JP2013001781A - Molded article and method for producing the same - Google Patents
Molded article and method for producing the same Download PDFInfo
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本発明は低い線膨張係数を有する成形品およびその製造方法に関するものである。 The present invention relates to a molded article having a low linear expansion coefficient and a method for producing the same.
一般的に物質は加熱すると膨張するが、特に有機樹脂材料の線膨張係数は大きいことが知られている。例えば精密光学系などに代表されるデバイスにおいて、有機樹脂材料から成る部材を使用する場合、線膨張係数が大きく、温度変化による部材の寸法変化が大きいと、光学系の位置ずれを引き起こす原因となり得る。 In general, substances expand when heated, but it is known that the coefficient of linear expansion of organic resin materials is particularly large. For example, when a member made of an organic resin material is used in a device typified by a precision optical system or the like, if the linear expansion coefficient is large and the dimensional change of the member due to a temperature change is large, it may cause a displacement of the optical system .
この問題を解決する方法として、有機樹脂材料に無機微粒子を添加して線膨張係数を低下させ、位置ずれを少なくする方法が知られている（特許文献１）。 As a method for solving this problem, a method is known in which inorganic fine particles are added to an organic resin material to reduce the coefficient of linear expansion and reduce positional deviation (Patent Document 1).
また、他の線膨張係数を低減する方法として、負の線膨張（以下、負膨張）性を有する材料を、有機樹脂材料から成る部材の周辺に組み込み寸法変化を補償する方法、あるいは負膨張性を有する材料を有機樹脂材料に混合し線膨張係数を低減する方法がある。 As another method of reducing the linear expansion coefficient, a material having negative linear expansion (hereinafter referred to as negative expansion) is incorporated around a member made of an organic resin material to compensate for dimensional changes, or negative expansion There is a method of reducing the coefficient of linear expansion by mixing a material having an organic resin material.
負膨張性を有する材料として、タングステン酸ジルコニウムやリチウム−アルミニウム−シリコン酸化物、マンガンの窒化物などの無機材料が知られている（特許文献２、特許文献３、非特許文献１）。また有機材料でも液晶ポリマーや超高分子量ポリエチレン繊維などが負膨張性を示すことが知られている（特許文献４、特許文献５）。 As materials having negative expansibility, inorganic materials such as zirconium tungstate, lithium-aluminum-silicon oxide, and manganese nitride are known (Patent Document 2, Patent Document 3, and Non-Patent Document 1). In addition, it is known that liquid crystal polymers, ultrahigh molecular weight polyethylene fibers, and the like exhibit negative expansion properties even in organic materials (Patent Documents 4 and 5).
しかしながら、これまでに知られている有機樹脂材料に無機微粒子を加えて線膨張係数を低下させる方法においては、線膨張係数が１０×１０−６／℃以下を示す成形品を得ることが難しいため、精密光学系などに使用することが困難であった。 However, it is difficult to obtain a molded product having a linear expansion coefficient of 10 × 10 −6 / ° C. or less in the known methods of adding inorganic fine particles to an organic resin material to reduce the linear expansion coefficient. It was difficult to use for precision optical systems.
また有機樹脂材料の膨張分をマンガン窒化物からなる負膨張性材料により補償する場合、上述の負膨張性を有する無機材料は、その線膨張係数の絶対値が最大でも２５×１０−６／℃と小さい。同様に負膨張性を有する有機材料もその線膨張係数の絶対値が１０×１０−６／℃よりも小さい。そのため有機樹脂材料の温度変化による膨張を補償するためには、相当の厚みまたは量の負膨張性を有する材料を用いた成形体が必要である。 When the organic resin material is compensated for by the negative expansion material made of manganese nitride, the above-described inorganic material having negative expansion property has an absolute value of the linear expansion coefficient of 25 × 10 −6 / ° C. at the maximum. And small. Similarly, an organic material having negative expansibility also has an absolute value of linear expansion coefficient smaller than 10 × 10 −6 / ° C. Therefore, in order to compensate for the expansion due to the temperature change of the organic resin material, a molded body using a material having a negative expansion property having a considerable thickness or amount is required.
本発明は、この様な背景技術に鑑みてなされたものであり、低い線膨張係数を有する成形品およびその製造方法を提供するものである。 This invention is made | formed in view of such a background art, and provides the molded article which has a low linear expansion coefficient, and its manufacturing method.
上記の課題を解決する成形品は、少なくともアミノ基を有する官能基で表面修飾された無機微粒子とポリメタクリル酸メチルを含み、前記無機微粒子の含有量が３０ｖｏｌ％以上８０ｖｏｌ％以下である混合材料を成形してなる成形品であり、前記成形品の２０℃から６０℃の範囲の線膨張係数が１０×１０−６／℃以下（但し、負の線膨張係数を含む。）であることを特徴とする。 A molded article that solves the above-mentioned problem is a mixed material containing inorganic fine particles surface-modified with at least a functional group having an amino group and polymethyl methacrylate, and the content of the inorganic fine particles is 30 vol% or more and 80 vol% or less. A molded article formed by molding, wherein the molded article has a linear expansion coefficient of 10 × 10 −6 / ° C. or less (including a negative linear expansion coefficient) in a range of 20 ° C. to 60 ° C. And
上記の課題を解決する成形品の製造方法は、少なくともアミノ基を有する官能基で表面修飾された無機微粒子とポリメタクリル酸メチルとを、前記無機微粒子の含有量が３０ｖｏｌ％以上８０ｖｏｌ％以下になる様に混合して混合材料を得る工程、前記混合材料を加熱下で加圧成形する工程を有することを特徴とする。 In the method for producing a molded article that solves the above problems, the inorganic fine particles surface-modified with at least a functional group having an amino group and polymethyl methacrylate are used, and the content of the inorganic fine particles is 30 vol% or more and 80 vol% or less. It is characterized by having a step of obtaining a mixed material by mixing, and a step of pressure-molding the mixed material under heating.
本発明によれば、低い線膨張係数を有する成形品およびその製造方法を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the molded article which has a low linear expansion coefficient, and its manufacturing method can be provided.
本発明の成形品は、低い線膨張係数を有するので、光ファイバーやレンズなどの精密光学系デバイスに使用される低膨張部材や温度補償部材として好適に使用できる。 Since the molded article of the present invention has a low linear expansion coefficient, it can be suitably used as a low expansion member or a temperature compensation member used for precision optical devices such as optical fibers and lenses.
以下、本発明の実施の形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明に係る成形品は、少なくともアミノ基を有する官能基で表面修飾された無機微粒子とポリメタクリル酸メチルを含み、前記無機微粒子の含有量が３０ｖｏｌ％以上８０ｖｏｌ％以下である混合材料を成形してなる成形品であり、前記成形品の２０℃から６０℃の範囲の線膨張係数が１０×１０−６／℃以下（但し、負の線膨張係数を含む。）であることを特徴とする。 The molded article according to the present invention is formed by molding a mixed material containing inorganic fine particles surface-modified with at least a functional group having an amino group and polymethyl methacrylate, and the content of the inorganic fine particles is 30 vol% or more and 80 vol% or less. The molded article has a linear expansion coefficient of 10 × 10 −6 / ° C. or less (including a negative linear expansion coefficient) in the range of 20 ° C. to 60 ° C. .
本発明は、ポリメタクリル酸メチル（以下、ＰＭＭＡと記す。）に、アミノ基を有する官能基で表面修飾された無機微粒子を混合した後に成形を行うことで、低い線膨張係数を有する成形品を提供するものである。 In the present invention, polymethyl methacrylate (hereinafter referred to as PMMA) is mixed with inorganic fine particles whose surface is modified with a functional group having an amino group, and then molded, thereby forming a molded product having a low linear expansion coefficient. It is to provide.
本発明における無機微粒子は、アミノ基を有する官能基で表面修飾されている無機微粒子を用いることを特徴とする。従来、有機樹脂材料に無機微粒子を添加すると、有機樹脂材料の線膨張係数を低減する方法はよく知られているが、線膨張係数の低減が十分ではなかった。本発明は、線膨張係数を大きく低減させるために、アミノ基を有する官能基で表面修飾されている無機微粒子を選択して用いたものである。 The inorganic fine particles in the present invention are characterized by using inorganic fine particles whose surface is modified with a functional group having an amino group. Conventionally, when inorganic fine particles are added to an organic resin material, a method for reducing the linear expansion coefficient of the organic resin material is well known, but the linear expansion coefficient has not been sufficiently reduced. In the present invention, in order to greatly reduce the linear expansion coefficient, inorganic fine particles whose surface is modified with a functional group having an amino group are selected and used.
アミノ基を有する官能基としては、４−アミノブチル基、Ｎ−（２−アミノエチル）−３−アミノプロピル基、Ｎ−（２−アミノエチル）−１１−アミノウンデシル基、Ｎ−（６−アミノヘキシル）アミノプロピル基、Ｎ−フェニル−３−アミノプロピル基、（アミノエチルアミノメチル）フェニチル基、３−（ｍ−アミノフェノキシ）プロピル基、ｍ−アミノフェニル基、ｐ−アミノフェニル基、３−アミノプロピル基、３−ジメチルアミノプロピル基、Ｎ，Ｎ−ジメチルアミノプロピル基、Ｎ−メチルアミノプロピル基、ウレイドプロピル基などが挙げられるが、これらに限定されない。 Examples of the functional group having an amino group include 4-aminobutyl group, N- (2-aminoethyl) -3-aminopropyl group, N- (2-aminoethyl) -11-aminoundecyl group, N- (6 -Aminohexyl) aminopropyl group, N-phenyl-3-aminopropyl group, (aminoethylaminomethyl) phenethyl group, 3- (m-aminophenoxy) propyl group, m-aminophenyl group, p-aminophenyl group, Examples include, but are not limited to, 3-aminopropyl group, 3-dimethylaminopropyl group, N, N-dimethylaminopropyl group, N-methylaminopropyl group, ureidopropyl group, and the like.
無機微粒子は、特に限定されないが、例えば、シリカ、チタニア、ジルコニア、アルミナ、酸化ニオブ、酸化マグネシウム、酸化ベリリウム、酸化テルル、酸化イットリウム、インジウム錫酸化物等の金属酸化物粒子や、金、白金、銀等の金属粒子が挙げられる。特に、無機微粒子がシリカ微粒子であることが好ましい。 The inorganic fine particles are not particularly limited, but for example, metal oxide particles such as silica, titania, zirconia, alumina, niobium oxide, magnesium oxide, beryllium oxide, tellurium oxide, yttrium oxide, indium tin oxide, gold, platinum, Examples thereof include metal particles such as silver. In particular, the inorganic fine particles are preferably silica fine particles.
無機微粒子の粒子径は、特に限定されないが、平均一次粒子径が１ｎｍ以上３０ｎｍ以下、好ましくは７ｎｍ以上１２ｎｍ以下であることが望ましい。粒子径が３０ｎｍより大きいと表面積の減少に伴い低線膨張性が失われる可能性がある。 The particle diameter of the inorganic fine particles is not particularly limited, but the average primary particle diameter is 1 nm to 30 nm, preferably 7 nm to 12 nm. If the particle diameter is larger than 30 nm, the low linear expansion property may be lost as the surface area decreases.
アミノ基を有する官能基で表面修飾された無機微粒子には、ＲＡ２００Ｈ（シリカ、日本アエロジル社製）、ＮＡ５０Ｈ（シリカ、日本アエロジル社製）等の市販品を用いることができる。 Commercially available products such as RA200H (silica, manufactured by Nippon Aerosil Co., Ltd.) and NA50H (silica, manufactured by Nippon Aerosil Co., Ltd.) can be used for the inorganic fine particles whose surface is modified with a functional group having an amino group.
本発明の成形品は、上記のアミノ基を有する官能基で表面修飾された無機微粒子と、ポリメタクリル酸メチルを含有する混合材料を成形してなる成形品である。 The molded article of the present invention is a molded article formed by molding a mixed material containing inorganic fine particles whose surface is modified with the above functional group having an amino group and polymethyl methacrylate.
本発明の成形品に含有される無機微粒子の含有量は、３０ｖｏｌ％（体積パーセント）以上８０ｖｏｌ％以下、好ましくは３０ｖｏｌ％（体積パーセント）以上５０ｖｏｌ％以下が望ましい。３０ｖｏｌ％（体積パーセント）は、およそ４２重量パーセントである。無機微粒子の含有量が３０ｖｏｌ％以上になると成形品の線膨張係数が急激に低下する。確実に線膨張係数を低減するためには無機微粒子の含有量を多くすることが有効であるが、含有量が増えるにつれて脆くなり成形性が悪化するため、含有量は８０ｖｏｌ％以下であることが好ましい。 The content of the inorganic fine particles contained in the molded article of the present invention is 30 vol% (volume percent) to 80 vol%, preferably 30 vol% (volume percent) to 50 vol%. 30 vol% (volume percent) is approximately 42 weight percent. When the content of the inorganic fine particles is 30 vol% or more, the linear expansion coefficient of the molded product is rapidly reduced. In order to reliably reduce the linear expansion coefficient, it is effective to increase the content of inorganic fine particles. However, as the content increases, the content becomes brittle and the formability deteriorates, so the content may be 80 vol% or less. preferable.
また、同じ含有量においても無機微粒子の分散状態によっては異なる線膨張係数を有することがある。なお本発明における無機微粒子の含有量とは、熱重量分析（ＴＧＡ）装置によって成形品を８００℃まで昇温したときの残存重量パーセントを測定し、体積換算した数値を表す。 Even with the same content, it may have a different linear expansion coefficient depending on the dispersion state of the inorganic fine particles. The content of the inorganic fine particles in the present invention represents a numerical value converted into a volume by measuring the residual weight percentage when the molded product is heated to 800 ° C. by a thermogravimetric analysis (TGA) apparatus.
本発明の成形品は、２０℃から６０℃の範囲の線膨張係数が１０×１０−６／℃以下（但し、負の線膨張係数を含む。）であることを特徴とする。本発明の成形品の好ましい線膨張係数は、−１０×１０−６／℃以上１０×１０−６／℃以下、さらに好ましくは−５×１０−６／℃以上５×１０−６／℃以下である。−は負の線膨張係数を表す。線膨張係数が１０×１０−６／℃より大きくなると、温度変化による成形品の寸法変化が大きくなり、部材の位置ずれが発生するので好ましくない。本発明の成形品の２０℃から６０℃の範囲の線膨張係数が、負の線膨張係数であることが好ましい。 The molded article of the present invention has a linear expansion coefficient in the range of 20 ° C. to 60 ° C. of 10 × 10 −6 / ° C. or less (including a negative linear expansion coefficient). The linear expansion coefficient of the molded article of the present invention is preferably −10 × 10 −6 / ° C. or higher and 10 × 10 −6 / ° C. or lower, more preferably −5 × 10 −6 / ° C. or higher and 5 × 10 −6 / ° C. or lower. It is. -Represents a negative linear expansion coefficient. When the linear expansion coefficient is larger than 10 × 10 −6 / ° C., the dimensional change of the molded product due to the temperature change becomes large, and the position shift of the member occurs. The linear expansion coefficient in the range of 20 ° C. to 60 ° C. of the molded article of the present invention is preferably a negative linear expansion coefficient.
次に、本発明に係る成形品の製造方法について説明する。 Next, the manufacturing method of the molded product according to the present invention will be described.
本発明に係る成形品の製造方法は、少なくともアミノ基を有する官能基で表面修飾された無機微粒子とポリメタクリル酸メチルとを、前記無機微粒子の含有量が３０ｖｏｌ％以上８０ｖｏｌ％以下になる様に混合して混合材料を得る工程、前記混合材料を加熱下で加圧成形する工程を有することを特徴とする。 In the method for producing a molded article according to the present invention, the inorganic fine particles surface-modified with at least a functional group having an amino group and polymethyl methacrylate are used so that the content of the inorganic fine particles is 30 vol% or more and 80 vol% or less. It has a step of mixing to obtain a mixed material, and a step of pressure-molding the mixed material under heating.
前記混合材料を得る工程は、ＰＭＭＡを溶媒に溶解した状態で、前記無機微粒子または溶媒に分散した無機微粒子と混合した後、前記溶媒を除去して混合材料を得るのが好ましい。 In the step of obtaining the mixed material, it is preferable that PMMA is dissolved in a solvent and mixed with the inorganic fine particles or the inorganic fine particles dispersed in the solvent, and then the solvent is removed to obtain the mixed material.
ＰＭＭＡと無機微粒子の混合は、溶媒中にＰＭＭＡを溶解させて微粒子と混合し溶媒を除去する方法で行う。 PMMA and inorganic fine particles are mixed by a method in which PMMA is dissolved in a solvent, mixed with the fine particles, and the solvent is removed.
ＰＭＭＡが溶解する溶媒は、アセトン、トルエン、テトラヒドロフラン、酢酸エチル、酢酸ブチル、キシレン、ジメチルホルムアミドなどが挙げられる。残留溶媒は線膨張係数を悪化させる要因となるため、溶媒の除去は加熱・真空などにより確実に行う必要がある。従って溶媒を除去することを考えると、沸点の比較的低いアセトン、テトラヒドロフラン、酢酸エチルが好適である。 Examples of the solvent in which PMMA is dissolved include acetone, toluene, tetrahydrofuran, ethyl acetate, butyl acetate, xylene, dimethylformamide, and the like. Since the residual solvent causes a deterioration in the linear expansion coefficient, it is necessary to reliably remove the solvent by heating or vacuum. Therefore, in view of removing the solvent, acetone, tetrahydrofuran, and ethyl acetate having a relatively low boiling point are preferable.
無機微粒子は直接ＰＭＭＡの溶液に混合してもよいし、予め溶媒と混合した無機微粒子の含有液をＰＭＭＡの溶液に混合してもよい。溶媒の量は任意であるため、最終的に除去可能であれば適宜追加しても構わない。ＰＭＭＡと無機微粒子を混合した後、ホモジナイザーや超音波処理などにより混合溶液を均一化することが望ましい。 The inorganic fine particles may be directly mixed with the PMMA solution, or a liquid containing inorganic fine particles previously mixed with a solvent may be mixed with the PMMA solution. Since the amount of the solvent is arbitrary, it may be appropriately added as long as it can be finally removed. After mixing PMMA and inorganic fine particles, it is desirable to homogenize the mixed solution by a homogenizer or ultrasonic treatment.
ＰＭＭＡと無機微粒子は、無機微粒子の含有量が３０ｖｏｌ％以上８０ｖｏｌ％以下になるように混合される。 PMMA and inorganic fine particles are mixed so that the content of the inorganic fine particles is 30 vol% or more and 80 vol% or less.
ＰＭＭＡと無機微粒子を混合した混合材料は、射出成形やヒートプレス成形など、加熱下において加圧成形することで任意の形状に成形される。成形時の温度は低すぎると目的の形状を作製できず、高すぎると線膨張係数が高くなる原因となることから、１５０から３００℃の範囲が適当である。成形圧力は特に限定されないが、形状を転写させるために５０ＭＰａ以上であることが好ましい。 A mixed material obtained by mixing PMMA and inorganic fine particles is molded into an arbitrary shape by pressure molding under heating, such as injection molding or heat press molding. If the temperature at the time of molding is too low, the desired shape cannot be produced, and if it is too high, the linear expansion coefficient becomes high, so a range of 150 to 300 ° C. is appropriate. The molding pressure is not particularly limited, but is preferably 50 MPa or more in order to transfer the shape.
以下、実施例及び比較例を挙げて本発明を更に具体的に説明をする。本発明は何らこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. The present invention is not limited to these examples.
（実施例１）
＜ＰＭＭＡと無機微粒子の混合＞
ＰＭＭＡ（デルペット７０ＮＨ；旭化成ケミカルズ社製）をアセトンに対して５ｗｔ％になるように混合し、超音波処理により常温（２５℃）にてＰＭＭＡを溶解させ、ＰＭＭＡ／アセトン溶液を作製した。
Example 1
<Mixing of PMMA and inorganic fine particles>
PMMA (Delpet 70NH; manufactured by Asahi Kasei Chemicals Corporation) was mixed so as to be 5 wt% with respect to acetone, and PMMA was dissolved at room temperature (25 ° C.) by ultrasonic treatment to prepare a PMMA / acetone solution.
アミノ基を有する無機微粒子として、ＲＡ２００Ｈ（シリカ、平均一次粒子径１２ｎｍ、日本アエロジル社製）をアセトンに対して２．５ｗｔ％になるように混合し、無機微粒子／アセトン溶液を作製した。 As inorganic fine particles having an amino group, RA200H (silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.) was mixed at 2.5 wt% with respect to acetone to prepare an inorganic fine particle / acetone solution.
作製したＰＭＭＡ／アセトン溶液１０ｇに対し、無機微粒子／アセトン溶液を２０ｇ滴下し、超音波処理装置を用いてよく混合した。混合溶液中のアセトンをある程度自然乾燥させた後、真空加熱炉で約２１０℃にておよそ４時間過熱して溶媒の除去を行い、ＰＭＭＡ／無機微粒子の混合材料を得た。 20 g of inorganic fine particles / acetone solution was dropped into 10 g of the prepared PMMA / acetone solution, and well mixed using an ultrasonic treatment apparatus. After the acetone in the mixed solution was naturally dried to some extent, the solvent was removed by heating in a vacuum heating furnace at about 210 ° C. for about 4 hours to obtain a mixed material of PMMA / inorganic fine particles.
＜成形＞
成形はヒートプレスにて行った。
<Molding>
Molding was performed by a heat press.
φ１５ｍｍのプレス成形用金型の面に離型剤としてノベック−１７２０（住友スリーエム社製）を滴下してよく拭き取る。ＰＭＭＡ／無機微粒子の混合材料をプレス成形用金型に充填し、小型熱プレス機（アズワン社製）にセットしながら２５０℃まで加熱した。小型熱プレス機の上面と下面の温度が２５０℃に達した後に１１０ＭＰａの荷重を付与し、１００℃まで風冷しながら荷重を自然開放させた。１００℃で完全に荷重を除き、金型からＰＭＭＡ／無機微粒子の混合材料を離型することでコイン状の成形品を得た。 Novec-1720 (manufactured by Sumitomo 3M) is dropped as a mold release agent onto the surface of the press molding mold with a diameter of 15 mm. A mixed material of PMMA / inorganic fine particles was filled in a press molding die and heated to 250 ° C. while being set in a small heat press (manufactured by ASONE). A load of 110 MPa was applied after the temperature of the upper and lower surfaces of the small hot press machine reached 250 ° C., and the load was naturally released while cooling to 100 ° C. A coin-shaped molded article was obtained by completely removing the load at 100 ° C. and releasing the mixed material of PMMA / inorganic fine particles from the mold.
（実施例２）
実施例１において、無機微粒子／アセトン溶液を５ｗｔ％に調整し、ＰＭＭＡ／アセトン溶液９．４ｇに無機微粒子／アセトン溶液を１０．６ｇ加えた以外は実施例１と同様にして、成形品を得た。
(Example 2)
A molded article was obtained in the same manner as in Example 1 except that the inorganic fine particle / acetone solution was adjusted to 5 wt% in Example 1, and 10.6 g of the inorganic fine particle / acetone solution was added to 9.4 g of the PMMA / acetone solution. It was.
（実施例３）
実施例１において、ＰＭＭＡ／無機微粒子の混合材料を作製する際に、２．５ｗｔ％無機微粒子／アセトン溶液を１７ｇ滴下した他は実施例１と同様にして、成形品を得た。
(Example 3)
In Example 1, a molded product was obtained in the same manner as in Example 1 except that 17 g of 2.5 wt% inorganic fine particles / acetone solution was dropped when a mixed material of PMMA / inorganic fine particles was produced.
（実施例４）
実施例１において、ＰＭＭＡ／無機微粒子の混合材料を作製する際に、２．５ｗｔ％無機微粒子／アセトン溶液を１４ｇ滴下した他は実施例１と同様にして、成形品を得た。
Example 4
In Example 1, a molded product was obtained in the same manner as in Example 1 except that 14 g of 2.5 wt% inorganic fine particles / acetone solution was dropped when producing the mixed material of PMMA / inorganic fine particles.
（比較例１）
実施例１において、ＰＭＭＡ／無機微粒子の混合材料を作製する際に、２．５ｗｔ％無機微粒子／アセトン溶液を１０ｇ滴下した他は実施例１と同様にして、成形品を得た。
(Comparative Example 1)
In Example 1, a molded product was obtained in the same manner as in Example 1 except that 10 g of 2.5 wt% inorganic fine particle / acetone solution was dropped when the PMMA / inorganic fine particle mixed material was produced.
（比較例２）
実施例１において、ＰＭＭＡ／無機微粒子の混合材料を作製する際に、２．５ｗｔ％無機微粒子／アセトン溶液を５ｇ滴下した他は実施例１と同様にして、成形品を得た。
(Comparative Example 2)
In Example 1, a molded product was obtained in the same manner as in Example 1 except that 5 g of 2.5 wt% inorganic fine particles / acetone solution was dropped when producing the mixed material of PMMA / inorganic fine particles.
（比較例３）
実施例１において、無機微粒子を添加せずにＰＭＭＡのみをアセトンに溶解し、その他は実施例１と同様にして成形品を得た。
(Comparative Example 3)
In Example 1, a molded product was obtained in the same manner as in Example 1 except that only PMMA was dissolved in acetone without adding inorganic fine particles.
（実施例５）
＜ＰＭＭＡと無機微粒子の混合＞
ＰＭＭＡ（デルペット７０ＮＨ；旭化成ケミカルズ社製）をアセトンに対して５ｗｔ％になるように混合し、超音波処理により常温にてＰＭＭＡを溶解させ、ＰＭＭＡ／アセトン溶液を作製した。
(Example 5)
<Mixing of PMMA and inorganic fine particles>
PMMA (Delpet 70NH; manufactured by Asahi Kasei Chemicals Corporation) was mixed so as to be 5 wt% with respect to acetone, and PMMA was dissolved at room temperature by ultrasonic treatment to prepare a PMMA / acetone solution.
ＰＭＭＡ／アセトン溶液４０ｇに対し、ＲＡ２００Ｈを５．６ｇ添加し、ＲＡ２００Ｈが十分に浸漬するようにアセトンを任意量加え、超音波処理を行いよく混合した。アセトンをある程度自然乾燥させた後、真空加熱炉で約２１０℃にておよそ４時間加熱して溶媒の除去を行い、ＰＭＭＡ／無機微粒子の混合材料を得た。 5.6 g of RA200H was added to 40 g of the PMMA / acetone solution, an arbitrary amount of acetone was added so that RA200H was sufficiently immersed, and the mixture was subjected to ultrasonic treatment and mixed well. After the acetone was naturally dried to some extent, the solvent was removed by heating at about 210 ° C. for about 4 hours in a vacuum heating furnace to obtain a mixed material of PMMA / inorganic fine particles.
＜成形＞
成形は実施例１と同様にして行い、成形品を得た。
<Molding>
Molding was performed in the same manner as in Example 1 to obtain a molded product.
（実施例６）
実施例５において、アミノ基を有する無機微粒子をＲＡ２００ＨのかわりにＮＡ５０Ｈ（シリカ、平均一次粒子径３０ｎｍ、日本アエロジル社製）を用いて、ＰＭＭＡ／アセトン溶液１０ｇにＮＡ５０Ｈを１．２ｇ添加した以外は実施例５と同様にして成形品を得た。
(Example 6)
In Example 5, except that NA50H (silica, average primary particle size 30 nm, manufactured by Nippon Aerosil Co., Ltd.) was used instead of RA200H for inorganic fine particles having amino groups, and 1.2 g of NA50H was added to 10 g of PMMA / acetone solution. A molded product was obtained in the same manner as in Example 5.
（比較例４）
実施例５において、無機微粒子をＲ７１１（シリカ、平均一次粒子径１２ｎｍ、日本アエロジル社製）に変更し、ＰＭＭＡ／アセトン溶液５０ｇに対してＲ７１１を１．８ｇ添加した以外は実施例５と同様にして行い、成形品を得た。Ｒ７１１はメタクリロキシプロピル基で表面修飾されている。
(Comparative Example 4)
In Example 5, the inorganic fine particles were changed to R711 (silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.), and the same procedure as in Example 5 was performed except that 1.8 g of R711 was added to 50 g of the PMMA / acetone solution. To obtain a molded product. R711 is surface-modified with a methacryloxypropyl group.
（比較例５）
実施例１において、無機微粒子をＲ８０５（シリカ、平均一次粒子径１２ｎｍ、日本アエロジル社製）に変更した以外は実施例１と同様にして行い、成形品を得た。Ｒ８０５はオクチル基で表面修飾されている。
(Comparative Example 5)
A molded product was obtained in the same manner as in Example 1 except that the inorganic fine particles were changed to R805 (silica, average primary particle size 12 nm, manufactured by Nippon Aerosil Co., Ltd.). R805 is surface-modified with an octyl group.
（比較例６）
比較例５において、ＰＭＭＡ／無機微粒子の混合材料を作製する際に、２．５ｗｔ％無機微粒子／アセトン溶液を１０ｇ滴下した他は比較例５と同様にして、成形品を得た。
(Comparative Example 6)
In Comparative Example 5, a molded product was obtained in the same manner as Comparative Example 5 except that 10 g of 2.5 wt% inorganic fine particle / acetone solution was dropped when a mixed material of PMMA / inorganic fine particles was produced.
＜線膨張係数の評価＞
ＴＭＡ（ＴＭＡ Ｑ４００；ＴＡインスツルメント社製）にて、０から８０℃で３サイクル温度負荷を与え、厚み方向に対する２０から６０℃の線膨張係数を算出した。変位の測定には膨張プローブを使用した。
<Evaluation of linear expansion coefficient>
Using TMA (TMA Q400; manufactured by TA Instruments), a three-cycle temperature load was applied at 0 to 80 ° C., and a linear expansion coefficient of 20 to 60 ° C. with respect to the thickness direction was calculated. An expansion probe was used to measure the displacement.
＜無機微粒子の含有量の評価＞
無機微粒子の含有量は、熱重量分析（ＴＧＡ）装置によって成形品を８００℃まで昇温したときの残存重量パーセントを測定し、体積換算した数値を表す。無機微粒子の含有量の測定はＴＧＡ（ＴＧＡ Ｑ５００；ＴＡインスツルメント社製）を用いて行った。無機微粒子の含有量を重量パーセントからｖｏｌ％（体積パーセント）への換算に際し、ＰＭＭＡの比重値には１．１９、シリカ微粒子の比重値は２．００を使用した。なお評価に際して各成形品は適宜適当な大きさにカットした。
<Evaluation of content of inorganic fine particles>
The content of the inorganic fine particles represents a numerical value converted into a volume by measuring the residual weight percentage when the molded article is heated to 800 ° C. by a thermogravimetric analysis (TGA) apparatus. The content of the inorganic fine particles was measured using TGA (TGA Q500; manufactured by TA Instruments). When converting the content of the inorganic fine particles from weight percent to vol% (volume percent), 1.19 was used as the specific gravity value of PMMA, and 2.00 was used as the specific gravity value of the silica fine particles. In the evaluation, each molded product was appropriately cut into an appropriate size.
表１に実施例および比較例の成形品の評価結果を示した。また、図１に実施例１から４、比較例１から３で得られた成形品の無機微粒子含有量と線膨張係数の関係をプロットしたものを示した。 Table 1 shows the evaluation results of the molded products of Examples and Comparative Examples. FIG. 1 shows a plot of the relationship between the inorganic fine particle content and the linear expansion coefficient of the molded products obtained in Examples 1 to 4 and Comparative Examples 1 to 3.
本発明の成形品は、２０から６０℃の範囲において低い線膨張係数を示すので、光ファイバーやレンズなどの精密光学系デバイスに使用される低膨張部材や温度補償部材として利用することができる。 Since the molded product of the present invention exhibits a low linear expansion coefficient in the range of 20 to 60 ° C., it can be used as a low expansion member or a temperature compensation member used for precision optical devices such as optical fibers and lenses.
Claims (7)
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