JPH03187732A - Preparation of polyurethane roller with low hardness and electric conductivity - Google Patents
Preparation of polyurethane roller with low hardness and electric conductivityInfo
- Publication number
- JPH03187732A JPH03187732A JP1327794A JP32779489A JPH03187732A JP H03187732 A JPH03187732 A JP H03187732A JP 1327794 A JP1327794 A JP 1327794A JP 32779489 A JP32779489 A JP 32779489A JP H03187732 A JPH03187732 A JP H03187732A
- Authority
- JP
- Japan
- Prior art keywords
- polyol
- polyisocyanate
- low hardness
- polyurethane
- functional group
- 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.)
- Granted
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract 2
- 229920005862 polyol Polymers 0.000 claims abstract description 41
- 150000003077 polyols Chemical class 0.000 claims abstract description 41
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 21
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000004020 conductor Substances 0.000 claims abstract description 12
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 238000004519 manufacturing process Methods 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 229920005906 polyester polyol Polymers 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000843 powder Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 239000004970 Chain extender Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 239000003431 cross linking reagent Substances 0.000 description 5
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- -1 aliphatic glycols Chemical class 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 1
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
Landscapes
- Dry Development In Electrophotography (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
皮粟上皇肌里分立
本発明は、低硬度で導電性を有し、加圧現像方式による
電子写真複写機において、トナーを現像域まで搬送する
ためのトナーローラとして好適に用いることができる低
硬度導電性ポリウレタンローラの製造方法に関する。[Detailed description of the invention] The present invention has low hardness and conductivity, and is suitable as a toner roller for conveying toner to a developing area in an electrophotographic copying machine using a pressure development method. The present invention relates to a method of manufacturing a low hardness conductive polyurethane roller that can be used for.
ｌ来■技玉
例えば、加圧現像方式による電子写真複写機において、
トナーローラは、トナーをローラに付着させ、現像域ま
で搬送するために、トナーに対して逆極性に摩擦帯電す
る導電性を有すると共に、感光体に対してトナーを加圧
する際に、感光体を傷付けないように、低硬度であるこ
とが要求される。For example, in an electrophotographic copying machine using a pressure development method,
The toner roller has electrical conductivity that causes the toner to be frictionally charged to the opposite polarity in order to adhere the toner to the roller and transport it to the development area. Low hardness is required to prevent damage.
従来、ポリウレタンに導電性を付与するためには、導電
性材料をポリウレタンプレポリマー中に配合し、プレポ
リマーを架橋硬化させる方法が知られている。他方、ポ
リウレタンの低硬度化を図るためには、ポリウレタンプ
レポリマーにおけるイソシアネート基量を極力低減させ
、且つ、高分子量の鎖延長剤や架橋剤を用いて、架橋さ
せる方法が知られている。Conventionally, in order to impart electrical conductivity to polyurethane, a method has been known in which a conductive material is blended into a polyurethane prepolymer and the prepolymer is crosslinked and cured. On the other hand, in order to reduce the hardness of polyurethane, a method is known in which the amount of isocyanate groups in a polyurethane prepolymer is reduced as much as possible and crosslinking is performed using a high molecular weight chain extender or crosslinking agent.
しかしながら、プレポリマーに導電性材料を混合する方
法によれば、その粘度が著しく上昇し、導電性材料をプ
レポリマー中に均一に分散させることが困難であって、
導電特性が均一な成形品を得ることができない、他方、
ポリウレタンを低硬度化させるために、プレポリマーに
おけるイソシアネート基量を低減しても、同様に、プレ
ポリマーの粘度の上昇が著しく、注型が困難であって、
例えば、均一な導電性を有するローラを得ることができ
ない、従って、従来、知られている方法によれば、ポリ
ウレタンに導電性を付与しつつ、その低硬度化を図るこ
とができない。However, according to the method of mixing a conductive material into a prepolymer, the viscosity of the prepolymer increases significantly, making it difficult to uniformly disperse the conductive material in the prepolymer.
On the other hand, it is not possible to obtain a molded product with uniform conductive properties.
Even if the amount of isocyanate groups in the prepolymer is reduced in order to lower the hardness of polyurethane, the viscosity of the prepolymer similarly increases significantly, making casting difficult.
For example, it is not possible to obtain a roller having uniform conductivity, and therefore, according to conventionally known methods, it is not possible to reduce the hardness of polyurethane while imparting conductivity to it.
Ｂ ＜ ° しよ゛と る。B ゛゛.
本発明は、導電性で且つ低硬度のポリウレタンの製造方
法を提供することを目的とする。An object of the present invention is to provide a method for producing polyurethane that is electrically conductive and has low hardness.
量 ン るための
本発明による低硬度導電性ポリウレタンローラの製造方
法は、平均官能基数２．０を越えて、３．０以下である
ポリオールに予め導電性カーボンを混合し、このポリオ
ールをワン・ショット方式にてポリイソシアネートと反
応させることを特徴とする。The method for producing a low-hardness conductive polyurethane roller according to the present invention for the purpose of manufacturing is to mix conductive carbon in advance with a polyol having an average functional group number of more than 2.0 and less than 3.0, and to mix this polyol in one layer. It is characterized by reacting with polyisocyanate using a shot method.
本発明において用いるポリオールは、ポリイソシアネー
トとの反応によって、架橋構造を有するポリイソシアネ
ートを得るために、その平均官能基数が２．０を越える
ことが必要であり、他方、低硬度を図るためには、その
平均官能基数が３．０以下の範囲にあることが必要であ
り、特に、２．１〜２．５の範囲にあるのが好ましい。The polyol used in the present invention needs to have an average functional group number of more than 2.0 in order to obtain a polyisocyanate having a crosslinked structure by reaction with the polyisocyanate, and on the other hand, in order to achieve low hardness, It is necessary that the average number of functional groups is in the range of 3.0 or less, and in particular, it is preferably in the range of 2.1 to 2.5.
このようなポリオールとしては、その平均官能基数が上
記した範囲にある限りは、特に、限定されることなく、
例えば、種々のポリエステルポリオールを用いることが
できる。Such polyols are not particularly limited as long as the average number of functional groups is within the above range.
For example, various polyester polyols can be used.
かかるポリエステルポリオールとして、例えば、エチレ
ングリコール、プロピレングリコール、ブチレングリコ
ール、ペンタングリコール、ヘキセングリコール等の脂
肪族グリコール、ジエチレングリコール、ジプロピレン
グリコール等のポリアルキレングリコール等のグリコー
ル類と例えばトリメチロールプロパンのような三官能以
上の多価アルコールとをアルコール成分とし、これらを
アジピン酸、セバシン酸、スペリン酸、ブラシリン酸、
コハク酸等の脂肪族ジカルボン酸、テレフタル酸、イソ
フタル酸等の芳香族ジカルボン酸等を多塩基酸成分とし
て得られる縮合型ポリエステルポリオール等を挙げるこ
とができる。Such polyester polyols include, for example, aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, pentane glycol, and hexene glycol; glycols such as polyalkylene glycols such as diethylene glycol and dipropylene glycol; and glycols such as trimethylolpropane. The alcohol component is a polyhydric alcohol with a higher functional level, and these are combined into adipic acid, sebacic acid, speric acid, brassic acid,
Examples include condensed polyester polyols obtained as polybasic acid components such as aliphatic dicarboxylic acids such as succinic acid, aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid, and the like.
本発明においては、導電性材料としては、通常、金属粉
、導電性カーボン、界面活性剤等が好ましく用いられる
。In the present invention, metal powder, conductive carbon, surfactant, etc. are usually preferably used as the conductive material.
本発明においては、前述したようなポリオールに上記の
ような導電性材料を混練し、これを方法としてはそれ自
体既に知られているワン・ショット方式にてポリイソシ
アネートと反応させ、成形することによって、低硬度導
電性ポリウレタンローラを得る。In the present invention, the above-mentioned conductive material is kneaded with the above-mentioned polyol, and this is reacted with polyisocyanate by a one-shot method that is already known per se, and then molded. , obtain a low hardness conductive polyurethane roller.
本発明において用いるポリイソシアネートは、特に、限
定されるものではないが、屈曲した分子構造を有するポ
リイソシアネートが好ましく用いられる。このようなポ
リイソシアネートは、ポリウレタン鎖の結晶化を妨げる
ので、低硬度化が図りやすく、更に、分子鎖の絡み合い
を容易に形成し、いわば擬像架橋構造を有せしめるので
、脱型も容易である。特に、本発明にれば、ポリイソシ
アネートとしては、一般式
（式中、Ｒは炭素間結合又はアルキレン基を示し、Ｒ′
は水素又はアルキル基を示す、）
で表わされるものが好ましく用いられる。The polyisocyanate used in the present invention is not particularly limited, but polyisocyanate having a curved molecular structure is preferably used. Such polyisocyanates prevent the crystallization of polyurethane chains, making it easy to achieve low hardness.Furthermore, they easily form molecular chain entanglements, creating a so-called pseudo-crosslinked structure, making demolding easy. be. In particular, according to the present invention, the polyisocyanate has the general formula (wherein R represents a carbon-carbon bond or an alkylene group, and R'
represents hydrogen or an alkyl group) is preferably used.
このようなポリイソシアネートとしては、例えば、２．
４− ）ルエンジイソシアネート、２．６−トルエンジ
イソシアネート、これらの混合物、ｍ−テトラメチルキ
シリレンジイソシアネート、ｍ−キシレンジイソシアネ
ート、ｍ−フェニレンジイソシアネート等を挙げること
ができる。Examples of such polyisocyanates include 2.
4-) toluene diisocyanate, 2.6-toluene diisocyanate, mixtures thereof, m-tetramethylxylylene diisocyanate, m-xylylene diisocyanate, m-phenylene diisocyanate, and the like.
本発明においては、鎖延長剤又は架橋剤は、用いられな
い。一般にポリウレタンの製造に用いられている低分子
量多官能性の鎖延長剤や架橋剤を用いるときは、目的と
する低硬度のポリウレタンを得ることができず、他方、
多官能性の高分子量鎖延長剤や架橋剤を用いるときは、
それ自身の粘度が高いので、注型等の作業性に支障をき
たし、また、ポリウレタンを高硬度化する場合もある。In the present invention, no chain extenders or crosslinkers are used. When using low molecular weight polyfunctional chain extenders and crosslinking agents that are generally used in the production of polyurethane, it is not possible to obtain polyurethane with the desired low hardness;
When using polyfunctional high molecular weight chain extenders and crosslinking agents,
Since the viscosity of polyurethane itself is high, it may interfere with workability such as casting, and may also increase the hardness of polyurethane.
本発明においては、ポリオール及びポリイソシアネート
は、ポリオールに含まれている活性水素基とポリイソシ
アネートのイソシアネート基の化学当量比が０．５５〜
１．１０、好ましくは、０．６９〜１．０８の範囲にな
るように用いられる。また、反応に際して、加水分解防
止剤、難燃剤、充填剤、酸化防止剤、着色剤等、任意の
添加剤を用いることができる。必要に応じて、触媒も用
いられる。In the present invention, the polyol and polyisocyanate have a chemical equivalent ratio of active hydrogen groups contained in the polyol to isocyanate groups of the polyisocyanate of 0.55 to 1.
1.10, preferably in the range of 0.69 to 1.08. Further, during the reaction, arbitrary additives such as hydrolysis inhibitors, flame retardants, fillers, antioxidants, colorants, etc. can be used. A catalyst is also used if necessary.
光肌ｑ四来
以上のように、本発明によれば、所定の平均官能基数を
有するポリオールに予め導電性材料を混練し、これとポ
リイソシアネートとを鎖延長剤又は架橋剤なしに、ワン
・ショット法にて反応成形して、ポリウレタンローラを
得る。As described above, according to the present invention, a conductive material is kneaded in advance into a polyol having a predetermined average number of functional groups, and this and polyisocyanate are mixed together in one layer without a chain extender or crosslinking agent. A polyurethane roller is obtained by reaction molding using the shot method.
このように、本発明によれは、予めポリオールに導電性
材料を混合するので、その過程では粘度上昇が小さく、
しかも、導電性材料の配合量を任意に変更できると共に
、かかるポリオールとポリイソシアネートとの反応に際
して、鎖延長剤や架橋剤を用いないので、硬度の調整も
容易である。In this way, according to the present invention, since the conductive material is mixed with the polyol in advance, the increase in viscosity is small during the process.
Furthermore, the amount of the conductive material to be blended can be changed arbitrarily, and since no chain extender or crosslinking agent is used in the reaction between the polyol and polyisocyanate, the hardness can be easily adjusted.
従って、本発明によれば、導電性と硬度の程度を任意に
設計することができ、しかも、注型及び脱型作業を円滑
容易に行なって、低硬度と導電性とを同時に有する均一
なポリウレタンローラを得ることができる。Therefore, according to the present invention, the degree of conductivity and hardness can be arbitrarily designed, and the casting and demolding operations can be performed smoothly and easily, thereby producing a uniform polyurethane material having low hardness and conductivity at the same time. You can get rollers.
かくして得られる低硬度導電性ポリウレタンローラは、
加圧現像方式による電子写真複写機において、トナーを
現像域まで搬送するためのトナーローラとして好適に用
いることができる。The low hardness conductive polyurethane roller obtained in this way is
In an electrophotographic copying machine using a pressure development method, it can be suitably used as a toner roller for conveying toner to a development area.
実隻勇
以下に実施例を挙げて本発明を説明するが、本発明はこ
れら実施例により何ら限定されるものではない。EXAMPLES The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples in any way.
実施例１
ポリオールとして、ジエチレングリコールとトリメチロ
ールプロパンとアジピン酸との縮重合エステルである低
分岐ポリオール（日本ポリウレタン工業■製ニツボラン
Ｎ−４０３２、平均官能基数２．１５、水酸基価６０）
を用いた。Example 1 As a polyol, a low branched polyol which is a polycondensation ester of diethylene glycol, trimethylolpropane, and adipic acid (Nituboran N-4032 manufactured by Nippon Polyurethane Industries, average functional group number 2.15, hydroxyl value 60)
was used.
このポリオール１００重量部を４０℃に加熱し、これに
ケッチエンブラック１ｌｉ１部を加え、混合機で予備混
合した後、室温で２日間養生した。次いで、この混合物
を７０〜８０℃に加熱して、ペイントロールにて混練し
て、ケッチエンブラックをポリオール中に分散させた。100 parts by weight of this polyol was heated to 40° C., 1 part of Ketchen Black 1li was added thereto, premixed with a mixer, and then cured at room temperature for 2 days. Next, this mixture was heated to 70 to 80°C and kneaded with a paint roll to disperse Ketchien black in the polyol.
このようにして得られたポリオール組成物は、１００℃
において３０００ｃｐｓの粘度を有した。The polyol composition thus obtained was heated to 100°C.
It had a viscosity of 3000 cps.
次いで、このポリオール組成物を１４０℃に加熱し、ｌ
Ｏ〜２０ｓ＋Ｈｇの減圧下に攪拌して脱水乾燥させた。This polyol composition was then heated to 140°C and l
The mixture was dehydrated and dried by stirring under a reduced pressure of 0 to 20 s+Hg.
これを１１Ｏ〜１２０°Ｃに温度調整し、前記ポリオー
ル１００重量部に対して、２．４−トルエンジイソシア
ネートと２．６−トルエンジイソシアネートの混合物（
混合重量比８０／２０、ＴＤｒ−８０）７重量部を加え
、２分間激しく攪拌した後、１１０℃に加熱した金型に
注型し、２時間硬化させた後、１１０℃で２４時間、二
次架橋させて、低硬度導電性ポリウレタンローラを得た
。The temperature of this was adjusted to 110 to 120°C, and a mixture of 2.4-toluene diisocyanate and 2.6-toluene diisocyanate (
Mixing weight ratio 80/20, 7 parts by weight of TDr-80) was added, stirred vigorously for 2 minutes, poured into a mold heated to 110°C, cured for 2 hours, and then heated at 110°C for 24 hours. Next, crosslinking was performed to obtain a low hardness conductive polyurethane roller.
実施例２
実施例１において、ポリオール１００重量部に対して、
ＴＤＩ−８０を６．５重量部用いた以外は、実施例１と
同様にして、低硬度導電性ポリウレタンローラを得た。Example 2 In Example 1, with respect to 100 parts by weight of polyol,
A low hardness conductive polyurethane roller was obtained in the same manner as in Example 1 except that 6.5 parts by weight of TDI-80 was used.
実施例３
実施例１において、ポリオール１００重量部に対して、
ＴＤＩ−８０を８．５重量部用いた以外は、実施例１と
同様にして、低硬度導電性ポリウレタンローラを得た。Example 3 In Example 1, with respect to 100 parts by weight of polyol,
A low hardness conductive polyurethane roller was obtained in the same manner as in Example 1 except that 8.5 parts by weight of TDI-80 was used.
実施例４
実施例１において、ポリオール１００重量部に対して、
ケッチエンブラック２重量部を用いた以外は、実施例１
と同様にして、ポリオール組成物を調製した。このポリ
オール組成物は、１００″Ｃにおいて、４０００ｃｐｓ
の粘度を有した。Example 4 In Example 1, with respect to 100 parts by weight of polyol,
Example 1 except that 2 parts by weight of Ketchen Black was used.
A polyol composition was prepared in the same manner. This polyol composition produced 4000 cps at 100"C.
It had a viscosity of
次いで、ポリオール１００重量部に対して、ＴＤＩ−８
０を７．０重量部用いた以外は、実施例１と同様にして
、低硬度導電性ポリウレタンローラを得た。Next, TDI-8 was added to 100 parts by weight of the polyol.
A low hardness conductive polyurethane roller was obtained in the same manner as in Example 1 except that 7.0 parts by weight of 0 was used.
比較例１
ニラポランＮ−４０３２を５ｍｍＨｇの減圧下に７０°
Ｃで３時間、脱水乾燥させた後、このポリオール１００
重量部に対して、ＴＤＩ−８０を１４重量部加え（ＮＣ
Ｏ１０Ｈモル比２．０ ） 、ガラス製フラスコ内で窒
素雰囲気下に８０°Ｃで４時間反応させて、プレポリマ
ーを得た。このプレポリマーのイソシアネート量は３．
５８％、１００°Ｃにおける粘度は３９００ｃｐｓであ
った。Comparative Example 1 Niraporan N-4032 was heated at 70° under a reduced pressure of 5 mmHg.
After dehydrating and drying at C for 3 hours, this polyol 100
Add 14 parts by weight of TDI-80 to the parts by weight (NC
O10H molar ratio 2.0) was reacted in a glass flask under a nitrogen atmosphere at 80°C for 4 hours to obtain a prepolymer. The amount of isocyanate in this prepolymer is 3.
The viscosity at 58% and 100°C was 3900 cps.
前記ポリオール１００重量部に対して、ケッチエンブラ
ック２重量部を加え、引続き攪拌したところ、プレポリ
マーの粘度は１００°Ｃで１０００Ｑ ｃｐｓに達した
。更に、フラスコ内を減圧にして、プレポリマーを十分
に脱泡した後、これに十分に脱水した前記ポリオール１
００重量部を更に加えて、２〜３分間激しく撹拌混合し
、実施例１と同様にしてローラを得た。When 2 parts by weight of Ketchien Black was added to 100 parts by weight of the polyol and the mixture was continuously stirred, the viscosity of the prepolymer reached 1000 Q cps at 100°C. Furthermore, the pressure inside the flask was reduced to sufficiently degas the prepolymer, and then the polyol 1, which had been sufficiently dehydrated, was added to the prepolymer.
00 parts by weight was further added and mixed with vigorous stirring for 2 to 3 minutes, and a roller was obtained in the same manner as in Example 1.
但し、本比較例においては、プレポリマーが高粘度であ
るため、金型内に十分流れなかった。However, in this comparative example, since the prepolymer had a high viscosity, it did not flow sufficiently into the mold.
比較例２
実施例１と同じ低分岐ポリオール１００重・置部を４０
℃に加熱し、これにケッチエンブラック１重量部を加え
、混合機で予備混合した後、室温で２日間養生し、更に
、この混合物を７０〜８０°Ｃに加熱して、ペイントロ
ールにて混練して、ケッチエンブラックをポリオール中
に分散させた。Comparative Example 2 The same low branched polyol as in Example 1, 100 layers, 40
℃, 1 part by weight of Ketschen Black was added thereto, premixed with a mixer, cured at room temperature for 2 days, further heated to 70-80℃, and mixed with a paint roll. The Ketchien black was dispersed in the polyol by kneading.
次いで、このポリオール組成物を１４０°Ｃに加熱し、
ｌＯ〜２０＋ｓＨｇの減圧下に１２時間脱水乾燥させた
。このポリオール１００重量部に対して、ＴＤＩ−８０
を１４重量部加え（ＮＧＯ１０Ｈモル比２．０ ） 、
ガラス製フラスコ内で窒素雰囲気下に８０°Ｃで４時間
反応させて、プレポリマーを得た。このプレポリマーの
１００℃における粘度は１３０００ｃｐｓであった。This polyol composition was then heated to 140°C,
It was dehydrated and dried for 12 hours under a reduced pressure of lO~20+sHg. For 100 parts by weight of this polyol, TDI-80
Add 14 parts by weight of (NGO10H molar ratio 2.0),
A prepolymer was obtained by reacting in a glass flask at 80° C. for 4 hours under a nitrogen atmosphere. The viscosity of this prepolymer at 100°C was 13,000 cps.
このプレポリマーを十分に脱泡した後、これに十分に脱
水したポリエステルポリオール１００重量部を加えて、
２〜３分間激しく攪拌混合し、実施例１と同様にしてロ
ーラを得た。After sufficiently degassing this prepolymer, 100 parts by weight of a sufficiently dehydrated polyester polyol was added thereto.
The mixture was vigorously stirred and mixed for 2 to 3 minutes, and a roller was obtained in the same manner as in Example 1.
但し、本比較例においては、プレポリマーが高粘度であ
るため、金型内に十分流れなかった。However, in this comparative example, since the prepolymer had a high viscosity, it did not flow sufficiently into the mold.
比較例３
実施例１と同じ低分岐ポリオール１００重量部を７０℃
で３時間、減圧乾燥した後、これにＴＤＩ８０の１４重
量部（ＮＧＯ１０Ｈ当量比２．０）を加え、窒素雰囲気
中で８０°Ｃで４時間反応させてプレポリマーを得た。Comparative Example 3 100 parts by weight of the same low branched polyol as in Example 1 was heated at 70°C.
After drying under reduced pressure for 3 hours, 14 parts by weight of TDI80 (NGO10H equivalent ratio 2.0) was added thereto, and the mixture was reacted at 80°C for 4 hours in a nitrogen atmosphere to obtain a prepolymer.
このプレポリマーにおけるイソシアネート基量は３．５
５％であり、その粘度は１００℃で３９３０ｃｐｓであ
った。The amount of isocyanate groups in this prepolymer is 3.5
5%, and its viscosity was 3930 cps at 100°C.
このプレポリマーを１００℃で１時間減圧脱泡した後、
これに実施例１で得たポリオール組成物を１００重量部
加え、２〜３分間激しく攪拌混合して、粘度の非常に高
い混合物を得た。これを実施例１と同様に金型に注型し
て、ローラを得た。After degassing this prepolymer under reduced pressure at 100°C for 1 hour,
100 parts by weight of the polyol composition obtained in Example 1 was added to this and mixed with vigorous stirring for 2 to 3 minutes to obtain a mixture with very high viscosity. This was cast into a mold in the same manner as in Example 1 to obtain a roller.
比較例４
実施例１と同様にして、ケッチエンブラックをポリオー
ル１００重量部に対して１重量部混合し、次いで、上記
ポリオール１００重量部に対して、４．４°−ジフェニ
ルメタンジイソシアネー） （ＭＤＩ）１０．０重量部
を上記ポリオールとケッチエンブラックとかなる組成物
を加え、実施例１と同様にして、１１０°Ｃの金型に注
型した。Comparative Example 4 In the same manner as in Example 1, 1 part by weight of Ketchien Black was mixed with 100 parts by weight of the polyol, and then 4.4°-diphenylmethane diisocyanate (4.4°-diphenylmethane diisocyanate) was mixed with 100 parts by weight of the polyol. 10.0 parts by weight of MDI) was added to a composition consisting of the above polyol and Ketschen black, and cast into a mold at 110°C in the same manner as in Example 1.
しかし、２時間後及び４時間後のいずれにおいても、完
全に硬化せず、脱型が困難であったので、２６時間後に
型から取出した。二次架橋は行なわなかった。However, it was not completely cured either after 2 hours or after 4 hours, and it was difficult to remove it from the mold, so it was removed from the mold after 26 hours. No secondary crosslinking was performed.
以上のようにして得られたそれぞれのローラの硬さ及び
体積固有抵抗を第１表に示す。Table 1 shows the hardness and volume resistivity of each roller obtained as described above.
Claims (3)
ポリオールに予め導電性材料を混合し、このポリオール
をワン・ショット方式にてポリイソシアネートと反応さ
せることを特徴とする低硬度導電性ポリウレタンローラ
の製造方法。(1) Low hardness characterized by mixing a conductive material in advance with a polyol having an average functional group number of more than 2.0 and less than 3.0, and reacting this polyol with polyisocyanate in a one-shot method. Method for manufacturing conductive polyurethane rollers.
する請求項第１項記載の低硬度導電性ポリウレタンロー
ラの製造方法。(2) The method for manufacturing a low hardness conductive polyurethane roller according to claim 1, wherein the conductive material is conductive carbon.
は水素又はアルキル基を示す。） で表わされることを特徴とする請求項第１項記載の低硬
度導電性ポリウレタンローラの製造方法。(3) Polyisocyanate has the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R represents a carbon-carbon bond or an alkylene group, and R'
represents hydrogen or an alkyl group. ) The method for manufacturing a low hardness conductive polyurethane roller according to claim 1, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1327794A JPH0645205B2 (en) | 1989-12-18 | 1989-12-18 | Method for manufacturing low-hardness conductive polyurethane roller |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1327794A JPH0645205B2 (en) | 1989-12-18 | 1989-12-18 | Method for manufacturing low-hardness conductive polyurethane roller |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03187732A true JPH03187732A (en) | 1991-08-15 |
| JPH0645205B2 JPH0645205B2 (en) | 1994-06-15 |
Family
ID=18203066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1327794A Expired - Fee Related JPH0645205B2 (en) | 1989-12-18 | 1989-12-18 | Method for manufacturing low-hardness conductive polyurethane roller |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0645205B2 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0753860A (en) * | 1993-08-18 | 1995-02-28 | Bridgestone Corp | Conductive substrate |
| JPH07261542A (en) * | 1993-03-29 | 1995-10-13 | Bridgestone Corp | Developing roller and developing device |
| JPH08157556A (en) * | 1994-12-01 | 1996-06-18 | Bridgestone Corp | Polyurethane member |
| US6142922A (en) * | 1997-11-11 | 2000-11-07 | Tokai Rubber Industries, Ltd. | Conductive roller |
| JP2013213142A (en) * | 2012-04-02 | 2013-10-17 | Bando Chemical Industries Ltd | Conductive roller and method of producing the same |
-
1989
- 1989-12-18 JP JP1327794A patent/JPH0645205B2/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07261542A (en) * | 1993-03-29 | 1995-10-13 | Bridgestone Corp | Developing roller and developing device |
| JPH0753860A (en) * | 1993-08-18 | 1995-02-28 | Bridgestone Corp | Conductive substrate |
| JPH08157556A (en) * | 1994-12-01 | 1996-06-18 | Bridgestone Corp | Polyurethane member |
| US6142922A (en) * | 1997-11-11 | 2000-11-07 | Tokai Rubber Industries, Ltd. | Conductive roller |
| JP2013213142A (en) * | 2012-04-02 | 2013-10-17 | Bando Chemical Industries Ltd | Conductive roller and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0645205B2 (en) | 1994-06-15 |
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