JPS59179180A - Corrosion preventive coating method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anticorrosion coating method for forming a tough coating with excellent corrosion resistance on a coated object, particularly an iron plow.

2. Description of the Related Art Conventionally, resin linings for the purpose of preventing corrosion and rust of metals have been widely used mainly in various pollution control devices and chemical devices, tanks, oil tanks of ships, ship bottoms, and the like.

As for the 4K HP used for these resin linings, unsaturated polyester resin is used from the viewpoint of room temperature curability, on-site workability, price, etc., and as a lining method, tri F RP lining, that is, when lining construction is performed, Mix organic peroxide with resin in advance,
A commonly used method is to apply a sheet-like base material made of glass fiber to the base material to be lined, impregnate the base material with the resin using a felt roll or the like, degas it during lijing, and harden it.

Recently, in addition to this method, Eme has been jealous of a method in which a composition of extremely thin glass flakes mixed with resin is applied to the object with a trowel using a glass fiber base (flake lining). ), and some of them have already been put into practical use.

For example, the above-mentioned compositions include a coating composition for purulent retention and decoration containing fine glass flakes in an organic resin binder vehicle (Japanese Patent Publication No. 3/-2K3 Og), or a coating composition in a resin for lining. A lining material (Japanese Unexamined Patent Publication No. 52-30g!; No. 3) is known, which is filled with glass flakes as a corrosion-resistant material and glass fiber as a reinforcing material. In addition, by treating the surface of flaky glass with an appropriate substance, it can be made hydrophobic or leafing, and plastics, paints, insulating paper, etc. filled with this can be produced (% Publication No. 117-/Ag2/). is also known.

However, in consideration of various performance aspects of the film, the construction of the above compositions requires extremely thick films of 2 or more layers, and in addition, the construction cost is very high, so it is not suitable for general pot structures. It is not applicable, and as mentioned above, it is used for very limited and special purposes, and it is like a dormitory.

In addition, if flake lining, which is currently commonly used as a lining material, is used in a thin film of 2txrh or less in consideration of cost, it is impossible to obtain a predetermined film performance and is completely impractical.

In short, the problem with compositions using such glass flakes is how to arrange the glass flakes parallel to the base surface in order to take advantage of their characteristics and suppress the permeation of L'''C corrosive ions. It was.

By the way, flake lining, which conventionally uses glass flakes, is done by smoothing the film surface with a trowel or roller during construction, so that the alignment of the glass flakes in the coating film can be improved.
However, the construction method using trowels and rollers had the disadvantage that the processing costs were enormous and it was difficult to construct structures with complex shapes.

Therefore, a sprayable glass flake-containing composition has been proposed that solves such construction difficulties. (
For example, U.S. Patent No. 3A! ;39! ;'1) However, even when the composition is spray-painted, the glass flakes are not aligned parallel to the surface of the surface, and vary depending on the coating direction, and the variation is wide. The permeation suppressing effect was too good to be expected.

Therefore, as described above, there has been no known slip-out prevention method or composition in which the glass flakes are arranged substantially parallel to the base surface.

One of the problems with conventionally known unsaturated polyester resins is that they become hard due to radical polymerization, which inhibits hardening of the surface in contact with air.

Therefore, a method of adding paraffin wax or the like has been proposed. - This is due to the mechanism in which deeply added paraffin wax is pushed out to the coating surface during curing, and the surface hardens by cutting off air, but the conditions at the time of painting are very uncertain. This undermined the drawback of being easily influenced by

In addition, there are other types of resins in which the styrene evaporates without the addition of paraffin wax, resulting in an apparent surface dryness. However, since the surface layer of this glaze is not actually cross-linked, it swells, deteriorates, and appears chalky when exposed to hot water or other pedestrian fluids. In the case of inner coating II, there is a risk of contaminating the contents.
It also had various other drawbacks and was very inconvenient.

In the method of adding the shredded rough-in wax in No. 4 above, paraffin wax was added and if it floated sufficiently on the surface, there were few fatal problems, but in any case, wax floats on the surface. Due to the problem of delamination,
It is virtually impossible to recoat, so it is not suitable for cases where thick films require recoating or where repairs are necessary.

Furthermore, it is very difficult to control the floating of paraffin wax at a suitable level, and depending on the operating conditions, the floating may become insufficient, resulting in uneven hardening.

Furthermore, an unsaturated lt' IJ ester resin obtained by reacting a polybasic acid, a polyhydric alcohol, and a polyhydric alcohol allyl ether is used as a material having sufficient surface drying properties without cooling the paraffin wax. As an air-drying paint, it is widely used for painting furniture, interior decoration, household goods, etc.

However, this type of resin has inferior corrosion resistance compared to the conventional unsaturated polyester dog fat for heavy corrosion protection, and cannot be used for 1 corrosion protection.

The present invention aims to eliminate or improve the drawbacks of the prior art as described above. More specifically, a spray gun is used to arrange glass flakes almost parallel to the base surface of the object to be coated, resulting in excellent rust prevention, adhesion to the base, adhesion to the top coat, and durability such as weather resistance. The present invention relates to a corrosion-protective coating method that can provide a coating with a certain level of corrosion resistance.

That is, the present invention provides (112-functional bisphenol A-type epoxy resin) in which an unsaturated oro-lyester having allyl ether groups and carboxyl groups is bonded to the functional group in the 112-functional bisphenol A-type epoxy resin. Bo1 no ester tree U effect...100 heavy vessel part, thickness 0.3 to 70 microns, size/θ0 to 4t00 micron glass flakes...70 to 70 parts by weight, Ketonnoya A composition consisting of 0.7 parts by weight of monooxide, 0 parts by weight of hydroperoxide and 2,0 parts by weight of /17tVi peroxyester, O,!; An anti-corrosion coating method characterized by spray painting to a coating thickness of 300 to 1500 microns using a gun, and (a) an allyl ether group and a carboxyl group to the epoxy group in the 212-functional bisphenol A type epoxy resin. and (b) a modified unsaturated polyester having acrylic acid or methacrylic acid...700 parts by weight, thickness 0.0 to 10 microns, Glass flakes of 100 to 100 microns in size...10 to 70 nitrous kh1, ketone oxide...0.7 to 2.0 parts by weight, hydro/(-oxide and/or Ifi14 '−
Oxyester ・・・・・・0. A composition consisting of 2.0 parts by weight of S-2. An anti-corrosion coating method using a S~3m spray gun to spray paint to a thickness of 300~/300 microns.

Regarding.

The epoxy resin-modified unsaturated polyester resin used in the epoxy resin coating method of the present invention is as follows: (1) An unsaturated polyester resin having an allyl ether group and a carboxyl group in the nixyl group in the suction-functional bisphenol A type epoxy resin ( (hereinafter abbreviated as allyl ether group-containing unsaturated ester)? It consists of an epoxy resin-modified unsaturated polyester obtained by cooling and a polymerizable monomer, or (2) an allyl ether group-containing unsaturated polyester and acrylic acid are added to the epoxy group in bifunctional bisphenol A@epoxy chili resin. or methacrylic moromi (hereinafter abbreviated as (meth)acrylic acid), it is composed of an epoxy resin-modified unsaturated polyester and a polymerizable monomer. The content # is 65% by weight.

In the composition of the present invention, by using the epoxy resin-modified unsaturated polyester resin of the former (1), the coating Bt can be coated repeatedly and has excellent corrosion resistance and coating hardness.
It is possible to have 4.

Furthermore, by using the latter epoxy at tr modified unsaturated solidester resin, in addition to the above-mentioned properties, it is possible to significantly improve the dulling speed of the coating film and, by extension, the air drying properties.

The co-functional bisphenol A type epoxy resin (hereinafter simply referred to as epoxy resin) in the present invention is a compound having the following structural formula.

In this formula, n is usually appropriately selected from the range of 0 to 3.

The epoxy equivalent of the epoxy resin is in the range of about 700 to θθ, preferably about 7gO to 300. In the above range, if the nixie equivalent is about 100 or less, the glass transition temperature will be too low and the drying rate will tend to decrease. On the other hand, if it is about 500 or more, the functional group resistance of allyl ether groups and (meth)acryloxy groups is too low when producing the unsaturated polyester of the present invention, and the curing rate is decreased, so it is also not preferable.

The allyl ether group-containing unsaturated polyester used in the present invention must contain a free carboxyl group in its molecule, and the carboxyl group participates in the reaction with the epoxy group in the epoxy resin.

Such unsaturated polyesters can be produced by any method.

Generally, polybasic acids, polyhydric alcohols, and polyhydric alcohol allyl ethers are condensed to produce an allyl group-containing unsaturated polyester in which at least seven free carboxyl groups remain in the molecule.

As the polybasic acid, unsaturated polybasic acids such as maleic acid, fumaric acid, itaconic acid, distraconic acid, and anhydrides thereof are used, and if necessary, phthalic acid, isophthalic acid, terephthalic acid, het. Saturated polybasic acids such as adipic acid, sepacic acid, succinic acid, azelaic acid, and anhydrides thereof can also be used in combination.

Examples of polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, rimethylene glycol, triethylene glycol, trimethylo-A-x tan, trimethylolpropane, dihydroxypentadiene, inquerythritol, diglycerin, and ditrimethylol. You can enjoy gros, 9, etc.

Examples of polyhydric alcohol allyl ethers include glycerin monoallyl ether, trimethylolethane diallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, trimethylolethane diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, and pentaerythritol. triallyl ether, l, 2゜6-
Hexanetriol monoallyl ether, l.

Examples include hexanetriol diallyl ether, nrubitan monoallyl ether, and sorbitan diallyl ether. However, these compounds are merely examples, and the present invention is not limited to these compounds.

Furthermore, the allyl ether group-containing unsaturated polyester is not necessarily limited to the above composition, and contains at least a polybasic acid, preferably an unsaturated polycarboxylic acid such as maleic anhydride or fumaric acid, in the molecule. such as a partial esterified product of a with a polyhydric alcohol allyl ether having a hydroxyl group,
Even low molecular weight compounds can be used.

The above allyl ether group-containing nong! By reacting the Japanese polyester with an epoxy resin, the desired epoxy resin-modified unsaturated polyester can be obtained.

Specifically, for example, 1r of allyl group-containing unsaturated polyester is prepared in advance, and an epoxy resin is mixed therein and reacted. In addition, during the reaction of polybasic acid, polyhydric alcohol, and polyhydric alcohol allyl ether, which are the raw materials for the unsaturated polyester, to produce an allyl ether group-containing unsaturated polyester in the system, an epoxy resin F is further mixed into this. However, methods such as continuing the reaction may also be used as appropriate.

During this reaction, a small amount of cohydroxyethyl toluidine, cometerimidazole, trimethylbenzylammonium chloride, etc. is added as a catalyst.

The reaction temperature is Sθ~9o”c, preferably bo~70℃
is within the range of

In the present invention, by reacting an allyl ether group-containing unsaturated polyester with an epoxy resin as described above, unsaturated polyesters such as a bisphenol skeleton, an allyl ether group, and maleic anhydride can be added to the unsaturated thiester of the present invention. A saturated polybasic acid has an unsaturated acid double bond.

Therefore, due to the presence of these three strong components, corrosion resistance, coating hardness, etc. can be significantly improved without deteriorating the various performances of conventional air-drying paints.

In the above-mentioned epoxy resin-modified unsaturated polyester, the purpose can be sufficiently achieved if the epoxy resin component is present in an amount of 20 to 70% based on the total polymer, but it is more preferable that corrosion resistance is significant in the range of SO to 7%. It is demonstrated. If the epoxy resin component is less than 20% by weight, there is a tendency for the hardness of the coating film to decrease. On the contrary, go! If it is used in an amount exceeding x%, the viscosity becomes too high and a practical problem remains.

Further, the allyl ether group is selected from the range of S to 20% by weight based on the total polymer.

In the present invention, the allyl ether group-containing unsaturated Hf I
In addition to J ester, when (meth)acrylic acid is further bonded to the epoxy group in the epoxy resin, the curing speed of the coating film is significantly improved compared to when the allyl ether group-containing unsaturated polyester is used alone, that is, the air drying property is improved. A very good Nixie resin-modified unsaturated polyester is obtained.

As for the reaction, the carboxyl group in the molecule of (meth)acrylic acid also reacts with the epoxy group in the epoxy resin and bonds to it.

In order to bond an allyl ether group-containing unsaturated polyester and (meth)acrylic acid with an epoxy resin in a dud BAK, usually first, an allyl ether group-containing unsaturated polyester is produced by the various methods described above, and then a Nyxi pattern is applied. fat and (meth)acrylic acid at a temperature of 70~/10℃
A method of reacting is used. In addition, epoxy resin and unsaturated polyester containing allyl ether group; or epoxy resin and (meth)acrylic acid are reacted for the first time;
Next, a method for reacting the remaining l component 7 will be discussed. However, the present invention is limited to these methods.

In the above, (meth)acrylic acid is &-! ;01J4 quantity round is desirable.

The molecular weight of the epoxy resin-modified unsaturated polyester of the present invention thus obtained is approximately 0.000 to 3.000.
0, more preferably 7〈 is preferably in the range of about /S00 to 2500. In the above case, if the molecular weight is less than 1000, the coating viscosity will be too low and the curing speed will decrease. Also about 3.
If it is more than 000, the viscosity is too high, so if you use styrene etc. in a large amount, the desired coating viscosity will not be achieved.
This is likewise undesirable since it results in a decrease in curing speed.

In the present invention, the polymerizable monomers used together with the epoxy resin-modified polyester include styrene, vinyltoluene, chlorostyrene, α-methylstyrene, divinylbenzene, (meth)acrylic ester,
Glycidyl methacrylate, vinyl acetate, diallyl phthalate, triallyl siaslate, trimetherol glopan triacrylate, trimetherol derono and trimethacrylate, tung oil, linseed oil, soybean oil, HBseed oil, safflower oil, coconut oil, etc. can be mentioned.

The polymerizable monomer is added after producing the epoxy resin-modified unsaturated polyester so that the solid content is about 115 to 100% SM, as described above.

Furthermore, if necessary, it may be used as a reactive diluent to adjust the viscosity of the composition.

Further, the glass flakes used in the anticorrosive coating method of the present invention have an average thickness of 0.3 to 70 microns, preferably /-
They are extremely thin flat particles with an average size of 700 to 1 Ioo microns, preferably 0 to 3θ0 microns.

The glass flakes are layered in parallel to the material within the coating, increasing the strength of the coating and at the same time having the effect of blocking the permeation and penetration of external vapors, moisture, and other corrosive substances. ) is shown. The thickness of the glass flakes is 0. If the glass flakes are smaller than S micron, the strength of the glass flakes is so weak that they cannot be used practically. On the other hand, it's 70 microns! If it is thick, it tends to be difficult to arrange it parallel to the substrate.

However, if the size of the glass flakes is smaller than 700 microns, they will be difficult to arrange in parallel to the substrate, and the strength and corrosion resistance of the coating will not improve. On the other hand, in the case of glass flakes having a size exceeding 4 to θ microns, this is similarly undesirable because it impairs spray workability.

In the present invention, the mixing ratio of the epoxy resin-modified unsaturated polyester resin and the glass flakes is 1 ft.
o o 'yp volume, glass frame 0~
A range of 0.1 part (preferably 20 to 60 parts by weight) is suitable from the viewpoint of corrosion resistance and physical properties of the coating film.

In the above mixing ratio, if the glass flakes are not included in the weight part, the desired corrosion resistance cannot be obtained. On the other hand, if the amount exceeds 701 parts, the flexibility of the film decreases and the film becomes brittle, which is not preferable.

Next, in the present invention, ketone peroxide is used. As the ketone peroxide, methyl ethyl ketone peroxide is suitable.

Furthermore, in the present invention, hydroperoxide and
-+taha・ya-oxyester is used. Examples of the hydroperoxides include t-butyl-r-droperoxa-ide, cumene hydroperoxide, diisoglopyrupenzene hydroperoxide, ni-ya-ramen-tan-ha-f-drober oxide, co, S-dimethyl-ruco,
J-.Cybide robber-oxyhexane and the like are used.

In particular, cumene hydroglyoxide and t-butyl hydroperoxide are preferably used. These may be used as mixtures of glazes or glazes.

Furthermore, as the 7-oxyester, t-butylperoxyphthalate, t-butylnosooxybenzoate, t-butylpermexylaurate, t-butylnof-
Oxycoethylhexanoate, t-butyl peroxybivalate, t-butyl gloss-oxyacetate, t
-butylno-7-oxyimpetylate)%, and it is preferable to use t-butyl peroxyphthalate and t-butyl peroxylaurate. These can be used as a small mixture of 7 or 2 or more types.

In the present invention, by condensing ketone peroxide with hydroperoxide and/or peroxy ester, the pot life of the composition, i.e., the strength of the coating film]
Control the aging time.

As a result, the glass flakes become parallel in the sprayed coating, making it possible to carve a layer of glass flakes arranged parallel to the substrate.

Therefore, the amounts of ketone(-oxide, hydroperoxide and/or peroxyester) to be added are determined from the viewpoint of the above-mentioned actions (effects).

However, the amount of these compounds used is easily influenced by the outside temperature at the time of coating.

According to the experiments conducted by the present inventors, ketone peroxide is about /Q parts by weight for 700 parts by weight of epoxy temporary/T resin-modified unsaturated polyester resin at a temperature of 5°C.
It has been found that it is generally preferable to add an amount of around 0.4 parts when the temperature is θ°C, and around 0.4 parts when the temperature is 30°C. Also, is hydroperoxide and/or /4'-oxyester unsaturated with epoxy resin modification?
When the temperature is s°C, it is about t, about 3 parts by weight, when the temperature is 20°C, it is about 7.7 parts by weight, and when the temperature is 3θ°C, it is about 7.4 t1 (about 7.4 t1 by weight) of the polyester resin lθθ. It has been found that it is preferable to add an amount of around 10 parts.If the amount added at each temperature is too much than the above amount, the usable part interval becomes short and painting work becomes difficult.In addition, in a short time As the coating film hardens, parallel alignment of glass flakes is less likely to occur.

On the other hand, if the amount added is less than the above amount, the drying time will be too long, which is inappropriate.

In the present invention, it is essential to use ketone peroxide and hydroperoxide and/or peroxy ester in combination.

The former contributes to the radical reaction of the polyester resin, but when used alone, the curing reaction is too rapid, making it difficult to arrange glass flakes in parallel. Therefore, in order to control the radical reaction at room temperature, adding L to the hydroperoxide and/or (-oxyester) totally promotes the parallel arrangement of the glass flakes.

Also, hydroperoxide and/or...! - Oxyesters do not contribute to the curing reaction in a short period of time, but gradually decompose over a long period of time, proceeding with the crosslinking reaction and increasing the overall strength of the coating film. Therefore, these methods are essentially different from curing control using hydroquinone, catechol, etc., which are normally used as curing retarders.

In this way, a composition used in the method of the present invention is obtained, and if necessary, the composition contains a curing accelerator, a coloring pigment, an extender pigment, an anticorrosive pigment, a suspending agent, a dispersant, a diluent, and other substances. It is possible to add flat pigments and the like.

In the present invention, the composition thus obtained is applied to an object by spray coating.

As the Sosolet method, pressure-feed air spray, airless spray, etc. are suitable. In the case of pressure-fed air gray, the air pressure should be 9/On2 or more, in the case of airless spray, the primary air pressure should be 3K9/CN, 2 or more, the compression ratio 3θ: 2 or more, the spray tip diameter o, 3 to 3-(
There are a number of cases where the coating Φ is 0.73~λ%). In the above, the spray tip diameter is 0. ! If it is smaller than Swn, glass flakes will clog the chip, making it impossible to perform smooth painting work.

On the other hand, if the spray tip diameter is larger than the 3rd end, the spray will not spread properly and is inappropriate.

In the method of the present invention, by the coating method as described above,
Dry paint storage is about 300~/,! ;Apply on the damaged coating so that the thickness is OO microns (preferably S00~/20θ microns). If the coating film thickness is thinner than 300 microns within the above range, it is preferable because not only the anticorrosion properties of the coating film are reduced but also glass flakes are less likely to form in the 〒 row and IV column. do not have. On the other hand, the coating thickness is /3
If it is thicker than 0.00 microns, the coating film will be blurred and a royal coating film will be obtained. After application, the coating composition is dried to form a coating film.

As mentioned above, sedge 1/-
Glass flakes in the composition are removed by Coating I.
They will be arranged parallel to the substrate in I^. Therefore, the obtained @ film has excellent corrosion resistance, strong chemical resistance, weather resistance, adhesion, strength, etc.

Furthermore, if necessary, chlorinated rubber, alkyd resin, epoxy resin, urethane resin,
A top coat of acrylic resin, fluorine repair resin, etc., or a top coat of unsaturated polyester resin and glass flakes may be applied. The coating obtained by the method of the present invention exhibits excellent adhesion to these top coats.

The details of the present invention will be explained below with reference to Examples and Comparatives.

Blend of Examples / (Main ingredient) Weight part Engineering I Xylene modified unsaturated polyester resin A 3t organic bentonite [benton φ, ? 4'::Product name manufactured by National Red Company] 2.0 styrene
3. S...! ; Cobalt Nanthenate (
6% metallic cobalt content) 0.5 glass flakes [acid-resistant alkali-containing glass, average size 1so-, 2oo microns, average thickness 3-S microns]/s Talli
510θ, θ (curing agent) Methyl ethyl ketone oxide
0. /Kumene Hydro/Zoichi Oxide
. , 3 The epoxy resin-modified unsaturated polynisder resin A was obtained as follows; glycerin monoallyl ether 0. F5 anhydrous malein ell
The reaction was carried out for 6 hours at a total flow rate of 17.0 mol and 0.5 mol of ethylene glycol/gθ°C to obtain an allyl ether group-containing unsaturated polyester. To this, 0.0% bisphenol A diglycidyl ether was added as an epoxy resin component. S
After adding 0.3% co-hydroxy para-toluidine to the total system and reacting at 90°C for 7 hours, add 2.3% methanol to the total system and reacting for another 7 hours. , 10rrrmHP for 30 minutes, and then styrene was added to give a solid content of 60% and an acid value/gt.
An epoxy resin-modified unsaturated polyester resin having a viscosity of <oH/ff% of 3000 cps and a content of the epoxy resin component relative to the total polymer of 0% was obtained.

Add to this 0.03% hydroquinone as a polymerization inhibitor.
The added material was designated as epoxy resin-modified unsaturated polyester resin A.

The epoxy resin-modified unsaturated polyester resin and organic bentonite in the main component of the above formulation were mixed and rolled with a roller, and then the other ingredients were added and stirred with a disc/4'- to prepare a main component. /! ;O×! ;Ox/. Otsuka's mild steel plate (J
I 5-G-3/4t〆)' (After completely removing black scale, rust, and oil with i-Sandogelast, apply at airless spray with a hardening agent added to the main ingredient of the above formulation/(Tiglo diameter/.) The film was coated to a dry film thickness of 5000 SO microns, and after drying at θ°C for 7 days, it was subjected to a comparative test.

Example λ Compound C Main agent) Is the epoxy tatami mat fat denatured and incongruous? Reester resin s
4t.

Organic bentonite (same as Example 1) /. , 5
- Styrene/3 cobalt naphthenate (same as Example 1) 0.3 Glass flakes (Example 1 and jvJ->2, r Tal
the law of nature
/4100,0 (Curing agent) Methyl ethyl ketone(-oxide θ
．． /St-Butylperoxyfucrate 0.3
Xy resin modified unsaturated? Lyester shredded oil B was obtained as follows: diarylpentaerythritol θ,+,S-mol, maleic anhydride/80 mol, and phthalic anhydride 0.2 mol were reacted at 110°C for 2 hours. To the allyl ether group-containing unsaturated polyester obtained, 1 acrylic ek 0.3 mol, bisphenol A diglycidyl ether 0.5 mol, and 0.3% amount of Norhito 90 xyethyl para-toluidine gold to the entire system were added. Prepare 9
After reacting at 0°C for 10 hours, it was cooled to 60°C, methanol was added to λ% of the total system, and the reaction was further continued for 1 hour, /OwaH
After depressurizing for 30 minutes at fi', styrene was added to reduce the solid content to θ%, #value/3 m9K OH/ff%.
An epoxy resin-modified unsaturated polyester resin was obtained in which the contents of the niboxy resin component and the acrylic component were 70% and 50%, respectively, with respect to Viscous Jet 2000 cps % total f') Mani. Epoxy resin-modified unsaturated polyester resin B was obtained by adding 3% of hydroquinone θ and θ to this.

It was prepared and subjected to a comparative test.

Example formulation 3゜ (base ingredient) Weight part construction? Xy resin modification disharmony? Reester Seven H Monthly C50 Organic Bentonite (Example/Towards) /, Q Styrene 23.5 Cobalt Nanthenate (Same as Example 1) 0. S glass flakes (same as Example/) 20/θ0. θ (Curing agent) Methyl ethyl ketone (-oxide
0.3t-'7'' tirno-4-oxyphthalate 0.7 The above-mentioned epoxy M lipid-modified unsaturated polyester resin C is obtained as follows: 0.5 mol of diallylpentaerythritol; Anhydrous malein Wt, O mol,
0.3 mole of methacrylic acid and bisphenol A were added to the allyl ether group-containing unsaturated polyester obtained by reacting 0.3 mole of ethylene glycol at a temperature of 60°C for 2 hours.
After charging 0.5 mol of diglycidyl ether and 0.3% of cohydroxyether paratoluidine based on the total system and reacting at 90°C for 10 hours, I, 0
Cool to ℃, add methanol to the total system % power 1] Ehara 1 + 11
After reacting for 1/hour and performing vacuum treatment for 30 minutes using 1O fermentation Hp, styrene was added to give a solid content of 60% and an acid value of 77.
QKOH/P, viscosity 3 left θ0 cps, content of epoxy resin component and acrylic component relative to total polymer is q
An epoxy resin-modified unsaturated polyester resin with a light weight of 1/7% was obtained. 3% of hydroquinone θ was added to this to obtain a T5 resin-modified unsaturated polyester resin C.

Next, it was made into a paint in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test.

Example 1 Formula 1 Part by weight Epoxy resin modified unsaturated polyester resin D 37 Organic bentonite (same as Example 1) 2.0 Styrene
35. S cobalt naphthenate (same as example/) θ, S glass flakes (same as example/) 20 titanium dioxide
Slθθ, 0 (curing agent) Methyl ethyl ketone+-Joxide
0. /cumene hydropermoxide
0.3 The epoxy resin-modified unsaturated polyester resin was obtained as follows. To an allyl ether group-containing unsaturated polyester obtained by reacting i mol of maleic anhydride/Q mol at a temperature of 60° C. for a co-time period, 0.5 mol of acrylic acid and 0.5 mol of bisphenol A diglycidyl ether were added. S mol and 0.396 amount of Ω~hydroxyethyl/zolatuidine to the whole system were charged at once and allowed to react at 90°C for 10 hours, then cooled to θ°C, and methanol was added to % of the whole system. In addition, let the reaction continue for another 7 hours.
After depressurizing at ψ for 30 minutes, he added styrene to make the solid cedar θ%, acid value 3■KOH/ji', and viscosity 2!
To obtain an epoxy resin-modified unsaturated polyester resin in which the content of the resin component and the acrylic component relative to the total polymer was 0.00 cps, the content of the resin component and the acrylic component relative to the total polymer was 0.03% and 0.03%. The 1-wa polyester resin was set to 0.

Next, it was made into a paint in the same manner as in Example 1, and a test piece was prepared and subjected to a comparative test.

Example left Formulation left (main ingredient) Part by weight Epoxy resin modified unsaturated polyester column 1 effect E

5 θ organic bentonite (
Same as Example 1) /, 0 styrene
23. ! f Cobalt naphthenate (Example/
and rml) 0.3 glass flakes (Example 1
) 20 titanium dioxide
5100.0 (Curing agent) Methyl ethyl ketone peroxide θ
, 3t-bunalburoxyphthalate 0.7 @ 1 Epoxy resin-modified unsaturated polyester resin E was obtained as follows: partial ester of maleic anhydride and triallyl pentaerythritol o, lIs mol, acrylic e'eo, s mol, bisphenol A diglycidyl ether 0.5 mol, and 0 for the whole system.
．． After charging 3% sodium sulfur hydroxyethane latoluidine in bulk and reacting at 90°C for 10 hours, it was cooled to 60°C, 296 methanol was added to the whole system and reacted for another 1 hour, and then treated under reduced pressure at 10 H7 for 30 minutes. After doing this, add styrene to reduce the solid content to 4. t%, acid value 5. θ■KOH/ff
, Viscosity 3700 Cps % Total? The sensitization of the epoxy resin component and the acrylic component to the remer is S1;I, respectively.
-%, / 3 jX epoxy resin-modified unsaturated polyester grains/ This includes 0.03% hydroquinone.
was added to obtain epoxy-side fat-modified unsaturated polyester resin E.

Next, it was made into a paint in the same manner as in Example/1, and a test piece was prepared and subjected to a comparative test.

Comparison side 1/ Compound (main ingredient) Part by weight Isofucric acid-based unsaturated polyester resin [Rigorak/jf; QHR', trade name manufactured by Showa Kobunshi ■] 30 organic bentonite (Example 1 and PI-), 2. , t-styrene
22 Cobalt naphdate (Example/-11-) θ, S glass flakes (alkali-resistant glass, average particle size 90 microns, average thickness 3 to S microns) 20 Titanium oxide 5100.
0 (@1-izing agent) Methyl ethyl ketone peroxide /
, left The above-mentioned formulation B was made into a paint in the same manner as in Example f, and test pieces were prepared and subjected to a comparative test.

Comparative Example Blend 7 (Main ingredient) 1. Dobe isophthalic acid-based unsaturated polyester resin (same as Comparative Example 1) 4t5 Organic bentonite (Example 1 and (b)-) 2.3 Styrene 21.7 Cobalt naphthenate (Example) Example/same as) 00g glass flakes (★
Example/same as) 2S titanium oxide
S/θ0.0 (Curing agent) t-Butyl peroxybenzoate 2.0 The above formulation 7 was made into a paint in the same manner as in Example/1, and a test piece was prepared and subjected to a comparative test.

The coating films obtained in Example 4/l'l/~S and Comparative Examples 〆~C were subjected to comparative testing of hardness, corrosion resistance, adhesion, weather resistance, durability, etc. It is shown in Table 1.

JP-A-59-179180 (1t) Note/) The boatman's hardness after 2 hours was examined according to JIS K-Left 110/.

Note 2) Make a cross cut on the specimen, peel off the paint film for 500 hours, and check whether the cut has progressed from the cut part to the bottom of the paint film.

Note 3) Strength at 1 of coating film breakage per 1/2 inch measured by Tensilon tensile tester.

Note: Place the test piece in a test piece and test it with a weatherometer.
At 0θ hour, I glanced down at my eyelids and the paint film was on the edge of my skin.

Note 3) The condition of the coating film was checked by immersing it in tap water at θ℃ for θ months.

Note 6) Immersed in a 20% hydrochloric acid bath for a month.

Note 7) Leave it in the state of lOθ96RH for 5ooo hours.

From Table 1 above, the coating film obtained by the method of the present invention is as follows:
Not only does it have much improved rust prevention properties compared to coatings obtained using conventional compositions, but it also has excellent performance in terms of adhesion, weather resistance, and product resistance. It is clear that this shows that

Kazuo Wakasugi, Commissioner of the Japan Patent Office, 1. Indication of the case: Showa 5G Patent Application No. 5 ≠≠g Otsu 2
, Title of the invention Corrosion-proof coating method 3, Relationship with the case of the person making the amendment Applicant name (332) Inu Nippon Toyo Co., Ltd. 4, Agent 5, Motive for ordering the amendment Voluntary 6. /, The following parts of the specification is corrected as below.

F continuation? ii ″” 5B, 6.30 Commissioner of the Patent Office Kazuo Wakasugi Punishment 1, Indication of the case 1980 Patent Office No. 54486 2, Title of invention Corrosion-proof covering power method 3, ? Relationship with the case of a person who makes a diversion Applicant Name (332) Dainippon Toyo Co., Ltd. 4, Agent 5, Supplementary IF Order Attachment 11 Voluntarily, subject to amendment Mei 1) Detailed description of the invention in 1 Explanation column 7, Supplement 1, Uchitani 1, the above part of the description is corrected as follows.

Claims (1)

[Claims] (Niboxy resin-modified unsaturated polyester resin in which an unsaturated polyester having an allyl ether group and a carboxyl group is bonded to an epoxy group in a 112-functional bisphenol A type epoxy resin...100 Glass flakes with a size of 0.3 to 70 microns and a size of 100 to 1 loo microns...10. to 70 parts by weight Ketone peroxide...0.7 to 2.0 parts by weight A composition consisting of 0.5 to 2.0 parts by weight of hydroperoxide and/or peroxy ester is coated with a coating film thickness of 300 to 300 mm using a sugley gun with a diameter of 0S to 3 mm. An anticorrosive coating method characterized by coating y with sugure. The unsaturated polyester having an ether group and a carboxyl group at +2'+7 is coated with an unsaturated polybasic acid or its anhydride and one hydroxyl base Claim No. 1 (Anti-corrosion coating method according to Claim 11) wherein the partially esterified product with a polyhydric alcohol allyl ether having The anticorrosive coating method described in (2). (4) The epoxy group in the 2-functional i-bisphenol A-type epoxy dog fat contains (a) an unsaturated polyester having an allyl ether group and a carboxylic group, and (b) acrylic acid or Epoxy resin-modified unsaturated polyester bound with methacrylic acid...100 layers Thickness: 0.3-10 microns, size: 100-tioo microns Glass flakes...lO-70 layers A composition consisting of a proportion of ketone peroxide...0.7 to 2.01 Kurabe, hydroperoxide and/or peroxy ester...0.5-s, ohms. A patented anti-corrosion cladding method that involves spray painting to a coating thickness of 300-/S00 microns using Szoleteguro WO, S~3 sprayable. (5) The unsaturated material has an allyl ether group and a carboxylic group. Claim No. 4, wherein the polyester is a partial esterification product of an unsaturated polybasic acid or its anhydride and a polyhydric alcohol allyl ether having 7 hydroxyl groups.
Anti-corrosion coating method described in section. (6) The corrosion-resistant coating method according to claim (5), wherein the unsaturated polybasic acid or its anhydride is maleic anhydride.