JP2017039789A - Rubber composition and pneumatic tire using the same - Google Patents
Rubber composition and pneumatic tire using the same Download PDFInfo
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- JP2017039789A JP2017039789A JP2015160407A JP2015160407A JP2017039789A JP 2017039789 A JP2017039789 A JP 2017039789A JP 2015160407 A JP2015160407 A JP 2015160407A JP 2015160407 A JP2015160407 A JP 2015160407A JP 2017039789 A JP2017039789 A JP 2017039789A
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- phenolic resin
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- carbon black
- rubber
- resin
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 36
- 239000005060 rubber Substances 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 title claims abstract description 35
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000005011 phenolic resin Substances 0.000 claims abstract description 55
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 53
- 239000006229 carbon black Substances 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 11
- 235000019198 oils Nutrition 0.000 claims description 11
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 235000019492 Cashew oil Nutrition 0.000 claims description 4
- 229940059459 cashew oil Drugs 0.000 claims description 4
- 239000010467 cashew oil Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000002787 reinforcement Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000020169 heat generation Effects 0.000 description 8
- 230000003014 reinforcing effect Effects 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229920003986 novolac Polymers 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229920001342 Bakelite® Polymers 0.000 description 3
- 244000043261 Hevea brasiliensis Species 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920003052 natural elastomer Polymers 0.000 description 3
- 229920001194 natural rubber Polymers 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 244000226021 Anacardium occidentale Species 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 235000020226 cashew nut Nutrition 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 229920003049 isoprene rubber Polymers 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
- 230000000704 physical effect Effects 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- JQALNNOQTGZTJZ-UHFFFAOYSA-N [[4,6-bis[bis(methoxymethyl)amino]-1,3,5-triazin-2-yl]-(methoxymethyl)amino]methanol Chemical compound COCN(CO)C1=NC(N(COC)COC)=NC(N(COC)COC)=N1 JQALNNOQTGZTJZ-UHFFFAOYSA-N 0.000 description 1
- BJSBGAIKEORPFG-UHFFFAOYSA-N [[6-amino-1,2,3,4-tetramethoxy-4-(methoxyamino)-1,3,5-triazin-2-yl]-methoxyamino]methanol Chemical compound CONC1(N(C(N(C(=N1)N)OC)(N(CO)OC)OC)OC)OC BJSBGAIKEORPFG-UHFFFAOYSA-N 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
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、フェノール系樹脂配合による補強効果を最大限に高め得る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る。 The present invention relates to a rubber composition and a pneumatic tire using the same, and more particularly, to a rubber composition capable of maximizing the reinforcing effect by the phenolic resin composition and a pneumatic tire using the same. is there.
フェノール系樹脂はゴム用の補強材料として広く用いられ、カーボンブラック単体では出せないようなゴム強靭性と低発熱性を両立することが可能であり、ゴムを高性能化する上で有用な原料である。例えば、加硫ゴムにフェノール系樹脂および硬化剤を配合し、高硬度化を図る手法が提案されている（例えば特許文献１参照）。 Phenolic resin is widely used as a reinforcing material for rubber, and it is possible to achieve both rubber toughness and low heat generation, which cannot be achieved with carbon black alone, and is a useful raw material for improving the performance of rubber. is there. For example, a method has been proposed in which a phenolic resin and a curing agent are blended with vulcanized rubber to increase the hardness (see, for example, Patent Document 1).
しかしながら、このフェノール系樹脂の作用メカニズムは今だ判明しておらず、様々な説が立てられているもののゴムに配合したときのフェノール系樹脂と物性との関係は依然不明瞭である。
したがって、ゴム組成物においてフェノール系樹脂が本来有する能力を最大限に引き出すことが当業界で求められている。
However, the mechanism of action of this phenolic resin has not yet been clarified, and although various theories have been made, the relationship between the phenolic resin and the physical properties when blended in rubber remains unclear.
Accordingly, there is a demand in the art to maximize the inherent capability of the phenolic resin in the rubber composition.
本発明者らは鋭意研究を重ねた結果、フェノール系樹脂配合による補強効果はカーボンブラックのストラクチャー量、とくにカーボンブラックの配合量とストラクチャーとを乗じた“カーボンブラック総ストラクチャー”と相関することを見出した。
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 reinforcing effect of the phenolic resin composition correlates with the structure amount of carbon black, particularly “total structure of carbon black” obtained by multiplying the composition amount of carbon black and the structure. It was.
That is, the present invention is as follows.
１．ジエン系ゴム１００質量部に対し、少なくともカーボンブラックを３０〜２００質量部、フェノール系樹脂を０．１質量部以上、およびヘキサメチレンテトラミンおよび多価メトキシ化メチロールメラミンから選択された樹脂硬化剤を前記フェノール系樹脂に対し５〜５０質量％配合し、
前記フェノール系樹脂の体積Ａ（ｃｍ３）と前記カーボンブラックの配合量Ｂ（ｇ）と前記カーボンブラックのＤＢＰ吸油量Ｃ（ｃｍ３／ｇ）との間に、０．０１≦｛Ａ／（Ｂ×Ｃ）｝≦０．５の関係が成り立つ
ことを特徴とするゴム組成物。
２．前記カーボンブラックに吸着した前記フェノール系樹脂の体積をＤ（ｃｍ３）としたとき、０．００５≦｛Ｄ／（Ｂ×Ｃ）｝≦０．２５の関係が成り立つ
ことを特徴とする前記１に記載のゴム組成物。
３．使用されるフェノール系樹脂の全量に対し、カシューオイルによって変性されているフェノール系樹脂の割合が１０質量％以上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用いた空気入りタイヤ。
1. The resin curing agent selected from at least 30 to 200 parts by mass of carbon black, 0.1 parts by mass or more of phenolic resin, and hexamethylenetetramine and polyvalent methoxylated methylol melamine with respect to 100 parts by mass of diene rubber 5-50 mass% is mix | blended with respect to phenol-type resin,
Between the volume A (cm 3 ) of the phenolic resin, the blending amount B (g) of the carbon black, and the DBP oil absorption C (cm 3 / g) of the carbon black, 0.01 ≦ {A / ( B × C)} ≦ 0.5 is satisfied.
2. The above 1 is characterized in that a relationship of 0.005 ≦ {D / (B × C)} ≦ 0.25 is established, where D (cm 3 ) is the volume of the phenolic resin adsorbed on the carbon black. The rubber composition as described in 2.
3. 3. The rubber composition as described in 1 or 2 above, wherein the proportion of the phenolic resin modified with cashew oil is 10% by mass or more based on the total amount of the phenolic resin used.
4). A pneumatic tire using the rubber composition according to any one of 1 to 3 above.
本発明によれば、フェノール系樹脂の配合量とカーボンブラック総ストラクチャーとの比を最適化するとともに、ジエン系ゴムに対するカーボンブラック、フェノール系樹脂および樹脂硬化剤の配合量を特定化しているので、発熱性を損なわずにフェノール系樹脂配合による補強効果を最大限に高めることを可能にした。 According to the present invention, the ratio between the amount of phenolic resin and the carbon black total structure is optimized, and the amount of carbon black, phenolic resin and resin curing agent relative to the diene rubber is specified. It is possible to maximize the reinforcement effect by adding phenolic resin without impairing heat generation.
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末端変性されていても、エポキシ化されていてもよい。
(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. The molecular weight and microstructure are not particularly limited, and may be terminally modified with an amine, amide, silyl, alkoxysilyl, carboxyl, hydroxyl group or the like, or may be epoxidized.
（カーボンブラック）
本発明で使用されるカーボンブラックは、とくに制限されないが、ストラクチャーを示すＤＢＰ吸油量が０．２０〜２．００ｃｍ３／ｇであるのが好ましく、０．３０〜１．５０ｃｍ３／ｇであるのがさらに好ましい。なおＤＢＰ吸収量はＪＩＳ Ｋ６２１７−４吸油量Ａ法に準拠して求めた値である。
(Carbon black)
Carbon black used in the present invention is not particularly limited, but is preferably a DBP oil absorption indicating the structure is 0.20~2.00cm 3 / g, is 0.30~1.50cm 3 / g Is more preferable. The DBP absorption amount is a value determined in accordance with JIS K6217-4 oil absorption amount A method.
（フェノール系樹脂）
本発明で使用するフェノール系樹脂は、ノボラック型フェノール系樹脂が好適であり、具体的には、ノボラック型フェノール樹脂、ノボラック型クレゾール樹脂、ノボラック型レゾルシン樹脂、オイル変性ノボラック型フェノール樹脂のいずれかあるいはそれらの混合物が挙げられる。
とくに本発明では、使用されるフェノール系樹脂は、カシューオイルによって変性されているフェノール系樹脂が好ましい。この形態によれば、補強効果をさらに高めることができる。本発明において、使用されるフェノール系樹脂の全量に対し、カシューオイルによって変性されているフェノール系樹脂は１０質量％以上であるのがさらに好ましい。
また本発明で使用するフェノール系樹脂は、市販されているものを利用することができ、例えば田岡化学工業（株）製スミカノール６１０、６２０、インドスペック社製ペナコライトレジンＢ−１８−Ｓ、住友ベークライト（株）製ＰＲ−５０７３１、ＰＲ−ＹＲ−１７０等が挙げられる。
(Phenolic resin)
The phenolic resin used in the present invention is preferably a novolak type phenolic resin, specifically, either a novolac type phenol resin, a novolac type cresol resin, a novolac type resorcin resin, or an oil-modified novolac type phenol resin. A mixture thereof may be mentioned.
In particular, in the present invention, the phenolic resin used is preferably a phenolic resin modified with cashew oil. According to this embodiment, the reinforcing effect can be further enhanced. In the present invention, the phenolic resin modified with cashew oil is more preferably 10% by mass or more based on the total amount of phenolic resin used.
Moreover, what is marketed can be utilized for the phenol-type resin used by this invention, for example, Taoka Chemical Industry Co., Ltd. Sumikanol 610,620, Indian spec company Penacolite resin B-18-S, Sumitomo Bakelite Co., Ltd. PR-50731, PR-YR-170, etc. are mentioned.
（樹脂硬化剤）
本発明のゴム組成物は、本発明の効果の観点から、樹脂硬化剤としてヘキサメチレンテトラミンおよび多価メトキシ化メチロールメラミンから選択された少なくとも１種を使用する。多価メトキシ化メチロールメラミンとしては、ＨＭＭＭ（ヘキサメトキシメチロールメラミンの部分縮合物）、ＰＭＭＭ（ヘキサメチロールメラミンペンタメチルエーテルの部分縮合物）等が挙げられる。
(Resin curing agent)
From the viewpoint of the effects of the present invention, the rubber composition of the present invention uses at least one selected from hexamethylenetetramine and polyvalent methoxylated methylol melamine as a resin curing agent. Examples of the polyvalent methoxylated methylol melamine include HMMM (partial condensate of hexamethoxymethylol melamine), PMMM (partial condensate of hexamethylol melamine pentamethyl ether) and the like.
（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、少なくともカーボンブラックを３０〜２００質量部、フェノール系樹脂を０．１質量部以上、およびヘキサメチレンテトラミンおよび多価メトキシ化メチロールメラミンから選択された樹脂硬化剤を前記フェノール系樹脂に対し５〜５０質量％配合する。
カーボンブラックの配合量が３０質量部未満であると、フェノール系樹脂の有する補強効果を十分に発揮できない。逆に２００質量部を超えると発熱性が悪化する。
フェノール系樹脂の配合量が０．１質量部未満であると、配合量が少な過ぎて本発明の効果を奏することができない。
樹脂硬化剤の配合量が前記フェノール系樹脂に対し５質量％未満であると、フェノール系樹脂の有する補強効果を十分に発揮できず、また発熱性も悪化する。逆に５０質量％を超えると発熱性が悪化する。
(Rubber composition ratio)
The rubber composition of the present invention comprises at least 30 to 200 parts by mass of carbon black, 0.1 part by mass or more of phenolic resin, and hexamethylenetetramine and polyvalent methoxylated methylol melamine with respect to 100 parts by mass of diene rubber. The selected resin curing agent is blended in an amount of 5 to 50% by mass with respect to the phenolic resin.
When the blending amount of the carbon black is less than 30 parts by mass, the reinforcing effect of the phenolic resin cannot be sufficiently exhibited. Conversely, when it exceeds 200 mass parts, exothermic property will deteriorate.
When the blending amount of the phenolic resin is less than 0.1 parts by mass, the blending amount is too small to achieve the effects of the present invention.
When the blending amount of the resin curing agent is less than 5% by mass with respect to the phenolic resin, the reinforcing effect of the phenolic resin cannot be sufficiently exhibited, and the heat generation property is also deteriorated. On the other hand, if it exceeds 50% by mass, the exothermic properties deteriorate.
前記カーボンブラックのさらに好ましい配合量は、ジエン系ゴム１００質量部に対し、３０〜１５０質量部である。
前記フェノール系樹脂のさらに好ましい配合量は、ジエン系ゴム１００質量部に対し、１〜３０質量部である。
前記樹脂硬化剤のさらに好ましい配合量は、フェノール系樹脂に対し、６〜１５質量％である。
A more preferable blending amount of the carbon black is 30 to 150 parts by mass with respect to 100 parts by mass of the diene rubber.
A more preferable blending amount of the phenolic resin is 1 to 30 parts by mass with respect to 100 parts by mass of the diene rubber.
The more preferable compounding quantity of the said resin hardening | curing agent is 6-15 mass% with respect to a phenol-type resin.
本発明では、フェノール系樹脂の体積Ａ（ｃｍ３）と、カーボンブラックの配合量Ｂ（ｇ）とカーボンブラックのＤＢＰ吸油量Ｃ（ｃｍ３／ｇ）との間に、０．０１≦｛Ａ／（Ｂ×Ｃ）｝≦０．５の関係が成り立つことをさらに特徴としている。
この｛Ａ／（Ｂ×Ｃ）｝が０．０１未満、あるいは０．５を超えた場合は、フェノール系樹脂配合による補強効果を高めることができず、また発熱性が悪化することもある。
本発明では、０．０５≦｛Ａ／（Ｂ×Ｃ）｝≦０．３０であることがさらに好ましく、０．１０≦｛Ａ／（Ｂ×Ｃ）｝≦０．２０であることがとくに好ましい。なお体積Ａは、フェノール系樹脂の質量と比重から算出できる。
In the present invention, 0.01 ≦ {A between the volume A (cm 3 ) of the phenolic resin and the blending amount B (g) of carbon black and the DBP oil absorption C (cm 3 / g) of carbon black. It is further characterized in that the relationship /(B×C)}≦0.5 holds.
When {A / (B × C)} is less than 0.01 or exceeds 0.5, the reinforcing effect by the phenolic resin blending cannot be enhanced, and the exothermic property may be deteriorated.
In the present invention, it is more preferable that 0.05 ≦ {A / (B × C)} ≦ 0.30, and it is particularly preferable that 0.10 ≦ {A / (B × C)} ≦ 0.20. preferable. The volume A can be calculated from the mass and specific gravity of the phenolic resin.
上記｛Ａ／（Ｂ×Ｃ）｝を特定範囲に定めることによって、本発明の効果がなぜ発現するのか、その詳細は明らかではないが、本発明者の検討によれば、フェノール系樹脂による効果を最大に得るためにはフェノール系樹脂とカーボンブラックの存在比に適値がある、と推測される。 The details of why the effect of the present invention is manifested by setting {A / (B × C)} to a specific range are not clear, but according to the study of the present inventors, the effect of the phenolic resin is not clear. In order to obtain the maximum, it is presumed that there is an appropriate value for the abundance ratio of the phenolic resin and carbon black.
また本発明によれば、カーボンブラックに吸着したフェノール系樹脂の体積をＤ（ｃｍ３）としたとき、０．００５≦｛Ｄ／（Ｂ×Ｃ）｝≦０．２５の関係が成り立つことがさらに好ましい。この｛Ｄ／（Ｂ×Ｃ）｝の関係を満たすことにより、フェノール系樹脂配合による補強効果をさらに高めることができる。
上記体積Ｄは、細かく裁断した未加硫ゴムをアセトンに浸漬し、浸漬前後の質量差から配合を基に算出することができる。実験操作はJIS K6229、アセトンの項に詳述されている。
不溶樹脂量（％）＝｛浸漬前ゴム質量（ｇ）×全アセトン可溶分（質量部）／全配合量（質量部）− 乾燥前後質量差（ｇ）｝／｛{浸漬前ゴム質量（ｇ）×樹脂配合量（質量部）／全配合量（質量部）｝
本発明では、０．０１０≦｛Ｄ／（Ｂ×Ｃ）｝≦０．２００であることがさらに好ましく、０．０５０≦｛Ｄ／（Ｂ×Ｃ）｝≦０．１００であることがとくに好ましい。
Further, according to the present invention, when the volume of the phenolic resin adsorbed on the carbon black is D (cm 3 ), a relationship of 0.005 ≦ {D / (B × C)} ≦ 0.25 holds. Further preferred. By satisfying this {D / (B × C)} relationship, the reinforcing effect of the phenolic resin composition can be further enhanced.
The volume D can be calculated on the basis of the formulation from the mass difference before and after immersion after immersing finely cut unvulcanized rubber in acetone. The experimental procedure is detailed in JIS K6229, Acetone section.
Insoluble resin amount (%) = {rubber mass before immersion (g) × total acetone soluble content (part by mass) / total blending amount (part by mass) −mass difference before and after drying (g)} / {{rubber mass before immersion ( g) x resin blending amount (parts by mass) / total blending amount (parts by mass)}
In the present invention, 0.010 ≦ {D / (B × C)} ≦ 0.200 is more preferable, and 0.050 ≦ {D / (B × C)} ≦ 0.100 is particularly preferable. preferable.
上記｛Ｄ／（Ｂ×Ｃ）｝を特定範囲に定めることによって、本発明の効果がなぜ向上するのか、その詳細は明らかではないが、カーボンブラックに吸着したフェノール系樹脂の体積とカーボンブラックの存在比に適値がある、と推測される。 Although it is not clear why the effect of the present invention is improved by setting {D / (B × C)} in a specific range, the volume of the phenolic resin adsorbed on the carbon black and the carbon black It is presumed that there is an appropriate value for the abundance ratio.
（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；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 addition to the components described above, the rubber composition in the present invention is generally blended with a rubber composition such as a vulcanization or crosslinking agent; a vulcanization or crosslinking accelerator; various fillers; an anti-aging agent; Various additives can be blended, and such additives can be kneaded by a general method to form a composition, which can be used for vulcanization or crosslinking. 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いる。 The rubber composition of the present invention is suitable for producing a pneumatic tire according to a conventional method for producing a pneumatic tire.
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１〜１１、実施例１〜１４および比較例１〜１２
サンプルの調製
下記各表に示す配合（特記しない限りは質量部）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、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未加硫のゴム組成物および加硫ゴム試験片の物性を測定した。
Standard Examples 1-11, Examples 1-14, and Comparative Examples 1-12
Sample Preparation In the formulations shown in the following tables (parts by mass unless otherwise specified), the vulcanization accelerator and components other than sulfur were kneaded for 5 minutes in a 1.7 liter closed Banbury mixer, and then the vulcanization accelerator and Sulfur was added and further kneaded to obtain a rubber composition. Next, the obtained rubber composition was press vulcanized in a predetermined mold at 160 ° C. for 20 minutes to obtain a vulcanized rubber test piece, and an unvulcanized rubber composition and vulcanized rubber were tested by the following test method. The physical properties of the test piece were measured.
発熱性（ｔａｎδ（６０℃））：ＪＩＳ Ｋ６３９４に準拠して、東洋精機社製の粘弾性スペクトロメーターを用いて、伸長変形歪率＝１０％、振幅＝±２％、振動数＝２０Ｈｚ、温度６０℃の条件下ｔａｎδ（６０℃）を測定し、この値をもって発熱性を評価した。結果は、各標準例を１００として指数で示した。指数が小さいほど、低発熱性であることを示す。
弾性率：ＪＩＳ Ｋ６３９４に準拠し、東洋精機製作所製粘弾性スペクトロメータを用い、初期歪１０％、振幅±２％、周波数２０Ｈｚの条件下で、２０℃における貯蔵弾性率(Ｅ’)を求めた。結果は、各標準例で得られた値を１００として指数表示した。指数が大きいほど弾性率が高く、フェノール系樹脂による補強効果が高いものと認められる。
結果を表１〜５に併せて示す。
なお、カーボンブラックに吸着したフェノール系樹脂の体積をＤ（ｃｍ３）を、上記方法によって測定し、｛Ｄ／（Ｂ×Ｃ）｝を算出し、これらの値を表１〜５に示した。
Exothermic property (tan δ (60 ° C.)): In accordance with JIS K6394, using a viscoelastic spectrometer manufactured by Toyo Seiki Co., Ltd., elongation deformation strain rate = 10%, amplitude = ± 2%, frequency = 20 Hz, temperature Tan δ (60 ° C.) was measured under the condition of 60 ° C., and the exothermic property was evaluated with this value. The results are shown as an index with each standard example as 100. A smaller index indicates a lower exothermic property.
Elastic modulus: Based on JIS K6394, the storage elastic modulus (E ′) at 20 ° C. was determined using a viscoelastic spectrometer manufactured by Toyo Seiki Seisakusho under the conditions of initial strain 10%, amplitude ± 2%, and frequency 20 Hz. . The results were expressed as an index with the value obtained in each standard example as 100. It is recognized that the larger the index, the higher the elastic modulus, and the higher the reinforcing effect by the phenolic resin.
A result is combined with Tables 1-5 and shown.
The volume of the phenolic resin adsorbed on the carbon black was measured by the above method to calculate D (cm 3 ), and {D / (B × C)} was calculated. These values are shown in Tables 1 to 5. .
＊１：ＮＲ（ＲＳＳ＃３）
＊２：カーボンブラック−１（東海カーボン（株）製SEAST 9、ＤＢＰ吸油量＝１．１５ｃｍ３／ｇ）
＊３：カーボンブラック−２（東海カーボン（株）製SEAST 300、ＤＢＰ吸油量＝０．７５ｃｍ３／ｇ）
＊４：カーボンブラック−３（東海カーボン（株）製SEAST KH、ＤＢＰ吸油量＝１．１９ｃｍ３／ｇ）
＊５：カーボンブラック−４（東海カーボン（株）製SEAST SP、ＤＢＰ吸油量＝０．５１ｃｍ３／ｇ）
＊６：フェノール系樹脂（住友ベークライト（株）製ノボラック型フェノール樹脂、ＰＲ−５０７３１）
＊７：カシューオイル変性フェノール系樹脂（住友ベークライト（株）製商品名ＰＲ−ＮＲ−１）
＊８：樹脂硬化剤（東京化成工業（株）製ヘキサメチレンテトラミン）
＊９：酸化亜鉛（正同化学工業（株）製酸化亜鉛３種）
＊１０：ステアリン酸（東京化成工業（株）製ステアリン酸）
＊１１：硫黄（軽井沢精錬所製油処理イオウ）
＊１２：加硫促進剤（大内新興化学工業（株）製ノクセラー ＮＳ）
* 1: NR (RSS # 3)
* 2: Carbon black-1 (SEAST 9, manufactured by Tokai Carbon Co., Ltd., DBP oil absorption = 1.15 cm 3 / g)
* 3: Carbon black-2 (SEAST 300 manufactured by Tokai Carbon Co., Ltd., DBP oil absorption = 0.75 cm 3 / g)
* 4: Carbon black-3 (SEAST KH manufactured by Tokai Carbon Co., Ltd., DBP oil absorption = 1.19 cm 3 / g)
* 5: Carbon black-4 (SEAST SP manufactured by Tokai Carbon Co., Ltd., DBP oil absorption = 0.51 cm 3 / g)
* 6: Phenolic resin (Novolak type phenolic resin, PR-50731 manufactured by Sumitomo Bakelite Co., Ltd.)
* 7: Cashew oil-modified phenolic resin (trade name PR-NR-1 manufactured by Sumitomo Bakelite Co., Ltd.)
* 8: Resin hardener (Hexamethylenetetramine manufactured by Tokyo Chemical Industry Co., Ltd.)
* 9: Zinc oxide (3 types of zinc oxide manufactured by Shodo Chemical Industry Co., Ltd.)
* 10: Stearic acid (Stearic acid manufactured by Tokyo Chemical Industry Co., Ltd.)
* 11: Sulfur (Karuizawa Refinery refined sulfur)
* 12: Vulcanization accelerator (Noxeller NS, manufactured by Ouchi Shinsei Chemical Co., Ltd.)
上記の表１の結果から明らかなように、標準例１と比較例１〜２、実施例１〜３の結果を比較すると、実施例１〜３で得られたゴム組成物は、本発明で規定する各原料の配合割合を満たすとともに、上記｛Ａ／（Ｂ×Ｃ）｝の要件を満たしていることから、標準例１のゴム組成物に対し、発熱性を損なわずにＥ’が向上していることが分かる。
これに対し、比較例１は、｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する下限未満であるので、Ｅ’を高めることができなかった。
比較例２は、｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する上限を超えているので、Ｅ’および発熱性が悪化した。
また、カーボンブラックのＤＰＢ吸油量を変更した標準例２と比較例３〜４、実施例４〜５の結果を比較した場合も、上記と同様の結果であった。
As is clear from the results in Table 1 above, comparing the results of Standard Example 1, Comparative Examples 1-2 and Examples 1-3, the rubber compositions obtained in Examples 1-3 are E ′ improves without compromising exothermicity with respect to the rubber composition of Standard Example 1 because it satisfies the requirements of {A / (B × C)} while satisfying the blending ratio of each specified raw material. You can see that
In contrast, in Comparative Example 1, E ′ could not be increased because {A / (B × C)} was less than the lower limit specified in the present invention.
Since the comparative example 2 had {A / (B * C)} exceeding the upper limit prescribed | regulated by this invention, E 'and exothermic property deteriorated.
Moreover, when the results of Comparative Example 3 and Comparative Examples 3 to 4 and Examples 4 to 5 in which the DPB oil absorption amount of carbon black was changed were compared, the same result as described above was obtained.
上記の表２の結果から明らかなように、標準例３と比較例５の結果を比較すると、比較例５は｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する範囲内であるものの、カーボンブラックの配合量が本発明で規定する下限未満であるので、Ｅ’が悪化した。
標準例４〜６と実施例６〜８の結果をそれぞれ比較すると、実施例６〜８で得られたゴム組成物は、本発明で規定する各原料の配合割合を満たすとともに、上記｛Ａ／（Ｂ×Ｃ）｝の要件を満たしていることから、標準例４〜６のゴム組成物に対し、発熱性を損なわずにＥ’を向上させていることが分かる。
標準例７と比較例６の結果を比較すると、比較例６は｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する下限未満であり、またカーボンブラックの配合量が本発明で規定する上限を超えているので、発熱性が悪化した。
As is clear from the results of Table 2 above, when the results of the standard example 3 and the comparative example 5 are compared, the comparative example 5 has {A / (B × C)} within the range defined by the present invention. Since the blending amount of carbon black was less than the lower limit specified in the present invention, E ′ deteriorated.
Comparing the results of Standard Examples 4 to 6 and Examples 6 to 8, the rubber compositions obtained in Examples 6 to 8 satisfy the blending ratio of each raw material defined in the present invention, and the above {A / Since the requirement of (B × C)} is satisfied, it can be seen that E ′ is improved without impairing the heat generation properties of the rubber compositions of Standard Examples 4 to 6.
Comparing the results of standard example 7 and comparative example 6, in comparative example 6, {A / (B × C)} is less than the lower limit prescribed by the present invention, and the blending amount of carbon black is the upper limit defined by the present invention. Exceeded the exothermicity.
上記の表３の結果から明らかなように、カーボンブラックのＤＢＰ吸油量を変更した場合であっても、本発明で規定する各原料の配合割合を満たすとともに、上記｛Ａ／（Ｂ×Ｃ）｝の要件を満たす実施例９および１０は、標準例８および１０と比較すると、発熱性を損なわずにＥ’を向上させていることが分かる。
標準例９と比較例７とを比較すると、比較例７は｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する上限を超えているので、Ｅ’が悪化した。
標準例１１と比較例８とを比較すると、比較例８は｛Ａ／（Ｂ×Ｃ）｝が本発明で規定する上限を超えているので、Ｅ’が悪化した。
As is clear from the results in Table 3 above, even when the DBP oil absorption amount of carbon black is changed, the blending ratio of each raw material defined in the present invention is satisfied, and the above {A / (B × C) } It can be seen that Examples 9 and 10 satisfying the requirement of E} improve E ′ without impairing heat generation as compared with Standard Examples 8 and 10.
When the standard example 9 and the comparative example 7 were compared, since the comparative example 7 exceeded the upper limit which {A / (BxC)} prescribes | regulates by this invention, E 'deteriorated.
When the standard example 11 and the comparative example 8 were compared, since the comparative example 8 exceeded the upper limit which {A / (B * C)} prescribes | regulates by this invention, E 'deteriorated.
上記の表４の結果から明らかなように、実施例１１〜１４は、本発明で規定する各原料の配合割合を満たすとともに、上記｛Ａ／（Ｂ×Ｃ）｝の要件を満たしているので、Ｅ’および発熱性が改善されている。とくに実施例１１〜１３は、フェノール系樹脂としてカシューオイル変性フェノール系樹脂を用いているので、Ｅ’および発熱性が顕著に改善された。
比較例９および１０は、樹脂硬化剤を配合していない、あるいは樹脂硬化剤の配合量が本発明で規定する下限未満であるので、Ｅ’および発熱性が悪化した。
比較例１１は、樹脂硬化剤の配合量が本発明で規定する上限を超えているので、発熱性が悪化した。
As is clear from the results in Table 4 above, Examples 11 to 14 satisfy the above-mentioned requirements for {A / (B × C)} while satisfying the blending ratio of each raw material defined in the present invention. , E ′ and exotherm are improved. In particular, since Examples 11 to 13 used cashew oil-modified phenolic resin as the phenolic resin, E ′ and heat generation were remarkably improved.
In Comparative Examples 9 and 10, the resin curing agent was not blended, or the blending amount of the resin curing agent was less than the lower limit specified in the present invention, so that E ′ and heat generation were deteriorated.
In Comparative Example 11, since the compounding amount of the resin curing agent exceeded the upper limit defined in the present invention, the heat generation was deteriorated.
上記の表５の結果から明らかなように、フェノール系樹脂を用いずにウレア樹脂を用いた比較例１２は、併記した標準例１および実施例７に比べて、Ｅ’が悪化した。 As is clear from the results of Table 5 above, E ′ was worse in Comparative Example 12 using the urea resin without using the phenolic resin as compared with the standard example 1 and Example 7 described together.
Claims (4)
前記フェノール系樹脂の体積Ａ（ｃｍ３）と前記カーボンブラックの配合量Ｂ（ｇ）と前記カーボンブラックのＤＢＰ吸油量Ｃ（ｃｍ３／ｇ）との間に、０．０１≦｛Ａ／（Ｂ×Ｃ）｝≦０．５の関係が成り立つ
ことを特徴とするゴム組成物。 The resin curing agent selected from at least 30 to 200 parts by mass of carbon black, 0.1 parts by mass or more of phenolic resin, and hexamethylenetetramine and polyvalent methoxylated methylol melamine with respect to 100 parts by mass of diene rubber 5-50 mass% is mix | blended with respect to phenol-type resin,
Between the volume A (cm 3 ) of the phenolic resin, the blending amount B (g) of the carbon black, and the DBP oil absorption C (cm 3 / g) of the carbon black, 0.01 ≦ {A / ( B × C)} ≦ 0.5 is satisfied.
ことを特徴とする請求項１に記載のゴム組成物。 The relationship of 0.005 ≦ {D / (B × C)} ≦ 0.25 is established, where D (cm 3 ) is the volume of the phenolic resin adsorbed on the carbon black. 2. The rubber composition according to 1.
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| JP2012149135A (en) * | 2011-01-17 | 2012-08-09 | Sumitomo Rubber Ind Ltd | Bead apex rubber composition and pneumatic tire |
| JP2012251017A (en) * | 2011-05-31 | 2012-12-20 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2014037514A (en) * | 2012-08-20 | 2014-02-27 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2015054927A (en) * | 2013-09-12 | 2015-03-23 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire using the same |
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| JP2012082323A (en) * | 2010-10-12 | 2012-04-26 | Yokohama Rubber Co Ltd:The | Rubber composition for tire and pneumatic tire using the same |
| JP2012149135A (en) * | 2011-01-17 | 2012-08-09 | Sumitomo Rubber Ind Ltd | Bead apex rubber composition and pneumatic tire |
| JP2012251017A (en) * | 2011-05-31 | 2012-12-20 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2014037514A (en) * | 2012-08-20 | 2014-02-27 | Yokohama Rubber Co Ltd:The | Rubber composition for tire |
| JP2015054927A (en) * | 2013-09-12 | 2015-03-23 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire using the same |
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