TW201922893A - Elastomer resin composition and molded object - Google Patents
Elastomer resin composition and molded object Download PDFInfo
- Publication number
- TW201922893A TW201922893A TW107135249A TW107135249A TW201922893A TW 201922893 A TW201922893 A TW 201922893A TW 107135249 A TW107135249 A TW 107135249A TW 107135249 A TW107135249 A TW 107135249A TW 201922893 A TW201922893 A TW 201922893A
- Authority
- TW
- Taiwan
- Prior art keywords
- elastomer resin
- resin composition
- mass
- elastomer
- ethylene
- Prior art date
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本發明係關於一種彈性體樹脂組合物及包含該彈性體樹脂組合物之成形體。The present invention relates to an elastomer resin composition and a molded body comprising the elastomer resin composition.
於汽車或機械、電氣製品等各種領域中使用之彈性體中,為了提高機械特性或加工性等而調配有油等添加劑。例如專利文獻1中記載之防振橡膠構件中含有滲出性潤滑劑,為了賦予滑動性而設法控制滲油性。然而,為了控制滲油性,需要精密地控制彈性體組合物之微結構。In an elastomer used in various fields such as automobiles, machinery, and electrical products, additives such as oil are prepared in order to improve mechanical properties, workability, and the like. For example, the anti-vibration rubber member described in Patent Document 1 contains a bleed lubricant, and seeks to control the oil bleed property in order to impart slidability. However, in order to control oil permeability, it is necessary to precisely control the microstructure of the elastomer composition.
另一方面,彈性體製品存在若暴露於大氣中,則由於大氣中之臭氧之影響而於製品之表面產生無數龜裂之問題。因此,需要臭氧耐性優異之彈性體製品。 先前技術文獻 專利文獻On the other hand, when an elastomer product is exposed to the atmosphere, there are problems in that numerous cracks are generated on the surface of the product due to the influence of ozone in the atmosphere. Therefore, an elastomer product excellent in ozone resistance is required. Prior Technical Literature Patent Literature
專利文獻1:日本專利特開2013-11328號公報Patent Document 1: Japanese Patent Laid-Open Publication No. 2013-11328
[發明所欲解決之問題][The problem that the invention wants to solve]
本發明所欲解決之課題係提供一種臭氧耐性優異之交聯彈性體樹脂組合物、及包含該彈性體樹脂組合物之成形體。 [解決問題之技術手段]The problem to be solved by the present invention is to provide a crosslinked elastomer resin composition excellent in ozone resistance and a molded body comprising the elastomer resin composition. [Technical means to solve the problem]
本發明者等人為了解決上述課題而進行了銳意研究,結果發現藉由下述發明可解決該課題。即,本案發明係關於以下內容。 [1]一種彈性體樹脂組合物,其含有:彈性體樹脂(A);聚丙烯系樹脂(B),其根據熔解吸熱曲線所獲得之熔解吸熱量(ΔH-D)為0 J/g以上且80 J/g以下,上述熔解吸熱曲線係藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得;及添加劑(D);且 上述彈性體樹脂組合物相對於上述彈性體樹脂(A)及上述聚丙烯系樹脂(B)之合計量100質量%,包含上述彈性體樹脂(A)50質量%以上且99.5質量%以下、及上述聚丙烯系樹脂(B)0.5質量%以上且50質量%以下,且於230℃下不顯示流動性。 [2]如上述[1]中所記載之彈性體樹脂組合物,其中上述聚丙烯系樹脂(B)滿足下述(1)。 (1)未觀測到熔點(Tm-D)或熔點(Tm-D)為0℃以上且120℃以下,上述熔點(Tm-D)係定義為於藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得之熔解吸熱曲線之最高溫側觀測到之峰頂。 [3]如上述[1]或[2]中所記載之彈性體樹脂組合物,其中上述聚丙烯系樹脂(B)之極限黏度[η]為0.01 dL/g以上且2.50 dL/g以下。 [4]如上述[1]至[3]中任一項所記載之彈性體樹脂組合物,其中上述聚丙烯系樹脂(B)包含超過0莫耳%且為20莫耳%以下之選自由乙烯及碳數4~30之α-烯烴所組成之群中之至少1種結構單元。 [5]如上述[1]至[4]中任一項所記載之彈性體樹脂組合物,其中上述彈性體樹脂(A)包含源自選自由苯乙烯、二烯、含矽單體、含氟單體、乙烯及異戊二烯所組成之群中之至少1種之結構單元。 [6]如上述[5]中所記載之彈性體樹脂組合物,其中上述二烯為選自由丁二烯、異戊二烯、β-金合歡烯、環戊二烯、二環戊二烯、5-亞乙基-2-降𦯉烯及1,4-己二烯所組成之群中之至少1種。 [7]如上述[1]至[5]中任一項所記載之彈性體樹脂組合物,其中上述彈性體樹脂(A)包含源自苯乙烯之結構單元。 [8]如上述[1]至[5]中任一項所記載之彈性體樹脂組合物,其中上述彈性體樹脂(A)為苯乙烯與共軛二烯之共聚物。 [9]如上述[1]至[5]中任一項所記載之彈性體樹脂組合物,其中上述彈性體樹脂(A)為乙烯-丙烯-非共軛二烯系共聚物橡膠。 [10]如上述[1]至[5]中任一項所記載之彈性體樹脂組合物,其中上述彈性體樹脂(A)為共軛二烯系橡膠。 [11]如上述[1]至[10]中任一項所記載之彈性體樹脂組合物,其中上述添加劑(D)含有油。 [12]一種成形體,其包含如上述[1]至[11]中任一項所記載之彈性體樹脂組合物。 [發明之效果]The present inventors have conducted intensive studies to solve the above problems, and as a result, have found that the problem can be solved by the following invention. That is, the invention of the present invention relates to the following. [1] An elastomer resin composition comprising: an elastomer resin (A); and a polypropylene resin (B) having a melting heat absorption (ΔH-D) of 0 J/g or more obtained according to a melting endothermic curve. And 80 J/g or less, the melting endothermic curve is obtained by using a differential scanning calorimeter (DSC), maintaining the sample at -10 ° C for 5 minutes in a nitrogen atmosphere, and then raising the temperature at 10 ° C / min; And the additive (D); and the elastomer resin composition contains 100% by mass or more of the total amount of the elastomer resin (A) and the polypropylene resin (B), and the elastomer resin (A) is 50% by mass or more. In addition, the above-mentioned polypropylene resin (B) is 0.5% by mass or more and 50% by mass or less, and does not exhibit fluidity at 230 °C. [2] The elastomer resin composition according to the above [1], wherein the polypropylene resin (B) satisfies the following (1). (1) No melting point (Tm-D) or melting point (Tm-D) is observed to be 0 ° C or more and 120 ° C or less, and the above melting point (Tm-D) is defined by using a differential scanning calorimeter (DSC). After the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, the peak of the melting endothermic curve obtained at the highest temperature side was obtained by raising the temperature at 10 ° C / min. [3] The elastomer resin composition according to [1] or [2], wherein the polypropylene resin (B) has an ultimate viscosity [?] of 0.01 dL/g or more and 2.50 dL/g or less. [4] The elastomer resin composition according to any one of the above [1], wherein the polypropylene resin (B) contains more than 0 mol% and is 20 mol% or less selected from At least one structural unit of a group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms. [5] The elastomer resin composition according to any one of [1] to [4] wherein the elastomer resin (A) is derived from a material selected from the group consisting of styrene, a diene, a ruthenium-containing monomer, and the like. A structural unit of at least one of a group consisting of a fluorine monomer, ethylene, and isoprene. [6] The elastomer resin composition according to [5] above, wherein the diene is selected from the group consisting of butadiene, isoprene, β-farnesene, cyclopentadiene, and dicyclopentadiene. And at least one of the group consisting of 5-ethylidene-2-norbornene and 1,4-hexadiene. [7] The elastomer resin composition according to any one of [1] to [5] wherein the elastomer resin (A) comprises a structural unit derived from styrene. [8] The elastomer resin composition according to any one of [1] to [5] wherein the elastomer resin (A) is a copolymer of styrene and a conjugated diene. [9] The elastomer resin composition according to any one of [1] to [5] wherein the elastomer resin (A) is an ethylene-propylene-nonconjugated diene copolymer rubber. [10] The elastomer resin composition according to any one of the above [1], wherein the elastomer resin (A) is a conjugated diene rubber. [11] The elastomer resin composition according to any one of [1] to [10] wherein the additive (D) contains an oil. [12] A molded article comprising the elastomer resin composition according to any one of the above [1] to [11]. [Effects of the Invention]
本發明之彈性體樹脂組合物之臭氧耐性優異。又,本發明之彈性體樹脂組合物可控制添加劑之滲出,樹脂組合物之表面可被滲出之添加劑塗覆,從而提高臭氧耐性。The elastomer resin composition of the present invention is excellent in ozone resistance. Further, the elastomer resin composition of the present invention can control the bleeding of the additive, and the surface of the resin composition can be coated with the exuded additive to improve ozone resistance.
本實施形態之彈性體樹脂組合物含有:彈性體樹脂(A);聚丙烯系樹脂(B),其根據熔解吸熱曲線所獲得之熔解吸熱量(ΔH-D)為0 J/g以上且80 J/g以下,上述熔解吸熱曲線係藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得;及添加劑(D);上述彈性體樹脂組合物相對於上述彈性體樹脂(A)及上述聚丙烯系樹脂(B)之合計量100質量%,包含上述彈性體樹脂(A)50質量%以上且99.5質量%以下、及上述聚丙烯系樹脂(B)0.5質量%以上且50質量%以下,且於230℃下不顯示流動性。The elastomer resin composition of the present embodiment contains an elastomer resin (A) and a polypropylene resin (B) having a melting heat absorption (ΔH-D) obtained by a melting endothermic curve of 0 J/g or more and 80. Below J/g, the above melting endothermic curve is obtained by using a differential scanning calorimeter (DSC) to hold the sample at -10 ° C for 5 minutes under nitrogen atmosphere, and then raising the temperature at 10 ° C / min; (D), the elastomer resin composition contains 100% by mass of the total amount of the elastomer resin (A) and the polypropylene resin (B), and the elastomer resin (A) is 50% by mass or more and 99.5% by mass. % or less and the above-mentioned polypropylene-based resin (B) are 0.5% by mass or more and 50% by mass or less, and fluidity is not exhibited at 230 °C.
<彈性體樹脂(A)> 本實施形態中使用之彈性體樹脂(A)並無特別限定,可使用公知之各種烯烴系橡膠。此處,就彈性回覆性之觀點而言,彈性體樹脂(A)較佳為包含源自選自由苯乙烯、二烯、含矽單體、含氟單體、乙烯及異戊二烯所組成之群中之至少1種之結構單元,其中,包含源自苯乙烯或二烯之結構單元則耐熱性、成形性及彈性回覆性之平衡優異而更佳。<Elastomer resin (A)> The elastomer resin (A) used in the present embodiment is not particularly limited, and various known olefin rubbers can be used. Here, in terms of elastic reproducibility, the elastomer resin (A) preferably comprises a material selected from the group consisting of styrene, a diene, a ruthenium-containing monomer, a fluorine-containing monomer, ethylene, and isoprene. At least one structural unit of the group, wherein the structural unit derived from styrene or diene is excellent in balance of heat resistance, moldability, and elastic reproducibility.
作為二烯,可列舉丁二烯、異戊二烯、β-金合歡烯等共軛二烯;環戊二烯、二環戊二烯、5-亞乙基-2-降𦯉烯、1,4-己二烯等非共軛二烯。二烯較佳為選自由丁二烯、異戊二烯、β-金合歡烯、環戊二烯、二環戊二烯、5-亞乙基-2-降𦯉烯及1,4-己二烯所組成之群中之至少一種。Examples of the diene include conjugated dienes such as butadiene, isoprene, and β-farnesene; cyclopentadiene, dicyclopentadiene, and 5-ethylidene-2-norbornene; a non-conjugated diene such as 4-hexadiene. The diene is preferably selected from the group consisting of butadiene, isoprene, β-farnesene, cyclopentadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, and 1,4-hexene. At least one of the group consisting of diene.
作為彈性體樹脂(A),例如可列舉苯乙烯與共軛二烯之共聚物、及其氫化物、乙烯-α-烯烴系共聚物橡膠、共軛二烯系橡膠、丁二烯橡膠及腈橡膠等。又,亦可列舉包含乙烯、碳數3~20之α-烯烴及非共軛多烯之乙烯-α-烯烴-非共軛多烯共聚物橡膠,作為其具體例,可列舉乙烯-丙烯-非共軛二烯系共聚物橡膠。作為彈性體樹脂(A),較佳為苯乙烯與共軛二烯之共聚物、乙烯-丙烯-非共軛二烯系共聚物橡膠。Examples of the elastomer resin (A) include a copolymer of styrene and a conjugated diene, and a hydrogenated product thereof, an ethylene-α-olefin copolymer rubber, a conjugated diene rubber, a butadiene rubber, and a nitrile. Rubber, etc. Further, an ethylene-α-olefin-non-conjugated polyene copolymer rubber containing ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene may be mentioned, and specific examples thereof include ethylene-propylene- Non-conjugated diene copolymer rubber. The elastomer resin (A) is preferably a copolymer of styrene and a conjugated diene, or an ethylene-propylene-nonconjugated diene copolymer rubber.
乙烯-α-烯烴-非共軛多烯共聚物橡膠較佳為包含乙烯、碳原子數為3~20之α-烯烴及非共軛多烯之無定形無規之彈性共聚物,係指藉由與過氧化物混合並於加熱下進行混練從而交聯而降低流動性或變得不流動之烯烴系共聚物橡膠。作為此種烯烴系共聚物橡膠,具體而言可列舉乙烯-α-烯烴-非共軛二烯共聚物橡膠[乙烯/α-烯烴(莫耳比)=約90/10~50/50],較佳為乙烯-α-烯烴-非共軛二烯共聚物橡膠[乙烯/α-烯烴(莫耳比)=90/10~51/49]。The ethylene-α-olefin-non-conjugated polyene copolymer rubber is preferably an amorphous random copolymer comprising ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene. An olefin-based copolymer rubber which is mixed with a peroxide and kneaded under heating to crosslink to lower the fluidity or become non-flowing. Specific examples of such an olefin-based copolymer rubber include an ethylene-α-olefin-nonconjugated diene copolymer rubber [ethylene/α-olefin (mole ratio)=about 90/10 to 50/50]. Preferred is an ethylene-α-olefin-nonconjugated diene copolymer rubber [ethylene/α-olefin (mole ratio) = 90/10 to 51/49].
作為上述非共軛二烯,具體而言可列舉二環戊二烯、1,4-己二烯、環辛二烯、亞甲基降𦯉烯、亞乙基降𦯉烯等非共軛二烯等。該等之中,較佳為乙烯-丙烯-非共軛二烯共聚物橡膠、乙烯・1-丁烯・非共軛二烯共聚物橡膠,尤其是乙烯-丙烯-非共軛二烯共聚物橡膠、其中乙烯-丙烯-亞乙基降𦯉烯共聚物橡膠特佳。Specific examples of the non-conjugated diene include non-conjugated diene such as dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, methylene norbornene, and ethylene norbornene. Alkene and the like. Among these, ethylene-propylene-non-conjugated diene copolymer rubber, ethylene, 1-butene, non-conjugated diene copolymer rubber, and especially ethylene-propylene-nonconjugated diene copolymer are preferable. Rubber, among which ethylene-propylene-ethylene decene copolymer rubber is particularly preferred.
又,作為非共軛二烯以外之非共軛多烯,具體而言可列舉6,10-二甲基-1,5,9-十一烷三烯、5,9-二甲基-1,4,8-癸三烯、6,9-二甲基-1,5,8-癸三烯、6,8,9-三甲基-1,5,8-癸三烯、6-乙基-10-甲基-1,5,9-十一烷三烯、4-亞乙基-1,6-辛二烯、7-甲基-4-亞乙基-1,6-辛二烯、7-甲基-4-亞乙基-1,6-壬二烯、7-乙基-4-亞乙基-1,6-壬二烯、6,7-二甲基-4-亞乙基-1,6-辛二烯、6,7-二甲基-4-亞乙基-1,6-壬二烯、4-亞乙基-1,6-癸二烯、7-甲基-4-亞乙基-1,6-癸二烯、7-甲基-6-丙基-4-亞乙基-1,6-辛二烯、4-亞乙基-1,7-壬二烯、8-甲基-4-亞乙基-1,7-壬二烯、4-亞乙基-1,7-十一烷二烯等非共軛三烯等。Further, specific examples of the non-conjugated polyene other than the non-conjugated diene include 6,10-dimethyl-1,5,9-undecanetriene and 5,9-dimethyl-1. ,4,8-nonanetriene, 6,9-dimethyl-1,5,8-nonanetriene, 6,8,9-trimethyl-1,5,8-nonanetriene, 6-B Benzyl-10-methyl-1,5,9-undecanetriene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octane Alkene, 7-methyl-4-ethylidene-1,6-decadiene, 7-ethyl-4-ethylidene-1,6-decadiene, 6,7-dimethyl-4- Ethylene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-decadiene, 4-ethylene-1,6-decadiene, 7- Methyl-4-ethylidene-1,6-decadiene, 7-methyl-6-propyl-4-ethylidene-1,6-octadiene, 4-ethylene-1,7 a non-conjugated triene such as decadiene, 8-methyl-4-ethylidene-1,7-decadiene or 4-ethylidene-1,7-undecenediene.
就成形性與物性之平衡之觀點而言,乙烯-α-烯烴-非共軛多烯共聚物橡膠之慕尼黏度[ML(1+4),125℃]較佳為5以上,更佳為20以上,並且,較佳為150以下,更佳為100以下。又,乙烯-α-烯烴-非共軛多烯共聚物橡膠之碘值較佳為10以下。若碘值位於此種範圍,則可獲得部分平衡良好地交聯之熱塑性彈性體組合物。The Muni viscosity [ML (1+4), 125 ° C] of the ethylene-α-olefin-non-conjugated polyene copolymer rubber is preferably 5 or more, more preferably 20 or more, from the viewpoint of balance between formability and physical properties. And, it is preferably 150 or less, more preferably 100 or less. Further, the ethylene-α-olefin-nonconjugated polyene copolymer rubber preferably has an iodine value of 10 or less. If the iodine value is in this range, a partially balanced thermoplastic elastomer composition can be obtained.
作為彈性體樹脂(A)之具體例,可列舉乙烯-丙烯-二烯橡膠(EPDM)、苯乙烯-丁二烯橡膠(SBR)、丁二烯橡膠(BR)、氯丁二烯橡膠(CR)、異戊二烯橡膠(IR)、丙烯腈-丁二烯橡膠(NBR)、苯乙烯-異戊二烯共聚物、丁二烯-異戊二烯共聚物、聚丁二烯、苯乙烯-異戊二烯-丁二烯三元共聚物、丙烯腈-氯丁二烯橡膠(ACR)、丁基橡膠(IIR)、苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、苯乙烯-乙烯-丁烯-苯乙烯嵌段共聚物(SEBS)、苯乙烯-丁二烯-丁烯-苯乙烯嵌段共聚物(SBBS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、苯乙烯-乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEEPS)、苯乙烯-乙烯-丙烯-苯乙烯嵌段共聚物(SEPS)、苯乙烯-異戊二烯-苯乙烯嵌段共聚物(SIS)、苯乙烯-乙烯-丙烯共聚物(SEP)等。又,該等亦可使用經含氧不飽和乙烯性單體改性者。 此外,作為彈性體樹脂(A)之具體例,可列舉天然橡膠(NR)、乙烯-丙烯橡膠(EPR)、苯乙烯-異戊二烯-丁二烯橡膠(SIBR)、乙烯-丙烯酸系橡膠(EA)、聚降𦯉烯橡膠、氯磺化聚乙烯(CSM)、聚胺基甲酸酯橡膠、表氯醇橡膠、環氧丙烷橡膠、丙烯酸系橡膠、氯化聚乙烯、矽酮橡膠、氟橡膠等。Specific examples of the elastomer resin (A) include ethylene-propylene-diene rubber (EPDM), styrene-butadiene rubber (SBR), butadiene rubber (BR), and chloroprene rubber (CR). ), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), styrene-isoprene copolymer, butadiene-isoprene copolymer, polybutadiene, styrene - isoprene-butadiene terpolymer, acrylonitrile-chloroprene rubber (ACR), butyl rubber (IIR), styrene-butadiene-styrene block copolymer (SBS), Styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-butadiene-butene-styrene block copolymer (SBBS), styrene-ethylene-propylene-styrene block copolymerization (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-isoprene-benzene Ethylene block copolymer (SIS), styrene-ethylene-propylene copolymer (SEP), and the like. Further, these may also be modified by an oxygen-containing unsaturated ethylenic monomer. Further, specific examples of the elastomer resin (A) include natural rubber (NR), ethylene-propylene rubber (EPR), styrene-isoprene-butadiene rubber (SIBR), and ethylene-acrylic rubber. (EA), polypyrene rubber, chlorosulfonated polyethylene (CSM), polyurethane rubber, epichlorohydrin rubber, propylene oxide rubber, acrylic rubber, chlorinated polyethylene, fluorenone rubber, Fluororubber, etc.
作為苯乙烯系彈性體樹脂之市售品,可列舉Clayton公司製造之「D系列」、「G系列」,JSR(股)製造之「TR系列」、「Dynaron」,旭化成(股)製造之「Tufprene」、「Asaprene」、「Tuftec」,Kuraray(股)製造之「Septon」、「HYBRAR」等。As a commercial product of the styrene-based elastomer resin, "D series" and "G series" manufactured by Clayton Co., Ltd., "TR series" and "Dynaron" manufactured by JSR (shares), and manufactured by Asahi Kasei Co., Ltd. Tufprene, "Asaprene", "Tuftec", "Septon" and "HYBRAR" manufactured by Kuraray Co., Ltd.
上述彈性體樹脂組合物中之彈性體樹脂(A)之含量相對於彈性體樹脂(A)及聚丙烯系樹脂(B)之合計量100質量%為50質量%以上且99.5質量%以下。若未達50質量%,則有使彈性體樹脂組合物之彈性體性降低之虞,若超過99.5質量%,則有彈性體樹脂組合物之添加劑之滲出之控制變困難之虞。就此種觀點而言,相對於彈性體樹脂(A)及聚丙烯系樹脂(B)之合計量100質量%,彈性體樹脂(A)之含量較佳為60質量%以上,更佳為65質量%以上,進而較佳為70質量%以上,而且較佳為99質量%以下,更佳為98質量%以下,進而較佳為95質量%以下。The content of the elastomer resin (A) in the elastomer resin composition is 50% by mass or more and 99.5% by mass or less based on 100% by mass of the total of the elastomer resin (A) and the polypropylene resin (B). When the amount is less than 50% by mass, the elastomeric property of the elastomer resin composition is lowered. When the amount is more than 99.5% by mass, the control of the bleeding of the additive of the elastomer resin composition becomes difficult. In view of the above, the content of the elastomer resin (A) is preferably 60% by mass or more, and more preferably 65% by mass based on 100% by mass of the total of the elastomer resin (A) and the polypropylene resin (B). % or more is more preferably 70% by mass or more, and is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 95% by mass or less.
<聚丙烯系樹脂(B)> 本實施形態中使用之聚丙烯系樹脂(B)根據熔解吸熱曲線所獲得之熔解吸熱量(ΔH-D)為0 J/g以上且80 J/g以下,上述熔解吸熱曲線係藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得。若熔解吸熱量(ΔH-D)未達0 J/g,則於彈性體樹脂組合物中無法控制添加劑之滲出,若超過80 J/g,則有使彈性體樹脂組合物之柔軟性降低之虞。就此種觀點而言,熔解吸熱量(ΔH-D)較佳為20 J/g以上,更佳為25 J/g以上,進而較佳為27 J/g以上,進而更佳為30 J/g以上,而且較佳為50 J/g以下,更佳為45 J/g以下,進而較佳為40 J/g以下。 上述熔解吸熱量(ΔH-D)係藉由將連結無熱量變化之低溫側之點與無熱量變化之高溫側之點之線作為基準線,求出利用DSC測定而獲得之熔解吸熱曲線之包含在最高溫側所觀測到之波峰之線部分與該基準線所包圍之面積而算出。再者,熔解吸熱量(ΔH-D)可藉由適當調整單體濃度或反應壓力而進行控制。<Polypropylene-based resin (B)> The polypropylene-based resin (B) used in the present embodiment has a melting heat absorption (ΔH-D) obtained by a melting endothermic curve of 0 J/g or more and 80 J/g or less. The melting endothermic curve was obtained by using a differential scanning calorimeter (DSC) to hold the sample at -10 ° C for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C / min. When the heat of fusion (ΔH-D) is less than 0 J/g, the bleeding of the additive cannot be controlled in the elastomer resin composition, and if it exceeds 80 J/g, the flexibility of the elastomer resin composition is lowered. Hey. From this point of view, the heat of fusion (ΔH-D) is preferably 20 J/g or more, more preferably 25 J/g or more, still more preferably 27 J/g or more, and still more preferably 30 J/g. The above is preferably 50 J/g or less, more preferably 45 J/g or less, still more preferably 40 J/g or less. The melting heat absorption amount (ΔH-D) is obtained by determining a melting endothermic curve obtained by DSC measurement by using a line connecting a point on the low temperature side where no heat is changed and a point on the high temperature side where no heat is changed as a reference line. The line portion of the peak observed on the highest temperature side is calculated from the area surrounded by the reference line. Further, the heat of fusion (ΔH-D) can be controlled by appropriately adjusting the monomer concentration or the reaction pressure.
聚丙烯系樹脂(B)較佳為滿足下述(1)。 (1)未觀測到熔點(Tm-D)或熔點(Tm-D)為0℃以上且120℃以下,上述熔點(Tm-D)係定義為於藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得之熔解吸熱曲線之最高溫側所觀測到之峰頂。The polypropylene resin (B) preferably satisfies the following (1). (1) No melting point (Tm-D) or melting point (Tm-D) is observed to be 0 ° C or more and 120 ° C or less, and the above melting point (Tm-D) is defined by using a differential scanning calorimeter (DSC). After the sample was kept at -10 ° C for 5 minutes in a nitrogen atmosphere, the peak top observed on the highest temperature side of the melting endothermic curve was obtained by raising the temperature at 10 ° C / min.
就提高彈性體樹脂組合物之柔軟性,控制添加劑(D)之滲出之觀點而言,聚丙烯系樹脂(B)之熔點(Tm-D)較佳為未被觀測到或為0℃以上且120℃以下。觀測到熔點之情形時,就相同之觀點而言,更佳為30℃以上,進而較佳為35℃以上,進而更佳為40℃以上,並且更佳為100℃以下,進而較佳為90℃以下,進而更佳為85℃以下。 再者,熔點能夠藉由適當調整單體濃度或反應壓力而進行控制。The melting point (Tm-D) of the polypropylene resin (B) is preferably not observed or is 0 ° C or more from the viewpoint of improving the flexibility of the elastomer resin composition and controlling the bleeding of the additive (D). Below 120 °C. When the melting point is observed, from the same viewpoint, it is more preferably 30 ° C or more, further preferably 35 ° C or more, further preferably 40 ° C or more, and more preferably 100 ° C or less, and further preferably 90. It is below °C, and more preferably 85 °C or less. Further, the melting point can be controlled by appropriately adjusting the monomer concentration or the reaction pressure.
又,聚丙烯系樹脂(B)之極限黏度[η]較佳為0.01 dL/g以上,更佳為0.10 dL/g以上,進而較佳為0.30 dL/g以上,進而更佳為0.40 dL/g以上,並且較佳為2.50 dL/g以下,更佳為2.00 dL/g以下,進而較佳為1.80 dL/g以下,進而更佳為1.70 dL/g以下,進而更佳為1.00 dL/g以下。藉由將極限黏度[η]設為0.01 dL/g以上,可進一步提高上述彈性體樹脂(A)與聚丙烯系樹脂(B)之混合性。又,藉由設為2.50 dL/g以下,可進一步改善加工性。此例如於包含滑石等填料之樹脂組合物中亦相同。Further, the ultimate viscosity [η] of the polypropylene resin (B) is preferably 0.01 dL/g or more, more preferably 0.10 dL/g or more, still more preferably 0.30 dL/g or more, and still more preferably 0.40 dL/ g or more, and preferably 2.50 dL/g or less, more preferably 2.00 dL/g or less, further preferably 1.80 dL/g or less, further preferably 1.70 dL/g or less, and further preferably 1.00 dL/g. the following. By setting the ultimate viscosity [η] to 0.01 dL/g or more, the mixing property of the above elastomer resin (A) and polypropylene resin (B) can be further improved. Further, by setting it to 2.50 dL/g or less, the workability can be further improved. This is also the same, for example, in a resin composition containing a filler such as talc.
再者,上述極限黏度[η]係於135℃之萘滿中,藉由烏氏黏度計測定比濃黏度(ηSP /c),使用下述式(赫金斯式)而算出。 ηSP /c=[η]+K[η]2 c ηSP /c(dL/g):比濃黏度 [η](dL/g):極限黏度 c(g/dL):聚合物黏度 K=0.35(赫金斯常數)Further, the above-mentioned ultimate viscosity [?] was calculated in a tetralin at 135 ° C, and the specific viscosity (η SP /c) was measured by a Ubbel viscometer, and was calculated by the following formula (Higkins type). η SP /c=[η]+K[η] 2 c η SP /c(dL/g): specific viscosity [η](dL/g): ultimate viscosity c(g/dL): polymer viscosity K= 0.35 (Huggins constant)
聚丙烯系樹脂(B)之分子量分佈(Mw/Mn)較佳為3.0以下,更佳為2.8以下,進而較佳為2.6以下,進而更佳為2.5以下,並且較佳為1.5以上,更佳為1.6以上,進而較佳為1.7以上,進而更佳為1.8以上。藉由將分子量分佈(Mw/Mn)設為上述範圍內,可進一步提高彈性體樹脂組合物之柔軟性,進一步抑制彈性體樹脂組合物之黏膩。 再者,於本實施形態中,分子量分佈(Mw/Mn)係根據藉由凝膠滲透層析(GPC)法測得之聚苯乙烯換算之重量平均分子量Mw及數量平均分子量Mn而算出之值。The molecular weight distribution (Mw/Mn) of the polypropylene resin (B) is preferably 3.0 or less, more preferably 2.8 or less, still more preferably 2.6 or less, still more preferably 2.5 or less, and still more preferably 1.5 or more. It is 1.6 or more, more preferably 1.7 or more, still more preferably 1.8 or more. By setting the molecular weight distribution (Mw/Mn) within the above range, the flexibility of the elastomer resin composition can be further improved, and the stickiness of the elastomer resin composition can be further suppressed. Further, in the present embodiment, the molecular weight distribution (Mw/Mn) is a value calculated from a polystyrene-equivalent weight average molecular weight Mw and a number average molecular weight Mn measured by a gel permeation chromatography (GPC) method. .
聚丙烯系樹脂(B)之上述熔解吸熱量(ΔH-D)只要滿足上述範圍,則並無特別限定,例如較佳為選自丙烯均聚物、丙烯-乙烯嵌段共聚物、丙烯-丁烯嵌段共聚物、丙烯-α-烯烴嵌段共聚物、丙烯-乙烯無規共聚物、丙烯-丁烯無規共聚物、丙烯-乙烯-丁烯三元無規共聚物、丙烯-α-烯烴無規共聚物、或丙烯-α-烯烴接枝共聚物等之丙烯系聚合物,更佳為選自丙烯均聚物、丙烯-乙烯無規共聚物、丙烯-丁烯無規共聚物、丙烯-α-烯烴無規共聚物、丙烯-乙烯-丁烯三元無規共聚物之丙烯系聚合物,進而較佳為丙烯均聚物。The melting heat absorption amount (ΔH-D) of the polypropylene resin (B) is not particularly limited as long as it satisfies the above range. For example, it is preferably selected from the group consisting of a propylene homopolymer, a propylene-ethylene block copolymer, and a propylene-butyl group. Alkene block copolymer, propylene-α-olefin block copolymer, propylene-ethylene random copolymer, propylene-butene random copolymer, propylene-ethylene-butylene ternary random copolymer, propylene-α- The propylene-based polymer such as an olefin random copolymer or a propylene-α-olefin graft copolymer is more preferably selected from the group consisting of a propylene homopolymer, a propylene-ethylene random copolymer, and a propylene-butene random copolymer. A propylene-based polymer of a propylene-α-olefin random copolymer or a propylene-ethylene-butylene ternary random copolymer is further preferably a propylene homopolymer.
聚丙烯系樹脂(B)為共聚物之情形時,就抑制由交聯所導致之凹凸小點產生,提高彈性體樹脂組合物之柔軟性之觀點而言,較佳為包含超過0莫耳%且為20莫耳%以下之選自由乙烯及碳數4~30之α-烯烴所組成之群中之至少1種結構單元。就此種觀點而言,更佳為0.5莫耳%以上,進而較佳為1.0莫耳%以上,並且更佳為18.5莫耳%以下,進而較佳為15.0莫耳%以下,進而更佳為10.0莫耳%以下。When the polypropylene resin (B) is a copolymer, it is preferable to contain more than 0 mol% from the viewpoint of suppressing generation of irregularities due to crosslinking and improving the flexibility of the elastomer resin composition. Further, it is at least one structural unit selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms, which is 20 mol% or less. More preferably, it is 0.5 mol% or more, more preferably 1.0 mol% or more, and still more preferably 18.5 mol% or less, further preferably 15.0 mol% or less, and still more preferably 10.0. Mole% or less.
又,於聚丙烯系樹脂(B)為含有碳數為2之烯烴之共聚物之情形時,碳數為2之烯烴(即乙烯單體)之結構單元較佳為超過0莫耳%且為20莫耳%以下,更佳為超過0莫耳%且為18莫耳%以下,進而較佳為超過0莫耳%且為16莫耳%以下,進而更佳為超過0莫耳%且為14莫耳%以下。又,含有碳數為4以上之α烯烴之共聚物之情形時,碳數為4以上之α-烯烴含量較佳為超過0莫耳%且為30莫耳%以下,更佳為超過0莫耳%且為25莫耳%以下,進而較佳為超過0莫耳%且為20莫耳%以下。Further, when the polypropylene resin (B) is a copolymer containing an olefin having 2 carbon atoms, the structural unit of the olefin having 2 carbon atoms (i.e., ethylene monomer) is preferably more than 0 mol% and is 20 mol% or less, more preferably more than 0 mol% and 18 mol% or less, further preferably more than 0 mol% and 16 mol% or less, and more preferably more than 0 mol% and more 14 moles below. Further, in the case of a copolymer containing an α-olefin having 4 or more carbon atoms, the α-olefin content having 4 or more carbon atoms is preferably more than 0 mol% and 30 mol% or less, more preferably more than 0 mol. The ear % is 25 mol% or less, more preferably more than 0 mol% and 20 mol% or less.
作為聚丙烯系樹脂(B),可使用市售品。作為具體例,可列舉「L-MODU」(註冊商標)(出光興產(股)製造)之「S400」、「S600」、「S901」。作為非晶質聚α-烯烴之市售品,亦可列舉REXtac, LLC公司製造之「REXtac」、Evonik公司製造之「Vestoplast」、Eastman公司製造之「Eastoflex」、「Aerafin」等(均為商品名)。作為丙烯系彈性體之市售品,亦可列舉三井化學(股)製造之「Tafmer XM」、「Tafmer PN」、「Tafmer SN」;住友化學(股)製造之「Tafthren」;Prime Polymer(股)製造之「Prime TPO」;Dow Chemical(股)製造之「Versify」;Exxon Mobil公司製造之「Vistamaxx」、「Linxar」;Clariant公司製造之「Licocene」;Basell公司製造之「Adflex」等(均為商品名)。 尤其是使用「L-MODU」作為聚丙烯系樹脂(B)之情形時,有滲出而形成於樹脂組合物表面之塗覆層之透明性高於蠟而外觀優異之特徵。又,關於塗覆層之機械強度,使用「L-MODU」之情形亦有韌性較高,與使用蠟之情形相比較不脆故而不易產生龜裂,耐久性變得更高之特徵。A commercially available product can be used as the polypropylene resin (B). As a specific example, "S400", "S600", and "S901" of "L-MODU" (registered trademark) (manufactured by Idemitsu Kosan Co., Ltd.) can be cited. As a commercial product of the amorphous poly-α-olefin, REXtac, LLC's "REXtac", Evonik's "Vestoplast", Eastman's "Eastoflex", "Aerafin", etc. name). As a commercial item of the propylene-based elastomer, "Tafmer XM", "Tafmer PN", "Tafmer SN" manufactured by Mitsui Chemicals Co., Ltd.; "Tafthren" manufactured by Sumitomo Chemical Co., Ltd.; Prime Polymer (shares) "Prime TPO" manufactured; "Versify" manufactured by Dow Chemical; "Vistamaxx" and "Linxar" manufactured by Exxon Mobil; "Licocene" manufactured by Clariant; "Adflex" manufactured by Basell, etc. For the product name). In particular, when "L-MODU" is used as the polypropylene-based resin (B), the coating layer formed on the surface of the resin composition which is oozing out has a higher transparency than the wax and is excellent in appearance. In addition, in the case of using the "L-MODU", the mechanical strength of the coating layer is also high in toughness, and is not brittle as compared with the case of using the wax, so that cracking is less likely to occur and durability is higher.
聚丙烯系樹脂(B)可於齊格勒-納塔型之觸媒或二茂金屬觸媒等聚合觸媒之存在下使單體聚合而獲得。其中,聚丙烯系樹脂(B)較佳為藉由二茂金屬觸媒獲得之聚丙烯系樹脂。二茂金屬觸媒係均相觸媒之一種,獲得之聚合物成為具有狹窄分子量分佈或狹窄組成分佈之均勻之聚合物。The polypropylene resin (B) can be obtained by polymerizing a monomer in the presence of a polymerization catalyst such as a Ziegler-Natta type catalyst or a metallocene catalyst. Among them, the polypropylene resin (B) is preferably a polypropylene resin obtained by a metallocene catalyst. The metallocene catalyst is one of the homogeneous catalysts, and the obtained polymer becomes a uniform polymer having a narrow molecular weight distribution or a narrow composition distribution.
上述彈性體樹脂組合物中之聚丙烯系樹脂(B)之含量相對於彈性體樹脂(A)及聚丙烯系樹脂(B)之合計量100質量%為0.5質量%以上且50質量%以下。若未達0.5質量%,則有使彈性體樹脂組合物之柔軟性降低之虞,若超過50質量%,則有使彈性體樹脂組合物之彈性回覆性降低之虞。就此種觀點而言,相對於彈性體樹脂(A)及聚丙烯系樹脂(B)之合計量100質量%,聚丙烯系樹脂(B)之含量較佳為1質量%以上,更佳為2質量%以上,進而較佳為5質量%以上,並且較佳為40質量%以下,更佳為35質量%以下,進而較佳為30質量%以下。The content of the polypropylene resin (B) in the elastomer resin composition is 0.5% by mass or more and 50% by mass or less based on 100% by mass of the total of the elastomer resin (A) and the polypropylene resin (B). When the amount is less than 0.5% by mass, the flexibility of the elastomer resin composition is lowered. When the amount is more than 50% by mass, the elastic reproducibility of the elastomer resin composition is lowered. In this view, the content of the polypropylene resin (B) is preferably 1% by mass or more, and more preferably 2%, based on 100% by mass of the total of the elastomer resin (A) and the polypropylene resin (B). The mass% or more is more preferably 5% by mass or more, and is preferably 40% by mass or less, more preferably 35% by mass or less, and still more preferably 30% by mass or less.
上述彈性體樹脂組合物中之彈性體樹脂(A)及聚丙烯系樹脂(B)之合計含量相對於彈性體樹脂組合物100質量%,較佳為35質量%以上,更佳為50質量%以上,進而較佳為70質量%以上,進而更佳為75質量%以上。The total content of the elastomer resin (A) and the polypropylene resin (B) in the elastomer resin composition is preferably 35 mass% or more, and more preferably 50 mass%, based on 100% by mass of the elastomer resin composition. The above is more preferably 70% by mass or more, and still more preferably 75% by mass or more.
<聚丙烯系樹脂(C)> 就強度之觀點而言,本實施形態之彈性體樹脂組合物進而較佳為含有熔點(Tm-D)超過120℃且為180℃以下之聚丙烯系樹脂(C),上述熔點(Tm-D)係定義為於藉由使用示差掃描式熱量計(DSC),將試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得之熔解吸熱曲線之最高溫側所觀測到之峰頂。聚丙烯系樹脂(C)之熔點(Tm-D)較佳為130℃以上,更佳為140℃以上,並且較佳為170℃以下,更佳為165℃以下。若聚丙烯系樹脂(C)之熔點為上述範圍內,則就維持高溫下之硬度之觀點而言較佳。<Polypropylene-based resin (C)> The elastomer resin composition of the present embodiment further preferably contains a polypropylene resin having a melting point (Tm-D) of more than 120 ° C and 180 ° C or less (in terms of strength). C), the above melting point (Tm-D) is defined as the temperature is raised at 10 ° C / min after holding the sample at -10 ° C for 5 minutes in a nitrogen atmosphere by using a differential scanning calorimeter (DSC). The peak top observed on the highest temperature side of the melting endotherm curve obtained. The melting point (Tm-D) of the polypropylene resin (C) is preferably 130 ° C or higher, more preferably 140 ° C or higher, and is preferably 170 ° C or lower, more preferably 165 ° C or lower. When the melting point of the polypropylene resin (C) is within the above range, it is preferable from the viewpoint of maintaining the hardness at a high temperature.
作為聚丙烯系樹脂(C),較佳為選自丙烯均聚物、丙烯-乙烯嵌段共聚物、丙烯-丁烯嵌段共聚物、丙烯-α-烯烴嵌段共聚物、丙烯-乙烯無規共聚物、丙烯-丁烯無規共聚物、丙烯-α-烯烴無規共聚物、丙烯-α-烯烴接枝共聚物等之丙烯系聚合物(C')。The polypropylene-based resin (C) is preferably selected from the group consisting of a propylene homopolymer, a propylene-ethylene block copolymer, a propylene-butene block copolymer, a propylene-α-olefin block copolymer, and propylene-ethylene. A propylene-based polymer (C') such as a copolymer, a propylene-butene random copolymer, a propylene-α-olefin random copolymer, or a propylene-α-olefin graft copolymer.
進而,就獲得之成形體之剛性之觀點而言,丙烯系聚合物(C')較佳為聚合物中含有之乙烯結構單元之含量為1莫耳%以下,更佳為不含乙烯結構單元之丙烯均聚物。 再者,上述聚合物可為使用源自石油、煤之單體之聚合物,亦可為使用源自生質之單體之聚合物。Further, from the viewpoint of the rigidity of the obtained molded body, the propylene-based polymer (C') preferably has a content of the ethylene structural unit contained in the polymer of 1 mol% or less, more preferably an ethylene-free structural unit. A propylene homopolymer. Further, the above polymer may be a polymer using a monomer derived from petroleum or coal, or a polymer using a monomer derived from a raw material.
本實施形態之彈性體樹脂組合物含有聚丙烯系樹脂(C)之情形時,其含量相對於彈性體樹脂組合物100質量%較佳為5質量%以上,更佳為8質量%以上,進而較佳為11質量%以上,並且較佳為30質量%以下,更佳為20質量%以下。若為5質量%以上,則可期待組合物之強度提高,若為30質量%以下,則不損害柔軟性。When the elastomer resin composition of the present embodiment contains the polypropylene resin (C), the content thereof is preferably 5% by mass or more, more preferably 8% by mass or more, based on 100% by mass of the elastomer resin composition. It is preferably 11% by mass or more, and more preferably 30% by mass or less, and still more preferably 20% by mass or less. When it is 5% by mass or more, the strength of the composition can be expected to be improved, and if it is 30% by mass or less, the flexibility is not impaired.
<其他熱塑性樹脂> 於本實施形態之彈性體樹脂組合物中,根據目的,可將上述彈性體樹脂(A)之一部分、或上述聚丙烯系樹脂(C)之一部分或全部置換成上述彈性體樹脂(A)及上述聚丙烯系樹脂(C)以外之其他熱塑性樹脂。作為其他熱塑性樹脂之具體例,並無特別限定,可例示聚丙烯酸甲酯、聚甲基丙烯酸甲酯、乙烯-丙烯酸乙酯共聚物等丙烯酸系樹脂、聚苯乙烯樹脂、尼龍6、尼龍66、尼龍12等聚醯胺系樹脂、聚醯亞胺系樹脂、乙酸酯系樹脂、聚醚磺酸樹脂、聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯等飽和酯系樹脂、聚碳酸酯、熱塑性聚胺基甲酸酯樹脂、熱塑性彈性體、氯乙烯系樹脂、聚氟乙烯、聚偏二氟乙烯等氟乙烯系樹脂、矽酮樹脂。<Other thermoplastic resin> In the elastomer resin composition of the present embodiment, part or all of the elastomer resin (A) or one or all of the polypropylene resin (C) may be replaced with the elastomer according to the purpose. A thermoplastic resin other than the resin (A) and the above polypropylene resin (C). Specific examples of the other thermoplastic resin are not particularly limited, and examples thereof include acrylic resins such as polymethyl acrylate, polymethyl methacrylate, and ethylene-ethyl acrylate copolymer, polystyrene resin, nylon 6, and nylon 66. Saturated ester resin such as polyacrylamide resin such as nylon 12, polyimide resin, acetate resin, polyether sulfonate resin, polyethylene terephthalate or polybutylene terephthalate A fluoroethylene resin such as polycarbonate, a thermoplastic polyurethane resin, a thermoplastic elastomer, a vinyl chloride resin, a polyvinyl fluoride or a polyvinylidene fluoride, or an anthrone resin.
<添加劑(D)> 本實施形態之彈性體樹脂組合物含有添加劑(D)。添加劑之種類根據彈性體樹脂組合物之使用目的而適當決定。例如就柔軟性或潤滑性之觀點而言,添加劑(D)較佳為含有油。本實施形態之彈性體樹脂組合物可含有1種添加劑,亦可含有2種以上之添加劑。<Additive (D)> The elastomer resin composition of the present embodiment contains the additive (D). The type of the additive is appropriately determined depending on the purpose of use of the elastomer resin composition. The additive (D) preferably contains an oil, for example, from the viewpoint of flexibility or lubricity. The elastomer resin composition of the present embodiment may contain one type of additive or may contain two or more types of additives.
(油) 作為油,並無特別限定,可例示石蠟系加工處理油、環烷系加工處理油、異構石蠟系油等礦物油、芳香族系之礦物油系烴、聚丁烯、聚丁二烯、聚(α-烯烴)等低分子量物等合成樹脂系烴、烷基苯或蓖麻油、亞麻籽油、菜籽油、椰子油等脂肪油系軟化劑、鄰苯二甲酸二丁酯、鄰苯二甲酸二辛酯、己二酸二辛酯、癸二酸二辛酯等酯系塑化劑等。其中,較佳為使用礦物油系烴、石蠟系加工處理油、環烷系加工處理油。特佳為石蠟系烴之碳數占總碳數之50%之石蠟系油。 又,礦物油系烴之重量平均分子量較佳為50~2,000,特佳為100~1,500,40℃之動黏度較佳為3~800 cSt,特佳為5~600 cSt,進而流動點較佳為-40~0℃,特佳為-30~0℃,引火點(COC法)較佳為200~400℃,特佳為250~350℃。 再者,動黏度係依據ISO3104測定之值,流動點係依據JIS K2269:1987測定之值,引火點係依據JIS K2265-4:2007(ASTM-D92,克氏開杯式)測定之值。(Oil) The oil is not particularly limited, and examples thereof include mineral oils such as paraffin-based processing oils, naphthenic processing oils, and isoparaffin oils, aromatic mineral oils, polybutenes, and polybutenes. a synthetic resin-based hydrocarbon such as a low molecular weight substance such as a diene or a poly(α-olefin), a fatty oil softener such as alkylbenzene or castor oil, linseed oil, rapeseed oil or coconut oil, or dibutyl phthalate. An ester plasticizer such as dioctyl phthalate, dioctyl adipate or dioctyl sebacate. Among them, mineral oil-based hydrocarbons, paraffin-based processed oils, and naphthenic processed oils are preferably used. It is particularly preferred to be a paraffinic oil having a carbon number of paraffinic hydrocarbons of 50% of the total carbon number. Further, the weight average molecular weight of the mineral oil-based hydrocarbon is preferably from 50 to 2,000, particularly preferably from 100 to 1,500, and the dynamic viscosity at 40 ° C is preferably from 3 to 800 cSt, particularly preferably from 5 to 600 cSt, and further preferably a flow point is obtained. It is -40 to 0 ° C, particularly preferably -30 to 0 ° C, and the ignition point (COC method) is preferably 200 to 400 ° C, particularly preferably 250 to 350 ° C. Further, the dynamic viscosity is a value measured according to ISO 3104, the flow point is a value measured in accordance with JIS K2269:1987, and the ignition point is a value measured in accordance with JIS K2265-4:2007 (ASTM-D92, Kelvin open cup type).
作為石蠟系加工處理油之市售品,可列舉出光興產(股)製造之「Diana Process Oil PW-32」、「Diana Process Oil PW-90」、「Diana Process Oil PW-150」、「Diana Process Oil PS-32」、「Diana Process Oil PS-90」、「Diana Process Oil PS-430」;Chevron USA公司製造之「Kaydol Oil」、「ParaLux Oil」等(均為商品名)。As a commercial product of the paraffin-based processing oil, "Diana Process Oil PW-32", "Diana Process Oil PW-90", "Diana Process Oil PW-150", "Diana" manufactured by K.K. Process Oil PS-32", "Diana Process Oil PS-90", "Diana Process Oil PS-430"; "Kaydol Oil" and "ParaLux Oil" manufactured by Chevron USA (both trade names).
作為油以外之添加劑,例如可列舉表面改質劑;防老化劑(胺系、酚系、硫系、磷系、蠟);硫化劑;硫化促進劑(亞磺醯胺系、秋蘭姆系、噻唑系、胍系);鋅白等硫化促進助劑;硫化抑制劑;素煉促進劑;白色填充劑;偶合劑;自由基產生劑;聚烯烴;滑澤劑;抗黏連劑;熱穩定劑;酚系抗氧化劑、亞磷酸酯系抗氧化劑、硫醚系抗氧化劑等抗氧化劑;光穩定劑;紫外線吸收劑;結晶成核劑;抗黏連劑;密封性改良劑;硬脂酸、矽酮油等脫模劑;聚乙烯蠟等潤滑劑;著色劑;陶瓷、碳黑、棕土、富鐵黃土、高嶺土、鈦鎳黃、鈷藍、色母粒灰、喹酞酮、吡咯并吡咯二酮、喹吖啶酮、二㗁 𠯤、酞菁藍、酞菁綠等顏料;滑石、二氧化矽、碳酸鈣、碳酸鎂、氫氧化鋁、硫酸鋇、玻璃纖維、碳纖維、合成纖維、天然纖維、玻璃粉、玻璃中空球等無機中空填料;陶瓷粉、雲母、氧化鋁、滑石、碳酸鈣、矽灰石、黏土等無機填充劑;木塞粉末、木粉、石墨等有機填充劑;發泡劑;水合化合物、紅磷、聚磷酸銨、銻、矽酮等阻燃劑;抗靜電劑;抗菌劑;分散劑、相溶劑、松香衍生物等黏著賦予劑(增黏劑);「LEOSTOMER(註冊商標)B」(商品名,Rikentechnos(股)製造)等接著性彈性體;薰草咔樹脂、薰草咔-茚樹脂、酚萜樹脂等。Examples of the additives other than the oil include surface modifiers; anti-aging agents (amine, phenol, sulfur, phosphorus, and wax); vulcanizing agents; vulcanization accelerators (sulfinamide, thiuram) , thiazole series, lanthanide series; zinc white and other vulcanization accelerators; vulcanization inhibitors; mastic accelerators; white fillers; coupling agents; free radical generators; polyolefins; slip agents; anti-blocking agents; Stabilizer; antioxidants such as phenolic antioxidants, phosphite antioxidants, thioether antioxidants; light stabilizers; ultraviolet absorbers; crystal nucleating agents; anti-blocking agents; seal improvers; stearic acid , release agent such as ketone oil; lubricant such as polyethylene wax; colorant; ceramic, carbon black, brown earth, rich iron loess, kaolin, titanium nickel yellow, cobalt blue, masterbatch ash, quinophthalone, pyrrole Pigments such as pyrrole dione, quinacridone, diterpene, phthalocyanine blue, phthalocyanine green; talc, ceria, calcium carbonate, magnesium carbonate, aluminum hydroxide, barium sulfate, glass fiber, carbon fiber, synthetic fiber Inorganic hollow fillers such as natural fibers, glass powder, and glass hollow spheres; Inorganic fillers such as porcelain powder, mica, alumina, talc, calcium carbonate, ash stone, clay; organic fillers such as cork powder, wood powder, graphite; foaming agent; hydrated compound, red phosphorus, ammonium polyphosphate, Flame retardants such as hydrazine and fluorenone; antistatic agents; antibacterial agents; adhesion promoters such as dispersants, phase solvents, and rosin derivatives (tackifiers); "LEOSTOMER (registered trademark) B" (trade name, Rikentechnos) ) manufacturing) an adhesive elastomer; scented scented resin, scented scented enamel resin, phenolphthalein resin, and the like.
作為抗氧化劑,可例示亞磷酸三(壬基苯基)酯、二硬脂基季戊四醇二亞磷酸酯、Adekastab 1178(ADEKA(股)製造,「Adekastab」為註冊商標)、Sumilizer TNP(住友化學(股)製造,「Sumilizer」為註冊商標)、Irgafos 168(BASF公司製造,「Irgafos」為註冊商標)、Sandostab P-EPQ(Sandoz公司製造,「Sandostab」為註冊商標)等磷系抗氧化劑,2,6-二第三丁基-4-甲基苯酚、3-(3',5'-二第三丁基-4'-羥基苯基)丙酸正十八烷基酯、Irganox 1010(BASF公司製造,「Irganox」為註冊商標)等酚系抗氧化劑,3,3'-硫代二丙酸二月桂酯、季戊四醇四(3-月桂基硫代丙酸酯)、Sumilizer TPL(住友化學(股)製造)、DSTP「Yoshitomi」(三菱化學(股)製造,「Yoshitomi」為註冊商標)、Antiox L(日油(股)製造,「Antiox」為註冊商標)等硫系抗氧化劑等。Examples of the antioxidant include tris(nonylphenyl)phosphite, distearyl pentaerythritol diphosphite, Adekastab 1178 (made by ADEKA Co., Ltd., "Adekastab" is a registered trademark), and Sumilizer TNP (Sumitomo Chemical (" Manufactured by the company, "Sumilizer" is a registered trademark), Irgafos 168 (manufactured by BASF, "Irgafos" is a registered trademark), Sandostab P-EPQ (manufactured by Sandoz, "Sandostab" is a registered trademark), etc., 2 , 6-di-tert-butyl-4-methylphenol, 3-(3',5'-di-t-butyl-4'-hydroxyphenyl)propionic acid n-octadecyl ester, Irganox 1010 (BASF A phenolic antioxidant such as "Irganox" is a registered trademark), dilauryl 3,3'-thiodipropionate, pentaerythritol tetrakis(3-laurylthiopropionate), Sumilizer TPL (Sumitomo Chemical ( It is a sulfur-based antioxidant such as DSTP "Yoshitomi" (manufactured by Mitsubishi Chemical Co., Ltd., "Yoshitomi" is a registered trademark), Antiox L (made by Nippon Oil Co., Ltd., "Antiox" is a registered trademark).
本實施形態之彈性體樹脂組合物可發泡。作為發泡劑,可列舉二氧化碳氣體、氮氣;偶氮二異丁腈、偶氮二甲醯胺、偶氮二羧酸鋇等偶氮系化合物;N,N'-二亞硝基五亞甲基四胺、三亞甲基三硝基胺等N-亞硝基系化合物;對甲苯磺醯肼、二苯碸-3,3'-二磺醯肼、4,4'-氧雙(苯磺醯肼)、烯丙基雙(磺醯肼)等磺醯肼系化合物;對甲苯基磺醯半卡肼、4,4'-氧雙(苯磺醯半卡肼)等磺醯半卡肼系化合物。該等可單獨使用1種,亦可併用2種以上。The elastomer resin composition of the present embodiment can be foamed. Examples of the foaming agent include carbon dioxide gas and nitrogen; azo compounds such as azobisisobutyronitrile, azodimethylamine, and azobiscarboxylate; and N,N'-dinitrosium penta N-nitroso compounds such as tetramine, trimethylenetrinitroamine; p-toluenesulfonate, diphenylguanidine-3,3'-disulfonium, 4,4'-oxybis(benzenesulfonate) Sulfonium compound such as 醯肼), allyl bis(sulfonate); sulfonium sulfonium compound such as p-tolylsulfonium semicarbazone or 4,4'-oxybis(phenylsulfonium sulfonium) a compound. These may be used alone or in combination of two or more.
添加劑(D)為油之情形之含量相對於彈性體樹脂組合物100質量%,較佳為10質量%以上,更佳為20質量%以上,並且較佳為70質量%以下,更佳為60質量%以下,進而較佳為50質量%以下。若為10質量%以上,則可期待由添加劑產生之效果,若為70質量%以下,則可期待添加劑之滲出之控制。The content of the additive (D) in the case of the oil is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 70% by mass or less, and more preferably 60% by mass based on 100% by mass of the elastomer resin composition. The mass% or less is more preferably 50% by mass or less. When it is 10% by mass or more, the effect by the additive can be expected, and if it is 70% by mass or less, the control of the bleeding of the additive can be expected.
進而,於本實施形態之彈性體樹脂組合物中,能夠添加交聯劑或交聯助劑等而使其部分交聯。 作為交聯劑,可列舉有機過氧化物、硫、硫化合物、酚樹脂等酚系硫化劑等。該等之中,較佳為有機過氧化物。作為有機過氧化物之具體例,可列舉2,5-二甲基-2,5-二(第三丁基過氧基)-己烷、2,5-二甲基-2,5-二(第三丁基過氧基)-3-己炔;2,5-二甲基-2,5-二(苯甲醯基過氧基)-己烷;過氧化苯甲酸第三丁酯;過氧化二異丙苯;過氧化第三丁基異丙苯;氫過氧化二異丙基苯;1,3-雙(第三丁基過氧基異丙基)苯;過氧化苯甲醯;1,1-二(第三丁基過氧基)-3,3,5-三甲基環己烷;過氧化二第三丁基;4,4-雙(第三丁基過氧基)戊酸正丁酯;過氧化對氯苯甲醯;過氧化2,4-二氯苯甲醯;過氧化異丙基碳酸第三丁酯;過氧化二乙醯;過氧化月桂醯等。該等之中,就臭氣性、焦化穩定性之觀點而言,較佳為2,5-二甲基-2,5-二(第三丁基過氧基)己烷、2,5-二甲基-2,5-二(第三丁基過氧基)-3-己炔、1,3-雙(第三丁基過氧基異丙基)苯、1,1-雙(第三丁基過氧基)-3,3,5-三甲基環己烷、4,4-雙(第三丁基過氧基)戊酸正丁酯,其中,最佳為1,3-雙(第三丁基過氧基異丙基)苯。Further, in the elastomer resin composition of the present embodiment, a crosslinking agent, a crosslinking assistant or the like can be added and partially crosslinked. Examples of the crosslinking agent include a phenolic vulcanizing agent such as an organic peroxide, sulfur, a sulfur compound, and a phenol resin. Among these, an organic peroxide is preferred. Specific examples of the organic peroxide include 2,5-dimethyl-2,5-di(t-butylperoxy)-hexane and 2,5-dimethyl-2,5-di. (t-butylperoxy)-3-hexyne; 2,5-dimethyl-2,5-bis(benzhydrylperoxy)-hexane; tert-butyl peroxybenzoate; Dicumyl peroxide; tert-butyl cumene peroxide; diisopropylbenzene hydroperoxide; 1,3-bis(t-butylperoxyisopropyl)benzene; benzoyl peroxide ; 1,1-di(t-butylperoxy)-3,3,5-trimethylcyclohexane; di-tert-butyl peroxide; 4,4-bis(t-butylperoxy N-butyl valerate; p-chlorobenzhydryl peroxide; 2,4-dichlorobenzhydryl peroxide; tert-butyl isopropyl peroxycarbonate; diethyl hydrazine peroxide; Among these, from the viewpoints of odor and coking stability, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5- is preferred. Dimethyl-2,5-di(t-butylperoxy)-3-hexyne, 1,3-bis(t-butylperoxyisopropyl)benzene, 1,1-double (first Tributylperoxy)-3,3,5-trimethylcyclohexane, 4,4-bis(t-butylperoxy)pentanoic acid n-butyl ester, of which the optimum is 1,3- Bis(t-butylperoxyisopropyl)benzene.
又,作為交聯助劑,例如可列舉N-甲基-N,4-二亞硝基苯胺、亞硝基苯、二苯胍、二乙烯苯、三羥甲基丙烷三(甲基)丙烯酸酯、伸乙基二(甲基)丙烯酸酯、二乙二醇二(甲基)丙烯酸酯、(甲基)丙烯酸烯丙酯、鄰苯二甲酸二烯丙酯、氰尿酸三烯丙酯、醌二肟、p,p'-二苯甲醯基醌二肟、雙馬來醯亞胺、伸苯基雙馬來醯亞胺、三羥甲基丙烷-N,N'-間伸苯基二馬來醯亞胺、乙二醇二甲基丙烯酸酯、乙烯醇縮丁醛、硬脂酸乙烯酯、不飽和矽烷化合物、硫等。藉由使用此種交聯助劑,可期待均勻且緩和之交聯反應。 該等交聯助劑之中,較佳為氰尿酸三烯丙酯、乙二醇二甲基丙烯酸酯、二乙烯苯、雙馬來醯亞胺。該等容易操作,與作為被交聯處理物之主成分之彈性體樹脂(A)及聚丙烯系樹脂(B)之相溶性良好,且具有溶解有機過氧化物之作用,發揮作為有機過氧化物之分散劑之作用,故可獲得利用熱處理所得之交聯效果均質,取得柔軟性與物性之平衡之彈性體樹脂組合物。Further, examples of the crosslinking assistant include N-methyl-N,4-dinitrosoaniline, nitrosobenzene, diphenylguanidine, divinylbenzene, and trimethylolpropane tri(meth)acrylic acid. Ester, ethyl di(meth) acrylate, diethylene glycol di(meth) acrylate, allyl (meth) acrylate, diallyl phthalate, triallyl cyanurate, Bismuth, p,p'-dibenzimidylindole, bismaleimide, phenyl bismaleimide, trimethylolpropane-N, N'-metaphenyl Dimaleimide, ethylene glycol dimethacrylate, vinyl butyral, vinyl stearate, unsaturated decane compounds, sulfur, and the like. By using such a crosslinking assistant, a uniform and mild crosslinking reaction can be expected. Among these crosslinking assistants, triallyl cyanurate, ethylene glycol dimethacrylate, divinylbenzene, and bismaleimide are preferred. These are easy to handle, and have good compatibility with the elastomer resin (A) and the polypropylene resin (B) which are main components of the crosslinked processed material, and have an action of dissolving an organic peroxide, and exhibit organic peroxide. Since the dispersing agent functions as a dispersing agent, it is possible to obtain an elastomer resin composition in which the crosslinking effect by heat treatment is uniform and a balance between flexibility and physical properties is obtained.
交聯劑及交聯助劑可分別使用1種,亦可組合2種以上使用。 使用交聯劑及交聯助劑之情形時相對於(A)~(D)成分之合計量100質量份,可於0.1~5質量份之範圍內任意使用而調整交聯度。 再者,使用不飽和矽烷化合物作為交聯助劑之情形時,可進一步於矽烷醇縮合觸媒之存在下與水分接觸而使交聯進行。The crosslinking agent and the crosslinking auxiliary agent may be used alone or in combination of two or more. In the case of using a crosslinking agent and a crosslinking auxiliary agent, the crosslinking degree can be adjusted arbitrarily in the range of 0.1 to 5 parts by mass based on 100 parts by mass of the total of the components (A) to (D). Further, when an unsaturated decane compound is used as the crosslinking assistant, the crosslinking can be further progressed by contact with moisture in the presence of a decyl alcohol condensation catalyst.
<彈性體樹脂組合物之製造> 本實施形態之彈性體樹脂組合物係藉由添加上述彈性體樹脂(A)、聚丙烯系樹脂(B)、及添加劑(D),進而視需要添加聚丙烯系樹脂(C)進行調配、熔融混練而獲得。本實施形態之彈性體樹脂組合物可採用硫化橡膠之製造方法進行製造。 又,本實施形態之彈性體樹脂組合物亦可採用熱塑性樹脂組合物之製造方法進行製造。例如可乾摻彈性體樹脂(A)及聚丙烯系樹脂(B)之顆粒後,投入至擠出機之料斗進行熔融混練。又,亦可藉由聚合裝置製造聚丙烯系樹脂(B)後,添加彈性體樹脂(A)之顆粒,使用連結於聚合裝置之擠出機進行熔融混練。又,亦可於溶劑中存在聚丙烯系樹脂(B)之狀態下,添加彈性體樹脂(A),經過溶劑去除及乾燥步驟而獲得顆粒或塊(bale)。進而,亦可使彈性體樹脂(A)聚合後,於溶劑脫氣前將聚丙烯系樹脂(B)進行溶液混合並脫溶劑而製造彈性體樹脂(A)及聚丙烯系樹脂(B)之組合物。其後,視需要亦可進行造粒。不論造粒步驟之有無,均可將包含彈性體樹脂(A)及聚丙烯系樹脂(B)之上述混練後之組合物與添加劑(D)、進而視需要與聚丙烯系樹脂(C)進行混練。藉由採取此種步驟,例如添加劑(D)為油之情形時,將彈性體樹脂(A)與油進行混練時,即便不預先將彈性體樹脂(A)浸入至油中,亦能夠使兩者容易地進行混練。 混練可使用通常使用之機器,例如可使用高速混合機、班布里混合機、連續捏合機、單軸或雙軸擠出機、輥、布氏塑性測定器等通常之混合混練機進行。亦可藉由擠出機以外之混練機進行混練後,使用擠出機進行顆粒化。<Production of the elastomer resin composition> The elastomer resin composition of the present embodiment is added with the above-mentioned elastomer resin (A), polypropylene resin (B), and additive (D), and optionally polypropylene. The resin (C) is obtained by blending and melt-kneading. The elastomer resin composition of the present embodiment can be produced by a method for producing a vulcanized rubber. Further, the elastomer resin composition of the present embodiment can also be produced by a method for producing a thermoplastic resin composition. For example, the particles of the elastomer resin (A) and the polypropylene resin (B) may be dry-blended, and then placed in a hopper of an extruder to be melt-kneaded. Further, after the polypropylene resin (B) is produced by a polymerization apparatus, the particles of the elastomer resin (A) are added, and the mixture is melt-kneaded by using an extruder connected to a polymerization apparatus. Further, the elastomer resin (A) may be added in a state where the polypropylene resin (B) is present in a solvent, and a pellet or a block may be obtained by a solvent removal and drying step. Further, after the elastomer resin (A) is polymerized, the polypropylene resin (B) may be solution-mixed and desolventized before the solvent is degassed to produce the elastomer resin (A) and the polypropylene resin (B). combination. Thereafter, granulation can also be carried out as needed. The above-mentioned kneaded composition containing the elastomer resin (A) and the polypropylene resin (B), the additive (D), and optionally the polypropylene resin (C) may be used regardless of the granulation step. Mixed. By taking such a step, for example, when the additive (D) is an oil, when the elastomer resin (A) is kneaded with the oil, even if the elastomer resin (A) is not immersed in the oil in advance, two can be made. It is easy to carry out mixing. The kneading can be carried out using a commonly used machine, for example, a general mixing kneader such as a high speed mixer, a Banbury mixer, a continuous kneader, a uniaxial or biaxial extruder, a roll, a Brookfield tester, or the like. It is also possible to perform granulation using an extruder after kneading by a kneader other than an extruder.
<彈性體樹脂組合物之物性> 就耐熱性之觀點而言,本實施形態之彈性體樹脂組合物需要於230℃下不顯示流動性。於本發明中,「於230℃下不顯示流動性」係指於烘箱空氣下以230℃加熱對彈性體樹脂組合物進行熱壓成形而獲得之5 mm×5 mm×厚度1 mm之成形體15分鐘時維持形狀。<Physical Properties of Elastomer Resin Composition> The elastomer resin composition of the present embodiment does not exhibit fluidity at 230 ° C from the viewpoint of heat resistance. In the present invention, "the fluidity is not exhibited at 230 ° C" means a molded body of 5 mm × 5 mm × 1 mm thick which is obtained by hot press forming an elastomer resin composition by heating at 230 ° C under an oven atmosphere. Maintain shape at 15 minutes.
本實施形態之彈性體樹脂組合之臭氧耐性優異。由於臭氧耐性越高則耐久性變得越高,故依據JIS K6259-1:2015之附屬文件JA進行之關於龜裂狀態之評價較佳為96小時後不破斷,更佳為未達到「A-5」、「B-5」及「C-5」,進而較佳為未達到「A-4」、「B-4」及「C-4」,進而更佳為未達到「A-3」、「B-3」及「C-3」,特佳為未達到「A-2」、「B-2」及「C-2」。 再者,如JIS K6259-1:2015之附屬文件JA中所記載,組合龜裂之數目及大小進行評價。關於龜裂之數目,分A、B、C之3個等級進行評價,較佳為龜裂較少之評價A。又,關於龜裂之大小,分1~5之5個等級進行評價,較佳為龜裂較小之評價1。The elastomer resin combination of the present embodiment is excellent in ozone resistance. Since the durability is higher as the ozone resistance is higher, the evaluation of the crack state according to the attached document JA of JIS K6259-1:2015 is preferably not broken after 96 hours, and more preferably not reached "A- 5", "B-5" and "C-5", and preferably not "A-4", "B-4" and "C-4", and even better not "A-3" "B-3" and "C-3" are particularly good for "A-2", "B-2" and "C-2". Furthermore, as described in the attached document JA of JIS K6259-1:2015, the number and size of the combined cracks were evaluated. Regarding the number of cracks, it is evaluated in three grades of A, B, and C, and it is preferable to evaluate A which has less cracks. Further, the size of the crack is evaluated in five grades of 1 to 5, and it is preferable to evaluate the crack 1 which is small.
<成形體> 本發明之成形體係包含上述樹脂組合物者。 可藉由利用公知之成形方法,例如利用模具之加壓成形等方法使上述樹脂組合物成形而獲得所需形狀之成形體。又,成形體亦可藉由利用壓延、積層、模具、擠出、壓入式成形使上述樹脂組合物成形後,加熱使其交聯而獲得。 實施例<Molded body> The molding system of the present invention contains the above resin composition. The resin composition can be molded by a known molding method, for example, by press molding using a mold to obtain a molded body having a desired shape. Further, the molded body can be obtained by molding the resin composition by rolling, laminating, die, extrusion, and press-molding, followed by heating and crosslinking. Example
其次藉由實施例具體地說明本發明,但本發明毫不受該等例限定。The invention will be specifically described by way of examples, but the invention is not limited by the examples.
實施例及比較例中使用之原料如下所示。 <彈性體樹脂(A)> ・(A-1)「Nordel(註冊商標)IP 4760P」:乙烯-丙烯-亞乙基降𦯉烯共聚物,Dow Chemical公司製造,乙烯單元含量:67重量%,亞乙基降𦯉烯單元含量:4.9重量%,慕尼黏度(ML(1+4),125℃):60 ・(A-2)「JSR IR2200」:聚異戊二烯橡膠,JSR(股)製造,慕尼黏度(ML(1+4),125℃):82 ・(A-3)「JSR SL552」:溶液聚合苯乙烯丁二烯橡膠(S-SBR),JSR(股)製造,鍵結苯乙烯:23.5%,乙烯基鍵結量:33.5%,比重:0.94,慕尼黏度(ML(1+4),125℃):55 ・(A-4)天然橡膠(NR),RSS3號The materials used in the examples and comparative examples are as follows. <Elastomer resin (A)> ・(A-1) "Nordel (registered trademark) IP 4760P": ethylene-propylene-ethylene decene copolymer, manufactured by Dow Chemical Co., Ltd., ethylene unit content: 67% by weight, Ethylene norbornene unit content: 4.9 wt%, Mooney viscosity (ML (1+4), 125 ° C): 60 ・(A-2) "JSR IR2200": Polyisoprene rubber, manufactured by JSR (share) , Mooney viscosity (ML (1+4), 125 ° C): 82 ・(A-3) "JSR SL552": solution polymerization styrene butadiene rubber (S-SBR), manufactured by JSR (share), bonded styrene : 23.5%, vinyl bond amount: 33.5%, specific gravity: 0.94, Mui viscosity (ML (1+4), 125 ° C): 55 ・(A-4) natural rubber (NR), RSS3
<聚丙烯系樹脂(B)> ・(B-1)「L-MODU S400」:藉由二茂金屬觸媒而獲得之聚丙烯系樹脂,出光興產(股)製造,熔解吸熱量(ΔH-D)=36 J/g,熔點(Tm-D)=80℃,極限黏度[η]=0.51 dL/g,分子量分佈(Mw/Mn)=2.0<Polypropylene resin (B)> ・(B-1) "L-MODU S400": Polypropylene resin obtained by a metallocene catalyst, manufactured by Idemitsu Kosan Co., Ltd., melting heat absorption (ΔH) -D)=36 J/g, melting point (Tm-D)=80°C, ultimate viscosity [η]=0.51 dL/g, molecular weight distribution (Mw/Mn)=2.0
<添加劑(D)> ・(D1-1)「Diana Process Oil PW-90」:石蠟系油,出光興產(股)製造,40℃之動黏度90 cSt,流動點-17.5℃,引火點266℃ ・(D1-2)「Diana Process Oil NS-100」:環烷系油,出光興產(股)製造,40℃之動黏度95 cSt,流動點-37.5℃,引火點226℃ ・(D2-1)硬脂酸,分散劑/潤滑劑,日油(股)製造 ・(D2-2)「Struktol EF44」,分散劑/潤滑劑,S&S Japan(股)製造 ・(D3)氧化鋅(第2種),硫化促進助劑,堺化學工業(股)製造 ・(D4-1)碳黑(高耐磨爐黑(HAF,High Abrasion Furnace)),補強劑,三菱化學(股)製造 ・(D4-2)碳黑(超耐磨爐黑(SAF,Super Abrasion Furnace)),補強劑,Tokai Carbon(股)製造 ・(D4-3)「Nipsil VN3」:二氧化矽,補強劑,Tosoh Silica(股)製造 ・(D5-1)「SANCELER NS」:亞磺醯胺(SA)系硫化促進劑,N-(第三丁基)-2-苯并噻唑亞磺醯胺(TBBS),三新化學工業(股)製造 ・(D5-2)「Nocceler CZ」:亞磺醯胺(SA)系硫化促進劑,N-環己基-2-苯并噻唑亞磺醯胺,三新化學工業(股)製造 ・(D5-3)「Nocceler D」:胍系硫化促進劑,1,3-二苯胍,三新化學工業(股)製造 ・(D6)硫,硫化劑,細井化學工業(股)製造 ・(D7-1)「Sunnoc」:特殊蠟系防老化劑,大內新興化學工業(股)製造 ・(D7-2)「Nocrac 6C」:芳香族二級胺系防老化劑,大內新興化學工業(股)製造 ・(D7-3)「Nocrac 224」:胺-酮系防老化劑,大內新興化學工業(股)製造 ・(D8)「Si 69」:矽烷偶合劑,Evonik公司製造 ・(D9)「Struktol AW-1」,抗靜電劑,S&S Japan(股)製造<Additive (D)> ・(D1-1) "Diana Process Oil PW-90": Paraffin-based oil, manufactured by Idemitsu Kosan Co., Ltd., with a dynamic viscosity of 40 cSt at 40 ° C, a flow point of -17.5 ° C, and a fire point of 266 °C ・(D1-2) "Diana Process Oil NS-100": naphthenic oil, manufactured by Idemitsu Kosan Co., Ltd., with a dynamic viscosity of 40 cSt at 40 ° C, a flow point of -37.5 ° C, and a fire point of 226 ° C. -1) Stearic acid, dispersant/lubricant, manufactured by Nippon Oil Co., Ltd., (D2-2) "Struktol EF44", dispersant/lubricant, manufactured by S&S Japan, (D3) zinc oxide (No.) (2 types), vulcanization accelerator, 堺Chemical Industry Co., Ltd., (D4-1) carbon black (High Abrasion Furnace), reinforcing agent, Mitsubishi Chemical Co., Ltd. D4-2) Carbon black (Super Abrasion Furnace), reinforcing agent, manufactured by Tokai Carbon (D4-3) "Nipsil VN3": cerium oxide, reinforcing agent, Tosoh Silica (Stock) Manufacture (D5-1) "SANCELER NS": sulfinamide (SA) vulcanization accelerator, N-(t-butyl)-2-benzothiazole sulfinamide (TBBS), three New Chemical Industry Co., Ltd. (D5-2) "Nocceler CZ": Sulfaguanamine (SA) is sulfur Promoter, N-cyclohexyl-2-benzothiazole sulfinamide, manufactured by Sanshin Chemical Industry Co., Ltd. (D5-3) "Nocceler D": lanthanide vulcanization accelerator, 1,3-diphenyl hydrazine , Sanshin Chemical Industry Co., Ltd. (D6) Sulfur, Vulcanizing Agent, Manufacturing of Sosui Chemical Industry Co., Ltd. (D7-1) "Sunnoc": Special Wax Anti-Aging Agent, Ouchi Emerging Chemical Industry Co., Ltd. Manufacture (D7-2) "Nocrac 6C": an aromatic secondary amine anti-aging agent, manufactured by Ouchi Shinko Chemical Co., Ltd. (D7-3) "Nocrac 224": an amine-ketone anti-aging agent, (D8) "Si 69": decane coupling agent, manufactured by Evonik, (D9) "Struktol AW-1", antistatic agent, manufactured by S&S Japan Co., Ltd.
<交聯劑> ・「Perhexa 25B」:2,5-二甲基-2,5-二(第三丁基過氧基)己烷,日油(股)製造<Crosslinking agent> ・"Perhexa 25B": 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, manufactured by Nippon Oil Co., Ltd.
再者,聚丙烯系樹脂(B-1)之物性係藉由下述方法測定。 [DSC測定] 根據熔解吸熱曲線求出熔解吸熱量(ΔH-D),上述熔解吸熱曲線係藉由使用示差掃描式熱量計(Perkin Elmer公司製造,「DSC-7」),將10 mg之試樣於氮氣環境下在-10℃下保持5分鐘後,以10℃/min升溫而獲得。又,根據於獲得之熔解吸熱曲線之最高溫側所觀測到之波峰之峰頂求出熔點(Tm-D)。 再者,熔解吸熱量(ΔH-D)係將連接無熱量變化之低溫側之點與無熱量變化之高溫側之點之線作為基準線,藉由求出利用使用示差掃描式熱量計(Perkin Elmer公司製造,「DSC-7」)之DSC測定而獲得之熔解吸熱曲線之包含波峰之線部分與該基準線所包圍之面積而算出。Further, the physical properties of the polypropylene resin (B-1) were measured by the following methods. [DSC measurement] The melting endothermic amount (ΔH-D) was determined from the melting endothermic curve, and the melting endothermic curve was tested by using a differential scanning calorimeter ("DSC-7", manufactured by Perkin Elmer Co., Ltd.). After maintaining at -10 ° C for 5 minutes under a nitrogen atmosphere, the temperature was raised at 10 ° C / min. Further, the melting point (Tm-D) was determined from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve. Further, the heat of fusion (ΔH-D) is obtained by using a differential scanning calorimeter (Perkin) using a line connecting a point on the low temperature side where no heat is changed and a point on the high temperature side where no heat is changed as a reference line. The melting endothermic curve obtained by the DSC measurement of the "DSC-7" manufactured by Elmer Corporation is calculated by the area of the peak including the peak and the area surrounded by the reference line.
[極限黏度[η]] 使用黏度計(離合公司(股)製造,商品名:「VMR-053U-PC・F01」)、烏氏黏度管(測時球容積:2~3 mL,毛細管直徑:0.44~0.48 mm)、及作為溶劑之萘滿,於135℃下測定0.02~0.16 g/dL之溶液。 [分子量分佈(Mw/Mn)] 藉由凝膠滲透層析(GPC)法測定重量平均分子量(Mw)及數量平均分子量(Mn),求出分子量分佈(Mw/Mn)。測定係使用下述裝置及條件,獲得聚苯乙烯換算之重量平均分子量及數量平均分子量。分子量分佈(Mw/Mn)係由該等重量平均分子量(Mw)及數量平均分子量(Mn)算出之值。 <GPC測定裝置> 管柱:Tosoh(股)製造之「TOSO GMHHR-H(S)HT」 檢測器:液相層析圖用折射率(RI,Refractive Index)檢測 Waters Corporation製造之「WATERS 150C」 <測定條件> 溶劑:1,2,4-三氯苯 測定溫度:145℃ 流速:1.0 mL/min 試樣濃度:2.2 mg/mL 注入量:160 μL 校準曲線:通用校準(Universal Calibration) 解析程式:HT-GPC(Ver.1.0)[Limited viscosity [η]] Using a viscometer (manufactured by Clutch Corporation, trade name: "VMR-053U-PC・F01"), Ubbelohde viscosity tube (measuring ball volume: 2 to 3 mL, capillary diameter: 0.44 to 0.48 mm), and a tetralin as a solvent, a solution of 0.02 to 0.16 g/dL was measured at 135 °C. [Molecular weight distribution (Mw/Mn)] The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by a gel permeation chromatography (GPC) method, and the molecular weight distribution (Mw/Mn) was determined. The measurement was carried out using the following apparatus and conditions to obtain a weight average molecular weight and a number average molecular weight in terms of polystyrene. The molecular weight distribution (Mw/Mn) is a value calculated from the weight average molecular weight (Mw) and the number average molecular weight (Mn). <GPC measuring device> Column: "TOSO GMHHR-H(S)HT" manufactured by Tosoh (detector): Liquid chromatogram is used to detect "WATERS 150C" manufactured by Waters Corporation using refractive index (RI, Refractive Index) <Measurement conditions> Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C Flow rate: 1.0 mL/min Sample concentration: 2.2 mg/mL Injection amount: 160 μL Calibration curve: Universal Calibration analysis program :HT-GPC (Ver.1.0)
(評價) 藉由以下所示之測定條件,進行各實施例及比較例中所獲得之彈性體樹脂組合物及加壓板之特性之測定以及評價。(Evaluation) Measurement and evaluation of the properties of the elastomer resin composition and the pressurizing plate obtained in each of the examples and the comparative examples were carried out under the measurement conditions shown below.
(1)滲油性 藉由預先測定過重量之吸油紙(65 mm×97 mm)夾著樣品之加壓板後,進而藉由鋁板(45 mm×45 mm)夾著利用吸油紙夾著之樣品之上下。將其置於槽(vat)內,於其上放置0.5 kg之砝碼,設置於預先設定為70℃之恆溫槽。24小時後自恆溫槽取出樣品,於室溫下放置24小時後,測定吸油紙之重量,將增加之重量作為滲出之油之重量。若滲出之油之重量超過0 g/m2 且為0.40 g/m2 以下,則判定為合格。(1) Oil bleed by sandwiching the pressure plate of the sample with a pre-measured weight of the blotting paper (65 mm × 97 mm), and sandwiching the sample sandwiched by the blotting paper by an aluminum plate (45 mm × 45 mm) Above. It was placed in a vat, and a weight of 0.5 kg was placed thereon, and it was set in a thermostat previously set to 70 °C. After 24 hours, the sample was taken out from the constant temperature bath, and after standing at room temperature for 24 hours, the weight of the oil-absorbing paper was measured, and the increased weight was taken as the weight of the oozing oil. If the weight of the oozing oil exceeds 0 g/m 2 and is 0.40 g/m 2 or less, it is judged to be acceptable.
(2)拉伸彈性模數 使用自製作之加壓板採取之200 mm×15 mm之短條狀之試片,藉由拉力試驗機以夾頭間距離150 mm、拉伸速度100 mm/min進行拉伸,於將伸長率(應變)作為橫軸、將應力作為縱軸之二維座標軸上畫出關係線(曲線),求出降伏點前之關係線之斜率作為「拉伸彈性模數」。再者,拉伸彈性模數之值越高,則加壓板之剛性越優異。(2) Tensile modulus The test piece of 200 mm × 15 mm short strips taken from the produced compression plate was used. The distance between the chucks was 150 mm and the tensile speed was 100 mm/min. Stretching, drawing the relationship line (curve) on the two-dimensional coordinate axis with the elongation (strain) as the horizontal axis and the stress as the vertical axis, and finding the slope of the relationship line before the drop point as the "tensile elastic modulus" "." Further, the higher the value of the tensile elastic modulus, the more excellent the rigidity of the pressure plate.
(3)拉伸斷裂強度 於上述(2)拉伸彈性模數測定中,係藉由用樣品破斷時之應力除以樣品截面積而算出。(3) Tensile breaking strength In the above (2) tensile elastic modulus measurement, it was calculated by dividing the stress at the time of breaking the sample by the cross-sectional area of the sample.
(4)拉伸斷裂伸長率 於上述(2)拉伸彈性模數測定中,將樣品破斷時之伸長率作為拉伸斷裂伸長率。(4) Tensile elongation at break In the above (2) measurement of tensile modulus of elasticity, the elongation at break of the sample was taken as the tensile elongation at break.
(5)蕭氏A硬度 依據JIS K6253-3:2012(類型A)而測定。(5) Shore A hardness is measured in accordance with JIS K6253-3: 2012 (type A).
(6)230℃流動性 於200℃下使用加壓機對彈性體樹脂組合物進行熱壓成形4分鐘,獲得15 mm×15 mm×厚度1 mm之加壓板。自該加壓板切出5 mm×5 mm×厚度1 mm之樣品。將玻璃管烘箱(柴田科學(股)製造,「GTO-200型」)內預先升溫至230℃,於其中將樣品放置於鋁箔上進行設置。加熱15分鐘後,目視觀察是否維持樣品之形狀。將維持樣品之形狀之情形判定為「無:於230℃下不顯示流動性」,將未維持樣品之形狀之情形判定為「有:於230℃顯示流動性」。(6) Flowability at 230 ° C The elastomer resin composition was subjected to hot press forming at 200 ° C for 4 minutes using a press machine to obtain a pressurizing plate of 15 mm × 15 mm × 1 mm in thickness. A sample of 5 mm × 5 mm × 1 mm thickness was cut out from the pressurizing plate. The glass tube oven (manufactured by Shibata Science Co., Ltd., "GTO-200 type") was previously heated to 230 ° C, and the sample was placed on an aluminum foil to be set. After heating for 15 minutes, it was visually observed whether or not the shape of the sample was maintained. The case where the shape of the sample was maintained was judged as "None: no fluidity was exhibited at 230 ° C", and the case where the shape of the sample was not maintained was judged as "there is: liquidity at 230 ° C".
(7)臭氧劣化試驗 使用電熱壓機(大竹機械工業(股)製造)以160℃對彈性體樹脂組合物進行熱壓成形12分鐘,獲得啞鈴狀1號形之形狀之試片。依據JIS K6259-1:2015,於以下之條件下進行靜態臭氧劣化試驗。 臭氧濃度:50±5 pphm 試驗溫度:40±2℃ 狀態調節溫度:23±2℃ 拉伸應變:20% 使用試驗機:「臭氧耐候試驗機 OMS-HE」(Suga Test Instruments(股)製造)(7) Ozone Deterioration Test The elastomer resin composition was subjected to hot press forming at 160 ° C for 12 minutes using a hot press (manufactured by Otake Machinery Co., Ltd.) to obtain a dumbbell-shaped No. 1 shape test piece. The static ozone deterioration test was carried out under the following conditions in accordance with JIS K6259-1:2015. Ozone concentration: 50±5 pphm Test temperature: 40±2°C Condition adjustment temperature: 23±2°C Tensile strain: 20% Using the test machine: “Ozone weathering test machine OMS-HE” (manufactured by Suga Test Instruments)
將試片暴露於臭氧後,自試驗開始24小時後、48小時後、72小時後、96小時後自試驗槽取出,觀察並記錄龜裂之狀態。評價係依據JIS K6259-1:2015之附屬文件JA進行。再者,如JIS K6259-1:2015之附屬文件JA中所記載,組合龜裂之數目及大小進行評價。關於龜裂之數目,分A、B、C之3個等級進行評價,較佳為龜裂較少之評價A。又,關於龜裂之大小,分1~5之5個等級進行評價,較佳為龜裂較小之評價1。After the test piece was exposed to ozone, it was taken out from the test tank 24 hours later, 48 hours later, 72 hours later, and 96 hours after the start of the test, and the state of the crack was observed and recorded. The evaluation was carried out in accordance with the subsidiary document JA of JIS K6259-1:2015. Furthermore, as described in the attached document JA of JIS K6259-1:2015, the number and size of the combined cracks were evaluated. Regarding the number of cracks, it is evaluated in three grades of A, B, and C, and it is preferable to evaluate A which has less cracks. Further, the size of the crack is evaluated in five grades of 1 to 5, and it is preferable to evaluate the crack 1 which is small.
於本發明中,比起龜裂之數目,龜裂之大小係更重要之因子,較佳為龜裂較小。例如若將A-5評價與B-4評價進行比較,則比起B-4評價,A-5評價之龜裂之數目雖較少,但龜裂較大。此處,龜裂之數目少且龜裂大之A-5評價中,拉伸應力將會集中於較少之龜裂。因此,比起龜裂之數目雖多但其長度卻短之B-4評價,結果A-5評價更易引起開裂。In the present invention, the size of the crack is a more important factor than the number of cracks, and it is preferable that the crack is small. For example, when the A-5 evaluation is compared with the B-4 evaluation, the number of cracks evaluated by the A-5 is smaller than that of the B-4 evaluation, but the crack is large. Here, in the A-5 evaluation in which the number of cracks is small and the crack is large, the tensile stress will concentrate on fewer cracks. Therefore, compared with the B-4 which has a large number of cracks but a short length, the A-5 evaluation is more likely to cause cracking.
實施例1~2、比較例1~2、及參考例1 使用Laboplastomill於230℃下對表1中所記載之種類及調配量之各成分進行熔融混練3分鐘,製備彈性體樹脂組合物。於200℃下使用加壓機對獲得之彈性體樹脂組合物進行熱壓成形4分鐘,獲得30 mm×30 mm×厚度1 mm之加壓板。再者,表1中,空欄表示未調配。Examples 1 to 2, Comparative Examples 1 and 2, and Reference Example 1 Each component of the type and the amount described in Table 1 was melt-kneaded at 230 ° C for 3 minutes using a Laboplastomill to prepare an elastomer resin composition. The obtained elastomer resin composition was subjected to hot press forming at 200 ° C for 4 minutes using a press machine to obtain a pressurizing plate of 30 mm × 30 mm × 1 mm in thickness. Furthermore, in Table 1, the blank column indicates that it is not allocated.
實施例3~4、比較例2 於下述條件下對表2中所記載之種類及調配量之各成分進行利用輥之混練,製備彈性體樹脂組合物。再者,表2中,空欄表示未調配。 試驗機:池田機械工業(股)製造,6英吋高溫輥 輥尺寸:6"×16" 前輥旋轉數:25 rpm 前後輥旋轉比:1(前):1.22(後) 輥溫度:80±5℃ 切膠次數:進行3/4切膠3個來回 打卷次數:6次Examples 3 to 4 and Comparative Example 2 Each component of the type and the amount described in Table 2 was kneaded by a roll under the following conditions to prepare an elastomer resin composition. Furthermore, in Table 2, the blank column indicates that it is not allocated. Testing machine: Ikeda Machinery Industry Co., Ltd., 6-inch high-temperature roll size: 6" ×16" Front roller rotation number: 25 rpm Front and rear roller rotation ratio: 1 (front): 1.22 (rear) Roller temperature: 80±5°C Number of times of cutting: 3/4 cutting of rubber 3 times of rolling back and forth: 6 times
實施例5 於下述條件下對表3中所記載之種類及調配量之各成分進行利用輥之混練,製備彈性體樹脂組合物。 試驗機:DAIHAN(股)製造,8英吋水冷輥「HF-2R」 輥尺寸:8"×18" 前輥旋轉數:20 rpm 前後輥旋轉比:1(前):1.15(後) 輥溫度:23℃ 切膠次數:左右各3次 打卷寬度:輥間隙約0.8 mm 打卷次數:5次Example 5 Each component of the type and the amount described in Table 3 was kneaded by a roll under the following conditions to prepare an elastomer resin composition. Testing machine: manufactured by DAIHAN (share), 8 inch water-cooled roll "HF-2R" Roll size: 8" ×18" Front roller rotation number: 20 rpm Front and rear roller rotation ratio: 1 (front): 1.15 (rear) Roller temperature: 23 °C Number of times of cutting: 3 times each side Rolling width: Roll gap: about 0.8 mm Number of shots: 5 times
[表1]
[表2]
[表3]
根據表1~3之結果,可知本發明之彈性體樹脂組合物之臭氧耐性優異。又,根據表1之結果,可知本發明之彈性體樹脂組合物可控制彈性體樹脂組合物中之油之滲出。認為藉由將滲出量控制於適當之範圍內,樹脂組合物之表面被滲出之添加劑塗覆,從而提高臭氧耐性。又,根據表2之結果,可知相比使用蠟系防老化劑(D7-1)之比較例2,使用聚丙烯系樹脂(B)之實施例3及4之臭氧耐性更優異。 [產業上之可利用性]From the results of Tables 1 to 3, it was found that the elastomer resin composition of the present invention is excellent in ozone resistance. Further, from the results of Table 1, it was found that the elastomer resin composition of the present invention can control the bleeding of oil in the elastomer resin composition. It is considered that the surface of the resin composition is coated with the exuded additive by controlling the amount of bleeding within an appropriate range, thereby improving ozone resistance. Further, from the results of Table 2, it was found that the ozone resistance of Examples 3 and 4 using the polypropylene resin (B) was more excellent than Comparative Example 2 using the wax-based anti-aging agent (D7-1). [Industrial availability]
本發明之彈性體樹脂組合物可適當地用於輪胎;緣飾、雨刮器、保險桿等汽車外裝材;儀錶板、中央面板、中央控制台盒、門飾板、車柱、輔助握把、方向盤、氣囊罩蓋等汽車內裝材;齒條與小齒輪套、懸架套、等速接頭套等汽車功能零件;遙控開關、辦公自動化(OA,Office Automation)設備之各種鍵頂、電視、音響、吸塵器等之家電零件;電器製品;泳鏡、防水相機等之罩蓋;各種墊圈;密封材、接著劑;輥;日用雜貨、工業材料、食品等之包裝用片材、膜;食品容器;嬰兒/嬰幼兒用品;電線被覆材、消音齒輪;運動鞋、時尚涼鞋等鞋類;表皮材;皮帶、軟管、管;運動用品;門、窗框材等建材用材料;振動吸收材;各種套圈;閥零件;醫療用石膏、導液管、輸液袋、醫療用注射器墊圈等醫療用品等。The elastomer resin composition of the present invention can be suitably used for tires; automotive exterior materials such as edge trims, wipers, and bumpers; instrument panels, center panels, center console boxes, door trims, pillars, auxiliary grips, Steering wheel, airbag cover and other automotive interior materials; rack and pinion sleeve, suspension sleeve, constant velocity joint sleeve and other automotive functional parts; remote control switch, office automation (OA, Office Automation) equipment, various key tops, TV, audio Household appliances such as vacuum cleaners; electrical appliances; covers for goggles, waterproof cameras, etc.; various gaskets; sealing materials, adhesives; rollers; packaging sheets and films for daily groceries, industrial materials, foods, etc.; Baby/infant products; wire covering materials, silencer gears; sports shoes, fashion sandals and other footwear; skin materials; belts, hoses, tubes; sporting goods; doors, window frames and other building materials; vibration absorption materials; Various ferrules; valve parts; medical gypsum, catheter, infusion bag, medical syringe gasket and other medical supplies.
本發明之彈性體樹脂組合物由於臭氧耐性優異,故可抑制包含彈性體樹脂組合物之成形體之老化。又,根據本發明,於包含彈性體樹脂組合物之成形體中,可藉由適度地控制添加劑之滲出速度使添加劑慢慢滲出,從而於成形品表面發揮添加劑之效果。尤其是於輪胎用途中,含有油作為添加劑之情形時,可抑制由脫油所導致之輪胎之裂紋。又,於輪胎、纜線用途等中,含有蠟作為添加劑之情形時,可藉由適度控制蠟之滲出速度使蠟自輪胎慢慢滲出,從而塗覆輪胎表面,防止輪胎之老化。Since the elastomer resin composition of the present invention is excellent in ozone resistance, deterioration of the molded body including the elastomer resin composition can be suppressed. Moreover, according to the present invention, in the molded body including the elastomer resin composition, the additive can be gradually exuded by appropriately controlling the bleeding rate of the additive, thereby exerting the effect of the additive on the surface of the molded article. In particular, in the case of using a tire as an additive, it is possible to suppress cracking of the tire caused by deoiling. Further, in the case of using a wax as an additive in tires, cable applications, and the like, the wax can be gradually ooze out from the tire by appropriately controlling the bleeding rate of the wax to coat the surface of the tire to prevent aging of the tire.
Claims (12)
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-202703 | 2017-10-19 | ||
JP2017202703 | 2017-10-19 | ||
JP2017252446A JP2019077851A (en) | 2017-10-19 | 2017-12-27 | Elastomer resin composition and molding |
JP2017-252446 | 2017-12-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
TW201922893A true TW201922893A (en) | 2019-06-16 |
Family
ID=66627323
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW107135249A TW201922893A (en) | 2017-10-19 | 2018-10-05 | Elastomer resin composition and molded object |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP2019077851A (en) |
TW (1) | TW201922893A (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7328062B2 (en) * | 2019-08-06 | 2023-08-16 | 住友電気工業株式会社 | cable |
CN110483882B (en) * | 2019-08-13 | 2022-06-03 | 特步(中国)有限公司 | Composition for transparent wear-resistant sole and preparation method thereof |
JP7389702B2 (en) * | 2020-03-31 | 2023-11-30 | 出光興産株式会社 | process oil |
JP6782505B1 (en) * | 2020-04-03 | 2020-11-11 | 株式会社Tbm | A resin composition for producing a stretched sheet, a stretched sheet, and a method for producing a stretched sheet. |
KR102577827B1 (en) * | 2021-06-14 | 2023-09-18 | 주식회사 후레쉬메이트 | Airtight container with excellent antibacterial and antifungal properties, and manufacturing method thereof |
-
2017
- 2017-12-27 JP JP2017252446A patent/JP2019077851A/en active Pending
-
2018
- 2018-10-05 TW TW107135249A patent/TW201922893A/en unknown
Also Published As
Publication number | Publication date |
---|---|
JP2019077851A (en) | 2019-05-23 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW201922893A (en) | Elastomer resin composition and molded object | |
KR101572776B1 (en) | Foam composition, method for producing same, and foam | |
TWI480339B (en) | A crosslinking composition, a method for producing a crosslinked composition, and a molded product | |
JP5972200B2 (en) | Thermoplastic elastomer composition, molded article using the same, and use | |
JP2016113614A (en) | Thermoplastic elastomer composition, crosslinked article, molded body, member, weather seal and corner member for weather seal | |
JP2014210869A (en) | Thermoplastic polymer composition and application thereof | |
KR101577363B1 (en) | Thermoplastic elastomer composition having advanced vibration isolation and thermal resistance and molded article manufactured therefrom | |
TW201837104A (en) | Thermoplastic resin composition and molded body | |
US7411017B2 (en) | Thermoplastic elastomer and molded article thereof | |
WO2019176796A1 (en) | LAMINATE INCLUDING ETHYLENE/α-OLEFIN/NONCONJUGATED POLYENE COPOLYMER COMPOSITION, AND ETHYLENE/α-OLEFIN/NONCONJUGATED POLYENE COPOLYMER COMPOSITION | |
JP6057827B2 (en) | Thermoplastic polymer composition and use thereof | |
JP5055072B2 (en) | Method for producing thermoplastic elastomer composition and molded body | |
JP6029746B2 (en) | Thermoplastic polymer composition and use thereof | |
WO2019077989A1 (en) | Elastomer resin composition and molded object | |
JP2018172532A (en) | Thermoplastic polymer composition and application thereof | |
KR102387508B1 (en) | Polymer compositions and uses thereof | |
JP2022149567A (en) | Thermoplastic elastomer composition, molding, skin for instrument panel, and method for producing thermoplastic elastomer composition | |
JP6994357B2 (en) | A method for manufacturing a resin composition for calender molding, an automobile interior skin material, and a molded product. | |
JP2009073894A (en) | Thermoplastic elastomer composition, production method thereof and molding using the same | |
JP2020111689A (en) | Resin composition, and synthetic wood using the same | |
JP2019044112A (en) | Dynamic crosslinking type thermoplastic elastomer composition for composite molding and composite molded body | |
JP2019044111A (en) | Dynamic crosslinking type thermoplastic elastomer composition and molded body thereof | |
US11746221B2 (en) | Thermoplastic elastomer composition | |
JP6792522B2 (en) | A thermoplastic elastomer composition with a soft touch and a molded product thereof | |
KR20240009507A (en) | Thermoplastic elastomer composition, molded body thereof, and use thereof |