Fixing member, method for manufacturing a fixing member, fixing apparatus, and image forming apparatus
Patent Information
- Application Number
- JP2025010957
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2025-01-24
- Publication Date
- 2026-10-01
- Estimated Expiration
- 2045-01-24
AI Technical Summary
【0007】 <1>に係る発明によれば、(A)成分および(B)成分を含む付加硬化性オルガノポリシロキサン組成物の付加硬化物を含む表層を有する定着部材において、(A)成分が、0.2≦b≦0.9、若しくは0.1≦(c+e+g)≦0.8を満足しない場合、(B)成分の含有量が10質量部未満若しくは300質量部超えである場合、表層の弾性率EAが10MPa未満若しくは200MPa超えである場合、又は表層の弾性率EBが20MPa未満若しくは100MPa超えである場合に比べ、高温離型性及び柔軟性の維持性に優れた表層を有する定着部材が提供される。
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Abstract
Description
[Technical Field]
[0001] The present invention relates to a fixing member, a method for manufacturing a fixing member, a fixing apparatus, and an image forming apparatus. [Background technology]
[0002] In image forming devices using the electrophotographic method (such as photocopiers, facsimile machines, and printers), a toner image formed on the surface of an image holder is transferred to the surface of a recording medium and fixed onto the recording medium to form an image.
[0003] For example, Patent Document 1 discloses "a fixing belt having an elastic layer made of heat-resistant rubber and a surface layer sequentially on a substrate, wherein an elastic layer of silicone rubber having 1 to 35% by weight of iron oxide containing 80% or more ferric oxide is provided on a sheet or endless belt made of a metal material such as stainless steel or nickel, or a heat-resistant resin such as polyimide or polyamide-imide, and a fluororesin is formed on the surface layer." Patent Document 1 discloses that the above configuration "provides a fixing belt that has appropriate flexibility and excellent toner release properties, durability and running stability, as well as an image forming apparatus having the same." [Prior art documents] [Patent Documents]
[0004] [Patent Document 1] Japanese Patent Publication No. 2002-268423 [Overview of the Initiative] [Problems that the invention aims to solve]
[0005] The object of the present invention is to provide a fixing member having a surface layer containing an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B), where, if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and the content of component (B) is less than 50 parts by mass or more than 300 parts by mass, the elastic modulus E of the surface layer A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B The objective is to provide a fixing member having a surface layer that exhibits superior high-temperature release properties and flexibility retention compared to cases where the pressure is less than 20 MPa or more than 100 MPa. [Means for solving the problem]
[0006] The means for solving the above problems include the following embodiments. <1> Having a base material and a surface layer, The aforementioned surface layer is (A) Organopolysiloxane resin having a constituent unit represented by the following formula (1), [ka] (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 2 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms (however, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%. 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0≦a≦0.6, 0.2≦b≦0.9, 0≦c≦0.8, 0≦d≦0.6, 0≦e≦0.8, 0≦f≦0.6, 0≦g≦0.8, and 0.1≦(c+e+g)≦0.8 and a+b+c+d+e+f+g=1, and h is a number satisfying 0≦h≦1. (B) Linear organopolysiloxane represented by the following formula (2) [Chemical Formula] (In formula (2), each R 4 independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, and each R 5 independently represents a hydrogen atom or an alkenyl group having 2 to 12 carbon atoms, and each R 6 independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms, and n is an integer of 0 to 1,200.) comprises an addition-cured product of an addition-curable organopolysiloxane composition containing the content of component (B) is 10 parts by mass or more and 300 parts by mass or less relative to 100 parts by mass of component (A), the elastic modulus E of the surface layer at 140°C A is 10 MPa or more and 200 MPa or less, after being left to heat at 200°C for 48 hours in an oxygen atmosphere, the elastic modulus E of the surface layer at 140°C B is 20 MPa or more and 100 MPa or less, fixing member. <2> (A) An organopolysiloxane resin having a constitutional unit represented by the following formula (1) [Chemical Formula] (In formula (1), each R 1 independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms and containing no aliphatic unsaturated bonds, and each R 2 independently represents a hydrogen atom or an alkenyl group having 2 to 12 carbon atoms (provided that the proportion of the number of hydrogen atoms in the total number of R 2 is 10 mol% or more and 90 mol% or less), R 3Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0≦a≦0.6, 0.2≦b≦0.9, 0≦c≦0.8, 0≦d≦0.6, 0≦e≦0.8, 0≦f≦0.6, 0≦g≦0.8, and 0.1≦(c+e+g)≦0.8 and a+b+c+d+e+f+g=1, and h is a number satisfying 0≦h≦1. (B) Linear organopolysiloxane represented by the following formula (2) [ka] (In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 5 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, and R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer between 0 and 1,200. and (C) Platinum group metal catalyst The process includes applying an addition-curable organopolysiloxane composition containing the above onto a substrate and curing it to form a surface layer. The content of component (B) in the composition is 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of component (A), The elastic modulus E of the surface layer at 140°C A However, the pressure is between 10 MPa and 200 MPa. The elastic modulus E of the surface layer at 140°C after being heated and left in an oxygen atmosphere at 200°C for 48 hours. B However, it is between 20 MPa and 100 MPa. A method for manufacturing a fixing member. <3> The content of component (C) relative to 100 parts by mass of component (A) is 0.00001 parts by mass or more and 0.005 parts by mass or less, based on the mass equivalent to platinum group metal atoms. <2> A method for manufacturing the fixing member described above. <4> The aforementioned R 1However, it is a methyl group or a phenyl group, and the R 2 The alkenyl group in this case is a vinyl group. <1> The fixing member described above. <5> The above a is 0. <1> or <4> The fixing member described above. <6> The above g is 0. <1> , <4> or <5> The fixing member described above. <7> The above c, e, and g are numbers that satisfy 0 ≤ c ≤ 0.4, 0.1 ≤ e ≤ 0.5, 0 ≤ g ≤ 0.4, and 0.1 ≤ (c + e + g) ≤ 0.8. <1> , or <4> ~ <6> A fixing member as described in any one of the items. <8> The alkenyl group content in component (A) is 0.05 mol / 100g or more and 0.6 mol / 100g or less. <1> , or <4> ~ <7> A fixing member as described in any one of the items. <9> The weight-average molecular weight (Mw) of component (A) in terms of polystyrene, as measured by gel permeation chromatography, is between 1,000 and 50,000. <1> , or <4> ~ <8> A fixing member as described in any one of the items. <10> The aforementioned R 4 However, it is a methyl group, and the R 5 However, it is a hydrogen atom, and the R 6 However, it is a methyl group. <1> , or <4> ~ <9> A fixing member as described in any one of the items. <11> The number of hydrogen atoms bonded to the silicon atoms in the addition-curable organopolysiloxane composition is 0.8 or more and 2.0 or less per alkenyl group bonded to the silicon atoms in the addition-curable organopolysiloxane composition. <1> , or <4> ~ <10> A fixing member as described in any one of the items. <12> The aforementioned surface layer further contains carbon <1> , or <4> ~ <11> A fixing member as described in any one of the items. <13> It comprises a first rotating body and a second rotating body positioned in contact with the outer surface of the first rotating body, At least one of the first rotating body and the second rotating body is <1> , or <4> ~ <12> A fixing device which is a fixing member described in any one of the items. <14> Image holder and, A charging device for charging the surface of the image holder, An electrostatic latent image forming apparatus for forming an electrostatic latent image on the surface of the charged image holder, A developing apparatus that develops an electrostatic latent image formed on the surface of the image holder with toner to form a toner image, A transfer device for transferring a toner image formed on the surface of the image holder to a recording medium, The toner image is fixed onto the recording medium. <13> The fixing device described above, An image forming apparatus having [Effects of the Invention]
[0007] <1> According to the invention relating to the present invention, in a fixing member having a surface layer containing an addition cured product of an addition curable organopolysiloxane composition containing component (A) and component (B), if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B Compared to cases where the pressure is less than 20 MPa or more than 100 MPa, a fixing member is provided having a surface layer with superior high-temperature release properties and flexibility retention.
[0008] <2> According to the invention relating to the present invention, in a method for manufacturing a fixing member, the step of applying an addition-curable organopolysiloxane composition containing component (A), component (B), and component (C) onto a substrate and curing it to form a surface layer, if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and if the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E BA method for manufacturing a fixing member having a surface layer with superior high-temperature release properties and flexibility retention is provided, compared to cases where the pressure is less than 20 MPa or more than 100 MPa.
[0009] <3> According to the invention, a fixing member is provided having a surface layer that exhibits superior high-temperature release properties and flexibility retention compared to cases where the content of component (C) per 100 parts by mass of component (A) is less than 0.00001 parts by mass or more than 0.005 parts by mass on a mass basis converted to platinum group metal atoms. <4> According to the invention relating to R 1 If R is a group other than a methyl group and a phenyl group, 2 Compared to cases where the alkenyl group is a group other than a vinyl group, a fixing member is provided having a surface layer with superior high-temperature release properties and flexibility retention. <5> According to the invention, a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where a is greater than 0. <6> According to the invention, a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where g is greater than 0. <7> According to the invention relating to this, a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where c, e, and g do not satisfy the above formula. <8> According to the invention, a fixing member is provided having a surface layer that exhibits superior high-temperature release properties and flexibility retention compared to cases where the alkenyl group content in component (A) is less than 0.05 mol / 100g or greater than 0.6 mol / 100g. <9> According to the invention, a fixing member is provided having a surface layer that exhibits superior high-temperature release properties and flexibility retention compared to cases where the weight-average molecular weight (Mw) of component (A) in terms of polystyrene in gel permeation chromatography is less than 1,000 or more than 50,000. <10> According to the invention relating to R 4 If R is a group other than a methyl group, 5 If R is a group other than a hydrogen atom, 6Compared to cases where the group is not a methyl group, a fixing member is provided having a surface layer that exhibits superior high-temperature release properties and flexibility retention. <11> According to the invention, a fixing member is provided having a surface layer with superior high-temperature release properties and flexibility retention compared to cases where the number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition is less than 0.8 or more than 2.0 per alkenyl group bonded to silicon atoms in the addition-curable organopolysiloxane composition. <12> According to the invention relating to the present invention, in a fixing member having a surface layer containing an addition cured product of an addition curable organopolysiloxane composition containing component (A) and component (B), if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B Compared to cases where the pressure is less than 20 MPa or more than 100 MPa, a fixing member is provided that has a surface layer containing carbon, which is excellent in maintaining high temperature release properties and flexibility.
[0010] <13> , or <14> According to the invention relating to the present invention, in a fixing member having a surface layer containing an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B), when a fixing member is applied in which component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, when a fixing member is applied in which the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus E of the surface layer A When an anchoring member with a coefficient of elasticity less than 10 MPa or greater than 200 MPa is applied, or when the elastic modulus of the surface layer E B Compared to cases where a fixing member with a pressure of less than 20 MPa or more than 100 MPa is used, a fixing device or image forming apparatus is provided that has a fixing member having a surface layer with superior high-temperature release properties and flexibility retention. [Brief explanation of the drawing]
[0011] [Figure 1]This is a schematic diagram showing an example of a fixing device according to the first embodiment. [Figure 2] This is a schematic diagram showing an example of a fixing device according to the second embodiment. [Figure 3] This is a schematic diagram showing an example of a fixing device according to the third embodiment. [Figure 4] This is a schematic diagram showing an example of a fixing device according to the fourth embodiment. [Figure 5] This is a schematic diagram showing an example of a fixing device according to the fifth embodiment. [Figure 6] This is a schematic diagram showing an example of a fixing device according to the sixth embodiment. [Figure 7] This is a schematic diagram showing an example of an image forming apparatus according to this embodiment. [Modes for carrying out the invention]
[0012] The following describes an embodiment that is an example of the present invention. These descriptions and examples are illustrative of embodiments and do not limit the scope of the embodiments.
[0013] In the numerical ranges described in stages within this embodiment, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in the numerical ranges described within this embodiment, the upper or lower limit of that range may be replaced with the values shown in the examples. In this embodiment, the term "process" includes not only independent processes but also any process that cannot be clearly distinguished from other processes, as long as its intended purpose is achieved. In this embodiment, when describing embodiments with reference to the drawings, the configuration of the embodiment is not limited to the configuration shown in the drawings. Furthermore, the sizes of the members in each figure are conceptual, and the relative relationships between the sizes of the members are not limited thereto. In this embodiment, each component may contain multiple types of the corresponding substance. In this embodiment, when referring to the amount of each component in the composition, if there are multiple types of the substance corresponding to each component in the composition, unless otherwise specified, it refers to the total amount of those multiple types of substances present in the composition.
[0014] <Fixing material> The fixing member according to this embodiment has a base material and a surface layer. The surface layer comprises (A) an organopolysiloxane resin having structural units represented by formula (1), and (B) an addition-cured product of an addition-curable organopolysiloxane composition containing a linear organopolysiloxane represented by formula (2). The content of component (B) per 100 parts by mass of component (A) is between 10 parts by mass and 300 parts by mass. Elastic modulus E of the surface layer at 140℃ A The pressure is between 10 MPa and 200 MPa. The elastic modulus E of the surface layer at 140°C after heating at 200°C for 48 hours in an oxygen atmosphere. B The pressure is between 20 MPa and 100 MPa.
[0015] The fixing member according to this embodiment, with the above configuration, is a fixing member having a surface layer that is excellent in high-temperature release properties and maintenance of flexibility. The reason for this is presumed to be as follows.
[0016] In fixing members, the surface layer is required to have high-temperature release properties. Conventionally, fluororesins such as tetrafluoroethylene perfluoroalkyl vinyl ether copolymer (PFA) have been used as materials to achieve high-temperature release properties in the surface layer.
[0017] Fluororesins are relatively less elastic than rubber materials. In other words, surface layers to which fluororesins are applied have low flexibility. As a result, they have poor conformability to the unevenness of the recording medium's surface, leading to uneven pressure and temperature distribution during fixing in recessed areas. These unevennesses cause the toner image to adhere to the surface of the fixing member (hereinafter also referred to as "offset").
[0018] In contrast, the use of rubber materials such as silicone rubber and fluororubber has been proposed as flexible materials. However, surface layers using rubber materials exhibit insufficient high-temperature release properties, even at the initial adhesion level of tens to hundreds of layers. In addition, repeated heating leads to a decrease in flexibility.
[0019] Therefore, the fixing member according to this embodiment applies an addition-cured product of an addition-curable organopolysiloxane composition containing specific amounts of component (A) and component (B) as the material for the surface layer, and the elastic modulus E of the surface layer A and E B Control it within the above range. The above addition-cured material has three-dimensional cross-linked polysiloxane moieties and linear polysiloxane moieties, and is characterized by an excellent balance of hardness and flexibility. Therefore, by incorporating the above addition-cured material, the elastic modulus of the surface layer E A and E B A surface layer whose properties are controlled within the above range possesses both release properties at high temperatures and flexibility, and also exhibits high maintenance.
[0020] From the above, it is presumed that the fixing member according to this embodiment will be a fixing member having a surface layer that is excellent in terms of high-temperature release properties and maintenance of flexibility.
[0021] The details of the fixing member according to this embodiment will be described below.
[0022] The fixing member according to this embodiment has a base material and a surface layer. A functional layer, such as an elastic layer or a metal layer, may be provided between the base material and the surface layer. Specifically, the fixing member according to this embodiment is a fixing member having the following layer configuration. (1) A fixing member having a layered structure in which the base material and the surface layer are provided in this order. (2) A fixing member having a layered structure in which a base material, an elastic layer, and a surface layer are provided in this order. (3) Fixing member having a layered structure in which a base material, a metal layer, an elastic layer, and a surface layer are provided in this order.
[0023] Furthermore, an intermediate layer may be provided between the elastic layer and the surface layer. Also, an adhesive layer may be provided between each layer (including the base material).
[0024] The fixing member according to this embodiment may be in the shape of a roll or a belt.
[0025] (base material) Examples of base materials include cylindrical base materials composed of metals (aluminum, stainless steel, iron, copper, etc.), alloys, ceramics, FRM (fiber-reinforced metal), etc. The outer diameter and wall thickness of the cylindrical base material should, for example, be between 10 mm and 50 mm in outer diameter. In the case of an aluminum cylindrical base material, the thickness should be, for example, between 0.5 mm and 4 mm, and in the case of a SUS (stainless steel) or iron cylindrical base material, the thickness should be, for example, between 0.1 mm and 2 mm.
[0026] Examples of base materials include metal belts and heat-resistant resin belts. Examples of metal belts include those made of nickel, aluminum, and stainless steel. Examples of heat-resistant resin belts include those made from polyimide, polyamide-imide, polyphenylene sulfide, polyetheretherketone, and polybenzimidazole. Furthermore, the heat-resistant resin belt may have its volume resistivity controlled by adding conductive powder or the like. Specifically, an example of a resin belt is a polyimide resin belt in which carbon black is dispersed. Another example of a heat-resistant resin belt is a resin belt made by combining the ends of a long polyimide sheet in a puzzle-like fashion and heat-pressing the combined parts together. Heat resistance refers to the property of not melting or decomposing even when the temperature of the fixing device is reached (for example, the fixing temperature).
[0027] The thickness of the belt base material is preferably, for example, 20 μm to 200 μm, more preferably 30 μm to 150 μm, and even more preferably 40 μm to 130 μm.
[0028] (metal layer) The metal layer has at least a metal heating layer. The metal layer may also have at least one of a base metal layer provided on the inner circumferential surface of the metal heating layer and a metal protective layer provided on the outer circumferential surface of the metal heating layer.
[0029] The base metal layer is a layer that is formed in advance on the outer surface of the substrate in order to form a metal heating layer by electroplating. Examples of the base metal layer include electroless nickel plating layers and electroless copper plating layers. Note that "nickel plating layer" refers to a plating layer containing Ni (e.g., a nickel layer, a nickel alloy layer, etc.), and "copper plating layer" refers to a plating layer containing Cu (e.g., a copper layer, a copper alloy layer, etc.). A metal heating layer is a heating layer that generates heat through eddy currents that occur within the layer when a magnetic field is applied, and is composed of a metal that exhibits electromagnetic induction. Examples of metals that exhibit electromagnetic induction include single metals such as nickel, iron, copper, gold, silver, aluminum, chromium, tin, and zinc, or alloys containing two or more types of metals. The metal protective layer is provided in contact with the metal heating layer to improve the film strength of the metal heating layer, suppress cracking due to repeated deformation and oxidative degradation due to repeated heating over long periods, and maintain the heating characteristics. The metal protective layer is preferably a thin film with high tensile strength, high durability and oxidation resistance, and preferably an oxide-resistant metal. Specifically, it is often composed of copper or nickel, and in particular, it is preferable to include nickel (or a nickel alloy), which is an oxide-resistant metal, from the viewpoint of suppressing the occurrence of cracks due to repeated deformation and oxidative degradation due to repeated heating.
[0030] (Elastic layer) The elastic layer is preferably a layer that returns to its original shape even when deformed by an external force of 1 MPa. The elastic layer contains a heat-resistant elastic material. Heat resistance refers to the property of not melting or decomposing even when the temperature of the fixing device is raised (e.g., the fixing temperature).
[0031] A typical example of a heat-resistant elastic material is silicone rubber. Examples of silicone rubber include RTV silicone rubber, HTV silicone rubber, and liquid silicone rubber. Specifically, examples include polydimethyl silicone rubber (MQ), methyl vinyl silicone rubber (VMQ), methylphenyl silicone rubber (PMQ), and fluorosilicone rubber (FVMQ).
[0032] As for the silicone rubber, those with an addition reaction type as the crosslinking mechanism are preferred. Furthermore, various types of functional groups are known for silicone rubber, and dimethyl silicone rubber having methyl groups, methylphenyl silicone rubber having methyl and phenyl groups, and vinyl silicone rubber having vinyl groups (vinyl group-containing silicone rubber) are preferred. Furthermore, as the silicone rubber, vinyl silicone rubber having vinyl groups is more preferred, and silicone rubber having an organopolysiloxane structure having vinyl groups and a hydrogen organopolysiloxane structure having hydrogen atoms (SiH) bonded to silicon atoms is even more preferred.
[0033] The elastic layer may be a foamed elastic layer or a non-foamed elastic layer. However, from the viewpoint of improving adhesion, when the fixing member is applied to a heating member, a non-foamed elastic layer is preferred. On the other hand, from the viewpoint of energy saving, when the fixing member is applied to a pressurizing member, a foamed elastic layer is preferred.
[0034] The elastic layer may contain other additives. Examples of other additives include fillers, conductive agents, softeners (paraffin-based, etc.), processing aids (stearic acid, etc.), antioxidants (amine-based, etc.), and vulcanizing agents (sulfur, metal oxides, peroxides, etc.).
[0035] When the fixing member is a fixing belt, the thickness of the elastic layer is preferably, for example, 30 μm or more and 600 μm or less, and more preferably 100 μm or more and 500 μm or less. When the fixing member is a fixing roll, the thickness of the elastic layer is preferably, for example, 50 μm or more and 7 mm or less, and more preferably 100 μm or more and 5 mm or less.
[0036] (surface) The surface layer contains an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B).
[0037] -(A) component- Component (A) is an organopolysiloxane resin having a constituent unit represented by the following formula (1). [ka] (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 2 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms (however, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%. 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. a, b, c, d, e, f, and g are numbers satisfying the following inequalities: 0 ≤ a ≤ 0.6, 0.2 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.6, 0 ≤ e ≤ 0.8, 0 ≤ f ≤ 0.6, 0 ≤ g ≤ 0.8, and 0.1 ≤ (c + e + g) ≤ 0.8 and a + b + c + d + e + f + g = 1. h is a number satisfying 0 ≤ h ≤ 1.
[0038] In formula (1), R 1 The monovalent hydrocarbon group represented is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, R 1Examples of monovalent hydrocarbon groups represented by include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl and tolyl groups; and aralkyl groups such as benzyl and phenethyl groups. R 1 Examples of monovalent hydrocarbon groups represented by include substituted alkyl groups, substituted cycloalkyl groups, substituted aryl groups, or substituted aralkyl groups, in which some or all of the hydrogen atoms of an alkyl group, cycloalkyl group, aryl group, or aral group are substituted with substituents such as halogen atoms.
[0039] R 1 As the monovalent hydrocarbon group represented by R, methyl and phenyl groups are preferred from the viewpoint of improving high-temperature release properties. 1 It is preferable that this is a methyl group or a phenyl group.
[0040] In formula (1), R 2 The alkenyl group represented by is preferably an alkenyl group having 2 to 10 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms. Specifically, R 2 Examples of alkenyl groups represented by include vinyl, allyl, butenyl, pentenyl, and hexenyl groups. In particular, R 2 From the viewpoint of ease of synthesis and cost, the alkenyl group represented is preferably a vinyl group.
[0041] Here, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%. As a result, the composition has excellent curability, and the resulting addition-cured product has excellent mechanical properties, thereby improving the high-temperature release properties and flexibility of the surface layer. R 2 The proportion of hydrogen atoms in the total number of atoms is preferably 20 mol% to 80 mol%, and more preferably 30 mol% to 70 mol%.
[0042] R 2 The proportion of hydrogen atoms in the total number of (A) components is1 It can be calculated from the integral value of the signals originating from alkenyl groups bonded to silicon atoms and hydrogen atoms bonded to silicon atoms in the 1H-NMR (Nuclear Magnetic Resonance) spectrum.
[0043] In formula (1), R 3 The alkyl group represented is preferably an alkyl group having 1 to 3 carbon atoms. R 3 Examples of alkyl groups represented by include methyl, ethyl, propyl, and butyl groups. From the viewpoint of improving high-temperature release properties, R 3 The alkyl group represented is preferably a methyl group.
[0044] In formula (1), it is preferable that a, b, c, d, e, f, g, and h satisfy the following conditions from the viewpoint of improving the high-temperature release properties and flexibility of the surface layer.
[0045] It is preferable that a satisfies 0 ≤ a ≤ 0.3, and more preferably that a is 0. b preferably satisfies 0.2 ≤ b ≤ 0.7, and more preferably 0.3 ≤ b ≤ 0.6. c preferably satisfies 0 ≤ c ≤ 0.4, and more preferably is 0. It is preferable that d satisfies 0 ≤ d ≤ 0.5, and more preferably that d satisfies 0 ≤ d ≤ 0.4. e preferably satisfies 0.1 ≤ e ≤ 0.5, and more preferably satisfies 0.1 ≤ e ≤ 0.3. It is preferable that f satisfies 0.1 ≤ f ≤ 0.4, and more preferably that f satisfies 0.1 ≤ f ≤ 0.2. g preferably satisfies 0 ≤ g ≤ 0.4, and more preferably 0. It is preferable that h satisfies 0 ≤ h ≤ 0.2, and more preferably that it satisfies 0 ≤ h ≤ 0.1.
[0046] It is preferable that 0.1 ≤ (c + e + g) ≤ 0.5 is satisfied, and it is more preferable that 0.1 ≤ (c + e + g) ≤ 0.3 is satisfied.
[0047] Here, in equation (1), c, e, and g are preferably numbers that satisfy 0 ≤ c ≤ 0.4, 0.1 ≤ e ≤ 0.5, 0 ≤ g ≤ 0.4, and 0.1 ≤ (c + e + g) ≤ 0.8.
[0048] In particular, in equation (1), a, b, c, d, e, f and g are, a=0, 0.3 ≤ b ≤ 0.6, c=0, 0≦d≦0.4, 0.1 ≤ e ≤ 0.3, 0.1 ≤ f ≤ 0.2, g=0 and a+b+c+d+e+f+g=1, It is preferable that h is a number that satisfies 0 ≤ h ≤ 0.1.
[0049] (A) The alkenyl group content of component (A) is preferably 0.05 mol / 100g or more and 0.6 mol / 100g or less, and more preferably 0.1 mol / 100g or more and 0.3 mol / 100g or less, from the viewpoint of the curability of the composition. Improved curability of the composition makes it easier for the surface layer to exhibit its functions (i.e., high-temperature release properties and maintenance of flexibility). The alkenyl group content is, 1 H-NMR and 29 It can be calculated from the average structure of component (A), which is obtained from the integral value of the Si-NMR detection spectrum.
[0050] (A) The weight-average molecular weight (Mw) of component (A) in terms of polystyrene in gel permeation chromatography is preferably 1,000 to 50,000, and more preferably 5,000 to 20,000, from the viewpoint of the storage stability of the composition and the ability to form a film. By improving the storage stability and film-forming properties of the composition, the surface function (i.e., high-temperature release properties and maintenance of flexibility) is more easily exhibited.
[0051] (A) The weight-average molecular weight (Mw) of component is the value measured under the following conditions: -Measurement Conditions for Weight Average Molecular Weight (Mw)- Apparatus: HLC-8220 (manufactured by Tosoh Corporation) Columns: TSKgel GMHXL-L, TSKgel G4000HXL, TSKgel G2000HXL ×2 Developing solvent: Tetrahydrofuran (THF) Flow rate: 1 mL / min Detector: RI Column thermostatic chamber temperature: 40°C Standard sample for molecular weight calibration curve: Monodisperse polystyrene standard sample
[0052] Specific examples of component (A) are as follows, but are not limited thereto. Note that Me represents a methyl group, Ph represents a phenyl group, and Vi represents a vinyl group (the same applies hereinafter). (MeSiO 3 / 2 ) 0.5 (MeViSiO 2 / 2 ) 0.15 (MeHSiO 2 / 2 ) 0.15 (Me3SiO 1 / 2 ) 0.2 (HO 1 / 2 ) 0.02 (PhSiO 3 / 2 ) 0.5 (MeViSiO 2 / 2 ) 0.15 (MeHSiO 2 / 2 ) 0.15 (Me3SiO 1 / 2 ) 0.2 (HO 1 / 2 ) 0.02 (SiO 4 / 2 ) 0.1 (MeSiO 3 / 2 ) 0.43 (MeViSiO 2 / 2 ) 0.15 (MeHSiO 2 / 2 ) 0.15 (Me3SiO 1 / 2 ) 0.17 (HO 1 / 2 ) 0.02
[0053] The synthesis method for component (A) can be, for example, according to the method described in Japanese Patent Publication No. 2020-111657, and is obtained by hydrolyzing and condensing a chlorosilane and / or alkoxysilane, or a partially hydrolyzed condensate thereof, which can form siloxane units constituting the polysiloxane resin represented by formula (1) above by hydrolysis and condensation, in an organic solvent capable of dissolving the raw material silane compound and the resulting polysiloxane resin under acidic conditions. To obtain a polysiloxane with a desired weight-average molecular weight, it is possible to adjust the monomer mixing ratio, reaction temperature and time, and the amounts of water and organic solvent used. The polysiloxane resin (component (A)) produced in this manner is subjected to the removal of organic solvents as needed, and precipitates are removed by filtration.
[0054] -(B) Component- Component (B) is a linear organopolysiloxane represented by the following formula (2). [ka] In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 5 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, and R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer from 0 to 1,200.
[0055] In formula (2), R 4 The monovalent hydrocarbon group represented by is R in formula (1). 1 This is synonymous with the monovalent hydrocarbon group represented by , and the preferred range is also the same. In formula (2), R 5 The alkenyl group represented by is R in formula (1). 2 This is synonymous with the alkenyl group represented by , and the preferred range is also the same. However, from the viewpoint of improving high-temperature release properties and flexibility, in formula (2), R 4 It is a methyl group, and R 5It is preferable that it be a hydrogen atom.
[0056] In formula (2), R 6 The monovalent hydrocarbon group represented is preferably a monovalent hydrocarbon group having 1 to 10 carbon atoms, and more preferably a monovalent hydrocarbon group having 1 to 8 carbon atoms. Specifically, R 6 Examples of monovalent hydrocarbon groups represented by include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl and tolyl groups; aralkyl groups such as benzyl and phenethyl groups; and alkenyl groups such as vinyl, allyl, butenyl, pentenyl, and hexenyl groups. R 6 From the viewpoint of improving high-temperature release properties, the monovalent hydrocarbon group represented is preferably a methyl group or a vinyl group, with the methyl group being more preferred.
[0057] In equation (2), n is preferably an integer between 0 and 1,000, and more preferably between 10 and 1,000.
[0058] (B) The alkenyl group content of component (B) is preferably 0 mol / 100g or more and 1.0 mol / 100g or less, and more preferably 0 mol / 100g or more and 0.2 mol / 100g or less, from the viewpoint of the curability of the composition and the flexibility of the cured product. By improving the curability of the composition and the flexibility of the cured product, the functions of the surface layer (i.e., high-temperature release properties and maintenance of flexibility) are more easily exhibited. (B) The weight-average molecular weight (Mw) of component (B) in terms of polystyrene in gel permeation chromatography is preferably 100 to 100,000, and more preferably 500 to 80,000, from the viewpoint of the storage stability of the composition and the ability to form a film. By improving the storage stability of the composition and the ability to form a film, the functions of the surface layer (i.e., high-temperature release properties and maintenance of flexibility) are more easily exhibited.
[0059] The method for measuring the alkenyl group content and weight-average molecular weight (Mw) of component (B) is the same as the method for measuring the alkenyl group content and weight-average molecular weight (Mw) of component (A).
[0060] (B) Specific examples of component are as follows, but are not limited to these. HMe2SiO-(Me2SiO) 10 -SiMe2H HMe2SiO-(Me2SiO) 20 -SiMe2H HMe2SiO-(Me2SiO) 40 -SiMe2H HMe2SiO-(Me2SiO) 400 -SiMe2H HMe2SiO-(Me2SiO) 1000 -SiMe2H ViMe2SiO-(Me2SiO) 10 -SiMe2Vi ViMe2SiO-(Me2SiO) 20 -SiMe2Vi ViMe2SiO-(Me2SiO) 40 -SiMe2Vi ViMe2SiO-(Me2SiO) 400 -SiMe2Vi ViMe2SiO-(Me2SiO) 1000 -SiMe2Vi Vi3SiO-(Me2SiO) 10 -SiVi3 Vi3SiO-(Me2SiO) 20 -SiVi3 Vi3SiO-(Me2SiO) 40 -SiVi3 Vi3SiO-(Me2SiO) 400 -SiVi3 Vi3SiO-(Me2SiO) 1000 -SiVi3
[0061] Component (B) can be synthesized by known methods. For example, component (B) can be obtained by equilibration polymerization using a cyclic siloxane such as octamethylcyclotetrasiloxane and an end-capturing agent such as 1,1,3,3-tetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, or hexavinyldisiloxane as raw materials, in the presence of an acid catalyst such as sulfuric acid, trifluoromethanesulfonic acid, or methanesulfonic acid. If an acid is used as a catalyst, the acid can be removed, for example, by washing with water. A solvent may also be used in the above equilibration reaction, in which case the solvent can be removed by vacuum distillation.
[0062] -Content of components (A) to (B), and the addition cured product of the addition-curable organopolysiloxane composition- The content of components (A) and (B) shall be as follows, from the viewpoint of improving high-temperature release properties and flexibility. Component (A) is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 85% by mass or less, relative to the solid content of the addition-curable organopolysiloxane composition. The content of component (B) per 100 parts by mass of component (A) is 10 parts by mass or more and 300 parts by mass or less, preferably 25 parts by mass or more and 250 parts by mass or less, and more preferably 30 parts by mass or more and 200 parts by mass or less.
[0063] Here, the content of the addition-cured product in the addition-curable organopolysiloxane composition is preferably 70% by mass or less, more preferably 80% by mass or less, and even more preferably 90% by mass or less, relative to the surface layer.
[0064] -Number of hydrogen atoms bonded to silicon atoms- The number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition is preferably 0.8 to 2.0 per alkenyl group bonded to silicon atoms, and more preferably 1.0 to 1.7 per alkenyl group. This improves the reactivity of the addition reaction, thereby enhancing the high-temperature release properties and flexibility of the surface layer.
[0065] Here, the number of hydrogen atoms bonded to silicon atoms in the composition refers to the total number of hydrogen atoms bonded to silicon atoms contained in component (A) and component (B). The alkenyl groups bonded to silicon atoms in the composition refer to the alkenyl groups bonded to silicon atoms in components (A) and (B).
[0066] The number of hydrogen atoms bonded to a silicon atom is 1 H-NMR and 29 It can be calculated from the structures of components (A) and (B) obtained from the integrated values of the Si-NMR detection spectrum.
[0067] -Other additives- The surface layer may contain other additives. Other additives include non-reactive oils, reactive oils, heat-resistant additives, control agents, natural rubber, inorganic particles, and carbon. In particular, it is preferable that the surface layer further contains carbon. Carbon is a material that functions as both a filler and a conductive agent. Therefore, by including carbon in the surface layer, the hardness of the surface layer is increased and conductivity can be imparted to the surface layer. This improves the wear resistance of the surface layer and suppresses image distortion caused by triboelectric charging during fixing.
[0068] Examples of carbon include carbon black, pyrolytic carbon, graphite, single-layer or multi-layer graphene, short or long carbon nanotubes, single-layer or multi-layer carbon nanotubes, fullerenes, carbon fibers, activated carbon, and graphite materials (artificial graphite, natural graphite). Among these, carbon black is preferred as the carbon from the viewpoint of improving wear resistance and conductivity.
[0069] Examples of carbon black include Ketjen black, oil furnace black, channel black (i.e., gas black), and acetylene black. Surface-treated carbon black (hereinafter also referred to as "surface-treated carbon black") may also be used. Surface-treated carbon black is obtained by imparting, for example, carboxyl groups, quinone groups, lactone groups, hydroxyl groups, etc., to its surface. Examples of surface treatment methods include air oxidation, in which carbon black is reacted in contact with air under a high-temperature atmosphere; a method of reacting carbon black with nitrogen oxides or ozone at room temperature (e.g., 22°C); and a method of air oxidation under a high-temperature atmosphere followed by oxidation with ozone at a low temperature.
[0070] The carbon content is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and even more preferably 20% by mass or more and 30% by mass or less.
[0071] Other additives besides carbon include, for example, conductive agents, fillers, softeners (paraffin-based, etc.), processing aids (stearic acid, etc.), and antioxidants (amine-based, etc.).
[0072] -Surface layer thickness- The surface film thickness is preferably 10 μm to 100 μm, and more preferably 20 μm to 50 μm.
[0073] (Adhesive layer) The adhesive layer is provided, for example, between the substrate and the elastic layer, between the elastic layer and the surface layer, between the elastic layer and the intermediate layer, between the intermediate layer and the surface layer, etc., to bond each layer together.
[0074] Examples of adhesive layers include cured layers of adhesive compositions containing adhesive. Examples of adhesives include silane coupling agent-based adhesives, silicone-based adhesives, epoxy resin-based adhesives, and urethane resin-based adhesives. The adhesive composition may contain other components as needed. Other components include, for example, inorganic particles (e.g., iron oxide, silica, etc.).
[0075] The thickness of the adhesive layer is preferably 1 μm to 100 μm, and more preferably 2 μm to 50 μm.
[0076] (Modular modulus of the surface layer) - Surface elastic modulus E A - Elastic modulus of the surface layer at 140℃ E A The pressure is between 10 MPa and 200 MPa. Therefore, the surface layer has high flexibility. From the perspective of improving the flexibility of the surface layer, the elastic modulus E of the surface layer A The pressure is preferably between 15 MPa and 100 MPa, and more preferably between 20 MPa and 100 MPa. Surface elastic modulus E A To achieve the above range, the composition of the addition-cured product of the above addition-curable organopolysiloxane composition is set to the above range.
[0077] - Surface elastic modulus E B - The elastic modulus E of the surface layer at 140°C after heating at 200°C for 48 hours in an oxygen atmosphere. B However, the pressure is between 10 MPa and 200 MPa. Therefore, it maintains the flexibility of the surface layer well. From the perspective of improving the maintenance of surface flexibility, the elastic modulus E of the surface B The pressure is preferably between 15 MPa and 100 MPa, and more preferably between 20 MPa and 100 MPa. Surface elastic modulus E B To achieve the above range, the composition of the addition-cured product of the above addition-curable organopolysiloxane composition is set to the above range.
[0078] - Surface elastic modulus E A and modulus of elasticity E B Measurement method - First, a 4mm x 50mm sample is obtained from the surface layer of the fixing material to be measured. For the sample being measured, a dynamic viscoelasticity analyzer (RheoVibron) was used to perform constant velocity measurements from room temperature (25°C) to 200°C under the following conditions: measurement frequency of 10 Hz, elongation rate of 0.4%. The elastic modulus E at 140°C was then measured. A Measure.
[0079] On the other hand, after obtaining the sample for measurement, the sample is heated and left in a circulating oven at 200°C for 48 hours under a normal air atmosphere. For the sample measured after heating, the elastic modulus E of the surface layer A Similarly, the elastic modulus E of the surface layer B Measure.
[0080] (Method of manufacturing the fixing member) The method for manufacturing the fixing member according to this embodiment includes the step of applying an addition-curable organopolysiloxane composition containing (A) an organopolysiloxane resin having a structural unit represented by formula (1), (B) a linear organopolysiloxane represented by the following formula (2), and (C) a platinum group metal catalyst onto a substrate and curing it to form a surface layer. Here, as described above for the fixing member according to this embodiment, the content of component (B) relative to 100 parts by mass of component (A) is 10 parts by mass or more and 300 parts by mass or less. Furthermore, in the resulting fixing member, the elastic modulus E of the surface layer at 140°C A However, the elastic modulus E of the surface layer at 140°C is between 10 MPa and 200 MPa, and the elastic modulus E is obtained after heating at 200°C for 48 hours in an oxygen atmosphere. B However, the pressure is between 20 MPa and 100 MPa.
[0081] -(C)Platinum group metal catalyst- As for the platinum group metal catalyst, there are no particular restrictions as long as it is a catalyst that promotes the addition reaction of component (A) and component (B), and known platinum group metal catalysts can be used. Platinum group metal catalysts specifically include elemental platinum group metals such as platinum (including platinum black), rhodium, and palladium; H2PtCl4·nH2O, H2PtCl6·nH2O, NaHPtCl6·nH2O, KHPtCl6·nH2O, Na2PtCl6·nH2O, K2PtCl4·nH2O, PtCl4·nH2O, PtCl2, Na2HPtCl4·nH2O (wherein n in the chemical formula is an integer from 0 to 6, and is either 0 or 6). Preferred materials include platinum chloride, platinum chloride acid, and platinum chloride salts; alcohol-modified platinum chloride; complexes of platinum chloride acid and olefins; catalysts in which platinum group metals such as platinum black and palladium are supported on a carrier such as alumina, silica, or carbon; rhodium-olefin complexes; Wilkinson catalyst [chlorotris(triphenylphosphine)rhodium]; and complexes of platinum chloride, platinum chloride acid, or platinum chloride salts with vinyl group-containing siloxanes. These platinum group metal catalysts may be used individually or in combination of two or more. Among these platinum group metal catalysts, platinum and platinum compounds are preferred.
[0082] From the viewpoint of improving high-temperature release properties and flexibility, the content of component (C) (i.e., platinum group metal catalyst) per 100 parts by mass of component (A) is preferably 0.00001 parts by mass or more and 0.005 parts by mass or less, and more preferably 0.0001 parts by mass or more and 0.003 parts by mass or less, based on the mass equivalent to platinum group metal atoms.
[0083] -Curing conditions for addition-curable organopolysiloxane compositions- The curing conditions for the addition-curable organopolysiloxane composition are as follows, for example, from the viewpoint of improving high-temperature release properties and flexibility. Curing temperature: 100°C to 250°C (preferably 150°C to 200°C) Curing time: 0.5 hours to 12 hours (preferably 1 hour to 6 hours) Curing atmosphere: Atmospheric atmosphere
[0084] <Fusing device> The fixing device described herein is It comprises a first rotating body and a second rotating body positioned in contact with the outer surface of the first rotating body, At least one of the first rotating body and the second rotating body is composed of the fixing member according to the present embodiment.
[0085] The fixing device according to this embodiment includes a well-known fixing device comprising a heating roll or heating belt as a first rotating body and a pressure roll or pressure belt as a second rotating body. The fixing device according to this embodiment also includes well-known fixing devices such as electromagnetic induction heating devices. Furthermore, in the fixing device according to this embodiment, the fixing member according to this embodiment may be applied to any of the pressure roll, heating belt, pressure roll, and pressure belt. However, when an electromagnetic induction heating type fixing device is applied to the fixing device according to this embodiment, the fixing member according to this embodiment is a fixing member having a metal heating layer that generates heat by electromagnetic induction.
[0086] A typical embodiment of the fixing device according to this embodiment will be described below.
[0087] (First Embodiment) The fixing device according to the first embodiment will be described with reference to Figure 1. Figure 1 is a schematic diagram showing an example of the fixing device according to the first embodiment.
[0088] As shown in Figure 1, the fixing device 200 is configured to include, for example, a rotating heated roll 201, a pressure belt 202, and a pressing pad 203. The heated roll 201 is an example of a first rotating body. The pressure belt 202 is an example of a second rotating body. The pressure pad 203 is a pad that presses against the heating roll 201 via the pressure belt 202. The pressure pad 203 only needs to be relatively pressurized, for example, between the pressure belt 202 and the heating roll 201. Therefore, the pressure belt 202 may be pressed against the heating roll 201, or the heating roll 201 may be pressed against the pressure belt 202.
[0089] A halogen lamp 204 (an example of a heating device) is installed inside the heating roll 201. The heating device is not limited to a halogen lamp; other heat-generating components may be used.
[0090] On the other hand, a temperature-sensing element 205 is positioned in contact with the surface of the heating roll 201, for example. Based on the temperature measured by the temperature sensing element 205, the illumination of the halogen lamp 204 is controlled, and the surface temperature of the heating roll 201 is maintained at the desired set temperature (for example, 140°C).
[0091] The pressure belt 202 is rotatably supported, for example, by an internally positioned pressure pad 203 and a belt travel guide 206. In the clamping region N (nip portion), it is pressed against the heating roll 201 by the pressure pad 203.
[0092] The pressure pad 203 is positioned, for example, inside the pressure belt 202, and is pressed against the heating roll 201 via the pressure belt 202, forming a clamping region N between it and the heating roll 201. The pressing pad 203 includes, for example, a front clamping member 203A positioned on the entrance side of the clamping area N to secure a wide clamping area N, and a peeling clamping member 203B positioned on the exit side of the clamping area N to impart distortion to the heating roll 201. The concave-shaped front clamping member 203A, which conforms to the outer surface of the heating roll 201, ensures a wider clamping area N compared to a configuration without the front clamping member 203A. The peeling and clamping member 203B, which is positioned to protrude from the outer surface of the heating roll 201, is configured to locally increase the strain of the heating roll 201 at the exit region of the clamping region N. By arranging the peeling and clamping member 203B in this manner, for example, when the fixed paper K passes through the peeling and clamping region, it will pass through a locally large amount of strain, making it easier for the paper K to peel off from the heating roll 201.
[0093] A sheet-like sliding member 207 is provided on the surfaces of the front clamping member 203A and the peeling clamping member 203B that are in contact with the pressure belt 202. The sliding member 207 reduces the sliding resistance between the inner circumferential surface of the pressure belt 202 and the pressing pad 203. The pressing pad 203 and the sliding member 207 are held together by a metal retaining member 208. The sliding member 207 is provided, for example, so that its sliding surface contacts the inner circumferential surface of the pressure belt 202. The sliding member 207 is involved in retaining and supplying the oil present between it and the pressure belt 202.
[0094] A belt guide 206 is attached to the holding member 208, for example. The pressure belt 202 rotates guided by the belt guide 206. Furthermore, the belt travel guide 206 may be equipped with a lubricant supply device 209 that supplies lubricant (oil) to the inner circumferential surface of the pressure belt 202.
[0095] The fixing device 200 includes, for example, a peeling member 210 positioned downstream of the clamping area N of the heating roll 201 as an auxiliary peeling device. The peeling member 210 includes, for example, a peeling claw 210A and a holding member 210B that holds the peeling claw 210A in a position where the peeling claw 210A is in close proximity to the heating roll 201 in a direction opposite to the rotation direction of the heating roll 201 (counter direction).
[0096] In the fixing device 200, for example, the heating roll 201 is rotated by a drive motor (not shown). Following the rotation of the heating roll 201, the pressure belt 202 rotates in the opposite direction to the rotation of the heating roll 201. That is, for example, while the heating roll 201 rotates clockwise in Figure 2, the pressure belt 202 rotates counterclockwise.
[0097] Then, the paper K (an example of a recording medium) having an unfixed toner image is guided, for example, by a fuser entrance guide 211 and transported to the sandwiching area N. As the paper K passes through the sandwiching area N, the unfixed toner image on the paper K is fixed by the pressure and heat acting on the sandwiching area N.
[0098] (Second embodiment) The fixing device according to the second embodiment will be described with reference to Figure 2. Figure 2 is a schematic diagram showing an example of the fixing device according to the second embodiment.
[0099] As shown in Figure 2, the fixing device 300 according to the second embodiment is configured to include, for example, a fixing belt module 303 equipped with a heating belt 301, and a pressure roll 302 (an example of a second rotating body) pressed against the heating belt 301 (i.e., the fixing belt module 303). A pinching region N (i.e., a nip) is formed at the contact point between the heating belt 301 (i.e., the fixing belt module 303) and the pressure roll 302. In the pinching region N, the paper K (an example of a recording medium) is pressurized and heated, and the toner image is fixed. The heating belt 301 is an example of the first rotating body. The pressure roll 302 is an example of the second rotating body.
[0100] The fixing belt module 303 includes, for example, an endless heating belt 301, a heating and pressing roll 304, and a support roll 305. The heated pressing roll 304 has a heated belt 301 wrapped around it on the side of the pressure roll 302, and is rotated by the rotational force of a motor (not shown), while simultaneously pressing the heated belt 301 from its inner circumference toward the pressure roll 302. The support roll 305 is a roll that supports the heating belt 301 from the inside at a different position from the heating and pressing roll 304.
[0101] The fixing belt module 303 is provided with, for example, a support roll 306, a posture correction roll 307, and a support roll 308. The support roll 306 is a roll positioned on the outside of the heating belt 301 and defines its circumferential path. The posture correction roll 307 is a roll that corrects the posture of the heating belt 301 from the heating and pressing roll 304 to the support roll 305. The support roll 308 is a roll that applies tension to the heating belt 301 from its inner circumferential surface downstream of the clamping region N formed by the heating belt 301 and the pressure roll 302.
[0102] In the downstream region of the nip section N, which is the area where the fixing belt module 303 and the pressure roll 302 are in contact, and on the inside of the heating belt 301, a peeling pad 309 is provided, which is arranged around the heating pressure roll 304 and peels the heating belt 301 from the outer surface of the heating pressure roll 304. The release pad 309 is an arc-shaped member comprising a curved inner surface 309A facing the heating pressure roll 304, a pressing surface 309B that presses the heating belt 301 toward the pressure roll 302, and an outer surface 309C that bends the heating belt 301 at a predetermined angle with respect to the pressing surface 309B. In detail, the corner U formed by the pressing surface 309B and the outer surface 309C bends the heating belt 301 pressed against the corner U by the pressure roll 302, and separates the leading edge of the paper K from the heating belt 301 as the leading edge of the paper K passes through the corner U.
[0103] Inside the heated pressing roll 304, for example, a halogen heater 304A (an example of a heating device) is provided. The halogen heater 304A heats the heated belt 301 from the inner circumferential side. Inside the support roll 305, for example, a halogen heater 305A (an example of a heating device) is provided. The halogen heater 304A heats the heating belt 301 from the inner circumferential side. The support roll 306 is equipped with, for example, a halogen heater 306A (an example of a heating device). The halogen heater 306A heats the heating belt 301 from the outer circumferential side. In other words, the fixing device 300 is configured such that the heating belt 301 is heated by, for example, a heating and pressing roll 304, a support roll 305, and a support roll 306.
[0104] Near the posture correction roll 307, an end position measuring mechanism (not shown) is positioned to measure the end position of the heating belt 301. The posture correction roll 307 is equipped with, for example, an axial displacement mechanism (not shown) that displaces the contact position of the heating belt 301 in the axial direction according to the measurement results of the end position measuring mechanism. The posture correction roll 307 is configured to control the meandering of the heating belt 301.
[0105] The pressure roll 302 is supported, for example, so as to be rotatable. The pressure roll 302 is pressed against the portion where the heating belt 301 is wound around the heating pressure roll 304 by a biasing device, for example, a spring (not shown).
[0106] In the fixing device 300, the heating belt 301 (i.e., the heating and pressing roll 304) of the fixing belt module 303 rotates. Consequently, the pressure roll 302 rotates in conjunction with the heating belt 301 (i.e., the heating and pressing roll 304).
[0107] The paper K, which has an unfixed toner image (not shown), is then transported and guided to the clamping area N of the fixing device 300. As the paper K passes through the clamping area N, the unfixed toner image on the paper K is fixed by the pressure and heat acting on the clamping area N.
[0108] (Third embodiment) The fixing device according to the third embodiment will be described with reference to Figure 3. Figure 3 is a schematic diagram showing an example of the fixing device according to the third embodiment. As shown in Figure 3, the fixing device 400 according to the third embodiment includes a heating belt 401 having a metal heating layer, a pressure roll 402, an electromagnetic induction heating device 403 (an example of a heating device), a latch mechanism 404, and a temperature sensor 408. The heating belt 401 is an example of the first rotating body. The pressure roll 402 is an example of the second rotating body.
[0109] Inside the heating belt 401 are a sliding sheet 405, a pressing pad 406, and a support member 407. The sliding sheet 405 is provided between the pressure pad 406 and the heating belt 401. The sliding sheet 405 reduces the sliding resistance between the heating belt 401 and the pressure pad 406. The pressure pad 406 is positioned to press against the pressure roll 402 via the heating belt 401. The support member 407 is provided to support the pressure pad 406.
[0110] The electromagnetic induction heating device 403 is a device that heats the metal heating layer of the heating belt 401 by electromagnetic induction. The electromagnetic induction heating device 403 is equipped with multiple excitation coils 403A that generate a magnetic field by supplying power from a fixing power supply. The electromagnetic induction heating device 403 modifies the magnetic field generated from the excitation coil 403A using an excitation circuit. This generates eddy currents in the metal heating layer of the heating belt 401. These eddy currents are converted into Joule heat by the electrical resistance of the metal heating layer, causing the metal heating layer to heat up. As a result, the heating belt 401 is heated.
[0111] The latch mechanism 404 is a mechanism that allows the pressure roll 402 to move between a separated position and a pressurized position when the fixing device 400 is in operation.
[0112] When the pressure roll 402 is in a separated position, the target of the drive device (motor, etc.) (not shown) is switched to the heating belt 401. The heating belt 401 is then rotated by the drive device. On the other hand, when the pressure roll 402 is moved to the pressurized position by the latch mechanism 404, the target of the drive device (motor, etc.) not shown is switched to the pressure roll 402, and the pressure roll 402 is rotated by the drive device. At this time, the heating belt 401 is also driven to rotate along with the rotation of the pressure roll 402.
[0113] The temperature sensor 408 is located around the heating belt 401. The temperature sensor 408 measures the surface temperature of the heating belt.
[0114] In the fixing device 400, for example, before the start of fixing, the pressure belt 401, which is separated from the pressure roll 402, is rotated, and the electromagnetic induction heating device 403 is used to heat the metal heating layer of the heating belt 401. Then, the heating belt 401 and the pressure roll 402 are brought into contact, and fixing is started.
[0115] Specifically, for example, in the fixing device 400, when image formation is started, the heating belt 401 is rotated while the pressure roll 402 is in a separated position before fixing begins. Here, the rotation speed of the heating belt 401 is lower than the rotation speed during fixing. Next, a magnetic field is generated from the excitation coil 403A of the electromagnetic induction heating device 403, causing the metal heating layer of the heating belt 401 to heat up. This heats the heating belt 401. Next, the latch mechanism 404 moves the pressure roll 402 to the pressurized position, and the pressure roll 402 is pressed against the pressure pad 406 via the heating belt 401 and the sliding sheet 405. Then, with the heating belt 401 and the pressure roll 402 under pressure, the paper K (an example of a recording medium) on which the toner image has been transferred is transported to the contact area between the heating belt 401 and the pressure roll 402. This fixes the toner image onto the paper K. After the fixing operation is complete, the latch mechanism 404 moves the pressure roll 402 to the separated position.
[0116] (Fourth embodiment) A fixing device according to the fourth embodiment will be described with reference to Figure 4. Figure 4 is a schematic diagram showing an example of a fixing device according to the fourth embodiment.
[0117] The fixing device 500 according to the fourth embodiment includes a heating belt 501, a pressure roll 502, and a halogen heater 503 (an example of a heating device), as shown in Figure 4. The heating belt 501 is an example of a first rotating body. The pressure roll 502 is an example of a second rotating body. The halogen heater 503 is an example of a heating device.
[0118] Inside the heating belt 501 are a sliding sheet 504, a pressing pad 505, a support member 506, and a reflective sheet 507. The sliding sheet 504 is provided between the pressure pad 505 and the heating belt 501. The sliding sheet 504 reduces the sliding resistance between the heating belt 501 and the pressure pad 505. The support member 506 is provided to support the pressure pad 505. The reflective sheet 507 is a component that reflects radiant heat emitted from the halogen heater 503. The reflective sheet 507 is positioned opposite the inner circumferential surface of the heating belt 501 via the halogen heater 503, and in a position where the radiant heat emitted from the halogen heater 503 does not reach the sandwiched area N.
[0119] The pressure roll 502 is positioned opposite the heating belt 501. The pressure roll 502 is positioned in a pressed state against the pressure pad 505 via the heating belt 501 and the sliding sheet 504. As a result, in the clamping region N, the pressure roll 502 is positioned in pressure against the heating belt 501. The pressure roll 502 is connected to a drive device (not shown) via gears or the like (not shown). The drive device rotates the pressure roll 502. The heating belt 501 rotates in response to the rotation of the pressure roll 502.
[0120] The halogen heater 503 is a heating device that emits radiant heat. The halogen heater 503 is located inside the heating belt 501, between the reflective sheet 507 and the heating belt 501. The halogen heater 503 heats the heating belt 501 from inside the heating belt 501 by the radiant heat it emits and the radiant heat reflected by the reflective sheet 507.
[0121] In the fixing device 500, a sheet K onto which a toner image has been transferred is conveyed to the nipping area N. In the nipping area N, the toner image is heated and pressed by a heating belt 501 and a pressure roll 502, and the toner image is fixed onto the sheet K (an example of a recording medium). Then, the sheet K with the fixed toner image is peeled from the heating belt 501 in the exit area of the nipping area N due to the change in curvature of the heating belt 501.
[0122] (Fifth Embodiment) The fixing device according to the fifth embodiment will be described with reference to Fig. 5. Fig. 5 is a schematic diagram illustrating an example of the fixing device according to the fifth embodiment.
[0123] As shown in Fig. 5, a fixing device 600 according to the fifth embodiment includes a heating roll 601, a pressure roll 602, and a peeling claw 603. The heating roll 601 is an example of a first rotating body. The pressure roll 602 is an example of a second rotating body.
[0124] Inside the heating roll 601, a halogen heater 605 (an example of a heating device) that heats the heating roll 601 is provided. Around the heating roll 601, an oil supply device 604 that supplies oil to the surface of the heating roll 601 is provided.
[0125] In the fixing device 600, the heating roll 601 and the pressure roll 602 are arranged so as to be capable of rotating freely. The heating roll 601 is connected to a non-illustrated drive source (e.g., a motor or the like) via a non-illustrated power transmission member (e.g., a gear or the like). Power generated by the drive source (e.g., a motor or the like) is transmitted to the heating roll 601 by the power transmission member (e.g., a gear or the like). Thereby, the heating roll 601 is rotationally driven. The pressure roll 602 is arranged so as to be pressed against the heating roll 601 by a non-illustrated spring or the like. The pressure roll 602 rotates following the rotational driving of the heating roll.
[0126] The peeling claw 603 is provided on the downstream side in the rotation direction of the heating roll 601 (that is, the downstream side in the conveyance direction of the sheet K) relative to the contact portion between the heating roll 601 and the pressure roll 602. The peeling claw 603 is in contact with the heating roll 601 and peels the sheet K, which has passed through the contact portion between the heating member and the pressure member, from the heating roll 601. This suppresses the winding of the sheet K around the heating roll 601. In order to fulfill this function, the tip end portion of the peeling claw 603 is pressed against the surface of the heating roll 601 by a spring or the like (not shown).
[0127] In the fixing device 60, oil is supplied to the surface of the heating roll 601 by an oil supply device 604. In this state, the sheet K (an example of a recording medium) having an unfixed toner image transferred thereon enters the contact portion between the heating roll 601 heated by a halogen heater 605 and the pressure roll 602 via a conveyance mechanism (not shown). The toner image transferred onto the sheet K is heated and pressurized at the contact portion between the heating roll 601 and the pressure roll 602. As a result, the toner image is fixed onto the sheet K. When the fixed sheet K is wound around the heating roll 601, the sheet K is peeled from the heating roll 601 by the peeling claw 603.
[0128] (Sixth Embodiment) A fixing device according to a sixth embodiment will be described with reference to FIG. 6. FIG. 6 is a schematic diagram illustrating an example of the fixing device according to the sixth embodiment. As shown in FIG. 6, the fixing device 700 according to the sixth embodiment includes: a heating unit 710 having a heating belt 701; and a pressure unit 720 that has a pressure roll 702 and is opposed to the heating unit 710. The heating belt 701 is an example of a first rotating body. The pressure roll 702 is an example of a second rotating body.
[0129] The heating section 710 includes a heating belt 701, a planar heating element 703 (an example of a heating device) located inside the heating belt 701 that heats the heating belt 701 from the inner circumferential surface, a holding member 704 that holds the planar heating element 703, and a frame member 705 that supports the holding member 704. In this case, the holding member 704 is supported by the frame member 705 and has a structure that can withstand the pressure from the pressurizing section 720. The inner surface of the heating belt 701 that is in contact with the planar heating element 703 may be coated with a lubricant such as lubricating grease.
[0130] In the heating section 710, the heating belt 701 is supported at both ends in the longitudinal direction of the heating belt 701. For example, support members (not shown) are provided at each end. A heating member gear (not shown) that rotates the heating belt 701 is provided on this support member, and one end of this heating member gear is connected to a drive device (not shown), such as a motor. Alternatively, a heating element gear may be omitted from the heating belt 701, and the heating belt 701 may be driven to rotate in conjunction with the rotation of the pressure roll 702.
[0131] In the heating section 710, the planar heating element 703 is formed, for example, as a long plate-like body along the longitudinal direction of the heating section 710. The planar heating element 703 includes, for example, an electrically insulating substrate, an insulating layer formed of a polyimide-based heat-resistant resin, a pair of electrodes for power supply, and a resistive heating element, for example, made of stainless steel, which generates heat when power is supplied from the electrodes. In the planar heating element 703, the electrodes and the resistance heating portion are connected by a power supply portion, and the electrodes, power supply portion, and resistance heating portion are embedded in an insulating layer. Furthermore, the electrodes of the planar heating element 703 are grounded with the heating element side resistor 706 in between.
[0132] In the heating section 710, the holding member 704 has, for example, a groove 707 formed along its longitudinal direction on the side facing the pressurizing section 720 for holding the planar heating element 703.
[0133] The holding member 704, while holding the planar heating element 703 in the groove 707, is pressed by the pressurizing portion 720, thereby forming a clamping region N.
[0134] In the heating section 710, the frame member 705 supports, for example, the holding member 434, and both ends of the frame member 705 are fixed to support members (not shown). The frame member 705 is configured such that the holding member 704 can withstand pressure from the pressurizing section 720. Furthermore, the heating section 710 may be equipped with a thermistor or the like for temperature detection.
[0135] The pressurizing section 720 has a pressurizing roll 702 and is positioned opposite the heating section 710. It is pressed against the outer surface of the heating belt 701 of the heating section 710 and rotated by a drive device (not shown).
[0136] In the pressurizing section 720, the pressurizing roll 702 is grounded, and the shaft portion of the pressurizing roll 702 is grounded with the pressurizing section side resistor 708 in between. By grounding the pressure roll 702 with the pressure section side resistor 708 in between, current leakage (leakage current) from the electrodes of the planar heating element 703 of the heating section 710 can be suppressed.
[0137] In the pressurizing section 720, the pressurizing roll 702 is pressed against the heating section 710 by a pressing member (not shown) made of an elastic material such as a coil spring.
[0138] In the fixing device 700, the clamping region N is formed with the heating belt 701 being held between the pressure roll 702 of the pressurizing section 720 and the unit consisting of the planar heating element 703, holding member 704 and frame member 705 of the heating section 710. Then, by passing a piece of paper (an example of a recording medium) containing an unfixed toner image in the insertion area N through the paper, heat and pressure are applied to fix the unfixed toner image onto the recording medium.
[0139] <Image forming apparatus> Next, the image forming apparatus according to the present embodiment will be described. The image forming apparatus according to the present embodiment is comprising: an image holding member; a charging device that charges a surface of the image holding member; an electrostatic latent image forming device that forms an electrostatic latent image on the surface of the charged image holding member; a developing device that accommodates a developer containing toner, and develops the electrostatic latent image formed on the surface of the image holding member with the developer to form a toner image; a transfer device that transfers the toner image to a surface of a recording medium; and a fixing device that fixes the toner image to the surface of the recording medium. The fixing device according to the present embodiment is applied as the fixing device.
[0140] Here, in the image forming apparatus according to the present embodiment, each fixing device may be formed as a cartridge so as to be attachable to and detachable from the image forming apparatus. That is, the image forming apparatus according to the present embodiment may include the fixing device according to the present embodiment as a component device of a process cartridge.
[0141] Hereinafter, the image forming apparatus according to the present embodiment will be described with reference to the drawings. FIG. 7 is a schematic configuration diagram showing the configuration of the image forming apparatus according to the present embodiment.
[0142] As shown in FIG. 7, the image forming apparatus 100 according to the present embodiment is, for example, an intermediate transfer type image forming apparatus generally called a tandem type. The image forming apparatus 100 includes a plurality of image forming units 1Y, 1M, 1C, 1K, an intermediate transfer belt 15, a primary transfer section 10, a secondary transfer section 20, and a fixing device 60. The image forming apparatus 100 also includes a control section 40 that controls operations of each device (or each section). Here, the image forming units 1Y, 1M, 1C, 1K are image forming units that form toner images of respective color components by an electrophotographic method. The primary transfer section 10 is a transfer section that causes the color component toner images formed by the image forming units 1Y, 1M, 1C, 1K to be sequentially transferred (primary-transferred) onto the intermediate transfer belt 15. The secondary transfer unit 20 is a transfer unit that transfers the superimposed toner image transferred onto the intermediate transfer belt 15 to the recording medium, paper K, in one go (secondary transfer). The fixing device 60 is a device that fixes the secondary transferred image onto the paper K.
[0143] Each image forming unit 1Y, 1M, 1C, and 1K of the image forming apparatus 100 is equipped with a photoreceptor 11 that rotates in the direction of arrow A, as an example of an image holder that holds the toner image formed on its surface.
[0144] Around the photoreceptor 11, a charger 12 is provided as an example of a charging device to charge the photoreceptor 11. Around the photoreceptor 11, a laser exposure unit 13 (indicated by the symbol Bm in the figure) is provided as an example of an electrostatic latent image forming device to write an electrostatic latent image onto the photoreceptor 11.
[0145] Surrounding the photoreceptor 11, a developer unit 14 is provided, as an example of a developing device. This unit contains toners for each color component and visualizes the electrostatic latent image on the photoreceptor 11 using the toners. A primary transfer roll 16 is provided around the photoreceptor 11, which transfers the toner images of each color component formed on the photoreceptor 11 to the intermediate transfer belt 15 via the primary transfer unit 10.
[0146] A photoreceptor cleaner 17 is provided around the photoreceptor 11 to remove any residual toner on the photoreceptor 11. Around the photoreceptor 11, electrophotographic devices such as a charger 12, a laser exposure unit 13, a developer unit 14, a primary transfer roll 16, and a photoreceptor cleaner 17 are sequentially arranged along the rotational direction of the photoreceptor 11. These image forming units 1Y, 1M, 1C, and 1K are arranged in a nearly linear fashion from the upstream side of the intermediate transfer belt 15, in the order of yellow (Y), magenta (M), cyan (C), and black (K).
[0147] The intermediate transfer belt 15 is driven (rotated) by various rolls in the direction of arrow B shown in Figure 7 at a speed appropriate for the purpose. The various rolls include a drive roll 31, a support roll 32, a tensioning roll 33, a back roll 25, and a cleaning back roll 34. The drive roll 31 is a roll that rotates the intermediate transfer belt 15, driven by a motor (not shown) with excellent constant-speed performance. The support roll 32 is a roll that supports the intermediate transfer belt 15, which extends substantially in a straight line along the arrangement direction of each photoreceptor 11. The tension-applying roll 33 is a roll provided in the secondary transfer section 20 that applies tension to the intermediate transfer belt 15 and functions as a corrective roll to prevent the intermediate transfer belt 15 from meandering. The cleaning back roll 34 is a roll provided in the cleaning section that scrapes off residual toner from the intermediate transfer belt 15.
[0148] The primary transfer section 10 consists of a primary transfer roll 16 positioned opposite the photoreceptor 11, with an intermediate transfer belt 15 in between.
[0149] The primary transfer roll 16 is then pressed against the photoreceptor 11 with the intermediate transfer belt 15 in between, and a voltage (primary transfer bias) with the opposite polarity to the charge polarity of the toner (negative polarity; the same applies hereafter) is applied to the primary transfer roll 16. As a result, the toner images on each photoreceptor 11 are sequentially electrostatically attracted to the intermediate transfer belt 15, and superimposed toner images are formed on the intermediate transfer belt 15.
[0150] The secondary transfer section 20 comprises a back roll 25 and a secondary transfer roll 22 positioned on the toner image holding surface side of the intermediate transfer belt 15.
[0151] The secondary transfer roll 22 is then pressed against the back roll 25 with the intermediate transfer belt 15 in between, and the secondary transfer roll 22 is grounded to form a secondary transfer bias between itself and the back roll 25, thereby secondary transferring the toner image onto the paper K that is transported to the secondary transfer section 20.
[0152] Furthermore, an intermediate transfer belt cleaner 35 is provided downstream of the secondary transfer section 20 of the intermediate transfer belt 15 so as to be able to move toward and away from the intermediate transfer belt 15. The intermediate transfer belt cleaner 35 is a cleaner that removes residual toner and paper dust from the intermediate transfer belt 15 after secondary transfer, and cleans the surface of the intermediate transfer belt 15.
[0153] The intermediate transfer belt 15, the primary transfer section 10 (primary transfer roll 16), and the secondary transfer section 20 (secondary transfer roll 22) are examples of a transfer apparatus.
[0154] On the other hand, a reference sensor (home position sensor) 42 is installed upstream of the yellow image forming unit 1Y. The reference sensor 42 is a sensor that generates a reference signal that serves as a reference for determining the image formation timing in each image forming unit 1Y, 1M, 1C, and 1K. The reference sensor 42 recognizes a mark provided on the back of the intermediate transfer belt 15 and generates a reference signal. Based on the recognition of this reference signal, the control unit 40 issues instructions, and each image forming unit 1Y, 1M, 1C, and 1K is configured to start image formation. A black image forming unit 1K is located downstream of an image density sensor 43 for adjusting image quality.
[0155] The image forming apparatus 100 includes a paper storage section 50, a paper feed roll 51, a transport roll 52, a transport guide 53, a transport belt 55, and a fuser entrance guide 56. The paper storage section 50 is a storage section for storing paper K, which is a transport device for transporting paper K. The paper feed roll 51 is a roll that takes out and transports the paper K accumulated in the paper storage section 50 at predetermined timings. The transport roll 52 is a roll that transports the paper K that has been fed out by the paper feed roll 51. The transport guide 53 is a guide that feeds the paper K, which has been transported by the transport roll 52, to the secondary transfer section 20. The conveyor belt 55 is a belt that conveys the paper K, which has been secondarily transferred by the secondary transfer roll 22, to the fixing device 60. The fuser entrance guide 56 is a guide 56 that guides the paper K to the fuser unit 60.
[0156] Next, the basic image formation process of the image forming apparatus 100 according to this embodiment will be described. In the image forming apparatus 100 according to this embodiment, image data output from an image reading device (not shown) or a personal computer (PC) (not shown) is processed by an image processing device (not shown), and then image formation is performed by image forming units 1Y, 1M, 1C, and 1K.
[0157] The image processing device performs various image processing operations on the input image data, including shading correction, positional shift correction, brightness / color space conversion, gamma correction, frame removal, color editing, and movement editing. The processed image data is converted into four-color chromatic data (Y, M, C, K) and output to the laser exposure unit 13.
[0158] In the laser exposure unit 13, according to the input color tone data, an exposure beam Bm emitted from, for example, a semiconductor laser is irradiated onto each of the photoreceptors 11 of the image forming units 1Y, 1M, 1C, and 1K. After the surface of each photoreceptor 11 of the image forming units 1Y, 1M, 1C, and 1K is charged by the charger 12, the surface is scanned and exposed by the laser exposure unit 13, and an electrostatic latent image is formed. The formed electrostatic latent image is then developed as toner images of the respective colors Y, M, C, and K by the respective image forming units 1Y, 1M, 1C, and 1K.
[0159] The toner images formed on the photoreceptors 11 of the image forming units 1Y, 1M, 1C, and 1K are transferred onto the intermediate transfer belt 15 in the primary transfer section 10, where each photoreceptor 11 comes into contact with the intermediate transfer belt 15. More specifically, in the primary transfer section 10, a primary transfer roll 16 applies a voltage (primary transfer bias) with the opposite polarity to the toner's charge polarity (negative polarity) to the substrate of the intermediate transfer belt 15, and the toner images are sequentially superimposed on the surface of the intermediate transfer belt 15 to perform primary transfer.
[0160] After the toner image is sequentially transferred to the surface of the intermediate transfer belt 15, the intermediate transfer belt 15 moves and the toner image is transported to the secondary transfer section 20. When the toner image is transported to the secondary transfer section 20, the transport device rotates the paper feed roll 51 in time with the transport of the toner image to the secondary transfer section 20, and paper K of the desired size is supplied from the paper storage section 50. The paper K supplied by the paper feed roll 51 is transported by the transport roll 52 and reaches the secondary transfer section 20 via the transport guide 53. Before reaching the secondary transfer section 20, the paper K is temporarily stopped, and the position of the paper K and the position of the toner image are aligned by rotating the alignment roll (not shown) in time with the movement of the intermediate transfer belt 15 holding the toner image.
[0161] In the secondary transfer section 20, the secondary transfer roll 22 is pressed against the back roll 25 via the intermediate transfer belt 15. At this time, the paper K, which has been transported in sync with the timing, is sandwiched between the intermediate transfer belt 15 and the secondary transfer roll 22. When a voltage (secondary transfer bias) with the same polarity as the charge polarity (negative polarity) of the toner is applied from the power supply roll 26, a transfer electric field is formed between the secondary transfer roll 22 and the back roll 25. Then, the unfixed toner image held on the intermediate transfer belt 15 is electrostatically transferred all at once onto the paper K in the secondary transfer section 20, which is pressed by the secondary transfer roll 22 and the back roll 25.
[0162] Subsequently, the paper K on which the toner image has been electrostatically transferred is peeled off the intermediate transfer belt 15 by the secondary transfer roll 22 and transported as is. The paper K is transported to a transport belt 55 located downstream of the secondary transfer roll 22 in the paper transport direction. The transport belt 55 transports the paper K to the fuser 60 at an optimal transport speed for the fuser 60. The unfixed toner image on the paper K transported to the fuser 60 is fixed to the paper K by the fuser 60 through a fixing process using heat and pressure. The paper K with the fixed image formed is then transported to a paper discharge and storage section (not shown) located in the discharge section of the image forming apparatus 100.
[0163] Meanwhile, after the transfer to paper K is complete, any residual toner remaining on the intermediate transfer belt 15 is transported to the cleaning section as the intermediate transfer belt 15 rotates. The residual toner is removed from the intermediate transfer belt 15 by the cleaning back roll 34 and the intermediate transfer belt cleaner 35.
[0164] <Developer> Hereinafter, an example of a developer (hereinafter also referred to as "electrostatic image developer according to this embodiment") applied to the image forming apparatus according to this embodiment will be described.
[0165] The electrostatic image developer according to this embodiment may be a one-component developer containing only toner, or a two-component developer containing a mixture of toner and a carrier.
[0166] (toner) The toner contains toner particles. The toner may also contain external additives.
[0167] ((Toner particles)) The toner particles may contain, for example, a resin, a colorant, a release agent, or other additives.
[0168] -resin- There are no particular restrictions on the resin, and it can be appropriately selected according to the purpose. Examples include vinyl resins made from homopolymers of monomers such as styrenes (e.g., styrene, parachlorostyrene, α-methylstyrene, etc.), (meth)acrylic acid esters (e.g., methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, lauryl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, lauryl methacrylate, 2-ethylhexyl methacrylate, etc.), ethylenically unsaturated nitriles (e.g., acrylonitrile, methacrylonitrile, etc.), vinyl ethers (e.g., vinyl methyl ether, vinyl isobutyl ether, etc.), vinyl ketones (vinyl methyl ketone, vinyl ethyl ketone, vinyl isopropenyl ketone, etc.), and olefins (e.g., ethylene, propylene, butadiene, etc.), or copolymers of two or more of these monomers. Examples of resins include non-vinyl resins such as epoxy resins, polyester resins, polyurethane resins, polyamide resins, cellulose resins, polyether resins, and modified rosin; mixtures of these with the aforementioned vinyl resins; and graft polymers obtained by polymerizing vinyl monomers in the presence of these. These resins may be used individually or in combination of two or more types. These resins may be included as binder resins, two or more may be included as binder resins, or they may be included as binder resins and (encapsulated) resin particles.
[0169] In particular, it is preferable to use both amorphous and crystalline resins. However, the mass ratio of crystalline resin to amorphous resin (crystalline resin / amorphous resin) is preferably 1 / 99 or more and 50 / 50 or less, more preferably 2 / 98 or more and 30 / 70 or less, and even more preferably 3 / 97 or more and 20 / 80 or less.
[0170] Here, a crystalline resin refers to a resin that exhibits a clear endothermic peak rather than a stepwise change in endothermic quantity in differential scanning calorimetry (DSC). Specifically, this means that the full width at half maximum (FWHM) of the endothermic peak measured at a heating rate of 10°C / min is within 10°C. An amorphous resin refers to a resin whose FWHM exceeds 10°C, exhibits a stepwise change in endothermic quantity, or does not show a clear endothermic peak. Specifically, for example, a crystalline resin means that the full width at half maximum (FWHM) of the endothermic peak measured at a heating rate of 10°C / min is within 10°C, while an amorphous resin means a resin whose FWHM exceeds 10°C, or a resin in which no clear endothermic peak is observed.
[0171] Examples of amorphous resins include known amorphous resins such as amorphous polyester resin, amorphous vinyl resin (e.g., styrene-acrylic resin), epoxy resin, polycarbonate resin, and polyurethane resin. Among these, amorphous polyester resin and amorphous vinyl resin (particularly styrene-acrylic resin) are preferred, and amorphous polyester resin is more preferred. A combination of amorphous polyester resin and styrene-acrylic resin is also a more preferred embodiment.
[0172] Amorphous polyester resin In addition to unmodified amorphous polyester resins, modified amorphous polyester resins can also be mentioned as examples of amorphous polyester resins. Modified amorphous polyester resins are amorphous polyester resins that have bonding groups other than ester bonds, or amorphous polyester resins in which resin components other than polyester are bonded together by covalent bonds or ionic bonds, etc. Examples of modified amorphous polyester resins include resins obtained by reacting an amorphous polyester resin, which has functional groups such as isocyanate groups introduced at its ends, with an active hydrogen compound to modify the ends. In a more preferable embodiment, the amorphous polyester resin may also be an amorphous resin having amorphous polyester resin segments and styrene acrylic resin segments. Amorphous polyester resins may have their hydrophobicity and compatibility controlled by modifying and / or grafting the ends of the polyester chains.
[0173] Examples of amorphous polyester resins include condensation polymers of polycarboxylic acids and polyhydric alcohols. The amorphous polyester resin may be a commercially available product or a synthesized one.
[0174] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., alkenyl succinic acids such as oxalic acid, malonic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, hexenyl succinic acid, octenyl succinic acid, dodecenyl succinic acid, pentadecenyl succinic acid, and their anhydrides, adipic acid, sebacic acid, etc.), alicyclic dicarboxylic acids (e.g., cyclohexanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., terephthalic acid, isophthalic acid, orthophthalic acid, naphthalenedicarboxylic acid, etc.), their anhydrides, or their lower alkyl esters (e.g., with 1 to 5 carbon atoms). Among these, aromatic dicarboxylic acids are preferred as polycarboxylic acids. Polycarboxylic acids may be used in combination with dicarboxylic acids, or with trivalent or higher carboxylic acids that have a cross-linked or branched structure. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, or their lower alkyl esters (e.g., having 1 to 5 carbon atoms). Polycarboxylic acids may be used individually or in combination of two or more.
[0175] Examples of polyhydric alcohols include aliphatic diols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, hexanediol, neopentyl glycol, etc.), alicyclic diols (e.g., cyclohexanediol, cyclohexanedimethanol, hydrogenated bisphenol A, etc.), and aromatic diols (e.g., ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, etc.). Among these, aromatic diols and alicyclic diols are preferred as polyhydric alcohols, and aromatic diols are more preferred. As for the polyhydric alcohol, a trihydric or higher polyhydric alcohol with a cross-linked or branched structure may be used in combination with the diol. Examples of trihydric or higher polyhydric alcohols include glycerin, trimethylolpropane, and pentaerythritol. Polyhydric alcohols may be used individually or in combination of two or more types.
[0176] Amorphous polyester resins can be obtained by well-known manufacturing methods. Specifically, for example, they can be obtained by a method in which the polymerization temperature is set to 180°C or higher and 230°C or lower, and the reaction system is subjected to reduced pressure as needed, while removing water and alcohol generated during condensation.
[0177] The amorphous polyester resin is preferably 60% to 98% by mass of the total resin, more preferably 65% to 95% by mass, and even more preferably 70% to 90% by mass.
[0178] • Styrene acrylic resin Styrene acrylic resin is a copolymer obtained by copolymerizing at least a styrene monomer (a monomer having a styrene skeleton) and a (meth)acrylic monomer (a monomer having (meth)acrylic groups, preferably monomers having (meth)acryloxy groups). Styrene acrylic resin includes, for example, copolymers of styrene monomers and (meth)acrylic acid ester monomers. Furthermore, the acrylic resin portion in styrene-acrylic resin is a substructure formed by polymerizing either an acrylic monomer or a methacrylic monomer, or both. Also, "(meth)acrylic" is an expression that includes both "acrylic" and "methacrylic." Examples of styrene monomers include styrene, α-methylstyrene, metachlorostyrene, parachlorostyrene, parafluorostyrene, paramethoxystyrene, meta-tert-butoxystyrene, para-tert-butoxystyrene, paravinylbenzoic acid, and paramethyl-α-methylstyrene. Styrene monomers may be used individually or in combination of two or more. Examples of (meth)acrylic monomers include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. A single (meth)acrylic monomer may be used, or two or more may be used in combination. The polymerization ratio of styrene monomers to (meth)acrylic monomers is preferably 70:30 to 95:5 by mass, where styrene monomers : (meth)acrylic monomers are equal. Styrene-acrylic resins may have a crosslinked structure. Styrene-acrylic resins having a crosslinked structure can be produced, for example, by copolymerizing a styrene monomer, a (meth)acrylic monomer, and a crosslinkable monomer. The crosslinkable monomer is not particularly limited, but a (meth)acrylate compound with two or more functions is preferred.
[0179] There are no particular restrictions on the method for producing styrene-acrylic resin; for example, solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization, and emulsion polymerization can be used. Known operations (e.g., batch, semi-continuous, continuous, etc.) can be used for the polymerization reaction.
[0180] The styrene-acrylic resin preferably accounts for 60% to 98% by mass of the total resin, more preferably 65% to 95% by mass, and even more preferably 70% to 90% by mass.
[0181] Polyester resins containing modified groups such as isocyanate groups, epoxy groups, and urea groups (hereinafter also referred to as "modified polyester resins") Examples of modified polyester resins include resins obtained by reacting a polyester resin having active hydrogen groups with a compound having a modifying group such as an isocyanate group, epoxy group, or urea group, and resins obtained by reacting a compound containing active hydrogen groups with a polyester resin having active hydrogen groups and a compound having a modifying group such as an isocyanate group or epoxy group. The active hydrogen-containing group includes at least one group selected from hydroxyl groups, mercapto groups, amino groups, carboxyl groups, phosphate groups, sulfonic acid groups, and sulfate groups, which can readily bond with isocyanate compounds, epoxy compounds, etc. Two or more such groups may be included. Polyester resins having active hydrogen groups can be obtained, for example, by polycondensation of a polycarboxylic acid and a polyhydric alcohol. The polycarboxylic acid and polyhydric alcohol can be those exemplified above, either individually or in combination. There are no particular restrictions on the compounds containing active hydrogen groups, as long as they have active hydrogen groups, and they can be appropriately selected according to the purpose. When an isocyanate group is included as a modifying group, amines may be used as the active hydrogen group-containing compound.
[0182] There are no particular restrictions on the amines used, and they can be appropriately selected depending on the purpose. Examples include diamines, polyamines with a valency of 3 or higher, amino alcohols, amino mercaptans, amino acids, and amines with the amino group blocked. Specifically, examples of amines include aromatic diamines, aliphatic diamines, ethylenetriamine, triethylenetetramine, ethanolamine, hydroxyethylaniline, aminoethyl mercaptan, aminopropyl mercaptan, aminopropionic acid, aminocaproic acid, and ketimine compounds and oxazolizone compounds obtained from any of these amines (diamines, polyamines with a valency of 3 or higher, amino alcohols, amino mercaptans, amino acids, etc.) and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.).
[0183] Compounds containing an isocyanate group include, for example, aliphatic polyisocyanates (tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, trimethylhexane diisocyanate, tetramethylhexane diisocyanate, etc.); alicyclic polyisocyanates (isophorone diisocyanate, cyclohexylmethane diisocyanate, etc.); and aromatic diisocyanates (tolylene diisocyanate, diphenylmethane diisocyanate, etc.). Examples include cyanates, 1,5-naphthylene diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, etc.; aromatic aliphatic diisocyanates (α,α,α',α'-tetramethylxylylene diisocyanate, etc.); isocyanurates (tris-isocyanatoalkyl-isocyanurate, triisocyanatocycloalkyl-isocyanurate, etc.); phenol derivatives thereof; and those blocked with oximes, caprolactams, etc. These may be used individually or in combination of two or more.
[0184] There are no particular limitations on the method for synthesizing resins obtained by reacting a polyester resin having active hydrogen groups with a compound having a modifying group such as an isocyanate group, epoxy group, or urea group, or resins obtained by reacting a compound containing active hydrogen groups with a polyester resin having active hydrogen groups and a compound having a modifying group such as an isocyanate group or epoxy group. For example, in the case of resins obtained by reacting a polyester resin having active hydrogen groups with a compound having a modifying group such as an isocyanate group or epoxy group, examples include a method of synthesis by reacting a hydroxyl group-containing polyester resin obtained by the above-mentioned well-known manufacturing method with a compound having a modifying group, or a method of synthesis by stretching reaction and / or crosslinking reaction. Because it has active hydrogen groups, it acts as an extender and / or crosslinking agent in stretching reaction and / or crosslinking reaction. The stretching reaction and / or crosslinking reaction may be stopped as needed with a reaction stopper (such as a monoamine blocked by diethylamine, dibutylamine, butylamine, laurylamine, or ketimine compounds).
[0185] Amorphous resin having polyester resin segments and styrene-acrylic resin segments (hereinafter also referred to as "hybrid polyester resin") Hybrid polyester resin is a polyester resin in which a polyester resin segment and a styrene-acrylic resin segment are chemically bonded together. Examples of hybrid polyester resins include: a resin having a main chain made of polyester resin and side chains made of styrene-acrylic resin chemically bonded to the main chain; a resin having a main chain made of styrene-acrylic resin and side chains made of polyester resin chemically bonded to the main chain; a resin having a main chain formed by the chemical bonding of polyester resin and styrene-acrylic resin; a resin having a main chain formed by the chemical bonding of polyester resin and styrene-acrylic resin, a side chain made of polyester resin chemically bonded to the main chain, and at least one of the side chains made of styrene-acrylic resin chemically bonded to the main chain; and so on.
[0186] The polyester resin and styrene-acrylic resin used in each segment are as described above, and therefore no further explanation is provided.
[0187] The total amount of polyester resin segments and styrene acrylic resin segments in the entire hybrid polyester resin is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 100% by mass.
[0188] In the hybrid polyester resin, the proportion of the styrene-acrylic resin segment to the total amount of the polyester resin segment and the styrene-acrylic resin segment is preferably 20% by mass or more and 90% by mass or less, more preferably 25% by mass or more and 80% by mass or less, and even more preferably 30% by mass or more and 70% by mass or less.
[0189] Hybrid polyester resins are preferably manufactured by one of the following methods (i) to (iii). (i) Polyester resin segments are prepared by condensation polymerization of a polyhydric alcohol and a polyhydric carboxylic acid, and then the monomers constituting the styrene acrylic resin segments are subjected to addition polymerization. (ii) Styrene acrylic resin segments are prepared by addition polymerization of addition polymerizable monomers, and then polyhydric alcohols and polyhydric carboxylic acids are subjected to condensation polymerization. (iii) Condensation polymerization of a polyhydric alcohol and a polyhydric carboxylic acid is carried out in parallel with addition polymerization of an addition polymerizable monomer.
[0190] The hybrid polyester resin is preferably present in an amount of 60% to 98% by mass of the total binder resin, more preferably 65% to 95% by mass, and even more preferably 70% to 90% by mass.
[0191] • Glass transition temperature of amorphous resins The glass transition temperature (Tg) of amorphous resins is preferably 50°C to 80°C, and more preferably 50°C to 65°C. The glass transition temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC), and more specifically, it is determined by the "extracorporeal glass transition onset temperature" described in the method for determining the glass transition temperature in JIS K 7121-1987 "Method for Measuring the Transition Temperature of Plastics".
[0192] • Molecular weight of amorphous resins The weight-average molecular weight (Mw) of the amorphous resin is preferably 3,000 to 1,000,000, and more preferably 7,000 to 500,000. The number-average molecular weight (Mn) of the amorphous resin is preferably between 2,000 and 100,000. The molecular weight distribution (Mw / Mn) of the amorphous resin is preferably 1.5 to 100, and more preferably 2 to 60. The weight-average molecular weight and number-average molecular weight are measured by gel permeation chromatography (GPC). GPC molecular weight measurement is performed using a Tosoh GPC-HLC-8320GPC analyzer, a Tosoh TSKgel SuperHM-M (15cm) column, and THF solvent. The weight-average molecular weight and number-average molecular weight are calculated from these measurement results using a molecular weight calibration curve prepared with monodisperse polystyrene standard samples.
[0193] Amorphous resins may be used individually or in combination of two or more types. When using two or more types in combination, for example, a high molecular weight resin and a low molecular weight resin, or a high glass transition temperature (Tg) resin and a low glass transition temperature (Tg) resin may be used together.
[0194] • Crystalline polyester resin Crystalline polyester resins include, for example, polycondensates of polycarboxylic acids and polyhydric alcohols. Commercially available crystalline polyester resins may be used, or synthesized resins may be used. Here, a polycondensate using polymerizable monomers having linear aliphatic structures is preferred over polymerizable monomers having aromatic structures, as it facilitates the formation of a crystalline structure. From the viewpoint of compatibility with amorphous resins, a polycondensate using polymerizable monomers having aromatic structures, or the above-mentioned modified polyesters, hybrid resins, etc., may also be used. Crystalline polyester resins may be used individually or in combination of two or more types.
[0195] Examples of polycarboxylic acids include aliphatic dicarboxylic acids (e.g., oxalic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,14-tetradecanedicarboxylic acid, 1,18-octadecanedicarboxylic acid, etc.), aromatic dicarboxylic acids (e.g., phthalic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, etc.), their anhydrides, or their lower alkyl esters (e.g., having 1 to 5 carbon atoms). Polycarboxylic acids may be used in combination with dicarboxylic acids, or with trivalent or higher carboxylic acids that have a crosslinked or branched structure. Examples of trivalent or higher carboxylic acids include trimellitic acid, pyromellitic acid, their anhydrides, or their lower alkyl esters (e.g., having 1 to 5 carbon atoms). In addition to these dicarboxylic acids, polycarboxylic acids with sulfonic acid groups and dicarboxylic acids with ethylenic double bonds may also be used in combination. Polycarboxylic acids may be used individually or in combination of two or more.
[0196] Examples of polyhydric alcohols include aliphatic diols (for example, linear aliphatic diols in which the main chain has 2 to 20 carbon atoms). Examples of aliphatic diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, 1,14-tetradecanediol, 1,18-octadecanediol, and 1,20-icosanediol. Among these, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol are preferred as aliphatic diols. Polyhydric alcohols may be used in combination with diols, including trihydric or higher alcohols that have a cross-linked or branched structure. Examples of trihydric or higher alcohols include glycerin, trimethylolethane, trimethylolpropane, and pentaerythritol. Polyhydric alcohols may be used individually or in combination of two or more types.
[0197] Here, the polyhydric alcohol is preferably composed of 80 mol% or more of aliphatic diols, and more preferably 90 mol% or more.
[0198] The melting temperature of the crystalline polyester resin is preferably 50°C to 100°C, more preferably 55°C to 90°C, and even more preferably 60°C to 85°C. The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) using the "melting peak temperature" described in JIS K7121-1987 "Method for determining the transition temperature of plastics".
[0199] The weight-average molecular weight (Mw) of the crystalline polyester resin is preferably between 6,000 and 50,000.
[0200] Crystalline polyester resins can be obtained, for example, by well-known manufacturing methods, similar to amorphous polyesters.
[0201] The resin content is preferably 40% to 95% by mass, more preferably 50% to 90% by mass, and even more preferably 60% to 90% by mass, relative to the total toner particles.
[0202] Here, if the toner particles contain resin as resin particles, they may also contain crosslinked resin particles. The crosslinking agent for the crosslinked resin particles may be used alone or in combination of two or more types. The average primary particle diameter of the resin particles is preferably 10 nm to 500 nm, more preferably 20 nm to 300 nm, and even more preferably 30 nm to 250 nm. The average primary particle size of resin particles is a value measured using a transmission electron microscope (TEM). For example, the Hitachi High-Tech S4800 transmission electron microscope can be used. Specifically, the method for measuring the average primary particle diameter of resin particles is as follows: The toner particles are cut into pieces approximately 0.1 μm thick using a microtome. A 10,000x magnification image of the cross-section of the toner particles is taken using a transmission electron microscope. For 100 resin particles dispersed within the toner particles, the equivalent diameter of each circle is calculated from the individual cross-sectional area, and the arithmetic mean of these values is taken as the average primary particle diameter. The resin particle content is preferably 0% to 30% by mass relative to the toner particles, more preferably 1% to 25% by mass, and even more preferably 3% to 20% by mass.
[0203] -Colorants- Examples of colorants include carbon black, chrome yellow, Hansa yellow, benzidine yellow, surene yellow, quinoline yellow, pigment yellow, permanent orange GTR, pyrazolone orange, balkan orange, Watch Young red, permanent red, brilliant carmine 3B, brilliant carmine 6B, DuPont oil red, pyrazolone red, risole red, rhodamine B lake, lake red C, pigment red, rose bengal, aniline blue, ultramarine blue, and calco oil blue. Examples of colorants include various pigments such as methylene blue chloride, phthalocyanine blue, pigment blue, phthalocyanine green, and malachite green oxalate; inorganic pigments such as titanium compounds, silica, aluminum, and mica; and various dyes such as acridine, xanthene, azo, benzoquinone, azine, anthraquinone, thioindigo, dioxazine, thiazine, azomethine, indigo, phthalocyanine, aniline black, polymethine, triphenylmethane, diphenylmethane, and thiazole. The colorant is not limited to substances that absorb in the visible light region. For example, the colorant may be a substance that absorbs in the near-infrared region, a fluorescent colorant, or a colorant that exhibits luminescence. Colorants may be used individually or in combination of two or more types.
[0204] The coloring agent may be a surface-treated coloring agent as needed, and may be used in combination with a dispersant. Furthermore, multiple types of coloring agents may be used in combination.
[0205] The colorant content is preferably 1% to 30% by mass, and more preferably 3% to 15% by mass, relative to the total toner particles.
[0206] The coloring agent may be incorporated into the resin or used in a compound form, as needed. There are no particular restrictions on the resin used, but from the viewpoint of compatibility, it is preferable to use the resins mentioned above or resins with similar structures.
[0207] -Release agent- Examples of release agents include hydrocarbon waxes; natural waxes such as carnauba wax, rice wax, and candelilla wax; synthetic or mineral / petroleum waxes such as montan wax; and ester waxes such as fatty acid esters and montanic acid esters. There are no particular restrictions on the release agent, and it can be appropriately selected depending on the purpose, with hydrocarbon waxes and ester waxes being preferred. These release agents may be used individually or in combination of two or more types.
[0208] The melting temperature of the release agent is preferably 50°C to 110°C, and more preferably 60°C to 100°C. The melting temperature is determined from the DSC curve obtained by differential scanning calorimetry (DSC) using the "melting peak temperature" described in JIS K 7121-1987 "Method for determining the transition temperature of plastics".
[0209] The release agent content is preferably 1% to 20% by mass, and more preferably 4% to 15% by mass, relative to the total toner particles.
[0210] Furthermore, the release agent may be used either incorporated into the resin or compounded with it, as needed. There are no particular restrictions on the resin used, but from the viewpoint of compatibility, it is preferable to use the resins mentioned above or resins with similar structures.
[0211] -Other additives- Other additives include well-known additives such as magnetic materials, charge control agents, and inorganic powders. These additives are preferably included in the toner particles as internal additives. There are no particular restrictions on the charge control agent, and it can be appropriately selected depending on the purpose. Examples include nigrosine dyes, triphenylmethane dyes, chromium-containing metal complex dyes, molybdate chelate pigments, rhodamine dyes, alkoxyamines, quaternary ammonium salts (including fluorine-modified quaternary ammonium salts), alkylamides, elemental or compound phosphorus, elemental or compound tungsten, fluorine-based surfactants, metal salicylic acid salts, and metal salts of salicylic acid derivatives. When used as a negatively charged toner, azo complex salt dyes such as chromium and iron, complex compounds of salicylic acid such as chromium, zinc, aluminum, and boron, and charge control resins can be used as charge control agents. There are no particular restrictions on the content of the charge control agent, and it can be appropriately selected depending on the purpose, but it is preferably 0.1 parts by mass or more and 10 parts by mass or less, and more preferably 0.2 parts by mass or more and 5 parts by mass or less, per 100 parts by mass of the toner. Examples of inorganic powders include layered inorganic powders and layered inorganic minerals in which at least some of the interlayer ions are modified with organic ions. Examples include montmorillonite, bentonite, hectorite, attapulgite, sepiolite, and mixtures thereof. Among these, organically modified montmorillonite or bentonite is preferred as the inorganic powder because it does not affect the toner properties, allows for easy viscosity adjustment, and enables the addition of small amounts. It may be used when manufacturing toner by the ester extension method described later. The inorganic powder content is preferably 0.2% to 2.0% by mass relative to the toner particles, and more preferably 0.7% to 1.5% by mass.
[0212] -Characteristics of toner particles, etc.- The toner particles may be single-layer toner particles, or they may be toner particles with a so-called core-shell structure, consisting of a core (core particle) and a coating layer (shell layer) that covers the core. Here, the core-shell structure of the toner particles may consist, for example, a core composed of a resin and optionally a colorant, release agent, and other additives, and a coating layer composed of a resin. The coating layer may have a multilayer structure. The type of resin, glass transition temperature (Tg), SP value, and other physical properties may be changed for each layer of the core or coating layer, and the presence or type of colorant and release agent may also be changed.
[0213] In this case, the coating layer may be formed when manufacturing the toner particles, or a step may be provided to form the coating layer after manufacturing the toner particles. For example, multiple manufacturing methods may be used, such as producing toner particles by the kneading and grinding method described later, followed by forming a coating layer by a wet manufacturing method. Alternatively, a coating layer may be formed by attaching polymerization components and / or crosslinking components, followed by polymerization and / or crosslinking reactions. A coating layer may also be formed by depositing organosilicon compounds / polymers or organotitanium compounds / polymers on the surface of the toner particles using a sol-gel manufacturing method or the like. The coating layer may be cured by surface solidification treatment using hot air or dry milling, or by surface treatment with amines or compounds containing isocyanate groups, thermosetting resins, thermoplastic resins, etc. The coating layer may contain organic and / or inorganic components, and may also contain the aforementioned resins and the external additives described later. The coverage ratio of the coating layer over the core can be adjusted according to the purpose, and depending on the purpose, the coating layer may cover part or all of the surface of the core.
[0214] The volume-average particle size (D50v) of the toner particles is preferably 2 μm or more and 10 μm or less, and more preferably 4 μm or more and 8 μm or less.
[0215] The average particle size and particle size distribution indices of the toner particles are measured using a Coulter Multisizer 4e (manufactured by Beckman Coulter), and the electrolyte is measured using an ISOTON-II (manufactured by Beckman Coulter). For measurement, add 0.5 mg to 50 mg of the sample to be measured in 2 ml of a 5% aqueous solution of a surfactant (preferably sodium alkylbenzenesulfonate) as a dispersant. Add this to 100 ml to 150 ml of electrolyte. The electrolyte containing the suspended sample is dispersed in an ultrasonic disperser for 1 minute. The particle size distribution of particles with a diameter of 1 μm to 30 μm is then measured using a Coulter Multisizer II with a 50 μm aperture. The number of particles sampled is 50,000. Based on the measured particle size distribution, a cumulative distribution of volume and number is drawn for each divided particle size range (channel) from the smallest diameter side. The particle size at which the cumulative total reaches 16% is defined as the volume particle size D16v and the number particle size D16p, the particle size at which the cumulative total reaches 50% is defined as the volume average particle size D50v and the cumulative number average particle size D50p, and the particle size at which the cumulative total reaches 84% is defined as the volume particle size D84v and the number particle size D84p. Using these, the volume particle size distribution index (GSDv) is (D84v / D16v) 1 / 2 The GSDp index is (D84p / D16p) 1 / 2 It is calculated as follows.
[0216] The average circularity of the toner particles is preferably 0.90 or more and 1.00 or less, and more preferably 0.92 or more and 0.98 or less.
[0217] The average circularity of toner particles is determined by (circular equivalent perimeter) / (perimeter) [(perimeter of a circle with the same projected area as the particle image) / (perimeter of the particle projection image)]. Specifically, it is a value measured by the following method. First, the toner particles to be measured are collected by suction, a flattened flow is formed, and a strobe flash is instantaneously activated to capture a still image of the particles. This particle image is then analyzed using a flow-type particle image analyzer (Paasche analyzer PAS, manufactured by Hosokawa Micron Corporation). The number of samples used to determine the average circularity is 10,000. If the toner contains external additives, the toner (developer) to be measured is dispersed in water containing a surfactant, and then ultrasonic treatment is performed to obtain toner particles from which the external additives have been removed.
[0218] (External additive) Examples of external additives include inorganic particles. These inorganic particles include SiO2, TiO2, Al2O3, SrTiO3, CaTiO3, CuO, ZnO, SnO2, CeO2, Fe2O3, MgO, BaO, CaO, K2O, Na2O, ZrO2, CaO·SiO2, and K2O·(TiO2). n Examples include Al2O3·2SiO2, CaCO3, MgCO3, BaSO4, and MgSO4.
[0219] The surface of the inorganic particles used as an external additive should preferably be hydrophobic. Hydrophobic treatment is carried out, for example, by immersing the inorganic particles in a hydrophobic agent. The hydrophobic agent is not particularly limited, but examples include silane-based coupling agents, silicone oil, titanate-based coupling agents, aluminum-based coupling agents, and other silicon compounds. These may be used individually or in combination of two or more. The amount of hydrophobic treatment agent is typically, for example, 1 to 30 parts by mass per 100 parts by mass of inorganic particles.
[0220] Examples of external additives include resin particles (such as polystyrene, polymethyl methacrylate (PMMA), and melamine resin), and cleaning lubricants (for example, metal salts of higher fatty acids represented by zinc stearate, and higher alcohols).
[0221] The amount of external additive added is preferably 0.01% by mass or more and 10% by mass or less relative to the toner particles, and more preferably 0.01% by mass or more and 8.0% by mass or less.
[0222] (Toner manufacturing method) Next, a description of the toner manufacturing method according to this embodiment will be given. The toner according to this embodiment is obtained by manufacturing toner particles and then adding an external additive to the toner particles.
[0223] Toner particles may be manufactured by either a dry process (e.g., kneading and grinding) or a wet process (e.g., agglomeration, suspension polymerization, dissolution-suspension, ester extension). There are no particular restrictions on the manufacturing method of toner particles, and any well-known method may be used.
[0224] The kneading and grinding method involves melt-kneading the resin with, if necessary, colorants, antistatic agents, and release agents, then cooling, finely grinding, and further classifying toner particles. The kneaded material may be ground using a grinder such as a jet mill, turbo mill, cryptron, or inomizer (grinding step), and the ground material may be classified using a classifier such as an elbow jet, turboplex, or dispersion separator.
[0225] The agglomeration and coalescence method involves the following steps to produce toner particles: preparing a resin particle dispersion in which resin particles to be made are dispersed (resin particle dispersion preparation step); agglomerating the resin particles (and other particles as needed) in the resin particle dispersion (or in a dispersion after mixing with other particle dispersions as needed) to form agglomerated particles (agglomerated particle formation step); and heating the agglomerated particle dispersion in which the agglomerated particles are dispersed to fuse and coalesce the agglomerated particles to form toner particles (fusion and coalescence step).
[0226] The dissolution suspension method involves dispersing or emulsifying resins or resin precursors in an aqueous medium containing an organic solvent to produce toner particles.
[0227] The ester extension method is a dissolution suspension method in which an oil phase composition containing a resin precursor having a reactive functional group is emulsified or dispersed in an aqueous medium containing resin fine particles, and toner particles are produced by reacting an active hydrogen group-containing compound with the resin precursor in the aqueous medium.
[0228] In addition, in any of the manufacturing methods, colorants, release agents, and other additives (such as antistatic agents) may be used as needed.
[0229] (Career) There are no particular restrictions on the carriers, and known carriers can be used. Examples of carriers include coated carriers in which a coating resin is applied to the surface of a core material made of magnetic powder; magnetic powder dispersed carriers in which magnetic powder is dispersed and blended in a matrix resin; and resin-impregnated carriers in which resin is impregnated into porous magnetic powder. Furthermore, magnetic powder dispersed carriers and resin-impregnated carriers may be carriers in which the constituent particles of the carrier are used as a core material and coated with a coating resin.
[0230] Examples of magnetic powders include magnetic metals such as iron, nickel, and cobalt, and magnetic oxides such as ferrite and magnetite. Magnetite and ferrite are particularly preferred. Magnetic powders can also be used as particles dispersed in a resin.
[0231] Examples of coating resins and matrix resins include polyethylene, polypropylene, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl butyral, polyvinyl chloride, polyvinyl ether, polyvinyl ketone, vinyl chloride-vinyl acetate copolymer, styrene-acrylic acid ester copolymer, straight silicone resin or modified thereof containing organosiloxane bonds, fluororesin, polyester, polycarbonate, phenolic resin, epoxy resin, and the like.
[0232] Furthermore, the coating resin and matrix resin may contain conductive particles or other additives. Examples of conductive particles include metals such as gold, silver, and copper, as well as carbon black, titanium oxide, zinc oxide, tin oxide, barium sulfate, aluminum borate, and potassium titanate. Other additives include inorganic particles, metal oxide particles such as silica, titanium dioxide, zinc oxide, and tin oxide; metal compound particles such as barium sulfate, aluminum borate, and potassium titanate; and metal particles such as gold, silver, and copper.
[0233] To coat the surface of the core material with a coating resin, one method is to coat it with a coating layer-forming solution prepared by dissolving the coating resin and, if necessary, various additives in a suitable solvent. The solvent is not particularly limited and should be selected considering the coating resin used, its suitability for coating, etc. Specific resin coating methods include the immersion method, in which the core material is immersed in a coating layer forming solution; the spray method, in which the coating layer forming solution is sprayed onto the surface of the core material; the fluidized bed method, in which the coating layer forming solution is sprayed onto the core material while it is suspended by fluidized air; and the kneader coater method, in which the carrier core material and the coating layer forming solution are mixed in a kneader coater and the solvent is removed.
[0234] In a two-component developer, the mixing ratio (mass ratio) of toner and carrier is preferably toner:carrier = 1:100 to 30:100, and more preferably 3:100 to 20:100.
[0235] Although this embodiment has been described above, it is not intended to be interpreted as being limited to the above embodiment, and various modifications, changes, and improvements are possible. [Examples]
[0236] The embodiment will be described in more detail below with reference to examples, but this embodiment is not limited to the following examples. In the following, "part" refers to "mass parts" unless otherwise specified.
[0237] <Example 1> (Formation of resin substrate layer) An N-methyl-2-pyrrolidone (NMP) solution (solid content concentration 18% by mass) of polyimide precursor (polyimide varnish "U Varnish-S", manufactured by UBE Co., Ltd.) was spirally coated onto a mold with a diameter of φ30 mm to a film thickness of 60 μm, and fired to 380°C by the following step heating procedure. The step heating procedure involved raising the temperature from 25°C to 120°C, maintaining it at 120°C for 1 hour, raising the temperature from 120°C to 250°C, maintaining it at 250°C for 1 hour, raising the temperature from 250°C to 380°C, maintaining it at 380°C for 1 hour, and then cooling it down from 380°C to 25°C. This resulted in a tubular polyimide resin belt (hereinafter referred to as PI substrate) consisting of a single layer of polyimide resin with an outer diameter of 30 mm, a film thickness of 60 μm, and a width of 400 mm. This was used as the resin substrate layer.
[0238] A liquid honing device (LH-8TTHiS, manufactured by Fuji Seiki Co., Ltd.) was used to roughen the surface of the PI substrate, resulting in a surface roughness Ra of 0.5 μm to 1.0 μm. The honing conditions were abrasive #320, spray pressure of 0.3 MPa, spray distance of 100 mm, and processing time of 1.5 minutes. After the abrasive particles on the roughened surface of the PI substrate were washed off with deionized water, the moisture on the surface of the PI substrate was removed with compressed air.
[0239] (Formation of an elastic layer) Next, a solution was prepared by mixing equal amounts of solution A and solution B of PRIMER-NO.32 (two-component silicone rubber primer, manufactured by Shin-Etsu Chemical Co., Ltd.), stirring it, and applying it to the surface of the PI substrate using a spiral coating apparatus. The solution was then air-dried at room temperature for 30 minutes and baked at 170°C for 20 minutes to form an adhesive layer with a thickness of 0.2 μm.
[0240] Next, silicone rubber (X34-3160-A, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with butyl acetate to a solid content concentration of 85% by mass to obtain a coating solution for forming an elastic layer. The coating solution for forming an elastic layer was applied to the surface (i.e., the outer surface) of the adhesive layer to a thickness of 500 μm using a spiral coating apparatus to form a coating film. Next, the formed coating film was subjected to a self-smoothing treatment (30°C for 5 minutes) and primary vulcanization (120°C for 20 minutes) to form an elastic layer.
[0241] (Formation of the surface layer) Next, a coating solution was prepared by mixing components (A) to (C) shown in Table 1 in the amounts (parts by mass) shown in Table 1 using a spiral coating apparatus on the surface of the elastic layer. This addition-curable organopolysiloxane composition was then diluted with butyl acetate to a solid content concentration of 80%. The resulting coating solution was applied to the elastic layer, dried at 23°C for 30 minutes, and then heated at 200°C for 240 minutes to form a 30 μm surface layer.
[0242] The fixing belt was obtained through the above process.
[0243] <Examples 2-7, Comparative Example 1> A fixed belt was obtained in the same manner as in Example 1, except that the type and amount of each component were changed according to Table 1 when forming the surface layer. However, in Examples 5 to 7, carbon black was added to the addition-curable organopolysiloxane composition according to Table 1 to form a surface layer. The carbon black was added to the addition-curable organopolysiloxane composition in parts per 100 parts by mass of resin (PHR as shown in Table 1).
[0244] <Comparative Example 2> A fixing belt was obtained in the same manner as in Example 1, except that the surface layer was formed as follows. Synthesized with reference to Examples 1-3 of International Publication No. 2023 / 157603 (R 1 -SiO 3 / 2 ) m and (R 1 R 2 -SiO 2 / 2 ) n Organopolysiloxane compounds containing structural units (m / n=7, R 1 =methyl group, R 2 = vinyl group, and in the following formula (I), X = ethylene group, Y = bond to the silicon atom represented by * below, and trimethoxysilyl group, R 4 A methyl group (represented by L=9, Mw=6,000) was diluted with n-heptane to a solid content concentration of 80% to prepare a coating solution for surface formation. A coating film was formed on the elastic layer by applying a surface-forming coating solution to a thickness of 30 μm using a spiral coating apparatus. The coating film was then left to stand at room temperature for 7 days to form a 30 μm surface layer.
[0245] <Comparative Example 3> A fixing belt was obtained in the same manner as in Example 1, except that the surface layer was formed as follows. The composition of the organopolysiloxane compound in Comparative Example 2 was given as "m / n=7, R 1=methyl group, R 2 = vinyl group, and in the following formula (I), X = ethylene group, Y = bond to the silicon atom represented by * and trimethoxysilyl group, R 4 A 30 μm surface layer was formed in the same manner as in Comparative Example 2, except that the group was changed to a methyl group, represented by L=15, and Mw=10,000.
[0246] <Comparative Example 4) A fixing belt was obtained in the same manner as in Example 1, except that the surface layer was formed as follows. The composition of the organopolysiloxane compound in Comparative Example 2 was given as "m / n=7, R 1 =methyl group, R 2 = vinyl group, and in the following formula (I), X = ethylene group, Y = bond to the silicon atom represented by * and a dimethoxymethyl group, R 4 A 30 μm surface layer was formed in the same manner as in Comparative Example 2, except that the group was changed to a methyl group, represented by L=19, and Mw=23,000.
[0247] [ka]
[0248] <Comparative Example 5> A fixing belt was obtained in the same manner as in Example 1, except that the surface layer was formed as follows. Silicone rubber (X-34-3160-A, manufactured by Shin-Etsu Chemical Co., Ltd.) was diluted with butyl acetate to a solid content concentration of 30% by mass to obtain a coating solution for surface formation. A coating film was formed on the surface of the elastic layer by applying a surface-forming coating solution to a thickness of 30 μm using a spiral coating apparatus. Next, the formed coating film was subjected to a self-smoothing treatment (30°C x 5 minutes), primary vulcanization (120°C x 20 minutes), and secondary vulcanization (200°C x 4 hours) to form a surface layer.
[0249] The materials used are described below. <(A) component> (A-1: Organopolysiloxane resin obtained in Synthesis Example 1 below (A-1)) -Synthesis Example 1 of Organopolysiloxane Resin (A-1)- 4,086.6 g of methyltrimethoxysilane was placed in a glass flask equipped with a stirrer, thermometer, condenser, and dropping device. Then, 486 g of 1N hydrochloric acid was added dropwise over 1 hour while stirring, and the mixture was reacted at 67°C for 2 hours. The resulting solution was neutralized with 29.2 g of propylene oxide, and polysilsesquioxane (A-0) was obtained by distilling off the volatile components and solvent. 2,252 g of the obtained polysilsesquioxane (A-0), 1,090 g of vinylmethyldimethoxysilane, 876 g of methyldimethoxysilane, 1,292 g of hexamethyldisiloxane, and 4,137 g of toluene were mixed with 60 g of methanesulfonic acid while stirring. Then, 539 g of water was added dropwise over 1 hour, and the mixture was reacted at 67°C for 2 hours, and then at a temperature range of 80°C to 90°C for 3 hours. The resulting solution was washed with water until the extract water was neutral, and the solvent was removed by distillation to obtain the product. The obtained organopolysiloxane resin (A-1) 1 H-NMR and 29 The proportions of each constituent unit in equation (1), calculated from the results of Si-NMR measurements, are a=0, b=0.5, c=0, d=0, e=0.3, f=0.2, g=0, and h=0.02, respectively. 1 R is a methyl group, 2 The vinyl group:hydrogen atom = 50:50 (molar ratio), R 3 It was a hydrogen atom, with a weight-average molecular weight of 10,000 and an alkenyl group content of 0.2 moles / 100g.
[0250] <(B) component> B-1: In the above equation (2), R 4 =methyl group, R 5 = Hydrogen atom, R 6 = A linear polysiloxane (B-1) represented by a methyl group and n=20.
[0251] B-2: In the above equation (2), R 4 =methyl group, R 5= Hydrogen atom, R 6 = A linear polysiloxane (B-2) represented by a methyl group and n=40.
[0252] <(C) component> C-1: Toluene solution of platinum-divinyltetramethyldisiloxane complex (platinum concentration 0.5% by mass)
[0253] <Carbon> PRINTEX Kappa70: Orion Engineered Carbons' "PRINTEX Kappa70" Ketjenblack EC600JD: Lion Specialty Chemicals Co., Ltd. "Ketjenblack EC600JD"
[0254] <Rating> (Characteristic evaluation) The following characteristics of the anchoring belt in each example were measured. • High-temperature release properties of the surface layer (however, the release properties of the surface layer were measured as follows.) • Elastic modulus of the surface layer at 140℃ E A • The elastic modulus E of the surface layer at 140°C after being heated at 200°C for 48 hours in an oxygen atmosphere. B • Surface elongation (however, surface elongation was measured as follows.)
[0255] -Method for measuring the high-temperature release properties of the surface layer- The high-temperature release properties of the surface layer of the fixing belt in each example were measured as follows. As preparation, prepare A4-sized P-paper (manufactured by Fujifilm Business Innovation Co., Ltd.) and use a Fujifilm Business Innovation Co., Ltd. copier (ApeosPort-V C3375) to print a full-page process black image onto the test paper. Also, take a 10mm x 10mm square sample from the fuser belt to be measured. Next, the sample piece is attached to the probe of a tack tester (TA-500, manufactured by UBM) at room temperature (25°C) or preheated to 140°C. The probe is then brought close to the test paper at a speed of 0.1 mm / s, pressed against the image surface of the test paper, held for 10 seconds with a pressing load of 5.0 kgf / cm², and the peeling force is measured when the probe is pulled up at a pulling speed of 10 mm / s.
[0256] -Method for measuring surface elongation- Sample pieces were taken from the surface layer of the anchoring belt in each example. The sample pieces were then placed on a tensile testing machine, and the elongation at break (tensile elongation) was measured under the following conditions. • Sample size: No. 7 dumbbell (JIS K 6251:2023) • Test equipment: Tabletop load testing machine FTN1-13A (manufactured by Aiko Engineering Co., Ltd.) • Pulling speed: 200 mm / min
[0257] In Table 1, the number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition per alkenyl group bonded to silicon atoms in the addition-curable organopolysiloxane composition is shown as H / Vi.
[0258] (Actual device evaluation) The fixing belts of Examples 1-4 and Comparative Examples 1-5 were mounted as heating belts in the fixing unit of the evaluation image forming apparatus "Fujifilm Business Innovation Co., Ltd. 'ApeosPort-V C3375'". The following evaluations were then performed. The fixing belts from Examples 5-7 were used as pressure belts and attached to the fixing unit of the evaluation image forming apparatus "ApeosPrint C5240" manufactured by Fujifilm Business Innovation Co., Ltd. The following evaluation was then performed.
[0259] - Toner offset (a phenomenon in which toner is transferred to the fixing material due to insufficient toner melting) and paper staining - Using an evaluation image forming apparatus, image patterns were printed on both sides of A4 paper (P paper, OSC 127 paper, Lezack 66 paper) in yellow (Y), magenta (M), cyan (C), black (K), red (R), green (G), blue (B), and pink (PK) at a position 5 mm from the leading edge of the paper, with each pattern measuring 40 mm x 40 mm. The image quality and paper smudges of the 100th sheet were then visually evaluated. The evaluation criteria are as follows: -Evaluation Criteria for Toner Offset- A: No toner offset is visible. B: Upon close inspection, slight toner offset is visible, but there are no problems in actual use. C: Toner offset is visible. In Examples 1-4 and Comparative Examples 1-5, toner offset was evaluated based on the image on the heating belt side, while in Examples 5-7, it was evaluated based on the image on the pressure belt side. -Evaluation criteria for paper stains- A: No toner stains are visible on the paper. B: Upon close inspection, minor toner stains can be seen on the paper, but there are no problems with practical use. C: Toner stains are visible on the paper. Furthermore, paper staining was evaluated based on toner stains on the paper caused by the accumulation of toner in wrinkles or cracks that occur on the surface of the fuser belt due to its low flexibility.
[0260] [Table 1]
[0261] [Table 2]
[0262] From the above results, it can be seen that the fixing belt of this embodiment has superior release properties at high temperatures compared to the fixing belt of the comparative example. Furthermore, the elastic modulus E of the surface layer A and the elastic modulus E of the surface layer B It can be seen that both the stretchability and flexibility are high, and that the ability to maintain flexibility is also excellent. Furthermore, it can be seen that the fuser belt in this embodiment suppresses toner offset and reduces paper smudging compared to the fuser belt in the comparative example.
[0263] This embodiment includes the following aspects. (((1))) Having a base material and a surface layer, The aforementioned surface layer is (A) Organopolysiloxane resin having a constituent unit represented by the following formula (1), [ka] (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 2 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms (however, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%. 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0≦a≦0.6, 0.2≦b≦0.9, 0≦c≦0.8, 0≦d≦0.6, 0≦e≦0.8, 0≦f≦0.6, 0≦g≦0.8, and 0.1≦(c+e+g)≦0.8 and a+b+c+d+e+f+g=1, and h is a number satisfying 0≦h≦1. (B) Linear organopolysiloxane represented by the following formula (2) [ka] (In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 5 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, and R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer between 0 and 1,200. The composition includes an addition-cured product of an addition-curable organopolysiloxane composition containing, The content of component (B) relative to 100 parts by mass of component (A) is 10 parts by mass or more and 300 parts by mass or less. The elastic modulus E of the surface layer at 140°C A However, the pressure is between 10 MPa and 200 MPa. The elastic modulus E of the surface layer at 140°C after heating at 200°C for 48 hours in an oxygen atmosphere. B However, it is between 20 MPa and 100 MPa. Fixing member. (((2))) (A) Organopolysiloxane resin having a constituent unit represented by the following formula (1) [ka] (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 2 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms (however, R 2 (The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%), R 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0≦a≦0.6, 0.2≦b≦0.9, 0≦c≦0.8, 0≦d≦0.6, 0≦e≦0.8, 0≦f≦0.6, 0≦g≦0.8, and 0.1≦(c+e+g)≦0.8 and a+b+c+d+e+f+g=1, and h is a number satisfying 0≦h≦1. (B) Linear organopolysiloxane represented by the following formula (2) [ka] (In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, and R 5Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, and R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer between 0 and 1,200. and (C) Platinum group metal catalyst The process includes applying an addition-curable organopolysiloxane composition containing the above onto a substrate and curing it to form a surface layer. The content of component (B) in the composition is 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of component (A), The elastic modulus E of the surface layer at 140°C A However, the pressure is between 10 MPa and 200 MPa. The elastic modulus E of the surface layer at 140°C after being heated and left in an oxygen atmosphere at 200°C for 48 hours. B However, it is between 20 MPa and 100 MPa. A method for manufacturing a fixing member. (((3))) A method for manufacturing a fixing member as described in (((2))), wherein the content of component (C) relative to 100 parts by mass of component (A) is 0.00001 parts by mass or more and 0.005 parts by mass or less on a mass basis converted to platinum group metal atoms. (((4))) The aforementioned R 1 However, it is a methyl group or a phenyl group, and the R 2 The fixing member according to (((1))), wherein the alkenyl group in (((1))) is a vinyl group. (((5))) The fixing member described in (((1))) or (((4))) wherein a is 0. (((6))) The fixing member according to (((1))), (((4))), or (((5))), wherein the aforementioned g is 0. (((7))) The fixing member according to any one of the following items (((1))) or (((4))) to (((6))), wherein c, e, and g are numbers that satisfy 0 ≤ c ≤ 0.4, 0.1 ≤ e ≤ 0.5, 0 ≤ g ≤ 0.4, and 0.1 ≤ (c + e + g) ≤ 0.8. (((8))) The fixing member according to any one of the following items (((1))) or (((4))) to (((7))), wherein the alkenyl group content in component (A) is 0.05 mol / 100g or more and 0.6 mol / 100g or less. (((9))) The fixing member according to any one of the following items (((1))) or (((4))) to (((8))), wherein the weight-average molecular weight (Mw) of component (A) in terms of polystyrene in gel permeation chromatography is 1,000 or more and 50,000 or less. (((10))) The aforementioned R 4 However, it is a methyl group, and the R 5 However, it is a hydrogen atom, and the R 6 However, the fixing member is a methyl group as described in (((1))) or any one of (((4))) to (((9))). (((11))) The fixing member according to any one of the following items (((1))) or (((4))) to (((10))), wherein the number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition is 0.8 or more and 2.0 or less per alkenyl group bonded to silicon atoms in the addition-curable organopolysiloxane composition. (((12))) The fixing member according to any one of the following items, wherein the surface layer further contains carbon (((1))), or (((4))) to (((11))). (((13))) It comprises a first rotating body and a second rotating body positioned in contact with the outer surface of the first rotating body, A fixing device in which at least one of the first rotating body and the second rotating body is a fixing member described in any one of the items (((1))) or (((4))) to (((12))). (((14))) Image holder and, A charging device for charging the surface of the image holder, An electrostatic latent image forming apparatus for forming an electrostatic latent image on the surface of the charged image holder, A developing apparatus that develops an electrostatic latent image formed on the surface of the image holder with toner to form a toner image, A transfer device for transferring a toner image formed on the surface of the image holder to a recording medium, A fixing device described in (((13))) for fixing the toner image onto the recording medium, An image forming apparatus having
[0264] The effects of the above embodiment are as follows: According to the invention of (((1))), in a fixing member having a surface layer containing an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B), if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B Compared to cases where the pressure is less than 20 MPa or more than 100 MPa, a fixing member is provided having a surface layer with superior high-temperature release properties and flexibility retention.
[0265] According to the invention of (((2))), in a method for manufacturing a fixing member, the step of applying an addition-curable organopolysiloxane composition containing component (A), component (B), and component (C) onto a substrate and curing it to form a surface layer, if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and if the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B A method for manufacturing a fixing member having a surface layer with superior high-temperature release properties and flexibility retention is provided, compared to cases where the pressure is less than 20 MPa or more than 100 MPa.
[0266] According to the invention of (((3))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility maintenance compared to a case where the content of component (C) per 100 parts by mass of component (A) is less than 0.00001 parts by mass or more than 0.005 parts by mass on a mass basis converted to platinum group metal atoms. According to the invention relating to (((4))), R 1 If R is a group other than a methyl group and a phenyl group, 2 Compared to cases where the alkenyl group is a group other than a vinyl group, a fixing member is provided having a surface layer with superior high-temperature release properties and flexibility retention. According to the invention of (((5))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility maintenance compared to the case where a is greater than 0. According to the invention of (((6))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where g is greater than 0. According to the invention of (((7))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where c, e, and g do not satisfy the above formula. According to the invention of (((8))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to the case where the alkenyl group content in component (A) is less than 0.05 mol / 100g or greater than 0.6 mol / 100g. According to the invention of (((9))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to cases where the weight-average molecular weight (Mw) of component (A) in terms of polystyrene in gel permeation chromatography is less than 1,000 or more than 50,000. According to the invention relating to (((10))), R 4 If R is a group other than a methyl group, 5 If R is a group other than a hydrogen atom, 6 Compared to cases where the group is not a methyl group, a fixing member is provided having a surface layer that exhibits superior high-temperature release properties and flexibility retention. According to the invention of (((11))), a fixing member is provided having a surface layer that is superior in high-temperature release properties and flexibility retention compared to cases where the number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition is less than 0.8 or more than 2.0 per alkenyl group bonded to silicon atoms in the addition-curable organopolysiloxane composition. According to the invention of (((12))), in a fixing member having a surface layer containing an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B), if component (A) does not satisfy 0.2 ≤ b ≤ 0.9 or 0.1 ≤ (c + e + g) ≤ 0.8, and the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus of the surface layer E A If the pressure is less than 10 MPa or more than 200 MPa, or if the elastic modulus of the surface layer is E B Compared to cases where the pressure is less than 20 MPa or more than 100 MPa, a fixing member is provided that has a surface layer containing carbon, which is excellent in maintaining high temperature release properties and flexibility.
[0267] According to the inventions of (((13))) or (((14))), in a fixing member having a surface layer containing an addition-cured product of an addition-curable organopolysiloxane composition containing component (A) and component (B), when a fixing member is applied in which component (A) does not satisfy 0.2≦b≦0.9 or 0.1≦(c+e+g)≦0.8, when a fixing member is applied in which the content of component (B) is less than 10 parts by mass or more than 300 parts by mass, the elastic modulus E of the surface layer A When an anchoring member with a coefficient of elasticity less than 10 MPa or greater than 200 MPa is applied, or when the elastic modulus of the surface layer E B Compared to cases where a fixing member with a pressure of less than 20 MPa or more than 100 MPa is used, a fixing device or image forming apparatus is provided that has a fixing member having a surface layer with superior high-temperature release properties and flexibility retention. [Explanation of Symbols]
[0268] 100 Image forming apparatus 1Y, 1M, 1C, 1K Image Forming Unit 10 Primary Transfer Section 11 Photoreceptor 12 Chargers 13. Laser exposure unit 14. Developer 15 Intermediate transfer belt 16 Primary transfer roll 17 Photoconductor Cleaner 20 Secondary transfer section 22 Secondary transfer roll 25 Back Roll 26 Power supply roll 31 Drive Roll 32 support rolls 33 Tension-applying roll 34 Cleaning back roll 35 Intermediate Transfer Belt Cleaner 40 Control Unit 42 Reference Sensor 43 Image density sensor 50 Paper storage compartments 51 Paper feed roll 52 Conveyor Rolls 53 Conveyor Guide 55 Conveyor belt 56 Fixing entrance guide 60 Fixing device
Claims
1. Having a base material and a surface layer, The aforementioned surface layer is (A) Organopolysiloxane resin having a constituent unit represented by the following formula (1), 【Chemistry 1】 (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, R 2 Each of these independently represents a hydrogen atom or an alkenyl group having 2 to 12 carbon atoms (however, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%. 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0 ≤ a ≤ 0.6, 0.2 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.6, 0 ≤ e ≤ 0.8, 0 ≤ f ≤ 0.6, 0 ≤ g ≤ 0.8, and 0.1 ≤ (c + e + g) ≤ 0.8 and a + b + c + d + e + f + g = 1, and h is a number satisfying 0 ≤ h ≤ 1. (B) Linear organopolysiloxane represented by the following formula (2) 【Chemistry 2】 (In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, R 5 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer from 0 to 1,200. The composition includes an addition-cured product of an addition-curable organopolysiloxane composition containing, The content of component (B) relative to 100 parts by mass of component (A) is 10 parts by mass or more and 300 parts by mass or less. The elastic modulus E of the surface layer at 140°C A However, the pressure is between 10 MPa and 200 MPa. Elastic modulus E of the surface layer at 140°C after heating and leaving to stand at 200°C for 48 hours in an oxygen atmosphere B is 20 MPa or more and 100 MPa or less, Fixing member.
2. (A) Organopolysiloxane resin having a constituent unit represented by the following formula (1) 【Transformation 3】 (In formula (1), R 1 Each of these independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, R 2 Each of these independently represents a hydrogen atom or an alkenyl group having 2 to 12 carbon atoms (however, R 2 The proportion of hydrogen atoms in the total number of atoms is between 10 mol% and 90 mol%, R 3 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a, b, c, d, e, f, and g are numbers satisfying 0 ≤ a ≤ 0.6, 0.2 ≤ b ≤ 0.9, 0 ≤ c ≤ 0.8, 0 ≤ d ≤ 0.6, 0 ≤ e ≤ 0.8, 0 ≤ f ≤ 0.6, 0 ≤ g ≤ 0.8, and 0.1 ≤ (c + e + g) ≤ 0.8 and a + b + c + d + e + f + g = 1, and h is a number satisfying 0 ≤ h ≤ 1. (B) Linear organopolysiloxane represented by the following formula (2) 【Chemistry 4】 (In formula (2), R 4 Each of these independently represents a monovalent hydrocarbon group having 1 to 12 carbon atoms that does not contain an aliphatic unsaturated bond, R 5 Each of these independently represents a hydrogen atom or an alkenyl group with 2 to 12 carbon atoms, R 6 Each of these independently represents a monovalent hydrocarbon group with 1 to 12 carbon atoms, and n is an integer from 0 to 1,200. and (C) Platinum group metal catalyst The process includes applying an addition-curable organopolysiloxane composition containing the above onto a substrate and curing it to form a surface layer. The content of component (B) in the composition is 10 parts by mass or more and 300 parts by mass or less per 100 parts by mass of component (A), The elastic modulus E of the surface layer at 140°C A However, the pressure is between 10 MPa and 200 MPa. The elastic modulus E of the surface layer at 140°C after being heated and left in an oxygen atmosphere at 200°C for 48 hours. B However, the pressure is between 20 MPa and 100 MPa. A method for manufacturing a fixing member.
3. The method for manufacturing a fixing member according to claim 2, wherein the content of component (C) relative to 100 parts by mass of component (A) is 0.00001 parts by mass or more and 0.005 parts by mass or less on a mass basis converted to platinum group metal atoms.
4. The aforementioned R 1 However, it is a methyl group or a phenyl group, and the R 2 The fixing member according to claim 1, wherein the alkenyl group is a vinyl group.
5. The fixing member according to claim 1, wherein a is 0.
6. The fixing member according to claim 1, wherein g is 0.
7. The fixing member according to claim 1, wherein c, e, and g are numbers satisfying 0 ≤ c ≤ 0.4, 0.1 ≤ e ≤ 0.5, 0 ≤ g ≤ 0.4, and 0.1 ≤ (c + e + g) ≤ 0.
8.
8. The fixing member according to claim 1, wherein the alkenyl group content in component (A) is 0.05 mol / 100g or more and 0.6 mol / 100g or less.
9. The fixing member according to claim 1, wherein the weight-average molecular weight (Mw) of component (A) in terms of polystyrene in gel permeation chromatography is 1,000 or more and 50,000 or less.
10. The aforementioned R 4 However, it is a methyl group, and the R 5 However, it is a hydrogen atom, and the R 6 However, the fixing member according to claim 1 is a methyl group.
11. The fixing member according to claim 1, wherein the number of hydrogen atoms bonded to silicon atoms in the addition-curable organopolysiloxane composition is 0.8 or more and 2.0 or less per alkenyl group bonded to silicon atoms in the addition-curable organopolysiloxane composition.
12. The fixing member according to claim 1, wherein the surface layer further comprises carbon.
13. It comprises a first rotating body and a second rotating body arranged in contact with the outer surface of the first rotating body, A fixing device in which at least one of the first rotating body and the second rotating body is a fixing member as described in claim 1 or any one of claims 4 to 12.
14. Image holder and, A charging device for charging the surface of the image holder, An electrostatic latent image forming apparatus for forming an electrostatic latent image on the surface of the charged image holder, A developing apparatus that develops an electrostatic latent image formed on the surface of the image holder with toner to form a toner image, A transfer device for transferring a toner image formed on the surface of the image holder to a recording medium, A fixing device according to claim 13 for fixing the toner image onto the recording medium, An image forming apparatus having
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