WO2012023547A1 - 改質ポリマー基材およびその製造方法ならびに表面処理剤 - Google Patents
改質ポリマー基材およびその製造方法ならびに表面処理剤 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/02—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices
- G03G15/0208—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus
- G03G15/0216—Apparatus for electrographic processes using a charge pattern for laying down a uniform charge, e.g. for sensitising; Corona discharge devices by contact, friction or induction, e.g. liquid charging apparatus by bringing a charging member into contact with the member to be charged, e.g. roller, brush chargers
- G03G15/0233—Structure, details of the charging member, e.g. chemical composition, surface properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/28—Reaction with compounds containing carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/83—Chemically modified polymers
- C08G18/837—Chemically modified polymers by silicon containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/14—Polyamide-imides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/06—Apparatus for electrographic processes using a charge pattern for developing
- G03G15/08—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
- G03G15/0806—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
- G03G15/0818—Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the structure of the donor member, e.g. surface properties
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G15/00—Apparatus for electrographic processes using a charge pattern
- G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
- G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer
- G03G15/1665—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat
- G03G15/167—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer by introducing the second base in the nip formed by the recording member and at least one transfer member, e.g. in combination with bias or heat at least one of the recording member or the transfer member being rotatable during the transfer
- G03G15/1685—Structure, details of the transfer member, e.g. chemical composition
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
Definitions
- the present invention relates to a modified polymer substrate, a method for producing the same, and a surface treatment agent, and more specifically, a modified polymer substrate suitable as a polymer substrate constituting a surface of a conductive member for electrophotographic equipment, a wiper of an automobile, and the like.
- the present invention relates to a material, a manufacturing method thereof, and a surface treatment agent.
- polymer products using polymers such as resin, rubber, and elastomer have been manufactured in various fields.
- the polymer base material of the polymer product is required to have a function corresponding to the application on the surface thereof.
- the surface of the polymer substrate may be required to have a plurality of functions instead of a single function.
- toner or the like adheres to the surface of a conductive member for an electrophotographic apparatus such as a developing roll used in an electrophotographic apparatus, but it is required that the toner does not adhere to the surface when left for a long time. Further, if the toner is continuously used, a phenomenon called filming is likely to deposit on the roll surface. In order to suppress this phenomenon, it is also required that the friction coefficient is small. Further, it is also required to charge the toner appropriately by friction with the toner.
- a method of imparting a function corresponding to the application to the surface of the polymer substrate is often employed.
- a method of imparting a function corresponding to the application to the surface of the polymer substrate for example, there is a method in which a functional layer is formed on the surface of a polymer substrate with a paint containing a compound for imparting a predetermined function.
- the physical properties of the polymer base material and the material forming the functional layer are greatly different, the physical properties such as the hardness of the surface of the polymer base material may be greatly changed, and adjustment may be difficult.
- Patent Document 1 discloses a method for modifying the surface of a polymer base material mainly composed of urethane rubber or silicone rubber using a surface treatment agent containing isocyanate.
- the method of Patent Document 1 uses an isocyanate group as a reactive group, it is effective for a polymer substrate having a specific functional group such as a hydroxy group or an amino group that can react with the isocyanate group.
- a polymer substrate having no specific functional group for example, an unsaturated carbon-carbon double bond
- the method of Patent Document 1 is not suitable for modifying the surface of a polymer substrate having an unsaturated carbon-carbon double bond.
- Patent Documents 2 and 3 Methods for modifying the surface of a polymer substrate having an unsaturated carbon-carbon double bond are disclosed in Patent Documents 2 and 3, for example.
- Patent Document 2 (A) a —CONX— bond (X is a halogen atom) in a molecule is placed on the surface of a rubber layer containing rubber having an unsaturated bond, located on the outermost periphery of a roll for an electrophotographic apparatus. It is disclosed that a compound having (B) BF 3 is brought into contact with each other to introduce a halogen atom derived from the (A) compound and a fluorine atom derived from the (B) compound.
- Patent Document 3 discloses a method for surface treatment of a rubber vulcanizate with a solution containing an organic active halogen compound having a functional group represented by the formula -CONX- (X is a halogen atom) as a solute. ing.
- Patent Document 2 can improve the releasability of the toner adhering to the surface of the rubber layer with respect to the external additive, the effect of reducing the friction coefficient is small, and a specific function is provided on the surface of the rubber layer. It was limited to be able to give limited. Further, for example, when the method described in Patent Document 3 is applied to a polymer base material of a conductive member for an electrophotographic apparatus, the releasability with respect to toner adhering to the surface of the polymer base material can be improved, but the friction coefficient The reduction effect is not sufficient, and similarly, a specific function can be limitedly given to the surface of the rubber layer.
- the problem to be solved by the present invention is a modified polymer substrate capable of having both excellent releasability with respect to deposits adhering to the surface of the substrate and other functions depending on the application, and production thereof It is to provide a method.
- the modified polymer substrate according to the present invention has an organic group having a functional group for imparting a function to the surface of the polymer substrate via the isocyanuric acid skeleton on the surface of the polymer substrate.
- the main point is that they are combined.
- silicone group fluorine-containing group, perfluoroalkyl group, ester group, amide group, imide group, ether group, aryl group, azo group, diazo group, nitro group, epoxy group, carbonyl group,
- the organic group is preferably a group derived from an organic compound having an unsaturated carbon-carbon double bond.
- the surface of the polymer base material is preferably provided with an uneven shape.
- the method for producing a modified polymer substrate according to the present invention comprises (a) trichloroisocyanuric acid and (b) unsaturated, on the surface of the polymer substrate containing an organic component having an unsaturated carbon-carbon double bond.
- the gist of the invention is to have a step of contacting a treatment liquid containing a compound having a carbon-carbon double bond and an organic group having a functional group for imparting a function to the surface of the polymer substrate.
- the surface treatment agent according to the present invention is a surface treatment agent that is brought into contact with the surface of a polymer substrate containing an organic component having an unsaturated carbon-carbon double bond, and includes (a) trichloroisocyanuric acid and (b ) It contains a compound having an unsaturated carbon-carbon double bond and an organic group having a functional group for imparting a function to the surface of the polymer substrate.
- an organic group having a functional group for imparting a function to the surface of the polymer substrate is bonded to the surface of the polymer substrate via an isocyanuric acid skeleton.
- the surface of the polymer base material containing an organic component having an unsaturated carbon-carbon double bond is excellent against deposits adhering to the base material surface.
- it has excellent mold releasability for deposits that adhere to the substrate surface, and other functions depending on the application.
- a modified polymer base material can also be provided.
- trichloroisocyanuric acid and (b) an organic compound having a functional group for imparting a function to the surface of the polymer base material and an unsaturated carbon-carbon double bond. Since it contains a compound having a group, it has an excellent releasability to the adherent adhering to the surface of the polymer substrate containing an organic component having an unsaturated carbon-carbon double bond, Other than the above, functions according to applications can be given together.
- FIG. 1 is a cross-sectional view in the circumferential direction of a conductive roll for electrophotographic equipment shown as an example of a modified polymer substrate of the present invention
- FIG. 1 (a) is a single-layer structure
- FIG. 1 (b) is a two-layer structure. belongs to.
- the modified polymer substrate according to the present invention will be described in detail.
- the modified polymer substrate of the present invention has a structure in which an organic group having a specific functional group is bonded to the surface of the polymer substrate via an isocyanuric acid skeleton.
- the modified polymer substrate of the present invention can be used as a polymer substrate for various polymer products.
- the surface of the polymer substrate is suitable as a polymer substrate of a polymer product that requires a plurality of functions instead of a single function.
- a conductive roll development roll
- Examples thereof include conductive members for electrophotographic equipment such as charging rolls, transfer rolls, toner supply rolls, conductive belts (transfer belts, etc.), conductive blades (cleaning blades), and automobile wipers.
- the roll for printing, the roll for papermaking, a conveyance roll, a lamination roll, etc. can also be mentioned.
- the modified polymer substrate of the present invention is suitable as the outermost layer.
- the electroconductive roll 10 having a structure in which one elastic layer 14 is formed on the outer periphery of the shaft body 12, or in FIG.
- a conductive roll 20 in which two elastic layers 24 and 26 are formed on the outer periphery of the shaft 22 can be exemplified.
- three or more elastic layers may be formed on the outer periphery of the shaft body.
- the inner elastic layer 24 is a base layer
- the outer elastic layer 26 is a resistance adjusting layer or the like.
- the elastic layer 14 is the outermost layer of the roll, and therefore the modified polymer substrate of the present invention is preferably applied to the elastic layer 14.
- the outer elastic layer 26 is the outermost layer of the roll, so the modified polymer substrate of the present invention is preferably applied to the outer elastic layer 26.
- a conductive belt for an electrophotographic apparatus as shown in FIG. 2, a conductive belt having a configuration in which an outer elastic layer 34 as a surface layer is formed on the outer periphery of an inner elastic layer 32 as a base layer. 30.
- the modified polymer substrate of the present invention may be applied to the outer elastic layer 34.
- the polymer substrate may be any of rubber, resin, and elastomer. More specifically, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile-butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber (CR), butyl rubber (IIR).
- natural rubber NR
- isoprene rubber IR
- butadiene rubber acrylonitrile-butadiene rubber
- SBR styrene butadiene rubber
- CR chloroprene rubber
- IIR butyl rubber
- Ethylene-propylene diene rubber EPDM
- acrylic rubber ACM
- fluoro rubber FKM
- chlorosulfonated polyethylene CSM
- hydrin rubber CO, ECO, etc.
- silicone Q
- urethane U
- ethylene -Vinyl acetate copolymer EVA
- the specific functional group is a functional group for imparting a specific function to the surface of the polymer substrate.
- Functional groups include silicone groups, fluorine-containing groups, perfluoroalkyl groups, ester groups, amide groups, imide groups, ether groups, aryl groups, azo groups, diazo groups, nitro groups, epoxy groups, carbonyl groups, and heterocyclic groups. , Mesoionic groups, halogen groups, amino groups, imino groups, alkyl groups, sulfonic acid groups, hydroxy groups, acyl groups, formyl groups, carboxylic acid groups, urea groups, urethane groups, cyano groups, and the like. In the organic group, only one type of these functional groups may be included, or two or more types of functional groups may be included.
- heterocyclic group examples include a pyridyl group, an imidazole group, and an oxazole group.
- mesoionic group examples include a sydnone group and a munhenone group.
- a functional group contains a silicone group or a fluorine-containing group (particularly a perfluoroalkyl group), for example, in a conductive member for an electrophotographic apparatus, a toner attached to the surface of a substrate, a toner external additive, etc. It is possible to have both excellent releasability with respect to deposits and a function of reducing the coefficient of friction. In addition, surface tackiness, bleeding out of components in the member, and the like can be suppressed.
- an amide group or an ester group is included as a functional group, for example, in a conductive member for electrophotographic equipment, excellent releasability with respect to deposits such as toner and toner external additives that adhere to the substrate surface And high toner chargeability.
- an alkyl ether such as propylene glycol
- an electrophotographic apparatus conductive member excellent release from an adherent such as a toner or a toner external additive adhering to the surface of the substrate And antistatic properties that lower the electrical resistance of the surface.
- a functional group other than these is included, for example, in a conductive member for an electrophotographic apparatus, a specific function based on each functional group, such as a toner attached to the substrate surface or a toner external additive It can be combined with excellent releasability against deposits.
- the organic group having a specific functional group is bonded to the N atom of the isocyanuric acid skeleton.
- the isocyanuric acid skeleton is bonded to the polymer substrate with N atoms. Since there are three N atoms in one isocyanuric acid skeleton, one organic group having a specific functional group may be bonded to one isocyanuric acid skeleton. May be combined.
- the isocyanuric acid skeleton is bonded to the polymer substrate with one N atom.
- the isocyanuric acid skeleton may be bonded to the polymer substrate with one N atom or bonded with two N atoms. May be.
- the organic group having a specific functional group can be a group derived from an organic compound having a specific functional group and an unsaturated carbon-carbon double bond.
- the specific functional group may be directly bonded to the carbon atom of the unsaturated carbon-carbon double bond or indirectly bonded through another structural site such as a carbon chain. Also good.
- a specific functional group is directly or indirectly bonded to one carbon atom of the carbon-carbon single bond derived from the unsaturated carbon-carbon double bond of the organic compound, and the other carbon atom is Thus, the N atom of the isocyanuric acid skeleton is bonded.
- Suitable organic compounds include those represented by the following formulas 1 to 4.
- R 1 is —X 2 —X 1 or —X 1
- X 1 is a specific functional group, preferably a silicone group or a fluorine-containing group
- X 2 is an ester group (— C (O) O—), ether group (—O—), carbonyl group (—CO—), urethane group (—NH—C (O) O—), amide group (—NH—CO—)
- R 2 ⁇ R 4 may be a hydrogen group or an alkyl group, may be the same group as R 1, may be a group having a different particular functional group as R 1.
- R 2 to R 4 are preferably a hydrogen group or an alkyl group, more preferably a hydrogen group, from the viewpoint of stability or the like.
- R 1 to R 4 may be different from each other, or some or all of R 1 to R 4 may be the same group.
- R 1 is —X 2 —X 1 or —X 1
- X 1 is a specific functional group, preferably a silicone group or a fluorine-containing group
- X 2 is an ester group, ether Any of a group, a carbonyl group, a urethane group, and an amide group, preferably an ester group.
- R 2 ⁇ R 7 may be a hydrogen group or an alkyl group, may be the same group as R 1, may be a group having a different particular functional group as R 1.
- R 2 to R 7 are preferably a hydrogen group or an alkyl group, more preferably a hydrogen group, from the viewpoint of stability or the like.
- R 1 to R 7 may be groups different from each other, or some or all of R 1 to R 7 may be the same group.
- X 3 to X 4 are any of an ester group, an ether group, a carbonyl group, a urethane group, and an amide group, and preferably an ester group.
- X 3 to X 4 may have different structures or the same structure.
- R 1 and R 1 ′ are —X 2 —X 1 or —X 1
- X 1 is a specific functional group, preferably a silicone group or a fluorine-containing group
- X 2 is Any of an ester group, an ether group, a carbonyl group, a urethane group and an amide group, preferably an ester group.
- R 2 ⁇ R 4 may be a hydrogen group or an alkyl group, may be the same group as R 1, may be a group having a different particular functional group as R 1.
- R 2 to R 4 are preferably a hydrogen group or an alkyl group, more preferably a hydrogen group, from the viewpoint of stability or the like.
- R 1 to R 4 may be different from each other, or some or all of R 1 to R 4 may be the same group.
- X 3 is any of an ester group, an ether group, a carbonyl group, a urethane group, and an amide group, and preferably an ester group.
- R 1 ′′ is —X 2 —X 1 —X 2 — or —X 1 —
- X 1 is a specific functional group, preferably a silicone group or a fluorine-containing group
- 2 is an ester group, an ether group, a carbonyl group, a urethane group or an amide group, preferably an ester group.
- R 2 ⁇ R 13 may be a hydrogen group or an alkyl group, may be the same group as R 1, may be a group having a different particular functional group as R 1.
- R 2 to R 13 are preferably a hydrogen group or an alkyl group, more preferably a hydrogen group, from the viewpoint of stability or the like.
- R 1 to R 13 may be different from each other, or some or all of R 1 to R 13 may be the same group.
- X 3 to X 8 are any of an ester group, an ether group, a carbonyl group, a urethane group, and an amide group, and preferably an ester group.
- X 3 to X 8 may have different structures from each other, or some or all of X 3 to X 8 may have the same structure.
- n is a positive integer.
- organic compound described in Formula 1 include the compounds described in Formulas 7 to 9 below in addition to those described in Formulas 5 to 6 above.
- n is a positive integer.
- an ester group is obtained, for example, by a condensation reaction between a compound having a carboxylic acid group and a compound having a hydroxyl group.
- the amide group is obtained, for example, by a condensation reaction between a compound having a carboxylic acid group and a compound having an amino group.
- the urethane group is obtained, for example, by a condensation reaction between a compound having an isocyanate group and a compound having a hydroxyl group.
- FIGS. 3 (a) to 3 (c) An example of the surface state of the modified polymer substrate of the present invention is schematically shown in FIGS. 3 (a) to 3 (c).
- the modified polymer substrate 1 has an organic group having a specific functional group R 1 bonded to the surface of the polymer substrate 2 through an isocyanuric acid skeleton.
- FIG. 3A shows a configuration in which the isocyanuric acid skeleton is bonded to the polymer substrate 2 with two N atoms and one organic group is bonded to one isocyanuric acid skeleton.
- FIG. 3B shows a configuration in which the isocyanuric acid skeleton is bonded to the polymer substrate 2 with one N atom, and one organic group is bonded to one isocyanuric acid skeleton.
- FIG. 3C shows a configuration in which the isocyanuric acid skeleton is bonded to the polymer substrate 2 with one N atom, and two organic groups are bonded to one isocyanuric acid skeleton.
- the two organic groups may have different functional groups, or may have the same functional group.
- chlorine atoms are also bonded to the surface of the polymer substrate 2.
- chlorine atoms are present not only on the surface but also on the inside, but the abundance of chlorine atoms is inclined and increased from the inside toward the surface.
- the modified polymer substrate of the present invention may have a part of the structures shown in FIGS. 3 (a) to 3 (c) or may have all of these structures. .
- the surface treatment is performed with the surface treatment agent in the method for producing the modified polymer substrate described later. Although it can be sufficiently estimated from this, it can be detected by, for example, XPS or NMR.
- the amount of chlorine atoms, silicon atoms, fluorine atoms, etc. on the surface of the modified polymer substrate 1 can be analyzed.
- the amount of silicon atom, fluorine atom, etc. the amount of a specific functional group can be analyzed.
- NMR for example, the material of the surface portion of the modified polymer substrate 1 can be scraped off and subjected to chemical decomposition treatment as necessary, and analyzed by 13 C-NMR or 1 H-NMR.
- the presence / absence of an isocyanuric skeleton, its bonding position, its amount, etc., the presence / absence of a silicon atom, a fluorine atom, its bonding position, its amount, etc. can be determined.
- the surface configuration of the modified polymer substrate 1 can be detected.
- the organic group having the functional group R 1 for imparting a function to the surface of the polymer substrate 2 is formed on the surface of the polymer substrate 2 with an isocyanuric acid skeleton. Since it is couple
- the surface treating agent according to the present invention comprises (a) trichloroisocyanuric acid and (b) a compound having an unsaturated carbon-carbon double bond and an organic group having a specific functional group.
- the component (a) trichloroisocyanuric acid is represented by the structural formula (A) of the formula (14).
- the component (b) is represented by the structural formula (B) in the formula (14).
- R 1 is a substituent having a specific functional group.
- the (a) component is added to the unsaturated carbon-carbon double bond of the (b) component to form the structural formula (C).
- the new compound shown has been formed. This reaction proceeds sufficiently at room temperature.
- the compound represented by the structural formula (C) has an N—Cl bond that undergoes an addition reaction with an unsaturated carbon-carbon double bond. Therefore, depending on conditions such as the ratio of the component (a) and the component (b), in the surface treatment agent according to the present invention, the compound represented by the structural formula (C) is further converted into the unsaturated carbon-carbon dioxygen compound (b). It is presumed that a new compound represented by the formula (15) is also formed by adding 1 or 2 to the heavy bond. That is, in the surface treating agent according to the present invention, it is presumed that the compound represented by the structural formula (C) and the compound represented by the formula (15) are present in a predetermined ratio.
- the specific functional group is a functional group for imparting a specific function to the surface of the polymer substrate.
- Functional groups include silicone groups, fluorine-containing groups, perfluoroalkyl groups, ester groups, amide groups, imide groups, ether groups, aryl groups, azo groups, diazo groups, nitro groups, epoxy groups, carbonyl groups, and heterocyclic groups. , Mesoionic groups, halogen groups, amino groups, imino groups, alkyl groups, sulfonic acid groups, hydroxy groups, acyl groups, formyl groups, carboxylic acid groups, urea groups, urethane groups, cyano groups, and the like. In the organic group, only one type of these functional groups may be included, or two or more types of functional groups may be included.
- R 2, R 3, R 4 may be the same substituents as R 1, may be a substituent having a different particular functional group as R 1, It may be a hydrogen group or an alkyl group.
- R 1 , R 2 , R 3 , and R 4 may be substituents having specific functional groups different from each other, and some of R 1 , R 2 , R 3 , and R 4 are the same. It may be a substituent. More preferably, from the viewpoint of stability and the like, R 2 , R 3 and R 4 are preferably hydrogen groups.
- Formulas (16) to (19) Examples suitable for the component (b) are shown in formulas (16) to (19).
- Formulas (16) and (17) are examples in which the organic group has a silicone group and an ester group.
- Formula (18) is an example in which the organic group has an alkyl group and an ester group.
- Formula (19) is an example in which the organic group has an alkyl group.
- the surface treatment agent according to the present invention may contain one type of component (b) or two or more types of component (b).
- the molecular weight of the component (b) is preferably in the range of 50 to 10,000. More preferably, it is within the range of 70 to 5000. When the molecular weight is less than 50, the volatility of the component (b) is likely to increase, so that it is difficult to handle. On the other hand, if the molecular weight is greater than 10,000, the reactivity with the component (a) tends to decrease, so that it is difficult to impart a desired function to the polymer substrate.
- the blending amount of the component (b) is too small and falls outside the above range, the effect of imparting a specific function based on the specific functional group of the component (b) to the polymer substrate tends to be lowered.
- the amount of component (a) is too small and falls outside the above range, the reactivity with respect to the polymer substrate tends to decrease, so that it is difficult to sufficiently impart the desired function to the polymer substrate. Or durability cannot be obtained.
- the surface treatment agent according to the present invention can contain a solvent for dissolving or dispersing the component (a) and the component (b).
- the solvent is not particularly limited, but ether solvents (THF, diethyl ether, dioxane, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), ketone solvents (acetone, MEK, etc.), amides, etc. Examples include solvents (DMF, DMAC, NMP, etc.), tertiary alcohols (tert-butyl alcohol, etc.), water and the like. These may be used alone or in combination of two or more.
- the solvent for example, two types of solvents may be used: a solvent that dissolves or disperses the component (a) and a solvent that dissolves or disperses the component (b).
- the concentration of the component (a) with respect to the solvent is preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the solvent. More preferably, it is in the range of 2 to 5 parts by mass.
- concentration of the component (a) is too low and falls outside the above range, the reactivity with respect to the polymer substrate is likely to be lowered, so that it is difficult to sufficiently impart the desired function to the polymer substrate.
- concentration of the component (a) is too high and falls outside the above range, the processing unevenness on the polymer substrate tends to increase.
- the surface treatment agent according to the present invention may contain other components in addition to the component (a) and the component (b).
- other components include acids, bases, catalysts such as metal salts, and surfactants.
- the compound represented by the structural formula (C) or the compound represented by the formula (15) is formed in the surface treatment agent, and an unsaturated carbon-carbon double bond is formed.
- the compound represented by the structural formula (C) or the formula (C) is bonded to the unsaturated carbon-carbon double bond of the polymer substrate.
- the compound shown in 15) is added with 1,2 at the N—Cl bond portion derived from trichloroisocyanuric acid, and an organic group having a specific functional group is bonded to the surface of the polymer substrate via the isocyanuric acid skeleton.
- the modified polymer substrate of the present invention is obtained.
- This manufacturing method includes a step of bringing a specific treatment liquid into contact with the surface of a specific polymer substrate.
- the surface treatment agent according to the present invention can be used for the specific treatment liquid.
- Specified polymer substrate is a polymer substrate containing an organic component having an unsaturated carbon-carbon double bond.
- the organic component may be a polymer component of a polymer substrate, or may be a low molecular weight component or an oligomer component mixed with the polymer component. That is, the polymer component itself may have an unsaturated carbon-carbon double bond, or a low molecular weight component or an oligomer component mixed with the polymer component may have an unsaturated carbon-carbon double bond.
- the polymer component may be any of rubber, resin, and elastomer.
- Polymer components having unsaturated carbon-carbon double bonds include natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber ( CR), butyl rubber (IIR), ethylene propylene diene rubber (EPDM) and the like.
- NR natural rubber
- IR isoprene rubber
- BR butadiene rubber
- NBR acrylonitrile butadiene rubber
- SBR styrene butadiene rubber
- chloroprene rubber CR
- butyl rubber IIR
- EPDM ethylene propylene diene rubber
- the unsaturated carbon-carbon double bond is formed by copolymerization with a monomer component having an unsaturated carbon-carbon double bond. It can be an introduced polymer component.
- Such polymer components that normally have no unsaturated carbon-carbon double bond include acrylic rubber (ACM), fluororubber (FKM), chlorosulfonated polyethylene (CSM), hydrin rubber (CO, ECO, etc.) ), Silicone (Q), urethane (U), ethylene-vinyl acetate copolymer (EVA), polyethylene resin, epoxy resin, polyamide and the like.
- Examples of the monomer component having an unsaturated carbon-carbon double bond include liquid rubber and butadiene diol.
- an unsaturated carbon-carbon double bond can be introduced into urethane by adding liquid butadiene diol to the two-component urethane coating.
- FIG. 4 the compound shown in the structural formula (C) is shown as an example of the substrate in the treatment liquid, but the compound shown in the structural formula (C) exists as a substrate in the treatment liquid. It is an example of a compound, it is not limited to this, The compound etc. which are shown in Formula (15) may be contained.
- the temperature of the treatment liquid 3 is sufficient at room temperature, but is preferably in the range of 20 to 100 ° C., more preferably in the range of 25 to 70 ° C.
- the temperature of the treatment liquid 3 is less than 20 ° C.
- the reactivity between the substrate in the treatment liquid such as the compound represented by the structural formula (C)
- the unsaturated carbon-carbon double bond existing on the surface of the polymer substrate 2. Is prone to decline.
- the temperature of the processing liquid 3 exceeds 100 ° C., uneven processing tends to occur.
- the immersion time does not require a long time. For example, about 10 seconds to 1 hour is sufficient. More preferably, it is within the range of 30 seconds to 5 minutes. When the immersion time is less than 10 seconds, the contact time is too short and it is difficult to obtain a sufficient surface treatment effect. On the other hand, even if the immersion time exceeds 1 hour, the improvement of the surface treatment effect cannot be expected and the productivity is lowered.
- the polymer substrate 2 After immersing the polymer substrate 2 in the treatment liquid 3, the polymer substrate 2 may be pulled up from the treatment liquid 3, washed, and dried as shown in FIG. 4 (c).
- the cleaning liquid is not particularly limited as long as it is easily mixed with the solvent of the processing liquid 3 and can wash away the unreacted substrate.
- the same solvent as one or more of the solvents in the treatment liquid 3 can be used.
- the cleaning time does not require a long time. For example, about 10 seconds to 10 minutes is sufficient. If the cleaning time is less than 10 seconds, it is too short and it is difficult to obtain a sufficient cleaning effect. Therefore, an unreacted substrate tends to remain on the surface of the polymer substrate 2. On the other hand, even if the cleaning time exceeds 10 minutes, the improvement of the cleaning effect cannot be expected and the productivity is lowered.
- the room temperature is sufficient as the drying temperature, but it is preferably in the range of room temperature to 250 ° C, more preferably in the range of room temperature to 100 ° C.
- the drying temperature is lower than room temperature, the solvent is difficult to volatilize and has a long drying time.
- the drying temperature is higher than 250 ° C., the polymer substrate 2 is likely to be deteriorated. Moreover, the energy required for drying becomes too large.
- This production method can be applied in the production of polymer substrates of various polymer products, but in particular in the production of polymer substrates of polymer products that require a plurality of functions on the surface of the polymer substrate rather than a single function.
- it can be suitably applied in the production of a polymer base material constituting the surface of a conductive member for electrophotographic equipment or a wiper of an automobile.
- it can be suitably applied to the production of printing rolls, papermaking rolls, transport rolls, laminate rolls and the like.
- conductive members for electrophotographic equipment include conductive rolls (developing rolls, charging rolls, transfer rolls, toner supply rolls, etc.), conductive belts (transfer belts, etc.), and conductive blades (cleaning blades). it can.
- the conductive roll can be manufactured, for example, as follows. First, the shaft body is coaxially installed in the hollow portion of the roll molding die. Next, a conductive composition is injected into the mold. Next, the conductive composition is heated and cured, and then demolded. Thereby, the single layer electroconductive roll of the structure which formed one elastic layer (base layer) in the outer periphery of a shaft body can be manufactured.
- an elastic layer base layer
- the conductive composition is injected into the die.
- a two-layer conductive roll having a configuration in which two elastic layers are formed on the outer periphery of the shaft body can be manufactured by demolding.
- the conductive belt can be manufactured, for example, as follows. First, the conductive composition is spray-coated on the surface of the cylindrical mold. Next, the conductive composition is heated and cured. Thereby, the base layer of the conductive belt is formed. Next, the conductive composition is spray coated on the surface of the base layer. Next, the conductive composition is heated and cured. Thereby, an elastic layer is formed on the surface of the base layer of the conductive belt. Next, the conductive belt can be manufactured by blowing air between the base layer and the cylindrical mold to extract the cylindrical mold.
- the elastic layer of the single-layer conductive roll, the elastic layer outside the two-layer conductive roll, and the elastic layer outside the conductive belt are layers located on the surface of the conductive roll or the conductive belt.
- the conductive composition of the layer located on the surface of each member is obtained by copolymerization with the polymer component having the unsaturated carbon-carbon double bond or the monomer component having the unsaturated carbon-carbon double bond. It is preferable that a specific polymer component indicated by a polymer component into which an unsaturated carbon-carbon double bond is introduced is included.
- conductive agents electroconductive agents such as carbon black and ionic conductive agents such as quaternary ammonium salts, quaternary phosphonium salts, borates, and surfactants
- additives include fillers, reinforcing agents, processing aids, curing agents, cross-linking agents, cross-linking accelerators, foaming agents, antioxidants, plasticizers, UV absorbers, silicone oils, lubricants, auxiliary agents, surfactants. And so on.
- the conductive composition of the base layer of the two-layer conductive roll and the base layer of the conductive belt may or may not contain the specific polymer component.
- the polymer component of the conductive composition of the base layer natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), styrene butadiene rubber (SBR), chloroprene rubber (CR), Butyl rubber (IIR), ethylene propylene diene rubber (EPDM), acrylic rubber (ACM), fluoro rubber (FKM), chlorosulfonated polyethylene (CSM), hydrin rubber (CO, ECO, etc.), silicone (Q), urethane (U) And ethylene-vinyl acetate copolymer (EVA), polyethylene resin, epoxy resin, polyamide and the like.
- the conductive composition of the base layer may contain a conductive agent, various additives, and the like as necessary.
- the shaft body is not particularly limited as long as it has conductivity. Specific examples include solid bodies made of metal such as iron, stainless steel, and aluminum, and a cored bar made of a hollow body. You may apply
- the modified polymer substrate according to the present invention may be one in which an uneven shape is imparted to the surface of the polymer substrate.
- the surface of the polymer substrate is provided with a concavo-convex shape, for example, when applied to the outermost layer of the developing roll, the toner transportability can be further improved. Further, toner filming can be further suppressed.
- the concavo-convex shape may be imparted, for example, by 1) the roughness forming particles forming the surface roughness being included inside the polymer substrate, or 2) the surface of the polymer substrate in contact with the mold. It may be provided by molding a polymer substrate using a molding die provided with a plurality of recesses corresponding to the concavo-convex shape on the inner surface of the mold. In the latter case of 2) molding, the plurality of recesses on the inner surface of the mold may be formed, for example, by 2-1) blasting the inner surface of the mold, or 2-2) metal on the inner surface of the mold. It may be formed by plating defects at the time of plating, or 2-3) formed by removing resin particles from the plating layer containing resin particles formed on the inner surface of the mold. There may be.
- acrylic particles, silica particles, urethane particles, crosslinked polymethyl methacrylate particles, urea resin particles and the like can be used as the roughness forming particles. These may be used alone or in combination.
- the average particle diameter ⁇ of the roughness forming particles is not particularly limited, but is 6 to 20 ⁇ m from the viewpoint of excellent toner conveyance amount in relation to the particle diameter of the toner and appropriate irregularities being formed. It is preferable to be within the range.
- the average particle diameter of the roughness forming particles can be measured by, for example, a particle size measuring instrument Microtrac UPA-ST150 (manufactured by Nikkiso Co., Ltd.).
- the defect in plating is a result of intentional electroless plating, and hydrogen gas generated during the plating reaction is adsorbed on the surface of the deposited plating, and in the adsorbed part. Formed by inhibiting further deposition of the plating.
- hydrocarbon-based cationic surfactants such as lauryltrimethylammonium chloride
- an amphoteric surfactant such as lauryl betaine.
- the plating metal include nickel, cobalt, copper, tin, palladium, and gold.
- a reducing agent, a complexing agent, and the like used in a normal plating bath for electroless composite plating can be appropriately mixed in the plating bath.
- the plating layer is formed by performing electroless plating using a plating solution containing resin particles.
- the resin particles are dissolved and removed from the plating layer using a solvent, thereby forming a recess in the portion where the resin particles existed.
- resin particles resin particles that are soluble in a solvent are used. Examples of such resin particles include acrylic particles, styrene particles, urethane particles, nylon particles, silicone particles, and cellulose particles.
- the plating solution contains metal ions, a reducing agent, a complexing agent, a pH buffering agent, the resin particles, and the like.
- the metal ions are plating metal ions. Examples of the plating metal include nickel, cobalt, copper, gold, and silver.
- complexing agents include carboxylic acids and amine compounds.
- carboxylic acid and the amine compound are used in combination, the resin particles can be co-deposited with the plating metal at a high density.
- the plated metal can be grown in a columnar shape. Thereby, the depth of a recessed part can be made larger than the particle diameter of a resin particle.
- a solid columnar iron bar with a diameter of 12 mm was prepared as a core bar to be a shaft body, and an adhesive was applied to the outer peripheral surface of the core bar.
- NBR manufactured by JSR, N222L
- a plasticizer manufactured by DIC, Polysizer W-4000
- a closed mixer whose temperature was adjusted to 50 ° C. for 10 minutes.
- Nickel sulfate hexahydrate 26g / L Sodium hypophosphite monohydrate (reducing agent) 32 g / L Glycine (complexing agent) 7.5g / L Sodium citrate dihydrate (complexing agent) 30 g / L Acrylic particles ⁇ 1> 20 g / L Cationic surfactant 0.1g / L
- a two-layer conductive roll was produced in the same manner as the material A4 to be treated except that the following resin layer forming composition (2) was used. This was designated as material B1.
- the resin layer forming composition (2) is different from the resin layer forming composition (1) in that it does not contain a C ⁇ C bond-containing polyol
- a two-layer conductive roll was produced in the same manner as the material to be treated A4 except that the following resin layer forming composition (3) was used. This was designated as A5.
- ⁇ Preparation of resin layer forming composition (3)> 90 parts by mass of urethane resin (Nipporan 5199 manufactured by Nippon Polyurethane Industry Co., Ltd.) as a binder resin, 10 parts by mass of a C ⁇ C bond-containing polyol (“Poly bdR-45HT” manufactured by Idemitsu Petrochemical Co., Ltd.), and isocyanate MDI as a crosslinking agent 40 parts by mass (“Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.), 30 parts by mass of carbon black (“Dia Black # 3030” manufactured by Mitsubishi Chemical Corporation) as a conductive agent, and C C bond-containing silicone oil (manufactured by Shin-Etsu Silicone) , X-22-174DX) 1 part
- a two-layer conductive roll was produced in the same manner as the material to be treated A4 except that the following resin layer forming composition (4) was used. This was designated as A6.
- the following elastic layer forming composition (1) is spray coated on the surface of the base layer, heated from room temperature to 170 ° C. over 5 minutes, and then heated at 170 ° C. for 30 minutes. Went. Thereby, an elastic layer (thickness: 170 ⁇ m) was formed on the surface of the base layer. Next, air was blown between the base layer and the cylindrical mold to extract the cylindrical mold, thereby producing a conductive belt. This was designated as A7.
- a conductive belt was produced in the same manner as the material A7 except that the following elastic layer forming composition (2) was used. This was designated as A8.
- ⁇ Preparation of elastic layer forming composition (2)> 100 parts by mass of liquid NBR (NH 2 modified NBR, manufactured by Emerald Performance Materials, "ATBN1300x45”), 1 part by mass of C C bond-containing silicone oil (manufactured by Shin-Etsu Silicone, X-22-174DX), By mixing 35 parts by mass of blocked isocyanate (“Coronate 2507” manufactured by Nippon Polyurethane Industry Co., Ltd.) as a crosslinking agent and cyclohexanone (solvent ratio: 30% by mass) as a solvent, the elastic layer forming composition (2) is obtained. Prepared.
- the composition (2) for forming an elastic layer is different from the composition (1) for forming an elastic layer in that it further contains a C ⁇ C bond-containing silicone oil.
- ⁇ Preparation of surface treatment agent A1> 5 parts by mass of trichloroisocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part by mass of C C bond-containing silicone oil (manufactured by Shin-Etsu Silicone, X-22-174DX), 80 parts by mass of tert-butyl alcohol, and ethyl acetate Surface treatment agent A1 was prepared by mixing 20 parts by mass.
- ⁇ Preparation of surface treatment agent A3> By mixing 5 parts by mass of trichloroisocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.5 parts by mass of perfluorohexylethylene, 80 parts by mass of tert-butyl alcohol, and 20 parts by mass of ethyl acetate, a surface treatment agent A3 was prepared.
- Surface treatment agent B1 was prepared by mixing 5 parts by mass of trichloroisocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 80 parts by mass of tert-butyl alcohol, and 20 parts by mass of ethyl acetate.
- a C C bond-containing silicone oil (X-22-174DX, manufactured by Shin-Etsu Silicone) was used as the surface treatment agent B2.
- a surface treating agent B3 was prepared by mixing 5 parts by mass of diphenylmethane diisocyanate, 2 parts by mass of an OH group-containing acrylic silicone resin (manufactured by NOF Corporation, "Modiper FS700”) and 100 parts by mass of ethyl acetate.
- ⁇ Preparation of surface treatment agent B4 2 parts by mass of trichloroisocyanuric acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2 parts by mass of boron trifluoride-diethyl ether complex (manufactured by Kanto Chemical Co., Inc., containing 48% by mass of BF 3 ), 80 parts by mass of tert-butyl alcohol,
- the surface treatment agent B4 was prepared by mixing 20 parts by mass of ethyl acetate.
- Example 1 Using the material to be treated A1, the roll surface was immersed in the surface treatment agent A1 at 25 ° C. for 30 seconds, washed with ethyl acetate at 25 ° C. for 30 seconds, and then dried at 100 ° C. for 10 minutes. Thereby, the single layer conductive roll of Example 1 was obtained.
- Comparative Examples 2-3 Surface treatment was performed in the same manner as in Example 1 except that the material to be treated A1 was used, and the surface treatment agents B1 and B2 were used instead of the surface treatment agent A1. As a result, single-layer conductive rolls of Comparative Examples 2 to 3 were obtained.
- Comparative Example 4 Using the material to be treated A1, the roll surface was immersed in the surface treatment agent B3 for 30 seconds at 25 ° C. and then heated at 120 ° C. for 60 minutes. As a result, a single-layer conductive roll of Comparative Example 4 was obtained.
- Example 2 Using the material to be treated A2, the roll surface was immersed in the surface treatment agent A1 at 25 ° C. for 30 seconds, washed with ethyl acetate at 25 ° C. for 30 seconds, and then dried at 100 ° C. for 10 minutes. As a result, a single-layer conductive roll of Example 2 was obtained.
- Example 3 A single-layer conductive roll of Example 3 was obtained in the same manner as in Example 2 except that the material A2 was used and the surface treatment agent A2 was used instead of the surface treatment agent A1.
- Example 4 A single-layer conductive roll of Example 4 was obtained in the same manner as Example 2 except that the material to be treated A3 was used.
- Example 5 Using the material to be treated A4, the roll surface was immersed in the surface treatment agent A1 at 25 ° C. for 30 seconds, washed with ethyl acetate at 25 ° C. for 30 seconds, and then dried at 100 ° C. for 10 minutes. Thereby, the two-layer conductive roll of Example 5 was obtained.
- Comparative Example 7 A two-layer conductive roll of Comparative Example 7 was obtained in the same manner as in Example 5 except that the material to be treated B1 was used instead of the material to be treated A4.
- Example 6 A double-layer conductive roll of Example 6 was obtained in the same manner as Example 5 except that the material A6 was used instead of the material A4.
- Example 7 Using the material to be treated A7, the belt surface was dipped in the surface treatment agent A1 at 25 ° C. for 30 seconds, the roll surface was washed with ethyl acetate at 25 ° C. for 30 seconds, and then dried at 100 ° C. for 10 minutes. As a result, a conductive belt of Example 7 was obtained.
- Example 8 A conductive belt of Example 8 was obtained in the same manner as in Example 7 except that the material A7 was used and the surface treatment agent A3 was used instead of the surface treatment agent A1.
- Comparative Examples 10 and 11 Conductive belts of Comparative Examples 10 and 11 were obtained in the same manner as in Example 7 except that the material A7 was used and the surface treatment agents B1 and B4 were used instead of the surface treatment agent A1.
- the characteristics were evaluated using each conductive roll and each conductive belt produced.
- the measurement method and evaluation method are shown below.
- Each conductive roll was incorporated into a commercially available color printer (Color Laser Jet 4700dn, manufactured by Japan HP) as a developing roll, and the adhesion state of the toner to the roll surface after printing 20,000 sheets was visually evaluated. The case where the toner did not adhere to the roll surface was indicated as “ ⁇ ”, and the case where the toner was attached was indicated as “X”.
- Each conductive belt is used as an intermediate transfer belt and incorporated in a commercially available full-color digital multi-function peripheral (by Konica Minolta Business Technologies, bizhab C550). Outputs 100,000 images under a 23.5 ° C x 53% RH environment (test pattern) Printing). Thereafter, the surface of the belt was visually observed, and “ ⁇ ” indicates that no cracks were observed, and “ ⁇ ” indicates that cracks were observed but were very fine and did not adversely affect image quality. In addition, “ ⁇ ” indicates that cracks that adversely affect the image quality are recognized.
- Comparative Example 1 the material to be treated A1 is not surface-treated with the surface treatment agent.
- the material to be treated A1 is surface treated with a surface treatment agent B1 made of only isocyanuric acid except for the solvent.
- the material to be treated A1 is surface-treated with the surface treatment agent B2 made of only silicone oil.
- the material to be treated A1 is surface-treated with a surface treatment agent B3 containing isocyanate.
- Example 2 the material A2 having NBR on the surface of the single-layer conductive roll is surface-treated with the surface treatment agent A1 as in Example 1.
- Example 3 the material to be treated A2 is surface-treated with a surface treatment agent A2 containing trichloroisocyanuric acid, a C ⁇ C bond-containing silicone oil, and butyl acrylate.
- a surface treatment agent A2 containing trichloroisocyanuric acid, a C ⁇ C bond-containing silicone oil, and butyl acrylate it was confirmed that the coefficient of friction after the initial test and after the fixing test was kept low, and the toner fixing and filming were suppressed.
- Example 4 the material A3 having a convex shape is molded by using a mold having a large number of concave shapes on the surface. As a result, it was confirmed that the friction coefficient after the initial test and after the fixing test was kept low, and that the toner sticking and filming were suppressed. It was also confirmed that the toner was more excellent in the effect of suppressing toner fixation and filming.
- Comparative Example 5 the material A2 is not surface-treated with the surface treatment agent. As a result, it can be seen that the coefficient of friction is high at the initial stage or after the fixing test, and toner fixing and filming are not suppressed.
- Example 5 as in Example 1, it was confirmed that the initial and post-adhesion coefficient of friction was kept low, and toner adhesion and filming were suppressed.
- the material to be treated A6 is surface treated with the surface treatment agent A1 as in Example 5.
- Example 6 as in Example 5 it was confirmed that the initial and post-adhesion coefficient of friction was kept low, and toner adhesion and filming were suppressed. It was also confirmed that the toner was more excellent in the effect of suppressing toner fixation and filming.
- Comparative Example 6 the material to be treated A4 is not surface-treated with the surface treatment agent.
- Comparative Example 7 the material to be treated B1 that does not contain a C ⁇ C bond is surface-treated with the surface treatment agent A1.
- Comparative Example 8 instead of surface treatment with the surface treatment agent A1 containing the C ⁇ C bond-containing silicone oil, the C ⁇ C bond-containing silicone oil is contained in the material to be treated A5.
- Example 7 the material to be treated A7 having a C ⁇ C bond in the elastic layer on the surface of the conductive belt is surface-treated with the surface treatment agent A1 as in Example 1.
- Example 7 as in Example 1, it was confirmed that the initial and post-adhesion coefficient of friction was kept low, and toner adhesion and filming were suppressed.
- Example 8 the material to be treated A7 is surface-treated with a surface treatment agent A2 containing trichloroisocyanuric acid and perfluorohexylethylene.
- Example 8 as in Example 7, it was confirmed that the initial and post-adhesion coefficient of friction was kept low, and toner adhesion and filming were suppressed.
- Comparative Example 9 the material A7 is not surface-treated with the surface treatment agent.
- the material to be treated A7 is surface-treated with the surface treatment agent B1 made only of isocyanuric acid other than the solvent.
- the material to be treated A7 is surface treated with a surface treatment agent B4 made of isocyanuric acid and boron trifluoride complex except for the solvent.
- Comparative Example 12 instead of surface treatment with the surface treatment agent A1 containing the C ⁇ C bond-containing silicone oil, the C ⁇ C bond-containing silicone oil is contained in the material to be treated A8.
Abstract
Description
軸体となる芯金として直径12mmの中実円柱状鉄棒を準備し、芯金の外周面に接着剤を塗布した。接着剤を塗布した芯金を成形用金型内にセットした後、導電剤が配合された液状シリコーンゴム(信越化学工業社製、X-34-264A/B、混合比A/B=70/30)を金型内に射出し、190℃ で30分加熱し硬化させた後、脱型した。これにより、芯金の外周に、C=C結合を表面に残したシリコーンゴムを含むゴム弾性層(厚み2mm)を1層有する単層導電性ロールを作製した。これを被処理材A1とした。
NBR(JSR社製、N222L)100質量部と、酸化亜鉛5質量部と、ステアリン酸2質量部と、テトラブチルアンモニウムパークロレート(試薬)1質量部と、粉末硫黄0.8質量部と、ポリエステル可塑剤(DIC社製、ポリサイザーW-4000)10質量部と、を50℃に温度調節した密閉型ミキサーにて10分間混練して、原料コンパウンドを調製した。ゴム弾性層の形成材料として、この原料コンパウンドを用いた以外は被処理材A1と同様にして、芯金の外周に、NBRを含むゴム弾性層(厚み2mm)を1層有する単層導電性ロールを作製した。これを被処理材A2とした。
注型する金型を下記の金型にした以外は被処理剤A2と同様にして単層導電性ロールを作製した。これを被処理材A3とした。
<表面粗さを付与した成形型の作製>
内径16mmの円筒形の金型基材の型内面に、下記のめっき液を用いて、めっき液pH8、めっき液温度80℃、めっき時間120分の条件で、無電解めっきを行い、アクリル粒子を含んだ無電解めっき層を形成した。(めっき厚さ16μm)。その後、無電解めっき層に取り込まれたアクリル粒子をアセトンにて溶解除去することにより、型内面に多数の凹部を有する成形型を得た。
カチオン性界面活性剤(ラウリルトリメチルアンモニウムクロライド)を用いてアクリル粒子<1>(根上工業製、アートパールGR600、平均粒子径10μm)を水中に分散させた樹脂粒子分散液を基本めっき液に添加することにより、下記の組成のめっき液を調製した。
硫酸ニッケル六水和物26g/L
次亜リン酸ナトリウム一水和物(還元剤)32g/L
グリシン(錯化剤)7.5g/L
クエン酸ナトリウム二水和物(錯化剤)30g/L
アクリル粒子<1>20g/L
カチオン性界面活性剤0.1g/L
ゴム弾性層の形成材料として、導電剤が配合された液状シリコーンゴム(信越化学工業社製、X-34-264A/B、混合比A/B=50/50)を用いた以外は被処理材A1と同様にして、芯金の外周に、シリコーンゴムを含むゴム弾性層(厚み2mm)を形成した。次いで、このゴム弾性層の外周面に、ロールコート法により、下記の樹脂層形成用組成物(1)を塗工した後、乾燥処理(180℃×60分)を行うことにより、ベースロールの外周面に厚さ10μmの樹脂層を形成した。これにより、二層導電性ロールを作製した。これを被処理材A4とした。
<樹脂層形成用組成物(1)の調製>
バインダー樹脂としてウレタン樹脂(日本ポリウレタン工業社製「ニッポラン5199」)90質量部と、C=C結合含有ポリオール(出光石油化学社製「Poly bdR-45HT」)10質量部と、架橋剤としてイソシアネートMDI(日本ポリウレタン工業社製「コロネートL」)40質量部と、導電剤としてカーボンブラック(三菱化学社製「ダイアブラック♯3030」)30質量部と、を十分に混合し、有機溶剤(メチルエチルケトン)に溶解させて濃度20質量%のコーティング液とした。
樹脂層形成用組成物(1)に代えて、下記の樹脂層形成用組成物(2)を用いた以外は被処理材A4と同様にして、二層導電性ロールを作製した。これを被処理材B1とした。
<樹脂層形成用組成物(2)の調製>
バインダー樹脂としてウレタン樹脂(日本ポリウレタン工業社製「ニッポラン5199」)100質量部と、架橋剤としてイソシアネートMDI(日本ポリウレタン工業社製「コロネートL」)40質量部と、導電剤としてカーボンブラック(三菱化学社製「ダイアブラック♯3030」)30質量部と、を十分に混合し、有機溶剤(メチルエチルケトン)に溶解させて濃度20質量%のコーティング液とした。樹脂層形成用組成物(2)は、樹脂層形成用組成物(1)と比較して、C=C結合含有ポリオールを含有していない点が異なる。
樹脂層形成用組成物(1)に代えて、下記の樹脂層形成用組成物(3)を用いた以外は被処理材A4と同様にして、二層導電性ロールを作製した。これを被処理材A5とした。
<樹脂層形成用組成物(3)の調製>
バインダー樹脂としてウレタン樹脂(日本ポリウレタン工業社製「ニッポラン5199」)90質量部と、C=C結合含有ポリオール(出光石油化学社製「Poly bdR-45HT」)10質量部と、架橋剤としてイソシアネートMDI(日本ポリウレタン工業社製「コロネートL」)40質量部と、導電剤としてカーボンブラック(三菱化学社製「ダイアブラック♯3030」)30質量部と、C=C結合含有シリコーンオイル(信越シリコーン社製、X-22-174DX)1質量部とを十分に混合し、有機溶剤(メチルエチルケトン)に溶解させて濃度20質量%のコーティング液とした。樹脂層形成用組成物(3)は、樹脂層形成用組成物(1)と比較して、C=C結合含有シリコーンオイルをさらに含有している点が異なる。
樹脂層形成用組成物(1)に代えて、下記の樹脂層形成用組成物(4)を用いた以外は被処理材A4と同様にして、二層導電性ロールを作製した。これを被処理材A6とした。
<樹脂層形成用組成物(4)の調製>
バインダー樹脂としてウレタン樹脂(日本ポリウレタン工業社製「ニッポラン5199」)90質量部と、C=C結合含有ポリオール(出光石油化学社製「Poly bdR-45HT」)10質量部と、架橋剤としてイソシアネートMDI(日本ポリウレタン工業社製「コロネートL」)40質量部と、導電剤としてカーボンブラック(三菱化学社製「ダイアブラック♯3030」)30質量部と、粗さ粒子として、ウレタン粒子(根上工業社製「アートパールC800透明」)15重量部を十分に混合し、有機溶剤(メチルエチルケトン)に溶解させて濃度20質量%のコーティング液とした。
ポリアミドイミド樹脂(東洋紡績社製、「HR-16NN」)100質量部と、カーボンブラック(電気化学工業社製、「デンカブラックHS-100」)10質量部と、NMP(溶剤)800質量部とを混合することにより、ポリアミドイミド樹脂分散溶液を調製した。次いで、円筒形金型の表面にポリアミドイミド樹脂分散溶液をスプレーコーティングして、常温~250℃まで2時間かけて昇温させた後、250℃で1時間保持することにより加熱処理を行った。これにより、導電性ベルトの基層(厚さ80μm)を形成した。
<弾性層形成用組成物(1)の調製>
液状NBR(NH2変性NBR、エメラルド・パフォーマンス・マテリアルズ社製、「ATBN1300x45」)と、架橋剤としてのブロックイソシアネート(日本ポリウレタン工業社製「コロネート2507」)35質量部と、溶剤としてのシクロヘキサノン(溶剤比率30質量%)とを混合することにより、弾性層形成用組成物(1)を調製した。
弾性層形成用組成物(1)に代えて、下記の弾性層形成用組成物(2)を用いた以外は被処理材A7と同様にして、導電性ベルトを作製した。これを被処理材A8とした。
<弾性層形成用組成物(2)の調製>
液状NBR(NH2変性NBR、エメラルド・パフォーマンス・マテリアルズ社製、「ATBN1300x45」)100質量部と、C=C結合含有シリコーンオイル(信越シリコーン社製、X-22-174DX)1質量部と、架橋剤としてのブロックイソシアネート(日本ポリウレタン工業社製「コロネート2507」)35質量部と、溶剤としてのシクロヘキサノン(溶剤比率30質量%)とを混合することにより、弾性層形成用組成物(2)を調製した。弾性層形成用組成物(2)は、弾性層形成用組成物(1)と比較して、C=C結合含有シリコーンオイルをさらに含有している点が異なる。
トリクロロイソシアヌル酸(東京化成工業社製)5質量部と、C=C結合含有シリコーンオイル(信越シリコーン社製、X-22-174DX)1質量部と、tert-ブチルアルコール80質量部と、酢酸エチル20質量部とを混合することにより、表面処理剤A1を調製した。
トリクロロイソシアヌル酸(東京化成工業社製)2.5質量部と、C=C結合含有シリコーンオイル(信越シリコーン社製、X-22-174DX)0.2質量部と、ブチルアクリレート2質量部と、tert-ブチルアルコール80質量部と、酢酸エチル20質量部とを混合することにより、表面処理剤A2を調製した。
トリクロロイソシアヌル酸(東京化成工業社製)5質量部と、パーフルオロヘキシルエチレン0.5質量部と、tert-ブチルアルコール80質量部と、酢酸エチル20質量部とを混合することにより、表面処理剤A3を調製した。
トリクロロイソシアヌル酸(東京化成工業社製)5質量部と、tert-ブチルアルコール80質量部と、酢酸エチル20質量部とを混合することにより、表面処理剤B1を調製した。
C=C結合含有シリコーンオイル(信越シリコーン社製、X-22-174DX)を表面処理剤B2とした。
ジフェニルメタンジイソシアネート5質量部と、OH基含有アクリルシリコーン樹脂(日油社製、「モディパーFS700」)2質量部と、酢酸エチル100質量部とを混合することにより、表面処理剤B3を調製した。
トリクロロイソシアヌル酸(東京化成工業社製)2質量部と、三フッ化ホウ素-ジエチルエーテル錯体(関東化学社製、BF3を48質量%含有)2質量部と、tert-ブチルアルコール80質量部と、酢酸エチル20質量部とを混合することにより、表面処理剤B4を調製した。
被処理材A1を用い、表面処理剤A1中にロール表面が浸るように25℃で30秒間浸漬し、酢酸エチルでロール表面を25℃で30秒間洗浄した後、100℃で10分間乾燥した。これにより、実施例1の単層導電性ロールを得た。
被処理材A1について、表面処理剤による表面処理を行わなかった。
被処理材A1を用い、表面処理剤A1に代えて、表面処理剤B1~B2を用いた以外は実施例1と同様にして表面処理を行った。これにより、比較例2~3の単層導電性ロールを得た。
被処理材A1を用い、表面処理剤B3中にロール表面が浸るように25℃で30秒間浸漬した後、120℃で60分間加熱した。これにより、比較例4の単層導電性ロールを得た。
被処理材A2を用い、表面処理剤A1中にロール表面が浸るように25℃で30秒間浸漬し、酢酸エチルでロール表面を25℃で30秒間洗浄した後、100℃で10分間乾燥した。これにより、実施例2の単層導電性ロールを得た。
被処理材A2を用い、表面処理剤A1に代えて表面処理剤A2を用いた以外は実施例2と同様にして実施例3の単層導電性ロールを得た。
被処理材A2について、表面処理剤による表面処理を行わなかった。
被処理材A3を用いた以外は実施例2と同様にして実施例4の単層導電性ロールを得た。
被処理材A4を用い、表面処理剤A1中にロール表面が浸るように25℃で30秒間浸漬し、酢酸エチルでロール表面を25℃で30秒間洗浄した後、100℃で10分間乾燥した。これにより、実施例5の二層導電性ロールを得た。
被処理材A4について、表面処理剤による表面処理を行わなかった。
被処理材A4に代えて、被処理材B1を用いた以外は実施例5と同様にして、比較例7の二層導電性ロールを得た。
被処理材A4に代えて被処理材A5を用い、被処理材A5について表面処理剤による表面処理を行わなかった。
被処理材A4に代えて、被処理材A6を用いた以外は実施例5と同様にして、実施例6の二層導電性ロールを得た。
被処理材A7を用い、表面処理剤A1中にベルト表面が浸るように25℃で30秒間浸漬し、酢酸エチルでロール表面を25℃で30秒間洗浄した後、100℃で10分間乾燥した。これにより、実施例7の導電性ベルトを得た。
被処理材A7を用い、表面処理剤A1に代えて表面処理剤A3を用いた以外は実施例7と同様にして実施例8の導電性ベルトを得た。
被処理材A7について、表面処理剤による表面処理を行わなかった。
被処理材A7を用い、表面処理剤A1に代えて表面処理剤B1、B4を用いた以外は実施例7と同様にして比較例10、11の導電性ベルトを得た。
被処理材A7に代えて被処理材A8を用い、被処理材A8について表面処理剤による表面処理を行わなかった。
静動摩擦係数計(協和界面科学社製)を用い、鋼球(直径3mm)圧子、移動速度1cm/秒、荷重100gの条件下で、導電性ロールまたは導電性ベルトの表面の初期摩擦係数を測定した。
キヤノンLBP5050のイエロートナーをロール表面またはベルト表面に均一にまぶした状態で、導電性ロールまたは導電性ベルトを、50℃、95%湿度の条件下で湿熱槽に1週間投入した。その後、導電性ロールまたは導電性ベルトを取り出し、室温まで冷却した後、ロール表面またはベルト表面をエアブローした。表面にまぶしたトナーがほぼ全量取り除かれた場合を「○」とし、表面にまぶしたトナーが取り除かれなかった場合を「×」とした。
トナー固着試験を行った導電性ロールまたは導電性ベルトの表面を不織布で丁寧に拭き取った後、初期摩擦係数の測定条件と同条件で、この表面の摩擦係数を測定した。
各導電性ロールを現像ロールとして市販のカラープリンター(日本HP社製、Color Laser Jet4700dn)に組み込み、2万枚印字後のロール表面へのトナーの付着状態を目視評価した。ロール表面へのトナーの付着がないものを「○」とし、トナーの付着があるものを「×」とした。
各導電性ベルトを中間転写ベルトとして市販のフルカラーデジタル複合機(コニカミノルタビジネステクノロジーズ社製、bizhab C550)に組み込み、23.5℃×53%RHの環境下で10万枚の画像出力(テストパターン印刷)を行った。その後、ベルト表面を目視で観察し、クラックが全く認められないものを「○」とし、クラックは認められるものの非常に微細であって画質に悪影響を与えるほどのものではないものを「△」とし、画質に悪影響を与えるほどのクラックが認められるものを「×」とした。
Claims (6)
- ポリマー基材の表面に、前記ポリマー基材の表面に機能を付与するための官能基を有する有機基がイソシアヌル酸骨格を介して結合されていることを特徴とする改質ポリマー基材。
- 前記官能基は、シリコーン基、フッ素含有基、パーフルオロアルキル基、エステル基、アミド基、イミド基、エーテル基、アリール基、アゾ基、ジアゾ基、ニトロ基、エポキシ基、カルボニル基、ヘテロ環基、メソイオン基、ハロゲン基、アミノ基、イミノ基、アルキル基、スルホン酸基、ヒドロキシ基、アシル基、ホルミル基、カルボン酸基、ウレア基、ウレタン基、シアノ基から選択された1種または2種以上の官能基であることを特徴とする請求項1に記載の改質ポリマー基材。
- 前記有機基は、不飽和炭素-炭素二重結合を持つ有機化合物に由来する基であることを特徴とする請求項1または2に記載の改質ポリマー基材。
- 前記ポリマー基材の表面には凹凸形状が付与されていることを特徴とする請求項1から3のいずれか1項に記載の改質ポリマー基材。
- 不飽和炭素-炭素二重結合を持つ有機成分を含有するポリマー基材の表面に、下記の(a)成分および(b)成分を含有する処理液を接触させる工程を有することを特徴とする改質ポリマー基材の製造方法。
(a)トリクロロイソシアヌル酸
(b)不飽和炭素-炭素二重結合と、前記ポリマー基材の表面に機能を付与するための官能基を有する有機基とを持つ化合物 - 不飽和炭素-炭素二重結合を持つ有機成分を含有するポリマー基材の表面に接触させる表面処理剤であって、
下記の(a)成分および(b)成分を含有することを特徴とする表面処理剤。
(a)トリクロロイソシアヌル酸
(b)不飽和炭素-炭素二重結合と、前記ポリマー基材の表面に機能を付与するための官能基を有する有機基とを持つ化合物
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US7887790B2 (en) * | 2004-02-20 | 2011-02-15 | Cornell Research Foundation, Inc. | Polymers and polymer coatings |
US8292791B2 (en) * | 2005-04-07 | 2012-10-23 | Bridgestone Corporation | Electrical conductive roller |
ATE532828T1 (de) * | 2006-01-18 | 2011-11-15 | Kaneka Corp | Härtbare zusammensetzung |
EP2147946A4 (en) * | 2007-05-08 | 2011-11-30 | Idemitsu Kosan Co | POLYCARBONATE POLYMER, COATING LIQUID, AND ELECTRO-PHOTOGRAPHIC LIGHT-SENSITIVE BODY |
KR101800015B1 (ko) * | 2007-12-10 | 2017-11-21 | 카네카 코포레이션 | 알칼리 현상성을 갖는 경화성 조성물 및 그것을 사용한 절연성 박막 및 박막 트랜지스터 |
JP5453773B2 (ja) * | 2008-02-18 | 2014-03-26 | 株式会社リコー | 電子写真用中間転写ベルト及び電子写真装置 |
US8530567B2 (en) * | 2010-02-18 | 2013-09-10 | Basf Se | Polymer dispersion which comprises a highly branched polycarbonate having unsaturated fatty acid groups |
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2011
- 2011-08-16 JP JP2012502336A patent/JP5421452B2/ja active Active
- 2011-08-16 WO PCT/JP2011/068537 patent/WO2012023547A1/ja active Application Filing
- 2011-08-16 CN CN201180028733.0A patent/CN102958985B/zh active Active
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2012
- 2012-11-28 US US13/687,474 patent/US20130084428A1/en not_active Abandoned
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JPH02251536A (ja) * | 1988-12-06 | 1990-10-09 | Yokohama Rubber Co Ltd:The | 加硫ゴムとウレタンエラストマーとの接着方法 |
JP2002539279A (ja) * | 1999-03-10 | 2002-11-19 | コモンウェルス サイエンティフィック アンド インダストリアル リサーチ オーガナイゼイション | 加硫ゴム質物体の表面改質 |
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Cited By (7)
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US9095870B2 (en) | 2011-08-30 | 2015-08-04 | Sumitomo Riko Company Limited | Conductive roll |
JP2014073489A (ja) * | 2012-09-12 | 2014-04-24 | Turner Shikisai Kk | エラストマー塗装方法、ゴム塗装面変色防止剤およびゴム用塗料 |
JP2015137304A (ja) * | 2014-01-22 | 2015-07-30 | 三菱電線工業株式会社 | ゴムシール用表面処理液および該表面処理液を用いたゴムシールの表面改質方法 |
JP2016084456A (ja) * | 2014-10-29 | 2016-05-19 | 三菱電線工業株式会社 | ゴム製品の製造方法 |
JP2016132767A (ja) * | 2015-01-22 | 2016-07-25 | 三菱電線工業株式会社 | ゴム製品の製造方法 |
JP2021060511A (ja) * | 2019-10-07 | 2021-04-15 | 信越ポリマー株式会社 | 現像ローラ、現像装置及び画像形成装置 |
JP7314013B2 (ja) | 2019-10-07 | 2023-07-25 | 信越ポリマー株式会社 | 現像ローラ、現像装置及び画像形成装置 |
Also Published As
Publication number | Publication date |
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JPWO2012023547A1 (ja) | 2013-10-28 |
CN102958985A (zh) | 2013-03-06 |
JP5421452B2 (ja) | 2014-02-19 |
CN102958985B (zh) | 2014-03-19 |
US20130084428A1 (en) | 2013-04-04 |
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