JPH0134272B2 - - Google Patents
Info
- Publication number
- JPH0134272B2 JPH0134272B2 JP7574981A JP7574981A JPH0134272B2 JP H0134272 B2 JPH0134272 B2 JP H0134272B2 JP 7574981 A JP7574981 A JP 7574981A JP 7574981 A JP7574981 A JP 7574981A JP H0134272 B2 JPH0134272 B2 JP H0134272B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- dispersant
- parts
- soluble polymer
- sachin white
- 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
Links
- 239000002270 dispersing agent Substances 0.000 claims description 32
- 229920003169 water-soluble polymer Polymers 0.000 claims description 29
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000002431 hydrogen Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 21
- 238000006116 polymerization reaction Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 4
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 description 3
- 239000004342 Benzoyl peroxide Substances 0.000 description 3
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- -1 amine salts Chemical class 0.000 description 3
- 235000019400 benzoyl peroxide Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229940047670 sodium acrylate Drugs 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- YLWFSLCGNVNUCH-UHFFFAOYSA-M [O-]S(O)=O.OS(O)=O.OS(O)=O.O.[Na+] Chemical compound [O-]S(O)=O.OS(O)=O.OS(O)=O.O.[Na+] YLWFSLCGNVNUCH-UHFFFAOYSA-M 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940048086 sodium pyrophosphate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
Landscapes
- Paper (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Description
本発明はサチンホワイト用分散剤に関するもの
である。より詳しくは、分散性及び安定性に優
れ、且つ高濃度でも低粘度のサチンホワイト水分
散体を与える分散剤に関するものである。
サチンホワイトは針状結晶状の白色顔料で、一
般には水酸化カルシウム懸濁液に硫酸アルミニウ
ム水溶液を添加反応させて得られる3CaO・
Al2O3・3CaSO4・31〜32H2Oなる化学式で示さ
れるスルホアミン酸カルシウムである。通常70〜
75重量%の水分を含む固いケーキ状のサチンホワ
イトペーストとして供給されているのが、分散化
困難な顔料の1つとされてきている。
従来よりサチンホワイトは特徴ある塗被顔料と
してカオリンクレー、炭酸カルシウム等とともに
用いられている。例えば、サチンホワイトを用い
て得られた塗被紙は白色度、光沢度、印刷適性等
に優れている。しかしこの場合、顔料粒子はその
粒子径が極微であり更にその分散性が優れている
ことが強く要求される。特に、現在の様に高速度
で塗工する場合、顔料の分散性が悪ければ塗工液
の見掛け粘度が増大し、流動性が悪化するため良
好な塗布はむずかしく、得られた塗被紙の諸物性
が悪くなる。
従来、サチンホワイトの分散剤としては、ピロ
リン酸ソーダ、ヘキサメタリン酸ソーダ、ポリア
クリル酸ソーダ等が知られている。しかしこれら
の分散剤ではサチンホワイト水分散体に充分な流
動性を持たせるために添加量を多くしなければな
らず、またハイシエアーでの流動特性が著しく悪
い等の欠点を有している。この様な欠点を克服す
るため、無機弗素化合物を分散剤として用いる方
法(特開昭50−117825号)が提案されているが、
易水溶性塩である無機弗素化合物を多量に添加す
ることになり、好ましくない。又、その他にも分
散剤としてアクリル酸とイタコン酸の共重合体
(特公昭47−33055号)やポリアクリル酸エステル
のケン化物(特公昭47−45411号)が開示されて
いる。しかし、これらの方法はいずれもサチンホ
ワイトが20%の低濃度での分散効果を示している
にすぎない。
本発明者等は、このような現状に鑑み、鋭意研
究を重ねた結果、サチンホワイト用分散剤として
優れた作用効果を有し、上記の如き問題点を解決
する水溶性重合体を見い出して本発明を完成する
に至つた。
従つて本発明の目的は、紙塗工用に適し、少量
の添加により高濃度且つ低粘度で、分散安定性に
優れたサチンホワイト水分散液を溶易に製造する
ことが出来る分散剤を提供するものである。
即ち、本発明のサチンホワイト用分散剤は、
一般式
(但し、式中m及びnは0又は正の整数でm+n
=1〜100であり、(−C2H4O)−単位と(−C3H6O)−
単位とはどのような順序に結合していてもよい。)
で示されるポリアルキレングリコールモノアリル
エーテル()、及び
一般式
(但し、式中R1は水素又はメチル基を表わし、
Xは水素、一価金属、二価金属、アンモニウム基
又は有機アミン基を表わす。)で示される(メタ)
アクリル酸系単量体()を、()と()の
合計に対して()が0.1重量%以上5.0重量%未
満となる比率で重合開始剤を用いて共重合させ、
必要により更にアルカリ性物質で中和して得た水
溶性重合体からなるものである。
本発明で用いられるポリアルキレングリコール
モノアリルエーテル()は前記の一般式で示さ
れるものであり、アルキレンオキシドの付加モル
数m+nが1〜100のものである。付加モル数m
+nが0では得られる共重合体のサチンホワイト
用分散剤としての性能が充分でなく、逆に100を
超える場合にはその様なポリアルキレングリコー
ルモノアリルエーテルの共重合反応性が低く、本
発明の分散剤として有効な重合体が得られない。
ポリアルキレングリコールモノアリルエーテル
()は、KOHやNaOH等のアルカリを触媒と
してアリルアルコールにエチレンオキシド及び/
又はプロピレンオキシドを直接付加する公知の方
法で合成することができる。
(メタ)アクリル酸系単量体()は前記の一
般式で示されるものであるが、具体的にはアクリ
ル酸、メタクリル酸並びにそれらの一価金属塩、
二価金属塩、アンモニウム塩及び有機アミン塩を
挙げることができる。そしてこれらの1種又は2
種以上を用いることができる。
ポリアルキレングリコールモノアリルエーテル
()及び(メタ)アクリル酸系単量体()か
ら重合開始剤を用いて共重合させて本発明の分散
剤として用いられる水溶性重合体を製造するに
は、溶媒中での重合や塊状重合等の方法により行
なうことができる。
溶媒中での重合は回分式でも連続式でも行うこ
とができ、その際使用される溶媒としては、水、
低級アルコール、水−低級アルコールの混合溶
媒、芳香族炭化水素、脂肪族炭化水素、ケトン化
合物、あるいは酢酸エチル等を挙げることができ
る。そして重合触媒としては用いられる溶媒に対
応して種々の水溶性重合開始剤、パーオキシド、
ハイドロパーオキシド及びこれらと重合促進剤と
の組合わせ、あるいはアゾ化合物等が用いられ
る。
重合温度は、用いられる溶媒や重合開始剤によ
り適宜定められるが、通常0〜120℃の範囲内で
行われる。
水を溶媒とする場合、重合触媒として亜硫酸水
素ナトリウム−酸素を用いてもよい。この場合重
合は、原料単量体を含む溶媒中に亜硫酸水素ナト
リウムを添加しながら、酸素ガスあるいは酸素と
不活性気体との混合ガスを溶媒中に吹き込み、5
〜80℃の温度範囲内で重合反応を進めることによ
り行うことができる。
塊状重合は、重合開始剤としてパーオキシド、
ハイドロパーオキシドあるいはアゾ化合物等を用
い、50〜150℃の温度範囲内で行われる。
このようにして水溶性重合体を製造するに際し
て、ポリアルキレングリコールモノアリルエーテ
ル()と(メタ)アクリル酸系単量体()と
の仕込比率、用いる重合開始剤の量、重合温度、
溶媒中での重合の場合は溶媒の種類と量等によ
り、得られる水溶性重合体の分子量を適宜調節す
ることができる。そして、本発明のサチンホワイ
ト用分散剤として用いられる水溶性重合体の分子
量は500〜100000、好ましくは1000〜20000の範囲
のものが特に有効である。
このようにして得られた水溶性重合体はそのま
までも本発明のサチンホワイト用分散剤として用
いられるが、必要に応じて更にアルカリ性物質で
中和してもよい。この様なアルカリ性物質として
は、一価金属及び二価金属の水酸化物、塩化物及
び炭酸塩、アンモニア、有機アミン等が好ましい
ものとして挙げられる。
本発明のサチンホワイト用分散剤を用いてサチ
ンホワイト水分散体を得るには、該分散剤の存在
下にサチンホワイトを水に分散させればよい。分
散剤の使用量はサチンホワイト100重量部に対し
て0.1〜5重量部、好ましくは0.5〜3重量部であ
る。
サチンホワイトを分散させる方法としては、例
えば分散剤を溶解した水溶液中にサチンホワイト
ペーストを添加して撹拌混合する方法、あるいは
サチンホワイトペーストに分散剤と水とを加えて
撹拌混合する方法等を挙げることができ、これら
の方法により作業性良く、容易にサチンホワイト
水分散体を得ることができる。撹拌混合する方法
としては例えばリボンミキサー、ニーダー、高速
デイスパー等一般に用いられる撹拌装置を使用す
ることができる。しかし、この様な分散剤及びサ
チンホワイトの添加方法や撹拌方法により本発明
の範囲が制限されるものではない。
このようにして本発明の分散剤を用いて得られ
たサチンホワイト水分散体は、従来の分散剤に比
べて少量の添加量で固形分濃度が25重量%と高濃
度で低粘度を示し、且つ分散安定性にすぐれてい
るので取り扱いがきわめて容易である。
以下、実施例及び比較例により更に詳しく説明
するが、本発明はこれらの例だけで制限されない
ことはいうまでもない。又、例中の部及び%は特
にことわりのない限り重量部及び重量%を表わす
ものとする。尚、例中の分散剤水溶液の粘度及び
サチンホワイト水分散体の粘度はすべて精機工業
研究所製ビスメトロン粘度計を用い、25℃、
60rpmの条件で測定した。又、分子量の測定はゲ
ルパーメーシヨンクロマトグラフイー(ウオータ
ーズ社製244型)を用いて行つた。
実施例 1
温度計、撹拌機、滴下ロート、ガス導入管及び
還流冷却器を備えたガラス製反応容器にポリエチ
レングリコールモノアリルエーテル(平均1分子
当り5個のエチレンオキシド単位を含むもの)
7.5部及び水389.9部を仕込み、撹拌下に反応容器
内を窒素置換し、窒素雰囲気中で95℃に加熱し
た。その後、38%アクリル酸ナトリウム水溶液
506.6部と5%過流酸アンモニウム水溶液80部と
をそれぞれ120分で添加した。添加終了後、更に
16部の5%過硫酸アンモニウム水溶液を20分で添
加した。モノマー水溶液の添加完結後、120分間
95℃に温度を保持して重合反応を完了し、水溶性
重合体(1)を得た。減圧下で濃縮して得たこの水溶
性重合体(1)の40%水溶液のPHは7.3、粘度は
267cpsであつた。又、この水溶性重合体(1)の分子
量は4100であつた。
上記の水溶性重合体(1)を分散剤として用いてサ
チンホワイト(白石工業社製)に対する分散能を
次の手順に従つて評価した。即ち、脱イオン水、
サチンホワイト及び第1表に示した量の水溶性重
合体(1)の水溶液を内容積1のステンレス製ビー
カーに仕込み、ラボデイスバー(特殊機化工業社
製、MR−L型)にて20分間撹拌を行ない、25%
のサチンホワイトスラリーを調製して各スラリー
の粘度を測定した。その結果は第1表に示した通
りであつた。
第1表に示した如く、本発明の分散剤は、従来
よりこの分野で用いられている低分子量ポリアク
リル酸ナトリウム(分子量5000)に比べて少量の
添加量で優れた分散能を有している。
実施例 2
実施例1と同じ反応容器にポリエチレングリコ
ールモノアリルエーテル(平均1分子当り10個の
エチレンオキシド単位を含むもの)9.8部及び水
441.7部を仕込み、撹拌下に反応容器内を窒素置
換し、窒素雰囲気中で沸点まで加熱した。その後
38%アクリル酸ナトリウム水溶液500.5部と5%
過硫酸アンモニウム水溶液40部とをそれぞれ120
分で添加し、添加終了後更に8部の5%過硫酸ア
ンモニウム水溶液を20分で添加した。モノマーの
添加完結後、120分間沸点に温度を保持して重合
反応を完了し、水溶性重合体(2)を得た。この水溶
性重合体(2)の40%水溶液のPHは7.5、粘度は
348cpsであつた。又、水溶性重合体(2)の分子量は
4700であつた。
上記の水溶性重合体(2)を分散剤として用いて実
施例1と同様の方法によりサチンホワイトの分散
能を評価した。その結果は第1表に示した通りで
あつた。
実施例 3
実施例1と同じ反応容器にポリプロピレングリ
コールモノアリルエーテル(平均1分子当り2個
のプロピレンオキシド単位を含むもの)1部と、
イソプロピルアルコール(以下IPAと略す。)と
水との共沸組成物(IPA/水=87.4/12.6(重量
比))495.5部とを仕込み、撹拌下に反応容器内を
窒素置換し、沸点まで加熱した。その後アクリル
酸199部、ベンゾイルパーオキシド6部及びIPA
−水共沸組成物298.5部の混合物を120分で添加し
た。添加終了後、120分間沸点に温度を保持して
重合反応を完了させた。その後40%カセイソーダ
水溶液276.2部にて中和を行ない、IPAを留去し
て水溶性重合体(3)を得た。この水溶性重合体(3)の
45%水溶液のPHは8.5、粘度は830cpsであつた。
又、水溶性重合体(3)の分子量は2800であつた。
上記の水溶性重合体(3)を分散剤として用いて実
施例1と同様の方法によりサチンホワイトの分散
能を評価した。その結果は第1表に示した通りで
あつた。
実施例 4
実施例1と同じ反応容器にイソプロピルアルコ
ール(以下IPAと略す。)285部を仕込み、撹拌下
に反応容器内を窒素置換し、窒素雰囲気中で沸点
まで加熱した。その後ポリアルキレングリコール
モノアリルエーテル(平均1分子当り18個のエチ
レンオキシド単位と2個のプロピレンオキシド単
位を含むもの)4.5部、アクリル酸295.5部、ベン
ゾイルパーオキシド3部及びIPA300部の混合物
を120分で添加し、添加終了後、更に0.6部のベン
ゾイルパーオキシドをIPA11.4部に分散させたも
のを30分毎に2回に分けて添加した。モノマー混
合物の添加完結後、120分間沸点に温度を保持し
て重合反応を完了させた。その後、40%カセイソ
ーダ水溶液410.1部にて中和した。次いでIPAを
留去し、水溶性重合体(4)を得た。この水溶性重合
体(4)の45%水溶液のPHは8.5、粘度は1920cpsであ
つた。又、水溶性重合体(4)の分子量は3000であつ
た。
上記の水溶性重合体(4)を分散剤として用いて実
施例1と同様の方法によりサチンホワイトの分散
能を評価した。その結果は第1表に示した通りで
あつた。
実施例 5
実施例1と同じ反応容器に水438.8部を仕込み、
撹拌下に反応容器内を窒素置換し、95℃に加熱し
た。その後、10%ポリエチレングリコールモノア
リルエーテル(平均1分子当り30個のエチレンオ
キシド単位を含むもの)水溶液63部と部分中和し
たアクリル酸ナトリウム(80モル%中和)の38%
水溶液378.2部及び5%過硫酸アンモニウム水溶
液120部をそれぞれ120分で添加した。添加終了
後、120分間95℃に温度を保持して重合反応を完
了させた。その後、カセイソーダ水溶液にて完全
中和して水溶性重合体(5)を得た。この水溶性重合
体(5)の40%水溶液のPHは9.0、粘度は403cpsであ
つた。又、水溶性重合体(5)の分子量は4800であつ
た。
上記の水溶性重合体(5)を分散剤として用いて実
施例1と同様の方法によりサチンホワイトの分散
能を評価した。その結果は第1表に示した通りで
あつた。
比較例 1
実施例1において、分散剤として市販の低分子
量ポリアクリル酸ナトリウム(分子量5000)を用
いる他は実施例1と同様にしてサチンホワイトス
ラリーを調製し、粘度を測定した。結果は第1表
に示した通りであつた。
The present invention relates to a dispersant for Sachin White. More specifically, the present invention relates to a dispersant that provides a satin white aqueous dispersion with excellent dispersibility and stability and low viscosity even at high concentrations. Sachin white is a white pigment in the form of needle-like crystals, and is generally obtained by adding and reacting an aqueous solution of aluminum sulfate to a suspension of calcium hydroxide.
It is calcium sulfomate represented by the chemical formula Al2O3.3CaSO4.31 ~ 32H2O . Usually 70~
Supplied as a hard cake-like sachin white paste containing 75% water by weight, it has been found to be one of the most difficult pigments to disperse. Traditionally, Sachin White has been used as a distinctive coating pigment along with kaolin clay, calcium carbonate, etc. For example, coated paper obtained using Sachin White has excellent whiteness, gloss, printability, etc. However, in this case, it is strongly required that the pigment particles have extremely fine particle diameters and excellent dispersibility. In particular, when coating at high speeds like the current one, if the dispersibility of the pigment is poor, the apparent viscosity of the coating solution will increase and the fluidity will deteriorate, making it difficult to achieve good coating. Physical properties deteriorate. Sodium pyrophosphate, sodium hexametaphosphate, sodium polyacrylate, and the like are conventionally known as dispersants for Sachin White. However, these dispersants require a large amount to be added in order to give the Sachin White aqueous dispersion sufficient fluidity, and they also have drawbacks such as extremely poor fluidity at high shear conditions. In order to overcome these drawbacks, a method using an inorganic fluorine compound as a dispersant has been proposed (Japanese Patent Application Laid-Open No. 117825/1982).
This is not preferable because a large amount of an inorganic fluorine compound, which is a readily water-soluble salt, is added. In addition, as dispersants, a copolymer of acrylic acid and itaconic acid (Japanese Patent Publication No. 47-33055) and a saponified product of polyacrylic acid ester (Japanese Patent Publication No. 47-45411) have been disclosed. However, all of these methods only demonstrate the dispersion effect at a low concentration of Sachin White of 20%. In view of the current situation, the present inventors have conducted extensive research and have discovered a water-soluble polymer that has excellent effects as a dispersant for Sachin White and solves the above problems. The invention was completed. Therefore, an object of the present invention is to provide a dispersant that is suitable for paper coating and that can easily produce a sachin white aqueous dispersion with high concentration, low viscosity, and excellent dispersion stability by adding a small amount. It is something to do. That is, the dispersant for Sachin White of the present invention has the general formula: (However, in the formula, m and n are 0 or positive integers, and m+n
= 1 to 100, and (-C 2 H 4 O)- unit and (-C 3 H 6 O)-
Units may be combined in any order. )
Polyalkylene glycol monoallyl ether () represented by, and general formula (However, in the formula, R 1 represents hydrogen or a methyl group,
X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. ) (meta)
Copolymerizing the acrylic acid monomer () using a polymerization initiator at a ratio such that () is 0.1% by weight or more and less than 5.0% by weight with respect to the total of () and (),
It consists of a water-soluble polymer obtained by further neutralizing with an alkaline substance if necessary. The polyalkylene glycol monoallyl ether () used in the present invention is represented by the above general formula, and has an added mole number m+n of 1 to 100 of alkylene oxide. Number of moles added m
If +n is 0, the resulting copolymer will not have sufficient performance as a dispersant for Sachin White, and if it exceeds 100, the copolymerization reactivity of such polyalkylene glycol monoallyl ether will be low, and the present invention A polymer that is effective as a dispersant cannot be obtained. Polyalkylene glycol monoallyl ether () is produced by converting ethylene oxide and/or allyl alcohol into allyl alcohol using an alkali such as KOH or NaOH as a catalyst.
Alternatively, it can be synthesized by a known method of directly adding propylene oxide. The (meth)acrylic acid monomer () is represented by the above general formula, and specifically includes acrylic acid, methacrylic acid, and their monovalent metal salts,
Mention may be made of divalent metal salts, ammonium salts and organic amine salts. and one or two of these
More than one species can be used. To produce the water-soluble polymer used as the dispersant of the present invention by copolymerizing polyalkylene glycol monoallyl ether () and (meth)acrylic acid monomer () using a polymerization initiator, a solvent This can be carried out by a method such as polymerization in a vacuum or bulk polymerization. Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used in this case include water,
Examples include lower alcohols, mixed solvents of water and lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ketone compounds, and ethyl acetate. Depending on the solvent used, various water-soluble polymerization initiators, peroxides,
Hydroperoxides, combinations of these with polymerization accelerators, azo compounds, etc. are used. The polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but it is usually carried out within the range of 0 to 120°C. When water is used as a solvent, sodium hydrogen sulfite-oxygen may be used as a polymerization catalyst. In this case, the polymerization is carried out by blowing oxygen gas or a mixed gas of oxygen and an inert gas into the solvent while adding sodium hydrogen sulfite to the solvent containing the raw material monomer.
This can be carried out by proceeding the polymerization reaction within a temperature range of ~80°C. Bulk polymerization uses peroxide as a polymerization initiator,
It is carried out using hydroperoxide or an azo compound, etc., within a temperature range of 50 to 150°C. When producing a water-soluble polymer in this way, the charging ratio of polyalkylene glycol monoallyl ether () and (meth)acrylic acid monomer (), the amount of polymerization initiator used, the polymerization temperature,
In the case of polymerization in a solvent, the molecular weight of the resulting water-soluble polymer can be adjusted as appropriate by adjusting the type and amount of the solvent. The molecular weight of the water-soluble polymer used as the dispersant for Sachin White of the present invention is particularly effective in the range of 500 to 100,000, preferably 1,000 to 20,000. The water-soluble polymer thus obtained can be used as it is as the dispersant for Sachin White of the present invention, but it may be further neutralized with an alkaline substance if necessary. Preferred examples of such alkaline substances include hydroxides, chlorides, and carbonates of monovalent metals and divalent metals, ammonia, and organic amines. In order to obtain an aqueous dispersion of Sachin White using the dispersant for Sachin White of the present invention, Sachin White may be dispersed in water in the presence of the dispersant. The amount of the dispersant used is 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, based on 100 parts by weight of Sachin White. Examples of methods for dispersing Sachin White include adding Sachin White Paste to an aqueous solution containing a dispersant and stirring and mixing, or adding a dispersant and water to Sachin White Paste and stirring and mixing. By these methods, a sachin white aqueous dispersion can be easily obtained with good workability. As a method for stirring and mixing, commonly used stirring devices such as a ribbon mixer, kneader, and high-speed disper can be used. However, the scope of the present invention is not limited by such methods of adding and stirring the dispersant and Sachin White. The Sachin White aqueous dispersion thus obtained using the dispersant of the present invention exhibits low viscosity at a high solids concentration of 25% by weight with a small amount added compared to conventional dispersants. In addition, it has excellent dispersion stability and is extremely easy to handle. The present invention will be explained in more detail below using Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these Examples. Furthermore, parts and percentages in the examples represent parts by weight and percentages by weight unless otherwise specified. In addition, the viscosity of the dispersant aqueous solution and the viscosity of the Sachin White aqueous dispersion in the examples were all measured using a Bismethron viscometer manufactured by Seiki Kogyo Research Institute at 25°C.
Measurement was performed at 60 rpm. Furthermore, the molecular weight was measured using gel permation chromatography (Model 244, manufactured by Waters). Example 1 Polyethylene glycol monoallyl ether (containing an average of 5 ethylene oxide units per molecule) was placed in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a gas inlet tube, and a reflux condenser.
7.5 parts and 389.9 parts of water were charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95°C in a nitrogen atmosphere. Then, 38% sodium acrylate aqueous solution
506.6 parts and 80 parts of a 5% ammonium persulfate aqueous solution were each added over 120 minutes. After addition, further
16 parts of 5% ammonium persulfate aqueous solution was added over 20 minutes. 120 minutes after completion of addition of monomer aqueous solution
The temperature was maintained at 95°C to complete the polymerization reaction, and a water-soluble polymer (1) was obtained. A 40% aqueous solution of this water-soluble polymer (1) obtained by concentrating under reduced pressure has a pH of 7.3 and a viscosity of
It was 267cps. Further, the molecular weight of this water-soluble polymer (1) was 4,100. Using the above water-soluble polymer (1) as a dispersant, the dispersibility for Sachin White (manufactured by Shiraishi Kogyo Co., Ltd.) was evaluated according to the following procedure. i.e. deionized water,
Sachin White and an aqueous solution of the water-soluble polymer (1) in the amount shown in Table 1 were placed in a stainless steel beaker with an internal volume of 1, and stirred for 20 minutes using a Labo Dice Bar (manufactured by Tokushu Kika Kogyo Co., Ltd., Model MR-L). 25%
A sachin white slurry was prepared and the viscosity of each slurry was measured. The results were as shown in Table 1. As shown in Table 1, the dispersant of the present invention has excellent dispersion ability even when added in a small amount compared to the low molecular weight sodium polyacrylate (molecular weight 5000) conventionally used in this field. There is. Example 2 In the same reaction vessel as in Example 1, 9.8 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) and water were added.
After charging 441.7 parts, the inside of the reaction vessel was purged with nitrogen while stirring, and heated to the boiling point in a nitrogen atmosphere. after that
500.5 parts of 38% sodium acrylate aqueous solution and 5%
40 parts of ammonium persulfate aqueous solution and 120 parts each
After the addition was complete, 8 parts of a 5% aqueous ammonium persulfate solution was added over 20 minutes. After the addition of the monomers was completed, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction, yielding a water-soluble polymer (2). A 40% aqueous solution of this water-soluble polymer (2) has a pH of 7.5 and a viscosity of
It was 348cps. Also, the molecular weight of the water-soluble polymer (2) is
It was 4700. The dispersibility of Sachin White was evaluated in the same manner as in Example 1 using the above water-soluble polymer (2) as a dispersant. The results were as shown in Table 1. Example 3 In the same reaction vessel as in Example 1, 1 part of polypropylene glycol monoallyl ether (containing on average 2 propylene oxide units per molecule),
Charge 495.5 parts of an azeotropic composition of isopropyl alcohol (hereinafter referred to as IPA) and water (IPA/water = 87.4/12.6 (weight ratio)), replace the inside of the reaction vessel with nitrogen while stirring, and heat to the boiling point. did. Then 199 parts of acrylic acid, 6 parts of benzoyl peroxide and IPA
- A mixture of 298.5 parts of water azeotrope was added in 120 minutes. After the addition was complete, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction. Thereafter, neutralization was performed with 276.2 parts of a 40% caustic soda aqueous solution, and IPA was distilled off to obtain a water-soluble polymer (3). This water-soluble polymer (3)
The 45% aqueous solution had a pH of 8.5 and a viscosity of 830 cps.
Further, the molecular weight of the water-soluble polymer (3) was 2,800. The dispersibility of Sachin White was evaluated in the same manner as in Example 1 using the above water-soluble polymer (3) as a dispersant. The results were as shown in Table 1. Example 4 285 parts of isopropyl alcohol (hereinafter abbreviated as IPA) was charged into the same reaction vessel as in Example 1, the inside of the reaction vessel was replaced with nitrogen while stirring, and the mixture was heated to the boiling point in a nitrogen atmosphere. Thereafter, a mixture of 4.5 parts of polyalkylene glycol monoallyl ether (containing an average of 18 ethylene oxide units and 2 propylene oxide units per molecule), 295.5 parts of acrylic acid, 3 parts of benzoyl peroxide, and 300 parts of IPA was added over 120 minutes. After the addition was completed, 0.6 parts of benzoyl peroxide dispersed in 11.4 parts of IPA was added in two portions every 30 minutes. After the addition of the monomer mixture was completed, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction. Thereafter, it was neutralized with 410.1 parts of a 40% caustic soda aqueous solution. Next, IPA was distilled off to obtain a water-soluble polymer (4). A 45% aqueous solution of this water-soluble polymer (4) had a pH of 8.5 and a viscosity of 1920 cps. Furthermore, the molecular weight of the water-soluble polymer (4) was 3,000. The dispersibility of Sachin White was evaluated in the same manner as in Example 1 using the above water-soluble polymer (4) as a dispersant. The results were as shown in Table 1. Example 5 438.8 parts of water was charged into the same reaction vessel as in Example 1,
While stirring, the inside of the reaction vessel was purged with nitrogen and heated to 95°C. Thereafter, 63 parts of a 10% aqueous solution of polyethylene glycol monoallyl ether (containing an average of 30 ethylene oxide units per molecule) and 38% of partially neutralized sodium acrylate (80 mol% neutralization) were added.
378.2 parts of an aqueous solution and 120 parts of a 5% ammonium persulfate aqueous solution were each added over 120 minutes. After the addition was complete, the temperature was maintained at 95° C. for 120 minutes to complete the polymerization reaction. Thereafter, it was completely neutralized with a caustic soda aqueous solution to obtain a water-soluble polymer (5). A 40% aqueous solution of this water-soluble polymer (5) had a pH of 9.0 and a viscosity of 403 cps. Further, the molecular weight of the water-soluble polymer (5) was 4,800. The dispersibility of Sachin White was evaluated in the same manner as in Example 1 using the above water-soluble polymer (5) as a dispersant. The results were as shown in Table 1. Comparative Example 1 Sachin white slurry was prepared in the same manner as in Example 1 except that a commercially available low molecular weight sodium polyacrylate (molecular weight 5000) was used as a dispersant, and the viscosity was measured. The results were as shown in Table 1.
【表】
第1表に示した如く、本発明の分散剤を用いれ
ば、少量の使用でも優れた分散能を発揮する。
又、従来用いられている低分子量ポリアクリル酸
ナトリウムに比べても、少量の添加で粘度の低い
サチンホワイトスラリーが得られる[Table] As shown in Table 1, when the dispersant of the present invention is used, excellent dispersion ability is exhibited even when a small amount is used.
Also, compared to the conventionally used low molecular weight sodium polyacrylate, a sachin white slurry with a lower viscosity can be obtained by adding a small amount.
Claims (1)
1〜100であり、(−C2H4O)−単位と(−C3H6O)−単
位とはどのような順序に結合していてもよい。)
で示されるポリアルキレングリコールモノアリル
エーテル()、及び一般式 (但し、式中R1は水素又はメチル基を表わし、
Xは水素、一価金属、二価金属、アンモニウム基
又は有機アミン基を表わす。)で示される(メタ)
アクリル酸系単量体()を、()と()の
合計に対して()が0.1重量%以上5.0重量%未
満となる比率で重合開始剤を用いて共重合させ、
必要により更にアルカリ性物質で中和して得た水
溶性重合体からなるサチンホワイト用分散剤。[Claims] 1. General formula (However, in the formula, m and n are 0 or positive integers, and m+n=
1 to 100, and the (-C 2 H 4 O)- and (-C 3 H 6 O)- units may be bonded in any order. )
Polyalkylene glycol monoallyl ether () represented by and the general formula (However, in the formula, R 1 represents hydrogen or a methyl group,
X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group or an organic amine group. ) (meta)
Copolymerizing the acrylic acid monomer () using a polymerization initiator at a ratio such that () is 0.1% by weight or more and less than 5.0% by weight with respect to the total of () and (),
A dispersant for Sachin White made of a water-soluble polymer obtained by further neutralizing with an alkaline substance if necessary.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7574981A JPS57192469A (en) | 1981-05-21 | 1981-05-21 | Dispersing agent for satin white |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP7574981A JPS57192469A (en) | 1981-05-21 | 1981-05-21 | Dispersing agent for satin white |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS57192469A JPS57192469A (en) | 1982-11-26 |
JPH0134272B2 true JPH0134272B2 (en) | 1989-07-18 |
Family
ID=13585216
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP7574981A Granted JPS57192469A (en) | 1981-05-21 | 1981-05-21 | Dispersing agent for satin white |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS57192469A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4714032B2 (en) * | 2006-02-01 | 2011-06-29 | 日東紡績株式会社 | Diallylamine copolymer and method for producing the same |
-
1981
- 1981-05-21 JP JP7574981A patent/JPS57192469A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS57192469A (en) | 1982-11-26 |
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