JPH0244332B2 - - Google Patents
Info
- Publication number
- JPH0244332B2 JPH0244332B2 JP58139264A JP13926483A JPH0244332B2 JP H0244332 B2 JPH0244332 B2 JP H0244332B2 JP 58139264 A JP58139264 A JP 58139264A JP 13926483 A JP13926483 A JP 13926483A JP H0244332 B2 JPH0244332 B2 JP H0244332B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- pigment
- present
- dye
- vulcanization
- 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 - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 claims description 32
- 239000005060 rubber Substances 0.000 claims description 32
- 239000000203 mixture Substances 0.000 claims description 21
- 238000004073 vulcanization Methods 0.000 claims description 8
- 239000012860 organic pigment Substances 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000001023 inorganic pigment Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 239000003086 colorant Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 2
- 239000012039 electrophile Substances 0.000 claims description 2
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 239000011669 selenium Substances 0.000 claims description 2
- 229910052714 tellurium Inorganic materials 0.000 claims description 2
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- -1 ZnO and PbO Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 150000004053 quinones Chemical class 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000004 White lead Inorganic materials 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 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
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- REQPQFUJGGOFQL-UHFFFAOYSA-N dimethylcarbamothioyl n,n-dimethylcarbamodithioate Chemical compound CN(C)C(=S)SC(=S)N(C)C REQPQFUJGGOFQL-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229920001897 terpolymer Polymers 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
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は加硫により着色ゴム組成物を形成する
ための未加硫ゴム組成物に関する。
従来黒以外の赤色、青色等に着色したゴムは、
未加硫ゴムに単に顔料等を混合して、その後加硫
して製造されている。この場合、加硫ゴム中にお
いて、顔料とゴム分子とが混合物の形をなしてい
る。しかしこのような顔料とゴム成分との混合物
が外的条件にさらされた時、水分で顔料が流れ出
たり、日光等の直射によつて顔料自体が分解した
り、ゴム分子自体の崩壊により、顔料自体の流出
が生じた。このような顔料の流出は、ゴム製品の
退色を意味する。したがつて従来において、黒以
外の着色ゴムの用途は主として室内に限られてい
た。又そのような着色ゴムは屋外に使用されたり
しても、１〜２月で交換しなければならないか、
又は退色したまま放置して使用しているのが現状
であつた。
本発明者は、ゴム分子中の二重結合または、活
性点に着目し、退色又は変色しないゴムについて
幅広い研究を行なつた結果、顔料又は染料分子を
ゴム分子に結合させたと考えられる方法によつて
退色又は変色しないゴムの開発に成功し本発明に
至つた。
本発明は、含硫黄化合物、テルル又はセレン、
１種又はそれ以上の求電子試薬、前記求電子試薬
の作用により変性され得る基を有する有機顔料又
は染料および無機顔料からなる群から選ばれた着
色剤を混入したことを特徴とする、加硫により着
色ゴム組成物を形成するための未加硫ゴム組成物
に関する。
含硫黄化合物としてはTMTM，TMTD、そ
の外に公知の含硫黄加硫剤が使用できる。
本発明組成物を加熱した時、加硫が行なわれる
と同時に有機顔料あるいは染料に存在している極
性基又は無機顔料の金属原子がゴム分子中に存在
する活性点に結合して、退色又は変色しない着色
ゴム組成物が形成されると考えられる。
本発明において使用されるべきゴムとしては天
然ゴム（NR）および合成ゴムのようなすべての
ゴムが使用可能である。例えばスチレンブタジエ
ンゴム（SBR）、アクリロニトリルブタジエンゴ
ム（NBR）、クロロプレンゴム（CR）、ブチルゴ
ム（IIR）、ポリイソプレンゴム（IR）、ポリブタ
ジエンゴム（BR）、エチレンプロピレンゴム
（EPR）、およびエチレン−プロピレン−ジエン
三元重合体ゴム（EPDM）、クロロスルホン化ポ
リエチレン（CMS）、エチレン酢酸ビニル共重合
体（EVA）、等の合成ゴムが使用できる。
ゴム成分としては二重結合または、活性点を持
つていることが要件である。
求電子試薬は有機顔料又は染料の末端の極性基
又は無機顔料の金属原子から電子を取つて、これ
らをに荷電させる役割を果す。キノン類、四塩
化スズ、塩化アルミニウム、およびZnO，PbO等
の両性金属酸化物と、それらの金属の弱酸塩との
混合物である。特に四塩化スズ、ZnOとZnCO3と
の混合物、キノン類、AlCl3が好ましい。この求
電子試薬は未加硫ゴム組成物100部に対し、0.2−
20重量部、好ましくは１−12重量部である。加硫
ゴム組成物の性質を害せず又は加硫中に分解する
ものであればこれらの求電子試薬をもつと多く使
用できる。
有機顔料又は染料としては求電子試薬によつて
変性され得る基を有する公知のものがすべて使用
できる。特にベンゼン核上にNH2，NO2，
OCH3，OCH5，CONH2，Cl，CF3等が存在する
顔料又は染料が好ましい。
又は無機顔料はほとんどすべて金属原子を有す
るので、本発明において使用できる。例えば、亜
鉛華、アルミナ白、酸化チタン、ベンガラ、リサ
ージ、鉛丹、黄鉛、鉛白、亜鉛黄、モリブデン
赤、カドミウム黄等である。
顔料又は染料の使用量は本発明のゴム組成物か
ら形成される加硫ゴム組成物の用途による。
その他未加硫ゴム組成物には通常のゴム成分に
添加される公知の含硫黄加合物、樹脂加硫促進
剤、補強剤、軟化剤、着色剤、増量剤、老化防止
剤および、紫外線の吸収剤等が添加されていても
良い。
本発明では加硫前に求電子試薬および特定な顔
料又は染料をゴム組成物に加えるので、通常条件
の加硫工程中にその顔料又は染料がゴム分子に結
合すると考えられる。
本発明の組成物を使用した場合、その顔料又は
染料分子が一部分又は全部がゴム成分に結合する
ので、従来のものより、退色又は変色が起りにく
い。又そのような顔料の作用によつて加硫ゴムの
強度がさらに増加したという特徴を有する。
以下に本発明の実施例を示す。単位は重量によ
る。
実施例 １−３
以下の表１に示した組成を有する未加硫ゴム組
成物を160℃、10分間150Kg／cm2の圧力で加硫し
た。その加硫ゴムの性質は表１に示す。
The present invention relates to unvulcanized rubber compositions for forming colored rubber compositions by vulcanization. Traditionally, rubber colored in colors other than black, such as red or blue,
It is manufactured by simply mixing pigments etc. with unvulcanized rubber and then vulcanizing it. In this case, the pigment and rubber molecules are in the form of a mixture in the vulcanized rubber. However, when such a mixture of pigment and rubber components is exposed to external conditions, the pigment may flow out due to moisture, the pigment itself may decompose due to direct sunlight, or the rubber molecules themselves may disintegrate. A leak of its own occurred. Such pigment outflow means fading of the rubber product. Therefore, in the past, the use of colored rubber other than black was mainly limited to indoor use. Also, even if such colored rubber is used outdoors, it must be replaced every January or February.
Or, the current situation was that they were left undiscolored and used. The present inventor focused on the double bonds or active sites in rubber molecules and conducted extensive research on rubber that does not fade or discolor.As a result, the inventors discovered that a method believed to have been used to bond pigment or dye molecules to rubber molecules. As a result, they succeeded in developing a rubber that does not fade or change color, leading to the present invention. The present invention provides a sulfur-containing compound, tellurium or selenium,
Vulcanization, characterized in that it contains one or more electrophilic reagents, a coloring agent selected from the group consisting of organic pigments or dyes having groups that can be modified by the action of said electrophilic reagents and inorganic pigments. The present invention relates to an unvulcanized rubber composition for forming a colored rubber composition. As the sulfur-containing compound, TMTM, TMTD, and other known sulfur-containing vulcanizing agents can be used. When the composition of the present invention is heated, at the same time as vulcanization occurs, the polar groups present in the organic pigment or dye or the metal atoms of the inorganic pigment bond to the active sites present in the rubber molecules, resulting in fading or discoloration. It is believed that a colored rubber composition is formed that does not. As the rubber to be used in the present invention, all rubbers can be used, such as natural rubber (NR) and synthetic rubber. For example, styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber (IIR), polyisoprene rubber (IR), polybutadiene rubber (BR), ethylene-propylene rubber (EPR), and ethylene-propylene. - Synthetic rubbers such as diene terpolymer rubber (EPDM), chlorosulfonated polyethylene (CMS), and ethylene vinyl acetate copolymer (EVA) can be used. The rubber component is required to have double bonds or active sites. The electrophilic reagent plays the role of taking electrons from the terminal polar group of an organic pigment or dye or a metal atom of an inorganic pigment to charge them. It is a mixture of quinones, tin tetrachloride, aluminum chloride, amphoteric metal oxides such as ZnO and PbO, and weak acid salts of these metals. Particularly preferred are tin tetrachloride, a mixture of ZnO and ZnCO 3 , quinones, and AlCl 3 . This electrophilic reagent is 0.2-
20 parts by weight, preferably 1-12 parts by weight. Many of these electrophilic reagents can be used as long as they do not impair the properties of the vulcanized rubber composition or are decomposed during vulcanization. As the organic pigment or dye, all known organic pigments or dyes having a group that can be modified with an electrophilic reagent can be used. In particular, NH 2 , NO 2 ,
Pigments or dyes in which OCH 3 , OCH 5 , CONH 2 , Cl, CF 3 and the like are present are preferred. Alternatively, almost all inorganic pigments have metal atoms and can therefore be used in the present invention. Examples include zinc white, alumina white, titanium oxide, red iron oxide, litharge, red lead, yellow lead, white lead, zinc yellow, molybdenum red, and cadmium yellow. The amount of pigment or dye used depends on the use of the vulcanized rubber composition formed from the rubber composition of the present invention. Other unvulcanized rubber compositions include known sulfur-containing compounds, resin vulcanization accelerators, reinforcing agents, softeners, colorants, fillers, anti-aging agents, and ultraviolet ray resistant additives added to ordinary rubber components. An absorbent or the like may be added. Since the present invention adds an electrophile and a specific pigment or dye to the rubber composition prior to vulcanization, it is believed that the pigment or dye becomes attached to the rubber molecules during the vulcanization process under normal conditions. When using the composition of the present invention, fading or discoloration is less likely to occur than with conventional compositions because the pigment or dye molecules are partially or fully bound to the rubber component. Furthermore, the strength of the vulcanized rubber is further increased by the action of such pigments. Examples of the present invention are shown below. Units are based on weight. Example 1-3 An unvulcanized rubber composition having the composition shown in Table 1 below was vulcanized at 160° C. for 10 minutes at a pressure of 150 kg/cm 2 . The properties of the vulcanized rubber are shown in Table 1.
【表】【table】
Claims (1)
それ以上の求電子試薬、有機顔料又は染料および
無機顔料からなる群から選ばれた着色剤を混入し
たことを特徴とする、加硫により着色ゴム組成物
を形成するための未加硫ゴム組成物。1. A rubber composition colored by vulcanization, characterized in that it contains a coloring agent selected from the group consisting of a sulfur-containing compound, tellurium or selenium, one or more electrophiles, an organic pigment or dye, and an inorganic pigment. Unvulcanized rubber composition for forming objects.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13926483A JPS6031543A (en) | 1983-07-29 | 1983-07-29 | Unvulcanized rubber composition which forms colored rubber composition by vulcanization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13926483A JPS6031543A (en) | 1983-07-29 | 1983-07-29 | Unvulcanized rubber composition which forms colored rubber composition by vulcanization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6031543A JPS6031543A (en) | 1985-02-18 |
| JPH0244332B2 true JPH0244332B2 (en) | 1990-10-03 |
Family
ID=15241231
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13926483A Granted JPS6031543A (en) | 1983-07-29 | 1983-07-29 | Unvulcanized rubber composition which forms colored rubber composition by vulcanization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6031543A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0643521B2 (en) * | 1983-08-26 | 1994-06-08 | 横浜ゴム株式会社 | Rubber composition for hose to be vulcanized by lead |
| JPH02155938A (en) * | 1988-12-07 | 1990-06-15 | Three Bond Co Ltd | Self-lubricating rubber composition and preparation thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5212254A (en) * | 1975-07-21 | 1977-01-29 | Dainichi Seika Kogyo Kk | Colorants for rubber |
-
1983
- 1983-07-29 JP JP13926483A patent/JPS6031543A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5212254A (en) * | 1975-07-21 | 1977-01-29 | Dainichi Seika Kogyo Kk | Colorants for rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6031543A (en) | 1985-02-18 |
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