethyl methacrylate, isopropyl methacrylate, t-methacrylate.
Cycloalkyl groups such as butyl, s-butyl methacrylate, n-butyl methacrylate, amyl methacrylate, octyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, phenyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, and benzyl Methacrylates having 1 to 12 carbon atoms of an alkyl group containing a group; bornyl methacrylate, isobornyl methacrylate, fentyl methacrylate, methacrylic acid 1
-Methacrylates having an alkyl group having 8 to 20 carbon atoms or an alicyclic hydrocarbon group such as menthyl, adamantyl methacrylate, dimethyladamantyl methacrylate; methyl acrylate, ethyl acrylate, isopropyl acrylate, butyl acrylate Acrylates such as t-butyl acrylate, amyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate; styrene, α-methylstyrene, Vinyl aromatics such as paramethylstyrene, isopropenylstyrene and vinyltoluene; unsaturated nitriles such as acrylonitrile and methacrylonitrile;
Unsaturated carboxylic acids such as methacrylic acid, acrylic acid, and maleic anhydride; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Examples include, but are not limited to, polyunsaturated compounds such as divinylbenzene, and these may be used alone or in combination of two or more.
【００１０】使用される単量体の組成は、通常メタクリ
ル酸メチル６０〜１００質量部に対し他の共重合可能な
ビニル系モノマー４０〜０質量部の範囲であるが、改質
目的によっては共重合可能なビニル系モノマーの使用量
を、重合して得られるメタクリル樹脂本来の物性を損な
わない程度の使用量として１０質量部以下にすることが
好ましい。The composition of the monomer used is usually in the range of 60 to 100 parts by mass of methyl methacrylate and 40 to 0 parts by mass of another copolymerizable vinyl monomer. The amount of the polymerizable vinyl monomer used is preferably 10 parts by mass or less as an amount that does not impair the intrinsic physical properties of the methacrylic resin obtained by polymerization.
【００１１】本発明においては上記単量体混合物が重合
に供せられるが、この単量体混合物中にこの単量体混合
物の重合物を含有する部分重合体（以下、シラップとい
う）を単量体混合物の代わりに重合に供しても何等差し
支えない。In the present invention, the above-mentioned monomer mixture is subjected to polymerization, and a partial polymer (hereinafter, referred to as syrup) containing a polymer of this monomer mixture is added to the monomer mixture in a single amount. Anything can be used for the polymerization instead of the body mixture.
【００１２】この単量体混合物またはシラップには、通
常のメタクリル樹脂あるいはその変性品を製造する際に
用いられる種々の添加剤を加えることもできる。ここで
いう添加剤としては、着色に用いられる染料、顔料；酸
化防止剤、紫外線吸収剤等の安定剤；難燃剤、連鎖移動
剤、架橋剤等が挙げられる。To the monomer mixture or syrup, various additives used in producing ordinary methacrylic resins or modified products thereof can be added. Examples of the additives include dyes and pigments used for coloring; stabilizers such as antioxidants and ultraviolet absorbers; flame retardants, chain transfer agents, and crosslinking agents.
【００１３】本発明で用いる２−エチルヘキシルアシッ
ドフォスフェートとは、C8H17OP(O)(OH)2で表わされる
モノエステル、(C8H17)2OP(O)OHで表わされるジエステ
ルまたはこれらの混合物であり、混合物であることが好
ましい。モノエステルとジエステルとの混合比率は１対
９〜９対１が好ましく、３対７〜７対３がより好まし
く、５対５が更に好ましい。アルキル鎖の炭素数が７以
下のものは製造用鋳型を汚染し、炭素数が９以上のもの
は離型性を悪化させることがある。また、２−エチルヘ
キシルアシッドフォスフェートの使用量は、単量体混合
物またはシラップ１００質量部に対して０．００１〜
０．０５質量部の範囲で用いるのが好ましい。その使用
量が０．００１質量部未満では樹脂板の鋳型から高温剥
離する際の離型性が十分でなく、また、使用量が０．０
５質量部を超えると得られるメタクリル系樹脂板の吸水
率の増加や樹脂表面に悪影響を与えることがある。The 2-ethylhexyl acid phosphate used in the present invention is a monoester represented by C 8 H 17 OP (O) (OH) 2 or a diester represented by (C 8 H 17 ) 2 OP (O) OH. Or a mixture thereof, and preferably a mixture. The mixing ratio of the monoester and the diester is preferably 1: 9 to 9: 1, more preferably 3: 7 to 7: 3, and even more preferably 5: 5. When the alkyl chain has 7 or less carbon atoms, the production mold is contaminated, and when the alkyl chain has 9 or more carbon atoms, the mold releasability may be deteriorated. The amount of 2-ethylhexyl acid phosphate used is 0.001 to 100 parts by mass of the monomer mixture or syrup.
Preferably, it is used in the range of 0.05 parts by mass. If the amount used is less than 0.001 part by mass, the releasability at the time of high temperature peeling from the mold of the resin plate is not sufficient, and the amount used is 0.0%.
If the amount exceeds 5 parts by mass, the water absorption of the obtained methacrylic resin plate may increase and the resin surface may be adversely affected.
【００１４】本発明で用いるスルホ琥珀酸エステル塩と
しては、スルホ琥珀酸ジ（２−エチルヘキシル）ナトリ
ウム、スルホ琥珀酸ジヘキシルナトリウム、スルホ琥珀
酸ジブチルナトリウム等が挙げられる。スルホ琥珀酸エ
ステル塩は、一般にナトリウム塩のものが多用される
が、ナトリウム塩以外のものも使用できる。スルホ琥珀
酸エステル塩の使用量は単量体混合物またはシラップ１
００質量部に対して０．００２〜０．１質量部の範囲で
用いるのが好ましい。その使用量が０．００２質量部未
満では樹脂板の鋳型から高温剥離する際の離型性が十分
でなく、また、使用量が０．１質量部を超えると得られ
るメタクリル系樹脂板の表面に悪影響を与えることがあ
る。Examples of the sulfosuccinate ester salt used in the present invention include di (2-ethylhexyl) sodium sulfosuccinate, dihexyl sodium sulfosuccinate, dibutyl sodium sulfosuccinate and the like. As the sulfosuccinate salt, a sodium salt is generally widely used, but a salt other than the sodium salt can also be used. The amount of sulfosuccinate used is monomer mixture or syrup 1
It is preferably used in the range of 0.002 to 0.1 parts by mass with respect to 00 parts by mass. If the amount used is less than 0.002 parts by mass, the releasability at the time of high temperature peeling from the mold of the resin plate is not sufficient, and if the amount used exceeds 0.1 parts by mass, the surface of the methacrylic resin plate obtained is May be adversely affected.
【００１５】本発明で用いられるラジカル重合開始剤と
しては、アゾビスイソブチロニトリル、２，２’−アゾ
ビス−（２，４−ジメチルバレロニトリル）等のアゾ系
重合開始剤、ベンゾイルパーオキサイド、ｔ−ブチルパ
ーオキシ２−エチルヘキサノエート、ｔ−ヘキシルパー
オキシピバレート等の有機過酸化物等が挙げられる。ま
た、必要に応じて用いられる分子量調節剤としては、ｎ
−ブチルメルカプタン、ｎ−ドデシルメルカプタン、オ
クチルメルカプタン等のアルキルメルカプタン等が挙げ
られる。The radical polymerization initiator used in the present invention includes azo-based polymerization initiators such as azobisisobutyronitrile and 2,2′-azobis- (2,4-dimethylvaleronitrile), benzoyl peroxide, Organic peroxides such as t-butylperoxy 2-ethylhexanoate and t-hexylperoxypivalate are exemplified. In addition, as the molecular weight regulator used as needed, n
And alkyl mercaptans such as -butyl mercaptan, n-dodecyl mercaptan and octyl mercaptan.
【００１６】本発明における重合温度は、使用する重合
開始剤の種類により異なるが、一般に４０〜１７０℃で
あり、第１段目を４０〜９０℃、第２段目を１００〜１
４０℃とする２段階の重合温度で重合するのが好まし
い。The polymerization temperature in the present invention varies depending on the type of polymerization initiator used, but is generally 40 to 170 ° C., the first stage being 40 to 90 ° C., and the second stage being 100 to 1 to 100 ° C.
The polymerization is preferably carried out at a two-stage polymerization temperature of 40 ° C.
【００１７】重合硬化物を鋳型から取り出す際の温度
（以下、剥離温度という）は、樹脂組成物の組成によっ
ても多少異なるが、７０〜１１０℃の範囲が好ましい。
剥離温度が７０℃未満では樹脂表面に小さなキズを生じ
る場合がある。剥離温度は７５℃以上であることがより
好ましく、８０℃以上であることがさらに好ましい。ま
た、１１０℃を超えると樹脂表面にスジ状の欠陥が生じ
るので、メタクリル樹脂の優れた透明性・光学特性を失
う場合がある。The temperature at which the polymerized cured product is removed from the mold (hereinafter referred to as the peeling temperature) varies somewhat depending on the composition of the resin composition, but is preferably in the range of 70 to 110 ° C.
If the peeling temperature is lower than 70 ° C., small scratches may be generated on the resin surface. The peeling temperature is more preferably at least 75 ° C, further preferably at least 80 ° C. On the other hand, when the temperature exceeds 110 ° C., streak-like defects occur on the resin surface, so that the excellent transparency and optical characteristics of the methacrylic resin may be lost.
【００１８】本発明のメタクリル系樹脂板は、上記の単
量体混合物またはシラップに、ラジカル重合開始剤、酸
性アルキルリン酸エステルおよびスルホ琥珀酸エステル
塩を添加混合した後、鋳型、例えば強化ガラス、クロム
メッキ板、ステンレス板等の板状体と軟質塩化ビニル等
のガスケットで構成したものや、相対して同一方向へ同
一速度で走行する２枚のエンドレスベルトと、その相対
する面側の両端部において両エンドレスベルトと同一速
度で走行するガスケットとで構成され、２枚のエンドレ
スベルトの間隙があらかじめ設定されたものの中に注入
して重合することにより製造することができる。本発明
の製造方法は金属製の鋳型を用いた場合に効果が高く、
特にエンドレスベルト装置による製造の場合に効果が高
い。エンドレスベルト装置で製造する場合は、その２枚
のエンドレスベルトは常圧〜０．１Ｍｐａの圧力で加圧
されていることが好ましい。The methacrylic resin plate of the present invention is obtained by adding a radical polymerization initiator, an acidic alkyl phosphate ester and a sulfosuccinate ester salt to the above-mentioned monomer mixture or syrup, and then mixing the resulting mixture with a mold, for example, a tempered glass. A chrome-plated plate, a plate made of stainless steel, etc. and a gasket made of soft vinyl chloride, etc., or two endless belts running in the same direction and at the same speed, and both ends on the opposite surface side And a gasket running at the same speed. The gap between the two endless belts is injected into a preset belt and polymerized. The production method of the present invention is highly effective when using a metal mold,
In particular, the effect is high in the case of manufacturing with an endless belt device. In the case of manufacturing with an endless belt device, the two endless belts are preferably pressurized at a pressure of normal pressure to 0.1 Mpa.
【００１９】[0019]
【実施例】以下、実施例により本発明を詳しく説明する
が、本発明はこれらに限定されるものではない。なお、
実施例における物性評価は下記の方法に基づいて行っ
た。 １）高温離型性 メタクリル系樹脂板を重合した後、鋳型から各実施例記
載の温度で重合硬化物を取り出した際の鋳型からの離型
性を下記の基準により評価した。 良好：鋳型から樹脂板を剥離する際、なめらかに剥離で
きる。 不良：鋳型から樹脂板を剥離する際、途中に引っ掛かり
があり、表面欠陥を生ずる。 ２）鋳型汚染性 メタクリル系樹脂板の重合を、途中に鋳型を洗浄せず
に、同一鋳型で繰り返し２０回重合した後に、暗所の照
明下で鋳型表面の汚染状況を観察した。 ３）樹脂板外観 鋳型から取り出したメタクリル系樹脂板の外観を、暗所
の照明下で観察した。 実施例１ 冷却管、温度計及び撹拌機を備えた反応機に、メタクリ
ル酸メチル９３質量部およびアクリル酸ブチル７質量部
供給し、分子量調節剤としてｎ−ドデシルメルカプタン
を６３０ｐｐｍ添加した後、撹拌しながら加熱し内温が
８０℃になった時点で２，２’−アゾビス−（２，４−
ジメチルバレロニトリル）５００ｐｐｍを添加し、更に
内温９０℃まで加熱し１３分間保持した後、室温まで冷
却して重合率約２６％、２０℃における粘度２Ｐａ・ｓ
のシラップを得た。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In addition,
Evaluation of the physical properties in the examples was performed based on the following methods. 1) High-Temperature Releasability After the methacrylic resin plate was polymerized, the releasability from the mold when the polymerized cured product was taken out from the mold at the temperature described in each example was evaluated according to the following criteria. Good: When peeling the resin plate from the mold, it can be peeled smoothly. Poor: When the resin plate is peeled off from the mold, it is caught in the middle and causes surface defects. 2) Contamination of the mold The polymerization of the methacrylic resin plate was repeated 20 times with the same mold without washing the mold in the middle, and the contamination on the mold surface was observed under illumination in a dark place. 3) Appearance of resin plate The appearance of the methacrylic resin plate taken out of the mold was observed under illumination in a dark place. Example 1 To a reactor equipped with a cooling pipe, a thermometer and a stirrer, 93 parts by mass of methyl methacrylate and 7 parts by mass of butyl acrylate were supplied, and after adding 630 ppm of n-dodecyl mercaptan as a molecular weight regulator, the mixture was stirred. At the time when the internal temperature reached 80 ° C., 2,2′-azobis- (2,4-
(Dimethylvaleronitrile) 500 ppm, further heated to an internal temperature of 90 ° C. and maintained for 13 minutes, and then cooled to room temperature to obtain a polymerization rate of about 26% and a viscosity at 20 ° C. of 2 Pa · s.
I got a syrup.
【００２０】次いで、このシラップ１００質量部に、ｎ
−ドデシルメルカプタン０．０１質量部、ｔ−ヘキシル
パーオキシピバレート０．３２質量部、２−エチルヘキ
シルアシッドフォスフェート（モノエステルとジエステ
ルとの混合比率５対５）０．０１質量部およびスルホ琥
珀酸ジ（２−エチルヘキシル）ナトリウム０．００５質
量部を添加した後、撹拌し、ポリ塩化ビニル製ガスケッ
トを介して３ｍｍの間隔で相対する２枚のＳＵＳ３０４
板で形成した鋳型に注入した。７８℃の温水中に３０分
間浸漬し重合硬化させた後、１３５℃の空気加熱炉中で
６０分間熱処理し、８１℃に冷却した後、型枠を脱枠し
て板厚約３ｍｍのメタクリル系樹脂板を得た。この樹脂
板の製造を、鋳型を洗浄せず２０回繰り返したところ、
毎回の高温剥離性は問題なく、外観良好な樹脂板が得ら
れた。また、鋳型の汚染も無かった。Next, 100 parts by mass of this syrup was added with n
-0.01 parts by mass of dodecyl mercaptan, 0.32 parts by mass of t-hexyl peroxypivalate, 0.01 parts by mass of 2-ethylhexyl acid phosphate (mixing ratio of monoester to diester 5 to 5) and sulfosuccinic acid After adding 0.005 parts by mass of sodium di (2-ethylhexyl), the mixture was stirred, and two pieces of SUS304 opposed to each other at a distance of 3 mm via a polyvinyl chloride gasket.
It was poured into a mold formed of plates. After immersion in hot water of 78 ° C. for 30 minutes for polymerization and curing, heat treatment in an air heating furnace at 135 ° C. for 60 minutes, cooling to 81 ° C., removal of the formwork, and a methacrylic material having a sheet thickness of about 3 mm A resin plate was obtained. When the production of this resin plate was repeated 20 times without washing the mold,
There was no problem with the high-temperature peelability each time, and a resin plate having a good appearance was obtained. There was no contamination of the mold.
【００２１】実施例２ 実施例１と同じ反応装置に、メタクリル酸メチル１００
質量部を供給し、撹拌しながら加熱して内温が８０℃に
なった時点で２，２’−アゾビス−（２，４−ジメチル
バレロニトリル）５００ｐｐｍを添加し、更に内温９０
℃まで加熱し８分間保持した後、室温まで冷却して重合
率約２２％、２０℃における粘度１．５Ｐａ・ｓのシラ
ップを得た。Example 2 In the same reactor as in Example 1, methyl methacrylate 100
When the internal temperature reached 80 ° C. while stirring and heating, 500 ppm of 2,2′-azobis- (2,4-dimethylvaleronitrile) was added, and the internal temperature was further increased to 90 ° C.
After heating to ℃ and holding for 8 minutes, it was cooled to room temperature to obtain a syrup having a polymerization rate of about 22% and a viscosity at 20 ° C of 1.5 Pa · s.
【００２２】次いで、このシラップ１００質量部に、
２，２’−アゾビス−（２，４−ジメチルバレロニトリ
ル）０．０８３質量部、２−エチルヘキシルアシッドフ
ォスフェート（モノエステルとジエステルとの混合比率
５対５）０．００５質量部およびスルホ琥珀酸ジ（２−
エチルヘキシル）ナトリウム０．０１質量部を添加した
後、攪拌し、実施例１と同様にして鋳型中に注入した。
重合硬化の後、熱処理を行い１００℃に冷却後、型枠を
脱枠して板厚約３ｍｍのメタクリル系樹脂板を得た。こ
の製板操作を途中鋳型を洗浄せずに２０回繰り返したと
ころ、毎回の高温離型性は良好であり、外観良好な樹脂
板が得られ、鋳型の汚染も無かった。Next, to 100 parts by mass of the syrup,
0.083 parts by mass of 2,2′-azobis- (2,4-dimethylvaleronitrile), 0.005 parts by mass of 2-ethylhexyl acid phosphate (mixing ratio of monoester to diester 5: 5) 0.005 part by mass and sulfosuccinic acid Di (2-
After adding 0.01 parts by mass of sodium ethylhexyl), the mixture was stirred and poured into a mold in the same manner as in Example 1.
After the polymerization and curing, a heat treatment was performed and the temperature was cooled to 100 ° C., and the mold was deframed to obtain a methacrylic resin plate having a plate thickness of about 3 mm. When this plate making operation was repeated 20 times without washing the mold during the process, the mold release property at each time was good, a resin plate having a good appearance was obtained, and there was no contamination of the mold.
【００２３】実施例３ 実施例２と同様のシラップ１００質量部に、２，２’−
アゾビス−（２，４−ジメチルバレロニトリル）０．０
８３質量部、２−エチルヘキシルアシッドフォスフェー
ト（モノエステルとジエステルとの比率５対５）０．０
０５質量部およびスルホ琥珀酸ジ（２−エチルヘキシ
ル）ナトリウム０．０１質量部を添加した後、攪拌し、
相対して同一方向へ同一速度で走行する幅１２００ｍ
ｍ、厚さ１ｍｍの鏡面仕上げしたＳＵＳ３０４製エンド
レスベルトと、その相対する面側の両端部において両エ
ンドレスベルトと同一速度で走行するポリ塩化ビニル製
ガスケットとで構成され、２枚のエンドレスベルトの間
隙があらかじめ３ｍｍの厚みになるように設定された鋳
型に定量ポンプを用いて一定流量で注入した。ベルトの
移動と共に７８℃の温水シャワーで３０分間重合硬化さ
せた後、遠赤外線ヒーターで１３５℃の熱処理を２０分
間行い、送風により１０分間かけて１００℃に冷却後、
ベルトから樹脂板を剥離して板厚約３ｍｍのメタクリル
系樹脂板を得た。この製板操作を途中にベルトの洗浄を
行なわずに２０周繰り返したところ、毎回の高温離型性
は問題なく、外観良好な樹脂板が得られ、またエンドレ
スベルトの汚染も無かった。Example 3 The same syrup as in Example 2 was added to 100 parts by mass of 2,2'-
Azobis- (2,4-dimethylvaleronitrile) 0.0
83 parts by mass, 2-ethylhexyl acid phosphate (ratio of monoester to diester 5: 5) 0.0
After adding 0.05 parts by mass and 0.01 parts by mass of di (2-ethylhexyl) sodium sulfosuccinate, the mixture was stirred,
1200m width running in the same direction and at the same speed
m, a 1 mm thick mirror-finished endless belt made of SUS304 and a gasket made of polyvinyl chloride running at the same speed as both endless belts at both ends on the opposite surface side, and a gap between the two endless belts Was injected at a constant flow rate using a metering pump into a mold previously set to have a thickness of 3 mm. After polymerizing and curing with a warm water shower at 78 ° C. for 30 minutes along with the movement of the belt, heat treatment at 135 ° C. was performed with a far-infrared heater for 20 minutes.
The methacrylic resin plate having a thickness of about 3 mm was obtained by peeling the resin plate from the belt. When this plate making operation was repeated 20 times without washing the belt in the middle, there was no problem with the high-temperature releasability each time, and a resin plate having a good appearance was obtained, and there was no contamination of the endless belt.
【００２４】実施例４ 実施例２と同様の方法でシラップを鋳型に仕込み、重合
硬化ののち熱処理を行い、５０℃に冷却した後鋳型から
樹脂板を取り出した。この製板操作を途中鋳型を洗浄せ
ずに２０回繰り返したところ、毎回の高温離型性は良好
であり、鋳型の汚染も無かったが、得られた樹脂板は、
樹脂板の熱収縮時にＳＵＳ３０４板と接触したことによ
る細かなキズがあった。Example 4 A syrup was charged into a mold in the same manner as in Example 2, heat-treated after polymerization and curing, cooled to 50 ° C., and the resin plate was taken out of the mold. When this plate making operation was repeated 20 times without washing the mold in the middle, the mold release property at each time was good and there was no contamination of the mold, but the obtained resin plate was
There were fine scratches due to contact with the SUS304 plate during thermal contraction of the resin plate.
【００２５】実施例５ 実施例３の剥離温度を５０℃にした以外は実施例３と同
様の方法で樹脂板を得る操作を繰り返した。この製板操
作を途中にベルトの洗浄を行なわずに２０周繰り返した
ところ、毎回の高温離型性は問題なく、エンドレスベル
トの汚染も無かったが、樹脂板が熱収縮時にエンドレス
ベルトと接触したことによる細かなキズが認められた。Example 5 The procedure of Example 3 was repeated except that the peeling temperature was changed to 50 ° C., and a procedure for obtaining a resin plate was repeated. When this plate making operation was repeated 20 times without washing the belt in the middle, there was no problem with the high-temperature release property each time and there was no contamination of the endless belt, but the resin plate came into contact with the endless belt during heat shrinkage. Minor scratches were observed.
【００２６】比較例１ ２−エチルヘキシルアシッドフォスフェートの代わりに
エチルアシッドフォスフェート０．０１質量部を用いた
以外は、実施例１と全く同様の方法で樹脂板の製造操作
を繰り返し実施した。その結果、高温離型性に問題は無
かったが、５回目の製板以降には鋳型が汚染されて洗浄
が必要な状態となり、洗浄せずに得られた樹脂板の表面
は白化して透明性が低下した。Comparative Example 1 A resin plate manufacturing operation was repeated in exactly the same manner as in Example 1, except that 0.01 parts by mass of ethyl acid phosphate was used instead of 2-ethylhexyl acid phosphate. As a result, there was no problem with the high-temperature release property, but after the fifth plate making, the mold was contaminated and required to be washed, and the surface of the resin plate obtained without washing became white and transparent. Sex decreased.
【００２７】比較例２ ２−エチルヘキシルアシッドフォスフェートの代わりに
オクタデシルアシッドフォスフェート０．０１質量部を
用いた以外は、実施例１と同様にして鋳型内にシラップ
を仕込み、重合硬化の後、熱処理を行った。８１℃に冷
却した後、鋳型から硬化物を取り出そうとしたところ、
ポリ塩化ビニル製ガスケット付近の樹脂がＳＵＳ３０４
板と接着し、高温離型性が不良であり、得られた樹脂板
もスジ状の欠陥を有するものとなった。Comparative Example 2 A syrup was charged into a mold in the same manner as in Example 1 except that 0.01 parts by mass of octadecyl acid phosphate was used in place of 2-ethylhexyl acid phosphate. Was done. After cooling to 81 ° C, when I tried to remove the cured product from the mold,
The resin near the gasket made of polyvinyl chloride is SUS304
It adhered to the plate and the high-temperature releasability was poor, and the resulting resin plate also had streak-like defects.
【００２８】比較例３ 実施例２で用いたスルホ琥珀酸ジ（２−エチルヘキシ
ル）ナトリウムを添加しなかった以外は、実施例２と全
く同様にしてシラップを鋳型に仕込み、重合硬化ののち
熱処理を行い１００℃に冷却した後、鋳型から樹脂板を
取り出した。その結果、得られた樹脂板は高温離型性不
良によるスジ状欠陥が生じており、メタクリル系樹脂の
特徴である優れた透明性・光学特性を失っていた。Comparative Example 3 A syrup was charged into a mold in exactly the same manner as in Example 2, except that the sodium di (2-ethylhexyl) sulfosuccinate used in Example 2 was not added. After cooling to 100 ° C., the resin plate was taken out of the mold. As a result, the obtained resin plate had streak-like defects due to poor high-temperature releasability, and lost the excellent transparency and optical characteristics characteristic of methacrylic resin.
【００２９】[0029]
【発明の効果】本発明によれば、高温での鋳型からの取
り出しが可能で、透明性に優れ、外観欠陥のないメタク
リル系樹脂板が収率良く製造できる。また、繰り返し使
用する製造用鋳型が汚染されることがない。According to the present invention, a methacrylic resin plate which can be taken out of a mold at a high temperature, has excellent transparency, and has no appearance defect can be produced with high yield. Further, the production mold used repeatedly is not contaminated.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｊ 5/00 ＣＥＹ Ｃ０８Ｊ 5/00 ＣＥＹ Ｃ０８Ｋ 5/42 Ｃ０８Ｋ 5/42 5/521 5/521 // Ｂ２９Ｋ 33:04 Ｂ２９Ｋ 33:04 Ｂ２９Ｌ 7:00 Ｂ２９Ｌ 7:00 (72)発明者 沢野 哲哉 富山県富山市海岸通３番地 三菱レイヨン 株式会社富山事業所内 Ｆターム(参考） 4F071 AA33 AF30 AH19 BA02 BB01 BB02 BC01 BC03 4F204 AA21E AB04 AB22 AG01 EA03 EA04 EB01 EB02 EE02 EE23 EF01 4J002 BG061 EV257 EW046 FD166 FD167 4J011 GA03 GB01 PA45 PA46 PA69 PB32 PC02 PC15 4J100 AB01Q AB02Q AB03Q AB04Q AB16Q AJ02Q AK32Q AL03P AL03Q AL04Q AL05Q AL08Q AL11Q AL62Q AL66Q AM02Q BA02Q BC04Q BC07Q BC08Q BC09Q BC43Q CA01 CA04 DA62 JA00 JA32 ──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) C08J 5/00 CEY C08J 5/00 CEY C08K 5/42 C08K 5/42 5/521 5/521 // B29K 33:04 B29K 33:04 B29L 7:00 B29L 7:00 (72) Inventor Tetsuya Sawano 3 Kaigandori, Toyama City, Toyama Prefecture Mitsubishi Rayon Co., Ltd. Toyama Works F-term (reference) 4F071 AA33 AF30 AH19 BA02 BB01 BB02 BC01 BC03 4F204 AA21E AB04 AB22 AG01 EA03 EA04 EB01 EB02 EE02 EE23 EF01 4J002 BG061 EV257 EW046 FD166 FD167 4J011 GA03 GB01 PA45 PA46 PA69 PB32 PC02 PC15 4J100 AB01Q AB02Q AB03Q AB04Q AB16QAQQ BC16QAQQ BC43Q CA01 CA04 DA62 JA00 JA32
Claims (3)
００質量％と他の共重合可能なビニル系モノマー単位４
０〜０質量％とからなる重合体１００質量部に対して、
０．００１〜０．０５質量部の２−エチルヘキシルアシ
ッドフォスフェートおよび０．００２〜０．１質量部の
スルホ琥珀酸エステル塩が添加されてなるメタクリル系
樹脂組成物。1. Methyl methacrylate monomer unit 60-1
00% by mass and another copolymerizable vinyl monomer unit 4
With respect to 100 parts by mass of a polymer consisting of 0 to 0% by mass,
A methacrylic resin composition comprising 0.001 to 0.05 parts by mass of 2-ethylhexyl acid phosphate and 0.002 to 0.1 parts by mass of a sulfosuccinate salt.
と他の共重合可能なビニル系モノマー４０〜０質量％と
からなる単量体混合物または該単量体混合物と該単量体
混合物の重合体との混合物１００質量部、２−エチルヘ
キシルアシッドフォスフェート０．００１〜０．０５質
量部およびスルホ琥珀酸エステル塩０．００２〜０．１
質量部を、ラジカル重合開始剤の存在下、鋳型内で重合
し、重合硬化物を７０〜１１０℃の温度下で鋳型から取
り出すことを特徴とするメタクリル系樹脂成形品の製造
方法。2. 60 to 100% by weight of methyl methacrylate
Of 100% by mass of a monomer mixture composed of 40% by mass and 40% by mass of another copolymerizable vinyl monomer, or a mixture of the monomer mixture and a polymer of the monomer mixture, 2-ethylhexyl acid phosphate 0.001 to 0.05 parts by mass and sulfosuccinate ester salt 0.002 to 0.1
A method for producing a methacrylic resin molded product, characterized in that a mass part is polymerized in a mold in the presence of a radical polymerization initiator, and a polymer cured product is taken out from the mold at a temperature of 70 to 110 ° C.
走行する２枚のエンドレスベルトと、エンドレスベルト
の相対する面側の両端部においてエンドレスベルトと同
一速度で走行するガスケットとで構成され、２枚のエン
ドレスベルトの間隙があらかじめ設定されたものである
請求項２のメタクリル系樹脂成形品の製造方法。3. A mold comprises two endless belts running at the same speed in the same direction and a gasket running at the same speed as the endless belts at both ends of the endless belt facing each other. 3. The method for producing a methacrylic resin molded product according to claim 2, wherein a gap between the two endless belts is set in advance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35773399A JP3865554B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing methacrylic resin molded product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35773399A JP3865554B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing methacrylic resin molded product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2001172462A true JP2001172462A (en) | 2001-06-26 |
| JP3865554B2 JP3865554B2 (en) | 2007-01-10 |
Family
ID=18455649
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35773399A Expired - Fee Related JP3865554B2 (en) | 1999-12-16 | 1999-12-16 | Method for producing methacrylic resin molded product |
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| Country | Link |
|---|---|
| JP (1) | JP3865554B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006290620A (en) * | 2005-03-15 | 2006-10-26 | Mitsubishi Rayon Co Ltd | Sheet-shaped article washing method, sheet-shaped article washing device using therefor, and manufacturing method of plate polymer |
| CN114854477A (en) * | 2022-04-27 | 2022-08-05 | 重庆渝江压铸有限公司 | Silicon-free mold release agent with excellent mold release performance and preparation method thereof |
-
1999
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006290620A (en) * | 2005-03-15 | 2006-10-26 | Mitsubishi Rayon Co Ltd | Sheet-shaped article washing method, sheet-shaped article washing device using therefor, and manufacturing method of plate polymer |
| CN114854477A (en) * | 2022-04-27 | 2022-08-05 | 重庆渝江压铸有限公司 | Silicon-free mold release agent with excellent mold release performance and preparation method thereof |
| CN114854477B (en) * | 2022-04-27 | 2023-08-08 | 重庆渝江压铸有限公司 | Silicon-free release agent with excellent release performance and preparation method thereof |
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