JP3131076B2 - Paint matting agent and method for producing the same - Google Patents
Paint matting agent and method for producing the sameInfo
- Publication number
- JP3131076B2 JP3131076B2 JP05146282A JP14628293A JP3131076B2 JP 3131076 B2 JP3131076 B2 JP 3131076B2 JP 05146282 A JP05146282 A JP 05146282A JP 14628293 A JP14628293 A JP 14628293A JP 3131076 B2 JP3131076 B2 JP 3131076B2
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- JP
- Japan
- Prior art keywords
- silica
- pore volume
- paint
- precipitated silica
- matting agent
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【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、詳細には透明性，漆黒
性に優れた沈澱法シリカからなる塗料艶消し剤に関する
ものである。さらに本発明は沈澱法による該シリカの製
造方法に関するものである。BACKGROUND OF THE INVENTION This invention relates to silica useful as a coating filler, in particular those related to the paint matting agent consisting transparency, jet-black excellent in precipitation silica. Further, the present invention relates to a method for producing the silica by a precipitation method.
【０００２】[0002]
【従来の技術】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。湿式法は中性またはアル
カリ性下で反応させ比較的濾過し易い沈澱ケイ酸を得る
沈澱法と、酸性下で反応させ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 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. The wet method is classified into a precipitation method in which precipitated silica is reacted under neutral or alkaline conditions to obtain precipitated silica which is relatively easy to filter, and a gel method in which reaction is performed under acidic conditions to obtain gel-like silica.
【０００３】沈澱法シリカは、例えば、特公昭３９−１
２０７号等に開示されているように、中和反応によって
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、乾燥および引き続いて粉砕し製品とされ
る。即ち静置乾燥あるいは噴霧乾燥の後に、目的に応じ
て適当な粉砕機、例えばビンなどの間での衝撃剪断・摩
擦作用を利用して粉砕するビンミル、或は高圧のジエツ
ト気流に粒子をまきこんで相互衝突により粉砕するジエ
ツト粉砕機等（最新超微粉砕プロセス技術：ソフト技研
出版部編、新技術情報センター発行、１９８５年、８〜
１０頁）を用いて粉砕される。これらの方法によって知
られる一般的な沈澱法シリカは、ＢＥＴ比表面積が通常
１００〜４００ｍ2 ／ｇの範囲であり、主として汎用の
ゴム補強充填剤、農薬の吸着担体、塗料の艶消し剤、或
は種々の媒体の粘度調整剤等として使用されている。[0003] Precipitated silica is described, for example, in Japanese Patent Publication No. 39-1.
As disclosed in Japanese Patent No. 207 or the like, precipitated silica obtained by growing primary particles so as to have a structure by a neutralization reaction is dried and subsequently ground to obtain a product. That is, after drying by standing or spray drying, the particles are introduced into an appropriate pulverizer according to the purpose, for example, a bin mill for pulverizing by utilizing the impact shearing / frictional action between bottles, or a high-pressure jet stream. Jet crusher for crushing by mutual collision (Latest ultra-fine crushing process technology: Soft Giken Publishing Division, published by New Technology Information Center, 1985, 8 ~
10 pages). The general precipitated silica known by these methods has a BET specific surface area usually in the range of 100 to 400 m 2 / g, and is mainly used for general-purpose rubber reinforcing fillers, adsorbents for pesticides, matting agents for paints, Is used as a viscosity modifier for various media.
【０００４】一般的な沈澱法シリカは、塗料分野におい
て艶消し剤として高い艶消し効果を発揮するが、塗膜の
透明性を重視し例えばサンドミル等の高シェアー下で分
散させるような使用分野においては、粒子が砕け易い性
質の為かその効果が失われてしまうという傾向がある。
そのため合成皮革、プラスチック等のコーティングの分
野において艶消しに有用な添加剤としては利用されてい
なかつた。[0004] Generally, precipitated silica exhibits a high matting effect as a matting agent in the field of coatings, but is used in a field of use where emphasis is placed on the transparency of the coating film and, for example, it is dispersed under a high share such as a sand mill. Tends to lose its effect, probably because of the fragile nature of the particles.
Therefore, it has not been used as an additive useful for matting in the field of coating of synthetic leather, plastic, and the like.
【０００５】ゲル法シリカは、例えばＵＳＰ２，４６
６，８４２号等に開示されているように、酸性反応によ
って得られたゲルを水洗、乾燥後、粉砕して得られる。
これらゲル法シリカは、一般的に沈澱法シリカに比ベて
高構造性を有しており、高シェアー下において粒子が剪
断を受けてもその構造性を保つので、合成皮革、プラス
チツク等のコーティングの分野の用途には有効に使用さ
れている。[0005] Gel method silica is disclosed, for example, in USP 2,46.
As disclosed in US Pat. No. 6,842 or the like, a gel obtained by an acidic reaction is washed with water, dried, and then crushed.
These gel silicas generally have a higher structure than precipitated silicas and maintain their structure even when the particles are subjected to shearing under high shear, so they can be used for coating of synthetic leather, plastics, etc. It has been used effectively for applications in the field.
【０００６】しかしながら、一般に透明塗料や黒色塗料
において、これらの沈澱法シリカやゲル法シリカを艶消
し剤として使用すると、塗膜が白っぽくなるという欠点
を有していた。この塗膜が白っぽくなる現象はＢＥＴ比
表面積の比較的小さい沈澱法シリカにおいてしばしば見
られるが、ゲル法シリカにおいても、構造性を維持する
凝集力が強すぎ分散が悪くなるためか、少なからずこの
現象が見られ、この点について物性面の改善が期待され
ている。However, in general, clear paint and black paint, when used in these precipitation method silica or a gel method silica with matting agent, it had the drawback that the coating film becomes whitish. This phenomenon that the coating film becomes whitish is often seen in precipitated silica having a relatively small BET specific surface area.However, even in gel silica, the cohesive force for maintaining the structural properties is too strong and the dispersion is poor. A phenomenon was observed, and improvement in physical properties is expected in this regard.
【０００７】更には、ゲル法は、アルカリ金属ケイ酸塩
水溶液と鉱酸とをｐＨｌ〜２という強酸性域で反応させ
る必要があり、また洗浄工程においては硬い塊状のヒド
ロゲル中から副生するボウ硝等の塩類を完全に除去する
目的で３６〜４８時間という長時間をかけて洗浄する必
要がある。従って製造設備的には強酸性雰囲気に対する
耐食材料が要求され、また長時間の洗浄を必要とするの
で、洗浄工程での設備投資が増大するといった問題点を
有している。Further, the gel method requires that an aqueous solution of an alkali metal silicate and a mineral acid be reacted in a strongly acidic region of pH 1 to 2, and in a washing step, a by-product of by-produced from a hard massive hydrogel. It is necessary to wash for a long time of 36 to 48 hours in order to completely remove salts such as nitrate. Therefore, a corrosion-resistant material against a strongly acidic atmosphere is required in a manufacturing facility, and a long-time cleaning is required. Therefore, there is a problem that capital investment in a cleaning process increases.
【０００８】[0008]
【発明が解決しようとする課題】従来、高構造性を有し
高シェアー下で分散させるような使用分野において透明
性に優れかつ艶消し効果の如き機能を有するシリカは沈
澱法では得られていなかつた理由として次の理由が考え
られる。Heretofore, silica having excellent transparency and a function such as a matting effect has not been obtained by a precipitation method in a field of use which has a high structure and is dispersed under a high shear. The following reasons can be considered.
【０００９】一般的に沈澱法は、シリカの重合速度が速
い高温のアルカリ下で一次粒子を成長させ、これを凝集
させ沈澱法シリカを得ている。かかる沈澱法シリカの場
合、一次粒子が十分に成長した後に一次粒子の凝集が起
こるので、シロキサンによる粒子の結合が少なく、その
結合は比較的弱いものとなっている。かかる沈澱法シリ
カでは高シェアーのかかる分散においては容易に構造は
破壊されてしまい、透明性は有するものの艶消しに有効
な添加剤としては有効なものとならないことが予想され
る。Generally, in the precipitation method, primary particles are grown under a high-temperature alkali at which the polymerization rate of silica is high, and the primary particles are aggregated to obtain precipitated silica. In the case of such precipitated silica, the primary particles are aggregated after the primary particles have sufficiently grown, so that the bonding of the particles by the siloxane is small and the bonding is relatively weak. In such a precipitated silica, it is expected that the structure is easily destroyed in such a dispersion having a high shear, and that the silica is transparent but is not effective as an additive effective for matting.
【００１０】そこで本発明者等は、沈澱法の設備の特徴
をいかしながら、透明性に優れかつ艶消し効果を有する
理想的なシリカを製造すべく、鋭意研究を重ね体系的な
検討を進めた結果、本発明を完成するに至った。Accordingly, the present inventors have conducted intensive studies and systematically studied to produce ideal silica having excellent transparency and a matting effect while making use of the characteristics of the equipment of the precipitation method. As a result, the present invention has been completed.
【００１１】[0011]
【課題を解決するための手段】即ち本発明は、細孔直径
２０〜３０００Åの全細孔容積が１．５ｃｃ／ｇ以上、
細孔直径１００〜３００Åの細孔容積が全細孔容積の５
０％以上であり、且つ細孔直径３００Å以上の細孔容積
が全細孔容積の２０％以上である沈澱法シリカからなる
ことを特徴とする塗料艶消し剤を提供するものである。That is, according to the present invention, the total pore volume of pores having a pore diameter of 20 to 3000 ° is at least 1.5 cc / g,
The pore volume having a pore diameter of 100 to 300 ° is 5% of the total pore volume.
A paint matting agent characterized by comprising precipitated silica having a pore volume of 0% or more and a pore diameter of 300 ° or more of 20% or more of the total pore volume. is there.
【００１２】本発明者等は、塗料艶消し剤としてのシリ
カの物性と、塗膜の透明性、艶消し効果の関係を詳細に
調ベた結果、塗膜の性能は単に粒子の分散性のみに影響
されているのではなく、その細孔分布に大きく影響され
ていることが判明した。即ち本発明の塗料艶消し剤は、
沈澱法シリカからなり、細孔直径２０〜３０００Åの全
細孔容積が１．５ｃｃ／ｇ以上、より好ましくは１．６
ｃｃ／ｇ以上、細孔直径１００〜３００Åの細孔容積が
全細孔容積の５０％以上であり、且つ細孔直径３００Å
以上の細孔容積が全細孔容積の２０％以上、より好まし
くは２０〜４０％であるのが良い。The present inventors have examined in detail the relationship between the physical properties of silica as a paint matting agent and the transparency and the matting effect of the coating film, and as a result, the performance of the coating film is determined only by the dispersibility of the particles. It was found that the pore size distribution was not greatly influenced by the pore distribution. That is, the paint matting agent of the present invention is:
It is made of precipitated silica and has a total pore volume of 1.5 cc / g or more, more preferably 1.6 , having a pore diameter of 20 to 3000 °.
cc / g or more, the pore volume of the pore diameter of 100 to 300 ° is 50% or more of the total pore volume, and the pore diameter is 300 °
The above pore volume is preferably 20% or more of the total pore volume, more preferably 20 to 40%.
【００１３】湿式法シリカの細孔分布とＢＥＴ比表面積
には相関関係があり、上記細孔分布を有する本発明のシ
リカは、ＢＥＴ比表面積値２５０〜４００ｍ2 ／ｇを示
す。本発明において、上記細孔直径２０〜３０００Åの
全細孔容積が１．５ｃｃ／ｇ未満である場合、これはシ
リカの構造性が低く、凝集密度が高くなるためか艶消性
能が悪くなる。There is a correlation between the pore distribution of the wet process silica and the BET specific surface area, and the silica of the present invention having the above pore distribution exhibits a BET specific surface area value of 250 to 400 m 2 / g. In the present invention, when the total pore volume of the pore diameter of 20 to 3000 ° is less than 1.5 cc / g, the silica has a low structure and a high agglomeration density, possibly deteriorating the matting performance.
【００１４】又、細孔直径１００〜３００Åの細孔容積
が全細孔容積の５０％未満である場合は、シリカの二次
凝集粒子の構造が不均一であることが予想されるが、こ
の不均一性によるためか高構造性を維持する凝集力が弱
く、特に、高シェアー下でシリカを分散させるような使
用分野において艶消性能を維持することが困難となる。If the pore volume with a pore diameter of 100 to 300 ° is less than 50% of the total pore volume, the structure of the silica secondary aggregated particles is expected to be non-uniform. Possibly due to the non-uniformity, the cohesive force for maintaining high structure is weak, and it is particularly difficult to maintain the matting performance in a field of use where silica is dispersed under a high shear.
【００１５】更に、３００Å以上の細孔容積の全細孔容
積に対する比率が上記範囲より小さい２０％未満である
と、沈澱法シリカの二次凝集粒子の均一な系が予想され
るが、粒子同士の凝集力が強いためか塗膜の透明性，漆
黒性が悪くなる。又、上記範囲より大きい場合は、高シ
ェアー下で分散させるような使用分野において、透明性
等は良好であっても艶消性能が低くなる。Further, when the ratio of the pore volume of 300 ° or more to the total pore volume is less than 20%, which is smaller than the above range, a uniform system of the secondary aggregated particles of precipitated silica is expected. The transparency and jet-blackness of the coating film deteriorate due to the strong cohesion of the film. On the other hand, when it is larger than the above range, the matting performance is low even if the transparency is good in the field of use in which the dispersion is performed under a high shear.
【００１６】本発明の塗料艶消し剤であるシリカを製造
する方法においては、高シェアー下で分散させるような
使用分野においても、その高構造性を維持するためにア
ルカリ金属ケイ酸塩と硫酸との中和反応において、ＢＥ
Ｔ比表面積５００ｍ2 ／ｇ以上、より好ましくは６００
〜１０００ｍ2 ／ｇのシリカスラリーを調製しておき、
このシリカスラリーを水熱処理することによって前記し
た物性を有するシリカを合成するのが良い。In the method for producing silica as a paint matting agent according to the present invention, an alkali metal silicate and sulfuric acid are used in order to maintain the high structure even in a field of use in which the silica is dispersed under a high shear. BE in the neutralization reaction of
T specific surface area of 500 m 2 / g or more, more preferably 600
~ 1000 m 2 / g silica slurry is prepared,
It is preferable to synthesize silica having the above-mentioned properties by subjecting this silica slurry to hydrothermal treatment.
【００１７】ＢＥＴ比表面積が低い場合は、細孔直径１
００〜３００Åの範囲の細孔容積の全細孔容積に対する
比率が大きくならず、高シェアーの分散に耐える構造性
を維持することが困難となる。When the BET specific surface area is low, a pore diameter of 1
The ratio of the pore volume in the range of 00 to 300 ° to the total pore volume does not increase, and it becomes difficult to maintain a structure that can withstand high shear dispersion.
【００１８】又、本発明の塗料艶消し剤であるシリカの
乾燥粉砕は、通常の静置乾燥、続いてビンミルのような
粉砕方法では、塗料艶消し剤として適切な１〜３μｍ程
度の粒子径に調製することや、細孔直径３００Å以上の
細孔容積の全細孔容積に対する比率を前記範囲とするこ
とが難しいので、加熱空気又は過熱蒸気を用いたジエツ
ト粉砕機中で同時に乾燥粉砕するのが望ましい。In the drying and pulverization of the silica as the paint matting agent of the present invention, the usual static drying, followed by a pulverization method such as a bin mill, is suitable for a coating matting agent in a particle size of about 1 to 3 μm. It is difficult to adjust the ratio of the pore volume with a pore diameter of 300 mm or more to the total pore volume within the above range. Therefore, it is necessary to simultaneously dry-pulverize in a jet pulverizer using heated air or superheated steam. Is desirable.
【００１９】尚、本発明の塗料艶消し剤であるシリカを
製造する際の他の条件としては、特に限定されず種々の
方法が採用可能である。本発明の製造方法において、ア
ルカリ金属ケイ酸塩水溶液と硫酸との中和反応を実施
し、５００ｍ2 ／ｇ以上、例えば６００〜１０００ｍ2
／ｇのＢＥＴ比表面積を有するシリカスラリーを調製す
る方法としては、弱酸性域で中和反応を実施する方法、
又は反応温度を５〜４０℃付近に維持し弱アルカリ性域
で中和反応を実施する方法等が適切に用いられる。次い
で得られたシリカスラリー液を水熱処理する条件として
は、ｐＨ８〜１０、温度７０〜１００℃で必要に応じ１
〜１０時間程度実施すれば良い。水熱処理後のシリカス
ラリー液は常法に従って酸性化後、濾過洗浄し、３００
℃以上好ましくは３５０〜６００℃の加熱空気又は過熱
蒸気を用いたジエツト粉砕機中で同時に乾燥粉砕し、必
要に応じて分級すれば良い。The other conditions for producing silica as a paint matting agent of the present invention are not particularly limited, and various methods can be adopted. In the production method of the present invention, a neutralization reaction between an aqueous solution of an alkali metal silicate and sulfuric acid is performed, and the reaction is performed at 500 m 2 / g or more, for example, 600 to 1000 m 2.
/ G of silica slurry having a BET specific surface area includes a method of performing a neutralization reaction in a weakly acidic region,
Alternatively, a method in which the reaction temperature is maintained at about 5 to 40 ° C. and the neutralization reaction is carried out in a weakly alkaline region is appropriately used. Then, the obtained silica slurry liquid is subjected to hydrothermal treatment under conditions of pH 8 to 10 and temperature of 70 to 100 ° C., if necessary.
It may be carried out for about 10 hours. The silica slurry liquid after the hydrothermal treatment is acidified according to a conventional method, and then filtered and washed.
Drying and pulverization may be performed simultaneously in a jet pulverizer using heated air or superheated steam at a temperature of 350 ° C. or more, preferably 350 to 600 ° C., and classification may be performed as necessary.
【００２０】本発明のシリカが、塗料艶消し剤用のシリ
カとして優れている理由は定かではないが、シリカ製造
の初期段階において、５００ｍ2 ／ｇ以上、即ちシリカ
の一次粒子としては非常に小さいものが合成され、次い
で水熱処理によりＢＥＴ比表面積２５０〜４００ｍ2 ／
ｇ程度にまで粒子成長することによって、一次粒子同士
の結合が強くなり、細孔直径３００Å以上の細孔容積が
適度に保持され、高シェアー下での構造性を維持する凝
集力と分散性が適度に調和された状態にあるものと推察
される。Although the reason why the silica of the present invention is excellent as a silica for a paint matting agent is not clear, it is not less than 500 m 2 / g, that is, very small as a primary particle of silica in an initial stage of silica production. Are synthesized and then subjected to hydrothermal treatment to obtain a BET specific surface area of 250 to 400 m 2 /
By growing the particles to about g, the bonding between the primary particles becomes stronger, the pore volume of the pore diameter of 300 mm or more is appropriately maintained, and the cohesive force and dispersibility that maintain the structure under a high shear are improved. It is presumed that they are in a moderately harmonized state.
【００２１】[0021]
【実施例】以下、本発明を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いて各種試験は、
下記の方法によって行った。EXAMPLES The present invention will be described below in more detail with reference to Examples, but it should be understood that the present invention is by no means restricted to such specific Examples. In addition, various tests in Examples and Comparative Examples
It carried out by the following method.
【００２２】（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。(1) BET Specific Surface Area (Nitrogen Method) The BET specific surface area was measured by a one-point method using a canta soap (manufactured by Quantachrome, USA).
【００２３】（２）細孔分布及び細孔容積（窒素法） ＡＳＡＰ−２４００（島津製作所製）を用いて測定し
た。(2) Pore distribution and pore volume (nitrogen method) Measured using ASAP-2400 (manufactured by Shimadzu Corporation).
【００２４】（３）二次凝集粒子の粒度分布並びに平均
粒径（体積平均径） コールターカウンターＴＡ−II（Ｃｏｕｌｔｅｒｅｌｅ
ｃｔｏｒｏｎｉｃｓＩｎＣ．製）を用いて３０μｍアパ
ーチャーチューブにより測定した。(3) Particle size distribution and average particle diameter (volume average diameter) of secondary aggregated particles Coulter counter TA-II (Coulterele)
ctonicsInC. Was measured using a 30 μm aperture tube.
【００２５】（４）光沢度 スガのグロスメーターを用いて∠６０°の反射率を測定
した。数値の低い方が艶が消えている。(4) Gloss The reflectance at 60 ° was measured using a Suga gloss meter. The lower the value, the less the luster.
【００２６】（５）漆黒性 色差計を用いてその漆黒性を測定した。数値が低い方が
漆黒性が良い。(5) Jetness The jetness was measured using a color difference meter. The lower the value, the better jet-blackness.
【００２７】（６）透過率 色差計を用いてその透過度を測定した。数値は高い方が
透明性が良い。(6) Transmittance The transmittance was measured using a color difference meter. The higher the value, the better the transparency.
【００２８】（７）分散度 グラインドゲージを使用し測定した。(7) Dispersion Measured using a grind gauge.
【００２９】（８）塗膜外観 目視による。(8) Appearance of coating film Visually observed.
【００３０】実施例１ 珪酸ナトリウムと硫酸との同時滴下中和反応において、
反応温度を３０℃に維持し全中和反応を行った後、水熱
処理をｐＨ９，温度８０℃，２時間で実施し、酸性化後
濾過−洗浄した後、シリカのケークを得た。次いで該ケ
ークをスラリー化し、過熱蒸気の温度を５５０℃、粉砕
圧力３．０（ｋｇ／ｃｍ2 Ｇ）の条件において流体エネ
ルギーミル（フルードエナジー社製）を使用し同時乾燥
粉砕を行った。この時流体エネルギーミルの出口温度が
ｌ７０℃になるように該スラリーを定量ポンプを用いて
フィードした。得られた沈澱法シリカをｌ００℃の乾燥
気流中で風力分級機を用いて分級し、表ｌのシリカが得
られた。尚、水熱処理前のシリカ反応液を一部取り出
し、シリカのＢＥＴ比表面積を測定したところ７４４ｍ
2 ／ｇであった。Example 1 In a simultaneous dropping neutralization reaction of sodium silicate and sulfuric acid,
After performing a total neutralization reaction while maintaining the reaction temperature at 30 ° C., a hydrothermal treatment was performed at pH 9 and a temperature of 80 ° C. for 2 hours. After acidification, filtration and washing were performed, a silica cake was obtained. Next, the cake was slurried and simultaneously dried and pulverized using a fluid energy mill (Fluid Energy) under the conditions of a superheated steam temperature of 550 ° C. and a pulverization pressure of 3.0 (kg / cm 2 G). At this time, the slurry was fed using a metering pump so that the outlet temperature of the fluid energy mill became 170 ° C. The obtained precipitated silica was classified in a dry air stream at 100 ° C. using an air classifier to obtain the silica shown in Table 1. A part of the silica reaction liquid before the hydrothermal treatment was taken out, and the BET specific surface area of the silica was measured to be 744 m
2 / g.
【００３１】次いで塗膜形成としてアミノアルキツド樹
脂（日本ペイント社製）を用い、樹脂１００重量部に対
して、キシレンｌ０重量部、沈澱法シリカ４重量部を配
合し、ペイントシェーカーを用いて３０分分散した。こ
の時の分散度を測定した。さらに分散液を、Ｎｏ．２０
バーコーターによりブリキ板（ｌ００×２００ｍｍ）に
塗布した後、ｌ２０℃で２０分乾燥し塗膜を形成した。
この塗膜の光沢度，漆黒性を測定した結果を分散度と共
に表ｌに示した。この評価において、分散度は３０μｍ
以下、光沢度は７５％以下及び漆黒性は１．９以下の塗
料物性を有することが望ましい。Next, 10 parts by weight of xylene and 4 parts by weight of precipitated silica were blended with 100 parts by weight of an aminoalkyd resin (manufactured by Nippon Paint Co., Ltd.) to form a coating film, and dispersed for 30 minutes using a paint shaker. did. The degree of dispersion at this time was measured. Further, the dispersion was 20
After coating on a tin plate (100 × 200 mm) with a bar coater, the coating was dried at 120 ° C. for 20 minutes to form a coating film.
The results of measuring the glossiness and jet-blackness of this coating film are shown in Table 1 together with the degree of dispersion. In this evaluation, the degree of dispersion was 30 μm
In the following, it is desirable that the glossiness is 75% or less and the jetness is 1.9 or less.
【００３２】また、塗膜形成剤としてアクリルクリアー
樹脂（関西ぺイント社製）を用いて、樹脂１００重量部
に対して、専用シンナー４５０重量部、試料を４重量部
を配合し、ぺイントシェーカーを用いて３０分分散し
た。この時の分散度を測定した。さらに分散液をｌ００
μｍアプリケーターによりガラス板（５０×１００×３
ｍｍ）に塗布した後、２０℃で３０分乾燥し塗膜を形成
した。この塗膜の透過率を測定した結果を分散度ととも
に表２に示した。Also, using an acrylic clear resin (manufactured by Kansai Paint Co., Ltd.) as a coating film forming agent, 450 parts by weight of a special thinner and 4 parts by weight of a sample were mixed with 100 parts by weight of the resin. For 30 minutes. The degree of dispersion at this time was measured. Further, the dispersion is
Glass plate (50 × 100 × 3) with μm applicator
mm), and dried at 20 ° C. for 30 minutes to form a coating film. The results of measuring the transmittance of this coating film are shown in Table 2 together with the degree of dispersion.
【００３３】実施例２ 実施例ｌにおいて反応温度を２０℃に維持した以外は、
同様にして沈澱法シリカを得た。尚水熱法制処理前のシ
リカ反応液を一部取り出し、ＢＥＴ比表面積を測定した
ところ６７５ｍ2 ／ｇであった。得られたシリカの特性
及び塗料充填後の物性を測定した結果は第１表に示し
た。Example 2 Except that the reaction temperature was maintained at 20 ° C. in Example 1,
Similarly, precipitated silica was obtained. A part of the silica reaction liquid before the hydrothermal treatment was taken out, and the BET specific surface area was measured to be 675 m 2 / g. Table 1 shows the results of measuring the properties of the obtained silica and the physical properties after filling the paint.
【００３４】実施例３ 実施例１において反応温度を４０℃に維持した以外は、
同様にして沈澱法シリカを得た。尚水熱処理前のシリカ
反応液を一部取り出し、ＢＥＴ比表面積を測定したとこ
ろ６１１ｍ2 ／ｇであった。得られたシリカの特性及び
塗料充填後の物性を測定した結果は第１表に示した。Example 3 Example 1 was repeated except that the reaction temperature was maintained at 40 ° C.
Similarly, precipitated silica was obtained. A part of the silica reaction solution before the hydrothermal treatment was taken out, and the BET specific surface area was measured to be 611 m 2 / g. Table 1 shows the results of measuring the properties of the obtained silica and the physical properties after filling the paint.
【００３５】実施例４ ケイ酸ナトリウムと硫酸との同時滴下中和反応におい
て、反応温度を３０℃に維持し全中和反応を行った後、
水熱処理をｐＨ９，温度８０℃，５時間で実施し、酸性
化後濾過洗浄した後、シリカのケークを得た。それ以外
は実施例１と同様の操作で製造を行った。得られたシリ
カの特性及び塗料充填後の物性を測定した結果は表１に
示した。Example 4 In the simultaneous dropping neutralization reaction of sodium silicate and sulfuric acid, the reaction temperature was maintained at 30 ° C., and the whole neutralization reaction was carried out.
Hydrothermal treatment was carried out at pH 9, at a temperature of 80 ° C for 5 hours, and after acidification and filtration and washing, a silica cake was obtained. Except for this, the production was performed in the same manner as in Example 1. Table 1 shows the results of measuring the properties of the obtained silica and the physical properties after filling the paint.
【００３６】実施例５ 実施例１において乾燥方法としてスプレードライヤーを
用い、粉砕方法としてミクロンジエツト（細川ミクロン
社製）を用いた以外は同様にして沈澱法シリカを得た。
得られたシリカの特性及び塗料充填後の物性を測定した
結果は第１表に示した。Example 5 Precipitated silica was obtained in the same manner as in Example 1 except that a spray dryer was used as a drying method and a micron jet (manufactured by Hosokawa Micron Corporation) was used as a pulverizing method.
Table 1 shows the results of measuring the properties of the obtained silica and the physical properties after filling the paint.
【００３７】比較例１ ケイ酸ナトリウムと硫酸を混合ノズルを用いてｐＨｌ．
５で反応を行い、硬い塊状のヒドロゲルを得て、９０℃
のアルカリ水溶液にて４８時間洗浄を行い、過熱蒸気の
温度５５０℃、粉砕圧力３．０（ｋｇ／ｍ2 Ｇ）の条件
において流体エネルギーミル（前出）を使用し同時乾燥
粉砕を行った。この時流体エネルギーミルの出口温度は
ｌ７０℃になるように該スラリーを定量ポンプを用いて
フィードした。得られたシリカゲルをｌ００℃の乾燥気
流中で風力分級機を用いて分級し、表１のシリカゲルが
得られた。次いで、実施例１と同様に塗料評価を行っ
た。その結果を表１，２に示した。COMPARATIVE EXAMPLE 1 A mixture of sodium silicate and sulfuric acid was adjusted to pH 1 using a mixing nozzle.
5 to obtain a hard lump hydrogel,
Was washed with an aqueous alkaline solution for 48 hours, and simultaneously dried and pulverized using a fluid energy mill (described above) under the conditions of a superheated steam temperature of 550 ° C. and a pulverizing pressure of 3.0 (kg / m 2 G). At this time, the slurry was fed using a metering pump so that the outlet temperature of the fluid energy mill became 170 ° C. The obtained silica gel was classified in a dry air stream at 100 ° C. using an air classifier, and the silica gel shown in Table 1 was obtained. Next, paint evaluation was performed in the same manner as in Example 1. The results are shown in Tables 1 and 2.
【００３８】比較例２ 市販品ニップシールＨＤ（日本シリカ工業製品）を用い
て、塗料充填時の諸物性を測定した。結果は第１表に示
した。Comparative Example 2 Using a commercially available nip seal HD (manufactured by Nippon Silica Kogyo Co., Ltd.), various physical properties at the time of filling the paint were measured. The results are shown in Table 1.
【００３９】比較例３ 実施例１において２０時問水熱処理を行った以外は同様
にして沈澱法シリカを得た。得られたシリカの特性及び
塗料充填後の物性を測定した。結果は表ｌに示した。Comparative Example 3 Precipitated silica was obtained in the same manner as in Example 1 except that the hydrothermal treatment was performed for 20 hours. The properties of the obtained silica and the physical properties after filling the paint were measured. The results are shown in Table 1.
【００４０】比較例４ 実施例ｌにおいてシリカのケークを得た後静置乾燥を行
い、ミクロンジエツト（前出）を用いて粉砕して沈澱ケ
イ酸を得た。得られたシリカの特性及び塗料充填後の物
性を測定した。結果は表１に示した。Comparative Example 4 The silica cake obtained in Example 1 was dried by standing, and then pulverized using a micro-diet (described above) to obtain precipitated silicic acid. The properties of the obtained silica and the physical properties after filling the paint were measured. The results are shown in Table 1.
【００４１】比較例５ 実施例１において１時間水熱処理を行った以外は同様に
して沈澱法シリカを得た。得られたシリカの特性及び塗
料充填後の物性を測定した結果は。表１に示した。Comparative Example 5 Precipitated silica was obtained in the same manner as in Example 1 except that the hydrothermal treatment was performed for 1 hour. What are the results of measuring the properties of the obtained silica and the physical properties after filling the paint? The results are shown in Table 1.
【００４２】[0042]
【表１】 [Table 1]
【００４３】[0043]
【表２】 [Table 2]
【００４４】[0044]
【発明の効果】本発明により得られた沈澱法シリカから
なる新規な塗料艶消し剤は、特殊な細孔分布を有するも
のであり、塗料艶消し剤として、透明性，漆黒性に優れ
ている。According to the precipitated silica obtained according to the present invention,
It becomes the new paint matting agents are those which have a special pore distribution, as a paint flatting agents, transparency is excellent in jet-blackness.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 201/00 C09C 3/04 C09D 5/00 ──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int. Cl. 7 , DB name) C09D 201/00 C09C 3/04 C09D 5/00
Claims (2)
が１．５ｃｃ／ｇ以上、細孔直径１００〜３００Åの細
孔容積が全細孔容積の５０％以上であり、且つ細孔直径
３００Å以上の細孔容積が全細孔容積の２０％以上であ
る沈澱法シリカからなることを特徴とする塗料艶消し
剤。1. The total pore volume with a pore diameter of 20 to 3000 mm is 1.5 cc / g or more, the pore volume with a pore diameter of 100 to 300 mm is 50% or more of the total pore volume, and the pore diameter is A matte paint comprising a precipitated silica having a pore volume of 300% or more of 20% or more of the total pore volume.
Agent .
下中和反応によって、ＢＥＴ比表面積が５００ｍ2 ／ｇ
以上であるシリカのスラリーを調製し、引き続き水熱処
理を実施し、得られた沈澱法シリカを加熱空気または過
熱蒸気を用いたジエツト粉砕機の中で乾燥粉砕を同時に
行うことを特徴とする請求項１の物性を有する塗料艶消
し剤の製造方法。2. A BET specific surface area of 500 m 2 / g by simultaneous drop neutralization reaction of an alkali metal silicate and sulfuric acid.
A silica slurry as described above is prepared, hydrothermal treatment is subsequently performed, and the obtained precipitated silica is simultaneously dried and pulverized in a jet pulverizer using heated air or superheated steam. Matte paint with physical properties of 1
A method for producing a lacquer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05146282A JP3131076B2 (en) | 1993-06-17 | 1993-06-17 | Paint matting agent and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP05146282A JP3131076B2 (en) | 1993-06-17 | 1993-06-17 | Paint matting agent and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH073182A JPH073182A (en) | 1995-01-06 |
| JP3131076B2 true JP3131076B2 (en) | 2001-01-31 |
Family
ID=15404192
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP05146282A Expired - Lifetime JP3131076B2 (en) | 1993-06-17 | 1993-06-17 | Paint matting agent and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3131076B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3935563B2 (en) * | 1997-08-04 | 2007-06-27 | 富士シリシア化学株式会社 | Matting agent for paint and method for producing matting agent for paint |
| KR100283124B1 (en) * | 1998-06-09 | 2001-04-02 | 서경배 | A method for preparation of composite pigment for make-up cosmetics and make-up cosmetic compositions containing composite pigments made thereby |
| DE10148851A1 (en) * | 2001-10-04 | 2003-04-17 | Henkel Kgaa | Surface treatment to improve the storage stability and non-adhesiveness of active agents such as detergent ingredients or pharmaceuticals involves coating with a powder which has been milled under drying conditions |
| JP2006255667A (en) | 2005-03-18 | 2006-09-28 | Toshiba Corp | Carbon dioxide absorbent and method for preparing it |
| JP6042085B2 (en) * | 2012-03-27 | 2016-12-14 | 株式会社トクヤマ | Aerogel and matting agent comprising said airgel |
| JP6166440B2 (en) * | 2016-08-26 | 2017-07-19 | 株式会社トクヤマ | Aerogel and matting agent comprising said airgel |
| CN113755033A (en) * | 2021-08-14 | 2021-12-07 | 南通双华纳米新材料有限公司 | High-temperature treatment device for processing red carbon black and high-temperature treatment method thereof |
| CN115159530A (en) * | 2022-08-08 | 2022-10-11 | 确成硅化学股份有限公司 | Synthesis process of large-pore-volume precipitated silica for coating flatting agent |
-
1993
- 1993-06-17 JP JP05146282A patent/JP3131076B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH073182A (en) | 1995-01-06 |
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