JP3692201B2 - Long glass fiber reinforced polypropylene resin composition with excellent paintability - Google Patents

Description

（式中のＲ₁及びＲ₂は、水素原子又は炭素数１〜５までのアルキル基を示す）で表される化合物とのポリプロピレン共重合体と、
平均繊維長が１ｍｍ以上のガラス繊維とを含有する塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物であって、
当該樹脂組成物の成形体の塗料を塗布した面に切れ目を入れて１ｍｍ角の１００個の升目を作製し、前記升目の上にセロハンテープ（ＪＩＳ Ｚ １５２２に規定されたもの）をはった後、前記セロハンテープを剥がす升目試験において、前記成形体の面に残存する前記升目の数が１００個中７８個以上であることを特徴とする。
【００１０】
請求項２記載の塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物は、ポリプロピレン共重合体中に含まれる上記化２式で示される化合物の割合が 0.1〜10.0重量％であることを特徴とする。
【００１１】
請求項３記載の塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物は、上記化２で示される化合物が、ポリプロピレン共重合体中でブロック共重合体を形成していることを特徴とする。
【００１２】
請求項４記載の塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物は、ポリプロピレン共重合体のメルトフローレートが４〜300g／10分であることを特徴とする。
【００１３】
請求項５記載の塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物は、ポリプロピレン共重合体が、有機アルミニウムオキシ化合物とシクロペンタジエニル骨格含有配位子を含む周期律表第４族遷移金属の混合物からなるオレフィン重合用触媒を用いて、プロピレンと上記化２式で示される化合物とを共重合して得られるポリプロピレン共重合体であることを特徴とする。
【００１４】
請求項６記載の塗装性に優れたガラス長繊維強化ポリプロピレン樹脂組成物は、ガラス長繊維強化ポリプロピレン樹脂組成物中のガラス繊維の含有量が10〜70重量％であることを特徴とする。
【００１５】
【発明の実施の形態】
本発明で用いるポリプロピレン共重合体は、プロピレンと次の化３式
【化３】

で表される化合物との共重合体である。
【００１６】
化３式で表される化合物として好適なものは、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸ブチル、メタクリル酸プロピル、メタクリル酸ペンチル、メタクリル酸、アクリル酸メチル、アクリル酸エチル、アクリル酸プロピル、アクリル酸ブチル、アクリル酸ペンチル、アクリル酸などが挙げられる。
【００１７】
本発明のポリプロピレン共重合体中に含まれる化３式で表される化合物の割合は、好ましくは、0.1 〜10.0重量％であり、かかる化合物の割合がこの範囲であると、ガラス長繊維強化ポリプロピレン樹脂組成物の機械的強度がより向上し、良好な塗装性が得られる。
更に好適な範囲は0.3 〜8.0 重量％であり、かかる範囲であると更に上記効果が向上する。
【００１８】
上記ポリプロピレン共重合体中に含まれる化３で表わされる化合物は、ポリプロピレン共重合体中でブロック共重合体を形成していることが好ましい。またその重合度は特に限定されないが、５〜100 であることが塗装性の点から好ましい。
【００１９】
塗装性が良好になる理由は、明確ではないが、特定の分子構造を有する極性物質を重合過程でプロピレンと共重合することによって、ポリプロピレン主鎖中に、高濃度で、塗料との親和性に優れるポリマー鎖、例えば、化３式で表される化合物のブロック重合体を導入できるものと考えられる。
【００２０】
本発明のポリプロピレン共重合体の構造は例えば、下記化４式及び化５式で示される構造を有する。
【化４】

【化５】

【００２１】
また、ポリプロピレン共重合体のメルトフローレートは４〜300g／10分であることが好ましい。メルトフローレートがかかる範囲の場合には、ガラスロービング中への含浸が十分であり、ガラス長繊維強化ポリプロピレン樹脂組成物の機械的強度がより向上する。
【００２２】
本発明のポリプロピレン共重合体の重合に用いる触媒はメタロセン系重合触媒であれば特に限定されないが、有機アルミニウムオキシ化合物とシクロペンタジエニル骨格含有配位子を含む周期律表第４族遷移金属からなるオレフィン重合用触媒が反応性の点から好ましい。
【００２３】
有機アルミニウムオキシ化合物としては、例えば水とアルキルアルミニウムとの縮合物が含まれ、特にアルモキサンが好ましい。
更に、シクロペンタジエニル骨格含有配位子を含む周期律表第４族遷移金属中の遷移金属としてはZrおよびHfが好ましい。オレフィン重合用触媒は、上記有機アルミニウムオキシ化合物と、上記シクロペンタジエニル骨格含有配位子を含む周期律表第４族遷移金属とから成り、その割合は、特に制限されないが、好ましくはAl原子に対して周期律表第４族遷移金属原子の割合が10：１〜２：１の範囲である。
【００２４】
ポリプロピレン樹脂組成物中のガラス長繊維の含有量は、好ましくは10〜70重量％、さらに好ましくは、30〜60重量％である。この範囲内であると、長繊維強化ポリプロピレン樹脂組成物の機械的強度が向上し、表面でのガラスの露出が防止され、表面性や成形性が向上する。
【００２５】
本発明の組成物中には、その効果を損なわない範囲内でエチレン−プロピレンゴム、ＥＰＤＭ、スチレン−エチレン−ブチレン−スチレン共重合ゴム、スチレン−ブタジエン−スチレン共重合ゴムなどを添加してもよい。さらに、酸化防止剤、可塑剤、光安定剤などの添加剤や、タルク、マイカ、炭酸カルシウムなどのフィラーおよびカーボンブラックやカーボン繊維なども添加してもよい。
【００２６】
本発明に用いるポリプロピレン共重合体の製造法としては、特に制限されないが、例えば、不活性な重合溶剤中で、前記重合触媒の存在下、プロピレンガスに続いて、上記化３で示される化合物を供給し、所定時間反応させた後、アルコール等を添加して触媒を不活性化することで得られる。
【００２７】
上記ポリプロピレン共重合体中に平均繊維長が１mm以上のガラス繊維を配合する方法としては、例えば、ガラスロービングに、溶融したポリプロピレンを含浸させ、得られたストランドを数十〜数mm程度にカットし、それを射出成形する方法などがある。ガラス繊維の平均繊維長が１mm未満の場合には、ガラス長繊維強化ポリプロピレン樹脂組成物の機械的強度が十分ではなく好ましくない。
【００２８】
【実施例】
本発明を以下の実施例及び比較例により具体的に説明する。
実施例１
攪拌機を備えた内容積100 リットルのステンレス製反応器内をプロピレンガスで置換したのち、重合溶剤として、ヘプタン40リットルを入れた。器内温度を55℃に保ち、触媒としてジメチルシリルビス（2,4-ジメチルシクロペンタジニエル）ジルコニウムジクロリド11g およびメチルアルミノキサン11g を加えた。続いて、プロピレンと水素との混合ガス（体積割合＝９：１）を 1.1kg／時で供給し、器内温度を60℃に昇温した。プロピレンの供給を開始して、10分後にメタクリル酸エチルを 0.075kg／時で供給開始した。プロピレンの供給を開始して45分後に原料の供給を停止し、さらに10分重合を続けた後、器内を常圧に戻した。得られたスラリーにブタノール0.5 リットルを加えて60℃にて一時間処理し、更に水と充分に接触させ、水層を分離することで、触媒の不活性化ならびに触媒残さの除去を行った（メタクリル酸エチルモノマーの割合は5.3 重量％) 。
【００２９】
得られたポリプロピレン共重合体を50kg／時の速度で溶融しながら含浸装置（温度260 ℃) に供給する一方、同時にガラスロービングを50kg／時の速度で含浸装置に供給してノズルを通してストランド化した後、ストランドカッターを用いてガラス繊維の長さを約４mmとし、本発明のガラス長繊維強化ポリプロピレン樹脂（ガラス繊維含有量50重量％) を得た。
【００３０】
実施例２〜７
実施例１におけるメタクリル酸エチルを、以下の表１に示した化合物に変えた以外は実施例１と同じ方法で、本発明のガラス長繊維強化ポリプロピレン樹脂を得た。
【００３１】
【表１】

【００３２】
実施例８
実施例１の重合反応時において、プロピレンと水素の混合ガス（体積割合＝９：１）を 1.1kg／時で供給し、器内温度を60℃に昇温後、プロピレンの供給を開始して、10分後にメタクリル酸エチルを 0.075kg／時で供給開始し、プロピレンの供給を開始して45分後に原料の供給を停止し、さらに２分重合を続けた後、器内を常圧に戻した以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂を得た。
【００３３】
実施例９
実施例１の重合反応時において、プロピレンと水素の混合ガス（体積割合＝９：１）を 1.1kg／時で供給し、器内温度を60℃に昇温後、プロピレンの供給を開始して、10分後にメタクリル酸エチルを 0.075kg／時で供給開始し、プロピレンの供給を開始して45分後に原料の供給を停止し、さらに20分重合を続けた後、器内を常圧に戻した以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂を得た。
【００３４】
実施例 10
実施例１のガラスロービング中への樹脂含浸工程において、ポリプロピレン共重合体の含浸装置への供給速度を90kg／時、ガラスロービングの供給速度を10kg／時とした以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂（ガラス繊維含浸量10重量％) を得た。
【００３５】
実施例 11
実施例１のガラスロービング中への樹脂含浸工程において、ポリプロピレン共重合体の含浸装置への供給速度を30kg／時、ガラスロービングの供給速度を70kg／時とした以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂（ガラス繊維含有量70重量％) を得た。
【００３６】
実施例 12
実施例１の重合反応時において、メタクリル酸エチルの供給量を0.0015kg／時とした以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂を得た（メタクリル酸エチルモノマーの割合は 0.1重量％) 。
【００３７】
実施例 13
実施例１の重合反応時において、メタクリル酸エチルの供給量を0.15kg／時とした以外は、実施例１と同様の方法で本発明のガラス長繊維強化ポリプロピレン樹脂を得た（メタクリル酸エチルモノマーの割合は10.0重量％) 。
【００３８】
比較例１
実施例１において、メタクリル酸エチルを用いなかった以外は実施例１と同様の方法でポリプロピレン(MFR＝18g/10分) を製造し、ガラス長繊維強化ポリプロピレン樹脂を得た。
【００３９】
比較例２
市販のポリプロピレン（住友化学工業製ホモポリプロピレン W101)と無水マレイン酸変性ポリプロピレン（三井石油化工業学製アドマー QB505) を各々、90重量％と10重量％の割合でドライブレンドした混合物(MFR＝30g/10分) を用いて、実施例１と同様の方法でガラス長繊維強化ポリプロピレン樹脂を得た。
【００４０】
試験例
上記実施例１〜13及び比較例１〜２で得られたガラス繊維強化ポリプロピレン樹脂の機械的強度試験及び塗装性試験を実施した。
【００４１】
（試験例１）
各ガラス繊維強化ポリプロピレン樹脂ペレットを、シリンダー温度230 ℃、金型温度80℃の射出成形機を用いて、10.0cm×15.0cmの平板のJIS 規格に準拠した曲げ強度および引っ張り強度測定用試験片に成形した。
【００４２】
上記平板の表面をトルエンで洗浄した後、日本ビーケミカル社製２液型ウレタン系塗料を塗布し、120 ℃で20分間硬化させた。
【００４３】
次いで、得られた試験片に機械的強度、即ち引張強度、曲げ強度、曲げ弾性率およびIzod衝撃強度を、引張強度は、ASTM D638 により、曲げ強度は、ASTM D790 により、曲げ弾性率は、ASTM D790 により、Izod衝撃強度は、ASTM D256 により試験した。
【００４４】
（試験例２）
塗装性を、升目試験により評価した。升目試験は、塗料を塗布した面に、約１ｍｍ角に１００個の切れ目をカッターナイフで入れ、この上にセロハンテープ（ＪＩＳ Ｚ １５２２に規定されたもの）をはり、剥がすことにより行った。この試験の結果は、この際に残存する升目の数で示す。
【００４５】
（試験例３）
ポリプロピレン共重合体のメルトフローレート(MFR) はJIS K 7210(230℃, 2.16kgf)にしたがって測定した。
【００４６】
（試験例４）
ガラス繊維強化ポリプロピレン樹脂成形品を600 ℃で焼成して樹脂成分を除いた後、残存するガラス繊維(GF)の平均繊維長を光学顕微鏡写真により求めた。
【００４７】
上記機械的強度試験、枡目試験、メルトフローレートおよびガラス繊維の平均繊維長の測定結果を表２に示す。
【００４８】
【表２】

【００４９】
ポリプロピレンのみを用いてガラス長繊維強化樹脂を製造した場合（比較例１）、無水マレイン酸変性ポリプロピレンとポリプロピレンとの混合物を用いてガラス長繊維強化樹脂を製造した場合（比較例２）に比して、本発明の組成物は塗装性および機械的強度に優れている。
【００５０】
【発明の効果】
本発明のガラス長繊維強化ポリプロピレン樹脂は、ガラス長繊維強化ポリプロピレンの優れた機械的強度を低下させることなく、同時に優れた塗装性を示す。従って、本発明のガラス長繊維強化ポリプロピレン樹脂は、その優れた機械的強度と塗装性から、自動車部品、電器部品、建材等の広範囲な分野での使用が可能となる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a long glass fiber reinforced polypropylene resin composition excellent in paintability.
[0002]
[Prior art]
Polypropylene resins are used in various fields because they are excellent in moldability, heat resistance, mechanical strength, solvent resistance, and the like. A short glass fiber reinforced polypropylene resin composition obtained by kneading polypropylene and glass chopped strands with an extruder or the like is also known. This short glass fiber reinforced polypropylene resin composition has improved mechanical strength compared to unreinforced polypropylene resin.
[0003]
However, this short glass fiber reinforced polypropylene resin composition has a problem in that sufficient strength cannot be obtained because the glass fiber is severely broken by the screw of the extruder during the production process. Furthermore, in kneading using an extruder, it is difficult to make the glass fiber content 50% by weight or more, and there is a limit to improvement in mechanical strength.
[0004]
In recent years, instead of chopped strands, glass roving was used, and this was impregnated with molten polypropylene, and the resulting strands were cut to about several tens of millimeters, and then injection-molded. Compositions with long fiber lengths have been proposed. Since this composition has a longer glass fiber length than the short glass fiber reinforced polypropylene obtained by an extruder, the mechanical strength is further improved as compared with the short glass fiber reinforced polypropylene.
[0005]
In addition, since the base resin polypropylene has high crystallinity and no polarity, the wettability with the paint is poor and the paintability is poor. For this reason, when it uses for the exterior components for motor vehicles, the use is limited.
[0006]
As a method for improving the paintability of polypropylene, a method of adding a thermoplastic elastomer for the purpose of lowering crystallinity is disclosed in JP-A-61-233048 and the like, and maleic anhydride-modified polypropylene is used for the purpose of improving polarity. A method of adding is disclosed in JP-A-4-50248.
[0007]
However, when the method of adding the thermoplastic elastomer is applied to the long glass fiber reinforced polypropylene, the high mechanical strength characteristic of the long glass fiber reinforced polypropylene is reduced, and the method of adding the maleic anhydride modified polypropylene Although the polarity is slightly improved, the paintability is still insufficient.
[0008]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide a polypropylene resin composition having excellent paintability without reducing the mechanical strength of the long glass fiber reinforced polypropylene resin.
[0009]
[Means for Solving the Problems]
That is, the long glass fiber reinforced polyurethane resin composition excellent in paintability according to claim 1,
Propylene and the following general formula

(Wherein R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and a polypropylene copolymer with a compound represented by:
A glass long fiber reinforced polypropylene resin composition excellent in paintability containing glass fibers having an average fiber length of 1 mm or more ,
100 mm squares of 1 mm square were prepared by cutting the surface of the resin composition molded body coated with the paint, and cellophane tape (specified in JIS Z 1522) was put on the squares. Thereafter, in the cell test for removing the cellophane tape, the number of the cells remaining on the surface of the molded body is 78 or more out of 100 .
[0010]
The long glass fiber reinforced polypropylene resin composition having excellent paintability according to claim 2, wherein the proportion of the compound represented by the above formula 2 contained in the polypropylene copolymer is 0.1 to 10.0% by weight. To do.
[0011]
The long glass fiber reinforced polypropylene resin composition having excellent paintability according to claim 3 is characterized in that the compound represented by Chemical Formula 2 forms a block copolymer in the polypropylene copolymer.
[0012]
The long glass fiber reinforced polypropylene resin composition excellent in paintability according to claim 4 is characterized in that the melt flow rate of the polypropylene copolymer is 4 to 300 g / 10 min.
[0013]
The long glass fiber reinforced polypropylene resin composition excellent in paintability according to claim 5, wherein the polypropylene copolymer comprises an organoaluminumoxy compound and a cyclopentadienyl skeleton-containing ligand. It is a polypropylene copolymer obtained by copolymerizing propylene and a compound represented by the above formula 2 using an olefin polymerization catalyst comprising a mixture of
[0014]
The glass long fiber reinforced polypropylene resin composition excellent in paintability according to claim 6 is characterized in that the glass fiber content in the glass long fiber reinforced polypropylene resin composition is 10 to 70% by weight.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
The polypropylene copolymer used in the present invention comprises propylene and the following formula 3

It is a copolymer with the compound represented by these.
[0016]
Suitable compounds represented by the formula 3 are methyl methacrylate, ethyl methacrylate, butyl methacrylate, propyl methacrylate, pentyl methacrylate, methacrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, acrylic Examples include butyl acid, pentyl acrylate, and acrylic acid.
[0017]
The ratio of the compound represented by Formula 3 contained in the polypropylene copolymer of the present invention is preferably 0.1 to 10.0% by weight. When the ratio of the compound is within this range, the glass long fiber reinforced polypropylene is used. The mechanical strength of the resin composition is further improved, and good paintability is obtained.
A more preferable range is 0.3 to 8.0% by weight, and the above effect is further improved when it is within this range.
[0018]
The compound represented by Chemical Formula 3 contained in the polypropylene copolymer preferably forms a block copolymer in the polypropylene copolymer. The degree of polymerization is not particularly limited, but is preferably 5 to 100 from the viewpoint of paintability.
[0019]
The reason why the paintability is good is not clear, but by copolymerizing a polar substance having a specific molecular structure with propylene in the polymerization process, it becomes highly compatible in the polypropylene main chain with a high concentration of paint. It is considered that an excellent polymer chain, for example, a block polymer of a compound represented by Formula 3 can be introduced.
[0020]
The structure of the polypropylene copolymer of the present invention has, for example, structures represented by the following chemical formulas 4 and 5.
[Formula 4]

[Chemical formula 5]

[0021]
The melt flow rate of the polypropylene copolymer is preferably 4 to 300 g / 10 min. When the melt flow rate is within such a range, the impregnation into the glass roving is sufficient, and the mechanical strength of the long glass fiber reinforced polypropylene resin composition is further improved.
[0022]
The catalyst used for the polymerization of the polypropylene copolymer of the present invention is not particularly limited as long as it is a metallocene polymerization catalyst. From the group 4 transition metal of the periodic table containing an organoaluminumoxy compound and a cyclopentadienyl skeleton-containing ligand. An olefin polymerization catalyst is preferable from the viewpoint of reactivity.
[0023]
The organoaluminum oxy compound includes, for example, a condensate of water and alkylaluminum, and alumoxane is particularly preferable.
Furthermore, Zr and Hf are preferable as the transition metal in the Group 4 transition metal containing a cyclopentadienyl skeleton-containing ligand. The catalyst for olefin polymerization is composed of the organoaluminum oxy compound and a Group 4 transition metal containing the cyclopentadienyl skeleton-containing ligand, and the ratio is not particularly limited, but preferably an Al atom The ratio of Group 4 transition metal atoms in the periodic table is in the range of 10: 1 to 2: 1.
[0024]
The content of the long glass fiber in the polypropylene resin composition is preferably 10 to 70% by weight, more preferably 30 to 60% by weight. Within this range, the mechanical strength of the long fiber reinforced polypropylene resin composition is improved, the exposure of the glass on the surface is prevented, and the surface properties and moldability are improved.
[0025]
In the composition of the present invention, ethylene-propylene rubber, EPDM, styrene-ethylene-butylene-styrene copolymer rubber, styrene-butadiene-styrene copolymer rubber, etc. may be added within the range not impairing the effect. . Furthermore, additives such as antioxidants, plasticizers, light stabilizers, fillers such as talc, mica and calcium carbonate, carbon black and carbon fibers may be added.
[0026]
The method for producing the polypropylene copolymer used in the present invention is not particularly limited. For example, in the presence of the polymerization catalyst in the presence of the polymerization catalyst, the compound represented by the above chemical formula 3 is added. After supplying and reacting for a predetermined time, the catalyst is inactivated by adding alcohol or the like.
[0027]
As a method of blending glass fibers having an average fiber length of 1 mm or more in the polypropylene copolymer, for example, glass roving is impregnated with molten polypropylene, and the obtained strand is cut into several tens to several mm. And a method of injection molding it. When the average fiber length of the glass fiber is less than 1 mm, the mechanical strength of the long glass fiber reinforced polypropylene resin composition is not sufficient, which is not preferable.
[0028]
【Example】
The present invention will be specifically described with reference to the following examples and comparative examples.
Example 1
After replacing the inside of a 100 liter stainless steel reactor equipped with a stirrer with propylene gas, 40 liters of heptane was added as a polymerization solvent. The internal temperature was maintained at 55 ° C., and 11 g of dimethylsilylbis (2,4-dimethylcyclopentadiniel) zirconium dichloride and 11 g of methylaluminoxane were added as catalysts. Subsequently, a mixed gas of propylene and hydrogen (volume ratio = 9: 1) was supplied at 1.1 kg / hour, and the internal temperature was raised to 60 ° C. Propylene supply was started, and 10 minutes later, ethyl methacrylate was supplied at 0.075 kg / hour. After 45 minutes from the start of the supply of propylene, the supply of the raw material was stopped, and the polymerization was continued for another 10 minutes. The resulting slurry was added with 0.5 liter of butanol and treated at 60 ° C. for 1 hour, further contacted with water sufficiently, and the aqueous layer was separated to inactivate the catalyst and remove the catalyst residue ( (The ratio of ethyl methacrylate monomer is 5.3% by weight).
[0029]
The obtained polypropylene copolymer was supplied to the impregnation apparatus (temperature 260 ° C.) while being melted at a rate of 50 kg / hour, and at the same time, glass roving was supplied to the impregnation apparatus at a speed of 50 kg / hour to form a strand through a nozzle. Thereafter, the length of the glass fiber was set to about 4 mm using a strand cutter, and the glass long fiber reinforced polypropylene resin (glass fiber content 50% by weight) of the present invention was obtained.
[0030]
Examples 2-7
A glass long fiber reinforced polypropylene resin of the present invention was obtained in the same manner as in Example 1 except that the ethyl methacrylate in Example 1 was changed to the compounds shown in Table 1 below.
[0031]
[Table 1]

[0032]
Example 8
In the polymerization reaction of Example 1, a propylene / hydrogen mixed gas (volume ratio = 9: 1) was supplied at 1.1 kg / hour, the temperature in the vessel was raised to 60 ° C., and then the supply of propylene was started. 10 minutes later, ethyl methacrylate started to be supplied at 0.075 kg / hour, propylene supply was started, 45 minutes later, the supply of raw materials was stopped, and the polymerization was continued for 2 minutes. Except for the above, the glass long fiber reinforced polypropylene resin of the present invention was obtained in the same manner as in Example 1.
[0033]
Example 9
In the polymerization reaction of Example 1, a propylene / hydrogen mixed gas (volume ratio = 9: 1) was supplied at 1.1 kg / hour, the temperature in the vessel was raised to 60 ° C., and then the supply of propylene was started. After 10 minutes, start supplying ethyl methacrylate at 0.075 kg / hour, start supplying propylene, stop supplying the raw material 45 minutes later, continue polymerization for another 20 minutes, and then return the interior to normal pressure Except for the above, the glass long fiber reinforced polypropylene resin of the present invention was obtained in the same manner as in Example 1.
[0034]
Example 10
In the resin impregnation step in the glass roving of Example 1, the same as in Example 1 except that the supply rate of the polypropylene copolymer to the impregnation apparatus was 90 kg / hour and the glass roving supply rate was 10 kg / hour. By the method, the glass long fiber reinforced polypropylene resin of the present invention (glass fiber impregnation amount 10% by weight) was obtained.
[0035]
Example 11
In the resin impregnation step in the glass roving of Example 1, the same as in Example 1 except that the supply rate of the polypropylene copolymer to the impregnation apparatus was 30 kg / hour and the glass roving supply rate was 70 kg / hour. By the method, the glass long fiber reinforced polypropylene resin of the present invention (glass fiber content: 70% by weight) was obtained.
[0036]
Example 12
A glass long fiber reinforced polypropylene resin of the present invention was obtained in the same manner as in Example 1 except that the amount of ethyl methacrylate supplied was 0.0015 kg / hour during the polymerization reaction of Example 1 (ethyl methacrylate monomer). Is 0.1% by weight).
[0037]
Example 13
A glass long fiber reinforced polypropylene resin of the present invention was obtained in the same manner as in Example 1 except that the amount of ethyl methacrylate supplied was 0.15 kg / hour during the polymerization reaction of Example 1 (ethyl methacrylate monomer). The ratio is 10.0% by weight).
[0038]
Comparative Example 1
In Example 1, polypropylene (MFR = 18 g / 10 min) was produced in the same manner as in Example 1 except that ethyl methacrylate was not used, and a glass long fiber reinforced polypropylene resin was obtained.
[0039]
Comparative Example 2
Commercially blended polypropylene (Homopolypropylene W101 manufactured by Sumitomo Chemical Co., Ltd.) and maleic anhydride-modified polypropylene (Admer QB505 manufactured by Mitsui Petrochemical Industries) in a dry blend ratio of 90% by weight and 10% by weight, respectively (MFR = 30g / 10 minutes), a glass long fiber reinforced polypropylene resin was obtained in the same manner as in Example 1.
[0040]
Test Example A mechanical strength test and a paintability test of the glass fiber reinforced polypropylene resins obtained in Examples 1 to 13 and Comparative Examples 1 and 2 were performed.
[0041]
(Test Example 1)
Each glass fiber reinforced polypropylene resin pellet is used as a test piece for measuring bending strength and tensile strength in compliance with JIS standards on a 10.0cm x 15.0cm flat plate using an injection molding machine with a cylinder temperature of 230 ° C and a mold temperature of 80 ° C. Molded.
[0042]
After the surface of the flat plate was washed with toluene, a two-component urethane-based paint manufactured by Nippon Bee Chemical Co. was applied and cured at 120 ° C. for 20 minutes.
[0043]
Next, the obtained test piece was subjected to mechanical strength, that is, tensile strength, bending strength, bending elastic modulus and Izod impact strength, tensile strength according to ASTM D638, bending strength according to ASTM D790, and bending elastic modulus according to ASTM. According to D790, Izod impact strength was tested according to ASTM D256.
[0044]
(Test Example 2)
The paintability was evaluated by a grid test. The grid test was carried out by putting 100 cuts in a square of about 1 mm square with a cutter knife on the surface to which the paint was applied, applying cellophane tape ( as defined in JIS Z 1522 ) on the surface, and peeling it off. The result of this test is indicated by the number of cells remaining at this time.
[0045]
(Test Example 3)
The melt flow rate (MFR) of the polypropylene copolymer was measured according to JIS K 7210 (230 ° C., 2.16 kgf).
[0046]
(Test Example 4)
After the glass fiber reinforced polypropylene resin molded product was baked at 600 ° C. to remove the resin component, the average fiber length of the remaining glass fibers (GF) was determined from an optical micrograph.
[0047]
Table 2 shows the measurement results of the mechanical strength test, the mesh test, the melt flow rate, and the average fiber length of the glass fibers.
[0048]
[Table 2]

[0049]
Compared to the case of producing a long glass fiber reinforced resin using only polypropylene (Comparative Example 1) and the case of producing a glass long fiber reinforced resin using a mixture of maleic anhydride-modified polypropylene and polypropylene (Comparative Example 2). In addition, the composition of the present invention is excellent in paintability and mechanical strength.
[0050]
【The invention's effect】
The long glass fiber reinforced polypropylene resin of the present invention exhibits excellent paintability at the same time without reducing the excellent mechanical strength of the long glass fiber reinforced polypropylene. Therefore, the long glass fiber reinforced polypropylene resin of the present invention can be used in a wide range of fields such as automobile parts, electric parts and building materials because of its excellent mechanical strength and paintability.

Claims (6)

Propylene and the following general formula

(Wherein R ₁ and R ₂ represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) and a polypropylene copolymer with a compound represented by:
A glass long fiber reinforced polypropylene resin composition excellent in paintability containing glass fibers having an average fiber length of 1 mm or more ,
100 mm squares of 1 mm square were prepared by cutting the surface of the resin composition molded body on which the paint was applied, and cellophane tape (specified in JIS Z 1522) was put on the squares. Thereafter, in the cell test for removing the cellophane tape, the number of cells remaining on the surface of the molded body is 78 or more out of 100, and the glass long fiber reinforced polypropylene resin composition having excellent paintability .   2. The glass long fiber reinforced polypropylene having excellent paintability according to claim 1, wherein the proportion of the compound represented by the above formula 1 contained in the polypropylene copolymer is 0.1 to 10.0% by weight. Resin composition.   3. The glass long fiber reinforced polypropylene resin composition having excellent paintability according to claim 1 or 2, wherein the compound represented by Chemical Formula 1 forms a block copolymer in the polypropylene copolymer.   The melt flow rate of a polypropylene copolymer is 4 to 300 g / 10 minutes, The glass long fiber reinforced polypropylene resin composition excellent in paintability according to any one of claims 1 to 3.   Polypropylene copolymer is a compound represented by the above formula 1 using propylene and a catalyst for olefin polymerization consisting of a transition metal of Group 4 transition metal containing an organoaluminum oxy compound and a cyclopentadienyl skeleton-containing ligand. The long glass fiber reinforced polypropylene resin composition having excellent paintability according to any one of claims 1 to 4, which is a polypropylene copolymer obtained by copolymerization of   The glass long fiber reinforcement excellent in paintability according to any one of claims 1 to 5, wherein the glass fiber content in the glass long fiber reinforced polypropylene resin composition is 10 to 70% by weight. Polypropylene resin composition.