JPS6352669B2 - - Google Patents
Info
- Publication number
- JPS6352669B2 JPS6352669B2 JP55080137A JP8013780A JPS6352669B2 JP S6352669 B2 JPS6352669 B2 JP S6352669B2 JP 55080137 A JP55080137 A JP 55080137A JP 8013780 A JP8013780 A JP 8013780A JP S6352669 B2 JPS6352669 B2 JP S6352669B2
- Authority
- JP
- Japan
- Prior art keywords
- nitrocellulose
- organic solvent
- inert
- isocyanate groups
- molded
- 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
Links
- 239000000020 Nitrocellulose Substances 0.000 claims description 170
- 229920001220 nitrocellulos Polymers 0.000 claims description 170
- 239000000203 mixture Substances 0.000 claims description 109
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 93
- 239000002904 solvent Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 61
- 239000003960 organic solvent Substances 0.000 claims description 48
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 29
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 23
- 238000000465 moulding Methods 0.000 claims description 22
- 239000012046 mixed solvent Substances 0.000 claims description 21
- 239000008188 pellet Substances 0.000 claims description 20
- 239000008187 granular material Substances 0.000 claims description 18
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000008096 xylene Substances 0.000 claims description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 10
- 230000001070 adhesive effect Effects 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 5
- XLLIQLLCWZCATF-UHFFFAOYSA-N ethylene glycol monomethyl ether acetate Natural products COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 claims description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 claims description 4
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 4
- 229940090181 propyl acetate Drugs 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 4
- -1 iclohexanone Chemical compound 0.000 claims description 3
- JSZOAYXJRCEYSX-UHFFFAOYSA-N 1-nitropropane Chemical compound CCC[N+]([O-])=O JSZOAYXJRCEYSX-UHFFFAOYSA-N 0.000 claims description 2
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- MCSAJNNLRCFZED-UHFFFAOYSA-N nitroethane Chemical compound CC[N+]([O-])=O MCSAJNNLRCFZED-UHFFFAOYSA-N 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims 1
- KTSWBLUMAWETAK-UHFFFAOYSA-N heptane octane Chemical compound CCCCCCC.CCCCCCCC.CCCCCCC KTSWBLUMAWETAK-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 description 51
- 235000019441 ethanol Nutrition 0.000 description 31
- 239000007787 solid Substances 0.000 description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- 238000004898 kneading Methods 0.000 description 15
- 239000003973 paint Substances 0.000 description 9
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000012948 isocyanate Substances 0.000 description 5
- 229920005749 polyurethane resin Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 150000002513 isocyanates Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- 235000010724 Wisteria floribunda Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005421 electrostatic potential Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000006247 magnetic powder Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 1
Description
本発明は実質的にアルコール類および／また
は、水を含有しない新規な成型されたニトロセル
ロース組成物及びその製造方法に関するものであ
る。
ニトロセルロース製品は、取扱時の安全性から
通常、エチルアルコール、イソプロピルアルコー
ル、ブチルアルコール等のアルコール類および／
または水で湿潤化させて使用に供されている。
ニトロセルロースは塗料中に配合されてすぐれ
た乾燥性、顔料分散性を与えるため、アクリル樹
脂塗料を始め多くの塗料、インキおよび接着剤に
加えて使用されている。また、この特性を与える
ため近年ポリウレタン樹脂塗料に加えて使用する
試みも増加している。
しかし、アルコール類および／または水を含有
するニトロセルロースはポリウレタン樹脂塗料に
加えて使用する場合、ポリウレタン樹脂塗料中の
イソシアネート基とアルコール類および水が反応
し、イソシアネート基を消費するため、ウレタン
樹脂塗料本来の性状および性能に著しい悪影響を
及ぼす欠陥を有している。これらの欠点を是正す
るための工業的な試みはいづれも成功していな
い。
一つの方法はアルコール類および／または水で
湿潤化したニトロセルロースを乾燥し、アルコー
ル類および／または水を蒸発させて除き乾燥ニト
ロセルロースにすることであるが、乾燥したニト
ロセルロースは自然分解等の危険性から社会通念
上許されざるべきものである。
他の方法は、トリオールで湿潤化したニトロセ
ルロースも提案されているが、これは帯電性が強
く、また取扱い中にトルエンが揮発するとニトロ
セルロースが粉になり易く、これが飛散して掃除
困難な場所に溜り易く自然発火等の危険があり、
帯電性との危険性と合せて安全上の保障がなされ
ていないため製品化されていない。
さらに他の一つの方法は、アルコール類およ
び／または水で湿潤化したニトロセルロースの湿
潤剤をフタル酸エステル類等の可塑剤、たとえば
フタル酸ジブチルと置きかえた固形状のニトロセ
ルロース組成物「市販名：クリヤーチツプ旭化
成工業(株)製」も提案されている。これは当然アル
コール類および／または水を実質的に含有しない
こと、帯電性はトルエン湿潤ニトロセルロースよ
りも改善されていることを生かして使用されてい
るものの、フタル酸エステル等の可塑剤を使用し
ているため塗膜の硬さ、乾燥性を阻害することか
ら好まれない分野も多い。
このようなことから、特にポリウレタン樹脂被
覆組成物に適したニトロセルロース製造の提供を
市場から強く要請されているにも拘らず解決され
るに至つていない。
本発明者等はこれらの点に留意し、鋭意検討を
重ねた結果、本発明に至つたものである。
すなわち、本発明の第１の発明は、
(a) ニトロセルロース、
(b) イソシアネート基に不活性でかつニトロセル
ロースを溶解する有機溶剤、
および
(c) イソシアネート基に不溶性でかつニトロセル
ロースを溶解しない有機溶剤
から成り、この３者は均一な固相を形成してお
り、(a)の含有量は50〜80重量％、(b)／(c)＝15〜
80／20―85（重量比）であり、非粘着性の粒状、
チツプ状またはペレツト状であることを特徴とす
る成型されたニトロセルロース組成物であり、第
２の発明は、アルコール類および／または水で湿
潤化したニトロセルロースに、イソシアネート基
に不活性でありかつニトロセルロースを溶解する
有機溶剤の単独または該有機溶剤とイソシアネー
ト基に不活性でありかつニトロセルロースを溶解
しない有機溶剤との混合物からなる混合溶剤を、
上記ニトロセルロースが少くとも部分的に溶解
し、かつ得られた混合物が常温では機械的な力を
加えないと容易に流動しない程度の量で以つて加
え、混練または捏和した後、機械的に粒状、チツ
プ状またはペレツト状に成型する工程と、該成型
品にイソシアネート基に不活性でかつニトロセル
ロースを溶解しない有機溶剤の単独または該有機
溶剤とイソシアネート基に不活性でかつニトロセ
ルロースを溶解する有機溶剤との混合物を加え、
加熱および／または減圧により、アルコール類お
よび／または水を使用した有機溶剤の一部ととも
に実質的に除去する留出工程から成る成型された
ニトロセルロース組成物の製造方法である。
本発明に用いられるニトロセルロースは、ニト
ロセルロースの窒素分（Ｎ％）および粘度（平均
重合度）を特に制限するものではなく、いづれも
使用できるが、好ましくはJIS―Ｋ―6703に記載
される工業用ニトロセルロースで、ニトロセルロ
ースのＮ％が10.7〜12.2％、粘度記号がＬ1/8〜
１／２およびＨ1/16〜120であり、エチルアルコー
ル、イソプロピルアルコールまたはブチルアルコ
ール等のアルコール類および／または水で湿潤化
したものである。
本発明に用いられるイソシアネート基に不活性
なニトロセルロース可溶性有機溶剤（以下、可溶
性溶剤という）は、公知のニトロセルロースを溶
解する有機溶剤のうちOH基、COOH基、NH2基
等のイソシアネート基と活性な反応基を有しない
有機溶剤であり、例えば代表的なものとして酢酸
エチル、酢酸プロピル、酢酸ブチル、エチレング
リコールモノメチルエーテルアセテート、エチレ
ングリコールモノエチルエーテルアセテート等の
酢酸エステル類、メチルエチルケトン、メチルイ
ソブチルケトン、イソホロン、シクロヘキサノン
等のケトン類およびニトロメタン、ニトロエタ
ン、ニトロプロパン等のニトロパラフイン類をあ
げることができる。これらのうちニトロセルロー
スの溶解性、取扱い時の臭気、経済性等を考慮し
たとき酢酸エチル、酢酸プロピル、酢酸ブチル、
メチルエチルケトンおよびメチルイソブチルケト
ンが好ましい。
本発明に用いられるイソシアネート基に不活性
なニトロセルロース不溶性有機溶剤（以下、不溶
性溶剤という）の代表的なものとしてヘキサン、
ペンタン、オクタン、シクロヘキサン、メチルシ
クロヘキサン、ソルベントナフタ、石油スピリツ
ト、ケロシン、ベンゼントルエン、キシレン等の
脂肪族、脂環族および芳香族の炭化水素類および
トリクロルエチレン、四塩化炭素等のハロゲン化
炭化水素類をあげることができる。これらのう
ち、取扱時の臭気、経済性等を考慮したときトル
エン、キシレンおよびヘキサンが好ましい。
本発明の構成および効果を図面にて説明する。
第１図はニトロセルロースイソシアネートに不
活性でかつニトロセルロースを溶解する有機溶剤
およびイソシアネートに不活性でかつニトロセル
ロースを溶解しない有機溶剤の３者の構成を示す
三角図表であり、Ａは本発明組成物の構成範囲を
示すもので、この範囲の３者から成るニトロセル
ロース組成物は粘着性を有さず、かつ任意の形状
に成型してもその形状で保つ範囲を示す。Ｂはこ
の範囲の３者から成るニトロセルロース組成物は
粘着性を有し、従つて任意の形状に成型しても、
時間の経過とともに融着がはじまり、遂には成型
形状を保てなくなる範囲を示す。Ｃはこの範囲の
３者から成るニトロセルロース組成物はニトロセ
ルロースが相分離をおこしニトロセルロースと両
有機溶剤が分離して均一相をなさない範囲を示
す。
たとえば、まずニトロセルロース20ｇを酢酸エ
チル（ニトロセルロースを溶解する溶剤）80ｇに
溶解させた場合の挙動を説明すると、この組成は
第１図のａで示され、粘着性が著しく、成形品に
なりえない液状である。これをこのまゝ濃縮する
と酢酸エチルは蒸発により除去され、同図のｂ
点、ｃ点をとおるがいずれも粘着性を有する液状
もしくはペースト状で仮に成型されたとしても、
すぐ成型品どおしが合一をおこし、実質的には成
型品になり得ない。更に濃縮を続けるとついには
酢酸エチルは実質的にすべて除去され、ニトロセ
ルロース単独となり、発火の危険性が生じてく
る。またニトロセルロース20ｇを酢酸エチル（ニ
トロセルロースを溶解する溶剤）50ｇ、キシレン
（ニトロセルロースを溶解しない溶剤）30ｇの混
合溶剤に溶解した場合の挙動を同じく第１図で説
明する。この組成は同図のｄで示され、粘着性が
著しく成形品になり得ない液状である。これを蒸
留すると両溶剤は蒸発により除去されるものの蒸
気圧の関係から酢酸エチルが先に除去されるため
ほゞｃ点、ｆ点をとおり濃縮される。ｅ点は粘着
性を有するペースト状で仮にこの点で成型された
としても、すぐ成型品どおしが合一し実質的に成
形品になり得ない。ｆ点ではニトロセルロースが
析出し、ニトロセルロースと両有機溶剤が二層分
離する。この点では３者が均一固相を呈さず勿論
成型品にはなり得ない。
このように限られた３者の構成組成でもつての
み非粘着性の粒状、チツプ状またはペレツト状
の、かつ３者が均一固相を呈する成型されたニト
ロセルロース組成物となるのである。
また、特公昭44−20230号公報実施例１，２で
得られた組成は第１図のｇ，ｈ点で示され、いず
れもニトロセルロースを溶解する有機溶剤を含有
しないので、ニトロセルロースを溶解しない溶剤
とニトロセルロースから成り、この２者は均一固
相とならず、単に物理的付着のみを生じている。
また特公昭45−9397号公報の実施例１で得られ
た組成は第１図のｉ点で示されるが、これはニト
ロセルロースと水すなわちニトロセルロースを溶
解せずイソシアネート基に活性な溶剤から成り、
この２者は均一固相とならず、単に物理的付着の
み生じている。
本発明の製造方法は、アルコール類および／ま
たは水で湿潤化した繊維状ニトロセルロースに、
可溶性溶剤の単独または該可溶性溶剤と不溶性溶
剤との混合溶剤を、該ニトロセルロースが少くと
も部分的に溶解し、かつ、得られた組成物が常温
では機械的な力を加えないと容易に流動しない程
度の量で以て加え、混練または捏和したのち、機
械的に粒状チツプ状またはペレツト状に成型する
成型工程と、ついで、この成型工程で得られたア
ルコール類及び／または水を含んだ成型品に、不
溶性溶剤の単独または該不溶性溶剤と可溶性溶剤
との混合溶剤を加えたのち、加熱および／または
減圧を行つてアルコールおよび／または水を使用
した有機溶剤の一部とともに実質的に留出除去す
る留出工程とよりなる。
本発明方法における成型工程で混練または捏和
したのち、機械的に粒状、チツプ状またはペレツ
ト状に成型する方法としては、混練または捏和
し、ついで成型する方法と、混練または捏和と成
型を連続的に行う方法等があり、いづれの方法も
実施できる。
これらのうち経済性、作業能率等から混練また
は捏和から成型までを連続的に行なう方法が好ま
しい。
また、成型工程で粒状、チツプ状またはペレツ
ト状に成型された成型品は、次の留出工程および
製品でもその形状をほゞ保持できるので、得られ
た組成物を成型するのは、次の点から特に有意義
である。即ち繊維状ニトロセルロースの様な繊維
による絡み合いによる嵩高性がなく、嵩密度も大
きくなり、流動性も非常に優れたものになり、従
つて容器への充填密度が大きくなるため輸送費の
軽減ができること、収納容器からの取扱い作業性
が非常に改善されることである。さらに機械的に
粒状、チツプ状またはペレツト状に成型する形状
を特に制限するものではないが、上記の意味から
最も好ましい成形品の形状は例えば一定の形状を
有するダイスから押圧しこれを短かくカツトする
とか或いはロール等でシート状にし、これを一定
の大きさにカツトした粒状、ペレツト状またはチ
ツプ状の形状に成型した成型品である。
本発明方法の混練または捏和したのち、粒状、
チツプ状またはペレツト状に成型するまでの機器
としてその代表的なものは、ニーダーミキサー、
インターナルミキサー、ポニーミキサー、パグミ
ル、ギヤーコンパウダー、ロールミル、コニーダ
ー、スクリユー押出し機、ポテーター、シユレツ
ダーカツター、ブリケツトマシン、ロールカツタ
ー等をあげることができる。これらの機器を用い
て粒状、チツプ状またはペレツト状に成型するま
での雰囲気および／または次の留出工程までの保
管方法は、空気中、窒素ガス中、水中のいづれで
も行うことができる。ニトロセルロースに有機溶
剤を加えた場合には、一般的に、ニトロセルロー
スの粘度記号が大きい程、有機溶剤溶液中で高い
粘度（平均重合度）を与える。可溶性溶剤の種類
によつても溶かされたニトロセルロースの粘度が
異なる。さらに可溶性溶剤と不溶性溶剤との混合
割合によつても溶かされたニトロセルロースの粘
度が異る。さらにまた、同一溶剤ではその添加量
が多くなるとその粘度が低くなる等の粘度特性が
絡み合つて影響するので、本発明のアルコール類
および／または水で湿潤化したニトロセルロース
に可溶性溶剤の単独または該可溶性溶剤と不溶性
溶剤とからなる混合溶剤を、上記ニトロセルロー
スが少くとも部分的に溶解し、かつ得られた組成
物が常温では機械的な力を加えないと容易に流動
しない程度の量で以て加え、混練または捏和した
のち、機械的に粒状、チツプ状またはペレツト状
に成型する本発明方法においても加える有機溶剤
量の範囲の特定も容易ではないが、得られた組成
物の流動が容易であると成型品の形状の保持が難
かしいので好ましくない。これらのことを考慮し
て該組成物が常温では機械的な力を加えないと容
易には流動しない程度の範囲の粘度は、50000cps
（20℃）以下であり、好ましくは100000cps（20℃）
以下である。さらに最も好ましくはニトロセルロ
ースが部分的に溶解しても完全に溶解せず、不溶
解部分のニトロセルロースを含み常温では機械的
な力を加えないと流動しない程度の形状保持性の
ある範囲である。
成型工程で用いるニトロセルロースと可溶性溶
剤の割合は前述の如く、ニトロセルロースの粘度
特性および湿潤剤の種類、量及び、可溶性溶剤単
独であるか、可溶性溶剤と不溶性溶剤との混合溶
剤であるかまたは混合溶剤の混合比率等多くの因
子が絡み合つてその範囲の特定は非常に困難であ
るが、本発明の理解をさらに容易にするために一
例を示す次の通りである。即ち、水で湿潤化した
Ｈ1/2ニトロセルロースのニトロセルロース100重
量部に対して、可溶性溶剤の単独の場合は可溶性
溶剤25〜150重量部であり、可溶性溶剤と不溶性
溶剤の比率が50：50の混合溶剤の場合は、該混合
溶剤が40〜180重量部である。
機械的に粒状、チツプ状またはペレツト状に成
型したアルコール類および／または水を含む成型
品を得るために加える混合溶剤は、不溶性溶剤を
80重量％以下であり、好ましくは約70重量％以下
である。不溶性溶剤が約80重量％以上になるとニ
トロセルロースを少くとも部分的に溶解し、得ら
れた組成物が常温では機械的な力を加えないと容
易に流動しない程度の量で以て加え、混練または
捏和して、機械的に粒状、チツプ状またはペレツ
ト状に成型するとまたは成型品の形状の保持が難
かしくなるためである。さらに成型品中の可溶性
溶剤の含有量が異常に少くなり成型品の帯電性が
増加し、取扱い作業性に悪影響を及ぼす。
本発明方法の成型工程でえられたアルコール類
および／または水を含む成型品は、繊維状ニトロ
セルロースが可溶性溶剤と機械的成型時の力の作
用によりニトロセルロースの成型品になつている
ことが好ましい。
次にアルコール類および／または水を含む成型
品に、不溶性溶剤の単独または該不溶性溶剤と可
溶性溶剤との混合溶剤を加え、加熱および／また
は減圧してアルコール類および／または水を前記
両有機溶剤の一部とともに実質的に除去するため
の溶剤は、アルコール類および／または水より沸
点が高いか、またはアルコール類および／または
水と共沸する不溶性溶剤を用いる方法があり、い
づれの方法も使用できる。また、アルコール類お
よび／または水で湿潤化したニトロセルロース
に、水で湿潤化したニトロセルロースを使用する
場合は、水と最低共沸点を有する不溶性溶剤の単
独または該不溶性溶剤と可溶性溶剤との混合溶剤
を用いるのが経済的であり特に好ましい。さら
に、アルコール類および／または水を含む成型品
に、不溶性溶剤の単独または該不溶性溶剤と可溶
性溶剤との混合溶剤を加え、加熱および／または
減圧してアルコール類およびまたは水を前記両有
機溶剤の一部とともに実質的に除去する方法は、
減圧下、常圧下または減圧下で加熱蒸留する方法
であり、いづれも有効である。またニトロセルロ
ースは加熱温度を高める程、ニトロセルロース自
身の分解を促進し、危険性が増すため、実用上は
100℃以上の高温で加熱蒸留することは好ましく
なく、溶剤の沸点が高い場合は100℃以下の温度
で減圧蒸留することが好ましい。さらにまた、該
アルコール類および／または水を含む成型品に加
える不溶性溶剤と可溶性溶剤との混合溶剤は、可
溶性溶剤を20重量％以下含有する混合溶剤でもよ
い。該混合溶剤において可溶性溶剤の含有量が20
重量％以上になると可溶性溶剤の割合が増加する
とともに、成型品間の付着が起り易くなり、つい
には全体が集塊状になり易くなる、これを防ぐた
めに非常に多量の該混合溶剤を使用せねばならず
実用上は好ましくない。
トルエン、キシレンの単独または混合物と可溶
性溶剤とからなる混合溶剤を使用する場合の可溶
性有機溶剤の含有割合は15重量％以下が特に好ま
しい。
本発明の成型ニトロセルロース組成物は、ニト
ロセルロース50〜80重量％、好ましくは50〜75重
量％よりなり、含有する混合溶剤中の可溶性溶剤
量は15〜80重量％、好ましくは20〜70重量％であ
る。また成型ニトロセルロース組成物は、繊維状
のニトロセルロースや粉末状ニトロセルロースを
実質的に含まず、成型時の形状をほゞ保持した固
形に成型されていることである。これは従来のア
ルコール類および／または水で湿潤化したニトロ
セルロースに見られる様な取扱作業中に湿潤分が
揮発してニトロセルロースが乾燥状態に近づき、
短繊維状等のニトロセルロースの粉塵が飛散し掃
除の困難な場所に溜り、そのまゝ放置すると自然
分解等による安全上の問題を起こすのに比べ、成
型ニトロセルロース組成物は任意の大きさに成型
されて容易には飛散し難くなつているため、これ
らの問題は起らず安全上も取扱い易いこと、さら
に繊維状ニトロセルロースの様な繊維状の絡みが
ないため充填容器からの取扱作業性に優れてい
る。さらに、成型ニトロセルロース組成物は意外
にも比較的に帯電性が少いことである。これは火
災等の危険性があり取扱上の安全性が重要なニト
ロセルロースにあつては大きな特徴である。この
特徴は、成型ニトロセルロース組成物が成型工程
において、可溶性溶剤を少くともニトロセルロー
スの一部が溶解する程度に加えられ、混練または
捏和したのち、機械的に粒状、チツプ状またはペ
レツト状にする成型工程と次の留出工程の効果に
より、可溶性溶剤がニトロセルロースに実質的に
ほゞ均一に選択吸着されてほゞ均質になり、前記
両有機溶剤の液状および／またはガス状の雰囲気
の中にあること、粒状、チツプ状またはペレツト
状に成型してあるため繊維状ニトロセルロースよ
りも重量当りの表面積が小さくなつていることに
よるものであろう。この成型ニトロセルロース組
成物の帯電性は成型ニトロセルロース組成物中に
含まれる前記両有機溶剤のうち可溶性溶剤の割合
が増すに従つて帯電性は少くなつて来る。前記
「クリヤーチツプ」と同程度の帯電性を示す可
溶性溶剤の割合は、成型ニトロセルロース組成物
中に含まれる可溶性溶剤と不溶性溶剤の割合で示
すと、可溶性溶剤が15重量％以上でありより安全
な側にするには好ましくは20重量％以下である。
さらにまた、成型ニトロセルロース組成物は、イ
ソシアネート基に活性なアルコール類および／ま
たは水を実質的に含まないこと、被覆組成物に好
ましくない影響を及ぼすフタル酸エステル等の可
塑剤を含まないことが特徴であり、今まで開発さ
れなかつた全く新規な成型ニトロセルロース組成
物であるため、ポリウレタン樹脂塗料等のイソシ
アネート基を有する被覆組成物、特に磁気粉を含
むポリウレタン被覆組成物等の顔料分散剤、初期
乾燥剤として有効である、また塗料製造時におい
て水を好まないアクリル樹脂塗料、ラツカー、イ
ンキおよび接着剤の分野も有効である。
粒状、チツプ状またはペレツト状に成型された
ものは、流動性がよく、溶解仕込時の容器からの
取出し性がよい。また、粒状、チツプ状またはペ
レツト状に成型されたものは不定形の大きい塊の
あるものより、容器への充填性がよく、輸送費が
安くなる。さらに、不定形の大きい塊のあるもの
よりも、粒状、チツプ状またはペレツト状のもの
は、形が整つていて、ラツカーに溶解する作業
で、分散溶解性がよく、溶解作業が短時間に終了
するので、需要家から非常に好まれる。
以下、本発明を実施例により詳細に説明する。
実施例中の部および％は特に示さない限り重量部
および重量％を示す。
実施例 １
水分を30％含有するＨ1/2ニトロセルロース143
ｇにメチルイソブチルケトン（以下MIBKと略
す）100ｇを加え、手で軽く混練してペースト状
の組成物を得た、得られた組成物を出口に２ｍ／
ｍφの細穴を多数つけたダイスのある手廻しスク
リユー押出器に仕込み、予め準備しておいたトル
エン300ｇ中に押出した、トルエン中の成型物を
長さ約20ｍ／ｍにカツトして水を含むペレツト状
の成型品とし、前記トルエンを含む全量をロータ
リーエバポレーター（ヤマト科学(株)製）に移し、
80℃に加熱した水浴中で200Torrに減圧蒸留し
て、固形物65％の成型ニトロセルロース組成物
153ｇを得た。この成型ニトロセルロース組成物
は繊維状ニトロセルロースは見られず、流動性の
よい固形状であり、包装容器への付着性もなく、
取出し作業性も非常に良好であつた。該成型ニト
ロセルロース組成物中のニトロセルロースはＨ1/
２の粘度特性を有し、該成型ニトロセルロース組
成物中の水分をカールフイツシヤー法で、溶剤組
成をガスクロマトフイー法で測定したところ、水
分0.7％、MIBKとトルエンの比率は４／６であ
つた。
実施例 ２
水分を25％含有するＨ1/2ニトロセルロース134
ｇにMIBK30ｇとトルエン70ｇを加え、手で軽く
混練して、やゝ硬いペースト状の組成物を得た。
得られた組成物を、予め準備していたトルエン
480ｇとMIBK120ｇの混合溶剤中に実施例１と同
様の方法で押出しカツトして、水を含む成型品を
得た。前記混合溶剤を含む成型品の全量を実施例
１と同様の方法で減圧蒸留し、固形分61％の成型
ニトロセルロース組成物163ｇを得た、該成型ニ
トロセルロース組成物は水分0.5％で、MIBKと
トルエンの比率は25／75であつた。また該成型ニ
トロセルロース組成物は繊維状ニトロセルロース
は見られず、成型時の形状をほゞ保持した流動性
のよい固形物で包装容器からの取出し作業性も非
常に良好であつた。
実施例 ３
水分25％を含有するＨ1/2ニトロセルロース134
ｇにMIBK65ｇとトルエン45ｇを加え、手で軽く
混練して、やゝ軟かいが殆んど流動のないペース
ト状の組成物を得た、得られた組成物を予め準備
していたトルエン300ｇの中に実施例１と同様の
方法で押出しカツトして、水を含む成型品を得
た、該トルエンを含む成型品の全量を実施例１と
同様の方法で、150Torrに減圧蒸留し、固形分70
％の成型ニトロセルロース組成物142ｇを得た、
該成型ニトロセルロース組成物は水分0.8％、
MIBKとトルエンの比率は18／82であつた。また
該成型ニトロセルロース組成物は繊維状のニトロ
セルロースは見られず、成型時の形状をほゞ保持
した流動性のよい固形物で包装容器からの取出し
作業性も非常に良好であつた。
実施例 ４
水分30％を含有するＨ1/2ニトロセルロース143
ｇにMIBK100ｇを加え、手で軽く混練してペー
スト状の組成物を得た、得られた組成物を予め準
備しておいたキシレン300ｇ中に実施例１と同様
の方法で押出しカツトして、水を含む成型品を得
た。該キシレンを含む成型品の全量を実施例１と
同様の方法で、50Torrに減圧蒸留し、固形分75
％の成型ニトロセルロース組成物133ｇを得た、
該成型ニトロセルロース組成物は水分0.6％、
MIBKとキシレンの比率は19／81であつた。
実施例 ５
水分30％を含有するＨ1/4ニトロセルロース143
ｇに酢酸ブチル100ｇを加え、手で軽く混練して
ペースト状の組成物を得た、得られた組成物を予
め準備しておいたキシレン350ｇ中に実施例１と
同様の方法で押出しカツトして、水を含む成型品
を得た。キシレンを含む成型品の全量を実施例１
と同様の方法で、50Torrに減圧蒸留し、固形分
75％の成型ニトロセルロース組成物133ｇを得た。
該成型ニトロセルロース組成物は水分0.5％、酢
酸ブチルとキシレンの比率は21／79であつた。
実施例 ６
イソプロピルアルコールを30％含有するＨ1/4
ニトロセルロース143ｇにMIBK35ｇとキシレン
35ｇを加え、手で混練してやゝ軟かいペースト状
の組成物を得た。得られた組成物をブルツクフイ
ールド粘度計（以下Ｂ型粘度計と称す）を用い
て、20℃における粘度を測定したが100000cps以
上で測定できなかつた。この組成物を予め準備し
ておいたキシレン600ｇ中に実施例１と同様の方
法で押出しカツトして、水を含む成型品を得た、
キシレンを含むこの成型品の全量を実施例１と同
様の方法で、50Torrに減圧蒸留し、固形分70％
の成型ニトロセルロース組成物142ｇを得た。該
成型ニトロセルロース組成物は水分0.6％、
MIBKとキシレンの比率は２／８であつた。さら
にガスクロマトフイー法でイソプロピルアルコー
ルを測定したが、瘍跡程度した検出できなかつ
た。該成型ニトロセルロース組成物中に含まれる
ニトロセルロースはＨ1/4の粘度特性を示した。
実施例 ７
水分25％を含有するＬ1/2ニトロセルロースに
MIBK100ｇを加え、手で混練してペースト状の
組成物を得た、得られた組成物を予め準備してお
いたトルエン300ｇ中に実施例１と同様の方法で
押出しカツトして、水を含む成型品を得た。この
トルエンを含むこの成型品の全量を実施例１と同
様の方法で200Torrで減圧蒸留し、固形分65％の
成型ニトロセルロース組成物152ｇを得た。該成
型ニトロセルロース組成物は水分1.0％、MIBK
とトルエンの比率は４／６であつた。該成型ニト
ロセルロース組成物に含まれるニトロセルロース
はＬ1/2の粘度特性を示した。また該成型ニトロ
セルロース組成物は繊維状のニトロセルロースは
見られず、成型時の形状をほゞ保持した流動性の
よい固形で、包装容器からの取出し作業性も非常
に良好であつた。
実施例 ８
水分25％を含有するＨ1/2ニトロセルロース134
ｇにメチルエチルケトン100ｇを加え、手で混練
してペースト状の組成物を得た。得られた組成物
を予め準備しておいたトルエン500ｇ中に実施例
１と同様の方法で押出しカツトして、水を含む成
型品を得た。このトルエンを含む成型品の全量を
実施例１と同様の方法で200Torrで減圧蒸留し、
固形分65％の成型ニトロセルロース組成物153ｇ
を得た。該成型ニトロセルロース組成物は水分
0.7％であつた。
実施例 ９
水分25％を含有するＨ1/4ニトロセルロース134
ｇに酢酸エチル60ｇとトルエン40ｇを加え、手で
混練して繊維状ニトロセルロースは殆んどみられ
ないやゝ硬いペースト状の組成物を得た。得られ
た組成物を予め準備しておいたトルエン300ｇ中
に実施例１と同様の方法で押出しカツトして、水
を含む成型品を得た。このトルエンを含む成型品
の全量を実施例１と同様の方法で200Torrで減圧
蒸留し、固形分68％の成型ニトロセルロース組成
物146ｇを得た。該成型ニトロセルロース組成物
は水分0.6％、酢酸エチルとトルエンの比率は
19／81であつた。また該成型ニトロセルロース組
成物は成型時の形状をほゞ保持した付着性のない
固形物で、包装容器からの取出し作業性も良好で
あつた。
実施例 10
コニーダー〔型式KDH60（不二パウダル(株)製）〕
を撹拌し乍ら、水を25％含有するＨ1/2ニトロセ
ルロース４Kgを入れる。さらに予め準備していた
MIBK1.2Kgとトルエン0.45Kgの混合液をゆつくり
振かけ（所要時間約２分）続けて10分間混練し、
部分的にニトロセルロースが溶解した小集塊状の
組成物を得た。得られた小集塊状組成物を２ｍ／
ｍφの細穴を多数有するダイスを出口部に取付け
たペレタイザー〔型式EXKF（不二パウダル(株)
製）〕に仕込み、丸い紐状物とした後、MIBKを
飽和した水浴中に入れ、長さ約10ｍ／ｍにカツト
して、水を含む成型品を得た。この成型品を水浴
中から有孔盤を有する水切器に移し水を自然分離
したものと、予め準備していたトルエン7.125Kg
とMIBK0.375Kgからなる混合溶剤とを加熱用ジ
ヤケツト付回転式減圧釜に仕込み、90〜95℃で加
熱を続けながら500Torrで減圧蒸留を100分間行
ない、成型ニトロセルロース組成物を作つた。該
成型ニトロセルロース組成物は固形分70％、水分
0.6％、MIBKとトルエンの比率は26／74であつ
た。また該成型ニトロセルロース組成物は成型時
の形状をほぼ保持し、繊維状または粉状のニトロ
セルロースを実質的に含まず、流動性のよい固形
物で、包装容器からの取出し性も非常に良好であ
つた。さらに、静電位測定値は、0.4KVであつ
た。
実施例11〜17 比較例１〜９
成型ニトロセルロース組成物の製造方法のうち
次の条件を変更した以外は実施例10と同様の条件
で製造した。その条件及び結果を表―１に示す。
The present invention relates to a novel shaped nitrocellulose composition that is substantially free of alcohol and/or water and a method for producing the same. Nitrocellulose products are usually made with alcohols such as ethyl alcohol, isopropyl alcohol, butyl alcohol, etc. for safety during handling.
Alternatively, it is used after being moistened with water. Nitrocellulose is added to many paints, inks, and adhesives including acrylic resin paints because it provides excellent drying properties and pigment dispersibility when incorporated into paints. Furthermore, in recent years, attempts have been made to use it in addition to polyurethane resin paints in order to provide this property. However, when nitrocellulose containing alcohols and/or water is used in addition to polyurethane resin paints, the isocyanate groups in the polyurethane resin paints react with the alcohols and water, consuming the isocyanate groups. It has defects that have a significant negative impact on its original properties and performance. All industrial attempts to correct these deficiencies have been unsuccessful. One method is to dry nitrocellulose moistened with alcohol and/or water, and remove the alcohol and/or water by evaporation to obtain dry nitrocellulose. It is dangerous and should not be tolerated based on conventional wisdom. Another method that has been proposed is nitrocellulose moistened with triol, but this has strong electrostatic properties, and when toluene evaporates during handling, nitrocellulose tends to turn into powder, which scatters and becomes difficult to clean. There is a risk of spontaneous combustion as it tends to accumulate in
It has not been commercialized due to the risk of electrostatic charge and the lack of safety guarantees. Yet another method is to prepare a solid nitrocellulose composition by replacing the wetting agent of nitrocellulose moistened with alcohols and/or water with a plasticizer such as a phthalate ester, e.g. dibutyl phthalate. : Clear chip manufactured by Asahi Kasei Industries, Ltd.' has also been proposed. Although this is naturally used because it does not substantially contain alcohol and/or water and has improved charging properties compared to toluene-moistened nitrocellulose, it does not contain plasticizers such as phthalate esters. It is not preferred in many fields because it inhibits the hardness and drying properties of the coating film. For these reasons, although there is a strong demand from the market for the production of nitrocellulose particularly suitable for use in polyurethane resin coating compositions, this problem has not yet been resolved. The inventors of the present invention have taken these points into consideration and, as a result of extensive studies, have arrived at the present invention. That is, the first invention of the present invention comprises (a) nitrocellulose, (b) an organic solvent that is inert to isocyanate groups and dissolves nitrocellulose, and (c) an organic solvent that is insoluble in isocyanate groups and does not dissolve nitrocellulose. The three components form a uniform solid phase, with the content of (a) being 50 to 80% by weight, and (b)/(c) being 15 to 80% by weight.
80/20-85 (weight ratio), non-adhesive granules,
The second invention is a molded nitrocellulose composition characterized in that it is in the form of chips or pellets, and the second invention is a nitrocellulose composition that is inert to isocyanate groups and that is inert to isocyanate groups and is added to nitrocellulose moistened with alcohol and/or water. A mixed solvent consisting of an organic solvent that dissolves nitrocellulose alone or a mixture of the organic solvent and an organic solvent that is inert to isocyanate groups and does not dissolve nitrocellulose,
The nitrocellulose is added in an amount that is at least partially dissolved and the resulting mixture does not flow easily at room temperature without the application of mechanical force, and after kneading or kneading, mechanically A step of molding into granules, chips, or pellets, and applying an organic solvent that is inert to isocyanate groups and does not dissolve nitrocellulose to the molded product alone or together with the organic solvent that is inert to isocyanate groups and dissolves nitrocellulose. Add a mixture with an organic solvent;
This is a method for producing a shaped nitrocellulose composition, which comprises a distillation step in which alcohols and/or water are substantially removed together with a portion of an organic solvent by heating and/or reduced pressure. The nitrocellulose used in the present invention is not particularly limited in its nitrogen content (N%) and viscosity (average degree of polymerization), and any of the nitrocellulose can be used, but preferably the nitrocellulose described in JIS-K-6703 is used. For industrial nitrocellulose, the N% of nitrocellulose is 10.7 to 12.2%, and the viscosity symbol is L1/8 to
1/2 and H1/16 to 120, and is moistened with alcohols such as ethyl alcohol, isopropyl alcohol, or butyl alcohol, and/or water. The nitrocellulose-soluble organic solvent that is inert to isocyanate groups (hereinafter referred to as soluble solvent) used in the present invention is a nitrocellulose-soluble organic solvent that is inert to isocyanate groups such as OH group, COOH group, and NH2 group among known organic solvents that dissolve nitrocellulose. It is an organic solvent that does not have an active reactive group, and typical examples include acetate esters such as ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl ethyl ketone, and methyl isobutyl ketone. , isophorone, cyclohexanone and other ketones; and nitroparaffins such as nitromethane, nitroethane and nitropropane. Among these, considering the solubility of nitrocellulose, odor during handling, economic efficiency, etc., ethyl acetate, propyl acetate, butyl acetate,
Methyl ethyl ketone and methyl isobutyl ketone are preferred. Typical nitrocellulose-insoluble organic solvents (hereinafter referred to as insoluble solvents) that are inert to isocyanate groups used in the present invention include hexane,
Aliphatic, alicyclic and aromatic hydrocarbons such as pentane, octane, cyclohexane, methylcyclohexane, solvent naphtha, petroleum spirits, kerosene, benzene toluene and xylene, and halogenated hydrocarbons such as trichloroethylene and carbon tetrachloride. can be given. Among these, toluene, xylene and hexane are preferred in consideration of odor during handling, economic efficiency, etc. The configuration and effects of the present invention will be explained with reference to the drawings. FIG. 1 is a triangular diagram showing the composition of three types: an organic solvent that is inert to nitrocellulose isocyanate and dissolves nitrocellulose, and an organic solvent that is inert to isocyanate and does not dissolve nitrocellulose. This indicates the composition range of a product, and indicates the range in which a nitrocellulose composition consisting of three components within this range does not have stickiness and maintains its shape even if it is molded into an arbitrary shape. B is a nitrocellulose composition composed of the three components in this range, which has adhesive properties, so even if it is molded into any shape,
This shows the range where fusion begins over time and the molded shape can no longer be maintained. C indicates a range in which nitrocellulose undergoes phase separation and nitrocellulose and both organic solvents do not separate to form a homogeneous phase in a nitrocellulose composition consisting of three components within this range. For example, to explain the behavior when 20 g of nitrocellulose is dissolved in 80 g of ethyl acetate (a solvent that dissolves nitrocellulose), this composition is shown as a in Figure 1, and it is extremely sticky and does not form into a molded product. It is in liquid form. If this is concentrated as it is, ethyl acetate will be removed by evaporation, and b
Even if it were to be molded in a liquid or paste form that passes through points C and C, both of which have adhesive properties,
The molded products immediately coalesce and cannot become a molded product. If the concentration continues, substantially all of the ethyl acetate is removed, leaving only nitrocellulose, which poses a risk of ignition. Further, the behavior when 20 g of nitrocellulose is dissolved in a mixed solvent of 50 g of ethyl acetate (a solvent that dissolves nitrocellulose) and 30 g of xylene (a solvent that does not dissolve nitrocellulose) is also explained with reference to FIG. This composition is shown by d in the same figure, and is in a liquid state that is extremely sticky and cannot be formed into a molded product. When this is distilled, both solvents are removed by evaporation, but ethyl acetate is removed first due to its vapor pressure, so it is concentrated through approximately points c and f. Point e is in the form of a sticky paste, and even if molded at this point, the molded products will immediately coalesce and cannot become a molded product. At point f, nitrocellulose precipitates and the nitrocellulose and both organic solvents separate into two layers. In this respect, the three materials do not exhibit a uniform solid phase, and of course cannot be made into a molded product. Even with such a limited composition of the three components, a molded nitrocellulose composition can only be obtained in the form of non-adhesive granules, chips or pellets, and in which the three components exhibit a uniform solid phase. In addition, the compositions obtained in Examples 1 and 2 of Japanese Patent Publication No. 44-20230 are shown at points g and h in Figure 1, and since neither contains an organic solvent that dissolves nitrocellulose, it dissolves nitrocellulose. These two substances do not form a homogeneous solid phase, but only physically adhere to each other. In addition, the composition obtained in Example 1 of Japanese Patent Publication No. 45-9397 is shown at point i in Figure 1, and it consists of nitrocellulose and water, that is, a solvent that does not dissolve nitrocellulose and is active on isocyanate groups. ,
These two do not form a uniform solid phase, but only physical adhesion occurs. In the production method of the present invention, fibrous nitrocellulose moistened with alcohol and/or water,
The nitrocellulose is at least partially dissolved in a soluble solvent alone or a mixture of a soluble solvent and an insoluble solvent, and the resulting composition easily flows at room temperature without applying mechanical force. A molding step is performed in which the alcohol and/or water obtained in this molding step is added in such an amount that the alcohol and/or water obtained in this molding step is added, kneaded or kneaded, and then mechanically molded into granular chips or pellets. After adding an insoluble solvent alone or a mixed solvent of the insoluble solvent and a soluble solvent to the molded product, heating and/or depressurization are performed to substantially distill the alcohol and/or water together with a portion of the organic solvent used. It consists of a distillation process to remove the water. After kneading or kneading in the molding step of the method of the present invention, methods of mechanically molding into granules, chips or pellets include a method of kneading or kneading and then molding, and a method of kneading or kneading and then molding, and a method of kneading or kneading and then molding. There are methods to perform this continuously, and any of these methods can be implemented. Among these methods, a method in which the steps from kneading or kneading to molding are carried out continuously is preferred from the viewpoint of economy, work efficiency, and the like. In addition, the molded product formed into granules, chips, or pellets in the molding process can maintain its shape in the next distillation process and product, so the molding of the resulting composition is This is particularly meaningful from this point of view. In other words, unlike fibrous nitrocellulose, it does not have the bulkiness caused by the entanglement of fibers, has a high bulk density, and has excellent fluidity. Therefore, the packing density in containers is high, which reduces transportation costs. What is possible is that the handling efficiency from the storage container is greatly improved. Furthermore, although there is no particular restriction on the shape that can be mechanically molded into granules, chips, or pellets, from the above point of view, the most preferable shape of the molded product is, for example, when the molded product is pressed from a die having a certain shape and cut into short pieces. Alternatively, it is a molded product that is formed into a sheet using a roll or the like, and then cut into a certain size and molded into granules, pellets, or chips. After kneading or kneading according to the method of the present invention, granules,
Typical equipment used to form chips or pellets is a kneader mixer,
Examples include internal mixers, pony mixers, pug mills, gear-con powders, roll mills, co-kneaders, screw extruders, potators, shredder cutters, briquette machines, roll cutters, and the like. The atmosphere before forming into granules, chips, or pellets using these devices and/or storage method until the next distillation step can be carried out in air, nitrogen gas, or water. When an organic solvent is added to nitrocellulose, generally, the larger the viscosity symbol of nitrocellulose, the higher the viscosity (average degree of polymerization) in the organic solvent solution. The viscosity of dissolved nitrocellulose also differs depending on the type of soluble solvent. Furthermore, the viscosity of the dissolved nitrocellulose varies depending on the mixing ratio of the soluble solvent and the insoluble solvent. Furthermore, if the same solvent is added in a large amount, the viscosity properties will be affected, such as a decrease in viscosity. The mixed solvent consisting of the soluble solvent and the insoluble solvent is used in an amount such that the nitrocellulose is at least partially dissolved and the resulting composition does not flow easily at room temperature without applying mechanical force. Even in the method of the present invention, in which the organic solvent is added, kneaded or kneaded, and then mechanically formed into granules, chips, or pellets, it is not easy to specify the range of the amount of organic solvent to be added; If this is easy, it is difficult to maintain the shape of the molded product, which is not preferable. Taking these things into consideration, the viscosity of the composition is 50,000 cps, which does not flow easily at room temperature without applying mechanical force.
(20℃) or less, preferably 100000cps (20℃)
It is as follows. Most preferably, the range is such that nitrocellulose is partially dissolved but not completely dissolved, and that it contains an undissolved portion of nitrocellulose and has shape retention to the extent that it does not flow at room temperature unless mechanical force is applied. . As mentioned above, the ratio of nitrocellulose and soluble solvent used in the molding process depends on the viscosity characteristics of nitrocellulose, the type and amount of wetting agent, and whether the soluble solvent is used alone, or a mixed solvent of a soluble solvent and an insoluble solvent is used. Although it is very difficult to specify the range because many factors such as the mixing ratio of the mixed solvent are intertwined, an example is shown below to further facilitate understanding of the present invention. That is, for 100 parts by weight of nitrocellulose of H1/2 nitrocellulose moistened with water, when a soluble solvent is used alone, the soluble solvent is 25 to 150 parts by weight, and the ratio of soluble solvent to insoluble solvent is 50:50. In the case of a mixed solvent, the mixed solvent is 40 to 180 parts by weight. The mixed solvent added to obtain a molded product containing alcohol and/or water that is mechanically molded into granules, chips, or pellets does not contain an insoluble solvent.
It is not more than 80% by weight, preferably not more than about 70% by weight. When the insoluble solvent is about 80% by weight or more, the nitrocellulose is at least partially dissolved, and the resulting composition is added in such an amount that it does not flow easily at room temperature without the application of mechanical force, and the mixture is kneaded. Alternatively, if the mixture is kneaded and mechanically molded into particles, chips, or pellets, it becomes difficult to maintain the shape of the molded product. Furthermore, the content of soluble solvent in the molded product becomes abnormally low, increasing the electrostatic property of the molded product, which adversely affects handling workability. In the molded product containing alcohol and/or water obtained in the molding process of the method of the present invention, the fibrous nitrocellulose is transformed into a nitrocellulose molded product by the action of the soluble solvent and the force during mechanical molding. preferable. Next, an insoluble solvent alone or a mixed solvent of the insoluble solvent and a soluble solvent is added to the molded product containing alcohol and/or water, and the alcohol and/or water is mixed with both of the organic solvents by heating and/or reducing the pressure. The solvent used to substantially remove a portion of the alcohol may be an insoluble solvent that has a higher boiling point than the alcohol and/or water or is azeotropic with the alcohol and/or water; either method may be used. can. In addition, when using nitrocellulose moistened with alcohol and/or water, an insoluble solvent having the lowest azeotropic point with water may be used alone or in a mixture of the insoluble solvent and a soluble solvent. It is economical and particularly preferable to use a solvent. Furthermore, an insoluble solvent alone or a mixed solvent of the insoluble solvent and a soluble solvent is added to the molded product containing alcohol and/or water, and the alcohol and/or water is dissolved by heating and/or under reduced pressure. The method of substantially removing it along with some of the
This method involves heating and distilling under reduced pressure, normal pressure, or reduced pressure, all of which are effective. In addition, the higher the heating temperature for nitrocellulose, the more it accelerates its decomposition and becomes more dangerous.
It is not preferable to carry out heating distillation at a high temperature of 100°C or higher, and if the boiling point of the solvent is high, it is preferable to carry out vacuum distillation at a temperature of 100°C or lower. Furthermore, the mixed solvent of an insoluble solvent and a soluble solvent added to the molded product containing alcohol and/or water may be a mixed solvent containing 20% by weight or less of the soluble solvent. The content of soluble solvent in the mixed solvent is 20
If it exceeds % by weight, the proportion of soluble solvent increases, and adhesion between molded products tends to occur, and eventually the whole becomes apt to become agglomerated. To prevent this, a very large amount of the mixed solvent must be used. This is not desirable in practice. When a mixed solvent consisting of toluene or xylene alone or a mixture thereof and a soluble solvent is used, the content of the soluble organic solvent is particularly preferably 15% by weight or less. The molded nitrocellulose composition of the present invention is composed of 50 to 80% by weight of nitrocellulose, preferably 50 to 75% by weight, and the amount of soluble solvent in the mixed solvent contained is 15 to 80% by weight, preferably 20 to 70% by weight. %. Furthermore, the molded nitrocellulose composition does not substantially contain fibrous nitrocellulose or powdered nitrocellulose, and is molded into a solid that substantially retains its shape when molded. This is because the wet content evaporates during the handling process, which occurs with conventional nitrocellulose moistened with alcohol and/or water, and the nitrocellulose approaches a dry state.
Compared to short fibers and other nitrocellulose dust that scatters and accumulates in places that are difficult to clean, which can cause safety problems due to natural decomposition if left as is, molded nitrocellulose compositions can be made into any size. Since it is molded and does not easily scatter, these problems do not occur and it is easy to handle in terms of safety.Furthermore, since there is no fibrous entanglement like fibrous nitrocellulose, it is easier to handle from the filled container. Excellent. Additionally, shaped nitrocellulose compositions are surprisingly relatively unchargeable. This is a major feature in the case of nitrocellulose, which has a risk of fire and the like and safety in handling is important. This characteristic is that during the molding process, the molded nitrocellulose composition is mixed with a soluble solvent to the extent that at least a portion of the nitrocellulose is dissolved, kneaded or kneaded, and then mechanically formed into granules, chips, or pellets. Due to the effects of the molding step and the subsequent distillation step, the soluble solvent is selectively adsorbed substantially uniformly on the nitrocellulose, becoming almost homogeneous, and the liquid and/or gaseous atmosphere of both organic solvents is removed. This is probably because the surface area per weight of nitrocellulose is smaller than that of fibrous nitrocellulose because it is formed into granules, chips, or pellets. The chargeability of the molded nitrocellulose composition decreases as the proportion of the soluble solvent among the two organic solvents contained in the molded nitrocellulose composition increases. The proportion of soluble solvent that exhibits the same level of chargeability as the above-mentioned "clear chip" is expressed as the ratio of soluble solvent to insoluble solvent contained in the molded nitrocellulose composition, and the soluble solvent is 15% by weight or more, which is safer. In order to have a high content, the content is preferably 20% by weight or less.
Furthermore, the molded nitrocellulose composition is substantially free of isocyanate group-active alcohols and/or water, and is free of plasticizers such as phthalate esters that have an undesirable effect on the coating composition. Because it is a completely new molded nitrocellulose composition that has not been developed until now, it can be used as a pigment dispersant for coating compositions having isocyanate groups such as polyurethane resin paints, especially polyurethane coating compositions containing magnetic powder, It is also useful in the field of acrylic resin paints, lacquers, inks and adhesives which are effective as initial desiccants and which do not prefer water during the production of paints. When molded into granules, chips, or pellets, they have good fluidity and are easy to take out from the container during dissolution and preparation. In addition, products formed into granules, chips, or pellets are easier to fill into containers than products with large amorphous lumps, and transportation costs are lower. In addition, granules, chips, or pellets have a regular shape, have better dispersion and solubility, and can be dissolved in a shorter time than those with large, irregularly shaped lumps. It is highly preferred by consumers. Hereinafter, the present invention will be explained in detail with reference to Examples.
Parts and percentages in the examples are by weight unless otherwise specified. Example 1 H1/2 nitrocellulose 143 containing 30% water
100 g of methyl isobutyl ketone (hereinafter abbreviated as MIBK) was added to g and kneaded lightly by hand to obtain a paste-like composition.
The molded product in toluene was placed in a hand screw extruder equipped with a die with many mφ holes and extruded into 300 g of toluene prepared in advance. The molded product in toluene was cut to a length of about 20 m/m and water was added. A pellet-like molded product is formed, and the entire amount containing toluene is transferred to a rotary evaporator (manufactured by Yamato Scientific Co., Ltd.),
Molded nitrocellulose composition with 65% solids by vacuum distillation to 200 Torr in a water bath heated to 80°C
Obtained 153g. This molded nitrocellulose composition does not contain fibrous nitrocellulose, is solid with good fluidity, and does not adhere to packaging containers.
The take-out workability was also very good. The nitrocellulose in the molded nitrocellulose composition has H1/
The molded nitrocellulose composition has a viscosity characteristic of 2, and when the water content in the molded nitrocellulose composition was measured by the Karl Fischer method and the solvent composition by the gas chromatography method, the water content was 0.7%, and the ratio of MIBK to toluene was 4/6. It was hot. Example 2 H1/2 nitrocellulose 134 containing 25% water
30 g of MIBK and 70 g of toluene were added to the mixture and kneaded lightly by hand to obtain a slightly hard paste-like composition.
The resulting composition was mixed with toluene, which had been prepared in advance.
A molded product containing water was obtained by extruding and cutting into a mixed solvent of 480 g and MIBK 120 g in the same manner as in Example 1. The entire amount of the molded product containing the mixed solvent was distilled under reduced pressure in the same manner as in Example 1 to obtain 163 g of a molded nitrocellulose composition with a solid content of 61%. The ratio of toluene and toluene was 25/75. Further, the molded nitrocellulose composition did not contain any fibrous nitrocellulose, and was a solid material with good fluidity that almost retained its shape at the time of molding, and was very easy to remove from the packaging container. Example 3 H1/2 nitrocellulose 134 containing 25% moisture
65 g of MIBK and 45 g of toluene were added to the 300 g of toluene that had been prepared in advance. A molded product containing water was obtained by extrusion cutting in the same manner as in Example 1.The entire amount of the molded product containing toluene was distilled under reduced pressure to 150 Torr in the same manner as in Example 1 to reduce the solid content. 70
% molded nitrocellulose composition was obtained,
The molded nitrocellulose composition has a water content of 0.8%;
The ratio of MIBK to toluene was 18/82. Further, the molded nitrocellulose composition did not contain any fibrous nitrocellulose, and was a solid material with good fluidity that almost retained its shape at the time of molding, and was very easy to remove from the packaging container. Example 4 H1/2 nitrocellulose 143 containing 30% moisture
100g of MIBK was added to 100g of MIBK and kneaded lightly by hand to obtain a paste-like composition.The resulting composition was extruded and cut into 300g of xylene prepared in advance in the same manner as in Example 1. A molded product containing water was obtained. The entire amount of the molded product containing the xylene was distilled under reduced pressure to 50 Torr in the same manner as in Example 1, and the solid content was reduced to 75
% molded nitrocellulose composition was obtained,
The molded nitrocellulose composition has a water content of 0.6%;
The ratio of MIBK to xylene was 19/81. Example 5 H1/4 nitrocellulose 143 containing 30% moisture
100g of butyl acetate was added to 100g of butyl acetate and kneaded lightly by hand to obtain a paste-like composition.The resulting composition was extruded into 350g of xylene prepared in advance in the same manner as in Example 1. A molded product containing water was obtained. Example 1 The total amount of molded products containing xylene
Distilled under reduced pressure to 50 Torr in the same manner as above to reduce the solid content.
133 g of a 75% molded nitrocellulose composition was obtained.
The molded nitrocellulose composition had a water content of 0.5% and a butyl acetate to xylene ratio of 21/79. Example 6 H1/4 containing 30% isopropyl alcohol
143g of nitrocellulose, 35g of MIBK and xylene
35 g was added and kneaded by hand to obtain a composition in the form of a soft paste. The viscosity of the obtained composition at 20° C. was measured using a Bruckfield viscometer (hereinafter referred to as B-type viscometer), but the viscosity could not be measured at 100,000 cps or more. This composition was extruded and cut into 600 g of xylene prepared in advance in the same manner as in Example 1 to obtain a molded product containing water.
The entire amount of this molded product containing xylene was distilled under reduced pressure to 50 Torr in the same manner as in Example 1, and the solid content was reduced to 70%.
142 g of a molded nitrocellulose composition was obtained. The molded nitrocellulose composition has a water content of 0.6%;
The ratio of MIBK to xylene was 2/8. Furthermore, isopropyl alcohol was measured using gas chromatography, but it could not be detected as much as a tumor scar. The nitrocellulose contained in the molded nitrocellulose composition exhibited viscosity characteristics of H1/4. Example 7 L1/2 nitrocellulose containing 25% moisture
100g of MIBK was added and kneaded by hand to obtain a paste-like composition.The obtained composition was extruded and cut into 300g of toluene prepared in advance in the same manner as in Example 1 to contain water. A molded product was obtained. The entire amount of this molded product containing toluene was distilled under reduced pressure at 200 Torr in the same manner as in Example 1 to obtain 152 g of a molded nitrocellulose composition with a solid content of 65%. The molded nitrocellulose composition has a moisture content of 1.0%, MIBK
The ratio of toluene and toluene was 4/6. The nitrocellulose contained in the molded nitrocellulose composition exhibited viscosity characteristics of L1/2. Further, the molded nitrocellulose composition did not contain any fibrous nitrocellulose, and was a solid with good fluidity that almost retained its shape at the time of molding, and the workability of removing it from the packaging container was also very good. Example 8 H1/2 Nitrocellulose 134 containing 25% moisture
100 g of methyl ethyl ketone was added to the mixture and kneaded by hand to obtain a paste composition. The resulting composition was extruded and cut into 500 g of toluene prepared in advance in the same manner as in Example 1 to obtain a molded product containing water. The entire amount of the molded product containing toluene was distilled under reduced pressure at 200 Torr in the same manner as in Example 1.
153 g of molded nitrocellulose composition with 65% solids content
I got it. The molded nitrocellulose composition contains water.
It was 0.7%. Example 9 H1/4 Nitrocellulose 134 containing 25% moisture
60 g of ethyl acetate and 40 g of toluene were added to the mixture and kneaded by hand to obtain a hard paste-like composition in which almost no fibrous nitrocellulose was observed. The obtained composition was extruded and cut into 300 g of toluene prepared in advance in the same manner as in Example 1 to obtain a molded product containing water. The entire amount of this molded product containing toluene was distilled under reduced pressure at 200 Torr in the same manner as in Example 1 to obtain 146 g of a molded nitrocellulose composition with a solid content of 68%. The molded nitrocellulose composition has a moisture content of 0.6% and a ratio of ethyl acetate to toluene.
It was 19/81. Further, the molded nitrocellulose composition was a non-adhesive solid that substantially retained its shape when molded, and had good workability when taken out from the packaging container. Example 10 Co-kneader [Model KDH60 (manufactured by Fuji Paudal Co., Ltd.)]
While stirring, add 4 kg of H1/2 nitrocellulose containing 25% water. I also prepared in advance
Slowly sprinkle a mixture of 1.2 kg of MIBK and 0.45 kg of toluene (takes about 2 minutes) and continue kneading for 10 minutes.
A composition in the form of small agglomerates in which nitrocellulose was partially dissolved was obtained. The obtained small agglomerate composition was
Pelletizer with a die having many mφ holes attached to the outlet [Model: EXKF (Fuji Paudal Co., Ltd.)
After making a round string-like object, it was placed in a water bath saturated with MIBK and cut into a length of about 10 m/m to obtain a molded product containing water. This molded product was transferred from the water bath to a drainer with a perforated plate to naturally separate the water, and 7.125 kg of toluene had been prepared in advance.
A mixed solvent consisting of 0.375 kg of MIBK and 0.375 kg of MIBK were placed in a rotary vacuum pot with a heating jacket, and vacuum distillation was carried out at 500 Torr for 100 minutes while continuing to heat at 90 to 95°C to produce a molded nitrocellulose composition. The molded nitrocellulose composition has a solids content of 70% and a water content of 70%.
The ratio of MIBK to toluene was 26/74. In addition, the molded nitrocellulose composition almost retains its shape when molded, does not substantially contain fibrous or powdered nitrocellulose, is a solid with good fluidity, and is very easy to remove from packaging containers. It was hot. Additionally, the electrostatic potential measurement was 0.4KV. Examples 11 to 17 Comparative Examples 1 to 9 Molded nitrocellulose compositions were manufactured under the same conditions as in Example 10 except that the following conditions were changed. The conditions and results are shown in Table-1.
【表】【table】
【表】【table】
【表】
実施例 18
実施例10で得た成型ニトロセルロース組成物と
イソプロピルアルコール30％湿潤Ｈ1/2ニトロセ
ルロースを用いて、それぞれを室内に放置し、揮
発性物質の揮発性と落槌感度を測定した。その結
果を表―２及び表―３に示す。[Table] Example 18 Using the molded nitrocellulose composition obtained in Example 10 and H1/2 nitrocellulose moistened with 30% isopropyl alcohol, each was left indoors and the volatility of volatile substances and drop hammer sensitivity were measured. did. The results are shown in Table-2 and Table-3.
【表】【table】
【表】
以上の結果からも分るように本発明の成型ニト
ロセルロース組成物は、アルコール類および／ま
たは水を実質的に含まず、またフタル酸ジブチル
等の可塑剤を含まないため、被覆組成物中でニト
ロセルロース本来の機能を充分に発揮できる製品
である。さらに成型されているため流動性がよ
い、これは繊維状ニトロセルロース欠点である繊
維状物の絡み合いによる流動性の悪さから来る取
扱い作業性の悪さを非常によく改良している。さ
らにもう一つの特徴はトリオール湿ニトロセルロ
ースの欠点の一つであつた帯電性による危険もよ
く改善され、現在市販されている「クリヤーチツ
プ」と同等またはそれ以下になること、さらに
揮発性物質の揮発はイソプロピルアルコール湿潤
ニトロセルロースよりもおそく、かつ落槌感度か
らみても耐衝撃性に優れた新規な成型ニトロセル
ロース組成物であり、有用性の高いものである。[Table] As can be seen from the above results, the molded nitrocellulose composition of the present invention does not substantially contain alcohols and/or water, and does not contain plasticizers such as dibutyl phthalate, so the coating composition This is a product that can fully demonstrate the original functions of nitrocellulose in materials. Furthermore, since it is molded, it has good fluidity, which greatly improves the poor handling and workability caused by poor fluidity due to entanglement of fibrous materials, which is a drawback of fibrous nitrocellulose. Another feature is that the danger of electrostatic charge, which was one of the disadvantages of triol-wet nitrocellulose, has been greatly improved, and it is equivalent to or lower than the "clear chips" currently on the market, and it is also free of volatile substances. This is a novel molded nitrocellulose composition that volatilizes more slowly than isopropyl alcohol-moistened nitrocellulose and has excellent impact resistance in terms of drop hammer sensitivity, making it highly useful.
第１図は、ニトロセルロース、イソシアネート
に不活性でかつニトロセルロースを溶解する有機
溶剤及びイソシアネートに不活性でかつニトロセ
ルロースを溶解しない有機溶剤の３者の構成を示
す三角図表である。図中、Ａは本発明のニトロセ
ルロース組成物の範囲、Ｂは粘着性を有し、時間
の経過と共に融着が始まり、遂には成型された形
状を保てなくなる範囲、Ｃはニトロセルロースと
有機溶剤が相分離を起す範囲を示す。また、図
中、ａ，ｂ，ｃはニトロセルロース20ｇと酢酸エ
チル80ｇよりなる組成物の挙動を、ｄ，ｅ，ｆは
ニトロセルロース20ｇを酢酸エチル50ｇとキシレ
ン30ｇとの混合溶剤に溶解した組成物の挙動を、
ｇ，ｈは特公昭44−20230号公報の実施例１及び
２で得られた組成物、ｉは特公昭45−9397号公報
の実施例１で得られた組成物を示す。
FIG. 1 is a triangular diagram showing the three compositions of nitrocellulose, an organic solvent that is inert to isocyanates and dissolves nitrocellulose, and an organic solvent that is inert to isocyanates and does not dissolve nitrocellulose. In the figure, A is the range of the nitrocellulose composition of the present invention, B is the range where the nitrocellulose composition has adhesiveness and begins to fuse with the passage of time, and can no longer maintain its molded shape, and C is the range of the nitrocellulose and organic This indicates the range in which the solvent undergoes phase separation. In addition, in the figure, a, b, and c represent the behavior of a composition consisting of 20 g of nitrocellulose and 80 g of ethyl acetate, and d, e, and f represent the behavior of a composition consisting of 20 g of nitrocellulose and 80 g of ethyl acetate. the behavior of things,
g and h are the compositions obtained in Examples 1 and 2 of Japanese Patent Publication No. 44-20230, and i is the composition obtained in Example 1 of Japanese Patent Publication No. 45-9397.
Claims (1)
ロースを溶解する有機溶剤、および (c) イソシアネート基に不活性でかつニトロセル
ロースを溶解しない有機溶剤 から成り、この３者は均一な固相を形成してお
り、(a)の含有量は50〜80重量％、(b)／(c)＝15〜
80／20〜85（重量比）であり、非粘着性の粒状、
チツプ状またはペレツト状であることを特徴とす
る成型されたニトロセルロース組成物。 ２ アルコール類および／または水で湿潤化した
(a)ニトロセルロースに、(b)イソシアネート基に不
活性でかつニトロセルロースを溶解する有機溶剤
の単独または該有機溶剤と(c)イソシアネート基に
不活性でかつニトロセルロースを溶解しない有機
溶剤との混合物から成る混合溶剤を、上記ニトロ
セルロースが少なくとも部分的に溶解しかつ得ら
れた混合物が常温では機械的な力を加えないと容
易に流動しない程度の量で以つて加え、混練また
は捏和した後、機械的に粒状、チツプ状またはペ
レツト状に成型する工程と、該成型品にイソシア
ネート基に不活性でかつニトロセルロースを溶解
しない有機溶剤の単独または該有機溶剤のとイソ
シアネート基に不活性でかつニトロセルロースを
溶解する有機溶剤との混合物を加え、加熱およ
び／または減圧により、アルコール類および／ま
たは水を使用した有機溶剤の一部とともに実質的
に除去する留出工程からなることを特徴とする(a)
を50〜80重量％合み、(b)／(c)が15〜80／20〜85
（重量比）である非粘着性の均一な固相に成型さ
れたニトロセルロース組成物の製造方法。 ３ 成型工程で使用する有機溶剤がイソシアネー
ト基に不活性なニトロセルロース不溶性有機溶剤
80重量％以下とイソシアネート基に不活性なニト
ロセルロース可溶性有機溶剤とからなることを特
徴とする特許請求の範囲第２項記載の製造方法。 ４ 留出工程で使用する有機溶剤がイソシアネー
ト基に不活性なニトロセルロース可溶性有機溶剤
20重量％以下とイソシアネート基に不活性なニト
ロセルロース不溶性有機溶剤とからなることを特
徴とする特許請求の範囲第２項記載の製造方法。 ５ イソシアネート基に不活性なニトロセルロー
ス可溶性有機溶剤が酢酸エチル、酢酸プロピル、
酢酸ブチル、エチレングリコールモノメチルエー
テルアセテート、エチレングリコールモノエチル
エーテルアセテート、メチルエチルケトン、メチ
ルイソブチルケトン、イソホロン、イクロヘキサ
ノン、ニトロエタンおよびニトロプロパンからな
る群から選ばれた少なくとも一種であることを特
徴とする特請求の範囲第２項記載の製造方法。 ６ イソシアネート基に不活性なニトロセルロー
ス可溶性有機溶剤が酢酸エチル、酢酸プロピル、
酢酸ブチル、メチルエチルケトン、メチルイソブ
チルケトンからなる群から選ばれた少なくとも一
種であることを特徴とする特請求の範囲第２項ま
たは第５項記載の製造方法。 ７ イソシアネート基に不活性なニトロセルロー
ス不溶性有機溶剤がヘキサン、ヘプタンオクタ
ン、ソルベントナフタ、シクロヘキサン、ベンゼ
ン、トルエンよびキシレンからなる群から選ばれ
た少なくとも一種であることを特徴とする特請求
の範囲第２項記載の製造方法。 ８ イソシアネート基に不活性なニトロセルロー
ス不溶性有機溶剤がトルエン、キシレンおよびヘ
キサンからなる群から選ばれた少なくとも一種で
あることを特徴とする特請求の範囲第２項または
第７項記載の製造方法。[Scope of Claims] 1 (a) nitrocellulose, (b) an organic solvent that is inert to isocyanate groups and dissolves nitrocellulose, and (c) an organic solvent that is inert to isocyanate groups and does not dissolve nitrocellulose. These three substances form a uniform solid phase, and the content of (a) is 50-80% by weight, (b)/(c) = 15-80% by weight.
80/20~85 (weight ratio), non-adhesive granules,
A shaped nitrocellulose composition characterized in that it is in the form of chips or pellets. 2 Moisturized with alcohol and/or water
(a) nitrocellulose, (b) an organic solvent that is inert to isocyanate groups and dissolves nitrocellulose alone or together with (c) an organic solvent that is inert to isocyanate groups and does not dissolve nitrocellulose. A mixed solvent consisting of the mixture was added in an amount such that the nitrocellulose was at least partially dissolved and the resulting mixture did not flow easily at room temperature without the application of mechanical force, and the mixture was kneaded or kneaded. After that, there is a step of mechanically molding it into granules, chips or pellets, and the molded product is treated with an organic solvent that is inert to isocyanate groups and does not dissolve nitrocellulose, or in combination with the organic solvent. and a distillation step in which a mixture with an organic solvent that dissolves nitrocellulose is added, and by heating and/or reduced pressure, alcohols and/or water are substantially removed together with a part of the organic solvent. do(a)
50~80% by weight, (b)/(c) is 15~80/20~85
(weight ratio) A method for producing a nitrocellulose composition molded into a non-adhesive uniform solid phase. 3 The organic solvent used in the molding process is a nitrocellulose-insoluble organic solvent that is inert to isocyanate groups.
3. The method according to claim 2, comprising 80% by weight or less of a nitrocellulose-soluble organic solvent that is inert to isocyanate groups. 4 The organic solvent used in the distillation process is a nitrocellulose-soluble organic solvent that is inert to isocyanate groups.
3. The method according to claim 2, comprising 20% by weight or less of a nitrocellulose-insoluble organic solvent that is inert to isocyanate groups. 5 The nitrocellulose-soluble organic solvent inert to isocyanate groups is ethyl acetate, propyl acetate,
The claimed invention is characterized in that it is at least one member selected from the group consisting of butyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, isophorone, iclohexanone, nitroethane, and nitropropane. The manufacturing method according to scope 2. 6 The nitrocellulose-soluble organic solvent inert to isocyanate groups is ethyl acetate, propyl acetate,
6. The manufacturing method according to claim 2 or 5, characterized in that at least one selected from the group consisting of butyl acetate, methyl ethyl ketone, and methyl isobutyl ketone is used. 7. Claim 2, wherein the nitrocellulose-insoluble organic solvent inert to isocyanate groups is at least one selected from the group consisting of hexane, heptane octane, solvent naphtha, cyclohexane, benzene, toluene, and xylene. Manufacturing method described in section. 8. The manufacturing method according to claim 2 or 7, wherein the nitrocellulose-insoluble organic solvent inert to isocyanate groups is at least one selected from the group consisting of toluene, xylene, and hexane.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8013780A JPS575730A (en) | 1980-06-16 | 1980-06-16 | Molding nitrocellulose composition and its preparation |
| GB8034602A GB2067568B (en) | 1979-12-28 | 1980-10-28 | Nitrocellulose composition and process for production thereof |
| DE3041085A DE3041085C2 (en) | 1979-12-28 | 1980-10-31 | Nitrocellulose mixtures, process for their production and their use as additives to polyurethane varnishes |
| FR8023374A FR2472578B1 (en) | 1979-12-28 | 1980-10-31 | NITROCELLULOSE COMPOSITION AND PROCESS FOR THE PRODUCTION THEREOF |
| US06/206,312 US4483714A (en) | 1979-12-28 | 1980-11-12 | Nitrocellulose composition and process for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8013780A JPS575730A (en) | 1980-06-16 | 1980-06-16 | Molding nitrocellulose composition and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS575730A JPS575730A (en) | 1982-01-12 |
| JPS6352669B2 true JPS6352669B2 (en) | 1988-10-19 |
Family
ID=13709856
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8013780A Granted JPS575730A (en) | 1979-12-28 | 1980-06-16 | Molding nitrocellulose composition and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS575730A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3526921A1 (en) * | 1985-07-27 | 1987-02-05 | Mauser Werke Gmbh | TANK |
| JPS62109739A (en) * | 1985-10-25 | 1987-05-20 | 昭和電工株式会社 | Drum made of synthetic resin |
| JPS62135150A (en) * | 1985-11-29 | 1987-06-18 | 昭和電工株式会社 | Drum made of synthetic resin |
| DE19909230A1 (en) * | 1999-03-03 | 2000-09-07 | Wolff Walsrode Ag | Process for the production of compressed free-flowing paint raw materials |
| DE102007017014A1 (en) * | 2007-04-07 | 2008-10-09 | Dow Wolff Cellulosics Gmbh | Process for the preparation of low-water nitrocellulose solutions |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54110236A (en) * | 1978-02-16 | 1979-08-29 | Fujikura Kasei Kk | Under coating compound for vacuum metallizing |
| JPS5693737A (en) * | 1979-12-28 | 1981-07-29 | Asahi Chem Ind Co Ltd | Nitrocellulose composition and production thereof |
-
1980
- 1980-06-16 JP JP8013780A patent/JPS575730A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54110236A (en) * | 1978-02-16 | 1979-08-29 | Fujikura Kasei Kk | Under coating compound for vacuum metallizing |
| JPS5693737A (en) * | 1979-12-28 | 1981-07-29 | Asahi Chem Ind Co Ltd | Nitrocellulose composition and production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS575730A (en) | 1982-01-12 |
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