JPH0615032B2 - Method for producing fine particle inorganic filler-dispersion liquid - Google Patents
Method for producing fine particle inorganic filler-dispersion liquidInfo
- Publication number
- JPH0615032B2 JPH0615032B2 JP61122907A JP12290786A JPH0615032B2 JP H0615032 B2 JPH0615032 B2 JP H0615032B2 JP 61122907 A JP61122907 A JP 61122907A JP 12290786 A JP12290786 A JP 12290786A JP H0615032 B2 JPH0615032 B2 JP H0615032B2
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- Prior art keywords
- dispersion
- inorganic filler
- fine particle
- solvent
- powder
- Prior art date
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Colloid Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
【発明の詳細な説明】 [発明の分野] 本発明は、アミド系溶媒を分散媒とする微粒子状無機フ
ィラー分散液の製造法に関する。さらに詳しくは本発明
は、アミド系溶媒と該溶媒に対して20重量%以下の一
次粒子径が1.0μm以下の凝集塊状の微粒子状無機フ
ィラーとを混合して得られた混合物からフィラーの凝集
状態が低下した微粒子状無機フィラー分散液を製造する
方法に関する。Description: FIELD OF THE INVENTION The present invention relates to a method for producing a fine particle inorganic filler dispersion using an amide solvent as a dispersion medium. More specifically, the present invention relates to aggregation of fillers from a mixture obtained by mixing an amide-based solvent and an agglomerated particulate inorganic filler having a primary particle size of 20% by weight or less with respect to the solvent and having a primary particle size of 1.0 μm or less. The present invention relates to a method for producing a fine particle inorganic filler dispersion liquid in which the state is lowered.
[発明の背景] 微粒子状の二酸化チタン、シリカなどの微粒子状無機フ
ィラーを易滑剤として含む芳香族ポリイミドフィルム
は、たとえばポリイミドの前駆体であるポリアミック酸
(ポリアミド酸)を溶解状態で、そして微粒子状無機フ
ィラーを分散状態でそれぞれ含むアミド系溶媒からなる
組成物を金属面の上に流延塗布し、得られた塗布膜を加
熱して溶媒の除去と重合・イミド化を行なうような方法
により得られている。BACKGROUND OF THE INVENTION Aromatic polyimide films containing fine particulate inorganic fillers such as titanium dioxide and silica as a slip agent are, for example, polyamic acid (polyamic acid) which is a precursor of polyimide in a dissolved state and fine particulate. A composition consisting of an amide-based solvent containing an inorganic filler in a dispersed state is cast-coated on a metal surface, and the obtained coating film is heated to remove the solvent and obtain a polymer by a method such as imidization. Has been.
上記のポリアミック酸、微粒子状無機フィラーそしてア
ミド系溶媒を含む組成物は、微粒子状無機フィラーを分
散状態で含むアミド系溶媒分散液(フィラー分散液)に
ポリアミック酸もしくはポリアミック酸の製造原料(芳
香族テトラカルボン酸成分と芳香族ジアミン成分)を溶
解させて得ることができる。The composition containing the polyamic acid, the fine particle inorganic filler and the amide solvent is a polyamic acid or a raw material for producing a polyamic acid (aromatic compound) in an amide solvent dispersion liquid (filler dispersion liquid) containing the fine particle inorganic filler in a dispersed state. It can be obtained by dissolving a tetracarboxylic acid component and an aromatic diamine component).
上記のフィラー分散液は、微粒子状無機フィラーをアミ
ド系溶媒中に分散させることにより得ることができる
が、その分散操作には従来ではボールミル、サンドミル
などの機械式分散装置が用いられてきた。すなわち、微
粒子状無機フィラーとアミド系溶媒との混合物を上記の
ような機械式分散装置に導入し、これにより分散液を得
る方法が一般的に利用されてきている。The above-mentioned filler dispersion can be obtained by dispersing a fine-particle inorganic filler in an amide-based solvent, and a mechanical dispersing device such as a ball mill or a sand mill has been conventionally used for the dispersing operation. That is, a method of introducing a mixture of a fine-particle inorganic filler and an amide-based solvent into the above mechanical dispersion device to obtain a dispersion liquid is generally used.
通常の粉末の分散は上記のような機械式分散装置を用
い、所望の均一度になるまで分散操作を行なうことによ
り容易に実現できる。しかしながら、本発明者の検討に
よると、一次粒子径が極度に小さい微粒子状のフィラー
粉末をアミド系溶媒に分散する場合には、上記のような
機械式分散装置による通常の分散操作では、充分な分散
が困難であることがわかった。Ordinary powder dispersion can be easily realized by performing the dispersion operation using the mechanical dispersion device as described above until the desired homogeneity is achieved. However, according to the study of the present inventor, in the case of dispersing a fine particle filler powder having an extremely small primary particle size in an amide solvent, a normal dispersion operation using a mechanical dispersion device as described above is sufficient. It turned out to be difficult to disperse.
すなわち、たとえば一次粒子径が1.0μm程度以下の
二酸化チタン、シリカなどの微粒子状無機フィラーは、
通常の粉末状態では二次粒子、三次粒子などの凝集塊と
して存在しており、この微粒子状無機フィラーの凝集塊
は通常の分散操作によっては殆ど凝集がほどけることな
く、ほぼそのままの凝集塊として分散液に導入される。
このため、そのような凝集体を単に分散した分散液の調
製については従来の分散方法は充分に有効であるが、凝
集体の凝集状態が明らかに低下した分散液を得るために
は従来の分散方法は有効とはいえない。勿論、従来機械
式分散装置を用いる分散方法であっても、その分散条件
(たとえば、付与するせん断応力、分散時間)などを通
常の程度より過酷にすることによって、分散の程度を向
上させることは可能であるが、その分散の向上は僅かで
あって、充分とはいえない。またそのような過酷な条件
下にて機械式分散操作を行なった場合、分散装置からの
摩耗粉末の混入が無視できない量となるとの問題もあ
る。That is, for example, a fine particle inorganic filler such as titanium dioxide or silica having a primary particle diameter of about 1.0 μm or less is
In the normal powder state, it exists as agglomerates such as secondary particles and tertiary particles, and the agglomerates of the fine particle-like inorganic filler hardly agglomerate by the usual dispersion operation, and as agglomerates almost as they are. Introduced into the dispersion.
Therefore, the conventional dispersion method is sufficiently effective for the preparation of a dispersion liquid in which such agglomerates are simply dispersed, but in order to obtain a dispersion liquid in which the agglomeration state of the agglomerates is obviously reduced, the conventional dispersion method is used. The method is not effective. Of course, even in the conventional dispersion method using a mechanical dispersion device, the degree of dispersion cannot be improved by making the dispersion conditions (for example, shear stress to be applied, dispersion time) and the like more severe than usual. Although possible, the improvement in dispersion is slight and not sufficient. Further, when mechanical dispersion operation is performed under such harsh conditions, there is a problem that the amount of abrasion powder mixed in from the dispersion device becomes a nonnegligible amount.
上記の微粒子状無機フィラーの分散操作における凝集体
の解離の不充分さは、特に無機フィラーの量が少ない場
合に顕著になる。すなわち、たとえば無機フィラーの量
が分散媒体に対して20重量%程度以下、特に10重量
%以下のように少ない場合には、機械式分散操作によっ
て無機フィラー凝集体に付与されるせん断応力が低いレ
ベルにとどまるため、凝集体の解離はますます困難にな
る。The insufficient dissociation of the aggregate in the above-mentioned fine particle inorganic filler dispersion operation becomes remarkable especially when the amount of the inorganic filler is small. That is, for example, when the amount of the inorganic filler is as small as about 20% by weight or less, particularly 10% by weight or less with respect to the dispersion medium, the shear stress imparted to the inorganic filler aggregate by the mechanical dispersion operation is at a low level. Therefore, dissociation of aggregates becomes more and more difficult.
前記芳香族ポリイミドフィルム中の微粒子状無機フィラ
ーは易滑剤としてフィルム表面を適度な状態の粗面とす
る(換言すれば、フィルムの表面に適度な大きさの凹凸
を形成する)ために利用される。この場合において、無
機フィラーとして一次粒子径の非常に小さな微粒子状無
機フィラーを用いても、その凝集状態がほどけることな
くフィルム製造用組成物に導入された場合には、そのフ
ィラーは、得られるフィルム内にも同等な凝集状態で導
入されるため、フィルムの表面に形成される凹凸が大き
なものとなり、その充填目的に適合しなくなる。The fine particulate inorganic filler in the aromatic polyimide film is used as a lubricant to make the film surface a rough surface in an appropriate state (in other words, to form unevenness of an appropriate size on the surface of the film). . In this case, even if a fine particle-like inorganic filler having a very small primary particle size is used as the inorganic filler, when introduced into the film-forming composition without unraveling the aggregated state, the filler is obtained. Since it is introduced into the film in the same agglomerated state, the unevenness formed on the surface of the film becomes large and it becomes unsuitable for the filling purpose.
[発明の構成] 本発明は、少なくとも一部が凝集状態にある微粒子無機
フィラーを、その凝集状態をほどきながらアミド系溶媒
に分散して高い分散性を有する分散液を製造するための
方法を提供することを目的とする。[Structure of the Invention] The present invention provides a method for producing a dispersion having high dispersibility by dispersing a particulate inorganic filler, at least a part of which is in an aggregated state, in an amide solvent while unwinding the aggregated state. The purpose is to provide.
本発明は特に、少なくとも一部が凝集状態にある微粒子
状無機フィラーを用いて低い濃度の微粒子状無機フィラ
ーのアミド系溶媒分散液を製造する方法であって、その
凝集状態をほどきながらアミド系溶媒に分散して高い分
散性を有する分散液を製造する方法を提供することを目
的とする。The present invention is particularly a method for producing an amide-based solvent dispersion of a low-concentration fine-particle inorganic filler by using a fine-particle inorganic filler at least a part of which is an amide-based dispersion while unwinding the aggregation state. It is an object of the present invention to provide a method for producing a dispersion having high dispersibility by dispersing it in a solvent.
本発明は、アミド系溶媒と該溶媒に対して20重量%以
下の一枚粒子径が1.0μm以下の凝集塊状の微粒子状
無機フィラーとを混合して得られた混合物を分散操作に
かけてフィラー分散液を調製するに際して、該混合物中
に芳香族スルホン酸塩系分散剤を0.05〜5重量%そ
して水を0.05〜5重量%、それぞれ存在させた状態
で分散操作を施すことを特徴とする微粒子状無機フィラ
ー分散液の製造法からなる。In the present invention, a mixture obtained by mixing an amide solvent and 20% by weight or less with respect to the solvent of an agglomerate fine particle inorganic filler having a particle size of 1.0 μm or less is subjected to a dispersion operation to disperse the filler. When preparing the liquid, the dispersion operation is performed in a state in which 0.05 to 5% by weight of an aromatic sulfonate dispersant and 0.05 to 5% by weight of water are present in the mixture. And a method of producing a fine particle inorganic filler dispersion.
上記の微粒子状無機フィラー分散液の製造法は微粒子状
無機フィラーをアミド系溶媒中に0.1〜10重量%の
範囲の濃度で含まれる分散液を製造する際に特に有利で
ある。The above method for producing a fine particle inorganic filler dispersion is particularly advantageous for producing a dispersion containing a fine particle inorganic filler in an amide solvent at a concentration in the range of 0.1 to 10% by weight.
次に、本発明について詳しく説明する。Next, the present invention will be described in detail.
本発明において分散対象とされる微粒子状無機フィラー
は、一次粒子径が1.0μm以下の凝集塊状の微粒子状
無機フィラーであり、その例としては、微粒子状の銅粉
末、亜鉛粉末、アルミニウム粉末、鉄粉末、コバルト粉
末、ニッケル粉末などの金属粉末、微粒子状の二酸化チ
タン粉末、二酸化ケイ素(シリカ)粉末、酸化マグネシ
ウム粉末、酸化アルミニウム(アルミナ)粉末、酸化亜
鉛粉末などの無機酸化物粉末、微粒子状の窒化ケイ素粉
末、窒化チタン粉末などの無機室化物粉末、炭化ケイ素
粉末、炭化チタン粉末、炭化タングステン粉末などの無
機炭化物粉末、および微粒子状の炭酸カルシウム粉末、
硫酸カルシウム粉末、硫酸バリウム粉末などの無機塩粉
末を挙げることができる。これらの微粒子状無機フィラ
ーは二種以上組合せて使用されてもよい、 本発明で用いられるアミド系溶媒は芳香族ポリイミドの
製造用として用いられるものであり、その代表例として
は、ジメチルアセトアミド、ジメチルホルムアミド、N
−メチルピロリドンなどを挙げることができるが、分子
内にアミド結合を有する有機溶媒である限り特に限定は
ない。また、アミド系溶媒は、たとえばアルコール系溶
媒、ケトン系溶媒、エーテル系溶媒、エステル系溶媒、
炭化水素系溶媒、ハロゲン化炭化水素系溶媒などの各種
の公知の有機溶媒を含んでいてもよい。ただし、これら
の有機溶媒がアミド溶媒と混合される場合には、該有機
溶媒は全体量の50重量%以下であることが好ましく、
特に20重量%以下であることが好ましい。なお、本発
明において用いる芳香族スルホン酸塩系分散剤は水に対
して高い溶解性を示すため、アミド系溶媒中に少量の水
(全体量の0.05〜2重量%、特に好ましくは0.1
5〜1.5重量%)が存在していることが、本発明の目
的である高い分散効果をもたらすために必要である。The fine-particle inorganic filler to be dispersed in the present invention is an agglomerate fine-particle inorganic filler having a primary particle diameter of 1.0 μm or less, and examples thereof include fine-particle copper powder, zinc powder, aluminum powder, Metal powder such as iron powder, cobalt powder, nickel powder, fine particle titanium dioxide powder, silicon dioxide (silica) powder, magnesium oxide powder, aluminum oxide (alumina) powder, inorganic oxide powder such as zinc oxide powder, fine particle shape Silicon nitride powder, inorganic nitride powder such as titanium nitride powder, silicon carbide powder, titanium carbide powder, inorganic carbide powder such as tungsten carbide powder, and fine calcium carbonate powder,
Inorganic salt powders such as calcium sulfate powder and barium sulfate powder can be mentioned. These fine particulate inorganic fillers may be used in combination of two or more, the amide solvent used in the present invention is used for the production of aromatic polyimide, and its representative examples are dimethylacetamide and dimethyl. Formamide, N
-Methylpyrrolidone and the like can be mentioned, but there is no particular limitation as long as it is an organic solvent having an amide bond in the molecule. The amide-based solvent is, for example, an alcohol-based solvent, a ketone-based solvent, an ether-based solvent, an ester-based solvent,
It may contain various known organic solvents such as hydrocarbon solvents and halogenated hydrocarbon solvents. However, when these organic solvents are mixed with the amide solvent, the amount of the organic solvent is preferably 50% by weight or less of the total amount,
It is particularly preferably 20% by weight or less. Since the aromatic sulfonate dispersant used in the present invention has high solubility in water, a small amount of water (0.05 to 2% by weight of the total amount, particularly preferably 0%) in the amide solvent is used. .1
The presence of 5 to 1.5% by weight is necessary in order to bring about the high dispersing effect which is the object of the present invention.
本発明においては、アミド系溶媒への微粒子状無機フィ
ラーの分散補助剤として芳香族スルホン酸塩系分散剤が
用いられる。In the present invention, an aromatic sulfonate dispersant is used as a dispersion aid for the fine particle inorganic filler in the amide solvent.
芳香族スルホン酸塩系分散剤は、ベンゼン、ナフタリ
ン、アントラセン、ジフェニルなどのような芳香環ある
いはこれを水素添加した炭素環を少なくとも一個有し、
通常はこれにアルキル基などの鎖状の疎水基が結合して
なる大きな疎水基単位と親水性のスルホン酸塩が結合し
てなるものである。上記のアルキル基は通常は分岐鎖も
しくは直鎖の炭素数1〜18のアルキル基である。The aromatic sulfonate dispersant has at least one aromatic ring such as benzene, naphthalene, anthracene, and diphenyl, or a carbon ring obtained by hydrogenating the same.
Usually, a large hydrophobic group unit in which a chain-like hydrophobic group such as an alkyl group is bonded to this and a hydrophilic sulfonate are bonded. The above alkyl group is usually a branched or straight chain alkyl group having 1 to 18 carbon atoms.
芳香族スルホン酸塩系分散剤の例としては、アルキルベ
ンゼンスルホン酸塩、アルキルナフタリンスルホン酸
塩、アルキルナフタリンスルホン酸塩のホルマリン縮合
物、アルキルテトラヒドロナフタリンスルホン酸塩、ア
ルキルジフェニルスルホン酸塩、アルキルアリールスル
ホン酸塩のケトン化合物を挙げることができる。Examples of the aromatic sulfonate dispersant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, formalin condensate of alkylnaphthalene sulfonate, alkyltetrahydronaphthalene sulfonate, alkyldiphenyl sulfonate, alkylaryl sulfone. Mention may be made of ketone compounds of acid salts.
芳香族スルホン酸塩系分散剤としては、芳香族スルホン
酸塩のアルカリ金属塩(ナトリウム塩、カリウム塩な
ど)、芳香族スルホン酸のアンモニウム塩、あるいは芳
香族スルホン酸と有機アミン化合物との塩を用いること
が好ましい。As the aromatic sulfonate dispersant, an alkali metal salt of an aromatic sulfonate (sodium salt, potassium salt, etc.), an ammonium salt of an aromatic sulfonic acid, or a salt of an aromatic sulfonic acid and an organic amine compound is used. It is preferable to use.
本発明において用いる芳香族スルホン酸塩系分散剤とし
て特に好ましいのは、アルキルナフタリンスルホン酸ナ
トリウム塩のホルマリン縮合物である。Particularly preferred as the aromatic sulfonate dispersant used in the present invention is a formalin condensate of alkylnaphthalene sulfonic acid sodium salt.
アミド系溶媒と該溶媒に対して20重量%以下の一次粒
子径が1.0μm以下の凝集塊状の微粒子状無機フィラ
ーとを混合して得られた混合物を分散操作にかけてフィ
ラー分散液を調製するに際して、有機溶媒に溶解しやす
い公知のポリカルボン酸系分散剤などの通常の有機溶媒
系用分散剤を用いた場合には、その分散効果は充分でな
く、このような一般的な有機溶媒系用分散剤は通常の分
散操作を利用する限り、本発明の目的である微粒子状無
機フイラーの高度な分散を達成することができない。ま
た、通常の有機溶媒系溶分散剤を用いた場合には、高度
に分散された分散液が一旦生成しても、短時間のうちに
再凝集が発生する傾向がある。When preparing a filler dispersion liquid by subjecting a mixture obtained by mixing an amide-based solvent and 20% by weight or less of the solvent to a particulate inorganic filler in the form of agglomerates having a primary particle size of 1.0 μm or less When a conventional organic solvent-based dispersant such as a well-known polycarboxylic acid-based dispersant that is easily dissolved in an organic solvent is used, the dispersing effect is not sufficient, and such a general organic solvent-based dispersant is used. The dispersant cannot achieve a high degree of dispersion of the finely divided inorganic filler, which is the object of the present invention, as long as the usual dispersing operation is used. In addition, when an ordinary organic solvent-based dispersant is used, reaggregation tends to occur within a short time even if a highly dispersed dispersion liquid is produced.
本発明の分散液の製造法は、まず、アミド系溶媒と該ア
ミド系溶媒に対して20重量%以下の微粒子無機フィラ
ーと芳香族スルホン酸塩系分散剤(通常は10〜50重
量%濃度の水溶液として導入)とを混合して混合物を得
たのち、これに分散操作を施すことにより実施する。な
お、本発明の分散液の製造法は特に、アミド系溶媒と該
アミド系溶媒に対して0.1〜10重量%の微粒子状無
機フィラーとを混合した混合物から所望の分散液を調製
する場合に特に有効である。In the method for producing the dispersion liquid of the present invention, first, an amide solvent, a fine particle inorganic filler of 20 wt% or less with respect to the amide solvent, and an aromatic sulfonate dispersant (usually having a concentration of 10 to 50 wt% (Introduced as an aqueous solution) to obtain a mixture, which is then dispersed. The method for producing the dispersion liquid of the present invention is particularly suitable when a desired dispersion liquid is prepared from a mixture of an amide solvent and 0.1 to 10% by weight of a particulate inorganic filler with respect to the amide solvent. Especially effective for.
アミド系溶媒と微粒子状無機フィラーとの混合物は通常
の添加操作により得ることができる。なお、この混合物
には所望により公知の分散剤を併用してもよい。The mixture of the amide solvent and the particulate inorganic filler can be obtained by a usual addition operation. If desired, a known dispersant may be used in combination with this mixture.
上記のようにして得られたアミド系溶媒と微粒子状無機
フィラーとの混合物には、次に分散操作が施される。分
散操作は機械式分散装置あるいは超音波分散装置を単独
で、あるいは組合せて用いることにより行なうことがで
きる。特に、機械式分散操作と超音波分散操作とをこの
順に組合せた分散操作によることが好ましい。The mixture of the amide solvent and the particulate inorganic filler obtained as described above is then subjected to a dispersing operation. The dispersing operation can be performed by using a mechanical dispersing device or an ultrasonic dispersing device alone or in combination. In particular, it is preferable to use a dispersion operation in which a mechanical dispersion operation and an ultrasonic dispersion operation are combined in this order.
上記の機械式分散操作は公知の機械式分散装置を利用し
て行なわれる。利用することのできる機械式分散装置の
例としては、ボールミル、サンドミル、自動乳鉢、ロー
ルミル、インペラーミル、ホモジナイザーなどを挙げる
ことができる。このような機械式分散装置は、一般に回
転数700〜12000rpmの条件にて回転して固体
粒子の分散を行なう装置である。The above mechanical dispersion operation is performed using a known mechanical dispersion device. Examples of mechanical dispersing devices that can be used include ball mills, sand mills, automatic mortars, roll mills, impeller mills, and homogenizers. Such a mechanical dispersion device is generally a device that rotates under the condition of a rotation speed of 700 to 12000 rpm to disperse solid particles.
本発明における機械式分散装置はは20分間〜2時間程
度で実施するこが望ましい。この分散操作を長時間実施
すると、分散装置の摩耗粉末が少なからぬ量で分散液に
混入することがある。The mechanical dispersion device of the present invention is preferably carried out for about 20 minutes to 2 hours. If this dispersion operation is carried out for a long time, the abrasion powder of the dispersion device may be mixed in a considerable amount in the dispersion liquid.
本発明にて利用することのできる超音波分散操作は、超
音波洗浄やエマルジョンの調製などの目的にて、既に利
用されている操作である。このような操作は公知の超音
波振動子を用いて行なわれる。本発明における超音波分
散操作は、強い分散能力を達成するために15〜30K
Hz程度の低い周波数にて行なうことが望ましい。ま
た、超音波分散操作は約15分間〜10時間の範囲の操
作時間にて行なうことが望ましい。なお、超音波分散操
作によって分散液の液温が上昇する傾向があるため、超
音波分散操作が施される装置は冷却下に置くことが望ま
しい。The ultrasonic dispersion operation that can be used in the present invention is an operation that has already been used for the purpose of ultrasonic cleaning or emulsion preparation. Such an operation is performed using a known ultrasonic transducer. The ultrasonic dispersion operation in the present invention is 15 to 30K in order to achieve a strong dispersion ability.
It is desirable to perform at a frequency as low as Hz. Further, it is desirable that the ultrasonic dispersion operation is performed for an operation time in the range of about 15 minutes to 10 hours. Since the liquid temperature of the dispersion liquid tends to rise due to the ultrasonic dispersion operation, it is desirable to keep the device to which the ultrasonic dispersion operation is performed under cooling.
[発明の効果] アミド系溶媒と微粒子状無機フィラーとを混合して得ら
れた混合物からフィラー分散液を調製するに際して、本
発明に従って芳香族スルホン酸塩系分散剤を特定量そし
て水を特定量、それぞれ存在させた状態で分散操作を施
すことによって、均一な分散と凝集体の低減とが達成さ
れた分散液を容易に得ることができる。[Effects of the Invention] In preparing a filler dispersion from a mixture obtained by mixing an amide solvent and a particulate inorganic filler, a specific amount of an aromatic sulfonate dispersant and a specific amount of water according to the present invention are used. By performing the dispersion operation in the state of being respectively present, it is possible to easily obtain a dispersion liquid in which uniform dispersion and reduction of aggregates are achieved.
また、本発明に従って得られた分散液は再凝集が発生し
にくく、長期にわたって安定な分散液として存在すると
の利点もある。Further, the dispersion liquid obtained according to the present invention is less likely to cause re-aggregation, and has an advantage that it exists as a stable dispersion liquid for a long period of time.
[実施例と比較例] [実施例1] ジメチルアセトアミド494gとアルキルナフタリンス
ルホン酸ナトリウム塩のホルマリン縮合物の40重量%
水溶液3.5gとを容量1のビーカーに入れ、ホモミ
キサーを用い8000rpmの回転速度で3分間、撹拌
混合した。次に一次粒子径0.03μmに二酸化チタン
2.5gを加えてホモミキサーを用いて8000rpm
の回転速度で1時間撹拌して分散を行なった。[Examples and Comparative Examples] [Example 1] 40% by weight of a formalin condensate of 494 g of dimethylacetamide and sodium salt of alkylnaphthalenesulfonic acid.
3.5 g of the aqueous solution was placed in a beaker having a volume of 1, and mixed with stirring using a homomixer at a rotation speed of 8000 rpm for 3 minutes. Next, 2.5 g of titanium dioxide was added to the primary particle diameter of 0.03 μm and a homomixer was used to obtain 8000 rpm.
Dispersion was carried out by stirring at a rotation speed of 1 hour.
得られた分散液中の二酸化チタンの平均粒子径は0.7
5μm(堀場製作所(株)製遠心沈降式粒径分布測定装置
CAPA−500による測定値、以下同じ)であった。The average particle size of titanium dioxide in the obtained dispersion was 0.7.
5 μm (measured by centrifugal sedimentation type particle size distribution analyzer CAPA-500 manufactured by Horiba, Ltd., the same applies hereinafter).
[比較例1] アルキルナフタリンスルホン酸ナトリウム塩のホルマリ
ン縮合物の水溶液を添加しなかった以外は実施例1と同
様にして、二酸化チタンの分散操作を行なった。Comparative Example 1 Titanium dioxide was dispersed in the same manner as in Example 1 except that the aqueous solution of the formalin condensate of alkylnaphthalenesulfonic acid sodium salt was not added.
得られた分散液中の二酸化チタンの平均粒子径は1.6
μmであった。The average particle size of titanium dioxide in the obtained dispersion was 1.6.
was μm.
[比較例2] アルキルナフタリンスルホン酸ナトリウム塩のホルマリ
ン縮合物の水溶液の代りに有機溶媒溶解性アクリル径カ
ルボン酸分散剤を1.5g添加した以外は実施例1と同
様にして、二酸化チタンの分散操作を行なった。得られ
た分散液中の二酸化チタンの平均粒子径は1.0μmで
あった。[Comparative Example 2] Dispersion of titanium dioxide was carried out in the same manner as in Example 1 except that 1.5 g of an organic solvent-soluble acrylic carboxylic acid dispersant was added in place of the aqueous solution of the formalin condensate of alkylnaphthalenesulfonic acid sodium salt. The operation was performed. The average particle size of titanium dioxide in the obtained dispersion was 1.0 μm.
[実施例2] ジメチルアセトアミド97.3gとアルキルナフタリン
スルホン酸ナトリウム塩のホルマリン縮合物の40重量
%水溶液0.7gとを容量200mlのビーカーに入れ、
スターラチップを用いて5分間、撹拌混合した。次に一
次粒子径0.44μmの二酸化チタン(表面にアルミナ
処理が施されたもの)2.0gを加え、超音波洗浄器
(BRANSON社製、ウルトラクリーナ)で2時間分
散を行なった。[Example 2] 97.3 g of dimethylacetamide and 0.7 g of a 40% by weight aqueous solution of a formalin condensate of sodium salt of alkylnaphthalenesulfonic acid were placed in a beaker having a capacity of 200 ml.
Stir-mix using a stirrer tip for 5 minutes. Next, 2.0 g of titanium dioxide having a primary particle diameter of 0.44 μm (the surface of which was treated with alumina) was added, and the mixture was dispersed for 2 hours with an ultrasonic cleaner (Ultra Cleaner manufactured by BRANSON).
得られた分散液中の二酸化チタンの平均粒子径は0.5
5μmであった。The average particle size of titanium dioxide in the obtained dispersion is 0.5.
It was 5 μm.
[比較列3] アルキルナフタリンスルホン酸ナトリウム塩のホルマリ
ン縮合物の水溶液を添加しなかった以外は実施例2と同
様にして、二酸化チタンの分散操作を行なった。[Comparative column 3] Titanium dioxide was dispersed in the same manner as in Example 2 except that the aqueous solution of the formalin condensate of alkylnaphthalenesulfonic acid sodium salt was not added.
得られた分散液中の二酸化チタンの平均粒子径は1.9
μmであった。The average particle size of titanium dioxide in the obtained dispersion was 1.9.
was μm.
[実施例3] ジメチルアセトアミド4750g、アルキルナフタリン
スルホン酸ナトリウム塩のホルマリン縮合物の40重量
%水溶液50g、そして一次粒子径0.04μmの酸化
ケイ素を回転型撹拌機を用い5分間、撹拌混合した。次
に超音波ホモジナイザー(日本精機製作所(株)製、RU
S600)で4.5時間の分散を行なった。Example 3 4750 g of dimethylacetamide, 50 g of a 40% by weight aqueous solution of a formalin condensate of alkylnaphthalenesulfonic acid sodium salt, and silicon oxide having a primary particle diameter of 0.04 μm were stirred and mixed for 5 minutes using a rotary stirrer. Next, ultrasonic homogenizer (RU made by Nippon Seiki Co., Ltd., RU
In S600), dispersion was performed for 4.5 hours.
得られた分散液中の酸化ケイ素の平均粒子径は0.09
μmであった。The average particle size of silicon oxide in the obtained dispersion is 0.09.
was μm.
[実施例4] ジメチルアセトアミド97.8gとアルキルナフタリン
スルホン酸ナトリウム塩のホルマリン縮合物の40重量
%水溶液0.7gとを容量200mlのビーカーに入
れ、スターラチップを用いて5分間、撹拌混合した。次
に、一次粒子径0.03μmの二酸化チタン2.0gを
加え、超音波洗浄器(ウルトラクリーナ)で2時間の分
散を行なった。[Example 4] 97.8 g of dimethylacetamide and 0.7 g of a 40 wt% aqueous solution of a formalin condensate of sodium alkylnaphthalenesulfonate were placed in a beaker having a volume of 200 ml, and mixed with stirring using a stirrer chip for 5 minutes. Next, 2.0 g of titanium dioxide having a primary particle diameter of 0.03 μm was added, and dispersion was carried out for 2 hours with an ultrasonic cleaner (ultra cleaner).
得られた分散液中の二酸化チタンの平均粒子径は0.2
6μmであった。この分散液を1日間そして9日間静置
したのち、再度平均粒子径を測定を行なったところ平均
粒子径はそれぞれ0.28μmと0.27μmであり、
実質的な変化は認められず、この分散液が長期にわたっ
て安定であることがわかった。The average particle size of titanium dioxide in the obtained dispersion is 0.2.
It was 6 μm. After the dispersion was allowed to stand for 1 day and 9 days, the average particle size was measured again. The average particle sizes were 0.28 μm and 0.27 μm, respectively.
No substantial change was observed, demonstrating that this dispersion is stable over time.
[比較列4] アルキルナフタリンスルホン酸ナトリウム塩のホルマリ
ン縮合物の水溶液の代りに有機溶媒溶解性ポリカルボン
酸分散剤を0.3g添加した以外は実施例4と同様にし
て、二酸化チタンの分散操作を行なった。 得られた分
散液中の二酸化チタンの平均粒子径は0.12μmであ
った。この分散液を1日間と9日間静置したのち、再度
平均粒子径の測定を行なったところ平均粒子系はそれぞ
れ0.95μmと1.75μmであり、明らかな再凝集
が認められた。[Comparative column 4] Titanium dioxide dispersion operation was performed in the same manner as in Example 4 except that 0.3 g of an organic solvent-soluble polycarboxylic acid dispersant was added instead of the aqueous solution of the alkyl naphthalene sulfonic acid sodium salt formalin condensate. Was done. The average particle size of titanium dioxide in the obtained dispersion was 0.12 μm. After this dispersion was allowed to stand for 1 day and 9 days, the average particle size was measured again. The average particle sizes were 0.95 μm and 1.75 μm, respectively, and clear reaggregation was observed.
[実施例5] 二酸化チタンの代りに一次粒子径が0.016μmの酸
化マグネシウムを用いた以外は実施例4と同様にして、
酸化マグネシウムの分散操作を行なった。[Example 5] In the same manner as in Example 4 except that magnesium oxide having a primary particle diameter of 0.016 µm was used in place of titanium dioxide,
Dispersion operation of magnesium oxide was performed.
得られた分散液中の酸化マグネシウムの平均粒子径は
0.40μmであった。この分散液を1日間と9日間静
置したのち、再度平均粒子径の測定を行なったところ平
均粒子径はそれぞれ0.40μmと0.37μmであ
り、実質的な変化は認められず、この分散液が長期にわ
たって安定であることがわかった。The average particle size of magnesium oxide in the obtained dispersion was 0.40 μm. The dispersion was allowed to stand for 1 day and 9 days, and the average particle size was measured again. The average particle sizes were 0.40 μm and 0.37 μm, respectively, and no substantial change was observed. The liquid was found to be stable over the long term.
Claims (4)
以下の一次粒子径が1.0μm以下の凝集塊状の微粒子
状無機フィラーとを混合して得られた混合物を分散操作
にかけてフィラー分散液を調製するに際して、該混合物
中に芳香族スルホン酸塩系分散剤を0.05〜5重量%
そして水を0.05〜5重量%、それぞれ存在させた状
態で分散操作を施すことを特徴とする微粒子無機フィラ
ー分散液の製造法。1. An amide-based solvent and 20% by weight based on the solvent.
When a filler dispersion is prepared by subjecting a mixture obtained by mixing the following aggregated fine particle inorganic filler having a primary particle diameter of 1.0 μm or less to a filler dispersion liquid, an aromatic sulfonate dispersion in the mixture is prepared. 0.05 to 5% by weight
A method for producing a fine particle inorganic filler dispersion, which comprises performing dispersion operation in the presence of 0.05 to 5% by weight of water.
フタリンスルホン酸のナトリウム塩であることを特徴と
する特許請求の範囲第1項記載の微粒子状無機フィラー
分散液の製造法。2. The method for producing a fine particle inorganic filler dispersion according to claim 1, wherein the aromatic sulfonate dispersant is a sodium salt of alkylnaphthalene sulfonic acid.
がアミド系溶媒に対して0.1〜10重量%の範囲にあ
ることを特徴とする特許請求の範囲第1項記載の微粒子
状無機フィラー分散液の製造法。3. The particulate inorganic material according to claim 1, wherein the amount of the agglomerated particulate inorganic filler mixed is in the range of 0.1 to 10% by weight with respect to the amide solvent. Manufacturing method of filler dispersion.
ン粉末、酸化ケイ素粉末、アルミナ粉末あるいは酸化マ
グネシウム粉末であることを特徴とする特許請求の範囲
第1項記載の微粒子状無機フィラー分散液の製造法。4. The method for producing a fine particle inorganic filler dispersion according to claim 1, wherein the fine particle inorganic filler is fine particle titanium dioxide powder, silicon oxide powder, alumina powder or magnesium oxide powder. .
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61122907A JPH0615032B2 (en) | 1986-05-27 | 1986-05-27 | Method for producing fine particle inorganic filler-dispersion liquid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP61122907A JPH0615032B2 (en) | 1986-05-27 | 1986-05-27 | Method for producing fine particle inorganic filler-dispersion liquid |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62279837A JPS62279837A (en) | 1987-12-04 |
JPH0615032B2 true JPH0615032B2 (en) | 1994-03-02 |
Family
ID=14847562
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP61122907A Expired - Lifetime JPH0615032B2 (en) | 1986-05-27 | 1986-05-27 | Method for producing fine particle inorganic filler-dispersion liquid |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0615032B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20070078190A1 (en) | 2005-09-30 | 2007-04-05 | Distefano Frank V | Use of 2,3-dihydroxynaphthalene-6-sulfonic acid salts as dispersants |
JP6343269B2 (en) * | 2015-10-14 | 2018-06-13 | 永嶋 良一 | Method for decomposing agglomerated structure, and method for producing fine agglomerates composed of primary particles and / or primary particles including the same as a process |
CN115806747B (en) * | 2022-11-19 | 2024-03-29 | 中信钛业股份有限公司 | Preparation method of titanium dioxide pigment for photovoltaic backboard film |
-
1986
- 1986-05-27 JP JP61122907A patent/JPH0615032B2/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
JPS62279837A (en) | 1987-12-04 |
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