JP2018188532A - Chloroprene rubber composition and vulcanizate thereof - Google Patents
Chloroprene rubber composition and vulcanizate thereof Download PDFInfo
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- 229920001084 poly(chloroprene) Polymers 0.000 title claims abstract description 53
- 239000000203 mixture Substances 0.000 title claims abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 14
- 239000011256 inorganic filler Substances 0.000 claims abstract description 14
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 14
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- -1 alkoxy alkylsilanes Chemical class 0.000 claims description 3
- 125000003161 (C1-C6) alkylene group Chemical group 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 35
- 239000005060 rubber Substances 0.000 description 35
- 150000001412 amines Chemical class 0.000 description 12
- 238000013329 compounding Methods 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- PUSFNJAULLXORZ-UHFFFAOYSA-N n',n'-dimethyl-n-octadecylpropane-1,3-diamine Chemical compound CCCCCCCCCCCCCCCCCCNCCCN(C)C PUSFNJAULLXORZ-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- UJAWGGOCYUPCPS-UHFFFAOYSA-N 4-(2-phenylpropan-2-yl)-n-[4-(2-phenylpropan-2-yl)phenyl]aniline Chemical compound C=1C=C(NC=2C=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C=CC=1C(C)(C)C1=CC=CC=C1 UJAWGGOCYUPCPS-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IOKYPACLTOWHCM-UHFFFAOYSA-N n,n-diethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(CC)CC IOKYPACLTOWHCM-UHFFFAOYSA-N 0.000 description 1
- AVOKRHSASDONRL-UHFFFAOYSA-N n,n-diethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(CC)CC AVOKRHSASDONRL-UHFFFAOYSA-N 0.000 description 1
- MNOIOAHRVYPSPE-UHFFFAOYSA-N n,n-diethyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(CC)CC MNOIOAHRVYPSPE-UHFFFAOYSA-N 0.000 description 1
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、クロロプレンゴム組成物及びそれを用いた加硫物に関し、更に詳しくは、クロロプレンゴム組成物へのシリカの分散性を改良し、未加硫ゴムの粘度低減を改良できて加工性も良好となるクロロプレンゴム組成物及びその加硫物に関する。 The present invention relates to a chloroprene rubber composition and a vulcanized product using the same. More specifically, the dispersibility of silica in the chloroprene rubber composition can be improved, the viscosity reduction of unvulcanized rubber can be improved, and the processability can be improved. The present invention relates to an improved chloroprene rubber composition and a vulcanized product thereof.
近年、高減衰性部材やカラー配合等の用途において、クロロプレンゴムとシリカの複合化に対する需要が増加している。 In recent years, there has been an increasing demand for composites of chloroprene rubber and silica in applications such as highly attenuating members and color blending.
シリカは、その表面官能基であるシラノール基の水素結合により粒子同士が凝集する傾向にあり、ゴム中へのシリカの分散を良くするためには混練時間を長くする必要がある。また、シラノール基と金属の親和性が高いため、シリカを配合したゴムは金属ロールに粘着し、加工が困難であった。また、ゴム中へのシリカの分散が不十分なためゴム組成物のムーニー粘度が高くなり、押出しなどの加工性に劣るなどの欠点を有していた。更に、シリカ粒子の表面が酸性であることから、加硫促進剤として使用される塩基性物質を吸着し、ゴム組成物の加硫が十分に行われず、貯蔵弾性率が上がらないという欠点を有していた。そのため、従来からシリカ配合ゴム組成物における分散性や加工性等の改良が求められている。 Silica tends to agglomerate particles due to hydrogen bonding of silanol groups which are surface functional groups, and it is necessary to increase the kneading time in order to improve the dispersion of silica in rubber. Moreover, since the affinity between the silanol group and the metal is high, the rubber compounded with silica adheres to the metal roll and is difficult to process. Further, since the silica is not sufficiently dispersed in the rubber, the rubber composition has a high Mooney viscosity, and has disadvantages such as inferior processability such as extrusion. Furthermore, since the surface of the silica particles is acidic, the basic substance used as a vulcanization accelerator is adsorbed, the rubber composition is not sufficiently vulcanized, and the storage elastic modulus does not increase. Was. Therefore, improvement in dispersibility, workability, etc. in a silica-containing rubber composition has been conventionally demanded.
従来において、シリカ配合ゴム組成物における諸物性等を改良する技術として、例えば、（Ａ）天然ゴム及び／又はジエン系合成ゴム、（Ｂ）シリカ及び（Ｃ）特定の構造を持つシラン化合物を含むゴム組成物（例えば、特許文献１参照）が知られている。 Conventionally, as a technique for improving various physical properties and the like in a silica-containing rubber composition, for example, (A) natural rubber and / or diene synthetic rubber, (B) silica and (C) a silane compound having a specific structure are included. A rubber composition (see, for example, Patent Document 1) is known.
また、天然ゴム及び／又はクロロプレンゴム以外のジエン系合成ゴムにおける諸物性等を改良する技術として、白色充填剤と、特定構造のアミドアミン類の少なくとも一種、例えば、Ｎ−ステアイルアミノプロピル−Ｎ、Ｎ−ジメチルアミン等とを配合してなることを特徴とするゴム組成物（例えば、特許文献２参照）が知られている。 In addition, as a technique for improving various physical properties and the like in diene-based synthetic rubbers other than natural rubber and / or chloroprene rubber, at least one of a white filler and an amidoamine having a specific structure, for example, N-steylaminopropyl-N, A rubber composition (for example, see Patent Document 2) characterized by blending N-dimethylamine or the like is known.
しかしながら、上記の従来技術だけではクロロプレンゴムに対する未加硫ゴムの粘度低減及び金属ロール粘着性改良効果は不十分であり、更なる改善が切望されているのが現状である。 However, the above prior art alone is insufficient in reducing the viscosity of the unvulcanized rubber and improving the metal roll adhesiveness with respect to the chloroprene rubber, so that further improvement is eagerly desired.
本発明者らは、上記従来技術の課題等に鑑み、鋭意検討した結果、クロロプレンゴムに対して、無機充填剤と、特定の化合物の少なくとも一種を配合することにより、クロロプレンゴム組成物へのシリカの分散性を改良し、未加硫ゴムの粘度及びロール粘着性低減を改良できて加工性も良好となるクロロプレンゴム組成物及びその加硫物が得られることを見出し、本発明を完成するに至った。 As a result of intensive investigations in view of the above-mentioned problems of the prior art, the present inventors have formulated silica in a chloroprene rubber composition by blending an inorganic filler and at least one of specific compounds with chloroprene rubber. In order to complete the present invention, the present inventors have found that a chloroprene rubber composition and a vulcanized product thereof can be obtained that can improve the dispersibility of the rubber, improve the viscosity and roll adhesiveness reduction of the unvulcanized rubber, and have good processability. It came.
すなわち、本発明は、
（１）クロロプレンゴム１００質量部に対し、無機充填材５〜１００質量部、及び下記式（Ｉ)で表される化合物の少なくとも一種１〜１０質量部とを配合してなることを特徴とするクロロプレンゴム組成物、
〔式（Ｉ）中、Ｒ１〜Ｒ３のうち少なくとも１つが、炭素数１〜２４のアルキル基を表し、残余のＲ１〜Ｒ３が、下記式（ＩＩ）で表される基を表す。〕
〔式（ＩＩ）中、Ｒ４は、炭素数１〜６のアルキレン基であり、また、ｎは、１〜５となる整数であり、ｍは０〜３となる整数である。〕
（２）無機充填材がシリカであることを特徴とする（１）に記載のクロロプレンゴム組成物、
（３）更に、シリカ１００質量部に対し、アルコキシアルキルシラン及び／又はジシラザン１〜２０質量部を配合することを特徴とする（２）に記載のクロロプレンゴム組成物、
（４）（１）〜（３）のいずれか一項に記載のクロロプレンゴム組成物からなる加硫物である。
That is, the present invention
(1) To 100 parts by mass of chloroprene rubber, 5 to 100 parts by mass of an inorganic filler and 1 to 10 parts by mass of at least one compound represented by the following formula (I) are characterized. Chloroprene rubber composition,
In [Formula (I), at least one of R 1 to R 3, represents an alkyl group having 1 to 24 carbon atoms, the remainder of R 1 to R 3, a group represented by the following formula (II) . ]
[In Formula (II), R 4 is an alkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 5, and m is an integer of 0 to 3. ]
(2) The chloroprene rubber composition according to (1), wherein the inorganic filler is silica,
(3) The chloroprene rubber composition according to (2), further comprising 1 to 20 parts by mass of alkoxyalkylsilane and / or disilazane with respect to 100 parts by mass of silica,
(4) A vulcanized product comprising the chloroprene rubber composition according to any one of (1) to (3).
本発明によれば、クロロプレンゴム組成物へのシリカの分散性を改良し、未加硫ゴムの粘度及びロール粘着性低減を改良できて加工性も良好となるクロロプレンゴム組成物及びその加硫物が提供される。 According to the present invention, a chloroprene rubber composition and a vulcanized product of which the dispersibility of silica in the chloroprene rubber composition can be improved, the viscosity and roll adhesiveness of unvulcanized rubber can be reduced, and the processability can be improved. Is provided.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明のクロロプレンゴム組成物は、クロロプレンゴム１００質量部に対して、無機充填剤５〜１００質量部、及び下記式（Ｉ）で表される化合物の少なくとも一種１〜１０質量部とを配合してなることを特徴とするものである。
〔式（Ｉ）中、Ｒ１〜Ｒ３のうち少なくとも１つが、炭素数１〜２４のアルキル基を表し、残余のＲ１〜Ｒ３が、下記式（ＩＩ）で表される基を表す。〕
〔式（ＩＩ）中、Ｒ４は、炭素数１〜６のアルキレン基であり、また、ｎは１〜５となる整数であり、ｍは０〜３となる整数である。〕
The chloroprene rubber composition of the present invention contains 5 to 100 parts by mass of an inorganic filler and 1 to 10 parts by mass of at least one compound represented by the following formula (I) with respect to 100 parts by mass of chloroprene rubber. It is characterized by.
In [Formula (I), at least one of R 1 to R 3, represents an alkyl group having 1 to 24 carbon atoms, the remainder of R 1 to R 3, a group represented by the following formula (II) . ]
[In Formula (II), R 4 is an alkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 5, and m is an integer of 0 to 3. ]
本発明に用いるクロロプレンゴムとしては、メルカプタン変性タイプ、キサントゲン変性タイプ、硫黄変性タイプが挙げられ、一種単独で用いても、二種以上をブレンドして用いてもよい。 Examples of the chloroprene rubber used in the present invention include mercaptan-modified types, xanthogen-modified types, and sulfur-modified types, which may be used alone or in a blend of two or more.
本発明のクロロプレンゴム組成物に用いる無機充填剤としては、シリカ、水酸化アルミニウム、アルミナ、クレー、炭酸カルシウム等が挙げられ、これらの中でも、補強性の観点から、シリカ及び水酸化アルミニウムが好ましく、シリカが特に好ましい。
用いるシリカとしては、特に制限はなく、市販のゴム組成物に使用されているものが使用でき、中でも湿式シリカ（含水ケイ酸）、乾式シリカ（無水ケイ酸）、コロイダルシリカ等を使用することができ、特に、湿式シリカの使用が好ましい。
Examples of the inorganic filler used in the chloroprene rubber composition of the present invention include silica, aluminum hydroxide, alumina, clay, calcium carbonate, etc. Among these, silica and aluminum hydroxide are preferable from the viewpoint of reinforcing properties, Silica is particularly preferred.
There is no restriction | limiting in particular as silica to be used, The thing currently used for the commercially available rubber composition can be used, and wet silica (hydrous silicic acid), dry-type silica (anhydrous silicic acid), colloidal silica etc. can be used especially. In particular, the use of wet silica is preferred.
これらの無機充填剤の配合量は、クロロプレンゴム１００質量部に対して５〜１００質量部の範囲であり、好ましくは、２０〜１００質量部の範囲であり、更に好ましくは、３０〜９０質量部であり、特に好ましくは４０〜８０質量部の範囲である。
特に、本発明の場合、シリカがクロロプレンゴム１００質量部に対して７０質量部以上の高い配合であっても、本発明の効果を発揮できるものである。
この無機充填剤の配合量が好ましくは、クロロプレンゴム１００質量部に対してヒステリシスを向上させる効果の観点から、５質量部以上であり、一方、作業性の低下を防ぐ観点から１００質量部以下である。
The compounding amount of these inorganic fillers is in the range of 5 to 100 parts by mass, preferably in the range of 20 to 100 parts by mass, and more preferably in the range of 30 to 90 parts by mass with respect to 100 parts by mass of the chloroprene rubber. Especially preferably, it is the range of 40-80 mass parts.
In particular, in the case of the present invention, the effect of the present invention can be exhibited even if the silica content is as high as 70 parts by mass or more with respect to 100 parts by mass of the chloroprene rubber.
The blending amount of the inorganic filler is preferably 5 parts by mass or more from the viewpoint of improving the hysteresis with respect to 100 parts by mass of the chloroprene rubber, and on the other hand, 100 parts by mass or less from the viewpoint of preventing workability deterioration. is there.
無機充填剤としてシリカを用いる場合には、分散性をさらに向上させる目的よりアルコキシアルキルシラン及び／又はジシラザンを用いることが好ましい。
アルコキシアルキルシラン及び／又はジシラザンは、特に制限なく、例えば、メチルトリエトキシシラン、フェニルトリエトキシシラン、ヘキサメチルジシラザンなどの少なくとも１種が挙げられる。
When silica is used as the inorganic filler, it is preferable to use alkoxyalkylsilane and / or disilazane for the purpose of further improving dispersibility.
The alkoxyalkylsilane and / or disilazane is not particularly limited, and examples thereof include at least one kind such as methyltriethoxysilane, phenyltriethoxysilane, and hexamethyldisilazane.
これらのアルコキシアルキルシラン及び／又はジシラザンの配合量は、シリカの配合量によって変動するものであるが、シリカ１００質量部に対し、１〜２０質量部であり、好ましくは、加工性の観点から、５〜１５質量部である。
アルコキシアルキルシラン及び／又はジシラザンの配合量が好ましくは、シリカ１００質量部に対し、アルコキシアルキルシラン及び／またはジシラザンを入れる効果の観点から、５質量部以上であり、一方、ヒステリシスを維持する観点から、２０質量部以下である。
The compounding amount of these alkoxyalkylsilanes and / or disilazanes varies depending on the compounding amount of silica, but is 1 to 20 parts by mass with respect to 100 parts by mass of silica, preferably from the viewpoint of workability. 5 to 15 parts by mass.
The amount of alkoxyalkylsilane and / or disilazane is preferably 5 parts by mass or more from the viewpoint of the effect of adding alkoxyalkylsilane and / or disilazane to 100 parts by mass of silica, while maintaining hysteresis. 20 parts by mass or less.
本発明では、上記無機充填剤以外にも補強性充填剤として、カーボンブラックなどを併用できる。
カーボンブラックは、特に制限なく、例えば、ＦＥＦ、ＳＲＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ等のグレードを用いることができる。
これらのカーボンブラックの配合量も、特に限定されるものではないが、クロロプレンゴム１００質量部に対し、０〜６０質量部が好ましく、更に好ましくは、１０〜５０質量部である。なお、スコーチタイムを維持する観点から、６０質量部以下が好ましい。
In this invention, carbon black etc. can be used together as a reinforcing filler other than the said inorganic filler.
Carbon black is not particularly limited, and grades such as FEF, SRF, HAF, ISAF, and SAF can be used.
The blending amount of these carbon blacks is also not particularly limited, but is preferably 0 to 60 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the chloroprene rubber. In addition, from a viewpoint of maintaining a scorch time, 60 mass parts or less are preferable.
本発明に用いる下記式（Ｉ）で表される化合物は、シリカ配合クロロプレンゴムの未加硫ゴム粘度低減と、ロール粘着性低減を改良して本発明の効果を発揮させるために配合するものである。
〔式（Ｉ）中において、Ｒ１〜Ｒ３のうち少なくとも１つが、炭素数１〜２４のアルキル基を表し、残余のＲ１〜Ｒ３が、下記式（ＩＩ）で表される基を表す。〕
〔式（ＩＩ）中、Ｒ４は、炭素数１〜６のアルキレン基であり、また、ｎは、１〜５となる整数であり、ｍは０〜３となる整数である。〕
The compound represented by the following formula (I) used in the present invention is compounded in order to improve the unvulcanized rubber viscosity reduction and roll adhesiveness reduction of the silica-blended chloroprene rubber and exert the effects of the present invention. is there.
[In In formula (I), at least one of R 1 to R 3, represents an alkyl group having 1 to 24 carbon atoms, the remainder of R 1 to R 3, a group represented by the following formula (II) Represent. ]
[In Formula (II), R 4 is an alkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 5, and m is an integer of 0 to 3. ]
上記式（Ｉ）中において、Ｒ１〜Ｒ３のうち少なくとも１つが、炭素数１〜２４のアルキル基を表し、残余のＲ１〜Ｒ３が、上記式（ＩＩ）で表される基を表すものであり、好ましくは、Ｒ１〜Ｒ３のうちの１つが炭素数１〜２４のアルキル基を表し、残余の２つが上記式（ＩＩ)で表される基を表すものである。 In In the above formula (I), at least one of R 1 to R 3, represents an alkyl group having 1 to 24 carbon atoms, the remainder of R 1 to R 3, a group represented by the formula (II) Preferably, one of R 1 to R 3 represents an alkyl group having 1 to 24 carbon atoms, and the remaining two represent groups represented by the above formula (II).
上記式（ＩＩ）において、Ｒ４は、炭素数１〜６のアルキレン基が挙げられ、エチレン基やプロピレン基が好ましく、また、ｎは１〜５の整数となるものであり、ｎは１〜３の整数となるものが好ましい。なお、ｎのＲ４は同一でも異なってもよい。また、ｍは０〜３の整数であり、１〜２が好ましく、１が更に好ましい。具体的には、メチル基、エチル基、プロピル基、イソプロピル基である。 In the above formula (II), R 4 includes an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group or a propylene group, n is an integer of 1 to 5, and n is 1 to 1 What becomes the integer of 3 is preferable. In addition, R 4 of n may be the same or different. M is an integer of 0 to 3, preferably 1 to 2, and more preferably 1. Specifically, they are a methyl group, an ethyl group, a propyl group, and an isopropyl group.
具体的に用いることができる上記式（Ｉ）で表される化合物としては、Ｎ−ラウリル−Ｎ，Ｎ−ジメチルアミン、Ｎ−ラウリル−Ｎ，Ｎ−ジエチルアミン、Ｎ−ラウリル−Ｎ，Ｎ−ジ（ジグリコール）アミン、Ｎ−ラウリル−Ｎ，Ｎ−ジ（トリグリコール）アミン、Ｎ−ラウリル−Ｎ，Ｎ−ジ（テトラグリコール）アミン、Ｎ−ラウリル−Ｎ，Ｎ−ジ（ペンタグリコール）アミン、Ｎ−パルミチル−Ｎ，Ｎ−ジメチルアミン、Ｎ−パルミチル−Ｎ，Ｎ−ジエチルアミン、Ｎ−パルミチル−Ｎ，Ｎ−ジ（ジグリコール）アミン、Ｎ−パルミチル−Ｎ，Ｎ−ジ（トリグリコール）アミン、Ｎ−パルミチル−Ｎ，Ｎ−ジ（テトラグリコール）アミン、Ｎ−パルミチル−Ｎ，Ｎ−ジ（ペンタグリコール）アミン、Ｎ−ステアリル−Ｎ，Ｎ−ジメチルアミン、Ｎ−ステアリル−Ｎ，Ｎ−ジエチルアミン、Ｎ−ステアリル−Ｎ，Ｎ−ジ（ジグリコール）アミン、Ｎ−ステアリル−Ｎ，Ｎ−ジ（トリグリコール）アミン、Ｎ−ステアリル−Ｎ，Ｎ−ジ（テトラグリコール）アミン、Ｎ−ステアリル−Ｎ，Ｎ−ジ（ペンタグリコール）アミンから選ばれる１種以上の使用が好ましい。
なお、上記式（Ｉ）で表される化合物であるアミン類の合成法は、既知であり、種々の製法により得ることができ、また、市販のものを使用してもよい。
Specific examples of the compound represented by the above formula (I) include N-lauryl-N, N-dimethylamine, N-lauryl-N, N-diethylamine, and N-lauryl-N, N-di. (Diglycol) amine, N-lauryl-N, N-di (triglycol) amine, N-lauryl-N, N-di (tetraglycol) amine, N-lauryl-N, N-di (pentaglycol) amine N-palmityl-N, N-dimethylamine, N-palmityl-N, N-diethylamine, N-palmityl-N, N-di (diglycol) amine, N-palmityl-N, N-di (triglycol) Amine, N-palmityl-N, N-di (tetraglycol) amine, N-palmityl-N, N-di (pentaglycol) amine, N-stearyl-N, N-dimethyla N-stearyl-N, N-diethylamine, N-stearyl-N, N-di (diglycol) amine, N-stearyl-N, N-di (triglycol) amine, N-stearyl-N, N- It is preferable to use one or more selected from di (tetraglycol) amine and N-stearyl-N, N-di (pentaglycol) amine.
In addition, the synthesis | combining method of amine which is a compound represented by the said formula (I) is known, can be obtained by various manufacturing methods, and may use a commercially available thing.
これらの化合物の少なくとも一種の配合量は、クロロプレンゴム１００質量部に対して、１〜１０質量部であり、本発明の更なる効果を発揮せしめる観点から、２〜８質量部が好ましく、３〜５質量部が特に好ましい。
この化合物の少なくとも一種の配合量が、クロロプレンゴム１００質量部に対して、１質量部以上では、未加硫ゴム粘度低減効果が高く、一方、１０質量部以下では、表面へのブリード性への影響が小さく好ましい。
The compounding amount of at least one of these compounds is 1 to 10 parts by mass with respect to 100 parts by mass of chloroprene rubber, and is preferably 2 to 8 parts by mass from the viewpoint of exerting further effects of the present invention. 5 parts by mass is particularly preferred.
When the compounding amount of at least one kind of this compound is 1 part by mass or more with respect to 100 parts by mass of chloroprene rubber, the effect of reducing the viscosity of the unvulcanized rubber is high, while when it is 10 parts by mass or less, the bleedability to the surface is improved. The influence is small and preferable.
本発明のクロロプレンゴム組成物には、クロロプレンゴム、無機充填剤、上記式（Ｉ）で表される化合物の他に、ゴム工業界で通常使用される配合剤、例えば、老化防止剤、軟化剤、ステアリン酸、亜鉛華、加硫促進剤、加硫促進助剤、加硫剤等を、本発明の目的を阻害しない範囲内で適宜選択して配合することができる。これら配合剤としては、市販品を好適に使用することができる。
また、本発明のクロロプレンゴム組成物は、クロロプレンゴムと、シリカと、上記式（Ｉ）で表される化合物の少なくとも一種と、必要に応じて適宜選択した各種配合剤とをロール、インターナルミキサー等の混練り機を用いて混練り、熱入れ、押出等することにより得られ、成形加工後、加硫を行い、防振ゴム、ベルト，ホース、ゴムロールその他の工業製品等の用途に用いることができる。
The chloroprene rubber composition of the present invention includes a chloroprene rubber, an inorganic filler, a compound represented by the above formula (I), a compounding agent usually used in the rubber industry, such as an anti-aging agent and a softening agent. , Stearic acid, zinc white, vulcanization accelerator, vulcanization acceleration aid, vulcanizing agent, and the like can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used.
Further, the chloroprene rubber composition of the present invention comprises a roll, an internal mixer, a chloroprene rubber, silica, at least one compound represented by the above formula (I), and various compounding agents appropriately selected as necessary. It is obtained by kneading using a kneading machine such as kneading, heat-injection, extrusion, etc., and after molding, vulcanize and use it for applications such as anti-vibration rubber, belts, hoses, rubber rolls and other industrial products. Can do.
このように構成されるクロロプレンゴム組成物が、何故、クロロプレンゴム組成物への無機充填剤、特に、シリカの分散性を改良し、未加硫ゴムの粘度低減を改良できて加工性も良好となるかは以下のように推察される。
すなわち、本発明のクロロプレンゴム組成物において、クロロプレンゴムに対して、シリカを配合した配合系に、上記式（Ｉ）で表される化合物の少なくとも一種が配合されると、シリカ表面の疎水化により、シリカ同士の凝集を抑制し、未加硫ゴムの粘度を低減し、また、シリカ表面の金属ロールへの吸着を抑制するため、加工性も良好となるものと推察される。
The chloroprene rubber composition constituted in this way can improve the dispersibility of the inorganic filler, especially silica, and improve the viscosity reduction of the unvulcanized rubber and improve the processability. It is guessed as follows.
That is, in the chloroprene rubber composition of the present invention, when at least one compound represented by the above formula (I) is blended in the blending system in which silica is blended with chloroprene rubber, the silica surface is hydrophobized. It is presumed that the workability is also improved because the aggregation of silica is suppressed, the viscosity of the unvulcanized rubber is reduced, and the adsorption of the silica surface to the metal roll is suppressed.
以下に、実施例及び比較例を挙げて本発明を更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.
〔実施例１〜４及び比較例１〜４〕
下記表１に示す各成分のうちクロロプレンゴム（デンカクロロプレンＳ−４０Ｖ）を素練りしながら、先ず亜鉛華及び加硫促進剤以外の成分を加えて混練し、最後に架橋剤を加えて、更に混練してクロロプレンゴム組成物を調製した。表中の数値は質量部である。
得られた各クロロプレンゴム組成物について、下記測定方法により、未加硫ゴム粘度の測定を行った。これらの結果を表１に示す。
[Examples 1-4 and Comparative Examples 1-4]
While kneading chloroprene rubber (Denka Chloroprene S-40V) among the components shown in Table 1 below, first, components other than zinc white and vulcanization accelerator are added and kneaded, and finally a crosslinking agent is added. A chloroprene rubber composition was prepared by kneading. The numerical value in a table | surface is a mass part.
About each obtained chloroprene rubber composition, the unvulcanized rubber viscosity was measured with the following measuring method. These results are shown in Table 1.
〔未加硫ゴム粘度の測定方法〕
未加硫ゴム粘度は、ＪＩＳ Ｋ ６３００−１：２００１（ムーニー粘度）に準拠して行った。
なお、未加硫ゴム粘度は、値が小さいほど作業性が良好であることを示す。
[Measurement method of unvulcanized rubber viscosity]
The unvulcanized rubber viscosity was measured in accordance with JIS K 6300-1: 2001 (Mooney viscosity).
In addition, unvulcanized rubber viscosity shows that workability | operativity is so favorable that a value is small.
〔ロール粘着性の評価方法〕
下記に示す５点スケールを用いて評価を行った。
１点：粘着性が強い。切り返しができない。
２点：粘着性が強い。何とか切り返しができる。
３点：粘着性ややある。切り返し生地を強く引きながらできる。
４点：粘着性わずかにある。切り返しは生地を引くだけでできる。
５点：粘着性なし。ナイフを入れるだけで生地がはがれる。
[Roll adhesive evaluation method]
Evaluation was performed using a 5-point scale shown below.
1 point: Strong tackiness. Cannot switch back.
2 points: Strong adhesion. You can cut back somehow.
3 points: Slightly sticky. You can do it while pulling the dough.
4 points: Slightly sticky. Cutting can be done simply by drawing the dough.
5 points: No tackiness. The dough can be peeled just by inserting a knife.
〔ブリード性の評価方法〕
下記に示す指標で肉眼で確認し、評価を行った。
○：混練り後の未加硫ゴムシート表面に液状のものがにじみ出てこない。
×：混練り後の未加硫ゴムシート表面に液状のものがにじみ出てくる。
[Bleedability evaluation method]
The following indicators were used for confirmation and evaluation with the naked eye.
○: Liquid does not ooze out on the surface of the unvulcanized rubber sheet after kneading.
X: Liquid oozes out on the surface of the unvulcanized rubber sheet after kneading.
上記表１の＊１〜＊７は下記の通りである。
＊１）旭カーボン社製 「旭（＃５０）」
＊２）東ソー・シリカ社製「ニップシールＡＱ」
＊３）４,４'-ビス（α,α-ジメチルベンジル）ジフェニルアミン
＊４）ポリオキシエチレンアルキルアミン（第一工業製薬社製「アミラヂンＤ」）
＊５）ステアリルジメチルアミノプロピルアミド（第一工業製薬社製「カチオーゲンＳＰＡ」）
＊６）２−メルカプトイミダゾリン
＊７）テトラメチルチウラムジスルフィド
* 1 to * 7 in Table 1 are as follows.
* 1) "Asahi (# 50)" manufactured by Asahi Carbon Co., Ltd.
* 2) “Nip Seal AQ” manufactured by Tosoh Silica
* 3) 4,4'-bis (α, α-dimethylbenzyl) diphenylamine * 4) Polyoxyethylene alkylamine (“Amiradin D” manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
* 5) Stearyl dimethylaminopropylamide (Daiichi Kogyo Seiyaku Co., Ltd. “Katiogen SPA”)
* 6) 2-Mercaptoimidazoline * 7) Tetramethylthiuram disulfide
上記表１中、比較例３は粘度が大きく、加工することができなかった。 In Table 1 above, Comparative Example 3 had a large viscosity and could not be processed.
上記表１から明らかなように、本発明範囲となる実施例１〜４のクロロプレンゴム組成物は、本発明の範囲外となる比較例１〜３に比べて、未加硫ゴム粘度及び金属ロール加工性、加硫物の評価結果から、未加硫ゴムの粘度低減効果と、金属ロール加工性が良好となるクロロプレンゴム組成物となることが判明した。 As is apparent from Table 1 above, the chloroprene rubber compositions of Examples 1 to 4 within the scope of the present invention were compared with Comparative Examples 1 to 3 outside the scope of the present invention, and the unvulcanized rubber viscosity and metal roll From the evaluation results of processability and vulcanizate, it was found that the chloroprene rubber composition has an effect of reducing the viscosity of unvulcanized rubber and has good metal roll processability.
上記表１から明らかなように、本発明範囲となる実施例１〜４のクロロプレンゴム組成物は、特許文献２記載の化合物（アミドアミン類）である、ステアリルジメチルアミノプロピルアミドを用いた比較例４と比べて、未加硫ゴムの粘度低減効果が良好となるクロロプレンゴム組成物となることが判明した。
また、各実施例のクロロプレンゴム組成物を加硫したところクロロプレンゴム組成物の加硫物が得られた。
以上の結果から、本発明によれば、未加硫ゴムの粘度及びロール粘着性低減を改良できて加工性も良好となるクロロプレンゴム組成物及びその加硫物が得られることが確認された。
As is clear from Table 1 above, the chloroprene rubber compositions of Examples 1 to 4 within the scope of the present invention were Comparative Examples 4 using stearyldimethylaminopropylamide, which is a compound (amidoamines) described in Patent Document 2. It was found that a chloroprene rubber composition in which the effect of reducing the viscosity of the unvulcanized rubber is good is obtained.
Moreover, when the chloroprene rubber composition of each Example was vulcanized, a vulcanized product of the chloroprene rubber composition was obtained.
From the above results, according to the present invention, it was confirmed that a chloroprene rubber composition and a vulcanized product thereof that can improve the viscosity and roll adhesiveness reduction of the unvulcanized rubber and have good processability can be obtained.
防振ゴム、ベルト、ホース、ゴムロールなどのゴム製品に好適に用いることができる。 It can be suitably used for rubber products such as anti-vibration rubber, belts, hoses and rubber rolls.
Claims (4)
〔式（Ｉ）中、Ｒ１〜Ｒ３のうち少なくとも１つが、炭素数１〜２４のアルキル基を表し、残余のＲ１〜Ｒ３が、下記式（ＩＩ）で表される基を表す。〕
〔式（ＩＩ）中、Ｒ４は、炭素数１〜６のアルキレン基であり、また、ｎは、１〜５となる整数であり、ｍは０〜３となる整数である。〕 A chloroprene rubber composition comprising 5 to 100 parts by mass of an inorganic filler and 1 to 10 parts by mass of at least one compound represented by the following formula (I) with respect to 100 parts by mass of chloroprene rubber. object.
In [Formula (I), at least one of R 1 to R 3, represents an alkyl group having 1 to 24 carbon atoms, the remainder of R 1 to R 3, a group represented by the following formula (II) . ]
[In Formula (II), R 4 is an alkylene group having 1 to 6 carbon atoms, n is an integer of 1 to 5, and m is an integer of 0 to 3. ]
The vulcanizate which consists of a chloroprene rubber composition as described in any one of Claims 1-3.
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| WO2020071058A1 (en) | 2018-10-03 | 2020-04-09 | 富士電機株式会社 | Semiconductor device |
| WO2023157827A1 (en) * | 2022-02-21 | 2023-08-24 | デンカ株式会社 | Rubber composition, vulcanizate, and vulcanized molded object |
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| WO2020071058A1 (en) | 2018-10-03 | 2020-04-09 | 富士電機株式会社 | Semiconductor device |
| WO2023157827A1 (en) * | 2022-02-21 | 2023-08-24 | デンカ株式会社 | Rubber composition, vulcanizate, and vulcanized molded object |
| JPWO2023157827A1 (en) * | 2022-02-21 | 2023-08-24 |
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