JP2017165867A - Rubber composition for fender - Google Patents
Rubber composition for fender Download PDFInfo
- Publication number
- JP2017165867A JP2017165867A JP2016052622A JP2016052622A JP2017165867A JP 2017165867 A JP2017165867 A JP 2017165867A JP 2016052622 A JP2016052622 A JP 2016052622A JP 2016052622 A JP2016052622 A JP 2016052622A JP 2017165867 A JP2017165867 A JP 2017165867A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- parts
- fender
- sbr
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 137
- 239000005060 rubber Substances 0.000 title claims abstract description 137
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- 239000006229 carbon black Substances 0.000 claims abstract description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 28
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 28
- 229920001194 natural rubber Polymers 0.000 claims abstract description 28
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 22
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 84
- 238000002156 mixing Methods 0.000 claims description 67
- 239000002174 Styrene-butadiene Substances 0.000 description 72
- 235000019241 carbon black Nutrition 0.000 description 44
- 238000004132 cross linking Methods 0.000 description 43
- 239000003921 oil Substances 0.000 description 34
- 235000019198 oils Nutrition 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 20
- 229910052717 sulfur Inorganic materials 0.000 description 20
- 239000011593 sulfur Substances 0.000 description 20
- 239000000872 buffer Substances 0.000 description 13
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000004014 plasticizer Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003712 anti-aging effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 230000003014 reinforcing effect Effects 0.000 description 7
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 6
- 230000003139 buffering effect Effects 0.000 description 6
- 229920003049 isoprene rubber Polymers 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 239000003431 cross linking reagent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000006173 Good's buffer Substances 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 2
- KKPWQIDJDXUWPG-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)benzene-1,4-diamine Chemical compound CC(C)CC(C)NC1=CC=C(N)C=C1 KKPWQIDJDXUWPG-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000703 anti-shock Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 235000012343 cottonseed oil Nutrition 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000003032 molecular docking Methods 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- GPNLWUFFWOYKLP-UHFFFAOYSA-N s-(1,3-benzothiazol-2-yl)thiohydroxylamine Chemical compound C1=CC=C2SC(SN)=NC2=C1 GPNLWUFFWOYKLP-UHFFFAOYSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A30/00—Adapting or protecting infrastructure or their operation
- Y02A30/30—Adapting or protecting infrastructure or their operation in transportation, e.g. on roads, waterways or railways
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、例えば岸壁等に設置されて、船舶の接岸時や係留時に緩衝材として機能する防舷材の形成材料としての防舷材用ゴム組成物に関するものである。 The present invention relates to a rubber composition for a fender as a material for forming a fender that is installed on, for example, a quay and functions as a buffer when a ship is berthed or moored.
岸壁等に設置されて、船舶等の接岸時や係留時に緩衝材として機能する防舷材としては、その全体を弾性材料、特にゴムの架橋物によって一体に形成したものが、構造が簡単でしかも壊れにくいため広く一般に普及している。
かかる防舷材は、架橋性のゴム分にカーボンブラックなどの充填剤、ゴム分を架橋させるための架橋成分、ならびに各種添加剤等を配合して調製したゴム組成物を、所定の防舷材の立体形状に成形するとともにゴム分を架橋させて製造される(例えば特許文献1等)。
As a fender that is installed on a quay and functions as a cushioning material when docking or mooring a ship, etc., the entire structure is made of an elastic material, especially a rubber cross-linker, and the structure is simple. Widely popular because it is hard to break.
Such a fender is prepared from a rubber composition prepared by blending a crosslinkable rubber with a filler such as carbon black, a cross-linking component for cross-linking the rubber, and various additives. And is produced by crosslinking the rubber component (for example, Patent Document 1).
架橋性のゴム分としては、ゴム硬さや切断時伸び、引張強さなどのゴムとしての物性(ゴム物性)を適度にバランスさせて防舷材に良好な緩衝性能を付与すること等を考慮して、あるいは入手のしやすさ等の観点から、天然ゴムが好適に使用される。
天然ゴムは単独で使用してもよいし、例えばスチレンブタジエンゴム等の他のゴムと併用してもよい。
For the cross-linkable rubber component, it is necessary to give a good cushioning performance to the fender by appropriately balancing the rubber properties (rubber properties) such as rubber hardness, elongation at break, and tensile strength. From the viewpoint of availability, etc., natural rubber is preferably used.
Natural rubber may be used alone or in combination with other rubber such as styrene butadiene rubber.
また上記天然ゴムを含むゴム分を架橋させるための架橋成分としては、硫黄(架橋剤)と、当該硫黄によるゴム分の架橋を促進する作用を有する架橋促進剤との組み合わせ等が好適に採用される。
防舷材には、設置場所でスペースを取らずに良好な緩衝性能を発現したり、使用材料を少なくして生産コストを低減したりするために、小型化しても高い反力を有することが求められる。
Further, as a crosslinking component for crosslinking the rubber component including the natural rubber, a combination of sulfur (crosslinking agent) and a crosslinking accelerator having an action of promoting the crosslinking of the rubber component by the sulfur is suitably employed. The
The fender has a high reaction force even if it is miniaturized in order to exhibit good shock-absorbing performance without taking up space at the installation location, or to reduce the production cost by using less materials. Desired.
また防舷材には、特に高温(酷暑)環境下で長期間に亘って使用し続けても、緩衝性能が低下したり、圧縮と伸長を繰り返した際にクラックを生じたりしにくいことも求められる。
すなわち防舷材は、通常は屋外に設置されるものであって、設置される地域や季節等によっては、例えば常時40℃以上といった高温環境下で使用され続ける場合がある。
The fender is also required to be resistant to reduced buffering performance and cracking when repeated compression and expansion, even if it is used for a long period of time, especially in high temperature (severe heat) environments. It is done.
In other words, the fender is usually installed outdoors, and depending on the area or season of installation, the fender may continue to be used in a high temperature environment such as 40 ° C. or higher.
また例えば設置場所によっては、直射日光を受ける等して防舷材の表面温度が80℃以上といった高温に達する場合すらある。
しかも防舷材は、一度設置すると数年ないし十数年といった単位で、長期間に亘って同一場所で使用し続けられるものでもある。
ところがゴム製の防舷材は、特に上述した高温環境下で、例えばゴム硬さが上昇したり切断時伸びが低下したりしてゴム物性のバランスが崩れやいため、比較的短期間で、良好な緩衝性能を維持できなくなったりクラックを生じたりしやすいという問題がある。
Further, for example, depending on the installation location, the surface temperature of the fender may even reach a high temperature of 80 ° C. or more due to direct sunlight.
In addition, once installed, the fender can be used in the same place for a long time in units of several years to several tens of years.
However, rubber fenders are good in a relatively short period of time, especially in the above-mentioned high temperature environment, for example, because the rubber hardness is increased or the elongation at the time of cutting is reduced and the balance of rubber properties is easily lost. There is a problem that it is difficult to maintain a sufficient cushioning performance or cracks are likely to occur.
特許文献2では、ゴム製の防舷材に、高温環境下でも常温環境下と大差ない緩衝性能を発現させるべく、温度23℃での最大反力R23と、温度60℃での最大反力R60との比R60/R23で表される圧縮性能変化率を0.90より大きくすることが提案されている。
しかし特許文献2に記載の発明では、緩衝性能の低下やクラックの発生等を抑制することまでは考慮されていないため、かかる防舷材を特に高温環境下で使用し続けた際に、短期間でこれらの問題を生じやすいことには変わりはない。
In Patent Document 2, the maximum reaction force R 23 at a temperature of 23 ° C. and the maximum reaction force at a temperature of 60 ° C. are exhibited in a rubber fender so as to exhibit a buffer performance that is not significantly different from that in a normal temperature environment even in a high temperature environment. the compression performance change rate expressed by the ratio R 60 / R 23 and R 60 be greater than 0.90 has been proposed.
However, since the invention described in Patent Document 2 does not take into account the suppression of a decrease in buffer performance, the occurrence of cracks, etc., when such a fender is continuously used particularly in a high temperature environment, a short period of time is required. However, it is easy to cause these problems.
本発明の目的は、緩衝性能に優れ、小型化しても高い反力を有する上、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくい高耐久の防舷材を形成しうる、新規な防舷材用ゴム組成物を提供することにある。 The object of the present invention is to provide a highly durable anti-shock material that is excellent in shock-absorbing performance, has a high reaction force even if it is downsized, and is unlikely to cause a decrease in shock-absorbing performance or cracks even when used for a long period of time in a high-temperature environment. It is an object of the present invention to provide a novel rubber composition for fenders that can form a fender.
本発明は、少なくとも天然ゴムおよびスチレンブタジエンゴムを含むゴム分、ならびにカーボンブラックを含み、前記スチレンブタジエンゴムは、ビニル含量が30質量%以上、45質量%以下、スチレン含量が25質量%以上、40質量%以下であるとともに、前記スチレンブタジエンゴムの配合割合は、前記ゴム分の総量100質量部中の10質量部以上、40質量部以下である防舷材用ゴム組成物である。 The present invention includes at least a rubber component including natural rubber and styrene butadiene rubber, and carbon black. The styrene butadiene rubber has a vinyl content of 30% by mass to 45% by mass, a styrene content of 25% by mass or more, 40%. The blending ratio of the styrene butadiene rubber is 10% by mass or more and 40% by mass or less in the total amount of the rubber content, and is a rubber composition for a fender.
本発明によれば、緩衝性能に優れ、小型化しても高い反力を有する上、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくい高耐久の防舷材を形成しうる、新規な防舷材用ゴム組成物を提供できる。 According to the present invention, it has excellent shock-absorbing performance, has a high reaction force even if it is downsized, and has a high durability that is unlikely to cause a decrease in shock-absorbing performance or cracks even when used continuously for a long period of time in a high-temperature environment. A novel rubber composition for fenders that can form a fender can be provided.
上記のように本発明は、少なくとも天然ゴムおよびスチレンブタジエンゴム(SBR)を含むゴム分、ならびにカーボンブラックを含み、前記スチレンブタジエンゴムは、ビニル含量が30質量%以上、45質量%以下、スチレン含量が25質量%以上、40質量%以下であるとともに、前記スチレンブタジエンゴムの配合割合は、前記ゴム分の総量100質量部中の10質量部以上、40質量部以下である防舷材用ゴム組成物である。 As described above, the present invention includes at least a rubber component including natural rubber and styrene butadiene rubber (SBR), and carbon black, and the styrene butadiene rubber has a vinyl content of 30% by mass to 45% by mass, and a styrene content. Is 25 mass% or more and 40 mass% or less, and the blending ratio of the styrene butadiene rubber is 10 mass parts or more and 40 mass parts or less in the total amount of 100 mass parts of the rubber. It is a thing.
かかる本発明の防舷材ゴム組成物によれば、上記特定のビニル含量、スチレン含量を有するSBRを、天然ゴムとともに上記所定の割合でゴム分として併用することによって、後述する実施例、比較例の結果からも明らかなように、緩衝性能に優れ、小型化しても高い反力を有する上、耐熱性に優れ高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくい高耐久の防舷材を形成できる。 According to the anti-mold rubber composition of the present invention, the SBR having the specific vinyl content and the styrene content is used together with natural rubber as a rubber component at the predetermined ratio, and the examples and comparative examples described later are used. As is clear from the results, the buffering performance is excellent, it has a high reaction force even if it is downsized, it has excellent heat resistance, and even if it continues to be used for a long time in a high temperature environment, the buffering performance is deteriorated or cracked. A highly durable fender that is unlikely to occur can be formed.
すなわち天然ゴムは、前述したように主にゴム物性を適度にバランスさせて防舷材に良好な緩衝性能を付与するために機能する。またSBRは、天然ゴムと併用することで、上記防舷材の耐熱性を向上するために機能する。
しかしビニル含量が30質量%未満であるSBRは上記の機能が不十分であり、特に前述したように高温環境下で防舷材のゴム物性のバランスが崩れて、緩衝性能が低下したりクラックを生じたりしやすい。
That is, natural rubber functions mainly to moderately balance rubber physical properties as described above and to impart good cushioning performance to the fender. SBR functions in combination with natural rubber to improve the heat resistance of the fender.
However, SBR with a vinyl content of less than 30% by mass has insufficient functions as described above, and particularly, as described above, the balance of the rubber physical properties of the fender is lost in a high temperature environment, resulting in reduced buffering performance and cracks. It is easy to occur.
またビニル含量が45質量%を超えるSBRは充填剤としてのカーボンブラックの分散性が低く、当該カーボンブラックによる補強効果が十分に得られないため防舷材の強度や剛性が不足したりしやすい。また、かかるSBRは架橋速度が遅いため、防舷材の生産性が低下するおそれもある。
またスチレン含量が25質量%未満であるSBRは破壊エネルギーが低いため防舷材の強度が不十分になりやすく、一方でスチレン含量が40質量%を超えるSBRは脆性破壊しやすいため防舷材の耐摩耗性を低下させるおそれがある。
Further, SBR having a vinyl content exceeding 45% by mass has a low dispersibility of carbon black as a filler, and the reinforcing effect of the carbon black cannot be sufficiently obtained, so that the strength and rigidity of the fender are easily insufficient. In addition, since the SBR has a low crosslinking rate, the productivity of the fender may be lowered.
In addition, SBR having a styrene content of less than 25% by mass has a low fracture energy, and thus the strength of the fender is likely to be insufficient. On the other hand, SBR having a styrene content exceeding 40% by mass is susceptible to brittle fracturing. There is a risk of reducing the wear resistance.
またSBRの配合割合がゴム分の総量100質量部中の10質量部未満では、当該SBRを配合することによる、耐熱性を向上する効果が十分に得られず、特に前述したように高温環境下で防舷材のゴム物性のバランスが崩れて、緩衝性能が低下したりクラックを生じたりしやすい。
また天然ゴムは、ゴム物性を適度にバランスさせることで防舷材に発生したクラックの成長を抑制する機能をするが、SBRの配合割合がゴム分の総量100質量部中の40質量部を超える場合には相対的に天然ゴムの割合が少なくなるため、かかる機能が十分に得られずクラックが成長しやすくなる。また防舷材の緩衝性能が低下したり、小型化した際に高い反力が得られなかったりするおそれもある。
Moreover, when the blending ratio of SBR is less than 10 parts by weight in 100 parts by weight of the total amount of rubber, the effect of improving heat resistance by blending the SBR cannot be sufficiently obtained, and particularly in a high temperature environment as described above. Thus, the balance of the rubber physical properties of the fender is lost, and the buffer performance is likely to be lowered or cracks are likely to occur.
Natural rubber has a function of suppressing the growth of cracks generated in the fender by appropriately balancing the physical properties of the rubber, but the blending ratio of SBR exceeds 40 parts by mass in 100 parts by mass of the total amount of rubber. In some cases, since the proportion of natural rubber is relatively small, such a function cannot be obtained sufficiently and cracks are likely to grow. Further, the cushioning performance of the fender may be reduced, or a high reaction force may not be obtained when the fender is downsized.
そのため上記いずれの場合にも、製造される防舷材は、特に小型化した際に高い反力が得られない上、特に高温環境下で長期間に亘って使用し続けた際に緩衝性能が低下したり、クラックを生じたりしやすいという問題がある。
これに対し、SBRのビニル含量、スチレン含量、およびSBRの配合割合をそれぞれ上記の範囲に設定することにより、上記各種の問題が生じるのを抑制して、前述したように緩衝性能に優れ、小型化しても高い反力を有する上、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくい高耐久の防舷材を形成できる。
Therefore, in any of the above cases, the manufactured fender can not obtain a high reaction force particularly when downsized, and has a buffering performance when used for a long period of time particularly in a high temperature environment. There exists a problem that it falls easily or a crack is easy to be produced.
On the other hand, by setting the SBR vinyl content, styrene content, and SBR blending ratio within the above ranges, it is possible to suppress the occurrence of the above-mentioned various problems, and as described above, the buffer performance is excellent, and the compact size. Even if it is made, a highly durable fender can be formed which has a high reaction force and is less likely to cause a decrease in buffer performance or crack even when used for a long period of time, particularly in a high temperature environment.
なお、かかる効果をより一層向上することを考慮するとSBRのビニル含量は、上記の範囲でも35質量%以上であるのが好ましく、42質量%以下であるのが好ましい。
またスチレン含量は、上記の範囲でも29質量%以上であるのが好ましく、34質量%以下であるのが好ましい。
〈ゴム分〉
ゴム分としては、前述したように特定のビニル含量、スチレン含量を有するSBRと、天然ゴムとを少なくとも併用する。
In consideration of further improving this effect, the vinyl content of SBR is preferably 35% by mass or more, and more preferably 42% by mass or less even in the above range.
In addition, the styrene content is preferably 29% by mass or more, and more preferably 34% by mass or less even in the above range.
<Rubber>
As the rubber component, as described above, at least SBR having a specific vinyl content and styrene content and natural rubber are used in combination.
(SBR)
このうちSBRとしては、スチレンと1,3−ブタジエンとを乳化重合法、溶液重合法等の種々の重合法によって共重合させて合成される種々のSBRのうち、ビニル含量が30質量%以上、45質量%以下で、かつスチレン含量が25質量%以上、40質量%以下であるものが選択して使用される。
(SBR)
Among these, as SBR, among various SBRs synthesized by copolymerizing styrene and 1,3-butadiene by various polymerization methods such as emulsion polymerization method and solution polymerization method, vinyl content is 30% by mass or more, Those having 45% by mass or less and having a styrene content of 25% by mass or more and 40% by mass or less are selected and used.
またSBRとしては、伸展油を加えて柔軟性を調整した油展タイプのものと、加えない非油展タイプのものとがあるが、本発明ではいずれのタイプのSBRも使用可能である。
かかるSBRとしては、例えば住友化学(株)製のSE0372〔ビニル含量:41質量%、スチレン含量:33質量%、SBR100質量部あたり20質量部の伸展油を含む油展SBR〕、SE6701〔ビニル含量:36質量%、スチレン含量:30質量%、SBR100質量部あたり15質量部の伸展油を含む油展SBR〕等の少なくとも1種が挙げられる。
The SBR includes an oil-extended type in which flexibility is adjusted by adding an extending oil and a non-oil-extended type in which flexibility is not added. In the present invention, any type of SBR can be used.
As such SBR, for example, SE0372 manufactured by Sumitomo Chemical Co., Ltd. [vinyl content: 41% by mass, styrene content: 33% by mass, oil-extended SBR containing 20 parts by mass of extended oil per 100 parts by mass of SBR], SE6701 [vinyl content : 36% by mass, styrene content: 30% by mass, and oil-extended SBR containing 15 parts by mass of extended oil per 100 parts by mass of SBR].
なおSBRとして油展SBRを用いる場合は、当該油展SBR中に含まれる伸展油を除外した、固形分としてのSBR自体の質量部を基準としてゴム分の総量や、当該ゴム分の総量中でのSBRの質量部等を設定することとする。
(天然ゴム)
天然ゴムとしては、例えばTSR20、RSS#3等の各種グレードの天然ゴムや、あるいは各種の脱蛋白天然ゴム等の1種または2種以上が挙げられる。
When oil-extended SBR is used as SBR, the total amount of rubber or the total amount of rubber is excluded based on the mass part of SBR itself as a solid, excluding the extension oil contained in the oil-extended SBR. The mass part of the SBR is set.
(Natural rubber)
Examples of the natural rubber include one or more of various grades of natural rubber such as TSR20 and RSS # 3, and various deproteinized natural rubbers.
天然ゴムの配合割合はSBRや、次に説明するその他のゴム分の残量とする。すなわちSBR、そして必要に応じてその他のゴム分を所定の割合で配合するとともに、天然ゴムを、ゴム分の総量が100質量部となるように配合すればよい。
(その他のゴム分)
ゴム分としては、上記SBRおよび天然ゴムの2種のみを併用するのが、構成を簡略化しつつ良好な効果を得る上で好ましいが、防舷材の特性を調整したりするために、さらに上記2種以外の他のゴム分を併用してもよい。
The blending ratio of natural rubber is the remaining amount of SBR and other rubber described below. That is, SBR and, if necessary, other rubber components are blended at a predetermined ratio, and natural rubber may be blended so that the total amount of rubber components is 100 parts by mass.
(Other rubber)
As the rubber component, it is preferable to use only two kinds of SBR and natural rubber together in order to obtain a good effect while simplifying the structure. However, in order to adjust the characteristics of the fender, Other rubber components other than the two types may be used in combination.
かかる他のゴム分としては、例えばビニル含量、スチレン含量のうちの少なくとも一方が前述した範囲外であるSBRが挙げられる他、例えばイソプレンゴム(IR)、ブタジエンゴム(BR)、ブチルゴム(IIR)、エチレンプロピレンジエンゴム(EPDM)、アクリロニトリルブタジエンゴム(NBR)、クロロプレンゴム(CR)等の合成ゴムの1種または2種以上が挙げられる。 Examples of such other rubber components include SBR in which at least one of the vinyl content and the styrene content is outside the above-mentioned range, for example, isoprene rubber (IR), butadiene rubber (BR), butyl rubber (IIR), Examples thereof include one or more synthetic rubbers such as ethylene propylene diene rubber (EPDM), acrylonitrile butadiene rubber (NBR), and chloroprene rubber (CR).
ただし、上述した特定のSBRと天然ゴムとを併用することによる効果を良好に発現させることを考慮すると、かかる他のゴム分を併用する場合、その配合割合はゴム分の総量100質量部中の10質量部以下、特に5質量部以下であるのが好ましい。
〈カーボンブラック〉
カーボンブラックとしては、ゴム分の充填剤、補強剤として機能しうる種々のカーボンブラックが使用可能である。
However, considering that the effect of using the specific SBR and natural rubber in combination is well expressed, when the other rubber component is used in combination, the blending ratio is 100 parts by mass of the total rubber component. It is preferably 10 parts by mass or less, particularly 5 parts by mass or less.
<Carbon black>
As the carbon black, various carbon blacks that can function as a filler and a reinforcing agent for rubber can be used.
ただしカーボンブラックとしては、ゴム分の総量に対する配合割合と補強効果との兼ね合い等を考慮すると、当該ゴム分の総量より少量の配合でゴム硬さを大きくして、防舷材の緩衝性能をより一層効率よく向上させるために、比較的粒径が小さくかつストラクチャが発達した、表面積の大きいグレードのものを用いるのが好ましい。
特に窒素吸着比表面積が70m2/g以上、120m2/g以下、DBP吸油量が90cm3/100g以上、130cm3/100g以下であるカーボンブラックが好適に使用される。
However, when considering the balance between the blending ratio and the reinforcing effect with respect to the total amount of rubber for carbon black, the rubber hardness is increased with a smaller amount of blending than the total amount of the rubber, and the cushioning performance of the fender is increased. In order to improve more efficiently, it is preferable to use a grade having a relatively small particle size and a developed structure and a large surface area.
In particular the nitrogen adsorption specific surface area of 70m 2 / g or more, 120 m 2 / g or less, DBP oil absorption of 90cm 3/100 g or more, the carbon black is not more than 130 cm 3/100 g is preferably used.
窒素吸着比表面積が70m2/g未満であるカーボンブラックは粒径が大きすぎ、またDBP吸油量が90cm3/100g未満であるカーボンブラックはストラクチャの発達が不十分であるため、このいずれを使用した場合にも上述した補強効果が十分に得られず、ゴム硬さを十分に大きくできないため防舷材に良好な緩衝性能を付与できないおそれがある。 Since the nitrogen adsorption specific surface area is less than 70m 2 / g carbon black particle size is too large, also carbon black DBP oil absorption amount is less than 90cm 3/100 g is insufficient development of the structure, using either the Even in this case, the above-described reinforcing effect cannot be obtained sufficiently, and the rubber hardness cannot be increased sufficiently, so that there is a possibility that good cushioning performance cannot be imparted to the fender.
一方、窒素吸着比表面積が120m2/gを超えるカーボンブラックは粒径が小さすぎ、またDBP吸油量が130cm3/100gを超えるカーボンブラックはストラクチャの発達が過剰であるため、このいずれを使用した場合にも上述した補強効果が強くなりすぎ、ゴム硬さが大きくなりすぎたり切断時伸びが小さくなりすぎたりして、やはり防舷材に良好な緩衝性能を付与できないおそれがある。 On the other hand, since carbon black nitrogen adsorption specific surface area exceeds 120 m 2 / g particle size is too small, also carbon black DBP oil absorption exceeds 130 cm 3/100 g is the development of structures is excessive, using either the Even in this case, the reinforcing effect described above becomes too strong, the rubber hardness becomes too large, or the elongation at the time of cutting becomes too small, so that there is a possibility that good cushioning performance cannot be imparted to the fender.
これに対し、窒素吸着比表面積およびDBP吸油量がともに前述した範囲であるカーボンブラックを選択的に使用することにより、適度の補強効果を確保して、防舷材に良好な緩衝性能を付与できる。
上記特性を満足するカーボンブラックとしては、例えば東海カーボン(株)製のシースト6〔ISAF、窒素吸着比表面積:119m2/g、DBP吸油量:114cm3/100g〕、シースト5H〔IISAF、窒素吸着比表面積:99m2/g、DBP吸油量:129cm3/100g〕、シーストKH〔N399、窒素吸着比表面積:93m2/g、DBP吸油量:119cm3/100g〕、シースト3H〔HAF−HS、窒素吸着比表面積:82m2/g、DBP吸油量:126cm3/100g〕、シーストNH〔N351、窒素吸着比表面積:74m2/g、DBP吸油量:127cm3/100g〕、シースト3〔HAF、窒素吸着比表面積:79m2/g、DBP吸油量:101cm3/100g〕、シーストN〔LI−HAF、窒素吸着比表面積:74m2/g、DBP吸油量:101cm3/100g〕等の1種または2種以上が挙げられる。
On the other hand, by selectively using carbon black whose nitrogen adsorption specific surface area and DBP oil absorption amount are both in the above-mentioned range, it is possible to secure an appropriate reinforcing effect and to impart good buffer performance to the fender. .
The carbon black satisfying the above characteristics, for example, by Tokai Carbon Co., Ltd. Seast 6 [ISAF, nitrogen adsorption specific surface area: 119m 2 / g, DBP oil absorption: 114 cm 3/100 g], SEAST 5H [IISAF, nitrogen adsorption specific surface area: 99m 2 / g, DBP oil absorption: 129 cm 3/100 g], Seast KH [N399, the nitrogen adsorption specific surface area: 93m 2 / g, DBP oil absorption: 119cm 3 / 100g], SEAST 3H [HAF-HS, nitrogen adsorption specific surface area: 82m 2 / g, DBP oil absorption: 126 cm 3/100 g], SEAST NH [N351, the nitrogen adsorption specific surface area: 74m 2 / g, DBP oil absorption: 127 cm 3/100 g], SEAST 3 [HAF, nitrogen adsorption specific surface area: 79m 2 / g, DBP oil absorption: 101 cm 3/100 g], the Strike N [LI-HAF, nitrogen adsorption specific surface area: 74m 2 / g, DBP oil absorption: 101 cm 3/100 g] one or more of the like.
カーボンブラックの配合割合は、ゴム分の総量100質量部あたり30質量部以上、特に40質量部以上であるのが好ましく、85質量部以下、特に80質量部以下であるのが好ましい。
カーボンブラックの配合割合がこの範囲未満では補強効果が十分に得られず、ゴム硬さを十分に大きくできないため防舷材に良好な緩衝性能を付与できないおそれがある。
The blending ratio of carbon black is preferably 30 parts by mass or more, particularly preferably 40 parts by mass or more, more preferably 85 parts by mass or less, and particularly preferably 80 parts by mass or less, per 100 parts by mass of the total amount of rubber.
If the blending ratio of the carbon black is less than this range, a sufficient reinforcing effect cannot be obtained, and the rubber hardness cannot be increased sufficiently, so that there is a possibility that good cushioning performance cannot be imparted to the fender.
一方、カーボンブラックの配合割合が上記の範囲を超える場合には隣り合うカーボンブラック同士の距離が近すぎるため、防舷材を繰り返し変形させた際にカーボンブラックが摩耗しやすくなって、経時変化による防舷材の緩衝性能の低下やクラック等を生じやすくなるおそれがある。
これに対し、カーボンブラックの配合割合を上記の範囲とすることにより、当該カーボンブラックによる補強効果を適度の範囲に調整して、防舷材に良好な緩衝性能を付与できる。また上記防舷材を、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくくできる。
On the other hand, when the blending ratio of the carbon black exceeds the above range, the distance between the adjacent carbon blacks is too close, so that when the fender is repeatedly deformed, the carbon black is likely to wear, and due to changes over time. There is a risk that the cushioning performance of the fender will be lowered, cracks, etc. likely to occur.
On the other hand, by setting the blending ratio of carbon black within the above range, the reinforcing effect of the carbon black can be adjusted to an appropriate range, and good cushioning performance can be imparted to the fender. Further, even if the fender is continuously used over a long period of time particularly in a high temperature environment, it is possible to prevent the buffer performance from being lowered and cracks are hardly generated.
〈架橋成分〉
本発明の防舷材用ゴム組成物には、従来同様に架橋成分を配合できる。
架橋成分としては、前述したように架橋剤としての硫黄、および当該硫黄によるゴム分の架橋を促進する機能を有する架橋促進剤を併用するのが好ましい。
(硫黄)
このうち硫黄としては、ゴム分の架橋剤として機能しうる種々の硫黄が使用可能である。
<Crosslinking component>
In the rubber composition for fenders of the present invention, a crosslinking component can be blended as in the prior art.
As the cross-linking component, it is preferable to use sulfur as a cross-linking agent and a cross-linking accelerator having a function of accelerating the cross-linking of rubber by the sulfur as described above.
(sulfur)
Among these, various sulfur which can function as a crosslinking agent for rubber can be used as sulfur.
硫黄の配合割合は、ゴム分の総量100質量部あたり0.5質量部以上であるのが好ましく、3質量部以下であるのが好ましい
硫黄の配合割合がこの範囲未満では、防舷材用ゴム組成物の全体での架橋速度が遅くなり、架橋に要する時間が長くなって防舷材の生産性が低下するおそれがある。
また硫黄の配合割合が上記の範囲を超える場合には、架橋後の圧縮永久ひずみが大きくなったり、過剰の硫黄が防舷材の表面にブルームしたりするおそれがある。
The blending ratio of sulfur is preferably 0.5 parts by weight or more per 100 parts by weight of the total amount of rubber, and preferably 3 parts by weight or less. If the blending ratio of sulfur is less than this range, the rubber for fenders There is a possibility that the cross-linking speed of the composition as a whole becomes slow, the time required for cross-linking becomes long, and the productivity of the fender is lowered.
Moreover, when the compounding ratio of sulfur exceeds the above range, the compression set after crosslinking may increase, or excess sulfur may bloom on the surface of the fender.
これに対し、硫黄の配合割合を上記の範囲とすることにより、架橋密度を適度の範囲に調整して、防舷材に良好な緩衝性能を付与できる。また上記防舷材を、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくくできる。
なお、例えば硫黄としてオイル入り粉末硫黄、分散性硫黄等を使用する場合、上記配合割合は、それぞれの中に含まれる有効成分としての硫黄自体の割合とする。
On the other hand, by setting the mixing ratio of sulfur within the above range, the crosslink density can be adjusted to an appropriate range, and good buffer performance can be imparted to the fender. Further, even if the fender is continuously used over a long period of time particularly in a high temperature environment, it is possible to prevent the buffer performance from being lowered and cracks are hardly generated.
For example, when oil-containing powdered sulfur, dispersible sulfur, or the like is used as sulfur, the blending ratio is the ratio of sulfur itself as an active ingredient contained therein.
(架橋促進剤)
架橋促進剤としては、例えば消石灰、マグネシア(MgO)、リサージ(PbO)等の無機促進剤や、グアニジン系促進剤、チアゾール系促進剤、スルフェンアミド系促進剤、チウラム系促進剤、ジチオカルバミン酸塩系促進剤、チオウレア系促進剤等の有機促進剤の1種または2種以上が挙げられる。特に遅効性の架橋促進剤を選択して用いるのが好ましい。
(Crosslinking accelerator)
Examples of the crosslinking accelerator include inorganic accelerators such as slaked lime, magnesia (MgO) and risurge (PbO), guanidine accelerators, thiazole accelerators, sulfenamide accelerators, thiuram accelerators, dithiocarbamates. 1 type, or 2 or more types of organic promoters, such as a system accelerator and a thiourea type accelerator, are mentioned. In particular, it is preferable to select and use a slow-acting crosslinking accelerator.
一般に防舷材は、防舷材用ゴム組成物を金型内に充填する等して防舷材の立体形状に成形した状態で、例えば130〜160℃の温度で3〜20時間程度の時間をかけて架橋させることによって製造される。
そのため遅効性の架橋促進剤を選択して用いることにより、上記成形時のスコーチなど良好に抑制できる。
In general, the fender is formed into a three-dimensional shape of the fender by filling the mold with a rubber composition for the fender, for example, at a temperature of 130 to 160 ° C. for about 3 to 20 hours. It is manufactured by crosslinking by applying.
Therefore, by selecting and using a slow-acting crosslinking accelerator, it is possible to satisfactorily suppress the scorch during the molding.
かかる遅効性の架橋促進剤としては、特にスルフェンアミド系促進剤が好ましい。
またスルフェンアミド系促進剤としては、例えばN−tert−ブチル−2−ベンゾチアゾリルスルフェンアミド(NS)、N−シクロヘキシル−2−ベンゾチアゾリルスルフェンアミド(CZ)、N−オキシジエチレン−2−ベンゾチアゾリルスルフェンアミド(MSA)等の1種または2種以上が挙げられる。
As such a slow-acting crosslinking accelerator, a sulfenamide accelerator is particularly preferable.
Examples of the sulfenamide accelerator include N-tert-butyl-2-benzothiazolylsulfenamide (NS), N-cyclohexyl-2-benzothiazolylsulfenamide (CZ), N-oxydiethylene- One type or two or more types such as 2-benzothiazolylsulfenamide (MSA) can be mentioned.
スルフェンアミド系促進剤は単独(2種以上のスルフェンアミド系促進剤を併用する場合を含む。以下同様。)で使用してもよいし、他の架橋促進剤と併用してもよい。
スルフェンアミド系促進剤と併用する他の架橋促進剤としては、上記スコーチの発生を抑制しながら、なおかつスルフェンアミド系促進剤を活性化して架橋速度を上昇させ、架橋時間を短縮して防舷材の生産性を向上できる架橋促進剤等が挙げられる。
The sulfenamide accelerator may be used alone (including the case where two or more sulfenamide accelerators are used in combination; the same applies hereinafter), or may be used in combination with other crosslinking accelerators.
Other cross-linking accelerators used in combination with sulfenamide accelerators include preventing the occurrence of the above scorch and activating the sulfenamide accelerators to increase the cross-linking speed and shortening the cross-linking time to prevent this. Examples thereof include a crosslinking accelerator that can improve the productivity of the straw material.
かかる他の架橋促進剤としては、前述した有機促進剤のうち例えばチウラム系促進剤、グアニジン系促進剤、チアゾール系促進剤、ジチオカルバミン酸系促進剤等の1種または2種以上が挙げられる。
スルフェンアミド系促進剤を単独で使用する場合の配合割合は、ゴム分の総量100質量部あたり0.5質量部以上であるのが好ましく、2質量部以下であるのが好ましい。
Examples of such other crosslinking accelerators include one or more of the organic accelerators described above, such as thiuram accelerators, guanidine accelerators, thiazole accelerators, dithiocarbamic acid accelerators, and the like.
When the sulfenamide-based accelerator is used alone, the blending ratio is preferably 0.5 parts by mass or more and preferably 2 parts by mass or less per 100 parts by mass of the total amount of rubber.
スルフェンアミド系促進剤の配合割合がこの範囲未満では、当該スルフェンアミド系促進剤を配合することによる、硫黄とゴム分との架橋反応を促進する効果が十分に得られないためゴム硬さが不足して、防舷材に良好な緩衝性能を付与できないおそれがある。
一方、スルフェンアミド系促進剤の配合割合が上記の範囲を超える場合には架橋密度が高くなりすぎるため、特に高温環境下で長期間に亘って使用し続けた際に緩衝性能が低下したり、クラックを生じたりしやすくなるおそれがある。
If the blending ratio of the sulfenamide accelerator is less than this range, the effect of promoting the cross-linking reaction between sulfur and the rubber component by blending the sulfenamide accelerator is not sufficiently obtained. There is a possibility that good cushioning performance cannot be imparted to the fender.
On the other hand, when the blending ratio of the sulfenamide accelerator exceeds the above range, the crosslinking density becomes too high, so that the buffer performance may be deteriorated particularly when used for a long period of time in a high temperature environment. There is a risk that cracks are likely to occur.
これに対し、スルフェンアミド系促進剤の配合割合を上記の範囲とすることにより、架橋密度を適度の範囲に調整して、防舷材に良好な緩衝性能を付与できる。また上記防舷材を、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくくできる。
〈その他の成分〉
本発明の防舷材用ゴム組成物には、さらに必要に応じて可塑剤、老化防止剤、架橋助剤、ワックス、粘着付与剤等を任意の割合で配合してもよい。
On the other hand, by setting the blending ratio of the sulfenamide-based accelerator within the above range, the crosslinking density can be adjusted to an appropriate range, and good buffer performance can be imparted to the fender. Further, even if the fender is continuously used over a long period of time particularly in a high temperature environment, it is possible to prevent the buffer performance from being lowered and cracks are hardly generated.
<Other ingredients>
The rubber composition for an antifungal material of the present invention may further contain a plasticizer, an anti-aging agent, a crosslinking aid, a wax, a tackifier, and the like as required.
(可塑剤)
可塑剤は、防舷材用ゴム組成物を調製する際や防舷材の形状に成形する際等の加工性を向上したり、当該防舷材用ゴム組成物の架橋物からなる防舷材の柔軟性を向上したりするために機能する。
可塑剤としては、例えばオイルや液状ゴムが挙げられる。
(Plasticizer)
The plasticizer improves the processability when preparing a rubber composition for a fender or forms it into the shape of a fender, or a fender made of a crosslinked product of the rubber composition for a fender. It works to improve flexibility.
Examples of the plasticizer include oil and liquid rubber.
このうちオイルとしては、例えば出光興産(株)製のダイアナ(登録商標)プロセスオイルPW、NP、NS、NR、NM、AC、AH等の各種グレードのオイルの1種または2種以上が挙げられる。
また液状ゴムとしては、例えば液状イソプレンゴム、水添液状イソプレンゴム、液状ブタジエンゴム、液状スチレンブタジエンゴム、あるいはこれらの末端変性物等の1種または2種以上が挙げられる。特に天然ゴムとの相溶性に優れた液状イソプレンゴムが好ましい。
Of these, examples of the oil include one or more of various grades of oil such as Diana (registered trademark) process oil PW, NP, NS, NR, NM, AC, AH manufactured by Idemitsu Kosan Co., Ltd. .
Examples of the liquid rubber include one or more of liquid isoprene rubber, hydrogenated liquid isoprene rubber, liquid butadiene rubber, liquid styrene butadiene rubber, and terminal modified products thereof. In particular, liquid isoprene rubber having excellent compatibility with natural rubber is preferred.
液状イソプレンゴムとしては、例えば(株)クラレ製のクラプレン(登録商標)LIR−30(数平均分子量:28000)、LIR−50(数平均分子量:54000)等が挙げられる。
可塑剤の配合割合は、ゴム分の総量100質量部あたり10質量部以上であるのが好ましく、30質量部以下であるのが好ましい。
Examples of the liquid isoprene rubber include Kuraray (trademark) LIR-30 (number average molecular weight: 28000), LIR-50 (number average molecular weight: 54000) manufactured by Kuraray Co., Ltd., and the like.
The blending ratio of the plasticizer is preferably 10 parts by mass or more, preferably 30 parts by mass or less, per 100 parts by mass of the total amount of rubber.
可塑剤の配合割合がこの範囲未満では、上述した、防舷材用ゴム組成物の加工性を向上したり防舷材の柔軟性を向上したりする効果が十分に得られないおそれがある。
一方、可塑剤の配合割合が上記の範囲を超える場合には架橋物の引張強さ自体が低下して、特に高温環境下で長期間に亘って使用し続けた際に緩衝性能が低下したり、クラックを生じたりしやすくなるおそれがある。
If the blending ratio of the plasticizer is less than this range, the above-described effects of improving the processability of the rubber composition for fenders and improving the flexibility of the fenders may not be sufficiently obtained.
On the other hand, when the blending ratio of the plasticizer exceeds the above range, the tensile strength itself of the cross-linked product is lowered, and the buffer performance is lowered particularly when the plasticizer is used for a long time in a high temperature environment. There is a risk that cracks are likely to occur.
これに対し、可塑剤の配合割合を上記の範囲とすることにより、防舷材用ゴム組成物の加工性や防舷材の柔軟性を良好に維持しながら、上記防舷材を特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくくできる。
なおSBRとして油展SBRを用いる場合は、当該油展SBR中に含まれる伸展油(可塑剤として機能する)を含めた可塑剤の合計の配合割合が上記の範囲となるように設定すればよい。
On the other hand, by setting the blending ratio of the plasticizer within the above range, the above-mentioned anti-mold material is particularly high-temperature environment while maintaining the processability of the anti-mold rubber composition and the flexibility of the anti-mold material. Even if it continues to be used for a long period of time, it is possible to make it difficult to cause a decrease in buffer performance and cracks.
When oil-extended SBR is used as SBR, the total blending ratio of plasticizers including the extender oil (functioning as a plasticizer) contained in the oil-extended SBR may be set within the above range. .
(老化防止剤)
老化防止剤としては、特に高温環境下での経時変化による緩衝性能の低下やクラック等を良好に抑制すること等を考慮して、かかる高温環境下で使用しても揮発しにくい2,2,4−トリメチル−1,2−ジヒドロキノリン重合体(224)が好適に使用される。
当該2,2,4−トリメチル−1,2−ジヒドロキノリン重合体の配合割合は、ゴム分の総量100質量部あたり1質量部以上であるのが好ましく、3質量部以下であるのが好ましい。
(Anti-aging agent)
As an anti-aging agent, in particular, it is difficult to volatilize even when used in such a high temperature environment in consideration of satisfactorily suppressing a decrease in buffer performance or cracks due to a change over time in a high temperature environment. 4-Trimethyl-1,2-dihydroquinoline polymer (224) is preferably used.
The blending ratio of the 2,2,4-trimethyl-1,2-dihydroquinoline polymer is preferably 1 part by mass or more and preferably 3 parts by mass or less per 100 parts by mass of the total amount of rubber.
また老化防止剤としては、上記2,2,4−トリメチル−1,2−ジヒドロキノリン重合体とともに、例えば日光亀裂、オゾン亀裂、および屈曲亀裂などの防止効果に優れたN−フェニル−N′−(1,3−ジメチルブチル)−p−フェニレンジアミン(6C)、2−メルカプトベンズイミダゾール(MB)等の2次老化防止剤を併用してもよい。
2次老化防止剤の配合割合は、ゴム分の総量100質量部あたり1質量部以上であるのが好ましく、5質量部以下であるのが好ましい。
In addition, as an anti-aging agent, for example, N-phenyl-N′- excellent in the effect of preventing sunlight cracking, ozone cracking, bending cracking and the like together with the 2,2,4-trimethyl-1,2-dihydroquinoline polymer. Secondary anti-aging agents such as (1,3-dimethylbutyl) -p-phenylenediamine (6C) and 2-mercaptobenzimidazole (MB) may be used in combination.
The blending ratio of the secondary antiaging agent is preferably 1 part by mass or more and preferably 5 parts by mass or less per 100 parts by mass of the total amount of rubber.
(架橋助剤)
架橋助剤としては、例えば酸化亜鉛等の金属化合物;ステアリン酸、オレイン酸、綿実脂肪酸等の脂肪酸その他、従来公知の架橋助剤の1種または2種以上が挙げられる。
架橋助剤の配合割合は、個別に、ゴム分の総量100質量部あたり0.5質量部以上であるのが好ましく、7質量部以下であるのが好ましい。
(Crosslinking aid)
Examples of the crosslinking aid include metal compounds such as zinc oxide; fatty acids such as stearic acid, oleic acid, and cottonseed fatty acid, and one or more conventionally known crosslinking aids.
The blending ratio of the crosslinking aid is preferably individually 0.5 parts by mass or more and preferably 7 parts by mass or less per 100 parts by mass of the total amount of rubber.
(ワックス)
ワックスは、防舷材の表面に皮膜を形成して、老化防止剤との併用により日光き裂、オゾン亀裂を防止するために機能する。
かかるワックスとしては、例えばパラフィンワックス等の石油系ワックスなどが挙げられる。
(wax)
The wax functions to form a film on the surface of the fender and prevent sun cracks and ozone cracks when used together with the anti-aging agent.
Examples of such wax include petroleum waxes such as paraffin wax.
またパラフィン系ワックスとしては、例えば大内新興化学工業(株)製のサンノック(登録商標)、サンノックN、サンノックP、日本精鑞(株)製のオゾエース(登録商標)0355、パラメルト社製のOK5258H等の1種または2種以上が挙げられる。
ワックスの配合割合は、ゴム分の総量100質量部あたり0.5質量部以上であるのが好ましく、2質量部以下であるのが好ましい。
As the paraffin wax, for example, Sannoc (registered trademark), Sannock N, Sannock P, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., Ozoace (registered trademark) 0355 manufactured by Nippon Seiki Co., Ltd., OK5258H manufactured by Paramelt Co., Ltd. 1 type, or 2 or more types, etc. are mentioned.
The blending ratio of the wax is preferably 0.5 parts by mass or more and preferably 2 parts by mass or less per 100 parts by mass of the total amount of rubber.
本発明の防舷材用ゴム組成物は、例えば上記各成分のうち架橋成分以外の各成分を、まずバンバリミキサ等を用いて混練したのち、さらに架橋成分を加えて混練する等して調製できる。
調製した防舷材用ゴム組成物を用いて防舷材を製造する工程は従来同様でよい。すなわち製造する防舷材の大きさや形状に応じて成形、シート成形、組み立て、および架橋等の任意の工程を組み合わせて防舷材を製造することができる。
The rubber composition for fenders of the present invention can be prepared, for example, by first kneading each component other than the cross-linking component among the above components using a Banbury mixer or the like and then kneading by adding the cross-linking component.
The process of manufacturing a fender using the prepared rubber composition for fenders may be the same as before. That is, the fender can be produced by combining arbitrary processes such as molding, sheet molding, assembly, and crosslinking according to the size and shape of the fender to be produced.
〈実施例1〉
ゴム分としては天然ゴム(TSR20)70質量部、および油展SBR〔前出の住友化学(株)製のSE6701、ビニル含量:36質量%、スチレン含量:30質量%、SBR100質量部あたり15質量部の伸展油を含む〕34.5質量部を併用した。
両ゴムを、下記表1に示す各成分のうち架橋成分以外の成分とともに、バンバリミキサを用いて150℃で5分間混練した後、さらに架橋成分を加えて2軸オープンロールを用いて70℃で5分間混練してシート状の防舷材用ゴム組成物を調製した。
<Example 1>
As rubber, 70 parts by weight of natural rubber (TSR20) and oil-extended SBR [SE6701, manufactured by Sumitomo Chemical Co., Ltd., vinyl content: 36% by weight, styrene content: 30% by weight, 15 parts by weight per 100 parts by weight of SBR 34.5 parts by mass were used in combination.
Both rubbers were kneaded together with components other than the crosslinking component among the components shown in Table 1 below at 150 ° C. for 5 minutes using a Banbury mixer, and then further added with a crosslinking component, and 5 ° C. at 70 ° C. using a biaxial open roll. A sheet-shaped rubber composition for fenders was prepared by kneading for a minute.
表1中の各成分は下記のとおり。また表中の質量部はゴム分の総量100質量部あたりの質量部を示す。
カーボンブラック:HAF、前出の東海カーボン(株)製のシースト3、窒素吸着比表面積:79m2/g、DBP吸油量:101cm3/100g
オイル:前出の出光興産(株)製のダイアナプロセスオイルNR26
ノクラック(登録商標)224:2,2,4−トリメチル−1,2−ジヒドロキノリン重合体、大内新興化学工業(株)製
ノクラック6C:N−フェニル−N′−(1,3−ジメチルブチル)−p−フェニレンジアミン、大内新興化学工業(株)製
ワックス:前出の日本精鑞(株)製のオゾエース0355
酸化亜鉛2種:架橋助剤、三井金属鉱業(株)製
ステアリン酸:架橋助剤、日油(株)製の商品名つばき
硫黄:架橋剤、鶴見化学工業(株)製の5%オイル入り粉末硫黄中の硫黄分
スルフェンアミド系促進剤:N−tert−ブチル−2−ベンゾチアゾリルスルフェンアミド、三新化学工業(株)製のサンセラー(登録商標)NS−G
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
Each component in Table 1 is as follows. Moreover, the mass part in a table | surface shows the mass part per 100 mass parts of total amounts of rubber | gum content.
Carbon black: HAF, supra Tokai Carbon Co., Ltd. of SEAST 3, nitrogen adsorption specific surface area: 79m 2 / g, DBP oil absorption: 101cm 3 / 100g
Oil: Diana Process Oil NR26 made by Idemitsu Kosan Co., Ltd.
NOCRACK (registered trademark) 224: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, manufactured by Ouchi Shinsei Chemical Co., Ltd. NOCRACK 6C: N-phenyl-N '-(1,3-dimethylbutyl) ) -P-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd. Wax: Ozoace 0355 manufactured by Nippon Seiki Co., Ltd.
2 types of zinc oxide: Cross-linking aid, manufactured by Mitsui Mining & Smelting Co., Ltd. Stearic acid: Cross-linking aid, product name Tsubaki manufactured by NOF Corporation Sulfur: Cross-linking agent, 5% oil from Tsurumi Chemical Co., Ltd. Sulfur content in powdered sulfur Sulfenamide accelerator: N-tert-butyl-2-benzothiazolylsulfenamide, Sunseller (registered trademark) NS-G manufactured by Sanshin Chemical Industry Co., Ltd.
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
〈実施例2〉
SBRとして、ビニル含量が41質量%、スチレン含量が33質量%である油展SBR〔前出の住友化学(株)製のSE0372、SBR100質量部あたり20質量部の伸展油を含む〕36質量部を配合するとともに、オイルの量を14質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
<Example 2>
As SBR, oil-extended SBR having a vinyl content of 41% by mass and a styrene content of 33% by mass (including the above-mentioned SE0372 manufactured by Sumitomo Chemical Co., Ltd., including 20 parts by mass of extended oil per 100 parts by mass of SBR) 36 parts by mass And a sheet-like rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of oil was 14 parts by mass.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈実施例3〉
天然ゴムの量を90質量部、油展SBRの量を11.5質量部、オイルの量を18.5質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 3>
A sheet-shaped rubber for fenders in the same manner as in Example 1 except that the amount of natural rubber was 90 parts by mass, the amount of oil-extended SBR was 11.5 parts by mass, and the amount of oil was 18.5 parts by mass. A composition was prepared.
SBRの配合割合は、ゴム分の総量100質量部中の10質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈実施例4〉
天然ゴムの量を75質量部、油展SBRの量を28.8質量部、オイルの量を16.2質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 10 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 4>
A rubber sheet for fenders in the same manner as in Example 1 except that the amount of natural rubber is 75 parts by mass, the amount of oil-extended SBR is 28.8 parts by mass, and the amount of oil is 16.2 parts by mass. A composition was prepared.
SBRの配合割合は、ゴム分の総量100質量部中の25質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈実施例5〉
天然ゴムの量を60質量部、油展SBRの量を46質量部、オイルの量を14質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 25 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 5>
A sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of natural rubber was 60 parts by mass, the amount of oil-extended SBR was 46 parts by mass, and the amount of oil was 14 parts by mass. did.
SBRの配合割合は、ゴム分の総量100質量部中の40質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈実施例6〉
カーボンブラックの量を30質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 40 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 6>
A sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of carbon black was 30 parts by mass.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり30質量部であった。
〈実施例7〉
カーボンブラックの量を40質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 30 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 7>
A sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of carbon black was 40 parts by mass.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり40質量部であった。
〈実施例8〉
カーボンブラックの量を80質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 40 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 8>
A sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of carbon black was 80 parts by mass.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり80質量部であった。
〈実施例9〉
カーボンブラックの量を85質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 80 parts by weight per 100 parts by weight of the total amount of rubber.
<Example 9>
A sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1 except that the amount of carbon black was 85 parts by mass.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり85質量部であった。
〈比較例1〉
SBRとして、ビニル含量が20質量%、スチレン含量が23.5質量%である非油展SBR〔住友化学(株)製の住友SBR1502〕30質量部を配合するとともに、オイルの量を20質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 85 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative example 1>
As SBR, 30 parts by mass of non-oil-extended SBR (Sumitomo SBR1502 manufactured by Sumitomo Chemical Co., Ltd.) having a vinyl content of 20% by mass and a styrene content of 23.5% by mass, and the amount of oil is 20 parts by mass. A sheet-like rubber composition for fenders was prepared in the same manner as in Example 1 except that.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈比較例2〉
SBRとして、ビニル含量が31質量%、スチレン含量が15質量%である非油展SBR〔日本ゼオン(株)製のNipol NS612〕30質量部を配合するとともに、オイルの量を20質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative example 2>
As SBR, 30 parts by mass of non-oil-extended SBR [Nipol NS612 manufactured by Nippon Zeon Co., Ltd.] having a vinyl content of 31% by mass and a styrene content of 15% by mass, and the amount of oil was 20 parts by mass. Except that, a sheet-like rubber composition for fenders was prepared in the same manner as in Example 1.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈比較例3〉
SBRとして、ビニル含量が61質量%、スチレン含量が30質量%である非油展SBR〔旭化成ケミカルズ(株)製のN207〕30質量部を配合するとともに、オイルの量を20質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative Example 3>
As SBR, 30 parts by mass of non-oil-extended SBR (N207 manufactured by Asahi Kasei Chemicals Co., Ltd.) having a vinyl content of 61% by mass and a styrene content of 30% by mass, and the amount of oil was 20 parts by mass. Except for the above, a sheet-shaped rubber composition for fenders was prepared in the same manner as in Example 1.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈比較例4〉
SBRとして、ビニル含量が67質量%、スチレン含量が21質量%である非油展SBR〔日本ゼオン(株)製のNipol NS616〕30質量部を配合するとともに、オイルの量を20質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative example 4>
As SBR, 30 parts by mass of non-oil-extended SBR [Nipol NS616 manufactured by Nippon Zeon Co., Ltd.] having a vinyl content of 67% by mass and a styrene content of 21% by mass, and the amount of oil was 20 parts by mass. Except that, a sheet-like rubber composition for fenders was prepared in the same manner as in Example 1.
SBRの配合割合は、ゴム分の総量100質量部中の30質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈比較例5〉
天然ゴムの量を95質量部、油展SBRの量を5.8質量部、オイルの量を19.2質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 30 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative Example 5>
A sheet-shaped rubber for fenders in the same manner as in Example 1 except that the amount of natural rubber was 95 parts by mass, the amount of oil-extended SBR was 5.8 parts by mass, and the amount of oil was 19.2 parts by mass. A composition was prepared.
SBRの配合割合は、ゴム分の総量100質量部中の5質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈比較例6〉
天然ゴムの量を55質量部、油展SBRの量を51.8質量部、オイルの量を13.2質量部としたこと以外は実施例1と同様にしてシート状の防舷材用ゴム組成物を調製した。
The blending ratio of SBR was 5 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Comparative Example 6>
A sheet-shaped rubber for fenders in the same manner as in Example 1 except that the amount of natural rubber was 55 parts by mass, the amount of oil-extended SBR was 51.8 parts by mass, and the amount of oil was 13.2 parts by mass. A composition was prepared.
SBRの配合割合は、ゴム分の総量100質量部中の45質量部、カーボンブラックの配合割合は、ゴム分の総量100質量部あたり60質量部であった。
〈サンプルの作製〉
上記各実施例、比較例で調製したシート状の防舷材用ゴム組成物を140℃で50分間プレス成形して、架橋させたシート状のサンプルを作製した。
The blending ratio of SBR was 45 parts by weight in 100 parts by weight of the total amount of rubber, and the blending ratio of carbon black was 60 parts by weight per 100 parts by weight of the total amount of rubber.
<Sample preparation>
The sheet-shaped rubber composition for fenders prepared in each of the above Examples and Comparative Examples was press-molded at 140 ° C. for 50 minutes to prepare a crosslinked sheet-shaped sample.
〈引張試験〉
作製したシート状のサンプルを打ち抜いて、日本工業規格JIS K6251:2010「加硫ゴム及び熱可塑性ゴム−引張特性の求め方」に規定されたダンベル状3号形試験片を作製し、標準試験温度下で、同規格に規定された引張試験をして引張強さTS(MPa)、および切断時伸びEb(%)を求めた。
<Tensile test>
The produced sheet-like sample was punched out to produce a dumbbell-shaped No. 3 test piece defined in Japanese Industrial Standard JIS K6251 : 2010 “vulcanized rubber and thermoplastic rubber—how to obtain tensile properties”, and the standard test temperature Below, the tensile test prescribed | regulated to the same specification was done, and tensile strength TS (MPa) and elongation at break Eb (%) were calculated | required.
引張強さTSは、16MPa未満を「×」、16MPa以上、20MPa未満を「○」、20MPa以上を「◎」と評価した。
また切断時伸びEbは、350%未満を「×」、350%以上、400%未満を「○」、400%以上を「◎」と評価した。
〈ゴム硬さ測定〉
作製したシート状のサンプルのタイプAデュロメータ硬さを、標準試験温度下で、日本工業規格JIS K6253−3:2012「加硫ゴム及び熱可塑性ゴム硬さの求め方−第3部:デュロメータ硬さ」に規定された測定方法に則って測定した。
The tensile strength TS was evaluated as “X” when less than 16 MPa, “◯” when less than 16 MPa, “◯” when less than 20 MPa, and “◎” when more than 20 MPa.
Further, the elongation Eb at the time of cutting was evaluated as “x” when less than 350%, “◯” when less than 350%, “◯” when less than 400%, and “◎” when 400% or more.
<Rubber hardness measurement>
The type A durometer hardness of the prepared sheet-like sample was measured under the standard test temperature, Japanese Industrial Standard JIS K6253-3 : 2012 “How to Obtain Vulcanized Rubber and Thermoplastic Rubber Hardness—Part 3: Durometer Hardness The measurement was performed according to the measurement method defined in “1.
タイプAデュロメータ硬さは、65未満および80超を「×」、65以上、80以下を「○」、特に上記○の範囲のうち70以上、75以下を「◎」と評価した。
〈高温耐久性試験〉
作製したシート状のサンプルを打ち抜いて、引張試験と同じダンベル状3号形試験片を作製し、日本工業規格JIS K6257:2003「加硫ゴム及び熱可塑性ゴム−熱老化特性の求め方」に準拠した強制循環形熱老化試験機を用いて100℃、360時間の条件で加熱して熱老化させた。
As for the type A durometer hardness, less than 65 and more than 80 were evaluated as “X”, 65 or more and 80 or less as “◯”, particularly 70 or more and 75 or less in the above range of “◯” as “」 ”.
<High temperature durability test>
The produced sheet-like sample is punched out to produce the same dumbbell-shaped No. 3 test piece as in the tensile test, and conforms to Japanese Industrial Standard JIS K6257 : 2003 "Vulcanized rubber and thermoplastic rubber-How to obtain heat aging characteristics" Was subjected to heat aging by heating at 100 ° C. for 360 hours using the forced circulation heat aging test machine.
次いでデマッチャ屈曲試験機を用いて、温度80℃の環境下、試験周波数5Hz、伸長率50%の条件で伸長試験を繰り返した際に、上記試験片が破断に至る伸長の繰り返し回数を103回単位で、最多100×103回までカウントした。
そして30×103回未満の伸長によって破断したものを「×」、30×103回以上、100×103回未満の伸長によって破断したものを「○」、100×103回の伸長でも破断しなかったものを「◎」と評価した。
Next, when the elongation test was repeated using a Dematcher bending tester under the conditions of a temperature of 80 ° C. and a test frequency of 5 Hz and an elongation rate of 50%, the number of repetitions of elongation until the test piece was broken was 10 3 times. The unit was counted up to a maximum of 100 × 10 3 times.
And "×" those broken by extension of less than 30 × 10 3 times, 30 × 10 3 times or more, "○" and those broken by extension of less than 100 × 10 3 times, at 100 × 10 3 times extension Those that did not break were evaluated as “◎”.
〈総合評価〉
上記各試験の結果が全て「◎」であったものを「◎」、「◎」と「○」であったものを「○」、一つでも「×」であったものを「×」と評価した。
以上の結果を表2〜表4に示す。
<Comprehensive evaluation>
All the above test results were “◎”, “◎”, “○” and “○” were “○”, and any one was “×” was “×”. evaluated.
The above results are shown in Tables 2-4.
表2〜表4の実施例1〜9、比較例1〜4の結果より、ビニル含量が30質量%以上、45質量%以下で、かつスチレン含量が25質量%以上、40質量%以下であるSBRを選択して用いることにより、緩衝性能に優れ、小型化しても高い反力を有する上、特に高温環境下で長期間に亘って使用し続けても緩衝性能の低下やクラックを生じにくい高耐久の防舷材を形成できることが判った。 From the results of Examples 1 to 9 and Comparative Examples 1 to 4 in Tables 2 to 4, the vinyl content is 30% by mass or more and 45% by mass or less, and the styrene content is 25% by mass or more and 40% by mass or less. By selecting and using SBR, it has excellent buffering performance and has a high reaction force even if it is miniaturized. It has been found that a durable fender can be formed.
だたし実施例1、3〜5、比較例5、6の結果より、上記の効果を得るためには、上記特定のSBRの配合割合を、ゴム分の総量100質量部中の10質量部以上、40質量部以下とする必要があることが判った。
また実施例1、2の結果より、上記の効果をさらに向上するためには、SBRのビニル含量を、上記の範囲でも35質量%以上、42質量%以下、スチレン含量を、上記の範囲でも29質量%以上、34質量%以下とするのが好ましいことが判った。
However, from the results of Examples 1, 3 to 5 and Comparative Examples 5 and 6, in order to obtain the above effect, the specific SBR blending ratio is 10 parts by mass in 100 parts by mass of the total amount of rubber. As mentioned above, it turned out that it is necessary to set it as 40 mass parts or less.
Further, from the results of Examples 1 and 2, in order to further improve the above effect, the SBR vinyl content was 35% by mass or more and 42% by mass or less in the above range, and the styrene content was 29 or more in the above range. It was found that the content is preferably not less than 34% by mass and not more than 34% by mass.
さらに実施例1、6〜9の結果より、上記の効果をさらに向上するためには、カーボンブラックの配合割合を、ゴム分の総量100質量部あたり30質量部以上、特に40質量部以上で、かつ85質量部以下、特に80質量部以下とするのが好ましいことが判った。 Furthermore, from the results of Examples 1 and 6 to 9, in order to further improve the above effect, the blending ratio of carbon black is 30 parts by mass or more, particularly 40 parts by mass or more, per 100 parts by mass of the total amount of rubber. In addition, it was found that the content is preferably 85 parts by mass or less, particularly 80 parts by mass or less.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016052622A JP6718589B2 (en) | 2016-03-16 | 2016-03-16 | Rubber composition for fender |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016052622A JP6718589B2 (en) | 2016-03-16 | 2016-03-16 | Rubber composition for fender |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2017165867A true JP2017165867A (en) | 2017-09-21 |
JP6718589B2 JP6718589B2 (en) | 2020-07-08 |
Family
ID=59912845
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2016052622A Active JP6718589B2 (en) | 2016-03-16 | 2016-03-16 | Rubber composition for fender |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP6718589B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019085512A (en) * | 2017-11-08 | 2019-06-06 | 住友ゴム工業株式会社 | Fender rubber composition |
-
2016
- 2016-03-16 JP JP2016052622A patent/JP6718589B2/en active Active
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019085512A (en) * | 2017-11-08 | 2019-06-06 | 住友ゴム工業株式会社 | Fender rubber composition |
Also Published As
Publication number | Publication date |
---|---|
JP6718589B2 (en) | 2020-07-08 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6494082B2 (en) | Rubber composition for fenders and fenders | |
JP5614308B2 (en) | Method for producing rubber composition for tire | |
JP5873063B2 (en) | Rubber composition for anti-vibration rubber and anti-vibration rubber | |
JP2018080531A (en) | Rubber composition for fender | |
JP4991163B2 (en) | Rubber composition for crosslinking | |
JP4402535B2 (en) | Rubber composition and pneumatic tire using the same | |
JP6718589B2 (en) | Rubber composition for fender | |
JP2014077050A (en) | Rubber composition for vibration-proof rubber and vibration-proof rubber | |
JP7004202B2 (en) | Fender | |
JP2009001603A (en) | Rubber sheet for rubber support coating, and coating material for rubber support | |
JP2020111674A (en) | tire | |
JP6548008B2 (en) | Rubber composition for fenders and fenders | |
JP2009007422A (en) | Rubber composition and tire | |
JP6697668B2 (en) | Rubber composition for fender | |
JP4871553B2 (en) | Process for producing rubber composition and rubber product obtained thereby | |
JP6960086B2 (en) | Rubber composition for fender | |
JP6909396B2 (en) | Rubber composition for fender | |
JP5082571B2 (en) | Rubber composition for tire tread | |
JP6597999B2 (en) | Fender | |
JP4871554B2 (en) | Manufacturing method of rubber composition | |
JP2009298905A (en) | Rubber composition for crawler | |
WO2016120991A1 (en) | Rubber composition for vibration damping rubbers, and vibration damping rubber | |
JP7523005B2 (en) | Rubber composition for fender and fender using same | |
JP2022190973A (en) | Rubber composition for fender, and fender using the same | |
JP2009091375A (en) | Rubber composition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190107 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20200110 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20200116 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20200310 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20200514 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20200527 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 6718589 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |