JPH04339814A - Polypropylene resin composition - Google Patents
Polypropylene resin compositionInfo
- Publication number
- JPH04339814A JPH04339814A JP4727191A JP4727191A JPH04339814A JP H04339814 A JPH04339814 A JP H04339814A JP 4727191 A JP4727191 A JP 4727191A JP 4727191 A JP4727191 A JP 4727191A JP H04339814 A JPH04339814 A JP H04339814A
- Authority
- JP
- Japan
- Prior art keywords
- polypropylene
- weight
- ethylene
- resin composition
- olefin copolymer
- 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.)
- Granted
Links
- -1 Polypropylene Polymers 0.000 title claims abstract description 34
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 32
- 239000011342 resin composition Substances 0.000 title abstract description 20
- 239000004711 α-olefin Substances 0.000 claims abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 19
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 6
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 abstract description 23
- 238000000576 coating method Methods 0.000 abstract description 23
- 239000000203 mixture Substances 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 229920005989 resin Polymers 0.000 abstract description 11
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 239000003973 paint Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920003051 synthetic elastomer Polymers 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 4
- 238000010422 painting Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 2
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-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
- 102100028215 BTB/POZ domain-containing protein KCTD7 Human genes 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 102100026891 Cystatin-B Human genes 0.000 description 2
- 101001007222 Homo sapiens BTB/POZ domain-containing protein KCTD7 Proteins 0.000 description 2
- 101000912191 Homo sapiens Cystatin-B Proteins 0.000 description 2
- 208000033255 Progressive myoclonic epilepsy type 1 Diseases 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 208000023353 progressive myoclonic epilepsy type 3 Diseases 0.000 description 2
- 208000023804 progressive myoclonic epilepsy type 7 Diseases 0.000 description 2
- 208000027071 progressive myoclonus epilepsy 3 Diseases 0.000 description 2
- 208000027021 progressive myoclonus epilepsy 7 Diseases 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- WTQBISBWKRKLIJ-UHFFFAOYSA-N 5-methylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C)CC1C=C2 WTQBISBWKRKLIJ-UHFFFAOYSA-N 0.000 description 1
- 208000025048 Action myoclonus-renal failure syndrome Diseases 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 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
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 208000037059 Progressive myoclonic epilepsy type 5 Diseases 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
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001253 acrylic acids Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 150000001261 hydroxy acids Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229920006113 non-polar polymer Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920006112 polar polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 208000029049 progressive myoclonic epilepsy type 6 Diseases 0.000 description 1
- 208000027025 progressive myoclonus epilepsy 4 Diseases 0.000 description 1
- 208000027016 progressive myoclonus epilepsy 6 Diseases 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 208000002916 sensory ataxic neuropathy, dysarthria, and ophthalmoparesis Diseases 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- LYDRKKWPKKEMNZ-UHFFFAOYSA-N tert-butyl benzoate Chemical compound CC(C)(C)OC(=O)C1=CC=CC=C1 LYDRKKWPKKEMNZ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は，塗膜密着性に優れたポ
リプロピレン系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 with excellent coating film adhesion.
【０００２】0002
【従来技術】ポリプロピレン系樹脂組成物は，成形性が
良く，またその成形品は機械的性質，耐薬品性に優れ，
しかも安価である。そのため，汎用プラスチックとして
，自動車部品，電気製品等の成形品において，多用され
ている。一方，ポリプロピレン系樹脂組成物は，非極性
ポリマーであるため，一般に塗料（主として極性ポリマ
ーを塗装成分とする）との密着性が良くなく，塗膜密着
性が悪い。そのため，その成形品に塗装を施すに際して
は，予め，プライマー処理，プラズマ処理等の前処理を
施しておく必要がある。しかし，かかる前処理は面倒で
あり，塗装作業の生産性を低下させる。そこで，従来，
塗膜密着性を向上させるため，ポリプロピレンとエチレ
ン−α−オレフィン系共重合体とのポリマー混合系であ
って無水マレイン酸等の不飽和カルボン酸及び／又はそ
の誘導体を有機ラジカル発生剤と共に添加，混合し，加
熱処理してなるポリプロピレン系樹脂組成物が提案され
ている（特開昭６２−２８０２６７号公報参照）。[Prior art] Polypropylene resin compositions have good moldability, and molded products thereof have excellent mechanical properties and chemical resistance.
Moreover, it is inexpensive. Therefore, it is widely used as a general-purpose plastic in molded products such as automobile parts and electrical products. On the other hand, since polypropylene resin compositions are non-polar polymers, they generally do not have good adhesion to paints (mainly polar polymers are the paint component) and have poor paint film adhesion. Therefore, before painting the molded product, it is necessary to perform pretreatment such as primer treatment and plasma treatment in advance. However, such pretreatment is troublesome and reduces the productivity of painting operations. Therefore, conventionally,
In order to improve the adhesion of the coating film, a polymer mixture of polypropylene and ethylene-α-olefin copolymer is added with an unsaturated carboxylic acid such as maleic anhydride and/or its derivatives together with an organic radical generator. A polypropylene resin composition prepared by mixing and heat-treating has been proposed (see Japanese Patent Laid-Open No. 62-280267).
【０００３】0003
【解決しようとする課題】しかしながら，発明者らの実
験検討の結果では，上記公報に示される樹脂組成物は，
塗膜密着性が未だ充分でない。また，上記公報の樹脂組
成物において，不飽和カルボン酸として最も好ましいと
されている無水マレイン酸を用いた場合でも，充分な塗
膜密着性を得ることができない（後述する実施例におけ
る比較例参照）。本発明は，かかる従来の問題点に鑑み
，ポリプロピレンの優れた機械的性質を有し，成形品に
前処理を施す必要がなく，塗膜密着性に優れたポリプロ
ピレン系樹脂組成物を提供しようとするものである。[Problem to be Solved] However, according to the results of the inventors' experimental studies, the resin composition shown in the above publication is
Paint film adhesion is still not sufficient. In addition, in the resin composition of the above publication, even when maleic anhydride, which is considered to be the most preferable unsaturated carboxylic acid, is used, sufficient coating film adhesion cannot be obtained (see comparative examples in the examples below). ). In view of these conventional problems, the present invention aims to provide a polypropylene resin composition that has the excellent mechanical properties of polypropylene, does not require pre-treatment of molded products, and has excellent coating film adhesion. It is something to do.
【０００４】0004
【課題の解決手段】本発明は，（Ａ）ポリプロピレン９
０〜３０重量％と，（Ｂ）ムーニー粘度ＭＬ１＋４ （
１００℃）５０以下で，かつプロピレン含量２０重量％
以上であるエチレン−α−オレフィン系共重合体１０〜
７０重量％とからなる樹脂混合物１００重量部に対して
，（Ｃ）分子内に少なくとも１つの水酸基を有する不飽
和カルボン酸及び／又はその誘導体からなる不飽和単量
体０．１重量部以上と，（Ｄ）有機ラジカル発生剤とを
添加，混合し，次いで，加熱処理して得られたことを特
徴とするポリプロピレン系樹脂組成物にある。[Means for solving the problems] The present invention provides (A) polypropylene 9
0 to 30% by weight, (B) Mooney viscosity ML1+4 (
100℃) 50 or less, and propylene content 20% by weight
The above ethylene-α-olefin copolymer 10~
(C) 0.1 part by weight or more of an unsaturated monomer consisting of an unsaturated carboxylic acid and/or a derivative thereof having at least one hydroxyl group in the molecule; , (D) an organic radical generating agent, the polypropylene resin composition is obtained by adding and mixing, and then heat-treating the composition.
【０００５】本発明において最も注目すべきことは，上
記特定のムーニー粘度及びプロピレン含有量のエチレン
−α−オレフィン系共重合体を用いること，上記不飽和
単量体として少なくとも１つの水酸基を有する上記特定
の不飽和単量体を用いること，更にこれらを前記ポリプ
ロピレンに対して特定割合で添加することである。また
，本発明においては，上記ポリプロピレンとエチレン−
α−オレフィン系共重合体とからなる樹脂混合物１００
重量部に対して，上記不飽和単量体０．１重量部以上と
有機ラジカル発生剤を添加混合する。The most noteworthy feature of the present invention is the use of an ethylene-α-olefin copolymer having the specified Mooney viscosity and propylene content, and the use of the above-mentioned unsaturated monomer having at least one hydroxyl group. The method involves using specific unsaturated monomers and adding these monomers in specific proportions to the polypropylene. In addition, in the present invention, the above polypropylene and ethylene-
Resin mixture 100 consisting of α-olefin copolymer
0.1 part by weight or more of the unsaturated monomer and an organic radical generator are added and mixed based on the weight part.
【０００６】そして，上記樹脂混合物は，ポリプロピレ
ン９０〜３０重量％と上記エチレン−α−オレフィン系
共重合体１０〜７０重量％とよりなる。ポリプロピレン
が，９０重量％を超えると成形品への塗膜密着性が低く
なる。一方ポリプロピレンが３０重量％未満となると，
エチレン−α−オレフィン系共重合体の量が過大となり
，成形品のゴム的性質が強くなりすぎ，ポリプロピレン
樹脂本来の優れた機械的，耐薬品性が低下するおそれが
ある。なお，更に好ましくは，ポリプロピレン７０〜４
０重量％，エチレン−α−オレフィン系共重合体３０〜
６０重量％である。この場合には，特に塗膜密着性の点
が優れている。The resin mixture comprises 90 to 30% by weight of polypropylene and 10 to 70% by weight of the ethylene-α-olefin copolymer. If the polypropylene content exceeds 90% by weight, the adhesion of the coating film to the molded article will decrease. On the other hand, when polypropylene is less than 30% by weight,
If the amount of the ethylene-α-olefin copolymer is too large, the rubbery properties of the molded product may become too strong, and the excellent mechanical and chemical resistance inherent to polypropylene resin may be reduced. Furthermore, more preferably polypropylene 70-4
0% by weight, ethylene-α-olefin copolymer 30~
It is 60% by weight. In this case, the coating film adhesion is particularly excellent.
【０００７】上記ポリプロピレンとしては，特に限定す
るものではないが，ポリプロピレン単独重合体，及び／
又はエチレン成分を２５重量％以下含有するブロック共
重合体を用いることが好ましい。また，上記エチレン−
α−オレフィン系共重合体は，ムーニー粘度ＭＬ１＋４
（１００℃）が５０以下で，かつプロピレン含量が２
０重量％以上のものを用いる。上記のムーニー粘度ＭＬ
１＋４ （１００℃）とは，ムーニー剪断円板式粘度計
で測定した粘度単位，即ち大円板，予熱１００℃，１分
間，回転開始４分後における計器の指示値をいう。ここ
に，ムーニー粘度ＭＬ１＋４ （１００℃）が５０を超
えると，塗膜密着性の向上効果が小さい（比較例５，６
），プロピレン２０重量％未満では耐屈曲疲労性が低い
（比較例４）ので，実用的でない。[0007] The polypropylene mentioned above is not particularly limited, but may include polypropylene homopolymer and/or polypropylene.
Alternatively, it is preferable to use a block copolymer containing 25% by weight or less of an ethylene component. In addition, the above ethylene-
The α-olefin copolymer has a Mooney viscosity of ML1+4
(100℃) is 50 or less, and the propylene content is 2
Use 0% by weight or more. Mooney viscosity ML above
1+4 (100°C) refers to the viscosity unit measured with a Mooney shear disk viscometer, that is, the reading on the meter after preheating the large disk to 100°C for 1 minute and 4 minutes after the start of rotation. Here, if Mooney viscosity ML1+4 (100°C) exceeds 50, the effect of improving coating film adhesion is small (Comparative Examples 5 and 6).
), less than 20% by weight of propylene is not practical because the bending fatigue resistance is low (Comparative Example 4).
【０００８】また，上記エチレン−α−オレフィン系共
重合体中における，エチレン；α−オレフィン；非共役
ジエンの割合（重量分率）は，０．２〜０．８：０．２
〜０．８：０〜０．１であることが好ましい。即ち，エ
チレン−α−オレフィン系共重合体はエチレン・プロピ
レン共重合体，或いはエチレン・α−オレフィン，共役
ジエン共重合体である。[0008] Furthermore, the ratio (weight fraction) of ethylene: α-olefin: non-conjugated diene in the above ethylene-α-olefin copolymer is 0.2 to 0.8:0.2.
-0.8: It is preferable that it is 0-0.1. That is, the ethylene-α-olefin copolymer is an ethylene/propylene copolymer or an ethylene/α-olefin or conjugated diene copolymer.
【０００９】また，エチレン−α−オレフィン系共重合
体中におけるα−オレフィンとしては，炭素数３〜１２
のもの，例えばプロピレン，１−ブテン，４−メチル−
１−ペンテン，１−ヘキセン等の１種又は２種以上があ
る。この中，エチレン−α−オレフィン系共重合体は，
α−オレフィンがプロピレンである，エチレン・プロピ
レン共重合体（ＥＰＭ），又はエチレン・プロピレン・
非共役ジエン三元共重合体であることが好ましい。この
場合には，可撓性，低コストの点で優れている。また，
非共役ジエンとしては，エチリデンノルボルネン，シク
ロペンタジエン，１，４−ヘキサジエン，メチレンノル
ボルネン等を挙げることができる。この中，エチリデン
ノルボルネンが一般的で，商業的である。In addition, the α-olefin in the ethylene-α-olefin copolymer has 3 to 12 carbon atoms.
such as propylene, 1-butene, 4-methyl-
There are one or more types such as 1-pentene and 1-hexene. Among these, ethylene-α-olefin copolymer is
Ethylene-propylene copolymer (EPM), where the α-olefin is propylene, or ethylene-propylene copolymer (EPM), where the α-olefin is propylene.
Preferably, it is a non-conjugated diene terpolymer. This case is superior in terms of flexibility and low cost. Also,
Examples of the non-conjugated diene include ethylidenenorbornene, cyclopentadiene, 1,4-hexadiene, methylenenorbornene, and the like. Among these, ethylidenenorbornene is common and commercially available.
【００１０】また，エチレン−α−オレフィン系共重合
体中のプロピレン含量は２０重量％以上とする。２０重
量％未満では成形品の耐寒衝撃性が低く，実用的でない
。なお，このプロピレン含量は柔軟性の点より，６０重
量％未満とすることが好ましい。次に，上記樹脂混合物
１００重量部に対して，前記不飽和単量体０．１重量部
以上と有機ラジカル発生剤を添加，混合する。不飽和単
量体が，０．１重量部未満では塗膜密着性を向上させる
ことができない。また，不飽和単量体の上限は，成形品
の剛性，衝撃強度，表面光沢等に悪影響を与えるため，
１０重量部とすることが好ましい。Further, the propylene content in the ethylene-α-olefin copolymer is 20% by weight or more. If the amount is less than 20% by weight, the cold impact resistance of the molded article will be low, making it impractical. Note that the propylene content is preferably less than 60% by weight from the viewpoint of flexibility. Next, 0.1 part by weight or more of the unsaturated monomer and an organic radical generator are added and mixed with 100 parts by weight of the resin mixture. If the amount of unsaturated monomer is less than 0.1 part by weight, coating film adhesion cannot be improved. In addition, the upper limit of unsaturated monomers has a negative effect on the rigidity, impact strength, surface gloss, etc. of molded products, so
The amount is preferably 10 parts by weight.
【００１１】そして，上記不飽和単量体としては，分子
中に少なくとも１つの水酸基（−ＯＨ）を有する不飽和
カルボン酸及びその誘導体の一方又は双方がある。かか
る不飽和単量体としては，酸アミドのアルキルアルコー
ルＮ置換体（例えばＮ−メチロールアクリルアミド），
アクリル酸類のポリオールエステル（例えば，２−ヒド
ロキシエチルメタクリレート，３−ヒドロキシプロピル
アクリレート），ヒドロキシ酸（例えば，ヒドロアクリ
ル酸）など，及びこれらの誘導体がある。[0011] The unsaturated monomers include one or both of unsaturated carboxylic acids and derivatives thereof having at least one hydroxyl group (-OH) in the molecule. Such unsaturated monomers include alkyl alcohol N-substituted acid amide (e.g. N-methylolacrylamide),
Examples include polyol esters of acrylic acids (eg, 2-hydroxyethyl methacrylate, 3-hydroxypropyl acrylate), hydroxy acids (eg, hydroacrylic acid), and derivatives thereof.
【００１２】また，有機ラジカル発生剤は，主として，
上記不飽和カルボン酸を上記樹脂混合物，即ちポリプロ
ピレン及びエチレン−α−オレフィン系共重合体のポリ
マーにグラフト重合させる作用を行わせるものである。
そして，その添加量は，不飽和カルボン酸の種類，配合
量に関連して定められるが，通常はモル比で不飽和カル
ボン酸／有機ラジカル発生剤＝１５〜８５とする。また
，上記樹脂混合物１００重量部に対しては，０．０１〜
０．５重量部とする。[0012] Furthermore, the organic radical generator is mainly used for
The unsaturated carboxylic acid is graft-polymerized to the resin mixture, that is, a polymer of polypropylene and ethylene-α-olefin copolymer. The amount added is determined in relation to the type and amount of unsaturated carboxylic acid, but usually the molar ratio of unsaturated carboxylic acid/organic radical generator is 15 to 85. In addition, for 100 parts by weight of the above resin mixture, 0.01 to
The amount is 0.5 part by weight.
【００１３】また，上記有機ラジカル発生剤としては，
下記の有機過酸化物や，アゾ化合物等慣用のものが使用
可能である。即ち，２，５−ジメチル−２，５−ジ（ｔ
−ブチルペルオキシ）−３−ヘキシン，２，５−ジメチ
ル−２，５−ジ（ｔ−ブチルペルオキシ）ヘキサン，１
，３−ビス（ｔ−ブチルペルオキシイソプロピル）ベン
ゼン，２，２， −ビス（ｔブチルペルオキシ）−Ｐ−
ジイソプロピルベンゼン，ジクミルペルオキシド，ジ−
ｔ−ブチルペルオキシド，ｔ−ブチルベンゾエート，ジ
ベンゾイルペルオキシド，アゾビスイソブチロニトリル
などがある。また，上記のうち，１，３−ビス（ｔ−ブ
チルペルオキシイソプロピル）ベンゼンが塗膜密着性の
点で最も好ましい。[0013] Furthermore, as the organic radical generator,
Commonly used organic peroxides and azo compounds listed below can be used. That is, 2,5-dimethyl-2,5-di(t
-butylperoxy)-3-hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1
,3-bis(t-butylperoxyisopropyl)benzene,2,2, -bis(t-butylperoxy)-P-
Diisopropylbenzene, dicumyl peroxide, di-
Examples include t-butyl peroxide, t-butyl benzoate, dibenzoyl peroxide, and azobisisobutyronitrile. Among the above, 1,3-bis(t-butylperoxyisopropyl)benzene is most preferred in terms of coating film adhesion.
【００１４】なお，過流酸塩等の無機系過酸化物も使用
することができる。次に，樹脂組成物の調整に当たって
は，上記樹脂混合物に上記不飽和単量体及び有機ラジカ
ル発生剤を添加混合し，押出機又はバンバリーニーダー
等の混合機を使用して，１７０〜２８０℃，０．２〜３
分間の加熱処理を行う。また，上記樹脂組成物の製造に
当たっては，必要に応じて，酸化防止剤，熱安定剤，紫
外線吸収剤，着色剤，無機充填剤（炭酸カルシウム，タ
ルク，ガラス繊維など）等を添加することもできる。ま
た，上記加熱処理の工程を経て，ペレット等の成形材料
とする。そして，該成形材料を，射出成形機，押出成形
機等の成形機を用いて，所望形状の成形品に成形する。Incidentally, inorganic peroxides such as persulfates can also be used. Next, in preparing the resin composition, the unsaturated monomer and organic radical generator are added and mixed to the resin mixture, and heated at 170 to 280°C using a mixer such as an extruder or a Banbury kneader. 0.2-3
Perform heat treatment for 1 minute. In addition, when producing the above resin composition, antioxidants, heat stabilizers, ultraviolet absorbers, colorants, inorganic fillers (calcium carbonate, talc, glass fiber, etc.), etc. may be added as necessary. can. Further, the material is made into a molding material such as pellets through the heat treatment process described above. Then, the molding material is molded into a molded product of a desired shape using a molding machine such as an injection molding machine or an extrusion molding machine.
【００１５】また，このようにして得た成形品には，ウ
レタン系，アクリル系，アルキッド系，エポキシ系等の
汎用のプラスチック用塗料を塗装する。また，上記塗料
中，ウレタン系塗料が塗膜性能，塗膜密着性の面で優れ
ている。なお，塗装に当たっては，トリクロロエタン等
の塩素系有機溶剤で，成形品表面を洗浄しておくことが
好ましい。また，塗装に先立って，プライマー処理を施
しても良い。The molded product thus obtained is coated with a general-purpose plastic paint such as urethane, acrylic, alkyd, or epoxy. Furthermore, among the above paints, urethane paints are superior in terms of film performance and film adhesion. Note that before painting, it is preferable to clean the surface of the molded product with a chlorinated organic solvent such as trichloroethane. Additionally, a primer treatment may be applied prior to painting.
【００１６】[0016]
【作用及び効果】本発明のポリプロピレン系樹脂組成物
は，ポリプロピレンと特定の上記エチレン−α−オレフ
ィン系共重合体とからなる樹脂混合物に上記特定の不飽
和単量体及び有機ラジカル発生剤を，特定割合で添加混
合し，加熱処理したものである。そのため，本発明の樹
脂組成物は前記従来のポリプロピレン系樹脂組成物に比
してその塗膜密着性が一層優れている。また，該樹脂組
成物は，ポリプロピレン本来の機械的性質を余り低下さ
せることがない。したがって，本発明によれば，ポリプ
ロピレンの優れた機械的性質を有し，成形品に前処理を
施す必要がなく，塗膜密着性に優れたポリプロピレン系
樹脂組成物を提供することができる。[Operations and Effects] The polypropylene resin composition of the present invention includes the above-mentioned specific unsaturated monomer and organic radical generator in a resin mixture consisting of polypropylene and the above-mentioned specific ethylene-α-olefin copolymer. It is added and mixed in a specific ratio and heat-treated. Therefore, the resin composition of the present invention has better coating film adhesion than the conventional polypropylene resin composition. Furthermore, the resin composition does not significantly reduce the mechanical properties inherent to polypropylene. Therefore, according to the present invention, it is possible to provide a polypropylene resin composition that has the excellent mechanical properties of polypropylene, does not require pretreatment of molded articles, and has excellent coating film adhesion.
【００１７】[0017]
【実施例】以下，本発明にかかる実施例を比較例と共に
説明する。本例においては，ポリプロピレン系樹脂組成
物を調整し，次いで該樹脂組成物を，射出成形して成形
品となし，その表面に塗料を塗布し，その塗膜密着性に
つき測定した。また，破断強度（％），曲げ弾性率（Ｍ
Ｐａ），アイゾット衝撃強さ（−３０℃，Ｊ／ｍ），塗
膜剥離強度（ｇ／ｃｍ）についても測定した。これらの
結果を表１，表２に示した。[Examples] Examples according to the present invention will be described below together with comparative examples. In this example, a polypropylene resin composition was prepared, the resin composition was then injection molded into a molded article, a paint was applied to the surface of the molded article, and the adhesion of the paint film was measured. Also, breaking strength (%), bending elastic modulus (M
Pa), Izod impact strength (-30°C, J/m), and coating peel strength (g/cm) were also measured. These results are shown in Tables 1 and 2.
【００１８】上記ポリプロピレン系樹脂組成物の調整に
当たっては，ポリプロピレン（以下，ＰＰという）とエ
チレン−α−オレフィン系共重合体（以下，ＥＰＲとい
う）との樹脂混合物１００重量部に対して，不飽和単量
体と有機ラジカル発生剤とを混合し，同方向二軸押出機
を使用して溶融混合，押出してペレット状の射出成形用
材料とした。上記混合割合は，表１，表２に示した。ま
た，上記押出しの条件は，シリンダ入口温度１５０℃，
出口温度２００℃，スクリュー回転数３００ｒｐｍとし
た。また，上記ＥＰＲとしては，エチレン・プロピレン
共重合体（以下，ＥＰＭという），又はエチレン・プロ
ピレン・非共役ジエン三元共重合体（以下，ＥＰＤＭと
いう）を用いた。In preparing the above-mentioned polypropylene resin composition, unsaturated A monomer and an organic radical generator were mixed, melt-blended and extruded using a co-directional twin-screw extruder to obtain a pellet-shaped injection molding material. The above mixing ratios are shown in Tables 1 and 2. In addition, the above extrusion conditions are: cylinder inlet temperature 150℃;
The outlet temperature was 200°C and the screw rotation speed was 300 rpm. Further, as the EPR, an ethylene-propylene copolymer (hereinafter referred to as EPM) or an ethylene-propylene-nonconjugated diene terpolymer (hereinafter referred to as EPDM) was used.
【００１９】次に，上記各原料としては，下記のものを
用いた。
ＰＰ．．．“ハイポールＪ−３００Ｐ”三井石油化学（
株）製，ＭＦＲ（メルト・フロー・レート）：１．４ｇ
／１０ｍｉｎ
ＥＰＭ１．．．“ＥＰ９２１”日本合成ゴム（株）製，
ＭＬ１＋４ （１００℃）：２７，プロピレン含量：５
０％ＥＰＭ２．．．“ＥＰ１１”日本合成ゴム（株）製
，ＭＬ１＋４ （１００℃）：４０，プロピレン含量：
４９％ＥＰＭ３．．．“ＥＰ０１Ｐ”日本合成ゴム（株
）製，ＭＬ１＋４ （１００℃）：１９，プロピレン含
量：２２％ＥＰＭ４．．．“ＥＰ０２Ｐ”日本合成ゴム
（株）製，ＭＬ１＋４ （１００℃）：２４，プロピレ
ン含量：２６％Next, the following materials were used as the above raw materials. PP. ．． ．． “Hypol J-300P” Mitsui Petrochemical (
Co., Ltd., MFR (melt flow rate): 1.4g
/10min EPM1. ．． ．． “EP921” manufactured by Japan Synthetic Rubber Co., Ltd.
ML1+4 (100°C): 27, Propylene content: 5
0% EPM2. ．． ．． “EP11” manufactured by Japan Synthetic Rubber Co., Ltd., ML1+4 (100°C): 40, Propylene content:
49% EPM3. ．． ．． “EP01P” manufactured by Japan Synthetic Rubber Co., Ltd., ML1+4 (100°C): 19, Propylene content: 22% EPM4. ．． ．． “EP02P” manufactured by Japan Synthetic Rubber Co., Ltd., ML1+4 (100°C): 24, Propylene content: 26%
【００２０】ＥＰＭ５．．．“ＥＰ９１
２Ｐ”日本合成ゴム（株）製，ＭＬ１＋４ （１００℃
）：１０，プロピレン含量：２２％
ＥＰＭ６．．．“ＥＰ９１１Ｐ”日本合成ゴム（株）製
，ＭＬ１＋４ （１００℃）：１５，プロピレン含量：
１５％
ＥＰＭ７．．．“ＥＰ９６１ＳＰ”日本合成ゴム（株）
製，ＭＬ１＋４ （１００℃）：６３，プロピレン含量
：２３％
ＥＰＤＭ．．．“ＥＰ５７Ｐ”日本合成ゴム（株）製，
ＭＬ１＋４ （１００℃）：８８，プロピレン含量：２
８％[0020]EPM5. ．． ．． “EP91
2P” manufactured by Japan Synthetic Rubber Co., Ltd., ML1+4 (100℃
): 10, Propylene content: 22% EPM6. ．． ．． “EP911P” manufactured by Japan Synthetic Rubber Co., Ltd., ML1+4 (100°C): 15, Propylene content:
15% EPM7. ．． ．． “EP961SP” Japan Synthetic Rubber Co., Ltd.
manufactured by EPDM., ML1+4 (100°C): 63, propylene content: 23%. ．． ．． “EP57P” manufactured by Japan Synthetic Rubber Co., Ltd.
ML1+4 (100℃): 88, Propylene content: 2
8%
【００２１】有機ラジカル発生剤．．．“パーカド
ックス１４”アクゾ（株）製，１，３−ビス）ｔ−ブチ
ルペルオキシイソプロピル）ベンゼン。
熱安定剤．．．“イルガノックス１０１０”チバガイギ
ー（株）製，ヒンダードフェノール系。
なお，上記「ＭＦＲ（メルト・フロー・レート）」は，
樹脂材料が２３０℃で２１６０ｇの力を受けたときに，
直径２．１ｍｍのオリフィスから１０分間に押出される
樹脂材料のｇ数で示した。また，ムーニー粘度ＭＬ１＋
４ については前記した。Organic radical generator. ．． ．． “Perkadox 14” manufactured by Akzo Co., Ltd., 1,3-bis)t-butylperoxyisopropyl)benzene. Heat stabilizer. ．． ．． “Irganox 1010” manufactured by Ciba Geigy, hindered phenol type. The above “MFR (melt flow rate)” is
When the resin material is subjected to a force of 2160g at 230℃,
It is expressed as the number of grams of resin material extruded in 10 minutes from an orifice with a diameter of 2.1 mm. Also, Mooney viscosity ML1+
4 has been described above.
【００２２】また，成形品は，上記ペレット状材料を，
入口温度１５０℃，出口温度１８０℃において射出成形
することにより作製した。該成形品は，４０×１１０×
２ｍｍの大きさであった。次に，該成形品を塩素系有機
溶剤（トリクロロエタン）で脱脂処理した後，ウレタン
系塗料を塗膜厚み３０μｍに塗布し，９０℃，４０分の
条件で，焼付けし，各試料とした。上記塗料は，日本ビ
ーケミカル社製の“Ｒ２７８”（主剤），“Ｒ２７１”
（硬化剤）からなる二液型のものを用いた。[0022] Furthermore, the molded product can be made by using the pellet-like material as described above.
It was manufactured by injection molding at an inlet temperature of 150°C and an outlet temperature of 180°C. The molded product is 40×110×
The size was 2 mm. Next, the molded product was degreased with a chlorinated organic solvent (trichloroethane), and then a urethane paint was applied to a film thickness of 30 μm and baked at 90° C. for 40 minutes to prepare each sample. The above paints are “R278” (main agent) and “R271” manufactured by Nippon B Chemical Co., Ltd.
A two-component type product consisting of (curing agent) was used.
【００２３】また，上記塗膜密着性試験は，ＪＩＳＫ−
６８５４に準じて，１８０度剥離の方法を用いて，その
塗膜剥離強度（ｇ／ｃｍ）を測定することにより行った
。表１及び２より知られるごとく，本発明に関する実施
例１〜８は，いずれも４６０ｇ／ｃｍ以上という塗膜剥
離強度を示している。特に，ＥＰＭ１を３０〜６０重量
％用いた実施例２〜４，ＥＰＭ３を４５重量％用いた実
施例６は１２００（ｇ／ｃｍ）程度以上という高い塗膜
剥離強度を示している。なお，アイゾッド衝撃強さの欄
の「ＮＢ」は，試料が破断しなかったことを意味する。[0023] Furthermore, the above coating film adhesion test was carried out in accordance with JISK-
The peeling strength (g/cm) of the coating film was measured using a 180-degree peeling method in accordance with 6854. As can be seen from Tables 1 and 2, Examples 1 to 8 related to the present invention all exhibit a coating peel strength of 460 g/cm or more. In particular, Examples 2 to 4 using 30 to 60% by weight of EPM1 and Example 6 using 45% by weight of EPM3 exhibit high coating peel strengths of about 1200 (g/cm) or more. Note that "NB" in the Izod impact strength column means that the sample did not break.
【００２４】一方，比較例１〜６は全般に塗膜剥離強度
が低い。特に，ＰＰとＥＰＭのみで，不飽和単量体及び
有機ラジカル発生剤を加えていない比較例２は，塗膜剥
離強度が５ｇ／ｃｍで，塗装膜密着性が極端に悪い。ま
た，比較例４は塗膜剥離強度が８７０ｇ／ｃｍと高いが
，耐寒衝撃性の点で本発明品に劣っている。また，比較
例３は，不飽和カルボン酸として水酸基を有していない
無水マレイン酸（従来例）を用いた例で，塗膜剥離強度
は６０５ｇ／ｃｍあるが，破断伸度が極端に低くなって
いる。また，比較例５はＥＰＭ７がムーニー粘度６３と
高く，また比較例６はＥＰＤＭがムーニー粘度８８と高
いため，ともに塗膜剥離強度が低い。On the other hand, in Comparative Examples 1 to 6, the peel strength of the coating film was generally low. In particular, Comparative Example 2, which contained only PP and EPM without adding any unsaturated monomer or organic radical generator, had a coating peel strength of 5 g/cm and extremely poor coating adhesion. Comparative Example 4 had a high coating peel strength of 870 g/cm, but was inferior to the product of the present invention in terms of cold impact resistance. Comparative Example 3 is an example in which maleic anhydride (conventional example), which does not have a hydroxyl group, is used as the unsaturated carboxylic acid, and the coating peel strength is 605 g/cm, but the elongation at break is extremely low. ing. Further, in Comparative Example 5, EPM7 has a high Mooney viscosity of 63, and in Comparative Example 6, EPDM has a high Mooney viscosity of 88, so both have low coating film peel strength.
【００２５】[0025]
【表１】[Table 1]
【００２６】[0026]
【表２】[Table 2]
Claims (1)
，（Ｂ）ムーニー粘度ＭＬ１＋４ （１００℃）５０以
下で，かつプロピレン含量２０重量％以上であるエチレ
ン−α−オレフィン系共重合体１０〜７０重量％とから
なる樹脂混合物１００重量部に対して，（Ｃ）分子内に
少なくとも１つの水酸基を有する不飽和カルボン酸及び
／又はその誘導体からなる不飽和単量体０．１重量部以
上と，（Ｄ）有機ラジカル発生剤とを添加，混合し，次
いで，加熱処理して得られたことを特徴とするポリプロ
ピレン系樹脂組成物。Claim 1: (A) 90 to 30% by weight of polypropylene, and (B) 10 to 10% of ethylene-α-olefin copolymer having a Mooney viscosity of ML1+4 (100°C) 50 or less and a propylene content of 20% by weight or more. (C) 0.1 part by weight or more of an unsaturated monomer consisting of an unsaturated carboxylic acid and/or a derivative thereof having at least one hydroxyl group in the molecule; , (D) an organic radical generating agent, and then heat-treated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047271A JP2541387B2 (en) | 1991-01-29 | 1991-01-29 | Polypropylene resin molded product with excellent coating film adhesion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3047271A JP2541387B2 (en) | 1991-01-29 | 1991-01-29 | Polypropylene resin molded product with excellent coating film adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04339814A true JPH04339814A (en) | 1992-11-26 |
| JP2541387B2 JP2541387B2 (en) | 1996-10-09 |
Family
ID=12770632
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3047271A Expired - Fee Related JP2541387B2 (en) | 1991-01-29 | 1991-01-29 | Polypropylene resin molded product with excellent coating film adhesion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2541387B2 (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751734A (en) * | 1980-09-13 | 1982-03-26 | Idemitsu Petrochem Co Ltd | Resin composition with improved paintability |
| JPS58154732A (en) * | 1982-03-10 | 1983-09-14 | Showa Denko Kk | Coating of molding of olefin polymer composition |
| JPS62207344A (en) * | 1986-03-07 | 1987-09-11 | Showa Denko Kk | Rropylene polymer composition |
| JPS6341552A (en) * | 1986-08-07 | 1988-02-22 | Showa Denko Kk | Propylene based polymer composition |
| JPS6485206A (en) * | 1986-10-29 | 1989-03-30 | Mitsui Petrochemical Ind | Thermoplastic elastomer composition having excellent heat-adhesiveness |
-
1991
- 1991-01-29 JP JP3047271A patent/JP2541387B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5751734A (en) * | 1980-09-13 | 1982-03-26 | Idemitsu Petrochem Co Ltd | Resin composition with improved paintability |
| JPS58154732A (en) * | 1982-03-10 | 1983-09-14 | Showa Denko Kk | Coating of molding of olefin polymer composition |
| JPS62207344A (en) * | 1986-03-07 | 1987-09-11 | Showa Denko Kk | Rropylene polymer composition |
| JPS6341552A (en) * | 1986-08-07 | 1988-02-22 | Showa Denko Kk | Propylene based polymer composition |
| JPS6485206A (en) * | 1986-10-29 | 1989-03-30 | Mitsui Petrochemical Ind | Thermoplastic elastomer composition having excellent heat-adhesiveness |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2541387B2 (en) | 1996-10-09 |
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