KR800001402B1 - Anticorrosion primer coating composition - Google Patents

Abstract

Anticorrosion primers contained a poly(vinyl butyral) resin(I), an organo functional silane(II), a borate or polyphosphate H3PO4, a phenolic resin, and a metal powder. Thus, Hitanol 4020(phenolic resin) 11, I 9, KBM 303(II) 0.5, yellow Fe oxide 3, phthalocyanine blue 0.3, carbon black 0.3, Al polyphosphate 2.5, talc 1, Al powder paste 5, Ba metaborate 2.5, org. bentonite 1, BuOH 11,Me2CHOH 22.9, and PhMe 30 parts were kneaded and ground, and the mixt. was mixed(80 parts) with 20 parts mixt. of 85% aq. H3PO4 9, water 5, and Me2CHOH 86 parts to give a coating compn.

Description

Primary anticorrosive coating composition

The present invention,

(i) polyvinyl butylal resin,

(ii) organo functional sillanes,

(iii) borate compounds and / or poly phosphates,

(iv) phosphoric acid, (v) phenolic resins, and

(vi) A composition mill consisting of metal powder, generally for metals called wash primers, shop primers, etch primers or prefabrication primers. It relates to the field of primary anticorrosive coating compositions.

Conventionally, steel frames or metal plates for steel structures, such as ships and bridges, are completely rusted or mill scale removed by blasting in order to prevent rusting during processing and assembling. After that, it was common to coat a car anticorrosive coating, that is, a shop primer.

For example, D.A. Bayliss et al. Present and compare various prefabrication (shop) primers in the Journal of the Oil and Color Chemists 'Association, volume 51, pages 792-815 (1968), published by the Oil and Color Chemists' Association. . In such shop primers, there are wash primers, also referred to as chemical conversion coatings, in which chemical conversion and painting are performed simultaneously.

The wash primer is generally a composition in which polyvinyl butyl al resin is added as a colorant and phosphoric acid, chromic anhydride, zinc chromate, alcohol, and the like are added.

For example, there is a long-term exposure type wash primer obtained by an additive comprising a polyvinyl butylal resin and a phenol resin as a colorant, a zinc chromate pigment blended therein, and an alcohol solution of phosphoric acid. It coats and obtains adhesiveness with a metal and a favorable coating film. In other words, in order to be used in the case of a long period of time to the top coat, anticorrosiveness of about 6 months or more is required.

As an example of using a long term exposure type wash primer such as the foregoing, for example, US Pat. 3791850 is known.

However, since the conventional wash primer mixes zinc chromate pigment and chromic anhydride, there is a problem of so-called chromium pollution caused by chromium metal ions when the paint worker sucks spray dust generated during coating. .

In particular, in recent years, chromium pollution has become a widely social problem, and therefore, the emergence of pollution-free wash primer instead of this is strongly desired in the industry.

As part of this, attempts have been made to replace chromium-based pigments with other pollution-free pigments. However, the obtained coating film was a defect in corrosion resistance and adhesiveness, and the pollution-free wash primer currently available cannot be obtained.

Specifically, for example, a primary anticorrosive coating composed of polyvinyl butyl al resin, zinc chromate, and barium metaborate is known as Japanese Patent Application Laid-Open No. 48-44322.

However, this paint replaced only part of zinc chromate with barium metaborate, and the problem of safety and hygiene has not been solved at all.

In addition, as described in this publication, in the combination of polyvinyl butyl alginate and barium metaborate only, it is pollution-free since there is no chromium once, but the corrosion resistance is remarkably bad and cannot be used practically. Also known are pate compositions containing oil varnish, oil-modified alkido resins or drying oils as a colorant and containing barium borate (US Pat. No. 2,818,344) .The composition is a mold-resistance or choke- It gives a film with improved resistance to chalk-resistance and hardly has any characteristics as a wash primer.

Meanwhile, the use of molybdenum salt compounds as anticorrosive pigments for wash primers is known as US Pat. Nos. 3,272,663 and 3,528,860.

However, the paint coating is markedly bad.

Furthermore, a test is also undertaken to replace zinc chromate pigments with phosphates such as zinc phosphate (E. D. A. Bayliss et al.). Heat-resistant or corrosion-resistant consisting of white pigments such as silicon phosphate, zirconium phosphate, zinc phosphate, titanium phosphate, alkyd resin, epoxy rat, air-dried oil, phenol resin, polyvinylacetate, vinyl chloride resin, or polyvinyl acetal Although known as a paint (US Pat. No. 3,892,577), it also has very few characteristics as a wash primer. Moreover, it is known as a so-called zinc rich primer which mix | blended zinc powder in high concentration in the coloring agent as a kind of shop primer. However, this primer had the disadvantage that weldability was bad although it was very excellent in corrosion resistance.

That is, the steel material of this primer application | coating has a fault that welding strength becomes low by generation | occurrence | production of the pore (blow hole) by the gas which arises at the time of welding.

In addition, worker health and safety hygiene problems due to the generation of zinc fumes remain unresolved. In other words, in the recent shipbuilding industry, a so-called electrophotomarking process is employed in which an image is transparent and developed directly by electrophotographic on a coated steel sheet for the purpose of reducing labor. have. In this case, a paint having both conductivity and corrosion resistance is usually applied to the coated steel sheet. In particular, the wash primer which provided electroconductivity is used a lot.

Therefore, in the method of using the wash primer as described above, the solution of safety and hygiene problems due to chromium toxicity has been strongly demanded from the consumer.

As described above, an excellent shop primer has not yet been provided in terms of anticorrosiveness, top coatability, concave contact property, electrophotographic marking ability, workability (problem in environmental hygiene during work) and the like.

The present invention is intended to eliminate the drawbacks of conventional paint compositions in view of this point.

It is a first object of the present invention to provide a pollution-free primary anticorrosive coating composition which is free of chromium toxicity.

Another object of the present invention is to provide a primary anticorrosive coating composition which gives a coating film excellent in anticorrosion, welding, blownability, adhesiveness, and the like.

In addition, the present invention is to provide a primary anticorrosive coating composition excellent in electronic marking properties.

In other words, the present invention relates to (i) polyvinyl butyl resin, (ii) organo functional silanes, (iii) borate compounds and / or poly phosphates, (iv) phosphoric acid, (v) phenolic resins. And (vi) long-term exposure type primary anticorrosive coating composition consisting of metal powder.)

As the polyvinyl butyl al resin used in the present invention, those having an average degree of polymerization of about 500-1,000 and a degree of butylation of 57 to 70 mol% can be used as they are usually commercially available. Moreover, as a silane coupling agent used for this invention, For example, General formula,

Wherein R 'is a divalent hydrocarbon group having 1 to 4 carbon atoms, R ² and R ³ are a monovalent hydrocarbon group having 1 to 4 carbon atoms, Z is a hydrogen atom or an aminoalkyl group, and m is 1 or 0 Amino alkoxysilane compounds, or general formula,

(Wherein R ₄ is a divalent hydrocarbon group having 1 to ₄ carbon atoms, R ⁵ and R ⁶ are a monovalent hydrocarbon group having 1 to 4 carbon atoms, Q is methacryl oxy group, acrylic oxy group, glycidoxy group or epoxycyclohex) N is an alkylalkoxysilane compound represented by 1).

Specific examples of the former compound include amino methyltrimethoxysilane, aminomethylethoxysilane, N- (β-aminoethyl) aminomethyltrimethoxysilane, aminomethyldiethoxysilane, N- (aminoethyl) aminomethyltribu Oxysilane, γ-aminopropyltriepoxysilane, γ-aminophoromethylmethyldiethoxysilane, γ-aminoisobutyltrimethoxysilane, N- (β-aminoethyl) -γ-amino propyltrimethoxysilane and N -(β-aminoethyl)-[gamma] -propylmethoxysilane and the like can be enumerated.

Moreover, as a specific example of the latter compound, (gamma)-glycidoxy propyl metal dimethoxysilane, (beta)-(3, 4- epoxy cyclohexyl) ethyl trimethoxysilane, (beta)-(3, 4- epoxy cyclohexyl) ethyl tree Ethoxysilane, (beta)-(3, 4- epoxycyclohexyl) ethylmethyldimethoxysilane, (gamma)-methacryloxypropyl trimethoxysilane, etc. can be mentioned.

Moreover, what contains vinyl groups, such as vinyl triethoxysilane and vinyl tris- (beta)-methoxy ethoxysilane, as another silane cappoly is also included in this invention.

The foregoing compound can be used as one kind or a mixture of two or more kinds.

In the present invention, the use of an alkoxysilane compound represented by the above formula 92) in the electric silane coupling agent is preferable.

More preferably, the use of β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxy propyltrimethoxysilane, and γ-methacryloxypropyltrimethoxysilane is preferable.

As the catalyst for the silane coupling agent, organic metal compounds such as dibutyltin dilaurate, dibutyltin di (2-ethylhexate), tin oleate, tin naphthenate, tin tin, and tin tin It is possible to add 1% by weight or less.

In addition, as a borate compound for use in the present invention, zinc borate _{(2ZnO · 3B 2 O 3 ·} 5H 2 O), boric acid barium _{(BaB 2 O 4 · H 2} O), boric acid, calcium _{(CaCo · B 2 O 3 ·} 5H ₂ O), potassium tetraborate (K ₂ B ₄ O ₇ · 5H ₂ O), calcium tetraborate (CaB ₄ O ₇ · 6H ₂ O), sodium tetraborate (Na ₂ B ₄ O ₇ ), barium tetraborate ( BaB ₄ O ₇ ), manganese tetraborate (MnB ₄ O ₇ · 8H ₂ O), zinc tetraborate (ZnB ₄ O ₇ ), tribasic borate (Li ₂ B ₄ O ₇ ), magnesium metaborate (Mg ₂ B ₂ O ₄ · 8H ₂ O), and alumino aluminate (Al ₂ O ₃ · B ₂ O ₃ ) and the like, and these are used as one kind or a mixture of two or more kinds.

Particular preference is given to the use of zinc borate and / or barium borate.

In addition, a condensed phosphate compound used in the present invention, in a phosphoric acid and 2 (denoted as X) 6-valent metal or an oxide thereof or a hydroxide in a proportion of a molar ratio _{P 2 O 5 / X = 1-6} , in a heated It is a compound obtained by condensation reaction. Examples of electricity X include metals such as Mg, Al, Ca, Zn, Mn, Fe, and Ba: MgO, Al ₂ O ₃ , CaO, Zno, oxides such as MnO ₂ , FeO, MoO ₃ , BaO, and WO ₃ : Mg (OH ) _2, can be exemplified hydroxides such as _{Al (OH) 2, Zn (} OH) 2, Ba (OH) 2, Fe (OH) 3.

The electrocondensed phosphate compound is used as one kind or a mixture of two or more kinds. Especially preferably, they are 1 type, or 2 or more types of mixtures of condensed zinc phosphate, condensed aluminum phosphate, and condensed calcium phosphate.

As the condensed aluminum phosphate, commercially available K-50, K-80, K-82 (manufactured by KKK), HB-Hardner (trade name, manufactured by Weiss), and the like can be used.

Furthermore, phosphoric acid used in the present invention refers to an acid obtained by hydration of diphosphate pentaoxide.

Specifically, metaphosphoric acid, pyrophosphoric acid, oxophosphoric acid, triphosphoric acid, tetraphosphoric acid, etc. can be mentioned. These can be used as 1 type, or 2 or more types of mixtures.

Moreover, the metal powder used for this invention should just be what can provide electroconductivity to a coating film. Usual metal powders of about 500-180 mesh sizes are available.

Specifically, aluminum powder; Alloy powders of one or two or more metals such as aluminum, zinc, magnesium, tin, silicon, copper, and manganese. Aluminum powder is particularly preferable.

The metal powder in the present invention may be used as one kind or a combination of two or more kinds.

Moreover, what is marketed as a normal coating material can be used as it is as an electric phenol resin as it is. This resin is obtained by condensation reaction between phenols and aldehydes in a conventional manner and has an average molecular weight of about 100-1,000.

In the coating composition of the present invention, the borate compound and the condensed phosphate compound are each 9 / 1-1 / 9 alone or in a weight ratio, based on 100 parts by weight of polyvinyl butyl al resin, preferably a mixture of 8 / 2-4 / 6. 20-350 parts by weight, preferably 50-250 parts by weight, silane coupling agent 1-25 parts by weight, preferably 3-15 parts by weight, 5-50 parts by weight of phosphoric acid, preferably 15-40 parts by weight The ratio gave the preferable result.

In the example of the electrical ratio, when the mixture of the borate compound and the condensed phosphate compound or the silane coupling agent was outside the electric range, all showed a tendency to deteriorate the corrosion resistance.

The phenol resin is preferably 200 parts by weight or less, preferably 70 to 170 parts by weight, based on 100 parts by weight of vinyl butyl al resin. In the former example, when it exceeds 200 weight part of phenol resins, adhesiveness with a top coat will fall.

In the coating composition of the present invention, the metal powder is used in an amount of 10-130 parts by weight, preferably 15-90 parts by weight, based on 100 parts by weight of polyvinyl butyl resin.

When the metal powder does not reach 10 parts by weight, electrophotographic marking property is lowered, whereas when it is over 130 parts by weight, corrosion resistance and adhesion of the coating film tend to be lowered.

The paint composition of the present invention has an essential composition of the above-mentioned polyvinyl butyl al resin, phosphoric acid, borate and / or condensed phosphate compound, nepol resin, metal powder and silane coupling agent.

That is, polyvinyl butyl resin, phenol resin, metal powder, phosphoric acid, borate compound or combination of condensed phosphate (if silane coupling agent is absent) or polyvinyl butyl resin, phenol resin, its powder, phosphoric acid and silane coupling agent In combination (when there is no borate compound or condensate phosphate compound), it is hardly expected to obtain a coating film that satisfies the anticorrosive properties of the present invention.

Therefore, as the primary anticorrosive coating composition of the present invention, a composition consisting of polyvinyl butyl al resin, a silane coupling agent, a borate compound, a condensed phosphate compound, phosphoric acid, and a metal powder shows the best effect in corrosion resistance.

In the composition of the present invention, a polyvinyl butyl resin, a borate compound and / or a condensed phosphate compound, a silane coupling agent, a phenol resin, a metal powder, a solvent used in a conventional wash primer, an alcohol solvent, and, if necessary, Other pigments, such as extender pigments or colored pigments, may be blended together with other compatible resins or additives.

Phosphoric acid solvents, on the other hand, are made differently and mixed with the electric subject when used. The composition of this invention obtained in this way is used according to a normal coating method. For example, it is applied to coated objects such as iron, aluminum, and zinc.

The coating film obtained after application | coating strongly adheres to a metal by synergism of a borate compound, a condensation phosphate compound, a metal powder, and a silane coupling agent, and gives the coating film which has the outstanding anticorrosiveness and electrophotographic marking property.

In the primary anticorrosive coating composition of the present invention, a system comprising a polyvinyl butyl alginate, a phosphoric acid, a borate compound and a mixture of a condensed phosphate compound or a molybdate compound, a metal powder, and a phenol resin is used as a self-exposure wash primer. In this case, since the excellent anticorrosiveness, welding, melting property, electrophotographic marking property, and top coat are achieved, and it is a chromium-free pollution-free coating composition, the industrial value as a shop primer is extremely high.

Hereinafter, the details of the present invention will be described by way of examples.

In the examples, "part" or "%" denotes "parts by weight" or "% by weight".

Example 1

The main body from which the electro-aluminum alloy powder was removed was blended with a pot mill overnight, and then a prescribed amount of aluminum alloy conflict paste was added to the blend and lightly dispersed to make it uniform.

The coating composition of this invention was obtained by mixing in 80 parts of this subject matter and 20.0 parts of additives.

Next, it coated on the mild steel plate so that it might become a film thickness of 20 micrometers by air spray, and it dried for 3 days in the room of 20 degreeC and 75% RH, and used for the comparative test.

The results are shown in the third table.

Moreover, electrophotographic marking was performed as follows.

First, 10 parts of silicone resin (50% solution of xylol and toluol mixture), 10 parts of vinyl acetate resin (50% solution of xylol and toluol mixture), 50 parts of zinc oxide, 20 parts of xylol and 10 parts of ethyl acetate The resulting dispersion was mixed and dispersed in a ball mill, and the resulting dispersion was dried by heating and pulverized to prepare a photoconductive powder having an average particle of 20 µ.

Next, the electrical paint composition is uniformly dispersed in the coated mild steel plate with an electrostatic powder coating machine, and after the xenon lamp is projected through a positive circularity to obtain an electrostatic latent image, The photoconductive component powder of the part was selectively removed and collected by air pressure to obtain a mark. Then, it was settled by heating to 130 degreeC for 30 minutes.

[Example 2-12]

After mixing the subject matter shown by the compound of the following 1st table | surface similarly to Example 1, this subject matter and the additive were mixed in the ratio of 85:15, and it provided for the comparative test like Example 1. As a result, the anticorrosive property or electrophotographic marking property of the resulting coating film was excellent.

[Table 1]

Note 1) Brand name KBM # 403 (γ-glycidoxypropyl trimethoxysilane)

Note 2) Brand name KBM # 503 (γ-glycidoxypropyl trimethoxysilane)

Note 3) Equivalent mixture of KBM # 303 and KBM # 403.

Note 4) Electricity: KBM # 303

Note 5) Zinc borate (2ZnO, 3B ₂ O ₃ , 3.5H ₂ O)

Note 6) Equivalent mixture of barium borate (BaB ₂ O ₄ · H ₂ O) with zinc borate.

Note 7) The barium borate _{(BaB 2 O 4 · H 2} O)

Note 8) Condensed phosphate aluminium (same as Example 1)

Day 9) and was Zno of 85% phosphoric acid with P ₂ O ₅ / ZnO heated with stirring to a blended raw material so as to refrain from 3.5 (磁製) crucible, and 250 ℃ two hours later. Next, condensed zinc phosphate obtained by heating the contents in an electric furnace adjusted to 400 degreeC for 4 hours, and cooling and grinding.

NOTE 10 Mixture of 1: 1 (weight ratio) of condensed aluminum phosphate with condensed zinc phosphate.

Note 11) Product name Alpaste 1700NL (64% of solid content: mineral net pen solution) manufactured by Toyo Aluminum Co., Ltd.

Comparative Example 1-5

[Table 2]

1) Molly White 212 manufactured by Sherwin Williams Chemicals, Ltd.

Note 2) Electrical paste 1100N

The subject matter shown in the said 2nd table | surface was mix | blended like Example 1, this subject matter and the additive were mixed in the ratio of 80:20 (weight ratio), and it carried out similarly to Example 1, and provided for the comparative test. The results are shown in Table 3.

[Table 3]

Note 1) 5% NaCl aqueous solution for salt spray test

Note 2) Outdoor exposure test

◎ Table: No abnormality ○ Table: Slight rust and expansion △ Table: 10-50% rust and expansion. × Table: Almost front rust and expansion

Note 3) Judging by eyes

으로 표시.Note 4) of photoconductive component

Marked as.

Note 5) Deceleration time to 60 Lux (seconds)

As can be clearly seen in Table 3, the comparative test results, like the paint composition of the present invention, polyvinyl butyl resin, phenol resin, silane coupling agent, zinc borate compound and / or condensed phosphate compound, metal powder and phosphoric acid The paint composition (long-term exposure type: Examples 1,3,5,7,9,11), which is composed of a long anti-corrosive wash primer (Comparative Example 1), has excellent corrosion resistance, and furthermore, Because it is a non-polluting paint, it shows an excellent effect that is incomparable in workability (safety and hygiene of workers and the environment). In addition, electrophotographic marking properties were superior to the conventional ones and were inferior in performance. In addition, it is obvious from the combination that the weldability is further improved as compared with the conventional zinc rich paint.

In addition, in the conventional long-term exposure type wash primer, another anticorrosive pigment was added in place of the zinc chromate pigment, and the coating without chromium (Comparative Example 2-4) was significantly inferior to the conventional wash primer. There is no practical use at all.

Claims (1)

Primary anticorrosive coating composition, characterized in that consisting of.