JP2981567B2 - Corrosion resistant resin - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin capable of forming a strong metal chelate complex on a metal surface to prevent metal corrosion.

2. Description of the Related Art Conventionally, in order to prevent metal corrosion, (1) metal surface treatment for forming an inorganic coating such as phosphate or chromate on a metal surface, (2) epoxy resin or phenol Techniques such as a coating corrosion prevention technique of forming an organic coating such as a resin on a metal surface have been used.

However, in the case of metal surface treatment, there are drawbacks such as generation of environmental pollution due to heavy metal waste liquid, use of toxic substances such as acids, alkalis, and cyan, and complicated steps.

Further, in the case of coating corrosion protection, there is a problem that the bonding force with the metal is not strong enough to completely suppress the corrosion reaction.

At present, anti-corrosion technology that is non-polluting, practical and has excellent anti-corrosion properties has not been established, and its development is awaited.

Means for Solving the Problems In view of the above situation, the present inventor can use as a non-polluting surface treatment agent in place of an inorganic surface treatment agent such as a phosphate or a chromate, and an epoxy resin or a phenol resin. In order to obtain a new and non-polluting resin that shows superior corrosion protection, we have been conducting research by comprehensively applying surface chemistry, thermodynamics, electrochemistry, complex chemistry, etc.

As a result, focusing on the fact that a polymer compound capable of forming a chelate complex binds to a metal much more strongly than a resin such as an epoxy resin or a phenol resin, the polymer compound capable of forming a chelate complex has a group capable of forming a chelate complex. By using a group in which a thioether group and a carboxyl group are bonded via a divalent o-phenylene group, the binding energy to the metal due to chelation exceeds the corrosion reaction energy, and the charge of the metal ion And the like, and found that the present invention was completed.

That is, the present invention uses the formula It is an object of the present invention to provide a corrosion-inhibiting resin having at least one chelate-forming group in a molecule represented by the formula:

The resin of the present invention needs to have a chelate-forming group represented by the following formula [I].

In the resin of the present invention, the chelate-forming group is a portion which forms a stable non-ionic intramolecular complex salt type six-membered ring chelate complex with a +2 or +3 metal ion. The chelating group The chelate complex thus formed is modeled as follows.

As described above, three sets of chelating groups are bonded to the +3 valent metal ion, and two sets of chelating groups are bonded to the +2 valent metal ion. A six-membered ring chelate complex neutralized by the rate ion is formed. The formed chelate complex is neutralized in charge and is nonionic, so that corrosion current does not easily flow against metal corrosion, and is structurally stable because it forms a six-membered ring. . If the number of intervening carbon atoms exceeds 2, the formed complex becomes a 7-membered ring or more, which is not preferable because the stability is reduced.

In the resin of the present invention, it is necessary that the above-mentioned chelate-forming group is bonded to the resin base by a thioether bond.

Examples of a method for obtaining the resin of the present invention by bonding the base portion of the resin and the chelate forming group by a thioether bond include the following methods (1) to (4).

(1) A method in which a polymerizable double bond is provided at a terminal or a side chain of a resin forming a base portion, and a compound represented by the following formula [II] is added to the double bond.

(2) An addition reaction product of a compound having both a functional group such as a hydroxyl group and a polymerizable double bond with the compound represented by the above formula [II], and a reaction with a functional group such as a hydroxyl group in the reaction product A method of reacting with a polymer having a functional group such as an isocyanate group having a property.

(3) A method of copolymerizing a compound having a chelate-forming group of the formula [I] and a polymerizable double bond with another polymerizable unsaturated monomer.

(4) A method of adding the compound represented by the formula [II] to a silane compound or resin having an etherified silanol group and a polymerizable double bond. Further, a compound or resin having a structural part of the formula [I] and an etherified silanol group obtained by this method is partially condensed or partially co-condensed with another silane compound having an etherified silanol group. How to let.

In the method (1), the resin having a polymerizable double bond at a terminal or a side chain is not particularly limited, and various resins obtained by a known method can be used.
For example, copolymers of epoxy group-containing polymerizable unsaturated monomers such as glycidyl (meth) acrylate and allyl glycidyl ether with other polymerizable monomers, and various epoxy resins such as bisphenol resins, and resins having an epoxy group at the terminal or side chain thereof. A carboxy group-containing polymerizable unsaturated compound such as (meth) acrylic acid is added to open the epoxy group,
It is obtained by introducing a polymerizable unsaturated group into the resin. This addition reaction can be performed by heating both at about 50 to 150 ° C. for about 30 minutes to 8 hours.

Further, isocyanate ethyl (meth) acrylate, m-α, is used for a hydroxyl group in a resin such as an acrylic resin having a hydroxyl group, a polyester resin, an alkyd resin, and an epoxy resin.
It can also be obtained by adding a polymerizable unsaturated group-containing isocyanate compound such as α'-isopropenylphenyl isocyanate to introduce a polymerizable unsaturated group. This addition reaction can be performed, for example, by reacting both at 20 to 100 ° C. for about 1 to 10 hours in the presence of a tin-based catalyst such as dibutyltin octylate.

The resin having a polymerizable double bond at the terminal or side chain obtained as described above is reacted with the compound represented by the formula (II) to form a chelating group represented by the formula (I) in the resin. Is introduced. The thiosalicylic acid represented by the above formula [II] has little odor and is easy to handle. The addition reaction of the compound represented by the formula [II] to the polymerizable double bond in the resin is carried out by reacting both at, for example, usually about 20 to 100 ° C. for about 1 to 24 hours in the presence of an amine catalyst. be able to.

In the method (2), the reaction order in the method (1) is changed, and a reaction product having a chelate-forming group represented by the formula [I] and a functional group is first prepared,
This is a method of reacting the functional group with a functional group in a polymer to increase the molecular weight.

In the above method (3), the compound having a chelate-forming group of the formula [I] and a polymerizable double bond is, for example,
The hydroxyl group in the addition product of the compound represented by the formula [II] and a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth) acrylate is converted to isocyanatoethyl (meth) acrylate, m-α, α'-iso It can be obtained by a method of adding to a polymerizable double bond-containing monoisocyanate compound such as propenylphenyl isocyanate. The reaction between the compound represented by the formula (II) and the hydroxyl group-containing unsaturated monomer is carried out, for example, by reacting both at an equimolar amount at about 20 to 100 ° C. for about 1 to 24 hours in the presence of an amine catalyst. Can be. The addition product obtained thereby has a hydroxyl group, and the addition reaction of this with a polymerizable double bond-containing monoisocyanate compound is carried out, for example, in the presence of a tin-based catalyst at an equimolar ratio of about 20 to 100 ° C. About 1
The reaction can be carried out for up to 10 hours.
The compound having a chelating group of the formula [I] and a polymerizable double bond can be obtained by a method other than the above. For example, it is obtained by reacting 2 mol of the compound represented by the formula [II] with 2 mol of a polymerizable double bond-containing halogenated hydrocarbon such as allyl bromide in the presence of 1 mol of a complex-forming metal salt such as nickel chloride. Pickling the resulting precipitate.

In the method (3), other polymerizable unsaturated monomers used for copolymerization with the compound having a chelate-forming group of the above formula [I] and a polymerizable double bond include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n- butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, C ₁ ~ of (meth) acrylic acid and lauryl (meth) acrylate
C ₁₈ alkyl ester; 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate such as (meth) hydroxyl group-containing unsaturated monomers such as C ₂ -C ₈ hydroxyalkyl esters and allyl alcohols of acrylic acid: styrene And vinyl monomers such as vinyl acetate, (meth) acrylamide, (meth) acrylonitrile, and N-methylol (meth) acrylamide butyl ether, each of which may be used alone. Alternatively, two or more kinds can be used in combination.

The copolymerization of the polymerizable double bond-containing adduct and the other polymerizable unsaturated monomer can be carried out by a known copolymerization method.For example, the above-mentioned components are added in the presence of a polymerization catalyst and preferably an organic solvent. And a heating reaction.

In the above method (4), a silane compound having a polymerizable double bond and an etherified silanol group is preferably a silane compound represented by the following general formula [V] or one of these silane compounds. Or a resin in which two or more kinds are partially condensed, and a partial cocondensate of these silane compounds with another silane having a silanol group etherified.

[In the formula, A represents an unsaturated hydrocarbon group or an unsaturated carbonyloxyalkyl group, X represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and 6 carbon atoms. -8 aryloxy groups or an aliphatic cyclohydrocarbonoxy group having 5-8 carbon atoms. Y and Z are the same or different and each represents an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 8 carbon atoms or an aliphatic cyclohydrocarbonoxy group having 5 to 8 carbon atoms, and is the same as X It may be. Preferred examples of the above A include a vinyl group, an allyl group,
Examples include a methacryloyloxyethyl group, an acryloyloxyethyl group, a methacryloyloxypropyl group, and an acryloyloxypropyl group.

In the above X, Y and Z, an alkoxy group having 1 to 18 carbon atoms, an aryloxy group having 6 to 8 carbon atoms, and 5 carbon atoms
Preferred among the alicyclic hydrocarbon oxy groups are methoxy, ethoxy, propoxy, butoxy, hexoxy, octoxy, methoxyethoxy groups and other alkoxy groups having 1 to 8 carbon atoms, phenoxy groups, And a cyclohexyloxy group.

In the above X, preferred among the hydrocarbon groups having 1 to 18 carbon atoms are alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl and n-hexyl. An aryl group having 6 to 8 carbon atoms such as phenyl, methylphenyl and ethylphenyl;
5-8 carbon atoms such as cyclopentyl and cyclohexyl
Alicyclic hydrocarbon groups.

Representative examples of the silane compound represented by the general formula [V] include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (n-propoxy) silane, vinylbis (methoxy) methylsilane, vinylbis (ethoxy) methylsilane, and vinylbis (n -Propoxy) methylsilane, allyltrimethoxysilane, β-acryloyloxyethyltrimethoxysilane, β-methacryloyloxyethyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxy Propyl (methyldiethoxy) silane, β
Methacryloyloxyethyltriethoxysilane, γ
-Methacryloyloxypropyltriethoxysilane,
γ-methacryloyloxypropyltris (2-methoxyethoxy) silane, β-methacryloyloxypropyltris (n-butoxy) silane, γ-methacryloyloxypropyltris (isobutoxy) silane, γ-methacryloyloxypropyltris (isopropoxy)
Examples include silane.

As the other silane compound having an etherified silanol group that can be partially cocondensed with the silane compound represented by the formula [V], a silane compound having two or more etherified silanol groups can be used. For example, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, ethyltrimethoxysilane, dimethyldimethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, Examples thereof include silane compounds such as diisobutyldimethoxysilane and diisobutyldipropoxysilane, and partial cocondensates of these silane compounds.

Partial condensation of the silane compound represented by the above formula [V] and partial cocondensation of the silane compound represented by the above formula [V] with another silane compound having an etherified silanol group can be carried out by a conventionally known etherified silane. It can be carried out according to the condensation method of the compound, and generally, it is heated to a temperature from normal temperature to a boiling point or lower, preferably 50 to 90 ° C. in the presence of an organic acid such as acetic acid, an acid such as an inorganic acid such as hydrochloric acid, and water. Can be done by The amount of water may be appropriately increased or decreased according to the degree of condensation.

By adding the silane compound or resin having the condensable double bond and the etherified silanol group to the compound represented by the formula [II], the chelating group of the formula [I] and the etherified silanol are added. A silane compound or a resin having a group is obtained. The above addition reaction is
Both are usually brought to about 20 to 100 ° C. in the presence of an amine catalyst, for example.
For about 1 to 24 hours. The resin obtained by this method is included in the resin of the present invention.

The resin of the present invention can also be obtained by partially condensing the silane compound or the resin obtained by the above addition reaction or partially cocondensing with another silane compound having an etherified silanol group.

As the other silane compound having an etherified silanol group, those described as other silane compounds that can be partially co-condensed with the silane compound of the formula [V] can be used. The partial condensation and the partial cocondensation can be performed in the same manner as the above-mentioned partial (co) condensation method.

The resin of the present invention obtained by the method (4) includes:
It has an etherified silanol group, and this group reacts with moisture in the air, hydrolyzes to form a silanol group, and undergoes a cross-linking reaction.

The resin obtained by the method (1), (2) or (3) can also be made to be a moisture-curable type by introducing etherified silanol groups into the resin. In order to introduce an etherified silanol group into the resin, for example, a hydroxyl group is present in the resin, and a monoisocyanate compound having a silanol group etherified into the hydroxyl group is used in the presence of, for example, a tin-based catalyst. About
A method of reacting at 20 to 100 ° C. for about 1 to 10 hours can be used. Representative examples of the monoisocyanate compound having an etherified silanol group include, for example, γ-
Examples include isocyanatopropyltrimethoxysilane and γ-isocyanatopropyltriethoxysilane.

The resin of the present invention may be obtained by a method other than the above-mentioned methods (1) to (4) and these modification methods.

The resin of the present invention preferably has a film-forming ability, and has a number average molecular weight of about 570 to 100,000, more preferably about 8 to 10,000.
Suitably, it is in the range of 00 to 50000. Further, the resin of the present invention needs to have at least one chelating group described above in the molecule, and the chelating group should have 0.2 to 3.5 Avogadro, and more preferably 0.3 to 3.0 Avogadro in 1000 g of the resin. Is preferred.

In the resin of the present invention, various resins can be used as the base resin as described above, for example, an acrylic resin,
Epoxy resins, polyester resins, alkyd resins, silicon-containing resins and the like can be mentioned.

The resin of the present invention may be used after being diluted with an organic solvent,
Further, the amount of carboxy groups in the resin, for example, the acid value is 30-13
Adjusted to be 0, the carboxyl group is an organic amine,
It may be neutralized with a base such as ammonia and dispersed or dissolved in water.

In the resin of the present invention, a reactive group such as a hydroxyl group may be present in addition to the above-described chelate-forming group in the resin, and the resin may be used in combination with a crosslinking agent that reacts with the reactive group. For example, when the reactive group is a hydroxyl group, as a crosslinking agent,
Formaldehyde condensates of known polyisocyanate compounds, blocked polyisocyanate compounds, and aminoplast resins, ie, nitrogen-containing compounds such as urea, melamine, and benzoguanamine, and lower alkyl etherified products of these condensates (the carbon number of the alkyl group is Crosslinking can be carried out at room temperature or by heating using 1) to 4).

Effect of the Invention The resin of the present invention is used alone or in combination with a crosslinking agent to be excellent against metals that generate +2 or +3 metal ions by corrosion of iron, zinc, copper, aluminum and the like. It can impart anti-corrosion properties and is pollution-free. For this reason, the resin of the present invention is extremely useful as a metal surface treatment agent or anticorrosion paint.

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples.

Hereinafter, "parts" and "%" mean "parts by weight" and "% by weight", respectively, unless otherwise specified.

Production Example 1 245.3 parts of methyl isobutyl ketone were mixed in a flask, heated to 50 ° C., nitrogen gas was blown into the flask to replace the inside of the flask with nitrogen gas, and the following mixture was further mixed.

2-hydroxyethyl acrylate 116 parts Thioglycolic acid 92 parts Triethylamine 1.8 parts After mixing the above mixture, the mixture was heated at 50 ° C for 5 hours, and then 80 parts.
The mixture was heated and reacted at 1 ° C. for 1 hour to obtain a hydroxyl group-containing adduct solution. In the obtained solution, the fact that the SH group of thioglycolic acid was added to 2-hydroxyethyl acrylate and no SH group remained remained by using 5,5′-dithiobis (2-nitrobenzoic acid). Confirmed by color reaction.

Then, instead of blowing nitrogen into the flask, air was blown, and the following mixture was blended into the above adduct solution.

m-α, α'-Isopropenyl phenyl isocyanate 116 parts Dibutyltin diacetate 0.2 part Hydroquinone 0.4 part After blending the above mixture, heat at 50 ° C for 5 hours under air blowing, and then heat at 80 ° C for 1 hour. A monomer A solution was obtained. The solid content of the obtained resin solution was about 60%. The main structure of monomer A is represented by the general formula It is represented by

Production Example 2 1000 parts of water was blended in a flask, and nitrogen gas was blown into the flask to replace with nitrogen gas, and the following compounds were blended.

γ-methacryloyloxypropyl trimethoxysilane 248 parts thiosalicylic acid 154 parts triethylamine 3.0 parts methoxypropanol 402 parts After mixing the above compounds, stirring, and then stirring at 50 ° C. under a nitrogen gas purge.
For 5 hours, and then reacted at 80 ° C. for 1 hour to obtain a silane B solution having a solid content of about 50%. The main structure of silane B has the general formula It is represented by

Production Example 3 2000 parts of water was blended in a flask, and nitrogen gas was blown into the flask to replace with nitrogen gas, and the following compounds were blended.

Thiosalicylic acid 308 parts Allyl bromide 242 parts Nickel chloride 238 parts Sodium carbonate 106 parts After blending and stirring each of the above compounds, the mixture was allowed to stand at room temperature (20 ° C.) for 24 hours under a nitrogen gas atmosphere to obtain a precipitate. The precipitate was washed with water and added to another flask containing 1000 parts of a 5N acetic acid aqueous solution. After stirring, the mixture was filtered and the residue was dried to obtain allylthiosalicylic acid.

194 parts of allyl thiosalicylic acid were dissolved in 427 parts of methyl isobutyl ketone, and 78 parts of mercaptoethanol was added thereto, and the mixture was reacted at 80 ° C. for 8 hours under nitrogen gas suction and stirring to obtain a solid content of about 39%. % Hydroxyethylthiopropylthiosalicylic acid solution was obtained. Add 699 parts of this solution to 50
After cooling to 50 ° C., the following compounds were blended therein under suction of air, and heated at 50 ° C. for 7 hours to obtain a monomer C solution.

Isocyanatoethyl methacrylate 155 parts Dibutyltin diacetate 0.21 parts Hydroquinone 0.43 parts The solid content of the obtained solution was about 50%. Monomer C
Is of the general formula It is represented by

Production Example 4 47 parts of metal isobutyl ketone were mixed in a flask,
The mixture was heated to 50 ° C. and the following compounds were blended under nitrogen blowing.

Hydroxyethyl thiopropylthiosalicylic acid having a solid content of about 39% used in Production Example 3 699 parts γ-isocyanatopropyltrimethoxysilane 205 parts Dibutyltin diacetate 0.24 parts After blending each of the above compounds, the mixture was blown with nitrogen at 50 ° C. After heating for 7 hours at 80 ° C. and then reacting at 80 ° C. for 1 hour, the mixture was cooled and diluted by adding 636 parts of ethanol to obtain a silane D solution. The solids content of the resulting solution was about 30%.

The main structure of silane D has the general formula It is represented by

Production Example 5 In a flask, 1000 parts of water, 194 parts of allylthiosalicylic acid and 101 parts of triethylamine were blended and uniformly dissolved. To this, 2,3-dimercapto-1-propanol 6
2 parts and 0.5 parts of chloroplatinic acid were added, and the mixture was heated and reacted at 80 ° C. for 8 hours under stirring and nitrogen gas blowing, and then cooled to give 1-hydroxypropane-2,3-di-diamine represented by the following formula. (Thio-
S-γ-propylthiosalicylic acid) was obtained.

In a separate flask, 446 parts of methyl isobutyl ketone were blended, heated to 50 ° C., and the following compounds were blended while blowing air.

1-hydroxypropane-2,3-di (thio-S-γ-
Propylthiosalicylic acid) 514 parts Isocyanatoethyl methacrylate 155 parts Dibutyltin diacetate 0.33 parts Hydroquinone 0.66 parts After blending each of the above compounds, 7
The mixture was heated and reacted for an hour to obtain a monomer E solution. The resulting solution had a solids content of about 60%. The main structure of monomer E is represented by the general formula It is represented by

Production Example 6 In a flask, 719 parts of methyl isobutyl ketone were blended, heated to 50 ° C., and the following compounds were blended under blowing of nitrogen gas.

1-hydroxypropane-2,3-di (thio-S-γ-
Propylthiosalicylic acid) 514 parts γ-isocyanatopropyltolmethoxysilane 205 parts Dibutyltin diacetate 0.36 parts After blending each of the above compounds, the mixture is heated at 50 ° C for 7 hours under nitrogen gas blowing, and then heated at 80 ° C for 1 hour. After heating and reacting for an hour, the mixture was cooled and 959 parts of ethyl alcohol was added to obtain a silane F solution. The solid content of the obtained solution was 30%. The main structure of silane F is a general formula It is represented by

Reference Example 1 20 parts of isobutyl alcohol and 38.7 parts of methyl isobutyl ketone were mixed in a flask, and 90 parts of nitrogen were blown into the flask.
The mixture was heated to and maintained at ℃, and a homogeneous mixed solution of the following monomer and polymerization initiator was added dropwise thereto over 4 hours.

20 parts of a monomer A solution having a solid content of about 60% obtained in Production Example 1 20 parts Hydroxyethyl methacrylate 20 parts Styrene 30 parts n-butylactylate 38 parts 2,2'-azobisisobutyronitrile 1.5 parts At temperature, 30.8 parts of toluene and 2,2'-
A half amount of a mixture of 1.0 part of azobis-2,4-dimethylvaleronitrile was added dropwise over 1 hour. Next, the temperature was increased to 100 ° C., and the remaining half was dropped over 1 hour. After the dropping was completed, the temperature was maintained at the same temperature for 1 hour, cooled, and 50 parts of isopropyl alcohol was mixed to obtain a resin solution. . The solids content of the resulting solution was about 40%. The number average molecular weight of the resin was about 26,000. The following components were added to this resin solution to obtain composition A.

80 parts of the resin solution having a solid content of about 40% Cymer 303 ^{(Note 1)} 8 parts Triethylamine 6.8 parts Isopropanol 10.2 parts Deionized water 95 parts The solid content of the obtained composition A was about 20%.

(Note 1) Cymel 303: manufactured by Mitsui Cyanamid, methyl etherified melamine resin, solid content: about 98%.

Example 1 20 parts of isobutyl acetate and 31.7 parts of methyl isobutyl ketone were mixed in a flask, heated and maintained at 90 ° C. while blowing nitrogen gas, and a homogeneous mixed solution of the following monomers and a polymerization initiator was added thereto for 4 hours. It dripped over.

30 parts of the monomer C solution having a solid content of about 50% obtained in Production Example 3 30 parts acrylonitrile 20 parts n-butyl acrylate 35 parts 2-hydroxyethyl methacrylate 30 parts 2,2'-azobisisobutyronitrile 1.0 part At the same temperature, 16.2 parts of isobutyl acetate, 16.2 parts of methyl isobutyl ketone and 2,2′-azobis-2,4-
Half of the mixture of 1.0 part of dimethylvaleronitrile was added dropwise over 1 hour. Then, the temperature was raised to 100 ° C., and the remaining half was dropped over 1 hour.
After holding for a time, it was cooled. Next, 53.0 parts of γ-isocyanatopropyltrimethoxysilane and 0.08 part of dibutyltin diacetate were added thereto, and reacted at 50 ° C. for 9 hours. After cooling, 410.9 parts of ethanol and 100 parts of toluene were added, and a resin C solution was added. I got The solids content of the resulting solution is about 20%
Met. The number average molecular weight of the resin C was about 30,000.

Example 2 A flask was mixed with 59 parts of methyl isobutyl ketone,
The mixture was heated to and maintained at 90 ° C. while blowing nitrogen gas, and a homogeneous mixed solution of the following monomer and polymerization initiator was added dropwise thereto over 4 hours.

1.67 parts of a monomer E solution having a solid content of about 60% obtained in Production Example 5 2-hydroxyethyl acrylate 22 parts n-isobutyl methacrylate 58 parts Acrylic acid 10 parts 2,2'-azobisisobutyronitrile 1.0 part After dropping, At the same temperature, a half amount of a mixture of 31.4 parts of toluene and 2 parts of 2,2'-azobis-2,4-dimethylvaleronitrile was added dropwise over 1 hour. Then, the temperature was raised to 100 ° C., and the remaining half was added dropwise over 1 hour. After completion of the addition, the temperature was maintained for 1 hour. After cooling, 70 parts of isobutyl acetate and 63.2 parts of methyl isobutyl ketone were added. A solution was obtained. The solids content of the resulting solution was about 30%.
The number average molecular weight of the resin was about 20,000.

The following components were blended with this resin solution to obtain composition E
I got

 The resin solution having a solid content of about 30% 80 parts Isophorone diisocyanate 6 parts Isobutyl ketone 14 parts The solid content of the obtained composition E was about 30%.

Example 3 The following mixture was compounded in a flask.

The silane B solution having a solid content of about 50% obtained in Production Example 2 482 parts Vinyltrimethoxysilane 296 parts Phenyltrimethoxysilane 198 parts Ethanol 115 parts Distilled water 194 parts Toluene 1038 parts This mixture is heated and reacted at 80 ° C. for 8 hours. Thereafter, the solvent was removed, and 1300 parts of the solvent was distilled off. Next, the reaction product in the flask was cooled and mixed with 1410 parts of ethanol to obtain a resin B solution. The solids content of the resulting solution was about 20%.

Example 4 The following mixture was compounded in a flask.

477 parts of a silane D solution having a solid content of about 30% obtained in Preparation Example 4 477 parts of vinyltrimethoxysilane 136 parts of methyltrimethoxysilane 136 parts of toluene 538.5 parts of deionized water 124.2 parts After blending, the mixture was heated at 80 ° C. for 8 hours. Then, the solution was removed, and 795.9 parts of the solvent was distilled off. Next, the reaction product in the flask was cooled, and 2511.2 parts of ethanol was added to obtain a resin D solution. The solids content of the resulting solution was about 20%.

Example 5 The following mixture was compounded in a flask.

Silane F solution having a solid content of about 30% obtained in Production Example 6 719 parts Vinyltrimethoxysilane 215.1 parts Ethanol 250.3 parts Deionized water 95 parts After blending, the mixture was heated at 80 ° C for 8 hours, and then the solvent was removed. 340 parts of solvent were distilled off. Next, the reaction product in the flask was cooled and mixed with 4902 parts of ethanol to obtain a resin F solution. The solid content of the resulting solution was about 5%.

Reference Example 2 The following mixture was blended in a flask, and
The reaction was performed at 5 ° C. for 10 hours.

Epicoat 1001 ^{(Note 2)} 1000 parts Acrylic acid 72 parts Tetraethylammonium bromide 5.4 parts Hydroquinone 1.1 parts Methoxypropanol 1065.5 parts Then, the mixture is cooled to 100 ° C and mixed with 106 parts of 2-mercaptopropionic acid and 70 parts of triethylamine. ° C
For 8 hours, and then cooled to obtain a resin solution.
The resulting solution was about 50% solids.

(Note 2) Epicoat 1001: a trade name of bisphenol A type epoxy resin (molecular weight: about 900) manufactured by Shell Chemical Company.

The following components were added to the resin solution obtained above to obtain a composition G.

 80 parts of the resin solution having a solid content of about 50% Cymer 303 10 parts Deionized water 410 parts The solid content of the obtained composition G was about 10%.

Test Examples 1 to 7 Conditions shown in Table 1 such that the resin solutions or compositions A to H obtained in Reference Example 1, Examples 1 to 5 and Reference Example 2 were dried on various materials to a dry film thickness of 0.5 μm. And dried. An epoxy-melamine-based paint was applied thereon to a dry film thickness of about 5 μm, and baked and cured at 140 ° C. for 20 minutes. The obtained coated plate was subjected to a salt water spray test, a yarn rust generation test, and an outdoor backlash test. The test results are shown in Table 1.

In addition, as a comparative test example, conventionally known chromic acid treatment,
Table 1 shows the test results of the epoxy-melamine-based paints applied and baked and cured in the same manner on the treated plate and the untreated plate treated with zinc phosphate.

Test method Salt spray test (SST): A test was performed according to JIS Z 2371 in which a cross cut was made on a coated plate. The salt spray time was 500 hours.

Yarn rust resistance test (FCT): After the coated surface of a coated plate with a cross cut cut down on the top of a beaker containing 12N hydrochloric acid, the hydrochloric acid vapor is applied to the coated surface and sealed, and then exposed to steam for 1 hour , 50 ± 2 ℃, 98 ± 2% RH
I went for 1000 hours.

Outdoor back-cloth test (EPT): A cross-cut coated plate was subjected to a 6-month test under the condition of a south surface of 30 mm according to JIS K 5400 9.9.

With respect to the coated plate after each test, the strip width on one side of the cross cut portion and the maximum length of the rusting width were determined, and these are shown in Table 1.

As apparent from Table 1 below, the resin of the present invention and the composition obtained by combining the resin of the present invention with a crosslinking agent and the like have excellent resistance to various materials as compared with conventional surface treatment compositions. Corrosion ability can be provided.

──────────────────────────────────────────────────続 き Continued on front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C08F 8/34 CAS

Claims (1)

(57) [Claims] (1) Expression A corrosion-inhibiting resin having at least one chelate-forming group in a molecule represented by the formula: