JP4517484B2 - Low viscosity silica dispersion - Google Patents
Low viscosity silica dispersion Download PDFInfo
- Publication number
- JP4517484B2 JP4517484B2 JP2000288145A JP2000288145A JP4517484B2 JP 4517484 B2 JP4517484 B2 JP 4517484B2 JP 2000288145 A JP2000288145 A JP 2000288145A JP 2000288145 A JP2000288145 A JP 2000288145A JP 4517484 B2 JP4517484 B2 JP 4517484B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- water
- acrylate
- meth
- silica particles
- 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
Links
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、シリカ粒子を水中に分散させるのに適する分散剤に関するものであり、詳しくは高濃度かつ低粘度なシリカ粒子の水系スラリー分散液に関するものである。
【0002】
【従来の技術】
シリカは塗料用の添加剤や、インクジェット受理紙の塗布剤、樹脂添加剤、研磨剤、化粧品、セメント用混和剤など多くの用途に使用されている。
シリカ粒子を水系で使用する場合、シリカ分散スラリーは比較的低濃度でも高粘度化し易いために、高濃度のスラリーを得ることは一般的に容易でない。この傾向は表面積の大きいシリカ粒子すなわち多孔質シリカ粒子で顕著であり、具体的には比表面積が250m2/g以上のシリカ粒子では低粘度で高濃度のスラリーを得ることは極めて困難であった。
シリカ分散水性スラリーの低粘度化に関して、特開平8−333144号には、ポリカルボン酸塩を分散剤として用いる方法が開示されている。しかしながら、同方法で使用されるシリカ粒子は特定なものに限定されており、同方法は一般的とは言えない。他方特開平10−310416号には、分散剤を使用せずに低粘度なシリカスラリーを得る方法として高圧ホモジナイザーを用いる方法が記載されているが、この方法には特別な装置を必要とするという問題があった。
【0003】
【発明が解決しようとする課題】
本発明は、シリカ粒子の割合が高濃度でかつ得られる分散液の粘度が低粘度なシリカ分散液を容易に得る方法を提供する。
【0004】
【課題を解決するための手段】
本発明者らは、上記課題を解決するために鋭意研究を重ねた結果、本発明を完成するに至った。すなわち、本発明は、構成単位の合計量を基準にして、(メタ)アクリル酸ヒドロキシアルキル単量体単位を60モル%以上有する水溶性重合体からなるシリカ粒子用分散液であり、該水溶性重合体が、(メタ)アクリル酸ヒドロキシアルキル重合体、あるいは(メタ)アクリル酸ヒドロキシアルキル単位と(メタ)アクリル酸若しくはそれらの塩単位又は(メタ)アクリル酸メチル単位のみからなる共重合体であるシリカ分散液である。
【0005】
【発明の実施の形態】
本発明においては、構成単位の合計量を基準にして、(メタ)アクリル酸ヒドロキシアルキル単量体単位を60モル%以上有する水溶性重合体(以下水溶性重合体という)をシリカ粒子用分散剤として使用する。水溶性重合体における(メタ)アクリル酸ヒドロキシアルキル単量体単位の好ましい割合は、80〜100モル%である。水溶性重合体における(メタ)アクリル酸ヒドロキシアルキル単量体単位の割合が60モル%未満であると、水溶性重合体によるシリカ粒子の分散性が劣る。(メタ)アクリル酸ヒドロキシアルキルの具体例としては、(メタ) アクリル酸2−ヒドロキシエチル、(メタ)アクリル酸2−ヒドロキシプロピルおよび( メタ) アクリル酸ヒドロキシブチル等が挙げられ、これらは単独でまたは2種以上併用して使用できる。この中ではアクリル酸2−ヒドロキシエチルが好ましい。
【0006】
水溶性重合体を構成する単量体として、上記(メタ)アクリル酸ヒドロキシアルキル単量体以外の単量体を使用することができる。該単量体としては、(メタ)アクリル酸若しくはそれらの塩又は(メタ)アクリル酸メチルである。
【0007】
水溶性重合体の重量平均分子量は、500〜50,000が好ましく、さらに好ましくは1,000〜20,000であり、特に好ましくは1,000〜10,000である。なお、本発明における重量平均分子量は、ゲルパーミエーションクロマトグラフィーによるポリアクリル酸ナトリウム換算のものである。
【0008】
水溶性重合体は、公知のラジカル重合法等で製造できる。例えば、水溶性単量体とそれ以外の共重合可能な単量体を通常の重合開始剤系、例えばアンモニウムまたはアルカリ金属の過硫酸塩、アゾビスイソブチロニトリル等のアゾ化合物、t−ブチルパーオキサイド等の有機過酸化物、過酸化水素等の重合開始剤、および必要に応じ亜硫酸塩、アミン化合物等の促進剤を用い、水またはアルコール系等の溶媒中で50〜150℃の温度条件下に、1〜10時間程度重合反応させ、必要に応じて溶媒の一部または全部を留出させることにより、所定の濃度の重合体溶液や粉末として重合体が得られる。必要に応じて、重合体溶液には水酸化ナトリウム等のようなアルカリ金属含有化合物および/またはアンモニアの水溶液や塩酸、硫酸等を添加してPHを調整することができる。
【0009】
上記水溶性重合体を分散剤として適用するシリカ粒子としては、比表面積が250m2/g以上である平均粒径1〜5μm程度のシリカ粒子である。また、シリカを単に水と混合して得られるシリカ濃度が50重量%のスラリー粘度が1万cps以上となるシリカに対し、本発明の分散剤を適用することが好ましい。上記のような性質を有するシリカ粒子は、通常珪酸ナトリウムと硫酸との反応によって合成される。また、シリカ粒子自体が物理的または化学的に変性されたものであってもよい。分散剤の使用量は、シリカ粒子に対し0. 1〜10重量%が好ましく、より好ましくは0. 1〜5重量%である。
【0010】
本発明における分散剤は、分散媒が水または水と極性溶媒の混合物(本発明では水媒体という)のスラリーに適用することができる。水と併用される好ましい極性溶媒としては、例えばエチレングリコールやジメチルホルムアミド、メタノール、エタノール等が挙げられる。分散媒における極性溶媒の占める比率にも特に制限はないが、スラリーを低粘度化し易い点で、極性溶媒は50重量%以下で使用するのが好ましい。本発明における分散剤の使用方法に制限はなく、シリカに対する分散効果を発現できる方法であれば、どのような方法を用いてもよい。例えば、水と分散剤を混合した水溶液にシリカを加えて撹拌しスラリーを作製した後、各種用途に用いる方法や、塗料等に分散剤を添加しシリカを混合する方法、シリカを配合した塗料等に分散剤を添加する方法等が挙げられる。
【0011】
【実施例】
以下に実施例および比較例を挙げ、本発明を更に具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、以下において、重量%は単に%と表記する。
<合成例1>
容量2リットルの四ツ口フラスコに水590. 0g を入れ、90℃に加温した後、アクリル酸2-ヒドロキシエチル400. 0g および20%過硫酸ナトリウム水溶液15. 0g をそれぞれ4時間かけて滴下し、アクリル酸2-ヒドロキシエチル重合体の水溶液を得た。得られた水溶液の固形分は40. 1%、粘度は230m Pa ・s であった。
【0012】
<合成例2>
容量2リットルの四ツ口フラスコに水590. 0g を入れ、90℃に加温した後、アクリル酸2-ヒドロキシエチル369. 6g とアクリル酸メチル30. 4g との混合液および20%過硫酸ナトリウム水溶液15. 0g をそれぞれ4時間かけて滴下し、アクリル酸2-ヒドロキシエチル/アクリル酸メチル共重合体の水溶液を得た。得られた水溶液の固形分は40. 0%、粘度は410m Pa ・s であった。
<合成例3>
容量2リットルの四ツ口フラスコに水800. 0g を入れ、90℃に加温した後、アクリル酸2-ヒドロキシエチル260. 0g と36%アクリル酸ナトリウム水溶液390. 0g との混合液および20%過硫酸ナトリウム水溶液25. 0g をそれぞれ5時間かけて滴下した後、水の一部を減圧留去してアクリル酸2-ヒドロキシエチル/アクリル酸ナトリウム共重合体の水溶液を得た。得られた水溶液の固形分は40. 0%、粘度は520m Pa ・s であった。
【0013】
<比較合成例1>
容量2リットルの四ツ口フラスコに水800. 0g を入れ、90℃に加温した後、アクリル酸2-ヒドロキシエチル94. 3g と36%アクリル酸ナトリウム水溶液849. 1g との混合液および20%過硫酸ナトリウム水溶液30. 0g をそれぞれ6時間かけて滴下した後、水の一部を減圧留去してアクリル酸2-ヒドロキシエチル/アクリル酸ナトリウム共重合体の水溶液を得た。得られた水溶液の固形分は40. 3%、粘度は620m Pa ・s であった。
上記各例で得られた重合体の単量体組成と粘度物性を一覧表にしたものが表1である。なお、表中、HEAはアクリル酸2-ヒドロキシエチル、ANa はアクリル酸ナトリウム、MAはアクリル酸メチルを示す。
【0014】
【表1】
【0015】
【実施例1〜3および比較例1〜2】
合成例1〜3で得られた重合体溶液、比較合成例1で得られた重合体溶液および市販のポリアクリル酸ナトリウム系分散剤(アロンT−40;東亞合成製)を分散剤として使用し、シリカ粒子(ニップシールHD−2;日本シリカ工業製)またはシリカ粒子(ミズカシルP−527;水澤化学工業製)を水媒体中に分散させ、以下の分散試験1および2を行った。
○分散試験1
以下の操作によって、固形分比でシリカの0.8%の分散剤を加えたシリカ濃度30%のスラリーを調製した。
容器に所定量の分散剤を水に混合し良く撹拌した後、シリカ(ニップシールHD−2;日本シリカ工業製)を投入して撹拌棒にて全体をなじませた後、ロボミックス(特殊機化工業製)にてデゾルバー羽根を使用し2000rpm で5分間撹拌し、得られたスラリーの粘度を測定した。その結果は表2に示した。
比較として分散剤を用いないスラリーの粘度も示した。
○分散試験2
分散試験1と同様の操作によりシリカ(ミズカシルP−527;水澤化学工業製)の分散を行い、固形分比でシリカの0.4%の分散剤を加えたシリカ濃度35%のスラリーを調製した。
得られたスラリー粘度の測定結果は表2に示したとおりである。
【0016】
【表2】
【0017】
【発明の効果】
本発明の水溶性重合体を使用すれば、比表面積の大きいシリカ粒子を水性媒体中に高濃度に分散させることができ、スラリーの粘度が低いシリカ分散液を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a dispersant suitable for dispersing silica particles in water, and particularly to an aqueous slurry dispersion of silica particles having a high concentration and low viscosity.
[0002]
[Prior art]
Silica is used in many applications such as paint additives, ink-jet receiving paper coatings, resin additives, abrasives, cosmetics and cement admixtures.
When silica particles are used in an aqueous system, it is generally not easy to obtain a high-concentration slurry because the silica-dispersed slurry is easily increased in viscosity even at a relatively low concentration. This tendency is remarkable for silica particles having a large surface area, that is, porous silica particles. Specifically, it is extremely difficult to obtain a slurry having a low viscosity and a high concentration with silica particles having a specific surface area of 250 m 2 / g or more. .
Regarding lowering the viscosity of a silica-dispersed aqueous slurry, JP-A-8-333144 discloses a method using a polycarboxylate as a dispersant. However, the silica particles used in the method are limited to specific ones, and the method is not general. On the other hand, JP-A-10-310416 describes a method using a high-pressure homogenizer as a method for obtaining a low-viscosity silica slurry without using a dispersant, but this method requires a special apparatus. There was a problem.
[0003]
[Problems to be solved by the invention]
The present invention provides a method for easily obtaining a silica dispersion having a high silica particle ratio and a low viscosity of the resulting dispersion.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention is a dispersion for silica particles comprising a water-soluble polymer having a hydroxyalkyl (meth) acrylate monomer unit of 60 mol% or more based on the total amount of structural units. polymer is a copolymer consisting only of (meth) hydroxyalkyl polymers of acrylic acid, or (meth) acrylic acid hydroxyalkyl units (meth) acrylic acid or salts thereof unit or (meth) acrylate units Silica dispersion.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, based on the total amount of the structural units, a water-soluble polymer (hereinafter referred to as a water-soluble polymer ) having a hydroxyalkyl monomer unit (meth) acrylate of 60 mol% or more is used as a dispersant for silica particles. Use as A preferred ratio of the hydroxyalkyl (meth) acrylate monomer unit in the water-soluble polymer is 80 to 100 mol%. If the proportion of the hydroxyalkyl (meth) acrylate monomer unit in the water-soluble polymer is less than 60 mol%, the dispersibility of the silica particles by the water-soluble polymer is poor. Specific examples of the hydroxyalkyl (meth) acrylate include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate, which are used alone or Two or more types can be used in combination. Of these, 2-hydroxyethyl acrylate is preferred.
[0006]
As the monomer constituting the water-soluble polymer , monomers other than the above-mentioned (meth) acrylic acid hydroxyalkyl monomer can be used. The monomer is (meth) acrylic acid or a salt thereof or methyl (meth) acrylate.
[0007]
The weight average molecular weight of the water-soluble polymer is preferably 500 to 50,000, more preferably 1,000 to 20,000, and particularly preferably 1,000 to 10,000. In addition, the weight average molecular weight in this invention is a sodium polyacrylate conversion by gel permeation chromatography.
[0008]
The water-soluble polymer can be produced by a known radical polymerization method or the like. For example, a water-soluble monomer and another copolymerizable monomer are mixed with a conventional polymerization initiator system, for example, an ammonium or alkali metal persulfate, an azo compound such as azobisisobutyronitrile, t-butyl, etc. Temperature conditions of 50 to 150 ° C. in a solvent such as water or alcohol using an organic peroxide such as peroxide, a polymerization initiator such as hydrogen peroxide, and an accelerator such as sulfite or an amine compound as necessary. Below, a polymer is obtained as a polymer solution or powder having a predetermined concentration by allowing the polymerization reaction to proceed for about 1 to 10 hours and distilling part or all of the solvent as necessary. If necessary, PH can be adjusted by adding an alkali metal-containing compound such as sodium hydroxide and / or an aqueous solution of ammonia, hydrochloric acid, sulfuric acid or the like to the polymer solution.
[0009]
The above water-soluble polymer and silica particles to be applied as a dispersant, a specific surface area of silica particles having an average particle size of about 1~5μm is 250 m @ 2 / g or more. In addition, it is preferable to apply the dispersant of the present invention to silica obtained by simply mixing silica with water and having a silica concentration of 50% by weight and a slurry viscosity of 10,000 cps or more. Silica particles having the above properties are usually synthesized by a reaction between sodium silicate and sulfuric acid. Further, the silica particles themselves may be physically or chemically modified. The amount of the dispersant used is preferably 0.1 to 10% by weight, more preferably 0.1 to 5% by weight, based on the silica particles.
[0010]
The dispersant in the present invention can be applied to a slurry in which the dispersion medium is water or a mixture of water and a polar solvent (referred to as an aqueous medium in the present invention) . Preferred polar solvents used in combination with water include, for example, ethylene glycol, dimethylformamide, methanol, ethanol and the like. The ratio of the polar solvent in the dispersion medium is not particularly limited, but the polar solvent is preferably used in an amount of 50% by weight or less from the viewpoint of easily reducing the viscosity of the slurry. There is no restriction | limiting in the usage method of the dispersing agent in this invention, What kind of method may be used if it is a method which can express the dispersion effect with respect to a silica. For example, after adding silica to an aqueous solution in which water and a dispersant are mixed and stirring to prepare a slurry, a method used for various purposes, a method of adding a dispersant to a paint and mixing silica, a paint containing silica, etc. And a method of adding a dispersant to the above.
[0011]
【Example】
EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples. In the following,% by weight is simply expressed as%.
<Synthesis Example 1>
In a two-liter four-necked flask, add 590.0 g of water and warm to 90 ° C. Then, 40.0 g of 2-hydroxyethyl acrylate and 15.0 g of a 20% aqueous sodium persulfate solution are added dropwise over 4 hours. An aqueous solution of 2-hydroxyethyl acrylate polymer was obtained. The obtained aqueous solution had a solid content of 40.1% and a viscosity of 230 m Pa · s.
[0012]
<Synthesis Example 2>
In a four-necked flask with a capacity of 2 liters, 590.0 g of water was added and heated to 90 ° C., then, a mixture of 369.6 g of 2-hydroxyethyl acrylate and 30.4 g of methyl acrylate and 20% sodium persulfate An aqueous solution of 2-hydroxyethyl acrylate / methyl acrylate copolymer was obtained by dropping 15.0 g of the aqueous solution over 4 hours. The obtained aqueous solution had a solid content of 40.0% and a viscosity of 410 m Pa · s.
<Synthesis Example 3>
After putting 80.0 g of water in a two-liter four-necked flask and heating to 90 ° C., a mixture of 200.0 g of 2-hydroxyethyl acrylate and 390.0 g of 36% aqueous sodium acrylate solution and 20% After 25.0 g of an aqueous sodium persulfate solution was added dropwise over 5 hours, a part of the water was distilled off under reduced pressure to obtain an aqueous solution of 2-hydroxyethyl acrylate / sodium acrylate copolymer. The obtained aqueous solution had a solid content of 40.0% and a viscosity of 520 m Pa · s.
[0013]
<Comparative Synthesis Example 1>
After putting 80.0 g of water in a two-liter four-necked flask and heating to 90 ° C., a mixture of 94.3 g of 2-hydroxyethyl acrylate and 849.1 g of 36% aqueous sodium acrylate solution and 20% After 30.0 g of an aqueous sodium persulfate solution was added dropwise over 6 hours, a part of the water was distilled off under reduced pressure to obtain an aqueous solution of 2-hydroxyethyl acrylate / sodium acrylate copolymer. The obtained aqueous solution had a solid content of 40.3% and a viscosity of 620 mPa · s.
Table 1 shows a list of monomer compositions and viscosity properties of the polymers obtained in the above examples. In the table, HEA represents 2-hydroxyethyl acrylate, ANa represents sodium acrylate, and MA represents methyl acrylate.
[0014]
[Table 1]
[0015]
Examples 1-3 and Comparative Examples 1-2
The polymer solution obtained in Synthesis Examples 1 to 3, the polymer solution obtained in Comparative Synthesis Example 1 and a commercially available sodium polyacrylate dispersant (Aron T-40; manufactured by Toagosei Co., Ltd.) were used as dispersants. Silica particles (Nipseal HD-2; manufactured by Nippon Silica Industry Co., Ltd.) or silica particles (Mizukasil P-527; manufactured by Mizusawa Chemical Industry Co., Ltd.) were dispersed in an aqueous medium, and the following dispersion tests 1 and 2 were conducted.
○ Dispersion test 1
A slurry with a silica concentration of 30% was prepared by adding a 0.8% dispersant of silica in a solid content ratio by the following operation.
After mixing a predetermined amount of the dispersant in water and stirring well, add silica (Nipseal HD-2; manufactured by Nippon Silica Kogyo Co., Ltd.) and blend the whole with a stirring rod. (Manufactured by Kogyo Co., Ltd.) and stirred at 2000 rpm for 5 minutes using a resolver blade, and the viscosity of the resulting slurry was measured. The results are shown in Table 2.
For comparison, the viscosity of a slurry without a dispersant is also shown.
○ Dispersion test 2
Silica (Mizukasil P-527; made by Mizusawa Chemical Co., Ltd.) was dispersed by the same operation as in dispersion test 1, and a slurry with a silica concentration of 35% was prepared by adding a 0.4% dispersant of silica in the solid content ratio. .
The measurement results of the obtained slurry viscosity are as shown in Table 2.
[0016]
[Table 2]
[0017]
【The invention's effect】
If the water-soluble polymer of the present invention is used, silica particles having a large specific surface area can be dispersed in an aqueous medium at a high concentration, and a silica dispersion having a low slurry viscosity can be obtained.
Claims (3)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000288145A JP4517484B2 (en) | 2000-09-22 | 2000-09-22 | Low viscosity silica dispersion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000288145A JP4517484B2 (en) | 2000-09-22 | 2000-09-22 | Low viscosity silica dispersion |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2002095949A JP2002095949A (en) | 2002-04-02 |
JP4517484B2 true JP4517484B2 (en) | 2010-08-04 |
Family
ID=18771782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000288145A Expired - Lifetime JP4517484B2 (en) | 2000-09-22 | 2000-09-22 | Low viscosity silica dispersion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4517484B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB0526231D0 (en) | 2005-12-22 | 2006-02-01 | Eastman Kodak Co | Dispersant for reducing viscosity of solids |
JP4767093B2 (en) * | 2006-06-06 | 2011-09-07 | 住友大阪セメント株式会社 | Dispersant for silica fume slurry, silica fume slurry and method for producing concrete |
DE102006044520A1 (en) * | 2006-09-21 | 2008-04-03 | H.C. Starck Gmbh | Process for the preparation of solids-rich silica sols |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60123564A (en) * | 1983-12-07 | 1985-07-02 | Kansai Paint Co Ltd | Aqueous pigment dispersion |
JPH09132740A (en) * | 1995-11-07 | 1997-05-20 | Asahi Glass Co Ltd | Ink for ink jet and substrate with color filter |
JPH10324842A (en) * | 1997-05-27 | 1998-12-08 | Sekisui Chem Co Ltd | Coating composition |
-
2000
- 2000-09-22 JP JP2000288145A patent/JP4517484B2/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS60123564A (en) * | 1983-12-07 | 1985-07-02 | Kansai Paint Co Ltd | Aqueous pigment dispersion |
JPH09132740A (en) * | 1995-11-07 | 1997-05-20 | Asahi Glass Co Ltd | Ink for ink jet and substrate with color filter |
JPH10324842A (en) * | 1997-05-27 | 1998-12-08 | Sekisui Chem Co Ltd | Coating composition |
Also Published As
Publication number | Publication date |
---|---|
JP2002095949A (en) | 2002-04-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5028565B2 (en) | Method for producing heavy calcium carbonate slurry | |
EP2107087A1 (en) | Process for Grinding Minerals in Aqueous Dispersion Using A Dispersing Agent Comprising Homopolymers and/or Copolymers of (Meth)Acrylic Acid | |
TW552298B (en) | Starch degradation/graft polymerization composition process, and uses thereof | |
EP2742013B1 (en) | Process for drying concrete dispersants | |
JP4517484B2 (en) | Low viscosity silica dispersion | |
JPS60155567A (en) | Manufacture of binder bor ceramic | |
JP2007533787A (en) | Water-soluble sulfo group-containing copolymers and terpolymers, processes for their preparation and their use as stabilizers for aqueous building material systems, aqueous paint systems and aqueous coating systems | |
TW200406460A (en) | Synthetic resin emulsion powder | |
JPWO2020085123A1 (en) | Composition for aqueous coating liquid containing a polymer of N-vinylcarboxylic acid amide | |
JP4071182B2 (en) | Admixture or joint material for synthetic resin powder and hydraulic material | |
JP2913719B2 (en) | Dispersant | |
JP4457447B2 (en) | Pigment dispersant | |
JP2010077541A (en) | Water-soluble polymer dispersion, paper-strengthening agent, freeness-improving agent for making paper and yield-improving agent for making paper | |
JP2001342260A (en) | Synthetic resin emulsion powder | |
JPH1095943A (en) | Aqueous pigment-containing recording liquid | |
WO1998044044A1 (en) | Highly stable aqueous solution of partially saponified vinyl ester resin | |
JP4738726B2 (en) | Synthetic resin emulsion powder and use thereof | |
JP4913462B2 (en) | Aqueous emulsion | |
WO2007094076A1 (en) | Process for producing slurry of heavy calcium carbonate | |
JPS59193964A (en) | Dispersing agent for light calcium carbonate | |
JP3728485B2 (en) | Aqueous emulsion composition | |
JP4435292B2 (en) | Water-based adhesive composition for ball-point pen type adhesive and ball-point pen-type adhesive incorporating the same | |
JP3481788B2 (en) | Synthetic resin powder | |
JP2004131719A (en) | Powder from synthetic resin emulsion | |
JPH0555179B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070219 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100202 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100224 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20100323 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100406 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100427 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100510 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 4517484 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140528 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
EXPY | Cancellation because of completion of term |