JPS58204061A - Water paint - Google Patents
Water paintInfo
- Publication number
- JPS58204061A JPS58204061A JP57086202A JP8620282A JPS58204061A JP S58204061 A JPS58204061 A JP S58204061A JP 57086202 A JP57086202 A JP 57086202A JP 8620282 A JP8620282 A JP 8620282A JP S58204061 A JPS58204061 A JP S58204061A
- Authority
- JP
- Japan
- Prior art keywords
- value
- paint
- calcium carbonate
- water
- wet
- 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.)
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Links
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Abstract
Description
【発明の詳細な説明】
本発明は、炭酸カルシウムを顔料とする水系塗料の、粘
度、光沢、隠蔽性１作業性、刷毛さばき性９Ｍ候性など
の諸性質の綜合的な改善に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the comprehensive improvement of various properties of a water-based paint containing calcium carbonate as a pigment, such as viscosity, gloss, concealing property, 1 workability, brush handling property, and 9M weatherability.
水系塗料に含まれる顔料としての炭酸カルシウムは、そ
の粒子径だけでなく製造法によっても、塗料の粘度、光
沢、隠蔽性、刷毛さばき性、作業性、耐候性表どに大き
く影響を及ぼすことがよく知られている。従来、この種
の炭酸カルシウムは製造法の点から大別してλ通りがあ
る。化学的に合成してつくる沈降性炭酸カルシウムと石
灰岩から機械的に粉砕され７’Ｃ重質炭酸カルシウムと
である。前者は、その粒子径が均一であるがきわめて微
粒のものであるため、配合菫を比較的に少−にとどめて
も、塗料の増粘化が激しく、プリン状になるトラブルが
出る場合すらあり、その二次凝集を防ぐために処理剤を
使うと塗布時の泡立ちが多いという欠点も出てくる。Calcium carbonate, which is a pigment contained in water-based paints, can greatly affect the viscosity, gloss, hiding properties, brushability, workability, weather resistance, etc. of the paint, depending not only on its particle size but also on the manufacturing method. well known. Conventionally, this type of calcium carbonate has been broadly classified into λ types based on the manufacturing method. They are precipitated calcium carbonate, which is chemically synthesized, and 7'C heavy calcium carbonate, which is mechanically crushed from limestone. The former has a uniform particle size but is very fine, so even if the amount of violet added is kept relatively small, the viscosity of the paint will thicken significantly and may even cause problems such as becoming pudding-like. However, if a treatment agent is used to prevent secondary agglomeration, the disadvantage is that there is a lot of foaming during application.
一方、機械的に粉砕された重質炭酸カルシウムは、粒度
分布範囲が広く均質性に乏しく、風簸、水被による分級
能力にも限界があるため、阻大粒子の混入が避けられな
い。このため、塗膜の光沢性、隠藪性、耐候性が著しく
低下し、単に増緻剤としての役割しか与えられていない
現状である。On the other hand, mechanically pulverized heavy calcium carbonate has a wide particle size distribution range and lacks homogeneity, and its ability to classify by elutriation and water coverage is limited, so contamination with large particles is unavoidable. For this reason, the gloss, hiding property, and weather resistance of the coating film are significantly reduced, and the current situation is that it is only used as a thickening agent.
ところで最近、湿式粉砕によれば分布範囲が狭い粒度分
布の災酸カルシウムが得られることが知られるようにな
って米た。ということは、たとえば、粘度良好の罠めの
粘度分布はどうあるべきかがテストされ得るということ
である。Recently, however, it has become known that wet pulverization can produce calcium oxides with a narrow particle size distribution. This means, for example, that it can be tested what the viscosity distribution of a trap with good viscosity should be.
湿式粉砕にしろ乾式粉砕にしろ、また、化学合成にしろ
、製造法に違いがあれば炭酸カルシウムの粒子の性状が
異なるかもしれない、この点の実証も可能になる。そこ
で、粒度分布からの分析が論じられる必狭が出て米る。It will also be possible to demonstrate that the properties of calcium carbonate particles may differ if there are differences in the manufacturing method, whether it is wet pulverization, dry pulverization, or chemical synthesis. Therefore, it becomes necessary to discuss analysis based on particle size distribution.
そのだめの粒度分布の分析は、一般に、次に述べる比表
面積のｌｆｆ１．即ち、Ｓ値で表現される。今、次表で
示すｌ／階級で分級することにする。Analysis of the particle size distribution of the pellet is generally performed using the following specific surface area lff1. That is, it is expressed as an S value. Now, we will classify by l/class shown in the following table.
この賢で、ｄｉは各階級の粒子径の中央値である。この
分級を用いて、モ均粒子ｔＬ Ｄ ｌｒ次式＋１１式で
定義する。In this equation, di is the median particle size of each class. Using this classification, the uniform particle tL D lr is defined by the following equation + 11 equation.
但し、 ｄｉの単位は／θ−６１Ｂ％町は試料を分級し
ｉ番目の階級にある全粒子の重量チで測定きれた値を表
わす。りｖｉは／Ｑθチの社である。さらに、この平均
粒子音りと用いて、比表面積、叩ち、Ｓ値を次式（２）
式で定義しておく。However, the unit of di is /θ-61B% represents the value measured by the weight of all particles in the i-th class after classifying the sample. Rivi is a company of /Qθchi. Furthermore, using this average particle sound, the specific surface area, hitting, and S value can be calculated using the following formula (2).
Define it using the formula.
各階級に属する全粒子の全重着チの測定は次のように行
なう。粒度分布６１１１定器（この明細書におけるデー
タは晶津遠心沈降型粒度分布測定器ＣＰ−３０型を用い
て得られたものである）を用い、ヘキサメタリン酸ナト
リウム４２重Ｒ％の水溶液中、ａ！〜ツθ重ｉｔチの試
料を加えて、 １０分間振とうさせたのちに行なう。The total weight of all particles belonging to each class is measured as follows. Using a particle size distribution analyzer 6111 (the data in this specification was obtained using a Shojin centrifugal sedimentation type particle size distribution analyzer CP-30 model), a. ! Add 10 to 100% of the sample and shake for 10 minutes.
このように定義されたＳ値の炭酸カルシウム、たとえば
、Ｓ値が低い炭酸カルシウムは、粒子が粗大である。Ｓ
値が大きくなＶ過ぎると粒子が微小に過ぎ、粘度その他
の性質で塗料としては適さないものになる。それでは、
ちょうど都合のよいＳ値のものがあるかどうかであるが
、乾式粉砕で得られる炭酸カルシウムは、Ｓ値が過大で
も過少でもないところにあるものでも、粒塵分布の拡が
りが広範囲であるとと、もに、粗大粒子が混入しており
、粗大粒子の混入を回継することが不可能に近く、粗大
粒子の存在−を十分に少なくしようとすると、Ｓ値が過
大になってしまう。Calcium carbonate having an S value defined in this way, for example, calcium carbonate having a low S value, has coarse particles. S
If the value of V is too large, the particles will be too small and will be unsuitable as a paint due to viscosity and other properties. Well then,
The question is whether there is a suitable S value, but calcium carbonate obtained by dry grinding has a wide range of particle dust distribution even if the S value is neither too high nor too low. Both of them contain coarse particles, and it is almost impossible to repeat the contamination of coarse particles, and if the presence of coarse particles is attempted to be sufficiently reduced, the S value will become excessive.
本発明は、ｐ、、２＋、＜分布の拡がりが狭いという湿
式粉砕の性質Ｅて噛目し、Ｓ値がどのような範囲にある
のがよいか全突きとめるとともに、どの程度に湿式粉砕
をすればよいかの条件をも明らかにして、そのような・
多件下、適切な範囲のＳ値を与え、上述したｄ＃性質を
綜合的に改善した貞質炭酸カルシウムを顔料として含む
水系塗料の提供を目的とする。The present invention takes into consideration the property E of wet grinding that p, 2+ < narrow spread of distribution, fully ascertains what range the S value should be in, and determines to what extent wet grinding should be carried out. Clarify the conditions under which such
The object of the present invention is to provide a water-based paint containing pure calcium carbonate as a pigment, giving an S value in an appropriate range and comprehensively improving the above-mentioned d# properties.
本発明に係る炭酸カルシウムは、湿式で粉砕されており
、湿式粉砕後の上記（シ・）式で与えらり。The calcium carbonate according to the present invention is wet-milled, and is given by the above formula (C) after wet-milling.
るＳ＋！が、湿式粉砕後のＳ値を以下Ｓ１で表わすと、
ムθ４ Ｓｌ ｌ；、 ？、θ ・・・
・・８）上記（３）式で与えられる範囲に入っているも
のである。Ru S+! However, when the S value after wet grinding is expressed as S1 below, θ4 Sl l;, ? , θ...
...8) It falls within the range given by equation (3) above.
湿式粉砕を行なえば、粗大粒子、たとえば、第７７階級
に入る径の大きな粒子も細かく砕かれると同時に、粒径
分布は狭くなり、即ち、第ｌ／階級の粒子は存在しなく
なるか、あっても、きわめて微量とな９、しかも、Ｓｉ
ｔ直が大きくなるということもない。湿式粉砕ではｉｆ
ｒ級の高いものから速やかに破壊されて行く傾向が乾式
粉砕のものに較べて著しく強いからである。If wet grinding is carried out, coarse particles, for example, particles with a large diameter that fall into the 77th class, will be finely ground, and at the same time, the particle size distribution will be narrowed, that is, particles in the 1st/class will not exist or will be present. Also, the amount of Si is extremely small9.
There is no possibility that the t-shift becomes large. In wet grinding, if
This is because the tendency for materials with a high R-class to be destroyed quickly is significantly stronger than that of materials that are dry-milled.
ｌｉ式粉砕の程度も重要である。たとえば、石灰岩を乾
式で機械粉砕された従来の炭酸カルシウムは、上記表に
もとづいてＳ値を算出したとき（湿式粉砕前のＳ値を以
下Ｓｏで表わす）に、Ｓｏ値が仮に第Ｇ３１式の範囲に
人っていても、粗大粒子の量が少ないとは言えない。本
発明品では、Ｓ＞＝９３ で、もつとも良質の塗料が
・潜られるが、機械乾式粉砕のものではそれのＳｏ値が
ζｊであっても１，７．１階級のものも第１／階級のも
のも多く混在していて、塗料としての性能はきわめて悪
い。従って、乾式粉砕のものも必らず一度は湿式で再開
粉砕される必要がある。湿式粉砕は必らず必要であるが
その度合がきわめて重要である。そのＩＷばは、次式（
４）で与えられる。The degree of li-grinding is also important. For example, when the S value of conventional calcium carbonate obtained by dry mechanically crushing limestone is calculated based on the above table (the S value before wet crushing is hereinafter expressed as So), the So value is based on the formula G31. Even if there are people in the area, it cannot be said that the amount of coarse particles is small. With the product of the present invention, when S>=93, it is possible to obtain a high quality paint, but with the mechanical dry grinding product, even if the So value is ζj, the paint of class 1/7.1 can be obtained. Many of these substances are mixed together, and its performance as a paint is extremely poor. Therefore, even those that are dry-ground must be wet-ground again at least once. Although wet pulverization is absolutely necessary, the degree of wet pulverization is extremely important. The IW value is calculated by the following formula (
4) is given by
Ｓｔ ’ｈｖ’Ｓｏ２＋ａ 、、
、、、 （４）一般に、
Ｓｏ／：Ｓｌ
であるから、
Ｓ、＝ ５ 、 、 、 、、（５）で、
一般に必らずａ〉θである。このａはＳｏの関数で与え
られるであろうが、６＼ｊとすルば一役的ＶＣ十分であ
り、より好ましくはα≧７０−Ｃある。St'hv'So2+a,,
,,, (4) Generally, since So/:Sl, S,= 5, , , , , (5),
In general, a>θ is always satisfied. This a may be given by a function of So, but if 6\j is used, a single VC is sufficient, and more preferably α≧70−C.
（３）式と（４）式とを、横軸を８０％ 慣軸１ｋＳＸ
としてグラフに示すと、本発明品は第７図で交叉斜線部
に属する。７点４線で示すＳｏ ＝ ＳＬの直゛腺より
下方の領域は一般的Ｖこにちゃえないが、夕＜Ｓ。(3) and (4), horizontal axis is 80%, inertial axis 1kSX
When shown in a graph as , the product of the present invention belongs to the cross-hatched area in FIG. The area below the vertical gland of So = SL shown by 7 points and 4 lines cannot be considered as a general V, but E < S.
〈９の同にあっても、曲線グと直線ｊとの間の領域Ａに
嘱する湿式粉砕の炭酸カルシウム粉には、まだ粗大粒Ｆ
Ｖｃついての粉砕が不十分であるゆえに、粗大粒子の混
入量が多くて、塗料は良質ではない。〈Even in the case of 9, there are still coarse particles F in the wet-pulverized calcium carbonate powder in the area A between the curved line and the straight line j.
Since the pulverization with respect to Vc is insufficient, there is a large amount of coarse particles mixed in, and the paint is not of good quality.
そこで、いろいろなＳｏの値のものについて、Ｓよ＝ｊ
からＳｚ ＝りまでを何段階かに区切り、もつとも良質
の塗料が得られる（５）式中のａの値を実測値として求
めておき、また、その値ａにおいて、（５）式で建まる
Ｓｙ−を得るときの、湿式粉砕条件を確定しておけば実
施上好都合である。Therefore, for various values of So, S = j
Divide the range from Sz = ri into several stages, obtain the value of a in formula (5) as an actual measurement value that will give you the best quality paint, and then calculate the value of a in formula (5) at that value a. It is convenient for implementation if the wet pulverization conditions for obtaining Sy- are determined.
一度湿式に粉砕されていて本、粉砕後に（４）式を充足
するＳｉ値が得られない場合には、粗大粒子が多く混入
されている恐れがあるのは前述の通りでろ９、従って、
この際は再度湿式に粉砕しなければならないが、何回湿
式粉砕をしても要するに最後の湿式粉砕によって得られ
るときのＳ値ｉＳｉとし、７回も湿式粉砕されていない
ときのｓ ｔｔをＳＯとして、（４）式が適用される。As mentioned above, if the Si value that satisfies equation (4) cannot be obtained after being wet-pulverized, there is a possibility that large amounts of coarse particles are mixed in.9 Therefore,
In this case, it must be wet-pulverized again, but no matter how many times it is wet-pulverized, the S value obtained by the last wet-pulverization is iSi, and s tt is SO when it has not been wet-pulverized seven times. As such, equation (4) is applied.
湿式粉砕には、ボールミル、サンドミル等の粉砕機が用
いられる。たとえば、回転軸／に取付けられた複数葉の
粉砕羽根コをケーシング３の中で回転させ、取入ログか
ら予め小粒にした石灰岩と水とを・尊大し、スリット板
又は金＠ｊでふるいにかけて取出口６から取出す。この
ようにして取出された湿式粉砕後のＳ値が８１で表わさ
れ、取入ログから導入されるものは、それが一度も湿式
粉砕されていないときに、Ｓｏで表わされる。For wet pulverization, a pulverizer such as a ball mill or a sand mill is used. For example, a multi-leaf crushing impeller attached to the rotating shaft is rotated in the casing 3, and limestone and water, which have been made into small particles from the intake log, are sieved with a slit plate or a gold plate. Take it out from outlet 6. The S value after wet milling thus extracted is represented by 81, and the one introduced from the intake log, when it has never been wet milled, is represented by So.
湿式粉砕で得られた（３）式を満足するＳ値のル質炭酸
カルシウムを蛸科として用いた水系伍料は、塗膜の光沢
、隠蔽性、ｉ耐候性などの性質において綜合的に峡も良
質であり、粘度が経時的に着しく増大するということが
なく、泡立ちが少なく作栗住にすぐれ、塗布中の刷毛さ
ばきも ′良好である。Water-based materials using rutinous calcium carbonate, which has an S value that satisfies formula (3) obtained by wet grinding, are comprehensively superior in properties such as gloss, hiding properties, and weather resistance of the coating film. It is also of good quality, does not increase its viscosity over time, has little foaming, has excellent consistency, and has good brush control during application.
しかし、Ｓ１１直が９を越えるものは、それ以上に５Ｌ
ＩＩＩＩが大きくなればなるほど、粒子が極バ門に微粒
化されているので、塗料作成時点ですでに粘度が高く、
塗布時の、ｉｌ＋ＩＪ毛さばきが、法＜、１砥融性も低
下する。However, if the S11 shift exceeds 9, the 5L
The larger III is, the finer the particles are, so the viscosity is already high at the time of paint creation.
During application, the il+IJ hair handling is lower than 1, and the abrasiveness is also reduced.
逆に、Ｓｌ値がｊを下回ると、乾式塩炭と同！美丸べ、
隠蔽性谷の諸物性が低下し、単なる噌量剤としてのみの
利用方法しかみい出せない。On the other hand, when the Sl value is less than j, it is the same as dry salt coal! Mimarube,
The physical properties of the concealing valley deteriorate, and it is only possible to use it as a mere filler.
湿式粉砕は、重質炭酸カルシウム懸濁液中に、沈降性炭
酸カルシウム、クレー、メルク等の他の顔料を同時に層
温させて行なわれてもよいが、その場合には、メルク等
ｔよ板状結晶で壊れやすいので、炭カルリンチなどとす
る混合割合に注意する必要が実施上ある。Wet grinding may be carried out by simultaneously layering other pigments such as precipitated calcium carbonate, clay, and Merck in a suspension of heavy calcium carbonate; Since it is a crystal-like crystal and easily breaks, it is necessary to be careful about the mixing ratio of charcoal, etc. in practice.
また、水系ｍ材中に配合する場合、実際上は塗料固形分
を上げるため−Ｃきる限９篩い炭酸カルシウムスラリー
固形分が必要であるため、一般に顔料の分散剤として使
用されるポリアクリル＃Ｒ塩、リン酸塩、無水マレイン
酸共重合体などを層積以上、戻戚カルシウムの水懸濁液
中に添加して、懸濁液の粘ｆを低下させてから、湿式粉
砕を行なうのが有利である。粉砕後のＮ質炭酸カルシウ
ムスラリーは、運送上の問題などから必要に応じて脱水
操作を行なって固形分湿１１ｆｔＩＱＩめてから使われ
る。In addition, when blending into water-based m-materials, it is actually necessary to increase the solid content of calcium carbonate slurry through a -C 9 sieve to increase the solid content of the paint, so polyacrylic #R is generally used as a pigment dispersant. It is best to add a layer or more of salt, phosphate, maleic anhydride copolymer, etc. to the aqueous suspension of returned calcium to lower the viscosity f of the suspension, and then perform wet pulverization. It's advantageous. The N-quality calcium carbonate slurry after pulverization is dehydrated as necessary due to transportation problems, etc., and the slurry is used after the solid content is 11 ft IQI.
以下、試験物について報告する。実施例、比較例をタリ
記する。なお、実施例、比較例とも下記のごとく、２種
の塗料配合について最終塗料性能を評価した。The test items are reported below. Examples and comparative examples are listed below. In both Examples and Comparative Examples, the final paint performance was evaluated for two types of paint formulations as shown below.
〔塗料配合１） ＰＶＣ＝コθチ
０ミルペース
水 ／θθ重１部
分散削（第−工業製溪、デスコートＮ／ダ）♂ −
分散剤（、ノイゲンＦＡ／、２θ）
２ ＃
凍結防止剤（プロピレングリコール）りθ Ｉチタン白
（６原産業、Ｒ−６３θ） ／り！ Ｉ貞ス炭・シカ
ルシウム（固形分２０チスラリー）７３ ’−
Ｏレットダウン
ミルペース
エマルジョン（大日本インキ、ボンコートＴＤ（１２／
、、３−０チ） ６７２重１部り’ＳＩＩ Ａ
ＩＪ （エチレングリコール−モノ−Ｎ−ブチルエーテ
ル） ７θ Ｉ
保護コロイド（ＨＥＣ，２６％５ｏｌ） ７３ １Ｐ
Ｈ調整剤（水酸化アンモニウム、、２ｔ％Ｓｏ／ ）２
重Ｊ部
〔塗料配合２）ＰＶＣ＝４θチ
Ｏミルベース
分散剤（射−工業製薬、テスコー）Ｎ／ダ）／り塩一部
分散剤（Ｉ ｌノイゲンＥＡ／２０）Ｉ
凍結防止剤（プロピレングリコール） ２θ ｌｆｌ炭
酸カルシウム（固形分１ｏｔｓスラリー）４ｔｏｏ
’
チタン白（６原産業、Ｒ−６３０） ２３θ ＩＯフ
レットウン
ミルベース
エマルジョン（大日本インキ、ボンコー）２３／θ〔ア
クリルスチレン樹脂”１６６％）
／、１５’グ虚違部
造膜助剤（エチレングリコール−モノ−Ｎ−ブチルエー
テル） ３０ ′
保護コロイド（ｌｌＥＣ、２Ｊ９６ Ｓｏｌ ）
ｔθ東醍部Ｐ Ｈ、Ｊ！幣剤（水酸化アンモニウム、２
３％５ｏｌ）３ ＃
実悔囲−／
５ｏ＝−２，♂の重質炭酸カルシウム７００部と分散剤
としてポリアクリル酸ソーダ４２部を固形分濃度７θチ
になるよう水中に懸濁させ、ラボディスパー攪拌機（特
殊機化）にて懸濁液を作成し、これをダイノコミル（Ｗ
ＡＢ社製、ｐｒ−ＬＯＴ型）にてＳ２＝ジｊとなるよう
湿式粉砕を行なった。このようにして得た重質炭酸カル
シウムを用い、上記塗料配合１及び２によって水系塗料
組成物を調整し、塗料性能を評価した。[Paint formulation 1] PVC = Ko θ 0 mil pace water / θ θ heavy 1 part milling (Dai-Kogyo Seikei, Descoat N/DA) ♂ - Dispersant (, Neugen FA/, 2 θ) 2 # Antifreeze agent ( Propylene glycol) Ri θ I Titanium White (6 Hara Sangyo, R-63 θ) / Ri! I Teisu charcoal/Sicalcium (solid content 20% slurry) 73'- O let down mill pace emulsion (Dainippon Ink, Boncourt TD (12/
,,3-0chi) 672 layers 1 part ri'SII A
IJ (ethylene glycol-mono-N-butyl ether) 7θ I Protective colloid (HEC, 26% 5ol) 73 1P
H regulator (ammonium hydroxide, 2t% So/) 2
Heavy J Part [Paint Formulation 2] PVC = 4θ Thio Mill-based Dispersant (Instrument Kogyo Seiyaku, Tesco) N/Da)/Resalt Part Dispersant (I Neugen EA/20) I Antifreeze (Propylene Glycol) 2θ lfl calcium carbonate (solid content 1 ots slurry) 4too
'Titanium white (6 Hara Sangyo, R-630) 23θ IO fret-unmill base emulsion (Dainippon Ink, Bonko) 23/θ [acrylic styrene resin" 166%) /, 15'g gap film forming agent (ethylene Glycol-mono-N-butyl ether) 30' Protective colloid (llEC, 2J96 Sol)
tθ Higashidaibe P H, J! Powder (ammonium hydroxide, 2
3%5ol) 3 #Repentance-/5o=-2, 700 parts of male heavy calcium carbonate and 42 parts of sodium polyacrylate as a dispersant were suspended in water to a solid content concentration of 7θ, and Create a suspension using a disper stirrer (Tokushu Kikaku) and add this to Dynoco Mill (W
Wet pulverization was performed using a pr-LOT type (manufactured by AB Company) so that S2=Jj. Using the thus obtained heavy calcium carbonate, water-based paint compositions were prepared according to the above paint formulations 1 and 2, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
実施例−コ
Ｓｏ＝λθの本質炭酸カルシウム７００部と分散剤とし
てポリアクリル酸ソーダ４３部を用い、実姉例−／のご
とく懸濁液を作成し、グイノーミルにてＳよ−ぺ３とな
るよう湿式粉砕を行ない、かかる重質炭酸カルシウムを
上記塗料配合ｌ及びλによって水系塗料組成物に調整し
、塗料性能を評価した。Example - Using 700 parts of essential calcium carbonate with So = λθ and 43 parts of sodium polyacrylate as a dispersant, a suspension was prepared as in the actual sister example, and it was made into S Yo-Pe 3 using Guino Mill. Wet grinding was performed, and the heavy calcium carbonate was prepared into a water-based paint composition using the above paint formulations 1 and λ, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
実施例−３
Ｓ０＝２２ の重質炭酸カルシウム１００部と分散剤
としてポリアクリル酸ソーダ４！部を実施例１及び２の
ごとく懸濁させ、湿式粉砕を行ない、Ｓｘ＝７ｇ とし
た。かかる重質炭酸カルシウムを上記塗料配合１及び２
によって水系塗料組成物を調整し、塗料性能を評価した
。Example-3 100 parts of heavy calcium carbonate with S0=22 and 4 parts of sodium polyacrylate as a dispersant. A portion was suspended as in Examples 1 and 2 and wet milled to give Sx = 7 g. Such heavy calcium carbonate is added to the above paint formulations 1 and 2.
A water-based paint composition was prepared and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
実施例−ダ
Ｓｏ ＝ ２１の重質炭酸カルシウムを固形分濃度３３
％となるよう水中和ラボディスパー攪拌機にて懸濁させ
、サンドグラインダーミル（五十嵐機械製造社、にＧ型
）にてＳｚ ＝ｔｊグまで湿式粉砕し、かかる重質炭酸
カルシウムを油圧式手動プレス（神藤金属工業所）にて
固形分濃度２θチまで脱水した後、重質炭酸カルシウム
固形分１０θ部に対して２θ部のポリアクリル酸ソーダ
を添加し、ラボディスパーにてスラリー化した。このよ
うにして得た重質炭酸カルシウムを塗料配合ｌ及び２に
よって水系塗料組成物を調整し、塗料性能を評価した。Example - Heavy calcium carbonate with DaSo = 21 at a solid concentration of 33
% using a water-hydration lab body spar stirrer, wet-grinding using a sand grinder mill (Igarashi Kikai Seizo Co., Ltd., model G) until Sz = tj, and then suspending the heavy calcium carbonate using a hydraulic manual press ( After dehydration to a solid content concentration of 2θ1 at Shindo Metal Industry Co., Ltd., 2θ parts of sodium polyacrylate was added to 10θ parts of heavy calcium carbonate solid content, and the mixture was slurried using a laboratory spar. Water-based paint compositions were prepared from the thus obtained heavy calcium carbonate using paint formulations 1 and 2, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
実施例−夕
５ｏ＝４０の重質炭酸カルシウム１００部と分散剤とし
てポリアクリル酸ソーダ４３部を固形分濃度７０％にな
るよう水中に懸濁させ、ラボディスパー攪拌機にて＋ｓ
ｌｌｋｌｇを作成し、これをダイノーミルにてＳ ｚ
＝ ６０ となるよう湿式粉砕を行なった。かかる重
質炭酸カルシウムの２０チ固形分水懸濁液を用い上記塗
料配合１及び２によって水系塗料を調整し、塗料性能を
評価した、
得られた結果を表に示す。Example - 100 parts of heavy calcium carbonate of 5 o = 40 and 43 parts of sodium polyacrylate as a dispersant were suspended in water to a solid content concentration of 70%, and mixed with a lab body spar stirrer for +s
Create a llklg and use a dyno mill to make S z
Wet pulverization was carried out so that the particle size was 60. A water-based paint was prepared using the 20% solid content aqueous suspension of heavy calcium carbonate according to the above paint formulations 1 and 2, and the paint performance was evaluated. The results obtained are shown in the table.
筐た上記作成した重質炭酸カルシウムは、グラインドメ
ーター（太（右手幾材’ｇｏ〜１０θＵ隅型）にて測定
しても〃μ鴎を越える粗粒子を認められなかった。Even when the above-prepared heavy calcium carbonate was measured using a grindmeter (thick (right-handed, 10θU corner type)), no coarse particles larger than 〃μ〃μ were found.
実施例−６
ｓ０＝４０の重質炭酸カルシウム１００部と分散剤とし
てポリアクリル酸ソーダ４３部を用い、実施例−ｊのご
とく懸濁液を作成し、湿式粉砕を行ないＳｓ ＝乙、θ
とした。かかる重質炭酸カルシウムの７０チ固形分水懸
濁液を用い上記塗料配合１及び２によって水系塗料を調
整し、迩科性能を評価した。Example-6 Using 100 parts of heavy calcium carbonate with s0 = 40 and 43 parts of sodium polyacrylate as a dispersant, a suspension was prepared as in Example-j and wet-pulverized to obtain Ss = B, θ.
And so. Water-based paints were prepared using the 70% solid content aqueous suspension of heavy calcium carbonate according to the paint formulations 1 and 2 above, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
また上記作成し九重質炭酸カルシウムは、グラインドメ
ーター（太佑機材製θ〜１１００ｔｔ＊型）にて測定し
ても〃μ隅を越える粗粒子ｔ−認められなかった。In addition, even when the nine-dimensional calcium carbonate prepared above was measured using a grindmeter (Model θ~1100tt* manufactured by Taiyu Kikai Co., Ltd.), no coarse particles beyond the μ corner were observed.
比較例−７
ｓｏ＝ ｘ ４ｔの重質炭酸カルシウムｔ−実施例−グ
のとと＜Ｓ＞ ＝９．コとなるよう湿式粉砕し、塗料配
合１及び２によって水系塗料組成物を調整し、塗料性能
を評価した。Comparative Example-7 so=x 4t of heavy calcium carbonate t-Example-Gnoto <S> =9. The water-based paint compositions were prepared using paint formulations 1 and 2, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
比較例−コ
Ｓ＝ｊθの乾式粉砕１分級による重質炭酸カルシウム７
００部に対し、分散剤としてポリアクリル酸ソーダ４７
部を添加し、固形分＃度７０％となるよう水中にラボデ
ィスパーにてＭＩＲＪさせ、塗料配合１及び２によって
水系塗料組成物を調整し、塗料性能を評価した。Comparative Example - Heavy calcium carbonate 7 by dry grinding 1 classification with S=jθ
00 parts, 47 parts of sodium polyacrylate as a dispersant
Aqueous paint compositions were prepared using paint formulations 1 and 2, and the paint performance was evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
比較例−３
化学反応による沈降性炭酸カルシウムを用い、塗料配合
１によって水系塗料組成物をａ４整し、塗料性能を評価
した。ただし、塗料配合２においては、高粘度のためプ
リン状となり、他の塗料性能を評価するに至らなかった
。Comparative Example 3 Using precipitated calcium carbonate produced by a chemical reaction, a water-based paint composition was adjusted to A4 according to Paint Formulation 1, and the paint performance was evaluated. However, in paint formulation 2, due to its high viscosity, it became pudding-like, and other paint properties could not be evaluated.
得られた結果を表に示す。The results obtained are shown in the table.
比較例−グ
実験室にて風簸によりＳ。−３，０の貞質炭酸力′１１
ルシウムを作成し、これを７００部としてポリアクリル
酸ン〜ダＱ３部とともに７θチ固形分となるよう水中に
投入し、ラボディスパーにて懸濁液を作成し九。かかる
重質炭酸カルシウムスラリーを用い上記塗料配合１およ
び２によって塗料性能を評価した。Comparative example - S by elutriation in the laboratory. -Create 700 parts of lucium with a carbonation capacity of -3.0 and add it to water with 3 parts of polyacrylic acid to give a solid content of 7θ, and make a suspension using a laboratory spar. Create nine. Using this heavy calcium carbonate slurry, paint performance was evaluated using the paint formulations 1 and 2 above.
また、このようにして得た重質炭酸カルシウムには、グ
ラインドメーターにて測定すると３０μ渦程度の粗大粒
子が含まれている。Furthermore, the thus obtained heavy calcium carbonate contains coarse particles of about 30 micron vortices when measured with a grind meter.
比較例−！
実験室にて風簸にエリ作成した重質炭酸カルシウム（５
Ｏ＝ｊ；７）を７００部としポリアクリル酸ソーダを分
散剤として４３部を用いてＳＬ＝乙、θまで湿式粉砕を
行なった。他の条件は同じ。Comparative example-! Heavy calcium carbonate (5
Wet pulverization was performed using 700 parts of O=j; 7) and 43 parts of sodium polyacrylate as a dispersant until SL=B and θ. Other conditions are the same.
（２０ｆｉｇＩｓ以上の粗大粒子が混入している。）比
較例−６
Ｓｏ＝弐〇の重質炭酸カルシウムをＳｚ＝達グまで湿式
粉砕。他の条件は同じ、
（ｘｔｐ畷以上の粗大粒子が混入している。Ｊ比較例−
７
Ｓｏ＝４．θの重質炭酸カルシウムをスラリー化。曲の
条件は比較例−グと同じ。(Coarse particles of 20 figs or more are mixed in.) Comparative Example-6 Heavy calcium carbonate of So=2〇 was wet-pulverized to Sz=Dagu. Other conditions are the same, (XTP coarse particles larger than Nawate are mixed.
7 So=4. θ heavy calcium carbonate is made into a slurry. The song conditions are the same as in the comparative example.
（３０μｍ以上の粗大粒子。）
塗料配合１による塗料試験成績
塗料配合２による塗料試験成績
粘 度 ＢＭ型粘度計畜３およびＡ′グローター４０ｒ
ｐｍの〃０Ｃの値を測定
光 沢 でき上り塗料を４（ｒｎｉｅのドクターブレ−
トでガラス板に塗布２ｃＰｃ ２日放置後の値を測定
耐候性 ウェザ−テスター／θ♂分カーボンアーク、７
２分シャワー塗頓温ｊｙｊθ０Ｃの条件で２００時間後
の光沢を測定、初期値の保持率で表示
へケさばき注 でき上がった塗料を実際に塗布し、その
作菓性の良し悪しにより◎〜Ｘ
で表示
隠蔽率 でき上がった塗料を隠蔽率試験紙ＴｌＣ２ｍ１
ｚのドクターブレードで塗布乾燥後黒地の白色度と白地
の白色度を測定（
黒地の白色度／白地の°白色度）Ｘ１０θのイＩＩＬで
表示
以上のごとく、本発明による粒度範囲を特定した湿式粉
砕重質炭酸カルシウムを水系塗料組成物として配合する
ことにより、水系塗料の性能を向上さ？ることかできる
。(Coarse particles of 30 μm or more.) Paint test results for paint formulation 1 Paint test results for paint formulation 2 Viscosity BM type viscosity meter 3 and A' grouter 40r
Measure the 0C value of pm Gloss Finished paint with 4 (rnie doctor brake)
2cPc applied to a glass plate with a 2-day stand.Weather resistance Weather tester/θ♂min carbon arc, 7
Measure the gloss after 200 hours under the conditions of 2-minute shower coating temperature jyjθ0C, and display according to the initial value retention rate. Display concealment rate: Put the finished paint on concealment rate test paper TlC2m1
Measure the whiteness of the black background and the whiteness of the white background after coating with a Z doctor blade and drying. Can the performance of water-based paints be improved by blending ground heavy calcium carbonate into water-based paint compositions? I can do that.
第７図１よ％ｓｏ １−ｔとＳｌ値との関係を示すグラ
フ図、第２図は、湿式粉砕方法の具体的装置を示す断面
図である。
（゛、男ＥFIG. 7 is a graph showing the relationship between %so 1-t and Sl value as shown in FIG. 1, and FIG. 2 is a sectional view showing a specific apparatus for the wet grinding method. (゛、Male E
Claims (1)
粒子径の中央１庶をｄｉ Ｘ １０−’ ｍで示し、４
７階級の中火１直ｄ１を、ｄｌ−（θ十Ｑグ）／コ＊／
Ｑ”’ ｍｓ第２ ｐｉｅ Ｇｌの中央：１ｄ２ｆ、ｄ
２＝（４ｇ−１−４ｊ）／−２・／θ−６講とし、偵次
、第３階級、第Ｚ１若級１６０１、第１θ：）６級のそ
れぞれの中央値ｄ３、”４ 、、、、 ％ ’ｎｏを−
ｄｓ＝０．３６、ｄ４ ＝（２６３ｓ ｄａ ＝（２７
Ｋ、ｄｅ＝０９、ｄマ＝が１、 ｄｅ＝２３ ％ ｄ９
＝ ３．ｊ ｓ ’ｓｏ ＝乞ｊ１とし、粒子径
が式０以上のもの全てを、４１１階級として一律にｄｚ
ｚ＝、９夕（粒子ｆｆの単ｆ）ｒはｌθづ鱒）とし、各
階級のものの京艙チをｗ５で示す）の値を用いて、次式
（１） に工って算出されるＳ１直が、次式（２）ユθイＳ乙２
θ ・・・・・（２）で示される範囲内
にあるように湿式粉砕されており、かつ、湿式粉砕が一
度もされていないときのＳ籠、即ち、Ｓｏ値が、次式（
３）％式％（３） で下されるものでｂつ７ｃ憲質炭酸カルシウムであって
、上記算出の罠めの粒子径の測定が、当咳嵐實戻戚カル
シウムの湿式粉砕前、湿式粉砕後のそれぞれの試料を、
ヘギサメタリン酸ナトリウム４２ムａＳ水メ准中、該水
〆液に対して４！〜λ＊＊Ｓ加えてｉｏ分間振とうさせ
たのちに行なわれ友ものｆｔｊｉＩｉｉ料として含んで
いることを特徴とする、水系塗料。[Claims] Semi-average particle diameter D1 (However, all particles are divided into 77 classes according to diameter, and the center of the particle diameter of each class is indicated by di x 10-' m, and 4
7 class medium heat 1 direct d1, dl-(θ1Qg)/ko*/
Q"' ms 2nd pie Gl center: 1d2f, d
2=(4g-1-4j)/-2・/θ-6 class, the median value d3, ``4'' for each of Tatsuji, 3rd grade, Z1 young grade 1601, 1st θ:)6 grade, ,,%'no−
ds=0.36, d4=(263s da=(27
K, de=09, dma=1, de=23% d9
= 3. j s 'so = bej1, and all particles with a particle diameter of formula 0 or more are uniformly dz as 411 class.
It is calculated by using the following formula (1) using the value of z = 9 (single f of particle ff, r is lθ), and the weight of each class is indicated by w5) S1 direct is the following formula (2) U θ I S Otsu 2
θ...The S basket, that is, the So value when it has been wet-milled to be within the range shown in (2) and has never been wet-milled, is calculated by the following formula (
3) It is determined by the % formula % (3), and the particle size of the above-mentioned calculation is determined by the wet grinding of the calcium carbonate. Each sample after crushing,
Sodium hegisametaphosphate 42 mu aS water solution, 4 for the water solution! ~λ**S and shaking for io minutes, and then containing the water-based paint as an additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57086202A JPS58204061A (en) | 1982-05-20 | 1982-05-20 | Water paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57086202A JPS58204061A (en) | 1982-05-20 | 1982-05-20 | Water paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58204061A true JPS58204061A (en) | 1983-11-28 |
Family
ID=13880190
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57086202A Pending JPS58204061A (en) | 1982-05-20 | 1982-05-20 | Water paint |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58204061A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6160767A (en) * | 1984-08-31 | 1986-03-28 | Maruo Calcium Kk | Water based paint |
| JPS61115971A (en) * | 1984-11-10 | 1986-06-03 | Maruo Calcium Kk | Water paint |
| JP2007537320A (en) * | 2004-05-12 | 2007-12-20 | アルファ カルツィット フィルシュトッフ ゲゼルシャフト エム・ベー・ハー | Surface-modified inorganic fillers and pigments |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5423635A (en) * | 1977-07-25 | 1979-02-22 | Shiraishi Kogyo Kaisha Ltd | Calcium carbonate pigment for use in coating |
| JPS5438077A (en) * | 1977-09-01 | 1979-03-22 | Mitsubishi Heavy Ind Ltd | Three-dimensional automatic warehouse |
| JPS5562296A (en) * | 1978-10-30 | 1980-05-10 | Omya Sa | High solid content coating agent |
| JPS5575461A (en) * | 1978-12-04 | 1980-06-06 | Aoki Kenzai Kogyo Kk | Powder substrate for synthetic resin emulsion sand wall spraying material and synthetic resin emulsion sand wall spraying material using powder substrate |
| JPS5727927A (en) * | 1980-07-23 | 1982-02-15 | Tetsuya Hanano | Modifying method for calcium carbonate particle |
-
1982
- 1982-05-20 JP JP57086202A patent/JPS58204061A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5423635A (en) * | 1977-07-25 | 1979-02-22 | Shiraishi Kogyo Kaisha Ltd | Calcium carbonate pigment for use in coating |
| JPS5438077A (en) * | 1977-09-01 | 1979-03-22 | Mitsubishi Heavy Ind Ltd | Three-dimensional automatic warehouse |
| JPS5562296A (en) * | 1978-10-30 | 1980-05-10 | Omya Sa | High solid content coating agent |
| JPS5575461A (en) * | 1978-12-04 | 1980-06-06 | Aoki Kenzai Kogyo Kk | Powder substrate for synthetic resin emulsion sand wall spraying material and synthetic resin emulsion sand wall spraying material using powder substrate |
| JPS5727927A (en) * | 1980-07-23 | 1982-02-15 | Tetsuya Hanano | Modifying method for calcium carbonate particle |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6160767A (en) * | 1984-08-31 | 1986-03-28 | Maruo Calcium Kk | Water based paint |
| JPS61115971A (en) * | 1984-11-10 | 1986-06-03 | Maruo Calcium Kk | Water paint |
| JP2007537320A (en) * | 2004-05-12 | 2007-12-20 | アルファ カルツィット フィルシュトッフ ゲゼルシャフト エム・ベー・ハー | Surface-modified inorganic fillers and pigments |
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