JP4420096B2 - Method for producing silica-containing natural rubber composition and silica-containing natural rubber composition obtained thereby - Google Patents
Method for producing silica-containing natural rubber composition and silica-containing natural rubber composition obtained thereby Download PDFInfo
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- JP4420096B2 JP4420096B2 JP2007257847A JP2007257847A JP4420096B2 JP 4420096 B2 JP4420096 B2 JP 4420096B2 JP 2007257847 A JP2007257847 A JP 2007257847A JP 2007257847 A JP2007257847 A JP 2007257847A JP 4420096 B2 JP4420096 B2 JP 4420096B2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 100
- 239000000377 silicon dioxide Substances 0.000 title claims description 44
- 239000000203 mixture Substances 0.000 title claims description 40
- 244000043261 Hevea brasiliensis Species 0.000 title claims description 26
- 229920003052 natural elastomer Polymers 0.000 title claims description 26
- 229920001194 natural rubber Polymers 0.000 title claims description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920006173 natural rubber latex Polymers 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- -1 carboxyl ion Chemical class 0.000 claims description 14
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 13
- 229920000126 latex Polymers 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 239000004816 latex Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- 230000035939 shock Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000004594 Masterbatch (MB) Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 239000002280 amphoteric surfactant Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- BADXJIPKFRBFOT-UHFFFAOYSA-N dimedone Chemical compound CC1(C)CC(=O)CC(=O)C1 BADXJIPKFRBFOT-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000004636 vulcanized rubber Substances 0.000 description 2
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)C(C)C(C)N Chemical compound CC(*)C(C)C(C)N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920006317 cationic polymer Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Description
本発明は、シリカ含有天然ゴム組成物の製造方法及びそれによって得られるシリカ含有天然ゴム組成物に関し、更に詳しくはシリカスラリー、天然ゴムラテックス及び両性界面活性剤から優れた低発熱性のシリカ含有天然ゴム組成物を製造方法並びにそれによって得られるシリカ含有天然ゴム組成物に関する。 TECHNICAL FIELD The present invention relates to a method for producing a silica-containing natural rubber composition and a silica-containing natural rubber composition obtained thereby, and more particularly, a silica-containing natural rubber having excellent low heat generation from silica slurry, natural rubber latex and amphoteric surfactant. The present invention relates to a method for producing a rubber composition and a silica-containing natural rubber composition obtained thereby.
特許文献１にはシランカップリング剤の存在下に、ゴムラテックス、シリカ及びカチオン性高分子を混合してゴムラテックス中のゴムとシリカを共凝固させてシリカをゴム中に良好に分散させることが記載されているが、両性界面活性剤を添加して乾燥することについての記載は認められない。 In Patent Document 1, rubber latex, silica and a cationic polymer are mixed in the presence of a silane coupling agent to co-coagulate the rubber and silica in the rubber latex so that the silica is well dispersed in the rubber. Although described, there is no description about adding an amphoteric surfactant and drying.
従って、本発明の目的は、シリカスリラーとラテックス状態の天然ゴムとを一緒にして乾燥することで、優れた低発熱性を示すゴム組成物を与えるシリカマスターバッチを製造することにある。 Accordingly, an object of the present invention is to produce a silica masterbatch that gives a rubber composition exhibiting excellent low heat build-up by drying together a silica chiller and latex natural rubber.
本発明に従えば、天然ゴムラテックス、シリカ並びに、以下の式（Ｉ）で示される、分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を分子中に有する化合物を含有する液状組成物から水分を除去することを特徴とするシリカ含有天然ゴム組成物の製造方法並びにそれによって得られたシリカ含有天然ゴム組成物が提供される。 According to the present invention, water is removed from a liquid composition containing natural rubber latex, silica, and a compound represented by the following formula (I) having both a quaternary ammonium salt structure and a carboxyl ion in the molecule. There is provided a process for producing a silica-containing natural rubber composition, characterized by removing water, and a silica-containing natural rubber composition obtained thereby.
本発明によれば、シリカスラリーとラテックス状態の天然ゴムに、特定の両性界面活性剤を添加して乾燥することによって、天然ゴムに常法に従ってシリカを配合混練したシリカ配合天然ゴム組成物よりもゴム組成物の低発熱化を図ることができる。 According to the present invention, by adding a specific amphoteric surfactant to a silica slurry and a natural rubber in a latex state and drying, a natural rubber composition containing silica is blended and kneaded in accordance with a conventional method. The heat generation of the rubber composition can be reduced.
本発明者らは、前記課題を解決すべく研究を進めた結果、シリカスリラーとラテックス状態の天然ゴムに、以下に説明するような両性界面活性剤を添加（溶解又は撹拌）した後に、乾燥することによって、優れた低発熱性を示すゴム組成物を与えるシリカマスターバッチを製造できることを見出した。 As a result of conducting research to solve the above-mentioned problems, the present inventors have added (dissolved or stirred) an amphoteric surfactant as described below to silica chiller and latex natural rubber, and then dried. It has been found that a silica masterbatch that gives a rubber composition exhibiting excellent low heat buildup can be produced.
本発明において使用する４級アンモニウム塩構造及びカルボキシルイオンを有する化合物は以下の式（Ｉ）で示される化合物である。 Compounds having a quaternary ammonium salt structure and a carboxyl ion used in the present invention is a compound represented by the following formula (I).
（式中、Ｒ1，Ｒ2及びＲ3は、それぞれ独立に、炭素数１〜２０（好ましくは１〜１０）のアルキル基、炭素数６〜２０（好ましくは６〜１０）のアリール基、炭素数７〜２０（好ましくは７〜１０）のアラルキル基から選ばれる少なくとも１つの有機基であり、エステル結合及びアミド結合を含んでもよく、Ｒ4は炭素数１〜１２（好ましくは１〜６）のアルキレン基を示す。） (Wherein R 1 , R 2 and R 3 each independently represents an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10), an aryl group having 6 to 20 carbon atoms (preferably 6 to 10 carbon atoms), It is at least one organic group selected from aralkyl groups having 7 to 20 carbon atoms (preferably 7 to 10 carbon atoms), and may contain an ester bond and an amide bond, and R 4 has 1 to 12 carbon atoms (preferably 1 to 6 carbon atoms). ) Represents an alkylene group.)
前記４級アンモニウム塩構造及びカルボキシルイオンを有する化合物の添加量は、シリカの質量に対して、０．００１〜５質量％、好ましくは０．０５〜２質量％である。この添加量が少ないとｔａｎδが高くなり（発熱性が増大）、逆に多いと加硫後のゴムの強度が低下してしまうので好ましくない。 The amount of the compound having a quaternary ammonium salt structure and a carboxyl ion is 0.001 to 5% by mass, preferably 0.05 to 2% by mass, based on the mass of silica. If the amount added is small, tan δ increases (exothermic property increases), while if it is large, the strength of the rubber after vulcanization decreases, which is not preferable.
本発明によれば、前記４級アンモニウム構造及びカルボキシルイオンを分子中に有する化合物を含むシリカ含有天然ゴムラテックスは任意の方法で調製することができる。例えば常温、大気中で所定量の前記化合物を天然ゴムラテックスに添加して撹拌することで調製することができる。本発明の好ましい態様では前記シリカ含有天然ゴムラテックスを水分を除去して乾燥する。水分を除去、乾燥する方法としては、一般に知られている方法を使用することができるが、前記シリカ含有天然ゴムラテックスをパルス雰囲気に噴霧して乾燥する方法は比較的低温で短時間での乾燥ができるので好適に利用できる。パルス乾燥は上記天然ゴムラテックスを、例えば特開平７−７１８７５号公報などに記載のパルス衝撃波を発生させるパルス燃焼機を用いて、乾燥してゴムを製造できる。本発明ではこのようなパルス燃焼機を用いて、好ましくは固形分濃度７０質量％以下のラテックスを、好ましくは周波数２５０〜１２００Hz、更に好ましくは３００〜１０００Hzで、好ましくは温度１４０℃以下、更に好ましくは４０〜１００℃，１００〜２００dB（デシベル）の条件下に乾燥室にラテックスを噴射乾燥させる。 According to the present invention, the silica-containing natural rubber latex containing a compound having a quaternary ammonium structure and a carboxyl ion in the molecule can be prepared by any method. For example, it can be prepared by adding a predetermined amount of the above compound to natural rubber latex and stirring in normal temperature and air. In a preferred embodiment of the present invention, the silica-containing natural rubber latex is dried after removing moisture. As a method for removing moisture and drying, a generally known method can be used. However, the method of spraying and drying the silica-containing natural rubber latex in a pulse atmosphere is drying at a relatively low temperature in a short time. Can be suitably used. In the pulse drying, rubber can be produced by drying the natural rubber latex using a pulse combustor that generates a pulse shock wave described in, for example, JP-A-7-71875. In the present invention, using such a pulse combustor, a latex having a solid content concentration of 70% by mass or less is preferably used, preferably at a frequency of 250 to 1200 Hz, more preferably 300 to 1000 Hz, and preferably a temperature of 140 ° C. or less. , The latex is spray-dried into a drying chamber under conditions of 40 to 100 ° C. and 100 to 200 dB (decibel).
天然ゴムは、経時的に粘度が増大していくことが一般的に知られている。このため従来から天然ゴム中に恒粘度剤を含ませることによって天然ゴムの粘度上昇を抑えることが行われている場合がある。本発明においても、必要に応じ、パルス燃焼による衝撃波の雰囲気下に噴射乾燥させる天然ゴムラテックス中に従来から知られている恒粘度剤を配合することができる。 Natural rubber is generally known to increase in viscosity over time. For this reason, conventionally, the viscosity increase of the natural rubber may be suppressed by including a viscosity stabilizer in the natural rubber. Also in the present invention, conventionally known constant viscosity agents can be blended in natural rubber latex that is spray-dried in a shock wave atmosphere by pulse combustion, if necessary.
本発明において使用することができ従来から知られている恒粘度剤としては、前記パルス乾燥条件下において分解するおそれのない一般に使用されている任意の恒粘度剤を用いることができ、具体的には例えば硫酸ヒドロキシルアミン（（ＮＨ2ＯＨ）2・Ｈ2ＳＯ4）、セミカルバシド（ＮＨ2ＣＯＮＨＮＨ2）、ジメドン（１，１−ジメチルシクロヘキサン−３，５−ジオン）などの少なくとも一種を用いることができる。 As the conventionally known thickener that can be used in the present invention, any generally used thickener that does not have the possibility of decomposing under the pulse drying conditions can be used. Is, for example, at least one of hydroxylamine sulfate ((NH 2 OH) 2 .H 2 SO 4 ), semicarbaside (NH 2 CONHNH 2 ), dimedone (1,1-dimethylcyclohexane-3,5-dione), etc. it can.
本発明において使用するシリカは従来からゴム組成物用に配合することができる任意のシリカを常法に従って湿式スラリー化して用いることができる。 As the silica used in the present invention, any silica that can be conventionally blended for a rubber composition can be used in the form of a wet slurry according to a conventional method.
本発明において使用するスラリー状態の天然ゴムは任意の天然ゴムスラリーを用いることができ、例えばフィールドラテックス、濃縮ラテックス、などやそれらの任意の混合物を用いることができる。 As the natural rubber in the slurry state used in the present invention, any natural rubber slurry can be used. For example, field latex, concentrated latex, and any mixture thereof can be used.
本発明に従って、天然ゴムのラテックス、シリカ水分散スラリー並びに分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物を混合する順には特に制限はないが、乾燥中や乾燥後のシリカ粒子どうしの凝集防止の観点から、分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物とシリカ水分散スラリーとを混合し、次にこれに天然ゴムスラリーを混合、撹拌するのが好ましい。 According to the present invention, there is no particular limitation on the order of mixing the natural rubber latex, the silica water dispersion slurry, and the compound having both the quaternary ammonium salt structure and the carboxyl ion in the molecule. From the viewpoint of preventing aggregation, it is preferable to mix a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule with an aqueous silica dispersion slurry, and then mix and agitate the natural rubber slurry.
本発明に係るゴム組成物には、前記した成分に加えて、カーボンブラックなどのその他の補強剤（フィラー）、加硫又は架橋剤、加硫又は架橋促進剤、各種オイル、老化防止剤、可塑剤などのタイヤ用、その他のゴム組成物用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は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。 In addition to the components described above, the rubber composition according to the present invention includes other reinforcing agents (fillers) such as carbon black, vulcanization or crosslinking agents, vulcanization or crosslinking accelerators, various oils, anti-aging agents, plastics Various additives that are generally blended for tires such as additives and other rubber compositions can be blended, and these additives are kneaded into a composition by a general method to be vulcanized or crosslinked. Can be used to do. As long as the amount of these additives is not contrary to the object of the present invention, a conventional general amount can be used.
以下、実施例によって本発明を更に説明するが、本発明の範囲をこれらの実施例に限定するものでないことはいうまでもない。 EXAMPLES Hereinafter, although an Example demonstrates this invention further, it cannot be overemphasized that the scope of the present invention is not limited to these Examples.
実施例１〜２及び比較例１〜４
１．シリカマスターバッチの作製
実施例１
（１）シリカスラリーの調製
沈降性シリカ（日本シリカ工業（株）製ニップシールＶＮ３）１００ｇを水５００ｇに添加してスギノマシン社製アルティマイザーを使用して混合分散させシリカスラリーを得た。このシリカスラリーに、分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物として、下記式のアデカアンホートＡＢ−３５Ｌ１．０ｇを添加し、撹拌分散させた。このシリカスラリー中のシリカの平均粒子径は約０．１５μｍであった。
Examples 1-2 and Comparative Examples 1-4
1. Preparation of silica masterbatch
Example 1
(1) Preparation of Silica Slurry 100 g of precipitated silica (nip seal VN3 manufactured by Nippon Silica Industry Co., Ltd.) was added to 500 g of water and mixed and dispersed using an optimizer manufactured by Sugino Machine to obtain a silica slurry. As a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule, 1.0 g of Adeka Anhhot AB-35L of the following formula was added to this silica slurry, and the mixture was stirred and dispersed. The average particle diameter of silica in this silica slurry was about 0.15 μm.
（２）天然ゴムラテックスの調製
タイ国ハジャイ市近郊で採取された天然ゴムラテックス（Ｆ−ＬＴＸ）に１．０質量％のアンモニアを安定化剤兼防腐剤として加えたものをウェストフェリア社製遠心分離装置で遠心分離して濃縮ラテックス（Ｃ−ＬＴＸ）を得た。このＣ−ＬＴＸの固形分は３０質量％であった。
(2) Preparation of natural rubber latex Centrifugal made by Westferia Co., Ltd., natural rubber latex (F-LTX) collected in the suburbs of Hat Yai, Thailand, with 1.0 mass% of ammonia added as a stabilizer and preservative. Centrifugation was performed with a separator to obtain concentrated latex (C-LTX). The solid content of this C-LTX was 30% by mass.
（３）マスターバッチの作製
（１）のシリカスラリー及び（２）のＣ−ＬＴＸをゴム／シリカ＝１００／６０（質量比）となるように混合して液状組成物を得た。この液状組成物を定量ポンプで吸収してパルテック社製パルス燃焼乾燥装置ハイパルコンに導入し水分を除去しシリカ含有ゴム組成物を得た。なお、本乾燥装置の運転条件は以下の通りであった。
（１）と（２）の混合溶液を周波数１０００Ｈｚ、温度６０℃の条件でパルス衝撃波乾燥機を用いて乾燥させた。衝撃エネルギーは１３０ｄｂ〜１４０ｄｂであった。
(3) Preparation of master batch The silica slurry of (1) and C-LTX of (2) were mixed so as to be rubber / silica = 100/60 (mass ratio) to obtain a liquid composition. The liquid composition was absorbed by a metering pump and introduced into a pulse combustion dryer Hipalcon manufactured by Partec Co., Ltd. to remove water and obtain a silica-containing rubber composition. In addition, the operating conditions of this drying apparatus were as follows.
The mixed solution of (1) and (2) was dried using a pulse shock wave dryer under conditions of a frequency of 1000 Hz and a temperature of 60 ° C. The impact energy was 130 db-140 db.
実施例２
（１）シリカスラリーの調製
分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物として、以下の式のアデカアンホートＰＢ−３０Ｌを１．０ｇ使用した以外は実施例１と同様にした。
Example 2
(1) Preparation of silica slurry The same procedure as in Example 1 was carried out except that 1.0 g of Adeka Anhhot PB-30L of the following formula was used as a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule.
（２）天然ゴムラテックスの調製
実施例１と同じものを使用した。
(2) Preparation of natural rubber latex The same one as in Example 1 was used.
（３）マスターバッチの作製
実施例１と同様に実施した。
(3) Preparation of master batch The same as in Example 1.
比較例１
（１）シリカスラリーの調製
分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物を添加しなかった以外は実施例１と同様にして調製した。
Comparative Example 1
(1) Preparation of silica slurry The silica slurry was prepared in the same manner as in Example 1 except that a compound having both a quaternary ammonium salt structure and a carboxyl ion was not added to the molecule.
（２）天然ゴムラテックスの調製
実施例１と同じものを使用した。
(2) Preparation of natural rubber latex The same one as in Example 1 was used.
（３）マスターバッチの作製
実施例１と同様に実施した。
(3) Preparation of master batch The same as in Example 1.
比較例２
（１）シリカスラリーの調製
分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物のかわりにシランカップリング剤（デグッサ社製Ｓｉ６９）をシリカの重量に対して６．６７ｇ添加した以外は実施例１と同様にした。
Comparative Example 2
(1) Preparation of silica slurry Except that 6.67 g of a silane coupling agent (Si69 manufactured by Degussa) was added to the weight of silica instead of a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule. Same as Example 1.
（２）天然ゴムラテックスの調製
実施例１と同じものを使用した。
(2) Preparation of natural rubber latex The same one as in Example 1 was used.
（３）マスターバッチの作製
実施例１と同様に実施した。
(3) Preparation of master batch The same as in Example 1.
２．比較例３と比較例４に使用する天然ゴムの作製
比較例３及び４で使用したシリカは日本シリカ工業（株）製ニップシールＶＮ３である。
実施例１の（２）に記載に従って作製したＣ−ＬＴＸを定量ポンプで吸引してパルテック社製パルス燃焼乾燥装置に導入し水分を除去することによって作製した。乾燥装置の運転条件は実施例１と同様にした。使用前に１．５Ｌの密閉型混合機で約１２０℃で２分３０秒間素練りを行った。
2. Production of Natural Rubber Used in Comparative Example 3 and Comparative Example 4 The silica used in Comparative Examples 3 and 4 is a nip seal VN3 manufactured by Nippon Silica Kogyo Co., Ltd.
C-LTX produced according to the description in (2) of Example 1 was sucked with a metering pump, introduced into a pulse combustion drying apparatus manufactured by Partec, and removed to remove moisture. The operating conditions of the drying apparatus were the same as in Example 1. Prior to use, the mixture was masticated at about 120 ° C. for 2 minutes and 30 seconds with a 1.5 L closed mixer.
ゴム配合評価
サンプルの調製
表Ｉに示す配合において、加硫促進剤と硫黄を除く成分を０．６リットルの密閉型ミキサーでローター回転後５０rpmで１２分間混練し、１４５℃に達したときに放出してマスターバッチを得た。このマスターバッチに加硫促進剤と硫黄をオープンロールで混練し、ゴム組成物を得た。このゴム組成物を用いて、以下に示す試験法で未加硫物性を評価した。結果は表Ｉに示す。
Rubber compounding evaluation
Sample preparation In the formulation shown in Table I, the ingredients other than the vulcanization accelerator and sulfur were kneaded with a 0.6 liter closed mixer for 12 minutes at 50 rpm after rotating the rotor and released when the temperature reached 145 ° C. Got a batch. A vulcanization accelerator and sulfur were kneaded with this masterbatch with an open roll to obtain a rubber composition. Using this rubber composition, unvulcanized physical properties were evaluated by the following test methods. The results are shown in Table I.
次に得られたゴム組成物を１５×１５×０．２cmの金型中で１６０℃で１０分間加硫して加硫ゴムシートを調製し、以下に示す試験法で加硫ゴムの物性を測定した。結果は表Ｉに示す。 Next, the resulting rubber composition was vulcanized in a 15 × 15 × 0.2 cm mold at 160 ° C. for 10 minutes to prepare a vulcanized rubber sheet. The physical properties of the vulcanized rubber were measured by the following test methods. It was measured. The results are shown in Table I.
ゴム物性評価試験法
ムーニー粘度：ＪＩＳ Ｋ６３００に基づき１００℃で測定した。
Rubber property evaluation test method Mooney viscosity: measured at 100 ° C. based on JIS K6300.
レオメーター試験：ＪＩＳ Ｋ６３００に基づき１６０℃で測定した。 Rheometer test: Measured at 160 ° C. based on JIS K6300.
ＪＩＳ硬度：ＪＩＳ Ｋ６２５３に基づき所定の各温度で測定した。 JIS hardness: Measured at predetermined temperatures based on JIS K6253.
引張試験：ＪＩＳ Ｋ６２５１に基づき室温で測定した。 Tensile test: Measured at room temperature based on JIS K6251.
粘弾性試験：東洋精機製作所製の粘弾性スペクトロメーターを用いて初期歪１０％、動歪±２％、周波数２０Hzで測定した。 Viscoelasticity test: Measured using a viscoelasticity spectrometer manufactured by Toyo Seiki Seisakusho at an initial strain of 10%, a dynamic strain of ± 2%, and a frequency of 20 Hz.
リュプケ反発弾性：ＪＩＳ Ｋ６２５５に基づき表Ｉに記載の温度で測定した。 Lupke rebound resilience: measured at the temperatures listed in Table I based on JIS K6255.
耐摩耗性試験（ランボーン型）：ＪＩＳ Ｋ６２６４に基づき岩本製作所（株）製ランボーン摩耗試験機を使用して荷重５kg、スリップ率２５％で摩耗減量を測定し比較例１の摩耗減量を１００として指数表示した。（数字が大きい程耐摩耗性が良い。） Wear resistance test (Lambourne type): Based on JIS K6264, the wear loss was measured at a load of 5 kg and a slip rate of 25% using a Lambone wear tester manufactured by Iwamoto Seisakusho. displayed. (The larger the number, the better the wear resistance.)
表Ｉ脚注
＊１：フレキシス（株）製サントフレックス１３
＊２：日本油脂（株）製ビーズステアリン酸ＮＹ
＊３：正同化学工業（株）製亜鉛華３号
＊４：デグッサ（株）製Ｓｉ６９
＊５：出光興産（株）製ダイアナプロセスＡＨ−２０
＊６：大内新興化学工業（株）製ノクセラーＣＺ−Ｇ
＊７：大内新興化学工業（株）製ノクセラーＤＰ
＊８：鶴見化学工業（株）製粉末イオウ
Table I footnote * 1: Santoflex 13 manufactured by Flexis Co., Ltd.
* 2: NY stearate NY produced by NOF Corporation
* 3: Zinc Hua 3 manufactured by Shodo Chemical Industry Co., Ltd. * 4: Si69 manufactured by Degussa Co., Ltd.
* 5: Diana Process AH-20 manufactured by Idemitsu Kosan Co., Ltd.
* 6: Ouchi Shinsei Chemical Co., Ltd. Noxeller CZ-G
* 7: Nouchi Cellar DP manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
* 8: Powder sulfur manufactured by Tsurumi Chemical Co., Ltd.
本発明によれば、天然ゴムラテックス、シリカ並びに分子中に４級アンモニウム塩構造及びカルボキシルイオンの双方を有する化合物を含む液状組成物から水分を除去することによって低発熱性に優れたシリカ含有天然ゴム組成物を製造することができ、各種タイヤ用材料や各種の産業用ゴム製品などとして使用するのに適している。 According to the present invention, a silica-containing natural rubber excellent in low heat build-up by removing water from a natural rubber latex, a liquid composition containing silica and a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule. The composition can be produced and is suitable for use as various tire materials and various industrial rubber products.
Claims (6)
で表される、４級アンモニウム塩構造及びカルボキシルイオンの双方を分子中に有する化合物を含有する液状組成物から水分を除去することを特徴とするシリカ含有天然ゴム組成物の製造方法。 Natural rubber latex, silica and formula (I):
A method for producing a silica-containing natural rubber composition, comprising removing water from a liquid composition containing a compound having both a quaternary ammonium salt structure and a carboxyl ion in the molecule.
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| JP2007257847A JP4420096B2 (en) | 2007-10-01 | 2007-10-01 | Method for producing silica-containing natural rubber composition and silica-containing natural rubber composition obtained thereby |
| MYPI20083601 MY143748A (en) | 2007-10-01 | 2008-09-16 | Method of production of silica-containing natural rubber composition and silica-containing natural rubber composition obtained therefrom |
| CN2008101492718A CN101402748B (en) | 2007-10-01 | 2008-09-22 | Method for producing silicon dioxide-containing nature rubber composition and silicon dioxide-containing nature rubber composition produced with the method |
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| CN101914229B (en) * | 2010-08-24 | 2011-10-12 | 中国热带农业科学院农产品加工研究所 | Method for preparing kieselguhr/natural rubber composite material |
| WO2013097317A1 (en) * | 2011-12-27 | 2013-07-04 | 确成硅化学股份有限公司 | Method for blending natural latex and silica slurry |
| JP5845102B2 (en) * | 2012-02-01 | 2016-01-20 | 住友ゴム工業株式会社 | Method for producing rubber composition |
| CN104672542A (en) * | 2013-11-28 | 2015-06-03 | 招远市东晟橡胶制品有限公司 | Rubber tube |
| CN104311906B (en) * | 2014-11-12 | 2017-11-10 | 海南天然橡胶产业集团股份有限公司 | A kind of preparation method of tire belt white carbon/NR masterbatch |
| CN104893024B (en) * | 2015-06-29 | 2016-09-14 | 确成硅化学股份有限公司 | The method that natural emulsion is blended with precipitated silica |
| JP6170270B1 (en) * | 2016-02-25 | 2017-07-26 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| EP3421535B1 (en) * | 2016-02-25 | 2020-11-18 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
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| WO1998049241A1 (en) * | 1997-04-30 | 1998-11-05 | The Yokohama Rubber Co., Ltd. | Process for producing modified carbon black for reinforcing rubber and process for producing rubber composition containing modified carbon black |
| US6322721B1 (en) * | 1998-08-24 | 2001-11-27 | Technical Processing, Inc. | Quaternary ammonium salt vulcanization accelerators for rubbers and plastics |
| JP5031151B2 (en) * | 2001-07-18 | 2012-09-19 | 電気化学工業株式会社 | Chloroprene-based rubber composition |
| EP1607408B1 (en) * | 2001-07-27 | 2010-11-17 | Bridgestone Corporation | Natural rubber master batch, production method thereof, and natural rubber composition |
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