JPS5841994A - Paper coating composition - Google Patents
Paper coating compositionInfo
- Publication number
- JPS5841994A JPS5841994A JP13872681A JP13872681A JPS5841994A JP S5841994 A JPS5841994 A JP S5841994A JP 13872681 A JP13872681 A JP 13872681A JP 13872681 A JP13872681 A JP 13872681A JP S5841994 A JPS5841994 A JP S5841994A
- Authority
- JP
- Japan
- Prior art keywords
- paper
- coating composition
- water
- reaction
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyamides (AREA)
- Phenolic Resins Or Amino Resins (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】
本発明は紙用塗工組成物に関するものであり、その目的
は、インキ転移性向上に降れ、高P (1時の耐水性が
良好であり、しかも、塗工紙からのホルムアルデヒドの
発生量が極めな
で少なく、着色性がφい、オフセット輪転印f61.l
での耐ブリスジ−性が良好であるなどの印刷用塗工紙と
して優れた性能を付与する紙用塗工組成物を提供するこ
と曝こある。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a coating composition for paper, and the purpose thereof is to improve ink transfer properties, have high P (1 hour water resistance), and coated paper with good water resistance. An offset rotary press f61.l with extremely low formaldehyde generation and poor coloring properties.
It is an object of the present invention to provide a coating composition for paper that provides excellent performance as a coated paper for printing, such as good blistering resistance.
従来より、水性バインダーあるいはそのほか1こ顔料等
の助剤を含む紙用塗工組成物を紙基体に塗布し、紙表面
に塗被層を設けて塗工紙を製造することは公知であり、
この際塗被層に耐水性を付うする目的で種々の耐水化剤
が利用されている。It is conventionally known to manufacture coated paper by applying a paper coating composition containing an aqueous binder or one other auxiliary agent such as a pigment to a paper substrate and providing a coating layer on the paper surface.
At this time, various waterproofing agents are used for the purpose of imparting water resistance to the coating layer.
しかしながら、近年の紙塗工技術および印刷技術の発達
はめざましいものがあり、省力化、合理化をはかる上で
も塗工時および印刷時の高速化が進められている。特に
塗工紙の旬造工即の分野においては、省エネルギー、省
資源を図るため塗工組成物中に配合する顔料として炭酸
力Iレシウムの使用の増加が目ざましく、印刷技術の分
野1こおいてはオフセット輪転印刷の普及および塗工紙
の多様化にともない、塗工紙には種々の性能が要求され
るに至り、水性バインダー成分の改質や補助成分の改良
など多くの対応策が提案されている、すなわち、塗工紙
としては、印刷インキ転移性、網点再現性および耐水性
やオフ輪印刷の耐ブリスター性の向上が従来以上曝こ望
まれているのも一つである。However, recent advances in paper coating technology and printing technology have been remarkable, and efforts are being made to increase the speed of coating and printing in order to save labor and streamline the process. Particularly in the field of coated paper, there has been a remarkable increase in the use of lesium carbonate as a pigment added to coating compositions in order to conserve energy and resources. With the spread of offset rotary printing and the diversification of coated paper, various performances have come to be required of coated paper, and many countermeasures have been proposed, such as modifying the aqueous binder component and improving auxiliary components. In other words, for coated paper, improvements in printing ink transferability, halftone dot reproducibility, water resistance, and blister resistance in off-wheel printing are more desired than ever.
耐水性(湿時強度)は例えば、顔料に対する水性バイン
ダー成分の増量などで効果的に改良しうるが、一方では
印刷時のインキ転移性が低下するなどのに点があり、有
効な方法がなく、この問題を改良しうる手段として、と
くに補助成分としての耐水化剤の配合1こよる方法が行
なわれているのが現状である、この場合の、耐水化剤の
代表的なものは水性バインダーの耐水化剤であるが、従
来から使用ないし提案されている耐水化剤はいずれも有
効な長所を有する反面、同時に重要な欠のではなかった
。Water resistance (wet strength) can be effectively improved by, for example, increasing the amount of aqueous binder component relative to the pigment, but on the other hand, there are drawbacks such as a decrease in ink transfer during printing, and there is no effective method. Currently, as a means to improve this problem, a method is currently being used that involves adding a water-resistant agent as an auxiliary component.A typical water-resistant agent in this case is a water-based binder. However, while all of the previously used or proposed water resistance agents have effective advantages, at the same time they do not have important deficiencies.
例えばメラミン−ホルムアルデヒド初期縮合物は塗工紙
の印刷インキの転移性が不十分であり、又塗工組成物の
pHが高い場合、耐水効果が不十分であり、又塗工紙か
らの遊離ホルムアルデヒドの発生量が多(作業衛生環境
上好ましくないなどの問題があった。又、ポリアミドポ
リ尿素とホルムアルデヒドのみとの反応生成物は塗工紙
の印刷インキの転移性向上効果にすぐれ、耐水性も良好
で塗工紙からの遊離ホルムアルデヒドの発生量も少ない
利点を有しているが、持に塗工組成物の高pH時での耐
水効果および立上り性やインキ転移性向上効果會こ、今
−歩劣るものである。For example, melamine-formaldehyde initial condensates have insufficient transferability of printing ink on coated paper, and when the pH of the coating composition is high, the water resistance effect is insufficient, and free formaldehyde from coated paper There were problems such as the generation of a large amount of (unfavorable in terms of work hygiene).In addition, the reaction product of polyamide polyurea and formaldehyde alone has an excellent effect on improving the transferability of printing ink on coated paper, and has excellent water resistance. It has the advantage that the amount of free formaldehyde generated from the coated paper is small. It is inferior.
またグリオキザールなどのジアルデヒドは塗工紙の着色
があり、耐水効果の経時劣化や印刷インキの転移性向上
効果が劣る。ジルコニウムなどの多価金属塩は塗工液に
著しい増粘があって作業性に劣る。更にrトン−ホルム
アルデヒド初期縮合物は動水効果、印刷インキの転移性
向上効果で劣る。Further, dialdehydes such as glyoxal cause coloring of coated paper, deteriorate water resistance over time, and have poor effects on improving printing ink transferability. Polyvalent metal salts such as zirconium significantly increase the viscosity of the coating solution, resulting in poor workability. Furthermore, the r-ton-formaldehyde initial condensate is inferior in hydrodynamic effect and effect on improving transferability of printing ink.
このようなことから、本発明者らは塗工組成物のpHが
高い場合の耐水効果1こ優れるとともに、上述した各種
の欠点がなく、かつ印刷時のインキ転移性向上効果−こ
極めて優れる紙用塗工組成物を開発すべく、鋭意検討の
結果、特定の方法により製造した熱硬化性樹脂水溶液を
耐水化剤として含有せしめてなる紙用塗工組成物が上記
目的を満足せしめ、画めてすぐれた効果を有することを
見出し、本発明に至った。For this reason, the present inventors have developed a paper that has excellent water resistance when the pH of the coating composition is high, is free from the various drawbacks mentioned above, and has an extremely excellent effect of improving ink transfer during printing. As a result of intensive studies to develop a coating composition for paper, a coating composition for paper containing an aqueous solution of a thermosetting resin produced by a specific method as a water-resistant agent satisfied the above objectives, and It was discovered that this method has excellent effects, leading to the present invention.
すなわち本発明は、水性バインダーおよび耐水化剤を含
有してなる紙用塗工組成物1ζおいて、耐水化剤として
、尿素とポリアルキレンポリアミンを脱アンモニア反応
させ、次いで二塩基性カルボン酸と脱水縮合させ、更に
と二塩基性カルボン酸と脱水縮合させ、次いで尿素と脱
アンモニア反応させて得られるボリアミドポリ域素に、
水溶液中でエビ7Nロヒドリン及びホルムアルデヒドを
反応せしめることにより得られる熱硬化性樹脂水溶液を
用いてなる紙用塗工組成物を提供するものである。That is, in the paper coating composition 1ζ containing an aqueous binder and a water-resistant agent, urea and a polyalkylene polyamine are subjected to a deammonia reaction as a water-resistant agent, and then a dibasic carboxylic acid and a dehydrated A polyamide polyester obtained by condensation, dehydration condensation with dibasic carboxylic acid, and deammonia reaction with urea,
The present invention provides a paper coating composition using an aqueous thermosetting resin solution obtained by reacting shrimp 7N lohydrin and formaldehyde in an aqueous solution.
本発明に使用されるポリアルキレンポリアミンとは分子
中に2個の第1級アミノ基および少なくとも1個の第2
級アミノ基を有するポリアルキレンポリアミンであり、
例えばジエチレントリアミン、トリエチレンテトラミン
、テトラエチレンペン9にン、fイミノビスプロビルア
ミン、8−アザヘキサン−1,6−ジアミン、4.7−
シアザデカンー1.10−ジアミン等が挙げられる。こ
れらポリアルキレンポリアミンは一種のみならず二種以
上の混合物としても用いることができる。The polyalkylene polyamine used in the present invention has two primary amino groups and at least one secondary amino group in the molecule.
A polyalkylene polyamine having a class amino group,
For example, diethylenetriamine, triethylenetetramine, tetraethylene penne, fiminobisprobylamine, 8-azahexane-1,6-diamine, 4.7-
Examples include cyazadecane-1,10-diamine. These polyalkylene polyamines can be used not only alone but also as a mixture of two or more.
また、本発明に於いて使用される二塩基性カルボン酸と
してはコハク酸、グルクル酸、アレピン酸、セバシン酸
、マレイン酸、フマ−ル酸の如き脂肪族カルボン酸、イ
ソフタル酸、テレフタル酸の如き芳香族カルボン酸およ
びこれらの混合物が挙げられる。Further, dibasic carboxylic acids used in the present invention include aliphatic carboxylic acids such as succinic acid, glucuric acid, arepic acid, sebacic acid, maleic acid, and fumaric acid, isophthalic acid, and terephthalic acid. Mention may be made of aromatic carboxylic acids and mixtures thereof.
本発明で使用するエピハロヒドリンとしてエピクロルヒ
ドリン、エビブロムヒドリン等が挙げられるが、エピク
ロルヒドリンが特−コ好ましい。Epihalohydrin used in the present invention includes epichlorohydrin, ebibromohydrin, etc., and epichlorohydrin is particularly preferred.
本発明1こいうポリアミドポリ尿素は、尿素とポリアル
キレンポリアミンを脱アンモニア反応させ、次いで二塩
基性カルボン酸と脱水縮合させ、更−ζ尿素と脱アンモ
ニア反応させて得られるポリアミドポリ尿素(以下ポリ
アミドポリ尿素(lと称する−1)又はポリアルキレン
ポリアミンと二塩基性カルボン酸を脱水縮合させ、次い
で尿素と脱アンモニア反応させて得られるポリアミドポ
リ尿素(以下ポリアミドポリ尿素(B)と称する)であ
る。The polyamide polyurea of the present invention 1 is a polyamide polyurea (hereinafter referred to as polyamide polyurea) obtained by subjecting urea and polyalkylene polyamine to a deammoniation reaction, followed by dehydration condensation with a dibasic carboxylic acid, and further deammoniation reaction with ζ-urea. It is a polyamide polyurea (hereinafter referred to as polyamide polyurea (B)) obtained by dehydration condensation of polyurea (referred to as -1) or polyalkylene polyamine and dibasic carboxylic acid, and then deammonia reaction with urea. .
ポリアミドポリ尿素(A〕1ζおいで、尿素とポ、リア
ルキレンポリアミンとのモル比はおよそ1:2付近で実
施することが好ましい。In the polyamide polyurea (A) 1ζ, the molar ratio of urea and poly-, realkylene polyamine is preferably around 1:2.
反応温度は100〜200℃好ましくは120〜170
℃が適当であり、発生するアンモニアを系外也こ除去し
つつ、2〜8時間反応せしめる。次いでポリアルキレン
ポリアミン1モル嶺こ対し、0,8〜1.2モルの二塩
基性カルボン酸と脱水縮合せしめる。反応温度120〜
250℃好ましくは140〜200℃1こて、生成する
水を系外に除去しながら、2〜10時間反応を行なう。The reaction temperature is 100-200℃, preferably 120-170℃
℃ is appropriate, and the reaction is allowed to proceed for 2 to 8 hours while removing the generated ammonia from the system. Next, 1 mole of polyalkylene polyamine is subjected to dehydration condensation with 0.8 to 1.2 moles of dibasic carboxylic acid. Reaction temperature 120~
The reaction is carried out at 250° C., preferably 140° C. to 200° C., for 2 to 10 hours while removing produced water from the system.
このようにして得られた縮合反応生成物を更場ζ腋素と
反応させる。尿素の量は、原料ポリアルキレンポリアミ
ン中の第二級アミノ基1モル当たり、0.2〜1.5モ
ル好ましくは0.5〜1.1モルである。反応温度は1
00〜180℃好ましくは120〜150℃であり、こ
の温度で1〜5時間、発生するアンモニアを系外1こ除
去しながら反応を行なら。このようにしてポリアミ・ド
ポリ尿素(A)が得られる。The condensation reaction product thus obtained is reacted with Saraba ζaxillary element. The amount of urea is 0.2 to 1.5 moles, preferably 0.5 to 1.1 moles, per mole of secondary amino groups in the raw material polyalkylene polyamine. The reaction temperature is 1
The reaction temperature is 00 to 180°C, preferably 120 to 150°C, and the reaction is carried out at this temperature for 1 to 5 hours while removing one portion of generated ammonia from the system. In this way, polyamide polyurea (A) is obtained.
ポリアミドポリ尿素CB)において、ポリアルキレンポ
リアミンと二塩基性カルボン酸との反応は、温度120
〜250℃好ましくは140〜200℃にて、生成する
水を系外に除去しながら2〜10時間行なわれる。二塩
基性カルボン酸1モルーζ対し、ポリアルキレンポリア
ミン1.4〜8.0モル好ましくは1.8〜2.5 モ
ルのモル比で反応を行なう。このようにして得ら′6た
脱水縮合反応生成物を次いで尿素と反応させる。尿素の
使用量は、原料ポリアルキレンポリアミン中のアミノ基
1モル当たり、0.2〜1.0モル好ましくは0.4〜
0.8モルである。反応温度は100〜180℃である
が、120〜150℃が好適である。In the polyamide polyurea CB), the reaction between the polyalkylene polyamine and the dibasic carboxylic acid is carried out at a temperature of 120
The reaction is carried out at a temperature of -250°C, preferably 140-200°C, for 2-10 hours while removing generated water from the system. The reaction is carried out at a molar ratio of 1.4 to 8.0 mol, preferably 1.8 to 2.5 mol, of the polyalkylene polyamine per 1 mol ζ of the dibasic carboxylic acid. The dehydration condensation reaction product thus obtained is then reacted with urea. The amount of urea used is 0.2 to 1.0 mol, preferably 0.4 to 1.0 mol, per 1 mol of amino groups in the raw material polyalkylene polyamine.
It is 0.8 mol. The reaction temperature is 100 to 180°C, preferably 120 to 150°C.
コノ温度で1〜5時間発生するアンモニアを系外1こ除
去しつつ反応を行なう6尿素の仕込方法として所要量を
一括して仕込み反応せしめることも、また所要量の一部
を仕込み、脱アンモニア反応を完結せしめた後、残りの
線素を仕込み鍔度脱アンモニア反応を行なうことも可能
である。このよう昏ζして、ポリアミドポリ尿素CB)
が得られる。The reaction is carried out while removing the ammonia that is generated from the system for 1 to 5 hours at a temperature of 6. As a method of preparing 6-urea, it is possible to charge the required amount all at once and allow the reaction to take place, or to charge a part of the required amount and remove the ammonia. After the reaction is completed, it is also possible to charge the remaining wire elements and perform the deammonification reaction. In this way, polyamide polyurea CB)
is obtained.
上記のよう竜こして得られたポリアミドポリ尿素を水に
溶解せしめ、エピハロヒドリン及びホルムアルデヒドと
反応せしめる。反応順序として、■ポリアミドポリ尿素
とエピハロヒドリンを反応させ、次いでホルムアルデヒ
ドと反応させる、■ポリアミドポリ尿素とホルムアルデ
ヒドを反応させ、次イテエヒハロヒドリンを反応させる
。■エビ710ヒドリンとホルムアルデヒドを同時に反
応させる、のいずれの方法でも本発明の目的は達成され
る。The polyamide polyurea obtained by straining as described above is dissolved in water and reacted with epihalohydrin and formaldehyde. The reaction order is: 1. Polyamide polyurea and epihalohydrin are reacted, and then formaldehyde is reacted. 2. Polyamide polyurea and formaldehyde are reacted, and then epihalohydrin is reacted. (2) The object of the present invention can be achieved by any method in which shrimp 710 hydrin and formaldehyde are reacted simultaneously.
ただし、ホルムアルデヒドとの反応は、後述するよう−
こ酸性下で、もしくは一旦アルカリ性下で行なった後更
1こ酸性下で行なうことが好ましい。However, the reaction with formaldehyde is -
It is preferable to carry out the reaction under acidic conditions, or once under alkaline conditions, and then further under acidic conditions.
ポリアミドポリ尿素とエピハロヒドリン及びホルムアル
デヒドとの反応は、濃度20〜70重量%、好ましくは
80〜60%の水溶液中で、反応温度80〜80℃で2
〜15時間行なわれる。エピハロヒドリンとの反応はp
H3〜12といった広いpH範囲で行ないうるが、ホ
ルムアルデヒドとの反応は、pK7以下好ましくはpH
8〜6,5となるよう1こ酸、例えば塩酸、硫酸、リン
酸、ギ酸、酢酸等1こより調整した後行なうか、もしく
は、−目PH7〜12といったアルカリ性下で反応を行
ない、ついでPHを7以下、好ましくはpH8〜6.5
1こ調整して反応を続けることがアIレキルンlリアミ
ン中のアミノ基1モル当たり0.02〜0.8モル、好
ましくは0.04〜0.2モルである。また、ポリアミ
ドポリ尿素の製造に使用した全尿素1モル当たり、0.
(16〜1モルのホルムアルデヒド好ましくは0.1〜
06モルのホルムアルデヒドが使用される。The reaction of polyamide polyurea with epihalohydrin and formaldehyde is carried out in an aqueous solution with a concentration of 20 to 70% by weight, preferably 80 to 60%, at a reaction temperature of 80 to 80°C.
It will last for ~15 hours. The reaction with epihalohydrin is p
Although the reaction with formaldehyde can be carried out in a wide pH range such as H3 to H12, the reaction with formaldehyde is preferably carried out at a pH of 7 or below.
The reaction is carried out after adjusting the pH from 1 to 1 to 6.5, such as hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, etc., or the reaction is carried out under alkaline conditions such as pH 7 to 12, and then the pH is adjusted. 7 or less, preferably pH 8-6.5
The reaction is continued by adjusting the amount by 0.02 to 0.8 mol, preferably 0.04 to 0.2 mol, per mol of amino group in the amine. In addition, per mole of total urea used in the production of polyamide polyurea, 0.
(16-1 mol of formaldehyde, preferably 0.1-1 mol)
0.6 mol of formaldehyde are used.
かくして本発明1ζ用い得る熱硬化性樹脂水溶液を得る
ことができる。In this way, an aqueous thermosetting resin solution that can be used in the present invention 1ζ can be obtained.
本発明の紙用塗工組成物は、耐水化剤として本発明)こ
特定する熱硬化性樹脂水溶液を用いる以外は従来法と全
く同様にして調整されるが、その効果を有効1こ発揮さ
せるため、該熱硬化性樹脂水溶液は固型分として通常水
性バインダー(@型分)100重量部あたり0.8〜2
0重東部配合される。The paper coating composition of the present invention is prepared in exactly the same manner as the conventional method except for using the thermosetting resin aqueous solution specified by the present invention as a water-resistant agent, but the paper coating composition of the present invention can effectively exhibit its effects. Therefore, the thermosetting resin aqueous solution usually has a solid content of 0.8 to 2 parts by weight per 100 parts by weight of the aqueous binder (@type part).
Contains 0 heavy Tobu.
また、本発明tこ用いる熱硬化性1に水溶液は耐水化剤
としてこれ単独でも充分にその効果を発揮するが、場合
−こよってはその一部を他の耐水化剤で置き換えること
も可能である。In addition, the aqueous solution used in the thermosetting agent 1 of the present invention is sufficiently effective as a water-resistant agent alone, but in some cases, it is also possible to replace a part of it with another water-resistant agent. be.
本発明の紙用塗工組成物を調整する1こ際して用いられ
る水性バインダーは従来より公知のものがそのまま適用
される。As the aqueous binder used in preparing the paper coating composition of the present invention, conventionally known aqueous binders can be used as they are.
かかる水性バインダーの例としては、たとえばで紀ぶん
、酸化でへぶん、変性でんぷん、チルセルロース、大豆
タンパクなどの水溶性バインダー、スチレソーブケジェ
ン系樹脂、酢酸ビニル樹脂、エチレン−酢酸ビニル樹脂
、メチルメタクリレート樹脂などの水乳化、分散系のバ
インダーが例示される。Examples of such aqueous binders include water-soluble binders such as dekibun, oxidation hebun, modified starch, chilled cellulose, soybean protein, styresorbent resin, vinyl acetate resin, ethylene-vinyl acetate resin, methyl Examples include water emulsion and dispersion type binders such as methacrylate resins.
本発明の紙用塗工組成物は、前記熱硬化性樹脂水溶液お
よび水性バインダーの他顔料、分散剤、増粘剤、減粘剤
、消泡剤、抑泡剤、防腐剤、防カビ剤、流動調整剤、剥
離剤、染料、顔料などの着色剤、導電剤などの特殊性能
付与剤などを必要iこ応じて配合することもでき、これ
亀こより本発明の効果が妨げられるものではない。The paper coating composition of the present invention includes, in addition to the thermosetting resin aqueous solution and aqueous binder, pigments, dispersants, thickeners, thinners, antifoaming agents, foam suppressants, preservatives, antifungal agents, Flow control agents, release agents, coloring agents such as dyes and pigments, special performance imparting agents such as conductive agents, etc. may be added as necessary, and the effects of the present invention will not be hindered.
顔料の例としては、例えばカオリンクレー、タルク、二
酸化チタン、水酸化アIレミニクム、炭酸カルシウム、
サテンホワイト、硫酸バリウムなどの無機顔料およびス
チレン、尿素などを主成分とする有機顔料が例示され、
これらはそれぞれ単独あるいは任意の割合で2種以上が
混合使用される。Examples of pigments include kaolin clay, talc, titanium dioxide, aluminum hydroxide, calcium carbonate,
Examples include inorganic pigments such as satin white and barium sulfate, and organic pigments whose main components are styrene and urea.
These may be used alone or in combination of two or more in any proportion.
また本発明の塗工組成物はS度eの他の調整条件も従来
法とまったく同様に通常の方法によって調整することが
でき、特に制限はない。例えば予め水乳化、分散系のバ
インダー、水溶性バインダーなどの接着剤成分あるいは
顔料スラリー等に本発明の熱硬化性1fi1411#水
溶液の必要量を配合しておいてもよく、eの他任意の順
序で配合することができる。Further, other conditions for adjusting the S degree e of the coating composition of the present invention can be adjusted by conventional methods in exactly the same manner as conventional methods, and there are no particular limitations. For example, the required amount of the thermosetting 1fi1411# aqueous solution of the present invention may be blended in advance with an adhesive component such as a water emulsion, a dispersion binder, a water-soluble binder, or a pigment slurry, or in any order other than e. It can be blended with
持、C本発明の熱硬化性m1ll水溶液を、スチレソー
ブ5!ジエン系樹脂、メチルメタクリレート樹脂などの
水乳化、分散系バインダー1こ予め配合しておくことは
、塗工組成物が容易番こ調整でき、かつ、塗工組成物の
安定性が極めで優れることや、塗工作褒も容易である点
でもっとも好ましい方法であり、本発明の目的とする潰
工紙をも好ましく得ることができる。The thermosetting ml aqueous solution of the present invention was added to STIRESORB 5! Pre-blending a water emulsion or dispersion binder such as diene resin or methyl methacrylate resin allows the coating composition to be easily adjusted, and the stability of the coating composition is extremely excellent. This is the most preferable method in that it is easy to obtain coating results, and it is also possible to preferably obtain crushed paper, which is the object of the present invention.
本発明の紙用塗工組成物は、従来より公知の方法で、す
なわちブレードコーター、エアデ
一本イフコー費−、ロールコーク−、サイズプレスコー
費−、キャストコーク−など通常用いられている方法で
紙基体上に塗工し、通常の方法で必要な乾燥を行ない、
更に必要に応じてスーパーカレンダー、マシンカレンダ
ーなどの処理を施すことにより塗工紙を製造することが
できる。The paper coating composition of the present invention can be prepared by conventionally known methods, such as blade coater, air dryer, roll coke, size press coat, cast coke, etc. Coating on a paper substrate, drying as required using normal methods,
Furthermore, coated paper can be produced by subjecting the paper to a super calender, machine calender, or other treatment, if necessary.
かかる本発明の紙用塗工組成物は、カラーシーツク(組
成物の著しい増粘、顔料の凝集など)もなく、塗工液の
安定性、と優れ、これを紙基体上−こ塗布して得た塗工
紙は塗被層の耐水性に優れ、ホルムアルデヒドの発生が
著しく少なく、インキ転移性の向上に優れるととも−こ
、着色も認められない、オフセット輪転印刷での耐ブリ
スター性の向上1こも有効であるという種々のすぐれた
特徴を有する。The paper coating composition of the present invention has excellent coating liquid stability without color shedding (significant thickening of the composition, agglomeration of pigments, etc.), and when coated on a paper substrate. The coated paper obtained by this process has excellent water resistance in the coated layer, produces significantly less formaldehyde, has excellent ink transfer properties, and has no coloration, and has excellent blister resistance in rotary offset printing. It has various excellent features that make it even more effective.
以下、実施例により本発明を説明する。The present invention will be explained below with reference to Examples.
実施例1
(11熱硬化性樹脂水溶液の製造
温度計、還流冷却器、撹拌棒を備えた四ツ目フラスコに
トリエチレンテトラミン292fc2モル)と尿素60
F(1モル)を仕込み145〜150℃で、発生するア
ンモニニアを系外働ζ除去しながら4時間反応を行ない
、次いでアジピン酸1465’(1モル)を加え、15
0〜155℃で5時間線合反応を行なった。120℃ま
で冷却した後尿素24 Of (4モア1/ )を加え
125〜180℃で2時間脱アンモニア反応を行なった
。Example 1 (Preparation of 11 thermosetting resin aqueous solution In a four-eye flask equipped with a thermometer, reflux condenser, and stirring bar, 292 fc2 moles of triethylenetetramine) and 60 ml of urea were added.
F (1 mol) was charged and the reaction was carried out at 145-150°C for 4 hours while removing the generated ammonia from the system. Then, adipic acid 1465' (1 mol) was added and 15
Linearization reaction was carried out at 0 to 155°C for 5 hours. After cooling to 120°C, 24 Of (4 moles) of urea was added, and ammonia removal reaction was carried out at 125 to 180°C for 2 hours.
eの後、水180tを徐々に加え、ポリアミドポリ尿素
の水溶液を得た。After step e, 180 t of water was gradually added to obtain an aqueous solution of polyamide polyurea.
次・こ、87%ホルマリン202.5 tc2.5モル
)を加え、濃塩酸にてpHを5Iこ調整した後、65℃
1こで4時間保温攪拌した。After adding 87% formalin (202.5 tc 2.5 mol) and adjusting the pH by 5 I with concentrated hydrochloric acid, it was heated to 65°C.
The mixture was stirred and kept warm for 4 hours.
次いでエピクロルヒドリン87j’(0,4モル)及び
水86tを加え、60℃にて8時間保温攪拌した。eの
後25Cまで冷却し、固型分80%の熱硬化性樹脂水溶
液を得た。Next, 87j' (0.4 mol) of epichlorohydrin and 86 t of water were added, and the mixture was stirred at 60° C. for 8 hours. After e, the mixture was cooled to 25C to obtain a thermosetting resin aqueous solution with a solid content of 80%.
実施例2
温度計、還流冷却器、撹拌棒を備えた四ソロフラスコ・
こジエチレントリアミ・ン206tc2モル)、水10
F及びアジピン酸146f(1モル)を仕込み、150
℃まで昇温した。次いで生成する水を留去させながら、
150−155℃で6時間保温した後、180Cまで冷
却し、尿素240fC4モル)を仕込み、125〜18
0cで発生するアンモニアを系外1ζ除去しながら8時
間瞬アンモニア反応を9行なった。七の後、水48゜t
を徐々に加えポリアミドポリ尿素の水溶液を得た。Example 2 Four solo flasks equipped with a thermometer, reflux condenser, and stirring bar.
diethylenetriamine (206 tc2 mol), water 10
F and adipic acid 146f (1 mol) were charged, and 150
The temperature was raised to ℃. Then, while distilling off the water produced,
After incubating at 150-155℃ for 6 hours, cooled to 180C, charged with 240fC4 mol of urea,
Nine 8-hour flash ammonia reactions were carried out while removing 1ζ of ammonia generated at 0C from the system. After 7, water 48゜t
was gradually added to obtain an aqueous solution of polyamide polyurea.
得られたポリアミドポリ尿素水溶液−こ、エピクロルヒ
ドリン55.5f(0,6モル)及び水800fを加え
、65cにて5時間保温攪拌した。次いで87%ホルマ
リン129.6f(1,6モル)を加え、濃塩酸に’(
pHを4に調整した後、70℃−ごて8時間保温撹拌し
た。80℃まで冷却した後、30%苛性ソーダ水溶液−
とてpHを6 +C調県し、固型分40%の熱硬化性樹
脂水溶液を得た。To the obtained polyamide polyurea aqueous solution, 55.5 f (0.6 mol) of epichlorohydrin and 800 f of water were added, and the mixture was stirred at 65° C. for 5 hours while keeping it warm. Next, 129.6f (1.6 mol) of 87% formalin was added and diluted with concentrated hydrochloric acid (
After adjusting the pH to 4, the mixture was stirred at 70° C. for 8 hours using a trowel. After cooling to 80°C, 30% caustic soda aqueous solution -
The pH was adjusted to 6+C to obtain an aqueous thermosetting resin solution with a solid content of 40%.
(2)紙用塗工組成物の作成
あらかじめ分散せしめた顔料スラリーに、あらかじめ糊
化した酸化でんぷん水溶液およびスチレンーブシジエン
ラテックスを加え、更に耐水化剤として前記熱硬化性樹
脂水溶液を添加し、よく混合して紙用塗工組成物を作成
した。(2) Preparation of coating composition for paper Adding a pre-gelatinized oxidized starch aqueous solution and styrene-butydiene latex to a pre-dispersed pigment slurry, and further adding the thermosetting resin aqueous solution as a water resistant agent, A paper coating composition was prepared by mixing well.
尚、配合割合(固型分重りは第1表に
示すとおりであり、該組成物は苛性°ノーダ水溶液でp
H中9.5となるよう1と、また固型分#度が55重暇
%となるように調整した。The blending ratio (solid content weight) is as shown in Table 1, and the composition is
The solid content was adjusted to 1 so that it became 9.5 in H, and the solid content was adjusted to 55%.
得られた紙用塗工組成物は熱硬化性11Hj水溶液の添
加時のカラーシーツクもなく、なめらかむ流動性を示し
た。The obtained paper coating composition exhibited smooth fluidity without any color sheak upon addition of the thermosetting 11Hj aqueous solution.
塗工組成物の粘度、pHおよび1日放置後の粘度を第2
表に示す。The viscosity and pH of the coating composition and the viscosity after being left for one day were
Shown in the table.
第 1 表
これら組成物を、コーチインブロンドを用いて、86Y
iコ一ト原紙に乾燥固型分で片面的15f/mとなるよ
う叡ζ両面塗工し、120℃XaO秒間熱風乾燥を行な
った。Table 1 These compositions were prepared using coach-in-blond, 86Y
One coat of base paper was coated on both sides with a dry solid content of 15 f/m on one side, and then dried with hot air at 120°C for 2 seconds.
この塗工紙を、調湿後(20℃、65 %RH)、スー
パーカレンダー(60’C160kQ / cm、2回
通し)1こかけ、テスト用試料を作成し、各種試峨法1
こ基づいて評価を行なった。結果は第2表に示す。After conditioning the humidity (20°C, 65% RH), apply one coat of this coated paper to a super calender (60'C160kQ/cm, 2 passes) to create a test sample, and apply various test methods 1.
The evaluation was made based on this. The results are shown in Table 2.
比較例1
実施例1と同様の装置lこトリエチレンテトラi :/
292 f (2モル)と尿素60f(1モル)を仕
込み145〜150℃で、発生するアンモニアを系外−
ζ除却しむがら4時間反応を行ない、次いでアジピン酸
146F(1%ル)加え、150−155℃で54峠間
縮合反応を行なった。120Cまで冷却した後尿素24
0t(4v−ル)を加え125〜180℃まで2時1f
fl脱アンモニア反応を行なった。その後、水1850
1Fをを得た。Comparative Example 1 Using the same apparatus as Example 1, triethylenetetra:/
292f (2 mol) and urea 60f (1 mol) were charged at 145 to 150°C, and the generated ammonia was removed from the system.
The reaction was carried out for 4 hours while removing ζ, and then adipic acid 146F (1%) was added and a 54-pass condensation reaction was carried out at 150-155°C. After cooling to 120C, urea 24
Add 0t (4v-le) and heat to 125-180℃ for 2 hours and 1f.
A fl deammonification reaction was performed. After that, water 1850
I got 1F.
次1ζ、87%ホルマリン202.5 t (2,5モ
ル)を加え、濃塩酸−ごてpHを5Iζ調整した後65
℃にて4時間保温攪拌した。その後30℃まで冷却し、
30%苛性ソーダ水溶液SこでpHを81と調整し、固
型分30%の熱硬化性樹脂水溶液を得た。Next, add 202.5 t (2.5 mol) of 87% formalin and adjust the pH with a trowel with concentrated hydrochloric acid.
The mixture was stirred and kept warm at ℃ for 4 hours. Then cool to 30℃,
The pH was adjusted to 81 using a 30% caustic soda aqueous solution S to obtain a thermosetting resin aqueous solution with a solid content of 30%.
この熱硬化性樹脂水溶液を用いて、実施例1.2と同様
、こして紙用塗工組成物を作成し、同様に塗工紙を作成
した。Using this aqueous thermosetting resin solution, a coating composition for paper was strained in the same manner as in Example 1.2, and coated paper was produced in the same manner.
得られた塗工紙1こついC実施例1.2と同様1こeの
性能試噛を行ない、第2表6ζ示す結果を得た。The resulting coated paper was tested for performance in the same manner as in Example 1.2, and the results shown in Table 2 were obtained.
比較例2
熱硬化性樹脂水溶液の代わl)+こスミレ−ズレジン6
18(メラミン−ホルムアルデヒドFf14脂、生友化
学工貰社製)を用いる以外は実施例1.2と同様iこし
C紙用塗工組成物を作成し、同様番こ塗工紙を作成した
。Comparative Example 2 Substitute for thermosetting resin aqueous solution 1) + this violet resin 6
A coating composition for i-Koshi C paper was prepared in the same manner as in Example 1.2, except that 18 (melamine-formaldehyde Ff14 fat, manufactured by Seitomo Kagaku Kogyo Co., Ltd.) was used, and a coated paper was prepared in the same manner.
比較例8
熱硬化性樹脂水溶液の代わりにグリオキザ−jしを用い
る以外は実施例1.2と同様らこして紙用塗工組成を作
成し、同様すこ塗工紙を作成した。Comparative Example 8 A paper coating composition was prepared in the same manner as in Example 1.2 except that glyoxazine was used instead of the thermosetting resin aqueous solution, and a thin coated paper was prepared in the same manner.
比較例4
耐水化剤を使用しないこと以外は実施例1.2=同様も
こして紙用塗工組成物を作成し、同様に塗工紙を作成し
た。Comparative Example 4 A paper coating composition was prepared in the same manner as Example 1.2 except that no water-resisting agent was used, and coated paper was prepared in the same manner.
比較例2〜4の得られた塗工紙について、実施例1.2
と同様もこその性能試喰を行ない、第2表に示す結果を
得た。For the coated papers obtained in Comparative Examples 2 to 4, Example 1.2
Similar performance tests were conducted and the results shown in Table 2 were obtained.
(8)試噴法
塗工紙を温度20℃、湿度65%R)1にて48時間調
湿後、測定試噴に供した。(8) Test Spraying Method The coated paper was conditioned for 48 hours at a temperature of 20° C. and a humidity of 65% (R) 1, and then subjected to measurement test spraying.
0塗工液のpH
ガラス電1ilj p H計を使用、測定温度20O塗
工液の粘度
B型粘度計使用、回転数6Q rpm 、測定。0 pH of the coating liquid using a glass electrode 1ilj pH meter, measurement temperature 20O Viscosity of the coating liquid using a B-type viscometer, rotation speed 6Q rpm, measurement.
a度20℃
0塗暎の耐水性
(イ) Wet ’Rub 法
コート面上にイオン交換水を約0.1 MI M下し、
指先で7回摩擦し、溶出量を黒紙1こ移行させて溶出量
を肉眼で判定した。Water resistance of 0 coating at a degree of 20℃ (a) Wet 'Rub method: Pour ion exchange water of about 0.1 MIM onto the coated surface,
The amount of elution was determined with the naked eye by rubbing it with a fingertip 7 times and transferring the amount of elution onto a sheet of black paper.
判定基準壜は次のよう1こ行なった。The evaluation criteria bottle was subjected to the following steps.
耐水性(劣)1〜5(優)
(o) Wet Pick法
RI試1検機(明製作所#)を使用して、塗被面を給水
ロール1こて湿潤したのち印刷し、塗被面の脱落、損傷
状態を肉眼観、察し、判定した。判定基準はWe t
R11b法と同様である。Water resistance (poor) 1 to 5 (excellent) (o) Using a Wet Pick method RI test 1 tester (Mei Seisakusho #), wet the coated surface with a water supply roll 1 and then print. The falling off and damage state was visually observed and judged. The criteria is Wet
This is the same as the R11b method.
0堕工紙からのホルムアルデヒドの定噴J18L−10
41液相拙出法(2)アセチルアセトン法1こ準拠
なおホルムアルデヒド蟻の測定は、ポリエチレン袋番こ
密封するなどして他からの移行、発散を防止して測定I
C供した。Constant spray of formaldehyde from 0-corrupt paper J18L-10
41 Liquid phase extraction method (2) Acetyl acetone method (1) For formaldehyde measurement, measure by sealing a polyethylene bag to prevent migration and dispersion from other sources.
C provided.
Ot工紙のインキ転移性
RI試験法を用いて下記の方法で印刷し、インキ転移性
を肉眼で観察、判定した。Printing was performed in the following manner using the ink transferability RI test method for Ot paper, and the ink transferability was observed and determined with the naked eye.
判定基準は、(1)5〜l(劣)とした。The evaluation criteria were (1) 5-1 (poor).
(イ) A 法 練り込み中のインキ1こ、水を滴下した後に印刷する。(b) A Method Print after adding a drop of water to the ink being mixed.
(C2) 方法 塗被面を給水ロール1こて濤潤させた後、こ印刷する、 (ハ)C法 上記、A、方法の組み合せ方法もこより印刷する。(C2) Method After moistening the surface to be coated with a water supply roll, print. (c) C method A combination of methods A and A above will also be printed.
O塗工紙の白変および耐熱白変
150℃で80分間熱風乾燥機で熱4埋する前後の塗工
紙の白変を、JI8P−8128+こ準拠し、ハンター
反射率計のB値を測定することにより試験した。White discoloration and heat-resistant white discoloration of coated paper The white discoloration of coated paper before and after heating in a hot air dryer at 150°C for 80 minutes was determined by measuring the B value using a Hunter reflectance meter in accordance with JI8P-8128+. It was tested by
数字の大きいもの村白変が良好である。The higher the number, the better the Murakuro discoloration.
0iIff4ブリスター性
R1試験機を用いてオフ輪用インキを使用し、両面塗工
紙に両面印刷を行ない、調湿後、加熱したシリコンオイ
ル浴中・こ浸し、ブリスジ−が発生する時の最低温度を
示す。0iIff4 Print on both sides of coated paper using off-circle ink using a blister property R1 tester, and after adjusting the humidity, soak in a heated silicone oil bath to determine the lowest temperature at which blistering occurs. shows.
実施例8
(1)熱硬化性樹脂水溶液の製造
実施例2と同様の反応装置−ζ、ジエチレントリアミン
108fT1モル)、トリエチレンテトラミン146f
(1モル)、水2Of及びコハク酸含122%、グルシ
ーし酸含@64%、アジピン酸含t14%からなる混合
二塩基性カルボン酸100f(二塩基性カルボン酸とし
て0.77モル)を仕込み、160〜165℃で8時間
脱水縮合させた。次いで尿素240F(4モル)を仕込
み、145〜150’CIこ”C4時間脱アンモニア反
応を行なった後、水410Fを徐々−こ加え、ポリアミ
ドポリ尿素水溶液を得た。ここへ87%ホルマリン97
.2 f(1,2モル)、エピクロ?レヒドリン129
.5F(1,4モル)及び水960fを仕込み、30%
苛性ソーダ水溶液にてpHをlOに鳴整した、eの後6
5℃で8時間保温攪拌した後、85%塩酸1こてpHを
4に調整し、50℃6ζて4時間保温攪拌した。反応終
了後、80℃まで冷却し、80%苛性ソーダ水溶液、こ
でpitを5.51ζ調整し、固型分80%の熱硬化性
樹脂水溶液を得た。Example 8 (1) Production of thermosetting resin aqueous solution Reactor similar to Example 2 - ζ, diethylenetriamine 108fT1 mol), triethylenetetramine 146f
(1 mol), water 2Of and mixed dibasic carboxylic acid 100f (0.77 mol as dibasic carboxylic acid) consisting of 122% succinic acid, 64% lucidic acid, and 14% adipic acid. , dehydration condensation was carried out at 160 to 165°C for 8 hours. Next, urea 240F (4 mol) was charged and deammonization was carried out at 145 to 150'C for 4 hours, after which water 410F was gradually added to obtain a polyamide polyurea aqueous solution.To this, 87% formalin 97 was added.
.. 2 f (1,2 mol), epicro? Rehydrin 129
.. Prepare 5F (1.4 mol) and water 960f to 30%
After adjusting the pH to lO with aqueous caustic soda solution, 6
After stirring while keeping warm at 5°C for 8 hours, the pH was adjusted to 4 with one trowel of 85% hydrochloric acid, and the mixture was stirred while keeping warm at 50°C for 4 hours. After the reaction was completed, the mixture was cooled to 80° C., and the pit was adjusted to 5.51ζ using an 80% caustic soda aqueous solution to obtain a thermosetting resin aqueous solution with a solid content of 80%.
(2)紙用塗工組成物の作成
あらかじめ糊化した酸化でんぷん水溶液畢ζ耐水化剤と
しC上記熱硬化性@脂水溶液を加え、固型分として第8
表1こ示す配合割合の紙用塗工組成物を作成した。尚、
該組成物は固型分濃度が11重量%となるよう電こ水を
加えて調整した。(2) Preparation of coating composition for paper A pre-gelatinized oxidized starch aqueous solution; Add the above thermosetting @ fat aqueous solution as a water resistant agent;
Paper coating compositions having the blending ratios shown in Table 1 were prepared. still,
The composition was adjusted by adding electric water so that the solid content concentration was 11% by weight.
第 8 表
比較例5
熱硬化性樹脂水溶液の代わり1こスミレ−ズレジン61
Bを用いる以外は実施例8と同様島こして紙用塗工組成
物を作成した。Table 8 Comparative Example 5 1 Violet Resin 61 instead of thermosetting resin aqueous solution
A coating composition for paper was prepared in the same manner as in Example 8 except that B was used.
比較例6
熱硬化性樹脂水溶液の代わりにグリオキザールを用いる
以外は実施例8と同様にして紙用塗工組成物を作成した
。Comparative Example 6 A paper coating composition was prepared in the same manner as in Example 8 except that glyoxal was used instead of the thermosetting resin aqueous solution.
比較例7
酸化でんぷんのlO重啜%水溶液を紙用塗工組成物とし
て、実施例8と同様にして紙用塗工組成物を作成した。Comparative Example 7 A paper coating composition was prepared in the same manner as in Example 8, using an aqueous solution of oxidized starch at 10% by weight as a paper coating composition.
(8)塗工紙の作成
これらの紙用φ工塗工組成物を、サイズプレスコーク−
を用いて米坪185F/Wlの上質紙、ζ塗布し、自然
乾燥したのち110℃で1分間キユアリング(熱板)を
施しで塗工紙を得た。(8) Preparation of coated paper These paper coating compositions were coated with size press coke.
The coated paper was coated with high quality paper of 185 F/Wl using ζ, air-dried, and then cured (hot plate) at 110° C. for 1 minute to obtain a coated paper.
この塗工紙を調湿(温度20℃、湿度65%Ru、48
時間)後、測定試験1と供した。Humidify this coated paper (temperature 20℃, humidity 65% Ru, 48℃)
After that time, measurement test 1 was carried out.
その結果を第4表1こ示す。The results are shown in Table 4.
(4)試験法
O塗工液の安定性
塗工液全温度50℃番こで20時間保存して、塗工液の
変化を観察した。(4) Test Method O Stability of Coating Solution The coating solution was stored at a total temperature of 50° C. for 20 hours, and changes in the coating solution were observed.
Oブロッキング性
試験紙を40℃、80%IL Hの条件1こて24時間
コ11湿したのち重ね合わし、加圧機1ζC温度50℃
、圧力1kq/−・ζて2時間叩圧し、接着状態、剥啼
した場合の紙面の破損状態を肉眼、じC観察し、判定し
た。O-blocking test paper was moistened with a trowel for 24 hours at 40°C and 80% IL H, then overlapped, and the pressure machine 1ζC temperature was 50°C.
, and a pressure of 1 kq/-·ζ for 2 hours, and the state of adhesion and the state of damage to the paper surface when peeled off were visually observed and judged.
ブロッキング性 IF)5〜l(劣)
O耐水性
イオン交換本釣0.1 stを塗工紙面会こ滴下し、指
先で7回摩擦し、塗工組成物の溶出状態を指先の触感お
よび溶出物・\の黒紙・\の移行会こより判定した。Blocking property IF) 5-1 (poor) O Water resistance Ion exchange main fishing 0.1 st was dropped on the surface of the coated paper, rubbed 7 times with a fingertip, and the dissolution state of the coating composition was measured by the touch of the fingertip and the dissolution. Judging from the thing, \'s black paper, and \'s transition party.
耐水性 (f)5〜l(劣)
O塗工紙からのホルムアルデヒドの定量実施例1.2と
同じ。Water resistance (f) 5-1 (poor) Quantification of formaldehyde from O-coated paper Same as Example 1.2.
O塗工紙の白変および耐熱性 実施例1.2と同じ。Whitening and heat resistance of O-coated paper Same as Example 1.2.
手続補正前(自発)
昭和56年テ月2γ日
特許庁長官 島 1)春樹 殿
1、事件の表示
昭和56年 特許順第 13gりz6 号2、発明の名
称
紙用塗工組成物
3、 補正をする者
事件との関係 特許出願人
住 所 大阪市東区北浜5丁目15番地名 称 (
209)住友化学工業株式会社代表者 土
方 武
4、代理人
住 所 大阪市東区北浜5丁目15番地昭和 年
月 日 (→り
手続補正前(自発)
6
昭和57年2月芦日
特許庁長官 島 1)春 樹
■、事件の表示
昭和56年 特許願第 H3872f 号2、発明の
名称
都悟###@φ療殊
成用塗工栖夜物
3、 補正をする者
事件との関係 特許用M人
住 所 大阪市東区北浜5丁目15番地名 称 (
209)住友化学工業株式会社代表者 土 方
式
%式%
5、補正の対象
明細書の発明の詳細な説明の欄
6、補正の内容
(1) 昭和56年9月29日付提出の浄書明細書第
8頁5行目の、「0.8〜1.2モル」とあるを、「0
.8〜0.7モル」と訂正する。Before procedural amendments (voluntary) July 2, 1980 Commissioner of the Japan Patent Office Shima 1) Haruki Tono1, Indication of the case 1981 Patent order No. 13grz6 No. 2, Title of invention Coating composition for paper 3, Amendment Relationship with the case of a person who does
209) Sumitomo Chemical Co., Ltd. Representative Sat
Takeshi 4, Agent Address: 5-15 Kitahama, Higashi-ku, Osaka, Showa
Month/Day (→Prior to procedural amendment (spontaneous) 6 February 1980 Ashiya, Commissioner of the Patent Office Shima 1) Haruki ■, Indication of the case 1982 Patent application No. H3872f No. 2, Name of the invention Togo### @φ Medical Treatment Coating Seiyamono 3, Relationship with the case of the person making the amendment Address of M person for patent purposes 5-15 Kitahama, Higashi-ku, Osaka Name (
209) Sumitomo Chemical Co., Ltd. Representative Hijikata
Formula % Formula % 5, Column 6 of the detailed description of the invention in the specification subject to amendment, Contents of the amendment (1) "0. 8 to 1.2 mole” is replaced with “0
.. 8 to 0.7 mol".
以上that's all
Claims (1)
組成物において、耐水化剤として、尿素とポリアルキレ
ンポリアミンを悦アンモニア反応させ、次いで二塩基性
カルボン酸と脱水縮合させ、更に尿素と悦アンモニア反
応させて得られるポリアミドポリ尿素、又。 素もと、水溶液中でエン4′ヒドリン及びホルムアルデ
ヒドを反応させることtこより得られる熱硬化性嗣田水
溶液を用いることを特許と−する紙用塗工組成物。[Claims] In a paper coating composition containing an aqueous binder and a water-resistant agent, urea and a polyalkylene polyamine are subjected to an ammonia reaction as the water-resistant agent, and then dehydrated and condensed with a dibasic carboxylic acid. A polyamide polyurea obtained by further reacting urea with ammonia. This patented paper coating composition uses a thermosetting aqueous solution obtained by reacting ene-4'hydrin and formaldehyde in an aqueous solution.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13872681A JPS5841994A (en) | 1981-09-02 | 1981-09-02 | Paper coating composition |
JP22084188A JPS6477696A (en) | 1981-09-02 | 1988-09-02 | Paper coating composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP13872681A JPS5841994A (en) | 1981-09-02 | 1981-09-02 | Paper coating composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5841994A true JPS5841994A (en) | 1983-03-11 |
JPH0323679B2 JPH0323679B2 (en) | 1991-03-29 |
Family
ID=15228714
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP13872681A Granted JPS5841994A (en) | 1981-09-02 | 1981-09-02 | Paper coating composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5841994A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58126395A (en) * | 1982-01-19 | 1983-07-27 | 住友化学工業株式会社 | Paper coating composition |
EP0220960A2 (en) * | 1985-10-28 | 1987-05-06 | Sumitomo Chemical Company, Limited | Production of urea-polyamine resins for paper coating compositions |
JPS62103158A (en) * | 1985-10-30 | 1987-05-13 | Futaki Itsuo | Thermal head |
JPS62104996A (en) * | 1985-07-01 | 1987-05-15 | 旭化成株式会社 | Synthetic adhesive for paper coating and paper coating liquid composition using the same |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS582331A (en) * | 1981-06-30 | 1983-01-07 | Dick Hercules Kk | Preparation of aqueous solution of thermosetting resin |
-
1981
- 1981-09-02 JP JP13872681A patent/JPS5841994A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS582331A (en) * | 1981-06-30 | 1983-01-07 | Dick Hercules Kk | Preparation of aqueous solution of thermosetting resin |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58126395A (en) * | 1982-01-19 | 1983-07-27 | 住友化学工業株式会社 | Paper coating composition |
JPH0380920B2 (en) * | 1982-01-19 | 1991-12-26 | Sumitomo Chemical Co | |
JPS62104996A (en) * | 1985-07-01 | 1987-05-15 | 旭化成株式会社 | Synthetic adhesive for paper coating and paper coating liquid composition using the same |
JPH034680B2 (en) * | 1985-07-01 | 1991-01-23 | Asahi Chemical Ind | |
EP0220960A2 (en) * | 1985-10-28 | 1987-05-06 | Sumitomo Chemical Company, Limited | Production of urea-polyamine resins for paper coating compositions |
US5158611A (en) * | 1985-10-28 | 1992-10-27 | Sumitomo Chemical Co., Ltd. | Paper coating composition |
JPS62103158A (en) * | 1985-10-30 | 1987-05-13 | Futaki Itsuo | Thermal head |
Also Published As
Publication number | Publication date |
---|---|
JPH0323679B2 (en) | 1991-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN107268332A (en) | A kind of heat-sensitive paper and preparation method thereof | |
JPS5932597B2 (en) | Coating composition for paper | |
US4246153A (en) | Process for producing aqueous solution of polyureapolyamide thermosetting resin | |
JPS5841994A (en) | Paper coating composition | |
JPH09501745A (en) | Paper or cardboard having a coating layer provided by a cast coating method, its manufacturing method and use | |
EP0081994B1 (en) | Preparation of thermosetting resins and of pigmented compositions thereof for coating on paper | |
US4464505A (en) | Coating composition for providing water and blister resistant, ink-receptive paper | |
JPS59137597A (en) | Paper coating composition | |
US4444943A (en) | Coating compositions for providing water and blister resistance to ink-receptive paper | |
JPS58126394A (en) | Paper coating composition | |
JP3351105B2 (en) | Coating composition for paper | |
JPH0356578B2 (en) | ||
JPS58126395A (en) | Paper coating composition | |
CN101798777B (en) | Resin for paper spread coating and composition for paper spread coating | |
JP3214119B2 (en) | Coating composition for paper | |
JP2516739B2 (en) | Method for producing coating composition for paper | |
JPS58180695A (en) | Paper coating composition | |
JP2617309B2 (en) | Printability improver for paper and coating composition | |
JPH04343794A (en) | Production of coated paper | |
JP3269221B2 (en) | Paper coating resin and paper coating composition containing the same | |
JP2601269B2 (en) | Printability improver for paper and coating composition | |
JP2864738B2 (en) | Coating composition for paper | |
JPH0121278B2 (en) | ||
JPH064956B2 (en) | Coating composition for paper | |
JPS62104995A (en) | Paper coating composition |