JPH04359942A - Fluorescent-colored polypropylene resin composition - Google Patents
Fluorescent-colored polypropylene resin compositionInfo
- Publication number
- JPH04359942A JPH04359942A JP16086591A JP16086591A JPH04359942A JP H04359942 A JPH04359942 A JP H04359942A JP 16086591 A JP16086591 A JP 16086591A JP 16086591 A JP16086591 A JP 16086591A JP H04359942 A JPH04359942 A JP H04359942A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- parts
- polypropylene resin
- compd
- fluorescent
- 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
- -1 polypropylene Polymers 0.000 title claims abstract description 58
- 239000004743 Polypropylene Substances 0.000 title claims description 33
- 229920001155 polypropylene Polymers 0.000 title claims description 33
- 239000011342 resin composition Substances 0.000 title claims description 10
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000011347 resin Substances 0.000 claims abstract description 37
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims abstract description 9
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012965 benzophenone Substances 0.000 claims abstract description 5
- 239000012964 benzotriazole Substances 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000007850 fluorescent dye Substances 0.000 claims description 10
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical group OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001558 benzoic acid derivatives Chemical class 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 abstract description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 abstract description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 abstract description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 2
- 150000003254 radicals Chemical class 0.000 abstract 1
- 238000000034 method Methods 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 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 3
- 239000003381 stabilizer Substances 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229920001384 propylene homopolymer Polymers 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- WTJWFFXZUSGGKB-UHFFFAOYSA-N (4-octoxyphenyl)-phenylmethanone Chemical compound C1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 WTJWFFXZUSGGKB-UHFFFAOYSA-N 0.000 description 1
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 description 1
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical group CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005653 propylene-ethylene copolymer Polymers 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は蛍光色に着色され、且つ
耐候性が良好なポリプロピレン樹脂組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polypropylene resin composition that is fluorescently colored and has good weather resistance.
【０００２】0002
【従来の技術】ポリプロピレン樹脂は成形性が優れ、且
つ機械的強度、耐熱性、耐薬品性が優れ、又、吸湿性が
無く、しかも他樹脂に較べ安価で軽量であることから広
く家電部品や自動車部品、雑貨等に使用されている。[Prior Art] Polypropylene resin has excellent moldability, excellent mechanical strength, heat resistance, and chemical resistance. It is also non-hygroscopic, and is cheaper and lighter than other resins, so it is widely used in home appliance parts. Used in automobile parts, miscellaneous goods, etc.
【０００３】これら用途において、外観を向上させ、商
品価値を上げる為に各種顔料による着色が成されている
。更に、より鮮やかな外観を得る為には蛍光色の着色が
考えられる。蛍光を発する樹脂を得る為には蛍光染料の
樹脂への添加が考えられる。しかしながら、ポリプロピ
レン樹脂は可染性が悪く、鮮やかな外観が得られないこ
と、及び、長期使用で染料の浮き出しが生じる等の問題
がある。又、一般に蛍光染料は通常の樹脂用顔料と併用
されることが多く、この場合にはその樹脂成形品の外観
はあまり鮮やかにはならない。[0003] In these uses, coloring with various pigments is performed to improve the appearance and increase the commercial value. Furthermore, in order to obtain a more vivid appearance, fluorescent coloring may be considered. In order to obtain a resin that emits fluorescence, it is possible to add a fluorescent dye to the resin. However, polypropylene resin has problems such as poor dyeability, failure to obtain a vivid appearance, and dye embossment after long-term use. Furthermore, fluorescent dyes are generally used in combination with ordinary pigments for resins, and in this case, the appearance of the resin molded product is not very bright.
【０００４】又、蛍光染料のみで着色した場合には、耐
候性が大幅に低下する為、戸外で使用する部品等への適
用が出来ない。即ち、非常に優れた蛍光色を有し、且つ
、耐候性が良好で、あらゆる用途に適合するポリプロピ
レン樹脂が無いのが現状である。[0004] Furthermore, when colored only with a fluorescent dye, the weather resistance is significantly reduced, so that it cannot be applied to parts to be used outdoors. That is, at present, there is no polypropylene resin that has excellent fluorescent color, good weather resistance, and is suitable for all kinds of uses.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、上記
問題を解決すること、即ち非常に優れた蛍光色を有し、
耐候性が良好であり、あらゆる用途に適合するポリプロ
ピレン樹脂組成物を提供することである。OBJECTS OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, that is, to have an extremely excellent fluorescent color,
An object of the present invention is to provide a polypropylene resin composition that has good weather resistance and is suitable for all kinds of uses.
【０００６】[0006]
【課題を解決するための手段】本発明者等は上記欠点を
解消し、非常に優れた蛍光色を有し、且つ、耐候性が良
好であるポリプロピレン樹脂組成物を得るべく鋭意検討
を重ねた結果、ポリプロピレン樹脂に（ａ）ペリレン系
蛍光化合物、（ｂ）ベンゾトリアゾール系化合物、ベン
ゾエート系化合物及びベンゾフェノン系化合物からなる
群から選ばれた少なくとも一種類、及び（ｃ）ラジカル
重合性不飽和化合物をグラフト重合させたポリプロピレ
ン樹脂を添加した組成物が、これらの要求性能を満たす
ことを見出し本発明に到達した。[Means for Solving the Problems] The present inventors have made extensive studies to eliminate the above-mentioned drawbacks and to obtain a polypropylene resin composition that has an extremely excellent fluorescent color and good weather resistance. As a result, at least one type selected from the group consisting of (a) a perylene-based fluorescent compound, (b) a benzotriazole-based compound, a benzoate-based compound, and a benzophenone-based compound, and (c) a radically polymerizable unsaturated compound were added to the polypropylene resin. The present invention was achieved by discovering that a composition containing a graft-polymerized polypropylene resin satisfies these required performances.
【０００７】即ち、本発明は、ポリプロピレン樹脂１０
０重量部に対して、（ａ）ペリレン系蛍光化合物を０．
００１〜１．０重量部、（ｂ）ベンゾトリアゾール系化
合物、ベンゾエート系化合物及びベンゾフェノン系化合
物からなる群から選ばれた少なくとも一種類を０．０１
〜１．０重量部、及び（ｃ）ラジカル重合性不飽和化合
物をグラフト重合させたポリプロピレン樹脂を０．０１
〜５．０重量部添加したことを特徴とするポリプロピレ
ン樹脂組成物である。That is, the present invention provides polypropylene resin 10
(a) perylene-based fluorescent compound to 0 parts by weight.
(b) 0.01 to 1.0 parts by weight of at least one selected from the group consisting of benzotriazole compounds, benzoate compounds, and benzophenone compounds;
~1.0 parts by weight, and (c) 0.01 parts of polypropylene resin graft-polymerized with a radically polymerizable unsaturated compound.
This is a polypropylene resin composition characterized in that ~5.0 parts by weight is added.
【０００８】本発明で用いるポリプロピレン樹脂はプロ
ピレンホモポリマー、プロピレン−エチレン共重合体、
プロピレン−α−オレフィン共重合体、エチレン−プロ
ピレン−α−オレフィン共重合体等のいずれでもよく、
これらの共重合体はいかなる製造方法によって得られた
ものでもよく、ランダム共重合体であってもブロック共
重合体であってもよい。本発明においては、特に、プロ
ピレン−エチレンブロック共重合体を用いると本発明の
樹脂組成物の蛍光が特に鮮やかになり、好ましい結果を
与える。このプロピレン−エチレンブロック共重合体は
例えばプロピレンのホモ重合の後にプロピレンとエチレ
ンを種々の比率で共重合させる公知の方法で製造された
ものでよく、市販されているいずれのプロピレン−エチ
レンブロック共重合体も使用できる。The polypropylene resin used in the present invention is a propylene homopolymer, a propylene-ethylene copolymer,
Any of propylene-α-olefin copolymers, ethylene-propylene-α-olefin copolymers, etc. may be used,
These copolymers may be obtained by any production method, and may be random copolymers or block copolymers. In the present invention, in particular, when a propylene-ethylene block copolymer is used, the fluorescence of the resin composition of the present invention becomes particularly bright, giving preferable results. This propylene-ethylene block copolymer may be produced, for example, by a known method of homopolymerizing propylene and then copolymerizing propylene and ethylene in various ratios, and may be any commercially available propylene-ethylene block copolymer. Combination can also be used.
【０００９】本発明で用いるペリレン系蛍光化合物は公
知のいかなるペリレン系蛍光化合物であってよく、例え
ば下記の一般式で表される化合物：The perylene-based fluorescent compound used in the present invention may be any known perylene-based fluorescent compound, such as a compound represented by the following general formula:
【００１０】0010
【化１】
（式中、Ｒ１ はそれぞれ水素原子、アルキル基、アル
コキシ基、Ｃ１ 〜Ｃ１０アルキルチオハロゲン、特に
Ｃｌ 、Ｂｒ 又はＦ及び／又はシアノ基で置換された
Ｃ１ 〜Ｃ１８アルキル基、２、６−ジイソプロピルベ
ンゼン基、Ｒ２ 〜Ｒ５ はそれぞれハロゲン原子、ア
ルコキシ基、フェノキシ基であり、ａ＋ｂ＋ｃ＋ｄ＝０
〜５であり、Ｒ６ 及びＲ７は水素原子、ハロゲン原子
、低級アルキル基又は低級アルコキシ基である）、具体
的には或いは特開昭５８−４０３５９号公報に開示され
ているペリレン系蛍光化合物がある。[Formula 1] (wherein R1 is a hydrogen atom, an alkyl group, an alkoxy group, a C1-C10 alkylthiohalogen, in particular a C1-C18 alkyl group substituted with Cl, Br or F and/or a cyano group, 2, 6 -diisopropylbenzene group, R2 to R5 are each a halogen atom, an alkoxy group, and a phenoxy group, a+b+c+d=0
-5, and R6 and R7 are a hydrogen atom, a halogen atom, a lower alkyl group, or a lower alkoxy group), or specifically, perylene-based fluorescent compounds disclosed in JP-A-58-40359. .
【００１１】これらのペリレン系蛍光化合物の添加量は
ポリプロピレン樹脂１００重量部に対して０．００１〜
１．０重量部、好ましくは０．１〜０．７重量部である
。０．００１重量部未満で使用した場合には、良好な蛍
光を発する製品が得られない。又、１．０重量部を越え
て使用した場合にその効果はその使用量に比例して改良
されるものではなく、コスト高になるのみで好ましくな
い。[0011] The amount of these perylene fluorescent compounds added is 0.001 to 100 parts by weight of the polypropylene resin.
The amount is 1.0 parts by weight, preferably 0.1 to 0.7 parts by weight. If less than 0.001 part by weight is used, a product that emits good fluorescence cannot be obtained. Moreover, if more than 1.0 parts by weight is used, the effect will not be improved in proportion to the amount used, and the cost will only increase, which is not preferable.
【００１２】本発明で用いることのできるベンゾトリア
ゾール系化合物の添加量はポリプロピレン樹脂１００重
量部に対して０．０１〜１．０重量部、好ましくは０．
０５〜０．６重量部である。０．０１重量部未満では耐
候性の改良効果が不充分であり、又、１．０重量部を越
えて使用した場合にその効果はその使用量に比例して改
良されるものではなく、コスト高になり、又、成形品に
浮き出しが生じる等の問題がある。本発明で用いるベン
ゾトリアゾール系化合物としては特に２−（３−ｔ−ブ
チル−５−メチル−２−ヒドロキシフェニル）−５−ク
ロロベンゾトリアゾールが好ましい。The amount of the benzotriazole compound that can be used in the present invention is 0.01 to 1.0 parts by weight, preferably 0.01 to 1.0 parts by weight, per 100 parts by weight of the polypropylene resin.
05 to 0.6 parts by weight. If it is less than 0.01 part by weight, the effect of improving weather resistance is insufficient, and if it is used in excess of 1.0 part by weight, the effect will not be improved in proportion to the amount used, and the cost will increase. There are also problems such as the height of the molded product and the occurrence of embossment on the molded product. As the benzotriazole compound used in the present invention, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole is particularly preferred.
【００１３】本発明で用いることのできるベンゾエート
系化合物の添加量はポリプロピレン樹脂１００重量部に
対して０．０１〜１．０重量部、好ましくは０．０５〜
０．６重量部である。０．０１重量部未満では耐候性の
改良効果が不充分であり、又、１．０重量部を越えて使
用した場合にその効果はその使用量に比例して改良され
るものではなく、コスト高になり、又、成形品に浮き出
しが生じる等の問題がある。本発明で用いるベンゾエー
ト系化合物としては特に２，４−ジ−ｔ−ブチル−フェ
ニル−３′，５′−ジ−ｔ−ブチル−４′−ヒドロキシ
−ベンゾエートが好ましい。The amount of the benzoate compound that can be used in the present invention is 0.01 to 1.0 parts by weight, preferably 0.05 to 1.0 parts by weight, per 100 parts by weight of the polypropylene resin.
It is 0.6 part by weight. If it is less than 0.01 part by weight, the effect of improving weather resistance is insufficient, and if it is used in excess of 1.0 part by weight, the effect will not be improved in proportion to the amount used, and the cost will increase. There are also problems such as the height of the molded product and the occurrence of embossment on the molded product. As the benzoate compound used in the present invention, 2,4-di-t-butyl-phenyl-3',5'-di-t-butyl-4'-hydroxy-benzoate is particularly preferred.
【００１４】本発明で用いることのできるベンゾフェノ
ン系化合物の添加量はポリプロピレン樹脂１００重量部
に対して０．０１〜１．０重量部、好ましくは０．０５
〜０．６重量部である。０．０１重量部未満では耐候性
の改良効果が不充分であり、又、１．０重量部を越えて
使用した場合にその効果はその使用量に比例して改良さ
れるものではなく、コスト高になり、又、成形品に浮き
出しが生じる等の問題がある。本発明で用いるベンゾフ
ェノン系化合物としては特に２−ヒドロキシ−４−オク
トキシ−ベンゾフェノンが好ましい。The amount of the benzophenone compound that can be used in the present invention is 0.01 to 1.0 parts by weight, preferably 0.05 parts by weight, based on 100 parts by weight of the polypropylene resin.
~0.6 part by weight. If it is less than 0.01 part by weight, the effect of improving weather resistance is insufficient, and if it is used in excess of 1.0 part by weight, the effect will not be improved in proportion to the amount used, and the cost will increase. There are also problems such as the height of the molded product and the occurrence of embossment on the molded product. As the benzophenone compound used in the present invention, 2-hydroxy-4-octoxy-benzophenone is particularly preferred.
【００１５】本発明で用いるグラフト化ポリプロピレン
樹脂は、結晶性ポリプロピレン樹脂に有機過酸化物触媒
によりラジカル重合性不飽和化合物をグラフト重合させ
る公知の方法、例えば上記反応を有機溶媒中で行う方法
、同様に押出機中で行う方法などで製造できる。ここに
使用する結晶性ポリプロピレン樹脂としては主要構成部
分がポリプロピレン樹脂であり且つ結晶性を有するもの
であれば良い。また炭化水素溶媒は、芳香族炭化水素、
アルキル芳香族炭化水素、ハロゲン化芳香族炭化水素、
脂肪族炭化水素、脂環式炭化水素、ハロゲン化脂肪族炭
化水素等である。The grafted polypropylene resin used in the present invention can be obtained by a known method of graft polymerizing a radically polymerizable unsaturated compound onto a crystalline polypropylene resin using an organic peroxide catalyst, such as a method in which the above reaction is carried out in an organic solvent. It can be manufactured in a method such as in an extruder. The crystalline polypropylene resin used here may be any resin as long as its main component is a polypropylene resin and has crystallinity. Hydrocarbon solvents include aromatic hydrocarbons,
Alkyl aromatic hydrocarbons, halogenated aromatic hydrocarbons,
These include aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated aliphatic hydrocarbons, and the like.
【００１６】グラフト重合の際に使用する有機過酸化物
としては通常のラジカル重合に使用されるものはいずれ
でも使用出来る。又、ラジカル重合性不飽和化合物とし
ては、α、β−不飽和脂肪族モノカルボン酸およびその
誘導体、α、β−不飽和脂肪族ジカルボン酸およびその
誘導体、アルケニルベンゼンおよびその誘導体、アルケ
ニルピリジンおよびその誘導体、α−オレフィン等が上
げられ、これらは単独で、あるいは２種以上混合して用
いることが出来る。これらラジカル重合性不飽和化合物
の使用量は結晶性ポリプロピレン樹脂１００重量部に対
して０．０１〜５．０重量部、好ましくは０．５〜３．
０重量部の範囲で使用される。[0016] As the organic peroxide used in graft polymerization, any organic peroxide used in ordinary radical polymerization can be used. In addition, as radically polymerizable unsaturated compounds, α,β-unsaturated aliphatic monocarboxylic acids and their derivatives, α,β-unsaturated aliphatic dicarboxylic acids and their derivatives, alkenylbenzenes and their derivatives, alkenylpyridines and their derivatives, etc. Examples include derivatives, α-olefins, etc., and these can be used alone or in combination of two or more. The amount of these radically polymerizable unsaturated compounds used is 0.01 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, per 100 parts by weight of the crystalline polypropylene resin.
It is used in a range of 0 parts by weight.
【００１７】本発明で用いるグラフト化ポリプロピレン
樹脂はポリプロピレン樹脂１００重量部に対して０．０
１〜５．０重量部、好ましくは０．５〜３．０重量部で
ある。０．０１重量％未満では可染性が悪く、又５．０
重量％を越えて添加しても効果はそれ程向上せず、コス
ト高になる。The grafted polypropylene resin used in the present invention is 0.0 parts by weight per 100 parts by weight of the polypropylene resin.
The amount is 1 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight. If it is less than 0.01% by weight, dyeability is poor;
Even if it is added in excess of this weight percent, the effect will not improve much and the cost will increase.
【００１８】尚、本発明の効果を損なわない範囲で、他
の熱可塑性樹脂、ゴム、無機充填剤を混合してもよい。
更に必要に応じて、ポリプロピレン樹脂に一般に用いら
れている熱安定剤、滑剤、中和剤、帯電防止剤、結晶核
剤等を添加してもよい。しかしながら上記各種安定剤の
なかには、蛍光色を阻害する化合物が多く、とりわけヒ
ンダードフェノール系熱安定剤にその傾向がつよいので
、それらの使用は避けることが望ましい。。Note that other thermoplastic resins, rubbers, and inorganic fillers may be mixed as long as the effects of the present invention are not impaired. Furthermore, if necessary, heat stabilizers, lubricants, neutralizing agents, antistatic agents, crystal nucleating agents, etc. commonly used for polypropylene resins may be added. However, among the above-mentioned various stabilizers, there are many compounds that inhibit fluorescent color, and hindered phenol heat stabilizers in particular have this tendency, so it is desirable to avoid their use. .
【００１９】本発明の組成物は、ポリプロピレン樹脂を
造粒する一般的方法を用いて製造することが出来る。即
ち、所定量をヘンシェルミキサー、リボンブレンダー、
ドラムブレンダー等で混合し、更にスクリュー型押出機
等を用いて溶融混練して製造することができる。この溶
融混練は一般に１７０〜３００℃で実施される。The composition of the present invention can be manufactured using a conventional method of granulating polypropylene resin. That is, a predetermined amount is mixed with a Henschel mixer, a ribbon blender,
It can be produced by mixing with a drum blender or the like and then melt-kneading using a screw extruder or the like. This melt-kneading is generally carried out at 170-300°C.
【００２０】本発明の組成物を用い、射出成形、吹込成
形、シート成形、フィルム成形等の既存の成形法を用い
て製品を得ることができる。[0020] Using the composition of the present invention, products can be obtained using existing molding methods such as injection molding, blow molding, sheet molding, and film molding.
【００２１】[0021]
【実施例】以下、実施例にて本発明を更に詳細に説明す
る。[Examples] The present invention will be explained in more detail with reference to Examples below.
【００２２】実施例１
プロピレン−エチレンブロック共重合体（三井東圧化学
社製“三井ノーブレンＢＪＳ”、ＭＩ＝１．５ｇ／１０
ｍｉｎ ）１００重量部に、ペリレン系蛍光化合物であ
るルモゲン（Ｌｕｍｏｇｅｎ） Ｆ Ｒｅｄ ３００
（ＢＡＳＦ製製）０．０５重量部、２−（３−ｔ−ブチ
ル−５−メチル−２−ヒドロキシフェニル）−５−クロ
ロベンゾトリアゾール０．３重量部、無水マレイン酸グ
ラフトポリプロピレン（無水マレイン酸グラフト率１０
％）２．０重量部、ステアリン酸カルシウム０．１重量
部及びテトラキス（２，４−ジ−ｔ−ブチルフェニル）
４，４′−ビフェニレンジホスホネート０．０５重量部
をヘンシェルミキサーにて混合し、この混合物をスクリ
ュー型押出機にて２４０℃の樹脂温度で溶融混練し、次
いで造粒した。このペレットから１００トンの型締力を
有する射出成形機を用いて長さ１７０ｍｍ、幅８０ｍｍ
、厚み２ｍｍのシートを製造した。この際の樹脂温度は
２３０℃であり、金型温度は５０℃であった。Example 1 Propylene-ethylene block copolymer (“Mitsui Noblen BJS” manufactured by Mitsui Toatsu Chemical Co., Ltd., MI = 1.5 g/10
Lumogen F Red 300, a perylene-based fluorescent compound, is added to 100 parts by weight (min) of 100 parts by weight.
(manufactured by BASF) 0.05 parts by weight, 0.3 parts by weight of 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, maleic anhydride grafted polypropylene (maleic anhydride) Graft rate 10
%) 2.0 parts by weight, 0.1 parts by weight of calcium stearate and tetrakis (2,4-di-t-butylphenyl)
0.05 parts by weight of 4,4'-biphenylene diphosphonate was mixed in a Henschel mixer, the mixture was melt-kneaded in a screw extruder at a resin temperature of 240°C, and then granulated. Using an injection molding machine with a mold clamping force of 100 tons, this pellet is molded into a product with a length of 170 mm and a width of 80 mm.
, a sheet with a thickness of 2 mm was manufactured. The resin temperature at this time was 230°C, and the mold temperature was 50°C.
【００２３】製造されたシートの蛍光性能について目視
をもって評価を行った。目視による評価の評点は下記に
よる：
◎：製品が蛍光を発して極めて鮮やかである、○：製品
が蛍光を発して鮮やかである、△：製品がある程度蛍光
を発している、×：製品が蛍光を発していない。The fluorescent performance of the produced sheet was visually evaluated. The visual evaluation is based on the following: ◎: The product emits fluorescence and is extremely bright, ○: The product emits fluorescence and is bright, △: The product emits some fluorescence, ×: The product is fluorescent. is not emitted.
【００２４】又、同様に製造されたシートの蛍光性能を
光沢を測定して評価した。光沢の測定はＡＳＴＭ Ｄ
−５２３に準じて行った。その結果を表１に示す。[0024]Furthermore, the fluorescent performance of the sheet produced in the same manner was evaluated by measuring the gloss. Gloss measurement is ASTM D
-523. The results are shown in Table 1.
【００２５】製造されたシートの耐候性について、サン
シャインウェザーメーターにて評価を行った。暴露条件
は６３℃、１８分／２時間の降雨であった。シート表面
にチョーキングが生じる時間を耐候時間とした。その結
果を表１に示す。The weather resistance of the produced sheet was evaluated using a sunshine weather meter. The exposure conditions were 63°C and 18 minutes/2 hours of rain. The time during which chalking occurred on the sheet surface was defined as the weathering time. The results are shown in Table 1.
【００２６】製造されたシートの染色性についてガソリ
ン浸漬による蛍光化合物の浮き出しを目視により観察す
ることにより評価した。浸漬条件は１０分間で、ガソリ
ンの着色の度合により下記にて評点をつけた：○：ガソ
リンの着色無し、
△：ガソリンの着色わずかに有り、
×：ガソリンの着色有り。
その結果を表１に示す。The dyeability of the produced sheet was evaluated by visually observing the embossment of the fluorescent compound due to immersion in gasoline. The immersion conditions were 10 minutes, and the following ratings were given according to the degree of coloration of the gasoline: ○: No coloration of gasoline, △: Slight coloration of gasoline, ×: Coloration of gasoline. The results are shown in Table 1.
【００２７】実施例２
実施例１の方法において、２−（３−ｔ−ブチル−５−
メチル−２−ヒドロキシフェニル）−５−クロロベンゾ
トリアゾール０．３重量部の代わりに２，４−ジ−ｔ−
ブチル−フェニル−３′，５′−ジ−ｔ−ブチル−４′
−ヒドロキシ−ベンゾエート０．３重量部を添加し、他
は実施例１と同様に実施して評価を行った。その結果を
表１に示す。Example 2 In the method of Example 1, 2-(3-t-butyl-5-
2,4-di-t-instead of 0.3 parts by weight of methyl-2-hydroxyphenyl)-5-chlorobenzotriazole
Butyl-phenyl-3',5'-di-t-butyl-4'
Evaluation was carried out in the same manner as in Example 1 except that 0.3 parts by weight of -hydroxy-benzoate was added. The results are shown in Table 1.
【００２８】実施例３
実施例１の方法において、２−（３−ｔ−ブチル−５−
メチル−２−ヒドロキシフェニル）−５−クロロベンゾ
トリアゾール０．３重量部の代わりに２−ヒドロキシ−
４−オクトキシ−ベンゾフェノン０．３重量部を添加し
て、他は実施例１と同様に実施して評価を行った。その
結果を表１に示す。Example 3 In the method of Example 1, 2-(3-t-butyl-5-
2-hydroxy- in place of 0.3 parts by weight of methyl-2-hydroxyphenyl)-5-chlorobenzotriazole
Evaluation was carried out in the same manner as in Example 1 except that 0.3 parts by weight of 4-octoxy-benzophenone was added. The results are shown in Table 1.
【００２９】実施例４
実施例１の方法において、更に２，４−ジ−ｔ−ブチル
−フェニル−３′，５′−ジ−ｔ−ブチル−４′−ヒド
ロキシ−ベンゾエート０．３重量部を添加し、他は実施
例１同様に実施して評価を行った。その結果を表１に示
す。Example 4 In the method of Example 1, 0.3 parts by weight of 2,4-di-t-butyl-phenyl-3',5'-di-t-butyl-4'-hydroxy-benzoate was added. The evaluation was carried out in the same manner as in Example 1 except for the following. The results are shown in Table 1.
【００３０】実施例５
実施例４の方法において、更に２−ヒドロキシ−４−オ
クトキシ−ベンゾフェノン０．３重量部を添加し、他は
実施例１同様に実施して評価を行った。その結果を表１
に示す。Example 5 Evaluation was carried out in the same manner as in Example 1 except that 0.3 parts by weight of 2-hydroxy-4-octoxy-benzophenone was added in the same manner as in Example 4. Table 1 shows the results.
Shown below.
【００３１】実施例６
実施例１の方法において、プロピレン−エチレンブロッ
ク共重合体の代わりにプロピレンホモポリマー（三井東
圧化学社製“三井ノーブレンＪＨＨ”、ＭＩ＝８．０ｇ
／１０ｍｉｎ ）を使用し、他は実施例１と同様に実施
して評価を行った。その結果を表１に示す。Example 6 In the method of Example 1, propylene homopolymer ("Mitsui Noblen JHH" manufactured by Mitsui Toatsu Chemical Co., Ltd., MI = 8.0 g) was used instead of the propylene-ethylene block copolymer.
/10min), and the other conditions were the same as in Example 1 for evaluation. The results are shown in Table 1.
【００３２】実施例７
実施例１の方法において、プロピレン−エチレンブロッ
ク共重合体の代わりにプロピレン−エチレンランダム共
重合体（三井東圧化学社製“三井ノーブレンＭＦＬ”、
ＭＩ＝８．０ｇ／１０ｍｉｎ 、エチレン含有率３．１
重量％）を使用し、他は実施例１と同様に実施して評価
を行った。その結果を表１に示す。Example 7 In the method of Example 1, a propylene-ethylene random copolymer (“Mitsui Noblen MFL” manufactured by Mitsui Toatsu Chemical Co., Ltd.) was used instead of the propylene-ethylene block copolymer.
MI=8.0g/10min, ethylene content 3.1
Weight %) was used, and the evaluation was carried out in the same manner as in Example 1 except for the following. The results are shown in Table 1.
【００３３】比較例１
実施例１の方法において、無水マレイン酸グラフトポリ
プロピレンを添加しなかった以外は実施例１同様に実施
して評価を行った。その結果を表２に示す。Comparative Example 1 Evaluation was carried out in the same manner as in Example 1 except that maleic anhydride grafted polypropylene was not added. The results are shown in Table 2.
【００３４】比較例２
実施例１の方法において、使用した安定剤である２−（
３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル
）−５−クロロベンゾトリアゾール及びテトラキス（２
，４−ジ−ｔ−ブチルフェニル）４，４′−ビフェニレ
ンジホスホネートに代えて、ペンタエリシリチル〔３−
（３，５−ジターシャリ−ブチル−４−ヒドロキシフェ
ニル）プロピオネート〕（チバガイギー社製１０１０）
を０．２重量部使用し、他は実施例１同様に実施して評
価を行った。その結果を表２に示す。Comparative Example 2 In the method of Example 1, the stabilizer 2-(
3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and tetrakis(2
, 4-di-t-butylphenyl) 4,4'-biphenylene diphosphonate, pentaerysilithyl [3-
(3,5-ditertiary-butyl-4-hydroxyphenyl)propionate (1010 manufactured by Ciba Geigy)
Evaluation was conducted in the same manner as in Example 1 except that 0.2 parts by weight of . The results are shown in Table 2.
【００３５】比較例３
実施例１の方法において、使用した安定剤である２−（
３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル
）−５−クロロベンゾトリアゾール及びテトラキス（２
，４−ジ−ｔ−ブチルフェニル）４，４′−ビフェニレ
ンジホスホネートに代えて、２，６−ジターシャリーブ
チルクレゾール０．２重量部使用し、他は実施例１同様
に実施して評価を行った。その結果を表２に示す。Comparative Example 3 In the method of Example 1, the stabilizer 2-(
3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and tetrakis(2
, 4-di-t-butylphenyl) 4,4'-biphenylene diphosphonate, 0.2 parts by weight of 2,6-ditertiary butyl cresol was used, and the evaluation was carried out in the same manner as in Example 1, except that went. The results are shown in Table 2.
【００３６】[0036]
【表１】[Table 1]
【００３７】[0037]
【表２】[Table 2]
【００３８】[0038]
【発明の効果】以上に説明したように、本発明のポリプ
ロピレン樹脂組成物は非常に優れた蛍光色を有し、耐候
性が良好であり、従ってあらゆる用途に適合する。As explained above, the polypropylene resin composition of the present invention has an excellent fluorescent color and good weather resistance, and is therefore suitable for all kinds of uses.
Claims (4)
して、（ａ）ペリレン系蛍光化合物を０．００１〜１．
０重量部、（ｂ）ベンゾトリアゾール系化合物、ベンゾ
エート系化合物及びベンゾフェノン系化合物からなる群
から選ばれた少なくとも一種類を０．０１〜１．０重量
部、及び（ｃ）ラジカル重合性不飽和化合物をグラフト
重合させたポリプロピレン樹脂を０．０１〜５．０重量
部添加したことを特徴とするポリプロピレン樹脂組成物
。1. Perylene-based fluorescent compound (a) is added in an amount of 0.001 to 1.0 parts by weight per 100 parts by weight of polypropylene resin.
0 parts by weight, (b) 0.01 to 1.0 parts by weight of at least one selected from the group consisting of benzotriazole compounds, benzoate compounds, and benzophenone compounds, and (c) a radically polymerizable unsaturated compound. A polypropylene resin composition characterized in that 0.01 to 5.0 parts by weight of a polypropylene resin graft-polymerized is added.
２−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフ
ェニル）−５−クロロベンゾトリアゾールであることを
特徴とする請求項１記載のポリプロピレン樹脂組成物。2. The polypropylene resin according to claim 1, wherein the benzotriazole compound is 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole. Composition.
ジ−ｔ−ブチル−フェニル−３′，５′−ジ−ｔ−ブチ
ル−４′−ヒドロキシ−ベンゾエートであることを特徴
とする請求項１記載のポリプロピレン樹脂組成物。Claim 3: The above benzoate compound is 2,4-
The polypropylene resin composition according to claim 1, characterized in that it is di-t-butyl-phenyl-3',5'-di-t-butyl-4'-hydroxy-benzoate.
ヒドロキシ−４−オクトキシ−ベンゾフェノンであるこ
とを特徴とする請求項１記載のポリプロピレン樹脂組成
物。Claim 4: The above benzophenone compound is 2-
The polypropylene resin composition according to claim 1, characterized in that it is hydroxy-4-octoxy-benzophenone.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16086591A JPH04359942A (en) | 1991-06-06 | 1991-06-06 | Fluorescent-colored polypropylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16086591A JPH04359942A (en) | 1991-06-06 | 1991-06-06 | Fluorescent-colored polypropylene resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04359942A true JPH04359942A (en) | 1992-12-14 |
Family
ID=15724048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16086591A Pending JPH04359942A (en) | 1991-06-06 | 1991-06-06 | Fluorescent-colored polypropylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04359942A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6312132B1 (en) | 2000-09-12 | 2001-11-06 | 3M Innovative Properties Company | Fluorescent red article and retroreflective article made therefrom |
| WO2002022761A1 (en) * | 2000-09-12 | 2002-03-21 | 3M Innovative Properties Company | Fluorescent red composition and articles made therefrom |
| KR100367114B1 (en) * | 2000-08-04 | 2003-01-09 | 주식회사 화승 인더스트리 | Biaxially oriented polypropylene film for fluorescence sensor and process for preparation thereof |
-
1991
- 1991-06-06 JP JP16086591A patent/JPH04359942A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100367114B1 (en) * | 2000-08-04 | 2003-01-09 | 주식회사 화승 인더스트리 | Biaxially oriented polypropylene film for fluorescence sensor and process for preparation thereof |
| US6312132B1 (en) | 2000-09-12 | 2001-11-06 | 3M Innovative Properties Company | Fluorescent red article and retroreflective article made therefrom |
| WO2002022761A1 (en) * | 2000-09-12 | 2002-03-21 | 3M Innovative Properties Company | Fluorescent red composition and articles made therefrom |
| US6572977B1 (en) | 2000-09-12 | 2003-06-03 | 3M Innovative Properties Company | Fluorescent red composition and articles made therefrom |
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