JPH08170030A - Matte silica for topcoat - Google Patents
Matte silica for topcoatInfo
- Publication number
- JPH08170030A JPH08170030A JP6316639A JP31663994A JPH08170030A JP H08170030 A JPH08170030 A JP H08170030A JP 6316639 A JP6316639 A JP 6316639A JP 31663994 A JP31663994 A JP 31663994A JP H08170030 A JPH08170030 A JP H08170030A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- particle size
- particles
- transparency
- top coat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は塗料用充填剤として有用
なシリカに関するものであり、詳細には合成皮革，家電
製品等のトップコート用艶消し剤として有用な、特に透
明性，漆黒性に優れたシリカに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to silica useful as a filler for paints, and in particular, it is useful as a matting agent for top coats of synthetic leather, home appliances, etc., especially in transparency and jetness. It relates to excellent silica.
【０００２】[0002]
【従来の技術】一般にシリカはアルカリ金属ケイ酸塩水
溶液と鉱酸の中和反応によつて製造することができ、そ
の製造方法は湿式法と呼ばれている。この湿式法は、中
性あるいはアルカリ性下で反応させて比較的濾過し易い
沈澱ケイ酸を得る沈澱法と、酸性で反応させてゲル状の
ケイ酸を得るゲル法とに分類される。2. Description of the Related Art Generally, silica can be produced by a neutralization reaction between an aqueous solution of an alkali metal silicate and a mineral acid, and its production method is called a wet method. This wet method is classified into a precipitation method in which a precipitated silicic acid is obtained by reacting under neutral or alkaline conditions to obtain a precipitated silicic acid which is relatively easy to filter, and a gel method in which a silicic acid in a gel state is obtained by reacting under acidic conditions.
【０００３】上記の沈澱法シリカの製造法は、例えば特
公昭３９−１２０７号等に開示されており、中和反応に
よつて構造性を有するように一次粒子を成長させて得ら
れた沈澱ケイ酸を水洗，乾燥及び粉砕することで製品と
される。この方法によって得られた沈澱法シリカは、主
として汎用のゴム補強剤，農薬の担体，塗料の艶消し
剤，粘度調整剤として従来使用されている。The above-mentioned method for producing precipitated silica is disclosed, for example, in Japanese Examined Patent Publication No. 39-1207, and the precipitated silica obtained by growing primary particles so as to have a structure by a neutralization reaction. The product is made by washing the acid with water, drying and crushing. The precipitated silica obtained by this method has been conventionally used mainly as a general-purpose rubber reinforcing agent, pesticide carrier, paint delusterant, and viscosity modifier.
【０００４】一方、ゲル法シリカの製造法は、例えば米
国特許第２４６８４２号等に開示されており、酸性反応
によって得られたゲル状のケイ酸を水洗，乾燥後、粉砕
することで製品とされる。この方法によって得られたゲ
ル法シリカは、沈澱法シリカに比べて一般に構造性が高
く、高シェアー下においてもその構造性を保持できるの
で、合成皮革，プラスッチック等のコーテイング剤，樹
脂フィルムのアンチブロッキング剤，吸着剤，分離剤，
触媒として従来使用されている。On the other hand, a method for producing gel silica is disclosed in, for example, US Pat. No. 246842, and a gel-like silicic acid obtained by an acidic reaction is washed with water, dried, and then pulverized to obtain a product. It The gel method silica obtained by this method is generally higher in structure than the precipitated method silica and can retain its structure even under high shear, so synthetic leather, coating materials such as plastics, anti-blocking of resin film, etc. Agent, adsorbent, separating agent,
Conventionally used as a catalyst.
【０００５】以上のようなシリカの種々の用途のうち
で、商品の最外層の塗膜を形成するための塗料（通常ト
ップコート用塗料と称される）に添加されるシリカは、
塗装した商品の外観として目にみえる最外層の塗膜を形
成するため、その品質は従来から厳しく管理されてい
る。例えば、シリカを艶消し剤として使用する場合には
分散不良による「ブツ」の発生等、商品価値の低下を抑
止することが求められるが、高シェアーによる分散処理
を行うと、構造性，凝集力の不足から構造の破壊を生じ
て粒子径が小さくなる沈澱法シリカは艶消し効果が著し
く低下する傾向を招いて不適当となる場合が多い。この
ため、トップコート用塗料に添加される艶消し剤として
のシリカにはゲル法シリカが使用される場合が多い。Among the various uses of silica as described above, silica added to a paint for forming a coating film of the outermost layer of a product (usually referred to as a top coat paint) is
In order to form the outermost coating film that can be seen as the appearance of the painted product, its quality has been strictly controlled. For example, when silica is used as a matting agent, it is required to prevent the deterioration of the product value such as the generation of "bugs" due to poor dispersion. Precipitated silica, which has a structure whose size is reduced due to its lack of a small amount, tends to have a significantly reduced matting effect, and is therefore unsuitable in many cases. For this reason, gel method silica is often used as silica as a matting agent added to the top coat paint.
【０００６】なおトップコート用塗料は、着色顔料を含
む有色塗料と、着色顔料を含まないクリヤー塗料とに分
類され、使用目的によつて使い分けられている。The top coat paints are classified into colored paints containing color pigments and clear paints not containing color pigments, and are used properly according to the purpose of use.
【０００７】[0007]
【発明が解決しようとする課題】ところで、上記のよう
なトップコート用塗料の艶消し用添加剤としてシリカを
使用すると、塗膜が白つぽくなるという欠点を有してお
り、クリヤー塗料における透明性の低下，あるいは有色
塗料における色相の変化といった問題が挙げられ、トッ
プコートとして重要な因子となる広い視覚範囲における
透明性，色相の変化の小さい艶消し剤用シリカが強く望
まれていた。By the way, when silica is used as a matting additive for the above-mentioned top coat paint, it has a drawback that the coating film becomes white and transparent. There are problems such as deterioration of properties and changes in hue in colored paints, and there has been a strong demand for silica for a matting agent, which is an important factor for a topcoat, has a small transparency and transparency in a wide visual range.
【０００８】本発明者等はかかる問題点を解決するため
鋭意研究を重ねた結果、特定の物性を有するシリカをト
ップコート用の艶消し剤として使用することにより広い
視覚範囲において優れた透明性，色相の変化の小さな塗
膜が得られ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 conducted extensive studies in order to solve such problems, and as a result, by using silica having specific physical properties as a matting agent for a top coat, excellent transparency in a wide visual range, The inventors have found that a coating film with a small change in hue can be obtained, and completed the present invention.
【０００９】[0009]
【課題を解決するための手段】本発明の特徴は、ＢＥＴ
比表面積が２５０〜３５０ｍ2 ／ｇであり、コールター
カウンター法による平均粒径が１．２〜１．８μｍで、
かつ８μｍ以上の粗粒子が存在せずｌμｍ以下の粒子が
全体の１０〜３０％であるトップコート用艶消しシリカ
を提供するところにある。The feature of the present invention is that BET
The specific surface area is 250 to 350 m 2 / g, the average particle size by Coulter counter method is 1.2 to 1.8 μm,
Moreover, the present invention provides a matte silica for topcoat in which coarse particles of 8 μm or more are not present and particles of 1 μm or less account for 10 to 30% of the whole.
【００１０】以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
【００１１】本発明のシリカは以下の方法で得られる。
ゲル法シリカの常法に基づく反応、つまり珪酸ナトリウ
ム，珪酸カリウム，珪酸リチウム等の珪酸アルカリ金属
塩水溶液と、硫酸，塩酸，硫酸等の鉱酸と、を酸過剰下
において反応させて均一なシリカヒドロゾルを得る。つ
いでゲル化させた後、解砕し水洗する。水洗工程では通
常、副生塩を除去すると共に比表面積を下げる目的で水
酸化ナトリウムやアンモニア水溶液を添加，加熱し水熱
処理を行う。水熱処理は特に限定されるものでなく、適
度なアルカリ度，温度，時間で行われる。その後シリカ
ヒドロゲルを乾燥，粉砕して目的とするシリカを得る。The silica of the present invention can be obtained by the following method.
A reaction based on the ordinary method of gel method silica, that is, a uniform silica is obtained by reacting an aqueous solution of an alkali metal silicate such as sodium silicate, potassium silicate or lithium silicate with a mineral acid such as sulfuric acid, hydrochloric acid or sulfuric acid in an excess of acid. Obtain the hydrosol. Then, after gelling, it is crushed and washed with water. In the water washing step, hydrothermal treatment is usually carried out by adding and heating an aqueous solution of sodium hydroxide or ammonia in order to remove by-product salts and reduce the specific surface area. The hydrothermal treatment is not particularly limited, and is performed at an appropriate alkalinity, temperature and time. Then, the silica hydrogel is dried and pulverized to obtain the desired silica.
【００１２】上記乾燥は一般に静置乾燥機，バンドドラ
イヤー，パドルドライヤー，流動乾燥機等が使用される
が特に限定されるものではない。この乾燥は一般に、細
孔コントロールの点から、シリカヒドロゲルの水分を４
０％以上に制御するのが好ましく、４０％未満の水分ま
で乾燥を行うと毛管凝縮による細孔容積の低下を生じ好
ましくない。また粉砕はピンミルのような粉砕方法では
粉砕力が弱いために適当でなく、過熱空気，あるいは過
熱蒸気を用いたジェットミルで粉砕するのが好ましい
が、粒度分布の制御を容易にする目的で適宜、ジェット
ミル粉砕前にピンミル等で予備粉砕を行つてもよい。For the above-mentioned drying, a static dryer, a band dryer, a paddle dryer, a fluid dryer, etc. are generally used, but the dryer is not particularly limited. This drying generally removes the water content of the silica hydrogel to 4% from the viewpoint of pore control.
It is preferable to control it to 0% or more, and drying to a water content of less than 40% undesirably causes a decrease in pore volume due to capillary condensation. Further, the crushing is not suitable in a crushing method such as a pin mill because the crushing force is weak, and it is preferable to crush with a jet mill using superheated air or superheated steam, but it is appropriate for the purpose of facilitating control of particle size distribution. Before crushing with a jet mill, preliminary crushing may be performed with a pin mill or the like.
【００１３】上記範囲の粒度分布を有するシリカを得る
には分級工程は必要不可欠であり、特にミクロンセパレ
ーター（ホソカワミクロン社製）のような風力分級機が
好ましい。この時、効率良く分級し、且つ分級後の再凝
集を防ぐ目的で系内の空気の相対湿度を５０％以下，好
ましくは１０％以下にするのが好ましい。これは本発明
のごとき微細粒子においてはフアンデルワールス力の増
加により凝集し易い傾向にあり、これに水分が存在する
と水をバインダーとして大きな凝集粒子を形成するため
風力分級に用いる空気の水分を限定することがよい。A classifying step is indispensable for obtaining silica having a particle size distribution in the above range, and an air classifier such as a micron separator (manufactured by Hosokawa Micron) is particularly preferable. At this time, the relative humidity of the air in the system is preferably 50% or less, more preferably 10% or less for the purpose of efficiently classifying and preventing re-aggregation after classification. This is because fine particles such as the present invention tend to agglomerate due to an increase in Van der Waals force, and when water is present in the particles, water is used as a binder to form large agglomerated particles. Good to do.
【００１４】即ち、本発明のシリカを得るには、乾燥工
程における水分及び分級時の系内の水分について上記し
た両条件をみたすことが必要であり、これらの条件を満
足しないと本発明の特定された物性を有するシリカを製
造することができない。That is, in order to obtain the silica of the present invention, it is necessary to satisfy both of the above-mentioned conditions regarding the water content in the drying step and the water content in the system at the time of classification. It is not possible to produce silica having the specified physical properties.
【００１５】本発明のシリカはＢＥＴ比表面積２５０〜
３５０ｍ2 ／ｇが好ましい。２５０ｍ2 ／ｇ未満ではト
ップコート用塗料に用いられるシリカ粒子の構造性が高
シェアーに耐えられず艶消し効果が劣る。３５０ｍ2 ／
ｇを超えると粉砕が困難になり、所定の粒度分布を得る
ことが難しくなる。更に塗膜にした時、塗膜外観が荒く
なり好ましくない。The silica of the present invention has a BET specific surface area of 250 to
350 m 2 / g is preferred. If it is less than 250 m 2 / g, the structure of the silica particles used in the coating material for top coat cannot withstand a high share and the matte effect is poor. 350m 2 /
If it exceeds g, it becomes difficult to pulverize and it becomes difficult to obtain a predetermined particle size distribution. Further, when the coating film is formed, the appearance of the coating film becomes rough, which is not preferable.
【００１６】また本発明のシリカは、コールターカウン
ター法による平均粒子径１．２〜１．８μｍで、かつ８
μｍ以上の粗粒子が存在せずｌμｍ以下の粒子が全体の
１０〜３０％であることが必要である。平均粒子径が
１．２μｍ未満では艶消し効果が劣るため好ましくな
く、反対に平均粒子径が１．８μｍを超えると分散が困
難となり、高シェアー下の分散を実施しても分散が悪
く、塗膜外観が荒くなり透明性が悪く色相の変化も大き
くなるため不都合を生じる。又、平均粒子径が１．２〜
１．８μｍの範囲においても、８μｍ以上の粗粒子が存
在すると、分散不良による塗膜中にブツを生じ好ましく
ない。更に、ｌμｍ以下の粒子が全体の１０％以下にな
ると塗料に添加した際、粘度上昇がほとんど起こらず塗
装時に液ダレを生じ好ましくなく、３０％以上になると
塗料中に分散させた時にフアンデルワールス力による再
凝集を生じ分散不良によるブツの発生が起こりやはり好
ましくない。また塗膜の艶消しに寄与しない粒子が増
え、透明性の低下及び色相の変化が大きくなるために好
ましくない。The silica of the present invention has an average particle size of 1.2 to 1.8 μm as measured by the Coulter counter method, and 8
It is necessary that there are no coarse particles of 1 μm or more and 10 to 30% of the total particles are 1 μm or less. If the average particle size is less than 1.2 μm, the matting effect is poor, which is not preferable. On the contrary, if the average particle size exceeds 1.8 μm, it becomes difficult to disperse. The appearance of the film becomes rough, the transparency is poor, and the change in hue becomes large, which causes a problem. Also, the average particle size is 1.2 to
Even in the range of 1.8 μm, if coarse particles of 8 μm or more are present, it is not preferable because coarse particles are generated in the coating film due to poor dispersion. Furthermore, when particles of 1 μm or less make up less than 10% of the total, no viscosity increase occurs when added to the paint, and liquid dripping occurs undesirably at the time of coating, and when it exceeds 30%, van der Waals when dispersed in the paint. Re-aggregation due to force may occur, and spots may be generated due to poor dispersion. In addition, the number of particles that do not contribute to the mattness of the coating film increases, the transparency decreases and the change in hue increases, which is not preferable.
【００１７】以上の物性を有する本発明のシリカは更
に、細孔容積は１．５〜２．０ｃｃ／ｇで、その平均細
孔径が２００〜３００Åのものであることが好ましい。
細孔容積１．５ｃｃ／ｇ未満，平均細孔径２００Å未満
になると、細孔内への塗料の保持，すなわち吸塗料量が
低くなり、膜厚が厚くなり艶消し効果が劣る。一方、
２．０ｃｃ／ｇを越える細孔容積、３００Åを越える平
均細孔径になると、空隙率の上昇により、ゲル法シリカ
の特徴である構造性が保持できなくなり、結果として艶
消し効果が劣る。又、吸塗料量の低下は、透明性の低
下，色相の変化を生じ好ましくない。Further, the silica of the present invention having the above physical properties preferably has a pore volume of 1.5 to 2.0 cc / g and an average pore diameter of 200 to 300 Å.
When the pore volume is less than 1.5 cc / g and the average pore diameter is less than 200Å, the amount of the coating material retained in the pores, that is, the amount of the absorbed coating material becomes low, and the film thickness becomes large, resulting in poor matting effect. on the other hand,
When the pore volume exceeds 2.0 cc / g and the average pore diameter exceeds 300 Å, the porosity increases, so that the structure characteristic of the gel-processed silica cannot be maintained, resulting in poor matting effect. In addition, a decrease in the amount of paint to be absorbed is not preferable because it causes a decrease in transparency and a change in hue.
【００１８】本発明のシリカをトップコート用艶消し剤
として添加した塗料は、スプレー塗装、ロールコーター
塗装などの塗装方法により塗工される。この場合、塗工
方法により塗料に要求される最適粘度は異なる。The coating composition of the present invention to which silica is added as a matting agent for a top coat is applied by a coating method such as spray coating or roll coater coating. In this case, the optimum viscosity required for the coating material differs depending on the coating method.
【００１９】[0019]
【作用】本発明のシリカによれば、トップコート用艶消
し剤として使用することにより、優れた透明性、且つ色
相の変化の小さな塗膜を得ることができる。又、広い視
角範囲においても優れた透明性と色相の変化の小さな塗
膜となる。By using the silica of the present invention as a matting agent for a top coat, a coating film having excellent transparency and a small change in hue can be obtained. Further, the coating film has excellent transparency and a small change in hue even in a wide viewing angle range.
【００２０】このような作用が発揮される理由は定かで
はないが、本発明のシリカは、その粒度分布特性、細孔
特性を細かくコントロールできる結果、塗料中における
分散挙動を制御でき、これを塗膜中に均一に分散させ
て、艶消しに効果のある凹凸を均一の大きさで非常に緻
密な塗膜表面に形成できるためと考えられる。又、その
凹凸の大きさを艶消しに効果のある最小のものにできる
ため、塗膜の風合いに優れ、且つ広い視角範囲において
も優れた透明性を保ち、色相の変化も小さいものと考え
られる。Although the reason why such an effect is exerted is not clear, the silica of the present invention can finely control the particle size distribution characteristic and the pore characteristic, and as a result, the dispersion behavior in the coating material can be controlled. It is considered that this is because it is possible to uniformly disperse in the film and form irregularities effective for matting on a very dense coating surface with a uniform size. In addition, since the size of the unevenness can be made the smallest that is effective for matting, it is considered that the coating film has excellent texture, has excellent transparency even in a wide viewing angle range, and has a small change in hue. .
【００２１】[0021]
【実施例】以下、本発明を更に具体的に説明するために
実施例を示すが、本発明はこれらの実施例に限定される
ものではない。尚、実施例及び比較例における各評価は
以下の方法に従つて行つた。EXAMPLES Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these examples. Each evaluation in Examples and Comparative Examples was performed according to the following methods.
【００２２】粉体特性： （１）ＢＥＴ比表面積（窒素法） カンタソープ（米国 Quantachrome 社製）を用いて１点
法により測定した。Powder Properties: (1) BET Specific Surface Area (Nitrogen Method) The BET specific surface area was measured by a one-point method using Kantasoap (manufactured by Quantachrome, USA).
【００２３】（２）細孔容積（窒素法） ＡＳＡＰ−２４００（島津製作所製）を用いて、細孔容
積，平均細孔径を測定した。(2) Pore Volume (Nitrogen Method) ASAP-2400 (manufactured by Shimadzu Corporation) was used to measure the pore volume and average pore diameter.
【００２４】（３）平均粒子径及び粒度分布（コールタ
ーカウンター法） マルチサイザーII（コールターカウンター社製）で３０
μｍのアパチャーチューブを使用し測定した。試料の分
散は、４０秒間の超音波分散を行い分散液は付属のIsot
on II 液を使用した。(3) Average particle size and particle size distribution (Coulter counter method) 30 with Multisizer II (manufactured by Coulter Counter)
The measurement was performed using a μm aperture tube. Disperse the sample by ultrasonic dispersion for 40 seconds, and use the supplied Isot
on II solution was used.
【００２５】塗料に分散した後の塗料特性 （４）粘度 室温（約２０℃）でＢＬ型粘度計により、６ｒｐｍ，１
２０秒後の粘度を測定した。Characteristics of paint after dispersion in paint (4) Viscosity: 6 rpm, 1 rpm at room temperature (about 20 ° C) with a BL type viscometer
The viscosity after 20 seconds was measured.
【００２６】（５）分散度 塗料一般試験法 ＪＩＳ Ｋ５４００のつぶの試験方法
に準じて測定した。２０以下であれば良好と判断され
る。(5) Dispersion degree General test method for coating material The measurement was carried out according to the test method of JIS K5400. If it is 20 or less, it is judged to be good.
【００２７】（６）光沢度 グロスメーター（スガ試験機社製）を使用し、∠３０〜
∠８０°の反射率を測定した。数値が低いほど艶消しの
効果が高いと評価される。(6) Glossiness A gloss meter (manufactured by Suga Test Instruments Co., Ltd.) is used and ∠30-
The reflectance of ∠80 ° was measured. The lower the value, the higher the matting effect.
【００２８】（７）透明性 測色計（スガ試験機社製）を用いてその透過度を測定し
た。１００％に近いほど透明性が高いと評価される。(7) Transparency The transmittance was measured using a colorimeter (Suga Test Instruments Co., Ltd.). The closer it is to 100%, the higher the transparency is evaluated.
【００２９】（８）塗膜外観 塗膜の表面状態を目視観察して、表面状態が良ければ
○，表面状態が粗いかブツ等が見られる場合を×とし、
中間的な状態を△とした。(8) Appearance of coating film The surface condition of the coating film is visually observed, and if the surface condition is good, it is indicated by ○, and if the surface condition is rough or spots, etc.
The intermediate state was set as Δ.
【００３０】実施例１ ２５ｗｔ％のケイ酸ソーダ水溶液と４０ｗｔ％の硫酸水
溶液を、混合ノズルを用いて反応させ、シリカヒドロゾ
ルを得、放置しシリカヒドロゲルとした。次いで該シリ
カヒドロゲルを篩を用いて約１０ｍｍに粗砕した後、９
０℃，ＰＨ９．５の条件で６時間水熱処理し、その後、
洗浄した。更に洗浄後のシリカヒドロゲルを流動乾燥機
を用いて、水分６５％に調整した後、過熱蒸気を用いた
ジェットミルにより５５０℃，５．５ｋｇ／ｃｍ2 の粉
砕条件で粉砕した。粉砕後、風力分級機（ミクロンセパ
レーター：細川ミクロン社製）により分級を行いシリカ
を得た。Example 1 A 25 wt% aqueous solution of sodium silicate and a 40 wt% aqueous solution of sulfuric acid were reacted using a mixing nozzle to obtain silica hydrosol, which was allowed to stand to obtain silica hydrogel. The silica hydrogel was then crushed to about 10 mm using a sieve and
Hydrothermal treatment for 6 hours at 0 ° C, PH 9.5, then
Washed. Further, the silica hydrogel after washing was adjusted to have a water content of 65% using a fluid dryer, and then pulverized by a jet mill using superheated steam under pulverization conditions of 550 ° C. and 5.5 kg / cm 2 . After crushing, classification was performed by an air classifier (micron separator: manufactured by Hosokawa Micron Co., Ltd.) to obtain silica.
【００３１】この時、分級機の系内の相対湿度は５％以
下であった。シリカのＢＥＴ比表面積，細孔容積，平均
粒子径，粒度分布を測定し表１に示した。At this time, the relative humidity in the system of the classifier was 5% or less. The BET specific surface area, pore volume, average particle size and particle size distribution of silica were measured and are shown in Table 1.
【００３２】実施例２，３ 実施例１の反応条件，流動乾燥機による乾燥条件，粉砕
条件，分級条件を変化させて下記表１に示した実施例
２，３の粉体特性を有するシリカを得た。各例のシリカ
のＢＥＴ比表面積，細孔容積，平均粒子径，粒度分布を
測定し表１に示した。Examples 2 and 3 By changing the reaction conditions of Example 1, drying conditions by a fluidized dryer, pulverization conditions and classification conditions, silica having powder characteristics of Examples 2 and 3 shown in Table 1 below was obtained. Obtained. The BET specific surface area, pore volume, average particle size and particle size distribution of the silica of each example were measured and shown in Table 1.
【００３３】比較例１〜４ 実施例１の反応条件，流動乾燥機による乾燥条件，粉砕
条件，分級条件を変化させて下記表１に示した比較例１
〜４の粉体特性を有するシリカを得た。各例のシリカの
ＢＥＴ比表面積，細孔容積，平均粒子径，粒度分布を測
定し表１に示した。Comparative Examples 1 to 4 Comparative Example 1 shown in Table 1 below by changing the reaction conditions of Example 1, the drying conditions by a fluidized dryer, the crushing conditions and the classification conditions.
A silica having powder properties of ˜4 was obtained. The BET specific surface area, pore volume, average particle size and particle size distribution of the silica of each example were measured and shown in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】参考例 塗膜形成剤としてアクリルクリヤー樹脂（関西ペイント
社製）を用い、樹脂１００重量部に対して、専用シンナ
ー５０重量部、実施例１〜３及び比較例１〜４のシリカ
各１０重量部を配合し、ハイスピードミキサーを用いて
１５００ｒｐｍ，２０分間分散した。この時の分散度及
び粘度を測定し表２に示した。更に分散液をＮｏ．１０
のバーコーターを用いてガラス板（５０×１００×３ｍ
ｍ）に塗布した後、常温で１時間乾燥し光沢度並びに透
明性を測定し，塗膜外観を観察した。結果を表２に示し
た。Reference Example An acrylic clear resin (manufactured by Kansai Paint Co., Ltd.) was used as a coating film forming agent, and 50 parts by weight of dedicated thinner, 100 parts by weight of the resin, and silica of each of Examples 1 to 3 and Comparative Examples 1 to 4 were used. 10 parts by weight were mixed and dispersed using a high speed mixer at 1500 rpm for 20 minutes. The dispersity and viscosity at this time were measured and are shown in Table 2. Further, the dispersion liquid was 10
Glass plate (50 × 100 × 3m
After coating on m), it was dried at room temperature for 1 hour, the glossiness and transparency were measured, and the appearance of the coating film was observed. The results are shown in Table 2.
【００３６】[0036]
【表２】 [Table 2]
【００３７】[0037]
【発明の効果】以上の説明からも明らかなように本発明
のシリカ、即ち、ＢＥＴ比表面積が２５０〜３５０ｍ2
／ｇであり、コールターカウンター法による平均粒径が
１．２〜１．８μｍ、且つ８μｍ以上の粗粒子が存在せ
ずｌμｍ以下の粒子が全体の１０〜３０％であるトップ
コート用艶消しシリカを使用することにより、分散性に
優れ且つ艶消し効果が高いために塗膜外観に優れたトッ
プコートを得ることができるという効果がある。As is apparent from the above description, the silica of the present invention, that is, the BET specific surface area is 250 to 350 m 2.
/ G, the average particle size by Coulter Counter method is 1.2 to 1.8 μm, and there are no coarse particles of 8 μm or more, and the particles of 1 μm or less account for 10 to 30% of the total, and matte silica for top coat The use of is advantageous in that a top coat having excellent dispersibility and a high matting effect can be obtained, and thus a coating film appearance is excellent.
【００３８】またこのトップコート用艶消しシリカを用
いることにより、広い視覚範囲においても優れた透明性
と色相の変化の小さなトップコートを得ることができる
という効果が得られる。Further, by using this matte silica for top coat, it is possible to obtain a top coat having excellent transparency and small change in hue even in a wide visual range.
Claims (3)
ｇであり、コールターカウンター法による平均粒径が
ｌ．２〜１．８μｍで、かつ８μｍ以上の粗粒子が存在
せずｌμｍ以下の粒子が全体の１０〜３０％であること
を特徴とするトップコート用艶消しシリカ。1. A BET specific surface area of 250 to 350 m 2 /
and the average particle size by the Coulter Counter method is l. A matte silica for a top coat, characterized in that there are no coarse particles of 2 to 1.8 μm and 8 μm or more and particles of 1 μm or less are 10 to 30% of the whole.
つ平均細孔径が２００〜３００Åであることを特徴とす
る請求項１に記載のトップコート用艶消しシリカ。2. The matte silica for a top coat according to claim 1, which has a pore volume of 1.5 to 2.0 cc / g and an average pore diameter of 200 to 300 Å.
とする請求項１又は２に記載のシリカ。3. The silica according to claim 1, wherein the silica is a gel method silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6316639A JP3004184B2 (en) | 1994-12-20 | 1994-12-20 | Matted silica for top coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6316639A JP3004184B2 (en) | 1994-12-20 | 1994-12-20 | Matted silica for top coat |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08170030A true JPH08170030A (en) | 1996-07-02 |
| JP3004184B2 JP3004184B2 (en) | 2000-01-31 |
Family
ID=18079278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6316639A Expired - Fee Related JP3004184B2 (en) | 1994-12-20 | 1994-12-20 | Matted silica for top coat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3004184B2 (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1149992A (en) * | 1997-08-04 | 1999-02-23 | Fuji Silysia Chem Ltd | Delustering agent for paint and manufacture thereof |
| KR100855423B1 (en) * | 2002-09-27 | 2008-08-29 | 다이니폰 인사츠 가부시키가이샤 | Compound for forming mat layer, release sheet produced by using the same, and synthetic leather produced by using the release sheet |
| JP2008251877A (en) * | 2007-03-30 | 2008-10-16 | Nippon Kodoshi Corp | Flexible printed board |
| US7842129B2 (en) | 2004-06-16 | 2010-11-30 | Evonik Degussa Gmbh | Lacquer formulation for improving surface properties |
| JP2013203804A (en) * | 2012-03-27 | 2013-10-07 | Tokuyama Corp | Aerogel and matting agent comprising the same |
| JP2013226690A (en) * | 2012-04-25 | 2013-11-07 | Dic Corp | Incombustible coating decorative laminated sheet |
| JP2015077691A (en) * | 2013-10-15 | 2015-04-23 | Dic株式会社 | Decorative sheet, decorative sheet set and method of constructing decorative sheet |
| US20150118929A1 (en) * | 2012-05-11 | 2015-04-30 | Toray Industries, Inc. | Sheet-shaped article and production method therof (as amended) |
| JP2016137718A (en) * | 2016-02-18 | 2016-08-04 | Dic株式会社 | Nonflammable coated decorative board |
| JP6131517B1 (en) * | 2016-08-09 | 2017-05-24 | 東洋インキＳｃホールディングス株式会社 | Matte coating composition, cosmetic material and method for producing the same |
-
1994
- 1994-12-20 JP JP6316639A patent/JP3004184B2/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1149992A (en) * | 1997-08-04 | 1999-02-23 | Fuji Silysia Chem Ltd | Delustering agent for paint and manufacture thereof |
| KR100855423B1 (en) * | 2002-09-27 | 2008-08-29 | 다이니폰 인사츠 가부시키가이샤 | Compound for forming mat layer, release sheet produced by using the same, and synthetic leather produced by using the release sheet |
| US8038830B2 (en) | 2002-09-27 | 2011-10-18 | Dai Nippon Printing Co., Ltd. | Composition for matte layer formation, release sheet using the same, and synthetic leather produced using said release sheet |
| US8137789B2 (en) | 2002-09-27 | 2012-03-20 | Dai Nippon Printing Co., Ltd. | Composition for matte layer formation, release sheet using the same, and synthetic leather produced using said release sheet |
| US7842129B2 (en) | 2004-06-16 | 2010-11-30 | Evonik Degussa Gmbh | Lacquer formulation for improving surface properties |
| JP2008251877A (en) * | 2007-03-30 | 2008-10-16 | Nippon Kodoshi Corp | Flexible printed board |
| JP2013203804A (en) * | 2012-03-27 | 2013-10-07 | Tokuyama Corp | Aerogel and matting agent comprising the same |
| JP2013226690A (en) * | 2012-04-25 | 2013-11-07 | Dic Corp | Incombustible coating decorative laminated sheet |
| US20150118929A1 (en) * | 2012-05-11 | 2015-04-30 | Toray Industries, Inc. | Sheet-shaped article and production method therof (as amended) |
| JP2015077691A (en) * | 2013-10-15 | 2015-04-23 | Dic株式会社 | Decorative sheet, decorative sheet set and method of constructing decorative sheet |
| JP2016137718A (en) * | 2016-02-18 | 2016-08-04 | Dic株式会社 | Nonflammable coated decorative board |
| JP6131517B1 (en) * | 2016-08-09 | 2017-05-24 | 東洋インキＳｃホールディングス株式会社 | Matte coating composition, cosmetic material and method for producing the same |
| JP2018024744A (en) * | 2016-08-09 | 2018-02-15 | 東洋インキＳｃホールディングス株式会社 | Matte coating composition, decorative material and production method of the same |
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