JP2005256070A - Inorganic-organic composite treated zinc-base plated steel sheet for blade supporting member - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inorganic-organic composite treated zinc-base plated steel sheet for a blade supporting member which does not contain harmful chromate in a treated film, permits omission of a primer treatment, and is excellent in adhesion to a blade member. <P>SOLUTION: The inorganic-organic composite treated zinc-base plated steel sheet for the blade supporting member is formed with a zinc phosphate treated film on the surface of the oxide-base plated steel sheet and has an organic-base post treated film thereon. The organic-base post treated film is composed of 10 to 100 mass% amino group-containing silane coupling agent and 0 to 90 mass% other silane coupling agents and or organic alkoxysilane compound. Preferably the amount of the zinc phosphate treated film is 0.3 to 5 g/m<SP>2</SP>and the amount of the organic-base post treated film is 0.01 to 1 g/m<SP>2</SP>. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an inorganic / organic composite-treated galvanized steel sheet for blade support members.

It is essential for the blade to ensure adhesion through the blade support member, blade member, and adhesive constituting the blade. On the other hand, manufacturers that manufacture toner blades punch steel plates for blade support members supplied from steel plate manufacturers to improve adhesion between the blade members and blade support members, press form and degrease them, then silane couplings. Primer treatment with agent is performed.
In recent years, manufacturers that manufacture toner blades are requested to omit the primer treatment in the production process, and there is an increasing demand for a blade support member of the primer treatment omitted type.

The following techniques have been proposed as the above example.
Used in electrophotographic image forming devices such as copying machines and printers, a metal holder for adhering and supporting an elastic blade without applying a primer, and a chromate film on an electrogalvanized steel sheet A blade characterized by being formed of a steel plate having an organic lubricating film layer is disclosed (for example, see Patent Document 1).
In a blade body for an electrophotographic apparatus comprising a support member, an adhesive layer, and a blade member bonded to the support member via the adhesive layer, it is disclosed that the support member is made of an organic lubricating film steel plate. Has been. (For example, refer to Patent Document 2).
It consists of a blade member made of a thermosetting urethane elastomer, a support member and an adhesive layer, and the thermosetting urethane elastomer is an elastomer having water absorption, and the adhesive layer contains a hydrolyzable organosilane compound. There has been disclosed a cleaning blade for an electrophotographic apparatus characterized by comprising a moisture-curing adhesive (see, for example, Patent Document 3).
A cleaning blade for an electrophotographic apparatus in which a blade member made of a urethane elastomer is bonded to a support member with an adhesive, and a solution of a hot melt adhesive dissolved in a solvent is used as the adhesive, and the hot melt adhesive Discloses a cleaning blade for an electrophotographic apparatus in which a silane coupling agent is added (see, for example, Patent Document 4).
A cleaning blade for an electrophotographic apparatus in which a blade member made of a thermosetting type urethane elastomer is bonded to a support member with an adhesive, and a modified product of a polyvinyl acetal resin by a formaldehyde condensation type thermosetting resin as the adhesive Among the cleaning blades for an electrophotographic apparatus characterized in that is used, it is disclosed that the support member is surface-treated with a silane coupling agent (see, for example, Patent Document 5). ).
JP 7-334059 A JP-A-9-26735 JP-A-8-36337 JP-A-7-334050 JP 7-319354 A

  As in the above-mentioned patent document, a zinc-based plated steel sheet that has been chromated as a blade support member has been generally used. However, in recent years, against the background of growing environmental problems, the development of various surface treatment techniques that do not use highly toxic chromate is awaited, and the development of types that do not contain environmentally hazardous substances such as hexavalent chromium as blade support members It is essential. On the other hand, as shown in the above patent document, a silane coupling agent or an organosilane compound is added to the adhesive connecting the blade member and the blade support member in order to omit the primer treatment at the toner blade manufacturer. Proposals have been made.

  The above proposed blade does not have sufficient adhesion between the adhesive connecting the blade member and the blade support member, and further improvement in adhesion is desired in practice. In the first place, the adhesive strength and the adhesive strength tend to vary in strength due to uneven local bonding force at the interface between different materials, and are often unstable. The main performance requirement that the blade should have is to secure a high strength adhesion between the blade member and the blade support member, and it cannot be said that the blade satisfies the sufficient performance.

  In order to further improve the adhesion between the blade member and the blade support member, since the adhesion force between the blade support member and the adhesive is insufficient in strengthening the cross-linking structure of the adhesive itself, In order to improve the adhesion at each interface, it is considered that an optimum coating design is essential to improve the adhesion and adhesion of the coating on the blade support member surface.

  In view of the present situation, the present invention can omit the primer treatment, does not contain harmful chromate in the treated film, and has excellent adhesion to the blade member. The object is to provide a plated steel sheet.

The present invention is an inorganic-organic composite-treated zinc-based plated steel sheet for blade support members having a zinc phosphate-treated film formed on the surface of a zinc-based plated steel sheet and an organic post-treated film thereon. Inorganic organics for blade support members, characterized in that the system post-treatment film comprises 10 to 100% by mass of an amino group-containing silane coupling agent, another silane coupling agent and / or an organic alkoxysilane compound of 0 to 90% by mass It is a composite treated zinc-based plated steel sheet.
The zinc phosphate treatment film amount is preferably 0.3 to 5 g / m ² , and the organic post-treatment film amount is preferably 0.01 to 1 g / m ² .

  According to the present invention, the zinc phosphate-treated film on the lower layer of the inorganic-organic composite-treated zinc-based plated steel sheet contributes to strong adhesion to the steel sheet surface and an increase in surface area due to surface irregularities, and the organic post-treatment on the upper layer is applied to the lower layer. As it contributes to the adhesion to the zinc phosphate-treated film and the blade member or adhesive adhered on it, the resulting film does not contain harmful chromate and does not require primer treatment in the blade manufacturing process. In addition, it is possible to obtain an inorganic / organic composite-treated zinc-based plated steel sheet for a blade support member having excellent adhesion to the blade member.

The present invention is described in detail below.
The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has a zinc phosphate-treated film on the surface of the zinc-based plated steel sheet, and further has an amino group-containing silane coupling agent of 10 to 100% by mass, A silane coupling agent and / or an organic post-treatment film composed of 0 to 90% by mass of an alkoxysilane compound. By having these two kinds of films, a blade member or a blade member via an adhesive The adhesiveness of this is greatly improved.
The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is obtained by forming a zinc phosphate-treated film as a lower layer film on the surface of a zinc-based plated steel sheet. Since the zinc phosphate-treated film layer is formed so that needle-like, leaf-like, or granular grains are biting into the plating surface layer of the zinc-based plated steel sheet, high adhesion is exhibited.

The zinc phosphate-treated film is formed with a film amount having a lower limit of 0.3 g / m ² and an upper limit of 5 g / m ² . If it is less than 0.3 g / m ² , there will be more sites where a dense zinc phosphate-treated film will not be formed, so there is a risk of insufficient adhesion with the plating, and if it exceeds 5 g / m ² , Because of the coarsening of the particle size, the particle density of the bite with the plating surface is lowered, so that the adhesive force at the interface between the plating and the zinc phosphate treatment film is also lowered. Further, in this coating amount region, peeling is likely to occur between the lower layer and the secondary nuclei in the zinc phosphate-treated coating due to the secondary nucleus growth, so that the adhesion strength is also lowered. The lower limit is more preferably 0.5 g / m ² , and the upper limit is more preferably 2.5 g / m ² .

The zinc phosphate-treated film can be formed by a conventionally known zinc phosphate treatment agent containing phosphate ions and zinc ions. As a source of zinc ions and phosphate ions, zinc and phosphate are contained. If it is a compound to be used, there is no particular limitation, and other components that can be used in the zinc phosphate treating agent may be appropriately contained.
The treatment liquid for forming the zinc phosphate treatment film is a commercially available treatment mainly containing phosphate ions and zinc ions, and further containing metal ions other than zinc, nitrate ions, fluoride ions and the like as necessary. Liquid can be used.

As a zinc phosphate treatment method for a zinc-based plated steel sheet with the zinc phosphate treatment agent, a zinc phosphate treatment film can be formed by any of a reactive treatment and a coating treatment. As the reactive treatment, for example, a zinc phosphate-treated film is formed by degreasing, rinsing and surface-adjusting a zinc-based plated steel sheet, then bringing it into contact with the zinc phosphating solution, washing and drying. Can do. The coating amount of the zinc phosphate-treated film can be adjusted, for example, by changing the treatment time or the treatment agent concentration.
As the coating type treatment, for example, the zinc phosphate-treated liquid in an amount corresponding to the required coating amount is applied to a zinc-based plated steel sheet by a roll coating method, and after being applied by a dipping method or a spray method, a roll squeezing method There is also a method of adjusting to a necessary coating amount. After applying the zinc phosphate treatment agent to the zinc-based plated steel sheet, the zinc phosphate treatment film is formed by drying using a drying furnace or the like.

The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is obtained by forming an organic post-treatment film as a second film on the zinc phosphate-treated film. By forming the organic post-treatment film on the zinc phosphate-treated film, the adhesion at the interface between the zinc phosphate-treated film and the organic post-treatment film can be improved.
That is, since the zinc phosphate-treated film is formed as a dense aggregate of grains on the plating surface, the organic post-treated film thereon is filled in the gap between the zinc phosphate-treated film and the zinc phosphate-treated film. An interface between an organic post-treatment film and a zinc phosphate treatment film that is formed along the uneven surface of the film and is excellent due to the action of hydrogen bonding and strong van der Waals force between the upper organic film and the lower zinc phosphate treatment film. Can be obtained. In addition, even if the organic post-treatment film is coated, the anchor effect (throwing effect) due to the uneven surface of the zinc phosphate treatment film and the interaction or chemical bond due to the functional group contained in the organic post-treatment film and the adhesive or blade member Thus, adhesion to a blade member such as rubber bonded via a blade member or an adhesive resin layer, or an adhesive layer is obtained.

  The organic post-treatment film is composed of 10 to 100% by mass of an amino group-containing silane coupling agent, another silane coupling agent, and / or an organic component characterized by comprising 0 to 90% by mass of an organic alkoxysilane compound. Is done. The amino group-containing silane coupling agent, the other silane coupling agent, and the organic alkoxysilane compound may be used alone, in a mixture of two or more, or a derivative thereof. .

  Examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N- (2-aminoethyl) 3aminopropyltrimethoxysilane, and N- (2-aminoethyl). 3aminopropyltriethoxysilane, N- (2-aminoethyl) 3aminopropylmethyldimethoxysilane, N-phenyl-3aminopropyltrimethoxysilane, bis (trimethoxysilylpropyl) amine, N, N′-bis [3 -(Trimethoxysilyl) propyl] ethylenediamine and the like and oligomers thereof.

  Other silane coupling agents include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (Triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc., and oligomers thereof.

  Examples of the organic alkoxysilane compound include tetramethoxysilane, tetraethoxysilane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, and oligomers thereof.

  In the amino group-containing silane coupling agent, other silane coupling agents, and organic alkoxysilane compounds, the alkoxysilyl group is converted to a silanol group by hydrolysis. The silanol group forms a strong hydrogen bond with the lower zinc phosphate-treated film crystal, while it forms a polymer by self-condensation to form a strong post-treated film. Therefore, the organic post-treatment film exhibits extremely high adhesion to the zinc phosphate treatment film.

The silane coupling agent is effective for improving adhesion by interaction or chemical bond between the functional group and the functional group contained in the adhesive or blade member, but the silane coupling agent particularly contains an amino group. The effect is remarkable in some cases. It is considered that the amino group is highly polar and has various reactivity, so that it is particularly suitable for the interaction with the functional group contained in the adhesive or the blade member and the formation of a chemical bond.
A silane coupling agent having a functional group other than an amino group and / or an organoalkoxysilane compound is used to adjust the concentration of amino groups and the degree of crosslinking so that the organic post-treatment film exhibits optimum adhesive strength. Used for
Content in the organic post-processing film | membrane of the said amino group containing silane coupling agent is 10-100 mass%, Preferably it is 30-90 mass%. When the content is less than 10% by mass, the adhesion with a blade member such as rubber or an adhesive layer bonded via a blade member or an adhesive resin layer may be lowered.

The organic post-treatment film is formed with a film amount having a lower limit of 0.01 g / m ² and an upper limit of 1 g / m ² . If it is less than 0.01 g / m ² , the organic post-treatment film is not sufficiently filled in the gaps of the zinc phosphate treatment film, and the uneven surface of the zinc phosphate treatment film is unevenly coated. Since bond strength and van der Waals force are not secured, there is a possibility that the adhesion of the interface between the zinc phosphate-treated film and the organic post-treated film may not be improved. If it exceeds 1 g / m ² , the organic post-treated The film masks the irregularities of the zinc phosphate-treated film, the anchoring effect is lowered, and the adhesion to the blade member such as rubber or the adhesive layer bonded via the blade member or the adhesive resin layer is lowered. There is a fear. The lower limit is more preferably 0.03 g / m ² , and the upper limit is more preferably 0.7 g / m ² .

The organic post-treatment film is formed on the zinc-based plated steel sheet on which the zinc phosphate-treated film is formed, on the amino group-containing silane coupling agent, or on the amino group-containing silane coupling agent and other silane coupling agents, Alternatively, it can be formed by applying an organic post-treatment agent obtained by diluting an organic alkoxysilane compound with a diluent such as water or alcohol and drying it. The application method is not particularly limited, and examples thereof include an immersion method, a spray method, an airless spray method, and a roll method. The said drying is implemented at 40-180 degreeC as an ultimate board temperature, for example using a hot air furnace, a direct-fired furnace, IH furnace etc., Preferably it is 60-150 degreeC.
The organic post-treatment can be performed as a sealer treatment at the toner blade manufacturing site, but it is more uniform in the steel plate manufacturer when the zinc phosphate treatment and the organic post-treatment are successively performed. Is more preferable in that it can be formed and an effect that the on-site primer treatment which is one of the objects of the present invention can be omitted is obtained.

  The zinc-based plated steel sheet used for the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention is not particularly limited. -Zinc-based electroplating such as iron-plated steel plate, zinc-chromium-plated steel plate, zinc-manganese-plated steel plate, hot-dip plated, zinc-plated alloy-plated steel plate, etc.

The inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has a zinc phosphate-treated film formed on the surface of a zinc-based plated steel sheet with a coating amount of 0.3-5 g / m ² , and an amino group-containing silane An organic post-treatment film comprising a coupling agent or an amino group-containing silane coupling agent and other silane coupling agent and / or an organic alkoxysilane compound is formed at a film amount of 0.01 to 1 g / m ^2. Therefore, the entire surface of the steel sheet can be covered with a uniform and uneven film. As a result, the adhesion between the plating surface of the zinc-based plated steel sheet and the zinc phosphate treatment film, the zinc phosphate treatment film and the organic post-treatment film, the organic post-treatment film and each interface of the adhesive or blade member is improved. Therefore, it is possible to secure a high strength and stable adhesion between the blade member and the blade support member, which is the main performance requirement of the blade. Therefore, sufficient adhesion performance can be satisfied by using the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention as a blade support member.

  Furthermore, the inorganic-organic composite-treated zinc-based plated steel sheet of the present invention has a coating composition having a zinc phosphate-treated film on the surface of the zinc-based plated steel sheet and an organic post-treated film thereon, so that it can be used at room temperature. In addition, it is also suitable for high-temperature adhesive applications exceeding 250 ° C., which cannot be applied to organic post-treatment films equivalent to the prior art.

EXAMPLES Hereinafter, although an Example is hung up and demonstrated in more detail, this invention is not limited only to these Examples.
(Processing method for galvanized steel sheet)
Table 1 shows the plating plate used. After the alkaline degreasing treatment, the test plate was prepared by sequentially performing zinc phosphate treatment and post-treatment.
Zinc phosphate treatment is carried out at a temperature of 45 ° C. at a treatment time of 1 to 10 seconds by a spray method using a bath prepared as shown in Table 2 after a commercially available TiO ₂ colloidal surface conditioning treatment, Washed with water and dried.
Table 3 shows the components and composition of the organic post-treatment. All treatments were applied using a roll coater and dried with a hot air drier at a final plate temperature of 110 ° C.
Examples 1 to 23, 34 to 56 and Comparative Examples 24 to 33, 57 to 66
Test plates were manufactured so as to satisfy the conditions shown in Table 4 (type of original plate, type of zinc phosphate treatment and coating amount, type of organic post-treatment and coating amount). EG20 or GI70 in Table 1 is used as the original plate, and No. 1 in Table 2 is used as the zinc phosphate treatment bath. No. 1 to No. 3 in Table 3 are used as organic post-treatment agents. 1-7 were used. The coating amount after the zinc phosphate treatment was calculated from the difference in mass before and after dissolving the zinc phosphate treatment coating with chromic acid. Each organic post-treatment agent was applied to the sample after the zinc phosphate treatment, dried at an ultimate plate temperature of 110 ° C., allowed to cool in the room, and left to dry. The film amount of the organic post-treatment film was calculated from the mass difference before and after coating.

(Blade adhesion evaluation method)
The treated galvanized steel sheet is shear sheared into a 20 mm square sample, and a wet-curing urethane adhesive preheated to 120 ° C. is applied to the cartridge can so that end surface burrs do not warp on the adhesive surface. Immediately after placing a small amount on the adherend by extrusion from the tip, immediately press the urethane rubber that is a blade member (10 mm × 20 mm strip with a thickness of 1 mm), pressurize at 49 N / 100 mm ² for several seconds, The thickness of the adhesive between the blade member and the steel plate was set to be 0.1 ± 0.05 mm. Thereafter, after standing in the room for 1 hr, 1 day aging was performed in a constant temperature and humidity chamber of 35 ° C. and 60% RH. After taking out, it was left in the room for 3 hours to evaluate blade adhesion.

The steel plate is fixed horizontally with a jig, and the longitudinal direction of the rubber strip is firmly sandwiched with the jig with the chuck, and the jig with the chuck is 10 mm / min. Raised at the speed of. At this time, the initial peel strength at which the rubber was peeled off was monitored and used as a blade adhesion evaluation value. The evaluation criteria were as follows.
○: Over 85 N / 10 mm Δ; 75-85 N / 10 mm
X: Table 4 shows the evaluation results of less than 75 N / 10 mm.

EG20, zinc phosphate treatment bath Nо. 1-3, organic post-treatment agent No. The test plates using Examples 1 to 5 (Examples 1 to 23) were excellent in blade adhesion in any combination of coating amounts. Further, even when GI70 was used (Examples 34 to 56), it was possible to obtain a blade having excellent blade adhesion in any combination of coating amounts (scores Δ to ○).
On the other hand, the test plates obtained in Comparative Examples 24-33 when EG20 was used and Comparative Examples 57-66 when GI70 was used were not able to obtain those having excellent blade adhesion (score). X). That is, a zinc phosphate-treated film on the lower layer of the surface of the zinc-based plated steel sheet, 10-100% by mass of the amino group-containing silane coupling agent on the upper layer, 0-90% of other silane coupling agents and / or organic alkoxysilane compounds. It has been found that the blade adhesion can be remarkably improved by having an organic post-treatment film composed of mass%.

In addition, when a steel sheet having a chromate film and an organic lubricating film layer on an electrogalvanized steel sheet according to Patent Documents 1 and 2 corresponding to the prior art is used and the adhesion is evaluated by the above evaluation method, the score is x. It was.
Further, the evaluation method described above using Nippon Steel's bonded steel sheet, which is the prior art of Patent Documents 3 and 4, and a moisture-curable adhesive containing a hydrolyzable organosilane compound or a hot melt adhesive to which a silane coupling agent is added. When the adhesion evaluation according to the above was performed, the score was x.

Claims (2)

An inorganic-organic composite-treated zinc-based plated steel sheet for blade support members having a zinc phosphate-treated film formed on the surface of a zinc-based plated steel sheet and having an organic after-treated film thereon, wherein the organic after-treated film Is composed of 10 to 100% by mass of an amino group-containing silane coupling agent, another silane coupling agent, and / or an organic alkoxysilane compound of 0 to 90% by mass. Plated steel sheet. ^{2. The} inorganic / organic composite-treated zinc system for blade support members according to claim 1, wherein the zinc phosphate-treated film amount is 0.3 to 5 g / m ² and the organic post-treated film amount is 0.01 to 1 g / m ^2. Plated steel sheet.