JP5342200B2 - Reactive diluent for epoxy resin and thermosetting epoxy resin composition - Google Patents

Description

  The present invention relates to a reactive diluent for an epoxy resin and a thermosetting epoxy resin composition containing the same. More specifically, the present invention relates to a reactive diluent excellent in reactivity, dilutability, compatibility and mechanical properties of a cured product, particularly heat resistance and flexibility.

  Conventionally, epoxy resin has been used in various fields as a material for civil engineering / architecture, electrical / electronic parts, and transportation equipment, such as paints, adhesives, sealants, casting agents, laminates, and sealants, due to its excellent properties. Widely used. Among them, liquid bisphenol A type epoxy resins are excellent in physical properties and economically and are most frequently used. However, this type of resin has a high viscosity, and as it is, the viscosity is high and the workability is problematic. Therefore, various diluents are generally used and adjusted to a viscosity suitable for work.

Diluents can be divided into non-reactive and reactive.
As the non-reactive diluent, an organic solvent or a plasticizer is generally used. However, the organic solvent is generally limited to a field such as a paint using volatility and has a problem of toxicity and air pollution. In addition, since the plasticizer cannot be bonded to the skeleton of the epoxy resin and remains in the cured product as it is, there is a problem that the original performance of the epoxy resin cannot be exhibited and the physical properties are remarkably deteriorated.
On the other hand, the reactive diluent has an epoxy group in the molecule, so that it reacts with the curing agent to become a part of the cured product. . Among them, a glycidyl ether of a higher alcohol has been proposed as a useful reactive diluent (for example, Patent Document 1).

However, this technique is excellent in dilution performance and effective in imparting flexibility, but has a problem that heat resistance is insufficient. In general, it is known that flexibility and heat resistance conflict. Therefore, a reactive diluent that satisfies both flexibility and heat resistance while maintaining dilution performance has been desired.
JP-A-6-172336

  Then, it aims at providing the reactive diluent for epoxy resins which can obtain the thermosetting epoxy resin hardened | cured material which was excellent in dilution performance, and was compatible with flexibility and heat resistance.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention comprises an epoxy resin reactive diluent (B) comprising an epoxy compound (A) represented by the following general formula (1) as an essential component; this reactive diluent for epoxy resin (B) A thermosetting epoxy resin composition comprising an epoxy resin and a curing agent.

[In Formula (1), R < ¹ >, R < ² > is a hydrogen atom or a methyl group each independently, and does not become a hydrogen atom simultaneously ; R < ³ > is a hydrogen atom, a C1-C16 alkyl group, a phenyl group Or a phenylalkyl group having 7 to 12 carbon atoms; R ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms. m is a number from 1 to 3, and n is a number from 1 to 50. ]

  By using the reactive diluent for epoxy resin of the present invention, the epoxy resin can be adjusted to a viscosity suitable for work, and an epoxy resin cured product excellent in both flexibility and heat resistance can be obtained. it can.

  The present invention comprises, as an essential component, an epoxy compound (A) represented by the above general formula (1), a reactive diluent for epoxy resin (B), and a reactive diluent for epoxy resin (B) ), An epoxy resin (C), and a curing agent (D).

  The epoxy compound (A) represented by the general formula (1) is obtained by adding alkylene oxide to styrenated phenols (a) obtained by reacting phenols with styrenes, and styrenated phenols alkylene oxides. After obtaining the adduct (b), it can be obtained by glycidyl etherification.

Regarding styrenes, R ¹ and R ² in the general formula (1) each independently represent a hydrogen atom or a methyl group.
Specific examples include styrene and α-methylstyrene.

Regarding phenols, R ³ in the general formula (1) represents a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, a phenyl group, or a phenylalkyl group having 7 to 12 carbon atoms.
Specifically, examples include alkylphenols such as carboxylic acid, cresol, xylenol, ethylphenol, propylphenol, butylphenol, hexylphenol, octylphenol, and nonylphenol, and phenols having an aromatic substituent such as phenylphenol and cumylphenol. It is done.

Styrenated phenols (a) include phenols and styrenes, inorganic acids such as sulfuric acid, phosphoric acid and hydrochloric acid, organic acids such as oxalic acid and toluenesulfonic acid, silica-alumina, zeolite, ion exchange resin, acidic clay. It can be obtained by reacting in the presence of an acid catalyst such as a solid acid such as boron trifluoride.
Of these, preferred as the styrenated phenols (a) are those obtained by the reaction of carboxylic acid, octylphenol, nonylphenol, cumylphenol and styrene.

  The added mole number m of styrenes in the general formula (1) is usually 1 to 3 with respect to the phenols. When m is less than 1, the heat resistance cannot be satisfied. When m exceeds 3, the viscosity becomes high and sufficient dilution performance cannot be exhibited.

The styrenated phenols alkylene oxide adduct (b) can be obtained by adding alkylene oxides to the styrenated phenols (a).
R ⁴ O in the general formula (1) represents an oxyalkylene group having 2 to 4 carbon atoms, and n is the added mole number of alkylene oxide.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, butylene oxide and the like.
Of these, ethylene oxide, propylene oxide, and a combination thereof are preferable.
The addition form may be either homopolymerization, two or more types of random copolymerization, or block copolymerization.
The added mole number n is usually 1 to 50, preferably 1 to 20, and more preferably 1 to 10. When n is less than 1, flexibility cannot be imparted, and when n exceeds 50, flexibility can be imparted but heat resistance cannot be satisfied.

The epoxy compound (A), which is an essential component of the present invention, is obtained by glycidyl etherification of the above-mentioned styrenated phenols alkylene oxide adduct (b). In the presence of a solid alkali metal hydroxide, (b) is epichlorohydrin. The glycidyl group can be introduced by reacting.
The amount of epichlorohydrin is preferably 1.2 to 2.5 equivalents, more preferably 1.5 to 2.0 equivalents, relative to 1 equivalent of the hydroxyl group of the alcohol. When it is 1.2 equivalents or more, the reaction time does not become long, and a side reaction between the produced glycidyl ether and epichlorohydrin hardly occurs. When the amount is 2.5 equivalents or less, the yield per reaction batch does not decrease and the production efficiency is good.

  The reaction may be carried out by adding a hydrocarbon solvent. Examples of hydrocarbon solvents include those having a boiling point of 60 ° C. or higher, specifically n-hexane (boiling point: about 69 ° C.), cyclohexane (boiling point: about 81 ° C.), n-heptane (boiling point: about 98 ° C.). , Aliphatic or alicyclic hydrocarbons such as n-octane (boiling point 126 ° C.), and aromatic hydrocarbons such as toluene (boiling point 111 ° C.) and xylene (boiling point about 140 ° C.), preferably n-hexane. Yes, more preferably cyclohexane. The amount of the hydrocarbon solvent is usually 3% by weight or more based on epichlorohydrin. When the amount of the hydrocarbon solvent is less than 3% by weight with respect to epichlorohydrin, a large amount of epichlorohydrin self-condensate is produced.

Examples of the solid alkali metal hydroxide used include solids of sodium hydroxide, potassium hydroxide and lithium hydroxide, preferably potassium hydroxide, more preferably sodium hydroxide.
These solid alkali metal hydroxides may be used alone or as a mixture of two or more. These solid alkali metal hydroxides may be in the form of granules, flakes, or powders. The size is preferably 1 to 5 mm in diameter for granular materials, 0.5 to 3 cm square for flakes, and preferably 30 to 100 μm for powders, but the present invention is not limited thereto. Granularity is preferable for the handling of workers.

The amount of the solid alkali metal hydroxide used is preferably 1.1 to 2.5 equivalents, more preferably 1.3 to 1.9 equivalents, relative to 1 equivalent of the hydroxyl group of the alcohol. When the amount is 1.1 equivalents or more, the generated salt does not adhere to the surface of the solid alkali and the activity of the alkali surface does not decrease, so that the reaction proceeds efficiently. If the amount is 2.5 equivalents or less, the product is not colored.

Reaction temperature is 40 degrees C or less normally, Preferably it is 10-40 degreeC, More preferably, it is 20-30 degreeC. If it exceeds 40 ° C., a side reaction between the produced glycidyl ether and epichlorohydrin tends to occur.
The reaction time is preferably 10 to 30 hours, more preferably 12 to 20 hours. When the reaction time is 10 hours or longer, the reaction rate does not decrease. When the reaction time is 30 hours or shorter, the side reaction between the produced glycidyl ether and epichlorohydrin hardly occurs.

  The reaction is preferably carried out under an inert gas atmosphere such as nitrogen (oxygen concentration: preferably 1,000 ppm or less), and when the solid alkali metal hydroxide is introduced, it is placed in a sealed container directly connected to the reaction container. It is preferable to put solid alkali hydroxide into an inert gas atmosphere and gradually add it to the reaction vessel.

  The order of mixing and adding alcohols, epichlorohydrin, solid alkali metal hydroxide, and hydrocarbon solvent may be mixed with alcohols and hydrocarbon solvent, and the solid alkali metal hydroxide and epichlorohydrin may be mixed and charged simultaneously. Alternatively, a mixture of a hydrocarbon solvent and epichrome and a solid alkali metal hydroxide may be mixed and added to the alcohols at the same time. Preferred is a method in which alcohols, epichlorohydrin and hydrocarbon solvent are mixed, and finally a solid alkali metal hydroxide is mixed and charged. Finally, when solid alkali metal hydroxide is mixed and charged, it is preferable that coloring does not occur.

Although the reaction is carried out in the presence of a solid alkali metal hydroxide, it is preferable to use a freshly pulverized solid.
As a pulverizing device for pulverizing the solid alkali metal hydroxide, devices such as a pulverizer, a mixer and a homogenizer can be used. Examples of crushers and mixers include cone mills, roll crushers, screw crushers, edge runners, ring roll mills, rod mills, ball mills, impact fine crushers, jet crushers, tower type grinders, colloid mills, screw mixers, etc. Is mentioned. Examples of the homogenizer include a Potter LB homogenizer, an Atterworkman homogenizer, and a Waring blender.
As a pulverization method in this case, a pulverization device is installed outside the reaction vessel, and the reaction mixture is circulated from the reaction vessel through the pulverization device; a pulverization device is installed in the reaction vessel, and the reaction mixture is pulverized; Examples thereof include a method in which a pulverizing device is installed and the reaction mixture is continuously pulverized, and a method in which a plurality of pulverizing devices are installed and the reaction mixture is continuously pulverized is preferable. As an example of the wet pulverizer, for example, a commercially available Komatsu dice integrator (manufactured by Komatsu Zenoa Co., Ltd.) can be used.
The shape of the pulverized product pulverized by the pulverizing device is powdery, and the size is preferably several μm to 20 μm.

  Water of 40 ° C. or lower, preferably 10 to 40 ° C., is usually added to the reaction mixture after the reaction to dissolve and separate excess alkali metal hydroxide and product salt. After separation, an alkali adsorbent is added to the organic layer, and epichlorohydrin, hydrocarbon solvent, water and alcohols are distilled off together preferably at 70 to 120 ° C. under reduced pressure (preferably −85 KPaG or less), followed by filtration. By doing so, a high purity aliphatic glycidyl ether can be obtained.

  When water is added to the reaction mixture to dissolve the excess alkali metal hydroxide and the generated salt, a self-condensate of glycidyl ether is hardly generated when the temperature of the water is 40 ° C. or lower.

  Examples of the alkali adsorbent to be added to the organic layer after the liquid separation include synthetic magnesium silicate (for example, “KYOWARD 600” manufactured by Kyowa Chemical Industry Co., Ltd.), synthetic aluminum silicate (for example, “KYOWARD 700”: the same as above), Hydrotalcites (for example, “Kyoward 2000”: the same as above), activated clay (for example, “Galeon Earth”: the same as above)), and the like, preferably synthetic magnesium silicate. A diatomaceous earth filter aid (for example, “Radiolite”: the same as above) may be used together with these adsorbents. The addition amount of the alkali adsorbent is preferably 0.1 to 2.0% by weight with respect to the organic layer after the liquid separation.

  The temperature for distilling epichlorohydrin, hydrocarbon solvent, water and alcohols is preferably 70 to 120 ° C, more preferably 90 to 115 ° C. When the distillation temperature is 70 ° C. or higher, a practical distillation rate can be obtained, and when it is 120 ° C. or lower, the distillation of the epichloro self-condensate formed in the reaction system can be suppressed, so that it can be recycled. . The pressure is preferably −85 KPaG or less, more preferably −95 KPaG or less. When it is −85 KPaG or less, a practical distillation rate can be obtained.

For the reaction with epichlorohydrin, a known phase transfer catalyst may be used if necessary.
Preferred examples of the phase transfer catalyst include quaternary ammonium salts, quaternary phosphonium salts, quaternary arsonium salts, and the like, and more preferably quaternary ammonium salts. Examples of the quaternary ammonium salt include tetramethylammonium chloride, benzyltrimethylammonium chloride, benzyltriethylammonium chloride, benzyltributylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium hydrosulfate, trioctylammonium chloride, n-laurylpyridinium chloride. Etc. are included. The quaternary phosphonium salt includes, for example, tetraethylphosphonium chloride, dimethyldicyclohexylphosphonium bromide, and triphenylmethylphosphonium iodide. Quaternary arsonium salts include, for example, tetramethylarsonium chloride, tetraethylarsonium bromide, and tetraethylarsonium hydroxide.
When the phase transfer catalyst is added to the reaction system of the present invention, the amount added is preferably 0.5% by weight or less, more preferably 0.2% by weight or less, particularly preferably based on the alcohol. 0.1% by weight or less. When 0.5 wt% or less is used, epichlorohydrin self-condensate can be suppressed and a practical reaction rate can be obtained.
There is no particular limitation on the mixing method and timing, but it is preferable to add before the reaction.

The reactive diluent (B) of the present invention contains the epoxy compound (A) as an essential component.
Although only the epoxy compound (A) can be used as the reactive diluent (B), other components such as an organic solvent may be contained as necessary within a range not causing an adverse effect.

  Another thermosetting epoxy resin composition according to the present invention comprises the above-described reactive diluent for epoxy resin (B), epoxy resin (C), and curing agent (D).

  Examples of the epoxy resin (C) include glycidyl ether type epoxide (C1), glycidyl ester type epoxide (C2), glycidylamine type epoxide (C3), and alicyclic epoxide (C4).

Examples of the glycidyl ether type epoxide (C1) include glycidyl ether of dihydric phenol, glycidyl ether of polyhydric phenol, glycidyl ether of dihydric alcohol, and glycidyl ether of polyhydric alcohol.
Examples of the glycidyl ether of dihydric phenol include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, and bisphenol S diglycidyl ether.
Examples of the glycidyl ether of polyhydric phenol include dihydroxynaphthyl cresol triglycidyl ether, tris (hydroxyphenyl) methane triglycidyl ether and dinaphthyltriol triglycidyl ether, phenol novolac glycidyl ether, cresol novolac glycidyl ether and the like.
Examples of the glycidyl ether of dihydric alcohol include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol [weight average molecular weight (hereinafter, Mw): 150-4,000] diglycidyl ether and polypropylene glycol (Mw: 180-5,000) diglycidyl ether.
Examples of the glycidyl ether of polyhydric alcohol include trimethylolpropane triglycidyl ether, glycerin triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol hexaglycidyl ether, and poly (degree of polymerization 2 to 5) glycerin polyglycidyl ether.

As the glycidyl ester type epoxide (C2), glycidyl ester of carboxylic acid, glycidyl ester type polyepoxide and the like are used.
Examples of the glycidyl ester of carboxylic acid include glycidyl methacrylate, diglycidyl phthalate, diglycidyl isophthalate, diglycidyl terephthalate, and triglycidyl trimellitic acid.

As the glycidylamine type epoxide (C3), glycidyl aromatic amine, glycidyl alicyclic amine, glycidyl heterocyclic amine and the like are used.
Examples of glycidyl aromatic amines include N, N-diglycidylaniline, N, N-diglycidyltoluidine, N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl. Examples include diaminodiphenyl sulfone and N, N, N ′, N′-tetraglycidyl diethyldiphenylmethane.
Examples of glycidyl alicyclic amines include bis (N, N-diglycidylaminocyclohexyl) methane (hydrogenated compound of N, N, N ′, N′-tetraglycidyldiaminodiphenylmethane) and N, N, N ′, N ′. -Tetraglycidyl dimethylcyclohexylenediamine (hydrogenated compound of N, N, N ', N'-tetraglycidylxylylenediamine) and the like.
Examples of the glycidyl heterocyclic amine include trisglycidylmelamine and N-glycidyl-4-glycidyloxypyrrolidone.

  Alicyclic epoxides (C4) include vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, bis (2,3-epoxycyclopentyl) ether, ethylene glycol bisepoxy dicyclopentyl ether and 3,4-epoxy- Examples include 6-methylcyclohexylmethyl-3 ′, 4′-epoxy-6′-methylcyclohexanecarboxylate.

  Among these epoxy resins, glycidyl ether type epoxides, glycidyl ester type epoxides and glycidyl amine type epoxides are preferable from the viewpoint of price and heat resistance, and glycidyl ether type epoxides and glycidyl ester type epoxides are more preferable. These epoxy resins may be used alone or in combination of two or more selected from these.

The curing agent (D) used in the present invention is not particularly limited as long as it can cure the epoxy resin.
Examples of such curing agents include polyfunctional phenols, amines, imidazole compounds, acid anhydrides, organic phosphorus compounds and their halides, polyamides, polysulfides, boron trifluoride, and the like.

  Examples of polyfunctional phenols include hydroquinone, resorcinol, catechol, monocyclic bifunctional phenols, bisphenol A, bisphenol F, bisphenol S, naphthalenediols, biphenols, and halides thereof. And alkyl group-substituted products. Moreover, phenol resins such as phenol novolac resins, resol resins, bisphenol A novolac resins and cresol novolac resins, which are polycondensates of these phenols and aldehydes.

  Examples of amines include aliphatic or aromatic primary amines, secondary amines, tertiary amines, quaternary ammonium salts and aliphatic cyclic amines, guanidines, urea derivatives, and the like.

  Examples of imidazole compounds include imidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, 2- Heptadecylimidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-isopropylimidazole, 2,4-dimethylimidazole, 2-phenyl-4 -Methylimidazole, 2-ethylimidazoline, 2-phenyl-4-methylimidazoline, benzimidazole, 1-cyanoethylimidazole and the like.

  Examples of the acid anhydride include phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, and the like.

  The organic phosphorus compound is not particularly limited as long as it is a phosphorus compound having an organic group. For example, hexamethylphosphoric triamide, tri (dichloropropyl) phosphate, tri (chloropropyl) phosphate, phosphorous acid Examples include triphenyl, trimethyl phosphate, phenylphosphonic acid, triphenylphosphine, tri-n-butylphosphine, diphenylphosphine, and the like.

  These curing agents can be used alone or in combination.

  Moreover, the thermosetting epoxy resin composition of the present invention is necessary in addition to the reactive diluent (B), epoxy resin (C), and curing agent (D) of the present invention as long as the characteristics are not impaired. Depending on fillers, mold release agents, surface treatment agents, flame retardants, viscosity modifiers, plasticizers, antifungal agents, leveling agents, antifoaming agents, coloring agents, anti-coloring agents, antioxidants, stabilizers, cups You may mix | blend a ring agent etc.

The method for producing the thermosetting epoxy resin composition of the present invention is not particularly limited as long as it can mix and disperse the materials used, and examples thereof include the following methods.
(I) Knead by hand with a stir bar, spatula, etc. in a suitable container such as a glass beaker, can, or plastic cup.
(Ii) Kneading with a double helical ribbon blade, a gate blade or the like.
(Iii) Kneading with a planetary mixer.
(Iv) Kneading with a bead mill.
(V) Kneading with three rolls.
(Vi) Kneading with an extruder-type kneading extruder.

  The thermosetting epoxy resin composition of the present invention comprises a paint (heavy anticorrosion paint, anticorrosion coating agent, coating for flooring, exterior paint, automotive (electrodeposition) paint, powder paint, primer, etc.), adhesive (Structural adhesives, elastic adhesives, solvent-type reactive adhesives, adhesives, pressure sensitive adhesives, etc.), sealants (architectural sealants, automotive sealants, etc.), casting agents (repair injections for concrete) , Casting insulating materials, etc.), sealing agents (semiconductor sealing agents, repair putty, etc.), casting / molding materials (matrix resins for laminates such as fiber reinforced laminates, interlayer insulation materials, etching resist materials, Plating resist, solder resist, etc.), and other resins used for impregnation, casting, molding, and the like.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1
66 parts of phenol and 150 parts of toluene were charged into a flask, which was kept at 80 ° C., and 3 parts of boron trifluoride was added. Next, 200 parts of styrene was added dropwise at 80 ° C. with stirring and reacted for 2 hours. After completion of the reaction, water was added to quench the catalyst. Thereafter, a condenser was attached to the flask, and distillation was started at normal pressure. After distillation of toluene, unreacted phenol was recovered to obtain 263 parts of styrenated phenol (a-1) remaining in the flask. The molecular weight of (a-1) was 380 in terms of hydroxyl value.

  In a 2-liter stainless steel autoclave with stirring and temperature control function, which was previously dried in a thermostat at 150 ° C. for 8 hours, 609 parts of the styrenated phenol (a-1) and 2.0 parts of 45% aqueous potassium hydroxide solution were added. And the inside of the mixed system was replaced with nitrogen. The oxygen concentration at this time was 50 ppm. Thereafter, dehydration was performed at 100 ° C. for 2 hours under reduced pressure (1 to 5 mmHg). The moisture at this time was 200 ppm. Subsequently, 391 parts of propylene oxide (hereinafter abbreviated as PO) was introduced so that the gauge pressure would be 1 to 3 kgf / cm <2> to obtain a styrenated phenol alkylene oxide adduct (b-1). The molecular weight of (b-1) was 632 in terms of hydroxyl value.

  Into a reaction vessel equipped with a stirrer, temperature control measures, and a wet pulverizer (attached to the outside of the reaction vessel), 917 parts of the styrenated phenol PO adduct (b-1), 269 parts of epichlorohydrin, and 250 parts of toluene were charged. Then, the inside of the reaction vessel was placed in a nitrogen atmosphere (oxygen concentration: 730 ppm), and 116 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. was dropped intermittently at 19-29 ° C. over 9.5 hours. The sodium hydroxide is pulverized using a wet pulverizer. Thereafter, the reaction was aged at 25 to 29 ° C. for 5 hours to glycidyl etherify (b-1). The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening.

 After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was filtered and circulated using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A-1). The epoxy equivalent was 765.

Production Example 2
In a 2 liter stainless steel autoclave with stirring and temperature control function, which was previously dried in a thermostat at 150 ° C. for 8 hours, 673 parts of styrenated phenols (a-1) and 2.0 parts of 45% aqueous potassium hydroxide solution were added. The mixed system was replaced with nitrogen. The oxygen concentration at this time was 50 ppm. Thereafter, dehydration was performed at 100 ° C. for 2 hours under reduced pressure (1 to 5 mmHg). The moisture at this time was 200 ppm. Next, 327 parts of ethylene oxide (hereinafter abbreviated as EO) was introduced so that the gauge pressure was 1 to 3 kgf / cm <2> to obtain a styrenated phenol alkylene oxide adduct (b-2). The molecular weight of (b-2) was 573 in terms of hydroxyl value.

  Next, 910 parts of the styrenated phenol EO adduct (b-2), 294 parts of epichlorohydrin, and toluene 250 were added to a reaction tank equipped with a stirrer, a temperature control measure, and a wet pulverizer (attached to the outside of the reaction tank). Part of the reaction vessel was placed in a nitrogen atmosphere (oxygen concentration: 730 ppm), and 127 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. was dropped intermittently at 19-29 ° C. over 9.5 hours. Sodium hydroxide in the reaction vessel is pulverized using a wet pulverizer. Thereafter, the reaction was aged at 25 to 29 ° C. for 5 hours to glycidyl etherify (b-2). The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was filtered and circulated using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A-2). The epoxy equivalent was 699.

Production Example 3
233 parts of cumylphenol and 150 parts of toluene were charged into a flask, which was kept at 80 ° C., and 3 parts of boron trifluoride was added. Next, 200 parts of styrene was added dropwise at 80 ° C. with stirring and reacted for 2 hours. After completion of the reaction, water was added to quench the catalyst. Thereafter, a condenser was attached to the flask, and distillation was started at normal pressure. After distillation of toluene, unreacted phenol was recovered to obtain 430 parts of styrenated cumylphenol (a-2) remaining in the flask. The molecular weight of (a-2) was 390 in terms of hydroxyl value.

  Into a 2 liter stainless steel autoclave with stirring and temperature control function, which was previously dried in a thermostatic bath at 150 ° C. for 8 hours, 615 parts of the styrenated cumylphenol (a-2) and 45% aqueous potassium hydroxide solution 2. 0 parts was added and the inside of the mixed system was replaced with nitrogen. The oxygen concentration at this time was 50 ppm. Thereafter, dehydration was performed at 100 ° C. for 2 hours under reduced pressure (1 to 5 mmHg). The moisture at this time was 200 ppm. Subsequently, 385 parts of propylene oxide (hereinafter abbreviated as PO) was introduced so that the gauge pressure was 1 to 3 kgf / cm <2> to obtain a styrenated cumylphenol alkylene oxide adduct (b-3). The molecular weight of (b-3) was 634 in terms of hydroxyl value.

  920 parts of styrenated cumylphenol propylene oxide adduct (b-3), 269 parts of epichlorohydrin, 250 parts of toluene are added to a reaction tank equipped with a stirrer, temperature control measures, and a wet pulverizer (attached to the outside of the reaction tank). The reaction vessel was charged with a nitrogen atmosphere (oxygen concentration: 730 ppm), and 116 parts of granular sodium hydroxide under a nitrogen atmosphere at 19 ° C. was dropped intermittently at 19-29 ° C. over 9.5 hours. The inside sodium hydroxide is pulverized using a wet pulverizer. Thereafter, the reaction was aged at 25 to 29 ° C. for 5 hours to glycidyl etherify (b-3). The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was filtered and circulated using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A-3). The epoxy equivalent was 768.

Production Example 4
103 parts of phenol and 150 parts of toluene were charged into a flask, which was kept at 80 ° C., and 3 parts of boron trifluoride was added. Next, 200 parts of styrene was added dropwise at 80 ° C. with stirring and reacted for 2 hours. After completion of the reaction, water was added to quench the catalyst. Thereafter, a condenser was attached to the flask, and distillation was started at normal pressure. After the distillation of toluene, unreacted phenol was recovered to obtain 300 parts of styrenated phenol (a-3) remaining in the flask. The molecular weight of (a-3) was 274 in terms of hydroxyl value.

  529 parts of styrenated phenol (a-3) and 2.0 parts of 45% aqueous potassium hydroxide solution are put into a 2 liter stainless steel autoclave with stirring and temperature control function that has been dried in a constant temperature bath at 150 ° C. for 8 hours in advance. The inside of the mixed system was replaced with nitrogen. The oxygen concentration at this time was 50 ppm. Thereafter, dehydration was performed at 100 ° C. for 2 hours under reduced pressure (1 to 5 mmHg). The moisture at this time was 200 ppm. Subsequently, 471 parts of propylene oxide (hereinafter abbreviated as PO) was introduced so that the gauge pressure was 1 to 3 kgf / cm <2> to obtain a styrenated phenol alkylene oxide adduct (b-4). The molecular weight of (b-4) was 510 in terms of hydroxyl value.

  In a reaction vessel equipped with a stirrer, a temperature control measure, a wet pulverizer (attached to the outside of the reaction vessel), 900 parts of a styrenated phenolpropylene oxide adduct (b-4), 326 parts of epichlorohydrin, 250 parts of toluene are charged. The inside of the reaction vessel was placed in a nitrogen atmosphere (oxygen concentration: 730 ppm), and 141 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. was dropped intermittently at 19-29 ° C. over 9.5 hours. Sodium hydroxide is pulverized using a wet pulverizer. Thereafter, the reaction was aged at 25 to 29 ° C. for 5 hours to glycidyl etherify (b-4). The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was filtered and circulated using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A-4). The epoxy equivalent was 630.

Comparative production example 1
777 parts of higher alcohol (carbon number 12 / carbon number 13 = 10/90 mol%, side chain ratio 87%) in a reaction tank equipped with a stirrer, temperature control measures, and a wet pulverizer (attached to the outside of the reaction tank) , 724 parts of epichlorohydrin and 500 parts of toluene were prepared, the inside of the reaction vessel was placed in a nitrogen atmosphere (oxygen concentration: 730 ppm), and 313 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. was taken at 19-29 ° C. over 30 hours. During this period, the sodium hydroxide in the reaction vessel is pulverized using a wet pulverizer. Thereafter, the reaction was aged at 25-29 ° C. for 5 hours to glycidyl etherize the higher alcohol. The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was subjected to filtration circulation using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A′-1). The epoxy equivalent was 284.

Comparative production example 2
A reaction vessel equipped with a stirrer, a temperature control measure, and a wet pulverizer (attached to the outside of the reaction vessel) was charged with 870 parts of the styrenated phenol (a-1), 423 parts of epichlorohydrin, and 350 parts of toluene. The inside was placed in a nitrogen atmosphere (oxygen concentration: 730 ppm), and 183 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. was dropped intermittently at 19-29 ° C. over 15 hours. During this period, sodium hydroxide in the reaction vessel was Grind using a wet grinder. Thereafter, reaction aging was performed at 25 to 29 ° C. for 5 hours, and styrenated phenol (a-1) was glycidyl etherified. The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was subjected to filtration circulation using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A′-2). The epoxy equivalent was 486.

Comparative production example 3
In a 2 liter stainless steel autoclave with stirring and temperature control function, which was previously dried in a thermostat at 150 ° C. for 8 hours, 100 parts of the styrenated phenol (a-1) and 2.0 parts of 45% aqueous potassium hydroxide solution were added. And the inside of the mixed system was replaced with nitrogen. The oxygen concentration at this time was 50 ppm. Thereafter, dehydration was performed at 100 ° C. for 2 hours under reduced pressure (1 to 5 mmHg). The moisture at this time was 200 ppm. Subsequently, 900 parts of propylene oxide (hereinafter abbreviated as PO) was introduced so that the gauge pressure was 1 to 3 kgf / cm <2> to obtain a styrenated phenol alkylene oxide adduct (b-5). The molecular weight of (b-5) was 3700 in terms of hydroxyl value.

(B-5) 985 parts, epichlorohydrin 50 parts, toluene 250 parts were charged in a reaction tank equipped with a stirrer, temperature control measures, and a wet pulverizer (attached to the outside of the reaction tank), and the inside of the reaction tank was in a nitrogen atmosphere. (Oxygen concentration: 730 ppm), 22 parts of granular sodium hydroxide in a nitrogen atmosphere at 19 ° C. is dropped intermittently at 19-29 ° C. over 4 hours. During this time, the sodium hydroxide in the reaction vessel uses a wet pulverizer. And pulverize. Thereafter, the reaction was aged at 25 to 29 ° C. for 5 hours to glycidyl etherify (b-5). The wet pulverizer was operated continuously from the start of dropping sodium hydroxide to the end of reaction ripening. After cooling the inside of the tank to 16 ° C., 200 parts of 23 ° C. water was added in the range of 20 to 28 ° C., stirred for 0.5 hours, and allowed to stand at 17 ° C. for 0.5 hours. 10 parts of “KYOWARD 600” (manufactured by Kyowa Chemical Industry Co., Ltd .; alkali adsorbent) was added to the remaining upper layer (organic layer), the temperature was increased under reduced pressure, and the mixture of epichlorohydrin and toluene was increased to 120 ° C. and −98.0 KPaG. The residue was subjected to filtration circulation using “Radiolite # 700” (manufactured by Kyowa Chemical Industry Co., Ltd .; diatomaceous earth filter aid) to obtain glycidyl ether (A′-3). The epoxy equivalent was 4175.

Examples 1-4, Comparative Examples 1-3
The glycidyl ethers (A-1) to (A-4) and (A′-1) to (A′-3) themselves obtained in the above Production Examples 1 to 4 and Comparative Production Examples 1 to 3, respectively, are reactive. Dilution performance when used as diluents (B-1) to (B-4) and (B′-1) to (B′-3) was evaluated by the following method. The results are summarized in Table 1.

<Evaluation method of dilution performance>
Epicoat 828 (trade name, manufactured by Japan Epoxy Resin Co., Ltd., bisphenol A type epoxy resin, epoxy equivalent 190) has a dilution viscosity at 25 ° C. of 1000 Pa · s {B-type viscometer (No. 3 spindle, rotation speed 60 rpm)} In order to make it, it evaluated in the number of addition parts required.
Dilution performance (%) = (number of parts of reactive diluent) ÷ {(number of parts of Epicoat 828) + (number of parts of reactive diluent)}
The viscosity at 25 ° C. of Epicoat 828 itself used at this time was 12,000 mPa · s. The viscosity was measured with a B-type viscometer (No. 4 spindle, rotation speed 30 rpm) according to JIS K 7117-1 (1999).

  Furthermore, as Examples 1 to 4 and Comparative Examples 1 to 3, the hardness (Shore D) and glass transition temperature of the cured products obtained by blending at the weight ratios described in Table 1 and curing under the following conditions were measured. The flexibility and heat resistance were evaluated.

Triethylenetetramine as a curing agent was added to the blend diluted with Epicoat 828 and adjusted to a viscosity of 1000 mPa · s, mixed well, cured at room temperature for 2 days, and cured at 100 ° C. for 2 hours.
The cured product characteristics were evaluated by hardness (Shore D) and glass transition temperature, and the results are shown in Table 1.

<Flexibility evaluation method>
The hardness (Shore D) was measured according to ASTM D-2240 to evaluate flexibility.

<Method for evaluating heat resistance>
The glass transition temperature is measured using a differential scanning calorimeter (RDC-220, manufactured by SII Nanotechnology Co., Ltd.) at a temperature range of 30 ° C. to 350 ° C. at a rate of temperature increase of 10 ° C./min. The glass transition temperature (° C) was measured for the points, and the heat resistance was evaluated.

From the measurement results of hardness (Shore D) and glass transition temperature, Examples 1 to 4 are both compatible with flexibility and heat resistance.
On the other hand, Comparative Example 1 and Comparative Example 3 are excellent in flexibility but lack heat resistance, and Comparative Example 2 is excellent in heat resistance but lacks flexibility.

  The reactive diluent for epoxy resin of the present invention satisfies both flexibility and heat resistance while maintaining dilution performance. Due to its excellent characteristics, it is a paint, adhesive, sealant, casting It is useful as a thermosetting epoxy resin for civil engineering / architecture, electrical / electronic parts, and transportation equipment such as adhesives, laminates, and sealants.

Claims (10)

A reactive diluent (B) for an epoxy resin comprising an epoxy compound (A) represented by the following general formula (1) as an essential component.

[In Formula (1), R < ¹ >, R < ² > is a hydrogen atom or a methyl group each independently, and does not become a hydrogen atom simultaneously ; R < ³ > is a hydrogen atom, a C1-C16 alkyl group, a phenyl group Or a phenylalkyl group having 7 to 12 carbon atoms; R ⁴ O represents an oxyalkylene group having 2 to 4 carbon atoms. m is a number from 1 to 3, and n is a number from 1 to 50. ]   The reactive diluent for an epoxy resin according to claim 1, wherein the epoxy compound (A) is a glycidyl ether of an alkylene oxide adduct of styrenated phenol.   N in Formula (1) is 1-20, The reactive diluent for epoxy resins of Claim 1 or 2.   A thermosetting epoxy resin composition comprising the reactive diluent for epoxy resin (B) according to claim 1, an epoxy resin (C), and a curing agent (D).   The coating film which consists of a thermosetting epoxy resin composition of Claim 4.   An adhesive comprising the thermosetting epoxy resin composition according to claim 4.   A sealant comprising the thermosetting epoxy resin composition according to claim 4.   A casting agent comprising the thermosetting epoxy resin composition according to claim 4.   The sealing agent which consists of a thermosetting epoxy resin composition of Claim 4.   A cast product or a molded product obtained by curing the thermosetting epoxy resin composition according to claim 4.