JPH083042B2 - Modified synthetic resin composition, modified synthetic resin product, and method for producing modified synthetic resin product - Google Patents
Modified synthetic resin composition, modified synthetic resin product, and method for producing modified synthetic resin productInfo
- Publication number
- JPH083042B2 JPH083042B2 JP4013408A JP1340892A JPH083042B2 JP H083042 B2 JPH083042 B2 JP H083042B2 JP 4013408 A JP4013408 A JP 4013408A JP 1340892 A JP1340892 A JP 1340892A JP H083042 B2 JPH083042 B2 JP H083042B2
- Authority
- JP
- Japan
- Prior art keywords
- synthetic resin
- modified synthetic
- soluble polymer
- product
- polymer powder
- 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.)
- Expired - Fee Related
Links
- 229920003002 synthetic resin Polymers 0.000 title claims description 135
- 239000000057 synthetic resin Substances 0.000 title claims description 135
- 239000000203 mixture Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims description 73
- 239000003531 protein hydrolysate Substances 0.000 claims description 41
- 229920003169 water-soluble polymer Polymers 0.000 claims description 36
- 239000007864 aqueous solution Substances 0.000 claims description 35
- 150000003839 salts Chemical class 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 12
- 238000000465 moulding Methods 0.000 claims description 12
- ZNOZWUKQPJXOIG-XSBHQQIPSA-L [(2r,3s,4r,5r,6s)-6-[[(1r,3s,4r,5r,8s)-3,4-dihydroxy-2,6-dioxabicyclo[3.2.1]octan-8-yl]oxy]-4-[[(1r,3r,4r,5r,8s)-8-[(2s,3r,4r,5r,6r)-3,4-dihydroxy-6-(hydroxymethyl)-5-sulfonatooxyoxan-2-yl]oxy-4-hydroxy-2,6-dioxabicyclo[3.2.1]octan-3-yl]oxy]-5-hydroxy-2-( Chemical compound O[C@@H]1[C@@H](O)[C@@H](OS([O-])(=O)=O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H]2OC[C@H]1O[C@H](O[C@H]1[C@H]([C@@H](CO)O[C@@H](O[C@@H]3[C@@H]4OC[C@H]3O[C@H](O)[C@@H]4O)[C@@H]1O)OS([O-])(=O)=O)[C@@H]2O ZNOZWUKQPJXOIG-XSBHQQIPSA-L 0.000 claims description 9
- 229920001817 Agar Polymers 0.000 claims description 7
- 235000010419 agar Nutrition 0.000 claims description 7
- 229920002148 Gellan gum Polymers 0.000 claims description 4
- 229920000161 Locust bean gum Polymers 0.000 claims description 4
- 239000000216 gellan gum Substances 0.000 claims description 4
- 235000010492 gellan gum Nutrition 0.000 claims description 4
- 239000000711 locust bean gum Substances 0.000 claims description 4
- 235000010420 locust bean gum Nutrition 0.000 claims description 4
- 239000000451 gelidium spp. gum Substances 0.000 claims description 3
- 235000002639 sodium chloride Nutrition 0.000 claims description 3
- 239000000047 product Substances 0.000 description 59
- 239000010408 film Substances 0.000 description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 17
- 229920000642 polymer Polymers 0.000 description 17
- 150000004676 glycans Chemical class 0.000 description 16
- 229920001282 polysaccharide Polymers 0.000 description 16
- 239000005017 polysaccharide Substances 0.000 description 16
- 239000004744 fabric Substances 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 238000011282 treatment Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 238000010828 elution Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 229920001661 Chitosan Polymers 0.000 description 9
- 229920001525 carrageenan Polymers 0.000 description 9
- 239000002649 leather substitute Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 239000000679 carrageenan Substances 0.000 description 8
- 229940113118 carrageenan Drugs 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- 108010010803 Gelatin Proteins 0.000 description 7
- 239000008273 gelatin Substances 0.000 description 7
- 229920000159 gelatin Polymers 0.000 description 7
- 235000019322 gelatine Nutrition 0.000 description 7
- 235000011852 gelatine desserts Nutrition 0.000 description 7
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000008272 agar Substances 0.000 description 4
- 235000010418 carrageenan Nutrition 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920005749 polyurethane resin Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 239000012209 synthetic fiber Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 239000004745 nonwoven fabric Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000011800 void material Substances 0.000 description 3
- 239000002759 woven fabric Substances 0.000 description 3
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 3
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 210000004243 sweat Anatomy 0.000 description 2
- QCVGEOXPDFCNHA-UHFFFAOYSA-N 5,5-dimethyl-2,4-dioxo-1,3-oxazolidine-3-carboxamide Chemical compound CC1(C)OC(=O)N(C(N)=O)C1=O QCVGEOXPDFCNHA-UHFFFAOYSA-N 0.000 description 1
- 102000011632 Caseins Human genes 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 102000002322 Egg Proteins Human genes 0.000 description 1
- 108010000912 Egg Proteins Proteins 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 108010076876 Keratins Proteins 0.000 description 1
- 102000011782 Keratins Human genes 0.000 description 1
- 102000035195 Peptidases Human genes 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 235000014103 egg white Nutrition 0.000 description 1
- 210000000969 egg white Anatomy 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 239000005445 natural material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003578 releasing effect Effects 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000004758 synthetic textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Description
【０００１】[0001]
【産業上の利用分野】この発明は、改質合成樹脂組成
物、改質合成樹脂製品および改質合成樹脂製品の製造方
法に関し、詳しくは、各種製品の製造に用いたときに、
その表面の風合いや吸放湿性等の諸性質を改善すること
のできる改質合成樹脂組成物と、このような改質合成樹
脂組成物を用いた製品、ならびに、このような改質合成
樹脂製品を製造する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 modified synthetic resin composition, a modified synthetic resin product and a method for producing a modified synthetic resin product.
Modified synthetic resin composition capable of improving various properties such as texture and moisture absorption / release property, products using such modified synthetic resin composition, and such modified synthetic resin product The present invention relates to a method of manufacturing.
【０００２】[0002]
【従来の技術】従来、合成繊維生地等を製造する際に、
その表面性状を改善するために、表面改質用の合成樹脂
フィルムを積層したり、表面改質用の合成樹脂コーティ
ングを施すことが行われている。これは、通常の合成繊
維生地は、天然の材料に比べて、吸湿性や防水性あるい
は表面の風合いに劣る等の欠点があり、これらの欠点を
解消するために、合成繊維または生地の表面のみを別の
改質合成樹脂で覆っておくことが行われるのである。例
えば、ナイロンやポリエステル生地の防水性を改善する
ために、これらの生地にポリウレタン樹脂で表面加工す
ることが行われている。2. Description of the Related Art Conventionally, when manufacturing synthetic fiber cloth,
In order to improve the surface properties, a synthetic resin film for surface modification is laminated or a synthetic resin coating for surface modification is applied. This is because ordinary synthetic fiber fabrics have drawbacks such as inferior hygroscopicity, waterproofness or surface texture compared to natural materials, and in order to eliminate these disadvantages, only synthetic fiber or fabric surface is used. Is covered with another modified synthetic resin. For example, in order to improve the waterproofness of nylon and polyester fabrics, these fabrics are surface-treated with a polyurethane resin.
【０００３】このようなポリウレタン樹脂による表面改
質加工では、表面の感触にべとつき感がないことや、表
面の光沢が強過ぎず、生地の風合いを損なわない等とい
う機能が要求される。また、天然の皮革や生地に劣らな
い吸放湿性を有することも必要である。ここで、吸放湿
性とは、単に湿気を吸収保持する性質だけでなく、外部
環境との湿度差によっては、吸収した湿気を外部環境に
容易に放出し、フィルムやシート等の表裏面を湿気が通
過し易いという、いわゆる透湿性をも意味する性能であ
る。Such surface modification processing using a polyurethane resin is required to have a function that the surface feels non-greasy, the surface gloss is not too strong, and the texture of the cloth is not impaired. Further, it is also necessary to have a moisture absorption / release property that is not inferior to that of natural leather or cloth. Here, the moisture absorption and desorption property is not only the property of absorbing and retaining moisture, but depending on the difference in humidity from the external environment, the absorbed moisture is easily released to the external environment, and the front and back surfaces of a film, sheet, etc. Is a performance that also means so-called moisture permeability, which means that water easily passes through.
【０００４】なお、上記表面改質加工用のポリウレタン
樹脂以外にも、各種の合成樹脂を利用する際に、その目
的や要求性能に合わせて、吸放湿性や表面の風合い等を
改善することが要望されている。そこで、本願発明者ら
は、前記ポリウレタン樹脂その他の合成樹脂において、
合成樹脂から製造される製品の吸放湿性や表面の風合い
等が良好に改善される改質合成樹脂組成物、および、こ
のような改質効果が良好に発揮される改質合成樹脂製品
を製造できる方法を開発し、先に、特願平３−１６１８
８７号等で特許出願している。When various synthetic resins other than the above-mentioned surface-modifying polyurethane resin are used, it is possible to improve the moisture absorption and desorption property and the surface texture according to the purpose and required performance. Is requested. Therefore, the inventors of the present invention, in the polyurethane resin and other synthetic resins,
Manufacture of modified synthetic resin compositions in which moisture absorption and desorption of products manufactured from synthetic resins and surface texture are improved, and modified synthetic resin products in which such modifying effects are exhibited well Developed a method that can be done, and first, Japanese Patent Application No.
Patent application has been filed under No. 87 etc.
【０００５】この方法は、合成樹脂に、キトサン塩やカ
ラギーナンなどの親水性多糖類の微粉末を含有させてお
くことにより、この合成樹脂から成形された合成樹脂製
品の前記諸性能を改善するものである。また、合成樹脂
成形品を、温水や熱水に浸漬することによって、成形品
中の親水性多糖類粉末を溶出除去し、この親水性多糖類
粉末が除去された跡に残る空隙で、前記吸放湿性を発揮
させる方法も開示されている。合成樹樹脂に、前記親水
性多糖類粉末とともに、加水分解ゼラチンなどの蛋白質
加水分解物の水溶液を含有させておき、成形後に親水性
多糖類粉末および蛋白質加水分解物を溶出除去すれば、
親水性多糖類粉末が除去された跡に残る粒状の空隙と、
蛋白質加水分解物が除去された跡に残る網目状の空隙と
が一体的に連結した、連続多孔質構造が構成できる結
果、前記した諸性能の向上効果がより高まることも示さ
れている。This method improves the above-mentioned various performances of a synthetic resin product molded from the synthetic resin by incorporating fine powder of hydrophilic polysaccharide such as chitosan salt and carrageenan into the synthetic resin. Is. Further, by immersing the synthetic resin molded article in warm water or hot water, the hydrophilic polysaccharide powder in the molded article is eluted and removed, and in the voids left behind after the removal of the hydrophilic polysaccharide powder, the absorption A method of exhibiting moisture releasing property is also disclosed. Synthetic resin, together with the hydrophilic polysaccharide powder, by containing an aqueous solution of a protein hydrolyzate such as hydrolyzed gelatin, if the hydrophilic polysaccharide powder and the protein hydrolyzate are eluted and removed after molding,
Granular voids that remain after the hydrophilic polysaccharide powder is removed,
It has also been shown that as a result of the continuous porous structure in which the network-like voids remaining after the protein hydrolyzate is removed are integrally connected to be formed, the above-mentioned effect of improving the various performances is further enhanced.
【０００６】[0006]
【発明が解決しようとする課題】ところが、上記従来技
術では、液状の合成樹脂に、親水性多糖類粉末と水溶液
とを含有させた状態で、この樹脂調液を保管しておく
と、沈殿が生じてしまい、使用し難くなる場合があると
いう問題がある。また、樹脂調液を塗布してフィルムあ
るいは薄い膜を形成しようとすると、塗布ムラが生じ、
平滑な表面が得られ難い場合もあった。However, in the above-mentioned prior art, if the liquid synthetic resin is made to contain the hydrophilic polysaccharide powder and the aqueous solution and the resin preparation is stored, precipitation will occur. However, there is a problem that it may be difficult to use. In addition, when trying to form a film or a thin film by applying the resin preparation, coating unevenness occurs,
In some cases, it was difficult to obtain a smooth surface.
【０００７】このような問題が生じるのは、親水性多糖
類粉末と水溶液との相互作用によって、沈殿を生じた
り、塗布性が悪くなったりするものと考えられる。具体
的には、水溶液の添加により合成樹脂液中に含まれるこ
とになった水分が、親水性多糖類粉末に作用して、親水
性多糖類を溶かしてしまい、成形後に、親水性多糖類粉
末による粒状の空隙が十分に形成されないという問題が
生じる。親水性多糖類粉末が合成樹脂液中の水分では完
全には溶けなかったとしても、親水性多糖類粉末の表面
が溶けると、親水性多糖類粉末同士がくっついてしまっ
たり、いわゆるブロック状に固まってしまったりする。
そうなると、親水性多糖類粉末を、合成樹脂液中に均一
に混合させておくことができず、沈殿を生じたり、塗布
性が悪くなったり、成形された合成樹脂製品の品質性能
が低下してしまったりするのである。It is considered that such a problem is caused by the interaction between the hydrophilic polysaccharide powder and the aqueous solution, which causes precipitation or deteriorates the coating property. Specifically, the water contained in the synthetic resin liquid due to the addition of the aqueous solution acts on the hydrophilic polysaccharide powder to dissolve the hydrophilic polysaccharide, and after molding, the hydrophilic polysaccharide powder There is a problem in that the granular voids are not formed sufficiently. Even if the hydrophilic polysaccharide powder is not completely dissolved by the water content of the synthetic resin liquid, if the surface of the hydrophilic polysaccharide powder is dissolved, the hydrophilic polysaccharide powders may stick to each other or solidify into a so-called block shape. It will be lost.
If this happens, the hydrophilic polysaccharide powder cannot be uniformly mixed in the synthetic resin liquid, resulting in precipitation, poor coatability, and poor quality performance of the molded synthetic resin product. It gets lost.
【０００８】そこで、この発明の課題は、合成樹脂に親
水性多糖類粉末と水溶液とを含有させておいても、沈殿
が生じず、塗布性も良好な改質合成樹脂組成物と、この
ような改質合成樹脂組成物から製造された製品、およ
び、この製品を製造する方法を提供することにある。Therefore, an object of the present invention is to provide a modified synthetic resin composition which does not cause precipitation even when a synthetic resin contains a hydrophilic polysaccharide powder and an aqueous solution, and has good coatability. The present invention provides a product manufactured from the modified synthetic resin composition and a method for manufacturing the product.
【０００９】[0009]
【課題を解決するための手段】上記課題を解決する、こ
の発明にかかる改質合成樹脂組成物は、合成樹脂に、ι
・κ−カラギーナンＫ・Ｃａ塩、ローカストビーンガ
ム、寒天、ジェランガムからなる群から選ばれた少なく
とも１種の温水溶解性高分子粉末と蛋白質加水分解物水
溶液とを含有してなる。The modified synthetic resin composition according to the present invention, which solves the above-mentioned problems, has the following characteristics:
It contains at least one kind of hot water-soluble polymer powder selected from the group consisting of κ-carrageenan K · Ca salt, locust bean gum, agar and gellan gum, and a protein hydrolyzate aqueous solution.
【００１０】合成樹脂としては、各種の製品を製造する
ための材料として利用されている任意の合成樹脂が使用
できる。具体的には、前記ポリウレタンのほか、ポリス
チレン、ポリプロピレン、ポリエステル、ナイロン、ポ
リアクリレート、ポリエチレン、ポリ塩化ビニル等が挙
げられる。温水溶解性高分子粉末は、天然原料あるいは
合成原料から得られる各種の高分子のうち、温水溶解性
を有する材料を粉末状に調製したものである。この発明
で温水溶解性とは、通常、改質合成樹脂液を調製する際
の処理温度である常温あるいは比較的弱い加温状態程度
では溶解しないものを意味する。具体的には、５０℃以
下の水には溶解せず、５０℃を超える温水で溶解可能な
ものを用いる。なお、１００℃程度の熱水にも溶解しな
いものは、不溶性高分子粉末であり、この発明における
温水溶解性高分子粉末から除外する。また、蛋白質加水
分解物水溶液と一緒に合成樹脂に含有させたときに、相
互作用で変質したり、特性が低下しないものを用いる。
具体的には、温水溶解性高分子粉末として、ι・κ−カ
ラギーナンＫ・Ｃａ塩、ローカストビーンガム、寒天、
ジェランガムからなる群から選ばれた少なくとも１種の
温水溶解性高分子粉末を用いる。カラギーナンには、λ
−カラギーナンやι・κ−カラギーナンのＮａ塩なども
存在するが、これらのカラギーナンは、常温で溶解し、
この発明で用いる材料としては好ましくない。As the synthetic resin, any synthetic resin used as a material for manufacturing various products can be used. Specific examples include polyurethane, polystyrene, polypropylene, polyester, nylon, polyacrylate, polyethylene, and polyvinyl chloride. The hot water-soluble polymer powder is a powder prepared by preparing a hot water-soluble material out of various polymers obtained from natural or synthetic raw materials. In the present invention, the hot water solubility generally means that it does not dissolve at room temperature, which is the processing temperature for preparing the modified synthetic resin liquid, or at a relatively weakly heated state. Specifically, it is not soluble in water at 50 ° C. or lower, but is soluble in warm water at 50 ° C. or higher. Insoluble polymer powders that do not dissolve in hot water at about 100 ° C. are excluded from the hot water-soluble polymer powders of the present invention. Further, when the synthetic resin is contained together with the aqueous solution of protein hydrolyzate, the one which is not deteriorated due to the interaction or the characteristic is not deteriorated is used.
Specifically, as hot water-soluble polymer powder, ι · κ-carrageenan K · Ca salt, locust bean gum, agar,
At least one hot water-soluble polymer powder selected from the group consisting of gellan gum is used. Carrageenan has λ
-There are carrageenan and Na salt of ι · κ-carrageenan, but these carrageenans dissolve at room temperature,
It is not preferable as the material used in the present invention.
【００１１】温水溶解性高分子粉末は、通常、溶液状態
で抽出あるいは製造されたものを、加熱乾燥や凍結乾燥
により固形化してから粉砕したり、噴霧乾燥したりして
得られる２００メッシュ通過以下（粒径７４μｍ以下）
の粉末を用いる。高分子材料を粉末化するための手段
は、上記以外にも、通常の各種薬剤、化学製品における
粉末化手段が適用できる。The hot water-soluble polymer powder is usually 200 mesh or less, which is obtained by solidifying the powder extracted or produced in a solution state by heating drying or freeze drying and then pulverizing or spray drying. (Particle size 74 μm or less)
Powder is used. As means for powdering the polymer material, in addition to the above, usual powdering means for various chemicals and chemical products can be applied.
【００１２】温水溶解性高分子粉末は、大きさすなわち
粒径が小さい程、合成樹脂と良好に混練されたり、製造
された製品に良好な多孔質構造を構成できて、製品表面
の風合いを均一に改善出来る等の作用効果がある。この
発明の作用効果を十分に発揮させるには、粒径の上限が
前記２００メッシュ通過以下であることが必要である。
２００メッシュ通過を超える粉末では、製造された合成
樹脂製品の表面性状に凹凸やムラ、バラツキが出たり、
改質効果が十分に発揮出来なくなったりする。また、合
成樹脂製品の強度や耐久性を大幅に低下させる問題が生
じる。粒径の下限としては、粉末製造の手間や経済性等
を考慮して適当な範囲に設定すればよい。実用上好まし
い粉末の大きさは、粒径０．１〜３５μｍ程度のもので
ある。[0012] The smaller the size of the hot water-soluble polymer powder, that is, the smaller the particle size, the better the kneading with the synthetic resin, the better the porous structure can be formed in the manufactured product, and the more uniform the surface texture of the product. It has the effect that it can be improved. In order to fully exert the effects of the present invention, the upper limit of the particle size needs to be 200 mesh or less.
If the powder exceeds 200 mesh, the surface properties of the manufactured synthetic resin product may have irregularities, unevenness, or variations,
The modification effect may not be fully exerted. Further, there arises a problem that the strength and durability of the synthetic resin product are significantly reduced. The lower limit of the particle size may be set to an appropriate range in consideration of the time and cost of powder production. The size of the powder that is practically preferable is a particle size of about 0.1 to 35 μm.
【００１３】蛋白質加水分解物水溶液は、コラーゲン、
ゼラチン、卵白、カゼイン、ケラチン、大豆、小麦など
の蛋白質材料を加水分解したものである。蛋白質加水分
解物の分子量として、１０００〜２００００程度のもの
が好ましい。蛋白質材料を加水分解する方法としては、
酸・アルカリ存在下での加熱・高圧処理や、蛋白質分解
酵素処理など、通常の加水分解手段が採用できる。この
ようにして得られた蛋白質加水分解物は、常温水にも良
好に溶解する。蛋白質加水分解物水溶液を、ｐＨ調製し
ておいたり、各種塩類を添加しておくと、合成樹脂に含
まれる有機溶媒などとの相溶性を改善することができ
る。The aqueous solution of protein hydrolyzate contains collagen,
It is a hydrolyzed protein material such as gelatin, egg white, casein, keratin, soybean and wheat. The molecular weight of the protein hydrolyzate is preferably about 1,000 to 20,000. As a method of hydrolyzing a protein material,
Usual hydrolysis means such as heating / high-pressure treatment in the presence of acid / alkali or proteolytic enzyme treatment can be adopted. The protein hydrolyzate thus obtained is well dissolved in normal temperature water. When the pH of the aqueous solution of protein hydrolyzate is adjusted or various salts are added, the compatibility with the organic solvent contained in the synthetic resin can be improved.
【００１４】前記のような温水溶解性高分子粉末と蛋白
質加水分解物水溶液とを、前記合成樹脂に均一に混合も
しくは混練して、得られた改質合成樹脂組成物を各種の
用途に使用する。合成樹脂に対する温水溶解性高分子粉
末の添加量は、目的とする製品の用途によっても異なる
が、通常、合成樹脂固形分１００重量部に対して約５〜
１５０重量部、好ましくは１０〜１２５重量部の範囲で
ある。また、蛋白質加水分解物水溶液の添加量は、合成
樹脂固形分１００重量部に対して、通常、蛋白質加水分
解物水溶液固形分として約５〜４０重量部、好ましくは
１０〜２５重量部の範囲である。なお、合成樹脂には水
分を嫌うものもあり、その場合には、蛋白質加水分解物
水溶液の固形分濃度を１０％以上とする。The hot water-soluble polymer powder and the aqueous solution of protein hydrolyzate as described above are uniformly mixed or kneaded with the synthetic resin, and the obtained modified synthetic resin composition is used for various purposes. . The amount of the hot water-soluble polymer powder added to the synthetic resin varies depending on the intended use of the product, but is usually about 5 to 100 parts by weight of the synthetic resin solid content.
It is in the range of 150 parts by weight, preferably 10 to 125 parts by weight. The amount of the protein hydrolyzate aqueous solution added is usually in the range of about 5 to 40 parts by weight, preferably 10 to 25 parts by weight, as the protein hydrolyzate aqueous solution solid content, relative to 100 parts by weight of the synthetic resin solid content. is there. Some synthetic resins do not like water, and in that case, the solid content concentration of the protein hydrolyzate aqueous solution is set to 10% or more.
【００１５】合成樹脂には、目的とする製品や用途に応
じて、温水溶解性高分子粉末および蛋白質加水分解物水
溶液以外の任意の添加剤を添加することができる。具体
的には、着色剤、可塑剤、硬化剤、安定剤、滑剤、発泡
剤等、通常の合成樹脂に対する添加剤と同様のものであ
る。上記のような改質合成樹脂組成物を、フィルムやシ
ートその他の形状に成形した後、得られた改質合成樹脂
成形品に対して、温水溶解性高分子粉末および蛋白質加
水分解物を溶出除去して改質合成樹脂製品を得る。Any additive other than the hot water-soluble polymer powder and the aqueous solution of the protein hydrolyzate can be added to the synthetic resin depending on the intended product or application. Specifically, it is the same as an additive to an ordinary synthetic resin such as a colorant, a plasticizer, a curing agent, a stabilizer, a lubricant, a foaming agent and the like. After molding the modified synthetic resin composition as described above into a film, sheet or other shape, the modified synthetic resin molded product obtained is eluted and removed with hot water-soluble polymer powder and protein hydrolyzate. To obtain a modified synthetic resin product.
【００１６】蛋白質加水分解物は、常温水でも溶出除去
できるので、改質合成樹脂成形品を水に処理するだけで
も、蛋白質加水分解物を除去することができる。温水溶
解性高分子粉末は、前記した溶解温度以上の温水もしく
は熱水で溶出除去できる。溶出除去処理が行われた改質
合成樹脂製品には、溶けだした温水溶解性高分子粉末お
よび蛋白質加水分解物が存在していた部分に、微細な空
隙が残ることになる。そして、この空隙が、透湿作用を
果たす。溶出除去処理は、蛋白質加水分解物は勿論、温
水溶解性高分子粉末も完全に除去するようにしておいて
もよいが、合成樹脂製品の品質性能に悪影響がなけれ
ば、温水溶解性高分子粉末の一部が残存していても構わ
ない。温水溶解性高分子粉末自体にもある程度の吸放湿
性はあるので、合成樹脂製品に残存する温水溶解性高分
子粉末による吸放湿性を利用することもできる。但し、
通常は、合成樹脂液に含有させた温水溶解性高分子粉末
のうち、少なくとも７０％以上、好ましくは８０％以上
が溶出する程度に、溶出除去処理の処理時間その他の処
理条件を設定する。温水溶解性高分子粉末の溶出割合が
少ないと、良好な空隙構造が形成されない。Since the protein hydrolyzate can be eluted and removed even at room temperature water, the protein hydrolyzate can be removed only by treating the modified synthetic resin molded article with water. The hot water-soluble polymer powder can be eluted and removed with warm water or hot water having a melting temperature or higher as described above. In the modified synthetic resin product that has been subjected to the elution and removal treatment, fine voids will remain in the portions where the dissolved hot water-soluble polymer powder and the protein hydrolyzate were present. Then, the voids have a moisture permeable effect. The elution removal treatment may be performed so as to completely remove not only the protein hydrolyzate but also the hot water-soluble polymer powder, but if the quality performance of the synthetic resin product is not adversely affected, the hot water-soluble polymer powder It does not matter even if some of them remain. Since the hot water-soluble polymer powder itself has some moisture absorption / release property, the moisture absorption / release property of the warm water-soluble polymer powder remaining in the synthetic resin product can also be utilized. However,
Usually, the treatment time of the elution removal treatment and other treatment conditions are set such that at least 70% or more, preferably 80% or more, of the hot water-soluble polymer powder contained in the synthetic resin liquid is eluted. If the elution ratio of the hot water-soluble polymer powder is small, a good void structure cannot be formed.
【００１７】以上に説明した、特定の温水溶解性高分子
粉末と蛋白質加水分解物水溶液とを含有する改質合成樹
脂組成物は、通常の合成樹脂に対する成形方法および前
記した溶出除去処理を経て、各種合成樹脂製品を製造す
ることができる。改質合成樹脂組成物から得られた成形
品は、そのままで改質合成樹脂製品として利用できるほ
か、別な合成樹脂製品の表面や一部のみを、改質合成樹
脂成形品で構成するようにしてもよい。さらに、改質合
成樹脂組成物を、合成樹脂成形品や繊維、布生地、合成
皮革その他の物品にコーティングし、改質合成樹脂成形
物からなるコーティング膜を形成することによって、コ
ーティング製品の表面性状を改善するために用いること
もできる。具体的なコーティング手段は、通常の表面改
質コーティング技術と同様に行われる。不織布や織物か
らなる布にコーティングする場合は、布の表面だけでな
く、内部まで浸透させて、個々の繊維そのものをコーテ
ィングすることもできる。改質合成樹脂製品の表面ある
いはコーティングされた改質合成樹脂層に対して、各種
の表面処理加工を施すことができる。例えば、合成皮革
の表面にコーティングされた改質合成樹脂層に対して、
サンディングや革シボ加工を施すことができる。The modified synthetic resin composition containing the specific hot water-soluble polymer powder and the aqueous solution of protein hydrolyzate described above undergoes a molding method for a conventional synthetic resin and the above-mentioned elution removal treatment, Various synthetic resin products can be manufactured. A molded product obtained from the modified synthetic resin composition can be used as it is as a modified synthetic resin product, or the surface or part of another synthetic resin product can be composed of the modified synthetic resin molded product. May be. Further, the modified synthetic resin composition is coated on a synthetic resin molded article, fiber, cloth material, synthetic leather or other article to form a coating film made of the modified synthetic resin molded article to obtain a surface property of the coated product. Can also be used to improve The specific coating means is performed in the same manner as the usual surface modification coating technique. In the case of coating a cloth made of a non-woven fabric or a woven fabric, not only the surface of the cloth but also the inside can be permeated to coat the individual fibers themselves. Various surface treatments can be applied to the surface of the modified synthetic resin product or the coated modified synthetic resin layer. For example, for the modified synthetic resin layer coated on the surface of synthetic leather,
Can be sanded or textured.
【００１８】この発明にかかる改質合成樹脂製品の具体
例について説明する。まず、改質合成樹脂フィルムが製
造できる。改質合成樹脂フィルムの成形もしくは製造方
法は、通常の合成樹脂フィルムと同様の方法が採用でき
る。特に、溶媒で適当な濃度に調整された改質合成樹脂
組成物液を薄く塗布した後、溶媒を蒸発させて膜形成す
る方法が好ましい。改質合成樹脂フィルムは、それ自体
で吸放湿性に優れたフィルム材料として各種の用途に使
用できるほか、この改質合成樹脂フィルムを、各種合成
樹脂成形品や布、合成皮革等の表面に積層して、これら
の製品の表面改質加工に使用することができる。Specific examples of the modified synthetic resin product according to the present invention will be described. First, a modified synthetic resin film can be manufactured. As a method for molding or producing the modified synthetic resin film, the same method as that for a normal synthetic resin film can be adopted. Particularly preferred is a method of thinly applying a modified synthetic resin composition liquid adjusted to an appropriate concentration with a solvent and then evaporating the solvent to form a film. The modified synthetic resin film itself can be used for various purposes as a film material with excellent moisture absorption and desorption, and this modified synthetic resin film is laminated on the surface of various synthetic resin molded products, cloth, synthetic leather, etc. Then, it can be used for surface modification processing of these products.
【００１９】不織布や織物からなる布を、前記改質合成
樹脂組成物液に浸漬して、布の表面だけでなく内部全体
に合成樹脂液を含浸させた後、改質合成樹脂組成物を乾
燥硬化させれば、吸放湿性が改善された改質布が得られ
る。不織布あるいは織物を構成する繊維材料は、通常の
合成繊維等からなるものが使用できる。A cloth made of a non-woven fabric or a woven fabric is dipped in the modified synthetic resin composition liquid to impregnate the entire surface of the cloth with the synthetic resin liquid, and then the modified synthetic resin composition is dried. When cured, a modified cloth with improved moisture absorption / release is obtained. As the fibrous material forming the non-woven fabric or the woven fabric, those made of ordinary synthetic fibers can be used.
【００２０】[0020]
【作用】可溶性の高分子粉末と蛋白質加水分解物水溶液
とを含有させた合成樹脂を、適当な形状に成形した後、
可溶性高分子粉末および蛋白質加水分解物を水または温
水に溶出させて除去すると、吸放湿性に優れた多孔質構
造を備えた合成樹脂製品が得られる。これは、つぎのよ
うな作用による。[Function] After molding a synthetic resin containing a soluble polymer powder and an aqueous solution of protein hydrolyzate into an appropriate shape,
When the soluble polymer powder and the protein hydrolyzate are eluted with water or warm water and removed, a synthetic resin product having a porous structure excellent in moisture absorption and desorption can be obtained. This is due to the following action.
【００２１】溶出除去処理を行うことによって改質合成
樹脂製品に形成される空隙の形状や大きさは、合成樹脂
に含有させておく高分子粉末および蛋白質加水分解物の
形態によって変わる。可溶性高分子粉末の場合には、粉
末の粒形状に対応する空隙が形成される。この場合は、
ひとつひとつの空隙が独立している。蛋白質加水分解物
水溶液の場合には、樹脂構造の隙間に液状物が連続して
つながった状態で浸入して均等に分布することになるの
で、蛋白質加水分解物が除去された後には微細な網の目
状に連通した空隙が形成される。The shape and size of the voids formed in the modified synthetic resin product by the elution removal treatment vary depending on the forms of the polymer powder and the protein hydrolyzate contained in the synthetic resin. In the case of soluble polymer powder, voids corresponding to the particle shape of the powder are formed. in this case,
Each void is independent. In the case of an aqueous solution of protein hydrolyzate, liquid matter will continuously penetrate into the gaps of the resin structure and will be evenly distributed. The voids communicating with each other are formed.
【００２２】したがって、可溶性高分子粉末の跡に残る
粒状の独立した空隙が、蛋白質加水分解物の跡に残る網
目状の空隙でつながって、互いにあるいは外界と連通し
た構造の多孔質構造が構成される。また、蛋白質加水分
解物および可溶性高分子が、連通状態の空隙を通して外
部に流出するので、合成樹脂製品の内部の奥深い個所か
らも容易に流出することになり、蛋白質加水分解物およ
び可溶性高分子の除去を効率良くかつ充分に行うことが
できる。Therefore, the granular independent voids remaining in the traces of the soluble polymer powder are connected by the mesh-like voids remaining in the traces of the protein hydrolyzate to form a porous structure having a structure communicating with each other or the outside. It Further, since the protein hydrolyzate and the soluble polymer flow out to the outside through the voids in the communicating state, they easily flow out from a deep part inside the synthetic resin product, and the protein hydrolyzate and the soluble polymer are The removal can be performed efficiently and sufficiently.
【００２３】上記のように、粒状の独立した空隙と網目
状の空隙が、合成樹脂製品の表面から奥深い個所まで連
続して形成されていれば、この空隙内部に、湿気や水分
を大量に吸い込んでおいたり、吸い込んだ水分を合成樹
脂製品の表面から良好に放出することが可能になる。す
なわち、合成樹脂液に可溶性の高分子粉末のみを含有さ
せておいた場合、あるいは、水溶液のみを含有させてお
いた場合に比べて、はるかに優れた吸放湿性を発揮でき
るのである。As described above, if the granular independent voids and the mesh voids are continuously formed from the surface of the synthetic resin product to the deep part, a large amount of moisture or water is sucked into the voids. It becomes possible to satisfactorily release the moisture absorbed or absorbed from the surface of the synthetic resin product. That is, much better moisture absorption and desorption can be exhibited as compared with the case where only the soluble polymer powder is contained in the synthetic resin liquid or the case where only the aqueous solution is contained.
【００２４】以上に説明したように、合成樹脂に、可溶
性高分子粉末と蛋白質加水分解物水溶液を含有させてお
くと、各種の優れた作用が発揮できるが、可溶性高分子
粉末の種類によっては、可溶性高分子粉末と蛋白質加水
分解物水溶液との相互作用で、合成樹脂調液に、沈殿が
生じたり塗布性が悪くなる。しかし、この発明で使用す
る前記特定の温水溶解性高分子粉末の場合、蛋白質加水
分解物水溶液と同時に合成樹脂に含有させておいても、
沈殿が生じず、塗布性もきわめて良好になる。すなわ
ち、この発明で使用する特定の温水溶解性高分子粉末
は、水には溶けず、一定温度以上の温水のみで溶けるの
で、この溶解温度以下で改質合成樹脂組成物を調製した
り、取り扱ったりすれば、水溶液とともに温水溶解性高
分子粉末を合成樹脂液に含有させておいても、温水溶解
性高分子粉末が溶ける心配はない。温水溶解性高分子粉
末が溶けなければ、粉末同士がくっついたり、ブロック
状に固まったりすることもなく、合成樹脂液中に温水溶
解性高分子粉末を良好に混合しておける。As described above, when the synthetic resin contains the soluble polymer powder and the aqueous solution of protein hydrolyzate, various excellent effects can be exhibited. However, depending on the type of the soluble polymer powder, Due to the interaction between the soluble polymer powder and the aqueous solution of protein hydrolyzate, precipitation occurs in the synthetic resin preparation or the coatability deteriorates. However, in the case of the specific hot water-soluble polymer powder used in the present invention, even if it is contained in the synthetic resin at the same time as the aqueous protein hydrolyzate solution,
No precipitation occurs and the coatability is extremely good. That is, since the specific hot water-soluble polymer powder used in the present invention is insoluble in water and can be dissolved only in hot water having a certain temperature or higher, a modified synthetic resin composition may be prepared or handled at a temperature below the melting temperature. By so doing, even if the warm water-soluble polymer powder is contained in the synthetic resin liquid together with the aqueous solution, there is no concern that the warm water-soluble polymer powder will dissolve. If the hot water-soluble polymer powder does not dissolve, the powder does not stick to each other or solidify into a block, and the hot water-soluble polymer powder can be mixed well in the synthetic resin liquid.
【００２５】その結果、改質合成樹脂組成物を、長時間
保管しておいたり、成形するために塗布したりしても、
沈殿を生じたり、塗布性が悪くなったりすることがな
い。製造された合成樹脂製品には、温水溶解性高分子粉
末の跡に残る独立した粒状の空隙が良好に形成され、蛋
白質加水分解物水溶液の跡に残る網状の空隙とともに、
良好な連続多孔質状の空隙が形成され、合成樹脂製品の
吸放湿性など使用性能も優れたものとなる。As a result, even if the modified synthetic resin composition is stored for a long time or applied for molding,
No precipitation will occur and the coatability will not deteriorate. In the produced synthetic resin product, independent granular voids remaining in the traces of the hot water-soluble polymer powder are well formed, and together with the mesh-like voids remaining in the traces of the aqueous solution of protein hydrolyzate,
Good continuous porous voids are formed, and the synthetic resin product has excellent usage properties such as moisture absorption and desorption.
【００２６】[0026]
【実施例】下記に示す高分子粉末と蛋白質加水分解物水
溶液を合成樹脂に混合して、改質合成樹脂組成物を製造
し、その特性を比較した。 ＜高分子粉末＞ キトサン乳酸塩微粉砕物Ａ（粒径２〜１３μｍ、平
均９μｍ） キトサン乳酸塩微粉砕物Ｂ（粒径２〜６３μｍ、平
均２２μｍ） ι−カラギーナンＮａ塩微粉砕物（粒径２〜１４μ
ｍ、平均６μｍ） κ−カラギーナンＫ塩微粉砕物（粒径３〜３２μ
ｍ、平均１０μｍ） 寒天微粉砕物（粒径３〜６２μｍ、平均１６μｍ） ＜蛋白質加水分解物水溶液＞ 加水分解ゼラチン（固型分３０％） ＜合成樹脂＞ ウレタン樹脂剤：ＮＢ−６３０、大日本インキ工業製、
合成皮革用、不揮発分２９〜３１％ 上記のようにして得られた合成樹脂調液の安定性を評価
した。EXAMPLE A polymer powder and an aqueous solution of protein hydrolyzate shown below were mixed with a synthetic resin to produce a modified synthetic resin composition, and the characteristics of the modified synthetic resin compositions were compared. <Polymer powder> Chitosan lactate finely ground product A (particle size 2 to 13 μm, average 9 μm) Chitosan lactate finely ground product B (particle size 2 to 63 μm, average 22 μm) ι-carrageenan Na salt finely ground product (particle size 2-14μ
m, average 6 μm) K-carrageenan K salt finely pulverized product (particle size 3 to 32 μm
m, average 10 μm) Agar finely ground product (particle size 3 to 62 μm, average 16 μm) <Protein hydrolyzate aqueous solution> Hydrolyzed gelatin (solid content 30%) <Synthetic resin> Urethane resin agent: NB-630, Dainippon Made by Ink Industry,
For synthetic leather, non-volatile content 29-31% The stability of the synthetic resin preparation obtained as described above was evaluated.
【００２７】＜安定性試験＞合成樹脂調液を一定時間静
置した後、沈殿の有無を目視観察した。表１に、その結
果を示している。<Stability Test> After the synthetic resin preparation was allowed to stand for a certain period of time, the presence or absence of precipitation was visually observed. The results are shown in Table 1.
【００２８】[0028]
【表１】 ───────────────────────────────── 経 過 時 間 hr 高分子粉末 ０ １ ２ ３ ６ ───────────────────────────────── 実施例1.1 κ−カラギーナンＫ塩 ○ ○ ○ ○ ○ 実施例1.2 寒天 ○ ○ ○ ○ ○ 比較例1.1 キトサン塩Ａ ○ △ × × × 比較例1.2 キトサン塩Ｂ ○ × × × × 比較例1.3 ι−カラギーナンＮａ塩 ○ △ △ × × ───────────────────────────────── ○：沈殿物確認できず △：沈殿物あり ×：かなりの沈殿物あり 以上の結果、この発明の実施例では、調液後６時間経過
しても、沈殿物は全く発生せず、良好に使用できること
が確認できた。[Table 1] ───────────────────────────────── Elapsed time hr Polymer powder 0 1 2 3 6 ───────────────────────────────── Example 1.1 κ-Carrageenan K salt ○ ○ ○ ○ ○ Example 1.2 Agar ○ ○ ○ ○ ○ Comparative Example 1.1 Chitosan Salt A ○ △ × × × Comparative Example 1.2 Chitosan Salt B ○ × × × × Comparative Example 1.3 ι-Carrageenan Na Salt ○ △ △ × × ────────── ─────────────────────── ○: Precipitate cannot be confirmed △: Precipitate is present ×: Significant precipitate is present In the example, even after 6 hours from the preparation of the solution, no precipitate was generated and it was confirmed that the composition could be used satisfactorily.
【００２９】＜合成樹脂フィルムの製造＞前記工程で得
られた実施例および比較例の合成樹脂組成物を用いて合
成樹脂フィルムを作製し、その特性を比較した。 (a) 製膜条件：ドクターブレード（ヨシミツ精機 クリ
アランス５０、１００、２００μｍ）を用いて製膜 (b) 乾燥条件：８０℃、５分間の乾燥を行った後、１３
０℃で３分間乾燥させた。<Production of Synthetic Resin Film> Synthetic resin films were produced using the synthetic resin compositions of the examples and comparative examples obtained in the above steps, and their characteristics were compared. (a) Film formation conditions: film formation using a doctor blade (Yoshimitsu Seiki clearance 50, 100, 200 μm) (b) Drying conditions: 80 ° C., 5 minutes, and then 13
It was dried at 0 ° C. for 3 minutes.
【００３０】合成樹脂組成物の調液直後と３時間静置保
管した後で、それぞれ合成樹脂フィルムを製造した。ア
プリケータで離型紙に製膜した際における合成樹脂調液
の塗布性を評価した。Immediately after preparation of the synthetic resin composition and after storage for 3 hours, a synthetic resin film was produced. The applicability of the synthetic resin preparation when the release paper was formed into a film with an applicator was evaluated.
【００３１】[0031]
【表２】 ──────────────────────────────── クリアランス μｍ 高分子粉末 ５０ １００ ２００ ──────────────────────────────── 実施例2.1 κ−カラギーナンＫ塩 ○／○ ○／○ ○／○ 実施例2.2 寒天 ○／○ ○／○ ○／○ 比較例2.1 キトサン塩Ａ △／× △／× ○／○ 比較例2.2 キトサン塩Ｂ ×／× △／× ○／× 比較例2.3 ι−カラギーナンＮａ塩 △／× ○／× ○／○ ──────────────────────────────── ○：塗布筋、塗布ムラなし △：塗布ムラあり ×：塗布筋あり 評価は、（調液直後）／（３時間後）で表した。上記結
果をみれば、この発明の実施例では、調液直後および３
時間保管後の何れの場合も、クリアランスすなわち製膜
厚みに関係なく、良好な塗布性を示した。これに対し、
比較例では、製膜厚みが分厚い場合にはそれほどでもな
いが、製膜厚みが薄くなると、塗布性が低下し、特に、
保管後に使用した場合には塗布性が顕著に低下してい
る。[Table 2] ──────────────────────────────── Clearance μm Polymer powder 50 100 100 200 ─────── ────────────────────────── Example 2.1 κ-Carrageenan K salt ○ / ○ ○ / ○ ○ / ○ Example 2.2 Agar ○ / ○ ○ / ○ ○ / ○ Comparative Example 2.1 Chitosan Salt A △ / × △ / × ○ / ○ Comparative Example 2.2 Chitosan Salt B × / × △ / × ○ / × Comparative Example 2.3 ι-Carrageenan Na Salt △ / × ○ / × ○ / ○ ──────────────────────────────── ○: Coating streaks and coating unevenness △: Coating unevenness ×: The evaluation with coating streaks was expressed as (immediately after preparation of liquid) / (after 3 hours). From the above results, in the example of the present invention, immediately after the preparation and 3
In all cases after the time storage, good coatability was exhibited regardless of the clearance, that is, the film thickness. In contrast,
In the comparative example, when the film-forming thickness is thick, it is not so great, but when the film-forming thickness becomes thin, the coatability decreases, and in particular,
When used after storage, the coatability is significantly reduced.
【００３２】＜合成樹脂製品の性能確認＞この発明の実
施品の使用性能を確認した。下記配合で、合成樹脂調液
を作製した。材料および処理方法は、前記実施例と同様
であった。 配合：重量部 ＮＢ−６３０ １００ ＭＥＫ ３５ 添加物 表３参照 なお、添加物中、加水分解ゼラチン水溶液は、加水分解
ゼラチン水溶液（平均分子量１０，０００、固形分３０
％）を用いた。<Confirmation of Performance of Synthetic Resin Product> The usage performance of the product of the present invention was confirmed. A synthetic resin preparation was prepared with the following composition. The materials and treatment method were the same as in the previous example. Formulation: parts by weight NB-630 100 MEK 35 Additives See Table 3 In the additives, the hydrolyzed gelatin aqueous solution is a hydrolyzed gelatin aqueous solution (average molecular weight 10,000, solid content 30
%).
【００３３】[0033]
【表３】 ──────────────────────────── 添 加 物（配合量 重量部） ──────────────────────────── 実施例3.1 κ−カラギーナンＫ塩（３） ＋加水分解ゼラチン水溶液（１０） 比較例3.1 無 し 比較例3.2 キトサン塩Ａ（６） 比較例3.3 ι−カラギーナンＮａ塩（６） 比較例3.4 κ−カラギーナンＫ塩（６） 比較例3.5 キトサン塩Ａ（３） ＋加水分解ゼラチン水溶液（１０） ──────────────────────────── 製膜条件および乾燥条件は、ドクターブレードのクリア
ランスを２００μｍに設定した以外は、前記実施例と同
じであった。[Table 3] ──────────────────────────────────────────────────────────── ─────────────────── Example 3.1 κ-Carrageenan K salt (3) + hydrolyzed gelatin aqueous solution (10) Comparative example 3.1 None Comparative example 3.2 Chitosan salt A ( 6) Comparative Example 3.3 ι-Carrageenan Na Salt (6) Comparative Example 3.4 κ-Carrageenan K Salt (6) Comparative Example 3.5 Chitosan Salt A (3) + Hydrolyzed Gelatin Aqueous Solution (10) ────────── ─────────────────── The film forming conditions and the drying conditions were the same as in the above-mentioned example except that the clearance of the doctor blade was set to 200 μm.
【００３４】成形された合成樹脂フィルムに、６０℃の
温水で３０分間の溶出除去処理を行い、製品フィルムを
得た。この製品フィルムの透湿度をＪＩＳ Ｚ−０２０
８に準拠して測定した。また、溶出除去処理の前後にお
ける合成樹脂フィルムの重量変化から、溶出率を測定し
た。その結果を表４に示している。The molded synthetic resin film was subjected to elution and removal treatment with warm water at 60 ° C. for 30 minutes to obtain a product film. The moisture permeability of this product film is measured according to JIS Z-020.
It measured based on 8. Further, the elution rate was measured from the weight change of the synthetic resin film before and after the elution removal treatment. The results are shown in Table 4.
【００３５】[0035]
【表４】 以上の結果をみれば、合成樹脂に、特定の温水溶解性高
分子粉末と蛋白質加水分解物水溶液を含有させておき、
この合成樹脂を成形した後、溶出除去処理を行うことに
より、合成樹脂製品の透湿性を大幅に改善できることが
実証された。[Table 4] Based on the above results, the synthetic resin was allowed to contain a specific hot water-soluble polymer powder and a protein hydrolyzate aqueous solution,
It has been proved that the moisture permeability of the synthetic resin product can be greatly improved by performing elution removal treatment after molding the synthetic resin.
【００３６】[0036]
【発明の効果】以上に述べた、この発明にかかる改質合
成樹脂組成物、改質合成樹脂製品および改質合成樹脂製
品の製造方法によれば、合成樹脂に、特定の温水溶解性
高分子粉末と蛋白質加水分解物水溶液とを含有させてお
くことによって、合成樹脂調液を保管しているうちに沈
殿を生じることがなく、塗布性が悪くなることもない。As described above, according to the modified synthetic resin composition, the modified synthetic resin product and the method for producing the modified synthetic resin product according to the present invention, the synthetic resin contains a specific hot water-soluble polymer. By containing the powder and the aqueous solution of protein hydrolyzate, precipitation does not occur during storage of the synthetic resin preparation, and the coatability does not deteriorate.
【００３７】このように、温水溶解性高分子粉末と蛋白
質加水分解物水溶液が良好に混合された改質合成樹脂組
成物を成形した後、温水溶解性高分子粉末および蛋白質
加水分解物水溶液を溶出除去して得られる改質合成樹脂
製品は、その内部構造に複雑な連続多孔質状の空隙を備
えていることにより、吸湿性と透湿性の両方を兼ね備え
た吸放湿性の良好な合成樹脂製品となる。As described above, after molding the modified synthetic resin composition in which the hot water-soluble polymer powder and the protein hydrolyzate aqueous solution are well mixed, the hot water-soluble polymer powder and the protein hydrolyzate aqueous solution are eluted. The modified synthetic resin product obtained by removal has a complex continuous porous void in its internal structure, so that it is a synthetic resin product that has both moisture absorption and moisture permeability and good moisture absorption and desorption properties. Becomes
【００３８】改質合成樹脂組成物に温水溶解性高分子粉
末が均一に混合されていれば、長期間にわたって安定し
て保管しておくことができ、成形時の塗布性も良好にな
り、品質性能に優れた合成樹脂製品を製造することが可
能になる。得られた改質合成樹脂製品は、風合いや外観
性の点でも、従来の合成樹脂に比べて、はるかに天然の
素材に近い良好なものが得られる。しかも、温水溶解性
高分子粉末および蛋白質加水分解物水溶液は何れも、天
然材料から製造されるものが多いので、人体に対する安
全性も高く、人体に直接触れる衣料等にも好適に使用で
きる。If the modified synthetic resin composition is uniformly mixed with the hot water-soluble polymer powder, it can be stably stored for a long period of time, and the coating property at the time of molding becomes good, and the quality is improved. It becomes possible to manufacture synthetic resin products with excellent performance. The modified synthetic resin product thus obtained is superior in terms of texture and appearance to that of a natural material as compared with conventional synthetic resins. Moreover, since both the hot water-soluble polymer powder and the aqueous solution of protein hydrolyzate are mostly manufactured from natural materials, they are highly safe to the human body and can be suitably used for clothing directly in contact with the human body.
【００３９】その結果、合成皮革や繊維製品等の表面仕
上げ加工用樹脂や各種のフィルム・シート、塗料や接着
剤、その他の製品に利用したときに、優れた吸放湿性あ
るいは風合い等を発揮でき、これらの製品の品質性能の
向上および用途の拡大に大きく貢献することができる。
具体的には、例えば、合成皮革の表面層を構成する層材
料として用いたり、合成皮革を構成する繊維層に含浸さ
せて用いたりした場合には、天然の皮革と同程度の優れ
た吸放湿性を発揮し、肌触りが滑らかで、強過ぎない自
然な光沢を示すものとなり、従来の合成皮革の欠点であ
ったムレ感やベトツキ感を解消して、合成皮革の品質向
上を果たすことができる。As a result, when used in surface finishing resins such as synthetic leather and textile products, various films and sheets, paints and adhesives, and other products, they can exhibit excellent moisture absorption and release properties or texture. , Can greatly contribute to improving the quality performance of these products and expanding their applications.
Specifically, for example, when it is used as a layer material constituting a surface layer of synthetic leather or impregnated into a fiber layer constituting synthetic leather, it has excellent absorption and release properties comparable to those of natural leather. It exhibits moistness, has a smooth texture, and shows a natural luster that is not too strong, eliminating the stuffiness and stickiness that were the drawbacks of conventional synthetic leather and improving the quality of synthetic leather. .
【００４０】各種の衣料の表面仕上げあるいは繊維の表
面加工に用いた場合には、汗の吸収性が良くなるととも
に、吸収した汗をすぐに放出することができるので、さ
わやかな着心地感を与えることができる。When it is used for surface finishing of various kinds of clothing or surface treatment of fibers, the absorbability of sweat is improved and the absorbed sweat can be immediately released, so that a refreshing feeling is provided. be able to.
Claims (3)
Ｃａ塩、ローカストビーンガム、寒天、ジェランガムか
らなる群から選ばれた少なくとも１種の温水溶解性高分
子粉末と蛋白質加水分解物水溶液とを含有してなること
を特徴とする改質合成樹脂組成物。1. A synthetic resin containing ι · κ-carrageenan K ·
A modified synthetic resin composition comprising at least one hot water-soluble polymer powder selected from the group consisting of Ca salt, locust bean gum, agar and gellan gum, and an aqueous solution of protein hydrolyzate. .
脂製品を製造する方法において、合成樹脂組成物に、ι
・κ−カラギーナンＫ・Ｃａ塩、ローカストビーンガ
ム、寒天、ジェランガムからなる群から選ばれた少なく
とも１種の温水溶解性高分子粉末と蛋白質加水分解物水
溶液とを含有させておき、この合成樹脂組成物を成形し
た後、温水溶解性高分子粉末と蛋白質加水分解物を溶出
除去することを特徴とする改質合成樹脂製品の製造方
法。2. A method for producing a synthetic resin product by molding and curing the synthetic resin composition, comprising:
This synthetic resin composition containing at least one hot water-soluble polymer powder selected from the group consisting of κ-carrageenan K / Ca salt, locust bean gum, agar, and gellan gum and a protein hydrolyzate aqueous solution. A method for producing a modified synthetic resin product, characterized in that after molding the product, the hot water-soluble polymer powder and the protein hydrolyzate are eluted and removed.
方法により製造された改質合成樹脂製品。3. Production of the modified synthetic resin product according to claim 2.
A modified synthetic resin product produced by the method .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4013408A JPH083042B2 (en) | 1992-01-28 | 1992-01-28 | Modified synthetic resin composition, modified synthetic resin product, and method for producing modified synthetic resin product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4013408A JPH083042B2 (en) | 1992-01-28 | 1992-01-28 | Modified synthetic resin composition, modified synthetic resin product, and method for producing modified synthetic resin product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05202298A JPH05202298A (en) | 1993-08-10 |
| JPH083042B2 true JPH083042B2 (en) | 1996-01-17 |
Family
ID=11832309
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4013408A Expired - Fee Related JPH083042B2 (en) | 1992-01-28 | 1992-01-28 | Modified synthetic resin composition, modified synthetic resin product, and method for producing modified synthetic resin product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH083042B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5427854B2 (en) * | 1973-08-08 | 1979-09-12 | ||
| JPH01192874A (en) * | 1988-01-22 | 1989-08-02 | Ain Kk | Moisture-permeable and waterproof cloth |
| JPH01289457A (en) * | 1988-02-04 | 1989-11-21 | Takeda Chem Ind Ltd | Edible film |
| JPH035110A (en) * | 1989-06-02 | 1991-01-10 | Ain Kk | Leather-patterned molding and its molding method |
-
1992
- 1992-01-28 JP JP4013408A patent/JPH083042B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05202298A (en) | 1993-08-10 |
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