JPS6113488B2 - - Google Patents
Info
- Publication number
- JPS6113488B2 JPS6113488B2 JP16647379A JP16647379A JPS6113488B2 JP S6113488 B2 JPS6113488 B2 JP S6113488B2 JP 16647379 A JP16647379 A JP 16647379A JP 16647379 A JP16647379 A JP 16647379A JP S6113488 B2 JPS6113488 B2 JP S6113488B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose acetate
- parts
- acetone
- weight
- resin composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 36
- 229920002301 cellulose acetate Polymers 0.000 claims description 36
- 239000000203 mixture Substances 0.000 claims description 10
- 239000004014 plasticizer Substances 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 8
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical class NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 claims description 6
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 6
- 230000021736 acetylation Effects 0.000 claims description 4
- 238000006640 acetylation reaction Methods 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- -1 alkyl phthalate Chemical compound 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000002904 solvent Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 8
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 3
- 229960001826 dimethylphthalate Drugs 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 235000013773 glyceryl triacetate Nutrition 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 229960002622 triacetin Drugs 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OVOUKWFJRHALDD-UHFFFAOYSA-N 2-[2-(2-acetyloxyethoxy)ethoxy]ethyl acetate Chemical compound CC(=O)OCCOCCOCCOC(C)=O OVOUKWFJRHALDD-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002168 ethanoic acid esters Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003655 tactile properties Effects 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、成形過程では熱可塑性と熱接着性を
示し、成型過程を経た後は良好な熱変形抵抗性と
耐溶剤性を発揮する酢酸セルロース樹脂組成物に
関するものであり、更に詳しくは酢酸セルロース
100重量部と酢酸セルロース用可塑剤５〜60重量
部及び架橋剤0.5〜100重量部を混合して成る酢酸
セルロース樹脂組成物に関するものである。
一般に酢酸セルロースは耐衝撃性、感触性、耐
油性などに優れていることが知られており、プラ
スチツクス、繊維として広く使用されている。し
かしながら、酢酸セルロースは耐熱性、耐溶剤性
が充分でないために一部の用途に対しでは、その
使用が制限されている。特にプラスチツクスとし
て用いる場合は、可塑剤を配合するのが通常であ
り、そのため耐熱性がよくない。
本発明は、酢酸セルロースが有する耐衝撃性、
感触性、耐油性などの優れた特徴を損うことな
く、熱接着性、熱変形抵抗性、耐溶剤性を付与し
得ることのできる新規な酢酸セルロース樹脂組成
物に関するものである。
従来、熱可塑性樹脂の耐熱性を向上させること
を目的として熱可塑性樹脂に熱硬化性樹脂又はそ
のプレポリマーをブレンドする方法が知られてい
るが、これまで酢酸セルロースに関しては有効な
方法は知られていなかつた。
本発明者らは鋭意研究の結果、酢酸セルロース
に酢酸セルロース用可塑剤と架橋剤を混合するこ
とにより熱接着性を有し且つ成型過程後、良好な
熱変形抵抗性と耐溶剤性を示すに到る樹脂組成物
が得られることを見出し、本発明に到達した。
即ち、本発明の組成物とは酢酸セルロース100
重量部に脂肪族多価アルコールの酢酸エステル又
はフタル酸のアルキルエステル５〜60重量部とア
セトン可溶性のアルキル化メチロールメラミン、
アルキル化メチロール尿素、アルキル化メチロー
ルベンゾグアナミン、多価イソシアネート又はそ
れらの混合物0.5〜100重量部を混合して成る組成
物であつて、本組成物は熱可塑性と熱接着性を有
し、本組成物を加熱を伴う成型過程に付すること
により、熱変形抵抗性と耐溶剤性の良好な成型物
を得ることができる。
尚、本発明の組成物に於いて、これを構成する
酢酸セルロース用可塑剤量が酢酸セルロース100
重量部に対して５重量部以下では熱成型時に酢酸
セルロースを充分可塑化することが難しく、逆に
60重量部以上では得られる熱成型物の熱変形抵抗
性が低下する傾向を示して共に好ましくない。又
架橋剤についても同じく0.5重量部以下では得ら
れる成型物が良好な熱変形抵抗性と耐溶剤性を示
さなくなり、逆に100重量部以上では感触性など
の酢酸セルロースの特徴が失われる傾向があるこ
とと、特にアルキル化メチロール尿素の場合に成
型物が著しく褐変することがあり好ましくない。
本発明でいうところの脂肪族多価アルコールの
酢酸エステルとは、例えばグリセリントリアセテ
ート、ジグリセンテトラアセテート、トリエチレ
ングリコールジアセテートであり、フタル酸アル
キルエステルとは、例えばフタル酸ジメチル、フ
タル酸ジエチルである。これらはいずれも酢酸セ
ルロースに対する可塑化力が強く、少量の配合に
より可塑化効果を発揮するものである。
又本発明で使用する酢酸セルロースとしてはア
セトン可溶性の酢化度が48〜57％、好ましくは52
〜55％、25℃アセトン溶液での極限粘度が0.15〜
2.2、好ましくは0.8〜1.9のものがよい。
本発明の組成物を得る手段として、酢酸セルロ
ース、酢酸セルロース用可塑剤及び架橋剤の３者
を直接混合してもよいし、共通の溶剤例えばアセ
トンの存在下で混合した後溶剤を除去してもよ
い。
本発明の組成物の特徴は加熱を伴う成型過程で
熱可塑性と熱接着性を示し、成型過程を経た後は
良好な熱変形抵抗性と耐溶剤性を有する成型物と
なることである。得られた成型物が良好な熱変形
抵抗性と耐溶剤性を示す理由としては酢酸セルロ
ースの分子内水酸基と架橋剤との間で、いわゆる
架橋を起こし、新しい化合物が生成するためと推
定される。
本発明の組成物の用途としては、例えば眼鏡
枠、ブローチなどの成型品、ホツトメルト接着
剤、加熱硬化型塗料樹脂、粉体塗料などが考えら
れる。
以下に本発明を実施例を挙げて説明するが、い
うまでもなく記実施例は本発明を限定するもので
はない。但し、酢酸セルロースの酸化度は次の方
法で求めた。
粉砕絶乾試料約0.5gを精秤し、共栓付300mlフ
ラスコ内で精製アセトン50mlに溶解させた後50ml
の0.2規定水酸化ナトリウム水溶液を加えて25℃
下で３時間鹸化する。次に0.2規定塩酸水50mlを
加え、15分間放置後フエノールフタレインを指示
薬として、0.2規定水酸化ナトリウム水溶液で逆
滴定する。尚、ブランクテストを同時に行なう。
酸化度（％）＝（Ａ−Ｂ）×Ｆ×１．２０１／試料重
量（ｇ）
Ａ：試料の0.2規定水酸化ナトリウム水溶液
の滴定ml数
Ｂ：ブランクの0.2規定水酸化ナトリウム水
溶液の滴定ml数
Ｆ：0.2規定水酸化ナトリウム水溶液のフア
クター
又酢酸セルロースの極限粘度は次の方法で求め
た。
粉砕絶乾試料0.5gを精秤後、100mlメスフラス
コ内で精製アセトンに溶解して、全体量を100ml
とし、オスワルド粘度計により、25±0.1℃の恒
温水槽中で落下秒数を測定する。尚精製アセトン
のみについても同様の測定を行なう。
ηre（相対粘度）＝ｔ／t0
〔η〕（極限粘度）
＝2.3026×ogηre／Ｃ
ｔ：試料液の落下秒数
t0：精製アセトンの落下秒数
Ｃ：試料液濃度（ｇ／ｄ）
尚、実施例及び参考例中、部又は％とあるのは
いずれも重量部、重量％である。
実施例 １
酢酸セルロース（酢化度54.7％、極限粘度
1.69）100部、フタル酸ジメチル40部及びメチル
化メチロールメラミン（住友化学〓製スミマール
Ｍ−100C）５部乃至10部又はメチル化メチロー
ル尿素（三井東圧化学〓製UFR−65）10部乃至
20部にアセトン200部を加え、常温でよく撹拌し
て得られた粘稠溶液を平滑面上に、約3m／ｍ厚
さに流延し、そのまま60℃雰囲気中に放置してア
セトンを蒸発させた後、裁断してペレツトを作製
した。次にこのペレツトを温度180℃、圧力35
Kg／cm2の条件で５分間プレスし、冷却後約3m／
ｍ厚さの成型物を得た。この成型物と、比較して
メチル化メチロールメラミン及びメチル化メラロ
ール尿素を配合せず、同様の方法で得た成型物の
アセトン溶解度、衝撃強度及び耐熱性をまとめて
第１表に示す。尚アセトン溶解度は成型物を30℃
アセトン中に72時間浸漬後の溶解度、衝撃強度は
JISK6791によりアイゾツト衝撃強度、耐熱性は
200℃オーブン中に４分間放置したときの熔融状
態を示す。
The present invention relates to a cellulose acetate resin composition that exhibits thermoplasticity and thermal adhesiveness during the molding process, and exhibits good thermal deformation resistance and solvent resistance after the molding process.
The present invention relates to a cellulose acetate resin composition prepared by mixing 100 parts by weight of a cellulose acetate plasticizer with 5 to 60 parts by weight of a cellulose acetate plasticizer and 0.5 to 100 parts by weight of a crosslinking agent. Cellulose acetate is generally known to have excellent impact resistance, tactility, oil resistance, etc., and is widely used as plastics and fibers. However, cellulose acetate does not have sufficient heat resistance or solvent resistance, so its use is limited in some applications. Particularly when used as plastics, it is common to add a plasticizer, which results in poor heat resistance. The present invention provides impact resistance that cellulose acetate has,
The present invention relates to a novel cellulose acetate resin composition that can provide thermal adhesiveness, thermal deformation resistance, and solvent resistance without impairing excellent characteristics such as tactility and oil resistance. Conventionally, a method of blending a thermosetting resin or its prepolymer with a thermoplastic resin has been known for the purpose of improving the heat resistance of the thermoplastic resin, but until now no effective method has been known for cellulose acetate. I wasn't there. As a result of intensive research, the present inventors have found that by mixing cellulose acetate with a plasticizer for cellulose acetate and a crosslinking agent, it has thermal adhesive properties and exhibits good thermal deformation resistance and solvent resistance after the molding process. The inventors have discovered that the following resin compositions can be obtained, and have arrived at the present invention. That is, the composition of the present invention is cellulose acetate 100
5 to 60 parts by weight of acetate ester of aliphatic polyhydric alcohol or alkyl ester of phthalic acid and acetone-soluble alkylated methylolmelamine;
A composition comprising 0.5 to 100 parts by weight of an alkylated methylol urea, an alkylated methylol benzoguanamine, a polyvalent isocyanate, or a mixture thereof, which has thermoplasticity and thermal adhesive properties; By subjecting the material to a molding process that involves heating, a molded product with good thermal deformation resistance and solvent resistance can be obtained. In addition, in the composition of the present invention, the amount of plasticizer for cellulose acetate constituting this is 100% cellulose acetate.
If it is less than 5 parts by weight, it is difficult to sufficiently plasticize cellulose acetate during thermoforming;
If it exceeds 60 parts by weight, the heat deformation resistance of the resulting thermoformed product tends to decrease, which is not preferable. Similarly, if the crosslinking agent is less than 0.5 parts by weight, the resulting molded product will not exhibit good heat deformation resistance and solvent resistance, and if it is more than 100 parts by weight, the characteristics of cellulose acetate such as tactile properties tend to be lost. In addition, especially in the case of alkylated methylol urea, the molded product may brown significantly, which is not preferable. In the present invention, acetic acid esters of aliphatic polyhydric alcohols include, for example, glycerin triacetate, diglycene tetraacetate, and triethylene glycol diacetate, and phthalic acid alkyl esters include, for example, dimethyl phthalate and diethyl phthalate. be. All of these have a strong plasticizing power for cellulose acetate, and can exhibit a plasticizing effect when added in small amounts. Furthermore, the cellulose acetate used in the present invention has an acetone-soluble acetylation degree of 48 to 57%, preferably 52%.
~55%, intrinsic viscosity in acetone solution at 25℃ is ~0.15
2.2, preferably 0.8 to 1.9. As a means of obtaining the composition of the present invention, the three components of cellulose acetate, a plasticizer for cellulose acetate, and a crosslinking agent may be directly mixed together, or they may be mixed in the presence of a common solvent, such as acetone, and then the solvent is removed. Good too. The composition of the present invention is characterized in that it exhibits thermoplasticity and thermal adhesiveness during the molding process that involves heating, and that after the molding process it becomes a molded product that has good thermal deformation resistance and solvent resistance. The reason why the obtained molded product exhibits good thermal deformation resistance and solvent resistance is presumed to be because so-called crosslinking occurs between the intramolecular hydroxyl group of cellulose acetate and the crosslinking agent, resulting in the formation of a new compound. . Possible uses of the composition of the present invention include, for example, molded products such as eyeglass frames and brooches, hot melt adhesives, heat-curable coating resins, and powder coatings. The present invention will be explained below with reference to Examples, but it goes without saying that the Examples are not intended to limit the present invention. However, the degree of oxidation of cellulose acetate was determined by the following method. Precisely weigh approximately 0.5g of the pulverized bone-dried sample, dissolve it in 50ml of purified acetone in a 300ml flask with a stopper, and then add 50ml of the sample.
Add 0.2N aqueous sodium hydroxide solution and heat at 25°C.
Saponify under water for 3 hours. Next, add 50 ml of 0.2N hydrochloric acid, leave for 15 minutes, and then back titrate with 0.2N sodium hydroxide aqueous solution using phenolphthalein as an indicator. Incidentally, a blank test is conducted at the same time. Oxidation degree (%) = (A-B) x F x 1.201/sample weight (g) A: Titration ml of 0.2N sodium hydroxide aqueous solution of sample B: Titration ml of blank 0.2N sodium hydroxide aqueous solution Number F: Factor of 0.2N aqueous sodium hydroxide solution The intrinsic viscosity of cellulose acetate was determined by the following method. After accurately weighing 0.5g of the crushed bone-dried sample, dissolve it in purified acetone in a 100ml volumetric flask to make a total volume of 100ml.
Then, the number of seconds it falls is measured using an Oswald viscometer in a constant temperature water bath at 25±0.1℃. A similar measurement is also performed for purified acetone alone. ηre (relative viscosity) = t/t 0 [η] (limiting viscosity) = 2.3026×ogηre/C t: Number of seconds for sample solution to fall t 0 : Number of seconds for purified acetone to fall C: Sample solution concentration (g/d) In addition, in Examples and Reference Examples, all parts or % are parts by weight or % by weight. Example 1 Cellulose acetate (degree of acetylation 54.7%, intrinsic viscosity
1.69) 100 parts, 40 parts of dimethyl phthalate and 5 to 10 parts of methylated methylolmelamine (Sumimar M-100C manufactured by Sumitomo Chemical Co., Ltd.) or 10 parts to 10 parts of methylated methylol urea (UFR-65 manufactured by Mitsui Toatsu Chemical Co., Ltd.)
Add 200 parts of acetone to 20 parts, stir well at room temperature, and cast the resulting viscous solution onto a smooth surface to a thickness of about 3 m/m, and leave it in an atmosphere of 60°C to evaporate the acetone. After that, the pellets were cut into pellets. Next, this pellet is heated at a temperature of 180℃ and a pressure of 35℃.
Pressed for 5 minutes at Kg/cm 2 and cooled down to approximately 3m/cm2.
A molded product with a thickness of m was obtained. Table 1 summarizes the acetone solubility, impact strength, and heat resistance of this molded product and a molded product obtained in the same manner without methylated methylolmelamine or methylated melarol urea. The acetone solubility of the molded product is 30℃.
Solubility and impact strength after 72 hours immersion in acetone are
Izotsu impact strength and heat resistance according to JISK6791
This shows the melted state when left in an oven at 200°C for 4 minutes.
【表】
即ち、本発明の組成物は成型過程を経た後に耐
熱変形抵抗性が向上し、アセトン溶解度が顕著に
減少した。第１表に於けるアセトン溶解分は可塑
剤（フタル酸ジメチル）によるものであり、酢酸
セルロース自体は不溶性となつている。これは酢
酸セルロースと架橋剤が反応し、架橋構造を有す
る成型物が得られたことによるものと考えられ
る。
実施例 ２
酢酸セルロース（酸化度55.5％、極限粘度
0.80）100部、トリアセチン（グリセリントリア
セテート）50部及びメチル化メチロールメラミン
（住友化学〓製スミマールＭ−40W）10部又はメ
チル化メチロール尿素（三井東圧化学〓製ユーラ
ミンＴ−101）20部をアセトン350部に溶解させた
後、ガラス板上に流延し、アセトンを蒸発させて
厚さ40μのフイルムを作製した。このフイルムを
２枚のアルミ箱（厚さ50μ）、綿布（サテン、
晒）及びセロハン（厚さ21μ）の間に、それぞれ
挾み、温度180℃、圧力２Kg／cm2で10秒又は120秒
間熱接着した。次に得られた熱接着物を１cm幅に
切り取り、50mm／分の剥離速度で90゜剥離により
熱着強度を測定した。その結果を第２表に示す。
又比較として、上記と同様の方法により作製した
酢酸セルロースとメチル化メチロールメラミン、
酢酸セルロースとメチル化メチロール尿素あるい
は酢酸セルロースとトリアセチンのみからなるそ
れぞれのフイルム（厚さ40μ）の接着強度も併せ
て示す。尚、いずれのフイルムも、熱接着時に異
臭は感じられなかつた。[Table] That is, after the composition of the present invention was subjected to the molding process, the heat resistance and deformation resistance were improved, and the acetone solubility was significantly reduced. The amount dissolved in acetone in Table 1 is due to the plasticizer (dimethyl phthalate), and cellulose acetate itself is insoluble. This is thought to be due to the reaction between cellulose acetate and the crosslinking agent, resulting in a molded product having a crosslinked structure. Example 2 Cellulose acetate (oxidation degree 55.5%, intrinsic viscosity
0.80), 50 parts of triacetin (glycerol triacetate) and 10 parts of methylated methylolmelamine (Sumimar M-40W manufactured by Sumitomo Chemical Co., Ltd.) or 20 parts of methylated methylol urea (Eulamine T-101 manufactured by Mitsui Toatsu Chemical Co., Ltd.) in acetone. After dissolving the solution in 350 parts, it was cast onto a glass plate and the acetone was evaporated to produce a film with a thickness of 40 μm. This film was placed in two aluminum boxes (thickness 50μ) and cotton cloth (satin,
They were sandwiched between 180° C. and 2 kg/cm 2 of pressure for 10 seconds or 120 seconds, respectively. Next, the obtained thermally bonded product was cut into a 1 cm width, and the thermal bond strength was measured by peeling at 90° at a peeling speed of 50 mm/min. The results are shown in Table 2.
For comparison, cellulose acetate and methylated methylolmelamine, which were produced by the same method as above,
The adhesion strength of each film (thickness: 40μ) consisting only of cellulose acetate and methylated methylolurea or cellulose acetate and triacetin is also shown. Incidentally, no strange odor was detected in any of the films during thermal bonding.
【表】
参考例
実用的な成型過程の条件とは対応しないが、本
発明の組成物のうち可塑剤を含まないものにつき
加熱により耐溶剤性が向上する傾向を参考例とし
て示す。
即ち、酢酸セルロース（酢化度55.0％、極限粘
度1.70）100部及び各種架橋剤20部のアセトン溶
液から流延法にて作製してフイルムと架橋剤を含
まない酢酸セルロースのみのフイルムを180℃オ
ーブン中で30分間熱処理した後、30℃アセトン及
び30℃メチレンクロライド／メタノール（90部／
10部）混合溶剤中に72時間浸漬し、両溶剤に対す
る各フイルムの溶解度を求めた。その結果は第３
表の通りであつた。[Table] Reference Example Although it does not correspond to the conditions of a practical molding process, the tendency for the solvent resistance of compositions of the present invention that do not contain a plasticizer to improve upon heating is shown as a reference example. That is, a film made by a casting method from an acetone solution of 100 parts of cellulose acetate (degree of acetylation 55.0%, intrinsic viscosity 1.70) and 20 parts of various crosslinking agents was heated at 180°C. After heat treatment in an oven for 30 minutes, 30℃ acetone and 30℃ methylene chloride/methanol (90 parts/
(10 parts) immersed in a mixed solvent for 72 hours, and the solubility of each film in both solvents was determined. The result is the third
It was as shown in the table.
【表】【table】
Claims (1)
ス用可塑剤５〜60重量部と、水酸基との結合能力
を有する架橋剤0.5〜100重量部より成る酢酸セル
ロース樹脂組成物。 ２ 酢酸セルロース用可塑剤が脂肪族多価アルコ
ール酢酸エステル又はフタル酸アルキルエステル
である特許請求の範囲第１項記載の樹脂組成物。 ３ 架橋剤がアセトン可溶性のアルキル化メチロ
ールメラミン、アルキル化メチロール尿素、アル
キル化メチロールベンゾクアナミン、多価イソシ
アネート又はそれらの混合物である特許請求の範
囲第１項記載の樹脂組成物。 ４ 酢酸セルロースが酢化度48〜57％、25℃に於
けるアセトン溶液の極限粘度0.15〜2.2の範囲の
ものである特許請求の範囲第１項記載の樹脂組成
物。[Scope of Claims] 1. A cellulose acetate resin composition comprising 100 parts by weight of cellulose acetate, 5 to 60 parts by weight of a plasticizer for cellulose acetate, and 0.5 to 100 parts by weight of a crosslinking agent capable of bonding to hydroxyl groups. 2. The resin composition according to claim 1, wherein the plasticizer for cellulose acetate is an aliphatic polyhydric alcohol acetate or an alkyl phthalate. 3. The resin composition according to claim 1, wherein the crosslinking agent is an acetone-soluble alkylated methylolmelamine, alkylated methylolurea, alkylated methylolbenzoquanamine, polyvalent isocyanate, or a mixture thereof. 4. The resin composition according to claim 1, wherein the cellulose acetate has a degree of acetylation of 48 to 57% and an intrinsic viscosity of an acetone solution at 25°C of 0.15 to 2.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16647379A JPS5688440A (en) | 1979-12-21 | 1979-12-21 | Noval cellulose acetate resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16647379A JPS5688440A (en) | 1979-12-21 | 1979-12-21 | Noval cellulose acetate resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5688440A JPS5688440A (en) | 1981-07-17 |
| JPS6113488B2 true JPS6113488B2 (en) | 1986-04-14 |
Family
ID=15832041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16647379A Granted JPS5688440A (en) | 1979-12-21 | 1979-12-21 | Noval cellulose acetate resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5688440A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011208339A (en) * | 2010-03-30 | 2011-10-20 | Taiwan Textile Research Inst | Cellulose-based masterbatch with network structure, application thereof and method for preparing the same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7510768B2 (en) | 2005-06-17 | 2009-03-31 | Eastman Chemical Company | Thermoplastic articles comprising cyclobutanediol having a decorative material embedded therein |
| US8304086B2 (en) | 2005-05-26 | 2012-11-06 | Eastman Chemical Company | Crosslinkable, cellulose ester compositions and films formed therefrom |
| US9598533B2 (en) | 2005-11-22 | 2017-03-21 | Eastman Chemical Company | Polyester compositions containing cyclobutanediol having a certain combination of inherent viscosity and moderate glass transition temperature and articles made therefrom |
| US9169388B2 (en) | 2006-03-28 | 2015-10-27 | Eastman Chemical Company | Polyester compositions which comprise cyclobutanediol and certain thermal stabilizers, and/or reaction products thereof |
| US8895654B2 (en) | 2008-12-18 | 2014-11-25 | Eastman Chemical Company | Polyester compositions which comprise spiro-glycol, cyclohexanedimethanol, and terephthalic acid |
| JP2011208103A (en) * | 2010-03-30 | 2011-10-20 | Fujifilm Corp | Resin composition, molded article, and housing for electric and electronic equipment |
| US20130217830A1 (en) | 2012-02-16 | 2013-08-22 | Eastman Chemical Company | Clear Semi-Crystalline Articles with Improved Heat Resistance |
| JP6488230B2 (en) * | 2015-12-28 | 2019-03-20 | 富士フイルム株式会社 | Cellulose ester film, polarizing plate and image display device. |
-
1979
- 1979-12-21 JP JP16647379A patent/JPS5688440A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011208339A (en) * | 2010-03-30 | 2011-10-20 | Taiwan Textile Research Inst | Cellulose-based masterbatch with network structure, application thereof and method for preparing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5688440A (en) | 1981-07-17 |
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