JPS59193964A - Dispersing agent for light calcium carbonate - Google Patents
Dispersing agent for light calcium carbonateInfo
- Publication number
- JPS59193964A JPS59193964A JP6760483A JP6760483A JPS59193964A JP S59193964 A JPS59193964 A JP S59193964A JP 6760483 A JP6760483 A JP 6760483A JP 6760483 A JP6760483 A JP 6760483A JP S59193964 A JPS59193964 A JP S59193964A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- calcium carbonate
- light calcium
- copolymer
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は軽質炭酸カルシウム用分散剤に関するものであ
る。さらに詳しくハ、低粘度で安定性の優れた軽質炭酸
カルシウムスラリーを可能とする分散剤に関するもので
ある。従来、炭酸カルシウム用分散剤としては、アクリ
ル酸またはメタアクリル酸重合体の塩、アクリル酸とマ
レイン酸またはフマール酸との共重合体の塩、アクリル
酸とスルホ基含有モノマーおよびマレイン酸、フマール
酸、イタコン酸などの２塩基酸よりなる共重合体の塩な
どが知られている。またアクリル酸のアルカリ金属塩８
５〜９８．５重量係とイタコン酸のアルカリ金属塩１．
５多〜１５重量係の共重合体（特公昭４７−８８０５５
） 、アクリル酸８０〜９８モルチとマレイン酸、フ
マール酸およびイタコン酸からなる群より選らばれた二
塩基酸２〜２０モル係との共重合体の塩（特開昭４８−
７９２８０）などら知られている。しかしながらこれら
の分散剤は軽質炭酸カルシウム、特に微粒子の軽質炭酸
カルシウムに対して十分な効果を発揮することができな
かった。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dispersant for light calcium carbonate. More specifically, the present invention relates to a dispersant that enables a light calcium carbonate slurry with low viscosity and excellent stability. Conventionally, dispersants for calcium carbonate include salts of acrylic acid or methacrylic acid polymers, salts of copolymers of acrylic acid and maleic acid or fumaric acid, acrylic acid and sulfo group-containing monomers, maleic acid, and fumaric acid. , salts of copolymers made of dibasic acids such as itaconic acid, and the like are known. Also, alkali metal salts of acrylic acid 8
5-98.5 weight factor and alkali metal salt of itaconic acid 1.
Copolymer with a weight ratio of 5 to 15 (Japanese Patent Publication No. 47-88055)
), a salt of a copolymer of 80 to 98 mol of acrylic acid and 2 to 20 mol of a dibasic acid selected from the group consisting of maleic acid, fumaric acid and itaconic acid (Japanese Patent Application Laid-Open No. 1983-1993)
79280), etc. However, these dispersants have not been able to exhibit sufficient effects on light calcium carbonate, particularly on fine particles of light calcium carbonate.
すなわち近年軽質炭酸カル７ウムは、紙コーティング用
顔料、填料、塗料用顔料などとしてますます重要な原料
となってきており、軽質炭酸カルシウノ・を高濃度のス
ラリーとして輸送したシまｔこ紙コーテイング用のカラ
ー用として使用する場合が多くなってきたが、従来の分
散剤では低粘度で経］」安定性の良い高濃度スラリーを
得ることは困難であった。In other words, in recent years, light calcium carbonate has become an increasingly important raw material for paper coating pigments, fillers, paint pigments, etc. However, with conventional dispersants, it has been difficult to obtain high-concentration slurries with low viscosity and good stability over time.
本発明者らはこれらの欠点を改良すべく研究を重ねた結
果本発明に到達した。すなわち本発明はアクリル酸およ
びメタアクリル酸から成る群より選らばれた不飽和モノ
カルシボン酸３０モル係以上〜８０モル係未満とイタコ
ン酸７０モル係未満〜２０モル係超過との共重合体の塩
よシなる軽質炭酸カルシウム用分散剤である。本発明に
おいて使用される不飽和モノカルボン酸はアクリル酸と
メタアクリル酸であり、両者共はぼ同等の効果を有して
いる。The present inventors have conducted repeated research to improve these drawbacks, and as a result they have arrived at the present invention. That is, the present invention provides a salt of a copolymer of an unsaturated monocarciboxylic acid selected from the group consisting of acrylic acid and methacrylic acid, from 30 to less than 80 mol, and itaconic acid, from less than 70 mol to more than 20 mol. This is a dispersant for light calcium carbonate. The unsaturated monocarboxylic acids used in the present invention are acrylic acid and methacrylic acid, and both have approximately the same effect.
不飽和モノカルボン酸とイタコン酸とのモル比は通常不
飽和モノカルボン酸３０モルチ以上〜８０モル係未満、
イタコン酸７０モル係未満〜２０モル係超過である。さ
らに好ましくは不飽和モノカルボン酸４０〜７９モル係
、イタコン酸６０〜２１モル係である。イタコン酸のモ
ル比が２０モル係以下の場合には軽質炭酸カルシ、ラム
スラリーの低粘度化が困難であり、特に６０チ以上の高
濃度スラリーを得ようとする場合スラリー粘度が高くな
ると共に経口的にスラリー粘僕の上昇が起るので好まし
くない。The molar ratio of unsaturated monocarboxylic acid to itaconic acid is usually 30 mol or more to less than 80 mol of unsaturated monocarboxylic acid,
Itaconic acid is less than 70 molar parts to more than 20 molar parts. More preferably, unsaturated monocarboxylic acid has a mole ratio of 40 to 79, and itaconic acid has a mole ratio of 60 to 21 mole. When the molar ratio of itaconic acid is less than 20 moles, it is difficult to reduce the viscosity of light calci or rum slurry, and especially when trying to obtain a highly concentrated slurry of 60 moles or more, the slurry viscosity becomes high and oral This is undesirable because it causes a rise in slurry viscosity.
イタコン酸のモル比が７０モル係以上の場合には重合度
の調節がむずかしくなシ分散性能が低下する。When the molar ratio of itaconic acid is more than 70 molar ratio, it is difficult to control the degree of polymerization and the dispersion performance deteriorates.
本発明の共重合体の塩としては、リチウム、すｌ・リウ
ム、カリウムなどのアルカリ金属塩、力ＩＬ／γウム塩
、アンモニウム塩およびアミン塩などがあげられる。こ
れらのうち好ましいものはナトリウム、カリウムおよび
アンモニウム塩である。しかし一部がカルボン酸として
残存していても−ｔｔこアルカリ土類金属塩や亜鉛など
の他の金属塩となってもよい。本発明の分散剤の重量平
均分子量は、ポリエチレングリコールを標準物質として
ゲルパーメーションクロマトグラフイーにて測定して、
通常５．０００〜２５０，０００であシ、好ましくは８
，０００〜２ Ｑ Ｏ，０００さらに好ましくは１０，
０００〜１５０，０００である。Examples of the salts of the copolymer of the present invention include alkali metal salts such as lithium, sulfur lithium, and potassium salts, IL/γ salts, ammonium salts, and amine salts. Preferred among these are sodium, potassium and ammonium salts. However, even if a part remains as a carboxylic acid, it may become other metal salts such as alkaline earth metal salts and zinc. The weight average molecular weight of the dispersant of the present invention is determined by gel permeation chromatography using polyethylene glycol as a standard substance.
Usually 5,000 to 250,000, preferably 8
,000-2 Q O,000 more preferably 10,
000 to 150,000.
重量平均分子量が５０００未満の場合には分散剤の使用
量を多く必要とすると共に粘度低下効果が低くまた２５
０．０００ ＪＪ、上の場合にも粘度低下効果が低下す
るので好捷しくない。本発明の分散剤の製造方法は、通
常の公知の方法を用いることができる。When the weight average molecular weight is less than 5,000, a large amount of dispersant is required and the viscosity lowering effect is low.
Even in the case of 0.000 JJ or more, the viscosity lowering effect is lowered, which is not preferable. The dispersant of the present invention can be produced by any conventional known method.
例えば、不飽和モノカルボン酸とイタコン酸とを通常の
重合開始剤）アソビスイソブチ′石二トルのようなアゾ
系化合物為過硫酸ナトリウム、過硫酸アンモニウムのよ
うな過硫酸塩、アスコルヒン酸−過酸化水素のようなレ
ドックス系開始剤の存在下）水またはアルコール系の溶
媒中で１０°Ｃ〜１３０°Ｃにて１〜１５時間重合させ
た後、アンモニアやアルカリにより中和することにより
容易に得ることができる。捷だ不飽和モノカルボン酸お
よびイタコン酸の一部又は全量を中和して塩の形とした
後重合することもできる。重合の方法としては単量体の
全ＩＩｌを重合槽に仕込んで重合してもよくまた滴下市
合法を用いてもよい。さらに一部の単量体を重合槽中に
入れ一部の単量体を滴下していく方法を用いてもよい。For example, unsaturated monocarboxylic acid and itaconic acid are combined with common polymerization initiators) azo compounds such as azobisisobutylene nitrate, persulfates such as sodium persulfate and ammonium persulfate, ascorhinic acid and hydrogen peroxide. It can be easily obtained by polymerizing in water or an alcoholic solvent at 10°C to 130°C for 1 to 15 hours, followed by neutralization with ammonia or alkali. can. It is also possible to neutralize part or all of the unsaturated monocarboxylic acid and itaconic acid to form a salt, followed by polymerization. As the polymerization method, all of the monomers may be charged into a polymerization tank and polymerized, or a dropping method may be used. Furthermore, a method may be used in which some of the monomers are placed in a polymerization tank and some of the monomers are dropped.
重合開始剤は重合槽中に存在させてもまた重合中に連続
的に投入していく方法を用いてもよい。本発明の分散剤
は通常、前述のように水またはアルコール系溶媒中にて
溶液重合法により製造されるが、乳化剤を存在させた鉱
油。The polymerization initiator may be present in the polymerization tank or may be continuously added during the polymerization. The dispersant of the present invention is usually produced by a solution polymerization method in water or an alcoholic solvent as described above, and mineral oil in the presence of an emulsifier.
ナフサ。１１−ヘキサン、イソパラフィンなどの疎水性
有機溶剤中に単量体の水溶液を滴下していく乳化重合法
によっても製造することができる。naphtha. It can also be produced by an emulsion polymerization method in which an aqueous solution of the monomer is dropped into a hydrophobic organic solvent such as 11-hexane or isoparaffin.
本発明の分散剤は軽質炭酸カルシウムに対して特に優れ
た効果を発揮するが、その他の顔料フレ１重質炭酸カル
シウム、酸化チタン、アルミナ。Although the dispersant of the present invention exhibits particularly excellent effects on light calcium carbonate, it can also be used with other pigments such as heavy calcium carbonate, titanium oxide, and alumina.
サテンホワイトなどの顔料に対しても有効テアル。Effective teal for pigments such as satin white.
本発明の分散剤の使用量は通常顔料に対して００１〜５
チ、好ましくは００５〜３％ さらに好ましくは０．１
〜２係である。０．０１％未満では分散効果が不十分で
ありまた５係より多い場合にはスラリーやコーティング
カラーに増粘傾向が出るので好ましくない。本発明の分
散剤は低粘度で高濃度の軽質炭酸カルシウムスラリーを
製造することが出来、得られたスラリーの経口女性性が
極めて優れているという特長を有している。また軽質炭
酸力ルンウムを含むコーティングカラー用の分散剤とし
て使用する場合においても同様の効果を発揮する。さら
にコーティングカラーを塗工する場合の塗工特性に優れ
、ストリーク等の塗工トラプルを生じさせないと共にツ
ー１〜紙の耐水性、印刷適性に悪影響を与えないという
特長ケ有している。The amount of the dispersant used in the present invention is usually 001 to 50% relative to the pigment.
H, preferably 0.05% to 3%, more preferably 0.1%
~This is Section 2. If it is less than 0.01%, the dispersion effect is insufficient, and if it is more than 5%, the slurry or coating color tends to thicken, which is not preferable. The dispersant of the present invention has the advantage that it is possible to produce a light calcium carbonate slurry with low viscosity and high concentration, and the resulting slurry has extremely excellent oral femininity. It also exhibits similar effects when used as a dispersant for coating colors containing light carbonate. Furthermore, it has excellent coating properties when applying a coating color, does not cause coating troubles such as streaks, and does not adversely affect the water resistance and printability of the paper.
以下実施例により本発明をさらに説明すが、本発明はこ
れらに限定されるものではない。The present invention will be further explained below with reference to Examples, but the present invention is not limited thereto.
製造例
アクリル酸１８０．２．９ （２，５モル）とイタコン
酸９１．８ｇ（０，７０６モル）、水２５０ｇおよび過
硫酸カリ１０ｇ２３５℃にて混合し均一溶解して、モノ
マー−触媒の混合溶液を作成した。Production Example Acrylic acid 180.2.9 (2.5 mol), itaconic acid 91.8 g (0,706 mol), water 250 g and potassium persulfate 10 g are mixed at 235°C and uniformly dissolved to mix the monomer and catalyst. A solution was created.
滴下ロート、温度計、還流冷却器、窒素導入管を備えた
４つ目フラスコに水９０．＠ ’ｉ仕込んだ後系内を窒
素置換した。攪拌下にフラスコ温度を９０゛Ｃとした後
、先に作成したモノマー−触媒混合溶液を滴下ロートよ
９３時間にわたって連続的に滴下重合を行った。この間
重合温度を８５〜９５°Ｃに保った。滴下終了後、４９
襲苛性ソーダａｉＢｙ １加えｐｔｌ ｆ ７．５に調
整し１アクリル酸−イタコン酸の共重合体ソーダ塩の水
溶液（固形分濃度４０％）を得た。（試料■）
下記のモノマー−触媒混合溶液を用いて上記と同様の重
合操作を行い試料■、■、■、■を得た。In a fourth flask equipped with a dropping funnel, thermometer, reflux condenser, and nitrogen inlet tube, add 90% water. @'i After charging, the system was replaced with nitrogen. After the flask temperature was brought to 90° C. with stirring, the previously prepared monomer-catalyst mixed solution was continuously added dropwise to the dropping funnel for 93 hours to carry out polymerization. During this time, the polymerization temperature was maintained at 85-95°C. After completion of dripping, 49
Caustic soda aiBy 1 was added and PTL f was adjusted to 7.5 to obtain an aqueous solution (solid content concentration 40%) of acrylic acid-itaconic acid copolymer soda salt. (Sample ■) Using the following monomer-catalyst mixed solution, the same polymerization operation as above was carried out to obtain samples ■, ■, ■, and ■.
東洋ソーダ製ＧＰＣカラムＧＥＬ ＰＷ （Ｇ −５０
００、Ｇ −８０００）’を使用して各試料の分子量を
測定した結果は下記の通シであった。（標準物質として
ポリエチレングリコールを使用した０ ）
比較製造例
製造例と同様の方法を用いて下記モノマー−触媒混合溶
液の重合を行い比較試料■、■を得た。Toyo Soda GPC column GEL PW (G-50
The molecular weight of each sample was measured using 00, G-8000)' and the results were as follows. (0 using polyethylene glycol as a standard substance) Comparative Production Example The following monomer-catalyst mixed solution was polymerized using the same method as in the Production Example to obtain comparative samples (1) and (2).
、比較試料■、■の重量平均分子量は製造例と同様の測
定法にて測定した結果各々２０，０００ 、４０，００
０であった。The weight average molecular weights of Comparative Samples ① and ② were measured using the same method as in the production example and were 20,000 and 40,00, respectively.
It was 0.
実施例１〜５および比較例６〜８
平均粒子径０４μｍのカルサイト系立方体状の軽質炭酸
カルシウム（奥多摩工業株式会社製月こ・表−１に示す
分散剤と水とを固形分が６５％をこなるように加え、ミ
キサーで４０分間攪拌処理した。得られｔコスラリーの
製造直後の粘度および７日後の粘度を測定し経口安定性
を調べ、その結果を表−１に示した。Examples 1 to 5 and Comparative Examples 6 to 8 Calcite-based cubic light calcium carbonate with an average particle diameter of 04 μm (Gekko manufactured by Okutama Kogyo Co., Ltd.) The dispersant shown in Table 1 and water were mixed with a solid content of 65%. The viscosity of the resulting t-cos slurry immediately after production and after 7 days was measured to examine its oral stability, and the results are shown in Table 1.
表−１に示した結果の通り、本発明の試料■〜■ケ分散
剤として作成した軽質炭酸カルシウムスラリーは、比較
例１の試料■〜■を分散剤としたスラリーに比べ明らか
に低粘度を示し、また、スラリーの経口安定性も優れて
いた。As shown in Table 1, the light calcium carbonate slurry prepared as the dispersant for Samples ① to ② of the present invention clearly has a lower viscosity than the slurry in which Samples ① to ② of Comparative Example 1 were used as the dispersant. The oral stability of the slurry was also excellent.
実施例６
平均粒子径０．２μｍのアラゴナイト系柱状の軽質炭酸
カルシウム（奥多摩工業株式会社製）に試料■の分散剤
１．０重量％（対軽質炭酸カルシウム）と水とを固形分
が７３ｑ６となるように添加し実施例１と同様の処理を
行いスラリーを傷ｔこ。得られたスラリー製造直後の粘
度は５０ ｃｐｓ （２５°Ｃ）、７日後の粘度は６１
ｃｐｓ （２５°Ｃ）であった。Example 6 Aragonite columnar light calcium carbonate (manufactured by Okutama Kogyo Co., Ltd.) with an average particle diameter of 0.2 μm was mixed with 1.0% by weight of the dispersant of sample (2) (based on light calcium carbonate) and water so that the solid content was 73q6. The slurry was added in the same manner as in Example 1 and scratched. The resulting slurry had a viscosity of 50 cps (25°C) immediately after production, and a viscosity of 61 after 7 days.
cps (25°C).
Claims (3)
選らばれた不飽和モノカルボン酸３０モル係以上〜８０
モル係未満とイタコン酸７０モル係未満〜２゜モル係超
過との共重合体の塩よシなる軽質炭酸カルシウム用分散
剤。(1) Unsaturated monocarboxylic acid selected from the group consisting of acrylic acid and methacrylic acid with a molar ratio of 30 or more to 80
A dispersant for light calcium carbonate comprising a salt of a copolymer of less than 70 molar proportions and itaconic acid in excess of 2 mmolar proportions.
シ選らばれた不飽和モノカルボン酸４０〜７９モル係と
イタコン酸６０〜２１モル係との共重合体のアルカリ金
属またはアンモニウム塩よりなる特許請求の範囲第１項
記載の分散剤。(2) Consisting of an alkali metal or ammonium salt of a copolymer of 40 to 79 mol of unsaturated monocarboxylic acid selected from the group consisting of acrylic acid and methacrylic acid and 60 to 21 mol of itaconic acid. The dispersant according to claim 1.
０，０００である特許請求の範囲第１項および第２項記
載の分散剤。(3) The weight average molecular weight of the copolymer is 5. OO'0~25
0,000, the dispersant according to claims 1 and 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58067604A JPH0653870B2 (en) | 1983-04-15 | 1983-04-15 | Light calcium carbonate dispersant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58067604A JPH0653870B2 (en) | 1983-04-15 | 1983-04-15 | Light calcium carbonate dispersant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59193964A true JPS59193964A (en) | 1984-11-02 |
| JPH0653870B2 JPH0653870B2 (en) | 1994-07-20 |
Family
ID=13349691
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58067604A Expired - Lifetime JPH0653870B2 (en) | 1983-04-15 | 1983-04-15 | Light calcium carbonate dispersant |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653870B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2574086A1 (en) * | 1984-12-03 | 1986-06-06 | Coatex Sa | WATER-SOLUBLE DISPERSING AGENT FOR PIGMENTED AQUEOUS COMPOSITIONS |
| US4775420A (en) * | 1986-08-22 | 1988-10-04 | Coatex, S.A. | Complex pigment compositions for coating of paper |
| US4818783A (en) * | 1986-11-07 | 1989-04-04 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for production of aqueous dispersion of inorganic pigment |
| WO1999023185A1 (en) * | 1997-10-30 | 1999-05-14 | Sanyo Chemical Industries, Ltd. | Pigment dispersant and pigment dispersion composition |
| JP2005290165A (en) * | 2004-03-31 | 2005-10-20 | Kao Corp | Dispersant for inorganic pigment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879230A (en) * | 1972-01-25 | 1973-10-24 | ||
| JPS5385828A (en) * | 1977-01-07 | 1978-07-28 | Rohm & Haas | Improved aqueous emulsion paint |
-
1983
- 1983-04-15 JP JP58067604A patent/JPH0653870B2/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4879230A (en) * | 1972-01-25 | 1973-10-24 | ||
| JPS5385828A (en) * | 1977-01-07 | 1978-07-28 | Rohm & Haas | Improved aqueous emulsion paint |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2574086A1 (en) * | 1984-12-03 | 1986-06-06 | Coatex Sa | WATER-SOLUBLE DISPERSING AGENT FOR PIGMENTED AQUEOUS COMPOSITIONS |
| US4775420A (en) * | 1986-08-22 | 1988-10-04 | Coatex, S.A. | Complex pigment compositions for coating of paper |
| US4818783A (en) * | 1986-11-07 | 1989-04-04 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method for production of aqueous dispersion of inorganic pigment |
| US4892902A (en) * | 1986-11-07 | 1990-01-09 | Nippon Shokubai Kagaku, Co., Ltd. | Method for production of aqueous dispersion of inorganic pigment |
| WO1999023185A1 (en) * | 1997-10-30 | 1999-05-14 | Sanyo Chemical Industries, Ltd. | Pigment dispersant and pigment dispersion composition |
| JP2005290165A (en) * | 2004-03-31 | 2005-10-20 | Kao Corp | Dispersant for inorganic pigment |
| JP4563065B2 (en) * | 2004-03-31 | 2010-10-13 | 花王株式会社 | Dispersant for inorganic pigment |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0653870B2 (en) | 1994-07-20 |
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