JPH09208664A - Epoxy resin modified with polymerized fatty acid, its preparation, and curable resin composition comprising the resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an epoxy resin completely soluble in an aliph. hydrocarbon solvent with a flash point 40 deg.C or above at ordinary temp., to provide a process for preparing the same, and to obtain and a curable compsn. capable of forming a coating film excellent in adhesion, corrosion resistance, etc. SOLUTION: This modified epoxy resin has an arom. glycidyl ether unit content of 15 to 45wt.% and an epoxy equivalent of 170 to 2,000g/eq. It is prepd. by reacting an arom. glycidyl ether with a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms, or by reacting the above compds. together with a polyglycidyl ester of a polymerized fatty acid. This curable compsn. comprises the epoxy resin modified with the polymerized fatty acid and an epoxy curing agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a paint, an adhesive, a flooring material, an insulating material, a casting material, a flexibility-imparting agent which is completely dissolved in an aliphatic hydrocarbon solvent having a high flash point at room temperature. The present invention relates to an epoxy resin that can be used in a wide range of fields such as adhesives, a method for producing the same, and a curable composition containing the epoxy resin, and in particular, a composition that provides a cured product having excellent adhesion, corrosion resistance, and the like. Is provided.

[0002]

2. Description of the Related Art Epoxy resins have been conventionally used for bridges, tanks, and tanks because of their excellent corrosion resistance, adhesion and chemical resistance.
It is widely used for heavy-duty anticorrosion paints for ships and the like, but is generally used by dissolving a bisphenol type epoxy resin in an organic solvent having a low flash point and a low boiling point, such as xylene and toluene, which is highly toxic. For this reason, there is a problem that the working environment is deteriorated due to the solvent odor at the time of coating, there is a risk of fire, and further, when the old coating is applied, the old coating swells and is lifted. In order to improve these problems, it is necessary to use a solvent with low odor during coating and a high flash point,
Since conventional epoxy resins have low solubility in these solvents, there have been problems such as paint turbidity and viscosity increase.
As measures for improving these problems, Solvesso 10 is disclosed in JP-A-4-11623 and JP-B-7-68491.
Although a polymerized fatty acid-modified epoxy resin which is soluble in an aromatic hydrocarbon solvent having 9 to 11 carbon atoms such as 0 has been reported, there is a problem that the aromatic hydrocarbon solvent cannot eliminate the odor during the coating operation. there were. Therefore, it has been desired to develop an epoxy resin, such as mineral spirits, which can dissolve in an aliphatic hydrocarbon solvent having a high flash point and can obtain a coating film having excellent adhesion and corrosion resistance.

On the other hand, polymerized fatty acid-modified epoxy resin is known, and polymerized fatty acid polyglycidyl ester obtained by reaction of polymerized fatty acid with epichlorohydrin is also known. As the polymerized fatty acid-modified epoxy resin, for example, JP-A-5-39440 discloses a bisphenol A type epoxy resin having an epoxy equivalent of 500 to 1,500 modified with 4 to 30% by weight of dimer acid. The known polymerized fatty acid-modified epoxy resin was not completely dissolved in an aliphatic solvent having a high flash point. Further, although the polymerized fatty acid polyglycidyl ester is soluble in the above-mentioned solvent, it has the drawback of being inferior in coating properties, especially in corrosion resistance.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present inventors have earnestly studied to develop an epoxy resin which is soluble in an aliphatic solvent having a high flash point and a low odor. A polymerized fatty acid-modified epoxy resin containing a fatty acid skeleton and an aromatic glycidyl ether skeleton in a specific ratio is completely dissolved in an aliphatic solvent having a flash point of 40 ° C. or higher at room temperature, and the epoxy resin and the epoxy resin are cured. A curable composition comprising an agent has been found to be a curable composition that gives a coating film excellent in adhesion, corrosion resistance, etc., and has led to the completion of the present invention. The objective is to provide a curable composition comprising a polymerized fatty acid-modified epoxy resin soluble in an aliphatic solvent at a point, and the epoxy resin and an epoxy curing agent that provide a coating film having excellent adhesion and corrosion resistance. Do

[0005]

The gist of the present invention is a polymerized fatty acid-modified epoxy resin obtained by modifying an aromatic glycidyl ether with a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms. The content of aromatic glycidyl ether is 15 to 45% by weight, and
The epoxy equivalent of the polymerized fatty acid-modified epoxy resin is 170.
To 2,000 g / eq, and a curable composition of a polymerized fatty acid-modified epoxy resin and an epoxy curing agent, or a polymerized fatty acid-modified epoxy resin and an amine-based curing agent. A curable composition comprising an agent and an aliphatic solvent. Then, as a method for producing the polymerized fatty acid-modified epoxy resin, a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms are reacted with an aromatic glycidyl ether, or a modified epoxy having an aromatic glycidyl ether content of 55 to 80% by weight. A resin is formed and then a polymerized fatty acid polyglycidyl ester is added and reacted, or an aromatic glycidyl ether is reacted with a polymerized fatty acid polyglycidyl ester, a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms.

The present invention will be described in detail below. Examples of the aromatic glycidyl ethers used in the present invention include a bisphenol type epoxy resin, a novolac type epoxy resin, a glycidyl amine type epoxy resin and the like, but a bisphenol type epoxy resin is preferable.
As the bisphenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin,
Examples thereof include bisphenol S-type epoxy resin, bisphenol C-type epoxy resin, bisphenol AD-type epoxy resin, and a mixture thereof. Among them, bisphenol A or bisphenol F-type epoxy resin is particularly preferable. The epoxy resin may have a molecular weight range of about 320 to about 1,500. These commercially available epoxy resins include YD-12 manufactured by Tohto Kasei Co., Ltd.
8, YD-134, YD-011, YDF-170, Y
DF-2001 and the like can be mentioned.

The polymerized fatty acid used in the present invention is a dimer of unsaturated fatty acid (dimer acid), but may contain a small amount of a monomer or trimer. The unsaturated fatty acid as a raw material is a carboxylic acid compound having 12 to 18 carbon atoms (including carbon atoms of a carboxyl group) and one or more unsaturated bonds in one molecule, and examples thereof include oleic acid, sorbic acid, and linole. Examples thereof include acids, linoleic acid, and fatty acids obtained from animal and vegetable oils, such as tall oil fatty acid, soybean oil fatty acid, and flaxseed oil fatty acid. Examples of commercially available products include Versadim 216 and 288 manufactured by Henkel Hakusui Co., Ltd., and Haridimer 200, 250 and 300 manufactured by Harima Chemicals.

The fatty acid used in the present invention has 12 to 18 carbon atoms (including the carbon atom of the carboxyl group) and is saturated,
They are unsaturated fatty acid monomers and tertiary fatty acids. Examples of saturated fatty acids include lauric acid, palmitic acid, and stearic acid, and examples of tertiary fatty acids include neoic acid and versatic acid. Further, the unsaturated fatty acid is preferably a carboxylic acid compound having one or more unsaturated bonds in one molecule, for example, oleic acid, sorbic acid, linoleic acid, linoleic acid, fatty acids obtained from animal and vegetable oils, such as tall. Examples thereof include oil fatty acid, soybean oil fatty acid, and flaxseed oil fatty acid. Examples of commercially available products include Hartol FA-1 manufactured by Harima Chemicals, and Alifat 47 manufactured by Henkel Hakusui.

The polymerized fatty acid-modified epoxy resin of the present invention is
Aromatic glycidyl ether content is 15 to 45% by weight
And the epoxy equivalent is 170 to 2,000 g /
It is characterized by being eq. When the content of the aromatic glycidyl ether is 15 wt% or less, sufficient coating film strength cannot be obtained, and when it is 45 wt% or more, low temperature solubility in mineral spirits is deteriorated, and more preferably 25 to 35 wt%. . The epoxy equivalent is 170
~ 2,000 g / eq, preferably 250-1,000
It is g / eq. Epoxy equivalents of 170 g / eq or less are difficult to synthesize, and epoxy equivalents of 2,000 g / e
The reason for exceeding q is that the crosslink density becomes sparse and the properties of the cured product such as corrosion resistance and chemical resistance are impaired.

As the method for producing the polymerized fatty acid-modified epoxy resin of the present invention, a method of reacting an aromatic glycidyl ether with a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms, or a polymerized fatty acid polyglycidyl ester, a polymerized fatty acid and carbon number A mixture of 12 to 18 fatty acids and an aromatic glycidyl ether having an aromatic glycidyl ether content of 15
It can be produced by a method of reacting so as to be in the range of up to 45% by weight. In the former method, after producing a modified epoxy resin having an aromatic glycidyl ether content of 55 to 80% by weight, a polymerized fatty acid polyglycidyl ester is added so that the aromatic glycidyl ether content is 15 to It can be adjusted to be 45% by weight.

The polymerized fatty acid polyglycidyl ester used in this production method can be obtained by reacting the above-mentioned polymerized fatty acid with epichlorohydrin as a catalyst in the presence of an alkali metal hydroxide. Commercially available products include YD-171 manufactured by Toto Kasei.

The polymerized fatty acid-modified epoxy resin of the present invention is
It can be produced by any of the following methods (1) to (3). (1) After the aromatic glycidyl ether, the polymerized fatty acid, and the fatty acid having 12 to 18 carbon atoms are added all at once, they are reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst. (2) Aromatic glycidyl ether, polymerized fatty acid, and fatty acid having 12 to 18 carbon atoms are added all at once, reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst, and then polymerized fatty acid polyglycidyl ester is added. . (3) Aromatic glycidyl ether, polymerized fatty acid, and fatty acid having 12 to 18 carbon atoms are collectively charged, and then reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst. The fatty acid used as the raw material is preferably 30% by weight or less, more preferably 15% by weight or less, based on the polymerized fatty acid. When the amount of the fatty acid used is large, the drying property and strength of the coating film are deteriorated. However, it is preferable to add a small amount according to the purpose because the resin viscosity can be lowered by blending the fatty acid.

The catalyst used in the reaction includes triethylamine, dimethylbenzylamine, pyridine and the like.
Quaternary ammonium salts such as secondary amine, tetramethylammonium chloride, benzyltrimethylammonium chloride and triphenylphosphonium bromide, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, triphenylphosphine and triethylphosphine Organophosphorus compounds and the like are used. The amount of catalyst used in the reaction is 10 to 10,000 ppm, preferably 50 to 3,000 ppm, relative to the polymerized fatty acid used for modification.

The polymerized fatty acid-modified epoxy resin according to the present invention constitutes a curable composition by adding a curing agent and a solvent. As the curing agent used in the curable composition of the present invention, amine-based curing agents, mercaptan-based curing agents, acid anhydride-based curing agents and the like can be used, but amine-based curing agents are most commonly used for heavy-duty anticorrosion applications. Used. Examples of the curing agent include polyaminoamides, epoxy resin amine adducts, aliphatic polyamines, modified polyamines, tertiary amines,
The curing agents used for ordinary epoxy resins such as hydrazide and imidazole can be used, but polyaminoamides and epoxy resin amine adducts are particularly preferable.

As the solvent used in the curable composition of the present invention, in addition to an aliphatic solvent (mineral spirits) having a flash point of 40 ° C. or higher, if necessary, toluene, xylene, and aromatic compounds such as high-boiling naphtha are used. System solvents, ketones, alcohols, esters, glycol ethers and mixtures thereof can also be used.

The curable composition of the present invention can be used alone, but if necessary, one or more selected from petroleum resin, coumarone indene resin, xylene resin, ketone resin, acrylic resin and the like. The above resin can be contained in a desired purpose range. The composition of the present invention includes fillers such as talc, calcium carbonate, silica and carbon, pigments such as red iron oxide, titanium oxide, zinc sulfide and iron oxide, thickeners, defoamers, plasticizers and the like according to various uses. An appropriate amount of an additive such as an agent can be blended. As a paint forming means, a paint can be prepared by mixing and dispersing a mixture of the above components excluding the curing agent component with a dispersing device such as a roll mill, a ball mill and a sand grind mill. This is mixed with a curing agent just before coating, applied by a usual coating means such as spray coating, roller coating, brush coating, and the like, and a cured coating film is formed by natural drying and forced drying.

[0017]

The polymerized fatty acid-modified epoxy resin of the present invention is soluble in an aliphatic hydrocarbon solvent having a high flash point, and the curable composition thereof can improve the working environment at the time of coating, Further, it is possible to prevent the lifting phenomenon caused by dissolving or swelling the old coating film when applied on the old coating film. Furthermore, since it has a low viscosity, it can contribute to environmental protection by reducing the amount of organic solvent by making it highly solid or solvent-free.

[0018]

EXAMPLES AND COMPARATIVE EXAMPLES The present invention will be specifically described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples. Examples 1 to 6 and Comparative Examples 1 to 3 YD-128 manufactured by Tohto Kasei Co., Ltd. as an aromatic glycidyl ether in a reactor equipped with a stirrer, a thermometer and a cooling pipe.
(Bisphenol A type liquid epoxy resin; epoxy equivalent 186 g / eq, viscosity 12,600 mPa · s / 25
C.) or YDF-170 (bisphenol F type epoxy resin; epoxy equivalent 170 g / eq, viscosity 3,500 m)
Pa · s / 25 ° C.), polymerized fatty acid polyglycidyl ester manufactured by Tohto Kasei Co., Ltd. YD-171 (polyglycidyl ester of dimer acid; epoxy equivalent 451 g / eq, viscosity 650 mPa · s / 25 ° C.), polymerized fatty acid manufactured by Henkel Hakusui Co., Ltd. Versadim 288 and 12 to 1 carbon atoms
As the fatty acid of No. 8, HARTOL FA-1 manufactured by Harima Kasei Co., Ltd. was charged at the ratio (parts by weight) shown in Table 1 and the temperature was raised to 120 ° C., and 1,000 ppm of triphenylphosphine as a catalyst was added to the polymerized fatty acid, and 150 ° C. Up to 50m, react at the same temperature and measure the acid value every hour
The reaction was terminated when it became gKOH / g or less. still,
In Example 6, after the aromatic glycidyl ether, the polymerized fatty acid and the fatty acid were charged and reacted, the polymerized fatty acid polyglycidyl ester was added.

The properties of the resulting polymerized fatty acid-modified epoxy resin are shown in Table 1. The epoxy equivalent (solid content) is J
The viscosity was measured by IS K 7236, and the viscosity was measured by a BH type rotational viscometer at 25 ° C. The low-temperature solubility was determined by visually inspecting the presence or absence of separation after dissolving the polymerized fatty acid-modified epoxy resin in mineral spirits to form a varnish having a nonvolatile content of 70% by weight and allowing it to stand at 5 ° C. for 24 hours (◯: separation None, x; separated).

Next, the polymerized fatty acid-modified epoxy resin thus obtained is dissolved in mineral spirits to produce a polymerized fatty acid-modified epoxy resin varnish having a nonvolatile content of 70%.
Amount of amine curing agent ZX-1478 manufactured by Tohto Kasei Co., Ltd. (amine value 106 mgKOH /
g), and then 32 parts of titanium oxide, 25 parts of precipitated barium sulfate, and 8 parts of zinc phosphate were mixed to prepare a coating composition.
The obtained coating was applied to mild steel plate SPCC-SB (1.6 × 70 ×
(150 mm) degreased with methyl ethyl ketone and then sandblasted (emery sand # 180)
Paint with a brush to a dry film thickness of 100 μm, 20 ℃
And dried for a week. The results of evaluating the appearance, adhesion, and corrosion resistance performance tests of the obtained coating film are shown in the coating film physical properties column of the curable composition in Table 1. The appearance of the coating film was visually determined (◯: good, Δ: somewhat good, ×: bad). The adhesiveness was evaluated by the adhesive cross-cut tape peeling test method of JIS K-5400.
A grid of mm × 1 mm was cut with a cutter knife at a depth reaching the substrate, cellophane tape was attached, and the grid was momentarily peeled off. The number of grids remaining on the substrate was visually determined. Regarding corrosion resistance, JIS K 54
After spraying salt water for 300 hours in accordance with the salt water resistance spray test of No. 00, the appearance of the coating film was visually evaluated for rust resistance according to the following classification (○: good, Δ: slightly blister due to rust generation, ×; There is significant blistering due to rusting).

[0021]

[Table 1]

As is clear from Table 1, the polymerized fatty acid-modified epoxy resin of the present invention and the curable composition thereof have excellent solubility in mineral spirits, and the resulting coating film has excellent adhesion and corrosion resistance.

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[Procedure amendment]

[Submission date] February 22, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

The polymerized fatty acid-modified epoxy resin of the present invention is
It can be produced by any of the following methods (1) to (3). (1) After the aromatic glycidyl ether, the polymerized fatty acid, and the fatty acid having 12 to 18 carbon atoms are added all at once, they are reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst. (2) Aromatic glycidyl ether, polymerized fatty acid, and fatty acid having 12 to 18 carbon atoms are added all at once, reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst, and then polymerized fatty acid polyglycidyl ester is added. . (3) Aromatic glycidyl ether, polymerized fatty acid, polymerized fat
After the fatty acid polyglycidyl ester and the fatty acid having 12 to 18 carbon atoms are added all at once, they are reacted at 80 to 200 ° C. for 1 to 20 hours in the presence of a catalyst. The fatty acid used as the raw material is preferably 30% by weight or less, more preferably 15% by weight or less, based on the polymerized fatty acid. When the amount of the fatty acid used is large, the drying property and strength of the coating film are deteriorated. However, it is preferable to add a small amount according to the purpose because the resin viscosity can be lowered by blending the fatty acid.

Claims (6)

[Claims] 1. A polymerized fatty acid-modified epoxy resin obtained by modifying an aromatic glycidyl ether with a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms, wherein the content of the aromatic glycidyl ether in the polymerized fatty acid-modified epoxy resin is 15 to Four
The polymerized fatty acid-modified epoxy resin is 5% by weight, and the epoxy equivalent of the polymerized fatty acid-modified epoxy resin is 170 to 2,000 g / eq. 2. The method for producing a polymerized fatty acid-modified epoxy resin according to claim 1, wherein the aromatic glycidyl ether is reacted with a polymerized fatty acid and a fatty acid having 12 to 18 carbon atoms to produce a polymerized fatty acid-modified epoxy resin. Method. 3. The method for producing a polymerized fatty acid-modified epoxy resin according to claim 1, wherein a modified epoxy resin having an aromatic glycidyl ether content of 55 to 80% by weight is produced, and then the polymerized fatty acid polyglycidyl ester is added. A method for producing a polymerized fatty acid-modified epoxy resin, which comprises adding. 4. The method for producing a polymerized fatty acid-modified epoxy resin according to claim 1, wherein the aromatic glycidyl ether is reacted with a polymerized fatty acid polyglycidyl ester, a polymerized fatty acid, and a fatty acid having 12 to 18 carbon atoms. Process for producing fatty acid-modified epoxy resin. 5. A curable composition comprising the polymerized fatty acid-modified epoxy resin according to claim 1 and an epoxy curing agent. 6. A curable composition comprising the polymerized fatty acid-modified epoxy resin according to claim 1, an amine-based curing agent, and an aliphatic solvent.