JP2009179691A - Method for producing methacrylic resin composition - Google Patents
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本発明は、メタクリル樹脂と金属酸化物粒子とを含有するメタクリル樹脂組成物の製造方法に関する。 The present invention relates to a method for producing a methacrylic resin composition containing a methacrylic resin and metal oxide particles.
メタクリル樹脂と金属酸化物粒子とを含有するメタクリル樹脂組成物は、メタクリル樹脂の優れた透明性に加え、高い表面硬度を有しうるため、例えば、学校・病院等の安全窓ガラス、携帯電話等の窓材、表示板、ディスプレイパネル、防音板、間仕切り等の材料として有望視されている。そして、該メタクリル樹脂組成物が優れた透明性を持ちつつ、高い表面硬度を獲得するには、金属酸化物粒子をメタクリル樹脂中に良好に分散させる必要があることが知られている。 A methacrylic resin composition containing a methacrylic resin and metal oxide particles can have high surface hardness in addition to the excellent transparency of the methacrylic resin. For example, safety window glass such as a school / hospital, a mobile phone, etc. It is promising as a material for window materials, display boards, display panels, soundproof boards, partitions, etc. In order to obtain high surface hardness while the methacrylic resin composition has excellent transparency, it is known that the metal oxide particles need to be well dispersed in the methacrylic resin.
一方、メタクリル樹脂と金属酸化物粒子とを含有するメタクリル樹脂組成物の製造方法として、非特許文献１には、メタクリル樹脂と（３−アクリロキシ）トリメトキシシランで表面処理されたシリカ粒子とをシングルスクリュー混練機により混練する方法が記載されている。また、非特許文献２には、オクタデシルメチルベタインによりイオン交換された親油性のモンモリロナイトを、メタクリル酸メチルモノマー中に加えた後、超音波処理して該モノマー中に分散させ、次いで重合反応を行う方法が記載されている。 On the other hand, as a method for producing a methacrylic resin composition containing a methacrylic resin and metal oxide particles, Non-Patent Document 1 discloses a single methacrylic resin and silica particles surface-treated with (3-acryloxy) trimethoxysilane. A method of kneading with a screw kneader is described. Further, in Non-Patent Document 2, lipophilic montmorillonite ion-exchanged with octadecylmethylbetaine is added to methyl methacrylate monomer, and then subjected to ultrasonic treatment to be dispersed in the monomer, followed by polymerization reaction. A method is described.
しかしながら、非特許文献１に記載の方法では、メタクリル樹脂中に金属酸化物粒子であるシリカ粒子を分散させるために所定の化合物でシリカ粒子を表面処理する必要があり、操作が煩雑であった。また、メタクリル樹脂と該シリカ粒子を所定の混練機で機械的に混練するため、分散性の点で必ずしも満足のいくものではなかった。 However, in the method described in Non-Patent Document 1, it is necessary to surface-treat the silica particles with a predetermined compound in order to disperse the silica particles that are metal oxide particles in the methacrylic resin, and the operation is complicated. Further, since the methacrylic resin and the silica particles are mechanically kneaded with a predetermined kneader, the dispersibility is not always satisfactory.
また、非特許文献２に記載の方法では、メタクリル酸メチルモノマー中にモンモリロナイトを分散させるために所定の化合物でモンモリロナイトを処理する必要があり、また、該モノマーと該モンモリロナイトとの混合物を超音波処理した後、重合反応を行うため、操作が煩雑であった。 Further, in the method described in Non-Patent Document 2, it is necessary to treat montmorillonite with a predetermined compound in order to disperse montmorillonite in a methyl methacrylate monomer, and ultrasonically treat the mixture of the monomer and the montmorillonite. Then, since the polymerization reaction was performed, the operation was complicated.
そこで、本発明の目的は、金属酸化物粒子をメタクリル樹脂中に簡便かつ良好に分散させ、良好な透明性と表面硬度を有するメタクリル樹脂組成物を製造しうる方法を提供することにある。 Accordingly, an object of the present invention is to provide a method capable of producing a methacrylic resin composition having good transparency and surface hardness by simply and satisfactorily dispersing metal oxide particles in a methacrylic resin.
かかる状況の下、本発明者らは鋭意検討の結果、メタクリル樹脂が炭素数２〜４の１価アルコール及び水の混合溶媒に溶解してなる溶液と、金属酸化物粒子とを混合することにより、簡便かつ良好に金属酸化物粒子を分散させることができ、該混合物から前記溶媒を除去することで、良好な透明性と表面硬度を有するメタクリル樹脂組成物を製造できることを見出し、本発明を完成するに至った。 Under such circumstances, as a result of intensive studies, the present inventors have mixed a solution in which a methacrylic resin is dissolved in a mixed solvent of a monohydric alcohol having 2 to 4 carbon atoms and water with metal oxide particles. The present invention has been completed by finding that a methacrylic resin composition having good transparency and surface hardness can be produced by easily and satisfactorily dispersing metal oxide particles and removing the solvent from the mixture. It came to do.
すなわち本発明は、メタクリル樹脂が炭素数２〜４の１価アルコール及び水の混合溶媒に溶解してなる溶液と、金属酸化物粒子とを混合した後、該混合物から前記溶媒を除去することを特徴とするメタクリル樹脂組成物の製造方法を提供するものである。 That is, the present invention is to remove the solvent from the mixture after mixing a solution obtained by dissolving a methacrylic resin in a mixed solvent of monohydric alcohol having 2 to 4 carbon atoms and water with metal oxide particles. The manufacturing method of the characteristic methacrylic resin composition is provided.
本発明によれば、金属酸化物粒子をメタクリル樹脂中に簡便かつ良好に分散させ、良好な透明性と表面硬度を有するメタクリル樹脂組成物を製造することができる。 According to the present invention, metal oxide particles can be easily and satisfactorily dispersed in a methacrylic resin to produce a methacrylic resin composition having good transparency and surface hardness.
以下、本発明を詳細に説明する。本発明では、メタクリル樹脂が炭素数２〜４の１価アルコール及び水の混合溶媒に溶解してなる溶液と、金属酸化物粒子とを混合する。このように、メタクリル樹脂が所定のアルコール及び水の混合溶媒には溶解するという特性を利用し、分散性よく該溶液と金属酸化物粒子とを混合するものである。 Hereinafter, the present invention will be described in detail. In the present invention, a solution in which a methacrylic resin is dissolved in a mixed solvent of a monohydric alcohol having 2 to 4 carbon atoms and water is mixed with metal oxide particles. As described above, the solution and the metal oxide particles are mixed with good dispersibility by utilizing the property that the methacrylic resin dissolves in a predetermined solvent mixture of alcohol and water.
本発明で使用するメタクリル樹脂は、メタクリル酸メチルを主体とする重合体であり、メタクリル酸メチルの単独重合体であってもよいし、メタクリル酸メチル５０重量％以上とこれ以外の単量体５０重量％以下との共重合体であってもよい。共重合体である場合、メタクリル酸メチルの割合は、好ましくは７０重量％以上であり、より好ましくは９０重量％以上である。尚、上述したメタクリル酸メチルの割合は、メタクリル樹脂が上記混合溶媒に溶解する範囲内で適宜調整される。 The methacrylic resin used in the present invention is a polymer mainly composed of methyl methacrylate, and may be a homopolymer of methyl methacrylate, 50% by weight or more of methyl methacrylate, and other monomers 50 It may be a copolymer with a weight percent or less. In the case of a copolymer, the proportion of methyl methacrylate is preferably 70% by weight or more, more preferably 90% by weight or more. In addition, the ratio of the methyl methacrylate mentioned above is suitably adjusted within the range which a methacryl resin melt | dissolves in the said mixed solvent.
メタクリル酸メチル以外の単量体は、分子内にラジカル重合可能な二重結合を１個以上有するものであり、メタクリル酸メチル以外の（メタ）アクリル酸エステルや、（メタ）アクリル酸、ビニルスルホン酸が好ましく用いられる。メタクリル酸メチル以外の（メタ）アクリル酸エステルの例としては、アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸ベンジル、（メタ）アクリル酸２−エチルヘキシル等が挙げられる。 Monomers other than methyl methacrylate have one or more double bonds capable of radical polymerization in the molecule, such as (meth) acrylic acid esters other than methyl methacrylate, (meth) acrylic acid, vinyl sulfone. An acid is preferably used. Examples of (meth) acrylic esters other than methyl methacrylate include methyl acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate and the like.
メタクリル樹脂は、耐衝撃剤、帯電防止剤、酸化防止剤、滑剤、離型剤、染料、顔料などの着色剤を含有してもよい。 The methacrylic resin may contain a colorant such as an impact resistance agent, an antistatic agent, an antioxidant, a lubricant, a release agent, a dye, and a pigment.
炭素数２〜４の１価アルコールとしては、例えば、エタノール、１−プロパノール、イソプロパノール、１−ブタノール、２−ブタノール、２−メチル−１−プロパノール、２−メチル−２−プロパノールが挙げられる。また、必要に応じてそれらの２種以上を用いることもできる。 Examples of the monohydric alcohol having 2 to 4 carbon atoms include ethanol, 1-propanol, isopropanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, and 2-methyl-2-propanol. Moreover, those 2 or more types can also be used as needed.
炭素数２〜４の１価アルコール及び水の使用量は、メタクリル樹脂が該アルコール及び水の混合溶媒に溶解しうる量であれば特に制限はなく、メタクリル樹脂１重量部に対して、該混合溶媒は通常１〜４０重量部、好ましくは５〜３０重量部である。 The amount of monohydric alcohol having 2 to 4 carbon atoms and water used is not particularly limited as long as the methacrylic resin can be dissolved in a mixed solvent of the alcohol and water. A solvent is 1-40 weight part normally, Preferably it is 5-30 weight part.
炭素数２〜４の１価アルコール及び水の使用割合については、該アルコールと水とが均一に交じり合うよう適宜調整され、好ましくは、該アルコール及び水の合計１００重量部に対して、該アルコールは６０〜９７重量部である。 About the usage rate of C2-C4 monohydric alcohol and water, it adjusts suitably so that this alcohol and water may mix uniformly, Preferably, this alcohol and water with respect to a total of 100 weight part, this alcohol Is 60 to 97 parts by weight.
メタクリル樹脂を炭素数２〜４の１価アルコール及び水の混合溶媒に溶解させる温度は、使用するアルコールにもよるが、通常１０〜９０℃、好ましくは２０〜８０℃である。 The temperature at which the methacrylic resin is dissolved in the mixed solvent of monohydric alcohol having 2 to 4 carbon atoms and water is usually 10 to 90 ° C, preferably 20 to 80 ° C, although it depends on the alcohol used.
メタクリル樹脂を上記混合溶媒に溶解させるのに要する時間は、通常０．５〜４０時間程度である。 The time required for dissolving the methacrylic resin in the mixed solvent is usually about 0.5 to 40 hours.
かくしてメタクリル樹脂が炭素数２〜４の１価アルコール及び水の混合溶媒に溶解してなる溶液を得ることができる。次いで、この溶液と金属酸化物粒子とを混合する。 Thus, a solution in which the methacrylic resin is dissolved in a mixed solvent of monohydric alcohol having 2 to 4 carbon atoms and water can be obtained. Next, this solution and the metal oxide particles are mixed.
金属酸化物粒子は、メタクリル樹脂中に分散させて該樹脂といわゆる複合化しうる従来公知の金属酸化物粒子であることができる。かかる金属酸化物として、好ましくはシリカ、アルミナ、チタニア、ジルコニアが挙げられる。また、必要に応じてそれらの２種以上を用いることもできる。 The metal oxide particles can be conventionally known metal oxide particles that can be dispersed in a methacrylic resin and so-called complexed with the resin. Preferred examples of such metal oxide include silica, alumina, titania, and zirconia. Moreover, those 2 or more types can also be used as needed.
金属酸化物粒子の使用量は特に制限されないが、メタクリル樹脂１００重量部に対して、通常２００重量部以下、好ましくは１００重量部以下、更に好ましくは１〜５０重量部である。 The amount of metal oxide particles used is not particularly limited, but is usually 200 parts by weight or less, preferably 100 parts by weight or less, and more preferably 1 to 50 parts by weight with respect to 100 parts by weight of methacrylic resin.
金属酸化物粒子の中心粒子径は、動的光散乱法により測定することができ、入手容易性の点から１ｎｍ以上が好ましく、得られるメタクリル樹脂組成物の透明性の点から１５０ｎｍ以下が好ましく、１００ｎｍ以下がより好ましい、２０ｎｍ以下がさらに好ましい。 The central particle diameter of the metal oxide particles can be measured by a dynamic light scattering method, preferably 1 nm or more from the viewpoint of availability, and preferably 150 nm or less from the transparency of the resulting methacrylic resin composition, 100 nm or less is more preferable, and 20 nm or less is more preferable.
上記溶液と金属酸化物粒子とを混合する方法としては、例えば、金属酸化物粒子を上記溶液に加えてもよいし、金属酸化物粒子に上記溶液を加えてもよい。また、金属酸化物粒子を炭素数２〜４の１価アルコールに分散させてゾルとし、このゾルを上記溶液に加えてもよいし、このゾルに上記溶液を加えてもよい。また、上記溶液中のアルコールと、ゾル中のアルコールは同一であってもよく、異なっていてもよい。本発明で得られるメタクリル樹脂組成物の透明性や、金属酸化物粒子の分散性の点からは、上記ゾルを用いるのが好ましい。 As a method of mixing the solution and the metal oxide particles, for example, the metal oxide particles may be added to the solution, or the solution may be added to the metal oxide particles. Alternatively, the metal oxide particles may be dispersed in a monohydric alcohol having 2 to 4 carbon atoms to form a sol, and the sol may be added to the solution, or the solution may be added to the sol. The alcohol in the solution and the alcohol in the sol may be the same or different. From the viewpoint of the transparency of the methacrylic resin composition obtained in the present invention and the dispersibility of the metal oxide particles, it is preferable to use the sol.
上記溶液と金属酸化物粒子との混合温度は、メタクリル樹脂が上記混合溶媒に溶解している温度であればよく、使用するアルコールにもよるが、通常１０〜９０℃、好ましくは２０〜８０℃である。また、混合時間は、通常１〜２０時間、好ましくは１〜１０時間である。 The mixing temperature of the solution and the metal oxide particles may be a temperature at which the methacrylic resin is dissolved in the mixed solvent, and is usually 10 to 90 ° C, preferably 20 to 80 ° C, although it depends on the alcohol used. It is. Moreover, mixing time is 1 to 20 hours normally, Preferably it is 1 to 10 hours.
上述のとおり混合した後、該混合物から上記溶媒を除去する。除去方法としては、例えば、上記溶媒を蒸発させて乾燥する等、従来公知の方法を採用することができる。好ましくは、室温〜１２０℃程度で、数時間から数日間かけて蒸発させ、乾燥する。 After mixing as described above, the solvent is removed from the mixture. As a removal method, for example, a conventionally known method such as evaporation of the solvent and drying may be employed. Preferably, it is evaporated at room temperature to about 120 ° C. over several hours to several days and dried.
尚、上記溶液と金属酸化物粒子との混合物を一旦冷却してゲル化し、かかるゲルから上記溶媒を除去することもできる。 In addition, the mixture of the solution and the metal oxide particles can be once cooled to gel, and the solvent can be removed from the gel.
かくして金属酸化物粒子をメタクリル樹脂中に簡便かつ良好に分散させ、良好な透明性と表面硬度を有するメタクリル樹脂組成物を製造することができる。このメタクリル樹脂組成物は、例えば、プレス成形等、従来公知の成形法により成形することができる。 Thus, the metal oxide particles can be easily and satisfactorily dispersed in the methacrylic resin to produce a methacrylic resin composition having good transparency and surface hardness. This methacrylic resin composition can be molded by a conventionally known molding method such as press molding.
以下、実施例によって本発明をより詳細に説明するが、本発明は、かかる実施例によって限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by this Example.
尚、以下の実施例における各種物性の測定方法および評価方法は以下のとおりである。 In addition, the measuring method and evaluation method of various physical properties in the following examples are as follows.
（１）メタクリル樹脂組成物中の金属酸化物粒子の含有率
メタクリル樹脂組成物を一定量（Ｗ０）秤取り、ＴＧＡ（熱重量分析装置）により室温（約２５℃）から１０℃／分の昇温速度で５００℃まで昇温し、５００℃に到達したときの重量（Ｗ１）を測定し、下記式（２）から金属酸化物粒子の含有率を算出した。
金属酸化物粒子の含有率（％）＝（Ｗ１／Ｗ０）×１００ （２）
(1) Content of metal oxide particles in methacrylic resin composition A fixed amount (W0) of a methacrylic resin composition is weighed, and increased by 10 ° C / min from room temperature (about 25 ° C) using a TGA (thermogravimetric analyzer). The temperature was raised to 500 ° C. at a temperature rate, the weight (W1) when reaching 500 ° C. was measured, and the content of the metal oxide particles was calculated from the following formula (2).
Metal oxide particle content (%) = (W1 / W0) × 100 (2)
（２）全光線透過率
ＪＩＳ Ｋ７３６１−１に準拠して、村上色彩技術研究所製ＨＲ−１００を用いて全光線透過率（％）を求めた。
(2) Total light transmittance Based on JIS K7361-1, total light transmittance (%) was calculated | required using Murakami Color Research Laboratory HR-100.
（３）ヘイズ値
ＪＩＳ Ｋ７１３６：２０００に準拠して、村上色彩技術研究所製ＨＲ−１００を用いてヘイズ値を測定した。
(3) Haze value Based on JIS K7136: 2000, the haze value was measured using HR-100 made by Murakami Color Research Laboratory.
（４）鉛筆硬度
ＪＩＳ Ｋ５４００の鉛筆硬度試験に従い、厚さ２ｍｍの平板状に成形した成形品を試験片として鉛筆硬度試験を行い、表面硬度（鉛筆硬度）を求めた。
(4) Pencil Hardness According to the pencil hardness test of JIS K5400, a pencil hardness test was performed using a molded product formed into a flat plate with a thickness of 2 mm as a test piece to obtain a surface hardness (pencil hardness).
実施例１
メタクリル酸メチル９６重量％及びアクリル酸メチル４重量％が重合してなる共重合体樹脂ペレット（重量平均分子量；１２万）８ｇを、エタノール１５０ｇ及び水４０ｇの混合溶媒に加えた後、６０℃で３時間攪拌混合し、該樹脂が溶解した溶液を得た。この溶液に、シリカがイソプロパノールに分散してなるゾル（シリカ含有率；３０重量％、シリカの中心粒子径；１０〜１５ｎｍ、日産化学社製）１０ｇを加え、６０℃で６時間攪拌混合した。該混合物を約０℃に冷却し、ゲル化した。このゲルを室温で１日間風乾した後、５０℃で２日間、くわえて１２０℃で３日間乾燥させ、メタクリル樹脂組成物を得た。この樹脂組成物をプレス成形加工機によりプレス成形し、厚さ２ｍｍのプレス板を得た。このプレス板の全光線透過率は７８．２％、ヘイズ値は７７．９％、シリカ含有率は１．９重量％、鉛筆硬度は４Ｈであった。
Example 1
After adding 8 g of copolymer resin pellets (weight average molecular weight; 120,000) obtained by polymerizing 96% by weight of methyl methacrylate and 4% by weight of methyl acrylate to a mixed solvent of 150 g of ethanol and 40 g of water, the mixture was heated at 60 ° C. The mixture was stirred for 3 hours to obtain a solution in which the resin was dissolved. To this solution, 10 g of a sol (silica content: 30% by weight, silica central particle size: 10 to 15 nm, manufactured by Nissan Chemical Co., Ltd.) in which silica is dispersed in isopropanol was added and mixed with stirring at 60 ° C. for 6 hours. The mixture was cooled to about 0 ° C. and gelled. The gel was air-dried at room temperature for 1 day and then dried at 50 ° C. for 2 days and additionally at 120 ° C. for 3 days to obtain a methacrylic resin composition. This resin composition was press-molded by a press molding machine to obtain a press plate having a thickness of 2 mm. The press plate had a total light transmittance of 78.2%, a haze value of 77.9%, a silica content of 1.9% by weight, and a pencil hardness of 4H.
実施例２
メタクリル酸メチル９６重量％及びアクリル酸メチル４重量％が重合してなる共重合体樹脂ペレット（重量平均分子量；１２万）８ｇを、イソプロパノール１５０ｇ及び水４０ｇの混合溶媒に加えた後、６５℃で３時間攪拌混合し、該樹脂が溶解した溶液を得た。この溶液に、シリカがイソプロパノールに分散してなるゾル（シリカ含有率；３０重量％、シリカの中心粒子径；１０〜１５ｎｍ、日産化学社製）１０ｇを加え、６５℃で６時間攪拌混合した。該混合物を約０℃に冷却し、ゲル化した。このゲルを室温で１日間風乾した後、５０℃で２日間、くわえて１２０℃で３日間乾燥させ、メタクリル樹脂組成物を得た。この樹脂組成物をプレス成形加工機によりプレス成形し、厚さ２ｍｍのプレス板を得た。このプレス板の全光線透過率は７９．８％、ヘイズ値は８２．６％、シリカ含有率は５重量％、鉛筆硬度は４Ｈであった。
Example 2
After adding 8 g of copolymer resin pellets (weight average molecular weight; 120,000) obtained by polymerizing 96% by weight of methyl methacrylate and 4% by weight of methyl acrylate to a mixed solvent of 150 g of isopropanol and 40 g of water, at 65 ° C. The mixture was stirred for 3 hours to obtain a solution in which the resin was dissolved. To this solution was added 10 g of a sol (silica content: 30% by weight, silica center particle size: 10 to 15 nm, manufactured by Nissan Chemical Co., Ltd.) in which silica was dispersed in isopropanol, and the mixture was stirred and mixed at 65 ° C. for 6 hours. The mixture was cooled to about 0 ° C. and gelled. The gel was air-dried at room temperature for 1 day and then dried at 50 ° C. for 2 days and additionally at 120 ° C. for 3 days to obtain a methacrylic resin composition. This resin composition was press-molded by a press molding machine to obtain a press plate having a thickness of 2 mm. The press plate had a total light transmittance of 79.8%, a haze value of 82.6%, a silica content of 5% by weight, and a pencil hardness of 4H.
実施例３
メタクリル酸メチル及びアクリル酸の混合物であって、メタクリル酸メチル９モルに対しアクリル酸１モルである混合物に、重合開始剤を加えた後、７３℃で３時間、１２０℃で１時間熱処理をして重合反応を行った。得られた重合物８ｇをイソプロパノール１５５ｇ及び水４０ｇの混合溶媒に加えた後、６５℃で６時間攪拌混合し、該樹脂が溶解した溶液を得た。この溶液に、シリカがイソプロパノールに分散してなるゾル（シリカ含有率；３０重量％、シリカの中心粒子径；１０〜１５ｎｍ、日産化学社製）５ｇを加え、６５℃で６時間攪拌混合した。該混合物を約０℃に冷却し、ゲル化した。このゲルを室温で２日間風乾した後、５０℃で２日間、くわえて１２０℃で３日間乾燥させ、メタクリル樹脂組成物を得た。この樹脂組成物をプレス成形加工機によりプレス成形し、厚さ２ｍｍのプレス板を得た。このプレス板の全光線透過率は７２．５％、ヘイズ値は５４．２％、シリカ含有率は１７．４重量％、鉛筆硬度は４Ｈであった。
Example 3
After adding a polymerization initiator to a mixture of methyl methacrylate and acrylic acid that is 1 mol of acrylic acid with respect to 9 mol of methyl methacrylate, heat treatment was performed at 73 ° C. for 3 hours and 120 ° C. for 1 hour. The polymerization reaction was carried out. 8 g of the obtained polymer was added to a mixed solvent of 155 g of isopropanol and 40 g of water, and then stirred and mixed at 65 ° C. for 6 hours to obtain a solution in which the resin was dissolved. To this solution was added 5 g of a sol in which silica was dispersed in isopropanol (silica content: 30% by weight, silica central particle size: 10 to 15 nm, manufactured by Nissan Chemical Industries, Ltd.), and the mixture was stirred and mixed at 65 ° C. for 6 hours. The mixture was cooled to about 0 ° C. and gelled. The gel was air-dried at room temperature for 2 days and then dried at 50 ° C. for 2 days and additionally at 120 ° C. for 3 days to obtain a methacrylic resin composition. This resin composition was press-molded by a press molding machine to obtain a press plate having a thickness of 2 mm. The press plate had a total light transmittance of 72.5%, a haze value of 54.2%, a silica content of 17.4% by weight, and a pencil hardness of 4H.
実施例４
メタクリル酸メチル及びビニルスルホン酸の混合物であって、メタクリル酸メチル９９モルに対しビニルスルホン酸１モルである混合物に、重合開始剤を加えた後、７３℃で３時間、１２０℃で１時間熱処理をして重合反応を行った。得られた重合物８ｇをイソプロパノール１６０ｇ及び水４０ｇの混合溶媒に加えた後、６５℃で６時間攪拌混合し、該樹脂が溶解した溶液を得た。この溶液に、シリカがイソプロパノールに分散してなるゾル（シリカ含有率；３０重量％、シリカの中心粒子径；１０〜１５ｎｍ、日産化学社製）５ｇを加え、６５℃で６時間攪拌混合した。該混合物をアルミ製のバットに入れ、室温で２日間風乾した後、５０℃で２日間、くわえて１２０℃で３日間乾燥させ、メタクリル樹脂組成物を得た。この樹脂組成物をプレス成形加工機によりプレス成形し、厚さ２ｍｍのプレス板を得た。このプレス板の全光線透過率は６８．５％、ヘイズ値は５８．８％、シリカ含有率は７．４重量％、鉛筆硬度は５Ｈであった。
Example 4
After adding a polymerization initiator to a mixture of methyl methacrylate and vinyl sulfonic acid, which is 1 mol of vinyl sulfonic acid with respect to 99 mol of methyl methacrylate, heat treatment at 73 ° C. for 3 hours and at 120 ° C. for 1 hour The polymerization reaction was carried out. 8 g of the resulting polymer was added to a mixed solvent of 160 g of isopropanol and 40 g of water, and then stirred and mixed at 65 ° C. for 6 hours to obtain a solution in which the resin was dissolved. To this solution was added 5 g of a sol in which silica was dispersed in isopropanol (silica content: 30% by weight, silica central particle size: 10 to 15 nm, manufactured by Nissan Chemical Industries, Ltd.), and the mixture was stirred and mixed at 65 ° C. for 6 hours. The mixture was placed in an aluminum vat and air-dried at room temperature for 2 days, and then dried at 50 ° C. for 2 days and additionally at 120 ° C. for 3 days to obtain a methacrylic resin composition. This resin composition was press-molded by a press molding machine to obtain a press plate having a thickness of 2 mm. The press plate had a total light transmittance of 68.5%, a haze value of 58.8%, a silica content of 7.4% by weight, and a pencil hardness of 5H.
比較例１
メタクリル酸メチル９６重量％及びアクリル酸メチル４重量％が重合してなる共重合体樹脂ペレット（重量平均分子量；１２万）８ｇを、エタノール２００ｇに加えた後、６０℃で１５時間攪拌混合したが、該樹脂は溶解しなかった。
Comparative Example 1
Although 8 g of copolymer resin pellets (weight average molecular weight; 120,000) obtained by polymerizing 96 wt% of methyl methacrylate and 4 wt% of methyl acrylate were added to 200 g of ethanol, the mixture was stirred and mixed at 60 ° C. for 15 hours. The resin did not dissolve.
比較例２
メタクリル酸メチル９６重量％及びアクリル酸メチル４重量％が重合してなる共重合体樹脂ペレット（重量平均分子量；１２万）８ｇを、イソプロパノール２００ｇに加えた後、６５℃で１５時間攪拌混合したが、該樹脂は溶解しなかった。
Comparative Example 2
8 g of copolymer resin pellets (weight average molecular weight; 120,000) obtained by polymerizing 96% by weight of methyl methacrylate and 4% by weight of methyl acrylate were added to 200 g of isopropanol, and then stirred and mixed at 65 ° C. for 15 hours. The resin did not dissolve.
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| JP2016166269A (en) * | 2015-03-09 | 2016-09-15 | 富士フイルム株式会社 | Method for producing resin composition, resin composition, method for producing laminated material and laminated material |
| JP2022062187A (en) * | 2016-05-20 | 2022-04-19 | 住友化学株式会社 | Injection molded body |
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| JP2016166269A (en) * | 2015-03-09 | 2016-09-15 | 富士フイルム株式会社 | Method for producing resin composition, resin composition, method for producing laminated material and laminated material |
| JP2022062187A (en) * | 2016-05-20 | 2022-04-19 | 住友化学株式会社 | Injection molded body |
| JP7283593B2 (en) | 2016-05-20 | 2023-05-30 | 住友化学株式会社 | injection molding |
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