JP4012159B2 - Adhesive for blade for electrophotographic apparatus and blade for electrophotographic apparatus - Google Patents

Description

This invention forms a thin film while triboelectrically charging toner in a developing blade and a cleaning blade for removing residual toner on a photoreceptor (drum, belt, etc.) in an electrophotographic copying machine, printer, facsimile, etc. Two-component thermosetting urethane adhesive for joining blade material and metal blade holder in continuous production of electrophotographic device blades (hereinafter also referred to as blades) such as developing blades. The present invention relates to a non-solvent two-component thermosetting urethane adhesive for joining a material and a metal blade holder, and a joined blade.
The present invention is not limited to blades that remove toner or form a uniform thin film of toner, but can be used in blades that are used to scrape off other powders or liquid films existing on a surface. Is.

As shown in FIGS. 1 and 2, this type of blade (101) for an electrophotographic apparatus has an elongated polyurethane sheet (102) (in the same manner as an elongated metal plate (103) (referred to as a holder) having a cross-sectional “he” shape. A blade material) is bonded with an adhesive 104. This blade for an electrophotographic apparatus is used as a developing blade and a cleaning blade.

Generally, a sheet-like blade material that is a thermosetting polyurethane elastomer (102)
Are a centrifugal molding method, a mold molding method, and a continuous belt-shaped molding method proposed by the present inventors (Patent Document 1:
(Japanese Patent No. 2645980).

Polyurethane resin adhesives are frequently used as an adhesive for joining the blade material for an electrophotographic apparatus and a metal holder (see Japanese Patent Publication No. 7-103355), and these urethane resin adhesives include: A urethane prepolymer having a terminal isocyanate, a crosslinking agent such as a polyol, and various amines, dibutyltin dilaurate, dibutyltin 2-
Organic metal compounds such as ethyl hexoate, alkali metal compounds such as alkali metal hydroxides and fatty acid salts, radical generators such as benzoyl peroxide and azobisisobutyronitrile, 1,8-diazabicyclo [5,4, 0] -7-undecene, 1,5-diazabicyclo [4]
, 4,0] -5-decene, 1,5-diazabicyclo [4,3,0] -5-nonene or the like, or salts with various organic or inorganic acids, or quaternary It has been used in the form of ammonium salts.

The problem with thermosetting polyurethane elastomer cleaning blades is that the photosensitive drum is contaminated due to catalyst bleed-out, and toner adheres insufficiently to the photosensitive drum, resulting in white spots on the copy screen. Issues to be pointed out are pointed out. The isocyanate group reaction catalyst generally bleeds out to the blade surface over time because of its low molecular weight, low reactivity with the isocyanate group, and poor affinity with the polyurethane resin produced by heat polymerization. It has a problem of precipitation. In the case of the cleaning blade, the surface of the photosensitive drum that is in direct contact is contaminated, and as a result, the toner adheres insufficiently to the photosensitive drum, causing defects such as white spots in the copied image. Yes. One proposal for solving this problem by using this hydroxyamine as a catalyst is disclosed in Japanese Patent Application Laid-Open No. 7-2906.
03). This is because a mold for cleaning blade is prepared, and a prepolymer (hereinafter, “polyisocyanate and polyol” partially polymerized in the mold).
A batch for producing a cleaning blade material by injecting a liquid cleaning blade molding composition mainly composed of a urethane rubber-forming prepolymer) and a curing agent, curing the composition, and then demolding the cured product. This is a proposal to solve the bleed-out by devising the catalyst used in the treatment.
Japanese Patent No. 2645980 Japanese Patent Publication No. 7-103355 JP 7-290603 A

The present inventor has discovered that the problem of bleed-out has also occurred from adhesives in addition to the cleaning blade and the polyurethane sheet to be formed, and has researched and developed a countermeasure. As a bleed-out phenomenon caused by the adhesive, the present inventor considered that the bleed-out reaction catalyst evaporates and aggregates the toner in a lump to cause uneven charging failure and cause roller contamination and toner contamination. I found that. The present invention finds out that the problem of bleed-out is caused not only by the polyurethane used as the material of the cleaning blade but also by the adhesive that joins the polyurethane sheet of the blade material and the metal holder, and is suitable for the continuous manufacturing method of the blade. It is an object of the present invention to develop an adhesive that solves the bleed-out problem and to provide a blade bonded using the adhesive.

(1) Continuously forming a strip blade material made of a two-component curable polyurethane resin, and joining the cut blade material for an electrophotographic apparatus and a metal blade holder using a two-component curable polyurethane resin adhesive In the continuous manufacturing method of the blade,
As a means for continuously forming the strip blade material, a forming drum having a forming groove and an internal heating device, and a heating means for heating from the outside of the forming drum are used.
As a joining means between the electrophotographic blade material and the metal blade holder, the metal blade holder is preheated, and a thermosetting resin adhesive is applied to the electrophotographic blade material, and the heated metal is applied. A two-part curable polyurethane resin synthetic resin for blades and / or a two-part curable polyurethane resin adhesive as a two-part curable polyurethane resin adhesive, and a hydroxyl group represented by the general formula [I] A continuous production method of a blade, characterized in that an amidine compound having the above is used as a catalyst .
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl or alkylene group having 1 to 16 carbon atoms, or a phenyl group. Also, R ¹ and R ² May combine with each other to form a ring having 5 to 8 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m represents an integer of 2 to 4.)
(2) The method for producing a blade according to (1), wherein heating is performed from the outside of the molding drum immediately after the synthetic resin is discharged.
(3) The continuous blade material forming method for belt-shaped blades feeds along the outer periphery of the forming drum by following the rotation of the forming drum while covering the forming groove with the synthetic resin supply means, the external heating means, and the forming drum. The endless belts are sequentially arranged, and the synthetic resin material supplied to the molding groove has a predetermined width and thickness depending on the molding drum heat, the heat from the external heating means, and the molding space formed by the endless belt and the molding groove. The method for producing a blade according to (1) or (2), wherein the belt-like blade sheet is formed by a rotation of a forming drum.
(4) A blade for an electrophotographic apparatus, produced by the production method according to any one of (1) to (3).

1. Two-component curable polyurethane resins used for blade material molding and adhesives are suitable for continuous production because of their high temperature sensitivity.
2. Bleed-out caused by the blade material and the adhesive can be prevented, and defects such as white spots in the electrophotographic image can be prevented.
3. Bleed-out from the adhesive causes defects such as agglomeration of the toner in a lump due to transpiration, but this transpiration can be prevented.
4). The bleed-out bleed-out substance accumulates at a high concentration when not used for a long period of time, and in particular, it has an adverse effect on the toner, so it tends to appear as an error at the time of initial error at the time of shipment or restarting after consecutive holidays. It is possible to reduce the cause of the initial error and the error at the time of restart.
5). Furthermore, by using a blade material that can prevent bleed-out, an effect of synergistically preventing bleed-out can be achieved.

<Catalyst>
As described above, the amidine compound having a hydroxyl group is represented by the general formula [I], in which R ¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 3 carbon atoms include a methyl group, an ethyl group, and an n-propyl group. R ² represents a hydrogen atom, an alkyl or alkylene group having 1 to 16 carbon atoms, or a phenyl group. Examples of the alkyl group or alkylene group having 1 to 16 carbon atoms include saturated alkyl groups such as methyl group, ethyl group, hexyl group and stearyl group; alkylene groups such as 3-butylene group and 7-octylene group; butoxymethyl group , Phenoxymethyl group, methacryloyloxymethyl group,
Examples thereof include substituted alkyl groups such as a benzoyloxymethyl group, a fluoromethyl group, and a chloromethyl group. Further, when R ² is a phenyl group, the phenyl group may be substituted with a halogen group, an alkyl group, a substituted alkyl group, and the like, and examples thereof include a fluoro group methyl group and a 4-chloromethylphenyl group. It is done.

R ¹ and R ² may be combined with each other to form a ring having 5 to 8 carbon atoms. R ¹
Examples of the ring having 5 to 8 carbon atoms formed by bonding R ² and R ² include a cyclopentane ring, a cyclohexane ring, a norbornane ring, and a cyclooctane ring. These rings may have various substituents, and examples of the substituent include a methyl group, a vinyl group, and a 1-methylvinyl group.

R ³ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and examples of the alkyl group having 1 to ³ carbon atoms in R ³ include a methyl group, an ethyl group, and an n-propyl group.

Among R ¹ , R ² , and R ³ described above, R ¹ , R ² , and R ³ are both hydrogen atoms, or R ¹ , from the viewpoint of ease of distillation purification in the production of the amidine compound of the present invention. R ³ is preferably a hydrogen atom and R ² is preferably a methyl group. In the above formula, m is an integer of 2 to 4, but 2 or 4 is preferable for the same reason. That is, as a preferable specific example of the novel amiodin compound of the present invention,
6- (2-hydroxyethyl) -1,8-diazabicyclo [5,4,0] -7-undecene), 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] -7 -Undecene, 7- (2-hydroxyethyl) -1,5-diazabicyclo [4,3,0] -5
Nonene, 7- (2-hydroxypropyl) -1,5-diazabicyclo [4,3,0] -5
Nonen etc. are mentioned.
As an example of the catalyst used in the present invention, there is an example disclosed in JP-A-2003-81975.

<Urethane adhesive component>
As components of the non-solvent type two-component thermosetting polyurethane resin adhesive in which these catalysts are used, polyisocyanate prepolymer (component A) and polyol (component B) conventionally known components can be used. For example, it is illustrated in Japanese Patent Publication No. 7-103355.

Examples of the component A polyisocyanate include xylylene diisocyanate, polyphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, naphthalene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate. Diisocyanate such as dicyclohexylmethane diisocyanate, or a polymer thereof, and further a compound having a plurality of isocyanate groups such as allophanate bond, isocyanurate bond, carbodiimide bond, etc., for example, a condensate of diphenylmethane diisocyanate. It can also be used as a compound.

Examples of the B component polyol include ethylene glycol, propylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol, hexamethylene glycol, glycerin, 1,3-butylene glycol, 1,4-
Polyhydric alcohols such as butanediol, hexanetriol, pentaerythritol, sorbitol, neopentyl glycol; polyether polyols obtained by addition polymerization of the polyhydric alcohols with alkylene oxides such as ethylene oxide and propylene oxide; Polyester polyols obtained by condensation reaction of polyhydric alcohols with polybasic acids such as maleic acid, succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid and isophthalic acid; lactones such as ε-caprolactone and γ-valerolactone Polyester polyols obtained by ring-opening polymerization of polymers; polymerizable monomers containing hydroxyl groups such as hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester Monomers that are polymerized alone or copolymerizable therewith,
For example, acrylic polyols obtained by copolymerizing acrylic acid, methacrylic acid, styrene, acrylonitrile, α-methylstyrene, etc .; castor oil or derivatives thereof; epoxy resins having epoxy groups at both ends, monoethanolamine, diethanolamine, etc. And an epoxy polyol obtained by reacting with each other.

  The catalyst mentioned above is normally added in the 2nd component which contains B component as a main component.

<Reaction catalyst properties of amidine compounds having a hydroxyl group>
(1) Bleed-out prevention performance 1,8-diazabicyclo [5,4,0] -7-undecene) and hydroxyl group-introduced, ie, 6- (2-hydroxypropyl) -1,8-diazabicyclo [5 , 4,0] -7-undecene as reaction catalysts, 44.1 parts by weight of polypropylene glycol (PP-1000, molecular weight 1,000), 11.9 parts by weight of 1,4-butylene glycol (1,4-BG) Part of the resin, 39.1 parts by weight of isophorone diisocyanate (IPDI) and 0.5 parts by weight of the reaction catalyst were synthesized, and these resins were separately dissolved in dimethylformamide. 8-Diazabicyclo [5,4,0] -7-undecene and 6- (2-hydroxypropyl) -1,8-diazabicyclo [5 4,0] -7-undecene was determined by gas chromatography.
As a result, 1,8-diazabicyclo [5,4,0] -7-undecene added as a reaction catalyst remained in 60% by weight, whereas 6- (2-hydroxypropyl) -1, 8-Diazabicyclo [5,4,0] -7-undecene is almost completely incorporated into the urethane resin and is a reactive catalyst that can prevent bleed out and transpiration.

(2) Unreactive at low temperatures In continuous manufacturing processes, it is necessary to supply the adhesive in a stable state. When using a two-component polyurethane resin adhesive, always supply two components while mixing them. Yes. At the same time as the mixing, a reaction starts, and it may remain in the mixing device or the like, causing a supply failure of the adhesive or a failure after bonding. For this reason, cooling is performed from the mixing device to the adhesive supply device by means such as air cooling so that the reaction does not proceed in a low temperature state.
The urethane resin using 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] -7-undecene is a test result combined with the following reaction acceleration at a high temperature (3) As can be seen from this, it is a resin that does not easily react at low temperatures.

(3) Rapid reactivity at high temperature The size of the blade is, for example, a thickness t of 1.2 mm or 2.0 mm, a width L2 of 15 mm,
The length of the adhesive glue L1 with the metal holder is 305 mm and the width is 4 mm. Thus, unless the adhesive is applied accurately and uniformly to the elongated area and the bonding is completed with high accuracy, the fine toner cannot be scraped and a beautiful image cannot be formed. For this reason, the joining of the blades is performed under high temperature by heating in order to rapidly cure after application of the adhesive and realize precise bonding.
A urethane resin using 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,4,0] -7-undecene is a resin that can obtain rapid reaction acceleration at high temperatures.

(4) Temperature Sensitivity The characteristics of unreacted at low temperature (2) and rapid reactivity at high temperature (3) were confirmed as follows. The following aliphatic and aromatic isocyanates were used.
Polycaprolactone ester diol 200 (PCL200); 88.1 parts by weight, 1,
4-butylene glycol; 11.9 parts by weight, isophorone diisocyanate; 39.1 parts by weight, catalyst; 0.5 part by weight of polyurethane resin is cured for a period of time until it can be removed from the hot plate of the gelation tester, The results were compared and the results are shown in Table 1. Similarly, GP-3700M; 20
. Table 2 compares the time required to demold the aromatic polyurethane resin consisting of 0 parts by weight, Millionate MR-200; 2.2 parts by weight, catalyst; 0.03 parts by weight from the hot plate of the gelation tester. showed that.

<Continuous manufacturing process>
Since the present invention is excellent in temperature sensitivity when applied to continuous production, it can be continuously applied and rapidly cured.
Continuous molding of polyurethane tape of blade material (mixing process-> casting to heating rotating drum for molding-> primary cross-linking-> take-out polyurethane blade material cooling)-> fixed size cut-> secondary cross-linking-> joining with metal holder ( Adhesive mixing->application-> heat curing)-> inspection.
In this continuous manufacturing process, the pot life of the urethane resin at a low temperature and the fast curability at a high temperature are required in a molding process into a tape shape with a molding drum and a joining process with a metal holder.
As the belt-like continuous forming method, the previously proposed method can be used, and for example, it can be manufactured by the apparatus shown in FIG. The molding size is 1.2 mm thick and 15 mm wide as an example of a developing blade, and 2.0 mm thick and 15 mm wide as an example of a cleaning blade.

<Polyurethane resin for blade material>
The composition of the polyurethane resin for forming the blade material is basically known, and the composition of the non-solvent two-component thermosetting polyurethane previously proposed by the present applicant can be adopted. Patent No. 2942
The example disclosed in No. 183 is described. As the catalyst, it is desirable to use the catalyst exemplified for the adhesive that can withstand bleed-out and continuous processing as well as the adhesive.

High molecular weight polyols for blade materials include polyoxyalkylene glycols such as polyethylene glycol, polypropylene glycol and polyoxytetramethylene glycol, or polyethers of alkylene oxide adducts such as bisphenol A, glycerin ethylene oxide and propylene oxide. Type polyols and dibasic acids such as adipic acid, phthalic anhydride, isophthalic acid, maleic acid, fumaric acid and ethylene glycol,
Examples thereof include polyester type polyols obtained by polymerization reaction with glycols such as propylene glycol, 1,4 butanediol, 1,6 hexanediol, and trimethylolpropane, polycaprolactone diol, and polycarbonate diol.
These high molecular weight polyols have a number average molecular weight of 500 to 5,000, particularly preferably 10.
The range is 00 to 3000.

Diisocyanate compounds for blade materials include tolylene diisocyanate, 4,
Examples include 4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and 1,4 cyclohexane diisocyanate. Chain extenders include ethylene glycol, 1,4 butanediol, diethylene glycol, 1,6
Examples thereof include low molecular weight diols such as hexanediol and neopentyl glycol, and diamines such as ethylenediamine, hexamethylenediamine and isophoronediamine.
Desirably, a low molecular weight diol is used. Furthermore, you may add a trimethylol propane, a triethanolamine, glycerol, and these ethylene oxide and a propylene oxide adduct as a polyfunctional component as needed. These polyols and diisocyanate compounds may be reacted by any one of the one-shot method, pseudo-prepolymer method, and prepolymer method employed in the conventional polyurethane production method, but the pseudo-prepolymer method or prepolymer method. The physical properties of the product obtained by using the are stable and the properties are good.

In the production of the above polyurethane, the equivalent ratio of OH group / NCO group is preferably 0.8 to 1.05, more preferably 0.85 to 1.00, from the physical properties of the polyurethane to be produced. If necessary, an amidine compound catalyst having a hydroxyl group represented by the general formula [I] may be used as a reaction accelerator.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to this.
Needless to say, the characteristics of the adhesive are not limited to the production method of the blade material.

<Adjustment of polyurethane for blade material and molding of blade material>
66.1 parts by weight of polycaprolactone ester diol (average molecular weight 2000) at 70 ° C.
And dehydrated by heating and stirring under reduced pressure (5 mmHg) for 3 hours, and charged into a reaction vessel.
Subsequently, 27.8 parts by weight of 4,4 diphenylmethane diisocyanate was added to the reaction vessel and stirred at 70 ° C. for 1 to 4 hours in a nitrogen gas atmosphere to obtain a liquid urethane prepolymer having a residual isocyanate group content of 7.0%. . Isocyanate group / hydroxyl group equivalence ratio is 3.4

On the other hand, 4.3 parts by weight of 1,4 butanediol, 1.8 parts by weight of trimethylolpropane and catalyst 6- (2-hydroxypropyl) -1,8-diazabicyclo [5,
0.07 part by weight of 4,0] -7-undecene was heated and stirred under reduced pressure (5 mmHg) for 3 hours at 70 ° C. to dehydrate it to obtain a crosslinking agent having a hydroxyl group equivalent of 45.

The prepolymer and the crosslinking agent obtained as described above are put into the tanks (201) and (202) of the mixer (200) shown in FIG. 7, and heated and stirred so that the liquid temperature becomes 70 ° C. The mixture is fed to the mixing head (207) by the metering pumps (203) and (204) of the two-component quantitative mixing casting machine, and uniformly stirred and mixed so that the equivalent ratio of OH group / NCO group is 0.95. It discharged from the discharge port in the groove | channel for shaping | molding of the shaping | molding drum adjusted to 145 degreeC.

<Manufacturing equipment>
Embodiments of the blade of the present invention and the manufacturing apparatus thereof are shown in FIGS.
This will be described with reference to FIGS.
FIG. 3 is an overall front view schematically showing an embodiment of a blade manufacturing apparatus used in an electrophotographic apparatus. The blade manufacturing equipment consists of a forming drum (3), a supply port (1) for supplying resin, an external heating device (2), an endless belt (4), a cooling conveyor (10), a cutting device (14), and an unloading device. Conveyor (15) etc.
The discharge port (1) for the liquid material of the polyurethane resin is disposed at a clockwise position at about 10 o'clock from the apex of the molding drum (3), followed by the external heating device (2), followed by molding. An endless belt (4) that covers the outer peripheral surface of the drum and covers approximately half of the drum is disposed. Subsequently, the strip-shaped blade material S that has been peeled off is cooled and conveyed, and a cutting device that cuts the paper in a fixed order, and a conveying device. It is arranged.
The forming drum (3) is made of, for example, hard aluminum or stainless steel, and includes a rotational drive, a forming groove, and a built-in heating structure.
The forming groove is formed with a concavely shaped cross-sectionally shaped groove engraved with a predetermined dimension corresponding to the width and thickness of the blade material. This forming groove corresponds to a mold. The heating means supplies heat for curing a resin such as polyurethane. The heating temperature is appropriately determined depending on the resin used, the rotation speed, and the like. For example, it is set to 110 ° C to 150 ° C. The rotation direction is set clockwise in the drawing.
The resin supply port (1) supplies the resin component to be used to the molding groove of the molding drum (3) continuously through a two-component mixing controller shown in FIG.
The external heating device (2) fulfills the function of irradiating and heating the resin cast into the molding groove from the supply port (1). This heat promotes curing of the resin surface side. Curing of the cast resin is accelerated by the heat of the molding drum and heat from the outside, the viscosity is increased, and the flow of the endless belt into the contact start end can be controlled. The installation position of the external heating device can be adjusted between the discharge port (1) and the preheating roll (6). This position can also be determined by the type of resin and the thickness of the blade. In this example, it is installed near the top of the forming drum. The external heating device can be omitted.
The endless belt (4) has a structure in which a space is formed to cover the molding groove and the polyurethane liquid material is filled. A cavity for molding is formed by the endless belt (4) and the molding groove, the outer shape of the blade material is adjusted, and the resin curing reaction proceeds. The section where the endless belt (4) covers the molding groove of the molding drum (3) needs to be designed to such an extent that the resin can be hardened and peeled off from the molding groove as a strip-like tape. For example, 180 ° corresponding to a section from 2 o'clock to 8 o'clock on the watch is an easy-to-operate area.
The cooling conveyor (10) conveys the blade material molded into a resin band peeled from the molding groove (3) of the molding drum to the subsequent process while cooling it. Note that this cooling conveyor may not require cooling depending on the blade material. If cooling is not required, this conveyor can be a transfer device to a subsequent process or can be omitted.
The cutting device (14) is a device that cuts a continuous belt-like material into the length of a blade. By this cutting, the blade material is formed into a final shape. After this, it is carried out to the adhering process to the metal blade holder. In order to synchronize with the action of this cutting device, a feed roll (13) for controlling the feed is arranged immediately before the cutting device (14), and in order to cope with the speed of feed by the feed roll (13), the feed roll Provide a space for the tape to sag before (13) and measure the timing of the cooling conveyor (10) and the cutting device (14).
In addition, a heating process can be added as needed as a post process for the secondary bridge | crosslinking which performs a secondary bridge | crosslinking and finally implement | achieves hardening reaction.

An endless belt (4) for forming a molding space (metal mold) made of a metal strip such as stainless steel is brought into contact with the outer peripheral surface of almost half of the molding drum (3). This endless belt (4)
Is a preheating roll (6) for preheating the endless belt (4), a guide roll (7) for adjusting belt running, a tension roll (8) for applying tension to the endless belt, and cooling for cooling the endless belt (4). It is stretched over the roll (9) and rotated by the rotation of the forming drum (3). The endless belt (4) is heated to a predetermined temperature (for example, around 145 ° C., which is about the same as that of the molding drum) by a heater, and this temperature prevents a temperature drop of the polyurethane liquid material.

As a means for supplying the molding resin to this molding drum, a two-component quantitative mixing and casting machine shown in FIG.
200) is used.
Pipes (205) and (206) provided with two tanks (201) and (202) and provided with metering pumps (203) and (204) from the outlets of the respective tanks (201) and (202) are mixed heads (two liquids). (Quantitative mixing casting machine) (207). Mixing head (2
07) and the tanks (201) and (202) are connected to circulation pipes (205a) and (206), respectively.
connected by a). In addition, the mixing head (207) has a liquid material inlet at the upper end and a liquid discharge port at the lower end center, and a stirring rotor is supported rotatably at the upper end center. In addition, it has a known structure that is rotationally driven by an upper motor (207c).
Tank (201) and (2 of pre-polymer and cross-linking agent, respectively
02) and degassed by heating, decompression and stirring. The prepolymer and the crosslinking agent thus obtained are supplied to the mixing head (207) by the metering pumps (203) and (204), and the temperature is adjusted to 145 ° C. from the discharge port while stirring and mixing uniformly. (3)
It is discharged into the molding groove. At this time, the forming drum (3) has a predetermined speed (1 rotation / 80 seconds).
The required amount corresponding to the peripheral speed of the forming drum (3) and the engraving depth and width of the forming groove is continuously injected.

A polyurethane liquid material is measured in a molding groove of a molding drum (3) whose temperature is adjusted to a predetermined temperature, for example, 145 ° C., from a discharge port (1) while measuring a prepolymer and a crosslinking agent and stirring and mixing uniformly. Is discharged and cast. At this time, the forming drum (3) has a predetermined speed (for example, 80 seconds /
1 turn), and the necessary amount corresponding to the peripheral speed of the drum (3) and the engraving depth and width of the groove is continuously injected.

The liquid polyurethane is from point A directly below the discharge port (1) disposed at about 10 o'clock from the top of the molding drum (3) to point C directly above the molding drum (heating position by an external heating device). After the reaction is started, it is heated by an external heating device at the point C, and then heated only by the forming drum, and is heated with a preheated roll from the contact start position E of the endless belt, for example, 145
The endless belt for molding heated to 0 ° C. is heated and held between point E and point G of the forming drum (3). As a result, the urethane polymerization reaction of the liquid material is almost completed, and a blade molding material having a necessary width and thickness and a smooth mirror surface is continuously formed into a strip shape.
The position of the discharge port (1) is adjusted by the type of resin, the thickness of the blade, the manufacturing speed, and the like. In this example, it is installed at a clock position from 9 o'clock to 12 o'clock in the counter-rotating direction of the forming drum. Preferably, it is installed around 10:00. The synthetic resin liquid discharged toward the counter-rotation direction tends to fall according to gravity, and is lifted toward the top of the molding drum as the molding drum rotates.
In this example, the time required for the liquid polyurethane material to rotate and move from point A to point E is 13
Second, the movement time from point E to point G is set to about 40 seconds. As described above, the position of point E is changed by the approach / separation operation of the preheating roll (6) with respect to the forming drum (3). By changing the angle between the point A and the point E and the angle between the point C and the point G, the reaction of the liquid substance and the molding time can be finely adjusted.

It is desirable that the reaction does not proceed until the mixed urethane composition is ejected, and the reaction proceeds in a time of about 40 to 60 seconds from the point G after ejection until it is pulled out in the form of a tape. Needs to be molded.

The band-shaped blade molding continuously formed in this way is peeled off from the groove of the forming drum (3) at point G and guided onto the endless conveyor belt of the cooling conveyor (10). Thereafter, the blade material is cooled, conveyed, and cut into a predetermined length of blade material.

The blade material manufactured in this way has one side edge bonded to a metal holder (103) with an adhesive (104) as shown in FIG. Complete.
In addition, the side edge which is the free end of the blade material (102) is
Further, it is possible to form a ridge line by adjusting and cutting.
Further, in the case of the present invention, unlike the conventional centrifugal molding method, the blades (102) are continuously manufactured one by one, so the blade (102) is also used in the step of bonding to the holder or the ridge line forming step. Can be processed one by one, which makes it easy to automate these processes. On the other hand, in the method using a mold, burring is unavoidable, and it is necessary to form a ridge line on the tip side of the blade by cutting. Waste due to cutting of burrs or the like is generated, and many resin materials are wasted.

<Adhesive adjustment>
As a non-solvent type two-component thermosetting polyurethane resin adhesive, a main agent “MLT2300A” and a curing agent “MLT2363” manufactured by ETEC Co., Ltd. were used.
-(2-Hydroxypropyl) -1,8-diazabicyclo [5,4,0] -7-undecene (0.3 parts by weight) was added, and each was put into a two-component quantitative mixer. It mixed and used for joining with the braid | blade raw material which consists of a polyurethane resin manufactured from the said manufacturing process, and a metal blade holder.

<Joint process>
Using a mixing device similar to the supply of a two-component polyurethane composition for blades, each of the main agent and the curing agent to which the catalyst has been added is metered and transferred with a gear pump so that the NCO group / OH group is 1.05. , By mixing mechanically with a mixing head, the band-shaped blade material was cut to a fixed length of 233 mm, and the thickness of 4 mm was applied to the planned bonding part of the polyurethane blade material with a width of 11.5 mm. A metal holder made of a lubricated resin-treated steel plate pre-heated to 100 ° C. was overlaid, held for 30 seconds while being heated, and then cooled to obtain a cleaning blade. The mixing head portion is air-cooled to 20 ° C. in order to suppress the temperature rise due to mixing.
Similarly, a developing blade having a fixed length of 226 mm, a thickness of 1.2 mm, and a width of 14.0 mm was obtained.

<Comparative example>
Comparative Examples 1-4 used the adhesive agent of the same composition except having changed the catalyst.
Development blade and cleaning blade are LBP IPSIO NX6 manufactured by Ricoh Co., Ltd.
10 cartridges were assembled.
Evaluation was made into the following 1-4, and the result is shown in Table 3.

Evaluation 1: The operation of applying the adhesive to the blade was repeated every 10 seconds to check the application state.
The mixing head is cooled in order to prevent the reaction of urethane (adhesive) before coating, but depending on the type of catalyst, the reaction proceeds even at low temperatures. As a result, the cured product is deposited near the discharge port, and the adhesive is difficult to come out, so that it cannot be applied uniformly. Further, the groove of the mixing portion of the mixing head is filled with the hardened deposit, so that the original mixing performance cannot be exhibited, and mixing failure tends to occur.
In particular, in the continuous manufacturing method to which the present invention is applied, since it is necessary to continuously supply the adhesive, a failure in the mixing head is not preferable as a production system, and it must be avoided because it causes a defective product. I must.
Specifically, the following abnormalities appear.
(1) Contamination of foreign matter: Swelling occurs on the blade from the adhesive surface, and the contact of the blade is not uniform.
In the case of the cleaning blade, a problem occurs in scraping off the toner. In the case of the developing blade, problems such as a toner layer not being uniformly formed on the surface of the developing roller and a non-uniform toner charge amount occur.
(2) Cannot be applied uniformly: The amount of adhesive protruding from the end of the core is not uniform, and the free end length of the blade is not uniform, so the contact of the blade is not uniform. Trouble with toner scraping. In the case of the developing blade, problems such as a toner layer not being uniformly formed on the surface of the developing roller and a non-uniform toner charge amount occur.
(3) Poor mixing: The reaction of the two-component urethane does not occur, and an unreacted part is formed, so that the physical properties as an original adhesive are not exhibited. That is, adhesion failure occurs, and the blade has problems such as peeling during use.

Evaluation 2: Contamination of developing sleeve A cartridge equipped with a cleaning blade and a developing blade is 40 ° C. × 95% R
After being left in the H environment for 7 days, it was incorporated into the printer body and 10 50% gray images were taken out to check for abnormalities.

Evaluation 3: Toner contamination A cartridge equipped with a developing blade and a cleaning blade is installed in the printer body, 200 images of 5% character charts are printed, the cartridge is removed from the printer body, and the environment is 40 ° C. × 95% RH for 7 days. After leaving it alone, it was again incorporated into the printer body and 10 50% gray images were taken out to check for any abnormalities.

Evaluation 4: Photoconductor contamination A cartridge equipped with a developing blade and a cleaning blade is 40 ° C. × 95% R
After being left in the H environment for 7 days, it was incorporated into the printer body, 10 images of 50% gray images were taken out, and the presence or absence of abnormality was confirmed.

Test results The following can be said.
<About Evaluation Item 1>
Examples that can withstand continuous application for 6 hours or more are Example 1 and Comparative Example 1.
<About Evaluation Item 2>
Catalyst in developer blade adhesive (1,8-diazabicyclo (5,4,0) undecene-
7) adheres to the developing sleeve due to volatilization or the like in a high temperature and high humidity environment, and the function of the developing sleeve is obstructed by some action only in that portion, and the developability of the toner is lower than the other portions, that is, the image density is low. It is estimated that
<About Evaluation Item 3>
Catalyst in developing blade adhesive (N, N ', N "-Tris (dimethylaminopropyl)
Hexahydro-S-triazine) is expected to adhere to the toner on the developing sleeve due to volatilization in a high-temperature and high-humidity environment, and the toner forms secondary agglomeration, thereby impairing the fluidity of the original toner. . Because the lump of toner with impaired fluidity is fixed on the sleeve,
It is presumed that the image becomes darker than the other portions because the gap between the developing sleeve and the photosensitive member is narrowed only in that portion, and the amount of toner developed on the photosensitive member is increased.
<About Evaluation Item 4>
The catalyst (1,2-dimethylimidazole) in the cleaning blade adhesive adheres to the photosensitive drum due to volatilization in a high-temperature and high-humidity environment, and only that portion inhibits the function of the photosensitive drum by some action. It is presumed that the developability of the toner is lower than that of the above portion, that is, the image density is reduced.
In addition, “Evaluation 2” and “Evaluation 3” in which defects occurred as the developing blade were also carried out for LBP-1210 manufactured by Canon Inc., and it was confirmed that the same tendency was observed.
<Comprehensive evaluation>
As a catalyst, “6- (2-hydroxypropyl) -1,8-diazabicyclo (5,4,0
It was confirmed that the results using ") -7-undecene" were excellent in adhesion performance and product performance. As a result, 6- (2-hydroxypropyl) -1,8-diazabicyclo (5
, 4,0) -7-Undecene and other two-component polyurethane adhesives are suitable for continuous production of blades, and the manufactured blades are not affected by bleed-out and are high-performance products. I understand. This two-component polyurethane adhesive using the hydroxylated amidine compound catalyst represented by the general formula [I] exhibits excellent ability not only in severe conditions such as continuous production but also in batch processing. Needless to say.

Blade perspective view Blade cross section Continuous production equipment Drum molding part Molding drum Band-shaped blade material molding schematic diagram Two-component quantitative mixing and casting machine

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Polyurethane liquid discharge port 2 External heating device 3 Molding drum 4 Endless belt 5 Molding roll rotating shaft 6 Preheating roll 7 Guide roll 8 Tension roll 9 Cooling roll 10 Cooling conveyor 11 Cooling device 12 Sag detector 13 Feeding roll 14 Cutting Device 15 Conveyor 16 Upper sensor 17 Lower sensor 101 Blade 102 Blade material 103 Metal holder 104 Adhesive 200 Two-component quantitative mixing and casting machine 201 202 Tank 203 204 Metering pump 207 Mixing head 207c Motor

Claims (4)

A blade for continuously forming a two-part curable polyurethane resin band-shaped blade material and joining the cut blade material for an electrophotographic apparatus and a metal blade holder using a two-part curable polyurethane resin adhesive. In the continuous manufacturing method,
As a means for continuously forming the strip blade material, a forming drum having a forming groove and an internal heating device, and a heating means for heating from the outside of the forming drum are used.
As a joining means between the electrophotographic blade material and the metal blade holder, the metal blade holder is preheated, and a thermosetting resin adhesive is applied to the electrophotographic blade material, and the heated metal is applied. A two-part curable polyurethane resin synthetic resin for blades and / or a two-part curable polyurethane resin adhesive as a two-part curable polyurethane resin adhesive, and a hydroxyl group represented by the general formula [I] A continuous production method of a blade, characterized in that an amidine compound having the above is used as a catalyst .
(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R ² represents a hydrogen atom, an alkyl or alkylene group having 1 to 16 carbon atoms, or a phenyl group. Also, R ¹ and R ² May combine with each other to form a ring having 5 to 8 carbon atoms, R ³ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and m represents an integer of 2 to 4.) 2. The method of manufacturing a blade according to claim 1, wherein heating is performed from the outside of the molding drum immediately after the synthetic resin is discharged. The continuous blade material forming method for strip blades supplies synthetic resin to the forming groove along the outer periphery of the forming drum.
Means, external heating means, and rotation of the forming drum while covering the forming groove of the forming drum.
The endless belt is arranged in sequence, and the synthetic resin material supplied to the molding groove is made to have a predetermined width and thickness by the heat of the molding drum, the heat from the external heating means, and the molding space formed by the endless belt and the molding groove. The method for producing a blade according to claim 1 or 2, wherein the belt-like blade sheet is formed by a forming method according to rotation of a forming drum. An electrophotographic apparatus blade produced by the method according to claim 1.