JP4518464B2 - Paper processing agent and paper - Google Patents
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- JP4518464B2 JP4518464B2 JP2003186089A JP2003186089A JP4518464B2 JP 4518464 B2 JP4518464 B2 JP 4518464B2 JP 2003186089 A JP2003186089 A JP 2003186089A JP 2003186089 A JP2003186089 A JP 2003186089A JP 4518464 B2 JP4518464 B2 JP 4518464B2
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- 125000002947 alkylene group Chemical group 0.000 description 10
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- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
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- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 description 1
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- 238000005809 transesterification reaction Methods 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は紙類に柔軟性、吸水性を付与することのできる紙類処理剤及び、その処理剤で処理した紙類に関する。
【０００２】
【従来の技術】
紙や紙製品、特にトイレットペーパーやティッシュペーパー等の家庭用の紙類には適度な柔軟性、吸水性が要求されている。このような要求に応えるため、処理剤によって紙類を処理することが行われており、従来より、グリセリン、脂肪酸エステル類、油脂類、パラフィン類等を用いて処理する方法が知られている。また第四級アンモニウム塩で処理する方法（特許文献１）、第四級アンモニウム塩とグリセリン、脂肪族アルコールを含む処理剤で処理する方法（特許文献２）、ポリシロキサンで処理する方法（特許文献３）等が知られている。
【０００３】
【特許文献１】
特開昭６３−１６５５９７号公報
【特許文献２】
特開平４−１００９９５号公報
【特許文献３】
特開平３−９００号公報
【０００４】
【発明が解決しようとする課題】
しかしながら、グリセリンを用いて処理する方法では、紙類に十分な柔軟性を付与するために多量のグリセリンを使用する必要があり、処理コストが高くつくという問題があった。また脂肪酸エステル類、油脂類、パラフィン類を用いて処理する方法では、処理剤が油性成分で構成されるために紙類に要求される吸水性を阻害し、手にべたつき感が残り使用者に不快感を与え易いという問題があった。一方、特許文献１、２に記載されている方法は、皮膚刺激性のある第四級アンモニウム塩を用いるため安全性が十分とは言い難かった。また特許文献３に記載されている方法は、柔軟性と吸水性とを同時に付与することは困難であるとともに、柔軟性付与効果の高いアミノ変性型のポリシロキサンを用いた場合には、紙類の白度が低下するという問題があった。
【０００５】
本発明は上記従来の問題に鑑みなされたもので、従来の紙類処理剤の欠点を解決し、紙類に柔軟性、吸水性を効果的に付与できる紙類処理剤及び紙類を提供することを目的とする。
【０００６】
【課題を解決するための手段】
即ち本発明の紙類処理剤は、三価以上の多価アルコール類と、二塩基酸類及び二塩基酸類の１／１．５倍モル以上、４倍モル以下の脂肪酸類の混合物との反応により得られるエステル化合物を必須成分とすることを特徴とする。
【０００７】
また本発明の紙類は、上記紙類処理剤によりエステル化合物が０．０１〜１０．０重量％含有されるように紙類処理剤により処理されていることを特徴とする。
【０００８】
【発明の実施の形態】
本発明の紙類処理剤は、三価以上の多価アルコール類と、二塩基酸類及び脂肪酸類の混合物とのエステル反応生成物（エステル化合物）の少なくとも１種を必須成分として含有する。エステル化合物を構成する三価以上の多価アルコール類としては、１分子中に水酸基を３個以上有する多価アルコールやそのアルキレンオキシド付加体が挙げられる。三価以上の多価アルコールとしては、グリセリン、ソルビトール、ペンタエリスリトール、トリメチロールプロパン、ヒマシ油、水添硬化ヒマシ油等が挙げられる。これらのうち、グリセリン、水添硬化ヒマシ油、が好ましい。多価アルコールのアルキレンオキシド付加体は、多価アルコールにアルカリの存在下で、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等のアルキレンオキシドを付加させる等により得ることができる。多価アルコールのアルキレンオキシド付加体は、多価アルコールの全ての水酸基にアルキレンオキシドが付加した構造のものであっても、多価アルコールの水酸基の一部にアルキレンオキシドが付加した構造のものであっても良い。またアルキレンオキシドは１種のみが付加したものでも２種以上が付加したものでも良く、２種以上のアルキレンオキシドが付加した付加体は、ランダム付加体でもブロック付加体でも良い。アルキレンオキシド付加体としてはエチレンオキシド付加体が好ましい。またアルキレンオキシドの多価アルコールに対する付加モル数は、多価アルコール１モル当たり１〜１００モルが好ましい。
【００１０】
一方、二塩基酸類としては、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸などの飽和二塩基酸、マレイン酸等の不飽和二塩基酸やが挙げられるが、アジピン酸、セバシン酸、コハク酸、スベリン酸が、柔軟化効果の高い紙類処理剤を得る上で好まし。また脂肪酸類としては、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、ベヘン酸が挙げられるが、ステアリン酸、ベヘン酸やこれらの低級アルコールエステルが好ましい。
【００１１】
エステル化合物は、三価以上の多価アルコール類と、二塩基酸と脂肪酸との混合物を、触媒の存在下で脱水縮合してエステル化させるか、或いは、三価以上の多価アルコール類と、二塩基酸の低級アルコールエステルと脂肪酸の低級アルコールエステルの混合物とのエステル交換反応によるエステル化によって得ることができる。
【００１２】
上記脱水縮合によるエステル化の触媒としては、ｐ−トルエンスルホン酸ナトリウム、水酸化ナトリウム、水酸化カリウム、ナトリウムアルコラート等が用いられる。エステル化合物を得る場合、二塩基酸類と脂肪酸類との混合割合は、脂肪酸類は二塩基酸類の１／１．５倍モル以上、４倍モル以下である。
【００１３】
三価以上の多価アルコール類と二塩基酸とのエステルに較べ、三価以上の多価アルコール類と、二塩基酸及び脂肪酸の混合物とのエステルは、末端にアルキル基を有することによって、紙類にすべり感や柔軟性を付与できるなどの効果がある。
【００１４】
本発明の紙類処理剤には、上記エステル化合物の他に、更に必要に応じて他の成分、例えば鉱物油、脂肪酸エステル等の平滑剤、ポリ（オキシエチレン）アルキルエーテル、ポリ（オキシエチレン）脂肪酸エステル等の乳化剤等を配合することもできる。
【００１５】
本発明の紙類処理剤は、上記エステル化合物を水に溶解または分散した水溶液或いは乳化液として使用する。本発明の紙類処理剤により紙類の処理を行う場合、通常、上記エステル化合物を１．０〜５０．０重量％程度含む水溶液、乳化液として使用する。この水溶液、乳化液中には保湿成分等の他の成分を更に配合することができる。本発明の紙類処理剤により紙類を処理するには、紙類に噴霧器によりスプレーする方法、含浸機により浸漬処理する方法等が挙げられる。本発明の紙類は、上記本発明の処理剤によって処理されたものであって、処理後の紙類中に上記エステル化合物が固形換算量として０．０１〜１０．０重量％含有されているものである。より好ましくは、処理後の紙類中に上記エステル化合物が固形分換算量として０．１〜５．０重量％含有されていることである。上記エステル化合物の含有率が０．０１重量％未満では、紙類に十分な柔軟性が付与されない。また、１０．０重量％を超えるとベタ付き感などによりかえって紙類の風合い等が悪くなる。
【００１６】
本発明処理剤が処理対象とする紙類とは、ペーパータオル、ティッシュペーパー、トイレットペーパー、フェイシャルティッシュ、ちり紙、ペーパーナプキン京花紙等が挙げられる。
【００１７】
【実施例】
以下、実施例を挙げて本発明を更に詳細に説明する。実施例の処理剤に使用したエステル化合物は以下の通りである。
【００１８】
エステル化合物ａ：グリセリン１．０モル、セバシン酸０．６モルの割合でエステル化反応させて得たエステル化合物。
【００１９】
エステル化合物ｂ：グリセリンエチレンオキシド（９モル）付加体１．０モル、アジピン酸０．８モル及びステアリン酸１．４モルの割合でエステル化反応させて得たエステル化合物。
【００２０】
エステル化合物ｃ：ペンタエリスリトール１．０モル、ひまし油エチレンオキシド（２０モル）付加体１．０モル、セバシン酸１．５モル、ステアリン酸１．０モルの割合でエステル化反応させて得たエステル化合物。
【００２１】
エステル化合物ｄ：グリセリン１．０モル、ポリオキシエチレンポリオキシプロピレングリコール（ランダム重合体：平均分子量１３０００、エチレンオキシド成分比７５重量％）０．５モル、ポリエチレングリコール（平均分子量６０００）０．３モル、セバシン酸１．２モルの割合でエステル化反応させて得たエステル化合物。
【００２２】
エステル化合物ｅ：グリセリンエチレンオキシド（９モル）付加体１．０モル、ポリオキシエチレンポリオキシプロピレングリコール（ランダム重合体：平均分子量１３０００、エチレンオキシド成分比７５重量％）０．５モル、セバシン酸０．８モル、ベヘン酸０．５モルの割合でエステル化反応させて得たエステル化合物。
【００２３】
エステル化合物ｆ：エステル化合物ａとエステル化合物ｃの１：１（重量比）混合物。
【００２４】
エステル化合物ｇ：エステル化合物ｂ、エステル化合物ｄ、エステル化合物ｅの１：１：１（モル比）混合物。
【００２５】
実施例１〜８
上記エステル化合物を用い、エステル化合物の含有率が４０．０重量％となるように、処理剤を水に溶解又は分散させて表１に示す処理液を調整した。各処理液を、柔軟処理を施していないティッシュペーパーに、付着量が表１に示す量（エステル化合物の固形分換算量）となるようにスプレー噴霧処理した後、２４時間風乾させ、その後、更に恒温恒湿室（温度２０℃、湿度６５％ＲＨ）内で１２時間以上放置し、含有水分率が平衡になった後、ティッシュペーパーの柔軟性、吸水性を評価した。結果を未処理のティッシュペーパーの場合とあわせて表１に示す。
【００２６】
処理後のティッシュペーパーの柔軟性、吸水性は以下のようにして評価した。
柔軟性
被試験紙を５枚片手で握り、柔軟性の官能性評価を行った。評価基準は以下の５段階とした。
５：非常に柔らかい
４：柔らかい
３：やや柔らかい
２：柔軟剤未使用と同等
１：柔らかくない
【００２７】
吸水性
処理後のティッシュペーパーにスポイトから水滴（イオン交換水）を滴下し、吸水状態を未処理のティッシュペーパーと比較して以下の基準で評価した。
○：未処理のものに比べて吸水性が同程度乃至は良好となる。
×：未処理のものより吸水性が悪くなり、紙本来の吸水性が阻害される。
【００２８】
【表１】
比較例１〜１０
表２に示す処理剤主成分の含有率が４０．０重量％（乳化剤を併用した場合には乳化剤も含めた合計の含有率が４０重量％）となるように水に溶解又は分散させて表２に示す処理液を調整した。比較例８〜１０については、表２に示す量の乳化剤を併用し、温水加水法により乳化して処理液を調整した。尚、乳化剤として、比較例８はポリオキシエチレン（３０モル）ラウリルエーテルを、比較例９はポリオキシエチレン（２０モル）ステアリルエーテルを、比較例１０はポリオキシエチレン（８モル）セチルエーテルを使用した。
【００３０】
【表２】
各処理液を、柔軟処理を施していないティッシュペーパーに表２に示す処理剤主成分付着量（乳化剤を併用した場合には乳化剤も含めた合計の付着量）となるように噴霧処理した後、２４時間風乾させ、その後、更に恒温恒湿室（温度２０℃、湿度６５％ＲＨ）内で１２時間以上放置して、含有水分率が平衡になった後、ティッシュペーパーの柔軟性、吸水性を実施例と同様に評価した。これらの結果を表２に示す。
【００３２】
【発明の効果】
以上説明したように本発明の紙類処理剤は、紙類に優れた柔軟性を付与できる。従来の処理剤のように柔軟性を付与しようとすると紙類の吸水性が低下するという問題がなく、本発明の処理剤で処理した紙類は柔軟性．吸水性に優れる効果がある。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper processing agent capable of imparting flexibility and water absorption to paper and paper treated with the processing agent.
[0002]
[Prior art]
Appropriate flexibility and water absorption are required for paper and paper products, especially household paper such as toilet paper and tissue paper. In order to meet such demands, papers are treated with a treating agent, and conventionally, a method of treating with glycerin, fatty acid esters, fats and oils, paraffins, and the like is known. Also, a method of treating with a quaternary ammonium salt (Patent Document 1), a method of treating with a treating agent containing a quaternary ammonium salt, glycerin and an aliphatic alcohol (Patent Document 2), a method of treating with a polysiloxane (Patent Document) 3) etc. are known.
[0003]
[Patent Document 1]
JP-A 63-165597 [Patent Document 2]
JP-A-4-100995 [Patent Document 3]
Japanese Patent Laid-Open No. 3-900 [0004]
[Problems to be solved by the invention]
However, in the method of treating with glycerin, it is necessary to use a large amount of glycerin in order to impart sufficient flexibility to papers, and there is a problem that the treatment cost is high. Also, in the method of treatment using fatty acid esters, fats and oils, paraffins, the treatment agent is composed of oily components, which inhibits the water absorption required for papers, and the user feels sticky to the user. There was a problem that it was easy to give discomfort. On the other hand, the methods described in Patent Documents 1 and 2 are not sufficiently safe because they use a skin-irritating quaternary ammonium salt. In addition, the method described in Patent Document 3 is difficult to simultaneously impart flexibility and water absorption, and when an amino-modified polysiloxane having a high flexibility imparting effect is used, There was a problem that the whiteness of the paper decreased.
[0005]
The present invention has been made in view of the above-described conventional problems, and provides a paper processing agent and papers that can solve the disadvantages of conventional paper processing agents and can effectively impart flexibility and water absorption to papers. For the purpose.
[0006]
[Means for Solving the Problems]
That is, the paper treating agent of the present invention is obtained by reacting a trihydric or higher polyhydric alcohol with a dibasic acid and a mixture of fatty acids of 1 / 1.5 times mol and 4 times mol of dibasic acids. that the resulting ester compound as essential components you characterized.
[0007]
The paper of the present invention is characterized in that it is treated with the paper treating agent so that the ester compound is contained in an amount of 0.01 to 10.0% by weight with the paper treating agent.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The paper treating agent of the present invention contains at least one ester reaction product (ester compound ) of a trihydric or higher polyhydric alcohol and a mixture of dibasic acids and fatty acids as an essential component. Examples of the trihydric or higher polyhydric alcohols constituting the ester compound include polyhydric alcohols having 3 or more hydroxyl groups in one molecule and alkylene oxide adducts thereof. Examples of the trihydric or higher polyhydric alcohol include glycerin, sorbitol, pentaerythritol, trimethylolpropane, castor oil, hydrogenated hydrogenated castor oil, and the like. Of these, glycerin and hydrogenated hydrogenated castor oil are preferred. An alkylene oxide adduct of a polyhydric alcohol can be obtained by adding an alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide to the polyhydric alcohol in the presence of an alkali. The alkylene oxide adduct of a polyhydric alcohol has a structure in which alkylene oxide is added to all hydroxyl groups of the polyhydric alcohol, but has a structure in which alkylene oxide is added to part of the hydroxyl groups of the polyhydric alcohol. May be. Further, the alkylene oxide may be a single adduct or two or more adducts, and the adduct with two or more alkylene oxides added may be a random adduct or a block adduct. The alkylene oxide adduct is preferably an ethylene oxide adduct. The number of moles of alkylene oxide added to the polyhydric alcohol is preferably 1 to 100 moles per mole of polyhydric alcohol.
[0010]
On the other hand, examples of the dibasic acids include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, saturated dibasic acid such as sebacic acid, and unsaturated dibasic acid such as maleic acid. Adipic acid, sebacic acid, succinic acid, and suberic acid are preferred for obtaining paper processing agents with a high softening effect. Examples of the fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, and behenic acid, but stearic acid, behenic acid, and lower alcohol esters thereof are preferable.
[0011]
The ester compound may be esterified by dehydration condensation of a mixture of a trihydric or higher polyhydric alcohol and a dibasic acid and a fatty acid in the presence of a catalyst, or a trihydric or higher polyhydric alcohol and It can be obtained by esterification by a transesterification reaction of a mixture of a lower alcohol ester of a dibasic acid and a lower alcohol ester of a fatty acid.
[0012]
As the catalyst for esterification by dehydration condensation, sodium p-toluenesulfonate, sodium hydroxide, potassium hydroxide, sodium alcoholate, or the like is used. When obtaining an ester compound , the mixing ratio of dibasic acids and fatty acids is 1 / 1.5 times mol or more and 4 times mol or less of dibasic acids of dibasic acids .
[0013]
Compared to ester le with trihydric or higher polyhydric alcohols and dibasic acids, and tri- or higher polyhydric alcohols, ester le with a mixture of dibasic acids and fatty acids, by having an alkyl group at the end It has the effect of imparting a slipperiness and flexibility to papers.
[0014]
In addition to the above ester compounds, the paper treating agent of the present invention further contains other components as necessary, for example, smoothing agents such as mineral oil and fatty acid esters, poly (oxyethylene) alkyl ethers, poly (oxyethylene) Emulsifiers such as fatty acid esters can also be blended.
[0015]
The paper treating agent of the present invention is used as an aqueous solution or emulsion in which the ester compound is dissolved or dispersed in water. When paper is treated with the paper treating agent of the present invention, it is usually used as an aqueous solution or emulsion containing about 1.0 to 50.0% by weight of the ester compound. In this aqueous solution and emulsion, other components such as a moisturizing component can be further blended. In order to treat paper with the paper treating agent of the present invention, a method of spraying paper with a sprayer, a method of dipping treatment with an impregnator, and the like can be mentioned. The paper of the present invention has been treated with the treatment agent of the present invention, and the ester compound is contained in the treated paper in an amount of 0.01 to 10.0% by weight as a solid conversion amount. Is. More preferably, the treated ester paper contains 0.1 to 5.0% by weight of the ester compound as a solid content conversion amount. When the content of the ester compound is less than 0.01% by weight, sufficient flexibility cannot be imparted to the papers. On the other hand, if it exceeds 10.0% by weight, the texture of the paper will be deteriorated due to the stickiness.
[0016]
Examples of the paper to be treated by the treatment agent of the present invention include paper towel, tissue paper, toilet paper, facial tissue, dust paper, paper napkin Kyoto flower paper and the like.
[0017]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples. The ester compounds used in the treatment agents of the examples are as follows.
[0018]
Ester compound a: ester compound obtained by esterification at a ratio of 1.0 mol of glycerol and 0.6 mol of sebacic acid.
[0019]
Ester compound b: an ester compound obtained by esterification at a ratio of 1.0 mol of glycerin ethylene oxide (9 mol) adduct, 0.8 mol of adipic acid and 1.4 mol of stearic acid.
[0020]
Ester compound c: an ester compound obtained by esterification at a ratio of 1.0 mol of pentaerythritol, 1.0 mol of castor oil ethylene oxide (20 mol) adduct, 1.5 mol of sebacic acid and 1.0 mol of stearic acid.
[0021]
Ester compound d: glycerol 1.0 mol, polyoxyethylene polyoxypropylene glycol (random polymer: average molecular weight 13000, ethylene oxide component ratio 75 wt%) 0.5 mol, polyethylene glycol (average molecular weight 6000) 0.3 mol, An ester compound obtained by an esterification reaction at a ratio of 1.2 mol of sebacic acid.
[0022]
Ester compound e: glycerin ethylene oxide (9 mol) adduct 1.0 mol, polyoxyethylene polyoxypropylene glycol (random polymer: average molecular weight 13000, ethylene oxide component ratio 75% by weight) 0.5 mol, sebacic acid 0.8 An ester compound obtained by an esterification reaction at a ratio of 0.5 mole of behenic acid.
[0023]
Ester compound f: 1: 1 (weight ratio) mixture of ester compound a and ester compound c.
[0024]
Ester compound g: 1: 1: 1 (molar ratio) mixture of ester compound b, ester compound d, and ester compound e.
[0025]
Examples 1-8
Using the ester compound, the treatment liquid shown in Table 1 was prepared by dissolving or dispersing the treatment agent in water so that the ester compound content was 40.0% by weight. Each treatment solution is spray-sprayed on tissue paper that has not been subjected to softening treatment so that the amount of adhesion is the amount shown in Table 1 (the amount converted to the solid content of the ester compound), then air-dried for 24 hours, and then further After leaving in a constant temperature and humidity chamber (temperature 20 ° C., humidity 65% RH) for 12 hours or more and the water content was balanced, the softness and water absorption of the tissue paper were evaluated. The results are shown in Table 1 together with the case of untreated tissue paper.
[0026]
The softness and water absorption of the treated tissue paper were evaluated as follows.
The flexibility test paper was evaluated by grasping 5 sheets of flexible test paper with one hand. The evaluation criteria were as follows.
5: Very soft 4: Soft 3: Slightly soft 2: Equivalent to softener not used 1: Not soft [0027]
Water drops (ion-exchanged water) were dropped from a dropper onto tissue paper after water absorption treatment, and the water absorption state was evaluated according to the following criteria in comparison with untreated tissue paper.
○: The water absorption is comparable or better than that of untreated.
X: Water absorption is worse than that of untreated paper, and the original water absorption of paper is inhibited.
[0028]
[Table 1]
Comparative Examples 1-10
The content of the main component of the treating agent shown in Table 2 is dissolved or dispersed in water so that the content is 40.0% by weight (when the emulsifier is used in combination, the total content including the emulsifier is 40% by weight). The processing liquid shown in 2 was prepared. About Comparative Examples 8-10, the emulsifier of the quantity shown in Table 2 was used together, and it emulsified with the warm water addition method, and adjusted the process liquid. As an emulsifier, Comparative Example 8 uses polyoxyethylene (30 mol) lauryl ether, Comparative Example 9 uses polyoxyethylene (20 mol) stearyl ether, and Comparative Example 10 uses polyoxyethylene (8 mol) cetyl ether. did.
[0030]
[Table 2]
After each treatment solution is spray-treated so that the amount of the treatment agent main component adhesion amount shown in Table 2 (total adhesion amount including the emulsifier when emulsifier is used together) on tissue paper not subjected to softening treatment, Allow to air dry for 24 hours, and then leave it in a constant temperature and humidity chamber (temperature 20 ° C., humidity 65% RH) for 12 hours or more to equilibrate the moisture content. Evaluation was performed in the same manner as in the examples. These results are shown in Table 2.
[0032]
【The invention's effect】
As described above, the paper treatment agent of the present invention can impart excellent flexibility to paper. There is no problem that the water absorption of papers decreases when trying to impart flexibility like conventional treatment agents, and papers treated with the treatment agent of the present invention are flexible. There is an effect excellent in water absorption.
Claims (2)
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295100A (en) * | 1992-04-22 | 1993-11-09 | Kao Corp | Self-dispersed water-based polyester resin, its production and surface treating agent composition for paper therefrom |
| JPH10226986A (en) * | 1997-02-13 | 1998-08-25 | Kouno Seishi Kk | Paper product and its production |
| WO1999063156A1 (en) * | 1998-06-02 | 1999-12-09 | Kao Corporation | Paper bulking agents |
| JP2003138498A (en) * | 2001-10-31 | 2003-05-14 | Miyoshi Oil & Fat Co Ltd | Treating agent for paper and paper |
| JP2003166195A (en) * | 2001-11-27 | 2003-06-13 | Japan Pmc Corp | Filler modifier, filler containing filler modifier and paper making method using the filler |
-
2003
- 2003-06-30 JP JP2003186089A patent/JP4518464B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05295100A (en) * | 1992-04-22 | 1993-11-09 | Kao Corp | Self-dispersed water-based polyester resin, its production and surface treating agent composition for paper therefrom |
| JPH10226986A (en) * | 1997-02-13 | 1998-08-25 | Kouno Seishi Kk | Paper product and its production |
| WO1999063156A1 (en) * | 1998-06-02 | 1999-12-09 | Kao Corporation | Paper bulking agents |
| JP2003138498A (en) * | 2001-10-31 | 2003-05-14 | Miyoshi Oil & Fat Co Ltd | Treating agent for paper and paper |
| JP2003166195A (en) * | 2001-11-27 | 2003-06-13 | Japan Pmc Corp | Filler modifier, filler containing filler modifier and paper making method using the filler |
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