JP2017206573A - Rubber composition and pneumatic tire using the same and reinforcer for rubber - Google Patents
Rubber composition and pneumatic tire using the same and reinforcer for rubber Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 38
- 239000005060 rubber Substances 0.000 title claims abstract description 38
- 239000000203 mixture Substances 0.000 title claims abstract description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 115
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 57
- 239000011148 porous material Substances 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- 229920003244 diene elastomer Polymers 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000004381 surface treatment Methods 0.000 claims description 12
- 238000004448 titration Methods 0.000 claims description 10
- 239000012744 reinforcing agent Substances 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 abstract description 21
- 239000000945 filler Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 8
- 238000005299 abrasion Methods 0.000 abstract description 6
- 238000002835 absorbance Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 238000004073 vulcanization Methods 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-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
- 239000011164 primary particle Substances 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- -1 siloxanes Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 230000004580 weight loss Effects 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、ゴム組成物およびそれを用いた空気入りタイヤに関するものであり、詳しくは、低転がり抵抗性、硬度および耐摩耗性を同時に向上させ得るゴム組成物およびそれを用いた空気入りタイヤ並びにゴム用補強剤に関するものである。 TECHNICAL FIELD The present invention relates to a rubber composition and a pneumatic tire using the same, and more specifically, a rubber composition capable of simultaneously improving low rolling resistance, hardness and wear resistance, and a pneumatic tire using the same, and The present invention relates to a rubber reinforcing agent.
近年、空気入りタイヤは、ラベリング（表示方法）制度が開始され、タイヤの要求性能として転がり抵抗の低減が求められるようになっている。タイヤの低転がり抵抗化には、シリカなどのフィラーを高分散化する方法が有効であるが、該方法では硬度が低下し、操縦安定性を損なうという問題点がある。
一方、高硬度化のために充填剤量を増加させると、充填剤間の相互作用が増加し、転がり抵抗を悪化させてしまう。
また、一般的に低転がり抵抗性、硬度、耐摩耗性の性能はいずれも背反特性に位置するため、これらの特性を同時に満足させることは当業界で困難な事項とされていた。
なお、ゴム組成物に多孔質シリカを配合する技術は、下記特許文献１〜３等に開示されている。
In recent years, a labeling (display method) system has been started for pneumatic tires, and a reduction in rolling resistance is required as a required performance of the tire. In order to reduce the rolling resistance of the tire, a method of highly dispersing a filler such as silica is effective, but this method has a problem that the hardness is lowered and steering stability is impaired.
On the other hand, when the amount of the filler is increased for increasing the hardness, the interaction between the fillers is increased and the rolling resistance is deteriorated.
In general, low rolling resistance, hardness, and wear resistance are all in the contradictory characteristics, and satisfying these characteristics at the same time has been a difficult matter in the industry.
In addition, the technique of mix | blending porous silica with a rubber composition is disclosed by the following patent documents 1-3.
したがって本発明の目的は、低転がり抵抗性、硬度および耐摩耗性を同時に向上させ得るゴム組成物およびそれを用いた空気入りタイヤ並びにゴム用補強剤を提供することにある。 Accordingly, an object of the present invention is to provide a rubber composition capable of simultaneously improving low rolling resistance, hardness and abrasion resistance, a pneumatic tire using the rubber composition, and a rubber reinforcing agent.
本発明者らは鋭意研究を重ねた結果、ジエン系ゴムに対し、特定範囲のＤＢＰ吸油量および細孔容積を満たす多孔質シリカを特定量でもって配合することにより、上記課題を解決できることを見出し、本発明を完成することができた。
すなわち本発明は以下の通りである。
As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved by blending diene rubber with a specific amount of porous silica satisfying a specific range of DBP oil absorption and pore volume. The present invention has been completed.
That is, the present invention is as follows.
１．ジエン系ゴム１００質量部に対し、ＤＢＰ吸油量が３００ｍｌ／１００ｇを超えかつ８００ｍｌ／１００ｇ以下であり、なおかつ細孔容積Ｖｐが２〜１０ｍｌ／ｇである多孔質シリカを１〜５０質量部配合してなることを特徴とするゴム組成物。
２．前記多孔質シリカのメタノール滴定による疎水化度が３０〜６０容量％であることを特徴とする前記１に記載のゴム組成物。
３．前記多孔質シリカが表面処理され、かつ前記表面処理濃度が炭素濃度として５〜１０％であることを特徴とする前記１または２に記載のゴム組成物。
４．前記１〜３のいずれかに記載のゴム組成物を使用した空気入りタイヤ。
５．ＤＢＰ吸油量が３００ｍｌ／１００ｇを超えかつ８００ｍｌ／１００ｇ以下であり、なおかつ細孔容積Ｖｐが２〜１０ｍｌ／ｇである多孔質シリカよりなるジエン系ゴム用補強剤。
６．前記多孔質シリカのメタノール滴定による疎水化度が３０〜６０容量％であることを特徴とする前記５に記載のジエン系ゴム用補強剤。
７．前記多孔質シリカが表面処理され、かつ前記表面処理濃度が炭素濃度として５〜１０％であることを特徴とする前記５または６に記載のジエン系ゴム用補強剤。
1. 1 to 50 parts by mass of porous silica having a DBP oil absorption of more than 300 ml / 100 g and 800 ml / 100 g or less and a pore volume Vp of 2 to 10 ml / g with respect to 100 parts by mass of diene rubber. A rubber composition characterized by comprising:
2. 2. The rubber composition according to 1 above, wherein the degree of hydrophobicity of the porous silica by methanol titration is 30 to 60% by volume.
3. 3. The rubber composition as described in 1 or 2 above, wherein the porous silica is surface-treated and the surface treatment concentration is 5 to 10% as a carbon concentration.
4). A pneumatic tire using the rubber composition according to any one of 1 to 3 above.
5. A diene rubber reinforcing agent comprising porous silica having a DBP oil absorption of more than 300 ml / 100 g and 800 ml / 100 g or less and a pore volume Vp of 2 to 10 ml / g.
6). 6. The reinforcing agent for diene rubbers according to 5 above, wherein the degree of hydrophobicity of the porous silica by methanol titration is 30 to 60% by volume.
7). 7. The reinforcing agent for diene rubber according to 5 or 6, wherein the porous silica is surface-treated and the surface treatment concentration is 5 to 10% as a carbon concentration.
本発明によれば、ジエン系ゴムに対し、特定範囲のＤＢＰ吸油量および細孔容積を満たす多孔質シリカを特定量でもって配合したので、低転がり抵抗性、硬度および耐摩耗性を同時に向上させ得るゴム組成物およびそれを用いた空気入りタイヤを提供することができる。
また本発明のゴム用補強材は、特定範囲のＤＢＰ吸油量および細孔容積を満たす多孔質シリカからなることを特徴としているので、ゴムの低転がり抵抗性、硬度および耐摩耗性を同時に向上させることができる。
According to the present invention, since the diene rubber is blended with a specific amount of porous silica satisfying a specific range of DBP oil absorption and pore volume, low rolling resistance, hardness and wear resistance are simultaneously improved. A rubber composition to be obtained and a pneumatic tire using the same can be provided.
Further, the rubber reinforcing material of the present invention is characterized by comprising porous silica satisfying a specific range of DBP oil absorption and pore volume, thereby simultaneously improving the low rolling resistance, hardness and wear resistance of the rubber. be able to.
以下、本発明をさらに詳細に説明する。 Hereinafter, the present invention will be described in more detail.
（ジエン系ゴム）
本発明で使用されるジエン系ゴムは、ゴム組成物に配合することができる任意のジエン系ゴムを用いることができ、例えば、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合体ゴム（ＳＢＲ）、アクリロニトリル−ブタジエン共重合体ゴム（ＮＢＲ）、エチレン−プロピレン−ジエンターポリマー（ＥＰＤＭ）等が挙げられる。これらは、単独で用いてもよく、２種以上を併用してもよい。また、その分子量やミクロ構造はとくに制限されず、アミン、アミド、シリル、アルコキシシリル、カルボキシル、ヒドロキシル基等で変性されていても、エポキシ化されていてもよい。
これらのジエン系ゴムの中でも、本発明の効果の点からジエン系ゴムはＮＲ、ＳＢＲおよびＢＲがとくに好ましい。
(Diene rubber)
As the diene rubber used in the present invention, any diene rubber that can be blended in the rubber composition can be used, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR). Styrene-butadiene copolymer rubber (SBR), acrylonitrile-butadiene copolymer rubber (NBR), ethylene-propylene-diene terpolymer (EPDM), and the like. These may be used alone or in combination of two or more. Moreover, the molecular weight and microstructure are not particularly limited, and may be modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
Among these diene rubbers, NR, SBR and BR are particularly preferable as the diene rubber from the viewpoint of the effect of the present invention.
（多孔質シリカ）
本発明では、ＤＢＰ吸油量が３００ｍｌ／１００ｇを超えかつ８００ｍｌ／１００ｇ以下であり、なおかつ細孔容積Ｖｐが２〜１０ｍｌ／ｇである多孔質シリカを使用する。
多孔質シリカのＤＢＰ吸油量が３００ｍｌ／１００ｇ以下では、低転がり抵抗性、硬度および耐摩耗性を同時に向上させることができない。またＤＢＰ吸油量が８００ｍｌ／１００ｇを超えると混合加工性が著しく低下し、その結果、フィラーの分散が悪化する。
本発明において、多孔質シリカのＤＢＰ吸油量は、４５０〜７５０ｍｌ／１００ｇが好ましく、４００〜６００ｍｌ／１００ｇがさらに好ましい。
なお、多孔質シリカのＤＢＰ吸油量は、ＪＩＳ Ｋ６２１７−４に準拠して求めるものとする。
(Porous silica)
In the present invention, porous silica having a DBP oil absorption of more than 300 ml / 100 g and 800 ml / 100 g or less and a pore volume Vp of 2 to 10 ml / g is used.
When the DBP oil absorption amount of the porous silica is 300 ml / 100 g or less, the low rolling resistance, hardness and wear resistance cannot be improved at the same time. On the other hand, when the DBP oil absorption exceeds 800 ml / 100 g, the mixing processability is remarkably lowered, and as a result, the filler dispersion is deteriorated.
In the present invention, the DBP oil absorption of the porous silica is preferably 450 to 750 ml / 100 g, and more preferably 400 to 600 ml / 100 g.
In addition, the DBP oil absorption amount of porous silica shall be calculated | required based on JISK6217-4.
多孔質シリカの細孔容積Ｖｐが２ｍｌ／ｇ未満であると低転がり抵抗性、硬度および耐摩耗性を同時に向上させることができない。また細孔容積Ｖｐが１０ｍｌ／ｇを超えると耐摩耗性が悪化する。
本発明において、多孔質シリカの細孔容積Ｖｐは、２．５〜７ｍｌ／ｇが好ましく、３〜６ｍｌ／ｇがさらに好ましい。
なお、多孔質シリカの細孔容積Ｖｐは、測定対象のサンプルを、１ｋＰａ以下の真空下において、１５０℃の温度で２時間以上乾燥させ、その後液体窒素温度における窒素の吸着剤のみの吸着等温線を取得し、ＢＪＨ法（Ｂａｒｒｅｔｔ，Ｅ．Ｐ．；Ｊｏｙｎｅｒ，Ｌ．Ｇ．；Ｈａｌｅｎｄａ，Ｐ．Ｐ．，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．７３，３７３（１９５１））により解析して得られる細孔半径１ｎｍ以上１００ｎｍ以下の細孔に由来する細孔容積である。
When the pore volume Vp of the porous silica is less than 2 ml / g, the low rolling resistance, hardness and wear resistance cannot be improved at the same time. Further, when the pore volume Vp exceeds 10 ml / g, the wear resistance is deteriorated.
In the present invention, the pore volume Vp of the porous silica is preferably 2.5 to 7 ml / g, more preferably 3 to 6 ml / g.
The pore volume Vp of the porous silica is determined by drying the sample to be measured for 2 hours or more at a temperature of 150 ° C. under a vacuum of 1 kPa or less. And obtained by analysis according to the BJH method (Barrett, E.P .; Joyner, LG; Halenda, P.P., J. Am. Chem. Soc. 73, 373 (1951)). It is a pore volume derived from pores having a pore radius of 1 nm or more and 100 nm or less.
本発明で使用される多孔質シリカの製造方法は公知であり、例えば特開平１０−２３６８１７号、特開２０１３−２０３８０４号等に開示されている方法が挙げられる。 The manufacturing method of the porous silica used by this invention is well-known, For example, the method currently disclosed by Unexamined-Japanese-Patent No. 10-236817, Unexamined-Japanese-Patent No. 2013-203804, etc. is mentioned.
本発明で使用される多孔質シリカの比表面積は、３００ｍ２／ｇ〜８００ｍ２／ｇであることが好ましく、３５０ｍ２／ｇ〜７００ｍ２／ｇであることがより好ましく、４００ｍ２／ｇ〜６００ｍ２／ｇであることが特に好ましい。
なお、多孔質シリカの比表面積は、測定対象のサンプルを１ｋＰａ以下の真空下において１５０℃の温度で２時間以上乾燥させ、その後、液体窒素温度における窒素の吸着側のみの吸着等温線を測定し、該吸着等温線をＢＥＴ法により解析して求めた値であって、その際の解析に用いる圧力範囲は、相対圧０．１〜０．２５の範囲である。
本発明で使用される多孔質シリカの一次粒子径は、例えば３ｎｍ〜１０ｎｍ、好ましくは３ｎｍ〜７ｎｍである。
The specific surface area of the porous silica used in the present invention is preferably 300m 2 / g~800m 2 / g, more preferably 350m 2 / g~700m 2 / g, 400m 2 / g~ Particularly preferred is 600 m 2 / g.
The specific surface area of the porous silica is determined by drying the sample to be measured at 150 ° C. for 2 hours or more under a vacuum of 1 kPa or less, and then measuring the adsorption isotherm only on the nitrogen adsorption side at the liquid nitrogen temperature. The value obtained by analyzing the adsorption isotherm by the BET method, and the pressure range used for the analysis at that time is a range of a relative pressure of 0.1 to 0.25.
The primary particle diameter of the porous silica used in the present invention is, for example, 3 nm to 10 nm, preferably 3 nm to 7 nm.
通常、多孔質シリカは複数の粒子が集まって二次粒子を形成し、一次粒子同士で形成される間隙部によって多孔質化する。この間隙部にゴムが入り込むことにより、ゴムと多孔質シリカの強固な複合体が形成され、ゴムの分子運度が遮られ、硬度並びに耐摩耗性の発現に寄与するものと推測される。 Usually, the porous silica forms a secondary particle by collecting a plurality of particles, and is made porous by a gap formed by the primary particles. It is presumed that when rubber enters this gap, a strong composite of rubber and porous silica is formed, the molecular mobility of the rubber is blocked, and it contributes to the development of hardness and wear resistance.
また本発明の多孔質シリカは、メタノール滴定による疎水化度が３０〜６０容量（ｖｏｌ）％であることが好ましい。疎水化度が当該範囲を満たすことにより、低転がり抵抗性、硬度および耐摩耗性をさらに高次に満足させることができる。
本発明において、多孔質シリカの疎水化度は、４０〜５５容量％がさらに好ましい。
上記疎水化度を達成するには、多孔質シリカを表面処理する際の処理剤量等の条件を調整するの方法等がある。
なお、多孔質シリカの疎水化度は、多孔質シリカを水に加え、攪拌下にメタノールを滴定により加え、多孔質シリカの全量が水に懸濁した際のメタノール−水混合溶媒中のメタノールの濃度（容量％）の値を求めたものである。
Further, the porous silica of the present invention preferably has a degree of hydrophobicity by methanol titration of 30 to 60 volume (vol)%. When the degree of hydrophobicity satisfies this range, low rolling resistance, hardness, and wear resistance can be further satisfied.
In the present invention, the hydrophobicity of the porous silica is more preferably 40 to 55% by volume.
In order to achieve the above-mentioned degree of hydrophobicity, there is a method of adjusting conditions such as the amount of treatment agent when the surface treatment of porous silica is performed.
The degree of hydrophobicity of the porous silica is determined by adding the porous silica to water, adding methanol by titration with stirring, and the amount of methanol in the methanol-water mixed solvent when the entire amount of the porous silica is suspended in water. The concentration (volume%) value is obtained.
また本発明の多孔質シリカは表面処理され、かつ前記表面処理濃度が炭素濃度として５〜１０％であることが好ましい。炭素濃度が当該範囲を満たすことにより、低転がり抵抗性、硬度および耐摩耗性をさらに高次に満足させることができる。
本発明において、上記炭素濃度は６〜９％であることがさらに好ましい。
ここで言う表面処理とは、例えばシランカップリング剤を用いた処理、シリル化剤を用いた処理、シロキサン類を用いた処理等が挙げられる。
多孔質シリカの表面処理方法としては、例えばシリル化剤を用いた処理の場合、特開２０１３−２０３８０４号に開示される方法により処理することができる。
なお、炭素濃度は、多孔質シリカを完全燃焼させ、得られた燃焼ガス中の炭素ガスを定量し、換算することによって求めることができる。具体的には、エレメンタール社製のＶａｒｉｏ Ｍｉｃｒｏ ｃｕｂｅ等の市販の元素分析装置により測定することが可能である。
The porous silica of the present invention is preferably surface-treated and the surface treatment concentration is 5 to 10% as the carbon concentration. When the carbon concentration satisfies this range, low rolling resistance, hardness, and wear resistance can be further satisfied.
In the present invention, the carbon concentration is more preferably 6 to 9%.
Examples of the surface treatment herein include treatment using a silane coupling agent, treatment using a silylating agent, treatment using siloxanes, and the like.
As a surface treatment method for porous silica, for example, in the case of treatment using a silylating agent, treatment can be performed by a method disclosed in JP2013-203804A.
In addition, carbon concentration can be calculated | required by carrying out complete combustion of the porous silica, and quantifying and converting the carbon gas in the obtained combustion gas. Specifically, it can be measured by a commercially available elemental analyzer such as Vario Micro cube manufactured by Elemental.
以上説明した本発明の多孔質シリカは、ゴムの低転がり抵抗性、硬度および耐摩耗性を同時に向上させ得るので、ゴム用補強材として有用である。 The porous silica of the present invention described above is useful as a rubber reinforcing material because it can simultaneously improve the low rolling resistance, hardness, and wear resistance of rubber.
（ゴム組成物の配合割合）
本発明のゴム組成物は、ジエン系ゴム１００質量部に対し、上記多孔質シリカを１〜５０質量部配合してなることを特徴とする。
多孔質シリカの配合割合が１質量部未満であると、添加量が少なすぎて本発明の効果を奏することができない。逆に５０質量部を超えると、耐摩耗性が悪化する。
多孔質シリカの配合割合は、ジエン系ゴム１００質量部に対し、５〜４５質量部がさらに好ましく、１０〜３０質量部がとくに好ましい。
なお、本発明のゴム組成物は、多孔質シリカ以外のその他のシリカを併用することもできる。その場合、多孔質シリカおよびその他のシリカの合計量は、ジエン系ゴム１００質量部に対し、例えば３０〜２００質量部であることができる。
(Rubber composition ratio)
The rubber composition of the present invention is characterized in that 1 to 50 parts by mass of the porous silica is blended with 100 parts by mass of the diene rubber.
When the blending ratio of the porous silica is less than 1 part by mass, the added amount is too small to achieve the effects of the present invention. Conversely, when it exceeds 50 mass parts, abrasion resistance will deteriorate.
The blending ratio of the porous silica is more preferably 5 to 45 parts by mass and particularly preferably 10 to 30 parts by mass with respect to 100 parts by mass of the diene rubber.
In addition, the silica composition of this invention can also use silica other than porous silica together. In that case, the total amount of porous silica and other silica can be, for example, 30 to 200 parts by mass with respect to 100 parts by mass of the diene rubber.
（その他成分）
本発明におけるゴム組成物には、前記した成分に加えて、加硫又は架橋剤；加硫又は架橋促進剤；酸化亜鉛、カーボンブラック、クレー、タルク、炭酸カルシウムのような各種充填剤；老化防止剤；可塑剤などのゴム組成物に一般的に配合されている各種添加剤を配合することができ、かかる添加剤は一般的な方法で混練して組成物とし、加硫又は架橋するのに使用することができる。これらの添加剤の配合量も、本発明の目的に反しない限り、従来の一般的な配合量とすることができる。
(Other ingredients)
In the rubber composition of the present invention, in addition to the above-described components, a vulcanization or crosslinking agent; a vulcanization or crosslinking accelerator; various fillers such as zinc oxide, carbon black, clay, talc, calcium carbonate; Various additives generally blended in rubber compositions such as plasticizers can be blended, and these additives are kneaded by a general method to form a composition for vulcanization or crosslinking. Can be used. The blending amounts of these additives can be set to conventional general blending amounts as long as the object of the present invention is not violated.
また本発明のゴム組成物は従来の空気入りタイヤの製造方法に従って空気入りタイヤを製造するのに適しており、トレッド、とくにキャップトレッドに適用するのがよい。 The rubber composition of the present invention is suitable for producing a pneumatic tire in accordance with a conventional method for producing a pneumatic tire, and is preferably applied to a tread, particularly a cap tread.
以下、本発明を実施例および比較例によりさらに説明するが、本発明は下記例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example further demonstrate this invention, this invention is not restrict | limited to the following example.
標準例、実施例１〜６および比較例１〜７
サンプルの調製
表１に示す配合（質量部）において、加硫促進剤と硫黄を除く成分を１．７リットルの密閉式バンバリーミキサーで５分間混練した後、混練物をミキサー外に放出させて室温冷却させた。その後、同バンバリーミキサーにおいて加硫促進剤および硫黄を加えてさらに混練し、ゴム組成物を得た。次に得られたゴム組成物を所定の金型中で１６０℃、２０分間プレス加硫して加硫ゴム試験片を得、以下に示す試験法で加硫ゴム試験片の物性を測定した。
Standard example, Examples 1-6 and Comparative Examples 1-7
Sample Preparation In the formulation (parts by mass) shown in Table 1, the components other than the vulcanization accelerator and sulfur were kneaded for 5 minutes with a 1.7 liter closed Banbury mixer, and then the kneaded product was discharged out of the mixer at room temperature. Allow to cool. Thereafter, in the same Banbury mixer, a vulcanization accelerator and sulfur were added and further kneaded to obtain a rubber composition. Next, the obtained rubber composition was press vulcanized at 160 ° C. for 20 minutes in a predetermined mold to obtain a vulcanized rubber test piece, and the physical properties of the vulcanized rubber test piece were measured by the following test method.
硬度（２０℃）：ＪＩＳ Ｋ６２５３に基づき、２０℃にて測定した。結果は、標準例の値を１００として指数で示した。指数が大きいほど硬度が高いことを示す。
損失コンプライアンス：東洋精機製作所製の粘弾性スペクトロメーターを用い、歪１０±２%、周波数２０Ｈｚ、雰囲気温度６０℃の条件にて測定した。結果は、標準例の値を１００として指数で示した。指数が小さいほど低い転がり抵抗であることを示す。
耐摩耗性：岩本製作所（株）製のランボーン摩耗試験機を用い、荷重５ｋｇ（４９Ｎ）、スリップ率２５％、時間４分、室温の条件にて測定し摩耗減量を求めた。結果は、標準例の値を１００として指数で示した。指数が大きいほど耐摩耗性に優れることを示す。
結果を表１に併せて示す。
Hardness (20 ° C.): Measured at 20 ° C. based on JIS K6253. The results are shown as an index with the value of the standard example being 100. The larger the index, the higher the hardness.
Loss compliance: Measured using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of a strain of 10 ± 2%, a frequency of 20 Hz, and an ambient temperature of 60 ° C. The results are shown as an index with the value of the standard example being 100. The smaller the index, the lower the rolling resistance.
Abrasion resistance: Using a Lambourn abrasion tester manufactured by Iwamoto Seisakusho Co., Ltd., the weight loss was determined by measurement under the conditions of a load of 5 kg (49 N), a slip rate of 25%, a time of 4 minutes, and room temperature. The results are shown as an index with the value of the standard example being 100. It shows that it is excellent in abrasion resistance, so that an index | exponent is large.
The results are also shown in Table 1.
＊１：ＳＢＲ（旭化成（株）製Ｅ−５８１、油展量＝ＳＢＲ１００質量部に対し３７．５質量部）
＊２：ＢＲ（日本ゼオン（株）製Ｎｉｐｏｌ ＢＲ１２２０）
＊３：シリカ−１（Solvay社製Zeosil 1165MP）
＊４：シリカ−２（トクヤマ社製KS30SC）
＊５：多孔質シリカ−１
ＤＢＰ吸油量＝４９２ｍｌ／１００ｇ、
細孔容積Ｖｐ＝３．８ｍｌ／ｇ、
メタノール滴定による疎水化度＝４８容量％、
オクタメチルシクロテトラシロキサンによる表面処理有り（炭素濃度＝８．１％）、
比表面積＝５０２ｍ２／ｇ
D50＝２．２μｍ
＊６：多孔質シリカ−２
ＤＢＰ吸油量＝４８８ｍｌ／１００ｇ、
細孔容積Ｖｐ＝４．０ｍｌ／ｇ、
メタノール滴定による疎水化度＝４８容量％、
オクタメチルシクロテトラシロキサンによる表面処理有り（炭素濃度＝８．１％）
比表面積＝５０５ｍ２／ｇ
D50＝３．５μｍ
＊７：多孔質シリカ−３
ＤＢＰ吸油量＝４８７ｍｌ／１００ｇ、
細孔容積Ｖｐ＝４．１ｍｌ／ｇ、
メタノール滴定による疎水化度＝４８容量％、
オクタメチルシクロテトラシロキサンによる表面処理有り（炭素濃度＝８．１％）
比表面積＝４９９ｍ２／ｇ
D50＝７．５μｍ
＊８：多孔質シリカ−４
ＤＢＰ吸油量＝１５０ｍｌ／１００ｇ、
細孔容積Ｖｐ＝１．０ｍｌ／ｇ、
メタノール滴定による疎水化度＝４６容量％、
オクタメチルシクロテトラシロキサンによる表面処理有り（炭素濃度＝７．５％）、
比表面積＝５０９ｍ２／ｇ
D50＝３．０μｍ
＊９：カーボンブラック（東海カーボン（株）製シースト６）
＊１０：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊１１：ステアリン酸（日油（株）製ビーズステアリン酸）
＊１２：老化防止剤（フレキシス社製６ＰＰＤ）
＊１３：ワックス（大内新興化学工業（株）製パラフィンワックス）
＊１４：加工助剤（ジルアンドザイラッハー社製EF44）
＊１５：プロセスオイル（昭和シェル石油（株）製エキストラクト４号Ｓ）
＊１６：硫黄（鶴見化学工業（株）製金華印油入微粉硫黄）
＊１７：加硫促進剤−１（大内新興化学工業（株）製ノクセラーＣＺ−Ｇ）
＊１８：加硫促進剤−２（大内新興化学工業（株）製ノクセラーＤ）
* 1: SBR (E-581 manufactured by Asahi Kasei Co., Ltd., oil extended amount = 37.5 parts by mass with respect to 100 parts by mass of SBR)
* 2: BR (Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.)
* 3: Silica-1 (Zeosil 1165MP manufactured by Solvay)
* 4: Silica-2 (KS30SC manufactured by Tokuyama)
* 5: Porous silica-1
DBP oil absorption = 492 ml / 100 g,
Pore volume Vp = 3.8 ml / g,
Hydrophobic degree by methanol titration = 48% by volume,
With surface treatment with octamethylcyclotetrasiloxane (carbon concentration = 8.1%),
Specific surface area = 502 m 2 / g
D50 = 2.2μm
* 6: Porous silica-2
DBP oil absorption = 488 ml / 100 g,
Pore volume Vp = 4.0 ml / g,
Hydrophobic degree by methanol titration = 48% by volume,
Surface treatment with octamethylcyclotetrasiloxane (carbon concentration = 8.1%)
Specific surface area = 505 m 2 / g
D50 = 3.5μm
* 7: Porous silica-3
DBP oil absorption = 487 ml / 100 g,
Pore volume Vp = 4.1 ml / g,
Hydrophobic degree by methanol titration = 48% by volume,
Surface treatment with octamethylcyclotetrasiloxane (carbon concentration = 8.1%)
Specific surface area = 499 m 2 / g
D50 = 7.5μm
* 8: Porous silica-4
DBP oil absorption = 150 ml / 100 g,
Pore volume Vp = 1.0 ml / g,
Hydrophobic degree by methanol titration = 46% by volume,
With surface treatment with octamethylcyclotetrasiloxane (carbon concentration = 7.5%),
Specific surface area = 509 m 2 / g
D50 = 3.0μm
* 9: Carbon black (Toast Carbon Co., Ltd. Seest 6)
* 10: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 11: Stearic acid (beef stearic acid manufactured by NOF Corporation)
* 12: Anti-aging agent (6PPD manufactured by Flexis)
* 13: Wax (paraffin wax manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 14: Processing aid (EF44 manufactured by Jill and Sailacher)
* 15: Process oil (Extract No. 4 S manufactured by Showa Shell Sekiyu KK)
* 16: Sulfur (fine powdered sulfur with Jinhua seal oil from Tsurumi Chemical Co., Ltd.)
* 17: Vulcanization accelerator-1 (Noxeller CZ-G manufactured by Ouchi Shinsei Chemical Co., Ltd.)
* 18: Vulcanization accelerator-2 (Noxeller D manufactured by Ouchi Shinsei Chemical Co., Ltd.)
表１の結果から、実施例のゴム組成物は、ジエン系ゴムに対し、特定範囲のＤＢＰ吸油量および細孔容積を満たす多孔質シリカを特定量でもって配合したので、従来の代表的な標準例の組成物に比べ、低転がり抵抗性、硬度および耐摩耗性が同時に改善されていることが分かる。
これに対し、比較例１〜２は単にシリカの配合量を増加させた例であるので、低転がり抵抗性、硬度および耐摩耗性を同時に改善することができなかった。
比較例３〜４は、多孔質シリカのＤＢＰ吸油量および細孔容積が本発明で規定する下限未満であるので、低転がり抵抗性、硬度および耐摩耗性がいずれも悪化している。
比較例５〜６は、実施例における多孔質シリカとほぼ同等の比表面積を有するシリカを使用した例であるが、低転がり抵抗性、硬度および耐摩耗性を同時に改善することができなかった。
比較例７は、多孔質シリカの配合量が本発明で規定する上限を超えているので、耐摩耗性が悪化した。
From the results in Table 1, the rubber compositions of the examples were blended with a specific amount of porous silica satisfying the DBP oil absorption amount and pore volume in a specific range with respect to the diene rubber, so that the conventional representative standard It can be seen that the low rolling resistance, hardness and wear resistance are simultaneously improved compared to the example composition.
On the other hand, Comparative Examples 1 and 2 are examples in which the amount of silica is simply increased, and thus the low rolling resistance, hardness and wear resistance could not be improved at the same time.
In Comparative Examples 3 to 4, since the DBP oil absorption amount and pore volume of the porous silica are less than the lower limits specified in the present invention, the low rolling resistance, hardness, and wear resistance are all deteriorated.
Comparative Examples 5 to 6 are examples in which silica having a specific surface area substantially equivalent to the porous silica in the examples was used, but the low rolling resistance, hardness and wear resistance could not be improved at the same time.
In Comparative Example 7, the wear resistance deteriorated because the compounding amount of the porous silica exceeded the upper limit defined in the present invention.
Claims (7)
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| JP2018002902A (en) * | 2016-07-04 | 2018-01-11 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
| JP2018002919A (en) * | 2016-07-05 | 2018-01-11 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
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| JPS60231409A (en) * | 1984-04-06 | 1985-11-18 | ローヌ‐プーラン シミー ドウ バーズ | Novel sedimentary silica with improved morphological properties, manufacture and application as filler |
| JPH0375215A (en) * | 1989-08-17 | 1991-03-29 | Nippon Shirika Kogyo Kk | Preparation of porous silica |
| JP2005002225A (en) * | 2003-06-12 | 2005-01-06 | Asahi Kasei Chemicals Corp | Rubber composition |
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| JPS60231409A (en) * | 1984-04-06 | 1985-11-18 | ローヌ‐プーラン シミー ドウ バーズ | Novel sedimentary silica with improved morphological properties, manufacture and application as filler |
| JPH0375215A (en) * | 1989-08-17 | 1991-03-29 | Nippon Shirika Kogyo Kk | Preparation of porous silica |
| JP2005002225A (en) * | 2003-06-12 | 2005-01-06 | Asahi Kasei Chemicals Corp | Rubber composition |
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| JP2018002902A (en) * | 2016-07-04 | 2018-01-11 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
| JP2018002919A (en) * | 2016-07-05 | 2018-01-11 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
| JP7149686B2 (en) | 2016-07-05 | 2022-10-07 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
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