於本說明書中，「(甲基)丙烯酸」包含甲基丙烯酸及丙烯酸，「(甲基)丙烯酸酯」包含甲基丙烯酸酯及丙烯酸酯。 [1.改質聚烯烴系樹脂] 本發明之改質聚烯烴系樹脂係於成分(A)：聚烯烴樹脂或其改質物接枝有成分(B)：包含源自上述通式(I)所表示之(甲基)丙烯酸酯之結構單元(i)且玻璃轉移溫度(Tg)為0℃以下之聚合物而成之共聚物。 [1-1.成分(A)] 成分(A)係聚烯烴樹脂或聚烯烴樹脂之改質物。 [1-1-1.聚烯烴樹脂] 作為成分(A)之聚烯烴樹脂係烯烴之聚合物。關於作為成分(A)之聚烯烴樹脂，較佳為使用齊格勒-納塔(Ziegler Natta)觸媒或茂金屬觸媒作為聚合觸媒而製造之聚烯烴樹脂，更佳為使用齊格勒-納塔觸媒或茂金屬觸媒作為聚合觸媒而製造之使聚丙烯、或丙烯及α-烯烴(例如乙烯、丁烯、3-甲基-1-丁烯、3-甲基-1-庚烯)共聚合而獲得之聚烯烴樹脂。再者，有時將使丙烯及α-烯烴進行無規共聚合而獲得之聚烯烴樹脂稱為丙烯系無規共聚物。作為丙烯系無規共聚物，例如可列舉：乙烯-丙烯共聚物、丙烯-丁烯共聚物、乙烯-丙烯-二烯共聚物、乙烯-丙烯-丁烯共聚物。聚烯烴樹脂進而較佳為使用茂金屬觸媒作為聚合觸媒而製造之聚丙烯或丙烯系無規共聚物，尤佳為使用茂金屬觸媒作為聚合觸媒而製造之聚丙烯、乙烯-丙烯共聚物、丙烯-丁烯共聚物、或乙烯-丙烯-丁烯共聚物。該等樹脂可單獨為一種，亦可為複數種樹脂之組合。 作為上述茂金屬觸媒，可使用公知者。作為茂金屬觸媒，具體而言，例如可列舉將以下所述之成分(1)及(2)、進而視需要之(3)進行組合而獲得之觸媒，較佳為將以下所述之成分(1)及(2)、進而視需要之(3)進行組合而獲得之觸媒。 ·成分(1)：作為具有至少一個共軛五員環配位基之週期表第4～6族之過渡金屬化合物的茂金屬錯合物。 ·成分(2)：離子交換性層狀矽酸鹽。 ·成分(3)：有機鋁化合物。 使用茂金屬觸媒所合成之聚烯烴樹脂具有分子量分佈狹窄、無規共聚合性優異且組成分佈狹窄、且能夠共聚合之共聚單體之範圍寬廣等特徵，因此，較佳為作為成分(A)。 作為成分(A)之聚烯烴樹脂之結構並無特別限定，可為能夠獲得通常之高分子化合物之同排結構、雜排結構、對排結構等中之任一者。若考慮到對聚烯烴基材之附著性、尤其是低溫乾燥時之附著性，則作為成分(A)，較佳為使用茂金屬觸媒進行聚合而成之同排結構之聚烯烴樹脂。 作為成分(A)之聚烯烴樹脂之成分組成並無特別限定，較佳為成分(A)之丙烯成分較佳為60莫耳%以上，更佳為70莫耳%以上，進而較佳為80莫耳%以上。於成分(A)之丙烯成分為60莫耳%以上之情形時，對丙烯基材之附著性(接著性)變得更加良好。 [1-1-2.聚烯烴樹脂之改質物] 成分(A)亦可為聚烯烴樹脂之改質物。聚烯烴樹脂之改質物中之聚烯烴樹脂之例及較佳例係如於上述項目[1-1-1.聚烯烴樹脂]中既已說明般。 改質種類並無特別限定，例如可列舉：氯化；環氧化；羥基化；羧酸酐化；羧酸化等公知之改質。聚烯烴樹脂之改質物可藉由使用公知之方法將聚烯烴樹脂改質而獲得。作為成分(A)之聚烯烴樹脂之改質物較佳為氯化聚烯烴樹脂。下文對聚烯烴樹脂之氯化方法進行說明。 於成分(A)為氯化聚烯烴樹脂之情形時，作為成分(A)之氯化聚烯烴樹脂之氯含有率較佳為15重量%以上，更佳為20重量%以上。若氯含有率為15重量%以上，則改質聚烯烴系樹脂於乙醇、異丙醇等醇類中之分散性優異。作為成分(A)之氯化聚烯烴樹脂中之氯含有率之上限較佳為40重量%以下，更佳為35重量%以下。若氯含有率為40重量%以下，則改質聚烯烴系樹脂對聚烯烴系基材之附著性優異。 再者，樹脂之氯含有率可基於JIS-K7229進行測定。 又，本發明之改質聚烯烴系樹脂中之成分(A)之氯含有率通常與藉由成分(B)進行接枝前之作為原料之成分(A)之氯含有率一致。 作為成分(A)之改質物亦可為聚烯烴樹脂藉由酸進行改質而成之酸改質物。作為用以進行改質之酸，並無特別限定，例如可列舉：α,β-不飽和羧酸及α,β-不飽和羧酸之衍生物(例如馬來酸、馬來酸酐、富馬酸、檸康酸、檸康酸酐、中康酸、伊康酸、伊康酸酐、烏頭酸、烏頭酸酐、雙環庚烯二甲酸酐、(甲基)丙烯酸)，較佳為α,β-不飽和羧酸之酸酐，更佳為馬來酸酐。 作為將聚烯烴樹脂藉由酸進行改質方法，可使用公知之方法，例如可列舉將聚烯烴樹脂熔融並添加用以進行改質之酸及自由基反應起始劑而獲得酸改質聚烯烴樹脂之方法。反應裝置並無特別限定，例如亦可使用擠出機進行改質反應。 作為成分(A)之改質物亦可為聚烯烴樹脂藉由複數種改質材料進行改質而成之改質物。因此，作為成分(A)之改質物亦可為將氯化聚烯烴樹脂藉由酸(例如α,β-不飽和羧酸或α,β-不飽和羧酸之衍生物)進行改質而獲得之酸改質氯化聚烯烴樹脂。 成分(A)較佳為氯化聚烯烴樹脂或酸改質氯化聚烯烴樹脂。 [1-1-3.成分(A)之重量平均分子量] 成分(A)之重量平均分子量(Mw)較佳為5,000以上。若重量平均分子量為5,000以上，則樹脂之凝聚力充分且對基材之附著性優異。成分(A)之重量平均分子量之上限較佳為150,000以下。若重量平均分子量為150,000以下，則與塗料或油墨中包含之其他樹脂之相容性良好，且對基材之附著性良好。再者，重量平均分子量可藉由凝膠滲透層析法(GPC，gel permeation chromatography)法且根據標準聚苯乙烯檢量線求出。 成分(A)之重量平均分子量較佳為5,000～150,000。 此處，成分(A)之重量平均分子量通常與對將成分(B)接枝前之作為原料之成分(A)測得之重量平均分子量一致。 [1-2.成分(B)] 成分(B)係包含源自通式(I)所表示之(甲基)丙烯酸酯之結構單元(i)且玻璃轉移溫度(Tg)為0℃以下之聚合物。 [1-2-1.結構單元(i)] 成分(B)包含源自通式(I)所表示之(甲基)丙烯酸酯之結構單元(i)。 CH2
=C(R1
)COOR2
…(I) 通式(I)中，R1
表示氫原子或甲基，R2
表示-Cn
H2n ＋ 1
所表示之基，n表示1～18之整數。 作為-Cn
H2n ＋ 1
所表示之基，可為直鏈烷基，亦可為支鏈烷基。 此處，所謂源自某單體之結構單元，係指將某單體用於聚合反應之情形時所獲得之結構單元。 結構單元(i)較佳為碳原子數為4以上、較佳為12以下。結構單元(i)較佳為碳原子數為4～12。藉此，改質聚烯烴系樹脂之耐碎裂性能夠變得更優異。此處，結構單元(i)之碳原子數通常與作為結構單元(i)來源之通式(I)所表示之(甲基)丙烯酸酯之碳原子數相同。 於成分(B)包含碳原子數為4～12之結構單元(i)(以下，亦稱為結構單元(i4-12
))之情形時，成分(B)中之結構單元(i4-12
)之含有率較佳為40重量%以上，更佳為60重量%以上，且較佳為100重量%以下。藉此，於將改質聚烯烴系樹脂與其他成分組合而製成組合物(例如塗料組合物)之情形時，與其他成分之相容性變得良好。 成分(B)中之結構單元(i4-12
)之含有率(%)通常與通式(I)所表示之(甲基)丙烯酸酯且碳原子數為4～12之某單體相對於製造成分(B)之聚合物時所使用之總單體重量的重量百分率一致。 成分(B)中包含之結構單元(i)可單獨為一種，亦可為兩種以上。 成分(B)中亦可包含結構單元(i)以外之結構單元。作為成分(B)中可包含之結構單元(i)以外之結構單元，例如可列舉源自α,β-不飽和羧酸之結構單元(例如源自(甲基)丙烯酸之結構單元)、及結構單元(i)以外之源自α,β-不飽和羧酸酯之結構單元(例如(甲基)丙烯酸烷基酯、(甲基)丙烯酸羥基烷基酯)。 [1-2-2.成分(B)之玻璃轉移溫度] 成分(B)係玻璃轉移溫度(Tg)為0℃以下，較佳為-20℃以下，更佳為 -25℃以下，進而較佳為-30℃以下。於Tg超過0℃之情形時，改質聚烯烴系樹脂之柔軟性下降，因此，耐碎裂性較差。Tg通常為-70℃以上，較佳為-65℃以上，更佳為-60℃以上。 玻璃轉移溫度(Tg)能夠使用將構成成分(B)之各單體單元製成均聚物之情形時之各玻璃轉移溫度之值及成分(B)中之各單體單元之重量比率，並藉由下述FOX式算出。各均聚物之Tg可使用聚合物手冊(Wiley-Interscience Publication，第4版，1999)及製品資料中刊載之Tg。 成分(B)中之各單體單元之重量比率通常與各單體相對於製造成分(B)之聚合物時所使用之總單體重量的重量比率(調配比率)一致。 ＜FOX式＞1/Tg=W1
/Tg1
＋W2
/Tg2
＋W3
/Tg3
＋…Wn
/Tgn
上述式中，使成分(B)由n種單體單元U1
～Un
構成，且將單體單元U1
～Un
之均聚物之玻璃轉移溫度分別設為Tg1
～Tgn
，將單體單元U1
～Un
之重量比率分別設為W1
～Wn
。其中，將單體單元U1
～Un
之重量比率之合計設為1。 作為成分(B)之玻璃轉移溫度，可使用對接枝於成分(A)前之作為原料之成分(B)之聚合物測得之玻璃轉移溫度。作為原料之成分(B)之玻璃轉移溫度例如能夠使用示差掃描熱量計(例如「DSC6200R熱分析系統」，由Seiko Instruments Inc.提供)進行測定。 較佳為，本發明之成分(B)之玻璃轉移溫度係使用將構成成分(B)之各單體單元製成均聚物之情形時之各玻璃轉移溫度之值及成分(B)中之各單體單元之重量比率，並藉由上述FOX式算出之值。 [1-2-3.成分(B)之重量平均分子量] 成分(B)之重量平均分子量(Mw)並無特別限定，較佳為1,000以上，更佳為3,000以上，且較佳為100,000以下，更佳為20,000以下。 成分(B)之重量平均分子量較佳為1,000～100,000，更佳為3,000～20,000。 此處，成分(B)之重量平均分子量通常與對接枝於成分(A)前之作為原料之成分(B)之聚合物測得之重量平均分子量一致。 [1-2-4.成分(B)之羥值] 成分(B)之羥值並無特別限定，較佳為5 mgKOH/g以上，且較佳為560 mgKOH/g以下，更佳為280 mgKOH/g以下，進而較佳為168 mgKOH/g以下。 若成分(B)之羥值為5 mgKOH/g以上，則於將改質聚烯烴系樹脂與其他成分組合而製成組合物(例如塗料組合物)之情形時，與其他成分之相容性變得良好。若成分(B)之羥值為560 mgKOH/g以下，則改質聚烯烴系樹脂之極性程度適當，因此，於將改質聚烯烴系樹脂與其他成分組合而製成組合物之情形時，與其他成分之相容性變得良好。 成分(B)之羥值較佳為5～560 mgKOH/g，更佳為5～280 mgKOH/g，進而較佳為5～168 mgKOH/g。 若成分(B)由n種(n為1以上之整數)單體單元U1
～Un
構成，且將單體單元U1
～Un
之均聚物之羥值分別設為X1
～Xn
(mgKOH/g)，將成分(B)中之單體單元U1
～Un
之重量比率分別設為Y1
～Yn
(其中，將單體單元U1
～Un
之重量比率之合計設為1)，則成分(B)之羥值XB
係藉由下述式算出。 XB
=X1
Y1
＋X2
Y2
＋…Xn
Yn
實施例中之成分(B)之羥值亦係藉由上述方法算出之值。 [1-3.改質聚烯烴系樹脂] 本發明之改質聚烯烴系樹脂係於上述成分(A)：聚烯烴樹脂或其改質物接枝有上述成分(B)而成之共聚物。 本發明之改質聚烯烴系樹脂可為於成分(A)接枝有成分(B)之共聚物，亦可為於用以於成分(A)接枝成分(B)之接枝聚合反應之後，進而藉由改質劑(例如藉由氯及/或酸)進行改質而成之共聚物，亦可為於接枝聚合反應後不進行進一步利用改質劑改質之共聚物。 本發明之改質聚烯烴系樹脂係於成分(A)接枝有成分(B)之聚合物。本發明之改質聚烯烴系樹脂可為藉由於作為原料之成分(A)利用接枝聚合反應接枝作為原料之成分(B)之聚合物而製造之樹脂，亦可為藉由於作為原料之成分(A)逐次或同時利用接枝聚合反應接枝用以構成成分(B)之聚合物(嵌段)之單體而製造之樹脂。 本發明之改質聚烯烴系樹脂可為經氯化之接枝改質聚烯烴系樹脂、經酸改質之接枝改質聚烯烴系樹脂、或經酸改質及氯化之接枝改質聚烯烴系樹脂。 本發明之改質聚烯烴系樹脂較佳為氯化樹脂。「氯化樹脂」包含成分(A)經氯化之樹脂、成分(B)經氯化之樹脂、成分(A)及(B)經氯化之樹脂。本發明之改質聚烯烴系樹脂更佳為成分(A)經氯化之氯化樹脂。 於改質聚烯烴系樹脂為氯化樹脂之情形時，改質聚烯烴系樹脂之氯含有率較佳為10重量%以上，更佳為15重量%以上。改質聚烯烴系樹脂中之氯含有率之上限較佳為35重量%以下，更佳為30重量%以下。 推測藉由改質聚烯烴系樹脂之氯含有率處於本範圍，而改質聚烯烴系樹脂之極性增強，而且改質聚烯烴系樹脂因氯原子彼此之立體排斥而容易顯示出直鏈結構，因此，推測於高極性溶劑(例如醇類)中之分散性優異。 [1-3-1.改質聚烯烴系樹脂之重量平均分子量] 本發明之改質聚烯烴系樹脂之重量平均分子量並無特別限定，較佳為10,000以上，更佳為30,000以上，且較佳為200,000以下，更佳為150,000以下。 藉由改質聚烯烴系樹脂之重量平均分子量為10,000以上，而附著性提昇。又，若改質聚烯烴系樹脂之重量平均分子量為200,000以下，則於將改質聚烯烴系樹脂與其他成分組合而形成組合物之情形時，與其他成分之相容性變得良好。 本發明之改質聚烯烴系樹脂之重量平均分子量較佳為10,000～200,000，更佳為30,000～150,000。 [1-3-2.成分(B)之含有率] 本發明之改質聚烯烴系樹脂中之成分(B)之含有率並無特別限定，較佳為20重量%以上，更佳為30重量%以上，進而較佳為50重量%以上。上限較佳為80重量%以下。 所謂改質聚烯烴系樹脂中之成分(B)之含有率係指接枝於成分(A)之成分(B)部分相對於改質聚烯烴系樹脂之重量比率。 成分(B)部分相對於改質聚烯烴系樹脂之重量比率(%)通常與製造改質聚烯烴系樹脂時對成分(A)進行接枝聚合之成分(B)之調配率(%)一致(其中，將成分(A)之調配重量及成分(B)之調配重量之合計設為100%)。 [1-3-3.成分(A)/成分(B)] 本發明之改質聚烯烴系樹脂中之成分(A)相對於成分(B)之重量比率並無特別限定，較佳為20/80以上，更佳為30/70以上，進而較佳為50/50以上，且較佳為80/20以下。 本發明之改質聚烯烴系樹脂中之成分(A)相對於成分(B)之重量比率較佳為20/80以上且80/20以下。 [2.改質聚烯烴系樹脂之製造方法] 本發明之改質聚烯烴系樹脂之製造方法例如包括如下步驟：於成分(A)：聚烯烴樹脂或其改質物上接枝聚合成分(B)：包含源自上述通式(I)所表示之(甲基)丙烯酸酯之結構單元(i)且玻璃轉移溫度(Tg)為0℃以下之聚合物。其中，式(I)中，R1
表示氫原子或甲基，R2
表示-Cn
H2n ＋ 1
所表示之基，n表示1～18之整數。 成分(A)及成分(B)與項目[1.改質聚烯烴系樹脂]中分別說明之成分(A)及成分(B)相同。 作為將成分(B)藉由接枝共聚合導入至成分(A)之方法，例如可列舉：於作為原料之成分(A)上接枝共聚合作為原料之成分(B)：包含源自上述通式(I)所表示之(甲基)丙烯酸酯之結構單元(i)且玻璃轉移溫度(Tg)為0℃以下之聚合物之方法；於作為原料之成分(A)上接枝共聚合作為用以構成成分(B)之聚合物之原料的上述通式(I)所表示之(甲基)丙烯酸酯之方法。 於對作為原料之成分(A)接枝共聚合上述通式(I)所表示之(甲基)丙烯酸酯之情形時，可將上述通式(I)所表示之(甲基)丙烯酸酯逐次添加至作為原料之成分(A)，亦可一次地添加至作為原料之成分(A)。又，亦可將上述通式(I)所表示之(甲基)丙烯酸酯以外之單體添加至作為原料之成分(A)。 接枝聚合之條件並無特別限定，例如可基於熔融法、溶液法等公知之方法。於利用熔融法之情形時，具有操作簡便並且能夠以短時間進行反應之優點。於利用溶液法之情形時，副反應較少而能夠獲得均勻之接枝聚合物。 於利用熔融法之情形時，於自由基反應起始劑之存在下，將成分(A)加熱熔解(加熱熔融)，使之與成分(B)反應。成分(B)可為聚合前之單體形態，亦可為聚合後之聚合物形態。加熱熔解之溫度只要為成分(A)之熔點以上即可，較佳為成分(A)之熔點以上且300℃以下。加熱熔解時，可使用班布里混合機、捏合機、擠出機等機器。 於利用溶液法之情形時，使成分(A)溶解於有機溶劑後，於自由基反應起始劑之存在下與成分(B)加熱攪拌而進行反應。成分(B)可為聚合前之單體形態，亦可為聚合後之聚合物形態。 作為有機溶劑，較佳為使用甲苯、二甲苯等芳香族烴溶劑。反應時之溫度較佳為100～180℃。 作為熔融法及溶液法時所使用之自由基反應起始劑，並無特別限定，例如可列舉有機過氧化物系化合物或偶氮腈類。作為有機過氧化物系化合物，例如可列舉：二(第三丁基)過氧化物、過氧化二異丙苯、第三丁基過氧化異丙苯、過氧化苯甲醯、二月桂基過氧化物、2,5-二甲基-2,5-二(過氧化第三丁基)己烷、氫過氧化異丙苯、氫過氧化第三丁基、1,1-雙(過氧化第三丁基)-3,5,5-三甲基環己烷、1,1-雙(過氧化第三丁基)環己烷、過氧化環己酮、過氧化苯甲酸第三丁酯、過氧化異丁酸第三丁酯、過氧化3,5,5-三甲基己酸第三丁酯、過氧化2-乙基己酸第三丁酯、過氧化異丙基碳酸第三丁酯、過氧化辛酸異丙苯酯等，可根據進行自由基聚合之溫度，選擇具有適當之半衰期溫度者。 於本發明之改質聚烯烴系樹脂之製造方法中，成分(A)亦可以除成分(A)以外還包含任意穩定劑之組合物之形態進行接枝聚合。 作為任意之穩定劑，例如可列舉：環氧化合物；用作聚氯乙烯樹脂之穩定劑之硬脂酸鈣、硬脂酸鉛等金屬皂類；二丁基二月桂酸錫、馬來酸二丁酯等有機金屬化合物類；鋁碳酸鎂類化合物。環氧化合物並無特別限定，較佳為能夠與經氯化等改質之樹脂相容之環氧化合物。作為環氧化合物，可例示環氧當量為100至500左右且每分子具有1個以上環氧基之化合物，作為此種環氧化合物，例如可列舉：將天然之具有不飽和基之植物油藉由過乙酸等過酸進行環氧化而獲得之環氧化植物油(環氧化大豆油、環氧化亞麻籽油等)；將油酸、妥爾油脂肪酸、大豆油脂肪酸等不飽和脂肪酸進行環氧化而成之環氧化脂肪酸酯類；環氧化四氫鄰苯二甲酸酯等環氧化脂環式化合物；將雙酚A或多元醇與表氯醇縮合而獲得之例如雙酚A縮水甘油醚、乙二醇縮水甘油醚、丙二醇縮水甘油醚、甘油聚縮水甘油醚、山梨糖醇聚縮水甘油醚等醚類；及以丁基縮水甘油醚、2-乙基己基縮水甘油醚、癸基縮水甘油醚、硬脂基縮水甘油醚、烯丙基縮水甘油醚、苯基縮水甘油醚、第二丁基苯基縮水甘油醚、第三丁基苯基縮水甘油醚、苯酚聚環氧乙烷縮水甘油醚等為代表之單環氧化合物類。穩定劑可單獨為一種，亦可為兩種以上之組合。於成分(A)以包含穩定劑之組合物之形態進行接枝聚合之情形時，穩定劑相對於成分(A)之重量比率較佳為1～20重量%(固形物成分換算)。 本發明之改質聚烯烴系樹脂之製造方法除上述步驟以外，還可包含任意之步驟。 作為任意之步驟，例如可列舉於成分(A)接枝聚合成分(B)而獲得接枝改質聚烯烴系樹脂後，進而將接枝改質聚烯烴系樹脂進行改質之步驟。改質種類並無特別限定，例如可列舉：氯化；環氧化；羥基化；羧酸酐化；羧酸化等公知之改質。 該等改質可藉由公知之方法進行。 例如，於改質聚烯烴系樹脂為氯化樹脂之情形時，本發明之製造方法亦可包含於其製造之任一階段將樹脂氯化之步驟，例如亦可包含：將聚烯烴樹脂氯化之步驟；於聚烯烴樹脂接枝聚合成分(B)後將所獲得之接枝改質聚烯烴系樹脂氯化之步驟。 因此，作為用以獲得作為氯化樹脂之改質聚烯烴系樹脂之製造方法，例如可列舉：將成分(B)接枝於成分(A)後進行氯化之方法；於將聚烯烴樹脂氯化而獲得作為成分(A)之氯化聚烯烴樹脂後，將成分(B)接枝於成分(A)之方法。 作為氯化之方法，可使用公知之方法，並無特別限定，例如可列舉將樹脂溶解於氯仿等氯化溶劑後吹入氯氣以導入氯之方法等。更具體而言，氯化可藉由將樹脂分散或溶解於水、四氯化碳、或氯仿等介質，於觸媒之存在下或紫外線之照射下，於加壓或常壓下，於50～140℃之溫度範圍內吹入氯氣而進行。 於在製造氯化樹脂時使用氯化溶劑之情形時，所使用之氯化溶劑通常可藉由減壓等而蒸餾去除，或者可利用其他有機溶劑進行置換。 於將聚烯烴樹脂氯化而獲得作為成分(A)之氯化聚烯烴樹脂之情形時，作為成分(A)之氯化聚烯烴樹脂之氯含有率較佳為15重量%以上，更佳為20重量%以上。若氯含有率為15重量%以上，則所獲得之改質聚烯烴系樹脂於乙醇、異丙醇等醇類中之分散性優異。作為成分(A)之氯化聚烯烴樹脂中之氯含有率之上限較佳為40重量%以下，更佳為35重量%以下。若氯含有率為40重量%以下，則所獲得之改質聚烯烴系樹脂對聚烯烴系基材之附著性優異。 [3.改質聚烯烴系樹脂組合物] 本發明之改質聚烯烴系樹脂可與其他任意成分一起構成改質聚烯烴系樹脂組合物。作為任意成分，例如可列舉用以抑制氯之脫附之穩定劑。穩定劑並無特別限定，例如可列舉：環氧化合物；用作聚氯乙烯樹脂之穩定劑之硬脂酸鈣、硬脂酸鉛等金屬皂類；二丁基二月桂酸錫、馬來酸二丁酯等有機金屬化合物類；鋁碳酸鎂類化合物，較佳為環氧化合物。環氧化合物並無特別限定，例如可列舉於上述[2.改質聚烯烴系樹脂之製造方法]中作為成分(A)之組合物可包含之任意穩定劑所例示之環氧化合物，較佳為與經氯改質之改質聚烯烴樹脂相容之環氧化合物。作為穩定劑，可僅使用該等中之一種，亦可併用兩種以上。 又，例如，改質聚烯烴系樹脂組合物亦可為包含改質聚烯烴系樹脂及分散介質之分散組合物之形態。再者，於本說明書中，「分散介質」包含可使改質聚烯烴系樹脂溶解之溶劑，「分散組合物」亦可為改質聚烯烴系樹脂組合物之溶液。 作為分散介質，例如可列舉：甲苯、二甲苯等芳香族烴；環己烷、甲基環己烷等脂環式烴；己烷、庚烷、辛烷等脂肪族烴；丙酮、甲基乙基酮、甲基異丁基酮等酮；乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸異丙酯、乙酸正丁酯等酯；甲醇、乙醇、正丙醇、異丙醇、正丁醇、異丁醇等醇；乙二醇、乙基溶纖劑、丁基溶纖劑等二醇；水等。 分散介質可單獨為一種，亦可為兩種以上之組合。 [4.改質聚烯烴系樹脂之用途] 本發明之改質聚烯烴系樹脂可用作金屬及/或樹脂用接著劑、底塗劑、塗料用黏合劑及油墨用黏合劑。本發明之改質聚烯烴系樹脂因附著性良好且耐碎裂性優異，故尤其是作為汽車塗料用黏合劑、汽車塗佈用底塗劑有用。 [實施例] 其次，藉由實施例及比較例對本發明進行詳細說明，但本發明並不限定於該等。「份」及「%」只要無特別說明，則分別指「重量份」及「重量%」。以下之操作只要無特別說明，則係於常溫常壓大氣中進行。 ＜製造例A1＞聚烯烴樹脂 將以茂金屬觸媒作為聚合觸媒而製造之丙烯系無規共聚物(丙烯單元含量：80重量%，乙烯單元含量20重量%)供給至料筒溫度設定為350℃之雙軸擠出機而進行熱降解，從而獲得重量平均分子量5,000之聚丙烯系樹脂(A1)。 ＜製造例A2＞聚烯烴樹脂 使用以茂金屬觸媒作為聚合觸媒而製造之丙烯系無規共聚物(丙烯單元含量：90重量%，乙烯單元含量10重量%)，除此以外，以與製造例A1相同之方式獲得重量平均分子量111,000之聚丙烯系樹脂(A2)。 ＜製造例A3＞聚烯烴樹脂 使用以茂金屬觸媒作為聚合觸媒而製造之丙烯系無規共聚物(丙烯單元含量：94重量%，乙烯單元含量6重量%)，除此以外，以與製造例A1相同之方式獲得重量平均分子量100,000之聚丙烯系樹脂(A3)。 ＜製造例A4＞聚烯烴樹脂 使用以茂金屬觸媒作為聚合觸媒而製造之丙烯系無規共聚物(丙烯單元含量：90重量%，乙烯單元含量5重量%，丁烯單元含量5重量%)，除此以外，以與製造例A1相同之方式獲得重量平均分子量45,000之聚丙烯系樹脂(A4)。 ＜製造例A5＞聚烯烴樹脂 將以茂金屬觸媒作為聚合觸媒而製造之丙烯系無規共聚物(丙烯單元含量：80重量%，乙烯單元含量20重量%)供給至料筒溫度設定為400℃之雙軸擠出機而進行熱降解，從而獲得重量平均分子量2,000之聚丙烯系樹脂(A5)。 ＜製造例CL1＞氯化聚烯烴樹脂 將製造例A1中獲得之聚丙烯系樹脂(A1)100重量份投入至經玻璃襯裡之反應釜。向其中添加氯仿，於2 kg/cm2
之壓力下，一面照射紫外線，一面吹入氯氣及氧氣，進行氯化直至氯含有率成為32 wt%。反應結束後，添加6重量份之環氧化合物(Epocizer W-100EL，大日本油墨化學工業(股)製造)作為穩定劑，並供給至於螺桿部具備脫溶劑用抽吸部之附通風孔之擠出機，進行脫溶劑、固形化，而獲得作為氯化聚烯烴樹脂之重量平均分子量5000之氯化聚丙烯系樹脂(A1CL1)。 ＜製造例CL2＞氯化聚烯烴樹脂 使用製造例A5中獲得之聚丙烯系樹脂(A5)，除此以外，以與製造例CL1相同之方式獲得重量平均分子量2,000之氯化聚丙烯系樹脂(A5CL2)。 ＜製造例CL3＞氯化聚烯烴樹脂 使用製造例A4中獲得之聚丙烯系樹脂(A4)，除此以外，以與製造例CL1相同之方式獲得重量平均分子量50,000之氯化聚丙烯系樹脂(A4CL3)。 ＜製造例M1＞酸改質聚烯烴樹脂 將製造例A3中獲得之聚丙烯系樹脂(A3)100重量份放入至安裝有攪拌機、滴液漏斗、及單體回流用冷卻管之三口燒瓶中，於180℃之油浴中進行完全溶解。對燒瓶內進行約10分鐘氮氣置換後，一面進行攪拌，一面歷時約5分鐘投入馬來酸酐4重量份，其次，將二第三丁基過氧化物0.4重量份溶解於庚烷1重量份中，利用滴液漏斗歷時約30分鐘投入。其後，將系統內保持於180℃，進而繼續反應1小時後，利用吸出器一面對燒瓶內進行減壓一面歷時約1小時去除未反應之馬來酸酐，而獲得重量平均分子量105,000之酸改質聚烯烴樹脂(A3M1)。 ＜製造例MCL1＞酸改質氯化聚烯烴樹脂 (酸改質) 將製造例A2中獲得之聚丙烯系樹脂(A2)100重量份與馬來酸酐4重量份、二第三丁基過氧化物2重量份均勻地混合，並供給至雙軸擠出機(L/D=60，f=15 mm，第1料筒～第14料筒)。於滯留時間為10分鐘、轉數200 rpm、料筒溫度為100℃(第1、2料筒)、200℃(第3～8料筒、90℃(第9、10料筒)、110℃(第11～14料筒)之條件下進行反應，藉由減壓處理將未反應之馬來酸酐去除，而獲得馬來酸酐改質聚丙烯系樹脂(A2M2)。 (氯化) 將所獲得之馬來酸酐改質聚丙烯系樹脂(A2M2)100重量份投入至經玻璃襯裡之反應釜。向其中添加氯仿，於2 kg/cm2
之壓力下，一面照射紫外線，一面吹入氯氣及氧氣，進行氯化直至氯含有率成為32 wt%。反應結束後，添加6重量份之環氧化合物(Epocizer W-100EL，大日本油墨化學工業(股)製造)作為穩定劑，並供給至於螺桿部具備脫溶劑用抽吸部之附通風孔之擠出機，進行脫溶劑、固形化，而獲得作為氯化聚烯烴樹脂之重量平均分子量143,000之酸改質氯化聚丙烯系樹脂(A2M2CL1)。 ＜製造例MCL2＞酸改質氯化聚烯烴樹脂 使用製造例A1中獲得之聚丙烯系樹脂A1，除此以外，以與製造例MCL1相同之方式獲得重量平均分子量5,000之酸改質氯化聚丙烯系樹脂(A1M2CL2)。 ＜製造例MCL3＞酸改質氯化聚烯烴樹脂 使用製造例A3中獲得之聚丙烯系樹脂A3，除此以外，以與製造例MCL1相同之方式獲得重量平均分子量110,000之酸改質氯化聚丙烯系樹脂(A3M2CL3)。 ＜製造例MCL4＞酸改質氯化聚烯烴樹脂 使用製造例A4中獲得之聚丙烯系樹脂A4，除此以外，利用與製造例M1相同之方法獲得酸改質聚烯烴系樹脂(A4M1)。繼而，使用所獲得之酸改質聚烯烴系樹脂(A4M1)，除此以外，以與製造例CL1相同之方式進行氯化，而獲得重量平均分子量75,000之酸改質氯化聚丙烯系樹脂(A4M1CL4)。 ＜實施例1＞ (丙烯酸系聚合物(B1)之製造) 於在氮氣氛圍下加溫至85℃之甲苯233份中，添加過氧酯系過氧化物(Nyper BMT-K40，日本油脂(股)製造)2.8重量份後，以表2之實施例1中記載之調配比，將各丙烯酸系單體以各丙烯酸系單體之合計添加100重量份，以85℃反應6小時以上，其後進行冷卻，而獲得玻璃轉移溫度-66℃之丙烯酸系聚合物(B1)。 (改質聚烯烴系樹脂之製造) 將製造例CL1中獲得之作為成分(A)之氯化聚丙烯系樹脂(A1CL1)80份與作為成分(B)之丙烯酸系聚合物(B1)20份添加至於氮氣氛圍下加溫至70℃之甲苯233份中後，以70℃反應4小時並進行冷卻，其後添加1重量份之環氧化合物(Epocizer W-100EL，大日本油墨化學工業(股)製造)作為穩定劑，而獲得包含改質聚烯烴系樹脂(C1)之甲苯分散液。 ＜實施例2＞ 以表2之實施例2中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-33℃之丙烯酸系聚合物(B2)。 使用製造例MCL1中獲得之酸改質氯化聚丙烯系樹脂(A2M2CL1)50份代替氯化聚丙烯系樹脂(A1CL1)80份，而且使用丙烯酸系聚合物(B2)50份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C2)之甲苯分散液。 ＜實施例3＞ 以表2之實施例3中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-1℃之丙烯酸系聚合物(B3)。 使用製造例MCL2中獲得之酸改質氯化聚丙烯系樹脂(A1M2CL2)20份代替氯化聚丙烯系樹脂(A1CL1)80份，而且使用丙烯酸系聚合物(B3)80份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C3)之甲苯分散液。 ＜實施例4＞ 以表2之實施例4中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-55℃之丙烯酸系聚合物(B4)。 使用製造例MCL3中獲得之酸改質氯化聚丙烯系樹脂(A3M2CL3)70份代替氯化聚丙烯系樹脂(A1CL1)80份，而且使用丙烯酸系聚合物(B4)30份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C4)之甲苯分散液。 ＜實施例5＞ 以表2之實施例5中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-46℃之丙烯酸系聚合物(B5)。 使用製造例MCL4中獲得之酸改質氯化聚丙烯系樹脂(A4M1CL4)60份代替氯化聚丙烯系樹脂(A1CL1)80份，而且使用丙烯酸系聚合物(B5)40份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C5)之甲苯分散液。 ＜實施例6＞ 以表2之實施例6中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-43℃之丙烯酸系聚合物(B6)。 使用製造例CL3中獲得之氯化聚丙烯系樹脂(A4CL3)代替氯化聚丙烯系樹脂(A1CL1)，而且使用丙烯酸系聚合物(B6)代替丙烯酸系聚合物(B1)，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C6)之甲苯分散液。 ＜實施例7＞ 以表2之實施例7中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-60℃之丙烯酸系聚合物(B7)。 使用氯化聚丙烯系樹脂(A1CL1)60份，而且使用丙烯酸系聚合物(B7)40份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C7)之甲苯分散液。 ＜實施例8＞ 以表2之實施例8中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-66℃之丙烯酸系聚合物(B8)。 使用製造例CL2中獲得之氯化聚丙烯系樹脂(A5CL2)70份代替氯化聚丙烯系樹脂(A1CL1)80份，而且使用丙烯酸系聚合物(B8)30份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C8)之甲苯分散液。 ＜實施例9＞ 以表2之實施例9中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-24℃之丙烯酸系聚合物(B9)。 使用氯化聚丙烯系樹脂(A1CL1)50份，使用丙烯酸系聚合物(B9)50份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C8)之甲苯分散液。 ＜實施例10＞ 以表2之實施例10中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度-66℃之丙烯酸系聚合物(B10)。 使用製造例M1中獲得之酸改質聚丙烯系樹脂(A3M1)60份代替氯化聚丙烯系樹脂(A1CL1)80份，使用丙烯酸系聚合物(B10)40份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C10)之甲苯分散液。 ＜比較例1＞ 以表2之比較例1中記載之調配比添加各丙烯酸系單體，除此以外，以與實施例1中記載之丙烯酸系聚合物(B1)之製造相同之方式獲得玻璃轉移溫度27℃之丙烯酸系聚合物(B11)。 使用製造例MCL3中獲得之酸改質氯化聚丙烯系樹脂(A3M2CL3)50份代替氯化聚丙烯系樹脂(A1CL1)80份，使用丙烯酸系聚合物(B11)50份代替丙烯酸系聚合物(B1)20份，除此以外，以與實施例1相同之方式獲得包含改質聚烯烴系樹脂(C10)之甲苯分散液。 ＜評價＞ 藉由下述方法對實施例及比較例中獲得之改質聚烯烴系樹脂進行評價。將結果表示於表3。 ＜重量平均分子量(Mw)＞ 利用GPC，按照下述條件進行測定。 裝置：HLC-8320GPC(由Tosoh股份有限公司提供) 管柱：TSK-gel G-6000 H×L，G-5000 H×L，G-4000 H×L，G-3000 H×L，G-2000 H×L(由Tosoh股份有限公司提供) 溶離液：THF 流速：1 mL/min 溫度：泵烘箱、柱烘箱40℃ 注入量：100 μL 標準物質：聚苯乙烯EasiCal PS-1(由Agilent Technology提供) ＜玻璃轉移溫度(Tg)＞ 使用已判明之將製造成分(B)之聚合物時所使用之各單體製成均聚物之情形時之各玻璃轉移溫度、及製造成分(B)時所使用之各單體之調配比率，藉由上述FOX式算出。 ＜成分(B)(丙烯酸系聚合物)之羥值(mgKOH/g)＞ 使用已判明之將製造之成分(B)之聚合物時所使用之各單體製成均聚物之情形時之羥值、及製造成分(B)時所使用之各單體之調配比率，藉由上述方法算出。 ＜樹脂分散液之穩定性＞ 針對實施例及比較例中獲得之包含改質聚烯烴系樹脂之甲苯分散液，利用下述基準目視評價剛製造後及製造後經過1週後之性狀。若為良好便能夠使用。 最好：剛製造後及經過1週後均未見分散液之分離，為良好之溶液性狀。 良好：經過1週後，能夠目視確認分散液之分離，或者分散液產生混濁，但剛製造後之分散液未見分離。 不良：剛製造後及經過1週後均可見分散液之分離。 ＜塗料穩定性＞ 將實施例及比較例中獲得之改質聚丙烯系樹脂之甲苯分散液與甲苯進行調配，而製備固形物成分20%之甲苯分散液。於聚胺酯樹脂(日立化成工業製造，固形物成分30 wt%)90重量份中，添加所製備之甲苯分散液(固形物成分20 wt%)15重量份，利用振盪機攪拌10分鐘，於室溫下靜置1天後，觀察溶液性狀，根據溶液之分離狀態目視判斷塗料穩定性(調配樹脂之相容性)。 A：未見溶液之增黏、分離，為良好之溶液性狀。 B：雖溶液略有增黏，但未見分離等。 C：雖無成分之分離，但於溶液中確認到微粒子。 D：能夠目視確認成分之分離。 ＜試片之製作＞ 將實施例及比較例中獲得之分散液調整為固形物成分濃度30重量%，並塗佈於聚丙烯基材，於80℃下乾燥5分鐘後，塗佈二液聚胺酯塗料，於80℃下乾燥30分鐘，而製作試片(塗佈板)，然後進行各試驗。 ＜附著性試驗＞ 於塗佈板之塗膜上以1 mm間隔，縱橫地劃入直達基底之線狀劃痕，而形成100個區間(柵格)，使透明黏著帶密接於其上後沿180°方向進行剝離。針對100個相同之區間進行10次使透明黏著帶密接後將其剝離之操作，按照以下所示之基準對附著性(接著性)進行評價。若剝離之塗膜之區間為50個以下，則實用上無問題。 (附著性之評價基準) A：無塗膜之剝離。 B：剝離之塗膜之區間為1個以上且10個以下。 C：剝離之塗膜之區間多於10個且為50個以下。 D：剝離之塗膜之區間多於50個。 ＜耐酒精汽油性試驗＞ 將塗佈板於普通汽油/乙醇=9/1(v/v)中浸漬120分鐘，並觀察塗膜之狀態，按照以下所示之基準對耐酒精汽油性進行評價。若塗膜表面未產生剝離，則實用上無問題。 (耐酒精汽油性之評價基準) A：塗膜表面無變化。 B：塗膜表面可見少許變化但未見剝離。 C：塗膜表面可見變化但未產生剝離。 D：塗膜表面產生剝離。 ＜耐碎裂試驗＞ 於冷卻至-20℃之低溫室內對塗佈板進行冷卻，以從水平成為角度90°之方式將試驗板垂直固定於飛石試驗機(Suga Test Instruments股份有限公司，JA-400型)之試驗板安裝部，以5 kgf/cm2
之氣壓，將7號碎石100 g吹送5秒鐘，而使試驗板受損。其後，對塗佈板進行水洗，並使之乾燥，使透明黏著帶密接於塗面，捏住膠帶之一端將其剝離，將因碎裂而隆起之塗膜去除，按照下述基準對剝離損傷之程度進行評價。剝離損傷之評價係於被衝擊部之長70 mm×寬70 mm之框架內進行。 A：最好。每評價面積之剝離面積率為0.0%以上且未達0.7%。 B：良好。每評價面積之剝離面積率為0.7%以上且未達1.2%。 C：較差。每評價面積之剝離面積率為1.2%以上且未達3.5%。 D：最差。每評價面積之剝離面積率為3.5%以上。 [表1]
表1之項目「樹脂骨架」中，「P」表示丙烯，「E」表示乙烯，「B」表示丁二烯。 [表2]
表2中，「2EHA」表示丙烯酸2-乙基己酯，「HEA」表示丙烯酸2-羥基乙酯，「BA」表示丙烯酸丁酯，「INA」表示丙烯酸異壬酯，「AA」表示丙烯酸，「LMA」表示甲基丙烯酸月桂酯，「LA」表示丙烯酸月桂酯，「HEMA」表示甲基丙烯酸2-羥基乙酯，「EA」表示丙烯酸乙酯。 C4-12
之比率係指碳原子數為4～12且通式(I)所表示之(甲基)丙烯酸酯相對於所調配之單體之總重量的重量百分率(%)。 [表3]
根據表3，可知實施例之改質聚烯烴系樹脂與比較例1相比，耐碎裂性優異。又，可知實施例之改質聚烯烴系樹脂於對作為非極性基材之聚丙烯之附著性及製成樹脂分散液或塗料之情形時之穩定性方面無問題。In this specification, "(meth)acrylic acid" includes methacrylic acid and acrylic acid, and "(meth)acrylate" includes methacrylate and acrylate. [1. Modified polyolefin-based resin] The modified polyolefin-based resin of the present invention is based on component (A): a polyolefin resin or its modified product grafted with The indicated (meth)acrylate structural unit (i) is a copolymer of a polymer having a glass transition temperature (Tg) of 0°C or lower. [1-1. Component (A)] Component (A) is a polyolefin resin or a modified product of a polyolefin resin. [1-1-1. Polyolefin resin] The polyolefin resin as the component (A) is a polymer of an olefin. The polyolefin resin as the component (A) is preferably a polyolefin resin produced using a Ziegler-Natta catalyst or a metallocene catalyst as a polymerization catalyst, more preferably a Ziegler-Natta catalyst -Natta catalysts or metallocene catalysts are used as polymerization catalysts to produce polypropylene, or propylene and α-olefins (such as ethylene, butene, 3-methyl-1-butene, 3-methyl-1 -heptene) is a polyolefin resin obtained by copolymerization. In addition, a polyolefin resin obtained by random copolymerizing propylene and an α-olefin may be referred to as a propylene-based random copolymer. Examples of the propylene-based random copolymers include ethylene-propylene copolymers, propylene-butene copolymers, ethylene-propylene-diene copolymers, and ethylene-propylene-butene copolymers. The polyolefin resin is further preferably polypropylene or propylene-based random copolymer produced by using a metallocene catalyst as a polymerization catalyst, especially polypropylene, ethylene-propylene produced by using a metallocene catalyst as a polymerization catalyst copolymer, propylene-butene copolymer, or ethylene-propylene-butene copolymer. These resins may be one kind alone or a combination of plural kinds of resins. As said metallocene catalyst, a well-known thing can be used. Specific examples of the metallocene catalyst include catalysts obtained by combining the following components (1) and (2) and, if necessary, (3), and preferably the following A catalyst obtained by combining components (1) and (2) and, if necessary, (3). Component (1): a metallocene complex which is a transition metal compound of Groups 4 to 6 of the periodic table having at least one conjugated five-membered ring ligand. • Ingredient (2): ion-exchangeable layered silicate. • Component (3): Organoaluminum compound. The polyolefin resin synthesized by using the metallocene catalyst has the characteristics of narrow molecular weight distribution, excellent random copolymerizability, narrow composition distribution, and a wide range of copolymerizable comonomers. Therefore, it is preferably used as the component (A) ). The structure of the polyolefin resin as the component (A) is not particularly limited, and may be any of a homologous structure, a heterostructure, and an opposite structure that can obtain a common polymer compound. In consideration of the adhesion to the polyolefin substrate, especially the adhesion during low-temperature drying, the component (A) is preferably a polyolefin resin with an in-line structure polymerized using a metallocene catalyst. The component composition of the polyolefin resin as the component (A) is not particularly limited, but the propylene component of the component (A) is preferably 60 mol % or more, more preferably 70 mol % or more, and more preferably 80 mol % or more. More than mol%. When the propylene content of the component (A) is 60 mol % or more, the adhesion (adhesion) to the propylene substrate becomes more favorable. [1-1-2. Modified product of polyolefin resin] The component (A) may be a modified product of polyolefin resin. Examples and preferred examples of the polyolefin resin in the modified polyolefin resin are as described in the above-mentioned item [1-1-1. Polyolefin resin]. The type of modification is not particularly limited, and examples thereof include known modification such as chlorination; epoxidation; hydroxylation; carboxylic acid anhydride; and carboxylation. The modified substance of the polyolefin resin can be obtained by modifying the polyolefin resin using a known method. The modified substance of the polyolefin resin as the component (A) is preferably a chlorinated polyolefin resin. The chlorination method of the polyolefin resin is explained below. When the component (A) is a chlorinated polyolefin resin, the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight or more. When the chlorine content is 15% by weight or more, the dispersibility of the modified polyolefin-based resin in alcohols such as ethanol and isopropyl alcohol is excellent. The upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less. If the chlorine content is 40% by weight or less, the modified polyolefin-based resin is excellent in adhesion to the polyolefin-based substrate. In addition, the chlorine content rate of resin can be measured based on JIS-K7229. In addition, the chlorine content rate of the component (A) in the modified polyolefin resin of the present invention is usually the same as the chlorine content rate of the component (A) as a raw material before grafting with the component (B). The modified substance as the component (A) may be an acid modified substance obtained by modifying a polyolefin resin with an acid. The acid for modification is not particularly limited, and examples thereof include α,β-unsaturated carboxylic acid and derivatives of α,β-unsaturated carboxylic acid (for example, maleic acid, maleic anhydride, fumaric acid, etc.) acid, citraconic acid, citraconic anhydride, mesaconic acid, itaconic acid, itaconic anhydride, aconitic acid, aconitic anhydride, bicycloheptenedicarboxylic anhydride, (meth)acrylic acid), preferably α,β-no The acid anhydride of saturated carboxylic acid is more preferably maleic anhydride. As a method for modifying the polyolefin resin with an acid, a known method can be used. For example, the acid-modified polyolefin is obtained by melting the polyolefin resin and adding an acid and a radical reaction initiator for the modification. resin method. The reaction apparatus is not particularly limited, and for example, an extruder may be used to perform the reforming reaction. The modified substance as the component (A) may be a modified substance in which the polyolefin resin is modified by a plurality of modified materials. Therefore, the modified substance of the component (A) can also be obtained by modifying the chlorinated polyolefin resin with an acid (for example, α,β-unsaturated carboxylic acid or a derivative of α,β-unsaturated carboxylic acid). acid-modified chlorinated polyolefin resin. The component (A) is preferably a chlorinated polyolefin resin or an acid-modified chlorinated polyolefin resin. [1-1-3. Weight average molecular weight of component (A)] The weight average molecular weight (Mw) of the component (A) is preferably 5,000 or more. When the weight average molecular weight is 5,000 or more, the cohesive force of the resin is sufficient and the adhesion to the base material is excellent. The upper limit of the weight average molecular weight of the component (A) is preferably 150,000 or less. If the weight average molecular weight is 150,000 or less, the compatibility with other resins contained in the paint or ink is good, and the adhesion to the substrate is good. In addition, the weight average molecular weight can be calculated|required by the standard polystyrene calibration curve by the gel permeation chromatography (GPC) method. The weight average molecular weight of the component (A) is preferably 5,000 to 150,000. Here, the weight average molecular weight of the component (A) generally corresponds to the weight average molecular weight measured for the component (A) as a raw material before grafting the component (B). [1-2. Component (B)] The component (B) contains the structural unit (i) derived from the (meth)acrylate represented by the general formula (I) and has a glass transition temperature (Tg) of 0° C. or lower polymer. [1-2-1. Structural unit (i)] The component (B) contains the structural unit (i) derived from the (meth)acrylate represented by the general formula (I). CH 2 =C(R 1 )COOR 2 ...(I) In the general formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by -C n H 2n + 1 , and n represents 1 to 18 the integer. The group represented by -C n H 2n + 1 may be a straight-chain alkyl group or a branched-chain alkyl group. Here, the structural unit derived from a certain monomer means a structural unit obtained when a certain monomer is used for a polymerization reaction. The structural unit (i) preferably has 4 or more carbon atoms, more preferably 12 or less. The structural unit (i) preferably has 4 to 12 carbon atoms. Thereby, the chipping resistance of the modified polyolefin-based resin can be further improved. Here, the number of carbon atoms of the structural unit (i) is usually the same as the number of carbon atoms of the (meth)acrylate represented by the general formula (I) from which the structural unit (i) is derived. When the component (B) contains a structural unit (i) having 4 to 12 carbon atoms (hereinafter, also referred to as a structural unit (i 4-12 )), the structural unit (i 4-12 ) in the component (B) 12 ) The content rate is preferably 40% by weight or more, more preferably 60% by weight or more, and preferably 100% by weight or less. Thereby, when combining the modified polyolefin resin and other components to form a composition (for example, a coating composition), compatibility with other components becomes favorable. The content rate (%) of the structural unit (i 4-12 ) in the component (B) is usually relative to a (meth)acrylate represented by the general formula (I) and a certain monomer having 4 to 12 carbon atoms. The weight percent of the total monomer weight used in the manufacture of the polymer of component (B) is the same. The structural unit (i) contained in the component (B) may be alone or may be two or more. Structural units other than the structural unit (i) may be contained in the component (B). As a structural unit other than the structural unit (i) that can be contained in the component (B), for example, a structural unit derived from an α,β-unsaturated carboxylic acid (for example, a structural unit derived from (meth)acrylic acid), and Structural units derived from α,β-unsaturated carboxylic acid ester other than the structural unit (i) (for example, alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate). [1-2-2. Glass transition temperature of component (B)] The glass transition temperature (Tg) of the component (B) is 0°C or lower, preferably -20°C or lower, more preferably -25°C or lower, and more preferably It is preferably -30°C or lower. When Tg exceeds 0 degreeC, since the softness|flexibility of a modified polyolefin resin falls, chipping resistance is inferior. Tg is usually -70°C or higher, preferably -65°C or higher, more preferably -60°C or higher. The glass transition temperature (Tg) can use the value of each glass transition temperature when each monomer unit constituting the component (B) is made into a homopolymer and the weight ratio of each monomer unit in the component (B), and Calculated by the following FOX formula. As the Tg of each homopolymer, the Tg published in the polymer handbook (Wiley-Interscience Publication, 4th edition, 1999) and the product information can be used. The weight ratio of each monomer unit in the component (B) generally corresponds to the weight ratio (compounding ratio) of each monomer with respect to the total monomer weight used in producing the polymer of the component (B). <FOX formula> 1/Tg=W 1 /Tg 1 +W 2 /Tg 2 +W 3 /Tg 3 +...W n /Tg n In the above formula, component (B) is composed of n kinds of monomer units U 1 to U n The glass transition temperature of the homopolymer of the monomer units U 1 to Un is set to Tg 1 to Tg n , respectively, and the weight ratio of the monomer units U 1 to Un is set to W 1 to W n , respectively. Here, the sum of the weight ratios of the monomer units U 1 to U n is set to 1. As the glass transition temperature of the component (B), the glass transition temperature measured on the polymer of the component (B) which is a raw material before being grafted to the component (A) can be used. The glass transition temperature of the component (B) as a raw material can be measured, for example, using a differential scanning calorimeter (for example, "DSC6200R thermal analysis system", provided by Seiko Instruments Inc.). Preferably, the glass transition temperature of the component (B) of the present invention is the value of the glass transition temperature when each monomer unit constituting the component (B) is made into a homopolymer and the value of the glass transition temperature in the component (B) is used. The weight ratio of each monomer unit is the value calculated by the above-mentioned FOX formula. [1-2-3. Weight average molecular weight of component (B)] The weight average molecular weight (Mw) of component (B) is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, and preferably 100,000 or less , more preferably 20,000 or less. The weight average molecular weight of the component (B) is preferably from 1,000 to 100,000, more preferably from 3,000 to 20,000. Here, the weight average molecular weight of the component (B) generally corresponds to the weight average molecular weight measured on the polymer of the component (B) as a raw material before being grafted to the component (A). [1-2-4. Hydroxyl value of component (B)] The hydroxyl value of component (B) is not particularly limited, but is preferably 5 mgKOH/g or more, more preferably 560 mgKOH/g or less, more preferably 280 mgKOH/g or less, more preferably 168 mgKOH/g or less. If the hydroxyl value of the component (B) is 5 mgKOH/g or more, when the modified polyolefin-based resin is combined with other components to form a composition (for example, a coating composition), the compatibility with other components become good. If the hydroxyl value of the component (B) is 560 mgKOH/g or less, the degree of polarity of the modified polyolefin-based resin is appropriate. Therefore, when the modified polyolefin-based resin is combined with other components to form a composition, Compatibility with other ingredients becomes good. The hydroxyl value of the component (B) is preferably 5-560 mgKOH/g, more preferably 5-280 mgKOH/g, and still more preferably 5-168 mgKOH/g. When the component (B) is composed of n kinds (n is an integer of 1 or more) monomer units U 1 to U n , and the hydroxyl values of the homopolymers of the monomer units U 1 to U n are set as X 1 to X, respectively n (mgKOH/g), let the weight ratio of the monomer units U 1 to U n in the component (B) be Y 1 to Y n respectively (wherein, the total weight ratio of the monomer units U 1 to U n is As 1), the hydroxyl value X B of the component (B) is calculated by the following formula. X B =X 1 Y 1 +X 2 Y 2 +...X n Y n The hydroxyl value of the component (B) in the examples is also the value calculated by the above method. [1-3. Modified Polyolefin-Based Resin] The modified polyolefin-based resin of the present invention is a copolymer obtained by grafting the above-mentioned component (B) to the above-mentioned component (A): a polyolefin resin or a modified product thereof. The modified polyolefin-based resin of the present invention may be a copolymer in which the component (A) is grafted with the component (B), or may be used after the graft polymerization reaction for grafting the component (B) to the component (A). , and further modified by a modifier (eg, by chlorine and/or acid), the copolymer can also be a copolymer that is not further modified by a modifier after the graft polymerization reaction. The modified polyolefin resin of the present invention is a polymer in which the component (A) is grafted with the component (B). The modified polyolefin-based resin of the present invention may be a resin produced by grafting the polymer of the component (B) as a raw material by a graft polymerization reaction as the raw material component (A), or may be a resin produced by grafting the polymer of the raw material component (B) by a graft polymerization reaction. The component (A) is a resin produced by grafting the monomers used to constitute the polymer (block) of the component (B) sequentially or simultaneously by graft polymerization. The modified polyolefin-based resin of the present invention can be a chlorinated graft-modified polyolefin-based resin, an acid-modified graft-modified polyolefin-based resin, or an acid-modified and chlorinated graft-modified polyolefin-based resin. Quality polyolefin resin. The modified polyolefin resin of the present invention is preferably a chlorinated resin. "Chlorinated resin" includes component (A) chlorinated resin, component (B) chlorinated resin, components (A) and (B) chlorinated resin. The modified polyolefin-based resin of the present invention is more preferably a chlorinated resin in which the component (A) is chlorinated. When the modified polyolefin-based resin is a chlorinated resin, the chlorine content of the modified polyolefin-based resin is preferably 10% by weight or more, more preferably 15% by weight or more. The upper limit of the chlorine content in the modified polyolefin-based resin is preferably 35% by weight or less, more preferably 30% by weight or less. It is presumed that when the chlorine content of the modified polyolefin-based resin is within this range, the polarity of the modified polyolefin-based resin is enhanced, and the modified polyolefin-based resin tends to exhibit a linear structure due to the steric repulsion of chlorine atoms. Therefore, it is presumed that the dispersibility in a highly polar solvent (for example, alcohols) is excellent. [1-3-1. Weight-average molecular weight of modified polyolefin-based resin] The weight-average molecular weight of the modified polyolefin-based resin of the present invention is not particularly limited, but is preferably 10,000 or more, more preferably 30,000 or more, and Preferably it is 200,000 or less, More preferably, it is 150,000 or less. Adhesion is improved by the weight average molecular weight of the modified polyolefin resin being 10,000 or more. Moreover, when the weight average molecular weight of the modified polyolefin-based resin is 200,000 or less, when the modified polyolefin-based resin is combined with other components to form a composition, compatibility with other components becomes favorable. The weight average molecular weight of the modified polyolefin resin of the present invention is preferably 10,000 to 200,000, more preferably 30,000 to 150,000. [1-3-2. Content ratio of component (B)] The content ratio of the component (B) in the modified polyolefin-based resin of the present invention is not particularly limited, but is preferably 20% by weight or more, more preferably 30% by weight or more % by weight or more, more preferably 50% by weight or more. The upper limit is preferably 80% by weight or less. The content rate of the component (B) in the modified polyolefin-based resin refers to the weight ratio of the component (B) part grafted to the component (A) with respect to the modified polyolefin-based resin. The weight ratio (%) of the component (B) with respect to the modified polyolefin-based resin is usually the same as the compounding ratio (%) of the component (B) obtained by graft-polymerizing the component (A) in the production of the modified polyolefin-based resin. (However, let the total of the compounding weight of the component (A) and the compounding weight of the component (B) be 100%.) [1-3-3. Component (A)/Component (B)] The weight ratio of the component (A) to the component (B) in the modified polyolefin resin of the present invention is not particularly limited, but is preferably 20 /80 or more, more preferably 30/70 or more, still more preferably 50/50 or more, and more preferably 80/20 or less. The weight ratio of the component (A) to the component (B) in the modified polyolefin-based resin of the present invention is preferably 20/80 or more and 80/20 or less. [2. Manufacturing method of modified polyolefin-based resin] The manufacturing method of the modified polyolefin-based resin of the present invention includes, for example, the steps of: graft-polymerizing the component (B) on the component (A): polyolefin resin or its modified product ): a polymer containing a structural unit (i) derived from the (meth)acrylate represented by the general formula (I) and having a glass transition temperature (Tg) of 0° C. or lower. Here, in formula (I), R 1 represents a hydrogen atom or a methyl group, R 2 represents a group represented by -C n H 2n + 1 , and n represents an integer of 1 to 18. The component (A) and the component (B) are the same as the component (A) and the component (B) described in the item [1. Modified polyolefin-based resin], respectively. As a method of introducing the component (B) into the component (A) by graft copolymerization, for example, graft copolymerization of the component (A) as the raw material on the A method of polymerizing the structural unit (i) of the (meth)acrylate represented by the general formula (I) and having a glass transition temperature (Tg) of 0°C or lower; graft copolymerization on the component (A) as a raw material It is the method of the (meth)acrylate represented by the said general formula (I) used as the raw material of the polymer which comprises a component (B). When the (meth)acrylate represented by the above-mentioned general formula (I) is graft-copolymerized with respect to the component (A) as a raw material, the (meth)acrylates represented by the above-mentioned general formula (I) can be successively It may be added to the component (A) as a raw material, and may be added to the component (A) as a raw material at one time. Moreover, you may add the monomer other than the (meth)acrylate represented by the said general formula (I) to the component (A) which is a raw material. The conditions of the graft polymerization are not particularly limited, and for example, known methods such as a melt method and a solution method can be used. In the case of using the melting method, there are advantages that the operation is simple and the reaction can be carried out in a short time. In the case of using the solution method, there are fewer side reactions and a uniform graft polymer can be obtained. In the case of using the melting method, the component (A) is heated and melted (heated and melted) in the presence of a radical reaction initiator to react with the component (B). The component (B) may be in a monomer form before polymerization or may be in a polymer form after polymerization. The temperature for heating and melting may be equal to or higher than the melting point of the component (A), and preferably equal to or higher than the melting point of the component (A) and 300° C. or lower. When heating and melting, machines such as a Banbury mixer, a kneader, and an extruder can be used. When using the solution method, after dissolving the component (A) in an organic solvent, it reacts with the component (B) by heating and stirring in the presence of a radical reaction initiator. The component (B) may be in a monomer form before polymerization or may be in a polymer form after polymerization. As the organic solvent, aromatic hydrocarbon solvents such as toluene and xylene are preferably used. The temperature during the reaction is preferably 100 to 180°C. The radical reaction initiator used in the melt method and the solution method is not particularly limited, and examples thereof include organic peroxide-based compounds and azonitriles. Examples of the organic peroxide-based compound include di(tert-butyl) peroxide, dicumyl peroxide, tert-butyl cumyl peroxide, benzyl peroxide, and dilauryl peroxide. oxide, 2,5-dimethyl-2,5-bis(tert-butyl peroxide)hexane, cumene hydroperoxide, tert-butyl hydroperoxide, 1,1-bis(tert-butyl peroxide) tert-butyl)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butyl peroxide) cyclohexane, cyclohexanone peroxide, tert-butyl peroxybenzoate , tertiary butyl peroxyisobutyrate, 3,5,5-trimethylhexanoate tertiary peroxide, 3rd butyl peroxide 2-ethylhexanoate, tertiary isopropyl peroxycarbonate Butyl ester, cumyl peroxyoctanoate, etc., can be selected according to the temperature at which radical polymerization is carried out, which has an appropriate half-life temperature. In the method for producing a modified polyolefin-based resin of the present invention, the component (A) may be graft-polymerized in the form of a composition containing an arbitrary stabilizer in addition to the component (A). Examples of optional stabilizers include: epoxy compounds; metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resins; dibutyltin dilaurate, dibutyl maleate Organometallic compounds such as butyl ester; aluminum magnesium carbonate compounds. The epoxy compound is not particularly limited, but is preferably an epoxy compound compatible with the resin modified by chlorination or the like. As the epoxy compound, a compound having an epoxy equivalent of about 100 to 500 and having one or more epoxy groups per molecule can be exemplified. Examples of such an epoxy compound include: Epoxidized vegetable oil (epoxidized soybean oil, epoxidized linseed oil, etc.) obtained by epoxidizing peracid such as peracetic acid; obtained by epoxidizing unsaturated fatty acids such as oleic acid, tall oil fatty acid, and soybean oil fatty acid Epoxidized fatty acid esters; epoxidized alicyclic compounds such as epoxidized tetrahydrophthalate; obtained by condensing bisphenol A or polyhydric alcohol with epichlorohydrin, such as bisphenol A glycidyl ether, ethylene glycol Glycidyl ether, propylene glycol glycidyl ether, glycerol polyglycidyl ether, sorbitol polyglycidyl ether and other ethers; and butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, hard Fatty glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, 2-butyl phenyl glycidyl ether, 3-butyl phenyl glycidyl ether, phenol polyethylene oxide glycidyl ether, etc. are Representative of the single epoxy compounds. The stabilizer may be used alone or in combination of two or more. When the component (A) is graft-polymerized in the form of a composition containing a stabilizer, the weight ratio of the stabilizer to the component (A) is preferably 1 to 20% by weight (in terms of solid content). The production method of the modified polyolefin resin of the present invention may include any steps in addition to the steps described above. As an arbitrary process, after the component (A) is graft-polymerized with the component (B) to obtain a graft-modified polyolefin-based resin, for example, a step of modifying the graft-modified polyolefin-based resin can be mentioned. The type of modification is not particularly limited, and examples thereof include known modification such as chlorination; epoxidation; hydroxylation; carboxylic acid anhydride; and carboxylation. These modifications can be carried out by known methods. For example, when the modified polyolefin resin is a chlorinated resin, the production method of the present invention may also include the step of chlorinating the resin in any stage of its production, for example, may also include: chlorinating the polyolefin resin the step of chlorinating the obtained graft-modified polyolefin-based resin after the polyolefin resin is graft-polymerized with component (B). Therefore, as a production method for obtaining a modified polyolefin resin as a chlorinated resin, for example, a method of grafting the component (B) to the component (A) and then performing chlorination; A method of grafting the component (B) to the component (A) after the chlorinated polyolefin resin as the component (A) is obtained by chemical conversion. As a method of chlorination, a well-known method can be used, and it does not specifically limit, For example, the method of melt|dissolving resin in a chlorinated solvent, such as chloroform, blows a chlorine gas, and introduce|transduces chlorine etc. are mentioned. More specifically, chlorination can be achieved by dispersing or dissolving the resin in a medium such as water, carbon tetrachloride, or chloroform, in the presence of a catalyst or under the irradiation of ultraviolet rays, under pressure or normal pressure, at 50°C. It is carried out by blowing chlorine gas in the temperature range of ~140°C. When a chlorinated solvent is used in the production of a chlorinated resin, the used chlorinated solvent can usually be removed by distillation under reduced pressure or the like, or can be replaced with another organic solvent. When the polyolefin resin is chlorinated to obtain the chlorinated polyolefin resin as the component (A), the chlorine content of the chlorinated polyolefin resin as the component (A) is preferably 15% by weight or more, more preferably 20% by weight or more. When the chlorine content is 15% by weight or more, the obtained modified polyolefin-based resin is excellent in dispersibility in alcohols such as ethanol and isopropanol. The upper limit of the chlorine content in the chlorinated polyolefin resin as the component (A) is preferably 40% by weight or less, more preferably 35% by weight or less. If the chlorine content is 40% by weight or less, the obtained modified polyolefin-based resin is excellent in adhesion to the polyolefin-based substrate. [3. Modified polyolefin-based resin composition] The modified polyolefin-based resin of the present invention may constitute a modified polyolefin-based resin composition together with other optional components. Examples of optional components include stabilizers for suppressing desorption of chlorine. The stabilizer is not particularly limited, for example, epoxy compounds; metal soaps such as calcium stearate and lead stearate used as stabilizers for polyvinyl chloride resins; dibutyltin dilaurate, maleic acid Organometallic compounds such as dibutyl ester; aluminum magnesium carbonate compounds, preferably epoxy compounds. Although the epoxy compound is not particularly limited, for example, the epoxy compound exemplified as an arbitrary stabilizer that can be contained in the composition of the component (A) in the above-mentioned [2. Manufacturing method of modified polyolefin resin], is preferable. It is an epoxy compound compatible with modified polyolefin resin modified by chlorine. As a stabilizer, only one of these may be used, or two or more of them may be used in combination. Moreover, for example, the modified polyolefin-based resin composition may be in the form of a dispersion composition containing the modified polyolefin-based resin and a dispersion medium. In addition, in this specification, "dispersion medium" contains the solvent which can melt|dissolve the modified polyolefin resin, and "dispersion composition" may be the solution of the modified polyolefin resin composition. Examples of the dispersion medium include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as hexane, heptane, and octane; methyl ketone, methyl isobutyl ketone and other ketones; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate and other esters; methanol, ethanol, n-propanol, isopropanol, n-butyl acetate, etc. Alcohols such as butanol and isobutanol; glycols such as ethylene glycol, ethyl cellosolve, and butyl cellosolve; water, etc. The dispersion medium may be used alone or in combination of two or more. [4. Use of the modified polyolefin resin] The modified polyolefin resin of the present invention can be used as an adhesive for metals and/or resins, a primer, an adhesive for paint, and an adhesive for ink. Since the modified polyolefin resin of the present invention has good adhesion and excellent chip resistance, it is particularly useful as an adhesive for automotive coatings and a primer for automotive coatings. [Examples] Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. Unless otherwise specified, "parts" and "%" refer to "parts by weight" and "% by weight", respectively. The following operations are carried out in the atmosphere at normal temperature and normal pressure unless otherwise specified. <Production Example A1> Polyolefin resin A propylene-based random copolymer (propylene unit content: 80% by weight, ethylene unit content: 20% by weight) produced using a metallocene catalyst as a polymerization catalyst was supplied until the cylinder temperature was set to Thermal degradation was performed in a biaxial extruder at 350° C. to obtain a polypropylene-based resin (A1) having a weight average molecular weight of 5,000. <Production Example A2> The polyolefin resin used a propylene-based random copolymer (content of propylene units: 90% by weight, content of ethylene units: 10% by weight) produced by using a metallocene catalyst as a polymerization catalyst, and the same In the same manner as in Production Example A1, a polypropylene-based resin (A2) having a weight average molecular weight of 111,000 was obtained. <Production Example A3> The polyolefin resin used a propylene-based random copolymer (content of propylene units: 94% by weight, content of ethylene units: 6% by weight) produced by using a metallocene catalyst as a polymerization catalyst, and the same In the same manner as in Production Example A1, a polypropylene-based resin (A3) having a weight average molecular weight of 100,000 was obtained. <Production Example A4> A propylene-based random copolymer (propylene unit content: 90% by weight, ethylene unit content: 5% by weight, butene unit content: 5% by weight) produced by using a metallocene catalyst as a polymerization catalyst was used as the polyolefin resin. ), except that, in the same manner as in Production Example A1, a polypropylene-based resin (A4) having a weight average molecular weight of 45,000 was obtained. <Production Example A5> Polyolefin resin A propylene-based random copolymer (propylene unit content: 80% by weight, ethylene unit content: 20% by weight) produced using a metallocene catalyst as a polymerization catalyst was supplied until the cylinder temperature was set to Thermal degradation was carried out in a twin-screw extruder at 400° C. to obtain a polypropylene-based resin (A5) having a weight average molecular weight of 2,000. <Production Example CL1> Chlorinated Polyolefin Resin 100 parts by weight of the polypropylene-based resin (A1) obtained in Production Example A1 was put into a glass-lined reactor. Chloroform was added to this, and chlorine gas and oxygen gas were blown in while irradiating ultraviolet rays under a pressure of 2 kg/cm 2 , and chlorination was performed until the chlorine content became 32 wt %. After the reaction was completed, 6 parts by weight of epoxy compound (Epocizer W-100EL, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) was added as a stabilizer, and supplied to the extruder with a ventilation hole with a desolventizing suction part in the screw part. Out of the machine, solvent removal and solidification were performed to obtain a chlorinated polypropylene resin (A1CL1) having a weight average molecular weight of 5000 as a chlorinated polyolefin resin. <Production Example CL2> Except that the polypropylene-based resin (A5) obtained in Production Example A5 was used as the chlorinated polyolefin resin, a chlorinated polypropylene-based resin (A5) having a weight average molecular weight of 2,000 was obtained in the same manner as in Production Example CL1. A5CL2). <Production Example CL3> A chlorinated polyolefin resin with a weight average molecular weight of 50,000 was obtained in the same manner as in Production Example CL1 except that the polypropylene-based resin (A4) obtained in Production Example A4 was used to obtain a chlorinated polypropylene-based resin ( A4CL3). <Production Example M1> Acid-modified polyolefin resin 100 parts by weight of the polypropylene-based resin (A3) obtained in Production Example A3 was put into a three-necked flask equipped with a stirrer, a dropping funnel, and a cooling pipe for monomer reflux , and dissolved completely in an oil bath at 180°C. After replacing the inside of the flask with nitrogen for about 10 minutes, while stirring, 4 parts by weight of maleic anhydride was added for about 5 minutes, and then 0.4 parts by weight of di-tert-butyl peroxide was dissolved in 1 part by weight of heptane. , using the dropping funnel for about 30 minutes. Then, the inside of the system was kept at 180°C, and the reaction was continued for 1 hour, and the unreacted maleic anhydride was removed for about 1 hour while depressurizing the inside of the flask with an aspirator to obtain an acid with a weight average molecular weight of 105,000. Modified polyolefin resin (A3M1). <Production Example MCL1> Acid-modified chlorinated polyolefin resin (acid-modified) 100 parts by weight of polypropylene-based resin (A2) obtained in Production Example A2, 4 parts by weight of maleic anhydride, and di-tert-butyl peroxide 2 parts by weight of the material were uniformly mixed and supplied to a twin-screw extruder (L/D=60, f=15 mm, 1st to 14th cylinders). The residence time is 10 minutes, the rotation speed is 200 rpm, and the barrel temperature is 100°C (1st and 2nd barrels), 200°C (3rd to 8th barrels, 90°C (9th and 10th barrels), 110°C (Cylinders 11 to 14) were reacted under the conditions, and unreacted maleic anhydride was removed by a reduced pressure treatment to obtain maleic anhydride-modified polypropylene-based resin (A2M2). (Chlorination) The obtained The maleic anhydride modified polypropylene resin (A2M2) 100 weight parts is put into the reactor through the glass lining.Add chloroform to it, under the pressure of 2 kg/cm , irradiate ultraviolet rays on one side, blow chlorine and oxygen on one side , perform chlorination until the chlorine content becomes 32 wt%. After the reaction is completed, add 6 parts by weight of an epoxy compound (Epocizer W-100EL, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) as a stabilizer, and supply it to the screw part An extruder equipped with a suction part for desolventization with ventilation holes was used for desolvation and solidification to obtain an acid-modified chlorinated polypropylene resin (A2M2CL1) having a weight average molecular weight of 143,000 as a chlorinated polyolefin resin. <Production example MCL2> Acid-modified chlorinated polyolefin resin was obtained in the same manner as in Production Example MCL1, except that the polypropylene-based resin A1 obtained in Production Example A1 was used to obtain an acid-modified chlorinated polyolefin having a weight average molecular weight of 5,000. Propylene-based resin (A1M2CL2). <Production Example MCL3> The acid-modified chlorinated polyolefin resin was obtained in the same manner as in Production Example MCL1, except that the polypropylene-based resin A3 obtained in Production Example A3 was used to obtain a weight average molecular weight of 110,000. The acid-modified chlorinated polypropylene-based resin (A3M2CL3). <Production Example MCL4> The acid-modified chlorinated polyolefin resin used the polypropylene-based resin A4 obtained in Production Example A4, and was used in the same manner as Production Example M1. The acid-modified polyolefin-based resin (A4M1) was obtained in the same manner as in the same manner as in Production Example CL1, except that the obtained acid-modified polyolefin-based resin (A4M1) was used for chlorination to obtain a weight Acid-modified chlorinated polypropylene resin (A4M1CL4) with an average molecular weight of 75,000. <Example 1> (Manufacture of acrylic polymer (B1)) To 233 parts of toluene heated to 85°C under nitrogen atmosphere, added After 2.8 parts by weight of peroxyester-based peroxide (Nyper BMT-K40, manufactured by NOF Corporation), each acrylic monomer was mixed with each acrylic monomer in the mixing ratio described in Example 1 of Table 2. A total of 100 parts by weight was added, reacted at 85° C. for 6 hours or more, and then cooled to obtain an acrylic polymer (B1) having a glass transition temperature of −66° C. (Manufacture of modified polyolefin-based resin) Production Example 80 parts of chlorinated polypropylene resin (A1CL1) as component (A) obtained in CL1 and 20 parts of acrylic polymer (B1) as component (B) were added and heated to 70 parts under nitrogen atmosphere After adding 233 parts of toluene at 70° C. for 4 hours and cooling, 1 part by weight of an epoxy compound (Epocizer W-100EL, manufactured by Dainippon Ink Chemical Co., Ltd.) was added as a stabilizer to obtain Toluene dispersion liquid containing modified polyolefin resin (C1). <Example 2> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 2 of Table 2. Acrylic polymer (B2) with a transfer temperature of -33°C. 50 parts of acid-modified chlorinated polypropylene resin (A2M2CL1) obtained in Production Example MCL1 was used instead of 80 parts of chlorinated polypropylene resin (A1CL1), and 50 parts of acrylic polymer (B2) was used instead of acrylic polymer Except for 20 parts of (B1), it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C2). <Example 3> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 3 of Table 2. Acrylic polymer (B3) with a transfer temperature of -1°C. 20 parts of acid-modified chlorinated polypropylene resin (A1M2CL2) obtained in Production Example MCL2 was used instead of 80 parts of chlorinated polypropylene resin (A1CL1), and 80 parts of acrylic polymer (B3) was used instead of acrylic polymer Except that (B1) 20 parts, it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C3). <Example 4> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 4 of Table 2. Acrylic polymer (B4) with a transfer temperature of -55°C. 70 parts of acid-modified chlorinated polypropylene resin (A3M2CL3) obtained in Production Example MCL3 was used instead of 80 parts of chlorinated polypropylene resin (A1CL1), and 30 parts of acrylic polymer (B4) was used instead of acrylic polymer Except for 20 parts of (B1), it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C4). <Example 5> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 5 of Table 2. Acrylic polymer (B5) with a transfer temperature of -46°C. 60 parts of acid-modified chlorinated polypropylene resin (A4M1CL4) obtained in Production Example MCL4 was used instead of 80 parts of chlorinated polypropylene resin (A1CL1), and 40 parts of acrylic polymer (B5) was used instead of acrylic polymer Except for 20 parts of (B1), it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin-type resin (C5). <Example 6> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 6 of Table 2. Acrylic polymer (B6) with a transfer temperature of -43°C. In addition to using the chlorinated polypropylene resin (A4CL3) obtained in Production Example CL3 instead of the chlorinated polypropylene resin (A1CL1) and using the acrylic polymer (B6) instead of the acrylic polymer (B1), the following In the same manner as in Example 1, a toluene dispersion liquid containing the modified polyolefin-based resin (C6) was obtained. <Example 7> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 7 of Table 2. Acrylic polymer (B7) with a transfer temperature of -60°C. Except using 60 parts of chlorinated polypropylene-based resin (A1CL1), and using 40 parts of acrylic polymer (B7) in place of 20 parts of acrylic polymer (B1), it was carried out in the same manner as in Example 1 to obtain the modified acrylic polymer. Toluene dispersion of high quality polyolefin resin (C7). <Example 8> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 8 of Table 2. Acrylic polymer (B8) with a transfer temperature of -66°C. 70 parts of chlorinated polypropylene-based resin (A5CL2) obtained in Production Example CL2 was used instead of 80 parts of chlorinated polypropylene-based resin (A1CL1), and 30 parts of acrylic polymer (B8) was used instead of acrylic polymer (B1) 20 parts, except for this, it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C8). <Example 9> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 9 of Table 2. Acrylic polymer (B9) with transfer temperature -24°C. Except using 50 parts of chlorinated polypropylene-based resin (A1CL1) and using 50 parts of acrylic polymer (B9) instead of 20 parts of acrylic polymer (B1), it was carried out in the same manner as in Example 1 to obtain a modified acrylic polymer Toluene dispersion of polyolefin resin (C8). <Example 10> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Example 10 of Table 2. Acrylic polymer (B10) with a transfer temperature of -66°C. Instead of 80 parts of chlorinated polypropylene-based resin (A1CL1), 60 parts of acid-modified polypropylene-based resin (A3M1) obtained in Production Example M1 was used, and 40 parts of acrylic-based polymer (B10) was used instead of acrylic-based polymer (B1) 20 parts, except for this, it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C10). <Comparative Example 1> Glass was obtained in the same manner as in the production of the acrylic polymer (B1) described in Example 1, except that each acrylic monomer was added at the mixing ratio described in Comparative Example 1 of Table 2. Acrylic polymer (B11) with a transition temperature of 27°C. 50 parts of acid-modified chlorinated polypropylene resin (A3M2CL3) obtained in Production Example MCL3 was used instead of 80 parts of chlorinated polypropylene resin (A1CL1), and 50 parts of acrylic polymer (B11) was used instead of acrylic polymer ( Except B1) 20 parts, it carried out similarly to Example 1, and obtained the toluene dispersion liquid containing the modified polyolefin resin (C10). <Evaluation> The modified polyolefin-based resins obtained in Examples and Comparative Examples were evaluated by the following methods. The results are shown in Table 3. <Weight Average Molecular Weight (Mw)> It was measured by GPC under the following conditions. Device: HLC-8320GPC (provided by Tosoh Co., Ltd.) Column: TSK-gel G-6000 H×L, G-5000 H×L, G-4000 H×L, G-3000 H×L, G-2000 H×L (provided by Tosoh Co., Ltd.) Eluent: THF Flow rate: 1 mL/min Temperature: Pump oven, column oven 40°C Injection volume: 100 μL Standard substance: Polystyrene EasiCal PS-1 (provided by Agilent Technology ) <Glass transition temperature (Tg)> When using each glass transition temperature when each monomer used for producing the polymer of the component (B) has been identified as a homopolymer, and when producing the component (B) The mixing ratio of each monomer to be used was calculated by the above-mentioned FOX formula. <Hydroxy value (mgKOH/g) of component (B) (acrylic polymer)> When using each monomer used for the polymer of component (B) that has been identified to be produced as a homopolymer The hydroxyl value and the compounding ratio of each monomer used when producing the component (B) were calculated by the above-mentioned method. <Stability of Resin Dispersion Liquid> About the toluene dispersion liquid containing the modified polyolefin resin obtained in the Example and the comparative example, the property immediately after manufacture and one week after manufacture was visually evaluated by the following reference|standard. If it is good, it can be used. Best: No separation of the dispersion was observed immediately after production and after 1 week, and it was a good solution. Good: After 1 week, the separation of the dispersion liquid was visually confirmed, or the dispersion liquid was cloudy, but the dispersion liquid was not separated immediately after production. Defect: The separation of the dispersion was observed immediately after production and after one week. <Coating stability> The toluene dispersion liquid of the modified polypropylene resin obtained in the Example and the comparative example was mix|blended with toluene, and the toluene dispersion liquid of 20% of solid content was prepared. In 90 weight parts of polyurethane resin (manufactured by Hitachi Chemical Industry, solid content 30 wt %), add 15 weight parts of the prepared toluene dispersion (solid content 20 wt %), use a shaker to stir for 10 minutes, at room temperature After standing for 1 day, the properties of the solution were observed, and the coating stability (compatibility of the formulated resin) was visually judged according to the separation state of the solution. A: There is no viscosity increase and separation of the solution, which is a good solution. B: Although the solution was slightly thickened, separation and the like were not observed. C: Although there was no separation of components, fine particles were observed in the solution. D: The separation of components can be visually confirmed. <Preparation of test piece> The dispersion liquid obtained in Examples and Comparative Examples was adjusted to a solid content concentration of 30% by weight, applied to a polypropylene substrate, dried at 80° C. for 5 minutes, and then applied with two-liquid polyurethane The coating material was dried at 80° C. for 30 minutes to prepare a test piece (coated plate), and then each test was performed. <Adhesion test> On the coating film of the coated plate, at an interval of 1 mm, line scratches that reach the substrate are drawn vertically and horizontally to form 100 sections (grids), and the transparent adhesive tape is closely attached to the upper and rear edges. 180° direction for peeling. The operation of peeling the transparent adhesive tape in close contact with 100 identical sections was performed 10 times, and the adhesiveness (adhesion) was evaluated according to the criteria shown below. There is no practical problem as long as the interval of the peeled coating film is 50 or less. (Evaluation Criteria of Adhesion) A: No peeling of the coating film. B: The interval of the peeled coating film is 1 or more and 10 or less. C: There are more than 10 and 50 or less sections of the peeled coating film. D: There are more than 50 sections of the peeled coating film. <Alcohol gasoline resistance test> The coated panel was immersed in regular gasoline/ethanol = 9/1 (v/v) for 120 minutes, and the state of the coating film was observed, and the alcohol gasoline resistance was evaluated according to the following criteria . There is no practical problem if peeling does not occur on the surface of the coating film. (Evaluation criteria for alcohol gasoline resistance) A: There is no change in the surface of the coating film. B: A little change was seen on the surface of the coating film, but no peeling was seen. C: Changes were seen on the surface of the coating film, but peeling did not occur. D: Peeling occurred on the surface of the coating film. <Crack resistance test> The coated panel was cooled in a low temperature chamber cooled to -20°C, and the test panel was vertically fixed to a flying stone tester (Suga Test Instruments Co., Ltd., JA- 400 type) of the test board installation part, blowing 100 g of No. 7 crushed stone for 5 seconds at an air pressure of 5 kgf/cm 2 to damage the test board. After that, the coated plate was washed with water and dried, and the transparent adhesive tape was adhered to the coated surface, and one end of the tape was peeled off. The degree of damage was evaluated. The evaluation of peeling damage is carried out in the frame of the impacted part with a length of 70 mm × width of 70 mm. A: Best. The peeling area ratio per evaluation area was 0.0% or more and less than 0.7%. B: Good. The peeling area ratio per evaluation area was 0.7% or more and less than 1.2%. C: Poor. The peeling area ratio per evaluation area was 1.2% or more and less than 3.5%. D: Worst. The peeling area ratio per evaluation area is 3.5% or more. [Table 1] In the item "resin skeleton" of Table 1, "P" represents propylene, "E" represents ethylene, and "B" represents butadiene. [Table 2] In Table 2, "2EHA" represents 2-ethylhexyl acrylate, "HEA" represents 2-hydroxyethyl acrylate, "BA" represents butyl acrylate, "INA" represents isononyl acrylate, "AA" represents acrylic acid, "LMA" means lauryl methacrylate, "LA" means lauryl acrylate, "HEMA" means 2-hydroxyethyl methacrylate, and "EA" means ethyl acrylate. The ratio of C 4-12 refers to the weight percentage (%) of the (meth)acrylate represented by the general formula (I) with 4 to 12 carbon atoms relative to the total weight of the monomers to be formulated. [table 3] From Table 3, it can be seen that the modified polyolefin-based resins of Examples are more excellent in chip resistance than Comparative Example 1. In addition, it can be seen that the modified polyolefin-based resins of the examples have no problems in terms of adhesion to polypropylene as a non-polar base material and stability when used as resin dispersions or paints.
