JP2007169360A - Stock solution for coating composition - Google Patents
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本発明は、金属、プラスチック、紙等の種々の基材の表面に耐候性、耐久性に優れた皮膜を形成する際に使用する被覆組成物用原液であり、塗料、特に、防錆塗料の調製に有用な原液に関する。 The present invention is a stock solution for a coating composition for use in forming a film having excellent weather resistance and durability on the surface of various substrates such as metal, plastic, paper, etc. It relates to stock solutions useful for preparation.
従来、被覆組成物において、バインダーとなる樹脂にシリカを配合してその皮膜特性を改良することが行われてきた。例えば、防錆用塗料において、シリカを添加することにより、鋼板と表面処理樹脂被覆層との密着性を向上させ、また、腐食環境下で緻密で安定な金属の腐食生成物の形成に寄与し、防錆性を発揮するとされている（例えば、特許文献１、２参照）。 Conventionally, in coating compositions, silica has been added to a resin serving as a binder to improve the film properties. For example, the addition of silica in a rust-preventing paint improves the adhesion between the steel sheet and the surface-treated resin coating layer, and contributes to the formation of a dense and stable metal corrosion product in a corrosive environment. It is said to exhibit rust prevention properties (see, for example, Patent Documents 1 and 2).
この場合、上記組成物へのシリカの配合は、シリカを水などの溶媒に分散させたシリカ分散液の状態で行われる。例えば、防錆塗料の用途においては、有機溶媒や、水溶性樹脂に上記シリカ分散液を混合することにより用いられる。 In this case, the silica is mixed into the composition in the form of a silica dispersion in which silica is dispersed in a solvent such as water. For example, in the use of a rust preventive paint, it is used by mixing the silica dispersion in an organic solvent or a water-soluble resin.
このようなシリカ分散液としては、四塩化珪素を原料として酸水素炎中で燃焼させて作る乾式シリカ、珪酸ナトリウムを中和して作る沈殿法シリカやゲル法シリカといった、いわゆる湿式シリカが優れており、かかるシリカを使用したシリカ分散液が注目されている。 As such a silica dispersion, so-called wet silica such as dry silica made by burning silicon tetrachloride as a raw material in an oxyhydrogen flame, precipitated silica made by neutralizing sodium silicate and gel silica is excellent. In addition, silica dispersions using such silica have attracted attention.
しかしながら、上記乾式シリカ、湿式シリカは凝集性が強いため、これを分散性良く溶媒に分散させることは困難である。そのため、これらのシリカを使用して製造されるシリカ分散液は、一概に安定性が悪く、特に、塗料等の被覆組成物の調製において遭遇する環境である、弱酸性から中性の領域での前記シリカ分散液は、数日でシリカの沈降やゲル化が起こるため、安定性に劣り、実用的ではなかった。 However, since the dry silica and wet silica have strong cohesiveness, it is difficult to disperse them in a solvent with good dispersibility. For this reason, silica dispersions produced using these silicas are generally poorly stable, particularly in the weakly acidic to neutral regions that are encountered in the preparation of coating compositions such as paints. The silica dispersion liquid is inferior in stability and impractical because silica sedimentation or gelation occurs within a few days.
そのような中、酸性条件下における安定性を向上させたものとして、コロイダルシリカを塩基性塩化アルミニウムの水溶液で処理したものや、酸性珪酸溶液にアルミニウム化合物を含有させ粒子成長させて、粒子内にアルミニウム化合物を内包させたものなどが知られている（例えば、特許文献３、４参照）。 Under such circumstances, as an improvement in stability under acidic conditions, colloidal silica treated with an aqueous solution of basic aluminum chloride, or an aluminum particle in an acidic silicic acid solution is allowed to grow to grow particles. Those containing an aluminum compound are known (see, for example, Patent Documents 3 and 4).
しかし、これらの方法で得られたシリカ分散液は、アルミニウムの存在により酸性条件下で安定性を有するものの、塩化物イオン等の腐食性イオンだけでなく、金属不純物、例えばナトリウムなどのアルカリの含有量が多くなるため、不純物分の存在が好まれない用途ではその使用範囲が限られるといった問題があった。 However, although the silica dispersion obtained by these methods has stability under acidic conditions due to the presence of aluminum, it contains not only corrosive ions such as chloride ions but also metal impurities such as alkali such as sodium. Since the amount is large, there is a problem that the range of use is limited in applications where the presence of impurities is not preferred.
また、塗料等の被覆用組成物を調製する際には、物流コスト、保管場所等の面から、前記調製時に希釈して使用する高濃度の状態、即ち、「原液」の状態での保管が要求され、前記シリカ分散液におけるシリカの沈降やゲル化の発生の問題が一層深刻となっている。 In addition, when preparing a coating composition such as a paint, it is necessary to store it in a high concentration state that is diluted and used at the time of preparation, that is, in the state of a “stock solution” from the viewpoint of distribution cost, storage location, etc. There has been a growing demand for the problems of sedimentation and gelation of silica in the silica dispersion.
従って、本発明の目的は、従来用いられてきたコロイダルシリカで問題となっている、ナトリウムイオンや塩化物イオン等の不純物イオンの残存が無く、しかも、シリカ濃度が１０重量％以上の、シリカ濃度が高い分散液においても、シリカ粒子が高度に分散し、弱酸性から中性領域で長期間の保存安定性が良好なシリカ分散液よりなる被覆組成物用原液を提供することにある。 Therefore, the object of the present invention is that there is no residue of impurity ions such as sodium ions and chloride ions, which is a problem with conventionally used colloidal silica, and the silica concentration is 10% by weight or more. Another object of the present invention is to provide a coating composition stock solution comprising a silica dispersion in which the silica particles are highly dispersed even in a high dispersion, and the storage stability is long in a weakly acidic to neutral range.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた。その結果、アミノ酸又はその塩を含有するシリカ分散液が、長期間の保存においてゲル化せず、またシリカ粒子の沈降が起こらないといった保存安定性において優れた特性を示すと共に、塗料等の被覆組成物の調製において遭遇する環境である、弱酸性から中性におけるｐＨの変化においても優れた安定性を発揮することができ、前記目的を全て解決し得ることを見出し、本発明を完成するに至った。 The inventors of the present invention have made extensive studies to solve the above problems. As a result, the silica dispersion containing an amino acid or a salt thereof does not gel during long-term storage and exhibits excellent storage stability such that silica particles do not settle, and coating compositions such as paints It has been found that it can exhibit excellent stability even in a pH change from weak acidity to neutrality, which is an environment encountered in the preparation of products, and can solve all of the above objects, and has completed the present invention. It was.
即ち、本発明は、平均一次粒子径が３０ｎｍ以下のシリカ粒子を、平均二次粒子径（平均凝集粒子径）が２００ｎｍ以下となるように水媒体に分散させたシリカ分散液よりなり、該シリカ分散液は、シリカ濃度が１０〜３０重量％であり、且つ、シリカ粒子１００重量部に対して０．０１〜１０重量部のアミノ酸又はその塩を含有することを特徴とする被覆組成物用原液である。 That is, the present invention comprises a silica dispersion in which silica particles having an average primary particle size of 30 nm or less are dispersed in an aqueous medium so that an average secondary particle size (average aggregated particle size) is 200 nm or less. The dispersion liquid has a silica concentration of 10 to 30% by weight, and contains 0.01 to 10 parts by weight of an amino acid or a salt thereof with respect to 100 parts by weight of silica particles. It is.
また、本発明は、上記被覆組成物用原液を一成分として使用してなることを特徴とする防錆塗料をも提供する。 The present invention also provides a rust-preventing paint characterized by using the above coating composition stock solution as a component.
本発明の被覆組成物用原液は、シリカ粒子が微分散しているシリカ分散液にアミノ酸又はその塩を含んでいるため、高濃度において、優れた分散安定性および保存安定性を示す。 The coating composition stock solution of the present invention contains an amino acid or a salt thereof in a silica dispersion in which silica particles are finely dispersed, and thus exhibits excellent dispersion stability and storage stability at high concentrations.
そして、上記特性を利用して、金属・プラスチック・紙等の表面にガスバリヤ性、耐食性、親水性、光沢性、吸液性、絶縁性等を付与するための各種被覆組成物の用途において、該被覆組成物を調製する際の原液として有効に使用することができ、調製後においても安定した被覆組成物を得ることができる。 And in the use of various coating compositions for imparting gas barrier properties, corrosion resistance, hydrophilicity, glossiness, liquid absorption, insulation, etc. to the surface of metal, plastic, paper, etc. It can be used effectively as a stock solution when preparing a coating composition, and a stable coating composition can be obtained even after preparation.
また、シリカとして乾式シリカ、湿式シリカ（含水シリカ）を使用する場合、実質的に塩化物イオン等の腐食性イオンが入っていないため好ましく、防錆塗料の原料として使用した場合、シリカによる防錆性だけでなく、アミノ酸又はその塩によって、金属表面に溶出する金属イオンを捕捉し、緻密な皮膜を形成できることから、防錆性の極めて高い防錆塗料を得ることが可能である。 In addition, when dry silica or wet silica (hydrous silica) is used as silica, it is preferable because it does not contain corrosive ions such as chloride ions. In addition to the property, it is possible to capture a metal ion eluted on the metal surface with an amino acid or a salt thereof and form a dense film, so that it is possible to obtain a rust-preventing paint having an extremely high rust-preventing property.
（シリカ）
本発明において、シリカは公知のシリカを特に制限なく使用することができる。また、これらのシリカは、単独或いは複数種を混合して用いることもできる。上記シリカのうち、四塩化珪素などのシラン系ガスを酸水素炎中で燃焼させて得られる乾式シリカ、珪酸ナトリウムなどの酸による中和により得られる湿式シリカが特に好ましい。
(silica)
In the present invention, known silica can be used without particular limitation. Moreover, these silica can also be used individually or in mixture of multiple types. Among the silicas, dry silica obtained by burning a silane-based gas such as silicon tetrachloride in an oxyhydrogen flame, and wet silica obtained by neutralization with an acid such as sodium silicate are particularly preferable.
即ち、上記の乾式シリカ及び湿式シリカは、一次粒子が集まった二次凝集粒子を形成している構造を有していることから、これを添加した被覆組成物において、密着性や加工性が良い皮膜を得ることができる。
本発明に用いられるシリカの平均一次粒子径は、３０ｎｍ以下であることが好ましい。平均一次粒子径が３０ｎｍよりも大きいシリカを用いた場合、原液において沈殿物が堆積しやすく、保存安定性が悪くなる。
That is, the above-mentioned dry silica and wet silica have a structure forming secondary agglomerated particles in which primary particles are gathered, and therefore, in a coating composition to which this is added, adhesion and workability are good. A film can be obtained.
The average primary particle diameter of the silica used in the present invention is preferably 30 nm or less. When silica having an average primary particle size larger than 30 nm is used, precipitates are likely to be deposited in the stock solution, resulting in poor storage stability.
本発明に用いられるシリカの比表面積は、防錆効果の点から、５０〜４００ｍ２／ｇの範囲にあるのが好ましい。 It is preferable that the specific surface area of the silica used for this invention exists in the range of 50-400 m < 2 > / g from the point of a rust prevention effect.
（アミノ酸又はその塩）
また、本発明において、アミノ酸は、同一分子内にアミノ基とカルボキシル基を有する化合物であり、公知のアミノ酸が特に制限なく使用される。また、アミノ酸には光学異性体が存在するものもあるが、本発明においては光学異性体による効果の差はなく、いずれの異性体も単独であるいはラセミ体で使用することができる。
(Amino acid or its salt)
Moreover, in this invention, an amino acid is a compound which has an amino group and a carboxyl group in the same molecule, and a well-known amino acid is used without a restriction | limiting in particular. Some amino acids have optical isomers, but in the present invention, there is no difference in effect due to optical isomers, and any isomer can be used alone or in racemic form.
本発明に使用されるアミノ酸を具体的に例示すれば、下記一般式（１）で表されるアミノ酸が好ましい。 If the amino acid used for this invention is illustrated concretely, the amino acid represented by following General formula (1) is preferable.
Ｈ２Ｎ−Ｒ−ＣＯＯＨ （１）
一般式（１）においてＲは任意の置換基を表し、炭素数が１０以下の置換基が好ましく、さらに好ましくは炭素数が８以下の置換基である。炭素数が１０より大きくなると、水に対する溶解性が低くなるため、好ましくない。
H 2 N-R-COOH ( 1)
In the general formula (1), R represents an arbitrary substituent, preferably a substituent having 10 or less carbon atoms, and more preferably a substituent having 8 or less carbon atoms. When the carbon number is larger than 10, the solubility in water is lowered, which is not preferable.
具体的なものを例示すると、グリシン、アラニン、バリン、ロイシン、イソロイシン、セリン、トレオニン、システイン、メチオニン、フェニルアラニン、トリプトファン、チロシン、プロリン、グルタミン、グルタミン酸、アスパラギン、アスパラギン酸、リシン、アルギニン、ヒスチジン等の化合物及びこれらの縮合物が挙げられ、その中でも、被覆組成物用原液中のシリカ粒子の分散性及び保存安定性の観点から、リシン、アルギニン、ヒスチジンが特に好ましい。 Specific examples include glycine, alanine, valine, leucine, isoleucine, serine, threonine, cysteine, methionine, phenylalanine, tryptophan, tyrosine, proline, glutamine, glutamic acid, asparagine, aspartic acid, lysine, arginine, histidine, etc. Among them, lysine, arginine, and histidine are particularly preferable from the viewpoints of dispersibility and storage stability of the silica particles in the coating composition stock solution.
また、本発明においては、上記アミノ酸の酢酸塩、ギ酸塩、乳酸塩、リン酸塩等の塩も使用することができる。 In the present invention, salts of the above amino acids such as acetates, formates, lactates and phosphates can also be used.
（原液）
本発明において、被覆組成物用原液を構成するシリカ分散液中のシリカの濃度は好ましくは１０〜３０重量％、より好ましくは、１０〜２５重量％が好ましい。即ち、上記シリカ分散液中のシリカ濃度が１０重量％以上の高濃度において、前記アミノ酸又はその塩を添加する、本発明の効果が特に顕著であり、また、原液として貯蔵、および輸送する際のコストを低減できる。また、３０重量％以下とすることにより、被覆組成物用原液の粘度の上昇を抑えることが出来る。
(Stock solution)
In the present invention, the concentration of silica in the silica dispersion constituting the coating composition stock solution is preferably 10 to 30% by weight, more preferably 10 to 25% by weight. That is, when the silica concentration in the silica dispersion is as high as 10% by weight or more, the effect of the present invention is particularly remarkable when the amino acid or a salt thereof is added. Cost can be reduced. Moreover, the raise of the viscosity of the stock solution for coating compositions can be suppressed by setting it as 30 weight% or less.
本発明において、シリカ分散液は前記のシリカを平均二次粒子径が、２００ｎｍ以下になるように微粒化して調製されたものである。このように微粒化したシリカ粒子を分散せしめることにより、良好な保存安定性を得ることができる。 In the present invention, the silica dispersion is prepared by atomizing the silica so that the average secondary particle diameter is 200 nm or less. By dispersing the finely divided silica particles, good storage stability can be obtained.
なお、本発明でいう二次粒子径は、光散乱回折式の粒度分布測定装置で測定した体積基準算術平均径の値である。 In addition, the secondary particle diameter as used in the field of this invention is a value of the volume reference | standard arithmetic mean diameter measured with the light-scattering diffraction type particle size distribution measuring apparatus.
本発明の被覆組成物用原液に用いられる分散媒は、水を主体とするものであるが、少量の有機溶剤例えば、低級アルコールや酢酸エチル等の低沸点溶剤を含んでもよい。その場合、有機溶剤は全分散媒に対し、２０重量％以下、更には１０重量％以下であることが好ましい。 The dispersion medium used in the stock solution for a coating composition of the present invention is mainly composed of water, but may contain a small amount of an organic solvent such as a low boiling point solvent such as lower alcohol or ethyl acetate. In that case, the organic solvent is preferably 20% by weight or less, more preferably 10% by weight or less, based on the total dispersion medium.
本発明において、アミノ酸又はその塩の添加量は、被覆組成物用原液が、増粘・ゲル化することなく安定に製造でき、且つ、得られた被覆組成物用原液の粘度を低くし、且つ、該原液の保存安定性を良くするために、シリカ１００重量部に対して、０．０１〜１０重量部、特に０．０２〜５重量部とすることが好ましい。 In the present invention, the addition amount of the amino acid or salt thereof is such that the stock solution for coating composition can be stably produced without thickening and gelling, and the viscosity of the obtained stock solution for coating composition is lowered, and In order to improve the storage stability of the stock solution, it is preferably 0.01 to 10 parts by weight, particularly 0.02 to 5 parts by weight, based on 100 parts by weight of silica.
即ち、上記アミノ酸又はその塩の添加量が、０．０１重量部未満の場合、シリカ粒子間の凝集を抑える効果が不十分であるため、好ましくない。また、１０重量部を超える場合、多量に添加しても効果は少なく、場合によっては、シリカ粒子の凝集を促進させることとなる。 That is, when the added amount of the amino acid or a salt thereof is less than 0.01 parts by weight, the effect of suppressing aggregation between silica particles is insufficient, which is not preferable. When the amount exceeds 10 parts by weight, the effect is small even if added in a large amount, and in some cases, aggregation of silica particles is promoted.
アミノ酸又はその塩の添加量に対する被覆組成物用原液のｐＨ、粘度及び保存安定性は、添加するアミノ酸の種類により多少異なるため、予め実験により、前記添加量の範囲より最適な添加量を選択することが好ましい。 Since the pH, viscosity, and storage stability of the coating composition stock solution with respect to the addition amount of amino acid or salt thereof are slightly different depending on the type of amino acid to be added, the optimum addition amount is selected from the range of the addition amount by experiment in advance. It is preferable.
尚、本発明において、原液の保存安定性や分散性を向上させるために、本発明の効果を損なわない範囲で、ｐＨ調整剤としての酸、又はシランカップリング剤等の界面活性剤や防カビ剤等を少量添加しても良い。 In the present invention, in order to improve the storage stability and dispersibility of the stock solution, an acid as a pH adjusting agent or a surfactant such as a silane coupling agent or an antifungal agent within the range not impairing the effects of the present invention. A small amount of an agent may be added.
本発明の被覆組成物用原液は、弱酸性から中性、即ちｐＨ５〜８であっても長期間に渡って分散安定性が保たれる。 The coating composition stock solution of the present invention maintains dispersion stability over a long period of time even if it is weakly acidic to neutral, that is, pH 5-8.
（原液の製造方法）
本発明において、原液は、水媒体中に、シリカ粒子とアミノ酸又はその塩とが均一に分散していれば良いが、シリカをできるだけ高分散させるために、下記の工程によって得られたものが好適に使用される。
(Method for producing undiluted solution)
In the present invention, the stock solution may be obtained by uniformly dispersing silica particles and an amino acid or a salt thereof in an aqueous medium, but in order to disperse silica as high as possible, a solution obtained by the following steps is preferable. Used for.
即ち、水媒体中にシリカ及びアミノ酸又はその塩を予備分散させた後、該予備分散液を微粒化する方法が好ましい。具体的には、予備分散液の調製は、水媒体中にアミノ酸又はその塩を混合した溶液に、シリカを直接添加し、混合・分散する方法、水媒体中にシリカを添加し、分散した後に、アミノ酸又はその塩を混合・分散する方法、シリカ粒子及びアミノ酸又はその塩をそれぞれ水媒体に分散した液を混合・分散する方法などが挙げられる。 That is, a method in which silica and an amino acid or a salt thereof are predispersed in an aqueous medium and then the predispersed liquid is atomized is preferable. Specifically, the preliminary dispersion is prepared by adding silica directly to a solution in which an amino acid or a salt thereof is mixed in an aqueous medium, mixing and dispersing, and after adding and dispersing silica in the aqueous medium. And a method of mixing and dispersing an amino acid or a salt thereof, a method of mixing and dispersing a liquid in which silica particles and an amino acid or a salt thereof are dispersed in an aqueous medium, and the like.
上記の予備分散に用いる分散機は特に制限されないが、具体的には、プロペラ羽根、タービン羽根、パドル翼等を有する一般攪拌機、ディスパーミキサー等の高速回転遠心放射型攪拌機、ホモジナイザー、ホモミキサー、ウルトラミキサー等の高速回転せん断型攪拌機、コロイドミル、プラネタリーミキサー、吸引式分散機などの分散機、更に、上記高速回転せん断型撹拌機とプロペラ羽根及びパドル翼を組み合わせた複合型分散機、プラネタリーミキサーと高速回転遠心放射型撹拌機又は高速せん断型撹拌機を組み合わせた複合型分散機等が挙げられる。 The disperser used for the preliminary dispersion is not particularly limited, and specifically, a general stirrer having propeller blades, turbine blades, paddle blades, etc., a high-speed rotary radial stirrer such as a disper mixer, a homogenizer, a homomixer, an ultra Dispersers such as high-speed rotary shear type agitators such as mixers, colloid mills, planetary mixers, and suction type dispersers, and further, composite type dispersers combining the above high-speed rotary shear type agitators, propeller blades and paddle blades, and planetary Examples thereof include a composite disperser in which a mixer and a high-speed rotation centrifugal radiation stirrer or a high-speed shear stirrer are combined.
また、上記の方法によって得られた予備混合液を微粒化する方法は、特に制限されず、公知の微粒化装置を使用した方法が採用される。具体的には、サンドミル、ビーズミル等の湿式メディア型分散機、超音波ホモジナイザー、高圧ホモジナイザー等を使用した微粒化方法が挙げられる。 Moreover, the method in particular of atomizing the preliminary liquid mixture obtained by said method is not restrict | limited, The method using a well-known atomization apparatus is employ | adopted. Specifically, the atomization method using wet media type | mold dispersers, such as a sand mill and a bead mill, an ultrasonic homogenizer, a high-pressure homogenizer, etc. are mentioned.
（その他の条件）
本発明において、被覆組成物用原液の製造途中で増粘・ゲル化などを起こすことなくより安定的に製造するために、４５℃以下、特に２０〜４０℃の温度範囲に制御することが好ましい。
(Other conditions)
In the present invention, in order to produce more stably without causing thickening or gelation during the production of the coating composition stock solution, it is preferable to control to a temperature range of 45 ° C. or less, particularly 20 to 40 ° C. .
上記温度範囲に制御する方式は特に限定されず、液の組成に影響を与えない公知の冷却手段が特に制限なく採用される。例えば、各分散槽外部へのジャケット式冷却器の設置、各分散槽内部への冷却配管設置、各機器入口又は出口配管部への熱交換器の設置、等の冷却手段を、適宜選択して適用すればよい。 The method for controlling the temperature range is not particularly limited, and a known cooling means that does not affect the composition of the liquid is employed without any particular limitation. For example, by appropriately selecting cooling means such as installation of a jacket type cooler outside each dispersion tank, installation of cooling piping inside each dispersion tank, installation of a heat exchanger at each equipment inlet or outlet piping section, etc. Apply.
（防錆塗料）
本発明の被覆組成物用原液を使用して調製される防錆塗料に含まれるアミノ酸又はその塩は、金属表面に配位し易く、それにより金属表面を不動態化させることができ、特に、亜鉛系被覆鋼等に有効である。本発明の防錆塗料は、皮膜形成目的で有機バインダーを混合する。
(Anti-rust paint)
The amino acid or salt thereof contained in the anticorrosive paint prepared using the stock solution for the coating composition of the present invention can be easily coordinated to the metal surface, thereby passivating the metal surface. Effective for zinc-based coated steel. The rust preventive paint of the present invention is mixed with an organic binder for the purpose of film formation.
上記有機バインダーは、塗料の調製に使用される公知の各種のバインダーを用いることができる。代表的なバインダーを具体的に示せば、ポリウレタン樹脂、ポリエステル樹脂、ポリアクリル樹脂、メラミン樹脂、エポキシ樹脂等を挙げることができる。また、上記バインダーを２種類以上混合したバインダーも使用可能である。 As the organic binder, various known binders used for preparing paints can be used. Specific examples of the binder include a polyurethane resin, a polyester resin, a polyacrylic resin, a melamine resin, and an epoxy resin. Moreover, the binder which mixed 2 or more types of the said binder can also be used.
本発明の防錆塗料において、シリカに対する有機バインダーの配合割合は、公知の塗料において一般に採用される割合が特に制限なく採用される。例えば、配合割合は、シリカ１００重量部に対して１００〜２，０００重量部、好ましくは、１５０〜１，０００重量部、更に好ましくは１８０〜５００重量部である。 In the rust-preventing paint of the present invention, the ratio of the organic binder to the silica is not particularly limited as it is generally used in known paints. For example, the blending ratio is 100 to 2,000 parts by weight, preferably 150 to 1,000 parts by weight, and more preferably 180 to 500 parts by weight with respect to 100 parts by weight of silica.
（その他の添加剤）
本発明の防錆剤は、本発明の効果を著しく低下させない範囲で、公知の任意の添加剤を配合することができる。代表的な添加剤を例示すれば、界面活性剤、ｐＨ調整剤、消泡剤、防カビ剤等を挙げることができる。
(Other additives)
The rust preventive agent of the present invention can contain any known additive as long as the effect of the present invention is not significantly reduced. Examples of typical additives include surfactants, pH adjusters, antifoaming agents, and antifungal agents.
以下、本発明の実施例を挙げて具体的に説明するが、本発明はこれら実施例によって何ら制限されるものではない。尚、被覆組成物用原液の物性測定、および防錆性評価は以下の方法により行った。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the physical-property measurement and rust-proof evaluation of the coating composition undiluted | stock solution were performed with the following method.
（１）粘度測定
被覆組成物用原液３００ｇを５００ｍｌ容器に採取し、３０℃の恒温槽に１０分間つけた後、Ｂ型粘度計（トキメック製、ＢＬ）を用いて６０ｒｐｍの条件で被覆組成物用原液の粘度を測定した。なお、粘度の経時変化は、得られた被覆組成物用原液を２５℃で３０日間経時させた粘度を上記と同様の方法で測定し、粘度変化を調べた。
(1) Viscosity measurement After collecting 300 g of the coating composition stock solution in a 500 ml container and placing it in a thermostatic bath at 30 ° C. for 10 minutes, the coating composition was used at 60 rpm using a B-type viscometer (manufactured by Tokimec, BL). The viscosity of the stock solution was measured. The change in viscosity over time was determined by measuring the viscosity of the resulting coating composition stock solution that had been aged for 30 days at 25 ° C. in the same manner as described above.
（２）ｐＨ測定
被覆組成物用原液３００ｇを５００ｍｌ容器に採取し、ｐＨメーター（堀場製作所製、Ｆ−２２）を用いて、被覆組成物用原液のｐＨを測定した。
(2) pH measurement 300 g of the coating composition stock solution was collected in a 500 ml container, and the pH of the coating composition stock solution was measured using a pH meter (H-22, manufactured by Horiba, Ltd.).
（３）平均二次粒子径の測定
被覆組成物用原液のシリカ濃度が１０重量％となるように、該原液をイオン交換水で希釈した後、光散乱回折式の粒度分布測定装置（ベックマンコールター製、コールターＬＳ−２３０）を用いて、体積基準算術平均径を測定し、この値を平均二次粒子径として採用した。
(3) Measurement of average secondary particle size After diluting the undiluted solution with ion-exchanged water so that the silica concentration of the undiluted solution for coating composition is 10% by weight, a light scattering diffraction type particle size distribution analyzer (Beckman Coulter) Manufactured by Coulter LS-230), the volume-based arithmetic average diameter was measured, and this value was adopted as the average secondary particle diameter.
尚、測定に際しては、水（分散媒）の屈折率１．３３２及びシリカの屈折率１．４５８をパラメーターとして入力した。 In the measurement, the refractive index of water (dispersion medium) 1.332 and the refractive index of silica 1.458 were input as parameters.
（４）防錆性評価
被覆組成物用原液と水溶性ポリウレタン樹脂（第一工業製薬製、スーパーフレックス１１０）をシリカ１００重量部に対して水溶性ポリウレタン樹脂が２００重量部となるように混合し、シリカ濃度５重量％、樹脂固形分濃度１０重量％の防錆塗料とした。
(4) Rust prevention evaluation The coating composition stock solution and water-soluble polyurethane resin (Daiichi Kogyo Seiyaku Co., Ltd., Superflex 110) are mixed so that the water-soluble polyurethane resin is 200 parts by weight with respect to 100 parts by weight of silica. A rust-proof paint having a silica concentration of 5% by weight and a resin solid content of 10% by weight was obtained.
防錆塗料で処理する金属板は、１５０ｍｍ×７０ｍｍ×０．８ｍｍの溶融合金化亜鉛めっき鋼板をアセトンを使用して脱脂し、次いで水洗、乾燥したものを用いた。次に、鋼板に上記防錆塗料を＃３のバーコーターにて塗布し、１５０℃に保たれた乾燥機で焼き付けて試験片を作製した。 As the metal plate to be treated with the anticorrosive paint, a 150 mm × 70 mm × 0.8 mm hot-dip alloyed galvanized steel plate was degreased using acetone, then washed and dried. Next, the above-mentioned rust preventive paint was applied to a steel plate with a # 3 bar coater, and baked with a drier kept at 150 ° C. to prepare a test piece.
評価は、試験板を５重量％塩化ナトリウム水溶液に浸漬した後、余滴を除去したものを３５℃、相対湿度８５％の湿潤雰囲気下に１２０時間放置し、試験片の腐食の程度を肉眼観察して下記の基準で判定した。 Evaluation was made by immersing the test plate in a 5% by weight aqueous sodium chloride solution, removing the remaining drops, leaving it in a humid atmosphere at 35 ° C. and a relative humidity of 85% for 120 hours, and visually observing the degree of corrosion of the test piece. The following criteria were used.
５：赤錆の発生なし、４：錆発生面積５％未満、３：錆発生面積５％以上１０％未満、２：錆発生面積１０％以上１５％未満、１：錆発生面積１５％以上２５％未満、０：錆発生面積２５％以上
実施例１
比表面積が３００ｍ２／ｇのヒュームドシリカ（トクヤマ製、レオロシールＱＳ−３０）をイオン交換水に徐々に添加しながら、液温度を３０℃に維持して、ウルトラミキサー（みづほ工業製、ウルトラミキサーＬＲ−２）で分散することにより、シリカ濃度１２重量％のシリカスラリーを得た。このシリカスラリーとリジン水溶液をシリカ１００重量部に対してリジンが０．１重量部となるように混合・分散し、予備混合液を得た。尚、予備混合中の液温度は３０℃を維持した。この予備混合液を高圧ホモジナイザー（ナノマイザー製、ナノマイザー、ＬＡ−３１）を用いて処理圧力８０ＭＰａの条件で微粒化処理することにより原液を得た。物性および評価結果を表１に示す。
5: No occurrence of red rust, 4: Rust generation area less than 5%, 3: Rust generation area from 5% to less than 10%, 2: Rust generation area from 10% to less than 15%, 1: Rust generation area from 15% to 25% Less than 0: Rust generation area 25% or more Example 1
While gradually adding fumed silica having a specific surface area of 300 m 2 / g (manufactured by Tokuyama, Leolosil QS-30) to ion-exchanged water, the liquid temperature was maintained at 30 ° C. By dispersing with LR-2), a silica slurry having a silica concentration of 12% by weight was obtained. This silica slurry and lysine aqueous solution were mixed and dispersed so that lysine was 0.1 parts by weight with respect to 100 parts by weight of silica to obtain a premixed solution. The liquid temperature during the preliminary mixing was maintained at 30 ° C. This premixed solution was atomized using a high-pressure homogenizer (Nanomizer, Nanomizer, LA-31) at a treatment pressure of 80 MPa to obtain a stock solution. Table 1 shows the physical properties and evaluation results.
実施例２
アミノ酸としてヒスチジンを用いた以外は、実施例１と同様にして原液を得た。物性および評価結果を表１に示す。
Example 2
A stock solution was obtained in the same manner as in Example 1 except that histidine was used as an amino acid. Table 1 shows the physical properties and evaluation results.
実施例３
アミノ酸としてアルギニンを用いた以外は、実施例１と同様にして原液を得た。物性および評価結果を表１に示す。
Example 3
A stock solution was obtained in the same manner as in Example 1 except that arginine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
実施例４
シリカ濃度を１６重量％とし、添加するヒスチジンの量を０．２重量部とした以外は、実施例２と同様にして原液を得た。物性および評価結果を表１に示す。
Example 4
A stock solution was obtained in the same manner as in Example 2 except that the silica concentration was 16% by weight and the amount of histidine to be added was 0.2 parts by weight. Table 1 shows the physical properties and evaluation results.
実施例５
シリカとして、比表面積が９０ｍ２／ｇのヒュームドシリカ（トクヤマ製、レオロシールＱＳ−０９）を用いた以外は、実施例３と同様にして原液を得た。物性および評価結果を表１に示す。
Example 5
A stock solution was obtained in the same manner as in Example 3 except that fumed silica (manufactured by Tokuyama, Leoroseal QS-09) having a specific surface area of 90 m 2 / g was used as silica. Table 1 shows the physical properties and evaluation results.
実施例６
市販のケイ酸ナトリウムとイオン交換水を反応槽中にケイ酸ナトリウムの濃度が５重量％となるように投入した。反応槽の温度を４０℃として、２２重量％硫酸を用いて中和反応（中和率５０％まで）を行った後、反応液の温度を９５℃とした。この反応液に中和率が１００％になるまで上記硫酸を加えた。生成したシリカにろ過、洗浄操作を繰り返し、シリカケーク（シリカ含有量１５重量％）を得た。次いで、この湿式シリカケークにイオン交換水を徐々に添加しながら、液温度を３０℃に維持して、ウルトラミキサー（みづほ工業製、ウルトラミキサーＬＲ−２）で分散することにより、シリカ濃度１２重量％のシリカスラリーを得た。このシリカスラリーとリジン水溶液をシリカ１００重量部に対してリジンが０．１重量部となるように混合・分散し、予備混合液を得た。尚、予備混合中の液温度は３０℃を維持した。この予備混合液を高圧ホモジナイザー（ナノマイザー製、ナノマイザー、ＬＡ−３１）を用いて処理圧力８０ＭＰａの条件で微粒化処理することにより原液を得た。物性および評価結果を表１に示す。
Example 6
Commercially available sodium silicate and ion-exchanged water were charged into the reaction vessel so that the concentration of sodium silicate was 5% by weight. The temperature of the reaction vessel was set to 40 ° C., neutralization reaction (up to a neutralization rate of 50%) was performed using 22 wt% sulfuric acid, and then the temperature of the reaction solution was set to 95 ° C. The sulfuric acid was added to the reaction solution until the neutralization rate reached 100%. Filtration and washing operations were repeated on the produced silica to obtain a silica cake (silica content 15% by weight). Next, while gradually adding ion-exchanged water to the wet silica cake, the liquid temperature is maintained at 30 ° C., and the mixture is dispersed with an ultramixer (manufactured by Mizuho Kogyo Co., Ltd., Ultramixer LR-2), whereby a silica concentration of 12% by weight is obtained. A silica slurry was obtained. This silica slurry and lysine aqueous solution were mixed and dispersed so that lysine was 0.1 parts by weight with respect to 100 parts by weight of silica to obtain a premixed solution. The liquid temperature during the preliminary mixing was maintained at 30 ° C. This premixed solution was atomized using a high-pressure homogenizer (Nanomizer, Nanomizer, LA-31) at a treatment pressure of 80 MPa to obtain a stock solution. Table 1 shows the physical properties and evaluation results.
実施例７
アミノ酸としてグリシンを用いた以外は、実施例６と同様にして原液を得た。物性および評価結果を表１に示す。
Example 7
A stock solution was obtained in the same manner as in Example 6 except that glycine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
実施例８
アミノ酸としてシステインを用いた以外は、実施例６と同様にして原液を得た。物性および評価結果を表１に示す。
Example 8
A stock solution was obtained in the same manner as in Example 6 except that cysteine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
実施例９
アミノ酸としてリジンを用いた以外は、実施例６と同様にして原液を得た。物性および評価結果を表１に示す。
Example 9
A stock solution was obtained in the same manner as in Example 6 except that lysine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
実施例１０
アミノ酸としてヒスチジンを用いた以外は、実施例６と同様にして原液を得た。物性および評価結果を表１に示す。
Example 10
A stock solution was obtained in the same manner as in Example 6 except that histidine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
実施例１１
アミノ酸としてアルギニンを用いた以外は、実施例６と同様にして原液を得た。物性および評価結果を表１に示す。
Example 11
A stock solution was obtained in the same manner as in Example 6 except that arginine was used as the amino acid. Table 1 shows the physical properties and evaluation results.
比較例１
リジンを添加しないこと以外は実施例１と同様にして原液を得た。物性および評価結果を表１に示す。
Comparative Example 1
A stock solution was obtained in the same manner as in Example 1 except that lysine was not added. Table 1 shows the physical properties and evaluation results.
比較例２
高圧ホモジナイザーで微粒化しないこと以外は実施例１と同様にして原液を得た。物性および評価結果を表１に示す。
Comparative Example 2
A stock solution was obtained in the same manner as in Example 1 except that it was not atomized with a high-pressure homogenizer. Table 1 shows the physical properties and evaluation results.
実施例１で得られた被覆組成物用原液は、アミノ酸を添加していない比較例１で得られた原液、および高圧微粒化処理をしていない比較例２で得られた被覆組成物用原液と比較して、安定性が大きいことがわかる。比較例２では平均二次粒子径が３１μｍと分散状態が悪いため、高分散の原液と比較して保存安定性が小さいと考えられる。 The coating composition stock solution obtained in Example 1 was the same as the stock solution obtained in Comparative Example 1 in which no amino acid was added, and the coating composition stock solution obtained in Comparative Example 2 that was not subjected to high-pressure atomization. It can be seen that the stability is larger than that. In Comparative Example 2, since the average secondary particle diameter is 31 μm and the dispersion state is poor, it is considered that the storage stability is small compared to the highly dispersed stock solution.
Claims (3)
A rust preventive paint comprising the coating composition stock solution according to claim 1 as a component.
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| JP2016537493A (en) * | 2013-10-07 | 2016-12-01 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． | Treated filler, composition containing it and article prepared therefrom |
| JP2016537481A (en) * | 2013-09-11 | 2016-12-01 | ピーアールシー−デソト インターナショナル，インコーポレイティド | Composition comprising magnesium oxide and an amino acid |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004231564A (en) * | 2003-01-30 | 2004-08-19 | Miyoshi Kasei Inc | Powder coated with specific lipoamino acid composition and cosmetic formulated with the same |
| WO2004094311A1 (en) * | 2003-04-24 | 2004-11-04 | Mitsui Chemicals, Inc. | Coating liquid for forming porous silica |
| JP2005231954A (en) * | 2004-02-20 | 2005-09-02 | Tokuyama Corp | Wet type silica dispersion liquid and method of manufacturing the same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0363838A (en) * | 1989-08-02 | 1991-03-19 | Nec Corp | Software program inspection system |
| JP2016537481A (en) * | 2013-09-11 | 2016-12-01 | ピーアールシー−デソト インターナショナル，インコーポレイティド | Composition comprising magnesium oxide and an amino acid |
| JP2016537493A (en) * | 2013-10-07 | 2016-12-01 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． | Treated filler, composition containing it and article prepared therefrom |
| JP2020023710A (en) * | 2013-10-07 | 2020-02-13 | ピーピージー・インダストリーズ・オハイオ・インコーポレイテッドＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ Ｏｈｉｏ，Ｉｎｃ． | Treated fillers, compositions containing the same, and articles prepared therefrom |
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| JP5219335B2 (en) | 2013-06-26 |
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