JP2008055341A - Member with film and film forming method - Google Patents
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本発明は、皮膜を有する部材及び皮膜形成方法に関する。 The present invention relates to a member having a film and a film forming method.
産業用製造ラインの部品に用いる部材には、業務用の接着剤の粘着や、成形樹脂の残留物の付着等を防止できること、つまり、非粘着性を有することが要求される。 A member used for parts in an industrial production line is required to be able to prevent adhesion of a commercial adhesive, adhesion of a molded resin residue, or the like, that is, non-adhesiveness.
特に、近年、精密性が要求される自動車部品及びＩＴ部品の製造ラインや、試験製造装置等の部品に好適に用いることができる非粘着性部材に関するニーズがある。 In particular, in recent years, there is a need for a non-adhesive member that can be suitably used for parts such as production lines for automobile parts and IT parts that require precision and test production equipment.
従来より、基材表面に、フッ素樹脂コーティング等により、部材に非粘着性、撥水性及び離型性を付与する技術がある。 Conventionally, there is a technique for imparting non-adhesiveness, water repellency, and releasability to a member by fluororesin coating or the like on the surface of the substrate.
しかしながら、フッ素樹脂コーティング等により皮膜を形成してなる部材は、塗膜の密着性が弱いため、耐摩耗性が劣る。つまり、耐久性の点で問題がある。 However, a member formed with a film by fluororesin coating or the like is inferior in wear resistance because the adhesion of the coating film is weak. That is, there is a problem in terms of durability.
この問題を解決した皮膜形成技術が特許文献１に開示されている。特許文献１の皮膜形成技術によれば、特定の下塗り塗膜層、中塗り塗膜層及び上塗り塗膜層を順次形成することにより、非粘着性及び離型性だけでなく、耐久性をも付与できる。 Patent Document 1 discloses a film forming technique that solves this problem. According to the film forming technique of Patent Document 1, by forming a specific undercoat film layer, intermediate coat film layer, and topcoat film layer in order, not only non-adhesiveness and releasability but also durability. Can be granted.
しかしながら、特許文献１の技術により皮膜を形成させる場合、皮膜の膜厚が数μｍ以上、場合によっては数十μｍ以上になりやすく、膜厚の薄い皮膜を形成させることが困難である。 However, when a film is formed by the technique of Patent Document 1, the film thickness of the film tends to be several μm or more, and in some cases, several tens of μm or more, and it is difficult to form a thin film.
特に、精密性が要求される自動車部品及びＩＴ部品（例えば半導体）の製造ラインや、試験製造装置等の部品に用いられる部材ついては、形状が複雑になるにつれて、膜厚をより薄く、具体的には膜厚を１μｍ以下にすることが求められている。
本発明の主な目的は、撥水性、非粘着性（離型性）及び耐久性に優れた皮膜を有する部材及び該皮膜の形成方法を提供することである。 The main object of the present invention is to provide a member having a film excellent in water repellency, non-adhesiveness (release property) and durability, and a method for forming the film.
本発明者は、上記のような従来技術の問題点に鑑みて鋭意研究を重ねた結果、特定の方法により形成された皮膜を有する部材が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies in view of the problems of the prior art as described above, the present inventor has found that a member having a film formed by a specific method can achieve the above object, and completes the present invention. It came.
すなわち、本発明は、下記の皮膜を有する部材及び皮膜形成方法に係る。
１． 金属基材又はセラミックス基材表面に、アミノ基含有シラノール誘導体を含む溶液を塗布することにより形成された皮膜を有する部材。
２． 金属が、合金鋼、炭素鋼、鋳鉄、アルミニウム又はアルミニウム合金である上記項１に記載の部材。
３． アミノ基含有シラノール誘導体が、下記一般式：
ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]m−[Ｓｉ(ＣＨ3)(Ｒ1ＮＨ2)Ｏ]n−Ｓｉ(ＯＲ2)3 （１）
（式中、ｍは１〜２０の整数、ｎは１〜２０の整数、Ｒ1はアルキレン基、Ｒ2は水素原子又はアルキル基を示す。）
で表される化合物である上記項１又は２に記載の部材。
４． 前記溶液がアミノ基含有シラノール誘導体を０．１〜１０容量％含む上記項１〜３のいずれかに記載の部材。
５． 部材が、プレス金型用部材又はインジェクション金型用部材である上記項１〜４のいずれかに記載の部材。
６． 部材が、ゴム成型用金型部材又は樹脂成形用金型部材である上記項１〜５のいずれかに記載の部材。
７． 金属基材又はセラミックス基材表面に皮膜を形成させる方法であって、
（１）前記基材表面にアミノ基含有シラノール誘導体を含む溶液を塗布することにより塗布物を得る工程、及び
（２）工程（１）により得られた塗布物を乾燥させることにより皮膜を形成させる工程
を含む皮膜形成方法。
８． 金属が、合金鋼、炭素鋼、鋳鉄、アルミニウム又はアルミニウム合金である上記項７に記載の皮膜形成方法。
９． アミノ基含有シラノール誘導体が、下記一般式：
ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]m−[Ｓｉ(ＣＨ3)(Ｒ1ＮＨ2)Ｏ]n−Ｓｉ(ＯＲ2)3 （１）
（式中、ｍは１〜２０の整数、ｎは１〜２０の整数、Ｒ１はアルキレン基、Ｒ２は水素原子又はアルキル基を示す。）
で表される化合物である上記項７又は８に記載の皮膜形成方法。
１０． 前記溶液がアミノ基含有シラノール誘導体を０．１〜１０容量％含む上記項７〜９のいずれかに記載の皮膜形成方法。
１１． 工程（１）において、はけ塗り法、カーテンコート法、遠心塗布法、ディッピング法及びスプレー法から選ばれる少なくとも１種の方法により前記基材表面に前記溶液を塗布する上記項７〜１０のいずれかに記載の皮膜形成方法。
１２． 部材が、プレス金型用部材又はインジェクション金型用部材である上記項７〜１１のいずれかに記載の皮膜形成方法。
１３． 部材が、ゴム成型用金型部材又は樹脂成形用金型部材である上記項７〜１２のいずれかに記載の皮膜形成方法。
That is, the present invention relates to a member having the following film and a film forming method.
1. A member having a film formed by applying a solution containing an amino group-containing silanol derivative to the surface of a metal substrate or ceramic substrate.
2. Item 2. The member according to Item 1, wherein the metal is alloy steel, carbon steel, cast iron, aluminum, or an aluminum alloy.
3. The amino group-containing silanol derivative has the following general formula:
CH 3 - [Si (CH 3 ) 2 O] m - [Si (CH 3) (R 1 NH 2) O] n -Si (OR 2) 3 (1)
(In the formula, m represents an integer of 1 to 20, n represents an integer of 1 to 20, R 1 represents an alkylene group, and R 2 represents a hydrogen atom or an alkyl group.)
Item 3. The member according to Item 1 or 2, which is a compound represented by the formula:
4). Item 4. The member according to any one of Items 1 to 3, wherein the solution contains 0.1 to 10% by volume of an amino group-containing silanol derivative.
5. Item 5. The member according to any one of Items 1 to 4, wherein the member is a member for a press mold or a member for an injection mold.
6). Item 6. The member according to any one of Items 1 to 5, wherein the member is a rubber molding die member or a resin molding die member.
7). A method of forming a film on the surface of a metal substrate or ceramic substrate,
(1) A step of obtaining a coated product by applying a solution containing an amino group-containing silanol derivative on the surface of the substrate, and (2) forming a film by drying the coated product obtained in step (1). A film forming method including a step.
8). Item 8. The film forming method according to Item 7, wherein the metal is alloy steel, carbon steel, cast iron, aluminum, or an aluminum alloy.
9. The amino group-containing silanol derivative has the following general formula:
CH 3 - [Si (CH 3 ) 2 O] m - [Si (CH 3) (R 1 NH 2) O] n -Si (OR 2) 3 (1)
(In the formula, m represents an integer of 1 to 20, n represents an integer of 1 to 20, R 1 represents an alkylene group, and R 2 represents a hydrogen atom or an alkyl group.)
Item 9. The film forming method according to Item 7 or 8, which is a compound represented by the formula:
10. Item 10. The film forming method according to any one of Items 7 to 9, wherein the solution contains 0.1 to 10% by volume of an amino group-containing silanol derivative.
11. Any of the above items 7 to 10, wherein in the step (1), the solution is applied to the substrate surface by at least one method selected from a brush coating method, a curtain coating method, a centrifugal coating method, a dipping method and a spraying method. The method for forming a film according to claim 1.
12 Item 12. The film forming method according to any one of Items 7 to 11, wherein the member is a member for a press die or a member for an injection die.
13. Item 13. The film forming method according to any one of Items 7 to 12, wherein the member is a rubber molding die member or a resin molding die member.
皮膜を有する部材
本発明の部材は、金属基材又はセラミックス基材表面に、アミノ基含有シラノール誘導体を含む溶液を塗布することにより形成された皮膜を有するものである。
Member having a film The member of the present invention has a film formed by applying a solution containing an amino group-containing silanol derivative to the surface of a metal substrate or a ceramic substrate.
本発明の部材は、皮膜を基材表面の全体又は一部に形成してなるものである。
基材に用いる金属としては、皮膜を好適に形成できるものであればよいが、特に合金鋼、炭素鋼、鋳鉄、アルミニウム又はアルミニウム合金が好ましい。
The member of the present invention is formed by forming a film on the whole or a part of the substrate surface.
The metal used for the substrate is not particularly limited as long as it can form a film suitably, but alloy steel, carbon steel, cast iron, aluminum or aluminum alloy is particularly preferable.
合金鋼としては、例えばステンレス鋼、耐火鋼、耐熱鋼等が挙げられる。 Examples of the alloy steel include stainless steel, refractory steel, and heat resistant steel.
アルミニウム合金としては、ＪＩＳ規格２０００系〜７０００系のアルミニウム合金を好適に使用できる。ＪＩＳ規格２０００系〜７０００系のアルミニウム合金としては、例えば、２０００系のＡｌ−Ｃｕ合金、３０００系のＡｌ−Ｍｎ合金、４０００系のＡｌ−Ｓｉ合金、５０００系のＡｌ−Ｍｇ合金、６０００系のＡｌ−Ｍｎ−Ｓｉ系合金、７０００系のＡｌ−Ｚｎ−Ｍｇ系合金等が挙げられる。 As the aluminum alloy, an aluminum alloy of JIS standard 2000 series to 7000 series can be suitably used. Examples of JIS standard 2000 series to 7000 series aluminum alloys include 2000 series Al-Cu alloys, 3000 series Al-Mn alloys, 4000 series Al-Si alloys, 5000 series Al-Mg alloys, and 6000 series aluminum alloys. Examples include Al—Mn—Si based alloys, 7000 based Al—Zn—Mg based alloys, and the like.
これら金属の中でも特に、炭素鋼及び鋳鉄が好ましい。
セラミックスとしては、例えば、アルミナ系セラミックス、シリカ系セラミックス、チタニア系セラミックス、炭化珪素系セラミックス、ジルコニア系セラミックス等が挙げられる。この中でも特に、ジルコニア系セラミックスが好ましい。
Among these metals, carbon steel and cast iron are particularly preferable.
Examples of the ceramic include alumina-based ceramics, silica-based ceramics, titania-based ceramics, silicon carbide-based ceramics, and zirconia-based ceramics. Among these, zirconia ceramics are particularly preferable.
基材の形状は特に限定されず、板状、円板状、棒状等のいずれの形状であってもよく、また、複雑な形状であってもよい。特に、後記の皮膜形成方法によれば、複雑な形状の基材に対しても好適に皮膜を形成させることができる。 The shape of the substrate is not particularly limited, and may be any shape such as a plate shape, a disk shape, or a rod shape, or may be a complicated shape. In particular, according to the film forming method described later, a film can be suitably formed even on a substrate having a complicated shape.
基材の表面粗さは、特に限定されないが、Ｒａ（中心線平均粗さ）が５μｍ未満が好ましく、０．００５μｍ〜０．３μｍがより好ましく、０．０３〜０．３μｍがさらに好ましい。Ｒａが０．３μｍ以下の場合、基材表面に対して皮膜をより確実に密着させることができる。なお、Ｒａが０．０３未満の場合、そのような基材を用意するのに高いコストがかかる。
また、Ｒｍａｘ（最大高さ）は５０μｍ未満が好ましく、０．３〜３μｍがより好ましい。Ｒｍａｘが０．３〜３μｍ、特に１μｍ程度の場合、アンカー効果による基材と皮膜との密着性の向上と、点接触になることによる非粘着性及び撥水性の向上を図ることができる。Ｒｍａｘが５０μｍを超える場合、非粘着性（離型性）の効果よりもアンカー効果の方が大きく影響することにより、本来非粘着性を発現したい相手材に対しても密着性を発現するおそれがある。
The surface roughness of the substrate is not particularly limited, but Ra (center line average roughness) is preferably less than 5 μm, more preferably 0.005 μm to 0.3 μm, and even more preferably 0.03 to 0.3 μm. When Ra is 0.3 μm or less, the coating can be more reliably adhered to the substrate surface. When Ra is less than 0.03, it is expensive to prepare such a substrate.
Rmax (maximum height) is preferably less than 50 μm, more preferably 0.3 to 3 μm. When Rmax is 0.3 to 3 μm, particularly about 1 μm, it is possible to improve the adhesion between the substrate and the film due to the anchor effect and to improve the non-adhesiveness and water repellency due to the point contact. When Rmax exceeds 50 μm, the anchor effect has a greater influence than the non-adhesive (releasing) effect, and thus there is a possibility that adhesiveness may be expressed even with a counterpart material that originally wants to exhibit non-adhesive properties. is there.
「アミノ基含有シラノール誘導体」とは、１分子内にアミノ基を含む有機基とシラノール基（またはその誘導体）とを有する化合物をいう。 The “amino group-containing silanol derivative” refers to a compound having an organic group containing an amino group and a silanol group (or a derivative thereof) in one molecule.
例えば、下記一般式：
ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]m−[Ｓｉ(ＣＨ3)(Ｒ1ＮＨ2)Ｏ]n−Ｓｉ(ＯＲ2)3 （１）
（式中、ｍは１〜２０の整数、ｎは１〜２０の整数、Ｒ1はアルキレン基、Ｒ2は水素原子又はアルキル基を示す。）
で表される化合物が挙げられる。
For example, the general formula:
CH 3 - [Si (CH 3 ) 2 O] m - [Si (CH 3) (R 1 NH 2) O] n -Si (OR 2) 3 (1)
(In the formula, m represents an integer of 1 to 20, n represents an integer of 1 to 20, R 1 represents an alkylene group, and R 2 represents a hydrogen atom or an alkyl group.)
The compound represented by these is mentioned.
以下、上記一般式（１）の化合物を代表例として説明する。 Hereinafter, the compound of the general formula (1) will be described as a representative example.
アルキレン基としては、炭素数１〜４０、好ましくは炭素数１〜５の直鎖または分岐鎖のアルキレン基が挙げられる。 Examples of the alkylene group include linear or branched alkylene groups having 1 to 40 carbon atoms, preferably 1 to 5 carbon atoms.
具体的には、(ＣＨ2)i（ｉは１〜４０の整数）、(ＣＨ2)jＣ(ＣＨ3)2（ｊは２〜３７の整数）等のアルキレン基、より具体的には、ＣＨＣＨ3ＣＨ2、ＣＨ2ＣＨＣＨ3、ＣＨＣＨ3(ＣＨ2)2、ＣＨ2ＣＨＣＨ3ＣＨ2、Ｃ(ＣＨ3)2ＣＨ2、ＣＨ2Ｃ(ＣＨ3)2等のアルキレン基を例示することができる。 Specifically, an alkylene group such as (CH 2 ) i (i is an integer of 1 to 40), (CH 2 ) j C (CH 3 ) 2 (j is an integer of 2 to 37), more specifically , CHCH 3 CH 2 , CH 2 CHCH 3 , CHCH 3 (CH 2 ) 2 , CH 2 CHCH 3 CH 2 , C (CH 3 ) 2 CH 2 , CH 2 C (CH 3 ) 2, etc. be able to.
アルキル基としては、炭素数１〜１０、好ましくは炭素数１〜５の直鎖または分岐鎖のアルキル基が挙げられる。 Examples of the alkyl group include linear or branched alkyl groups having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms.
上記の一般式（１）で表されるアミノ基含有シラノール誘導体は、公知の方法により製造することができる。また、市販品を入手してもよい。 The amino group-containing silanol derivative represented by the general formula (1) can be produced by a known method. Moreover, you may obtain a commercial item.
アミノ基含有シラノール誘導体を溶媒に溶解させることにより溶液を調製する。溶媒としては、アルコール系溶剤、水、酢酸等、またはこれらの混合溶媒等が例示される。 A solution is prepared by dissolving an amino group-containing silanol derivative in a solvent. Examples of the solvent include alcohol solvents, water, acetic acid and the like, or mixed solvents thereof.
特に、溶媒としては、揮発性の高い溶媒、すなわち、基材表面に溶液を塗布後、塗布物から容易に除去できる溶媒が好ましい。そのような溶媒としては、例えばメタノール、エタノール、ｎ−プロパノール、ｉｓｏ−プロパノール等が挙げられる。この中でも特に、アミノ基含有シラノール誘導体が均一に溶解し、且つ、均一に溶解した状態を長時間維持できる点から、ｉｓｏ−プロパノールが好ましい。 In particular, the solvent is preferably a highly volatile solvent, that is, a solvent that can be easily removed from the coated material after the solution is applied to the substrate surface. Examples of such a solvent include methanol, ethanol, n-propanol, iso-propanol and the like. Among these, iso-propanol is particularly preferable because the amino group-containing silanol derivative is uniformly dissolved and the uniformly dissolved state can be maintained for a long time.
溶液中のアミノ基含有シラノール誘導体の含有量は、溶液の安定性及び基材表面への単分子皮膜の形成のし易さの点から、通常０．１〜１０容量％程度、好ましくは１〜３容量％程度である。 The content of the amino group-containing silanol derivative in the solution is usually about 0.1 to 10% by volume, preferably 1 to 10% from the viewpoint of the stability of the solution and the ease of forming a monomolecular film on the surface of the substrate. About 3% by volume.
溶液を調製する際、本発明の効果を妨げない範囲で、塗布液の調製に通常使用される公知の添加剤を加えてもよい。 When preparing the solution, known additives usually used for preparing the coating solution may be added as long as the effects of the present invention are not impaired.
前記溶液を塗布することにより形成された皮膜は、基材由来のヒドロキシル基とアミノ基含有シラノール誘導体とが脱水縮合反応することにより、又は、ヒドロキシル基とアミノ基含有シラノール誘導体とが水素結合することにより形成されると考えられる。具体的には、一般式（１）のシラノール誘導体におけるＣＨ３基を含む基、ＮＨ２基を含む基又はＯＲ２基を含む基が、基材面側に配置し、図１のように、芝生構造を形成してなるものであると考えられる。特に、本発明においては、アミノ基を含む基が基材面側に配置していることが好ましい。なお、図１では、シラノール誘導体同士が独立して存在しているが、隣同士で相互作用していてもよい。 The film formed by applying the solution has a dehydration condensation reaction between the hydroxyl group derived from the substrate and the amino group-containing silanol derivative, or the hydroxyl group and the amino group-containing silanol derivative are hydrogen bonded. It is thought that it is formed by. Specifically, a group containing a CH 3 group, a group containing an NH 2 group or a group containing an OR 2 group in the silanol derivative of the general formula (1) is arranged on the substrate surface side, and as shown in FIG. It is thought that it is formed by forming a lawn structure. In particular, in the present invention, it is preferable that a group containing an amino group is arranged on the substrate surface side. In FIG. 1, silanol derivatives are present independently, but may be interacting with each other.
皮膜の厚さは、部材の使用環境、設置場所等に応じて適宜設定すればよいが、通常０．０１〜５μｍ程度、好ましくは０．０２〜０．５μｍ程度である。皮膜の厚さが０．０１μｍ未満の場合、表面を均一に覆うだけのアミノ基含有シラノール誘導体が供給されず、ムラが生じやすくなる。本発明において、前記膜は、単分子層を形成するように、アミノ基含有シラノール誘導体のアミノ基を含む基が基材面側に配置（結合）ないし相互作用したものであることが好ましい。そのため、膜厚が高すぎる場合（膜厚が５μｍを超える場合）、皮膜中の分子配向が乱れ、さらに、シラノール誘導体の基材からの距離が遠くなることにより、基材との結合ないし相互作用が弱くなり、結果、基材に対する皮膜の密着性が低下するおそれがある。なお、膜厚が高くなる原因としては、例えば、芝生構造を形成するシラノール誘導体上に、さらに他のシラノール誘導体が物理吸着する場合が挙げられる。 The thickness of the film may be appropriately set according to the use environment of the member, the installation location, etc., but is usually about 0.01 to 5 μm, preferably about 0.02 to 0.5 μm. When the thickness of the film is less than 0.01 μm, the amino group-containing silanol derivative sufficient to uniformly cover the surface is not supplied, and unevenness tends to occur. In the present invention, the film is preferably a film in which a group containing an amino group of an amino group-containing silanol derivative is arranged (bonded) or interacts on the substrate surface side so as to form a monomolecular layer. Therefore, when the film thickness is too high (when the film thickness exceeds 5 μm), the molecular orientation in the film is disturbed, and further, the distance from the base material of the silanol derivative is increased, so that the binding or interaction with the base material is caused. As a result, the adhesion of the film to the substrate may be reduced. In addition, as a cause which a film thickness becomes high, the case where another silanol derivative further carries out physical adsorption on the silanol derivative which forms a lawn structure, for example is mentioned.
特に、本発明の部材を精密性が要求される自動車部品及びＩＴ部品（例えば半導体）の製造ラインや、試験製造装置等の部品として用いる場合、皮膜の厚さは１μｍ以下が好ましく、０．０１〜０．１μｍがより好ましい。 In particular, when the members of the present invention are used as parts for automobile parts and IT parts (for example, semiconductors) production lines and test production apparatuses that require precision, the thickness of the coating is preferably 1 μm or less, 0.01 -0.1 micrometer is more preferable.
本発明の部材は、産業用製造ライン、特に、精密性が要求される自動車部品及びＩＴ部品（例えば半導体）の製造ラインや、試験製造装置等の部品に用いられる部材として用いることができる。特に、本発明の部材は、プレス金型用部材又はインジェクション金型用部材として好適に用いることができる。 The member of the present invention can be used as a member used in parts for industrial production lines, particularly automobile parts and IT parts (for example, semiconductor) production lines that require precision, and test production equipment. In particular, the member of the present invention can be suitably used as a press mold member or an injection mold member.
また、本発明の部材は、業務用の接着剤の粘着や、成形樹脂の残留物の付着等を有効に防止できるため、ゴム成型用金型部材又は樹脂成形用金型部材として特に好適に用いることができる。 Further, the member of the present invention can be effectively used as a rubber molding die member or a resin molding die member because it can effectively prevent sticking of adhesives for business use and adhesion of molding resin residues. be able to.
皮膜形成方法
本発明の皮膜形成方法は、金属基材又はセラミックス基材表面に皮膜を形成させる方法であって、
（１）前記基材表面にアミノ基含有シラノール誘導体を含む溶液を塗布することにより塗布物を得る工程、及び
（２）工程（１）により得られた塗布物を乾燥させることにより皮膜を形成させる工程
を含む。
Film Forming Method The film forming method of the present invention is a method of forming a film on the surface of a metal substrate or ceramic substrate,
(1) A step of obtaining a coated product by applying a solution containing an amino group-containing silanol derivative on the surface of the substrate, and (2) forming a film by drying the coated product obtained in step (1). Process.
金属基材及びセラミックス基材については、上記と同様のものを用いればよい。 About a metal base material and a ceramic base material, the thing similar to the above should just be used.
工程（１）
工程（１）では、前記基材表面にアミノ基含有シラノール誘導体を含む溶液を塗布することにより塗布物を得る。
Process (1)
In the step (1), a coated product is obtained by coating a solution containing an amino group-containing silanol derivative on the substrate surface.
アミノ基含有シラノール誘導体を含む溶液としては、上記と同様の溶液を用いればよい。 As a solution containing an amino group-containing silanol derivative, a solution similar to the above may be used.
前記溶液は、基材表面の全体又は一部に塗布すればよい。 What is necessary is just to apply | coat the said solution to the whole substrate surface or a part.
塗布方法としては、はけ塗り法、カーテンコート法、遠心塗布法、ディッピング法及びスプレー法から選ばれる少なくとも１種の方法を採用すればよい。これら塗布方法は、いずれも公知の方法に従って行えばよい。これら塗布方法の中でも特にスプレー法が好ましい。 As a coating method, at least one method selected from a brush coating method, a curtain coating method, a centrifugal coating method, a dipping method, and a spray method may be employed. Any of these coating methods may be performed according to known methods. Among these coating methods, the spray method is particularly preferable.
工程（２）
工程（２）では、工程（１）により得られた塗布物を乾燥させることにより皮膜を形成させる。塗布物を乾燥させることにより、シラノール誘導体を基材表面に配置することができる。また、溶液中の溶媒を除去することができる。
Process (2)
In step (2), a coating is formed by drying the coated product obtained in step (1). By drying the coated material, the silanol derivative can be arranged on the surface of the substrate. In addition, the solvent in the solution can be removed.
乾燥は、自然乾燥及び／又は加熱乾燥により行うことができる。特に本発明の皮膜形成方法では、加熱乾燥を行うことが好ましい。加熱乾燥を行うことにより、より脱水縮合を促進させることができるため、より強固な皮膜の形成が可能となる。その結果、より耐摩耗性、撥水性及び平滑性に優れた部材を得ることができる。また、加熱乾燥を行うことにより、脱水縮合反応をより短時間で進めることができる。 Drying can be performed by natural drying and / or heat drying. In particular, in the film forming method of the present invention, it is preferable to perform heat drying. By performing drying by heating, dehydration condensation can be further promoted, so that a stronger film can be formed. As a result, a member having more excellent wear resistance, water repellency and smoothness can be obtained. Moreover, dehydration condensation reaction can be advanced in a shorter time by performing heat drying.
自然乾燥、すなわち、室温（２５℃程度）下での乾燥の場合、乾燥時間は、使用する溶媒の種類等に応じて適宜設定すればよいが、通常２４〜９６時間程度であればよい。 In the case of natural drying, that is, drying at room temperature (about 25 ° C.), the drying time may be appropriately set according to the type of the solvent to be used, etc., but is usually about 24 to 96 hours.
加熱乾燥の場合、加熱温度は、１００〜４００℃程度、好ましくは１００〜１５０℃程度である。加熱時間は、通常２０分〜１時間程度であればよい。 In the case of heat drying, the heating temperature is about 100 to 400 ° C, preferably about 100 to 150 ° C. The heating time is usually about 20 minutes to 1 hour.
以上の方法により、金属基材又はセラミックス基材表面に皮膜を形成させることができる。 By the above method, a film can be formed on the surface of a metal substrate or a ceramic substrate.
また、工程（１）及び工程（２）をゾルゲル法により行うことによって、金属基材又はセラミックス基材表面に皮膜を形成させることもできる。具体的には、まず、上記アミノ基含有シラノール誘導体を水と共に攪拌することにより、溶液（ゾル）を調製する。得られた溶液を基材表面に塗布した後、１００〜１２０℃で１０〜２０分間乾燥させることにより、基材表面のゾルをゲル化させる。次いで、基材表面のゲルを１２０〜１５０℃で１〜２時間焼成することにより、基材表面に皮膜を形成させることができる。
皮膜形成の回数は、目的とする耐摩耗性、撥水性、非粘着性等に応じて設定すればよく、通常１〜５回程度、好ましくは２〜３回程度である。
皮膜形成を２回以上行うことにより、図１の芝生構造におけるシラノール誘導体同士の隙間を補充することができ、皮膜の密度を向上させることができる。その結果、より非粘着性に優れた部材を得ることができる。また、皮膜形成の回数が５回を超える場合、皮膜中の分子配向が乱れ、シラノール誘導体の基材からの距離が遠くなることにより、基材との結合ないし相互作用が弱くなり、結果、基材に対する皮膜の密着性が低下するおそれがある。
Moreover, a film can also be formed on the surface of a metal substrate or a ceramic substrate by performing the step (1) and the step (2) by a sol-gel method. Specifically, first, a solution (sol) is prepared by stirring the amino group-containing silanol derivative together with water. After apply | coating the obtained solution to the base-material surface, the sol on a base-material surface is gelatinized by making it dry for 10 to 20 minutes at 100-120 degreeC. Subsequently, a film can be formed on the substrate surface by baking the gel on the substrate surface at 120 to 150 ° C. for 1 to 2 hours.
What is necessary is just to set the frequency | count of film formation according to the target abrasion resistance, water repellency, non-adhesiveness, etc., and is normally about 1-5 times, Preferably it is about 2-3 times.
By performing film formation twice or more, gaps between silanol derivatives in the lawn structure of FIG. 1 can be replenished, and the density of the film can be improved. As a result, a member that is more excellent in non-adhesiveness can be obtained. In addition, when the number of film formations exceeds 5, the molecular orientation in the film is disturbed and the distance from the substrate of the silanol derivative is increased, so that the bond or interaction with the substrate is weakened. There is a risk that the adhesion of the film to the material may be reduced.
本発明の部材は、撥水性及び耐久性に優れているため、産業用製造ラインの部品の部材、特に、プレス金型用部材又はインジェクション金型用部材として好適に使用できる。
加えて、本発明の部材は、非粘着性に優れているため、業務用の接着剤や成形樹脂（例えばポリエチレン、ポリプロピレン、ＡＢＳ樹脂、ポリアミド樹脂、アクリル樹脂、フェノール樹脂、エポキシ樹脂等）、ゴム（例えばスチレン−ブタジエンゴム、ブタジエンゴム、ブチルゴム、エチレン‐プロピレンゴム等）の部材への付着等を有効に防止することができるため、メンテナンスが容易である。よって、本発明の部材は、特に、ゴム成型用金型部材又は樹脂成形用金型部材として好適に用いることができる。
本発明の皮膜形成方法によれば、撥水性、耐久性及び非粘着性に優れた部材を得ることができる。しかも、本発明の製造方法によれば、基材表面に厚みが1μｍ以下の皮膜を容易に形成させることができる。従って、本発明の皮膜形成方法によれば、精密性が要求される自動車部品及びＩＴ部品の製造ラインや、試験製造装置等の部品に用いる部材を得ることができる。
さらに、本発明の皮膜形成方法によれば、複雑な形状の基材に対しても容易に皮膜を形成させることができる。
本発明の皮膜形成方法は、簡便な手法であるため、低コストで基材に皮膜を形成させることができる。
Since the member of the present invention is excellent in water repellency and durability, it can be suitably used as a component member of an industrial production line, particularly as a press die member or an injection die member.
In addition, since the member of the present invention is excellent in non-tackiness, commercial adhesives and molding resins (for example, polyethylene, polypropylene, ABS resin, polyamide resin, acrylic resin, phenol resin, epoxy resin, etc.), rubber Since it is possible to effectively prevent adhesion (for example, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene rubber, etc.) to a member, maintenance is easy. Therefore, the member of the present invention can be suitably used particularly as a rubber molding die member or a resin molding die member.
According to the film forming method of the present invention, a member excellent in water repellency, durability and non-adhesiveness can be obtained. Moreover, according to the production method of the present invention, a film having a thickness of 1 μm or less can be easily formed on the surface of the substrate. Therefore, according to the film forming method of the present invention, it is possible to obtain a member used for parts such as a production line for automobile parts and IT parts, a test production apparatus and the like that require precision.
Furthermore, according to the film forming method of the present invention, a film can be easily formed even on a substrate having a complicated shape.
Since the film forming method of the present invention is a simple technique, the film can be formed on the substrate at low cost.
以下、実施例及び比較例を挙げて本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
実施例１
下記の通り、本発明の部材を作製した。
（１）アミノ基含有シラノール誘導体を含む溶液の調製
液温２５℃のｉｓｏ−プロパノールを撹拌しながら、ｉｓｏ−プロパノールに、アミノ基含有シラノール誘導体ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]5−[Ｓｉ(ＣＨ3)(Ｃ3Ｈ6ＮＨ2)Ｏ]10−Ｓｉ(ＯＣ2Ｈ5)3を少しずつ添加した後、１５〜３０分間撹拌することにより、アミノ基含有シラノール誘導体を１容量％及びｉｓｏ−プロパノールを９９容量％含有する溶液を調製した。
（２）基材
基材としては、寸法５０ｍｍ×５０ｍｍ×３ｍｍのＳＵＳ３０４をｉｓｏ−プロパノールにて払拭したものを用いた。
（３）皮膜の形成
まず、気温２５℃、湿度６０％の条件下で、上記（２）の基材表面に、上記（１）により調製された溶液をエアスプレーを用いて膜厚が０．０１μｍになるまで塗布した。
Example 1
The member of this invention was produced as follows.
(1) Preparation of a solution containing an amino group-containing silanol derivative While stirring iso-propanol at a liquid temperature of 25 ° C., the amino group-containing silanol derivative CH 3 — [Si (CH 3 ) 2 O] 5 — [Si (CH 3 ) (C 3 H 6 NH 2 ) O] 10 —Si (OC 2 H 5 ) 3 was added little by little, and then stirred for 15 to 30 minutes, so that 1 volume of amino group-containing silanol derivative was added. A solution containing 99% by volume and 99% by volume of iso-propanol was prepared.
(2) Base material As the base material, SUS304 having a size of 50 mm × 50 mm × 3 mm was wiped with iso-propanol.
(3) Formation of film First, under the conditions of an air temperature of 25 ° C. and a humidity of 60%, the solution prepared according to the above (1) is applied to the surface of the base material of the above (2) by using an air spray to have a film thickness of 0. It applied until it became 01 micrometer.
得られた塗布物を、室温（２５℃）下で、２４時間放置した後、熱風乾燥炉を用いて１５０℃で２０分間加熱処理を行うことにより、本発明の部材を得た。 The obtained coated material was allowed to stand at room temperature (25 ° C.) for 24 hours, and then heat-treated at 150 ° C. for 20 minutes using a hot air drying furnace to obtain a member of the present invention.
実施例２
実施例１にて得られた部材を基材とし、この部材表面に、実施例１と同様の方法によって再度皮膜の形成を行うことにより、本発明の部材を得た。
Example 2
The member obtained in Example 1 was used as a base material, and a film of the present invention was obtained by forming a film again on the surface of the member by the same method as in Example 1.
実施例３
基材として、寸法５０ｍｍ×５０ｍｍ×３ｍｍの鋳鉄（ＳＳ４００）をｉｓｏ−プロパノールにて払拭したものを用いた以外は、実施例１と同様にして、本発明の部材を得た。
Example 3
A member of the present invention was obtained in the same manner as in Example 1 except that a cast iron (SS400) having dimensions of 50 mm × 50 mm × 3 mm was wiped with iso-propanol.
比較例１
寸法５０ｍｍ×５０ｍｍ×３ｍｍのＳＵＳ３０４をエタノールにて払拭した。
Comparative Example 1
SUS304 having a size of 50 mm × 50 mm × 3 mm was wiped with ethanol.
次いで、基材表面にＰＴＦＥ（ポリテトラフルオロエチレン）微粉末を静電塗装した後、３５０℃で３０分間焼付け処理を行うことにより、フッ素樹脂コート層を有する部材を得た。
実施例１〜３及び比較例１にて得られた部材について、以下の方法により膜厚測定、接触角試験、耐摩耗性試験及び粘着試験を行った。
Next, after PTFE (polytetrafluoroethylene) fine powder was electrostatically coated on the surface of the substrate, a member having a fluororesin coat layer was obtained by performing a baking treatment at 350 ° C. for 30 minutes.
About the member obtained in Examples 1-3 and the comparative example 1, the film thickness measurement, the contact angle test, the abrasion resistance test, and the adhesion test were done with the following method.
試験例１（膜厚測定）
接触式膜厚計（DeFelsko社製「PosiTector6000」）を用いることにより、実施例１〜３及び比較例１で得られた部材表面の皮膜の厚みを測定した。
Test example 1 (film thickness measurement)
By using a contact-type film thickness meter (“PosiTector6000” manufactured by DeFelsko), the thickness of the film on the surface of the member obtained in Examples 1 to 3 and Comparative Example 1 was measured.
結果を表１に示す。 The results are shown in Table 1.
試験例２（接触角試験）
ＦＡＣＥ接触角測定装置（協和界面科学(株)製「ＣＡ−Ａ型」）を用いて、液滴法（マイクロシリンジにより２μＬの水滴を落として、正面から接触角を測定すること）により実施例１〜３及び比較例１で得られた部材表面の皮膜に対する水の接触角を測定した。
Test example 2 (contact angle test)
Example using the FACE contact angle measurement device (“CA-A type” manufactured by Kyowa Interface Science Co., Ltd.) with the droplet method (dropping a 2 μL water droplet with a microsyringe and measuring the contact angle from the front) The contact angle of water with respect to the film | membrane of the member surface obtained by 1-3 and the comparative example 1 was measured.
結果を表１に示す。 The results are shown in Table 1.
試験例３（耐摩耗性試験）
先端に羊毛フェルトを取付けた摺動試験器（大平理化工業(株)製）を用いて、加重１０００ｇで実施例１〜３及び比較例１で得られた部材の皮膜面に羊毛フェルトを押しつけながら、往復１０ｃｍの距離を摺動させた。２００往復後の重量変化および接触角の変化を測定した。
Test example 3 (Abrasion resistance test)
Using a sliding tester (made by Ohira Rika Kogyo Co., Ltd.) with a wool felt attached to the tip, the wool felt was pressed against the coating surface of the members obtained in Examples 1 to 3 and Comparative Example 1 at a weight of 1000 g. Slid back and forth at a distance of 10 cm. Changes in weight and contact angle after 200 reciprocations were measured.
結果を表１に示す。 The results are shown in Table 1.
なお、接触角については、上記試験例２と同様の方法により測定した。 The contact angle was measured by the same method as in Test Example 2 above.
試験例４（粘着試験）
実施例１〜３及び比較例１で得られた部材にＡＢＳ樹脂を０．５ｇ載せて、電気炉（入江(株)製マッフル炉「ＫＤＦ−Ｓ９０」）にて２６０℃で３０分間加熱処理を行った後に放冷することにより、部材にＡＢＳ樹脂の硬化物を付着させた。
Test Example 4 (Adhesion test)
0.5 g of ABS resin is placed on the members obtained in Examples 1 to 3 and Comparative Example 1, and heat treatment is performed at 260 ° C. for 30 minutes in an electric furnace (Muffle furnace “KDF-S90” manufactured by Irie Co., Ltd.). After performing, it allowed to cool, and the hardened | cured material of ABS resin was made to adhere to a member.
前記硬化物を基材表面から剥がす際に必要な力をピークホールド付きテンションゲージにより測定した。 The force required to peel the cured product from the substrate surface was measured with a tension gauge with a peak hold.
結果を表１に示す。 The results are shown in Table 1.
（１）表１から、実施例１〜３にて得られた部材の皮膜の厚みは、1μm以下であり、比較例１にて得られた部材の皮膜の厚みよりかなり小さいことがわかる。
（２）表１から、耐摩耗試験後において、実施例１の部材は、比較例１の部材に比べ、接触角が１０度大きい。つまり、実施例１の部材は、比較例１の部材に比べ、良好な撥水性を有することがわかる。
(1) From Table 1, it can be seen that the film thickness of the member obtained in Examples 1 to 3 is 1 μm or less, which is considerably smaller than the film thickness of the member obtained in Comparative Example 1.
(2) From Table 1, after the abrasion resistance test, the member of Example 1 has a contact angle 10 degrees larger than the member of Comparative Example 1. That is, it can be seen that the member of Example 1 has better water repellency than the member of Comparative Example 1.
また、皮膜形成を２回行うことにより得られた実施例２の部材は、実施例１の部材に比べ、さらに接触角が大きく、より良好な撥水性を有することがわかる。しかも、実施例２の部材は、耐摩耗性試験後においても接触角の変化が確認できず、好適な撥水性を持続できることがわかる。 Further, it can be seen that the member of Example 2 obtained by performing the film formation twice has a larger contact angle and better water repellency than the member of Example 1. Moreover, it can be seen that the member of Example 2 cannot maintain a change in contact angle even after the wear resistance test, and can maintain a suitable water repellency.
さらに、基材として鋳鉄を用いた実施例３の部材も良好な撥水性を有することがわかる。
（３）表１から、耐摩耗性試験において、実施例１〜３の部材はいずれも比較例１の部材に比べて重量変化が小さく、耐摩耗性に優れていることがわかる。
（４）表１から、実施例１〜３にて得られた部材の場合、付着したＡＢＳ樹脂の硬化物を、比較例１にて得られた部材の場合よりも、かなり小さい力で剥がすことができることがわかる。すなわち、実施例１〜３にて得られた部材は、比較例１にて得られた部材よりも非密着性に優れていることがわかる。
Furthermore, it can be seen that the member of Example 3 using cast iron as the substrate also has good water repellency.
(3) From Table 1, it can be seen that in the wear resistance test, all the members of Examples 1 to 3 have a smaller weight change than the member of Comparative Example 1, and are excellent in wear resistance.
(4) From Table 1, in the case of the members obtained in Examples 1 to 3, the cured ABS resin was peeled off with a considerably smaller force than in the case of the member obtained in Comparative Example 1. You can see that That is, it can be seen that the members obtained in Examples 1 to 3 are superior in non-adhesiveness to the member obtained in Comparative Example 1.
また、皮膜形成を２回行うことにより得られた実施例２の部材は、皮膜形成を１回行うことにより得られた実施例１の部材に比べ、より非密着性に優れていることがわかる。 Moreover, it turns out that the member of Example 2 obtained by performing film formation twice is more excellent in non-adhesiveness than the member of Example 1 obtained by performing film formation once. .
Claims (13)
ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]m−[Ｓｉ(ＣＨ3)(Ｒ1ＮＨ2)Ｏ]n−Ｓｉ(ＯＲ2)3 （１）
（式中、ｍは１〜２０の整数、ｎは１〜２０の整数、Ｒ1はアルキレン基、Ｒ2は水素原子又はアルキル基を示す。）
で表される化合物である請求項１又は２に記載の部材。 The amino group-containing silanol derivative has the following general formula:
CH 3 - [Si (CH 3 ) 2 O] m - [Si (CH 3) (R 1 NH 2) O] n -Si (OR 2) 3 (1)
(In the formula, m represents an integer of 1 to 20, n represents an integer of 1 to 20, R 1 represents an alkylene group, and R 2 represents a hydrogen atom or an alkyl group.)
The member according to claim 1, which is a compound represented by the formula:
（１）前記基材表面にアミノ基含有シラノール誘導体を含む溶液を塗布することにより塗布物を得る工程、及び
（２）工程（１）により得られた塗布物を乾燥させることにより皮膜を形成させる工程
を含む皮膜形成方法。 A method of forming a film on the surface of a metal substrate or ceramic substrate,
(1) A step of obtaining a coated product by applying a solution containing an amino group-containing silanol derivative on the surface of the substrate, and (2) forming a film by drying the coated product obtained in step (1). A film forming method including a step.
ＣＨ3−[Ｓｉ(ＣＨ3)2Ｏ]m−[Ｓｉ(ＣＨ3)(Ｒ1ＮＨ2)Ｏ]n−Ｓｉ(ＯＲ2)3 （１）
（式中、ｍは１〜２０の整数、ｎは１〜２０の整数、Ｒ１はアルキレン基、Ｒ２は水素原子又はアルキル基を示す。）
で表される化合物である請求項７又は８に記載の皮膜形成方法。 The amino group-containing silanol derivative has the following general formula:
CH 3 - [Si (CH 3 ) 2 O] m - [Si (CH 3) (R 1 NH 2) O] n -Si (OR 2) 3 (1)
(In the formula, m represents an integer of 1 to 20, n represents an integer of 1 to 20, R 1 represents an alkylene group, and R 2 represents a hydrogen atom or an alkyl group.)
The film forming method according to claim 7, wherein the film is a compound represented by the formula:
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| JP2011200912A (en) * | 2010-03-25 | 2011-10-13 | Tokyo Metropolitan Industrial Technology Research Institute | Method and die for pressing metallic member |
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