JPS642717B2 - - Google Patents
Info
- Publication number
- JPS642717B2 JPS642717B2 JP1656580A JP1656580A JPS642717B2 JP S642717 B2 JPS642717 B2 JP S642717B2 JP 1656580 A JP1656580 A JP 1656580A JP 1656580 A JP1656580 A JP 1656580A JP S642717 B2 JPS642717 B2 JP S642717B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polymer
- paper
- sizing agent
- manufacturing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000004513 sizing Methods 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 229920000642 polymer Polymers 0.000 claims description 25
- 239000006185 dispersion Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 125000000129 anionic group Chemical group 0.000 claims description 12
- 229920006317 cationic polymer Polymers 0.000 claims description 11
- 235000013808 oxidized starch Nutrition 0.000 claims description 7
- 239000001254 oxidized starch Substances 0.000 claims description 7
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 5
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- -1 alkyl ketene dimer Chemical compound 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical class CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical class CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 229920002978 Vinylon Polymers 0.000 description 1
- OBHBXMOWIKWQNI-UHFFFAOYSA-N [3-(dimethylamino)-2-hydroxypropyl] 2-methylprop-2-enoate Chemical class CN(C)CC(O)COC(=O)C(C)=C OBHBXMOWIKWQNI-UHFFFAOYSA-N 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 238000010009 beating Methods 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- TVWTZAGVNBPXHU-FOCLMDBBSA-N dioctyl (e)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C\C(=O)OCCCCCCCC TVWTZAGVNBPXHU-FOCLMDBBSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Paper (AREA)
Description
【発明の詳細な説明】
本発明は、耐油サイズ紙の製造方法に関し、更
に詳しく言えば、ロジン系サイズ剤を含有しない
原紙を、特定必須成分を含有する水性分散液にて
処理することからなる耐油性と共に良好なサイズ
性を付与された耐油サイズ紙の製造方法に関す
る。
パーフルオロアルキル基の如きポリフルオロア
ルキル基含有ポリマー（以下、Rfポリマーと略
記することがある）は、繊維用撥水撥油剤として
の用途の他に、紙などに耐油性を付与せしめ得る
ことが知られており、油脂含有食品包装紙、工業
用紙、機械包装紙などの製造にも使用されてい
る。例えば、特開昭51−133511号公報などを参
照。しかし、かかるRfポリマーで処理加工され
た耐油紙は、充分な耐油性は有するものの、水に
対する抵抗性（サイズ性）が若干劣り、特に一般
の表面サイズ剤と併用した場合には、良好なサイ
ズ性が得られ難いだけでなく、耐油性についても
不良となつてしまう。
紙の耐水、耐インキ性（サイズ効果）の向上に
は、一般に表面サイズ剤が使用され、かかる目的
には、従来から酸化澱粉が汎用されており、サイ
ズプレス加工剤といえば、表面強度向上用の酸化
澱粉が最も代表的なものとされてきた。
本発明者の研究によれば、酸化澱粉の如きアニ
オン性表面サイズ剤とRfポリマーとを併用して
紙に適用した場合、Rfポリマー単独の場合と比
べて耐油性、サイズ性ともに低下する傾向が認め
られる。
本発明者は、前記問題点の認識に基いて、Rf
ポリマー処理による耐油サイズ紙の製造について
種々の研究、検討を重ねた結果、次の如き興味深
い知見を得るに至つた。即ち、Rfポリマーに酸
化澱粉などと水溶性カチオン系ポリマーとを組合
せて併用すると、耐油性を低下せしめることな
く、良好なサイズ性を紙に付与し得るという新規
知見を得たものである。尚、ロジン系サイズ剤に
ついては、Rfポリマー及び水溶性カチオン系ポ
リマーの併用によつても、充分な効果が得られ難
く、原紙としてはロジン系サイズ剤を含有しない
ものが採用される。
かくして本発明は、ロジン系サイズ剤を含有し
ない原紙を、ポリフルオロアルキル基含有ポリマ
ー、アニオン性表面サイズ剤、及び水溶性カチオ
ン系ポリマーを必須成分として含有する水性分散
液にて処理することを特徴とする耐油サイズ紙の
製造方法を新規に提供するものである。
本発明において使用されるアニオン性表面サイ
ズ剤としては、酸化澱粉が好適であるが、これに
限定されることなく、他の澱粉類、繊維素誘導
体、アルギン酸塩など公知乃至周知のものも例示
され得る。そして、澱粉類としても、酵素変性澱
粉、アセチル化澱粉、ジアルデヒド澱粉などを挙
げることができる。繊維素誘導体としては、カル
ボキシメチルセルロースなど、アルギン酸塩とし
ては、アルギン酸ソーダなどを挙げ得る。これら
アニオン性表面サイズ剤は、一種類単独で使用可
能であり、また二種類以上で併用されても良い。
酸化澱粉は安価な表面サイズ剤であり、起泡性も
少ないので、取り扱い易く、本発明の実用上の価
値を高めるものである。
而して、水溶性カチオン系ポリマーとしては、
ポリエチレンイミン、ポリアミン変性物、ポリア
ミドポリアミン−エピクロルヒドリン反応物など
が好適であり、その他に、カチオン変性ポリアク
リルアミド、メラミン−ホルムアルデヒド樹脂、
尿素−ホルムアルデヒド樹脂、ジシアンジアミド
−ホルムアルデヒド樹脂なども例示され得る。
本発明において、Rfポリマー、表面サイズ剤、
カチオン系ポリマーの必須成分を含有する水性分
散液で原紙を処理する場合、水性分散液中のアニ
オン性表面サイズ剤の濃度は0.1〜10重量％、特
に0.1〜５重量％程度が一般的であり、水溶性カ
チオン系ポリマーは、アニオン性表面サイズ剤
100重量部当り１〜20重量部、好ましくは３〜10
重量部程度の添加量にて使用される。このよう
に、アニオン性表面サイズ剤と水溶性カチオン系
ポリマーとを組合せて、Rfポリマーと共に併用
することにより、耐油性、サイズ性は勿論のこ
と、表面強度、印刷適性なども大巾に向上せしめ
得る。
本発明において使用するRfポリマーとしては、
種々のものが例示され得る。通常は、ポリフルオ
ロアルキル基が炭素数４〜16個のパーフルオロア
ルキル基であるものが好適である。そして、紙へ
の適用の観点から、Rfポリマーが容易にフイル
ム化するもの、即ち造膜性の良好なものが選定さ
れ得る。例えばRf含有モノマー／塩化ビニリデ
ン系共重合体が好適なRfポリマーとして例示さ
れ、塩化ビニリデン10〜60重量％、特に30〜50重
量％程度が構成単位として含有されているものが
好ましい。かかるRfポリマーは、アクリルアミ
ド、メタクリルアミドなどを構成単位として１〜
10重量％程度含有していても良く、その他Ｎ−メ
チロールアクリルアミド、Ｎ−メチロールメタク
リルアミドなどを含有していても良い。更に、そ
の単独重合体のガラス転移温度（Tg）が０℃以
下の非フツ素系疎水性単量体、カチオン性単量体
などが10重量％以下の共重合割合で含有されても
良い。例えばｎ−ブチルアクリレート、エチルア
クリレート、２−エチルヘキシルアクリレート、
ジオクチルマレート、ブタジエン、プロピオン酸
ビニルなど、あるいはジメチルアミノエチルメタ
クリレート、ジエチルアミノエチルメタクリレー
ト、２−ヒドロキシ−３−ジメチルアミノプロピ
ルメタクリレートなどの塩（酢酸塩、塩酸塩な
ど）または第四級アンモニウム塩などをRfポリ
マーの構成単位として含有せしめ得る。
本発明における水性分散液には、前記必須成分
の他、常法に従いその他の一般的な添加剤、例え
ば顔料、消泡剤、分散剤などを含有しても良いこ
とは勿論である。また、Rfポリマーやカチオン
系ポリマーの他に、他の樹脂成分を含有しても良
く、本発明の目的乃至作用効果を阻害しない限
り、各種の変更や付加が可能である。尚、水性分
散液に使用する分散剤としての界面活性剤は、ノ
ニオン系界面活性剤が好適であるが、その他カチ
オン性やアニオン性であつても良く、これらを適
宜併用しても差し支えない。
本発明において、特定水性分散液による原紙の
処理は、サイズプレス、カレンダーサイズなどの
各種含浸機、又はスプレー、ロールコーター、グ
ラビアコーター、ナイフコーターなどの塗布機に
より含浸もしくは塗布する方法で実施され得る。
塗布または含浸後の乾燥は、熱風乾燥、赤外線加
熱乾燥、これらの併用など通常用いられる方法で
良く、乾燥温度については60〜130℃程度で充分
である。そして、原紙に付着させるRfポリマー
の量は、紙重量基準で0.1〜0.6重量％程度が一般
的である。
本発明では、種々の原紙が特に限定されること
なく採用され、無サイズ紙、アルキルケテンダイ
マー内添紙、カチオン性サイズ剤内添紙、パラフ
インワツクスサイズ内添紙などが好適に採用され
る。しかし、ロジン系サイズ剤内添紙に適用した
場合には、本発明の効果は発現され難い。そし
て、原紙に使用する素材パルプについては、特に
限定する理由がなく各種木材パルプ、麻パルプ、
コツトンリンターパルプ、竹パルプ、バガスパル
プ、レーヨン、ビニロン、アクリロニトリル繊
維、ポリオレフイン系合成パルプなど広範囲にわ
たつて例示され得る。また、アスベスト、セラミ
ツクフアイバー、ガラス繊維などの無機繊維から
なるものであつても良い。
尚、本発明において特定の必須成分の併用に当
つては、アニオン性表面サイズ剤と水溶性カチオ
ン系ポリマーを予め混合し、かかる混合物をRf
ポリマーに添加混合して水性分散液として調製す
るのが好適な結果を得るために望ましい。
本発明で得られる耐油サイズ紙は、耐油性、サ
イズ性を初めとして前記の如き優れた性能を有す
るので、かかる性能を利用した各種用途などに広
範囲の分野で使用され得る。例えば、食品包装紙
や、飼料、肥料包装紙、ゴミ袋、パラフイン原
紙、鉄板合紙、剥離原紙、裏カーボン紙等の産業
用紙材が列挙される。
次に、本発明の実施例について更に具体的に説
明するが、かかる説明によつて本発明が何ら限定
されることがないことは勿論である。尚、以下の
実施例における抄紙方法、測定法及び試験方法
は、次に規定する方法に準じて行なつた。
抄紙方法：JIS P8209
サイズ度試験：JIS P8122
耐油度試験：TAPPI RC338
表面強度：JIS P8129
実施例１〜５及び比較例１〜３
下記第１表に示す各種添加剤を含む水性分散液
を使用して、サイズプレスを用いて絞り率60％に
なるような速度で原紙を浸漬処理した。次いで、
100℃に加温したドラムドライヤーで10秒間乾燥
した。尚、原紙としてはLBKP70重量％と
NBKP30重量％の混合パルプを叩解度35゜SR、坪
量90ｇ／m2に抄紙し、硫酸バンド１重量％を内添
してなるものを用いた。また、Rfポリマーとし
ては、CH2＝CHCOOCH2CH2C9F1955重量％、
塩化ビニリデン41重量％、アクリルアミド2.5重
量％、及びCH2＝Ｃ（CH3）COOCH2CH2N
（CH3）3・Cl
1.5重量％からなる共重合体を使用
し、界面活性剤としてノニルフエノキシポリエチ
レングリコールを使用して水性分散液に調製し
た。尚、下記第１表における各種添加剤の添加量
は水性分散液中の固形重量％で示している。そし
て、処理された耐油紙の性能試験結果を下記第１
表にまとめて示す。
【表】DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing oil-resistant sizing paper, and more specifically, it comprises treating base paper that does not contain a rosin-based sizing agent with an aqueous dispersion containing certain essential components. The present invention relates to a method for producing oil-resistant size paper that has good sizing properties as well as oil resistance. Polyfluoroalkyl group-containing polymers (hereinafter sometimes abbreviated as R f polymers), such as perfluoroalkyl groups, can be used as water and oil repellents for textiles, and can also impart oil resistance to paper and the like. It is also used in the production of oil-containing food wrapping paper, industrial paper, machine wrapping paper, etc. For example, see Japanese Patent Application Laid-open No. 133511/1983. However, although oil-resistant paper treated with such R f polymer has sufficient oil resistance, its resistance to water (size properties) is slightly inferior, and especially when used in combination with general surface sizing agents, it has poor resistance to water. Not only is it difficult to obtain good size properties, but the oil resistance is also poor. Surface sizing agents are generally used to improve the water resistance and ink resistance (size effect) of paper, and oxidized starch has been widely used for this purpose, and size press processing agents are used to improve surface strength. Oxidized starch has been considered the most representative. According to the research of the present inventor, when an anionic surface sizing agent such as oxidized starch and R f polymer are applied to paper together, both oil resistance and sizing properties are lower than when R f polymer is used alone. A trend is observed. Based on the recognition of the above problems, the inventors have determined that R f
As a result of various studies and studies on the production of oil-resistant size paper by polymer treatment, we have come to the following interesting findings. In other words, new findings have been obtained that when R f polymer is used in combination with oxidized starch or the like and a water-soluble cationic polymer, good sizing properties can be imparted to paper without reducing oil resistance. Regarding the rosin-based sizing agent, it is difficult to obtain a sufficient effect even when R f polymer and water-soluble cationic polymer are used in combination, so a base paper that does not contain the rosin-based sizing agent is used. Thus, the present invention is characterized in that base paper containing no rosin sizing agent is treated with an aqueous dispersion containing a polyfluoroalkyl group-containing polymer, an anionic surface sizing agent, and a water-soluble cationic polymer as essential components. The present invention provides a new method for producing oil-resistant size paper. The anionic surface sizing agent used in the present invention is preferably oxidized starch, but is not limited thereto, and may also include other starches, cellulose derivatives, alginates, and other known or well-known agents. obtain. Examples of starches include enzyme-modified starch, acetylated starch, dialdehyde starch, and the like. Examples of the cellulose derivative include carboxymethyl cellulose, and examples of the alginate include sodium alginate. These anionic surface sizing agents can be used alone or in combination of two or more.
Oxidized starch is an inexpensive surface sizing agent and has low foaming properties, making it easy to handle and increasing the practical value of the present invention. Therefore, as a water-soluble cationic polymer,
Polyethyleneimine, polyamine-modified products, polyamide polyamine-epichlorohydrin reaction products, etc. are suitable; in addition, cation-modified polyacrylamide, melamine-formaldehyde resin,
Examples include urea-formaldehyde resin and dicyandiamide-formaldehyde resin. In the present invention, an R f polymer, a surface sizing agent,
When treating base paper with an aqueous dispersion containing the essential components of a cationic polymer, the concentration of anionic surface sizing agent in the aqueous dispersion is generally about 0.1 to 10% by weight, especially about 0.1 to 5% by weight. , water-soluble cationic polymer, anionic surface sizing agent
1 to 20 parts by weight, preferably 3 to 10 parts by weight per 100 parts by weight
It is used in an amount of about parts by weight. In this way, by combining an anionic surface sizing agent and a water-soluble cationic polymer and using them together with R f polymer, not only oil resistance and sizing properties but also surface strength and printability are greatly improved. It can be forced. The R f polymer used in the present invention includes:
Various things can be exemplified. Generally, it is preferable that the polyfluoroalkyl group is a perfluoroalkyl group having 4 to 16 carbon atoms. From the viewpoint of application to paper, an R f polymer that can be easily formed into a film, that is, one that has good film-forming properties, can be selected. For example, an R f -containing monomer/vinylidene chloride copolymer is exemplified as a suitable R f polymer, and one containing vinylidene chloride in an amount of 10 to 60% by weight, particularly 30 to 50% by weight as a structural unit is preferred. Such an R f polymer has 1 to 100% acrylamide, methacrylamide, etc. as a constituent unit.
It may contain about 10% by weight, and may also contain other substances such as N-methylol acrylamide and N-methylol methacrylamide. Furthermore, a fluorine-free hydrophobic monomer, a cationic monomer, etc. whose homopolymer has a glass transition temperature (Tg) of 0° C. or lower may be contained in a copolymerization ratio of 10% by weight or less. For example, n-butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate,
Dioctyl maleate, butadiene, vinyl propionate, etc., or salts (acetate, hydrochloride, etc.) or quaternary ammonium salts of dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, 2-hydroxy-3-dimethylaminopropyl methacrylate, etc. It can be included as a constituent unit of the R f polymer. It goes without saying that the aqueous dispersion of the present invention may contain, in addition to the above-mentioned essential components, other common additives such as pigments, antifoaming agents, dispersants, etc. in accordance with conventional methods. Further, in addition to the R f polymer and the cationic polymer, other resin components may be contained, and various changes and additions can be made as long as they do not impede the objectives or effects of the present invention. The surfactant as a dispersant used in the aqueous dispersion is preferably a nonionic surfactant, but it may also be a cationic or anionic surfactant, and these may be used in combination as appropriate. In the present invention, the treatment of base paper with the specific aqueous dispersion can be carried out by impregnation or coating using various impregnating machines such as a size press or calendar size, or coating machines such as a spray, roll coater, gravure coater, or knife coater. .
Drying after coating or impregnation may be carried out by a commonly used method such as hot air drying, infrared heating drying, or a combination thereof, and a drying temperature of about 60 to 130°C is sufficient. The amount of R f polymer attached to the base paper is generally about 0.1 to 0.6% by weight based on the weight of the paper. In the present invention, various base papers are employed without particular limitation, and sizeless paper, alkyl ketene dimer internally added paper, cationic sizing agent internally added paper, paraffin wax size internally added paper, etc. are suitably employed. . However, when applied to paper loaded with a rosin-based sizing agent, the effects of the present invention are difficult to achieve. There is no particular reason to limit the material pulp used for base paper, and there are various types of wood pulp, hemp pulp,
A wide range of examples may be used, such as cotton linter pulp, bamboo pulp, bagasse pulp, rayon, vinylon, acrylonitrile fiber, and polyolefin-based synthetic pulp. Further, it may be made of inorganic fibers such as asbestos, ceramic fibers, and glass fibers. In addition, in the case of using specific essential components in combination in the present invention, the anionic surface sizing agent and the water-soluble cationic polymer are mixed in advance, and the mixture is subjected to R f
Preparation by addition to the polymer as an aqueous dispersion is preferred to obtain suitable results. Since the oil-resistant size paper obtained by the present invention has the above-mentioned excellent properties including oil resistance and sizing properties, it can be used in a wide range of fields for various applications utilizing such properties. For example, industrial paper materials such as food wrapping paper, feed, fertilizer wrapping paper, garbage bags, paraffin base paper, iron plate laminated paper, release base paper, and back carbon paper are listed. Next, examples of the present invention will be described in more detail, but it goes without saying that the present invention is not limited in any way by such description. Note that the paper making method, measuring method, and testing method in the following examples were carried out in accordance with the methods specified below. Paper making method: JIS P8209 Sizing test: JIS P8122 Oil resistance test: TAPPI RC338 Surface strength: JIS P8129 Examples 1 to 5 and Comparative Examples 1 to 3 Aqueous dispersions containing various additives shown in Table 1 below were used. Then, the base paper was immersed using a size press at a speed that gave a reduction rate of 60%. Then,
It was dried for 10 seconds using a drum dryer heated to 100°C. In addition, the base paper is LBKP70% by weight.
A mixed pulp containing 30% by weight of NBKP was made into paper with a beating degree of 35°SR and a basis weight of 90g/m 2 and 1% by weight of banded sulfate was added internally. In addition, as the R f polymer, CH 2 =CHCOOCH 2 CH 2 C 9 F 19 55% by weight,
41% by weight vinylidene chloride, 2.5% by weight acrylamide, and CH2 =C( CH3 ) COOCH2CH2N
An aqueous dispersion was prepared using a copolymer consisting of 1.5% by weight of (CH 3 ) 3 Cl and nonylphenoxy polyethylene glycol as a surfactant. In addition, the amounts of various additives added in Table 1 below are shown in solid weight % in the aqueous dispersion. Then, the performance test results of the treated oil-resistant paper were evaluated as follows.
They are summarized in the table. 【table】
Claims (1)
フルオロアルキル基含有ポリマー、アニオン性表
面サイズ剤、及び水溶性カチオン系ポリマーを必
須成分として含有する水性分散液にて処理するこ
とを特徴とする耐油サイズ紙の製造方法。 ２ ポリフルオロアルキル基が炭素数４〜16個の
パーフルオロアルキル基である特許請求の範囲第
１項記載の製造方法。 ３ 水性分散液中のアニオン性表面サイズ剤の濃
度が0.1〜10重量％である特許請求の範囲第１項
記載の製造方法。 ４ 水溶性カチオン系ポリマーの添加量がアニオ
ン性表面サイズ剤100重量部当り１〜20重量部で
ある特許請求の範囲第１項又は第３項記載の製造
方法。 ５ アニオン性表面サイズ剤が酸化澱粉である特
許請求の範囲第１項又は第３項記載の製造方法。 ６ ポリフルオロアルキル基含有ポリマーが、ポ
リフルオロアルキル基含有モノマー／塩化ビニリ
デン系共重合体である特許請求の範囲第１項又は
第２項記載の製造方法。 ７ ポリフルオロアルキル基含有ポリマーが塩化
ビニリデン10〜60重量％及びアクリルアミド又は
メタクリルアミド１〜10重量％を構成単位として
ポリフルオロアルキル基含有モノマーに共重合さ
れたポリマーである特許請求の範囲第６項記載の
製造方法。 ８ 原紙に付着させるポリフルオロアルキル基含
有ポリマーの量が原紙重量基準で0.1〜0.6％とな
るように処理する特許請求の範囲第１項記載の製
造方法。[Claims] 1. Treating base paper that does not contain a rosin sizing agent with an aqueous dispersion that contains a polyfluoroalkyl group-containing polymer, an anionic surface sizing agent, and a water-soluble cationic polymer as essential components. A method for producing oil-resistant size paper characterized by: 2. The manufacturing method according to claim 1, wherein the polyfluoroalkyl group is a perfluoroalkyl group having 4 to 16 carbon atoms. 3. The manufacturing method according to claim 1, wherein the concentration of the anionic surface sizing agent in the aqueous dispersion is 0.1 to 10% by weight. 4. The manufacturing method according to claim 1 or 3, wherein the amount of the water-soluble cationic polymer added is 1 to 20 parts by weight per 100 parts by weight of the anionic surface sizing agent. 5. The manufacturing method according to claim 1 or 3, wherein the anionic surface sizing agent is oxidized starch. 6. The manufacturing method according to claim 1 or 2, wherein the polyfluoroalkyl group-containing polymer is a polyfluoroalkyl group-containing monomer/vinylidene chloride copolymer. 7. Claim 6, wherein the polyfluoroalkyl group-containing polymer is a polymer copolymerized with a polyfluoroalkyl group-containing monomer using 10 to 60% by weight of vinylidene chloride and 1 to 10% by weight of acrylamide or methacrylamide as constituent units. Manufacturing method described. 8. The manufacturing method according to claim 1, wherein the amount of the polyfluoroalkyl group-containing polymer attached to the base paper is 0.1 to 0.6% based on the weight of the base paper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1656580A JPS56118995A (en) | 1980-02-15 | 1980-02-15 | Production of oil resistant size paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1656580A JPS56118995A (en) | 1980-02-15 | 1980-02-15 | Production of oil resistant size paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS56118995A JPS56118995A (en) | 1981-09-18 |
| JPS642717B2 true JPS642717B2 (en) | 1989-01-18 |
Family
ID=11919802
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1656580A Granted JPS56118995A (en) | 1980-02-15 | 1980-02-15 | Production of oil resistant size paper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS56118995A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5795398A (en) * | 1980-12-02 | 1982-06-14 | Sumitomo Chemical Co | Production of paper or paperboard having oil resistance |
| JP3093965B2 (en) * | 1994-12-28 | 2000-10-03 | 日本製紙株式会社 | Printing paper and newspaper printing paper with improved water absorption |
| CN102666772B (en) * | 2009-11-13 | 2016-05-04 | 旭硝子株式会社 | Waterproofing/oilproofing agent composition, the article of being processed by it and their manufacture method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5522069A (en) * | 1978-08-03 | 1980-02-16 | Oji Paper Co | Production of oil resistant paper with low air permeability |
-
1980
- 1980-02-15 JP JP1656580A patent/JPS56118995A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS56118995A (en) | 1981-09-18 |
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