JP4455905B2 - Foam rubber roller - Google Patents
Foam rubber roller Download PDFInfo
- Publication number
- JP4455905B2 JP4455905B2 JP2004067322A JP2004067322A JP4455905B2 JP 4455905 B2 JP4455905 B2 JP 4455905B2 JP 2004067322 A JP2004067322 A JP 2004067322A JP 2004067322 A JP2004067322 A JP 2004067322A JP 4455905 B2 JP4455905 B2 JP 4455905B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- mass
- foam
- parts
- foamed
- 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
- 229920001821 foam rubber Polymers 0.000 title claims description 39
- 229920001971 elastomer Polymers 0.000 claims description 129
- 239000005060 rubber Substances 0.000 claims description 129
- 239000000203 mixture Substances 0.000 claims description 38
- 239000010410 layer Substances 0.000 claims description 36
- 238000004073 vulcanization Methods 0.000 claims description 35
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 19
- 239000006260 foam Substances 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- -1 morpholinodithio compound Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000002346 layers by function Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 40
- 238000005187 foaming Methods 0.000 description 29
- 229910021529 ammonia Inorganic materials 0.000 description 20
- 239000004156 Azodicarbonamide Substances 0.000 description 11
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 11
- 235000019399 azodicarbonamide Nutrition 0.000 description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 239000004202 carbamide Substances 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- JEHKKBHWRAXMCH-UHFFFAOYSA-N benzenesulfinic acid Chemical compound O[S@@](=O)C1=CC=CC=C1 JEHKKBHWRAXMCH-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 229920001084 poly(chloroprene) Polymers 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 235000019241 carbon black Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 108091008695 photoreceptors Proteins 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000010457 zeolite Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000010216 calcium carbonate Nutrition 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001739 density measurement Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229920005558 epichlorohydrin rubber Polymers 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010059 sulfur vulcanization Methods 0.000 description 2
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 2
- JCZPMGDSEAFWDY-TXICZTDVSA-N (2R,3R,4R,5R)-2,3,4,5,6-pentahydroxyhexanamide Chemical compound NC(=O)[C@H](O)[C@H](O)[C@H](O)[C@H](O)CO JCZPMGDSEAFWDY-TXICZTDVSA-N 0.000 description 1
- UJPKMTDFFUTLGM-UHFFFAOYSA-N 1-aminoethanol Chemical compound CC(N)O UJPKMTDFFUTLGM-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000005662 Paraffin oil Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- CSNJTIWCTNEOSW-UHFFFAOYSA-N carbamothioylsulfanyl carbamodithioate Chemical compound NC(=S)SSC(N)=S CSNJTIWCTNEOSW-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 150000002357 guanidines Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000219 mutagenic Toxicity 0.000 description 1
- 230000003505 mutagenic effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Images
Landscapes
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Rolls And Other Rotary Bodies (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Electrophotography Configuration And Component (AREA)
Description
本発明は、発泡ゴムローラに関し、さらに詳しくは、アンモニアの発生が無く、複写機、レーザープリンタ、ファクシミリなどの電子写真装置や静電記録装置などの画像形成装置用の部材として好適に使用される発泡ゴムローラに関するものである。 The present invention relates to a foamed rubber roller, and more particularly, is a foam that does not generate ammonia and is suitably used as a member for an image forming apparatus such as an electrophotographic apparatus such as a copying machine, a laser printer, or a facsimile, or an electrostatic recording apparatus. It relates to rubber rollers.
電子写真装置に用いられる帯電ローラ、転写ローラ等のゴムローラは、近年の装置の高速化、良画質化に応えるために、感光体との当接により一様なニップ幅を保つことが要求され、芯金の外周上の弾性体を発泡ゴムとした発泡ゴムローラが使用されている。発泡ゴムとしては、当接による一様なニップ幅を保つために高発泡化されている。 Rubber rollers such as charging rollers and transfer rollers used in electrophotographic apparatuses are required to maintain a uniform nip width by contact with a photoreceptor in order to meet the recent increase in speed and quality of the apparatus. A foam rubber roller is used in which an elastic body on the outer periphery of the core metal is foam rubber. The foamed rubber is highly foamed to maintain a uniform nip width due to contact.
従来このような発泡ゴムローラとしては、例えば、以下のようにして製造されている。原料ゴム組成物として、エチレン−プロピレン−ジエン共重合ゴム（ＥＰＤＭ）、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合ゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）等の各種原料ゴムに発泡剤、尿素のような発泡助剤、カーボンブラック等のフィラー類、加硫剤、加硫促進剤、軟化剤等を加えたものを混練りしたものを所定の形状に押出した後、熱風炉やマイクロ波加硫装置（ＵＨＦ）を用い発泡加硫して製造される発泡ゴムを用いた発泡ゴムローラや金型を用いて発泡加硫して製造される発泡ゴムを用いた発泡ゴムローラが知られる。また、工程を簡略化するために上記原料ゴム組成物をあらかじめ必要部分に接着剤を塗布した芯金上に配置し、芯金上で発泡加硫と接着を同時に行って製造される発泡ゴムを用いた発泡ゴムローラも知られている。 Conventionally, such a foam rubber roller is manufactured as follows, for example. As raw material rubber composition, ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), natural rubber (NR), butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), Kneaded with various raw rubbers such as chloroprene rubber (CR) to which foaming agents, foaming aids such as urea, fillers such as carbon black, vulcanizing agents, vulcanization accelerators, softeners, etc. are added. Is extruded and then foamed and vulcanized using a foamed rubber roller or mold using foamed rubber produced by foam vulcanization using a hot air oven or microwave vulcanizer (UHF). A foam rubber roller using foam rubber is known. Further, in order to simplify the process, a foamed rubber produced by placing the raw rubber composition on a cored bar having an adhesive applied to a necessary part in advance and simultaneously performing foam vulcanization and bonding on the cored bar is provided. The foam rubber roller used is also known.
発泡ゴムに使用される発泡剤としては、アゾジカルボンアミド（ＡＤＣＡ）、ｐ，ｐ’−オキシビスベンゼンスルホニルヒドラジド（ＯＢＳＨ）、Ｎ，Ｎ’−ジニトロソペンタメチレンヒドラジド（ＤＰＴ）等の発泡剤が知られている。 Examples of the foaming agent used for the foamed rubber include azodicarbonamide (ADCA), p, p′-oxybisbenzenesulfonyl hydrazide (OBSH), and N, N′-dinitrosopentamethylene hydrazide (DPT). Are known.
これらのうちＤＰＴは、安価であり発泡ガス量が多くスポンジゴムの製造に適したものであるが、易燃性であり発火の危険性がある上、発泡ガス中に毒性のあるホルムアルデヒドが発生することと、そのもの自体が変異原性となる可能性を疑われているものであり、人体への安全性に劣るという欠点を有する。また、ＤＰＴは分解温度が約２１０℃と高いためゴム発泡用の発泡剤として単独で使用されることは少なく、一般的には発泡助剤として尿素を併用して分解温度を低下させて使用される。尿素を混合して用いた発泡ゴムは、アンモニアを多く発生し、感光体を汚染し易くなるという問題がある。 Among these, DPT is inexpensive and has a large amount of foaming gas and is suitable for the production of sponge rubber. However, DPT is flammable and has a risk of ignition, and toxic formaldehyde is generated in the foaming gas. In addition, it itself is suspected of being mutagenic and has the disadvantage of being inferior in safety to the human body. In addition, since DPT has a high decomposition temperature of about 210 ° C., it is rarely used alone as a foaming agent for foaming rubber, and generally used as a foaming aid with urea being used to lower the decomposition temperature. The Foam rubber using a mixture of urea has a problem that it generates a large amount of ammonia and easily contaminates the photoreceptor.
ＡＤＣＡは、安価で発生ガス量も多く、自己消化性であり安全性に優れた化合物であるため広く使用されている。しかしながら、発泡ゴム中のＡＤＣＡの分解残渣からアンモニアが発生し、感光体を汚染して画像不良を引き起こす場合があるという問題がある。さらにＡＤＣＡにおいても分解温度が約２１０℃と高いためゴム発泡用の発泡剤として単独で使用されることは少なく、一般的には発泡助剤として尿素を併用して分解温度を低下させて使用される。尿素を混合して用いた発泡ゴムは、さらにアンモニアを多く発生し、発泡ゴムローラの発泡ゴム層としたとき、より感光体を汚染し易くなるという問題がある。 ADCA is widely used because it is a cheap compound with a large amount of generated gas, is a self-digesting compound and is excellent in safety. However, there is a problem that ammonia is generated from the decomposition residue of ADCA in the foamed rubber, and the photoconductor may be contaminated to cause an image defect. Furthermore, in ADCA, the decomposition temperature is as high as about 210 ° C., so it is rarely used alone as a foaming agent for foaming rubber. Generally, urea is used as a foaming aid to lower the decomposition temperature. The Foam rubber using a mixture of urea has a problem that ammonia is further generated, and when the foam rubber layer of the foam rubber roller is used, the photoconductor is more easily contaminated.
発泡助剤として尿素の代わりにベンゼンスルフィン酸金属塩を用いるとＡＤＣＡの分解温度を低下させることができ、尿素の分解からのアンモニアを無くすことができることが知られている（例えば、特許文献１）。同様に、ベンゼンスルフィン酸金属塩を用いて尿素の使用を回避し、同時に、ゼオライトを添加することでＡＤＣＡに基づくアンモニアをトラップすることが知られている（例えば、特許文献２）。 It is known that when a metal salt of benzenesulfinic acid is used instead of urea as a foaming aid, the decomposition temperature of ADCA can be lowered and ammonia from the decomposition of urea can be eliminated (for example, Patent Document 1). . Similarly, it is known that benzenesulfinic acid metal salts are used to avoid the use of urea, and at the same time, ammonia based on ADCA is trapped by adding zeolite (for example, Patent Document 2).
しかしながら、ベンゼンスルフィン酸金属塩は高価な化合物であるため経済性に劣り、発泡気泡（発泡セル）が不均一になりやすく、品質、コストにおいて不利になるという問題がある。また、ゼオライト添加によるアンモニアのトラップは、ゼオライトをＡＤＣＡに対して３〜５倍量と多量に添加しないとアンモニアの発生を抑制する効果はなく、また、アンモニアの発生を全くなくすことはできないという問題がある。 However, since benzenesulfinic acid metal salt is an expensive compound, it is inferior in economic efficiency, and foamed bubbles (foamed cells) tend to be non-uniform, resulting in disadvantages in quality and cost. Moreover, the trap of ammonia by adding zeolite has the effect of suppressing the generation of ammonia unless the zeolite is added in a large amount of 3 to 5 times the amount of ADCA, and the generation of ammonia cannot be eliminated at all. There is.
これに対して、ＯＢＳＨはそのもの自身の分解温度が約１６０℃と低く、発泡剤として単独使用可能なものであり、かつ単独使用した場合アンモニアを発生しないことが知られている。また、芯金の外周上にゴム組成物を配置せしめた後、無加圧下で発泡加硫（フリー発泡）して製造される発泡ゴムローラにおいても、発泡剤としてＯＢＳＨが単独使用できることが知られている（例えば、特許文献３）。しかしながら、ＯＢＳＨの発泡分解時に発生する酸性物質により加硫阻害が生じ、架橋密度が上がり難いという問題がある。 On the other hand, OBSH itself has a low decomposition temperature of about 160 ° C., and it is known that OBSH can be used alone as a foaming agent and does not generate ammonia when used alone. Also, it is known that OBSH can be used alone as a foaming agent in a foamed rubber roller manufactured by placing a rubber composition on the outer periphery of a metal core and then foaming and vulcanizing (free foaming) under no pressure. (For example, Patent Document 3). However, there is a problem in that vulcanization is inhibited by an acidic substance generated during foaming decomposition of OBSH, and it is difficult to increase the crosslinking density.
また、密度０．５０ｇ／ｃｍ3以下（加硫ゴム−密度測定（ＪＩＳ Ｋ６２６８））となるように高発泡化すると、芯金の外周上に原料ゴム組成物を配置せしめ、次いで発泡加硫と接着を同時に行う場合には、芯金から発泡ゴム層が浮き上がりやすく、したがって、接着が不十分になりやすいという問題があるが、これについては何ら検討されていない。
本発明はこれらの点に鑑みてなされたものであり、ＯＢＳＨを発泡剤として用いて製造した、画像不良を引き起こすアンモニアを発生しない発泡ゴムローラを提供することを課題とする。 The present invention has been made in view of these points, and an object of the present invention is to provide a foamed rubber roller that is produced using OBSH as a foaming agent and does not generate ammonia that causes image defects.
本発明者らは上記課題を解決するため、鋭意検討し、本発明に至った。 In order to solve the above problems, the present inventors have intensively studied to arrive at the present invention.
すなわち、本発明は、原料ゴム組成物を芯金の外周上に配置せしめた後、発泡加硫して製造された発泡ゴムローラであって、発泡ゴム層の密度が０．２０〜０．５０ｇ／ｃｍ3であり、該原料ゴム組成物が、ゴム成分を１００質量部としたとき、少なくともｐ，ｐ’−オキシビスベンゼンスルホニルヒドラジド２．５〜１５質量部、モルホリノジチオ化合物０．５〜３．０質量部および硫黄１．０〜４．０質量部を含有するものであることを特徴とする発泡ゴムローラである。 That is, the present invention is a foam rubber roller manufactured by foaming vulcanization after the raw rubber composition is placed on the outer periphery of the core metal, and the density of the foam rubber layer is 0.20 to 0.50 g / cm 3 , and when the raw rubber composition has 100 parts by mass of the rubber component, at least 2.5 to 15 parts by mass of p, p′-oxybisbenzenesulfonyl hydrazide , and morpholinodithio compound 0.5 to 3. The foamed rubber roller is characterized by containing 0 part by mass and 1.0 to 4.0 parts by mass of sulfur.
なお、発泡加硫が無加圧下で行われることが好ましく、原料ゴム組成物の１４０℃でのレオメータの加硫速度ｔｃ（１０）が１．５〜４．０分であること、原料ゴム組成物の主ゴム成分がエチレン−プロピレン−非共役ジエン共重合ゴムであること、発泡層の密度が０．２８〜０．４７ｇ／ｃｍ3であること、ＯＢＳＨの配合量が３〜１５質量部であることが好ましい。 The foam vulcanization is preferably performed under no pressure. The raw rubber composition has a rheometer vulcanization rate tc (10) at 140 ° C. of 1.5 to 4.0 minutes, and the raw rubber composition. The main rubber component of the product is an ethylene-propylene-nonconjugated diene copolymer rubber, the density of the foam layer is 0.28 to 0.47 g / cm 3 , and the blending amount of OBSH is 3 to 15 parts by mass. Oh and Turkey are preferable.
さらに、本発明は、原料ゴム組成物を芯金の外周上に配置せしめる方法が、押出し機を用いて原料ゴム組成物を押出すと同時に、連続的に芯金を押出し機のクロスヘッドダイを通過させて、芯金の外周上に該ゴム組成物を配置せしめる方法であることを特徴とする上記の発泡ゴムローラである。 Further, according to the present invention, the method of placing the raw rubber composition on the outer periphery of the core metal extrudes the raw rubber composition using an extruder, and at the same time, the core metal is continuously extruded from the crosshead die of the extruder. The foamed rubber roller described above, wherein the rubber composition is a method in which the rubber composition is disposed on the outer periphery of the cored bar.
また、本発明は、発泡ゴム層の外周上にさらに１層以上の機能層が形成されていることを特徴とする上記の発泡ゴムローラである。 The present invention is also the above foam rubber roller, wherein one or more functional layers are further formed on the outer periphery of the foam rubber layer.
本発明の発泡ゴムローラは、環境的に問題があり、外部への腐食の原因にもなるアンモニアの発生が抑制されており、電子写真装置や静電記録装置の各種ローラ部材として、アンモニアによる画像不良を引き起こすことはなく、良画質化が可能となるので、工業的利用価値は高い。 The foamed rubber roller of the present invention has environmental problems and suppresses the generation of ammonia, which also causes corrosion to the outside, and as a roller member of electrophotographic apparatus and electrostatic recording apparatus, image defects due to ammonia Therefore, the image quality can be improved and the industrial utility value is high.
以下、本発明の実施の形態について説明する。 Embodiments of the present invention will be described below.
図１に本発明の発泡ゴムローラの１例の断面図を示す。 FIG. 1 shows a cross-sectional view of one example of the foam rubber roller of the present invention.
図１において、１は芯金であり、その外周に発泡ゴム層２が形成されている。なお、発泡ゴム層の上にさらに１層以上の機能層が設けられても構わない。また、芯金１と発泡ゴム層２との間に接着剤層が形成されることが好ましい。
In FIG. 1, 1 is a metal core, and a
本発明に使用する原料ゴム組成物は、ゴム成分１００質量部に対し、少なくともＯＢＳＨ２．５〜１５質量部および硫黄１．０〜４．０質量部を含有させたものを用いること以外特に限定するものではない。 The raw rubber composition used in the present invention is particularly limited except that at least 2.5 to 15 parts by mass of OBSH and 1.0 to 4.0 parts by mass of sulfur are used with respect to 100 parts by mass of the rubber component. It is not a thing.
また、本発明の発泡ゴムローラは発泡ゴム層の密度（加硫ゴム−密度測定（ＪＩＳ Ｋ６２６８）による）が０．２０〜０．５０ｇ／ｃｍ3にあることが必須である。すなわち、発泡ゴム層の密度がこの範疇にあることは、つまり該発泡ゴム層が高発泡していることを意味するものである。なお、好ましくは、発泡ゴム層の密度が０．２８〜０．４７ｇ／ｃｍ3にあることである。発泡ゴム層の密度が０．５０ｇ／ｃｍ3を超えると画像形成装置のローラとして用いたときに必要なニップ幅がえられないことが多く、また、０．２０ｇ／ｃｍ3未満では得られる発泡ゴムローラを画像形成装置のローラとして用いたときにニップ幅が大きくなりすぎて所望の性能が得られない。さらに、発泡ゴム層の密度が０．２０ｇ／ｃｍ3未満では発泡ゴムローラを安定して製造することが困難となる。 In the foam rubber roller of the present invention, it is essential that the density of the foam rubber layer (vulcanized rubber-density measurement (JIS K6268)) is 0.20 to 0.50 g / cm 3 . That is, that the density of the foamed rubber layer is in this category means that the foamed rubber layer is highly foamed. In addition, Preferably, it is that the density of a foamed rubber layer exists in 0.28-0.47g / cm < 3 >. When the density of the foamed rubber layer exceeds 0.50 g / cm 3 , the necessary nip width is often not obtained when used as a roller of an image forming apparatus, and when the density is less than 0.20 g / cm 3 , foaming is obtained. When a rubber roller is used as a roller of an image forming apparatus, the nip width becomes too large and desired performance cannot be obtained. Furthermore, if the density of the foam rubber layer is less than 0.20 g / cm 3 , it becomes difficult to stably produce the foam rubber roller.
ＯＢＳＨは単独使用が可能であり、単独で使用すればアンモニアを発生しないが、発泡分解時に発生する酸性物質による加硫阻害により、圧縮永久歪みの悪化などの品質低下の問題がある。そこで、硫黄を一般的なゴム用途で使用するよりも多めで、すなわち、ゴム成分１００質量部に対して硫黄１．０〜４．０質量部を含有させる。そうすることで加硫阻害による架橋密度の低下を防ぐことが可能になる。硫黄の使用量が１．０質量部未満では架橋密度の低下を防げず、また、４．０質量部を超えると硫黄が浮き出て白くなるブルームが発生しやすくなり好ましくない。好ましい硫黄の使用量は１．５〜３．０質量部である。 OBSH can be used alone and does not generate ammonia if used alone, but there is a problem of quality deterioration such as deterioration of compression set due to inhibition of vulcanization by acidic substances generated during foam decomposition. Therefore, the amount of sulfur is larger than that used for general rubber applications, that is, 1.0 to 4.0 parts by mass of sulfur is contained with respect to 100 parts by mass of the rubber component. By doing so, it is possible to prevent a decrease in crosslink density due to inhibition of vulcanization. If the amount of sulfur used is less than 1.0 part by mass, the decrease in the crosslinking density cannot be prevented, and if it exceeds 4.0 parts by mass, blooming of sulfur and whitening tends to occur, which is not preferable. A preferable amount of sulfur used is 1.5 to 3.0 parts by mass.
本発明では、芯金上に原料ゴム組成物を配設した後の加硫発泡させるのであるが、加硫発泡については、従来公知の方法、例えば、金型内で発泡加硫させる方法、電気炉、熱風炉あるいはマイクロ波加熱装置中で無加圧下に発泡加硫させる方法等を採用できる。金型を用いる方法に比べ、無加圧下に発泡加硫する方が、発泡加硫ムラが少なくなるので、無加圧下に行うことが好ましい。 In the present invention, the raw rubber composition is disposed on the core metal and then vulcanized and foamed. Regarding the vulcanized foam, a conventionally known method such as foam vulcanization in a mold, A method of foaming and vulcanizing under no pressure in a furnace, a hot air furnace or a microwave heating apparatus can be employed. Compared with a method using a mold, foaming and vulcanization under no pressure reduces foaming vulcanization unevenness. Therefore, it is preferable to carry out without pressure.
ところで、ＯＢＳＨの単独使用によるもう一つの問題として、無加圧下に高発泡化した際、原料ゴム組成物の発泡加硫と芯金と発泡ゴム層の接着を同時に行う場合には、芯金から発泡ゴム層が浮き上がりやすく、接着が不十分になりやすくなることが挙げられる。 By the way, as another problem due to the single use of OBSH, when high foaming is performed under no pressure, when the foam vulcanization of the raw rubber composition and the bonding of the cored bar and the foamed rubber layer are performed simultaneously, For example, the foamed rubber layer tends to float and adhesion tends to be insufficient.
ここで発明者らは、ＯＢＳＨを含有すると初期加硫が速くなることに着眼し、初期加硫の速度を調整すること、つまり、原料ゴム組成物の１４０℃でのレオメータの加硫速度ｔｃ（１０）（以下、「ｔｃ（１０）」と表す。）が１．５〜４．０分に調整されることで、芯金上から発泡ゴム層が浮き難くなり、接着性が十分確保されることを見出した。原料ゴム組成物のｔｃ（１０）が１．５分未満では芯金上から発泡ゴム層が浮き易くなる。この原因は定かではないが、ｔｃ（１０）が１．５分未満では、発泡加硫工程において、ローラの外側からの加熱によりローラ表面側から原料ゴム組成物の加硫が進行するに従い、発生した発泡ガスがローラ表面より抜けずにまだ未加硫の芯金側へと流れ、芯金と発泡したゴム層の間に溜まることとなり、芯金より発泡ゴム層が浮き上がり易くなるからであると考えられる。また、ｔｃ（１０）が４．０分を超えると、ローラ表面の加硫の進行が遅いため、発生した発泡ガスがゴム層に保持されず、ガス抜け現象が発生して、高発泡の発泡ゴム層を得難くなることがある。より好ましくは、原料ゴム組成物のｔｃ（１０）が２．０〜３．５分である。 Here, the inventors pay attention to the fact that the initial vulcanization becomes faster when OBSH is contained, and adjust the initial vulcanization speed, that is, the vulcanization speed tc (rheometer of the raw rubber composition at 140 ° C. 10) (hereinafter referred to as “tc (10)”) is adjusted to 1.5 to 4.0 minutes, the foamed rubber layer hardly floats on the core metal, and sufficient adhesion is ensured. I found out. When the raw rubber composition has a tc (10) of less than 1.5 minutes, the foamed rubber layer tends to float from the cored bar. The cause of this is not clear, but when tc (10) is less than 1.5 minutes, it occurs as the raw rubber composition vulcanizes from the roller surface side by heating from the outside of the roller in the foam vulcanization process. This is because the foamed gas does not escape from the roller surface and still flows to the unvulcanized core metal side and accumulates between the core metal and the foamed rubber layer. Conceivable. If tc (10) exceeds 4.0 minutes, the progress of vulcanization on the roller surface is slow, so that the generated foaming gas is not retained in the rubber layer, causing a gas escape phenomenon, and high foaming foaming. It may be difficult to obtain a rubber layer. More preferably, the raw rubber composition has a tc (10) of 2.0 to 3.5 minutes.
また、原料ゴム組成物のｔｃ（１０）は加硫剤や加硫促進剤類により調整が可能であるが、ＯＢＳＨの添加量によっても調整ができる。ＯＢＳＨを含有すると初期加硫が速くなること利用して、ｔｃ（１０）をＯＢＳＨの添加量で調整するもので、ＯＢＳＨの添加量が２．５〜１５質量部あると、最適なｔｃ（１０）が得られやすい。好ましくは、ＯＢＳＨの添加量は３〜１５質量部であり、より好ましくは、４〜１０質量部である。また、ＯＢＳＨの添加量が２．５質量部未満であると、十分な発泡ガスが得られず、高発泡化が困難になり好ましくない。１５質量部を超えると発泡加硫と接着を同時に行う場合には、芯金上から発泡ゴム層が浮き上がりやすく接着性が不十分になりやすく好ましくない。 Further, tc (10) of the raw rubber composition can be adjusted by a vulcanizing agent or a vulcanization accelerator, but can also be adjusted by an amount of OBSH added. When OBSH is contained, tc (10) is adjusted by the addition amount of OBSH by utilizing the fact that initial vulcanization becomes faster. When the addition amount of OBSH is 2.5 to 15 parts by mass, the optimum tc (10 ) Is easily obtained. Preferably, the amount of OBSH added is 3 to 15 parts by mass, more preferably 4 to 10 parts by mass. On the other hand, if the amount of OBSH added is less than 2.5 parts by mass, a sufficient foaming gas cannot be obtained, making it difficult to achieve high foaming. When the amount exceeds 15 parts by mass, when foam vulcanization and adhesion are performed simultaneously, the foamed rubber layer tends to float from the core metal and the adhesiveness tends to be insufficient, which is not preferable.
本発明で使用する原料ゴム組成物用の原料ゴムとしては、特に限定するもではなく、エチレン−プロピレン−ジエン共重合ゴム（ＥＰＤＭ）、アクリロニトリル−ブタジエン共重合ゴム（ＮＢＲ）、天然ゴム（ＮＲ）、ブタジエンゴム（ＢＲ）、スチレン−ブタジエン共重合ゴム（ＳＢＲ）、クロロプレンゴム（ＣＲ）、エピクロルヒドリン系ゴム（ＣＯ、ＥＣＯ）等の各種原料ゴムが使用できるが、中でも耐オゾン性が優れる、耐熱性が優れる、安価であるという観点からエチレン−プロピレン−非共役ジエン共重合ゴムが好ましい。 The raw rubber for the raw rubber composition used in the present invention is not particularly limited, and ethylene-propylene-diene copolymer rubber (EPDM), acrylonitrile-butadiene copolymer rubber (NBR), natural rubber (NR). Various raw rubbers such as butadiene rubber (BR), styrene-butadiene copolymer rubber (SBR), chloroprene rubber (CR), epichlorohydrin rubber (CO, ECO), etc. can be used. From the viewpoint of being excellent and inexpensive, an ethylene-propylene-nonconjugated diene copolymer rubber is preferred.
また、本発明で使用する原料ゴム組成物には、導電性、補強性あるいは加工性等や増量充填の目的から、ケッチェンブラック（商品名）、コンダクテックス（商品名）等の導電性カーボンブラック、ＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＭＡＦ、ＦＥＦ、ＧＰＦ、ＳＲＦ、ＦＴ、ＭＴ等のゴム用カーボンブラック、各種重質炭酸カルシウム、各種軽質炭酸カルシウム、クレー類、炭酸マグネシウム、シリカ、珪酸マグネシウム、タルク等の各種フィラー類が添加できる。フィラー類の添加量は、原料ゴム１００質量部に対して１０〜１００質量部が好ましく、２０〜７０質量部が特に好ましい。 In addition, the raw rubber composition used in the present invention includes conductive carbon black such as Ketjen Black (trade name), Conductex (trade name), etc. for the purpose of conductivity, reinforcement, processability, and increased filling. , SAF, ISAF, HAF, MAF, FEF, GPF, SRF, FT, MT and other rubber carbon blacks, various heavy calcium carbonates, various light calcium carbonates, clays, magnesium carbonate, silica, magnesium silicate, talc, etc. Various fillers can be added. The amount of the filler added is preferably 10 to 100 parts by mass, particularly preferably 20 to 70 parts by mass with respect to 100 parts by mass of the raw rubber.
また、加硫剤としては、硫黄を使用するのであるが、さらに必要に応じて種々ものを併用することができる。特に、原料ゴム組成物の発泡及び加硫の制御を容易に行うことができる点から、硫黄加硫系とすることが好ましい。ここで、硫黄加硫系とは、硫黄と加硫促進剤との組み合わせ、あるいは含硫黄有機化合物をいう。加硫促進剤としては、チアゾール類，スルフェンアミド類，チオウレア類，チウラム類，ジチオカルバミン酸塩類，グアニジン類，アルデヒドアミン類，アルデヒドアンモニア類が挙げられ、これらの一種を単独で又は二種以上を混合して用いることができる。含硫黄有機化合物としては、例えば、モルホリンジスルフィド，テトラアルキルチウラムジスルフィド，ジペンタメチレンチウラムテトラスルフィド等が挙げられる。これら加硫剤の添加量は、原料ゴム１００質量部に対して０．５〜５質量部が好ましい。 Moreover, although sulfur is used as a vulcanizing agent, various things can be used together as needed. In particular, it is preferable to use a sulfur vulcanization system from the viewpoint that the foaming and vulcanization of the raw rubber composition can be easily controlled. Here, the sulfur vulcanization system refers to a combination of sulfur and a vulcanization accelerator, or a sulfur-containing organic compound. Examples of vulcanization accelerators include thiazoles, sulfenamides, thioureas, thiurams, dithiocarbamates, guanidines, aldehyde amines, and aldehyde ammonia. These may be used alone or in combination of two or more. It can be used by mixing. Examples of the sulfur-containing organic compound include morpholine disulfide, tetraalkyl thiuram disulfide, dipentamethylene thiuram tetrasulfide, and the like. The addition amount of these vulcanizing agents is preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the raw rubber.
中でもモルホリンジスルフィド等のモルホリノジチオ化合物は初期加硫を遅くする効果があり、本発明のＯＢＳＨと併用することにより、ｔｃ（１０）のコントロールを容易にするので好ましい。 Among them, morpholinodithio compounds such as morpholine disulfide are preferable because they have an effect of slowing initial vulcanization and can be easily used in combination with the OBSH of the present invention to control tc (10).
本発明に係る発泡ゴムには、上記の添加剤以外に、亜鉛華，ステアリン酸等の加硫促進助剤、パラフィン系プロセスオイル等の軟化剤、スコーチ防止剤、粘着付与剤、その他ゴム用添加剤を、本発明の効果を損なわない範囲で適宜添加することができる。 In addition to the above additives, the foamed rubber according to the present invention includes vulcanization acceleration aids such as zinc white and stearic acid, softeners such as paraffinic process oil, scorch inhibitor, tackifier, and other rubber additives. An agent can be appropriately added as long as the effects of the present invention are not impaired.
本発明の発泡ゴムローラの製造法は、各種方法が採用可能であるが、押出し機を用いて未加硫のゴム組成物を押出すと同時に、連続的に該芯金を押出し機のクロスヘッドダイを通過させて、芯金の外周上に未加硫のゴム組成物を配置せしめローラ形状にした後、発泡加硫工程を経て製造されることが低コストの観点から好ましい。また、発泡加硫方法は、上述のように、特に限定するものではないが、連続式の熱風炉を用いてなされることが好ましい。連続式の熱風炉は、押出し機と連結して生産することが可能であり、金型等を用いて生産する場合に比べて装置及び金型コスト上有利になる。なお、芯金としては、通常、鉄材からなり、表面を約３μｍ厚の化学メッキしたものが用いられる。また、該芯金には、例えば、ホットメルト接着剤、加硫接着剤等の接着剤を塗布しておくことが好ましい。 Various methods can be adopted as the method for producing the foamed rubber roller of the present invention. At the same time as the unvulcanized rubber composition is extruded using an extruder, the core metal is continuously removed from the crosshead die of the extruder. It is preferable from the viewpoint of low cost that the rubber composition is made through a foaming vulcanization step after passing the slag and placing an unvulcanized rubber composition on the outer periphery of the core metal to form a roller shape. Further, the foam vulcanization method is not particularly limited as described above, but it is preferable to use a continuous hot air furnace. The continuous hot stove can be produced by being connected to an extruder, which is advantageous in terms of apparatus and mold cost as compared with the case of producing using a mold or the like. The cored bar is usually made of an iron material and the surface is chemically plated with a thickness of about 3 μm. In addition, for example, an adhesive such as a hot melt adhesive or a vulcanized adhesive is preferably applied to the core metal.
なお、本発明の発泡ゴムローラは、さらなる表面平滑性の向上や抵抗調整や保護を目的として発泡ゴム層の外周上に１層以上の機能層を設けてもよく、例えば、発泡ゴム層の外周面に抵抗調整層として、ゴムや樹脂等によるチューブ層、塗装による導電層等を形成しても差し支えない。 The foamed rubber roller of the present invention may be provided with one or more functional layers on the outer periphery of the foamed rubber layer for the purpose of further improving the surface smoothness, resistance adjustment and protection, for example, the outer peripheral surface of the foamed rubber layer. In addition, a tube layer made of rubber or resin, a conductive layer made by coating, or the like may be formed as the resistance adjustment layer.
次に、本発明を実施例により、さらに詳細に説明するが、本発明は、これらの例により、なんら限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
なお、各例で得られた発泡ゴムローラの物性は、以下の方法に従って測定した。 The physical properties of the foam rubber roller obtained in each example were measured according to the following methods.
〔密度〕
ＪＩＳ Ｋ６２６８の加硫ゴム−密度の測定によった。
〔density〕
According to the measurement of vulcanized rubber density according to JIS K6268.
〔アスカーＣ硬さ〕
ＪＩＳ Ｓ６０５０に準じたスポンジ用スプリング式硬度計［アスカーＣ型硬度計 測定荷重５００ｇ（高分子計器株式会社製）］を用いて測定した。
[Asker C hardness]
It was measured using a spring-type hardness meter for sponges according to JIS S6050 [Asker C-type hardness meter, measuring load 500 g (manufactured by Kobunshi Keiki Co., Ltd.)].
〔１４０℃でのレオメータの加硫速度ｔｃ（１０）〕
発泡圧測定機能付き加硫試験機ＭＤＲ−２００Ｐ（アルファーテクノロジーズ社製）を用いて測定した。
[Rheometer vulcanization rate at 140 ° C. tc (10)]
It measured using the vulcanization tester MDR-200P with a foaming pressure measurement function (made by Alpha Technologies).
〔芯金と発泡ゴムの接着性〕
端部切断処理した後の発泡ゴムローラの端部を目視により観察し、下記基準により判断した。
○：芯金と発泡ゴムが密着している。
×：芯金と発泡ゴムの間にわずかでも隙間が観察され、剥がれがある。
[Adhesion between cored bar and foamed rubber]
The edge part of the foamed rubber roller after the edge part cutting treatment was visually observed and judged according to the following criteria.
○: The cored bar and foamed rubber are in close contact.
X: Even a slight gap is observed between the cored bar and the foamed rubber, and there is peeling.
〔ベタツキ〕
発泡ゴムローラの表面を手で触り、下記基準で判断した。
×：ベタツキ感や粘着感あり、ゴムが十分に加硫されていない。
○：ベタツキ感や粘着感なく、ゴムが十分に加硫されている。
[Sticky]
The surface of the foam rubber roller was touched by hand and judged according to the following criteria.
X: There is a sticky feeling or a sticky feeling, and the rubber is not sufficiently vulcanized.
○: Rubber is sufficiently vulcanized without stickiness or stickiness.
〔アンモニア発生の確認〕
発泡ゴムローラから発泡ゴム層５０ｍｇを切り取り、蒸留水３ｍｌを入れたふた無しのガラス瓶と共に５０ｍｌのふた付きガラス瓶の中に入れ、ガラス瓶内に密閉する。この密閉したガラス瓶を４０℃、湿度９５％の環境に設定された恒温恒湿槽に２４時間投入した後、恒温恒湿槽から密閉したガラス瓶を取り出し、室温下になったところで、ガラス瓶のふたを開け、アンモニア検知管［商品名「アンモニア３Ｌ」、ガステック株式会社製］によりアンモニアの発生の有無を確認する。
[Confirmation of ammonia generation]
Cut 50 mg of the foam rubber layer from the foam rubber roller, put it in a 50 ml glass bottle with a lid together with 3 ml of distilled water and seal it in the glass bottle. The sealed glass bottle was put into a thermostatic chamber set at 40 ° C. and a humidity of 95% for 24 hours, and then the sealed glass bottle was taken out from the thermostatic chamber, and when the room temperature was lowered, the lid of the glass bottle was opened. Open and check whether ammonia is generated by an ammonia detector tube [trade name “Ammonia 3L”, manufactured by Gastec Corporation].
〔実施例１〕
エチレン−プロピレン−非共役ジエン共重合ゴム（ＥＰＤＭ）［商品名：ＥＰＴ４０７０、三井化学株式会社製］１００質量部、
酸化亜鉛［商品名：亜鉛華２種、白水テック株式会社製］５質量部、
ステアリン酸［商品名：ステアリン酸Ｓ、花王株式会社製］１質量部、
導電性カーボン［商品名：ケッチェンブラックＥＣ、ケッチェンブラックインターナショナル社製］１１質量部、
ＦＥＦ級カーボンブラック［商品名：旭＃６０、旭カーボン株式会社製］３０質量部、
パラフィンオイル［商品名：ダイアナプロセスオイルＰＷ−３８０、出光興産株式会社製］５０質量部、
モルホリノジチオ化合物（ＭＤＢ）［商品名：ノクセラーＭＤＢ、大内振興化学工業株式会社製］２質量部、
２−メルカプトベンゾチアゾール（ＭＢＴ）［商品名：ノクセラーＭ、大内振興化学工業株式会社製］１質量部、
ジペンタメチレンチウラムテトラスルフィド（ＤＰＴＴ）［商品名：ノクセラーＴＲＡ、大内振興化学工業株式会社製］１質量部、
ジブチルジチオカルバミン酸亜鉛（ＺＤＢＣ）［商品名：ノクセラーＢＺ、大内振興化学工業株式会社製］１質量部、
硫黄［商品名：サルファックスＰＭＣ、鶴見化学工業株式会社製］２質量部、
ｐ、ｐ’−オキシビスベンゼンスルホニルヒドラジド（ＯＢＳＨ）［商品名：ネオセルボン１０００Ｓ、永和化成工業株式会社製］８質量部
以上の原料を混錬りし、原料ゴム組成物を作成した。
[Example 1]
100 parts by mass of ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) [trade name: EPT4070, manufactured by Mitsui Chemicals, Inc.]
5 parts by mass of zinc oxide [trade name: two types of zinc white, manufactured by Hakusui Tec Co., Ltd.]
1 part by mass of stearic acid [trade name: stearic acid S, manufactured by Kao Corporation]
Conductive carbon [trade name: Ketjen Black EC, manufactured by Ketjen Black International] 11 parts by mass,
FEF class carbon black [trade name: Asahi # 60, manufactured by Asahi Carbon Co., Ltd.] 30 parts by mass,
50 parts by mass of paraffin oil [trade name: Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.]
Morpholinodithio compound (MDB) [trade name: Noxeller MDB, manufactured by Ouchi Shinko Chemical Co., Ltd.] 2 parts by mass,
2-mercaptobenzothiazole (MBT) [trade name: Noxeller M, manufactured by Ouchi Shinko Chemical Co., Ltd.] 1 part by mass,
1 part by mass of dipentamethylene thiuram tetrasulfide (DPTT) [trade name: Noxeller TRA, manufactured by Ouchi Shinko Chemical Co., Ltd.]
1 part by mass of zinc dibutyldithiocarbamate (ZDBC) [trade name: Noxeller BZ, manufactured by Ouchi Shinko Chemical Co., Ltd.]
2 parts by mass of sulfur [trade name: Sulfax PMC, manufactured by Tsurumi Chemical Co., Ltd.]
p, p′-Oxybisbenzenesulfonylhydrazide (OBSH) [trade name: Neoselbon 1000S, manufactured by Eiwa Kasei Kogyo Co., Ltd.] 8 parts by mass The above raw materials were kneaded to prepare a raw rubber composition.
φ４０ｍｍのクロスヘッド付き押出し機を用いて原料ゴム組成物を押出すと同時に、連続的にホットメルト接着剤［商品名：スリーボンド３３１５Ｅ、スリーボンド株式会社製］を塗布したφ６ｍｍの鉄製の芯金（ニッケル化学メッキをしたもの）を押出し機のクロスヘッドダイを通過させて、芯金の外周上に厚み２ｍｍに原料ゴム組成物を配置せしめローラ形状にした後、２００℃の熱風炉に３０分間投入して、発泡加硫を行い、芯金上に厚み４ｍｍの発泡加硫ゴム層を形成した未研削の発泡ゴムローラを作成した。この成形体を、研磨砥石ＧＣ８０を取り付けた研削機にセットし、研削条件として回転速度２０００ＲＰＭ、送り速度５００ｍ／分で外径がφ１２ｍｍになるように研削し、発泡ゴムローラを作成した。 At the same time as extruding the raw rubber composition using an extruder with a cross head having a diameter of 40 mm, an iron core bar having a diameter of 6 mm coated with a hot melt adhesive [trade name: ThreeBond 3315E, manufactured by ThreeBond Co., Ltd.] (Chemical plating) is passed through the crosshead die of the extruder, and the raw rubber composition is placed on the outer periphery of the cored bar to form a roller shape, and then put into a 200 ° C hot air oven for 30 minutes. Thus, foam vulcanization was performed to prepare an unground foamed rubber roller in which a foam vulcanized rubber layer having a thickness of 4 mm was formed on the core metal. This molded body was set in a grinder equipped with a grinding wheel GC80, and ground as a grinding condition so that the outer diameter was 12 mm at a rotational speed of 2000 RPM and a feed speed of 500 m / min, to produce a foam rubber roller.
〔実施例２〕
実施例１において、硫黄の配合量を４質量部に増やした以外は実施例１と同様にして発泡ゴムローラを作成した。
[Example 2]
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the amount of sulfur was increased to 4 parts by mass.
〔実施例３〕
実施例１において、硫黄の配合量を１質量部に減らした以外は実施例１と同様にして発泡ゴムローラを作成した。
Example 3
In Example 1, a foam rubber roller was prepared in the same manner as in Example 1 except that the amount of sulfur was reduced to 1 part by mass.
〔実施例４〕
実施例１において、ＯＢＳＨの配合量を３質量部に減らした以外は実施例１と同様にして発泡ゴムローラを作成した。
Example 4
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the blending amount of OBSH was reduced to 3 parts by mass.
〔実施例５〕
実施例１において、ＯＢＳＨの配合量を１５質量部に増やした以外は実施例１と同様にして発泡ゴムローラを作成した。
Example 5
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the blending amount of OBSH was increased to 15 parts by mass.
〔実施例６〕
実施例１において、ＦＥＦ級カーボンを配合せず、ＯＢＳＨの配合量を１５質量部に増やした以外は実施例１と同様にして発泡ゴムローラを作成した。
Example 6
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that FEF-grade carbon was not blended and the blending amount of OBSH was increased to 15 parts by mass.
〔比較例１〕
実施例１において、硫黄の配合量を０．５質量部に減らした以外は実施例１と同様にして発泡ゴムローラを作成した。硫黄が少ないため、ゴム層の架橋密度が十分に上がらず、ベタツキや粘着が発生し、良品の発泡ゴムローラが得られなかった。
[Comparative Example 1]
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the amount of sulfur was reduced to 0.5 parts by mass. Since the sulfur content is low, the crosslink density of the rubber layer does not increase sufficiently, stickiness and adhesion occur, and a good foam rubber roller cannot be obtained.
〔比較例２〕
実施例１において、ＯＢＳＨの配合量を２質量部に減らした以外は実施例１と同様にして発泡ゴムローラを作成した。ＯＢＳＨの量が少ないため発泡が不十分になり、高発泡な発泡ゴムローラが得られなかった。
[Comparative Example 2]
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the blending amount of OBSH was reduced to 2 parts by mass. Since the amount of OBSH was small, foaming was insufficient, and a highly foamed foamed rubber roller could not be obtained.
〔比較例３〕
実施例１において、ＭＢＴ、ＤＰＴＴ、ＺＢＤＣおよびＯＢＳＨの配合量をそれぞれ１．５質量部、０．７質量部、１．５質量部、２質量部と変更し、ＭＤＢに代えてジメチルジチオカルバミン酸亜鉛（ＺＭＢＣ）［商品名：ノクセラーＰＺ、大内振興化学工業株式会社製］１．０質量部を用いた以外は実施例１と同様にして発泡ゴムローラを作成した。ＯＢＳＨの量が少ないため発泡が不十分になり、高発泡な発泡ゴムローラが得られなかった。
[Comparative Example 3]
In Example 1, the amounts of MBT, DPTT, ZBDC and OBSH were changed to 1.5 parts by mass, 0.7 parts by mass, 1.5 parts by mass and 2 parts by mass, respectively, and zinc dimethyldithiocarbamate instead of MDB. (ZMBC) [trade name: Noxeller PZ, manufactured by Ouchi Shinko Chemical Co., Ltd.] A foamed rubber roller was produced in the same manner as in Example 1 except that 1.0 part by mass was used. Since the amount of OBSH was small, foaming was insufficient, and a highly foamed foamed rubber roller could not be obtained.
〔比較例４〕
実施例１において、ＯＢＳＨの配合量を２０質量部に増やした以外は実施例１と同様にして発泡ゴムローラを作成した。ＯＢＳＨの量が多いため、芯金から発泡ゴム層が浮き上がり、良品の発泡ゴムローラが得られなかった。
[Comparative Example 4]
In Example 1, a foamed rubber roller was prepared in the same manner as in Example 1 except that the amount of OBSH was increased to 20 parts by mass. Since the amount of OBSH was large, the foamed rubber layer was lifted from the core metal, and a good foamed rubber roller could not be obtained.
〔比較例５〕
実施例１において、ＭＢＴ、硫黄およびＯＢＳＨの配合量をそれぞれ２質量部、１質量部、２質量部とし、ＭＤＢを全く使用せず、さらに、アゾジカルボンアミド（ＡＤＣＡ）［商品名：ビニホールＡＣ＃ＬＱ、永和化成工業株式会社製］８質量部および尿素［商品名：セルペースト１０１、永和化成工業株式会社製］２質量部を加えた以外は実施例１と同様にして発泡ゴムローラを作成した。この比較例で得られた発泡ゴムローラは、ＡＤＣＡおよび尿素を用いたためアンモニアの発生量があり、電子写真装置用のローラ部材としての使用に問題があると判断された。
[Comparative Example 5]
In Example 1, the blending amounts of MBT, sulfur, and OBSH were 2 parts by mass, 1 part by mass, and 2 parts by mass, respectively, MDB was not used at all, and azodicarbonamide (ADCA) [trade name: Binihol AC # A foamed rubber roller was prepared in the same manner as in Example 1 except that 8 parts by mass of LQ, manufactured by Eiwa Chemical Industry Co., Ltd. and 2 parts by mass of urea [trade name: Cell Paste 101, manufactured by Eiwa Chemical Industry Co., Ltd.] were added. Since the foamed rubber roller obtained in this comparative example uses ADCA and urea, the amount of ammonia generated is judged to be problematic for use as a roller member for an electrophotographic apparatus.
以上の実施例、比較例で作成した発泡ゴムローラについて、上記で記載した各物性を測定した結果を表１に示す。また、これらの結果から、発泡ゴムローラとして使用可能かどうかを総合判定した結果を表１に示す。 Table 1 shows the results of measuring the physical properties described above for the foamed rubber rollers prepared in the above Examples and Comparative Examples. Further, Table 1 shows the result of comprehensive determination as to whether or not the foam rubber roller can be used from these results.
実施例１または比較例５で得た発泡ゴムローラの外周上に抵抗調整するための導電層を設けたものを電子写真方式のプリンターの帯電ローラとして組み込んだ後、４０℃、９５％湿度に１ヶ月間保管し、その後標準パターンを画出し、得られた標準パターン上にアンモニア発生による感光体汚染の影響による画像不良が見られるか否かを調べた。実施例１の発泡ローラを用いたものでは全く問題はなかったが、比較例５の発泡ローラを用いたものでは感光体汚染の影響から画像不良が発生した。 After mounting the conductive layer for adjusting the resistance on the outer periphery of the foam rubber roller obtained in Example 1 or Comparative Example 5 as a charging roller of an electrophotographic printer, one month at 40 ° C. and 95% humidity It was stored for a while, and then a standard pattern was drawn out, and it was examined whether or not an image defect was observed on the obtained standard pattern due to the influence of photoreceptor contamination due to the generation of ammonia. In the case of using the foaming roller of Example 1, there was no problem at all, but in the case of using the foaming roller of Comparative Example 5, an image defect occurred due to the influence of the photosensitive member contamination.
１ 芯金
２ 発泡ゴム層
1
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004067322A JP4455905B2 (en) | 2004-03-10 | 2004-03-10 | Foam rubber roller |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004067322A JP4455905B2 (en) | 2004-03-10 | 2004-03-10 | Foam rubber roller |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2005257881A JP2005257881A (en) | 2005-09-22 |
| JP4455905B2 true JP4455905B2 (en) | 2010-04-21 |
Family
ID=35083681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2004067322A Expired - Lifetime JP4455905B2 (en) | 2004-03-10 | 2004-03-10 | Foam rubber roller |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4455905B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4931120B2 (en) * | 2006-09-21 | 2012-05-16 | 信越ポリマー株式会社 | Method for producing elastic roller |
| US7720426B2 (en) * | 2007-01-29 | 2010-05-18 | Kabushiki Kaisha Toshiba | Cleaning device and image forming apparatus using the same |
| JP5904670B2 (en) * | 2012-12-14 | 2016-04-13 | 住友ゴム工業株式会社 | Conductive rubber composition, transfer roller and method for producing the same, and image forming apparatus |
-
2004
- 2004-03-10 JP JP2004067322A patent/JP4455905B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005257881A (en) | 2005-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1921511B1 (en) | Toner supply roller | |
| JP5835973B2 (en) | Developing member, electrophotographic process cartridge, and electrophotographic image forming apparatus | |
| JP5449447B2 (en) | Conductive roller | |
| US9465315B2 (en) | Semiconductive roller | |
| JP6555526B2 (en) | Semi-conductive roller | |
| JP2008152201A (en) | Conductive rubber roller | |
| US10474068B2 (en) | Electrically conductive rubber composition, transfer roller, and image forming apparatus | |
| JP6288839B2 (en) | Toner supply roller and image forming apparatus | |
| JP4455905B2 (en) | Foam rubber roller | |
| JP5297636B2 (en) | Conductive rubber roller, method of manufacturing the same, and charging roller | |
| JP2016173487A (en) | Semiconductive roller | |
| WO2005059657A1 (en) | Conductive rubber roller | |
| JP2016197218A (en) | Semi-conductive roller | |
| JP2005281579A (en) | Foamed rubber roller | |
| JP2010134256A (en) | Conductive roller for electrophotographic device, charging roller, and method for manufacturing conductive roller for electrophotographic device | |
| JP2008216462A (en) | Conductive rubber roller and transfer roller | |
| JP2014162103A (en) | Method for manufacturing electroconductive roller, electroconductive roller, and image forming device | |
| JP2006293061A (en) | Conductive roller and charging roller | |
| JP4070011B2 (en) | Method of manufacturing foamed conductive rubber roller for image forming apparatus and transfer roller | |
| JP4988249B2 (en) | Foam rubber roller and foam rubber roller manufacturing method | |
| JP2011164179A (en) | Toner-supplying roller and method of producing the same | |
| JP2007065468A (en) | Method for manufacturing foamed rubber roller | |
| US20150315370A1 (en) | Semiconductive roller | |
| JP2009202353A (en) | Manufacturing method of rubber roller and rubber roller | |
| JP2005219383A (en) | Method for producing foamed rubber roller |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20070110 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20091026 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091028 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091225 |
|
| 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: 20100127 |
|
| 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: 20100204 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130212 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4455905 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140212 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 |
|
| S111 | Request for change of ownership or part of ownership |
Free format text: JAPANESE INTERMEDIATE CODE: R313113 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |