JPS60224895A - Coating composition for gravure printing paper - Google Patents
Coating composition for gravure printing paperInfo
- Publication number
- JPS60224895A JPS60224895A JP7445484A JP7445484A JPS60224895A JP S60224895 A JPS60224895 A JP S60224895A JP 7445484 A JP7445484 A JP 7445484A JP 7445484 A JP7445484 A JP 7445484A JP S60224895 A JPS60224895 A JP S60224895A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- coating composition
- copolymer latex
- gravure printing
- parts
- 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
- 239000008199 coating composition Substances 0.000 title claims description 24
- 238000007646 gravure printing Methods 0.000 title claims description 21
- 229920001577 copolymer Polymers 0.000 claims description 38
- 239000004816 latex Substances 0.000 claims description 34
- 229920000126 latex Polymers 0.000 claims description 34
- 239000000178 monomer Substances 0.000 claims description 27
- 239000000049 pigment Substances 0.000 claims description 15
- 229920002472 Starch Polymers 0.000 claims description 9
- 230000009477 glass transition Effects 0.000 claims description 9
- 239000008107 starch Substances 0.000 claims description 9
- 235000019698 starch Nutrition 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 4
- 150000005673 monoalkenes Chemical class 0.000 claims description 3
- 238000007639 printing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 7
- 238000006116 polymerization reaction Methods 0.000 description 7
- 206010016807 Fluid retention Diseases 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001254 oxidized starch Substances 0.000 description 4
- 235000013808 oxidized starch Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- -1 imprene Chemical compound 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010556 emulsion polymerization method Methods 0.000 description 2
- 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 2
- 238000000691 measurement method Methods 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- 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
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 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
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Paper (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
（１）発明の目的
本発明は、優れたグラピッ印刷紙用被覆組成物に関する
。DETAILED DESCRIPTION OF THE INVENTION (1) Object of the Invention The present invention relates to an excellent coating composition for graphic printing paper.
グラビア印刷方式は、被印刷体に限定がない、大量印刷
が可能である、印刷物の階調再限性が良い等の理由から
、近年出版印刷業界で広く適用されてきている。The gravure printing method has been widely applied in the publication printing industry in recent years due to the following reasons: there is no limitation on the printing substrate, large-scale printing is possible, and the gradation redefinability of printed matter is good.
しかし、従来のグラビア印刷方式では印刷時グラビア版
の個々のセルから被印刷紙へのインキの転写もれ、いわ
ゆるミスドツトが起こり印刷物の美感を著しく低下させ
る。このミスドツトの改良については、被印刷紙の表面
平滑性、クッション性、吸油性等の改良が必要とされ、
原紙、紙被覆顔料面、スーノクーキャレンダーなどの後
処理面等に於ける改良努力が塗工紙メーカーで実施され
、対処されてきている。However, in the conventional gravure printing method, ink transfer leakage from individual cells of the gravure plate to the printing paper occurs during printing, so-called misdots, which significantly deteriorates the aesthetic appearance of the printed matter. To improve these misdots, it is necessary to improve the surface smoothness, cushioning properties, oil absorption properties, etc. of the printing paper.
Efforts have been made by coated paper manufacturers to improve the base paper, the pigment surface of the paper coating, and the post-processing aspects such as Sunoque calenders.
又、顔料バインダーの点でも種々の工夫が行なわれてい
るが、グラビア印刷紙専用顔料バインダーとなると未だ
満足できるものが得られてないのが実情である。In addition, various efforts have been made regarding pigment binders, but the reality is that no satisfactory pigment binder specifically for gravure printing paper has yet been obtained.
本発明者らは、この様な現状にかんがみ、グラビア印刷
時のミスドツトを改良すべく鋭意研究を行なった結果、
特定の共重合体ラテックスと澱粉の組み合わせからなる
顔料バインダーを用いる事により、保水性、流動性が良
好で優れたグラビア印刷適性を有するグラビア印刷紙用
被覆組成物が得られることを見い出し、本発明に到達し
たものである。In view of the current situation, the inventors of the present invention have conducted extensive research to improve the problem of missed dots during gravure printing, and as a result, have found that:
It was discovered that by using a pigment binder consisting of a combination of a specific copolymer latex and starch, a coating composition for gravure printing paper having good water retention and fluidity and excellent suitability for gravure printing could be obtained, and the present invention has been reached.
（２） 発・明の構成
即ち、本発明は顔料１００重量部に対しく４）共役ジオ
レフィン系単量体５０．５〜８５重量％、エチレン系不
飽和カルボン酸単量体０５〜１０重量％、エチレン系不
飽和カルボン酸アミド単量体０〜１０重量％及びこれら
と共重合可能なモノオレフィン系単量体５〜４９重量％
を乳化重合させて得られるガラス転移温度が一２５℃以
下の共重合体ラテックス３〜１５重量部及び（Ｂ）澱粉
１〜３重量部からなることを特徴とするグラビア印刷適
性に優れたグラビア印刷紙用被覆組成物を提供するもの
である。(2) Constitution of the invention, that is, the present invention is based on 100 parts by weight of pigment, 4) 50.5 to 85% by weight of a conjugated diolefin monomer, and 05 to 10% by weight of an ethylenically unsaturated carboxylic acid monomer. %, ethylenically unsaturated carboxylic acid amide monomer 0 to 10% by weight and monoolefin monomer copolymerizable with these 5 to 49% by weight
Gravure printing with excellent suitability for gravure printing, characterized by comprising 3 to 15 parts by weight of a copolymer latex with a glass transition temperature of 125° C. or lower obtained by emulsion polymerization of A coating composition for paper is provided.
以下に本発明についてさらに詳細に説明する。The present invention will be explained in more detail below.
本発明で用いられる共重合体ラテックス中の共役ジオレ
フィン系単量体として蝶、ブタジェン、インプレン、ク
ロロプレンなどが使用でき、特にブタジェンが好適であ
る。As the conjugated diolefin monomer in the copolymer latex used in the present invention, butterfly, butadiene, imprene, chloroprene, etc. can be used, and butadiene is particularly preferred.
共役ジオレフィン系単量体の使用量は、５０．５〜８５
重量％であり、５０，５重量−未満では、塗工紙のグラ
ビア印刷適性が低下し、又、８５重量％を越えると、塗
工紙のスーバーキャレンダー仕上げ効果が劣り、グラビ
ア印刷適性の低下をきたす。The amount of conjugated diolefin monomer used is 50.5 to 85
If it is less than 50.5% by weight, the suitability for gravure printing of the coated paper will decrease, and if it exceeds 85% by weight, the supercalender finishing effect of the coated paper will be poor and the suitability for gravure printing will decrease. cause
エチレン系不飽和カルボン酸単量体としては、アクリル
酸、メタクリル酸、イタコン酸、フマール酸、マレイン
酸、クロトン酸及びジカルボン酸の無水物などがあげら
れる０これらは単独、あるいは２種以上併用して用いて
もよい。使用量は、０．５〜１０重量％の範囲である。Examples of ethylenically unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, and dicarboxylic acid anhydrides.These may be used alone or in combination of two or more. It may also be used. The amount used ranges from 0.5 to 10% by weight.
０．５重量−未満では共重合体ラテックスの安定性が低
下し、又、１０重量％を越えると、共重合体ラテックス
の粘度が著しく高くなり、いずれも被覆組成物の作成が
困難になる。If it is less than 0.5% by weight, the stability of the copolymer latex decreases, and if it exceeds 10% by weight, the viscosity of the copolymer latex becomes extremely high, making it difficult to prepare a coating composition.
エチレン系不飽和カルボン酸アミド単量体としては、ア
クリルアミド、メタクリルアミド、Ｎ−メチロールアク
リルアミド、グリシジルメククリルアミドなどがあげら
れる。これらは単独あるいは２種以上併用して用いても
よい。使用量は、０〜１０重量％であり、１０重量％を
越えると、本発明の特徴であるグラビア印刷適性の低下
をきたす。Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-methylol acrylamide, and glycidyl meccrylamide. These may be used alone or in combination of two or more. The amount used is 0 to 10% by weight, and if it exceeds 10% by weight, the suitability for gravure printing, which is a feature of the present invention, decreases.
また、これらと共重合可能なモノオレフィン系単量体と
しては、スチレン、α−メチルスチレンなどの芳香族ビ
ニル系単量体、アクリル酸メチル、アクリル酸エチル、
アクリル酸ブチル、メタクリル酸メチル、メタクリル酸
エチル、アクリル酸２−エチルヘキシル、アクリル酸２
−ヒドロキシエチルなどのエチレン系不飽和カルボン酸
のエステル、アクリロリロ
ニトリル、メタクーニトリル、塩化ビニル、酢酸ビニル
などのビニル系単量体があげられる。その使用量は、５
〜４９重量％であり、５重量−未満では、塗工紙のスー
ツく−キャレンダー仕上げ効果が劣り、グラビア印刷適
性が低下する。又、４９重量％を越えるとグラビア印刷
適性の低下をきたす。In addition, monoolefin monomers that can be copolymerized with these include aromatic vinyl monomers such as styrene and α-methylstyrene, methyl acrylate, ethyl acrylate,
Butyl acrylate, methyl methacrylate, ethyl methacrylate, 2-ethylhexyl acrylate, acrylic acid 2
Examples include esters of ethylenically unsaturated carboxylic acids such as -hydroxyethyl, vinyl monomers such as acrylolylonitrile, methacounitrile, vinyl chloride, and vinyl acetate. The amount used is 5
If the amount is less than 5% by weight, the suit-calendering effect of the coated paper will be poor and the suitability for gravure printing will be reduced. Moreover, if the content exceeds 49% by weight, suitability for gravure printing will decrease.
この様な単量体組成によって得られた共重るが、本発明
で用いられる共重合体ラテツクスのガラス転移温度は一
２５℃以下である事が必要である。Although the copolymer latex obtained with such a monomer composition is used in the present invention, it is necessary that the glass transition temperature of the copolymer latex used in the present invention is -25°C or lower.
即ち、本発明の単量体組成から得られた共重合ラテック
スでは、ポリマーのガラス転移温度とポリマーの柔軟性
に良い相関が見られ、ガラス転移温度が一２５℃以下の
低い領域ではポリマーの柔軟性が付与され、顔料バイン
ダーとして使用された場合、塗工紙のクッシＨ／性が向
上し優れたグラビア印刷適性を示す被覆組成物が得られ
る。That is, in the copolymerized latex obtained from the monomer composition of the present invention, a good correlation is observed between the glass transition temperature of the polymer and the flexibility of the polymer, and in the low glass transition temperature range of 125°C or less, the flexibility of the polymer decreases. When used as a pigment binder, a coating composition is obtained that improves the brushiness of the coated paper and exhibits excellent gravure printability.
本発明で用いられる共重合体ラテックスは通常の乳化重
合法で製造される。すなわち、反応器の中に、水、単量
体、乳化剤、電解質、連鎖移動剤、開始剤などを加え、
攪拌しながら、５０〜９０℃に加温し重合する。この際
、単量体等は、一度に全量添加することもできるし、共
重合体ラテックス粒子の異質多相構造化を図る為に、単
量体の一部を連続添加、又は間欠添加することもできる
０この様な乳化重合法で得られた異質多相構造を有する
共重合体う゛テックスは、優れた接着強度、グラビア印
刷適性を示した。The copolymer latex used in the present invention is produced by a conventional emulsion polymerization method. That is, water, monomers, emulsifiers, electrolytes, chain transfer agents, initiators, etc. are added to the reactor.
While stirring, the mixture is heated to 50 to 90°C for polymerization. At this time, the monomer etc. can be added in its entirety at once, or in order to create a heterogeneous multi-phase structure of the copolymer latex particles, a part of the monomer can be added continuously or intermittently. The copolymer vegetate having a heterogeneous multiphase structure obtained by such an emulsion polymerization method showed excellent adhesive strength and suitability for gravure printing.
特に、異質多相構造を有し、ガラス転移温度が一４０℃
以下の共重合体ラテックスの場合には、極めて良好な、
グラビア印刷適性を示した。In particular, it has a heterogeneous multiphase structure and a glass transition temperature of -40°C.
In the case of the following copolymer latexes, very good
Demonstrated suitability for gravure printing.
本発明の共重合体ラテックスと併用して用いられる澱粉
としては、酸化澱粉、エーテル化澱粉、エステル化澱粉
などがあげられる。Examples of the starch used in combination with the copolymer latex of the present invention include oxidized starch, etherified starch, and esterified starch.
この場合澱粉は、単に顔料バインダーとしてだけでなく
、紙被覆組成物としての粘度調節の効果、機械的安定性
への効果、高速ブレード塗工時のストリークなどのトラ
ブルの原因となる被覆組成物の保水性、高剪断下での流
動性への効果などの為に用いられ、本発明にしての使用
量は、顔料１００重量部に対して、共重合体ラテックス
３〜１５重量部、澱粉１〜３重量部である。In this case, starch is used not only as a pigment binder, but also as a viscosity control agent for paper coating compositions, an effect on mechanical stability, and a coating composition that causes problems such as streaks during high-speed blade coating. It is used for its effects on water retention and fluidity under high shear, and the amounts used in the present invention are 3 to 15 parts by weight of copolymer latex and 1 to 10 parts by weight of starch per 100 parts by weight of pigment. It is 3 parts by weight.
性が低下する０
本発明に於いては、アルカリ可溶型共重合体ラテックス
、カルボキシメチルセルロース、アルギン酸ナトリウム
などの保水剤を併用し用いることもできる０
本発明の紙被覆組成物に使用される顔料としては、通常
の鉱物性紙被覆用顔料が用いられる。例えば、クレー、
重質炭酸カルシウム、沈降性炭酸カルシウム、水酸化ア
ルミニウム、サテンホワイト、メルク、二酸化チタンな
どがあげられる０
なお、本発明の被覆組成物を作成するにあたっては、一
般に用いられる分散剤等が用いらｈ７＋−
以下に、本発明の特徴を示すべ〈実施例を示すが、本発
明は、これら実施例によって何ら限定されるものではな
い。又、本実施例における部数及びチは各々、重量部及
び重量％を意味する。In the present invention, water retention agents such as alkali-soluble copolymer latex, carboxymethyl cellulose, and sodium alginate may be used in combination.0 Pigments used in the paper coating composition of the present invention. As such, ordinary mineral paper coating pigments are used. For example, clay,
Examples include heavy calcium carbonate, precipitated calcium carbonate, aluminum hydroxide, satin white, Merck, titanium dioxide, etc. In preparing the coating composition of the present invention, commonly used dispersants and the like are not used. - Examples are shown below to illustrate the characteristics of the present invention, but the present invention is not limited to these Examples in any way. Further, parts and parts in this example mean parts by weight and weight %, respectively.
１、 共重合体ラテックスの製造
１）表−１に示した各単量体、ｔ−ドデシルメルカプタ
ンとアルキルベンゼンスルホン酸ソーダ１．２部、重ソ
ウ０．５部、過硫酸アンモニウム０．８部、水１００部
をＩＯＡ’オートクレーブに仕込み、攪拌しながら６５
℃で重合させた。得られた共重合体ラテックスをそれぞ
れＡ−Ｆとする。1. Production of copolymer latex 1) Each monomer shown in Table 1, t-dodecyl mercaptan, 1.2 parts of sodium alkylbenzenesulfonate, 0.5 parts of sodium bicarbonate, 0.8 parts of ammonium persulfate, and water. Pour 100 parts into IOA' autoclave and add 65 parts while stirring.
Polymerization was carried out at ℃. The obtained copolymer latexes are designated as A-F, respectively.
１） 表−２に示した第１段階に用いる各単量体、ｔ−
ドデシルメルカプタンとアルキルベンゼンスルホン酸ソ
ーダ１．２部、重ソウ０．５部、過硫酸アンモニウム０
，８部、水１００部を１０ＡＩオートクレーブに仕込み
、攪拌しながら、６５℃で重合させた。重合転化率が９
０−以上になったところで、第２段階の単量体を添加し
て重合を完結した。1) Each monomer used in the first stage shown in Table 2, t-
Dodecyl mercaptan, 1.2 parts of sodium alkylbenzenesulfonate, 0.5 parts of sodium bicarbonate, 0 ammonium persulfate
, and 100 parts of water were placed in a 10AI autoclave and polymerized at 65° C. with stirring. Polymerization conversion rate is 9
When the temperature reached 0- or higher, the second stage monomer was added to complete the polymerization.
得られた共重合体ラテックスをＧ、Ｈとする。The obtained copolymer latexes are designated as G and H.
厘）表−３に示した各単量体、ｔ−ドデシルメルカプタ
ンを用い、■）で使用した重合法と同じ方法により、共
重合体ラテックスＩ −Ｍを重合した。厘) Copolymer latex I-M was polymerized using each monomer shown in Table 3, t-dodecyl mercaptan, by the same polymerization method as used in ①).
ＩＶ） 表−４に示した各単量体、ｔ−ドデシルメルカ
プタンを用い、１）で使用した重合法と同じ方法により
、共重合体ラテックスＮを重合した。IV) Copolymer latex N was polymerized using each monomer shown in Table 4, t-dodecyl mercaptan, by the same polymerization method used in 1).
１）〜蘭共、得られたラテックスの重合転化率はすべて
９８％以上であった。1) - The polymerization conversion rate of the obtained latex was all 98% or more.
これらのラテックスの未反応単量体をストリッピングに
より除去した後２００メツシユ金網で炉遇し、試験に供
した。これらの共重合体ラテックスのガラス転移温度、
ゲル含有量を測定した。After removing unreacted monomers from these latexes by stripping, they were treated with a 200-mesh wire gauze and subjected to a test. The glass transition temperature of these copolymer latexes,
Gel content was measured.
測定及び評価方法
（１） 共重合体ラテックスのガラス転移温度（Ｔ））
室温乾燥にて、各々の共重合体ラテックスポリマーフィ
ルムを作成し、示差走査熱量計を用いて測定した。Measurement and evaluation method (1) Glass transition temperature (T) of copolymer latex)
A latex polymer film of each copolymer was prepared by drying at room temperature and measured using a differential scanning calorimeter.
（２）共重合体ラテックスのゲル含有量（チ）室温乾燥
にて、各々の共重合体ラテックスボリマ−フィルムラ作
成し、そのラテックスフィルムを約２００〜８００倍の
ベンゼンに入れ、４８時間放置溶解し、Ｆ紙（屋２）で
濾過後、表−１
表−２
表−３
表−４
２ラテックスの性能評価
１）共重合体ラテックスＡ−Ｎを用い、以下に示す顔料
被覆組成物を作成し、市販の上質紙に塗工し、塗工紙を
得た。(2) Gel content of copolymer latex (h) Create each copolymer latex polymer film by drying at room temperature, put the latex film in about 200 to 800 times the concentration of benzene, and leave it for 48 hours. After dissolving and filtering with F paper (Ya 2), Table 1 Table 2 Table 3 Table 4 2 Performance evaluation of latex 1) Using copolymer latex A-N, the following pigment coating composition was applied. It was prepared and coated on commercially available high-quality paper to obtain coated paper.
塗工量は片面１０ｙ／ｍ”で、スーパーキャレンダー処
理後、印刷試験に供した。The coating amount was 10 y/m'' on one side, and after being subjected to super calender treatment, it was subjected to a printing test.
被覆組成物
Ａ１カオリン ９０乾燥重量部
重質炭酸カルシウム １０
分 散 剤 ０．２
酸化澱粉 ２
共重合体ラテックス １０
固形分 ６０％に調整
（水酸化ナトリウムを用いＰＨ９に調製作成した各々の
被覆組成物の流動性、保水性及び塗工紙の性能評価結果
を表−５に示した。Coating composition A1 Kaolin 90 parts by dry weight Heavy calcium carbonate 10 Dispersant 0.2 Oxidized starch 2 Copolymer latex 10 Solid content adjusted to 60% (Each coating composition prepared to pH 9 using sodium hydroxide) The fluidity, water retention, and performance evaluation results of coated paper are shown in Table 5.
本発明の実施例である共重合体ラテックスＡ〜Ｈを用い
て作成した被覆組成物及び塗工紙は、比較例である共重
合体ラテックスエ〜Ｎを用いたものに比較して良好な流
動性、保水性及び塗工紙性能を示していた。Coating compositions and coated papers prepared using copolymer latexes A to H, which are examples of the present invention, have better fluidity than those using copolymer latexes A to N, which are comparative examples. properties, water retention properties, and coated paper performance.
１） 共重合体ラテックスＧ１及び■を用い、以下に示
す顔料被覆組成物を作成し、上記Ｉ）と同様にして、塗
工紙を得た。この場合、酸化澱粉量を０．５，１，３．
５部と変化し被覆組成物を作成した〇
評価結果を表−６に示した。1) A pigment coating composition shown below was prepared using copolymer latex G1 and (2), and a coated paper was obtained in the same manner as in I) above. In this case, the amount of oxidized starch is 0.5, 1, 3.
Table 6 shows the evaluation results of coating compositions prepared by changing the coating composition to 5 parts.
共重合体ラテックスＧと１〜３部の澱粉を組み合わせる
事により優れた塗工紙性能を有した塗工紙が得られた。Coated paper with excellent coated paper performance was obtained by combining copolymer latex G with 1 to 3 parts of starch.
被覆組成物
屋１カオリン ６ｏ乾燥重量部
沈降性炭酸カルシウム ３゜
サテンホワイト １０
分 散 剤 ０．５
酸化澱粉 前述
共重合体ラテックス １゜
固形分 ５０％に調製
（水酸化ナトリウムを用いＰＨ１１［調製）■）共重合
体ラテックスＨ，Ｎを用い以下に示す顔料被覆組成物を
作成し、上記Ｉ）と同様にして、塗工紙を得た０この場
合顔料配合比を各々変化させ作成した。Coating composition shop 1 Kaolin 6 o Parts by dry weight Precipitated calcium carbonate 3° Satin white 10 Dispersant 0.5 Oxidized starch Copolymer latex mentioned above 1° Solid content Adjusted to 50% (PH11 [prepared] using sodium hydroxide) (2) The following pigment coating compositions were prepared using copolymer latexes H and N, and coated papers were obtained in the same manner as in I) above.
評価結果を表−７に示した。。The evaluation results are shown in Table-7. .
本発明の実施例である共重合体ラテックスＨを用いた塗
工紙は、あらゆる顔料配合比においても、優れたグラビ
ア印刷適性を示していた０
被覆組成物
魚
分 散 剤 ０．２乾嚢重量部
リン酸エステル化澱粉 ３
共重合体ラテックス １０
固形分 ６０チに調製
（水酸化ナトリウムを用いＰＨ９に調製）〔測定及び評
価方法〕
（１） 塗料Ｂ型精度
ＢＬ型粘度計を用い、＃３０−ター、６０ ｒｐｍの条
件で測定した。The coated paper using copolymer latex H, which is an example of the present invention, showed excellent gravure printing suitability at all pigment blending ratios.Dry bag weight Partly phosphated starch 3 Copolymer latex 10 Solid content Adjusted to 60% (adjusted to pH 9 using sodium hydroxide) [Measurement and evaluation method] (1) Using a paint B type precision BL type viscometer, #30 -Measurements were made under conditions of 60 rpm.
（２） 被覆組成物のハイシェアー粘度バーキーリス
ハイシェアー粘度計を用いて、８０ Ｑ Ｏｒｐｍの所
の見掛は粘度を測定した。(2) High shear viscosity of the coating composition
Apparent viscosity was measured at 80 Q Orpm using a High Shear viscometer.
（３）被覆組成物の保水性
Ｓ、Ｄ、 Ｗａｒｒｅｎ法に準じて測定を行ない、良否
を判定し、◎（優） 、０／、０．△、×（劣）の分類
にて評価した。(3) Water retention of coating composition S, D, measured according to Warren method and judged as good or bad, ◎ (excellent), 0/, 0. Evaluation was made according to the classification of △ and × (poor).
（４）塗工紙ＲＩ Ｄｒｙ Ｐｉｃｋ強度ＲＩ印刷機を
用い、市販のオフセットインキにて印刷し、塗工紙のピ
ッキング状態を肉眼により判定し、◎（優）〜×（劣）
Ｋ分類した。(4) Coated paper RI Dry Pick strength Printed with commercially available offset ink using an RI printing machine, and visually judged the picking condition of the coated paper, ◎ (excellent) to × (poor).
Classified as K.
（５） 塗工紙グラビア印刷適性
大蔵省印刷研究所式グラビア印刷機を用い、網点グラビ
ア版を使用して印刷を行ないハーフトーンの所のミスド
ツトを数え、◎（優）〜×（劣）に分類し判定した。(5) Suitability for coated paper gravure printing Using a Ministry of Finance Printing Research Institute type gravure printing machine, print using a halftone gravure plate, count the misdots in the halftone area, and rate it as ◎ (excellent) to × (poor). Classified and judged.
Claims (1)
系単量体５０．５〜８５重量％、エチレン系不飽和カル
ボン酸単量体０．５〜１０重量％、エチレン系不飽和カ
ルボン酸アミド単量体０〜ＩＯ重量％、及びこれらと共
重合可能なモノオレフィン系単量体５〜４９重量％を乳
イヒ重合させて得られるガラス転移温度が一２５℃以下
の共重合体ラテックス３〜１５重量部およびΦ）澱粉１
〜３重景重量含むことを特徴とするグラビア印刷紙用被
覆組成物。 ２、共重合体ラテックスが異質多相構造を有する特許請
求の範囲第１項記載のグラビア印Ｉｌ１紙用被覆組成物
。 ３、共重合体ラテックスが異質多相構造を有し、その共
重合体ラテックスのガラス転移温度が一４０℃以下であ
る特許請求の範囲第１項又は第２項記載のグラビア印刷
紙用被覆組成物０[Claims] 1. With respect to 100 parts by weight of pigment, (A) conjugated diolefin monomer 50.5 to 85% by weight, ethylenically unsaturated carboxylic acid monomer 0.5 to 10% by weight, The glass transition temperature obtained by copolymerizing 0 to IO weight % of an ethylenically unsaturated carboxylic acid amide monomer and 5 to 49 weight % of a monoolefin monomer copolymerizable with these monomers is 125°C or lower. 3 to 15 parts by weight of copolymer latex and Φ) starch 1
A coating composition for gravure printing paper, characterized in that it contains .about.3 double weights. 2. The coating composition for gravure stamp Il1 paper according to claim 1, wherein the copolymer latex has a heterogeneous multiphase structure. 3. The coating composition for gravure printing paper according to claim 1 or 2, wherein the copolymer latex has a heterogeneous multiphase structure and the glass transition temperature of the copolymer latex is 140° C. or less. 0 things
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7445484A JPS60224895A (en) | 1984-04-12 | 1984-04-12 | Coating composition for gravure printing paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7445484A JPS60224895A (en) | 1984-04-12 | 1984-04-12 | Coating composition for gravure printing paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60224895A true JPS60224895A (en) | 1985-11-09 |
Family
ID=13547700
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7445484A Pending JPS60224895A (en) | 1984-04-12 | 1984-04-12 | Coating composition for gravure printing paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60224895A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149997A (en) * | 1985-12-25 | 1987-07-03 | ジェイエスアール株式会社 | Paper coating composition for gravure printing |
| JPS63270891A (en) * | 1987-04-24 | 1988-11-08 | ライオン株式会社 | Coating film forming agent for coat paper |
| JPH0219595A (en) * | 1988-07-08 | 1990-01-23 | Japan Synthetic Rubber Co Ltd | Coating composition for newspaper and coated paper for newspaper |
| JPH0274698A (en) * | 1988-09-07 | 1990-03-14 | Japan Synthetic Rubber Co Ltd | Light-weight coated paper |
| JPH04112038A (en) * | 1990-08-31 | 1992-04-14 | Dynic Corp | Nonwoven fabric for printing |
| JP2008261078A (en) * | 2007-04-13 | 2008-10-30 | Oji Paper Co Ltd | Bulky coated paper and method for producing the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5663096A (en) * | 1979-10-24 | 1981-05-29 | Japan Synthetic Rubber Co Ltd | Coating composition for gravure printing paper |
-
1984
- 1984-04-12 JP JP7445484A patent/JPS60224895A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5663096A (en) * | 1979-10-24 | 1981-05-29 | Japan Synthetic Rubber Co Ltd | Coating composition for gravure printing paper |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62149997A (en) * | 1985-12-25 | 1987-07-03 | ジェイエスアール株式会社 | Paper coating composition for gravure printing |
| JPS63270891A (en) * | 1987-04-24 | 1988-11-08 | ライオン株式会社 | Coating film forming agent for coat paper |
| JPH0219595A (en) * | 1988-07-08 | 1990-01-23 | Japan Synthetic Rubber Co Ltd | Coating composition for newspaper and coated paper for newspaper |
| JPH0274698A (en) * | 1988-09-07 | 1990-03-14 | Japan Synthetic Rubber Co Ltd | Light-weight coated paper |
| JPH04112038A (en) * | 1990-08-31 | 1992-04-14 | Dynic Corp | Nonwoven fabric for printing |
| JP2008261078A (en) * | 2007-04-13 | 2008-10-30 | Oji Paper Co Ltd | Bulky coated paper and method for producing the same |
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