JP2002097250A - Epoxy resin, its reaction product, and curable resin composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an epoxy resin excellent in heat resistance, flexibility and adhesive characteristic, and which is eco-friendly to the earth with high safety, and to provide its reaction product and a curable resin composition using the same. SOLUTION: The epoxy resin which is obtained by reacting with a phenol resin which is composed of 80 wt.%-99.9 wt.% phenol compound (A) shown by the formula (1) and 20 wt.%-0.1 wt.% phenol compound (B) shown by the formula (2), and an epihalohydorin is provided. And its reaction products and the curable resin composition using the same are provided. (R in the formula (1) and the formula (2) shows a 1-6 alkyl group, n shows an integer of 1 or more).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel epoxy resin, a reaction product thereof, and a curable resin composition using the same. More specifically, the present invention relates to an epoxy resin having excellent heat resistance, flexibility, corrosion resistance, and adhesiveness, and being environmentally friendly and highly safe, a reaction product thereof, and a curable resin composition using the same.

[0002]

2. Description of the Related Art Epoxy resins have been used as industrial materials in a wide range of fields because of their excellent properties such as heat resistance, corrosion resistance and adhesiveness. However, its use has been limited in fields such as paints, adhesives, and electrical and electronic applications. In recent years, with the increasing awareness of global environmental conservation, there has been a strong demand for the emergence of environmentally friendly and safer epoxy resins. The poor balance between the heat resistance and the flexibility described above means that epoxy resins having excellent heat resistance generally lack flexibility, whereas epoxy resins having excellent flexibility generally have poor flexibility. Poor heat resistance means a poor balance.

[0003] Various ortho-cresol novolak type epoxy resins are known as epoxy resins which give cured products having excellent heat resistance, but all of them have a binuclear content of about 10% by weight. Met. Further, in the orthocresol novolak type epoxy resin disclosed in JP-A-63-225621, there has been proposed a resin in which the binuclear content is further reduced than that described above. In addition, JP-A-63-163924 discloses a technique relating to an orthocresol novolak type epoxy resin having a diol component of 1000 ppm or less. Thus,
These conventional orthocresol novolak type epoxy resins having a low binuclear content have improved heat resistance as described above, but have a problem of poor flexibility. In addition, the impact resistance is insufficient, and in the electric and electronic fields, there is a problem in terms of internal stress due to insufficient flexibility.

On the other hand, propylene oxide-containing epoxy resins, urethane-modified epoxy resins, and the like have been proposed to impart flexibility to epoxy resins. However, contrary to the above, these epoxy resins have poor heat resistance, and have a decrease in corrosion resistance and moisture resistance due to a decrease in Tg in the field of paints and adhesives. Have been.

Attempts have been made to achieve a balance between both physical properties by mixing an epoxy resin having excellent heat resistance and an epoxy resin having excellent flexibility. At present, it has not been able to obtain a satisfactory level, such as only the characteristics of its physical properties. In addition, bisphenol A, which is one of the epoxy resin raw materials, has environmental problems as an estrogen-like substance, and countermeasures are urgently required.

[0006]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, is excellent in balance between both heat resistance and flexibility, has good corrosion resistance and adhesiveness, and is environmentally friendly. An object of the present invention is to provide a gentle and highly safe epoxy resin, a reaction product thereof, and a curable resin composition.

[0007]

Means for Solving the Problems As a result of intensive studies on the means for solving the above-mentioned problems, the present inventors have found that conventional ortho-cresol novolak type epoxy resins have the following characteristics.
Focusing on the fact that the nucleus content was only about 10% by weight at most, and when the content of the dinuclear nucleus was increased to 80% by weight or more, the balance between heat resistance and flexibility was excellent and safe. The inventors have found that an epoxy resin having high property can be obtained, and have reached the present invention.

That is, the present invention provides: 80% by weight to 99.9% by weight of a phenol compound (A) represented by the following general formula (1) and 20% by weight of a phenol compound (B) represented by the following general formula (2)
An epoxy resin obtained by a reaction between a phenol resin consisting of 0.1% by weight and epihalohydrin,

[0009]

Embedded image (R in the above formulas (1) and (2) represents an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 or more.)

[0010] 2. R in the general formulas (1) and (2)
2. The epoxy resin according to the above 1, wherein is a methyl group. The epoxy resin according to the above 1 or 2, wherein the amount of α-glycol is from 600 to 1 meq / kg,

4. The phenolic compound (A) represented by the above general formula (1) is 80% by weight to 99.9% by weight and the epoxy resin described in any one of the above 1 to 3 is represented by the above general formula (2). Phenol compound (B) 20% by weight
4. an epoxy resin obtained by reacting a phenol resin consisting of 0.1 to 0.1% by weight (R and n are as described above); The epoxy resin according to the above 4, wherein R in the general formulas (1) and (2) is a methyl group,

6. 6. An epoxy resin reaction product obtained by reacting the epoxy resin according to any one of the above 1 to 5 with an active hydrogen group-containing compound; 7. The epoxy resin reaction product according to the above item 6, wherein the active hydrogen group-containing compound is a phenol and / or a carboxylic acid. A curable resin composition comprising the epoxy resin and / or the epoxy resin reaction product according to any one of the above 1 to 7 and a curing agent for epoxy,

9. 9. a curable resin composition for paint containing the resin composition according to the above item 8, 10. A curable resin composition for electric / electronic use containing the resin composition according to the above item 8, 11. A curable resin composition for an adhesive, comprising the resin composition according to the above item 8, 12. A curable resin composition for civil construction containing the resin composition according to the above item 8, It is intended to provide a curable resin composition for a composite material containing the resin composition according to the above item 8.

Hereinafter, the present invention will be described in detail. The epoxy resin of the present invention is obtained by reacting an alkylphenol represented by the following general formula (3) with formaldehyde in the presence of an acidic catalyst or a basic catalyst.
Phenol compound (A) represented by the formula:
It is obtained by performing an epoxidation reaction using epihalohydrin using a phenol resin, which is 9% by weight and a phenolic resin (B) represented by the general formula (2), which is 20% by weight to 0.1% by weight as a raw material.

[0015]

Embedded image (R in the formula (3) represents an alkyl group having 1 to 6 carbon atoms.)

In the phenol compound (B) represented by the general formula (2), n in the formula (2) is an integer of 1 or more, particularly preferably 1 or more and 10 or less. Further, in the phenol resin, the amounts of the compounds (A) and (B) can be controlled by the reaction ratio between the alkylphenol and formaldehyde.
That is, by increasing the reaction ratio of the alkylphenol, a phenol resin having a higher content of the phenol compound (A) can be obtained. In general, in this embodiment, n = 1 is 90% or more, and the others are 10%.
It is as follows.

R in the general formulas (1) and (2) has 1 carbon atom.
When the number of carbon atoms of R is 7 or more, heat resistance and corrosion resistance decrease, which is not preferable. A particularly preferred alkyl phenol is orthocresol.

For the epoxidation reaction, a known method of reacting epihalohydrin with a phenolic hydroxyl group in the presence of a catalyst and then closing the ring with an alkali can be employed. An epoxy resin can be obtained.

For example, a low molecular weight epoxy resin can be obtained by carrying out the reaction under the condition of a large excess of epihalohydrin. Specifically, the phenol compound (A) represented by the general formula (1) is from 80% by weight to 99.9% by weight, and the phenol compound (B) represented by the general formula (2) is from 20% by weight to 20% by weight. By using a phenol resin consisting of 0.1% by weight as a raw material and reacting it with a 5-fold equivalent of epihalohydrin, by removing unreacted epihalohydrin,
Glycidyl compound (C) 8 represented by the following general formula (4)
0% to 99.9% by weight, 20% to 0.1% by weight of the glycidyl compound (D) represented by the following general formula (5)
Can be obtained.

[0020]

Embedded image

When the reaction is carried out under the condition that the amount of phenol resin is increased as compared with the above method, a high molecular weight epoxy resin can be obtained. That is, 80% by weight to 99.9% by weight of the phenol compound (A) represented by the general formula (1),
When a phenol resin comprising 20% to 0.1% by weight of the phenol compound (B) represented by the general formula (2) is used as a raw material and reacted with 1.1 to 1.5 equivalents of epihalohydrin, a molecular weight of about About 700 to 2000 epoxy resins can be obtained.

Further, the epoxy resin obtained by the method of the present invention is used as a raw material, and the phenol compound (A) represented by the general formula (1) is used in an amount of 80% by weight to 99.9% by weight.
A high-molecular-weight epoxy resin can be obtained by heating and reacting a phenol resin comprising 20% to 0.1% by weight of the phenol compound (B) represented by the general formula (2) in the presence of a basic catalyst.

When the content of the phenol compound (A) is less than 80% by weight, the flexibility of the cured product deteriorates.
When an active hydrogen group-containing compound is reacted or epihalohydrin having an equivalent amount or less is reacted, a gel is formed, which is not preferable. On the other hand, when the phenol compound (B) is not contained, the heat resistance is undesirably reduced. Preferably, the phenol compound (A) is 85% by weight to 99.9% by weight.
15% by weight to 0.1% by weight of the phenol compound (B).
An epoxy resin obtained by reacting 1% by weight of a phenol resin with epihalohydrin. Epichlorohydrin is preferred as epihalohydrin.

The range of the α-glycol content of the epoxy resin of the present invention is from 600 to 1 meq / Kg. The α-glycol referred to in the present invention is a terminal group of an epoxy resin represented by the following general formula (6), and is a group generated by hydrolysis of an epoxy group. The amount of α glycol is 600 meq /
When the amount is larger than Kg, not only the moisture resistance of the cured product is lowered but also components extracted from the cured product with water are increased. In particular, when applied to packaging materials such as food packaging containers, serious problems occur in terms of safety and health. In addition, 1 milliequivalent /
If it is less than Kg, there is a problem that the adhesiveness is reduced. A particularly preferred amount of α-glycol is in the range of 500 to 1 meq / Kg.

[0025]

Embedded image

The epoxy resin reaction product of the present invention is obtained by reacting the above epoxy resin with an active hydrogen group-containing compound. Here, the active hydrogen means a hydrogen atom bonded to an oxygen atom, a nitrogen atom, and a sulfur atom. Active hydrogen-containing compounds having these active hydrogens include phenols,
Examples include amines, imines, carboxylic acids, and thiols, and among them, phenols and carboxylic acids are preferred.

Specific examples of phenols include bisphenol A, bis (4-hydroxyphenyl) methane,
1,1-bis (4-hydroxyphenyl) ethane, 1,
1- (4-hydroxyphenyl) cyclohexane, 4,
Bisphenols such as 4'-dihydroxybenzophenone, 4,4'-dihydroxybiphenyl, 3,3 ', 5,5'-tetramethylbiphenyl, brominated bisphenol A, bis (4-hydroxyphenyl) sulfone; catechol, resorcinol, Mononuclear polyphenols such as hydroquinone and pyrogallol; polynuclear polyphenols such as naphthalene diol, resole type phenol resin and cresol novolak resin; and hydroxyphenyl type terminal aromatic polycarbonates, aromatic polyesters and aromatic polysulfones There are polymer-type phenols; other active hydrogen-containing phenols such as aminophenol; and derivatives thereof.

Specific examples of the carboxylic acids include aromatic polycarboxylic acids such as orthophthalic acid, isophthalic acid, terephthalic acid, toluenedicarboxylic acid, trimellitic acid, and hemimellitic acid; and polynuclear aromatic carboxylic acids such as naphthalenedicarboxylic acid. Other active hydrogen-containing aromatic carboxylic acids such as hydroxybenzoic acid and aminobenzoic acid; and derivatives thereof; aliphatic dicarboxylic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and undecandioic acid; dimers Acids, unsaturated aliphatic dicarboxylic acids such as dihydromuconic acid; tetrahydrophthalic anhydride;
Fatty (cyclic) polycarboxylic acids such as 2,3-propanetricarboxylic acid and 4-methylhexahydrophthalic acid; other active hydrogen-containing fatty (cyclic) carboxylic acids such as aminovaleric acid and oxyundecanoic acid; There are derivatives of

Specific examples of the amines include aliphatic monoamines such as methylamine, isoamylamine and allylamine; aliphatic diamines such as methylenediamine, ethylenediamine, tetramethylenediamine and hexamethylenediamine; 1,2,3-triamino Saturated polyvalent amines such as propane, tetra (aminomethyl) methane and polyalkylenepolyamine; alicyclic amines such as cyclopropylamine and cyclohexylamine; aromatic amines such as aniline, diaminodiphenylmethane and diaminodiphenylsulfone; guanamine and melamine And the like.

Specific examples of imines include ketimine, imidazole, piperazine, hydantoin and the like.
Examples of the thiols include polymercaptan, esters of thiogluconic acid and alcohols, and polysulfide resins.

The reaction between the epoxy resin and the active hydrogen group-containing compound is carried out by heating the epoxy resin and the active hydrogen group-containing compound in a solvent or without a solvent in the presence or absence of a catalyst. 1 to adjust molecular weight
An epoxy resin reaction product obtained by reacting in the presence of a trivalent phenol and / or a glycidylated product thereof can also be suitably used.

When the epoxy resin and / or reaction product of the epoxy resin of the present invention is cured using a usual curing agent for epoxy, a curable resin composition having a good balance between heat resistance and flexibility can be obtained.

Examples of the epoxy curing agent include amines, aminoplasts, phenols, anhydrides of polycarboxylic acids, and isocyanates. Among the polycarboxylic anhydrides, examples of suitable dicarboxylic anhydrides include phthalic anhydride, methylphthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride,
Fumaric anhydride, maleic anhydride and the like. Examples of suitable tricarboxylic anhydrides include 1,2,3-propanetricarboxylic anhydride, trimellitic anhydride, hemi-mellitic anhydride and the like. Examples of suitable tetracarboxylic anhydrides include pyromellitic anhydride, benzophenone-3,3 ′, 4,4′-tetracarboxylic acid and the like.

Examples of phenols include resols,
Novolak phenols, alkylphenol novolaks, for example, cresol novolak, nonylphenol novolak, polyalkenyl phenols, for example, poly-p-vinylphenol, poly-p-isopropenylphenol and the like can be mentioned.

Examples of amines and aminoplasts include aromatic amines such as diaminodiphenylmethane, m-phenylenediamine, 0- or p-phenylenediamine, diaminodiphenylsulfone, 2,6-diaminopyridine, benzylmethylamine , Tetramethylethylenediamine, N-methylmorpholine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, triethylenediamine, tetramethylguanidine, dicyandiamide, or Mannich bases comprising these amines and phenols, dimerization with amines or 3 Polyamidoamines produced from quantified fatty acids, adducts of amines and polyepoxides with a stoichiometric equivalent or less, methylolated melamine, butyrolated melamine, and the like. Examples of isocyanates include tolylene diisocyanate, MDI, polymeric MDI, and the like.

The equivalent ratio of the epoxy resin and / or the epoxy resin reaction product of the present invention to the curing agent for epoxy is 0.1.
It is used in the range of 5: 1 to 2: 1. Examples of the epoxy curing agent of the present invention include compounds having a catalytic action of causing epoxy groups to react with each other, such as tertiary amines, imidazoles, and cationic curing agents.

Examples of the tertiary amines include dimethylethanolamine and trialkylamines such as triethylamine, tripropylamine and tributylamine. Examples of the imidazoles include imidazole, 2-methylimidazole and 2-4-methylimidazole. , 2-phenylimidazole, 2-undecylimidazole, 2-
Heptadecyl imidazole, 1-benzyl-2-methylimidazole, 2-phenyl-4-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-aminoethyl-2-methylimidazole, 1- (cyanoethylaminoethyl) -2-methylimidazole, and the reaction product of these imidazoles and epoxy resin No.

Examples of cationic curing agents include boron trifluoride or antimony hexafluoride and complexes thereof, for example, chelates formed by reaction with amines or 1,3-diketones, Al silanol complexes, SnCl ₄ ,
AlCl _{3 and the} like. In the present invention, the epoxy resin and / or the compound having a catalytic action of causing the epoxy groups to react with each other on the epoxy resin reaction product 100 is used in the range of 0.01 to 50 parts by weight.

The epoxy resin and / or the epoxy resin reaction product of the present invention may be used in combination with another epoxy compound. Examples of the epoxy compound used in combination include a bisphenol A epoxy resin, a bisphenol F epoxy resin, an epoxy cresol novolak resin, and an epoxyphenol novolak resin. By using these resins and curing with a usual epoxy curing agent, a curable resin composition having a good balance between heat resistance and flexibility can be obtained.

The epoxy resin and the epoxy resin reaction product of the present invention may contain, if necessary, a curing accelerator, a pigment, an additive, a diluent, etc. in addition to the epoxy curing agent.

As a curing accelerator, a curing accelerator for epoxy resin can be suitably used. For example, tertiary amines or salts thereof, quaternary ammonium compounds, phosphines, phosphonium salts or alkali metal alkoxides can be used. Examples include n-benzyldimethylamine, 2,4,6-tris (dimethyl-aminomethyl) -phenol, imidazoles and trimethylammonium phenoxide, triphenylphosphine, ethyltriphenylphosphonium bromide and the like.

Also, boron trifluoride or antimony hexafluoride and its complexes, for example, amines or 1,3-
A chelate formed by a reaction with a diketone, an Al silanol complex, SnCl ₄ , AlCl _{3, and} other epoxy resin cationic curing agents can be used. In addition, metal nitrates, especially magnesium nitrate and manganese nitrate, fluorinated and chlorinated carboxylic acids and salts thereof (for example, magnesium trifluoroacetate, sodium trifluoroacetate, magnesium trichloroacetate and sodium trichloroacetate, trifluoromethanesulfonic acid and the like) Salts (eg, manganese, zinc, magnesium, nickel and cobalt salts) as well as magnesium perchlorate and magnesium perchlorate and calcium perchlorate can be used.

Examples of pigments include coloring pigments and extender pigments generally used for paint applications. Examples of color pigments include, as organic pigments; azo pigments, copper phthalocyanine pigments, basic dye lakes, acid dye lakes, mordant dye pigments, vat dye pigments, quinacridone pigments, dioxazine pigments, condensation Examples of carbon blacks and inorganic pigments such as azo pigments; oxides such as chromate, ferrocyanide, and titanium white; selenide sulfide; silicates, carbonates, phosphates, and metal powders. As the extender, barium sulfate, barium carbonate, powder, gypsum, alumina white, clay, silica, talc, calcium silicate, magnesium carbonate and the like can be used.

Examples of the additives include a dryer such as cobalt naphthenate, an anti-skinning agent such as methoxyphenol and cyclooxane oxime, a thickening agent such as highly polymerized linseed oil, organic bentonite and silica, a fatty acid, lecithin and silicone oil. And the like, an anti-floating agent such as benzoin, and a flow control agent such as Modaflow.

Further, various function-imparting agents can be used. For example, flame retardants such as antimony trioxide, Br-containing compounds and phosphorus-containing compounds; release agents such as natural waxes, synthetic waxes, higher fatty acids and metal salts thereof, and paraffins; surfaces such as silane coupling agents Processing agent;
Low stress agents such as polybutadiene, butadiene-acrylonitrile copolymer, silicone rubber, silicone oil; light stabilizers such as hindered amines; heat stabilizers such as hindered phenols; coloring agents such as carbon black. Can be used.

In addition, inorganic compounds which do not themselves contribute to the curing reaction but have the effect of improving mechanical strength, curing shrinkage, heat generation during curing, expansion coefficient, thermal conductivity and electrical properties, and which can be used as extenders Can be used. Examples thereof include various silica powders, alumina powders, talc powders, quartz glass powders, calcium carbonate, glass chops, asbestos, mica, calcium silicate, gypsum, barium sulfate, magnesium carbonate and the like.

Examples of diluents include non-reactive and / or
Alternatively, an organic solvent which is reactive and preferably used for decreasing the viscosity may be used. Water is also a suitable diluent if a dispersant or emulsifier is used.

Examples of non-reactive diluents are acetone,
Examples include methyl ethyl ketone, methyl isobutyl ketone, toluene, xylene, cellosolve, and the like. Examples of non-reactive diluents include acetone, methyl ethyl ketone,
Examples include methyl isobutyl ketone, toluene, xylene, cellosolve, Solvesso 100, N-methylpyrrolidone, dimethylformamide and the like. Examples of the reactive diluent include butyl glycidyl ether, neopentyl diglycidyl ether, 1.6-hexanediol, and the like. As reactive diluents, butyl glycidyl ether, neopentyl diglycidyl ether,
1.6-hexanediol and the like.

The curable composition of the present invention can be suitably used for paints, adhesives, civil engineering, electric / electronic devices, and composite materials. For paints, it is possible to provide packaging materials as protective materials for metals, woods, and plastic materials, and paints having excellent anticorrosion properties and flexibility for automobiles, ships, construction materials, and the like. An adhesive excellent in heat resistance and adhesiveness can be provided for adhesives, and a material excellent in chemical resistance can be provided for civil engineering, such as a coating material or an injection material for a concrete driving body. For electric / electronic use, it can be used as a material having excellent heat resistance and flexibility as a laminate, a sealing material, and other insulating materials. When used as a material for a composite material, a tough molding material can be provided. Among these, particularly suitable fields of application are paint applications, adhesive applications and electrical and electronic applications.

[0050]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The embodiments of the present invention will be specifically described below with reference to examples. The amount of α-glycol was measured by reacting α-glycol with ammonium periodate, reducing unreacted periodate with potassium iodide to generate iodine, and titrating this iodine with a sodium thiosulfate standard solution. .

(Synthesis Example 1) A 2 L round bottom flask equipped with a stirrer and a thermometer was charged with a binucleate content of 85% by weight and
376 g of orthocresol novolak having a content of 15% by weight or more of the nucleus was added, and epichlorohydrin was added to 1526%.
g, and the temperature was raised to 60 ° C., followed by 48% NaOH 19
8 g was dropped in 55 minutes, and further stirred for 1 hour,
The reaction was performed. After the obtained reaction solution was washed with 380 g of water, 132 g of 48% NaOH was further added dropwise for 40 minutes, and the reaction was carried out for 1 hour. Then, after washing with 500 g of water until the alkali disappears, 140 to 150 ° C.
The epichlorohydrin was removed by a rotary evaporator at the temperature described above to obtain an epoxy resin 1 having an epoxy equivalent of 183 and an α-glycol amount of 75 meq / Kg.

Synthesis Example 2 Epichlorohydrin 1526
g was replaced with 1521 g of epichlorohydrin and 5 g of glycidol in the same manner as in Synthesis Example 1, except that
Epoxy equivalent 185, α glycol amount 490 meq /
Kg of epoxy resin 2 was obtained.

(Synthesis Example 3) An epoxy resin 3 having an epoxy equivalent of 180 and an α-glycol content of 10 meq / Kg was obtained in the same manner as in Synthesis Example 1 except that 376 g of orthocresol novolak having a binuclear content of 100% by weight was used. I got

(Synthesis Example 4) The content of three or more nuclei is 100
An epoxy equivalent of 19 was obtained in the same manner as in Synthesis Example 1 except that 376 g of ortho-cresol novolak was used.
An epoxy resin 4 having an amount of 0, α glycol of 100 meq / Kg was obtained.

(Synthesis Example 5) Epichlorohydrin 1526
By the same operation as in Synthesis Example 1 except that 1515 g of epichlorohydrin and 11 g of glycidol were used instead of g, epoxy resin 5 having an epoxy equivalent of 193 and an α-glycol amount of 800 meq / Kg was obtained.

(Synthesis Example 6) Epoxy resin 1, 1000
g, binucleate content 85% by weight, trinuclear or higher content is 1
460 g of 5% by weight orthocresol novolak was placed in a 2 L round bottom flask equipped with a stirrer and a thermometer, and N 2 was added.
0.07 g of aOH was added and reacted at 180 ° C. for 10 hours to obtain an epoxy resin 6 having an epoxy equivalent of 1800.

(Synthesis Example 7) Epoxy resin 2, 1000
g, binucleate content 85% by weight, trinuclear or higher content is 1
An epoxy resin 7 having an epoxy equivalent of 1790 was obtained by the same operation as in Synthesis Example 6 except that 460 g of 5% by weight of orthocresol novolak was used.

(Synthesis Example 8) Epoxy resin 1, 1000
g, an epoxy resin 8 having an epoxy equivalent of 1810 was obtained in the same manner as in Synthesis Example 6 except that 460 g of orthocresol novolak having a binuclear content of 100% by weight was used.

(Synthesis Example 9) Epoxy resin 3, 1000
g, and an epoxy resin 9 having an epoxy equivalent of 1810 was obtained in the same manner as in Synthesis Example 6 except that 460 g of orthocresol novolak having a binuclear content of 100% by weight was used.

(Synthesis Example 10) Epoxy resin 4, 1000
g of epoxy resin 10 having an epoxy equivalent of 1760 by the same operation as in Synthesis Example 6 except that 460 g of orthocresol novolak having a binuclear content of 100% by weight was used.

(Synthesis Example 11) Epoxy resin 5, 1000
g, binucleate content 85% by weight, trinuclear or higher content is 1
An epoxy resin 11 having an epoxy equivalent of 1790 was obtained in the same manner as in Synthesis Example 6 except that 460 g of 5% by weight of orthocresol novolak was used.

[0062]

EXAMPLES Examples 1 to 3 and Comparative Examples 1 to 5 The formulations shown in Table 1 were prepared, and the viscosity was adjusted to 20 to 40 seconds with Ford Cup No. 4 using toluene, and the respective clear paints for cans were prepared. Prepared. The clear paint is sprayed on a mild steel plate by air spray and heat-cured at 180 ° C. for 30 minutes to produce a mild steel plate to be coated having a thickness of 30 to 40 μm.
Its physical properties were measured. In addition, the hot water extractability was performed in order to check the extraction from the coating film when a beverage was packed in a can and subjected to retort sterilization. The measurement results are shown in Table 1. The epoxy resin reaction product of the present invention is excellent in the balance between physical properties of salt spray resistance (indicating corrosion resistance of a coating film) and impact resistance (DuPont impact value is shown as representative of flexibility), and has a good effect. It can be seen that it has excellent eye adhesion and hot water extractability.

[0063]

[Table 1]

Examples 4 and 5 and Comparative Examples 6 to 11 The compositions shown in Table 2 were poured into a mold and heated at 180 ° C. for 5 minutes.
After curing for a time, a casting was obtained. The heat resistance (T
g) and Charpy impact (representing flexibility) were measured. Table 2 shows the measurement results. It can be seen that the epoxy resin of the present invention has an excellent balance of heat resistance (Tg), flexibility (Charpy) and physical properties of impact, and also has good water absorption.

[0065]

[Table 2]

[0066]

The epoxy resin and the epoxy resin reaction product of the present invention and the novel curable resin composition using the same are environmentally friendly and highly safe, and the cured product has heat resistance and flexibility. Has a good balance and is excellent in anticorrosion properties, adhesiveness, and hot water resistance.

Continued on front page F-term (reference) 4J036 AF06 AF08 DB18 DB20 DB21 DB22 FB07 JA01 JA06 JA07 JA08 4J038 DA062 DA132 DB071 DB461 DD062 DE012 DK012 GA03 HA106 HA476 JA20 JA33 JA39 JA41 JA42 JA63 JB03 JB04 JB05 JB06 JB30 JBJ JB30 JB30 NA03 NA12 NA14 NA27 PA19 PB05 PB07 PC02 4J040 EB022 EB072 EB152 EC081 ED042 EJ032 GA05 GA06 GA14 GA24 HA326 HB19 HB22 HB26 HB28 HB38 HC03 HC04 HC16 HC22 HC25 HD02 HD05 HD41 JA02 JB02 KA14 KA16 LA06

Claims (13)

[Claims] 1. A phenol compound (A) represented by the following general formula (1): from 80% by weight to 99.9% by weight, and a phenol compound (B) represented by the following general formula (2): from 20% by weight to 20% by weight. An epoxy resin obtained by reacting a phenol resin consisting of 0.1% by weight with epihalohydrin. Embedded image (R in the general formulas (1) and (2) has 1 to 1 carbon atoms.
6 represents an alkyl group, and n is an integer of 1 or more. ) 2. The epoxy resin according to claim 1, wherein R in the general formulas (1) and (2) is a methyl group. 3. The amount of α-glycol is 600 to 1 milliequivalent /
The epoxy resin according to claim 1, wherein the weight is kg. 4. The epoxy resin according to claim 1, wherein 80% to 99.9% by weight of a phenolic compound (A) represented by the following general formula (1) is used: 20% by weight or more of the phenolic compound (B)
An epoxy resin obtained by reacting a phenol resin consisting of 0.1% by weight. Embedded image (R in the general formulas (1) and (2) has 1 to 1 carbon atoms.
6 represents an alkyl group, and n is an integer of 1 or more. ) 5. The epoxy resin according to claim 4, wherein R in the general formulas (1) and (2) is a methyl group. 6. An epoxy resin reaction product obtained by reacting the epoxy resin according to claim 1 with an active hydrogen group-containing compound. 7. The epoxy resin reaction product according to claim 6, wherein the active hydrogen group-containing compound is a phenol and / or a carboxylic acid. 8. A curable resin composition comprising the epoxy resin and / or reaction product of the epoxy resin according to claim 1 and a curing agent for epoxy. 9. A curable resin composition for a paint, comprising the resin composition according to claim 8. 10. A curable resin composition for electric and electronic use containing the resin composition according to claim 8. 11. A curable resin composition for an adhesive, comprising the resin composition according to claim 8. 12. A curable resin composition for civil construction, comprising the resin composition according to claim 8. 13. A curable resin composition for a composite material, comprising the resin composition according to claim 8.