JP4209028B2 - Method for producing opacity improved paper - Google Patents

Description

（ただし、式中、Ｙ¹は（ｎ₁＋ｍ₁）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ¹はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であって、これらのアシル基の少なくとも一つは炭素数８〜２２であり、Ｘ¹は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ¹Ｏ)k₁Ｒ¹（ここでＢ¹は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ¹は水素原子又は炭素数２〜２２のアシル基であり、ｋ₁は１〜２０である。）であり、ｎ₁は１以上であり、ｍ₁は０以上であり、ｎ₁＋ｍ₁＝１〜１００であり、ｎ₁が２以上の場合複数のＡ¹は同一でも異なっていてもよく、ｍ₁が２以上の場合複数のＸ¹は同一でも異なっていてもよい。）、
（２）一般式［２］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる反応生成物を、酸で中和し、水に溶解又は分散し添加して、アニオン系若しくは両性系乾燥紙力剤を添加して、サイズ剤を添加して混合してパルプを調製し、該パルプを抄紙工程、プレス工程及び乾燥工程にかけることによって、前記反応生成物を添加しないで製造した紙の場合よりも、不透明度が８７.０％以上の領域において２.０％以上大きく、密度の差異は０.０２１ｇ／ｃｍ³以上小さく、かつサイズ度の低下が２秒以下の紙を得ることを特徴とする不透明度向上紙の製造方法、
【化８】

（ただし、式中、Ｙ²は炭素数８〜２２のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基の少なくとも一つと（ｎ₂＋ｍ₂）個の活性水素とを有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ²はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であり、Ｘ²は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ²Ｏ)k₂Ｒ²（ここでＢ²は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ²は水素原子又は炭素数２〜２２のアシル基であり、ｋ₂は１〜２０である。）であり、ｎ₂は０以上であり、ｍ₂は０以上であり、ｎ₂＋ｍ₂＝０〜１００であり、ｎ₂が２以上の場合複数のＡ²は同一でも異なっていてもよく、ｍ₂が２以上の場合複数のＸ²は同一でも異なっていてもよい。）、
（３）一般式［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる反応生成物を、酸で中和し、水に溶解又は分散し添加して、アニオン系若しくは両性系乾燥紙力剤を添加して、サイズ剤を添加して混合してパルプを調製し、該パルプを抄紙工程、プレス工程及び乾燥工程にかけることによって、前記反応生成物を添加しないで製造した紙の場合よりも、不透明度が８７.０％以上の領域において２.０％以上大きく、密度の差異は０.０２１ｇ／ｃｍ³以上小さく、かつサイズ度の低下が２秒以下の紙を得ることを特徴とする不透明度向上紙の製造方法、
【化９】

（ただし、式中、Ｙ³は（ｎ₃＋ｍ₃）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ³はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であり、Ｘ³は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ³Ｏ)k₃Ｒ³（ここでＢ³は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ³は水素原子又は炭素数２〜２２のアシル基であり、ｋ₃は１〜２０である。）であって、Ｘ³の少なくとも一つは炭素数８〜２２のアルキル基、アルケニル基又はアシル基を有する基であり、ｎ₃は０以上であり、ｍ₃は１以上であり、ｎ₃＋ｍ₃＝１〜１００であり、ｎ₃が２以上の場合複数のＡ³は同一でも異なっていてもよく、ｍ₃が２以上の場合複数のＸ³は同一でも異なっていてもよい。）、
（４）Ａ¹の少なくとも一つが、一般式［４］で表される基である第(１)項記載の不透明度向上紙の製造方法、
【化１０】

（ただし、式中、Ｒ⁴は、炭素数７〜２１のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基である。）、
（５）Ａ²の少なくとも一つが、一般式［５］で表される基である第(２)項記載の不透明度向上紙の製造方法、
【化１１】

（ただし、式中、Ｒ⁵は、炭素数７〜２１のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基である。）、及び、
（６）Ａ³の少なくとも一つが、一般式［６］で表される基である第(３)項記載の不透明度向上紙の製造方法、
【化１２】

（ただし、式中、Ｒ⁶は、炭素数７〜２１のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基である。）、
を提供するものである。
【０００５】
【発明の実施の形態】
本発明の紙用不透明化剤の第１の態様は、一般式［１］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる化合物を含有するものである。
【化１３】

一般式［１］において、Ｙ¹は（ｎ₁＋ｍ₁）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ¹はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であって、これらのアシル基の少なくとも一つは炭素数８〜２２であり、Ｘ¹は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ¹Ｏ)k₁Ｒ¹（ここでＢ¹は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ¹は水素原子又は炭素数２〜２２のアシル基であり、ｋ₁は１〜２０である。）であり、ｎ₁は１以上であり、ｍ₁は０以上であり、ｎ₁＋ｍ₁＝１〜１００であり、ｎ₁が２以上の場合複数のＡ¹は同一でも異なっていてもよく、ｍ₁が２以上の場合複数のＸ¹は同一でも異なっていてもよい。
本発明の紙用不透明化剤の第２の態様は、一般式［２］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる化合物を含有するものである。
【化１４】

一般式［２］において、Ｙ²は炭素数８〜２２のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基の少なくとも一つと（ｎ₂＋ｍ₂）個の活性水素とを有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ²はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であり、Ｘ²は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ²Ｏ)k₂Ｒ²（ここでＢ²は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ²は水素原子又は炭素数２〜２２のアシル基であり、ｋ₂は１〜２０である。）であり、ｎ₂は０以上であり、ｍ₂は０以上であり、ｎ₂＋ｍ₂＝０〜１００であり、ｎ₂が２以上の場合複数のＡ²は同一でも異なっていてもよく、ｍ₂が２以上の場合複数のＸ²は同一でも異なっていてもよい。
【０００６】
本発明の紙用不透明化剤の第３の態様は、一般式［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる化合物を含有するものである。
【化１５】

一般式［３］において、Ｙ³は（ｎ₃＋ｍ₃）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基であり、Ａ³はアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であり、Ｘ³は水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ³Ｏ)k₃Ｒ³（ここでＢ³は炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ³は水素原子又は炭素数２〜２２のアシル基であり、ｋ₃は１〜２０である。）であって、Ｘ³の少なくとも一つは炭素数８〜２２のアルキル基、アルケニル基又はアシル基を有する基であり、ｎ₃は０以上であり、ｍ₃は１以上であり、ｎ₃＋ｍ₃＝１〜１００であり、ｎ₃が２以上の場合複数のＡ³は同一でも異なっていてもよく、ｍ₃が２以上の場合複数のＸ³は同一でも異なっていてもよい。
本発明の紙用不透明化剤の第４の態様は、１〜１００個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物とを反応して得られる化合物の残余する活性水素に、アルキル化剤、アルケニル化剤又はアシル化剤を反応させて、置換基を有していてもよい炭素数８〜２２のアルキル基、アルケニル基又はアシル基を導入した化合物を含有するものである。
【０００７】
本発明において、一般式［１］〜［３］における残基Ｙ¹〜Ｙ³を与える化合物は、１個以上の活性水素を有し、その１個以上がアミド化することができるアミノ基又はエステル化することができる水酸基の活性水素である化合物である。このような化合物としては、例えば、メチルアミン、エチルアミン、ラウリルアミン、ステアリルアミン、オレイルアミン、１２−ヒドロキシ−９−オクタデセニルアミン、３−ヒドロキシプロペニルアミン、ジメチルアミン、ジエチルアミン、ジラウリルアミン、ジステアリルアミン、ジ(１２−ヒドロキシ)−９−オクタデセニルアミン、ジ(３−ヒドロキシ)プロペニルアミン、モノラウリルジメチルアミン、モノステアリルジメチルアミン、ジステアリルモノメチルアミン、トリメチルアミン、ジラウリルモノメチルアミン、ジ(３−ヒドロキシ)プロペニルモノメチルアミンなどのアルキルアミン類、アルケニルアミン類、ヒドロキシアルキルアミン類、ヒドロキシアルケニルアミン類及びこれらのアミン類のアルキレンオキシド付加物、アミノエチルエタノールアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、モノイソプロパノールアミンなどのアルカノールアミン類及びこれらのアミン類のアルキレンオキシド付加物、エチレンジアミン、ジエチレントリアミン、トリエチレンテトラミン、ペンタエチレンヘキサミン、ヘキサエチレンヘプタミン、ジプロピレントリアミン、トリプロピレンテトラミン、ヘキサメチレンジアミンなどのポリアルキレンポリアミン類及びこれらのアミン類のアルキレンオキシド付加物、グルタミン酸、アスコルビン酸などのアミノ酸類及びこれらのアミノ酸類のアルキレンオキシド付加物、さらに、これらのアミノ酸類が縮合されたポリペプチド結合を有する蛋白類など及びそれらのアルキレンオキシド付加物、ポリエチレンイミン、ポリプロピレンイミンなどの線状構造又は分岐構造を有するポリアルキレンイミン類、アリルアミン、ジアリルアミン、ポリアリルアミン、ジアリルメチルアミン、ポリジアリルメチルアミンやそれらを用いて得られた共重合物やメラミン又はその樹脂などの誘導体、アクリルアミドやそれらを用いて得られた重合物や共重合物などポリアクリルアミドとその共重合物やポリビニルアミンやその共重合物などを挙げることができる。ただし、一般式［２］におけるＹ²は、炭素数８〜２２のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基の少なくとも一つと０〜１００個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はその誘導体から活性水素を除いた残基に限られる。これらの残基Ｙ¹〜Ｙ³を与える化合物は、１種を単独で用いることができ、あるいは、２種以上を組み合わせて用いることもできる。
【０００８】
本発明において、一般式［１］〜［３］におけるＡ¹〜Ａ³は、アシル基、水酸基を有するアシル基又はアミノ基を有するアシル基である。このようなアシル基としては、例えば、アセチル基、プロピオニル基、ブチリル基、ラウロイル基、パルミトイル基、ステアロイル基、イソステアロイル基、オレオイル基などのアシル基、ラクトイル基、リシノレオイル基などの水酸基を有するアシル基、グリシル基、アラニル基などのアミノ基を有するアシル基、アビエチル基などの複脂環族のアシル基や、そのマレイン酸やフマル酸などの付加物などを挙げることができる。一般式［１］におけるＡ¹は、その少なくとも一つが炭素数８〜２２のアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基である。一般式［１］〜［３］において、ｎ₁〜ｎ₃が２以上であるとき、複数個のＡ¹〜Ａ³は、同一であっても異なっていてもよい。
本発明において、一般式［１］〜［３］におけるＸ¹〜Ｘ³は、水素原子、アルキル基、アルケニル基、アルキルエーテル基、アシル基又は−(Ｂ¹Ｏ)k₁Ｒ¹〜−(Ｂ³Ｏ)k₃Ｒ³であり、Ｂ¹〜Ｂ³は、炭素数２〜４のアルキレン基、フェニルエチレン基又はフェノキシメチルエチレン基であり、Ｒ¹〜Ｒ³は、水素原子又は炭素数２〜２２のアシル基であり、ｋ₁〜ｋ₃は、１〜２０である。アルキル基は、炭素数２〜２２のアルキル基又は水酸基を有するアルキル基であることが好ましく、アルケニル基は、ビニル基又は炭素数３〜２２のアルケニル基若しくは水酸基を有するアルケニル基であることが好ましい。これらのアルキル基、アルケニル基及びアルキルエーテル基は、直鎖状であっても分岐を有していてもよい。アルキル基としては、例えば、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ドデシル基、テトラデシル基、ヘキサデシル基、オクタデシル基、イコシル基、ドコシル基などを挙げることができる。水酸基を有するアルキル基としては、例えば、２−ヒドロキシエチル基、２−ヒドロキシプロピル基、４−ヒドロキシブチル基、１０−ヒドロキシオクタデシル基などを挙げることができる。アルケニル基としては、例えば、プロペニル基、ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、テトラデセニル基、ヘキサデセニル基、オクタデセニル基、イコセニル基、ドコセニル基などを挙げることができる。ヒドロキシアルケニル基としては、例えば、３−ヒドロキシプロペニル基、１２−ヒドロキシ−９−オクタデセニル基、複脂環族のコレステロイル基、ラノステロイル基、ジヒドロラノステロイル基、アビエチル基などを挙げることができる。一般式［３］におけるＸ³は、その少なくとも一つが炭素数８〜２２のアルキル基、アルケニル基又はアシル基を有する基である。一般式［１］〜［３］において、ｍ₁〜ｍ₃が２以上であるとき、複数個のＸ¹〜Ｘ³は、同一であっても異なっていてもよい。
【０００９】
本発明の紙用不透明化剤においては、一般式［１］、［２］又は［３］におけるＡ¹、Ａ²又はＡ³は、その少なくとも一つが、次式で表されるアシル基であることが好ましい。
【化１６】

ただし、式中、Ｒ⁴〜Ｒ⁶は、炭素数７〜２１のアルキル基、アルケニル基、水酸基を有するアルキル基又は水酸基を有するアルケニル基である。Ｒ⁴〜Ｒ⁶の炭素数が７〜２１であると、紙用不透明化剤が良好な作業性を維持したまま、紙に優れた不透明度を与えることができる。
本発明の紙用不透明化剤は、一般式［１］〜［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物を反応して得られる化合物を含有する。一般式［１］〜［３］で表される化合物は、それ自体で紙を不透明化することができるが、一般式［１］〜［３］で表される化合物で紙を処理すると、紙の強度と表面強度及びサイズ度が低下する。一般式［１］〜［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物を反応して得られる化合物は、紙の強度と表面強度及びサイズ度を低下させることなく、紙を不透明化することができる。一般式［１］〜［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物を反応して得られる化合物は未反応のグリシジル基を有し、パルプに定着したのち、紙を生産する際に、ドライヤーなどから熱を与えられて高分子量化するために、紙の強度と表面強度や、サイズ度に悪影響を与えることがないものと推定される。エピハロヒドリン若しくはグリシジルエーテル又はそれらから誘導された化合物の中で、エピハロヒドリンがより好ましく、エピクロルヒドリンが特に好ましい。
【００１０】
本発明に用いるエピハロヒドリンに特に制限はなく、例えば、エピクロルヒドリン、エピブロムヒドリン、エピヨードヒドリンなどを挙げることができる。本発明に用いるグリシジルエーテルに特に制限はなく、例えば、アリルグリシジルエーテル、１,６−ヘキサンジオールジグリシジルエーテル、レゾルシンジグリシジルエーテル、エチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、プロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテルなどを挙げることができる。本発明に用いるエピハロヒドリン又はグリシジルエーテル化合物から誘導される化合物に特に制限はなく、例えば、エピハロヒドリン又はグリシジルエーテルのオリゴマーや、エピハロヒドリン又はグリシジルエーテルと他の化合物との反応生成物などを挙げることができる。エピハロヒドリン又はグリシジルエーテルと反応させる他の化合物としては、例えば、カルボキシル基を有する化合物、アミノ基を有する化合物、水酸基を有する化合物、二重結合又は三重結合を有する化合物などを挙げることができる。エピハロヒドリンから誘導された化合物としては、例えば、グリシドール、エピヒドリンカルボン酸、エピシアンヒドリン、エピクロルヒドリン変性フェノール樹脂などを挙げることができる。グリシジルエーテルから誘導される化合物としは、例えば、アクリル酸グリシジルエステル、メタクリル酸グリシジルエステル、アジピン酸ジグリシジルエステル、フタル酸ジグリシジルエステルなどを挙げることができる。
【００１１】
一般式［１］〜［３］で表される化合物とエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物との反応比に特に制限はないが、１／１０〜１０／１（モル比）であることが好ましく、１／５〜２／１（モル比）であることがより好ましい。一般式［１］〜［３］で表される化合物とエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物との反応比が１／１０（モル比）未満であると、紙の不透明化の効果が低下するおそれがある。一般式［１］〜［３］で表される化合物とエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物との反応比が１０／１（モル比）を超えると、紙の強度と表面強度やサイズ度が低下するおそれがある。本発明において、一般式［１］〜［３］で表される化合物と、エピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物を反応する方法に特に制限はなく、例えば、無触媒において、あるいは、ルイス酸、硫酸、三フッ化ホウ素などの酸触媒や、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどのアルカリ触媒の存在下などにおいて反応することができる。
本発明に用いる一般式［１］〜［３］で表される化合物の製造方法に特に制限はなく、例えば、モノアミン、ポリアミン、ポリアルキレンイミンなどを出発物質とし、これらの化合物の１個以上のアミノ基又は水酸基に、高級脂肪酸などを反応させて、アミド化又はエステル化して得ることができる。アミド化又はエステル化工程においては、出発物質であるポリアミンなど化合物の中の１個以上のアミノ基又は水酸基を、無触媒又は酸やアルカリなどの触媒を用いて、脂肪酸などによる高温脱水アミド化又はエステル化反応することができ、あるいは、脂肪酸クロリドなどによる脱塩酸反応や、低級アルコール脂肪酸エステルなどを使用してアミド交換又はエステル交換反応を行うことができる。このとき使用する脂肪酸、脂肪酸クロライド、脂肪酸低級アルコールエステルとしては、炭素数８〜２２の脂肪酸若しくは水酸基を有する脂肪酸又はそのクロライド若しくは低級アルコールエステルであることが好ましく、炭素数１２〜１８の脂肪酸若しくは水酸基を有する脂肪酸又はそのクロライド若しくは低級アルコールエステルであることがより好ましい。
【００１２】
本発明に用いる一般式［１］〜［３］で表される化合物は、天然油脂や、天然油脂を水素添加して得られる硬化油脂などのすでにエステル化されている化合物と、アミノ基を有する化合物又は水酸基を有する化合物とのアミド交換又はエステル交換により製造することもできる。使用する油脂としては、例えば、豚脂、牛脂、骨脂、鯨油などの動物油、オリーブ油、パーム油、大豆油、菜種油、アマニ油、ヤシ油などの植物油、魚油及びこれらの硬化油、半硬化油やラノリン、ロジンなどの複脂環族を含む油脂などを挙げることができる。
本発明において、Ｙ¹〜Ｙ³を残基とする化合物には、アミノ基又は水酸基を有する化合物も含まれるが、脂肪酸などと反応した場合、アミド化又はエステル化されたものが含まれていれば、このような化合物を用いることもできる。また、アミド化又はエステル化の反応モル数や反応位置に特に制限はなく、それぞれ、いずれの反応モル数、反応位置で反応した化合物も用いることができる。
さらに、本発明においては、ポリアミン、ポリアルキレンイミンなど又はその誘導体を一般式［１］〜［３］で表される化合物の出発物質として使用することができる。例えば、モノアミン、ポリアミン、ポリアルキレンイミンなどに尿素、ジシアンジアミドなどのグアニジン類、ホルマリン、エピハロヒドリン、イソシアネート化合物、グリシジルエーテル、アルキレンイミン、アルキルハライド、アルキレンオキシド、ジカルボン酸などの多価カルボン酸類、アミノ酸、シリル化剤などの活性水素に反応する化合物を用いて、重合、縮合、付加反応、架橋反応などを行って得られる化合物、ジメチル硫酸、エピハロヒドリンなどを用いて窒素に付加反応して４級化などした化合物など、分子内に、１個以上のアミド化又はエステル化可能な活性水素を１個以上有する化合物を出発物質として使用することができる。この場合反応順序を変えて、出発物質である、モノアミン、ポリアミン、ポリアルキレンイミンなどの１個以上のアミノ基、水酸基に脂肪酸などを反応させ、アミド化又はエステル化したのち、重合、縮合、付加反応、架橋反応などを行って得られる化合物、ジメチル硫酸、エピハロヒドリンなどによって窒素に付加反応して４級化などした化合物などを用いることもできる。
【００１３】
ポリアミン化合物の中には、脂肪酸などでアミド化した場合、脱水が進んでイミダゾリン環を形成するものがあるが、すべてイミダゾリン環化した化合物や、一部イミダゾリン環化した化合物も用いることができ、また、これらとイミダゾリン環を有しない化合物との混合物も用いることができる。さらに２個以上のイミダゾリン環を形成する場合、イミダゾリン環の位置や数については特に制限はなく、いずれも使用することができる。
また、反応順序を変え、モノアミン、ポリアミン、ポリアルキレンイミンなどの出発物質にエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導される化合物を先に反応したのち、分子内に１個以上のアミド化又はエステル化可能な活性水素を１個以上有していれば、この化合物のアミノ基又は水酸基に高級脂肪酸などを反応させ、アミド化又はエステル化して得ることもできる。基本的に反応順序が変わっても、一般式［１］〜［３］で表される化合物の中に、１個以上の窒素を有し、一般式［１］の少なくとも一つのＡ¹が、炭素数８〜２２のアシル基、水酸基を有するアシル基又はアミノ基を有するアシル基であり、一般式［２］のＹ²である（ｎ₂＋ｍ₂）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はそれらの誘導体から、活性水素を除いた残基を与える化合物が、炭素数８〜２２のアルキル基、アルケニル基又、水酸基を有するアルキル基又は水酸基を有するアルケニル基を有する化合物であり、あるいは、一般式［３］の少なくとも一つのＸ³が、炭素数８〜２２のアルキル基、アルケニル基又はアシル基を有する基である化合物を用いることができる。すなわち、一般式［１］〜［３］のＹ¹〜Ｙ³である（ｎ₁＋ｍ₁）〜（ｎ₃＋ｍ₃）個の活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はそれらの誘導体から活性水素を除いた残基を与える化合物に、エピハロヒドリン若しくはグリシジルエーテル及び／又それらから誘導される化合物を反応させることができる。
本発明において、出発物質のポリアミン、ポリアルキレンイミン又はそれらの誘導体は、１種を単独で使用することができ、あるいは、２種以上を組み合わせて使用することもできる。また、またエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物を反応する一般式［１］〜［３］で表される化合物も、１種を単独で使用することができ、あるいは、２種以上を組み合わせて使用することもできる。また、反応させるエピハロヒドリン若しくはグリシジルエーテル及び／又はそれらから誘導された化合物も、１種を単独で使用することができ、あるいは、２種以上を組み合わせて使用することもできる。さらに、本発明の紙用不透明化剤も、１種を単独で使用することができ、あるいは、２種以上を組み合わせて使用することもできる。
【００１４】
本発明の紙用不透明化剤は、製紙工程において、原料であるパルプのいずれの工程においても添加することができる。例えば、離解工程直後、叩解前後、薬品などを添加する調整前後、抄紙前、古紙の場合などは再生処理前後などいずれの工程においても適用することができる。
本発明方法により製造される不透明度向上紙は、広義で考えられる紙で、植物繊維及び／又はその他の繊維をからみ合わせ膠着してできた薄層からなるものであり、使用するパルプなどの原料や薬品によって限定されるものではない。従来の木材パルプから得られる紙のみならず、例えば、バガス、ケナフ、竹パルプなどの植物繊維を含有する薄層体からも、本発明方法により不透明度向上紙を製造することができる。
本発明の紙用不透明化剤の使用方法に特に制限はなく、例えば、そのまま使用することができ、あるいは、水や溶剤に、溶解、分散又は乳化して使用することもできる。また、分散、乳化させるために、界面活性剤や溶剤を用い、蟻酸、酢酸などの酸で中和し、あるいはその他の化学薬品と混合することもできる。
本発明の紙用不透明化剤の形態に制限はなく、また、必要に応じて他の機能を付与するため、他の化学薬品を併用することもできる。このような化学薬品としては、例えば、湿潤紙力剤や乾燥紙力剤、澱粉、ポリビニルアルコールなどの紙力剤やドライヤー剥離剤、ピッチコントロール剤、スライムコントロール剤、脱墨剤、サイズ剤、紙質改善剤、填料、顔料、染料、消泡剤などを挙げることができる。
【００１５】
【実施例】
以下に、実施例を挙げて本発明をさらに詳細に説明するが、本発明はこれらの実施例によりなんら限定されるものではない。
なお、実施例及び比較例において、不透明度向上紙の評価は下記の方法により行った。
（１）不透明度
ＳＭカラーコンピューター［スガ試験機(株)］を用いて測定した。
（２）白色度
ＳＭカラーコンピューター［スガ試験機(株)］を用いて測定した。
（３）密度
ＪＩＳ Ｐ ８１１８に準じて測定した。
（４）乾燥比破裂強度
ＪＩＳ Ｐ ８１１２に準じて測定した。
（５）湿潤比破裂強度
試験紙を２０℃の水に１０分間浸漬したのち、ＪＩＳ Ｐ ８１１２に準じて測定した。
（６）表面強度
ＪＩＳ Ｐ ８１２９ ２.１のワックスを用いる方法に準じて測定した。
（７）サイズ度
ＪＩＳ Ｐ ８１２２に準じて測定した。
【００１６】
製造例１
テトラエチレンペンタミン６３.１ｇとステアリン酸１８９.７ｇ（モル比１／２）を、脱水管、温度計及び窒素ガス吹き込み管を取り付けた４つ口フラスコに取り、マントルヒーターで徐々に加熱し、窒素ガスを吹き込みながら、１８０℃〜２００℃にて５時間脱水反応を行い、中間体化合物ａを得た。この化合物１６９.８ｇを、コンデンサー、温度計及び滴下ロートを取り付けた４つ口フラスコに取り、マントルヒーターで９０℃に加熱し、エピクロルヒドリン４６.３ｇ（モル比１／２）を、発熱に気をつけ、温度を９０〜１００℃に保ちながら、滴下した。滴下終了後、温度を９０〜１００℃に保ちながら、４時間反応して、紙用不透明化剤成分を得た。この紙用不透明化剤成分を、紙用不透明化剤成分１とする。
製造例２
エピクロルヒドリンの量を６９.５ｇ（モル比１／３）とした以外は、製造例１と同様にして、紙用不透明化剤成分を得た。この紙用不透明化剤成分を、紙用不透明化剤成分２とする。
製造例３
アミノエチルエタノールアミン３４.７ｇとステアリン酸１８９.７ｇ（モル比１／２）と、触媒としてのパラトルエンスルホン酸０.５ｇを、脱水管、温度計及び窒素ガス吹き込み管を取り付けた４つ口フラスコに取り、マントルヒーターで徐々に加熱し、窒素ガスを吹き込みながら、２００〜２２０℃にて５時間脱水反応を行い、中間体化合物ｂを得た。この化合物１５９.３ｇを、コンデンサー、温度計及び滴下ロートを取り付けた４つ口フラスコに取り、マントルヒーターで９０℃に加熱したのち、エピクロルヒドリン２３.１ｇ（モル比１／１）を、発熱に気をつけ、温度を９０〜１００℃に保ちながら、滴下した。滴下終了後、温度を９０〜１００℃に保ちながら、４時間反応して、紙用不透明化剤成分を得た。この紙用不透明化剤成分を、紙用不透明化剤成分３とする。
【００１７】
製造例４
ジエチレントリアミン３４.４ｇに、ステアリン酸とラウリン酸のモル比１／１の混合物１６１.６ｇ（モル比１／２）と、触媒としてのパラトルエンスルホン酸０.５ｇを、脱水管、温度計及び窒素ガス吹き込み管を取り付けた４つ口フラスコに取り、マントルヒーターで徐々に加熱し、窒素ガスを吹き込みながら、２００〜２２０℃にて５時間脱水反応を行い、中間体化合物ｃを得た。この化合物１３８.０ｇを、コンデンサー、温度計及び滴下ロートを取り付けた４つ口フラスコに取り、マントルヒーターで９０℃に加熱したのち、エピクロルヒドリン２３.１ｇ（モル比１／１）を、発熱に気をつけ、温度を９０〜１００℃に保ちながら、滴下した。滴下終了後、温度を９０〜１００℃に保ちながら、４時間反応して、紙用不透明化剤成分を得た。この紙用不透明化剤成分を、紙用不透明化剤成分４とする。
製造例５
ジステアリルモノメチルアミン１３３.８ｇを、コンデンサー、温度計及び滴下ロートを取り付けた４つ口フラスコに取り、マントルヒーターで９０℃に加熱したのち、エピクロルヒドリン２３.１ｇ（モル比１／１）を、発熱に気をつけ、温度を９０〜１００℃に保ちながら、滴下した。滴下終了後、温度を９０〜１００℃に保ちながら、４時間反応して、紙用不透明化成分剤を得た。この紙用不透明化剤成分を、紙用不透明化剤成分５とする。
製造例６〜２０
活性水素を有するモノアミン、ポリアミン、ポリアルキレンイミン又はそれらの誘導体から活性水素を除いた残基Ｙ¹〜Ｙ³を与える化合物である出発物質と、アシル基、水酸基を有するアシル基又はアミノ基を有するアシル基Ａ¹〜Ａ³を与える化合物を製造例１〜５と同様に反応して、中間体化合物ｅ〜ｎを得た。
さらに、得られた中間体化合物に、エピクロルヒドリン、エピブロムヒドリン又はアリルグリシジルエーテルを製造例１〜５と同様に反応して、紙用不透明化剤成分６〜２０を得た。
製造例１〜２０で得られた中間体を第１表に、紙用不透明化剤成分を第２表に示す。
【００１８】
【表１】

【００１９】
【表２】

【００２０】
実施例１（紙用不透明化剤の調製）
紙用不透明化剤成分１〜２０は水に溶解しないので、これらの紙用不透明化剤成分を加熱融解したのち、酢酸で中和し、徐々に水又は熱水を加えながらスパーテルで撹拌して乳化し、１０重量％の乳化物を調製した。これらの乳化物を、それぞれ試験用ホモジナイザーに１回通して、本発明の紙用不透明化剤１〜２０を得た。
比較例１（比較紙用不透明化剤の調製）
紙用不透明化剤成分として、第３表に示す化合物を用いて、比較紙用不透明化剤１〜２０を調製した。比較紙用不透明化剤１〜１２と比較紙用不透明化剤１９は、実施例１と同様にして調製し、比較紙用不透明化剤１３〜１６と比較紙用不透明化剤１８は、界面活性剤としてソルビトールのエチレンオキシド付加物の脂肪酸エステル化物（ツイン由来）を紙用不透明化剤成分に２重量％配合して乳化し、比較紙用不透明化剤１７と２０は、１０重量％水溶液とした。
【００２１】
【表３】

【００２２】
実施例２（不透明度向上紙の作製と評価）
上質古紙の再生パルプ（フリーネス４２０ml）とＮＢＫＰ（フリーネス４２０ml）を重量比７０／３０に配合したパルプを、ケミスターラーを用いて撹拌しながら、１０分間の間隔をおいて、紙用不透明化剤１をパルプに対して０.３重量％添加、乾燥紙力剤（アニオン系）をパルプに対して０.４重量％添加、硫酸バンドでpHを４.５に調整、エマルジョンサイズ剤をパルプに対して１重量％添加、湿潤紙力剤（カチオン系）をパルプに対して１重量％添加した。その後、６０分撹拌を継続して、パルプの調製を終了した。
次いで、試験用角型シートマシンを用いて坪量８０ｇ／ｍ²に抄紙し、プレス機を用いて７kgで５分間プレス処理を行い、試験用のヤンキードライヤーを用いて１０５℃で３分乾燥して不透明度向上紙を得た。
得られた不透明度向上紙の不透明度８７.１％、白色度８６.３、密度０.５２９ｇ／cm³、乾燥比破裂強度２.２３、湿潤比破裂強度０.９３、表面強度７Ａ、サイズ度３９秒であった。
実施例３（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、紙用不透明化剤２〜２０を用い、実施例２と同様にして、１９種の不透明度向上紙を作製し、評価を行った。
比較例２（紙の作製と評価）
紙用不透明化剤を添加しない以外は、実施例２と同様にして紙を作製し、評価を行った。
得られた紙の不透明度８４.６％、白色度８４.９、密度０.５７２ｇ／cm³、乾燥比破裂強度２.３２、湿潤比破裂強度０.９８、表面強度７Ａ、サイズ度４０秒であった。
比較例３（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤１を用い、実施例２と同様にして不透明度向上紙を作製し、評価を行った。
得られた不透明度向上紙の不透明度８７.０％、白色度８６.０、密度０.５３４ｇ／cm³、乾燥比破裂強度１.６３、湿潤比破裂強度０.５７、表面強度６Ａ、サイズ度２７秒であった。
比較例４（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤２〜２０を用い、実施例２と同様にして、１９種の不透明度向上紙を作製し、評価を行った。
実施例２〜３の結果を第４表に、比較例２〜４の結果を第５表に示す。
【００２３】
【表４】

【００２４】
【表５】

【００２５】
第４表に見られるように、本発明の紙用不透明化剤１〜２０を用いて作製した実施例の不透明度向上紙は、不透明度と白色度が高く、密度が低く、比破裂強度、表面強度、サイズ度ともに大きく、優れた品質を有している。これに対して、第５表に見られるように、中間体ａ〜ｋを用いて調製した比較紙用不透明化剤１〜１１及び１９を用いて作製した比較例の不透明度向上紙は、不透明度と白色度は比較的良好であり、密度も低いが、比破裂強度、表面強度及びサイズ度がいずれも小さい。また、従来の紙用不透明化剤１２〜１８及び２０を用いて作製した比較例の不透明度向上紙は、比破裂強度、表面強度、サイズ度は比較的良好であるが、不透明度と白色度が劣り、密度が高い。
実施例４（不透明度向上紙の作製と評価）
新聞古紙の再生パルプ（フリーネス４５０ml）とＴＭＰ（フリーネス４５０ml）を重量比５５／４５に配合したパルプを、ケミスターラーを用いて撹拌しながら、１０分間の間隔をおいて、紙用不透明化剤１をパルプに対して０.３重量％添加、乾燥紙力剤（アニオン系）をパルプに対して０.２重量％添加、硫酸バンドでpHを４.５に調整、エマルジョンサイズ剤をパルプに対して０.４重量％添加、湿潤紙力剤（カチオン系）をパルプに対して０.４重量％添加した。その後、６０分撹拌を継続して、パルプの調製を終了した。
次いで、試験用角型シートマシンを用いて坪量４５ｇ／ｍ²に抄紙し、プレス機を用いて７kgで５分プレス処理を行い、試験用のヤンキードライヤーを用いて１０５℃で３分乾燥して不透明度向上紙を得た。
得られた不透明度向上紙の不透明度９２.０％、白色度５８.０、密度０.４７２ｇ／cm³、乾燥比破裂強度０.９８、湿潤比破裂強度０.２２、表面強度５Ａ、サイズ度７秒であった。
実施例５（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、紙用不透明化剤２〜２０を用い、実施例４と同様にして、１９種の不透明度向上紙を作製し、評価を行った。
比較例５（紙の作製と評価）
紙用不透明化剤を添加しない以外は、実施例４と同様にして紙を作製し、評価を行った。
得られた紙の不透明度８９.８％、白色度５６.２、密度０.５０６ｇ／cm³、乾燥比破裂強度１.００、湿潤比破裂強度０.２１、表面強度５Ａ、サイズ度８秒であった。
比較例６（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤１を用い、実施例４と同様にして不透明度向上紙を作製し、評価を行った。
得られた不透明度向上紙の不透明度９１.７％、白色度５７.８、密度０.４８５ｇ／cm³、乾燥比破裂強度０.６８、湿潤比破裂強度０.１１、表面強度４Ａ、サイズ度４秒であった。
比較例７（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤２〜２０を用い、実施例４と同様にして、１９種の不透明度向上紙を作製し、評価を行った。
実施例４〜５の結果を第６表に、比較例５〜７の結果を第７表に示す。
【００２６】
【表６】

【００２７】
【表７】

【００２８】
第６表に見られるように、本発明の紙用不透明化剤１〜２０を用いて作製した実施例の不透明度向上紙は、不透明度と白色度が高く、密度が低く、比破裂強度、表面強度、サイズ度ともに大きく、優れた品質を有している。これに対して、第７表に見られるように、中間体ａ〜ｋを用いて調製した比較紙用不透明化剤１〜１１及び１９を用いて作製した比較例の不透明度向上紙は、不透明度と白色度は比較的良好であり、密度も低いが、比破裂強度、表面強度及びサイズ度がいずれも小さい。また、従来の紙用不透明化剤１２〜１８及び２０を用いて作製した比較例の不透明度向上紙は、比破裂強度、表面強度、サイズ度は比較的良好であるが、不透明度と白色度が劣り、密度が高い。
実施例６（不透明度向上紙の作製と評価）
ＮＢＫＰ（フリーネス４００ml）とＬＢＫＰ（フリーネス４００ml）を重量比５０／５０に配合したパルプを、ケミスターラーを用いて撹拌しながら、１０分間の間隔をおいて、炭酸カルシウムをパルプに対して５重量％添加、紙用不透明化剤１をパルプに対して０.３重量％添加、アルキルケテンダイマータイプのサイズ剤をパルプに対して１.０重量％添加、乾燥紙力剤（両性系）をパルプに対して０.５重量％添加した。その後、６０分撹拌を継続して、パルプの調製を終了した。
次いで、試験用角型シートマシンを用いて坪量６５ｇ／ｍ²に抄紙し、プレス機を用いて７kgで５分プレス処理を行い、試験用のヤンキードライヤーを用いて１０５℃で３分乾燥して不透明度向上紙を得た。
得られた不透明度向上紙の不透明度８１.３％、白色度８８.０、密度０.４９８ｇ／cm³、乾燥比破裂強度１.９３、表面強度７Ａ、サイズ度２３秒であった。
実施例７（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、紙用不透明化剤２〜２０を用い、実施例６と同様にして、１９種の不透明度向上紙を作製し、評価を行った。
比較例８（紙の作製と評価）
紙用不透明化剤を添加しない以外は、実施例６と同様にして紙を作製し、評価を行った。
得られた紙の不透明度７８.７％、白色度８６.０、密度０.５２０ｇ／cm³、乾燥比破裂強度１.９６、表面強度６Ａ、サイズ度２４秒であった。
比較例９（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤２を用い、実施例６と同様にして不透明度向上紙を作製し、評価を行った。
得られた不透明度向上紙の不透明度８１.２％、白色度８７.７、密度０.４９９ｇ／cm³、乾燥比破裂強度１.３４、表面強度６Ａ、サイズ度１２秒であった。
比較例１０（不透明度向上紙の作製と評価）
紙用不透明化剤１の代わりに、比較紙用不透明化剤１〜２０を用い、実施例６と同様にして、２０種の不透明度向上紙を作製し、評価を行った。
実施例６〜７の結果を第８表に、比較例８〜１０の結果を第９表に示す。
【００２９】
【表８】

【００３０】
【表９】

【００３１】
第８表に見られるように、本発明の紙用不透明化剤１〜２０を用いて作製した実施例の不透明度向上紙は、不透明度と白色度が高く、密度が低く、比破裂強度、表面強度、サイズ度ともに大きく、優れた品質を有している。これに対して、第９表に見られるように、中間体ａ〜ｋを用いて調製した比較紙用不透明化剤１〜１１及び１９を用いて作製した比較例の不透明度向上紙は、不透明度と白色度は比較的良好であり、密度も低いが、比破裂強度、表面強度及びサイズ度がいずれも小さい。また、従来の紙用不透明化剤１２〜１８及び２０を用いて作製した比較例の不透明度向上紙は、比破裂強度、サイズ度は比較的良好であるが、不透明度、白色度と表面硬度が劣り、密度も高い。
実施例８（不透明度向上紙の作製と評価）
上質古紙の再生パルプ（フリーネス４２０ml）とＮＢＫＰ（フリーネス４２０ml）を重量比７０／３０に配合したパルプを、ケミスターラーを用いて撹拌しながら、１０分間の間隔をおいて、紙用不透明化剤１をパルプに対して０.１５重量％添加、乾燥紙力剤（アニオン系）をパルプに対して０.４重量％添加、硫酸バンドでpHを４.５に調整、エマルジョンサイズ剤をパルプに対して１重量％添加、湿潤紙力剤（カチオン系）をパルプに対して１重量％添加した。その後、６０分撹拌を継続して、パルプの調製を終了した。
次いで、試験用角型シートマシンを用いて坪量８０ｇ／ｍ²に抄紙し、プレス機を用いて７kgで５分プレス処理を行い、試験用のヤンキードライヤーを用いて１０５℃で３分乾燥して不透明度向上紙を得た。
得られた不透明度向上紙の不透明度８７.８％、白色度８７.２、密度０.５４３ｇ／cm³、乾燥比破裂強度２.３４、湿潤比破裂強度１.０３、表面強度７Ａ、サイズ度４５秒であった。
実施例９（不透明度向上紙の作製と評価）
紙用不透明化剤１を添加する１０分前に、酸化チタンをパルプに対して１重量％添加した以外は、実施例８と同様にして不透明度向上紙を作製した。
得られた不透明度向上紙の不透明度８８.９％、白色度８８.０、密度０.５４３ｇ／cm³、乾燥比破裂強度２.２３、湿潤比破裂強度１.００、表面強度７Ａ、サイズ度４４秒であった。
実施例１０（不透明度向上紙の作製と評価）
酸化チタンのパルプに対する添加量を、０重量％、１重量％、２.５重量％及び５重量％の４水準とし、紙用不透明化剤１又は３を用い、そのパルプに対する添加量を０.１５重量％及び０.３重量％の２水準として、実施例８又は実施例９と同様にして、不透明度向上紙を作製し、評価を行った。
比較例１１（不透明度向上紙の作製と評価）
比較紙用不透明化剤１又は２０を用い、あるいは紙用不透明化剤を添加することなく、実施例８又は実施例９と同様にして、紙を作製し、評価を行った。
実施例８〜１０の結果を第１０表に、比較例１１の結果を第１１表に示す。
【００３２】
【表１０】

【００３３】
【表１１】

【００３４】
第１０表に見られるように、本発明の紙用不透明化剤１又は３を用い、酸化チタンを添加することなく、又は、添加して作製した実施例の不透明度向上紙は、不透明度と白色度が高く、密度が低く、比破裂強度、表面強度、サイズ度ともに大きく、優れた品質を有している。また、紙用不透明化剤の添加量が多いほど、また、酸化チタンの添加量が多いほど、不透明度と白色度が向上している。これに対して、第１１表に見られるように、中間体ａを用いて調製した比較紙用不透明化剤１を用いて作製した比較例の不透明度向上紙は、不透明度と白色度は比較的良好であり、密度も低いが、比破裂強度、表面強度及びサイズ度がいずれも小さい。また、従来の紙用不透明化剤２０を用いて作製した比較例の不透明度向上紙は、比破裂強度、表面硬度、サイズ度は比較的良好であるが、不透明度と白色度が劣り、密度も高い。
【００３５】
【発明の効果】
本発明の不透明化剤を用いることにより、比破裂強度、表面強度、サイズ度を高い水準に維持したまま、不透明度と白色度を向上することができるので、紙製品のパルプ原料の使用量を低減し、製品の製造スピードを向上するとともに、原料コストを低減することができる。さらに、従来の填料を使用する方法を一部置き換えるか、又は、すべてを置き換えることにより、従来の填料を使用する方法が有する問題点を解消又は軽減することができ、さらには、従来の填料を使用する方法に追加することにより、さらに紙の不透明度を向上させるなど、紙製品の品質の向上やコストの低減が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper opacifier, a method for producing an opacity improving paper, and an opacity improving paper. More specifically, the present invention can improve the opacity of all paper products such as newsprint, printing paper, recording paper, wrapping paper, base paper for wallpaper, backing paper, etc., and can produce a paper product with high opacity. The present invention relates to an opacifying agent for paper, a method for producing an opacity improving paper, and an opacity improving paper produced by the method.
[0002]
[Prior art]
In recent years, efforts have been made to reduce the basis weight of paper products in order to reduce the amount of pulp used as much as possible due to a shortage of pulp resources, a rise in pulp prices, and the need to protect the global environment. For example, newspaper paper has a basis weight of 50 g / m. ² 40g / m from the stand ² Stand, further 30g / m ² By lowering it to the stand, we have dealt with global environmental problems, and have tried to reduce costs and improve papermaking speed. In addition, printing paper, recording paper, wrapping paper, base paper for wall paper, backing paper, etc. have a great effect on global environmental issues such as cost savings and securing of forest resources by further reducing the basis weight of paper products. It is thought to bring about.
However, various problems occur by reducing the basis weight of paper. One of the problems is a decrease in opacity. For example, in the case of newsprint, when the opacity decreases, the back side prints on the front side. Further, when the whiteness of newsprint is increased to a high grade, light absorption is reduced, and in order to maintain opacity, it is necessary to increase the basis weight. In order to make up for this drawback, gate roll coating, etc., is used in combination with sizing agents and starches, and inorganic fillers and organic pigments are applied to the surface, added internally, or colored with dyes and pigments. The opacity has been maintained by using colored waste paper as a raw material.
However, when inorganic fillers are used, paper dust remains on the dryer surface during production, and not only does paper dust occur when cutting paper such as ear cuts, but also damages the cutter blade. There is also a problem that it is easy. In addition, it damages machines such as wires, dryers, rolls, etc., and clogs and damages such as wet blankets, top blankets, and canvases shorten the life. Further, since the strength of the paper and the paper surface is lowered, in order to prevent the strength from being lowered, a paper strength agent, starch or the like must be used in a large amount.
As the inorganic filler, white clay (clay), kaolin, talc, talc, aluminum hydroxide, diatomaceous earth, barium sulfate, calcium sulfate and the like are used, and organic pigments such as polystyrene are also used. Since these fillers have a relatively low refractive index, opacity cannot be obtained unless they are used in a large amount. However, if they are used in a large amount, the above-mentioned problems occur. Titanium oxide is an inorganic filler that has a high refractive index and can be opaque with a relatively small addition amount. However, titanium oxide is expensive and expensive. Recently, calcium carbonate has been used, in which newsprint paper is made neutral and has a refractive index that is not as high as that of titanium oxide, but is relatively inexpensive and provides opacity. However, when paper containing calcium carbonate is recycled as waste paper, if calcium carbonate remains, carbon dioxide gas is generated during acidic papermaking, causing problems such as bubbles. In addition, when the paper is colored, the color of the paper is limited, and a high-grade paper with high whiteness cannot be obtained.
In the case of printing paper, recording paper, and wrapping paper, as with newsprint paper, when the basis weight is lowered, the opacity is lowered. For this reason, when papers are stacked, printing or recording appears on the front side from the back side, and conversely, printing or recording on the front side appears on the back side. For this reason, in order to maintain the opacity, the opacity has been maintained by coating the surface with an inorganic filler, adding it internally, or coloring it with a dye or pigment. However, the use of inorganic fillers inevitably causes problems such as the above-mentioned paper dust, machine damage, blanket life, and strength reduction. Even if an inorganic filler or the like is internally added or a yield improver is used, the yield rate is limited. Also, in the case of coating, although an opacity can be obtained if it is used excessively, it is contrary to the original purpose of reducing the basis weight. Even if the amount of pulp to be used is reduced, it is also a problem that the amount of inorganic filler used is increased. Moreover, it is inevitable that the paper is limited by coloring.
Even in the case of wallpaper, cardboard, backing paper, paperboard, and cardboard, the lower the basis weight, the lower the opacity, and the background color will be reflected when it is applied or pasted. In order to eliminate such a problem, similarly, an inorganic filler or the like is applied to the surface, internally added, or colored, or colored waste paper is used to maintain opacity. However, in this method, the above-mentioned problem occurs similarly. Furthermore, there is a method of improving opacity by making paper in multiple layers. In order to maintain the whiteness of the surface, there is a method of maintaining the opacity of the entire paper by making the surface layer paper white and coloring the back layer. There is also a method of gradually whitening the color from the back. However, in order to prevent the color of the back surface from appearing on the front surface, it is necessary to improve the opacity of the paper on the surface layer, and eventually it is necessary to increase the opacity of the surface layer by using an inorganic filler or the like. .
In this way, in order to increase the opacity of paper products, use inorganic fillers, etc. to improve the opacity by using the reflection and scattering of light by particles, and to absorb light such as coloring. There is a way to improve opacity by using it. However, there is a limit to the method of using inorganic filler and the yield rate is also limited. Even if the filler can be fixed at a high yield, the paper function is lost. In addition, when an extremely large amount of filler is applied, the opacity is improved, but the basis weight becomes high, which is contrary to the original purpose. Even if the amount of pulp used can be reduced, it is problematic if the amount of filler used increases. Also, the coloring method or the like cannot obtain paper with high whiteness, and the paper products to be produced are limited.
As described above, the above-mentioned method has already reached the limit, and in addition to this, there is a method of obtaining opacity by changing the content of the pulp itself or the paper layer structure in order to further improve the opacity. For example, there is a method of controlling the opacity by adjusting the beating degree of pulp to be used. In general, the opacity is improved by lowering the beating degree. However, this method also has problems. For example, there is little entanglement between the pulps, and the hydrogen bonds are weak, so the strength of the paper and the paper surface is weak. When it comes to multilayer papermaking, problems such as weak interlayer strength occur. In addition, the smoothness of the paper surface is low, and printability is reduced. In addition, the fixability of chemicals such as paper strength agents, sizing agents, dyes and pigments, and fillers is reduced.
Recently, chemicals that improve the opacity (organic opacifiers) have been released by changing the paper layer structure by using organic compounds, and there are cases where the effect of improving opacity has been recognized. The organic compound has the disadvantage that the strength and surface strength of the paper are reduced. Furthermore, there is a disadvantage that the sizing degree is lowered. In many paper products, such as newsprint, printing paper, recording paper, wrapping paper, paperboard, wallpaper, base paper and backing paper, paper strength, surface strength, and size are important qualities, which affect this quality. It must be said that it is a big fault.
[0003]
[Problems to be solved by the invention]
The present invention improves the opacity of all paper products such as newsprint, printing paper, recording paper, wrapping paper, wallpaper paper base, backing paper, etc., and has high opacity without reducing the strength and sizing of the paper An object of the present invention is to provide a paper opacifying agent capable of producing a paper product, a method for producing an opacity improving paper, and an opacity improving paper produced by the method.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have used an amine compound having an alkyl group, alkenyl group or acyl group having 8 or more carbon atoms and a compound obtained by reacting epichlorohydrin. It has been found that the opacity can be improved without lowering the strength, surface strength and sizing degree of the paper by processing, and the present invention has been completed based on this finding.
That is, the present invention
(1) A reaction product obtained by reacting a compound represented by the general formula [1] with epihalohydrin or glycidyl ether and / or a compound derived therefrom, Neutralize with acid, By dissolving or dispersing in water, adding an anionic or amphoteric dry paper strength agent, adding a sizing agent to prepare a pulp, and subjecting the pulp to a paper making process, a pressing process and a drying process More than 2.0% in the region where the opacity is 87.0% or more, and the density is 0.021 g / cm than the paper produced without adding the reaction product. ^Three A method for producing an opacity-enhanced paper, characterized in that it obtains a paper having a smaller size and a decrease in sizing of 2 seconds or less,
[Chemical 7]

(However, in the formula, Y ¹ Is (n ₁ + M ₁ A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ¹ Is an acyl group, an acyl group having a hydroxyl group, or an acyl group having an amino group, and at least one of these acyl groups has 8 to 22 carbon atoms, ¹ Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ¹ O) k ₁ R ¹ (Here B ¹ Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ¹ Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k ₁ Is 1-20. ) And n ₁ Is 1 or more and m ₁ Is greater than or equal to 0 and n ₁ + M ₁ = 1 to 100, n ₁ If A is 2 or more, multiple A ¹ May be the same or different and m ₁ If X is 2 or more, multiple X ¹ May be the same or different. ),
(2) A reaction product obtained by reacting the compound represented by the general formula [2] with epihalohydrin or glycidyl ether and / or a compound derived therefrom, Neutralize with acid, Dissolve or disperse in water and add, add anionic or amphoteric dry paper strength agent, add sizing agent and mix to prepare pulp, and use the pulp in paper making process, pressing process and drying process By applying, the density difference is 0.021 g / cm, which is larger by 2.0% or more in the region where the opacity is 87.0% or more than that of the paper produced without adding the reaction product. ^Three A method for producing an opacity-enhanced paper, characterized in that it obtains a paper having a smaller size and a decrease in sizing of 2 seconds or less,
[Chemical 8]

(However, in the formula, Y ² And at least one of an alkyl group having 8 to 22 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group (n ₂ + M ₂ A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ² Is an acyl group, an acyl group having a hydroxyl group or an acyl group having an amino group, and X ² Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ² O) k ₂ R ² (Here B ² Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ² Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k ₂ Is 1-20. ) And n ₂ Is greater than 0 and m ₂ Is greater than or equal to 0 and n ₂ + M ₂ = 0 to 100, n ₂ If A is 2 or more, multiple A ² May be the same or different and m ₂ If X is 2 or more, multiple X ² May be the same or different. ),
(3) A reaction product obtained by reacting the compound represented by the general formula [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom, Neutralize with acid, Dissolve or disperse in water and add, add anionic or amphoteric dry paper strength agent, add sizing agent and mix to prepare pulp, and use the pulp in paper making process, pressing process and drying process By applying, the density difference is 0.021 g / cm, which is 2.0% or more larger in the region where the opacity is 87.0% or more than that of the paper produced without adding the reaction product. ^Three A method for producing an opacity-enhanced paper, characterized in that it obtains a paper having a smaller size and a decrease in size of 2 seconds or less,
[Chemical 9]

(However, in the formula, Y ^Three Is (n _Three + M _Three A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ^Three Is an acyl group, an acyl group having a hydroxyl group or an acyl group having an amino group, and X ^Three Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ^Three O) k _Three R ^Three (Here B ^Three Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ^Three Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k _Three Is 1-20. ) Where X ^Three At least one of these is a group having an alkyl group, an alkenyl group or an acyl group having 8 to 22 carbon atoms, and n _Three Is greater than 0 and m _Three Is 1 or more and n _Three + M _Three = 1 to 100, n _Three If A is 2 or more, multiple A ^Three May be the same or different and m _Three If X is 2 or more, multiple X ^Three May be the same or different. ),
(4) A ¹ Wherein at least one of the groups is a group represented by the general formula [4],
[Chemical Formula 10]

(However, in the formula, R ^Four Is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group. ),
(5) A ² At least one of which is a group represented by the general formula [5], the method for producing an opacity-enhancing paper according to item (2),
Embedded image

(However, in the formula, R ^Five Is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group. ),as well as,
(6) A ^Three At least one of which is a group represented by the general formula [6], the method for producing an opacity-enhancing paper according to item (3),
Embedded image

(However, in the formula, R ⁶ Is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group. ),
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
A first embodiment of the paper opacifier for paper of the present invention contains a compound obtained by reacting a compound represented by the general formula [1] with epihalohydrin or glycidyl ether and / or a compound derived therefrom. To do.
Embedded image

In general formula [1], Y ¹ Is (n ₁ + M ₁ A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ¹ Is an acyl group, an acyl group having a hydroxyl group, or an acyl group having an amino group, and at least one of these acyl groups has 8 to 22 carbon atoms, ¹ Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ¹ O) k ₁ R ¹ (Here B ¹ Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ¹ Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k ₁ Is 1-20. ) And n ₁ Is 1 or more and m ₁ Is greater than or equal to 0 and n ₁ + M ₁ = 1 to 100, n ₁ If A is 2 or more, multiple A ¹ May be the same or different and m ₁ If X is 2 or more, multiple X ¹ May be the same or different.
A second embodiment of the paper opacifier for paper of the present invention contains a compound obtained by reacting a compound represented by the general formula [2] with epihalohydrin or glycidyl ether and / or a compound derived therefrom. To do.
Embedded image

In general formula [2], Y ² And at least one of an alkyl group having 8 to 22 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group (n ₂ + M ₂ A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ² Is an acyl group, an acyl group having a hydroxyl group or an acyl group having an amino group, and X ² Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ² O) k ₂ R ² (Here B ² Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ² Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k ₂ Is 1-20. ) And n ₂ Is greater than 0 and m ₂ Is greater than or equal to 0 and n ₂ + M ₂ = 0 to 100, n ₂ If A is 2 or more, multiple A ² May be the same or different and m ₂ If X is 2 or more, multiple X ² May be the same or different.
[0006]
A third aspect of the paper opacifier for paper of the present invention contains a compound obtained by reacting a compound represented by the general formula [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom. To do.
Embedded image

In general formula [3], Y ^Three Is (n _Three + M _Three A residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkylenimine or derivative thereof having one active hydrogen; ^Three Is an acyl group, an acyl group having a hydroxyl group or an acyl group having an amino group, and X ^Three Is a hydrogen atom, alkyl group, alkenyl group, alkyl ether group, acyl group or-(B ^Three O) k _Three R ^Three (Here B ^Three Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ^Three Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k _Three Is 1-20. ) Where X ^Three At least one of these is a group having an alkyl group, an alkenyl group or an acyl group having 8 to 22 carbon atoms, and n _Three Is greater than 0 and m _Three Is 1 or more and n _Three + M _Three = 1 to 100, n _Three If A is 2 or more, multiple A ^Three May be the same or different and m _Three If X is 2 or more, multiple X ^Three May be the same or different.
A fourth aspect of the paper opacifier of the present invention is a monoamine, polyamine, polyalkyleneimine or derivative thereof having 1 to 100 active hydrogens, and an epihalohydrin or glycidyl ether and / or a compound derived therefrom. An alkyl group, an alkenylating agent or an acylating agent is allowed to react with the remaining active hydrogen of the compound obtained by reacting with a C8-22 alkyl group or alkenyl group which may have a substituent. Alternatively, it contains a compound into which an acyl group has been introduced.
[0007]
In the present invention, the residue Y in the general formulas [1] to [3] ¹ ~ Y ^Three Is a compound having one or more active hydrogens, one or more of which is an active hydrogen of an amino group that can be amidated or a hydroxyl group that can be esterified. Examples of such compounds include methylamine, ethylamine, laurylamine, stearylamine, oleylamine, 12-hydroxy-9-octadecenylamine, 3-hydroxypropenylamine, dimethylamine, diethylamine, dilaurylamine, distearyl. Amine, di (12-hydroxy) -9-octadecenylamine, di (3-hydroxy) propenylamine, monolauryldimethylamine, monostearyldimethylamine, distearylmonomethylamine, trimethylamine, dilaurylmonomethylamine, di (3 Alkylamines such as (hydroxy) propenyl monomethylamine, alkenylamines, hydroxyalkylamines, hydroxyalkenylamines and alkylene oxide adducts of these amines, Alkanolamines such as minoethylethanolamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine and alkylene oxide adducts of these amines, ethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, hexaethyleneheptamine Polyalkylene polyamines such as dipropylene triamine, tripropylene tetramine, hexamethylene diamine and alkylene oxide adducts of these amines, amino acids such as glutamic acid and ascorbic acid, and alkylene oxide adducts of these amino acids, Proteins having a polypeptide bond condensed with these amino acids and their alkylene oxide adducts, Polyalkyleneimines having a linear or branched structure such as reethyleneimine and polypropyleneimine, allylamine, diallylamine, polyallylamine, diallylmethylamine, polydiallylmethylamine, copolymers obtained using them, melamine or the like Derivatives such as resins, acrylamide and polymers and copolymers obtained by using them, and polyacrylamide and copolymers thereof, polyvinylamine and copolymers thereof, and the like can be mentioned. However, Y in the general formula [2] ² Is active from a monoamine, polyamine, polyalkyleneimine or derivative thereof having at least one of an alkyl group having 8 to 22 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group and 0 to 100 active hydrogens. Limited to residues excluding hydrogen. These residues Y ¹ ~ Y ^Three The compound which gives can be used individually by 1 type, or can also be used in combination of 2 or more type.
[0008]
In the present invention, A in the general formulas [1] to [3] ¹ ~ A ^Three Is an acyl group, an acyl group having a hydroxyl group, or an acyl group having an amino group. Examples of such acyl groups include acyl groups such as acetyl group, propionyl group, butyryl group, lauroyl group, palmitoyl group, stearoyl group, isostearoyl group, and oleoyl group, and hydroxyl groups such as lactoyl group and ricinoleoyl group. An acyl group having an amino group such as an acyl group, a glycyl group or an alanyl group, a bialicyclic acyl group such as an abiethyl group, or an adduct such as maleic acid or fumaric acid can be used. A in general formula [1] ¹ Is at least one of an acyl group having 8 to 22 carbon atoms, an acyl group having a hydroxyl group, or an acyl group having an amino group. In general formulas [1] to [3], n ₁ ~ N _Three When A is 2 or more, a plurality of A ¹ ~ A ^Three May be the same or different.
In the present invention, X in the general formulas [1] to [3] ¹ ~ X ^Three Is a hydrogen atom, an alkyl group, an alkenyl group, an alkyl ether group, an acyl group or-(B ¹ O) k ₁ R ¹ ~-(B ^Three O) k _Three R ^Three And B ¹ ~ B ^Three Is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ¹ ~ R ^Three Is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, k ₁ ~ K _Three Is 1-20. The alkyl group is preferably an alkyl group having 2 to 22 carbon atoms or an alkyl group having a hydroxyl group, and the alkenyl group is preferably a vinyl group, an alkenyl group having 3 to 22 carbon atoms or an alkenyl group having a hydroxyl group. . These alkyl group, alkenyl group and alkyl ether group may be linear or branched. Examples of the alkyl group include ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group. Examples include groups. Examples of the alkyl group having a hydroxyl group include 2-hydroxyethyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 10-hydroxyoctadecyl group and the like. Examples of the alkenyl group include propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, icocenyl group, dococenyl group and the like. Can be mentioned. Examples of the hydroxyalkenyl group include 3-hydroxypropenyl group, 12-hydroxy-9-octadecenyl group, bialicyclic cholesteroyl group, lanosteroyl group, dihydrolanosteroyl group, and abiethyl group. X in general formula [3] ^Three Is a group having at least one alkyl group, alkenyl group or acyl group having 8 to 22 carbon atoms. In the general formulas [1] to [3], m ₁ ~ M _Three When X is 2 or more, a plurality of X ¹ ~ X ^Three May be the same or different.
[0009]
In the paper opacifier for the present invention, A in the general formula [1], [2] or [3] ¹ , A ² Or A ^Three Is preferably an acyl group represented by the following formula.
Embedded image

However, in the formula, R ^Four ~ R ⁶ Is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group. R ^Four ~ R ⁶ When the carbon number is 7 to 21, the paper opacifying agent can give excellent opacity to the paper while maintaining good workability.
The paper opacifying agent of the present invention contains a compound obtained by reacting a compound represented by the general formulas [1] to [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom. The compounds represented by the general formulas [1] to [3] can make the paper opaque by themselves, but when the paper is treated with the compounds represented by the general formulas [1] to [3], the paper The strength, surface strength, and sizing degree are reduced. Compounds obtained by reacting the compounds represented by the general formulas [1] to [3] with epihalohydrin or glycidyl ether and / or compounds derived therefrom reduce the strength, surface strength, and size of paper. The paper can be made opaque. A compound obtained by reacting a compound represented by the general formulas [1] to [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom has an unreacted glycidyl group, and is fixed to the pulp. Later, when paper is produced, heat is applied from a dryer or the like to increase the molecular weight, so that it is presumed that the paper strength and surface strength and sizing degree are not adversely affected. Of the epihalohydrins or glycidyl ethers or compounds derived therefrom, epihalohydrins are more preferred and epichlorohydrin is particularly preferred.
[0010]
There is no restriction | limiting in particular in the epihalohydrin used for this invention, For example, epichlorohydrin, epibromohydrin, epiiodohydrin etc. can be mentioned. The glycidyl ether used in the present invention is not particularly limited. For example, allyl glycidyl ether, 1,6-hexanediol diglycidyl ether, resorcin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane triglycidyl. Examples include ether, propylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. The compound derived from the epihalohydrin or glycidyl ether compound used in the present invention is not particularly limited, and examples thereof include oligomers of epihalohydrin or glycidyl ether, reaction products of epihalohydrin or glycidyl ether and other compounds, and the like. Examples of other compounds to be reacted with epihalohydrin or glycidyl ether include a compound having a carboxyl group, a compound having an amino group, a compound having a hydroxyl group, a compound having a double bond or a triple bond. Examples of the compound derived from epihalohydrin include glycidol, epihydrin carboxylic acid, epicyanhydrin, epichlorohydrin-modified phenol resin, and the like. Examples of the compound derived from glycidyl ether include acrylic acid glycidyl ester, methacrylic acid glycidyl ester, adipic acid diglycidyl ester, and phthalic acid diglycidyl ester.
[0011]
There is no particular limitation on the reaction ratio between the compound represented by the general formulas [1] to [3] and the epihalohydrin or glycidyl ether and / or the compound derived therefrom, but 1/10 to 10/1 (molar ratio). It is preferable that it is 1/5 to 2/1 (molar ratio). When the reaction ratio of the compound represented by the general formulas [1] to [3] and the epihalohydrin or glycidyl ether and / or the compound derived therefrom is less than 1/10 (molar ratio), the paper becomes opaque. The effect may be reduced. When the reaction ratio between the compound represented by the general formulas [1] to [3] and epihalohydrin or glycidyl ether and / or a compound derived therefrom exceeds 10/1 (molar ratio), the strength and surface strength of the paper And the size may be reduced. In the present invention, there is no particular limitation on the method for reacting the compound represented by the general formulas [1] to [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom, for example, without catalyst, or The reaction can be carried out in the presence of an acid catalyst such as Lewis acid, sulfuric acid or boron trifluoride, or an alkali catalyst such as sodium hydroxide, potassium hydroxide or sodium carbonate.
There is no restriction | limiting in particular in the manufacturing method of the compound represented by General formula [1]-[3] used for this invention, For example, a monoamine, polyamine, polyalkyleneimine etc. are used as a starting material, One or more of these compounds are used. It can be obtained by reacting an amino group or a hydroxyl group with a higher fatty acid or the like and amidation or esterification. In the amidation or esterification step, one or more amino groups or hydroxyl groups in a compound such as polyamine which is a starting material are subjected to high-temperature dehydration amidation with a fatty acid or the like using a non-catalyst or an acid or alkali catalyst. An esterification reaction can be performed, or a dehydrochlorination reaction with fatty acid chloride or the like, or an amide exchange or transesterification reaction using a lower alcohol fatty acid ester or the like can be performed. The fatty acid, fatty acid chloride, and fatty acid lower alcohol ester used at this time are preferably fatty acids having 8 to 22 carbon atoms or fatty acids having a hydroxyl group, or chlorides or lower alcohol esters thereof, and fatty acids or hydroxyl groups having 12 to 18 carbon atoms. It is more preferable that it is the fatty acid which has this, its chloride, or lower alcohol ester.
[0012]
The compounds represented by the general formulas [1] to [3] used in the present invention have an amino group with compounds already esterified such as natural fats and oils and hardened fats and oils obtained by hydrogenating natural fats and oils. It can also be produced by amide exchange or transesterification with a compound or a compound having a hydroxyl group. Examples of the fats and oils used include animal oils such as pork fat, beef tallow, bone fat and whale oil, vegetable oils such as olive oil, palm oil, soybean oil, rapeseed oil, linseed oil and coconut oil, fish oil, and hardened oils and semi-hardened oils thereof. And fats and oils containing a bialicyclic group such as lanolin and rosin.
In the present invention, Y ¹ ~ Y ^Three The compound having an amino acid group includes a compound having an amino group or a hydroxyl group, but if it reacts with a fatty acid or the like, if it contains an amidated or esterified compound, such a compound should be used. You can also. Moreover, there is no restriction | limiting in particular in the reaction mole number and reaction position of amidation or esterification, The compound which reacted with each reaction mole number and reaction position can also be used, respectively.
Furthermore, in the present invention, polyamines, polyalkyleneimines and the like or derivatives thereof can be used as starting materials for the compounds represented by the general formulas [1] to [3]. For example, monoamines, polyamines, polyalkyleneimines, etc., guanidines such as urea and dicyandiamide, formalins, epihalohydrins, isocyanate compounds, glycidyl ethers, alkyleneimines, alkyl halides, alkylene oxides, polycarboxylic acids such as dicarboxylic acids, amino acids, silyl A compound obtained by conducting polymerization, condensation, addition reaction, crosslinking reaction, etc. using a compound that reacts with active hydrogen, such as an agent, and quaternized by addition reaction to nitrogen using dimethyl sulfate, epihalohydrin, etc. A compound having one or more active hydrogens capable of being amidated or esterified in the molecule, such as a compound, can be used as a starting material. In this case, the reaction sequence is changed, and one or more amino groups such as monoamine, polyamine, polyalkyleneimine, and the like, which are starting materials, are reacted with fatty acids and the like, amidated or esterified, and then polymerized, condensed and added. A compound obtained by performing a reaction, a crosslinking reaction, or the like, a compound quaternized by addition reaction to nitrogen with dimethyl sulfate, epihalohydrin, or the like can also be used.
[0013]
Some polyamine compounds, when amidated with a fatty acid or the like, are dehydrated to form an imidazoline ring, but all imidazoline cyclized compounds and partially imidazoline cyclized compounds can also be used. Also, a mixture of these and a compound having no imidazoline ring can be used. Further, when two or more imidazoline rings are formed, the position and number of imidazoline rings are not particularly limited, and any of them can be used.
Further, after changing the reaction sequence and reacting a starting material such as monoamine, polyamine, polyalkyleneimine or the like with epihalohydrin or glycidyl ether and / or a compound derived therefrom, one or more amidation or ester in the molecule If it has at least one active hydrogen that can be converted, it can also be obtained by reacting an amino group or hydroxyl group of this compound with a higher fatty acid and amidating or esterifying it. Even if the reaction sequence basically changes, the compound represented by the general formulas [1] to [3] has one or more nitrogen atoms, and at least one A in the general formula [1]. ¹ Is an acyl group having 8 to 22 carbon atoms, an acyl group having a hydroxyl group or an acyl group having an amino group, and Y in the general formula [2] ² (N ₂ + M ₂ A compound giving a residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkyleneimine or derivative thereof having one active hydrogen is an alkyl group having 8 to 22 carbon atoms, an alkenyl group or an alkyl group having a hydroxyl group Or a compound having an alkenyl group having a hydroxyl group, or at least one X of the general formula [3] ^Three May be a compound having an alkyl group, an alkenyl group, or an acyl group having 8 to 22 carbon atoms. That is, Y in the general formulas [1] to [3] ¹ ~ Y ^Three (N ₁ + M ₁ ) To (n _Three + M _Three ) Epihalohydrin or glycidyl ether and / or a compound derived therefrom can be reacted with a compound which gives a residue obtained by removing active hydrogen from monoamine, polyamine, polyalkyleneimine or derivatives thereof having one active hydrogen. .
In the present invention, the starting polyamine, polyalkyleneimine or derivatives thereof can be used alone or in combination of two or more. In addition, compounds represented by the general formulas [1] to [3] that react with epihalohydrin or glycidyl ether and / or a compound derived therefrom can be used alone or in combination of two kinds. A combination of the above can also be used. Moreover, the epihalohydrin or glycidyl ether to be reacted and / or a compound derived therefrom can be used alone or in combination of two or more. Further, the paper opacifying agent of the present invention can be used alone or in combination of two or more.
[0014]
The paper opacifying agent of the present invention can be added in any step of pulp as a raw material in the paper making process. For example, the present invention can be applied to any process such as immediately after the disaggregation process, before and after beating, before and after adjustment for adding chemicals, before papermaking, and before and after the recycling process.
The opacity improving paper produced by the method of the present invention is a paper that can be considered in a broad sense, and is composed of a thin layer formed by tangling and sticking plant fibers and / or other fibers. It is not limited by chemicals or drugs. The paper with improved opacity can be produced by the method of the present invention not only from paper obtained from conventional wood pulp, but also from a thin layer containing plant fibers such as bagasse, kenaf and bamboo pulp.
There is no restriction | limiting in particular in the usage method of the paper opacifier for this invention, For example, it can use as it is, or it can also use it, melt | dissolving, disperse | distributing or emulsifying in water or a solvent. Further, in order to disperse and emulsify, a surfactant or a solvent can be used, neutralized with an acid such as formic acid or acetic acid, or mixed with other chemicals.
There is no restriction | limiting in the form of the paper opacifier of this invention, In order to provide another function as needed, other chemicals can also be used together. Such chemicals include, for example, wet paper strength agents, dry paper strength agents, starch, polyvinyl alcohol and other paper strength agents, dryer release agents, pitch control agents, slime control agents, deinking agents, sizing agents, paper quality Examples include improvers, fillers, pigments, dyes, and antifoaming agents.
[0015]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
In the examples and comparative examples, the evaluation of the opacity improving paper was performed by the following method.
(1) Opacity
Measurement was performed using an SM color computer [Suga Test Instruments Co., Ltd.].
(2) Whiteness
Measurement was performed using an SM color computer [Suga Test Instruments Co., Ltd.].
(3) Density
The measurement was performed according to JIS P 8118.
(4) Dry specific burst strength
It measured according to JIS P8112.
(5) Wet specific burst strength
The test paper was immersed in water at 20 ° C. for 10 minutes, and then measured according to JIS P8112.
(6) Surface strength
It measured according to the method using the wax of JIS P 8129 2.1.
(7) Size
It measured according to JIS P8122.
[0016]
Production Example 1
Taking 63.1 g of tetraethylenepentamine and 189.7 g of stearic acid (molar ratio 1/2) in a four-necked flask equipped with a dehydrating tube, a thermometer and a nitrogen gas blowing tube, gradually heating with a mantle heater, While blowing nitrogen gas, dehydration reaction was performed at 180 ° C. to 200 ° C. for 5 hours to obtain an intermediate compound a. Take 169.8 g of this compound in a four-necked flask equipped with a condenser, thermometer and dropping funnel, heat to 90 ° C. with a mantle heater, and pay attention to 46.3 g (molar ratio 1/2) of epichlorohydrin for exotherm. The solution was added dropwise while maintaining the temperature at 90 to 100 ° C. After completion of the dropping, the reaction was performed for 4 hours while maintaining the temperature at 90 to 100 ° C. to obtain a paper opacifier component. This paper opacifier component is designated as paper opacifier component 1.
Production Example 2
An opacifying agent component for paper was obtained in the same manner as in Production Example 1 except that the amount of epichlorohydrin was changed to 69.5 g (molar ratio 1/3). This paper opacifier component is designated as paper opacifier component 2.
Production Example 3
4 necks equipped with 34.7 g of aminoethylethanolamine, 189.7 g of stearic acid (molar ratio 1/2) and 0.5 g of paratoluenesulfonic acid as a catalyst, equipped with a dehydrating tube, thermometer and nitrogen gas blowing tube It took in the flask, heated with the mantle heater gradually, dehydration reaction was performed at 200-220 degreeC, blowing nitrogen gas for 5 hours, and the intermediate compound b was obtained. After taking 159.3 g of this compound in a four-necked flask equipped with a condenser, a thermometer and a dropping funnel, and heating to 90 ° C. with a mantle heater, 23.1 g of epichlorohydrin (molar ratio 1/1) Was added dropwise while maintaining the temperature at 90-100 ° C. After completion of the dropping, the reaction was performed for 4 hours while maintaining the temperature at 90 to 100 ° C. to obtain a paper opacifier component. This paper opacifier component is designated as paper opacifier component 3.
[0017]
Production Example 4
To 34.4 g of diethylenetriamine, 161.6 g (molar ratio 1/2) of a mixture of stearic acid and lauric acid in a molar ratio of 1/1 and 0.5 g of paratoluenesulfonic acid as a catalyst were added to a dehydrating tube, a thermometer and nitrogen. It took in the 4 necked flask which attached the gas blowing pipe | tube, it heated gradually with the mantle heater, dehydration reaction was performed at 200-220 degreeC, blowing nitrogen gas for 5 hours, and the intermediate compound c was obtained. After taking 138.0 g of this compound in a four-necked flask equipped with a condenser, a thermometer and a dropping funnel and heating to 90 ° C. with a mantle heater, 23.1 g of epichlorohydrin (molar ratio 1/1) Was added dropwise while maintaining the temperature at 90-100 ° C. After completion of the dropping, the reaction was performed for 4 hours while maintaining the temperature at 90 to 100 ° C. to obtain a paper opacifier component. This paper opacifier component is designated as paper opacifier component 4.
Production Example 5
After taking 133.8 g of distearyl monomethylamine in a four-necked flask equipped with a condenser, a thermometer and a dropping funnel and heating to 90 ° C. with a mantle heater, 23.1 g of epichlorohydrin (molar ratio 1/1) is exothermic. The solution was dropped while maintaining the temperature at 90 to 100 ° C. After completion of the dropping, the reaction was performed for 4 hours while maintaining the temperature at 90 to 100 ° C. to obtain an opacifying component for paper. This paper opacifier component is designated as paper opacifier component 5.
Production Examples 6 to 20
Residue Y obtained by removing active hydrogen from monoamine, polyamine, polyalkyleneimine or derivatives thereof having active hydrogen ¹ ~ Y ^Three And a starting material which is a compound that provides an acyl group, an acyl group having a hydroxyl group, or an acyl group A having an amino group ¹ ~ A ^Three Were reacted in the same manner as in Production Examples 1 to 5 to obtain intermediate compounds en.
Furthermore, epichlorohydrin, epibromohydrin or allyl glycidyl ether was reacted with the obtained intermediate compound in the same manner as in Production Examples 1 to 5 to obtain paper opacifier components 6 to 20.
The intermediates obtained in Production Examples 1 to 20 are shown in Table 1, and the paper opacifier components are shown in Table 2.
[0018]
[Table 1]

[0019]
[Table 2]

[0020]
Example 1 (Preparation of paper opacifier)
Since the paper opacifier components 1 to 20 do not dissolve in water, these paper opacifier components are heated and melted, neutralized with acetic acid, and stirred with a spatula while gradually adding water or hot water. The mixture was emulsified to prepare a 10% by weight emulsion. Each of these emulsions was passed once through a test homogenizer to obtain paper opacifiers 1 to 20 of the present invention.
Comparative Example 1 (Preparation of opacifying agent for comparative paper)
Comparative paper opacifiers 1 to 20 were prepared using the compounds shown in Table 3 as the paper opacifier component. Comparative paper opacifier 1-12 and comparative paper opacifier 19 were prepared in the same manner as in Example 1. Comparative paper opacifier 13-16 and comparative paper opacifier 18 were surface active. As an agent, a fatty acid esterified product of sorbitol ethylene oxide adduct (derived from twin) was blended and emulsified in a paper opacifier component, and the comparative paper opacifiers 17 and 20 were made into a 10% by weight aqueous solution.
[0021]
[Table 3]

[0022]
Example 2 (Preparation and Evaluation of Opacity Improvement Paper)
Paper pulp opacifying agent 1 at intervals of 10 minutes while stirring with a chemistrar, pulp mixed with recycled waste paper (freeness 420 ml) and NBKP (freeness 420 ml) at a weight ratio of 70/30 0.3% by weight to the pulp, 0.4% by weight of dry paper strength agent (anionic) added to the pulp, pH adjusted to 4.5 with sulfuric acid band, emulsion sizing agent to the pulp 1% by weight and 1% by weight of a wet paper strength agent (cationic) was added to the pulp. Thereafter, stirring was continued for 60 minutes to complete the pulp preparation.
Next, using a test square sheet machine, the basis weight is 80 g / m. ² Then, it was pressed at 7 kg for 5 minutes using a press machine, and dried at 105 ° C. for 3 minutes using a test Yankee dryer to obtain a paper with improved opacity.
The obtained opacity-enhanced paper has an opacity of 87.1%, a whiteness of 86.3, and a density of 0.529 g / cm. ^Three The dry specific burst strength was 2.23, the wet specific burst strength was 0.93, the surface strength was 7 A, and the sizing degree was 39 seconds.
Example 3 (Preparation and Evaluation of Opacity Improvement Paper)
19 types of opacity improving papers were prepared and evaluated in the same manner as in Example 2 using the paper opacifiers 2 to 20 instead of the paper opacifier 1.
Comparative Example 2 (Production and Evaluation of Paper)
Paper was prepared and evaluated in the same manner as in Example 2 except that no paper opacifier was added.
The resulting paper has an opacity of 84.6%, a whiteness of 84.9, and a density of 0.572 g / cm. ^Three The dry specific burst strength was 2.32, the wet specific burst strength was 0.98, the surface strength was 7 A, and the sizing degree was 40 seconds.
Comparative Example 3 (Preparation and Evaluation of Opacity Improvement Paper)
Using the comparative paper opacifying agent 1 instead of the paper opacifying agent 1, an opacity improving paper was prepared and evaluated in the same manner as in Example 2.
The resulting opacity-enhanced paper has an opacity of 87.0%, a whiteness of 86.0, and a density of 0.534 g / cm. ^Three The dry specific burst strength was 1.63, the wet specific burst strength was 0.57, the surface strength was 6 A, and the sizing degree was 27 seconds.
Comparative Example 4 (Production and Evaluation of Opacity Improvement Paper)
19 kinds of opacity improving papers were prepared and evaluated in the same manner as in Example 2 using the opacifying agents 2 to 20 for the comparative paper instead of the opacifying agent 1 for paper.
The results of Examples 2-3 are shown in Table 4, and the results of Comparative Examples 2-4 are shown in Table 5.
[0023]
[Table 4]

[0024]
[Table 5]

[0025]
As can be seen in Table 4, the opacity improving paper of the examples prepared using the paper opacifiers 1 to 20 of the present invention has high opacity and whiteness, low density, specific burst strength, Both surface strength and sizing are large and have excellent quality. On the other hand, as seen in Table 5, the opacity improving papers of comparative examples prepared using comparative paper opacifiers 1 to 11 and 19 prepared using intermediates a to k were The transparency and whiteness are relatively good and the density is low, but the specific burst strength, surface strength, and size are all small. Moreover, the opacity-enhanced paper of Comparative Example produced using conventional paper opacifiers 12 to 18 and 20 has relatively high specific burst strength, surface strength, and sizing, but opacity and whiteness. Is inferior and dense.
Example 4 (Production and Evaluation of Opacity Improvement Paper)
Paper pulp opacifying agent 1 at intervals of 10 minutes while stirring a recycled pulp (freeness 450 ml) and TMP (freeness 450 ml) of used newspaper in a weight ratio of 55/45 using a chemistor. 0.3% by weight of pulp, 0.2% by weight of dry paper strength agent (anionic), pH adjusted to 4.5 with sulfuric acid band, emulsion sizing agent to pulp 0.4% by weight, and 0.4% by weight of wet paper strength agent (cationic) was added to the pulp. Thereafter, stirring was continued for 60 minutes to complete the pulp preparation.
Then, using a test square sheet machine, the basis weight is 45 g / m. ² Then, it was pressed at 7 kg for 5 minutes using a press machine, and dried at 105 ° C. for 3 minutes using a test Yankee dryer to obtain a paper with improved opacity.
The obtained opacity-enhanced paper has an opacity of 92.0%, a whiteness of 58.0, and a density of 0.472 g / cm. ^Three The dry specific burst strength was 0.98, the wet specific burst strength was 0.22, the surface strength was 5 A, and the sizing degree was 7 seconds.
Example 5 (Preparation and Evaluation of Opacity Improvement Paper)
19 kinds of opacity improving papers were prepared and evaluated in the same manner as in Example 4 using the paper opacifiers 2 to 20 instead of the paper opacifier 1.
Comparative Example 5 (Production and Evaluation of Paper)
A paper was prepared and evaluated in the same manner as in Example 4 except that no paper opacifier was added.
The resulting paper has an opacity of 89.8%, a whiteness of 56.2, and a density of 0.506 g / cm. ^Three The dry specific burst strength was 1.00, the wet specific burst strength was 0.21, the surface strength was 5 A, and the sizing degree was 8 seconds.
Comparative Example 6 (Production and Evaluation of Opacity Improvement Paper)
Using the comparative paper opacifying agent 1 in place of the paper opacifying agent 1, an opacity improving paper was prepared and evaluated in the same manner as in Example 4.
The resulting opacity-enhanced paper has an opacity of 91.7%, a whiteness of 57.8, and a density of 0.485 g / cm. ^Three The dry specific burst strength was 0.68, the wet specific burst strength was 0.11, the surface strength was 4 A, and the sizing degree was 4 seconds.
Comparative Example 7 (Preparation and evaluation of opacity improved paper)
19 kinds of opacity improving papers were prepared and evaluated in the same manner as in Example 4 using the opacifying agents 2 to 20 for the comparative paper instead of the opacifying agent 1 for paper.
The results of Examples 4 to 5 are shown in Table 6, and the results of Comparative Examples 5 to 7 are shown in Table 7.
[0026]
[Table 6]

[0027]
[Table 7]

[0028]
As can be seen in Table 6, the opacity improving paper of the examples prepared using the paper opacifiers 1 to 20 of the present invention has high opacity and whiteness, low density, specific burst strength, Both surface strength and sizing are large and have excellent quality. On the other hand, as seen in Table 7, the opacity improving paper of Comparative Example prepared using Comparative Paper Opacifying Agents 1 to 11 and 19 prepared using Intermediates a to k is not suitable. The transparency and whiteness are relatively good and the density is low, but the specific burst strength, surface strength, and size are all small. Moreover, the opacity-enhanced paper of Comparative Example produced using conventional paper opacifiers 12 to 18 and 20 has relatively high specific burst strength, surface strength, and sizing, but opacity and whiteness. Is inferior and dense.
Example 6 (Preparation and evaluation of opacity improving paper)
While stirring a pulp mixed with NBKP (freeness 400 ml) and LBKP (freeness 400 ml) in a weight ratio of 50/50 using a chemistrar, the calcium carbonate is 5% by weight with respect to the pulp. Addition, 0.3% by weight of paper opacifier 1 added to pulp, 1.0% by weight of alkyl ketene dimer type sizing agent added to pulp, dry paper strength agent (amphoteric) to pulp On the other hand, 0.5% by weight was added. Thereafter, stirring was continued for 60 minutes to complete the pulp preparation.
Then, using a test square sheet machine, the basis weight is 65 g / m. ² Then, it was pressed at 7 kg for 5 minutes using a press machine, and dried at 105 ° C. for 3 minutes using a test Yankee dryer to obtain a paper with improved opacity.
The resulting opacity-enhanced paper has an opacity of 81.3%, a whiteness of 88.0, and a density of 0.498 g / cm. ^Three The dry specific burst strength was 1.93, the surface strength was 7 A, and the sizing degree was 23 seconds.
Example 7 (Preparation and Evaluation of Opacity Improvement Paper)
19 kinds of opacity improving papers were prepared and evaluated in the same manner as in Example 6 using the paper opacifiers 2 to 20 instead of the paper opacifier 1.
Comparative Example 8 (Production and Evaluation of Paper)
A paper was prepared and evaluated in the same manner as in Example 6 except that no paper opacifier was added.
The resulting paper has an opacity of 78.7%, a whiteness of 86.0, and a density of 0.520 g / cm. ^Three The dry specific burst strength was 1.96, the surface strength was 6 A, and the sizing degree was 24 seconds.
Comparative Example 9 (Preparation and Evaluation of Opacity Improvement Paper)
Using the comparative paper opacifying agent 2 instead of the paper opacifying agent 1, an opacity improving paper was prepared and evaluated in the same manner as in Example 6.
The resulting opacity-enhanced paper has an opacity of 81.2%, a whiteness of 87.7, and a density of 0.499 g / cm. ^Three The dry specific burst strength was 1.34, the surface strength was 6 A, and the sizing degree was 12 seconds.
Comparative Example 10 (Preparation and Evaluation of Opacity Improvement Paper)
20 types of opacity improving papers were prepared and evaluated in the same manner as in Example 6 using the opacifying agents for comparative paper 1 to 20 instead of the opacifying agent 1 for paper.
The results of Examples 6-7 are shown in Table 8, and the results of Comparative Examples 8-10 are shown in Table 9.
[0029]
[Table 8]

[0030]
[Table 9]

[0031]
As can be seen in Table 8, the opacity improving paper of the examples prepared using the paper opacifiers 1 to 20 of the present invention has high opacity and whiteness, low density, specific burst strength, Both surface strength and sizing are large and have excellent quality. On the other hand, as seen in Table 9, the opacity improving paper of the comparative example prepared using the opacifying agents for comparative paper 1 to 11 and 19 prepared using the intermediates a to k is not suitable. The transparency and whiteness are relatively good and the density is low, but the specific burst strength, surface strength, and size are all small. Moreover, the opacity-enhanced paper of Comparative Example produced using conventional paper opacifiers 12 to 18 and 20 has relatively good specific burst strength and sizing, but opacity, whiteness and surface hardness. Is inferior and the density is high.
Example 8 (Preparation and Evaluation of Opacity Improvement Paper)
Paper pulp opacifying agent 1 at intervals of 10 minutes while stirring with a chemistrar, pulp mixed with recycled waste paper (freeness 420 ml) and NBKP (freeness 420 ml) at a weight ratio of 70/30 0.15% by weight to the pulp, 0.4% by weight of dry paper strength agent (anionic) added to the pulp, pH adjusted to 4.5 with sulfuric acid band, emulsion sizing agent to the pulp 1% by weight and 1% by weight of a wet paper strength agent (cationic) was added to the pulp. Thereafter, stirring was continued for 60 minutes to complete the pulp preparation.
Next, using a test square sheet machine, the basis weight is 80 g / m. ² Then, it was pressed at 7 kg for 5 minutes using a press machine, and dried at 105 ° C. for 3 minutes using a test Yankee dryer to obtain a paper with improved opacity.
The resulting opacity-enhanced paper has an opacity of 87.8%, a whiteness of 87.2, and a density of 0.543 g / cm. ^Three The dry specific burst strength was 2.34, the wet specific burst strength was 1.03, the surface strength was 7 A, and the sizing degree was 45 seconds.
Example 9 (Preparation and Evaluation of Opacity Improvement Paper)
An opacity-enhanced paper was prepared in the same manner as in Example 8 except that 1% by weight of titanium oxide was added to the pulp 10 minutes before the addition of the paper opacifying agent 1.
The resulting opacity-enhanced paper has an opacity of 88.9%, a whiteness of 88.0, and a density of 0.543 g / cm. ^Three The dry specific burst strength was 2.23, the wet specific burst strength was 1.00, the surface strength was 7 A, and the sizing degree was 44 seconds.
Example 10 (Preparation and Evaluation of Opacity Improvement Paper)
Titanium oxide is added to the pulp in four levels of 0% by weight, 1% by weight, 2.5% by weight and 5% by weight, and the paper opacifier 1 or 3 is used, and the amount added to the pulp is set to 0. An opacity improving paper was prepared and evaluated in the same manner as in Example 8 or Example 9, with two levels of 15% by weight and 0.3% by weight.
Comparative Example 11 (Preparation and Evaluation of Opacity Improvement Paper)
Paper was prepared and evaluated in the same manner as in Example 8 or Example 9 using the comparative paper opacifier 1 or 20 or without adding the paper opacifier.
The results of Examples 8 to 10 are shown in Table 10, and the results of Comparative Example 11 are shown in Table 11.
[0032]
[Table 10]

[0033]
[Table 11]

[0034]
As seen in Table 10, the opacity-enhancing paper of Examples prepared using the paper opacifier 1 or 3 of the present invention with or without the addition of titanium oxide is Whiteness is high, density is low, specific burst strength, surface strength, and size are large, and it has excellent quality. Further, the opacity and whiteness are improved as the amount of the paper opacifier added is increased and as the amount of titanium oxide added is increased. On the other hand, as shown in Table 11, the opacity-enhanced paper of the comparative example produced using the comparative paper opacifying agent 1 prepared using the intermediate a was compared in opacity and whiteness. It has good density and low density, but its specific burst strength, surface strength and sizing degree are all small. Further, the opacity-enhanced paper of the comparative example prepared using the conventional paper opacifying agent 20 has relatively high specific burst strength, surface hardness, and sizing degree, but has poor opacity and whiteness, density. Is also expensive.
[0035]
【The invention's effect】
By using the opacifying agent of the present invention, the opacity and whiteness can be improved while maintaining the specific burst strength, surface strength, and sizing at a high level. This can reduce the production speed of the product and reduce the raw material cost. Furthermore, by replacing part of the method using the conventional filler or by replacing all of them, the problems of the method of using the conventional filler can be eliminated or alleviated. By adding to the method used, it is possible to improve the quality of paper products and reduce costs, such as further improving the opacity of the paper.

Claims (6)

A reaction product obtained by reacting the compound represented by the general formula [1] with epihalohydrin or glycidyl ether and / or a compound derived therefrom is neutralized with an acid, dissolved or dispersed in water and added. Then, an anionic or amphoteric dry paper strength agent is added, a sizing agent is added to prepare a pulp, and the pulp is subjected to a papermaking process, a pressing process, and a drying process, and the reaction product is added. A paper having an opacity of 87.0% or higher, a density of 2.0% or higher, a density of 0.021 g / cm ³ or lower, and a size reduction of 2 seconds or less is obtained. A method for producing an opacity improving paper.

Wherein Y ¹ is a residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkyleneimine or derivative thereof having (n ₁ + m ₁ ) active hydrogens, and A ¹ represents an acyl group or a hydroxyl group. An acyl group having an amino group or an amino group, wherein at least one of these acyl groups has 8 to 22 carbon atoms, and X ¹ is a hydrogen atom, an alkyl group, an alkenyl group, an alkyl ether group, an acyl group, or -(B ¹ O) k ₁ R ¹ (wherein B ¹ is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ¹ is a hydrogen atom or an acyl group having 2 to 22 carbon atoms. And k ₁ is 1 to 20.), n ₁ is 1 or more, m ₁ is 0 or more, n ₁ + m ₁ = 1 to 100, and n ₁ is 2 or more. multiple of a ¹ is be the same or different from each other , M ₁ is more X ¹ in the case of more than one may be the same or different.) A reaction product obtained by reacting the compound represented by the general formula [2] with epihalohydrin or glycidyl ether and / or a compound derived therefrom is neutralized with an acid, dissolved or dispersed in water and added. Then, an anionic or amphoteric dry paper strength agent is added, a sizing agent is added and mixed to prepare a pulp, and the pulp is subjected to a paper making process, a pressing process, and a drying process, thereby generating the reaction product. More than 2.0% in the region where the opacity is 87.0% or more, the difference in density is 0.021 g / cm ³ or less, and the sizing degree is lower than in the case of the paper manufactured without adding the material. A method for producing an opacity-enhanced paper, characterized by obtaining a paper of 2 seconds or less.

(Wherein Y ² is a monoamine having at least one of an alkyl group having 8 to 22 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group and (n ₂ + m ₂ ) active hydrogens). , A residue obtained by removing active hydrogen from a polyamine, polyalkyleneimine or a derivative thereof, A ² is an acyl group, an acyl group having a hydroxyl group or an acyl group having an amino group, X ² is a hydrogen atom, an alkyl group, An alkenyl group, an alkyl ether group, an acyl group, or — (B ² O) k ₂ R ² (where B ² is an alkylene group having 2 to 4 carbon atoms, a phenylethylene group or a phenoxymethylethylene group, and R ² is a hydrogen atom) An atom or an acyl group having 2 to 22 carbon atoms, k ₂ is 1 to 20, and n ₂ is 0 or more, m ₂ is 0 or more, and n ₂ + m ₂ = 0 to 100. In When n ₂ is 2 or more, the plurality of A ² may be the same or different, and when m ₂ is 2 or more, the plurality of X ² may be the same or different.) A reaction product obtained by reacting the compound represented by the general formula [3] with epihalohydrin or glycidyl ether and / or a compound derived therefrom is neutralized with an acid, dissolved or dispersed in water and added. Then, an anionic or amphoteric dry paper strength agent is added, a sizing agent is added and mixed to prepare a pulp, and the pulp is subjected to a paper making process, a pressing process, and a drying process, thereby generating the reaction product. More than 2.0% in the region where the opacity is 87.0% or more, the difference in density is 0.021 g / cm ³ or less, and the sizing degree is lower than in the case of the paper manufactured without adding the material. A method for producing an opacity-enhanced paper, characterized by obtaining a paper of 2 seconds or less.

(Wherein Y ³ is a residue obtained by removing active hydrogen from a monoamine, polyamine, polyalkyleneimine or derivative thereof having (n ₃ + m ₃ ) active hydrogens, and A ³ represents an acyl group or a hydroxyl group. X ³ is a hydrogen atom, an alkyl group, an alkenyl group, an alkyl ether group, an acyl group, or — (B ³ O) k ₃ R ³ (where B ³ is the number of carbon atoms) 2 to 4 alkylene group, phenylethylene group or phenoxymethylethylene group, R ³ is a hydrogen atom or an acyl group having 2 to 22 carbon atoms, and k ₃ is 1 to 20). ^At least one of ₃ is a group having an alkyl group, alkenyl group or acyl group having 8 to 22 carbon atoms, n ₃ is 0 or more, m ₃ is 1 or more, and n ₃ + m ₃ = 1 to 100 , and the case n ₃ is 2 or more The A ³ number may be the same or different, m ₃ are a plurality of X ³ and if more may be the same or different.) The method for producing opacity-enhancing paper according to claim ¹ , wherein at least one of A ¹ is a group represented by the general formula [4].

(In the formula, R ⁴ is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group.) The method for producing an opacity-enhancing paper according to claim ² , wherein at least one of A ² is a group represented by the general formula [5].

(In the formula, R ⁵ is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group.) The method for producing opacity-enhancing paper according to claim ³ , wherein at least one of A ³ is a group represented by the general formula [6].

(In the formula, R ⁶ is an alkyl group having 7 to 21 carbon atoms, an alkenyl group, an alkyl group having a hydroxyl group, or an alkenyl group having a hydroxyl group.)