JP6917129B2 - Paper containers and heavy bags - Google Patents
Paper containers and heavy bags Download PDFInfo
- Publication number
- JP6917129B2 JP6917129B2 JP2016178163A JP2016178163A JP6917129B2 JP 6917129 B2 JP6917129 B2 JP 6917129B2 JP 2016178163 A JP2016178163 A JP 2016178163A JP 2016178163 A JP2016178163 A JP 2016178163A JP 6917129 B2 JP6917129 B2 JP 6917129B2
- Authority
- JP
- Japan
- Prior art keywords
- paper
- coating layer
- coating
- pigment
- water vapor
- 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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- 239000011247 coating layer Substances 0.000 claims description 86
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 235000019710 soybean protein Nutrition 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Landscapes
- Bag Frames (AREA)
- Wrappers (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Description
本発明は、紙製容器に関する。具体的には食品、香料、消臭剤、芳香剤、防虫剤、化粧品などの匂い成分の漏れ防止性を有する紙管、重袋などの紙製容器に関する。 The present invention relates to a paper container. Specifically, the present invention relates to a paper container such as a paper tube and a heavy bag having a leakage prevention property for odor components such as foods, fragrances, deodorants, air fresheners, insect repellents, and cosmetics.
一般に、紙管は、主に紙、繊維、フィルム等を巻く為の軸として使用される。また、容器として用いられることもある。また、その強度を利用して家具や建築の材料として使用されるものもある。紙管は、クラフト紙や板紙などからなる帯状原紙の複数枚を互いにずらして重合接着させながらスパイラル状に巻着して形成するスパイラル紙管や、原紙を筒状に巻く平巻紙管などがある。紙管は、最近、環境負荷の低減やリサイクル性などの観点から、従来から使用されているプラスチック容器に代わるものとして着目されている。また、紙菅と同様にプラスチック容器の代替品として重袋も着目されている。 Generally, the paper tube is mainly used as a shaft for winding paper, fibers, films and the like. It may also be used as a container. In addition, some of them are used as materials for furniture and construction by utilizing their strength. Paper tubes include spiral paper tubes formed by winding multiple strips of kraft paper, paperboard, etc. in a spiral shape while shifting them from each other and adhering them to each other, and flat-rolled paper tubes that wind the base paper into a cylinder. .. Recently, paper tubes have been attracting attention as an alternative to the conventionally used plastic containers from the viewpoint of reducing the environmental load and recyclability. In addition, heavy bags are also attracting attention as a substitute for plastic containers, as is the case with paper tubes.
プラスチック容器の代替として、紙管や重袋などを用いる場合には、各種のバリア性を要求されるため、例えば、特許文献１に記載されているように、筒状体の両端に調湿性および汚染ガス吸着性を有する層を内側に備えた蓋を設けたり、防湿性および／またはガスバリア性を有する基材をさらに設けたりして、資料の保存性を高めた紙管が開示されている。また、特許文献２には、紙管本体の両端部に無塵紙粘着シートを貼着し、クリーンルーム内での使用を可能とした紙管が開示されている。 When a paper tube, a heavy bag, or the like is used as an alternative to the plastic container, various barrier properties are required. Therefore, for example, as described in Patent Document 1, humidity control properties and humidity control properties are provided at both ends of the tubular body. A paper tube is disclosed in which a lid having a layer having a contaminated gas adsorbing property is provided inside, and a base material having a moisture-proof property and / or a gas barrier property is further provided to improve the storage stability of the material. Further, Patent Document 2 discloses a paper tube in which dust-free paper adhesive sheets are attached to both ends of the paper tube main body so that the paper tube can be used in a clean room.
しかしながら、特許文献１、２に開示されている紙管では、食品、香料、消臭剤、芳香剤、防虫剤などの匂いに対するバリア性がなく、改善が求められている。 However, the paper tubes disclosed in Patent Documents 1 and 2 do not have a barrier property against odors such as foods, flavors, deodorants, air fresheners, and insect repellents, and improvement is required.
そこで、本発明は、食品、香料、消臭剤、芳香剤、防虫剤などの匂い漏れ防止性を有する紙製容器（紙管、重袋など）を提供することを目的とする。 Therefore, an object of the present invention is to provide a paper container (paper tube, heavy bag, etc.) having odor leakage prevention properties such as foods, fragrances, deodorants, air fresheners, and insect repellents.
本発明は以下の[１]〜[４]を提供する。
[１] 紙基材上に塗工層（Ａ）を設けた紙製材料を用いて形成された容器であって、該塗工層（Ａ）が水溶性高分子を含有することを特徴とする、紙製容器。
[２] 前記紙製材料が前記紙基材と塗工層（Ａ）の間に、顔料及び樹脂を含有する塗工層（Ｂ）を設けることを特徴とする、[１]に記載の紙製容器。
[３] 前記紙製容器が、複数の前記紙製材料を互いにずらしながら部分的に重ね合わせて接着した紙管であることを特徴とする、[１]または[２]に記載の紙製容器。
[４] 前記紙製容器が、重袋であることを特徴とする、[１]または[２]に記載の紙製容器。
The present invention provides the following [1] to [4].
[1] A container formed by using a paper material having a coating layer (A) provided on a paper base material, characterized in that the coating layer (A) contains a water-soluble polymer. Paper container.
[2] The paper according to [1], wherein the paper material provides a coating layer (B) containing a pigment and a resin between the paper base material and the coating layer (A). Making container.
[3] The paper container according to [1] or [2], wherein the paper container is a paper tube in which a plurality of the paper materials are partially overlapped and adhered while being displaced from each other. ..
[4] The paper container according to [1] or [2], wherein the paper container is a heavy bag.
本発明によれば、食品、香料、消臭剤、芳香剤、防虫剤、化粧品などの内容物の匂い漏れ防止性を有する紙製容器（紙管、重袋など）を提供することができる。また、紙製容器の内容物に容器外側の匂いが移るのを防ぐこともできる。加えて、本発明の紙製容器は、酸素バリア性、水蒸気バリア性を有するため内容物の酸化や湿気による固化を防ぐことができる。さらに、耐油性も有しているため内容物が油を含む場合でも、油が容器の外側に染み出すことを防ぐことができる。本発明の紙製容器は、紙でできているため、フィルムやプラスチック容器と比較して、環境負荷やリサイクル性に優れている。 According to the present invention, it is possible to provide a paper container (paper tube, heavy bag, etc.) having an odor leakage prevention property for contents such as foods, fragrances, deodorants, air fresheners, insect repellents, and cosmetics. It is also possible to prevent the odor on the outside of the paper container from being transferred to the contents of the paper container. In addition, since the paper container of the present invention has an oxygen barrier property and a water vapor barrier property, it is possible to prevent oxidation of the contents and solidification due to moisture. Further, since it also has oil resistance, it is possible to prevent the oil from seeping out to the outside of the container even when the content contains oil. Since the paper container of the present invention is made of paper, it is superior in environmental load and recyclability as compared with a film or plastic container.
本発明は、紙基材上に水溶性高分子を含有する塗工層（Ａ）を設けた紙製材料を用いて形成された容器であることを特徴としている。さらに、塗工層（Ａ）と紙基材の間に塗工層（Ｂ）が形成された容器であることを特徴としている。塗工層（Ａ）を設けることにより、匂い成分や酸素などのガスが漏れることを防止する機能（本明細書においては、ガスバリア性ともいう）、耐油性を付与することができる。 The present invention is characterized in that it is a container formed by using a paper material in which a coating layer (A) containing a water-soluble polymer is provided on a paper base material. Further, the container is characterized in that the coating layer (B) is formed between the coating layer (A) and the paper base material. By providing the coating layer (A), it is possible to impart a function of preventing gas such as an odor component and oxygen from leaking (also referred to as a gas barrier property in the present specification) and oil resistance.
本発明は、匂い漏れ防止性を有する紙製材料を複数枚ずらして重ねた紙管や匂い漏れ防止性を有する紙製材料を用いた重袋などの匂い漏れ防止性を有する紙製材料を用いた紙製容器に関する。 The present invention uses a paper material having an odor leakage prevention property, such as a paper tube in which a plurality of sheets of a paper material having an odor leakage prevention property are stacked in a staggered manner, or a heavy bag using a paper material having an odor leakage prevention property. Regarding the paper container that was used.
＜紙基材＞
本発明において紙基材とは、主としてパルプからなるシートであり、他に填料、各種助剤を含んでもよい。パルプとしては、広葉樹未晒クラフトパルプ（ＬＵＫＰ）、広葉樹漂白クラフトパルプ（ＬＢＫＰ）、針葉樹未晒クラフトパルプ（ＮＵＫＰ）、針葉樹漂白クラフトパルプ（ＮＢＫＰ）、サルファイトパルプ等の化学パルプ、ストーングラインドパルプ、サーモメカニカルパルプ等の機械パルプ、古紙パルプ、ケナフ、竹、麻等から得られた非木材繊維等である。これらの素材を適宜配合して用いることが可能である。これらの中でも、広葉樹未晒クラフトパルプ（ＬＵＫＰ）、広葉樹漂白クラフトパルプ(ＬＢＫＰ)、針葉樹未晒クラフトパルプ（ＮＵＫＰ）、針葉樹漂白クラフトパルプ(ＮＢＫＰ)等の化学パルプが好ましい。化学パルプは、原紙中への異物混入が発生し難いこと、使用後の紙容器を古紙原料に供してリサイクル使用する際に経時変色が発生し難いこと、高い白色度を有するため印刷時の面感が良好であり容器用の紙製材料として使用価値が高くなること、等の理由から適している。食品向けの容器として使用しない場合は古紙を含んでいてもよい。本発明の紙基材は、単層抄きでも多層抄きでもよい。本発明の紙基材の坪量は特に限定されないが、例えば一般的に用いられている３０ｇ／ｍ2〜５００ｇ／m２程度とすることができ、品種としては、上質紙、薄模造紙、晒クラフト紙、未晒クラフト紙、片艶クラフト紙、重袋クラフト紙、純白ロール紙、グラシン紙、カップ原紙、白板紙、紙管原紙、ライナー原紙などの包装用紙を好適に用いることができる。
<Paper base material>
In the present invention, the paper base material is a sheet mainly made of pulp, and may also contain a filler and various auxiliaries. Examples of the pulp include broadleaf unbleached kraft pulp (LUKP), broadleaf bleached kraft pulp (LBKP), conifer unbleached kraft pulp (NUKP), conifer bleached kraft pulp (NBKP), chemical pulp such as sulfite pulp, stone grind pulp, etc. Non-wood fibers obtained from mechanical pulp such as thermomechanical pulp, used paper pulp, kenaf, bamboo, hemp and the like. It is possible to appropriately mix and use these materials. Among these, chemical pulps such as broad-leaved unbleached kraft pulp (LUKP), broad-leaved bleached kraft pulp (LBKP), softwood unbleached kraft pulp (NUKP), and softwood bleached kraft pulp (NBKP) are preferable. Chemical pulp is less likely to cause foreign matter to enter the base paper, is less likely to discolor over time when the used paper container is used as a raw material for used paper and recycled, and has a high degree of whiteness, so it has a high whiteness on the surface during printing. It is suitable for reasons such as good feeling and high utility value as a paper material for containers. If it is not used as a container for food, it may contain used paper. The paper substrate of the present invention may be single-layer or multi-layer. The basis weight of the paper substrate of the present invention is not particularly limited, can be, for example, generally 30 g / m 2, which is used to 500 g / m 2 approximately, the breed, fine paper, thin construction paper, Wrapping paper such as bleached kraft paper, unbleached kraft paper, single-gloss kraft paper, heavy bag kraft paper, pure white roll paper, glassin paper, cup base paper, white paperboard, paper tube base paper, and liner base paper can be preferably used.
填料は添加してもしなくてもよいが、添加する場合は、ホワイトカーボン、タルク、カオリン、クレー、重質炭酸カルシウム、軽質炭酸カルシウム、酸化チタン、ゼオライト、合成樹脂填料等の公知の填料を使用することができる。また、硫酸バンドや各種のアニオン性、カチオン性、ノニオン性あるいは、両性の歩留まり向上剤、濾水性向上剤、紙力増強剤や内添サイズ剤等の抄紙用内添助剤を必要に応じて使用することができる。更に、染料、蛍光増白剤、ｐＨ調整剤、消泡剤、ピッチコントロール剤、スライムコントロール剤等も必要に応じて添加することができる。 The filler may or may not be added, but when added, known fillers such as white carbon, talc, kaolin, clay, heavy calcium carbonate, light calcium carbonate, titanium oxide, zeolite, and synthetic resin filler are used. can do. In addition, a sulfate band and various anionic, cationic, nonionic, or amphoteric yield improvers, drainage improvers, paper strength enhancers, internal sizing agents, and other papermaking aids are used as needed. Can be used. Further, a dye, a fluorescent whitening agent, a pH adjusting agent, a defoaming agent, a pitch control agent, a slime control agent and the like can be added as needed.
紙基材の製造（抄紙）方法は特に限定されるものではなく、公知の長網フォーマーマシン、オントップハイブリッドフォーマーマシン、ギャップフォーマーマシン、円網フォーマーマシンを用いて、酸性抄紙、中性抄紙、アルカリ抄紙方式で抄紙して単層あるいは多層の基材を製造することができる。また、紙基材は一般に塗工紙に用いられる坪量２５〜５００ｇ／ｍ２程度のものが好ましい。更に、紙基材の表面を各種薬剤で処理することが可能である。使用される薬剤としては、酸化澱粉、ヒドロキシエチルエーテル化澱粉、酸素変性澱粉、ポリアクリルアミド、ポリビニルアルコール、表面サイズ剤、耐水化剤、保水剤、増粘剤、滑剤等を例示することができ、これらを単独あるいは２種類以上を混合して用いることができる。紙基材の表面処理の方法は特に限定されるものではないが、ロッドメタリング式サイズプレス、ポンド式サイズプレス、ゲートロールコーター、スプレーコーター、ブレードコーター、カーテンコーター等公知の塗工装置を用いることができる。 The method for producing (papermaking) the paper base material is not particularly limited, and acid papermaking can be performed using a known long net former machine, on-top hybrid former machine, gap former machine, and circular net former machine. A single-layer or multi-layer base material can be produced by papermaking by a neutral papermaking method or an alkaline papermaking method. Further, the paper base material preferably has a basis weight of about 25 to 500 g / m 2 , which is generally used for coated paper. Further, the surface of the paper base material can be treated with various chemicals. Examples of the chemicals used include oxidized starch, hydroxyethyl etherified starch, oxygen-modified starch, polyacrylamide, polyvinyl alcohol, surface sizing agents, water resistant agents, water retaining agents, thickeners, lubricants, and the like. These can be used alone or in combination of two or more. The method of surface treatment of the paper substrate is not particularly limited, but a known coating device such as a rod metering type size press, a pound type size press, a gate roll coater, a spray coater, a blade coater, and a curtain coater is used. be able to.
＜塗工層（Ａ）について＞
本発明において、紙基材上の少なくとも片面に水溶性高分子を含有する塗工層（Ａ）を設ける。塗工層（Ａ）を形成する塗工液のバインダー樹脂として使用される水溶性高分子としては、完全ケン化ポリビニルアルコール、部分ケン化ポリビニルアルコール、エチレン共重合ポリビニルアルコール、ポリビニルピロリドン、デンプン、変性デンプン、デキストリン、メチルセルロース、カルボキシメチルセルロース、アルギン酸ナトリウム等を例示することができる。これらの中では、匂いの漏れ防止性、性の点から、ポリビニルアルコール、カルボキシメチルセルロースが好ましく、ポリビニルアルコールが更に好ましい。
<About coating layer (A)>
In the present invention, a coating layer (A) containing a water-soluble polymer is provided on at least one side of the paper substrate. Examples of the water-soluble polymer used as a binder resin for the coating liquid forming the coating layer (A) include fully saponified polyvinyl alcohol, partially saponified polyvinyl alcohol, ethylene copolymer polyvinyl alcohol, polyvinylpyrrolidone, starch, and modified products. Examples thereof include starch, dextrin, methyl cellulose, carboxymethyl cellulose, sodium alginate and the like. Among these, polyvinyl alcohol and carboxymethyl cellulose are preferable, and polyvinyl alcohol is more preferable, from the viewpoint of odor leakage prevention and sex.
（顔料について）
本発明において、塗工層（Ａ）に使用される顔料を添加することが可能であり、顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト、マイカ等の無機顔料及び密実型、中空型、又はコアーシェル型等の有機顔料がある。これらを単独又は２種類以上混合して使用することができる。これらの中では、匂いの漏れ防止性の点から無機顔料を使用することが好ましく、平均粒子径３μｍ以上、且つアスペクト比が１０以上の無機顔料（特にカオリン）を使用することが更に好ましく、平均粒子径５μｍ以上、且つアスペクト比が５０以上の無機顔料（特にカオリン）を使用することが特に好ましい。塗工層（Ａ）に顔料を含有させた場合、気体状の匂い成分は顔料を迂回して通過するため、顔料を含有していない水溶性高分子からなる塗工層と比較して、優れた匂い成分の漏れ防止性を有する。
(About pigments)
In the present invention, the pigment used in the coating layer (A) can be added, and the pigments include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, and talc. , Titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white, mica and other inorganic pigments and solid, hollow or core-shell type organic pigments. These can be used alone or in combination of two or more. Among these, it is preferable to use an inorganic pigment from the viewpoint of preventing odor leakage, and it is more preferable to use an inorganic pigment (particularly kaolin) having an average particle size of 3 μm or more and an aspect ratio of 10 or more, and the average. It is particularly preferable to use an inorganic pigment (particularly kaolin) having a particle size of 5 μm or more and an aspect ratio of 50 or more. When the coating layer (A) contains a pigment, the gaseous odor component bypasses the pigment and passes through the coating layer (A), which is superior to the coating layer made of a water-soluble polymer containing no pigment. Has the ability to prevent leakage of odorous components.
本発明において、塗工層（Ａ）に含有する顔料と水溶性高分子の配合比率（乾燥重量）は顔料／水溶性高分子が１／１００〜１０００／１００であることが好ましい。顔料の比率が上記範囲外であると充分な匂い成分の漏れ防止性が発揮しない。 In the present invention, the blending ratio (dry weight) of the pigment and the water-soluble polymer contained in the coating layer (A) is preferably 1/100 to 1000/100 for the pigment / water-soluble polymer. If the ratio of the pigment is out of the above range, sufficient odor component leakage prevention property will not be exhibited.
（架橋剤について）
本発明において、塗工層（Ａ）に多価金属塩等に代表される架橋剤を添加することが可能である。架橋剤は水溶性高分子の水酸基どうしを架橋構造にて結合させるため、高湿度となった場合に結合が緩む（又は切れる）水酸基量が減少し、層全体の耐水性が向上するため、高湿度下での匂い成分の濡れ防止性の低下が抑制できる。
(About cross-linking agent)
In the present invention, it is possible to add a cross-linking agent typified by a polyvalent metal salt or the like to the coating layer (A). Since the cross-linking agent bonds the hydroxyl groups of the water-soluble polymer in a cross-linked structure, the amount of hydroxyl groups that loosen (or break) the bonds when the humidity is high decreases, and the water resistance of the entire layer improves, so it is high. It is possible to suppress a decrease in the wetting prevention property of the odor component under humidity.
本発明において、架橋剤の種類としては特に限定されるものではなく、塗工層（Ａ）に含有されるバインダーの種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタン等の多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物等のイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸等を適宜選択して使用することができる。架橋剤の配合部数においても塗工可能な塗料濃度や塗料粘度の範囲内であれば特に限定されることなく配合することができる。なお、架橋効果発現の観点から、多価金属塩を使用することが好ましく、カリウムミョウバンを使用することがより好ましい。 In the present invention, the type of the cross-linking agent is not particularly limited, and a polyvalent metal salt (copper, zinc, silver, iron, potassium, etc.) is used according to the type of binder contained in the coating layer (A). Polyvalent metals such as sodium, zirconium, aluminum, calcium, barium, magnesium and titanium are bonded to ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide and boron oxide. Compounds), amine compounds, amide compounds, aldehyde compounds, hydroxyic acids and the like can be appropriately selected and used. The number of parts of the cross-linking agent to be blended is not particularly limited as long as it is within the range of the paint concentration and the paint viscosity that can be applied. From the viewpoint of exhibiting the cross-linking effect, it is preferable to use a polyvalent metal salt, and it is more preferable to use potassium alum.
架橋剤の添加量は、塗工層（Ａ）に使用される樹脂１００重量部に対して、１〜１０重量部であり、より好ましくは３〜５重量部である。１重量部より少ないと、十分な効果が得られず、１０重量部より多いと、塗工液の粘度が著しく増加するため、塗工困難になる。 The amount of the cross-linking agent added is 1 to 10 parts by weight, more preferably 3 to 5 parts by weight, based on 100 parts by weight of the resin used for the coating layer (A). If it is less than 1 part by weight, a sufficient effect cannot be obtained, and if it is more than 10 parts by weight, the viscosity of the coating liquid increases remarkably, which makes coating difficult.
（添加剤）
本発明において、顔料を水溶性高分子中に配合する際に、顔料を水分散してスラリー化したものを添加し混合することが好ましい。
(Additive)
In the present invention, when the pigment is blended in the water-soluble polymer, it is preferable to add and mix the pigment in water-dispersed slurry.
本発明において、塗工層（Ａ）には、水溶性高分子、顔料の他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を使用することができる。 In the present invention, in addition to water-soluble polymers and pigments, dispersants, thickeners, water-retaining agents, defoaming agents, water-resistant agents, dyes, fluorescent dyes and the like are usually used for the coating layer (A). Various auxiliaries can be used.
＜塗工層（Ｂ）について＞
本発明において、紙基材と塗工層（Ａ）の間に、顔料及び樹脂を含有する塗工層（Ｂ）を設けることが好ましい。塗工層（Ｂ）を設けることにより、紙基材への塗工層（Ａ）を形成するための塗工液の浸透が抑制されるため、均一な塗工層（Ａ）を形成させることができ、よりガスバリア性能を発揮しやすい。また、塗工層（Ｂ）が水蒸気バリア性（水に対するバリア性）を有している場合、容器内の内容物への水分の影響を抑制できるとともに、紙基材から浸透する水分の塗工層（Ａ）への影響を抑制することができる。
<About the coating layer (B)>
In the present invention, it is preferable to provide a coating layer (B) containing a pigment and a resin between the paper base material and the coating layer (A). By providing the coating layer (B), the permeation of the coating liquid for forming the coating layer (A) into the paper substrate is suppressed, so that a uniform coating layer (A) is formed. It is easier to demonstrate gas barrier performance. Further, when the coating layer (B) has a water vapor barrier property (barrier property against water), the influence of moisture on the contents in the container can be suppressed, and the coating of moisture permeating from the paper base material can be suppressed. The influence on the layer (A) can be suppressed.
＜塗工層（Ｂ）：水蒸気バリア性なし＞
塗工層（Ｂ）の主たる役割は、紙基材への塗工層（Ａ）を形成するための塗工液の浸透を抑制し、均一な塗工層（Ａ）を形成することである。塗工層（Ｂ）に、水蒸気バリア性を付与しない場合は、印刷用紙などで一般的に用いられている塗工層を設ければよい。
<Coating layer (B): No water vapor barrier property>
The main role of the coating layer (B) is to suppress the penetration of the coating liquid for forming the coating layer (A) into the paper substrate and to form the uniform coating layer (A). .. When the water vapor barrier property is not imparted to the coating layer (B), a coating layer generally used for printing paper or the like may be provided.
（顔料及び樹脂）
樹脂としては、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体、ポリビニルアルコール、無水マレイン酸共重合体、およびアクリル酸・メチルメタクリレート系共重合体等の合成系樹脂；カゼイン、大豆蛋白、合成蛋白等の蛋白質類；酸化澱粉、陽性澱粉、尿素燐酸エステル化澱粉、ヒドロキシエチルエーテル化澱粉等のエーテル化澱粉、デキストリン等の澱粉類；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、ヒドロキシメチルセルロース等のセルロース誘導体等が挙げられる。
(Pigment and resin)
As the resin, various copolymers such as styrene / butadiene type, styrene / acrylic type, ethylene / vinyl acetate type, butadiene / methyl methacrylate type, vinyl acetate / butyl acrylate type, polyvinyl alcohol, maleic anhydride copolymer, and Synthetic resins such as acrylic acid / methyl methacrylate copolymers; proteins such as casein, soybean protein, and synthetic proteins; etherified starches such as oxidized starch, positive starch, urea phosphate esterified starch, and hydroxyethyl etherified starch, Distillates such as dextrin; cellulose derivatives such as carboxymethyl cellulose, hydroxyethyl cellulose, hydroxymethyl cellulose and the like can be mentioned.
本発明においては、合成系接着剤と澱粉類を併用することが好ましい。好ましい態様において、これらの接着剤は合計で、顔料１００重量部当たり５〜５０重量部、より好ましくは８〜３０重量部、より好ましくは、８〜１５重量部程度の範囲で使用される。 In the present invention, it is preferable to use a synthetic adhesive and starches in combination. In a preferred embodiment, these adhesives are used in total in the range of 5 to 50 parts by weight, more preferably 8 to 30 parts by weight, more preferably about 8 to 15 parts by weight per 100 parts by weight of the pigment.
顔料としては、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、焼成クレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイトなどの無機顔料および密実型、中空型、またはコアーシェル型などの有機顔料などを必要に応じて単独または二種類以上混合して使用することができる。 Pigments include kaolin, clay, engineered kaolin, delaminated clay, calcined clay, heavy calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica. , Inorganic pigments such as satin white and organic pigments such as solid type, hollow type, or core-shell type can be used alone or in combination of two or more, if necessary.
また、塗工層（Ｂ）を形成する塗工液には、必要に応じて、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、着色剤、界面活性剤等、通常の塗工紙用顔料に配合される各種助剤を適宜使用できる。 In addition, the coating liquid forming the coating layer (B) may contain, if necessary, a dispersant, a thickener, a water retention agent, a defoaming agent, a water resistant agent, a colorant, a surfactant, or the like. Various auxiliaries blended in coating paper pigments can be used as appropriate.
本発明の塗工層（Ｂ）を形成させる塗工液の固形分濃度は、４０〜７５重量％であり、より好ましくは５０〜７０重量％であり、さらに好ましくは６０〜７０重量％である。 The solid content concentration of the coating liquid forming the coating layer (B) of the present invention is 40 to 75% by weight, more preferably 50 to 70% by weight, and further preferably 60 to 70% by weight. ..
＜塗工層（Ｂ）：水蒸気バリア性あり＞
（樹脂について）
塗工層（Ｂ）に含有させる樹脂としては、スチレン・ブタジエン系、スチレン・アクリル系、エチレン・酢酸ビニル系、ブタジエン・メチルメタクリレート系、酢酸ビニル・ブチルアクリレート系等の各種共重合体、無水マレイン酸共重合体、アクリル酸・メチルメタクリレート系共重合体等を単独あるいは２種類以上混合して使用することができる。これらの中ではスチレン・ブタジエン系樹脂が水蒸気バリア性の点から好ましい。
<Coating layer (B): Water vapor barrier property>
(About resin)
Examples of the resin contained in the coating layer (B) include various copolymers such as styrene / butadiene type, styrene / acrylic type, ethylene / vinyl acetate type, butadiene / methyl methacrylate type, vinyl acetate / butyl acrylate type, and male anhydride. An acid copolymer, an acrylic acid / methyl methacrylate-based copolymer, or the like can be used alone or in combination of two or more. Among these, styrene-butadiene resin is preferable from the viewpoint of water vapor barrier property.
本発明においてスチレン・ブタジエン系合成樹脂とは、スチレンとブタジエンを主構成モノマーとし、これに変性を目的とする各種のコモノマーを組み合わせ、乳化重合したものである。コモノマーの例として、メチルメタクリルレート、アクリロニトリル、アクリルアミド、ヒドロキシエチルアクリレートや、イタコン酸、マレイン酸、アクリル酸等の不飽和カルボン酸等が挙げられる。 In the present invention, the styrene-butadiene synthetic resin is obtained by emulsion-polymerizing styrene and butadiene as main constituent monomers by combining them with various comonomer for the purpose of modification. Examples of comonomer include methyl methacrylate, acrylonitrile, acrylamide, hydroxyethyl acrylate, unsaturated carboxylic acids such as itaconic acid, maleic acid, and acrylic acid.
樹脂は、水を分散剤とし、乳化したエマルジョンタイプの塗工料として使用する。乳化剤としては、オレイン酸ナトリウム、ロジン酸石鹸、アルキルアリルスルホン酸ナトリウム、ジアルキルスルホコハク酸ナトリウム等のアニオン性界面活性剤である。これらを単独、又はノニオン性界面活性剤と組み合わせて用いることができる。更に、必要に応じて両性又はカチオン性界面活性剤を用いても良い。 The resin uses water as a dispersant and is used as an emulsified emulsion-type coating material. Examples of the emulsifier include anionic surfactants such as sodium oleate, soap rosinate, sodium alkylallyl sulfonate, and sodium dialkyl sulfosuccinate. These can be used alone or in combination with a nonionic surfactant. Further, an amphoteric or cationic surfactant may be used if necessary.
本発明において、塗工層（Ａ）がはじかない範囲で、塗工層（Ｂ）を形成する塗工液に炭化水素、シリコーン系樹脂、フッ素系樹脂、脂肪酸及び脂肪酸とアルコールのエステル等の撥水成分を含有させることができる。 In the present invention, the coating liquid forming the coating layer (B) is repelled by hydrocarbons, silicone-based resins, fluororesins, fatty acids, and esters of fatty acids and alcohols, to the extent that the coating layer (A) does not repel. It can contain a water component.
（顔料について）
本発明において、塗工層（Ｂ）に顔料を含有させることにより、水蒸気バリア性の向上、塗工層（Ａ）との密着性を向上させることができる。
(About pigments)
In the present invention, by incorporating the pigment in the coating layer (B), the water vapor barrier property can be improved and the adhesion to the coating layer (A) can be improved.
顔料としては、無機顔料、有機顔料がある。無機顔料は、カオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト等である。有機顔料は、密実型、中空型、又はコアーシェル型等である。これらの顔料を単独又は２種類以上混合して使用することができる。 Pigments include inorganic pigments and organic pigments. Inorganic pigments are kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, silicic acid, silicate, colloidal silica, satin white. And so on. The organic pigment is a solid type, a hollow type, a core-shell type, or the like. These pigments can be used alone or in combination of two or more.
顔料は、扁平形状で大きなものが適している。更に、大粒径と小粒径を併用することにより水蒸気バリア性が向上する。 The pigment is suitable to have a flat shape and a large size. Further, the water vapor barrier property is improved by using the large particle size and the small particle size together.
これらの顔料の中でも、形状が扁平なカオリン等の無機顔料は、水蒸気のバリア性を向上させる。特に、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンがより好ましい。扁平な顔料は塗工層に平行に分布し、水蒸気バリア層内に浸透した水蒸気は、扁平な顔料によって厚さ方向に移動することが遮られ、迂回して移動することとなり、水蒸気が水蒸気バリア層を通過する経路が長くなり、バリア性が向上する。添加する顔料のアスペクト比が小さいと塗工層中を水蒸気が迂回する回数が減少し、移動する距離が短くなるため、結果として水蒸気バリア性は、扁平で大粒径の顔料よりも劣ることとなる。 Among these pigments, inorganic pigments such as kaolin having a flat shape improve the barrier property of water vapor. In particular, kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more is more preferable. The flat pigment is distributed parallel to the coating layer, and the water vapor that has permeated into the water vapor barrier layer is blocked from moving in the thickness direction by the flat pigment and moves around, and the water vapor moves to the water vapor barrier. The path through the layer becomes longer and the barrier property is improved. If the aspect ratio of the pigment to be added is small, the number of times water vapor circulates in the coating layer is reduced and the distance traveled is shortened. As a result, the water vapor barrier property is inferior to that of the flat and large particle size pigment. Become.
扁平な顔料は、ガスバリア層でも同様の作用が期待できる。 The flat pigment can be expected to have the same effect on the gas barrier layer.
扁平な顔料として、カオリンの他、マイカやモンモリロナイトを使用することも可能である。しかしながら、マイカ、モンモリロナイトの分散液はカオリンの分散液より低濃度であり、マイカ、モンモリロナイトを用いた水蒸気バリア層用の塗工液は低濃度となるため、形成される水蒸気バリア層中でおいて、顔料が配向しにくくなるため、カオリンの方が適している。 In addition to kaolin, mica and montmorillonite can also be used as the flat pigment. However, the dispersion of mica and montmorillonite has a lower concentration than the dispersion of kaolin, and the coating solution for the water vapor barrier layer using mica and montmorillonite has a lower concentration. , Kaolin is more suitable because the pigment is less likely to be oriented.
水蒸気バリア層に上記した扁平な顔料添加に加えて平均粒子径が５μｍ以下の顔料を更に添加することにより、水蒸気バリア性を更に向上させることができる。この小粒径の顔料は扁平である必要はない。 By further adding a pigment having an average particle size of 5 μm or less in addition to the above-mentioned addition of the flat pigment to the water vapor barrier layer, the water vapor barrier property can be further improved. This small particle size pigment does not have to be flat.
本発明において、塗工層（Ｂ）を設ける場合には、水蒸気バリア性の向上、及び塗工層（Ａ）との密着性の点から、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンを含有する水蒸気バリア層に、更に平均粒子径５μｍ以下の顔料を含有させることが好ましい。重層的に存在する均粒子径５μｍ以上且つアスペクト比１０以上のカオリンの間に平均粒子径５μｍ以下の顔料が入り込む構造となって、扁平なカオリンの面に沿って移動を余儀なくされる水蒸気は、この小さな顔料粒子により移動が阻止されることとなる。つまり、水蒸気バリア層に扁平性と平均粒子径の異なる顔料を含有させた場合、水蒸気バリア層中で、隣接する扁平で大きな粒子径の顔料の間に形成される空隙に小さな粒子径の顔料が充填された状態となり、水蒸気は顔料を迂回して通過するため、小さな粒子径の顔料を混入していない水蒸気バリア層と比較して、高い水蒸気バリア性を発揮する。 In the present invention, when the coating layer (B) is provided, kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more is used from the viewpoint of improving the water vapor barrier property and adhesion to the coating layer (A). It is preferable that the water vapor barrier layer contained further contains a pigment having an average particle size of 5 μm or less. Water vapor, which has a structure in which a pigment having an average particle size of 5 μm or less is inserted between kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more, which exists in multiple layers, is forced to move along a flat surface of kaolin. The movement is blocked by these small pigment particles. That is, when the water vapor barrier layer contains pigments having different flatness and average particle size, pigments having a small particle size are formed in the voids formed between adjacent flat and large particle size pigments in the water vapor barrier layer. Since it is in a filled state and water vapor passes around the pigment, it exhibits a high water vapor barrier property as compared with a water vapor barrier layer in which a pigment having a small particle size is not mixed.
本発明において、平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンと平均粒子径５μｍ以下の顔料の配合比率が乾燥重量で、５０／５０〜９９／１であることが好ましい。平均粒子径５μｍ以上且つアスペクト比１０以上のカオリンの比率が上記範囲より少ないと水蒸気が塗工層中を迂回する距離が短くなるため、十分な水蒸気バリア性を得ることができない。一方、上記範囲より多いと、塗工層中の大粒径顔料が形成する空隙を平均粒子径５μｍ以下の顔料で十分に埋めることができないため、水蒸気バリア性の向上は見られない。 In the present invention, the blending ratio of kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more and a pigment having an average particle size of 5 μm or less is preferably 50/50 to 99/1 in terms of dry weight. If the ratio of kaolin having an average particle size of 5 μm or more and an aspect ratio of 10 or more is less than the above range, the distance through which water vapor circulates in the coating layer becomes short, so that sufficient water vapor barrier properties cannot be obtained. On the other hand, if the amount exceeds the above range, the voids formed by the large particle size pigment in the coating layer cannot be sufficiently filled with the pigment having an average particle size of 5 μm or less, so that the water vapor barrier property is not improved.
本発明において、平均粒子径５μｍ以下の顔料としてはカオリン、クレー、エンジニアードカオリン、デラミネーテッドクレー、重質炭酸カルシウム、軽質炭酸カルシウム、タルク、二酸化チタン、硫酸バリウム、硫酸カルシウム、酸化亜鉛、珪酸、珪酸塩、コロイダルシリカ、サチンホワイト等の無機顔料及び密実型、中空型、又はコアーシェル型等の有機顔料等を単独又は２種類以上混合して使用することができる。これらの顔料の中では、重質炭酸カルシウムが好ましい。 In the present invention, pigments having an average particle size of 5 μm or less include kaolin, clay, engineered kaolin, delaminated clay, heavy calcium carbonate, light calcium carbonate, talc, titanium dioxide, barium sulfate, calcium sulfate, zinc oxide, and silicic acid. , Inorganic pigments such as silicate, colloidal silica, and satin white, and organic pigments such as solid type, hollow type, and core-shell type can be used alone or in combination of two or more. Among these pigments, heavy calcium carbonate is preferable.
塗工層（Ｂ）に顔料を含有させる場合、樹脂と顔料の配合量は、顔料（乾燥重量）１００重量部に対して、樹脂（乾燥重量）５〜２００重量部の範囲で使用されることが好ましく、より好ましくは樹脂２０〜１５０重量部である。また、水蒸気バリア層には、樹脂、顔料の他、分散剤、増粘剤、保水剤、消泡剤、耐水化剤、染料、蛍光染料等の通常使用される各種助剤を使用することができる。 When the coating layer (B) contains a pigment, the blending amount of the resin and the pigment shall be in the range of 5 to 200 parts by weight of the resin (dry weight) with respect to 100 parts by weight of the pigment (dry weight). Is preferable, and more preferably 20 to 150 parts by weight of the resin. In addition to resins and pigments, various commonly used auxiliaries such as dispersants, thickeners, water retention agents, defoamers, water resistant agents, dyes, and fluorescent dyes can be used for the water vapor barrier layer. can.
（架橋剤）
本発明において、水蒸気バリア層に多価金属塩等に代表される架橋剤を添加することが好ましい。架橋剤は水蒸気バリア層に含有されるバインダーと架橋反応を起こすため、水蒸気バリア層内の結合の数（架橋点）が増加する。つまり、水蒸気バリア層が緻密な構造となり、良好な水蒸気バリア性を発揮する。
(Crosslinking agent)
In the present invention, it is preferable to add a cross-linking agent typified by a polyvalent metal salt or the like to the water vapor barrier layer. Since the cross-linking agent causes a cross-linking reaction with the binder contained in the water vapor barrier layer, the number of bonds (cross-linking points) in the water vapor barrier layer increases. That is, the water vapor barrier layer has a dense structure and exhibits good water vapor barrier properties.
本発明において、架橋剤の種類としては特に限定されるものではなく、水蒸気バリア層に含有されるバインダーの種類に合わせて、多価金属塩（銅、亜鉛、銀、鉄、カリウム、ナトリウム、ジルコニウム、アルミニウム、カルシウム、バリウム、マグネシウム、チタン等の多価金属と、炭酸イオン、硫酸イオン、硝酸イオン、燐酸イオン、珪酸イオン、窒素酸化物、ホウ素酸化物等のイオン性物質が結合した化合物）、アミン化合物、アミド化合物、アルデヒド化合物、ヒドロキシ酸等から適宜選択して使用することができる。架橋剤の配合部数は、塗工可能な塗料濃度や塗料粘度の範囲内であれば特に限定されることなく配合することができる。なお、水蒸気バリア性に優れた効果を発揮するスチレン・ブタジエン系、スチレン・アクリル系等のスチレン系の水蒸気バリア性樹脂を用いた場合、架橋効果発現の観点から、多価金属塩を使用することが好ましい。更に、カリウムミョウバンがより好ましい。 In the present invention, the type of the cross-linking agent is not particularly limited, and the polyvalent metal salt (copper, zinc, silver, iron, potassium, sodium, zirconium) is matched according to the type of the binder contained in the water vapor barrier layer. , A compound in which polyvalent metals such as aluminum, calcium, barium, magnesium and titanium are combined with ionic substances such as carbonate ion, sulfate ion, nitrate ion, phosphate ion, silicate ion, nitrogen oxide and boron oxide). It can be appropriately selected and used from an amine compound, an amide compound, an aldehyde compound, a hydroxy acid and the like. The number of copies of the cross-linking agent can be blended without particular limitation as long as it is within the range of the paint concentration and the paint viscosity that can be applied. When a styrene-based water vapor barrier resin such as styrene / butadiene or styrene / acrylic, which exhibits an excellent effect on water vapor barrier, is used, a polyvalent metal salt should be used from the viewpoint of exhibiting the cross-linking effect. Is preferable. In addition, potassium alum is more preferred.
架橋剤の添加量は、水蒸気バリア層に使用されるバインダー樹脂１００重量部に対して、１〜１０重量部である。より好ましくは３〜５重量部である。１重量部より少ないと、十分な効果が得られず、１０重量部より多いと、塗工液の粘度が著しく増加するため、塗工困難になる。 The amount of the cross-linking agent added is 1 to 10 parts by weight with respect to 100 parts by weight of the binder resin used for the water vapor barrier layer. More preferably, it is 3 to 5 parts by weight. If it is less than 1 part by weight, a sufficient effect cannot be obtained, and if it is more than 10 parts by weight, the viscosity of the coating liquid increases remarkably, which makes coating difficult.
本発明において、水蒸気バリア層を形成させる塗工液に架橋剤を添加する場合、水酸化アンモニウム溶液等の極性溶媒に架橋剤を溶解させてから塗工液へ添加することが好ましい。架橋剤を極性溶媒に溶解することにより、架橋剤と極性溶媒で結合を作るため塗工液へ配合しても直ちにラテックスとの架橋反応は起こらず、塗料の増粘を抑制することができる。その場合、紙への塗工後に乾燥することにより極性溶媒成分が揮発し、バインダーとの架橋反応が起こり、緻密な水蒸気バリア層が形成されると推測される。 In the present invention, when the cross-linking agent is added to the coating liquid for forming the water vapor barrier layer, it is preferable to dissolve the cross-linking agent in a polar solvent such as an ammonium hydroxide solution and then add the cross-linking agent to the coating liquid. By dissolving the cross-linking agent in a polar solvent, a bond is formed between the cross-linking agent and the polar solvent, so that the cross-linking reaction with the latex does not occur immediately even if the cross-linking agent is added to the coating liquid, and the thickening of the paint can be suppressed. In that case, it is presumed that the polar solvent component is volatilized by drying after coating on the paper, a cross-linking reaction with the binder occurs, and a dense water vapor barrier layer is formed.
（接触角）
本発明において、紙基材上に設ける塗工層（Ｂ）表面の水との接触角は、９０°未満が好ましく、より好ましくは８５°未満、更に好ましくは８０°未満である。水との接触角が９０°以上であると、均一な塗工層（Ａ）を設けることが困難となり、高い匂い漏れ防止性を発揮することが困難となる。９０°未満の場合には、塗工層（Ｂ）と塗工層（Ａ）の反発性を抑えて両層間の剥離を抑制することできる。この接触角は塗工層（Ｂ）と塗工層（Ａ）の親和性を推測する目安となる。なお、塗工層（Ｂ）表面の水との接触角を調整する方法としては、限定されるものではないが、水との接触角の低い樹脂の使用、顔料の添加等を挙げることができる。
(Contact angle)
In the present invention, the contact angle of the surface of the coating layer (B) provided on the paper substrate with water is preferably less than 90 °, more preferably less than 85 °, still more preferably less than 80 °. When the contact angle with water is 90 ° or more, it becomes difficult to provide a uniform coating layer (A), and it becomes difficult to exhibit high odor leakage prevention property. When the temperature is less than 90 °, the resilience of the coating layer (B) and the coating layer (A) can be suppressed and the peeling between the two layers can be suppressed. This contact angle serves as a guide for estimating the affinity between the coating layer (B) and the coating layer (A). The method for adjusting the contact angle of the surface of the coating layer (B) with water includes, but is not limited to, the use of a resin having a low contact angle with water, the addition of a pigment, and the like. ..
＜各塗工層の塗工量について＞
本発明において、塗工層（Ａ）の塗工量は、乾燥重量で０．２〜１０ｇ／ｍ２、好ましくは２〜６ｇ／ｍ２とすることがよい。塗工量が０．２ｇ／ｍ２未満であると均一な塗工層を形成することができないため、十分な匂い漏れ防止性が得られない問題がある。一方、１０ｇ／ｍ２を超えると、塗工時の乾燥負荷が大きくなり、操業面、コスト面の両方の観点より好ましくない。
<About the coating amount of each coating layer>
In the present invention, the coating amount of the coating layer (A) is preferably 0.2 to 10 g / m 2 by dry weight, preferably 2 to 6 g / m 2. If the coating amount is less than 0.2 g / m 2 , a uniform coating layer cannot be formed, so that there is a problem that sufficient odor leakage prevention property cannot be obtained. On the other hand, if it exceeds 10 g / m 2 , the drying load at the time of coating becomes large, which is not preferable from the viewpoint of both operation and cost.
本発明において、水蒸気バリア性を有する塗工層（Ｂ）を設ける場合は、その塗工量は、乾燥重量で４〜３０ｇ／ｍ２とすることが好ましく、より好ましくは６〜２５ｇ／ｍ2であり、更に好ましくは１０〜２０ｇ／ｍ２であることが好ましい。塗工量が３ｇ／ｍ２以下であると原紙を塗工液が完全に被覆することが困難となり、塗工層（Ａ）が紙基材に浸透するため、均一な塗工層（Ａ）が得られないため、匂い漏れ防止性の向上は見込めない。一方、３０ｇ／ｍ２を超えると、塗工時の乾燥負荷が大きくなり、操業面、コスト面の両方の観点より好ましくない。 In the present invention, when the coating layer (B) having a water vapor barrier property is provided, the coating amount thereof is preferably 4 to 30 g / m 2 in terms of dry weight, and more preferably 6 to 25 g / m 2. It is more preferably 10 to 20 g / m 2 . If the coating amount is 3 g / m 2 or less, it becomes difficult for the coating liquid to completely cover the base paper, and the coating layer (A) permeates the paper substrate, so that the uniform coating layer (A) is used. Therefore, it is not expected to improve the odor leakage prevention property. On the other hand, if it exceeds 30 g / m 2 , the drying load at the time of coating becomes large, which is not preferable from the viewpoint of both operation and cost.
本発明において、水蒸気バリア性を有する塗工層（Ｂ）に代えて、水蒸気バリア性を有さない塗工層（Ｂ）を設ける場合、その塗工量は、乾燥重量で２．０〜２０ｇ／ｍ２とすることが好ましい。塗工量が２．０ｇ／ｍ２未満であると原紙を塗工液が完全に被覆することが困難となり、塗工層（Ａ）が紙基材に浸透するため、均一な塗工層（Ａ）が得られないため、匂い漏れ防止性の向上は見込めない。一方、２０ｇ／ｍ２を超えると、塗工時の乾燥負荷が大きくなり、操業面、コスト面の両方の観点より好ましくない。 In the present invention, when a coating layer (B) having no water vapor barrier property is provided in place of the coating layer (B) having a water vapor barrier property, the coating amount thereof is 2.0 to 20 g in dry weight. It is preferably / m 2. If the coating amount is less than 2.0 g / m 2 , it becomes difficult for the coating liquid to completely cover the base paper, and the coating layer (A) permeates the paper substrate, so that a uniform coating layer ( Since A) cannot be obtained, improvement in odor leakage prevention is not expected. On the other hand, if it exceeds 20 g / m 2 , the drying load at the time of coating becomes large, which is not preferable from the viewpoint of both operation and cost.
＜塗工方法について＞
本発明において、塗工層（Ａ）、塗工層（Ｂ）の塗工方法については特に限定されるものではなく、公知の塗工装置を用いることができる。例えば、ブレードコーター、バーコーター、ロールコーター、エアナイフコーター、リバースロールコーター、カーテンコーター、スプレーコーター、エアナイフコーター、サイズプレスコーター、ゲートロールコーター等が挙げられる。なかでも、塗工層（Ａ）については、カーテンコーター、エアナイフコーター、スプレーコーターなどの非接触型コーターが好ましい。また、塗工層を乾燥させる手法としては、例えば、蒸気加熱ヒーター、ガスヒーター、赤外線ヒーター、電気ヒーター、熱風加熱ヒーター、マイクロウェーブ、シリンダードライヤー等の通常の方法が用いられる。
<About coating method>
In the present invention, the coating method of the coating layer (A) and the coating layer (B) is not particularly limited, and a known coating apparatus can be used. For example, a blade coater, a bar coater, a roll coater, an air knife coater, a reverse roll coater, a curtain coater, a spray coater, an air knife coater, a size press coater, a gate roll coater and the like can be mentioned. Among them, for the coating layer (A), a non-contact type coater such as a curtain coater, an air knife coater, or a spray coater is preferable. Further, as a method for drying the coating layer, for example, a usual method such as a steam heater, a gas heater, an infrared heater, an electric heater, a hot air heater, a microwave, or a cylinder dryer is used.
本発明において、紙基材上に少なくとも塗工層（Ａ）を設けた紙製材料に、ポリエチレン、ポリプロピレン、ポリ酢酸ビニル重合体等のシーラント層を設けることができる。シーラント層の積層方法については特に制限されるものではないが、従来の溶融押し出しラミ法やフィルムを用いたドライラミ法、直接溶融コート法等公知の方法を用いることができる。 In the present invention, a sealant layer such as polyethylene, polypropylene, or polyvinyl acetate polymer can be provided on a paper material having at least a coating layer (A) provided on a paper base material. The method for laminating the sealant layer is not particularly limited, but a known method such as a conventional melt-extruded laminating method, a dry laminating method using a film, or a direct melt coating method can be used.
＜紙基材に塗工層（Ａ）を設けた紙製材料の酸素バリア性＞
本発明の紙製材料の酸素透過度（２３℃、０％ＲＨ）は、０．３〜０．８ｍｌ／ｍ２・ｄａｙであることが好ましい。
<Oxygen barrier property of a paper material having a coating layer (A) on a paper substrate>
Oxygen permeability of the paper material of the present invention (23 ℃, RH 0%) is preferably 0.3~0.8ml / m 2 · day.
＜紙基材に塗工層（Ａ）及び塗工層（Ｂ）を設けた紙製材料の水蒸気バリア性＞
本発明の紙製材料の水蒸気バリア性としては、温度４０±０．５℃、相対湿度９０±２％の条件下で、水蒸気透過度が５００ｇ／ｍ２・ｄａｙ以下であることが好ましく、３００ｇ／ｍ２・ｄａｙ以下であることがより好ましい。
<Water vapor barrier property of a paper material provided with a coating layer (A) and a coating layer (B) on a paper substrate>
The water vapor barrier properties of the paper material of the present invention, the temperature 40 ± 0.5 ° C., under a relative humidity of 90 ± 2%, preferably water vapor permeability is not more than 500g / m 2 · day, 300g It is more preferably less than / m 2 · day.
＜容器について＞
本発明において、紙製容器とは、紙箱、小袋、角底袋、手提げ袋、封筒、重袋などの袋、紙管容器など、または、原紙に各種フィルムをラミネートして、三方シール、四方シール、スティック包装、ピロー、スタンディングパウチなどの各種包装形態、カップ、液体容器、飲料容器等としたものをいう。また、本発明の紙製容器とは、「主として紙製」のもの、詳しくは、すべてが紙素材からなるもの、紙とプラあるいは紙とプラとアルミ箔、などの複合素材の容器包装において、重量で一番多い素材が紙であるものをいう。また、プラスチック注出口などの異素材の部材を有する複合容器においても、紙が一番多い場合も該当する。
<About the container>
In the present invention, the paper container is a paper box, a pouch, a square bottom bag, a handbag, an envelope, a bag such as a heavy bag, a paper tube container, etc. It refers to various packaging forms such as stick packaging, pillows, and standing pouches, cups, liquid containers, beverage containers, and the like. Further, the paper container of the present invention refers to a container "mainly made of paper", specifically, a container made entirely of paper material, a container or packaging made of a composite material such as paper and plastic or paper and plastic and aluminum foil. Paper is the heaviest material in terms of weight. In addition, even in a composite container having members made of different materials such as a plastic spout, the case where the amount of paper is the largest is also applicable.
本発明の紙製材料は、ポリエチレン、ポリプロピレン、ＰＥＴなど各種樹脂フィルムやアルミニウムなどの他の素材と組み合わせて使用することもできる。フィルムとしてバリア性を有するフィルムを用いることもできる。 The paper material of the present invention can also be used in combination with various resin films such as polyethylene, polypropylene and PET, and other materials such as aluminum. A film having a barrier property can also be used as the film.
本発明の紙製材料にシーラントをラミネートしてヒートシール性を付与することもできる。ヒートシール性を付与した袋等は、密封性が向上するため、ガスバリア性、水蒸気バリア性は優れている。ヒートシール性を付与する樹脂としては、一般に用いられているものを適宜利用できる。例えば、低密度ポリエチレン、無延伸ポリプロピレンなどを用いることができるが、ヒートシール性を有する樹脂であればこれに限られない。 It is also possible to impart heat sealability by laminating a sealant on the paper material of the present invention. A bag or the like to which heat-sealing property is imparted has excellent gas barrier property and water vapor barrier property because the sealing property is improved. As the resin that imparts heat-sealing property, a commonly used resin can be appropriately used. For example, low-density polyethylene, unstretched polypropylene, and the like can be used, but the resin is not limited to this as long as it has a heat-sealing property.
本発明の紙製材料をもちいて、紙管容器にした場合は、つなぎ目が少ない構造のため、ラミネート等をしなくても比較的密閉に近い容器とすることができ、バリア性を保持することができる。さらにすべて紙製なので環境負荷の低減やリサイクル性の観点からも好適である。 When the paper material of the present invention is used to make a paper tube container, the structure has few joints, so that the container can be made relatively closed without laminating, and the barrier property is maintained. Can be done. Furthermore, since it is made entirely of paper, it is suitable from the viewpoint of reducing the environmental load and recyclability.
本発明において、紙基材上に少なくとも塗工層（Ａ）を設けた紙製材料を、複数枚重ねて重袋に用いた場合は、紙のみから成るバリア性の重袋であり、匂いの漏れやすい原料等の包装材料として好適である。複数枚重ねることにより、バリア性を向上させることができる。 In the present invention, when a plurality of paper materials having at least a coating layer (A) provided on a paper base material are stacked and used as a heavy bag, the heavy bag has a barrier property consisting of only paper and has an odor. It is suitable as a packaging material for leaky raw materials. By stacking a plurality of sheets, the barrier property can be improved.
本発明の容器は、香料またはそれを含有するもの（芳香剤、お香など）、防虫剤、たばこ、漢方原料、匂いの強い食品、化粧品などの容器として好適である。 The container of the present invention is suitable as a container for fragrances or those containing them (fragrances, incense, etc.), insect repellents, tobacco, Chinese herbal ingredients, foods with strong odors, cosmetics, and the like.
＜紙管について＞
本発明においては、前記の紙基材上に少なくとも塗工層（Ａ）を形成させた紙製材料を用いて、常法によりスパイラル状または平巻の紙管を製造することができる。使用する紙製材料の坪量、厚さなどは、内容物の形状、種類によって、適宜調整することが好ましい。紙管は、複数の帯状の原紙を互いにずらしながら接着し、バリア面に途切れや隙間がない筒状となるため、紙箱に比べ、バリア性を保持しやすい。また、紙管は複数枚の材料を重ねあわせることによって製造されるが、匂い漏れ防止性を付与するには、紙管原紙のうち、１枚以上を紙基材上に塗工層（Ａ）を形成させた紙製材料を用いることが必要となる。また、紙管の蓋は、本発明のバリア基材を用いて、密着性の高い態様で製造することができる。また、紙菅の蓋には、紙基材上に塗工層（Ａ）を形成させた紙製材料、金属製、プラスチック製の蓋、ヒートシール性を有するラミネート層を設けた材料を使用することができる。
<About paper tubes>
In the present invention, a spiral or flat-rolled paper tube can be produced by a conventional method using a paper material in which at least a coating layer (A) is formed on the paper substrate. It is preferable to appropriately adjust the basis weight, thickness, etc. of the paper material to be used depending on the shape and type of the contents. The paper tube adheres a plurality of strip-shaped base papers while shifting each other to form a tubular shape with no breaks or gaps on the barrier surface, so that it is easier to maintain the barrier property as compared with the paper box. Further, the paper tube is manufactured by superimposing a plurality of sheets of material, and in order to impart odor leakage prevention property, one or more sheets of the paper tube base paper are coated on the paper base material (A). It is necessary to use a paper material on which the above is formed. Further, the lid of the paper tube can be manufactured in a highly adhesive manner by using the barrier base material of the present invention. Further, for the lid of the paper tube, a paper material having a coating layer (A) formed on a paper base material, a metal or plastic lid, and a material having a heat-sealing laminate layer are used. be able to.
以下に、本発明について、実施例を挙げて具体的に説明するが、本発明はこれらに限定されるものではない。なお、本明細書において、特に断らない限り、「％」はすべて「重量％」であり、数値範囲はその端点を含むものとする。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In the present specification, unless otherwise specified, "%" is all "% by weight", and the numerical range includes the end points thereof.
評価方法
（１）坪量：ＪＩＳ Ｐ ８１２４：２０１１に準拠して測定した
（２）紙厚：ＪＩＳ Ｐ ８１１８：１９９８に準拠して測定した。
（３）水蒸気透過度：温度４０±０．５℃、相対湿度９０±２％の条件下で、透湿度測定器（Ｄｒ．Ｌｙｓｓｙ社製 Ｌ８０−４０００）を用いて測定した。
（４）酸素透過度：ＭＯＣＯＮ社製 ＯＸ−ＴＲＡＮ２／２１を使用し、２３℃、０％ＲＨ条件及び２３℃、８５％ＲＨ条件にて測定した。
（５）接触角度：２３℃、５０％ＲＨ雰囲気下で、動的表面接触角測定装置（Ｆｉｂｒｏ社製 ダイナミックアブソープションテスタ ＤＡＴ１１００）を用い、水滴を滴下後０．１秒後の表面接触角を測定した。
（６）平均粒子径：試料スラリーを分散剤ヘキサメタリン酸ソーダ０．２重量％添加した純水中で滴下混合して均一分散体とし、レーザー法粒度測定機（使用機器：マルバーン社製 マスターサイザーＳ型）を使用して粒度測定する。
（７）アスペクト比：顔料の平面方向及び断面方向を、ＳＥＭ（走査型電子顕微鏡）を用いて撮影し、顔料配向面の直系と長さを測定して、［アスペクト比＝顔料配向面の直径／厚さ］により算出した。
（８）匂い漏れ防止性：内容物を密閉２４時間後、紙管から漏れてくる匂いを官能評価により３段階で評価した。
◎：まったく匂いが漏れない、○：少し匂いが漏れる、×：かなり匂いが漏れる
（９）酸化度評価方法：メチルレッド０．１ｇとブロムチモールブルー０．３ｇをエチルアルコール１５０ｍｌに溶かしてから、精製水５０ｍｌを加え２００ｍｌとし、酸化度指示薬原液を作成する。酸化度指示原液と精製水を１：５０の割合で混合し酸化度指示液とする。精米１０ｇを試験管に入れる。試験管に前記酸化度指示液を１０ｍｌ加え、試験管の口を閉じ、振とうする。試験管立てに試験管を静置する。
静置直後の液の呈色状況を判定する。
緑→黄緑→黄→オレンジ→赤に呈色するほど酸化が進んでいる。
Evaluation method (1) Basis weight: Measured according to JIS P 8124: 2011 (2) Paper thickness: Measured according to JIS P 8118: 1998.
(3) Moisture vapor transmission rate: Measured using a moisture permeability measuring device (L80-4000 manufactured by Dr. Lyssy) under the conditions of a temperature of 40 ± 0.5 ° C. and a relative humidity of 90 ± 2%.
(4) Oxygen permeability: Measured using OX-TRAN2 / 21 manufactured by MOCON under 23 ° C. and 0% RH conditions and 23 ° C. and 85% RH conditions.
(5) Contact angle: Surface contact angle 0.1 seconds after dropping water droplets using a dynamic surface contact angle measuring device (Dynamic Absorption Tester DAT1100 manufactured by Fibro) under a 50% RH atmosphere at 23 ° C. Was measured.
(6) Average particle size: The sample slurry was dropped and mixed in pure water to which 0.2% by weight of sodium hexametaphosphate as a dispersant was added to obtain a uniform dispersion, and a laser particle size measuring machine (equipment used: Mastersizer S manufactured by Malvern) was used. Use the mold) to measure the particle size.
(7) Aspect ratio: The plane direction and the cross-sectional direction of the pigment are photographed using an SEM (scanning electron microscope), and the direct line and the length of the pigment orientation surface are measured. / Thickness] was calculated.
(8) Smell leakage prevention property: After 24 hours after sealing the contents, the odor leaking from the paper tube was evaluated on a three-point scale by sensory evaluation.
◎: No odor leaks at all, ○: Slight odor leaks, ×: Quite odor leaks (9) Oxidation evaluation method: After dissolving 0.1 g of methyl red and 0.3 g of bromothymol blue in 150 ml of ethyl alcohol, Add 50 ml of purified water to make 200 ml, and prepare an oxidation degree indicator stock solution. Oxidation degree indicator stock solution and purified water are mixed at a ratio of 1:50 to obtain an oxidation degree indicator solution. Put 10 g of polished rice in a test tube. Add 10 ml of the oxidation degree indicator solution to the test tube, close the mouth of the test tube, and shake. Place the test tube on the test tube rack.
Determine the coloration status of the liquid immediately after standing.
Oxidation progresses as the color develops from green to yellowish green to yellow to orange to red.
実施例１
（塗工層（Ａ）用塗工液（塗工液Ａ）の調製）
大粒径エンジニアードカオリン（イメリス社製 バリサーフＨＸ、粒子径９．０μｍ、アスペクト比８０−１００）に分散剤としてポリアクリル酸ソーダを添加し（対無機顔料０．２部）、セリエミキサーで分散し固形分濃度５５％の大粒径カオリンスラリーを調整した。ポリビニルアルコール（クラレ社製 ＰＶＡ１１７）を固形分濃度１０％となるよう調製し、ＰＶＡ溶液を得た。得られたカオリンスラリーと、ＰＶＡ溶液を固形分で顔料：ＰＶＡ溶液＝１００：１００として固形分濃度が１０％となるよう混合し、塗工液Ａを調整した。
(塗工層（Ｂ）用塗工液（塗工液Ｂ）の調製)
大粒径エンジニアードカオリン（イメリス社製 バリサーフＨＸ、粒子径９．０μｍ、アスペクト比８０−１００）に分散剤としてポリアクリル酸ソーダを添加し（対無機顔料０．２部）、セリエミキサーで分散して固形分濃度５５％の大粒径カオリンスラリーを調製した。得られたカオリンスラリー中にスチレン・ブタジエン系ラテックス（日本ゼオン社製 ＰＮＴ７８６８）を対顔料１００部（固形分）となるように配合し、固形分濃度５０％の塗工液Ｂを得た。
Example 1
(Preparation of coating liquid (coating liquid A) for coating layer (A))
Sodium polyacrylate was added as a dispersant to large particle size engineered kaolin (Varisurf HX manufactured by Imeris, particle size 9.0 μm, aspect ratio 80-100) (0.2 parts of inorganic pigment) and dispersed with a serie mixer. A large particle size kaolin slurry having a solid content concentration of 55% was prepared. Polyvinyl alcohol (PVA117 manufactured by Kuraray Co., Ltd.) was prepared so as to have a solid content concentration of 10%, and a PVA solution was obtained. The obtained kaolin slurry and the PVA solution were mixed with a solid content of pigment: PVA solution = 100: 100 so that the solid content concentration was 10%, and the coating liquid A was adjusted.
(Preparation of coating liquid (coating liquid B) for coating layer (B))
Sodium polyacrylate was added as a dispersant to large particle size engineered kaolin (Varisurf HX manufactured by Imeris, particle size 9.0 μm, aspect ratio 80-100) (0.2 parts of inorganic pigment) and dispersed with a serie mixer. A large particle size kaolin slurry having a solid content concentration of 55% was prepared. Styrene-butadiene latex (PNT7868 manufactured by Zeon Corporation) was blended into the obtained kaolin slurry so as to have 100 parts (solid content) of the pigment to obtain a coating liquid B having a solid content concentration of 50%.
（紙製材料１の作成）
カップ原紙（坪量２７０ｇ／ｍ２）上に塗工液Ｂを塗工量（乾燥重量）１５ｇ／ｍ２となるよう塗工速度３００ｍ／分でブレードコーターを用いて片面塗工、乾燥した後、その上に塗工液Ａを塗工量（乾燥重量）２．０ｇ／ｍ２となるよう塗工速度３００ｍ／分でエアナイフコーターを用いて片面塗工し、坪量２８７ｇ／ｍ２、紙厚０.３ｍｍの紙製材料を得た。
得られた紙製材料１の酸素透過度（乾燥下）は、１．０ｍｌ／ｍ２・ｄａｙ、酸素透過度（高湿度下）は２００ｍｌ／ｍ２・ｄａｙ、水蒸気バリア層塗工後の接触角は７５°、水蒸気透過度は２５０ｇ／ｍ２・ｄａｙであった。
(Creation of paper material 1)
Apply coating liquid B on the cup base paper (basis weight 270 g / m 2 ) to a coating amount (dry weight) of 15 g / m 2 at a coating speed of 300 m / min using a blade coater on one side and after drying. On top of this, the coating liquid A was applied on one side using an air knife coater at a coating speed of 300 m / min so that the coating amount (dry weight) was 2.0 g / m 2, and the basis weight was 287 g / m 2 , paper. A paper material having a thickness of 0.3 mm was obtained.
The oxygen permeability (under drying) of the obtained paper material 1 is 1.0 ml / m 2 · day, the oxygen permeability (under high humidity) is 200 ml / m 2 · day, and the contact after coating the water vapor barrier layer. corner 75 °, the water vapor transmission rate was 250g / m 2 · day.
（紙製材料２の作成）
紙基材を片艶クラフト紙（坪量７０ｇ／ｍ２）とした以外は、上記と同様にして、坪量８７ｇ／ｍ２、紙厚０．１ｍｍのバリア原紙（片艶クラフト紙）を得た。
得られた紙製材料２の酸素透過度（乾燥下）は、１．０ｍｌ／ｍ２・ｄａｙ、酸素透過度（高湿度下）は２００ｍｌ／ｍ２・ｄａｙ、水蒸気バリア層塗工後の接触角は７５°、水蒸気透過度は２５０ｇ／ｍ２・ｄａｙであった。
(Creation of paper material 2)
A barrier base paper (single-gloss kraft paper) having a basis weight of 87 g / m 2 and a paper thickness of 0.1 mm was obtained in the same manner as above, except that the paper base material was single-gloss kraft paper (basis weight 70 g / m 2). rice field.
The oxygen permeability (under drying) of the obtained paper material 2 is 1.0 ml / m 2 · day, the oxygen permeability (under high humidity) is 200 ml / m 2 · day, and the contact after coating the water vapor barrier layer. corner 75 °, the water vapor transmission rate was 250g / m 2 · day.
（紙管容器１の製造）
上記紙製材料１（カップ原紙）をスリッター加工して、８４ｍｍ幅、８４．２ｍｍ幅各１丁、上記紙製材料２をスリッター加工して、９５ｍｍ幅１丁用意し、紙管の内側から、紙製材料１（カップ原紙）８４ｍｍ幅、紙製材料１（カップ原紙）８４．２ｍｍ幅、紙製材料２（片艶クラフト紙）９５ｍｍ幅の順で、バリア塗工面を内側にしてずらしながら重ね、常法により紙管製造装置によってφ５１の紙層３層がバリア性の紙製材料から成るスパイラル紙管を得た。次に、紙菅に内容物（お香（ラベンダー）、室内消臭芳香剤（ラベンダー）、パラゾール防虫剤）を入れた後、紙管の両端に、紙製材料２を酢酸ビニル系の接着剤で張り付けて密閉した。
(Manufacturing of paper tube container 1)
The paper material 1 (cup base paper) is slitter-processed to prepare one each of 84 mm width and 84.2 mm width, and the paper material 2 is slitter-processed to prepare one 95 mm width. Paper material 1 (cup base paper) 84 mm width, paper material 1 (cup base paper) 84.2 mm width, and paper material 2 (single gloss kraft paper) 95 mm width. A spiral paper tube having three φ51 paper layers made of a barrier paper material was obtained by a paper tube manufacturing apparatus by a conventional method. Next, after putting the contents (incense (lavender), indoor deodorant air freshener (lavender), parasol insect repellent) in the paper tube, paper material 2 is applied to both ends of the paper tube with a vinyl acetate adhesive. It was pasted with and sealed.
比較例１
通常の実施例１で使用したカップ原紙（塗工層なし）、片艶クラフト紙（塗工層なし）を用いた他は、実施例と同様にした。
Comparative Example 1
The same as in the examples except that the cup base paper (without the coating layer) and the single-gloss kraft paper (without the coating layer) used in the usual Example 1 were used.
表１より、実施例１の紙管容器１は匂い漏れの防止の効果が認められた。 From Table 1, the paper tube container 1 of Example 1 was found to have an effect of preventing odor leakage.
（紙管容器２の製造）
バリア性のない通常のカップ原紙（坪量２７０ｇ／ｍ2）をスリッター加工して、９０．５ｍｍ幅、９１ｍｍ幅各１丁、上記紙製材料２（片艶クラフト紙）をスリッター加工して、９５ｍｍ幅１丁、通常の晒クラフト紙（坪量１００ｇ／ｍ2）をスリッター加工し、９６ｍｍ幅を用意した。
紙管外筒：紙管の内側から、カップ原紙９０．５ｍｍ幅、カップ原紙９１ｍｍ幅、紙製材料２（片艶クラフト紙）９５ｍｍ幅、晒クラフト紙９６ｍｍ幅の順で、バリア塗工面を内側にしてずらしながら重ね、常法により紙管製造装置によってφ５２．５のスパイラル紙管外筒を得た。この紙管容器外筒は、紙層４層のうち、最外層より一層内側がバリア性の紙製材料から成る。
紙管内筒：通常の晒クラフト紙９６ｍｍ幅、カップ原紙９０．５ｍｍ幅を用いて内側から晒クラフト紙、カップ原紙、晒クラフト紙の順に重ね、５１φのスパイラル紙管内筒を得た。上下のメンコ部分は、紙製材料２をコート白ボールに貼合したものを用い、印籠型紙管を得た。
(Manufacturing of paper tube container 2)
Normal cup base paper (basis weight 270 g / m 2 ) without barrier properties is slitter processed, and 90.5 mm width and 91 mm width 1 each, and the above paper material 2 (single gloss kraft paper) is slitter processed. One 95 mm wide, ordinary bleached kraft paper (basis weight 100 g / m 2 ) was slitter processed to prepare a 96 mm wide.
Paper tube outer cylinder: From the inside of the paper tube, the barrier coating surface is inside in the order of cup base paper 90.5 mm width, cup base paper 91 mm width, paper material 2 (single gloss kraft paper) 95 mm width, bleached kraft paper 96 mm width. A spiral paper tube outer cylinder having a diameter of 52.5 was obtained by a paper tube manufacturing apparatus by a conventional method. The outer cylinder of the paper tube container is made of a paper material having a barrier property inside the outermost layer of the four layers of the paper layer.
Paper tube inner cylinder: Using normal bleached kraft paper 96 mm width and cup base paper 90.5 mm width, bleached kraft paper, cup base paper, and bleached kraft paper were stacked in this order from the inside to obtain a spiral paper tube inner cylinder of 51φ. For the upper and lower menco parts, a paper material 2 was bonded to a coated white ball to obtain an inro-shaped paper tube.
（紙管容器３の製造）
通常のカップ原紙（坪量２７０ｇ／ｍ2）と紙製材料１（カップ原紙）をスリッター加工して、９０．５ｍｍ幅、９１ｍｍ幅各１丁、上記紙製材料２をスリッター加工して、９５ｍｍ幅１丁、通常の晒クラフト紙をスリッター加工し、９６ｍｍ幅を用意した。
紙管外筒：紙管の内側から、カップ原紙９０．５ｍｍ幅、カップ原紙９１ｍｍ幅、紙製材料２（片艶クラフト紙）９５ｍｍ幅、晒クラフト紙９６ｍｍ幅の順で、バリア塗工面を内側にしてずらしながら重ね、常法により紙管製造装置によってφ５２．５のスパイラル紙管外筒を得た。この紙管容器外筒は、紙層４層のうち、最外層より一層内側がバリア性の紙製材料から成る。
紙管内筒：紙製材料２（片艶クラフト紙）９６ｍｍ幅、紙製材料１（カップ原紙）９０．５ｍｍ幅を用いて内側から紙製材料２、紙製材料１、晒クラフトの順に重ね、スパイラル紙管内筒を得た。上下のメンコ部分は、紙製材料２をコート白ボールに貼合したものを用い、印籠型紙管を得た。
(Manufacturing of paper tube container 3)
Normal cup base paper (basis weight 270 g / m 2 ) and paper material 1 (cup base paper) are slitter processed, 90.5 mm width, 91 mm width 1 each, and the above paper material 2 is slitter processed to 95 mm. A width of 96 mm was prepared by slitting ordinary bleached kraft paper.
Paper tube outer cylinder: From the inside of the paper tube, the barrier coating surface is inside in the order of cup base paper 90.5 mm width, cup base paper 91 mm width, paper material 2 (single gloss kraft paper) 95 mm width, bleached kraft paper 96 mm width. A spiral paper tube outer cylinder having a diameter of 52.5 was obtained by a paper tube manufacturing apparatus by a conventional method. The outer cylinder of the paper tube container is made of a paper material having a barrier property inside the outermost layer of the four layers of the paper layer.
Paper tube inner cylinder: Using paper material 2 (single gloss kraft paper) 96 mm width and paper material 1 (cup base paper) 90.5 mm width, stack paper material 2, paper material 1, and bleached kraft in this order from the inside. A spiral paper tube inner cylinder was obtained. For the upper and lower menco parts, a paper material 2 was bonded to a coated white ball to obtain an inro-shaped paper tube.
実施例２
（紙製材料３の作成）
紙基材を片艶クラフト紙（坪量７０ｇ／ｍ２）とし、塗工液Ａを塗工量（乾燥重量）４．０ｇ／ｍ２となるよう塗工した以外は、実施例１と同様にして、坪量８９ｇ／ｍ２、紙厚０．１ｍｍのバリア原紙（片艶クラフト紙）を得た。
Example 2
(Creation of paper material 3)
Same as in Example 1 except that the paper base material is single-gloss kraft paper (basis weight 70 g / m 2 ) and the coating liquid A is coated so that the coating amount (dry weight) is 4.0 g / m 2. Then, a barrier base paper (single gloss kraft paper) having a basis weight of 89 g / m 2 and a paper thickness of 0.1 mm was obtained.
得られた紙製材料３の酸素透過度（乾燥下）は、１０４．０ｍｌ／ｍ２・ｄａｙ、酸素透過度（高湿度下）は１４０ｍｌ／ｍ２・ｄａｙ、であった。 The oxygen permeability (under drying) of the obtained paper material 3 was 104.0 ml / m 2 · day, and the oxygen permeability (under high humidity) was 140 ml / m 2 · day.
（紙管容器４の製造）
紙管容器２の製造において、紙製材料２を紙製材料３に変更した以外は同様にして、印籠型紙管容器を得た。
(Manufacturing of paper tube container 4)
In the production of the paper tube container 2, an inro-shaped paper tube container was obtained in the same manner except that the paper material 2 was changed to the paper material 3.
実施例３
（紙製材料４の作成）両更クラフト
両更クラフト（坪量７０ｇ／ｍ２）上に塗工液Ｂを塗工量（乾燥重量）１５ｇ／ｍ2となるよう塗工速度３００ｍ／分でブレードコーターを用いて片面塗工、乾燥した後、その上に塗工液Ａを塗工量（乾燥重量）４．０ｇ／ｍ２となるよう塗工速度５０ｍ／分でエアナイフコーターを用いて片面塗工し、坪量８９ｇ／ｍ２、紙厚１０３μｍの紙製材料を得た。
得られた紙製材料４の酸素透過度（乾燥下）は、２．５ｍｌ／ｍ２・ｄａｙ、酸素透過度（高湿度下）は６１．８ｍｌ／ｍ２・ｄａｙ、水蒸気バリア層塗工後の接触角は７５°、水蒸気透過度は１４０ｇ／ｍ２・ｄａｙであった。
Example 3
(Creation of paper material 4) Ryosara Craft Ryosara Craft (basis weight 70 g / m 2 ) is coated with coating liquid B at a coating speed of 300 m / min so that the coating amount (dry weight) is 15 g / m 2. After coating on one side with a blade coater and drying, apply coating liquid A on it with an air knife coater at a coating speed of 50 m / min so that the coating amount (dry weight) is 4.0 g / m 2. By coating, a paper material having a basis weight of 89 g / m 2 and a paper thickness of 103 μm was obtained.
The oxygen permeability (under drying) of the obtained paper material 4 is 2.5 ml / m 2 · day, the oxygen permeability (under high humidity) is 61.8 ml / m 2 · day, after coating the water vapor barrier layer. the contact angle 75 °, the water vapor transmission rate was 140g / m 2 · day.
（紙管容器５の作成）
紙管容器２の製造において、紙製材料２を紙製材料４に変更した以外は同様にして、印籠型紙管容器を得た。
(Creation of paper tube container 5)
In the production of the paper tube container 2, an inro-shaped paper tube container was obtained in the same manner except that the paper material 2 was changed to the paper material 4.
＜匂い漏れ防止評価＞
紙管容器２〜５に、内容物（チョコレート、固形石鹸、コーヒー（粉）、お香）を入れた後、紙管の蓋をして密閉し、各内容物の匂い漏れを官能評価した。
<Smell leakage prevention evaluation>
After the contents (chocolate, bar soap, coffee (powder), incense) were put in the paper tube containers 2 to 5, the paper tube was covered and sealed, and the odor leakage of each content was sensory evaluated.
表２より、実施例１の紙管容器２、３、実施例２の紙管容器４、５は匂い漏れの防止の効果が認められた。 From Table 2, the paper tube containers 2 and 3 of Example 1 and the paper tube containers 4 and 5 of Example 2 were found to have an effect of preventing odor leakage.
＜米の劣化評価＞
紙管容器２に１０ｇの精米を入れ、３０℃、６０％ＲＨの恒温・恒温チャンバーにいれ、４０日間保存した。４０日経過後は、条件を４０℃、９０％として更に１０日間保存した。ブランクとして晒クラフトの角底袋を用いて、酸化度指示薬を用いて呈色試験をし、酸化評価を行った。
<Rice deterioration evaluation>
10 g of polished rice was placed in a paper tube container 2, placed in a constant temperature / constant temperature chamber at 30 ° C. and 60% RH, and stored for 40 days. After 40 days, the condition was set to 40 ° C. and 90%, and the mixture was stored for another 10 days. A bleached kraft square bottom bag was used as a blank, and a coloration test was conducted using an oxidation degree indicator to evaluate oxidation.
表３より、実施例１の紙管容器２は内容物の米の酸化防止の効果が認められた。 From Table 3, the paper tube container 2 of Example 1 was found to have an antioxidative effect on the rice content.
Claims (2)
該互いにずらしながら部分的に重ね合わせられる複数の帯状原紙のうち２枚以上が、紙基材上に水溶性高分子を含有する塗工層（Ａ）、紙基材と塗工層（Ａ）の間に、顔料及び樹脂を含有する塗工層（Ｂ）を設けた紙製材料からなる紙管容器。 It is a paper tube container in which a plurality of strip-shaped base papers are partially overlapped and adhered while being shifted from each other.
Two or more of the plurality of band-like sheet that is brought partially superimposed while shifting the該互physician, the coating layer containing the water-soluble polymer on a paper substrate (A), the paper substrate and the coating layer (A) A paper tube container made of a paper material provided with a coating layer (B) containing a pigment and a resin between the two.
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| GB201706847D0 (en) * | 2017-04-28 | 2017-06-14 | British American Tobacco Investments Ltd | A Pack |
| KR102493718B1 (en) | 2017-10-04 | 2023-01-30 | 닛폰세이시가부시키가이샤 | barrier material |
| SE544559C2 (en) * | 2019-09-27 | 2022-07-19 | Stora Enso Oyj | A tube package and the use of a fiber substrate in the production of the package |
| JP7228213B2 (en) * | 2020-03-28 | 2023-02-24 | 旭加工紙株式会社 | Reinforcement paper with cut tape used for heavy-duty packaging paper bags |
| JP7177228B2 (en) * | 2020-07-30 | 2022-11-22 | 日本製紙株式会社 | Antiviral sheet containing cellulose fiber |
| JP2022067879A (en) * | 2020-10-21 | 2022-05-09 | 凸版印刷株式会社 | Lid material and package |
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| JPS5695829A (en) * | 1979-12-17 | 1981-08-03 | Toyo Boseki | Pipe for can in laminated film |
| JPS641215Y2 (en) * | 1980-12-16 | 1989-01-12 | ||
| JPS633943A (en) * | 1986-06-24 | 1988-01-08 | 三ツ矢鉄工株式会社 | Production machine for spiral paper pipe |
| JP2004115054A (en) * | 2002-09-26 | 2004-04-15 | Toppan Printing Co Ltd | Draw-formed paper container and manufacturing method thereof |
| JP2005088274A (en) * | 2003-09-16 | 2005-04-07 | Ube Ind Ltd | Biodegradable laminated paper |
| JP2006151492A (en) * | 2004-12-01 | 2006-06-15 | Asahi Kasei Chemicals Corp | Heavy oil explosive heavy bag |
| JPWO2011040547A1 (en) * | 2009-09-30 | 2013-02-28 | 日本製紙株式会社 | Paper barrier material |
| JP5331265B1 (en) * | 2011-11-10 | 2013-10-30 | 日本製紙株式会社 | Paper barrier packaging material |
| JP2015024541A (en) * | 2013-07-25 | 2015-02-05 | 凸版印刷株式会社 | Odor barrier laminate |
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