JP4294528B2 - Tin fine particle production method and tin fine particle - Google Patents
Tin fine particle production method and tin fine particle Download PDFInfo
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Description
本発明は、錫微粒子の製造方法及び錫微粒子に関し、特に、黒色度、光遮蔽性に優れ、しかも安価な錫微粒子の製造方法及び錫微粒子に関するものである。 The present invention relates to a method for producing tin fine particles and tin fine particles, and more particularly to a method for producing tin fine particles and tin fine particles that are excellent in blackness and light shielding properties and inexpensive.
従来、黒色材料としては、カーボンブラック、低次酸化チタン、酸化鉄、クロム、銀微粒子等が知られている（例えば、特許文献１参照）。
これらの黒色材料は、黒色光遮蔽性フイルム、黒色光遮蔽性ガラス、黒色紙、黒色布、黒色インキ、プラズマディスプレイ（ＰＤＰ）や液晶ディスプレイ（ＬＣＤ）のブラックマトリックス材料、ブラックシール材、ブラックマスク材等に黒色や光遮蔽性を付与する材料として利用されている。
These black materials are black light shielding film, black light shielding glass, black paper, black cloth, black ink, black matrix material for plasma display (PDP) and liquid crystal display (LCD), black seal material, black mask material. For example, it is used as a material that imparts black color or light shielding properties.
ところで、従来のカーボンブラック、低次酸化チタン、酸化鉄等は、黒色ではあるが、光遮蔽性が不十分である。そのために、白色基材上に黒色の線を描く材料として用いた場合、下地の白色基材との境界線部分がぼやけてしまい、シャープな線を描くことができないという問題点があった。
これらの材料を光遮蔽材料として用いる場合、光遮蔽性を高めるためには材料中の体積比を多くする必要があり、相対的にバインダーの含有量が減少することになる。したがって、これらの材料を用いて黒色塗膜を作製した場合、塗膜の強度が低下し、塗膜を長期間に亘って維持することができないという問題点があった。
By the way, conventional carbon black, low-order titanium oxide, iron oxide and the like are black but have insufficient light shielding properties. Therefore, when it used as a material which draws a black line on a white base material, there was a problem that a boundary line part with a base white base material was blurred, and a sharp line could not be drawn.
When these materials are used as the light shielding material, it is necessary to increase the volume ratio in the material in order to improve the light shielding property, and the content of the binder is relatively reduced. Therefore, when a black coating film was produced using these materials, there was a problem that the strength of the coating film was lowered and the coating film could not be maintained for a long period of time.
また、クロムは、黒色度及び光遮蔽性に優れているものの、重金属である等、様々な理由から、適用可能な製品が制限されるという問題点があった。
また、写真フイルム等に用いられている臭化銀を還元することにより生成される銀粒子は、それ自体は黒色度及び光遮蔽性に優れているが、銀粒子を樹脂等と混合し、黒色材料として使用した場合、十分な黒色を得ることができないのが一般的である。しかも、銀は貴金属であり、錫よりも高価である。
Further, although chromium is excellent in blackness and light shielding properties, there is a problem that applicable products are limited for various reasons such as heavy metal.
In addition, the silver particles produced by reducing silver bromide used in photographic films and the like are themselves excellent in blackness and light shielding properties. When used as a material, it is common that sufficient black color cannot be obtained. Moreover, silver is a noble metal and is more expensive than tin.
本発明は、上記の課題を解決するためになされたものであって、黒色度、光遮蔽性に優れ、しかも安価な錫微粒子の製造方法及び錫微粒子を提供することを目的とする。 The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a tin fine particle production method and a tin fine particle that are excellent in blackness and light shielding properties and inexpensive.
本発明者は、光遮蔽性に優れる金属微粒子に着目し、さらには金属として安価な錫に注目し、鋭意検討を行った結果、塩化錫等の錫化合物、酒石酸、クエン酸等の錯化剤、ポリビニルアルコール等の保護剤を純水等の溶媒に溶解させ、次いで、この溶液の水素イオン指数（ｐＨ）を５〜１０に調整し、その後、この溶液に次亜リン酸ナトリウム等の還元剤を添加することにより、黒色度、光遮蔽性に優れた錫微粒子を容易かつ安価に得ることができることを見出し、本発明を完成するに至った。 The inventor of the present invention pays attention to fine metal particles having excellent light shielding properties, and further pays attention to inexpensive tin as a metal, and as a result of intensive studies, a complexing agent such as tin compounds such as tin chloride, tartaric acid and citric acid. Then, a protective agent such as polyvinyl alcohol is dissolved in a solvent such as pure water, and then the hydrogen ion index (pH) of this solution is adjusted to 5 to 10, and then a reducing agent such as sodium hypophosphite is added to this solution. As a result, it was found that tin fine particles having excellent blackness and light shielding properties can be obtained easily and inexpensively, and the present invention has been completed.
すなわち、本発明の錫微粒子の製造方法は、錫化合物、錯化剤及び保護剤を、溶液中の錫イオンの濃度が錫換算で０．０５〜２重量％となるように溶媒に溶解させ、この溶液の水素イオン指数を７以上かつ１０以下に調整した後、この溶液に還元剤を添加し、単相の結晶相からなる錫微粒子を析出させることを特徴とする。 That is, in the method for producing tin fine particles of the present invention, a tin compound, a complexing agent and a protective agent are dissolved in a solvent so that the concentration of tin ions in the solution is 0.05 to 2% by weight in terms of tin , After adjusting the hydrogen ion index of the solution to 7 or more and 10 or less, a reducing agent is added to the solution to precipitate tin fine particles composed of a single-phase crystal phase .
この錫微粒子の製造方法では、前記錫微粒子の平均一次粒子径は、２０〜３００ｎｍであることが好ましい。
前記錯化剤は、カルボン酸であることが好ましい。
前記錫化合物、錯化剤及び保護剤を溶媒に溶解させる際に、さらに緩衝剤を溶解させてもよい。
In the method for producing tin fine particles, the average primary particle diameter of the tin fine particles is preferably 20 to 300 nm.
The complexing agent is preferably a carboxylic acid.
When the tin compound, the complexing agent and the protective agent are dissolved in a solvent, a buffer may be further dissolved.
本発明の錫微粒子は、本発明の錫微粒子の製造方法により得られたことを特徴とする。 The tin fine particles of the present invention are obtained by the method for producing tin fine particles of the present invention.
本発明の錫微粒子の製造方法によれば、錫化合物、錯化剤及び保護剤を、溶液中の錫イオンの濃度が錫換算で０．０５〜２重量％となるように溶媒に溶解させ、この溶液の水素イオン指数を７以上かつ１０以下に調整した後、この溶液に還元剤を添加するので、粒子径が均一で安定しかつ単相の結晶相からなる錫微粒子を、容易かつ安価に作製することができる。したがって、黒色度、光遮蔽性に優れた錫微粒子を安価に作製することができる。 According to the method for producing fine tin particles of the present invention, a tin compound, a complexing agent, and a protective agent are dissolved in a solvent so that the concentration of tin ions in the solution is 0.05 to 2% by weight in terms of tin , After the hydrogen ion index of this solution is adjusted to 7 or more and 10 or less, a reducing agent is added to this solution, so that tin particles having a uniform and stable particle diameter and a single-phase crystal phase can be obtained easily and inexpensively. Can be produced. Therefore, tin fine particles having excellent blackness and light shielding properties can be produced at low cost.
本発明の錫微粒子によれば、本発明の錫微粒子の製造方法により得られたので、単相の結晶相からなる錫微粒子の粒子径を均一で安定したものとすることができる。したがって、黒色度、光遮蔽性共に優れたものとすることができる。
しかも、銀等の貴金属に比べて安価な錫を用いたので、黒色度、光遮蔽性に優れた微粒子を低価格にて供給することができる。
According to the tin fine particles of the present invention, the tin fine particles comprising the single-phase crystal phase can be made uniform and stable because they are obtained by the method for producing tin fine particles of the present invention. Therefore, both blackness and light shielding properties can be improved.
Moreover, since tin, which is cheaper than noble metals such as silver, is used, fine particles having excellent blackness and light shielding properties can be supplied at a low price.
本発明の錫微粒子の製造方法及び錫微粒子の最良の形態について説明する。
なお、この形態は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明を限定するものではない。
The method for producing tin fine particles and the best form of tin fine particles according to the present invention will be described.
This embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
本発明の錫微粒子の製造方法は、錫化合物、錯化剤及び保護剤を溶媒に溶解させ、この溶液の水素イオン指数（ｐＨ）を調整した後、この溶液に還元剤を添加し、錫微粒子を析出させる方法である。
ここで、錫化合物は錫イオン源となるもので、例えば、錫の塩等が好適に用いられる。
In the method for producing tin fine particles of the present invention, a tin compound, a complexing agent and a protective agent are dissolved in a solvent, and after adjusting the hydrogen ion index (pH) of this solution, a reducing agent is added to this solution, Is a method of precipitating.
Here, the tin compound serves as a tin ion source, and for example, a tin salt is preferably used.
錫の塩としては、例えば、塩化錫（II）（塩化第一錫）、塩化錫（IV）（塩化第二錫）等の塩化物、臭化錫（II）（臭化第一錫）、臭化錫（IV）（臭化第二錫）等の臭化物、酢酸錫、シュウ酸錫等の錫カルボン酸塩を用いることができ、特に、塩化錫（II）が好ましい。この錫化合物が溶媒に溶解することにより、溶媒中に錫イオンが生成される。 Examples of the tin salt include chlorides such as tin (II) chloride (stannic chloride) and tin (IV) chloride (stannic chloride), tin (II) bromide (stannic bromide), Bromides such as tin (IV) bromide (stannic bromide) and tin carboxylates such as tin acetate and tin oxalate can be used, and tin (II) chloride is particularly preferred. When this tin compound dissolves in the solvent, tin ions are generated in the solvent.
錯化剤は、溶液中に錯イオンを生じさせるもので、例えば、クエン酸、シュウ酸、フタル酸、フマル酸、マレイン酸、乳酸、りんご酸、酒石酸、アスコルビン酸、グリコール酸、グリセリン酸、タルトロン酸、ヒドロアクリル酸、エチレンジアミンテトラ酢酸、コハク酸、セバシン酸、グルタール酸、酢酸等の有機酸、ピロリン酸等の無機酸、あるいはアンモニア等から１種以上を選択使用することができる。
これらの有機酸では、カルボン酸が好ましく、カルボン酸の中でも特に、酒石酸またはクエン酸が好ましい。
Complexing agents are those that generate complex ions in solution, such as citric acid, oxalic acid, phthalic acid, fumaric acid, maleic acid, lactic acid, malic acid, tartaric acid, ascorbic acid, glycolic acid, glyceric acid, tartron. One or more kinds can be selected and used from acids, hydroacrylic acid, ethylenediaminetetraacetic acid, succinic acid, sebacic acid, glutaric acid, acetic acid and other inorganic acids, pyrophosphoric acid and other inorganic acids, and ammonia.
Among these organic acids, carboxylic acids are preferable, and among these carboxylic acids, tartaric acid or citric acid is preferable.
保護剤は、反応溶液中に生成した粒子の分散状態を安定的に維持するもので、例えば、ゼラチン、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）、ポリメチルビニルエーテル、デキストリン、メチルセルロース、エチルセルロース、界面活性剤等から１種以上を選択使用することができる。
これらの保護剤では、ポリビニルアルコール（ＰＶＡ）、ポリビニルピロリドン（ＰＶＰ）のいずれかが好ましい。
The protective agent stably maintains the dispersed state of the particles generated in the reaction solution. For example, gelatin, polyvinyl alcohol (PVA), polyvinyl pyrrolidone (PVP), polymethyl vinyl ether, dextrin, methyl cellulose, ethyl cellulose, interface One or more active agents can be selected and used.
Of these protective agents, polyvinyl alcohol (PVA) or polyvinyl pyrrolidone (PVP) is preferred.
溶媒としては、これら錫化合物、錯化剤、保護剤を溶解することができるものであれば、特に限定されないが、例えば、水、アルコール類、あるいはこれらの混合物等を用いることができる。取り扱いの容易さ及びコストを考慮すると、水が好ましい。 The solvent is not particularly limited as long as it can dissolve these tin compounds, complexing agents, and protective agents. For example, water, alcohols, or a mixture thereof can be used. In view of ease of handling and cost, water is preferable.
これら錫化合物、錯化剤及び保護剤を溶媒に溶解し、溶液を調整する。
この溶液中における錫イオンの濃度は、錫換算で０．０１重量％以上かつ５重量％以下が好ましく、より好ましくは０．０５重量％以上かつ２重量％以下である。錫イオンの濃度を上記の様に限定した理由は、濃度が０．０１重量％未満であると、錫微粒子の生成量が少なすぎるために生産性に劣ったものとなり、その結果、製造コストが高くなるからであり、また、濃度が２重量％を超えると、粒子径が均一で安定した微粒子を生成し難くなるからである。
These tin compounds, complexing agents and protective agents are dissolved in a solvent to prepare a solution.
The concentration of tin ions in this solution is preferably 0.01% by weight or more and 5% by weight or less, more preferably 0.05% by weight or more and 2% by weight or less in terms of tin. The reason for limiting the concentration of tin ions as described above is that when the concentration is less than 0.01% by weight, the production amount of tin fine particles is too small, resulting in inferior productivity. This is because when the concentration exceeds 2% by weight, it is difficult to produce fine particles having a uniform particle size and stability.
この溶液を作製する際に、さらに、必要により緩衝剤を加えることができる。
この緩衝剤は、錫化合物、錯化剤及び保護剤を含む溶液の急激なｐＨ変動を抑える役割をするものであり、例えば、カルボン酸系のアルカリ塩、ホウ酸のアルカリ塩、炭酸のアルカリ塩等を１種または２種以上選択使用することができる。
カルボン酸系のアルカリ塩としては、例えば、クエン酸３ナトリウム、クエン酸１水素２ナトリウム、クエン酸２水素１ナトリウム等のクエン酸ナトリウム、酢酸ナトリウム等を用いることができ、また、ホウ酸または炭酸のアルカリ塩としては、ホウ酸ナトリウム、炭酸ナトリウム等を用いることができる。これらの中でも、特に、クエン酸３ナトリウムが好ましい。
緩衝剤を上記の溶液に加えることにより、溶液のｐＨ変動が抑制され、粒子径の分散度が狭い錫微粒子を作製することが可能である。
In preparing this solution, a buffering agent can be further added as necessary.
This buffer serves to suppress rapid pH fluctuations in a solution containing a tin compound, a complexing agent and a protective agent. For example, a carboxylic acid alkali salt, an alkali salt of boric acid, an alkali salt of carbonic acid. Etc. can be used alone or in combination of two or more.
Examples of the carboxylic acid-based alkali salt include sodium citrate such as trisodium citrate, disodium 1hydrogen citrate, monosodium dihydrogen citrate, sodium acetate, and the like, and boric acid or carbonic acid. As the alkali salt, sodium borate, sodium carbonate and the like can be used. Among these, trisodium citrate is particularly preferable.
By adding a buffering agent to the above-mentioned solution, it is possible to produce tin microparticles in which the pH variation of the solution is suppressed and the degree of dispersion of the particle diameter is narrow.
次いで、この溶液のｐＨを、ｐＨ調整剤を用いて調整する。
ｐＨの値は、用いる錫化合物、錯化剤及び保護剤に応じて適宜選択されるが、５以上かつ１０以下が好ましく、より好ましくは７以上かつ１０以下である。ここで、ｐＨが５未満の強酸性の場合、粒子径が均一でかつ安定した微粒子が生成し難くなるからであり、また、ｐＨが１０を超える強塩基性の場合、錫の水酸化物が生成し易くなり、結晶相が単相の錫微粒子を得ることが難しくなるからである。
Next, the pH of the solution is adjusted using a pH adjuster.
The pH value is appropriately selected according to the tin compound, complexing agent and protective agent used, but is preferably 5 or more and 10 or less, more preferably 7 or more and 10 or less. Here, when the pH is strong acidity of less than 5, it is difficult to produce fine particles having a uniform particle size and stable, and when the pH is strongly basic exceeding 10, the tin hydroxide is This is because it becomes easy to produce and it is difficult to obtain tin fine particles having a single crystal phase.
ｐＨ調整剤としては、例えば、水酸化ナトリウム水溶液、水酸化カリウム水溶液、アンモニア水溶液、酢酸水溶液、シュウ酸水溶液、希塩酸、希硝酸等を１種以上用いることができる。
このｐＨ調整剤を用いて溶液のｐＨを調整した後、このｐＨ調整後の溶液に還元剤を添加する。
還元剤としては、例えば、次亜燐酸ナトリウム、亜燐酸カリウム、亜ジチオン酸ナトリウム、水素化ホウ素ナトリウム、ジメチルアミンボラン等のうち１種または２種以上を選択使用することができる。
As the pH adjuster, for example, one or more of sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, ammonia aqueous solution, acetic acid aqueous solution, oxalic acid aqueous solution, dilute hydrochloric acid, dilute nitric acid and the like can be used.
After adjusting the pH of the solution using this pH adjuster, a reducing agent is added to the solution after the pH adjustment.
As the reducing agent, for example, one or more of sodium hypophosphite, potassium phosphite, sodium dithionite, sodium borohydride, dimethylamine borane and the like can be selected and used.
上記の溶液中の錫イオンの濃度、錯化剤及び保護剤の濃度、ｐＨを調整することにより、錫微粒子の平均一次粒子径を調整することができる。
例えば、平均一次粒子径が１μｍ以下の金属錫微粒子を作製する場合、溶液中の錫イオンの濃度は錫換算で０．０１〜５重量％、ｐＨは５〜１０である。また、平均一次粒子径が２０〜３００ｎｍの金属錫微粒子を作製する場合、溶液中の錫イオンの濃度は錫換算で０．０５〜２重量％、ｐＨは７〜１０が好ましい。
The average primary particle diameter of the tin fine particles can be adjusted by adjusting the concentration of tin ions, the concentration of the complexing agent and the protective agent, and the pH in the solution.
For example, when producing metal tin fine particles having an average primary particle diameter of 1 μm or less, the concentration of tin ions in the solution is 0.01 to 5% by weight in terms of tin, and the pH is 5 to 10. Moreover, when producing metal tin fine particles having an average primary particle diameter of 20 to 300 nm, the concentration of tin ions in the solution is preferably 0.05 to 2% by weight in terms of tin, and the pH is preferably 7 to 10.
このようにして得られた錫微粒子は、Ｘ線回折図形により、単相の錫結晶であることを確認することができる。
この錫微粒子は、表面の活性が高いために、酸化錫の被膜で覆われた状態になっている場合もある。この被膜は極めて薄いために、Ｘ線回折図形により確認することは極めて難しい。
The tin fine particles thus obtained can be confirmed to be single-phase tin crystals by an X-ray diffraction pattern.
Since the tin fine particles have high surface activity, they may be covered with a tin oxide film. Since this film is extremely thin, it is extremely difficult to confirm with an X-ray diffraction pattern.
錫単体は卑金属であり、その標準電極電位が水素より卑で酸化され易いために、上記の溶液中にて合成された錫微粒子は、合成直後、あるいはその洗浄過程にて表面が酸化され、薄い酸化被膜に覆われた状態で、その形状および組成が維持されている場合もある。
このように、本実施形態の錫微粒子は、不可避的に表面が酸化された状態のものも含むものである。
Tin alone is a base metal, and its standard electrode potential is more base and easier to oxidize than hydrogen. Therefore, the tin fine particles synthesized in the above solution are thin because the surface is oxidized immediately after synthesis or in the cleaning process. In some cases, the shape and composition are maintained while being covered with an oxide film.
Thus, the tin fine particles of the present embodiment include those whose surface is inevitably oxidized.
本実施形態の錫微粒子の製造方法によれば、錫化合物、錯化剤及び保護剤を溶媒に溶解させて均一な溶液とし、この溶液のｐＨをｐＨ調整剤を用いて調整し、その後、この溶液に還元剤を添加するので、簡単な装置により、平均一次粒子径が１μｍ以下、好ましくは２０〜３００ｎｍの単相の結晶相からなる錫微粒子を、容易かつ安価に作製することができる。したがって、黒色度、光遮蔽性に優れ、粒子径の分散性が狭い錫微粒子を安価に作製することができる。 According to the method for producing tin fine particles of this embodiment, a tin compound, a complexing agent and a protective agent are dissolved in a solvent to obtain a uniform solution, and the pH of this solution is adjusted using a pH adjuster, Since the reducing agent is added to the solution, tin fine particles composed of a single-phase crystal phase having an average primary particle diameter of 1 μm or less, preferably 20 to 300 nm can be easily and inexpensively produced with a simple apparatus. Therefore, tin fine particles having excellent blackness and light shielding properties and narrow particle diameter dispersibility can be produced at low cost.
本実施形態の製造方法により得られた錫微粒子は、例えば、以下のように用いることができる。
上記の錫微粒子をセルロース（繊維素）中、あるいは樹脂中に含有させることにより、黒色性に優れたセルロース、あるいは樹脂組成物を得ることができる。 セルロースとしては、特に限定されないが、例えば、エチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、ニトロセルロース、エチルセルロース誘導体等から選択することができる。
Tin fine particles obtained by the production method of the present embodiment can be used, for example, as follows.
By containing the tin fine particles in cellulose (fibrin) or resin, cellulose or resin composition having excellent blackness can be obtained. Although it does not specifically limit as cellulose, For example, it can select from ethyl cellulose, hydroxyethyl cellulose, methyl cellulose, nitrocellulose, an ethyl cellulose derivative, etc.
また、樹脂としては、特に限定されないが、例えば、ポリビニルアルコール（ＰＶＡ）、ポリエチレンオキシド、ポリアルキレンオキシド、アクリル系樹脂、ブチラール樹脂、フェノール系樹脂、ポリウレタン樹脂、ポリエステル系樹脂、アルキッド樹脂、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体、スチレン系樹脂、エポキシ樹脂、アミノ樹脂、ポリイミド樹脂、メラミンアルキッド樹脂、レゾール樹脂、およびこれらの変性樹脂等から選択することができる。 The resin is not particularly limited. For example, polyvinyl alcohol (PVA), polyethylene oxide, polyalkylene oxide, acrylic resin, butyral resin, phenolic resin, polyurethane resin, polyester resin, alkyd resin, vinyl acetate resin. , Ethylene-vinyl acetate copolymer, styrene resin, epoxy resin, amino resin, polyimide resin, melamine alkyd resin, resol resin, and modified resins thereof.
上記の錫微粒子を溶媒中に分散させることにより、塗布液として用いることができる。
溶媒としては、特に限定されないが、例えば、水、アルコール類、フェノール類、エステル類、ケトン類、エーテル類、芳香族化合物等を用いることができる。
必要により、バインダー成分、分散剤、その他の添加物等を加えてもよい。
By dispersing the above tin fine particles in a solvent, it can be used as a coating solution.
Although it does not specifically limit as a solvent, For example, water, alcohol, phenols, ester, ketones, ethers, an aromatic compound, etc. can be used.
If necessary, a binder component, a dispersant, and other additives may be added.
バインダー成分としては、特に限定されないが、セルロースあるいは樹脂が用いられ、セルロースとしては、例えば、エチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、ニトロセルロース、エチルセルロース誘導体等から選択することができる。
樹脂としては、例えば、ポリビニルアルコール（ＰＶＡ）、ポリエチレンオキシド、ポリアルキレンオキシド、アクリル系樹脂、ブチラール樹脂、フェノール系樹脂、ポリウレタン樹脂、ポリエステル系樹脂、アルキッド樹脂、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体、スチレン系樹脂、エポキシ樹脂、アミノ樹脂、ポリイミド樹脂、メラミンアルキッド樹脂、レゾール樹脂、およびこれらの変性樹脂等から選択することができる。
上記の錫微粒子を溶媒中に分散させた塗布液を用いることにより、黒色性に優れた膜を基材上に形成することができる。
Although it does not specifically limit as a binder component, A cellulose or resin is used, As a cellulose, it can select from ethyl cellulose, a hydroxyethyl cellulose, methylcellulose, nitrocellulose, an ethylcellulose derivative etc., for example.
Examples of the resin include polyvinyl alcohol (PVA), polyethylene oxide, polyalkylene oxide, acrylic resin, butyral resin, phenolic resin, polyurethane resin, polyester resin, alkyd resin, vinyl acetate resin, ethylene-vinyl acetate copolymer It can be selected from coalescence, styrene resin, epoxy resin, amino resin, polyimide resin, melamine alkyd resin, resol resin, and modified resins thereof.
By using a coating solution in which the above tin fine particles are dispersed in a solvent, a film having excellent blackness can be formed on the substrate.
以下、実施例１〜３及び比較例１〜４により本発明を具体的に説明するが、本発明はこれらの実施例によって限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated concretely by Examples 1-3 and Comparative Examples 1-4, this invention is not limited by these Examples.
（実施例１）
０．４５ｍｏｌ／Ｌの塩化錫水溶液（関東化学社製）を１００ｇ、容量５００ｍｌのビーカーに分取し、この塩化錫水溶液にクエン酸（関東化学社製）を２０ｇ加え、溶解した後、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１％水溶液を１７ｇ加え、１５分間攪拌した。次いで、この溶液に５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を滴下してｐＨを６．０に調整した。その後、純水を加えて全体の量を４００ｍｌとし、この溶液を恒温槽内に静置し、その温度を４０℃に調整した。
Example 1
A 0.45 mol / L tin chloride aqueous solution (manufactured by Kanto Chemical Co., Inc.) was dispensed in a beaker having a capacity of 100 g and a volume of 500 ml, and 20 g of citric acid (manufactured by Kanto Chemical Co., Ltd.) was added to the tin chloride aqueous solution and dissolved. 17 g of 1% aqueous solution (Kuraraypoval PVA205) was added and stirred for 15 minutes. Subsequently, 5 mol / L sodium hydroxide aqueous solution was dripped at this solution, and pH was adjusted to 6.0. Thereafter, pure water was added to make the total amount 400 ml, and this solution was allowed to stand in a thermostatic bath, and its temperature was adjusted to 40 ° C.
ここで、水素化ホウ素ナトリウム（関東化学社製）２．５ｇを純水に溶解して全体の容積を１００ｍｌとし、この水素化ホウ素ナトリウム水溶液を温度が４０℃に調整された上記溶液に一気に投入し、１時間攪拌した。
得られた溶液を遠心分離洗浄することにより、５０ｍｌの錫微粒子分散液を得た。
Here, 2.5 g of sodium borohydride (manufactured by Kanto Chemical Co., Inc.) was dissolved in pure water to make the total volume 100 ml, and this sodium borohydride aqueous solution was poured into the above solution adjusted to a temperature of 40 ° C. all at once. And stirred for 1 hour.
The obtained solution was centrifuged and washed to obtain 50 ml of a tin fine particle dispersion.
この分散液中の錫微粒子を透過電子顕微鏡（ＴＥＭ）により観察し、また、この錫微粒子の粉末Ｘ線回折による同定を行った。
その結果、得られた錫微粒子は、平均一次粒子径が４０ｎｍ程度であり、単一の結晶相からなる金属錫であることが確認された。
Tin fine particles in this dispersion were observed with a transmission electron microscope (TEM), and the tin fine particles were identified by powder X-ray diffraction.
As a result, the obtained tin fine particles had an average primary particle diameter of about 40 nm and were confirmed to be metallic tin composed of a single crystal phase.
（実施例２）
シュウ酸（関東化学社製）を２０ｇ、容量５００ｍｌのビーカーに分取し、これに純水を２００ｇ加え、１５分間攪拌した。次いで、塩化錫（II）２水和物（ＳｎＣｌ２・２Ｈ２Ｏ:関東化学社製）１０ｇを加え、溶解した後、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１％水溶液を１７ｇ加え、２０分間攪拌した。次いで、この溶液にクエン酸３ナトリウムを５ｇ加え、溶解した後、さらにポリカルボン酸系分散剤（ポイズ５３２：花王社製）１％水溶液を１７ｇ加え、１５分間攪拌した。
(Example 2)
20 g of oxalic acid (manufactured by Kanto Chemical Co., Inc.) was taken into a beaker having a capacity of 500 ml, 200 g of pure water was added thereto, and the mixture was stirred for 15 minutes. Next, 10 g of tin (II) chloride dihydrate (SnCl 2 .2H 2 O: manufactured by Kanto Chemical Co., Inc.) was added and dissolved, and then 17 g of a 1% aqueous solution of polyvinyl alcohol (Kuraray Poval PVA205) was added and stirred for 20 minutes. . Next, 5 g of trisodium citrate was added to this solution and dissolved, and then 17 g of a 1% aqueous solution of a polycarboxylic acid-based dispersant (Poise 532: manufactured by Kao Corporation) was further added and stirred for 15 minutes.
次いで、この溶液に、５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を滴下してｐＨを８．０に調整した。その後、純水を加えて全体の量を４００ｍｌとし、この溶液を恒温槽内に静置し、その温度を４０℃に調整した。
ここで、水素化ホウ素ナトリウム（関東化学社製）２．５ｇを純水に溶解して全体の容積を１００ｍｌとし、この水素化ホウ素ナトリウム水溶液を温度が４０℃に調整された上記溶液に一気に投入し、１時間攪拌した。
得られた溶液を遠心分離洗浄することにより、５０ｍｌの錫微粒子分散液を得た。
Subsequently, 5 mol / L sodium hydroxide aqueous solution was dripped at this solution, and pH was adjusted to 8.0. Thereafter, pure water was added to make the total amount 400 ml, and this solution was allowed to stand in a thermostatic bath, and its temperature was adjusted to 40 ° C.
Here, 2.5 g of sodium borohydride (manufactured by Kanto Chemical Co., Inc.) was dissolved in pure water to make the total volume 100 ml, and this sodium borohydride aqueous solution was poured into the above solution adjusted to a temperature of 40 ° C. all at once. And stirred for 1 hour.
The obtained solution was centrifuged and washed to obtain 50 ml of a tin fine particle dispersion.
この分散液中の錫微粒子を透過電子顕微鏡（ＴＥＭ）により観察し、また、この錫微粒子の粉末Ｘ線回折による同定を行った。
その結果、得られた錫微粒子は、平均一次粒子径が１５０ｎｍ程度であり、単一の結晶相からなる金属錫であることが確認された。
Tin fine particles in this dispersion were observed with a transmission electron microscope (TEM), and the tin fine particles were identified by powder X-ray diffraction.
As a result, the obtained tin fine particles had an average primary particle diameter of about 150 nm and were confirmed to be metallic tin composed of a single crystal phase.
（実施例３）
酒石酸（関東化学社製）を２５ｇ、容量１０００ｍｌのビーカーに分取し、これにポリビニルピロリドン（Ｋ＝１５：関東化学社製）１％水溶液を２０ｇ加え、さらに純水を２００ｇ加え、１５分間攪拌した。次いで、この溶液に、塩化錫（II）２水和物（ＳｎＣｌ２・２Ｈ２Ｏ:関東化学社製）１００ｇを純水に溶解して全体量を１Ｌとした塩化錫水溶液を１００ｍｌ加え、５分間攪拌した。
(Example 3)
25 g of tartaric acid (manufactured by Kanto Chemical Co., Inc.) was dispensed into a beaker having a capacity of 1000 ml, 20 g of a 1% aqueous solution of polyvinylpyrrolidone (K = 15: manufactured by Kanto Chemical Co., Ltd.) was added thereto, 200 g of pure water was further added, and the mixture was stirred for 15 minutes. did. Next, 100 ml of a tin chloride aqueous solution in which 100 g of tin (II) chloride dihydrate (SnCl 2 .2H 2 O: manufactured by Kanto Chemical Co., Ltd.) was dissolved in pure water to make the total amount 1 L was added to this solution. Stir for minutes.
次いで、この溶液にクエン酸３ナトリウムを５ｇ加え、溶解した後、さらに５ｍｏｌ／Ｌの水酸化ナトリウム水溶液を滴下してｐＨを７．０に調整した。その後、純水を加えて全体の量を４００ｍｌとし、この溶液を恒温槽内に静置し、その温度を４０℃に調整した。
ここで、水素化ホウ素ナトリウム（関東化学社製）２．５ｇを純水に溶解して全体の容積を１００ｍｌとした水素化ホウ素ナトリウム水溶液を、温度が４０℃に調整された上記溶液に一気に投入し、１時間攪拌した。
得られた溶液を遠心分離洗浄することにより、５０ｍｌの錫微粒子分散液を得た。
Next, 5 g of trisodium citrate was added to this solution and dissolved, and then a 5 mol / L aqueous sodium hydroxide solution was added dropwise to adjust the pH to 7.0. Thereafter, pure water was added to make the total amount 400 ml, and this solution was allowed to stand in a thermostatic bath, and its temperature was adjusted to 40 ° C.
Here, a sodium borohydride aqueous solution in which 2.5 g of sodium borohydride (manufactured by Kanto Chemical Co., Ltd.) was dissolved in pure water to make the total volume 100 ml was poured into the above solution whose temperature was adjusted to 40 ° C. at once. And stirred for 1 hour.
The obtained solution was centrifuged and washed to obtain 50 ml of a tin fine particle dispersion.
この分散液中の錫微粒子を透過電子顕微鏡（ＴＥＭ）により観察し、また、この錫微粒子の粉末Ｘ線回折による同定を行った。得られた透過電子顕微鏡像（ＴＥＭ像）を図１に、また、Ｘ線回折図形を図２に、そ
れぞれ示す。
その結果、得られた錫微粒子は、平均一次粒子径が３０ｎｍ程度であり、単一の結晶相からなる金属錫であることが確認された。
Tin fine particles in this dispersion were observed with a transmission electron microscope (TEM), and the tin fine particles were identified by powder X-ray diffraction. The obtained transmission electron microscope image (TEM image) is shown in FIG. 1, and the X-ray diffraction pattern is shown in FIG.
As a result, the obtained tin fine particles had an average primary particle diameter of about 30 nm, and were confirmed to be metallic tin composed of a single crystal phase.
その後、この錫微粒子分散液に、錫固形分：ＰＶＡ＝５０：５０の体積比率となるように、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１０％水溶液を加え、次いで、この溶液を超音波分散機（ソニファイヤー４５０：BRANSON ULTRASONICS社製）で分散処理し、その後、成膜後の膜厚が０．５μｍとなるように分散液中の水分量を調節し、この分散液を厚み１．１ｍｍのガラス基板上にスピンコーターを用いて塗布し、実施例３の黒色膜を成膜した。 Thereafter, a 10% aqueous solution of polyvinyl alcohol (Kuraray Poval PVA205) was added to the tin fine particle dispersion so that the volume ratio of tin solids: PVA = 50: 50, and this solution was then added to an ultrasonic disperser (Soni Fire 450 (manufactured by BRANSON ULTRASONICS)), and then the amount of water in the dispersion is adjusted so that the film thickness after film formation is 0.5 μm, and this dispersion is 1.1 mm thick glass substrate. The black coating film of Example 3 was formed by coating on the top using a spin coater.
この黒色膜を室温（２５℃）にて乾燥した後、分光スペクトルメーターにより５５０ｎｍの波長の光に対する膜自体の光透過率を測定した。
また、この膜の黒色度を評価するために、この膜のＣＩＥ明度Ｌ＊を、ＣＩＥ（国際照明委員会）により規格化されたＬ＊ａ＊ｂ＊表色系に基づいて測定した。
これらの結果を表に示す。
After the black film was dried at room temperature (25 ° C.), the light transmittance of the film itself with respect to light having a wavelength of 550 nm was measured with a spectrospectrometer.
Further, in order to evaluate the blackness of the film, the CIE lightness L * of the film was measured based on the L * a * b * color system standardized by the CIE (International Lighting Commission).
These results are shown in the table.
（比較例１）
カーボンブラック（ＨＡ３：東海カーボン社製）に、実施例３と同様、カーボンブラック：ＰＶＡ＝５０：５０の体積比率となるように、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１０％水溶液を加え、次いで、この溶液に、実施例３と同様、分散処理及び水分量の調節を行い、この分散液を厚み１．１ｍｍのガラス基板上にスピンコーターを用いて塗布し、膜厚が０．５μｍの黒色膜を成膜した。
この黒色膜の光透過率及びＣＩＥ明度Ｌ＊を実施例３と同様にして測定した。
これらの結果を表に示す。
(Comparative Example 1)
To the carbon black (HA3: manufactured by Tokai Carbon Co., Ltd.), as in Example 3, a 10% aqueous solution of polyvinyl alcohol (Kuraraypoval PVA205) was added so that the volume ratio of carbon black: PVA = 50: 50 was obtained. In the same manner as in Example 3, the dispersion treatment and the amount of water were adjusted to the solution, and this dispersion was applied onto a glass substrate having a thickness of 1.1 mm using a spin coater to form a black film having a thickness of 0.5 μm. A film was formed.
The light transmittance and CIE brightness L * of this black film were measured in the same manner as in Example 3.
These results are shown in the table.
（比較例２）
チタンブラック（１３Ｍ：ジェムコ社製）に、実施例３と同様、チタンブラック：ＰＶＡ＝５０：５０の体積比率となるように、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１０％水溶液を加え、次いで、この溶液に、実施例３と同様、分散処理及び水分量の調節を行い、この分散液を厚み１．１ｍｍのガラス基板上にスピンコーターを用いて塗布し、膜厚が０．５μｍの黒色膜を成膜した。
この黒色膜の光透過率及びＣＩＥ明度Ｌ＊を実施例３と同様にして測定した。
これらの結果を表に示す。
(Comparative Example 2)
A titanium alcohol (Kuraraypoval PVA205) 10% aqueous solution was added to titanium black (13M: manufactured by Gemco) in a volume ratio of titanium black: PVA = 50: 50 in the same manner as in Example 3, and then this solution In the same manner as in Example 3, the dispersion treatment and the water content were adjusted, and this dispersion was applied onto a glass substrate having a thickness of 1.1 mm using a spin coater to form a black film having a thickness of 0.5 μm. Filmed.
The light transmittance and CIE brightness L * of this black film were measured in the same manner as in Example 3.
These results are shown in the table.
（比較例３）
銀ナノ粒子（住友大阪セメント社製）に、実施例３と同様、銀ナノ粒子：ＰＶＡ＝５０：５０の体積比率となるように、ポリビニルアルコール（クラレポバール ＰＶＡ２０５）１０％水溶液を加え、次いで、この溶液に、実施例３と同様、分散処理及び水分量の調節を行い、この分散液を厚み１．１ｍｍのガラス基板上にスピンコーターを用いて塗布し、膜厚が０．５μｍの黒色膜を成膜した。
この黒色膜の光透過率及びＣＩＥ明度Ｌ＊を実施例３と同様にして測定した。
これらの結果を表に示す。
(Comparative Example 3)
To the silver nanoparticles (manufactured by Sumitomo Osaka Cement Co., Ltd.), as in Example 3, a 10% aqueous solution of polyvinyl alcohol (Kuraraypoval PVA205) was added so that the volume ratio of silver nanoparticles: PVA = 50: 50 was obtained, In the same manner as in Example 3, this solution was subjected to dispersion treatment and adjustment of water content, and this dispersion was applied onto a glass substrate having a thickness of 1.1 mm using a spin coater, and a black film having a thickness of 0.5 μm. Was deposited.
The light transmittance and CIE brightness L * of this black film were measured in the same manner as in Example 3.
These results are shown in the table.
（比較例４）
アニリンブラック黒色染料（堀内化学研究所製）を用い、実施例３と同様にして膜厚が０．５μｍの黒色膜を成膜した。
この黒色膜の光透過率及びＣＩＥ明度Ｌ＊を実施例３と同様にして測定した。
これらの結果を表に示す。
(Comparative Example 4)
A black film having a thickness of 0.5 μm was formed in the same manner as in Example 3 using aniline black black dye (manufactured by Horiuchi Chemical Laboratory).
The light transmittance and CIE brightness L * of this black film were measured in the same manner as in Example 3.
These results are shown in the table.
この表によれば、実施例３の黒色膜は、比較例１〜４に対して光透過率、ＣＩＥ明度Ｌ＊共に優れており、遮光性及び黒色度に優れていることが確認された。
一方、比較例１、２の黒色膜は光透過率が高く、実施例３に対して遮光性が劣っていた。
また、比較例３の黒色膜は、実施例３と同等の遮光性が得られるものの、膜の色は灰色であり、色調の点で問題があった。
さらに、比較例４の黒色膜は光透過率が高く、遮光性が極めて劣ることが分かった。
According to this table, it was confirmed that the black film of Example 3 was superior in both light transmittance and CIE lightness L * to Comparative Examples 1 to 4, and excellent in light-shielding properties and blackness.
On the other hand, the black films of Comparative Examples 1 and 2 had high light transmittance and were inferior in light-shielding properties to Example 3.
Further, the black film of Comparative Example 3 has a light shielding property equivalent to that of Example 3, but the film has a gray color and has a problem in color tone.
Furthermore, it turned out that the black film of the comparative example 4 has high light transmittance, and its light-shielding property is very inferior.
本発明の錫微粒子は、黒色度、光遮蔽性に優れ、しかも安価であるから、プラズマディスプレイ（ＰＤＰ）や液晶ディスプレイ（ＬＣＤ）等の表示装置の遮光材料としてはもちろんのこと、窓材等の光遮蔽性を高めるフィルム等、建築や日用品等の分野においても、大いに期待されるものである。 Since the tin fine particles of the present invention are excellent in blackness, light shielding properties, and inexpensive, they can be used as light shielding materials for display devices such as plasma displays (PDP) and liquid crystal displays (LCD), as well as window materials. This is also highly expected in fields such as architecture and daily necessities, such as films that enhance light shielding.
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| TWI483999B (en) | 2009-06-15 | 2015-05-11 | Toray Industries | Black composite fine particle, black resin composition, color filter substrate and liquid crystal display |
| JP5830265B2 (en) * | 2011-04-12 | 2015-12-09 | 新日鉄住金化学株式会社 | Method for producing dispersion-stable tin fine particles and method for producing tin ink using the same |
| JP6367013B2 (en) * | 2014-06-05 | 2018-08-01 | 三井金属鉱業株式会社 | Tin powder and method for producing the same |
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