JP2021130828A - Manufacturing method of surface modification substrate and inspection method - Google Patents
Manufacturing method of surface modification substrate and inspection method Download PDFInfo
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- JP2021130828A JP2021130828A JP2021093404A JP2021093404A JP2021130828A JP 2021130828 A JP2021130828 A JP 2021130828A JP 2021093404 A JP2021093404 A JP 2021093404A JP 2021093404 A JP2021093404 A JP 2021093404A JP 2021130828 A JP2021130828 A JP 2021130828A
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- CCIYPTIBRAUPLQ-UHFFFAOYSA-M tetrabutylphosphanium;iodide Chemical compound [I-].CCCC[P+](CCCC)(CCCC)CCCC CCIYPTIBRAUPLQ-UHFFFAOYSA-M 0.000 description 1
- WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 description 1
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- XMRGUUXVQWPMAO-UHFFFAOYSA-M tributyl(5-phenylpentyl)azanium iodide Chemical compound [I-].C(C1=CC=CC=C1)CCCC[N+](CCCC)(CCCC)CCCC XMRGUUXVQWPMAO-UHFFFAOYSA-M 0.000 description 1
- SDSMZSUWTYFEBO-UHFFFAOYSA-M tributyl(methyl)phosphanium;bromide Chemical compound [Br-].CCCC[P+](C)(CCCC)CCCC SDSMZSUWTYFEBO-UHFFFAOYSA-M 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- HIACZXUUKNSHAN-UHFFFAOYSA-M trimethyl(octadecyl)azanium;iodide Chemical compound [I-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C HIACZXUUKNSHAN-UHFFFAOYSA-M 0.000 description 1
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Landscapes
- Polymerisation Methods In General (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
本発明は、表面改質基材の製造方法、その製造方法により製造される表面改質基材、及びその検査方法に関する。 The present invention relates to a method for producing a surface-modified base material, a surface-modified base material produced by the production method, and an inspection method thereof.
基材の改質方法として、その末端に基材と吸着又は反応しうる基を有するポリマーを基材に作用させることで、物理的又は化学的に結合したポリマー層を基材表面に形成する方法が知られている。また、基材表面に付与した重合性基を起点としてモノマーを重合させることで、基材表面からグラフトしたポリマー層を形成する方法も知られている。 As a method for modifying a base material, a method of forming a physically or chemically bonded polymer layer on the surface of the base material by allowing a polymer having a group capable of adsorbing or reacting with the base material at the end of the base material to act on the base material. It has been known. Further, there is also known a method of forming a polymer layer grafted from the surface of a base material by polymerizing a monomer starting from a polymerizable group imparted to the surface of the base material.
近年、１９９０年代に発展したリビングラジカル重合の技術を利用して基板上に高密度にグラフトされる、いわゆる「濃厚ポリマーブラシ」が研究されている。この濃厚ポリマーブラシでは、高分子鎖が１〜４ｎｍ間隔の高密度で基板上にグラフトされる。このような濃厚ポリマーブラシにより基材表面を改質し、低摩擦性、タンパク質吸着抑制、サイズ排除特性、親水性、撥水性等などの特徴を付与することができる（例えば、特許文献１及び２、非特許文献１〜３）。 In recent years, so-called "concentrated polymer brushes", which are grafted on a substrate at high density by utilizing the technology of living radical polymerization developed in the 1990s, have been studied. In this concentrated polymer brush, polymer chains are grafted onto the substrate at a high density of 1 to 4 nm intervals. The surface of the base material can be modified by such a concentrated polymer brush to impart features such as low friction, protein adsorption suppression, size exclusion characteristics, hydrophilicity, water repellency, and the like (for example, Patent Documents 1 and 2). , Non-Patent Documents 1 to 3).
しかし、基材表面に形成されるポリマー層は、その厚さがナノ〜ミクロンサイズと薄く、しかも透明であることが多い。したがって、ポリマー層の厚さを測定するには、原子間力顕微鏡やエリプソメトリーなどを使用する必要があるため、解析に手間と時間がかかるといった課題がある。また、ポリマー層の一部につけた傷を電子顕微鏡などで観察して、ポリマー層の厚さを測定する方法もあるが、この方法ではポリマー層の一部の厚さしか測定することができない。また、表面処理基材は工業的に大量生産される工業部品であることから、一定の品質が保たれていることを確認するには全量検査する必要がある。しかし、上記の厚さの測定方法等では全量検査に対応することは困難である。 However, the polymer layer formed on the surface of the base material is as thin as a nanometer to a micron size and is often transparent. Therefore, in order to measure the thickness of the polymer layer, it is necessary to use an atomic force microscope, ellipsometry, or the like, which causes a problem that analysis takes time and effort. There is also a method of measuring the thickness of the polymer layer by observing scratches on a part of the polymer layer with an electron microscope or the like, but this method can measure only the thickness of a part of the polymer layer. In addition, since the surface-treated base material is an industrial part that is mass-produced industrially, it is necessary to inspect the entire amount to confirm that a certain quality is maintained. However, it is difficult to support the total amount inspection by the above-mentioned thickness measuring method or the like.
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、傷や欠損等の欠陥の有無や程度を容易に確認することが可能なポリマー層をその表面に備えた表面改質基材の製造方法を提供することにある。また、本発明の課題とするところは、上記の製造方法によって製造される、傷や欠損等の欠陥の有無や程度を容易に確認することが可能なポリマー層をその表面に備えた表面改質基材を提供することにある。さらに、本発明の課題とするところは、上記の表面改質基材の検査方法を提供することにある。 The present invention has been made in view of the problems of the prior art, and the subject thereof is a polymer layer in which the presence or absence and degree of defects such as scratches and defects can be easily confirmed. It is an object of the present invention to provide a method for producing a surface-modified base material provided on the surface thereof. Further, an object of the present invention is a surface modification provided on the surface of a polymer layer produced by the above-mentioned production method, which can easily confirm the presence or absence and degree of defects such as scratches and defects. The purpose is to provide a base material. Further, an object of the present invention is to provide the above-mentioned method for inspecting a surface-modified base material.
すなわち、本発明によれば、以下に示す表面改質基材の製造方法が提供される。
［１］１００〜１，０００ＭＰａの圧力条件下、重合開始基が結合した基材の共存下で、ラジカル重合性蛍光色素を含むモノマーを表面開始ラジカル重合又は表面開始リビングラジカル重合し、前記基材の表面に結合した蛍光性ポリマーからなる膜厚１００ｎｍ以上の蛍光性ポリマー層を形成する工程を有する表面改質基材の製造方法。
［２］さらに、前記重合開始基と同一の開始基を有する開始基モノマーの共存下で表面開始ラジカル重合又は表面開始リビングラジカル重合して、前記蛍光性ポリマー層に含まれない遊離ポリマーを形成し、形成した前記遊離ポリマーの分子量から、前記蛍光性ポリマーの分子量を推測する前記［１］に記載の表面改質基材の製造方法。
［３］前記重合開始基が、下記一般式（１）又は（２）で表される前記［１］又は［２］に記載の表面改質基材の製造方法。
That is, according to the present invention, the following method for producing a surface-modified base material is provided.
[1] Under a pressure condition of 100 to 1,000 MPa, a monomer containing a radically polymerizable fluorescent dye is subjected to surface-initiated radical polymerization or surface-initiated living radical polymerization in the coexistence of a base material to which a polymerization initiating group is bonded, and the base material is subjected to surface-initiated radical polymerization or surface-initiated living radical polymerization. A method for producing a surface-modified base material, which comprises a step of forming a fluorescent polymer layer having a thickness of 100 nm or more, which is made of a fluorescent polymer bonded to the surface of the above.
[2] Further, surface-initiated radical polymerization or surface-initiated living radical polymerization is carried out in the coexistence of an initiating radical monomer having the same initiating group as the polymerization initiating group to form a free polymer not contained in the fluorescent polymer layer. The method for producing a surface-modified base material according to the above [1], wherein the molecular weight of the fluorescent polymer is estimated from the molecular weight of the formed free polymer.
[3] The method for producing a surface-modified base material according to the above [1] or [2], wherein the polymerization initiating group is represented by the following general formula (1) or (2).
［４］さらに、ハロゲン化第４級アンモニウム塩、ハロゲン化第４級ホスホニウム塩、及びハロゲン化アルカリ金属塩からなる群より選択される少なくとも一種の塩の共存下で、表面開始ラジカル重合又は表面開始リビングラジカル重合する前記［１］〜［３］のいずれかに記載の表面改質基材の製造方法。
［５］前記ラジカル重合性蛍光色素が、（メタ）アクリロイルオキシ基を有するモノマーである前記［１］〜［４］のいずれかに記載の表面改質基材の製造方法。
[4] Further, surface initiation radical polymerization or surface initiation in the coexistence of at least one salt selected from the group consisting of a quaternary halogenated ammonium salt, a quaternary halogenated phosphonium salt, and an alkali metal halide salt. The method for producing a surface-modified substrate according to any one of the above [1] to [3], which comprises living radical polymerization.
[5] The method for producing a surface-modified base material according to any one of the above [1] to [4], wherein the radically polymerizable fluorescent dye is a monomer having a (meth) acryloyloxy group.
また、本発明によれば、以下に示す表面改質基材が提供される。
［６］前記［１］及び［３］〜［５］のいずれかに記載の製造方法によって製造される表面改質基材。
Further, according to the present invention, the following surface-modified base materials are provided.
[6] A surface-modified base material produced by the production method according to any one of the above [1] and [3] to [5].
さらに、本発明によれば、以下に示す表面改質基材の検査方法が提供される。
［７］前記［６］に記載の表面改質基材の前記蛍光性ポリマー層に紫外線を照射して発生させた蛍光により、前記蛍光性ポリマー層の状態を確認する工程を有する表面改質基材の検査方法。
Further, according to the present invention, the following methods for inspecting a surface-modified substrate are provided.
[7] A surface modifying group having a step of confirming the state of the fluorescent polymer layer by irradiating the fluorescent polymer layer of the surface modifying substrate according to the above [6] with ultraviolet rays and generating fluorescence. Material inspection method.
本発明によれば、傷や欠損等の欠陥の有無や程度を容易に確認することが可能なポリマー層をその表面に備えた表面改質基材の製造方法を提供することができる。また、本発明によれば、上記の製造方法によって製造される、傷や欠損等の欠陥の有無や程度を容易に確認することが可能なポリマー層をその表面に備えた表面改質基材を提供することができる。さらに、本発明によれば、上記の表面改質基材の検査方法を提供することができる。 INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing a surface-modified base material provided with a polymer layer on the surface thereof, which allows the presence or absence and degree of defects such as scratches and defects to be easily confirmed. Further, according to the present invention, a surface-modified base material produced by the above-mentioned production method and provided with a polymer layer on its surface capable of easily confirming the presence or absence and degree of defects such as scratches and defects. Can be provided. Furthermore, according to the present invention, it is possible to provide the above-mentioned method for inspecting a surface-modified base material.
＜表面改質基材及びその製造方法＞
以下、本発明の実施の形態について説明するが、本発明は以下の実施の形態に限定されるものではない。本発明の表面改質基材の製造方法は、常圧〜１，０００ＭＰａの圧力条件下、重合開始基が結合した基材の共存下で、ラジカル重合性蛍光色素を含むモノマーを表面開始ラジカル重合又は表面開始リビングラジカル重合し、前記基材の表面に結合した蛍光性ポリマーからなる蛍光性ポリマー層を形成する工程（重合工程）を有する。また、本発明の表面改質基材は、上記の製造方法によって製造されるものである。以下、本発明の表面改質基材及びその製造方法の詳細について説明する。
<Surface modified base material and its manufacturing method>
Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. In the method for producing a surface-modified base material of the present invention, a monomer containing a radically polymerizable fluorescent dye is subjected to surface-initiated radical polymerization under a pressure condition of normal pressure to 1,000 MPa in the coexistence of a base material to which a polymerization initiating group is bonded. Alternatively, it has a step (polymerization step) of forming a fluorescent polymer layer made of a fluorescent polymer bonded to the surface of the base material by surface-initiated living radical polymerization. Further, the surface-modified base material of the present invention is produced by the above-mentioned production method. Hereinafter, the details of the surface-modified base material of the present invention and the method for producing the same will be described.
従来、基材の表面からビニル系ポリマーをグラフトさせて表面改質する方法が知られている。基材表面にポリマーをグラフトさせる方法としては、例えば、基材表面からポリマーを重合させる、いわゆる表面開始重合方法がある。表面開始重合方法としては、基材表面に放射線等を照射して発生させたラジカルから重合を開始する方法；基材表面に導入したアゾ基や過酸化物基を有する化合物から重合を開始する方法；などがある。これに対して、本発明の表面改質基材の製造方法では、ラジカルを発生させる基である重合開始基がその表面に結合した基材を使用し、この重合開始基からラジカル重合又はリビングラジカル重合してポリマーをグラフトさせ、基材の表面にポリマー層を形成する。 Conventionally, a method of grafting a vinyl polymer from the surface of a base material to modify the surface has been known. As a method of grafting a polymer on the surface of a base material, for example, there is a so-called surface initiation polymerization method of polymerizing a polymer from the surface of a base material. As a surface-initiated polymerization method, a method of initiating polymerization from radicals generated by irradiating the surface of the base material with radiation or the like; a method of initiating polymerization from a compound having an azo group or a peroxide group introduced into the surface of the base material. ;and so on. On the other hand, in the method for producing a surface-modified base material of the present invention, a base material in which a polymerization initiating group, which is a radical-generating group, is bonded to the surface thereof is used, and radical polymerization or living radicals are used from the polymerization initiating group. It polymerizes and grafts the polymer to form a polymer layer on the surface of the substrate.
（基材）
基材の種類は特に限定されず、天然物、人工物、無機部材、有機部材のいずれであっても用いることができる。また、塊状物、粉末、シート、フィルム、ペレット、板などのさまざまな形状の基材を用いることができる。なかでも、重合溶液に耐えうる基材を用いることが好ましい。基材の具体例としては、金属、金属酸化物、金属窒化物、金属炭化物、セラミックス、木材、ケイ素化合物、熱可塑性樹脂、熱硬化性樹脂、セルロース、ガラス等のフィルム、繊維、シートなどを挙げることができる。
(Base material)
The type of the base material is not particularly limited, and any of natural products, artificial materials, inorganic members, and organic members can be used. In addition, various shapes of substrates such as lumps, powders, sheets, films, pellets, and plates can be used. Of these, it is preferable to use a base material that can withstand the polymerization solution. Specific examples of the base material include metals, metal oxides, metal nitrides, metal carbides, ceramics, wood, silicon compounds, thermoplastic resins, thermosetting resins, cellulose, films such as glass, fibers, and sheets. be able to.
基材には表面処理を施してもよい。表面処理としては、シランカップリング処理、シリカコート処理、シリカアルミナ処理などの無機処理；プラズマ処理、紫外線照射処理、オゾン酸化処理、放射線処理、Ｘ線処理、電子線処理、レーザー処理などの洗浄・活性化処理などを挙げることができる。 The base material may be surface-treated. Surface treatments include inorganic treatments such as silane coupling treatment, silica coating treatment, and silica alumina treatment; cleaning such as plasma treatment, ultraviolet irradiation treatment, ozone oxidation treatment, radiation treatment, X-ray treatment, electron beam treatment, and laser treatment. Activation treatment and the like can be mentioned.
（重合開始基）
重合開始基としては、通常の（リビング）ラジカル重合で用いられる開始基を用いることができる。リビングラジカル重合としては、ニトロキサイド化合物を開始化合物として熱解離させてラジカルを発生させるＮＭＰ法；ハロゲン基を有する化合物を開始化合物として、銅やルテニウムの金属錯体を触媒として酸化還元で行う原子移動ラジカル重合（ＡＴＲＰ法）；ジチオエステル基を有する化合物を使用する可逆的付加開裂型連鎖移動重合（ＲＡＦＴ法）；有機テルルを開始化合物とするＴＥＲＰ法；ヨウ素基を有する化合物を開始化合物とし、触媒としてヨウ素をラジカルとして引き抜くことができる有機化合物を触媒として行う可逆的移動触媒重合（ＲＴＣＰ法）；ハロゲン基を有する化合物を開始化合物として、触媒としてハロゲン化第４級アンモニウム塩等を使用して重合する可逆的触媒媒介重合（ＲＣＭＰ法）；ハロゲン交換重合；などがある。これらの重合法で用いられる開始基をその表面に導入した基材を使用し、その開始基を起点として（リビング）ラジカル重合することで、基材の表面に蛍光性ポリマーが結合（グラフト）した蛍光性ポリマー層を形成することができる。
(Polymerization initiator)
As the polymerization initiating group, an initiating group used in ordinary (living) radical polymerization can be used. Living radical polymerization is an NMP method in which a nitroxide compound is used as a starting compound to thermally dissociate to generate radicals; an atomic transfer radical polymerization is carried out by oxidation-reduction using a compound having a halogen group as a starting compound and using a metal complex of copper or ruthenium as a catalyst. (ATRP method); Reversible addition cleavage type chain transfer polymerization using a compound having a dithioester group (RAFT method); TERP method using an organic tellurium as an initiating compound; Reversible mobile catalytic polymerization (RTCP method) using an organic compound capable of extracting radicals as a radical; reversible polymerization using a compound having a halogen group as a starting compound and using a halogenated quaternary ammonium salt or the like as a catalyst. Radical-mediated polymerization (RCMP method); halogen exchange polymerization; etc. A fluorescent polymer was bonded (grafted) to the surface of the base material by using a base material in which the starting radicals used in these polymerization methods were introduced onto the surface thereof and performing radical polymerization starting from the starting radical (living group). A fluorescent polymer layer can be formed.
ニトロキサイド化合物を使用するＮＭＰ法、有機テルル化合物を使用するＴＥＲＰ法、及びジチオエステル基を有する化合物を使用するＲＡＦＴ法の場合、開始化合物は特殊であり、コスト的にもさほど有利であるとは言えない。このため、下記一般式（１）又は（２）で表される重合開始基を用いることが好ましい。一般式（１）又は（２）中のＸがラジカルとして脱離するとともに、生成した炭素ラジカルにしてモノマーが挿入されて重合する。これにより、開始基を末端とするポリマーが形成される。 In the case of the NMP method using a nitroxide compound, the TERP method using an organic tellurium compound, and the RAFT method using a compound having a dithioester group, the starting compound is special and is not so advantageous in terms of cost. No. Therefore, it is preferable to use the polymerization initiating group represented by the following general formula (1) or (2). X in the general formula (1) or (2) is eliminated as a radical, and a monomer is inserted into the generated carbon radical to polymerize. As a result, a polymer ending with an initiating group is formed.
一般式（１）中、Ｘが結合している炭素原子は第３級炭素原子又は第４級炭素原子である。Ｒ１及びＲ２の少なくとも１つはアルキル基以外の基であることが好ましい。すなわち、Ｒ１及びＲ２の少なくとも１つがアルキル基以外の電子供与性基であると、Ｘが脱離しやすくなる。なかでも、Ｘが第４級炭素原子に結合していると、ラジカルを発生させるのにより好ましい。 In the general formula (1), the carbon atom to which X is bonded is a tertiary carbon atom or a quaternary carbon atom. At least one of R 1 and R 2 is preferably a group other than an alkyl group. That is, when at least one of R 1 and R 2 is an electron donating group other than the alkyl group, X is easily eliminated. Among them, when X is bonded to a quaternary carbon atom, it is more preferable to generate radicals.
一般式（２）中、Ｘが結合している炭素原子は第３級炭素原子又は第４級炭素原子である。エステル基又はアミド基が電子供与性基であるので、Ｒ３及びＲ４のいずれもがアルキル基であってもよい。また、Ｘが第４級炭素原子に結合していると、ラジカルを発生させるのにより好ましい。 In the general formula (2), the carbon atom to which X is bonded is a tertiary carbon atom or a quaternary carbon atom. Since the ester group or the amide group is an electron donating group, both R 3 and R 4 may be alkyl groups. Further, it is more preferable that X is bonded to a quaternary carbon atom because it generates radicals.
重合開始基を基材の表面に導入する（結合させる）方法としては、例えば、重合開始基を有する化合物を、塗布、蒸着、転写、電着、ラミネート、単層膜形成などの方法で基材に付与する方法を挙げることができる。なかでも、重合開始基及び基材と反応する基を有する化合物や；重合開始基を有するポリマーを基材に付与することが好ましい。重合開始基を有するポリマーとしては、三次元架橋構造を有するポリマーや、基材と反応する基をさらに有するポリマーが好ましい。基材と反応する基を有する化合物やポリマーを基材に付与することで、基材表面に重合開始基を基材表面に強固に導入することができる。 As a method of introducing (bonding) the polymerization initiating group to the surface of the base material, for example, a compound having a polymerization initiating group is applied to the base material by a method such as coating, vapor deposition, transfer, electrodeposition, lamination, or monolayer film formation. The method of giving to is given. Among them, it is preferable to impart a compound having a polymerization initiating group and a group that reacts with the base material; or a polymer having a polymerization initiating group to the base material. As the polymer having a polymerization initiating group, a polymer having a three-dimensional crosslinked structure and a polymer having a group further reacting with a base material are preferable. By imparting a compound or polymer having a group that reacts with the base material to the base material, the polymerization initiating group can be firmly introduced into the surface of the base material.
反応性基は、基材の種類にあわせて適宜選択すればよい。例えば、シリコン基板、金属、金属酸化物、水酸基を有する無機化合物等を基材として用いる場合には、アルコキシシリル基、エポキシ基などが反応性基として好ましい。また、セルロースなどの水酸基を有する有機化合物を基材として用いる場合には、酸ハロゲン化物、酸無水物、イソシアネート基などが反応性基として好ましい。 The reactive group may be appropriately selected according to the type of the base material. For example, when a silicon substrate, a metal, a metal oxide, an inorganic compound having a hydroxyl group or the like is used as a base material, an alkoxysilyl group, an epoxy group or the like is preferable as the reactive group. When an organic compound having a hydroxyl group such as cellulose is used as a base material, an acid halide, an acid anhydride, an isocyanate group or the like is preferable as the reactive group.
重合性基を有するポリマーとしては、下記一般式（３）で表されるモノマーと、（メタ）アクリロシロキシプロピルトリメチルシリルや（メタ）アクリロイロキシプロピルトリエトキシシリルなどのアルコキシシリル基を有するモノマーと、を含むモノマー成分を重合して得られるポリマー（ポリマータイプの処理剤）を用いることが好ましい。 Examples of the polymer having a polymerizable group include a monomer represented by the following general formula (3) and a monomer having an alkoxysilyl group such as (meth) acrylosiloxypropyltrimethylsilyl or (meth) acryloyloxypropyltriethoxysilyl. It is preferable to use a polymer (polymer type treatment agent) obtained by polymerizing a monomer component containing.
また、重合開始基を有する化合物としては、下記式（４）で表される、重合開始基及び基材と反応する基（アルコキシシリル基）を有する化合物を用いることが好ましい。 Further, as the compound having a polymerization initiating group, it is preferable to use a compound having a polymerization initiating group and a group (alkoxysilyl group) that reacts with the substrate, which is represented by the following formula (4).
（ラジカル重合性蛍光色素）
ラジカル重合性蛍光色素は、不飽和結合等を含むラジカル重合性基を有する蛍光色素である。このようなラジカル重合性蛍光色素を含むモノマーを重合することで、基材の表面に結合した蛍光性ポリマーからなる蛍光性ポリマー層を形成することができる。ラジカル重合性蛍光色素としては、メロシアニン系蛍光色素、ペリレン系蛍光色素、アクリジン系蛍光色素、ルシフェリン系蛍光色素、ピラニン系蛍光色素、スチルベン系蛍光色素、ローダミ系蛍光色素、クマリン系蛍光色素、アゾ系蛍光色素、ピラン系蛍光色素、ピロメテン系蛍光色素、フルオレセイン系蛍光色素、ウンベリフェロン系蛍光色素などの有機系色素；ユウロピウム系色素などの無機系色素；を挙げることができる。
(Radical polymerizable fluorescent dye)
The radically polymerizable fluorescent dye is a fluorescent dye having a radically polymerizable group containing an unsaturated bond or the like. By polymerizing a monomer containing such a radically polymerizable fluorescent dye, a fluorescent polymer layer made of a fluorescent polymer bonded to the surface of a base material can be formed. The radically polymerizable fluorescent dyes include merocyanine-based fluorescent dyes, perylene-based fluorescent dyes, acrydin-based fluorescent dyes, luciferin-based fluorescent dyes, pyranine-based fluorescent dyes, stilben-based fluorescent dyes, Rhodami-based fluorescent dyes, coumarin-based fluorescent dyes, and azo-based fluorescent dyes. Organic dyes such as fluorescent dyes, pyran-based fluorescent dyes, pyromethene-based fluorescent dyes, fluorescein-based fluorescent dyes, and umbelliferon-based fluorescent dyes; and inorganic dyes such as europium-based dyes; can be mentioned.
ラジカル重合性蛍光色素のより具体的な例としては、下記一般式（５）〜（１１）（Ｒは水素原子又はメチル基を示す）で表される（メタ）アクリロイルオキシ基を有するモノマーを挙げることができる。また、下記一般式（５）〜（１１）中のＲは、メチル基であることが好ましい。 More specific examples of the radically polymerizable fluorescent dye include monomers having a (meth) acryloyloxy group represented by the following general formulas (5) to (11) (R represents a hydrogen atom or a methyl group). be able to. Further, R in the following general formulas (5) to (11) is preferably a methyl group.
重合させるモノマーの全てをラジカル重合性蛍光色素としてもよいが、濃度消光等により発光しにくくなったり、嵩高いモノマーであるために反応せずに残存したりする場合がある。また、ラジカル重合性色素は発光強度が高いため、使用量が少なくても強く発光する。このため、全モノマー中のラジカル重合性蛍光色素の量は、０．０１〜１０質量％とすることが好ましく、０．１〜５質量％とすることがさらに好ましい。 All of the monomers to be polymerized may be radically polymerizable fluorescent dyes, but they may be difficult to emit light due to concentration quenching or the like, or may remain without reacting because they are bulky monomers. Further, since the radically polymerizable dye has high emission intensity, it emits strong light even if the amount used is small. Therefore, the amount of the radically polymerizable fluorescent dye in all the monomers is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass.
（ラジカル重合性蛍光色素以外のモノマー）
ラジカル重合性蛍光色素以外のモノマー（その他のモノマー）としては、ラジカル重合しうる従来公知のモノマーをいずれも用いることができ、形成しようとする蛍光性ポリマー層の特性に合わせて適宜選択して用いればよい。なかでも、（メタ）アクリロイルオキシ基を有するモノマー（（メタ）アクリレート系モノマー）を用いることが好ましく、（メタクリロイルオキシ基を有するモノマー（メタクリレート系モノマー）を用いることがさらに好ましい。
(Monomers other than radically polymerizable fluorescent dyes)
As the monomer other than the radically polymerizable fluorescent dye (other monomer), any conventionally known monomer capable of radical polymerization can be used, and it is appropriately selected and used according to the characteristics of the fluorescent polymer layer to be formed. Just do it. Among them, it is preferable to use a monomer having a (meth) acryloyloxy group ((meth) acrylate-based monomer), and more preferably to use (a monomer having a methacryloyloxy group (methacrylate-based monomer)).
（重合方法）
重合工程では、上記のラジカル重合性蛍光色素を含むモノマーをラジカル重合又はリビングラジカル重合する。また、一般式（１）又は（２）で表される基などのハロゲン原子を有する基を重合開始基とする場合、従来公知の金属錯体を用いる原子移動ラジカル重合によってモノマーを重合することが好ましい。金属錯体としては、塩化銅、臭化銅と、ジノニルビピリジン、トリジメチルアミノエチルアミン、ペンタメチルジエチレントリアミンなどのポリアミンとの錯体や；ジクロロトリス（トリフェニルホスフィン）ルテニウム；などを挙げることができる。原子移動ラジカル重合は、バルク重合であってもよく、有機溶剤などを用いる溶液重合であってもよい。有機溶剤としては、炭化水素系溶剤、エステル系溶剤、グリコール系溶剤、エーテル系溶剤、アミド系溶剤、アルコール系溶剤、スルホキシド系溶剤、尿素系溶剤、イオン液体などを用いることができる。
(Polymerization method)
In the polymerization step, the monomer containing the above radically polymerizable fluorescent dye is radically polymerized or living radically polymerized. When a group having a halogen atom such as a group represented by the general formula (1) or (2) is used as a polymerization initiator group, it is preferable to polymerize the monomer by atom transfer radical polymerization using a conventionally known metal complex. .. Examples of the metal complex include a complex of copper chloride and copper bromide with polyamines such as dinonylbipyridine, tridimethylaminoethylamine and pentamethyldiethylenetriamine; and dichlorotris (triphenylphosphine) ruthenium; and the like. The atom transfer radical polymerization may be bulk polymerization or solution polymerization using an organic solvent or the like. As the organic solvent, a hydrocarbon solvent, an ester solvent, a glycol solvent, an ether solvent, an amide solvent, an alcohol solvent, a sulfoxide solvent, a urea solvent, an ionic liquid and the like can be used.
原子移動ラジカル重合では重金属を用いるため、着色や環境への負荷を考慮する必要があるとともに、反応系から除去する必要もある。このため、重金属を用いない汎用の有機化合物の存在下で重合することが好ましい。具体的には、ハロゲン化第４級アンモニウム塩、ハロゲン化第４級ホスホニウム塩、及びハロゲン化アルカリ金属塩からなる群より選択される少なくとも一種の塩の共存下で、ラジカル重合性蛍光色素と（メタ）アクリレート系モノマーを含むモノマーを重合することが好ましい。これにより、市販の安価な有機材料や無機塩で重合することができる。また、金属を除去する必要がないため、環境に対する負荷を減ずることができるとともに、工程を簡略化することもできる。 Since heavy metals are used in atom transfer radical polymerization, it is necessary to consider coloring and environmental load, and it is also necessary to remove them from the reaction system. Therefore, it is preferable to polymerize in the presence of a general-purpose organic compound that does not use heavy metals. Specifically, in the coexistence of at least one salt selected from the group consisting of a quaternary ammonium salt of halogenation, a quaternary phosphonium halide salt, and an alkali metal halide salt, the radically polymerizable fluorescent dye ( It is preferable to polymerize a monomer containing a meta) acrylate-based monomer. As a result, it is possible to polymerize with a commercially available inexpensive organic material or inorganic salt. Moreover, since it is not necessary to remove the metal, the load on the environment can be reduced and the process can be simplified.
重合開始基中のＸ（ハロゲン）がラジカルとして脱離するとともに、Ｘの脱離とともに生成した炭素ラジカルにモノマーが挿入されて重合が進行する。その際、上記の特定の塩を共存させることで、ハロゲンラジカルの引き抜き又はハロゲン交換が生じ、生成した炭素ラジカルからモノマーの重合が進行して蛍光性ポリマーが形成される。 X (halogen) in the polymerization initiation group is eliminated as a radical, and a monomer is inserted into the carbon radical generated by the elimination of X to proceed with the polymerization. At that time, by coexisting the above-mentioned specific salt, extraction or halogen exchange of halogen radicals occurs, and the polymerization of the monomer proceeds from the generated carbon radicals to form a fluorescent polymer.
ハロゲン化第４級アンモニウム塩としては、塩化ベンジルトリメチルアンモニウム、臭化テトラブチルアンモニウム、ヨウ化テトラブチルアンモニウム、ヨウ化テトラオクチルアンモニウム、塩化ノニルピリジニウム、塩化コリンなどを挙げることができる。ハロゲン化第４級ホスホニウム塩としては、塩化テトラフェニルホスホニウム、臭化メチルトリブチルホスホニウム、ヨウ化テトラブチルホスホニウムなどを挙げることができる。ハロゲン化アルカリ金属塩としては、臭化リチウム、ヨウ化カリウムなどを挙げることができる。 Examples of the quaternary ammonium salt halide include benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, tetraoctylammonium iodide, nonylpyridinium chloride, choline chloride and the like. Examples of the quaternary halogenated phosphonium salt include tetraphenylphosphonium chloride, methyltributylphosphonium bromide, tetrabutylphosphonium iodide and the like. Examples of the alkali metal halide include lithium bromide and potassium iodide.
塩としては、ヨウ化物塩を用いることが好ましい。ヨウ化物塩を用いることで、リビングラジカル重合が進行し、分子量分布がより狭いポリマーを得ることができる。また、ヨウ化第４級アンモニウム塩、ヨウ化第４級ホスホニウム塩、及びヨウ化アルカリ金属塩などの重合溶液に溶解しうる塩を用いることが好ましく、ヨウ化第４級アンモニウム塩を用いることがさらに好ましい。ヨウ化第４級アンモニウム塩としては、ヨウ化ベンジルテトラブチルアンモニウム、ヨウ化テトラブチルアンモニウム、ヨウ化テトラオクチルアンモニウム、ヨウ化ドデシルトリメチルアンモニウム、ヨウ化オクタデシルトリメチルアンモニウム、ヨウ化トリオクダデシルメチルアンモニウムなどを挙げることができる。 As the salt, it is preferable to use an iodide salt. By using the iodide salt, living radical polymerization proceeds and a polymer having a narrower molecular weight distribution can be obtained. Further, it is preferable to use a salt that can be dissolved in a polymerization solution such as a quaternary ammonium iodide salt, a quaternary phosphonium iodide salt, and an alkali metal iodide salt, and it is preferable to use a quaternary ammonium iodide salt. More preferred. Examples of the quaternary ammonium salt iodide include benzyltetrabutylammonium iodide, tetrabutylammonium iodide, tetraoctylammonium iodide, dodecyltrimethylammonium iodide, octadecyltrimethylammonium iodide, and trioctadecylmethylammonium iodide. Can be mentioned.
活性度を高めるとともに、より濃厚で高分子量のポリマーを得る観点から、重合開始基に対する塩の量は当モル以上とすることが好ましく、１０倍モル以上とすることがさらに好ましく、１００倍モル以上としてもよい。 From the viewpoint of increasing the activity and obtaining a thicker and higher molecular weight polymer, the amount of the salt with respect to the polymerization initiating group is preferably at least this molar amount, more preferably 10 times mol or more, and more preferably 100 times mol or more. May be.
この第４級塩やハロゲン化物塩を使用する方法において、その重合条件は特に限定されない。従来公知の条件で行われる。好ましくは、温度は６０℃以上、溶媒として有機溶媒を使用することが好ましい。溶媒としては、従来公知の溶媒が使用でき、特に限定されない。その溶剤は前記した従来公知の有機溶剤が使用できるが、好ましくは、塩を溶解する溶剤を使用することがよく、アルコール系、グリコール系、アミド系、尿素系、スルホキシド系、イオン液体などの極性が高い有機溶剤が好ましい。 In the method using the quaternary salt or the halide salt, the polymerization conditions are not particularly limited. This is performed under conventionally known conditions. Preferably, the temperature is 60 ° C. or higher, and it is preferable to use an organic solvent as the solvent. As the solvent, a conventionally known solvent can be used and is not particularly limited. As the solvent, the above-mentioned conventionally known organic solvent can be used, but preferably, a solvent that dissolves a salt is used, and polarities such as alcohol-based, glycol-based, amide-based, urea-based, sulfoxide-based, and ionic liquid are used. An organic solvent having a high value is preferable.
重合工程では、常圧〜１，０００ＭＰａの圧力条件下、好ましくは１００〜１，０００ＭＰａ、さらに好ましくは２００〜８００ＭＰａ、特に好ましくは３００〜６００ＭＰａの圧力条件下で重合する。具体的には、モノマー及び基材を入れた重合容器の全体に、水などの媒体を介して均一に圧力を付与しながら重合する。圧力を付与した状態でラジカル重合することで、停止反応を抑制し、より高分子量の蛍光性ポリマーを形成することができる。 In the polymerization step, polymerization is carried out under pressure conditions of normal pressure to 1,000 MPa, preferably 100 to 1,000 MPa, more preferably 200 to 800 MPa, and particularly preferably 300 to 600 MPa. Specifically, the polymerization vessel containing the monomer and the base material is polymerized while uniformly applying pressure through a medium such as water. By radical polymerization under pressure, the termination reaction can be suppressed and a higher molecular weight fluorescent polymer can be formed.
圧力を付与した状態、好ましくは１００ＭＰａ以上の圧力条件下でラジカル重合することで、停止反応を抑制し、より高分子量の蛍光性ポリマーを形成することができる。なお、１，０００ＭＰａ超の圧力に耐えうる容器や装置を用意するのは困難であり、実用的ではない。形成される蛍光性ポリマーの分子量が大きくなるに伴い、基材表面に形成される蛍光性ポリマー層の膜厚が厚くなる。蛍光性ポリマー層の膜厚を厚くすることで、基材表面をこれまでにない特性を示すように改質することができる。蛍光性ポリマー層の膜厚は、例えば、数ｎｍから数μｍとすることができ、好ましくは１０ｎｍ以上、さらに好ましくは１００ｎｍ以上とすることができる。 By radical polymerization in a state where pressure is applied, preferably under a pressure condition of 100 MPa or more, the termination reaction can be suppressed and a higher molecular weight fluorescent polymer can be formed. It is difficult to prepare a container or device capable of withstanding a pressure of more than 1,000 MPa, which is not practical. As the molecular weight of the fluorescent polymer formed increases, the film thickness of the fluorescent polymer layer formed on the surface of the substrate increases. By increasing the film thickness of the fluorescent polymer layer, the surface of the base material can be modified to exhibit unprecedented characteristics. The film thickness of the fluorescent polymer layer can be, for example, from several nm to several μm, preferably 10 nm or more, and more preferably 100 nm or more.
重合容器としては、密閉可能であるとともに、高圧に耐えうる容器を用いることが好ましい。また、容器の内部に圧力が伝達される必要があるため、プラスチック製の軟質部分や伸縮部分などの、圧力で変形する部分を有する容器を用いることが好ましい。具体的には、ポリエチレン製の瓶、ペットボトル、レトルトパウチ、ブリスター容器など様々な容器を用いることができる。また、重合時の温度で変形しにくい、耐熱性を有する素材からなる容器が好ましい。さらに、重合用の溶剤等で侵されにくい、耐薬品性や耐溶剤性などの特性を有する素材からなる容器が好ましい。重合容器を構成する素材としては、例えば、ポリオレフィン系樹脂、フッ素系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、エンジニアプラスチック等を挙げることができる。また、重合時には、可能な限り、重合容器内に気体が入りこまないようにすることが好ましい。例えば、重合容器の容量の９０％以上に重合溶液を仕込むことが好ましい。 As the polymerization container, it is preferable to use a container that can be hermetically sealed and can withstand high pressure. Further, since pressure needs to be transmitted to the inside of the container, it is preferable to use a container having a portion that is deformed by pressure, such as a soft portion or an elastic portion made of plastic. Specifically, various containers such as polyethylene bottles, PET bottles, retort pouches, and blister containers can be used. Further, a container made of a heat-resistant material that is not easily deformed at the temperature at the time of polymerization is preferable. Further, a container made of a material having characteristics such as chemical resistance and solvent resistance, which is not easily attacked by a solvent for polymerization or the like, is preferable. Examples of the material constituting the polymerization container include polyolefin-based resin, fluorine-based resin, polyester-based resin, polyamide-based resin, engineering plastic, and the like. Further, at the time of polymerization, it is preferable to prevent gas from entering the polymerization container as much as possible. For example, it is preferable to charge the polymerization solution in 90% or more of the capacity of the polymerization vessel.
ラジカル重合性蛍光色素以外のモノマー（その他のモノマー）を適宜選択して用いることで、形成される蛍光性ポリマー層の特性を任意に設定することができる。例えば、その他のモノマーとしてフッ素系モノマーを用いることで、水や油をはじきやすい表面張力の低い蛍光性ポリマー層を形成することができる。また、その他のモノマーとしてポリエチレングリコール基やカルボキシ基などを有するモノマーを使用することで、当たった水蒸気が直ちに水滴となって曇りにくい親水性の蛍光性ポリマー層を形成することができる。さらに、タンパク等が付着しにくい生体適合性基材を製造することも可能である。また、形成された蛍光性ポリマー層を潤滑油等で膨潤させて潤滑膜とし、極低摩擦性のポリマー層とすることもできる。 By appropriately selecting and using a monomer other than the radically polymerizable fluorescent dye (other monomer), the characteristics of the formed fluorescent polymer layer can be arbitrarily set. For example, by using a fluorine-based monomer as another monomer, it is possible to form a fluorescent polymer layer having a low surface tension that easily repels water and oil. Further, by using a monomer having a polyethylene glycol group, a carboxy group, or the like as another monomer, the water vapor that hits the monomer immediately becomes water droplets to form a hydrophilic fluorescent polymer layer that is hard to fog. Furthermore, it is also possible to produce a biocompatible base material to which proteins and the like are less likely to adhere. Further, the formed fluorescent polymer layer can be swollen with a lubricating oil or the like to form a lubricating film, and a polymer layer having extremely low friction can be obtained.
形成されるポリマー層は、後述するように、紫外線を照射することで蛍光を発する蛍光性ポリマー層であることから、紫外線の照射によってポリマー層における傷や欠損等の欠陥の有無や程度を容易に確認することができる。但し、ポリマー層における欠陥の有無や程度を確認することは可能である一方で、形成された蛍光性ポリマー層を構成する蛍光性ポリマーの分子量を検証することは容易であるとは言えない。そこで、本発明の製造方法では、重合開始基と同一の開始基を有する開始基モノマーの共存下で表面開始ラジカル重合又は表面開始リビングラジカル重合することが好ましい。すなわち、基材に結合せずにフリーで存在する開始基モノマーをラジカル重合することで、蛍光性ポリマー層に含まれない遊離ポリマーが形成される。そして、形成された遊離ポリマーの分子量を定法にしたがって測定することで、基材表面に形成された蛍光性ポリマー層を構成する蛍光性ポリマーの分子量を推測することができる。 As will be described later, the polymer layer to be formed is a fluorescent polymer layer that emits fluorescence when irradiated with ultraviolet rays, so that the presence or absence and degree of defects such as scratches and defects in the polymer layer can be easily determined by irradiation with ultraviolet rays. You can check. However, while it is possible to confirm the presence or absence and degree of defects in the polymer layer, it is not easy to verify the molecular weight of the fluorescent polymer constituting the formed fluorescent polymer layer. Therefore, in the production method of the present invention, it is preferable to carry out surface-initiated radical polymerization or surface-initiated living radical polymerization in the presence of an initiating radical monomer having the same initiating group as the polymerization initiating group. That is, a free polymer that is not contained in the fluorescent polymer layer is formed by radical polymerization of a free radical monomer that does not bind to the substrate. Then, by measuring the molecular weight of the formed free polymer according to a conventional method, the molecular weight of the fluorescent polymer constituting the fluorescent polymer layer formed on the surface of the base material can be estimated.
開始基モノマーとしては、基材に結合した重合開始基と同一の基を有する化合物を用いる。具体的には、下記式（１２）〜（１４）で表される化合物を開始基モノマーとして用いることができる。 As the initiating group monomer, a compound having the same group as the polymerization initiating group bonded to the substrate is used. Specifically, the compounds represented by the following formulas (12) to (14) can be used as the starting group monomer.
重合系中の開始基モノマーの量は、０．０１質量％以下とすることが好ましく、０．００１質量％以下とすることがさらに好ましい。開始基モノマーの量が多すぎると、重合系が高粘度化してしまい、得られる表面改質基材を取り出しにくくなることがある。また、基材表面に付着した、開始基モノマーから形成された遊離ポリマーを洗浄して除去するのに時間がかかる場合がある。なお、形成される遊離ポリマーの、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定されるポリスチレン換算の数平均分子量（Ｍｎ）は、通常、１，０００〜１０，０００，０００であり、好ましくは１００，０００以上である。 The amount of the initiating group monomer in the polymerization system is preferably 0.01% by mass or less, and more preferably 0.001% by mass or less. If the amount of the initiating group monomer is too large, the polymerization system becomes highly viscous, and it may be difficult to take out the obtained surface-modified base material. In addition, it may take time to wash and remove the free polymer formed from the initiating group monomer adhering to the surface of the substrate. The polystyrene-equivalent number average molecular weight (Mn) of the formed free polymer measured by gel permeation chromatography (GPC) is usually 1,000 to 10,000,000, preferably 100, It is over 000.
本発明の製造方法によれば、基材の表面特性を顕著に改質した表面改質基材を簡便に製造することができる。このため、本発明の製造方法は、医療用部材、電子材料、ディスプレイ材料、半導体材料、機械部品、摺動部材、電池材料などの様々な分野で用いられる各種の基材を製造する方法として有用である。さらに、紫外線照射により蛍光を発する蛍光性ポリマー層を有することから、ダミー防止、セキュリティー用途、意匠用途、及び潜在画像表現等に使用することができる。 According to the production method of the present invention, a surface-modified base material in which the surface characteristics of the base material are remarkably modified can be easily produced. Therefore, the manufacturing method of the present invention is useful as a method for manufacturing various base materials used in various fields such as medical members, electronic materials, display materials, semiconductor materials, mechanical parts, sliding members, and battery materials. Is. Further, since it has a fluorescent polymer layer that fluoresces when irradiated with ultraviolet rays, it can be used for dummy prevention, security use, design use, latent image expression, and the like.
＜表面改質基材の検査方法＞
本発明の表面改質基材の検査方法は、上述の製造方法によって製造された表面改質基材の蛍光性ポリマー層に紫外線を照射して発生させた蛍光により、蛍光性ポリマー層の状態を確認する工程を有する。蛍光ポリマー層から発した蛍光を観察することで、基材表面がうまく改質されたか；基材表面の全体が改質されたか；すべての基材（全てのロット）の表面が改質されたか；等を確認することができる。すなわち、本発明の表面改質基材の検査方法は、製品を傷つけることなく検査することが可能な非破壊検査の一種である。
<Inspection method for surface modified base material>
In the method for inspecting the surface-modified base material of the present invention, the state of the fluorescent polymer layer is determined by fluorescence generated by irradiating the fluorescent polymer layer of the surface-modified base material produced by the above-mentioned production method with ultraviolet rays. Has a step to confirm. By observing the fluorescence emitted from the fluorescent polymer layer, was the surface of the substrate modified successfully; was the entire surface of the substrate modified; was the surface of all substrates (all lots) modified? ; Etc. can be confirmed. That is, the method for inspecting a surface-modified base material of the present invention is a kind of non-destructive inspection capable of inspecting a product without damaging it.
紫外線を照射する装置としては、例えば、２５４ｎｍ、３５０〜４００ｎｍなどの紫外線を発光する光源、ブラックライト、水銀ランプ、メタルハライドランプ、ＬＥＤライトなどを用いることができる。また、ハンディータイプの装置を使用して表面改質基材を個別に検査してもよいし、ベルトコンベア等の搬送手段に載せた複数の表面改質基材を機械的に連続して検査してもよい。さらには、蛍光顕微鏡を使用して、μｍオーダー以下の傷や欠損等を確認することもできる。また、分光蛍光光度計や紫外可視分光光度計などの分光光度計などを使用することもできる。 As the device for irradiating the ultraviolet rays, for example, a light source that emits ultraviolet rays such as 254 nm and 350 to 400 nm, a black light, a mercury lamp, a metal halide lamp, an LED light, and the like can be used. Further, the surface-modified base material may be individually inspected using a handy type device, or a plurality of surface-modified base materials mounted on a transport means such as a belt conveyor may be mechanically and continuously inspected. You may. Furthermore, a fluorescence microscope can be used to confirm scratches and defects on the order of μm or less. Further, a spectrophotometer such as a spectrofluorometer or an ultraviolet-visible spectrophotometer can also be used.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。 Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In addition, "part" and "%" in Examples and Comparative Examples are based on mass unless otherwise specified.
＜表面改質基材の製造（１）＞
（参考例１）
１ｃｍ×１ｃｍサイズのシリコン基板をイソプロピルアルコールで超音波洗浄した後、チップクリーナー（バイオフォースナノサイエンス社製）を使用してＵＶオゾン照射し、シリコン基板の表面に水酸基を形成させて活性化した。エタノール１００部、２８％アンモニア水溶液１０部、及び２−ブロモ−２−メチルプロピオニルオキシプロピルトリメトキシシラン（ＢＰＭ）１部を入れた容器に活性化したシリコン基板を１２時間浸漬させた。取り出したシリコン基板を、乾燥機を使用し、８０℃で１０分間乾燥させた。
<Manufacturing of surface modified base material (1)>
(Reference example 1)
A 1 cm × 1 cm size silicon substrate was ultrasonically cleaned with isopropyl alcohol and then irradiated with UV ozone using a chip cleaner (manufactured by Bioforce Nanoscience) to form hydroxyl groups on the surface of the silicon substrate for activation. The activated silicon substrate was immersed in a container containing 100 parts of ethanol, 10 parts of a 28% aqueous ammonia solution, and 1 part of 2-bromo-2-methylpropionyloxypropyltrimethoxysilane (BPM) for 12 hours. The removed silicon substrate was dried at 80 ° C. for 10 minutes using a dryer.
ガラス製のサンプル瓶に、第一臭化銅０．０９３０部、ジノニルビピリジン０．６４７３部、メタクリル酸メチル（ＭＭＡ）２０．０２４０部、一般式（５）で表される化合物（Ｒ＝メチル基、３”−メタクリロキシスピロベンゾ［ｃ］−フラン［１，９”］キサンテン−３−オン、極大吸収波長３４１ｎｍ、蛍光色素−１）０．１部、アニソール２０．０部、及びブロモイソ酪酸エチル（ＥＢＩＢ）の１．９５％アニソール溶液０．０１部を入れて均一化し、茶褐色の重合溶液を得た。 In a glass sample bottle, 0.0930 parts of primary copper bromide, 0.6473 parts of dinonylbipyridine, 20.0240 parts of methyl methacrylate (MMA), and a compound represented by the general formula (5) (R = methyl). Group, 3 "-methacryloxyspirobenzo [c] -furan [1,9"] xanthene-3-one, maximum absorption wavelength 341 nm, fluorescent dye-1) 0.1 part, anisole 20.0 part, and bromoisobutyric acid 0.01 part of a 1.95% anisole solution of ethyl (EBIB) was added and homogenized to obtain a brown polymerized solution.
得られた重合溶液１０部及び上記のシリコン基板を三方コック付きのガラス製シュレンク管に入れた。アルゴンガスを３０分間吹き込んだ後、三方コックを閉めて密閉し、アンプル管とした。このアンプル管を６０℃の湯浴に入れ、６時間重合した。冷却後、アンプル管内の重合溶液の一部をサンプリングし、テトラヒドロフラン（ＴＨＦ）を展開溶媒とするＧＰＣにて測定したポリマーのポリスチレン換算の数平均分子量（Ｍｎ）は１２０，０００であり、分子量分布（重量平均分子量（Ｍｗ）／数平均分子量（Ｍｎ）＝ＰＤＩ）は１．０５であった。アンプル管から取り出したシリコン基板をＴＨＦに１２時間浸漬し、虹色干渉を示すポリマー層が形成された表面改質基材を得た。 10 parts of the obtained polymerization solution and the above-mentioned silicon substrate were placed in a glass Schlenk tube with a three-way cock. After blowing argon gas for 30 minutes, the three-way cock was closed and sealed to form an ampoule tube. This ampoule tube was placed in a hot water bath at 60 ° C. and polymerized for 6 hours. After cooling, a part of the polymerization solution in the ampol tube was sampled, and the polystyrene-equivalent number average molecular weight (Mn) of the polymer measured by GPC using tetrahydrofuran (THF) as a developing solvent was 120,000, and the molecular weight distribution (molecular weight distribution (Mn). The weight average molecular weight (Mw) / number average molecular weight (Mn) = PDI) was 1.05. The silicon substrate taken out from the ampoule tube was immersed in THF for 12 hours to obtain a surface-modified substrate on which a polymer layer exhibiting iridescent interference was formed.
得られた表面改質基材に波長３６５ｎｍの紫外線を照射し、表面のポリマー層が発光したことを確認した。また、ポリマー層に傷や欠陥などは見当たらなかった。以上より、得られた表面改質基材には、Ｍｎ１２万のポリマーからなる塗膜欠損等のないポリマー層が形成されたことを確認した。エリプソメトリー（商品名「ＥＣ−４００」、ジェー・エー・ウーラム社製）を使用して測定したポリマー層の膜厚は７５ｎｍであった。 The obtained surface-modified substrate was irradiated with ultraviolet rays having a wavelength of 365 nm, and it was confirmed that the polymer layer on the surface emitted light. In addition, no scratches or defects were found on the polymer layer. From the above, it was confirmed that a polymer layer made of a polymer of Mn 120,000 and having no coating film defects was formed on the obtained surface-modified base material. The film thickness of the polymer layer measured using ellipsometry (trade name "EC-400", manufactured by JA Woolam) was 75 nm.
（比較例１）
蛍光色素−１を使用しないこと以外は前述の参考例１と同様にして、ポリマー層が形成された表面改質基材を得た。生成したポリマーのＭｎは１６５，０００であり、ＰＤＩは１．０６であった。また、形成されたポリマー層の膜厚は７８．５ｎｍであった。得られた表面改質基材に波長３６５ｎｍの紫外線を照射したが、表面のポリマー層が発光することはなかった。このため、形成されたポリマー層に欠損等が生じていたか否かを確認することはできなかった。
(Comparative Example 1)
A surface-modified base material on which a polymer layer was formed was obtained in the same manner as in Reference Example 1 described above except that the fluorescent dye-1 was not used. The produced polymer had a Mn of 165,000 and a PDI of 1.06. The film thickness of the formed polymer layer was 78.5 nm. The obtained surface-modified substrate was irradiated with ultraviolet rays having a wavelength of 365 nm, but the polymer layer on the surface did not emit light. Therefore, it was not possible to confirm whether or not the formed polymer layer had defects or the like.
（実施例２）
参考例１で用いたものと同様のシリコン基板及び重合溶液を用意した。ポリエチレン製のサンプル瓶にシリコン基板を入れた後、サンプル瓶を重合溶液で充たして蓋をした。重合溶液が漏れないようにテープを巻くとともに、アルミパウチに入れて空気が入らないようにラミネートした。加圧媒体として水を入れた高圧装置（商品名「ＰＶ−４００シリーズ」、シンコーポレーション社製）内にアルミパウチを入れ、６０℃に加温するとともに、４００ＭＰａに加圧して４時間重合し、シリコン基板の表面にポリマー層が形成された表面改質基材を得た。生成したポリマーのＭｎは１，５００，０００であり、ＰＤＩは１．０４であった。また、形成されたポリマー層の膜厚は７５０ｎｍであった。得られた表面改質基材に波長３６５ｎｍの紫外線を照射し、表面のポリマー層が発光したことを確認した。また、ポリマー層に傷や欠陥などは見当たらなかった。
(Example 2)
A silicon substrate and a polymerization solution similar to those used in Reference Example 1 were prepared. After putting the silicon substrate in the polyethylene sample bottle, the sample bottle was filled with the polymerization solution and covered. The tape was wrapped so that the polymerization solution did not leak, and it was placed in an aluminum pouch and laminated to prevent air from entering. An aluminum pouch is placed in a high-pressure device (trade name "PV-400 series", manufactured by Shin Corporation) containing water as a pressurizing medium, heated to 60 ° C., pressurized to 400 MPa, and polymerized for 4 hours. A surface-modified base material having a polymer layer formed on the surface of a silicon substrate was obtained. The produced polymer had a Mn of 1,500,000 and a PDI of 1.04. The film thickness of the formed polymer layer was 750 nm. The obtained surface-modified substrate was irradiated with ultraviolet rays having a wavelength of 365 nm, and it was confirmed that the polymer layer on the surface emitted light. In addition, no scratches or defects were found on the polymer layer.
（実施例３）
炭化ケイ素製の基材（直径１ｃｍ、厚さ２ｍｍの円板）を用意し、前述の参考例１と同様にして活性化させた。エタノール１００部、２８％アンモニア水溶液１０部、及び２−アイオド−２−メチルプロピオニルオキシヘキシルトリエトキシシシラン（ＩＨＥ）１部を入れた容器に活性化させた上記の基材を入れ、１２時間浸漬させた後、取り出して送風乾燥した。
(Example 3)
A base material made of silicon carbide (a disk having a diameter of 1 cm and a thickness of 2 mm) was prepared and activated in the same manner as in Reference Example 1 described above. Place the activated base material in a container containing 100 parts of ethanol, 10 parts of a 28% aqueous ammonia solution, and 1 part of 2-iodo-2-methylpropionyloxyhexyltriethoxysisilane (IHE) and soak for 12 hours. After that, it was taken out and air-dried.
ガラス製のサンプル瓶に、テトラブチルアンモニウムアイオダイド（ＴＢＡＩ）０．４０６部、ＭＭＡ５５．０７部、３−メトキシ−Ｎ，Ｎ−ジメチルプロピオンアミド（ＭＤＭＰＡ）５５．０７部、アイオド酪酸エチルの１．９５％ＭＤＭＰＡ溶液０．１部、及び一般式（１１）で表される化合物（Ｒ＝メチル基、９−（２−メタクリロイルオキシエトキシカルボニルフェニル）−３，６−ビス（ジエチルアミノ）キサンチリウムのビス（トリフルオロメタンスルホニル）イミド塩、極大吸収波長５５２ｎｍ、蛍光色素−２）０．８２６部を入れて均一化し、赤色透明の重合溶液を得た。 In a glass sample bottle, 0.406 parts of tetrabutylammonium iodide (TBAI), 55.07 parts of MMA, 55.07 parts of 3-methoxy-N, N-dimethylpropionamide (MDMPA), and 1. of ethyl iodobutyrate. 0.1 part of 95% MDMPA solution and bis of compound (R = methyl group, 9- (2-methacryloyloxyethoxycarbonylphenyl) -3,6-bis (diethylamino) xanthylium) represented by the general formula (11). Trifluoromethanesulfonyl) imide salt, maximum absorption wavelength 552 nm, fluorescent dye-2) 0.826 parts were added and homogenized to obtain a red transparent polymerization solution.
フッ素樹脂製のサンプル瓶に上記の基材を入れた後、サンプル瓶を重合溶液で充たしてシールし、アルミパウチに入れて空気が入らないようにラミネートした。高圧装置内にアルミパウチを入れ、８５℃に加温するとともに、４００ＭＰａに加圧して６時間重合し、炭化ケイ素製の基材の表面にポリマー層が形成された表面改質基材を得た。生成したポリマーのＭｎは１，２４０，０００であり、ＰＤＩは１．５２であった。また、形成されたポリマー層の膜厚は６２０ｎｍであった。ＧＰＣのＵＶ吸収検出器で測定したポリマーのＭｎは１，２７０，０００であり、ＰＤＩは１．４３であった。得られた表面改質基材をＴＨＦで洗浄した後、乾燥させた。ブラックライトの紫外線を照射し、表面のポリマー層が発光したことを確認した。また、ポリマー層に傷や欠陥などは見当たらなかった。表面改質基材をＴＨＦに浸漬し、超音波洗浄した後、乾燥させた。紫外線を再度照射し、表面のポリマー層が発光したことを確認した。 After putting the above-mentioned base material in a sample bottle made of fluororesin, the sample bottle was filled with a polymerization solution to seal it, and then put into an aluminum pouch and laminated so as not to allow air to enter. An aluminum pouch was placed in a high-pressure device, heated to 85 ° C., pressurized to 400 MPa and polymerized for 6 hours to obtain a surface-modified base material in which a polymer layer was formed on the surface of a base material made of silicon carbide. .. The produced polymer had a Mn of 1,240,000 and a PDI of 1.52. The film thickness of the formed polymer layer was 620 nm. The Mn of the polymer measured by the UV absorption detector of GPC was 1,270,000, and the PDI was 1.43. The obtained surface-modified substrate was washed with THF and then dried. It was confirmed that the polymer layer on the surface emitted light by irradiating with ultraviolet rays of black light. In addition, no scratches or defects were found on the polymer layer. The surface-modified substrate was immersed in THF, ultrasonically cleaned, and then dried. It was confirmed that the polymer layer on the surface emitted light by irradiating with ultraviolet rays again.
（実施例４）
ＩＨＥに代えてＢＰＭを用いるとともに、アイオド酪酸エチルに代えてＥＢＩＢを用いたこと以外は、前述の実施例３と同様にして、炭化ケイ素製の基材の表面にポリマー層が形成された表面改質基材を得た。生成したポリマーのＭｎは１，６２０，０００であり、ＰＤＩは２．８８であった。また、形成されたポリマー層の膜厚は５２０ｎｍであった。得られた表面改質基材をＴＨＦで洗浄した後、乾燥させた。ブラックライトの紫外線を照射し、表面のポリマー層が発光したことを確認した。また、ポリマー層に傷や欠陥などは見当たらなかった。
(Example 4)
Surface modification in which a polymer layer was formed on the surface of a silicon carbide base material in the same manner as in Example 3 above, except that BPM was used instead of IHE and EBIB was used instead of ethyl iodobutyrate. A quality substrate was obtained. The produced polymer had a Mn of 1,620,000 and a PDI of 2.88. The film thickness of the formed polymer layer was 520 nm. The obtained surface-modified substrate was washed with THF and then dried. It was confirmed that the polymer layer on the surface emitted light by irradiating with ultraviolet rays of black light. In addition, no scratches or defects were found on the polymer layer.
＜開始化合物の合成＞
（合成例１）
撹拌機、還流コンデンサー、温度計、及び窒素導入管を取り付けた反応装置にプロピレングリコールモノメチルエーテルアセテート（ＰＧＭＡｃ）１００部を入れて８０℃に加温し、窒素ガスを吹き込んだ。別容器に、２−（２−ブロモイソブチリルオキシ）エチルメタクリラート（ＢＢＥＭ）５０部、メタクリロイロキシプロピルトリエトキシシリル（ＭＯＰＳ）５０部、及びアゾビスイソブチロニトリル（ＡＩＢＮ）１．５部を入れ、撹拌して均一なモノマー混合液を調製した。反応装置中にモノマー混合液の半量を添加した後、残りを２時間かけて滴下し、次いで、８時間重合してポリマー液を得た。ポリマー液の一部をサンプリングして測定した固形分は４９．２％であり、ほとんどのモノマーが重合したことを確認した。ポリマー液中のポリマーのＭｎは２３，０００であり、ＰＤＩは２．５１であった。得られたポリマー液にＰＧＭＡｃを添加して希釈し、固形分１５％である開始基ポリマー１溶液を得た。開始基ポリマー１溶液中の開始基ポリマー１は、所定の開始基及びアルコキシシリル基を有する、ポリマータイプの処理剤である。
<Synthesis of starting compound>
(Synthesis Example 1)
100 parts of propylene glycol monomethyl ether acetate (PGMAc) was placed in a reactor equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, heated to 80 ° C., and nitrogen gas was blown into the reaction apparatus. In a separate container, 50 parts of 2- (2-bromoisobutyryloxy) ethylmethacrylate (BBEM), 50 parts of methacrylooxypropyltriethoxysilyl (MOPS), and 1.5 parts of azobisisobutyronitrile (AIBN). Parts were added and stirred to prepare a uniform monomer mixture. After adding half the amount of the monomer mixture into the reaction apparatus, the rest was added dropwise over 2 hours, and then polymerized for 8 hours to obtain a polymer solution. The solid content measured by sampling a part of the polymer liquid was 49.2%, and it was confirmed that most of the monomers were polymerized. The Mn of the polymer in the polymer liquid was 23,000, and the PDI was 2.51. PGMAc was added to the obtained polymer solution and diluted to obtain a starting group polymer 1 solution having a solid content of 15%. Starting Group Polymer 1 The starting group polymer 1 in the solution is a polymer type treatment agent having a predetermined starting group and an alkoxysilyl group.
＜表面改質基材の製造（２）＞
（実施例５）
３ｃｍ×３ｃｍサイズのガラス基板を用意し、前述の参考例１と同様に活性化させた。合成例１で調製した開始基ポリマー１溶液をガラス基板に２，０００回転で３０秒間スピンコートした後、９０℃で９０秒間、１５０℃で１０分間焼き付けて硬化させ、塗膜を形成した。エリプソメトリーで測定した塗膜の膜厚は１．６９μｍであった。そして、塗膜を形成した上記のガラス基板を用いたこと以外は、前述の実施例４と同様にして、ガラス基板の表面にポリマー層が形成された表面改質基材を得た。生成したポリマーのＭｎは１，４２０，０００であり、ＰＤＩは２．６３であった。また、開始基ポリマー１溶液で形成した塗膜を含むポリマー層の膜厚は、１．９７μｍであった。すなわち、塗膜上に形成されたポリマー層の膜厚は２８０ｎｍであった。得られた表面改質基材をＴＨＦで洗浄した後、乾燥させた。紫外線を照射し、表面のポリマー層が赤色に発光したことを確認した。また、ポリマー層に傷や欠陥などは見当たらなかった。
<Manufacturing of surface modified base material (2)>
(Example 5)
A glass substrate having a size of 3 cm × 3 cm was prepared and activated in the same manner as in Reference Example 1 described above. The starting group polymer 1 solution prepared in Synthesis Example 1 was spin-coated on a glass substrate at 2,000 rpm for 30 seconds, and then baked at 90 ° C. for 90 seconds and at 150 ° C. for 10 minutes to cure to form a coating film. The film thickness of the coating film measured by ellipsometry was 1.69 μm. Then, a surface-modified base material having a polymer layer formed on the surface of the glass substrate was obtained in the same manner as in Example 4 described above, except that the above-mentioned glass substrate on which the coating film was formed was used. The Mn of the produced polymer was 1,420,000 and the PDI was 2.63. The film thickness of the polymer layer containing the coating film formed of the starting group polymer 1 solution was 1.97 μm. That is, the film thickness of the polymer layer formed on the coating film was 280 nm. The obtained surface-modified substrate was washed with THF and then dried. It was confirmed that the polymer layer on the surface emitted red light by irradiating with ultraviolet rays. In addition, no scratches or defects were found on the polymer layer.
（実施例６）
１．５ｃｍ×１．５ｃｍ、厚さ２．５ｍｍのＳＵＳ４０２製の金属板を１２個用意し、前述の参考例１と同様に活性化させた後、ＢＰＭで表面処理した。金属板を３個収容可能なフッ素樹脂製のフォルダーを４セット用意し、これらのフォルダーにＢＰＭで表面処理した金属板をセットした。フッ素樹脂製のサンプル瓶にフォルダーを装填してグローブボックスに入れ、さらに、参考例１で調製した重合溶液で充たしてシールし、アルミパウチに入れて空気が入らないようにラミネートした。実施例２で使用した高圧装置内にアルミパウチを入れ、６０℃に加温するとともに、４００ＭＰａに加圧して６時間重合し、金属板の表面にポリマー層が形成された１２個の表面改質基材を得た。生成したポリマーのＭｎは１，０８０，０００であり、ＰＤＩは１．２３であった。また、形成されたポリマー層の膜厚は、いずれも６３０ｎｍであった。得られた表面改質基材をＴＨＦで洗浄した後、乾燥させた。表面改質基材の外観はすべて同様に見え、問題ないことを確認した。次いで、紫外線を照射したところ、発光していない部分（傷）を有するポリマー層が形成されていた表面改質基材が１つあった。これにより、１つの表面改質基材（ロット）が不合格であると判断することができた。
(Example 6)
Twelve metal plates made of SUS402 having a thickness of 1.5 cm × 1.5 cm and a thickness of 2.5 mm were prepared, activated in the same manner as in Reference Example 1 described above, and then surface-treated with BPM. Four sets of fluororesin folders capable of accommodating three metal plates were prepared, and metal plates surface-treated with BPM were set in these folders. A folder was loaded into a fluororesin sample bottle, placed in a glove box, filled with the polymerization solution prepared in Reference Example 1, sealed, and placed in an aluminum pouch to prevent air from entering. An aluminum pouch was placed in the high-pressure device used in Example 2, heated to 60 ° C., pressurized to 400 MPa and polymerized for 6 hours, and 12 surface modifications in which a polymer layer was formed on the surface of the metal plate. A substrate was obtained. The Mn of the produced polymer was 1,080,000 and the PDI was 1.23. The film thickness of the formed polymer layers was 630 nm. The obtained surface-modified substrate was washed with THF and then dried. The appearance of the surface-modified base material all looked the same, confirming that there was no problem. Next, when irradiated with ultraviolet rays, there was one surface-modified base material on which a polymer layer having a non-luminous portion (scratch) was formed. As a result, it was possible to determine that one surface-modified base material (lot) was unacceptable.
本発明の表面改質基材の製造方法によれば、自動車、航空機、電子機器、家電、電池部材、医療用材料、ディスプレイ材料などの部品の他、セキュリティー分野の部品や表示材料等の部品として用いられる基材を製造する方法として有用である。 According to the method for manufacturing a surface-modified base material of the present invention, as parts such as automobiles, aircraft, electronic devices, home appliances, battery members, medical materials, display materials, as well as parts in the security field and display materials. It is useful as a method for producing the base material used.
Claims (7)
A method for inspecting a surface-modified substrate, which comprises a step of confirming the state of the fluorescent polymer layer by irradiating the fluorescent polymer layer of the surface-modified substrate according to claim 6 with ultraviolet rays and generating fluorescence. ..
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