JP2012067402A - Oil-resistant paper and method for producing oil-resistant paper - Google Patents
Oil-resistant paper and method for producing oil-resistant paper Download PDFInfo
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- JP2012067402A JP2012067402A JP2010211718A JP2010211718A JP2012067402A JP 2012067402 A JP2012067402 A JP 2012067402A JP 2010211718 A JP2010211718 A JP 2010211718A JP 2010211718 A JP2010211718 A JP 2010211718A JP 2012067402 A JP2012067402 A JP 2012067402A
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- JP
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- Prior art keywords
- oil
- resistant
- meth
- acrylic resin
- paper
- 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.)
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
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- 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 2
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- MADOXCFISYCULS-UHFFFAOYSA-N octyl 2-sulfanylacetate Chemical compound CCCCCCCCOC(=O)CS MADOXCFISYCULS-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
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- 229940096992 potassium oleate Drugs 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 description 1
- 235000013324 preserved food Nutrition 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- ZNZJJSYHZBXQSM-UHFFFAOYSA-N propane-2,2-diamine Chemical compound CC(C)(N)N ZNZJJSYHZBXQSM-UHFFFAOYSA-N 0.000 description 1
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- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
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Landscapes
- Paper (AREA)
Abstract
Description
本発明は、動植物油等の油分の浸透を抑制する耐油紙および耐油紙の製造方法に関するものである。 The present invention relates to an oil-resistant paper that suppresses permeation of oil such as animal and vegetable oils and a method for producing the oil-resistant paper.
従来耐油紙は、洗剤、菓子、乾燥食品等の包装容器用素材として広く使用されていた。その用途としては様々なものがあるが、耐油性を付与した板紙については菓子等の食品用の箱、とりわけ油脂分を大量に含むチョコレート菓子等の箱としてや、薄葉紙に耐油性を付与したものについてはファーストフードなどの揚げ物を包装する容器やデパート、コンビニエンスストアなどでのテイクアウト食材の包装容器等に多く使用されている。 Conventionally, oil-resistant paper has been widely used as a material for packaging containers such as detergents, confectionery, and dried foods. There are various uses, but for paperboard with oil resistance, it is used as a box for food such as confectionery, especially as a box for chocolate confectionery containing a large amount of oils and fats. Is often used for containers for packaging fried foods such as fast food, and for take-out food packaging containers in department stores and convenience stores.
紙に耐油性を付与する手段としては、優れた耐油性を有するフッ素樹脂系の耐油剤が従来使用されており、例えば、紙、板紙の表面にフッ素樹脂系耐油剤を塗工して耐油層を設けたクッキングシートまたは紙層間にフッ素樹脂系耐油剤層を設けた菓子箱用の耐油板紙等が存在した。しかし、フッ素樹脂系耐油剤を使用した紙は、１００〜１８０℃の食品調理温度で加熱した場合、Ｃ８〜Ｃ１０のフッ素系アルコール化合物等、長期に残留しやすい成分が発生することが確認されている。また、これらフッ素樹脂系耐油剤を使用した紙を使用後焼却した際には、パーフルオロオクタン酸やパーフルオロスルホン酸等のフッ素化合物が発生し、健康または環境に悪影響を及ぼすことが懸念されるため、フッ素樹脂系耐油剤を使用しない耐油紙が求められている。 As a means for imparting oil resistance to paper, a fluororesin-based oil-resistant agent having excellent oil resistance has been conventionally used. For example, by applying a fluororesin-based oil-resistant agent on the surface of paper or paperboard, an oil-resistant layer There existed a cooking sheet provided with an oil-resistant paperboard for a confectionery box provided with a fluororesin-based oilproofing agent layer between paper sheets. However, it has been confirmed that papers using fluororesin-based oilproofing agents are likely to remain for a long time, such as C8-C10 fluorinated alcohol compounds, when heated at a food cooking temperature of 100-180 ° C. Yes. In addition, when papers using these fluororesin-based oil-proofing agents are incinerated after use, fluorine compounds such as perfluorooctanoic acid and perfluorosulfonic acid are generated, and there is concern that they may adversely affect health or the environment. Therefore, there is a demand for oil-resistant paper that does not use a fluororesin-based oil resistant agent.
前記した熱分解するフッ素系薬品代替の耐油紙としては紙基材にアクリル樹脂系耐油剤を塗布したもの、ポリエチレンフィルム貼合紙、ポリエチレン樹脂を塗布したもの、シリコーン系、ワックス系耐油剤を使用したもの、熱を加えても不活性ガスを発生させないように製法が改良されたフッ素系樹脂を使用したもの等々の耐油紙ならびに該耐油紙の製造技術が開示されているが、それぞれ長短所があるため一部実用化されてはいるものの依然として、使用者からの改善要望は根強い。 As the above-mentioned oil-resistant paper as a substitute for fluorine-based chemicals that decompose thermally, paper base coated with acrylic resin-based oil-resistant agent, polyethylene film-bonded paper, polyethylene-coated resin, silicone-based, wax-based oil-resistant agent are used. Oil-resistant paper such as those using a fluorine-based resin whose production method has been improved so as not to generate an inert gas even when heat is applied, and a technique for producing the oil-resistant paper are disclosed. Although it is partly put into practical use, there is still a strong demand for improvement from users.
ところで、薬品の撥油性によって外部への油脂成分の滲出を防止するフッ素系樹脂を用いた耐油紙では必要耐油剤量が少量であるため、内部に添加、もしくはサイズプレスで該樹脂を表面に塗布させることが可能であった。 By the way, the oil-resistant paper using a fluorine resin that prevents the exudation of oil and fat components to the outside due to the oil repellency of chemicals requires a small amount of oil-resistant agent, so it is added inside or applied to the surface with a size press It was possible to make it.
一方、アクリル系樹脂エマルションの塗工により製造した耐油紙は、耐油層をピンホールなく成膜させて外部への油脂成分の滲出を防止することにより耐油性を発現させているため、フッ素系樹脂と比較すると、同等の耐油性を発現させるために必要な耐油剤量が多くなってしまうという問題がある。例えば、特許文献１〜３にはアクリル系樹脂をオフコーターもしくは印刷機を用いて基紙上に幾層にもわたり塗布する技術が開示されているが、いずれも幾層にもわたり塗布することにより耐油性は確保できるもののその手間の多さからコストが極端に高くなる。
また、特許文献４には耐油剤をエアーナイフコーターで単層のみ塗布する技術が開示されているが、エアーナイフコーターでの塗工の場合は、塗料濃度を比較的低く抑えなければならないため、乾燥負荷が増大し、生産効率が低下するため好ましくない。
On the other hand, oil-resistant paper produced by coating acrylic resin emulsions is made of a fluororesin because oil-resistant layers are formed without pinholes to prevent oil and fat components from leaching to the outside. In comparison with the above, there is a problem that the amount of the oil-resistant agent necessary for developing the equivalent oil resistance is increased. For example, Patent Documents 1 to 3 disclose a technique in which an acrylic resin is applied over several layers on a base paper using an off coater or a printing machine. Although oil resistance can be ensured, the cost is extremely high due to the large amount of time and effort.
Further, Patent Document 4 discloses a technique for applying only a single layer of an oil resistant agent with an air knife coater, but in the case of coating with an air knife coater, the coating concentration must be kept relatively low, Since drying load increases and production efficiency falls, it is not preferable.
そこで、効率的に塗布を行う手段として高速塗工が可能なトランスファーロールコーター方式の適用が考えられる。このトランスファーロールコーター方式は、オンマシンやオフマシンで使用されており、特に、ゲートロールコーターのようなトランスファーロールコーター方式は、抄紙機のサイズプレス装置としても使用されているが、耐油剤としてアクリル系樹脂を用いたトランスファーロールコーター方式による耐油紙の製造において所望の耐油性を発現させる塗工量を確保するのが困難であるというのが現状である。 Therefore, it is conceivable to apply a transfer roll coater system capable of high-speed coating as a means for efficiently applying. This transfer roll coater method is used on-machine and off-machine. In particular, a transfer roll coater method such as a gate roll coater is also used as a size press device of a paper machine, but an acrylic oil resistance agent is used. In the present situation, it is difficult to secure a coating amount that exhibits desired oil resistance in the production of oil-resistant paper by a transfer roll coater method using a resin.
本発明は、耐油性樹脂層として、特定のアクリル系樹脂を使用する事により、フッ素系化合物を用いないで環境面での問題の少ない食品用耐油紙を、トランスファーロールコーター方式で必要量塗布し、高い生産性と高い耐油性の発現を両立させることを目的とする。 The present invention uses a specific acrylic resin as the oil-resistant resin layer, thereby applying a necessary amount of oil-resistant paper for foods with less environmental problems without using a fluorine compound by the transfer roll coater method. The objective is to achieve both high productivity and high oil resistance.
本発明は、以下の各発明を包含する。
（１）紙支持体の少なくとも片面に少なくとも１層のアクリル系樹脂を主成分とする耐油層を設けた耐油紙であって、該アクリル系樹脂の重量平均分子量が５万〜２００万、かつ酸価が５０〜２５０ｍｇＫＯＨである耐油紙。
The present invention includes the following inventions.
(1) An oil-resistant paper provided with an oil-resistant layer comprising at least one acrylic resin as a main component on at least one surface of a paper support, wherein the acrylic resin has a weight average molecular weight of 50,000 to 2,000,000 and an acid Oil-resistant paper having a value of 50 to 250 mg KOH.
（２）前記アクリル系樹脂がコアシェル型構造のエマルションである（１）に記載の耐油紙。 (2) The oil-resistant paper according to (1), wherein the acrylic resin is an emulsion having a core-shell structure.
（３）前記アクリル系樹脂が平均粒子径０．０１〜１．０μｍのエマルションである（１）または（２）に記載の耐油紙。 (3) The oil-resistant paper according to (1) or (2), wherein the acrylic resin is an emulsion having an average particle size of 0.01 to 1.0 μm.
（４）前記耐油層の塗工量が２.０〜１５．０ｇ／ｍ２である（１）〜（３）のいずれか１項に記載の耐油紙。 (4) The oil resistant paper according to any one of (1) to (3), wherein a coating amount of the oil resistant layer is 2.0 to 15.0 g / m 2 .
（５）請求項１〜３のいずれか１項に記載のアクリル系樹脂を主成分とする耐油層塗液をトランスファーロールコーターで塗工する耐油紙の製造方法。 (5) A method for producing an oil-resistant paper, wherein the oil-resistant layer coating liquid mainly comprising the acrylic resin according to any one of claims 1 to 3 is applied with a transfer roll coater.
（６）前記耐油層塗液のせん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が５０〜２００ｃｐｓである（５）に記載の耐油紙の製造方法。 (6) The method for producing oil-resistant paper according to (5), wherein the high shear viscosity measured at a shear rate of 46000 (1 / s) of the oil-resistant layer coating solution is 50 to 200 cps.
（７）前記耐油層塗液をオンマシンゲートロールコーターで塗工する（５）または（６）に記載の耐油紙の製造方法。 (7) The method for producing oil-resistant paper according to (5) or (6), wherein the oil-resistant layer coating solution is applied with an on-machine gate roll coater.
本発明により、酸価が高く、ハイシェア粘度の高いアクリル樹脂系エマルションを使用することで、トランスファーロールコーターでの耐油層塗液の付着量を増加させることが可能となり、高い生産性と高耐油性とを両立した耐油紙を提供することができる。 By using an acrylic resin emulsion having a high acid value and a high shear viscosity according to the present invention, it becomes possible to increase the adhesion amount of the oil-resistant layer coating liquid on the transfer roll coater, resulting in high productivity and high oil resistance. It is possible to provide an oil-resistant paper that satisfies both requirements.
本発明の耐油紙において、耐油性を有するアクリル系樹脂層を有し、紙支持体としては、各種の紙、板紙が使用できる。紙基材表面上に、本発明に用いる紙基材としては特に限定されず、少なくとも一方の表面に後述するアクリル系樹脂を主体とする耐油層を少なくとも１層設けることができるものであればよく、用途に応じて適宜選択することができる。具体的には、晒または未晒クラフト紙、上質紙、中質紙、微塗工紙、塗工紙、板紙、白板紙、ライナー、セミグラシン紙、グラシン紙、片艶紙、パーチメント紙等が挙げられる。
紙支持体の坪量には特に制限はなく、包装用としては２０ｇ／ｍ２〜１５０ｇ／ｍ２、箱等の成型容器用としては１５０ｇ／ｍ２〜５００ｇ／ｍ２が好適である。
The oil-resistant paper of the present invention has an acrylic resin layer having oil resistance, and various papers and paperboards can be used as the paper support. The paper substrate used in the present invention is not particularly limited on the surface of the paper substrate, as long as it can provide at least one oil-resistant layer mainly composed of an acrylic resin described later on at least one surface. Depending on the application, it can be appropriately selected. Specific examples include bleached or unbleached kraft paper, fine paper, medium quality paper, finely coated paper, coated paper, paperboard, white paperboard, liner, semi-glassine paper, glassine paper, glossy paper, parchment paper, etc. It is done.
There is no particular limitation on the basis weight of the paper support, the packaging 20g / m 2 ~150g / m 2 , as the for molding vessel such as a box is preferably 150g / m 2 ~500g / m 2 .
本発明でいうアクリル系樹脂とは、（ａ）エチレン性不飽和カルボン酸含有モノマーを必須成分として含み、（ｂ）（メタ）アクリル酸アルキルエステルモノマー、（ｃ）これらのモノマーと共重合可能な他のモノマーから選択される少なくとも１種のモノマーからなる共重合体である。 The acrylic resin referred to in the present invention includes (a) an ethylenically unsaturated carboxylic acid-containing monomer as an essential component, and (b) a (meth) acrylic acid alkyl ester monomer, (c) copolymerizable with these monomers. It is a copolymer comprising at least one monomer selected from other monomers.
本発明において用いられる（ａ）エチレン性不飽和カルボン酸含有モノマーとしては、例えば（メタ）アクリル酸、クロトン酸、マレイン酸、イタコン酸、フマル酸、モノアルキルマレイン酸、モノアルキルフマル酸、モノアルキルイタコン酸等が挙げられ、これらのうちから少なくとも１種を用いることが必要である。
トランスファーロールコーターでの塗工適性を確保するため、耐油層塗液のハイシェア粘度を制御する必要がある。粘度が低くなりすぎると、所望とする塗布量が得られなくなり、耐油性が悪化する。ハイシェア粘度が高すぎると、トランスファーロールコーター上での塗液の転写ムラが生じ、均一な塗工面が得られず、十分な耐油性を得ることができなくなる。
本発明においては、耐油剤であるアクリル系樹脂の重量平均分子量と酸価を制御することで塗液のハイシェア粘度について所望の粘度範囲に制御し、トランスファーロールコーターでの耐油層塗液の塗工適性を確保した。本発明においては、重量平均分子量と酸価は同時に満足するように所定の範囲内に制御することが極めて重要である。重量平均分子量を所定の範囲に制御しても酸価が５０ｍｇＫＯＨ以下であれば、塗工時の粘度が低くなり、２００ｍｇＫＯＨ以上であれば、所望の粘度よりも高くなるため、塗工適性が確保できない。
一方、アクリル系樹脂の酸価を所定の範囲に制御しても、重量平均分子量が５万以下であると、ハイシェア粘度が低くなり過ぎ、逆に重量平均分子量が２００万を超えると、耐油層塗液のハイシェア粘度が高くなり過ぎるため、塗工適性が確保できない。
Examples of the (a) ethylenically unsaturated carboxylic acid-containing monomer used in the present invention include (meth) acrylic acid, crotonic acid, maleic acid, itaconic acid, fumaric acid, monoalkylmaleic acid, monoalkylfumaric acid, and monoalkyl. Itaconic acid and the like can be mentioned, and it is necessary to use at least one of them.
In order to ensure coating suitability with a transfer roll coater, it is necessary to control the high shear viscosity of the oil-resistant layer coating solution. If the viscosity is too low, the desired coating amount cannot be obtained, and the oil resistance deteriorates. If the high shear viscosity is too high, transfer unevenness of the coating liquid occurs on the transfer roll coater, a uniform coated surface cannot be obtained, and sufficient oil resistance cannot be obtained.
In the present invention, by controlling the weight average molecular weight and acid value of the acrylic resin that is an oil resistant agent, the high shear viscosity of the coating liquid is controlled within a desired viscosity range, and the coating of the oil resistant layer coating liquid with a transfer roll coater is performed. Appropriateness was ensured. In the present invention, it is extremely important to control the weight average molecular weight and the acid value within a predetermined range so as to satisfy simultaneously. Even if the weight average molecular weight is controlled within a predetermined range, if the acid value is 50 mgKOH or less, the viscosity at the time of coating becomes low, and if it is 200 mgKOH or more, the viscosity becomes higher than the desired viscosity, thus ensuring coating suitability. Can not.
On the other hand, even if the acid value of the acrylic resin is controlled within a predetermined range, if the weight average molecular weight is 50,000 or less, the high shear viscosity becomes too low, and conversely if the weight average molecular weight exceeds 2 million, Since the high shear viscosity of the coating liquid becomes too high, coating suitability cannot be ensured.
本発明においてはアクリル系樹脂を主成分とする耐油層塗液のハイシェア粘度を制御するため、エチレン性不飽和カルボン酸含有モノマーの配合量を調節して酸価を５０〜２００ｍｇＫＯＨ、より好ましくは７０〜１８０ｍｇＫＯＨであり、特に好ましくは１００〜１５０ｍｇＫＯＨである。アクリル系樹脂の酸価が５０ｍｇＫＯＨ未満であると樹脂の機械的安定性、再溶解性、粘性等が劣り、重合安定性や塗工適性に悪影響を及ぼす。特に、耐油層塗液のハイシェア粘度が低くなり過ぎ、所望とする塗工量が得られなくなり、耐油性が悪化する。逆に、酸価が２００ｍｇＫＯＨを超えると耐油層塗膜の乾燥性、耐水性が劣り、また塗膜が硬くなり過ぎるのでクラックを発生し易くなり、耐油性が悪化する。ここで、酸価とは樹脂１ｍｇに含まれる遊離脂肪酸を中和するのに必要なＫＯＨのｍｇ数である。 In the present invention, in order to control the high shear viscosity of the oil-resistant layer coating liquid mainly composed of an acrylic resin, the acid value is adjusted to 50 to 200 mgKOH, more preferably 70 by adjusting the blending amount of the ethylenically unsaturated carboxylic acid-containing monomer. It is -180 mgKOH, Most preferably, it is 100-150 mgKOH. If the acid value of the acrylic resin is less than 50 mg KOH, the mechanical stability, re-solubility, viscosity, etc. of the resin are inferior, and the polymerization stability and coating suitability are adversely affected. In particular, the high shear viscosity of the oil-resistant layer coating solution becomes too low, and a desired coating amount cannot be obtained, resulting in deterioration of oil resistance. Conversely, when the acid value exceeds 200 mgKOH, the drying and water resistance of the oil-resistant layer coating film is poor, and the coating film becomes too hard, so that cracks are likely to occur and the oil resistance deteriorates. Here, the acid value is the number of mg of KOH required to neutralize free fatty acids contained in 1 mg of resin.
本発明において用いられる（ｂ）（メタ）アクリル酸アルキルエステルモノマーとしては、例えば（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−プロピル、（メタ）アクリル酸イソプロピル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ−ブチル、（メタ）アクリル酸ヘキシル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸オクチル、（メタ）アクリル酸２−エチルヘキシル、（メタ）アクリル酸ｎ−ノニル、（メタ）アクリル酸イソノニル、（メタ）アクリル酸ラウリル、（メタ）アクリル酸ステアリル、（メタ）アクリル酸デシル、（メタ）アクリル酸ウンデシル、（メタ）アクリル酸ドデシル等が挙げられ、これらのうちから少なくとも１種を用いることができる。 Examples of the (b) (meth) acrylic acid alkyl ester monomer used in the present invention include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, N-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, n-nonyl (meth) acrylate, isononyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, ( Meta) dodecyl acrylate, etc., and at least one of them It can be used.
本発明において用いられる（ｃ）これらのモノマーと共重合可能な他のモノマーとしては、スチレン、酢酸ビニル、塩化ビニル、塩化ビニリデン、（メタ）アクリロニトリル、エチレン、プロピレン、２−ヒドロキシエチル（メタ）アクリレート、２−ヒドロキシプロピル（メタ）アクリレート、２−ヒドロキシブチル（メタ）アクリレート、４−ヒドロキシプロピル（メタ）アクリレート、ポリエチレングリコールモノ（メタ）アクリレート、２−ヒドロキシ−３−フェノキシプロピル（メタ）アクリルレート、グリセロールモノ（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、ジエチレングリコールジ（メタ）アクリレート、トリエチレングリコールジ（メタ）アクリレート、（ポリ）エチレングリコールジ（メタ）アクリレート、ジプロピレングリコールジ（メタ）アクリレート、１，２−プロピレングリコールジ（メタ）アクリレート、１，３−プロピレングリコールジ（メタ）アクリレート、１，３−ブチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、テトラメチロールメタンテトラ（メタ）アクリレート、ジビニルベンゼン、１，４−ブタンジオールジ（メタ）アクリレート、１，６−ヘキサンジオールジ（メタ）アクリレート、ネオペンチルグリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジアリル（メタ）アクリレート、グリシジル（メタ）アクリレート、メチルグリシジル（メタ）アクリレート、Ｎ−メチロール（メタ）アクリルアミド、Ｎ−メトキシメチル（メタ）アクリルアミド、Ｎ−ブトキシメチル（メタ）アクリルアミド、Ｎ，Ｎ’−メチレンビス（メタ）アクリルアミド、ビニルスルホン酸ナトリウム、ｐ−スチレンスルホン酸ナトリウム、２−アクリルアミド−２−メチルプロパンスルホン酸、酸ホスホキシエチル（メタ）アクリレートエタノールアミンハーフ塩、３−アリロキシ−２−ヒドロキシプロパンスルホン酸ナトリウム、ポリオキシエチレンスチレン化フェニル硫酸ナトリウム、グリセリンモノアリルエーテルモノスルホコハク酸ナトリウム、２−スルホエチル（メタ）アクリル酸ナトリウム、（メタ）アクリルアミドステアリン酸ナトリウム、ｎ−アミル（メタ）アクリレート、イソアミル（メタ）アクリレート、ベンジル（メタ）アクリレート、２−メトキシエチル（メタ）アクリレート、エチルカルビトール（メタ）アクリレート、カプロラクトン変性（メタ）アクリレート、アクロレイン、ジアセトン（メタ）アクリルアミド、ホルミルスチロール、ビニルメチルケトン、ビニルエチルケトン、（メタ）アクリロオキシアルキルプロペナール、ジアセトン（メタ）アクリレート、アセトニル（メタ）アクリレート、アセトアセトキシエチル（メタ）アクリレート、３，４−エポキシシクロヘキシル（メタ）アクリレート、ジアリルフタレート、トリアリルシアヌレート等が挙げられ、これらのうちから少なくとも１種を用いることができる。 (C) Other monomers copolymerizable with these monomers used in the present invention include styrene, vinyl acetate, vinyl chloride, vinylidene chloride, (meth) acrylonitrile, ethylene, propylene, 2-hydroxyethyl (meth) acrylate. 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Glycerol mono (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, (poly) ethylene glycol di (meth) Acrylate, dipropylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylolpropane Tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate, divinylbenzene, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, diallyl (meth) acrylate, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, N-methylol (meth) acrylamide, N-meth Cymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N, N′-methylenebis (meth) acrylamide, sodium vinylsulfonate, sodium p-styrenesulfonate, 2-acrylamido-2-methylpropanesulfonic acid, acid Phosphoxyethyl (meth) acrylate ethanolamine half salt, sodium 3-allyloxy-2-hydroxypropane sulfonate, sodium polyoxyethylene styrenated phenyl sulfate, sodium glyceryl monoallyl ether monosulfosuccinate, 2-sulfoethyl (meth) acrylic acid Sodium, (meth) acrylamide sodium stearate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxy ester Chill (meth) acrylate, ethyl carbitol (meth) acrylate, caprolactone-modified (meth) acrylate, acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl ethyl ketone, (meth) acrylooxyalkylpropenal, Examples include diacetone (meth) acrylate, acetonyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, and the like. Can be used.
本発明において用いられるアクリル系樹脂は公知の乳化重合法によって得ることができる。例えば、所定の反応容器に上記の各種モノマー類、乳化剤および水を仕込み、ラジカル重合開始剤を加え、攪拌下、加温することにより得られる。 The acrylic resin used in the present invention can be obtained by a known emulsion polymerization method. For example, it can be obtained by charging the above-mentioned various monomers, emulsifier and water in a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring.
ラジカル重合開始剤としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム等の過硫酸塩、過酸化水素、ｔ−ブチルハイドロオキサイド、ｔ−ブチルパーオキシベンゾエート等の過酸化物、２，２−アゾビスイソブチロニトリル、２，２−アゾビス（２−ジアミノプロパン）ハイドロクロライド、２，２−アゾビス（２，４−ジメチルバレロニトリル）等のアゾ系化合物が挙げられる。なお、重合速度の促進や低温反応を望む場合には、重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸、ホルムアルデヒドスルホオキシレート塩等の還元剤を前記ラジカル重合開始剤と組合せて（レドックス系重合開始剤）用いることができる。 Examples of radical polymerization initiators include persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, peroxides such as hydrogen peroxide, t-butyl hydroxide, and t-butyl peroxybenzoate, and 2,2-azo. Examples thereof include azo compounds such as bisisobutyronitrile, 2,2-azobis (2-diaminopropane) hydrochloride, and 2,2-azobis (2,4-dimethylvaleronitrile). If acceleration of polymerization rate or low temperature reaction is desired, a reducing agent such as sodium bisulfite, ferrous chloride, ascorbic acid, formaldehyde sulfooxylate salt is combined with the radical polymerization initiator (redox polymerization initiation). Agent).
重合開始剤の使用量は、モノマー成分１００質量部に対して、通常０．０２〜３質量部であるが、好ましくは０．０５〜１質量部である。 Although the usage-amount of a polymerization initiator is 0.02-3 mass parts normally with respect to 100 mass parts of monomer components, Preferably it is 0.05-1 mass part.
使用する乳化剤としては、特に限定はなく、アニオン性乳化剤、ノニオン性乳化剤、反応性乳化剤が挙げられる。
アニオン性乳化剤としては、オレイン酸カリウム等の脂肪酸金属塩、ラウリル硫酸ナトリウム等のアルキル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスルホン酸塩、アルキルナフタレンスルホン酸ナトリウム等のアルキルスルホン酸塩、ジアルキルスルホコハク酸ナトリウム、ポリオキシエチレンアルキルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルアリルエーテル硫酸ナトリウム、ポリオキシエチレンアルキルエーテルリン酸エステル、ポリオキシエチレンアルキルアリルエーテルリン酸エステル等が挙げられる。
ノニオン性乳化剤としては、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アルキルアリルエーテル、ポリオキシエチレン・ポリオキシプロピレンブロックコポリマー、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。
反応性乳化剤としては、種々の分子量（ＥＯ付加モル数の異なる）のポリエチレングリコールモノ（メタ）アクリレート、ポリオキシエチレンアルキルフェノールエーテル（メタ）アクリレート、２−（メタ）アクリロイルオキシエチルスルホン酸アンモニウム、ポリエチレングリコールのモノマレイン酸エステルおよびその誘導体、（メタ）アクリロイルポリオキシアルキレンアルキルエーテルリン酸エステル等が挙げられる。
The emulsifier to be used is not particularly limited, and examples thereof include an anionic emulsifier, a nonionic emulsifier, and a reactive emulsifier.
Examples of anionic emulsifiers include fatty acid metal salts such as potassium oleate, alkyl sulfates such as sodium lauryl sulfate, alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate, alkyl sulfonates such as sodium alkyl naphthalene sulfonate, and dialkyl sulfosuccinates. Examples thereof include sodium acid, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl allyl ether sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl allyl ether phosphate, and the like.
Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene / polyoxypropylene block copolymers, polyethylene glycol fatty acid esters, polyoxyethylene sorbitan fatty acid esters, and the like.
As reactive emulsifiers, polyethylene glycol mono (meth) acrylate, polyoxyethylene alkylphenol ether (meth) acrylate, ammonium 2- (meth) acryloyloxyethylsulfonate, polyethylene glycol having various molecular weights (different EO addition mole numbers) Monomaleic acid esters and derivatives thereof, (meth) acryloyl polyoxyalkylene alkyl ether phosphates, and the like.
乳化剤の使用量は、通常、モノマー成分１００質量部に対して、０．１〜１０質量部程度使用すればよく、好ましくは０．２〜５質量部である。乳化剤の使用量がこの範囲にあることによって、凝固物を生じることなく、適度な平均粒子径のアクリル系樹脂エマルションが得られる。 The amount of the emulsifier used is usually about 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the monomer component. By using the amount of the emulsifier within this range, an acrylic resin emulsion having an appropriate average particle diameter can be obtained without producing a coagulated product.
本発明において用いられるアクリル系樹脂は前記のように水媒体中で乳化重合法により得られるが、アクリル系樹脂エマルションの固形分濃度を３０〜７５質量％、好ましくは４０〜６５質量％程度として行うことができる。重合反応は単一重合開始の場合では通常４０〜９５℃、好ましくは６０〜９０℃程度の反応温度で、１〜１０時間、好ましくは４〜８時間程度行えばよい。また、レドックス系重合開始剤の場合では反応温度はより低く、通常５〜９０℃、好ましくは２０〜７０℃程度である。モノマーの添加方法としては、一括添加法、分割添加法、連続添加法等で、モノマータップ法、モノマープレ乳化タップ法等の方法で行うことができる。好ましくは連続添加法で、モノマープレ乳化タップ法である。 The acrylic resin used in the present invention is obtained by an emulsion polymerization method in an aqueous medium as described above. The acrylic resin emulsion has a solid content concentration of 30 to 75% by mass, preferably about 40 to 65% by mass. be able to. In the case of starting single polymerization, the polymerization reaction is usually performed at a reaction temperature of about 40 to 95 ° C., preferably about 60 to 90 ° C., for 1 to 10 hours, preferably about 4 to 8 hours. In the case of a redox polymerization initiator, the reaction temperature is lower, usually 5 to 90 ° C, preferably about 20 to 70 ° C. As a monomer addition method, a batch addition method, a divided addition method, a continuous addition method, or the like, such as a monomer tap method or a monomer pre-emulsification tap method can be used. The monomer pre-emulsification tapping method is preferred by the continuous addition method.
本発明において用いられるアクリル系樹脂エマルションは平均粒子径が０．０１〜１．０μｍであることが好ましい。平均粒子径がこの範囲にあれば水分散性が良好となる。平均粒子径が０．０１μｍ未満であると、塗工時の機械的安定性が悪くなるおそれがあり、１．０μｍを超えるとハイシェア粘度が低く、所望の塗工量が得られなかったり、塗工面にストリーク等の塗工むらが発生するおそれがある。なお、平均粒子径については、乳化剤や重合開始剤の種類および添加量、添加方法、攪拌条件等を適宜設定することにより容易に調整することができる。ここで、エマルションの平均粒子径は光散乱法粒子径分布測定機（ＨＯＲＩＢＡ社製、商品名：ＬＢ−５５０）で測定したものである。 The acrylic resin emulsion used in the present invention preferably has an average particle size of 0.01 to 1.0 μm. If the average particle diameter is within this range, water dispersibility will be good. If the average particle diameter is less than 0.01 μm, the mechanical stability during coating may be deteriorated. If it exceeds 1.0 μm, the high shear viscosity is low, and a desired coating amount cannot be obtained. There is a risk of uneven coating such as streaks on the work surface. In addition, about an average particle diameter, it can adjust easily by setting suitably the kind and addition amount of an emulsifier and a polymerization initiator, the addition method, stirring conditions, etc. Here, the average particle size of the emulsion is measured with a light scattering particle size distribution analyzer (trade name: LB-550, manufactured by HORIBA).
本発明においてはトランスファーロールコーターでの塗工適性を確保するため、耐油層塗液のハイシェア粘度を制御する必要がある。そこで、アクリル系樹脂を乳化重合する際に分子量（重量平均分子量）を反応温度、反応時間、平均粒子径、酸価の制御により適宜調節することができる。さらに、公知の連鎖移動剤を用いることは好ましい実施態様である。このような連鎖移動剤としては、ブチルメルカプタン、ドデシルメルカプタン、チオグリコール酸オクチル、イソプロピルアルコール、メタノール、四塩化炭素等が挙げられる。その使用量は、モノマー成分１００質量部に対して０．００１〜２．０質量部であり、好ましくは０．０５〜１．０質量部である。 In the present invention, it is necessary to control the high shear viscosity of the oil-resistant layer coating solution in order to ensure coating suitability with a transfer roll coater. Therefore, when the acrylic resin is emulsion-polymerized, the molecular weight (weight average molecular weight) can be appropriately adjusted by controlling the reaction temperature, reaction time, average particle diameter, and acid value. Furthermore, it is a preferred embodiment to use a known chain transfer agent. Examples of such chain transfer agents include butyl mercaptan, dodecyl mercaptan, octyl thioglycolate, isopropyl alcohol, methanol, carbon tetrachloride and the like. The usage-amount is 0.001-2.0 mass parts with respect to 100 mass parts of monomer components, Preferably it is 0.05-1.0 mass part.
本発明において用いられるアクリル系樹脂はモノマー組成が異なる複数のモノマー成分の個々が重合する過程で一体化してなる樹脂複合体、すなわち、モノマーが異なる複数のモノマー成分を各段で用いた多段の乳化重合により容易に得られるものであり、いわゆるコアシェル型のエマルションであることが好ましい（以下コア部を構成する重合体をコア部、シェル部を構成する重合体をシェル部と略す場合がある）。さらに好ましくは、該コアシェル型のエマルションはそのコア部には低いガラス転移温度（Ｔｇ）の樹脂を配置することが可能で、それにより塗膜形成が容易になり、塗膜自体も強靭になる。また、シェル部に高いＴｇの水溶性樹脂を配置することにより硬度を高くすることが可能になり、耐ブロッキング性が向上する。このようなコアシェル型のエマルションは以下のようにして容易に得ることができる。 The acrylic resin used in the present invention is a resin composite formed by integrating a plurality of monomer components having different monomer compositions, that is, a multi-stage emulsification using a plurality of monomer components having different monomers in each stage. It is easily obtained by polymerization, and is preferably a so-called core-shell type emulsion (hereinafter, the polymer constituting the core part may be abbreviated as the core part and the polymer constituting the shell part may be abbreviated as the shell part). More preferably, in the core-shell type emulsion, a resin having a low glass transition temperature (Tg) can be disposed in the core portion, thereby facilitating the formation of the coating film and the coating film itself. Moreover, it becomes possible to raise hardness by arrange | positioning water-soluble resin with high Tg to a shell part, and blocking resistance improves. Such a core-shell type emulsion can be easily obtained as follows.
アクリル系樹脂をコアシェル型エマルションとする場合、モノマー組成の異なる複数のモノマー成分を各段で用いた多段の乳化重合工程を経て製造する。ここで、多段の乳化重合とは、前段までに用いたモノマー成分の８０質量％以上、好ましくは９０質量％以上が重合してから、新たにモノマー成分を加えて次の段の重合を行う重合方法をいう。乳化重合の段数は、特に限定されないが、製造工程を簡略化するためには、２段または３段が好ましい。
本発明のアクリル系樹脂の製造においては、第一段の乳化重合工程ではＴｇが低いモノマー成分を用い、最終段の乳化重合工程ではＴｇが高いモノマー成分を用いる。
When the acrylic resin is made into a core-shell type emulsion, it is produced through a multi-stage emulsion polymerization process in which a plurality of monomer components having different monomer compositions are used in each stage. Here, the multistage emulsion polymerization is a polymerization in which 80% by mass or more, preferably 90% by mass or more of the monomer component used up to the previous stage is polymerized, and then the monomer component is newly added to perform the next stage polymerization. Say the method. The number of stages of emulsion polymerization is not particularly limited, but two or three stages are preferable in order to simplify the production process.
In the production of the acrylic resin of the present invention, a monomer component having a low Tg is used in the first emulsion polymerization step, and a monomer component having a high Tg is used in the final emulsion polymerization step.
いずれにしても、前記したような適正な重量平均分子量、酸価、平均粒子径を有することでハイシェア粘度を高く保ちつつ、かつ、塗膜になった時に、各種成分が分離することなく、均質なポリマーに近い状態で製膜されることが必要である。そのことは、塗膜のガラス転移温度を測定した時に、モノマーの違いに由来する複数のＴｇが観測されないで、一つのＴｇが観測されることが望ましいということである。 In any case, while maintaining a high shear viscosity by having an appropriate weight average molecular weight, acid value, and average particle diameter as described above, and when it becomes a coating film, various components are not separated and are homogeneous. It is necessary to form a film in a state close to a new polymer. That is, when the glass transition temperature of the coating film is measured, it is desirable that one Tg is observed without observing a plurality of Tg derived from the difference in monomers.
本発明においてＴｇは下記Ｆｏｘの式より計算されるものである。
１／Ｔｇ＝Σ（Ｗｎ／Ｔｇｎ）／１００
ここで、Ｗｎはモノマーｎの質量％、ＴｇｎはモノマーｎからなるホモポリマーのＴｇ（Ｋ：絶対温度）を示す。
In the present invention, Tg is calculated from the following Fox equation.
1 / Tg = Σ (W n / Tg n ) / 100
Here, W n represents mass% of monomer n, and Tg n represents Tg (K: absolute temperature) of a homopolymer composed of monomer n.
コア部に適する樹脂としては、概ねＴｇが−５０〜＋２５℃程度とすることが好ましい。重合に使用するモノマーとしては、単独であれば、メチルアクリレート、イソプロピルアクリレート、ヒドロキシプロピルアクリレート、ｎ−ヘキシルメタクリレートなどが使用できるが、前記した好ましいＴｇを有するコア部を重合するためには、低Ｔｇのポリマーを形成できる低Ｔｇモノマーと、高いＴｇ（ここでは２５℃以上）のポリマーを形成できる高Ｔｇモノマーの共重合体が好ましい。 As a resin suitable for the core portion, it is generally preferable that Tg is about −50 to + 25 ° C. As a monomer used for polymerization, methyl acrylate, isopropyl acrylate, hydroxypropyl acrylate, n-hexyl methacrylate, and the like can be used alone, but in order to polymerize the core portion having the above preferable Tg, low Tg A copolymer of a low Tg monomer capable of forming a polymer with a high Tg monomer capable of forming a polymer having a high Tg (here, 25 ° C. or higher) is preferable.
シェル部にはＴｇが４０〜１４０℃の樹脂が好ましい。前記範囲とするためには、メチルメタクリレートを主成分とする共重合体が好ましく使用できる。共重合の相手のモノマーとしては、前記した各種のアクリル系モノマーが使用できる。また、シェル部には、後述するように、酸価が必要で、そのため、アクリル酸またはメタクリル酸等のエチレン性不飽和カルボン酸含有モノマーを共重合する必要がある。シェル部を構成する重合体には高いＴｇが必要となるので、酸としてはメタクリル酸が最適である。メタクリル酸は耐油性の向上にも寄与する。さらに、前記した好ましいＴｇを有するシェル部を構成するために、上記以外のモノマーを使用することも勿論可能である。 The shell portion is preferably a resin having a Tg of 40 to 140 ° C. In order to make it the said range, the copolymer which has a methyl methacrylate as a main component can be used preferably. As the copolymerization partner monomer, the various acrylic monomers described above can be used. Further, as described later, the shell portion needs an acid value. Therefore, it is necessary to copolymerize an ethylenically unsaturated carboxylic acid-containing monomer such as acrylic acid or methacrylic acid. Since the polymer constituting the shell portion requires high Tg, methacrylic acid is optimal as the acid. Methacrylic acid also contributes to improving oil resistance. Furthermore, it is of course possible to use a monomer other than those described above in order to constitute the shell portion having the above-mentioned preferable Tg.
上記コアシェル型アクリル系樹脂エマルションにおいて、コア部とシェル部の質量比率としてはシェル部が５〜８０質量％であることが好ましく、より好ましくはシェル部が１０〜６０質量％である。 In the core-shell type acrylic resin emulsion, the mass ratio of the core part to the shell part is preferably 5 to 80% by mass, more preferably 10 to 60% by mass.
本発明において用いられるアクリル系樹脂を構成するモノマー成分の配合比率としては、（ａ）エチレン性不飽和カルボン酸含有モノマー：１０〜６０質量％、（ｂ）（メタ）アクリル酸アルキルエステルモノマー：１０〜８０質量％、（ｃ）これらのモノマーと共重合可能な他のモノマー：０〜７０質量％が好ましく、この配合比率とすることにより適正な範囲のガラス転移温度とすることができる。 As the blending ratio of the monomer component constituting the acrylic resin used in the present invention, (a) ethylenically unsaturated carboxylic acid-containing monomer: 10 to 60% by mass, (b) (meth) acrylic acid alkyl ester monomer: 10 ˜80% by mass, (c) Other monomer copolymerizable with these monomers: 0 to 70% by mass is preferable, and the glass transition temperature in an appropriate range can be obtained by using this blending ratio.
本発明において用いられるアクリル系樹脂は重量平均分子量が５万〜２００万である必要がある。重量平均分子量の好ましい範囲としては、７万〜１００万であり、１０万〜５０万が特に好ましい。重量平均分子量が５万未満になると耐油層塗液のハイシェア粘度が低くなり過ぎ、所望とする塗工量が得られなくなり、耐油性が悪化する。逆に、重量平均分子量が２００万を超えると耐油層塗液のハイシェア粘度が高くなり過ぎ、トランスファーロールコーターでの塗工むらが発生し、耐油性が悪化する。
ところで、低分子化合物はすべて同一の分子量からなり、単分散である。一方、合成高分子化合物は分子量の異なる同族体の集合体である。したがって、高分子化合物は広い分子量分布をもっており、多分散性で、何らかの平均分子量でしか評価できない。
そこで、本発明においてはアクリル系樹脂の分子量は重量平均分子量で評価し、具体的には重量平均分子量はポリスチレン換算（分析装置：ＴＯＳＯＨ社製の「ＨＬＣ−８１２０ＧＰＣ」、カラム：「ＴＳＫｇｅｌ ＧＭＨ−Ｈ（Ｓ）」）で測定したものである。
The acrylic resin used in the present invention needs to have a weight average molecular weight of 50,000 to 2,000,000. A preferable range of the weight average molecular weight is 70,000 to 1,000,000, and 100,000 to 500,000 is particularly preferable. When the weight average molecular weight is less than 50,000, the high shear viscosity of the oil-resistant layer coating solution becomes too low, and a desired coating amount cannot be obtained, resulting in deterioration of oil resistance. On the other hand, if the weight average molecular weight exceeds 2 million, the high shear viscosity of the oil-resistant layer coating solution becomes too high, coating unevenness occurs on the transfer roll coater, and oil resistance deteriorates.
By the way, all the low molecular weight compounds have the same molecular weight and are monodispersed. On the other hand, a synthetic polymer compound is an aggregate of homologues having different molecular weights. Therefore, the polymer compound has a wide molecular weight distribution, is polydispersed, and can be evaluated only with some average molecular weight.
Therefore, in the present invention, the molecular weight of the acrylic resin is evaluated by the weight average molecular weight. Specifically, the weight average molecular weight is converted to polystyrene (analyzer: “HLC-8120GPC” manufactured by TOSOH, column: “TSKgel GMH-H”). (S) ").
本発明において用いられるアクリル系樹脂エマルションについて未反応モノマー、未反応重合開始剤等を減少させるため、重合時または重合終了後、必要に応じて残留モノマー、残留重合開始剤等を除去する操作を施すことが好ましい。 In order to reduce unreacted monomers, unreacted polymerization initiators, etc., in the acrylic resin emulsion used in the present invention, an operation for removing residual monomers, residual polymerization initiators, etc. is performed as necessary during or after polymerization. It is preferable.
具体的には、重合段階で残留モノマーを低減する具体的な手段としては、例えば、重合終期に水媒体中の残存モノマーを分離・除去する方法、アクリル系モノマーやビニル系モノマーと反応し、揮発除去され易い低沸点のスキャベンジャーモノマーを重合中に添加する方法等が挙げられる。
また、重合系から残留モノマーを除去する方法としては、例えば、重合開始時及び重合中に酢酸ビニル、ビニルブチルエーテル、アクリル酸メチル、スチレン等の比較的低沸点のスキャベンジャーモノマーを添加し、スキャベンジャーとともに除去する方法；重合終了時に、アクリル系重合体に対する貧溶媒、例えば、メタノール、エタノール、ｎ−ヘキサン、ｎ−ヘプタン等の低沸点溶媒を用いてアクリル系重合体を洗浄する方法；アクリル系樹脂エマルションが収容されているタンク内にスチームを通過させる方法；多段塔内でアクリル系樹脂エマルションとスチームを向流接触させるいわゆるスチームストリッピング法等が挙げられる。
Specifically, as a specific means for reducing the residual monomer in the polymerization stage, for example, a method of separating and removing the residual monomer in the aqueous medium at the end of the polymerization, a reaction with an acrylic monomer or a vinyl monomer, and volatilization Examples thereof include a method of adding a low-boiling scavenger monomer that is easily removed during polymerization.
Further, as a method for removing the residual monomer from the polymerization system, for example, a scavenger monomer having a relatively low boiling point such as vinyl acetate, vinyl butyl ether, methyl acrylate, or styrene is added at the start of polymerization or during polymerization. At the end of the polymerization; a method for washing the acrylic polymer using a poor solvent for the acrylic polymer, for example, a low-boiling solvent such as methanol, ethanol, n-hexane, n-heptane; Examples include a method of allowing steam to pass through a tank in which an emulsion is accommodated; a so-called steam stripping method in which an acrylic resin emulsion and steam are brought into countercurrent contact in a multistage tower.
本発明の耐油層塗液には該アクリル系樹脂エマルションの他に、さらにバインダー、顔料などを含んでもよい。また、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、着色剤等の通常用いられている各種助剤が適宜使用できる。 In addition to the acrylic resin emulsion, the oil-resistant layer coating solution of the present invention may further contain a binder, a pigment and the like. Moreover, various auxiliary agents normally used, such as a dispersing agent, a thickener, a water retention agent, an antifoaming agent, and a coloring agent, can be used as needed.
本発明に使用できるバインダーとしては、カゼイン、澱粉、変性澱粉、ポリビニルアルコールなどの水溶性高分子、またはポリエステル系樹脂、ポリウレタン系樹脂、スチレン−ブタジエン系樹脂、酢酸ビニル系樹脂、エチレン−酢酸ビニル系樹脂、アクリロニトリル−ブタジエン系樹脂、ポリエチレン系樹脂、ポリプロピレン系樹脂、カルボキシメチルセルロース系樹脂、ポリアミド系樹脂、塩化ビニル系樹脂、塩化ビニリデン系樹脂等の水分散液が使用できる。 Examples of binders that can be used in the present invention include water-soluble polymers such as casein, starch, modified starch, and polyvinyl alcohol, or polyester resins, polyurethane resins, styrene-butadiene resins, vinyl acetate resins, ethylene-vinyl acetate resins. Water dispersions such as resins, acrylonitrile-butadiene resins, polyethylene resins, polypropylene resins, carboxymethyl cellulose resins, polyamide resins, vinyl chloride resins, vinylidene chloride resins can be used.
本発明に使用できる顔料としてはクレー、カオリン、タルク、炭酸カルシウム、炭酸マグネシウム、酸化マグネシウム、水酸化アルミニウム、アルミナ、シリカ、アルミノ珪酸マグネシウム、珪酸カルシウム、ホワイトカーボン、ベントナイト、ゼオライト、セリサイト、スメクタイト、硫酸カルシウム、硫酸バリウム、合成マイカ、二酸化チタン、酸化亜鉛などの無機顔料、さらにはポリイソプレン、ポリネオプレン、ポリブタジエン等のポリジエン類、ポリブテン、ポリイソブチレン、ポリプロピレン等のポリアルケン類、酢酸ビニル、スチレン、（メタ）アクリル酸、（メタ）アクリル酸アルキルエステル、（メタ）アクリルアミド、メチルビニルエーテル等のビニル系モノマーの重合体や共重合体類、ポリウレタン系樹脂、ポリエステル系樹脂、ポリアミド系樹脂、尿素系樹脂、メラミン系樹脂、ベンゾグアナミン系樹脂等の各種の密実型、中空型、あるいは貫通孔型粒子等の有機顔料が挙げられ、前記顔料の１種又は２種以上を使用することができる。 Examples of pigments that can be used in the present invention include clay, kaolin, talc, calcium carbonate, magnesium carbonate, magnesium oxide, aluminum hydroxide, alumina, silica, magnesium aluminosilicate, calcium silicate, white carbon, bentonite, zeolite, sericite, smectite, Inorganic pigments such as calcium sulfate, barium sulfate, synthetic mica, titanium dioxide, and zinc oxide, and polydienes such as polyisoprene, polyneoprene, and polybutadiene, polyalkenes such as polybutene, polyisobutylene, and polypropylene, vinyl acetate, styrene, ( Polymers and copolymers of vinyl monomers such as (meth) acrylic acid, (meth) acrylic acid alkyl esters, (meth) acrylamide, methyl vinyl ether, polyurethane resins, polyesters And various organic pigments such as solid resin, polyamide resin, urea resin, melamine resin, benzoguanamine resin, etc., solid type, hollow type, or through-hole type particles. More than seeds can be used.
本発明の耐油層の層構成としては、前記紙支持体の少なくとも片面に少なくとも１層の耐油層を設けるものであるが、同じ塗工量を塗工する場合、多層構成とした方が単層構成よりも耐油性は得られやすい。多層構成の場合、各層は同じ構成（組成）でもよいし、異なっていてもよい。 As the layer structure of the oil-resistant layer of the present invention, at least one oil-resistant layer is provided on at least one side of the paper support, but when applying the same coating amount, a multilayer structure is a single layer. Oil resistance is easier to obtain than the configuration. In the case of a multilayer configuration, each layer may have the same configuration (composition) or may be different.
本発明の耐油層の塗工量は（多層の場合はその合計）２．０〜１５．０ｇ／ｍ２の範囲であることが好ましい。塗工量が２．０ｇ／ｍ２未満の場合は、満足な耐油性能が得られない。また、１５．０ｇ／ｍ２を超える場合は、耐油性能は得られるものの、コストの面で好ましくない。より好ましい範囲は２．３〜１２．０ｇ／ｍ２である。
耐油性樹脂層の耐油度は、キット耐油度で６級以上であることが特徴ではあるが、キット耐油度で１２級以上になっている事がさらに好ましい。
The coating amount of the oil-resistant layer of the present invention is preferably in the range of 2.0 to 15.0 g / m 2 (total in the case of multiple layers). When the coating amount is less than 2.0 g / m 2 , satisfactory oil resistance cannot be obtained. Moreover, when it exceeds 15.0 g / m < 2 >, although oil resistance performance is obtained, it is not preferable in terms of cost. A more preferable range is 2.3 to 12.0 g / m 2 .
The oil resistance of the oil-resistant resin layer is characterized by a kit oil resistance of 6 or higher, but it is more preferable that the kit oil resistance is 12 or higher.
本発明において紙支持体に耐油層塗液を塗工する方法としては、トランスファーロールコーターを用いることを特徴とする。塗工は、オンマシンあるいはオフマシンの何れかで行われる。ここでいうトランスファーロールコーター方式とは、前計量方式で、紙支持体に耐油層塗液を塗工する方式であり、２本以上のロールとアプリケータロールからなるゲートロールコーターや、アプリケータロール上の塗液を巻線バーやロッドにより計量するシムサイザー等が挙げられる。塗工については、オンマシンコーティングが生産効率の点で好ましい。 In the present invention, a transfer roll coater is used as a method for coating the paper support with the oil-resistant layer coating solution. Coating is performed either on-machine or off-machine. Here, the transfer roll coater method is a pre-weighing method in which an oil-resistant layer coating solution is applied to a paper support. A gate roll coater comprising two or more rolls and an applicator roll, or an applicator roll Examples include a shim sizer that measures the above coating liquid with a winding bar or a rod. As for coating, on-machine coating is preferable in terms of production efficiency.
本発明において、耐油層塗液のハイシェア粘度が５０〜２００ｃｐｓ（せん断速度４６０００（１／ｓ））であることが必要である。ハイシェア粘度が５０ｃｐｓ未満の場合、トランスファーロールコーターによる塗工で紙支持体への塗工量が低下し、満足な耐油性が得られない。ハイシェア粘度が２００ｃｐｓを超えると塗工面が悪化し、満足な耐油性が得られない。ここで、ハイシェア粘度は熊谷理機工業社製の商品名「ＫＲＫ高剪断型粘度計」にて２，２００ｒｐｍ、ボブＦで測定した。 In the present invention, the high shear viscosity of the oil-resistant layer coating liquid needs to be 50 to 200 cps (shear rate 46000 (1 / s)). When the high shear viscosity is less than 50 cps, the coating amount on the paper support is reduced by coating with a transfer roll coater, and satisfactory oil resistance cannot be obtained. When the high shear viscosity exceeds 200 cps, the coated surface is deteriorated and satisfactory oil resistance cannot be obtained. Here, the high shear viscosity was measured with Bob F at 2,200 rpm using a trade name “KRK High Shear Viscometer” manufactured by Kumagai Riki Kogyo Co., Ltd.
本発明の耐油紙は耐油層形成後、必要に応じて平滑化処理を行うことができる。平滑化処理は通常のスーパーキャレンダー、グロスキャレンダー、ソフトキャレンダー等の平滑化処理装置を用いて、オンマシンまたはオフマシンで行われる。なお、本発明の効果を損なわない限りにおいて、耐油層塗工前の原紙を平滑化処理することも可能である。 The oil resistant paper of the present invention can be smoothed as necessary after the oil resistant layer is formed. The smoothing process is performed on-machine or off-machine using a normal smoothing apparatus such as a super calendar, a gloss calendar, or a soft calendar. As long as the effects of the present invention are not impaired, the base paper before the oil-resistant layer coating can be smoothed.
以下に実施例および比較例を挙げて本発明をより具体的に説明するが、勿論本発明はこれらの実施例に限定されるものではない。また、実施例および比較例中の％および部数はそれぞれ質量％、質量部を示す。また、基紙上の塗布量は絶乾質量を示す。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. Moreover,% and part in an Example and a comparative example show the mass% and the mass part, respectively. Moreover, the coating amount on the base paper indicates an absolutely dry mass.
＜実施例１＞
坪量５０ｇ／ｍ２のセミグラシン原紙（フリーネス１９５ｍｌ・ＣＳＦ、ＬＢＫＰ１００％）の抄造パート後のゲートロールコーターにて、耐油層塗料として固形分濃度４０％、重量平均分子量１０〜２０万のコアシェル型スチレン−アクリル樹脂系エマルション（ＢＡＳＦジャパン社製、商品名：「ＰＤＸ７６８７」、シェル部を構成する樹脂の酸価１００ｍｇＫＯＨ）を片面に４．８ｇ／ｍ２オンマシン塗工後乾燥して耐油紙を得た。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が１１０ｃｐｓ、Ｂ型粘度が５００ｃｐｓ（２３℃）であった。
<Example 1>
Core-shell type styrene with a solid content concentration of 40% and a weight average molecular weight of 100-200,000 as an oil-resistant coating on a gate roll coater after the papermaking part of a semi-glassine base paper (freeness 195ml · CSF, LBKP 100%) with a basis weight of 50g / m 2 -Acrylic resin-based emulsion (BASF Japan, trade name: “PDX7687”, acid value of resin constituting the shell part: 100 mg KOH) coated on one side with 4.8 g / m 2 on-machine and dried to obtain oil-resistant paper It was. The viscosity of the oil-resistant coating material used was 110 cps for the high shear viscosity measured at a shear rate of 46000 (1 / s) and 500 cps (23 ° C.) for the B-type viscosity.
＜実施例２＞
実施例１の耐油紙の製造において、コアシェル型スチレン−アクリル樹脂系エマルションの固形分濃度を４０％から３８％に変更した以外は実施例１と同様にして耐油紙を得た。耐油層の塗工量は２．８ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が６０ｃｐｓ、Ｂ型粘度が２５０ｃｐｓ（２３℃）であった。
<Example 2>
In the production of the oil-resistant paper of Example 1, an oil-resistant paper was obtained in the same manner as in Example 1 except that the solid content concentration of the core-shell type styrene-acrylic resin emulsion was changed from 40% to 38%. The coating amount of the oil resistant layer was 2.8 g / m 2 . The viscosity of the oil-resistant coating material used was a high shear viscosity measured at a shear rate of 46000 (1 / s) of 60 cps and a B-type viscosity of 250 cps (23 ° C.).
＜実施例３＞
実施例１の耐油紙の製造において、耐油層塗料として固形分濃度４９％、重量平均分子量２０万のコアシェル型スチレンーアクリル樹脂系エマルジョン（ＢＡＳＦジャパン社製、商品名：「ＰＤＸ７３４１」、シェル部を構成する樹脂の酸価５１ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は２．６ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が５５ｃｐｓ、Ｂ型粘度が４００ｃｐｓ（２３℃）であった。
<Example 3>
In the production of the oil-resistant paper of Example 1, a core-shell type styrene-acrylic resin emulsion having a solid content concentration of 49% and a weight average molecular weight of 200,000 as an oil-resistant layer paint (BASF Japan, trade name: “PDX7341”, shell part) When on-machine coating was performed with a gate roll coater using an acid value of 51 mg KOH of the constituent resin, the coating amount of the oil-resistant layer was 2.6 g / m 2 . The viscosity of the oil-resistant coating material used was 55 cps, a high shear viscosity measured at a shear rate of 46000 (1 / s), and 400 cps (23 ° C.) B-type viscosity.
＜実施例４＞
実施例１の耐油紙の製造において、耐油層塗料として固形分濃度４９％、重量平均分子量２０万のコアシェル型スチレンーアクリル樹脂系エマルジョン（ＢＡＳＦジャパン社製、商品名：「ＰＤＸ７１８２」、シェル部を構成する樹脂の酸価１２５ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は５．５ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が１３０ｃｐｓ、Ｂ型粘度が１７００ｃｐｓ（２３℃）であった。
<Example 4>
In the production of the oil-resistant paper of Example 1, a core-shell type styrene-acrylic resin emulsion having a solid content concentration of 49% and a weight average molecular weight of 200,000 as an oil-resistant layer coating (BASF Japan, trade name: “PDX7182”, shell portion When an on-machine coating was performed with a gate roll coater using an acid value of the constituent resin (125 mgKOH), the coating amount of the oil-resistant layer was 5.5 g / m 2 . The viscosity of the oil-resistant coating material used was 130 cps as a high shear viscosity and 1700 cps (23 ° C.) as measured at a shear rate of 46000 (1 / s).
＜比較例１＞
実施例１の耐油紙の製造において、耐油層塗料として固形分濃度３９％、重量平均分子量２０万のコアシェル型スチレン−アクリル樹脂系エマルション（ＢＡＳＦジャパン社製、商品名：「ＰＤＸ７３２６Ｎ」、シェル部を構成する高分子の酸価が３８ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は１．２ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度はせん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が１９ｃｐｓ、Ｂ型粘度が１５０ｃｐｓ(２３℃)であった。
<Comparative Example 1>
In the production of the oil-resistant paper of Example 1, a core-shell type styrene-acrylic resin emulsion having a solid content concentration of 39% and a weight average molecular weight of 200,000 as an oil-resistant layer coating (BASF Japan, trade name: “PDX7326N”, shell part) When on-machine coating was performed with a gate roll coater using an acid value of the constituent polymer of 38 mgKOH, the coating amount of the oil-resistant layer was 1.2 g / m 2 . The oil-resistant paint used had a high shear viscosity of 19 cps and a B-type viscosity of 150 cps (23 ° C.) measured at a shear rate of 46000 (1 / s).
＜比較例２＞
比較例１の耐油紙の製造において、耐油層塗料にさらに増粘剤(ソマール社製、商品名：ソマレックス２７０Ｋ)０．５部添加、濃度３８％とした以外は実施例１と同様の処理を行い、耐油紙を得た。耐油層の塗工量は１．８ｇ／ｍ２であった。なお、使用した耐油層の粘度はせん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が２０ｃｐｓ、Ｂ型粘度が４８０ｃｐｓ（２３℃）であった。
<Comparative example 2>
In the production of the oil-resistant paper of Comparative Example 1, the same treatment as in Example 1 was conducted except that 0.5 part of a thickener (trade name: Somalex 270K, manufactured by Somar Co., Ltd.) was added to the oil-resistant layer coating and the concentration was 38%. And oil-resistant paper was obtained. The coating amount of the oil resistant layer was 1.8 g / m 2 . The oil-resistant layer used had a high shear viscosity of 20 cps and a B-type viscosity of 480 cps (23 ° C.) measured at a shear rate of 46000 (1 / s).
＜比較例３＞
実施例１の耐油紙の製造において、耐油層塗料として固形分濃度４９％、重量平均分子量２０万のコアシェル型スチレンーアクリル樹脂系エマルジョン（ＢＡＳＦジャパン社製、商品名：ＨＲＣ−１６４５Ｊ、シェル部を構成する高分子の酸価が２２ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は１．０ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が１０ｃｐｓ、Ｂ型粘度が５０ｃｐｓ（２３℃）であった。
<Comparative Example 3>
In the production of the oil-resistant paper of Example 1, a core-shell type styrene-acrylic resin emulsion having a solid content concentration of 49% and a weight average molecular weight of 200,000 as an oil-resistant layer coating (BASF Japan, trade name: HRC-1645J, shell part) When the on-machine coating was performed with a gate roll coater using an acid value of the constituting polymer of 22 mgKOH, the coating amount of the oil-resistant layer was 1.0 g / m 2 . The viscosity of the oil-resistant coating material used was 10 cps for the high shear viscosity measured at a shear rate of 46000 (1 / s) and 50 cps (23 ° C.) for the B-type viscosity.
＜比較例４＞
実施例１の耐油紙の製造において、耐油層塗料として下記に表示するコアシェル組成からなる固形分濃度３０％、重量平均分子量４万、平均Ｔｇ５８℃のコアシェル型アクリル樹脂系エマルジョン（シェル部を構成する高分子の酸価が１８８ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は０．８ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が１２ｃｐｓ、Ｂ型粘度が３０ｃｐｓ（２３℃）であった。
<Comparative example 4>
In the production of the oil-resistant paper of Example 1, a core-shell type acrylic resin emulsion having a solid-shell concentration of 30%, a weight-average molecular weight of 40,000, and an average Tg of 58 ° C. as an oil-resistant layer coating (shown below) When on-machine coating was performed with a gate roll coater using a polymer acid value of 188 mgKOH, the coating amount of the oil-resistant layer was 0.8 g / m 2 . The viscosity of the oil-resistant coating material used was 12 cps for the high shear viscosity measured at a shear rate of 46000 (1 / s) and 30 cps (23 ° C.) for the B-type viscosity.
平均Ｔｇ５８℃のコアシェル型アクリル樹脂エマルジョンのモノマー組成：（イ）コア部組成：メチルメタアクリレート／２エチルヘキシル＝６１／３９（Ｔｇ＝１０℃）（ロ）シェル部組成：メチルメタアクリレート／アクリル酸＝７０／３０（Ｔｇ＝１２６℃、酸価１８８）上記のコアシェル重量比を（イ）／（ロ）＝５０／５０とし、酸価＝９４とした。 Monomer composition of core-shell type acrylic resin emulsion having an average Tg of 58 ° C .: (A) Core composition: Methyl methacrylate / 2 ethylhexyl = 61/39 (Tg = 10 ° C.) (B) Shell composition: Methyl methacrylate / acrylic acid = 70/30 (Tg = 126 ° C., acid value 188) The above core-shell weight ratio was set to (A) / (B) = 50/50, and the acid value = 94.
＜比較例５＞
実施例１の耐油紙の製造において、耐油層塗料として下記に表示するコアシェル組成からなる固形分濃度３０％、重量平均分子量３万、平均Ｔｇ４３℃のコアシェル型アクリル樹脂系エマルジョン（シェル部を構成する高分子の酸価が１２６ｍｇＫＯＨ）を用いて、ゲートロールコーターでオンマシンコーティングを行ったところ、耐油層の塗工量は０．５ｇ／ｍ２であった。なお、使用した耐油層塗料の粘度は、せん断速度４６０００（１／ｓ）で測定されるハイシェア粘度が８ｃｐｓ、Ｂ型粘度が２０ｃｐｓ（２３℃）であった。
<Comparative Example 5>
In the production of the oil-resistant paper of Example 1, a core-shell type acrylic resin emulsion having a solid-shell concentration of 30%, a weight-average molecular weight of 30,000, and an average Tg of 43 ° C. as an oil-resistant layer coating (shown below) When on-machine coating was performed with a gate roll coater using a polymer acid value of 126 mgKOH, the coating amount of the oil-resistant layer was 0.5 g / m 2 . The viscosity of the oil-resistant coating material used was 8 cps for the high shear viscosity measured at a shear rate of 46000 (1 / s) and 20 cps (23 ° C.) for the B-type viscosity.
平均Ｔｇ４３℃のコアシェル型アクリル樹脂エマルジョンのモノマー組成：（ハ）コア部組成：メチルメタアクリレート／２エチルヘキシル＝５０／５０（Ｔｇ＝−９℃）（ニ）シェル部組成：メチルメタアクリレート／アクリル酸＝８０／２０（Ｔｇ＝１２６℃、酸価１２６）上記のコアシェル重量比を（イ）／（ロ）＝５０／５０とし、酸価＝６３とした。 Monomer composition of core-shell acrylic resin emulsion having an average Tg of 43 ° C .: (c) Core part composition: methyl methacrylate / 2 ethylhexyl = 50/50 (Tg = −9 ° C.) (d) Shell part composition: methyl methacrylate / acrylic acid = 80/20 (Tg = 126 ° C., acid value 126) The above core-shell weight ratio was (A) / (B) = 50/50, and the acid value = 63.
平面部の耐油度の評価基準：ＴＡＰＰＩ ＵＭ−５５７法（キット法）によって塗工面を測定した。耐油紙として使用可能なキット耐油度は５級以上であることが特徴ではあるが、高い耐油性を有する耐油紙としてはキット耐油度で１２級以上であることが特徴である。 Evaluation criteria for oil resistance of flat surface: The coated surface was measured by the TAPPI UM-557 method (kit method). The kit oil resistance that can be used as oil-resistant paper is characterized by a grade 5 or higher, but the oil-resistant paper having high oil resistance is characterized by a kit oil resistance of grade 12 or higher.
上記実施例、比較例を評価したものを表１に示す。本発明により、酸価が高く、かつハイシェア粘度を高いコアシェル型アクリル樹脂系エマルションを使用することで、トランスファーロールコーターでの塗料の付着量を増加させることが可能となり、高耐油性を有する耐油紙を提供することができる。 Table 1 shows the results of evaluating the above Examples and Comparative Examples. According to the present invention, by using a core-shell type acrylic resin emulsion having a high acid value and a high shear viscosity, it is possible to increase the amount of paint applied on a transfer roll coater, and an oil-resistant paper having high oil resistance. Can be provided.
本発明による耐油紙は、ファーストフードなどの揚げ物を包装する容器やデパート、コンビニエンスストアなどでのテイクアウト食材の包装容器等に使用可能であり、実用上極めて有用である。 The oil-resistant paper according to the present invention can be used in containers for packaging fried foods such as fast food, packaging containers for take-out foods in department stores, convenience stores, etc., and is extremely useful in practice.
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