JP2019019004A - Rotating sliding member - Google Patents

Abstract

To provide a rotating sliding member excellent in slidability and surface properties, having releasability and wettability, and excellent in adhesion between respective layers in a case of a laminate.SOLUTION: There is provided a rotating sliding member, including a tetrafluoroethylene-based polymer having at least one kind of adhesive functional group selected from a group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a rotary sliding member.

A seamless belt, which is a rotary sliding member, is used for an intermediate transfer belt, a transport belt of an electrophotographic image forming apparatus, a transport belt, an elastic belt, and the like of an ink jet image forming apparatus.
The seamless belt is required to have the following characteristics.
-In order to transfer toner uniformly, a seamless belt having excellent surface smoothness is required.
There is a need for a seamless belt that has excellent wettability so that the toner or ink does not scatter when the toner or ink adheres, and is excellent in releasability from the transferred material.
Since a residual toner on the surface of the intermediate transfer belt and toner or ink adhering to the surface of the conveying belt are easily worn by a cleaning blade, a seamless belt excellent in slidability is required.
-When a seamless belt is a laminated body, a seamless belt excellent in adhesion between each layer is required.

The following are proposed as a seamless belt excellent in slidability.
A seamless belt in which fine particles of fluororesin such as polytetrafluoroethylene (hereinafter referred to as PTFE) are dispersed on the surface of a resin film (Patent Document 1).
A seamless belt containing polyimide, a conductive filler, and a fluororesin filler such as PTFE (Patent Document 2).

JP 2000-155474 A JP 2011-240616 A

Since particles of fluororesin such as PTFE tend to aggregate in other resins such as polyimide, they tend to exist as coarse particles in the rotary sliding member. For this reason, since the smoothness of the surface of the seamless belt containing coarse particles is impaired, the transferability of the toner is deteriorated. Also, the toner or ink is likely to scatter when printing toner or discharging ink.
Furthermore, fluororesin particles such as PTFE have poor adhesion to other materials. Therefore, when the rotary sliding member is a laminate, the adhesion between the layers is inferior.

  The present invention provides a rotary sliding member that is excellent in slidability and surface properties, has releasability and wettability, and is excellent in adhesion between layers in the case of a laminate.

The present invention has the following aspects.
[1] A rotating slide containing a tetrafluoroethylene polymer having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group Moving member.
[2] Tetrafluoro, wherein the tetrafluoroethylene-based polymer has at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group The rotary sliding member according to [1], comprising units based on ethylene and units based on perfluoro (alkyl vinyl ether) or hexafluoropropylene.
[3] The rotating sliding member according to [1] or [2], including a polymer other than the tetrafluoroethylene-based polymer.
[4] The rotary sliding member according to [3], wherein the tetrafluoroethylene-based polymer is dispersed in the other polymer.
[5] The other polymer is a thermoplastic polyimide, a cured product of an epoxy resin, a cured product of a thermosetting polyimide, a polyphenylene sulfide, a polyetherimide, a polyetherketone, a polyethersulfone, a polytetrafluoroethylene, a polyfluoride. [3] or [4], which is at least one member selected from the group consisting of vinylidene chloride and polybutylene terephthalate.
[6] The rotary sliding member according to any one of [1] to [5], wherein the tetrafluoroethylene-based polymer is included in at least a part of the surface.
[7] The rotary sliding member according to any one of [1] to [6], wherein the arithmetic average roughness Ra of the surface is 0.05 to 30 μm.
[8] The rotating sliding member according to any one of [1] to [7], which is a seamless belt or an inkjet roller.
[9] The rotary sliding member according to any one of [1] to [8], which is an intermediate transfer belt.
[10] The rotating sliding member according to any one of [1] to [8], which is an elastic belt.

  The rotary sliding member of the present invention is excellent in slidability and surface properties, has releasability and wettability, and in the case of a laminate, it has excellent adhesion between layers.

10 is a scanning electron micrograph (5000 magnifications) of the cross section of the sample of Example 9. 2 is a scanning electron micrograph (5000 magnifications) of a cross section of a sample of Example 10. FIG. 2 is a scanning electron micrograph (400 magnifications) of the cross section of the sample of Example 11. FIG.

The meanings of the following terms in this specification are as follows.
“Unit based on monomer” is a general term for an atomic group directly formed by polymerizing one monomer molecule and an atomic group obtained by chemically converting a part of the atomic group. In the present specification, a unit based on a monomer is also simply referred to as a monomer unit.
The “melting point” is a temperature corresponding to the maximum value of the melting peak measured by the differential scanning calorimetry (DSC) method.
“Meltable and moldable” means exhibiting melt fluidity.
“Showing melt fluidity” means that there is a temperature at which the melt flow rate is 0.1 to 1000 g / 10 min at a temperature higher by 20 ° C. or more than the melting point of the resin under a load of 49 N.
The “melt flow rate” is a melt mass flow rate (MFR) defined in JIS K 7210: 1999 (corresponding international standard ISO 1133: 1997).
“Arithmetic average roughness Ra” is an arithmetic average roughness measured based on JIS B 0601: 2013 (corresponding international standard ISO 4287: 1997, Amd. 1: 2009).
"Dispersion particle size" is a length measurement function attached to the scanning electron microscope by observing the cross section of the rotating sliding member with a scanning electron microscope, and the particle size of 20 randomly selected domains (dispersion particles). The average particle size of 20 particles is obtained.
“˜” indicating a numerical range means that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.

<Rotating sliding member>
The rotary sliding member of the present invention includes a tetrafluoroethylene-based polymer having an adhesive functional group (hereinafter referred to as “adhesive fluoropolymer”).
The rotary sliding member of the present invention preferably contains a polymer other than the adhesive fluoropolymer from the viewpoint of conductivity and coloring.
The rotary sliding member of the present invention may contain other components as necessary within a range not impairing the effects of the present invention.

The rotary sliding member of the present invention may be a single-layer rotary sliding member consisting only of a layer containing an adhesive fluorine-containing polymer, and the outermost layer containing the adhesive fluorine-containing polymer and other layers. It may be a rotary sliding member made of a laminate. The rotary sliding member of the present invention preferably contains an adhesive fluoropolymer on at least a part of its surface.
Examples of other layers include a base material layer, a conductive layer, and a rubber elastic layer.
The material of the other layers is not particularly limited, and examples thereof include resins, metals such as aluminum, copper, and stainless steel, and ceramics.

Applications of the rotary sliding member of the present invention include a seamless belt, an ink jet roller, and the like, and more specifically, an intermediate transfer belt of an electrophotographic image forming apparatus, a conveying belt, an ink jet image forming apparatus. Examples thereof include a conveyance belt and an elastic belt.
As the rotary sliding member of the present invention, an intermediate transfer belt is preferable from the viewpoint that the effects of the present invention are effectively exhibited.
The rotary sliding member of the present invention may be used as an elastic belt. The elastic belt is a belt arranged to oppose the ink head. Because of its good trackability, it supports the paper firmly from the back and improves the quality of printing on various media such as paper and cloth. Further, since the heat resistance is improved, the life of the rotary sliding member is extended.
In addition to being used as a belt, the rotary sliding member of the present invention may be used by being wound around or coated on a drum, roll or the like.
The surface of the rotary sliding member of the present invention may be subjected to a surface treatment such as application of a treatment agent or polishing treatment in order to improve its appearance or release properties of toner or the like.

  The arithmetic average roughness Ra of the outer peripheral surface of the rotary sliding member of the present invention is preferably 0.05 μm to 30 μm, particularly preferably 0.05 μm to 20 μm. If the arithmetic average roughness Ra of the outer peripheral surface of the rotary sliding member is not less than the lower limit of the above range, the transportability of paper or the like is excellent. If the arithmetic average roughness Ra of the outer peripheral surface of the rotary sliding member is not more than the upper limit of the above range, the smoothness of the outer peripheral surface of the rotary sliding member and the wettability with respect to adhered matter such as ink and toner are excellent.

  The thickness of the rotary sliding member of the present invention is preferably from 0.1 μm to 0.5 mm, particularly preferably from 0.3 μm to 0.3 mm.

When the rotary sliding member of the present invention contains an adhesive fluorine-containing polymer and other polymers, the adhesive fluorine-containing polymer is contained in the other polymers from the viewpoint of wear resistance, sliding properties and smoothness. It is preferable that they are dispersed. In particular, when the rotating / sliding member is a seamless belt or an ink jet roller, if the surface has poor smoothness, the image quality of the initial image is significantly reduced. This is because if the irregularities on the surface are large, the toner is not stably held, and minute resistance unevenness occurs due to the difference in the toner layer, or the electrostatic adsorption force between the rotating sliding member and the toner can be different. Because. When the difference in electrostatic attraction force is large, it is difficult to control the voltage for efficient secondary transfer, which causes a decrease in secondary transferability.
The dispersed particle size of the adhesive fluoropolymer in the other polymer is preferably 1 to 10 μm, and more preferably 2 to 3 μm. When the dispersed particle size of the adhesive fluoropolymer in the other polymer is not less than the lower limit of the above range, the effect of the adhesive fluoropolymer is easily exhibited. If the dispersed particle size of the adhesive fluoropolymer in the other polymer is not more than the upper limit of the above range, the smoothness of the outer peripheral surface of the rotary sliding member is excellent.

(Adhesive fluoropolymer)
The adhesive fluoropolymer is a unit based on tetrafluoroethylene having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group It is a polymer containing.
The adhesive fluorine-containing polymer is preferably a polymer containing units based on tetrafluoroethylene and units based on perfluoro (alkyl vinyl ether) or hexafluoropropylene.

Adhesive functional groups are the main chain end groups and main chain pendants of the adhesive fluoropolymer because the dispersibility of the adhesive fluoropolymer in other polymers and the adhesion between each layer are further improved. It is preferably present as either or both of the groups.
1 type of adhesive functional groups may be sufficient, and 2 or more types may be sufficient as it.

The adhesive fluorine-containing polymer preferably has at least a carbonyl group-containing group as an adhesive functional group from the viewpoint that the dispersibility of the adhesive fluorine-containing polymer in other polymers and the adhesion between each layer are further excellent. .
Examples of the carbonyl group-containing group include a group having a carbonyl group between carbon atoms of a hydrocarbon group, a carbonate group, a carboxy group, a haloformyl group, an alkoxycarbonyl group, and an acid anhydride group.

Examples of the hydrocarbon group in the group having a carbonyl group between carbon atoms of the hydrocarbon group include alkylene groups having 2 to 8 carbon atoms. The number of carbon atoms of the alkylene group is the number of carbons in a state that does not include a carbonyl group. The alkylene group may be linear or branched.
The haloformyl group is represented by —C (═O) —X (where X is a halogen atom). Examples of the halogen atom in the haloformyl group include a fluorine atom and a chlorine atom, and a fluorine atom is preferable.
The alkoxy group in the alkoxycarbonyl group may be linear or branched, and is preferably an alkoxy group having 1 to 8 carbon atoms, more preferably a methoxy group or an ethoxy group.
An acid anhydride group is represented by —C (═O) —O—C (═O) —.

The content of the adhesive functional group in the adhesive fluoropolymer is preferably 10 to 60000, more preferably 100 to 50000, with respect to 1 × 10 ⁶ main chain carbon atoms of the adhesive fluoropolymer. 100 to 10,000 is more preferable, and 300 to 5000 is particularly preferable. When the content of the adhesive functional group is not less than the lower limit of the above range, the dispersibility of the adhesive fluoropolymer in other polymers and the adhesion between the layers are further improved. If the content of the adhesive functional group is not more than the upper limit of the above range, the adhesiveness between the layers is further improved even if the temperature at the time of producing the laminate is lowered.

  The content of the adhesive functional group can be measured by a method such as nuclear magnetic resonance (hereinafter referred to as “NMR”) analysis or infrared absorption spectrum analysis. For example, as described in Japanese Patent Application Laid-Open No. 2007-314720, using a method such as infrared absorption spectrum analysis, the proportion of units having an adhesive functional group in all units constituting the adhesive fluoropolymer (mol) %) And the content of the adhesive functional group can be calculated from the ratio.

100-325 degreeC is preferable, as for melting | fusing point of an adhesive fluoropolymer, 100-260 degreeC is more preferable, and 120-220 degreeC is further more preferable. When the melting point of the adhesive fluoropolymer is equal to or higher than the lower limit of the above range, the heat resistance of the rotary sliding member is excellent. If the melting point of the adhesive fluoropolymer is equal to or less than the upper limit of the above range, a general-purpose apparatus can be used when manufacturing the rotary sliding member. Moreover, the adhesiveness between each layer is further excellent.
The melting point of the adhesive fluoropolymer can be adjusted by the type and ratio of units constituting the adhesive fluoropolymer, the molecular weight of the adhesive fluoropolymer, and the like. For example, the melting point tends to increase as the proportion of the unit u1 described later increases.

The adhesive fluorine-containing polymer is preferably one that can be melt-molded from the viewpoint of easy production of a fluorine-containing resin sheet.
Examples of the adhesive fluoropolymer that can be melt-molded include known fluoropolymers that can be melt-molded (tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (hereinafter referred to as “PFA”)), tetra. Fluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer (hereinafter referred to as “ETFE”), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoro And the like.) Fluoropolymers in which an adhesive functional group is introduced into ethylene copolymer, etc .; Adhesive fluoropolymers include fluoropolymers with adhesive functional groups introduced into PFA, fluoropolymers with adhesive functional groups introduced into HFP, and ETFE from the viewpoint of dispersibility and compatibility. A fluorine-containing polymer into which a functional group is introduced and an adhesive fluorine-containing polymer A1 are preferable.

  The adhesive fluoropolymer has a melt flow rate of 0.1 to 1000 g / 10 min (preferably 0.5 at a temperature higher by 20 ° C. than the melting point of the adhesive fluoropolymer under a load of 21 N. ˜100 g / 10 min, more preferably 1-30 g / 10 min, still more preferably 5-20 g / 10 min) is used. When the melt flow rate is at least the lower limit of the above range, the adhesive fluoropolymer is excellent in moldability, and the rotating and sliding member is excellent in smoothness and appearance. If the melt flow rate is not more than the upper limit of the above range, the mechanical strength of the rotary sliding member is excellent.

Examples of the adhesive fluoropolymer include the followings depending on the production method.
-Adhesive fluoropolymer A having an adhesive functional group derived from at least one selected from the group consisting of a monomer, a chain transfer agent and a polymerization initiator used in the production of the polymer.
-The fluorine-containing polymer that does not have an adhesive functional group or has an adhesive functional group is subjected to a known surface treatment such as a corona discharge treatment, a plasma treatment, a plasma graft polymerization treatment, a wet etching treatment using metallic sodium, Adhesive fluoropolymer B having an adhesive functional group introduced therein.
-Adhesive fluorine-containing polymer C obtained by graft polymerization of a monomer having an adhesive functional group to a fluorine-containing resin having no adhesive functional group.

As the adhesive fluorine-containing polymer, the adhesive fluorine-containing polymer A is preferable because the dispersibility of the adhesive fluorine-containing polymer in other polymers and the adhesion between the respective layers are further improved.
When the adhesive functional group in the adhesive fluoropolymer A is derived from the monomer used for the production of the adhesive fluoropolymer A, the adhesive fluoropolymer A can be produced by the following method 1. . In this case, the adhesive functional group is present in a unit based on the monomer formed by polymerization of the monomer during production.
Method 1: When the adhesive fluoropolymer A is produced by polymerization of monomers, a monomer having an adhesive functional group is used.

When the adhesive functional group in the adhesive fluoropolymer A is derived from the chain transfer agent used for the production of the adhesive fluoropolymer A, the adhesive fluoropolymer A can be produced by the following method 2. . In this case, the adhesive functional group is present as a terminal group of the main chain of the adhesive fluoropolymer A.
Method 2: Adhesive fluoropolymer A is produced by polymerizing monomers in the presence of a chain transfer agent having an adhesive functional group.
Examples of the chain transfer agent having an adhesive functional group include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.

When the adhesive functional group in the adhesive fluoropolymer A is derived from the polymerization initiator used for the production of the adhesive fluoropolymer A, the adhesive fluoropolymer A can be produced by the following method 3. . In this case, the adhesive functional group is present as a terminal group of the main chain of the adhesive fluoropolymer A.
Method 3: Adhesive fluoropolymer A is produced by polymerizing monomers in the presence of a polymerization initiator such as a radical polymerization initiator having an adhesive functional group.
Examples of the radical polymerization initiator having an adhesive functional group include di-n-propyl peroxydicarbonate, diisopropyl peroxycarbonate, tert-butyl peroxyisopropyl carbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2- Examples include ethylhexyl peroxydicarbonate.

When the adhesive functional group in the adhesive fluoropolymer A is derived from two or more of the monomers, chain transfer agents, and polymerization initiators used in the production of the adhesive fluoropolymer A, adhesion The fluorinated polymer A can be produced by using two or more of the methods 1 to 3 in combination.
The adhesive fluorine-containing polymer A is an adhesive fluorine-containing polymer having an adhesive functional group derived from a monomer produced by Method 1 from the viewpoint that the content of the adhesive functional group can be easily controlled. A is preferred.
As the monomer having an adhesive functional group, a monomer having a carboxy group (maleic acid, itaconic acid, citraconic acid, undecylenic acid, etc.), a monomer having an acid anhydride group (itaconic anhydride (hereinafter referred to as “itaconic acid anhydride”)) "IAH"), citraconic anhydride (hereinafter referred to as "CAH"), 5-norbornene-2,3-dicarboxylic anhydride (hereinafter referred to as "NAH"), maleic anhydride, etc.) And vinyl ethers having a hydroxyl group and an epoxy group.

As the adhesive fluorine-containing polymer A having an adhesive functional group derived from a monomer, the dispersibility of the adhesive fluorine-containing polymer in other polymers and the adhesiveness between the respective layers are further improved. The adhesive fluoropolymer A1 is particularly preferred.
A unit u1 based on tetrafluoroethylene (hereinafter referred to as “TFE”) or chlorotrifluoroethylene (hereinafter referred to as “CTFE”), a unit u2 based on an acid anhydride group-containing cyclic hydrocarbon monomer, and An adhesive fluoropolymer A1 having a unit u3 based on a fluoromonomer (excluding TFE and CTFE).
Here, the acid anhydride group of the unit u2 corresponds to the adhesive functional group.

Examples of the acid anhydride group-containing cyclic hydrocarbon monomer constituting the unit u2 include IAH, CAH, NAH, and maleic anhydride. As the acid anhydride group-containing cyclic hydrocarbon monomer, one type may be used alone, or two or more types may be used in combination.
The acid anhydride group-containing cyclic hydrocarbon monomer is preferably at least one selected from the group consisting of IAH, CAH and NAH. When at least one selected from the group consisting of IAH, CAH and NAH is used, acid anhydride can be used without using a special polymerization method required when maleic anhydride is used (see JP-A-11-19312). An adhesive fluoropolymer A1 having a physical group can be easily produced.
As the acid anhydride group-containing cyclic hydrocarbon monomer, IAH or NAH is preferable because the dispersibility of the adhesive fluorine-containing polymer in other polymers and the adhesion between the layers are further improved.

As the fluorine-containing monomer constituting the unit u3, a fluorine-containing compound having one polymerizable carbon-carbon double bond is preferable, and fluoroolefin (vinyl fluoride, vinylidene fluoride, trifluoroethylene, hexafluoropropylene ( (Hereinafter referred to as “HFP”), hexafluoroisobutylene, etc., except TFE), CF ₂ = CFOR ^f1 (where R ^f1 has 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms) (It is a perfluoroalkyl group.) (Hereinafter referred to as “PAVE”), CF ₂ = CFOR ^f ₂ SO ₂ X ¹ (where R ^f2 is a perfluoro having 1 to 10 carbon atoms and may contain an oxygen atom between carbon atoms) an alkylene group, ^{X 1} is a halogen atom or a hydroxyl ^{_{group.), CF 2 = CFOR f3}} CO 2 X 2 ( provided that R ^f3 is also good perfluoroalkylene group contain an oxygen atom between carbon atoms at 1 to 10 carbon atoms, ^{X 2} is a hydrogen atom or an alkyl group having 1 to 3 carbon _{atoms.), CF 2 = CF (} CF ₂ ) _p OCF = CF ₂ (where p is 1 or 2), CH ₂ = CX ³ (CF ₂ ) _q X ⁴ (where X ³ is a hydrogen atom or a fluorine atom, q is 2 to 2) And X ⁴ is a hydrogen atom or a fluorine atom (hereinafter referred to as “FAE”), a fluorine-containing monomer having a ring structure (perfluoro (2,2-dimethyl-1,3). -Dioxole), 2,2,4-trifluoro-5-trifluoromethoxy-1,3-dioxole, perfluoro (2-methylene-4-methyl-1,3-dioxolane) and the like.

The fluorine-containing monomer is preferably at least one selected from the group consisting of HFP, PAVE, and FAE, from the viewpoint of excellent moldability of the adhesive fluorine-containing polymer A1, bending resistance of the rotary sliding member, and the like. One or both of FAE and HFP are more preferred.
Examples of PAVE include CF ₂ = CFOCF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₃ , CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ , CF ₂ = CFO (CF ₂ ) ₈ F, and the like. ₂ = CFOCF ₂ CF ₂ CF ₃ (hereinafter referred to as “PPVE”) is preferable.

The _{FAE, CH 2 = CF (CF} 2) 2 F, CH 2 = CF (CF 2) 3 F, CH 2 = CF (CF 2) 4 F, CH 2 = CF (CF 2) 5 F, CH 2 _{= CF (CF 2) 8 F} , CH 2 = CF (CF 2) 2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2) ₅ H, CH ₂ ═CF (CF ₂ ) ₈ H, CH ₂ ═CH (CF ₂ ) ₂ F (hereinafter referred to as “PFEE”), CH ₂ ═CH (CF ₂ ) ₃ F, CH ₂ ═CH (CF ₂ ) ₄ F (hereinafter referred to as “PFBE”), CH ₂ ═CH (CF ₂ ) ₅ F, CH ₂ ═CH (CF ₂ ) ₆ F, CH ₂ ═CH (CF ₂ ) ₈ F, _{CH 2 = CH (CF 2)} 2 H, CH 2 = CH (CF 2) 3 H, CH 2 = CH _{CF 2) 4 H, CH 2} = CH (CF 2) 5 H, CH 2 = CH (CF 2) 8 H , and the like.
The _{FAE, CH 2 = CH (CF} 2) q1 X 4 ( although, q1 is 2-6, 2-4 is preferred.) Are _{preferred, PFEE, CH 2 = CH (} CF 2) 3 F, PFBE, CH ₂ ═CF (CF ₂ ) ₃ H, CH ₂ ═CF (CF ₂ ) ₄ H are more preferable, and PFBE or PFEE is particularly preferable.

The adhesive fluoropolymer A1 has units u4 based on non-fluorinated monomers (except for acid anhydride group-containing cyclic hydrocarbon monomers) in addition to the units u1 to u3. Also good.
As the non-fluorinated monomer, a non-fluorinated compound having one polymerizable carbon-carbon double bond is preferable, and examples thereof include olefins (ethylene, propylene, 1-butene, etc.), vinyl esters (vinyl acetate, etc.) and the like. It is done. A non-fluorine-containing monomer may be used individually by 1 type, and may use 2 or more types together.
As the non-fluorinated monomer, ethylene, propylene, and 1-butene are preferable, and ethylene is particularly preferable from the viewpoint of excellent mechanical strength of the fluorine-containing resin layer.

The preferable ratio of each unit when it does not have the unit u4 is as follows.
The ratio of the unit u1 is preferably 90 to 99.89 mol%, more preferably 95 to 99.47 mol%, and more preferably 96 to 98.95 mol, out of the total 100 mol% of the units u1, u2 and u3. % Is more preferable.
The ratio of the unit u2 is preferably 0.01 to 3 mol%, more preferably 0.03 to 2 mol%, and more preferably 0.05 to 1 mol, out of the total 100 mol% of the unit u1, the unit u2 and the unit u3. % Is more preferable.
The proportion of the unit u3 is preferably 0.1 to 9.99 mol%, more preferably 0.5 to 9.97 mol%, out of a total of 100 mol% of the unit u1, the unit u2 and the unit u3. 9.95 mol% is more preferable.

The preferable ratio of each unit when the unit u4 is an ethylene unit is as follows.
The proportion of the unit u1 is preferably 25 to 80 mol%, more preferably 40 to 65 mol%, and further preferably 45 to 63 mol%, out of the total 100 mol% of the unit u1, unit u2, unit u3 and unit u4. preferable.
The ratio of the unit u2 is preferably 0.01 to 5 mol%, more preferably 0.03 to 3 mol%, out of a total of 100 mol% of the unit u1, the unit u2, the unit u3 and the unit u4, 0.05 More preferred is ˜1 mol%.
The proportion of the unit u3 is preferably 0.2 to 20 mol%, more preferably 0.5 to 15 mol%, out of a total of 100 mol% of the unit u1, the unit u2, the unit u3 and the unit u4. More preferred is mol%.
The ratio of the unit u4 is preferably 20 to 75 mol%, more preferably 35 to 50 mol%, and more preferably 37 to 55 mol% with respect to 100 mol% in total of the unit u1, the unit u2, the unit u3, and the unit u4. Further preferred.

When the ratio of each unit is within the above range, the rotational sliding member is excellent in flame retardancy, chemical resistance, and the like.
When the ratio of the unit u2 is within the above range, the dispersibility of the adhesive fluoropolymer in other polymers and the adhesiveness between the layers are further improved.
When the ratio of the unit u3 is within the above range, the adhesive fluoropolymer A1 is excellent in moldability, the bending resistance of the rotary sliding member, and the like.
The ratio of each unit can be calculated by melt NMR analysis, fluorine content analysis, infrared absorption spectrum analysis, etc. of the adhesive fluoropolymer A1.

  In the adhesive fluoropolymer A1, a part of the acid anhydride group in the unit u2 is hydrolyzed, and as a result, a dicarboxylic acid (itaconic acid, citraconic acid) corresponding to the acid anhydride group-containing cyclic hydrocarbon monomer is obtained. , Units based on 5-norbornene-2,3-dicarboxylic acid, maleic acid, etc.). When a unit based on the dicarboxylic acid is included, the ratio of the unit is included in the ratio of the unit u2.

Preferable specific examples of the adhesive fluoropolymer A1 include the following.
A copolymer having TFE units, NAH units and PPVE units;
A copolymer having TFE units, IAH units and PPVE units;
A copolymer having TFE units, CAH units and PPVE units;
A copolymer having TFE units, IAH units and HFP units;
A copolymer having TFE units, CAH units and HFP units;
A copolymer having a TFE unit, an IAH unit, a PFBE unit, and an ethylene unit;
A copolymer having TFE units, CAH units, PFBE units and ethylene units;
A copolymer having TFE units, IAH units, PFEE units and ethylene units;
A copolymer having TFE units, CAH units, PFEE units, and ethylene units;
Copolymers having TFE units, IAH units, HFP units, PFBE units and ethylene units.

The adhesive fluoropolymer can be produced by a conventional method. When producing an adhesive fluorine-containing polymer by polymerization of monomers, the polymerization method using a radical polymerization initiator is preferred.
Polymerization methods include bulk polymerization, solution polymerization using organic solvents (fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, etc.), aqueous media and appropriate organic solvents as required. And suspension polymerization methods using an aqueous medium and an emulsion polymerization method using an emulsifier and a solution polymerization method are preferred.

(Other polymers)
Examples of the other polymer include a cured product of a thermoplastic resin or a thermosetting resin.
Examples of the thermoplastic resin include a crystalline resin, an amorphous resin, and a thermoplastic elastomer.

  Examples of crystalline resins include polyesters (polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyethylene naphthalate, liquid crystal polyester, etc.), polyolefins (polyethylene, polypropylene, polybutylene, acid-modified polyethylene, acid-modified polypropylene, acid-modified polybutylene, etc.) , Polyoxymethylene, polyamide, polyarylene sulfide (polyphenylene sulfide, etc.), polyketone, polyetherketone, polyetheretherketone, polyetherketoneketone, polyethernitrile, fluorine-containing polymers other than adhesive fluoropolymers (poly Tetrafluoroethylene, polyvinylidene fluoride, etc.), liquid crystal polymers and the like.

  Amorphous resins include styrene resin (polystyrene, acrylonitrile styrene resin, acrylonitrile butadiene styrene resin, etc.), polycarbonate, polymethyl methacrylate, polyvinyl chloride, unmodified or modified polyphenylene ether, thermoplastic polyimide, polyamideimide, poly Examples include ether imide, polysulfone, polyether sulfone, polyarylate and the like.

  Examples of the thermoplastic elastomer include polystyrene elastomers, polyolefin elastomers, polyurethane elastomers, polyester elastomers, polyamide elastomers, polybutadiene elastomers, polyisoprene elastomers, and fluorine elastomers (excluding adhesive fluoropolymers). ) And acrylonitrile elastomers.

  Examples of thermosetting resins include epoxy resins, cyanate ester resins, unsaturated polyester resins, vinyl ester resins, phenol resins, urea / melamine resins, thermosetting polyimides, bismaleimide resins, and the like.

  Epoxy resins include glycidyl ether epoxy resins (bisphenol type epoxy resins, (poly) alkylene glycol type epoxy resins, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, etc.), glycidyl ester epoxy resins, glycidyl amine epoxy resins (N N, N ′, N′-tetraglycidyldiaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl isocyanurate, etc.), alicyclic epoxy resins, epoxy resins having a sulfur atom in the main chain, urethane-modified epoxy resins, Examples include rubber-modified epoxy resins.

  The other polymer is not particularly limited as long as it is a resin used in a seamless belt, but is not limited to thermoplastic polyimide, cured epoxy resin, cured thermosetting polyimide, polyphenylene sulfide, polyetherimide, poly At least one selected from the group consisting of ether sulfone, polyvinylidene fluoride and polybutylene terephthalate is preferable.

(Other ingredients)
Other components include conductive fillers, insulating fillers, ionic conductive agents (polymeric ionic conductive agents, surfactants, etc.), conductive polymers, antioxidants (hindered phenolic antioxidants, phosphorus-based compounds) Antioxidants, sulfur-based antioxidants, etc.), UV absorbers, organic pigments, inorganic pigments, pH adjusters, crosslinking agents, compatibilizers, release agents (silicone release agents, fluorine release agents, etc.) , Crosslinking agents, coupling agents, lubricants and the like.
Examples of the conductive filler include carbon black, carbon fiber, graphite, metal powder, conductive metal oxide (conductive titanium oxide, conductive tin oxide, conductive mica, etc.), an ionic conductive agent, and the like.
Insulating fillers include zinc oxide, barium sulfate, calcium sulfate, barium titanate, potassium titanate, strontium titanate, titanium oxide, magnesium oxide, magnesium hydroxide, aluminum hydroxide, talc, mica, clay, kaolin, hydro Examples include talcite, silica, alumina, ferrite, calcium carbonate, barium carbonate, nickel carbonate, glass powder, quartz powder, glass fiber, alumina fiber, potassium titanate fiber, and thermosetting resin fine particles.

(Manufacture of rotating sliding members)
The rotary sliding member can be manufactured by a conventional method. For example, the following method is mentioned as a manufacturing method of a seamless belt.
Method i: A method of forming a resin material containing an adhesive fluoropolymer into a cylindrical shape (see Japanese Patent Application Laid-Open No. 2017-1115011).
Method ii: A method in which a resin liquid containing an adhesive fluoropolymer is applied to the inner peripheral surface or outer peripheral surface of a cylindrical mold and solidified (see Patent Document 2).
Method iii: A method in which a resin liquid containing an adhesive fluoropolymer is filled in a casting mold having a cylindrical cavity and solidified (see Patent Document 2).
Method iv: A method of forming a cylindrical base material layer and forming an outermost layer containing an adhesive fluoropolymer on the outer peripheral surface of the base material layer (see Japanese Patent Application Laid-Open No. 2005-179652).
Method v: A method in which a resin material containing an adhesive fluoropolymer is formed into a test tubular preform, and the preform is stretched in the axial direction and the radial direction (see JP 2011-180275 A).

Hereinafter, the methods i to v will be described by taking as an example a method for producing a rotary sliding member in which an adhesive fluoropolymer is dispersed in another polymer.
Examples of the method for preparing the resin material in the method i include a method of melt-kneading powder, beads, pellets and the like of an adhesive fluoropolymer and powder, beads, pellets and the like of a thermoplastic resin. The adhesive fluoropolymer is dispersed in another polymer by melt kneading.
The melt flow rate of the resin material in Method i is preferably 0.5 to 100 g / 10 minutes, and more preferably 1 to 60 g / 10 minutes. When the melt flow rate is equal to or higher than the lower limit of the above range, the resin material is excellent in moldability and the rotating and sliding member is excellent in smoothness and appearance. If the melt flow rate is not more than the upper limit of the above range, the mechanical strength of the rotary sliding member is excellent.
Examples of the molding method of the resin material in the method i include an extrusion molding method, an inflation method, and a blow molding method.

In the method ii or the method iii, the resin liquid is prepared by mixing an adhesive fluorine-containing polymer powder with another polymer or a solution of a precursor thereof; an adhesive fluorine-containing polymer powder. And a method of mixing a liquid thermosetting resin. As the solvent in the solution of the other polymer or its precursor, a solvent that does not dissolve the adhesive fluoropolymer is used. Examples of the precursor of the other polymer include polyamic acid when the other polymer is polyimide.
Examples of the method for applying the resin liquid in the method ii include a dipping method, a rotary centrifugal molding method, and a spray method.

In the method iv, the base material layer is formed by applying the base layer resin liquid to the inner peripheral surface or the outer peripheral surface of the cylindrical mold and solidifying in the same manner as in the method ii; And a method of forming the base layer resin material into a cylindrical shape.
As a method for forming the outermost layer in the method iv, there is a method in which a resin liquid containing an adhesive fluoropolymer is applied to the outer peripheral surface of the base material layer and solidified in the same manner as in the method ii.
Examples of the molding method of the resin material for producing the test tubular preform in the method v include an injection molding method.

  The powder of the adhesive fluoropolymer is made of a resin material for forming a powder containing the adhesive fluoropolymer. The powder forming resin material may contain other components as necessary within the range not impairing the effects of the present invention.

  The average particle size of the powder of the adhesive fluoropolymer used for the preparation of the resin liquid containing the adhesive fluoropolymer is preferably 1 to 10 μm, and more preferably 2 to 5 μm. If the average particle size of the powder of the adhesive fluoropolymer is within the above range, the dispersed particle size of the adhesive fluoropolymer in the other polymer described above can easily be within the preferred range.

The powder of the adhesive fluoropolymer can be produced, for example, by the following procedure.
The adhesive fluoropolymer obtained by polymerization of the monomer is pulverized. The pulverized product is classified to obtain an adhesive fluoropolymer powder.

  Equipment that can mechanically grind adhesive fluoropolymers includes hammer mill, pin mill, disk mill, rotary mill, jet mill, fluidized bed air jet mill, jaw crusher, gyrate leak crusher, cage mill, pan crusher, ball mill , Pebble mill, rod mill, tube mill, disc attrition mill, attritor, disc refiner and the like.

  The adhesive fluoropolymer is preferably pulverized by cooling the adhesive fluoropolymer to a temperature of −40 ° C. or lower from the viewpoint of easily reducing the average particle size of the pulverized product. The cooling temperature is more preferably −100 ° C. or lower, and further preferably −160 ° C. or lower. Examples of the cooling method include a method using dry ice or liquid nitrogen.

(Mechanism of action)
In the rotary sliding member of the present invention described above, since the adhesive fluoropolymer has fluorine atoms, the surface of the rotary sliding member becomes slippery and excellent in slidability. Further, even when the rotary sliding member contains another polymer, the adhesive fluoropolymer has an adhesive functional group, so that the compatibility between the adhesive fluoropolymer and the other polymer is high. Good. Therefore, the adhesive fluoropolymer is less likely to aggregate in other polymers, the dispersibility of the adhesive fluoropolymer is good, and the surface properties (smoothness) of the surface of the rotary sliding member are not impaired. Moreover, since it contains an adhesive fluoropolymer, it has releasability and wettability. Moreover, since the adhesive fluoropolymer has an adhesive functional group, when the rotary sliding member is a laminate, the adhesiveness between the layers is excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
Examples 1, 2, 6, 7, 9, and 10 are production examples, and Examples 3 to 5, 8, and 11 are comparative production examples.

<Measurement and evaluation>
(Ratio of units in polymer)
The proportion of units in the fluoropolymer was determined by melt NMR analysis, fluorine content analysis and infrared absorption spectrum analysis.

(Adhesive functional group content)
The ratio of NAH units having an adhesive functional group in the adhesive fluoropolymer was determined by the following infrared absorption spectrum analysis.
The adhesive fluoropolymer was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, the absorption peak of NAH units in the adhesive fluoropolymer appears at 1778 cm ⁻¹ . The absorbance of the absorption peak was measured, and the NAH unit ratio (mol%) was determined using a molar absorption coefficient of NAH of 20810 mol ⁻¹ · l · cm ⁻¹ .
When the ratio of NAH units with a (mol%), the number of main chain adhesive functional groups to the number 1 × 10 ⁶ carbon (acid anhydride groups) is calculated as [a × ¹⁰ 6/100] Pieces .

(Melting point)
Using a differential scanning calorimeter (manufactured by Seiko Instruments Inc.), the melting peak when the fluoropolymer was heated at a rate of 10 ° C./min was recorded, and the temperature corresponding to the maximum value was taken as the melting point.

(Melting flow rate)
For the fluoropolymer, a melt indexer (manufactured by Techno Seven Co., Ltd.) was used, and the mass of the fluoropolymer flowing out in 10 minutes from a nozzle having a diameter of 2 mm and a length of 8 mm under the conditions of 372 ° C. and a load of 49 N (g ) Was measured.
For the resin material, a mass index (g) of the resin material flowing out from a nozzle having a diameter of 2 mm and a length of 8 mm under a condition of 400 ° C. and a load of 49 N for 10 minutes was measured using a melt indexer (manufactured by Techno Seven). .

(Average particle size)
After the fluoropolymer powder is dispersed in isopropyl alcohol by ultrasonic waves, a volume-based cumulative 50% diameter (D50) is determined by a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by Horiba, Ltd.). This was defined as the average particle size.

(Smoothness)
The surface of the sample (in the case of a laminate, the surface of the outermost layer) was visually observed, and the smoothness was evaluated according to the following criteria.
O (good): The fluoropolymer or thermoplastic resin is uniformly dispersed in the sample, and the surface is smooth.
X (defect): The fluoropolymer or the thermoplastic resin aggregates in the sample, and the surface is not smooth.

(Abrasion amount)
About Examples 1-5 and Examples 9-11, the abrasion loss was measured as follows.
The sample was cut using a contour machine (manufactured by Amada, V-400) to obtain a circular test piece having a diameter of 46 mm. The test piece was subjected to a friction and wear test using a Matsubara type friction and wear tester (Orientec). A test piece is fixed to a test jig, and a ring (material: SUS304, contact area: 2 cm ² ) as a mating member is applied to the surface of the test piece under a pressure of 7 kg / cm ² (686.49 kPa), and a rotation speed: 0.00. The contact amount was 5 m / sec and the test time was 1 hour, and the amount of wear was measured. The smaller the amount of wear, the better the slidability.

About Examples 6-8, the abrasion loss was measured as follows.
The sample was cut using a cutter to obtain a test piece. The test piece was subjected to a friction and wear test using a Matsubara type friction and wear tester (Orientec). A test piece is fixed to a test jig, and a ring, which is a mating member, is applied to the surface of the outermost layer of the test piece. Pressure: 1.5 kg / cm ² (147.10 kPa), rotation speed: 0.5 m / sec, test time : Contact was made for 3 minutes, and the amount of wear was measured. The smaller the amount of wear, the better the slidability.

(Dispersed particle size)
A sample frozen by immersion in liquid nitrogen was frozen, and the cross section of the portion containing the fluoropolymer was observed with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Technologies Corporation), and was randomly selected. The particle diameters of 20 domains were measured using a length measuring function attached to the scanning electron microscope, and the dispersed particle diameters were obtained by averaging the 20 particle diameters. The dispersed particle size is a guideline for judging the compatibility of each component in the sample.

(Dynamic friction coefficient)
About the surface of the part containing the fluoropolymer of a sample, the dynamic friction coefficient was measured using the friction abrasion tester (made by Orientec Co., Ltd.) by Matsubara type | formula. A test piece is fixed to a test jig, and a ring (material: SUS304, contact area: 2 cm ² ) as a mating member is applied to the surface of the test piece under a pressure of 7 kg / cm ² (686.49 kPa), and a rotation speed: 0.00. Contact was made under conditions of 5 m / sec and test time: 1 hour, and the dynamic friction coefficient was determined.

(Arithmetic mean roughness Ra)
About the surface of the part containing the fluoropolymer of the sample, the surface shape was measured at an magnification of 200 times and an observation range of 1117 × 1489.9 (μm) using an ultra-deep shape measuring microscope (manufactured by Keyence Corporation, VK-8500). Then, the average value of the arithmetic average roughness Ra on two arbitrarily selected lines was obtained.

(Wetting tension)
About the surface of the part containing the fluoropolymer of a sample, the liquid mixture for wet tension test (made by Wako Pure Chemical Industries Ltd.) was used, and it measured according to JISK6768: 1999.

(Interfacial peel strength)
A member sample having a fluoropolymer layer was cut into a rectangular shape having a length of 100 mm and a width of 10 mm to prepare a test piece. Next, using a tensile tester (manufactured by Orientec Co., Ltd.) with a position of 50 mm from one end in the length direction of the test piece as a center, the layer and the substrate of the fluoropolymer are 90 degrees at a tensile rate of 50 mm / min. The maximum load applied when the film was peeled was defined as the peel strength (N / cm). It shows that the adhesiveness of the layer of a fluoropolymer and a base material is excellent, so that peeling strength is large.

<Each component>
(Fluoropolymer)
Adhesive fluoropolymer:
Adhesive fluoropolymer beads were obtained according to the method described in Example 5 of WO2015 / 182702. The molar ratio of TFE unit / NAH unit / PPVE unit is 97.9 / 0.1 / 2, and the content of the adhesive functional group is 1 × 10 ⁶ carbon atoms in the main chain of the adhesive fluoropolymer. 1000 pieces, the melting point was 300 ° C., and the melt flow rate was 17.6 g / 10 min.

Adhesive fluoropolymer powder:
The adhesive fluoropolymer beads were pulverized to obtain an adhesive fluoropolymer powder having an average particle size of 3 μm.

PFA powder: PFA pellets having no adhesive functional group (Asahi Glass Co., Ltd., Fluon (registered trademark) PFA P-63P, melting point: 300 ° C., melt flow rate: 12.8 g / 10 min) were pulverized, PFA powder having an average particle size of 5 μm was obtained.
PTFE powder: PTFE powder having no adhesive functional group (Asahi Glass Co., Ltd., Fluon (registered trademark) PTFE L169J, average particle size: 17 μm, melting point: 332 ° C.).

(Thermosetting resin)
Thermosetting resin 1: bisphenol A type epoxy resin (manufactured by Adeka, Adeka Resin EP-4100).
Thermosetting resin 2: dicyclopentadiene type epoxy resin (manufactured by DIC, EPICLON HP-7200H-75M, liquid medium: methyl ethyl ketone (hereinafter referred to as “MEK”), solid content concentration: 75 mass%).

(Curing agent)
Curing agent 1: 4,4′-diaminodiphenyl sulfone (manufactured by Wako Pure Chemical Industries, Ltd.).
Curing agent 2: Phenol novolac resin (manufactured by DIC, Phenolite TD-2090-60M, solvent: MEK, solid content: 60% by mass).

(Thermoplastic resin)
Thermoplastic resin 1 powder: polyethersulfone (manufactured by Solvay Advanced Polymers, Veradel (registered trademark) 3000P).
Powder of thermoplastic resin 2: Thermoplastic polyimide (Mitsui Chemicals, Aurum (registered trademark) PD450).

<Preparation of sample>
(Example 1)
After mixing the thermosetting resin 1 and the adhesive fluoropolymer powder at 125 ° C. for 1.5 hours in the proportions shown in Table 1, the curing agent 1 was added to obtain a resin material. The resin material was defoamed and then poured into a mold (cavity size: thickness 4 mm, width 16 cm, length 12 cm). The mold was placed in a heat circulation oven, heated at 110 ° C. for 2 hours, and then heated at 200 ° C. for 4 hours. The mold was gradually cooled to obtain a sheet-like sample. Table 1 shows the smoothness and wear amount of the sample.

(Examples 2 to 5)
A sample was obtained in the same manner as in Example 1 except that the type and ratio of each component were changed as shown in Table 1. Table 1 shows the smoothness and wear amount of the sample.

Examples 1 and 2 containing an adhesive fluoropolymer were excellent in smoothness compared to Example 4 containing a fluoropolymer having no adhesive functional group.
Examples 1 and 2 containing an adhesive fluoropolymer were superior in slidability compared to Examples 3 and 5 not containing a fluoropolymer.

(Example 6)
A surfactant (manufactured by Nippon Emulsifier Co., Ltd., New Coal (registered trademark) 1308) was added to the adhesive fluoropolymer powder so as to be 3% by mass with respect to the adhesive fluoropolymer powder. . Further, MEK was added to adjust the solid content concentration to 40% by mass, and the mixture was stirred with a stirrer at 300 rpm for 1 hour and then at 1500 rpm for 15 minutes. Sonication was performed for 5 minutes with an ultrasonic homogenizer to obtain a dispersion.

The dispersion liquid is applied to the thermosetting resin 2 so that the proportion of the adhesive fluoropolymer powder in the total of the thermosetting resin 2 and the adhesive fluoropolymer powder is 20% by mass. Added. The curing agent 2 was added so that the mass ratio of the epoxy resin 2 and the curing agent 2 was 26: 9, and the mixture was stirred with a stirrer at 1000 rpm for 20 minutes to obtain a resin liquid.
The resin solution is filtered through a 100 mesh filter and then applied to the surface of an electrolytic copper foil (Fukuda Metal Foil Powder Co., Ltd., CF-T4X-SVR-12, thickness: 12 μm, surface roughness Rz: 1.2 μm). This was dried in a hot air circulation oven to obtain a sample having a thickness of 60 μm. The sample is a laminate comprising a conductive layer made of copper foil and an outermost layer containing an adhesive fluoropolymer. Table 2 shows the smoothness and wear amount of the sample.

(Example 7)
A sample was prepared in the same manner as in Example 6 except that the proportion of the adhesive fluoropolymer powder in the total of the thermosetting resin 2 and the adhesive fluoropolymer powder was changed to 25% by mass. Obtained. Table 2 shows the smoothness and wear amount of the sample.

(Example 8)
A sample was obtained in the same manner as in Example 6 except that the adhesive fluoropolymer powder was not used. Table 2 shows the smoothness and wear amount of the sample.

  Examples 6 and 7 containing the adhesive fluoropolymer were superior in slidability compared to Example 8 not containing the fluoropolymer.

(Example 9)
In the ratio shown in Table 3, the powder of the thermoplastic resin 2 and the beads of the adhesive fluorine-containing polymer are dry blended and put into a twin screw extruder (Technobel, KZW15TW-45MG), and the resin discharge amount : Melted and kneaded under the conditions of 2 kg / hour, screw rotation speed: 200 rpm, and set resin temperature: 410 ° C. to obtain a resin material. The melt flow rate of the resin material is shown in Table 3.

The resin material is extruded using a single screw extruder (manufactured by Tanabe Plastics Machine Co., Ltd., VS-30) and a 150 mm wide T die at a set resin temperature of 400 ° C., a rotation speed of 10 rpm, and a line speed of 0.8 m / min. Molding was performed to obtain a film-like sample having a thickness of 50 μm. A scanning electron micrograph (5000 magnifications) of the cross section of the sample is shown in FIG. Table 3 shows the dispersed particle size of the adhesive fluoropolymer in the sample, the dynamic friction coefficient, the wear amount, and the arithmetic average roughness Ra of the sample.
This film-like sample and copper foil (Mitsui Metal Mining Co., Ltd., product number: HS1-VSP-18) are stacked and vacuum hot pressed to have an adhesive fluoropolymer on the surface using the copper foil as another substrate. A rotating sliding member was obtained. The peel strength of this rotary sliding member was 13 N / cm.

(Example 10)
A sample was obtained in the same manner as in Example 9 except that the ratio of each component was changed as shown in Table 3. A scanning electron micrograph (5000 magnifications) of the cross section of the sample is shown in FIG. Table 3 shows the dispersed particle size of the adhesive fluoropolymer in the sample, the dynamic friction coefficient of the sample, and the amount of wear.

(Example 11)
A sample was obtained in the same manner as in Example 9, except that the adhesive fluoropolymer beads were changed to PTFE powder and the film thickness was changed to 250 μm.
A scanning electron micrograph (400 magnifications) of the cross section of the sample is shown in FIG. Table 3 shows the dispersed particle size of the adhesive fluoropolymer in the sample, the dynamic friction coefficient, the wear amount, and the arithmetic average roughness Ra of the sample.
This film-like sample and copper foil (Mitsui Mining & Mining Co., Ltd., product number: HS1-VSP-18) are layered, and rotation is performed in the same manner as in Example 9 with copper foil as another substrate and a fluoropolymer on the surface. A sliding member was obtained. The peel strength of this rotary sliding member was 3 N / cm.

  In Examples 9 and 10 using an adhesive fluoropolymer as compared to Example 11 using PTFE, the dispersed particle size of the fluoropolymer in the thermoplastic resin is small, and the adhesive fluorine-containing polymer is compared to PTFE. It can be judged that the polymer has good compatibility with the thermoplastic resin.

(Example 12)
In accordance with the coating method described in WO2018 / 070437, an adhesive fluoropolymer powder (average particle size 75 μm) is electrostatically applied to an aluminum substrate and heated at 340 ° C. for 10 minutes. Thus, the adhesive fluoropolymer was fired to obtain a rotary sliding member having an aluminum substrate as another base material and the adhesive fluoropolymer on the surface. The arithmetic average roughness of the surface of this rotary sliding member was 0.5 μm, the surface wetting tension was 22.6 mN / m, and the peel strength was 15 N / cm. When this rotary sliding member was an ink jet roller, even when ink jet droplets were scattered, the ink was not transferred to the roller, and there was no problem.

(Example 13)
A rotary sliding member having a ceramic substrate as another base material and an adhesive fluoropolymer on its surface was obtained in the same manner as in Example 12 except that a ceramic substrate was used instead of the aluminum substrate. The surface of this rotary sliding member had an arithmetic average roughness of 1 μm, a surface wetting tension of 23.2 mN / m, and a peel strength of 16 N / cm.

(Example 14)
A ceramic substrate is used as another base material in the same manner as in Example 12 except that a ceramic substrate is used in place of the aluminum substrate and the heating condition after electrostatic coating is 260 ° C. below the melting point of the adhesive fluoropolymer. A rotary sliding member having an adhesive fluoropolymer on its surface was obtained. The arithmetic average roughness of this rotary sliding member was 35 μm. When this rotary sliding member was an ink jet roller, when ink jet droplets were scattered, the ink soaked into the roller and a problem occurred.

  The rotary sliding member of the present invention is useful as a seamless belt or an ink jet roller, and particularly useful as an intermediate transfer belt, a transport belt of an electrophotographic image forming apparatus, a transport belt of an ink jet image forming apparatus, an elastic belt, or the like. It is.

Claims (10)

  A rotary sliding member comprising a tetrafluoroethylene-based polymer having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group and an isocyanate group.   The tetrafluoroethylene-based polymer is based on tetrafluoroethylene having at least one adhesive functional group selected from the group consisting of a carbonyl group-containing group, a hydroxy group, an epoxy group, an amide group, an amino group, and an isocyanate group. The rotary sliding member according to claim 1, comprising a unit and a unit based on perfluoro (alkyl vinyl ether) or hexafluoropropylene.   The rotary sliding member according to claim 1, comprising a polymer other than the tetrafluoroethylene-based polymer.   The rotary sliding member according to claim 3, wherein the tetrafluoroethylene-based polymer is dispersed in the other polymer.   The other polymer may be thermoplastic polyimide, cured epoxy resin, cured cured thermosetting polyimide, polyphenylene sulfide, polyetherimide, polyether ketone, polyether sulfone, polytetrafluoroethylene, polyvinylidene fluoride and The rotary sliding member according to claim 3 or 4, which is at least one selected from the group consisting of polybutylene terephthalate.   The rotation sliding member as described in any one of Claims 1-5 which contains the said tetrafluoroethylene-type polymer in at least one part of the surface.   The rotational sliding member according to any one of claims 1 to 6, wherein the arithmetic average roughness Ra of the surface is 0.05 to 30 µm.   It is a seamless belt or an inkjet roller, The rotation sliding member as described in any one of Claims 1-7.   The rotary sliding member according to any one of claims 1 to 8, which is an intermediate transfer belt.   The rotary sliding member according to any one of claims 1 to 8, which is an elastic belt.