JPH11309368A - Composition containing inorganic porous crystal-hydrophilic polymer composite body and its molded product - Google Patents
Composition containing inorganic porous crystal-hydrophilic polymer composite body and its molded productInfo
- Publication number
- JPH11309368A JPH11309368A JP4723599A JP4723599A JPH11309368A JP H11309368 A JPH11309368 A JP H11309368A JP 4723599 A JP4723599 A JP 4723599A JP 4723599 A JP4723599 A JP 4723599A JP H11309368 A JPH11309368 A JP H11309368A
- Authority
- JP
- Japan
- Prior art keywords
- inorganic porous
- hydrophilic polymer
- cellulose
- porous crystal
- composition
- 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
Classifications
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
- A46D1/006—Antimicrobial, disinfectant bristles, handle, bristle-carrier or packaging
-
- A—HUMAN NECESSITIES
- A46—BRUSHWARE
- A46D—MANUFACTURE OF BRUSHES
- A46D1/00—Bristles; Selection of materials for bristles
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、悪臭除去、ガス吸
着等の性質、さらには抗菌性、難燃性、保温性等を有
し、且つ強度、その他の特性に優れた、親水性高分子が
その実体内に無機多孔結晶を有する無機多孔結晶−親水
性高分子複合体と固化しうる担体とを含有する組成物お
よびその成形物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hydrophilic polymer having properties such as offensive odor removal and gas adsorption, as well as antibacterial properties, flame retardancy, heat retention, etc., and excellent strength and other properties. The present invention relates to a composition comprising an inorganic porous crystal-hydrophilic polymer composite having an inorganic porous crystal in its body and a solidifiable carrier, and a molded product thereof.
【０００２】[0002]
【従来の技術】ゼオライトやアルミノシリカゲル等の無
機化合物を、紙等のセルロース基材を始めとする親水性
高分子に担持させて機能性を付与した素材が知られてい
る。かかる素材は悪臭除去、ガス吸着等の性質や抗菌
性、難燃性、保温性を有するので種々の用途に使用しえ
るものである。2. Description of the Related Art There is known a material in which an inorganic compound such as zeolite or alumino-silica gel is supported on a hydrophilic polymer such as a cellulose substrate such as paper to impart functionality. Such a material has properties such as offensive odor removal and gas adsorption, antibacterial properties, flame retardancy, and heat retention, so that it can be used for various applications.
【０００３】[0003]
【発明が解決しようとする課題】上記素材は、様々な用
途展開が期待できるが、実際に消費者が求める用途によ
り、より高強度なもの等、種々の機能性を高めたものが
要求されている。本発明の目的はかかる要求に応える素
材を提供することであり、親水性高分子がその実体内に
無機多孔結晶を有する無機多孔結晶−親水性高分子複合
体の有する悪臭除去、ガス吸着等の性質や抗菌性、難燃
性、保温性に加えて、更に機能性を高めたものを提供す
ることにある。The above-mentioned materials can be expected to be used in various applications. However, depending on the applications actually demanded by consumers, materials having higher functions such as higher strength are required. I have. An object of the present invention is to provide a material that meets such demands, wherein the hydrophilic polymer has an inorganic porous crystal having an inorganic porous crystal in its body. Another object of the present invention is to provide a product having enhanced functionality in addition to antibacterial properties, flame retardancy, and heat retention.
【０００４】[0004]
【課題を解決するための手段】かかる目的は下記の本発
明によって解決される。すなわち、本発明は下記の通り
である。 （１）親水性高分子がその実体内に無機多孔結晶を有す
る無機多孔結晶−親水性高分子複合体と固化しうる担体
とを含有する組成物。 （２）無機多孔結晶がゼオライトであることを特徴とす
る上記（１）記載の組成物。 （３）無機多孔結晶が銀、銅、亜鉛、鉄、ニッケル、コ
バルト、パラジウムおよび白金からなる群より選択され
る少なくとも１種の金属を担持することを特徴とする上
記（１）または（２）記載の組成物。 （４）親水性高分子が天然セルロース、再生セルロー
ス、バクテリアセルロース、化学修飾セルロース、絹、
羊毛、ポリアクリルアミド、ポリビニルアルコール、架
橋型ポリビニルアルコール、キチン、キトサン、エチレ
ン酢酸ビニルコポリマーおよびポリビニルホルマールか
らなる群より選ばれる少なくとも１種からなることを特
徴とする 上記（１）記載の組成物。 （５）天然セルロースがパルプ、木綿、麻およびケナフ
からなる群より選ばれる少なくとも１種である上記
（４）記載の組成物。 （６）化学修飾セルロースがエチルセルロース、ヒドロ
キシエチルセルロース、ヒドロキシプロピルセルロー
ス、メチルセルロース、エチルヒドロキシエチルセルロ
ースおよびカルボキシメチルセルロースからなる群より
選ばれる少なくとも１種である上記（４）記載の組成
物。 （７）上記（１）〜（６）のいずれかに記載の組成物を
固化してなる成形物。This object is solved by the present invention described below. That is, the present invention is as follows. (1) A composition containing an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in its body and a solidifiable carrier. (2) The composition according to the above (1), wherein the inorganic porous crystal is zeolite. (3) The above (1) or (2), wherein the inorganic porous crystal carries at least one metal selected from the group consisting of silver, copper, zinc, iron, nickel, cobalt, palladium and platinum. A composition as described. (4) When the hydrophilic polymer is natural cellulose, regenerated cellulose, bacterial cellulose, chemically modified cellulose, silk,
The composition according to (1), comprising at least one selected from the group consisting of wool, polyacrylamide, polyvinyl alcohol, cross-linked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer, and polyvinyl formal. (5) The composition according to the above (4), wherein the natural cellulose is at least one selected from the group consisting of pulp, cotton, hemp and kenaf. (6) The composition according to the above (4), wherein the chemically modified cellulose is at least one selected from the group consisting of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose. (7) A molded product obtained by solidifying the composition according to any one of (1) to (6).
【０００５】本発明に用いられる固化しうる担体として
は、親水性高分子がその実体内に無機多孔結晶を有する
無機多孔結晶−親水性高分子複合体を当該担体に配合し
た後、何らかの手段で固化することができるものであれ
ば特に制限はなく、固化の手段としては、例えば加熱、
冷却、圧縮、化学反応（例えば、酸化反応、酵素反応
等）等が挙げられる。また、固化の程度は少なくとも成
形物を得ることができる程度であればよく、当該成形物
は可撓性を有するもの、変形しうるものであってもよ
い。かかる担体としては、例えば樹脂、無機系硬化剤等
が挙げられる。当該樹脂としては、天然樹脂、合成樹脂
またはこれらをブレンドした樹脂等が挙げられる。具体
的に、天然樹脂としては、松ヤニ、セラック、ワック
ス、コラーゲン、プロポリス、漆、木粉等が挙げられ
る。合成樹脂としては、例えば、ポリエチレン、ポリプ
ロピレン等のポリオレフィン、ポリアクリルアミド等の
ポリアミド、ポリビニルアルコール、ブタジエンゴム、
シリコーンゴム、フェノール樹脂等が挙げられる。好ま
しくは、価格、低沸点、汎用性の点から、ポリエチレン
である。天然樹脂および合成樹脂のブレンドは、自体公
知の方法により得られる。担体として樹脂を使用した組
成物の態様としては、例えば塗料等の流動体が、それを
固化したものとして、ゴム状の可撓体、ボード状物、シ
ート状物、ヒモ状物、網状物、クッション状物等が挙げ
られる。無機系硬化剤としては、例えば、セメント、石
膏、炭酸カルシウム、ケイ酸カルシウム、二酸化チタ
ン、ゼオライト、粘度鉱物、コロイダルシリカ、アパタ
イトまたはタルサイト様化合物等が挙げられる。また、
無機系硬化剤を含む組成物の固化後の形状には特に制限
はなく、例えば球状、立方体状、柱状、板状等の様々な
形状を挙げることができる。[0005] As a solidifiable carrier used in the present invention, an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in the substance is mixed with the carrier and then solidified by some means. There is no particular limitation as long as the solidification can be performed.
Cooling, compression, chemical reaction (for example, oxidation reaction, enzyme reaction, etc.) and the like can be mentioned. The degree of solidification may be at least such that a molded product can be obtained, and the molded product may be flexible or deformable. Examples of such a carrier include a resin and an inorganic curing agent. Examples of the resin include a natural resin, a synthetic resin, and a resin obtained by blending them. Specifically, examples of the natural resin include pine tar, shellac, wax, collagen, propolis, lacquer, and wood powder. As synthetic resins, for example, polyethylene, polyolefins such as polypropylene, polyamides such as polyacrylamide, polyvinyl alcohol, butadiene rubber,
Examples include silicone rubber and phenolic resin. Preferably, polyethylene is used in terms of price, low boiling point, and versatility. A blend of a natural resin and a synthetic resin can be obtained by a method known per se. As an embodiment of the composition using a resin as a carrier, for example, a fluid such as a paint, as a solidified product thereof, a rubber-like flexible body, a board-like substance, a sheet-like substance, a string-like substance, a net-like substance, Cushion-like materials are exemplified. Examples of the inorganic hardener include cement, gypsum, calcium carbonate, calcium silicate, titanium dioxide, zeolite, viscous mineral, colloidal silica, apatite, and talcite-like compound. Also,
The shape of the composition containing the inorganic curing agent after solidification is not particularly limited, and examples thereof include various shapes such as a sphere, a cube, a column, and a plate.
【０００６】本発明に用いられる無機多孔結晶−親水性
高分子複合体の無機多孔結晶としては、イオン交換能を
有する無機イオン交換体結晶および多孔部分に吸着能を
有する吸着体結晶が挙げられ、親水性高分子基材を溶
解、分解または崩壊させないものであれば特に制限はな
い。例えば、ゼオライト、ハイドロタルサイト、ハイド
ロキシアパタイト、粘土鉱物類等が挙げられる。中で
も、最も用途が広いという点からゼオライトが好まし
く、その中でも比較的合成が容易であるという点から４
Ａゼオライト〔Ｎａ12Ｓｉ12Ａｌ12Ｏ48・２７Ｈ2 Ｏ〕
が特に好ましい。Examples of the inorganic porous crystal of the inorganic porous crystal-hydrophilic polymer composite used in the present invention include an inorganic ion exchanger crystal having an ion exchange ability and an adsorbent crystal having an adsorption ability in a porous portion. There is no particular limitation as long as it does not dissolve, decompose or disintegrate the hydrophilic polymer substrate. Examples include zeolite, hydrotalcite, hydroxyapatite, clay minerals and the like. Among them, zeolites are preferred in that they are most versatile, and among them, zeolites are preferred because they are relatively easy to synthesize.
A zeolite [Na 12 Si 12 Al 12 O 48 · 27H 2 O ]
Is particularly preferred.
【０００７】本発明に用いられる無機多孔結晶−親水性
高分子複合体の親水性高分子としては、水に対して膨潤
するものであれば特に制限はない。例えば、天然セルロ
ース（パルプ、ケナフ、木綿、麻）、再生セルロース
（セロファン、セルロースビーズ、レーヨン、セルロー
ススポンジ等）、バクテリアセルロースおよびセルロー
スを化学修飾したエチルセルロース、ヒドロキシエチル
セルロース、ヒドロキシプロピルセルロース、メチルセ
ルロース、エチルヒドロキシエチルセルロースおよびカ
ルボキシメチルセルロース等のセルロース誘導体、更に
は絹、羊毛、麻、ポリビニルアルコール、架橋型ポリビ
ニルアルコール、キチン、キトサン、エチレン酢酸ビニ
ルコポリマー、ポリビニルホルマール等の天然、或いは
人工の親水性高分子、ポリアクリルアミド等の高吸水性
高分子ゲル、コラーゲン、プロポリス、漆、木粉等が挙
げられる。中でも、実際の使用形態、価格および取り扱
い易さの点からパルプや再生セルロースが担持用基材と
して好ましく使用される。The hydrophilic polymer of the inorganic porous crystal-hydrophilic polymer composite used in the present invention is not particularly limited as long as it swells in water. For example, natural cellulose (pulp, kenaf, cotton, hemp), regenerated cellulose (cellophane, cellulose beads, rayon, cellulose sponge, etc.), bacterial cellulose and ethyl cellulose obtained by chemically modifying cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxy Cellulose derivatives such as ethylcellulose and carboxymethylcellulose, and natural or artificial hydrophilic polymers such as silk, wool, hemp, polyvinyl alcohol, cross-linked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer, polyvinyl formal, and polyacrylamide And high-water-absorbing polymer gels such as collagen, propolis, lacquer, and wood powder. Above all, pulp and regenerated cellulose are preferably used as the supporting base material in terms of actual use form, price and ease of handling.
【０００８】上記の親水性高分子の実体内に無機多孔結
晶が担持され、本発明に用いられる無機多孔結晶−親水
性高分子複合体を形成する。ここで、親水性高分子の実
体内とは、例えば、親水性高分子がセルロースの場合、
セルロース基材を構成している高分子物質の内部を意味
し、例えば、セルロース基材の細胞壁表面、細胞壁内に
存在する細孔および細胞内腔（ルーメン）は含まれな
い。セルロース基材の実体内に無機多孔結晶を有すると
は、無機多孔結晶の一部または全部がセルロース基材の
実体内に存在することを意味する。[0008] Inorganic porous crystals are supported in the body of the above-mentioned hydrophilic polymer to form an inorganic porous crystal-hydrophilic polymer composite used in the present invention. Here, the entity of the hydrophilic polymer is, for example, when the hydrophilic polymer is cellulose,
It means the inside of the polymer material constituting the cellulose substrate, and does not include, for example, the cell wall surface of the cellulose substrate, pores existing in the cell wall, and cell lumen (lumen). Having inorganic porous crystals in the body of the cellulose substrate means that some or all of the inorganic porous crystals are present in the body of the cellulose substrate.
【０００９】当該無機多孔結晶−親水性高分子複合体は
以下のようにして製造される。例えば、無機多孔結晶が
ゼオライトであり、親水性高分子がセルロースであるゼ
オライト−セルロース複合体である場合、特願平８−２
４５５３８号記載の方法（具体的には、１．０〜１００
ｍｍｏｌ／ｌのケイ素化合物の水溶液を１０分〜２時間
含浸させたセルロース基材に、２０〜９０℃で１．０〜
１０００ｍｍｏｌ／ｌのアルミニウム化合物および１０
〜５０００ｍｍｏｌ／ｌの塩基性物質の混合水溶液に２
時間〜２０日間浸漬させる方法等）が挙げられる。親水
性高分子がパルプまたはレーヨンである場合、上記と同
様の方法によって、無機多孔結晶−パルプ複合体、無機
多孔結晶−セロハン複合体、無機多孔結晶−レーヨン複
合体を得ることができる。無機多孔結晶−親水性高分子
複合体中の無機多孔結晶と親水性高分子の割合は特に限
定されないが、好ましくは該複合体中無機多孔結晶が
１．０〜７０．０重量％、特に好ましくは１０．０〜５
０．０重量％である。The inorganic porous crystal-hydrophilic polymer composite is produced as follows. For example, when the inorganic porous crystal is a zeolite and the hydrophilic polymer is a zeolite-cellulose composite in which the hydrophilic polymer is cellulose, Japanese Patent Application No. Hei.
No. 45538 (specifically, from 1.0 to 100).
A cellulose substrate impregnated with an aqueous solution of a silicon compound of 10 mmol / l for 10 minutes to 2 hours was added at 20 to 90 ° C. for 1.0 to 1.0 μm.
1000 mmol / l aluminum compound and 10
2 to a mixed aqueous solution of ~ 5000 mmol / l basic substance
For 20 hours to 20 days. When the hydrophilic polymer is pulp or rayon, an inorganic porous crystal-pulp composite, an inorganic porous crystal-cellophane composite, and an inorganic porous crystal-rayon composite can be obtained by the same method as described above. The ratio between the inorganic porous crystal and the hydrophilic polymer in the inorganic porous crystal-hydrophilic polymer composite is not particularly limited, but the inorganic porous crystal in the composite is preferably 1.0 to 70.0% by weight, particularly preferably. Is 10.0-5
0.0% by weight.
【００１０】当該無機多孔結晶−親水性高分子複合体を
触媒機能を有する金属塩の水溶液に浸漬することによ
り、金属担持無機多孔結晶−親水性高分子複合体が得ら
れる。使用される金属としては、例えば、銀、銅、亜
鉛、鉄、ニッケル、コバルト、パラジウムおよび白金等
が挙げられ、これらの金属を複数併用してもよい。金属
塩の水溶液の濃度に特に制限はないが、好ましくは１．
０〜１００ｍｍｏｌ／ｌであり、浸漬する温度や時間に
も特に制限はない。この時、親水性高分子基材は水溶液
を浸透させうるので、親水性高分子基材の実体内の無機
多孔結晶全体に無駄なく金属を担持させることができ
る。金属担持無機多孔結晶−親水性高分子複合体中の金
属の量も特に限定されないが、好ましくは該複合体中
０．００１〜１０．０重量％、特に好ましくは０．０１
〜１．０重量％である。By immersing the inorganic porous crystal-hydrophilic polymer composite in an aqueous solution of a metal salt having a catalytic function, a metal-supported inorganic porous crystal-hydrophilic polymer composite can be obtained. Examples of the metal used include silver, copper, zinc, iron, nickel, cobalt, palladium, platinum, and the like, and a plurality of these metals may be used in combination. The concentration of the aqueous solution of the metal salt is not particularly limited, but is preferably 1.
It is 0 to 100 mmol / l, and there is no particular limitation on the temperature and time for immersion. At this time, since the aqueous solution of the hydrophilic polymer base material can permeate the aqueous solution, the metal can be carried on the entire inorganic porous crystal in the body of the hydrophilic polymer base material without waste. The amount of the metal in the metal-supported inorganic porous crystal-hydrophilic polymer composite is also not particularly limited, but is preferably 0.001 to 10.0% by weight, particularly preferably 0.01% by weight in the composite.
~ 1.0% by weight.
【００１１】例えば、銀、銅または亜鉛を担持させた無
機多孔結晶−親水性高分子複合体は抗菌性を示し、パラ
ジウムまたは白金を担持させた無機多孔結晶−親水性高
分子複合体はエチレンを吸着することができることか
ら、青果物の鮮度を保持する効果があり、銀または銅を
担持させた無機多孔結晶−親水性高分子複合体は、硫化
水素を吸着、分解できることから金属の防錆効果または
脱臭効果が、またアンモニアを吸着、分解できることか
ら防臭効果がある。また、銀を担持させた無機多孔結晶
−親水性高分子複合体はメチルメルカプタンを吸着、分
解できることから防臭効果がある。この時、親水性高分
子は気体を充分に透過させうるので、親水性高分子の実
体内の金属担持無機多孔結晶全体を無駄なく利用して、
気体を吸着、分解することができる。For example, an inorganic porous crystal-hydrophilic polymer composite carrying silver, copper or zinc exhibits antibacterial properties, and an inorganic porous crystal-hydrophilic polymer composite carrying palladium or platinum contains ethylene. Since it can be adsorbed, it has the effect of maintaining the freshness of fruits and vegetables, and the inorganic porous crystal-hydrophilic polymer composite carrying silver or copper can adsorb and decompose hydrogen sulfide, and thus has the rust-preventive effect of metals or It has a deodorizing effect and has an anti-odor effect because it can adsorb and decompose ammonia. In addition, the inorganic porous crystal-hydrophilic polymer composite carrying silver can adsorb and decompose methyl mercaptan, and thus has an odor preventing effect. At this time, since the hydrophilic polymer can sufficiently permeate the gas, the entirety of the metal-supported inorganic porous crystal in the entity of the hydrophilic polymer is used without waste,
Gas can be adsorbed and decomposed.
【００１２】本発明の組成物は、固化しうる担体中に親
水性高分子がその実体内に無機多孔結晶を有する無機多
孔結晶−親水性高分子複合体を添加することによって製
造される。例えば、塗料等の流動性のものは、製造時は
流動体であるが、これを被着体に塗布した後、皮膜形成
して成型物とされる。例えば、アクリル樹脂を配合した
塗料は、塗料の状態ではエマルジョンであるが、水分が
蒸発することによって皮膜を形成する。また、エポキシ
樹脂を配合した塗料は化学反応によって固化して成型物
とされる。当該成型物の厚さは１０〜５００μｍ、好ま
しくは２０〜１００μｍ程度である。無機系硬化剤を用
いて固化した成型物の厚さは、１〜１０ｃｍ程度であ
る。また成型物が球状の場合は、直径あるいは楕円の場
合は長径が０．１〜５ｃｍ、好ましくは０．５〜２ｃｍ
である。The composition of the present invention is produced by adding an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in its body to a solidifiable carrier. For example, a fluid material such as a paint is a fluid at the time of manufacture, but is applied to an adherend and then formed into a film to form a molded product. For example, a paint containing an acrylic resin is an emulsion in a paint state, but forms a film by evaporation of water. Further, the paint containing the epoxy resin is solidified by a chemical reaction to form a molded product. The thickness of the molded product is about 10 to 500 μm, preferably about 20 to 100 μm. The thickness of the molded product solidified using the inorganic curing agent is about 1 to 10 cm. When the molded product is spherical, the major axis is 0.1 to 5 cm, preferably 0.5 to 2 cm in the case of a diameter or an ellipse.
It is.
【００１３】以下、本発明の組成物を固化して得られる
成型物および本発明の組成物（流動体の態様）の製造方
法をより具体的な例を挙げて詳細に説明する。・固化し
て得られる成型物の製法 ａ．プラスチック系 ポリエチレンマスターバッチにゼオライト担持セルロー
スビーズを加え、１３０℃に設定したニーダーで混練す
る。混練したものを押し出し成型器に充填し、冷却させ
ることによって固化する。 ｂ．セメント系 市販のセメントを水に溶かし、これに二酸化チタン粉末
を加え混練した後に、ゼオライト担持パルプを加え、更
に混練する。型枠に入れ、ケイ酸カルシウム水和物の生
成によってボード状に固化する。 ｃ．皮膜系 アクリル樹脂またはメタクリル樹脂塗料にゼオライト担
持セルロースビーズを分散させ攪拌する。これを刷毛ま
たはロールによって石膏ボード、プラスチックボードに
塗工した後、水分が蒸発し皮膜ができることによって固
化する。 ｄ．ファイバーボード系 製材所等から得られる木粉とポリビニルアルコール系の
糊を混ぜ、これにゼオライト担持パルプを混練する。型
枠に入れ、圧力をかけ乾燥させることによって固化す
る。Hereinafter, a method for producing a molded product obtained by solidifying the composition of the present invention and a composition (an embodiment of a fluid) of the present invention will be described in more detail with reference to more specific examples. -Method for producing a molded product obtained by solidification a. Zeolite-supported cellulose beads are added to a plastic polyethylene master batch, and kneaded with a kneader set at 130 ° C. The kneaded material is filled in an extruder and solidified by cooling. b. Cement type Commercially available cement is dissolved in water, titanium dioxide powder is added and kneaded, and then zeolite-supporting pulp is added and further kneaded. It is placed in a mold and solidified into a board by the formation of calcium silicate hydrate. c. Film type Zeolite-supported cellulose beads are dispersed in an acrylic resin or methacrylic resin paint and stirred. After this is applied to a gypsum board or a plastic board by a brush or a roll, the water is evaporated and the film is solidified. d. Fiberboard-based wood flour obtained from a sawmill or the like and polyvinyl alcohol-based paste are mixed, and the pulp carrying zeolite is kneaded. It is placed in a mold and solidified by drying under pressure.
【００１４】・塗料等の流動体を得る製法 ａ．増粘剤系 カルボキシメチルセルロースを水に分散させ混練し、適
度な粘度（Ｂ型粘度計で測定した粘度が１０万〜１００
万センチポイズ程度）がでたところでゼオライト担持セ
ルロースビーズを加え、更に混練する。 ｂ．ポリビニルアルコール糊系 ポリビニルアルコールを６０℃程度の湯に分散させ、適
度な粘度（Ｂ型粘度計で測定した粘度が１万〜１０万セ
ンチポイズ程度）がでたところでゼオライト担持セルロ
ースビーズを加え、更に混練する。 ｃ．塗料系 亜鉛鉄板用塗料、亜鉛末錆止めペイント、アクリル樹脂
塗料、亜酸化鉛錆止めペイント、アセチルセルロース透
明ドープ、油ワニス、アミノアルキド樹脂塗料、アルキ
ド樹脂塗料、アルミニウムペイント、一般錆止め様ペイ
ント、ウッドシーラー、上塗り塗料、エッチングプライ
マー、エナメル銅線用ワニス、エナメルペイント、エマ
ルションペイント、オイルプライマー、カシュー樹脂塗
料、カビ防止塗料、揮発性ワニス、クリアラッカー蛍光
塗料、合成樹脂エマルションペイント、合成樹脂塗料、
シリコーン樹脂塗料、白ラックワニス、水性塗料、精製
漆、セラックニス、スーパーワニス、セルロースラッカ
ー、ニトロセルロースラッカー、フェノール樹脂塗料、
フタル酸樹脂塗料、不飽和ポリエステル樹脂塗料、メラ
ミン樹脂塗料等の塗料にゼオライト担持セルロースビー
ズを混練する。A method for obtaining a fluid such as a paint a. Thickener system Carboxymethylcellulose is dispersed in water and kneaded, and has an appropriate viscosity (viscosity of 100,000 to 100 measured with a B-type viscometer).
When about 10,000 centipoise comes out, the cellulose beads carrying zeolite are added and kneaded. b. Polyvinyl alcohol paste system Polyvinyl alcohol is dispersed in hot water of about 60 ° C., and when appropriate viscosity (viscosity measured by a B-type viscometer is about 10,000 to 100,000 centipoise) is added, cellulose beads carrying zeolite are added, and further kneading is performed. I do. c. Paint system Zinc iron plate paint, zinc dust rust preventive paint, acrylic resin paint, lead suboxide rust preventive paint, acetyl cellulose transparent dope, oil varnish, amino alkyd resin paint, alkyd resin paint, aluminum paint, general rust preventive paint, wood sealer, Topcoat paint, etching primer, varnish for enameled copper wire, enamel paint, emulsion paint, oil primer, cashew resin paint, anti-mold paint, volatile varnish, clear lacquer fluorescent paint, synthetic resin emulsion paint, synthetic resin paint,
Silicone resin paint, white lac varnish, water-based paint, purified lacquer, shellac varnish, super varnish, cellulose lacquer, nitrocellulose lacquer, phenolic resin paint,
Zeolite-supported cellulose beads are kneaded with a paint such as a phthalic acid resin paint, an unsaturated polyester resin paint, or a melamine resin paint.
【００１５】添加する無機多孔結晶−親水性高分子複合
体の割合は、固化しうる担体１００重量部に対し、１〜
６０重量部程度である。また、必要に応じて当該樹脂ま
たは無機系硬化剤には、界面活性剤、可塑剤、酸化防止
剤、分散剤、沈殿防止剤、ウッドフィラー、オイルステ
イン等の塗料補助剤を添加することができる。The ratio of the inorganic porous crystal-hydrophilic polymer composite to be added is 1 to 100 parts by weight of the solidifiable carrier.
It is about 60 parts by weight. If necessary, a coating aid such as a surfactant, a plasticizer, an antioxidant, a dispersant, a suspending agent, a wood filler, and an oil stain can be added to the resin or the inorganic curing agent. .
【００１６】本発明の組成物は、固化しうる担体中に親
水性高分子がその実体内に無機多孔結晶を有する無機多
孔結晶−親水性高分子複合体を添加することによって得
られ、無機多孔結晶−親水性高分子複合体の有するガス
吸着能、揮発性有機溶剤除去能、難燃性、保温性、重金
属および放射性元素除去能に加えて、固化させることに
よりその成型物は一般的に高強度となる。更に使用する
担体に応じて成型物は手触り等の触感、強度、親水性、
撥水性、防錆性等を改善することができる。当該成型物
は、例えば、肌着、足拭きマット、シーツ、手袋、枕カ
バー、枕・布団・ちゃんちゃんこ・クッション等の中
綿、障子紙、壁紙、衣装カバー、クッションカバー、布
団収納袋等に使用することができ、また防虫シート、掃
除機用パック、エアコンフィルター、空気清浄機用フィ
ルター、食器用束子、水切りゴミ袋、カーペット、ホッ
トカーペットカバー、カーテン、冷蔵庫用脱臭シート、
特殊濾紙、野菜・肉等の鮮度保存シート、鮮度保持輸送
用包装材料、壁材、床材、天井材、結露吸水シート等の
様々な用途に使用することができる。また、組成物自体
は塗料等として使用される。The composition of the present invention is obtained by adding an inorganic porous crystal-hydrophilic polymer composite having an inorganic porous crystal in a solidified carrier to a carrier capable of being solidified. -In addition to the gas adsorption ability, volatile organic solvent removal ability, flame retardancy, heat retention, heavy metal and radioactive element removal ability of the hydrophilic polymer composite, the molded product generally has high strength Becomes Further, depending on the carrier used, the molded product has a tactile sensation such as touch, strength, hydrophilicity,
Water repellency, rust prevention and the like can be improved. The molded product is used, for example, for underwear, foot wipe mats, sheets, gloves, pillowcases, batting, pillows, futons, chanchanko, cushions, etc., shoji paper, wallpaper, costume covers, cushion covers, futon storage bags, etc. Can also have insect repellent sheets, vacuum cleaner packs, air conditioner filters, air purifier filters, tableware bundles, drain garbage bags, carpets, hot carpet covers, curtains, deodorizing sheets for refrigerators,
It can be used for various applications such as special filter paper, freshness preserving sheet for vegetables and meat, packaging material for freshness preserving transportation, wall material, flooring material, ceiling material, dew condensation water absorbing sheet and the like. The composition itself is used as a paint or the like.
【００１７】特に、本発明の組成物に用いられる無機多
孔結晶−親水性高分子複合体に銀、銅または亜鉛等の金
属を担持させた金属担持無機多孔結晶−親水性高分子複
合体を用いることによって、上記の性質に加えて更に抗
菌性および悪臭除去能等の性質を付与することができ
る。従って、紙おむつ、おむつカバー、自動車用携帯ト
イレ、靴中敷き、人工皮革、自動車・列車・飛行機・船
舶等の内装（座席シート、シートカバー）、タオル、ト
イレ便座カバー等の様々な用途にも使用することができ
る。In particular, a metal-supported inorganic porous crystal-hydrophilic polymer composite in which a metal such as silver, copper, or zinc is supported on the inorganic porous crystal-hydrophilic polymer composite used in the composition of the present invention is used. Thereby, in addition to the above properties, properties such as antibacterial property and odor removing ability can be further provided. Therefore, it is also used for various uses such as disposable diapers, diaper covers, portable toilets for automobiles, insoles, artificial leather, interiors (seat seats, seat covers) of automobiles, trains, airplanes and ships, towels, toilet seat covers, etc. be able to.
【００１８】[0018]
【実施例】以下、実施例をあげて、本発明を説明する
が、本発明はこれらの実施例に限定されない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００１９】製造例１ 再生セルロースの粒状成型物であるセルロースビーズ
（平均粒径５ｍｍ）１０．０ｇをメタケイ酸ナトリウム
・９水和物の水溶液（５．６８ｇ／１００ｍｌ）に含浸
せしめた後、アルミン酸ナトリウム４．６８ｇおよび水
酸化ナトリウム１０．００ｇの混合水溶液１００ｍｌを
加え、２５℃で１０日間浸漬させることにより、ゼオラ
イト担持セルロースビーズ１１．２ｇを得た。このゼオ
ライト担持セルロースビーズのゼオライト担持率は２
０．８ｗｔ％であった。Production Example 1 An aqueous solution (5.68 g / 100 ml) of sodium metasilicate / 9 hydrate was impregnated with 10.0 g of cellulose beads (average particle size: 5 mm) as a granular product of regenerated cellulose, and then alumina 100 ml of a mixed aqueous solution of 4.68 g of sodium acid and 10.00 g of sodium hydroxide was added, and the mixture was immersed at 25 ° C. for 10 days to obtain 11.2 g of cellulose beads supporting zeolite. The zeolite carrying ratio of the cellulose beads carrying zeolite is 2
0.8 wt%.
【００２０】実施例１ 製造例１で得られたゼオライト担持セルロースビーズを
コロイダルシリカ、二酸化チタンを分散させた一般建材
用セメントに加え、均一に混練した。これを型枠に入
れ、放置することにより成型物（厚さ３．０ｃｍ）を得
た。Example 1 The cellulose beads carrying zeolite obtained in Production Example 1 were added to a cement for general building materials in which colloidal silica and titanium dioxide were dispersed, and kneaded uniformly. This was placed in a mold and left standing to obtain a molded product (thickness: 3.0 cm).
【００２１】製造例２ パルプ２００ｇをメタケイ酸ナトリウム・９水和物の水
溶液（１９０ｇ／５０００ｍｌ）に含浸せしめた後、ア
ルミン酸ナトリウム１５０ｇおよび水酸化ナトリウム３
３０ｇの混合水溶液５０００ｍｌを加え、９０℃で２時
間浸漬させることにより、ゼオライト担持パルプを得
た。得られたゼオライト担持パルプのゼオライト担持率
は３８．０ｗｔ％であった。Production Example 2 After 200 g of pulp was impregnated with an aqueous solution of sodium metasilicate nonahydrate (190 g / 5000 ml), 150 g of sodium aluminate and sodium hydroxide 3
Zeolite-supported pulp was obtained by adding 30 g of a mixed aqueous solution 5000 ml and immersing the mixture at 90 ° C. for 2 hours. The zeolite loading of the obtained zeolite-loaded pulp was 38.0% by weight.
【００２２】実施例２ 製造例２で得られたゼオライト担持パルプ１００ｇを木
粉３００ｇ、ポリビニルアルコールおよび酢酸ビニル系
接着剤５０ｇ、水２００ｇと混ぜ、型枠に入れ圧力をか
けることにより成型物（厚さ３．０ｃｍ）を得た。Example 2 100 g of the zeolite-supported pulp obtained in Production Example 2 was mixed with 300 g of wood flour, 50 g of polyvinyl alcohol and a vinyl acetate-based adhesive, and 200 g of water. 3.0 cm).
【００２３】実施例３ 製造例２で得られたゼオライト担持パルプを用いて坪量
１００ｇ／ｍ2 、紙幅５０ｃｍの紙を抄き、これに下塗
り塗料として用いられているフェノール樹脂（ノボラッ
ク型）をヘキサメチレンテトラミンと共重合させたもの
に含浸させた。余分な樹脂は掻き取り、担持パルプと樹
脂とが混合したものの厚さ（紙厚）を１００μｍとし
た。１０分後フェノール樹脂の硬化が始まることにより
成型物を得た。Example 3 A paper having a basis weight of 100 g / m 2 and a paper width of 50 cm was made using the zeolite-supported pulp obtained in Production Example 2, and a phenol resin (novolak type) used as an undercoat paint was prepared. The copolymerized with hexamethylenetetramine was impregnated. Excess resin was scraped off, and the thickness (paper thickness) of the mixture of the supported pulp and the resin was set to 100 μm. After 10 minutes, the cured product of the phenolic resin was obtained to obtain a molded product.
【００２４】実施例４ 製造例２で得られたゼオライト担持パルプ１００ｇを
０．３０ｍｍｏｌ／１０００ｍｌの塩化カルシウム水溶
液に浸漬し、当該ゼオライトを更に口径の大きい５Ａゼ
オライトに変えた。５Ａゼオライト担持パルプ１０．０
ｇに、コラーゲン５．０ｇおよびリン酸カルシウム１．
０ｇを加えることにより成型物（５ｃｍ×３ｃｍ×１ｃ
ｍ）を得た。Example 4 100 g of the zeolite-supporting pulp obtained in Production Example 2 was immersed in a 0.30 mmol / 1000 ml aqueous solution of calcium chloride to convert the zeolite into a 5A zeolite having a larger diameter. 5A zeolite supported pulp 10.0
g, collagen 5.0 g and calcium phosphate 1. g.
By adding 0 g, a molded product (5 cm × 3 cm × 1 c
m).
【００２５】実験例１ 実施例１で得られた成型物を一辺が１０ｃｍ×１０ｃｍ
の正方形に切り出し、試験片とした。内容量３．０リッ
トルのガスバリアー性の高いフィルムバッグに試験片を
入れ、一旦内部の空気を除去した。ここに１００ｐｐｍ
の二酸化窒素ガス３．０リットルを封入し、１５Ｗの蛍
光灯下３０ｃｍに置いた。また同様に準備したフィルム
バッグに１００ｐｐｍのアンモニアガス３．０リットル
を封入し、１５Ｗの蛍光灯下３０ｃｍに置いた。比較試
験片Ｎｏ．１としてゼオライト担持セルロースビーズ１
０ｇおよび比較試験片Ｎｏ．２としてコロイダルシリカ
と二酸化チタンのみを一般建材用セメントに分散させる
ことによって得た同形状の試験片を用いた。バッグ内部
の二酸化窒素ガス濃度を経時的に測定した結果を図１に
示す。また同様にアンモニアガス濃度を経時的に測定し
た結果を図２に示す。図１および２に示すように実施例
１で得られた成型物は二酸化窒素およびアンモニアに対
し最も優れたガス除去能を示した。Experimental Example 1 The molded product obtained in Example 1 was 10 cm × 10 cm on a side.
, And cut into squares. The test piece was placed in a film bag having an internal capacity of 3.0 liters and having a high gas barrier property, and the air inside was temporarily removed. 100 ppm here
3.0 liters of nitrogen dioxide gas, and placed 30 cm under a 15 W fluorescent lamp. Further, 3.0 liters of 100 ppm ammonia gas was sealed in a film bag prepared in the same manner, and placed at 30 cm under a 15 W fluorescent lamp. Comparative test piece no. Cellulose beads supporting zeolite 1 as 1
0 g and Comparative Test Specimen No. As Test No. 2, a test piece of the same shape obtained by dispersing only colloidal silica and titanium dioxide in cement for general building materials was used. FIG. 1 shows the results of measuring the concentration of nitrogen dioxide gas inside the bag over time. FIG. 2 shows the result of similarly measuring the ammonia gas concentration over time. As shown in FIGS. 1 and 2, the molded product obtained in Example 1 showed the best gas removing ability for nitrogen dioxide and ammonia.
【００２６】実験例２ 実施例２で得られた成型物を一辺が１０ｃｍ×１０ｃｍ
の正方形に切り出し、試験片とした。内容量３．０リッ
トルのガスバリアー性の高いフィルムバッグに試験片を
入れ、一旦内部の空気を除去した。ここに１００ｐｐｍ
のアンモニアガス３．０リットルを封入した。比較実験
片Ｎｏ．３としてゼオライト担持パルプを除いて同様に
成型することによって得た同形状の木質ボードを用い
た。バッグ内部のアンモニアガス濃度を経時的に測定し
た結果を図３に示す。図３に示すように実施例２で得ら
れた成型物はアンモニアに対し優れたガス除去能を示し
た。Experimental Example 2 The molded product obtained in Example 2 was 10 cm × 10 cm on a side.
, And cut into squares. The test piece was placed in a film bag having an internal capacity of 3.0 liters and having a high gas barrier property, and the air inside was temporarily removed. 100 ppm here
3.0 liters of ammonia gas was sealed. Comparative test piece No. A wood board of the same shape obtained by molding in the same manner as in Example 3 except for the pulp supporting zeolite was used. FIG. 3 shows the results of measuring the concentration of ammonia gas in the bag over time. As shown in FIG. 3, the molded product obtained in Example 2 showed an excellent gas removing ability for ammonia.
【００２７】実験例３ 実施例３で得られた成型物を一辺が１０ｃｍ×１０ｃｍ
の正方形に切り出し、試験片とした。１０ｐｐｍの濃度
に調整した硝酸銀水溶液１００ｃｍ3にこの試験片を浸
漬し、３０分後にこの水溶液中の銀濃度を調べたとこ
ろ、５０ｐｐｂとなり著しく銀濃度を減少させられるこ
とが判明した。Experimental Example 3 The molded product obtained in Example 3 was 10 cm × 10 cm on a side.
, And cut into squares. The test piece was immersed in 100 cm 3 of a silver nitrate aqueous solution adjusted to a concentration of 10 ppm, and after 30 minutes, the silver concentration in the aqueous solution was examined. As a result, it was found to be 50 ppb, and the silver concentration could be significantly reduced.
【００２８】実験例４ 実施例４で得られた成型物（５ｃｍ×３ｃｍ×１ｃｍ）
を人工体液１００ｃｍ 3に浸漬させ、３８℃で保持し
た。３０日後、成型物を取出し、乾燥後重量を測定した
ところ、測定開始時は１５．８ｇであったのに対し、１
６．５ｇに増加していた。表面の形状も実験開始時は滑
らかであったのに対し、ざらつきが認められ、人工骨が
生成していた。人工体液のカルシウムおよびリン濃度を
測定したところ、実験開始時の３０モル％に減少してい
た。Experimental Example 4 The molded product obtained in Example 4 (5 cm × 3 cm × 1 cm)
The artificial body fluid 100cm ThreeAnd kept at 38 ° C
Was. After 30 days, the molded product was taken out, dried, and weighed.
However, while the weight was 15.8 g at the start of the measurement, it was 1
It had increased to 6.5 g. The surface shape is smooth at the beginning of the experiment.
It was rough, but roughness was observed, and the artificial bone
Had been generated. Artificial fluid calcium and phosphorus concentration
When measured, it was reduced to 30 mol% at the start of the experiment.
Was.
【００２９】[0029]
【発明の効果】本発明の組成物は、樹脂または無機系硬
化剤に親水性高分子がその実体内に無機多孔結晶を有す
る無機多孔結晶−親水性高分子複合体を添加することに
よって、無機多孔結晶−親水性高分子複合体の有するガ
ス吸着能、揮発性有機溶剤除去能、難燃性、保温性、重
金属および放射性元素除去能に加えて、固化させること
によって成型物が高強度となり、更に手触り等の触感を
改善することができ、更なる機能性を有する素材として
有用である。さらに、無機多孔結晶に金属を担持させる
ことにより、抗菌性および悪臭除去能等の性質が更に付
与される。The composition of the present invention is obtained by adding an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in its body to a resin or an inorganic curing agent. In addition to the gas adsorption ability, volatile organic solvent removal ability, flame retardancy, heat retention, heavy metal and radioactive element removal ability of the crystal-hydrophilic polymer complex, the molded product becomes stronger by solidification, Tactile sensation such as touch can be improved, and it is useful as a material having further functionality. Further, by supporting a metal on the inorganic porous crystal, properties such as antibacterial properties and odor removing ability are further imparted.
【図１】実験例１での各試験片の二酸化窒素除去能を示
すグラフである。FIG. 1 is a graph showing the nitrogen dioxide removing ability of each test piece in Experimental Example 1.
【図２】実験例１での各試験片のアンモニア除去能を示
すグラフである。FIG. 2 is a graph showing ammonia removing ability of each test piece in Experimental Example 1.
【図３】実験例２での各試験片のアンモニア除去能を示
すグラフである。FIG. 3 is a graph showing the ammonia removing ability of each test piece in Experimental Example 2.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 藤本 好信 大阪市福島区大開４丁目１番186号 レン ゴー株式会社中央研究所内 ────────────────────────────────────────────────── ─── Continued on the front page (72) Yoshinobu Fujimoto Inventor 4-1-1, Okai, Fukushima-ku, Osaka City Rengo Co., Ltd. Central Research Laboratory
Claims (7)
晶を有する無機多孔結晶−親水性高分子複合体と固化し
うる担体とを含有する組成物。1. A composition comprising an inorganic porous crystal-hydrophilic polymer composite in which a hydrophilic polymer has an inorganic porous crystal in its body and a solidifiable carrier.
特徴とする請求項１記載の組成物。2. The composition according to claim 1, wherein the inorganic porous crystal is zeolite.
ケル、コバルト、パラジウムおよび白金からなる群より
選択される少なくとも１種の金属を担持することを特徴
とする請求項１または２記載の組成物。3. The inorganic porous crystal according to claim 1, wherein the inorganic porous crystal supports at least one metal selected from the group consisting of silver, copper, zinc, iron, nickel, cobalt, palladium and platinum. Composition.
ルロース、バクテリアセルロース、化学修飾セルロー
ス、絹、羊毛、ポリアクリルアミド、ポリビニルアルコ
ール、架橋型ポリビニルアルコール、キチン、キトサ
ン、エチレン酢酸ビニルコポリマーおよびポリビニルホ
ルマールからなる群より選ばれる少なくとも１種からな
ることを特徴とする請求項１記載の組成物。4. The hydrophilic polymer is composed of natural cellulose, regenerated cellulose, bacterial cellulose, chemically modified cellulose, silk, wool, polyacrylamide, polyvinyl alcohol, cross-linked polyvinyl alcohol, chitin, chitosan, ethylene vinyl acetate copolymer and polyvinyl formal. The composition according to claim 1, comprising at least one member selected from the group consisting of:
びケナフからなる群より選ばれる少なくとも１種である
請求項４記載の組成物。5. The composition according to claim 4, wherein the natural cellulose is at least one selected from the group consisting of pulp, cotton, hemp and kenaf.
ス、ヒドロキシエチルセルロース、ヒドロキシプロピル
セルロース、メチルセルロース、エチルヒドロキシエチ
ルセルロースおよびカルボキシメチルセルロースからな
る群より選ばれる少なくとも１種である請求項４記載の
組成物。6. The composition according to claim 4, wherein the chemically modified cellulose is at least one selected from the group consisting of ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, methyl cellulose, ethyl hydroxyethyl cellulose, and carboxymethyl cellulose.
を固化してなる成型物。7. A molded product obtained by solidifying the composition according to claim 1.
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|---|---|---|---|
| JP04723599A JP4018284B2 (en) | 1998-02-25 | 1999-02-24 | Composition containing inorganic porous crystal-hydrophilic polymer composite and molded product thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4353998 | 1998-02-25 | ||
| JP10-43539 | 1998-02-25 | ||
| JP04723599A JP4018284B2 (en) | 1998-02-25 | 1999-02-24 | Composition containing inorganic porous crystal-hydrophilic polymer composite and molded product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11309368A true JPH11309368A (en) | 1999-11-09 |
| JP4018284B2 JP4018284B2 (en) | 2007-12-05 |
Family
ID=26383325
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04723599A Expired - Fee Related JP4018284B2 (en) | 1998-02-25 | 1999-02-24 | Composition containing inorganic porous crystal-hydrophilic polymer composite and molded product thereof |
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| Country | Link |
|---|---|
| JP (1) | JP4018284B2 (en) |
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| JP2003034753A (en) * | 2001-07-24 | 2003-02-07 | Rengo Co Ltd | X-type zeolite-hydrophilic polymer composite and production method for the same |
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