JP4279286B2 - Oil-proof paper and method for producing the same - Google Patents
Oil-proof paper and method for producing the same Download PDFInfo
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- JP4279286B2 JP4279286B2 JP2005352340A JP2005352340A JP4279286B2 JP 4279286 B2 JP4279286 B2 JP 4279286B2 JP 2005352340 A JP2005352340 A JP 2005352340A JP 2005352340 A JP2005352340 A JP 2005352340A JP 4279286 B2 JP4279286 B2 JP 4279286B2
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- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000003921 oil Substances 0.000 claims description 138
- 239000000123 paper Substances 0.000 claims description 129
- 239000003795 chemical substances by application Substances 0.000 claims description 116
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 82
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 81
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 63
- 229910052731 fluorine Inorganic materials 0.000 claims description 63
- 239000011737 fluorine Substances 0.000 claims description 63
- 239000002939 oilproofing Substances 0.000 claims description 51
- 230000035699 permeability Effects 0.000 claims description 39
- 239000003973 paint Substances 0.000 claims description 26
- 239000000835 fiber Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000001993 wax Substances 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 23
- 230000035515 penetration Effects 0.000 description 19
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000000178 monomer Substances 0.000 description 9
- 229920001131 Pulp (paper) Polymers 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011122 softwood Substances 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 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 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011086 glassine Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000002655 kraft paper Substances 0.000 description 2
- 235000014593 oils and fats Nutrition 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000011087 paperboard Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 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 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 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 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-L fumarate(2-) Chemical class [O-]C(=O)\C=C\C([O-])=O VZCYOOQTPOCHFL-OWOJBTEDSA-L 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 150000002688 maleic acid derivatives Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013054 paper strength agent Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Description
本発明は、紙皿や食品包装などに使用される耐油紙及びその製造方法に関するものである。 The present invention relates to an oil-resistant paper used for paper plates, food packaging, and the like and a method for producing the same.
耐油紙は、ＪＩＳ Ｐ ０００１：１９９８「紙・板紙及びパルプ用語」では「１）耐油性をもたせた紙の総称。参考：高度に叩解した化学パルプを用いて抄造した紙、及び油脂類に対して抵抗性をもつように化学処理及び／又は塗工した紙がある。２）グリース又は脂肪の浸透に対して極めて大きな抵抗力をもった紙又は板紙。参考：ある種の紙、例えばカーボン原紙は、これらの物質の浸透を完全に阻止する。」と定義されている。 Oil-resistant paper is a generic term for “1) oil-resistant paper in JIS P 0001: 1998“ Paper / Board and Pulp Terminology. ”Reference: For paper made with highly beaten chemical pulp and oils and fats 2) Paper or paperboard that is extremely resistant to the penetration of grease or fat Reference: Some types of paper, such as carbon base paper Is completely deterred from penetration of these substances. "
耐油紙としては、例えば、グラシン紙、ポリエチレン加工紙、塩化ビニリデン加工紙、防湿セロハン紙、アルミ箔ラミネート紙がある。 Examples of the oil resistant paper include glassine paper, polyethylene processed paper, vinylidene chloride processed paper, moisture-proof cellophane paper, and aluminum foil laminated paper.
耐油紙には、耐油性に加え透気性が要求されるものがあり、例えば、ハンバーガー等の包装用紙には、油脂分を通過させない耐油性と、水蒸気を通過させる透気性の両方が要求される。しかし、前記グラシン紙等は、基紙を高密度に仕上げることにより基紙の空隙を減らす機構、或いは、耐油剤の材料を塗工、含浸又は貼合により基紙の空隙を塞ぐ機構であり、良好な耐油性は得られるが、透気性が得られない。 Some oil-resistant papers require air permeability in addition to oil resistance. For example, packaging paper such as a hamburger requires both oil resistance that does not allow oils and fats to pass and air permeability that allows water vapor to pass. . However, the glassine paper or the like is a mechanism that reduces the gap of the base paper by finishing the base paper at a high density, or a mechanism that closes the gap of the base paper by coating, impregnating, or pasting an oil resistant material, Good oil resistance is obtained, but air permeability is not obtained.
耐油性を付与しつつ透気性を得るためには、加工処理面の臨界表面張力を油性物質の表面張力より小さくする方法がある。このような機能を付与する薬品を耐油剤と称し、過フッ素炭化水素のアクリルレート又は過フッ素炭化水素のリン酸エステル等のフッ素系化合物を含有したフッ素系耐油剤を用いる方法が耐油紙の製造方法の主流となっている。フッ素系耐油剤を用いる方法では、紙の表面張力を下げて、油の濡れ性を低下させて油の浸透を防止する機構であり、基紙の空隙を減らす又は塞ぐ必要はないため、一般的な基紙と同等の透気性が維持される。さらに、フッ素系耐油剤を用いれば、耐油紙の使用時において、油は表面で十分に弾かれるため、気体が通過する空隙が油によって塞がれにくく、その結果、透気性の低下が生じにくい。これらの理由から、フッ素系耐油剤で処理した耐油剤が広く使用されている（例えば、特許文献１又は特許文献２を参照。）。 In order to obtain air permeability while imparting oil resistance, there is a method of making the critical surface tension of the processed surface smaller than the surface tension of the oily substance. The method of using a fluorine-based oil-resistant agent containing a fluorine-based compound such as a perfluorinated hydrocarbon acrylate or a phosphoric acid ester of perfluorinated hydrocarbon is referred to as an oil-resistant agent. The method has become mainstream. In the method using a fluorinated oil proofing agent, it is a mechanism that lowers the surface tension of the paper and reduces the wettability of the oil to prevent the penetration of the oil, and it is not necessary to reduce or close the gap of the base paper. Permeability equivalent to that of a new base paper is maintained. Furthermore, when using a fluorinated oil-resistant agent, when oil-resistant paper is used, the oil is sufficiently repelled on the surface, so that the voids through which the gas passes are not easily blocked by the oil, and as a result, the gas permeability is unlikely to decrease. . For these reasons, oil-resistant agents treated with fluorine-based oil-resistant agents are widely used (see, for example, Patent Document 1 or Patent Document 2).
フッ素系耐油剤は、その耐油性を生じさせる機構から、基紙の表面に均一に存在すれば耐油性を生ずるが、実際には、基紙が、それ自身に多くの細孔を有する多孔質繊維を主成分とする為、フッ素系耐油剤は基紙内部及び多孔質繊維に浸透している。このことによって、フッ素系耐油剤で処理した耐油紙の製造においては、高価なフッ素系耐油剤を余剰に使用しなくてはならないというコストアップの問題が生じていた。 Fluorine-based oil-resistant agent is oil-resistant if it exists uniformly on the surface of the base paper because of its oil-resistant mechanism, but in fact, the base paper is porous with many pores in itself. Since the fiber is the main component, the fluorine-based oilproof agent penetrates into the base paper and the porous fiber. As a result, in the production of oil-resistant paper treated with a fluorinated oil proofing agent, there has been a problem of cost increase that an expensive fluorinated oil proofing agent must be used excessively.
そこで、本発明は、このような問題点を解決すべく創案されたもので、その目的は、耐油性があり、且つ、透気性が一般的な紙と同等でありながら、フッ素系耐油剤のみを浸透させた耐油紙と比較して、フッ素系耐油剤の浸透を抑えることで、フッ素系耐油剤の使用量が少なく、安価な耐油紙を得ることである。 Therefore, the present invention was devised to solve such problems, and its purpose is oil resistance and air permeability is equivalent to that of general paper, but only fluorine-based oil resistance agents. Compared with oil-resistant paper that has been infiltrated with oil, the amount of fluorine-based oil-resistant agent used is small and inexpensive oil-resistant paper is obtained by suppressing the penetration of fluorine-based oil-resistant agents.
本発明者等は、前記課題を解決すべく鋭意検討した結果、フッ素系耐油剤をアニオン変性ポリビニルアルコールと混合状態となるように浸透させることにより、フッ素系耐油剤の浸透を抑えることができることを見出し、本発明を完成させた。すなわち、本発明に係る耐油紙は、多孔質繊維を主成分とし、かつ、内添サイズ剤を含有した基紙に、フッ素系耐油剤とアニオン変性ポリビニルアルコールとを混合した塗料が浸透されている耐油紙であって、前記フッ素系耐油剤と前記アニオン変性ポリビニルアルコールの固形分の質量比が、７：３〜３：７であり、かつ、前記多孔質繊維１００質量部に対して、０．１０質量部以上０．２６質量部未満のフッ素系耐油剤が浸透されていることを特徴とする。多孔質繊維１００質量部に対して、０．１０質量部以上０．２６質量部未満のフッ素系耐油剤が浸透されている場合、フッ素系耐油剤のみでは十分な耐油性が得られない量ではあるが、ポリビニルアルコールとの混合状態とすることで耐油性が安定して得られる。 また、アニオン変性ポリビニルアルコールを用いると、多孔質繊維の表面がアニオン性なので内部へ浸透しにくくなる。 As a result of intensive studies to solve the above-mentioned problems, the inventors have made it possible to suppress the penetration of the fluorinated oil proofing agent by allowing the fluorinated oil proofing agent to penetrate into the mixed state with the anion-modified polyvinyl alcohol. The headline and the present invention were completed. That is, the oil-resistant paper according to the present invention has a base material containing porous fibers as a main component and containing an internal sizing agent, and a paint in which a fluorine-based oil-resistant agent and an anion-modified polyvinyl alcohol are mixed. It is oil-resistant paper, Comprising: The mass ratio of the solid content of the said fluorine-type oil-resistant agent and the said anion modified polyvinyl alcohol is 7: 3 to 3: 7, and is 0.1. It is characterized by being permeated with 10 or more parts by mass and less than 0.26 parts by mass of a fluorinated oilproofing agent. When 0.10 parts by mass or more and less than 0.26 parts by mass of a fluorine-based oil proofing agent is permeated with respect to 100 parts by mass of the porous fiber, the amount of sufficient oil resistance cannot be obtained with only the fluorine-based oil proofing agent. However, oil resistance can be stably obtained by mixing with polyvinyl alcohol. In addition, when anion-modified polyvinyl alcohol is used, the surface of the porous fiber is anionic, so that it is difficult to penetrate into the inside.
本発明に係る耐油紙では、ＴＡＰＰＩ ＵＭ ５５７「Ｒｅｐｅｌｌｅｎｃｙ ｏｆ Ｐａｐｅｒ ａｎｄ Ｂｏａｒｄ ｔｏ Ｇｒｅａｓｅ，Ｏｉｌ，ａｎｄ Ｗａｘｅｓ（Ｋｉｔ Ｔｅｓｔ）」で規定される耐油度が５級以上であり、且つ、ＪＩＳ Ｐ ８１１７：１９９８「紙及び板紙−透気度試験方法−ガーレー試験機法」で規定される透気度が５０秒以下であることが好ましい。 In the oil-resistant paper according to the present invention, the oil resistance specified by TAPPI UM 557 “Repelency of Paper and Board to Grade, Oil, and Waxes (Kit Test)” is 5th grade or more, and JIS P 8117: 1998 “ It is preferable that the air permeability defined by “Paper and paperboard—Air permeability test method—Gurley tester method” is 50 seconds or less.
また、本発明に係る耐油紙の製造方法は、多孔質繊維を主成分とし、かつ、内添サイズ剤を含有した基紙の少なくとも片面側から、フッ素系耐油剤とアニオン変性ポリビニルアルコールを、固形分の質量比で７：３〜３：７の割合で含有した混合液を浸透させ、かつ、前記混合液の浸透量を、前記フッ素系耐油剤が前記多孔質繊維１００質量部に対して、０．１０質量部以上０．２６質量部未満となる量とする工程と、前記混合液を浸透させた前記基紙を乾燥する工程と、を有することを特徴とする。 In addition, the method for producing an oil-resistant paper according to the present invention is a method in which a fluorine-based oil resistant agent and an anion-modified polyvinyl alcohol are solidified from at least one side of a base paper containing porous fibers as a main component and containing an internal sizing agent. Infiltrate the mixed liquid containing 7: 3 to 3: 7 in a mass ratio of minutes, and the permeation amount of the mixed liquid with respect to 100 parts by mass of the porous oil-resistant agent, It has the process of setting it as the quantity used as 0.10 mass part or more and less than 0.26 mass part, and the process of drying the said base paper infiltrated with the said liquid mixture, It is characterized by the above-mentioned.
本発明に係る耐油紙の製造方法では、前記混合液を浸透させる工程において、抄紙機に付属する塗工機によって前記混合液を前記基紙に浸透させることが好ましい。耐油紙の生産効率を高めることができる。 In the method for producing oil-resistant paper according to the present invention, in the step of infiltrating the mixed liquid, it is preferable that the mixed liquid is infiltrated into the base paper by a coating machine attached to a paper machine. The production efficiency of oil-resistant paper can be increased.
本発明の耐油紙は、耐油性があり、且つ、透気性が一般的な紙と同等でありながら、フッ素系耐油剤のみを浸透させた耐油紙と比較して、フッ素系耐油剤の浸透を抑えることで、フッ素系耐油剤の使用量が少なく、安価である。 The oil-resistant paper of the present invention is oil-resistant and has the same permeability as general paper, but has a permeation of a fluorine-based oil-resistant agent as compared with an oil-resistant paper in which only a fluorine-based oil-resistant agent is infiltrated. By suppressing it, the amount of fluorine-based oilproofing agent used is small and inexpensive.
以下、本発明について実施形態を示して詳細に説明するが、本発明はこれらの記載に限定して解釈されない。 Hereinafter, although an embodiment is shown and explained in detail about the present invention, the present invention is limited to these descriptions and is not interpreted.
本実施形態に係る耐油紙は、多孔質繊維を主成分とした基紙に、フッ素系耐油剤とポリビニルアルコールが混合状態で浸透されている耐油紙であって、前記フッ素系耐油剤と前記ポリビニルアルコールの固形分の質量比が、７：３〜３：７である。この耐油紙は、フッ素系耐油剤をポリビニルアルコールと混合状態となるように浸透させる工程、例えば、フッ素系耐油剤とポリビニルアルコールの混合液を基紙に浸透させる工程を含む製造方法により得られる。 The oil-resistant paper according to the present embodiment is an oil-resistant paper in which a fluorine-based oil-resistant agent and polyvinyl alcohol are infiltrated in a mixed state into a base paper mainly composed of porous fibers, the fluorine-based oil-resistant agent and the polyvinyl-based paper. The mass ratio of the solid content of the alcohol is 7: 3 to 3: 7. This oil-resistant paper is obtained by a production method including a step of permeating a fluorine-based oil-resistant agent so as to be mixed with polyvinyl alcohol, for example, a step of permeating a mixed liquid of a fluorine-based oil-resistant agent and polyvinyl alcohol into the base paper.
多孔質繊維は、入手の容易さ等から木材パルプ繊維を主成分とするが、それ以外の非木材パルプ繊維を使用しても良い。木材パルプには、針葉樹クラフトパルプ、広葉樹クラフトパルプ、サルファイトパルプ等の化学パルプ、ストーングラインドパルプ、サーモメカニカルパルプ、リファイナーグラインドパルプの機械パルプ、又は、新聞、コート紙、上質紙等から得られる再生パルプを使用することができる。また、これらを適宜配合して使用することもできる。 The porous fibers are mainly composed of wood pulp fibers because of their availability, but other non-wood pulp fibers may be used. Wood pulp is recycled from chemical pulp such as softwood kraft pulp, hardwood kraft pulp, sulfite pulp, stone grind pulp, thermomechanical pulp, mechanical pulp of refiner grind pulp, or newspaper, coated paper, fine paper, etc. Pulp can be used. Moreover, these can also be mix | blended suitably and used.
基紙は多孔質繊維を主成分とするが、それ以外に無機繊維や填料を混合しても良い。また、その他必要に応じて、染料、紙力剤、湿潤紙力増強剤等の公知の内添剤を添加することができる。 The base paper is mainly composed of porous fibers, but may be mixed with inorganic fibers and fillers. In addition, known internal additives such as dyes, paper strength agents, and wet strength agents can be added as necessary.
基紙の抄造は、長網抄紙機、丸網抄紙機、トップワイヤーの付いた長網抄紙機、短網抄紙機あるいはそれらのコンビネーション抄紙機等で行われるが、これに限定されるものではない。 The base paper is made by a long paper machine, a round paper machine, a long paper machine with a top wire, a short paper machine, or a combination paper machine thereof, but is not limited thereto. .
フッ素系耐油剤として、ポリフルオロアルキル基を有するモノマの重合単位を含む重合体、又は、ポリフルオロアルキル基を有するリン酸エステル等のフッ素系化合物を使用することができる。 As the fluorine-based oilproofing agent, a polymer containing a monomeric polymer unit having a polyfluoroalkyl group or a fluorine-based compound such as a phosphate ester having a polyfluoroalkyl group can be used.
ポリフルオロアルキル基を有するモノマの重合単位を含む重合体は、ポリフルオロアルキル基（Ｒｆ基）及び１個のみの重合性不飽和基を有するモノマ（Ｒｆ基含有モノマ）を重合することにより、又は、Ｒｆ基含有モノマと重合性不飽和基を１個以上有し且つＲｆ基を含有しない重合性モノマ（共重合性モノマ）を重合することにより得られる。Ｒｆ基含有モノマは、例えば、Ｒｆ基含有（メタ）アクリレート類、Ｒｆ基含有スチレン類、Ｒｆ基含有ビニルエステル類、Ｒｆ基含有フマレート類である。浸透されている紙の柔軟性、繊維に対する接着性、汎用性、溶媒に対する溶解性及び乳化重合の容易さ等の観点から、Ｒｆ基含有（メタ）アクリレート類が好ましい。また、Ｒｆ基は、アルキル基の水素原子の全てがフッ素原子に置換されたパーフルオロアルキル基であることが好ましい。共重合性モノマとしては、例えば、（メタ）アクリレート類、（メタ）アクリルアミド類、ビニルエーテル類、ビニルエステル類、フマレート類又はマレエート類が挙げられる。Ｒｆ基含有モノマを以下に挙げるが、これらに限定されない。 A polymer containing a polymer unit of a monomer having a polyfluoroalkyl group is obtained by polymerizing a monomer having a polyfluoroalkyl group (Rf group) and only one polymerizable unsaturated group (Rf group-containing monomer), or And an Rf group-containing monomer and a polymerizable monomer having at least one polymerizable unsaturated group and not containing an Rf group (copolymerizable monomer). Rf group-containing monomers are, for example, Rf group-containing (meth) acrylates, Rf group-containing styrenes, Rf group-containing vinyl esters, and Rf group-containing fumarate. Rf group-containing (meth) acrylates are preferred from the viewpoints of the flexibility of the paper that has been infiltrated, the adhesiveness to fibers, the versatility, the solubility in solvents and the ease of emulsion polymerization. The Rf group is preferably a perfluoroalkyl group in which all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms. Examples of the copolymerizable monomer include (meth) acrylates, (meth) acrylamides, vinyl ethers, vinyl esters, fumarates, and maleates. Rf group-containing monomers are listed below, but are not limited thereto.
ＣＦ３（ＣＦ２）６ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７（ＣＨ２）４ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９（ＣＨ２ ）２ ＯＣＯＣＨ＝ＣＨ２ 、ＣＦ３（ＣＦ２）９（ＣＨ２ ）３ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９（ＣＨ２）１１ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９（ＣＦ２）２（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）１３（ＣＨ２）６ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）４ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）６ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）６Ｏ（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、Ｆ（ＣＦ２）１０（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）６（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）６（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）８（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）８（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）１０（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２、ＣＦ２Ｃｌ（ＣＦ２）９（ＣＨ２）３ＯＣＯＣＨ＝ＣＨ２、Ｈ（ＣＦ２）１０ＣＨ２ＯＣＯＣＨ＝ＣＨ２、 Ｈ（ＣＦ２）１０（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ２Ｃｌ（ＣＦ２）１０ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（ＣＨ３）（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ２Ｈ５）（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ３Ｈ７）（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ４Ｈ９）（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（ＣＨ３）（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ２Ｈ５）（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ３Ｈ７）（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）７ＳＯ２Ｎ（Ｃ４Ｈ９）（ＣＨ２）２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）７ＣＯＮＨ（ＣＨ２）３ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９ＣＯＮＨ（ＣＨ２）５ＯＣＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＣＯＮＨ（ＣＨ２）３ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＯＣＨ２Ｐｈ（ＣＨ２）２ＯＣＯＣＨ＝ＣＨ２、（ＣＦ３）２ＣＦ（ＣＦ２）８ＣＨ２ＣＨ（ＯＣＯＣＨ３）ＣＨ２ＯＣＯＣ（ＣＨ３）＝ＣＨ２、ＣＦ３（ＣＦ２）９ＣＨ２ＣＯＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９（ＣＨ２）２ＣＯＯＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＯＣＨ＝ＣＨ２、Ｈ（ＣＦ２）１０ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）１３ＳＯ２ＮＨ（ＣＨ２）２ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７ＣＯＮＨ（ＣＨ２）３ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）９ＣＯＮＨ（ＣＨ２）２ＣＨ＝ＣＨ２、ＣＦ３（ＣＦ２）７（ＣＨ２）２ＯＣＨ２ＰｈＣＨ＝ＣＨ２。 CF 3 (CF 2 ) 6 OCOCH═CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 2 OCOCH═CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 4 OCOCH═CH 2 , CF 3 (CF 2 ) 9 (CH 2 ) 2 OCOCH═CH 2 , CF 3 (CF 2 ) 9 (CH 2 ) 3 OCOCH═CH 2 , CF 3 (CF 2 ) 9 (CH 2 ) 11 OCOCH═CH 2 , CF 3 ( CF 2 ) 9 (CF 2 ) 2 (CH 2 ) 2 OCOCH═CH 2 , CF 3 (CF 2 ) 13 (CH 2 ) 6 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 4 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 6 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 6 O (CH 2) 2 OCOC (CH 3) = CH 2, F (CF 2 ) 10 (CH 2 ) 2 OCOC (CH 3 ) ═CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 (CH 2 ) 2 OCOCH═CH 2 , (CF 3 ) 2 CF (CF 2 ) 6 (CH 2 ) 3 OCOCH═CH 2 , (CF 3 ) 2 CF (CF 2 ) 8 (CH 2 ) 2 OCOCH═CH 2 , (CF 3 ) 2 CF (CF 2 ) 8 (CH 2 ) 3 OCOCH = CH 2 , (CF 3 ) 2 CF (CF 2 ) 10 (CH 2 ) 3 OCOCH═CH 2 , CF 2 Cl (CF 2 ) 9 (CH 2 ) 3 OCOCH═CH 2 , H (CF 2 ) 10 CH 2 OCOCH = CH 2, H ( CF 2) 10 (CH 2) 2 OCOCH = CH 2, CF 2 Cl (CF 2) 10 CH 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 O 2 N (CH 3) ( CH 2) 2 OCOCH = CH 2, CF 3 (CF 2) 7 SO 2 N (C 2 H 5) (CH 2) 2 OCOCH = CH 2, CF 3 (CF 2) 7 SO 2 N (C 3 H 7 ) (CH 2 ) 2 OCOCH═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (C 4 H 9 ) (CH 2 ) 2 OCOCH═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (CH 3 ) (CH 2 ) 2 OCOC (CH 3 ) ═CH 2 , CF 3 (CF 2 ) 7 SO 2 N (C 2 H 5 ) (CH 2 ) 2 OCOC (CH 3 ) = CH 2, CF 3 (CF 2 ) 7 SO 2 N (C 3 H 7) (CH 2) 2 OCOC (CH 3) = CH 2, CF 3 (CF 2) 7 SO 2 N (C 4 H 9) ( CH 2) 2 OCOC (CH 3 ) = CH 2, C 3 (CF 2) 7 CONH ( CH 2) 3 CH = CH 2, CF 3 (CF 2) 9 CONH (CH 2) 5 OCOCH = CH 2, CF 3 (CF 2) 7 CONH (CH 2) 3 CH = CH 2, CF 3 (CF 2 ) 7 (CH 2) 2 OCH 2 Ph (CH 2) 2 OCOCH = CH 2, (CF 3) 2 CF (CF 2) 8 CH 2 CH (OCOCH 3) CH 2 OCOC ( CH 3 ) ═CH 2 , CF 3 (CF 2 ) 9 CH 2 COOCH═CH 2 , CF 3 (CF 2 ) 9 (CH 2 ) 2 COOCH═CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 2 OCH═CH 2 , H (CF 2 ) 10 CH═CH 2 , CF 3 (CF 2 ) 13 SO 2 NH (CH 2 ) 2 CH═CH 2 , CF 3 (CF 2 ) 7 CONH (CH 2 ) 3 CH = CH 2 , CF 3 (CF 2 ) 9 CONH (CH 2 ) 2 CH═CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 2 OCH 2 PhCH═CH 2 .
また、ポリフルオロアルキル基を有するリン酸エステルとしては、以下に挙げるものが使用できるがこれらに限定されない。 Moreover, as a phosphate ester which has a polyfluoroalkyl group, the following can be used, but it is not limited to these.
［Ｃ６Ｆ１３ＣＨ２ＣＨ２Ｏ］３ＰＯ、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］３ＰＯ、［Ｃ１０Ｆ２１ＣＨ２ＣＨ２Ｏ］３ＰＯ、［Ｃ１２Ｆ２５ＣＨ２ＣＨ２Ｏ］３ＰＯ、［Ｃ６Ｆ１３ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ１０Ｆ２１ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ１２Ｆ２５ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ６Ｆ１３ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］２、［Ｃ１０Ｆ２１ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］２、［Ｃ１２Ｆ２５ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ４］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ４］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ３（ＣＨ２ＣＨ２ＯＨ）］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ３（ＣＨ２ＣＨ２ＯＨ）］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ（ＣＨ２ＣＨ２ＯＨ）３］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ（ＣＨ２ＣＨ２ＯＨ）３］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］ＰＯ（ＯＨ）（Ｏ−）［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ８Ｆ１７ＳＯ２Ｎ（Ｃ２Ｈ５）ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ８Ｆ１７ＳＯ２Ｎ（Ｃ２Ｈ５）ＣＨ２ＣＨ２Ｏ］ＰＯ（Ｏ−）２・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］２、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・（Ｎａ＋）、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・（Ｋ＋）、［Ｃ８Ｆ１７ＣＨ２ＣＨ２ＯＣＨ２ＣＨ２Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２ＯＣ３Ｈ６Ｏ］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］、［Ｃ８Ｆ１７ＣＨ２ＣＨ２Ｏ（ＣＨ２ＣＨ２Ｏ）６］２ＰＯ（Ｏ−）・［Ｎ＋Ｈ２（ＣＨ２ＣＨ２ＯＨ）２］。 [C 6 F 13 CH 2 CH 2 O] 3 PO, [C 8 F 17 CH 2 CH 2 O] 3 PO, [C 10 F 21 CH 2 CH 2 O] 3 PO, [C 12 F 25 CH 2 CH 2 O] 3 PO, [C 6 F 13 CH 2 CH 2 O] 2 PO (O -) · [N + H 2 (CH 2 CH 2 OH) 2], [C 8 F 17 CH 2 CH 2 O] 2 PO (O − ) · [N + H 2 (CH 2 CH 2 OH) 2 ], [C 10 F 21 CH 2 CH 2 O] 2 PO (O − ) · [N + H 2 (CH 2 CH 2 OH) 2], [C 12 F 25 CH 2 CH 2 O] 2 PO (O -) · [N + H 2 (CH 2 CH 2 OH) 2], [C 6 F 13 CH 2 CH 2 O] PO (O − ) 2. [N + H 2 (CH 2 CH 2 OH) 2 ] 2 , [C 8 F 1 7 CH 2 CH 2 O] PO (O − ) 2. [N + H 2 (CH 2 CH 2 OH) 2 ] 2 , [C 10 F 21 CH 2 CH 2 O] PO (O − ) 2. [N + H 2 (CH 2 CH 2 OH) 2 ] 2 , [C 12 F 25 CH 2 CH 2 O] PO (O − ) 2. [N + H 2 (CH 2 CH 2 OH) 2 ] 2 , [C 8 F 17 CH 2 CH 2 O ] 2 PO (O -) · [N + H 4], [C 8 F 17 CH 2 CH 2 O] PO (O -) 2 · [N + H 4] 2, [ C 8 F 17 CH 2 CH 2 O] 2 PO (O -) · [N + H 3 (CH 2 CH 2 OH)], [C 8 F 17 CH 2 CH 2 O] PO (O -) 2 · [ N + H 3 (CH 2 CH 2 OH)] 2, [C 8 F 17 CH 2 CH 2 O] 2 PO (O -) · [N H (CH 2 CH 2 OH) 3], [C 8 F 17 CH 2 CH 2 O] PO (O -) 2 · [N + H (CH 2 CH 2 OH) 3] 2, [C 8 F 17 CH 2 CH 2 O] PO (OH ) (O -) [N + H 2 (CH 2 CH 2 OH) 2], [C 8 F 17 SO 2 N (C 2 H 5) CH 2 CH 2 O] 2 PO (O − ) · [N + H 2 (CH 2 CH 2 OH) 2 ], [C 8 F 17 SO 2 N (C 2 H 5 ) CH 2 CH 2 O] PO (O − ) 2. [N + H 2 (CH 2 CH 2 OH) 2 ] 2 , [C 8 F 17 CH 2 CH 2 O] 2 PO (O − ) · (Na + ), [C 8 F 17 CH 2 CH 2 O] 2 PO ( O − ) · (K + ), [C 8 F 17 CH 2 CH 2 OCH 2 CH 2 O] 2 PO (O − ) · [N + H 2 (CH 2 CH 2 OH) 2], [C 8 F 17 CH 2 CH 2 OC 3 H 6 O] 2 PO (O -) · [N + H 2 (CH 2 CH 2 OH) 2], [C 8 F 17 CH 2 CH 2 O (CH 2 CH 2 O) 6] 2 PO (O -) · [N + H 2 (CH 2 CH 2 OH) 2].
ポリビニルアルコールとして、ケン化度が９５ｍｏｌ％を超える完全ケン化タイプといわれるポリビニルアルコールや、７０〜９０ｍｏｌ％の部分ケン化タイプといわれるポリビニルアルコールのいずれをも使用することができる。また、ポリビニルアルコールを変性した化合物、例えば、アセトアセチル化ポリビニルアルコール、ポリビニルアルコールと多価カルボン酸とのエステル化物、カルボキシ変性化ポリビニルアルコール、スルホン酸変性化ポリビニルアルコール、オレフィン変性化ポリビニルアルコール、ニトリル変性化ポリビニルアルコール、アミド変性化ポリビニルアルコール、ピロリドン変性化ポリビニルアルコール等の変性化ポリビニルアルコール化合物を使用することができる。ポリビニルアルコールは、多孔質繊維に存在する細孔や基紙内部への浸透性が低いものが好ましく、例えば、アニオン変性ポリビニルアルコールが好ましい。多孔質繊維の表面がアニオン性なので内部へ浸透しにくくなる。 As polyvinyl alcohol, any of polyvinyl alcohol which is said to be a completely saponified type having a degree of saponification exceeding 95 mol% and polyvinyl alcohol which is said to be a partially saponified type of 70 to 90 mol% can be used. Also, compounds modified with polyvinyl alcohol, such as acetoacetylated polyvinyl alcohol, esterified product of polyvinyl alcohol and polyvalent carboxylic acid, carboxy modified polyvinyl alcohol, sulfonic acid modified polyvinyl alcohol, olefin modified polyvinyl alcohol, nitrile modified Modified polyvinyl alcohol compounds such as modified polyvinyl alcohol, amide-modified polyvinyl alcohol, and pyrrolidone-modified polyvinyl alcohol can be used. The polyvinyl alcohol is preferably one having low permeability to the pores and the base paper present in the porous fiber, for example, anion-modified polyvinyl alcohol is preferred. Since the surface of the porous fiber is anionic, it is difficult to penetrate into the inside.
フッ素系耐油剤とポリビニルアルコールが混合状態であるとは、基紙内部において、フッ素系耐油剤が分散している領域にポリビニルアルコールが分散している状態である。フッ素系耐油剤とポリビニルアルコールの分散の程度は限定されないが、フッ素系耐油剤の分散の程度が高い状態ほど好ましい。フッ素系耐油剤がポリビニルアルコールと混合状態となることにより、フッ素系耐油剤の基紙内部への浸透が抑えられる。 The mixed state of the fluorinated oil proofing agent and polyvinyl alcohol means that the polyvinyl alcohol is dispersed in the region where the fluorinated oil proofing agent is dispersed inside the base paper. The degree of dispersion of the fluorinated oil proofing agent and polyvinyl alcohol is not limited, but the higher the degree of dispersion of the fluorinated oil proofing agent, the better. When the fluorinated oil proofing agent is mixed with polyvinyl alcohol, the penetration of the fluorinated oil proofing agent into the base paper is suppressed.
混合状態のフッ素系耐油剤とポリビニルアルコールの浸透は、表面から裏面までであっても良いが、表面から基紙内部の途中までであることが好ましい。すなわち、フッ素系耐油剤の浸透を表面から浅い地点までに抑えることが好ましい。フッ素系耐油剤を耐油性の発現に効果がある領域にだけ存在させることで、耐油性を低下させることなく、フッ素系耐油剤を低減できる。 The penetration of the mixed fluorine-based oilproof agent and polyvinyl alcohol may be from the front surface to the back surface, but is preferably from the front surface to the middle of the base paper. That is, it is preferable to suppress the penetration of the fluorinated oil resistant agent from the surface to a shallow point. By allowing the fluorinated oil proofing agent to exist only in a region that is effective in developing oil resistance, the fluorinated oil proofing agent can be reduced without lowering the oil resistance.
また、ポリビニルアルコールと混合状態のフッ素系耐油剤の濃度は、基紙表面において耐油性能が得られる濃度とする必要があり、基紙の深さ方向について、表面に近いほど濃度が高いことが好ましい。フッ素系耐油剤を、耐油性の発現に効果がある領域に多く存在させることで、耐油性を低下させることなく、フッ素系耐油剤を低減できる。 Further, the concentration of the fluorine-based oil proofing agent in a mixed state with polyvinyl alcohol needs to be a concentration at which oil resistance is obtained on the surface of the base paper, and the concentration is preferably higher as the surface is closer to the surface in the depth direction of the base paper. . By making a large amount of the fluorine-based oil proofing agent exist in a region effective in the expression of oil resistance, the fluorine-based oil proofing agent can be reduced without reducing the oil resistance.
基紙中でフッ素系耐油剤とポリビニルアルコールとを混合状態とする方法は、例えば、フッ素系耐油剤とポリビニルアルコールとの混合液を浸透させる方法、まずポリビニルアルコールの溶液を浸透させ、湿潤状態の間に、フッ素系耐油剤の溶液を浸透させる方法、まずポリビニルアルコールの溶液を浸透させ、乾燥状態とした後に、フッ素系耐油剤を浸透させる方法、又は、フッ素系耐油剤の溶液とポリビニルアルコールの溶液をスプレーで吹きつけて同時に浸透させる方法がある。 A method of mixing a fluorine-based oilproof agent and polyvinyl alcohol in a base paper is, for example, a method of infiltrating a mixed solution of a fluorine-based oilproof agent and polyvinyl alcohol, first, infiltrating a solution of polyvinyl alcohol, and in a wet state. In between, a method of infiltrating a solution of a fluorine-based oil proofing agent, a method of first infiltrating a solution of polyvinyl alcohol and making it dry, and then a method of infiltrating a fluorinated oil-proofing agent, or There is a method in which the solution is sprayed and simultaneously infiltrated.
上述したフッ素系耐油剤とポリビニルアルコールの混合液を浸透させる方法、すなわち、多孔質繊維を主成分とした基紙の少なくとも片面側から、フッ素系耐油剤とポリビニルアルコールを含有した混合液を浸透させる工程と、前記混合液を浸透させた前記基紙を乾燥する工程と、を有する製造方法では、フッ素系耐油剤の浸透が抑えられる効果が大きく、また、フッ素系耐油剤とポリビニルアルコールを１回の塗工で浸透させることができるため生産性が高い。 The above-described method of infiltrating a mixed solution of a fluorine-based oilproof agent and polyvinyl alcohol, that is, a solution containing a fluorine-based oilproofing agent and polyvinyl alcohol is infiltrated from at least one side of a base paper mainly composed of porous fibers. And a step of drying the base paper impregnated with the mixed solution has a great effect of suppressing the penetration of the fluorinated oil proofing agent, and the fluorinated oil proofing agent and polyvinyl alcohol are used once. Productivity is high because it can be penetrated by coating.
フッ素系耐油剤の溶液は、ポリビニルアルコールの溶液と比較して浸透性が高く、多孔質繊維に存在する細孔や基紙内部へ容易に浸透する。そのため、耐油性を発現するに十分な量のフッ素系耐油剤を表面に存在させるためには、大量のフッ素系耐油剤を必要とする。 The fluorine-based oil proofing agent solution has higher permeability than the polyvinyl alcohol solution, and easily penetrates into the pores existing in the porous fiber and the inside of the base paper. Therefore, a large amount of fluorine-based oilproof agent is required in order to allow a sufficient amount of fluorine-based oilproof agent to be exhibited on the surface.
これに対し、上述した混合液を浸透させる方法では、フッ素耐油剤のみを浸透させた耐油紙と比較して少ない量のフッ素系耐油剤でも耐油性が得られる。フッ素系耐油剤とポリビニルアルコールとの混合液は、フッ素系耐油剤の溶液と比較して浸透性が低いため、フッ素系耐油剤が多孔質繊維に存在する細孔や基紙内部へ浸透しにくくなり、その結果、フッ素系耐油剤を表面近くに留めておくことが可能となったと考えられる。 On the other hand, in the above-described method of infiltrating the mixed liquid, oil resistance can be obtained even with a small amount of the fluorine-based oil resistant agent as compared with the oil-resistant paper in which only the fluorine oil-resistant agent is infiltrated. The mixed liquid of fluorine-based oil proofing agent and polyvinyl alcohol has low permeability compared to the solution of fluorine-based oil proofing agent, so it is difficult for the fluorinated oil-proofing agent to penetrate into the pores and the base paper inside the porous fiber. As a result, it is considered that the fluorine-based oilproofing agent can be kept close to the surface.
また、この製造方法による基紙では、基紙の内部に空隙を多く残しており、透気性が得られる。 Moreover, in the base paper by this manufacturing method, many voids remain inside the base paper, and air permeability is obtained.
これに対し、フッ素系耐油剤を用いずにポリビニルアルコールのみを使用した場合は、耐油性を得るためにはポリビニルアルコールで基紙の表面の空隙を塞ぐ必要があり、透気性が得られない。 On the other hand, when only polyvinyl alcohol is used without using a fluorine-based oil resistant agent, it is necessary to block the voids on the surface of the base paper with polyvinyl alcohol in order to obtain oil resistance, and air permeability cannot be obtained.
本実施形態に係る耐油紙では、フッ素系耐油剤とポリビニルアルコールの固形分の質量比は、７：３〜３：７としている。好ましくは、６：４〜４：６である。フッ素系耐油剤の比率が７：３より大きくなるとポリビニルアルコールが少ないためフッ素系耐油剤の浸透を十分に抑えられない。フッ素系耐油剤の比率が３：７より小さくなるとポリビニルアルコールの影響で透気性が悪くなり品質上の問題を発生させる。 In the oil resistant paper according to the present embodiment, the mass ratio of the solid content of the fluorine-based oil resistant agent and the polyvinyl alcohol is set to 7: 3 to 3: 7. Preferably, it is 6: 4-4: 6. If the ratio of the fluorinated oil proofing agent is larger than 7: 3, the penetration of the fluorinated oil proofing agent cannot be sufficiently suppressed because of the small amount of polyvinyl alcohol. When the ratio of the fluorinated oil proofing agent is smaller than 3: 7, the air permeability is deteriorated due to the influence of polyvinyl alcohol, which causes quality problems.
本実施形態に係る耐油紙では、前記多孔質繊維１００質量部に対して、０．１０質量部以上０．２６質量部未満のフッ素系耐油剤が浸透されていることが好ましい。より好ましくは、０．１２質量部以上０．２０質量部未満であり、さらに好ましくは、０．１３質量部以上０．１８質量部未満である。フッ素系耐油剤のみでは十分な耐油性が得られない量ではあるが、ポリビニルアルコールとの混合状態とすることで耐油性が安定して得られる。 In the oil resistant paper according to the present embodiment, it is preferable that a fluorinated oil resistant agent of 0.10 parts by mass or more and less than 0.26 parts by mass permeates 100 parts by mass of the porous fiber. More preferably, it is 0.12 mass part or more and less than 0.20 mass part, More preferably, it is 0.13 mass part or more and less than 0.18 mass part. Although sufficient oil resistance cannot be obtained with only a fluorine-based oil resistant agent, oil resistance can be stably obtained by mixing with polyvinyl alcohol.
本実施形態に係る耐油紙では、前記ポリビニルアルコールの含有量が、多孔質繊維１００質量部に対して、０．０５質量部以上０．５０質量部未満であることが好ましい。より好ましくは０．０８質量部以上０．３０質量部未満であり、さらに好ましくは０．１０質量部以上０．２５質量部未満である。透気性を低下させることなく、フッ素系耐油剤の浸透を抑える効果が安定して得られる。 In the oil resistant paper according to this embodiment, the content of the polyvinyl alcohol is preferably 0.05 parts by mass or more and less than 0.50 parts by mass with respect to 100 parts by mass of the porous fiber. More preferably, it is 0.08 mass part or more and less than 0.30 mass part, More preferably, it is 0.10 mass part or more and less than 0.25 mass part. The effect of suppressing the penetration of the fluorinated oil resistance agent can be stably obtained without reducing the air permeability.
耐油性及び透気性は、フッ素系耐油剤とポリビニルアルコールを浸透させる量及びその固形分の質量比により調整することができる。例えば、透気性を落とさない範囲でポリビニルアルコールの量を増やすことで、フッ素系耐油剤の浸透がより抑えられ、フッ素系耐油剤の量を減らしても透気性と耐油性が得られる。本実施形態に係る耐油紙では、ＴＡＰＰＩ ＵＭ ５５７「Ｒｅｐｅｌｌｅｎｃｙ ｏｆ Ｐａｐｅｒ ａｎｄ Ｂｏａｒｄ ｔｏ Ｇｒｅａｓｅ，Ｏｉｌ，ａｎｄ Ｗａｘｅｓ（Ｋｉｔ Ｔｅｓｔ）」で規定される耐油度が５級以上であり、且つ、ＪＩＳ Ｐ ８１１７「紙及び板紙−透気度試験方法−ガーレー試験機法」で規定される透気度が５０秒以下であることが好ましく、耐油度と透気度がこの範囲となるように調整することが好ましい。 Oil resistance and gas permeability can be adjusted by the amount of the fluorine-based oil resistant agent and polyvinyl alcohol that permeates and the mass ratio of the solid content. For example, by increasing the amount of polyvinyl alcohol as long as the air permeability is not reduced, the penetration of the fluorine-based oil resistant agent can be further suppressed, and even if the amount of the fluorine-based oil resistant agent is decreased, the air permeability and oil resistance can be obtained. In the oil-resistant paper according to the present embodiment, the oil resistance specified by TAPPI UM 557 “Repelency of Paper and Board to Grade, Oil, and Waxes (Kit Test)” is 5th grade or more, and JIS P 8117 “Paper” And the paperboard-air permeability test method-Gurley tester method "is preferably 50 seconds or less, and the oil resistance and the air permeability are preferably adjusted to be in this range.
本実施形態に係る耐油紙は、耐油性と透気性が維持されれば、フッ素系耐油剤とポリビニルアルコールを浸透させた表面上にさらに塗工層が形成された形態であっても良い。また、フッ素系耐油剤とポリビニルアルコールを浸透させた基紙を複数枚重ね合わせた形態であっても良い。 The oil-resistant paper according to the present embodiment may have a form in which a coating layer is further formed on a surface infiltrated with a fluorine-based oil-resistant agent and polyvinyl alcohol as long as oil resistance and air permeability are maintained. Moreover, the form which overlap | superposed several sheets of the base paper which osmose | permeated the fluorine-type oilproof agent and polyvinyl alcohol may be sufficient.
フッ素系耐油剤とポリビニルアルコールの混合液、フッ素系耐油剤の溶液、及び、ポリビニルアルコールの溶液には、必要に応じて添加剤を添加することができる。このような添加剤としては、例えば、分散剤、消泡剤、増粘剤、耐水化剤、可塑剤、蛍光増白剤、着色顔料、着色染料、還元剤、紫外線吸収剤、酸化防止剤、香料、脱臭剤がある。 Additives can be added to the mixed solution of the fluorinated oil proofing agent and polyvinyl alcohol, the fluorinated oil proofing agent solution, and the polyvinyl alcohol solution, if necessary. Examples of such additives include dispersants, antifoaming agents, thickeners, water resistance agents, plasticizers, fluorescent whitening agents, coloring pigments, coloring dyes, reducing agents, ultraviolet absorbers, antioxidants, There are fragrances and deodorants.
フッ素系耐油剤及びポリビニルアルコールの基紙への浸透は、抄紙機に付属する塗工機で行うオンマシン塗工によっても良いし、抄紙機と切り離された塗工機で行うオフマシン塗工によっても良いが、本実施形態に係る耐油紙の製造方法では、前記混合液を浸透させる工程において、抄紙機に付属する塗工機によって前記混合液を前記基紙に浸透させることが好ましい。耐油紙の生産効率が高まる。抄紙機に付属する塗工機としては、サイズプレス、ゲートロール、シムサイザー等一般的に抄紙機に付属する塗工機を使用することができる。 Permeation of fluorine-based oil proofing agent and polyvinyl alcohol into the base paper may be performed by on-machine coating performed by a coating machine attached to the paper machine, or by off-machine coating performed by a coating machine separated from the paper machine. However, in the method for producing oil-resistant paper according to this embodiment, in the step of infiltrating the mixed solution, it is preferable that the mixed solution is infiltrated into the base paper by a coating machine attached to a paper machine. Increases oil-resistant paper production efficiency. As the coating machine attached to the paper machine, a coating machine generally attached to the paper machine such as a size press, a gate roll, and a shim sizer can be used.
フッ素系耐油剤とポリビニルアルコールの混合液を浸透させた基紙の乾燥は、多筒式抄紙機やヤンキー抄紙機等一般的に抄紙機に付属するドライヤーを使用することができる。 Drying of the base paper impregnated with a mixture of a fluorinated oilproofing agent and polyvinyl alcohol can be performed using a dryer generally attached to the paper machine such as a multi-cylinder paper machine or a Yankee paper machine.
又、上記耐油紙は、通常の抄紙機で行われる、プレス圧、乾燥温度、カレンダー圧、抄造速度等を調節することによって、好ましい平滑度や脱水状態のものとすることができる。 The oil-resistant paper can have a preferable smoothness or dehydrated state by adjusting a press pressure, a drying temperature, a calender pressure, a paper making speed, and the like, which are performed with a normal paper machine.
以下、本発明について実施例を挙げて詳細に説明するが、本発明の内容は実施例に限定されるものではない。なお、「％」及び「部」は固形分換算での「質量％」及び「質量部」を示す。 EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the content of this invention is not limited to an Example. “%” And “part” indicate “% by mass” and “part by mass” in terms of solid content.
（参考例１）
［塗料の調製］
フッ素系耐油剤（商品名：ＰＴ−５０４５、ソルベイソレクシス社製）とポリビニルアルコール（商品名：ＰＶＡ−２１７、クラレ社製）を、固形分の質量比５：５で混合して塗料を調製した。
［基紙の抄造］
針葉樹パルプ（Ｎ−ＢＫＰ）と広葉樹パルプ（Ｌ−ＢＫＰ）を３０％／７０％に混合し、叩解機により、ＣＦＳ４００ｍｌとなるように叩解処理した。これらのパルプスラリーに、全パルプ１００部に対して、内添サイズ剤としてロジン系エマルジョン（商品名：ＡＬ−１２００、星光ＰＭＣ製）を０．４部、硫酸バンドを０．１４部添加し、長網抄紙機で抄紙して坪量２３０ｇ／ｍ２の基紙を得た。
［塗料の浸透］
そして上記基紙をそのまま長網抄紙機に設備されているサイズプレスにて、上記［塗料の調製］に示す塗料を全パルプ１００部に対して、０．２６部浸透させ、ドライヤーで乾燥して、参考例１の耐油紙を得た。
( Reference Example 1 )
[Preparation of paint]
Fluorine-based oil-resistant agent (trade name: PT-5045, manufactured by Solvay Solexis) and polyvinyl alcohol (trade name: PVA-217, manufactured by Kuraray Co., Ltd.) are mixed at a mass ratio of 5: 5 to prepare a paint. did.
[Making paper]
Softwood pulp (N-BKP) and hardwood pulp (L-BKP) were mixed at 30% / 70%, and beaten with a beating machine to a CFS of 400 ml. To these pulp slurries, with respect to 100 parts of the total pulp, 0.4 parts of rosin emulsion (trade name: AL-1200, manufactured by Seiko PMC) as an internal sizing agent and 0.14 parts of sulfuric acid band were added, Paper was made with a long paper machine to obtain a base paper having a basis weight of 230 g / m 2 .
[Penetration of paint]
Then, the base paper is directly impregnated with 0.26 parts of the coating material shown in [Preparation of paint] with respect to 100 parts of the pulp in a size press installed in the long paper machine, and dried with a dryer. The oil-resistant paper of Reference Example 1 was obtained.
（実施例２）
［塗料の調製］において、ポリビニルアルコール（商品名：ＰＶＡ−２１７、クラレ社製）をアニオン変性ポリビニルアルコール（商品名：ＡＰ−１７、日本酢ビ・ポバール社製）へ変更した以外は、参考例１と同じ方法で実施例２の耐油紙を得た。
(Example 2)
Reference Example , except that polyvinyl alcohol (trade name: PVA-217, manufactured by Kuraray Co., Ltd.) was changed to anion-modified polyvinyl alcohol (trade name: AP-17, manufactured by Nippon Vinegar Pover Co.) in [Preparation of paint] The oil-resistant paper of Example 2 was obtained by the same method as 1 .
（実施例３）
［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．２０部へ変更した以外は、実施例２と同じ方法で実施例３の耐油紙を得た。
(Example 3)
In [Penetration of paint], the oil-resistant paper of Example 3 was obtained in the same manner as in Example 2, except that the amount of paint to be penetrated was changed from 0.26 parts to 0.20 parts.
（実施例４）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から７：３へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．１８部へ変更した以外は、実施例２と同じ方法で実施例４の耐油紙を得た。
(Example 4)
In [Preparation of paint], the mass ratio of the solid content of the fluorinated oil proofing agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 7: 3. The oil-resistant paper of Example 4 was obtained in the same manner as in Example 2 except that the amount was changed from 0.1 part to 0.18 part.
（実施例５）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から３：７へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．３４部へ変更した以外は、実施例２と同じ方法で実施例５の耐油紙を得た。
(Example 5)
In [Preparation of paint], the mass ratio of the solid content of the fluorinated oilproof agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 3: 7. The oil-resistant paper of Example 5 was obtained in the same manner as in Example 2 except that the amount was changed from 0.3 part to 0.34 part.
（実施例６）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から３：７へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．４３部へ変更した以外は、実施例２と同じ方法で実施例６の耐油紙を得た。
(Example 6)
In [Preparation of paint], the mass ratio of the solid content of the fluorinated oilproof agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 3: 7. The oil-resistant paper of Example 6 was obtained in the same manner as in Example 2 except that the amount was changed from 0.4 part to 0.43 part.
（比較例１）
［塗料の調製］を以下に示す方法で行った以外は実施例２と同じ方法で比較例１の耐油紙を得た。
［塗料の調整］
フッ素系耐油剤（商品名：ＰＴ−５０４５、ソルベイソレクシス社製）で塗料を調製した。
(Comparative Example 1)
An oil resistant paper of Comparative Example 1 was obtained in the same manner as in Example 2 except that [Preparation of paint] was carried out by the method shown below.
[Adjustment of paint]
A paint was prepared with a fluorine-based oilproofing agent (trade name: PT-5045, manufactured by Solvay Solexis).
（比較例２）
［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．１３部へ変更した以外は、比較例１と同じ方法で比較例２の耐油紙を得た。
(Comparative Example 2)
In [Penetration of paint], an oil-resistant paper of Comparative Example 2 was obtained in the same manner as Comparative Example 1 except that the amount of the paint to be penetrated was changed from 0.26 parts to 0.13 parts.
（比較例３）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から８：２へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．１６部へ変更した以外は、実施例２と同じ方法で比較例３の耐油紙を得た。
(Comparative Example 3)
In [Preparation of paint], the mass ratio of the solid content of the fluorine-based oilproof agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 8: 2, and in [Penetration of paint], the amount of paint to be permeated was 0.26. The oil-resistant paper of Comparative Example 3 was obtained in the same manner as in Example 2 except that the amount was changed from 0.1 part to 0.16 part.
（比較例４）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から２：８へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．５０部へ変更した以外は、実施例２と同じ方法で比較例４の耐油紙を得た。
(Comparative Example 4)
In [Preparation of paint], the mass ratio of the solid content of the fluorinated oilproof agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 2: 8, and in [Penetration of paint], the amount of paint to be permeated was 0.26. The oil-resistant paper of Comparative Example 4 was obtained in the same manner as in Example 2 except that the amount was changed from 0.5 part to 0.50 part.
（比較例５）
［塗料の調製］において、フッ素系耐油剤とアニオン変性ポリビニルアルコールの固形分の質量比を５：５から２：８へ変更し、［塗料の浸透］において、浸透させる塗料の量を０．２６部から０．４５部へ変更した以外は、実施例２と同じ方法で比較例５の耐油紙を得た。
(Comparative Example 5)
In [Preparation of paint], the mass ratio of the solid content of the fluorinated oilproof agent and the anion-modified polyvinyl alcohol was changed from 5: 5 to 2: 8, and in [Penetration of paint], the amount of paint to be permeated was 0.26. The oil-resistant paper of Comparative Example 5 was obtained in the same manner as in Example 2 except that the amount was changed from 0.4 part to 0.45 part.
（比較例６）
針葉樹パルプ（Ｎ−ＢＫＰ）と広葉樹パルプ（Ｌ−ＢＫＰ）を３０％／７０％に混合し、叩解機により、ＣＦＳ４００ｍｌとなるように叩解処理した。これらのパルプスラリー１００部に、内添サイズ剤としてロジン系エマルジョン（商品名：ＡＬ−１２００、星光ＰＭＣ製）を０．４部、硫酸バンドを０．１４部、フッ素系耐油剤（商品名：ＰＴ−５０４５、ソルベイソレクシス社製）を０．１３部、アニオン変性ポリビニルアルコール（商品名：ＡＰ−１７、日本酢ビ・ポバール社製）を０．１３部添加し、長網抄紙機で抄紙して、ドライヤーで乾燥して、坪量２３０ｇ／ｍ２の比較例６の耐油紙を得た。
(Comparative Example 6)
Softwood pulp (N-BKP) and hardwood pulp (L-BKP) were mixed at 30% / 70%, and beaten with a beating machine to a CFS of 400 ml. To 100 parts of these pulp slurries, 0.4 part of rosin emulsion (trade name: AL-1200, manufactured by Seiko PMC) as an internal sizing agent, 0.14 part of sulfuric acid band, fluorine-based oilproofing agent (trade name: 0.13 parts of PT-5045 (manufactured by Solvay Solexis) and 0.13 parts of anion-modified polyvinyl alcohol (trade name: AP-17, manufactured by Nihon Acetate / Poval) are added, and the paper is made with a long paper machine. And it dried with the dryer and obtained the oil-resistant paper of the comparative example 6 with a basic weight of 230 g / m < 2 >.
上記の参考例１、実施例２、３、４、５及び６並びに比較例１、２、３、４、５及び６の各試料について、耐油度及び透気度を測定した。これらの測定結果は、表１に示した。次に測定方法について説明する。 The oil resistance and air permeability of each sample of Reference Example 1, Examples 2, 3, 4, 5 and 6 and Comparative Examples 1, 2, 3, 4, 5 and 6 were measured. These measurement results are shown in Table 1. Next, the measurement method will be described.
（１）耐油度
ＴＡＰＰＩ ＵＭ ５５７「Ｒｅｐｅｌｌｅｎｃｙ ｏｆ Ｐａｐｅｒ ａｎｄ Ｂｏａｒｄ ｔｏ Ｇｒｅａｓｅ，Ｏｉｌ，ａｎｄ Ｗａｘｅｓ（Ｋｉｔ Ｔｅｓｔ）」によって測定した。現在市販されているフッ素系耐油剤を用いた耐油紙の耐油度は５級以上であることから、一般的な使用において問題の発生しない耐油度が５級以上を実用レベルとした。
(1) Oil resistance Measured by TAPPI UM 557 “Repelency of Paper and Board to Grade, Oil, and Waxes (Kit Test)”. Since the oil resistance of oil-resistant paper using a fluorine-based oil-proofing agent currently on the market is grade 5 or higher, the oil resistance level that does not cause problems in general use is grade 5 or higher.
（２）透気度
ＪＩＳ Ｐ ８１１７：１９９８「紙及び板紙−透気度試験方法−ガーレー試験機法」によって測定した。透気度の値は、一定面積を空気１００ミリリットルが通過する時間を示す。よって、透気度の値が大きいほど空気が通過し難いことを示す。透気度５０秒以下を実用レベルとした。
(2) Air permeability Measured according to JIS P 8117: 1998 “Paper and paperboard—Air permeability test method—Gurley tester method”. The air permeability value indicates the time required for 100 ml of air to pass through a certain area. Therefore, it shows that air is hard to pass, so that the value of air permeability is large. The air permeability of 50 seconds or less was regarded as a practical level.
参考例１、実施例２、３、４、５及び６では、フッ素系耐油剤とポリビニルアルコールの固形分の質量比を７：３〜３：７の範囲内とした混合液を基紙に浸透させており、いずれも耐油度と透気度は実用レベルであった。 In Reference Example 1, Examples 2, 3, 4, 5, and 6, the mixed liquid in which the mass ratio of the solid content of the fluorine-based oil resistant agent and polyvinyl alcohol was within the range of 7: 3 to 3: 7 was permeated into the base paper. Both oil resistance and air permeability were at practical levels.
比較例１及び２では、ポリビニルアルコールを浸透させずに、フッ素系耐油剤のみを基紙に浸透させた。比較例１では耐油度と透気度のいずれも実用レベルであったが、フッ素系耐油剤の量を減らした比較例２では、透気度は実用レベルであったが、耐油度が実用レベルでなかった。ポリビニルアルコールを浸透させない場合は、フッ素系耐油剤の量を減らすと実用レベルの耐油性が得られなくなる。これに対し、フッ素系耐油剤とポリビニルアルコールを浸透させた参考例１、実施例２、３、４、５及び６では耐油剤の量を減らしているにもかかわらず実用レベルの耐油性が得られる。 In Comparative Examples 1 and 2, only the fluorine-based oilproof agent was permeated into the base paper without permeating polyvinyl alcohol. In Comparative Example 1, both the oil resistance and the air permeability were at a practical level. In Comparative Example 2 in which the amount of the fluorine-based oil resistant agent was reduced, the air permeability was at a practical level, but the oil resistance was at a practical level. It was not. When polyvinyl alcohol is not infiltrated, a practical level of oil resistance cannot be obtained if the amount of the fluorine-based oil resistant agent is reduced. On the other hand, in Reference Example 1, Examples 2, 3, 4, 5, and 6 in which a fluorine-based oil resistant agent and polyvinyl alcohol were infiltrated, a practical level of oil resistance was obtained even though the amount of the oil resistant agent was reduced. It is done.
比較例３、４及び５では、フッ素系耐油剤とポリビニルアルコールを浸透させているが、その固形分の質量比が７：３〜３：７の範囲外であった。比較例３では耐油度が実用レベルでなかった。ポリビニルアルコールの割合が少ないとフッ素系耐油剤の浸透を抑える効果が不十分である。比較例４では、耐油度は実用レベルであったが、透気度が実用レベルでなかった。フッ素系耐油剤の量が少なくても、ポリビニルアルコールの割合を多くすることで耐油度は実用レベルとなるが、透気度が実用レベルでなくなる。比較例５では、フッ素系耐油剤とポリビニルアルコールの割合は比較例４と同じでその量を減らした。耐油剤と透気度のいずれも実用レベルとはならなかった。フッ素系耐油剤を減らした場合、フッ素系耐油剤とポリビニルアルコールの固形分の質量比が所定の範囲内とすることで耐油性と透気性を両立できる。 In Comparative Examples 3, 4 and 5, the fluorine-based oilproof agent and polyvinyl alcohol were permeated, but the mass ratio of the solid content was outside the range of 7: 3 to 3: 7. In Comparative Example 3, the oil resistance was not at a practical level. When the proportion of polyvinyl alcohol is small, the effect of suppressing penetration of the fluorinated oilproof agent is insufficient. In Comparative Example 4, the oil resistance was a practical level, but the air permeability was not a practical level. Even if the amount of the fluorinated oil proofing agent is small, by increasing the proportion of polyvinyl alcohol, the oil resistance becomes a practical level, but the air permeability becomes a practical level. In Comparative Example 5, the ratio of the fluorinated oil proofing agent and polyvinyl alcohol was the same as in Comparative Example 4, and the amount thereof was reduced. Neither oil proofing agent nor air permeability became practical level. When the fluorine-based oilproofing agent is reduced, the oil resistance and the air permeability can be compatible by setting the mass ratio of the solid content of the fluorine-based oilproofing agent and the polyvinyl alcohol within a predetermined range.
参考例１では変性していないポリビニルアルコールを使用し、実施例２ではアニオン変性ポリビニルアルコールを使用した。いずれも耐油度と透気度は実用レベルであったが、アニオン変性ポリビニルアルコールを使用した実施例２は耐油度がより良好となった。
In Reference Example 1 , unmodified polyvinyl alcohol was used, and in Example 2, anion-modified polyvinyl alcohol was used. In both cases, the oil resistance and air permeability were at practical levels, but Example 2 using anion-modified polyvinyl alcohol had a better oil resistance.
比較例６では、基紙を抄紙する段階でフッ素系耐油剤とポリビニルアルコールを内添させており、耐油性は実用レベルとはならなかった。フッ素系耐油剤とポリビニルアルコールは混合状態になっていると考えられるが、それらを浸透させていない場合は、フッ素系耐油剤が少ないと所望の耐油度が得られない。 In Comparative Example 6, a fluorine-based oilproofing agent and polyvinyl alcohol were added internally at the stage of making the base paper, and the oil resistance was not at a practical level. Although it is considered that the fluorinated oil proofing agent and the polyvinyl alcohol are in a mixed state, if they are not permeated, the desired oil resistance cannot be obtained if the amount of the fluorinated oil proofing agent is small.
Claims (4)
前記フッ素系耐油剤と前記アニオン変性ポリビニルアルコールの固形分の質量比が、７：３〜３：７であり、かつ、前記多孔質繊維１００質量部に対して、０．１０質量部以上０．２６質量部未満のフッ素系耐油剤が浸透されていることを特徴とする耐油紙。 A base paper containing a porous fiber as a main component and containing an internal sizing agent, an oil-resistant paper in which a paint mixed with a fluorine-based oil-resistant agent and an anion-modified polyvinyl alcohol is infiltrated,
The mass ratio of the solid content of the fluorinated oilproofing agent and the anion-modified polyvinyl alcohol is 7: 3 to 3: 7, and is 0.10 parts by mass or more and 0.1 to 0.3 parts by mass with respect to 100 parts by mass of the porous fiber. An oil-resistant paper in which less than 26 parts by mass of a fluorine-based oil-resistant agent is permeated.
前記混合液を浸透させた前記基紙を乾燥する工程と、を有することを特徴とする耐油紙の製造方法。 From at least one side of the base paper containing the porous fiber as a main component and containing the internal sizing agent, the fluorine-based oilproof agent and the anion-modified polyvinyl alcohol are in a mass ratio of 7: 3 to 3: 7 in terms of solid content. The mixed liquid contained in a proportion was infiltrated, and the amount of the mixed liquid infiltrated was 0.10 parts by mass or more and less than 0.26 parts by mass with respect to 100 parts by mass of the porous oilproof agent. An amount of steps,
And a step of drying the base paper infiltrated with the mixed liquid.
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