JPH0556380B2 - - Google Patents
Info
- Publication number
- JPH0556380B2 JPH0556380B2 JP21915384A JP21915384A JPH0556380B2 JP H0556380 B2 JPH0556380 B2 JP H0556380B2 JP 21915384 A JP21915384 A JP 21915384A JP 21915384 A JP21915384 A JP 21915384A JP H0556380 B2 JPH0556380 B2 JP H0556380B2
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- compound
- high molecular
- acid
- general formula
- 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 - Lifetime
Links
- 150000002605 large molecules Chemical class 0.000 claims description 16
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 8
- 125000005907 alkyl ester group Chemical group 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 5
- -1 polytetramethylene Polymers 0.000 description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 description 5
- MEEKGULDSDXFCN-UHFFFAOYSA-N 2-pentylphenol Chemical group CCCCCC1=CC=CC=C1O MEEKGULDSDXFCN-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000002334 glycols Chemical class 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000012644 addition polymerization Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 235000011118 potassium hydroxide Nutrition 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- XDESGXRLUIHEJT-UHFFFAOYSA-N 2,3,4-tribenzylphenol Chemical compound C=1C=CC=CC=1CC1=C(CC=2C=CC=CC=2)C(O)=CC=C1CC1=CC=CC=C1 XDESGXRLUIHEJT-UHFFFAOYSA-N 0.000 description 1
- PGEBXGLGFFYYFX-UHFFFAOYSA-N 2,3-dibenzylphenol Chemical compound C=1C=CC=CC=1CC=1C(O)=CC=CC=1CC1=CC=CC=C1 PGEBXGLGFFYYFX-UHFFFAOYSA-N 0.000 description 1
- ILJOIOLSOMYKNF-UHFFFAOYSA-N 2,3-didodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC(O)=C1CCCCCCCCCCCC ILJOIOLSOMYKNF-UHFFFAOYSA-N 0.000 description 1
- IXKVYSRDIVLASR-UHFFFAOYSA-N 2,3-dioctylphenol Chemical compound CCCCCCCCC1=CC=CC(O)=C1CCCCCCCC IXKVYSRDIVLASR-UHFFFAOYSA-N 0.000 description 1
- BYLSIPUARIZAHZ-UHFFFAOYSA-N 2,4,6-tris(1-phenylethyl)phenol Chemical compound C=1C(C(C)C=2C=CC=CC=2)=C(O)C(C(C)C=2C=CC=CC=2)=CC=1C(C)C1=CC=CC=C1 BYLSIPUARIZAHZ-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- CDMGNVWZXRKJNS-UHFFFAOYSA-N 2-benzylphenol Chemical compound OC1=CC=CC=C1CC1=CC=CC=C1 CDMGNVWZXRKJNS-UHFFFAOYSA-N 0.000 description 1
- YZBOVSFWWNVKRJ-UHFFFAOYSA-M 2-butoxycarbonylbenzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1C([O-])=O YZBOVSFWWNVKRJ-UHFFFAOYSA-M 0.000 description 1
- WCRKLZYTQVZTMM-UHFFFAOYSA-N 2-octadecylphenol Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1O WCRKLZYTQVZTMM-UHFFFAOYSA-N 0.000 description 1
- NTDQQZYCCIDJRK-UHFFFAOYSA-N 4-octylphenol Chemical compound CCCCCCCCC1=CC=C(O)C=C1 NTDQQZYCCIDJRK-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Polyethers (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
本発明は安定性に優れた組成物に関するもので
ある。
従来から水溶性高分子化合物としては、例えば
ポリビニルアルコール系（以下PVAという）、メ
チルセルロース系、ポリエチレンオキサイド系、
デンプン系、アクリル系及びヒドロキシプロピル
セルロース系等が知られているが、とリわけ今
日、水溶性フイルム又はシートにおいてはPVA
が主に使用されている。
PVAの水溶性フイルム又はシートは無色透明
で物性、例えば引裂強度等に優れ、適量の吸湿性
を有し、また耐油性があり、ほとんど大部分の有
機溶剤に溶解しない。
本発明者等は、かかる状況に鑑み、PVAの水
溶性フイルム又はシートと同様、若しくはそれ以
上の物性を有し、水溶性で、かつ特定の有機溶剤
に溶解する水溶性のフイルム、又はシートを提供
する新規高分子量化合物について種々検討した結
果、物性的に優れ、水溶性でかつ特定の有機溶剤
に溶解する水溶性のフイルム、又はシートを提供
する特定の高分子量化合物を知見した。これにつ
いては、すでに特許出願中である。
しかしながら、特定の高分子量化合物は、単独
で長時間空気中で加熱されたり、又は長時間日光
に晒されたりすると劣化が激しく、分子量が低下
することにより、それ自身のフイルム形成能が失
われる場合もあり、またフイルム状態では亀裂が
生じる場合もある。かかる欠点を改良するため、
さらに種々検討した結果、本発明を提供するにい
たつたものである。
すなわち、
(A) 平均分子量が8000以上で、かつエチレンオキ
シド鎖含有量が70重量％以上のポリオキシアル
キレングリコールと、多価カルボン酸又はその
無水物、又はその低級アルキルエステルとを反
応させて調製した平均分子量５万以上の高分子
量化合物に、
(B) 一般式(1)
〔ただし式中、Ａは炭素数５以上のアルキル基
又はアラルキル基を表す。Ｂは水素又はＡを表
す。Ｃは水素又はＡを表す。〕
で示される化合物（以下一般式(1)の化合物とい
う）１種以上を加えてなる安定性に優れた組成物
（以下組成物という）である。
本発明に使用する平均分子量が8000以上で、か
つエチレンオキシド鎖含有量が70重量％以上のポ
リオキシアルキレングリコール（以下特定のポリ
オキシアルキレングリコールという）としては、
活性水素基を２個有する有機化合物に、エチレン
オキサイドを含有するアルキレンオキサイドを付
加重合させて調製した平均分子量8000以上、エチ
レンオキシド鎖含有量70重量％以上のポリオキシ
アルキレングリコール等が挙げられる。
前記活性水素基とは、アルコール性水酸基、ア
ミノ基、フエノール性水酸基などである。該活性
水素基を２個有する有機化合物（以下出発物質と
いう）の具体例としては、例えばエチレングリコ
ール、ジエチレングリコール、ブロピレングリコ
ール、ジプロピレングリコール、１，４−ブタン
ジオール、１，６−ヘキサンジオール、ネオペン
チルリコール、ビスフエノールＡ、ポリエチレン
グリコール、ポリプロピレングリコール、ポリテ
トラメチレングリコール、ブチルアミン、アクチ
ルアミン、ラウリルアミン又はシクロヘキシルア
ミン等が挙げられる。
付加重合に使用するアルキレンオキサイドとし
ては、エチレンオキサイドを必須成分として含有
するものであり、エチレンオキサイド以外のアル
キレンオキサイドとしては、プロピレンオキサイ
ド、ブチレンオキサイド、スチレンオキサイド等
が挙げられる。
かかる付加重合は、好ましくは水酸化ナトリウ
ム、水酸化カリウム等の苛性アルカリを触媒と
し、約90〜200℃の温度で約２〜30時間行われる。
次に特定のポリオキシアルキレングリコール
に、多価カルボン酸、その無水物又はその低級ア
ルキルエステルを反応させることにより、平均分
子量５万以上の高分子量化合物とする。
該多価カルボン酸又はその無水物、又はその低
級アルキルエステルの具体例としては、
例えば、
(イ) マロン酸、コハク酸、マイレン酸、フマル
酸、アジピン酸、セバシン酸、フタル酸、イソ
フタル酸、テレフタル酸、イタコン酸、トリメ
リト酸、ピロメリト酸若しくはダイマー酸、
(ロ) (イ)の酸無水物
又は、
(ハ) (イ)のモノメチルエステル、ジメチルエステ
ル、モノエチルエステル、ジエチルエステル、
モノプロピルエステル、ジプロピルエステル、
モノブチルエステル若しくはジブチルエステ
ル、
等が挙げられる。
かかる反応は、特定のポリオキシアルキレング
リコールに多価カルポン酸、その無水物又はその
低級アルキルエステルを添加してから昇温し、80
〜250℃の加熱下に0.001〜20mmＨｇの減圧にして
脱水又は脱アルコールを行うことにより行われ
る。必要な反応時間は通常30分〜１時間が好まし
い。
高分子量化合物において、平均分子量が５万未
満の場合、フイルム又はシート形成能がないか、
又は強度の小さいものとなる。
次に本発明に使用する一般式(1)の化合物の具体
例としては、ターシヤリーアミルフエノール、ジ
ターシヤリーアミルフエノール、トリターシヤリ
ーアミルフエノール、パラオクチルフエノール、
ジオクチルフエノール、ノニルフエノール、ジノ
ニルフイルム、ドデシルフイルム、ジドデシルフ
エノール、スチレン化フエノール、ジスチレン化
フエノール、トリスチレン化フエノール、ベンジ
ルフエノール、ジベンジルフエノール、トリベン
ジルフエノール、ステアリルフエノール等が挙げ
られる。
本発明にかかる組成物としては、前記高分子量
化合物に、前記一般式(1)の化合物を加えたものが
挙げられる。
高分子量化合物に、一般式(1)の化合物を加える
場合、一般式(1)の化合物の添加量は、高分子量化
合物に対し、0.01〜10重量％である。
また添加方法としては、熱ロールにより60〜
100℃で所定量の両者を混練するか、又は反応さ
せて調製直後の高分子量化合物に一般式(1)の化合
物を添加混合する方法等が挙げられる。
本発明に従つて得られる組成物は、水溶性で、
かつ特定の溶剤に溶解し、さらに耐光性及び耐熱
性に優れていることから、フイルム又はシートの
分野はもちろん、それ以外の分野にも利用が拡大
してゆくことが考えられる。
次に実施例を挙げて、本発明を説明する。実施
例中、「％」及び「部」は、重量を基準とする。
製造例
オートクレーブ中にジエチレングリコール106
部及びフレーク苛性カリ20部を仕込み、130℃の
加熱下に２Kg／cm2Ｇ以下でエチレンオキサイド
12000部を徐々に加えながら反応させた。生成物
（中間体）の重量平均分子量をヒドロキシル価と
アルカリ価を測定して計算したところ、約10000
であつた。
次にこの生成物100部を採り、それにテレフタ
ル酸ジメチル1.94部を加え、120℃に昇温させた
のち、１mmＨｇの減圧の状態でエタノールを除去
し、高分子量化合物を得た。かかる高分子量化合
物の重量平均分子量を高速液体クロマトグラフイ
ーで測定したところ、約200000であつた。またそ
れの５部を採り、水又は溶剤95部に対する溶解性
を調べた。
同様にして、各種高分子量化合物を得た。それ
らを第１表に示す。
The present invention relates to a composition with excellent stability. Conventionally, water-soluble polymer compounds include, for example, polyvinyl alcohol (hereinafter referred to as PVA), methyl cellulose, polyethylene oxide,
Starch-based, acrylic-based and hydroxypropylcellulose-based are known, but today PVA is the most widely used in water-soluble films or sheets.
is mainly used. A water-soluble PVA film or sheet is colorless and transparent, has excellent physical properties such as tear strength, has a suitable amount of moisture absorption, is oil resistant, and does not dissolve in most organic solvents. In view of this situation, the present inventors have developed a water-soluble film or sheet that has physical properties similar to or better than that of PVA water-soluble film or sheet, is water-soluble, and is soluble in a specific organic solvent. As a result of various studies on the new high molecular weight compounds to be provided, we have discovered a specific high molecular weight compound that provides a water soluble film or sheet that has excellent physical properties, is water soluble, and dissolves in a specific organic solvent. A patent application for this is already pending. However, when certain high molecular weight compounds are heated alone in the air for long periods of time or exposed to sunlight for long periods of time, they deteriorate severely, and as a result of the decrease in molecular weight, they may lose their own film-forming ability. Also, cracks may occur in the film state. In order to improve these shortcomings,
As a result of further various studies, we have arrived at the present invention. That is, (A) prepared by reacting a polyoxyalkylene glycol with an average molecular weight of 8000 or more and an ethylene oxide chain content of 70% by weight or more and a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester. (B) General formula (1) for a high molecular weight compound with an average molecular weight of 50,000 or more [However, in the formula, A represents an alkyl group or an aralkyl group having 5 or more carbon atoms. B represents hydrogen or A. C represents hydrogen or A. ] This is a highly stable composition (hereinafter referred to as a composition) containing one or more compounds represented by the formula (hereinafter referred to as a compound of general formula (1)). The polyoxyalkylene glycols (hereinafter referred to as specific polyoxyalkylene glycols) having an average molecular weight of 8000 or more and an ethylene oxide chain content of 70% by weight or more used in the present invention include:
Examples include polyoxyalkylene glycols with an average molecular weight of 8,000 or more and an ethylene oxide chain content of 70% by weight or more, prepared by addition polymerizing an alkylene oxide containing ethylene oxide to an organic compound having two active hydrogen groups. The active hydrogen group includes an alcoholic hydroxyl group, an amino group, a phenolic hydroxyl group, and the like. Specific examples of the organic compound having two active hydrogen groups (hereinafter referred to as starting material) include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, Examples include neopentyl glycol, bisphenol A, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, butylamine, actylamine, laurylamine, and cyclohexylamine. The alkylene oxide used in addition polymerization contains ethylene oxide as an essential component, and examples of alkylene oxides other than ethylene oxide include propylene oxide, butylene oxide, and styrene oxide. Such addition polymerization is preferably carried out using a caustic alkali such as sodium hydroxide or potassium hydroxide as a catalyst at a temperature of about 90 to 200°C for about 2 to 30 hours. Next, a specific polyoxyalkylene glycol is reacted with a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester to form a high molecular weight compound having an average molecular weight of 50,000 or more. Specific examples of the polyhydric carboxylic acid, its anhydride, or its lower alkyl ester include (a) malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, phthalic acid, isophthalic acid, Terephthalic acid, itaconic acid, trimellitic acid, pyromellitic acid or dimer acid, (b) acid anhydride of (a), or (c) monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester of (a),
Monopropyl ester, dipropyl ester,
Examples include monobutyl ester and dibutyl ester. Such a reaction involves adding a polyhydric carboxylic acid, its anhydride, or its lower alkyl ester to a specific polyoxyalkylene glycol and then raising the temperature to 80°C.
Dehydration or dealcoholization is carried out under heating at ~250°C under reduced pressure of 0.001~20 mmHg. The required reaction time is usually preferably 30 minutes to 1 hour. In high molecular weight compounds, if the average molecular weight is less than 50,000, there is no ability to form a film or sheet;
Or the strength will be low. Specific examples of the compound of general formula (1) used in the present invention include tertiary amylphenol, ditertiary amylphenol, tritertiary amylphenol, paraoctylphenol,
Examples include dioctylphenol, nonylphenol, dinonyl film, dodecyl film, didodecyl phenol, styrenated phenol, distyrenated phenol, tristyrenated phenol, benzyl phenol, dibenzyl phenol, tribenzyl phenol, and stearyl phenol. The composition according to the present invention includes one in which the compound of the general formula (1) is added to the high molecular weight compound. When adding the compound of general formula (1) to the high molecular weight compound, the amount of the compound of general formula (1) added is 0.01 to 10% by weight based on the high molecular weight compound. In addition, as for the addition method, 60~
Examples include a method of kneading a predetermined amount of both at 100°C, or adding and mixing the compound of general formula (1) to a high molecular weight compound immediately after the reaction. The composition obtained according to the invention is water-soluble;
Since it is soluble in specific solvents and has excellent light resistance and heat resistance, it is thought that its use will expand not only to the field of films and sheets but also to other fields. Next, the present invention will be explained with reference to Examples. In the examples, "%" and "part" are based on weight. Production example Diethylene glycol 106 in autoclave
and 20 parts of flaked caustic potash were heated at 130°C to produce ethylene oxide at a concentration of 2 kg/cm 2 G or less.
The reaction was carried out while gradually adding 12,000 parts. The weight average molecular weight of the product (intermediate) was calculated by measuring the hydroxyl value and alkali value, and was found to be approximately 10,000.
It was hot. Next, 100 parts of this product were taken, 1.94 parts of dimethyl terephthalate was added thereto, the temperature was raised to 120°C, and ethanol was removed under reduced pressure of 1 mmHg to obtain a high molecular weight compound. The weight average molecular weight of this high molecular weight compound was measured by high performance liquid chromatography and was found to be approximately 200,000. Further, 5 parts of it was taken and its solubility in 95 parts of water or solvent was examined. Various high molecular weight compounds were obtained in the same manner. They are shown in Table 1.
【表】【table】
【表】【table】
【表】
実施例 １
各種高分子量化合物に一般式(1)の化合物を加え
て得た各種組成物の耐光性の評価を行つた。結果
を第２表に示す。
なお、組成物の評価は、約75℃の熱ロールによ
りフイルムを成形し、これらを日光に照射し、分
子量の経日変化を高速液体クロマトグラフイーで
測定した。[Table] Example 1 The light resistance of various compositions obtained by adding the compound of general formula (1) to various high molecular weight compounds was evaluated. The results are shown in Table 2. The composition was evaluated by forming a film using a hot roll at about 75°C, exposing it to sunlight, and measuring the change in molecular weight over time using high performance liquid chromatography.
【表】
実施例 ２
各種高分子量化合物に、一般式(1)の化合物を加
えて得た各種組成物の耐熱性の評価を行つた。結
果を第３表に示す。
なお、組成物の評価は、約75℃の熱ロールによ
りフイルムを成形し、これを80℃の熱風乾燥機中
に置き、分子量の経日変化を高速液体クロマトグ
ラフイーで測定した。[Table] Example 2 The heat resistance of various compositions obtained by adding the compound of general formula (1) to various high molecular weight compounds was evaluated. The results are shown in Table 3. The composition was evaluated by forming a film using a hot roll at about 75°C, placing it in a hot air dryer at 80°C, and measuring the change in molecular weight over time using high performance liquid chromatography.
Claims (1)
オキシド鎖含有量が70重量％以上のポリオキシ
アルキレングリコールと、多価カルボン酸又は
その無水物、又はその低級アルキルエステルと
を反応させて調製した平均分子量５万以上の高
分子量化合物に、 (B) 一般式(1) 〔ただし式中、 Ａは炭素数５以上のアルキル基又はアラルキ
ル基を表す。 Ｂは水素又はＡを表す。 Ｃは水素又はＡを表す。〕 で示される化合物１種以上を、高分子量化合物に
対し、0.01〜10重量％を加えてなる安定性に優れ
た組成物。[Scope of Claims] 1 (A) A polyoxyalkylene glycol having an average molecular weight of 8,000 or more and an ethylene oxide chain content of 70% by weight or more, and a polyhydric carboxylic acid or anhydride thereof, or a lower alkyl ester thereof. (B) General formula (1) [However, in the formula, A represents an alkyl group or an aralkyl group having 5 or more carbon atoms. B represents hydrogen or A. C represents hydrogen or A. ] A highly stable composition comprising 0.01 to 10% by weight of one or more compounds represented by the following to a high molecular weight compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21915384A JPS6197352A (en) | 1984-10-17 | 1984-10-17 | Composition having excellent stability |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21915384A JPS6197352A (en) | 1984-10-17 | 1984-10-17 | Composition having excellent stability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6197352A JPS6197352A (en) | 1986-05-15 |
| JPH0556380B2 true JPH0556380B2 (en) | 1993-08-19 |
Family
ID=16731031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21915384A Granted JPS6197352A (en) | 1984-10-17 | 1984-10-17 | Composition having excellent stability |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6197352A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014169317A (en) * | 2008-06-17 | 2014-09-18 | Millennium Pharmaceuticals Inc | Boronate ester compounds and pharmaceutical compositions thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5334424B2 (en) * | 2008-02-15 | 2013-11-06 | 住友化学株式会社 | Method for producing stabilized poly (alkylene oxide) |
-
1984
- 1984-10-17 JP JP21915384A patent/JPS6197352A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014169317A (en) * | 2008-06-17 | 2014-09-18 | Millennium Pharmaceuticals Inc | Boronate ester compounds and pharmaceutical compositions thereof |
| JP2014196310A (en) * | 2008-06-17 | 2014-10-16 | ミレニアム ファーマシューティカルズ， インコーポレイテッドＭｉｌｌｅｎｎｉｕｍ Ｐｈａｒｍａｃｅｕｔｉｃａｌｓ， Ｉｎｃ． | Boronate ester compounds and pharmaceutical compositions thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6197352A (en) | 1986-05-15 |
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