WO2018061762A1 - Polyurehtane base - Google Patents

Polyurehtane base Download PDF

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Publication number
WO2018061762A1
WO2018061762A1 PCT/JP2017/032987 JP2017032987W WO2018061762A1 WO 2018061762 A1 WO2018061762 A1 WO 2018061762A1 JP 2017032987 W JP2017032987 W JP 2017032987W WO 2018061762 A1 WO2018061762 A1 WO 2018061762A1
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Prior art keywords
polyurethane
base material
rubber elastic
isocyanate
cleaning
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PCT/JP2017/032987
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French (fr)
Japanese (ja)
Inventor
奈津美 木村
深澤　清文
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Nok株式会社
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Priority to JP2018518679A priority Critical patent/JP6544487B2/en
Publication of WO2018061762A1 publication Critical patent/WO2018061762A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/046—Forming abrasion-resistant coatings; Forming surface-hardening coatings
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G21/00—Arrangements not provided for by groups G03G13/00 - G03G19/00, e.g. cleaning, elimination of residual charge

Definitions

  • the present invention relates to a polyurethane base material. More specifically, the present invention relates to a polyurethane substrate that is effectively used as a cleaning blade body for an electrophotographic apparatus.
  • various cleaning blades are disposed in order to remove toner remaining on a toner carrier such as a photosensitive drum, a transfer belt, and an intermediate transfer member.
  • These cleaning blades are generally made of a thermoplastic or thermosetting polyurethane resin, but are mainly made of a thermosetting polyurethane resin from the viewpoint of plastic deformation and wear resistance.
  • the tip of the cleaning blade was caught in a photosensitive drum, etc., stretched and cut, and the tip of the cleaning blade was sometimes damaged. These problems are particularly noticeable when the hardness of the cleaning blade is low, resulting in a lack of durability of the cleaning blade.
  • Patent Document 1 an image bearing member contact portion of a polyurethane rubber elastic blade preform is impregnated with an ultraviolet curable composition containing a (meth) acrylate compound, and the impregnated portion is immersed in a cleaning solvent. After removing the (meth) acrylate compound-containing ultraviolet curable composition remaining in the substrate, the ultraviolet curable composition impregnated in the elastic blade preform is cured by irradiation with ultraviolet rays to form an elastic blade. Has been.
  • An object of the present invention is a blade body provided in a cleaning device for removing a developer from the surface of an electrostatic latent image carrier of an electrophotographic apparatus, wherein wear of a surface layer covering a tip ridge line portion is suppressed, and a long-term
  • An object of the present invention is to provide a polyurethane base material suitable as a cleaning blade body or the like that can maintain good cleaning properties over a wide range.
  • the object of the present invention is achieved by a polyurethane base material obtained by impregnating a polyurethane rubber elastic base material with a compound having a bifunctional acrylate group and an isocyanate group or an organic solvent solution thereof.
  • This polyurethane base material can further contain a photopolymerization initiator, which can be irradiated with ultraviolet rays.
  • a highly reactive isocyanate group reacts with a polyurethane rubber elastic body as a base material. Therefore, the isocyanate compound impregnated in the rubber elastic body is bonded inside the rubber elastic body. Give very good adhesion. Moreover, by having an acrylate group, a high-strength polymer in which the acrylate group is polymerized can be formed inside and on the surface of the rubber elastic body.
  • acrylate group-containing isocyanate compound a bifunctional type acrylate group is used, and a polymer thereof having flexibility can be formed.
  • the monofunctional type has a low degree of polymerization and thus does not increase the surface hardness.
  • a trifunctional or higher functional type increases the crosslink density too much and impairs flexibility, thus causing chipping and cracking.
  • the base material is formed from a polyurethane rubber elastic body.
  • the polyurethane-based rubber is formed by reacting a bifunctional isocyanate compound and a polyol, and then adding a low-molecular polyol as a cross-linking agent, followed by heat curing.
  • the polyurethane rubber elastic body may be a thermoplastic elastomer, a millable rubber, or the like, in addition to being formed by such a method.
  • the elastic modulus of the rubber elastic body is preferably about 5 to 20 MPa. If the elastic modulus of the rubber elastic body is smaller than 5 MPa, the torque of the contacted body, that is, the photosensitive drum increases, and the effect of suppressing filming (a phenomenon in which toner adheres to the photosensitive drum) decreases. On the other hand, if the elastic modulus of the rubber elastic body is greater than 20 MPa, sufficient adhesion between the photosensitive drum and the cleaning blade body cannot be obtained.
  • the acrylate group-containing isocyanate compound has improved adhesion to the base material due to the isocyanate group content, the difference in strain between the inside of the base material and the polymer layer of the treatment agent on the base material surface is small, so cracks are unlikely to occur, and blade rubber Improve the wear resistance of the elastic body.
  • the isocyanate group has high reactivity with the NCO group and OH group derived from the raw material remaining in the polyurethane rubber elastic body.
  • the acrylate group is easily polymerized by heat or ultraviolet irradiation, and when not added, the acrylate group does not polymerize in the organic solvent, so that the shelf life of the organic solvent solution is long.
  • acrylate group-containing isocyanate compound examples include 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 2-propyl-2-isocyanate-1,3-propanediol diacrylate, and the like.
  • the lower the molecular weight of this compound the easier it is to penetrate into the polyurethane rubber elastic body, and the content of the treatment liquid polymer increases, so that the surface hardness can be increased.
  • the acrylate group-containing isocyanate compound can itself be impregnated into the substrate when its viscosity is low, but is generally used as an organic solvent solution.
  • organic solvent include organic solvents inert to acrylate groups and isocyanate groups, such as methyl ethyl ketone, acetone, tetrahydrofuran, ethyl acetate, butyl acetate, toluene, xylene and the like.
  • organic solvents have higher solubility and lower drying speed as the boiling point is lower. That is, since it is a polar solvent, the solubility of the acrylate group-containing isocyanate compound is high and the drying is fast, so that a liquid pool after coating can be prevented and a smooth surface can be formed. From this viewpoint, methyl ethyl ketone, acetone, and ethyl acetate are preferably used.
  • the concentration of the organic solvent solution is about 50% by weight or less, generally about 10-50% by weight, preferably about 20-40% by weight. If the concentration is lower than 10% by weight, the surface hardening and low friction of the blade body by the processing solution cannot be sufficiently achieved, the torque between the photoconductor and the blade body increases, and the toner aggregates on the photoconductor to cause the photosensitivity. Toner sticking occurs on the body, and filming tends to occur. On the other hand, if the concentration is higher than this, the excess treatment liquid on the surface of the blade body becomes uneven in coating, causing variations in hardness, resulting in poor cleaning due to toner slipping. In addition, the storage life of the treatment liquid is also reduced.
  • a photopolymerization initiator in the treatment liquid comprising an acrylate group-containing isocyanate compound or an organic solvent solution thereof.
  • a photopolymerization initiator intramolecular bond cleavage represented by ⁇ -decomposition of the aromatic ketone group, or intermolecular hydrogen abstraction reaction from a hydrogen donor by a photopolymerization initiator such as benzophenone, benzyl, quinone derivatives, etc.
  • a photopolymerization initiator such as benzophenone, benzyl, quinone derivatives, etc.
  • Various known ones that function are available. If no photopolymerization initiator is contained, the curing of the impregnating solution is delayed, and the indentation elastic modulus may be smaller than that of rubber.
  • Irgacure series such as Irgacure 651, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure OXE01, etc. manufactured by BASF.
  • These photopolymerization initiators are used in a proportion of about 0.5 to 15% by weight, preferably about 1 to 10% by weight in the solid content of the treatment agent depending on the kind of the photopolymerization initiator used.
  • the impregnation of the polyurethane-based rubber elastic base material with the treatment liquid is performed by immersing the whole or part of the rubber elastic base material (blade body contact portion) before being bonded to the metal fitting in the treatment liquid. After infiltration treatment for about 0.5 to 15 minutes, it is pulled up at a speed of about 100 to 1000 mm / min, for example, 500 mm / min. Drying is performed at room temperature to about 150 ° C. for about 1 to 30 minutes, for example, about 10 minutes.
  • the permeation processing time is shorter than this, the penetration depth is small, the surface hardening of the blade body and low friction cannot be sufficiently achieved, the torque between the photoconductor and the blade body increases, and the toner is transferred to the photoconductor. Aggregation causes toner sticking to occur on the photoreceptor and causes filming.
  • the permeation treatment time is longer than this, the permeation depth increases, and the treatment liquid deposited on the blade body surface after drying increases, resulting in coating unevenness.
  • the ultraviolet irradiation treatment is performed, for example, by performing ultraviolet irradiation with a UV intensity of about 10 to 50,000 mW / cm 2 at a distance of about 1 to 500 mm from the light source for about 0.5 to 20 minutes.
  • a UV intensity of about 10 to 50,000 mW / cm 2 at a distance of about 1 to 500 mm from the light source for about 0.5 to 20 minutes.
  • the surface treatment layer is formed on the surface layer portion of the rubber elastic body with a thickness of about 10 to 100 ⁇ m, preferably about 10 to 50 ⁇ m. This thickness is extremely thin, about 1/10 of the thickness of the conventional surface treatment layer, but it has high hardness, low friction, and excellent wear resistance.
  • Example 1 Production of rubber elastic body After 100 parts by weight of caprolactone-based polyol (MW2000) and 38 parts by weight of 4,4′-diphenylmethane diisocyanate [MDI] were reacted at 115 ° C. for 20 minutes, a crosslinking agent (1 , A mixture of 6.1 parts by weight of 4-butanediol and 2.6 parts by weight of trimethylolpropane), and heated for 40 minutes in a mold kept at 140 ° C. to be cured.
  • a crosslinking agent (1 , A mixture of 6.1 parts by weight of 4-butanediol and 2.6 parts by weight of trimethylolpropane
  • This rubber elastic body had an elastic modulus of 10.0 MPa.
  • Indentation elastic modulus Using a dynamic ultra-micro hardness meter manufactured by Shimadzu Corporation, In accordance with JIS Z2255 and ISO 14577, a load-unload test is performed on the surface treatment layer under conditions of a holding time of 5 seconds, a maximum test load of 0.98 N, and a load speed of 0.14 N / sec. Bending test: Bending the surface-treated rubber elastic body in two and observing the presence of cracks on the surface when it is returned.
  • Comparative Example 1 In the examples, the same amount (30 parts by weight) of 2-isocyanate ethyl acrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
  • Comparative Example 2 In the Examples, the same amount (30 parts by weight) of decyl acrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
  • Comparative Example 5 In the examples, the same amount (30 parts by weight) of dipentaerythritol hexaacrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Cleaning In Electrography (AREA)
  • Electrophotography Configuration And Component (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)

Abstract

A polyurethane base which comprises a polyurethane-based rubber elastomer base and, infiltrated thereinto, either a bifunctional compound having an acrylate group and an isocyanate group or an organic solvent solution of the compound. This polyurethane base can further contain a photopolymerization initiator and can be irradiated with ultraviolet light. These polyurethane bases are suitable for use as, for example, cleaning blades to be provided to cleaning devices for removing developers from the surfaces of the electrostatic-latent-image holders of electrophotographic devices. The cleaning blade includes an end ridge covered with a surface layer inhibited from wearing, and can retain satisfactory cleaning properties over a long period.

Description

ポリウレタン基材Polyurethane substrate
　本発明は、ポリウレタン基材に関する。さらに詳しくは、電子写真装置用クリーニングブレード体等として有効に用いられるポリウレタン基材に関する。 The present invention relates to a polyurethane base material. More specifically, the present invention relates to a polyurethane substrate that is effectively used as a cleaning blade body for an electrophotographic apparatus.
　電子写真装置には、感光ドラム、転写ベルト、中間転写体等のトナー担持体上に残留するトナーを除去するために、種々のクリーニングブレードが配設されている。これらのクリーニングブレードは、一般に熱可塑性または熱硬化性のポリウレタン系樹脂により製造されるが、塑性変形や耐摩耗性の観点から、主に熱硬化性ポリウレタン系樹脂により製造される。 In the electrophotographic apparatus, various cleaning blades are disposed in order to remove toner remaining on a toner carrier such as a photosensitive drum, a transfer belt, and an intermediate transfer member. These cleaning blades are generally made of a thermoplastic or thermosetting polyurethane resin, but are mainly made of a thermosetting polyurethane resin from the viewpoint of plastic deformation and wear resistance.
　しかしながら、ポリウレタン系樹脂よりなる従来のクリーニングブレードを用いた場合、ブレード部材と感光ドラムとの間の摩擦係数が大きくなる場合があった。この結果、ブレードのめくれや異音の発生がみられ、感光ドラムの駆動トルクを大きくしなければならない場合がみられた。 However, when a conventional cleaning blade made of a polyurethane resin is used, the friction coefficient between the blade member and the photosensitive drum may be increased. As a result, blade turning and abnormal noise were observed, and the photosensitive drum drive torque had to be increased.
　また、クリーニングブレードの先端が感光ドラム等に巻き込まれ、引き延ばされて切断され、クリーニングブレードの先端が破損する場合もあった。そして、これらの問題は、クリーニングブレードの硬度が低い場合に特に顕著になり、その結果クリーニングブレードの耐久性が不足するという結果を招いている。 Also, the tip of the cleaning blade was caught in a photosensitive drum, etc., stretched and cut, and the tip of the cleaning blade was sometimes damaged. These problems are particularly noticeable when the hardness of the cleaning blade is low, resulting in a lack of durability of the cleaning blade.
　こうした問題を解決するため、従来からポリウレタン系樹脂製クリーニングブレードの当接部を、高硬度、低摩擦にするという試みが行われている。特許文献１には、ポリウレタンゴム製弾性ブレード予備形成体の像担持体当接部に(メタ)アクリレート化合物を含む紫外線硬化性組成物を含浸させ、該含浸部分を洗浄用溶剤に浸漬し、表面に残留している(メタ)アクリレート化合物含有紫外線硬化性組成物を取り除いた後、弾性ブレード予備形成体に含浸された紫外線硬化性組成物を紫外線照射して硬化させ、弾性ブレードとする方法が記載されている。 In order to solve these problems, attempts have been made to make the contact portion of the polyurethane resin cleaning blade high in hardness and low in friction. In Patent Document 1, an image bearing member contact portion of a polyurethane rubber elastic blade preform is impregnated with an ultraviolet curable composition containing a (meth) acrylate compound, and the impregnated portion is immersed in a cleaning solvent. After removing the (meth) acrylate compound-containing ultraviolet curable composition remaining in the substrate, the ultraviolet curable composition impregnated in the elastic blade preform is cured by irradiation with ultraviolet rays to form an elastic blade. Has been.
　しかしながら、十分な表面の高硬度化を図るためには、ゴム内部への含浸に加え、表面にアクリレート重合体層の存在が必要であり、表面層が厚くなると、平滑性および柔軟性が損なわれるおそれがある。 However, in order to sufficiently increase the hardness of the surface, it is necessary to have an acrylate polymer layer on the surface in addition to impregnation into the rubber, and when the surface layer becomes thick, smoothness and flexibility are impaired. There is a fear.
特開２０１５－１５８６５４号公報Japanese Patent Laying-Open No. 2015-158654
　本発明の目的は、電子写真装置の静電潜像担持体の表面より現像剤を除去するクリーニング装置に備えられるブレード体であって、先端稜線部を覆う表面層の摩耗が抑えられ、長期間にわたり良好なクリーニング性を維持することができるクリーニングブレード体等として好適なポリウレタン基材を提供することにある。 An object of the present invention is a blade body provided in a cleaning device for removing a developer from the surface of an electrostatic latent image carrier of an electrophotographic apparatus, wherein wear of a surface layer covering a tip ridge line portion is suppressed, and a long-term An object of the present invention is to provide a polyurethane base material suitable as a cleaning blade body or the like that can maintain good cleaning properties over a wide range.
　かかる本発明の目的は、２官能性アクリレート基およびイソシアネート基を有する化合物またはその有機溶媒溶液をポリウレタン系ゴム弾性体基材に含浸させたポリウレタン基材によって達成される。このポリウレタン基材には、さらに光重合開始剤を含有せしめ、これを紫外線照射することもできる。 The object of the present invention is achieved by a polyurethane base material obtained by impregnating a polyurethane rubber elastic base material with a compound having a bifunctional acrylate group and an isocyanate group or an organic solvent solution thereof. This polyurethane base material can further contain a photopolymerization initiator, which can be irradiated with ultraviolet rays.
　アクリレート基のみを有する化合物では、基材のポリウレタン系ゴム弾性体との反応点が無く、基材との密着性が十分確保されず、基材表面に形成されたアクリレート重合体と基材との間に歪などが発生し、それがクラック発生の原因ともなる。 In a compound having only an acrylate group, there is no reaction point with the polyurethane rubber elastic body of the base material, adhesion with the base material is not sufficiently ensured, and the acrylate polymer formed on the base material surface and the base material Strain or the like is generated in between, which causes cracks.
　本発明で用いられるアクリレート基含有イソシアネート化合物は、反応性の高いイソシアネート基と基材であるポリウレタン系ゴム弾性体とが反応するため、ゴム弾性体に含浸したイソシアネート化合物はゴム弾性体内部で結合し、非常に良い密着性を与える。また、アクリレート基を有することで、アクリレート基が重合した高強度な重合体を、ゴム弾性体の内部および表面に形成することができる。 In the acrylate group-containing isocyanate compound used in the present invention, a highly reactive isocyanate group reacts with a polyurethane rubber elastic body as a base material. Therefore, the isocyanate compound impregnated in the rubber elastic body is bonded inside the rubber elastic body. Give very good adhesion. Moreover, by having an acrylate group, a high-strength polymer in which the acrylate group is polymerized can be formed inside and on the surface of the rubber elastic body.
　アクリレート基含有イソシアネート化合物としては、アクリレート基は２官能タイプのものが用いられ、柔軟性を備えたそれの重合体を形成することができる。１官能タイプのものは、重合度が低いため表面硬度が上がらない。一方、３官能以上のタイプのものでは、架橋密度が上がりすぎ、柔軟性が損なわれるため、欠けやクラックを発生させる。 As the acrylate group-containing isocyanate compound, a bifunctional type acrylate group is used, and a polymer thereof having flexibility can be formed. The monofunctional type has a low degree of polymerization and thus does not increase the surface hardness. On the other hand, a trifunctional or higher functional type increases the crosslink density too much and impairs flexibility, thus causing chipping and cracking.
　基材は、ポリウレタン系ゴム弾性体より形成される。ポリウレタン系ゴムは、２官能性イソシアネート化合物およびポリオールを反応させた後、架橋剤である低分子ポリオールを加え、加熱硬化させることにより形成される。ポリウレタン系ゴム弾性体は、このような方法で形成される以外に、熱可塑性エラストマー、ミラブルゴム等であってもよい。 The base material is formed from a polyurethane rubber elastic body. The polyurethane-based rubber is formed by reacting a bifunctional isocyanate compound and a polyol, and then adding a low-molecular polyol as a cross-linking agent, followed by heat curing. The polyurethane rubber elastic body may be a thermoplastic elastomer, a millable rubber, or the like, in addition to being formed by such a method.
　また、ゴム弾性体の弾性率は約5～20MPaであることが好ましい。ゴム弾性体の弾性率を5MPaより小さくすると、被接触体、即ち感光体ドラムのトルクが上昇し、フィルミング(トナーが感光体ドラムに付着する現象)の抑制効果が低下してしまう。一方、ゴム弾性体の弾性率を20MPaより大きくすると、感光体ドラムとクリーニングブレード体との十分な密着性が得られなくなる。 The elastic modulus of the rubber elastic body is preferably about 5 to 20 MPa. If the elastic modulus of the rubber elastic body is smaller than 5 MPa, the torque of the contacted body, that is, the photosensitive drum increases, and the effect of suppressing filming (a phenomenon in which toner adheres to the photosensitive drum) decreases. On the other hand, if the elastic modulus of the rubber elastic body is greater than 20 MPa, sufficient adhesion between the photosensitive drum and the cleaning blade body cannot be obtained.
　アクリレート基含有イソシアネート化合物は、イソシアネート基含有による基材との密着性向上により、基材内部と基材表面の処理剤の重合層との歪の差が少ないため、クラックが発生し難く、ブレードゴム弾性体の耐摩耗性を向上させる。 Since the acrylate group-containing isocyanate compound has improved adhesion to the base material due to the isocyanate group content, the difference in strain between the inside of the base material and the polymer layer of the treatment agent on the base material surface is small, so cracks are unlikely to occur, and blade rubber Improve the wear resistance of the elastic body.
　その際、２官能性アクリレート基を重合させることで、基材の内部および表面において、高強度でかつ柔軟性を備えた重合体を形成することができる。そのため、高硬度による低摩擦化が図られ、また屈曲させた状態でもクラックが発生し難いため、平滑性を保ったまま使用することができ、トナーのすり抜けなどを有効に防止することができる。 At that time, by polymerizing the bifunctional acrylate group, a polymer having high strength and flexibility can be formed inside and on the surface of the substrate. Therefore, low friction due to high hardness is achieved, and cracks are hardly generated even in a bent state, so that it can be used while maintaining smoothness, and toner slipping and the like can be effectively prevented.
　イソシアネート基は、ポリウレタン系ゴム弾性体中に残存した原料由来のNCO基およびOH基との反応性が高い。アクリレート基は、熱または紫外線照射により容易に重合し、それらを加えない場合には、有機溶媒中では重合しないため、有機溶媒溶液の保存寿命が長い。 The isocyanate group has high reactivity with the NCO group and OH group derived from the raw material remaining in the polyurethane rubber elastic body. The acrylate group is easily polymerized by heat or ultraviolet irradiation, and when not added, the acrylate group does not polymerize in the organic solvent, so that the shelf life of the organic solvent solution is long.
　アクリレート基含有イソシアネート化合物としては、例えば1,1-ビス(アクリロイルオキシメチル)エチルイソシアネート、2-プロピル-2-イソシアネート-1,3-プロパンジオールジアクリレート等が挙げられる。この化合物は、分子量が低い程ポリウレタン系ゴム弾性体内部に浸透し易く、また処理液重合体の含有量が多くなるため、表面硬度を高くすることができる。 Examples of the acrylate group-containing isocyanate compound include 1,1-bis (acryloyloxymethyl) ethyl isocyanate, 2-propyl-2-isocyanate-1,3-propanediol diacrylate, and the like. The lower the molecular weight of this compound, the easier it is to penetrate into the polyurethane rubber elastic body, and the content of the treatment liquid polymer increases, so that the surface hardness can be increased.
　アクリレート基含有イソシアネート化合物は、その粘度が低い場合にはそれ自体基材に含浸させることができるが、一般には有機溶媒溶液として用いられる。有機溶媒としては、アクリレート基およびイソシアネート基に対して不活性な有機溶媒、例えばメチルエチルケトン、アセトン、テトラヒドロフラン、酢酸エチル、酢酸ブチル、トルエン、キシレン等が挙げられる。 The acrylate group-containing isocyanate compound can itself be impregnated into the substrate when its viscosity is low, but is generally used as an organic solvent solution. Examples of the organic solvent include organic solvents inert to acrylate groups and isocyanate groups, such as methyl ethyl ketone, acetone, tetrahydrofuran, ethyl acetate, butyl acetate, toluene, xylene and the like.
　これらの有機溶媒は、低沸点である程溶解性が高く、乾燥も速い。すなわち、極性溶媒であるためアクリレート基含有イソシアネート化合物の溶解性が高く、乾燥が速いため塗布後の液溜まりを防ぎ、平滑面を形成させることができる。かかる観点から、メチルエチルケトン、アセトン、酢酸エチルが好んで用いられる。 These organic solvents have higher solubility and lower drying speed as the boiling point is lower. That is, since it is a polar solvent, the solubility of the acrylate group-containing isocyanate compound is high and the drying is fast, so that a liquid pool after coating can be prevented and a smooth surface can be formed. From this viewpoint, methyl ethyl ketone, acetone, and ethyl acetate are preferably used.
　有機溶媒溶液の濃度は、約50重量％以下、一般には約10～50重量％、好ましくは約20～40重量％である。10重量％より低い濃度では、処理液によるブレード体の表面硬化、低摩擦化が十分に達成されず、感光体とブレード体との間のトルクが上昇し、トナーが感光体に凝集して感光体上にトナー固着が発生し、フィルミングが生ずる傾向を有するようになる。一方、これ以上の濃度では、ブレード体表面の余剰分の処理液が塗布ムラとなり、硬度のバラつきを生じ、トナーのすり抜けによるクリーニング不良が発生する。また、処理液の保存寿命も低下する。 The concentration of the organic solvent solution is about 50% by weight or less, generally about 10-50% by weight, preferably about 20-40% by weight. If the concentration is lower than 10% by weight, the surface hardening and low friction of the blade body by the processing solution cannot be sufficiently achieved, the torque between the photoconductor and the blade body increases, and the toner aggregates on the photoconductor to cause the photosensitivity. Toner sticking occurs on the body, and filming tends to occur. On the other hand, if the concentration is higher than this, the excess treatment liquid on the surface of the blade body becomes uneven in coating, causing variations in hardness, resulting in poor cleaning due to toner slipping. In addition, the storage life of the treatment liquid is also reduced.
　アクリレート基含有イソシアネート化合物またはその有機溶媒溶液よりなる処理液中には、光重合開始剤を含有せしめることが好ましい。光重合開始剤としては、それの芳香族ケトン基のα-分解に代表される分子内結合切断、あるいはベンゾフェノン、ベンジル、キノン誘導体等の光重合開始剤による水素ドナーからの分子間水素引抜き反応によって機能する公知のものが、種々利用可能である。光重合開始剤を含有せしめないと、含浸液の硬化が遅くなり、押し込み弾性率がゴムよりも小さくなることがある。 It is preferable to contain a photopolymerization initiator in the treatment liquid comprising an acrylate group-containing isocyanate compound or an organic solvent solution thereof. As the photopolymerization initiator, intramolecular bond cleavage represented by α-decomposition of the aromatic ketone group, or intermolecular hydrogen abstraction reaction from a hydrogen donor by a photopolymerization initiator such as benzophenone, benzyl, quinone derivatives, etc. Various known ones that function are available. If no photopolymerization initiator is contained, the curing of the impregnating solution is delayed, and the indentation elastic modulus may be smaller than that of rubber.
　具体的には、BASF社製品イルガキュア651、イルガキュア184、イルガキュア2959、イルガキュア907、イルガキュア369、イルガキュア379、イルガキュアOXE01等のイルガキュアシリーズのものが好適に例示される。これらの光重合開始剤は、使用される光重合開始剤の種類などに応じて、処理剤固形分中の約0.5～15重量％、好ましくは約1～10重量％の割合で用いられる。 Specific examples include Irgacure series such as Irgacure 651, Irgacure 184, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure OXE01, etc. manufactured by BASF. These photopolymerization initiators are used in a proportion of about 0.5 to 15% by weight, preferably about 1 to 10% by weight in the solid content of the treatment agent depending on the kind of the photopolymerization initiator used.
　ポリウレタン系ゴム弾性体基材への処理液の含浸は、金具に接着される前のゴム弾性体基材全体または一部(ブレード体当接部)を処理液中に浸漬させることにより行われる。約0.5～15分間浸透処理後、約100～1000mm／分、例えば500mm／分の速度で引き上げる。乾燥は、室温乃至約150℃で、約1～30分間、例えば10分間程度行われる。 The impregnation of the polyurethane-based rubber elastic base material with the treatment liquid is performed by immersing the whole or part of the rubber elastic base material (blade body contact portion) before being bonded to the metal fitting in the treatment liquid. After infiltration treatment for about 0.5 to 15 minutes, it is pulled up at a speed of about 100 to 1000 mm / min, for example, 500 mm / min. Drying is performed at room temperature to about 150 ° C. for about 1 to 30 minutes, for example, about 10 minutes.
　浸透処理時間がこれより短いと、浸透深さが小さく、ブレード体の表面硬化、低摩擦化が十分に達成されず、感光体とブレード体との間のトルクが上昇し、トナーが感光体に凝集して感光体上にトナー固着が発生し、フィルミングを生ずる。一方、浸透処理時間がこれよりも長いと、浸透深さが大きくなり、乾燥後ブレード体表面に析出する処理液が多くなり、塗布ムラを生ずる。 If the permeation processing time is shorter than this, the penetration depth is small, the surface hardening of the blade body and low friction cannot be sufficiently achieved, the torque between the photoconductor and the blade body increases, and the toner is transferred to the photoconductor. Aggregation causes toner sticking to occur on the photoreceptor and causes filming. On the other hand, if the permeation treatment time is longer than this, the permeation depth increases, and the treatment liquid deposited on the blade body surface after drying increases, resulting in coating unevenness.
　紫外線照射処理は、例えばUV強度約10～50,000mW／cm2の紫外線照射を、光源からの距離約1～500mmで約0.5～20分間の照射を行うことにより行われる。かかる紫外線照射処理により、アクリレート部分の重合度が増加し、硬化するようになる。 The ultraviolet irradiation treatment is performed, for example, by performing ultraviolet irradiation with a UV intensity of about 10 to 50,000 mW / cm 2 at a distance of about 1 to 500 mm from the light source for about 0.5 to 20 minutes. By such ultraviolet irradiation treatment, the degree of polymerization of the acrylate portion is increased and cured.
　以上の工程によって、表面処理層は、ゴム弾性体の表層部に、厚さ約10～100μm、好ましくは約10～50μmで形成される。この厚さは、従来の表面処理層の厚さの約1/10と極めて薄いものであるが、高硬度で低摩擦であり、且つ耐摩耗性に優れたものとなる。 Through the above steps, the surface treatment layer is formed on the surface layer portion of the rubber elastic body with a thickness of about 10 to 100 μm, preferably about 10 to 50 μm. This thickness is extremely thin, about 1/10 of the thickness of the conventional surface treatment layer, but it has high hardness, low friction, and excellent wear resistance.
　次に、実施例について本発明を説明する。 Next, the present invention will be described with reference to examples.
　実施例
　(1) ゴム弾性体の作製
　カプロラクトン系ポリオール(MW2000)100重量部と4,4′-ジフェニルメタンジイソシアネート〔MDI〕38重量部とを、115℃で20分間反応させた後、架橋剤(1,4-ブタンジオール6.1重量部とトリメチロールプロパン2.6重量部との混合物)を加え、140℃に保たれた金型で40分間加熱し、硬化させた。 Example (1) Production of rubber elastic body After 100 parts by weight of caprolactone-based polyol (MW2000) and 38 parts by weight of 4,4′-diphenylmethane diisocyanate [MDI] were reacted at 115 ° C. for 20 minutes, a crosslinking agent (1 , A mixture of 6.1 parts by weight of 4-butanediol and 2.6 parts by weight of trimethylolpropane), and heated for 40 minutes in a mold kept at 140 ° C. to be cured.
　成形後、12.3×324×2.0mmに切断加工し、ゴム弾性体とした。このゴム弾性体は、弾性率が10.0MPaであった。 After molding, it was cut into 12.3x324x2.0mm to obtain a rubber elastic body. This rubber elastic body had an elastic modulus of 10.0 MPa.
　(2) 表面処理液の調製
　　　1,1-（ビスアクリロイルオキシメチル）　　　　　　　　　30重量部
　　　　　エチルイソシアネート
　　　ヒドロキシシクロヘキシルフェニルケトン光重合開始剤　　 3　〃　
　　　メチルエチルケトン〔MEK〕　　　　　　　　　　　　　　 67　〃　
以上の各成分を混合し、表面処理液を調製した。 (2) Preparation of surface treatment solution 1,1- (Bisacryloyloxymethyl) 30 parts by weight Ethyl isocyanate Hydroxycyclohexyl phenyl ketone photopolymerization initiator 3
Methyl ethyl ketone [MEK] 67 〃
The above components were mixed to prepare a surface treatment liquid.
　(3) ゴム弾性体の表面処理
　上記ゴム弾性体を、23℃の温度に保たれた上記表面処理液に10分間浸漬し、約500mm／分の速度で引き上げた後、UV強度400mW／cm2の紫外線照射装置を使用し、ランプ中心からの距離100mmで10分間の照射を行った。 (3) Surface treatment of rubber elastic body The rubber elastic body was immersed in the surface treatment liquid maintained at a temperature of 23 ° C. for 10 minutes, pulled up at a speed of about 500 mm / min, and then UV intensity of 400 mW / cm 2. Was used for irradiation for 10 minutes at a distance of 100 mm from the center of the lamp.
　(4) 表面処理されたゴム弾性体について、押し込み弾性率の測定および屈曲試験が行われた。
　　押し込み弾性率：島津製作所製ダイナミック超微小硬度計を用いて、
　　　　　　　　　　JIS Z2255およびISO 14577に準拠して、負荷－除荷試
　　　　　　　　　　験により、保持時間5秒間、最大試験荷重0.98N、負荷
　　　　　　　　　　速度0.14N／秒の条件下で表面処理層について測定
　　　　　　　　　　弾性率80MPa以上を○、それより少ないものを×と評
　　　　　　　　　　価
　　屈曲試験：表面処理ゴム弾性体を２つに折り曲げ、それを戻した際の表
　　　　　　　面のクラックの有無を観察
　　　　　　　クラックなしを○と評価 (4) The surface-treated rubber elastic body was subjected to indentation elastic modulus measurement and bending test.
Indentation elastic modulus: Using a dynamic ultra-micro hardness meter manufactured by Shimadzu Corporation,
In accordance with JIS Z2255 and ISO 14577, a load-unload test is performed on the surface treatment layer under conditions of a holding time of 5 seconds, a maximum test load of 0.98 N, and a load speed of 0.14 N / sec. Bending test: Bending the surface-treated rubber elastic body in two and observing the presence of cracks on the surface when it is returned.
　比較例１
　実施例において、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートの代わりに、同量(30重量部)の2-イソシアネートエチルアクリレートが用いられた。 Comparative Example 1
In the examples, the same amount (30 parts by weight) of 2-isocyanate ethyl acrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
　比較例２
　実施例において、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートの代わりに、同量(30重量部)のデシルアクリレートが用いられた。 Comparative Example 2
In the Examples, the same amount (30 parts by weight) of decyl acrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
　比較例３
　実施例において、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートの代わりに、同量(30重量部)の1,6-ヘキサンジオールジアクリレートが用いられた。 Comparative Example 3
In the examples, the same amount (30 parts by weight) of 1,6-hexanediol diacrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
　比較例４
　実施例において、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートの代わりに、同量(30重量部)のペンタエリスリトールトリアクリレートが用いられた。 Comparative Example 4
In the Examples, the same amount (30 parts by weight) of pentaerythritol triacrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
　比較例５
　実施例において、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートの代わりに、同量(30重量部)のジペンタエリスリトールヘキサアクリレートが用いられた。 Comparative Example 5
In the examples, the same amount (30 parts by weight) of dipentaerythritol hexaacrylate was used instead of 1,1-bis (acryloyloxymethyl) ethyl isocyanate.
　比較例６
　表面処理されないゴム弾性体基材について測定が行われた。 Comparative Example 6
Measurements were made on a rubber elastic substrate that was not surface treated.
　以上の実施例および各比較例での測定および試験結果は、次の表に示される。
　　　　　　　　　　　　　　　　表
　　　　　　 例 　　　押し込み弾性率(単位：MPa)　　　屈曲試験　
　　　　　実施例　　　　　128　　　評価：○　　　　　　 ○ 　
　　　　　比較例１　　　　 44　　　　　　×　　　　　　 ○ 　
　　　　　　〃　２　　　　 42　　　　　　×　　　　　　 ○ 　
　　　　　　〃　３　　　　 55　　　　　　×　　　　　　 ○ 　
　　　　　　〃　４　　　　138　　　　　　○　　　　クラックあり
　　　　　　〃　５　　　　 45　　　　　　×　　　　クラックあり
　　　　　　〃　６　　　　 30　　　　　　×　　　　　　 ○ 　 Measurements and test results in the above examples and comparative examples are shown in the following table.
Table Example indentation modulus (unit: MPa) Bending Test
Example 128 Evaluation: ○ ○
Comparative Example 1 44 × ○
〃 2 42 × ○
３ 3 55 × ○
〃 4 138 ○ Cracked 〃 5 45 × Cracked 〃 6 30 × ○

Claims (10)

  1. 　２官能性アクリレート基およびイソシアネート基を有する化合物またはその有機溶媒溶液をポリウレタン系ゴム弾性体基材に含浸させたポリウレタン基材。 A polyurethane base material obtained by impregnating a polyurethane rubber elastic base material with a compound having a bifunctional acrylate group and an isocyanate group or an organic solvent solution thereof.
  2. 　２官能性アクリレート基およびイソシアネート基を有する化合物が、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートまたは2-プロピル-2-イソシアネート-1,3-プロパンジオールジアクリレートである請求項１記載のポリウレタン基材。 The polyurethane according to claim 1, wherein the compound having a bifunctional acrylate group and an isocyanate group is 1,1-bis (acryloyloxymethyl) ethyl isocyanate or 2-propyl-2-isocyanate-1,3-propanediol diacrylate. Base material.
  3. 　さらに光重合開始剤を含有せしめた請求項１記載のポリウレタン基材。 The polyurethane substrate according to claim 1, further comprising a photopolymerization initiator.
  4. 　紫外線照射した請求項３記載のポリウレタン基材。 4. The polyurethane substrate according to claim 3, which has been irradiated with ultraviolet rays.
  5. 　ポリウレタン系ゴム弾性体の弾性率が5～20MPaである請求項１記載のポリウレタン基材。 2. The polyurethane base material according to claim 1, wherein the elastic modulus of the polyurethane rubber elastic body is 5 to 20 MPa.
  6. 　有機溶媒溶液の濃度が50重量％以下である請求項１記載のポリウレタン基材。 2. The polyurethane substrate according to claim 1, wherein the concentration of the organic solvent solution is 50% by weight or less.
  7. 　有機溶媒溶液の濃度が10～50重量％である請求項６記載のポリウレタン基材。 The polyurethane substrate according to claim 6, wherein the concentration of the organic solvent solution is 10 to 50% by weight.
  8. 　含浸が0.5～15分間の浸透処理により行われた請求項１記載のポリウレタン基材。 2. The polyurethane base material according to claim 1, wherein the impregnation is performed by an infiltration treatment for 0.5 to 15 minutes.
  9. 　ゴム弾性体の表層部に厚さ10～100μmの表面処理層が形成された請求項１記載のポリウレタン基材。 2. The polyurethane base material according to claim 1, wherein a surface treatment layer having a thickness of 10 to 100 μm is formed on a surface layer portion of the rubber elastic body.
  10. 　電子写真装置用クリーニングブレード体として用いられる請求項１、４または９記載のポリウレタン基材。 The polyurethane substrate according to claim 1, 4 or 9, which is used as a cleaning blade body for an electrophotographic apparatus.
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JP2004280086A (en) * 2003-02-28 2004-10-07 Canon Chemicals Inc Method for manufacturing cleaning blade, cleaning blade manufactured by same manufacturing method, and electrophotographic device having same cleaning blade built in
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JP2021509921A (en) * 2018-11-28 2021-04-08 深▲せん▼創怡興実業有限公司Ｓｈｅｎｚｈｅｎ Ｆａｎｃｙ Ｃｒｅａｔｉｏｎ Ｉｎｄｕｓｔｒｉａｌ Ｌｉｍｉｔｅｄ Rubber scraper and its manufacturing method
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