JPH026693A - Paper coating composition with high solid content - Google Patents
Paper coating composition with high solid contentInfo
- Publication number
- JPH026693A JPH026693A JP11765389A JP11765389A JPH026693A JP H026693 A JPH026693 A JP H026693A JP 11765389 A JP11765389 A JP 11765389A JP 11765389 A JP11765389 A JP 11765389A JP H026693 A JPH026693 A JP H026693A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- coating composition
- paper coating
- latex
- paper
- 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.)
- Pending
Links
- 239000007787 solid Substances 0.000 title claims abstract description 24
- 239000008199 coating composition Substances 0.000 title claims abstract description 21
- 239000004816 latex Substances 0.000 claims abstract description 23
- 229920000126 latex Polymers 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 18
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000004927 clay Substances 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 7
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 6
- 150000001993 dienes Chemical class 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229920001577 copolymer Polymers 0.000 claims abstract description 3
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 3
- 239000000460 chlorine Substances 0.000 abstract 2
- 229910052801 chlorine Inorganic materials 0.000 abstract 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 3
- 239000000976 ink Substances 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000011115 styrene butadiene Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 239000002562 thickening agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 235000011148 calcium chloride Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000003490 calendering Methods 0.000 description 2
- 239000012986 chain transfer agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic acid Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229950005228 bromoform Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paper (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、紙塗被組成物、さらに詳しくは塗被紙に良好
な性状バランス特に光沢及び表面強度（紙むけ）特性を
与える良好な流動性を有する、固形物含量の高い紙塗被
組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a paper coating composition, more particularly a solids content having good flowability which gives the coated paper a good balance of properties, particularly gloss and surface strength (paper picking) properties. paper coating compositions with high
カルボキシル化スチレン−ブタジェンラテックスは、少
なくとも１９６０年代の初期から、紙塗被工業に提供さ
れている。その時代に販売された代表的なラテックスは
、ＡＲＣ０社から販売されたに−５５であり、スチレン
−ブタジェンラテックスは約１〜２％のカルボキシル基
を含有する。Carboxylated styrene-butadiene latexes have been available to the paper coatings industry since at least the early 1960's. A typical latex sold in that era was Ni-55, sold by ARC0, a styrene-butadiene latex containing about 1-2% carboxyl groups.
１９６８年８月２７日発行のＤｏｗ Ｃｈｅｍｉｃａ１
社に対するＵＳＰ ３３９９０８０には、カルボン酸２
〜１０重量％、０４〜Ｃ９−共役ジオレフィン６０〜５
０重量％及び単量体組成物（アルケニル単核芳香族単量
体１０〜１００重量％及び残余のアクリルニトリルから
成る）４８〜６８重量％から構成されたラテックス重合
体を使用することが開示されている。Dow Chemica1 published August 27, 1968
USP 3399080 to the company includes carboxylic acid 2
~10% by weight, 04-C9-conjugated diolefin 60-5
It is disclosed to use a latex polymer composed of 0% by weight and 48% to 68% by weight of the monomer composition (consisting of 10% to 100% by weight of alkenyl mononuclear aromatic monomer and the balance acrylonitrile). ing.
前記のラテックスは、中程度の固形物含量の紙塗被組成
物に用いられ、１９６０年代の中頃から１９７０年代の
中頃までの紙塗被工程での使用に好適であった。本発明
の紙塗被組成物は、ＵＳＰ ３３９９０８０の例中に教
示されている６０％の固形物含量より高い固形形含量を
有する。These latexes are used in medium solids content paper coating compositions and were suitable for use in paper coating processes from the mid-1960's to the mid-1970's. The paper coating compositions of the present invention have a solids content higher than the 60% solids content taught in the example of USP 3,399,080.
この技術における次の大きな進歩は、１９７９年５月１
５日発行のＰｏｔｌａｔｃｈ Ｆｏｒｅｓｔ社に対する
ＵＳＰ４１５４８９９ （Ｈｅｒｓｈｅｙ特許）であり
、そこには良好な流動性を有する固形物含量の高い紙塗
被料が開示されている。不運にも、Ｈｅｒｓｈｅｙ ％
許の組成物はカルボキシル化ラテックスの使用を特定し
ているにすぎない。本発明者らは、特定のカルボキシル
化ラテックスを用いることにより、好適な流動特性を保
持しながら、改善された表面強度及び光沢特性が得られ
ることを見出した。The next major advance in this technology occurred on May 1, 1979.
USP 4,154,899 (Hershey Patent) to Potlatch Forest, published on May 5, 2003, which discloses a high solids content paper coating with good flow properties. Unfortunately, Hershey%
The present composition only specifies the use of carboxylated latex. The inventors have discovered that by using certain carboxylated latexes, improved surface strength and gloss properties can be obtained while retaining suitable flow properties.
１９７６年１０月１２日発行のＭｏｏｒｅ ａｎｄＭｕ
ｎ ｇ ｅ ｒに対するＵＳＰ ３９８５９３２には、
固形物含量の高い紙塗被組成物が開示されている。この
組成物中の必須成分は、硬質の高分子量ワックスである
。本発明はこのようなワックスの使用を意図していない
。Moore and Mu, published October 12, 1976
USP 3985932 for n g e r
Paper coating compositions with high solids content are disclosed. An essential ingredient in this composition is a hard, high molecular weight wax. The present invention does not contemplate the use of such waxes.
日本特許８２３６１９５のケミカル・アブストラフ）９
７：１１１５２２ｕには、固形物含量の高い紙塗被組成
物が開示されている。この組成物には、結合剤として混
合エチレン性不飽和カルボン酸、ブタジェン、スチレン
及びメチルメタクリレートから成るラテックスが用いら
れる。本発明の重合体組成物はアルキル（メタ）アクリ
レートを含有しない。Chemical Abstraf (Japanese Patent No. 8236195) 9
7:111522u discloses paper coating compositions with a high solids content. This composition uses a latex consisting of mixed ethylenically unsaturated carboxylic acids, butadiene, styrene and methyl methacrylate as a binder. The polymer composition of the present invention does not contain alkyl (meth)acrylates.
本発明の目的は、良好な流動性及び多価好ましくは２価
のイオンに対する良好な安定性を有し、そして高い光沢
及び表面強度を含む特性が良好に調和した塗被紙を与え
る、固形分含量の高い単純な塗被組成物を提供すること
である。The object of the present invention is to provide a coated paper with good flowability and good stability towards multivalent, preferably divalent ions, and with a good blend of properties including high gloss and surface strength, with a solids content of The object of the present invention is to provide a simple coating composition with high content.
本発明は、クレー１００〜４０重量％及び炭酸カルシウ
ム、アルミニウム三水和物、二酸化チタン及び硫酸バリ
ウムから成る群から選ばれた１種以上の成分０〜６０重
量％から成る組成物９５〜８５乾燥重量％、ならびに
非置換の又は０１〜Ｃ４−アルキル基もしくは塩素原子
により置換された０８〜ｃ１□−ビニル芳香族単量体５
５〜６５重量％、非置換の又は塩素原子により置換され
た分枝状又は直鎖状のｃ４〜ｃ６〜共役ジオレフィン３
０〜４０重量％及び１種以上ノ０３〜Ｃ６−エチレン性
不飽和カルボン酸４〜１０重景重量共重合体から成り、
１０％ＣａＣｌ２に浸漬したときに０．５重量％未滴の
凝集物を生成するラテックス５〜１５乾燥重量％から構
成され、
６５〜７５重量％の固形物含量及び８０センチポイズ未
滴の粘度（Ｅボブ及び４０００００ダインｃｍ ／ ｃ
ｍのスプリングを有するハーキユルス高剪断粘度計によ
り４４００ ｒｌｌｌｌ及び１０５°Ｆで測定）を有す
る紙塗被組成物である。The present invention provides a composition comprising 100-40% by weight of clay and 0-60% by weight of one or more components selected from the group consisting of calcium carbonate, aluminum trihydrate, titanium dioxide and barium sulfate. % by weight and 08-c1□-vinyl aromatic monomers unsubstituted or substituted by 01-C4-alkyl groups or chlorine atoms 5
5-65% by weight, unsubstituted or substituted with chlorine atoms, branched or straight chain c4-c6-conjugated diolefin 3
0 to 40% by weight and one or more 4 to 10 weight percent copolymers of ethylenically unsaturated carboxylic acids,
Comprised of 5-15% dry weight latex that produces 0.5% solid aggregates when immersed in 10% CaCl2, with a solids content of 65-75% by weight and a solids viscosity of 80 centipoise (E Bob and 400000 dynes cm/c
4400 rllll and 105° F.) on a Hercules high shear viscometer with a spring of m.
本発明はさらに、前記の組成物を８〜１５１ｂ（乾燥）
／６３０００ｆｔ２（連）（９〜１７ｇ／ｍ２）の重量
で用いて塗被された紙を提供する。The present invention further provides the above composition with 8 to 151b (dry).
/63000 ft2 (ream) (9-17 g/m2) to provide coated paper.
本発明により塗被された紙は、シートの光沢、インキ遮
断（ｈｏｌｄｏｕｔ ）特性、白色度を含む特性の良好
な調和を有し、工（）Ｔ結合力（＃４粘着インキ）は４
００ｍ／秒以上である。Paper coated according to the present invention has a good balance of properties including sheet gloss, ink holdout properties, whiteness, and has a bond strength of 4.
00 m/sec or more.
本発明の紙塗被料は、９５〜８５重量％の顔料を含有す
る。顔料は全部がクレーであってよ（、そしてクレー１
００〜４０重量％好ましくは７０重量％以上、及び炭酸
カルシウム６０重量％以下好ましくは６０重量％未満か
ら成っていてもよい。好ましい顔料組成は、クレー７０
〜８０重量％及び炭酸カルシウム３０〜２０重量％から
成る。The paper coating of the invention contains 95 to 85% by weight of pigment. All pigments must be clay (and clay 1
00 to 40% by weight, preferably at least 70% by weight, and up to 60% by weight, preferably less than 60% by weight of calcium carbonate. A preferred pigment composition is clay 70
-80% by weight and 30-20% by weight of calcium carbonate.
一般に紙塗被組成物に用いられるクレーは、５μｍ未満
の平均粒径を有する。最も好ましくはクレーは２μｍ未
満の平均粒径を有する。本発明の塗被組成物に炭酸カル
シウムを用いる場合は、平均粒径は２μｍ未満である。Clays commonly used in paper coating compositions have an average particle size of less than 5 μm. Most preferably the clay has an average particle size of less than 2 μm. When calcium carbonate is used in the coating composition of the invention, the average particle size is less than 2 μm.
本発明に用いられるラテックス結合剤は、非置換の又は
Ｃ１〜Ｃ４−アルキル基もしくは塩素・原子により置換
された０８〜Ｃｌ２−ビニル芳香族単量体５５〜６５重
量％好ましくは５８〜６２重量％、
非置換の又は塩素原子により置換された分枝状又は直鎖
状のＣ４〜Ｃ６−共役ジオレフィン６０〜４０重量％好
ましくは３２〜３６重量％、及び１種１以上の０３〜Ｃ
６−エチレン性不飽和カルボン酸４〜１０重量％好まし
くは５〜７重量％から成る。The latex binder used in the present invention comprises 55-65% by weight of 08-Cl2-vinyl aromatic monomers, unsubstituted or substituted by C1-C4-alkyl groups or chlorine atoms, preferably 58-62% by weight. , unsubstituted or substituted with chlorine atoms, branched or linear C4-C6-conjugated diolefin 60-40% by weight, preferably 32-36% by weight, and one or more 03-C
It consists of 4-10% by weight, preferably 5-7% by weight of 6-ethylenically unsaturated carboxylic acid.
所望により重合体は、０３〜Ｃ６−エチレン性不飽和カ
ルボン酸のアミド（このアミドは非置換であるか、又は
窒素原子において０１〜Ｃ４−アルキル基及びヒドロキ
シアルキル基から成る群から選ばれた２個以下の基によ
り置換されている）及び０３〜Ｃ６−エチレン性不飽和
アルデヒドから成る群から選ばれた追加の機能性単量体
を５重量％未満の少量で好ましくは２重量％未満の量で
含有していてよい。Optionally, the polymer is an amide of an 03-C6 ethylenically unsaturated carboxylic acid, which amide is unsubstituted or contains at the nitrogen atom 2 selected from the group consisting of 01-C4 alkyl groups and hydroxyalkyl groups. of an additional functional monomer selected from the group consisting of It may be contained in
好適なＣ８〜Ｃｌ２−ビニル芳香族単量体は、スチレン
及びα−メチルスチレンを含む。有用な０４〜Ｃ６＃役
ジオレフインは、ブタジェン、インプレン及びクロロプ
レンを含む。好適な０３〜Ｃ６−エチレン性不飽和カル
ボン酸は、モノ−及びジカルボン酸例えばアクリル酸、
メタクリル酸、フマル酸、イタコン酸及びそれらの混合
物を含む。混合モノ−及びジ−カルボン酸を含有する重
合体を用いる場合に、特に有利な結果が得られる。混合
モノ−及びジ−カルボン酸を用いる場合は、これらを１
０：１ないし１：１０の重量比で使用できる。モノ−対
ジーカルボン酸単量体の重量比は約２＝１ないし８：１
特に約４：１ないしろ：１が好ましい。Suitable C8-Cl2-vinyl aromatic monomers include styrene and alpha-methylstyrene. Useful 04-C6# role diolefins include butadiene, imprene and chloroprene. Suitable 03-C6-ethylenically unsaturated carboxylic acids include mono- and dicarboxylic acids such as acrylic acid,
Contains methacrylic acid, fumaric acid, itaconic acid and mixtures thereof. Particularly advantageous results are obtained when using polymers containing mixed mono- and di-carboxylic acids. When using mixed mono- and di-carboxylic acids, these
A weight ratio of 0:1 to 1:10 can be used. The weight ratio of mono- to dicarboxylic acid monomers is about 2=1 to 8:1.
Particularly preferred is about 4:1 to about 1:1.
重合体の製造には普通の技術が用いられる。Conventional techniques are used to prepare the polymers.
一般にラテックスは固形物４５〜５５重量％を含有する
。好ましくは重合体は、連鎖移動剤０゜５〜２重量部特
に約１重量部の存在下に製造される。好ましい連鎖移動
剤は、０８〜Ｃｌ２−アルキルメルカプタンである。ク
ロロホルム及びブロモホルムも好適な連鎖移動剤である
。Generally latex contains 45-55% solids by weight. Preferably, the polymer is prepared in the presence of 0.5 to 2 parts by weight, especially about 1 part by weight, of a chain transfer agent. Preferred chain transfer agents are 08-Cl2-alkyl mercaptans. Chloroform and bromoform are also suitable chain transfer agents.
本発明の重合体は、多価イオン特にカルシウムイオンに
対して高い安定性を有する。１０％ＣａＣｌ２溶液の存
在下で１４日間に、痕跡量（０゜５％未満）の凝集物し
か生成しない。The polymers of the present invention have high stability towards multivalent ions, especially calcium ions. Only trace amounts (less than 0.5%) of aggregates are formed in the presence of 10% CaCl2 solution for 14 days.
塗被組成物の製造において、分散剤を顔料に添加するこ
とができる。必要に応じ増粘剤及び／又は不透明剤を塗
被組成物に添加し、水により必要な固形物含量に希釈し
てもよい。有用な分散剤及び増粘剤は、商品カタログ例
えばＴｈｅＭａｎｕｆａｃｔｕｒｉｎｇ Ｃｏｎｆｅｃ
ｔｉｏｎｅｒ Ｐｕｂｌｉｓｈｉｎｇ Ｃｏ。In preparing the coating composition, dispersants can be added to the pigment. If desired, thickeners and/or opacifying agents may be added to the coating composition and diluted with water to the required solids content. Useful dispersants and thickeners can be found in commercial catalogs such as The Manufacturing Confec.
tioner Publishing Co.
のＭｃＣｕｔｃｈｅｏｎ’ｓ部により毎年発行されるＭ
ｃＣｕｔｃｈｅｏｎ’ｓ Ｆｕｎｃｔｉｏｎａｌ Ｍａ
ｔｅｒｉａｌｓ （北米板及び国際版）に記載されてい
る。特定の機能性物質の選択は、塗料に望まれる特定の
性質に依存する。Published annually by McCutcheon's division of
cCutcheon's Functional Ma
terials (North American and international editions). The selection of the particular functional material will depend on the particular properties desired in the coating.
増粘剤を用いる場合は、その使用は最小限にすべきであ
る。固形物含量が６５〜７０重量％の組成物は、Ｅボブ
及び４０００００ダインｃｍ１ｍのスプリングを有する
ハーキユルス高剪断粘度計を用いて４４００ ｒ９ｍ及
び１０５°Ｆで測定して、８０センチポイズ以下好まし
くは２０〜７０センチポイズの粘度を有する。If thickeners are used, their use should be minimized. Compositions with a solids content of 65-70 wt. It has a viscosity of 70 centipoise.
本発明の塗被組成物により、普通の方法で紙を塗被し、
そして必要に応じ適当な条件下にカレンダー仕上げする
ことができる。得られる紙は、少なくとも４００ｍ／秒
の乾燥表面強度を有する。Coating paper with the coating composition of the invention in a conventional manner,
Calendar finishing can then be carried out under appropriate conditions if necessary. The resulting paper has a dry surface strength of at least 400 m/sec.
下記実施例中の部は特に指示のない限り重量部である。Parts in the following examples are parts by weight unless otherwise indicated.
実施例１
スチレン約６０部、ブタジェン３３部、アクリル酸及び
イタコン酸の混合物７部を、連鎖移動剤１部の存在下に
乳化重合させることにより基礎ラテックスを製造した。Example 1 A basic latex was prepared by emulsion polymerization of approximately 60 parts of styrene, 33 parts of butadiene, and 7 parts of a mixture of acrylic acid and itaconic acid in the presence of 1 part of a chain transfer agent.
このラテックスはストリッピング後に５０重量％の固形
物含量を有していた。This latex had a solids content of 50% by weight after stripping.
比較のため、約２．５重量％のカルボン酸単量体含量及
び約６３重量％のスチレン含量を有するＰＯＬＹＳＡＲ
の商標で販売されている市販のカルボキシル化スチレン
−ブタジェンラテックスを、対照として実験に用いた。For comparison, POLYSAR with a carboxylic acid monomer content of about 2.5% by weight and a styrene content of about 63% by weight
A commercially available carboxylated styrene-butadiene latex sold under the trade mark was used in the experiment as a control.
下記の成分から成る基礎組成物を調製した。A base composition was prepared consisting of the following ingredients.
クレー ７０ ＣａＣＯ３６０ ラテックス １２ 殿粉 ２ 水を加えて約６５％の固形物含量にする。Clay 70 CaCO360 Latex 12 Starch starch 2 Add water to approximately 65% solids content.
組成物の粘度は、Ｅボブ及び４０００００ダインｃｍ／
ｃｍのスプリングを有するハーキユルス高剪断粘度計に
より４４００ ｒｌｌｆｆｌ及び１０５’Ｆで測定した
。The viscosity of the composition is E bob and 400,000 dynes cm/
Measurements were made on a Hercules high shear viscometer with a cm spring at 4400 rllffl and 105'F.
塗被組成物を紙に９．５１ｂ／連の乾燥重量で塗布し、
模擬製造条件下でカレンダー仕上げした。applying the coating composition to paper at a dry weight of 9.51 b/ream;
Calendered under simulated manufacturing conditions.
塗被紙を７５°Ｆ及び相対湿度５０％で１夜状態調整し
た。The coated paper was conditioned overnight at 75°F and 50% relative humidity.
次いでこの紙を、シートの光沢、白色度（Ｄｉａｎｏ
Ｓ−４入及び＃４４部定格インキを用いる３ｍ１秒の増
加速度及び３５ ｋｇｆでのＩ（）Ｔ乾燥表面強度（モ
デルＡｌＣ２）について調べた。その結果を第１表に示
す。The paper was then tested for sheet gloss, whiteness (Diano
The I()T dry surface strength (model AlC2) at a 3ml/sec increase rate and 35 kgf using S-4 and #44 part rated inks was investigated. The results are shown in Table 1.
第１表
対照ラテン 実験ラテン
クス クス
ハーキユルス見かけ粘度 ２２ １８（
センチポイズ）
光沢−カレンダ−ニップ ０ ２８ ６０
４ ７０．４ ７２．０
印刷の光沢 ８５．５ ８６．８白
色度 ８４．８ ８４．５
ＩＧＴ乾燥表面強度 ３４３ ４０２（＃
４インキ、４部沙、３５ｋｇ４）
これは、本発明により製造された紙塗被組成物が先行技
術に比べて、より低い高剪断粘度を有し、そして同等又
は良好な印刷の光沢及び改善された乾燥表面強度を与え
ることを示している。Table 1 Comparative Latin Experimental Latinx Apparent viscosity 22 18 (
Centipoise) Gloss Calendar Nip 0 28 60
4 70.4 72.0 Print gloss 85.5 86.8 Whiteness 84.8 84.5 IGT dry surface strength 343 402 (#
4 ink, 4 parts, 35 kg 4) This means that the paper coating compositions produced according to the present invention have a lower high shear viscosity and equal or better print gloss and improved print gloss compared to the prior art. It has been shown that this gives a good dry surface strength.
実施例２
実施例１の対照及び実験ラテックスを下記のように配合
した。Example 2 The control and experimental latexes of Example 1 were formulated as follows.
クレー ６０
炭酸カルシウム ４０
ラテックス １６
殿粉 ６
滑剤 １
この組成物を水で希釈して、固形物含量を３６．６７重
量％及び７０重量％にした。Clay 60 Calcium Carbonate 40 Latex 16 Starch 6 Lubricant 1 The composition was diluted with water to a solids content of 36.67% and 70% by weight.
ラテックスを実施例１と同様に試験した。紙を、実験室
用塗装機により９．５１ｂ（乾燥）／連で塗被しだ。こ
の紙を実施例１と同様にカレンダー仕上げし、そして試
験した。その結果を第■表に示す。The latex was tested as in Example 1. The paper was coated with a laboratory coater at 9.51b (dry)/ream. The paper was calendered and tested as in Example 1. The results are shown in Table ①.
第■表 組成物の固形物に） 対照ラテックス 実験ラテックス たのち濾過した。凝固物は検出されなかった。Table ■ to the solids of the composition) contrast latex experimental latex It was then filtered. No clots were detected.
実施例１の対照ラテックスでは、１０％ＣａＣ１２溶液
により、１５％のラテックス凝固物が得られた。For the control latex of Example 1, a 10% CaC12 solution resulted in a 15% latex coagulum.
シートの光沢、７５°Ｆ ６５ ６９−６５
６９印刷の光沢 ７７ ８１ − ８０
８３ ８７白色度 ８２．４ ８１．９−８４
．１ ８４．５ ８５．５出願人 ビーニーニスエフ
・アクチェンゲゼルシャフト代理人 弁理士 高 橋
淳
対照ラテックスによる７０％固形分の塗被紙における試
験結果は、普通の塗布条件下で紙を塗被できないものと
考えられた。この結果は、本発明による高剪断流動性、
印刷の光沢及び乾燥表面強度における改善を示している
。Sheet gloss, 75°F 65 69-65
69 Printing gloss 77 81 - 80
83 87 Whiteness 82.4 81.9-84
．． 1 84.5 85.5 Applicant Bininisev Akchengesellschaft Agent Patent Attorney Atsushi Takahashi Test results on coated paper with 70% solids content using control latex show that the paper cannot be coated under normal coating conditions. It was considered a thing. This result shows that the high shear fluidity according to the present invention,
It shows an improvement in print gloss and dry surface strength.
実施例６
実施例１の実験ラテックスのカルシウムイオンに対する
安定性を調べた。Example 6 The stability of the experimental latex of Example 1 to calcium ions was investigated.
Claims (1)
ルミニウム三水和物、二酸化チタン及び硫酸バリウムか
ら成る群から選ばれた１種以上の成分０〜６０重量％か
ら成る組成物９５〜８５乾燥重量％、ならびに 非置換の又はＣ＿１〜Ｃ＿４−アルキル基もしくは塩素
原子により置換されたＣ＿８〜Ｃ＿１＿２−ビニル芳香
族単量体５５〜６５重量％、非置換の又は塩素原子によ
り置換された分枝状又は直鎖状のＣ＿４〜Ｃ＿６−共役
ジオレフィン３０〜４０重量％及び１種以上のＣ＿３〜
Ｃ＿６−エチレン性不飽和カルボン酸４〜１０重量％の
共重合体から成り、１０％ＣａＣｌ＿２に浸漬したとき
に０．５重量％未満の凝集物を生成するラテックス５〜
１５乾燥重量％から構成され、 ６５〜７５重量％の固形物含量及び８０センチポイズ未
満の粘度（Ｅボブ及び４０００００ダインｃｍ／ｃｍの
スプリングを有するハーキユルス高剪断粘度計により４
４００ｒｐｍ及び１０５°Ｆで測定）を有する紙塗被組
成物。 ２、６５〜７０重量％の固形物含量及び２０〜７０セン
チポイズの粘度（Ｅボブ及び４０００００ダインｃｍ／
ｃｍのスプリングを有するハーキユルス高剪断粘度計に
より４４００ｒｐｍ及び１０５°Ｆで測定）を有するこ
とを特徴とする、第１請求項に記載の紙塗被組成物。 ３、重合体が、モノ−及びジ−カルボン酸の両方を４：
１ないし６：１のモノ−対ジ−カルボン酸の重量比で含
有することを特徴とする、第２請求項に記載の紙塗被組
成物。 ４、重合体が、スチレン５８〜６２重量％、ブタジエン
３２〜３６重量％ならびにアクリル酸、メタクリル酸、
イタコン酸及びフマル酸から成る群から選ばれた１種以
上のカルボン酸５〜７重量％から成ることを特徴とする
、第３請求項に記載の紙塗被組成物。 ５、２μｍ未満の平均粒径を有するクレー７０〜８０重
量％及び２μｍ未満の平均粒径を有する炭酸カルシウム
３０〜２０重量％、ならびに重合体５〜１５重量％から
成ることを特徴とする、第４請求項に記載の紙塗被組成
物。 ６、第４請求項に記載の塗被料８〜１５ｌｂ／３３００
ｆｔ＾２を用いて塗被されており、そして４５０ｍ／秒
以上のＩＧＴ表面強度（＃４インキを用いて測定）を有
する紙。 ７、第５請求項に記載の塗被料８〜１５ｌｂ／３３００
ｆｔ＾２を用いて塗被されており、そして４５０ｍ／秒
以上のＩＧＴ表面強度（＃４インキを用いて測定）を有
する紙。[Claims] 1. A composition comprising 100 to 40% by weight of clay and 0 to 60% by weight of one or more components selected from the group consisting of calcium carbonate, aluminum trihydrate, titanium dioxide, and barium sulfate. 95-85% by dry weight of C_8-C_1_2-vinyl aromatic monomers, unsubstituted or substituted by C_1-C_4-alkyl groups or chlorine atoms, and 55-65% by weight, unsubstituted or substituted by chlorine atoms. 30-40% by weight of branched or linear C_4-C_6-conjugated diolefins and one or more C_3-
C_6 - a latex consisting of a copolymer of 4 to 10% by weight of ethylenically unsaturated carboxylic acid and producing less than 0.5% by weight of agglomerates when immersed in 10% CaCl_2
15% by dry weight, with a solids content of 65-75% by weight and a viscosity of less than 80 centipoise (4 by Hercules high shear viscometer with an E-bob and a spring of 400,000 dynes cm/cm).
400 rpm and 105°F). 2, solids content of 65-70% by weight and viscosity of 20-70 centipoise (E-bob and 400,000 dynes cm/
Paper coating composition according to claim 1, characterized in that it has a viscosity of 4400 rpm and 105° F. (measured on a Hercules high shear viscometer with a spring of cm). 3. The polymer contains both mono- and di-carboxylic acids 4:
Paper coating composition according to claim 2, characterized in that it contains a weight ratio of mono- to di-carboxylic acids of 1 to 6:1. 4. The polymer contains 58 to 62% by weight of styrene, 32 to 36% by weight of butadiene, and acrylic acid, methacrylic acid,
Paper coating composition according to claim 3, characterized in that it consists of 5 to 7% by weight of one or more carboxylic acids selected from the group consisting of itaconic acid and fumaric acid. 5, characterized in that it consists of 70-80% by weight of clay with an average particle size of less than 2 μm, 30-20% by weight of calcium carbonate with an average particle size of less than 2 μm, and 5-15% by weight of a polymer. The paper coating composition according to claim 4. 6. Coating material 8 to 15 lb/3300 according to claim 4
ft^2 and has an IGT surface strength (measured using #4 ink) of greater than 450 m/s. 7. Coating material according to claim 5 8-15 lb/3300
ft^2 and has an IGT surface strength (measured using #4 ink) of greater than 450 m/s.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US19358688A | 1988-05-13 | 1988-05-13 | |
| US193586 | 1988-05-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH026693A true JPH026693A (en) | 1990-01-10 |
Family
ID=22714241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11765389A Pending JPH026693A (en) | 1988-05-13 | 1989-05-12 | Paper coating composition with high solid content |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0341598A3 (en) |
| JP (1) | JPH026693A (en) |
| AU (1) | AU3471889A (en) |
| FI (1) | FI892260A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5611890A (en) * | 1995-04-07 | 1997-03-18 | The Proctor & Gamble Company | Tissue paper containing a fine particulate filler |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3793244A (en) * | 1972-08-17 | 1974-02-19 | J Megee | Water-retaining latexes of styrene-butadiene-itaconic acid terpolymers |
| JPS62268897A (en) * | 1986-05-15 | 1987-11-21 | 住化エイビーエス・ラテックス株式会社 | Paper coating composition |
-
1989
- 1989-05-05 EP EP19890108130 patent/EP0341598A3/en not_active Withdrawn
- 1989-05-10 FI FI892260A patent/FI892260A/en not_active Application Discontinuation
- 1989-05-12 JP JP11765389A patent/JPH026693A/en active Pending
- 1989-05-12 AU AU34718/89A patent/AU3471889A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| AU3471889A (en) | 1989-11-16 |
| FI892260A0 (en) | 1989-05-10 |
| FI892260A (en) | 1989-11-14 |
| EP0341598A2 (en) | 1989-11-15 |
| EP0341598A3 (en) | 1991-04-10 |
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