JPH0460034B2 - - Google Patents
Info
- Publication number
- JPH0460034B2 JPH0460034B2 JP59188208A JP18820884A JPH0460034B2 JP H0460034 B2 JPH0460034 B2 JP H0460034B2 JP 59188208 A JP59188208 A JP 59188208A JP 18820884 A JP18820884 A JP 18820884A JP H0460034 B2 JPH0460034 B2 JP H0460034B2
- Authority
- JP
- Japan
- Prior art keywords
- calcium carbonate
- pigment
- inkjet recording
- easily dispersible
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 58
- 239000000049 pigment Substances 0.000 claims description 37
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 9
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 239000011247 coating layer Substances 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000012808 vapor phase Substances 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 25
- 239000011575 calcium Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- -1 etc. Substances 0.000 description 5
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 5
- 239000004927 clay Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 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 3
- 239000002245 particle Substances 0.000 description 3
- 229920002261 Corn starch Polymers 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229940099112 cornstarch Drugs 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001254 oxidized starch Substances 0.000 description 2
- 235000013808 oxidized starch Nutrition 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 235000019353 potassium silicate Nutrition 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000004826 Synthetic adhesive Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 239000007864 aqueous solution Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001454 recorded image Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
- B41M5/52—Macromolecular coatings
- B41M5/5218—Macromolecular coatings characterised by inorganic additives, e.g. pigments, clays
Description
〔産業上の利用分野〕
本発明はインクジエツト記録用シートに関し、
さらに詳しくは水性インクを用いるインクジエツ
ト記録方式において、シート表面に付着したイン
クの吸収速度が大きく、インクドツトの広がりお
よびにじみが小さく、かつシート表面上での像が
鮮明かつ高濃度で記録可能なインクジエツト記録
用シートに関するものである。
〔従来の技術〕
インクジエツト記録方式において、高品位の記
録像を得るために、各種顔料および接着剤より成
る塗工層をシート上に設ける方法が、従来技術と
して、数多く提案されている。
これらの提案のうち、顔料として炭酸カルシウ
ム（重質、軽質）を用いる方法として、例えば、
特開昭57−82085号、特開昭57−120846号、特開
昭57−126691号、特開昭57−129778号、特開昭57
−157786号、特開昭57−187289号、特開昭58−
55283号等があるが、使用すべき炭酸カルシウム
の物性を考慮したものはなく、僅かに特開昭57−
120486号、特公昭57−129778号、特開昭58−
55283号の各号公報において「恒圧透気法で測定
した比表面積が28000cm2／ｇ以下の軽質炭酸カル
シウム」と特定しているに過ぎない。しかも、こ
れらの提案はいずれも特殊な接着剤（ヒドロキシ
エチルセルロース、メチルセルロース、ポリビニ
ルピロリドン等）を使用することを指示してい
る。
すなわち、一般に、炭酸カルシウム（重質、軽
質）を顔料として用いた塗工層を設けたインクジ
エツト記録用紙はインク滴の吸収速度を上げるこ
とはできるが、インクの色濃度および鮮明性を上
げることは困難とされてきた。
〔発明が解決しようとする問題点〕
本発明は水性インクを用いるインクジエツト記
録方式において、記録シート表面に付着したイン
ク滴の吸収速度が大きく、インクドツトの広がり
およびにじみが小さく、かつシート表面上で像が
鮮明かつ高濃度に記録可能な塗工層を設けること
を目的とする。
〔発明の構成〕
本発明はシート上支持体上に顔料と接着剤を主
成分とする塗工層を設けたインクジエツト記録用
シートにおいて、顔料としてJIS Ｋ 5101による
吸油量が70〜90ml／100ｇで、かつBET式気相吸
着法による比表面積が60〜100m2／ｇの易分散性
炭酸カルシウム系複合顔料を使用したことを特徴
とするインクジエツト記録用シートである。
本発明者等は、前に述べた従来技術の欠点を除
くため、種々の炭酸カルシウムについてその製造
法も含めて検討を重ねた結果、紙、合成紙等のシ
ート状支持体上に顔料としてJIS K5101に規定さ
れる吸油量が70〜90ml／100ｇで、かつBET式気
相吸着法による比表面積が60〜100m2／ｇの易分
散性炭酸カルシウムを用い、これと接着剤を主成
分とする塗工液をシート支持体上に塗布、乾燥す
ることにより高吸収性かつ高解像度、高濃度のイ
ンクジエツト記録を可能ならしめるインクジエツ
ト記録用シートが得られることを見出した。
本発明に用いられる吸油量が70〜90ml／100ｇ
以上、かつ比表面積が60〜100m2／ｇの特性を有
する易分散性炭酸カルシウム系複合顔料は次の如
き製法により製造することができる：
即ち、膠質の金属水酸化物を生成しうる水に可
溶性の金属塩、例えば亜鉛、マグネシウム、アル
ミニウム等の硫酸塩、酢酸塩の水溶液あるいはこ
れらと硫酸、酢酸等の混合液を水酸化カルシウム
１モルに対して0.02〜0.10モルの割合で、炭酸化
率（CaCO3重量／Ca（OH）2重量×100（％））３％
以内で注入を完了する様、炭酸ガス中に例えばエ
ジエクタを用いて噴霧状態で混入反応させる。
さらに炭酸化率が80％に達した時点で可溶性珪
酸、例えば珪酸アルカリ、例えば珪酸ソーダ、又
は珪酸ゾルをSiO2換算で水酸化カルシウム１モ
ルに対し0.02〜0.08モル添加して炭酸化反応を継
続する事により、径0.01×長さ0.05〜1.00μmの連
鎖状粒子で、凝集性の極めて少ない珪酸及び亜鉛
を複合した炭酸カルシウム系顔料が製造される。
上記方法において、ZnSO4あるいはH2SO4の合
計のモル比が0.02モル未満又は0.10モルを超えた
場合、それらの添加時点が炭酸化率３％を超えた
場合もしくはCa（OH）2の濃度が15重量％を超え
た場合、また温度が20℃未満又は30℃を超える場
合及びCO2ガスの濃度が20容量％未満または40容
量％を超える場合は所期の0.01×0.10μm粒子寸法
を有する連鎖状粒子を得る事は出来ず、さらに珪
酸ソーダ又は珪酸ゾルがSiO2換算で0.02モル未満
又は0.08モルを超えた場合は所期の易分散性は得
られない（特開昭59−164370号参照）。
本発明は顔料として、上記の如き製造法による
吸油量が70〜90ml／100ｇ、かつ比表面積が60〜
100m2／ｇの特性を有する易分散性炭酸カルシウ
ム系複合顔料を使用することを特徴とするが、こ
の製法に限定されるものではなく、かつこれに他
の白色顔料、例えば、一般の紙塗工に使用される
カオリンクレー、タルク、ゼオライト、ホワイト
カーボン、水酸化アルミニウム、有機顔料（プラ
スチツクピグメント）等を配合してもよい。
また、これら顔料とともに使用する接着剤とし
てはカゼイン等蛋白質、殿粉およびその誘導体等
を含む天然もしくは加工接着剤ならびにポリビニ
ルアルコール系、ポリ酢酸ビニル系、スチレンブ
タジエンゴム系、アクリル系等の溶液もしくはエ
マルジヨン（ラテツクス）の形態をとる合成接着
剤をそれぞれ単独でもしくは配合して使用するこ
とができる。
一般的に云つて、全顔料に占める本発明の特徴
とする易分散性炭酸カルシウム系複合顔料の割合
（重量比）は５〜100％、好ましくは10〜70％であ
り、全顔料（100部）に対する接着剤割合（重量
比）は10〜60部、好ましくは15〜50部である。
さらに、本発明に用いられるシート状支持体と
しては通常の天然パルプ紙、ポリプロピレン、ポ
リエチレン、ポリエステル等のプラスチツクフイ
ルムシート、または無機繊維、合成繊維、合成パ
ルプ等を含有する紙状シート、合成樹脂フイルム
を凝紙化（表面処理、表面コート、顔料埋込等に
よる）したいわゆる合成紙のいずれでもよい。
以下、実施例によつて本発明をさらに詳細に説
明する。
実施例 １
顔料として易分散性炭酸カルシウム系複合顔料
（トヨフアイン、東洋電化工業社）50部（絶乾重
量、以下同じ）と米国産カオリンクレー（UW−
90、エンゲルハード社）50部に分散剤および水を
加えて高速分散混合機（KDミル、米国カイネチ
ツクデイスパージヨン社）中で分散混合を行つた
後、この混合液中へ酸化殿粉（玉子エースＡ、王
子コーンスターチ社）20部を粉体のまゝ投入添加
し、分散混合機を作動させたまゝ昇温させ殿粉を
糊化（90℃まで昇温、その温度で約15分間保持）
させた後冷却し、スチレンブタジエンラテツクス
（ｓ−0692、日本合成ゴム社）10部を添加、十分
混合することにより塗工液を調成し、この塗工液
の濃度および粘度を添加水により所望の値になる
よう調整した後、デイクソンパイロツトコーター
（英THデイクソン社）ロツドコーチンク法によ
り坪量65ｇ／m2の上質紙に塗工量が約10ｇ／m2に
なるよう塗工し、所望の塗工紙を得た。
実施例 ２
実施例１に述べた操作と同様の操作により、顔
料として易分散性炭酸カルシウム系複合顔料（ト
ヨフアイン、東洋電化工業社）50部と酸性白土系
ゼオライト（シルトンＢ、水沢化学工業社）50
部、接着剤として酸化殿粉（王子エースＢ、王子
コーンスターチ社）20部とアクリル系エマルジヨ
ン（モビニール963、ヘキスト合成社）20部を用
いた塗工液を調成し、この塗工液を用いて実施例
１と同じ操作により塗工紙を作製した。
なお、実施例１および２で用いた易分散性炭酸
カルシウム系複合顔料（トヨフアイン）は次の方
法で製造されたものである。
25℃、濃度10％のCa（OH）2懸濁液10tに対し、
エジエクターで噴霧状態にした濃度10％のZnSO4
溶液をCa（OH）21モルに対し0.03モルの量で混入
した30℃、30容量％のCO2ガスを１m3／minの流
速で流入反応させる。
ZnSO4の添加終了後はCO2ガスのみの炭酸化反
応になるが、Ca（OH）2の炭酸化率が80％に達し
た時点で、濃度10％の３号水ガラスを、SiO2換
算で0.04モル添加し、さらに反応を続けて炭酸化
反応を完結する事により、0.01（径）×0.08（長さ）
μm；BET比表面積65m2／ｇ；吸油量75ml／100
ｇの連鎖状炭酸カルシウム系複合顔料を得た。
実施例 ３
水ガラス（３号）の添加量をCa（OH）21モルに
対して0.07モルとした以外は実施例１及び２で用
いた易分散性炭酸カルシウムの製造法と同じ反応
条件で操作を行い、実施例１及び２で得た連鎖状
炭酸カルシウム系複合顔料と同じ粒度で、BET
比表面積98m2／ｇ、吸油量90ml／100ｇを有する
顔料が得られた。
次いで、顔料としてこの顔料50部（絶乾重量、
以下同じ）と米国産カオリンクレー（UV−90）
50部とした以外は実施例１と同じにして、塗工量
10ｇ／m2の塗工紙を得た。
参考例 １〜４
実施例１における易分散性炭酸カルシウム系複
合顔料（トヨフアイン）の代わりに、他の沈降性
炭酸カルシウム３種と、別の易分散性炭酸カルシ
ウム系複合顔料（トヨフアイン）１種をそれぞれ
用いて、実施例１と全く同様の操作によりそれぞ
れ塗工紙を作成した。これらを参考例１から４と
するが、その番号と使用沈降性炭酸カルシウムの
名称および炭酸カルシウム系複合顔料の関係は次
の通りである：
参考例１…沈降性炭酸カルシウム（ツネツクス
Ｅ、白石工業社）
参考例２…沈降性炭酸カルシウム（白艷華PZ、
白石工業社）
参考例３…沈降性炭酸カルシウム（ブリリアント
15、白石工業社）
参考例４…易分散性炭酸カルシウム系複合顔料
（トヨフアイン）
〔ZnSO4溶液の添加量をCa（OH）21モルに対
し0.01モルとした以外は実施例１および２で
用いた易分散性炭酸カルシウム系複合顔料の
製造方法と同じ反応条件で操作を行い得られ
たものである。〕
これら実施例１〜３および参考例１〜４に使用
した各炭酸カルシウムの物性を表−１に、また各
塗工紙のインクジエツト記録ドツト濃度を表−２
にそれぞれ示す。なお、ドツト濃度はマイクロデ
ンシトメーター（コニカ株式会社）で測定した。
[Industrial Application Field] The present invention relates to an inkjet recording sheet,
More specifically, in the inkjet recording method that uses water-based ink, the absorption speed of ink adhering to the sheet surface is high, the spreading and bleeding of ink dots is small, and the image on the sheet surface can be recorded with clearness and high density. This relates to sheets for use. [Prior Art] In order to obtain a high-quality recorded image in an inkjet recording system, many methods have been proposed as conventional techniques in which a coating layer made of various pigments and adhesives is provided on a sheet. Among these proposals, as a method of using calcium carbonate (heavy or light) as a pigment, for example,
JP-A-57-82085, JP-A-57-120846, JP-A-57-126691, JP-A-57-129778, JP-A-57
−157786, JP-A-57-187289, JP-A-58-
No. 55283, etc., but none takes into consideration the physical properties of calcium carbonate to be used, and only a few
No. 120486, Special Publication No. 129778, No. 129778, Special Publication No. 129778, No. 129778
Each publication of No. 55283 only specifies that it is ``light calcium carbonate with a specific surface area of 28000 cm 2 /g or less measured by constant pressure permeation method.'' Moreover, all of these proposals call for the use of special adhesives (hydroxyethylcellulose, methylcellulose, polyvinylpyrrolidone, etc.). That is, in general, inkjet recording paper provided with a coating layer using calcium carbonate (heavy or light) as a pigment can increase the absorption speed of ink droplets, but cannot increase the color density and sharpness of the ink. It has been considered difficult. [Problems to be Solved by the Invention] The present invention provides an inkjet recording method using water-based ink, which has a high absorption speed of ink droplets attached to the surface of a recording sheet, a small spreading and bleeding of ink dots, and an image forming method on the sheet surface. The purpose is to provide a coating layer that can record clearly and with high density. [Structure of the Invention] The present invention provides an inkjet recording sheet in which a coating layer mainly composed of a pigment and an adhesive is provided on a sheet support, and the pigment has an oil absorption of 70 to 90 ml/100 g according to JIS K 5101. This is an inkjet recording sheet characterized by using an easily dispersible calcium carbonate composite pigment having a specific surface area of 60 to 100 m 2 /g determined by BET vapor phase adsorption method. In order to eliminate the drawbacks of the prior art described above, the present inventors have repeatedly studied various calcium carbonates, including their production methods, and as a result, have developed a JIS pigment as a pigment on a sheet-like support such as paper or synthetic paper. Easily dispersible calcium carbonate with an oil absorption amount of 70 to 90 ml/100 g as specified in K5101 and a specific surface area of 60 to 100 m 2 /g by BET vapor phase adsorption method is used, and this and an adhesive are the main components. It has been found that by applying a coating liquid onto a sheet support and drying it, an inkjet recording sheet that enables inkjet recording with high absorbency, high resolution, and high density can be obtained. Oil absorption amount used in the present invention is 70-90ml/100g
The easily dispersible calcium carbonate-based composite pigment having the above characteristics and a specific surface area of 60 to 100 m 2 /g can be produced by the following method: In other words, it can be produced by adding water that can form a colloidal metal hydroxide. Add an aqueous solution of soluble metal salts, such as sulfates and acetates of zinc, magnesium, aluminum, etc., or a mixture of these with sulfuric acid, acetic acid, etc. at a ratio of 0.02 to 0.10 mol per 1 mol of calcium hydroxide to increase the carbonation rate. (CaCO 3 weight/Ca(OH) 2 weight x 100 (%)) 3%
For example, using an ejector, the carbon dioxide gas is mixed in a spray state and reacted so that the injection can be completed within a few seconds. Furthermore, when the carbonation rate reaches 80%, soluble silicic acid, such as alkali silicate, such as sodium silicate, or silicate sol, is added in an amount of 0.02 to 0.08 mol per 1 mol of calcium hydroxide in terms of SiO 2 to continue the carbonation reaction. By doing this, a calcium carbonate-based pigment composite of silicic acid and zinc, which has chain particles with a diameter of 0.01 and a length of 0.05 to 1.00 μm and has extremely low agglomeration, is produced. In the above method, when the total molar ratio of ZnSO 4 or H 2 SO 4 is less than 0.02 mol or more than 0.10 mol, when the carbonation rate exceeds 3%, or when the concentration of Ca(OH) 2 If the CO2 gas concentration exceeds 15% by weight, the temperature is less than 20°C or more than 30°C, and the concentration of CO2 gas is less than 20% by volume or more than 40% by volume, the expected 0.01 x 0.10 μm particle size Furthermore, if the amount of sodium silicate or silicate sol is less than 0.02 mol or more than 0.08 mol in terms of SiO 2 , the desired easy dispersibility cannot be obtained (Japanese Patent Application Laid-Open No. 164370-1982). (see issue). The present invention is a pigment that has an oil absorption of 70 to 90 ml/100 g and a specific surface area of 60 to 60.
It is characterized by using an easily dispersible calcium carbonate-based composite pigment having a property of 100 m 2 /g, but it is not limited to this manufacturing method, and other white pigments, such as general paper coatings, can also be used. Kaolin clay, talc, zeolite, white carbon, aluminum hydroxide, organic pigments (plastic pigments), etc. used in the manufacturing process may be blended. Adhesives used with these pigments include natural or processed adhesives containing proteins such as casein, starch and their derivatives, and solutions or emulsions of polyvinyl alcohol, polyvinyl acetate, styrene-butadiene rubber, acrylic, etc. Synthetic adhesives in the form of (latex) can be used alone or in combination. Generally speaking, the proportion (weight ratio) of the easily dispersible calcium carbonate-based composite pigment, which is a feature of the present invention, in the total pigment is 5 to 100%, preferably 10 to 70%, and the total pigment (100 parts ) to the adhesive (weight ratio) is 10 to 60 parts, preferably 15 to 50 parts. Further, as the sheet-like support used in the present invention, ordinary natural pulp paper, plastic film sheets such as polypropylene, polyethylene, and polyester, paper-like sheets containing inorganic fibers, synthetic fibers, synthetic pulp, etc., and synthetic resin films can be used. Any of the so-called synthetic papers that have been hardened (through surface treatment, surface coating, pigment embedding, etc.) may be used. Hereinafter, the present invention will be explained in more detail with reference to Examples. Example 1 As pigments, 50 parts of easily dispersible calcium carbonate-based composite pigment (Toyofain, Toyo Denka Kogyo Co., Ltd.) (absolute dry weight, same hereinafter) and American kaolin clay (UW-
After adding a dispersant and water to 50 parts of 90, Engelhard, and performing dispersion mixing in a high-speed dispersion mixer (KD Mill, Kinetics Dispersion Co., USA), oxidized starch ( Add 20 parts of Egg Ace A (Oji Cornstarch Co., Ltd.) as a powder and heat it up while the dispersion mixer is running to gelatinize the starch (heat up to 90℃ and hold at that temperature for about 15 minutes) )
After cooling, add 10 parts of styrene-butadiene latex (s-0692, Japan Synthetic Rubber Co., Ltd.) and mix thoroughly to prepare a coating liquid. After adjusting to the desired value, coat it on high-quality paper with a basis weight of 65 g/m 2 using the rod coating method using a Dickson Pilot Coater (TH Dickson Ltd., UK) to a coating weight of approximately 10 g/m 2 . A coated paper was obtained. Example 2 By the same operation as described in Example 1, 50 parts of an easily dispersible calcium carbonate composite pigment (Toyofain, Toyo Denka Kogyo Co., Ltd.) and acid clay zeolite (Silton B, Mizusawa Chemical Industry Co., Ltd.) were added as pigments. 50
A coating solution was prepared using 20 parts of oxidized starch (Oji Ace B, Oji Cornstarch Co., Ltd.) and 20 parts of acrylic emulsion (Movinyl 963, Hoechst Gosei Co., Ltd.) as an adhesive. A coated paper was prepared in the same manner as in Example 1. The easily dispersible calcium carbonate composite pigment (Toyofain) used in Examples 1 and 2 was manufactured by the following method. For 10 t of Ca(OH) 2 suspension with a concentration of 10% at 25 °C,
ZnSO4 with a concentration of 10% sprayed with an ejector
The solution was mixed with 0.03 mol of Ca(OH) 2 in an amount of 0.03 mol per mol of Ca(OH) 2 at 30° C., and 30% by volume CO 2 gas was introduced at a flow rate of 1 m 3 /min to cause a reaction. After the addition of ZnSO 4 is completed, the carbonation reaction starts with only CO 2 gas, but when the carbonation rate of Ca(OH) 2 reaches 80%, No. 3 water glass with a concentration of 10% is converted into SiO 2 equivalent. By adding 0.04 mol and continuing the reaction to complete the carbonation reaction, 0.01 (diameter) x 0.08 (length)
μm; BET specific surface area 65m 2 /g; oil absorption 75ml/100
A chain-like calcium carbonate-based composite pigment of g was obtained. Example 3 The reaction conditions were the same as those for producing easily dispersible calcium carbonate used in Examples 1 and 2, except that the amount of water glass (No. 3) added was 0.07 mol per 1 mol of Ca(OH) 2 . With the same particle size as the chain calcium carbonate composite pigment obtained in Examples 1 and 2, BET
A pigment having a specific surface area of 98 m 2 /g and an oil absorption of 90 ml/100 g was obtained. Next, 50 parts of this pigment (absolutely dry weight,
(same below) and American kaolin clay (UV-90)
The coating amount was the same as Example 1 except that it was 50 parts.
A coated paper of 10 g/m 2 was obtained. Reference Examples 1 to 4 Instead of the easily dispersible calcium carbonate-based composite pigment (Toyohua In) in Example 1, three other types of precipitated calcium carbonate and one other easily dispersible calcium carbonate-based composite pigment (Toyohua In) were used. A coated paper was prepared using each of them in exactly the same manner as in Example 1. These are referred to as Reference Examples 1 to 4, and the relationships between their numbers, names of precipitated calcium carbonate used, and calcium carbonate-based composite pigments are as follows: Reference Example 1...Precipitated calcium carbonate (Tunetsu E, Shiraishi Kogyo Co., Ltd.) ) Reference example 2... Precipitated calcium carbonate (Shiraika PZ,
Reference example 3... Precipitated calcium carbonate (Brilliant
15, Shiraishi Kogyo Co., Ltd.) Reference Example 4...Easily dispersible calcium carbonate-based composite pigment (Toyofain) [Example 1 and 2 except that the amount of ZnSO 4 solution added was 0.01 mol per 1 mol of Ca(OH) 2 This was obtained by operating under the same reaction conditions as the method for producing the easily dispersible calcium carbonate-based composite pigment used. ] The physical properties of each calcium carbonate used in Examples 1 to 3 and Reference Examples 1 to 4 are shown in Table 1, and the inkjet recording dot density of each coated paper is shown in Table 2.
are shown respectively. Note that the dot density was measured using a microdensitometer (Konica Corporation).
【表】【table】
【表】【table】
以上の実施例および参考例に示した結果から、
顔料としてJIS Ｋ 5101に規定される吸油量が70
〜90ml／100ｇで、かつBET式気相吸着法による
比表面積が60〜100m2／ｇの易分散性炭酸カルシ
ウムを用いて製造したインクジエツト記録用シー
トは、印字ドツト濃度を従来法の炭酸カルシウム
を使用して製造したインクジエツト記録用シート
のそれに比較して格段と大きくすることを可能な
らしめるものであり、産業界に寄与するところ大
である。
From the results shown in the above examples and reference examples,
The oil absorption amount specified by JIS K 5101 as a pigment is 70.
The inkjet recording sheet manufactured using easily dispersible calcium carbonate with a specific surface area of ~90ml/100g and a specific surface area of 60~100m 2 /g by the BET gas phase adsorption method has a printing dot density that is lower than that of the conventional calcium carbonate method. This makes it possible to make the inkjet recording sheet much larger than that of the inkjet recording sheet manufactured using this method, and it will greatly contribute to the industrial world.
Claims (1)
する塗工層を設けたインクジエツト記録用シート
において、顔料としてJIS Ｋ 5101による吸油量
が70〜90ml／100ｇで、かつBET式気相吸着法に
よる比表面積が60〜100m2／ｇの易分散性炭酸カ
ルシウム系複合顔料を使用したことを特徴とする
インクジエツト記録用シート。1 In an inkjet recording sheet in which a coating layer mainly composed of pigment and adhesive is provided on a sheet support, the pigment has an oil absorption amount of 70 to 90 ml/100 g according to JIS K 5101, and has a BET vapor phase adsorption capacity. 1. An inkjet recording sheet characterized by using an easily dispersible calcium carbonate composite pigment having a specific surface area of 60 to 100 m 2 /g according to the method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59188208A JPS6166686A (en) | 1984-09-10 | 1984-09-10 | Sheet for ink jet recording |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59188208A JPS6166686A (en) | 1984-09-10 | 1984-09-10 | Sheet for ink jet recording |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6166686A JPS6166686A (en) | 1986-04-05 |
| JPH0460034B2 true JPH0460034B2 (en) | 1992-09-24 |
Family
ID=16219656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59188208A Granted JPS6166686A (en) | 1984-09-10 | 1984-09-10 | Sheet for ink jet recording |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6166686A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2725802B2 (en) * | 1988-09-27 | 1998-03-11 | 王子製紙株式会社 | Thermal transfer ink image receiving sheet |
| JP2762879B2 (en) * | 1992-12-07 | 1998-06-04 | 日本製紙株式会社 | Recording sheet for thermosensitive stencil printing |
| US5643631A (en) * | 1995-03-17 | 1997-07-01 | Minerals Tech Inc | Ink jet recording paper incorporating novel precipitated calcium carbonate pigment |
| US8361572B2 (en) * | 2009-10-30 | 2013-01-29 | Hewlett-Packard Development Company, L.P. | Coated medium for inkjet printing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS529074A (en) * | 1975-07-10 | 1977-01-24 | Sekisui Chemical Co Ltd | Material for recording |
| JPS57120486A (en) * | 1981-01-21 | 1982-07-27 | Jujo Paper Co Ltd | Water-color ink recording paper |
| JPS5855283A (en) * | 1981-09-30 | 1983-04-01 | Jujo Paper Co Ltd | Ink jet recording paper |
-
1984
- 1984-09-10 JP JP59188208A patent/JPS6166686A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS529074A (en) * | 1975-07-10 | 1977-01-24 | Sekisui Chemical Co Ltd | Material for recording |
| JPS57120486A (en) * | 1981-01-21 | 1982-07-27 | Jujo Paper Co Ltd | Water-color ink recording paper |
| JPS5855283A (en) * | 1981-09-30 | 1983-04-01 | Jujo Paper Co Ltd | Ink jet recording paper |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6166686A (en) | 1986-04-05 |
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