JPH09110847A - Monoepoxy compound containing cyclic terpene skeleton and epoxy resin composition using the same as reactive diluent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new cyclic terpene skeleton-containing monoepoxy compound useful as a reactive diluent for epoxy resins, having low viscosity, excellent in workability and useful for providing an epoxy resin composition excellent in corrosion resistance, gloss and adhesiveness. SOLUTION: This cyclic terpene skeleton-containing monoepoxy compound is obtained by reacting a cyclic terpene skeleton-containing monophenol compound obtained by adding 1mol phenols to 1mol cyclic terpene compound with an epihalohydin. The cyclic terpene includes e.g. limonene of formula I, terpinolene of formula II, pinene of formula III or formula IV, terpinene of formula V, etc. When the monoepoxy compound is used as a reactive diluent, the monoepoxy compound is blended in an amount of 1-50 pts.wt., preferably 10-35 pts.wt. based on 100 pts.wt. epoxy resin. When an alkylidenebisphenol polyglycidyl ether is used as the epoxy resin, an epoxy resin composition excellent in corrosion resistance, chemical resistance and adhesiveness to a substrate is obtained.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a monoepoxy compound containing a cyclic terpene skeleton, and more particularly to a low viscosity, excellent anticorrosion property and curability, without using an organic solvent harmful to the human body, and suitable for various substrates. The present invention relates to a monoepoxy compound containing a cyclic terpene skeleton, which is useful as a reactive diluent for an epoxy resin and which can provide a coating film exhibiting the adhesion.

[0002]

BACKGROUND OF THE INVENTION Epoxy resins are widely used in paints, adhesives, etc. because of their excellent adhesion to various substrates, heat resistance, chemical resistance, electrical properties and mechanical properties. ing.

When used in these applications, epoxy resin was generally used as a solvent type in which it was dissolved in various low-boiling solvents, but there was a risk of fire, harm to humans, and global environment. The use of low boiling point solvents has come to be restricted due to problems such as adverse effects on the solvent, and it is strongly sought to reduce the amount of solvent or switch to a weak solvent with high boiling point and low irritability such as terpenes, or to achieve solvent-free use. It has been demanded.

However, an epoxy resin or a phenol novolac type epoxy resin produced from polyhydric phenols such as bisphenol A or bisphenol F and epichlorohydrin, which have been widely used in the past, are resistant to a high boiling point and mild solvent such as terpene. The solubility was insufficient, and when the amount of the low boiling point solvent used was reduced, the viscosity became high, which was not practically satisfactory.

On the other hand, a method of using a reactive or non-reactive diluent without using a solvent to lower the viscosity of an epoxy resin and using it in a paint or the like without using a solvent has been conventionally practiced. Known as reactive diluents such as aromatic and aliphatic glycidyl ethers, dioctyl phthalate, dibutyl phthalate, higher alcohols,
When a non-reactive diluent such as coal tar is used, the viscosity can be reduced without using a solvent, but as an anticorrosive coating application, problems such as deterioration of physical properties and anticorrosion performance of the coating film occur and performance is deteriorated. However, the range of use was limited.

Japanese Unexamined Patent Publication No. 4-45121 and Japanese Unexamined Patent Publication No.
117420 and JP-A-5-222155 disclose a terpene skeleton-containing polyhydric phenol compound obtained by adding a phenol to a cyclic terpene compound, a condensation product of the polyhydric phenol and an aldehyde, and epichlorohydrin. An epoxy resin which can be obtained by a reaction has been proposed, and the epoxy resin has an electrical insulating property,
Since it has excellent heat resistance and water absorption, it is described that it is particularly useful for laminates in electrical and electronic applications. Further, in JP-A-4-359920, the above epoxy resin is further added to bisphenol A and the like. Polyphenol-modified epoxy resins obtained by reacting these polyphenol compounds have been proposed. Epoxy resins derived from these terpene skeleton-containing polyphenol compounds and their modified products are weak solvents such as terpenes. Although its solubility in water is excellent, the product during production is in a solid or semi-solid state, so in the actual manufacturing aspect, a harmful organic solvent is used in the steps such as filtration, washing and filling. Is required, and it is difficult to prepare a paint as it is a solventless paint that cannot be mixed with pigments and fillers before it is used for paints. There was.

Therefore, there is a demand for an epoxy resin composition capable of providing an anticorrosion coating having excellent corrosion resistance, chemical resistance, curability and adhesion of a coating film, low viscosity and low volatility and excellent workability. Was there.

Therefore, an object of the present invention is to provide a coating film having low viscosity, excellent anticorrosion property and curability, and adhesion to various substrates without using an organic solvent harmful to human body. Another object of the present invention is to provide an epoxy compound useful as a reactive diluent for an epoxy resin.

[0009]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that epihalohydrin is added to a monophenol compound containing a cyclic terpene skeleton obtained by adding phenols to the cyclic terpene compound. The epoxy compound obtained by reacting is a low viscosity, and when used in combination with an epoxy resin, corrosion resistance, chemical resistance, curability,
It has been found that it is useful as a reactive diluent for epoxy resins for solventless anticorrosion paints of low viscosity and low volatility that does not use low boiling point solvents because it gives a coating film with excellent adhesion.

The present invention has been made based on the above findings, and a cyclic terpene skeleton obtained by reacting a monophenol compound containing a cyclic terpene skeleton, which is obtained by adding 1 mol of a phenol to 1 mol of a cyclic terpene compound, with epihalohydrin. The present invention provides a monoepoxy compound containing the same.

The present invention also provides a reactive diluent for an epoxy resin, which comprises the monoepoxy compound containing the cyclic terpene skeleton.

The present invention also provides an epoxy resin composition containing the above reactive diluent for epoxy resin.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The monoepoxy compound containing a cyclic terpene skeleton of the present invention will be described in detail below.

The monoepoxy compound containing a cyclic terpene skeleton of the present invention (hereinafter simply referred to as "epoxy compound") is
It is obtained by reacting a monophenol compound containing a cyclic terpene skeleton, which is obtained by adding 1 mol of a phenol to 1 mol of a cyclic terpene compound, with epihalohydrin.

The cyclic terpene compound used in the present invention may be a monocyclic terpene compound or a bicyclic terpene compound. Specific examples thereof include the compounds shown in the following [Chemical formula 1] to [Chemical formula 5].

[0016]

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[0017]

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[0018]

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[0019]

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[0020]

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Examples of the phenols used in the present invention include phenol, cresol, xylenol, propylphenol, nonylphenol, methoxyphenol, bromophenol, and the like. Phenol or cresol, xylenol, propylphenol, nonylphenol. Are particularly preferred.

The method of adding the above-mentioned cyclic terpene compound and the above-mentioned phenols is preferably such that the phenols are used in an amount of 0.5 to 5 mol, and more preferably 0.8 to 1.5 mol, per 1 mol of the cyclic terpene compound. However, it can be easily carried out by reacting at 40 to 160 ° C. for 1 to 10 hours in the presence of an acid catalyst. The above reaction can also be carried out in a solvent such as aromatic hydrocarbons, alcohols, ethers and the like. Here, the amount of the phenols used is 0.5 with respect to 1 mol of the cyclic terpene compound.
If the amount is less than 5 mol or more than 5 mol, the reaction by-product described below tends to occur, which is not preferable. Also,
Examples of the acid catalyst used in the above reaction include hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, boron trifluoride or its complex, activated clay and the like.

The structure of the monophenol compound containing a cyclic terpene skeleton, which is composed of 1 mol of the above cyclic terpene compound and 1 mol of the above phenols, varies depending on the type of both and the site of addition reaction. It is a compound in which a cyclic terpene compound and phenols are added at a ratio of 1: 1 and is a compound represented by the following general formula (I).

[0024]

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Further, specific examples of the above-mentioned monophenol compound containing a cyclic terpene skeleton are shown in compounds (1) to (5) of the following [Chemical formula 7], but the present invention is not limited thereto.

[0026]

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Further, when the above-mentioned monophenol compound containing a cyclic terpene skeleton is produced, impurities containing many reaction by-products are produced, and it is difficult to completely remove these impurities. The purity of the phenol compound is preferably 70% or more, more preferably 80%
If it is above, it can be effectively used, and if it is such a purity, it can be easily obtained by a method such as vacuum distillation. If the above-mentioned purity of less than 70% is used, the viscosity becomes too high to function as a diluent, and the physical properties of the coating film, particularly corrosion resistance, adhesion and other non-reaction It is not preferable because the compatibility with the organic diluent becomes insufficient.

Here, the impurities include, for example, terpene polyhydric phenols, polyterpene monophenols, terpene polymers, high molecular weight substances, unreacted raw materials, etc., and specific examples thereof are shown below. (I) to () indicate.

[0029]

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The epoxy compound of the present invention can be obtained by carrying out an epoxidation reaction by a usual method in which a terpene phenol compound obtained by the addition of the above cyclic terpene compound and the above phenol is reacted with epihalohydrin. The compound obtained here is a mixture containing a monoepoxy compound, and the epoxy compound of the present invention is obtained by reacting the monophenol compound among the terpene phenol compounds obtained by the addition with the epihalohydrin. It was obtained.

The method of the epoxidation reaction will be described in detail. First, the terpene phenol compound is dissolved in an amount of epihalohydrin corresponding to 2 to 20 mol per mol of the phenolic hydroxyl group to homogenize it, and then the solution is stirred. Meanwhile, an aqueous solution of an alkali metal hydroxide in an amount of 1 to 1.5 mol per mol of the phenolic hydroxyl group is added and reacted. Here, when the amount of the epihalohydrin used is less than 2 mol per mol of the phenolic hydroxyl group, the epoxy equivalent becomes too large, and the epoxy group formed by the reaction may react with the unreacted phenolic hydroxyl group. If it exceeds 20 mol, the reaction rate may decrease, which is not preferable.

The above epoxidation reaction can be carried out under normal pressure or reduced pressure, and the reaction temperature is usually 6 under normal pressure.
It is carried out at 50 to 80 ° C. under a reduced pressure reaction at 0 to 120 ° C. Further, during the reaction, the reaction liquid is azeotropically distilled, and the condensed liquid obtained by cooling the vaporized vapor is separated into oil and water, and dehydration is carried out by a method of returning the oil content from which water has been removed to the reaction system. Further, the addition of the aqueous solution of the alkali metal hydroxide is intermittently or continuously carried out little by little over 1 to 8 hours in order to suppress the rapid progress of the reaction. The reaction time of all the above reactions is usually about 1 to 10 hours. After the completion of the above reaction, the insoluble by-product salt is filtered off, further washed with water, and the unreacted epihalohydrin is distilled off under reduced pressure to obtain the target epoxy compound.

As the epihalohydrin, epichlorohydrin or epibromohydrin is usually used, and as the alkali metal hydroxide, caustic soda, caustic potash, etc. are used. In the above epoxidation reaction, tetramethylammonium chloride,
Quaternary ammonium salts such as tetraethylammonium bromide, tertiary amines such as dimethylbenzylamine, 2,4,6-tris (dimethylaminomethyl) phenol,
A catalyst such as imidazoles such as 2-phenylimidazole and 2-ethyl-4-methylimidazole, phosphonium salts such as ethyltriphenylphosphonium iodide, and phosphines such as triphenylphosphine may be used. Further, in the above epoxidation reaction, an inert organic solvent such as an aprotic polar solvent such as alcohols, ketones, ethers, dimethylformamide and dimethylsulfoxide may be used.

The epoxy equivalent of the epoxy compound of the present invention obtained as described above is preferably 250 to 7
50, more preferably 290 to 500. When the epoxy equivalent is less than 250, the viscosity is high and it is difficult to use as a diluent, and when the epoxy equivalent is more than 750, the curability is poor and the physical properties of the coating film are deteriorated.

Next, the reactive diluent for an epoxy resin of the present invention comprises the above-mentioned monoepoxy compound containing a cyclic terpene skeleton, and the epoxy compound alone or together with other reactive diluents as necessary. , Used as a reactive diluent for an epoxy resin composition.

Further, the epoxy resin composition of the present invention comprises the above-mentioned reactive diluent for epoxy resin, general-purpose epoxy resin,
It can be obtained by adding other reactive diluent, non-reactive diluent, curing agent or the like as necessary.

In the epoxy resin composition of the present invention, the reactive diluent for epoxy resin is epoxy resin 100.
The amount is preferably 1 to 50 parts by weight, more preferably 10 to 35 parts by weight, based on parts by weight. If the compounding amount of the above reactive diluent for epoxy resin is less than 1 part by weight, the effect as a diluent may not be sufficiently exhibited, and if it exceeds 50 parts by weight, the physical properties of the coating film after curing are adversely affected. There is a risk that it is not preferable.

Examples of the epoxy resin used here include various polyhydric phenols (eg, bisphenol A, bisphenol F, resorcin, hydroquinone, methylresorcin, phenol novolac, cresol novolac, resorcin novolac, bisphenol A novolac). Etc., or various glycidyl ether type epoxy resins produced from polyhydric phenols and hydroxybenzaldehyde, crotonaldehyde, glyoxazole, polyhydric phenols obtained by condensation reaction with various other aldehydes) and epihalohydrin, Multifunctional epoxy resins such as various glycidyl ester type epoxy resins, various glycidyl amine type epoxy resins, various aliphatic epoxy resins, various halogenated type epoxy resins, etc. That.

Among the above epoxy resins, in particular, when at least one polyglycidyl ether compound selected from the group consisting of mononuclear polyhydric phenols or polyglycidyl ethers of polynuclear polyhydric phenols and aliphatic polyglycidyl ethers is used, In particular, the use of a polyglycidyl ether of alkylidene bisphenol represented by the following chemical formula [Chem. 9] is preferable because an epoxy resin composition excellent in corrosion resistance, chemical resistance, adhesion to a substrate and the like can be obtained.

[0040]

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The other reactive diluents mentioned above include
Examples thereof include aromatic monoglycidyl ethers such as phenyl glycidyl ether and cresyl glycidyl ether, and aliphatic monoglycidyl ethers such as oleyl glycidyl ether. Further, as the non-reactive diluent, dioctyl phthalate, dibutyl phthalate,
Examples thereof include benzyl alcohol, coal tar and the like, and terpene oils such as pinene, limonene and terpinolene. In particular, as the other reactive diluent, aromatic monoglycidyl ether such as cresyl glycidyl ether is preferable in terms of corrosion resistance, and as the non-reactive diluent, terpene oil such as limonene is safe. From the point of, it is preferable.

Examples of the curing agent include polyalkylene polyamines such as diethylenetriamine, triethylenetetramine and tetraethylenepentamine, 1,
2-diaminocyclohexane, 1,4-diamino-3,
Alicyclic polyamines such as 6-diethylcyclohexane and isophoronediamine, aliphatic polyamines such as xylenediamine, polyamine curing agents such as aromatic polyamines such as diaminodiphenylmethane and diaminodiphenylsulfone, dicarboxylic acids such as these polyamines and dimer acid A polyamide polyamine curing agent obtained by reacting by a conventional method, or an epoxy addition modified polyamine curing agent obtained by adding an epoxy resin to these polyamines or a Michael addition modified polyamine curing agent obtained by adding acrylonitrile and the like, and the like, Further, latent curing agents such as dicyandiamide, acid anhydrides and imidazoles can also be used.

The epoxy resin composition of the present invention contains fillers such as glass fiber, cellulose, silica sand, cement, kaolin, clay, aluminum hydroxide, bentonite, silica, titanium dioxide, carbon black, graphite and iron oxide. It is also possible to use commonly used additives such as pigments, thickeners, dispersants, flame retardants and defoamers, and also concomitant agents such as xylene resins and petroleum resins.

The epoxy resin composition of the present invention can be used in various fields of application such as various moldings, adhesives, paints, laminations, etc., but is preferably used for paints, particularly solventless. Corrosion resistance by using for anticorrosion paint
It is preferable because a coating film excellent in curability and adhesion can be obtained.

Further, the method for forming the epoxy resin composition of the present invention into a coating material includes, for example, the following methods. That is, an additive such as a filler is added to the epoxy resin composition and kneaded with glass beads, a ball mill or the like according to a conventional method to obtain a coating composition. The resulting paint formulation is
After mixing the curing agent, a coating film can be obtained by applying a predetermined film thickness using a bar coater and drying and curing.

[0046]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited by the following examples. In the following description, “%” means “% by weight”.

Embodiment 1

In a 2 L reactor equipped with a thermometer, a stirrer and a water separator equipped with a cooling tube, YP-90LL (Yasuhara Chemical Co., Ltd. terpene monophenol 90%) was added.
Compounds contained; average molecular weight 266, hydroxyl equivalent 300) 4
After charging 86 g and 649 g of epichlorohydrin and stirring to make a uniform solution, 150 g of 48% sodium hydroxide solution was added dropwise at 60 to 110 ° C. over 2 hours.
During this period, the water generated in the system was azeotropically distilled with epichlorohydrin and removed to the outside of the system by a water separator, and epichlorohydrin was refluxed into the system. After dropping, 100-120 ° C
After aging for 2 hours, the reaction end point was the time when the theoretical amount of water was distilled off.

To the obtained epihalohydrin solution of the epoxy compound, 800 g of toluene was added and washed with a large amount of water,
After removing the generated sodium chloride and excess sodium hydroxide, the mixture was neutralized with a 3% phosphoric acid aqueous solution. Then, the epichlorohydrin and toluene were distilled off under reduced pressure to obtain an epoxy equivalent of 43
A pale yellow transparent liquid of 0, 478 g of a monoepoxy compound containing a cyclic terpene skeleton was obtained. The saponified chlorine% of the monoepoxy compound containing a cyclic terpene skeleton is 0.01%,
The viscosity was 900 cp / 25 ° C.

The refractive index of the product was measured and found to be 1.538. As a result of infrared absorption spectrum analysis, the following characteristic absorption was obtained. 2920 cm ^-1 , 15
^{10cm -1, 1450cm -1, 1360cm -1} , 125
0cm ^-1, 830cm ^-1, 750cm ^-1

Example 2 A 1 L reactor equipped with a thermometer, a stirrer and a water separator equipped with a condenser was charged with 94 g of phenol and 1.84 g of boron trifluoride etherate at a temperature of 70 to 80 ° C. , 136 g of limonene were added dropwise over 1 hour, and the mixture was aged at the same temperature for 1 hour. Then, after washing 3 times with 1 L of distilled water, impurities were distilled off under reduced pressure, and finally 160 ° C.,
After maintaining at 5 mmHg for 1 hour, 204 g of a monophenol compound containing a cyclic terpene skeleton (hydroxyl equivalent 236) was obtained.

When analyzed by liquid chromatography, the desired monophenol compound containing a cyclic terpene skeleton had a purity of 99% or more.

A 2 L reactor equipped with a thermometer, a stirrer and a water separator equipped with a condenser was charged with 133 g of this terpenephenol and 285 g of epichlorohydrin, and the mixture was stirred to give a uniform solution, followed by 48% hydroxylation. 47 g of sodium solution was added dropwise at 60 to 110 ° C. over 2 hours. During this period, the water generated in the system was azeotropically distilled with epichlorohydrin and removed to the outside of the system by a water separator, and epichlorohydrin was refluxed into the system. 100-12 after dropping
The mixture was aged at 0 ° C. for 2 hours, and the reaction end point was at the time when the theoretical amount of water was distilled off.

To the obtained epihalohydrin solution of the epoxy compound was added 500 g of toluene and washed with a large amount of water,
After removing the generated sodium chloride and excess sodium hydroxide, the mixture was neutralized with a 3% phosphoric acid aqueous solution. Then, the epichlorohydrin and toluene were distilled off under reduced pressure to obtain an epoxy equivalent of 30
201 g of a yellow transparent liquid monoepoxy compound containing a cyclic terpene skeleton was obtained. The monoepoxy compound containing a cyclic terpene skeleton had a saponifiable chlorine% of 0.01% and a viscosity of 100 cp / 25 ° C.

Example 3 The cyclic terpene skeleton monoepoxy compound obtained in Example 1 was converted to ADEKA RESIN EP-4900 (Asahi Denka Kogyo KK).
Made bisphenol F type epoxy resin, epoxy equivalent 17
0, viscosity 2000-4000 cp) and a ratio of 20/80 (weight basis, the same applies hereinafter), and viscosity 1300 cp
An epoxy resin composition of / 25 ° C was obtained.

Example 4 The cyclic terpene skeleton monoepoxy compound obtained in Example 1 was converted into ADEKA RESIN EP-4100 (Asahi Denka Kogyo KK).
Made bisphenol A type epoxy resin, epoxy equivalent 19
0, viscosity 18,000 to 20,000 CP), 30/70
To obtain an epoxy resin composition having a viscosity of 1800 cp / 25 ° C.

Example 5 The cyclic terpene skeleton monoepoxy compound obtained in Example 1, ADEKA RESIN EP-4100, and ADEKA GLYSILOL ED-529 (cresol monoepoxy reactive diluent manufactured by Asahi Denka Co., Ltd., epoxy equivalent) 180) to 1
Blended in a ratio of 5/70/15, viscosity 1900 cp / 2
An epoxy resin composition having a temperature of 5 ° C. was obtained.

Example 6 Cyclic terpene skeleton monoepoxy compound obtained in Example 1, ADEKA RESIN EP-4900, and ADECA GLYSILOL ED-502 (long-chain aliphatic monoepoxy reactive diluent manufactured by Asahi Denka Co., Ltd.) , Epoxy equivalent 320) to 2
Formulated in a ratio of 0/70/10 and a viscosity of 800 cp / 25
An epoxy resin composition having a temperature of 0 ° C. was obtained.

Example 7 The cyclic terpene skeleton monoepoxy compound obtained in Example 2 was mixed with ADEKARESIN EP-4900 at a ratio of 30/70 to obtain an epoxy resin composition having a viscosity of 700 cp / 25 ° C.

Example 8 The cyclic terpene skeleton monoepoxy compound obtained in Example 2 was mixed with ADEKARESIN EP-4100 at a ratio of 30/70 to obtain an epoxy resin composition having a viscosity of 1500 cp / 25 ° C.

Comparative Example 1 YP-90 (Yasuhara Chemical Co., Ltd. terpene diphenol; average molecular weight 324, hydroxyl equivalent 310) was placed in a 2 L reactor equipped with a thermometer, a stirrer and a water separator equipped with a cooling tube. 324 g and epichlorohydrin 5
After charging 43 g and stirring to make a uniform solution, 91.4 g of 48% sodium hydroxide solution was added at 60-110 ° C. for 2 hours.
It was dropped over time. During this period, the water generated in the system was azeotropically distilled with epichlorohydrin and removed to the outside of the system by a water separator, and epichlorohydrin was refluxed into the system. After the dropping, the mixture was aged at 100 to 120 ° C. for 2 hours, and the reaction end point was the time when the theoretical amount of water was distilled off.

To the obtained epichlorohydrin solution of the epoxy compound was added 800 g of toluene, and the mixture was washed with a large amount of water to remove the generated sodium chloride and excess sodium hydroxide, and then neutralized with a 3% phosphoric acid aqueous solution. Then, epichlorohydrin and toluene were distilled off under reduced pressure to obtain 360 g of a brown semi-solid cyclic terpene skeleton epoxy compound having an epoxy equivalent of 380.

Comparative Example 2 ADEKA RESIN EP-4900 and ADEKA GLYSILOL ED-529 were mixed in a ratio of 80/20, and a viscosity of 90 was obtained.
An epoxy resin composition of 0 cp / 25 ° C. was obtained.

Comparative Example 3 ADEKA RESIN EP-4100 and ADEKA GLYSILOL ED-502 were mixed in a ratio of 70/30, and a viscosity of 12 was obtained.
An epoxy resin composition of 00 cp / 25 ° C. was obtained.

Comparative Example 4 Adekaresin EP-4100 and the cyclic terpene skeleton epoxy compound obtained in Comparative Example 1 were mixed in a ratio of 80/20, but it was impossible to form a paint in a semi-solid state.

(Coating Test) Examples 3 to 8 and Comparative Example 2
The epoxy resin composition varnish obtained by adjusting the viscosity to 2,000 cp or less in 3 to 3 was kneaded in a ball mill for 6 hours to prepare a white paint.

(Compounding) Parts by weight Epoxy resin composition varnish 100 Nikanol LL (Xylene resin manufactured by Mitsubishi Gas Chemical Co., Inc.) 100 Talc 80 Titanium dioxide 20

Using the obtained white paint as a curing agent, Adeka Hardener EH-340 (modified polyamide polyamine manufactured by Asahi Denka Co., Ltd .; active hydrogen equivalent 81) was used as an epoxy group / curing agent active hydrogen equivalent of the epoxy resin composition. Ratio 1/1
To prepare a coating composition.

Next, the coating composition thus obtained was coated on a metal plate test piece with a coating film of 100 μ using an applicator and dried and cured at room temperature for 7 days. The obtained coating film test piece was tested for flexibility test, SST corrosion resistance test, temperature gradient test, gloss and aluminum adhesion by the following methods. Epoxy resin using the result is EP-4900
Those of EP-4100 are shown in the following [Table 1], and those of EP-4100 are shown in the following [Table 2].

Flexibility: φ20 using Erichsen tester
The flexibility was evaluated under the conditions of mm and 8 mm.

Corrosion resistance: Based on JIS K-5400
The sandblast plate coating film test pieces were subjected to SST for 500 hours. The criteria for judgment are as follows. Flat part ○: No rust or blister △: Rust, blister slightly visible ×: Rust, blister often seen Cross-cut part ○: Rust, blister 0.5 mm or less △: Rust, blister 1.0-1.5 mm ×: Rust, swelling 2.0 mm or more Secondary adhesion ○: No peeling of the coating film when peeling the tape △: Partial peeling of the coating film when peeling the tape ×: Complete peeling of the coating film when peeling the tape

Temperature Gradient Test: A shot blast test piece was placed in a temperature gradient tester at a temperature setting of 40 ° C./20° C., and the state of swelling was observed for 3 days. Further, the secondary adhesion of the coating film was evaluated for the test piece which was subjected to the temperature gradient tester for 3 days under the same conditions.

Gloss: The coating film gloss is measured with a gloss meter and the specular reflectance is 6
It was measured at 0 °.

Aluminum adhesion: A coating film test piece was prepared in the same manner using an aluminum plate specified in JIS H-4000, put in a cross cut, and a tape peeling test was conducted to compare the peeling state of the coating film. did.

[0075]

[Table 1]

[0076]

[Table 2]

As is clear from the above Examples and Comparative Examples, a monophenol compound containing a cyclic terpene skeleton obtained by adding 1 mol of a phenol to 1 mol of a cyclic terpene compound is reacted with epihalohydrin of the present invention. Epoxy compounds (Examples 1 and 2) can be used as reactive diluents for epoxy resins to give low viscosity epoxy resin compositions (Examples 3-8),
It is also found that when it is used as a paint, it exhibits excellent coating film performance.

[0078]

INDUSTRIAL APPLICABILITY The epoxy compound of the present invention, when used as a reactive diluent for epoxy resin, has a low viscosity and excellent workability, and has excellent corrosion resistance, gloss and adhesion when formed into a coating film. A composition can be provided. In addition, the epoxy resin composition of the present invention is particularly useful as a solvent-free anticorrosive paint excellent in corrosion resistance, curability and adhesion.

Claims (4)

[Claims] 1. A cyclic terpene skeleton-containing monoepoxy compound obtained by reacting a cyclic terpene skeleton-containing monophenol compound obtained by adding 1 mol of a phenol to 1 mol of a cyclic terpene compound with epihalohydrin. 2. A reactive diluent for an epoxy resin, which comprises the monoepoxy compound containing a cyclic terpene skeleton according to claim 1. 3. An epoxy resin composition comprising the reactive diluent for epoxy resin according to claim 2. 4. The epoxy resin composition according to claim 3, which is for a solvent-free anticorrosive paint.