JPH0465862B2 - - Google Patents
Info
- Publication number
- JPH0465862B2 JPH0465862B2 JP59051038A JP5103884A JPH0465862B2 JP H0465862 B2 JPH0465862 B2 JP H0465862B2 JP 59051038 A JP59051038 A JP 59051038A JP 5103884 A JP5103884 A JP 5103884A JP H0465862 B2 JPH0465862 B2 JP H0465862B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- tinuvin
- weather resistance
- polyoxymethylene
- 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
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 13
- -1 Polyoxymethylene Polymers 0.000 claims description 13
- 229920006324 polyoxymethylene Polymers 0.000 claims description 13
- 150000001412 amines Chemical class 0.000 claims description 11
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 10
- 239000012964 benzotriazole Substances 0.000 claims description 10
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 10
- 239000004611 light stabiliser Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- OLFNXLXEGXRUOI-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4,6-bis(2-phenylpropan-2-yl)phenol Chemical compound C=1C(N2N=C3C=CC=CC3=N2)=C(O)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 OLFNXLXEGXRUOI-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 16
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 229920009382 Polyoxymethylene Homopolymer Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 241000156978 Erebia Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- SWZOQAGVRGQLDV-UHFFFAOYSA-N 4-[2-(4-hydroxy-2,2,6,6-tetramethylpiperidin-1-yl)ethoxy]-4-oxobutanoic acid Chemical compound CC1(C)CC(O)CC(C)(C)N1CCOC(=O)CCC(O)=O SWZOQAGVRGQLDV-UHFFFAOYSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 2
- 229920012196 Polyoxymethylene Copolymer Polymers 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BIIBYWQGRFWQKM-JVVROLKMSA-N (2S)-N-[4-(cyclopropylamino)-3,4-dioxo-1-[(3S)-2-oxopyrrolidin-3-yl]butan-2-yl]-2-[[(E)-3-(2,4-dichlorophenyl)prop-2-enoyl]amino]-4,4-dimethylpentanamide Chemical compound CC(C)(C)C[C@@H](C(NC(C[C@H](CCN1)C1=O)C(C(NC1CC1)=O)=O)=O)NC(/C=C/C(C=CC(Cl)=C1)=C1Cl)=O BIIBYWQGRFWQKM-JVVROLKMSA-N 0.000 description 1
- UYVWNPAMKCDKRB-UHFFFAOYSA-N 1,2,4,5-tetraoxane Chemical compound C1OOCOO1 UYVWNPAMKCDKRB-UHFFFAOYSA-N 0.000 description 1
- FQERLIOIVXPZKH-UHFFFAOYSA-N 1,2,4-trioxane Chemical compound C1COOCO1 FQERLIOIVXPZKH-UHFFFAOYSA-N 0.000 description 1
- MXAOILAHPVJWBS-UHFFFAOYSA-N 10-(azepan-1-yl)-10-oxodecanamide Chemical compound NC(=O)CCCCCCCCC(=O)N1CCCCCC1 MXAOILAHPVJWBS-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- DJZKNOVUNYPPEE-UHFFFAOYSA-N tetradecane-1,4,11,14-tetracarboxamide Chemical compound NC(=O)CCCC(C(N)=O)CCCCCCC(C(N)=O)CCCC(N)=O DJZKNOVUNYPPEE-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、耐候性の優れたポリオキシメチレン
組成物に関するものであり、更に詳しくは、特定
のベンゾトリアゾールとヒンダードアミンの併用
添加により耐候性を改良したポリオキシメチレン
組成物に関するものである。
ポリオキシメチレンは、その優れた強度、摩擦
摩耗特性、耐疲労特性、クリープ特性、電気特
性、寸法性などの故に、歯車、軸受などの機械部
品、電気部品に広く使用されている。しかしなが
ら耐候性においてやゝ劣り、特に着色品の場合長
期に日光に曝すと表面においてポリオキシメチレ
ンが光エネルギーにより分子切断される為白化現
象及びクレージングを起し、目立ち易いことか
ら、成形品の外観を著しく低下させ、さらに著し
い場合は機械的強度低下を起し実用に耐えない。
従つてこうした日光に対する抵抗性つまり耐候
性を改良することによつて、自動車などの高度な
耐候性が要求される分野へ用途拡大できることは
必至である。
従来、ポリオキシメチレンの耐候性を改良する
方法として、紫外線吸収剤、例えばベンゾフエノ
ン系、ベンゾトリアゾール系などを添加する方
法、紫外線吸収剤とヒンダードアミン系光安定剤
を併用する方法があるが、耐候性はまだ十分でな
い。またこれらの方法で十分な耐候性を得ようと
すれば、非常に多量の添加剤を添加しなければな
らず、添加剤のブリードなどによる外観不良、添
加剤による熱安定性、機械的強度低下などの問題
を生じ実用的でない。
本発明者らはこうした事に鑑み、ポリオキシメ
チレンの耐候性向上に対し鋭意研究の結果、ある
一種のベンゾトリアゾール系紫外線吸収剤とヒン
ダードアミン系光安定剤との組合せが特異的にポ
リオキシメチレンの耐候性を向上させることを発
見し、今発明に至つた。
すなわち本発明はポリオキシメチレンとそれの
100重量部に対し、構造式
で表わされるベンゾトリアゾール系紫外線吸収剤
0.01〜４重量部好ましくは0.05〜２重量部と、１
種あるいは２種以上のヒンダードアミン系光安定
剤0.01〜３重量部、好ましくは0.05〜1.5重量部を
併用含有したポリオキシメチレン組成物である。
また上記以外の紫外線吸収剤の併用も可能である
が、全紫外線吸収剤量から見れば効果は減ずる。
紫外線吸収剤の量が、この範囲より少なければ、
耐候性を向上させる効果が不充分であり、またこ
の範囲より多い場合には、成形品表面へのブリー
ドに帰因する外観不良、機械的特性の低下のため
実情的でない。
ヒンダードアミン系光安定剤の場合も同様に少
なければ、効果が不充分であり、多い場合には、
外観不良、熱安定性低下のため実用的でない。
本発明におけるベンゾトリアゾール系紫外線吸
収剤としては、チバガイギー社製チヌビン234（化
学構造式を表−１に示す）が用いられる。
また本発明に用いられるヒンダードアミン系光
安定剤としては、市販品としては三共(株)製サノー
ルLS770、LS744、LS944、LS2626、チバガイギ
ー社製、チヌビン622、アデカアーガス社製、
MARK、LA−57（化学構造式を表−１に示す）
などがあげられるが、必ずしもこれらに限定され
るものではない。
本発明に用いられるポリオキシメチレンとは、
ポリオキシメチレンホモポリマー又は主鎖の大部
分がオキシメチレン連鎖よりなるポリオキシメチ
レン共重合体であり、詳しくはホルムアルデヒド
もしくはホルムアルデヒドの環状オリゴマーであ
るトリオキサン、テトラオキサンなどを単独に、
又はこれらと共重合可能な１種以上のコモノマー
（たとえばエチレンオキサイド、１，４−ブタン
ジオールフオマールなど）をさらに組合せて、重
合又は共重合して得られたものを末端基からの分
解に対して安定化したものをいう。使用に際して
は、通常の熱安定剤、酸化防止剤を添加すること
ができ、従来公知の各種有機顔料、無機顔料およ
びガラス繊維などの種々補強剤の添加も許され
る。
以下実施例を挙げ説明するが、本発明はこれら
に限定されるものではない。
実施例 １
ポリオキシメチレンホモポリマー（メルトイン
デツクス15ｇ／10分）100重量部に対し熱安定剤
としてカプロラクタム／ヘキサメチレンアジパミ
ド／ヘキサメチレンセバカミドの三元共重合ポリ
アミド0.5重量部および、チバガイギー社製酸化
防止剤イルガノツクス1010を0.10重量部、着色用
顔料として、有機顔料（BASF製バリオゲンレツ
ド3911K0.066重量部およびBASF製シコバーサル
レツド39−1001を0.056重量部、耐候性向上剤と
して、チバガイギー社のベンゾトリアゾール系紫
外線吸収剤チヌビン−234を0.50重量部、三共社
製ヒンダードアミン系光安定剤サノールLS770を
0.10重量部を添加し、三井三池製作所ヘンシユル
ミキサーで常温、１分間ブレンド後、30mmφ押出
し機で溶融混合してペレツトを作つた。ペレツト
を80℃で５時間熱風乾燥した後、射出成形機によ
り、タテ９cm、ヨコ５cm、厚さ２mmの平板を成形
した。この平板をサンシヤインウエザーメーター
（スガ試験機(株)製、サンシヤインスーパーロング
ライフウユザーメーターWEL−SUN−HCブラ
ツクパネル83℃雨なし連続運転）に曝露し、200、
300、400、600時間の促進耐候試験を実施し平板
表面の観察をした。結果を表２に示す。比較例１
〜３と比べ優れた耐候性を示す。
比較例 １
実施例−１記載のうちチヌビン234をチバガイ
ギー社製ベンゾトリアゾール系紫外線吸収剤チヌ
ビン328に変えた結果を表２に示す。
比較例 ２
実施例−１記載のうちチヌビン234をチバガイ
ギー社製ベンゾトリアゾール系紫外線吸収剤チヌ
ビン327に変えた結果を表２に示す。
比較例 ３
実施例−１記載のうちチヌビン234をチバガイ
ギー社製ベンゾトリアゾール系紫外線吸収剤チヌ
ビン327に変えた場合の結果を表２に示す。
実施例 ２
実施例−１のうち、チヌビン234の量を1.0重量
部、サノールLS770の量を0.25重量部にかえ、同
様に行なつた。結果を表２に示す。
非常に優れた耐候性を示す。
実施例 ３
実施例−１のうち、三共(株)のサノールLS770
0.10重量部を同じくヒンダードアミン系光安定剤
サノールLS944 0.10重量部にかえ同様に行なつ
た。結果を表２に示す。比較例４に比べ耐候性に
優れている。
比較例 ４
実施例−３のうち、チヌビン234をチヌビン328
に変えた結果を表２に示す。
実施例 ４
実施例−１のうち、チヌビン234の量0.50重量
部を1.00重量部、サノールLS770 0.10重量部を、
サノールLS944 0.25重量部に変え同様に行なつ
た。結果を表２に示す。良好な耐候性を有してい
る。
実施例 ５
実施例−１のうち、サノールLS770 0.10重量
部を、アデカアーガス社製ヒンダードアミン系光
安定剤MARK LA−57 0.10重量部に変え同様に
行なつた。結果を表２に示す。比較例５に比べ耐
候性に優れている。
比較例 ５
実施例−５記載のうち、チヌビン234に変えチ
ヌビン328の場合での結果を表２に示す。
実施例 ６
実施例−１のうち、チヌビン234の量0.50重量
部を1.00重量部、サノール770 0.10重量部を、ア
デカアーガスMARK LA−57 0.25重量部に変え
た場合の結果を表２に示す。良好な耐候性を有し
ている。
実施例 ７
市販のポリオキシメチレンホモポリマー（旭化
成工業製テナツク5010）100重量部に対しチヌビ
ン234 0.50重量部サノール770 0.10重量部を添加
し、混合し、溶融押出後成形した。ポリオキシメ
チレン組成物の耐候試験結果を表２に示す。比較
例−６に比べ良好な耐候性を示す。
比較例 ６
実施例−７記載のうちチヌビン234を、チヌビ
ン328を用いた結果を表２に示す。
実施例 ８
実施例−７記載のうちポリオキシメチレンホモ
ポリマーに変え市販のポリオキシメチレンコポリ
マー（ポリプラスチツクス社製ジユラコンＭ−90
−02）を用いた場合の結果を表２に示す。比較例
−７に比べ耐候性に優れる。
比較例 ７
実施例−８記載のうち、チヌビン234を、チヌ
ビン328にかえた場合の結果を表２に示す。
比較例 ８
実施例−１のうち、サノールLS770を除いた配
合の結果を表２に示す。
比較例 ９
実施例−１のうち、チヌビン234を除いた配合
の結果を表２に示す。非常に耐候性が悪いことが
明らかである。
実施例 ９
実施例−１のうち、紫外線吸収剤チヌビン234
を0.10重量部ヒンダードアミン系光安定剤サノー
ルLS770を0.10重量に変えた場合の結果を表２に
示す。比較例−10に比べ耐候性に優れる。
比較例 10
実施例−９のうち、チヌビン234、サノール
LS770を除いた配合の結果を表２に示す。
実施例 10
実施例−１のうち、紫外線吸収剤チヌビン234
を２重量部、サノールLS770 1.5重量部に変え造
つたペレツトを射出成形して、平板を得た。この
平板を常温で24時間放置したが表面光沢は変化な
く、ブリードなしと判定。
比較例 11
実施例−10のうち、チヌビン234を５重量部サ
ノールLS770を４重量部に変え、射出成形平板を
得た。成形品表面は、光沢がなくトルエンを含ま
せたガーゼでふき取ることができた。ブリードあ
りと判定。
The present invention relates to a polyoxymethylene composition with excellent weather resistance, and more particularly to a polyoxymethylene composition whose weather resistance has been improved by the combined addition of a specific benzotriazole and a hindered amine. Polyoxymethylene is widely used in mechanical parts such as gears and bearings, and electrical parts because of its excellent strength, friction and wear properties, fatigue resistance properties, creep properties, electrical properties, dimensional properties, etc. However, they are somewhat inferior in weather resistance, and especially in the case of colored products, when exposed to sunlight for a long period of time, the molecules of polyoxymethylene on the surface are cut by light energy, causing a whitening phenomenon and crazing, which is easily noticeable, resulting in poor appearance of the molded product. If it is even more severe, the mechanical strength will be lowered and it will not be suitable for practical use. Therefore, by improving the resistance to sunlight, that is, the weather resistance, it is inevitable that the application can be expanded to fields that require a high degree of weather resistance, such as automobiles. Conventionally, methods for improving the weather resistance of polyoxymethylene include adding ultraviolet absorbers such as benzophenone and benzotriazole, and using a combination of ultraviolet absorbers and hindered amine light stabilizers. is still not enough. In addition, in order to obtain sufficient weather resistance using these methods, extremely large amounts of additives must be added, resulting in poor appearance due to additive bleed, and reductions in thermal stability and mechanical strength due to additives. It is not practical as it causes such problems. In view of the above, the present inventors have conducted extensive research into improving the weather resistance of polyoxymethylene, and have found that the combination of a certain type of benzotriazole ultraviolet absorber and hindered amine light stabilizer specifically improves the weather resistance of polyoxymethylene. They discovered that it improves weather resistance and have now invented it. That is, the present invention relates to polyoxymethylene and its
For 100 parts by weight, structural formula Benzotriazole ultraviolet absorber represented by
0.01 to 4 parts by weight, preferably 0.05 to 2 parts by weight, and 1
The polyoxymethylene composition contains 0.01 to 3 parts by weight, preferably 0.05 to 1.5 parts by weight of one or more hindered amine light stabilizers.
It is also possible to use UV absorbers other than those mentioned above, but the effect will be reduced in terms of the total amount of UV absorbers.
If the amount of UV absorber is less than this range,
The effect of improving weather resistance is insufficient, and if the amount exceeds this range, it is not practical due to poor appearance and deterioration of mechanical properties due to bleeding to the surface of the molded product. Similarly, in the case of hindered amine photostabilizers, if the amount is too low, the effect will be insufficient, and if the amount is too much, the effect will be insufficient.
Not practical due to poor appearance and reduced thermal stability. As the benzotriazole ultraviolet absorber in the present invention, Tinuvin 234 manufactured by Ciba Geigy (chemical structural formula is shown in Table 1) is used. As the hindered amine light stabilizer used in the present invention, commercially available products include Sanol LS770, LS744, LS944, LS2626 manufactured by Sankyo Co., Ltd., Tinuvin 622 manufactured by Ciba Geigy, Tinuvin 622 manufactured by Adeka Argus,
MARK, LA-57 (chemical structural formula is shown in Table-1)
These include, but are not necessarily limited to. The polyoxymethylene used in the present invention is
A polyoxymethylene homopolymer or a polyoxymethylene copolymer in which most of the main chain is composed of oxymethylene chains, specifically, formaldehyde or a cyclic oligomer of formaldehyde such as trioxane or tetraoxane alone,
Or, by further combining these with one or more comonomers copolymerizable (e.g., ethylene oxide, 1,4-butanediol foam, etc.), the resulting product can be polymerized or copolymerized to prevent decomposition from the terminal group. It refers to something that has been stabilized. When used, conventional heat stabilizers and antioxidants can be added, and various conventionally known organic pigments, inorganic pigments, and various reinforcing agents such as glass fibers can also be added. Examples will be described below, but the present invention is not limited thereto. Example 1 0.5 parts by weight of a terpolymer polyamide of caprolactam/hexamethylene adipamide/hexamethylene sebacamide as a heat stabilizer for 100 parts by weight of polyoxymethylene homopolymer (melt index 15 g/10 minutes) and 0.10 parts by weight of the antioxidant Irganox 1010 manufactured by Ciba Geigy as a coloring pigment, 0.066 parts by weight of organic pigments (0.066 parts by weight of Variogen Red 3911K manufactured by BASF and 0.056 parts by weight of Cicoversal Red 39-1001 manufactured by BASF, as a weather resistance improver, 0.50 parts by weight of Ciba Geigy's benzotriazole ultraviolet absorber Tinuvin-234 and Sankyo's hindered amine light stabilizer Sanol LS770.
0.10 parts by weight was added, blended for 1 minute at room temperature using a Mitsui Miike Machinery Mixer, and then melt-mixed using a 30 mmφ extruder to form pellets. After drying the pellets with hot air at 80° C. for 5 hours, they were molded into flat plates with a length of 9 cm, a width of 5 cm and a thickness of 2 mm using an injection molding machine. This flat plate was exposed to a Sunshine Weather Meter (Manufactured by Suga Test Instruments Co., Ltd., Sunshine Super Long Life User Meter WEL-SUN-HC Black Panel 83℃ continuous operation without rain),
Accelerated weathering tests were conducted for 300, 400, and 600 hours, and the surface of the flat plate was observed. The results are shown in Table 2. Comparative example 1
-Excellent weather resistance compared to 3. Comparative Example 1 Table 2 shows the results of replacing Tinuvin 234 in Example 1 with Tinuvin 328, a benzotriazole ultraviolet absorber manufactured by Ciba Geigy. Comparative Example 2 Table 2 shows the results of replacing Tinuvin 234 in Example 1 with Tinuvin 327, a benzotriazole ultraviolet absorber manufactured by Ciba Geigy. Comparative Example 3 Table 2 shows the results when Tinuvin 234 described in Example 1 was replaced with Tinuvin 327, a benzotriazole ultraviolet absorber manufactured by Ciba Geigy. Example 2 The same procedure as in Example 1 was carried out except that the amount of Tinuvin 234 was changed to 1.0 part by weight and the amount of Sanol LS770 was changed to 0.25 part by weight. The results are shown in Table 2. Shows excellent weather resistance. Example 3 Among Example-1, Sanol LS770 manufactured by Sankyo Co., Ltd.
The same procedure was carried out by replacing 0.10 parts by weight of the same hindered amine light stabilizer Sanol LS944. The results are shown in Table 2. It has excellent weather resistance compared to Comparative Example 4. Comparative Example 4 Among Example-3, Tinuvin 234 was replaced with Tinuvin 328.
The results are shown in Table 2. Example 4 In Example-1, 0.50 parts by weight of Tinuvin 234 was 1.00 parts by weight, 0.10 parts by weight of Sanol LS770,
The same procedure was carried out by changing to 0.25 parts by weight of Sanol LS944. The results are shown in Table 2. It has good weather resistance. Example 5 The same procedure as in Example 1 was carried out except that 0.10 parts by weight of Sanol LS770 was replaced with 0.10 parts by weight of MARK LA-57, a hindered amine light stabilizer manufactured by Adeka Argus. The results are shown in Table 2. It has better weather resistance than Comparative Example 5. Comparative Example 5 Table 2 shows the results when Tinuvin 328 was used instead of Tinuvin 234 among those described in Example-5. Example 6 Table 2 shows the results when the amount of Tinuvin 234 in Example-1 was changed from 0.50 parts by weight to 1.00 parts by weight, and 0.10 parts by weight of Sanol 770 was changed to 0.25 parts by weight of Adeka Argus MARK LA-57. It has good weather resistance. Example 7 0.50 parts by weight of Tinuvin 234 and 0.10 parts by weight of Sanol 770 were added to 100 parts by weight of a commercially available polyoxymethylene homopolymer (Tenatsuku 5010 manufactured by Asahi Kasei Corporation), mixed, and molded after melt extrusion. Table 2 shows the weathering test results of the polyoxymethylene composition. Shows better weather resistance than Comparative Example-6. Comparative Example 6 Table 2 shows the results using Tinuvin 234 and Tinuvin 328 among those described in Example-7. Example 8 The polyoxymethylene homopolymer described in Example 7 was replaced with a commercially available polyoxymethylene copolymer (Dyuracon M-90 manufactured by Polyplastics Co., Ltd.).
-02) is shown in Table 2. Excellent weather resistance compared to Comparative Example-7. Comparative Example 7 Table 2 shows the results when Tinuvin 234 in Example 8 was replaced with Tinuvin 328. Comparative Example 8 Table 2 shows the results of the formulation of Example-1 excluding Sanol LS770. Comparative Example 9 Table 2 shows the results of the formulation of Example-1 excluding Tinuvin 234. It is clear that the weather resistance is very poor. Example 9 Among Example-1, the ultraviolet absorber Tinuvin 234
Table 2 shows the results when 0.10 parts by weight of the hindered amine light stabilizer Sanol LS770 was changed to 0.10 parts by weight. Excellent weather resistance compared to Comparative Example-10. Comparative Example 10 Among Example-9, Tinuvin 234, Sanol
Table 2 shows the results of the formulations excluding LS770. Example 10 Among Example-1, the ultraviolet absorber Tinuvin 234
Pellets made by changing 2 parts by weight of Sanol LS770 and 1.5 parts by weight of Sanol LS770 were injection molded to obtain a flat plate. This flat plate was left at room temperature for 24 hours, but the surface gloss did not change, and it was determined that there was no bleeding. Comparative Example 11 In Example 10, Tinuvin 234 was changed to 5 parts by weight and Sanol LS770 was changed to 4 parts by weight to obtain an injection molded flat plate. The surface of the molded product had no gloss and could be wiped off with gauze soaked in toluene. It was determined that there was a bleed.
【表】【table】
【表】【table】
【表】【table】
【表】【table】
Claims (1)
対し、構造式 で表わされるベンゾトリアゾール系紫外線吸収剤
0.01〜４重量部と、ヒンダードアミン系光安定剤
0.01〜３重量部とからなる耐候性の改良されたポ
リオキシメチレン組成物。[Claims] 1. Polyoxymethylene and 100 parts by weight of the structural formula Benzotriazole ultraviolet absorber represented by
0.01 to 4 parts by weight and hindered amine light stabilizer
0.01 to 3 parts by weight of a polyoxymethylene composition with improved weather resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5103884A JPS60195155A (en) | 1984-03-19 | 1984-03-19 | Polyoxymethylene composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5103884A JPS60195155A (en) | 1984-03-19 | 1984-03-19 | Polyoxymethylene composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60195155A JPS60195155A (en) | 1985-10-03 |
| JPH0465862B2 true JPH0465862B2 (en) | 1992-10-21 |
Family
ID=12875629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5103884A Granted JPS60195155A (en) | 1984-03-19 | 1984-03-19 | Polyoxymethylene composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60195155A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6136339A (en) * | 1984-07-27 | 1986-02-21 | Polyplastics Co | Weather-resistant polyacetal resin composition |
| US5232965A (en) * | 1991-03-22 | 1993-08-03 | E. I. Du Pont De Nemours And Company | Stabilized polyacetal compositions |
| US5149723A (en) * | 1991-03-22 | 1992-09-22 | E. I. Du Pont De Nemours And Company | Stabilized polyacetal compositions containing a mixture of hals having tertiary functionality |
| JPH0585679U (en) * | 1992-04-21 | 1993-11-19 | 益弘 光山 | File |
| DE4229760A1 (en) * | 1992-09-05 | 1994-03-10 | Basf Ag | UV stabilized polyoxymethylene molding compounds |
| US5744527A (en) * | 1993-07-07 | 1998-04-28 | Polyplastics Co., Ltd. | Polyacetal resin composition |
| JP3281153B2 (en) * | 1993-11-30 | 2002-05-13 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| EP0758641B1 (en) | 1995-08-11 | 2000-08-30 | Daicel Chemical Industries, Ltd. | A fatty acid esters composition of a polyglycerine, a process for the preparation thereof, a process for the preparation of a highly-purified fatty acid esters composition of a polyglycerine, a highly-purified fatty acid esters composition of a polyglycerine, an additive for food-stuffs, a resin composition, and a composition for cosmetics or detergents |
| JP2853983B2 (en) * | 1995-11-27 | 1999-02-03 | 東レ株式会社 | Method for producing oxymethylene copolymer |
| JP2001164087A (en) | 1999-12-03 | 2001-06-19 | Polyplastics Co | Branched polyacetal resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126744A (en) * | 1973-03-08 | 1974-12-04 | ||
| JPS5058141A (en) * | 1973-06-09 | 1975-05-20 | ||
| JPS54153850A (en) * | 1978-05-22 | 1979-12-04 | Goodrich Co B F | Polymer composition having high resistance to photo deterioration |
-
1984
- 1984-03-19 JP JP5103884A patent/JPS60195155A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49126744A (en) * | 1973-03-08 | 1974-12-04 | ||
| JPS5058141A (en) * | 1973-06-09 | 1975-05-20 | ||
| JPS54153850A (en) * | 1978-05-22 | 1979-12-04 | Goodrich Co B F | Polymer composition having high resistance to photo deterioration |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60195155A (en) | 1985-10-03 |
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