JP5454362B2 - Water repellent paper - Google Patents
Water repellent paper Download PDFInfo
- Publication number
- JP5454362B2 JP5454362B2 JP2010125649A JP2010125649A JP5454362B2 JP 5454362 B2 JP5454362 B2 JP 5454362B2 JP 2010125649 A JP2010125649 A JP 2010125649A JP 2010125649 A JP2010125649 A JP 2010125649A JP 5454362 B2 JP5454362 B2 JP 5454362B2
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- JP
- Japan
- Prior art keywords
- water
- paper
- repellent
- wax
- polyacrylamide
- 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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- 238000001035 drying Methods 0.000 description 1
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- 239000008273 gelatin Substances 0.000 description 1
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- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
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- 229940094506 lauryl betaine Drugs 0.000 description 1
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- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
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- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
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- 229920001223 polyethylene glycol Polymers 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
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- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- QYPWRPSMKLUGJZ-UHFFFAOYSA-N pyridin-1-ium;sulfate Chemical compound [O-]S([O-])(=O)=O.C1=CC=[NH+]C=C1.C1=CC=[NH+]C=C1 QYPWRPSMKLUGJZ-UHFFFAOYSA-N 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229940001941 soy protein Drugs 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
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- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Chemical class 0.000 description 1
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- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 229940007718 zinc hydroxide Drugs 0.000 description 1
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Landscapes
- Paper (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Description
本発明は、熱による撥水性の低下が少ない撥水紙に関する。 The present invention relates to a water-repellent paper that is less likely to cause a decrease in water repellency due to heat.
従来から、各種包装用紙材、例えば段ボール、重袋、包装紙などは、輸送中における内容物の品質保全、安全輸送、強度劣化防止のため種々の処理、加工が行われている。特に青果物、水産物などの包装に用いる包装紙材においては、水分による強度劣化防止のため、撥水性を付与したものが広く使用されている。紙材料に撥水性を付与する手段としては、一般にワックス系エマルジョンからなる撥水剤をオンマシンコーターやオフマシンコーターで塗工したり、スプレーを用いて噴霧したりすることが広く行われてきた。 Conventionally, various wrapping paper materials, such as cardboard, heavy bags, wrapping paper, and the like, have been subjected to various processing and processing for quality maintenance of contents during transportation, safe transportation, and prevention of strength deterioration. In particular, wrapping paper materials used for packaging fruits and vegetables, marine products, and the like are widely used to impart water repellency to prevent strength deterioration due to moisture. As a means for imparting water repellency to paper materials, it has been widely practiced to apply a water-repellent agent composed of a wax-based emulsion with an on-machine coater or an off-machine coater, or to spray it with a spray. .
近年、特にライナーにおいて古紙パルプの配合率が高まっており、こうしたライナーではワックス系撥水剤を塗工しても、古紙パルプ由来の填料や微細繊維の影響で撥水性が発現し難く、段ボールシートに加工する際の熱処理で、撥水性がさらに低下し易くなっている。その対策としてワックス系撥水剤の塗工量を増やすといった方法が挙げられるが、塗工量の増加によりコストアップとなるばかりでなく、塗工時のコーター汚れが顕著になり生産に支障をきたす場合もある。このため、古紙パルプの配合率が高い紙材料においても、少ない撥水剤塗工量で十分な撥水性を得る方法が求められている。 In recent years, the percentage of recycled paper pulp has increased especially in liners, and even when a wax-based water repellent is applied to such liners, water repellency is hardly exhibited due to the effects of fillers and fine fibers derived from waste paper pulp. The water repellency is more likely to be lowered by the heat treatment during processing. As a countermeasure, there is a method of increasing the coating amount of the wax-based water repellent, but not only will the cost increase due to the increase in the coating amount, but also the coater stains at the time of coating will become noticeable and hinder production. In some cases. For this reason, there is a demand for a method for obtaining sufficient water repellency with a small amount of water repellent coating even in paper materials having a high content ratio of waste paper pulp.
こうした問題の解決方法として、正電荷のコロイダルシリカ水分散体を塗工した紙表面にアニオン性撥水剤を塗工する方法(特許文献1)や、カチオン性共重合体の4級化合物とポリアミドポリアミン−エピハロヒドリン樹脂からなる混合液を下塗り後、撥水剤を塗工する方法(特許文献2)や、カチオン性共重合体とカルボン酸含有のポリアミドあるいはアルキルケテンダイマーからなる混合液を下塗り後、撥水剤を塗工する方法(特許文献3)や、アニオン性モノマーと疎水性モノマーを重合させたアクリル系ポリマー乳化物を下塗り後、撥水剤を塗工する方法(特許文献4)や、特定のアニオン性高分子分散剤存在下で疎水性ビニルモノマーを乳化重合した乳化物を下塗り後、撥水剤を塗工する方法(特許文献5)などが提案されている。 To solve these problems, a method of applying an anionic water repellent to the paper surface coated with a positively charged colloidal silica aqueous dispersion (Patent Document 1), a quaternary compound of a cationic copolymer and a polyamide After undercoating a mixed solution composed of a polyamine-epihalohydrin resin, after applying a water repellent (Patent Document 2) or undercoating a mixed solution composed of a cationic copolymer and a carboxylic acid-containing polyamide or alkyl ketene dimer, A method of applying a water repellent (Patent Document 3), a method of applying a water repellent after applying an acrylic polymer emulsion obtained by polymerizing an anionic monomer and a hydrophobic monomer (Patent Document 4), A method of applying a water repellent after applying an emulsion obtained by emulsion polymerization of a hydrophobic vinyl monomer in the presence of a specific anionic polymer dispersant (Patent Document 5) has been proposed. .
これらの方法は、古紙パルプの配合率が高い紙材料においても、少ない撥水剤塗工量で十分な撥水性を得ることができるが、いずれも下塗り剤を塗工、乾燥後に撥水剤を塗工、乾燥するもので、撥水性付与のために片面当り2回以上の塗工が必要となり、製造が煩雑となるといった問題がある。特に片面当り1回の塗工しかできない製造設備では、下塗り剤を塗工、乾燥した下塗り紙を一度リールに巻き取った後、改めて塗工機にセットして撥水剤を塗工する必要があり、生産効率の低下が著しくなる。 These methods can obtain sufficient water repellency with a small amount of water repellent coating amount even in paper materials with a high content ratio of waste paper pulp. Since the coating and drying are performed, two or more coatings per side are required for imparting water repellency, and there is a problem that the production becomes complicated. In particular, in a production facility that can only apply once per side, it is necessary to coat the primer, wind up the dried primer paper once on a reel, and set it on the coating machine again to apply the water repellent. There is a significant reduction in production efficiency.
下塗り剤を塗工することなく、少ない撥水剤塗工量でも熱による撥水性の低下が少ない撥水紙を提供することを目的とする。 An object of the present invention is to provide a water-repellent paper that does not cause a decrease in water repellency due to heat even when applied with a small amount of water-repellent agent without applying a primer.
本発明者らは前記課題を解決すべく鋭意検討した結果、紙支持体にワックス系撥水剤とポリアクリルアミド系高分子を特定の配合比率で含む塗工層を設けることで前記課題が解決可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors can solve the above problems by providing a coating layer containing a wax-based water repellent and a polyacrylamide polymer at a specific blending ratio on a paper support. As a result, the present invention has been completed.
本発明は、以下の各発明から選択される発明である。
(1)紙支持体の少なくとも片面に塗工層を設けてなる撥水紙において、該塗工層中のワックス系撥水剤とポリアクリルアミド系高分子の固形分質量比が99.9〜98.0:0.1〜2.0であることを特徴とする撥水紙。
The present invention is an invention selected from the following inventions .
(1) In a water-repellent paper having a coating layer provided on at least one side of a paper support, the mass ratio of the solid content of the wax-based water repellent and the polyacrylamide polymer in the coating layer is 99.9 to 98. 0.0: 0.1 to 2.0, a water-repellent paper.
(2)前記ポリアクリルアミド系高分子の濃度0.5質量%水性液の20℃におけるJIS Z 8803−1991に規定されるB型粘度が50〜2000mPa・sである(1)に記載の撥水紙。 (2) The water repellent property according to (1), wherein the B-type viscosity defined in JIS Z 8803-1991 at 20 ° C. of the aqueous liquid having a concentration of 0.5% by mass of the polyacrylamide polymer is 50 to 2000 mPa · s. paper.
(3)前記塗工層中のワックス系撥水剤とポリアクリルアミド系高分子の合計塗工量が0.1〜1.0g/m2である(1)または(2)に記載の撥水紙。 (3) The water repellent according to (1) or (2), wherein the total coating amount of the wax-based water repellent and the polyacrylamide polymer in the coating layer is 0.1 to 1.0 g / m 2. paper.
本発明によれば、下塗りが不要のため生産効率を低下させることなく、熱による撥水性の低下が少ない撥水紙を提供することができる。 According to the present invention, it is possible to provide a water-repellent paper that is less likely to cause a decrease in water repellency due to heat without lowering the production efficiency because an undercoat is unnecessary.
本発明は紙支持体の少なくとも片面にワックス系撥水剤(A)とポリアクリルアミド系高分子(B)とを含む塗工層を設けた撥水紙であって、(A)と(B)の配合比が特定比率となるように配合したことを特徴とする。 The present invention is a water-repellent paper provided with a coating layer containing a wax-based water repellent (A) and a polyacrylamide-based polymer (B) on at least one side of a paper support, wherein (A) and (B) The blending ratio is characterized in that the blending ratio is a specific ratio.
本発明では、ワックス系撥水剤とポリアクリルアミド系高分子との混合液を紙支持体に塗工する際に、ポリアクリルアミド系高分子の増粘作用によりワックス系撥水剤の紙支持体内部への浸透を抑制し、ワックス成分を紙支持体表面に定着させるため、熱による撥水性の低下を抑制することができる。このため、ワックス系撥水剤(A)とポリアクリルアミド系高分子(B)との固形分質量比(配合比率)は(A):(B)=99.9〜98.0:0.1〜2.0の範囲とする必要があり、好ましくは(A):(B)=99.8〜99.0:0.2〜1.0の範囲である。ポリアクリルアミド系高分子の配合比率が0.1質量%未満、ワックス系撥水剤が99.9質量%以上であると、熱による撥水性の低下を抑制する効果が不十分となる。逆に、ポリアクリルアミド系高分子の配合比率が2.0質量%以上、ワックス系撥水剤が98.0質量%未満であると、ポリアクリルアミド系高分子に起因する親水性が強まり、十分な撥水性が発現しない。 In the present invention, when a mixed liquid of a wax-based water repellent and a polyacrylamide polymer is applied to a paper support, the inside of the paper support of the wax-based water repellent is increased by the thickening action of the polyacrylamide polymer. Inhibition of water penetration and fixing of the wax component on the surface of the paper support can suppress a decrease in water repellency due to heat. For this reason, the solid content mass ratio (blending ratio) of the wax-based water repellent (A) and the polyacrylamide-based polymer (B) is (A) :( B) = 99.9 to 98.0: 0.1. It is necessary to make it the range of -2.0, Preferably it is the range of (A) :( B) = 99.8-99.0: 0.2-1.0. When the blending ratio of the polyacrylamide polymer is less than 0.1% by mass and the wax-based water repellent is 99.9% by mass or more, the effect of suppressing the decrease in water repellency due to heat becomes insufficient. On the other hand, when the blending ratio of the polyacrylamide polymer is 2.0% by mass or more and the wax-based water repellent is less than 98.0% by mass, the hydrophilicity due to the polyacrylamide polymer is increased and sufficient No water repellency.
本発明で使用されるポリアクリルアミド系高分子は主にアクリルアミド、メタアクリルアミドなどのモノマーを重合したポリマーであり、前記モノマー以外に、イオン性モノマー、疎水性モノマー、親水性モノマー、分岐構造を付与できるモノマー、架橋構造を付与できる多官能性モノマーなども共重合することができる。 The polyacrylamide polymer used in the present invention is a polymer obtained by polymerizing monomers such as acrylamide and methacrylamide. In addition to the monomers, an ionic monomer, a hydrophobic monomer, a hydrophilic monomer, and a branched structure can be added. Monomers, polyfunctional monomers capable of imparting a crosslinked structure, and the like can also be copolymerized.
イオン性モノマーのうちアニオン性モノマーとしては、例えばアクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸などの不飽和カルボン酸およびそれらの塩、またはビニルスルホン酸、スチレンスルホン酸、アクリルアミドメチルプロパンスルホン酸などのスルホン酸類およびそれらの塩等が挙げられる。 Among the ionic monomers, anionic monomers include, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and their salts, or vinyl sulfonic acid, styrene sulfonic acid, acrylamidomethylpropane sulfone. Examples thereof include sulfonic acids such as acids and salts thereof.
また、カチオン性モノマーとしては、例えばN,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリレート、N,N−ジメチルアミノプロピル(メタ)アクリルアミド、N,N−ジエチルアミノプロピル(メタ)アクリルアミド等のアミンおよびそれらの塩、およびそれらの4級化物等が挙げられる。 Examples of the cationic monomer include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-dimethylamino. Examples thereof include amines such as propyl (meth) acrylamide and N, N-diethylaminopropyl (meth) acrylamide and salts thereof, and quaternized products thereof.
疎水性モノマーとしては、例えばアクリロニトリル、N,N−ジ−n−プロピル(メタ)アクリルアミド、N−n−ブチル(メタ)アクリルアミド、N−n−ヘキシル(メタ)アクリルアミド、N−n−オクチル(メタ)アクリルアミド、N−tert−オクチル(メタ)アクリルアミド、N−n−ドデシル(メタ)アクリルアミド等のN−アルキル(メタ)アクリルアミド誘導体、N,N−ジグリシジル(メタ)アクリルアミド、N−(4−グリシドキシブチル)(メタ)アクリルアミド、N−(5−グリシドキシペンチル)アクリルアミド、N−(6−グリシドキシヘキシル)アクリルアミド等のN−(ω−グリシドキシアルキル)(メタ)アクリルアミド誘導体、メチル(メタ)アクリレート、エチル(メタ)アクリレート、ブチル(メタ)アクリレート、ラウリル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、グリシジル(メタ)アクリレート等の(メタ)アクリレート誘導体、メタクリロニトリル、酢酸ビニル、塩化ビニル、塩化ビニリデン、エチレン、プロピレン、ブテン等のオレフィン類、スチレン、α−メチルスチレン、ブタジエン、イソプレン等を挙げることができる。 Examples of the hydrophobic monomer include acrylonitrile, N, N-di-n-propyl (meth) acrylamide, Nn-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide, Nn-octyl (meth) ) N-alkyl (meth) acrylamide derivatives such as acrylamide, N-tert-octyl (meth) acrylamide, Nn-dodecyl (meth) acrylamide, N, N-diglycidyl (meth) acrylamide, N- (4-glycid N- (ω-glycidoxyalkyl) (meth) acrylamide derivatives such as xylbutyl) (meth) acrylamide, N- (5-glycidoxypentyl) acrylamide, N- (6-glycidoxyhexyl) acrylamide, methyl (Meth) acrylate, ethyl (meth) acrylate, butyl ( ) Acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylate derivatives such as glycidyl (meth) acrylate, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride, ethylene, propylene, butene, etc. Olefins, styrene, α-methylstyrene, butadiene, isoprene and the like.
親水性モノマーとしては、例えばジアセトンアクリルアミド、N,N−ジメチル(メタ)アクリルアミド、N−エチル(メタ)アクリルアミド、N,N−ジエチル(メタ)アクリルアミド、N−プロピルアクリルアミド、N−アクリロイルピロリジン、N−アクリロイルピペリジン、N−アクリロイルモルホリン、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、各種のメトキシポリエチレングリコール(メタ)アクリレート、N−ビニルホルムアミド、N−ビニルアセトアミド、N−ビニル−2−ピロリドン等を挙げることができる。 Examples of the hydrophilic monomer include diacetone acrylamide, N, N-dimethyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-propyl acrylamide, N-acryloylpyrrolidine, N -Acryloylpiperidine, N-acryloylmorpholine, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, various methoxypolyethylene glycol (meth) acrylates, N-vinylformamide, N-vinylacetamide, N-vinyl-2-pyrrolidone Etc.
分岐構造を付与できるモノマーとしては、N,N−ジメチルアクリルアミドのような特定のN−置換アクリルアミド誘導体、あるいは(メタ)アリルスルホン酸およびその塩類等を挙げることができる。 Examples of the monomer capable of imparting a branched structure include specific N-substituted acrylamide derivatives such as N, N-dimethylacrylamide, (meth) allylsulfonic acid and salts thereof, and the like.
架橋構造を付与できるモノマーとしては、例えばメチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、ヘキサメチレンビス(メタ)アクリルアミド、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、ジビニルベンゼン、ジアリルアクリルアミドなどの2官能型架橋性モノマー、あるいは1,3,5−トリアクリロイルヘキサヒドロ−S−トリアジン、トリアリルイソシアヌレート、トリアクリル酸ペンタエリスリトール、トリメチロールプロパンアクリレート、トリアクリルモルマール、ジアクリロイルイミド等の多官能型架橋性モノマー等が挙げられる。 Examples of monomers capable of imparting a crosslinked structure include methylene bis (meth) acrylamide, ethylene bis (meth) acrylamide, hexamethylene bis (meth) acrylamide, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and triethylene glycol di Bifunctional crosslinkable monomers such as (meth) acrylate, divinylbenzene, diallylacrylamide, or 1,3,5-triacryloylhexahydro-S-triazine, triallyl isocyanurate, pentaerythritol triacrylate, trimethylolpropane acrylate , Polyfunctional type crosslinkable monomers such as triacryl mormar and diacryloyl imide.
これらモノマーの重合については、特に制限はなく、溶液重合法、乳化重合法などの従来公知の各種方法により行うことができる。例えば、所定の反応容器に各種モノマー、分散剤および水を仕込み、ラジカル重合開始剤を加え、撹拌下、加温することにより得られる。モノマーの仕込み方法は同時重合、連続滴下重合等の従来公知の各種方法により行うことができる。ラジカル重合開始剤としては、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩、またはこれらと亜硫酸水素ナトリウムといった還元剤とを組み合わせた形のレドックス系重合開始剤等を使用することができる。また、前記ラジカル重合開始剤には、アゾ系開始剤を用いてもよい。反応温度は単一重合開始剤の場合では一般に30〜100℃であり、レドックス系重合開始剤の場合ではより低く、一般に5〜90℃である。分散剤としては、アルキルベンゼンスルホン酸塩、アルキルスルホン酸塩、アルキル硫酸エステル塩、脂肪酸金属塩、ポリオキシアルキルエーテル硫酸エステル塩、ポリオキシエチレンカルボン酸エステル硫酸エステル塩、ポリオキシエチレンアルキルフェニルエーテル硫酸エステル塩、コハク酸ジアルキルエステルスルホン酸塩等のイオン性界面活性剤や、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンアルキルエーテルグリセリンホウ酸エステル、ポリオキシエチレンアルキルエーテルリン酸エステル、ソルビタン脂肪酸エステル、グリセリン脂肪酸エステル、ペンタエリスリトール脂肪酸エステル等のノニオン性界面活性剤が挙げられる。また、重合反応によって生成される高分子の分子量は、反応温度、反応時間で適宜調節することができ、ラジカル重合の場合、公知の連鎖移動剤の使用でも調節することができる。こうした分子量調節によりポリアクリルアミド系高分子水分散液の粘度を調節することができる。 There is no restriction | limiting in particular about superposition | polymerization of these monomers, It can carry out by various conventionally well-known methods, such as a solution polymerization method and an emulsion polymerization method. For example, it can be obtained by charging various monomers, a dispersant and water in a predetermined reaction vessel, adding a radical polymerization initiator, and heating with stirring. The monomer can be charged by various conventionally known methods such as simultaneous polymerization and continuous dropping polymerization. As the radical polymerization initiator, a persulfate such as potassium persulfate or ammonium persulfate, or a redox polymerization initiator in the form of a combination of these with a reducing agent such as sodium bisulfite can be used. An azo initiator may be used as the radical polymerization initiator. In the case of a single polymerization initiator, the reaction temperature is generally 30 to 100 ° C., and in the case of a redox polymerization initiator, it is lower, and generally 5 to 90 ° C. Dispersing agents include alkylbenzene sulfonate, alkyl sulfonate, alkyl sulfate ester, fatty acid metal salt, polyoxyalkyl ether sulfate, polyoxyethylene carboxylic ester sulfate, polyoxyethylene alkyl phenyl ether sulfate Ionic surfactants such as salts and dialkyl ester sulfonates of succinic acid, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether glycerin Borate ester, polyoxyethylene alkyl ether phosphate ester, sorbitan fatty acid ester, glycerin fatty acid ester, pentaerythritol fat Nonionic surfactants such as esters. In addition, the molecular weight of the polymer produced by the polymerization reaction can be appropriately adjusted depending on the reaction temperature and reaction time. In the case of radical polymerization, it can also be adjusted by using a known chain transfer agent. By adjusting the molecular weight, the viscosity of the polyacrylamide polymer aqueous dispersion can be adjusted.
前記ポリアクリルアミド系高分子の水性液のB型粘度は、固形分質量濃度0.5%、温度20℃において50〜2000mPa・sの範囲が好ましく、より好ましくは100〜1500mPa・sの範囲である。ポリアクリルアミド系高分子水分散液のB型粘度が50mPa・s未満になると、塗工時にワックス系撥水剤が紙支持体内部へ浸透して撥水性の低下を抑制する効果が不十分となるおそれがある。逆に、粘度が2000mPa・sを超えると、ポリアクリルアミド系高分子とワックス系撥水剤とが均一に混合し難くなるおそれがある。なお、本発明におけるB型粘度とは、JIS Z 8803−1991記載の単一円筒形回転粘度計による粘度測定方法によるものである。また、本発明において水性液とはポリアクリルアミド系高分子の水溶液または微粒子水分散液を意味する。 The B-type viscosity of the aqueous solution of the polyacrylamide polymer is preferably in the range of 50 to 2000 mPa · s, more preferably in the range of 100 to 1500 mPa · s at a solid content mass concentration of 0.5% and a temperature of 20 ° C. . When the B-type viscosity of the polyacrylamide-based polymer aqueous dispersion is less than 50 mPa · s, the wax-based water repellent penetrates into the inside of the paper support during coating, and the effect of suppressing the decrease in water repellency becomes insufficient. There is a fear. On the other hand, when the viscosity exceeds 2000 mPa · s, it may be difficult to uniformly mix the polyacrylamide polymer and the wax water repellent. In addition, the B type viscosity in this invention is based on the viscosity measuring method with a single cylindrical rotational viscometer described in JIS Z 8803-1991. In the present invention, the aqueous liquid means an aqueous solution or a fine particle aqueous dispersion of a polyacrylamide polymer.
本発明において使用される撥水剤は、ワックス系成分を分散質とする水性エマルジョンが好ましい。このエマルジョンにおいて、分散質となるワックス系成分は、パラフィンワックス、マイクロクリスタリンワックス、ポリエチレンワックスやマレイン化石油樹脂などの変性ワックス成分などを単独で使用してもよく、2種以上を混合して使用してもよい。また、ワックス系成分はロジン系樹脂あるいは不飽和高級アルコール等を含有しても差し支えない。なお、本発明において例示するポリエチレンワックスは重量平均分子量として1000〜10000、単独でフィルム状に成型できないものである。 The water repellent used in the present invention is preferably an aqueous emulsion having a wax component as a dispersoid. In this emulsion, the wax component used as a dispersoid may be a paraffin wax, a microcrystalline wax, a modified wax component such as polyethylene wax or maleated petroleum resin, or a mixture of two or more. May be. The wax component may contain rosin resin or unsaturated higher alcohol. In addition, the polyethylene wax illustrated in this invention is 1000-10000 as a weight average molecular weight, and cannot be shape | molded in a film form independently.
本発明において、ワックス系撥水剤に用いる分散剤には特に制限はなく、ノニオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤や両性界面活性剤が挙げられる。アニオン性界面活性剤としては、例えば高級アルコールの硫酸エステル塩、高級アルキルスルホン酸塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩、ビニルスルホサクシネート等が挙げられる。ノニオン性界面活性剤としては、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フェニルエーテル、ポリエチレングリコール脂肪酸エステル、エチレンオキサイド−プロピレンオキサイドブロック共重合体、ポリオキシエチレン脂肪酸アミド等のポリオキシエチレン構造を有する化合物や、ポリオキシエチレンソルビタン脂肪酸エステルなどのソルビタン誘導体等が挙げられる。カチオン性界面活性剤としては、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルベンジルアンモニウム塩、アシルアミノエチルジエチルアンモニウム塩、アシルアミノエチルジエチルアミン塩、アルキルアミドプロピルジメチルベンジルアンモニウム塩、アルキルピリジニウム塩、アルキルピリジニウム硫酸塩、ステアラミドメチルピリジニウム塩、アルキルキノリニウム塩、アルキルイソキノリニウム塩、脂肪酸ポリエチレンポリアミド、アシルアミノエチルピリジニウム塩、アシルコラミノホルミルメチルピリジニウム塩等の第4級アンモニウム塩、ステアロオキシメチルピリジニウム塩、脂肪酸トリエタノールアミン、脂肪酸トリエタノールアミンギ酸塩、トリオキシエチレン脂肪酸トリエタノールアミン、セチルオキシメチルピリジニウム塩、p−イソオクチルフェノキシエトキシエチルジメチルベンジルアンモニウム塩等のエステル結合アミンやエーテル結合第4級アンモニウム塩、アルキルイミダゾリン、1−ヒドロキシエチル−2−アルキルイミダゾリン、1−アセチルアミノエチル−2−アルキルイミダゾリン、2−アルキル−4−メチル−4−ヒドロキシメチルオキサゾリン等の複素環アミン、ポリオキシエチレンアルキルアミン、N−アルキルプロピレンジアミン、N−アルキルポリエチレンポリアミン、N−アルキルポリエチレンポリアミンジメチル硫酸塩、アルキルビグアニド、長鎖アミンオキシドなどのアミン誘導体等が挙げられる。両性界面活性剤としては、ラウリルベタイン、ラウリルジメチルアミンオキサイド等が挙げられる。 In the present invention, the dispersant used for the wax-based water repellent is not particularly limited, and examples thereof include nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants. Examples of the anionic surfactant include sulfate esters of higher alcohols, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyl sulfone salts. Examples include succinate. Nonionic surfactants include compounds having a polyoxyethylene structure such as polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol fatty acid ester, ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid amide, etc. And sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters. Cationic surfactants include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, acylaminoethyldiethylammonium salt, acylaminoethyldiethylamine salt, alkylamidopropyldimethylbenzylammonium salt, alkylpyridinium salt, alkyl Quaternary ammonium salts such as pyridinium sulfate, stearamide methylpyridinium salt, alkylquinolinium salt, alkylisoquinolinium salt, fatty acid polyethylene polyamide, acylaminoethylpyridinium salt, acylcoraminoformylmethylpyridinium salt, stearo Oxymethylpyridinium salt, fatty acid triethanolamine, fatty acid triethanolamine formate, trioxyethylene fatty acid tri Ester-bonded amines and ether-bonded quaternary ammonium salts such as tanolamine, cetyloxymethylpyridinium salt, p-isooctylphenoxyethoxyethyldimethylbenzylammonium salt, alkylimidazolines, 1-hydroxyethyl-2-alkylimidazolines, 1-acetyl Heterocyclic amines such as aminoethyl-2-alkylimidazoline, 2-alkyl-4-methyl-4-hydroxymethyloxazoline, polyoxyethylene alkylamine, N-alkylpropylenediamine, N-alkylpolyethylenepolyamine, N-alkylpolyethylenepolyamine Examples thereof include amine derivatives such as dimethyl sulfate, alkyl biguanide, and long chain amine oxide. Examples of amphoteric surfactants include lauryl betaine and lauryl dimethylamine oxide.
また、分散剤として保護コロイド作用を有する化合物、高酸価の酸変性化合物、水溶性高分子も使用可能である。該化合物としては、例えばポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、変性デンプン、ポリビニル2−ピロリドン、ポリアクリル酸およびその塩、アクリル酸−無水マレイン酸共重合体およびその塩、スチレン−(メタ)アクリル酸共重合体、エチレン−(メタ)アクリル酸共重合体、イソブチレン−無水マレイン酸交互共重合体、(メタ)アクリル酸−(メタ)アクリル酸アルキルエステル共重合体等の不飽和カルボン酸単位の含有量が26質量%以上のカルボキシル基含有ポリマーおよびその塩、ポリイタコン酸およびその塩、アミノ基を有する水溶性アクリル系共重合体、ゼラチン、アラビアゴム、カゼイン等、一般に微粒子の分散安定剤として用いられている化合物等が挙げられる。 Further, a compound having a protective colloid action, a high acid value acid-modified compound, and a water-soluble polymer can be used as a dispersant. Examples of the compound include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinyl 2-pyrrolidone, polyacrylic acid and salts thereof, acrylic acid-maleic anhydride copolymer, and Its salt, styrene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth) acrylic acid- (meth) acrylic acid alkyl ester copolymer Carboxyl group-containing polymer having an unsaturated carboxylic acid unit content of 26% by mass or more, such as a polymer, and a salt thereof, polyitaconic acid and a salt thereof, a water-soluble acrylic copolymer having an amino group, gelatin, gum arabic, casein, etc. ,one Compounds are used as a dispersion stabilizer particles and the like in.
次に、本発明において使用するワックス系撥水剤の製造方法について説明する。本発明において使用するワックス系撥水剤を得るための製造方法は特に限定されないが、例えば、可溶化式による乳化分散、機械力式による乳化分散などを挙げることができる。可溶化式による乳化分散では、溶融したワックス系成分と界面活性剤とを混合して加温水を少しずつ注加していく。このとき、油系のW/O乳化状態から可溶化状態を経て水系のO/W乳化状態へと移り、ワックス系成分の微細粒子を析出する。可溶化式による乳化分散は水の注加以外に、非イオン性界面活性剤を用いて温度を上下することによっても行うことができる。機械力式による乳化分散では、ワックス系成分、界面活性剤および水を全量容器に入れて温度80〜90℃に加熱しながらホモミキサーで撹拌し、十分均一になった後ホモジナイザーで分散させる。 Next, the manufacturing method of the wax-type water repellent used in this invention is demonstrated. The production method for obtaining the wax-type water repellent used in the present invention is not particularly limited, and examples thereof include a solubilization type emulsification dispersion and a mechanical force type emulsification dispersion. In the emulsification dispersion by the solubilization formula, the melted wax-based component and the surfactant are mixed and warm water is poured little by little. At this time, the oil-based W / O emulsified state passes through the solubilized state to the water-based O / W emulsified state, and fine particles of the wax-based component are precipitated. The emulsification dispersion by the solubilization formula can be performed by raising or lowering the temperature using a nonionic surfactant in addition to the addition of water. In the emulsification dispersion by the mechanical force method, the wax system component, surfactant and water are all put in a container, stirred with a homomixer while heating to a temperature of 80 to 90 ° C., and after being sufficiently uniform, dispersed with a homogenizer.
本発明において、ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液には、通常の塗工紙分野で使用される顔料、接着剤等を必要に応じて適宜混合することができる。 In the present invention, the coating liquid containing the wax-based water repellent and the polyacrylamide-based polymer can be appropriately mixed with a pigment, an adhesive, and the like used in a normal coated paper field as necessary. .
該顔料の具体例としては、重質炭酸カルシウム、軽質炭酸カルシウム、カオリン、焼成カオリン、タルク、硫酸カルシウム、硫酸バリウム、水酸化アルミニウム、二酸化チタン、酸化亜鉛、アルミナ、炭酸マグネシウム、酸化マグネシウム、シリカ、アルミノ珪酸マグネシウム、珪酸カルシウム、ベントナイト、ゼオライト、セリサイト、スメクタイト等の無機顔料や、密実型、中空型、貫通孔型などのプラスチックピグメント、バインダーピグメント等の有機顔料を例示できる。 Specific examples of the pigment include heavy calcium carbonate, light calcium carbonate, kaolin, calcined kaolin, talc, calcium sulfate, barium sulfate, aluminum hydroxide, titanium dioxide, zinc oxide, alumina, magnesium carbonate, magnesium oxide, silica, Examples thereof include inorganic pigments such as magnesium aluminosilicate, calcium silicate, bentonite, zeolite, sericite, and smectite, and plastic pigments such as solid, hollow, and through-hole types, and organic pigments such as binder pigments.
前記接着剤の具体例としては、例えば、酸化澱粉、エステル化澱粉、冷水可溶澱粉などの各種澱粉類、カゼイン、大豆蛋白、合成蛋白などの蛋白質類、カルボキシルメチルセルロース、メチルセルロースなどのセルロール誘導体、ポリビニルアルコールやその変性品等の水溶性接着剤、スチレン−ブタジエン共重合体、メチルメタクリレート−ブタジエン共重合体などの共役ジエン系共重合体ラテックス、アクリル酸アルキルエステルおよび/またはメタクリル酸アルキルエステルの重合体または共重合体ラテックス等のアクリル系(共)重合体ラテックスなどを例示できる。 Specific examples of the adhesive include, for example, various starches such as oxidized starch, esterified starch, and cold water-soluble starch, proteins such as casein, soy protein, and synthetic protein, cellulose derivatives such as carboxymethylcellulose and methylcellulose, polyvinyl Water-soluble adhesives such as alcohol and modified products thereof, conjugated diene copolymer latex such as styrene-butadiene copolymer, methyl methacrylate-butadiene copolymer, polymer of alkyl acrylate and / or alkyl methacrylate Alternatively, acrylic (co) polymer latex such as copolymer latex can be exemplified.
また、塗工液には通常の製紙分野で使用される表面紙力剤、表面サイズ剤等を必要に応じて適宜混合することができる。表面紙力剤、表面サイズ剤の具体例としては、澱粉、酸化澱粉および澱粉変性物、ポリビニルアルコールおよびその誘導体、スチレン−マレイン酸系共重合体、α−オレフィン−マレイン酸系共重合体、スチレン−(メタ)アクリル酸系共重合体、アルキルケテンダイマー等の水分散物等を例示できる。 Further, a surface paper strength agent, a surface sizing agent, and the like used in the normal papermaking field can be appropriately mixed with the coating liquid as necessary. Specific examples of surface paper strength agents and surface sizing agents include starch, oxidized starch and modified starch, polyvinyl alcohol and derivatives thereof, styrene-maleic acid copolymer, α-olefin-maleic acid copolymer, styrene. Examples thereof include aqueous dispersions such as-(meth) acrylic acid copolymers and alkyl ketene dimers.
さらに、塗工液には染料、有色顔料、蛍光染料、酸化防止剤、老化防止剤、消泡剤、紫外線吸収剤、分散剤、pH調整剤等の各種助剤を必要に応じて適宜混合して使用することができる。 Furthermore, various auxiliary agents such as dyes, colored pigments, fluorescent dyes, antioxidants, anti-aging agents, antifoaming agents, ultraviolet absorbers, dispersants, pH adjusters, etc. are mixed in the coating liquid as necessary. Can be used.
ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液の固形分濃度は通常1〜25質量%、好ましくは2〜20質量%の範囲である。 The solid content concentration of the coating liquid containing the wax-based water repellent and the polyacrylamide-based polymer is usually in the range of 1 to 25 mass%, preferably 2 to 20 mass%.
ワックス系撥水剤とポリアクリルアミド系高分子とを含む塗工液を紙支持体に塗工する設備としては、2本ロールサイズプレコーター、ゲートロールサイズプレスコーター、フィルムメタリングサイズプレスコーター、ブレードコーター、キャレンダー、チャンプレックスコーター、バーコーター、ロールコーター、リバースロールコーター、グラビアコーター、エアーナイフコーター、ダイスロットコーター、カーテンコーター、スプレーコーター等から適宜選択することができる。 Equipment for applying a coating liquid containing a wax-based water repellent and a polyacrylamide polymer to a paper support includes a two-roll size precoater, a gate roll size press coater, a film metering size press coater, and a blade. It can be appropriately selected from a coater, a calendar, a champlex coater, a bar coater, a roll coater, a reverse roll coater, a gravure coater, an air knife coater, a die slot coater, a curtain coater, a spray coater and the like.
本発明において、ワックス系撥水剤とポリアクリルアミド系高分子の合計塗工量は、片面当り0.1〜1g/m2の範囲が好ましい。塗工量が0.1g/m2未満であると、撥水性が不十分となるおそれがある。塗工量が1g/m2を超えると、撥水性が飽和し、経済的にも好ましくない。 In the present invention, the total coating amount of the wax water repellent and the polyacrylamide polymer is preferably in the range of 0.1 to 1 g / m 2 per side. If the coating amount is less than 0.1 g / m 2 , the water repellency may be insufficient. When the coating amount exceeds 1 g / m 2 , the water repellency is saturated, which is not preferable economically.
本発明において使用できる紙支持体としては、ライナー、ボール紙などの板紙や、上質紙、中質紙、クラフト紙等が挙げられる。 Examples of the paper support that can be used in the present invention include paperboard such as liner and cardboard, high quality paper, medium quality paper, and craft paper.
前記紙支持体に使用されるパルプとしては、例えば、一般に使用されている広葉樹晒クラフトパルプ(LBKP)、針葉樹晒クラフトパルプ(NBKP)等の漂白化学パルプや、砕木パルプ(GP)、加圧式砕木パルプ(PGW)、リファイナー砕木パルプ(RPM)、サーモメカニカルパルプ(TMP)等の機械パルプや、亜硫酸パルプ、古紙パルプなどが適宜混合使用される。古紙パルプとしては、段ボール古紙、雑誌古紙などが挙げられる。また、本発明の効果を損なわない範囲で必要に応じてケナフ等の非木材繊維原料から得られるパルプ繊維、合成パルプ、無機繊維等を混合することができる。 Examples of the pulp used for the paper support include bleached chemical pulp such as commonly used hardwood bleached kraft pulp (LBKP) and softwood bleached kraft pulp (NBKP), ground pulp (GP), and pressurized ground wood. Mechanical pulp such as pulp (PGW), refiner groundwood pulp (RPM), and thermomechanical pulp (TMP), sulfite pulp, waste paper pulp, and the like are appropriately mixed and used. Examples of the used paper pulp include cardboard used paper and magazine used paper. Moreover, pulp fiber, synthetic pulp, inorganic fiber, etc. which are obtained from non-wood fiber raw materials, such as kenaf, can be mixed as needed in the range which does not impair the effect of this invention.
紙支持体に内添される填料としては、例えば重質炭酸カルシウム、軽質炭酸カルシウム、亜硫酸カルシウム、石膏、タルク、カオリン、焼成カオリン、ホワイトカーボン、非晶質シリカ、珪藻土、炭酸マグネシウム、二酸化チタン、水酸化アルミニウム、水酸化カルシウム、水酸化マグネシウム、水酸化亜鉛等の無機顔料や、尿素−ホルマリン樹脂微粒子、微小中空粒子等の有機顔料等が例示できる。填料は2種類以上の混合使用も可能である。 Examples of the filler internally added to the paper support include heavy calcium carbonate, light calcium carbonate, calcium sulfite, gypsum, talc, kaolin, calcined kaolin, white carbon, amorphous silica, diatomaceous earth, magnesium carbonate, titanium dioxide, Examples thereof include inorganic pigments such as aluminum hydroxide, calcium hydroxide, magnesium hydroxide, and zinc hydroxide, and organic pigments such as urea-formalin resin fine particles and fine hollow particles. Two or more fillers can be used in combination.
紙支持体にはパルプと填料の他に、内添サイズ剤、アニオン性、ノニオン性、カチオン性あるいは両性の歩留り向上剤、濾水性向上剤、紙力増強剤等の抄紙用内添助剤を必要に応じて添加することができる。内添サイズ剤の具体例としては、例えば、アルキルケテンダイマー系、アルケニル無水コハク酸系、スチレン−アクリル系、高級脂肪酸系、石油樹脂系サイズ剤、ロジン系サイズ剤等が挙げられる。また、歩留り向上剤、濾水性向上剤、紙力増強剤の具体例としては、例えば、アルミニウム等の多価金属化合物(具体的には、硫酸バンド、塩化アルミニウム、アルミン酸ソーダ、塩基性アルミニウム化合物等)、各種澱粉類、ポリアクリルアミド、尿素樹脂、ポリアミド−ポリアミン樹脂、ポリエチレンイミン、ポリアミン、ポリビニルアルコール、ポリエチレンオキサイド等が例示できる。さらに、染料、pH調整剤、スライムコントロール剤、消泡剤、粘剤等の抄紙用添加助剤も用途に応じて適宜使用できる。 In addition to pulp and filler, the paper support contains internal additives for papermaking, such as internal sizing agents, anionic, nonionic, cationic or amphoteric yield improvers, drainage improvers, and paper strength enhancers. It can be added as necessary. Specific examples of the internally added sizing agent include alkyl ketene dimer, alkenyl succinic anhydride, styrene-acrylic, higher fatty acid, petroleum resin sizing agent, rosin sizing agent and the like. Specific examples of yield improvers, drainage improvers, and paper strength enhancers include, for example, polyvalent metal compounds such as aluminum (specifically, sulfate bands, aluminum chloride, sodium aluminate, basic aluminum compounds). Etc.), various starches, polyacrylamide, urea resin, polyamide-polyamine resin, polyethyleneimine, polyamine, polyvinyl alcohol, polyethylene oxide and the like. Furthermore, additive agents for papermaking such as dyes, pH adjusters, slime control agents, antifoaming agents, and stickers can be appropriately used depending on the application.
紙支持体の抄紙条件については特に制限はなく、例えば、長網式抄紙機、ギャップフォーマー型抄紙機、円網式抄紙機、短網式抄紙機、傾斜式抄紙機、各種コンビネーション抄紙機等の商業規模の抄紙機が、目的に応じて適宜選択して使用できる。また、本発明で上記抄紙工程から得られる紙支持体は単層のみならず、2層以上の抄き合せ紙でもよい。 There are no particular restrictions on the paper making conditions of the paper support. For example, a long net paper machine, a gap former type paper machine, a circular net paper machine, a short net paper machine, an inclined paper machine, various combination paper machines, etc. Commercial scale paper machines can be selected and used as appropriate according to the purpose. Further, the paper support obtained from the paper making process in the present invention may be not only a single layer but also two or more layers of paper.
以下に実施例を挙げて本発明を具体的に説明するが、もちろん、本発明はそれらに限定されるものではない。なお、特に断らない限り、例中の部および%はそれぞれ質量部、および質量%を示す。また、使用した薬剤の添加量は固形分換算の質量部を示す。 EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an example show a mass part and the mass%, respectively. Moreover, the addition amount of the used chemical | medical agent shows the mass part of solid content conversion.
実施例および比較例で得た撥水紙を以下の方法で評価し、その結果を表1に示した。 The water-repellent paper obtained in Examples and Comparative Examples was evaluated by the following method, and the results are shown in Table 1.
(B型粘度)
ポリアクリルアミド系高分子の濃度0.5質量%水性液について、液温を20℃に調整した後、JIS Z 8803−1991記載の単一円筒形回転粘度計による粘度測定方法でB型粘度を測定した。
(B type viscosity)
After adjusting the liquid temperature to 20 ° C. for an aqueous liquid having a polyacrylamide polymer concentration of 0.5 mass%, the B-type viscosity is measured by a viscosity measuring method using a single cylindrical rotational viscometer described in JIS Z 8803-1991. did.
(撥水度)
得られた評価用撥水紙を23℃、相対湿度50%の環境下において24時間調湿後、JAPAN TAPPI 紙パルプ試験方法 No.68:2000に規定される方法に準じて撥水度を評価した。また、撥水度の熱劣化を試験するため、定温乾燥機を用いて140℃の条件下で20分間熱処理した後、23℃、相対湿度50%の環境下において24時間調湿して、同様に撥水度を評価した。なお、撥水度の評価はR0からR10で判定され、Rの数字が大きいほど撥水性が良好であることを示している。
(Water repellency)
The obtained water-repellent paper for evaluation was conditioned for 24 hours in an environment of 23 ° C. and 50% relative humidity, and then evaluated for water repellency according to the method defined in JAPAN TAPPI Paper Pulp Test Method No. 68: 2000. did. In addition, in order to test the thermal deterioration of the water repellency, after heat treatment for 20 minutes at 140 ° C. using a constant temperature dryer, the humidity was adjusted for 24 hours in an environment of 23 ° C. and 50% relative humidity. The water repellency was evaluated. The evaluation of the water repellency is determined from R0 to R10, and the larger the R number, the better the water repellency.
<実施例1>
(ポリアクリルアミド系高分子水分散液の調製)
水に対してポリアクリルアミド系高分子水分散液(商品名:「ハイホルダーC503」、栗田工業社製)を撹拌しながら点滴して、最終的に固形分濃度0.5%のポリアクリルアミド系高分子水分散液を調製した。このとき、0.5%水分散液のB型粘度は990mPa・sであった。
(撥水処理塗工液の調製)
ワックス系撥水剤(商品名:「WR3936」、星光PMC社製)および前記0.5%ポリアクリルアミド系高分子水分散液をワックス系撥水剤:ポリアクリルアミド系高分子=99.5部:0.5部となるように混合し、最終的に固形分濃度が4%の撥水処理塗工液を調製した。
(撥水紙の作成)
未塗工のジュートライナー(坪量160g/m2)の表面に、上記で得た撥水処理塗工液を固形分塗工量(ワックス系撥水剤とポリアクリルアミド系高分子の合計)が0.4g/m2となるようメイヤーバーで塗工後、熱風乾燥機にて130℃、15秒間乾燥して撥水紙を得た。
<Example 1>
(Preparation of polyacrylamide polymer aqueous dispersion)
A polyacrylamide polymer aqueous dispersion (trade name: “HIHHOLDER C503”, manufactured by Kurita Kogyo Co., Ltd.) is instilled into water with stirring, and finally a polyacrylamide polymer with a solid content concentration of 0.5% is added. A molecular water dispersion was prepared. At this time, the B-type viscosity of the 0.5% aqueous dispersion was 990 mPa · s.
(Preparation of water repellent coating liquid)
Wax-based water repellent (trade name: “WR3936”, manufactured by Seiko PMC Co., Ltd.) and the 0.5% polyacrylamide-based polymer aqueous dispersion were used as wax-based water-repellent: polyacrylamide-based polymer = 99.5 parts: It mixed so that it might become 0.5 part, and finally the water-repellent treatment coating liquid whose solid content concentration is 4% was prepared.
(Create water-repellent paper)
On the surface of an uncoated jute liner (basis weight 160 g / m 2 ), the water-repellent treatment coating solution obtained above has a solid coating amount (total of wax-based water repellent and polyacrylamide polymer). After coating with a Mayer bar so as to be 0.4 g / m 2 , it was dried with a hot air dryer at 130 ° C. for 15 seconds to obtain a water-repellent paper.
<実施例2>
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤:ポリアクリルアミド系高分子=99.9部:0.1部とした以外は実施例1と同様にして撥水紙を得た。
<Example 2>
The water repellency was the same as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellant: polyacrylamide-based polymer = 99.9 parts: 0.1 parts. I got paper.
<実施例3>
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤:ポリアクリルアミド系高分子=98部:2部とした以外は実施例1と同様にして撥水紙を得た。
<Example 3>
A water-repellent paper was obtained in the same manner as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellent: polyacrylamide-based polymer = 98 parts: 2 parts. .
<実施例4>
ポリアクリルアミド系高分子水分散液を「ハイモロックFA230(ハイモ社製)」とした以外は、実施例1と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の濃度0.5%液のB型粘度は50mPa・sであった。
<Example 4>
A water-repellent paper was obtained in the same manner as in Example 1 except that the polyacrylamide-based polymer aqueous dispersion was “Himoloc FA230 (manufactured by Hymo Co.)”. The B type viscosity of the 0.5% concentration polyacrylamide polymer aqueous dispersion was 50 mPa · s.
<実施例5>
ポリアクリルアミド系高分子水分散液を「ハイホルダーA774(栗田工業社製)」とした以外は、実施例1と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の濃度0.5%液のB型粘度が1800mPa・sであった。
<Example 5>
A water-repellent paper was obtained in the same manner as in Example 1 except that “High Holder A774 (manufactured by Kurita Kogyo)” was used as the polyacrylamide polymer aqueous dispersion. The B-type viscosity of the 0.5% concentration polyacrylamide polymer aqueous dispersion was 1800 mPa · s.
<実施例6>
水に対してポリアクリルアミド系高分子粉末(商品名:「アコパール」、MTアクアポリマー社製)を撹拌しながら添加し、ポリアクリルアミド系高分子の固形分濃度が0.5%の水溶液を調製した。このとき、0.5%水溶液の20℃におけるB型粘度は640mPa・sであった。ポリアクリルアミド系高分子を上記の0.5%水溶液とした以外は、実施例1と同様にして撥水紙を得た。
<Example 6>
A polyacrylamide polymer powder (trade name: “Acopearl”, manufactured by MT Aquapolymer Co., Ltd.) was added to water while stirring to prepare an aqueous solution having a polyacrylamide polymer solid content concentration of 0.5%. . At this time, the B-type viscosity at 20 ° C. of the 0.5% aqueous solution was 640 mPa · s. A water repellent paper was obtained in the same manner as in Example 1 except that the polyacrylamide polymer was changed to the above 0.5% aqueous solution.
<比較例3>
ポリアクリルアミド系高分子水分散液を「ポリストロン1208F(荒川化学工業社製)」とした以外は、実施例1と同様にして撥水紙を得た。該ポリアクリルアミド系高分子水分散液の0.5%のB型粘度が15mPa・sであった。
< Comparative Example 3 >
A water-repellent paper was obtained in the same manner as in Example 1 except that “Polystron 1208F (manufactured by Arakawa Chemical Industries)” was used as the polyacrylamide-based polymer aqueous dispersion . The polyacrylamide polymer aqueous dispersion had a 0.5% B-type viscosity of 15 mPa · s.
<実施例7>
撥水処理塗工液の最終固形分濃度を0.5%とし、撥水処理塗工液を塗工する紙支持体を晒クラフト紙(坪量70g/m2)とし、撥水処理塗工液の塗工量を0.05g/m2とした以外は、実施例1と同様にして撥水紙を得た。
<Example 7 >
The final solid concentration of the water-repellent coating liquid is 0.5%, and the paper support on which the water-repellent coating liquid is coated is bleached kraft paper (basis weight 70 g / m 2 ). A water-repellent paper was obtained in the same manner as in Example 1 except that the coating amount of the liquid was 0.05 g / m 2 .
<実施例8>
撥水処理塗工液の最終固形分濃度を1%とし、撥水処理塗工液を塗工する紙支持体を晒クラフト紙(坪量70g/m2)とし、撥水処理塗工液の塗工量を0.1g/m2とした以外は、実施例1と同様にして撥水紙を得た。
<Example 8 >
The final solid content concentration of the water-repellent coating liquid is 1%, the paper support on which the water-repellent coating liquid is applied is bleached kraft paper (basis weight 70 g / m 2 ), and the water-repellent coating liquid A water-repellent paper was obtained in the same manner as in Example 1 except that the coating amount was 0.1 g / m 2 .
<実施例9>
撥水処理塗工液の最終固形分濃度を7%とし、撥水処理塗工液の塗工量を1g/m2とした以外は、実施例1と同様にして撥水紙を得た。
<Example 9 >
A water repellent paper was obtained in the same manner as in Example 1 except that the final solid content concentration of the water repellent treatment coating liquid was 7% and the coating amount of the water repellent treatment coating liquid was 1 g / m 2 .
<実施例10>
撥水処理塗工液の最終固形分濃度を10%とし、撥水処理塗工液の塗工量を1.5g/m2とした以外は、実施例1と同様にして撥水紙を得た。
<Example 10 >
A water-repellent paper was obtained in the same manner as in Example 1 except that the final solid content concentration of the water-repellent coating liquid was 10% and the coating amount of the water-repellent coating liquid was 1.5 g / m 2. It was.
<比較例1>
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤:ポリアクリルアミド系高分子=99.95部:0.05部とした以外は実施例1と同様にして撥水紙を得た。
<Comparative Example 1>
The water repellency was the same as in Example 1 except that the blending ratio of the wax-based water repellent and the polyacrylamide polymer was changed to wax-based water repellant: polyacrylamide polymer = 99.95 parts: 0.05 parts. I got paper.
<比較例2>
ワックス系撥水剤とポリアクリルアミド系高分子の配合比率を、ワックス系撥水剤:ポリアクリルアミド系高分子=97部:3部とした以外は実施例1と同様にして撥水紙を得た。
<Comparative example 2>
A water-repellent paper was obtained in the same manner as in Example 1 except that the mixing ratio of the wax-based water repellent and the polyacrylamide-based polymer was changed to wax-based water repellent: polyacrylamide-based polymer = 97 parts: 3 parts. .
表1から明らかなように、実施例1〜10は下塗り剤を塗工することなく、少ない撥水剤塗工量でも熱による撥水性の低下を効果的に抑制することができた。一方、比較例1〜3はポリアクリルアミド系高分子の配合比率が本発明の特定する範囲外であるため、熱による撥水性の低下が大きかった。
As is apparent from Table 1, Examples 1 to 10 were able to effectively suppress a decrease in water repellency due to heat without applying a primer, even with a small amount of water repellent coating. On the other hand, in Comparative Examples 1 to 3, since the blending ratio of the polyacrylamide polymer was outside the range specified by the present invention, the decrease in water repellency due to heat was large.
紙支持体にワックス系撥水剤とポリアクリルアミド系高分子の固形分質量比が99.9〜98.0:0.1〜2.0である塗工層を設けた本発明の撥水紙は、下塗り剤の塗工が不要で、熱による撥水性の低下が少なく、青果物、水産物等を包装する段ボール、重袋、包装紙等の各種包装用紙材として優れた適性を有していた。 The water-repellent paper of the present invention in which a coating layer having a solid mass ratio of a wax-based water repellent and a polyacrylamide polymer is 99.9 to 98.0: 0.1 to 2.0 is provided on a paper support. No coating of the undercoat was necessary, and the water repellency was hardly lowered by heat, and had excellent suitability as various packaging paper materials such as corrugated cardboard, heavy bags and wrapping paper for packaging fruits and vegetables.
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