JP4515004B2 - Rubber composition - Google Patents
Rubber composition Download PDFInfo
- Publication number
- JP4515004B2 JP4515004B2 JP2001279439A JP2001279439A JP4515004B2 JP 4515004 B2 JP4515004 B2 JP 4515004B2 JP 2001279439 A JP2001279439 A JP 2001279439A JP 2001279439 A JP2001279439 A JP 2001279439A JP 4515004 B2 JP4515004 B2 JP 4515004B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- plasticizer
- acid
- weight
- parts
- 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.)
- Expired - Fee Related
Links
Landscapes
- Polyethers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【0001】
【発明の属する技術分野】
本発明は、油性物質に抽出されにくく、且つゴムの耐寒性及び冬期の作業性を向上せしめるゴム用可塑剤及びそれを含有するゴム組成物に関する。
【0002】
【従来の技術及び発明が解決しようとする課題】
従来、ゴムの耐寒性を向上させる技術として、フタル酸エステル、アジピン酸エステルや、ポリエチレングリコール脂肪酸エステル等の可塑剤を添加する方法が知られている。しかし、これら従来の可塑剤ではグリース等の油性物質に接触すると抽出されてしまい、また高温下では揮発してしまい、当初の耐寒性が損なわれてしまうという問題がある。さらにポリエステル系可塑剤等は抽出や揮発が起こりにくいが、本来の耐寒性が劣るという問題もある。
【0003】
これらの問題点を解決する技術が、特開昭61−145236号や特開平7−292235号に開示されているが、これらの技術ではクロロプレンゴム系で−30℃〜0℃付近の温度でゴムが硬くなるという現象が見られる。
【0004】
本発明の課題は、油性物質と接触しても抽出されにくく、また高温下でも揮発しにくく、且つゴムの耐寒性、特にクロロプレンゴム系で−30℃〜0℃付近の温度でのゴムの耐寒性を向上させることができ、更に冬期の作業性にも優れるゴム用可塑剤及びゴム組成物を提供することにある。
【0005】
【課題を解決するための手段】
本発明は、式(I)で表される数平均分子量200〜5000のグリコールと炭素数6〜16の分岐脂肪酸とのエステルからなるゴム用可塑剤、並びにこのゴム用可塑剤を、ゴム100重量部に対して3〜50重量部含有するゴム組成物を提供する。
【0006】
【化2】
【0007】
〔式中、Xは水素原子又は炭素数1〜3のアルキル基、aは0〜2の数、m及びnは、n/(m+n)=0.03〜0.5となる数を示し、オキシテトラメチレン基と、(CH2)aCH(X)CH2Oで示される基はブロック付加でもランダム付加でも良い。但し、aが2の時Xは水素原子ではない。〕
【0008】
【発明の実施の形態】
本発明の可塑剤は、水酸基価から求めた数平均分子量が200〜5000である式(I)で表されるグリコールと、炭素数6〜16の分岐脂肪酸とのエステルであり、ジエステルを75重量%以上含むものが好ましい。
【0009】
本発明の可塑剤における式(I)で表されるグリコールの数平均分子量は、油性物質に対する抽出されにくさ、高温下での揮発しにくさ、及び耐寒性の観点から、200〜5000であり、好ましくは300〜3000、更に好ましくは400〜2000である。
【0010】
式(I)において、(CH2)aCH(X)CH2Oで示される基としては、Xがメチル基で、aが0〜2である基が好ましく、Xがメチル基で、aが0又は2である基が更に好ましく、オキシプロピレン基が特に好ましい。n/(m+n)は、凝固点を下げる観点から、0.03〜0.5が好ましく、0.05〜0.4が更に好ましく、0.1〜0.4が特に好ましい。更に凝固点を下げる観点から、mは、3〜50が好ましく、5〜30が更に好ましく、8〜15が特に好ましい。またnは、0.5〜10が好ましく、1〜8が更に好ましく、1〜5が特に好ましい。
【0011】
式(I)で表されるグリコールは、例えば、テトラヒドロフランと、エチレンオキサイド、プロピレンオキサイド、テトラヒドロ−2−メチルフラン等とを、ランダム重合あるいはブロック重合させることにより合成することができる。また、市販品を用いることもできる。
【0012】
本発明の可塑剤における炭素数6〜16の分岐脂肪酸としては、例えば、イソヘキサン酸、イソヘプタン酸、2−エチルヘキサン酸、イソノナン酸、イソデカン酸、イソトリデカン酸、イソミリスチン酸、イソパルミチン酸等が挙げられ、好ましくはイソヘプタン酸、2−エチルヘキサン酸、イソノナン酸、特に好ましくは2−エチルヘキサン酸、イソノナン酸である。これらは1種単独でも、2種以上を併用してもよい。分岐脂肪酸の炭素数が6〜16の範囲にあることが、ゴム組成物のブリードなどの問題が生じないため必須である。
【0013】
本発明の可塑剤は、公知の方法、例えば式(I)で表されるグリコールと、分岐脂肪酸と、ジブチルスズオキシド等の金属触媒を高温下で加熱脱水することで容易に合成することができる。
【0014】
ゴム組成物中の本発明の可塑剤の含有量は、耐寒性、ブリードや他物性への影響、更にコスト的観点から、ゴム100重量部に対して、3〜50重量部であり、好ましくは5〜40重量部、さらに好ましくは10〜30重量部である。
【0015】
本発明に係るゴムとしては、天然ゴム(NR)、ブタジエンゴム(BR)、イソプレンゴム(IR)、ブチルゴム(IIR)、スチレンブタジエンゴム(SBR)、アクリロニトリルブタジエンゴム(NBR)、エチレンプロピレンゴム(EPDM)、クロロプレンゴム(CR)、クロルスルホン化ポリエチレンゴム(CSM)、エピクロルヒドリンゴム(CHR)等が挙げられ、CR、CSM、CHRが好ましく、CRが特に好ましい。
【0016】
本発明のゴム組成物は通常の混練機、例えばバンバリーミキサー、ロール、インテンシブミキサー等で容易に製造することができる。また、カーボンブラック、シリカ等の補強剤や加硫促進剤、加硫剤等、通常ゴムに配合される薬剤はもちろん、必要に応じて炭酸カルシウム、タルク、クレー等の充填剤や着色剤、紫外線吸収剤、汎用の可塑剤(フタル酸系、トリメリット酸系、リン酸系、エポキシ系等)等を適宜添加することができる。
【0017】
【実施例】
例中の%は特記しない限り重量%である。
【0018】
合成例1
式(I)において、Xがメチル基で、aが2で、mが9で、nが1.6で、n/(m+n)が0.15である、数平均分子量800のグリコール(PTG−L800、保土谷化学工業(株)製)400gと、2−エチルヘキサン酸173g、触媒としてジブチルスズオキシド0.57gを1リットル四つ口フラスコに秤取り、窒素吹き込み下、230℃で脱水しながら、エステル化反応を5〜6時間行った後、過剰の2−エチルヘキサン酸を留去して、エステル(PTGR8002EH、組成:ジエステル90%、モノエステル10%)を得た。
【0019】
合成例2
式(I)において、Xがメチル基で、aが2で、mが11.5で、nが2で、n/(m+n)が0.15である、数平均分子量1000のグリコール(PTG−L1000、保土谷化学工業(株)製)500gと、2−エチルヘキサン酸173g、ジブチルスズオキシド0.67gを合成例1と同様の方法で反応させて、エステル(PTGR10002EH、組成:ジエステル85%、モノエステル15%)を得た。
【0020】
合成例3
式(I)において、Xがメチル基で、aが0で、mが10.5で、nが4.5で、n/(m+n)が0.3である、数平均分子量1000のグリコール(PPTG1000、保土谷化学工業(株)製)500gと、2−エチルヘキサン酸173g、ジブチルスズオキシド0.67gを合成例1と同様の方法で反応させて、エステル(PTGPO10002EH、組成:ジエステル75%、モノエステル25%)を得た。
【0021】
比較合成例1
アジピン酸321g、1,4−ブタンジオール180g、n−オクタノール58g及びジブチルスズオキシド0.55gを合成例1と同様の方法でエステル化を行い、脱アルコールして、仕込み値より計算した平均分子量約2500のポリエステルAを得た。
【0022】
比較合成例2
数平均分子量1000のポリオキシテトラメチレングリコール513gとラウリン酸200g、ジブチルスズオキシド0.7gを合成例1と同様の方法で反応させて、エステル(PTG1000L、組成:ジエステル87%、モノエステル13%)を得た。
【0023】
比較合成例3
数平均分子量600のポリプロピレングリコール400gと2−エチルヘキサン酸230g、ジブチルスズオキシド0.6gを合成例1と同様の方法で反応させて、エステル(PPG2EH、組成:ジエステル96%、モノエステル4%)を得た。
【0024】
実施例1〜6及び比較例1〜7
合成例1〜3及び比較合成例1〜3で得られたエステル、あるいは耐寒性向上に一般的に使われるジ2−エチルヘキシルアジペートを可塑剤として用い、表1に示す各種CR系ゴムで下記配合のゴム組成物を調製し、170℃、10分加硫を行い、厚さ2mmのテストピースを作製した。このテストピースについて、下記方法で耐寒性、対グリース抽出性、耐熱性、ブリード、流動点及び冷蔵庫保管後の流動性を評価した。結果を表1に示す。
【0025】
<ゴム組成物>
CR系ゴム 100.0重量部
SRFカーボン*1 60.0重量部
老防PA*2 5.0重量部
酸化マグネシウム 4.0重量部
酸化亜鉛 5.0重量部
ステアリン酸 2.0重量部
加硫促進剤22*3 0.5重量部
可塑剤 30.0重量部
*1 SRFカーボン:カーボンブラックSRF
*2 老防PA:N−フェニル−α−ナフチルアミン
*3 加硫促進剤22:エチレンチオ尿素
<耐寒性>
JIS K−6301(新JIS K−6261)の方法で、ゲーマン捻り試験で耐寒性の評価を行った。T100、T10、T5、T2はそれぞれ、常温(23℃)に比べ捻りモジュラスが100倍、10倍、5倍、2倍になる温度で、数字が低いほど耐寒性が良好なことを示す。
【0026】
<対グリース抽出性>
10×10cmに切断したテストピースに厚さ20mmになるようにグリースを塗布し、120℃の恒温機で50時間放置した。その後、室温でグリースを拭き取り、テストピースをJIS K−6301(新JIS K−6261)の方法で評価した。ゴム組成物中の可塑剤の対グリース抽出性は、耐寒性評価で判断することができ、グリースに抽出されにくいほど、対グリース抽出後の耐寒性は良好であることを示す。
【0027】
<耐熱性>
テストピースを3号ダンベル型に切断し、120℃、100時間恒温機で放置して重量変化から揮発分を測定した。揮発分が少ないほど耐熱性が良好である。
【0028】
<ブリード>
テストピースを40℃の雰囲気下で7日間保存し、その表面状態を肉眼で観察し、下記基準で評価した。
【0029】
○:可塑剤のブリードが見られない
△:若干のブリードがある
×:表面のブリードが激しい
<流動点>
直径約5mm、長さ約60mmのガラス管に可塑剤を半分の高さに封入し、ドライアイス+エタノール系の−70℃で固化させた後、そのガラス管をその温度から2℃/分の割合で昇温させていき、ガラス管中の可塑剤が流れ出す温度を測定し、流動点とした。
【0030】
<冷蔵庫保管後の流動性>
50mLのサンプル管に可塑剤を入れ、5℃の冷蔵庫に24時間保存した後の可塑剤の状態を下記基準で評価した。
【0031】
◎:透明であり、流動する
○:懸濁して不透明であるが、流動する
△:一部固化あるが、流動する
×:殆ど固化していて、流動しない
【0032】
【表1】
【0033】
*1:電気化学工業(株)製メルカプタン変性CR
*2:電気化学工業(株)製ザントゲン変性CR
*3:電気化学工業(株)製硫黄変性CR
*4:デュポン ダウ エラストマー ジャパン製
(昭和ディー・ディー・イー製造(株)製メルカプタン変性CR)
【0034】
【発明の効果】
本発明のゴム組成物は、低温における柔軟性、特にT2、T5での柔軟性に優れ、且つグリース等の油性物質による抽出が少なく、さらに高温下で揮発しにくいため耐寒性の保持に優れている。また、冬期においても固化することがなく、冬期作業性にも優れている。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a rubber plasticizer which is difficult to be extracted into an oily substance and improves the cold resistance of rubber and winter workability, and a rubber composition containing the same.
[0002]
[Prior art and problems to be solved by the invention]
Conventionally, as a technique for improving the cold resistance of rubber, a method of adding a plasticizer such as phthalic acid ester, adipic acid ester or polyethylene glycol fatty acid ester is known. However, these conventional plasticizers are extracted when they come into contact with an oily substance such as grease, and are volatilized at a high temperature, so that the initial cold resistance is impaired. Furthermore, polyester plasticizers and the like are less likely to be extracted or volatilized, but have a problem that the original cold resistance is poor.
[0003]
Techniques for solving these problems are disclosed in Japanese Patent Application Laid-Open Nos. 61-145236 and 7-292235. In these techniques, rubber is used at a temperature of about −30 ° C. to 0 ° C. in a chloroprene rubber system. There is a phenomenon that becomes hard.
[0004]
The problem of the present invention is that it is difficult to extract even when contacted with an oily substance, is not easily volatilized at a high temperature, and is cold resistant of rubber, in particular, cold resistance of rubber at a temperature of -30 ° C. to 0 ° C. in a chloroprene rubber system. It is an object of the present invention to provide a rubber plasticizer and a rubber composition that can improve the performance and are excellent in workability in winter.
[0005]
[Means for Solving the Problems]
The present invention relates to a rubber plasticizer comprising an ester of a glycol having a number average molecular weight of 200 to 5,000 represented by the formula (I) and a branched fatty acid having 6 to 16 carbon atoms, and this rubber plasticizer with 100 weight of rubber. A rubber composition containing 3 to 50 parts by weight with respect to parts is provided.
[0006]
[Chemical 2]
[0007]
[Wherein, X represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, a represents a number of 0 to 2, m and n represent a number such that n / (m + n) = 0.03 to 0.5, The oxytetramethylene group and the group represented by (CH 2 ) a CH (X) CH 2 O may be block addition or random addition. However, when a is 2, X is not a hydrogen atom. ]
[0008]
DETAILED DESCRIPTION OF THE INVENTION
The plasticizer of the present invention is an ester of a glycol represented by the formula (I) having a number average molecular weight of 200 to 5000 determined from a hydroxyl value and a branched fatty acid having 6 to 16 carbon atoms, and 75 weights of diester. % Or more is preferable.
[0009]
The number average molecular weight of the glycol represented by the formula (I) in the plasticizer of the present invention is 200 to 5000 from the viewpoint of difficulty in extraction with respect to oily substances, resistance to volatilization at high temperatures, and cold resistance. , Preferably 300 to 3000, more preferably 400 to 2000.
[0010]
In the formula (I), the group represented by (CH 2 ) a CH (X) CH 2 O is preferably a group in which X is a methyl group and a is 0 to 2, X is a methyl group, and a is A group which is 0 or 2 is more preferred, and an oxypropylene group is particularly preferred. From the viewpoint of lowering the freezing point, n / (m + n) is preferably 0.03 to 0.5, more preferably 0.05 to 0.4, and particularly preferably 0.1 to 0.4. Further, from the viewpoint of lowering the freezing point, m is preferably from 3 to 50, more preferably from 5 to 30, and particularly preferably from 8 to 15. N is preferably 0.5 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.
[0011]
The glycol represented by the formula (I) can be synthesized by, for example, random polymerization or block polymerization of tetrahydrofuran and ethylene oxide, propylene oxide, tetrahydro-2-methylfuran, or the like. Commercial products can also be used.
[0012]
Examples of the branched fatty acid having 6 to 16 carbon atoms in the plasticizer of the present invention include isohexanoic acid, isoheptanoic acid, 2-ethylhexanoic acid, isononanoic acid, isodecanoic acid, isotridecanoic acid, isomyristic acid, and isopalmitic acid. Preferred are isoheptanoic acid, 2-ethylhexanoic acid and isononanoic acid, and particularly preferred are 2-ethylhexanoic acid and isononanoic acid. These may be used alone or in combination of two or more. It is essential that the branched fatty acid has a carbon number in the range of 6 to 16 because problems such as bleeding of the rubber composition do not occur.
[0013]
The plasticizer of the present invention can be easily synthesized by a known method, for example, by heat-dehydrating a metal catalyst such as glycol represented by the formula (I), a branched fatty acid, and dibutyltin oxide at a high temperature.
[0014]
The content of the plasticizer of the present invention in the rubber composition is 3 to 50 parts by weight with respect to 100 parts by weight of rubber, preferably from the viewpoint of cold resistance, bleed and other physical properties, and cost. 5 to 40 parts by weight, more preferably 10 to 30 parts by weight.
[0015]
The rubber according to the present invention includes natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR), butyl rubber (IIR), styrene butadiene rubber (SBR), acrylonitrile butadiene rubber (NBR), ethylene propylene rubber (EPDM). ), Chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), epichlorohydrin rubber (CHR), and the like. CR, CSM, and CHR are preferable, and CR is particularly preferable.
[0016]
The rubber composition of the present invention can be easily produced with an ordinary kneader, for example, a Banbury mixer, a roll, an intensive mixer and the like. In addition to reinforcing agents such as carbon black and silica, vulcanization accelerators, vulcanizing agents, and other chemicals that are usually blended in rubber, fillers and colorants such as calcium carbonate, talc, and clay, as needed, UV rays Absorbers, general-purpose plasticizers (phthalic acid-based, trimellitic acid-based, phosphoric acid-based, epoxy-based, etc.) can be added as appropriate.
[0017]
【Example】
In the examples, “%” is by weight unless otherwise specified.
[0018]
Synthesis example 1
In formula (I), a glycol having a number average molecular weight of 800 (PTG−), wherein X is a methyl group, a is 2, m is 9, n is 1.6, and n / (m + n) is 0.15. L800, manufactured by Hodogaya Chemical Co., Ltd.), 173 g of 2-ethylhexanoic acid, and 0.57 g of dibutyltin oxide as a catalyst were weighed into a 1 liter four-necked flask and dehydrated at 230 ° C. while blowing nitrogen. After the esterification reaction was performed for 5 to 6 hours, excess 2-ethylhexanoic acid was distilled off to obtain an ester (PTGR8002EH, composition: diester 90%, monoester 10%).
[0019]
Synthesis example 2
In formula (I), a glycol having a number average molecular weight of 1000 (PTG−), wherein X is a methyl group, a is 2, m is 11.5, n is 2, and n / (m + n) is 0.15. L1000, manufactured by Hodogaya Chemical Co., Ltd.), 173 g of 2-ethylhexanoic acid, and 0.67 g of dibutyltin oxide were reacted in the same manner as in Synthesis Example 1 to produce an ester (PTGR10002EH, composition: 85% diester, mono Ester 15%) was obtained.
[0020]
Synthesis example 3
In formula (I), a glycol having a number average molecular weight of 1000, wherein X is a methyl group, a is 0, m is 10.5, n is 4.5, and n / (m + n) is 0.3 PPTG1000, manufactured by Hodogaya Chemical Co., Ltd.) 500 g, 2-ethylhexanoic acid 173 g, and dibutyltin oxide 0.67 g were reacted in the same manner as in Synthesis Example 1 to produce an ester (PTGPO10002EH, composition: 75% diester, mono Ester 25%) was obtained.
[0021]
Comparative Synthesis Example 1
321 g of adipic acid, 180 g of 1,4-butanediol, 58 g of n-octanol and 0.55 g of dibutyltin oxide were esterified in the same manner as in Synthesis Example 1, dealcoholized, and average molecular weight calculated from the charged value was about 2500. Polyester A was obtained.
[0022]
Comparative Synthesis Example 2
By reacting 513 g of polyoxytetramethylene glycol having a number average molecular weight of 1000, 200 g of lauric acid, and 0.7 g of dibutyltin oxide in the same manner as in Synthesis Example 1, an ester (PTG1000L, composition: diester 87%, monoester 13%) is produced. Obtained.
[0023]
Comparative Synthesis Example 3
By reacting 400 g of polypropylene glycol having a number average molecular weight of 600, 230 g of 2-ethylhexanoic acid and 0.6 g of dibutyltin oxide in the same manner as in Synthesis Example 1, an ester (PPG2EH, composition: 96% diester, 4% monoester) is obtained. Obtained.
[0024]
Examples 1-6 and Comparative Examples 1-7
Using the esters obtained in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 to 3 or di-2-ethylhexyl adipate generally used for improving cold resistance as a plasticizer, the following blends were made with various CR rubbers shown in Table 1. A rubber composition was prepared and vulcanized at 170 ° C. for 10 minutes to produce a test piece having a thickness of 2 mm. The test piece was evaluated for cold resistance, resistance to grease extraction, heat resistance, bleed, pour point, and fluidity after storage in the refrigerator by the following methods. The results are shown in Table 1.
[0025]
<Rubber composition>
CR rubber 100.0 parts by weight SRF carbon * 1 60.0 parts by weight anti-aging PA * 2 5.0 parts by weight magnesium oxide 4.0 parts by weight zinc oxide 5.0 parts by weight stearic acid 2.0 parts by weight vulcanized Accelerator 22 * 3 0.5 parts by weight Plasticizer 30.0 parts by weight
* 1 SRF Carbon: Carbon Black SRF
* 2 Anti-aging PA: N-phenyl-α-naphthylamine
* 3 Vulcanization accelerator 22: Ethylenethiourea <Cold resistance>
Cold resistance was evaluated by the Gehman torsion test by the method of JIS K-6301 (new JIS K-6261). T100, T10, T5, and T2 are temperatures at which the torsion modulus is 100 times, 10 times, 5 times, and 2 times that of normal temperature (23 ° C.), respectively, and the lower the number, the better the cold resistance.
[0026]
<Grease extractability>
Grease was applied to a test piece cut to 10 × 10 cm so as to have a thickness of 20 mm, and the test piece was left in a thermostat at 120 ° C. for 50 hours. Thereafter, the grease was wiped off at room temperature, and the test piece was evaluated by the method of JIS K-6301 (new JIS K-6261). The extractability of the plasticizer in the rubber composition with respect to grease can be determined by evaluation of cold resistance. The harder it is extracted into grease, the better the cold resistance after extraction with grease is.
[0027]
<Heat resistance>
The test piece was cut into a No. 3 dumbbell shape and allowed to stand in a constant temperature machine at 120 ° C. for 100 hours, and the volatile content was measured from the change in weight. The lower the volatile content, the better the heat resistance.
[0028]
<Bleed>
The test piece was stored for 7 days in an atmosphere of 40 ° C., and its surface condition was observed with the naked eye and evaluated according to the following criteria.
[0029]
○: No plasticizer bleed Δ: Slight bleed ×: Severe surface bleed <pour point>
A plasticizer is sealed at a half height in a glass tube having a diameter of about 5 mm and a length of about 60 mm, and solidified at -70 ° C. in dry ice + ethanol system. The temperature was raised at a rate, and the temperature at which the plasticizer in the glass tube flows out was measured and used as the pour point.
[0030]
<Fluidity after storage in refrigerator>
The plasticizer was put in a 50 mL sample tube and stored in a refrigerator at 5 ° C. for 24 hours, and the state of the plasticizer was evaluated according to the following criteria.
[0031]
◎: Transparent and fluidized ○: Suspended and opaque, but fluidized Δ: Partially solidified, but fluidized ×: Almost solidified, not fluidized [0032]
[Table 1]
[0033]
* 1: Mercaptan modified CR manufactured by Denki Kagaku Kogyo Co., Ltd.
* 2: Zandogen modified CR manufactured by Denki Kagaku Kogyo Co., Ltd.
* 3: Sulfur modified CR manufactured by Denki Kagaku Kogyo Co., Ltd.
* 4: DuPont Dow Elastomer Japan (Mercaptan-modified CR manufactured by Showa Dee Dee Manufacturing Co., Ltd.)
[0034]
【The invention's effect】
The rubber composition of the present invention is excellent in flexibility at low temperatures, particularly at T2 and T5, has little extraction by oily substances such as grease, and is excellent in maintaining cold resistance because it is difficult to volatilize at high temperatures. Yes. In addition, it does not solidify in winter and is excellent in winter workability.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001279439A JP4515004B2 (en) | 2001-09-14 | 2001-09-14 | Rubber composition |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2001279439A JP4515004B2 (en) | 2001-09-14 | 2001-09-14 | Rubber composition |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2003082221A JP2003082221A (en) | 2003-03-19 |
JP4515004B2 true JP4515004B2 (en) | 2010-07-28 |
Family
ID=19103630
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2001279439A Expired - Fee Related JP4515004B2 (en) | 2001-09-14 | 2001-09-14 | Rubber composition |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4515004B2 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4810798B2 (en) | 2004-06-01 | 2011-11-09 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61145236A (en) * | 1984-12-19 | 1986-07-02 | Kao Corp | Chloroprene rubber composition |
JPS62253643A (en) * | 1986-04-21 | 1987-11-05 | Kao Corp | Cold-and heat-resistant plasticizer for butadiene based rubber |
JPS63199744A (en) * | 1987-02-16 | 1988-08-18 | Showa Denko Du Pont Kk | Plasticizer for chloroprene rubber |
JPH07292235A (en) * | 1994-04-20 | 1995-11-07 | Sanyo Chem Ind Ltd | Low-temperature plasticizer |
JPH09263632A (en) * | 1996-03-29 | 1997-10-07 | Hodogaya Chem Co Ltd | Polyoxyalkylene derivative containing both acrylic group and hydroxyl group |
-
2001
- 2001-09-14 JP JP2001279439A patent/JP4515004B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61145236A (en) * | 1984-12-19 | 1986-07-02 | Kao Corp | Chloroprene rubber composition |
JPS62253643A (en) * | 1986-04-21 | 1987-11-05 | Kao Corp | Cold-and heat-resistant plasticizer for butadiene based rubber |
JPS63199744A (en) * | 1987-02-16 | 1988-08-18 | Showa Denko Du Pont Kk | Plasticizer for chloroprene rubber |
JPH07292235A (en) * | 1994-04-20 | 1995-11-07 | Sanyo Chem Ind Ltd | Low-temperature plasticizer |
JPH09263632A (en) * | 1996-03-29 | 1997-10-07 | Hodogaya Chem Co Ltd | Polyoxyalkylene derivative containing both acrylic group and hydroxyl group |
Also Published As
Publication number | Publication date |
---|---|
JP2003082221A (en) | 2003-03-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1782966B1 (en) | Rubber composition for tire and pneumatic tire using the same | |
US5728760A (en) | Use of ring-brominated benzoate compounds as flame retardants and/or plasticizers | |
US9394426B2 (en) | Vegetable oil derivatives as extender oils for elastomer compositions | |
US20150203657A1 (en) | Non-phthalic plasticiser | |
JP5882074B2 (en) | Rubber composition and pneumatic tire | |
JP4515004B2 (en) | Rubber composition | |
JP5120925B2 (en) | Rubber composition for tire and pneumatic tire using the same | |
JP2003064233A (en) | Polyvinyl chloride-based resin film for agriculture and polyvinyl chloride-based resin composition | |
JP4596405B2 (en) | Rubber composition | |
US7312266B2 (en) | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers | |
JP5139675B2 (en) | CROSSLINKER, RUBBER COMPOSITION CONTAINING THIS CROSSLINKER, AND TIRE PRODUCED BY USING THE RUBBER COMPOSITION | |
US6747081B2 (en) | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers | |
JPH06107867A (en) | Thermoplastic elastomer composition | |
US6927247B2 (en) | Organic thiol metal-free stabilizers and plasticizers for halogen-containing polymers | |
JP3467380B2 (en) | Rubber composition with improved chargeability and pneumatic tire using the same | |
CA1264163A (en) | Citrate esters and methods | |
JP2005068405A (en) | Rubber composition | |
JP2006016523A (en) | Rubber composition | |
JP2020002322A (en) | Rubber composition and pneumatic tire using the same | |
JP2019182920A (en) | Rubber composition and pneumatic tire using the same | |
JP5446380B2 (en) | Rubber composition for tire tread | |
JP2737252B2 (en) | Plasticizer for rubber | |
JPH04261443A (en) | Rubber additive and rubber composition | |
JP2008111071A (en) | Rubber composition and pneumatic tire having run-flat performance using the same | |
JPH05170972A (en) | Rubber composition for tires |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20071105 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071105 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20100426 |
|
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: 20100511 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100512 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130521 Year of fee payment: 3 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140521 Year of fee payment: 4 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
LAPS | Cancellation because of no payment of annual fees |