JPH0827280A - Production of decomposable composite material - Google Patents
Production of decomposable composite materialInfo
- Publication number
- JPH0827280A JPH0827280A JP16718094A JP16718094A JPH0827280A JP H0827280 A JPH0827280 A JP H0827280A JP 16718094 A JP16718094 A JP 16718094A JP 16718094 A JP16718094 A JP 16718094A JP H0827280 A JPH0827280 A JP H0827280A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- polymer
- lactic acid
- base material
- paper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Reinforced Plastic Materials (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、自然環境下での分解性
を持ったポリマーとセルロース繊維を含有する基材との
複合材料の製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a composite material of a polymer having degradability in a natural environment and a substrate containing cellulose fibers.
【０００２】[0002]
【従来技術】近年、農業用資材や衛生用品として、塩化
ビニル系樹脂、オレフィン系樹脂、酢酸ビニル系樹脂等
の汎用プラスチック製品が多用されている。例えば、農
業用マルチシート、畝カバー等は、雑草、土壌温度およ
び浸食の制御の目的で植物の畝間に敷かれており、風お
よび雨を含む過酷な条件下においても十分耐えうる強度
を有している。しかしながら、これらの汎用プラスチッ
ク製品は、利点がある反面、自然環境下で分解しない
か、または分解速度が極めて低いため、使用後放置され
たり、土中に埋設処理された場合、半永久的に地上や地
中に残存することになる。また、海洋投棄された場合
は、景観を損なったり、海洋生物の生活環境を破壊した
りする。特に、塩化ビニル系樹脂を焼却した場合は、塩
化水素等の有害ガスが発生し、大気を汚染するだけでな
く、焼却炉の劣化を促進するなど、消費の拡大と共に廃
棄物処理が社会問題となっている。これらの問題に伴っ
て、耐久性を必要としない農業用資材分野においては、
紙が基材として使用されている。この場合には、自然環
境中での分解性は速く、また、焼却時に有害なガスを発
生しないなどの利点が有るものの、汎用プラスチック製
品に比べ、強度が低く、耐水性に劣り、湿潤下では著し
く強度が低下する等の欠点があった。2. Description of the Related Art In recent years, general-purpose plastic products such as vinyl chloride resins, olefin resins and vinyl acetate resins have been widely used as agricultural materials and sanitary products. For example, agricultural mulch sheets, ridge covers, etc. are laid between the ridges of plants for the purpose of controlling weeds, soil temperature and erosion, and have sufficient strength to withstand even the harsh conditions including wind and rain. ing. However, while these general-purpose plastic products have the advantage, they do not decompose in the natural environment or have a very low decomposition rate, so if they are left unused or buried in the soil, they will be semipermanently or on the ground. It will remain in the ground. Also, when dumped into the ocean, it damages the landscape and destroys the living environment of marine life. In particular, when vinyl chloride resin is incinerated, harmful gas such as hydrogen chloride is generated, which not only pollutes the atmosphere but also accelerates deterioration of the incinerator. Has become. Due to these problems, in the field of agricultural materials that do not require durability,
Paper is used as the substrate. In this case, although it decomposes quickly in the natural environment and has the advantage that harmful gas is not generated when incinerated, it has lower strength than general-purpose plastic products, poor water resistance, and in wet conditions. There were drawbacks such as a marked decrease in strength.
【０００３】最近では、これら汎用プラスチック製品に
替わる材料として、強度と分解性を合わせ持ったポリヒ
ドロキカルボン酸のファイバー及びシートで、紙を強化
した分解性複合材料が開示されている（ＷＯ ９２／０
５３１１）。この分解性複合材料は、あらかじめポリマ
ーを繊維状に加工してパルプの中に入れ込む、あるいは
シート状に加工してから紙と貼り合わせて製造されるこ
とが記載されている。しかし、この方法では、ポリヒド
ロキシカルボン酸をあらかじめ繊維やシートに加工しな
ければならず、操作が煩雑で手間が掛かり、工業的に有
利な方法とは言えない。また、ポリマーの分子量は繊維
状あるいはシート状にするため、ある程度の機械的強度
を持たさなければ加工できず最低でも５０，０００以上
の分子量が必要である。Recently, as an alternative material to these general-purpose plastic products, a degradable composite material in which a paper and a fiber of polyhydroxycarboxylic acid having both strength and degradability are reinforced with paper has been disclosed (WO 92 / 0
5311). It is described that this degradable composite material is produced by previously processing the polymer into a fibrous form and inserting it into pulp, or after processing into a sheet form and then laminating it with paper. However, in this method, the polyhydroxycarboxylic acid has to be processed into a fiber or sheet in advance, the operation is complicated and troublesome, and it cannot be said to be an industrially advantageous method. In addition, since the polymer has a fibrous or sheet-like molecular weight, it cannot be processed unless it has a certain level of mechanical strength, and a molecular weight of at least 50,000 is required.
【０００４】その他の製造方法として、植物性繊維を主
成分とする基材に、重量平均分子量１００，０００以上
のポリ乳酸を粉体状で散布した後、熱プレスにより被覆
して複合材料を製造する方法が開示されている（特開平
４−３３４４４８）。しかしこの方法では、粉体を直
接、基材に散布しながら熱プレスをするため、工程途中
で粉体が飛び散り、工業的に有利な方法とは言えない。
また、得られた複合材料は、表面にポリ乳酸が厚く被覆
されているので、水に浮き易く、全く透水性が無いとい
うものである。さらに、ポリマーを溶剤に溶解した液を
紙に浸漬する方法はハロゲン系有機溶剤を使用しなけれ
ばならず、環境汚染にもつながる。As another production method, a polylactic acid having a weight average molecular weight of 100,000 or more is sprinkled in a powder form on a substrate containing vegetable fibers as a main component and then coated by hot pressing to produce a composite material. A method of doing so is disclosed (JP-A-4-334448). However, in this method, the powder is directly sprayed on the base material while hot pressing, so the powder is scattered during the process, which is not an industrially advantageous method.
In addition, the obtained composite material has a thick polylactic acid coating on its surface, so that it easily floats in water and has no water permeability at all. Furthermore, the method of immersing a liquid in which a polymer is dissolved in a paper must use a halogen-based organic solvent, which leads to environmental pollution.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、充分な強度
と透水性を有し、しかも、自然環境下で十分な分解性を
有する、分解性ポリマーとセルロース繊維を含有する基
材との複合材料を、簡単に、且つ、工業的に有利に製造
する方法を提供することを課題とする。DISCLOSURE OF THE INVENTION The present invention is a composite of a degradable polymer and a substrate containing cellulose fibers, which has sufficient strength and water permeability, and has sufficient degradability in a natural environment. An object of the present invention is to provide a method for easily and industrially producing a material.
【０００６】[0006]
【課題を解決するための手段】本発明者らは、前記課題
につき鋭意検討した結果、土中や水中などで分解する性
質を持つ重量平均分子量５０，０００以下のポリ乳酸、
または、乳酸とオキシカルボン酸とのコポリマーを主成
分とする分解性ポリマーが、簡単に湿式微粒化できるこ
とに着目し、平均粒径が５０μｍ以下のポリマー微粒子
の分散液を、セルロース繊維を含有する基材に、薄く、
均一に塗布した後、加熱処理する方法で強度と透水性を
持ち、しかも、自然環境下で分解する複合材料が、簡単
に、且つ、工業的に有利に製造できることを見出し、本
発明を完成した。すなわち、本発明は、ポリ乳酸、また
は、乳酸とオキシカルボン酸のコポリマーを主成分とす
る分解性ポリマーの分散液を、セルロース繊維を含有す
る基材に塗布した後、加熱処理することを特徴とする分
解性複合材料の製造方法に関するものである。Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that polylactic acid having a weight average molecular weight of 50,000 or less, which has a property of decomposing in soil or water,
Alternatively, focusing on the fact that a degradable polymer containing a copolymer of lactic acid and oxycarboxylic acid as a main component can be easily wet atomized, a dispersion liquid of polymer fine particles having an average particle diameter of 50 μm or less is used as a base containing a cellulose fiber. Thin,
The present invention has been completed by finding that a composite material having strength and water permeability by a method of uniformly applying and then heat-treating, and yet decomposing in a natural environment can be easily and industrially produced advantageously. . That is, the present invention is characterized in that a polylactic acid or a dispersion liquid of a degradable polymer containing a copolymer of lactic acid and an oxycarboxylic acid as a main component is applied to a substrate containing cellulose fibers and then heat-treated. The present invention relates to a method for producing a decomposable composite material.
【０００７】本発明の分解性複合材料は、セルロース繊
維を含有する基材に対して、ポリマーの量が少ないた
め、基材の透水性を失うこと無く、加熱処理により基材
に適度な強度を与えることができる。さらに、本発明で
用いるポリマー成分は、土中や水中などで分解するた
め、本来分解性であるセルロース繊維を含有する基材の
性質を損なうこともない。本発明に用いられる分解性ポ
リマーは、ポリ乳酸、または、乳酸とオキシカルボン酸
のコポリマーを主成分とするものであり、例えば、ポリ
乳酸、ポリ乳酸と他のオキシカルボン酸のポリマーとの
混合物、乳酸と他のオキシカルボン酸とのコポリマー等
が挙げられる。ポリマーを構成する乳酸としては、Ｌ−
乳酸、Ｄ−乳酸、またはそれらの混合物のいずれでも良
い。また、他のオキシカルボン酸としては、グリコール
酸、３−ヒドロキシ酪酸、４−ヒドロキシ酪酸、４−ヒ
ドロキシ吉草酸、５−ヒドロキシ吉草酸、６−ヒドロキ
シカプロン酸等が用いられる。The decomposable composite material of the present invention has a small amount of polymer with respect to the base material containing the cellulose fiber, so that the base material does not lose the water permeability of the base material and is heat-treated to have an appropriate strength. Can be given. Furthermore, since the polymer component used in the present invention decomposes in soil, water, etc., it does not impair the properties of the base material containing the originally decomposable cellulose fiber. The degradable polymer used in the present invention is mainly composed of polylactic acid or a copolymer of lactic acid and oxycarboxylic acid, for example, polylactic acid, a mixture of polylactic acid and a polymer of other oxycarboxylic acid, Examples thereof include copolymers of lactic acid and other oxycarboxylic acids. As lactic acid that constitutes the polymer, L-
Either lactic acid, D-lactic acid, or a mixture thereof may be used. As other oxycarboxylic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, 5-hydroxyvaleric acid, 6-hydroxycaproic acid, etc. are used.
【０００８】これらの分解性ポリマーは、乳酸あるいは
他のオキシカルボン酸から直接脱水重縮合することによ
って合成したものでも良いし、ラクタイド、グリコライ
ド、ε−カプロラクトン、またはそれらの混合物を、開
環重合することによって得られたものでも良い。また、
ポリ乳酸と他のオキシカルボン酸のポリマーを、高温
下、エステル交換反応することによって合成したコポリ
マーでも良い。本発明に使用する分解性ポリマーの重量
平均分子量は、１，０００〜５０，０００の範囲が好ま
しい。特に好ましくは、重量平均分子量３，０００〜５
０，０００である。重量平均分子量が１００，０００以
上になると、ポリマーが硬くなり、微粒化し難く加工性
に劣る。These degradable polymers may be those synthesized by direct dehydration polycondensation from lactic acid or other oxycarboxylic acid, or lactide, glycolide, ε-caprolactone, or a mixture thereof may be subjected to ring-opening polymerization. It may be obtained by doing. Also,
A copolymer prepared by subjecting a polymer of polylactic acid and another oxycarboxylic acid to a transesterification reaction at high temperature may be used. The weight average molecular weight of the degradable polymer used in the present invention is preferably in the range of 1,000 to 50,000. Particularly preferably, the weight average molecular weight is 3,000 to 5
It is 10,000. When the weight average molecular weight is 100,000 or more, the polymer becomes hard, and it is difficult to form fine particles, resulting in poor processability.
【０００９】本発明の分解性ポリマーの分散液は、ポリ
マーを粉砕した後、さらに湿式微粒化することによって
調製される。ポリマーの粉砕方法としては、重合により
得られたポリマーを冷却粉砕する方法、ポリマーを適当
な溶媒に加熱溶解させた後、冷却晶析又は再沈により、
微粒子状のポリマーを析出させる方法等が挙げられる
が、ポリマーの粒子径が７５μｍ以下（２００メッシ
ュ）の微粒子になれば、特に方法は限定されない。この
様にして得られたポリマーの微粒子を、非溶解性の溶媒
中に分散させ、例えば、ボールミル、アトライター、サ
ンドグラインダーなどで、球状の粉砕用メジャーを用い
て湿式微粒化を行い、分散液を調製する。分散液中のポ
リマーの平均粒径は、通常、０．１〜５０μｍ、好まし
くは０．１〜３０μｍであり、基材に塗布した時のポリ
マーの均一性を得るため、１〜１５μｍの範囲が特に好
ましい。The dispersion of the degradable polymer of the present invention is prepared by pulverizing the polymer and then subjecting it to wet atomization. As the pulverization method of the polymer, a method of cooling and pulverizing the polymer obtained by the polymerization, after heating and dissolving the polymer in a suitable solvent, by cooling crystallization or reprecipitation,
Examples thereof include a method of depositing a fine particle polymer, but the method is not particularly limited as long as the particle diameter of the polymer is 75 μm or less (200 mesh). The fine particles of the polymer thus obtained are dispersed in a non-soluble solvent, for example, wet milling is performed using a ball mill, attritor, sand grinder or the like with a spherical pulverizing measure, and the dispersion liquid is obtained. To prepare. The average particle size of the polymer in the dispersion is usually 0.1 to 50 μm, preferably 0.1 to 30 μm, and in order to obtain the homogeneity of the polymer when applied to the substrate, the range of 1 to 15 μm is used. Particularly preferred.
【００１０】湿式微粒化の際に用いる溶媒としては、水
が特に好ましい。また、分散液中のポリマーの濃度は、
ポリマー微粒子が十分に分散してスラリー状となれば良
く、１０〜５０ｗｔ％の濃度が特に好ましい。湿式微粒
化する際に、分散剤を使用してもよく、使用できる分散
剤の種類としては、特に限定はされないが、ポリビニル
アルコール等の水溶性高分子系分散剤が好ましい。例え
ば、完全鹸化型あるいは部分鹸化型のポリビニルアルコ
ール、または分子内にスルホン酸基を有するポリビニル
アルコール誘導体、ポリスチレンスルホン酸塩、ポリ−
α−メチルスチレンスルホン酸塩などのアニオン性水溶
性高分子が挙げられる。分散剤の使用量は、通常、ポリ
マー１００重量部当たり、０．１〜２０重量部が好まし
く、特に好ましくは、１〜１０重量部である。また、分
散効率を上げるため上記分散剤を併用して使用してもか
まわない。Water is particularly preferable as the solvent used in the wet atomization. The concentration of the polymer in the dispersion is
It is sufficient that the polymer fine particles are sufficiently dispersed to form a slurry, and a concentration of 10 to 50 wt% is particularly preferable. A dispersant may be used for wet atomization, and the type of dispersant that can be used is not particularly limited, but a water-soluble polymer dispersant such as polyvinyl alcohol is preferable. For example, completely saponified or partially saponified polyvinyl alcohol, polyvinyl alcohol derivatives having a sulfonic acid group in the molecule, polystyrene sulfonate, poly-
Examples thereof include anionic water-soluble polymers such as α-methylstyrene sulfonate. The amount of dispersant used is usually preferably 0.1 to 20 parts by weight, and particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the polymer. In addition, the above dispersants may be used in combination in order to increase the dispersion efficiency.
【００１１】本発明の分解性ポリマーの分散液を、セル
ロース繊維を含有する基材へ塗布する方法としては、ポ
リマー分散液を基材に、吹付、散布、浸積、または、バ
ーコーター、エアナイフコーター、ロールコーター、ブ
レードコーター等の機器を使用して塗布する方法等が挙
げられる。ポリマーの塗布量については、使用する基材
の強度または坪量によって異なるが、通常、乾燥重量で
表して、基材１００重量部当たり、１〜４０重量部であ
る。特に好ましくは、１〜２０重量部の範囲である。農
業用畝カバー等においては、透水性、分解性および高い
遮断性を有することが望ましいため、原紙の片面のみに
塗布し、ポリマーの塗布量を１０重量部以下にすること
が好ましい。The method for applying the dispersion of the degradable polymer of the present invention to a substrate containing cellulose fibers includes spraying, spraying, dipping, or a bar coater or an air knife coater on the substrate. A coating method using a device such as a roll coater or a blade coater may be used. The coating amount of the polymer varies depending on the strength or basis weight of the substrate used, but is usually 1 to 40 parts by weight per 100 parts by weight of the substrate, expressed as a dry weight. Particularly preferably, it is in the range of 1 to 20 parts by weight. Agricultural ridge covers and the like preferably have water permeability, decomposability, and high barrier properties, so it is preferable to coat only one side of the base paper and to coat the polymer in an amount of 10 parts by weight or less.
【００１２】さらに、特定の最終用途特性を付与するた
めに、他の添加物を分散液に配合することができる。他
の添加物の例としては、デンプン、蛋白、フッ化炭素、
クレー、二酸化チタン、活性炭等が挙げられる。本発明
の分解性複合材料に用いられるセルロース繊維を含有す
る基材としては、アート紙（塗被紙）、クラフト紙、ロ
ール紙、ライスペーパー、その他の加工原紙、クロス
紙、ボール紙などが用いられる。これらのセルロース繊
維を含有する基材は、再生したパルプを含んでもかまわ
ない。本発明の方法では、分解性ポリマー分散液をセル
ロース繊維を含有する基材に塗布した後、ポリマーを基
材に定着させるため、ポリマーの融点付近あるいは融点
以上に温度を上げてポリマーを溶融し、基材と接着する
加熱処理を行う。加熱処理温度は、通常、１００℃〜２
００℃の温度であり、ポリマーが基材と十分に接着でき
れば、熱ロールなどを用いても良い。In addition, other additives can be incorporated into the dispersion to impart specific end use properties. Examples of other additives include starch, protein, fluorocarbon,
Examples include clay, titanium dioxide, activated carbon and the like. As the base material containing cellulose fibers used in the degradable composite material of the present invention, art paper (coated paper), kraft paper, roll paper, rice paper, other processed base paper, cloth paper, cardboard, etc. are used. To be The substrate containing these cellulosic fibers may contain regenerated pulp. In the method of the present invention, after the degradable polymer dispersion is applied to a substrate containing cellulose fibers, in order to fix the polymer to the substrate, the polymer is melted by raising the temperature near or above the melting point of the polymer, Heat treatment for bonding to the substrate is performed. The heat treatment temperature is usually 100 ° C to 2 ° C.
A hot roll or the like may be used as long as the temperature is 00 ° C. and the polymer can sufficiently adhere to the substrate.
【００１３】[0013]
【実施例】以下、例をあげて本発明の方法を具体的に説
明するが、本発明はこれにより、なんら制限をうけるも
のではない。 実験例１ ステンレス製の１００ｃｃ容器に、晶析法により取り出
した２００メッシュパスのＬ−乳酸のポリマー（ＭＷ＝
４０，０００）５ｇ、ＰＶＡ系分散剤（日本合成化学社
製 ゴーセランＬ−３２６６ ３０ｗｔ％に調整）０．
８３ｇ、微粒化用ガラスビーズ（直径１ｍｍ）１５ｇお
よび水１９．１７ｇを入れ、良くなじませた後、スクリ
ュウ型の撹拌羽根（直径３５ｍｍ）を用いて、２０００
ｒｐｍで３時間撹拌し、微粒化した。目皿付の漏斗で濾
過してガラスビーズを除き、ポリマーの平均粒径５μｍ
の分散液を得た。上記分散液を、水で１０ｗｔ％に希釈
し、セルロース繊維を含有する基材であるＢ４サイズの
上質紙（坪量６０ｇ／ｍ2 ）の表面に、メイヤーバー＃
１０で塗布し、１７０℃で３分間乾燥させ、片面塗布紙
を作製した。乾燥後のポリマーの塗布量は３．０ｇ／ｍ
2 であった。このポリマー塗布紙を、３ｃｍ×１０ｃｍ
の短冊に切り、蒸留水中に１０秒間漬けた後、２００ｇ
の重りを吊るし、試験したが、ポリマー塗布紙は引き裂
けなかった。また、このポリマー塗布紙を、コンポスト
水抽出菌３倍希釈液中に入れ、３７℃で分解性試験をし
たところ、約３週間で完全分解した。EXAMPLES The method of the present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Experimental Example 1 A 200 mesh pass polymer of L-lactic acid (MW =
40,000) 5 g, PVA-based dispersant (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gocelan L-3266 30 wt%).
83 g, 15 g of glass beads for atomization (diameter 1 mm) and 19.17 g of water were put in and well blended, and then 2000 using a screw type stirring blade (diameter 35 mm)
The mixture was stirred at rpm for 3 hours and atomized. The glass beads were removed by filtration using a funnel with a plate, and the average particle size of the polymer was 5 μm.
A dispersion liquid of was obtained. The above dispersion was diluted to 10 wt% with water, and the Mayer bar # was formed on the surface of B4 size high-quality paper (basis weight 60 g / m 2 ) which is a base material containing cellulose fibers.
10 was applied and dried at 170 ° C. for 3 minutes to prepare a single-sided coated paper. The coating amount of the polymer after drying is 3.0 g / m
Was 2 . This polymer coated paper is 3 cm x 10 cm
Cut into strips and soak in distilled water for 10 seconds, then 200g
The weight was hung and tested, but the polymer coated paper did not tear. The polymer-coated paper was placed in a 3-fold diluted solution of compost water-extracting bacteria and subjected to a degradability test at 37 ° C., whereupon it was completely degraded in about 3 weeks.
【００１４】実験例２ 粉砕したＬ−乳酸とＤ−乳酸の９：１のコポリマー（Ｍ
Ｗ＝４０，０００）５ｇ、分散剤０．８３ｇ、ガラスビ
ーズ１５ｇ、水１９．１７ｇを用いて、実験例１と同様
にして、平均粒径７μｍの分散液を得た。上記分散液
を、水で、１０ｗｔ％に希釈し、Ｂ４サイズの上質紙
（坪量６０ｇ／ｍ2 ）の表面に、メイヤーバー＃１０で
塗布し、１７０℃で３分間乾燥させ、片面塗布紙を作製
した。乾燥後の塗布量は２．９ｇ／ｍ2 であった。この
ポリマー塗布紙を、実験例１と同様に試験したところ、
ポリマー塗布紙は引き裂けなかった。また、コンポスト
水抽出菌液中での分解性試験では、約３週間で完全分解
した。Experimental Example 2 Copolymer of ground L-lactic acid and D-lactic acid of 9: 1 (M
Using 5 g of W = 40,000, 0.83 g of a dispersant, 15 g of glass beads, and 19.17 g of water, a dispersion having an average particle size of 7 μm was obtained in the same manner as in Experimental Example 1. The above dispersion was diluted to 10 wt% with water, applied on the surface of B4 size wood free paper (basis weight 60 g / m 2 ) with Meyer bar # 10, dried at 170 ° C. for 3 minutes, and coated on one side. Was produced. The coating amount after drying was 2.9 g / m 2 . When this polymer-coated paper was tested in the same manner as in Experimental Example 1,
The polymer coated paper did not tear. Further, in the degradability test in the compost water-extracted bacterial solution, it was completely degraded in about 3 weeks.
【００１５】実験例３ 粉砕したＬ−乳酸とグリコ−ル酸の１：１のコポリマー
（ＭＷ＝３０，０００）５ｇ、分散剤０．８３ｇ、ガラ
スビーズ１５ｇ、水１９．１７ｇを用いて、実験例１と
同様にして、平均粒径約２μｍの分散液を得た。上記分
散液を、水で、１０ｗｔ％に希釈し、Ｂ４サイズの上質
紙（坪量６０ｇ／ｍ2 ）の表面に、メイヤーバー＃１０
で塗布し、１７０℃で３分間乾燥させ、片面塗布紙を作
製した。乾燥後の塗布量は２．９ｇ／ｍ2 であった。こ
のポリマー塗布紙を、実験例１と同様に試験したとこ
ろ、ポリマー塗布紙は引き裂けなかった。また、コンポ
スト水抽出菌液中での分解性試験では、約３週間で完全
分解した。Experimental Example 3 An experiment was conducted using 5 g of a 1: 1 copolymer of pulverized L-lactic acid and glyco-acrylic acid (MW = 30,000), 0.83 g of a dispersant, 15 g of glass beads, and 19.17 g of water. In the same manner as in Example 1, a dispersion having an average particle size of about 2 μm was obtained. The dispersion liquid was diluted with water to 10 wt%, and was applied to the surface of a B4 size fine paper (basis weight 60 g / m 2 ) on a Mayer bar # 10.
Was applied and dried at 170 ° C. for 3 minutes to prepare a single-sided coated paper. The coating amount after drying was 2.9 g / m 2 . When this polymer-coated paper was tested in the same manner as in Experimental Example 1, the polymer-coated paper did not tear. Further, in the degradability test in the compost water-extracted bacterial solution, it was completely degraded in about 3 weeks.
【００１６】実験例４ 粉砕したＬ−乳酸と６−ヒドロキシカプロン酸の１：１
のコポリマ−（ＭＷ＝３０，０００）５ｇ、分散剤０．
８３ｇ、ガラスビーズ１５ｇ、水１９．１７ｇを用い
て、実験例１と同様にして、平均粒径約３μｍの分散液
を得た。上記分散液を、水で、１０ｗｔ％に希釈し、Ｂ
４サイズの上質紙（坪量６０ｇ／ｍ2 ）の表面に、メイ
ヤーバー＃１０で塗布し、１７０℃で３分間乾燥させ、
片面塗布紙を作製した。乾燥後の塗布量は３．１ｇ／ｍ
2 であった。このポリマー塗布紙を、実験例１と同様に
試験したところ、ポリマー塗布紙は引き裂けなかった。
また、コンポスト水抽出菌液中での分解性試験では約３
週間で完全分解した。Experimental Example 4 1: 1 of ground L-lactic acid and 6-hydroxycaproic acid
Copolymer (MW = 30,000) 5 g, dispersant 0.
A dispersion having an average particle size of about 3 μm was obtained in the same manner as in Experimental Example 1 using 83 g, 15 g of glass beads, and 19.17 g of water. The above dispersion liquid was diluted to 10 wt% with water, and B
Apply to the surface of 4 size fine paper (basis weight 60 g / m 2 ) with Meyer bar # 10 and dry at 170 ° C. for 3 minutes,
A single-sided coated paper was prepared. The applied amount after drying is 3.1 g / m.
Was 2 . When this polymer-coated paper was tested in the same manner as in Experimental Example 1, the polymer-coated paper did not tear.
In addition, it was about 3 in the degradability test in the compost aqueous extract.
Completely decomposed in a week.
【００１７】実験例５ 粉砕したＬ−乳酸のポリマ−（ＭＷ＝１５０，０００）
５ｇ、分散剤０．８３ｇ、ガラスビーズ１５ｇ、水１
９．１７ｇを用いて、実験例１と同様にして、分散液を
得た。しかし、この分散液のポリマーの平均粒径は約６
０μｍであった。上記分散液を、水で、１０ｗｔ％に希
釈し、Ｂ４サイズの上質紙（坪量６０ｇ／ｍ2 ）の表面
に、メイヤーバー＃１０で塗布したところ、分散液がザ
ラ付き、均一な塗布面が得られなかった。Experimental Example 5 Ground L-lactic acid polymer (MW = 150,000)
5 g, dispersant 0.83 g, glass beads 15 g, water 1
A dispersion was obtained in the same manner as in Experimental Example 1 using 9.17 g. However, the average particle size of the polymer in this dispersion is about 6
It was 0 μm. The dispersion was diluted to 10 wt% with water and applied to a B4 size wood free paper (basis weight 60 g / m 2 ) with Meyer bar # 10. Was not obtained.
【００１８】実験例６ １５ｃｍ×１５ｃｍの上質紙（坪量６０ｇ／ｍ2 ）の表
面に、接着剤として、３０％ゼラチンを塗布し、Ｌ−乳
酸のポリマー（ＭＷ＝１００，０００）から得られた厚
み４０μｍのフィルムを重ね合わせ、１ｋｇ／ｃｍ2 の
圧力で、一晩圧着しラミネート紙を得た。このラミネー
ト紙について、実験例１と同様に試験したところ、この
ラミネート紙は水面に浮き、全く透水性の無いものであ
った。Experimental Example 6 Obtained from a polymer of L-lactic acid (MW = 100,000) by coating 30% gelatin as an adhesive on the surface of a 15 cm × 15 cm high-quality paper (basis weight 60 g / m 2 ). Films having a thickness of 40 μm were superposed and pressure-bonded overnight at a pressure of 1 kg / cm 2 to obtain a laminated paper. When this laminated paper was tested in the same manner as in Experimental Example 1, the laminated paper floated on the water surface and had no water permeability.
【００１９】実験例７ 実験例１〜６で使用した未処理紙について、同様にし
て、その湿潤強度を試験したところ、容易に引き裂け
た。また、コンポスト水抽出菌液中での分解性試験で
は、２週間以内に完全分解した。Experimental Example 7 The untreated papers used in Experimental Examples 1 to 6 were tested for wet strength in the same manner, and they were easily torn. Moreover, in the degradability test in the compost aqueous extract, complete decomposition occurred within 2 weeks.
【００２０】[0020]
【発明の効果】分解性ポリマー微粒子の分散液を、セル
ロース繊維を含有する基材に塗布し、加熱乾燥する本発
明の方法を用いることにより、強度と透水性に優れた分
解性複合材料を、工業的に有利に製造することができ
る。EFFECT OF THE INVENTION By using the method of the present invention in which a dispersion of degradable polymer particles is applied to a substrate containing cellulose fibers and dried by heating, a degradable composite material excellent in strength and water permeability can be obtained. It can be manufactured industrially advantageously.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山口 彰宏 神奈川県横浜市栄区笠間町1190番地 三井 東圧化学株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akihiro Yamaguchi 1190 Kasama-cho, Sakae-ku, Yokohama-shi, Kanagawa Mitsui Toatsu Chemical Co., Ltd.
Claims (5)
ン酸のコポリマーを主成分とする分解性ポリマーの分散
液を、セルロース繊維を含有する基材に塗布した後、加
熱処理することを特徴とする分解性複合材料の製造方
法。1. A method of applying a dispersion liquid of polylactic acid or a degradable polymer containing a copolymer of lactic acid and oxycarboxylic acid as a main component to a base material containing cellulose fibers and then heat-treating the base material. Manufacturing method of degradable composite material.
れらの混合物である請求項１記載の製造方法。2. The production method according to claim 1, wherein the lactic acid is D-lactic acid, L-lactic acid, or a mixture thereof.
たは６−ヒドロキシカプロン酸である請求項１記載の製
造方法。3. The production method according to claim 1, wherein the oxycarboxylic acid is glycolic acid or 6-hydroxycaproic acid.
０，０００以下である請求項１記載の製造方法。4. The weight average molecular weight of the degradable polymer is 5
The production method according to claim 1, which is not more than 10,000.
ン酸のコポリマーを主成分とする分解性ポリマーの分散
液を、セルロース繊維を含有する基材に塗布して、基材
の分解速度を遅らせる方法。5. A method of delaying the decomposition rate of a base material by applying a dispersion liquid of a degradable polymer containing polylactic acid or a copolymer of lactic acid and oxycarboxylic acid as a main component to a base material containing cellulose fibers. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16718094A JP3494474B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing degradable composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16718094A JP3494474B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing degradable composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0827280A true JPH0827280A (en) | 1996-01-30 |
| JP3494474B2 JP3494474B2 (en) | 2004-02-09 |
Family
ID=15844913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16718094A Expired - Lifetime JP3494474B2 (en) | 1994-07-19 | 1994-07-19 | Method for producing degradable composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3494474B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
-
1994
- 1994-07-19 JP JP16718094A patent/JP3494474B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103044871A (en) * | 2012-11-26 | 2013-04-17 | 浙江大学宁波理工学院 | Preparation method of polylactic acid/nano-cellulose composite material |
| CN103044871B (en) * | 2012-11-26 | 2015-08-26 | 浙江大学宁波理工学院 | A kind of preparation method of polylactic acid/nano-cellulose composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3494474B2 (en) | 2004-02-09 |
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