JP2003183684A - Coating composition for plating - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coating composition for zinc plating capable of imparting lubricant performance to a zinc-plating film while maintaining the rustproofing or corrosionproofing performance inherent in the film through maintaining it. <P>SOLUTION: This composition comprises an epoxy resin meeting at least one of the requirements: (a) <1,000 in number-average molecular weight, (b) liquid or semi-solid at 22-27°C and (c) ≤K in the viscosity at 25°C in the form of a 40 wt.% resin solid butyl carbitol solution determined by Gardner-Holdtz method, a curing agent and a solid lubricant; wherein it is preferable that the curing agent is an amine-based one selected from the group consisting of an aliphatic amine, alicyclic amine, cyclic amine, aromatic amine, polyaminoamide, epoxy compound-added polyamide, Michael-added polyamine, Mannich-added polyamine and tertiary amine compound. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a plating coating composition for imparting lubricity and wear resistance to a metal member having a galvanized surface.

[0002]

2. Description of the Related Art Zinc plating is widely used as an anticorrosive coating of iron, mainly for automobile parts, household electric parts, and sundries. The advantage of galvanizing is that not only does zinc physically cover the iron surface and blocks water and oxygen, which cause iron corrosion, from the iron surface, but it also has a greater ionization tendency than iron. It is possible to obtain excellent corrosion resistance and aesthetics of chromate by electrochemically rust-proofing iron even if there is a pinhole and by treating the chromate film on the zinc plating. For such a reason, the chromate coating is adopted in many galvanizing treatments, and the tendency is remarkable in precision equipment parts such as automobile parts and household electric parts.

In precision equipment parts such as automobiles, sliding parts are sometimes galvanized. In many cases, oil-based lubricants such as grease and paste are used to mitigate the adverse effects of friction. However, since the oil-based lubricant exerts a lubricating effect on a smooth surface, the minute surface irregularities that metal parts inevitably have are required to have a stable lubrication performance only after the irregularities are smoothly worn at the initial stage of friction. However, the initial partial wear of the galvanized surface cannot be denied. Further, the viscosity change due to the temperature and the original liquid form make it impossible to continue to exist on the sliding surface. For this reason, there is a problem in lubrication durability such that the required coefficient of friction is not obtained at times and malfunction may occur.

For example, in a latch for holding a striker of an automobile door lock device and a pole (also referred to as a ratchet or hook) which is a meshing partner of the latch,
Each of them is galvanized as an anticorrosion treatment. The reaction force of the weather strip of the entire door is constantly applied to the meshing surface, and when the door is unlocked, the latch or the pole moves in the direction in which the meshing is disengaged, and the contact area of the meshing surface decreases with the movement. . Therefore, when the door is unlocked, a large frictional resistance is generated, which adversely affects the operability of the door handle. Therefore, in many cases, in order to suppress the resistance, grease is applied to the meshing surface. However, since the meshing surface has fine irregularities, it is difficult to supply grease to the convex portions, frictional resistance sometimes increases, and the operation feeling of the door handle deteriorates. In addition, when using grease, there was concern about durability because the grease itself deteriorated over time, and temperature change and rainwater caused it to fall off the meshing surface.

Also, in a window regulator device of an automobile, glass guides, brackets, etc., which have a mechanism for holding and vertically moving a door glass, are galvanized for the purpose of preventing rust, and the meshing surface between the latch and the poles. Similarly, a method of reducing frictional resistance by applying grease is adopted, but similarly, there are problems due to temperature change and rainwater.

On the other hand, there is a general method in which the surface is coated with a paint containing a solid lubricant for the purpose of lubrication to obtain a lubricating effect. Usually, paints that provide lubricity use a binder that combines a high molecular weight epoxy resin and its curing agent, such as phenol resin, amino resin, or block isocyanate resin, or a binder such as phenol resin or polyamideimide resin. Temperature is 120
It is as high as ~ 230 ° C, and cracks and the like may occur due to exceeding the heat resistance of the chromate treatment, and the original performance of galvanization may be impaired, so it could not be used. When heated, the chromate cracks from a little over 80 ° C to 90 ° C, although to a lesser extent, and its corrosion resistance effect begins to be lost.
When it reaches 00 ° C, many cracks suddenly occur,
As a general heat resistant temperature, 80 ° C is a standard. Also, use a binder such as acrylic resin or urethane resin, and apply a material that is baked at around 80 ° C.
The material with the high baking temperature may be baked in the vicinity of 80 ° C. and used in an incompletely cured state, but the abrasion resistance of the coating,
It had poor chemical resistance. Further, there is a problem that the coating film is difficult to adhere to the galvanized surface having the chromate coating.

[0007]

SUMMARY OF THE INVENTION Therefore, the present invention provides a zinc plating coating composition capable of imparting lubricating performance while maintaining the galvanized coating to maintain the original rust prevention or corrosion resistance. The purpose is to do.

[0008]

DISCLOSURE OF THE INVENTION The inventors of the present invention have a coating composition capable of exhibiting lubricity and strength even by low-temperature baking, protecting the surface of a galvanized or further chromate-resistant corrosion resistant coating, and imparting lubricity for a long period of time. The composition was discovered and the present invention was completed. That is, according to the present invention, the following compositions are provided. (1) The following (a) to (c): (a) number average molecular weight of less than 1000, (b) liquid or semi-solid at a temperature of 22 ° C to 27 ° C, and (c) resin solid content of 40 wt. % Butyl carbitol solution having a viscosity (25 ° C.) by the Gardner-Holtz method of K or less, containing an epoxy resin satisfying at least one of the above, a curing agent, and a solid lubricant,
Composition for galvanizing coating. (2) The curing agent is selected from the group consisting of an aliphatic amine, an alicyclic amine, a cyclic amine, an aromatic amine, a polyaminoamide, an epoxy compound-added polyamide, a Michael-added polyamine, a Mannich-added polyamine, and a tertiary amine compound. The composition according to (1), which is an amine-based curing agent. (3) Furthermore, a reinforcing material is contained, (1) or (2)
The composition as described. (4) The composition according to any one of (1) to (3), wherein the epoxy resin is a chelate-modified epoxy resin. (5) The composition according to any one of (1) to (4), wherein the epoxy resin has an epoxy equivalent of less than 700. (6) A method for producing a galvanized member comprising a galvanized layer and a resin film on the surface side thereof, the resin film comprising the following steps; (C): (a) number average molecular weight is less than 1000,
(B) Liquid or semi-solid at a temperature of 22 ° C. to 27 ° C., and (c) Viscosity (25 ° C.) of a resin solid content of 40 wt% butyl carbitol solution measured by the Gardner-Holts method is K.
An epoxy resin that satisfies one or more of the following,
A method of forming by a step of supplying the curing agent and a step of reacting the epoxy resin and the curing agent at a temperature of 80 ° C. or lower to cure. According to these inventions, by using the epoxy resin, the curing agent and the solid lubricant satisfying any one of the above conditions, a cured film excellent in adhesion, film strength and lubricity is formed on the galvanized surface. To be done. As a coating with friction, the coating needs to be tough, and an epoxy resin having a number average molecular weight of less than 1000 is conventionally hard to be used as a coating with friction due to the drawback of being hard and brittle. However, when the solid lubricant is contained, since the viscosity is low, the wettability to the solid lubricant is high, and by effectively holding the solid lubricant, it is possible to release the stress applied to the coating and to withstand the friction. I can do it now. Furthermore, it has been found that the inclusion of a reinforcing agent can exert sufficient strength against friction. this is,
It is presumed that the epoxy resin has excellent adhesion and low-temperature reactivity, but the reason does not restrain the present invention. Therefore, according to these inventions, a film having excellent lubricity and strength can be formed on the surface without damaging the galvanized layer and / or the chromate film. This coating can exhibit sufficient lubricating performance even under load. As a result, it is possible to obtain a modified surface layer that has both rust resistance and corrosion resistance of the galvanized layer and the chromate film, as well as lubricity.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The galvanizing coating composition of the present invention contains an epoxy resin, a curing agent for the epoxy resin, and a solid lubricant. According to the composition of the present invention,
The epoxy resin and its curing agent are mixed, reacted, and cured to ensure adhesiveness with the zinc plating layer or the chromate layer, and form a coating film that covers the zinc plating surface. As the epoxy resin in the present invention, various conventionally known epoxy resins can be used. Specifically, glycidyl ether type bisphenol A
Type, bisphenol F type, novolac type, brominated type,
Examples thereof include glycidyl ester type such as dimer acid glycidyl ester, linear aliphatic epoxide type, alicyclic epoxide type, and modified products thereof such as urethane-modified epoxy resin, rubber-modified epoxy resin, and chelate-modified epoxy resin. In the present invention, these epoxy resins may be used alone or in combination of two or more. A chelate-modified epoxy resin is preferable.

The number average molecular weight of the epoxy resin is preferably less than 1000. When it is 1000 or more, the reactivity in the low temperature range is excessively lowered, and the curing reaction becomes difficult in a range that does not adversely affect the chromate film. Also, the viscosity is too high, and it becomes difficult to obtain adhesion during film formation. More preferably, it is 700 or less.
The number average molecular weight of the epoxy resin can be measured by a known method such as gel permeation chromatography. In addition, the epoxy resin, 22 ℃ ~ 2
It is preferably liquid or semi-solid at 7 ° C. (preferably 25 ° C.). Here, the liquid or semi-solid means a state having fluidity, and is intended to exclude the epoxy resin which solidifies at this temperature. Alternatively, it is preferable that the viscosity (25 ° C.) of the butyl carbitol solution having a resin solid content of 40 wt% by the Gardner-Holtz method is K or less. This is because the epoxy resin having such properties has a number average molecular weight of less than about 1000, has good reactivity in a low temperature range, and can secure adhesion at the time of film formation. The resin solid content of the measurement solution in the Gardner-Holts method may exceed 40 wt%. Four
If it becomes K or less in a 0 wt% butyl carbitol solution, the viscosity can be measured at a high resin solid content concentration of more than 40 wt%. The Gardner-Holts method is described in JIS K5400 4.5 Viscosity item, Gardner-type foam viscometer method, ASTM D1545-98. Preferably, the method described in JIS K5400 is used. Further, the epoxy equivalent is preferably less than 700. When the epoxy equivalent is 700 or more, the curing reactivity in the low temperature range becomes too low, a tough cured product cannot be obtained, and it is difficult to obtain chemical resistance. More preferably, it is 500 or less. A rubber-modified or urethane-modified epoxy resin is useful for increasing the toughness of a low molecular weight epoxy resin, and a chelate-modified epoxy resin is preferable for a zinc plating layer having a chromate, since it is most excellent in adhesion. Commercially available products are trade names Epikote 825, 827, 82.
8, 834, 1001, 1002, 806, 152, 1
54, 1031S, 604, 871, 191P, YX3
10 (above, Japan Epoxy Resin Co., Ltd.), Epotote YD-115, YD-128, YD-134, Y
DCN-701, YD-171, YD-172, YR-
450, YR-207 (all manufactured by Tohto Kasei Co., Ltd.),
Epomic R114, R130, R139, R140,
R301, R302, SR35, VSR3531, TE
CHMOREVG3101 (above, Mitsui Chemicals, Inc.), Epicron 840, 850, 855, 860, 1
050 (manufactured by Dainippon Ink and Chemicals, Inc.), ADEKA RESIN EP-4100, EP-4400, EP-400.
0, EP-4004, EPU-6, EPU-73, EP
U-78-11, EPU-1348, EPU-139
5, EPR-4023, EPR-4026, EPR-1
309, EPR1415-1, EPR-1508, EP
R-21, EPU-11, EPU-15, EP-49-
10, EP-49-20, EP-49-55C, EP-
6075, EP-6076, EP-777, EP-88
0, EP-9002, EP-9003 (above, Asahi Denka Kogyo KK), Araldite AER250, AER2
60, AER280, AER6041 (manufactured by Asahi Ciba Co., Ltd.) and the like.

As the curing agent for the epoxy resin in the present invention, aliphatic amine, alicyclic and cyclic amine, aromatic amine, polyaminoamide, modified polyamine, epoxy compound-added polyamine, Michael-added polyamine, Mannich-added polyamine, etc. Various conventionally known curing agents for epoxy resins such as acid anhydrides, polyphenols, polymercaptans, tertiary amine compounds, imidazole compounds, and isocyanate compounds can be used.
Preferably, a curing agent that can be cured at a curing temperature that does not easily cause cracks in the chromate coating of the galvanized layer is used.
Specifically, it is a curing agent that can complete the curing reaction at a temperature of 80 ° C. or lower. For example, aliphatic amine, alicyclic amine,
An amine-based curing agent selected from a cyclic amine, an aromatic amine, a polyaminoamide, an epoxy compound-added polyamide, a Michael-added polyamine, a Mannich-added polyamine, and a tertiary amine compound, or an isocyanate compound can be used. A curing agent is preferable, and it is preferable to use an aliphatic amine, an alicyclic amine, a modified aromatic amine, or a polyaminoamide, depending on the type of epoxy resin. More preferably, polyaminoamide,
It is an aliphatic polyamine. It is also possible to improve flex resistance and adhesion by using urethane-modified or rubber-modified amine. Specifically, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, polyaminoamide, menthenediamine, isophoronediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,
4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, metaxylenediamine, diaminophenylmethane,
Diaminodiphenylbutane, m-phenylenediamine and the like can be used. Among these, diethylenetriamine,
Triethylenetetramine, tetraethylenepentamine,
Diethylaminopropylamine, polyaminoamide, N
-Aminoethylpiperazine, 3,9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3)
-Methylcyclohexyl) methane and metaxylenediamine are preferred. Commercially available products include trade names of Epomate B002, RX2, RX221, RX3,
Epicure U, 3549 (above, Japan Epoxy Resin Co., Ltd.), Goodmide G-725, G-41
2, tote amine TH-431, TH-451, TH-
432, TH-452, KXH-429 (above, manufactured by Tohto Kasei Co., Ltd.), Epomic Q610, Q612, Q6
36, Q640, Q654 (above, manufactured by Mitsui Chemicals, Inc.), Epicron B-3150, B-3260 (above,
(Manufactured by Dainippon Ink and Chemicals, Inc.), Adeka Hardener EH455, EH-253-9, EH-404, EH3
932, EH3995, EH-3136, EH-54
9, Grandmide 625, 640, 645, 650, 6
56, 660, 665, 671, 675 (all manufactured by Asahi Denka Co., Ltd.), HY847, HY848, HY94.
3, HT9624, HT9624, XJ9002 (manufactured by Asahi Ciba Co., Ltd.), Fujicure 5420, ZS-4, F
XK-830, 4025, Tomide # 210, # 21
5-X, # 245, # 2500, # 423, # 437
(These are manufactured by Fuji Kasei Kogyo Co., Ltd.) and the like.

The amount of the curing agent added to the epoxy resin is
Calculate from the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the curing agent, and add the appropriate amount. In this case, the proper addition amount is such that the epoxy equivalent / active hydrogen equivalent is 0.5 to 2.0.
Is preferred. Further, although there is no limitation on the proper addition amount, it is 10 to 20 parts with respect to 100 parts by weight of the epoxy resin.
It is preferably 0 part by weight. When it is less than 10 parts by weight, the reaction rate is lowered and the crosslinking density is lowered, resulting in deterioration of physical properties such as heat resistance, and when it exceeds 200 parts by weight, chemical resistance and heat resistance are deteriorated. Sometimes.

Examples of solid lubricants include sulfides such as molybdenum disulfide and tungsten disulfide, layered flaky substances such as graphite, fluorinated graphite, boron nitride and mica, soft metals such as lead, zinc and copper, and polytetrafluorocarbon. Fluororesin such as oloethylene (PTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), ethylene / tetrafluoroethylene copolymer (ETFE) , Melamine cyanurate and the like. Molybdenum disulfide, graphite and polytetrafluoroethylene are preferred. In the present invention, one or more of these may be used. The average particle size of these solid lubricants is preferably 0.1 to 40 μm, and is 0.5 to 20 μm.
Is particularly preferable. Also, the mixing ratio is 10 parts by weight or more and 3 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and its curing agent.
It is preferably not more than 00 parts by weight. If less than 10 parts by weight,
The required effect of reducing the frictional resistance is low, and the coating film breaking load at the time of friction may be reduced due to the deterioration of the sliding characteristics. If it exceeds 300 parts by weight, the cohesive force of the coating film decreases,
Durability may not be obtained, and there is a risk that the sliding characteristics may deteriorate accordingly. More preferably, it is 25 parts by weight or more and 250 parts by weight or less.

Examples of the reinforcing agent include carbon black, metal oxides such as titanium oxide, iron oxide, chromium oxide, cobalt oxide and zinc oxide, aluminum hydroxide, talc, wollastonite, potassium titanate, barium sulfate and bases. Magnesium sulfate, sepiolite, xonotlite,
Aluminum borate or the like can be used. These can be used alone or in combination of two or more.
In particular, various metal oxides and aluminum hydroxides that can increase the hardness of the coating film and improve the abrasion resistance are preferable.
More preferably, titanium oxide, cobalt oxide, iron oxide,
It is aluminum hydroxide. Since the reinforcing effect is small when the particle size is large, the particle size is preferably 0.01 μm to 10 μm,
It is more preferably 0.01 to 3 μm. The compounding ratio of the reinforcing agent is 0.5 parts by weight or more 1 when the total amount of the resin is 100 parts by weight.
It is preferably not more than 00 parts by weight. When the amount of the reinforcing agent is large, the coefficient of friction tends to increase. More preferably 0.5
It is from 50 parts by weight to 50 parts by weight.

In the present invention, in addition to the above components, it can be modified with a general modifier. Examples of this modifier include thinning agents such as reactive diluents that control fluidity, thickening agents that control thixotropic properties, leveling agents and surfactants that control surface tension, adhesiveness and reinforcing agents. Examples thereof include a silane coupling agent that helps improve the affinity to a certain filler and an adhesive property, a solid lubricant, and a dispersant that helps disperse the filler.

In the present composition, the epoxy resin and its curing agent have a solid lubricant, reinforcing agent, etc. dispersed therein, or the epoxy resin and its curing agent are dissolved in an organic solvent or a solvent such as water. Alternatively, the solid lubricant and the reinforcing agent may be dispersed therein and dispersed therein. In addition,
The composition has curing reactivity in a relatively low temperature range. Therefore, the curing agent may be added to the epoxy resin immediately before use.

Next, a method of forming a resin film on the galvanized layer of the galvanized member with the present composition will be described. The composition prepared by mixing a curing agent in a solution in which a solid lubricant and a reinforcing agent are dispersed in an epoxy resin is applied to the surface of the galvanized layer. As a coating method, various conventionally known methods such as brush coating, dipping, spraying, screen printing, flow coater, roll coater and barrel coater can be adopted. The composition is provided as an upper layer portion of the galvanized layer of the galvanized member, but may be a galvanized layer on which a coating such as chromate is not formed, but zinc is preferred. It is applied to the surface where the plating layer is coated with a corrosion resistant film such as chromate. The chromate film can contain various kinds of chromium, that is, hexavalent chromium, and chromates of chromium having various valences such as trivalent chromium. Further, the coating is not limited to the corrosion resistant coating, and may be a coating having other functions and a good appearance (color etc.). First, the firing conditions are selected such that the zinc-plated chromate layer is not destroyed. Depending on the type of epoxy resin and its curing agent, it is preferably at room temperature to 80 ° C for 10 minutes to 1 week, more preferably at 60 ° C to 80 ° C for 10 minutes to 2 hours. This is because if the temperature is lower than 60 ° C., the work efficiency is low and the mass productivity becomes poor, and if the temperature exceeds 80 ° C., the chromate film is cracked. Coating thickness after baking is 3 μm or more 4
It is preferably 0 μm or less, particularly preferably 5 μm or more and 30 μm or less.

The cured film of the present composition thus obtained has good coating adhesion because it uses an epoxy resin. Therefore, the risk of the cured film being lost due to peeling or the like is avoided. The molecular weight is 1000
When an epoxy resin having an epoxy content of less than or equal to and / or an epoxy equivalent of less than 700 is used, in particular, a sufficient curing reaction can be achieved at a temperature of 80 ° C. or less, so that the chromate film is cracked. Nor. Therefore, the resin film is formed with good adhesion without damaging the plating layer and the chromate film. Also,
In particular, since the cured film of epoxy resin itself has sufficient abrasion resistance, it stably protects the plating layer and / or the chromate film for a long period of time even after the cured film is formed, and the original rust prevention And corrosion resistance can be exhibited. When a highly fluid epoxy resin having a molecular weight of less than 1000 is used, it adheres well to not only the concaves and convexes derived from the shape of the plated member but also the fine irregularities of the surface layer, It is possible to form a cured film that follows an arbitrary shape. Therefore, it is possible to protect the plating layer and provide lubricity regardless of the shape and surface layer form, and as a result, it is possible to form a coating film having excellent durability.

Further, since the main cured coating film contains a solid lubricant, it has good lubricity. In particular,
Due to the formation of a film in which a solid lubricant is dispersed in a lower viscosity epoxy resin having a molecular weight of less than 1000,
The solid lubricant is easily moistened, the solid lubricant is sufficiently retained in the resin matrix, and stable lubricating performance can be exhibited for a long period of time. A solid lubricant usually exerts a lubricating effect by its own shearing property and crushing property, but by being dispersed in an epoxy resin, it maintains the lubricating performance of the solid lubricant and has durability as a lubricating film. Can be given.

When the main cured coating film contains a reinforcing agent, the durability of the coating film is further improved. Further, as a result of improving the durability of the coating film, the lubricity can be exhibited more stably. An epoxy resin having a number average molecular weight of less than 1000 is also a preferable resin matrix for a reinforcing agent and can hold the reinforcing agent uniformly and satisfactorily in the cured epoxy resin film.

Applicable objects of the present composition are the latches and poles of the meshing surface of the door lock mechanism in automobiles, the brackets of window regulators, the glass guides, the mails and females of the door stoppers, the check links of the door check mechanism, and the check covers. , Control lever of sliding door mechanism, hinge pin, spring, washer, reclining pin of seat mechanism, link, ratchet, roof guide pin of roof mechanism, lever, etc., other precision equipment parts include spring, washer, bearing, Links, pins, slide rails, etc. can be mentioned, but all can be applied to parts having a zinc-plated layer having chromate on the surface. Therefore,
According to the present invention, there is provided a method for producing a galvanized member having a resin film by applying the composition to the surfaces of the galvanized layers of these members to form a cured film. Further, according to the present invention, there are also provided these galvanized members in which the cured film obtained by the present composition is provided on the surface of the galvanized layer.

The present composition is preferably applied to the mutually contacting portions of a pair of galvanized members that relatively move such as fitting, meshing, locking, screwing, sliding, or the like, and the composition is coated with the composition. By providing the film, higher durability can be exhibited. Although it is effective only by facing one another, even though there is galvanization, it is a metal-to-metal contact, so it can be applied to both in order to more effectively utilize the buffering effect of load and friction resistance by this composition. preferable. However, when it is applied to either one, it is effective to apply it to one having high hardness. When the cured film of the composition of the present invention is used in parts such as automobiles, oil-based lubricants such as mineral oil-based and synthetic oil-based greases and pastes can be used together. When used together, the coefficient of friction is further lowered and the durable life is often extended. Therefore, according to the present invention, the composition of the present invention is obtained by curing the composition of the present invention at the mutual contact site of each galvanized member of the galvanized member that moves relative to each other such as fitting, meshing, locking, screwing, and sliding. There is provided a structural member, which is provided with the cured film thus obtained and a liquid or fluid lubricant, and which is in relative contact with each other. The structural member includes an application target of the present composition described above.

As described above, according to the present invention, the galvanized layer, the chromate film and the like are not damaged.
It is possible to provide a cured film having excellent lubrication performance and abrasion resistance performance. Therefore, as a result, it is possible to impart a highly durable lubricating effect to the surface layer of the galvanized layer. In particular, by using the solid lubricant and the reinforcing agent together, the lubricating performance and the abrasion resistance can be easily and freely adjusted, so that the cured film having the desired performance can be obtained. Furthermore, by additionally using a liquid or fluid type lubricant such as grease or oil, it is possible to provide a further low friction coefficient and durability.

[0024]

EXAMPLES The present invention will be described below with reference to specific examples.
These specific examples are provided for the purpose of understanding the present invention and are not intended to limit the present invention. Epoxy resins, curing agents, solid lubricants, reinforcing agents, and solvents were blended according to the compositions shown in Tables 1 and 2 to prepare the compositions of Examples 1 to 20. The friction characteristics of the prepared composition were evaluated. The preparation procedure of Example 1 is described below. Examples 2 to 20 follow the compositions of Table 1 and Table 2 and
Each composition was prepared by performing an operation according to the operation of 1. The mixing ratio of each epoxy resin and the curing agent in Examples 1 to 20 was set such that the equivalent ratio of the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the curing agent was 1.0. Further, the friction characteristics were evaluated by the same method as in Example 1. Tables 1 and 2 show the results of evaluation of the friction characteristics of the compositions of all the examples. Tables 1 and 2 show the viscosities (poises) or Gardner viscosities of the resins used at 25 ° C.

Example 1 Bisphenol A diglycidyl ether (epoxy equivalent 190, number average molecular weight 38)
0, viscosity 135 poise / 25 ° C.) 61 parts by weight of a mixed solution of methyl ethyl ketone and toluene (mixing ratio (weight))
1: 1) Dissolved in 200 parts by weight and added with 39 parts by weight of polyaminoamide (amine value 360) to a mixed solution in which 20 parts by weight of polytetrafluoroethylene (PTFE) was dispersed, and uniformly stirred The composition of Example 1 was prepared.
This composition was treated with a test piece of chromate-containing galvanized steel plate (SPCC-S
B) It is applied so that the coating thickness becomes 20 μm, and it is 30 at 80 ° C.
The coating was cured by heating for a minute. This test piece is a load fluctuation type friction wear tester (Haydon 29P, manufactured by Shinto Scientific Co., Ltd.)
Attached to a steel ball as the mating material (dimension: φ3 mm, material: S
In the case of UJ-2), the coating film breaking load (critical load) and the friction coefficient at a load of 200 gf were measured. The coating film breaking load is a load at which the coating film breaks, the underlying zinc-plated layer is broken, and the steel material base is reached. Measurement conditions are load 0-10
00 gf, speed 13 mm / sec, cycle number 200 cycles. The coating film breaking load of this test piece is 280 g
It was f and the friction coefficient was 0.098.

With respect to the same compositions as in Examples 1, 7, 12, and 15, friction characteristics evaluation using grease (YM-102 manufactured by Dow Corning Asia) was also conducted (in Examples 17 to 20, respectively). Corresponding.).

(Comparative Examples 1 to 3) The compositions of Comparative Examples 1 to 3 were prepared in the same manner as in Example 1. Also,
Friction characteristics were evaluated by the same method as in Example 1. Table 3 shows the compositions of the compositions of Comparative Examples 1 to 3 and the evaluation results of the frictional characteristics.

Each mode of Comparative Example (Comparative Example 4: No coating, no lubricant, Comparative Examples 5 and 6: No coating, with grease, Comparative Examples 7 to 13: other compositions), firing conditions and evaluation of friction characteristics The results are shown in Table 4. The evaluation of frictional characteristics was also performed by the same method as in Example 1. Tables 3 and 4 show the viscosities (poises) or Gardner viscosities of the resins used at 25 ° C.

(Comparative Examples 4 to 6) Comparative Example 4 is the result of evaluating the frictional characteristics of the galvanized plate of the test piece which does not form the coating film without using the lubricant. Further, in Comparative Examples 5 and 6, an oil-based lubricant E paste, YM-102 (each manufactured by Dow Corning Asia) in which a solid lubricant is dispersed in a synthetic oil as a base oil is tested on a test piece that does not form a film. The results are obtained by uniformly applying the coating to the surface and testing.

Comparative Example 7 Acrylic polyol (hydroxyl value 30) (nonvolatile content 50%) 164.8 parts by weight (resin solid content 82.4 parts by weight) was mixed with methyl ethyl ketone and toluene (mixing ratio (weight)). 1: 1) dissolved in 100 parts by weight, and 30 parts by weight of PTFE dispersed therein were mixed with 17.6 parts by weight of hexamethylene diisocyanate (isocyanate content 21%), which is a curing agent,
The composition of Comparative Example 7 was prepared by uniformly stirring. This composition is applied to a steel plate (SPCC-SB) having a chromate-containing chromate coating of about 10 microns as a test piece so as to have a coating film thickness of 20 μm, and heated at 80 ° C. for 30 minutes to cure. Let The coating was evaluated for friction properties.

Comparative Examples 8 and 9 Each composition was prepared according to the procedure of Comparative Example 7 except that the composition and baking conditions shown in Table 4 were adopted to obtain coating films. The friction characteristics of the obtained coating film were evaluated.

Comparative Example 10 Oil-free polyester resin (solveso 100 and butyl cellosolve dissolved product,
Nonvolatile content 60%, Gardner viscosity X, acid value 5-8) 11
37.5 parts by weight of imino group-type mixed etherified melamine (N-butanol-dissolved product, nonvolatile content 80%, degree of polymerization 2.3) to 6.7 parts by weight (resin solid content: 3)
0 parts by weight) and mixed with a mixed solution of cyclohexanone and methyl ethyl ketone (mixing ratio (weight) 1: 1) diluted with 150 parts by weight, 90 parts by weight of molybdenum disulfide, 20 parts by weight of graphite, 20 parts by weight of cobalt oxide. Was dispersed to prepare a composition of Comparative Example 10. A coating film was formed from this composition in the same manner as in Comparative Example 7, and the friction characteristics were evaluated.

Comparative Example 11 Each composition was prepared according to the procedure of Comparative Example 7 except that the composition and baking conditions shown in Table 4 were adopted to obtain a coating film. The friction characteristics of the obtained coating film were evaluated.

(Comparative Example 12) 80 parts by weight of bisphenol A diglycidyl ether (average epoxy equivalent 925, viscosity Gardner-Holtz method butyl carbitol 40% (resin) solution viscosity Q to U) 80 parts by weight was mixed solution of cyclohexanone and methyl ethyl ketone. (Mixing ratio 1: 1) Dissolved in 200 parts by weight, further imino group type mixed etherified melamine (n-butanol dissolved product, nonvolatile content 80%, polymerization degree 2.
3) 25 parts by weight (resin solid content: 20 parts by weight) were mixed, and 90 parts by weight of molybdenum disulfide, 20 parts by weight of graphite, and 20 parts by weight of cobalt oxide were dispersed therein to prepare a composition of Comparative Example 12. A coating film was formed from this composition in the same manner as in Comparative Example 7, and the friction characteristics were evaluated.

Comparative Example 13 Each composition was prepared according to the procedure of Comparative Example 7 except that the composition and baking conditions shown in Table 4 were used to obtain a coating film. The friction characteristics of the obtained coating film were evaluated.

[0036]

[Table 1]

[Table 2]

[Table 3]

[Table 4] As shown in Tables 1 to 4, in all the examples, the critical load exceeded 280 gf, and the examples 2 to 5, 7, 8, 1
In 2 to 20, it exceeded 300 gf. That is,
It was found that the coating films obtained from any of the example compositions had good film strength at the time of rubbing. Also,
When a chelate-modified epoxy resin was used as the epoxy resin, a high critical load was obtained. In addition, the inclusion of the reinforcing agent tended to increase the critical load. On the other hand, all comparative examples have a critical load of 200.
It was below gf.

Further, in Examples 1 to 16, a sufficient friction coefficient was obtained without using grease.
Further, when the amount of the solid lubricant was large, the friction coefficient tended to be obviously small. Furthermore, by using grease together, the friction coefficient was about 50% of the conventional friction coefficient, and a high critical load was obtained, and a synergistic effect was confirmed. On the other hand, Comparative Examples 7-1 that do not use grease
In No. 3, the critical load was less than 200 gf, the coating film was destroyed, and an insufficient friction coefficient was obtained.

When the examples and the comparative examples are compared in detail, the strength of the cured film of the example group is remarkably high despite the same curing and baking conditions (80 ° C. × 30 minutes).
That is, in the comparative example, epoxy resin (without solid lubricant), acrylic polyol, hexamethylene diisocyanate, oil-free polyester, bisphenol A
Glycidin ether and imino group-type mixed ether melamine were used, and the lowest critical load value 2 in the examples.
The result was completely below 80 gf.

From the above, a cured film obtained by using an epoxy resin as a binder resin and an amine-based curing agent such as polyaminoamide or an aliphatic amine has high strength even at low temperature firing. It was found that it also has a low coefficient of friction. That is, synergistic with the fact that a coating film having high adhesiveness and excellent abrasion resistance was obtained by using a predetermined epoxy resin, and that the friction coefficient of the coating film could be reduced by the inclusion of a solid lubricant. It is clear that the effect improves the strength against a load during friction and reduces the friction coefficient under a load.

[0040]

According to the present invention, a hardened film having lubricity and strength and capable of exhibiting sufficient lubricating performance even under load can be formed on the zinc plating surface layer side. For this reason, it is possible to impart lubrication performance while maintaining the galvanized coating and maintaining the original rust prevention or corrosion resistance performance.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10M 125/10 C10M 125/10 125/22 125/22 133/04 133/04 147/02 147/02 149 / 18 149/18 C23C 28/00 C23C 28/00 A C // C10N 10:06 C10N 10:06 10:12 10:12 10:16 10:16 F term (reference) 4H104 AA04C AA13C AA19C BE02C BE06C BE07C BE27C BE29C CB12A CD02C CE13C EA02A EA03A EA04A EB03 FA03 FA06 FA08 QA12 QA14 4J038 CD122 CD132 DB001 HA026 HA08 HA356 HA476 HA546 KA03 MA14 4K044 AA03 AA06 BA10 BA21 BB03 BB04 BC01 BC02 CA11 CA18 CA53

Claims (6)

[Claims] 1. The following (a) to (c): (a) number average molecular weight less than 1000, (b) liquid or semi-solid at a temperature of 22 ° C. to 27 ° C., and (c) resin solid. 40 minutes
A zinc plating coating containing an epoxy resin satisfying at least one of a wt% butyl carbitol solution having a viscosity (25 ° C.) of K or less by Gardner-Holtz method, a curing agent, and a solid lubricant. Composition. 2. The curing agent is an aliphatic amine, alicyclic amine, cyclic amine, aromatic amine, polyaminoamide,
The composition according to claim 1, which is an amine-based curing agent selected from the group consisting of an epoxy compound-added polyamide, a Michael-added polyamine, a Mannich-added polyamine, and a tertiary amine compound. 3. The composition according to claim 1, further comprising a reinforcing material. 4. The composition according to claim 1, wherein the epoxy resin is a chelate-modified epoxy resin. 5. The epoxy resin has an epoxy equivalent of 7
The composition according to any one of claims 1 to 4, which is less than 00. 6. A method of manufacturing a galvanized member comprising a galvanized layer and a resin film on the surface layer side thereof, the resin film being subjected to the following steps; )-(C): (a) number average molecular weight less than 1000, (b) liquid or semi-solid at a temperature of 22 ° C to 27 ° C, and (c) Gardner of 40 wt% resin solids butyl carbitol solution. Viscosity by Holtz method (25 ℃)
Is K or less, and a step of supplying an epoxy resin satisfying at least one of the following and a curing agent thereof, and a step of reacting the epoxy resin and the curing agent at a temperature of 80 ° C. or less to cure the epoxy resin and the curing agent. How to form.