JP2009249308A - Discoloration preventive agent - Google Patents
Discoloration preventive agent Download PDFInfo
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- JP2009249308A JP2009249308A JP2008096873A JP2008096873A JP2009249308A JP 2009249308 A JP2009249308 A JP 2009249308A JP 2008096873 A JP2008096873 A JP 2008096873A JP 2008096873 A JP2008096873 A JP 2008096873A JP 2009249308 A JP2009249308 A JP 2009249308A
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- 238000002845 discoloration Methods 0.000 title abstract 3
- 230000003449 preventive effect Effects 0.000 title abstract 2
- 239000003112 inhibitor Substances 0.000 abstract description 72
- 238000006116 polymerization reaction Methods 0.000 abstract description 56
- 239000000178 monomer Substances 0.000 abstract description 25
- 239000003963 antioxidant agent Substances 0.000 abstract description 21
- 230000003078 antioxidant effect Effects 0.000 abstract description 18
- 150000001875 compounds Chemical class 0.000 abstract description 17
- 229920000642 polymer Polymers 0.000 abstract description 16
- 230000036961 partial effect Effects 0.000 abstract description 15
- 239000000835 fiber Substances 0.000 abstract description 8
- 239000003973 paint Substances 0.000 abstract description 8
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000976 ink Substances 0.000 abstract description 5
- 239000003607 modifier Substances 0.000 abstract description 5
- 239000012776 electronic material Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000002250 absorbent Substances 0.000 abstract description 2
- 238000004040 coloring Methods 0.000 description 57
- 238000012360 testing method Methods 0.000 description 30
- 239000003086 colorant Substances 0.000 description 24
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 22
- 230000000694 effects Effects 0.000 description 18
- 239000000523 sample Substances 0.000 description 17
- -1 amine compounds Chemical group 0.000 description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 11
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 11
- 230000002265 prevention Effects 0.000 description 11
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical group CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 8
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 230000006698 induction Effects 0.000 description 6
- 239000012488 sample solution Substances 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002216 antistatic agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 229920005668 polycarbonate resin Polymers 0.000 description 2
- 239000004431 polycarbonate resin Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- ZLHNYIHIHQEHJQ-UHFFFAOYSA-N N,N'-Diacetylhydrazine Chemical compound CC(=O)NNC(C)=O ZLHNYIHIHQEHJQ-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 229940067157 phenylhydrazine Drugs 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Polymerisation Methods In General (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
本発明は、重合性単量体またはその部分重合体、特に、アクリル系重合性単量体またはその部分重合体に添加して使用される重合抑制剤、特にフェノール系重合抑制剤、アミン系重合抑制剤または酸化防止剤に起因する着色を防止する着色防止剤および着色防止方法に関するものである。 The present invention relates to a polymerization monomer or a partial polymer thereof, in particular, a polymerization inhibitor used by being added to an acrylic polymerizable monomer or a partial polymer thereof, in particular a phenol polymerization inhibitor, an amine polymerization. The present invention relates to a coloring inhibitor and a coloring prevention method for preventing coloring caused by an inhibitor or an antioxidant.
着色防止剤としては、例えばメルカプタン系の化合物を重合調整剤として使用してメタクリル酸の重合の際に起こる着色を防止するためにトリフェニルホスフィンが有効であることが開示されている（特許文献１）。しかし、この文献には、ハイドロキノン、メトキシフェノール、ターシャリーブチルカテコール、メチルハイドロキノンなどのフェノール系化合物、アミン系化合物を重合抑制剤として用いることについての開示はなく、重合性単量体としてアクリル酸を使用することについては、教示も開示もない。 As a coloring inhibitor, for example, it is disclosed that triphenylphosphine is effective in order to prevent coloring that occurs during polymerization of methacrylic acid using a mercaptan-based compound as a polymerization regulator (Patent Document 1). ). However, this document does not disclose the use of phenolic compounds such as hydroquinone, methoxyphenol, tertiary butylcatechol, methylhydroquinone, and amine compounds as polymerization inhibitors, and acrylic acid is used as a polymerizable monomer. There is no teaching or disclosure of use.
また、電気、機械、自動車および医療分野で幅広く使用されているポリカーボネート樹脂の組成物の帯電防止剤としては、通常熱安定性に優れるホスホニウム塩が用いられている。ポリカーボネート樹脂は、表面固有抵抗が大きく、接触や摩擦などで誘起された静電気が消失し難いという性質を有する。ポリカーボネートの帯電防止剤としては、熱安定性や色相安定性が求められているが、しかし、ホスホニウム塩の場合には、着色するという問題があった。この問題を解決したものとして、熱安定性に優れた特定のアンモニウム塩の使用を提案している。その提案の中でトリフェニルホスフィンを安定剤として使用している（特許文献２）。 Further, as an antistatic agent for a polycarbonate resin composition widely used in the electrical, mechanical, automotive and medical fields, a phosphonium salt having excellent thermal stability is usually used. Polycarbonate resin has the property that the surface specific resistance is large and static electricity induced by contact or friction is difficult to disappear. As an antistatic agent for polycarbonate, thermal stability and hue stability are required. However, in the case of a phosphonium salt, there is a problem of coloring. As a solution to this problem, it has been proposed to use a specific ammonium salt having excellent thermal stability. Among the proposals, triphenylphosphine is used as a stabilizer (Patent Document 2).
また、芳香族ポリエステル組成物の製造において、機械的性質及び加熱時着色を防止する耐熱剤としてトリフェニルホスフィンの使用を開示されている（特許文献３）。なお、光沢、顔料分散性、粘度、印刷適正、効果速度などに優れた紫外線硬化型インキとして使用される多官能性オリゴマーの製造法において、重合抑制剤としてメトキシフェノールが、重合触媒としてトリフェニルホスフィンが、還元、酸化防止、着色防止などの諸機能を有する有機リン系化合物の具体例としてホスファイトが挙げられている（特許文献４）。 In addition, in the production of an aromatic polyester composition, the use of triphenylphosphine as a heat resistance agent that prevents mechanical properties and coloring during heating is disclosed (Patent Document 3). In addition, methoxyphenol is used as a polymerization inhibitor and triphenylphosphine is used as a polymerization catalyst in a method for producing a polyfunctional oligomer used as an ultraviolet curable ink excellent in gloss, pigment dispersibility, viscosity, printability, and effect speed. However, phosphite is mentioned as a specific example of an organic phosphorus compound having various functions such as reduction, oxidation prevention, and coloring prevention (Patent Document 4).
しかしながら、これらの何れの文献も、アクリル系重合性単量体またはその部分重合体に添加して使用される重合抑制剤または酸化防止剤に起因する着色の防止については教示も開示もない。 However, none of these documents teach or disclose the prevention of coloring caused by a polymerization inhibitor or an antioxidant used by being added to an acrylic polymerizable monomer or a partial polymer thereof.
ところで、酸化防止剤、重合抑制剤としてハイドロキノン、メトキシフェノール、ターシャリーブチルカテコール、メチルハイドロキノン等のフェノール系化合物、アミン系化合物が広く用いられる。しかし、これらの添加物はその効果を発現する際に発色を伴う場合が多く、この発色が添加した基材の着色をしばしば引き起こす。また、高温下での使用、日光の紫外線による劣化、排気ガス等による変質等により、最終製品としての使用環境によって着色を帯びてくることがあり、用途によっては支障をきたすことがある。具体的には、車両用透明部材、透明シート用部材では、光が通過した場合着色されると好ましくなく、光学機器部材であるレンズ、プリズム、光ディスク、シートは色相安定性を要する。同様に半導体用部材、電子材料、粘着剤、接着剤、高吸水性樹脂、インク、塗料、繊維、または塗料、樹脂、繊維の改質剤などの原材料についてもその使途によっては透明あるいは白色であることを必要とすることもある。 By the way, phenol compounds and amine compounds such as hydroquinone, methoxyphenol, tertiary butylcatechol, and methylhydroquinone are widely used as antioxidants and polymerization inhibitors. However, these additives often develop color when developing their effects, and this color often causes coloring of the added substrate. In addition, due to use under high temperature, deterioration of sunlight by ultraviolet rays, alteration due to exhaust gas, etc., coloring may occur depending on the usage environment as a final product, which may cause problems depending on the application. Specifically, the transparent member for a vehicle and the member for a transparent sheet are not preferably colored when light passes through, and the lens, prism, optical disc, and sheet that are optical device members need hue stability. Similarly, raw materials such as semiconductor materials, electronic materials, pressure-sensitive adhesives, adhesives, highly water-absorbing resins, inks, paints, fibers, or paints, resins, and fiber modifiers are transparent or white depending on the use. Sometimes it is necessary.
従って、重合性単量体、特に重合性単量体の保存安定性を目的として添加される酸化防止剤又は重合抑制剤に起因する最終製品での着色を防止することができる着色防止剤、及びその防止方法が要望されていた。 Accordingly, a coloring monomer, particularly a coloring agent that can prevent coloring in the final product due to an antioxidant or a polymerization inhibitor added for the purpose of storage stability of the polymerizable monomer, and There has been a demand for a prevention method.
酸化防止剤又は重合抑制剤に起因する重合性単量体の着色を防止し、かつ高温環境下、太陽光による劣化に対して耐久性を呈することで使用後であっても良好な透明性を保持することが可能であるため、電子材料、車両用透明部材、透明シート用部材、粘着剤、接着剤、高吸水性樹脂、インク、塗料、繊維、または塗料、樹脂、繊維の改質剤などの原材料などのより適用範囲の広い分野で使用可能な重合性単量体またはその部分重合体、特に、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステルなどの重合性単量体またはその部分重合体に添加して使用される重合抑制剤、特にフェノール系重合抑制剤、アミン系重合抑制剤または酸化防止剤に起因する着色を防止する着色防止剤および着色防止方法を提供することにある。 Good transparency even after use by preventing coloring of the polymerizable monomer due to the antioxidant or polymerization inhibitor and exhibiting durability against degradation under sunlight in a high temperature environment Electronic materials, transparent members for vehicles, transparent sheet members, adhesives, adhesives, super absorbent resins, inks, paints, fibers, or paints, resins, fiber modifiers, etc. A polymerizable monomer or a partial polymer thereof, which can be used in a wider range of applications such as raw materials, particularly a polymerizable monomer such as acrylic acid, acrylic ester, methacrylic acid or methacrylic ester or a portion thereof The present invention provides a coloring inhibitor and a coloring preventing method for preventing coloring caused by a polymerization inhibitor, particularly a phenol polymerization inhibitor, an amine polymerization inhibitor, or an antioxidant, which are used by being added to a polymer. .
本発明者らは、上記の課題を解決するために、種々検討の結果、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステルなどの重合性単量体またはその部分重合体と酸化防止剤又は重合抑制剤とからなる配合物に対して、酸化防止剤又は重合抑制剤１００質量部に対してアリールホスフィン化合物及びシラザン化合物からなる群より選ばれた少なくとも一種の化合物を外配で３〜１００質量部添加して使用することで上記の課題を解決できることを見出して、本発明を完成したものである。 In order to solve the above-mentioned problems, the present inventors have conducted various studies, and as a result, polymerizable monomers such as acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester, or partial polymers thereof and an antioxidant or 3 to 100 mass by weight of at least one compound selected from the group consisting of an arylphosphine compound and a silazane compound with respect to 100 mass parts of the antioxidant or the polymerization inhibitor with respect to the blend composed of the polymerization inhibitor. The present invention has been completed by finding out that the above-mentioned problems can be solved by adding a part.
なお、上記着色防止剤は、フェノール系重合抑制剤、アミン系重合抑制剤とともに併用すること、特に、ハイドロキノン、メトキシフェノール、ターシャリーブチルカテコール、メチルハイドロキノン等の重合抑制剤に起因する着色を防止するものであって、上記アリールホスフィン化合物及びシラザン化合物のうち、特にトリフェニルホスフィン、１，１，３，３−テトラメチルジシラザン、１，１，１，３，３，３−へキサメチルジシラザン等が優れた効果を示すことを見出した。 The anti-coloring agent is used in combination with a phenol-based polymerization inhibitor and an amine-based polymerization inhibitor, and in particular, prevents coloring due to a polymerization inhibitor such as hydroquinone, methoxyphenol, tertiary butylcatechol, and methylhydroquinone. Among the above arylphosphine compounds and silazane compounds, in particular, triphenylphosphine, 1,1,3,3-tetramethyldisilazane, 1,1,1,3,3,3-hexamethyldisilazane Etc. have been found to show excellent effects.
なお、上記アリールホスフィン化合物及びシラザン化合物からなる群より選ばれた少なくとも一種の化合物を着色防止に使用する場合には、重合性単量体またはその部分重合体に添加される酸化防止剤又は重合抑制剤とからなる配合物に対して、酸化防止剤又は重合抑制剤１００質量部に対して外配で３〜１００質量部、好ましくは、外配で１０〜１００質量部添加して使用することにより、着色防止が図れる。なお、対重合性単量体またはその部分重合体との関係では、その添加量は、通常、重合性単量体またはその部分重合体１００質量部に対して、０．００１〜１質量部程度の添加で十分な効果を発揮する。なお、本発明の着色防止剤は、重合抑制効果を阻害しないため、重合抑制剤とともに使用されてもその効果を充分発揮することができる。 In the case of using at least one compound selected from the group consisting of the arylphosphine compound and the silazane compound for preventing coloring, an antioxidant or a polymerization inhibitor added to the polymerizable monomer or a partial polymer thereof. By adding 3 to 100 parts by weight, preferably 10 to 100 parts by weight externally, with respect to 100 parts by weight of an antioxidant or a polymerization inhibitor, and adding 10 to 100 parts by weight. Coloring prevention can be achieved. In addition, in relation to the polymerizable monomer or its partial polymer, the amount added is usually about 0.001 to 1 part by mass with respect to 100 parts by mass of the polymerizable monomer or its partial polymer. Adds sufficient effect. In addition, since the coloring inhibitor of this invention does not inhibit the polymerization inhibitory effect, even if it is used with a polymerization inhibitor, the effect can fully be exhibited.
本発明に係る着色防止剤であるアリールホスフィン化合物及びシラザン化合物からなる群より選ばれた少なくとも一種の化合物を重合性単量体またはその部分重合体に添加することにより、実質的に酸化防止剤又は重合抑制剤に起因する着色を有効に防止することができる。 By adding at least one compound selected from the group consisting of an aryl phosphine compound and a silazane compound which is a coloring inhibitor according to the present invention to a polymerizable monomer or a partial polymer thereof, an antioxidant or Coloring due to the polymerization inhibitor can be effectively prevented.
本発明は、重合性単量体またはその部分重合体と、酸化防止剤、または、重合抑制剤とからなる配合物に添加し使用する、アリールホスフィン化合物およびジシラザン化合物からなる群から選ばれる少なくとも１種の化合物の着色防止剤としての使用に関する。添加量は、酸化防止剤又は重合抑制剤１００質量部に対して外配で３〜１００質量部、好ましくは、外配で１０〜１００質量部である。添加方法は、特に制限はなく、一般的には重合抑制剤と同時に添加すればよい。添加の形態についても特に制限はなく、着色防止剤をそのまま添加すればよい。さらに、酸化防止剤、重合抑制剤、着色防止剤以外に用途によって必要があれば、重合開始剤、可塑剤、改質剤、充填剤、補強剤、帯電防止剤、紫外線吸収剤、難燃剤等その他の安定剤等を添加しても、所望の効果を得ることができる。 The present invention provides at least one selected from the group consisting of an aryl phosphine compound and a disilazane compound, which is used by being added to a composition comprising a polymerizable monomer or a partial polymer thereof and an antioxidant or a polymerization inhibitor. It relates to the use of seed compounds as anti-coloring agents. The addition amount is 3 to 100 parts by mass, preferably 10 to 100 parts by mass, with respect to 100 parts by mass of the antioxidant or polymerization inhibitor. The addition method is not particularly limited, and generally it may be added simultaneously with the polymerization inhibitor. There is no restriction | limiting in particular also about the form of addition, What is necessary is just to add a coloring inhibitor as it is. In addition to antioxidants, polymerization inhibitors, and coloring inhibitors, if necessary depending on the application, polymerization initiators, plasticizers, modifiers, fillers, reinforcing agents, antistatic agents, ultraviolet absorbers, flame retardants, etc. Even if other stabilizers and the like are added, a desired effect can be obtained.
重合性単量体またはその部分重合体、特に、アクリル系重合性単量体またはその部分重合体には、予め酸化防止剤や重合抑制剤が添加されている。このような酸化防止剤や重合抑制剤には、フェノール系化合物、アミン系化合物が含まれる。例えば、フェノール系化合物としては、ハイドロキノン、メトキシフェノール、ターシャリーブチルカテコール、メチルハイドロキノン等が挙げられる。アミン系重合抑制剤としては、フェノチアジン、ジフェニルアミンなどなどが挙げられる。また、酸化防止剤としては、ノンフレックスＭＢＰ、ノンフレックスＥＢＰ、ノンフレックスＣＢＰ、ノンフレックス アルバ、ＢＨＴスワノックス、ＴＢＨ（以上製品名。精工化学（製））が挙げられる。 An antioxidant and a polymerization inhibitor are added in advance to the polymerizable monomer or a partial polymer thereof, in particular, the acrylic polymerizable monomer or the partial polymer thereof. Such antioxidants and polymerization inhibitors include phenolic compounds and amine compounds. For example, examples of the phenol compound include hydroquinone, methoxyphenol, tertiary butyl catechol, and methyl hydroquinone. Examples of amine polymerization inhibitors include phenothiazine and diphenylamine. Examples of the antioxidant include non-flex MBP, non-flex EBP, non-flex CBP, non-flex Aruba, BHT Swanox, TBH (product name: Seiko Chemical Co., Ltd.).
本発明に係るアリールホスフィン化合物としては、トリフェニルホスフィンが、また、本発明に係るシラザン化合物としては、１，１，３，３−テトラメチルジシラザン、または１，１，１，３，３，３−へキサメチルジシラザンなどが挙げられる。 The aryl phosphine compound according to the present invention is triphenylphosphine, and the silazane compound according to the present invention is 1,1,3,3-tetramethyldisilazane, or 1,1,1,3,3, Examples include 3-hexamethyldisilazane.
重合性単量体またはその部分重合体としては、アクリル酸、アクリル酸エステル、メタクリル酸、メタクリル酸エステルからなる群から選ばれる少なくとも一つであって、アクリル酸エステルの具体例にはアクリル酸メチル、アクリル酸エチル、アクリル酸ブチル、アクリル酸２−エチルヘキシル、メタクリル酸エステルの具体例としては、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸シクロヘキル、メタクリル酸２−エチルヘキシル、メタクリル酸ステアリル、メタクリル酸ラウリル等が挙げられる。好ましくはアクリル酸又はアクリル酸エステルであり、特に好ましくはアクリル酸２−エチルヘキシル等である。 The polymerizable monomer or a partial polymer thereof is at least one selected from the group consisting of acrylic acid, acrylic ester, methacrylic acid, and methacrylic ester, and specific examples of the acrylic ester include methyl acrylate. Specific examples of ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid ester include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, And lauryl methacrylate. Acrylic acid or acrylic acid ester is preferable, and 2-ethylhexyl acrylate is particularly preferable.
以下、試験例を用いて、本発明の効果を具体的に説明するが、本発明は以下の試験例に限定されるものではなく、本発明の主旨に逸脱しない限り、適宜変更・修正を加え使用することができることは、言うまでもない。 Hereinafter, the effects of the present invention will be specifically described using test examples. However, the present invention is not limited to the following test examples, and appropriate modifications and corrections may be made without departing from the gist of the present invention. It goes without saying that it can be used.
（着色防止性能試験１）
本発明に係る着色防止剤の性能を試験するために、溶媒としてＮ，Ｎ−ジメチルアセトアミドを用いてＮＯｘによる着色試験に供した。結果を表１に示す。ＮＯｘ処理前とＮＯｘ処理後の色数を求めた。まず、重合抑制剤および着色防止剤を所定量、溶媒である１５ｇのＮ，Ｎ−ジメチルアセトアミドに添加、溶解させた。完全に溶解させたサンプル液をバイアル瓶（３０ｍｌ）に１０ｇはかりとり、密栓した。ＪＩＳ Ｌ０８５５（酸化窒素ガスに対する染色堅ろう度試験方法）に準じ、酸化窒素ガス発生装置でＮＯｘガスを発生させ、発生させたＮＯｘガスをシリンジを使って２．０ｍｌ測り取り、サンプル液を入れたバイアルびんに注入し、よく振ってＮＯｘガスとサンプル液を混ぜ、再び密封した。このものを室温にて１時間放置後、ガードナー比色計で標準液と比較し色数を求めた。なお、この試験例で用いたガードナー比色計による色数は、ＪＩＳ Ｋ−００７１−２に準じた。
(Coloring prevention performance test 1)
In order to test the performance of the anti-coloring agent according to the present invention, it was subjected to a NOx coloring test using N, N-dimethylacetamide as a solvent. The results are shown in Table 1. The number of colors before NOx treatment and after NOx treatment was determined. First, a predetermined amount of a polymerization inhibitor and a coloring inhibitor were added and dissolved in 15 g of N, N-dimethylacetamide as a solvent. 10 g of the completely dissolved sample solution was weighed into a vial (30 ml) and sealed. According to JIS L0855 (Method of dyeing fastness to nitric oxide gas), NOx gas is generated with a nitrogen oxide gas generator, 2.0 ml of the generated NOx gas is measured using a syringe, and a vial containing a sample solution The bottle was poured and shaken well to mix the NOx gas and the sample solution and sealed again. This was allowed to stand at room temperature for 1 hour and then compared with the standard solution using a Gardner colorimeter to determine the number of colors. The number of colors by the Gardner colorimeter used in this test example conformed to JIS K-0071-2.
一般的に用いられる着色防止剤として使用されているフェニルヒドラジン、ベンゾフェニルヒドラゾン、ジアセチルヒドラジン等のヒドラジン化合物を重合抑制剤であるメトキシフェノールと併用して、使用した比較例１〜比較例４では着色防止剤を用いない参考例１と比較し、同程度か、あるいはそれよりも濃い着色が認められた。これに対し、トリフェニルホスフィン、１，１，３，３−テトラメチルジシラザン、及び１，１，１，３，３，３−へキサメチルジシラザンを着色防止剤として、重合抑制剤メトキシフェノールと併用した試験例１〜７においては、着色防止剤を用いない参考例１の色数１０と比較して色数の増加は抑えられている。また、重合抑制剤としてハイドロキノンを本発明に係る着色防止剤と併用した試験例４と参考例２、及びターシャリーブチルカテコールと本発明に係る着色防止剤を併用した試験例５と参考例３を比較すると、トリフェニルホスフィンを添加することによりＮＯｘ処理後の色数の増加は抑えられている。 In Comparative Examples 1 to 4 in which hydrazine compounds such as phenylhydrazine, benzophenylhydrazone, diacetylhydrazine and the like, which are generally used as coloring inhibitors, are used in combination with methoxyphenol as a polymerization inhibitor. Compared with Reference Example 1 in which the inhibitor was not used, the same or darker coloring was observed. In contrast, triphenylphosphine, 1,1,3,3-tetramethyldisilazane, and 1,1,1,3,3,3-hexamethyldisilazane as a coloring inhibitor, a polymerization inhibitor methoxyphenol. In Test Examples 1 to 7 used in combination, an increase in the number of colors is suppressed as compared with the number of colors 10 in Reference Example 1 in which no anti-coloring agent is used. Further, Test Example 4 and Reference Example 2 in which hydroquinone is used in combination with the coloring inhibitor according to the present invention as a polymerization inhibitor, and Test Example 5 and Reference Example 3 in which tertiary butylcatechol and the coloring inhibitor according to the present invention are used in combination. In comparison, the increase in the number of colors after the NOx treatment is suppressed by adding triphenylphosphine.
これにより、トリフェニルホスフィン、１，１，３，３−テトラメチルジシラザン、及び１，１，１，３，３，３−へキサメチルジシラザン、中でも特にトリフェニルホスフィンは、ＭＱ（４−ヒドロキシアニソール）、ＨＱ（ハイドロキノン）、ＴＢＣ（ｔ−ブチルカテコール）等のフェノール系重合抑制剤の着色を本発明に係る着色防止剤は防止する効果があることが確認された。 As a result, triphenylphosphine, 1,1,3,3-tetramethyldisilazane, and 1,1,1,3,3,3-hexamethyldisilazane, especially triphenylphosphine, are particularly suitable for MQ (4- It was confirmed that the anti-coloring agent according to the present invention has an effect of preventing coloring of a phenol-based polymerization inhibitor such as hydroxyanisole), HQ (hydroquinone), and TBC (t-butylcatechol).
（着色防止性能試験２）
上記の結果を受けて、本発明に係る着色防止剤の重合性単量体の共存下における性能を試験するために、上記試験で特に効果が顕著であったメトキシフェノールをＮＯｘによる着色試験に供した。ＮＯｘ処理前とＮＯｘ処理後の色数を求めることで、着色防止効果について知ることができる。まず、市販されている重合性単量体であるアクリル酸２−エチルヘキシルから、重合抑制剤を抽出除去して、改めて、重合抑制剤をアクリル酸２−エチルヘキシルに対して１質量％添加し、このものにこの重合抑制剤１００質量部に対して、１０質量部から１００質量部の範囲で本発明に係る着色防止剤を添加、溶解させた。次に完全に溶解させたサンプル液をバイアル瓶（３０ｍｌ）に１０ｇはかりとり、密栓した。ＪＩＳ Ｌ０８５５（酸化窒素ガスに対する染色堅ろう度試験方法）に準じて、酸化窒素ガス発生装置でＮＯｘガスを発生させ、発生させたＮＯｘガスをシリンジを使って０．１ｍｌ測り取り、サンプル液を入れたバイアル瓶に注入し、よく振ってＮＯｘガスとサンプル液を混ぜ、再び密封した。このものを室温にて１時間放置後、ガードナー比色計で標準液と比較し、色数を求めた。その結果を以下の表２に示す。なお、この試験例で用いたガードナー比色計による色数は、ＪＩＳ Ｋ−００７１−２に準じた。
(Coloring prevention performance test 2)
Based on the above results, in order to test the performance of the coloring inhibitor according to the present invention in the presence of the polymerizable monomer, methoxyphenol, which was particularly effective in the above test, was subjected to a NOx coloring test. did. By obtaining the number of colors before and after the NOx treatment, it is possible to know the coloring prevention effect. First, a polymerization inhibitor is extracted and removed from 2-ethylhexyl acrylate, which is a commercially available polymerizable monomer, and 1% by mass of the polymerization inhibitor is added to 2-ethylhexyl acrylate again. The coloring inhibitor according to the present invention was added to and dissolved in the range of 10 to 100 parts by mass with respect to 100 parts by mass of the polymerization inhibitor. Next, 10 g of the completely dissolved sample solution was weighed into a vial (30 ml) and sealed. According to JIS L0855 (Testing method for dyeing fastness to nitric oxide gas), NOx gas was generated with a nitric oxide gas generator, 0.1 ml of the generated NOx gas was measured using a syringe, and a sample solution was added. It was poured into a vial, shaken well, mixed with NOx gas and sample solution, and sealed again. This was allowed to stand at room temperature for 1 hour and then compared with a standard solution using a Gardner colorimeter to determine the number of colors. The results are shown in Table 2 below. The number of colors by the Gardner colorimeter used in this test example conformed to JIS K-0071-2.
着色防止剤を外配で１０〜１００質量部の割合で添加したものが着色防止効果を示した。ただし、トリフェニルホスフィンの場合、この試験では１０質量部添加した試験例４でも色数４で淡黄色であり、着色防止効果としては必ずしも充分ではなかった。しかし、１００質量部添加した試験例４においては色数２となり、実用的には充分な着色防止効果が得られた。また、（着色防止性能試験１）において溶媒を用いた試験でも色数４との良好な結果が得られていたテトラメチルジシラザンを着色防止剤として１０質量部用いた試験例６で色数は２であり、１００質量部用いた試験例３で色数は１と、最も良好な効果が得られた。全ての試験例１〜６において、肉眼ではほとんど着色は認められなかった。ほとんどの例についてＮＯｘ処理後には色数は２〜３の値が得られたが、３以下であれば、実用上問題のない範囲である。全く着色防止剤を用いない試験例７の場合は、色数４で淡黄色に着色していた。 What added the anticoloring agent in the ratio of 10-100 mass parts by external distribution showed the anticoloring effect. However, in the case of triphenylphosphine, even in Test Example 4 in which 10 parts by mass were added in this test, the color number was 4 and the color was pale yellow, which was not always sufficient as an anti-coloring effect. However, in Test Example 4 in which 100 parts by mass were added, the number of colors was 2, and a practically sufficient coloring prevention effect was obtained. In addition, the number of colors in Test Example 6 in which 10 parts by mass of tetramethyldisilazane was used as an anti-coloring agent, in which a good result with a color number of 4 was obtained even in a test using a solvent in (Anti-coloring performance test 1), The number of colors was 1 in Test Example 3 using 100 parts by mass, and the best effect was obtained. In all of Test Examples 1 to 6, almost no coloring was observed with the naked eye. For most examples, a value of 2-3 was obtained after the NOx treatment, but if it is 3 or less, there is no practical problem. In the case of Test Example 7 in which no anti-coloring agent was used, it was colored pale yellow with 4 colors.
また、いずれの着色防止剤も１０質量部よりは１００質量部において着色防止効果が高かった。さらに、着色防止性能試験１の試験例４及び５において良好な着色防止効果を示したハイドロキノン、ターシャリーブチルカテコールを重合性単量体を用いたＮＯｘによる着色試験に供したところ、着色防止剤として同様の効果が認められた。 In addition, any anti-coloring agent had a higher anti-coloring effect at 100 parts by mass than at 10 parts by mass. Furthermore, when the hydroquinone and tertiary butyl catechol which showed a good anti-coloring effect in Test Examples 4 and 5 of the anti-coloring performance test 1 were subjected to a coloring test with NOx using a polymerizable monomer, as a coloring preventing agent Similar effects were observed.
（重合抑制剤への影響に関する試験）
市販のアクリル酸エステルに含まれるＭＱを１０％ＮａＯＨ水溶液３０ｍｌで３回洗浄して抽出し、イオン交換水で３回洗浄してｐＨが中性になるのを確認する。無水硫酸マグネシウムを加え良く混ぜ濾過し、ＭＱを含まないアクリル酸エステル調整液とする。重合抑制剤を１０ｍｇ、着色防止剤を５ｍｇ量り、１０ｍｌメスフラスコに入れ調整液でメスアップする。この溶液０．１ｍｌをマイクロピペットで量り１０ｍｌメスフラスコに入れ調整液でメスアップし、アクリル酸エステルの重合抑制剤１０ｐｐｍ、着色防止剤５ｐｐｍ試験溶液とする。なお、比較のために、メトキシフェノールを１０ｐｐｍ含むが、本発明に係る着色防止剤を含まないアクリル酸エステルの試料（試料番号４）と重合抑制剤も本発明に係る着色防止剤も含まない試料（試料番号５）も用意して、試験に供した。
(Test on effects on polymerization inhibitors)
MQ contained in a commercially available acrylate ester is extracted by washing with 30 ml of 10% NaOH aqueous solution three times, and washed with ion exchange water three times to confirm that the pH becomes neutral. Add anhydrous magnesium sulfate, mix well, and filter to prepare an acrylate preparation solution containing no MQ. 10 mg of the polymerization inhibitor and 5 mg of the coloring inhibitor are weighed and placed in a 10 ml volumetric flask and made up with the adjusting solution. 0.1 ml of this solution is weighed with a micropipette, placed in a 10 ml volumetric flask and made up with a conditioning solution, and used as a test solution for 10 ppm of an acrylic ester polymerization inhibitor and 5 ppm of a coloring inhibitor. For comparison, a sample of acrylate ester (Sample No. 4) containing 10 ppm of methoxyphenol but not containing the anti-coloring agent according to the present invention and a sample containing neither the polymerization inhibitor nor the anti-coloring agent according to the present invention. (Sample No. 5) was also prepared and used for the test.
本発明に係る着色防止剤による重合抑制剤の重合防止効果への影響を試験した。評価には明に係る着色防止剤を添加していないものとの誘導時間と比較して判断した。 The influence on the polymerization prevention effect of the polymerization inhibitor by the coloring inhibitor according to the present invention was tested. The evaluation was made by comparison with the induction time with no addition of the light coloring inhibitor according to the light.
（ＴＧ−ＤＴＡ装置による測定）
装置内の所定の場所に被験材料を保持し、装置を操作標準に従い稼動させ、雰囲気温度の上昇（下降）によるサンプルの重量変化を、時間（温度）に対して記録したものをＴＧ曲線とする。サンプルホルダーに設けられた熱電対の起電力により、リファレンスとサンプルとの温度差を検出し、ＤＴＡ曲線とする。ＴＧ／ＤＴＡでは、加熱時におけるサンプルの重量変化と吸熱・発熱反応を同時に観測できるため、幅広く物質の評価が可能となる。この試験においては、アクリル酸エステルの重合が開始した時点で、発熱反応がおきるため、発熱のピークが立ち現れる。即ち、重合開始時点を、ＤＴＡのピークの立ち上がりの時と見なすことができる。
(Measurement with TG-DTA device)
The test material is held at a predetermined location in the apparatus, the apparatus is operated according to the operation standard, and the change in the weight of the sample due to the increase (decrease) in the ambient temperature is recorded with respect to time (temperature) as the TG curve. . A temperature difference between the reference and the sample is detected by an electromotive force of a thermocouple provided in the sample holder to obtain a DTA curve. With TG / DTA, changes in the weight of the sample and endothermic / exothermic reactions during heating can be observed at the same time. In this test, an exothermic peak appears because an exothermic reaction occurs when polymerization of the acrylate ester starts. That is, the polymerization start time can be regarded as the rise of the DTA peak.
（評価方法）
ＴＧ−ＤＴＡ装置測定器（リガク社 ＴＧ ８１２０）を用いた。上記のように調製した各試験溶液をＴＧ−ＤＴＡ装置測定用試料容器に入れ、試験開始時点では、試験温度１３５℃の場合には試料温度１２０℃、試験温度１６０℃の場合は試料温度１４５℃とし、空気雰囲気で１０℃/分の速度で昇温させた。そして、ＤＴＡの発熱ピークの立ち上がりまでを誘導時間とする。誘導時間が長いほど、重合抑制剤への影響が少ないことを示す。
(Evaluation methods)
A TG-DTA device measuring instrument (Rigaku TG 8120) was used. Each test solution prepared as described above is put into a TG-DTA apparatus measurement sample container. At the start of the test, the sample temperature is 120 ° C. when the test temperature is 135 ° C., and the sample temperature is 145 ° C. when the test temperature is 160 ° C. The temperature was raised at a rate of 10 ° C./min in an air atmosphere. The time until the rise of the exothermic peak of DTA is taken as the induction time. It shows that there is little influence on a polymerization inhibitor, so that induction time is long.
（測定結果）
測定結果を以下の表３に示す。この結果から、本発明に係る着色防止剤を添加した試料番号１ないし３の試料は、メトキシフェノールを１０ｐｐｍ含むが、本発明に係る着色防止剤を含まない比較試料、試料番号４と比較しても、誘導時間に遜色はなく、実質的に重合抑制剤の性能に悪影響を与えるものではないことが判る。即ち、本発明に係る着色防止剤は重合抑制剤と併用可能であることが証明された。なお、重合抑制剤も本発明に係る着色防止剤も含まない比較試料、試料番号５では、誘導時間が試料番号４の誘導時間と比較すると、その２倍強の速さであった。
(Measurement result)
The measurement results are shown in Table 3 below. From these results, the samples of Sample Nos. 1 to 3 to which the coloring inhibitor according to the present invention was added contained 10 ppm of methoxyphenol, but compared with the comparative sample that does not contain the coloring inhibitor according to the present invention, Sample No. 4. However, it can be seen that the induction time is not inferior and does not substantially adversely affect the performance of the polymerization inhibitor. That is, it was proved that the coloring inhibitor according to the present invention can be used in combination with a polymerization inhibitor. In addition, in the comparative sample, sample No. 5, which does not contain the polymerization inhibitor and the coloring inhibitor according to the present invention, the induction time was slightly more than twice that of the induction time of Sample No. 4.
重合抑制剤または酸化防止剤に起因する重合性単量体の着色を防止することで、良好な透明性および耐久性を有する、電子材料、車両用透明部材、透明シート用部材、粘着剤、接着剤、高吸水性樹脂、インク、塗料、繊維、または塗料、樹脂、繊維の改質剤などの原材料などに適する、より適用範囲の広い製品を提供することができる。 Electronic material, vehicle transparent member, transparent sheet member, pressure-sensitive adhesive, adhesive having good transparency and durability by preventing coloring of the polymerizable monomer due to the polymerization inhibitor or antioxidant It is possible to provide a product with a broader application range suitable for an agent, a superabsorbent resin, ink, paint, fiber, or a raw material such as a paint, resin, or fiber modifier.
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| CN111278880A (en) * | 2017-12-14 | 2020-06-12 | 三菱化学株式会社 | Active energy ray-curable resin composition and coating agent |
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| GB2579405B (en) | 2018-11-30 | 2022-09-14 | Si Group Switzerland Chaa Gmbh | Antioxidant compositions |
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