JPH0931408A - Highly reactive modified phenolic resin anticorrosion paint - Google Patents

Abstract

(57) [Summary] [Structure] (A) A modified phenolic resin obtained by polycondensing a heavy petroleum oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst is treated with an acid catalyst. An anticorrosive paint comprising a resin composition comprising a highly reactive modified phenol resin having a low molecular weight by reacting with a phenol in the presence of the above and (B) an epoxy resin. [Effect] It has excellent weather resistance, corrosion resistance (chemical resistance), heat resistance, etc. and does not substantially contain an acid, so it does not corrode the metal to be anticorrosive (corrosion proof) and has high adhesion to the metal. A coating film having excellent mechanical properties when heated is obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a novel highly reactive modified phenolic resin anticorrosion paint. More specifically, the present invention relates to an anticorrosion coating material containing a novel highly reactive modified phenolic resin obtained by reducing the molecular weight of a modified phenolic resin derived from heavy petroleum oils or pitches with phenols. More specifically, the anticorrosion coating composition of the present invention is excellent in weather resistance, corrosion resistance (chemical resistance), heat resistance and the like by using the above-mentioned novel highly reactive modified phenolic resin as an essential vehicle component. Since it does not substantially contain, it does not corrode the metal to be anticorrosive (corrosion proof) and has high adhesiveness to the metal,
It has the characteristic of exhibiting excellent mechanical properties when heated.

[0002]

2. Description of the Related Art Conventionally, various anticorrosive paints have been known for the purpose of anticorrosion of the inner surface of steel plates such as marine steel structures, steel pipes in contact with fresh water and seawater, water pipes and sewer pipes, and the surface of steel plates of ships.
As these, for example, coating materials such as coal tar enamel, tar epoxy, and epoxy resin are known.

In particular, epoxy resin anticorrosive paints have attracted attention because of their high adhesiveness, heat resistance and dimensional stability.
In order to further improve the anticorrosive property of the epoxy resin anticorrosive paint, it has been attempted to blend petroleum resin, coumarone resin, xylene resin and the like in addition to bituminous substances such as coal tar, pitch and asphalt.

[0004]

However, these anticorrosion paints are still insufficient in terms of weather resistance, corrosion resistance (chemical resistance), heat resistance, adhesiveness and the like. It is an object of the present invention to provide an anticorrosion paint whose corrosion resistance, heat resistance, weather resistance and the like are significantly improved.

[0005]

Means for Solving the Problems As a result of various studies on the above-mentioned problems, the present inventor has reduced the molecular weight of modified phenolic resins made from petroleum heavy oils or pitches with phenols as a vehicle for anticorrosion paints. By using a new highly reactive modified phenolic resin, it has excellent weather resistance, heat resistance, and excellent mechanical properties when heated. Furthermore, it contains substantially no acid, so it is anticorrosive (rustproof) treated. The inventors have found that it is possible to provide an anticorrosion paint that does not corrode the above-mentioned metal and has high adhesion to the metal, and has completed the present invention.

That is, the present invention: (A) a modified phenolic resin obtained by polycondensing a heavy petroleum oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst, Provided is a highly reactive modified phenolic resin anticorrosion coating composition, which comprises a resin composition comprising a highly reactive modified phenolic resin having a low molecular weight by reacting with a phenol in the presence of an epoxy resin and (B) an epoxy resin. Further, the above resin composition is also characterized in that it further contains a curing agent and / or a curing accelerator (C). Further, the compounding ratio of the highly reactive modified phenolic resin (A) / epoxy resin (B) is 10/90 to 90/10 (parts by weight).
It is also characterized in that

Hereinafter, the present invention will be described in detail. (1) Vehicle for anticorrosion paint Highly reactive modified phenolic resin component (A) (i) In the present specification, petroleum heavy oil or pitches, formaldehyde polymer and phenols are present in the presence of an acid catalyst. The reaction product obtained by polycondensation below is referred to as "modified phenol resin", and modified phenol resin having a low molecular weight with phenols used as a vehicle for anticorrosion paint in the present invention is referred to as "highly reactive modified phenol resin ( A) ", and they are usually used as free of impurities through purification steps.

The highly reactive modified phenolic resin (A) used in the present invention is basically prepared by modifying a modified phenolic resin obtained in a specific polycondensation step with a low molecular weight step of phenols under specific conditions. It is produced by a method consisting of polymerizing. The vehicle for anticorrosion paint of the present invention is characterized in that the highly reactive modified phenolic resin (A) is used as an essential component.

The vehicle for anticorrosion paints of the present invention is characterized by blending the highly reactive modified phenolic resin (A) and the epoxy resin (B) described below, and further the highly reactive modified phenolic resin (A). In addition to bituminous substances such as coal tar, pitch, and asphalt, which are known as vehicles for anticorrosion paints, in a small amount that does not impair the function of petroleum resin, coumarone resin, xylene resin and polycyclic aromatic hydrocarbon-based modified phenol resin. You may mix | blend thermosetting resins, such as such phenol resin. Of course, a curing agent and / or a curing accelerator (C) described below and various additives as necessary may be added to the vehicle for anticorrosion paint.

(2) Production of Modified Phenolic Resin The highly reactive modified phenolic resin (A), which is one component of the matrix constituting the laminate according to the present invention, is a modified phenolic resin obtained in a specific polycondensation step. It is produced by reducing the molecular weight in a molecular weight reduction step under specific conditions. The method for producing the modified phenolic resin is preferably carried out by the method described in Japanese Patent Application No. 5-40646, and more specifically by the following method. Modified phenol resin and method for producing the same The modified phenol resin raw material used in the present invention is polycondensed with petroleum heavy oils or pitches shown below, phenols and formaldehyde polymer in the presence of an acid catalyst.

(B) Petroleum-based heavy oils or pitches It is necessary to use petroleum-based heavy oils or pitches as a raw material. The petroleum heavy oils or pitches have an aromatic hydrocarbon fraction fa value and an aromatic ring hydrogen content Ha value of
It is desirable to use the one shown in the following formula.

[Equation 1] (The fa value can be determined by ¹³ C-NMR,
The Ha value can be determined by ¹ H-NMR. ) The aromatic hydrocarbon fraction fa value is 0.40 to 0.95,
Preferably 0.5 to 0.8, more preferably 0.55
˜0.75 and the aromatic ring hydrogen content Ha value is 20 to 80.
%, Preferably 25-60%, more preferably 25-
Desirably, it is 50%.

The petroleum heavy oils or pitches as raw materials are
The number of condensed rings of the aromatic hydrocarbon constituting this is not particularly limited, but it is preferably a condensed polycyclic aromatic hydrocarbon mainly having 2 to 4 rings. In the case of a condensed polycyclic aromatic hydrocarbon having five or more rings, the boiling point exceeds 450 ° C. in most cases, so that it is difficult to collect those having a narrow boiling point range and the quality is not stable. The heavy petroleum-based oils or pitches used as raw materials are
It is obtained as a distillation residual oil of crude oil, a hydrogenolysis residual oil, a catalytic cracking residual oil, a thermal decomposition residual oil of naphtha or LPG and a vacuum distillate of these residual oils, an extract by solvent extraction or a heat-treated product. From these, the fa value and H
It is preferable to select and use a suitable a value.

(B) Formaldehyde polymer As the formaldehyde polymer as a raw material, there can be mentioned linear polymer such as paraformaldehyde, polyoxymethylene (particularly, oligomer) and cyclic polymer such as trioxane. The mixing ratio of heavy petroleum oils or pitches (a) and formaldehyde polymer (b) is
The number of moles of the formaldehyde polymer in terms of formaldehyde is 1 to 15, preferably 2 to 12, and more preferably 3 to 11 per 1 mole of the average number of moles calculated from the average molecular weight of heavy petroleum oils or pitches. I need to be there.

If the mixing ratio is less than 1, it may not be possible to obtain an anticorrosion paint having sufficient physical properties, which is not preferable. On the other hand, when the mixing ratio is more than 15, both the performance of the obtained anticorrosion paint and the yield of the modified phenol resin are almost unchanged, so it is considered useless to use more formaldehyde polymer.
Further, the excess formaldehyde polymer may hinder the molecular weight reduction of the modified phenol resin in the molecular weight reduction step described later.

(C) Phenols Examples of phenols as raw materials include phenol, cresol, xylenol, resorcin, catechol, hydroquinone, bisphenol A, bisphenol F and α-.
One or more phenolic compounds selected from the group of naphthol and β-naphthol can be mentioned. The amount of phenols added is 0.3 to 5, preferably 0.5 to 3, as the number of moles of phenols per 1 mole of the average number of moles calculated from the average molecular weight of heavy petroleum oils or pitches. I need to be there.

When the amount added is less than 0.3, the reactivity of heavy petroleum oils or pitches with formaldehyde is inferior to that of phenols with formaldehyde, so that a sufficient crosslinking density is obtained. Therefore, an anticorrosive paint having sufficient physical properties cannot be obtained. On the other hand, when the addition amount of phenols exceeds 5, the modifying effect due to the modification of the phenol resin tends to decrease.

Phenols are preferably added sequentially by a method such as dropping. The rate of addition is from 0.05 to 5% by weight, preferably 0.1 to 2% by weight, based on the total weight of the reaction mixture. The timing for starting the addition of the phenols is not particularly limited, but the timing for starting the addition may be the time at which the reaction between the petroleum heavy oil or pitches and formaldehyde has not substantially progressed. In practice, from the state in which the reaction rate of formaldehyde estimated from the amount of remaining free formaldehyde is substantially 0,
It is desirable to start the sequential addition of phenols at the time of 0% or less, preferably 50% or less.

(D) Acid catalyst As the acid catalyst, a Bronsted acid or a Lewis acid can be used, but a Bronsted acid is preferably used. As the Bronsted acid, toluenesulfonic acid,
Xylene sulfonic acid, hydrochloric acid, sulfuric acid, formic acid and the like can be used, but p-toluene sulfonic acid and hydrochloric acid are particularly excellent.
The amount of the acid catalyst used is 0.1 to 30% by weight, preferably 1 to 30% by weight based on the total amount of the petroleum heavy oil or pitches, the formaldehyde polymer and the phenols, which are raw materials for production.
It is 20% by weight.

(E) Reaction conditions In order to produce a modified phenolic resin in the polycondensation step using the above raw materials and catalysts, for example, petroleum heavy oils or pitches and formaldehyde polymer should be in the above proportions. It is preferable that the mixture is heated and stirred in the presence of an acid catalyst, and phenols are successively added to the mixture until the above ratio is reached to polycondense these raw materials. At that time, the reaction temperature is 50 to 160 ° C, preferably 60 to 120 ° C. The reaction temperature is determined in consideration of the raw material composition, the reaction time, the properties of the resin produced, and the like.

The reaction time is 0.5 to 10 hours, preferably 1 to 5 hours. The reaction time depends on the raw material composition, reaction temperature,
It is determined in consideration of the addition rate of phenols, the properties of the resin produced, and the like. When the reaction is carried out batchwise, it can be carried out in one step, and it is preferably carried out in one step. Further, when the continuous method is used, it is not necessary to use a device which is difficult to control and which is used for a conventional modified phenolic resin, such as continuously mixing two or more kinds of reaction products at a constant amount,
A reaction vessel of a complete mixing type may be placed in the middle part, and the phenols to be added may be fed into the reaction vessel in fixed amounts. Such a device is relatively inexpensive and has good operability.

In the present invention, such a polycondensation reaction can be carried out without a solvent, but in that case, it is necessary to pay attention to the uniformity of the reaction. A suitable solvent may be used to reduce the viscosity of the reaction system so that a uniform reaction may occur.
The solvent is not particularly limited, but is, for example, aromatic hydrocarbon such as benzene, toluene, xylene;
Halogenated aromatic hydrocarbons such as chlorobenzene; Nitrated aromatic hydrocarbons such as nitrobenzene; Nitrated aliphatic hydrocarbons such as nitroethane and nitropropane; Halogenated fats such as perkrene, trichlene and carbon tetrachloride Examples thereof include group hydrocarbons.

Step of Purifying Modified Phenolic Resin The highly reactive modified phenolic resin according to the present invention is prepared by lowering the molecular weight of the modified phenolic resin obtained by the polycondensation reaction in the lowering molecular weight step according to the method of the present invention. it can. However, in the modified phenol resin obtained by the polycondensation step, in addition to the target modified phenol resin, an acid catalyst, unreacted components, reaction solvent, and the like may remain, and these are low molecular weight reaction. It affects the reaction conditions and the amount of raw materials, catalysts, etc. involved in the reaction. For example, when the modified phenol resin used in the step of lowering the molecular weight contains a large amount of a formaldehyde polymer which is a crosslinking agent as an unreacted component, a modified phenol resin,
The polycondensation reaction of the formaldehyde polymer and the phenols may precede the inhibition of lowering the molecular weight.

Therefore, in order to suitably set the reaction conditions in the low molecular weight conversion step so that the modified phenolic resin can efficiently lower the molecular weight by the reaction of the modified phenol resin and the phenols, it is necessary to use in the low molecular weight conversion step. It is desirable that the modified phenolic resin obtained does not contain an acid catalyst or formaldehyde polymer in an amount that inhibits the molecular weight reduction reaction. That is, after the polycondensation step, it is preferable to perform the following purification steps on the modified phenol resin in any order or, if necessary, simultaneously in order to control the reaction to reduce the molecular weight of the phenols.

(I) A purification step of treating / precipitating with a specific solvent to remove solvent-soluble components including unreacted components, and (i
i) A purification step of dissolving in a specific solvent to remove the catalyst residue and the cross-linking agent can be mentioned. That is, in the refining step (i) for removing such unreacted components, the reactivity contained in the raw material petroleum heavy oils or pitches is low, and the unreacted or insufficiently reacted. No ingredients,
And a step of removing the solvent used in the reaction.

Specifically, the reaction product obtained in the polycondensation step is treated with an aliphatic hydrocarbon having 10 or less carbon atoms or an alicyclic ring having 10 or less carbon atoms at any time after completion of the heating reaction. At least one selected from the group consisting of formula hydrocarbons
Pour into a specific solvent containing various compounds to precipitate the resin main component, and remove components soluble in the solvent, that is, components that remain unreacted and low reaction and reaction solvent during polycondensation reaction. Done by. Specific examples of such a hydrocarbon solvent include aliphatic or alicyclic hydrocarbons such as pentane, hexane, heptane, and cyclohexane, and n-hexane is particularly preferable.

In the purification step (ii) for removing the catalyst residue such as acid and the cross-linking agent, in order to remove the catalyst residue such as acid and the cross-linking agent remaining in the reaction mixture obtained by the polycondensation step, an acid catalyst is used. The solubility of the cross-linking agent is 0.1 or less, preferably 0.07 or less, and it is hardly soluble. However, it is performed by performing an extraction treatment using an extraction solvent that dissolves most of the modified phenolic resin. The extraction solvent is hardly soluble when the solubility of the acid catalyst and the cross-linking agent is 0.1 or less, but is not particularly limited as long as it is a solvent capable of dissolving most of the modified phenolic resin. For example, benzene, toluene, xylene, and other aromatic compounds. Group hydrocarbons are preferred, and toluene is more preferred.

In the present invention, the refining step (ii) is not limited to the conditions such as the temperature, but may be carried out under the condition that the above characteristics of the solvent are sufficiently exhibited. In the purification step (ii), the reaction product may be added to the solvent, or conversely, the solvent may be added to the reaction product. Of course, the catalyst residue such as acid and the cross-linking agent can be substantially removed only by the above extraction treatment. However, if desired, the modified phenolic resin after the purification step (ii) by the extraction treatment is usually followed by the following steps. Neutralization treatment and /
Alternatively, washing with water may be performed to further remove catalyst residues such as acids in the resin.

Particularly, after the extraction treatment, the neutralization treatment is preferably performed when a slight amount of acid catalyst or the like may remain in the extraction solution. Examples of the neutralization treatment include addition of a basic substance to the modified phenol resin after the purification step (ii). Examples of the basic substance include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and magnesium hydroxide, alkaline earth metal hydroxides; ammonia, diethylenetriamine, triethylenetetramine, aniline, phenylenediamine, etc. Can be mentioned.

In the purification step of the present invention, such purification steps (i) and (ii) can be performed in any order. However, the modified phenolic resin after the purification step (ii) is usually in the form of a varnish dissolved in a solvent, and this varnished modified phenolic resin is used as it is or after adjusting the resin concentration by concentrating or adding an organic solvent. It can be used as a raw material in the step of lowering the molecular weight. In addition, the varnish-like modified phenol resin is collected as a powdery modified phenol resin which is put into a solvent in which the modified phenol resin is insoluble, for example, n-hexane and is re-precipitated, and is a raw material for the subsequent low molecular weight conversion step. You may use as.

Production of Highly Reactive Modified Phenolic Resin The novel highly reactive modified phenolic resin of the present invention can be obtained by the method described in Japanese Patent Application No. 6-23617, for example, such a modified phenolic resin, that is, a polycondensation step. The reaction product thus obtained can be produced as it is or after purification, by reacting it with a phenol in the absence of a formaldehyde polymer and other cross-linking agent and in the presence of an acid catalyst to lower the molecular weight. In such a low molecular weight reaction, the modified phenolic resin is cut and dissociated by cutting and dissociating the acetal bond and / or methylene ether bond present in the molecule, and the phenols are bonded to the dissociated terminal portion. To increase the phenol content of the modified phenolic resin,
It is considered that a highly reactive modified phenolic resin having a low resin melt viscosity and an excellent reactivity with an epoxy resin can be obtained.

Therefore, the amount of the raw material and the acid catalyst used in the step of lowering the molecular weight, the type and combination thereof, the reaction conditions such as the reaction temperature, etc., are the lower molecular weight of the modified phenol resin and the reaction activity with the epoxy resin. There is no particular limitation as long as it is a range that can improve the above. However, it is important to appropriately select the reaction conditions such as the type and amount of the acid catalyst used in the molecular weight reduction step, the reaction temperature, and / or the type and amount of the reaction solvent. The phenols and acid catalysts used in the molecular weight reduction step may include the compounds exemplified in the polycondensation step.

In the step of lowering the molecular weight of the present invention, the phenols react sufficiently if they are 10% by weight or more based on the weight of the modified phenol resin, but if too much phenol is used, a large amount of unreacted phenols is used. Remains, resulting in an increase in the cost required for the post-treatment, so the content is preferably 10 to 300% by weight. Further, the addition of phenols does not necessarily have to be sequential addition, and the entire amount may be introduced into the reaction system at the start of the reaction.

The amount of the acid catalyst used is 0.1% by weight or more, preferably 0.1 to 1% by weight based on the weight of the modified phenolic resin.
It is desirable to use 5% by weight, more preferably 0.1 to 10% by weight, and even more preferably 0.2 to 10% by weight. In the step of lowering the molecular weight, the reaction solvent may or may not be used. The reaction solvent used is not particularly limited as long as it does not inhibit the above-mentioned molecular weight reduction reaction,
Examples thereof include solvents used in the polycondensation reaction, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone: alcohols such as methyl alcohol, ethyl alcohol and n-butyl alcohol: ethers such as tetrahydrofuran.

Such a solvent is preferably used in an amount of 0 to 300% by weight based on the modified phenolic resin. The reaction temperature is not particularly limited, but is usually 50 to 120 ° C, preferably 80 to 120 ° C. The reaction time is not particularly limited, and is, for example, 15 minutes to 3.0 hours, preferably 30 minutes to 2.0 hours.

Post-Treatment of Highly Reactive Modified Phenolic Resin Since the highly reactive modified phenolic resin may leave unreacted components, catalyst residues such as acids, etc., it may be purified by a method such as washing with water, It is necessary to remove catalyst residues such as reaction components and acids. Preferably, the reaction product is diluted using a mixed solvent of toluene and alcohols such as methanol and ethanol or a mixed solvent of toluene and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and then distilled water and / or Alternatively, washing treatment is performed with a mixed liquid of distilled water and isopropyl alcohol to remove unreacted components such as phenols and catalyst residues such as acids.

Further, the highly reactive modified phenolic resin is
After removing unreacted components and catalyst residues such as acids as described above, the extraction solvent is desolvated, or a solvent in which the highly reactive modified phenolic resin is insoluble, that is, an aliphatic or alicyclic group having 10 or less carbon atoms. The resin is preferably precipitated by treatment with a formula hydrocarbon or a mixed solvent thereof. Examples of such a hydrocarbon solvent include the solvents described in the step of purifying the modified phenolic resin, and n-hexane is particularly preferable.

Features of highly reactive modified phenolic resin (A) (a) The highly reactive modified phenolic resin (A) itself has the following features as compared with the modified phenolic resin. -The number average molecular weight decreases, and the number average molecular weight is 300-
It has a molecular weight of 800, improves reactivity with epoxy resin, and lowers resin melt viscosity. Therefore, when the highly reactive modified phenolic resin (A) is used as a mixture with the epoxy resin (B), the coating film is excellent in weather resistance, heat resistance and adhesion to metal, and does not substantially contain an acid. It does not corrode the metal to be subjected to anticorrosion treatment and exhibits excellent mechanical properties when heated.

Epoxy Resin Component (B) When the highly reactive modified phenolic resin (A) of the present invention is used as an essential component of a vehicle for anticorrosion paint, it is necessary to blend an epoxy resin. The anticorrosion coating material obtained in this way can be made to have further excellent dimensional stability of the coating film and excellent heat resistance and the like. In this case, it is a more preferable embodiment to incorporate a curing agent and / or a curing accelerator (C). Examples of the epoxy resin include glycidyl ether type, glycidyl ester type, glycidyl amine type, mixed type, and alicyclic type epoxy resins.

More specifically, as the glycidyl ether type (phenol type), bisphenol A type epoxy resin, biphenyl type epoxy resin, bisphenol F are used.
Type epoxy resin, tetrabromobisphenol A type epoxy resin, tetraphenylolethane type epoxy resin,
Phenol novolac type epoxy resin, o-cresol novolac type epoxy resin and the like; as glycidyl ether type (alcohol type), polypropylene glycol type epoxy resin, water-added bisphenol A type epoxy resin and the like;

Hexahydrophthalic anhydride type epoxy resin, dimer acid type epoxy resin and the like as glycidyl ester type; diaminodiphenylmethane type epoxy resin, isocyanuric acid type epoxy resin, hydantoic acid type epoxy resin and the like as glycidyl amine type. A mixed type includes p-aminophenol type epoxy resin, p-
Examples thereof include oxybenzoic acid type epoxy resin. Of the above epoxy resins, bisphenol A type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, and biphenyl type epoxy resin are preferable. A combination of two or more of the above epoxy resins can also be used.

The mixing ratio of the highly reactive modified phenolic resin (A) and the epoxy resin (B) is not particularly limited, but the highly reactive modified phenolic resin (A) and the epoxy resin (B) are included.
The total of 100 parts by weight is 10/90 to 90/10
(Parts by weight) is preferable, and more preferably 20
/ 80 to 80/20 (parts by weight). Here, if the weight ratio of the highly reactive modified phenolic resin (A) is less than 10 parts by weight, the effect of improving the heat resistance and weather resistance of the resulting coating film is not sufficient, and if it exceeds 90 parts by weight, the epoxy resin is added. The effect of compounding is halved, and the dimensional stability of the coating film, the adhesion to metal, etc. become poor.

Addition of Curing Agent and / or Curing Accelerator (C) The highly reactive modified phenolic resin (A) used as an essential component of the vehicle for the anticorrosion paint, together with the epoxy resin (B), the curing agent and / or the curing accelerator (C). ) Is desirable. Various things can be used as a hardening agent and / or a hardening accelerator (C). As the curing agent, for example,
Examples thereof include cyclic amines, aliphatic amines, polyamides, aromatic polyamines and acid anhydrides.

Specifically, for example, as cyclic amines, hexamethylenetetramine and the like; as aliphatic amines, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, isophoronediamine. , Bis (4-amino-3-methylcyclohexyl) methane, menthanediamine, etc .; as polyamides, vegetable oil fatty acid (dimer or trimer acid), aliphatic polyamine condensate, etc .;

As aromatic polyamines, m-phenylenediamine, 4,4'-diaminodiphenylmethane,
4,4′-diaminodiphenyl sulfone, m-xylylenediamine, etc .; as the acid anhydrides, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride,
Trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, chlorendic anhydride, dodecynyl succinic anhydride, methyltetrahydrophthalic anhydride,
Methyl endomethylene tetrahydrophthalic anhydride etc. can be mentioned.

The curing accelerator is not particularly limited as long as it accelerates the curing reaction, and for example, diazabicycloalkene such as 1,8-diazabicyclo (5,4,0) undecene-7 and its derivatives; triethylenediamine, Tertiary amines such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; 2-methylimidazole,
2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole,
2-Heptadecyl imidazole and other imidazoles; tributylphosphine, methyldiphenylphosphine, triphenylphosphine and other organic phosphines; tetraphenylphosphonium / tetraphenylborate and other tetra-substituted phosphonium / tetra-substituted borate; 2-ethyl-4-methyl Imidazole tetraphenylborate,
Tetraphenylboron salts such as N-methylmorpholine / tetraphenylborate, Lewis acids such as boron trifluoride-amine complex and tris (dimethylaminomethyl) phenol, benzyldimethylamine, dicyandiamide,
Examples thereof include Lewis bases such as adipic acid dihydrazide, and polymercaptans and polysulfides. Further, these curing agents and curing accelerators may be used alone or in combination of two or more.

Anticorrosion Paint (a) Addition of Various Additives Various additives are added to the anticorrosion paint of the present invention as necessary in order to enhance various physical properties such as strength and dimensional stability of the obtained coating film. It is desirable to do. In particular, in order to relieve the internal stress of the coating film, inorganic fillers (extensive pigments) such as talc, clay, calcium carbonate, and silicate; anticorrosion of barium chromate, zinc chromate, zinc phosphate, basic sulfuric acid, etc. Pigment: Color pigments such as red iron oxide, titanium oxide, and carbon black can be used as appropriate.

In this case, these pigments or fillers are 10 to 70% by weight, preferably 4% by weight, based on the weight of the coating film.
It is desirable to add 0 to 60% by weight. Other additives include thickeners such as coumarone resin and petroleum resin,
Examples thereof include an odor-changing agent, an antifoaming agent, an anti-sagging agent, an antioxidant, an ultraviolet absorber and a silane coupling agent.

(B) Organic solvent (diluent) The anticorrosive paint of the present invention requires an organic solvent (diluent) for dissolving the resin component constituting the vehicle and / or diluting the obtained vehicle liquid. It is an ingredient. Therefore, the organic solvent (diluent) used in the present invention is not particularly limited as long as it is a good solvent that can dissolve and / or dilute the vehicle component to be used as a soluble component as much as possible, and even a single solvent may be used. It may be a mixed solvent.

Examples of good solvents for the highly reactive modified phenolic resin (A) include aromatic hydrocarbons such as benzene, toluene and xylene; amides such as dimethylformamide; halogenated aromatic hydrocarbons such as chlorobenzene. Ethers such as tetrahydrofuran and dioxane; alcohols such as methanol and ethanol; glycols such as ethyl cellosolve; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone;
Esters such as ethyl acetate; chloroform, methylene chloride, perclen or a mixture thereof can be mentioned. Among them, it is preferable to use at least one organic solvent selected from aromatic hydrocarbons, amides, ketones, alcohols and halogenated aromatic hydrocarbons.

On the other hand, the good solvent for the epoxy resin (B) is selected from the organic solvents that have been widely used in the past and used. For example, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methanol, Preference is given to alcohols such as ethanol; aromatic hydrocarbons such as toluene and xylene, or a mixture thereof.

(C) Preparation of Anticorrosion Coating In addition to bituminous substances such as coal tar, pitch and asphalt, which are known as vehicles for anticorrosion coatings, within the range not impairing the intention of the present invention, petroleum resin, coumarone resin, xylene resin, A thermosetting resin such as a polycyclic aromatic hydrocarbon-based modified phenol resin may be blended. To produce the anticorrosion paint of the present invention, basically, a highly reactive modified phenolic resin (A) is used.
The epoxy resin (B) and, if necessary, the curing agent and / or the curing accelerator (C) are dissolved in an organic solvent to prepare a vehicle solution. An appropriate additive is added to and mixed with this to prepare an anticorrosion paint.

In dissolving the resin component such as the highly reactive modified phenolic resin (A) and the epoxy resin (B) and the curing agent and / or the curing accelerator (C) in an organic solvent,
Regarding the operation and conditions, the type of organic solvent used,
It may be appropriately selected according to the type of vehicle component. For example, the highly reactive modified phenolic resin (A) is added to the organic solvent at a ratio such that the solution becomes a 10 to 70% solution at room temperature or under heating, and after stirring for about 10 minutes to 1 hour, if necessary, Insoluble components are removed by filtration or the like, and further concentrated as necessary to produce a highly reactive modified phenol resin vehicle. Separately, an epoxy resin vehicle is manufactured by the same operation. After that, both vehicles are mixed at a predetermined ratio to obtain a vehicle for anticorrosion paint. This mixing method is operationally preferable.

Further, after the above-mentioned highly reactive modified phenolic resin vehicle is produced, an epoxy resin may be subsequently added to form a vehicle. Alternatively, conversely, the highly reactive modified phenolic resin may be added after the epoxy resin is added to the organic solvent. Further, the highly reactive modified phenolic resin and the epoxy resin may be simultaneously added to the organic solvent, or the highly reactive modified phenolic resin and the epoxy resin may be mixed in advance and then added to the organic solvent. Further, the curing agent and / or the curing accelerator (C) may be added at any stage during the production of the epoxy resin vehicle, the mixing of the two vehicles, and the like.

[0054]

The present invention is illustrated by the following examples, which do not limit the scope of the invention. In the following examples, all parts are by weight unless otherwise specified, and the properties of the raw material oil used as the raw material are shown in Table 1. These feedstocks are fluid catalytic cracking (FC
It is obtained by distilling the bottom oil obtained in C).

[0055]

[Table 1]

(Example 1) 334 g of raw material oil shown in Table 1,
Paraformaldehyde (370 g), p-toluenesulfonic acid monohydrate (137 g) and p-xylene (678.5 g) were charged into a glass reactor and heated to 95 ° C. with stirring. After holding at 95 ° C. for 1 hour, 209 g of phenol was appropriately applied at an appropriate rate of 1.3 g / min, and after completion of the appropriate amount of phenol, the mixture was further stirred for 15 minutes. Then the reaction mixture is n
-Pour into 3300 g of hexane to precipitate a reaction product, and filter to remove unreacted components and reaction solvent. 16
After washing the precipitate with 00 g of n-hexane, vacuum drying,
A crude modified phenolic resin powder containing an acid was obtained.

This resin powder was dissolved in 10 times the weight of toluene, and the insoluble material containing p-toluenesulfonic acid monohydrate as the main component was filtered. The obtained resin toluene solution was concentrated to a resin concentration of 50% by weight to obtain a modified phenol resin toluene solution. After a slight amount of triethylenetetramine was added to the solution for neutralization, the toluene solution was added to 3.
It was poured into 3 times the weight of n-hexane to precipitate a resin, which was filtered. Then, it is vacuum dried and modified phenol resin powder 5
80 g were obtained.

100 g of the obtained modified phenolic resin powder
250 g of phenol, 200 g of phenol, and 5 g of p-toluenesulfonic acid were put into a 500 ml glass reaction vessel, and 250 to 350
While stirring at a speed of rpm, raise the temperature to 95 ° C.,
The reaction reaction was carried out at 90 ° C. for 90 minutes to obtain a reaction product. The reaction product was dissolved in a toluene / methylisobutylketone mixed solution (mixing ratio 4/1) in an amount twice the amount of the product to prepare a resin solution.

The resin solution thus obtained was washed with distilled water / isopropanol mixed solution to extract and remove the acid and unreacted components contained in the reaction product, and then the toluene / methylisobutylketone mixed solution was removed with an evaporator. It was removed and vacuum dried under heating to obtain 190 g of a highly reactive modified phenol resin powder containing substantially no acid. Methyl ethyl ketone was added to this resin powder so that the resin concentration was 60% by weight, to obtain 317 g of a highly reactive modified phenol resin solution.

On the other hand, 285 g of bifunctional epoxy resin [Epicoat 828, manufactured by Yuka Shell Epoxy Co., Ltd.] and 2.85 g of 2-ethyl-4-methylimidazole were added to 71 g of methyl ethyl ketone to obtain an epoxy resin solution. . The highly reactive modified phenolic resin solution was mixed with the obtained epoxy resin solution to obtain a vehicle solution having a ratio of 4 parts by weight of the highly reactive modified phenolic resin and 6 parts by weight of the epoxy resin. Add 28.8 talc powder to this vehicle solution.
By weight, 5.0 parts by weight of titanium oxide and 0.9 parts by weight of an iodine modifier were mixed to prepare an anticorrosion paint. This anticorrosion paint is applied to an iron plate to form a coating film, which is heat-cured at 180 ° C for 3 hours,
The following tests were conducted and the results are summarized in Table 2.

(B) Salt water acceleration test: A test for swelling after immersion in salt water for 7 days. (B) Crude oil accelerating test: A test for the presence or absence of weight change after immersion in crude oil for 7 days. (C) Salt spray test: A test with a peeling width mm of the cross-cut portion after spraying for 30 days. (D) Temperature gradient test: 60 ° C. on the coating film side and 15 on the iron plate side
The period (days) in which blisters occur when kept at ℃. (E) Weather resistance test: A test depending on the degree of yellowing of the coating film with a weather meter.

Example 2 The same operation as in Example 1 was carried out to obtain a modified phenol resin powder containing substantially no acid.
500 g of 100 g of the obtained resin powder, 66 g of phenol, 40 g of toluene and 1.5 g of p-toluenesulfonic acid are added.
Charge to a ml glass reaction vessel, 250-350 rpm
The temperature was raised to 95 ° C with stirring at the speed of
The reaction was carried out by holding for a minute to obtain a reaction product containing a highly reactive modified phenolic resin. The reaction product is
Double volume of toluene / methyl alcohol mixture (mixing ratio 4 /
It melt | dissolved in 1) and prepared the resin solution.

The obtained resin solution is washed with distilled water / isopropanol mixed solution to extract and remove the acid and unreacted components contained in the reaction product, and then the toluene / methyl alcohol mixed solution is removed with an evaporator. Then, it was vacuum dried under heating to obtain 140 g of a highly reactive modified phenol resin powder containing substantially no acid. Methyl ethyl ketone was added to this resin powder so that the resin concentration was 60% by weight, to obtain 233 g of a highly reactive modified phenol resin solution.

On the other hand, to 31 g of methyl ethyl ketone, 50 g of a tetrafunctional epoxy resin [Araldite MY9512, manufactured by Ciba-Geigy Co., Ltd.] and 0.3 g of 2-ethyl-4-methylimidazole were added and dissolved to obtain an epoxy resin solution. The above-mentioned highly reactive modified phenolic resin solution was mixed with the obtained epoxy resin solution, and an anticorrosive coating material was prepared in the same manner as in Example 1. This anticorrosion paint was applied to an iron plate to form a coating film, which was heat-cured at 180 ° C. for 3 hours and then subjected to the same test as in Example 1, and the results are summarized in Table 2.

[0065]

[Table 2]

[0066]

As described above, according to the novel anticorrosion coating material of the present invention, it is excellent in weather resistance, corrosion resistance (chemical resistance), heat resistance, etc. It is possible to obtain a coating film which does not corrode the formed metal and has high adhesion to the metal and excellent mechanical properties when heated.

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[Procedure amendment]

[Submission date] August 25, 1995

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

[0010] (2) highly reactive modified phenolic resin which is one component that make up an anticorrosive coating according to the production present invention modified phenolic resin (A), identifying the modified phenolic resin obtained in particular polycondensation step It is manufactured by lowering the molecular weight in the molecular weight reduction step under the condition of. The method for producing the modified phenolic resin is preferably carried out by the method described in Japanese Patent Application No. 5-40646, and more specifically by the following method. Modified phenol resin and method for producing the same The modified phenol resin raw material used in the present invention is polycondensed with petroleum heavy oils or pitches shown below, phenols and formaldehyde polymer in the presence of an acid catalyst.

Claims (3)

[Claims] 1. A modified phenolic resin obtained by polycondensing (A) a petroleum heavy oil or pitches, a formaldehyde polymer and a phenol in the presence of an acid catalyst in the presence of an acid catalyst. A highly reactive modified phenolic resin-based anticorrosive paint comprising a resin composition comprising a highly reactive modified phenolic resin which is reacted with phenols to have a low molecular weight and (B) an epoxy resin. 2. The highly reactive modified phenolic resin anticorrosion coating composition according to claim 1, wherein the resin composition further contains a curing agent and / or a curing accelerator (C). 3. A highly reactive modified phenolic resin (A) / epoxy resin (B) compounding ratio of 10/90 to 90/10.
The high-reactivity modified phenolic resin anticorrosion paint according to claim 1, which is (part by weight).