TW201739776A - Modified polypropylene resin and method for producing modified polypropylene resin - Google Patents

Abstract

An object of the present invention is to provide a modified polypropylene resin that exhibits an excellent fluidity when it is heat-molten. To solve the problem, the present invention uses a polypropylene resin exhibiting the specific heat melting characteristics and viscoelasticity as a polypropylene resin that is a. raw material.

Description

改質聚丙烯系樹脂及改質聚丙烯系樹脂之製造方法 Modified polypropylene resin and modified polypropylene resin manufacturing method

本發明係有關改質聚丙烯系樹脂及改質聚丙烯系樹脂之製造方法。 The present invention relates to a method for producing a modified polypropylene resin and a modified polypropylene resin.

以往，由於聚丙烯系樹脂之機械性質及耐藥品性等優異，因此被應用作為各種成形品的原材料。 Conventionally, polypropylene resins are excellent in mechanical properties and chemical resistance, and are therefore used as raw materials for various molded articles.

就聚丙烯系樹脂製的成形品而言，已知由聚丙烯系樹脂發泡片熱成形之發泡成形品等。 In the molded article made of a polypropylene resin, a foam molded article obtained by thermoforming a polypropylene resin foam sheet or the like is known.

就該聚丙烯系樹脂發泡片，已知為發泡層單層者、及具有積層有發泡層與非發泡層之積層結構者。 The polypropylene-based resin foamed sheet is known as a single layer of a foamed layer, and has a laminated structure in which a foamed layer and a non-foamed layer are laminated.

在區分該等時，「發泡片」之用語係以狹義用來代指前者，而後者則稱為「積層發泡片」等。 In distinguishing between these, the term "foam sheet" is used in the narrow sense to refer to the former, while the latter is referred to as "layered foam sheet".

該發泡片和積層發泡片，在以往係藉由擠出發泡法而製作，但因聚丙烯系樹脂一般而言係具有結晶性，故熔融時的黏度及熔融張力容易有所不足，難以得到發泡狀態良好者。 The foamed sheet and the laminated foamed sheet are produced by an extrusion foaming method in the related art. However, since the polypropylene resin generally has crystallinity, the viscosity and the melt tension during melting are likely to be insufficient. A person who has a good foaming state is obtained.

為了解決如此之問題，有人探討將聚丙烯系樹脂以苯乙烯單體等芳香族乙烯基單體改質而調整熔融 特性之方法。 In order to solve such a problem, it has been proposed to adjust the melting of a polypropylene resin by modifying an aromatic vinyl monomer such as a styrene monomer. The method of characteristics.

例如，下述的專利文獻1中記載一種得到改質聚丙烯系樹脂之方法，該改質聚丙烯系樹脂係具有在熔融狀態所測定的伸長黏度會隨著應變量增加而急劇上升的性質(亦稱為“應變硬化性”)。 For example, Patent Document 1 listed below discloses a method of obtaining a modified polypropylene resin having a property in which the elongational viscosity measured in a molten state rapidly increases as the amount of strain increases (for example). Also known as "strain hardening").

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本特開平09-188728號公報 [Patent Document 1] Japanese Patent Publication No. 09-188728

如上述之改質聚丙烯系樹脂在熱熔融時會發揮高的熔融張力，但有未發揮充分的流動性之情形。 The modified polypropylene resin as described above exhibits a high melt tension when it is thermally melted, but may not exhibit sufficient fluidity.

本發明之課題係提供一種在熱熔融時發揮高的熔融張力，且顯示高的流動性之改質聚丙烯系樹脂。 An object of the present invention is to provide a modified polypropylene resin which exhibits high melt tension during hot melting and exhibits high fluidity.

本發明為了解決上述課題，提供一種改質聚丙烯系樹脂，其係聚丙烯系樹脂與芳香族乙烯基單體的反應物，且具有較前述聚丙烯系樹脂更高的熔融張力者，前述聚丙烯系樹脂在溫度230℃、額定荷重2.16kg的條件下所測定之熔融質量流率為4.0g/10分鐘以上。 In order to solve the above problems, the present invention provides a modified polypropylene resin which is a reaction product of a polypropylene resin and an aromatic vinyl monomer and which has a higher melt tension than the polypropylene resin. The propylene-based resin had a melt mass flow rate of 4.0 g/10 min or more measured under the conditions of a temperature of 230 ° C and a rated load of 2.16 kg.

而且，本發明為了解決上述課題，提供一種改質聚丙烯系樹脂之製造方法，其係使聚丙烯系樹脂與芳香族乙烯基單體反應而製作熔融張力較前述聚丙烯系樹 脂更高之改質聚丙烯系樹脂者，其中，係使用在溫度230℃、額定荷重2.16kg的測定條件下顯示4.0g/10分鐘以上的熔融質量流率之聚丙烯系樹脂作為前述聚丙烯系樹脂。 Further, in order to solve the above problems, the present invention provides a method for producing a modified polypropylene resin which is obtained by reacting a polypropylene resin with an aromatic vinyl monomer to produce a melt tension which is higher than the polypropylene tree. In the case of a modified polypropylene resin having a higher fat, a polypropylene resin having a melt mass flow rate of 4.0 g/10 minutes or more under a measurement condition of a temperature of 230 ° C and a rated load of 2.16 kg is used as the polypropylene. Resin.

依據本發明，可提供一種在熱熔融時發揮高的熔融張力且顯示高的流動性之改質聚丙烯系樹脂。 According to the present invention, it is possible to provide a modified polypropylene resin which exhibits high melt tension during heat fusion and exhibits high fluidity.

1‧‧‧積層發泡片 1‧‧‧Laminated foam

10‧‧‧發泡層 10‧‧‧Foam layer

20、20’‧‧‧非發泡層 20, 20' ‧ ‧ non-foaming layer

70‧‧‧第一擠出管線 70‧‧‧First extrusion line

80‧‧‧第二擠出管線 80‧‧‧Second extrusion line

90‧‧‧匯合模 90‧‧‧ Convergence mode

91‧‧‧滾輪 91‧‧‧Roller

92‧‧‧捲繞滾輪 92‧‧‧Winding roller

100‧‧‧圓模 100‧‧‧round die

200‧‧‧冷卻心軸 200‧‧‧Cooling mandrel

BM‧‧‧載台 BM‧‧‧ stage

CT‧‧‧分切裝置 CT‧‧‧ slitting device

CR1‧‧‧冷卻裝置 CR1‧‧‧Cooling device

FB、FB’‧‧‧積層發泡體 FB, FB’‧‧‧ laminated foam

ST‧‧‧攪拌子 ST‧‧‧ stirrer

TB‧‧‧高型燒杯 TB‧‧‧ high beaker

第1圖係一實施形態之使用改質聚丙烯系樹脂所成的積層發泡片之概略剖面圖。 Fig. 1 is a schematic cross-sectional view showing a laminated foam sheet obtained by using a modified polypropylene resin in an embodiment.

第2圖係表示用以製造同一積層發泡片之設備構造的概略圖。 Fig. 2 is a schematic view showing the structure of an apparatus for manufacturing the same laminated foam sheet.

第3圖係第2圖中由虛線圈起的A部分之詳細圖。 Fig. 3 is a detailed view of the portion A from the dotted circle in Fig. 2.

第4圖係表示用以測定膠化率之器具類的概略斜視圖。 Fig. 4 is a schematic perspective view showing an apparatus for measuring a gelation rate.

說明本發明之實施形態。 An embodiment of the present invention will be described.

以下，係以使用由聚丙烯系樹脂與芳香族乙烯基單體反應而得之改質聚丙烯系樹脂來製作具有積層結構的聚丙烯系樹脂發泡片的情況為例，並參照圖式加以說明。 In the following, a case where a polypropylene-based resin foamed sheet having a laminated structure is produced by using a modified polypropylene-based resin obtained by reacting a polypropylene-based resin and an aromatic vinyl monomer is used as an example, and reference is made to the drawings. Description.

第1圖係聚丙烯系樹脂發泡片的概略剖面圖，如圖式所示，本實施形態之使用改質聚丙烯系樹脂而成之聚丙烯系樹脂發泡片，係具備發泡層10及非發泡層20、20’。 1 is a schematic cross-sectional view of a polypropylene-based resin foamed sheet, and as shown in the drawing, a polypropylene-based resin foamed sheet obtained by using a modified polypropylene-based resin of the present embodiment is provided with a foamed layer 10 And non-foamed layers 20, 20'.

此外，以下，係將包含第1圖所示之態樣者在內為具備1層以上的發泡層及1層以上的非發泡層之聚丙烯系樹 脂發泡片以及具備2層以上的發泡層之聚丙烯系樹脂發泡片稱之為「積層發泡片」，以與發泡層單層的聚丙烯系樹脂發泡片作為區別。 In the following, a polypropylene tree having one or more foam layers and one or more non-foamed layers, including the one shown in Fig. 1, is included. The fat-foamed sheet and the polypropylene-based resin foam sheet having two or more foam layers are referred to as "laminated foam sheets", and are distinguished from the polypropylene-based resin foam sheets having a single layer of the foam layer.

因此，以下只要沒有特別的聲明，「積層發泡片」的用語即意指具有如第1圖所示之積層結構者，「發泡片」的用語則作為意指發泡層單層的薄片之用語使用。 Therefore, unless otherwise stated, the term "polymerized foam sheet" means the layered structure as shown in Fig. 1, and the term "foam sheet" means a sheet of a single layer of a foamed layer. The term is used.

如上所述，前述積層發泡片1係具備發泡層10及非發泡層20、20’。 As described above, the laminated foam sheet 1 includes the foamed layer 10 and the non-foamed layers 20 and 20'.

前述發泡層10係由利用擠出發泡法製作的發泡片所形成。 The foamed layer 10 is formed of a foamed sheet produced by an extrusion foaming method.

而且，前述非發泡層20、20’係由利用擠出法製作的樹脂膜所形成。 Further, the non-foamed layers 20, 20' are formed of a resin film produced by an extrusion method.

前述積層發泡片1係前述發泡層10與前述非發泡層20、20’之共擠出物。 The laminated foam sheet 1 is a coextruded product of the foam layer 10 and the non-foamed layers 20 and 20'.

亦即，前述積層發泡片1係將用以製作擠出發泡片與擠出膜之聚丙烯系樹脂組成物積層在匯合模，將該等以積層一體化的狀態從一個模縫(die-slit)予以擠出而成者。 In other words, the laminated foam sheet 1 is formed by laminating a polypropylene resin composition for producing an extruded foam sheet and an extruded film in a merged mold, and the laminate is integrated from a mold seam (die- Slit) is extruded.

前述積層發泡片1中，發泡層10及非發泡層20、20’係由含有改質聚丙烯系樹脂的聚丙烯系樹脂組成物所形成。 In the laminated foam sheet 1, the foamed layer 10 and the non-foamed layers 20 and 20' are formed of a polypropylene resin composition containing a modified polypropylene resin.

形成發泡層10及非發泡層20、20’的聚丙烯系樹脂組成物之中，形成發泡層10的第一聚丙烯系樹脂組成物係含有改質聚丙烯系樹脂，且更含有用以發泡的成分。 Among the polypropylene resin compositions forming the foamed layer 10 and the non-foamed layers 20 and 20', the first polypropylene-based resin composition forming the expanded layer 10 contains a modified polypropylene-based resin and further contains The ingredient used for foaming.

形成非發泡層20、20’的第二聚丙烯系樹脂組成物亦 含有改質聚丙烯系樹脂。 The second polypropylene resin composition forming the non-foamed layers 20, 20' is also Contains modified polypropylene resin.

形成發泡層10的第一聚丙烯系樹脂組成物及形成非發泡層20、20’的第二聚丙烯系樹脂組成物，所含有的改質聚丙烯系樹脂可為相同或相異。 The first polypropylene-based resin composition forming the foamed layer 10 and the second polypropylene-based resin composition forming the non-foamed layers 20 and 20' may be the same or different in the modified polypropylene-based resin.

本實施形態之改質聚丙烯系樹脂係利用特定的改質聚合物的製造方法製作者。 The modified polypropylene resin of the present embodiment is produced by a method for producing a specific modified polymer.

首先，說明改質聚丙烯系樹脂及其製造方法。 First, a modified polypropylene resin and a method for producing the same will be described.

(改質聚丙烯系樹脂) (modified polypropylene resin)

本實施形態之改質聚丙烯系樹脂係使含有(A)聚丙烯系樹脂、(B)有機過氧化物及(C)芳香族乙烯基單體的樹脂組成物(以下亦稱「原料組成物」)反應而得者。 The modified polypropylene resin of the present embodiment is a resin composition containing (A) a polypropylene resin, (B) an organic peroxide, and (C) an aromatic vinyl monomer (hereinafter also referred to as "raw material composition" ") The response is obtained.

本實施形態之改質聚丙烯系樹脂，較佳係採用在200℃的頻率分散動態黏彈性測定中所求得的相位角在頻率0.01Hz時為30°以上70°以下者。 The modified polypropylene resin of the present embodiment is preferably one in which the phase angle obtained by measuring the dynamic viscoelasticity at a frequency of 200 ° C is 30° or more and 70° or less at a frequency of 0.01 Hz.

在頻率分散動態黏彈性測定中，於低頻率區域容易出現黏滯力(viscous term)的影響。 In the frequency dispersion dynamic viscoelasticity measurement, the influence of the viscous term is likely to occur in the low frequency region.

亦即，本實施形態之改質聚丙烯系樹脂係在低頻率區域的相位角較小，不容易產生分子間的“滑動”者。 That is, the modified polypropylene resin of the present embodiment has a small phase angle in a low frequency region, and is unlikely to cause "gliding" between molecules.

因此，本實施形態之改質聚丙烯系樹脂，在為了形成發泡層而進行發泡時會顯示適當的延伸，抑制隨著氣泡成長使氣泡膜急劇變薄，故可防止膜的破壞(破泡)，有利於得到連續氣泡率低的發泡片。 Therefore, the modified polypropylene resin of the present embodiment exhibits appropriate elongation when foaming to form a foamed layer, and prevents the bubble film from being rapidly thinned as the bubble grows, thereby preventing the film from being broken (broken) Foam) is advantageous for obtaining a foamed sheet having a low continuous cell ratio.

更且，本實施形態之改質聚丙烯系樹脂亦有利於抑制 於非發泡層產生因延伸造成的破裂、開孔等現象(以下稱為「樹脂開裂」)而於非發泡層的表面形成露出發泡層之部位，和抑制以積層一體化的狀態從模縫擠出時之垂伸(draw down)。 Furthermore, the modified polypropylene resin of the present embodiment is also advantageous for suppressing In the non-foamed layer, a phenomenon such as cracking or opening due to stretching (hereinafter referred to as "resin cracking") is formed on the surface of the non-foamed layer to expose the foamed layer, and the state in which the laminated layer is integrated is suppressed. Draw down when the die seam is extruded.

此外，前述相位角係依下述的方式求出者。 Further, the phase angle described above is obtained in the following manner.

(相位角的求法) (method of phase angle)

動態黏彈性測定係以黏彈性測定裝置PHYSICA MCR301(Anton Paar公司製)、溫度控制系統CTD450進行測定。 The dynamic viscoelasticity measurement was performed by a viscoelasticity measuring apparatus PHYSICA MCR301 (manufactured by Anton Paar Co., Ltd.) and a temperature control system CTD450.

首先，將作為試料的改質聚丙烯系樹脂以熱壓機在溫度200℃×加熱5分鐘的條件下予以壓製，製作直徑25mm、厚度3mm的圓盤試樣。 First, the modified polypropylene resin as a sample was pressed by a hot press at a temperature of 200 ° C for 5 minutes to prepare a disk sample having a diameter of 25 mm and a thickness of 3 mm.

其次，將試樣設置在已加熱至測定溫度(200℃)的黏彈性測定裝置的試臺上，在氮氣環境下加熱達5分鐘，並進行熔融。 Next, the sample was placed on a test stand of a viscoelasticity measuring apparatus heated to a measurement temperature (200 ° C), heated in a nitrogen atmosphere for 5 minutes, and melted.

之後，以直徑25mm的平行板擠壓至間隔2.0mm為止，移除從試臺溢出的樹脂。 Thereafter, the mixture was pressed to a spacing of 2.0 mm with a parallel plate having a diameter of 25 mm to remove the resin overflowing from the test stand.

接著，在達到測定溫度±1℃之後再加熱5分鐘後，在應變5%、頻率0.01至100(Hz)、測定點的點數為21(5點/十次(point/decade))、測定溫度200℃的條件下進行動態黏彈性測定，測定相位角δ(°)。 Then, after heating for 5 minutes after reaching the measurement temperature of ±1 ° C, the strain was 5%, the frequency was 0.01 to 100 (Hz), and the number of points at the measurement point was 21 (5 points/decade). Dynamic viscoelasticity measurement was carried out at a temperature of 200 ° C, and the phase angle δ (°) was measured.

此外，測定起始係從高頻率側(100Hz)開始。 In addition, the measurement initiation system starts from the high frequency side (100 Hz).

並且，求出在頻率0.01Hz的相位角δ。 Further, a phase angle δ at a frequency of 0.01 Hz was obtained.

就更確實地發揮降低發泡層10的連續氣泡 率和抑制非發泡層20、20’的樹脂開裂之效果而言，不只是使改質聚丙烯系樹脂表現如上述之相位角，亦使第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物中的至少一者、較佳為兩者在溫度200℃、頻率0.01Hz時表現30°以上70°以下的相位角為較佳。 More effectively, the continuous bubble of the foamed layer 10 is lowered. The rate and the effect of suppressing the resin cracking of the non-foamed layers 20, 20' are not only the modified polypropylene-based resin exhibiting the phase angle as described above, but also the first polypropylene-based resin composition and the second polypropylene. It is preferable that at least one of the resin compositions preferably exhibits a phase angle of 30° or more and 70° or less at a temperature of 200 ° C and a frequency of 0.01 Hz.

第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物中所含的改質聚丙烯系樹脂，係改質成會表現較起始原料的(A)聚丙烯系樹脂更高的熔融張力者。 The modified polypropylene-based resin contained in the first polypropylene-based resin composition and the second polypropylene-based resin composition is modified to exhibit higher melting of the (A) polypropylene-based resin than the starting material. Tension.

改質聚丙烯系樹脂是否表現較作為原料使用的聚丙烯系樹脂更高的熔融張力乙事，可藉由例如在230℃的溫度比較兩者的熔融張力來辨別。 Whether the modified polypropylene resin exhibits a higher melt tension than the polypropylene resin used as the raw material can be distinguished by, for example, comparing the melt tension of the two at a temperature of 230 °C.

一般的聚丙烯系樹脂在230℃的熔融張力為未達5cN者，故可不與作為起始原料的(A)聚丙烯系樹脂比較，而將在230℃測定的熔融張力表現6cN以上的值者視為改質聚丙烯系樹脂。 In general, the polypropylene resin has a melt tension of less than 5 cN at 230 ° C. Therefore, the melt tension measured at 230 ° C can be expressed as a value of 6 cN or more as compared with the (A) polypropylene resin as a starting material. It is considered as a modified polypropylene resin.

改質聚丙烯系樹脂係以在230℃的熔融張力為6cN以上為較佳，在230℃的熔融張力為10cN以上為更佳，在230℃的熔融張力為15cN以上為特佳。 The modified polypropylene resin preferably has a melt tension at 230 ° C of 6 cN or more, a melt tension at 230 ° C of 10 cN or more, and a melt tension of 230 ° C of 15 cN or more.

但是，改質聚丙烯系樹脂的熔融張力過度高時，在擠出第一聚丙烯系樹脂組成物、第二聚丙烯系樹脂組成物時會有導致擠出機的負荷大之疑慮，故以在230℃時的值以30cN以下為較佳，在28cN以下為更佳。 However, when the melt tension of the modified polypropylene resin is excessively high, when the first polypropylene resin composition and the second polypropylene resin composition are extruded, there is a concern that the load on the extruder is large, so The value at 230 ° C is preferably 30 cN or less, more preferably 28 cN or less.

此外，對於改質聚丙烯系樹脂、積層發泡片等欲求熔融張力時，可以如下述的方法求出。 In addition, when a melt tension is desired for a modified polypropylene resin, a laminated foam sheet, or the like, it can be obtained by the following method.

[熔融張力測定方法] [Melt tension measurement method]

在測定對象為顆粒時係直接使用作為試料，在測定對象為積層發泡片等薄片狀時，則是採用使用製粒機(例如東洋精機製作所股份有限公司製的「Hand Truder型號PM-1」)將該薄片以筒體(cylinder)溫度220℃、從填充試料至開始擠出為止的待機時間2.5分鐘的條件顆粒化者。 When the measurement target is a pellet, it is used as a sample, and when the measurement target is a sheet-like foam sheet or the like, a granulator is used (for example, "Hand Truder model PM-1" manufactured by Toyo Seiki Seisakusho Co., Ltd. The sheet was granulated under the conditions of a cylinder temperature of 220 ° C and a standby time of 2.5 minutes from the filling of the sample to the start of extrusion.

熔融張力係使用雙料筒毛細管流變儀(twin bore capillary rheometer)Rheologic5000T(Italy Chiasuto公司製)進行測定。 The melt tension was measured using a twin bore capillary rheometer Rheologic 5000T (manufactured by Italy Chiasuto Co., Ltd.).

亦即，將測定試料樹脂填充於已加熱至試驗溫度之直徑15mm的料筒(barrel)後，預熱5分鐘之後，從上述測定裝置的毛細管模頭(口徑2.0mm、長度20mm、流入角度平面)以保持一定的活塞下降速度(0.1546mm/s)的方式擠出成股狀，同時使該股狀物通過位於上述毛細管模頭下方27cm的位置之張力檢測的皮帶輪後，使用捲繞捲筒並使其捲繞速度以初速8.7mm/s、加速度12mm/s²的方式緩慢地增加並進行捲繞，以股狀物剛要斷裂前的極大值與極小值之平均作為試料的熔融張力。 That is, the test sample resin was filled in a barrel having a diameter of 15 mm heated to the test temperature, and after preheating for 5 minutes, the capillary die (caliber 2.0 mm, length 20 mm, inflow angle plane) from the above measuring device The product is extruded into a strand shape while maintaining a certain piston descending speed (0.1546 mm/s), and the strand is passed through a tension detecting pulley located 27 cm below the capillary die, and a winding reel is used. The winding speed was gradually increased and wound at a first speed of 8.7 mm/s and an acceleration of 12 mm/s ² , and the average value of the maximum value and the minimum value immediately before the strand was broken was taken as the melt tension of the sample.

此外，在張力圖中只有1個極大點時，則採該極大點的極大值作為熔融張力。 Further, when there is only one maximum point in the tension map, the maximum value of the maximum point is taken as the melt tension.

為了使擠出時擠出機的負荷減輕，且使發泡層10發揮良好的發泡性，在非發泡層20、20’不會產生樹脂開裂等，改質聚丙烯系樹脂之熔融質量流率(MFR)較佳係表現既定的值者。 In order to reduce the load on the extruder during extrusion and to impart good foaming properties to the foamed layer 10, the non-foamed layers 20 and 20' do not undergo resin cracking or the like, and the melt quality of the modified polypropylene resin is improved. The flow rate (MFR) is preferably one that exhibits a predetermined value.

更具體而言，改質聚丙烯系樹脂係以MFR為0.5g/10分鐘以上為較佳，0.7g/10分鐘以上為更佳，1.0g/10分鐘以上為特佳。 More specifically, the modified polypropylene resin is preferably MGR of 0.5 g/10 min or more, more preferably 0.7 g/10 min or more, and particularly preferably 1.0 g/10 min or more.

就形成獨立氣泡性優異(連續氣泡率低)的發泡層而言，改質聚丙烯系樹脂的MFR係以0.7g/10分鐘以上為較佳。 In order to form a foamed layer having excellent closed cell properties (low open cell ratio), the MFR of the modified polypropylene resin is preferably 0.7 g/10 min or more.

但是，MFR過度高時，會有變得難以使發泡層10發揮良好的發泡性之情形，故改質聚丙烯系樹脂的MFR較佳為5.0g/10分鐘以下，更佳為3.0g/10分鐘以下。 However, when the MFR is excessively high, the foamed layer 10 may be difficult to exhibit good foaming properties. Therefore, the MFR of the modified polypropylene resin is preferably 5.0 g/10 min or less, more preferably 3.0 g. /10 minutes or less.

此外，改質聚丙烯系樹脂的MFR可以根據JIS K7210：1999「塑膠-熱塑性塑膠的熔融質量流率(MFR)及熔融體積流率(MVR)的試驗方法」之B法進行測定，並可以溫度230℃、額定荷重2.16kg的條件進行測定。 In addition, the MFR of the modified polypropylene resin can be measured according to the B method of JIS K7210:1999 "Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of plastic-thermoplastic plastic", and the temperature can be measured. The measurement was carried out under the conditions of 230 ° C and a rated load of 2.16 kg.

更具體而言，MFR係依以下的方式測定。 More specifically, MFR was measured in the following manner.

當測定對象為顆粒時，係直接使用作為測定用試料。 When the measurement target is a pellet, it is used as a sample for measurement.

當測定對象為發泡片時，則係利用東洋精機製作所股份有限公司製的製粒機「Hand Truder型號PM-1」使該發泡片顆粒化，以作為測定用試料。 When the measurement target is a foamed sheet, the foamed sheet is pelletized by a granulator "Hand Truder model PM-1" manufactured by Toyo Seiki Seisakusho Co., Ltd. as a sample for measurement.

此外，使用製粒機而由發泡片製作顆粒時之筒體溫度係設為220℃，從填充試料至開始擠出之間的待機時間係設為2.5分鐘。 Further, the temperature of the cylinder when the pellets were produced from the foamed sheet using a granulator was 220 ° C, and the standby time from the filling of the sample to the start of extrusion was set to 2.5 minutes.

熔融質量流率(MFR)係使用東洋精機製作所股份有限公司製的Semi-auto melt indexer 2A，藉由JIS K 7210：1999「塑膠-熱塑性塑膠的熔融質量流率(MFR)及熔融體積流率 (MVR)的試驗方法」之B法中所記載之「b)測定活塞移動既定距離的時間之方法」而測定。 The melt mass flow rate (MFR) is a semi-auto melt indexer 2A manufactured by Toyo Seiki Seisakusho Co., Ltd., and the melt mass flow rate (MFR) and melt volume flow rate of plastic-thermoplastic plastics by JIS K 7210:1999 (b) The method of measuring the time when the piston moves a predetermined distance is described in the "B method of the test method of (MVR)".

測定條件係設為：試料量3至8g、預熱時間270秒、負載維持時間30秒、試驗溫度230℃、試驗荷重21.18N、活塞移動距離(間隔)4mm。 The measurement conditions were as follows: a sample amount of 3 to 8 g, a preheating time of 270 seconds, a load holding time of 30 seconds, a test temperature of 230 ° C, a test load of 21.18 N, and a piston moving distance (interval) of 4 mm.

試驗次數為3次，以其平均值作為熔融質量流率(g/10分鐘)的值。 The number of tests was three, and the average value thereof was taken as the value of the melt mass flow rate (g/10 minutes).

就得到如此之改質聚丙烯系樹脂而言，作為其起始原料之(A)聚丙烯系樹脂較佳係具有既定的熔融特性者。 In order to obtain such a modified polypropylene-based resin, the (A) polypropylene-based resin which is a starting material thereof preferably has a predetermined melting property.

〔(A)聚丙烯系樹脂〕 [(A) Polypropylene resin]

(A)聚丙烯系樹脂係藉由使丙烯單體聚合而得之聚合物。 (A) A polypropylene-based resin is a polymer obtained by polymerizing a propylene monomer.

就用以得到改質聚丙烯系樹脂之原料組成物中所含的(A)聚丙烯系樹脂而言，可列舉丙烯單體的均聚物、丙烯單體與其他單體的共聚物等。 The (A) polypropylene-based resin contained in the raw material composition for obtaining the modified polypropylene-based resin may, for example, be a homopolymer of a propylene monomer, a copolymer of a propylene monomer and another monomer, or the like.

前述共聚物，例如以在聚合成分100質量%中，丙烯單體的含量係50質量%以上為較佳，丙烯單體的含量係80質量%以上為更佳，丙烯單體的含量係90質量%以上為特佳。 In the copolymer, for example, the content of the propylene monomer is preferably 50% by mass or more, and the content of the propylene monomer is preferably 80% by mass or more, and the content of the propylene monomer is 90% by mass. More than % is especially good.

共聚合可為無規共聚合，亦可為嵌段共聚合。 The copolymerization may be a random copolymerization or a block copolymerization.

聚丙烯系樹脂為共聚物時，丙烯單體以外的成分係以選自由乙烯單體及碳數4至8的α烯烴單體所組成群組之 1種以上為較佳，以乙烯單體及1-丁烯單體內的1種以上為更佳。 When the polypropylene resin is a copolymer, components other than the propylene monomer are selected from the group consisting of ethylene monomers and alpha olefin monomers having 4 to 8 carbon atoms. One or more kinds are preferable, and one or more of the ethylene monomer and the 1-butene monomer are more preferable.

作為(A)聚丙烯系樹脂，具體而言，可列舉丙烯均聚物、丙烯無規聚合物及丙烯嵌段聚合物等。 Specific examples of the (A) polypropylene-based resin include a propylene homopolymer, a propylene random polymer, and a propylene block polymer.

(A)聚丙烯系樹脂較佳為丙烯單體的均聚物，以丙烯均聚物為佳。 (A) The polypropylene resin is preferably a homopolymer of a propylene monomer, and a propylene homopolymer is preferred.

為了使改質聚丙烯系樹脂表現高MFR值，較佳係採用表現高MFR者作為(A)聚丙烯系樹脂。 In order to make the modified polypropylene-based resin exhibit a high MFR value, it is preferred to use (A) a polypropylene-based resin which exhibits a high MFR.

一般使用作為發泡片的形成材料之聚丙烯系樹脂，其MFR為1g/10分鐘以下左右，但作為改質聚丙烯系樹脂之起始原料的聚丙烯系樹脂，其熔融質量流率(MFR)較佳為4.0g/10分鐘以上。 Generally, a polypropylene resin which is a material for forming a foamed sheet has a MFR of about 1 g/10 minutes or less, but a polypropylene resin which is a starting material of a modified polypropylene resin has a melt mass flow rate (MFR). ) is preferably 4.0 g/10 minutes or more.

(A)聚丙烯系樹脂的MFR更佳為4.0g/10分鐘以上20.0g/10分鐘以下，特佳為7.0g/10分鐘以上18.0g/10分鐘以下。 The MFR of the (A) polypropylene resin is more preferably 4.0 g/10 min or more and 20.0 g/10 min or less, and particularly preferably 7.0 g/10 min or more and 18.0 g/10 min or less.

通常，就對改質聚丙烯系樹脂賦予高的熔融張力而言，係以(A)聚丙烯系樹脂在熔融質量流率的值愈低愈有利。 In general, it is advantageous to impart a high melt tension to the modified polypropylene resin because the value of the (A) polypropylene resin is lower at the melt mass flow rate.

因此，如上所述，只將高MFR的(A)聚丙烯系樹脂作為改質聚丙烯系樹脂的起始原料者，為了對改質聚丙烯系樹脂賦予高的熔融張力而增加(B)有機過氧化物、(C)芳香族乙烯基單體的使用量，結果是可能會造成改質聚丙烯系樹脂中含有大量的凝膠。 Therefore, as described above, only the (A) polypropylene resin having a high MFR is used as a starting material for the modified polypropylene resin, and (B) organic is added in order to impart a high melt tension to the modified polypropylene resin. The amount of the peroxide or (C) aromatic vinyl monomer used may cause a large amount of gel to be contained in the modified polypropylene resin.

於是，作為改質聚丙烯系樹脂的起始原料，係以併用 表現4.0g/10分鐘以上的MFR之第一聚丙烯系樹脂與MFR未達4.0g/10分鐘之第二聚丙烯系樹脂為較佳。 Therefore, as a starting material for the modified polypropylene resin, it is used in combination. It is preferred that the first polypropylene resin exhibiting an MFR of 4.0 g/10 minutes or more and the second polypropylene resin having an MFR of less than 4.0 g/10 minutes.

第一聚丙烯系樹脂較佳係由表現4.0g/10分鐘以上20g/10分鐘以下的MFR者之中選出者，更佳係由表現7.0g/10分鐘以上18.0g/10分鐘以下的MFR者之中選出。 The first polypropylene-based resin is preferably selected from those having an MFR of 4.0 g/10 min or more and 20 g/10 min or less, more preferably an MFR of 7.0 g/10 min or more and 18.0 g/10 min or less. Selected among them.

作為MFR較第一聚丙烯系樹脂更低的第二聚丙烯系樹脂，較佳係由表現0.1g/10分鐘以上且未達4.0g/10分鐘的MFR者之中選出，更佳係由表現0.5g/10分鐘以上且未達4.0g/10分鐘的MFR者之中選出。 The second polypropylene-based resin having a lower MFR than the first polypropylene-based resin is preferably selected from those having an MFR of 0.1 g/10 min or more and less than 4.0 g/10 min, and more preferably Among the MFRs of 0.5 g/10 minutes or more and less than 4.0 g/10 minutes, it was selected.

第一聚丙烯系樹脂與第二聚丙烯系樹脂，例如可以使質量比率(第一PP/第二PP)成為90/10至10/90的方式摻配使用。 The first polypropylene-based resin and the second polypropylene-based resin can be blended, for example, in such a manner that the mass ratio (first PP/second PP) is 90/10 to 10/90.

如此地，以複數種聚丙烯系樹脂作為改質聚丙烯系樹脂的起始原料時，混合有該複數種聚丙烯系樹脂的混合樹脂，MFR較佳為4.0g/10分鐘以上。 In the case where a plurality of kinds of polypropylene resins are used as starting materials for the modified polypropylene resin, the mixed resin of the plurality of polypropylene resins is mixed, and the MFR is preferably 4.0 g/10 minutes or more.

混合樹脂的MFR，例如可以與起始原料中所含的比率相同的比率摻配聚丙烯系樹脂，將經摻配的聚丙烯系樹脂熔融混合而製作測定用試料，藉由測定該測定用試料的MFR而求出。 The MFR of the mixed resin can be blended with a polypropylene resin in the same ratio as the ratio contained in the starting material, and the blended polypropylene resin can be melt-mixed to prepare a sample for measurement, and the sample for measurement can be measured. The MFR is obtained.

又，關於原料組成物，當將第一聚丙烯系樹脂的質量與第二聚丙烯系樹脂的質量之合計值中之第一聚丙烯系樹脂所占的質量百分率設為a₁(%)、第二聚丙烯系樹脂所占的質量百分率設為a₂(%)，且將第一聚丙烯系樹脂 的熔融質量流率之值設為A₁(g/10分鐘)、第二聚丙烯系樹脂的熔融質量流率之值設為A₂(g/10分鐘)時，係以至少滿足下述關係式(x)為較佳。 In the raw material composition, the mass percentage of the first polypropylene resin in the total of the mass of the first polypropylene resin and the mass of the second polypropylene resin is a ₁ (%), The mass percentage of the second polypropylene resin is a ₂ (%), and the value of the melt mass flow rate of the first polypropylene resin is A ₁ (g/10 minutes), and the second polypropylene system When the value of the melt mass flow rate of the resin is A ₂ (g/10 minutes), it is preferable to satisfy at least the following relationship (x).

[A₁×a₁+A₂×a₂]/100≧4.0．．．(x) [A ₁ × a ₁ + A ₂ × a ₂ ] / 100 ≧ 4.0. . . (x)

藉由使原料組成物中之第一聚丙烯系樹脂與第二聚丙烯系樹脂具有上述的關係，發揮可以得到用以得到連氣率低的擠出積層發泡片之改質聚丙烯系樹脂之效果。 By having the above-described relationship between the first polypropylene-based resin and the second polypropylene-based resin in the raw material composition, it is possible to obtain a modified polypropylene-based resin which can be used to obtain an extruded laminated foam sheet having a low gas content. The effect.

本實施形態之改質聚丙烯系樹脂，因為是使用MFR高的聚丙烯系樹脂作為起始原料，故即使在通過擠出機後仍得以發揮優異的應變硬化性。 Since the modified polypropylene resin of the present embodiment uses a polypropylene resin having a high MFR as a starting material, it exhibits excellent strain hardenability even after passing through an extruder.

積層發泡片之改質聚丙烯系樹脂不僅在初期狀態具有應變硬化性，在通過擠出機後，改質聚丙烯系樹脂仍會發揮應變硬化性，藉此可成為良好的發泡狀態。 The modified polypropylene resin of the laminated foam sheet has strain hardenability in an initial state, and the modified polypropylene resin exhibits strain hardenability after passing through the extruder, whereby a foamed state can be obtained.

具體而言，改質聚丙烯系樹脂在通過擠出機後，以溫度200℃、1.0/秒之一定應變速度來測定一軸伸長黏度時會表現應變硬化性，且在將橫軸設為應變量(ε)的對數(log(ε))、縱軸設為伸長黏度(η)的對數(log(η))之雙對數曲線圖中表示一軸伸長黏度的測定結果時，在應變量1以上3以下的範圍內之曲線圖的斜率較佳為1.0以上。 Specifically, the modified polypropylene resin exhibits strain hardenability when measured by a single strain elongation at a constant strain rate of 200 ° C and 1.0 / sec after passing through an extruder, and the horizontal axis is set as a strain amount. When the logarithm of (ε) (log(ε)) and the vertical axis are the logarithm of the logarithm of the elongational viscosity (η) (log(η)), the measurement results of the one-axis elongational viscosity are shown in the strain 1 or more. The slope of the graph in the following range is preferably 1.0 or more.

此外，本說明書中之所謂的「在應變量1以上3以下的範圍內之曲線圖的斜率」，原則上係意指對於前述曲線圖在應變量1至3之間以最小平方法作成近似直線時之該直線的斜率。 In addition, the term "slope of the graph in the range of the strain 1 or more and 3 or less" in the present specification means, in principle, an approximate straight line with the least squares method between the strains 1 to 3 for the aforementioned graph. The slope of the line at that time.

但是，在應變量成為3之前，伸長的樹脂若產生斷裂等而致使曲線圖在應變量1至3之間結束時，則例外地係由應變量1至前述曲線圖的終點為止以最小平方法作成近似直線，並將其斜率作為「在應變量1以上3以下的範圍內之曲線圖的斜率」來判斷。 However, before the strain becomes 3, if the elongation of the resin causes a curve or the like to end between the strains 1 to 3, the exception is from the strain 1 to the end point of the aforementioned graph by the least square method. An approximate straight line is formed, and the slope is determined as "the slope of the graph in the range of the strain 1 or more and 3 or less".

本實施形態之改質聚丙烯系樹脂所示之前述曲線圖的斜率，較佳為1.1以上，更佳為1.2以上。 The slope of the above-described graph shown by the modified polypropylene resin of the present embodiment is preferably 1.1 or more, and more preferably 1.2 or more.

前述曲線圖的斜率，通常為4以下，較佳為3以下，更佳為2.5以下，又更佳為1.6以下。 The slope of the aforementioned graph is usually 4 or less, preferably 3 or less, more preferably 2.5 or less, still more preferably 1.6 or less.

本說明書中之所謂的「通過擠出機後」，原則上係意指利用東洋精機製作所股份有限公司製之「Labo Plastomill(商品名)」擠出後的狀態。 In the present specification, the term "after passing through the extruder" means, in principle, the state in which "Labo Plastomill (trade name)" manufactured by Toyo Seiki Seisakusho Co., Ltd. is extruded.

更詳細而言，係在東洋精機製作所製的「Labo Plastomill」的本體(型號：4M150)裝設單軸擠出機{型號：D2020[附有口徑：20mm、L/D：20之標準螺桿(全螺紋型1條)]}，將單軸擠出機之3區域的溫度從擠出方向上游側朝向下游側依序設定為210℃、190℃、190℃，且將前端模具溫度設定為180℃，同時以使吐出量成為1kg/小時的方式固定螺桿的旋轉數，在本說明書中係將該通過「Labo Plastomill」後的狀態定義為「通過擠出機後」的狀態。 In more detail, the main body of the "Labo Plastomill" manufactured by Toyo Seiki Co., Ltd. (model: 4M150) is equipped with a single-axis extruder {Model: D2020 [with a diameter of 20 mm, L/D: 20 standard screw ( One thread of the full-thread type)]], the temperature of the three regions of the single-axis extruder was set to 210 ° C, 190 ° C, and 190 ° C from the upstream side toward the downstream side in the extrusion direction, and the front mold temperature was set to 180. At the same time, the number of rotations of the screw is fixed so that the discharge amount becomes 1 kg/hour. In the present specification, the state after passing the "Labo Plastomill" is defined as the state after "passing the extruder".

此外，一軸伸長黏度的測定，可對以上述方式設定之「Labo Plastomill」供應改質聚丙烯系樹脂並擠出成股束(strand)狀，使該股束狀的試料通過已置有20℃的水之1m的水槽中進行冷卻，將經冷卻的試料切斷而製作長度4mm 左右的棒狀顆粒而求出。 In addition, for the measurement of the elongation of the one-axis, the modified polypropylene resin can be supplied to the "Labo Plastomill" set as described above and extruded into a strand shape, so that the bundle-shaped sample has passed through 20 ° C. The water is cooled in a 1 m water tank, and the cooled sample is cut to make a length of 4 mm. The left and right rod-shaped particles were obtained.

更詳細而言，藉由使用黏彈性測定裝置來測定該棒狀顆粒的一軸伸長黏度，可測定改質聚丙烯系樹脂通過擠出機後之一軸伸長黏度的值。 More specifically, by measuring the one-axis elongational viscosity of the rod-shaped particles using a viscoelasticity measuring device, the value of the elongational viscosity of the modified polypropylene-based resin after passing through the extruder can be measured.

若更詳細說明，在通過擠出機後的改質聚丙烯系樹脂之一軸伸長黏度的值，可根據下述條件進行測定。 More specifically, the value of the axial elongational viscosity of one of the modified polypropylene-based resins after passing through the extruder can be measured according to the following conditions.

又，在需對通過擠出機之前的改質聚丙烯系樹脂進行一軸伸長黏度測定時，該一軸伸長黏度亦可以下述條件測定。 Further, when the one-axis elongational viscosity of the modified polypropylene resin before passing through the extruder is measured, the one-axis elongational viscosity can also be measured under the following conditions.

<一軸伸長黏度測定條件> <One-axis elongation viscosity measurement condition>

一軸伸長黏度測定係利用黏彈性測定裝置「PHYSICA MCR301」(Anton Paar公司製)、溫度控制系統「CTD450」進行測定。 The one-axis elongational viscosity measurement system was measured by a viscoelasticity measuring device "PHYSICA MCR301" (manufactured by Anton Paar Co., Ltd.) and a temperature control system "CTD450".

首先，將要測定的改質聚丙烯系樹脂以熱壓機在190℃的溫度壓製5分鐘，製作寬度10mm、厚度約0.8mm的長條狀試樣。 First, the modified polypropylene resin to be measured was pressed at a temperature of 190 ° C for 5 minutes in a hot press to prepare a long sample having a width of 10 mm and a thickness of about 0.8 mm.

其次，將該長條狀試樣以使長度成為20至25mm的方式切出，作成試驗片。 Next, the long sample was cut out so as to have a length of 20 to 25 mm to prepare a test piece.

將試驗片設置在已加熱至200℃的黏彈性測定裝置之一軸伸長黏度測定用治具(jig)(SER2)，在氮氣環境下以200℃±0.5℃的溫度條件待機10秒後，以應變速度1.0/秒測定一軸伸長黏度。 The test piece was placed in a jig-extension viscosity measuring jig (SER2) of a viscoelasticity measuring device heated to 200 ° C, and was allowed to stand at a temperature of 200 ° C ± 0.5 ° C for 10 seconds under a nitrogen atmosphere to be strained. The axial elongation viscosity was measured at a speed of 1.0/sec.

測定點間隔設定為「將測定點間隔以對數取得」，將開 始設為0.01秒，結束設為26秒。 The measurement point interval is set to "take the measurement point interval in logarithm" and it will be opened. It is set to 0.01 second and the end is set to 26 seconds.

測定點設為200。 The measurement point was set to 200.

關於測定結果，係採用將縱軸設為伸長黏度(η：Pa．s)的常用對數值(log(η))、橫軸設為應變量(ε：s/s)的常用對數值(log(ε))之雙對數軸曲線圖，在應變量1至3的範圍、或在應變量達3之前試驗片斷裂、偏離時，對於由應變量1至表示最大伸長黏度的應變量為止以最小平方法作成近似直線，求出該近似直線的斜率。 Regarding the measurement results, the common logarithmic value (log(η)) in which the vertical axis is the elongation viscosity (η:Pa.s) and the horizontal axis is the common logarithm (ε:s/s) (log) The double logarithmic axis graph of (ε)), in the range of strains 1 to 3, or when the test piece breaks or deviates before the strain amount reaches 3, the most variable from 1 to the maximum elongation viscosity The Xiaoping method is made to approximate the line, and the slope of the approximate line is obtained.

就通過擠出機後之一軸伸長黏度的曲線圖中前述斜率為1.0以上的改質聚丙烯系樹脂而言，可列舉於分子鏈具有分枝結構者。 The modified polypropylene-based resin having a slope of 1.0 or more in the graph of the axial elongation viscosity after passing through the extruder is exemplified by a branched structure having a molecular chain.

亦即，通過擠出機前的改質聚丙烯系樹脂(以下亦稱為「初期-mPP」)，在本實施形態中為具有分枝的分子結構者。 In other words, the modified polypropylene resin (hereinafter also referred to as "initial-mPP") before the extruder is a molecular structure having a branch in the present embodiment.

該「初期-mPP」較佳係分枝數多且分子鏈容易形成相互纏結者。 The "initial-mPP" is preferably such that the number of branches is large and the molecular chains are likely to form intertwined ones.

分枝少的改質聚丙烯系樹脂，會因擠出機中所施加的剪力使分子鏈的纏結容易解纏結，而容易使通過擠出機後的應變硬化性較通過擠出機前大幅下降。 The modified polypropylene resin with few branches will easily entangle the molecular chain due to the shear force applied in the extruder, and it is easy to pass the strain hardening property after passing through the extruder. Before the sharp decline.

欲藉由使用此種改質聚丙烯系樹脂之擠出發泡法製造積層發泡片時，改質聚丙烯系樹脂的應變硬化性在從模縫擠出之時便已喪失，而有無法得到發泡狀態良好的積層發泡片之虞。 When a laminated foam sheet is produced by an extrusion foaming method using such a modified polypropylene resin, the strain hardenability of the modified polypropylene resin is lost when it is extruded from the die slit, and it is impossible to obtain The flaw of the laminated foam sheet which is in a good foaming state.

另一方面，分枝數多且容易形成分子鏈的纏結之改質聚丙烯系樹脂，在擠出後仍可維持良好的應變 硬化性。 On the other hand, a modified polypropylene resin having a large number of branches and easily forming an entanglement of molecular chains can maintain good strain after extrusion. Hardenability.

就使改質聚丙烯系樹脂形成如此之分枝結構而言，係以採用如前述之表現高MFR者作為起始原料所使用之具有線型分子結構的聚丙烯系樹脂(以下亦稱為「線性PP」)較為有利。 In order to form the branched structure of the modified polypropylene resin, a polypropylene resin having a linear molecular structure (hereinafter also referred to as "linear" is used as a starting material using a high MFR as described above. PP") is more advantageous.

製作前述改質聚丙烯系樹脂時，因β裂解而產生線性PP的主鏈切斷，被切斷的分子與其他分子鍵結，藉此形成長鏈分枝。 When the modified polypropylene resin is produced, the main chain of the linear PP is cleaved by β cleavage, and the cleaved molecules are bonded to other molecules, thereby forming long-chain branches.

於是，作為改質聚丙烯系樹脂的起始原料之線性PP若為分子量大者，而添加大量的乙烯基單體、自由基產生劑時，樹脂的熔融黏度會變得過高，有不太能增加分枝數之虞。 Therefore, when the linear PP which is a starting material of the modified polypropylene resin is a large molecular weight, when a large amount of a vinyl monomer or a radical generator is added, the melt viscosity of the resin becomes too high, and there is a case where it is not too high. Can increase the number of branches.

另一方面，分子量小且具有高MFR之線性PP即使導入大量的分枝，熔融黏度也不會上升至造成實用上問題的程度。 On the other hand, a linear PP having a small molecular weight and a high MFR does not rise to a degree which causes a practical problem even if a large number of branches are introduced.

因此，為了得到在通過擠出機後仍表現良好的應變硬化性之改質聚丙烯系樹脂，係以採用MFR高的線性PP作為起始材料為較佳。 Therefore, in order to obtain a modified polypropylene resin which exhibits good strain hardenability after passing through an extruder, it is preferred to use a linear PP having a high MFR as a starting material.

依前述，作為改質聚丙烯系樹脂的起始原料之聚丙烯系樹脂的MFR，更佳為5.0g/10分鐘以上，又更佳為7.0g/10分鐘以上。 In the above, the MFR of the polypropylene-based resin which is a starting material of the modified polypropylene-based resin is more preferably 5.0 g/10 min or more, still more preferably 7.0 g/10 min or more.

該聚丙烯系樹脂的MFR較佳為20.0g/10分鐘以下，更佳為18.0g/10分鐘以下。 The MFR of the polypropylene resin is preferably 20.0 g/10 min or less, more preferably 18.0 g/10 min or less.

此外，作為改質聚丙烯系樹脂的起始原料 之(A)聚丙烯系樹脂的MFR，亦可與改質聚丙烯系樹脂的MFR同樣地根據JIS K7210：1999「塑膠-熱塑性塑膠的熔融質量流率(MFR)及熔融體積流率(MVR)之試驗方法」的B法，以溫度230℃、額定荷重2.16kg的條件進行測定。 In addition, as a starting material for the modified polypropylene resin The MFR of the (A) polypropylene-based resin may be the same as the MFR of the modified polypropylene-based resin according to JIS K7210:1999 "Melting-Molding-Molding-Molding Mass Flow Rate (MFR) and Melt Volume Flow Rate (MVR) The B method of the test method was measured under the conditions of a temperature of 230 ° C and a rated load of 2.16 kg.

前述改質聚丙烯系樹脂在通過擠出機後，在溫度180℃、應變速度0.1至8.5(sec^-1)測定一軸伸長黏度時，較佳係表現0.25以上的多分枝指數(MBI)。 The modified polypropylene-based resin preferably exhibits a multi-branched index (MBI) of 0.25 or more when the one-axis elongational viscosity is measured at a temperature of 180 ° C and a strain rate of 0.1 to 8.5 (sec ^-1 ) after passing through an extruder.

本說明書中之所謂的多分枝指數(MBI)，係意指在橫軸設為應變速度(v)的對數(log(v))、縱軸設為應變硬化度(SHI)之單對數的曲線圖中表示一軸伸長黏度的測定結果時之曲線圖的斜率。而且，所謂的應變硬化度(SHI)，係意指在橫軸設為應變量(ε)的對數(log(ε))、縱軸設為伸長黏度(η)的對數(log(η))之雙對數曲線圖中表示一軸伸長黏度的測定結果時，在應變量1以上3以下的範圍之曲線圖的斜率。 The so-called multi-branch index (MBI) in the present specification means a logarithm of the logarithm (log(v)) of the strain velocity (v) on the horizontal axis and a single logarithm of the strain hardening degree (SHI) on the vertical axis. The graph shows the slope of the graph when the measurement results of the one-axis elongational viscosity are measured. Further, the strain hardening degree (SHI) means a logarithm (log(ε)) in which the horizontal axis is the strain amount (ε), and a vertical axis is the logarithm (log(η)) of the elongation viscosity (η). In the double logarithmic graph, the slope of the graph in the range of the strain 1 or more and 3 or less is shown when the measurement result of the one-axis elongational viscosity is measured.

而且，求出多分枝指數(MBI)及應變硬化度(SHI)時的「曲線圖的斜率」，係意指以最小平方法作成近似直線時該直線的斜率。 Further, the "slope of the graph" when the multi-branch index (MBI) and the strain hardening degree (SHI) are obtained means the slope of the straight line when the approximate straight line is formed by the least square method.

本實施形態之改質聚丙烯系樹脂，在通過擠出機後以溫度180℃、應變速度0.1至8.5(sec^-1)測定一軸伸長黏度時，以採用不同的速度下仍會顯示應變硬化性者為較佳。 In the modified polypropylene resin of the present embodiment, when the one-axis elongational viscosity is measured at a temperature of 180 ° C and a strain rate of 0.1 to 8.5 (sec ^-1 ) after passing through an extruder, strain hardenability is exhibited at different speeds. It is better.

又，改質聚丙烯系樹脂的多分枝指數(MBI)，通常為0.6以下，較佳為0.5以下。 Further, the multi-branching index (MBI) of the modified polypropylene-based resin is usually 0.6 or less, preferably 0.5 or less.

在此所謂的「通過擠出機後」，如前所述，係意指用東洋精機製作所股份有限公司製之「Labo Plastomill(商品名)」擠出後的狀態。 As described above, "after passing through the extruder", it is a state in which "Labo Plastomill (trade name)" manufactured by Toyo Seiki Seisakusho Co., Ltd. is extruded.

<一軸伸長黏度測定條件> <One-axis elongation viscosity measurement condition>

求出應變硬化度(SHI)時之一軸伸長黏度測定，可使用黏彈性測定裝置「PHYSICA MCR301」(Anton Paar公司製)、溫度控制系統「CTD450」而實施。 The measurement of the axial elongation viscosity at the time of the strain hardening degree (SHI) can be carried out using a viscoelasticity measuring device "PHYSICA MCR301" (manufactured by Anton Paar Co., Ltd.) and a temperature control system "CTD450".

首先，將要測定的改質聚丙烯系樹脂以熱壓機在220℃的溫度壓製6分鐘，製作寬度10mm、厚度約0.8mm的長條狀試樣。 First, the modified polypropylene resin to be measured was pressed at a temperature of 220 ° C for 6 minutes in a hot press to prepare a long sample having a width of 10 mm and a thickness of about 0.8 mm.

其次，將該長條狀試樣以使長度成為20至25mm的方式切出，作成試驗片。 Next, the long sample was cut out so as to have a length of 20 to 25 mm to prepare a test piece.

將試驗片設置在已加熱至180℃的黏彈性測定裝置之一軸伸長黏度測定用治具(SER2)，在氮氣環境下以180℃±0.5℃的溫度條件待機10秒後，以應變速度(v)：於5點(0.1、0.3、1.0、3.0及8.5(s^-1))分別測定一軸伸長黏度。 The test piece was placed in a jig-elongation viscosity measuring jig (SER2) of a viscoelasticity measuring device heated to 180 ° C, and was allowed to stand at a temperature of 180 ° C ± 0.5 ° C for 10 seconds under a nitrogen atmosphere at a strain rate (v). ): One-axis elongational viscosity was measured at 5 points (0.1, 0.3, 1.0, 3.0, and 8.5 (s ^-1 )), respectively.

測定點間隔係設定為「將測定點間隔以對數取得」，將開始設為0.01秒，結束設為26秒。 The measurement point interval is set to "take the measurement point interval in logarithm", and the start is set to 0.01 second, and the end is set to 26 seconds.

測定點設為200。 The measurement point was set to 200.

多分枝指數(MBI)可依以下的方式求出。 The multi-branch index (MBI) can be obtained in the following manner.

首先，在橫軸為應變量(ε：s/s)的對數(log(ε))、縱軸為伸長黏度(η：Pa．s)的對數(log(η))之曲線圖中，表現以應變速度0.1(s^-1)實施的一軸伸長黏度之測定結果，在應變 量1至應變量3為止之間對於曲線圖以最小平方法作成近似直線，求出其斜率(應變硬化度(SHI_0.1))。 First, in the graph where the horizontal axis is the logarithm of the strain (ε: s/s) (log(ε)) and the vertical axis is the logarithm of the elongational viscosity (η: Pa.s) (log(η)), The measurement results of the one-axis elongational viscosity measured at a strain rate of 0.1 (s ^-1 ) were approximated to the curve by the least square method between the strain 1 and the strain 3, and the slope (strain hardening degree (SHI) was obtained. _0.1 )).

其次，將應變速度分別變更為0.3(s^-1)、1.0(s^-1)、3.0(s^-1)、及8.5(s^-1)而進行上述測定，對於各者求出應變硬化度(SHI_0.3、SHI_1.0、SHI_3.0、SHI_8.5)。 Next, the strain rate was changed to 0.3 (s ^-1 ), 1.0 (s ^-1 ), 3.0 (s ^-1 ), and 8.5 (s ^-1 ) to perform the above measurement, and the strain hardening degree was obtained for each ( SHI _0.3 , SHI _1.0 , SHI _3.0 , SHI _8.5 ).

然後，在縱軸為應變硬化度(SHI)、橫軸為應變速度的對數(log(v))之曲線圖中，將上述的結果作圖。 Then, the above results are plotted in a graph in which the vertical axis represents the strain hardening degree (SHI) and the horizontal axis represents the logarithm of the strain velocity (log (v)).

亦即，將(log(0.1),SHI_0.1)、(log(0.3),SHI_0.3)、(log(1.0),SHI_1.0)、(log(3.0),SHI_3.0)、(log(8.5),SHI_8.5)之5點作圖成曲線圖。 That is, (log(0.1), SHI _0.1 ), (log(0.3), SHI _0.3 ), (log(1.0), SHI _1.0 ), (log(3.0), SHI _3.0 ), (log(8.5), 5 points of SHI _8.5 ) are plotted as a graph.

然後，將該5點的作圖以最小平方法作成近似直線，以所得之斜率作為多分枝指數(MBI)。 Then, the plot of the 5 points was made into an approximate straight line by the least square method, and the obtained slope was used as the multi-branch index (MBI).

就得到具有如此之多分枝指數的改質聚丙烯系樹脂而言，使用作為起始原料的聚丙烯系樹脂，係以分子量相較小且顯示高熔融質量流率(MFR)者為較佳。 In order to obtain a modified polypropylene resin having such a plurality of branching indexes, it is preferred to use a polypropylene resin as a starting material, which has a small molecular weight phase and exhibits a high melt mass flow rate (MFR).

亦即，就得到表現如上述之多分枝指數的改質聚丙烯系樹脂而言，作為起始原料的聚丙烯系樹脂之熔融質量流率(MFR)，係以4.0g/10分鐘以上為較佳，5.0g/10分鐘以上為更佳，佳7.0g/10分鐘以上為又更佳。 In other words, in the modified polypropylene resin which exhibits the multi-branched index as described above, the melt mass flow rate (MFR) of the polypropylene-based resin as a starting material is 4.0 g/10 minutes or more. Good, 5.0g/10 minutes or more is better, and better 7.0g/10 minutes or more is better.

該聚丙烯系樹脂的MFR較佳為20.0g/10分鐘以下，更佳為18.0g/10分鐘以下。 The MFR of the polypropylene resin is preferably 20.0 g/10 min or less, more preferably 18.0 g/10 min or less.

改質聚丙烯系樹脂藉由使起始原料具有高MFR，不僅可表現如上述之多分枝指數(MBI)，亦可減低凝膠的含有率。 The modified polypropylene resin can exhibit not only the above-mentioned multi-branched index (MBI) but also the content of the gel by making the starting material have a high MFR.

改質聚丙烯系樹脂中所含的凝膠，係使發泡層形成粗大氣泡之原因，亦為使非發泡層樹脂開裂、形成微小突起之原因。 The gel contained in the modified polypropylene-based resin causes the foamed layer to form coarse bubbles, and also causes the non-foamed layer resin to be cracked to form minute projections.

然而，本實施形態之改質聚丙烯系樹脂，如上所述，係將MFR相異的複數種聚丙烯系樹脂作為起始原料，藉此可將其膠化率的值設為例如1.0質量%以下，較佳係將膠化率的值設為0.6質量%以下，特佳係設為0.3質量%以下。 However, as described above, the modified polypropylene-based resin of the present embodiment has a plurality of kinds of polypropylene-based resins having different MFRs as a starting material, whereby the value of the gelation ratio can be, for example, 1.0% by mass. In the following, it is preferable to set the value of the gelation ratio to 0.6% by mass or less, and more preferably to 0.3% by mass or less.

此外，針對改質聚丙烯系樹脂、積層發泡片求出凝膠含量(膠化率)時，可利用如第4圖所示之器具，以下述之方法求出。 Further, when the gel content (gelation ratio) is determined for the modified polypropylene resin or the laminated foam sheet, it can be obtained by the following method using an apparatus as shown in Fig. 4 .

[凝膠含量測定方法] [Method for measuring gel content]

試料為顆粒、珠粒時，係直接使用，發泡體係切割為1cm見方左右。 When the sample is granules or beads, it is used directly, and the foaming system is cut to about 1 cm square.

精秤該試料0.8g後，將之放入底部平坦且側面百折狀之200網孔金屬網。 After weighing 0.8 g of the sample, it was placed in a 200 mesh metal mesh with a flat bottom and a side fold.

在200mL高型燒杯(第4圖的符號TB)內放置載台(第4圖的符號BM)，在該載台與高型燒杯的杯底之間的空間放置攪拌子(第4圖的符號ST)。 Place the stage (symbol BM in Fig. 4) in a 200 mL high beaker (symbol TB in Fig. 4), and place the stirrer in the space between the stage and the bottom of the cup of the high beaker (symbol of Fig. 4) ST).

在載台上設置放置有試料的網孔金屬網，並加入二甲苯80mL。 A mesh metal mesh in which the sample was placed was placed on the stage, and 80 mL of xylene was added.

使用加熱攪拌乾浴裝置(AS ONE製HDBS-6)以130℃、80rpm攪拌3小時後，將高型燒杯內的200網孔金屬網以鑷子取出，在已加熱至130℃的二甲苯80mL中進行預洗，去除金屬網側面的附著物。 After stirring at 130 ° C and 80 rpm for 3 hours using a heated stirring dry bath apparatus (HDBS-6 manufactured by AS ONE), the 200 mesh metal mesh in the high type beaker was taken out as a tweezers in 80 mL of xylene which had been heated to 130 ° C. Pre-washing is performed to remove the attachment on the side of the metal mesh.

之後，將金屬網上的樹脂不溶物在通風櫃內自然乾燥，使二甲苯蒸發，最後將樹脂不溶物連同金屬網一起在恆溫乾燥器以120℃乾燥2小時。 Thereafter, the resin insoluble matter on the metal mesh was naturally dried in a fume hood to evaporate xylene, and finally the resin insoluble matter was dried together with the metal mesh at 120 ° C for 2 hours in a constant temperature drier.

在乾燥器內放冷後連同金屬網一起測定質量，根據下述式算出凝膠含量(質量%)。 After cooling in a desiccator, the mass was measured together with the metal mesh, and the gel content (% by mass) was calculated according to the following formula.

凝膠含量(質量%)=金屬網上的不溶樹脂質量(g)/試料質量(0.8g)×100 Gel content (% by mass) = insoluble resin mass on the metal mesh (g) / sample mass (0.8 g) × 100

(金屬網上的不溶樹脂質量=過濾乾燥後之金屬網的質量-僅過濾前之金屬網的質量) (Insoluble resin quality on the metal mesh = quality of the metal mesh after filtration and drying - only the quality of the metal mesh before filtration)

不僅藉由將MFR相異的複數種聚丙烯系樹脂作為起始原料可減低改質聚丙烯系樹脂中所含的凝膠之量，藉由對於與該起始原料反應之單體、用以使該單體與聚丙烯系樹脂反應之自由基產生劑之種類的選擇和用量的限制亦可減低改質聚丙烯系樹脂中所含的凝膠之量。 The amount of the gel contained in the modified polypropylene resin can be reduced by using a plurality of polypropylene resins different in MFR as a starting material, by using a monomer reactive with the starting material. The selection and the amount of the radical generating agent which reacts the monomer with the polypropylene resin can also reduce the amount of the gel contained in the modified polypropylene resin.

在本實施形態中，係使用有機過氧化物作為前述自由基產生劑，及使用芳香族乙烯基單體作為前述單體。 In the present embodiment, an organic peroxide is used as the radical generating agent, and an aromatic vinyl monomer is used as the monomer.

〔(B)有機過氧化物〕 [(B) Organic peroxide]

本實施形態之(B)有機過氧化物係對於聚丙烯系樹脂具有奪氫(hydrogen abstraction)能力者，並無特別限定，可列舉例如：過氧化氫、過氧化二烷、過氧化酯、過氧化二醯、過氧化二碳酸酯、過氧化縮酮及過氧化酮等。 (B) The organic peroxide of the present embodiment is not particularly limited as long as it has hydrogen abstraction ability to the polypropylene resin, and examples thereof include hydrogen peroxide, dioxane, peroxyester, and Dioxin, peroxydicarbonate, peroxyketal, and ketone peroxide.

作為前述過氧化氫，可列舉例如：過氧化氫對甲烷、過氧化氫二異丙基苯、過氧化氫異丙苯及過氧化氫第三丁基等。 Examples of the hydrogen peroxide include hydrogen peroxide to methane, diisopropylbenzene hydrogen peroxide, cumene hydroperoxide, and a hydrogen peroxide tert-butyl group.

作為前述過氧化二烷，可列舉例如：過氧化二異丙苯、過氧化二-第三丁基、及2,5-二甲基-2,5-二(過氧化第三丁基)-已炔-3等。 Examples of the dioxanes include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di(t-butylperoxy peroxide)- Alkyne-3 and the like.

作為前述過氧化酯，可列舉例如：過氧化2-乙基己基碳酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化苯甲酸第三己酯、過氧化苯甲酸第三丁酯、過氧化月桂酸第三丁酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化乙酸第三丁酯、2,5-二甲基2,5-二(過氧化苯甲醯基)己烷、及過氧化異丙基單碳酸第三丁酯等。 Examples of the peroxyester ester include: tert-butyl 2-ethylhexyl carbonate, third hexyl isopropyl peroxycarbonate, third hexyl peroxybenzoate, and third benzoic acid peroxide. Butyl ester, third butyl laurate, tert-butyl peroxy-3,5,5-trimethylhexanoate, tert-butyl peroxyacetate, 2,5-dimethyl 2,5- Di(benzoyl peroxide)hexane, and butyl tricarbonate monoperoxide.

作為前述過氧化二醯，可列舉例如：過氧化二苯甲醯、過氧化二(4-甲基苯甲醯)及過氧化二(3-甲基苯甲醯)等。 Examples of the bismuth peroxide include, for example, benzamidine peroxide, bis(4-methylbenzhydryl) peroxide, and bis(3-methylbenzhydrazide).

作為前述過氧化二碳酸酯，可列舉例如：過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二異丙酯等。 Examples of the peroxydicarbonate include di(2-ethylhexyl) peroxydicarbonate and diisopropyl peroxydicarbonate.

作為前述過氧化縮酮，可列舉例如：1,1-二-過氧化第三丁基-3,3,5-三甲基環己烷、1,1-二-過氧化第三丁基環己烷、2,2-二(過氧化第三丁基)-丁烷、4,4-二-(過氧化第三丁基)戊酸正丁酯、及2,2-雙(4,4-二-過氧化第三丁基環己基)丙烷等。 Examples of the peroxy ketal include 1,1-di-peroxide tert-butyl-3,3,5-trimethylcyclohexane, and 1,1-di-peroxide tert-butyl ring. Hexane, 2,2-di(t-butylperoxy)-butane, n-butyl 4,4-di-(t-butylperoxy)pentanoate, and 2,2-bis (4,4) -di-peroxidized tert-butylcyclohexyl)propane or the like.

作為前述過氧化酮，可列舉例如：過氧化甲基乙基酮、過氧化乙醯丙酮等。 The ketone peroxide may, for example, be methyl ethyl ketone peroxide or acetoxyacetone peroxide.

本實施形態之(B)有機過氧化物，較佳為過 氧化酯、過氧化二醯或過氧化二碳酸酯。 The organic peroxide of (B) of the present embodiment is preferably Oxidized ester, dioxane peroxide or peroxydicarbonate.

前述有機過氧化物較佳係具有下述通式(X)所示之結構。 The organic peroxide preferably has a structure represented by the following formula (X).

(惟，R¹係表示取代或未取代的苯基或是取代或未取代的烷氧基，R²係表示1價有機基)。 (R ¹ represents a substituted or unsubstituted phenyl group or a substituted or unsubstituted alkoxy group, and R ² represents a monovalent organic group).

此外，通式(X)內，「R¹」為烷氧基時，「R¹」較佳係氧原子鍵結於具有碳數為3至8個的分枝結構之烷基(例如：異丙基、第三丁基、第三己基、2-乙基己基等)之烷氧基。 Further, in the formula (X), when "R ¹ " is an alkoxy group, "R ¹ " is preferably an oxygen atom bonded to an alkyl group having a branched structure having 3 to 8 carbon atoms (for example, different Alkoxy group of propyl, tert-butyl, tert-hexyl, 2-ethylhexyl, etc.).

「R¹」為氧原子鍵結於2-乙基己基之烷氧基以外者時，氧原子較佳係鍵結於2級碳或3級碳，較佳係具有下述通式(Y)所示之結構。 When "R ¹ " is an oxygen atom bonded to alkoxy group of 2-ethylhexyl group, the oxygen atom is preferably bonded to the second-order carbon or the tertiary carbon, and preferably has the following formula (Y) The structure shown.

(惟，式中的「R¹¹」、「R¹²」表示其中之任一者為甲基且另一者為氫原子，「R¹⁴」表示碳數1至6的直鏈烷基，「R¹³」表示2級碳或3級碳。) (However, "R ¹¹ " and "R ¹² " in the formula indicate that either of them is a methyl group and the other is a hydrogen atom, and "R ¹⁴ " represents a linear alkyl group having 1 to 6 carbon atoms, "R ¹³ ” means grade 2 carbon or grade 3 carbon.)

此外，當「R¹」為取代或未取代的苯基之任一者時，「R¹」較佳為未取代的苯基，或1個氫原子經甲基 取代之取代苯基。 Further, when "R ¹ " is a substituted or unsubstituted phenyl group, "R ¹ " is preferably an unsubstituted phenyl group or a substituted phenyl group in which one hydrogen atom is substituted with a methyl group.

而且，「R²」亦以分枝烷基、苯基等具有巨大的結構者為較佳。 Further, "R ² " is also preferably a structure having a large structure such as a branched alkyl group or a phenyl group.

具體而言，較佳係具有下述通式(Z)所示之結構。 Specifically, it is preferred to have a structure represented by the following formula (Z).

(惟，式中的「R²¹」係表示碳數1至6的直鏈烷基、或具有苯基的1價有機基之任一者。) (However, in the formula "R ^21" represents a straight-chain alkyl-based 1 to 6 carbon atoms, or a monovalent organic group having any one of a phenyl group.)

作為具有通式(X)所示之結構的有機過氧化物，可列舉例如：過氧化2-乙基己基碳酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化異丙基單碳酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-二(過氧化苯甲醯基)已烷、過氧化二苯甲醯、過氧化二(4-甲基苯甲醯)、過氧化二碳酸二異丙酯等。 The organic peroxide having the structure represented by the general formula (X) includes, for example, tert-butyl 2-ethylhexyl carbonate, third hexyl peroxymonocarbonate, and isopropyl peroxide. Tert-butyl monocarbonate, third hexyl peroxybenzoate, 2,5-dimethyl-2,5-di(benzylidene peroxide)hexane, perylene peroxide, peroxidation Bis(4-methylbenzhydrazide), diisopropyl peroxydicarbonate, and the like.

在用以製作前述改質聚丙烯系樹脂的原料組成物中，相對於(A)聚丙烯系樹脂100質量份，(B)有機過氧化物的含量較佳為0.1質量份以上、1.5質量份以下。 In the raw material composition for producing the modified polypropylene resin, the content of the organic peroxide (B) is preferably 0.1 part by mass or more and 1.5 parts by mass based on 100 parts by mass of the (A) polypropylene resin. the following.

本實施形態之改質聚丙烯系樹脂之(B)有機過氧化物的含量過少時，因原料組成物的反應性變低，會有無法發揮良好的改質效果之虞。 When the content of the (B) organic peroxide in the modified polypropylene resin of the present embodiment is too small, the reactivity of the raw material composition is lowered, and a good reforming effect cannot be exhibited.

本實施形態之改質聚丙烯系樹脂之(B)有機過氧化物的含量過大時，因熔融混練時聚丙烯系樹脂容易產生分解 反應，有彈性成分變小而無法發揮良好的改質效果之虞。 When the content of the (B) organic peroxide in the modified polypropylene resin of the present embodiment is too large, the polypropylene resin is likely to be decomposed during melt kneading. In the reaction, the elastic component becomes small and the effect of the improvement is not exhibited.

亦即，藉由使(B)有機過氧化物的含量為0.1質量份以上、1.5質量份以下，即使未以高精度調控前述原料組成物在熔融混練時之反應條件，亦可製作具有優異的熔融張力之改質聚丙烯系樹脂。 In other words, when the content of the (B) organic peroxide is 0.1 part by mass or more and 1.5 parts by mass or less, the reaction conditions of the raw material composition at the time of melt kneading can be controlled without high precision, and it can be produced excellently. A modified polypropylene resin having a melt tension.

就更確實地製作具有優異的熔融張力之改質聚丙烯系樹脂而言，相對於(A)聚丙烯系樹脂100質量份，前述原料組成物之(B)有機過氧化物的含量較佳為0.3質量份以上，較佳為1.0質量份以下。 When the modified polypropylene resin having an excellent melt tension is more reliably produced, the content of the (B) organic peroxide of the raw material composition is preferably 100 parts by mass of the (A) polypropylene resin. 0.3 parts by mass or more, preferably 1.0 part by mass or less.

〔(C)芳香族乙烯基單體〕 [(C) Aromatic Vinyl Monomer]

(C)芳香族乙烯基單體係與(A)聚丙烯系樹脂進行化學性的結合，形成分枝結構，同時作為使聚丙烯系樹脂彼此間交聯的交聯劑而作用之成分。 (C) A component in which the aromatic vinyl single system is chemically bonded to the (A) polypropylene resin to form a branched structure and acts as a crosslinking agent for crosslinking the polypropylene resins.

原料組成物所含的(C)芳香族乙烯基單體可只為1種，亦可為2種以上。 The (C) aromatic vinyl monomer contained in the raw material composition may be one type or two or more types.

作為前述芳香族乙烯基單體，可列舉：苯乙烯；鄰-甲基苯乙烯、間-甲基苯乙烯、對-甲基苯乙烯、α-甲基苯乙烯、β-甲基苯乙烯、二甲基苯乙烯、三甲基苯乙烯等甲基苯乙烯；α-氯苯乙烯、β-氯苯乙烯、鄰-氯苯乙烯、間-氯苯乙烯、對-氯苯乙烯、二氯苯乙烯、三氯苯乙烯等氯苯乙烯；鄰-溴苯乙烯、間-溴苯乙烯、對-溴苯乙烯、二溴苯乙烯、三溴苯乙烯等溴苯乙烯；鄰-氟苯乙烯、間-氟苯乙烯、對-氟苯乙烯、二氟苯乙烯、三氟苯乙烯等氟苯乙烯； 鄰-硝基苯乙烯、間-硝基苯乙烯、對-硝基苯乙烯、二硝基苯乙烯、三硝基苯乙烯等硝基苯乙烯；鄰-羥基苯乙烯、間-羥基苯乙烯、對-羥基苯乙烯、二羥基苯乙烯、三羥基苯乙烯等乙烯苯酚；鄰-二乙烯基苯、間-二乙烯基苯、對-二乙烯基苯等二乙烯基苯；鄰-二異丙烯基苯、間-二異丙烯基苯、對-二異丙烯基苯等異丙烯基苯。 Examples of the aromatic vinyl monomer include styrene; o-methyl styrene, m-methyl styrene, p-methyl styrene, α-methyl styrene, and β-methyl styrene. Methylstyrene such as dimethylstyrene or trimethylstyrene; α-chlorostyrene, β-chlorostyrene, o-chlorostyrene, m-chlorostyrene, p-chlorostyrene, dichlorobenzene Chlorostyrene such as ethylene or trichlorostyrene; brominated styrene such as o-bromostyrene, m-bromostyrene, p-bromostyrene, dibromostyrene or tribromostyrene; o-fluorostyrene; - fluorostyrene such as fluorostyrene, p-fluorostyrene, difluorostyrene or trifluorostyrene; Nitrostyrene such as o-nitrostyrene, m-nitrostyrene, p-nitrostyrene, dinitrostyrene, trinitrostyrene; o-hydroxystyrene, m-hydroxystyrene, Ethylene phenol such as p-hydroxystyrene, dihydroxystyrene or trihydroxystyrene; divinylbenzene such as o-divinylbenzene, m-divinylbenzene or p-divinylbenzene; o-diisopropylene Isopropenylbenzene such as benzene, m-diisopropenylbenzene or p-diisopropenylbenzene.

其中，芳香族乙烯基單體尤以苯乙烯為較佳。 Among them, an aromatic vinyl monomer is particularly preferably styrene.

相對於(A)聚丙烯系樹脂100質量份，原料組成物中之(C)芳香族乙烯基單體的含量，較佳為0.1質量份以上10質量份以下。 The content of the (C) aromatic vinyl monomer in the raw material composition is preferably 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the (A) polypropylene resin.

改質聚丙烯系樹脂之(C)芳香族乙烯基單體的含量過少時，有無法在熔融混練時充分形成分枝、交聯結構之虞。而且，(C)芳香族乙烯基單體的含量過少時，因過氧化物對於樹脂的分解抑制亦不充分，故有無法發揮良好的改質效果之虞。 When the content of the (C) aromatic vinyl monomer in the modified polypropylene resin is too small, there is a possibility that the branching and crosslinked structure are not sufficiently formed during melt kneading. Further, when the content of the (C) aromatic vinyl monomer is too small, the decomposition of the resin against the decomposition of the resin is insufficient, so that a good reforming effect cannot be exhibited.

改質聚丙烯系樹脂之(C)芳香族乙烯基單體的含量過大時，在熔融混練時容易(C)芳香族乙烯基單體的一部分未進行反應。因此，(C)芳香族乙烯基單體的含量過大時，會使改質聚丙烯系樹脂含有大量的低聚物、因微相分離等導致形成具有白濁的問題者之虞。其結果為使得彈性成分的影響較大地反映在改質聚丙烯系樹脂的特性，有改質聚丙烯系樹脂的延伸不佳、無法顯示良好的改質效果之虞。 When the content of the (C) aromatic vinyl monomer in the modified polypropylene resin is too large, it is easy to react a part of the (C) aromatic vinyl monomer during melt-kneading. Therefore, when the content of the (C) aromatic vinyl monomer is too large, the modified polypropylene-based resin contains a large amount of oligomers, and the problem of formation of white turbidity due to microphase separation or the like is caused. As a result, the influence of the elastic component is largely reflected in the characteristics of the modified polypropylene-based resin, and the modified polypropylene-based resin has poor elongation and cannot exhibit a good reforming effect.

亦即，藉由使原料組成物中之(C)芳香族乙烯基單體的含量為0.1質量份以上、10質量份以下，即使未以高精度 調控熔融混練時之反應條件，亦可製作品質良好的改質聚丙烯系樹脂。 In other words, the content of the (C) aromatic vinyl monomer in the raw material composition is 0.1 part by mass or more and 10 parts by mass or less, even if it is not high precision. By adjusting the reaction conditions during melt-kneading, it is also possible to produce a modified polypropylene resin of good quality.

依如此方式所得之改質聚丙烯系樹脂，對於製作具備低連續氣泡率的發泡層之積層發泡片係為有效者。 The modified polypropylene-based resin obtained in this manner is effective for producing a laminated foamed sheet having a foamed layer having a low open cell ratio.

此外，視所需，原料組成物亦可含有芳香族乙烯基單體以外的單體。 Further, the raw material composition may contain a monomer other than the aromatic vinyl monomer, as needed.

作為該單體，可列舉例如：乙烯、1-丁烯、異丁烯、1-戊烯、3-甲基-1-丁烯、1-己烯、4-甲基-1-戊烯、3,4-二甲基-1-丁烯、1-庚烯、3-甲基-1-己烯、1-辛烯、1-癸烯等α-烯烴單體；環戊烯、降莰烯等環烯烴單體；5-亞甲基-2-降莰烯、5-亞乙基-2-降莰烯、1,4-己二烯、甲基-1,4-己二烯、7-甲基-1,6-辛二烯等二烯單體；氯乙烯、偏二氯乙烯等氯系單體；丙烯腈、丙烯酸、甲基丙烯酸、順丁烯二酸、丙烯酸乙酯、丙烯酸丁酯、丙烯酸縮水甘油酯、甲基丙烯酸甲酯、甲基丙烯酸縮水甘油酯、順丁烯二酸酐等丙烯酸系單體；環氧系單體；乙酸乙烯酯等乙酸酯系單體。 Examples of the monomer include ethylene, 1-butene, isobutylene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3. Α-olefin monomers such as 4-dimethyl-1-butene, 1-heptene, 3-methyl-1-hexene, 1-octene, 1-decene; cyclopentene, norbornene, etc. Cycloolefin monomer; 5-methylene-2-northene, 5-ethylidene-2-norbornene, 1,4-hexadiene, methyl-1,4-hexadiene, 7- a diene monomer such as methyl-1,6-octadiene; a chlorine monomer such as vinyl chloride or vinylidene chloride; acrylonitrile, acrylic acid, methacrylic acid, maleic acid, ethyl acrylate, and butyl acrylate An acrylic monomer such as an ester, glycidyl acrylate, methyl methacrylate, glycidyl methacrylate or maleic anhydride; an epoxy monomer; and an acetate monomer such as vinyl acetate.

[(D)自由基捕捉劑〕 [(D) radical scavenger]

為了得到前述改質聚丙烯系樹脂，前述原料組成物係以含有用以控制其反應性之(D)自由基捕捉劑為較佳。 In order to obtain the modified polypropylene-based resin, the raw material composition preferably contains a (D) radical scavenger for controlling the reactivity thereof.

(D)自由基捕捉劑的使用，對於提高改質聚丙烯系樹脂的熔融張力為有效。 (D) The use of the radical scavenger is effective for increasing the melt tension of the modified polypropylene resin.

亦即，就使用改質聚丙烯系樹脂來得到外觀良好的樹脂發泡體而言，(D)自由基捕捉劑為有效者。 In other words, the (D) radical scavenger is effective in obtaining a resin foam having a good appearance by using a modified polypropylene resin.

(D)自由基捕捉劑係可與烷基自由基物種反應者。 (D) A free radical scavenger is a person that can react with an alkyl radical species.

(D)自由基捕捉劑較佳係可與已鍵結烷基自由基後的芳香族乙烯基單體鍵結者。 (D) The radical scavenger is preferably bonded to the aromatic vinyl monomer after the alkyl radical has been bonded.

(D)自由基捕捉劑可只使用1種，亦可併用2種以上。 (D) The radical scavenger may be used alone or in combination of two or more.

作為(D)自由基捕捉劑，可列舉：醌化合物(醌類)、萘醌化合物(萘醌類)及啡噻(phenothiazine)化合物(啡噻類)等。 Examples of the (D) radical scavenger include an anthracene compound (anthraquinone), a naphthoquinone compound (naphthoquinone), and a thiophene (phenothiazine) compound Class) and so on.

作為前述醌化合物，可列舉：對-苯醌、對-萘醌、2-第三丁基-對-苯醌及2,5-二苯基-對-苯醌等。作為前述萘醌化合物，可列舉：1,4-萘醌、2-羥基-1,4-萘醌及維生素K等。 Examples of the hydrazine compound include p-benzoquinone, p-naphthoquinone, 2-tert-butyl-p-benzoquinone, and 2,5-diphenyl-p-benzoquinone. Examples of the naphthoquinone compound include 1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone, and vitamin K.

作為前述啡噻化合物，可列舉：啡噻、雙-(α-甲基苯甲基)啡噻、3,7-二辛基啡噻、及雙-(α-二甲基苯甲基)啡噻等。 As the aforementioned thiophene Compounds, exemplified by: Bis-(α-methylbenzyl) thiophene 3,7-dioctylmorphothiophene And bis-(α-dimethylbenzyl) thiophene Wait.

前述原料組成物中，相對於(A)聚丙烯系樹脂100質量份，(D)自由基捕捉劑的含量較佳為0.005質量份以上，更佳為0.05質量份以上。 In the raw material composition, the content of the (D) radical scavenger is preferably 0.005 parts by mass or more, and more preferably 0.05 parts by mass or more based on 100 parts by mass of the (A) polypropylene resin.

而且，相對於(A)聚丙烯系樹脂100質量份，(D)自由基捕捉劑的含量較佳為1質量份以下。 In addition, the content of the (D) radical scavenger is preferably 1 part by mass or less based on 100 parts by mass of the (A) polypropylene resin.

(D)自由基捕捉劑的含量為前述下限以上及前述上限以下時，可使改質聚丙烯系樹脂的熔融張力有效地變高，使發泡體的外觀變得更為良好。 When the content of the (D) radical scavenger is not less than the above lower limit and not more than the above upper limit, the melt tension of the modified polypropylene resin can be effectively increased, and the appearance of the foam can be further improved.

該等以外之原料組成物中所含的(E)其他成 分，可列舉各種添加劑。 (E) other ingredients contained in the raw material composition other than these A variety of additives can be mentioned.

〔(E)添加劑〕 [(E) Additive]

(E)添加劑係視各種目的而適當使用，並無特別限定。 The (E) additive is appropriately used depending on various purposes, and is not particularly limited.

作為(E)添加劑的具體例，可列舉耐候性安定劑、抗靜電劑、抗氧化劑、消臭劑、光安定劑、晶核劑、顏料、滑劑、以賦予光滑性或賦予抗結塊性為目的之界面活性劑、無機填充劑以及使無機填充劑的分散性提升之分散性提升劑等。 Specific examples of the (E) additive include weather stabilizers, antistatic agents, antioxidants, deodorants, light stabilizers, crystal nucleating agents, pigments, and slip agents to impart smoothness or impart anti-caking property. A surfactant, an inorganic filler, and a dispersibility improving agent for improving the dispersibility of the inorganic filler.

作為前述分散性提升劑，可列舉高級脂肪酸、高級脂肪酸酯及高級脂肪酸醯胺等。 Examples of the dispersibility improving agent include higher fatty acid, higher fatty acid ester, and higher fatty acid decylamine.

前述(E)添加劑，可在進行熔融混練前或熔融混練時含有在前述原料組成物中。 The above (E) additive may be contained in the raw material composition before melt kneading or during melt kneading.

而且，(E)添加劑亦可是在熔融混練後添加而使改質聚丙烯系樹脂含有(E)添加劑。 Further, the (E) additive may be added after melt-kneading to contain the (E) additive in the modified polypropylene-based resin.

(E)添加劑可只使用1種，亦可併用2種以上。 (E) The additive may be used alone or in combination of two or more.

本實施形態之改質聚丙烯系樹脂，可藉由將原料組成物熔融混練而容易地得到，前述原料組成物係含有相對於前述聚丙烯系樹脂100質量份為0.1質量份以上1.5質量份以下的前述有機過氧化物，且含有相對於前述聚丙烯系樹脂100質量份為0.1質量份以上10質量份以下的前述芳香族乙烯基單體。 The modified polypropylene-based resin of the present embodiment can be easily obtained by melt-kneading the raw material composition, and the raw material composition is contained in an amount of 0.1 part by mass or more and 1.5 parts by mass or less based on 100 parts by mass of the polypropylene-based resin. The above-mentioned aromatic vinyl monomer is contained in an amount of 0.1 part by mass or more and 10 parts by mass or less based on 100 parts by mass of the polypropylene-based resin.

本實施形態之改質聚丙烯系樹脂係適用於形成外觀良好且強度優異的發泡成形品者。 The modified polypropylene resin of the present embodiment is suitable for use in forming a foamed molded article having a good appearance and excellent strength.

本實施形態之改質聚丙烯系樹脂在進行發泡時不容易在內部產生破泡，可以得到連續氣泡率低且外觀良好的發泡成形品。 The modified polypropylene-based resin of the present embodiment does not easily cause foaming inside during foaming, and a foamed molded article having a low open cell ratio and a good appearance can be obtained.

而且，本實施形態之改質聚丙烯系樹脂有容易得到具有低連續氣泡率的發泡片之優點。 Further, the modified polypropylene-based resin of the present embodiment has an advantage that a foamed sheet having a low open cell ratio can be easily obtained.

再者，本實施形態之改質聚丙烯系樹脂係具有低膠化率且顯示良好的流動性，係不僅適合形成發泡層，亦適合作為非發泡層的形成材料者。 Further, the modified polypropylene resin of the present embodiment has a low gelation ratio and exhibits good fluidity, and is suitable not only for forming a foamed layer but also as a material for forming a non-foamed layer.

(改質聚丙烯系樹脂的製造方法) (Method for producing modified polypropylene resin)

在製造改質聚丙烯系樹脂時，可採用例如：將含有(A)聚丙烯系樹脂100質量份、(B)有機過氧化物0.1質量份以上1.5質量份以下及(C)芳香族乙烯基單體0.1質量份以上10質量份以下之原料組成物予以熔融混練，而得到改質聚丙烯系樹脂之方法。 When manufacturing a modified polypropylene resin, for example, 100 parts by mass of (A) polypropylene resin, (B) 0.1 part by mass or more of organic peroxide, 1.5 parts by mass or less, and (C) aromatic vinyl group may be used. A method of melt-kneading a raw material composition of 0.1 part by mass or more and 10 parts by mass or less of the monomer to obtain a modified polypropylene-based resin.

原料組成物在熔融混練時，為了使該原料組成物成為良好的熔融狀態，較佳係控制加熱溫度。 When the raw material composition is melt-kneaded, it is preferred to control the heating temperature in order to make the raw material composition into a good molten state.

前述原料組成物係藉由其熔融混練時之加熱而反應。 The raw material composition is reacted by heating during melt-kneading.

亦即，藉由前述加熱，使有機過氧化物產生自由基，該自由基攻擊鍵結於聚丙烯系樹脂的三級碳之氫而形成烷基自由基。 That is, by the aforementioned heating, the organic peroxide generates a radical which attacks the hydrogen which is bonded to the tertiary carbon of the polypropylene resin to form an alkyl radical.

此外，在原本之狀態下會產生β裂解而聚丙烯系樹脂產生分子切斷，但在本實施形態中，芳香族乙烯基單體係鍵結於該部位，形成分枝結構(交聯結構)。 Further, in the original state, β-cracking occurs and the polypropylene-based resin is molecularly cleaved. However, in the present embodiment, the aromatic vinyl single-system is bonded to the site to form a branched structure (crosslinked structure). .

從使(C)芳香族乙烯基單體的添加效果顯著 化的觀點來看，較佳係在將(A)聚丙烯系樹脂及(B)有機過氧化物混合而得到混合物之後，再將(C)芳香族乙烯基單體添加至所得之混合物中。 Significant effect of adding (C) aromatic vinyl monomer In view of the above, it is preferred to add (C) an aromatic vinyl monomer to the obtained mixture after mixing the (A) polypropylene resin and the (B) organic peroxide to obtain a mixture.

但是，(A)聚丙烯系樹脂、(B)有機過氧化物及(C)芳香族乙烯基單體亦可一起進行混合。 However, the (A) polypropylene resin, (B) organic peroxide, and (C) aromatic vinyl monomer may be mixed together.

(D)自由基捕捉劑可在添加(C)芳香族乙烯基單體之前添加，亦可在添加(C)芳香族乙烯基單體之後添加，也可與其他成分一起混合。 (D) The radical scavenger may be added before the addition of the (C) aromatic vinyl monomer, or may be added after the addition of the (C) aromatic vinyl monomer, or may be mixed together with other components.

(E)添加劑可在添加(C)芳香族乙烯基單體之前添加，亦可在添加(C)芳香族乙烯基單體之後添加，也可與其他成分一起混合。 The (E) additive may be added before the addition of the (C) aromatic vinyl monomer, or may be added after the addition of the (C) aromatic vinyl monomer, or may be mixed with other components.

此外，原料組成物的熔融混練可使用揉合機、班布里混合機(Banbury mixer)、擠出機等一般的機器而實施。 Further, the melt kneading of the raw material composition can be carried out by using a general machine such as a kneader, a Banbury mixer, or an extruder.

對前述原料組成物進行熔融混練時，較佳係使用擠出機。 When the raw material composition is melt-kneaded, it is preferred to use an extruder.

較佳為對擠出機供應前述原料組成物，使其在擠出機內進行交聯反應而形成改質聚丙烯系樹脂，同時從擠出機擠出改質聚丙烯系樹脂。 Preferably, the raw material composition is supplied to an extruder, and a crosslinking reaction is carried out in an extruder to form a modified polypropylene resin, and the modified polypropylene resin is extruded from the extruder.

對擠出機連續地供應前述原料組成物，從擠出機連續地擠出改質聚丙烯系樹脂，藉此可有效率地得到改質聚丙烯系樹脂。 The raw material composition is continuously supplied to the extruder, and the modified polypropylene resin is continuously extruded from the extruder, whereby the modified polypropylene resin can be efficiently obtained.

作為前述擠出機，可列舉單軸擠出機及二軸擠出機等。 Examples of the extruder include a single-shaft extruder and a two-axis extruder.

前述擠出機中，可作為單獨或複數個連結而成之串聯(tandem)型的擠出機使用於改質聚丙烯系樹脂的製造。 In the above extruder, a tandem type extruder which is a single or a plurality of connected ones can be used for the production of a modified polypropylene resin.

尤其，對於作為基材樹脂的聚丙烯系樹脂，從更進一步提高其他成分的分散性及反應性之觀點來看，較佳為二軸擠出機。 In particular, the polypropylene-based resin as the base resin is preferably a two-axis extruder from the viewpoint of further improving the dispersibility and reactivity of the other components.

該改質聚丙烯系樹脂的製造方法中，較佳係：在擠出機供應二氧化碳而於經熔融混練的混練物添加二氧化碳，再對添加有二氧化碳的混練物進行一定時間熔融混練後，使含有二氧化碳的氣體從混練物中排出。 In the method for producing the modified polypropylene resin, carbon dioxide is supplied to the extruder, carbon dioxide is added to the kneaded mixture, and the kneaded material to which carbon dioxide is added is melted and kneaded for a predetermined period of time. The carbon dioxide gas is discharged from the kneaded material.

亦即，在改質聚丙烯系樹脂的製造方法中，較佳係實施下列的步驟：藉由進行熔融混練而使聚合物與單體反應之反應步驟、在藉由反應步驟的熔融混練所得之混練物中添加二氧化碳之二氧化碳添加步驟、及使從前述添加有二氧化碳的混練物排出含有二氧化碳的氣體之脫氣步驟。 That is, in the method for producing a modified polypropylene resin, it is preferred to carry out the following steps: a reaction step of reacting a polymer with a monomer by melt-kneading, and a melt-kneading by a reaction step A carbon dioxide addition step of adding carbon dioxide to the kneaded material, and a degassing step of discharging the carbon dioxide-containing gas from the kneaded material to which the carbon dioxide is added.

以擠出機實施前述反應步驟時，較佳係以與反應步驟相同的擠出機、或與該擠出機連接之其他的擠出機來實施前述二氧化碳添加步驟。 When the above reaction step is carried out in an extruder, it is preferred to carry out the aforementioned carbon dioxide addition step by using the same extruder as the reaction step or another extruder connected to the extruder.

亦即，為前者時，例如可使用下述的擠出機而實施：在擠出機的出口附近設置有二氧化碳的供應地點，且在較該二氧化碳供應地點更上游側處設置有(A)聚丙烯系樹脂、(B)有機過氧化物及(C)芳香族乙烯基單體等原料組成物的材料供應地點之擠出機。 That is, in the former case, for example, an extruder may be used in which a supply point of carbon dioxide is provided near the outlet of the extruder, and (A) agglomerate is provided at an upstream side of the carbon dioxide supply point. An extruder for supplying a material of a raw material composition such as a propylene resin, (B) an organic peroxide, and (C) an aromatic vinyl monomer.

而且，為後者時，只要使用由上游側擠出機及下游側擠出機連結而成之串聯式擠出機，在上游側擠出機實施聚 丙烯系樹脂的改質，在下流側擠出機添加二氧化碳而實施進一步的熔融混練即可。 Further, in the latter case, the extruder is connected to the upstream side extruder by using a tandem extruder which is connected by an upstream side extruder and a downstream side extruder. In the modification of the propylene resin, carbon dioxide may be added to the downstream side extruder to carry out further melt kneading.

前述脫氣步驟，可只藉由從擠出機吐出混練物來實施，亦可應用設置有通氣孔機構的擠出機，藉由該通氣孔機構，在吐出混練物之前使二氧化碳從混練物中排出。 The degassing step can be carried out only by discharging the kneaded material from the extruder, or by using an extruder provided with a vent mechanism, by which the carbon dioxide can be taken from the kneading material before the kneading material is discharged. discharge.

藉由實施前述二氧化碳添加步驟、前述脫氣步驟，可使在反應步驟中未被反應消耗而殘留的單體、聚合物的分解生成物之低聚物、有機過氧化物分解所形成的醇類、酮類等伴隨二氧化碳一同排出，而可得到揮發性有機物經減低之改質聚丙烯系樹脂。 By performing the carbon dioxide addition step and the degassing step, the monomer, the oligomer of the decomposition product of the polymer, and the alcohol formed by the decomposition of the organic peroxide which are not consumed by the reaction in the reaction step can be obtained. A ketone or the like is discharged together with carbon dioxide to obtain a modified polypropylene resin having a reduced volatile organic substance.

為了將經改質的聚丙烯系樹脂應用於發泡層、非發泡層的形成，較佳係暫時予以顆粒化。 In order to apply the modified polypropylene-based resin to the formation of the foamed layer or the non-foamed layer, it is preferred to temporarily granulate.

因此，本實施形態之改質聚丙烯系樹脂的製造方法中，較佳係將混練物從裝設於擠出機的前端之模具擠出成薄片狀、股束狀而製作改質聚丙烯系樹脂薄片、改質聚丙烯系樹脂股束，以製粒機將該薄片或股束顆粒化。 Therefore, in the method for producing a modified polypropylene resin of the present embodiment, it is preferred to form a modified polypropylene system by extruding a kneaded product into a sheet shape or a strand shape from a die attached to the tip end of the extruder. The resin sheet, the modified polypropylene resin strand, and the pellet or strand are pelletized by a granulator.

使用如此之模具來製作股束時亦同，為了得到均勻的股束，作為改質聚丙烯系樹脂的起始原料之聚丙烯系樹脂的MFR係以5.0g/10分鐘以上為更佳，7.0g/10分鐘以上為又更佳。 When a strand is produced by using such a mold, in order to obtain a uniform strand, the MFR of the polypropylene-based resin which is a starting material of the modified polypropylene-based resin is preferably 5.0 g/10 min or more, 7.0. More than g/10 minutes is even better.

而且，本實施形態之改質聚丙烯系樹脂的製造方法中，亦可將混練物從裝設於擠出機的前端之模具擠出成股束狀，並且在該模出口間或地對股束切割而進行顆粒化。 Further, in the method for producing a modified polypropylene resin of the present embodiment, the kneaded product may be extruded into a strand shape from a die installed at the tip end of the extruder, and may be interposed between the die outlets or the ground. The beam is cut to pelletize.

在上述中，因為係成為薄片、股束之所謂比表面積較大的形狀而吐出混練物，故在本實施形態之改質聚丙烯系樹脂的製造方法中，可使含有二氧化碳及揮發性有機物的氣體有效率地從該薄片、股束中排出，而可得到揮發性有機物較少的改質聚丙烯系樹脂。 In the above, since the kneaded product is discharged into a shape having a large specific surface area of a sheet or a strand, the method for producing a modified polypropylene resin of the present embodiment can contain carbon dioxide and volatile organic compounds. The gas is efficiently discharged from the sheet and the strand, and a modified polypropylene resin having less volatile organic compounds can be obtained.

亦即，本實施形態中之脫氣步驟，可藉由從擠出機擠出混練物時之自然釋放而使氣體從混練物中排出之方法實施。 That is, the degassing step in the present embodiment can be carried out by discharging the gas from the kneaded material by natural release when the kneaded material is extruded from the extruder.

就容易得到揮發性有機物經減少的改質聚丙烯系樹脂之點而言，二氧化碳添加步驟，較佳係在二氧化碳成為超臨界狀態的條件下實施，較佳係使被供應至擠出機的二氧化碳成為超臨界狀態。 Insofar as it is easy to obtain a modified modified polypropylene resin having a volatile organic compound, the carbon dioxide addition step is preferably carried out under conditions in which carbon dioxide becomes a supercritical state, preferably by supplying carbon dioxide to the extruder. Become supercritical.

此時，添加於混練物中之二氧化碳的量較多者，可以減低改質聚丙烯系樹脂中所含的揮發性有機物之量。 At this time, when the amount of carbon dioxide added to the kneaded material is large, the amount of volatile organic substances contained in the modified polypropylene resin can be reduced.

但是，若過度地添加二氧化碳，則有在脫氣步驟會使改質聚丙烯系樹脂薄片、改質聚丙烯系樹脂股束產生發泡之虞。 However, if carbon dioxide is excessively added, the modified polypropylene resin sheet and the modified polypropylene resin strand may be foamed in the degassing step.

經發泡的改質聚丙烯系樹脂顆粒，會成為在藉由共擠出法製作積層發泡片時於發泡層形成粗大氣泡的原因、使非發泡層產生樹脂開裂的原因。 The foamed modified polypropylene resin particles cause the formation of coarse bubbles in the foam layer when the laminated foam sheet is produced by the co-extrusion method, and cause cracking of the resin in the non-foamed layer.

由上述內容來看，相對於所製作的改質聚丙烯系樹脂100質量份，在二氧化碳添加步驟所使用的二氧化碳之量較佳係設為1.0質量份以上、4.0質量份以下，更佳係設為2.0質量份以上、3.0質量份以下。 In view of the above, the amount of carbon dioxide used in the carbon dioxide addition step is preferably 1.0 part by mass or more and 4.0 parts by mass or less, more preferably 100 parts by mass, based on 100 parts by mass of the modified polypropylene resin to be produced. It is 2.0 parts by mass or more and 3.0 parts by mass or less.

此外，視所需，可使用含有二氧化碳，以及少量之例如甲烷、乙烷、丙烷等碳數5以下的烴、氮而成之混合氣體(例如含有95質量%以上的CO₂及5質量%以下的其他氣體之混合氣體)來實施二氧化碳添加步驟。 In addition, a mixed gas containing carbon dioxide and a small amount of a hydrocarbon having a carbon number of 5 or less, such as methane, ethane, or propane, or nitrogen (for example, containing 95% by mass or more of CO ₂ and 5% by mass or less) may be used. A mixture of other gases) to carry out the carbon dioxide addition step.

使用如此之混合氣體時，其比率較佳亦係設為如上述之範圍內。 When such a mixed gas is used, the ratio is preferably set within the above range.

在本實施形態中，可在顆粒化後實施二氧化碳添加步驟以取代在顆粒化前實施之二氧化碳添加步驟，亦可除了實施顆粒化前的二氧化碳添加步驟，亦實施顆粒化後的二氧化碳添加步驟。 In the present embodiment, the carbon dioxide addition step may be performed after the granulation to replace the carbon dioxide addition step performed before the granulation, or the granulated carbon dioxide addition step may be carried out in addition to the carbon dioxide addition step before the granulation.

對於經顆粒化的改質聚丙烯系樹脂添加二氧化碳之步驟，可藉由例如：將改質聚丙烯系樹脂顆粒放入壓力容器中，在該壓力容器內導入超臨界狀態的二氧化碳，而使超臨界狀態的二氧化碳含浸於改質聚丙烯系樹脂顆粒之方法實施。 For the step of adding carbon dioxide to the granulated modified polypropylene resin, for example, the modified polypropylene resin particles are placed in a pressure vessel, and supercritical carbon dioxide is introduced into the pressure vessel to cause super A method in which a critical state of carbon dioxide is impregnated with modified polypropylene-based resin particles is carried out.

此時，經過一定時間後，使二氧化碳從壓力容器內排出，並視需要將壓力容器內減壓至大氣壓以下，藉此可實施脫氣步驟。 At this time, after a certain period of time, carbon dioxide is discharged from the pressure vessel, and if necessary, the pressure inside the pressure vessel is reduced to atmospheric pressure or lower, whereby the degassing step can be performed.

依如此方式所得之改質聚丙烯系樹脂，可直接、或與其他聚合物成分摻配而作為本實施形態之積層發泡片的原材料(第一聚丙烯系樹脂組成物、第二聚丙烯系樹脂組成物)的主成分。 The modified polypropylene resin obtained in this manner can be used as a raw material (the first polypropylene resin composition and the second polypropylene system) of the laminated foam sheet of the present embodiment, either directly or in combination with other polymer components. The main component of the resin composition).

就使用作為積層發泡片的原材料之改質聚丙烯系樹脂以外之聚合物成分而言，較佳為未改質的聚丙 烯系樹脂。 The polymer component other than the modified polypropylene resin which is a raw material of the laminated foam sheet is preferably an unmodified polypropylene. An olefinic resin.

作該聚丙烯系樹脂，可列舉前述例示作為改質聚丙烯系樹脂的起始物質者。 The polypropylene resin is exemplified as the starting material of the modified polypropylene resin.

與改質聚丙烯系樹脂一起構成積層發泡片之聚丙烯系樹脂，較佳係藉由多段聚合法所得之軟質系者。 The polypropylene resin constituting the laminated foam sheet together with the modified polypropylene resin is preferably a soft one obtained by a multistage polymerization method.

亦即，就前述聚丙烯系樹脂而言，較佳係至少經由下述2階段的步驟所得者：進行丙烯的同元聚合或丙烯與乙烯的無規共聚合之第一階段；以及，在該第一階段後進行乙烯與1種以上之碳數3以上的α-烯烴之共聚合的第二階段。 That is, in the case of the above-mentioned polypropylene-based resin, it is preferred to obtain at least a first stage of the following steps: a first stage of homopolymerization of propylene or random copolymerization of propylene and ethylene; After the first stage, the second stage of copolymerization of ethylene and one or more α-olefins having 3 or more carbon atoms is carried out.

此外，使第一聚丙烯系樹脂組成物及第二聚丙烯系樹脂組成物含有改質聚丙烯系樹脂以外的聚合物成分時，改質聚丙烯系樹脂與其他樹脂，較佳係設為例如9：1至1：9(改質聚丙烯系樹脂：其他樹脂)的質量比例。 In addition, when the first polypropylene resin composition and the second polypropylene resin composition contain a polymer component other than the modified polypropylene resin, the modified polypropylene resin and other resins are preferably, for example, The mass ratio of 9:1 to 1:9 (modified polypropylene resin: other resin).

此外，在積層發泡片的形成中使用其他樹脂時，對於第一聚丙烯系樹脂組成物、第二聚丙烯系樹脂組成物亦與改質聚丙烯系樹脂同樣地以在200℃的頻率分散動態黏彈性測定中所求得的相位角係在頻率0.01Hz時表現為30°以上70°以下為較佳。 In addition, when the other resin is used for the formation of the laminated foam sheet, the first polypropylene resin composition and the second polypropylene resin composition are dispersed at a frequency of 200 ° C in the same manner as the modified polypropylene resin. The phase angle obtained in the dynamic viscoelasticity measurement is preferably 30° or more and 70° or less at a frequency of 0.01 Hz.

此外，第一聚丙烯系樹脂組成物的熔融質量流率(MFR1)與第二聚丙烯系樹脂組成物的熔融質量流率(MFR2)之間，係以具有下述(y)所示的關係為較佳。 Further, the relationship between the melt mass flow rate (MFR1) of the first polypropylene resin composition and the melt mass flow rate (MFR2) of the second polypropylene resin composition is as shown in the following (y) It is better.

(MFR1)≦(MFR2)．．．(y) (在此，「MFR1」係意指在溫度230℃、額定荷重2.16kg情況下的第一聚丙烯系樹脂組成物之熔融質量流率，「MFR2」係意指在溫度230℃、額定荷重2.16kg情況下的第二聚丙烯系樹脂組成物之熔融質量流率。) (MFR1) ≦ (MFR2). . . (y) (MFR1) means the melt mass flow rate of the first polypropylene resin composition at a temperature of 230 ° C and a rated load of 2.16 kg, and "MFR2" means a temperature of 230 ° C and a rated load of 2.16. The molten mass flow rate of the second polypropylene resin composition in the case of kg.)

為了藉由共擠出法而得到良好的積層發泡片，從使連續氣泡率降低下的觀點來看，理想係盡可能使擠出溫度下降。 In order to obtain a good laminated foam sheet by a co-extrusion method, it is desirable to lower the extrusion temperature as much as possible from the viewpoint of lowering the continuous cell ratio.

由於第一聚丙烯系樹脂組成物在形成發泡層時含有發泡劑，故可利用由發泡劑造成的可塑化效果使擠出溫度降低。 Since the first polypropylene-based resin composition contains a foaming agent at the time of forming the foamed layer, the plasticizing effect by the foaming agent can be utilized to lower the extrusion temperature.

另一方面，就形成非發泡層時所使用的第二聚丙烯系樹脂組成物而言，由於難以期待發揮如此的效果，故難以降低擠出溫度。 On the other hand, in the second polypropylene-based resin composition used for forming the non-foamed layer, it is difficult to expect such an effect, and it is difficult to lower the extrusion temperature.

因此，為了降低非發泡層的擠出溫度，較佳係使第一聚丙烯系樹脂組成物的熔融質量流率(MFR1)與第二聚丙烯系樹脂組成物的熔融質量流率(MFR2)滿足如上述的關係。 Therefore, in order to lower the extrusion temperature of the non-foamed layer, it is preferred to reduce the melt mass flow rate (MFR1) of the first polypropylene-based resin composition and the melt mass flow rate (MFR2) of the second polypropylene-based resin composition. Satisfy the relationship as described above.

為了藉由共擠出法而得到良好的積層發泡片，第一聚丙烯系樹脂組成物的相位角(PA1)與第二聚丙烯系樹脂組成物的相位角(PA2)之間，係以具有下述(z)所示的關係為較佳。 In order to obtain a good laminated foam sheet by a co-extrusion method, the phase angle (PA1) of the first polypropylene-based resin composition and the phase angle (PA2) of the second polypropylene-based resin composition are It is preferred to have the relationship shown by the following (z).

(PA1)≦(PA2)．．．(z)(在此，「PA1」係意指在200℃的頻率分散動態黏彈性測定 中所求得的第一聚丙烯系樹脂組成物在頻率0.01Hz時的相位角，「PA2」係意指在200℃的頻率分散動態黏彈性測定中所求得的第二聚丙烯系樹脂組成物在頻率0.01Hz時的相位角。) (PA1) ≦ (PA2). . . (z) (here, "PA1" means dispersion dynamic coelasticity measurement at a frequency of 200 ° C The phase angle of the first polypropylene-based resin composition obtained at a frequency of 0.01 Hz, and "PA2" means the composition of the second polypropylene-based resin obtained by measuring the dynamic viscoelasticity at a frequency of 200 ° C. The phase angle of the object at a frequency of 0.01 Hz. )

含有改質聚丙烯系樹脂的第一聚丙烯系樹脂組成物中，可含有用以形成發泡層所需的發泡劑、氣泡調整劑，藉由使該第一聚丙烯系樹脂組成物擠出發泡，可形成發泡層。 The first polypropylene-based resin composition containing the modified polypropylene-based resin may contain a foaming agent and a bubble adjusting agent required for forming the foamed layer, and the first polypropylene-based resin composition may be extruded. Foaming is formed to form a foamed layer.

作為前述發泡劑，可列舉：丙烷、正丁烷、異丁烷、正戊烷、異戊烷、環戊烷等烴、該等的鹵化物、二氧化碳氣體及氮。 Examples of the foaming agent include hydrocarbons such as propane, n-butane, isobutane, n-pentane, isopentane, and cyclopentane, and such halides, carbon dioxide gas, and nitrogen.

作為前述氣泡調整劑，可列舉例如：滑石、雲母、氧化矽、矽藻土、氧化鋁、氧化鈦、氧化鋅、氧化鎂、氫氧化鎂、氫氧化鋁、氫氧化鈣、碳酸鉀、碳酸鈣、碳酸鎂、硫酸鉀、硫酸鈀、玻璃珠粒等無機化合物粒子；聚四氟乙烯等有機化合物粒子等。 Examples of the bubble adjusting agent include talc, mica, cerium oxide, diatomaceous earth, alumina, titanium oxide, zinc oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, potassium carbonate, and calcium carbonate. Inorganic compound particles such as magnesium carbonate, potassium sulfate, palladium sulfate, and glass beads; and organic compound particles such as polytetrafluoroethylene.

更進一步，可以作為加熱分解型的發泡劑發揮功能的偶氮二甲醯胺、碳酸氫鈉、碳酸氫鈉與檸檬酸的混合物等亦可作為前述氣泡調整劑使用。 Further, a mixture of azomethicone, sodium hydrogencarbonate, sodium hydrogencarbonate and citric acid which can function as a heat-decomposable foaming agent can also be used as the bubble regulator.

該氣泡調整劑、前述發泡劑不需單獨使用1種，亦可併用2種以上使用。 The bubble modifier and the foaming agent are not required to be used alone or in combination of two or more.

而且，對於包含改質聚丙烯系樹脂的第二聚丙烯系樹脂組成物，亦可使其含有形成非發泡層所需的必要成分，將該第二聚丙烯系樹脂組成物與第一聚丙烯系 樹脂組成物一同進行共擠出而形成非發泡層。 Further, the second polypropylene resin composition containing the modified polypropylene resin may contain an essential component required for forming a non-foamed layer, and the second polypropylene resin composition may be combined with the first polypropylene resin composition. Propylene The resin composition is co-extruded together to form a non-foamed layer.

如此之積層發泡片的形成，例如可使用第2圖、第3圖所示的設備。 For the formation of such a laminated foam sheet, for example, the apparatus shown in Figs. 2 and 3 can be used.

第2圖係表示積層發泡片的製造時所使用之製造裝置的一例之構造圖，其係表示從圓模(circular die)將含有發泡劑的第一聚丙烯系樹脂組成物擠出發泡，同時從相同的圓模將第二聚丙烯系樹脂組成物以非發泡的狀態擠出，形成非發泡層疊合於發泡層的兩面之筒狀的積層發泡體後，使該積層發泡體沿著冷卻心軸的外周圍予以冷卻，將經冷卻的積層發泡體往上下分割為二後捲繞成捲筒之情形，而第3圖係用以表示第2圖由虛線圈起的A所示之部分的詳細內容之經放大的剖面圖。 Fig. 2 is a structural view showing an example of a manufacturing apparatus used in the production of a laminated foam sheet, which is obtained by extrusion-expanding a first polypropylene-based resin composition containing a foaming agent from a circular die. At the same time, the second polypropylene resin composition is extruded in a non-foamed state from the same circular die to form a cylindrical laminated foam which is non-foamed and laminated on both surfaces of the foamed layer, and then the laminate is laminated. The foam is cooled along the outer circumference of the cooling mandrel, and the cooled laminated foam is divided into two parts and then wound into a roll, and the third figure is used to indicate that the second figure is composed of a dotted circle. An enlarged cross-sectional view of the details of the portion shown in A.

本實施形態之製造裝置係具備：用以形成發泡層之第一擠出管線70、用以形成非發泡層之第二擠出管線80、使在第一擠出管線70經熔融混練的第一聚丙烯系樹脂組成物與在第二擠出管線80經熔融混練的第二聚丙烯系樹脂組成物匯合之匯合模90以及將在該匯合模匯合的第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物擠出成筒狀之圓模100。 The manufacturing apparatus of the present embodiment includes a first extrusion line 70 for forming a foamed layer, a second extrusion line 80 for forming a non-foamed layer, and melt-kneading in the first extrusion line 70. The merged mold 90 in which the first polypropylene-based resin composition merges with the second polypropylene-based resin composition melt-kneaded in the second extrusion line 80, and the first polypropylene-based resin composition that joins the merged mold The second polypropylene resin composition is extruded into a cylindrical die 100.

前述匯合模90係以使第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物成為圓筒狀之方式在內部形成有樹脂流道，以使第二聚丙烯系樹脂組成物在第一聚丙烯系樹脂組成物的內外兩側流動。 In the merged mold 90, a resin flow path is formed inside the first polypropylene resin composition and the second polypropylene resin composition in a cylindrical shape, so that the second polypropylene resin composition is in the first A polypropylene resin composition flows on both inner and outer sides.

積層發泡片的製造裝置係具備：將從圓模 100吐出成筒狀的積層發泡體FB自內側進行空氣冷卻之冷卻裝置CR1、用以使該筒狀的積層發泡體FB進行擴徑而形成既定大小的筒狀之冷卻心軸200、將通過該冷卻心軸200後的積層發泡體FB’分切而分割成2片帶狀的積層發泡片1之分切裝置CT、以及用以使經分切的帶狀積層發泡片1通過複數個滾輪91後進行捲繞之捲繞滾輪92。 The manufacturing device of the laminated foam sheet has: a circular mold 100. The cooling device CR1 that discharges the cylindrical foamed body FB from the inside, and expands the cylindrical laminated foam FB to form a cylindrical cooling mandrel 200 of a predetermined size. The slitting device CT which is divided into two strip-shaped laminated foam sheets 1 by slitting the laminated foam FB' after the cooling mandrel 200, and the strip-shaped laminated foam sheet 1 for slitting The winding roller 92 is wound by a plurality of rollers 91.

製造積層發泡片時，由於是採用發揮較一般的聚丙烯系樹脂更高的熔融張力之改質聚丙烯系樹脂作為發泡層的形成材料，故可從圓模100以高吐出量進行擠出發泡，同時可在冷卻心軸200以高的吹脹比(blow-up ratio)進行擴徑。 When a laminated foam sheet is produced, a modified polypropylene resin which exhibits a higher melt tension than a general polypropylene resin is used as a material for forming a foamed layer, so that it can be extruded from the round die 100 with a high discharge amount. Foaming is performed while expanding the diameter of the cooling mandrel 200 with a high blow-up ratio.

並且，因為前述積層發泡片是採用改質聚丙烯系樹脂作為非發泡層的形成材料，故對於發泡層的高速擠出及以高倍率的擴徑，非發泡層亦會顯示高的跟隨性而不易產生樹脂開裂等。 Further, since the laminated foam sheet is formed of a modified polypropylene resin as a non-foamed layer, the non-foamed layer is also high in high-speed extrusion of the foamed layer and expansion at a high magnification. The followability is not easy to cause resin cracking and the like.

為了減輕第二擠出管線80之擠出機的負荷，前述積層發泡片較佳係將第二聚丙烯系樹脂組成物的樹脂溫度設定為提高一定程度。 In order to reduce the load on the extruder of the second extrusion line 80, the laminated foam sheet preferably sets the resin temperature of the second polypropylene resin composition to a certain extent.

此外，進行如此之條件設定時，因經擠出發泡的發泡層會變得難以冷卻，故會設定成發泡層容易產生氣泡破裂之擠出條件。 Further, when such a condition is set, the foamed layer which is extruded by extrusion becomes difficult to be cooled, so that the extrusion condition in which the foamed layer is likely to cause bubble collapse is set.

然而，前述積層發泡片中，第一聚丙烯系樹脂組成物中所含的改質聚丙烯系樹脂的膠化率低，且MFR高。 However, in the laminated foam sheet, the modified polypropylene resin contained in the first polypropylene resin composition has a low gelation ratio and a high MFR.

亦即，因為成為氣泡膜破裂起點的凝膠少，且因為高 MFR而於氣泡膜發揮優異的伸展性，故前述積層發泡片係可減輕第二擠出管線80的擠出機之負荷，同時亦可使發泡層成為緻密且獨立氣泡性高的發泡狀態。 That is, since the gel which becomes the starting point of the bubble film breakage is small, and because it is high Since the MFR exhibits excellent stretchability in the bubble film, the laminated foam sheet can reduce the load of the extruder of the second extrusion line 80, and at the same time, the foamed layer can be made into a dense and high-bubble foam. status.

因此，所製作的積層發泡片在熱成形等時成形性亦優異。 Therefore, the produced laminated foam sheet is also excellent in moldability at the time of thermoforming or the like.

積層發泡片在進行如杯狀容器的深沖(deep drawing)成形時，非發泡層容易在底面部與側面部之邊界部產生樹脂開裂等，但前述積層發泡片由於在非發泡層中含有改質聚丙烯系樹脂，且該改質聚丙烯系樹脂表現高MFR，故不容易產生如此之障礙。 When the laminated foam sheet is subjected to deep drawing molding such as a cup-shaped container, the non-foamed layer is liable to cause resin cracking or the like at the boundary portion between the bottom surface portion and the side surface portion, but the laminated foam sheet is not foamed. The layer contains a modified polypropylene-based resin, and the modified polypropylene-based resin exhibits a high MFR, so that such a disorder is not easily caused.

亦即，前述積層發泡片，不僅有效於改善其製造時的效率，且有效於提升成形品的良率。 In other words, the laminated foam sheet is effective not only for improving the efficiency in production, but also for improving the yield of the molded article.

即使用若為傳統的積層發泡片則容易產生垂伸的吹脹比，使用本實施形態之改質聚丙烯系樹脂而成之積層發泡片亦不容易產生垂伸。 In other words, if a conventional laminated foam sheet is used, the inflation ratio of the drawdown is likely to occur, and the laminated foam sheet obtained by using the modified polypropylene resin of the present embodiment is less likely to cause a drawdown.

因此，可以優異的生產效率製作前述積層發泡片。 Therefore, the laminated foam sheet can be produced with excellent production efficiency.

積層發泡片較佳係以吹脹比為1.8以上的條件製造，更佳係以吹脹比為2.3以上的條件製造。 The laminated foam sheet is preferably produced under the conditions of a blow ratio of 1.8 or more, more preferably at a blow ratio of 2.3 or more.

此外，所謂的吹脹比，係意指根據冷卻心軸的直徑(D)相對於圓模的圓環狀吐出口的直徑(d)所求得的值(D/d)，圓模的吐出口之直徑(D)係意指通過吐出口的內緣之圓的直徑。 Further, the so-called inflation ratio means a value (D/d) obtained from the diameter (D) of the cooling mandrel with respect to the diameter (d) of the annular discharge port of the circular die, and the spit of the circular die. The diameter (D) of the outlet means the diameter of the circle passing through the inner edge of the discharge port.

而且，非發泡層的厚度較薄之積層發泡片容易在非發泡層產生樹脂開裂，惟前述積層發泡片即使在如此情況亦不會產生樹脂開裂，故可謂對於積層發泡片、成形品的輕 量化為有效。 Further, the laminated foamed sheet having a relatively small thickness of the non-foamed layer is liable to cause resin cracking in the non-foamed layer, and the laminated foamed sheet does not cause cracking of the resin even in such a case, so that it can be said that for the laminated foamed sheet, Light molded product Quantify as valid.

就此點而言，前述積層發泡片之非發泡的基重較佳為100g/m²以下，更佳為50g/m²以下。 In this regard, the non-foamed basis weight of the laminated foam sheet is preferably 100 g/m ² or less, more preferably 50 g/m ² or less.

前述積層發泡片，通常係製作成發泡層的表觀密度為0.025g/cm³以上0.5g/cm³以下者。 The laminated foam sheet is usually produced such that the foamed layer has an apparent density of 0.025 g/cm ³ or more and 0.5 g/cm ³ or less.

前述積層發泡片的表觀密度，係根據JIS K7222：1999「發泡塑膠及橡膠-表觀密度的測定」中所記載的方法而測定，具體而言係依如下所述的方法測定。 The apparent density of the laminated foamed sheet is measured according to the method described in JIS K7222:1999 "Measurement of foamed plastic and rubber-apparent density", and specifically measured by the method described below.

(密度測定方法) (density measurement method)

由積層發泡片製作100cm³以上的試料，將該試料在JIS K7100：1999的記號23/50、2級環境下調節狀態16小時後，測定其尺寸、質量，並根據下述式算出表觀密度。 A sample of 100 cm ³ or more was produced from the laminated foam sheet, and the sample was adjusted in a condition of 23/50 and a two-stage environment of JIS K7100:1999 for 16 hours, and then the size and mass thereof were measured, and the appearance was calculated according to the following formula. density.

表觀密度(g/cm³)=試料的質量(g)/試料的體積(cm³) Apparent density (g/cm ³ ) = mass of sample (g) / volume of sample (cm ³ )

此外，試料的尺寸測定時，可使用例如Mitutoyo Corporation公司製之「DIGIMATIC」CD-15型。 Further, in the measurement of the size of the sample, for example, "DIGIMATIC" CD-15 manufactured by Mitutoyo Corporation can be used.

前述積層發泡片之發泡層的連續氣泡率較佳為40%以下，更佳為30%以下。 The continuous cell ratio of the foamed layer of the laminated foam sheet is preferably 40% or less, more preferably 30% or less.

前述發泡層的連續氣泡率係由以下的方法測定。 The continuous cell ratio of the foamed layer was measured by the following method.

亦即，從積層發泡片切出複數片之縱長25mm、橫長25mm的薄片狀試樣，將切出的試樣以不產生間隙的方式疊合而作成厚度25mm的測定用試料，使用Mitutoyo公司製之「數位游標卡尺」來測定該測定用試料的外部尺寸到 1/100mm為止，求出表觀體積(cm³)。 In other words, a sheet-like sample having a length of 25 mm and a horizontal length of 25 mm was cut out from the laminated foam sheet, and the cut samples were laminated without a gap to prepare a sample for measurement having a thickness of 25 mm. The "digital vernier caliper" manufactured by Mitutoyo Co., Ltd. measures the external size of the sample for measurement to 1/100 mm, and obtains an apparent volume (cm ³ ).

其次，使用空氣比較式比重計1000型(tokyoscience公司製)，藉由1-1/2-1氣壓法來求出測定用試料的體積(cm³)。 Next, the volume (cm ³ ) of the sample for measurement was determined by a 1-1/2-1 gas pressure method using an air comparative type hydrometer model 1000 (manufactured by Tokyoscience Co., Ltd.).

利用該等所求得之值與下述式計算連續氣泡率(%)，求出試驗數5個的平均值。 The continuous bubble ratio (%) was calculated from the values obtained by the above and the following formula, and the average value of five test numbers was obtained.

此外，測定係在將測定用試料於JIS K7100-1999記號23/50、2級的環境下調節狀態16小時後，在JIS K7100-1999記號23/50、2級的環境下進行。 In addition, the measurement was carried out in an environment in which the measurement sample was adjusted to an environment of JIS K7100-1999 No. 23/50, Class 2 for 16 hours, and then carried out in an environment of JIS K7100-1999 No. 23/50, Class 2.

而且，空氣比較式比重計係用標準球(大28.9cc小8.5cc)進行校正。 Moreover, the air comparison type hydrometer was calibrated using a standard ball (large 28.9 cc small 8.5 cc).

連續氣泡率(%)=100×(表觀體積-以空氣比較式比重計測定的體積)/表觀體積 Open cell rate (%) = 100 × (apparent volume - volume measured by air comparative pycnometer) / apparent volume

前述積層發泡片，係以原本的狀態亦有用於作為緩衝薄片等發泡成形品，並且亦有用於作為藉由熱成形等賦予立體形狀所成之發泡成形品的原材料。 The laminated foamed sheet is used as a foamed molded article such as a cushion sheet in the original state, and is also used as a raw material for foam molding of a three-dimensional shape by thermoforming or the like.

作為該熱成形，可列舉例如真空成形、壓空成形、真空壓空成形、偶模成形(matched mold forming)、壓製成型等。 Examples of the thermoforming include vacuum molding, pressure forming, vacuum pressure forming, matched mold forming, press molding, and the like.

作為藉由該熱成形所製作之具體的製品，較佳為容器。 As a specific product produced by the thermoforming, a container is preferred.

依如此方式所製作的發泡樹脂製容器，不僅質輕且高強度，而且容易大量生產，故以應用作為各種包裝用容器為較佳。 The foamed resin container produced in this manner is not only lightweight and high in strength, but also easy to mass-produce, and therefore it is preferably used as a container for various packaging.

而且，發泡樹脂製容器由於阻熱性等亦優異，故較佳係使用在食品包裝。 Further, since the foamed resin container is excellent in heat resistance and the like, it is preferably used in food packaging.

在前述發泡成形品的表面，可視用途而積層不織布、金屬箔、化妝紙、印刷膜等。 On the surface of the foamed molded article, a non-woven fabric, a metal foil, a cosmetic paper, a printed film, or the like is laminated for use.

此外，在本實施形態中，係例示使用改質聚丙烯系樹脂作為積層發泡片的形成材料之情形，惟本發明之改質聚丙烯系樹脂亦可使用在其他用途。 In the present embodiment, a modified polypropylene resin is used as a material for forming a laminated foam sheet, but the modified polypropylene resin of the present invention can also be used for other purposes.

亦即，本發明並不為上述例示所限定。 That is, the present invention is not limited to the above examples.

(實施例) (Example)

以下列示實施例以更詳細說明本發明，惟本發明並不限定於該等例示。 The invention is illustrated in more detail by the following examples, but the invention is not limited thereto.

<第一探討點：熔融張力、MFR、相位角> <First discussion point: melt tension, MFR, phase angle> (實施例1) (Example 1) (1)改質聚丙烯系樹脂的製作 (1) Production of modified polypropylene resin

將聚丙烯系樹脂(均聚聚丙烯(homopolypropylene)樹脂，Prime Polymer公司製「PM600A」，MFR=7.5g/10分鐘，密度=0.9g/cm³)100質量份及過氧化異丙基碳酸第三丁酯(Kayaku Akzo公司製「Kayakarubon BIC-75」，1分鐘半衰期溫度：156℃)0.84質量份以帶式摻合機(ribbon blender)攪拌混合，而得到混合物。 Polypropylene resin (homopolypropylene resin, "PM600A" manufactured by Prime Polymer Co., Ltd., MFR = 7.5 g/10 min, density = 0.9 g/cm ³ ) 100 parts by mass and isopropyl peroxydicarbonate Tributyl ester (Kayakuubon BIC-75, manufactured by Kayaku Akzo Co., Ltd., 1 minute half-life temperature: 156 ° C), 0.84 parts by mass, was stirred and mixed with a ribbon blender to obtain a mixture.

將所得之混合物供應至口徑為41mm的二軸擠出機(L/D=42)，使用液體注入泵從二軸擠出機的中途將苯乙烯單體以相對於聚丙烯系樹脂100質量份的比率成為2.5質量份的方式供給。 The obtained mixture was supplied to a two-axis extruder (L/D=42) having a diameter of 41 mm, and a styrene monomer was used in an amount of 100 parts by mass relative to the polypropylene resin from the middle of the two-axis extruder using a liquid injection pump. The ratio is supplied in a form of 2.5 parts by mass.

將送料部的溫度設定為170℃，並將之後的溫度設定為230℃，以旋轉數120rpm、齒輪泵旋轉數25rpm的條件 在二軸擠出機中使原料組成物熔融混練，從裝設於擠出機的前端之口徑2mm、孔數9個的模頭以45kg/小時的吐出量將熔融混練物擠出成股束狀。 The temperature of the feed portion was set to 170 ° C, and the subsequent temperature was set to 230 ° C, with a rotation number of 120 rpm and a gear pump rotation number of 25 rpm. The raw material composition was melt-kneaded in a two-axis extruder, and the melt-kneaded product was extruded into a strand from a die having a diameter of 2 mm and a number of holes of 9 at the tip end of the extruder at a discharge amount of 45 kg/hour. shape.

其次，使擠出的股束狀之熔融混練物通過容納有30℃的水之冷卻水槽中而進行冷卻。 Next, the extruded strand-shaped melt kneaded material was cooled by passing through a cooling water tank containing water at 30 °C.

將經冷卻的股束狀混練物以製粒機切割，得到改質聚丙烯系樹脂的顆粒。對所得之改質聚丙烯系樹脂顆粒進行特性評估，結果示於表1。 The cooled strand-shaped kneaded material was cut with a granulator to obtain pellets of the modified polypropylene-based resin. The properties of the obtained modified polypropylene resin particles were evaluated, and the results are shown in Table 1.

(實施例2至7、比較例1至10) (Examples 2 to 7, Comparative Examples 1 to 10)

除了將使用的聚丙烯系樹脂、苯乙烯量、有機過氧化物之量變更成如下表所示以外，係以與上述同樣的方式製作改質聚丙烯系樹脂。 A modified polypropylene resin was produced in the same manner as described above except that the amount of the polypropylene resin, the amount of styrene, and the amount of the organic peroxide to be used was changed as shown in the following table.

此外，表中的「J105G」、「MA3H」、「MA3」、「J106」、「PM802A」、「PM900A」、「FY4」、「PL500A」、「E111G」、「E200GP」係意指如以下之聚丙烯系樹脂。 In addition, "J105G", "MA3H", "MA3", "J106", "PM802A", "PM900A", "FY4", "PL500A", "E111G" and "E200GP" in the table mean the following Polypropylene resin.

而且，比較例10中，將用於改質的聚丙烯系樹脂設為「PM802A」與「PM900A」的混合物。此外，該混合物中的「PM802A」與「PM900A」之質量比率係設為7：3(「PM802A」：「PM900A」)。 Further, in Comparative Example 10, the polypropylene resin used for the modification was a mixture of "PM802A" and "PM900A". Further, the mass ratio of "PM802A" to "PM900A" in the mixture is set to 7:3 ("PM802A": "PM900A").

「J105G」： "J105G":

均聚聚丙烯樹脂，Prime Polymer公司製「J105G」，MFR=9.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "J105G" manufactured by Prime Polymer Co., Ltd., MFR = 9.0 g/10 min, density = 0.9 g/cm ³

「MA3H」： "MA3H":

均聚聚丙烯樹脂，Japan Polypropylene公司製「MA3H」、MFR=10.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "MA3H" manufactured by Japan Polypropylene Co., Ltd., MFR = 10.0 g/10 min, density = 0.9 g/cm ³

「MA3」： "MA3":

均聚聚丙烯樹脂，Japan Polypropylene公司製「MA3」、MFR=11.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "MA3" manufactured by Japan Polypropylene Co., Ltd., MFR = 11.0 g/10 min, density = 0.9 g/cm ³

「FY4」： "FY4":

均聚聚丙烯樹脂，Japan Polypropylene公司製「FY4」、MFR=5.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "FY4" manufactured by Japan Polypropylene Co., Ltd., MFR = 5.0 g/10 min, density = 0.9 g/cm ³

「J106」： "J106":

均聚聚丙烯樹脂，Prime Polymer公司製「J106」、MFR=18.0g/10分鐘，密度=0.9g/cm³ Homopolymer polypropylene resin, "J106" manufactured by Prime Polymer Co., Ltd., MFR = 18.0 g/10 min, density = 0.9 g/cm ³

「PM802A」： "PM802A":

均聚聚丙烯樹脂，SunAllomer公司製「PM802A」、MFR=20.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "PM802A" manufactured by SunAllomer Co., Ltd., MFR = 20.0 g/10 min, density = 0.9 g/cm ³

「PM900A」： "PM900A":

均聚聚丙烯樹脂，SunAllomer公司製「PM900A」、MFR=30.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "PM900A" manufactured by SunAllomer Co., Ltd., MFR = 30.0 g/10 min, density = 0.9 g/cm ³

「PL500A」： "PL500A":

均聚聚丙烯樹脂，SunAllomer公司製「PL500A」、MFR=3.3g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "PL500A" manufactured by SunAllomer Co., Ltd., MFR = 3.3 g/10 min, density = 0.9 g/cm ³

「E111G」： "E111G":

均聚聚丙烯樹脂，Prime Polymer公司製「E111G」、MFR=0.5g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "E111G" manufactured by Prime Polymer Co., Ltd., MFR = 0.5 g/10 min, density = 0.9 g/cm ³

「E200GP」： "E200GP":

均聚聚丙烯樹脂，Prime Polymer公司製「E200GP」、MFR=2.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "E200GP" manufactured by Prime Polymer Co., Ltd., MFR = 2.0 g/10 min, density = 0.9 g/cm ³

由以上內容亦可知，藉由本發明，可得到在熱熔融時發揮高熔融張力且流動性優異的改質聚丙烯系樹脂。 As described above, according to the present invention, it is possible to obtain a modified polypropylene resin which exhibits high melt tension during heat fusion and is excellent in fluidity.

<第二探討點：股束的均勻性> <Second discussion point: uniformity of strands>

測定上述的改質聚丙烯系樹脂於製作時從前述模(口徑2mm、孔數9個(#1至#9))的各孔所擠出之各股束的吐出量之變異行。 The variation of the discharge amount of each strand extruded from each of the above-mentioned molds (having a diameter of 2 mm and a number of holes of 9 (#1 to #9)) at the time of production was measured.

測定結果顯示於以下。 The measurement results are shown below.

表中的「R」係表示各吐出量的最大值與最小值之差。 The "R" in the table indicates the difference between the maximum value and the minimum value of each discharge amount.

由以上內容可知，藉由本發明，在製作改質聚丙烯系樹脂時來自模的吐出量係均勻化。 As apparent from the above, according to the present invention, the amount of discharge from the mold is uniformized when the modified polypropylene resin is produced.

<第三探討點：連續氣泡率> <Third Discussion Point: Open Bubble Rate> (參考例1) (Reference example 1) (1)改質聚丙烯系樹脂的製作 (1) Production of modified polypropylene resin

將聚丙烯系樹脂(均聚聚丙烯樹脂，SunAllomer公司製「PM600A」，MFR=7.5g/10分鐘，密度=0.9g/cm³)100質量份、過氧化異丙基碳酸第三丁酯(Kayaku Akzo股份有限公 司製「KayakarubonBIC-75」，1分鐘半衰期溫度T1：156℃)0.84質量份以帶式摻合機攪拌混合，得到混合物。 Polypropylene resin (homopolypropylene resin, "PM600A" manufactured by Sun Allomer Co., Ltd., MFR = 7.5 g/10 min, density = 0.9 g/cm ³ ) 100 parts by mass, tert-butyl isopropyl peroxydicarbonate ( "Kayakarubon BIC-75" manufactured by Kayaku Akzo Co., Ltd., 1 minute half-life temperature T: 1256 ° C) 0.84 parts by mass was stirred and mixed with a belt blender to obtain a mixture.

將所得之混合物供應至口徑為41mm的二軸擠出機(L/D=42)，使用液體注入泵從二軸擠出機的中途將苯乙烯單體以相對於聚丙烯系樹脂100質量份的比率成為2.5質量份的方式供應。 The obtained mixture was supplied to a two-axis extruder (L/D=42) having a diameter of 41 mm, and a styrene monomer was used in an amount of 100 parts by mass relative to the polypropylene resin from the middle of the two-axis extruder using a liquid injection pump. The ratio is supplied in a way of 2.5 parts by mass.

將送料部的設定溫度設定為170℃，而後的溫度設定為230℃，以旋轉數120rpm、齒輪泵旋轉數25rpm的條件在二軸擠出機中使原料組成物熔融混練，從裝設於前端的口徑2mm、模唇(land)10mm、孔數9個的模以45kg/小時的吐出量將熔融混練物擠出成股束狀。 The set temperature of the feed portion was set to 170 ° C, and the subsequent temperature was set to 230 ° C. The raw material composition was melted and kneaded in a two-axis extruder under the conditions of a number of revolutions of 120 rpm and a number of revolutions of the gear pump of 25 rpm, and was installed at the front end. The mold having a diameter of 2 mm, a land of 10 mm, and a number of holes of 9 extruded the melt-kneaded product into a strand shape at a discharge amount of 45 kg/hour.

其次，使所擠出的股束狀熔融混練物通過容納有30℃的水之冷卻水槽中而進行冷卻。 Next, the extruded strand-shaped melt kneaded material was cooled by passing through a cooling water tank containing water at 30 °C.

將經冷卻的股束狀混練物以製粒機切割，得到改質聚丙烯系樹脂A(MFR=1.7g/10分鐘，熔融張力=18.5cN，以下稱為「改質PP-A」)的顆粒。 The cooled strand-shaped kneaded material was cut by a granulator to obtain a modified polypropylene resin A (MFR = 1.7 g/10 min, melt tension = 18.5 cN, hereinafter referred to as "modified PP-A"). Particles.

(2)發泡體的製作 (2) Production of foam

將所得之「改質PP-A」85質量份、SunAllomer公司製的熱塑性彈性體樹脂之商品名「Q100F」15質量份及氣泡調整劑(大日精化工業公司製「Fine Cell Master HCPO410K」)0.45質量份進行乾式摻配，而得到混合物。 85 parts by mass of the obtained "modified PP-A", 15 parts by mass of the product name "Q100F" of the thermoplastic elastomer resin manufactured by Sun Allomer Co., Ltd., and a bubble adjusting agent ("Fine Cell Master HCPO410K" manufactured by Daisei Seiki Co., Ltd.) 0.45 The mass parts were dry blended to obtain a mixture.

將該混合物供應至具有口徑50mm的No.1擠出機及口徑65mm的No.2擠出機之串聯型擠出機的No.1擠出機的料斗(hopper)，在No.1擠出機的料筒內進行加熱熔融混練 後，將作為發泡劑之混合丁烷氣體(正丁烷：異丁烷=7：3)以成為2.5質量%的比率之方式壓入No.1擠出機，使含有發泡劑的聚丙烯系樹脂組成物熔融混練而在該擠出機內調製發泡層形成用的第一聚丙烯系樹脂組成物。 The mixture was supplied to a hopper of a No. 1 extruder having a No. 1 extruder having a diameter of 50 mm and a tandem extruder of a No. 2 extruder having a diameter of 65 mm, and extruding at No. 1 Heat and melt kneading in the barrel of the machine Thereafter, the mixed butane gas (n-butane: isobutane = 7:3) as a blowing agent was pressed into a No. 1 extruder so as to have a ratio of 2.5% by mass to form a polymerization agent containing a foaming agent. The propylene resin composition was melted and kneaded, and a first polypropylene resin composition for forming a foam layer was prepared in the extruder.

之後，使該第一聚丙烯系樹脂組成物通過將No.1擠出機及No.2擠出機連接之移送部而流入No.2擠出機。 Thereafter, the first polypropylene resin composition was introduced into a No. 2 extruder by a transfer unit in which a No. 1 extruder and a No. 2 extruder were connected.

其次，在該No.2擠出機的料筒內使第一聚丙烯系樹脂組成物均均地冷卻後，流入匯合模。 Next, the first polypropylene-based resin composition was uniformly cooled in the cylinder of the No. 2 extruder, and then flowed into a confluent mold.

此時的樹脂溫度為180℃，來自No.2擠出機的吐出量為30kg/小時。 The resin temperature at this time was 180 ° C, and the discharge amount from the No. 2 extruder was 30 kg / hr.

另一方面，作為非發泡層用的第二聚丙烯系樹脂組成物，係使用含有上述「改質PP-A」作為改質聚丙烯系樹脂，且含有Basell公司製的商品名「Q100F」作為熱塑性彈性體及三洋化成股份有限公司製的商品名：「Pelestat 230」(聚醚-聚丙烯嵌段共聚物)作為高分子型抗靜電劑者。 On the other hand, the second polypropylene resin composition for the non-foaming layer is a modified polypropylene resin containing the above-mentioned "modified PP-A", and the product name "Q100F" manufactured by Basell Corporation is used. As a thermoplastic elastomer and a trade name of Sanyo Chemical Co., Ltd., "Pelestat 230" (polyether-polypropylene block copolymer) is used as a polymer type antistatic agent.

具體而言，係將含有比率為前述的「改質PP-A」74質量份、前述熱塑性彈性體13質量份及高分子型抗靜電劑13質量份之混合原料供應至口徑32mm的單軸擠出機的料斗，並進行熔融混練後，使其流入前述匯合模。 Specifically, a mixed raw material having a ratio of 74 parts by mass of the above-mentioned "modified PP-A", 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of the polymer type antistatic agent is supplied to a uniaxial extrusion having a diameter of 32 mm. After the hopper of the machine is melted and kneaded, it flows into the confluent die.

此時的吐出量為3kg/小時。 The discharge amount at this time was 3 kg/hour.

在製作具備發泡層及非發泡層的積層發泡片時，首先，係將在匯合模匯合的第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物送入至模縫的口徑為70mm 的圓模，從該圓模的圓環狀吐出口(模縫間隔0.4mm)予以共擠出成圓筒狀。 When a laminated foam sheet having a foamed layer and a non-foamed layer is produced, first, the first polypropylene resin composition and the second polypropylene resin composition which are combined in the merged mold are fed to the die slit. The caliber is 70mm The round die was coextruded into a cylindrical shape from the annular discharge port of the circular die (die gap 0.4 mm).

然後，將呈非發泡層積層在發泡層的狀態之圓筒狀發泡體以冷卻心軸進行冷卻成形後，藉由裝設於冷卻心軸的後部的切割器將圓筒狀發泡體切開而製作長條帶狀的積層發泡片，將該積層發泡片以拉取速度2.1m/分鐘進行捲繞。 Then, the cylindrical foam in a state in which the non-foamed laminated layer is in the foamed layer is cooled and formed by a cooling mandrel, and then the cylindrical foam is foamed by a cutter attached to the rear of the cooling mandrel. The laminated foamed sheet was formed by slitting, and the laminated foamed sheet was wound at a drawing speed of 2.1 m/min.

此時的積層發泡片的平均厚度為2.12mm。 The laminated foam sheet at this time had an average thickness of 2.12 mm.

(參考例2至4、比較參考例1至5) (Reference Examples 2 to 4, Comparative Reference Examples 1 to 5)

除了將用以得到改質聚丙烯系樹脂而使用的聚丙烯系樹脂、苯乙烯量、有機過氧化物量及用以得到積層發泡片而使用的改質聚丙烯系樹脂變更如下表以外，係以與上述同樣的方式製作積層發泡片。 The polypropylene resin used for obtaining the modified polypropylene resin, the amount of styrene, the amount of organic peroxide, and the modified polypropylene resin used to obtain the laminated foam sheet are changed as shown in the following table. A laminated foam sheet was produced in the same manner as above.

此外，表中的「J105G」、「FY4」、「E111G」、「E200GP」係與前述相同，而「PL400A」係意指如下述之聚丙烯系樹脂。 In addition, "J105G", "FY4", "E111G", and "E200GP" in the table are the same as the above, and "PL400A" means the following polypropylene resin.

「PL400A」： "PL400A":

均聚聚丙烯樹脂，SunAllomer公司製「PL400A」、MFR=2.0g/10分鐘，密度=0.9g/cm³ Homopolymerized polypropylene resin, "PL400A" manufactured by SunAllomer Co., Ltd., MFR = 2.0 g/10 min, density = 0.9 g/cm ³

由上述內容可知，流動性優異的改質聚丙烯系樹脂對於形成連續氣泡率低的積層發泡片係屬有用。 From the above, it is understood that the modified polypropylene resin having excellent fluidity is useful for forming a laminated foam sheet having a low open cell ratio.

<第四探討點：連續氣泡率及成形性> <Fourth point of discussion: continuous bubble rate and formability> [評估1] [Evaluation 1] (1)改質聚丙烯系樹脂(改質PP-a)的製作 (1) Production of modified polypropylene resin (modified PP-a)

將線性PP(PP1：具有線型分子結構之均聚聚丙烯樹脂，MFR=7.5g/10分鐘，密度=0.9g/cm³)100質量份、過氧化異丙基碳酸第三丁酯(Kayaku Akzo公司製「KayakarubonBIC-75」、1分鐘半衰期溫度：156℃)0.90質量份以帶式摻合機攪拌混合，而得到混合物。 Linear PP (PP1: homopolypropylene resin having a linear molecular structure, MFR = 7.5 g/10 min, density = 0.9 g/cm ³ ) 100 parts by mass, tert-butyl isopropyl peroxycarbonate (Kayaku Akzo) The company "Kayakarubon BIC-75", 1 minute half-life temperature: 156 ° C) 0.90 parts by mass was stirred and mixed by a belt blender to obtain a mixture.

將所得之混合物供應至口徑為41mm的二軸擠出機(L/D=42)，使用液體注入泵從二軸擠出機的中途將苯乙烯單體以相對於線性PP100質量份的比率成為3.0質量份的方式供應。 The obtained mixture was supplied to a two-axis extruder (L/D=42) having a diameter of 41 mm, and a ratio of styrene monomer to 100 parts by mass relative to linear PP was obtained from the middle of the two-axis extruder using a liquid injection pump. 3.0 parts by mass supply.

將送料部的設定溫度設定為170℃，而後的溫度設定為230℃，以旋轉數120rpm、齒輪泵旋轉數25rpm的條件在二軸擠出機中使原料組成物熔融混練，從裝設於擠出機的前端之口徑2mm、孔數9個的模中以45kg/小時的吐出量將熔融混練物擠出成股束狀。 The set temperature of the feed portion was set to 170 ° C, and the subsequent temperature was set to 230 ° C. The raw material composition was melted and kneaded in a two-axis extruder under the conditions of a number of revolutions of 120 rpm and a number of revolutions of the gear pump of 25 rpm. The molten kneaded material was extruded into a strand shape in a mold having a diameter of 2 mm and a number of holes of 9 at the tip end of the machine at a discharge amount of 45 kg/hour.

其次，使所擠出之股束狀的熔融混練物通過容納有30℃的水之冷卻水槽中而進行冷卻。 Next, the extruded strand-shaped melt kneaded material was cooled by passing through a cooling water tank containing water at 30 °C.

將經冷卻之股束狀的混練物以製粒機切割而得到改質聚丙烯系樹脂(改質PP-a)的顆粒。 The cooled strand-shaped kneaded material was cut by a granulator to obtain particles of a modified polypropylene-based resin (modified PP-a).

(2)改質PP的特性調査 (2) Investigation on the characteristics of modified PP

對於依上述方式所得之改質PP-a的顆粒之一軸伸長黏 度(非線型區域的斜率)、MFR及熔融張力進行測定。 One of the particles of the modified PP-a obtained by the above method is elongated and viscous The degree (slope of the non-linear region), MFR, and melt tension were measured.

此外，熔融張力係依下述方式測定。 Further, the melt tension was measured in the following manner.

[熔融張力測定方法] [Melt tension measurement method]

直接使用顆粒作為試料。 The particles were directly used as a sample.

熔融張力係使用雙料筒毛細管流變儀Rheologic5000T(Italy Chiasuto公司製)進行測定。 The melt tension was measured using a two-barrel capillary rheometer Rheologic 5000T (manufactured by Italy Chiasuto Co., Ltd.).

亦即，將測定試料樹脂填充在已加熱至試驗溫度(230℃)的直徑15mm之料筒後，預熱5分鐘之後，從上述測定裝置的毛細管模頭(口徑2.0mm、長度20mm、流入角度平面)以保持一定的活塞下降速度(0.1546mm/s)的方式擠出成股狀，同時使該股狀物通過位於上述毛細管模頭的下方27cm的位置之張力檢測的皮帶輪後，使用捲繞捲筒並使其捲繞速度以初速8.7mm/s、加速度12mm/s²的方式緩慢地增加並進行捲繞，以股狀物剛要斷裂前的極大值與極小值的平均作為試料的熔融張力。 That is, the test sample resin was filled in a cylinder having a diameter of 15 mm heated to a test temperature (230 ° C), and after preheating for 5 minutes, a capillary die (caliber 2.0 mm, length 20 mm, inflow angle) from the above measuring device was used. The flat surface is extruded into a strand shape while maintaining a certain piston descending speed (0.1546 mm/s), and the strand is passed through a pulley which is located at a position of 27 cm below the capillary die, and is wound. The reel is wound and the winding speed is slowly increased and wound at a preliminary velocity of 8.7 mm/s and an acceleration of 12 mm/s ² , and the average of the maximum value and the minimum value immediately before the strand is broken is used as the melting of the sample. tension.

此外，在張力圖中，極大點只有1個時，則採其極大值作為熔融張力。 In addition, in the tension diagram, when there is only one maximum point, the maximum value is taken as the melt tension.

(3)通過擠出機後的特性調査 (3) Investigation of characteristics after passing through the extruder

在東洋精機製作所製的「Labo Plastomill」之本體(型號：4M150)裝設單軸擠出機{型號：D2020[具備口徑：20mm、L/D：20的標準螺桿(1條全螺紋型)]}，將單軸擠出機的3區域的溫度從擠出方向上游側往下流側依序設定為210℃、 190℃、190℃，且將前端模具溫度設定為180℃，同時以使吐出量成為1kg/小時的方式固定螺桿的旋轉數。 Single-axis extruder installed in the body of the "Labo Plastomill" manufactured by Toyo Seiki Co., Ltd. (Model: 4M150) {Model: D2020 [Standard: 20mm, L/D: 20 standard screw (1 full-thread type)] }, the temperature of the three regions of the single-axis extruder is sequentially set to 210 ° C from the upstream side to the downstream side in the extrusion direction. At 190 ° C and 190 ° C, the front end mold temperature was set to 180 ° C, and the number of rotations of the screw was fixed so that the discharge amount became 1 kg / hour.

將上述所得之改質PP-a的顆粒供應至該「Labo Plastomill」而擠出成股束狀，使該股束狀的擠出物通過儲有20℃的冷卻水之水槽而進行冷卻。 The pellet of the modified PP-a obtained above was supplied to the "Labo Plastomill" and extruded into a strand shape, and the strand-shaped extrudate was cooled by a water tank in which a cooling water of 20 ° C was stored.

將冷卻後的股束切斷而顆粒化，再次測定所得之顆粒的一軸伸長黏度(應變量1至3時的「曲線圖的斜率」)、MFR及熔融張力。 The cooled strands were cut and pelletized, and the one-axis elongational viscosity of the obtained pellets (the "slope of the graph" when the strains 1 to 3), the MFR, and the melt tension were measured again.

(4)樹脂發泡片(積層發泡片)的製作 (4) Production of resin foam sheet (laminated foam sheet)

將所得之「改質PP-a」85質量份、SunAllomer公司製的熱塑性彈性體樹脂之商品名「Q100F」15質量份及氣泡調整劑(大日精化工業公司製「Fine Cell MasterHCPO410K」)0.45質量份進行乾式摻配，而得到混合物。 85 parts by mass of the obtained "modified PP-a", 15 parts by mass of the product name "Q100F" of the thermoplastic elastomer resin manufactured by Sun Allomer Co., Ltd., and a bubble adjusting agent ("Fine Cell Master HCPO410K" manufactured by Daisei Seiki Co., Ltd.) 0.45 mass The mixture was dry blended to obtain a mixture.

將該混合物供應至具備口徑50mm的No.1擠出機及口徑65mm的No.2擠出機之串聯型擠出機的No.1擠出機之料斗，在No.1擠出機的料筒內加熱熔融混練後，將作為發泡劑之混合丁烷氣體(正丁烷：異丁烷=7：3)以成為2.5質量%的比率之方式壓入No.1擠出機。使含有壓入的發泡劑之聚丙烯系樹脂組成物熔融混練而在該擠出機內調製發泡層形成用的第一聚丙烯系樹脂組成物後，使該第一聚丙烯系樹脂組成物通過將No.1擠出機及No.2擠出機連接的移送部而流入至No.2擠出機。 The mixture was supplied to a hopper of a No. 1 extruder equipped with a No. 1 extruder having a diameter of 50 mm and a tandem extruder of a No. 2 extruder having a diameter of 65 mm, and the material of the No. 1 extruder was used. After heating and melt-kneading in a cylinder, the mixed butane gas (n-butane: isobutane = 7:3) as a foaming agent was injected into a No. 1 extruder so as to have a ratio of 2.5% by mass. The polypropylene-based resin composition containing the injected foaming agent is melt-kneaded, and a first polypropylene-based resin composition for forming a foamed layer is prepared in the extruder, and then the first polypropylene-based resin is composed. The product was poured into a No. 2 extruder by a transfer unit that connected the No. 1 extruder and the No. 2 extruder.

其次，在該No.2擠出機的料筒內使第一聚丙烯系樹脂組成物均勻地冷卻後，流入匯合模。 Next, the first polypropylene-based resin composition was uniformly cooled in the cylinder of the No. 2 extruder, and then flowed into a confluent mold.

此時的樹脂溫度為180℃，來自No.2擠出機的吐出量為30kg/小時。 The resin temperature at this time was 180 ° C, and the discharge amount from the No. 2 extruder was 30 kg / hr.

另一方面，作為非發泡層用的第二聚丙烯系樹脂組成物，係使用含有上述「改質PP-a」作為改質聚丙烯系樹脂，且含有Basell公司製的商品名「Q100F」作為熱塑性彈性體及三洋化成股份有限公司製的商品名：「Pelestat230」(聚醚-聚丙烯嵌段共聚物)作為高分子型抗靜電劑者。 On the other hand, the second polypropylene resin composition for the non-foaming layer is a modified polypropylene resin containing the above-mentioned "modified PP-a", and contains the product name "Q100F" manufactured by Basell Corporation. As a thermoplastic elastomer and a trade name of Sanyo Chemical Co., Ltd., "Pelestat 230" (polyether-polypropylene block copolymer) is used as a polymer type antistatic agent.

具體而言，係將含有比率為前述的「改質PP-a」74質量份、前述熱塑性彈性體13質量份及高分子型抗靜電劑13質量份之混合原料供應至口徑32mm的單軸擠出機的料斗而進行熔融混練後，流入至前述匯合模。 Specifically, a mixed raw material having a ratio of 74 parts by mass of the above-mentioned "modified PP-a", 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of the polymer type antistatic agent is supplied to a uniaxial extrusion having a diameter of 32 mm. After the hopper of the machine is melted and kneaded, it flows into the confluent die.

此時的吐出量為3kg/小時。 The discharge amount at this time was 3 kg/hour.

發泡層與非發泡層，係將在匯合模匯合的第一聚丙烯系樹脂組成物與第二聚丙烯系樹脂組成物送入模縫的口徑為70mm的圓模，從該圓模之圓環狀的吐出口(模縫間隔0.4mm)予以共擠出成圓筒狀而製作。 The foamed layer and the non-foamed layer are obtained by feeding a first polypropylene-based resin composition and a second polypropylene-based resin composition which are combined in a merged mold into a die having a die diameter of 70 mm. The annular discharge port (mold gap 0.4 mm) was co-extruded into a cylindrical shape.

然後，將非發泡層積層在發泡層之狀態的圓筒狀發泡體以冷卻心軸冷卻成形後，藉由裝設於冷卻心軸的後部之切割器將圓筒狀發泡體切開，將長條帶狀的樹脂發泡片(積層發泡片1)以拉取速度2.1m/分鐘予以捲繞。 Then, after the cylindrical foam having the non-foamed laminated layer in the state of the foamed layer is cooled and formed by the cooling mandrel, the cylindrical foam is cut by a cutter attached to the rear of the cooling mandrel. The long-chain resin foam sheet (layered foam sheet 1) was wound at a take-up speed of 2.1 m/min.

此時的樹脂發泡片的平均厚度為2.18mm。 The resin foamed sheet at this time had an average thickness of 2.18 mm.

(改質PP-b至改質PP-f：積層發泡片2至5) (Modified PP-b to modified PP-f: laminated foam sheets 2 to 5)

除了將所使用的聚丙烯系樹脂、苯乙烯量、有機過氧化物之量變更如下表6以外，係以與改質PP-a同樣的方式製作改質聚丙烯系樹脂，調查各種物性。 A modified polypropylene resin was produced in the same manner as in the modified PP-a except that the amount of the polypropylene resin, the amount of styrene, and the amount of the organic peroxide to be used was changed as shown in the following Table 6, and various physical properties were examined.

而且，使用所得之改質聚丙烯系樹脂，以與改質PP-a時同樣的方式製作積層發泡片。 Further, using the obtained modified polypropylene resin, a laminated foam sheet was produced in the same manner as in the case of modifying PP-a.

(積層發泡片6、7) (Laminated foam sheets 6, 7)

使用改質PP-a及改質PP-f製作積層發泡片。 The laminated foam sheet was produced using the modified PP-a and the modified PP-f.

將「改質PP-a」39質量份、由Japan Polypropylene公司以商品名「BC6C」於市面販售之嵌段PP 55質量份、SunAllomer公司製的熱塑性彈性體樹脂之商品名「Q100F」6質量份及氣泡調整劑(大日精化工業公司製「Fine Cell Master HCPO410K」)1.5質量份進行乾式摻配而得到混合物。 39 parts by mass of "modified PP-a", 55 parts by mass of block PP sold by the company Japan Polypropylene under the trade name "BC6C", and the product name "Q100F" of the thermoplastic elastomer resin manufactured by SunAllomer Co., Ltd. 1.5 parts by mass of a bubble adjusting agent ("Fine Cell Master HCPO410K" manufactured by Daisei Seiki Co., Ltd.) was subjected to dry blending to obtain a mixture.

將該混合物供應至具備口徑50mm的No.1擠出機及口徑65mm的No.2擠出機之串聯型擠出機的No.1擠出機的料斗，在No.1擠出機的料筒內加熱熔融混練後，將作為發泡劑之混合丁烷氣體(正丁烷：異丁烷=7：3)以成為1.3質量%的比率之方式壓入No.1擠出機。使含有壓入的發泡劑之聚丙烯系樹脂組成物熔融混練而在該擠出機內調製發泡層形成用的第一聚丙烯系樹脂組成物後，使該第一聚丙烯系樹脂組成物通過將No.1擠出機與No.2擠出機連接的移送部而流入至No.2擠出機。 The mixture was supplied to a hopper of a No. 1 extruder equipped with a No. 1 extruder having a diameter of 50 mm and a tandem extruder of a No. 2 extruder having a diameter of 65 mm, and the material of the No. 1 extruder was used. After heating and melt-kneading in a cylinder, the mixed butane gas (n-butane: isobutane = 7:3) as a foaming agent was pressed into a No. 1 extruder so as to have a ratio of 1.3% by mass. The polypropylene-based resin composition containing the injected foaming agent is melt-kneaded, and a first polypropylene-based resin composition for forming a foamed layer is prepared in the extruder, and then the first polypropylene-based resin is composed. The product was poured into a No. 2 extruder by a transfer unit in which a No. 1 extruder and a No. 2 extruder were connected.

其次，在該No.2擠出機的料筒內將第一聚丙烯系樹脂組成物均勻地冷卻後，流入至匯合模。 Next, the first polypropylene-based resin composition was uniformly cooled in the cylinder of the No. 2 extruder, and then flowed into a confluent mold.

此時的樹脂溫度為180℃，來自No.2擠出機的吐出量為30kg/小時。 The resin temperature at this time was 180 ° C, and the discharge amount from the No. 2 extruder was 30 kg / hr.

另一方面，作為非發泡層用的第二聚丙烯系樹脂組成物，係使用含有上述「改質PP-a」作為改質聚丙烯系樹脂，且含有Basell公司製的商品名「Q100F」作為熱塑性彈性體及三洋化成股份有限公司製的商品名：「Pelestat230」(聚醚-聚丙烯嵌段共聚物)作為高分子型抗靜電劑者。 On the other hand, the second polypropylene resin composition for the non-foaming layer is a modified polypropylene resin containing the above-mentioned "modified PP-a", and contains the product name "Q100F" manufactured by Basell Corporation. As a thermoplastic elastomer and a trade name of Sanyo Chemical Co., Ltd., "Pelestat 230" (polyether-polypropylene block copolymer) is used as a polymer type antistatic agent.

具體而言，係將含有比率為前述的「改質PP-a」74質量份、前述熱塑性彈性體13質量份及高分子型抗靜電劑13質量份之混合原料供應至口徑32mm的單軸擠出機之料斗而進行熔融混練後，流入至前述匯合模。 Specifically, a mixed raw material having a ratio of 74 parts by mass of the above-mentioned "modified PP-a", 13 parts by mass of the thermoplastic elastomer, and 13 parts by mass of the polymer type antistatic agent is supplied to a uniaxial extrusion having a diameter of 32 mm. After the hopper of the machine is melted and kneaded, it flows into the above-mentioned merge mold.

並且，之後以與「積層發泡片1」同樣的方式製作樹脂發泡片(積層發泡片6)。 Then, a resin foam sheet (layered foam sheet 6) was produced in the same manner as in the "laminated foam sheet 1".

此時的吐出量為3kg/小時。 The discharge amount at this time was 3 kg/hour.

同樣地將改質PP-a置換成改質PP-f，而得到「積層發泡片8」。 Similarly, the modified PP-a was replaced with the modified PP-f to obtain "layered foamed sheet 8".

將改質PP-a至改質PP-e在通過擠出機前的特性與通過後的特性示於表7。 Table 7 shows the characteristics of the modified PP-a to the modified PP-e before passing through the extruder and the characteristics after the passage.

又，將使用改質PP-a至改質PP-f所製作的發泡片之特性示於表8。 Further, the characteristics of the foamed sheet produced by using the modified PP-a to the modified PP-f are shown in Table 8.

由上述結果可知，將MFR高的聚丙烯系樹脂改質後的改質聚丙烯系樹脂，在通過擠出機後表現特定的一軸伸長黏度，係適合在熔融狀態時以高剪切速度進行加工之用途。 From the above results, it is understood that the modified polypropylene resin modified by the polypropylene resin having a high MFR exhibits a specific one-axis elongational viscosity after passing through the extruder, and is suitable for processing at a high shear rate in a molten state. Use.

而且，由上述結果可知，藉由使用如此之改質PP，可得到獨立氣泡性高(連續氣泡率低)且發泡狀態良好之發泡片。 Further, from the above results, it has been found that by using such a modified PP, a foamed sheet having high closed cell properties (low open cell ratio) and good foaming state can be obtained.

[評估2] [Evaluation 2]

使用改質PP-a及改質PP-f製作單層結構的發泡片。 A foamed sheet having a single layer structure was produced using the modified PP-a and the modified PP-f.

(1)發泡片的製作(發泡片9、10) (1) Production of foamed sheet (foam sheet 9, 10)

將所得之「改質PP」85質量份、SunAllomer公司製的熱塑性彈性體樹脂之商品名「Q100F」15質量份進行乾式摻配而得到聚合物混合物。 85 parts by mass of the obtained "modified PP" and 15 parts by mass of the product name "Q100F" of a thermoplastic elastomer resin manufactured by Sun Allomer Co., Ltd. were dry-blended to obtain a polymer mixture.

將該聚合物混合物與化學發泡劑(大日精化工業公司製「Fine Cell Master HCPO410K」)一起以擠出機熔融混練，從裝設於該擠出機的前端之圓模予以擠出，並其使發泡而製作發泡片。 The polymer mixture was melt-kneaded together with a chemical foaming agent ("Fine Cell Master HCPO410K" manufactured by Dairi Seiki Co., Ltd.) in an extruder, and extruded from a round die installed at the front end of the extruder. This is foamed to produce a foamed sheet.

使用各改質PP所得之發泡片的特性如下所示。 The characteristics of the foamed sheet obtained by using each modified PP are as follows.

(2)成形性評估 (2) Formability evaluation

從所製作的各發泡片中切出縱長700mm×橫長1050mm之平面長方形狀的試驗片。 A test piece having a rectangular shape of a length of 700 mm × a length of 1050 mm was cut out from each of the produced foam sheets.

然後，準備單發成形機(東成產業公司製商品名「UNIC自動成形機FM-3A」)，將該單發成形機的上側加熱器的平均溫度設為274℃，下側加熱器的平均溫度設為237℃，上側環境溫度設為192℃，下側環境溫度設為185℃。 Then, a single-shot molding machine (trade name "UNIC Automatic Forming Machine FM-3A" manufactured by Tosoh Corporation) was prepared, and the average temperature of the upper heater of the single-shot molding machine was 274 ° C, and the average temperature of the lower heater was set. Set to 237 ° C, the upper ambient temperature was set to 192 ° C, and the lower ambient temperature was set to 185 ° C.

其次，將上述試驗片導入單發成形機並各別加熱14至18秒後，使用配置有22個直徑10mm(上面)×直徑35mm(底面)且高度不同之圓錐台的模具，並將模具表面溫度調溫至50℃，進行加熱成形。 Next, after the test piece was introduced into a single-shot molding machine and heated for 14 to 18 seconds, respectively, 22 molds having a truncated cone having a diameter of 10 mm (top surface) × a diameter of 35 mm (bottom surface) and different heights were used, and the mold surface was used. The temperature was adjusted to 50 ° C and heat forming was performed.

22個圓錐台的高度係如下述表所示。 The height of the 22 truncated cones is as shown in the table below.

然後，以目視觀察所得之成形體，將各圓錐形狀無破裂者之中高度最高的圓錐台的編號(No)彙整於下述表。 Then, the obtained molded body was visually observed, and the number (No) of the truncated cone having the highest height among the conical shapes without cracks was collected in the following table.

由上述的結果可知，以MFR高的聚丙烯系樹脂作為起始原料的改質PP，對於形成具有高獨立氣泡性(連續氣泡率低)且成形性良好(延伸良好)之樹脂發泡體為有效。 From the above results, it is understood that the modified PP having a polypropylene resin having a high MFR as a starting material is formed into a resin foam having high closed cell properties (low open cell ratio) and good moldability (extended elongation). effective.

<第五探討點：多分枝指數與成形性> <Fifth Discussion Point: Multi-branch Index and Formability>

除了將所使用的聚丙烯系樹脂、苯乙烯量、有機過氧 化物之量變更如下表12以外，其餘以與改質PP-a同樣的方式製作改質聚丙烯系樹脂。 In addition to the polypropylene resin used, the amount of styrene, organic peroxygen The modified amount of the compound was changed in the same manner as in the modified PP-a except that the amount of the compound was changed as shown in the following Table 12.

製作4種類(mPP1至mPP4)之通過擠出機前後的多分枝指數成為表13所示的狀態之改質聚丙烯系樹脂。 A modified polypropylene resin having a multi-branch index before and after passing through the extruder of four types (mPP1 to mPP4) was produced in the state shown in Table 13.

將該改質聚丙烯系樹脂的相位角、MFR及熔融張力一併顯示於表13。 The phase angle, MFR, and melt tension of the modified polypropylene resin are shown in Table 13.

將「mPP1」至「mPP4」85質量份、SunAllomer公司製的熱塑性彈性體樹脂之商品名「Q100F」15質量份進行乾式摻配而得到聚合物混合物。 85 parts by mass of "mPP1" to "mPP4" and 15 parts by mass of the product name "Q100F" of a thermoplastic elastomer resin manufactured by Sun Allomer Co., Ltd. were dry blended to obtain a polymer mixture.

將該聚合物混合物與化學發泡劑(大日精化工業公司製「Fine Cell Master HCPO410K」)一起以擠出機熔融混練，從裝設於該擠出機的前端之圓模予以擠出並使其發泡，而製作下述表14所示之發泡片。 The polymer mixture was melt-kneaded together with a chemical foaming agent ("Fine Cell Master HCPO410K" manufactured by Daisei Seiki Co., Ltd.) in an extruder, and extruded from a round die installed at the front end of the extruder. This was foamed to produce a foamed sheet shown in Table 14 below.

使用各mPP所得之樹脂發泡片的特性如下所示。 The properties of the resin foamed sheet obtained by using each mPP are as follows.

從所製作的各發泡片中切出縱長700mm×橫長1050mm之平面長方形狀的試驗片。 A test piece having a rectangular shape of a length of 700 mm × a length of 1050 mm was cut out from each of the produced foam sheets.

然後，準備單發成形機(東成產業公司製商品名「UNIC自動成形機FM-3A」)，將該單發成形機的上側加 熱器的平均溫度設為274℃，下側加熱器的平均溫度設為237℃，上側環境溫度設為192℃，下側環境溫度設為185℃。 Then, a single-shot molding machine (product name "UNIC automatic molding machine FM-3A" manufactured by Tosei Corporation) is prepared, and the upper side of the single-shot molding machine is added. The average temperature of the heater was set to 274 ° C, the average temperature of the lower heater was set to 237 ° C, the upper ambient temperature was set to 192 ° C, and the lower ambient temperature was set to 185 ° C.

其次，將上述試驗片導入單發成形機，並各別加熱14至18秒後，使用配置有22個直徑10mm(上面)×直徑35mm(底面)且高度不同之圓錐台的模具，並將模具表面溫度溫調至50℃，進行加熱成形。 Next, the test piece was introduced into a single-shot molding machine, and after heating for 14 to 18 seconds, respectively, a mold having 22 cones having a diameter of 10 mm (top surface) × a diameter of 35 mm (bottom surface) and different heights was used, and the mold was used. The surface temperature was adjusted to 50 ° C and heat formed.

22個圓錐台的高度係如前述表10所示。 The height of the 22 truncated cones is as shown in Table 10 above.

然後，以目視觀察所得之成形體，將各圓錐形狀無破裂者之中高度最高的圓錐台之編號(No)彙整於下述表。 Then, the obtained molded body was visually observed, and the number (No) of the truncated cone having the highest height among the conical shapes without cracks was collected in the following table.

由上述的結果可知，在通過擠出機後會顯示特定的多分枝指數之改質PP，適合在熔融狀態以高剪切速度進行加工之用途。 From the above results, it is understood that the modified PP having a specific multi-branched index after passing through the extruder is suitable for use in a molten state at a high shear rate.

而且，由上述的結果可知，藉由使用如此之改質PP，可得到具有高獨立氣泡性(連續氣泡率低)且成形性良好 (延伸良好)之樹脂發泡體。 Further, from the above results, it is understood that by using such a modified PP, it is possible to obtain a high independent bubble property (low continuous cell ratio) and good moldability. (extendedly extended) resin foam.

本案圖式為實施形態之積層發泡片之概略剖面圖、用以製造積層發泡片之設備的概略圖、詳細圖及用以測定膠化率之器具的概略圖，無法代表本案發明。故本案無指定代表圖。 The present invention is a schematic cross-sectional view of a laminated foam sheet of the embodiment, a schematic view, a detailed view of an apparatus for producing a laminated foam sheet, and a schematic view of an apparatus for measuring a gelation rate, which are not representative of the present invention. Therefore, there is no designated representative map in this case.

Claims (4)

一種改質聚丙烯系樹脂，其係聚丙烯系樹脂與芳香族乙烯基單體的反應物，且具有較前述聚丙烯系樹脂更高的熔融張力者；前述聚丙烯系樹脂在溫度230℃、額定荷重2.16kg的條件下所測定之熔融質量流率為4.0g/10分鐘以上。 A modified polypropylene resin which is a reaction product of a polypropylene resin and an aromatic vinyl monomer and which has a higher melt tension than the polypropylene resin; and the polypropylene resin has a temperature of 230 ° C. The melt mass flow rate measured under the conditions of a rated load of 2.16 kg was 4.0 g/10 min or more. 如申請專利範圍第1項所述之改質聚丙烯系樹脂，其中，在通過擠出機後，以溫度200℃、1.0/秒的一定應變速度測定一軸伸長黏度時係表現應變硬化性，而且在將橫軸設為應變量(ε)的對數(log(ε))、縱軸設為伸長黏度(η)的對數(log(η))之雙對數曲線圖中表示一軸伸長黏度的測定結果時，在應變量1以上3以下的範圍內之曲線圖的斜率為1.0以上。 The modified polypropylene-based resin according to claim 1, wherein the strain-curvability is measured when the one-axis elongational viscosity is measured at a constant strain rate of 200 ° C and 1.0 / sec after passing through the extruder, and The measurement result of the one-axis elongation viscosity is shown in the double logarithmic graph in which the horizontal axis is the logarithm (log(ε)) of the strain amount (ε) and the vertical axis is the logarithm (log(η)) of the elongation viscosity (η). In the case of the strain amount 1 or more and 3 or less, the slope of the graph is 1.0 or more. 如申請專利範圍第1項或第2項所述之改質聚丙烯系樹脂，其中，在通過擠出機後，以溫度180℃、應變速度0.1至8.5(sec^-1)測定一軸伸長黏度時，係表現0.25以上的多分枝指數(MBI)；惟，多分枝指數(MBI)係意指在將橫軸設為應變速度(v)的對數(log(v))、縱軸設為應變硬化度(SHI)之單對數曲線圖中表示一軸伸長黏度的測定結果時之曲線圖的斜率；而且，應變硬化度(SHI)係意指在將橫軸設為應變量(ε)的對數(log(ε))、縱軸設為伸長黏度(η)的對數(log(η))之雙對數曲線圖中顯示出一軸伸長黏度的測定結果時，在應變量1以上3以下的範圍之曲線圖 的斜率。 The modified polypropylene-based resin according to the first or second aspect of the invention, wherein the one-axis elongational viscosity is measured at a temperature of 180 ° C and a strain rate of 0.1 to 8.5 (sec ^-1 ) after passing through an extruder. The system exhibits a multi-branch index (MBI) of 0.25 or more; however, the multi-branch index (MBI) means that the horizontal axis is set to the logarithm (log(v)) of the strain velocity (v), and the vertical axis is set to strain hardening. The slope of the graph showing the measurement result of the one-axis elongational viscosity in the single logarithmic graph of degree (SHI); and the strain hardening degree (SHI) means the logarithm of the horizontal axis as the strain (ε) (log) (ε)), and the vertical axis is a logarithm of the logarithm (log(η)) of the elongational viscosity (η). When the measurement result of the one-axis elongational viscosity is measured, the curve is in the range of the strain 1 or more and 3 or less. The slope of. 一種改質聚丙烯系樹脂之製造方法，其係使聚丙烯系樹脂與芳香族乙烯基單體反應而製作熔融張力較前述聚丙烯系樹脂更高之改質聚丙烯系樹脂，其中，係使用在溫度230℃、額定荷重2.16kg的測定條件下表現4.0g/10分鐘以上的熔融質量流率之聚丙烯系樹脂作為前述聚丙烯系樹脂。 A method for producing a modified polypropylene resin, which comprises reacting a polypropylene resin with an aromatic vinyl monomer to produce a modified polypropylene resin having a higher melt tension than the polypropylene resin, wherein A polypropylene-based resin which exhibits a melt mass flow rate of 4.0 g/10 min or more under the measurement conditions of a temperature of 230 ° C and a rated load of 2.16 kg is used as the polypropylene-based resin.