JPS6138940B2 - - Google Patents
Info
- Publication number
- JPS6138940B2 JPS6138940B2 JP56109635A JP10963581A JPS6138940B2 JP S6138940 B2 JPS6138940 B2 JP S6138940B2 JP 56109635 A JP56109635 A JP 56109635A JP 10963581 A JP10963581 A JP 10963581A JP S6138940 B2 JPS6138940 B2 JP S6138940B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- formula
- carbon atoms
- alkyl
- following formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 239000000049 pigment Substances 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 150000003053 piperidines Chemical class 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 239000004611 light stabiliser Substances 0.000 claims description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 150000008366 benzophenones Chemical class 0.000 claims description 3
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical class OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 3
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 claims description 3
- 150000003872 salicylic acid derivatives Chemical class 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 2
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 2
- 125000003354 benzotriazolyl group Chemical class N1N=NC2=C1C=CC=C2* 0.000 claims 1
- -1 dodecyl-3-methyl-5-isopropyl-4-hydroxybenzoate Chemical compound 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000006096 absorbing agent Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 239000001023 inorganic pigment Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 4
- 238000005562 fading Methods 0.000 description 4
- 239000012860 organic pigment Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- YEYCMBWKTZNPDH-UHFFFAOYSA-N (2,2,6,6-tetramethylpiperidin-4-yl) benzoate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC=CC=C1 YEYCMBWKTZNPDH-UHFFFAOYSA-N 0.000 description 1
- XCPFSALHURPPJE-UHFFFAOYSA-N (3,5-ditert-butyl-4-hydroxyphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 XCPFSALHURPPJE-UHFFFAOYSA-N 0.000 description 1
- VNFXPOAMRORRJJ-UHFFFAOYSA-N (4-octylphenyl) 2-hydroxybenzoate Chemical compound C1=CC(CCCCCCCC)=CC=C1OC(=O)C1=CC=CC=C1O VNFXPOAMRORRJJ-UHFFFAOYSA-N 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- PITPRNOGWXAZAW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-methoxyphenol Chemical compound COC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 PITPRNOGWXAZAW-UHFFFAOYSA-N 0.000 description 1
- 239000005201 4-Octylphenyl Salicylate Substances 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
- VSFKXGZJZOIEEN-UHFFFAOYSA-N C(C=1C(O)=CC=CC1)(=O)OC1=CC=C(C=C1)C(C)CC Chemical compound C(C=1C(O)=CC=CC1)(=O)OC1=CC=C(C=C1)C(C)CC VSFKXGZJZOIEEN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 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 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- UBGPHZZYVGSNSW-UHFFFAOYSA-N methyl 4-hydroxy-3-methyl-5-propan-2-ylbenzoate Chemical compound COC(=O)C1=CC(C)=C(O)C(C(C)C)=C1 UBGPHZZYVGSNSW-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- GBNRNYYETPVZEU-UHFFFAOYSA-N phenyl 4-hydroxy-3,5-di(propan-2-yl)benzoate Chemical compound CC(C)C1=C(O)C(C(C)C)=CC(C(=O)OC=2C=CC=CC=2)=C1 GBNRNYYETPVZEU-UHFFFAOYSA-N 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は顔料を含んだ高分子材料の変退色防止
処方をした組成物に関するものである。さらにく
わしくは光安定剤である紫外線吸収剤とピペリジ
ン誘導体とを配合した高分子材料組成物に関する
ものである。その目的とするところは顔料を配合
した高分子成形加工品の初期の色調を維持するこ
とにある。高分子材料はすぐれた物理的および化
学的特性を有することにより、成形品、テープ、
繊維、フイルム等に大量に消費されておりその需
要は年々増加している。
これら高分子材料は顔料、染料等によつて容易
に着色できることが特徴であり、成形品、テー
プ、繊維およびフイルム等として消費される場
合、通常顔料、染料等が配合されて着色している
ことが多い。
しかし、高分子材料に配合された顔料および塗
料は日光または紫外線等により、保存中および使
用中に色調が変化するという欠点があり、この色
調変化のため商品価値をそこなう。したがつて顔
料、染料等を配合した高分子材料の初期色調の変
化を防止することは工業的にきわめて重要であ
る。
従来、このような欠点に対して有効であると知
られているカドミウム、鉛、クロムなどを含有す
る無機系の顔料は日光または紫外線の影響を受け
にくいきわめてすぐれたものであるが、カドミウ
ムや鉛、クロムなどは有害であり、カドミウムや
鉛、クロムなどを含有する無機系顔料を配合した
高分子材料を使用後に焼却あるいは廃棄する場合
等に問題があり、使用に当つての制限が次第に厳
しくなつている。
本発明は日光または紫外線等による変退色にす
ぐれた効果のあるカドミウムや鉛、クロムなどを
含有する無機系顔料をカドミウムや鉛、クロムな
どを含有しない無機および有機系顔料、特に有機
系顔料にかえた場合に生じる変退色を公知の紫外
線吸収剤とピペリジン誘導体である光安定剤とを
組合せて同時に配合することによつてこの目的を
達成しようとするものである。
本発明組成物におけるカドミウムや鉛、クロム
などを含有しない無機および有機系顔料の変退色
を防止するために高分子材料に配合する光安定剤
．紫外線吸収剤として次式（Ａ）
（ただし、式中、R1，R2およびR3は水素原子、
水酸基、ハロゲン原子、炭素原子数１〜６個の
アルキル基または炭素原子数１〜12個のアルコ
キシ基を表わす。）
で表わされるベンゾフエノン誘導体、
次式（Ｂ）
（ただし式中、R4，R5およびR6は水素原子、ハ
ロゲン原子、炭素原子数１〜６個のアルキル
基、シクロアルキル基または炭素原子数７〜12
個のフエニルアルキル基を表わす。）
で表わされるベンゾトリアゾール誘導体、
次式（Ｃ）
（ただし式中、R7およびR8は水素原子、炭素原
子数１〜６個のアルキル基またはシクロアルキ
ル基そしてR9は炭素原子数１〜18個のアルキ
ル基、フエニル基、炭素原子数１〜６個のアル
キル置換フエニル基、ベンジル基またはアルキ
ル置換ベンジル基を表わす。）
で表わされるヒドロキシベンゾエート誘導体、
次式（Ｄ）
（ただし式中、R10は水素原子、炭素原子数１〜
12個のアルキル基またはシクロアルキル基を表
わす。）
で表わされるサリチル酸誘導体等の紫外線吸収剤
の中から選ばれた１種または２種以上と、．ピ
ペリジン誘導体として、ビス（２，２，６，６―
テトラメチル―４―ピペリジン）セバテートおよ
び次式（Ｅ），（Ｆ）および（Ｇ）
The present invention relates to a composition formulated to prevent discoloration and fading of a polymeric material containing a pigment. More specifically, the present invention relates to a polymer material composition containing a UV absorber, which is a light stabilizer, and a piperidine derivative. The purpose is to maintain the initial color tone of the polymer molded article containing the pigment. Polymer materials have excellent physical and chemical properties, making them ideal for molded products, tapes, etc.
It is consumed in large quantities for textiles, films, etc., and the demand for it is increasing year by year. These polymeric materials are characterized by the fact that they can be easily colored with pigments, dyes, etc., and when they are consumed as molded products, tapes, fibers, films, etc., they are usually colored with pigments, dyes, etc. There are many. However, pigments and paints blended into polymeric materials have the disadvantage that their color tone changes during storage and use due to sunlight, ultraviolet rays, etc., and this change in color tone impairs their commercial value. Therefore, it is extremely important industrially to prevent changes in the initial color tone of polymeric materials containing pigments, dyes, etc. Conventionally, inorganic pigments containing cadmium, lead, chromium, etc., which are known to be effective against such defects, are extremely excellent and are not easily affected by sunlight or ultraviolet rays. , chromium, etc. are harmful, and there are problems when incinerating or disposing of polymeric materials containing inorganic pigments containing cadmium, lead, chromium, etc. after use, and restrictions on their use are becoming increasingly strict. ing. The present invention replaces inorganic pigments containing cadmium, lead, chromium, etc., which have excellent discoloration and fading effects due to sunlight or ultraviolet rays, with inorganic and organic pigments, especially organic pigments, that do not contain cadmium, lead, chromium, etc. This objective is attempted to be achieved by combining and simultaneously blending a known ultraviolet absorber and a light stabilizer, which is a piperidine derivative, to counteract the discoloration and fading that occurs in such cases. A light stabilizer added to a polymeric material to prevent discoloration and fading of inorganic and organic pigments that do not contain cadmium, lead, chromium, etc. in the composition of the present invention. As a UV absorber, the following formula (A) (However, in the formula, R 1 , R 2 and R 3 are hydrogen atoms,
It represents a hydroxyl group, a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. ) A benzophenone derivative represented by the following formula (B) (However, in the formula, R 4 , R 5 and R 6 are hydrogen atoms, halogen atoms, alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups, or 7 to 12 carbon atoms.
represents a phenylalkyl group. ) A benzotriazole derivative represented by the following formula (C) (In the formula, R 7 and R 8 are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group, and R 9 is an alkyl group having 1 to 18 carbon atoms, a phenyl group, or a cycloalkyl group having 1 to 6 carbon atoms.) ~ 6 alkyl-substituted phenyl groups, benzyl groups or alkyl-substituted benzyl groups), a hydroxybenzoate derivative represented by the following formula (D) (However, in the formula, R 10 is a hydrogen atom, the number of carbon atoms is 1 to
Represents 12 alkyl or cycloalkyl groups. ) and one or more UV absorbers selected from among the ultraviolet absorbers such as salicylic acid derivatives represented by . As a piperidine derivative, bis(2,2,6,6-
Tetramethyl-4-piperidine) sebatate and the following formulas (E), (F) and (G)
【式】【formula】
（ただし式中Ｘは酸素またはイオウ原子、Ｙは
酸素原子または基＝Ｎ−R15そしてR11，R12，
R13，R14およびR15は炭素原子数１〜20個のア
ルキル基、シクロアルキル基、アルケニル基、
アラルキル基およびヒドロキシアルキル基を表
わす。）
で表わされるものの中から選ばれた１種または２
種以上とを組合せたものからなることを特徴とす
る。
式（Ａ）で表わされる化合物の例としては
1) ２，４―ジヒドロキシベンゾフエノン
2) ２―ヒドロキシ―４―メトキシベンゾフエノ
ン
3) ２―ヒドロキシ―４―ｎ―オクトキシベンゾ
フエノン
4) ２―ヒドロキシ―４―オキシベンジルベンゾ
フエノン
5) ２，2′―ジヒドロキシ―４―メトキシベンゾ
フエノン
6) ２，2′―ジヒドロキシ―４―ｎ―オクトキシ
ベンゾフエノン
7) ２，2′―ジヒドロキシ―４―4′―ジメトキベ
ンゾフエノンシ
などがある。
式（Ｂ）で示される化合物の例としては
8) ２―（2′―ヒドロキシ―5′―メチルフエニ
ル）ベンゾトリアゾール
9) ２―（2′―ヒドロキシ―3′―第三ブチル―
5′メチルフエニル）ベンゾトリアゾール
10) ２―（2′―ヒドロキシ―3′―5′―ジ―第三
ブチルフエニル）―５―クロル―ベンゾトリアゾ
ール
11) ２―（2′―ヒドロキシ―5′―第三ブチルフ
エニル）ベンゾトリアゾール
12) ２―（2′―ヒドロキシ―5′―アルミフエニ
ル）ベンゾトリアゾール
13) ２―（2′―ヒドロキシ―５―メトキシフエ
ニル）ベンゾトリアゾール
などがある。
式（Ｃ）で治示される化合物の例としては
14) （2′，4′―ジ―第三ブチルフエニル）３，
５―ジ―第三ブチル―４―ヒドロキシベンゾエー
ト
15) メチル―３―メチル―５―イソプロピル―
４―ヒドロキシベンゾエート
16) イソブチル―３，５―ジ―第三アミル―４
―ヒドロキシベンゾエート
17) フエニル―３，５―ジイソプロピル―４―
ヒドロキシベンゾエート
18) ドデシル―３―メチル―５―イソプロピル
―４―ヒドロキシベンゾエート
などがある。
式（Ｄ）で示される化合物の例としては
19) サリチル酸フエニル
20) サリチル酸―４―第二ブチルフエニル
21) サリチル酸―４―オクチルフエニル
などがある。
またピペリジン誘導体の例としては
22) ビス（２，２，６，６―テトラメチル―４
―ピペリジン）セバテート（C10―1351三共社
製）
23) ４―ベンゾイルオキシ―２，２，６，６―
テトラメチルピペリジン（サノールLS744三共社
製）
24) ４―ｎ―ブトキシ―２，２，６，６―テト
ラメチル―デヒドロピペリジン
25) ４―ｎ―オクチルオキシ―２，２，６，６
―テトラメチル―デヒドロピペリジン
26) ４―ステアリルオキシ―２，２，６，６―
テトラメチル―デヒドロピペリジン
27) ４―ベンジルオキシ―２，２，６，６―テ
トラメチル―デヒドロピペリジン
これらの光安定剤は種々の濃度で顔料に添加さ
れる。ベンゾフエノン誘導体、ベンゾトリアゾー
ル誘導体、ヒドロキシベンゾエート誘導体および
サリチル酸誘導体の中から選ばれた１種または２
種以上の紫外線吸収剤の総量100重量部に対して
ピペリジン誘導体の中から選ばれた１種または２
種以上を１種の場合は５〜300部、望ましくは20
〜100部、２種以上の場合その総計が20〜600部、
望ましくは30〜200部の濃度で配合される。この
割合が好ましい理由は５および20部未満あるいは
300部および600部以上では十分な相乗効果が認め
られないからである。
この光安定剤を組合せたものを顔料100重量部
に対して５〜200部、望ましくは10〜100部の濃度
で使用される。
高分子材料としてはポリエチレン（共重合体を
含む）、ポリプロピレン（共重合体を含む）、ポリ
スチレン、ABS樹脂、ポリ塩化ビニルなど着色
して用いる樹脂であり、その中でもエチレンのホ
モ重合体、エチレンとオレフイン、ビニルエステ
ル、アクリル酸、アクリル酸などとの共重合体、
プロピレンのホモ重合体、プロピレンとエチレ
ン、他のオレフインなどとの共重合体などのポリ
オレフインが適している。
本発明のカドミウムや鉛、クロムなどを含有し
ない無機および有機系顔料と光安定剤の高分子材
料への添加は公知の方法、たとえばミキシングロ
ール、バンバリー、ミキサー、押出機等を使用し
て容易に行なわれる。またあらかじめ高濃度のマ
スターバツチをつくり、ブレンドしても良い。さ
らに本発明では酸化安定剤、中和剤、充填剤、加
硫促進剤、滑剤、帯電防止剤、アンチブロツキン
グ剤、銅害防止剤、樹脂可塑剤等通常使用されて
いる添加剤と組合せて使用してもさしつかえな
い。
以下実施例をもつて具体的に説明するが、これ
らの実施例は本発明の理解を簡単にするものであ
つて、発明の範囲を限定するものではない。
実施例１〜４、比較例１
ポリプロピレンの粉末（住友化学、固有粘度
2.0）に第１表に示した顔料、光安定剤、ピペリ
ジン誘導体（顔料以外は前記の化合物に付した番
号で示す。）とともに押出機での樹脂の著しい劣
化を防止する目的でポリプロピレン100重量部に
対して２，６―ジ―第三ブチル―４―メチルフエ
ノール0.2重量部、ジステアリルチオジプロピネ
ート0.2重量部、ステアリン酸カルシウム0.2重量
部を加え、ヘンシエルミキサーで10分間混合し
た。この混合物をシリンダー温度220℃、L/D＝
18，30mmφの押出機によつて溶融混練して造粒し
た。このペレツトを220℃の熱プレスにより、予
熱５分、加圧５分（100Kg/cm2）、30℃の水冷プレ
スで２分間冷却して厚さ１mmのプレスシートを作
成した。このプレスシートの色度を光音製作所の
色差計で測定し、次式(1)により黄色度（YI）を
算出した。
YI＝１００（１．２８ｘ−１．０６ｚ）／ｙ (1)
（ただし、ｘ，ｙおよびｚは標準光Ｃにおける
試験片の三刺激値である。）
この値を初期の黄色度とする。またこのプレス
シートを島津製作所のウエザーテスターで500時
間照射したのち、同様な方法で黄色度を算出し
た。黄色度の値は大きいほど黄色であることを示
す。この値に3.0以上の差があれば肉眼で明らか
に識別できる。したがつて初期とウエザーテスタ
ー照射後の黄色度の差が小さいものほど色調に変
化がなかつたことになる。 ( However, in the formula ,
R 13 , R 14 and R 15 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group,
Represents an aralkyl group and a hydroxyalkyl group. ) One or two selected from the following
It is characterized by consisting of a combination of more than one species. Examples of compounds represented by formula (A) are 1) 2,4-dihydroxybenzophenone 2) 2-hydroxy-4-methoxybenzophenone 3) 2-hydroxy-4-n-octoxybenzophenone 4 ) 2-Hydroxy-4-oxybenzylbenzophenone5) 2,2'-dihydroxy-4-methoxybenzophenone6) 2,2'-dihydroxy-4-n-octoxybenzophenone7) 2,2 '-Dihydroxy-4-4'-dimethoxybenzophenone and the like. Examples of compounds represented by formula (B) include 8) 2-(2'-hydroxy-5'-methylphenyl)benzotriazole9) 2-(2'-hydroxy-3'-tert-butyl-
5'-methylphenyl)benzotriazole10) 2-(2'-hydroxy-3'-5'-di-tert-butylphenyl)-5-chloro-benzotriazole11) 2-(2'-hydroxy-5'-tert butylphenyl) benzotriazole12) 2-(2'-hydroxy-5'-alumiphenyl) benzotriazole13) 2-(2'-hydroxy-5-methoxyphenyl) benzotriazole. Examples of compounds represented by formula (C) include 14) (2',4'-di-tert-butylphenyl)3,
5-di-tert-butyl-4-hydroxybenzoate15) Methyl-3-methyl-5-isopropyl-
4-Hydroxybenzoate 16) Isobutyl-3,5-di-tertiary amyl-4
-Hydroxybenzoate17) Phenyl-3,5-diisopropyl-4-
Hydroxybenzoate 18) Examples include dodecyl-3-methyl-5-isopropyl-4-hydroxybenzoate. Examples of the compound represented by formula (D) include 19) phenyl salicylate, 20) 4-sec-butylphenyl salicylate, 21) 4-octylphenyl salicylate. Examples of piperidine derivatives include 22) bis(2,2,6,6-tetramethyl-4
-piperidine) sebatate (C10-1351 manufactured by Sankyosha) 23) 4-benzoyloxy-2,2,6,6-
Tetramethylpiperidine (Sanol LS744 manufactured by Sankyo Co., Ltd.) 24) 4-n-butoxy-2,2,6,6-tetramethyl-dehydropiperidine25) 4-n-octyloxy-2,2,6,6
-Tetramethyl-dehydropiperidine26) 4-stearyloxy-2,2,6,6-
Tetramethyl-dehydropiperidine27) 4-Benzyloxy-2,2,6,6-tetramethyl-dehydropiperidine These light stabilizers are added to the pigment in various concentrations. One or two selected from benzophenone derivatives, benzotriazole derivatives, hydroxybenzoate derivatives and salicylic acid derivatives
One or two selected from piperidine derivatives per 100 parts by weight of the total amount of UV absorbers
In the case of one or more species, 5 to 300 parts, preferably 20 parts
~100 copies, in the case of two or more types, the total is 20-600 copies,
It is preferably blended at a concentration of 30 to 200 parts. This ratio is preferable because it is less than 5 and 20 parts or
This is because a sufficient synergistic effect is not observed when the amount exceeds 300 and 600 parts. The light stabilizer combination is used in a concentration of 5 to 200 parts, preferably 10 to 100 parts per 100 parts by weight of pigment. Polymer materials include colored resins such as polyethylene (including copolymers), polypropylene (including copolymers), polystyrene, ABS resin, and polyvinyl chloride, among which ethylene homopolymers, ethylene and Olefin, vinyl ester, acrylic acid, copolymer with acrylic acid, etc.
Polyolefins such as propylene homopolymers, copolymers of propylene and ethylene, other olefins, etc. are suitable. The inorganic and organic pigments and light stabilizers that do not contain cadmium, lead, chromium, etc. of the present invention can be easily added to polymeric materials using known methods such as mixing rolls, Banbury mixers, mixers, extruders, etc. It is done. Alternatively, a highly concentrated masterbatch may be prepared in advance and blended. Furthermore, in the present invention, combinations with commonly used additives such as oxidation stabilizers, neutralizing agents, fillers, vulcanization accelerators, lubricants, antistatic agents, antiblocking agents, copper damage inhibitors, resin plasticizers, etc. It is okay to use it. The present invention will be explained in detail below using examples, but these examples are intended to simplify the understanding of the present invention and are not intended to limit the scope of the invention. Examples 1 to 4, Comparative Example 1 Polypropylene powder (Sumitomo Chemical, intrinsic viscosity
2.0), along with the pigments, light stabilizers, and piperidine derivatives shown in Table 1 (other than pigments are indicated by the numbers attached to the above compounds), 100 parts by weight of polypropylene was added for the purpose of preventing significant deterioration of the resin in the extruder. 0.2 parts by weight of 2,6-di-tert-butyl-4-methylphenol, 0.2 parts by weight of distearyl thiodipropinate, and 0.2 parts by weight of calcium stearate were added to the mixture and mixed for 10 minutes using a Henschel mixer. This mixture was heated to a cylinder temperature of 220℃, L/D=
The mixture was melt-kneaded and granulated using an extruder with a diameter of 18 and 30 mm. The pellets were preheated for 5 minutes using a hot press at 220°C, pressed for 5 minutes (100 kg/cm 2 ), and cooled for 2 minutes using a water-cooled press at 30°C to produce a pressed sheet with a thickness of 1 mm. The chromaticity of this press sheet was measured using a color difference meter manufactured by Koon Seisakusho, and the yellowness index (YI) was calculated using the following formula (1). YI=100(1.28x-1.06z)/y (1) (However, x, y, and z are the tristimulus values of the test piece in standard light C.) This value is taken as the initial yellowness. In addition, this press sheet was irradiated for 500 hours using a Shimadzu weather tester, and then the yellowness was calculated using the same method. The larger the yellowness value, the more yellow it is. If there is a difference of 3.0 or more in this value, it can be clearly identified with the naked eye. Therefore, the smaller the difference in yellowness between the initial stage and after irradiation with the weather tester, the less change in color tone.
【表】
実施例５および比較例２〜４
ポリプロピレン粉末（住友化学、固有粘度
23.0）で第２表に示した４種のベレツトを実施例
１〜９と同様な方法でそれぞれ造粒した。これら
の４種のペレツトを第３表に示したそれぞれの添
加剤の配合割合となるように加え、ヘンシエルミ
キサーで20分間混合した。[Table] Example 5 and Comparative Examples 2 to 4 Polypropylene powder (Sumitomo Chemical, intrinsic viscosity
23.0) and four types of berets shown in Table 2 were granulated in the same manner as in Examples 1 to 9. These four types of pellets were added at the mixing ratio of each additive shown in Table 3, and mixed for 20 minutes using a Henschel mixer.
【表】【table】
【表】
この混合物をシリンダー温度240℃、L/D＝24
65mmφの押出機によつて溶融混練して造粒し、実
施例１と同様な方法で厚さ１mmのプレスシートを
作製した。このプレスシートの色度を光音製作所
の色差計で測定し、次式(2)より白度（Ｗ）を算出
した。この白度を初期の白度とする。
Ｗ＝100−√（2＋2）＋（100−）２ (2)
（ただし、Ｌは明度、ａは赤―緑軸に沿つた色
度、ｂは黄―青軸に沿つた色度である。）
またこのプレスシートを鳥津製作所のウエザーテ
スターで500時間照射したのを、同様な方法で白
度を算出した。白度の値は大きいほど純白に近い
ことを示す。
いずれも実施例は比較例より色調に変化がなか
つたことを示している。[Table] This mixture was prepared at a cylinder temperature of 240℃ and L/D=24.
The mixture was melt-kneaded and granulated using a 65 mmφ extruder, and a press sheet with a thickness of 1 mm was produced in the same manner as in Example 1. The chromaticity of this press sheet was measured using a color difference meter manufactured by Koon Seisakusho, and the whiteness (W) was calculated using the following formula (2). This whiteness is taken as the initial whiteness. W=100−√( 2 + 2 )+(100−) 2 (2) (L is the lightness, a is the chromaticity along the red-green axis, and b is the chromaticity along the yellow-blue axis. ) This press sheet was irradiated for 500 hours using a weather tester manufactured by Toritsu Seisakusho, and the whiteness was calculated using the same method. The larger the whiteness value, the closer to pure white it is. All examples show that there was no change in color tone compared to the comparative example.
【表】
実施例６，７、 比較例５，６
高圧法ポリエチレン（MI；２）に第４表に示
した顔料、紫外線吸収剤、ピペリジン誘導体とと
もに混練時の劣化を防止する目的で上記ポリエチ
レン100重量部に対してオクタデシル―３―
（３，５―ジ第三ブチル―４―ヒドロキシフエニ
ル）プロピオネート0.1重量部を加え、130℃に調
整した６インチ二軸ロール（各軸の回転数は20r.
p.m又は24r.p.m）で５分間混練した。この混練
物を140℃の熱プレスにより予熱５分、加圧５分
（50Kg/cm2）、30℃の水冷プレスで２分間冷却して
厚さ１mmのプレスシートを作製した。このシート
の色度を光音製作所の色差計でＬ，ａ，ｂを測定
し、この値を初期値とする。またこのシートを鳥
津製作所のウエザーテスターで500時間照射した
後同様に色度を測定し、この時の値をL′，a′，
b′とする。これらの値から次式(1)により△Ｅを計
算した。
△Ｅ＝√（−′）2＋（−′）2＋（−′
）2(1)
△Ｅが1.5〜3.0以上の値であれば肉眼で明らか
に識別でき、この値が大きい程色調の変化が大き
いことを示す。したがつて△Ｅの小さいもの程ウ
エザーテスター照射による色調の変化のなかつた
ことを示す。
実施例８，９、 比較例７，８
エチレン―酢酸ビニル共重合体（酢酸ビニル含
量10重量％、MI；２）に第４表に示した顔料、
紫外線吸収剤、ピペリジン誘導体を実施例６と同
じ方法で混練した。ただし、ロール混練温度のみ
120℃とした。このシートを実施例６と同様の方
法で色調およびウエザーテスターで照射し△Ｅを
測定した。[Table] Examples 6 and 7, Comparative Examples 5 and 6 The above polyethylene 100 was added to high-pressure polyethylene (MI; 2) together with the pigments, ultraviolet absorbers, and piperidine derivatives shown in Table 4 for the purpose of preventing deterioration during kneading. Octadecyl-3- to parts by weight
Added 0.1 part by weight of (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and adjusted the temperature to 130°C using a 6-inch twin-shaft roll (the rotation speed of each shaft was 20 rpm).
pm or 24 r.pm) for 5 minutes. This kneaded material was preheated for 5 minutes using a hot press at 140°C, pressed for 5 minutes (50 kg/cm 2 ), and cooled for 2 minutes using a water-cooled press at 30°C to produce a pressed sheet with a thickness of 1 mm. The chromaticity L, a, and b of this sheet is measured using a color difference meter manufactured by Koon Seisakusho, and these values are used as initial values. In addition, after irradiating this sheet for 500 hours with a weather tester manufactured by Toritsu Seisakusho, the chromaticity was measured in the same way, and the values at this time were L′, a′,
Let it be b′. From these values, ΔE was calculated using the following equation (1). △E=√(-') 2 +(-') 2 +(-'
) 2 (1) If ΔE is a value of 1.5 to 3.0 or more, it can be clearly identified with the naked eye, and the larger the value, the greater the change in color tone. Therefore, a smaller ΔE indicates that there was no change in color tone due to weather tester irradiation. Examples 8 and 9, Comparative Examples 7 and 8 Pigments shown in Table 4 were added to ethylene-vinyl acetate copolymer (vinyl acetate content 10% by weight, MI: 2),
A UV absorber and a piperidine derivative were kneaded in the same manner as in Example 6. However, only the roll kneading temperature
The temperature was 120℃. This sheet was irradiated with a color tone and weather tester in the same manner as in Example 6, and ΔE was measured.
【表】【table】
Claims (1)
式（Ａ） （式中、R1，R2およびR3は水素原子、水酸基、
ハロゲン原子、炭素原子数１〜６個のアルキル
基または炭素原子数１〜12個のアルコキシ基を
表わす。） で表わされるベンゾフエノン誘導体、 次式（Ｂ） （式中、R4，R5およびR6は水素原子、ハロゲン
原子、炭素原子数１〜６個のアルキル基、シク
ロアルキル基または炭素原子数７〜12個のフエ
ニルアルキル基を表わす。） で表わされるベンゾトリアゾール誘導体、 次式（Ｃ） （式中、R7およびR8は水素原子、炭素原子数１
〜６個のアルキル基またはシクロアルキル基、
そしてR9は炭素原子数１〜18個のアルキル
基、フエニル基、炭素原子数１〜６個のアルキ
ル置換フエニル基、ベンジル基またはアルキル
置換ベンジル基を表わす。） で表わされるヒドロキシベンゾエート誘導体、 次式（Ｄ） （式中、R10は水素原子、炭素原子数１〜12個の
アルキル基またはシクロアルキル基を表わ
す。） で表わされるサリチル酸誘導体の中から選ばれた
１種または２種以上と、．ピペリジン誘導体と
して、ビス（２，２，６，６―テトラメチル―４
―ピペリジン）セバテートおよび次式（Ｅ）、
（Ｆ）および（Ｇ） 【式】 【式】 （ただし式中Ｘは酸素またはイオウ原子、Ｙは
酸素原子または基＝Ｎ−R15そしてR11，R12，
R13，R14およびR15は炭素原子数１〜20個のア
ルキル基、シクロアルキル基、アルケニル基、
アラルキル基およびヒドロキシアルキル基を表
わす。）で表わされるものの中から選ばれた１
種または２種以上とを含有してなることを特徴
とする顔料を配合したポリオレフインからなる
高分子材料組成物。[Claims] 1. As a light stabilizer, . The following formula (A) which is an ultraviolet absorber (In the formula, R 1 , R 2 and R 3 are hydrogen atoms, hydroxyl groups,
It represents a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. ) A benzophenone derivative represented by the following formula (B) (In the formula, R 4 , R 5 and R 6 represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group, or a phenylalkyl group having 7 to 12 carbon atoms.) A benzotriazole derivative represented by the following formula (C) (In the formula, R 7 and R 8 are hydrogen atoms, number of carbon atoms is 1
~6 alkyl or cycloalkyl groups,
And R9 represents an alkyl group having 1 to 18 carbon atoms, a phenyl group, an alkyl-substituted phenyl group having 1 to 6 carbon atoms, a benzyl group, or an alkyl-substituted benzyl group. ) A hydroxybenzoate derivative represented by the following formula (D) (In the formula, R 10 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group.) One or more salicylic acid derivatives selected from the following: As a piperidine derivative, bis(2,2,6,6-tetramethyl-4
-piperidine) sebatate and the following formula (E),
(F) and (G) [Formula] [Formula] ( However, in the formula ,
R 13 , R 14 and R 15 are an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an alkenyl group,
Represents an aralkyl group and a hydroxyalkyl group. ) selected from among those represented by
A polymeric material composition comprising a polyolefin blended with a pigment characterized by containing one or more pigments.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10963581A JPS57119941A (en) | 1981-07-13 | 1981-07-13 | Polymeric material composition containing pigment and stabilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10963581A JPS57119941A (en) | 1981-07-13 | 1981-07-13 | Polymeric material composition containing pigment and stabilizer |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1055874A Division JPS5724372B2 (en) | 1974-01-23 | 1974-01-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57119941A JPS57119941A (en) | 1982-07-26 |
| JPS6138940B2 true JPS6138940B2 (en) | 1986-09-01 |
Family
ID=14515271
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10963581A Granted JPS57119941A (en) | 1981-07-13 | 1981-07-13 | Polymeric material composition containing pigment and stabilizer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57119941A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63132505A (en) * | 1986-11-24 | 1988-06-04 | Mitsubishi Electric Corp | Semiconductor device |
| JP2010529245A (en) * | 2007-06-06 | 2010-08-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Less dusty additives and pigment blends with improved color |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62236861A (en) * | 1986-04-09 | 1987-10-16 | Maruyama Kogyo Kk | Resin composition and awning sheet |
| US4983653A (en) * | 1986-11-12 | 1991-01-08 | Diafoil Company, Ltd. | Polyester shrinkable film containing benzotriazole |
| JPS63125545A (en) * | 1986-11-14 | 1988-05-28 | Sekisui Chem Co Ltd | Colored olefin resin composition |
| JPH0621234B2 (en) * | 1987-03-25 | 1994-03-23 | 大日精化工業株式会社 | Pigment composition and method for producing the same |
| JPH0621233B2 (en) * | 1987-03-25 | 1994-03-23 | 大日精化工業株式会社 | Pigment composition and method for producing the same |
| JP2710321B2 (en) * | 1987-12-28 | 1998-02-10 | 電気化学工業株式会社 | Resin composition with excellent weather resistance |
| JPH0246436U (en) * | 1988-09-27 | 1990-03-29 | ||
| JP2731660B2 (en) * | 1992-03-02 | 1998-03-25 | ポリプラスチックス株式会社 | Light discoloration resistant polyarylene sulfide resin composition |
| EP0559611B1 (en) * | 1992-03-05 | 1999-11-17 | Ciba SC Holding AG | Stabilization of pyrrolopyrrolpigments |
| EP0559613B1 (en) * | 1992-03-05 | 1999-12-15 | Ciba SC Holding AG | Stabilization of organic pigments |
| TW237471B (en) * | 1992-09-03 | 1995-01-01 | Ciba Geigy | |
| US5816238A (en) * | 1994-11-28 | 1998-10-06 | Minnesota Mining And Manufacturing Company | Durable fluorescent solar collectors |
| AU700888B2 (en) * | 1994-11-28 | 1999-01-14 | Minnesota Mining And Manufacturing Company | Articles exhibiting durable colour and/or fluorescent properties |
| US5700077A (en) * | 1995-03-23 | 1997-12-23 | Minnesota Mining And Manufacturing Company | Line light source including fluorescent colorant |
| US20060122293A1 (en) * | 2004-12-03 | 2006-06-08 | Rick Wilk | Ultraviolet light absorber stabilizer combination |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5058141A (en) * | 1973-06-09 | 1975-05-20 | ||
| JPS5858141A (en) * | 1981-09-30 | 1983-04-06 | Fukubi Kagaku Kogyo Kk | Apparatus for molding flexible graphite particle |
-
1981
- 1981-07-13 JP JP10963581A patent/JPS57119941A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5058141A (en) * | 1973-06-09 | 1975-05-20 | ||
| JPS5858141A (en) * | 1981-09-30 | 1983-04-06 | Fukubi Kagaku Kogyo Kk | Apparatus for molding flexible graphite particle |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63132505A (en) * | 1986-11-24 | 1988-06-04 | Mitsubishi Electric Corp | Semiconductor device |
| JP2010529245A (en) * | 2007-06-06 | 2010-08-26 | ビーエーエスエフ ソシエタス・ヨーロピア | Less dusty additives and pigment blends with improved color |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57119941A (en) | 1982-07-26 |
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