JP4928904B2 - Paper manufacturing method - Google Patents

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JP4928904B2
JP4928904B2 JP2006291739A JP2006291739A JP4928904B2 JP 4928904 B2 JP4928904 B2 JP 4928904B2 JP 2006291739 A JP2006291739 A JP 2006291739A JP 2006291739 A JP2006291739 A JP 2006291739A JP 4928904 B2 JP4928904 B2 JP 4928904B2
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崇紀 佐藤
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株式会社 伊藤園
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本発明は、消臭性、抗菌性を有する紙及びその製造方法に関する。より詳しくは、茶成分の配合に伴う着色、変形、加熱変色を抑制しつつ、消臭性、抗菌性が好適に付与された紙及びその製造方法に関する。   The present invention relates to deodorant and antibacterial paper and a method for producing the same. More specifically, the present invention relates to a paper to which deodorizing properties and antibacterial properties are suitably imparted while suppressing coloring, deformation, and heat discoloration associated with the blending of tea components, and a method for producing the same.

近年、消費者の健康飲料指向の高まりによって茶系飲料の需要が伸び、含水茶系残渣の排出量が年々増加している。含水茶系残渣は、放置しておくと腐敗して含有成分の変質等が起こるため、適切な廃棄物処理が必要となる。一般的な有機性廃棄物の処理方法としては、乾燥、堆肥化、焼却、炭化等が挙げられるが、茶系残渣の含水量は極めて高いため、上記の何れの処理を行うにしても、処理装置の負担軽減や処理速度向上のために、予め茶系残渣を脱水する必要がある。脱水処理は、脱水後の廃棄物の再利用にとってはメリットがあるが、脱水廃液を排出可能な状態にするための適切な水処理が必要となり、廃液処理に大型のプラントを建設しなければならず、多額の費用が必要になるというデメリットがある。   In recent years, demand for tea-based beverages has increased due to the increasing consumer-oriented health beverage orientation, and the amount of water-containing tea residue emissions has been increasing year by year. If the water-containing tea residue is left as it is, it will rot and change the content of the components, so that appropriate waste disposal is required. Common organic waste treatment methods include drying, composting, incineration, carbonization, etc., but the water content of the tea residue is extremely high. In order to reduce the burden on the apparatus and improve the processing speed, it is necessary to dehydrate the tea residue in advance. Dehydration is beneficial for reuse of waste after dehydration, but appropriate water treatment is necessary to make the dehydrated waste liquid ready for discharge, and a large plant must be constructed for waste liquid treatment. However, there is a demerit that a large amount of cost is required.

このため、茶殻の処理、再利用については様々な方法が考えられているにも拘わらず、上記のようなデメリットへの対応がリサイクルの進行を阻んでいる。   For this reason, in spite of various methods for processing and reusing tea husks, the response to the above disadvantages hinders the progress of recycling.

その一方で、茶葉に含まれるポリフェノール等の有効成分による抗菌、消臭機能を紙に付与することが試みられている。これは、大別すると、1)茶葉又は茶殻を利用する、2)茶成分エキス又はこれを含有する溶液等を利用する、3)製茶工程で排出されるその他の廃棄物を利用する、の3種の方法に分類することができる。   On the other hand, attempts have been made to impart antibacterial and deodorizing functions to paper using active ingredients such as polyphenols contained in tea leaves. This can be broadly divided into 1) using tea leaves or tea shells, 2) using tea component extracts or solutions containing the same, and 3) using other waste discharged in the tea production process. It can be classified into species methods.

例えば、下記特許文献1〜3では、上記1)の方法が提案されており、特許文献1では、紙パルプスラリーに茶葉又は茶粕を添加して模様紙を製紙することが開示され、特許文献2では、抄紙機のワイヤーパート手前の段階で茶葉を混合して紙繊維中に茶葉が散在した紙を得ることが開示され、特許文献3では、破片状に調製した茶殻と繊維状紙パルプとを絡み合わせて抄紙した茶殻配合紙が開示されている。   For example, in Patent Documents 1 to 3 below, the above method 1) has been proposed. In Patent Document 1, it is disclosed that paper leaves or teacups are added to a paper pulp slurry to make a pattern paper. 2 discloses that tea leaves are mixed in the stage before the wire part of the paper machine to obtain paper in which the tea leaves are scattered in the paper fiber. Tea husk blended paper made by entangled paper is disclosed.

上記2)の方法が提案されるものとしては、下記特許文献4〜8があり、特許文献4では、植物エキスを紙又は合成紙に塗布又は含浸することが開示され、植物エキスとして緑茶エキスが記載されている。特許文献5では、天然パルプ主体の紙の表面に茶抽出物を塗工した食品用抗菌紙が開示され、特許文献6では、水酸基が2つ以上置換したベンゼン核を有する化合物を水解紙製造のウェブ形成時又は後に配合することが開示され、この化合物としてカテキン系化合物が例示されている。特許文献7,8では、カテキン類を紙に含有させて、鮮度保持や抗菌・消臭等の用途に利用することが開示されている。   As the method proposed in 2) above, there are the following Patent Documents 4 to 8, which discloses that a plant extract is applied or impregnated on paper or synthetic paper, and a green tea extract is used as the plant extract. Are listed. Patent Document 5 discloses a food antibacterial paper in which a tea extract is applied to the surface of a natural pulp-based paper. Patent Document 6 discloses a compound having a benzene nucleus substituted with two or more hydroxyl groups for producing hydrolytic paper. It is disclosed that it is blended during or after the web formation, and catechin compounds are exemplified as this compound. Patent Documents 7 and 8 disclose that catechins are contained in paper and used for purposes such as freshness maintenance and antibacterial / deodorant.

上記3)の方法が提案されるものとしては、下記特許文献9があり、緑茶の製造工程で揉機に付着した皮状物質を原料パルプに混合して抄紙することが開示される。
特開平6−235198号公報 特開2002−242095号公報 特開2004−143640号公報 特開2005−119967号公報 特開2000−110099号公報 特開2001−3297号公報 特開2001−32195号公報 特開2002−17828号公報 特開平9−122216号公報
As the method proposed in 3) above, there is the following Patent Document 9, which discloses that paper material is mixed with a raw material pulp adhering to a koji machine in a green tea production process.
JP-A-6-235198 JP 2002-242095 A JP 2004-143640 A JP 2005-119967 A JP 2000-1110099 A JP 2001-3297 A JP 2001-32195 A Japanese Patent Laid-Open No. 2002-17828 Japanese Patent Laid-Open No. 9-12216

しかし、茶葉又は茶殻をパルプに配合する上記1)の方法の場合、茶葉又は茶殻の寸法が大きいと、紙に凹凸が生じたりして外観が悪くなるので、粉砕工程が必要となるが、このための設備に費用がかかる。また、抄紙後の乾燥において茶葉又は茶殻とパルプとで保持する含水率に差が生じるため、乾燥度がばらついて紙の変形や歪みを生じ易く、乾燥効率が悪いために乾燥装置に負担がかかる。しかも、乾燥が進むにつれてパルプと茶葉又は茶殻との間に隙間が生じて紙からパルプ繊維、茶葉又は茶殻が脱離し易くなる。更に、紙中の茶成分の分布も均一になり難い。   However, in the case of the above method 1) in which tea leaves or tea husks are blended with pulp, if the size of the tea leaves or tea husks is large, the paper looks uneven and the appearance deteriorates, so a pulverization step is necessary. Expensive equipment for In addition, there is a difference in the moisture content held between tea leaves or tea husks and pulp during drying after papermaking, and the degree of drying varies and the paper tends to be deformed or distorted. . Moreover, as drying progresses, a gap is formed between the pulp and the tea leaves or tea shells, and the pulp fibers, tea leaves or tea shells are easily detached from the paper. Furthermore, the distribution of tea components in the paper is difficult to be uniform.

また、茶成分エキス又はこれを含有する溶液等を紙に塗布する上記2)の方法の場合、乾燥時の加熱による茶成分の変色によって商品価値を損なう。変色を防止するために加熱温度を低下させると、乾燥に長時間を要し、紙の変形や生産効率の低下が問題となる。   Further, in the case of the above method 2) in which a tea component extract or a solution containing the same is applied to paper, the commercial value is impaired by discoloration of the tea component by heating during drying. When the heating temperature is lowered in order to prevent discoloration, it takes a long time for drying, and deformation of paper and a decrease in production efficiency become problems.

製茶工程で排出されるその他の廃棄物を利用する上記3)の方法の場合、上記1)の方法と同様に、廃棄物の粉砕工程が必要になる。特許文献9の方法について説明すると、揉機に付着する皮状の物質は、茶葉屑等の塊であり、紙パルプに添加するに適した寸法に粉砕したりして液体に分散する必要があり、上記1)又は2)の方法と同様な形態の工程を経ることから、上記の問題が同様に生じる。   In the case of the above method 3) using other waste discharged in the tea production process, a waste crushing step is required as in the above method 1). Explaining the method of Patent Document 9, the skin-like substance attached to the dredger is a lump such as tea leaf scraps, and it is necessary to disperse it in a liquid by crushing it to a size suitable for addition to paper pulp, The above-described problem is caused in the same manner because the process has the same form as the method 1) or 2).

上記のように、茶抽出成分や茶殻そのものを製紙に利用する際には、抄紙の加熱乾燥に関連した変形・変色やコスト、製造効率等の様々な問題があり、外観を損なわずに茶成分の抗菌・消臭機能を付与した紙が効率よく得られる紙の製造方法は知られていなかった。   As mentioned above, when using tea extract components and tea husks themselves for papermaking, there are various problems such as deformation / discoloration, cost, production efficiency, etc. related to heat drying of papermaking, and tea components are not impaired. No paper manufacturing method has been known that can efficiently obtain a paper with antibacterial and deodorant functions.

本発明は、茶の有効成分を紙に配合して着色、変形、加熱変色を抑制し、好適な抗菌性、消臭性を発揮する紙を提供することを課題とする。   It is an object of the present invention to provide a paper exhibiting suitable antibacterial and deodorizing properties by blending an active ingredient of tea with paper to suppress coloring, deformation, and heat discoloration.

又、本発明は、茶の有効成分による好適な抗菌性、消臭性を発揮し、美観に優れた紙を、低コストで効率よく提供可能な紙の製造方法を提供することを課題とする。   Another object of the present invention is to provide a method for producing paper that can efficiently provide paper having excellent antibacterial properties and deodorizing properties due to the active ingredients of tea and having excellent aesthetics at low cost. .

又、本発明は、抗菌性、消臭性を有し、美観に優れた紙を提供するに当たり、茶系飲料の製造残渣の有効利用に貢献し、地球環境に与える負荷を低減可能な紙の製造方法を提供することを課題とする。   In addition, the present invention provides an antibacterial and deodorant paper that contributes to the effective use of manufacturing residues of tea-based beverages and can reduce the load on the global environment. It is an object to provide a manufacturing method.

上記課題を解決するために、本発明では、紙の美観を損なわずに紙に茶の有効成分を配合する手法を開発し、茶の有効成分による抗菌性、消臭機能を十分に活用できる紙の提供を実現した。   In order to solve the above-mentioned problems, the present invention has developed a method for blending tea with active ingredients in paper without impairing the aesthetics of the paper, and can fully utilize the antibacterial and deodorizing functions of tea active ingredients. Realized the provision of.

本発明の一態様によれば、紙の製造方法は、0.10〜5MPaの圧力を加えた含水茶殻の搾汁液が配合された紙パルプスラリーを調製し、該紙パルプスラリーを抄紙し、抄紙した含水紙から水を除去することを特徴とす
ことを要旨とする。
According to one aspect of the present invention, a method for producing paper comprises preparing a paper pulp slurry containing a squeezed liquid of hydrated tea shells with a pressure of 0.10 to 5 MPa , papermaking the paper pulp slurry, The gist is that water is removed from the paper-containing water-containing paper.

又、本発明の他の態様によれば、紙の製造方法は、含水茶殻に圧力を加えて、茶由来のポリフェノールを含有し、粒径が10μm以上500μm未満の茶殻粒子を含む搾汁液を調製し、前記茶殻粒子を含む搾汁液を配合した紙パルプスラリーを調製し、該紙パルプスラリーを抄紙し、抄紙した含水紙から水を除去することを要旨とする。
According to another aspect of the present invention, a method for producing paper comprises applying pressure to hydrous tea husk to prepare tea juice liquid containing tea-derived polyphenol and tea husk particles having a particle size of 10 μm or more and less than 500 μm. Then, the gist is to prepare a paper pulp slurry blended with the juice containing the tea husk particles, paper-making the paper pulp slurry, and removing water from the paper-containing water-containing paper.

本発明によれば、色、形状等の美観を損なうことなく、茶の機能成分が紙に配合され、抗菌性、消臭性を有する紙を効率よく製造できる製造方法が確立され、好適な抗菌・消臭性を発揮する紙が安価に提供される。抗菌・消臭性を有する紙の提供に際し、茶系飲料の製造残渣の有効利用が進み、地球環境に与える負荷の低減に貢献する。   According to the present invention, a functional method of tea is blended into paper without impairing the aesthetics of color, shape, etc., and a production method capable of efficiently producing antibacterial and deodorant paper is established, and a suitable antibacterial -Paper that exhibits deodorant properties is provided at low cost. In the provision of antibacterial and deodorant paper, the effective use of tea-based beverage manufacturing residues will advance, contributing to the reduction of the burden on the global environment.

緑茶に含まれるポリフェノールは、抗菌性及び消臭性を有し、カテキンを配合して製品を製造することによって製品に抗菌性及び消臭性を付与することができる。消臭性成分については、カテキンだけでなく、それ以外のポリフェノール類にも存在し、緑茶、紅茶、ウーロン茶等の茶類やコーヒー等にも消臭性成分は含まれる。   The polyphenol contained in green tea has antibacterial properties and deodorizing properties, and the products can be imparted with antibacterial properties and deodorizing properties by blending catechins into the products. The deodorant component is present not only in catechin but also in other polyphenols, and the deodorant component is also contained in teas such as green tea, black tea, oolong tea, and coffee.

抗菌性及び消臭性を紙に付与するために上述のような緑茶の有効成分エキスを紙パルプに配合すると、抄紙後の乾燥において加熱による変色が起こる。しかし、緑茶葉から茶液を抽出した後の残渣である含水茶殻から回収される搾汁を用いた場合には、加熱乾燥時の変色を抑制しつつ、茶成分による抗菌性、消臭性等を紙に付与することができ、紅茶、ウーロン茶等の茶類やコーヒー等の抽出残渣の搾汁でも好適に消臭性を紙に付与できる。含水茶殻の搾汁液は、茶葉から茶液(第1煎)を熱水抽出した残渣の残留液であるので、水溶性成分量は茶液より少なく、圧搾によって小さい茶葉粒子が茶葉から放散し、分散粒子を構成している。抽出した茶液を用いて抄紙した場合の紙が最も加熱変色し易いことから、機能成分であるポリフェノール水に溶解又は極小粒子状に分散するポリフェノール以外の成分も加熱変色に関係することが考えられ、溶解している状態や極小粒子の場合では、活性の高さや表面積の比率が高いことにより反応が進行し易いために変色が顕著になり、逆に粒子がある程度大きい場合は粒子内部で保護されることにより変色し難くなることなどが考えられる。又、茶殻(抽出後の茶葉)を配合しても、加熱変色を抑制しつつ抗菌性及び消臭性を付与することができるが、この場合、茶殻と紙パルプ繊維との乾燥速度の違いや乾燥による茶殻の収縮等によって紙パルプ繊維から茶殻が容易に脱離・剥離する。これを防止するためには、茶殻の乾燥が促進され、且つ、茶殻の収縮が問題にならない程度に茶殻を粉砕して粒子寸法を小さくする必要がある。このようなことに留意すれば、茶飲料製造後の含水茶殻を利用して、加熱乾燥時の変色を抑制しつつ抗菌・消臭紙を好適に製造することができる。以下に詳細に説明する。尚、本願において、「茶葉」は、上述の茶の有効成分を含む茶樹組織を広く意味し、茎茶、棒茶等を含み得るものであって、「葉」に限定されるものではない。   When an active ingredient extract of green tea as described above is added to paper pulp to impart antibacterial and deodorant properties to paper, discoloration due to heating occurs during drying after paper making. However, when squeezed from water-containing tea husk, which is a residue after extracting tea liquid from green tea leaves, the antibacterial and deodorizing properties of tea components are suppressed while suppressing discoloration during heating and drying. Can be imparted to paper, and deodorant properties can be suitably imparted to paper even with teas such as black tea and oolong tea, and juices of extraction residues such as coffee. Since the squeezed liquid of the hydrous tea husk is a residual liquid of the residue obtained by hot water extraction of the tea liquid (first decoction) from the tea leaves, the amount of water-soluble components is less than that of the tea liquid, and by pressing the small tea leaf particles are released from the tea leaves, It constitutes dispersed particles. When paper is made using the extracted tea liquid, it is most likely to be discolored by heating, so it is considered that components other than polyphenols that are dissolved in the functional component polyphenol water or dispersed in the form of extremely small particles are also related to heat discoloration. In the case of dissolved or extremely small particles, discoloration becomes prominent because the reaction proceeds easily due to the high activity and the ratio of the surface area. Conversely, when the particles are somewhat large, they are protected inside the particles. It may be difficult to change the color. Moreover, even when blended with tea husk (tea leaf after extraction), antibacterial and deodorant properties can be imparted while suppressing heat discoloration. In this case, the difference in drying speed between tea husk and paper pulp fiber The tea husk is easily detached from the paper pulp fiber due to shrinkage of the tea husk by drying or the like. In order to prevent this, it is necessary to reduce the particle size by pulverizing the tea husk to such an extent that drying of the tea husk is promoted and shrinkage of the tea husk does not become a problem. With this in mind, antibacterial and deodorized paper can be suitably produced while suppressing discoloration during heating and drying using the water-containing tea shell after tea beverage production. This will be described in detail below. In the present application, “tea leaf” broadly means tea tree tissues containing the above-mentioned active ingredients of tea, and can include stem tea, stick tea, etc., and is not limited to “leaf”.

緑茶、紅茶、ウーロン茶等の狭義の茶(茶樹を原料とする茶)及びこれらを含む混合茶等の飲料成分には、ポリフェノールや他の消臭・抗菌等の機能性成分を含んでいる。本発明において用いる茶成分は、これらの飲料に含まれているが、本発明では、茶葉からこれらの飲料を製造する際の残渣である含水茶殻に含まれるものを使用する。含水茶殻も、ポリフェノール類等の機能性成分を含んでおり、これを利用して紙に抗菌・消臭機能を付与可能である。含水茶殻は、スクリュープレス機、フィルタープレス機、攪拌脱水機、遠心脱水機等を用いた圧搾・分離による含有水分の脱液によって搾汁され、ポリフェノール類や消臭機能成分を含有する粒径が10μm以上の粒子が分散した搾汁液が得られる。この搾汁液を、そのまま製紙に用いることができ、必要に応じて希釈又は濃縮して利用してもよい。圧搾の際の加圧圧力は0.1MPa以上において有効であり、5MPaを越えると装置の負荷が問題となるので、0.1〜5MPa程度が好ましい。また、搾汁液を一旦乾燥固形物に調製してもよく、その場合、固形物は均一な分散水に再調製して利用することが望ましい。又、荒茶製造工程で生じるライン洗浄水等のポリフェノールを含む廃液も、粒径が10μm以上であれば、搾汁液に添加して用いてもよい。   Beverage components such as green tea, black tea, oolong tea and the like (tea made from tea tree) and mixed tea containing them contain polyphenols and other functional components such as deodorant and antibacterial agents. The tea components used in the present invention are contained in these beverages, but in the present invention, those contained in the water-containing tea shell, which is a residue when these beverages are produced from tea leaves, are used. Water-containing tea shells also contain functional components such as polyphenols and can be used to impart antibacterial and deodorant functions to paper. Water-containing tea shells are squeezed by draining the water content by pressing and separating using a screw press machine, filter press machine, stirring dehydrator, centrifugal dehydrator, etc., and have a particle size containing polyphenols and deodorant functional components. A squeezed liquid in which particles of 10 μm or more are dispersed is obtained. This squeezed liquid can be used for papermaking as it is, and may be diluted or concentrated as necessary. The pressurizing pressure at the time of pressing is effective at 0.1 MPa or more, and if it exceeds 5 MPa, the load on the apparatus becomes a problem, so about 0.1 to 5 MPa is preferable. In addition, the juice may be once prepared into a dry solid. In that case, it is desirable that the solid is re-prepared into uniform dispersed water and used. Also, waste liquid containing polyphenols such as line washing water produced in the crude tea production process may be used by adding to the juice as long as the particle size is 10 μm or more.

搾汁液を得た後の茶殻にも上記機能成分は残留しているので、抗菌・消臭紙の製造に利用できる。茶殻の有機繊維質は、ポリフェノール等の機能成分を保護する役割をする。茶殻を製紙に用いる場合は、茶殻を粉砕して粒径が500μm未満の粉砕物を用いる。茶殻の粒径が500μm以上であると、抄紙後の紙のパルプ繊維から茶殻が剥離・脱離し易くなるので、粉砕後に篩い分けにより10〜500μmの粉砕物を選別して使用すると、紙の外観(表面)に視覚的影響を与えずに茶成分による機能を付与でき、熱変色も抑制できる。茶殻の粉砕は、茶殻を乾燥して行うと容易であるが、含水状態で切断したり水中で茶殻をミル等を用いて磨砕してもよい。また、搾汁液及び茶殻粉砕物の混合物を用いてもよい。   Since the above functional components remain in the tea husk after obtaining the juice, it can be used for the production of antibacterial and deodorized paper. The organic fiber of the tea husk serves to protect functional components such as polyphenols. When using tea husk for papermaking, crushed tea husk is pulverized and the particle size is less than 500 μm. If the particle size of the tea husk is 500 μm or more, the tea husk will be easily peeled off and detached from the pulp fiber of the paper after paper making. If the crushed material of 10 to 500 μm is sorted and used after pulverization, the appearance of the paper The function of the tea component can be imparted without visually affecting the (surface), and thermal discoloration can also be suppressed. Grinding of the tea husk is easy when the tea husk is dried. However, the tea husk may be cut in a water-containing state or ground in water using a mill or the like. Moreover, you may use the mixture of squeezed liquid and a tea-brush ground material.

搾汁液及び/又は茶殻粉砕物は、抄紙工程以前の紙パルプに配合し、抄紙脱水及び加熱乾燥を経ることにより紙が得られる。   The squeezed liquid and / or tea crushed powder is mixed with paper pulp before the paper making process, and paper is obtained by paper dehydration and heat drying.

紙パルプの原料としては、木チップ、古紙等から得られる化学パルプ、再生パルプ及び機械パルプが好適に用いられる。具体的には、木チップを原料とした場合は、木チップを蒸解し、脱リグニン処理を経て洗浄及び脱水を繰り返し行うことによって得られる無漂白パルプ、及び、この無漂白パルプを更に漂白・洗浄した漂白パルプの何れも本発明において使用でき、無漂白パルプ及び漂白パルプは、木チップをリファイナーによって磨り潰したものを用いて調製してもよい。古紙を原料とした場合は、パルパーを用いて古紙を解繊した後に洗浄して得られる無漂白パルプ、及び、この無漂白パルプを更に漂白・洗浄した漂白パルプの何れも使用可能である。このような化学パルプ、再生パルプ及び機械パルプは、単独で使用しても、適宜混合して用いてもよい。   As a raw material for paper pulp, chemical pulp, recycled pulp and mechanical pulp obtained from wood chips, waste paper, etc. are preferably used. Specifically, when wood chips are used as raw materials, the unbleached pulp obtained by digesting the wood chips, performing washing and dehydration through delignification treatment, and further bleaching and washing the unbleached pulp Any of the bleached pulps used can be used in the present invention, and unbleached pulp and bleached pulp may be prepared using wood chips ground by a refiner. When used paper is used as a raw material, any of unbleached pulp obtained by washing the used paper after pulping with a pulper and bleached pulp obtained by further bleaching and washing the unbleached pulp can be used. Such chemical pulp, regenerated pulp, and mechanical pulp may be used alone or in combination as appropriate.

上述のような紙パルプを用いて、適量の水にパルプ繊維が分散し、前述の搾汁液及び/又は茶殻粉砕物が配合されたスラリーを調製し、得られたパルプスラリーを抄紙する。搾汁液及び/又は茶殻粉砕物の配合は、スラリー調製の前後何れでもよく、最終水分量が抄紙に適した量になるようにスラリー調製に使用する水量を適宜調整する。搾汁液の濃度及び茶殻粉砕物の添加量は、最終紙製品に付与される抗菌・消臭機能を勘案して適宜調整する。抄紙条件が適切であれば、スラリー中のポリフェノール類のほぼ全量を抄紙した紙に導入できるので、使用する紙パルプと配合する搾汁液及び/又は茶殻粉砕物との割合によって最終紙製品中のポリフェノール含有量を調節できる。良好な抗菌・消臭機能を付与するためには、紙パルプに対する総ポリフェノールの割合(乾燥質量換算)が約0.10〜1.50質量%となることが好ましく、0.16質量%以上において各種消臭性での有効性が明らかであり、0.40質量%以上では抗菌機能の向上が顕著になり、約0.78質量%以上で優れた抗菌・消臭機能が発揮される。1.50質量%を超えると、コスト増加が問題となり、加熱変色が進行し易くなる。スラリー調製の際に、一般的な製紙で用いられる添加剤等を配合してもよい。茶殻粉砕物を利用する場合、得られる紙の強度などを考慮すると、紙パルプの乾燥質量に対する茶殻粉砕物の乾燥質量の割合が25%以下であることが好ましく、15%以下であると更に好ましい。   Using the above-described paper pulp, a pulp fiber is dispersed in an appropriate amount of water, and a slurry in which the above-mentioned squeezed juice and / or tea crushed powder is blended is prepared, and the resulting pulp slurry is made into paper. The squeezed liquid and / or the tea crushed powder may be blended either before or after the slurry preparation, and the amount of water used for the slurry preparation is appropriately adjusted so that the final water content is suitable for papermaking. The concentration of squeezed juice and the amount of crushed tea leaves are adjusted as appropriate in consideration of the antibacterial and deodorizing functions imparted to the final paper product. If the papermaking conditions are appropriate, almost all of the polyphenols in the slurry can be introduced into the papermaking paper, so the polyphenols in the final paper product will depend on the ratio of the pulp used and the squeezed liquor and / or crushed tea leaves. Content can be adjusted. In order to give a good antibacterial / deodorant function, the ratio of the total polyphenol to the paper pulp (in terms of dry mass) is preferably about 0.10 to 1.50% by mass, and at 0.16% by mass or more The effectiveness in various deodorizing properties is obvious. When the content is 0.40% by mass or more, the improvement of the antibacterial function becomes remarkable, and when the content is about 0.78% by mass or more, the excellent antibacterial / deodorizing function is exhibited. If it exceeds 1.50% by mass, an increase in cost becomes a problem, and heating discoloration tends to proceed. In preparing the slurry, additives used in general papermaking may be blended. In the case of using the crushed tea husk, the ratio of the dry weight of the crushed tea husk to the dry weight of the paper pulp is preferably 25% or less, and more preferably 15% or less in consideration of the strength of the obtained paper. .

スラリー状の紙パルプは、目開きが500μm未満の網上に流し込みながら所望の厚さのフェルト状に成形することによって抄紙する。抄紙時の網の目開きが500μm以上であると、搾汁液の茶成分及び茶殻粉砕物が紙パルプ繊維と絡まずに網を通して流出するので、紙パルプに茶成分の機能が十分に付与されず、製品の歩留まりが低下する。抄紙したパルプ成形物、つまり含水紙は、プレス機等を用いて脱水する。この際、脱水物の含水率が40〜60質量%程度になるように脱水圧力を調節することが好ましい。含水率を40質量%未満に減少させるような脱水は、脱水機の機械的負担が過大になり、装置寿命が短くなる。脱水後の含水率が60質量%を超えるものは、この後の乾燥工程での装置負担及びエネルギー消費が大きくなる。   Slurry paper pulp is made by forming into a felt shape having a desired thickness while pouring onto a net having an opening of less than 500 μm. If the mesh opening at the time of papermaking is 500 μm or more, the tea components and tea grounds in the juice will flow out through the net without entanglement with the paper pulp fibers, so that the function of the tea components will not be sufficiently imparted to the paper pulp. , The product yield decreases. The paper-made pulp molding, that is, the water-containing paper, is dehydrated using a press or the like. At this time, it is preferable to adjust the dehydrating pressure so that the water content of the dehydrated product is about 40 to 60% by mass. Dehydration that reduces the water content to less than 40% by mass results in an excessive mechanical load on the dehydrator and shortens the life of the apparatus. When the water content after dehydration exceeds 60% by mass, the equipment burden and energy consumption in the subsequent drying process increase.

脱水後の含水紙は、加熱乾燥により残留水分を十分に除去することにより、抗菌・消臭機能を有する紙が得られる。加熱乾燥時の温度は100〜160℃が好ましい。100℃未満では、乾燥が遅いため、未乾燥製品の混入が起こり易くなる。160℃を超える温度では紙パルプの変質が生じ、変色も激しくなる。乾燥中の紙の歪み等を防止する点では100〜130℃程度での乾燥が望ましく、空気乾燥との併用も好ましい。   The water-containing paper after dehydration can be obtained by removing residual moisture sufficiently by heat drying, thereby obtaining a paper having antibacterial and deodorizing functions. The temperature during heat drying is preferably 100 to 160 ° C. If it is less than 100 ° C., the drying is slow, so that undried products are likely to be mixed. When the temperature exceeds 160 ° C., the quality of the paper pulp is changed and the discoloration becomes severe. In order to prevent distortion of the paper during drying, drying at about 100 to 130 ° C. is desirable, and combined use with air drying is also preferable.

上述のようにして得られる紙は、抗菌・消臭機能を有し、悪臭物質の臭気放散を抑制する性質も備える。従って、雰囲気中の悪臭を吸収する性質を利用して壁紙や紙製展示製品として提供したり、又、悪臭放出抑制機能を利用して、悪臭発生物を処理するために利用するトイレットペーパーやティッシュペーパー、紙おむつ等の介護・生理用品、紙ナプキン、紙雑巾等の清掃用品として提供すると有用である。   The paper obtained as described above has an antibacterial and deodorizing function and also has a property of suppressing odor emission of malodorous substances. Therefore, toilet paper and tissue used to treat the generation of odors by using the property of absorbing bad odors in the atmosphere and providing them as wallpaper and paper display products, or using the odor emission suppression function. It is useful to provide it as a cleaning product such as a nursing or sanitary product such as paper or a disposable diaper, a paper napkin or a paper cloth.

尚、コーヒー飲料製造で排出される含水コーヒー残渣の搾汁液を用いても、消臭性を備えた紙の製造が可能である。   In addition, even if it uses the squeezed liquid of the water-containing coffee residue discharged | emitted by coffee drink manufacture, manufacture of the paper provided with deodorizing property is possible.

以下、実施例を参照して本発明を詳述する。本発明は以下の実施例により何ら制限されるものではない。   Hereinafter, the present invention will be described in detail with reference to examples. The present invention is not limited by the following examples.

<茶成分液の調製>
茶成分液として、下記のカテキン液A〜D、緑茶液A〜D及び搾汁液A〜Cを調製した。尚、以下の調製において、総ポリフェノール含有量は、酒石酸鉄と反応させて比色定量法に従って測定し、カテキン類の含有量は、高速液体クロマトグラフによって測定した。
<Preparation of tea component liquid>
The following catechin liquids AD, green tea liquids AD, and juice liquids AC were prepared as tea component liquids. In the following preparation, the total polyphenol content was measured according to a colorimetric method after reacting with iron tartrate, and the content of catechins was measured by a high performance liquid chromatograph.

(カテキン液A〜D)
緑茶葉に熱水を加えて緑茶飲料を抽出し、常法に従って緑茶飲料に含まれる成分を溶媒抽出及びカラム分離により精製して、カテキン乾燥物(総ポリフェノール含有量:38質量%、EGC:10質量%、EGCg:14質量%、EC:2質量%、ECg:4質量%、エピ型カテキン類総含有量:30質量%)を得た。
(Catechin liquids A to D)
Hot water is added to the green tea leaves to extract the green tea beverage, and the components contained in the green tea beverage are purified by solvent extraction and column separation according to a conventional method to obtain a dried catechin (total polyphenol content: 38% by mass, EGC: 10 Mass%, EGCg: 14 mass%, EC: 2 mass%, ECg: 4 mass%, epi-type catechins total content: 30 mass%).

このカテキン乾燥物を水に添加して、カテキン液A〜D[A(固形分:0.05質量%、総ポリフェノール:0.02質量%)、B(固形分:0.1質量%、総ポリフェノール:0.04質量%)、C(固形分:0.2質量%、総ポリフェノール:0.08質量%)、D(固形分:1.0質量%、総ポリフェノール:0.38質量%)]を調製した。   This catechin dried product was added to water, and catechin liquids A to D [A (solid content: 0.05 mass%, total polyphenol: 0.02 mass%), B (solid content: 0.1 mass%, total Polyphenol: 0.04 mass%), C (solid content: 0.2 mass%, total polyphenol: 0.08 mass%), D (solid content: 1.0 mass%, total polyphenol: 0.38 mass%) Was prepared.

尚、レーザー回折式粒度分布測定装置を用いて測定したカテキン液中の分散粒子の平均粒径は2.0μm、粒度分布は0.2〜6.7μmであった。   In addition, the average particle diameter of the dispersed particles in the catechin liquid measured using a laser diffraction particle size distribution measuring apparatus was 2.0 μm, and the particle size distribution was 0.2 to 6.7 μm.

(緑茶液A〜D)
緑茶葉に熱水を加えて(緑茶葉:総量の2.3質量%)緑茶成分を熱水に抽出し、目開き425μmの篩いに通して緑茶液A(固形分:2.3質量%、総ポリフェノール:0.37質量%)を得た。この緑茶液A中の分散粒子の平均粒径は50.2μm、粒度分布は8.4〜425μmであり、この乾燥固形物は、総ポリフェノール含有量:16質量%、EGC:5質量%、EGCg:7質量%、EC:1.1質量%、ECg:1.6質量%、エピ型カテキン類総含有量:14.7質量%であった。
(Green tea liquids A to D)
Hot water is added to the green tea leaves (green tea leaves: 2.3% by mass of the total amount), the green tea components are extracted into hot water, passed through a sieve with an opening of 425 μm, and green tea liquid A (solid content: 2.3% by mass, Total polyphenol: 0.37% by mass) was obtained. The average particle size of the dispersed particles in this green tea liquid A is 50.2 μm, the particle size distribution is 8.4 to 425 μm, and this dry solid has a total polyphenol content: 16% by mass, EGC: 5% by mass, EGCg : 7% by mass, EC: 1.1% by mass, ECg: 1.6% by mass, and total epicatechin content: 14.7% by mass.

この緑茶液Aの一部を用いて、水を加えて希釈することにより緑茶液B〜D[B(固形分:1.3質量%、総ポリフェノール:0.21質量%)、C(固形分:0.6質量%、総ポリフェノール:0.10質量%)、D(固形分:0.3質量%、総ポリフェノール:0.05質量%)]を調製した。   By using a part of this green tea liquid A and diluting it with water, green tea liquids B to D [B (solid content: 1.3 mass%, total polyphenol: 0.21 mass%), C (solid content) : 0.6 mass%, total polyphenol: 0.10 mass%), D (solid content: 0.3 mass%, total polyphenol: 0.05 mass%)].

尚、レーザー回折式粒度分布測定装置を用いて測定した緑茶液中の分散粒子の平均粒径は50.2μm、粒度分布は8.4〜425μmであった。   In addition, the average particle diameter of the dispersed particles in the green tea liquid measured using a laser diffraction particle size distribution measuring apparatus was 50.2 μm, and the particle size distribution was 8.4 to 425 μm.

(搾汁液A〜C)
上記緑茶液の調製における緑茶成分抽出後の残渣である含水茶殻(含水率85質量%)をフィルタープレス機で圧搾して茶殻を脱水し、圧搾液を目開き425μmの篩いに通して搾汁液A(固形分:2.3質量%、総ポリフェノール:0.41質量%、EGC:0.18質量%、EGCg:0.14質量%、EC:0.04質量%、ECg:0.02質量%、エピ型カテキン類総含有量:0.38質量%)を得た。搾汁液A中の分散粒子の平均粒径は52.5μm、粒度分布は10.1〜425μmであった。
(Squeezed juice AC)
The water-containing tea husk (water content 85 mass%), which is the residue after extraction of the green tea component in the preparation of the green tea liquor, is squeezed with a filter press to dehydrate the tea husk, and the squeezed liquor is passed through a sieve with an opening of 425 μm. (Solid content: 2.3 mass%, total polyphenol: 0.41 mass%, EGC: 0.18 mass%, EGCg: 0.14 mass%, EC: 0.04 mass%, ECg: 0.02 mass% , Epi-type catechins total content: 0.38% by mass). The average particle diameter of the dispersed particles in the juice A was 52.5 μm, and the particle size distribution was 10.1 to 425 μm.

この搾汁液Aの一部を用いて、水を加えて希釈することにより搾汁液B、C[B(固形分:1.2質量%、総ポリフェノール:0.21質量%)、C(固形分:0.60質量%、総ポリフェノール:0.10質量%)]を調製した。   By using a part of the juice A and diluting with water, the juice B, C [B (solid content: 1.2% by mass, total polyphenol: 0.21% by mass), C (solid content) : 0.60% by mass, total polyphenol: 0.10% by mass)].

尚、レーザー回折式粒度分布測定装置を用いて測定した搾汁液中の分散粒子の平均粒径は52.5μm、粒度分布は10.1〜425μmであった。   In addition, the average particle diameter of the dispersed particles in the squeezed liquid measured using a laser diffraction particle size distribution measuring apparatus was 52.5 μm, and the particle size distribution was 10.1 to 425 μm.

<茶成分液の色彩評価>
上記で調製した各茶成分液について、分光式色彩計(日本電色工業(株)社製)を用いて茶成分液のLab値を測定し、更に、150℃に加熱して30分及び120分経過した時の茶成分液のLab値を測定した。加熱による茶成分液の変色を評価するために、測定した加熱前後のLab値を用いて、茶成分液の色差ΔEを下記式1に従って算出した。結果を表1に示す。
<Evaluation of color of tea component liquid>
About each tea component liquid prepared above, the Lab value of a tea component liquid is measured using a spectroscopic color meter (made by Nippon Denshoku Industries Co., Ltd.), and further heated to 150 ° C. for 30 minutes and 120 The Lab value of the tea component liquid when minutes passed was measured. In order to evaluate the discoloration of the tea component liquid due to heating, the color difference ΔE of the tea component liquid was calculated according to the following formula 1, using the measured Lab values before and after heating. The results are shown in Table 1.

ΔE=[(ΔL)+(Δa)+(Δb)1/2 (式1)
表1によれば、茶成分液の種類に関わらず、茶成分濃度が増加するに従って加熱による色差ΔEが増大し、変色が激しくなることは共通である。しかし、総ポリフェノール量がほぼ同じであるカテキン液、緑茶液及び搾汁液を比較すると、色差は茶成分液の種類によって異なり、搾汁液の色差ΔEは、カテキン液及び緑茶液よりもかなり小さいことが明らかである。又、熱による色差変化についても、カテキン液及び緑茶液より、搾汁液の方が少なく色合いが安定している。従って、茶成分を配合した紙の加熱による変色を防止するには、茶殻の圧搾液を用いることが好適であることが分かる。この理由として、溶解又は極小粒子状に分散するポリフェノール以外の親水性成分が熱変色に関係する、あるいは、粒子が小さいことにより反応が進行し易くなるために熱変色が強くなるなどが考えられ、粒度分布が10μm以上であるものを用いるのが適している。
ΔE = [(ΔL) 2 + (Δa) 2 + (Δb) 2 ] 1/2 (Formula 1)
According to Table 1, regardless of the type of tea component liquid, it is common that the color difference ΔE due to heating increases as the tea component concentration increases and the discoloration becomes severe. However, when comparing catechin liquid, green tea liquid and squeezed liquid with almost the same amount of polyphenols, the color difference varies depending on the type of tea component liquid, and the color difference ΔE of the squeezed liquid may be considerably smaller than that of catechin liquid and green tea liquid. it is obvious. Further, regarding the color difference change due to heat, the squeezed liquid is less than the catechin liquid and the green tea liquid, and the hue is stable. Therefore, it can be seen that it is preferable to use a squeezed tea husk to prevent discoloration due to heating of the paper containing the tea component. The reason for this is that hydrophilic components other than polyphenols that are dissolved or dispersed in the form of extremely small particles are related to thermal discoloration, or because the reaction tends to proceed due to the small particles, the thermal discoloration becomes strong, etc. It is suitable to use one having a particle size distribution of 10 μm or more.

(表1)
加熱による変化
固形分量 総ポリフェノール 加熱による色差ΔE
(質量%) (質量%) 30分後 120分後
カテキン液A 0.05 0.02 1.38 1.86
カテキン液B 0.10 0.04 1.83 2.40
カテキン液C 0.20 0.08 1.86 3.21
カテキン液D 1.00 0.38 3.25 4.23
緑茶液A 2.30 0.37 4.53 5.01
緑茶液B 1.30 0.21 3.82 4.89
緑茶液C 0.60 0.10 2.85 4.52
緑茶液D 0.30 0.05 2.79 4.71
搾汁液A 2.30 0.41 1.53 2.58
搾汁液B 1.20 0.21 1.33 2.02
搾汁液C 0.60 0.10 1.02 1.52
(Table 1)
Changes due to heating
Solid content Color difference by total polyphenol heating ΔE
(Mass%) (mass%) 30 minutes later 120 minutes later Catechin solution A 0.05 0.02 1.38 1.86
Catechin liquid B 0.10 0.04 1.83 2.40
Catechin liquid C 0.20 0.08 1.86 3.21
Catechin liquid D 1.00 0.38 3.25 4.23
Green tea liquid A 2.30 0.37 4.53 5.01
Green tea liquid B 1.30 0.21 3.82 4.89
Green tea liquid C 0.60 0.10 2.85 4.52
Green tea liquid D 0.30 0.05 2.79 4.71
Juice fluid A 2.30 0.41 1.53 2.58
Juice B 1.20 0.21 1.33 2.02
Juice C 0.60 0.10 1.02 1.52

<乾燥茶殻の調製>
上記搾汁液の調製において得られる圧搾後の茶殻を105℃で乾燥して乾燥茶殻(総ポリフェノール:8.6質量%、EGC:2.1質量%、EGCg:1.3質量%、EC:0.6質量%、ECg:0.8質量%、エピ型カテキン類総含有量:4.8質量%)を得た。
<Preparation of dried tea husk>
The pressed tea husk obtained in the preparation of the juice is dried at 105 ° C. to dry tea husk (total polyphenol: 8.6 wt%, EGC: 2.1 wt%, EGC g: 1.3 wt%, EC: 0 0.6 mass%, ECg: 0.8 mass%, epi-catechins total content: 4.8 mass%).

<紙スラリーの調製>
無地のA4サイズ古紙25gを蒸留水1000mlに浸漬し、ジューサーミキサー(商品名:JC−L80MR、(株)東芝社製)で3分間攪拌して紙スラリーを調製した。
<Preparation of paper slurry>
25 g of plain A4 size waste paper was immersed in 1000 ml of distilled water, and stirred with a juicer mixer (trade name: JC-L80MR, manufactured by Toshiba Corporation) for 3 minutes to prepare a paper slurry.

<水分率の比較>
上記紙スラリーに蒸留水50ml及び上記乾燥茶殻2gを投入して2時間静置した後、目開き100μmの網上に流し込んで上から2kg/cmの圧力を加えて脱水した。この脱水物をピンセットで茶殻と紙パルプとにより分けて、各々の水分率を赤外線水分計(商品名:FD−620、(株)ケット科学研究所製)によって測定したところ、紙パルプの水分率は45.7質量%、茶殻の水分率は55.5質量%であった。
<Comparison of moisture content>
Distilled water (50 ml) and the dried tea husk (2 g) were added to the paper slurry and allowed to stand for 2 hours. Then, the paper slurry was poured onto a mesh having an opening of 100 μm and dehydrated by applying a pressure of 2 kg / cm 2 from above. This dehydrated product was divided into tea husk and paper pulp with tweezers, and the moisture content of each was measured with an infrared moisture meter (trade name: FD-620, manufactured by Kett Scientific Laboratory). Was 45.7% by mass, and the moisture content of the tea shells was 55.5% by mass.

上記のように、紙パルプと茶殻とで水分率に差があるため、上記脱水物を乾燥すると、水分率の低い紙パルプの方が茶殻より先に乾燥する。従って、完全に乾燥する際には、紙パルプが過乾燥状態になって品質低下を起こし、茶殻が紙パルプから剥離し易くなる。逆に、紙パルプの品質低下を避けると、茶殻が未乾燥状態となる。紙パルプの品質が低下することなく好適に乾燥できるためには、茶殻の乾燥が促進されるように紙スラリーに投入する茶殻の粒径を調整する必要がある。   As described above, since there is a difference in moisture content between the paper pulp and the tea husk, when the dehydrated product is dried, the paper pulp having a lower moisture content is dried before the tea husk. Therefore, when completely drying, the paper pulp becomes overdried, causing a deterioration in quality, and the tea shells are easily peeled off from the paper pulp. On the other hand, if the quality deterioration of the paper pulp is avoided, the tea husk becomes undried. In order to be able to dry suitably without deteriorating the quality of the paper pulp, it is necessary to adjust the particle size of the tea husk to be fed into the paper slurry so that the drying of the tea husk is promoted.

<茶殻粉砕物の調製>
上記乾燥茶殻を粉砕して篩い分けし、茶殻粉砕物A〜D(A:粒径1.6mm以上、B:粒径1mm以上1.6mm未満、C:粒径500μm以上1mm未満、D:粒径500μm未満)を得た。
<Preparation of ground tea powder>
The dried tea husk is crushed and sieved, and the crushed tea cakes A to D (A: particle size 1.6 mm or more, B: particle size 1 mm or more and less than 1.6 mm, C: particle size 500 μm or more and less than 1 mm, D: particle Diameter less than 500 μm).

<茶殻入り紙の調製>
上記茶殻粉砕物A〜Dの各々について、茶殻粉砕物2g及び蒸留水50mlを上記紙スラリー1000mlに投入し、ゆっくりと攪拌した後2時間静置して茶殻入りスラリーを得た。これを15cmx10cmの網(目開き100μm)上に流し込んで上から0.67kg/cmの圧力を加えて脱水した。この脱水物を105℃で3時間乾燥して茶殻入り紙A〜Dを得た。尚、乾燥後の茶殻入り紙の水分率は何れも5質量%以下であった。
<Preparation of tea-shelled paper>
For each of the above tea crushed powders A to D, 2 g of tea crushed powder and 50 ml of distilled water were added to 1000 ml of the above paper slurry, stirred slowly and allowed to stand for 2 hours to obtain a slurry containing tea husk. This was poured onto a 15 cm × 10 cm net (aperture 100 μm) and dehydrated by applying a pressure of 0.67 kg / cm 2 from above. This dehydrated product was dried at 105 ° C. for 3 hours to obtain tea leaves-containing papers A to D. In addition, the moisture content of the tea-shelled paper after drying was 5% by mass or less.

得られた茶殻入り紙について、下記に従って表面観察及び成分分散性の評価を行った。   About the obtained tea-shelled paper, surface observation and component dispersibility evaluation were performed according to the following.

<搾汁液入り紙の調製>
乾燥固形物量2gに相当する量の上記搾汁液Aを上記紙スラリー1000mlに投入して蒸留水50ml加え、ゆっくりと攪拌した後2時間静置して搾汁液入りスラリーを得た。これを15cmx10cmの網(目開き100μm)上に流し込んで上から0.67kg/cmの圧力を加えて脱水した。この脱水物を105℃で3時間乾燥して搾汁液成分入り紙を得た。この紙の水分率は5質量%以下であった。
<Preparation of paper containing juice>
An amount of the juice A corresponding to 2 g of the dry solid was added to 1000 ml of the paper slurry, 50 ml of distilled water was added, and the mixture was slowly stirred and allowed to stand for 2 hours to obtain a slurry containing the juice. This was poured onto a 15 cm × 10 cm net (aperture 100 μm) and dehydrated by applying a pressure of 0.67 kg / cm 2 from above. This dehydrated product was dried at 105 ° C. for 3 hours to obtain a paper containing the juice component. The moisture content of this paper was 5% by mass or less.

得られた搾汁液成分入り紙について、下記に従って表面観察及び成分分散性の評価を行った。   About the obtained paper containing squeezed liquid component, surface observation and component dispersibility evaluation were performed according to the following.

<表面観察>
茶殻入り紙A〜D及び搾汁液入り紙の各々を2cmx4cmに切断して、直径5cmの円柱の側面に沿って張り付け、紙の表面状態を目視及び実態顕微鏡(商品名:BS−D8000 Ver.6.14、ソニック(株)社製)によって観察した。目視において茶殻の少なくとも一部が紙面から脱離しているものを「C」、目視で茶殻の脱離は確認されないが、倍率50〜100倍の顕微鏡観察において茶殻の少なくとも一部が紙面から脱離している部分が10箇所以上確認されるものを「B」、目視で茶殻の脱離は確認されず、倍率50〜100倍の顕微鏡観察において確認される茶殻の少なくとも一部が紙面から脱離している部分が10箇所未満であるものを「A」と評価した。結果を表2に示す。
<Surface observation>
Each of the papers A to D with tea leaves and the paper with squeezed juice is cut into 2 cm x 4 cm and pasted along the side of a cylinder with a diameter of 5 cm, and the surface state of the paper is visually and actually observed (trade name: BS-D8000 Ver.6.14). , Manufactured by Sonic Corporation). “C” indicates that at least a portion of the tea husk is detached from the paper surface visually, but no detachment of the tea husk is visually confirmed, but at least a portion of the tea husk is detached from the paper surface under a microscope observation at a magnification of 50 to 100 times. "B" indicates that 10 or more parts are confirmed, and no detachment of the tea husk is visually confirmed, and at least part of the tea husk confirmed by microscopic observation at a magnification of 50 to 100 times is detached from the paper surface. Those having less than 10 portions were evaluated as “A”. The results are shown in Table 2.

<成分分散性>
茶殻入り紙A〜D及び搾汁液入り紙の各々を5cmx5cmに切断して、鉄イオンを含む水溶液を紙表面に噴霧し、ポリフェノールと鉄イオンとの反応による黒色変化を利用してポリフェノールを含む部分の分布を確認した。観察結果から、全体が均一に黒色変化したものを良好、黒色変化が部分的で不均一なものを不良、黒色変化が見られないものを未反応とした。
<Component dispersibility>
Each of the papers A to D with tea leaves and the paper with squeezed juice is cut into 5 cm x 5 cm, an aqueous solution containing iron ions is sprayed on the paper surface, and the portion containing polyphenols utilizing the black change caused by the reaction between polyphenols and iron ions The distribution of was confirmed. From the observation results, those in which the whole was uniformly changed to black were good, those in which the black change was partial and non-uniform were defective, and those in which no black change was seen were unreacted.

表2の結果は、茶殻の粒径が500μm未満の茶殻入り紙Dにおいて、茶殻の脱離が少なく、ポリフェノールの分散性も良好であることを示している。又、茶殻入り紙A〜Cを顕微鏡観察した際に、茶殻と紙パルプ繊維との間に空隙が確認された。これは、含水状態の茶殻が乾燥する時の体積減少によるものと考えられる。従って、茶殻の粒径が大きいと、体積減少による空隙が大きくなり、茶殻の剥離が起こり易くなると考えられる。   The results in Table 2 indicate that in the tea-shell-containing paper D having a tea-shell particle size of less than 500 μm, there is little detachment of the tea-shell and good dispersibility of the polyphenol. Further, when the papers A to C containing the tea husk were observed with a microscope, a gap was observed between the tea husk and the paper pulp fiber. This is thought to be due to a decrease in volume when the dried tea leaves are dried. Therefore, it is considered that when the particle size of the tea husk is large, voids due to volume reduction become large, and peeling of the tea husk easily occurs.

表1及び表2の結果を総合すると、紙パルプスラリーに添加する茶成分液としての適性を判断する際に、粒度分布が10μm以上500μm未満のものを選択することが有効であると考えられる。   When the results of Tables 1 and 2 are combined, it is considered effective to select a particle having a particle size distribution of 10 μm or more and less than 500 μm when determining suitability as a tea component liquid added to the paper pulp slurry.

(表2)
茶殻による影響
茶殻入り紙 搾汁液成分
A B C D 入り紙
表面観察 C C B A A
(脱離箇所) (15箇所)(8箇所)(0箇所)
成分分散性 不良 不良 不良 良好 良好
(Table 2)
Effects of tea leaves
Ingredients for tea squeezed paper juice
A ABCD paper
Surface observation C C B A A
(Desorption location) (15 locations) (8 locations) (0 locations)
Component dispersibility Defect Defect Defect Good Good

<搾汁液入り紙の調製>
表3の配合割合に従って、上記搾汁液A及び蒸留水を上記紙スラリー1000mlに投入して攪拌した後2時間静置して搾汁液入りスラリーを得た。これを100ml分取し、15cm×10cmの網(目開き100μm)上に流し込んで上から0.67kg/cmの圧力を加えて水分率が約50%になるまで脱水した。この脱水物を105℃で2時間乾燥して紙A0及び搾汁液入り紙A1〜A5を得た。紙の水分率は何れも5質量%以下であった。尚、表3中のポリフェノール配合率(%)は、混合スラリー中の総ポリフェノール量を示す。
<Preparation of paper containing juice>
According to the blending ratios in Table 3, the juice A and distilled water were added to 1000 ml of the paper slurry and stirred, and then allowed to stand for 2 hours to obtain a slurry containing the juice. 100 ml of this was collected, poured onto a 15 cm × 10 cm net (aperture 100 μm), and dehydrated until a water content of about 50% was applied by applying a pressure of 0.67 kg / cm 2 from above. This dehydrated product was dried at 105 ° C. for 2 hours to obtain paper A0 and paper A1 to A5 containing juice. The moisture content of the paper was 5% by mass or less. In addition, the polyphenol compounding ratio (%) in Table 3 indicates the total amount of polyphenol in the mixed slurry.

(表3)
抄紙用スラリーの配合割合
搾汁液入り紙
A0 A1 A2 A3 A4 A5
紙スラリー(ml) 1000 1000 1000 1000 1000 1000
搾汁液A(ml) 0 10 25 50 75 100
蒸留水(ml) 100 90 75 50 25 0
ポリフェノール
配合率(%) 0 0.04 0.10 0.21 0.31 0.41
乾物質量当りの
ポリフェノール(%) 0 0.16 0.40 0.78 1.15 1.50
(Table 3)
Mixing ratio of slurry for papermaking
Paper with juice
A0 A1 A2 A3 A4 A5
Paper slurry (ml) 1000 1000 1000 1000 1000 1000
Juice juice A (ml) 0 10 25 50 75 100
Distilled water (ml) 100 90 75 50 25 0
Polyphenol
Mixing rate (%) 0 0.04 0.10 0.21 0.31 0.41
Per dry matter
Polyphenol (%) 0 0.16 0.40 0.78 1.15 1.50

<搾汁液入り紙の評価>
上記紙A0及び搾汁液入り紙A1〜A5について、下記に従って悪臭放出抑制試験、消臭試験及び抗菌試験を行って、紙の消臭性、悪臭放出抑制及び抗菌性を評価した。結果を表4に示す。
<Evaluation of paper with juice juice>
About the said paper A0 and paper A1-A5 containing squeezed liquid, the malodor emission suppression test, the deodorization test, and the antibacterial test were done according to the following, and the deodorizing property, malodor discharge suppression, and antibacterial property of paper were evaluated. The results are shown in Table 4.

(消臭試験)
紙A0〜A5を各々3cm×3cmの試料に切断し、悪臭物質としてアンモニア(初期濃度:140ppm)及びホルムアルデヒド(初期濃度:30ppm)を含有する空気2Lと共にテドラーバックに詰め、常温で3時間静置した後、ガステック社製ガス検知管を用いてバック内の空気に存在する各悪臭物質の残存濃度を測定し、各悪臭物質における初期濃度及び残存濃度から、下記計算式に従って消臭率を算出した。結果を表4に示す。
(Deodorization test)
Paper A0 to A5 were cut into 3 cm x 3 cm samples, packed in a Tedlar bag with 2 L of air containing ammonia (initial concentration: 140 ppm) and formaldehyde (initial concentration: 30 ppm) as malodorous substances, and allowed to stand at room temperature for 3 hours. After that, the residual concentration of each malodorous substance present in the air in the bag was measured using a gas detection tube manufactured by Gastec, and the deodorization rate was calculated from the initial concentration and residual concentration of each malodorous substance according to the following formula. . The results are shown in Table 4.

消臭率(%)=100×(初期濃度−残存濃度)/初期濃度
搾汁液を配合しない紙A0における消臭率は、アンモニアでは19%、ホルムアルデヒドでは35%であったことから、これらを消臭性の基準として、アンモニアについては29%以上(基準+10%以上)を良好、19%超29%未満を有効、ホルムアルデヒドについては45%以上(基準+10%以上)を良好、35%超45%未満を有効と評価した。
Deodorization rate (%) = 100 × (initial concentration−residual concentration) / initial concentration The deodorization rate in paper A0 containing no juice was 19% for ammonia and 35% for formaldehyde. As a odor standard, 29% or more (standard + 10% or more) is good for ammonia, more than 19% is effective if it is less than 29%, 45% or more (standard + 10% or more) is good for formaldehyde, more than 35% is 45% Less than rated as effective.

(悪臭放出抑制試験)
試料が同重量になるように、紙A0〜A5を各々約4cm角の試料に切断し、アンモニア希釈水溶液(和光純薬(株)社製25%アンモニア水を蒸留水で2500倍に希釈したもの)0.5mlを浸透させた後に空気3Lと共にテドラーバッグに封入して常温で1時間静置した。この後、テドラーバック内の空気中のアンモニアガス濃度Aaをガステック社製アンモニアガス検知管で測定した。
(Odor odor emission suppression test)
Paper A0 to A5 are cut into approximately 4 cm square samples so that the sample has the same weight, and an ammonia diluted aqueous solution (25% ammonia water manufactured by Wako Pure Chemical Industries, Ltd. diluted 2500 times with distilled water) ) After impregnating 0.5 ml, it was sealed in a Tedlar bag together with 3 L of air and allowed to stand at room temperature for 1 hour. Thereafter, the ammonia gas concentration Aa in the air in the Tedlar bag was measured with an ammonia gas detector tube manufactured by Gastec.

別途、上記アンモニア希釈水溶液0.5mlを空気3Lと共にテドラーバックに封入して常温で1時間放置した後、テドラーバック内の空気中のアンモニアガス濃度Cを測定した。この測定値は20ppmであった。   Separately, 0.5 ml of the ammonia diluted aqueous solution was sealed in a Tedlar bag together with 3 L of air and left at room temperature for 1 hour, and then the ammonia gas concentration C in the air inside the Tedlar bag was measured. This measured value was 20 ppm.

測定されたアンモニアガス濃度Aa,Cから、下記計算式に従って悪臭放出抑制率(%)を算出した。結果を表4に示す。   The malodor emission suppression rate (%) was calculated from the measured ammonia gas concentrations Aa and C according to the following formula. The results are shown in Table 4.

悪臭放出抑制率=100×(C−Aa)/C
上記悪臭放出抑制率は、搾汁液を配合しない紙A0における悪臭放出抑制率が63%であることを考慮して、10%以上の改善が見られる74%以上のものを良好、65%超74%未満のものを有効と評価した。
Odor emission suppression rate = 100 × (C−Aa) / C
The above-mentioned malodor emission suppression rate is good when it is 74% or more where improvement of 10% or more is seen, considering that the malodor emission suppression rate in paper A0 without blending juice is 63%, more than 65% 74 Less than% was evaluated as effective.

(抗菌試験)
紙A0〜A5を、5cm×5cmの試料に切断し、1/500普通ブイヨンに浸漬した後に取り出し、抗菌製品技術協議会が定めるフィルム密着法に従って24時間経過後の試料上の菌液(MRSA:メスチリン耐性黄色ブドウ球菌)の生菌数(CFU/枚)を測定した。
(Antimicrobial test)
Paper A0 to A5 are cut into 5 cm × 5 cm samples, dipped in 1/500 ordinary bouillon, taken out, and taken on the sample after 24 hours according to the film adhesion method defined by the Antibacterial Products Technical Council (MRSA: The viable count (CFU / plate) of methicillin-resistant Staphylococcus aureus was measured.

また、紙A0〜A5を、3cm×3cmの試料に切断し、菌液(MRSA)の混合平板培地上に密着貼付して35℃で24時間培養した後、試料周辺の培地に生じる透明な生育阻止体(ハロー)の有無を調べた。   In addition, the paper A0 to A5 is cut into 3 cm × 3 cm samples, adhered onto a mixed plate medium of fungus solution (MRSA), cultured at 35 ° C. for 24 hours, and then transparent growth occurring in the medium around the samples. The presence or absence of a blocker (halo) was examined.

上記試験において、24時間後の生菌数が3.9×10未満であり、ハローが確認されたものをA、24時間後の生菌数が3.9×10未満であり、ハローが確認されなかったものをB、24時間後の生菌数が3.9×10以上であり、ハローが確認されなかったものをCと判定した。結果を表4に示す。 In the above test, the number of viable bacteria after 24 hours was less than 3.9 × 10 3 and halo was confirmed as A, the number of viable cells after 24 hours was less than 3.9 × 10 3 , and halo No was confirmed as B, and the number of viable bacteria after 24 hours was 3.9 × 10 3 or more, and no halo was confirmed as C. The results are shown in Table 4.

表4によれば、含水茶殻の圧搾液は、消臭性や抗菌性等を有する紙の製造に有用であることが明らかであり、配合されるポリフェノール量が増加するに従って付与される機能も増大する。含水茶殻の圧搾液は加熱による色差増加が少ないので、紙の着色を抑制しつつ好適に茶成分の機能を付与することができる。圧搾液中の茶成分は、ほぼ全量が製紙・乾燥後の紙に移行し、得られる紙中の総ポリフェノールの割合は、紙A4において約1.15質量%、紙A5において約1.50質量%である。

Figure 0004928904
According to Table 4, it is clear that the squeezed tea squeezed liquid is useful for the production of paper having deodorant properties, antibacterial properties, etc., and the function imparted as the amount of polyphenol blended increases. To do. Since the squeezed liquid of the water-containing tea shells has little increase in color difference due to heating, the function of the tea component can be suitably imparted while suppressing the coloring of the paper. The tea component in the pressing liquid is almost entirely transferred to the paper after papermaking and drying, and the ratio of the total polyphenols in the obtained paper is about 1.15% by mass in paper A4 and about 1.50 mass in paper A5. %.
Figure 0004928904

Claims (8)

0.10〜5MPaの圧力を加えた含水茶殻の搾汁液が配合された紙パルプスラリーを調製し、該紙パルプスラリーを抄紙し、抄紙した含水紙から水を除去することを特徴とする紙の製造方法。   A paper pulp slurry containing a hydrated tea squeezed juice squeezed with a pressure of 0.10 to 5 MPa is prepared, the paper pulp slurry is made, and water is removed from the paper-containing hydrated paper. Production method. 前記含水茶殻は、水を用いて原料茶葉から飲料茶を抽出した抽出残渣であり、前記搾汁液は、前記含水茶殻の粒径500μm未満の粒子を含み、ポリフェノールを含有する請求項1記載の紙の製造方法。   2. The paper according to claim 1, wherein the water-containing tea shell is an extraction residue obtained by extracting beverage tea from raw tea leaves using water, and the juice contains particles having a particle size of less than 500 μm of the water-containing tea shell and contains polyphenol. Manufacturing method. 前記原料茶葉は緑茶葉を含み、前記ポリフェノールはカテキンを含む請求項2記載の紙の製造方法。   The method for producing paper according to claim 2, wherein the raw tea leaves include green tea leaves and the polyphenols include catechins. 含水茶殻に圧力を加えて、茶由来のポリフェノールを含有し、粒径が10μm以上500μm未満の茶殻粒子を含む搾汁液を調製し、前記茶殻粒子を含む搾汁液を配合した紙パルプスラリーを調製し、該紙パルプスラリーを抄紙し、抄紙した含水紙から水を除去することを特徴とする紙の製造方法。 Pressure is applied to the water-containing tea shell to prepare a juice juice containing tea-derived polyphenols and containing tea shell particles having a particle size of 10 μm or more and less than 500 μm, and a paper pulp slurry containing the juice juice containing the tea shell particles is prepared. A method for producing paper, characterized in that the paper pulp slurry is paper-made and water is removed from the paper-containing water-containing paper. 前記茶由来のポリフェノールは、緑茶由来ポリフェノールであり、カテキンを含む請求項4記載の紙の製造方法。   The method for producing paper according to claim 4, wherein the tea-derived polyphenol is a green tea-derived polyphenol and contains catechin. 前記紙パルプスラリーは、紙パルプの乾燥質量に対する総ポリフェノール量が0.10〜1.50質量%となる割合のポリフェノールを含有する請求項1〜5の何れかに記載の紙の製造方法。   The said paper pulp slurry is a manufacturing method of the paper in any one of Claims 1-5 containing the polyphenol of the ratio used as the total polyphenol amount with respect to the dry mass of paper pulp becoming 0.10-1.50 mass%. 前記含水紙は、加熱乾燥によって水を除去する請求項1〜6の何れかに記載の紙の製造方法。   The said water-containing paper is a paper manufacturing method in any one of Claims 1-6 which removes water by heat drying. 前記加熱乾燥における加熱温度は、100〜160℃である請求項7記載の紙の製造方法。   The paper manufacturing method according to claim 7, wherein a heating temperature in the heat drying is 100 to 160 ° C.
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WO2014081093A1 (en) * 2012-11-22 2014-05-30 Son Won Gil Method for manufacturing functional pulp and paper by using coffee grounds
WO2018136763A1 (en) 2017-01-19 2018-07-26 Javacube, Inc. Cellulosic composition containing coffee parchment cellulose and uses thereof

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JP5580259B2 (en) * 2011-08-01 2014-08-27 株式会社 伊藤園 Clay calcined product, method for producing the same, and clay composition for producing clay calcined product
JP6553320B1 (en) 2017-12-28 2019-07-31 コアレックス信栄株式会社 Deodorant paper manufacturing method

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WO2014081093A1 (en) * 2012-11-22 2014-05-30 Son Won Gil Method for manufacturing functional pulp and paper by using coffee grounds
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