JP2020187263A - Seamless belt with carrier layer, manufacturing method of the same and manufacturing method of transfer belt with elastic layer for image formation apparatus - Google Patents
Seamless belt with carrier layer, manufacturing method of the same and manufacturing method of transfer belt with elastic layer for image formation apparatus Download PDFInfo
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- JP2020187263A JP2020187263A JP2019091883A JP2019091883A JP2020187263A JP 2020187263 A JP2020187263 A JP 2020187263A JP 2019091883 A JP2019091883 A JP 2019091883A JP 2019091883 A JP2019091883 A JP 2019091883A JP 2020187263 A JP2020187263 A JP 2020187263A
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- elastic layer
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- 238000012546 transfer Methods 0.000 title claims abstract description 66
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
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- 238000003618 dip coating Methods 0.000 description 2
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- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
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- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 description 2
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- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- ZYIPKNMNGBFPRA-UHFFFAOYSA-N 2-[2-(oxiran-2-yl)ethylidene]butanedioic acid Chemical compound OC(=O)CC(C(O)=O)=CCC1CO1 ZYIPKNMNGBFPRA-UHFFFAOYSA-N 0.000 description 1
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- 125000003504 2-oxazolinyl group Chemical group O1C(=NCC1)* 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- XRMBQHTWUBGQDN-UHFFFAOYSA-N [2-[2,2-bis(prop-2-enoyloxymethyl)butoxymethyl]-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(CC)COCC(CC)(COC(=O)C=C)COC(=O)C=C XRMBQHTWUBGQDN-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229920006020 amorphous polyamide Polymers 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
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- 238000005520 cutting process Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- ZJZXSOKJEJFHCP-UHFFFAOYSA-M lithium;thiocyanate Chemical compound [Li+].[S-]C#N ZJZXSOKJEJFHCP-UHFFFAOYSA-M 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003866 tertiary ammonium salts Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Electrophotography Configuration And Component (AREA)
- Electrostatic Charge, Transfer And Separation In Electrography (AREA)
- Laminated Bodies (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Abstract
Description
本発明は、電子写真方式の画像形成装置に用いられる電子写真感光体から一次転写されたトナー像を表面に担持し、紙等の転写媒体への二次転写領域まで搬送するための中間転写ベルトやトナー像が転写される紙などの転写媒体を表面に担持して搬送するための転写搬送ベルトなどの転写ベルトの製造に使用するキャリア層付きシームレスベルトに関する。 The present invention is an intermediate transfer belt for carrying a toner image primaryly transferred from an electrophotographic photosensitive member used in an electrophotographic image forming apparatus on a surface and transporting the toner image to a secondary transfer region to a transfer medium such as paper. The present invention relates to a seamless belt with a carrier layer used for manufacturing a transfer belt such as a transfer transport belt for carrying a transfer medium such as paper on which a toner image is transferred by supporting it on a surface.
従来、電子写真方式のプリンター、複写機、ファクシミリ等の画像形成装置にはシームレスベルトが使用されている。シームレスベルトとしては、中抵抗領域の導電性を付与した合成樹脂を筒状に成形したものが知られている。最近では、トナーの抜けなどのない鮮明な画像を得るために、基材層の上に弾性層を配したシームレスベルトが提案されている。 Conventionally, seamless belts have been used in image forming devices such as electrophotographic printers, copiers, and facsimiles. As a seamless belt, a belt obtained by molding a synthetic resin having conductivity in a medium resistance region into a tubular shape is known. Recently, a seamless belt in which an elastic layer is arranged on a base material layer has been proposed in order to obtain a clear image without toner loss.
例えば、特許文献１には、ポリイミドまたはポリアミドイミド製の基材を遠心成形法で作製し、その上に溶剤に溶かしたゴム系弾性層をコートすることにより形成した弾性層を有するシームレスベルトの製造方法が記載されている。特許文献２には、遠心成形法で製造したポリイミド製の基材上へポリウレタンの原料であるイソシアネート化合物とジオール化合物との混合物をコートすることにより形成した弾性層を有するシームレスベルトの製造方法が記載されている。特許文献３には、基材を形成する樹脂の溶液を金型の外周面上に塗布・乾燥・イミド化した後、弾性層を形成するゴム弾性層形成材料を塗布・乾燥後架橋することにより形成した弾性層を有するシームレスベルトの製造方法が記載されている。これらの特許文献記載の製造方法は、遠心成形法で作製した基材上へ弾性層形成用材料を塗布する方法で製造されているため、製造工程が少なくとも２工程必要となり、製造方法が煩雑かつコスト面に課題がある。 For example, in Patent Document 1, a seamless belt having an elastic layer formed by producing a base material made of polyimide or polyamide-imide by a centrifugal molding method and coating a rubber-based elastic layer dissolved in a solvent on the substrate is manufactured. The method is described. Patent Document 2 describes a method for producing a seamless belt having an elastic layer formed by coating a mixture of an isocyanate compound and a diol compound, which are raw materials for polyurethane, on a polyimide base material produced by a centrifugal molding method. Has been done. In Patent Document 3, a solution of a resin forming a base material is applied, dried, and imidized on the outer peripheral surface of a mold, and then a rubber elastic layer forming material for forming an elastic layer is applied, dried, and then crosslinked. A method for manufacturing a seamless belt having the formed elastic layer is described. Since the manufacturing methods described in these patent documents are manufactured by applying a material for forming an elastic layer onto a base material manufactured by a centrifugal molding method, at least two manufacturing steps are required, and the manufacturing method is complicated. There is a problem in terms of cost.
また、特許文献４には、表面平滑性に優れた転写ベルトを得るために、共押出機を用いて基材層と表面層よりなる二層の円筒状のフィルムを成形した後、表面層を剥離して表面平滑性のよいフィルムを得る方法が記載されている。具体的には、基材層として非晶ポリアミド、カルボキシ変性ＮＢＲ、またはポリカーボネート、表面層にはポリエチレンやポリプロピレンが記載され、基材層と表面層を共押出した後、表面層を剥離することにより表面平滑性に優れた転写ベルトを得ている。 Further, in Patent Document 4, in order to obtain a transfer belt having excellent surface smoothness, a coextruder is used to form a two-layer cylindrical film composed of a base material layer and a surface layer, and then the surface layer is formed. A method of peeling to obtain a film having good surface smoothness is described. Specifically, amorphous polyamide, carboxy-modified NBR, or polycarbonate is described as the base material layer, and polyethylene or polypropylene is described as the surface layer. By coextruding the base material layer and the surface layer and then peeling off the surface layer. A transfer belt with excellent surface smoothness has been obtained.
特許文献５には、シームレスベルトと表面保護層との界面の平滑性が高いため、表面保護層を剥離した後コート層を塗布しても、下地のベルト表面に起因してベルト表面の光沢度が高くなる事が記載されている。ベルト上へのトナーの載り量はベルト表面の光沢度と光沢度ムラをセンサーで読み取り算出しているため、光沢度の高いベルトは長時間使用すると光沢度が低下し光沢度ムラが生じ、その制御が困難となる。ベルト表面の光沢度を下げるためには、コート層をベルト表面に塗布する際の塗布条件で調整可能であるが、僅かな塗布条件で光沢度が不均一になり易く、均一な所望の光沢度が得られにくいという問題があった。
このような課題に対し、特許文献５記載の発明は、シームレスベルトの表面に凹凸を形成する目的で、フィラーを配合した表面保護層を基材上に被せて加熱融着させ、基材表面に凹凸を形成させたシームレスベルトが記載されているが、表面保護層にフィラーを配合しなければならないという煩雑さがあった。
In Patent Document 5, since the interface between the seamless belt and the surface protective layer is highly smooth, even if the coat layer is applied after the surface protective layer is peeled off, the glossiness of the belt surface is caused by the underlying belt surface. It is stated that will be higher. Since the amount of toner on the belt is calculated by reading the glossiness and uneven glossiness of the belt surface with a sensor, if a belt with high glossiness is used for a long time, the glossiness will decrease and uneven glossiness will occur. It becomes difficult to control. In order to reduce the glossiness of the belt surface, the glossiness can be adjusted by the coating conditions when the coat layer is applied to the belt surface, but the glossiness tends to be non-uniform under a slight coating condition, and a uniform desired glossiness is obtained. There was a problem that it was difficult to obtain.
In response to such a problem, in the invention described in Patent Document 5, for the purpose of forming irregularities on the surface of the seamless belt, a surface protective layer containing a filler is placed on the base material and heat-fused to the surface of the base material. Although a seamless belt having irregularities is described, there is a complexity that a filler must be blended in the surface protective layer.
このような状況に鑑み、押出成形法で低硬度の弾性層を有するシームレスベルトを製造する方法を検討した結果、弾性層を形成する熱可塑性エラストマーは結晶化が遅く、冷却固化した後も表面タック性を有しているため、ダイスから吐出された樹脂チューブを引き取るピンチロール等に巻きつくという課題があった。さらにはベルト表面が平滑で光沢度が高い転写ベルトは長時間使用すると、光沢度が変化するという課題があった。 In view of this situation, as a result of investigating a method for producing a seamless belt having an elastic layer having a low hardness by an extrusion molding method, the thermoplastic elastomer forming the elastic layer is slow to crystallize and has a surface tack even after cooling and solidifying. Since it has a property, there is a problem that it is wound around a pinch roll or the like that takes over the resin tube discharged from the die. Further, a transfer belt having a smooth belt surface and a high glossiness has a problem that the glossiness changes when it is used for a long time.
本発明は、上述の課題に鑑みなされたものであり、基材層と弾性層とキャリア層を順に備えるキャリア層付きシームレスベルトの製造方法において、製膜時にフィルムがピンチロール等に巻きつかず、次工程でキャリア層を剥離・除去する作業が簡便であること、およびベルト表面の光沢度を低下させ、転写ベルトの使用に伴う光沢度変化を抑制することができるキャリア層付きシームレスベルト及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above-mentioned problems. In a method for manufacturing a seamless belt with a carrier layer, which includes a base material layer, an elastic layer, and a carrier layer in order, the film does not wrap around a pinch roll or the like during film formation. A seamless belt with a carrier layer and its manufacture that can easily peel off and remove the carrier layer in the next step, reduce the glossiness of the belt surface, and suppress the change in glossiness due to the use of the transfer belt. The purpose is to provide a method.
すなわち、本発明は、
（１）基材層と弾性層とキャリア層を順に備えるキャリア層付きシームレスベルトにおいて、
前記基材層は、熱可塑性樹脂を含有し、
前記弾性層は、ショアＡ硬度が８０以下のウレタン系エラストマーまたはアクリル系エラストマーを含有し、
前記キャリア層は、密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を含有し、かつ前記弾性層に含まれるウレタン系エラストマーまたはアクリル系エラストマーと前記キャリア層に含まれるポリエチレン系樹脂の２００℃、１００ｋｇｆにおける溶融粘度の差が１００００ｐｏｉｓｅ以下であることを特徴とするキャリア層付きシームレスベルト；
（２）前記弾性層は、導電性物質として高分子型のイオン伝導性材料を含有することを特徴とする（１）記載のキャリア層付きシームレスベルト；
（３）前記基材層は、導電性物質として高分子型のイオン伝導性材料を含有することを特徴とする（１）または（２）記載のキャリア層付きシームレスベルト；
（４）前記基材層は、導電性物質として電子伝導性材料を含有することを特徴とする（１）乃至（３）のいずれか記載のキャリア層付きシームレスベルト；
（５）熱可塑性樹脂と導電性物質を含有した引張弾性率が１０００ＭＰａ以上である基材層を形成する樹脂組成物と、ショアＡ硬度が８０以下のウレタン系エラストマーまたはアクリル系エラストマーと導電性物質とを含有した弾性層を形成する樹脂組成物と、密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を含有し、前記弾性層に含まれるウレタン系エラストマーまたはアクリル系エラストマーと前記キャリア層に含まれるポリエチレン系樹脂の２００℃、１００ｋｇｆにおける溶融粘度の差が１００００ｐｏｉｓｅ以下であるキャリア層を形成する樹脂組成物とを、別々の押出機に供給し、環状ダイスより共押出して、基材層、弾性層、キャリア層とを順に備えキャリア層が外側に位置するチューブ状に成形することを特徴とするキャリア層付きシームレスベルトの製造方法；
（６）基材層と弾性層と表面層を順に備える画像形成装置用弾性層付き転写ベルトの製造方法において、（１）乃至（４）のいずれか記載のキャリア層付きシームレスベルトの最外層であるキャリア層を剥離した後、前記弾性層表面の外側に、表面層形成用塗工液を塗布して活性エネルギー線もしくは熱で硬化させることにより表面層を形成することを特徴とする画像形成装置用弾性層付き転写ベルトの製造方法；
を要旨とするものである。
That is, the present invention
(1) In a seamless belt with a carrier layer having a base material layer, an elastic layer, and a carrier layer in this order.
The base material layer contains a thermoplastic resin and
The elastic layer contains a urethane-based elastomer or an acrylic-based elastomer having a shore A hardness of 80 or less.
The carrier layer contains a polyethylene resin having a density of 0.940 g / cm3 or more, and the urethane-based elastomer or acrylic elastomer contained in the elastic layer and the polyethylene-based resin contained in the carrier layer are at 200 ° C. and 100 kgf. Seamless belt with a carrier layer, characterized in that the difference in melt viscosity is 10000 polyethylene or less;
(2) The seamless belt with a carrier layer according to (1), wherein the elastic layer contains a polymer-type ionic conductive material as a conductive substance;
(3) The seamless belt with a carrier layer according to (1) or (2), wherein the base material layer contains a polymer-type ionic conductive material as a conductive substance;
(4) The seamless belt with a carrier layer according to any one of (1) to (3), wherein the base material layer contains an electron conductive material as a conductive substance;
(5) A resin composition containing a thermoplastic resin and a conductive substance to form a base material layer having a tensile elasticity of 1000 MPa or more, and a urethane-based elastomer or acrylic elastomer having a Shore A hardness of 80 or less and a conductive substance. A resin composition for forming an elastic layer containing the above, and a polyethylene-based resin having a density of 0.940 g / cm3 or more are contained, and the urethane-based elastomer or acrylic-based elastomer contained in the elastic layer and the carrier layer are contained. A resin composition for forming a carrier layer in which the difference in melt viscosity of a polyethylene resin at 200 ° C. and 100 kgf is 10,000 poise or less is supplied to separate extruders and co-extruded from an annular die to obtain a base material layer and an elastic layer. , A method for manufacturing a seamless belt with a carrier layer, which comprises forming a carrier layer in order and forming the carrier layer into a tubular shape located on the outside;
(6) In the method for manufacturing a transfer belt with an elastic layer for an image forming apparatus, which comprises a base material layer, an elastic layer, and a surface layer in this order, the outermost layer of the seamless belt with a carrier layer according to any one of (1) to (4). An image forming apparatus characterized in that a surface layer is formed by applying a coating liquid for forming a surface layer to the outside of the surface of the elastic layer after peeling off a certain carrier layer and curing the surface layer with active energy rays or heat. Method of manufacturing a transfer belt with an elastic layer for use;
Is the gist.
本発明は、基材層と弾性層とキャリア層を形成する樹脂組成物を、キャリア層が外側、基材層が内側に形成されるように別々の押出機に供給し、環状ダイスにより共押出してチューブ状に形成するキャリア層付きシームレスベルトおよびその製造方法であり、製膜時にフィルムがピンチロール等に巻きつくことがなく、キャリア層付きシームレスベルトを安価に製造することができる。さらに、シームレスベルトの表面に特定の表面粗さを付与することで、ベルト表面の光沢度を低下させ、転写ベルトの使用に伴う光沢度変化を抑制することができる。また、共押出されたキャリア層付きシームレスベルトのキャリア層を剥離して、弾性層上に表面層を設けることにより、トナーとの離型性を担保でき、転写ベルト表面へクリーニング性を付与して転写効率が良好な画像形成装置用の転写ベルトを製造することができる。 In the present invention, the resin composition forming the base material layer, the elastic layer and the carrier layer is supplied to separate extruders so that the carrier layer is formed on the outside and the base material layer is formed on the inside, and coextruded with an annular die. This is a seamless belt with a carrier layer formed in a tubular shape and a method for manufacturing the same. The film does not wrap around a pinch roll or the like during film formation, and the seamless belt with a carrier layer can be manufactured at low cost. Further, by imparting a specific surface roughness to the surface of the seamless belt, it is possible to reduce the glossiness of the belt surface and suppress the change in glossiness due to the use of the transfer belt. Further, by peeling off the carrier layer of the co-extruded seamless belt with a carrier layer and providing a surface layer on the elastic layer, releasability with toner can be ensured and cleaning property is imparted to the surface of the transfer belt. A transfer belt for an image forming apparatus having good transfer efficiency can be manufactured.
以下、本発明を実施するための形態について詳細に説明する。なお、本発明において「（メタ）アクリル」とは、アクリルおよび／またはメタクリルの意味で用いている。 Hereinafter, embodiments for carrying out the present invention will be described in detail. In the present invention, "(meth) acrylic" is used to mean acrylic and / or methacrylic.
［キャリア層付きシームレスベルト］
本発明のキャリア層付きシームレスベルトは、基材層と弾性層とキャリア層を順に備えた少なくとも３層構造のチューブ状のベルトである。基材層と弾性層とキャリア層を順に備えていれば良く、基材層、弾性層が多層構成、基材層と弾性層との間に樹脂層、基材層の弾性層と接する側の反対側の表面に樹脂層を形成してもよい。キャリア層付きシームレスベルトは、それ自体で電子写真方式のプリンター、複写機、ファクシミリ等の画像形成装置に組み込まれるものではなく、後述する電子写真方式のプリンター、複写機、ファクシミリ等の画像形成装置に組み込む転写ベルトを製造する上で必要となる半製品のことである。
[Seamless belt with carrier layer]
The seamless belt with a carrier layer of the present invention is a tubular belt having at least a three-layer structure including a base material layer, an elastic layer, and a carrier layer in this order. It suffices to provide the base material layer, the elastic layer, and the carrier layer in this order, and the base material layer and the elastic layer have a multi-layer structure, and the resin layer between the base material layer and the elastic layer and the side in contact with the elastic layer of the base material layer. A resin layer may be formed on the opposite surface. The seamless belt with a carrier layer is not incorporated into an image forming apparatus such as an electrophotographic printer, a copier, or a facsimile by itself, but is incorporated into an image forming apparatus such as an electrophotographic printer, a copier, or a facsimile described later. It is a semi-finished product required to manufacture a transfer belt to be incorporated.
［弾性層付き転写ベルト］
本発明の弾性層付き転写ベルトは、前述したキャリア層付きシームレスベルトの最表面側に位置するキャリア層を剥離し、弾性層の表面に表面層形成用塗布液を塗布して活性エネルギー線硬化もしくは熱硬化により表面層を形成することにより製造される。従って、本発明の弾性層付き転写ベルトは、基材層、弾性層、表面層を順に備えた少なくとも３層のチューブ状のシームレスベルトであり、電子写真方式のプリンター、複写機、ファクシミリ等の画像形成装置に組み込まれて、中間転写ベルトや転写搬送ベルトとして使用される。
[Transfer belt with elastic layer]
In the transfer belt with an elastic layer of the present invention, the carrier layer located on the outermost surface side of the seamless belt with a carrier layer described above is peeled off, and a coating liquid for forming a surface layer is applied to the surface of the elastic layer to cure active energy rays. Manufactured by forming a surface layer by thermosetting. Therefore, the transfer belt with an elastic layer of the present invention is a tubular seamless belt having at least three layers including a base material layer, an elastic layer, and a surface layer in this order, and is an image of an electrophotographic printer, a copying machine, a facsimile, or the like. It is incorporated into a forming device and used as an intermediate transfer belt or a transfer transfer belt.
［基材層］
本発明の基材層は、熱可塑性樹脂を含有していることが必須であり、基材層を形成する成分の主成分が熱可塑性樹脂からなることが好ましい。ここでいう主成分とは、基材層を形成する成分の内、全量の７０重量％以上を占める成分を指す。なお、これらの熱可塑性樹脂は、必要に応じて単独或は２種以上を混合使用してもよい。
画像形成装置用の転写ベルトとして使用するためには、プリンター等の高速化に対応して、転写ベルト駆動時に転写ベルトが伸びて、転写位置がずれないように比較的高い引張弾性率が要求されており、基材層の引張弾性率は１０００ＭＰａ以上であることが好ましい。基材層に用いられる樹脂としては特に制限はないが、引張弾性率が１０００ＭＰａ以上である材料としては、例えば、フッ素系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミドイミド系樹脂、ポリイミド系樹脂などを挙げることができ、これらを単独で、または２種以上の材料をブレンドして用いても良く、更には、多層にして用いてもよい。特に、押出加工の観点からフッ素系樹脂、ポリアミド系樹脂、またはフッ素系樹脂とポリアミド樹脂のブレンドした材料が好ましい。
[Base layer]
It is essential that the base material layer of the present invention contains a thermoplastic resin, and it is preferable that the main component of the component forming the base material layer is a thermoplastic resin. The main component referred to here refers to a component that accounts for 70% by weight or more of the total amount of the components that form the base material layer. In addition, these thermoplastic resins may be used individually or in mixture of 2 or more types as needed.
In order to use it as a transfer belt for an image forming apparatus, a relatively high tensile elastic modulus is required so that the transfer belt stretches when the transfer belt is driven and the transfer position does not shift in response to the increase in speed of a printer or the like. The tensile elastic modulus of the base material layer is preferably 1000 MPa or more. The resin used for the base material layer is not particularly limited, and examples of the material having a tensile elasticity of 1000 MPa or more include a fluorine-based resin, a polyamide-based resin, a polyester-based resin, a polycarbonate-based resin, and a polyamide-imide-based resin. Polyamide-based resins and the like can be mentioned, and these may be used alone or in a blend of two or more kinds of materials, or may be used in multiple layers. In particular, from the viewpoint of extrusion processing, a fluorine-based resin, a polyamide-based resin, or a material obtained by blending a fluorine-based resin and a polyamide resin is preferable.
これらの中で、フッ素系樹脂は、他の樹脂とは異なりそれ自身が難燃性を有し、且つ押出し成形が容易であり、画像形成装置に用いられる転写ベルトの基材に好適である。このようなフッ素系樹脂としては、ポリフッ化ビニリデン、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体、エチレン−テトラフルオロエチレン共重合体、ポリヘキサフルオロプロピレン、エチレン−フッ化ビニリデン共重合体、フッ化ビニリデン−テトラフルオロエチレン共重合体、フッ化ビニリデン−ヘキサフルオロプロピレン−テトラフルオロエチレン共重合体などが挙げられる。なお、これらのフッ素系樹脂は、単独或は２種以上を混合使用してもよい。 Among these, the fluororesin, unlike other resins, has flame retardancy by itself and is easy to extrude, and is suitable as a base material for a transfer belt used in an image forming apparatus. Examples of such fluororesins include polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, polyhexafluoropropylene, ethylene-vinylidene fluoride copolymer, and vinylidene fluoride. -Tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene copolymer and the like can be mentioned. In addition, these fluorine-based resins may be used individually or in combination of 2 or more types.
ポリアミド系樹脂は、ジアミンとジカルボン酸との重縮合、α,ω−アミノカルボン酸の重縮合、ラクタム類の開環重合などによって得られ、十分な分子量を有する熱可塑性樹脂である。ポリアミド樹脂としては、例えば、ナイロン６、ナイロン４、ナイロン６，６、ナイロン１１、ナイロン１２、ナイロン６，１０、ナイロン６，１２、ナイロン６／６，６、ナイロン６／６，６／１２、ナイロン６，ＭＸＤ（ＭＸＤはｍ−キシリレンジアミン成分を表す）、ナイロン６，６Ｔ（Ｔはテレフタル酸成分を表す）、ナイロン６，６Ｉ（Ｉはイソフタル酸成分を表す）などが挙げられる。これらの中でも、吸水率が低いポリアミド樹脂が好ましく、吸水率が低いポリアミド樹脂は、湿潤環境における電気抵抗の安定性に優れる。ポリアミド樹脂の吸水率は、１．５％以下であることが好ましく、１．０％以下であることがより好ましい。吸水率が１．５％以下のポリアミド樹脂としては、ナイロン１１、ナイロン１２、ナイロン６，１０、ナイロン６，１２などが挙げられ、吸水率が１．０％以下のポリアミド樹脂としては、ナイロン１１、ナイロン１２が挙げられる。なお、これらのポリアミドは、単独或は２種以上を組み合わせて用いても良い。 The polyamide-based resin is a thermoplastic resin obtained by polycondensation of diamine and dicarboxylic acid, polycondensation of α, ω-aminocarboxylic acid, ring-opening polymerization of lactams, and the like, and has a sufficient molecular weight. Examples of the polyamide resin include nylon 6, nylon 4, nylon 6, 6, nylon 11, nylon 12, nylon 6,10, nylon 6,12, nylon 6/6, 6, nylon 6/6/6/12, and the like. Nylon 6, MXD (MXD represents the m-xylylene diamine component), nylon 6,6T (T represents the terephthalic acid component), nylon 6,6I (I represents the isophthalic acid component) and the like. Among these, a polyamide resin having a low water absorption rate is preferable, and a polyamide resin having a low water absorption rate is excellent in stability of electrical resistance in a wet environment. The water absorption rate of the polyamide resin is preferably 1.5% or less, more preferably 1.0% or less. Examples of the polyamide resin having a water absorption rate of 1.5% or less include nylon 11, nylon 12, nylon 6,10, and nylon 6,12, and examples of the polyamide resin having a water absorption rate of 1.0% or less include nylon 11. , Nylon 12 and the like. In addition, these polyamides may be used alone or in combination of 2 or more types.
基材層の引張弾性率を上げるために、平板状フィラー、ウィスカー等の補強材を添加することもできる。また、基材層の厚みは、上記性能を満たすように５０〜３００μｍが好ましく、７５〜２００μｍがより好ましい。 In order to increase the tensile elastic modulus of the base material layer, a reinforcing material such as a flat plate filler or whiskers can be added. The thickness of the base material layer is preferably 50 to 300 μm, more preferably 75 to 200 μm so as to satisfy the above performance.
［弾性層］
本発明の弾性層は、ショアＡ硬度が８０以下である樹脂であることが必要である。これら弾性層に用いられるエラストマーは、ショアＡ硬度が７０以下のものが好ましく、ショアＡ硬度が６０以下のものがさらに好ましい。弾性層のショアＡ硬度が高すぎる場合は、厚さ方向の圧縮弾性率が高いため、トナー転写時にトナーへかかる圧力が高くなって転写効率が悪くなり、その結果弾性層を形成させた効果が小さくなる。
[Elastic layer]
The elastic layer of the present invention needs to be a resin having a shore A hardness of 80 or less. The elastomer used for these elastic layers preferably has a shore A hardness of 70 or less, and more preferably has a shore A hardness of 60 or less. If the shore A hardness of the elastic layer is too high, the compressive elastic modulus in the thickness direction is high, so that the pressure applied to the toner during toner transfer increases and the transfer efficiency deteriorates, resulting in the effect of forming the elastic layer. It becomes smaller.
本発明の弾性層は、さらに、キャリア層との相性から、ウレタン系エラストマーまたはアクリル系エラストマーを含有することが特徴である。弾性層の機能を付与するため、ショアＡ硬度が８０以下のウレタン系エラストマーまたはアクリル系エラストマーを主成分とすることが好ましい。ここで、主成分とは、弾性層を形成する成分のうち、全量の７０重量％以上を占める成分を指す。なお、これらの熱可塑性エラストマーは、必要に応じて単独或は２種以上を混合使用してもよい。さらに、イオン導電剤で抵抗を制御しやすいウレタン系エラストマーがより好ましい。 The elastic layer of the present invention is further characterized by containing a urethane-based elastomer or an acrylic-based elastomer from the viewpoint of compatibility with the carrier layer. In order to impart the function of the elastic layer, it is preferable to use a urethane-based elastomer or an acrylic-based elastomer having a shore A hardness of 80 or less as a main component. Here, the main component refers to a component that occupies 70% by weight or more of the total amount of the components forming the elastic layer. As for these thermoplastic elastomers, they may be used alone or in combination of two or more, if necessary. Further, a urethane-based elastomer whose resistance can be easily controlled by an ionic conductive agent is more preferable.
ショアＡ硬度が８０以下である熱可塑性エラストマーにはスチレン系エラストマーがあるが、様々なキャリア層を検討したにもかかわらず、スチレン系エラストマーとキャリア層との剥離強度が非常に高く、キャリア層付きシームレスベルトとした場合、キャリア層の剥離性が良好ではなかった。 Thermoplastic elastomers with a shore A hardness of 80 or less include styrene-based elastomers, but despite the examination of various carrier layers, the peel strength between the styrene-based elastomer and the carrier layer is extremely high, and a carrier layer is attached. When the seamless belt was used, the peelability of the carrier layer was not good.
弾性層の厚みは、柔軟性を付与するために８０μｍ〜６００μｍが好ましく、さらに２００μｍ〜５００μｍが好ましい。 The thickness of the elastic layer is preferably 80 μm to 600 μm, more preferably 200 μm to 500 μm in order to impart flexibility.
［キャリア層］
本発明のキャリア層は、弾性層との剥離性及びキャリア層を剥離した弾性層の表面粗さの観点から、密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を含有することが特徴であり、密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を主成分とすることが好ましい。ここで、主成分とは、キャリア層を形成する成分のうち、全量の７０重量％以上を占める成分を指す。なお、これらの樹脂は、必要に応じて単独或は２種以上を混合使用してもよい。本発明では密度が０．９４０ｇ／ｃｍ３以上のポリエチレンを用いる事により、キャリア層にフィラー等を配合せずに弾性層表面へ特定の表面粗さを付与することができる。 また、本発明は、弾性層に含まれるウレタン系エラストマーまたはアクリル系エラストマーとキャリア層に含まれるポリエチレン系樹脂との溶融粘度の差が１００００ｐｏｉｓｅ以下であることが特徴であり、弾性層とキャリア層を形成する樹脂との溶融粘度の差を特定の範囲に調整することで、キャリア層を剥離した弾性層の表面に適度な凹凸を付与することが可能となる。表面の凹凸は、中心線平均粗さＲａで表すことが可能であり、転写ベルトの表面の光沢度を低下させるためには、中心線平均表面粗さＲａは０．１３以上が好ましく、０．１４以上がより好ましい。
[Career layer]
The carrier layer of the present invention is characterized by containing a polyethylene resin having a density of 0.940 g / cm 3 or more from the viewpoint of releasability from the elastic layer and surface roughness of the elastic layer from which the carrier layer has been peeled off. It is preferable that the main component is a polyethylene resin having a density of 0.940 g / cm 3 or more. Here, the main component refers to a component that occupies 70% by weight or more of the total amount of the components forming the carrier layer. It should be noted that these resins may be used alone or in combination of two or more, if necessary. In the present invention, by using polyethylene having a density of 0.940 g / cm 3 or more, it is possible to impart a specific surface roughness to the surface of the elastic layer without adding a filler or the like to the carrier layer. Further, the present invention is characterized in that the difference in melt viscosity between the urethane-based elastomer or acrylic-based elastomer contained in the elastic layer and the polyethylene-based resin contained in the carrier layer is 10,000 poise or less, and the elastic layer and the carrier layer are formed. By adjusting the difference in melt viscosity with the resin to be formed within a specific range, it is possible to impart appropriate unevenness to the surface of the elastic layer from which the carrier layer has been peeled off. The unevenness of the surface can be represented by the center line average roughness Ra, and in order to reduce the glossiness of the surface of the transfer belt, the center line average surface roughness Ra is preferably 0.13 or more, and 0. 14 or more is more preferable.
一方、本願発明のシームレスベルトを中間転写ベルトとして使用する場合、感光体から中間転写ベルトへトナーが転写され、そのトナーを再び紙などに転写し、ベルト上に残ったトナーはクリーニングブレードやブラシでクリーニングされるが、その際、中間転写ベルト表面の凹凸が大きいとクリーニング不良が発生する。このような観点から、転写ベルトの表面粗さは中心線平均粗さＲａで０．４μｍ以下が好ましい。
また、キャリア層付きシームレスベルトから画像形成装置に組み込む転写ベルトを製造するためには、弾性層とキャリア層の界面でキャリア層のみを剥離する必要がある。つまり、弾性層とキャリア層との間の剥離強度の値が小さい必要があり、弾性層とキャリア層の間の剥離強度が１００ｇ／１０ｍｍ幅以下が好ましく、特に後加工において剥離する観点から５０ｇ／１０ｍｍ幅以下がより好ましい。このような観点から、ポリエチレン系樹脂は、安価で弾性層と共押出した場合でも容易に剥離できるためキャリア層として好ましい。
On the other hand, when the seamless belt of the present invention is used as an intermediate transfer belt, toner is transferred from the photoconductor to the intermediate transfer belt, the toner is transferred to paper or the like again, and the toner remaining on the belt is removed by a cleaning blade or a brush. It is cleaned, but at that time, if the surface of the intermediate transfer belt is uneven, cleaning failure occurs. From this point of view, the surface roughness of the transfer belt is preferably 0.4 μm or less in terms of the center line average roughness Ra.
Further, in order to manufacture a transfer belt to be incorporated into an image forming apparatus from a seamless belt with a carrier layer, it is necessary to peel off only the carrier layer at the interface between the elastic layer and the carrier layer. That is, the value of the peel strength between the elastic layer and the carrier layer needs to be small, and the peel strength between the elastic layer and the carrier layer is preferably 100 g / 10 mm width or less, and particularly from the viewpoint of peeling in post-processing, 50 g /. A width of 10 mm or less is more preferable. From this point of view, the polyethylene resin is preferable as a carrier layer because it is inexpensive and can be easily peeled off even when coextruded with the elastic layer.
［転写ベルトの表面層］
転写効率の優れた転写ベルトは、弾性層表面に形成されたキャリア層を剥離し、弾性層の上に表面層を形成することにより得られ、画像形成装置用弾性層付き転写ベルトとして利用可能である。表面層は、トナーとの離型性やクリーニング性を有し、弾性層と強固に接着し、弾性層の柔らかさを阻害せずクラックの発生しない特性が求められる。
[Surface layer of transfer belt]
A transfer belt having excellent transfer efficiency can be obtained by peeling off the carrier layer formed on the surface of the elastic layer and forming a surface layer on the elastic layer, and can be used as a transfer belt with an elastic layer for an image forming apparatus. is there. The surface layer is required to have releasability from toner and cleanability, to adhere firmly to the elastic layer, to not hinder the softness of the elastic layer, and to prevent cracks from occurring.
本発明の表面層は、電離放射線硬化型もしくは熱硬化型の塗工剤を弾性層の表面に塗布した後、電離放射線もしくは熱により架橋硬化させて形成させることが好ましい。表面層は、前記塗工剤をロールコート、バーコート、ディップコート、スプレーコート等、好ましくはロールコート、スプレーコートにより塗布し、溶剤を含有する場合は乾燥後、電離放射線を照射することにより、あるいは加熱することにより塗工剤を硬化させて形成することができる。 The surface layer of the present invention is preferably formed by applying an ionizing radiation-curable or thermosetting coating agent to the surface of the elastic layer and then cross-linking and curing the elastic layer with ionizing radiation or heat. The surface layer is coated with the coating agent by roll coating, bar coating, dip coating, spray coating, etc., preferably roll coating or spray coating, and if it contains a solvent, it is dried and then irradiated with ionizing radiation. Alternatively, it can be formed by curing the coating agent by heating.
ここで電離放射線としては、特に制限がなく、例えば、紫外線、電子線、アルファ線、ベータ線、ガンマ線、エックス線、中性子線などが挙げられ、その照射量は、紫外線の場合、通常１００〜１５，０００ｍＪ／ｃｍ２、好ましくは３００〜８０００ｍＪ／ｃｍ２である。 Here, the ionizing radiation is not particularly limited, and examples thereof include ultraviolet rays, electron beams, alpha rays, beta rays, gamma rays, X-rays, and neutron rays, and the irradiation amount thereof is usually 100 to 15 in the case of ultraviolet rays. It is 000 mJ / cm 2 , preferably 300 to 8000 mJ / cm 2 .
電離放射線硬化型の塗工剤は、（メタ）アクリルモノマー又は（メタ）アクリルオリゴマー、特に多官能アクリレートオリゴマー、多官能アクリレートモノマーを主成分とするのが好ましい。 The ionizing radiation curable coating agent preferably contains a (meth) acrylic monomer or a (meth) acrylic oligomer, particularly a polyfunctional acrylate oligomer or a polyfunctional acrylate monomer as a main component.
多官能アクリレートモノマーとしては、ジペンタエリスリトールヘキサアクリレート、ペンタエリスリトールトリアクリレート、ジトリメチロールプロパンテトラアクリレート、トリメチロールプロパントリアクリレート等が挙げられる。また、多官能アクリレートオリゴマーとしては、ノボラック型、ビスフェノール型エポキシ樹脂をアクリレート変性したエポキシアクリレート、ポリイソシアネートとポリオールとを反応させて得られるウレタン化合物のアクリレート変性物であるウレタンアクリレート、ポリエステル樹脂をアクリレート変性したポリエステルアクリレート等が挙げられる。これらは１種を単独で用いてもよく、２種以上を混合して用いてもよい。 Examples of the polyfunctional acrylate monomer include dipentaerythritol hexaacrylate, pentaerythritol triacrylate, ditrimethylolpropane tetraacrylate, and trimethylolpropane triacrylate. As the polyfunctional acrylate oligomer, epoxy acrylate obtained by acrylate-modified a novolak type or bisphenol type epoxy resin, urethane acrylate which is an acrylate-modified product of a urethane compound obtained by reacting polyisocyanate with a polyol, and polyester resin are acrylate-modified. Examples thereof include polyester acrylate. One of these may be used alone, or two or more thereof may be mixed and used.
電離放射線硬化型の塗工剤は、これらの（メタ）アクリルモノマー及び／又は（メタ）アクリルオリゴマーの他に、光重合開始剤、増感剤、界面活性剤、防汚成分等の各種添加剤、更には希釈溶媒等を配合して用いることが好ましい。 In addition to these (meth) acrylic monomers and / or (meth) acrylic oligomers, ionizing radiation-curable coating agents include various additives such as photopolymerization initiators, sensitizers, surfactants, and antifouling components. Further, it is preferable to use a diluting solvent or the like in combination.
熱硬化型の塗工剤は、水系ウレタン樹脂、シリコーン・アクリル系ハイブリッド樹脂、シリコーン・フッ素共重合樹脂等が挙げられる。 Examples of the thermosetting coating agent include water-based urethane resin, silicone / acrylic hybrid resin, and silicone / fluorine copolymer resin.
なお、表面層の硬化後の厚みは、０．２μｍ〜８．０μｍが好ましく、さらには０．４μｍ〜５．０μｍであることが好ましい。表面層の厚みが薄すぎると耐久性に問題が生じ、逆に厚すぎると表面層に割れが発生し、耐屈曲性が悪くなるため好ましくない。 The thickness of the surface layer after curing is preferably 0.2 μm to 8.0 μm, and more preferably 0.4 μm to 5.0 μm. If the thickness of the surface layer is too thin, there will be a problem in durability, and if it is too thick, the surface layer will crack and the bending resistance will deteriorate, which is not preferable.
［画像形成装置用弾性層付き転写ベルトの体積抵抗］
本発明の画像形成装置用弾性層付き転写ベルトを電子写真方式のプリンター、コピー機等の中間転写ベルト、転写搬送ベルト、搬送ベルトとして用いるには、その体積抵抗率を半導電性領域（１×１０５〜１×１０１３Ω・ｃｍ）にすることが求められる。体積抵抗率が１×１０５Ω・ｃｍ未満の転写ベルトの場合、転写ベルトの片面から電圧を印加して帯電させたベルト上の電荷が直ちに放電してしまい、電荷によって用紙やトナーを吸着するという転写ベルトとしての機能を発揮できない。また、体積抵抗率が１×１０１３Ω・ｃｍを超える転写ベルトの場合、ベルト上に発生させた電荷がいつまでもベルト上に残留し、用紙やトナーを吸着し続けるので電荷によって用紙やトナーを脱着するという転写ベルトとしての機能を発揮できない。
本発明の転写ベルトは、体積抵抗率が１０７〜１０１２Ω・ｃｍであることが好ましい。特に転写ベルトの体積抵抗率を上記の範囲に制御するために、本発明の目的を妨げない範囲で基材層及び／又は弾性層に導電性物質を配合することができる。導電性物質には電子伝導性材料とイオン伝導性材料があり、電子伝導性材料としては、例えば、カーボンブラック、グラフト化カーボンブラック、カーボンナノチューブ等のカーボン系材料、ポリアニリン、ポリチオフェン、ポリアセチレンなどの導電性高分子、導電性無機粒子が挙げられる。
[Volume resistance of transfer belt with elastic layer for image forming apparatus]
In order to use the transfer belt with an elastic layer for an image forming apparatus of the present invention as an intermediate transfer belt, a transfer transfer belt, a transfer belt for an electrophotographic printer, a copier, etc., the volume resistivity thereof is set to a semi-conductive region (1 ×). It is required to be 10 5 to 1 × 10 13 Ω · cm). In the case of a transfer belt with a volume resistivity of less than 1 × 10 5 Ω · cm, the electric charge on the belt charged by applying a voltage from one side of the transfer belt is immediately discharged, and the electric charge adsorbs paper and toner. It cannot function as a transfer belt. In the case of a transfer belt having a volume resistivity of more than 1 × 10 13 Ω · cm, the electric charge generated on the belt remains on the belt indefinitely and continues to adsorb the paper and toner, so that the paper and toner are desorbed by the electric charge. It cannot exert its function as a transfer belt.
Transfer belt of the present invention, it preferably has a volume resistivity of 10 7 ~10 12 Ω · cm. In particular, in order to control the volume resistivity of the transfer belt within the above range, a conductive substance can be blended in the base material layer and / or the elastic layer within a range that does not interfere with the object of the present invention. Conductive materials include electron conductive materials and ion conductive materials. Examples of the electron conductive materials include carbon-based materials such as carbon black, grafted carbon black, and carbon nanotubes, and conductivity such as polyaniline, polythiophene, and polyacetylene. Examples include polypolymers and conductive inorganic particles.
導電性無機粒子としては、例えばアルミニウム・亜鉛酸化物、アンチモン・スズ酸化物、インジウム・スズ酸化物、カーボンブラック等で表面処理を行った無機粒子などが挙げられる。 Examples of the conductive inorganic particles include inorganic particles whose surface has been surface-treated with aluminum / zinc oxide, antimony / tin oxide, indium tin oxide, carbon black and the like.
カーボンブラックは、ファーネスブラック、チャンネルブラック、ケッチェンブラック、アセチレンブラック等を挙げることができる。
グラフト化カーボンブラックは、カルボキシル基、水酸基、エポキシ基、アミノ基、オキサゾリン基、から選ばれる１種以上の官能基を有するポリマーをカーボンブラックの表面にグラフト付加されたカーボンブラックを意味する。
カーボンナノチューブは、平均径が１ｎｍ〜２００ｎｍ、平均長さが０．１μｍ〜１００μｍ、アスペクト比が１０〜１００００の範囲内であることが好ましい。カーボンナノチューブとしては、単層カーボンナノチューブ、多層カーボンナノチューブ（特開平１−２７０５４３、特公平３−６４６０６、特公平３−７７２８８、特開２００４−２９９９８６）、カップ積層型カーボンナノチューブ（特開２００３−７３９２８、特開２００４−３６００９９）、プレートレット型カーボンナノファイバー（特開２００４−３００６３１）、釣鐘状構造単位集合体（特開２０１２−４６８６４、特開２０１１−４７０８１、特開２０１１−４６８５２）などが挙げられる。これらの中でも、単層カーボンナノチューブ、多層カーボンナノチューブ、釣鐘状構造単位集合体が好ましい。
Examples of carbon black include furnace black, channel black, ketjen black, and acetylene black.
The grafted carbon black means a carbon black in which a polymer having one or more functional groups selected from a carboxyl group, a hydroxyl group, an epoxy group, an amino group and an oxazoline group is grafted onto the surface of the carbon black.
The carbon nanotubes preferably have an average diameter of 1 nm to 200 nm, an average length of 0.1 μm to 100 μm, and an aspect ratio in the range of 10 to 10,000. Examples of carbon nanotubes include single-walled carbon nanotubes, multi-walled carbon nanotubes (Japanese Patent Laid-Open No. 1-270543, JP-A-3-64606, JP-B-3-77288, JP-A-2004-299986), and cup-stacked carbon nanotubes (Japanese Patent Laid-Open No. 2003-73928). , JP-A-2004-3660099), platelet-type carbon nanofibers (Japanese Patent Laid-Open No. 2004-360391), bell-shaped structural unit aggregates (JP-A-2012-46864, JP-A-2011-47081, JP-A-2011-46852) and the like. Be done. Among these, single-walled carbon nanotubes, multi-walled carbon nanotubes, and bell-shaped structural unit aggregates are preferable.
イオン伝導性材料としては、例えば、ポリエーテルエステルアミド、ポリエチレンオキサイド−エピクロルヒドリン、ポリエーテルエステル、ポリエーテルアミド、ポリエチレンオキサイド、ポリエチレンオキサイド共重合体、部分架橋ポリエチレンオキサイド共重合体、４級アンモニウム塩含有アクリレート重合体、ポリスチレンスルホン酸、イオン電解質などがあげられ、これらを単独で、あるいは二種類以上を併用することができる。さらに、イオン電解質としては、アルカリ金属のチオシアン酸塩、リン酸塩、スルホン酸塩、硫酸塩、ハロゲン含有酸素酸塩、第１〜３級アンモニウム塩や４級アンモニウム塩などを単独または複数種組合わせて用いることができ、これらのうち特に、過塩素酸リチウム、過塩素酸ナトリウム、過塩素酸カリウム、チオシアン酸リチウム、チオシアン酸ナトリウム、チオシアン酸カリウムが好ましい。このようなイオン伝導性材料の中でも、共押出し時や後述するアニール工程時のような高温にさらされた場合、イオン伝導性材料が樹脂中を移行することを考慮すると、高分子型が好ましい。なお、本明細書では、高分子型のイオン伝導性材料とは数平均分子量が３０００以上のイオン伝導性材料のことをいう。 Examples of the ionic conductive material include polyether ester amide, polyethylene oxide-epichlorohydrin, polyether ester, polyether amide, polyethylene oxide, polyethylene oxide copolymer, partially crosslinked polyethylene oxide copolymer, and quaternary ammonium salt-containing acrylate. Examples thereof include polymers, polystyrene sulfonic acid, and ionic electrolytes, and these can be used alone or in combination of two or more. Further, as the ion electrolyte, one or a plurality of types of alkali metal thiocyanate, phosphate, sulfonate, sulfate, halogen-containing oxygenate, tertiary ammonium salt, quaternary ammonium salt, etc. are used. It can be used together, and among these, lithium perchlorate, sodium perchlorate, potassium perchlorate, lithium thiocyanate, sodium thiocyanate, and potassium thiocyanate are particularly preferable. Among such ionic conductive materials, the polymer type is preferable in consideration of the fact that the ionic conductive material migrates into the resin when exposed to a high temperature such as during coextrusion or during the annealing step described later. In addition, in this specification, a polymer type ion conductive material means an ion conductive material having a number average molecular weight of 3000 or more.
基材層に半導電性を付与するためには、導電性物質を含有する必要がある。
基材層にイオン伝導性材料を配合して導電性を付与する場合、熱可塑性樹脂としてはフッ素系樹脂が好ましく、特にポリフッ化ビニリデンおよびその共重合体が好ましい。イオン伝導性材料はポリフッ化ビニリデンおよびその共重合体と親和性があり、イオン伝導性材料を配合したポリフッ化ビニリデンおよびその共重合体に電圧を印加すると、当該樹脂中のイオンが移動し、当該樹脂が導電性を示す。
In order to impart semiconductivity to the base material layer, it is necessary to contain a conductive substance.
When an ionic conductive material is blended in the base material layer to impart conductivity, a fluororesin is preferable as the thermoplastic resin, and polyvinylidene fluoride and a copolymer thereof are particularly preferable. The ionic conductive material has an affinity for polyvinylidene fluoride and its copolymer, and when a voltage is applied to polyvinylidene fluoride and its copolymer containing the ionic conductive material, the ions in the resin move, and the resin is said to be present. The resin is conductive.
基材層にポリアミド系樹脂を使用した場合、導電性物質としてはカーボンナノチューブを含有することが好ましい。ポリアミド系樹脂とカーボンナノチューブとの配合割合は、特に制限されるものではないが、ポリアミド系樹脂とカーボンナノチューブの合計量のうち、ポリアミド系樹脂を８０〜９９重量％、カーボンナノチューブを２０〜１重量％含むことが好ましく、１０〜１重量％含むことがより好ましい。カーボンナノチューブの配合量が２０重量％を超えると樹脂組成物は押出適性に劣る為、得られるチューブの表面が平滑でなくなる恐れがある。また、カーボンナノチューブの配合量が１重量％未満では、半導電性領域の体積抵抗率を付与することが困難となる。 When a polyamide resin is used for the base material layer, it is preferable to contain carbon nanotubes as the conductive substance. The blending ratio of the polyamide resin and the carbon nanotubes is not particularly limited, but 80 to 99% by weight of the polyamide resin and 20 to 1% by weight of the carbon nanotubes in the total amount of the polyamide resin and the carbon nanotubes. % Is preferably contained, and more preferably 10 to 1% by weight. If the blending amount of the carbon nanotubes exceeds 20% by weight, the resin composition is inferior in extrusion suitability, so that the surface of the obtained tube may not be smooth. Further, if the blending amount of the carbon nanotubes is less than 1% by weight, it becomes difficult to impart the volume resistivity in the semi-conductive region.
基材層にフッ素系樹脂とポリアミド系樹脂をブレンドした樹脂組成物を使用した場合、導電剤としてカーボンブラックを含有し、さらに相溶化剤を含有したものが好ましい。相溶化剤を含有することにより、フッ素系樹脂マトリクス中にポリアミド系樹脂が微分散した海島構造を呈し、これにより半導電性領域での電気抵抗の均一性を示す。配合割合は、特に制限されるものではないが、フッ素系樹脂とポリアミド系樹脂との合計量のうち、フッ素系樹脂を５０〜９５重量％、ポリアミド系樹脂を５０〜５重量％含有していることが好ましい。カーボンブラックの配合量は、フッ素系樹脂とポリアミド系樹脂との合計量１００重量部に対し、３〜２５重量部であることが好ましい。相溶化剤の配合量は、フッ素系樹脂とポリアミド系樹脂との合計量１００重量部に対し、０．５〜１０重量部であることが好ましい。相溶化剤は、アルキル鎖の炭素数が３以下の（メタ）アクリル酸アルキルエステル単量体由来の構成単位と、エポキシ基を有するビニル単量体由来の構成単位とを含む共重合体であって、１分子中に１個以上のエポキシ基を含有するものが好ましい。アルキル鎖の炭素数が３以下の（メタ）アクリル酸アルキルエステル単量体由来の構成単位としては、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸プロピル、（メタ）アクリル酸イソプロピルが挙げられる。エポキシ基を有するビニル単量体由来の構成単位としては、（メタ）アクリル酸グリシジル、アリルグリシジルエーテル、エタクリン酸グリシジル、イタコン酸グリシジル等が挙げられる。 When a resin composition in which a fluorine-based resin and a polyamide-based resin are blended is used for the base material layer, those containing carbon black as a conductive agent and further containing a compatibilizer are preferable. By containing the compatibilizer, the polyamide-based resin exhibits a sea-island structure in which the polyamide-based resin is finely dispersed in the fluorine-based resin matrix, thereby exhibiting the uniformity of electrical resistance in the semi-conductive region. The blending ratio is not particularly limited, but contains 50 to 95% by weight of the fluorine-based resin and 50 to 5% by weight of the polyamide-based resin in the total amount of the fluorine-based resin and the polyamide-based resin. Is preferable. The blending amount of carbon black is preferably 3 to 25 parts by weight with respect to 100 parts by weight of the total amount of the fluorine-based resin and the polyamide-based resin. The blending amount of the compatibilizer is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the total amount of the fluorine-based resin and the polyamide-based resin. The compatibilizer is a copolymer containing a structural unit derived from a (meth) acrylic acid alkyl ester monomer having 3 or less carbon atoms in an alkyl chain and a structural unit derived from a vinyl monomer having an epoxy group. It is preferable that one molecule contains one or more epoxy groups. The structural units derived from the (meth) acrylic acid alkyl ester monomer having 3 or less carbon atoms in the alkyl chain include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth). Examples include isopropyl acrylate. Examples of the structural unit derived from the vinyl monomer having an epoxy group include glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl etacrynate, and glycidyl itaconic acid.
弾性層に半導電性を付与するためには、導電性物質を含有させる必要がある。導電性物質としては、特に上述したイオン伝導性材料を配合することが好ましい。弾性層に導電性物質としてカーボンブラックやカーボンナノチューブなどの電子導電剤を配合した場合、導電性はカーボンブラックなどの導電剤の粒子の接触による導電経路の形成もしくは分散したカーボンブラックなどの導電剤の粒子間を電子がジャンプするトンネル効果（粒子間のポテンシャル障壁を越える電子の走り抜けの現象のこと）により発現すると考えられている。しかしながら、基材層上にカーボンブラックなどの電子導電剤を配合した弾性層を形成した弾性層付き転写ベルトは弾性層が柔軟であるため、転写ベルト駆動時に弾性層が伸縮し、長時間使用すると導電剤粒子間の距離が変化するため、電気抵抗が部分的に変動し、電気抵抗のばらつきが生じるため好ましくない。 In order to impart semiconductivity to the elastic layer, it is necessary to contain a conductive substance. As the conductive substance, it is particularly preferable to blend the above-mentioned ion conductive material. When an electronic conductive agent such as carbon black or carbon nanotube is blended in the elastic layer as a conductive substance, the conductivity of the conductive agent such as carbon black formed or dispersed by the contact of particles of the conductive agent such as carbon black. It is thought to be manifested by the tunnel effect in which electrons jump between particles (a phenomenon in which electrons run through the potential barrier between particles). However, a transfer belt with an elastic layer in which an elastic layer containing an electronic conductive agent such as carbon black is formed on a base material layer has a flexible elastic layer, so that the elastic layer expands and contracts when the transfer belt is driven, and when used for a long time Since the distance between the conductive agent particles changes, the electric resistance partially fluctuates, which is not preferable because the electric resistance varies.
イオン伝導性材料は、分極が大きい熱可塑性樹脂と親和性があり、特にポリフッ化ビニリデンや熱可塑性ポリウレタンへ配合し電圧を印加すると当該樹脂中でイオンが移動し、導電性を発現させることができる。
基材層と弾性層とキャリア層を順に備えるキャリア層付きシームレスベルトの場合、基材層と弾性層のどちらか、または両方に数平均分子量が３０００未満の低分子型イオン伝導性材料を配合すると、共押出時またはアニール工程（周長を均一にするため押出機から押出したチューブ状原反を円筒状の金型に挿入し加熱処理する）時に、イオン伝導性材料がより親和性の高い樹脂層へ移行し、所定の電気抵抗を発現させるために配合したイオン伝導性材料の濃度が変化し、電気抵抗が変動するという不都合が発生した。
この結果に鑑み、イオン伝導性材料は数平均分子量が３０００以上、好ましくは８０００以上の高分子型を使用するのが好ましい。具体的には、基材層にイオン伝導性材料を配合し、弾性層にイオン伝導性材料を配合する場合、基材層と弾性層に用いるイオン伝導性材料の数平均分子量は３０００以上が好ましく、８０００以上がより好ましい。基材層はポリフッ化ビニリデン系樹脂が好ましく、弾性層はウレタン系エラストマーが好ましい。また、基材層に電子導電性材料を配合し、弾性層にイオン伝導性材料を配合する場合、弾性層に用いるイオン伝導性材料の数平均分子量は３０００以上が好ましく、さらには８０００以上が好ましい。
The ionic conductive material has an affinity with a thermoplastic resin having a large polarization, and in particular, when it is blended with polyvinylidene fluoride or thermoplastic polyurethane and a voltage is applied, ions move in the resin to exhibit conductivity. ..
In the case of a seamless belt with a carrier layer having a base material layer, an elastic layer, and a carrier layer in this order, when a low molecular weight ion conductive material having a number average molecular weight of less than 3000 is blended in either or both of the base material layer and the elastic layer. , A resin with which the ionic conductive material has a higher affinity during coextrusion or during the annealing process (the tubular raw material extruded from the extruder is inserted into a cylindrical mold and heat-treated to make the circumference uniform). The inconvenience that the concentration of the ionic conductive material blended in order to move to the layer and develop a predetermined electric resistance changes and the electric resistance fluctuates occurs.
In view of this result, it is preferable to use a polymer type having a number average molecular weight of 3000 or more, preferably 8000 or more, as the ionic conductive material. Specifically, when an ionic conductive material is blended in the base material layer and an ionic conductive material is blended in the elastic layer, the number average molecular weight of the ionic conductive material used in the base material layer and the elastic layer is preferably 3000 or more. , 8000 or more is more preferable. The base material layer is preferably a polyvinylidene fluoride resin, and the elastic layer is preferably a urethane elastomer. When an electron conductive material is blended in the base material layer and an ion conductive material is blended in the elastic layer, the number average molecular weight of the ion conductive material used in the elastic layer is preferably 3000 or more, more preferably 8000 or more. ..
［キャリア層付きシームレスベルトの製造方法］
基材層、弾性層、キャリア層を順に備えるキャリア層付きシームレスベルトは、共押出法で製造する。具体的に説明すると、３台の押出機と、該押出機の下方に該押出機に連通して環状ダイスが配置され、その環状ダイスの下方には、環状ダイスから下向きに押し出される溶融樹脂を冷却固化する装置が配設された押出成形装置を用いて、基材層を形成する樹脂組成物と弾性層を形成する樹脂組成物とキャリア層を形成する樹脂組成物を、キャリア層が外側、基材層が内側に形成されるようにそれぞれ別々の押出機に供給し、連通した環状ダイスにより共押出して、チューブ状に形成する方法が挙げられる。また、共押出した後の冷却固化には、例えば溶融したチューブをエアリングより吹出される冷風により冷却固化する方法、マンドレルの外周に接触させて冷却固化する方法などが挙げられる。また、得られたチューブ状の成形体を所定長さに切断することにより、キャリア層付きシームレスベルトを得ることができる。
[Manufacturing method of seamless belt with carrier layer]
A seamless belt with a carrier layer having a base material layer, an elastic layer, and a carrier layer in this order is manufactured by a coextrusion method. Specifically, three extruders and an annular die are arranged below the extruder so as to communicate with the extruder, and a molten resin extruded downward from the annular die is placed below the annular die. Using an extrusion molding device provided with a device for cooling and solidifying, a resin composition for forming a base material layer, a resin composition for forming an elastic layer, and a resin composition for forming a carrier layer are formed on the outside of the carrier layer. Examples thereof include a method in which the base material layer is supplied to separate extruders so as to be formed inside, and coextruded with a continuous annular die to form a tube shape. Further, examples of the cooling and solidifying after coextrusion include a method of cooling and solidifying a molten tube with cold air blown from an air ring, a method of contacting the outer periphery of a mandrel and cooling and solidifying. Further, by cutting the obtained tubular molded body to a predetermined length, a seamless belt with a carrier layer can be obtained.
［転写ベルトの製造方法］
次に、画像形成装置に実際に使用する転写ベルトの製造方法について説明する。
まず、最初にキャリア層付きシームレスベルトの外側に位置するキャリア層のみを剥離する。次いで、キャリア層を剥離されたシームレスベルトの弾性層表面に、表面層形成用塗工液を塗布して活性エネルギー線もしくは熱により硬化することにより、表面層を形成させる。塗工液の塗布方法は、例えば、ロールコート、バーコート、ディップコート、スプレーコート等が挙げられる。
[Manufacturing method of transfer belt]
Next, a method of manufacturing a transfer belt actually used in the image forming apparatus will be described.
First, only the carrier layer located on the outside of the seamless belt with the carrier layer is peeled off. Next, a coating liquid for forming a surface layer is applied to the surface of the elastic layer of the seamless belt from which the carrier layer has been peeled off, and the surface layer is formed by curing with active energy rays or heat. Examples of the coating method for applying the coating liquid include roll coating, bar coating, dip coating, and spray coating.
以下、本発明について、実施例によりさらに詳しく説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
実施例、および比較例で作製したキャリア層付きシームレスベルトは、以下の項目について評価し、その結果を表１に示す。
（１）溶融粘度
長さ１０ｍｍ×直径１ｍｍのダイを取り付けた島津製作所製高化式フローテスターを用いて溶融粘度を測定（測定条件：温度２００℃、荷重１００ｋｇｆ）した。なお、その単位を（ｐｏｉｓｅ）として表した。また、本発明で用いた溶融粘度の差とは、弾性層を形成する樹脂の溶融粘度からキャリア層を形成する溶融粘度の差の絶対値で表すものとする。
（２）数平均分子量
ポリエチレンオキサイドの数平均分子量は、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）を用い、溶媒に水を用いて測定した。数平均分子量はポリエチレンオキサイド換算で算出した。なお、ＧＰＣで他のイオン伝導性材料の数平均分子量の測定をする場合は、イオン伝導性材料をよく溶解する溶媒を用いる。
（２）ショアＡ硬度（弾性層）
厚さ２ｍｍのシートを３枚重ねて厚み６ｍｍとし、デューロメータ タイプＡ（上島製作所製）を用いて測定した。
（３）引張弾性率（基材層）
１００ｋｇのセルを取り付けたオートグラフ（試料幅１０ｍｍ、チャック間１００ｍｍ、引張速度５０ｍ／ｍｉｎ）を用いてＴＤ方向の引張弾性率を６点測定し、その平均値を引張弾性率とした。
（４）体積抵抗率
キャリア層付きシームレスベルトのキャリア層を剥離したもの（基材層／弾性層の積層体）について、ＵＲＳプローブを取り付けたハイレスタＵＰ（ＭＣＰ−ＨＴ４５０、ダイヤインスツルメンツ社製）を用い、４６０ｍｍ×４００ｍｍのサンプルについてＴＤ方向に１０点、ＭＤ方向に１０点の体積抵抗率を測定し、その平均値を体積抵抗率とした。なお、体積抵抗率の単位を（Ω・ｃｍ）として表した。
（５）表面抵抗率
キャリア層付きシームレスベルトのキャリア層を剥離したもの（基材層／弾性層の積層体）について、ＵＲＳプローブを取り付けたハイレスタＵＰ（ＭＣＰ−ＨＴ４５０、ダイヤインスツルメンツ社製）を用い、４６０ｍｍ×４００ｍｍのサンプルについてＴＤ方向に１０点、ＭＤ方向に１０点のサンプルの表側（弾性層側表面から測定）の表面抵抗率を測定し、その平均値を表面抵抗率とした。なお、表面抵抗率の単位を（Ω／□）として表した。
（６）剥離強度
キャリア層付きシームレスベルトより１０ｍｍ幅の短冊を切り出し、オートグラフを用い、５０ｍｍ／ｍｉｎの引張速度で剥離させ、弾性層とキャリア層との剥離強度を測定した。
（７）中心線平均粗さＲａ
本発明でいう中心線平均粗さＲａは、ＪＩＳ Ｂ０６０１：１９９４年記載の中心線表面粗さのことである。キャリア層付きシームレスベルトのキャリア層を剥離したもの（基材層／弾性層の積層体）について、表面粗さ測定機械（東京精密社製サーフコム５７０A）を用い、カットオフ０．２５ｍｍ、トラバーススピード０．３ｍｍ／secの条件（測定範囲：２．５ｍｍ）で測定した。
The seamless belts with carrier layers produced in Examples and Comparative Examples were evaluated for the following items, and the results are shown in Table 1.
(1) Melt Viscosity The melt viscosity was measured using a high-grade flow tester manufactured by Shimadzu Corporation equipped with a die having a length of 10 mm and a diameter of 1 mm (measurement conditions: temperature 200 ° C., load 100 kgf). In addition, the unit was expressed as (poise). The difference in melt viscosity used in the present invention is expressed as an absolute value of the difference in melt viscosity from the resin forming the elastic layer to the melt viscosity forming the carrier layer.
(2) Number average molecular weight The number average molecular weight of polyethylene oxide was measured by using gel permeation chromatography (GPC) and using water as a solvent. The number average molecular weight was calculated in terms of polyethylene oxide. When measuring the number average molecular weight of other ionic conductive materials by GPC, a solvent that dissolves the ionic conductive materials well is used.
(2) Shore A hardness (elastic layer)
Three sheets having a thickness of 2 mm were stacked to make a thickness of 6 mm, and the measurement was performed using a durometer type A (manufactured by Ueshima Seisakusho).
(3) Tensile elastic modulus (base material layer)
Tensile elastic modulus in the TD direction was measured at 6 points using an autograph (sample width 10 mm, chuck distance 100 mm, tensile speed 50 m / min) to which a 100 kg cell was attached, and the average value was taken as the tensile elastic modulus.
(4) Volume resistivity For the seamless belt with carrier layer from which the carrier layer has been peeled off (layer of base material layer / elastic layer), use High Resta UP (MCP-HT450, manufactured by Dia Instruments) with a URS probe attached. The volume resistivity of 10 points in the TD direction and 10 points in the MD direction was measured for a sample of 460 mm × 400 mm, and the average value was taken as the volume resistivity. The unit of volume resistivity was expressed as (Ω · cm).
(5) Surface resistivity For the seamless belt with carrier layer from which the carrier layer has been peeled off (layer of base material layer / elastic layer), use High Resta UP (MCP-HT450, manufactured by Dia Instruments) with a URS probe attached. For a sample of 460 mm × 400 mm, the surface resistivity of the front side (measured from the surface on the elastic layer side) of the sample at 10 points in the TD direction and 10 points in the MD direction was measured, and the average value was taken as the surface resistivity. The unit of surface resistivity is expressed as (Ω / □).
(6) Peeling strength A strip having a width of 10 mm was cut out from a seamless belt with a carrier layer, peeled off at a tensile speed of 50 mm / min using an autograph, and the peeling strength between the elastic layer and the carrier layer was measured.
(7) Center line average roughness Ra
The center line average roughness Ra referred to in the present invention is the center line surface roughness described in JIS B0601: 1994. For the seamless belt with carrier layer with the carrier layer peeled off (base material layer / elastic layer laminate), a surface roughness measuring machine (Surfcom 570A manufactured by Tokyo Seimitsu Co., Ltd.) was used to cut off 0.25 mm and traverse speed 0. It was measured under the condition of .3 mm / sec (measurement range: 2.5 mm).
原料としては、下記のものを用いた。
＜基材層の原料＞
原料１−１：
二軸混練機を用いて、ナイロン１２を９６．５重量％とカーボンナノチューブ３．５重量％とを溶融混練して原料１−１とした。なお、本原料を用いた基材層の引張弾性率を測定すると１６００ＭＰａであった。
The following raw materials were used.
<Raw material for base material>
Raw material 1-1:
Using a twin-screw kneader, 96.5% by weight of nylon 12 and 3.5% by weight of carbon nanotubes were melt-kneaded to obtain raw material 1-1. The tensile elastic modulus of the base material layer using this raw material was measured and found to be 1600 MPa.
＜弾性層の原料＞
原料２−１：
二軸混練機を用いて、エステル系の熱可塑性ポリウレタン（ショアＡ硬度：６０、溶融粘度：４２００）９９重量％に対し、ポリエチレンオキサイド（数平均分子量：８００，０００）０．９重量％、過塩素酸リチウム０．１重量％を溶融混練して原料２−１とした。
原料２−２：
二軸混練機を用いて、エステル系の熱可塑性ポリウレタン（ショアＡ硬度：６０、溶融粘度：８３９０）９９重量％に対し、ポリエチレンオキサイド（数平均分子量：８００，０００）０．９重量％、過塩素酸リチウム０．１重量％を溶融混練して原料２−２とした。
原料２−３：
イオン導電剤を含有した部分架橋エーテル系の熱可塑性ポリウレタン（ショアＡ硬度：４５、溶融粘度：９５５０）
原料２−４：
イオン導電剤を含有した部分架橋エーテル系の熱可塑性ポリウレタン（ショアＡ硬度：４５、溶融粘度：２７６０）
<Raw material for elastic layer>
Raw material 2-1:
Using a biaxial kneader, polyethylene oxide (number average molecular weight: 800,000) 0.9% by weight, excess with respect to 99% by weight of ester-based thermoplastic polyurethane (shore A hardness: 60, melt viscosity: 4200). 0.1% by weight of lithium chlorate was melt-kneaded to obtain raw material 2-1.
Raw material 2-2:
Using a biaxial kneader, polyethylene oxide (number average molecular weight: 800,000) 0.9% by weight, excess with respect to 99% by weight of ester-based thermoplastic polyurethane (shore A hardness: 60, melt viscosity: 8390). 0.1% by weight of lithium chlorate was melt-kneaded to obtain a raw material 2-2.
Ingredients 2-3:
Partially crosslinked ether-based thermoplastic polyurethane containing an ionic conductive agent (Shore A hardness: 45, melt viscosity: 9550)
Raw material 2-4:
Partially crosslinked ether-based thermoplastic polyurethane containing an ionic conductive agent (Shore A hardness: 45, melt viscosity: 2760)
＜キャリア層の原料＞
原料３−１：
高密度ポリエチレン（密度：０．９５０、溶融粘度：５０００）
原料３−２：
高密度ポリエチレン（密度：０．９４１、溶融粘度：９５３０）
原料３−３：
高密度ポリエチレン（密度：０．９５０、溶融粘度：９９３０）
原料３−４：
高密度ポリエチレン（密度：０．９５２、溶融粘度：１５１００）
原料３−５：
低密度ポリエチレン（密度：０．９２４、溶融粘度：１７７０）
原料３−６：
低密度ポリエチレン（密度：０．９２２、溶融粘度：５６１０）
原料３−７：
ポリアセタール共重合体
<Raw material for carrier layer>
Raw material 3-1:
High density polyethylene (density: 0.950, melt viscosity: 5000)
Raw material 3-2:
High density polyethylene (density: 0.941, melt viscosity: 9530)
Raw material 3-3:
High density polyethylene (density: 0.950, melt viscosity: 9930)
Raw material 3-4:
High density polyethylene (density: 0.952, melt viscosity: 15100)
Raw material 3-5:
Low density polyethylene (density: 0.924, melt viscosity: 1770)
Raw material 3-6:
Low density polyethylene (density: 0.922, melt viscosity: 5610)
Raw material 3-7:
Polyacetal copolymer
［実施例１乃至１０、比較例１乃至８］
シリンダー径５０ｍｍの押出機３台の先端に３層の環状ダイを装着した装置を用い、基材層を形成する樹脂組成物と弾性層を形成する樹脂組成物とキャリア層を形成する樹脂組成物を、キャリア層が外側、弾性層が中間、基材層が内側に形成されるように別々の押出機に供給し、環状ダイスにより共押出して、チューブ状に成形後、長さ４００ｍｍにカットし、内層である基材層の厚さ１２０μｍ、弾性層の厚さ３００μｍ、キャリア層の厚さ１００μｍ、周長８５０ｍｍ、幅４００ｍｍのキャリア層付きシームレスベルトを得た。
[Examples 1 to 10, Comparative Examples 1 to 8]
A resin composition for forming a base material layer, a resin composition for forming an elastic layer, and a resin composition for forming a carrier layer using a device in which a three-layer annular die is attached to the tip of three extruders having a cylinder diameter of 50 mm. Is supplied to separate extruders so that the carrier layer is formed on the outside, the elastic layer is formed on the middle, and the base material layer is formed on the inside, co-extruded with an annular die, formed into a tube shape, and then cut to a length of 400 mm. A seamless belt with a carrier layer having a thickness of 120 μm for the base material layer as an inner layer, a thickness of 300 μm for the elastic layer, a thickness of 100 μm for the carrier layer, a circumference length of 850 mm, and a width of 400 mm was obtained.
実施例、および比較例で作製したキャリア層付きシームレスベルトは、以下項目について評価し、その結果を表１及び表２に示す。 The seamless belts with carrier layers produced in Examples and Comparative Examples were evaluated for the following items, and the results are shown in Tables 1 and 2.
表１に示すように、弾性層を形成する樹脂としてショアＡ硬度が８０以下であるウレタン系エラストマーを含有し、キャリア層を形成する樹脂として密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を含有し、かつ弾性層に含まれるウレタン系エラストマーまたはアクリル系エラストマーとキャリア層に含まれるポリエチレン系樹脂の溶融粘度の差が１００００ｐｏｉｓｅ以下である実施例１乃至１０は、弾性層とキャリア層が良好な易剥離性を示し、キャリア層を剥離した弾性層の中心線平均粗さＲａが０．１４以上を示し、さらにキャリア層を剥離したシームレスベルトの体積抵抗値及び表面抵抗値も安定的に半導電性領域を示した。 As shown in Table 1, the resin forming the elastic layer contains a urethane-based elastomer having a Shore A hardness of 80 or less, and the resin forming the carrier layer contains a polyethylene-based resin having a density of 0.940 g / cm3 or more. In Examples 1 to 10, the difference in melt viscosity between the urethane-based elastomer or acrylic-based elastomer contained in the elastic layer and the polyethylene-based resin contained in the carrier layer is 10,000 poise or less, and the elastic layer and the carrier layer are easily formed. The elastic layer with the carrier layer peeled off has a centerline average roughness Ra of 0.14 or more, and the seamless belt with the carrier layer peeled off has a stable semi-conductive volume resistance and surface resistance. The area is shown.
一方、キャリア層を形成する樹脂として、密度が０．９４ｇ／ｃｍ３未満であるポリエチレン樹脂を含有した比較例２、３、５、６、７は、キャリア層を剥離した弾性層の中心線平均粗さＲａが０．１４未満を示し、シームレスベルトの表面粗さが低下した。また、弾性層を形成する樹脂とキャリア層を形成する樹脂の溶融粘度の差が１０９００ｐｏｉｓｅである比較例１は、弾性層とキャリア層との剥離強度は良好な値を示したがキャリア層を剥離した弾性層の中心線平均粗さＲａが０．４０μｍを超えた。弾性層を形成する樹脂とキャリア層を形成する樹脂の溶融粘度の差が１２３４０ｐｏｉｓｅである比較例８は、弾性層とキャリア層との剥離強度が１００ｇ／１０ｍｍを超え、剥離強度が大きく、且つ表面粗さが大きい値を示した。また、キャリア層を形成する樹脂として他の熱可塑性樹脂との接着性が悪いポリアセタール系樹脂を使用した比較例４は、剥離強度が非常に大きい値を示した。 On the other hand, in Comparative Examples 2, 3, 5, 6 and 7 containing a polyethylene resin having a density of less than 0.94 g / cm 3 as the resin forming the carrier layer, the center line average of the elastic layer from which the carrier layer was peeled off. The roughness Ra was less than 0.14, and the surface roughness of the seamless belt was reduced. Further, in Comparative Example 1 in which the difference in melt viscosity between the resin forming the elastic layer and the resin forming the carrier layer was 10900 poise, the peel strength between the elastic layer and the carrier layer showed a good value, but the carrier layer was peeled off. The average roughness Ra of the center line of the elastic layer was more than 0.40 μm. In Comparative Example 8 in which the difference in melt viscosity between the resin forming the elastic layer and the resin forming the carrier layer is 12340 poise, the peel strength between the elastic layer and the carrier layer exceeds 100 g / 10 mm, the peel strength is large, and the surface surface is large. It showed a value with a large roughness. Further, in Comparative Example 4 in which a polyacetal resin having poor adhesiveness to other thermoplastic resins was used as the resin forming the carrier layer, the peel strength showed a very large value.
＜参考例１＞
分子量７００００、（メタ）アクリル基１個当たりの分子量が１３８０のウレタンアクリレートオリゴマー（根上工業製）９７重量部、光重合開始剤として２−ヒドロキシ−２−メチル−１−フェニル−プロパン−１−オン２．８５重量部、シリコーン系撥水剤０．１５重量部に溶剤であるメチルイソブチルケトンを１０００重量部加え、均一に溶解して表面層形成用塗布液を調整した。
次に、ディッピング法にて実施例１のキャリア層付きシームレスベルトのキャリア層を剥離したシームレスベルトの弾性層表面に表面層形成用塗布液を塗布して、乾燥後、紫外線を３０００ｍＪ／ｃｍ２を照射し、厚さ１．０μｍの表面層を形成して弾性層付き転写ベルトを得た。
<Reference example 1>
97 parts by weight of urethane acrylate oligomer (manufactured by Negami Kogyo) with a molecular weight of 70000 and a molecular weight of 1380 per (meth) acrylic group, 2-hydroxy-2-methyl-1-phenyl-propane-1-one as a photopolymerization initiator 1000 parts by weight of methyl isobutyl ketone as a solvent was added to 2.85 parts by weight and 0.15 parts by weight of the silicone-based water repellent, and the mixture was uniformly dissolved to prepare a coating liquid for forming a surface layer.
Next, a coating liquid for forming a surface layer is applied to the surface of the elastic layer of the seamless belt from which the carrier layer of the seamless belt with a carrier layer of Example 1 has been peeled off by a dipping method, and after drying, ultraviolet rays are applied to 3000 mJ / cm 2 . After irradiation, a surface layer having a thickness of 1.0 μm was formed to obtain a transfer belt with an elastic layer.
参考例１で作製した弾性層付き転写ベルトを中間転写ベルトとしてカラープリンターに装着し、画像出しを行った結果、転写画像に全く中抜けがなく、ＪＩＳ Ｐ８１１５に準拠した耐折性試験（荷重４．９Ｎで１００００回折り曲げ）では、クラックの発生が見られず、中間転写ベルトとして良好な性能を示した。
The transfer belt with elastic layer produced in Reference Example 1 was attached to a color printer as an intermediate transfer belt, and as a result of image output, there was no hollow in the transfer image, and a folding resistance test (load 4) conforming to JIS P8115. No cracks were observed at 1.9 N and 10000 bending), showing good performance as an intermediate transfer belt.
Claims (6)
前記基材層は、熱可塑性樹脂を含有し、
前記弾性層は、ショアＡ硬度が８０以下のウレタン系エラストマーまたはアクリル系エラストマーを含有し、
前記キャリア層は、密度が０．９４０ｇ／ｃｍ３以上のポリエチレン系樹脂を含有し、かつ前記弾性層に含まれるウレタン系エラストマーまたはアクリル系エラストマーと前記キャリア層に含まれるポリエチレン系樹脂の２００℃、１００ｋｇｆにおける溶融粘度の差が１００００ｐｏｉｓｅ以下であることを特徴とするキャリア層付きシームレスベルト。 In a seamless belt with a carrier layer having a base material layer, an elastic layer, and a carrier layer in this order,
The base material layer contains a thermoplastic resin and
The elastic layer contains a urethane-based elastomer or an acrylic-based elastomer having a shore A hardness of 80 or less.
The carrier layer contains a polyethylene resin having a density of 0.940 g / cm 3 or more, and the urethane-based elastomer or acrylic elastomer contained in the elastic layer and the polyethylene-based resin contained in the carrier layer at 200 ° C. A seamless belt with a carrier layer, characterized in that the difference in melt viscosity at 100 kgf is 10,000 poise or less.
In the method for manufacturing a transfer belt with an elastic layer for an image forming apparatus, which comprises a base material layer, an elastic layer, and a surface layer in this order, the carrier layer which is the outermost layer of the seamless belt with the carrier layer according to any one of claims 1 to 4 is peeled off. After that, a coating liquid for forming a surface layer is applied to the outside of the surface of the elastic layer and cured with active energy rays or heat to form a surface layer, which is a transfer with an elastic layer for an image forming apparatus. How to make a belt.
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| JP7535072B2 (en) | 2022-03-07 | 2024-08-15 | キヤノン株式会社 | Resin composition, resin molded product, and method for producing resin molded product |
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| JPS6461219A (en) * | 1987-09-02 | 1989-03-08 | Mitsui Toatsu Chemicals | Manufacture of thermoplastic polyurethane film |
| JPH07285158A (en) * | 1994-04-20 | 1995-10-31 | Sekisui Chem Co Ltd | Manufacture of thermoplastic resin sheet |
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| JP2010256719A (en) * | 2009-04-27 | 2010-11-11 | Okura Ind Co Ltd | Transfer belt for image forming apparatus |
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| JPS6186262A (en) * | 1984-10-04 | 1986-05-01 | 凸版印刷株式会社 | Multilayer material |
| JPS6461219A (en) * | 1987-09-02 | 1989-03-08 | Mitsui Toatsu Chemicals | Manufacture of thermoplastic polyurethane film |
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| JP2005234127A (en) * | 2004-02-18 | 2005-09-02 | Okura Ind Co Ltd | Seamless belt with surface protective layer and manufacturing method of the same |
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| JP7535072B2 (en) | 2022-03-07 | 2024-08-15 | キヤノン株式会社 | Resin composition, resin molded product, and method for producing resin molded product |
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