JPH04258682A - Thermal and oxidative deterioration inhibitor - Google Patents
Thermal and oxidative deterioration inhibitorInfo
- Publication number
- JPH04258682A JPH04258682A JP1862491A JP1862491A JPH04258682A JP H04258682 A JPH04258682 A JP H04258682A JP 1862491 A JP1862491 A JP 1862491A JP 1862491 A JP1862491 A JP 1862491A JP H04258682 A JPH04258682 A JP H04258682A
- Authority
- JP
- Japan
- Prior art keywords
- oxidative deterioration
- diol
- deterioration inhibitor
- bis
- thermal oxidative
- 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.)
- Pending
Links
- 239000003112 inhibitor Substances 0.000 title claims abstract description 40
- 230000006866 deterioration Effects 0.000 title claims abstract description 39
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 38
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- SDDLEVPIDBLVHC-UHFFFAOYSA-N Bisphenol Z Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)CCCCC1 SDDLEVPIDBLVHC-UHFFFAOYSA-N 0.000 claims description 6
- CPXHDGJIYPGMMZ-UHFFFAOYSA-N 1,1,4,4-tetraphenylbut-2-yne-1,4-diol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C#CC(O)(C=1C=CC=CC=1)C1=CC=CC=C1 CPXHDGJIYPGMMZ-UHFFFAOYSA-N 0.000 claims description 5
- WXTPRAZNOXQAFY-UHFFFAOYSA-N 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(O)C#CC#CC(O)(C=1C=CC=CC=1)C1=CC=CC=C1 WXTPRAZNOXQAFY-UHFFFAOYSA-N 0.000 claims description 5
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 5
- PFANXOISJYKQRP-UHFFFAOYSA-N 2-tert-butyl-4-[1-(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(CCC)C1=CC(C(C)(C)C)=C(O)C=C1C PFANXOISJYKQRP-UHFFFAOYSA-N 0.000 claims description 5
- PPTXVXKCQZKFBN-UHFFFAOYSA-N (S)-(-)-1,1'-Bi-2-naphthol Chemical compound C1=CC=C2C(C3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 PPTXVXKCQZKFBN-UHFFFAOYSA-N 0.000 claims description 4
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 claims description 4
- YDMVFEUUJCFXNW-UHFFFAOYSA-N 1,1,6,6-tetrakis(2,4-dimethylphenyl)hexa-2,4-diyne-1,6-diol Chemical compound CC1=CC(C)=CC=C1C(O)(C=1C(=CC(C)=CC=1)C)C#CC#CC(O)(C=1C(=CC(C)=CC=1)C)C1=CC=C(C)C=C1C YDMVFEUUJCFXNW-UHFFFAOYSA-N 0.000 claims description 4
- GLQWGVMBEKNKTP-UHFFFAOYSA-N 1,1-bis(2,4-dimethylphenyl)prop-2-yn-1-ol Chemical compound CC1=CC(C)=CC=C1C(O)(C#C)C1=CC=C(C)C=C1C GLQWGVMBEKNKTP-UHFFFAOYSA-N 0.000 claims description 4
- CJETXAUUVYDHTN-UHFFFAOYSA-N 1,6-bis(2-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol Chemical compound C=1C=CC=CC=1C(C=1C(=CC=CC=1)Cl)(O)C#CC#CC(O)(C=1C(=CC=CC=1)Cl)C1=CC=CC=C1 CJETXAUUVYDHTN-UHFFFAOYSA-N 0.000 claims description 4
- FTGCTVWKHSDTEQ-UHFFFAOYSA-N 2,5-bis(2,4-dimethylphenyl)benzene-1,4-diol Chemical compound CC1=CC(C)=CC=C1C1=CC(O)=C(C=2C(=CC(C)=CC=2)C)C=C1O FTGCTVWKHSDTEQ-UHFFFAOYSA-N 0.000 claims description 4
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims description 4
- OSEHBGZOVPNBNK-UHFFFAOYSA-N 9,10-bis(4-methylphenyl)anthracene-9,10-diol Chemical compound C1=CC(C)=CC=C1C1(O)C2=CC=CC=C2C(O)(C=2C=CC(C)=CC=2)C2=CC=CC=C21 OSEHBGZOVPNBNK-UHFFFAOYSA-N 0.000 claims description 4
- RYFIDGIWTNANMO-UHFFFAOYSA-N 9,10-diphenylanthracene-9,10-diol Chemical compound C12=CC=CC=C2C(O)(C=2C=CC=CC=2)C2=CC=CC=C2C1(O)C1=CC=CC=C1 RYFIDGIWTNANMO-UHFFFAOYSA-N 0.000 claims description 4
- MDNWOSOZYLHTCG-UHFFFAOYSA-N Dichlorophen Chemical compound OC1=CC=C(Cl)C=C1CC1=CC(Cl)=CC=C1O MDNWOSOZYLHTCG-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- BHQCQFFYRZLCQQ-OELDTZBJSA-N cholic acid Chemical compound C([C@H]1C[C@H]2O)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 BHQCQFFYRZLCQQ-OELDTZBJSA-N 0.000 claims description 4
- KXGVEGMKQFWNSR-LLQZFEROSA-N deoxycholic acid Chemical compound C([C@H]1CC2)[C@H](O)CC[C@]1(C)[C@@H]1[C@@H]2[C@@H]2CC[C@H]([C@@H](CCC(O)=O)C)[C@@]2(C)[C@@H](O)C1 KXGVEGMKQFWNSR-LLQZFEROSA-N 0.000 claims description 4
- KXGVEGMKQFWNSR-UHFFFAOYSA-N deoxycholic acid Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 KXGVEGMKQFWNSR-UHFFFAOYSA-N 0.000 claims description 4
- KDENVQZUIOWUSY-UHFFFAOYSA-N n,n-dicyclohexyl-2-[2-(dicyclohexylcarbamoyl)phenyl]benzamide Chemical compound C=1C=CC=C(C=2C(=CC=CC=2)C(=O)N(C2CCCCC2)C2CCCCC2)C=1C(=O)N(C1CCCCC1)C1CCCCC1 KDENVQZUIOWUSY-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- BHQCQFFYRZLCQQ-UHFFFAOYSA-N (3alpha,5alpha,7alpha,12alpha)-3,7,12-trihydroxy-cholan-24-oic acid Natural products OC1CC2CC(O)CCC2(C)C2C1C1CCC(C(CCC(O)=O)C)C1(C)C(O)C2 BHQCQFFYRZLCQQ-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004380 Cholic acid Substances 0.000 claims description 2
- 229920002261 Corn starch Polymers 0.000 claims description 2
- 229960002471 cholic acid Drugs 0.000 claims description 2
- 235000019416 cholic acid Nutrition 0.000 claims description 2
- 239000008120 corn starch Substances 0.000 claims description 2
- 229940099112 cornstarch Drugs 0.000 claims description 2
- 229960003964 deoxycholic acid Drugs 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 230000003064 anti-oxidating effect Effects 0.000 abstract 1
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 10
- 239000000057 synthetic resin Substances 0.000 description 7
- 229920003002 synthetic resin Polymers 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004826 Synthetic adhesive Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XOUQAVYLRNOXDO-UHFFFAOYSA-N 2-tert-butyl-5-methylphenol Chemical compound CC1=CC=C(C(C)(C)C)C(O)=C1 XOUQAVYLRNOXDO-UHFFFAOYSA-N 0.000 description 2
- VKJLYEDTHCTCOH-UHFFFAOYSA-N 3-(3-octadecoxy-3-oxopropyl)sulfanylpropanoic acid Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(O)=O VKJLYEDTHCTCOH-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- UEOYYXOZJDMHDD-UHFFFAOYSA-N 2-(dodecylsulfanylmethyl)prop-2-enoic acid methane Chemical compound C.C=C(C(=O)O)CSCCCCCCCCCCCC.C=C(C(=O)O)CSCCCCCCCCCCCC.C=C(C(=O)O)CSCCCCCCCCCCCC.C=C(C(=O)O)CSCCCCCCCCCCCC UEOYYXOZJDMHDD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229940123973 Oxygen scavenger Drugs 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 230000003405 preventing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Anti-Oxidant Or Stabilizer Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】[Detailed description of the invention]
【０００１】0001
【産業上の利用分野】本発明は熱酸化劣化防止剤に係り
、特に、熱酸化劣化防止効果を長期間に亘って持続し得
る粉末状熱酸化劣化防止剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermal oxidative deterioration inhibitor, and more particularly to a powdered thermal oxidative deterioration inhibitor that can maintain its thermal oxidative deterioration inhibiting effect over a long period of time.
【０００２】0002
【従来の技術】現在、各種分野で広く使用されている合
成樹脂や、接着剤、特にホットメルト型接着剤等には、
その製造、加工ないし使用時に加えられる熱や酸素によ
る劣化を防止する目的で、微粉末状の酸化防止剤が配合
添加されている。[Prior Art] Currently, synthetic resins and adhesives, especially hot melt adhesives, etc., are widely used in various fields.
Finely powdered antioxidants are added to prevent deterioration due to heat and oxygen applied during manufacture, processing, and use.
【０００３】0003
【発明が解決しようとする課題】しかしながら、従来の
酸化防止剤では、■ １種類の酸化防止剤を添加した
だけでは、その効果が長期間持続しない場合が多い。■
数種類の酸化防止剤を組み合わせることにより、効
果を持続させることができる場合もあるが、その場合、
用いる酸化防止剤の適当な組み合わせを見出すことは非
常に困難である。といった問題点がある。しかして、従
来においては、効果の持続性を高めるために、大量の酸
化防止剤を添加しているが、大量の酸化防止剤を添加す
ることは、コスト的に不利である上に、添加対象に悪影
響を及ぼす場合があるなどの欠点がある。[Problems to be Solved by the Invention] However, with conventional antioxidants, (1) Adding just one type of antioxidant often does not maintain its effect for a long period of time. ■
In some cases, the effect can be sustained by combining several types of antioxidants, but in that case,
Finding the right combination of antioxidants to use is very difficult. There are some problems. Conventionally, large amounts of antioxidants have been added to increase the sustainability of the effect, but adding large amounts of antioxidants is not only disadvantageous in terms of cost, but also There are drawbacks such as the fact that it may have a negative effect on
【０００４】なお、従来、合成樹脂と接触する水中の酸
素除去を目的として、水系用の脱酸素剤を多分子系ホス
ト化合物で包接化合物としたものを、合成樹脂に粘り込
んだ合成樹脂材料が提案されている（特開平１−２９２
０９３号）が、このものは、上記の如く、水系の酸化防
止処理を目的とするものであって、合成樹脂や接着剤な
どの製造、加工ないし使用時の熱による酸化劣化を防止
するものではない。[0004] Conventionally, in order to remove oxygen from water that comes into contact with synthetic resin, synthetic resin materials have been prepared in which a water-based oxygen scavenger is made into a clathrate compound with a polymolecular host compound and is infused into synthetic resin. has been proposed (Japanese Patent Application Laid-Open No. 1-292
No. 093), but as mentioned above, this product is intended for water-based oxidation prevention treatment, and is not intended to prevent oxidative deterioration due to heat during the manufacture, processing, or use of synthetic resins, adhesives, etc. do not have.
【０００５】本発明は上記従来の実情に鑑み、合成樹脂
や接着剤の製造、加工ないし使用時の熱酸化劣化を、長
期間安定かつ効果的に防止することができる熱酸化劣化
防止剤を提供することを目的とする。In view of the above-mentioned conventional circumstances, the present invention provides a thermal oxidative deterioration inhibitor that can stably and effectively prevent thermal oxidative deterioration during the production, processing, or use of synthetic resins and adhesives for a long period of time. The purpose is to
【０００６】[0006]
【課題を解決するための手段】本発明の熱酸化劣化防止
剤は、熱酸化劣化防止剤と、次の（１）〜（２４）から
選ばれる１種又は２種以上の多分子系ホスト化合物とが
反応して得られた包接化合物を含むことを特徴とする。[Means for Solving the Problems] The thermal oxidative deterioration inhibitor of the present invention comprises a thermal oxidative deterioration inhibitor and one or more polymolecular host compounds selected from the following (1) to (24). It is characterized by containing an clathrate compound obtained by reacting with.
【０００７】（１） １，１，６，６−テトラフェニ
ル−２，４−ヘキサジイン−１，６−ジオール（２）
１，６−ビス（２−クロロフェニル）−１，６−ジフ
ェニルヘキサ−２，４−ジイン−１，６−ジオール
（３） １，１−ビス（２，４−ジメチルフェニル）
−２−プロピン−１−オール
（４） ２，５−ビス（２，４−ジメチルフェニル）
ハイドロキノン
（５） １，１，４，４−テトラフェニル−２−ブチ
ン−１，４−ジオール
（６） １，１，２，２−テトラフェニルエタン−１
，２−ジオール
（７） １，１−ビ−２−ナフトール（８） ９，
１０−ジフェニル−９，１０−ジヒドロアントラセン−
９，１０−
ジオール
（９） １，１，６，６−テトラキス（２，４−ジメ
チルフェニル）−２，４−ヘキサジイン−１，６−ジオ
ール
（１０） ９，１０−ビス（４−メチルフェニル）−
９，１０−ジヒドロアントラセン−９，１０−ジオール
（１１） １，１−ビス（４−ヒドロキシフェニル）
シクロヘキサン
（１２） Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（シクロ
ヘキシル）−（１，１’−ビフェニル）−２，２’−ジ
カルボキシアミド
（１３） １，４−ジアザビシクロ−（２，２，２）
−オクタン
（１４） ４，４’−スルホニルビスフェノール（１
５） ４，４’−ブチリデンビス（３−メチル−６−
ｔｅｒｔ−ブチルフェノール）
（１６） ２，２’−メチレンビス（４−メチル−６
−ｔｅｒｔ−ブチルフェノール）
（１７） ４，４’−チオビス（３−メチル−６−ｔ
ｅｒｔ−ブチルフェノール）
（１８） ２，２’−メチレンビス（４−クロロフェ
ノール）
（１９） デオキシコール酸
（２０） ｔ−ブチルヒドロキノン
（２１） ２，５−ジ−ｔｅｒｔ−ブチルヒドロキノ
ン（２２） コール酸
（２３） 顆粒状コーンスターチ（ポーラスＹ−２０
）（２４） α，α，α’，α’−テトラフェニル−
１’，１’−ビフェニル−２，２’−ジメタノール以下
に本発明を詳細に説明する。本発明の熱酸化劣化防止剤
において、熱酸化劣化防止剤としては特に制限はないが
、例えば、下記に示すチオエーテル系又はホスファイト
系酸化防止剤が挙げられる。
（Ａ） チオエーテル系
（Ａ）−■ テトラキス［メチレン−３−（ラウリル
チオ）プロピオネート］メタン
Ｃ（ＣＨ２ ＯＣＯＣＨ２ ＣＨ２ ＣＨ２ ＳＣ１２
Ｈ２５）４（Ａ）−■ チオジプロピオン酸ステアリ
ルＳ（ＣＨ２ ＣＨ２ ＣＯＯＣ１８Ｈ３７）２（Ｂ）
ホフファイト系
（Ｂ）−■ トリス（ノニルフェニル）ホスファイト
Ｐ（Ｏ−Ｐｈ−Ｃ９ Ｈ１９）３
（Ｂ）−■ トリス（２，４−ジ−ｔｅｒｔ−ブチル
フェニル）ホスファイト
Ｐ［Ｏ−Ｐｈ−（ｏ） Ｃ（ＣＨ３ ）３ ，（ｐ）Ｃ
（ＣＨ３ ）３ ］３
なお、（Ｂ）−■，（Ｂ）−■において、Ｐｈはベンゼ
ン環を示す。(1) 1,1,6,6-tetraphenyl-2,4-hexadiyn-1,6-diol (2)
1,6-bis(2-chlorophenyl)-1,6-diphenylhexa-2,4-diyne-1,6-diol (3) 1,1-bis(2,4-dimethylphenyl)
-2-propyn-1-ol (4) 2,5-bis(2,4-dimethylphenyl)
Hydroquinone (5) 1,1,4,4-tetraphenyl-2-butyne-1,4-diol (6) 1,1,2,2-tetraphenylethane-1
,2-diol (7) 1,1-bi-2-naphthol (8) 9,
10-diphenyl-9,10-dihydroanthracene-
9,10-diol (9) 1,1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyne-1,6-diol (10) 9,10-bis(4-methylphenyl )−
9,10-dihydroanthracene-9,10-diol (11) 1,1-bis(4-hydroxyphenyl)
Cyclohexane (12) N,N,N',N'-tetrakis(cyclohexyl)-(1,1'-biphenyl)-2,2'-dicarboxamide (13) 1,4-diazabicyclo-(2,2, 2)
-Octane (14) 4,4'-sulfonylbisphenol (1
5) 4,4'-butylidene bis(3-methyl-6-
tert-butylphenol) (16) 2,2'-methylenebis(4-methyl-6
-tert-butylphenol) (17) 4,4'-thiobis(3-methyl-6-t
ert-butylphenol) (18) 2,2'-methylenebis(4-chlorophenol) (19) Deoxycholic acid (20) t-butylhydroquinone (21) 2,5-di-tert-butylhydroquinone (22) Cholic acid (23) Granular cornstarch (Porous Y-20
) (24) α, α, α', α'-Tetraphenyl-
1',1'-Biphenyl-2,2'-dimethanol The present invention will be explained in detail below. In the thermal oxidative deterioration inhibitor of the present invention, the thermal oxidative deterioration inhibitor is not particularly limited, but examples include the following thioether-based or phosphite-based antioxidants. (A) Thioether system (A) -■ Tetrakis[methylene-3-(laurylthio)propionate]methane C (CH2 OCOCH2 CH2 CH2 SC12
H25) 4(A)-■ Stearyl thiodipropionate S(CH2 CH2 COOC18H37) 2(B)
Hoffite system (B)-■ Tris(nonylphenyl)phosphite P(O-Ph-C9 H19)3 (B)-■ Tris(2,4-di-tert-butylphenyl)phosphite P[O-Ph -(o)C(CH3)3,(p)C
(CH3)3]3 In (B)-■ and (B)-■, Ph represents a benzene ring.
【０００８】一方、これらの熱酸化劣化防止剤と反応し
て包接化合物を形成し得る化合物、即ち、当該熱酸化劣
化防止剤をゲスト化合物として包接化合物を形成し得る
、ホスト化合物としては、前記（１）〜（２４）から選
ばれる１種又は２種以上の多分子系ホスト化合物を用い
ることができる。本発明においては、前記（１）〜（２
４）の多分子系ホスト化合物のうち、特に、１，１−ビ
ス（４−ヒドロキシフェニル）シクロヘキサン、４，４
’−ブチリデンビス（３−メチル−６−ｔｅｒｔ−ブチ
ルフェノール）又は２，２’−メチレンビス（４−メチ
ル−６−ｔｅｒｔ−ブチルフェノール）等のフェノール
系ホスト化合物を用いるのが好ましい。On the other hand, compounds that can react with these thermal oxidative deterioration inhibitors to form clathrate compounds, that is, host compounds that can form clathrate compounds using the thermal oxidative deterioration inhibitors as guest compounds, include: One or more types of multimolecular host compounds selected from the above (1) to (24) can be used. In the present invention, the above (1) to (2)
4) Among the polymolecular host compounds, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4
Preferably, a phenolic host compound such as '-butylidenebis(3-methyl-6-tert-butylphenol) or 2,2'-methylenebis(4-methyl-6-tert-butylphenol) is used.
【０００９】本発明の熱酸化劣化防止剤は、常法に従っ
て、合成樹脂又は接着剤に添加配合して使用されるが、
その使用量については特に制限はなく、所望の効果が得
られる範囲で適宜決定される。The thermal oxidative deterioration inhibitor of the present invention is used by being added to a synthetic resin or adhesive according to a conventional method.
There is no particular restriction on the amount used, and it is appropriately determined within a range that provides the desired effect.
【００１０】0010
【作用】本発明の熱酸化劣化防止剤では、有効成分であ
る熱酸化劣化防止剤が、耐熱性に優れた包接化合物とし
て作用するため、使用時の加熱処理等によってもそれ自
体が分解劣化することなく、長期間良好な効果を発揮す
る。[Function] In the thermal oxidative deterioration inhibitor of the present invention, the active ingredient, the thermal oxidative deterioration inhibitor, acts as a clathrate compound with excellent heat resistance, so it will not decompose or deteriorate itself even if it is subjected to heat treatment during use. Demonstrates good effects over a long period of time.
【００１１】特に、フェノール系ホスト化合物を用いた
熱酸化劣化防止剤では、フェノール系ホスト化合物が、
まず一次酸化防止剤として作用し、次に、この包接化合
物ないし分子間会合物中に含まれる熱酸化劣化防止剤が
二次酸化防止剤として作用する。このように二段階の作
用により、効率的かつ効果的な酸化防止効果が奏される
。なお、この場合、一次酸化防止剤と二次酸化防止剤と
の分子間距離は通常の混合物よりも極めて近接している
。このため、酸化防止作用は迅速に、連続的、かつ効果
的になされる。In particular, in the thermal oxidative deterioration inhibitor using a phenolic host compound, the phenolic host compound is
First, it acts as a primary antioxidant, and then the thermal oxidative deterioration inhibitor contained in this clathrate compound or intermolecular association acts as a secondary antioxidant. In this way, the two-stage action provides an efficient and effective antioxidant effect. In this case, the intermolecular distance between the primary antioxidant and the secondary antioxidant is much closer than in a normal mixture. Therefore, the antioxidant effect is achieved quickly, continuously, and effectively.
【００１２】0012
【実施例】以下に実施例を挙げて本発明をより具体的に
説明するが、本発明はその要旨を超えない限り、以下の
実施例に限定されるものではない。[Examples] The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist thereof.
【００１３】実施例１
熱酸化劣化防止剤として下記［Ｉ］、下記■又は■をホ
スト化合物として、それぞれメタノール溶液中に加え、
常温下撹拌しながらモル比１：１の包接化合物とし、該
包接化合物を接着剤添加剤用流動パラフィンオイル（以
下単に「オイル」と略称する。）中に、熱酸化劣化防止
剤の割合が１重量％となるように添加し、１８０℃で４
８時間保持した後のオイルの色を観察し、下記評価基準
で判定した。
熱酸化劣化防止剤［Ｉ］：テトラキス［メチレン−３−
（ラウリルチオ）プロピオネート］メタンホスト化合物
■：１，１−ビス（４−ヒドロキシフェニル）シクロヘ
キサン
ホスト化合物■：４，４’−ブチリデンビス（３−メチ
ル−６−ｔｅｒｔ−ブチルフェノール）評価基準：
Ａ＝無色透明（非常に良い。）
Ｂ＝やや褐色（良い。）
Ｃ＝褐色（悪い。）
Ｄ＝黒色（非常に悪い。）
同様に、熱酸化劣化防止剤［Ｉ］単独、ホスト化合物■
単独、又は、ホスト化合物■単独についても実験、判定
を行なった。結果を表１に示す。Example 1 As a thermal oxidative deterioration inhibitor, the following [I], the following ■ or ■ were added as host compounds to a methanol solution, respectively.
While stirring at room temperature, the clathrate compound is prepared at a molar ratio of 1:1, and the clathrate compound is added to liquid paraffin oil for adhesive additive (hereinafter simply referred to as "oil") in a proportion of a thermal oxidative deterioration inhibitor. was added to give a concentration of 1% by weight, and heated at 180°C for 4
The color of the oil after being held for 8 hours was observed and judged based on the following evaluation criteria. Thermal oxidative degradation inhibitor [I]: Tetrakis [methylene-3-
(laurylthio)propionate] methane host compound ■: 1,1-bis(4-hydroxyphenyl)cyclohexane host compound ■: 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) Evaluation criteria: A = colorless and transparent (Very good.) B = Slightly brown (good) C = brown (bad) D = black (very bad) Similarly, thermal oxidative deterioration inhibitor [I] alone, host compound■
Experiments and judgments were also conducted for the host compound (1) alone or for the host compound (2) alone. The results are shown in Table 1.
【００１４】[0014]
【表１】[Table 1]
【００１５】表１より、本発明の熱酸化劣化防止剤は良
好な酸化防止効果を示すことが明らかである。From Table 1, it is clear that the thermal oxidative deterioration inhibitor of the present invention exhibits a good antioxidant effect.
【００１６】実施例２
熱酸化劣化防止剤として下記［ＩＩ］を用い、前記実施
例１の■をホスト化合物として、実施例１と同様にモル
比１：１の包接化合物とし、実施例１と同様にして実験
、判定を行なった。
熱酸化劣化防止剤［ＩＩ］：チオジプロピオン酸ステア
リル
同様に、熱酸化劣化防止剤［ＩＩ］単独についても実験
、判定を行なった。結果を表２に示す。Example 2 Using the following [II] as a thermal oxidative deterioration inhibitor, using the above-mentioned Example 1 (■) as a host compound, and using a clathrate compound at a molar ratio of 1:1 as in Example 1, Example 1 Experiments and judgments were conducted in the same manner. Thermal oxidative deterioration inhibitor [II]: Similar to stearyl thiodipropionate, experiments and evaluations were also performed on the thermal oxidative deterioration inhibitor [II] alone. The results are shown in Table 2.
【００１７】[0017]
【表２】[Table 2]
【００１８】表２より、本発明の熱酸化劣化防止剤は良
好な酸化防止効果を示すことが明らかである。なお、Ｎ
ｏ．６（本発明例）のものは、１８０℃で７２時間保持
後においても、評価Ｂを維持することができ、十分実用
可能な結果を示した。From Table 2, it is clear that the thermal oxidative deterioration inhibitor of the present invention exhibits a good antioxidant effect. In addition, N
o. Sample No. 6 (Example of the present invention) was able to maintain the evaluation B even after being held at 180° C. for 72 hours, and showed a sufficiently practical result.
【００１９】実施例３
熱酸化劣化防止剤として実施例２の［ＩＩ］を用い、前
記実施例１の■をホスト化合物として、モル比１：１の
包接化合物とし、該包接化合物をエチレン−酢酸ビニル
共重合体（ＶＡｃ：２７〜２９％）／精製パラフィンワ
ックス／ロジンエステル＝１／１／１（重量比）で溶融
混合したホットメルト型接着剤中に、熱酸化劣化防止剤
の割合が０．５重量％となるように添加し、１８０℃で
４８時間保持した後の色を観察し、前記判定基準により
判定を行なった。同様に熱酸化劣化防止剤［ＩＩ￥単独
についても実験を行なった。結果を表３に示す。Example 3 Using [II] of Example 2 as a thermal oxidative deterioration inhibitor, and using ■ of Example 1 as a host compound, a clathrate compound was prepared at a molar ratio of 1:1, and the clathrate compound was mixed with ethylene. - Ratio of thermal oxidative deterioration inhibitor in hot melt adhesive melt-mixed with vinyl acetate copolymer (VAc: 27-29%)/purified paraffin wax/rosin ester = 1/1/1 (weight ratio) was added so as to be 0.5% by weight, and the color was observed after being maintained at 180°C for 48 hours, and the judgment was made according to the above-mentioned criteria. Similarly, experiments were also conducted using the thermal oxidative deterioration inhibitor [II ¥ alone. The results are shown in Table 3.
【００２０】[0020]
【表３】[Table 3]
【００２１】表３より、本発明の熱酸化劣化防止剤は良
好な酸化防止効果を示すことが明らかである。From Table 3, it is clear that the thermal oxidative deterioration inhibitor of the present invention exhibits a good antioxidant effect.
【００２２】[0022]
【発明の効果】以上詳述した通り、本発明の熱酸化劣化
防止剤は、優れた熱酸化劣化防止効果を長時間に亘って
維持することができる。しかして、このような良好な熱
酸化劣化防止効果及びその持続性を示す本発明の熱酸化
劣化防止剤によれば、少ない使用量にて、極めて良好な
効果を得ることが可能とされる。[Effects of the Invention] As detailed above, the thermal oxidative deterioration inhibitor of the present invention can maintain an excellent thermal oxidative deterioration preventing effect for a long period of time. According to the thermal oxidative deterioration inhibitor of the present invention, which exhibits such a good thermal oxidative deterioration prevention effect and its sustainability, it is possible to obtain extremely good effects with a small amount of use.
Claims (1)
２４）から選ばれる１種又は２種以上の多分子系ホスト
化合物とが反応して得られた包接化合物を含むことを特
徴とする粉末状熱酸化劣化防止剤。 （１） １，１，６，６−テトラフェニル−２，４−
ヘキサジイン−１，６−ジオール （２） １，６−ビス（２−クロロフェニル）−１，
６−ジフェニルヘキサ−２，４−ジイン−１，６−ジオ
ール （３） １，１−ビス（２，４−ジメチルフェニル）
−２−プロピン−１−オール （４） ２，５−ビス（２，４−ジメチルフェニル）
ハイドロキノン （５） １，１，４，４−テトラフェニル−２−ブチ
ン−１，４−ジオール （６） １，１，２，２−テトラフェニルエタン−１
，２−ジオール （７） １，１−ビ−２−ナフトール（８） ９，
１０−ジフェニル−９，１０−ジヒドロアントラセン−
９，１０−ジオール （９） １，１，６，６−テトラキス（２，４−ジメ
チルフェニル）−２，４−ヘキサジイン−１，６−ジオ
ール （１０） ９，１０−ビス（４−メチルフェニル）−
９，１０−ジヒドロアントラセン−９，１０−ジオール
（１１） １，１−ビス（４−ヒドロキシフェニル）
シクロヘキサン （１２） Ｎ，Ｎ，Ｎ’，Ｎ’−テトラキス（シクロ
ヘキシル）−（１，１’−ビフェニル）−２，２’−ジ
カルボキシアミド （１３） １，４−ジアザビシクロ−（２，２，２）
−オクタン （１４） ４，４’−スルホニルビスフェノール（１
５） ４，４’−ブチリデンビス（３−メチル−６−
ｔｅｒｔ−ブチルフェノール） （１６） ２，２’−メチレンビス（４−メチル−６
−ｔｅｒｔ−ブチルフェノール） （１７） ４，４’−チオビス（３−メチル−６−ｔ
ｅｒｔ−ブチルフェノール） （１８） ２，２’−メチレンビス（４−クロロフェ
ノール） （１９） デオキシコール酸 （２０） ｔ−ブチルヒドロキノン （２１） ２，５−ジ−ｔｅｒｔ−ブチルヒドロキノ
ン（２２） コール酸 （２３） 顆粒状コーンスターチ（ポーラスＹ−２０
）（２４） α，α，α’，α’−テトラフェニル−
１’，１’−ビフェニル−２，２’−ジメタノール[Claim 1] A thermal oxidative deterioration inhibitor and the following (1) to (
24) A powdery thermal oxidative deterioration inhibitor comprising a clathrate compound obtained by reacting with one or more polymolecular host compounds selected from 24). (1) 1,1,6,6-tetraphenyl-2,4-
Hexadiyne-1,6-diol (2) 1,6-bis(2-chlorophenyl)-1,
6-diphenylhexa-2,4-diyne-1,6-diol (3) 1,1-bis(2,4-dimethylphenyl)
-2-propyn-1-ol (4) 2,5-bis(2,4-dimethylphenyl)
Hydroquinone (5) 1,1,4,4-tetraphenyl-2-butyne-1,4-diol (6) 1,1,2,2-tetraphenylethane-1
,2-diol (7) 1,1-bi-2-naphthol (8) 9,
10-diphenyl-9,10-dihydroanthracene-
9,10-diol (9) 1,1,6,6-tetrakis(2,4-dimethylphenyl)-2,4-hexadiyne-1,6-diol (10) 9,10-bis(4-methylphenyl )−
9,10-dihydroanthracene-9,10-diol (11) 1,1-bis(4-hydroxyphenyl)
Cyclohexane (12) N,N,N',N'-tetrakis(cyclohexyl)-(1,1'-biphenyl)-2,2'-dicarboxamide (13) 1,4-diazabicyclo-(2,2, 2)
-Octane (14) 4,4'-sulfonylbisphenol (1
5) 4,4'-butylidene bis(3-methyl-6-
tert-butylphenol) (16) 2,2'-methylenebis(4-methyl-6
-tert-butylphenol) (17) 4,4'-thiobis(3-methyl-6-t
ert-butylphenol) (18) 2,2'-methylenebis(4-chlorophenol) (19) Deoxycholic acid (20) t-butylhydroquinone (21) 2,5-di-tert-butylhydroquinone (22) Cholic acid (23) Granular cornstarch (Porous Y-20
) (24) α, α, α', α'-Tetraphenyl-
1',1'-biphenyl-2,2'-dimethanol
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1862491A JPH04258682A (en) | 1991-02-12 | 1991-02-12 | Thermal and oxidative deterioration inhibitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1862491A JPH04258682A (en) | 1991-02-12 | 1991-02-12 | Thermal and oxidative deterioration inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04258682A true JPH04258682A (en) | 1992-09-14 |
Family
ID=11976780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1862491A Pending JPH04258682A (en) | 1991-02-12 | 1991-02-12 | Thermal and oxidative deterioration inhibitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04258682A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179654A (en) * | 2003-11-27 | 2005-07-07 | Jsr Corp | Hot-melt adhesive composition |
-
1991
- 1991-02-12 JP JP1862491A patent/JPH04258682A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005179654A (en) * | 2003-11-27 | 2005-07-07 | Jsr Corp | Hot-melt adhesive composition |
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