JP2008127685A - Density lowering agent of paper, and method for producing low-density paper - Google Patents
Density lowering agent of paper, and method for producing low-density paper Download PDFInfo
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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、低密度化性に優れ、サイズ度低下の少ない低密度紙を容易に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。 The present invention relates to a paper density reducing agent and a method for producing low density paper. More specifically, the present invention relates to a paper density-reducing agent and a method for producing low-density paper that can easily produce low-density paper that is excellent in density reduction and has little reduction in size.
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、板紙、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求められており、紙の嵩を高くした密度の低い紙が要望されている。従来より、紙の嵩を高くする方法として、架橋パルプを用いる方法や、合成繊維との混抄、パルプ繊維に無機物を充填するなどの方法が行われている。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、コスト的にも高くなり、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。これらの欠点を解消するために、抄紙時に有機化合物を添加して嵩を高くする低密度化剤が検討されている。
例えば、紙力を損なうことなく低密度化されたシートが得られる紙用低密度化剤として、油脂系非イオン界面活性剤、糖アルコール系非イオン界面活性剤又は糖系非イオン界面活性剤を含有する紙用低密度化剤（特許文献１）、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低密度化剤（特許文献２）、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低密度化剤（特許文献３）が提案されている。
しかし、これらの化合物は、イオン性がないために紙に対する自己定着性が低く、使用量の割には紙の低密度化効果が低い。また、使用量を増加すると、定着性が低いために抄紙系中に低密度化剤が蓄積し、低密度化のコントロールが難しく、発泡、浮き種などの問題を起こしやすい。また、紙の強度、表面強度やサイズ度を低下させやすい。さらに、高級アルコールのアルキレンオキシド付加物、高級脂肪酸のアルキレンオキシド付加物、油脂系非イオン活性剤などには、分子内に親水性の高いポリアルキレンオキシド鎖が存在するために、サイズ度が著しく低下する。
サイズ剤の効果を損なうことなく低密度化されたシートが得られる紙用低密度化剤として、オキシアルキレン基を有する多価アルコール脂肪酸エステル化合物（特許文献４）が提案されている。
しかし、この化合物は、水とのなじみが悪く、そのままでは使用できないために、非イオン界面活性剤、アニオン界面活性剤、カチオン界面活性剤などの界面活性剤を使用しなければ、水や熱水に分散又は乳化させることが困難であり、この際に使用する界面活性剤によって、発泡や浮き種などの問題が発生する。また、紙の強度、表面強度、サイズ度も低下するといった問題があった。
On the other hand, there is a demand for high-quality paper with printability and volume feeling, and there is a demand for low-density paper with high paper bulk. Conventionally, as a method for increasing the bulk of paper, a method using a cross-linked pulp, a mixed paper with synthetic fibers, and a method of filling pulp fibers with an inorganic substance have been performed. However, the method using cross-linked pulp or the method based on blending with synthetic fibers makes it difficult to recycle the paper and increases the cost, and the method based on filling with inorganic substances has a drawback that the strength of the paper is significantly reduced. . In order to eliminate these drawbacks, low density agents that increase the bulk by adding an organic compound during papermaking have been studied.
For example, an oil-based nonionic surfactant, a sugar alcohol-based nonionic surfactant, or a sugar-based nonionic surfactant is used as a paper density reducing agent for obtaining a sheet having a reduced density without impairing paper strength. Low density agent for paper containing (Patent Document 1), Low density agent for paper containing alkylene oxide adduct of higher fatty acid (Patent Document 2), Low density for paper containing alkylene oxide adduct of higher alcohol An agent (Patent Document 3) has been proposed.
However, since these compounds are not ionic, they have low self-fixing property to paper, and the effect of reducing the density of paper is low for the amount used. Further, when the amount used is increased, the fixing property is low, so that the density reducing agent accumulates in the papermaking system, and it is difficult to control the density reduction, and problems such as foaming and floating seeds are likely to occur. In addition, the strength, surface strength and sizing degree of the paper are likely to be reduced. Furthermore, higher alcohol alkylene oxide adducts, higher fatty acid alkylene oxide adducts, and oil-based nonionic active agents have a highly hydrophilic polyalkylene oxide chain in the molecule, resulting in a significant reduction in size. To do.
A polyhydric alcohol fatty acid ester compound having an oxyalkylene group (Patent Document 4) has been proposed as a paper density reducing agent for obtaining a low density sheet without impairing the effect of the sizing agent.
However, since this compound is not compatible with water and cannot be used as it is, water or hot water must be used unless a surfactant such as a nonionic surfactant, an anionic surfactant, or a cationic surfactant is used. It is difficult to disperse or emulsify, and the surfactant used in this case causes problems such as foaming and floating seeds. Further, there is a problem that the strength, surface strength, and sizing degree of the paper are also reduced.
本発明は、低密度化性に優れ、サイズ度低下の少ない低密度紙を容易に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。 The present invention has been made for the purpose of providing a low-density agent for paper and a method for producing low-density paper, which can easily produce low-density paper with excellent density reduction and little reduction in size. It is.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、平均炭素数１２〜２２のアルキル基又はアルケニル基を有する２級アミンとエピハロヒドリンとを反応して得られるアミノ化合物を、紙の製造に使用するパルプに添加することにより、優れた低密度化性を有し、サイズ度低下の少ない低密度紙を効率よく製造し得ることを見いだし、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）平均炭素数１２〜２２のアルキル基又はアルケニル基を少なくとも１個有する２級アミンと、エピハロヒドリンとを反応して得られるアミノ化合物を含有することを特徴とする紙用低密度化剤、
（２）２級アミンが、平均炭素数１２〜１８のアルキル基を２個有する(１)に記載の紙用低密度化剤、及び、
（３）紙の製造に使用するパルプに、(１)又は(２)に記載の紙用低密度化剤を添加することを特徴とする低密度紙の製造方法、
を提供するものである。
As a result of intensive studies to solve the above problems, the present inventors have obtained an amino compound obtained by reacting a secondary amine having an alkyl group or an alkenyl group having an average carbon number of 12 to 22 with an epihalohydrin, By adding to the pulp used for paper manufacture, we found that low density paper with excellent density reduction and little reduction in size could be efficiently produced, and the present invention was completed based on this finding. It came to do.
That is, the present invention
(1) A paper density-reducing agent comprising an amino compound obtained by reacting a secondary amine having at least one alkyl group or alkenyl group having an average carbon number of 12 to 22 and an epihalohydrin,
(2) The density reducing agent for paper according to (1), wherein the secondary amine has two alkyl groups having an average carbon number of 12 to 18, and
(3) A method for producing low-density paper, comprising adding the paper density-reducing agent described in (1) or (2) to pulp used for paper production,
Is to provide.
本発明の低密度化剤及び低密度紙の製造方法によれば、低密度性に優れ、サイズ度低下の少ない低密度紙を容易に製造することができ、パルプ原料の使用量を低減し、地球環境保護に寄与することができる。 According to the low-density agent and the low-density paper manufacturing method of the present invention, it is possible to easily manufacture low-density paper that is excellent in low-density properties and has little reduction in sizing, reducing the amount of pulp raw material used, It can contribute to global environmental protection.
本発明の紙用低密度化剤は、平均炭素数１２〜２２のアルキル基又はアルケニル基を少なくとも１個有する２級アミンと、エピハロヒドリンとを反応して得られるアミノ化合物を含有する。
本発明に用いられる平均炭素数１２〜２２のアルキル基又はアルケニル基を少なくとも１個有する２級アミンのアルキル基としては、例えば、ラウリル基、ミリスチル基、パルミチル基、ステアリル基、ベヘニ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、オレイル基などを挙げることができる。
このような平均炭素数１２〜２２のアルキル基又はアルケニル基を少なくとも１個有する２級アミンとしては、例えば、ジラウリルアミン、ジミリスチルアミン、ジパルミチルアミン、ジステアリルアミン、ジエイコシルアミン、ジベヘニルアミン、メチルラウリルアミン、メチルミリスチルアミン、メチルパルミチルアミン、メチルステアリルアミン、メチルベヘニルアミンなどの２級アルキルアミン；ジヤシアミン、ジ牛脂アミン、ジ硬化牛脂アミンなどの混合２級アルキルアミン；ジオレイルアミンなどの２級アルケニルアミンなどを挙げることができる。混合アミンのアルキル基又はアルケニル基の平均炭素数は、各アミン成分のモル平均数より算出する。これらの２級アミンは、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。用いる２級アミンのアルキル基又はアルケニル基の平均炭素数が１２〜２２の範囲内であれば、炭素数１２未満のアルキル基又はアルケニル基を有する２級アミンや、炭素数が２２を超えるアルキル基又はアルケニル基を有する２級アミンが含まれていてもよい。２級アミンのアルキル基又はアルケニル基の平均炭素数が１２未満であると、製造される紙の低密度化性が低下し、サイズ度が低下するおそれがある。２級アミンのアルキル基又はアルケニル基の平均炭素数が２２を超えると、得られるアミノ化合物の水に対する分散性又は乳化性が低下し、低密度化剤の分散に界面活性剤が必要になって、紙の低密度化性やサイズ度が低下するおそれがある。
The paper density-reducing agent of the present invention contains an amino compound obtained by reacting a secondary amine having at least one alkyl group or alkenyl group having an average carbon number of 12 to 22 with an epihalohydrin.
Examples of the alkyl group of the secondary amine having at least one alkyl group or alkenyl group having an average carbon number of 12 to 22 used in the present invention include lauryl group, myristyl group, palmityl group, stearyl group, and behenyl group. be able to. As an alkenyl group, an oleyl group etc. can be mentioned, for example.
Examples of the secondary amine having at least one alkyl group or alkenyl group having an average carbon number of 12 to 22 include dilaurylamine, dimyristylamine, dipalmitylamine, distearylamine, dieicosylamine, and diamine. Secondary alkylamines such as behenylamine, methyllaurylamine, methylmyristylamine, methylpalmitylamine, methylstearylamine, methylbehenylamine; mixed secondary alkylamines such as dicoconut amine, di-tallow amine, di-cured tallow amine; dioleylamine Secondary alkenylamines such as The average carbon number of the alkyl group or alkenyl group of the mixed amine is calculated from the molar average number of each amine component. These secondary amines can be used alone or in combination of two or more. If the average carbon number of the alkyl group or alkenyl group of the secondary amine used is in the range of 12 to 22, the secondary amine having an alkyl group or alkenyl group having less than 12 carbon atoms, or an alkyl group having more than 22 carbon atoms Or the secondary amine which has an alkenyl group may be contained. If the average carbon number of the alkyl group or alkenyl group of the secondary amine is less than 12, the density of the produced paper may be lowered, and the sizing degree may be lowered. If the average carbon number of the alkyl group or alkenyl group of the secondary amine exceeds 22, the dispersibility or emulsifiability of the resulting amino compound in water decreases, and a surfactant is required to disperse the density-reducing agent. Further, there is a possibility that the density reduction and the sizing degree of the paper are lowered.
本発明において、２級アミンは、平均炭素数１２〜１８のアルキル基を２個有することが好ましい。平均炭素数１２〜１８のアルキル基を２個有する２級アミンからは、優れた低密度化性や、サイズ度低下の少ない低密度紙を容易に製造することができる。
本発明に用いるエピハロヒドリンとしては、例えば、エピクロロヒドリン、エピブロモヒドリン、エピヨードヒドリンなどを挙げることができる。これらの中で、エピクロロヒドリンは、価格が安く、反応性が大きく、生成物の有用性に優れるので、好適に用いることができる。
本発明において、２級アミンとエピハロヒドリンを反応して得られるアミノ化合物を製造する方法に特に制限はなく、例えば、１種の２級アミンを単独で、若しくは、２種以上の２級アミンの混合物として、あるいは、エピハロヒドリンと反応可能な他の３級アミンとの混合物として、アミンに対して、エピハロヒドリンを好ましくは０.３〜５.０モル倍、より好ましくは０.４〜２.２モル倍、さらに好ましくは０.６〜１.６モル倍添加し、必要に応じて溶媒を用いて２０〜１００℃で反応させ、未反応のエピハロヒドリンを除去してアミノ化合物を製造することができる。この方法によれば、２級アミンとエピハロヒドリンとの反応により、アゼチジニウム環構造又はエポキシ構造が形成される場合もある。エピハロヒドリンの量がアミンに対して０.３モル倍未満であると、未反応のアミンが残存し、低密度化性や、サイズ度が低下するおそれがある。エピハロヒドリンの量がアミンに対して５.０モル倍を超えると、バッチスケールが大幅に低下し、生産性が低下するのみならず、エピハロヒドリン由来の不純物が多く生成するおそれがある。反応に用いる溶媒としては、例えば、水、メタノール、エタノール、イソプロパノール、ブタノール、ヘキサン、ヘプタン、シクロヘキサン、トルエン、ジクロロエタン、クロロホルム、テトラヒドロフラン、ジオキサンなどを挙げることができる。エピハロヒドリンと反応可能な他の３級アミンとしては、例えば、トリメチルアミン、トリエチルアミン、トリブチルアミン、トリヘキシルアミン、トリオクチルアミン、トリデシルアミン、トリラウリルアミン、ジメチルオクチルアミン、ジメチルデシルアミン、ジメチルラウリルアミン、ジメチルミリスチルアミン、ジメチルパルミチルアミン、ジメチルステアリルアミン、ジメチルベヘニルアミン、ジメチルヤシアミン、ジメチル牛脂アミン、ジメチル硬化牛脂アミン、ジデシルメチルアミン、ジラウリルメチルアミン、ジ硬化牛脂メチルアミン、ジオレイルメチルアミンなどを挙げることができる。
In the present invention, the secondary amine preferably has two alkyl groups having an average carbon number of 12 to 18. From a secondary amine having two alkyl groups having an average carbon number of 12 to 18, it is possible to easily produce a low density paper with excellent density reduction and little reduction in size.
Examples of the epihalohydrin used in the present invention include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin can be suitably used because of its low price, high reactivity, and excellent product usefulness.
In the present invention, the method for producing an amino compound obtained by reacting a secondary amine with an epihalohydrin is not particularly limited. For example, one kind of secondary amine is used alone, or a mixture of two or more kinds of secondary amines. Or as a mixture with other tertiary amines capable of reacting with epihalohydrin, the epihalohydrin is preferably 0.3 to 5.0 moles, more preferably 0.4 to 2.2 moles to the amine. More preferably, it is added at a molar ratio of 0.6 to 1.6, and if necessary, it is reacted at 20 to 100 ° C. using a solvent to remove unreacted epihalohydrin to produce an amino compound. According to this method, an azetidinium ring structure or an epoxy structure may be formed by a reaction between a secondary amine and an epihalohydrin. When the amount of epihalohydrin is less than 0.3 mol times the amount of amine, unreacted amine remains, and there is a possibility that the density reduction and sizing degree may decrease. When the amount of the epihalohydrin exceeds 5.0 moles with respect to the amine, the batch scale is greatly reduced, productivity is lowered, and there is a possibility that many impurities derived from epihalohydrin are generated. Examples of the solvent used in the reaction include water, methanol, ethanol, isopropanol, butanol, hexane, heptane, cyclohexane, toluene, dichloroethane, chloroform, tetrahydrofuran, dioxane and the like. Other tertiary amines that can react with epihalohydrin include, for example, trimethylamine, triethylamine, tributylamine, trihexylamine, trioctylamine, tridecylamine, trilaurylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, Dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethylbehenylamine, dimethyl palmamine, dimethyl beef tallow amine, dimethyl hardened tallow amine, didecylmethylamine, dilaurylmethylamine, dicured tallow methylamine, dioleylmethylamine And so on.
本発明において、アミノ化合物は、水や溶剤に乳化、分散又は溶解することを容易としたり、製品安定性を向上させる目的で、酸により塩として用いることができる。用いる酸に特に制限はなく、例えば、蟻酸、酢酸、酪酸、乳酸、クエン酸、リンゴ酸などの有機酸や、塩酸、硫酸、硝酸、リン酸などの無機酸を挙げることができる。これらの中で、蟻酸、酢酸、酪酸、乳酸、クエン酸、リンゴ酸などの有機酸を好適に用いることができる。酸により塩とするには、反応後のアミノ化合物に酸を添加して塩とすることができ、あるいは、酸の水溶液に、アミノ化合物を添加して塩とすることもできる。
本発明の低密度化剤の剤型に特に制限はなく、例えば、アミノ化合物をそのまま固体又は液状で用いることができ、あるいは、水や溶剤に乳化、分散又は溶解して用いることもできる。また、低密度化剤としての性能を損なわない範囲で、微量の界面活性剤などを用いて、水や溶剤に乳化、分散又は溶解して使用することもできる。
In the present invention, the amino compound can be used as a salt with an acid for the purpose of facilitating emulsification, dispersion or dissolution in water or a solvent, or improving product stability. The acid to be used is not particularly limited, and examples thereof include organic acids such as formic acid, acetic acid, butyric acid, lactic acid, citric acid and malic acid, and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. Among these, organic acids such as formic acid, acetic acid, butyric acid, lactic acid, citric acid, and malic acid can be suitably used. In order to form a salt with an acid, an acid can be added to the amino compound after the reaction to make a salt, or an amino compound can be added to an acid aqueous solution to make a salt.
There is no restriction | limiting in particular in the dosage form of the density reducing agent of this invention, For example, an amino compound can be used in solid or liquid state as it is, or it can also emulsify, disperse | distribute or melt | dissolve in water and a solvent, and can also use it. Further, it can be used by emulsifying, dispersing or dissolving in water or a solvent using a trace amount of a surfactant or the like as long as the performance as a density reducing agent is not impaired.
本発明の低密度紙の製造方法においては、紙の製造に使用するパルプに、本発明の紙用低密度化剤を添加する。本発明の紙用低密度化剤をパルプに添加する工程としては、例えば、離解工程直後、叩解前後、薬品などを添加する紙料調成前後、抄紙前、古紙の再生処理前後などを挙げることができる。
本発明方法において、紙の製造に使用するパルプに対する紙用低密度化剤の添加量に特に制限はないが、パルプ１００質量部に対しアミノ化合物量として０.０１〜１０.０質量部であることが好ましく、０.０５〜５.０質量部であることがより好ましく、０.１〜３.０質量部であることがさらに好ましい。
本発明方法に使用するパルプに特に制限はなく、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、古紙再生パルプなどの植物繊維、パルプモールドなどの繊維材料などを挙げることができる。また、本発明方法により製造する低密度紙は、植物繊維、その他の繊維を膠着させて製造したものであって、素材としてレーヨン、ポリエステルなどの合成高分子物質を用いて製造した合成紙や、繊維状無機材料を配合した紙なども含まれる。
In the method for producing low-density paper of the present invention, the paper density-reducing agent of the present invention is added to the pulp used for paper production. Examples of the process of adding the paper densifying agent of the present invention to the pulp include immediately after the disaggregation process, before and after beating, before and after preparation of a paper material to which chemicals and the like are added, before paper making, and before and after recycling of used paper. Can do.
In the method of the present invention, the amount of the paper densifying agent added to the pulp used for the production of paper is not particularly limited, but is 0.01 to 10.0 parts by weight as an amino compound with respect to 100 parts by weight of the pulp. It is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass.
The pulp used in the method of the present invention is not particularly limited, and examples thereof include wood pulp obtained from broad-leaved trees, conifers, plant fibers such as bagasse, kenaf, bamboo pulp, and recycled paper, and fiber materials such as pulp molds. Can do. The low-density paper produced by the method of the present invention is produced by gluing plant fibers and other fibers, and synthetic paper produced using a synthetic polymer substance such as rayon or polyester as a material, Also included are papers containing fibrous inorganic materials.
本発明方法により製造する低密度紙の種類に特に制限はなく、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、ティッシュペーパー、トイレットペーパーなどの衛生用紙などの紙製品などを挙げることができる。紙の形態にも特に制限はなく、例えば、感熱記録紙、インクジェット記録紙、コート紙、アート紙、微コート紙などの塗被紙にも適用することができる。また、低密度化する目的にも特に制限はなく、例えば、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、層間剥離のしやすさ、吸水性、吸油性、吸樹脂性、不透明性、含水進伸度の低下、コスト低減、パルプ使用量の節減などを挙げることができる。
本発明方法においては、低密度化の性能を損なわない程度に、他の薬剤を添加することができる。他の薬剤としては、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。これらの他の薬剤は、紙料調成工程において、単独に添加することができ、あるいは、あらかじめ本発明の紙用低密度化剤に混合して添加することもできる。
There are no particular restrictions on the type of low-density paper produced by the method of the present invention. For example, corrugated paper such as newsprint, printing paper, recording paper, wrapping paper, paperboard, liner, core, wallpaper, base paper, and its backing Paper products such as sanitary paper such as paper, tissue paper, and toilet paper can be exemplified. The form of the paper is not particularly limited, and can be applied to coated paper such as thermal recording paper, ink jet recording paper, coated paper, art paper, and fine coated paper. Also, there is no particular limitation on the purpose of reducing the density, for example, easiness of turning, printability, flexibility, volume, texture, touch, etc., prevention of paper cracking, ease of delamination, water absorption, oil absorption Properties, resin-absorbing properties, opacity, reduced water content, cost reduction, and reduced pulp usage.
In the method of the present invention, other chemicals can be added to such an extent that the performance of reducing the density is not impaired. Other agents 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, and paper quality improving agents. , Fillers, pigments, dyes, antifoaming agents and the like. These other chemicals can be added alone in the paper preparation step, or can be added in advance to the paper density-reducing agent of the present invention.
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、低密度紙の評価は下記の方法により行った。
（１）低密度化性
ＪＩＳ Ｐ ８１１８：１９９８に従って、密度を測定し、下式により低密度化率を求めた。密度が小さいほど、低密度化率が大きいほど、低密度化性が良好である。
低密度化率（％）＝ {(Ａ−Ｂ)／Ａ} ×１００
Ａ：低密度化剤無添加時の密度
Ｂ：低密度化剤添加時の密度
（２）サイズ度
ＪＩＳ Ｐ ８１１２：２００４に従って、ステキヒト・サイズ度を測定した。
また、以下の実施例の文中において、平均炭素数はアミンの窒素原子に結合した１個のアルキル基又はアルケニル基の平均炭素数を表す。
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 Examples and Comparative Examples, low density paper was evaluated by the following method.
(1) Density reduction The density was measured in accordance with JIS P 8118: 1998, and the density reduction rate was determined by the following equation. The lower the density and the higher the density reduction rate, the better the density reduction.
Densification rate (%) = {(A−B) / A} × 100
A: Density without addition of a low-density agent B: Density with addition of a low-density agent (2) Sizing degree According to JIS P 8112: 2004, the Steecht sizing degree was measured.
In the text of the following examples, the average carbon number represents the average carbon number of one alkyl group or alkenyl group bonded to the nitrogen atom of the amine.
比較例１
広葉樹晒しクラフトパルプを、フリーネス４４０ｍＬ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、角型シートマシン［熊谷理機工業(株)］を用いて坪量８０ｇ／ｍ2となるように抄紙し、プレス機［熊谷理機工業(株)］により０.７ＭＰａで５分間プレスしたのち、ヤンキードライヤー［熊谷理機工業(株)］を用いて１０５℃で３分間乾燥して試験紙を得た。得られた試験紙の密度は０.６１０ｇ／ｃｍ3であり、サイズ度は０であった。
実施例１
フラスコに、アルキル基の平均炭素数１７.２の混合ジステアリルアミン［花王(株)、ファーミン(登録商標)Ｄ８６］１００.１ｇ（０.２モル）を仕込み、エピクロロヒドリン１８.５ｇ（０.２モル）を、７０℃で４時間かけて滴下し、滴下終了後さらに４時間反応した。反応終了後、減圧にして６ｋＰａの圧力下、５０℃で未反応のエピクロロヒドリンを留去してアミノ化合物を得た。次に、１０質量％となるように水を添加して、乳化液状の低密度化剤を得た。
広葉樹晒しクラフトパルプを、フリーネス４４０ｍＬ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、ラボスターラー［ヤマト(株)］を用いて撹拌しながら、低密度化剤中のアミノ化合物量として対パルプ０.８質量％になるように低密度化剤を添加し、５分間撹拌した。次に、角型シートマシン［熊谷理機工業(株)］を用いて坪量８０ｇ／ｍ2となるように抄紙し、プレス機［熊谷理機工業(株)］により０.７ＭＰａで５分間プレスしたのち、ヤンキードライヤー［熊谷理機工業(株)］を用いて１０５℃で３分間乾燥して低密度紙を得た。得られた低密度紙の密度は０.５５５ｇ／ｃｍ3、低密度化率９.０％であり、サイズ度は６２であった。
実施例２
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.６の混合ジオレイルアミン［ライオン(株)、アーミン(商品名)２Ｏ］１０１.６ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５６ｇ／ｃｍ3、低密度化率８.９％であり、サイズ度は１７であった。
実施例３
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.２の混合ジ硬化牛脂アミン［ライオン(株)、アーミン(商品名)２ＨＴ］１００.１ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５５ｇ／ｃｍ3、低密度化率９.０％であり、サイズ度は５７であった。
実施例４
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１２.７の混合ヤシアミン［ライオン(株)、アーミン(商品名)２Ｃ］７４.７ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６６ｇ／ｃｍ3、低密度化率７.２％であり、サイズ度は２３であった。
Comparative Example 1
A pulp slurry was prepared by beating hardwood bleached kraft pulp to 440 mL of freeness. This pulp slurry is made into a paper having a basis weight of 80 g / m 2 using a square sheet machine [Kumagaya Riki Kogyo Co., Ltd.], and is 0.7 MPa by a press machine [Kumagaya Riki Kogyo Co., Ltd.]. After pressing for 5 minutes, a test paper was obtained by drying at 105 ° C. for 3 minutes using a Yankee dryer [Kumagaya Riki Kogyo Co., Ltd.]. The density of the obtained test paper was 0.610 g / cm 3 and the sizing degree was 0.
Example 1
A flask was charged with 100.1 g (0.2 mol) of mixed distearylamine [Kao Corporation, Pharmin® D86] having an average alkyl group carbon number of 17.2 and 18.5 g of epichlorohydrin ( 0.2 mol) was added dropwise at 70 ° C. over 4 hours, and the reaction was further continued for 4 hours after completion of the addition. After completion of the reaction, unreacted epichlorohydrin was distilled off at 50 ° C. under reduced pressure and 6 kPa to obtain an amino compound. Next, water was added so that it might become 10 mass%, and the emulsified liquid low density agent was obtained.
A pulp slurry was prepared by beating hardwood bleached kraft pulp to 440 mL of freeness. While stirring this pulp slurry using a lab stirrer [Yamato Co., Ltd.], a density reducing agent was added so that the amount of amino compound in the density reducing agent was 0.8% by mass with respect to pulp. Stir for minutes. Next, paper is made using a square sheet machine [Kumagaya Riki Kogyo Co., Ltd.] so as to have a basis weight of 80 g / m 2, and it is 0.7 MPa by a press machine [Kumagaya Riki Kogyo Co., Ltd.] for 5 minutes. After pressing, a low density paper was obtained by drying at 105 ° C. for 3 minutes using a Yankee dryer [Kumaya Riki Kogyo Co., Ltd.]. The density of the obtained low density paper was 0.555 g / cm 3 , the density reduction rate was 9.0%, and the sizing degree was 62.
Example 2
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 101.6 g (0.2 mol) of mixed dioleylamine having an average carbon number of 17.6 [Lion Corporation, Armin (trade name) 2O] A density reducing agent was obtained in the same manner as in Example 1 except that was used.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.556 g / cm 3 , the density reduction rate was 8.9%, and the sizing degree was 17.
Example 3
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 100.1 g (0.2%) of mixed dicured tallow amine [Lion Corporation, Armin (trade name) 2HT] having an average carbon number of 17.2 Mol) was used in the same manner as in Example 1 to obtain a densifying agent.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.555 g / cm 3 , the density reduction rate was 9.0%, and the sizing degree was 57.
Example 4
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 74.7 g (0.2 mol) of mixed coconut amine [Lion Corporation, Armin (trade name) 2C] having an average carbon number of 12.7 A density reducing agent was obtained in the same manner as in Example 1 except that it was used.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.566 g / cm 3 , the density reduction rate was 7.2%, and the sizing degree was 23.
実施例５
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.２の混合ジステアリルアミン７３.１ｇ（０.１４モル）と平均炭素数１２.７の混合ヤシアミン２２.４ｇ（０.０６モル）からなる平均炭素数１５.９の混合アミンを使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５８ｇ／ｃｍ3、低密度化率８.５％であり、サイズ度は５２であった。
実施例６
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.２の混合ジステアリルアミン８０.１ｇ（０.１６モル）と５０質量％ジメチルアミン水溶液３.６ｇ（０.０４モル）からなる混合アミンを使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６３ｇ／ｃｍ3、低密度化率７.７％であり、サイズ度は２０であった。
実施例７
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、メチルステアリルアミン５６.７ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６８ｇ／ｃｍ3、低密度化率６.９％であり、サイズ度は２７であった。
実施例８
使用するエピクロロヒドリンの量を２７.８ｇ（０.３モル）とした以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５９ｇ／ｃｍ3、低密度化率８.４％であり、サイズ度は４９であった。
実施例９
使用するエピクロロヒドリンの量を３７.０ｇ（０.４モル）とした以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６２ｇ／ｃｍ3、低密度化率７.９％であり、サイズ度は２７であった。
Example 5
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 73.1 g (0.14 mol) of mixed distearylamine having an average carbon number of 17.2 and 22.1 of mixed coconutamine having an average carbon number of 12.7. A densifying agent was obtained in the same manner as in Example 1 except that a mixed amine having an average carbon number of 15.9 consisting of 4 g (0.06 mol) was used.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.558 g / cm 3 , the density reduction rate was 8.5%, and the sizing degree was 52.
Example 6
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 80.1 g (0.16 mol) of mixed distearylamine having an average carbon number of 17.2 and 3.6 g (0 The density reducing agent was obtained in the same manner as in Example 1 except that a mixed amine consisting of .04 mol) was used.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.563 g / cm 3 , the density reduction ratio was 7.7%, and the sizing degree was 20.
Example 7
A density reducing agent was obtained in the same manner as in Example 1 except that 56.7 g (0.2 mol) of methylstearylamine was used instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2. .
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.568 g / cm 3 , the density reduction rate was 6.9%, and the sizing degree was 27.
Example 8
A density reducing agent was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin used was 27.8 g (0.3 mol).
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.559 g / cm 3 , the density reduction ratio was 8.4%, and the sizing degree was 49.
Example 9
A densifying agent was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin used was 37.0 g (0.4 mol).
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.562 g / cm 3 , the density reduction rate was 7.9%, and the sizing degree was 27.
実施例１０
使用するエピクロロヒドリンの量を１３.０ｇ（０.１４モル）とした以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５６ｇ／ｃｍ3、低密度化率８.９％であり、サイズ度は５８であった。
実施例１１
使用するエピクロロヒドリンの量を９.３ｇ（０.１モル）とした以外は、実施例１と同様にしてアミノ化合物を得た。次に、１０質量％となるように蟻酸４.６ｇ（０.１モル）を含む水を添加して、乳化液状の低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５６ｇ／ｃｍ3、低密度化率８.９％であり、サイズ度は３６であった。
実施例１２
フラスコに、エピクロロヒドリン１８.５ｇ（０.４モル）を仕込み、溶融させたアルキル基の平均炭素数１７.２の混合ジステアリルアミン１００.１ｇ（０.２モル）を７０℃で４時間かけて滴下し、滴下終了後さらに４時間反応した。反応終了後、減圧にして６ｋＰａの圧力下、５０℃で未反応のエピクロロヒドリンを留去してアミノ化合物を得た。次に、１０質量％となるように水を添加して、乳化液状の低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６１ｇ／ｃｍ3、低密度化率８.０％であり、サイズ度は６１であった。
実施例１３
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.２の混合ジステアリルアミン８０.１ｇ（０.１６モル）と３０質量％トリメチルアミン水溶液７.９ｇ（０.０４モル）からなる混合アミンを使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５６２ｇ／ｃｍ3、低密度化率７.９％であり、サイズ度は２６であった。
実施例１４
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、平均炭素数１７.２の混合ジステアリルアミン８０.１ｇ（０.１６モル）とラウリルジメチルアミン［花王(株)、ファーミン (登録商標)ＤＭ０８９８］８.５ｇ（０.０４モル）からなる混合アミンを使用した以外は、実施例１と同様にしてアミノ化合物を得た。次に、１０質量％となるように蟻酸３.７ｇ（０.０８モル）を含む水を添加して、乳化液状の低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５５７ｇ／ｃｍ3、低密度化率８.７％であり、サイズ度は５７であった。
Example 10
A density reducing agent was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin used was 13.0 g (0.14 mol).
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.556 g / cm 3 , the density reduction rate was 8.9%, and the sizing degree was 58.
Example 11
An amino compound was obtained in the same manner as in Example 1 except that the amount of epichlorohydrin used was changed to 9.3 g (0.1 mol). Next, water containing 4.6 g (0.1 mol) of formic acid so as to be 10% by mass was added to obtain an emulsified liquid density reducing agent.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.556 g / cm 3 , the density reduction rate was 8.9%, and the sizing degree was 36.
Example 12
A flask was charged with 18.5 g (0.4 mol) of epichlorohydrin, and 100.1 g (0.2 mol) of a mixed distearylamine having an average carbon number of 17.2 of the molten alkyl group was 4 at 70 ° C. The solution was added dropwise over a period of time, and reacted for another 4 hours after the completion of the addition. After completion of the reaction, unreacted epichlorohydrin was distilled off at 50 ° C. under reduced pressure and 6 kPa to obtain an amino compound. Next, water was added so that it might become 10 mass%, and the emulsified liquid low density agent was obtained.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.561 g / cm 3 , the density reduction rate was 8.0%, and the sizing degree was 61.
Example 13
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 80.1 g (0.16 mol) of mixed distearylamine having an average carbon number of 17.2 and 7.9 g of 30% by weight trimethylamine aqueous solution (0.1%) A density reducing agent was obtained in the same manner as in Example 1 except that a mixed amine consisting of (04 mol) was used.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.562 g / cm 3 , the density reduction rate was 7.9%, and the sizing degree was 26.
Example 14
Instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2, 80.1 g (0.16 mol) of mixed distearylamine having an average carbon number of 17.2 and lauryldimethylamine [Kao Corporation, Farmin ( (Registered trademark) DM0898] An amino compound was obtained in the same manner as in Example 1 except that a mixed amine consisting of 8.5 g (0.04 mol) was used. Next, water containing 3.7 g (0.08 mol) of formic acid was added so as to be 10% by mass to obtain an emulsified liquid reducing agent.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.557 g / cm 3 , the density reduction ratio was 8.7%, and the sizing degree was 57.
比較例２
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、ジデシルアミン５９.５ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５７１ｇ／ｃｍ3、低密度化率６.４％であり、サイズ度は２であった。
比較例３
平均炭素数１７.２の混合ジステアリルアミン１００.１ｇの代わりに、ラウリルジメチルアミン４２.７ｇ（０.２モル）を使用した以外は、実施例１と同様にして低密度化剤を得た。
得られた低密度化剤を用い、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５７３ｇ／ｃｍ3、低密度化率６.１％であり、サイズ度は０であった。
比較例４
低密度化剤として、ステアリルアルコールのエチレンオキシド５モル付加物を、水により１０質量％となるように乳化・分散させた分散液を用いた以外は、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５８８ｇ／ｃｍ3、低密度化率３.６％であり、サイズ度は０であった。
比較例５
低密度化剤として、ペンタエリスリトールトリステアレート／ラウリルアルコールのエチレンオキシド１０モル・プロピレンオキシド７.５モルランダム付加物（質量比９０／１０）を、水により１０質量％となるように乳化・分散させた分散液を用いた以外は、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５７６ｇ／ｃｍ3、低密度化率５.６％であり、サイズ度は０であった。
比較例６
低密度化剤として、エチレンジアミンジオレイルアミド酢酸塩／ラウリルアルコールのエチレンオキシド１０モル・プロピレンオキシド７.５モルランダム付加物（質量比９０／１０）を、水により１０質量％となるように乳化・分散させた分散液を用いた以外は、実施例１と同じ操作を行って、低密度紙を得た。得られた低密度紙の密度は０.５７５ｇ／ｃｍ3、低密度化率５.７％であり、サイズ度は０であった。
実施例１〜１４及び比較例２〜３で用いた低密度化剤の合成に用いたアミン及びエピハロヒドリンの種類と量を第１表に、比較例１及び比較例４〜６で用いた低密度化剤を第２表に、実施例１〜１４及び比較例１〜６で得られた低密度紙の密度、低密度化率及びサイズ度を第３表に示す。
Comparative Example 2
A densifying agent was obtained in the same manner as in Example 1 except that 59.5 g (0.2 mol) of didecylamine was used instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2.
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.571 g / cm 3 , the density reduction ratio was 6.4%, and the sizing degree was 2.
Comparative Example 3
A density reducing agent was obtained in the same manner as in Example 1 except that 42.7 g (0.2 mol) of lauryldimethylamine was used instead of 100.1 g of mixed distearylamine having an average carbon number of 17.2. .
Using the obtained density-reducing agent, the same operation as in Example 1 was performed to obtain a low-density paper. The density of the obtained low density paper was 0.573 g / cm 3 , the density reduction rate was 6.1%, and the sizing degree was 0.
Comparative Example 4
As the density reducing agent, the same operation as in Example 1 was performed except that a dispersion obtained by emulsifying and dispersing stearyl alcohol ethylene oxide 5 mol adduct so as to be 10% by mass with water was performed. I got paper. The density of the obtained low density paper was 0.588 g / cm 3 , the density reduction rate was 3.6%, and the sizing degree was 0.
Comparative Example 5
As a density reducing agent, pentaerythritol tristearate / lauryl alcohol ethylene oxide 10 mol / propylene oxide 7.5 mol random adduct (mass ratio 90/10) is emulsified and dispersed with water so as to be 10% by mass. A low density paper was obtained by performing the same operation as in Example 1 except that the above dispersion was used. The density of the obtained low density paper was 0.576 g / cm 3 , the density reduction ratio was 5.6%, and the sizing degree was 0.
Comparative Example 6
Emulsified / dispersed ethylenediaminediolaleamide acetate / ethylene lauryl alcohol 10 mol / propylene oxide 7.5 mol random adduct (mass ratio 90/10) with water as 10% by mass as density reducing agent A low density paper was obtained by performing the same operation as in Example 1 except that the dispersed liquid was used. The density of the obtained low density paper was 0.575 g / cm 3 , the density reduction rate was 5.7%, and the sizing degree was 0.
Table 1 shows the types and amounts of amine and epihalohydrin used in the synthesis of the low-density agent used in Examples 1 to 14 and Comparative Examples 2 to 3, and the low density used in Comparative Examples 1 and 4 to 6 Table 2 shows the density of the low-density paper obtained in Examples 1 to 14 and Comparative Examples 1 to 6, and the degree of size reduction.
第３表に見られるように、本発明の低密度化剤を用いて製造した実施例１〜１４の低密度紙は、密度が低く、低密度化性が良好であり、サイズ度が高い。これに対して、アルキル基の炭素数が１０である２級アミンとエピクロロヒドリンとの反応物を用いて製造した比較例２の低密度紙及び３級アミンとエピクロロヒドリンとの反応物を用いて製造した比較例３の低密度紙では、低密度化効果は多少得られるものの、サイズ度が全く得られていない。また、従来の低密度化剤であるステアリルアルコールのエチレンオキシド付加物を用いた比較例４の低密度紙、従来の低密度化剤であるペンタエリスリトールトリステアレートと非イオン界面活性剤を併用した比較例５の低密度紙、従来の低密度化剤であるエチレンジアミンジオレイルアミド酢酸塩と非イオン界面活性剤を併用した比較例６の低密度紙では、いずれも低密度化効果は多少得られるものの、サイズ度が全く得られていない。 As seen in Table 3, the low-density papers of Examples 1 to 14 produced using the density-reducing agent of the present invention have a low density, good density reduction, and a high sizing degree. In contrast, the low density paper of Comparative Example 2 produced using a reaction product of a secondary amine having an alkyl group with 10 carbon atoms and epichlorohydrin, and the reaction of a tertiary amine with epichlorohydrin. In the low density paper of Comparative Example 3 produced using the product, although the effect of reducing the density is somewhat obtained, the sizing degree is not obtained at all. Moreover, the comparison of the low density paper of the comparative example 4 using the ethylene oxide adduct of stearyl alcohol which is a conventional density reducing agent, and the combined use of the conventional density reducing agent pentaerythritol tristearate and a nonionic surfactant. Although the low density paper of Example 5 and the low density paper of Comparative Example 6 in which ethylenediaminedioleamide acetate, which is a conventional densification agent, and a nonionic surfactant are used in combination, the density reduction effect is somewhat obtained. No degree of sizing is obtained.
本発明の低密度化剤及び低密度紙の製造方法によれば、低密度性に優れ、サイズ度低下の少ない低密度紙を容易に製造することができ、パルプ原料の使用量を低減し、地球環境問題に寄与することができる。 According to the low-density agent and the low-density paper manufacturing method of the present invention, low-density paper can be easily manufactured with low density and low in size reduction, reducing the amount of pulp raw material used, It can contribute to global environmental problems.
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| JP2000141881A (en) * | 1998-11-13 | 2000-05-23 | Nicca Chemical Co Ltd | Ink jet recording paper and water-resistant improver therefor |
| JP2004143634A (en) * | 2002-10-25 | 2004-05-20 | Katayama Chem Works Co Ltd | Fixing agent of size for paper-making processes, and method for producing paper |
| JP2005188001A (en) * | 2003-12-26 | 2005-07-14 | Nicca Chemical Co Ltd | Method for producing coated paper |
| WO2005064079A1 (en) * | 2003-12-26 | 2005-07-14 | Nippon, Paper, Industries, Co., Ltd. | Coated paper adapted to newsprint printing ink and process for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61192734A (en) * | 1985-02-21 | 1986-08-27 | Mitsubishi Monsanto Chem Co | Production of water-soluble cationic polymer |
| JP2000141881A (en) * | 1998-11-13 | 2000-05-23 | Nicca Chemical Co Ltd | Ink jet recording paper and water-resistant improver therefor |
| JP2004143634A (en) * | 2002-10-25 | 2004-05-20 | Katayama Chem Works Co Ltd | Fixing agent of size for paper-making processes, and method for producing paper |
| JP2005188001A (en) * | 2003-12-26 | 2005-07-14 | Nicca Chemical Co Ltd | Method for producing coated paper |
| WO2005064079A1 (en) * | 2003-12-26 | 2005-07-14 | Nippon, Paper, Industries, Co., Ltd. | Coated paper adapted to newsprint printing ink and process for producing the same |
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