JPH0445111A - Anticorrosive resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin, having specific chelating groups, capable of imparting excellent anticorrosive properties to metal such as Fe or Zr producing bi- or trivalent metallic ions by corrosion and useful as non-pollution anticorrosive coatings, etc. CONSTITUTION:The objective resin having chelating groups selected from groups expressed by formulas I and II (R<1> and R<2> are H or 1-8C alkyl; R<3> to R<6> are H, 1-8C alkyl or together with two C atoms to which they are linked may form bifunctional o-phenylene group). The aforementioned resin is obtained by adding a carboxyl group-containing polymerizable compound such as (meth) acrylic acid to a bisphenol type epoxy resin, opening the ring of epoxy group, thereby introducing polymerizable unsaturated groups into the resin and then adding a compound expressed by formula III or IV to the resultant resin having the above-mentioned polymerizable double bonds. Furthermore, thiosalicylic acid is preferred as the compound expressed by formula III or IV.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a resin capable of forming a strong metal chelate complex on a metal surface to prevent metal corrosion.

Conventional technologies and their problems Conventionally, in order to prevent metal corrosion, (1) metal surface treatment to form an inorganic film such as phosphate or chromate on the surface of metal materials, (2) epoxy resin or phenol resin. Anti-corrosion technology has been used to form organic coatings on metal surfaces.

However, in the case of metal surface treatment, there are drawbacks such as: (1) the occurrence of environmental pollution due to heavy metal waste liquid; (2) the use of highly toxic substances such as acids, alkalis, and cyanide; and (2) the need for complicated processes.

Furthermore, in the case of anti-corrosion coatings, there is a problem in that the bonding force with metal is not strong enough to completely suppress corrosion reactions.

Currently, no anti-corrosion technology has been established that is non-polluting, practical, and exhibits excellent anti-corrosion properties, and its development is awaited.

Means for Solving the Problems In view of the above-mentioned current situation, the inventors of the present invention have proposed that epoxy resins and phenolic resins can be used as non-polluting surface treatment agents in place of inorganic surface treatment agents such as phosphates and chromates. In order to obtain a new, non-polluting resin that exhibits superior anti-corrosion properties, we have conducted research by comprehensively applying interfacial chemistry, thermodynamics, electrochemistry, complex chemistry, etc.

As a result, they focused on the fact that polymer compounds that can form chelate complexes bond to metals much more strongly than resins such as epoxy resins and phenol resins, and found that in polymer compounds that can form chelate complexes, chelate-forming groups As,
We discovered that by using a group in which a thioether group and a carboxyl group are bonded via a carbon atom, the bonding energy with the metal due to chelate formation exceeds the corrosion reaction energy, and that the charge of the metal ion can be neutralized. , we have completed the present invention.

That is, the present invention provides a group represented by the formula (wherein R1 and R2 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and a group represented by the formula (wherein and R6 are (respectively the same or different, each represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, or together with two bonded carbon atoms, forms a divalent 0-phenylene group) The object of the present invention is to provide a corrosion-inhibiting resin having at least one chelate-forming group selected from the group consisting of:

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

o -3-C-C-OH(I) (In the formula, R1 and R2 are the same as above) 3R5 o -3-C-C-C-OH[II)R' R60 (In the formula, R3, R4, R5 and R6 are the same as above) Representative examples of the above [I] or (III group) include chelate form 5-CH2-C-OH II -5-CH2CH2-C-OH 0HO represented by the formula. .

In the resin of the present invention, the above-mentioned chelate-forming group is a stable 5-membered ring (for example, in the case of formula 13) or a 6-membered ring (in the case of formula 13) or a nonionic intramolecular complex salt type with a dodecvalent or +3-valent metal ion.
For example, a model of the chelate complex formed by formula [n) is as follows.

[In the case of a +3-valent metal ion] [In the case of a +2-valent metal ion] As mentioned above, three sets of chelate-forming groups bind to a +3-valent metal ion, and to a +2-valent metal ion, Two sets of chelate-forming groups combine to form a 5- or 6-membered chelate complex in which the charge of the metal ion is neutralized by the carboxylate ion. The formed chelate complex has a neutralized charge and is nonionic, making it difficult for corrosion current to flow when corroding metals. Also, since it forms a 5-membered ring or a 6-membered ring, it is structurally It is stable. If the number of intervening carbon atoms exceeds 2, the complex formed will have a 7-membered ring or more, resulting in decreased stability, which is not preferable.

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

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

(1) The resin forming the base portion has a polymerizable double bond at the end or side chain, and this double bond has the following formula (III).
Or a method of conducting an addition reaction with the compound shown in [■].

(In the formula, R1 and R2 have the same meanings as above.) 3R5 HS -C-C-C-OH(IV3 RA R60 (In the formula, R3, R4, R5 and R6 have the same meanings as above.) ) (2) An addition reaction product of a compound having both a functional group such as a hydroxyl group and a polymerizable double bond and a compound represented by the above formula (1111) or (IVI), and an addition reaction product of a compound having both a functional group such as a hydroxyl group and a polymerizable double bond, and A method of reacting a functional group with a polymer having a reactive functional group such as an isocyanate group.

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

(4) A method of adding a compound represented by the formula [m] or [IV) to a silane compound or resin having an etherified silanol group and a polymerizable double bond. Alternatively, a compound or resin having the structural moiety of the formula [I) or [II] obtained by this method and an etherified silanol group may be partially condensed, or another silane compound having an etherified silanol group. A method of partial co-condensation with.

In the method (1), the resin having a polymerizable double bond at the terminal or side chain is not particularly limited, and various resins obtained by known methods 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 moats, and various epoxy resins such as bisphenol type having epoxy groups at the terminal or side chain. A carboxyl group-containing polymerizable unsaturated compound such as (meth)acrylic acid is added to the resin to open the epoxy group,
It is obtained by introducing a polymerizable unsaturated group into a resin. This addition reaction can be carried out by heating both at, for example, about 50 to 150°C for about 30 minutes to 8 hours.

In addition, isocyanate ethyl (meth)acrylate, m-α, α isocyanate ethyl (meth)acrylate, m-α, α
It can also be obtained by introducing a polymerizable unsaturated group by adding an isocyanate compound containing a polymerizable unsaturated group such as '-isopropenyl phenyl isocyanate. This addition reaction can be carried out, 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 can be formed into the resin by reaction with a compound represented by the above [■] or (IV) formula.
A chelating group of the formula I[) is introduced. Typical examples of the compound represented by the above formula (m) or [IV3 include thiosalicylic acid, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptopropionic acid, etc. Among these, thiosalicylic acid has an odor. The addition reaction of the compound represented by the formula Cm) or [■] to the polymerizable double bond in the resin is carried out in the presence of an amine catalyst, for example, using a conventional
This can be carried out by reacting at 0 to 100°C for about 1 to 24 hours.

The method (2) above is a modification of the reaction order in the method (1), in which a reaction product having a chelate-forming group and a functional group represented by the formula CI) or CI[) is first produced. In this method, the functional groups of this material are reacted with the functional groups in the polymer to increase the molecular weight.

In the method (3) above, the formula (I) or [II]
A compound having a chelate-forming group and a polymerizable double bond is, for example, a combination of a compound represented by the above formula (m) or [IV) and a hydroxyl group-containing unsaturated monomer such as 2-hydroxyethyl (meth)acrylate. The hydroxyl group in the addition product is
Isocyanate ethyl (meth)acrylate, m-α,
It can be obtained by addition to a polymerizable double bond-containing monoisocyanate compound such as α'-isopropenyl phenyl isocyanate. Formula (IID or [I
The reaction between the compound represented by V) and the hydroxyl group-containing unsaturated monomer can be carried out, for example, by reacting equimolar amounts of both in the presence of an amine catalyst at about 20 to 100°C for about 1 to 24 hours. . The addition product obtained by this has a hydroxyl group, and the addition reaction between this product and a polymerizable double bond-containing monoisocyanate compound is carried out, for example, in the presence of a tin-based catalyst in equimolar amounts of both at about 20 to 100°C. Approximately 1
This can be carried out by reacting for ~10 hours.

The compound having a chelate-forming group and a polymerizable double bond of formula CI) or (II) can also be obtained by methods other than those described above. For example, 2 moles of a compound represented by formula Cm) or [IV) and 2 moles of a halogenated hydrocarbon containing a polymerizable double bond such as allyl bromide are reacted in the presence of 1 mole of a complex-forming metal salt such as nickel chloride. An example of this method is to pickle the resulting precipitate.

In the method (3), other polymerizable unsaturated monomers used for copolymerizing with the compound having a chelate-forming group and a polymerizable double bond of formula (I) or (n) include, for example, methyl ( meth)acrylate, ethyl(meth)
01-C18 alkyl ester of (meth)acrylic acid such as acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate; 2 - Hydroxyl group-containing unsaturated monomers such as 02-C8 hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, and allyl alcohol: styrene, α-methylstyrene,
Aromatic vinyl compounds such as vinyltoluene; vinyl acetate,
(meth)acrylamide, (meth)acrylonitrile,
Monomers such as N-methylol (meth)acrylamide butyl ether can be mentioned, and these can be used alone or in combination of two or more.

The copolymerization of the polymerizable double bond-containing adduct with the polymerizable unsaturated monomer having the above properties can be carried out by a known copolymerization method, for example, by combining the above components in the presence of a polymerization catalyst and preferably an organic solvent. This can be carried out by heating the reaction.

In the method (4) above, the silane compound or resin having a polymerizable double bond and an etherified silanol group is preferably a silane compound represented by the following general formula [■], or one type of these silane compounds. Alternatively, resins obtained by partially condensing two or more types of silane compounds, and partial co-condensates of these silane compounds and other silanes having an etherified silanol group may be mentioned.

A-3i-Z[V) [wherein A represents an unsaturated hydrocarbon group or an unsaturated carbonyloxyalkyl group, X is a hydrogen atom, and has 1 to 18 carbon atoms]
hydrocarbon group, 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. 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 aryloxy group having 5 to 8 carbon atoms.
represents an aliphatic cyclohydrocarbonoxy group, and may be the same as X. ] Preferred examples of the above A include a vinyl group, an allyl group, a methacryloyloxyethyl group, an acryloyloxyethyl group, a methacryloyloxypropyl group, an acryloyloxypropyl group, and the like.

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
Among the ~8 alicyclic hydrocarbon oxy groups, preferred are, for example, alkoxy groups having 1 to 8 carbon atoms such as methoxy, ethoxy, propoxy, butoxy, hexoxy, octoxy, and methoxyethoxy groups, phenoxy groups, Examples include cyclohexyloxy group.

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

Representative examples of the silane compound represented by the above general formula [v] include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(n-propoxy)silane, vinylbis(methoxy)methylsilane, vinylbis(ethoxy)methylsilane, vinylbis(n-propoxy)silane, vinylbis(methoxy)methylsilane, vinylbis(n-propoxy)silane, vinylbis(methoxy)methylsilane, -propoxy)methylsilane, allyltrimethoxysilane, β-acryloyloxyethyltrimethoxysilane, β-methacryloyloxyethyltrimethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-methacryloyloxinepropyltrimethoxysilane, γ-methacryloyloxysilane, Quinpropyl(methyljethoxy)silane, β-methacryloyloxyethyltriethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-
Methacryloyloxypropyltris(2-methoxyethoxy)silane, β-methacryloyloxypropyltris(n-butoxy)silane, γ-methacryloyloxypropyltris(isobutoxy)silane, γ-methacryloyloxypropyltris(isopropoxy)silane, etc. Can be mentioned.

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

The partial condensation of the silane compound represented by the above formula [v] and the partial co-condensation of the silane compound represented by the above formula [V] with another silane compound having an etherified silanol group can be carried out using conventionally known etherified silanes. It can be carried out according to the condensation method of compounds, and is generally heated to room temperature to a temperature below the boiling point, preferably 50 to 90°C, in the presence of an acid such as an organic acid such as acetic acid, an inorganic acid such as hydrochloric acid, and water. This can be done by: The amount of water may be increased or decreased as appropriate depending on the degree of condensation.

The above formula [■] or [I
By addition with the compound represented by V), a silane compound or resin having a chelate forming group of the formula CI) or [■] and an etherified silanol group is obtained. The above addition reaction can be carried out by reacting both, for example, in the presence of an amine catalyst, usually at about 20 to 100°C for about 1 to 24 hours. Resins obtained by this method are included in the resins of the present invention.

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

As the other silane compound having the etherified silanol group, those shown as other silane compounds that can be partially co-condensed with the silane compound of the formula [■] can be used.

Partial condensation and partial co-condensation can be performed in the same manner as the partial (co)condensation method described above.

The resin of the present invention obtained by the method (4) has an etherified silanol group, and this group reacts with moisture in the air, hydrolyzes to form a silanol group, and undergoes a crosslinking reaction. It can be a so-called moisture curing type.

Furthermore, the resin obtained by the method (1), (2) or (3) above can also be made moisture-curable by introducing an etherified silanol group into the resin. To introduce an etherified silanol group into a resin, for example, a hydroxyl group is made to exist in the resin, and a monoisocyanate compound having a silanol group etherified to the hydroxyl group is added to the hydroxyl group in the presence of a tin-based catalyst. about 2
A method such as reacting at 0 to 100°C for about 1 to 10 hours can be used. Representative examples of the monoisocyanate compound having an etherified silanol group include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and the like.

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

The resin of the present invention preferably has film-forming ability, and suitably has a number average molecular weight in the range of about 570 to 100,000, more preferably about 800 to 50,000. Furthermore, the resin of the present invention must have at least one of the above-mentioned chelate-forming groups in the molecule, and the resin 10
It is preferable to have several chelate-forming groups in 0.0g, more preferably 0.2 to 3.5 avogadros, more preferably 0.3 to 3.0 avogadros.

In the resin of the present invention, various types of base resins can be used as described above, such as acrylic resins, epoxy resins, polyester resins, alkyd resins,
Examples include silicon-containing resins.

The resin of the present invention may be used after being diluted with an organic solvent, and the amount of carboxyl groups in the resin may be adjusted, for example, to an acid value of 30 to
130, the carboxyl group is neutralized with a base such as an organic amine or ammonia, and the mixture may be used by dispersing or dissolving it in water.

Furthermore, the resin of the present invention can have a reactive group such as a hydroxyl group present in the resin in addition to the above-mentioned chelate-forming group, and can be used in combination with a crosslinking agent that reacts with this reactive group. For example, when the above-mentioned reactive group is a hydroxyl group, the crosslinking agent may be a known polyisocyanate compound, a blocked polyisocyanate compound, an aminoplast resin, or a formaldehyde condensation product of a nitrogen-containing compound such as urea, melamine, or benzoguanamine. or a lower alkyl etherified product of this condensate (the alkyl group has 1 to 4 carbon atoms), etc., and can be crosslinked at room temperature or by heating.

Effects of the Invention The resin of the present invention, when used alone or in combination with a crosslinking agent, has excellent properties against metals that generate +2 or +3 valent metal ions due to corrosion, such as iron, zinc, copper, and aluminum. It can provide excellent corrosion resistance and is non-polluting. Therefore, the resin of the present invention is extremely useful as a surface treatment agent for metals or an anticorrosion paint.

Example Hereinafter, the present invention will be explained in more detail with reference to Examples.

In addition, hereinafter, "1 part" and "%" mean "part by weight" and "% by weight", respectively, unless otherwise specified.

Production Example 1 3 parts of 245°C of methyl isobutyl ketone were blended 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 blended.

2-Hydroxyethyl acrylate 116 parts Thioglycolic acid 92 parts Triethylamine 1.8 parts After blending the above mixture, 5 parts
The mixture was heated at 0°C for 5 hours and then heated at 80°C for 1 hour to obtain a hydroxyl group-containing adduct solution. Regarding the obtained solution, it was confirmed that the SH group of thioglycolic acid was added to 2-hydroxyethyl acrylate and that no SH group remained. Confirmed by color reaction.

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

m-α, α′ -isopropenyl phenyl isocyanate 116 parts dibutyltin diacetate 0.2 parts hydroquinone
0.4 part After blending the above mixture, it was heated at 50°C for 5 hours under air blowing, and then heated at 80°C for 1 hour.
A monomer A solution was obtained by heating for a period of time. The solid content of the resulting resin solution was about 60%. The main structure of monomer A is represented by the general formula.

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

γ-Methacryloyloxypropyltrimethoxysilane 248 parts Thiosalicylic acid 154 parts Triethylamine 3.0 parts Methoxypropanol
402 parts The above compounds were blended, stirred, heated at 50°C for 5 hours under nitrogen gas substitution, and then heated at 80°C.
The mixture was heated and reacted for 1 hour to obtain a silane B solution with a solid content of about 50%. The main structure of Silane B is the general formula (%) 2000 parts of water was blended into a flask, nitrogen gas was blown into the flask to replace the nitrogen gas, and the following compounds were blended.

Thiosalicylic acid 308 parts Allyl bromide 242 parts Nickel chloride
238 parts sodium carbonate
After blending and stirring 106 parts of each of the above compounds, the mixture was left to stand at room temperature (20° C.) for 24 hours under nitrogen gas substitution to obtain a precipitate. After filtering this precipitate and washing with water, 5N acetic acid aqueous solution 1000
Allylthiosalicylic acid was obtained by adding the mixture into a separate flask, stirring, filtering, and drying the filtration residue.

194 parts of allylthiosalicylic acid was dissolved in 427 parts of methyl isobutyl ketone, and 7 parts of mercaptoethanol was added to the solution.
8 parts were added thereto, and the reaction was carried out at 80° C. for 8 hours under nitrogen gas blowing and stirring to obtain a hydroxyethylthiopropylthiosalicylic acid solution with a solid content of about 39%. This solution 6
99 parts were cooled to 50°C, the following compounds were blended therein under air blowing, and the mixture was heated at 50°C for 7 hours to obtain a monomer C solution.

Isocyanatoethyl methacrylate 155 parts Dibutyltin diacetate 0.21 part Hydroquinone
The solid content of the solution obtained was approximately 50%. The main structure of monomer C is the general formula % 47 parts of methyl isobutyl ketone is blended in a flask.
The mixture was heated to 50° C. and the following compounds were blended under nitrogen blowing.

699 parts of hydroxyethylthiopropylthiosalicylic acid with a solid content of about 39% used in Production Example 3 205 parts of γ-isocyanatopropyltrimethoxysilane 0.24 parts of dibutyltin diacetate After blending each of the above compounds, under nitrogen blowing, After heating at 50° C. for 7 hours and then heating at 80° C. for 1 hour to react, the mixture was cooled and diluted with 636 parts of ethanol to obtain a Silane D solution. The solids content of the resulting solution was approximately 30%.

The main structure of Silane D is the general formula It is expressed as

Production Example 5 1000 parts of water, 19 parts of allylthiosalicylic acid in a flask
4 parts and 101 parts of triethylamine were blended and uniformly dissolved. 62 parts of 2,3-dimercapto-1-propatool and 0.5 part of chloroplatinic acid were added to this, and while stirring,
After a heating reaction at 80°C for 8 hours under nitrogen gas blowing, the mixture was cooled to produce 1-hydroxypropane represented by the following formula.
2,3-di(thio-8-γ-propylthiosalicylic acid)
I got it.

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

1-hydroxypropane-2,3 monodi(thio-8-γ-propylthiosalicylic acid) 514 parts isocyanatoethyl methacrylate 155 parts dibutyltin diacetate) 0.33 parts hydroquinone
After blending 0.66 parts of each of the above compounds, the monomer E was reacted by heating at 50°C for 7 hours under air blowing.
A solution was obtained. The solids content of the resulting solution was approximately 60%.

The main structure of monomer E is the general formula % Formula % 719 parts of methyl isobutyl ketone was blended in a flask, heated to 50°C, and the following compounds were blended under nitrogen gas blowing.

1-Hydroxypropane-2,3-di(thio-8-γ-propylthiosalicylic acid) 514 parts γ-isocyanatopropyltormethoxysilane 205 parts Dibutyltin diacetate 0.36 parts After blending each of the above compounds, nitrogen gas The reaction mixture was heated at 50° C. for 7 hours under blowing, then heated at 80° C. for 1 hour, cooled, and 959 parts of ethyl alcohol was added to obtain a Silane F solution. The solids content of the resulting solution was 30%. The main structure of Silane F is the general formula % Formula % 20 parts of isobutyl alcohol and 38.7 parts of methyl isobutyl ketone are mixed in a flask, heated to 90°C under nitrogen gas blowing, maintained, and the following monomers are added to this "1". A homogeneous mixed solution of polymerization initiator and polymerization initiator was added dropwise over 4 hours.

60% solids monomer A solution obtained in Production Example 1 20 parts Hydroxyethyl methacrylate 20 fS3 steel
30 parts n-butyl acrylate 38 parts 2.2'
- After finishing dropping 1.5 parts of azobisisobutyronitrile,
At the same temperature, half of a mixture of 30.8 parts of toluene and 1.0 part of 2,2'-azobis-2,4-dimethylvaleronitrile was added dropwise over 1 hour. Next, the temperature was raised to 100°C, the remaining half amount was added dropwise over 1 hour, and after the dropwise addition was completed, the same temperature was maintained for 1 hour, then cooled, and 50 parts of isopropyl alcohol was added to obtain a resin solution. .

The solids content of the resulting solution was approximately 40%. The number average molecular weight of the resin was approximately 26,000. Composition A was obtained by blending the following components with this resin solution.

The above resin solution with a solid content of approximately 40% 80 parts Sasumel 303 (Note 13) 8 parts triethylamine 6.8 parts isopropanol
10.2 parts deionized water
The solid content of 95 parts of Composition A was about 20%.

(Note 1) Cynulus 03: Manufactured by Mitsui Cyanamid Co., Ltd., methyl etherified melamine resin, solid content approximately 98%.

Example 2 20 parts of isobutyl acetate and 31.7 parts of methyl isobutyl ketone were mixed in a flask and heated at 90° under nitrogen gas blowing.
C., and a uniform mixed solution of the following monomer and polymerization initiator was added dropwise thereto over 4 hours.

Monomer C solution with 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 Dropping completed rear,
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 containing 1.0 part of dimethylvaleronitrile was added dropwise over 1 hour. Then the temperature was increased to 100°C,
The remaining half amount was added dropwise over 1 hour, and after the addition was completed, the temperature was kept at the same temperature for 1 hour, and then cooled. Next, 53.0 parts of γ-isocyanatopropyltrimethoxysilane and 0.08 parts of dibutyltin diacetate were added to this, and the mixture was heated at 50°C.
After reacting for an hour, it was cooled, and 410.9 parts of ethanol and 100 parts of toluene were added to obtain a resin C solution. The solids content of the resulting solution was approximately 20%. Further, the number average molecular weight of Resin C was about 30,000.

Example 3 59 parts of methyl isobutyl ketone was blended in a flask,
The mixture was heated and maintained at 90° C. under nitrogen gas blowing, and a homogeneous mixed solution of the following monomer and polymerization initiator was added dropwise thereto over 4 hours.

Monomer E solution with a solid content of about 60% obtained in Production Example 5 1.67 parts 2-hydroxyethyl acrylate 22 parts n-isobutyl methacrylate 58 parts acrylic acid
10 parts 2.2'-Azobisisobutyronitrile 1.0 part After completion of dropping,
At the same temperature, 31.4 parts of toluene and 2.2'-azobis-
Half of a mixture of 2 parts of 2,4-dimethylvaleronitrile was added dropwise over 1 hour. Next, the temperature was raised to 100°C, and the remaining half amount was added dropwise over 1 hour. After the dropwise addition was completed, the temperature was maintained for 1 hour, then cooled, and 70% of isobutyl acetate was added.
1 part and 63.2 parts of methyl isobutyl ketone were added to obtain a resin solution. The solids content of the resulting solution was approximately 30%. The number average molecular weight of the resin was approximately 20,000.

The following components are added to this resin solution;-1 Composition E
I got it.

The above 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 4 The following mixture was blended into a flask.

Silane B solution with a solid content of approximately 50% obtained in Production Example 2 482 parts Vinyltrimethoxysilane 296 parts Phenyltrimethoxysilane 198 parts Ethanol
115 parts Distilled water 194 parts Toluene
1038 parts of this mixture was heated and reacted at 80° C. for 8 hours, and then the solvent was removed to distill out 1300 parts of the solvent. The reaction mixture in the flask was then cooled and 14 mL of ethanol was added.
A resin B solution was obtained by blending 10 parts. The solids content of the resulting solution was approximately 20%.

Example 5 The following mixture was blended into a flask.

Monomer D solution with a solid content of approximately 30% obtained in Production Example 4 477 parts Vinyltrimethoxysilane 148 parts Methyltrimethoxysilane 136 parts Toluene
538. 5 parts deionized water
After mixing 124.2 parts, 8 parts of this mixture
Heated at 0°C for 8 hours, then desolvented to give 795.9
part of the solvent was distilled off. Next, the reactant in the flask was cooled, and 2,511.2 parts of ethanol was added to obtain a resin solution. The solids content of the resulting solution was approximately 20%.

Example 6 The following mixture was blended into a flask.

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

Example 7 The following mixture was blended in a flask, and under air blowing, 11
The reaction was carried out at 5°C for 10 hours.

Epicoat 1001 Axis 2' 1000 parts Acrylic acid 72 parts Tetraethylammonium bromide 5.4 parts Hydroquinone 1.1 parts Metkin propatool 1065.5 parts Then cooled to 100°C, and added with 106 parts of 2-mercaptopropionic acid and 70 parts of triethylamine. The mixture was reacted at 100° C. for 8 hours, and then cooled to obtain a resin solution. The resulting solution had a solids content of approximately 50%.

(Note 2) Epicote 1001 is a trade name of bisphenol A epoxy resin (molecular weight 900) manufactured by Nisiel Chemical Co., Ltd.

Add the following ingredients to the resin solution obtained above,
Composition G was obtained.

80 parts of the above resin solution with a solid content of approximately 50% Sasumel 303 10 parts deionized water
The solid content of 410 parts of composition G obtained was about 10%.

Test Examples 1 to 7 The resin solutions or compositions A to 7 obtained in Examples 1 to 7 were applied onto various materials to a dry film thickness of 065 μm and dried under the conditions shown in Table 1. On top of this, epoxy/melamine paint was applied to a dry film thickness of 5 μm, and heated to 140°C.
Baking was performed for 20 minutes to harden. The obtained coated board was subjected to a salt spray resistance test, a yarn rust resistance test, and an outdoor vacuum test. The test results are shown in Table 1.

In addition, as a comparative test example, the above-mentioned epoxy/melamine paint was applied in the same manner on a treated board that had been subjected to conventional chromic acid treatment and zinc phosphate treatment, and on an untreated board, and the baking was cured. The results are also shown in Table 1.

Test Methods Salt Spray Resistance Test (SST): The test was conducted according to JIS 2 2371 by making crosscuts on the coated plate. The salt water spray time was 500 hours.

Thread rust resistance test (FCT): A beaker containing 12N hydrochloric acid was placed in a beaker with a cross-cut cut on top, and the coated surface of the plate was sealed so that the hydrochloric acid vapor hit the coated surface for 1 hour. Thereafter, a humidity test was conducted for 1000 hours at 50±2° C. and 198±2% RH.

Outdoor Bakuro Test (EPT): According to JIS K 5400 9.9 for coated plates with cross cuts,
Tests were conducted for 6 months under the condition of facing south at 30°.

For each coated plate after the test, the peeling width on one side of the cross-cut portion and the maximum length during rusting were determined, and these are shown in Table 1.

As is clear from Table 1 below, the resin of the present invention and the composition that combines the resin of the present invention with a crosslinking agent, etc. have better resistance to various materials than conventional surface treatment compositions. Corrosion ability can be imparted.

Claims (1)

[Claims] [1] Formula ▲ Numerical formula, chemical formula, table, etc. There are groups represented by the formula ▲ mathematical formulas, chemical formulas, tables, etc. A chelate-forming group selected from the groups represented by (1 to 8 alkyl groups, or which together with two bonded carbon atoms form a divalent O-phenylene group) is present in the molecule. Corrosion-preventing resin having at least one.