WO2006073004A1 - Resin composition excellent in rust inhibition and electroconductivity, and member coated with the resin composition - Google Patents

Resin composition excellent in rust inhibition and electroconductivity, and member coated with the resin composition Download PDF

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Publication number
WO2006073004A1
WO2006073004A1 PCT/JP2005/006690 JP2005006690W WO2006073004A1 WO 2006073004 A1 WO2006073004 A1 WO 2006073004A1 JP 2005006690 W JP2005006690 W JP 2005006690W WO 2006073004 A1 WO2006073004 A1 WO 2006073004A1
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Prior art keywords
resin composition
mass
resin
group
component
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PCT/JP2005/006690
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French (fr)
Japanese (ja)
Inventor
Kazuo Kobayashi
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Shieldtechs, Inc.
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Priority to JP2005001924 priority Critical
Priority to JP2005-001924 priority
Application filed by Shieldtechs, Inc. filed Critical Shieldtechs, Inc.
Publication of WO2006073004A1 publication Critical patent/WO2006073004A1/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes

Abstract

A resin composition which comprises a resin and a scaly foil fine powder in the form of a clad comprising (a) Zn and/or Al and (b) Cu and/or Ni, each being formed into a fine powder in a scaly foil form. The above resin composition is useful as a pollution-free rust inhibitor which can be applied with ease and simplicity, while making good use of advantages of a conventional rust inhibiting (anti-corrosive) method, exhibits rust-inhibiting characteristics being comparable with or superior to those of the hot dip plating, is free from the cause of heat brittleness in a base material, is free from the need of an additional treatment such as a hole sealing treatment, is free from the fear of residual stress even in the case of a thick application, and can be so executed as to respond to the deterioration due to the elapse of time, and further as a pollution-free electromagnetic wave shielding agent which can solve problems in a conventional electromagnetic wave shielding technique, can be executed on any place, can form a coating having a uniform coating film structure, and exhibits good electromagnetic wave shielding characteristics.

Description

 Description Resin composition excellent in anti-shock properties and conductive properties, and resin composition coating material Technical Field The present invention can be applied simply and has electrical conductivity by blending a small amount of metal powder. In addition, a resin composition having an excellent anti-corrosion property equivalent to or better than that of zinc plating, and also exhibiting excellent shielding properties for blocking electromagnetic waves, and coating such a resin composition It is a resin-coated member.

 m Dodan technology It is necessary to protect the surface of steel materials with anticorrosion.

5) (I) A coating method that blocks hornworms with oxygen, sulfides, halides, etc. by coating the surface with a multilayer film with paint or other organic resin materials , (II) Molten zinc, molten zinc alloy, and a melting method in which the workpiece is immersed for a certain period of time and zinc-aluminum is adhered and formed. (III) Zinc and aluminum There is known a metal spraying method or the like in which a metal flame is melted with a gas frame or an arc and adhered to the surface of a steel material or the like, and the sacrificial anodic reaction due to the potential difference of the metal is applied for prevention (for example, a special technique). Open 2 0 0 1 — 2 7 1 1 5 2, JP-A-9

― 1 2 5 2 2 1, JP-A-9 1 3 6 1 4, JP-A-8 — 1 7 6 7 8

No. 1).

On the other hand, with the widespread use of various electronic devices, wireless LANs, mobile phones, etc. and the arrival of the ubiquitous era, electromagnetic interference and information leakage are seen as problems, and the importance of electromagnetic shielding has increased. Electromagnetic shield materials are made of electromagnetic seal K paint. As such a technique, a technique of attaching a metal plate, a technique of attaching a shield plate mixed with a conductive filler to a building material, and the like are known. It is also metallic in synthetic rubber and synthetic resin. An electromagnetic shielding material containing an electromagnetic shield material containing no violet is also proposed (for example, Japanese Unexamined Patent Application Publication No. 2 0 0 2-3 0 9 1

No. 07, Japanese Patent Laid-Open No. 10 — 3 1 6 9 0 1). Furthermore, a technique for improving electromagnetic shielding properties by imparting conductivity by a method such as metal plating or metal vapor deposition is also known.

 It has been pointed out that the various methods described above (corrosion protection) have the following problems. First, (I) In the anti-corrosion (corrosion prevention) method by painting, organic solvent-based paints are mainly used, but the hardness is insufficient and scratches due to surface damage or wear occur. This causes problems such as deterioration of the barrier function and separation from the atmosphere, and corrosion due to damage due to deterioration caused by ultraviolet rays.

 (II) Although the melting method has a corrosion resistance of 10 to 15 years, a large plant for immersing the workpiece in molten zinc or the like is required to implement it. Therefore, there is a problem that it cannot be applied to the maintenance of existing steel structures. In particular, it is not applicable to sheet steels or long steels due to problems such as melting temperature, immersion pool, and distortion of workpieces due to high temperatures.

 Recently, technologies for zinc and aluminum alloys have also been advanced, but the cost of facilities such as ceramic furnaces is high, and environmental regulations are also applied to wastewater treatment of harmful substances used. However, there is a problem from the economic aspect as well. In addition, zinc and aluminum alloy zinc—aluminium—

 From the difference in the cooling temperature of the cum, the zinc and aluminum of the generated? h 曰

 Since the size of the Γ and mouth HH grains is different, there is also a characteristic problem that corrosion is likely to occur from the so-called grain interface.

(III) The metal spraying method has the feature that a functional surface such as zinc or helium alloy is formed directly on the surface of the steel material, so the internal metal is protected by the sacrificial anode reaction. Although it can exhibit corrosion resistance more than zinc plating, it requires mechanical equipment for metal spraying (spraying gun, power supply device, blower, wire rod feeding / feeding device, spraying extension, etc.) Therefore, construction efficiency is also a determinant of craftsman's technology, and even with the heavy burden of equipment installation and maintenance, it is necessary to consider profitability and spraying to existing steel structures And difficult to apply to narrow structures When there is a problem. In addition, in order to melt zinc 'aluminum and force it to adhere to the surface of the object to be treated, the steel structure surface is subjected to a sandblasting sandplast treatment and a rough surface forming agent is used. In order to enhance the effect of metal spraying, if the metal spray surface is made thicker, internal strain and residual stress due to the difference in heat dissipation effect will be generated. There is also a problem that adhesion deterioration such as peeling of the metal sprayed layer is observed. In addition, since a spongy hole is formed on the surface of the sprayed material, it is pointed out that a further sealing process is necessary.

 The following problems have been pointed out in the electromagnetic shielding methods proposed so far. For example, with a method in which a metal plate is stretched and a shield plate with conductive filler mixed in the building material is stretched, it is impossible to install narrow spaces, complex shapes, uneven surfaces, mating portions, etc. Even in the flat part, electromagnetic waves leak from the gap between the bonded parts, and there is a problem that even if it is blocked with a conductive tape, the electromagnetic waves cannot be completely cut off. The disadvantage is that it is expensive. In conductive shield paints, it is possible to apply narrow parts, complex shapes, and uneven parts to prevent electromagnetic wave leakage. However, organic paints and organic solvents (such as toluene) are used as paint components. Therefore, environmental problems due to volatilization of residual materials (formaldehyde, etc.), and electromagnetic leakage from cracks due to aging due to temperature, humidity, and ultraviolet rays can be cited as problems. Furthermore, even with synthetic rubber electromagnetic wave sheets and electromagnetic wave sealing films, there is a problem that even if the seam is closed with a conductive tape, the electromagnetic wave cannot be completely blocked due to peeling of the tape.

The present invention has been made under such circumstances, and its purpose is to be able to easily apply while taking advantage of the conventional anti-corrosion (corrosion-prevention) method, and to be equivalent to melting It exhibits the above-mentioned excellent anti-fouling properties, does not cause thermal embrittlement in the base material, does not require additional processing such as sealing, and can cope with aging degradation without worrying about thickness or residual stress. As a non-polluting antifungal agent that can be applied, the problem with the conventional electromagnetic shielding technology is solved, and the electromagnetic wave has a uniform coating structure with the conventional coating method regardless of the construction site. Non-polluting electricity with shield characteristics It is an object of the present invention to provide a resin composition useful as a magnetic wave shielding agent, and a resin-coated member in which such a resin composition is coated on a substrate surface. DISCLOSURE OF THE INVENTION The resin composition of the present invention capable of achieving the above object includes: (a) Zn and / or A1, and (b) Cu and The present invention has a gist in that a fine powder of a clad scale foil made of pi or Ni is blended in a resin. If necessary, this resin composition may contain a powder of one or more elements selected from the group force consisting of Mn, Mg, Mo, Li, C, and Ag, or an alloy powder. I like to do it.

The resin used in the resin composition of the present invention has a general formula: R ^ NS i (OR 2 ) 4 -N (wherein R 1 is a hydrocarbon group having 1 to 10 carbon atoms, R 2 is an alkyl group having 1 to 3 carbon atoms, an acyl group having 2 to 3 carbon atoms, or <is an alkoxy group having 3 to 5 carbon atoms, and N is an integer of 0 to 2). Examples thereof include a curable resin composed of a silane compound or a partially hydrolyzed condensate thereof.

 In the resin composition of the present invention, if necessary, metal al = 1

It is also useful to contain <1) except 1alkoxy K, which can further improve the properties of the resin composition.

By coating the base material surface with the above five resin compositions, a resin composition-coated member having excellent anti-rust properties and conductivity can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS FIG. Fig. 2 is a graph showing the sealing effect of the electric field due to the resin composition over a wide frequency range, and Fig. 2 is a graph showing the sealing effect of the magnetic field due to the resin composition over a wide frequency range. is there. Best mode for carrying out The present inventor has intensively studied to achieve the above object. As a result, (a) Zn and Z or A1 and

(b) It has been found that a resin composition that can achieve the above-mentioned purpose can be realized by mixing a clad scale fine powder composed of Cu and / or Ni with a resin. The present invention has been completed.

 The components (a) and (b) above are finely scaled powders.

“Scaly foil-like fine powder” means a flaky fine powder, which can be produced by applying a stamping mill or a pole mill. For example, with A 1, the A 1 foil can be made into aluminum scale foil-like fine powder by the above method. In addition, by combining the components (a) and (b) formed into a scale-foil-shaped fine powder as appropriate and applying impulsive pressure in an inert atmosphere with a vibration mill, etc., the difference in hardness and impact Due to the electrostatic effect of energy, other powders are irregularly pressed onto the powder surface, resulting in a fine powder of clad scale foil.

 The resin composition of the present invention must contain both of the above component (a) component (b) component, but the combination of the clad scale fine powder is not necessarily limited to (a) component. It is not necessary to use the components (b) and (b), but it is also possible to use a clad scale fine powder composed of (a) components or (b) components. For example, the Z 11 powder and A 1 powder formed into a scale-foil-like fine powder are pulverized into fine grains with a vibration mill, so that the hardness of the surface of the Zn scale foil powder as a base material is reduced. The low A 1 scale foil powder is irregularly pressed and is clad by completely or partially coating the Zn powder surface, resulting in a composite material of dissimilar metals. The situation is the same for (b) components or between (a) and (b) components.

The component (a) is a scale-like Zn and / or A 1 fine powder, but its size (particle size) is about 10 to 50 im, thickness:! About 10 / zm is preferable, and more preferable is a size of 15-30 / m and a thickness of 2-6 / m. The component (b) is a scaly Cu and / or Ni fine powder, but its size (particle size) is about 10 to 30 / zm and thickness is 0.5 to 5 μm. About πι is preferable, and more preferable is a size of about 10 to 20 im and a thickness of about 1 to 3 / zm. ·-By blending the above-mentioned fine powder of scale-like scales into the resin, a resin composition with excellent antifungal properties and electrical conductivity was realized, so that Although the reason why the above effect was obtained by adopting was not fully understood, it was possible to think as follows. That is, when the clad foil fine powder as described above is blended in the resin, the metal powder can be made uniform in the resin and the coating film structure is uniform. It was thought that it would be excellent in antibacterial properties and mi-guided properties.

 In order to exert the effect of the present invention, it is preferable that the resin blending ratio of the clad scale fine powder is 50% by mass or more, but if it is excessively blended, the resin ratio Since the paintability deteriorates with less

It is preferable to make it 0 mass% or less.

 The clad scale fine powder used in the antifungal agent of the present invention preferably has a size (particle size) of about 10 to 50 μπι and a thickness of about 1 to 8 / xm. More preferably, the size is 20 to 40 / zm and the thickness is 2 to 5 / x.

 It should be noted that the ratio of cladding in each component may be set as appropriate. For example, when Z Z and A 1 are combined, the zinc component is 7% of the total mass of Zn and A 1. It should be in the range of 0 to 95% by mass <, preferably in the range of 85% to 95% by mass. The volume with respect to the ratio of zinc to gallium and bismuth is close to the same capacity. Indeed, the sacrificial anode effect due to the difference of the quasi-electrode i-position is more pronounced.

 For example, in the zinc / aluminum cladding scale fine powder, by laminating each component, the standard electrode potential of A 1 is 1.662 V and the standard electrode potential of zinc is 0.1. Since 7 6 2 V and the standard electrode potential of iron are 0.44 7 V, the sacrificial anode effect due to the potential difference between them is improved.

 The component (a) contributes to the improvement of anti-mold properties, and the component (b) contributes to the conductivity (electromagnetic shielding properties). What is necessary is just to set arbitrarily about the mixing ratio of (a) component and (b) component according to the required characteristic.

If necessary, the resin composition of the present invention contains M n, M g, M o, L It is also useful to mix one or more elements selected from the group consisting of i, c, and Ag with an alloy powder. By reducing the gap between the powder particles in the resin, these components make the dispersion state of the powder particles more airtight, making the metal powder uniform and uniform in the resin. Further improve the membrane structure. These components are also effective for imparting electrical conductivity, like the (1) component. In order to exert these effects, it is appropriate that the blending ratio of the resin is about 1 to 12% by mass. Of these components, C powder (graphite powder) formed into a scale foil shape is particularly preferred. Also, in order to more effectively demonstrate the effects of the blending of these components, the size (particle size) is preferably about 1 to 10 μm.

 As the resin used in the resin composition of the present invention, various resins such as a modified silicone resin and a curable silicone resin can be used, and the type thereof is not particularly limited, but will be described later. A curable compound comprising a silane compound represented by the general formula (1) or a partially hydrolyzed condensate thereof.

V resin is listed as preferred 0

 As the curable silicone resin, conventionally, a so-called silicone varnish solution in which a curable silicone resin having a terminal silanol group is dissolved in an organic solvent such as toluene or xylene has been widely used. This has the following problems (1) and (2).

 (1) An organic solvent with a low flash point is an essential component

 (2) In general, cured film formation requires heating and curing at a temperature of 150 ° C or higher for a long time.Therefore, a large amount of energy is required for curing, and the application range is limited. On-site application is basically impossible

 Because of these problems, it does not contain organic solvents and can be suspended and hardened.

As a non-solvent room-temperature-curing silicone resin, a part of the organosilane is hydrolyzed and condensed, and, if necessary, this silicone corn silicone resin. Considering the addition of a curing catalyst that promotes moisture curing, it is possible to cure at room temperature by using the resin represented by the general formula (1). Maintenance of indoor and outdoor electromagnetic wave shields Has become adaptable.

 By combining the clad scale powder with the curable silicone resin as described above, it is possible to form a uniform laminated film and further improve the film characteristics. A resin composition is obtained.

 The inorganic zinc paints used in the past are washed with a type in which powders such as zinc are mixed with inorganic polymer silicone paints and modified silicones just before use. However, the electrical conductivity cannot be exhibited unless it is contained about 90 to 96% by mass of zinc powder as a solid metal component. In addition, organic or inorganic antifouling paint mixed with single scale metal powder is also included, but since it is a mixture of single metal powder, the anti-fouling (anticorrosion) effect is uneven due to irregular arrangement in the coating film. In addition, the conductivity cannot be exhibited unless the metal solid component is contained in an amount of 90 to 96% by mass of zinc powder.

 On the other hand, in the resin composition according to the present invention, it is possible to impart conductivity by blending a small amount of the clad scale powder, and it is possible to secure good anti-corrosion properties. It becomes. Further, when 90 to 96% by mass of the metal powder is blended, the formed surface becomes rough and porous, so that the effect is not exhibited unless the film thickness is 100 m or more. In the film formation by the resin composition, even if the film thickness is about 50 μm, the effect is exhibited. The resin composition of the present invention has excellent workability such that it can be applied simply as in the conventional coating method, and even if the amount of the metal powder is reduced, the obtained film has an inorganic zinc paint, organic In addition to exhibiting excellent antibacterial properties equivalent to or better than inorganic antifouling paints, hot dip galvanizing and metal spraying methods, it has various advantages such as eliminating the need for troublesome post-treatment such as sealing treatment.

As described above, in the resin composition in which the clad scale powder is mixed with the curable silicone resin, the hydrolyzable reactive group OR (a) of the curable silicone resin is hydrolyzed. It reacts and adsorbs in a hydrogen bond with the hydroxyl group on the metal surface (M e), and then undergoes a dehydration condensation reaction to form a chemical bond (Me 1 O—S i -OR), which is strong in the steel structure A film adhered to can be formed. In addition, the fine powder of the clad-like scale foil is a heterogeneous metal bond (for example, OR—A 1 — O—S i —) by hydrolysis / dehydration condensation reaction. O-Zn-O-Si—partial chemical bonding state such as OR), so that the metal powder can be firmly fixed in the film and applied to the cured silicone resin. Since it has no residual harmful components and has excellent weather resistance, it exhibits durable and non-polluting anti-corrosion properties. The curable silicone resin preferably used in the present invention contains an alkoxysilyl group, which is a silane compound represented by the following general formula (1), or Or a part (co) hydrolysis condensate of one or a mixture of two or more.

R ^ S i (OR 2 ) 4 _ N- (1)

R 1 in the general formula (1) may be the same or different, ash? It is an unsubstituted or substituted monovalent hydrocarbon group having a β number of 1 to 10, and physically includes a methyl / le group, an ethyl group, a propyl group, a butynole group, a hexyl group, an octyl group, Examples include alkyl groups such as decyl groups, cycloalkynole groups such as cyclohexyl groups, vinylenole groups such as vinylol groups, vinylol groups, arylene groups such as phenol groups, tolyl groups such as vinyl groups. It is done.

R 2 is an alkyl group having 1 to 3 carbon atoms, an acyl group having 23 carbon atoms, or an alkoxyalkyl group having 3 to 5 carbon atoms, specifically, a methyl group, An alkyl group selected from an ethyl group, a propyl group, an isopropyl group, an acyl group such as an acetyl group, a methoxetyl group, an ethoxychetyl group, a propoxycetyl group, a methoxyp pill group, an etoxy group Examples include an alkoxyalkyl group such as a xypropyl group.

 N in the above general formula (1) is an integer of 0 to 2 (N = 0, 1, 2), but the curability of the resin composition, the surface hardness of the cured coating film, and the adhesion to the substrate In view of the above, in the curable silicone resin, the proportion of N = 1 silan compound or its part (co) hydrolysis condensate is 30 mol% or more Is preferred, more preferred is 40-1

0 0 mole 0/0 der Ru's good. In addition, the proportion of the N = 0 silane compound / or its partial (co) hydrolysis condensate is preferably 40 mol% or less in the curable silicone resin. However, the proportion of the silane compound of N = 2 and / or its partial (co) hydrolysis condensate may be 60 mol% or less in the curable silicone resin. It is preferable. As a curable silicone resin component, N = l silane compound

In addition to / or its part (co) hydrolysis condensate, N = 0 silan compound and z or its part (co) hydrolysis condensate, the surface hardness of the cured film (resin film) However, if the amount is too large, cracks may occur on the coating surface.

Use of N = 2 silane compound and / or its partial (co) hydrolysis condensate gives toughness and flexibility to the cured coating, but if the amount is too large, sufficient crosslinking density is obtained. The surface hardness and the hardenability may decrease.

 Examples of such silan compounds and their partial (co) hydrolysis condensates include tetramethoxysilan, tetraxysilan, methylmethoxysilan. , Methyltriethoxysilane, methyltrisoxypoxyllan, methyltriacetoxysilan, methyltris (methyxoxy) silan, methyltrisyl (Methoxypropoxy) silan, ethyltrimethoxysilan, probuilt-trimethylsilan, butyl-dimethylsilanyl-hexyltrimethoxysilan, octyl-methyl Lime xysilan, T sill 卜 V xyxy lanthanum π hexyl 卜 Dimethyl xysilan, vinyl 卜 V 卜 xysilan ゝ vinyl 卜 V xyxylan, aryl 卜y Xysilan, phenyl 卜 lime xysilan phenoxysilan, 卜 卜 卜 xysilan, cyanoethyl 卜 V ethoxysilan, y ― gushi K Mexyxylan, Uniglycisic P-Pill 卜 Jexy xylan, β ― (3,4 hexoxy π xylyl) ethyl 卜 dimethysilane, V ― metal V π xyp Mouth pill 卜 V 卜 xysilan, Ύ ― V V xy p n ル 卜 V methoxysilan, y ― ァ

 Henopir Trimele xylsilan, Ύ ァ ァ, 口 ピ 卜 y 卜 xysilan, N N β (ァ ァ チ ル) チ ル ァ ァ

Hemp mouth pills 卜 V mexylsilan, N 1-phenyl-― Aminopor pill meristyl silane, y ― Mel force top pill P pill 卜 Dimethyxylalanine, Dimethyl dimethyl xysilan, dimethyl methyl xysilan, dimethyl dimethyl xysilan, methyl ethyl dimethyl silan, methyl propyl dimethyl xysilan, methyl vinyl dimethyl xysilan, methyl dimethyl dimethyl silane Two Dimethyoxysilan, Diphnioretoxysilan, Methinolev Distiller Dimethyxylsilan, γ — Propinomethyl dimethoxysilan,

3 3 1 L-oxypropylmethyldimethyoxysilan, Υ-amino propylenemethylediethyloxysilan, N-β (anoxyl) γ-amino propylmethylmethyoxysilan, monomelic power Examples thereof include alkoxysilanes such as pyrmethyldiethyloxysilan or acyloxysilanes, and partial (co) hydrolysis condensates thereof.

Among these silane compounds and silane compounds as precursors of partial (co) hydrolysis condensates, when used as electromagnetic shielding agents, versatility, cost and antifungal agents From the viewpoint of the curability of the film, the coating film (film) characteristics, etc., R 1 in the general formula (1) is a group selected from a methyl group and a phenyl group, and R is a methyl group. It is preferable to use a silan compound which is a group selected from a propyl group, and specifically, methyl 卜 V methoxysilane, methyltriethoxysilane, and phenyl 卜. Examples include V-methoxysilane, phenethylsilane, dimethyldimethylsilane, dimethylmethoxysilane, dimethylmethoxysilane, and diphenyldiethoxysilane.

 Partial (dfc) hydrolyzed ¾ 'As the mouthpiece, the above and other silane compounds 2 and

 1 to 100 mer (which is a cis-xane unit obtained by removing 2 moles of alcohol by allowing 1 mole of water to act on the silane compound 2 monole), preferably 2 50-mer, more preferably <2 to 30-mer can be preferably used, and a part derived from two or more silane compounds (using hydrolyzed condensate). You can also.

As the curable silicone resin that may be used in the resin composition of the present invention, the above silane compound or its partial (co) hydrolyzed condensate may be used alone. However, it is also possible to use two or more types of silan compounds or partial (co) hydrolysis condensates with different structures, or to use silan compounds and partial (co) hydrolysis condensates in combination. . However, the volatility, workability, and curability of the components when mixing and painting From the viewpoint of the ease of water and the amount of alcohol generated by moisture curing, it is preferable to use a partial (co) hydrolysis condensate as an essential component. Hydrolyzed condensates can be used as those sold as silicone diol sesame. , Anore Le, as a hydrolyzable sila down the starting compounds of the can and this for connexion produced by the and this that the byproduct is removed such as hydrochloric acid, example 7 places the I'll have Do are two 2 key Shishira emissions such When Nyxoxysilanes are used, the use of acids such as hydrochloric acid, sulfuric acid, etc., sodium hydroxide, sodium hydroxide, etc. Al forces such as hydroxide and triethylamine In the case of direct production from chlorosilanes, water or alcohol can be reacted with hydrochloric acid produced as a catalyst. It ’s good.

 In addition, the viscosity of the curable silicone resin component at 25 ° C when considering the workability when mixing each component, the coating properties of the antifungal agent and electromagnetic shielding agent, and the antifungal effect and shielding effect. (Mechanical viscosity) is preferably 1 ~

20 mPa • s, more preferably 5 to 50 mPa · s, and even more preferably <10 to 30 Pa • s <Good, viscosity and hardening The above-mentioned silane compounds can be used to adjust the properties, and in some cases, solvent components such as allyls can be used in combination. Furthermore, for the purpose of improving the adhesion to the substrate, a silane coupling agent having an epoxy group, an amino group, a mercapto group or the like is blended, or the coating film properties are improved. It is possible to use a part of silanol resin containing silanol group.

In the resin composition of the present invention, it is also effective to contain a metal alkoxide if necessary. The metal alkoxide penetrates between the three-dimensional crosslinks formed by the curable scene resin, and has a moisture content. In contrast, the metal ion released increases the conductivity of the film, enhances the sacrificial anode I response and electromagnetic shielding characteristics, and improves the anti-fouling and electromagnetic shielding effects. Can As the types of metal alcoholides, various alkoxys such as A1, Li, Sn, Zr, and Fe ゝ Zn can be used, but from the viewpoint of metal ionization. S i alkoxide cannot be used. Of these, A 1 alkoxide is particularly effective in increasing conductivity, and can be preferably used. Examples of the alkoxy group may include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a hexyloxy group, and a phenoxy group. The isopoxy group is preferred because of its ease of handling. Particularly preferred are ar and two-sodium propoxy groups.

 When the above metal alkoxide is used, it may be used in combination with alcohols. As the rules used in this case, -valent alcohols are preferred, and 2 -propanol is particularly preferred. The content of the metal alkoxide is 1 to 20 parts by mass with respect to 100 parts by mass of the resin component from the viewpoint of the ratio of the metal powder and metal ion and the prevention of gelation of the silicone resin. The range should be 8 and preferably 8

˜15 parts by mass.

 In the resin composition of the present invention, if necessary (when a curable silicone resin is used), the curable silicone resin containing an alkoxy group is moisture-cured. Examples of such curing catalysts include acids such as phosphoric acid; organic amines such as triethanolamine; organic compounds such as dimethylenolean acetate. Amines salts; Tetramethinoreamonium hydride quaternary amine salts such as sodium carbonate; Alkaline of organic acids such as sodium hydrogen carbonate (earth) ) Metal salts; Amino alkyl silane compounds such as hepro-propyl ethoxysilane; Powerful rubonic acid metal salts such as octyl / zinc acid; Dioctyltin dilaur Organic tin compounds such as lathe; Tetra sopro piltitane 卜, Te ラ ブ love Titanium phosphate esters such as Ruchitane bets; Asechiruase preparative Na Rumi two © beam metal chelate Bok compounds such salts thereof

The compounding amount of the curing catalyst varies depending on the type of curable silicone resin component used and the desired curing rate, but the curability and workability are too small and too large. since there m force s storage stability and film properties are generally curable sheet re corn resin component:. 1 0 0 parts by weight 1 D. 1 to 20 parts by mass, preferably 0-

D ~ 1 0

 It is better to mix in the Satobe range.

 In the resin composition of the present invention, various pigments, dyes, fillers, adhesion improvers, leveling improvers in addition to the above components, as long as the effects of the present invention are not hindered depending on the purpose of use. It is optional to add inorganic and organic ultraviolet absorbers, storage stability improvers, plasticizers, anti-aging agents, etc. In producing the resin composition of the present invention, the The scale-like fine powder may be mixed in the resin. Specifically, the resin component and the metal alkoxide are first mixed thoroughly in a dispersion stirrer,

Add a certain amount of clad scale fine powder composed of (a) component and (b) component • Mix and agitate for 60 minutes to 120 minutes. In addition, it is preferable to perform this mixing in a nitrogen atmosphere in order to prevent hydrolyzable groups such as alkoxy groups from hydrolyzing due to water contamination.

1 1

 As a base material on which the resin composition of the present invention is coated, a steel material such as pig iron or the like is representative for the purpose of imparting anti-rust properties. For example, wood, gypsum board materials, concrete materials, and plastic materials can be cited as places where the purpose is to impart electromagnetic shielding properties. Examples of the coating method (coating method) at this time include a dipping method, a spray method, and a brush coating method, and it is also possible to perform on-site coating. In addition, the coating amount of the resin composition varies depending on the type and purpose of the substrate, but generally the coating thickness after curing is in the range of 120 to 30 ^ um. Preferably, it is in the range of 70 50 / zm.

The curing conditions of the resin composition are not particularly limited. However, since the film is cured by moisture in the air to form a film, it is not particularly necessary to perform heating and other operations at room temperature. It can be dried by leaving it for about 2 minutes to 2 hours (surface tack-free state), and then the hardening reaction can be completed by leaving it for several hours to several days. Although it is optional to perform additional heat treatment within a range that does not adversely affect the properties of the substrate to be coated and the coating film, it is possible to increase the temperature from the initial stage of the drying process. When exposed to water, the silane compound in the curable silicone resin will evaporate, and the moisture necessary for curing will not be supplied. The resin composition according to the present invention bonds dissimilar metals in the form of a bond by chemical bonding, becomes stronger with time due to the sharing of internal electrons between metals, and cracks and peels off. A film that can be permanently bonded can be formed, and a resin composition-coated member having excellent antibacterial and electrical conductivity can be obtained by coating such a film on the substrate surface. Examples Hereinafter, the effects of the present invention will be described more specifically by way of examples. However, the present invention is not limited by the following examples, and may be adapted to the purpose described above and below. The design can be changed as appropriate within the scope, and these are all included in the technical scope of the present invention.

 As the components in the resin composition of the present invention, the following (A) to (H) were prepared, and using these components, the resin compositions of Examples 1 to 8 below were prepared.

 (A) Ingredients (Zinc Z aluminum fine powder formed in the clad scale foil powder, Nickel aluminum fine powder formed in the clad scale foil powder, Nickel / "copper fine powder, formed into a ladder-like scale foil powder) (A—1): The ratio of the clad component is 100% by mass in total of zinc / aluminum fine powder. In contrast, zinc powder: 88% by mass, aluminum powder: 12% by mass; size (particle size): 20 to 40 / zm, thickness:! ~ 5μΐη (purity 9 8 %)

(Α—2): Cladding component ratio is Zinc Z Aluminum Fine Powder Total 100 mass 0 /. Zinc powder: 90% by mass, aluminum powder: 10% by mass; Size (particle size): 20 to 40 m, thickness 4 to 7 / χ πι (purity 9 8%)

(A - 3): click La head component ratio, with respect to nickel aluminate two © beam powder Total 1 0 0 mass 0/0, nickel powder: 9 0 wt%, aluminum two © beam powder: 1 0 mass 0/0; size (particle diameter): 1 5 ~ 3 0 m , thickness 3-6 111 (pure 9 8%) (A-4): The ratio of the clad component is nickel / copper fine powder total 100 mass%, nickel powder: 98 mass%, copper powder: 2 mass%, size ( Particle size): 1 5 to 30 μ ιη, thickness 3 to 6 ΠΙ (purity 98%) (Β) component (curing silicone resin)

 (Β _ 1): Partially hydrolyzed condensate of methyltrimethoxysilane (average degree of polymerization: 5, viscosity 5 m Pa ■ s

 (B-2): Partial hydrolysis-condensation product of methyltrimethoxysilane (average polymerization degree: 25, viscosity: 15 mPa · s

(B - 3): Main Tilt Li E preparative Kishishi run-8 5 mole 0/0 and Ziv et Niruji main preparative Kishishira down 1 5 mol% and partial cohydrolysis-condensation product of (average polymerization degree: 1 0, viscosity : 3 5 m P a · s)

 (B-4): Partially co-hydrolyzed condensate of 70% by mole of methyltrimethoxysilane and 30% by mole of dimethyldimethoxysilane (average degree of polymerization: 20; viscosity: l OO m P a · s)

 (B-5): Dimethyldimethoxysilan

 (C) component (metal alkoxide)

 (C— 1): Aluminum Triiso Proboxide

 (D) Other components (curing catalyst, solvent)

 (D — 1): Di-n-butoxy ether acetate aluminum

 (D— 2): Tetriso propoxy titan

 (D— 3): Anhydrous ethanol

 (E) component (nickel fine powder formed in scale foil shape)

 (E-1) Size (particle size): 10 to 30 / z m, thickness l to 5 / x m (purity 98%)

 Component (F) (Nickel fine powder formed into granules)

 (F — 1) Size (particle size): 7 to 10 m (Purity 9 8%)

 Component (G) (graphite fine powder formed in a scale foil shape)

 (G— 1) Size (particle size): 4-8 μ πι

 (Η) Ingredients (silver fine powder formed into granules)

 (Η— 1) Size (particle size): 0.5 to 2 μ πι (purity 98%)

[Example 1] (1) In a nitrogen atmosphere at room temperature, (B-1): 6 2 parts by mass, (B-2): 18 parts by mass, (B 5): 2 parts by mass was stirred and mixed, and (D-1): 8 parts by mass was further added and stirred as a curing catalyst. To this mixture of components (B) and (D), (C 11): 10 parts by mass as a metal alkoxide of component (C) was further added and stirred and mixed again.

 (2) (A-1): 100 parts by mass were prepared as the component (A).

 (3) (B), (C), (D) component mixture prepared in step (1): 45 parts by mass and (A) component mixed powder prepared in step (2): 55 mass The mixture was mixed and thoroughly stirred and mixed in a nitrogen atmosphere while maintaining the temperature at 28 ° C. or lower by water cooling using a dispersion stirrer.

 (4) For viscosity adjustment, the mixture of components (A) to (D) prepared in step (3): 100 parts by mass, and as a solvent, (D-3): 4 parts by mass Then, the mixture was stirred and mixed to obtain a resin composition. The viscosity of this resin composition was 60 mPa · s.

 [Example 2]

 (1) The amount of each component used in Example 1 was determined in the same manner as in step (2) except that (A) component (A-2): 100 parts by mass was prepared. Obtained. The viscosity of this resin composition is 50 m Pa · s.

 [Example 3]

(1) The amount of each component used in Example 1 was determined in the step (1) as the curable silicone resin of the component (B): (B-2): 18 parts by mass, (B-3) : 6 8 parts by mass, (B-5): 2 parts by mass with stirring, and further as a curing catalyst (D-2): The same except that 2 parts by mass were added and mixed Adjustment was performed to obtain a resin composition. The viscosity of this resin composition was 90 m Pa · s.

 [Example 4]

 In step (1), the amount of each component used in Example 1 was determined as (B-1): 40 parts by mass, (B-4) as (B) component curable silicone resin. : 30 parts by mass, (B-5): 1 2 parts by mass were stirred and mixed, and (D-1): 8 parts by mass was added and mixed as a curing catalyst. A resin composition was obtained. The viscosity of this resin composition was 90 m Pa · s.

 [Example 5]

 The same amount of each component used in Example 1 was prepared except that (A-3): 100 parts by mass was prepared as component (A) in step (2). Got. The viscosity of this resin composition was 90 m Pa · s.

 [Example 6]

 (1) In a nitrogen atmosphere at room temperature, (B-1): 5 9 parts by mass, (B-2): 18 parts by mass, (B 5): 2 parts by mass were stirred and mixed, and (D-1): 8 parts by mass were further added as a curing catalyst and stirred. To this mixture of components (B) and (D), (C-1): 12 parts by mass of a metal alkoxide of component (C) was further added and stirred and mixed again.

 (2) As component (A), (A-4): 94.5 parts by mass were prepared.

(3) (F-1): 5 parts by mass were prepared as the (F) component, and (G 1 1): 0.5 part by mass as the (G) component.

(4) Mixture of components (B), (C), (D) prepared in step (1): 4 0 parts by mass and (A), (F), (G) components prepared in steps (2) and (3): 60 parts by mass were mixed at 28 ° C by water cooling using a dispersion stirrer. While maintaining the following, the mixture was sufficiently stirred and mixed under a nitrogen atmosphere.

 (5) For viscosity adjustment, (A) to (D), (F),

(G) Component mixture: 100 parts by mass, and further as a solvent (D

― 3): 5 parts by mass were added and mixed with stirring to obtain a resin composition. The viscosity of the resin composition was 60 m Pa · s.

 [Example 7]

 (1) The amount of each component used in Example 6 was determined in step (4).

Mixture of (B), (C), (D) component: 45 parts by mass and (A), (F), (G) component prepared in steps (2), (3): 55 parts by mass A resin composition was obtained by blending and performing the same operation except that the mixture was sufficiently stirred and mixed in a nitrogen atmosphere while maintaining at 28 ° C. or lower by water cooling using a dispersion stirrer.

The viscosity of the resin composition 5 0 m P a · s at a thickness 7 this 0

 [Example 8]

 (1) The amount of each component used in Example 6 was determined in step (1).

As the component (E), (E-1): 94.5 parts by mass was prepared. (B), (C), (D) component mixture prepared in step (4): 40 parts by mass, step

(E), (F), (G) components prepared in (2) and (3): 60 parts by mass

Then, using a dispersion stirrer, the mixture was sufficiently stirred and mixed under a nitrogen atmosphere while maintaining the temperature at 28 ° C. or lower by water cooling.

 (B)-(D), (E)-created in step (4) for viscosity adjustment

The mixture of component (G): 100 parts by mass, (D 13): 5 parts by mass were further added as a solvent, and the mixture was stirred and mixed to obtain a resin composition.

The viscosity of the resin composition was 55 mPa · s. [Comparative Example 1]

 The amount of each component used in Example 1 was agitated in the step (1) (B 1 1): 7 2 parts by mass, (B_2): 18 parts by mass, (B-5): 2 parts by mass Further, (D-1): 8 parts by mass as a curing catalyst was added and mixed and stirred. At this time, the component (C) was not used, and the other adjustments were made in the same manner to obtain a resin composition. The viscosity of this resin composition was 60 mPa · s.

 [Comparative Example 2]

 A galvanized steel sheet was prepared. This galvanized steel sheet was obtained by immersing a test piece of the same size as the test piece produced in the example, and having a coating thickness of 60 μπιι.

 [Comparative Example 3]

 An organic zinc paint was prepared. An acrylic resin product with a zinc content of 98% by mass was used.

 [Comparative Example 4]

 Inorganic zinc paint was prepared. An acrylic silicate resin product with a zinc content of 98% by mass was used.

 [Comparative Example 5]

 (1) In a nitrogen atmosphere at room temperature, ()) component curable silicone resin (Β — 1): 5 9 parts by mass, (Β— 2): 18 parts by mass, (Β 5): 2 parts by mass were stirred and mixed, and (D-1): 8 parts by mass were further added and stirred as a curing catalyst. To this mixture of components (B) and (D), (C 1): 12 parts by mass was added as a metal alkoxide of component (C), and the mixture was stirred and mixed again.

(2) (E-4): 94.5 parts by mass were prepared as the component (E). (3) (F —): 5.5 parts by mass were prepared as component (F).

 (4) Mixture of components (B), (C), (D) prepared in step (1): 40 parts by mass, prepared in steps (2), (3) (E;), (F) Ingredients: 60 parts by mass were blended and sufficiently stirred and mixed in a nitrogen atmosphere while maintaining at 28 ° C. or lower by water cooling using a dispersion stirrer.

 (5) To adjust viscosity, (B) to (D), (E),

Mixture of component (F): 100 parts by mass, (D 13): 5 parts by mass were further added as a solvent, and the mixture was stirred and mixed to obtain a resin composition. The viscosity of this resin composition was 60 mPa · s.

 [Comparative Example 6]

 The amount of each component used in Comparative Example 1 was prepared in step (2) as follows: (E-1): 94 parts by mass, (F-1): 5 parts by mass, (H-1): 1 part by mass Except for the above, the same adjustment was performed to obtain a resin composition. The viscosity of this resin composition was 55 mPa · s.

 For each of the resin compositions, the anti-rust opto-electromagnetic shielding property was evaluated by the following method.

 [Preparation of anti-rust test piece and anti-rust test method]

 Surface treatment of steel plate (material: SPCC, 1.0 mm X 7 O mm X l 5 O mm) with sandblast (detail: average surface roughness ζ ζ 15 μμιη), followed by 2-propanol Degrease, wash, and dry with an air spray gun. Apply each resin composition to a coating thickness of 60 μπιι at a temperature of 25 ° C and humidity of 55%. The cured film was left to stand for a day and used as a test piece.

 Each of the above specimens is a type of zinc plating test, and an anti-fouling test is conducted according to the accelerated durability test (JISH 8 5 20) (test temperature: 50 ± 2 ° C, 3 60 hours), the anti-mold property was evaluated by visually observing the presence or absence of soot.

[Measurement of electromagnetic shielding properties] Measured by Dovantest (near electromagnetic field). At this time, the measurement specimen used the resin composition of Example 8 having low electrical resistance.

 Table 1 below shows the blending amount (mass%), electrical resistance value, and viscosity at 25 ° C of each component in each resin composition. In addition, Table 2 below shows the results of the antifungal test for each resin composition, together with the curability of the resin composition. The electromagnetic shielding properties are shown in Fig. 1 (electric field) and Fig. 2 (magnetic field).

Table 2

 These results can be considered as follows. First, an embodiment that satisfies the requirements defined in the present invention:! It can be seen that the products with ˜4 exhibit excellent antibacterial properties, and the electromagnetic shielding properties are those of Example 8 with low electrical resistance. The results are measured in the chapter β in the frequency range of 0 z ζ 1 GHz, but the sealing effect increases as the frequency becomes higher, and the electric field is 60. d

It is possible to understand that _ and B are equal to or greater than B (frequency band of 500 Μ Η ζ). In the present invention, (a) Z n and / or A1 and (b) a fine powder of clathrate scales consisting of Cu and / or Ni can be easily applied by blending the resin with a small amount of metal. Resin that has excellent anti-corrosion properties that are equivalent to or better than dt and have excellent anti-shielding properties that cut off electromagnetic waves, as well as dt when it is electrically conductive with powder blending The composition included in the realization

Claims

The scope of the claims
1. A clad scale fine powder composed of (a) Zn and / or A1 and () Cu and Z or Ni was formed into a resin. A resin composition having excellent anti-bacterial properties and conductivity, characterized by being a product.
 2. Further, a claim selected from the group consisting of Mn, Mg, Mo, Li, C, and Ag: a powder of one or more elements or an alloy powder. 1. The resin composition according to 1.
3. The coconut oil is represented by the general formula: R 1 N Si (OR 2 ) 4 N (where R 1 is a hydrocarbon group having 1 10 carbon atoms, and R 2 is 1 to An anoalkyl group of 3 or 2 or 3 or an alkenyloxy group of 3 to 5 carbon atoms, and N is an integer of 0 to 2), or The resin composition according to claim 1 or 2, which is a curable silicone resin comprising the partially hydrolyzed condensate.
 4. The resin composition according to any one of claims 1 to 3, which further contains a metal anoloxide (excluding si alkoxide).
 5. A resin composition-covered member excellent in anti-rust and electrical conductivity, which is obtained by coating the surface of the substrate with the resin composition according to any one of claims 1 to 4
PCT/JP2005/006690 2005-01-06 2005-03-30 Resin composition excellent in rust inhibition and electroconductivity, and member coated with the resin composition WO2006073004A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2005001924 2005-01-06
JP2005-001924 2005-01-06

Publications (1)

Publication Number Publication Date
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105219261A (en) * 2015-11-03 2016-01-06 吴朝霞 A kind of corrosion-resistant sewer pipeline

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57113505A (en) * 1981-01-07 1982-07-15 Matsushita Electric Ind Co Ltd Conductive composition
JPS63201047A (en) * 1987-02-14 1988-08-19 Sumitomo Cement Co Minute material with characterized coating layer
JPS63265803A (en) * 1977-05-17 1988-11-02 Studiengesellschaft Kohle Mbh Manufacture of nitrided alkali metal
JPH0222333A (en) * 1987-10-29 1990-01-25 Hiraoka & Co Ltd Amorphous metal-containing flexible sheet
JPH0528829A (en) * 1991-07-12 1993-02-05 Tokyo Cosmos Electric Co Ltd Conductive coating and conductive film formation thereof
JPH065116A (en) * 1992-06-19 1994-01-14 Shin Etsu Polymer Co Ltd Low melting point metal joined type anisotropic conductive film
JPH08227613A (en) * 1994-10-20 1996-09-03 Internatl Business Mach Corp <Ibm> Conductive material and using method thereof
JPH1145618A (en) * 1997-06-18 1999-02-16 Internatl Business Mach Corp <Ibm> Conductive paste structure and manufacture thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63265803A (en) * 1977-05-17 1988-11-02 Studiengesellschaft Kohle Mbh Manufacture of nitrided alkali metal
JPS57113505A (en) * 1981-01-07 1982-07-15 Matsushita Electric Ind Co Ltd Conductive composition
JPS63201047A (en) * 1987-02-14 1988-08-19 Sumitomo Cement Co Minute material with characterized coating layer
JPH0222333A (en) * 1987-10-29 1990-01-25 Hiraoka & Co Ltd Amorphous metal-containing flexible sheet
JPH0528829A (en) * 1991-07-12 1993-02-05 Tokyo Cosmos Electric Co Ltd Conductive coating and conductive film formation thereof
JPH065116A (en) * 1992-06-19 1994-01-14 Shin Etsu Polymer Co Ltd Low melting point metal joined type anisotropic conductive film
JPH08227613A (en) * 1994-10-20 1996-09-03 Internatl Business Mach Corp <Ibm> Conductive material and using method thereof
JPH1145618A (en) * 1997-06-18 1999-02-16 Internatl Business Mach Corp <Ibm> Conductive paste structure and manufacture thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105219261A (en) * 2015-11-03 2016-01-06 吴朝霞 A kind of corrosion-resistant sewer pipeline

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