JP4128057B2 - Low density agent for paper and method for producing low density paper - Google Patents
Low density agent for paper and method for producing low density paper Download PDFInfo
- Publication number
- JP4128057B2 JP4128057B2 JP2002277528A JP2002277528A JP4128057B2 JP 4128057 B2 JP4128057 B2 JP 4128057B2 JP 2002277528 A JP2002277528 A JP 2002277528A JP 2002277528 A JP2002277528 A JP 2002277528A JP 4128057 B2 JP4128057 B2 JP 4128057B2
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- paper
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- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 125000003342 alkenyl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000005020 hydroxyalkenyl group Chemical group 0.000 claims description 16
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000000123 paper Substances 0.000 description 76
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- 239000000194 fatty acid Substances 0.000 description 26
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- -1 fatty acid ester Chemical class 0.000 description 17
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- 238000004513 sizing Methods 0.000 description 12
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000013055 pulp slurry Substances 0.000 description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- JTQQDDNCCLCMER-CLFAGFIQSA-N (z)-n-[(z)-octadec-9-enyl]octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCNCCCCCCCC\C=C/CCCCCCCC JTQQDDNCCLCMER-CLFAGFIQSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- 229940114072 12-hydroxystearic acid Drugs 0.000 description 1
- ZONJATNKKGGVSU-UHFFFAOYSA-N 14-methylpentadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCC(O)=O ZONJATNKKGGVSU-UHFFFAOYSA-N 0.000 description 1
- FHPUNDSYXHZZNA-UHFFFAOYSA-N 18-aminooctadecan-7-ol Chemical compound CCCCCCC(O)CCCCCCCCCCCN FHPUNDSYXHZZNA-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
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- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DPUOLQHDNGRHBS-UHFFFAOYSA-N Brassidinsaeure Natural products CCCCCCCCC=CCCCCCCCCCCCC(O)=O DPUOLQHDNGRHBS-UHFFFAOYSA-N 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- 241000218631 Coniferophyta Species 0.000 description 1
- 239000004129 EU approved improving agent Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- URXZXNYJPAJJOQ-UHFFFAOYSA-N Erucic acid Natural products CCCCCCC=CCCCCCCCCCCCC(O)=O URXZXNYJPAJJOQ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241001149900 Fusconaia subrotunda Species 0.000 description 1
- 240000000797 Hibiscus cannabinus Species 0.000 description 1
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- CQXMAMUUWHYSIY-UHFFFAOYSA-N Lignoceric acid Natural products CCCCCCCCCCCCCCCCCCCCCCCC(=O)OCCC1=CC=C(O)C=C1 CQXMAMUUWHYSIY-UHFFFAOYSA-N 0.000 description 1
- QXYCISFUJXCMSU-UHFFFAOYSA-N Lumequesaeure Natural products CCCCCCCCC=CCCCCCCCCCCCCCCCCCCCC(O)=O QXYCISFUJXCMSU-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 1
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- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は、紙用低密度化剤及び低密度紙の製造方法に関する。さらに詳しくは、本発明は、低起泡性で使いやすく、サイズ度の低下が少なく、低密度性、不透明度、白色度に優れ、含水伸度の小さい低密度紙を製造することができる紙用低密度化剤及び低密度紙の製造方法に関する。
【０００２】
【従来の技術】
近年、パルプ資源の不足、パルプ価格の高騰、地球環境保護の必要性などによって、パルプの使用量をできるだけ抑えるために、紙製品の坪量を下げる努力がなされている。新聞用紙、印刷用紙、記録用紙、包装用紙、壁紙襖用原紙、裏打ち紙などの紙製品の坪量を低減することにより、コスト低減はもちろん、森林資源の確保など、地球環境問題の解決に大きな効果をもたらすと考えられる。
また、一方では、印刷適性やボリューム感のある高品質の紙が要望されており、紙の嵩を高くした密度の低い紙が求められている。従来より、紙の密度を低くする方法として、架橋パルプを用いる方法や、合成繊維との混抄による方法、パルプ繊維に無機物を充填する方法などが行われている。しかし、架橋パルプを用いる方法や、合成繊維との混抄による方法では、紙のリサイクルが難しくなり、コスト的にも高くなる。また、無機物の充填による方法では、紙の強度を著しく低下させるという欠点がある。
最近になって、抄紙時に有機化合物を添加することによって、密度を低くする薬剤が開発されている。例えば、低密度化剤として、高級脂肪酸のアルキレンオキシド付加物を含有する紙用嵩高剤が提案されている（特許文献１）。また、高級アルコールのアルキレンオキシド付加物を含有する紙用嵩高剤も提案されている（特許文献２）。しかしながら、高級アルコールや高級脂肪酸のアルキレンオキシド付加物などの非イオン活性剤は、分子内に親水性の高いポリエーテル基が存在するために、紙のサイズ度を著しく低下させる。さらに、これらの化合物は起泡性が高いために、しばしば泡による浮き種や、紙のピンホールなどのトラブルが生ずる。
【特許文献１】
特開平１１−２００２８４号公報（第５頁）
【特許文献２】
特再Ｗ０９８／０３７３０号公報（第１２−１４頁）
【０００３】
【発明が解決しようとする課題】
本発明は、低起泡性で使いやすく、サイズ度の低下が少なく、低密度性、不透明度、白色度に優れ、含水伸度の小さい低密度紙を製造することができる紙用低密度化剤及び低密度紙の製造方法を提供することを目的としてなされたものである。
【０００４】
【課題を解決するための手段】
本発明者らは、上記の問題を解決すべく鋭意研究を重ねた結果、末端に長鎖の疎水基を有するアルキルアミンのポリオキシアルキレン脂肪酸エステルを製紙工程に添加することにより、工程での起泡性の問題を生ずることなく、サイズ度の低下が少なく、不透明度、白色度に優れ、含水伸度の低い低密度紙が得られることを見いだし、この知見に基づいて本発明を完成するに至った。
すなわち本発明は、
（１）一般式［１］又は一般式［２］で表される化合物を含有することを特徴とする紙用低密度化剤、
【化３】
（２）一般式［１］又は一般式［２］で表される化合物を製紙工程に添加することを特徴とする低密度紙の製造方法。
【化４】
を提供するものである。
【０００５】
【発明の実施の形態】
本発明の紙用低密度化剤は、一般式［１］又は一般式［２］で表される化合物を含有する。本発明の低密度紙の製造方法においては、一般式［１］又は一般式［２］で表される化合物を製紙工程に添加する。
【化５】
一般式［１］又は一般式［２］において、Ｒ1、Ｒ4及びＲ5は、炭素数８〜３６、より好ましくは炭素数１２〜２４のアルキル基、ヒドロキシアルキル基、アルケニル基又はヒドロキシアルケニル基である。Ｒ1、Ｒ4又はＲ5の炭素数が７以下であると、得られる紙の密度が十分に低下せず、サイズ度の低下が極めて高くなるおそれがある。Ｒ1、Ｒ4又はＲ5の炭素数が３７以上であると、紙用低密度化剤の取り扱いが困難になるおそれがある。
【０００６】
一般式［１］又は一般式［２］において、Ｒ1、Ｒ4及びＲ5で表される炭素数８〜３６のアルキル基、ヒドロキシアルキル基、アルケニル基又はヒドロキシアルケニル基は、直鎖状であっても、分岐を有していてもよい。このようなアルキル基としては、例えば、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、トリアコンチル基などを挙げることができる。ヒドロキシアルキル基としては、例えば、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、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、１２−ヒドロキシ−９−オクタデセニル基などを挙げることができる。
一般式［１］又は一般式［２］において、Ｒ2、Ｒ3及びＲ6は、炭素数７〜３５、より好ましくは炭素数１１〜２３のアルキル基、ヒドロキシアルキル基、アルケニル基又はヒドロキシアルケニル基である。Ｒ2、Ｒ3又はＲ6の炭素数が６以下であると、得られる紙の密度が十分に低下せず、起泡性が高くなり、サイズ度の低下が極めて高くなるおそれがある。Ｒ2、Ｒ3又はＲ6の炭素数が３６以上であると、紙用低密度化剤の取り扱いが困難になるおそれがある。
【０００７】
一般式［１］又は一般式［２］において、Ｒ2、Ｒ3又はＲ6で表される炭素数７〜３５のアルキル基、ヒドロキシアルキル基、アルケニル基又はヒドロキシアルケニル基は、直鎖状であっても、分岐を有していてもよい。このようなアルキル基としては、例えば、ヘプチル基、オクチル基、ノニル基、ウンデシル基、トリデシル基、ヘプタデシル基、ノナデシル基、ヘンイコシル基などを挙げることができる。ヒドロキシアルキル基としては、例えば、９−ヒドロキシヘプ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、ヘプテニル基、オクテニル基、ノネニル基、ウンデセニル基、トリデセニル基、ペンタデセニル基、ヘプタデセニル基、ノナデセニル基、ヘンイ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、１２−ヒドロキシ−９−オクタデセニル基などを挙げることができる。
一般式［１］又は一般式［２］において、Ａ1、Ａ2及びＡ3は、炭素数２〜４のアルキレン基である。炭素数２〜４のアルキレン基としては、例えば、エチレン基、プロピレン基、トリメチレン基、エチルエチレン基、テトラメチレン基などを挙げることができる。一般式［１］又は一般式［２］において、ｐ、ｑ及びｒは、１〜４０であり、より好ましくは１〜２０である。ｐ、ｑ又はｒが４０を超えると、サイズ度の低下が極めて高くなるおそれがある。ｐ、ｑ及びｒが２０以下であると、サイズ度の低下が少なくなる。
【０００８】
構造(Ａ1Ｏ)p、(Ａ2Ｏ)q及び(Ａ3Ｏ)rにおいて、アルキレンオキシ基は１種の単独重合体構造とすることができ、２種以上の共重合体構造とすることもできる。また、共重合体構造は、ランダム共重合体構造、ブロック共重合体構造、ランダム構造とブロック構造の入り混じった共重合体構造のいずれともすることができる。一般式［１］又は一般式［２］において、(Ａ1Ｏ)p、(Ａ2Ｏ)q又は(Ａ3Ｏ)r構造のアルキレンオキシ基の種類、モル数、組み合わせを適宣選択することにより、低起泡性で水に容易に溶解又は分散し、取り扱いやすい低密度化剤を得ることができる。
従来の高級脂肪酸や高級アルコールのアルキレンオキシド付加物などの非イオン活性剤は、分子内に親水性の高いポリエーテル基が存在するために、紙用低密度化剤として使用すると、紙のサイズ度を著しく低下させる。本発明の紙用低密度化剤は、末端に長鎖の疎水基が存在する一般式［１］又は一般式［２］で表される化合物を含有するので、紙のサイズ度の低下を抑えることができる。さらに、一般式［１］又は一般式［２］で表される化合物は、末端に炭素数の多い疎水基が３個存在することにより、界面活性剤としての配向性が悪くなり、起泡性が低下する。
【０００９】
本発明に用いる一般式［１］又は一般式［２］で表される化合物の製造方法に特に制限はなく、例えば、アルキルアミンやジアルキルアミンなどのアミン化合物を出発原料にして、無触媒又はアルカリや酸などの触媒を用いてアルキレンオキシドを付加することによって中間体を得る。この中間体に、酸やアルカリなどの触媒を用いて、脂肪酸との脱水反応、脂肪酸クロリドによる脱塩化水素反応、低級アルコール脂肪酸エステルとのエステル交換反応などによって製造することができる。
一般式［１］又は一般式［２］で表される化合物の出発物質であるアミン化合物は、１種を単独で用いることができ、あるいは、２種以上を組み合せて用いることもできる。一般式［１］又は一般式［２］で表される化合物の製造に使用するアミン化合物としては、例えば、オクチルアミン、２−エチルヘキシルアミン、ノニルアミン、ラウリルアミン、ミリスチルアミン、セチルアミン、ステアリルアミン、イソステアリルアミン、オレイルアミン、ベヘニルアミン、ココナッツアミン、１２−ヒドロキシステアリルアミン、ジラウリルアミン、ジステアリルアミン、ジオレイルアミン、その他合成アミンなどを挙げることができる。
【００１０】
一般式［１］又は一般式［２］で表される化合物の製造において、脂肪酸又はその誘導体は、１種を単独で用いることができ、あるいは、２種以上を組み合せて用いることもできる。一般式［１］又は一般式［２］で表される化合物の製造に用いる炭素数８〜３６の脂肪酸の構造に特に制限はなく、飽和脂肪酸、不飽和脂肪酸、直鎖状脂肪酸、分岐を有する脂肪酸、ヒドロキシル基を有する脂肪酸など、いずれの脂肪酸も用いることができる。このような脂肪酸としては、例えば、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、アラキン酸、ベヘニン酸、リグノセリン酸、オレイン酸、リノール酸、リノレン酸、エルカ酸、２１−トリアコンテン酸、１２−ヒドロキシステアリン酸、リシノール酸、イソノナン酸、イソデカン酸、イソトリデカン酸、イソミリスチン酸、イソパルミチン酸、イソステアリン酸、脂肪酸を複量化したダイマー酸、トール油脂肪酸、牛脂脂肪酸、やし脂肪酸、ひま脂肪酸やそれらの硬化脂肪酸などを挙げることができる。
本発明方法において、一般式［１］又は一般式［２］で表される化合物を添加する製紙工程に特に制限はなく、例えば、離解工程、叩解工程、薬品などを配合する調成工程、抄紙前などを挙げることができる。また、古紙などの場合は、再生処理工程などを挙げることができる。一般式［１］又は一般式［２］で表される化合物の添加方法に特に制限はなく、例えば、そのまま添加することができ、あるいは、微量の界面活性剤、水、溶剤などを配合して水に自己乳化するように製剤化したのち添加することもでき、さらに、水、溶剤などに溶解、分散又は乳化して添加することもできる。
【００１１】
本発明方法においては、紙料に他の薬品を添加することができる。他の薬品としては、例えば、湿潤紙力剤、乾燥紙力剤、澱粉、ポリビニルアルコールなどの紙力剤、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。
本発明方法により低密度化させる紙は、植物繊維及び／又はその他の繊維をからみ合わせ膠着することによって得られる薄層物である。使用するパルプなどの原料に特に制限はなく、例えば、広葉樹、針葉樹などから得られる木材パルプ、バガス、ケナフ、竹パルプなどの植物繊維、レーヨンなどの再生繊維、ポリエステル、ポリアミドなどの合成繊維、繊維状無機材料などを挙げることができる。本発明方法は、また、パルプモールドなどの繊維材料にも適用することができる。
本発明方法により製造する低密度紙に特に制限はなく、例えば、新聞用紙、印刷用紙、記録用紙、包装用紙、板紙、ライナー、中芯などのダンボール用紙、壁紙、襖紙原紙やその裏打ち紙などを挙げることができる。紙を低密度化することにより、めくりやすさ、印刷適性、ボリューム感、風合い、手触りなどの柔軟性、紙の割れ防止性、層間剥離のしやすさ、吸水性、吸油性、吸樹脂性、不透明性などを改良し、コストを低減することができる。
本発明の紙用低密度化剤及び低密度紙の製造方法によれば、起泡による問題がなく、サイズ度の低下が少なく、紙を低密度化し得るのみならず、紙の不透明性と白色度を向上させ、紙の含水伸度を低下させることができる。
【００１２】
【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、試験紙は下記の方法により評価した。
（１）密度
ＪＩＳ Ｐ ８１１８にしたがって測定する。
（２）不透明度
ＪＩＳ Ｐ ８１３８にしたがい、COLORIMETER［(株)村上色彩技術研究所、ＣＭ−５３Ｄ］を用いて測定する。
（３）白色度
ＪＩＳ Ｐ ８１２３にしたがって測定する。
（４）サイズ度
ＪＩＳ Ｐ ８１２２にしたがって測定する。
（５）含水伸度
ＪＩＳ Ｐ ８１１１にしたがって前処置した試験紙に、鉛筆で長さ１５ｃｍの実線を５ケ所に描き、２０℃の水に１５分浸漬した後の実線の長さを測定し、含水伸度の平均値を算出する。
（６）起泡性
実施例又は比較例で用いる化合物の０.０１質量％分散液又は溶液を、１Ｌのメスシリンダーに２００ｍＬ入れ、温度を４０℃に調節し、エアーポンプよりガラスボールフィルターを通して空気を１Ｌ／分で吹き込み、吹き込みを始めてから１分後、２分後、３分後における泡の高さを測定する。また、空気を３分間吹き込んだのち停止し、その１分後の泡の高さを測定する。
【００１３】
実施例１
耐圧反応容器に、ステアリルアミン２６９ｇ（１モル）を仕込み、内部を窒素ガスで置換し、１３０℃に昇温し、エチレンオキシド８８ｇ（２モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下に保ちながら、約２時間で耐圧反応容器に吹き込んだ。次に、冷却して８０℃以下にしたのち、触媒として水酸化ナトリウム１.０ｇを添加し、内部を窒素ガスで置換し、１３０℃に昇温し、エチレンオキシド１７６ｇ（４モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら、約３時間で耐圧反応容器に吹き込んだ。次いで、リン酸で触媒を中和し、真空脱水を行い、析出した結晶をろ別して、ステアリルアミンのエチレンオキシド６モル付加物５３３ｇを得た。
ステアリルアミンのエチレンオキシド６モル付加物２６６.５ｇ（０.５モル）、トール油脂肪酸２８９ｇ（１モル）及び触媒としてパラトルエンスルホン酸０.７ｇを４つ口フラスコに仕込み、窒素ガス気流下、温度１８０〜２４０℃で約５時間脱水エステル化反応を行ない、ステアリルアミンエチレンオキシド６モル付加物のトール油脂肪酸の２モルエステル化物を得た。
広葉樹晒しクラフトパルプと針葉樹晒しクラフトパルプを質量比７０／３０に配合し、カナダ標準型ろ水度４２０ｍＬに叩解してパルプスラリーを調製した。このパルプスラリーをケミスターラーを用いて撹拌しながら、上記のステアリルアミンエチレンオキシド６モル付加物のトール油脂肪酸の２モルエステル化物を水に乳化分散した分散液を低密度化剤として用い、パルプに対して０.２質量％になるように添加し、５分後に乾燥紙力剤［ハリマ化成(株)、ハーマイドＣ−１０、アニオン性］をパルプに対して０.４質量％添加し、その５分後に硫酸バンドを用いてｐＨを４.５に調整し、さらにその５分後にエマルジョンサイズ剤［日本ＰＭＣ(株)、ＡＬ−１２０Ｆ］をパルプに対して１質量％添加した。その後１０分間撹拌を継続して、紙料の調成を終了した。
この紙料を、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７００ｋＰａで５分間プレス処理を行い、さらに試験用のヤンキードライヤーを用いて１０５℃で３分間乾燥し、試験紙を得た。
得られた試験紙は、密度０.５８４ｇ／ｃｍ3、不透明度８５.５％、白色度７８.４、サイズ度２０秒、含水伸度１.０７％であった。
また、上記のステアリルアミンエチレンオキシド６モル付加物のトール油脂肪酸の２モルエステル化物の０.０１質量％水分散液について、エア曝気法により起泡性試験を行った結果、泡の高さはエアー吹き込み開始１分後、２分後、３分後ともに３０ｍｍであり、停止１分後０ｍｍであった。
【００１４】
実施例２〜４
第１表に示すアミン、アルキレンオキシド及び脂肪酸を用い、実施例１と同様にして一般式［１］で表される化合物を合成し、実施例１と同様にして試験紙を作製して評価するとともに、該化合物について起泡性試験を行った。
実施例５
耐圧反応容器に、ココナッツアミン［花王(株)、ファーミンＣＳ］１９７ｇ（１モル）を仕込み、内部を窒素ガスで置換し、１３０℃に昇温し、エチレンオキシド８８ｇ（２モル）を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下に保ちながら、約２時間で耐圧反応容器に吹き込んだ。次に、冷却して８０℃以下にしたのち、触媒として水酸化ナトリウム１.０ｇを添加し、内部を窒素ガスで置換し、１３０℃に昇温して、エチレンオキシド１７６ｇ（４モル）とプロピレンオキシド２３２ｇ（４モル）の混合物を反応温度１４０〜１５０℃、圧力３９２ｋＰａ以下を保ちながら、約４時間で耐圧反応容器に吹き込んだ。次いで、リン酸で触媒を中和し、真空脱水を行い、析出した結晶をろ別して、ココナッツアミンのエチレンオキシド２モルブロック、エチレンオキシド４モルプロピレンオキシド４モルランダム付加物６９３ｇを得た。
ココナッツアミンのエチレンオキシド２モルブロック、エチレンオキシド４モルプロピレンオキシド４モルランダム付加物３４７ｇ（０.５モル）、ステアリン酸７１ｇ（０.２５モル）、パルミチン酸１９２ｇ（０.７５モル）及び触媒としてパラトルエンスルホン酸０.７ｇを４つ口フラスコに仕込み、窒素ガス気流下、温度１８０〜２４０℃で約５時間脱水エステル化反応を行ない、ココナッツアミンのエチレンオキシド２モルブロック、エチレンオキシド４モルプロピレンオキシド４モルランダム付加物のステアリン酸／パルミチン酸の２モルエステル化物を得た。
このエステル化物を用い、実施例１と同様にして試験紙を作製して評価するとともに、エステル化物について起泡性試験を行った。
【００１５】
実施例６〜１０
第１表に示すアミン、アルキレンオキシド及び脂肪酸を用い、実施例１と同様にして一般式［１］又は一般式［２］で表される化合物を合成し、実施例１と同様にして試験紙を作製して評価するとともに、該化合物について起泡性試験を行った。
ただし、実施例８で得られた化合物は、単独では水に分散しないので、実施例１で得られた化合物１０質量部と実施例８で得られた化合物１００質量部を混合して予備乳化し、さらにホモジナイザーを用いて圧力３００ｋＰａで１パスして分散液とし、試験紙の作製と起泡性試験を行なった。
比較例１
低密度化剤を添加することなく、実施例１と同様にして試験紙を作製し、評価を行った。また、低密度化剤を添加しない水について、起泡性試験を行った。
比較例２
ステアリン酸ナトリウムを水に乳化分散した分散液を低密度化剤として用い、添加量がパルプに対して０.２質量％になるように添加し、実施例１と同様にして試験紙を作製して評価を行うとともに、ステアリン酸ナトリウムについて起泡性試験を行った。
比較例３〜８
第２表に示す低密度化剤を用い、実施例１と同様にして試験紙を作製して評価を行うとともに、該低密度化剤について起泡性試験を行った。
実施例１〜１０で合成し、試験した低密度化剤の原料組成を第１表に、比較例１〜８で用いた低密度化剤を第２表に、実施例１〜１０及び比較例１〜８の結果を第３表に示す。
【００１６】
【表１】
【表２】
【表３】
第３表に見られるように、本発明の紙用低密度化剤を用いて本発明方法により作製した実施例１〜１０の試験紙は、密度０.５８３〜０.５９１ｇ／ｃｍ3、不透明度８５.１〜８５.５％、白色度７８.１〜７８.４、サイズ度１０〜２０秒、含水伸度１.０７〜１.０９％であり、低密度化剤として優れた性能を有している。また、起泡性試験における泡の高さは、低密度化剤を添加しない水について測定した比較例１と同じか、あるいは、わずかに高いだけであり、優れた低起泡性を有している。
これに対して、従来の低密度化剤を用いて作製した比較例２〜８の試験紙は、密度０.５９４〜０.６１３ｇ／ｃｍ3、不透明度８４.５〜８４.８％、白色度７７.７〜７７.９、サイズ度は４４秒の１例を除いて他の６例はすべて０秒、含水伸度１.１２〜１.１９％であり、実施例において得られた低密度紙より全般的に性能が劣り、特にサイズ度の低下が著しい。また、起泡性試験における泡も高く、低起泡性を有していない。
【００２０】
【発明の効果】
本発明の紙用低密度化剤及び低密度紙の製造方法によれば、紙製品のパルプ原料の使用量を低減し、製品の生産性を向上し、原料コストを低減することができる。また、印刷適性に優れ、ボリューム感のある高品質の紙を製造することができる。さらに、不透明度の向上によって、紙製品のパルプ原料及び無機填料の使用量を低減することができ、白色度の向上によって、良品質の紙の製造が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper density reducing agent and a method for producing low density paper. More specifically, the present invention is a paper capable of producing a low-density paper having low foaming properties, easy to use, little reduction in sizing, low density, opacity, whiteness, and low moisture content. The present invention relates to a low-density agent and a method for producing low-density paper.
[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. By reducing the basis weight of paper products such as newsprint, printing paper, recording paper, wrapping paper, wallpaper paper, backing paper, etc., it will be a great solution to global environmental problems such as securing forest resources, as well as reducing costs. It is thought to bring about an effect.
On the other hand, there is a demand for high-quality paper with printability and volume, and there is a demand for low-density paper with a high paper bulk. Conventionally, as a method for reducing the density of paper, a method using a cross-linked pulp, a method using a mixed paper with synthetic fibers, a method of filling pulp fibers with an inorganic substance, and the like have been performed. However, the method using cross-linked pulp or the method based on blending with synthetic fibers makes it difficult to recycle paper and increases the cost. Further, the method of filling with an inorganic substance has a drawback that the strength of the paper is remarkably lowered.
Recently, drugs have been developed that reduce the density by adding organic compounds during papermaking. For example, a paper bulking agent containing an alkylene oxide adduct of a higher fatty acid has been proposed as a densification agent (Patent Document 1). A bulking agent for paper containing an alkylene oxide adduct of a higher alcohol has also been proposed (Patent Document 2). However, nonionic active agents such as higher alcohols and higher fatty acid alkylene oxide adducts significantly reduce the size of paper due to the presence of highly hydrophilic polyether groups in the molecule. Furthermore, since these compounds have high foaming properties, troubles such as floating seeds due to foam and paper pinholes often occur.
[Patent Document 1]
JP-A-11-200284 (page 5)
[Patent Document 2]
Tokushu W098 / 03730 (pages 12-14)
[0003]
[Problems to be solved by the invention]
The present invention is a low-foaming paper that can be used to produce low-density paper that has low foaming properties, is easy to use, has little reduction in sizing, is excellent in low-density properties, opacity, and whiteness, and has low moisture content. It was made for the purpose of providing the manufacturing method of an agent and a low density paper.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have added a polyoxyalkylene fatty acid ester of an alkylamine having a long-chain hydrophobic group at the terminal to the papermaking process, thereby starting in the process. The present inventors have found that low density paper with low decrease in sizing degree, excellent opacity and whiteness, and low water content elongation can be obtained without causing foaming problems, and to complete the present invention based on this finding. It came.
That is, the present invention
(1) A paper density-reducing agent comprising a compound represented by the general formula [1] or [2],
[Chemical 3]
(2) A method for producing low-density paper, comprising adding a compound represented by the general formula [1] or the general formula [2] to a papermaking process.
[Formula 4]
Is to provide.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
The paper density-reducing agent of the present invention contains a compound represented by the general formula [1] or the general formula [2]. In the method for producing low-density paper of the present invention, a compound represented by the general formula [1] or the general formula [2] is added to the papermaking process.
[Chemical formula 5]
In General Formula [1] or General Formula [2], R 1 , R 4, and R 5 are each an alkyl group, a hydroxyalkyl group, an alkenyl group, or a hydroxyalkenyl group having 8 to 36 carbon atoms, more preferably 12 to 24 carbon atoms. It is a group. If the carbon number of R 1 , R 4, or R 5 is 7 or less, the density of the obtained paper is not sufficiently lowered, and the sizing degree may be extremely lowered. When the carbon number of R 1 , R 4 or R 5 is 37 or more, handling of the paper densifying agent may be difficult.
[0006]
In General Formula [1] or General Formula [2], the alkyl group, hydroxyalkyl group, alkenyl group or hydroxyalkenyl group having 8 to 36 carbon atoms represented by R 1 , R 4 and R 5 is linear. Or may have a branch. Examples of such an alkyl group include octyl group, nonyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, docosyl group, and triacontyl group. Examples of the hydroxyalkyl group include a 10-hydroxyoctadecyl group. Examples of the alkenyl group include octenyl group, nonenyl group, decenyl group, dodecenyl group, tetradecenyl group, hexadecenyl group, octadecenyl group, icocenyl group, dococenyl group and the like. Examples of the hydroxyalkenyl group include a 12-hydroxy-9-octadecenyl group.
In the general formula [1] or [2], R 2 , R 3, and R 6 are each an alkyl group, hydroxyalkyl group, alkenyl group, or hydroxyalkenyl having 7 to 35 carbon atoms, more preferably 11 to 23 carbon atoms. It is a group. If the carbon number of R 2 , R 3, or R 6 is 6 or less, the density of the resulting paper is not sufficiently lowered, the foaming property is increased, and the reduction in sizing degree may be extremely increased. If the carbon number of R 2 , R 3 or R 6 is 36 or more, handling of the paper densifying agent may be difficult.
[0007]
In General Formula [1] or General Formula [2], the alkyl group, hydroxyalkyl group, alkenyl group, or hydroxyalkenyl group having 7 to 35 carbon atoms represented by R 2 , R 3, or R 6 is linear. Or may have a branch. Examples of such an alkyl group include a heptyl group, an octyl group, a nonyl group, an undecyl group, a tridecyl group, a heptadecyl group, a nonadecyl group, and a hencicosyl group. Examples of the hydroxyalkyl group include a 9-hydroxyheptadecyl group. Examples of the alkenyl group include a heptenyl group, an octenyl group, a nonenyl group, an undecenyl group, a tridecenyl group, a pentadecenyl group, a heptadecenyl group, a nonadecenyl group, and a henicocenyl group. Examples of the hydroxyalkenyl group include a 12-hydroxy-9-octadecenyl group.
In General Formula [1] or General Formula [2], A 1 , A 2, and A 3 are alkylene groups having 2 to 4 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, a trimethylene group, an ethylethylene group, and a tetramethylene group. In general formula [1] or general formula [2], p, q, and r are 1-40, More preferably, it is 1-20. When p, q, or r exceeds 40, there is a possibility that the decrease in sizing degree becomes extremely high. When p, q, and r are 20 or less, a decrease in sizing degree is reduced.
[0008]
In the structures (A 1 O) p, (A 2 O) q, and (A 3 O) r, the alkyleneoxy group can be one homopolymer structure, and can be two or more copolymer structures. You can also. The copolymer structure can be any of a random copolymer structure, a block copolymer structure, and a copolymer structure in which a random structure and a block structure are mixed. In general formula [1] or general formula [2], the type, number of moles, and combination of alkyleneoxy groups of (A 1 O) p, (A 2 O) q or (A 3 O) r structure are selected appropriately. As a result, it is possible to obtain a low-density agent that has low foaming properties, is easily dissolved or dispersed in water, and is easy to handle.
Conventional nonionic active agents such as higher fatty acids and alkylene oxide adducts of higher alcohols have polyether groups with high hydrophilicity in the molecule. Is significantly reduced. The paper density-reducing agent of the present invention contains a compound represented by the general formula [1] or the general formula [2] in which a long-chain hydrophobic group is present at the terminal, and therefore suppresses a decrease in the size of paper. be able to. Furthermore, in the compound represented by the general formula [1] or the general formula [2], the presence of three hydrophobic groups having a large number of carbons at the terminal deteriorates the orientation as a surfactant and causes foaming properties. Decreases.
[0009]
There is no particular limitation on the method for producing the compound represented by the general formula [1] or the general formula [2] used in the present invention. For example, an amine compound such as alkylamine or dialkylamine is used as a starting material, and no catalyst or alkali is used. An intermediate is obtained by adding an alkylene oxide using a catalyst such as or acid. This intermediate can be produced by a dehydration reaction with a fatty acid, a dehydrochlorination reaction with a fatty acid chloride, a transesterification reaction with a lower alcohol fatty acid ester, etc., using a catalyst such as an acid or an alkali.
The amine compound which is a starting material of the compound represented by the general formula [1] or the general formula [2] can be used alone or in combination of two or more. Examples of the amine compound used for the production of the compound represented by the general formula [1] or [2] include octylamine, 2-ethylhexylamine, nonylamine, laurylamine, myristylamine, cetylamine, stearylamine, Examples include stearylamine, oleylamine, behenylamine, coconutamine, 12-hydroxystearylamine, dilaurylamine, distearylamine, dioleylamine, and other synthetic amines.
[0010]
In the production of the compound represented by the general formula [1] or the general formula [2], one type of fatty acid or a derivative thereof can be used alone, or two or more types can be used in combination. There is no restriction | limiting in particular in the structure of a C8-C36 fatty acid used for manufacture of the compound represented by General formula [1] or General formula [2], It has a saturated fatty acid, an unsaturated fatty acid, a linear fatty acid, and a branch Any fatty acid such as a fatty acid or a fatty acid having a hydroxyl group can be used. Examples of such fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, oleic acid, linoleic acid, linolenic acid, erucic acid, 21- Triacontenoic acid, 12-hydroxystearic acid, ricinoleic acid, isononanoic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, isopalmitic acid, isostearic acid, dimer acid obtained by diluting fatty acid, tall oil fatty acid, beef tallow fatty acid, palm Examples thereof include fatty acids, castor fatty acids, and hardened fatty acids thereof.
In the method of the present invention, there is no particular limitation on the papermaking process to which the compound represented by the general formula [1] or the general formula [2] is added. For example, a disaggregation process, a beating process, a preparation process in which chemicals are blended, papermaking The previous one can be mentioned. Further, in the case of used paper, a recycling treatment process can be exemplified. There is no particular limitation on the method for adding the compound represented by the general formula [1] or the general formula [2]. For example, the compound can be added as it is, or a trace amount of a surfactant, water, a solvent and the like can be added. It can also be added after being formulated so as to be self-emulsified in water, and can also be added after being dissolved, dispersed or emulsified in water, a solvent or the like.
[0011]
In the method of the present invention, other chemicals can be added to the stock. Other chemicals include, for example, wet paper strength agents, dry paper strength agents, starch strength, polyvinyl alcohol and other paper strength agents, dryer release agents, pitch control agents, slime control agents, deinking agents, sizing agents, paper quality improving agents. , Fillers, pigments, dyes, antifoaming agents and the like.
The paper to be reduced in density by the method of the present invention is a thin layer obtained by entanglement and sticking of vegetable fibers and / or other fibers. The raw materials such as pulp to be used are not particularly limited. For example, wood pulp obtained from broad-leaved trees, conifers, plant fibers such as bagasse, kenaf, bamboo pulp, regenerated fibers such as rayon, synthetic fibers such as polyester and polyamide, fibers And inorganic inorganic materials. The method of the present invention can also be applied to fiber materials such as pulp molds.
There is no particular limitation on the low density paper produced by the method of the present invention, for example, newspaper paper, printing paper, recording paper, wrapping paper, cardboard paper such as paperboard, liner, core, wallpaper, base paper, backing paper thereof, etc. Can be mentioned. By reducing the density of paper, it is easy to turn, printability, voluminous feel, texture, touch, etc., paper crack prevention, ease of delamination, water absorption, oil absorption, resin absorption, The opacity and the like can be improved and the cost can be reduced.
According to the paper density-reducing agent and the method for producing low-density paper of the present invention, there is no problem due to foaming, there is little decrease in sizing degree, and the paper can be reduced in density. The degree of moisture content of the paper can be reduced.
[0012]
【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 test paper was evaluated by the following method.
(1) Density Measured according to JIS P 8118.
(2) Opacity Measured according to JIS P 8138 using COLORIMETER [Murakami Color Research Laboratory, CM-53D].
(3) Whiteness Measured according to JIS P 8123.
(4) Sizing degree Measured in accordance with JIS P 8122.
(5) Water content elongation On a test paper pretreated according to JIS P 8111, a 15 cm long solid line is drawn at five locations with a pencil, and the length of the solid line after being immersed in water at 20 ° C. for 15 minutes is measured. The average value of water content elongation is calculated.
(6) Foaming property 200 mL of a 0.01 mass% dispersion or solution of the compound used in Examples or Comparative Examples is placed in a 1 L graduated cylinder, the temperature is adjusted to 40 ° C., and air is passed through a glass ball filter from an air pump. Is measured at 1 L / min, and the height of the foam is measured after 1 minute, 2 minutes and 3 minutes after the start of blowing. Moreover, after blowing air for 3 minutes, it stops and the height of the bubble after 1 minute is measured.
[0013]
Example 1
Into a pressure-resistant reaction vessel, 269 g (1 mol) of stearylamine was charged, the inside was replaced with nitrogen gas, the temperature was raised to 130 ° C., and 88 g (2 mol) of ethylene oxide was maintained at a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less. Then, it was blown into the pressure-resistant reaction vessel in about 2 hours. Next, after cooling to 80 ° C. or lower, 1.0 g of sodium hydroxide is added as a catalyst, the inside is replaced with nitrogen gas, the temperature is raised to 130 ° C., and 176 g (4 mol) of ethylene oxide is added at a reaction temperature of 140 ° C. While maintaining ˜150 ° C. and a pressure of 392 kPa or less, it was blown into the pressure resistant reactor in about 3 hours. Next, the catalyst was neutralized with phosphoric acid, vacuum dehydration was performed, and the precipitated crystals were separated by filtration to obtain 533 g of a stearylamine ethylene oxide 6 mol adduct.
A stearylamine 6-mole ethylene oxide 6-mol adduct 266.5 g (0.5 mol), tall oil fatty acid 289 g (1 mol) and p-toluenesulfonic acid 0.7 g as a catalyst were charged into a four-necked flask under a nitrogen gas stream under temperature. A dehydration esterification reaction was carried out at 180 to 240 ° C. for about 5 hours to obtain a 2 mol esterified product of stearylamine ethylene oxide 6 mol adduct tall oil fatty acid.
A pulp slurry was prepared by blending hardwood bleached kraft pulp and softwood bleached kraft pulp in a mass ratio of 70/30 and beating to a Canadian standard freeness of 420 mL. While stirring this pulp slurry with a chemistrar, using a dispersion obtained by emulsifying and dispersing 2 mol esterified product of the above-mentioned stearylamine ethylene oxide 6 mol adduct of tall oil fatty acid in water, 0.2% by weight, and after 5 minutes, 0.4% by weight of dry paper strength agent [Harima Kasei Co., Ltd., Hermide C-10, anionic] was added to the pulp. After 5 minutes, the pH was adjusted to 4.5 using a sulfuric acid band, and further 5 minutes later, 1% by mass of an emulsion sizing agent [Japan PMC Co., Ltd., AL-120F] was added to the pulp. Thereafter, stirring was continued for 10 minutes to complete the preparation of the stock.
This stock is made into a paper having a basis weight of 80 g / m 2 using a test square sheet machine, subjected to press treatment at 700 kPa for 5 minutes using a press machine, and at 105 ° C. using a test Yankee dryer. It was dried for 3 minutes to obtain a test paper.
The obtained test paper had a density of 0.584 g / cm 3 , an opacity of 85.5%, a whiteness of 78.4, a size of 20 seconds, and a water content elongation of 1.07%.
Moreover, as a result of conducting a foaming property test by an air aeration method with respect to a 0.01% by mass aqueous dispersion of 2-mole esterified product of the above-mentioned stearylamine ethylene oxide 6-mole adduct of tall oil fatty acid, the height of the foam was air. It was 30 mm after 1 minute, 2 minutes, and 3 minutes after the start of blowing, and 0 mm after 1 minute from the stop.
[0014]
Examples 2-4
Using the amine, alkylene oxide and fatty acid shown in Table 1, the compound represented by the general formula [1] was synthesized in the same manner as in Example 1, and a test paper was prepared and evaluated in the same manner as in Example 1. At the same time, a foamability test was performed on the compound.
Example 5
A pressure-resistant reaction vessel was charged with 197 g (1 mol) of coconut amine [Kao Corporation, Farmin CS], the inside was replaced with nitrogen gas, the temperature was raised to 130 ° C., and 88 g (2 mol) of ethylene oxide was added at a reaction temperature of 140 to While maintaining at 150 ° C. and a pressure of 392 kPa or less, the pressure-resistant reaction vessel was blown in about 2 hours. Next, after cooling to 80 ° C. or lower, 1.0 g of sodium hydroxide was added as a catalyst, the inside was replaced with nitrogen gas, the temperature was raised to 130 ° C., and 176 g (4 mol) of ethylene oxide and propylene oxide were added. While maintaining a reaction temperature of 140 to 150 ° C. and a pressure of 392 kPa or less, 232 g (4 mol) of the mixture was blown into the pressure resistant reactor in about 4 hours. Next, the catalyst was neutralized with phosphoric acid, vacuum dehydration was performed, and the precipitated crystals were separated by filtration to obtain 693 g of a coconut amine ethylene oxide 2 mol block and ethylene oxide 4 mol propylene oxide 4 mol random adduct.
Ethylene oxide 2 mol block of coconut amine, ethylene oxide 4 mol propylene oxide 4 mol random adduct 347 g (0.5 mol), stearic acid 71 g (0.25 mol), palmitic acid 192 g (0.75 mol) and paratoluene as catalyst 0.7 g of sulfonic acid was charged into a four-necked flask and subjected to dehydration esterification reaction at a temperature of 180 to 240 ° C. for about 5 hours under a nitrogen gas stream. Ethanol oxide 2 mol block of coconut amine, ethylene oxide 4 mol propylene oxide 4 mol random An adduct, 2-mole esterified product of stearic acid / palmitic acid, was obtained.
Using this esterified product, a test paper was prepared and evaluated in the same manner as in Example 1, and a foamability test was performed on the esterified product.
[0015]
Examples 6-10
Using the amine, alkylene oxide and fatty acid shown in Table 1, the compound represented by the general formula [1] or the general formula [2] was synthesized in the same manner as in Example 1, and the test paper was tested in the same manner as in Example 1. Were prepared and evaluated, and a foaming test was performed on the compound.
However, since the compound obtained in Example 8 alone is not dispersed in water, it is pre-emulsified by mixing 10 parts by mass of the compound obtained in Example 1 and 100 parts by mass of the compound obtained in Example 8. Furthermore, using a homogenizer, a pass was made at a pressure of 300 kPa to obtain a dispersion, and a test paper was prepared and a foaming test was performed.
Comparative Example 1
A test paper was prepared and evaluated in the same manner as in Example 1 without adding a density-reducing agent. Moreover, the foamability test was done about the water which does not add a density reducing agent.
Comparative Example 2
A dispersion obtained by emulsifying and dispersing sodium stearate in water was used as a densification agent, and added so that the addition amount was 0.2% by mass with respect to the pulp. A test paper was prepared in the same manner as in Example 1. The foaming property test was conducted on sodium stearate.
Comparative Examples 3-8
Using the density reducing agent shown in Table 2, a test paper was prepared and evaluated in the same manner as in Example 1, and the foaming property test was conducted on the density reducing agent.
The raw material composition of the low-density agent synthesized and tested in Examples 1 to 10 is shown in Table 1, the low-density agent used in Comparative Examples 1 to 8 is shown in Table 2, Examples 1 to 10 and Comparative Examples The results of 1 to 8 are shown in Table 3.
[0016]
[Table 1]
[Table 2]
[Table 3]
As can be seen in Table 3, the test papers of Examples 1 to 10 prepared by the method of the present invention using the paper densifying agent of the present invention have a density of 0.583 to 0.591 g / cm 3 , It has a transparency of 85.1 to 85.5%, a whiteness of 78.1 to 78.4, a size of 10 to 20 seconds and a water content elongation of 1.07 to 1.09%, and has excellent performance as a low density agent. Have. In addition, the foam height in the foaming test is the same as or slightly higher than that of Comparative Example 1 measured for water without the addition of a densifying agent, and has an excellent low foaming property. Yes.
On the other hand, the test papers of Comparative Examples 2 to 8 prepared using conventional densifying agents have a density of 0.594 to 0.613 g / cm 3 , an opacity of 84.5 to 84.8%, and a white color. Except for one case of degree 77.7 to 77.9 and sizing of 44 seconds, all the other 6 cases were 0 seconds and the water content elongation was 1.12 to 1.19%. The performance is generally inferior to that of the density paper, and particularly the size degree is significantly reduced. Moreover, the foam in a foamability test is also high and does not have low foamability.
[0020]
【The invention's effect】
According to the paper density-reducing agent and the method for producing low-density paper of the present invention, the amount of pulp raw material used in paper products can be reduced, product productivity can be improved, and raw material costs can be reduced. In addition, high-quality paper with excellent printability and volume can be produced. Furthermore, the increase in opacity can reduce the amount of pulp raw materials and inorganic filler used in paper products, and the improvement in whiteness enables the production of good quality paper.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05244743A (en) * | 1992-02-27 | 1993-09-21 | Sankyo Seiki Mfg Co Ltd | Air-core coil and manufacture thereof |
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| JP2007197855A (en) * | 2006-01-25 | 2007-08-09 | Meisei Kagaku Kogyo Kk | Density-lowering agent for making paper, method for making paper with density-lowering agent for making paper, and paper containing the density-lowering agent for making paper |
| JP2008063691A (en) * | 2006-09-07 | 2008-03-21 | Kurita Water Ind Ltd | Paper making method |
| JP7499216B2 (en) * | 2021-06-10 | 2024-06-13 | 伯東株式会社 | Bulking agents for fiber-containing boards and their use in building boards |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH05244743A (en) * | 1992-02-27 | 1993-09-21 | Sankyo Seiki Mfg Co Ltd | Air-core coil and manufacture thereof |
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